TW201345987A - Near infrared absorptive liquid composition, near infrared cut filter using the same, and camera module and method of manufacturing the same - Google Patents

Abstract

Provided is a near infrared absorptive liquid composition which may be formed into a layer by coating, and is excellent in near infrared shielding performance. A near infrared absorptive liquid composition comprising a copper compound, a compound having a polymerizable group, and 50 to 80% by mass of a solvent.

Description

Near-infrared light absorbing liquid composition, near-infrared optical cut filter using the same, manufacturing method thereof, and photographic module and manufacturing method thereof

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

In recent years, CCD and CMOS image sensors have been used as solid-state image sensing devices for color imaging, which can be incorporated into video cameras, digital still cameras, and camera phones with camera functions. These solid-state image sensing devices use a sensitive photodiode in the near-infrared region in their light-receiving sections, thus requiring luminosity correction. Near-infrared optical cut-off filters are commonly used for this purpose.

The near-infrared light absorbing composition is known as a material constituting such a near-infrared light cut filter (Patent Document 1). According to Patent Document 1, a near-infrared light absorbing composition The layer is usually formed by vacuum evaporation to form a near-infrared light shielding layer. However, there is a need for a near-infrared light absorbing liquid composition which can be formed into a film by coating.

Reference list [Patent Literature]

[Patent Document 1] International Patent WO99/26952, Single Line (Pamphlet)

The present invention has been conceived to solve the above problems, and an object thereof is to provide a near-infrared light absorbing liquid composition which can be formed into a layer by coating and has excellent near-infrared light shielding performance.

Under these circumstances, the inventors have found by a large number of studies that the problem can be solved by using a copper phosphate compound as a near-infrared light absorber. More specifically, the problem can be solved by the following configuration <1>, preferably from configuration <2> to configuration <16>.

<1> A near-infrared light absorbing composition comprising a copper compound, a compound having a polymerizable group, and 50% by mass to 80% by mass of a solvent.

<2> The near-infrared light absorbing composition according to <1>, wherein the copper compound is a copper compound containing phosphorus or a copper sulfonate compound.

<3> The near-infrared light absorbing composition according to <1>, wherein the copper compound is a copper phosphate compound.

The near-infrared light absorbing liquid composition according to any one of <1> to <3> wherein the compound having a polymerizable group is a polyfunctional monomer.

The near-infrared light absorbing liquid composition according to any one of <1> to <4> wherein the compound having a polymerizable group is represented by the following formula (MO-1) to (MO- 5) Any of the polymerizable monomers represented by:

(In the formula, n represents 0 to 14, respectively, and m represents 1 to 8. Each of a plurality of R, T, and Z in a single molecule may be the same or different, respectively. When T represents an alkylene group, The carbon end is bonded to R. At least one R is a polymerizable group.)

The near-infrared light absorbing liquid composition according to any one of <1> to <4> wherein the compound having a polymerizable group has a polymerizable group in a side chain thereof.

The near-infrared light absorbing liquid composition according to any one of <1> to <6>, further comprising a polymerization initiator.

The near-infrared light absorbing liquid composition according to any one of <3>, wherein the copper phosphate compound is formed using a compound represented by the following formula (1): (1) (HO) ) _n -P(=O)-(OR ² _)3-n

(In the formula, R ² represents C _1-18 alkyl, C _6-18 aryl, C _1-18 aralkyl or C _1-18 alkenyl, or -OR ² represents C _4-100 polyoxyl Alkyl, C _4-100 (meth) propylene decyloxyalkyl or C _4-100 (meth) acryl decyl polyoxyalkyl, and n represents 1 or 2.)

<9> The near-infrared light absorbing liquid composition according to <8>, wherein in the formula (1), -OR ² represents C _4-100 (meth) propylene decyloxyalkyl group or C _{4- 100} (meth)acryloyl fluorenyl polyoxyalkyl.

The near-infrared light absorbing liquid composition according to any one of <1> to <9> wherein the compound having a polymerizable group contains a (meth) acryloxy group.

The near-infrared light absorbing liquid composition according to any one of <1> to <10>, which is used in the form of a film applied to an image sensor of a solid-state image sensing device.

<12> A near-infrared light-cutting filter which is produced by using the near-infrared light absorbing liquid composition according to any one of <1> to <11>.

<13> A camera module comprising a solid-state image sensing device substrate and a near-infrared light cut filter disposed in <12> on a light receiving side of the solid-state image sensing device substrate.

<14> A method of manufacturing a camera module, comprising: a solid-state image sensing device substrate; and a near-infrared optical cut filter disposed on a light receiving side of the solid-state image sensing device substrate, the method comprising : A film is formed by coating the near-infrared light absorbing liquid composition according to any one of <1> to <11> on the light-receiving side of the substrate of the solid-state image sensing device.

<15> The method of manufacturing a camera module according to <14>, wherein the film is formed on a microlens on a light receiving side of the solid-state image sensing device substrate.

<16> The method of manufacturing a photographic module according to <14> or <15>, which comprises curing a film formed by coating the composition of the infrared absorbing liquid by irradiation with light.

With the present invention, it is now possible to form a near-infrared light absorbing layer by coating.

10‧‧‧矽 substrate

12‧‧‧Image sensing device

13‧‧‧Insulation interlayer

14‧‧‧ basal layer

15B‧‧‧Blue Filter

15G‧‧‧Green Filter

15R‧‧‧Red Filter

16‧‧‧Overcoat

17‧‧‧Microlens

18‧‧‧Shade film

20‧‧‧Adhesive parts

22‧‧‧Insulation film

23‧‧‧Metal electrodes

24‧‧‧solder layer

26‧‧‧Internal electrodes

27‧‧‧ device surface electrode

30‧‧‧ glass substrate

40‧‧‧Image sensing lens

42‧‧‧Near-infrared cut-off filter

44‧‧‧Light and electromagnetic masks

45‧‧‧Adhesive parts

46‧‧‧Destivation layer

50‧‧‧Lens Holder

60‧‧‧ solder balls

70‧‧‧ circuit board

100‧‧‧Solid image sensing device substrate

200‧‧‧ camera module

1 illustrates a schematic cross-sectional view of a configuration of a camera module having a solid-state image sensing device in accordance with an embodiment of the present invention.

2 illustrates a schematic cross-sectional view of a solid state image sensing device substrate in accordance with the described embodiments of the present invention.

The invention will now be described in detail below. Although the components may be described based on representative embodiments of the invention, the invention is not limited to the representative embodiments. Please note that any numerical range expressed by the word "to" means a range of values that include values that are placed as a lower and upper limit before and after "to".

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acryloyl (meth)acryl" It means acryl and methacryl, and "(meth)acryloyl" means acryloyl and methacryloyl. ). In the case of the present invention, a monomer is distinguished from an oligomer or a polymer, and means a compound having a weight average molecular weight of 2,000 or less. In the present specification, a polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. A polymerizable functional group means a group that participates in a polymerization reaction. Please note that in this manual, there is no "taken" in front. There is no "unsubstituted" term "group (atomic group)" which includes a group having a substituent and a group having no substituent. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group).

In the case of the present invention, near-infrared light radiation means light in the wavelength range of 700 nm to 2500 nm.

Hereinafter, the near-infrared light absorbing composition of the present invention, a near-infrared light cut filter, a camera module having such a near-infrared light cut filter and a substrate of such a solid-state image sensing device, and the manufacture of such a photograph will be described in detail. The method of the module. Although the components are described below based on representative embodiments of the invention, it is not intended to limit the invention to these embodiments.

The near-infrared light absorbing liquid composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention") characteristically contains a copper compound, a compound having a polymerizable group (sometimes referred to as "polymerizable compound"), and 50 Mass% to 80% by mass of solvent. These components will be described in detail below.

<copper compound>

The copper compound used in the present invention is not particularly limited as long as it exhibits a maximum absorption wavelength in the range of from 700 nm to 1000 nm (near-infrared region).

The copper compound used in the present invention may be a copper complex or not a copper complex, of which a copper complex is preferred.

When the copper compound used in the present invention is a copper complex, the ligand L is not particularly limited as long as it can coordinate on the copper ion. Examples of the ligand include a compound having the following: sulfonic acid, phosphoric acid, phosphate, phosphonic acid, phosphonate, phosphinic acid, phosphonite, carboxylic acid, carbonyl (ester, ketone), amine, hydrazine Amine, sulfonamide, amine Formate, urea, alcohol, mercaptan, etc. Among them, sulfonic acid, phosphoric acid, phosphate, phosphonic acid, phosphonate, phosphinic acid and phosphonite are preferred, and sulfonic acid, phosphate, phosphonate and phosphonite are more preferred.

The specific example of the copper compound used in the present invention is preferably a copper compound containing phosphorus, a copper sulfonate compound, a copper carboxylate compound or a copper compound represented by the following formula (A). Phosphorus-containing compounds can be found in the compounds described in column 25, column 27 to page 7, column 20 of WO 2005/030898, the disclosure of which is incorporated herein by reference.

The copper phosphate compound used in the present invention will be described in detail below.

<<Copper phosphate compound>>

The composition of the present invention preferably contains a copper phosphate compound, a polymerizable compound, and a solvent of 50% by mass to 80% by mass.

The composition of the present invention contains a copper phosphate compound, and its content is preferably from 20% by mass to 95% by mass, and more preferably from 30% by mass to 80% by mass based on the solid content of the composition. The copper phosphate compound may be composed of one type or two or more types. When the copper phosphate is composed of two or more kinds, the total content is in the above range.

The copper phosphate compound used in the present invention is preferably formed by using a phosphate compound and more preferably by using a compound represented by the following formula (1): (1)(HO) _n -P(=O)-(OR ² ) _3-n

(In the formula, each R ² represents C _1-18 alkyl, C _6-18 aryl, C _1-18 aralkyl or C _1-18 alkenyl, or each -OR ² represents C _4-100 a polyoxyalkyl group, a C _4-100 (meth) propylene decyloxyalkyl group or a C _4-100 (meth) acryl decyl polyoxyalkyl group, and n represents 1 or 2.

When n is 1, R ² may be the same or different from each other.

In the formula, at least one -OR ² preferably represents C _4-100 (meth) propylene decyloxyalkyl or C _4-100 (meth) acryl decyl polyoxyalkyl, and more preferably C _4-100 (meth)acryloxyalkyl group.

C _4-100 polyoxyalkyl, C _4-100 (meth) propylene decyloxy or C _4-100 (meth) propylene decyl polyoxyalkyl preferably has 4 to 20 carbon atoms, and More preferably, it has 4 to 10 carbon atoms.

In the formula (1), R ^{2 is} preferably a C _1-18 alkyl group or a C _6-18 aryl group, more preferably a C _1-10 alkyl group or a C _6-10 aryl group, more preferably a C _6-10 group. Aryl, and especially phenyl.

In the present invention, when n is 1, one R ² preferably preferably represents C _4-100 (meth) propylene decyloxyalkyl or C _4-100 (meth) acryl decyl polyoxyalkyl. The form of -OR ² is present, and the other R ^{2 is} preferably present in the form of -OR ² or represents an alkyl group.

Examples of the phosphate compound of the present invention are a phosphoric acid monoester (n = 2 in the formula (1)) and a phosphodiester (n = 1 in the formula (1)), wherein near-infrared light shielding effectiveness and solubility From the viewpoint, a phosphodiester is preferred.

The copper phosphate complex exists in the form of a copper complex (copper compound) in which the phosphate is coordinated on the copper as the central metal. The copper in the copper phosphate complex is divalent copper and can be prepared usually by a reaction between a copper salt and a phosphate. Therefore, any near-infrared light absorbing compound (a compound containing copper and a phosphate) is expected to form a copper phosphate complex.

The molecular weight of the copper phosphate compound used in the present invention is preferably from 300 to 1,500, and more preferably from 320 to 900.

Examples of the phosphate compound which is a source of the copper phosphate compound which is preferably used in the present invention will be listed below. Of course, the invention is not limited to the compounds.

In the following table, R ¹ and R ² represent a group in the following formula. In the table below, "*" indicates a bonding site of an oxygen atom in the following formula.

Specific examples of the phosphate compound preferably used in the present invention can be referred to in paragraphs [0041] to [0045] of JP-A-2001-354945 (corresponding U.S. Patent No. 2003/0160217 A1, paragraph [0059]). The description of the patent is incorporated herein by reference.

The synthesis method and preferred examples of the copper phosphate compound used in the present invention can be referred to the disclosure of the International Patent Publication No. WO99/26952, the disclosure of which is incorporated herein by reference.

In the synthesis of copper phosphate compounds, commercially available phosphonic acid products such as Fisimo can be used. (Phosmer) M, Fesimo PE, Fesimo PP (from Unichemical Co. Ltd.).

<<Other copper compounds>>

In addition to the above copper compound containing phosphorus, the following copper compound having a carboxylate ligand can also be used as the copper compound usable in the present invention. Of course, the invention is not limited to the compounds. In the following table, R ¹ represents the formula of R ^1. In the table, "*" indicates a bonding site of a COOH group in the following formula.

The copper compound used in the present invention may also be a compound represented by the following formula (A): Cu(L) _n1 ‧ (X) _n2 (A)

In the formula (A), L represents a ligand which can coordinate on copper, and X does not exist or represents a halogen atom, H ₂ O, NO ₃ , ClO ₄ , SO ₄ , CN, SCN, BF ₄ , PF ₆ , BPh ₄ (Ph represents phenyl) or alcohol. N1 and n2 each independently represent an integer of 1 to 4.

The ligand L has a substituent containing C, N, O or S as an atom capable of coordinating on copper, and more preferably has a group containing N, O or S having a lone pair of electrons thereon. The ligand L is preferably synonymous with the above ligand L. The coordinating group contained in the molecule is not limited to one, and may be two or more than two, and may be in a dissociated form or a non-dissociated form. If the group has a non-dissociated form, then X is absent.

<Compound having a polymerizable group>

The composition of the present invention contains a polymerizable compound. A family of such compounds is widely known in the art and can be used in the present invention without particular limitation. It can have, for example, monomers, oligomers, prepolymers, and any chemical form of the polymer.

