KR20160103040A - Curable resin composition, anti-reflective coating using same, solid-state imaging element, and camera module - Google Patents

Abstract

A curable resin composition comprising colloidal silica particles and a polymerizable compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable resin composition, an antireflection film, a solid-state imaging device, and a camera module using the curable resin composition,

The present invention relates to a curable resin composition, an antireflection film, a solid-state imaging device and a camera module using the same.

The antireflection film is applied to the surface of the transparent substrate to prevent reflection of incident light. Its application fields are wide, and it is applied to products of various fields such as optical instruments, building materials, observation instruments and window glasses. The antireflection film is usually made of a transparent material having a low refractive index. As materials, various materials are used regardless of whether they are organic or inorganic, and they have become objects of development.

Particularly, in recent years, materials for optical devices have been actively developed. Specifically, in a display panel such as a liquid crystal or an organic EL, an optical lens, or an image sensor, a search for a material having suitable physical properties and processability for the product is underway.

BACKGROUND ART [0002] In an antireflection film applied to precision optical instruments such as image sensors, fine and precise process formability is required. Hitherto, a vapor deposition method such as a vacuum deposition method or a sputtering method suitable for microfabrication has been adopted. As the material thereof, for example, a single layer film made of MgF ₂ , cryolite, or the like has been put to practical use. In addition, application of metal oxides such as SiO ₂ , TiO ₂ , and ZrO ₂ has also been attempted.

On the other hand, the vapor-phase method such as the vacuum evaporation method or the sputtering method has a problem that the manufacturing cost is increased because the apparatus is expensive. In response to this, recently, a coating method such as a sol-gel method has been proposed (see Patent Documents 1 and 2).

Patent Document 1: JP-A-9-208898 Patent Document 2: JP-A-2013-253145

In the technique of Patent Document 2 described above, it has been proposed to use a colloidal silica in the form of beads in the coating liquid. As a result, when the antireflection film is formed, the antireflection effect can be improved with a low refractive index, and the wettability of the film surface can be improved, so that it is considered that the film can be suitably applied to the coating of a high refractive index film.

However, in the above-described precision optical apparatus such as the image sensor, it is necessary to accurately form the antireflection film in a desired shape in a very fine area. For example, an antireflection film (low refractive index film) is formed only on a necessary portion along the dimension of the microlens. The technique using the coating liquid described above is excellent in terms of cost reduction and improvement in workability, but it can not always be satisfied from the viewpoint of microfabrication.

Accordingly, an object of the present invention is to provide a curable resin composition which can realize favorable transparency and low refractive index, can be suitably applied to coating processing, and also imparts high resolution at the time of curing, thereby also having excellent microformability.

Another object of the present invention is to provide an antireflection film formed by using the curable resin composition, a solid-state image pickup device having the same, and a camera module.

The above problem has been solved by the following means.

[1] A curable resin composition comprising colloidal silica particles and a polymerizable compound.

[2] The curable resin composition according to [1], wherein the polymerizable compound has a ClogP value of 2 or more.

[3] The curable resin composition according to [1] or [2], wherein the polymerizable compound has a ClogP value of 2 to 10.

[4] The curable resin composition according to any one of [1] to [3], further comprising a polymerization initiator.

[5] The curable resin composition according to any one of [1] to [4], further comprising a solvent.

[6] The curable resin composition according to any one of [1] to [5], further comprising an alkali-soluble resin as a binder.

[7] The curable resin composition according to any one of [1] to [6], wherein the colloidal silica particles have a form in which the spherical silica particles are connected in the form of a bead.

[8] The curable resin composition according to any one of [1] to [7], wherein the colloidal silica particle comprises a plurality of spherical silica particles having an average particle diameter of 5 to 50 nm and a bonding portion for bonding the plurality of spherical particles to each other.

[9] The curable resin composition according to any one of [1] to [8], wherein the colloidal silica particles have the following specifications.

The number average particle diameter D1 measured by the dynamic light scattering method is 30 to 300 nm.

The ratio of the average particle diameter D2 determined from the specific surface area to the above-mentioned D1, D1 / D2, is 3 or more.

[10] The curable resin composition according to [7], wherein the spherical silica particles are connected in a planar manner.

[11] A curable resin composition according to any one of [1] to [10], which further contains a polysiloxane component.

[12] The curable resin composition according to any one of [1] to [11], wherein the polymerizable compound is a compound represented by any one of the following formulas (MO-1) to (MO-7).

[Chemical Formula 1]

T is a connector. R is a group having a hydroxyl group, an alkyl group or a vinyl group at the terminal. Provided that at least one group in the molecule has a vinyl group. Z is a linking group.

[13] The curable resin composition according to any one of [1] to [12], wherein the polymerizable compound is contained in an amount of 30 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the colloidal silica particles.

[14] The curable resin composition according to any one of [1] to [13], which is used for forming a low refractive index film.

[15] An antireflection film obtained by curing the curable resin composition according to [14].

[16] A solid-state imaging device comprising an antireflection film according to [15].

[17] A camera module incorporating the solid-state imaging device according to [16].

In the notation of the group (atom group) in the present specification, the notations in which substitution and non-substitution are not described include those having no substituent group and having a substituent group as long as the effect of the present invention is not impaired . For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is also true for each compound.

In the present specification, the terms "monomer" and "monomer" are synonyms. Monomers in the present specification are distinguished from oligomers and polymers, and unless otherwise stated, refer to compounds having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in the polymerization reaction.

In the present specification, Me in the formula represents a methyl group, Et represents an ethyl group, Pr indicates a propyl group, Bu indicates a butyl group, and Ph indicates a phenyl group.

The curable resin composition of the present invention can realize favorable transparency and low refractive index when it is used as a cured film, can be suitably applied to coating processing, and is also excellent in microformability by giving high resolution at the time of curing. In addition, the surface wettability of the cured film can be enhanced, so that it can be made suitable for coating.

The antireflection film formed using the curable resin composition exhibits good transparency and antireflection properties, and the solid-state image pickup device and camera module having the antireflection film exhibit excellent performance.

These and other features and advantages of the present invention will become more apparent from the following description.

The curable resin composition of the present invention can be suitably used for forming an antireflection film having a low refractive index. As its component, it contains colloidal silica particles and a polymerizable compound. Examples of optional components include a polymerization initiator, a dispersant, a solvent, a binder, and an alkoxysilane hydrolyzate. Hereinafter, preferred embodiments of the present invention will be described, focusing on the description of each component of the composition.

[Colloidal silica particles]

As the bead-shaped colloidal silica particles, it is preferable to bond the silica nanoparticles via a metal oxide-containing silica, a sol in which fumed silica is dispersed, and a mixture thereof. The above-mentioned bead-shaped colloidal silica particles have a mean particle diameter (D1 nm) measured by a dynamic light scattering method of the spherical colloidal silica particles and a specific surface area Sm ² / g measured by a nitrogen adsorption method of the spherical colloidal silica particles It is preferable that the ratio D1 / D2 of the average particle diameter (D2 nm) obtained by the equation of D2 = 2720 / S is 3 or more, the D1 is 30 to 300 nm, and the spherical colloidal silica particles are connected only in one plane . The upper limit of D1 / D2 is not particularly limited, but is preferably 20 or less. By setting the particle shape and the particle diameter to such a range, it is possible to exhibit good optical properties and to exhibit excellent manufacturability without causing agglomeration in the manufacturing process of developing or the like.