The polymerizable compound may be a monofunctional compound or a polyfunctional compound, wherein it is preferably a polyfunctional compound. By containing the polyfunctional compound, the near-infrared light shielding performance and heat resistance of the composition can be further improved. The number of functional groups is preferably from 2 to 8, but is not particularly limited.

<<Polymerizable monomer and polymerizable oligomer>>

A first preferred embodiment of the composition of the present invention contains a monomer having a polymerizable group (polymerizable monomer) or an oligomer having a polymerizable group (polymerizable oligomer) (polymerizable monomer and The polymerized oligomers may hereinafter be collectively referred to as "polymerizable monomers and the like" as polymerizable compounds.

Examples of the polymerizable monomer and the like include an unsaturated carboxylic acid (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) and esters thereof and decylamine, and preferably contain an unsaturated group. An ester formed between a carboxylic acid and an aliphatic polyol compound and a guanamine formed between the unsaturated carboxylic acid and the aliphatic polyvalent amine compound. It is also preferred to use an unsaturated carboxylic acid ester or hydrazine having a nucleophilic substituent such as a hydroxyl group, an amine group or a thiol group. An adduct of an amine with a monofunctional or polyfunctional isocyanate or epoxy compound; and a dehydrated condensation product thereof with a monofunctional or polyfunctional carboxylic acid. It is also preferred to use an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or an adduct of a guanamine with a monofunctional or polyfunctional alcohol, an amine or a thiol; and having a removable substitution A substituted product of an unsaturated carboxylic acid ester such as a halogen group or a tosyloxy group or a guanamine and a monofunctional or polyfunctional alcohol, amine or thiol. Other examples usable herein include compounds obtained by substituting an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like to replace the above unsaturated carboxylic acid.

Specific examples of these compounds are described in paragraphs [0095] to [0108] of JP-A-2009-288705, each of which is also preferably used in the present invention.

The polymerizable monomer or the like is also preferably a compound having at least one addition-polymerizable ethyl group having an ethylenically unsaturated group and exhibiting a boiling point of 100 ° C or higher at normal pressure. Examples thereof include polyfunctional acrylates and methacrylates and mixtures thereof, examples of which are monofunctional acrylates and methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylic acid. An ester and a phenoxyethyl (meth)acrylate; a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then converting to a (meth) acrylate, such as polyethylene glycol (Meth) acrylate, trimethylolethane tri(meth) acrylate, neopentyl glycol di(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate , dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tris(propylene methoxy propyl) ether, tris (propylene) Ethoxyethyl)isocyanurate, glycerin and trimethylolethane; (meth)acrylic acid urethane such as JP-B-S48-41708, JP-B-S50-6034 and JP -A-S51-37193 (meth)acrylic acid urethane; polyester acrylic acid Ester, such as the polyester acrylate described in JP-A-S48-64183, JP-B-S49-43191, and JP-B-S52-30490; and by reacting an epoxy polymer with (meth)acrylic acid The epoxy acrylate obtained.

Other examples include polyfunctional (meth) acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated group, such as glycidyl (meth)acrylate.

Other examples of preferred polymerizable monomers usable herein include compounds having an anthracene ring and two or more ethylenic polymerizable groups, and cardo polymers such as JP-A-2010-160418 A polymerizable monomer described in JP-A-2010-129825, Japanese Patent No. 4,364,216, and the like.

As a compound having an ethylenically unsaturated group and exhibiting a boiling point of 100 ° C or higher at normal pressure, the compound described in paragraphs [0254] to [0257] of JP-A-2008-292970 also It is better.

A compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then converting it into a (meth) acrylate may also be used as a polymerizable monomer, such as from the formula (1) and formula (2). ) A compound which is specifically listed in JP-A-H10-62986.

The polymerizable monomer used in the present invention is more preferably a polymerizable monomer represented by the following formula (MO-1) to formula (MO-5): [Chemical Formula 2]

(In the formula, each n represents 0 to 14, and each m represents 1 to 8. A plurality of R, T and Z in a single molecule may each be the same or different from each other. When T represents an alkylene group, The carbon end is bonded to R. At least one R represents a polymerizable group.)

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

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

R preferably represents the following groups: Jia said the following groups:

A specific example of the radical polymerizable monomer represented by the formula (MO-1) to the formula (MO-5) is the one described in paragraphs [0248] to [0251] of JP-A-2007-269779 The body is also preferably used in the present invention.

In particular, the polymerizable monomer or the like is preferably dipentaerythritol triacrylate (purchased from Nippon Kayaku Co., Ltd. by KAYARAD D-330), dipentaerythritol tetraacrylate. Ester (purchased from Nippon Kayaku Co. Ltd. by Kayarad D-320) and dipentaerythritol penta (meth) acrylate (purchased from Nippon Kayak D-310 from Nippon Kayaku) Nippon Kayaku Co. Ltd., dipentaerythritol hexa(meth) acrylate (purchased from Nippon Kayaku Co. Ltd. in Kayad DPHA) or via ethylene glycol Or the structure of these (meth) acryloyl groups bonded by a propylene glycol residue. Oligomer type compounds can also be used.

An example is RP-1040 (from Nippon Kayaku Co. Ltd.).

The polymerizable monomer or the like may also be a polyfunctional monomer, and may have an acid group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group or the like. Thus, any polymerizable monomer having an unreacted carboxyl group (such as in the case where the olefinic compound is a mixture of the above) may be used in its intact form, or, if necessary, the olefinic compound may be made by reacting its hydroxy group with a non-aromatic carboxylic anhydride. The reaction introduces an acid group. Specific examples of non-aromatic carboxylic anhydrides useful herein include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, Succinic anhydride and maleic anhydride.

In the present invention, the monomer having an acid group is an ester formed between an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and preferably by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. a polyfunctional monomer which is introduced into an acid group by reaction, and is especially obtained by using pentaerythritol and/or dipentaerythritol as an aliphatic polyhydroxy compound. The resulting esters. Examples of commercially available polyacid-modified acrylic oligomers include the Aronix series M-305, M-510, and M-520 (from Toagosei Co. Ltd).

The acid value of the polyfunctional monomer having an acid group is preferably from 0.1 mgKOH/g to 40 mgKOH/g, and especially from 5 mgKOH/g to 30 mgKOH/g. If the acid value of the polyfunctional monomer is too small, the solubility in the developing process may be lowered, and if it is too large, manufacturing and handling become difficult, photopolymerization efficiency may be lowered, and curing is characterized by the surface smoothness of the pixel. Performance may be reduced. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination or when a polyfunctional monomer having no acid group is used in combination, it is necessary to adjust the acid value of the entire polyfunctional monomer to keep it at Within the above range.

The composition also preferably contains a polyfunctional monomer having a caprolactone structure as a polymerizable monomer or the like.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule. Examples thereof include a polyfunctional (meth) acrylate modified with ε-caprolactone, which can be obtained by esterifying (meth)acrylic acid and ε-caprolactone with a polyol such as the following: trishydroxymethyl Alkane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol or trimethylol melamine. Among them, a polyfunctional monomer having a caprolactone structure represented by the following formula (1) is preferred.

(In the formula, all or one to five of the six Rs are represented by the following formula (2) The group represented, and the rest represents a group represented by the following formula (3). )

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 or 2, and "*" represents an atomic bond.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and "*" represents an atomic bond.) The polyfunctional monomer having a caprolactone structure can be purchased, for example, under the trade name Kayad DPCA series. Nippon Kayaku Co. Ltd., which contains DPCA-20 (a compound represented by the formula (1) to the formula (3), wherein m=1, the number of groups represented by the formula (2) 2, all R ¹ represents a hydrogen atom), DPCA-30 (in the same formula, m=1, the number of groups represented by the formula (2) is 3, all R ¹ represents a hydrogen atom), DPCA-60 (in the same formula, m=1, the number of groups represented by the formula (2) is 6, all R ¹ represents a hydrogen atom) and DPCA-120 (in the same formula, m=2, from the formula (2) The number of groups represented is 6, and all R ¹ represent a hydrogen atom).

In the present invention, one type of polyfunctional monomer having a caprolactone structure may be used alone or two or more types may be used in a mixed manner.

The polymerizable monomer or the like of 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).

[Chemical Formula 8]

In formula (i) and formula (ii), each E independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, each y independently An integer of 0 to 10 is represented, and each X independently represents an acryloyl group, a methacrylinyl group, a hydrogen atom or a carboxyl group.

In the formula (i), the total number of the acryl fluorenyl group and the methacryl fluorenyl group is 3 or 4, each m independently represents an integer of 0 to 10, and the individual m sum is an integer of 0 to 40. When the sum of individual m is 0, any X represents a carboxyl group.

In the formula (ii), the total number of the acrylonitrile group and the methacryl group is 5 or 6, each n independently represents an integer of 0 to 10, and the individual n sum is an integer of 0 to 60. When the sum of individual n is 0, any X represents a carboxyl group.

In the formula (i), m preferably represents an integer of 0 to 6, and more preferably represents an integer of 0 to 4. The sum of the individual m is preferably an integer of from 2 to 40, more preferably an integer of from 2 to 16, and especially an integer of from 4 to 8.

In the formula (ii), n preferably represents an integer of 0 to 6, and more preferably represents 0 to 4. The sum of the individual n is preferably an integer from 3 to 60, more preferably an integer from 3 to 24, and especially an integer from 6 to 12.

In the formula (i) or (ii), -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- is preferably at the end of the oxygen atom side Combined with X.

A compound represented by the formula (i) or the formula (ii) may be used alone, or two or more of them may be used in combination. In particular, it is preferred that in the formula (ii), six compounds in which X is an acrylonitrile group are preferred.

The compound represented by the formula (i) or the formula (ii) can be synthesized by a publicly known method, such as a method of ring-opening addition polymerization of pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide to combine a ring-opening skeleton. And a method of introducing, for example, (meth)acrylofluorene chloride with a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth)acrylonitrile group. Since individual methods are well known, those skilled in the art will readily synthesize compounds represented by formula (i) or formula (ii).

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

More specifically, examples are compounds represented by the following formulas (a) to (f) (also referred to as "exemplary compound (a) to exemplary compound (f)"), and wherein the exemplary compound (a) The exemplary compound (b), the exemplary compound (e) and the exemplary compound (f) are preferred.

Examples of commercially available polymerizable monomers and the like represented by the formula (i), the formula (ii) include: SR-494 from Sartomer, which is a tetrafunctional having four ethoxylated chains. Acrylate; DPCA-60, which is a hexafunctional acrylate having six pentyloxy chains; and TPA-330, which is a trifunctional acrylate having three isobutoxy chains, both of which are derived from Nippon Kayaku Co. Ltd.

Other preferred examples of the polymerizable monomer and the like include the amine amide group described in JP-B-S48-41708, JP-A-S51-37193, JP-B-H2-32293, and JP-B-H2-16765. An acid group having an ethylene oxide-based skeleton as described in JP-B-S58-49860, JP-B-S56-17654, JP-B-S62-39417, and JP-B-S62-39418 Formate compound. In addition, by using JP-A-S63-277653, An addition polymerizable monomer having an amine structure or a sulfide structure in a molecule as described in JP-A-S63-260909 and JP-A-H01-105238 as a polymerizable monomer, etc. The curable composition is obtained at a high speed.

Examples of commercially available polymerizable monomers and the like include urethane oligomers UAS-10, UAB-140 (from Sanyo-Kokusaku Pulp Co. Ltd.), UA-7200 (from Shin-Nakamura Chemical Co., Ltd., DPHA-40H (from Nippon Kayaku Co. Ltd.), and UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (from Kyoeisha Chemical Co. Ltd.).

A polyfunctional thiol compound having two or more sulfhydryl groups (SH) in the molecule is also preferred as the polymerizable monomer or the like. In particular, a compound represented by the following formula (I) is preferred.

(In the formula, R ¹ represents an alkyl group, R ² represents an aliphatic group having a valence of n, which may contain an atom other than a carbon atom, R ⁰ represents an alkyl group but not H, and n represents 2 to 4 .)

Examples of the polyfunctional thiol compound represented by the formula (I) and the structural formula are 1,4-bis(3-mercaptobutyloxy)butane [formula (II)], 1,3,5-tri (3) - mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione [formula (III)] and pentaerythritol tetrakis(3-mercaptobutyrate) [Formula (IV)]. Only one of these polyfunctional thiols can be used alone, or Two or more of them may be used in combination.

For the composition of the present invention, a polymerizable monomer or oligomer having two or more epoxy groups or oxetanyl groups in the molecule is preferably used as the polymerizable monomer or the like. Specific examples of these compounds are described in the section "Polymers having a polymerizable group in a side chain" hereinafter.

<<Polymers with polymerizable groups in side chains>>

A second preferred embodiment of the composition of the present invention relates to a composition comprising a polymer having a polymerizable group having a side chain as a polymerizable compound.

Examples of the polymerizable group include an ethylenically unsaturated double bond group, an epoxy group, and an oxetanyl group.

<<<Polymers with ethylenically unsaturated bonds in side chains>>>

The polymer having an ethylenically unsaturated bond in the side chain is preferably a polymer having at least one functional group selected from the functional groups represented by the following formulas (1) to (3) as an unsaturated double bond moiety.

In the formula (1), R ¹ to R ³ each independently represent a hydrogen atom or a monovalent organic group. A preferred example of R ¹ is a hydrogen atom or an alkyl group which may have a substituent, and in detail, a hydrogen atom and a methyl group are preferred because of their high radical reactivity. Examples of R ² and R ³ are each independently 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 an aromatic group which may have a substituent. Alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamine group which may have a substituent, an arylamine group which may have a substituent, an alkylsulfonyl group which may have a substituent And an arylsulfonyl group which may have a substituent. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferred because of their high radical reactivity.

X represents an oxygen atom, a sulfur atom or -N(R ¹² )-, and R ¹² represents a hydrogen atom or a monovalent organic group. An example of R ¹² is an alkyl group which may have a substituent, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferred because of their high radical reactivity.

Examples of the substituent which may be introduced herein include 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 arylamino group, a carboxyl group, an alkoxy group. A carbonyl group, a sulfo group, a nitro group, a cyano group, a decylamino group, an alkylsulfonyl group, and an arylsulfonyl group.