As described above, the colloidal silica particles to be contained in the curable resin composition of the present invention are preferably in the form of beads. Specifically, it is preferable that the bead-shaped colloidal silica particles are formed by joining a plurality of spherical silica particles with a bonding portion such as a metal oxide-containing silica. The use of such a colloidal silica particle in the form of beads is preferable because the refractive index of the film after formation is sufficiently lowered and the haze of the film is not increased by the unevenness of the film surface. Among these, the average particle size (D2) of the spherical silica particles is preferably 2 nm or more, more preferably 5 nm or more. The upper limit is preferably 100 nm or less, more preferably 50 nm or less, particularly preferably 30 nm or less. Also, is the average particle diameter (D2) of the spherical silica particles, refers to the average particle diameter measured by a BET method (an average obtained by D2 = formula of 2720 / S from the specific surface area Sm ² / g measured by the nitrogen adsorption method particle size ).

The average particle diameter D2 obtained from the specific surface area can be substituted by the circle equivalent diameter D0 in the projection of the spherical portion measured by a transmission electron microscope (TEM). The average particle diameter by circle equivalent diameter is evaluated by the number average of 50 or more particles unless otherwise specified.

In the present specification, the term "spherical" means a substantially spherical shape, and may be modified within the range of exhibiting the effect of the present invention. For example, a shape having a concavo-convex surface, or a flat shape having a long length in a predetermined direction. The "bead shape" may be referred to as "necklace shape ", and typically refers to a structure in which a plurality of spherical particles are connected to each other at a joint portion having a smaller outer diameter. The outer diameter of the joint can be defined as the diameter of the cross section perpendicular to the direction of connection.

The number average particle diameter (D1 nm) measured by the dynamic light scattering method of the colloidal silica particles (bead shaped silica particles) is preferably 25 nm or more, more preferably 30 nm or more, particularly preferably 35 nm or more. The upper limit is preferably 1000 nm or less, more preferably 700 nm or less, still more preferably 500 nm or less, particularly preferably 300 nm or less. It is also preferable that the spherical silica particles are connected only in one plane.

Examples of the metal oxide-containing silica constituting the bonding portion include amorphous silica, amorphous alumina and the like.

≪ Measurement method of number average particle diameter &

In the present specification, the measurement of the average particle diameter (D1) measured by the dynamic light scattering method is performed using a dynamic light scattering particle size distribution measuring apparatus (Nanotrac Nanotrac Wave-EX150 [trade name] manufactured by Nikkiso Co., Ltd.) . The procedure is as follows: A sample of the following particle dispersion is taken in a 20 ml sample bottle and diluted with toluene so that the solid component concentration becomes 0.2 mass%. The dispersed sample after dilution is irradiated with ultrasound at 40 kHz for 1 minute and used immediately after the test. Data injection was performed 10 times using 2 ml of quartz cell for measurement at a temperature of 25 캜, and the obtained "number average" was taken as the average particle size. For other detailed conditions, refer to the description of JISZ8828: 2013 "Particle size analysis - Dynamic light scattering method" as necessary. Five samples are prepared for one level and the average value is adopted.

Examples of the medium for dispersing the bead colloidal silica particles include alcohols (e.g., methanol, ethanol, isopropanol (IPA)), ethylene glycol, glycol ethers (e.g., propylene glycol monomethyl Ether), glycol ether acetate (for example, propylene glycol monomethyl ether acetate), and the like. In the raw material silica sol before the curable resin composition, the SiO ₂ concentration is preferably 5 to 40% by mass. As the silica sol in which such bead-shaped colloidal silica particles are dispersed, for example, silica sol described in Japanese Patent Publication No. 4328935 can be used.

As the bead-shaped colloidal silica particles, those commercially available as liquid sol can be used. For example, "Snowtex OUP", "Snowtex UP", "IPA-ST-UP", "Snowtex PS-M", "Snowtex PS-MO", "Snowtex PS -S "," Snowtex PS-SO "," Fine Catalyst F-120 "manufactured by Shokubai Kasei Kogyo Co., Ltd., and" Quatron PL "manufactured by FUSO KAGAKU KOGYO KABUSHIKI KAISHA . These beads-shaped fine particles have a structure in which a plurality of primary particles made of silicon oxide are bonded to each other and three-dimensionally curved.