[Chemical Formula 14]

In the formula (2), R ⁴ to R ⁸ each independently represent a hydrogen atom or a monovalent organic group. R ⁴ to R ^{8 are} each preferably 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, and may have An aryl group of a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamine group which may have a substituent, an arylamine group which may have a substituent, an alkane which may have a substituent A sulfonyl group and an arylsulfonyl group which may have a substituent. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.

Examples of the substituent which can be introduced here are similar to the substituent in the functional group represented by the formula (1). Y represents an oxygen atom, a sulfur atom or -N(R ¹² )-. R ¹² of formula (1) in the same meaning as R ^12, also goes to apply to their preferred examples.

In the formula (3), a preferred example of R ⁹ is a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom and a methyl group are preferred because of their high radical reactivity. R ¹⁰ and R ¹¹ each independently represent 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, and may have An aryl group of a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamine group which may have a substituent, an arylamine group which may have a substituent, an alkane which may have a substituent A sulfonyl group and an arylsulfonyl group which may have a substituent. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferred because of their high radical reactivity.

Examples of the substituent which can be introduced here are similar to the substituent in the functional group represented by the formula (1). Z represents an oxygen atom, a sulfur atom, -N(R ¹³ )- or a stretched phenyl group which may have a substituent. An example of R ¹³ is an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and an isopropyl group are preferred because of their high radical reactivity.

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

The polymer compound containing a structural unit having a group represented by the formula (1) to the formula (3) can be synthesized based on the method described in paragraphs [0027] to [0057] of JP-A-2003-262958. In the method, the synthesis method 1) described in the patent document is preferably used, which will be described below.

(Polymer having an ethylenically unsaturated bond and an acid group in the side chain)

The polymer having an ethylenically unsaturated bond is preferably a polymer having an acid group.

In the case of the present invention, the acid group is a dissociative group having a pKa of 14 or less, and preferred examples thereof include -COOH, -SO ₃ H, -PO ₃ H ₂ , -OSO ₃ H, -OPO ₂ H ₂ , -PhOH, -SO ₂ H, -SO ₂ NH ₂ , -SO ₂ NHCO-, and -SO ₂ NHSO ₂ -. Among them, -COOH, -SO ₃ H and -PO ₃ H ₂ are preferred, and -COOH is more preferred.

A polymer having an acid group and an ethylenically unsaturated bond in a side chain can be, for example, a carboxylic acid having an ethylenically unsaturated group-containing epoxy compound and a carboxyl group-containing alkali-soluble polymer. Gai is acquired.

The carboxyl group-containing polymer comprises 1) a polymer obtained by radical polymerization or ionic polymerization of a monomer having a carboxyl group, 2) a monomer radical or ionic polymerization containing an acid anhydride, followed by hydrolysis or half esterification of the acid anhydride unit. The obtained polymer, and 3) an epoxy acrylate obtained by modifying an epoxy polymer with an unsaturated monocarboxylic acid and an acid anhydride.

Specific examples of the vinyl group-containing polymer containing a carboxyl group include a homopolymer obtained by polymerization of an unsaturated carboxylic acid such as the following as a monomer having a carboxyl group: (meth)acrylic acid, 2-butyldioxime methacrylate 2-succinoloyloxyethyl methacrylate, 2-malenoloyloxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-hexahydro methacrylate a decyloxyethyl ester, maleic acid, fumaric acid, itaconic acid, and crotonic acid; and copolymerization obtained by polymerizing these unsaturated carboxylic acids with a vinyl monomer such as the following carboxyl group-free : styrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid Butyl ester, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethacrylate, glycidyl ether butyrate, (A) Acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate N-methylol acrylamide, N,N-dimethylpropenylamine, N-methylpropenylmorpholine, N,N-dimethylaminoethyl (meth)acrylate and N,N - Dimethylaminoethyl acrylamide.

Other examples include copolymerization of maleic anhydride with styrene, alpha-methylstyrene or the like and subsequent use of a monohydric alcohol such as methanol, ethanol, propanol, butanol or hydroxyethyl (meth)acrylate Ester) semi-esterified or hydrolyzed maleic anhydride unit And the polymer obtained.

Among them, a polymer containing a carboxyl group and particularly a (meth)acrylic (co)polymer containing (meth)acrylic acid is preferred. Specific examples of such copolymers include methyl methacrylate/methacrylic acid copolymer described in JP-A-S60-208748, methyl methacrylate/methyl acrylate as described in JP-A-S60-214354 /methacrylic acid copolymer, benzyl methacrylate / methyl methacrylate / methacrylic acid / 2-ethylhexyl acrylate copolymer described in JP-A-H5-36581, JP-A-H5 Methyl methacrylate/n-butyl methacrylate/2-ethylhexyl acrylate/methacrylic acid copolymer as described in 333,542, styrene/methacrylic acid described in JP-A-H7-261407 Methyl ester/methyl acrylate/methacrylic acid copolymer, methyl methacrylate/n-butyl acrylate/2-ethylhexyl acrylate/methacrylic acid copolymer described in JP-A-H10-110008, and JP Methyl methacrylate/n-butyl acrylate/2-ethylhexyl acrylate/styrene/methacrylic acid copolymer as described in A-H10-198031.

The polymer having an acid group and a polymerizable group in the side chain of the present invention is preferably a polymer having at least one structural unit represented by the following formula (1-1) to formula (3-1) as an unsaturated double bond moiety. .

In the formulae (1-1) to (3-1), A ¹ , A ² and A ³ each independently represent an oxygen atom, a sulfur atom or -N(R ²¹ )-, wherein R ²¹ represents a 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 )-, wherein R ²² represents an alkyl group which may have a substituent. Y represents an oxygen atom, a sulfur atom, a phenyl group which may have a substituent or -N(R ²³ )-, wherein R ²³ represents an alkyl group which may have a substituent. R ¹ to R ²⁰ each independently represent a monovalent substituent.

In the formula (1-1), R ¹ to R ³ each independently represent a monovalent substituent, and examples thereof are a hydrogen atom and an alkyl group additionally having a substituent. Wherein R ¹ and R ² each preferably represent a hydrogen atom, and R ³ preferably represents a hydrogen atom or a methyl group.

R ⁴ to R ⁶ each independently represent a monovalent substituent. Examples of R ⁴ are a hydrogen atom or an alkyl group which may additionally have a substituent. Among them, a hydrogen atom, a methyl group and an ethyl group are preferred. R ⁵ and R ⁶ each independently represent 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, an aryl group which may have a substituent, and may additionally have The alkoxy group of the substituent, the aryloxy group which may additionally have a substituent, the alkylsulfonyl group which may additionally have a substituent, and the arylsulfonyl group which may additionally have a substituent. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.

Examples of the substituent which may be introduced herein include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

A ¹ represents an oxygen atom, a sulfur atom or -N(R ²¹ )-, and X represents an oxygen atom, a sulfur atom or -N(R ²² )-. Examples of each of R ²¹ and R ²² are an alkyl group which may have a substituent.

G ¹ represents a divalent organic group, and an alkylene group which may have a substituent is preferred. More preferably, examples of G ¹ are a C _1-20 alkylene group which may have a substituent, a C _3-20 cycloalkyl group which may have a substituent, and a C _6-20 aromatic group which may have a substituent. Wherein a C _1-10 linear or branched alkyl group which may have a substituent, a C _3-10 cycloalkyl group which may have a substituent, and a C _6-12 aromatic group which may have a substituent It is preferred that the performance is related to developability.

The substituent on G ¹ is preferably a hydroxyl group.

In the formula (2-1), R ⁷ to R ⁹ each independently represent a monovalent substituent, and a preferred example thereof is a hydrogen atom and an alkyl group which may have a substituent, wherein R ⁷ and R ⁸ each preferably represent hydrogen. An atom, and R ⁹ preferably represents a hydrogen atom or a methyl group.

R ¹⁰ to R ¹² each independently represent a monovalent substituent. Specific examples of the substituent include a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a further substituent, an aryl group which may have a substituent, An alkoxy group which may further have a substituent, an aryloxy group which may additionally have a substituent, an alkylsulfonyl group which may additionally have a substituent, and an arylsulfonyl group which may additionally have a substituent. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.

Examples of the substituent which can be introduced here are similar to the substituent in the structural unit represented by the formula (1-1).

A ² represents an oxygen atom, a sulfur atom or -N(R ²¹ )-, wherein an example of R ²¹ is a hydrogen atom and an alkyl group which may have a substituent.

G ² represents a divalent organic group, which is preferably an alkylene group which may have a substituent. More preferably, examples of G ² are a C _1-20 alkylene group which may have a substituent, a C _3-20 cycloalkyl group which may have a substituent, and a C _6-20 aromatic group which may have a substituent. Wherein a C _1-10 linear or branched alkyl group which may have a substituent, a C _3-10 cycloalkyl group which may have a substituent, and a C _6-12 aromatic group which may have a substituent It is preferred that the performance is related to developability.

The substituent on 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. Examples of R ²³ are a hydrogen atom and an alkyl group which may have a substituent.

In the formula (3-1), R ¹³ to R ¹⁵ each independently represent a monovalent substituent, and examples thereof are a hydrogen atom and an alkyl group which may have a substituent. Wherein R ¹³ and R ¹⁴ each preferably represent a hydrogen atom, and R ¹⁵ preferably represents a hydrogen atom or a methyl group.

R ¹⁶ to R ²⁰ each independently represent a monovalent substituent, wherein each of R ¹⁶ to R ²⁰ is a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or the like. Further, an alkyl group having a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may additionally have a substituent, an alkylsulfonyl group which may additionally have a substituent, and Further, an arylsulfonyl group having a substituent. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable. Examples of the substituent which can be introduced here are similar to the substituent in the functional group represented 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 )-. Examples of R ²¹ and R ²² are similar to those in the functional group represented by the formula (1).

G ³ represents a divalent organic group, which is preferably an alkylene group which may have a substituent. Preferred examples of G ³ are a C _1-20 alkylene group which may have a substituent, a C _3-20 cycloalkyl group which may have a substituent, and a C _6-20 aromatic group which may have a substituent. Wherein a C _1-10 linear or branched alkyl group which may have a substituent, a C _3-10 cycloalkyl group which may have a substituent, and a C _6-12 aromatic group which may have a substituent It is preferred that the performance is related to developability.

The substituent on G ³ is preferably a hydroxyl group.

The polymer having an acid group and a polymerizable group in the side chain of the present invention preferably contains 20 mol% or more than 20 mol% and less than 95 in the molecule for the purpose of improving curability and reducing residue in development. The compound of the structural unit represented by the formula (1-1) to the formula (3-1). The content is more preferably from 25 mol% to 90 mol%, and still more preferably 30 mol% or more than 30 mol% and less than 85 mol%.

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

[Chemical Formula 20]

From the viewpoint of improving light sensitivity, a polymer having an acid group and an ethylenically unsaturated bond in a side chain of the present invention must have a photopolymerizable unsaturated bond, and from the viewpoint of making the polymer alkali developable, It is necessary to have an acid group such as COOH, SO ₃ H, PO ₃ H ₂ , OSO ₃ H, OPO ₂ H ₂ . The acid value of the polymer having an acid group and an ethylenically unsaturated bond in the side chain of the present invention is preferably from 20 to 300, preferably from 40 to 200, in view of coordinating dispersion stability, developability and sensitivity. More preferably 60 to 150.

(Polymer having an ethylenically unsaturated bond and a urethane group in the side chain)

The polymer having a polymerizable group in the side chain is also preferably a polymer having an ethylenically unsaturated bond and a urethane group in the side chain (hereinafter sometimes referred to as "urethane polymer").

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

OCN-X ⁰ -NCO type (4)

HO-Y ⁰ -OH formula (5)

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

When at least one of the diisocyanate compound represented by the formula (4) and the diol compound represented by the formula (5) has at least one of the groups represented by the formula (1) to the formula (3) corresponds to at least one of The unsaturated double bond moiety is prepared by introducing a specific polyurethane polymer having a group represented by the formula (1) to the formula (3) into a side chain as a reaction product of a diisocyanate compound and a diol compound. According to this method, the specific polyurethane polymer of the present invention can be easily produced, which is easier to manufacture than the method of replacing or introducing the desired side chain after the reaction and preparation of the polyurethane polymer.

1) Diisocyanate compound

An example of the diisocyanate compound represented by the formula (4) is a compound obtained by an addition reaction of a triisocyanate compound with one equivalent of a monofunctional alcohol or a monofunctional amine having an unsaturated group.

Examples of triisocyanate compounds are, but are not limited to, the following compounds.

[Chemical Formula 21]

An example of a monofunctional alcohol or a monofunctional amine compound having an unsaturated group is (but not limited to) the following compounds.

l, m, n, o = 1 to 20 integer

The method of introducing an unsaturated group to the side chain of the polyurethane polymer is preferably, for example, a diisocyanate compound having an unsaturated group in a side chain as a source material for producing a polyurethane polymer. An example of a diisocyanate compound obtained by an addition reaction of a triisocyanate compound with one equivalent of a monofunctional alcohol or a monofunctional amine compound having an unsaturated group and having an unsaturated group in a side chain is, but not limited to, the following compounds.

[Chemical Formula 27]

[Chemical Formula 28]

[Chemical Formula 29]

[Chemical Formula 30]

[Chemical Formula 31]

[Chemical Formula 32]

[Chemical Formula 33]

[Chemical Formula 34]

The specific polyurethane polymer used in the present invention may, for example, be in addition to the above-mentioned unsaturated group, from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. The diisocyanate compound other than the diisocyanate compound is copolymerized.

Examples of the diisocyanate compound to be copolymerized are the following compounds. The diisocyanate compound represented by the following formula (6) is preferred.

OCN-L ¹ -NCO type (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 have other functional groups that do not react with isocyanate groups, such as esters, urethanes, guanamines, and urea groups.

The diisocyanate compound represented by the formula (6) particularly contains the following compounds Things.

Examples include aromatic diisocyanate compounds such as 2,4-tolylene diisocyanate, 2,4-toluene diisocyanate dimer, 2,6-exenyldiene diisocyanate (2 ,6-tolylenedilene diisocyanate), p -xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmetane diisocyanate , 1,5-naphthylene diisocyanate and 3,3'-dimethylbiphenyl-4,4'-diisocyanate (3,3'-dimethylbiphenyl-4,4'-diisocyanate An aliphatic diisocyanate compound such as hexamethylene diisocyanate, trimethyl hexane diisocyanate, diisocyanate diisocyanate and dimer acid diisocyanate; alicyclic diisocyanate compound such as isofluoride Keto diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4-(or-2,6-)diisocyanate and 1,3-(isocyanatemethyl) ring Hexane; and a diisocyanate compound obtained as a reaction product of a diol and a diisocyanate, such as 1 molar 1,3-butane And adducts of 2 mole of isopropyl toluene dicyanate.