The content of the colloidal silica particles in the curable resin composition of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, and particularly preferably 2% by mass or more based on the solid content in the composition. The upper limit is preferably 90 mass% or less, more preferably 80 mass% or less, and particularly preferably 70 mass% or less.

It is preferable to add at least one component (referred to as an alkoxysilane hydrolyzate) selected from the group consisting of hydrolysates of alkoxysilane and alkoxysilane to the silica sol. As a result, it is possible to exhibit the effect of strongly bonding the bead-shaped colloidal silica particles to each other at the time of film formation, thereby improving the porosity of the film at the time of film formation. The wettability of the film surface can be improved by using the alkoxysilane hydrolyzate.

It is preferable that the alkoxysilane hydrolyzate is formed by condensation by hydrolysis of the alkoxysilane compound (A) represented by the following formula (S1). Further, it is more preferable to be formed by condensation by hydrolysis of the alkoxysilane compound (A) and the alkoxysilane compound (B) containing a fluoroalkyl group represented by the following formula (S2).

Si (OR ^S1 ) _p (R ^S2 ) _q (S1)

In the formula, R ^S1 represents an alkyl group having 1 to 5 carbon atoms. R ^S2 represents an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 2 to 5 carbon atoms, or an aryl group of 6 to 10 carbon atoms. p is an integer of 1 to 4; q is an integer of 0 to 3; p + q is 4.

CF ₃ (CF ₂ ) _n CH ₂ CH ₂ Si (OR ³ ) ₃ (S 2)

In the formula, R ^S3 represents an alkyl group having 1 to 5 carbon atoms. n represents an integer of 0 to 8;

Specific examples of the alkoxysilane compound (A) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxy Silane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like can be given. Of these, tetramethoxysilane is preferable in that a film having a high hardness is obtained.

Specific examples of the alkoxysilane compound (B) containing a fluoroalkyl group include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, Tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and the like can be given.

The hydrolyzate of the alkoxysilane compound (A) and the fluoroalkyl group-containing alkoxysilane compound (B) can be produced by hydrolysis (condensation) in an organic solvent. Specifically, the alkoxysilane compound (A) and, if necessary, the alkoxysilane compound (B) containing the fluoroalkyl group are mixed in a ratio of 1: 0.3 to 1.6 (A: B) in a mass ratio. The ratio of the alkoxysilane compound (A) and the fluoroalkyl group-containing alkoxysilane compound (B) is preferably 1: 0.5 to 1.3 (A: B) in mass ratio. 0.5 to 5 parts by mass of water (C), 0.005 to 0.5 parts by mass of an organic acid (for example, formic acid) (D), 1 part by mass of alcohol, It is preferable that the organic solvent (E) of the ether acetate is mixed at a ratio of 0.5 to 5 parts by mass to proceed the hydrolysis reaction of the alkoxysilane compound (A) and the alkoxysilane compound (B) containing the fluoroalkyl group. Of these, the ratio of water (C) is preferably 0.8 to 3 parts by mass. As the water (C), it is preferable to use ion-exchanged water, pure water or the like in order to prevent mixing of impurities. The ratio of the organic acid (formic acid) (D) is preferably 0.008 to 0.2 parts by mass.

Examples of the alcohol used in the organic solvent (E) include methanol, ethanol, propanol, isopropyl alcohol (IPA) and the like. Examples of the glycol ether include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol Ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monoethyl ether, and dipropylene glycol monoethyl ether. Examples of the glycol ether acetate include ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether acetate, and the like. The reason why the organic solvent (E) is limited to these alcohols, glycol ethers or glycol ether acetates is that it is easy to mix the silicon alkoxide (A) and the silicon alkoxide (B) containing the fluoroalkyl group to be. Of these, ethanol, IPA, ethylene glycol monomethyl ether, and ethylene glycol monomethyl ether acetate are preferable from the viewpoint of easy control of the hydrolysis reaction and good coatability at the time of film formation . The ratio of the organic solvent (E) is preferably 0.5 to 3.5 parts by mass.

In the curable resin composition of the present invention, the alkoxy silane hydrolyzate and colloidal silica particles, the alkoxy silane to SiO ₂ minutes of the hydrolyzate upon 100 parts by weight, SiO ₂ of the colloidal silica particles minute from 50 to 500 parts by mass It is preferable that they are mixed and prepared. This range is preferable because the refractive index of the film after formation is sufficiently lowered, the film thickness is made uniform, and the haze is not increased. The proportion of the colloidal silica particles is preferably such that the SiO ₂ content of the colloidal silica particles is 150 to 350 parts by mass relative to 100 parts by mass of the SiO _{2 content} of the polysiloxane.

[Polymerizable compound]

The polymerizable compound to be contained in the curable resin composition of the present invention preferably has a ClogP value of 2 or more, more preferably 2 to 10, further preferably 2.0 to 6.0, particularly preferably 2.0 to 4.0 . If the above ClogP value is too small, sufficient resolution can not be obtained, and defects and cracks may be generated at the ends of fine pixels. On the contrary, when the ClogP value is too large, it becomes viscous and the workability may be poor. Alternatively, the surface of the cured film may be in a roughened state.

In the present invention, it is understood that the adjustment of the ClogP value of the polymerizable compound not only has a balance of hydrophilic property and hydrophobic property, but exerts a special action in combination with the above colloidal silica particles. Specifically, it is interpreted that the colloidal silica particles have a property of being easily aggregated when the composition (coating liquid or the like) is used. Although the behavior is unclear, by setting the ClogP value of the polymerizable compound used in combination in the appropriate range as described above, the agglomeration of the colloidal silica particles is suppressed or prevented, and when it is cured, a satisfactory property It is considered that a film can be formed. It is interpreted that such an action is remarkable particularly when used in combination with colloidal silica particles in the form of beads.

· ClogP

The ClogP value of a compound herein is defined by the following definition.

The octanol-water partition coefficient (log P value) can be measured by a flask permeation method generally described in JIS Japan Industrial Standard Z7260-107 (2000). In addition, the octanol-water partition coefficient (logP value) can be estimated by a computational chemical method or an empirical method instead of actual measurement. As a calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Broto's fragmentation method (Eur. J. Med. Chem., Chim. Theor., 19, 71 (1984)). In the present invention, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) is used.

The ClogP value is a value obtained by calculating the logarithm of the logarithm of the partition coefficient P of 1-octanol and water. ClogP programs introduced in Daylight Chemical Information Systems' system: PCModels will be used in the present invention unless otherwise described.

As the polymerizable compound, specifically, it is preferable to be selected from compounds having at least one, and preferably two or more, terminal ethylenic unsaturated bonds. The polymerizable compound may be any of a monomer, a prepolymer, that is, a chemical form such as a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. The polymerizable compounds may be used alone or in combination of two or more.

Specific examples of the polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, , Preferably an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and a multimer thereof. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group, an addition reaction product of a monofunctional or polyfunctional isocyanate or an epoxy or an addition reaction product of a monofunctional or polyfunctional carboxylic acid Dehydration condensation reaction product and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of a monofunctional or polyfunctional alcohol, an amine or a thiol, Unsaturated carboxylic acid esters or amides having salicylic substituent groups and mono- or polyfunctional alcohols, amines and thiol substitution reactants are also suitable. As another example, in place of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like.

As specific compounds of these compounds, compounds described in paragraph [0095] to [0108] of Japanese Laid-Open Patent Publication No. 2009-288705 can be suitably used in the present invention.