2) diol compound

A wide range of examples of the diol compound represented by the formula (5) are a polyether diol compound, a polyester diol compound, and a polycarbonate diol compound.

A preferred method of introducing an unsaturated group to the side chain of the polyurethane polymer other than the above method is, for example, using a diol compound having an unsaturated group in a side chain as a polyurethane polymer. Source material. The diol compound may be a commercially available product such as trimethylolpropane monoallyl ether, or may be a carboxylic acid having an unsaturated group which can be easily used by a halogenated diol compound, a triol compound or an amino diol compound. Acid, acid chloride, isocyanate, alcohol, amine, thiol or halogenated alkyl compound And the compound produced. Examples of such compounds are, but not limited to, the following compounds.

[Chemical Formula 36]

[Chemical Formula 37]

[Chemical Formula 38]

An example of a more preferable polymer of the present invention is that a diol compound represented by the following formula (G) is used as a diol having at least one ethylenically unsaturated linking group in the process of synthesizing a polyurethane Polyurethane resin obtained as a compound.

In the 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 )-, wherein R ¹² represents a hydrogen atom or a monovalent organic group.

Note ¹ to R ³ and X are the same meaning as in the formula (G) R ¹ to R ³ and X have the formula R (1) in the, preferred examples thereof also goes apply.

By using a polyurethane polymer derived from the diol compound, it is assumed that excessive molecular motion of the polymer backbone is inhibited by the action of a secondary sterically hindered alcohol, thereby improving film strength.

Specific examples of the diol compound represented by the formula (G) which can be preferably used for the synthesis of a specific polyurethane polymer are listed below.

[Chemical Formula 42]

The specific polyurethane polymer used in the present invention may, for example, be in addition to the above-mentioned unsaturated group, from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. The diol compound other than the diol compound is copolymerized.

Examples of the diol compound are the above polyether diol compound, polyester diol compound, and polycarbonate diol compound.

Examples of the polyether diol compound are compounds represented by the following formulas (7), (8), (9), (10), and (11), and ethylene oxide and epoxy having terminal hydroxyl groups. A random copolymer composed of propane.

[Chemical Formula 43]

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

Examples of the polyether diol compound represented by the formula (7) and the formula (8) are, in particular, the following compounds.

Examples include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1,2-propanediol, tri-1,2 -propylene glycol, tetra-1,2-propanediol, hexa-1,2-propanediol, di-1,3-propanediol, tri-1,3-propanediol, tetra-1,3-propanediol, di-1,3-butane Glycol, tri-1,3-butanediol, hexa-1,3-butanediol, polyethylene glycol having a weight average molecular weight of 1,000, polyethylene glycol having a weight average molecular weight of 1,500, and a weight average molecular weight of 2,000 Polyethylene glycol, polyethylene glycol having a weight average molecular weight of 3,000, polyethylene glycol having a weight average molecular weight of 7,500, weight average molecular weight A polypropylene glycol having a weight of 400, a polypropylene glycol having a weight average molecular weight of 700, a polypropylene glycol having a weight average molecular weight of 1,000, a polypropylene glycol having a weight average molecular weight of 2,000, a polypropylene glycol having a weight average molecular weight of 3,000, and a polypropylene having a weight average molecular weight of 4,000. Propylene glycol.

Examples of the polyether diol compound represented by the formula (9) are the following compounds.

Examples include PTMG650, PTMG1000, PTMG2000, and PTMG3000 (trade name) (from Sanyo Chemical Industries, Ltd.).

Examples of the polyether diol compound represented by the formula (10) are, in particular, the following compounds.

Examples include Newpole PE-61, Newbie PE-62, Newbie PE-64, Newbie PE-68, Newbie PE-71, Newbie PE-74, Nurburger PE-75, and Nubo PE -78, Nürburger PE-108, Nippon PE-128, and Nippon PE-61 (trade name) (from Sanyo Chemical Industries, Ltd.).

Examples of the polyether diol compound represented by the formula (11) are, in particular, the following compounds.

Examples include Newbie BPE-20, Newbie BPE-20F, Newbie BPE-20NK, Newbie BPE-20T, Newbie BPE-20G, Newbie BPE-40, Newbie BPE-60, and Newbie BPE-100. Newbie BPE-180, Newbie BPE-2P, Newbie BPE-23P, Newbie BPE-3P, and Nubo BPE-5P (trade name) (from Sanyo Chemical Industries, Ltd.).

Examples of the random copolymer composed of ethylene oxide having a terminal hydroxyl group and propylene oxide are the following copolymers.

Examples include the Nürburg 50HB-100, the Nürburg 50HB-260, and the Nürburg 50HB-400. Nürburger 50HB-660, Nürburger 50HB-2000, and Nürburger 50HB-5100 (trade name) (from Sanyo Chemical Industries, Ltd.).

Examples of the polyester diol compound are compounds represented by the following formula (12) and formula (13).

In the formulae (12) and (13), L ² , L ³ and L ⁴ may be the same or different from each other, each of which represents a divalent aliphatic or aromatic hydrocarbon group, and L ⁵ represents a divalent aliphatic hydrocarbon group. Preferably, L ² to L ⁴ each independently represent an alkylene group, an alkenyl group, an alkynylene group or an extended aryl group, and L ⁵ represents an alkylene group. Each of L ² to L ⁵ may contain 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. N1 and n2 each independently represent an integer of 2 or more, and preferably represent an integer of 2 to 100.

An example of the polycarbonate diol compound is a compound represented by the following formula (14).

In the formula (14), L ⁶ may be the same or different from each other, each of which represents a divalent aliphatic or aromatic hydrocarbon group. L ⁶ preferably represents an alkyl group, an alkenyl group, an alkynyl group and an extended aryl group. L ⁶ may contain other functional groups which are not reactive with isocyanate groups, such as ethers, carbonyls, esters, cyano groups, olefins, urethanes, guanamines, ureido groups or halogen atoms. N3 represents 2 or an integer greater than 2, and preferably represents an integer from 2 to 100.

a diol compound represented by formula (12), formula (13) or formula (14), especially The following (exemplary compound No. 1) is included to (exemplary compound No. 18). In a particular example, n represents 2 or an integer greater than 2.

In the synthesis of a specific polyurethane polymer, a diol compound having a substituent which does not react with an isocyanate group can be used in addition to the above diol compound. Examples of the diol compound include the following compounds.

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 from each other, and each of the representatives may have a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group). And a halogen atom, such as a divalent aliphatic hydrocarbon group of -F, -Cl, -Br, -I), an aromatic hydrocarbon group or a heterocyclic group. Each of L ⁷ and L ⁸ may have other functional groups which do not react with an isocyanate group, such as a carbonyl group, an ester group, a urethane group, a guanamine group or a urea group, as needed. L ⁷ and L ⁸ may form a ring.

In the synthesis of a specific polyurethane polymer, a diol compound having a carboxyl group can be used in addition to the above diol compound.

Examples of the diol compound include compounds represented by the formula (17) to the formula (19).

[Chemical Formula 50]

In the formulae (17) to (19), R ¹⁵ represents a hydrogen atom, may have a substituent (example is a cyano group, a nitro group, a halogen atom (such as -F, -Cl, -Br, -I), -CONH ₂ , -COOR ¹⁶ , -OR ¹⁶ , -NHCONHR ¹⁶ , -NHCOOR ¹⁶ , -NHCOR ¹⁶ and -OCONHR ¹⁶ (R ¹⁶ represents a C _1-10 alkyl group or a C _7-15 aralkyl group) An alkyl group, an aralkyl group, an aryl group, an alkoxy group or an aryloxy group, and preferably represents a hydrogen atom, a C _1-8 alkyl group or a C _6-15 aryl group. L ⁹ , L ¹⁰ and L ¹¹ may be the same or different from each other, and each of them represents a single bond or a divalent group which may have a substituent such as an alkyl group, an aralkyl group, an aryl group, an alkoxy group and a halogen group. The aliphatic or aromatic hydrocarbon group preferably represents a C _1-20 alkylene group or a C _6-15 extended aryl group, and more preferably a C _1-8 alkylene group. L ⁹ to L ¹¹ may have other functional groups which do not react with isocyanate groups, such as a carbonyl group, an ester, a urethane, a guanamine, a ureido group or an ether group, as needed. Any two or three of R ¹⁵ , L ⁷ , L ⁸ and L ⁹ may form a ring.

Ar represents a trivalent aromatic hydrocarbon group, and preferably represents a C _6-15 aromatic group.

Examples of the diol compound having a carboxyl group represented by the formula (17) to the formula (19) are the following compounds.

Examples include 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-hydroxybenzene) Acetate, 2,2-bis(hydroxymethyl)butyric acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, tartaric acid, N,N-dihydroxyethylglycine, and N,N- Bis(2-hydroxyethyl)-3-carboxy-propanamide.

Due to the presence of a carboxyl group, it is preferred to impart a hydrogen bond-forming ability and alkali solubility to the polyurethane polymer. More specifically, the polyurethane polymer having an ethylenically unsaturated bonding group in its side chain is a polymer having a carboxyl group in a side chain. More specifically, the polyaminocarboxylic acid having a side chain of 0.3 meq/g or more than 0.3 meq/g of an ethylenically unsaturated binding group and having a side chain of 0.4 meq/g or more than 0.4 meq/g. Ester polymers are especially preferred for use as the binder polymer of the present invention.

In order to synthesize a specific polyurethane polymer, in addition to the above diol, a compound derived from a tetracarboxylic dianhydride which is a ring-opening derivative of a diol compound represented by the following formula (20) to formula (22) can be used. Examples of the diol compound include the following compounds.

In the formulae (20) to (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 halogen group, an ester group, and an amidino group is preferred) a divalent aliphatic or aromatic hydrocarbon group, -CO-, -SO-, -SO ₂ -, -O- or -S-, and preferably represents a single bond, a C _1-15 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, a C _1-8 alkyl group, a C _6- group. ₁₅ aryl, C _1-8 alkoxy or halo. Any two of L ¹² , R ¹⁷ and R ¹⁸ may be combined 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 arylalkyl group, an aryl group or a halogen group, and preferably represents a hydrogen atom, a C _1-8 alkyl group or a C _6-15 aryl group. Any two of L ¹² , R ¹⁹ and R ²⁰ may be combined 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, and preferably represents a C _6-18 aromatic ring.

The compound represented by the formula (20), the formula (21) or the formula (22) contains the following compounds.

Examples include aromatic tetracarboxylic dianhydrides such as 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 acid Anhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 4,4'-[3,3'-(alkyl Phosphonium diphenyl) bis(iminocarbonyl)]diphthalic dianhydride, hydroquinone diacetate and trimellitic anhydride adduct and diethyl hydrazine An adduct of an amine with trimellitic anhydride; an alicyclic tetracarboxylic dianhydride such as 5-(2,5-di-oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dimethyl Anhydride (Epiclon B-4400 from DIC Corporation), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5- Cyclohexane tetracarboxylic dianhydride and tetrahydrofuran tetracarboxylic dianhydride; And aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,4,5-pentanetetracarboxylic dianhydride.

An example of a method of introducing the compound derived from a free diol compound ring-opened tetracarboxylic dianhydride into a polyurethane polymer is the method exemplified below: a) a method of reacting an alcohol-terminated compound obtained by ring-opening a tetracarboxylic dianhydride with a diol compound with a diisocyanate compound; and b) using a diisocyanate compound and an excess of a diol compound A method of reacting an alcohol-terminated urethane compound obtained by a reaction with a tetracarboxylic dianhydride.

Examples of the diol compound used for the ring opening reaction are, in particular, the following compounds.

Examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6 - hexanediol, 2-butene-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane , cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F Ethylene oxide adduct, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxy ether , p-xylene glycol, dihydroxyethyl hydrazine, bis(2-hydroxyethyl)-2,4-toluenedicarbamate, 2,4-toluene-bis(2-hydroxyethylcarbeniumamine ), bis(2-hydroxyethyl)-m-xylylenedicarbamate and bis(2-hydroxyethyl) isophthalate.

The specific polyurethane polymer usable in the present invention can be known by dissolving a diisocyanate compound and a diol compound in an aprotic solvent by adding an activity having reactivity suitable for both. The catalyst is synthesized by heating the mixture. The molar ratio (M _a : M _b ) of the diisocyanate to the diol compound used for the synthesis is preferably from 1:1 to 1.2:1. By treatment with an alcohol or an amine, a product having the desired characteristics in terms of molecular weight or viscosity can be obtained, with no residual isocyanate groups remaining in the final form.

The amount of the ethylenically unsaturated bond introduced into the specific polyurethane polymer of the present invention is preferably 0.3 meq/g or more than 0.3 meq/g and more preferably 0.35 meq in terms of the side chain. / gram to 1.50 meq/g of an ethylenically unsaturated binding group. When the polyurethane polymer contains 0.4 meq/g or more than 0.4 meq/g and more preferably 0.45 meq/r to 1.00 meq/g of carboxyl groups in the side chain together with the ethylenically unsaturated binding group It is especially preferred as the binder polymer of the present invention.

The molecular weight of the specific polyurethane polymer of the present invention is preferably 10,000 or more, and more preferably 40,000 to 200,000, by weight average molecular weight. In particular, by adjusting the weight average molecular weight to the above range, the polyurethane polymer plays an excellent role in the strength of the image forming region, and the developability of the non-image forming region for the alkali developing aqueous solution will be Excellent.

It is also preferred to use a specific polyurethane polymer of the present invention having an unsaturated group at the polymer terminal or in the main chain. Due to the presence of unsaturated groups in the polymer terminal or main chain, the crosslinking reaction between the polymerizable compound and the specific polyurethane polymer or between the specific polyurethane polymer can be increased, thereby The strength of the photocured product can be increased. In view of the ease of the crosslinking reaction, the unsaturated group herein particularly preferably contains a carbon-carbon double bond.

A method of introducing an unsaturated group to a polymer end includes a method as described below. That is, in the synthesis of the above-mentioned polyurethane polymer, it is sufficient to use an alcohol or an amine having an unsaturated group in the treatment of the residual isocyanate group at the terminal of the polymer with an alcohol or an amine. Examples of such compounds are particularly similar to the above as having A compound of an exemplary compound listed as a monofunctional alcohol or a monofunctional amine compound of a saturated group.

In view of controlling the ease of introduction, increasing the amount of introduction, and improving the efficiency of the crosslinking reaction, it is more preferred to introduce an unsaturated group into the side chain of the polymer rather than at the end of the polymer.

The ethylenically unsaturated bonding group to be introduced is preferably a methacryl fluorenyl group, an acryl fluorenyl group or a styryl group, and more preferably a methacrylic group, from the viewpoint of formability of a film which is hardened by crosslinking. Sulfhydryl or acrylonitrile. The methacrylonitrile group is more preferable from the viewpoint of the formability and storability of the film which is hardened by crosslinking.

As described previously, the amount of the methacrylonitrile group introduced is preferably 0.30 meq/g or more than 0.30 meq/g, and more preferably in the range of 0.35 meq/gram to 1.50 meq/g. Briefly, a polyurethane polymer incorporating 0.35 meq/g to 1.50 meq/g methacrylonitrile in the side chain is one of the preferred embodiments of the binder polymer of the present invention.

An example of a method of introducing an unsaturated group into a main chain is a method of synthesizing a polyurethane polymer using a diol compound having an unsaturated group in a main chain. Examples of the diol compound having an unsaturated group in the main chain are the following compounds.

Examples include cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, and polybutadiene diol.

The particular polyurethane polymer of the present invention can be used with an alkali soluble polymer containing a polyurethane polymer having a structure different from that of a particular polyurethane polymer. For example, a particular polyurethane polymer can be used with a polyurethane polymer having an aromatic group in the backbone and/or side chains.

(styrene-based polymer having an ethylenically unsaturated bond in its side chain)

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

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.

The styrene double bond represented by the formula (23) is bonded to the polymer main chain via a single bond or a bonding group composed of any atom or atomic group, wherein the bonding mode is not particularly limited.

Preferred examples of the repeating unit of the polymer having a functional group represented by the formula (23) are listed below, but the invention is not intended to be limited to these examples.

[Chemical Formula 53]

[Chemical Formula 54]

[Chemical Formula 55]

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. The pyridinium ring may have a benzopyridinium form condensed with a benzene ring as a substituent, and examples thereof include a quinolinyl group and an isoquinolinyl group.

a bonding group composed of a vinylpyridinium group represented by the formula (24) via a single bond A linking group composed of a group or an arbitrary atom or a group of atoms is bonded to the polymer main chain, and the bonding mode is not particularly limited.

Preferred examples of the repeating unit of the polymer compound having a functional group represented by the formula (24) are listed below, but the invention is not intended to be limited to these examples.

One possible method of synthesizing a styrenic polymer is, for example, between any of the monomers having a functional group represented by formula (23) or formula (24) and having a functional group copolymerizable with other copolymerizable components. A known copolymerization process reaction is disclosed. The styrenic polymer herein may be a homopolymer composed of only one functional group represented by any one of the formulas (23) and (24), or may be composed of two or more kinds. A copolymer composed of a functional group represented by either or both of the formula (23) and the formula (24).

The styrenic polymer may also be a copolymer containing other copolymerizable monomers without these functional groups. In this case, in order to impart a polymer to the aqueous alkali solution For the purpose of solubility, the copolymerizable monomer is preferably a monomer having a carboxyl group, and examples are acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, crotonic acid, and cis-butane. Aenedioic acid, fumaric acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, and 4-carboxystyrene.

It is also preferred to synthesize the subsequent use of the (poly) polymer by introducing a monomer component other than the monomer having a carboxyl group into the copolymer. In this case, the monomer which can be introduced into the copolymer can be suitably selected from the group consisting of styrene derivatives such as styrene, 4-methylstyrene, 4-hydroxystyrene, 4-ethene oxide. Styrene, 4-carboxystyrene, 4-aminostyrene, chloromethylstyrene and 4-methoxystyrene; vinylphosphonic acid, vinylsulfonic acid and its salts, styrenesulfonic acid and Salt, 4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole, N-vinylcarbazole, 4-vinylbenzyltrimethylammonium chloride, N-ethylene tetramerized with methyl chloride Imidazole, 4-vinylbenzylpyridinium chloride, acrylonitrile, methacrylonitrile, phenyl maleimide, hydroxyphenyl maleimide; vinyl ester, such as vinyl acetate Ester, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; N-vinyl pyrrolidone, Propylene decylmorpholine, vinyl chloride, vinylidene chloride, allyl alcohol, and vinyl trimethoxy decane.

When the above copolymer is used as the styrene-based polymer, the ratio of the repeating unit having a functional group represented by the formula (23) and/or the formula (24) to the total copolymer composition is preferably 20% by mass or more. 20% by mass, and more preferably 40% by mass or more than 40% by mass. Within this range, a crosslinking system which is excellent in exhibiting the effects of the present invention and has high sensitivity can be provided.

A styrenic polymer has a quaternary salt structure in its repeating unit. It can become water soluble. When the polymerizable composition of the present invention containing the polymer is used for a recording layer of a lithographic printing plate precursor, the recording layer can now be developed with water after exposure.

In particular, the styrenic polymer has a functional group represented by the formula (23) in its repeating unit and has four stages in the linking group of the bonded main chain and the functional group represented by the formula (23). In the case of a salt structure (for example, specific example P-6, example P-23, and example P-24), the styrenic polymer may be a homopolymer having the structure, and in other cases, it is preferably The following copolymers of other copolymerizable monomers. Examples include 4-vinylbenzyltrimethylammonium chloride, propyleneoxyethyltrimethylammonium chloride, methylpropenyloxyethyltrimethylammonium chloride, dimethylamine tetramerized with methyl chloride. Propyl acrylamide, N-vinylimidazole quaternized with methyl chloride, and 4-vinylbenzylpyridinium chloride.

When the styrenic polymer has a functional group represented by the formula (24) in its repeating unit, the styrenic polymer may be a homopolymer or may be a copolymer with other copolymerizable monomers.

In the case where the styrenic polymer is configured to introduce a copolymer of a carboxyl group, the polymer can now also be developed with an aqueous alkali solution. In any of these cases, the ratio of the repeating unit having a functional group represented by the formula (23) and/or the formula (24) is preferably 20% by mass or more. Any other repeating unit may be arbitrarily selected depending on the purpose.

The molecular weight of the styrenic polymer is preferably in the range of from 10,000 to 300,000, more preferably in the range of from 15,000 to 200,000, and most preferably in the range of from 20,000 to 150,000, by weight average molecular weight.

(other polymers having an ethylenically unsaturated bond in the side chain)

An example of another polymer having a side chain having an ethylenically unsaturated bond is an ethylenic group having a side chain. A novolac polymer of an unsaturated group, and an example thereof is, in particular, an introduction of an olefinic group to a side chain of a polymer described in JP-A-H9-269596 by the method described in JP-A-2002-62648 A polymer obtained by unsaturated bonds.

Examples include an acetal polymer having an ethylenically unsaturated bond in a side chain as described in JP-A-2002-162741.

The example also includes a polyamine polymer having an ethylenically unsaturated bond in a side chain as described in Japanese Patent Application Laid-Open No. 2003-321022, and a method thereof as described in JP-A-2002-62648 A polymer obtained by introducing an ethylenically unsaturated bond into a side chain of the polyamine polymer cited.

The example also includes a polyimine polymer having an ethylenically unsaturated bond in a side chain as described in Japanese Patent Application No. 2003-339785, and a method thereof by the method described in JP-A-2002-62648 A polymer obtained by introducing an ethylenically unsaturated bond into a side chain of a polyimine polymer cited.

(polymers having an epoxy group or an oxetane group in the side chain)

In the present invention, it is also preferred to contain a polymer having an epoxy group or an oxetane group in its side chain. Examples of the polymer having an epoxy group in the side chain and the polymerizable monomer or oligomer having two or more epoxy groups in the molecule are, in particular, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin. Resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, and aliphatic epoxy resin.

These compounds are commercially available or can be obtained by introducing an epoxy group into the side chain of the polymer.

For example, bisphenol A type epoxy resin can be JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (all from Japan Epoxy Co., Ltd. (Japan Epoxy Resin Co. Ltd.)), Epiclon 860, Eplon 1050, Ai Pilron 1051, and Eplon 1055 (both from DIC Corporation) Phenol F-type epoxy resins can be JER806, JER807, JER4004, JER4005, JER4007, JER4010 (both from Japan Epoxy Resin Co. Ltd.), Eplon 830, and Eplon 835 (all from Dainippon Ink Chemical Industry Co., Ltd. (DIC Corporation), LCE-21, RE-602S (both from Nippon Kayaku Co., Ltd.), etc., phenolic novolac type epoxy resin JER152, JER154, JER157S70, JER157S65 (both from Japan Epoxy Resin Co. Ltd.), Ai Peilong N-740, Neptune N-740, Neptune N-770, Audemars Piguet Long N-775 (both from DIC Corporation), etc., cresol novolac type epoxy resin can be used in Apollo N-660, Ai Pyle N-665, Ai Peilong N -670, Abyssor N-673, Achilles last N-680, Neptune N-690, Neptune N-695 (all from Japan Epoxy Co., Ltd. (Japan Ep Oxy Resin Co. Ltd.)), EOCN-1020 (both from Nippon Kayaku Co. Ltd.), and the like, and the aliphatic epoxy resin can be ADEKA RESIN EP- 4080S, Adico resin EP-4085S, Adico resin EP-4088S (both from Adeka Corporation), Celloxide 2021P, Cyrusid 2081, Cyrusid 2083, Cyrusid 2085, EHPE3150, EPOLEAD PB 3600, Eplide PB 4700 (both from Daicel Chemical Industries, Ltd.), Denacol (Denacol) EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (all from Nagase ChemteX Corporation) were purchased. Other examples include Adico resin EP-4000S, Adico resin EP-4003S, Adico resin EP-4010S, Adico resin EP-4011S (both from Adeka Corporation), NC-2000, NC-3000, NC -7300, XD-1000, EPPN-501, EPPN-502 (both from Adeka Corporation) and JER1031S (from Japan Epoxy Resin Co. Ltd.).

Examples of the polymer having a oxetane group in the side chain and a polymerizable monomer or oligomer having two or more oxetanyl groups in the molecule are, in particular, Ailong oxetane ( Aron Oxethane) OXT-121, OXT-221, OX-SQ, PNOX (both from Toagosei Co. Ltd.).

For the synthesis based on the introduction into the side chain of the polymer, by using a tertiary amine such as triethylamine and benzylmethylamine; a quaternary ammonium salt such as dodecyltrimethylammonium chloride, chlorination Tetramethylammonium and tetraethylammonium chloride); pyridine, triphenyl or the like as a catalyst, the introduction reaction is carried out in an organic solvent at a reaction temperature of 50 ° C to 150 ° C for several hours to several tens of hours. The amount of introduction of the alicyclic epoxy unsaturated compound is preferably controlled to adjust the acid value of the obtainable polymer to 5 KOH. Mg/g to 200KOH. Mg/g. The weight average molecular weight is preferably from 500 to 5,000,000, and more preferably from 1,000 to 500,000.

Although a compound having a glycidyl group as an epoxy group such as glycidyl (meth)acrylate and allyl glycidyl ether can be used as the epoxy unsaturated compound, it is preferably an alicyclic epoxy group. Unsaturated compounds are actually listed below.

[Chemical Formula 58]

The details of these polymerizable compounds, including their structure, used alone or in combination, and the amount added, can be arbitrarily selected depending on the final performance design of the near-infrared light absorbing composition. For example, from the viewpoint of sensitivity, the larger the content of the unsaturated group per molecule, the better, and two or more of the functional groups are preferred. From the viewpoint of improving the strength of the near-infrared light cut filter, three or more than three functional groups are preferred. It is also effective to control both sensitivity and strength by using polymerizable compounds (acrylates, methacrylates, styrenics, vinyl ethers, etc.) having different numbers of functional groups and different polymerizable groups. . Further, in consideration of compatibility and dispersibility with other components (metal oxides, dyes, polymerization initiators, and the like) contained in the composition of the near-infrared light absorbing liquid, the selection and use of the polymerizable compound are Key factor. For example, compatibility can be improved by using low purity compounds or by using two or more compounds in combination. Out of The 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 in the composition of the present invention is from 1% by weight to 80% by weight, more preferably from 15% by weight to 70% by weight, and especially from 20% by weight to 60% by weight, based on the total solid content of the solvent.

The polymerizable compound may be one kind or two or more than two. When two or more than two are used, the total content is adjusted to the above range.

<Binder Polymer>

The near-infrared light absorbing composition of the present invention may further contain a binder polymer, as needed, for example, for the purpose of improving film characteristics, in addition to the polymerizable compound. It is preferred to use an alkali-soluble resin as a binder polymer. The use of an alkali-soluble resin can effectively improve heat resistance and finely control coatability.

The alkali-soluble resin can be suitably selected from linear organic polymers having at least one group capable of improving alkali solubility in a molecule (preferably, a molecule having an acrylic copolymer or a styrene copolymer in the main chain). From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, and a propylene/acrylamide copolymer resin are preferable, and can be developed for control. From the viewpoint of properties, an acrylic resin, an acrylamide resin, and a propylene/acrylamide copolymer resin are preferred.

Examples of the group capable of improving alkali solubility (hereinafter also referred to as "acid group") are a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. A group which makes the resin soluble in an organic solvent and which can be developed with a weakly basic aqueous solution is preferred. (Meth)acrylic acid is especially preferred. The acid groups may be one kind or two or more than two.

Examples of the monomer capable of adding an acid group after polymerization include a monomer having a hydroxyl group, Such as 2-hydroxyethyl (meth)acrylate; a monomer having an epoxy group such as glycidyl (meth)acrylate; and a monomer having an isocyanate group such as 2-isocyanate ethyl (meth) acrylate . The group for introducing an acid group may be one kind or two or more than two. The acid group can be introduced into the alkali-soluble property by, for example, polymerizing a monomer having an acid group and/or a monomer capable of adding an acid group after polymerization (hereinafter sometimes referred to as "acid-based introduction monomer") as a monomer component. In the adhesive. In the case where an acid group is introduced as a monomer component by using a monomer capable of introducing an acid group after polymerization, a treatment of adding an acid group described later is required after the polymerization.

The alkali-soluble resin can be produced, for example, by disclosing a known radical polymerization process. Polymerization conditions regarding temperature, pressure, type and amount of radical initiator, and solvent type can be easily adjusted by those skilled in the art, and the conditions can also be determined experimentally.

The linear organic high polymer 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, a butenoic acid copolymer, and a cis-butane. a olefinic acid copolymer, a partially esterified maleic acid copolymer, an alkali-soluble phenolic resin (such as a novolac type resin), an acidic cellulose derivative having a carboxylic acid in a side chain, and a hydroxyl group-containing polymer and an acid anhydride. Adduct. A copolymer composed of (meth)acrylic acid and other monomers copolymerizable therewith is particularly preferred as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth)acrylic acid are alkyl (meth)acrylate, aryl (meth)acrylate, and vinyl compounds. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, (Methacrylate Toluene ester, naphthyl (meth) acrylate and cyclohexyl (meth) acrylate; and examples of the vinyl compound include styrene, α-methyl styrene, vinyl toluene, glycidyl methacrylate, acrylonitrile Vinyl acetate, N-vinylpyrrolidone, tetrahydrofuran methacrylate, polystyrene macromonomer, and polymethyl methacrylate macromonomer. As the N-substituted maleimide monomer described in JP-A-H10-300922, examples are N-phenyl maleimide and N-cyclohexyl-n-butylene Imine. Other monomers copolymerizable with (meth)acrylic acid may be one type or two or more types.

The alkali-soluble resin preferably further contains the polymer (a) substantially containing a compound represented by the following formula (ED) (hereinafter referred to as "ether dimer") as the basic polymer component (A):

(In the formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a C _1-25 hydrocarbon group which may have a substituent). In this manner, the composition of the present invention can form a cured coating film which is particularly excellent in heat resistance and translucency. In the formula (1) representing the ether dimer, an example of the C _1-25 hydrocarbon group which may have a substituent represented by R ¹ and R ² is, but not particularly limited to, a linear or branched alkyl group such as a Base, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, third pentyl, stearyl, lauryl and 2-ethylhexyl; aryl, such as phenyl An alicyclic group such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; Alkoxy-substituted alkyl groups such as 1-methoxyethyl and 1-ethoxyethyl; and aryl-substituted alkyl groups such as benzyl. Among them, from the viewpoint of heat resistance, it is preferred to have a substituent (such as a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group) which is less likely to remove a primary or secondary carbon by acid or heat.

Specific examples of ether dimers include dimethyl 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2'-[oxybis(methylene)]bis-2 - diethyl acrylate, 2,2'-[oxybis(methylene)]bis-2-n-propyl acrylate, 2,2'-[oxybis(methylene)] double 2-(isopropyl)acrylate, 2,2'-[oxybis(methylene)]bis-2-n-butyl acrylate, 2,2'-[oxybis( Methylene)]bis(isobutyl) bis-2-acrylate, di(tert-butyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2 '-[oxybis(methylene)]bis(tripentyl) bis-2-acrylate, 2,2'-[oxybis(methylene)]bis-2-propenoic acid di(stearyl) Ester, 2,2'-[oxybis(methylene)]bis-2-laurate, 2,2'-[oxybis(methylene)]bis-2- Di(2-ethylhexyl) acrylate, bis(1-methoxyethyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2'-[oxygen Bis(methylene)]bis(1-ethoxyethyl) bis-2-acrylate, diphenyl 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2'-[oxybis(methylene)]di-2-phenyl acrylate, 2,2'-[oxybis(methylene)]bis-2-propene Dicyclohexyl acid ester, bis(t-butylcyclohexyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2'-[oxybis(methylene) )] bis(dicyclopentadienyl) bis-2-acrylate, bis(tricyclodecyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, 2, 2'-[oxybis(methylene)]bis(isobornyl) bis-2-acrylate, 2,2'-[oxybis(methylene)]bis-2-acrylic acid diamantane Ester and bis(2-methyl-2-adamantyl) 2,2'-[oxybis(methylene)]bis-2-propenoate. Among them, particularly preferred is 2,2'-[oxybis(methylene)]bis-2-acrylic acid dimethyl ester, 2,2'-[oxybis(methylene)]bis-2-acrylic acid. Diethyl ester, 2,2'-[oxybis(methylene)]bis-2-cyclohexyl acrylate and 2,2'-[oxybis(methylene)]bis-2-acrylic acid Benzyl methyl ester. The ether dimer may be one type or may be two types Or more than two. The structure of the compound represented by the derivative free form (ED) can be copolymerized with other monomers.

An example of the novolak resin is a condensate obtained by condensing a phenol with an aldehyde in the presence of an acid catalyst. Examples of phenols are phenol, cresol, ethyl phenol, butyl phenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol and bisphenol A.

Examples of aldehydes are formaldehyde, trioxane, acetaldehyde, propionaldehyde and benzaldehyde.

The phenol and the aldehyde may be used singly or in combination of two or more.

Specific examples of the novolak resin include a condensate of m-cresol, p-cresol or a mixture thereof with formalin.

The molecular weight distribution of the novolac resin can usually be controlled by fractionation. The novolac resin may also be mixed with a low molecular weight component having a phenolic hydroxyl group such as bisphenol C and bisphenol A.

As the alkali-soluble resin, a multicomponent copolymer such as a benzyl (meth)acrylate/(meth)acrylic acid copolymer and a benzyl (meth)acrylate/(meth)acrylic acid/other is particularly preferable. A multicomponent copolymer composed of monomers. Other examples include a copolymer copolymerized with 2-hydroxyethyl methacrylate and a copolymer described in JP-A-H7-140654, comprising 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer /Methyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromer / benzyl methacrylate / methacrylic acid copolymer , 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer and 2-hydroxyethyl methacrylate/polystyrene macromer/methyl Benzyl acrylate/methacrylic acid copolymer.

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

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, and most preferably from 7,000 to 20,000.

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

<solvent>

The composition of the present invention contains 50% by mass to 80% by mass of the solvent with respect to the entire composition. The solvent may be one kind or two or more than two. When two or more than two are used, the total content is adjusted to the above range. The content of the solvent in the composition is preferably from 50% by mass to 75% by mass, and more preferably from 51% by mass to 70% by mass.

The solvent used in the present invention is appropriately selected depending on the purpose, and is not particularly limited as long as the individual components of the composition of the present invention can be uniformly dissolved or dispersed therein. Examples include water; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, and n-hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, rings Ethyl ketone, diisobutyl ketone, cyclohexanone and cyclopentanone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, Ethyl benzoate, propylene glycol monomethyl ether acetate and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, dichloromethane and monochlorobenzene; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol and Propylene glycol monomethyl ether; dimethylformamide, dimethylacetamide, dimethyl hydrazine and cyclobutyl hydrazine.

<Polymerization initiator>

The composition of the present invention may also contain a polymerization initiator. The polymerization initiator may be one kind or two or more than two. When two or more than two are used, the total content is adjusted to the following range. The content is preferably from 0.01% by mass to 30% by mass, more preferably from 0.1% by mass to 20% by mass, and especially from 0.1% by mass to 15% by mass.

The polymerization initiator may be appropriately selected depending on the purpose, and is not particularly limited as long as polymerization of the polymerizable compound can be initiated by light and/or heat, and is preferably a photopolymerizable compound. When the polymerization is initiated by light, the polymerization initiator preferably exhibits light sensitivity to ultraviolet radiation to visible light.

On the other hand, when the polymerization is initiated by heating, the polymerization initiator is preferably decomposed at 150 ° C to 250 ° C.

The polymerization initiator preferably has at least one aromatic group, and examples are a mercaptophosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, a ketal derivative compound. , thioxanthone compound, hydrazine compound, hexaarylbiimidazole compound, trihalomethyl compound, azo compound, organic peroxide, diazonium compound, hydrazine compound, hydrazine compound, azine compound, benzoin ether compound a ketal-derived compound, an onium salt compound, a metallocene compound, an organoborate compound, and a diterpene compound.

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

Examples of the polymerization initiators preferably used in the present invention are listed below, but are not intended to limit the invention.

Specific examples of the acetophenone compound include 2,2-diethoxyacetophenone, p-Dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4'-isopropyl-2-hydroxyl -2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 1,2-tolyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 1,2-methyl-1-[4-(methylthio)phenyl ]-2-morpholinylacetone, 1,2-methyl-1-(4-methylthienyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamine 1-(4-morpholinylphenyl)-butanone, 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( 4-morpholinyl)phenyl]-1-butanone and 2-methyl-1-(4-methylthienyl)-2-morpholinylpropan-1-one.

The trihalomethyl compound is more preferably a s-triazine derivative composed of at least one methyl group substituted with a monohalogen, dihalogen or trihalogen in combination with a s-triazine ring, an example of which is 2, 4 ,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine , 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α ,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(pair Methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)- 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-isopropyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2- (p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-naphthyloxynaphthyl)-4,6-bis(trichloromethyl)-all three Pyrazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylsulfanyl-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 and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

Examples of the hexaarylbiimidazole compound are various compounds described in the specification of JP-B-H6-29285, U.S. Patent No. 3,479, 185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286, the examples of which are specifically 2, 2 '-Bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4',5,5'- Tetraphenylbiimidazole, 2,2'-bis(o-p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl) -4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(o-,o-di-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 and 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

An example of a bismuth compound is the British Chemical Society: Berkin Journal 2 (1979) 1653-1660 (JCS Perkin II (1979) 1653-1660), British Chemical Society: Berkin Journal 2 ( 1979) 156-162 (JCS Perkin II (1979) 156-162), Journal of Photopolymer Science and Technology (1995) 202-232 (Journal of Photopolymer Science and Technology (1995) 202-232), JP-A-2000 -66385, JP-A-2000-80068, the various compounds described in the published Japanese translation of the PCT International Publication No. 2004-534797, IRGACURE OXE 01 (1-[4- (phenylthio)-, 2-(O-benzylidenehydrazide)-1,2-octanedione), Yanjiagu OXE 02(1-[9-ethyl-6-(2-A) Benzobenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl)ethyl ketone (both from BASF Japan Ltd.) and 2-(B) Nonyloxyimidomethyl)thioxan-9-one.

The cyclic anthraquinone compound described in JP-A-2007-231000 and JP-A-2007-322744 is also preferably used.

Preferred examples include the specific substituents described in JP-A-2007-269779 An anthracene compound and an anthracene compound having a thioaryl group as described in JP-A-2009-191061.

More specifically, the hydrazine compound is preferably a compound represented by the following formula (1). With respect to the N-O bond of hydrazine, the hydrazine compound may be either the (E)-isomer or the (Z)-isomer or the mixture of the (E)-isomer and the (Z)-isomer.

(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 R is preferably a monovalent non-metal atomic group. Examples of monovalent non-metal radicals are alkyl, aryl, decyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclyl, alkylthiocarbonyl and arylthiocarbonyl. Each of these groups may have one or more substituents. The substituent 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, and an aryl group.

The ruthenium compound can be referred to, for example, the ruthenium compound described in paragraphs [0515] to [0538] of JP-A-2012-208494 (corresponding U.S. Patent No. 2012/0235099, paragraphs [0636] to [0659]). The content of the patent is incorporated herein by reference.

Specific examples (C-4) to specific examples (C-13) of the hydrazine compound to be preferably used are listed below, but are not intended to limit the present invention.

[Chemical Formula 61]

The maximum absorption wavelength of the ruthenium compound is preferably in the range of from 350 nm to 500 nm, more preferably in the range of from 360 nm to 480 nm, and especially in the range of from 365 nm to 455 nm.

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

The molar absorption coefficient of the compound can be measured by any publicly known method, and is preferably carried out using, for example, a UV spectrophotometer (Carry-5 spectrophotometer). Varian Inc. and measured using 0.01 g/L of ethyl acetate as a solvent.

A compound selected from the group consisting of a ruthenium compound, an acetophenone compound, and a mercaptophosphine compound is more preferred as a photopolymerization initiator. More specifically, for example, an amino acetophenone type initiator as described in JP-A-H10-291969, and a ruthenium phosphine phosphine initiator as described in Japanese Patent No. 4225899 can also be used. The above-mentioned anthraquinone initiators and other anthraquinone initiators described in JP-A 2001-233842.

The acetophenone-based initiators are commercially available as Yanjiao-907, Yanjiagu-369, and Yanjiagu-379 (trade name: all from BASF Japan Ltd.). The mercaptophosphine initiators are commercially available as Yanjiao-819 and DAROCUR-TPO (trade name: all from BASF Japan Ltd.).

<Surfactant>

The composition of the present invention may contain a surfactant. The surfactants may be one or more than two or more than one or a combination. The amount of the surfactant 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, and still more preferably from 0.01% by mass to 0.1% by mass based on the total mass of the composition of the present invention.

Various surfactants can be used, such as fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, anthrone-based surfactants.

In particular, since the composition of the present invention improves liquid characteristics (especially fluidity) by containing a fluorine-containing surfactant when it is prepared as a coating liquid, coating thickness uniformity and liquid retention characteristics can be further improved.

More specifically, by using a group containing a fluorosurfactant by using When the coating liquid prepared by the preparation forms a film, the interfacial tension between the surface to be coated and the coating liquid is lowered, thereby improving the wetness on the surface to be coated, and improving the coatability on the surface to be coated. In view of forming a film having a slightly uneven thickness in a more appropriate manner, it is advantageous even when a film having a thickness of several micrometers or a thickness is formed using a small amount of liquid.

The fluorine content in the fluorine-containing surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, and particularly from 7% by mass to 25% by mass. The fluorine-containing surfactant having a fluorine content adjusted to these ranges is effective in coating thickness uniformity and liquid retention property, and is excellent in solubility in a near-infrared light absorbing composition.

Examples of fluorosurfactants include Megafac F171, Megfans F172, Meg Vanes F173, Meg Vanes F176, Meg Vans F177, Meg Vans F141, Megfan F142, Meg Vans F143, Meg Vans F144, Meg Vans R30, Meg Vans F437, Meg Vans F475, Meg Vans F479, Meg Vans F482, Meg Vans F554 , Meg Vanes F780, Meg Vanes F781 (both from DIC Corporation), Flora FC430, Flora FC431, Flora FC171 (both from Sumitomo 3M) Sumitomo 3M Ltd.), Surflon S-382, Chevron SC-101, Chevron SC-103, Chevron SC-104, Chevron SC-105, Schaeff Long SC1068, Chevron SC-381, Chevron SC-383, Chevron S393, Chevron KH-40 (both from Asahi Glass Co. Ltd.), PF636, PF656, PF6320 , PF6520 and PF7002 (from OMNOVA Solutions Inc.).

Specific examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (eg, glycerol propylene) Oxide and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic) 304, 701, 704, 901, 904, and 150R1 (from BASF) and Solsperse 20000 (from Lubrizol Japan Ltd.).

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: Efka (EFKA)-745, from Morishita & Co. Ltd.); an organic siloxane polymer KP341 (from Shin-Etsu Chemical Co. Ltd.; (meth)acrylic (co)polymer Polyflow No. 75, No. 90, No. 95 (from the co-prosperity Kyoeisha Chemical Co. Ltd.) and W001 (from Yusho Co. Ltd.).

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

Examples of the anthrone-based surfactant include "Toray Silicone DC3PA", "Torayone SH7PA", "Torayone DC11PA", "Torayone SH21PA", "Torayone" SH28PA", "Torayone SH29PA", "Torayone SH30PA" and "Torayone SH8400" (from Dow Corning Toray Co. Ltd.); "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460" and "TSF-4452" (from Momentive Performance Materials Inc.); "KP341", "KF6001", "KF6002" (from Shin-Etsu Chemical Co. Ltd.); and BYK 307, BYK 323 and BYK 330 (from BYK Chemie).

<Other components>

In addition to the essential components and preferred additives, other components may be appropriately selected for use in the near-infrared light absorbing liquid composition of the present invention, as long as the effects of the present invention are not impaired, depending on the purpose.

Examples of other components usable herein include a binder polymer, a dispersing aid, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a heat curing accelerator, a thermal polymerization inhibitor, and a plasticizer, and Also includes an adhesion enhancer for the surface of the susceptor and other auxiliaries (eg, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, perfumes, surface tension modifiers, and Chain transfer agent).

By appropriately containing these components, the stability of the target near-infrared light cut filter and characteristics such as film characteristics can now be adjusted.

These components can be referred to, for example, paragraph [0183] and subsequent contents of JP-A-2012-003225 and paragraphs [0103] to [0104] and [0107] to [0109] of JP-A-2008-250074. Section, the contents of which are incorporated herein by reference.

The near-infrared light absorbing liquid composition of the present invention has a liquid form, and thus can be easily formed into a film by a simple process such as spin coating, thereby easily fabricating a near-infrared light cut filter. Therefore, the above-described manufacturability of the conventional near-infrared optical cut filter can be improved.

The application of the near-infrared light absorbing composition of the present invention includes, but is not limited to, a near-infrared light cut filter disposed on a light receiving side of a solid-state image sensing device substrate (for example, a near-infrared light cutoff for a wafer level lens) Filter) and near-infrared light cut filter disposed on the rear side of the substrate of the solid-state image sensing device (the side opposite to the light receiving side) The wave device in which the light shielding film is disposed on the light receiving side of the substrate of the solid-state image sensing device is preferable. In particular, in the present invention, the near-infrared light absorbing composition is preferably used to form a film by coating on an image sensor of a solid-state image sensing device.

The viscosity of the near-infrared light absorbing composition of the present invention is preferably 1 mPa ‧ s or more than 1 mPa ‧ and 3,000 mPa ‧ s or less than 3,000 mPa ‧ s, more preferably 10 mPa ‧ s or more than 10 mPa ‧ s and 2,000 mPa ‧ s or less than 2,000 mPa‧s, and more preferably 100 mPa‧s or more than 100 mPa‧s and 1,500 mPa‧s or less than 1,500 mPa‧s.

When the near-infrared light absorbing composition of the present invention is used to form a near-infrared optical cut filter disposed on a light receiving side of a substrate of a solid-state image sensing device, from the viewpoint of thick film formability and coating uniformity, The viscosity is preferably 10 mPa‧s or more than 10 mPa‧s and 3,000 mPa‧s or less than 3,000 mPa‧s, more preferably 500 mPa‧s or more than 500 mPa‧s and 1,500 mPa‧s or less than 1,500 mPa‧s, and the best It is 700 mPa ‧ or more than 700 mPa ‧ and 1,400 mPa ‧ or less than 1,400 mPa ‧

The present invention also relates to a near-infrared optical cut filter obtained by using the above-described near-infrared light absorbing composition of the present invention. The near-infrared light cut filter formed by using the near-infrared light absorbing liquid composition of the present invention has excellent light-shielding performance (near-infrared light shielding effect) in the near-infrared region, and translucency in visible light region (visible light transmission) The rate is excellent, and the weather resistance (such as light fastness and moisture resistance) is excellent. In particular, the present invention is advantageously used as a near-infrared optical cut-off filter for the wavelength range from 700 nm to 2,500 nm.

The invention further relates to a method of fabricating a near-infrared optical cut-off filter having a process of coating on a light-receiving side of a substrate of a solid-state image sensing device (preferably spin coating, slot coating, screen printing or applicator) Coating) The near-infrared light absorbing composition of the present invention.

In the process of forming a near-infrared light cut filter, a film is first formed using the near-infrared light absorbing liquid composition of the present invention. The film is not particularly limited as long as it is formed to contain a near-infrared light absorbing liquid composition, and the thickness, the layer structure, and the like may be appropriately selected depending on the purpose.

The method of forming a film is generally such as coating (preferably coating) the near-infrared light absorbing liquid composition of the present invention directly on a support (in the coating liquid, the solid content of the composition is dissolved, emulsified or dispersed in a solvent Medium), and then dried.

The support may be a solid-state image sensing device substrate or another substrate (such as a glass substrate 30 described later) or a layer provided on the light receiving side of the solid-state image sensing device substrate (such as a light receiving side provided on the substrate of the solid-state image sensing device) Flattening layer).

The near-infrared light absorbing liquid composition (coating liquid) can be coated on the support by using, for example, a spin coater, a slit coater, or the like.

The conditions for drying the coating film vary depending on the kind of the individual components and the solvent and the ratio of use, and are generally carried out at 60 ° C to 150 ° C for 30 seconds to 15 minutes or an approximate time.

The film thickness may be appropriately selected depending on the purpose, and is not particularly limited, and it is preferably from 1 μm to 300 μm, more preferably from 1 μm to 200 μm, still more preferably from 1 μm to 100 μm, still more preferably from 1 μm to 50 microns, and especially from 1.0 microns to 4.0 microns.

The method of manufacturing a near-infrared light cut filter using the near-infrared light absorbing composition of the present invention may include other processes.

Other processes may be appropriately selected depending on the purpose, and are not particularly limited, and examples are surface treatment of the susceptor, preheating process (prebaking), curing process, and post-heating process (post-baking).

<Preheating process, post heating process>

The heating temperature in the preheating process and the postheating process is generally from 80 ° C to 200 ° C, and preferably from 90 ° C to 150 ° C.

The heating time in the preheating process and the postheating process is generally from 30 seconds to 240 seconds, and preferably from 60 seconds to 180 seconds.

<curing process>

A curing process is provided as needed to cure the formed film. By the process, the mechanical strength of the near-infrared light cut filter can be improved.

The curing process may be appropriately selected depending on the purpose, and is not particularly limited. Preferred examples include overall exposure and overall heating. Note that in the context of the present invention, the word "exposure" is used not only for exposure to light of various wavelengths, but also for exposure by electron beams and irradiated radioactive rays such as X-rays.

Exposure is preferably carried out by irradiation with radioactive rays. Particularly preferred examples of radioactive rays that can be used for exposure include electron beams, ultraviolet radiation, and visible light (such as KrF, ArF, g-line, h-line, and i-line). In particular, KrF, g line, h line, and i line are preferred.

Exposure methods include exposure using a stepper and exposure using a high pressure mercury lamp.

The exposure energy is preferably from 5 mJ/cm 2 to 3,000 mJ/cm 2 , more preferably from 10 mJ/cm 2 to 2,000 mJ/cm 2 , and most preferably from 50 mJ/cm to 1,000 mJ / square centimeters.

An example of an overall exposure method is a method of exposing the entire surface of the formed film. When the near-infrared light absorbing composition contains a polymerizable compound, curing of the polymerizable component produced by the composition in the film is promoted to further cure the film, and mechanical strength and durability are improved.

The device that implements the overall exposure can be selected according to the purpose, which is not subject to special restrictions. system. A preferred embodiment includes a UV exposure apparatus that typically uses an ultra-high pressure mercury lamp.

An example of a method of the integral heating process is a method of heating the entire surface of the formed film. The strength of the patterned film can be increased by overall heating.

The heating temperature in the overall heating is preferably from 120 ° C to 250 ° C, and more preferably from 120 ° C to 250 ° C. If the heating temperature is 120 ° C or higher, the film strength can be increased by heating, and if it is 250 ° C or lower, the film can be prevented from becoming brittle due to decomposition of components in the film.

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

The apparatus for carrying out the overall heating may be appropriately selected from the publicly known apparatuses depending on the purpose, and is not particularly limited and examples are a drying oven, a hot plate, and an IR heater.

The invention also relates to a camera module, comprising: a solid-state image sensing device substrate and a near-infrared optical cut filter disposed on a light receiving side of the solid-state image sensing device substrate, wherein the near-infrared optical cut-off filter is near the present invention Infrared light cut-off filter.

The camera module of the embodiment of the present invention is described below with reference to FIGS. 1 and 2, but the present invention is not limited to the following specific examples.

Please note that all components that appear in common in Figures 1 and 2 will be given the same reference numerals or signs.

In the description, the words "upper", "upper" and "upper side" are used on the far side when viewed from the substrate 10, and "lower", "lower" and "lower" are on the side closer to the substrate 10 use.

1 is a schematic cross-sectional view illustrating a configuration of a camera module equipped with a solid-state image sensing device.

The camera module 200 illustrated in FIG. 1 is connected to a circuit substrate 70 as a mounting substrate while placing solder balls 60 therebetween as a connection assembly.

In more detail, the camera module 200 is configured to have: a solid-state image sensing device substrate 100 having an image sensing device region provided on a first principal plane of the germanium substrate; sensing the solid-state image a planarization layer 46 (not illustrated in FIG. 1) provided on a first principal plane side (light receiving side) of the device substrate 100; a near-infrared optical cut filter 42 provided on the planarization layer 46; provided in near-infrared light cutoff a glass substrate 30 (translucent substrate) above the filter 42; a lens holder 50 disposed above the glass substrate 30 and having the image sensing lens 40 disposed therein; and a lens substrate 100 disposed adjacent to the solid-state image sensing device The light of the glass substrate 30 and the electromagnetic mask 44. The individual components are bonded using an adhesive member 20 (not illustrated in FIG. 1) and an adhesive member 45.

The invention also relates to a method of manufacturing a camera module comprising a solid state image sensing device substrate and a near infrared light cut filter disposed on a light receiving side of the solid state image sensing device substrate. The method includes a process of forming a film by coating a near-infrared light absorbing composition of the present invention on a light receiving side of a solid-state image sensing device substrate.

Therefore, in the camera module of this embodiment, the near-infrared light cut filter 42 is formed into a film by coating the near-infrared light absorbing liquid composition of the present invention on the planarization layer 46. The method of manufacturing a near-infrared light cut filter by coating to form a film is as described above.

The camera module 200 is configured such that incident light h from the outside can sequentially pass through the image sensing lens 40, the glass substrate 30, the near-infrared light cut filter 42 and the planarization layer 46 to reach the solid-state image sensing device substrate. The image sensing device area on the 100.

The camera module 200 is connected to the circuit substrate 70 on the second principal plane side of the solid-state image sensing device substrate 100 via solder balls 60 (connection components).

FIG. 2 is an enlarged cross-sectional view illustrating the solid-state image sensing device substrate 100 of FIG. 1.

The solid-state image sensing device substrate 100 is configured to have a ruthenium substrate 10 as a susceptor, an image sensing device 12, an insulating interlayer 13, a base layer 14, a red filter 15R, a green filter 15G, and a blue 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 device surface electrode 27.

Please note that the solder resist layer 24 can be omitted.

First, the configuration of the solid-state image sensing device substrate 100 will be described mainly on the first principal plane side.

As illustrated in FIG. 2, an image sensing device region is provided on a first principal plane side of the germanium substrate 10 as a base of the solid-state image sensing device substrate 100, wherein a plurality of image sensing devices are arranged in a two-dimensional manner. 12 (such as CCD or CMOS).

In the image sensing device region, an insulating interlayer 13 is formed on the image sensing device 12, and a base layer 14 is formed on the insulating interlayer 13. A red filter 15R, a green filter 15G, and a blue filter 15B (hereinafter collectively referred to as "color filter 15" in some cases) are provided on the base layer 14 to correspond to the image sensing device 12, respectively.

An unillustrated light-shielding film may be provided to the boundary of the red filter 15R, the green filter 15G, and the blue filter 15B and the periphery of the image sensing device region. The light shielding film can be manufactured, for example, by using a black resist known in the art.

An overcoat layer 16 is formed on the color filter 15 and microlenses 17 are formed on the overcoat layer 16 to correspond to the image sensing device 12 (color filter 15), respectively.

A planarization layer 46 is provided on the microlens 17.

Peripheral circuits (not illustrated) and internal electrodes 26 are provided on the first principal plane side at the periphery of the image sensing device region, wherein the internal electrodes 26 are electrically connected to the image sensing device 12 via peripheral circuits.

Further, the device surface electrode 27 is formed on the internal electrode 26 while the insulating interlayer 13 is placed therebetween. Contact plugs (not illustrated) are formed in the insulating interlayer 13 between the internal electrode 26 and the device surface electrode 27 to electrically connect the electrodes. The device surface electrode 27 is used to apply a voltage and read signals through the contact plug and internal electrode 26.

A base layer 14 is formed on the device surface electrode 27. An overcoat layer 16 is formed on the base layer 14. The base layer 14 and the overcoat layer 16 are perforated above the device surface electrode 27 to form a pad hole in which one of the device surface electrodes 27 is partially exposed.

The configuration of the solid-state image sensing device substrate 100 on the first principal plane side is as described above. Instead of providing a near-infrared light cut filter 42 on the planarization layer 46, alternatively provided on the microlens 17, between the base layer 14 and the color filter 15, or between the color filter 15 and the outer coating 16. Near-infrared light cut-off filter. In particular, it is preferably provided within 2 mm (more preferably within 1 mm) of the surface of the microlens 17. By providing a near-infrared light cut filter at this position, the formation process can be simplified, and unnecessary near-infrared light radiation in the microlens can be completely removed, thereby further improving the near-infrared light shielding performance.

On the first main plane side of the solid-state image sensing device substrate 100, an adhesive member 20 is provided around the image sensing device region, and the solid-state image sensing device substrate 100 is bonded to the glass substrate 30 by means of the adhesive member 20.

A through hole is formed in the crucible substrate 10 to extend through the crucible substrate 10 and extend through A via electrode is provided as a portion of the metal electrode 23 in the via hole of the overlying substrate 10. The image sensing device region and the circuit substrate 70 are electrically connected by means of via electrodes.

Subsequently, the configuration of the solid-state image sensing device substrate 100 is explained mainly on the second principal plane side.

On the second principal plane side, an insulating film 22 is formed to extend on the second principal plane and the inner wall of the through hole.

A metal electrode 23 is provided on the insulating film 22, which is patterned to extend from a region on the second principal plane of the substrate 10 to the inside of the via. The metal electrode 23 is an electrode that connects the image sensing device region and the circuit substrate 70 in the solid-state image sensing device substrate 100.

The via electrode is a part of the metal electrode 23 formed in the via hole. The via electrode extends through a portion of the germanium substrate 10 and the insulating interlayer to reach the lower side of the inner electrode 26 and is electrically connected to the inner electrode 26.

A solder resist layer 24 (protective insulating film) is additionally provided on the second principal plane side, which is formed to cover the second principal plane on which the metal electrode 23 is formed, and has a hole to expose a portion of the metal electrode 23 therethrough .

A light shielding film 18 is additionally provided on the second principal plane side, which is formed to cover the second principal plane on which the solder resist layer 24 is formed, and has a hole to expose a portion of the metal electrode 23 therethrough.

Although the light shielding film 18 illustrated in FIG. 2 is patterned to cover a portion of the metal electrode 23 and expose the remaining portion, it may alternatively be patterned to expose the entire portion of the metal electrode 23 (this also applies to the resistance Patterning of the solder layer 24).

Alternatively, the solder resist layer 24 may be omitted, and the light shielding film 18 may be provided directly on the second principal plane on which the metal electrode 23 is formed.

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

The solid-state image sensing device substrate 100 configured as described above can be obtained by, for example, paragraphs [0033] to [0068] of JP-A-2009-158863 and paragraphs [0036] of JP-A-2009-99591. [0065] Any of the publicly known methods described in the paragraphs are made.

One embodiment of a camera module has been described above with reference to Figures 1 and 2, but the one embodiment is not intended to be limited to the embodiment illustrated in Figures 1 and 2.

[Example]

The invention will be described in further detail below with reference to examples. The materials, usage amounts, ratios, process details, process procedures, and the like described in the following examples may be arbitrarily modified without departing from the spirit of the invention. Therefore, the scope of the invention should not be construed as being limited by the following examples. In the examples, the word "parts" used to describe the usage means "parts by weight" unless otherwise specified.

The abbreviations used in the examples are listed below:

MO-A: KARAYAD DPHA (from Nippon Kayaku Co. Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

MO-B: RP-1040 (pentaerythritol polyethoxy tetraacrylate) (from Nippon Kayaku Co. Ltd.)

MO-C: A-DPH-12E (dipentaerythritol polyethoxy hexaacrylate) (from Shin-Nakamura Chemical Co., Ltd.)

MO-D: Cyclomer ACA230AA (thiol-modified acrylate) (from Daicel Corporation)

MO-E: MX2-RD-F8 (acrylic polymer) (from Nippon Shokubai Co. Ltd.)

MO-F: methacrylic acid (138-10805 from Wako Pure Chemical Industries Ltd.)

MO-G: EHPE-3150 (epoxy resin, from Daicel Chemical Industries, Ltd.)

MO-H: JER157S65 (epoxy resin, from Japan Epoxy Resin Co. Ltd.)

ADD-A: F-781 (from Dainippon Ink Chemical Industry Co., Ltd. (DIC Corporation); surfactant)

ADD-B: R-30 (from DIC CorporBtion; surfactant)

I-A: OXE-01 (from BASF Japan Ltd.)

I-B: OXE-02 (from BASF Japan Ltd.)

I-C: Percumyl D (from Japan Oil & Fats Corporation (NOF Corporation))

P-1: a polymer composed of benzyl methacrylate and methacrylic acid at a molar ratio of 80:20 (Mw = 30,000; binder)

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

CYH: cyclohexanone

(Compound A and its preparation method)

5 g of anhydrous copper benzoate and 7 g of phosphoric acid (methacryloxy)ethyl ester (from Johoku Chemical Co. Ltd.) were dissolved in In 25 cubic centimeters of acetone, the mixture was allowed to react at room temperature for 3 hours with stirring. The obtained reaction product was added dropwise to a hexane solvent and the precipitate was collected by filtration, followed by drying to obtain the objective product.

(Compound B and its preparation method)

In addition to using bis((2-methylpropenyloxy)ethyl]phosphate (from Johoku Chemical Co. Ltd.) instead of phosphoric acid (methacryloxy)ethyl ester, The target product was obtained in the same manner as Compound A.

(Compound C and its preparation method)

The target product was obtained in the same manner as Compound A except that Fesimo PP (from Unichemical Co. Ltd.) was used instead of phosphoric acid (methacryloxy)ethyl ester.

(Compound D)

EPOLIGHT 1178 (diimonium dye, from Epolin, Inc.) was used.

(Compound E)

The target product was obtained in the same manner as Compound A except that diphenyl phosphate was used instead of phosphoric acid (methacryloxy)ethyl ester.

(Example 1)

The following compounds were mixed to prepare the near-infrared light absorbing composition of Example 1.

■Compound A (copper phosphate compound) 10 parts by mass

■MO-A (polymerizable compound) 9.98 parts by mass

■cyclohexanone (solvent) 80 parts by mass

■Add-A (surfactant) 0.02 parts by mass

In addition to copper phosphate compounds, polymerizable compounds, polymerization initiators, solvents The near-infrared light absorbing composition of the individual examples and the comparative examples was prepared based on the same composition as in Example 1 except that the kinds of the additives were selected as listed in the following Table. For the composition to which the polymerization initiator was added, the ratio of the polymerizable compound was adjusted to 9.88 parts by mass, and the ratio of the polymerization initiator was adjusted to 0.1 part by mass. The mark "-" in the table cell indicates that the substance does not exist.

The "exposure?" in the table indicates whether or not exposure is performed in the process of manufacturing a near-infrared optical cut filter.

The near-infrared light absorbing composition thus obtained was evaluated as follows.

[evaluation method]

<Assessing Near Infrared Light Absorbing Liquid Composition>

(Manufacture of near-infrared light cut-off filter)

Each of the individual examples and comparative examples was spin-coated on a glass substrate using a spin coater (Mikasa Spin Coater 1H-D7 (from Mikasa Co. Ltd.); 340 rpm) The infrared light absorbing composition was prebaked at 100 ° C for 120 seconds. Subsequently, as shown in the table, a part of the sample was subjected to overall exposure at 2000 mJ/cm 2 using an i-line stepper. All samples were then heated on a hot plate at 180 ° C for 180 seconds to obtain a near-infrared light cut filter.

(Evaluating near-infrared light shielding effectiveness)

The transmittance of the thus obtained near-infrared light cut filter at 900 nm was measured using a spectrophotometer U-4100 (from Hitachi High-Technologies Corporation). The minimum value of the transmittance (%) in the near-infrared region at 1,000 nm was used as an indicator of the shielding effectiveness. The transmittance in the near-infrared region of 5% or less is understood to be an indicator of good near-infrared light shielding effectiveness for practical use.

(evaluation of heat resistance)

The substrate of each of the examples and the comparative examples was further heated on a hot plate at 220 ° C for 3 minutes. Before and after the heat resistance test, a spectrophotometer U-4100 (from Hitachi High-Technologies Corporation) was used to measure each near-infrared optical cut-off filter in the wavelength range of 700 nm to 1,400 nm. The maximum absorbance (Abs λ max) and the minimum absorbance (Abs λ Amin) in the wavelength range of 400 nm to 700 nm, and the absorbance ratio represented by "Abs λ max / Abs λ min" was determined. The absorbance ratio change rate indicated by | (absorbance ratio before test - absorbance ratio after test) | / absorbance ratio before test × 100 (%) was evaluated according to the following criteria: A: rate of change of absorbance ratio 2%; B: 2% < absorbance ratio change rate 4%; C: 4% < absorbance ratio change rate 7%; and D: 7% < absorbance ratio change rate.

As apparent from the table, it was found that the near-infrared light absorbing liquid composition each containing a copper phosphate compound, a compound having a polymerizable group, and a solvent of 50% by mass to 80% by mass is excellent in near-infrared light shielding performance and heat resistance.

From the results, it was confirmed that by using the near-infrared light absorbing liquid composition of the present invention, a near-infrared light cut filter having excellent near-infrared light shielding performance, light resistance, and heat resistance can be obtained.

Since the near-infrared light absorbing liquid composition of the present invention is a liquid, the near-infrared light cut filter can be easily fabricated by a simple process such as forming a film by spin coating, thereby improving the conventional near-infrared light cut filter. It is not manufacturable.

As described above, the near-infrared light absorbing composition of the present invention is suitable for fabricating a substrate having a solid-state image sensing device substrate and a substrate disposed on the solid-state image sensing device substrate. The camera module of the side near-infrared light cut filter.

The present invention relates to the subject matter contained in Japanese Patent Application No. 037239/2013, filed on Feb. 27, 2013, and the Japanese Patent Application No. 106450/2012, filed on May 8, 2012, The application is expressly incorporated herein by reference in its entirety. All publications mentioned in the specification are also expressly incorporated herein by reference in their entirety.

The above description of the preferred embodiments of the present invention is intended to The description is chosen to be illustrative of the principles of the invention and the embodiments of the inventions The scope of the invention is not intended to be limited by the description, but is defined by the scope of the following claims.

30‧‧‧ glass substrate

40‧‧‧Image sensing lens

42‧‧‧Near-infrared cut-off filter

44‧‧‧Light and electromagnetic masks

45‧‧‧Adhesive parts

50‧‧‧Lens Holder

60‧‧‧ solder balls

70‧‧‧ circuit board

100‧‧‧Solid substrate of solid-state image sensing device

200‧‧‧ camera module

Claims (16)

A near-infrared light absorbing liquid composition comprising a copper compound, a compound having a polymerizable group, and a solvent of 50% by mass to 80% by mass. The near-infrared light absorbing liquid composition according to claim 1, wherein the copper compound is a copper compound containing phosphorus or a copper sulfonate compound. The near-infrared light absorbing composition according to claim 1 or 2, wherein the copper compound is a copper phosphate compound. The near-infrared light absorbing composition according to claim 1 or 2, wherein the compound having a polymerizable group is a polyfunctional monomer. The near-infrared light absorbing liquid composition according to claim 1 or 2, wherein the compound having a polymerizable group is represented by the following formula (MO-1) to (MO-5) Any of the polymerizable monomers indicated: In the formula, n represents 0 to 14, respectively, and m represents 1 to 8, respectively, and a plurality of R, T, and Z in a single molecule may be the same or different, and when T represents an alkylene group, the carbon terminal is bonded. At R, at least one R is a polymerizable group. The near-infrared light absorbing composition according to claim 1 or 2, wherein the compound having a polymerizable group has a polymerizable group in a side chain thereof. The near-infrared light absorbing liquid composition as described in claim 1 or 2, further comprising a polymerization initiator. The near-infrared light absorbing composition according to claim 3, wherein the copper phosphate compound is formed using a compound represented by the following formula (1): (1)(HO) _n -P(=O) -(OR ² _)3-n In the formula, R ² represents C _1-18 alkyl, C _6-18 aryl, C _1-18 aralkyl or C _1-18 alkenyl, or -OR ² represents C _4-100 polyoxyalkyl, C _4-100 (meth) propylene decyloxy or C _4-100 (meth) propylene decyl polyoxyalkyl, and n represents 1 or 2. The near-infrared light absorbing liquid composition according to claim 8, wherein in the formula (1), -OR ² represents a C _4-100 (meth) acryloxyalkyl group or a C _4-100 ( Methyl) propylene fluorenyl polyoxyalkyl. The near-infrared light absorbing liquid composition according to the above item 1, wherein the compound having a polymerizable group contains a (meth) acryloxy group. The composition of the near-infrared light absorbing liquid according to claim 1 or 2, which is used in the form of a film applied to an image sensor of a solid-state image sensing device. A near-infrared optical cut-off filter, which is used as claimed in the first patent scope The near-infrared light absorbing liquid composition according to any one of item 11, wherein. A camera module includes a solid-state image sensing device substrate and a near-infrared optical cut filter disposed on the light receiving side of the solid-state image sensing device substrate as described in claim 12. A method for manufacturing a camera module, the camera module comprising a solid-state image sensing device substrate and a near-infrared light-cut filter disposed on a light receiving side of the solid-state image sensing device substrate, wherein the camera module is manufactured The method comprises: forming a near-infrared light absorbing liquid composition according to any one of claims 1 to 11 on the light-receiving side of the substrate of the solid-state image sensing device. membrane. The method of manufacturing a camera module according to claim 14, wherein the film is formed on a microlens on the light receiving side of the solid-state image sensing device substrate. A method of manufacturing a camera module according to claim 14, comprising curing the film formed by coating the infrared light absorbing composition by irradiation with light.