As the polymerizable compound, a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of at least 100 캜 under atmospheric pressure is preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; (Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol propol paint (acryloyloxypropyl) ether (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane, and (meth) acrylate, Japanese Examined Patent Publication 48 -41708, JP-A-50-6034, JP-A-51-37193, and the like. The urethane (meth) acrylates , JP-A-48-64183, JP-A-49-43191, JP-A-52-30490, polyester acrylates, epoxy resins and (meth) acrylic acid Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products, and mixtures thereof.

(Meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether such as glycidyl (meth) acrylate and a compound having an ethylenic unsaturated group.

Examples of other preferable polymerizable compounds include compounds having a fluorene ring and having two or more ethylenic polymerizable groups, as described in JP-A-2010-160418, JP-A-2010-129825, JP-A- , It is possible to use a cadmium resin.

As the compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 占 폚 or higher at normal pressure, the compounds described in paragraphs [0254] to [0257] of Japanese Laid-Open Patent Publication No. 2008-292970 are also suitable.

The monomer having an ethylenically unsaturated double bond is preferably one having the following reactive group RA in the molecule.

(Reactive group RA: vinyl group, (meth) acryloyl group, or (meth) acryloyloxy group)

As the monomer having an ethylenically unsaturated double bond, a radically polymerizable monomer represented by any one of the following formulas (MO-1) to (MO-7) can be suitably used. In the formula, when T is an oxyalkylene group, it is preferable that the terminal on the carbon atom side is bonded to R.

(2)

In the formulas, R is a group having a hydroxyl group, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, particularly preferably 1 to 3) at the terminal, or a group having a vinyl group. It is preferable that at least one vinyl group is contained in the molecule and that the number of the vinyl groups is two or more, more preferably three or more. R is preferably any one of the following R 1 to R 6 substituents. T is a linking group, preferably a linking group relating to any one of the following T1 to T9, or a combination thereof. Z is a linking group and is preferably Z ¹ below. Z ² is a linking group, and it is preferable that Z ² is the following formula. In addition, the directions of T1 to T9 may be reversed according to the equation.

(3)

In the formula, n is an integer, and each is preferably 0 to 14, more preferably 0 to 5, and particularly preferably 0 to 3. m is 1 to 12, preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. The plurality of R, T and Z present in one molecule may be the same or different. When T is an oxyalkylene group, it is preferable that the terminal on the carbon atom side is bonded to R. R is preferably a polymerizable group, and more preferably three are polymerizable groups. Z ³ is a linking group, preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms. Among them, a 2,2-propane diyl group is particularly preferable.

As a specific example of the radically polymerizable monomer, a compound described in Paragraph Nos. 0248 to 0251 of Japanese Patent Application Laid-Open No. 2007-269779 can be suitably used in the present embodiment.

Of these, dipentaerythritol triacrylate (KAYARAD D-330 manufactured by Nippon Kayaku K.K.) and dipentaerythritol tetraacrylate (KAYARAD D-320 manufactured by Nippon Kayaku Co., Ltd.) are commercially available as polymerizable monomers, (Trade name: KAYARAD D-310 manufactured by Nippon Kayaku K.K.), pentaerythritol tetraacrylate (A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.) , 1,6-hexanediol diacrylate (KAYARAD HDDA manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd. as a commercial product) (Meth) acryloyl group interposed between ethylene glycol and propylene glycol moieties, and a structure in which diglycerin EO (ethylene oxide) -substituted (meth) acrylate M-460 (Doogose) is preferable as the article. These oligomer types can also be used.

The multifunctional monomer is particularly preferably at least one member selected from a compound represented by the following formula (i) and a compound represented by the formula (ii).

[Chemical Formula 4]

In the formula, E, _{respectively, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - represents _{the, - ((CH 2) y} CH 2 O) - is preferred.

y each represent an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1 to 3.

X represents a hydrogen atom, an acryloyl group, a methacryloyl group or a carboxyl group, respectively.

In the formula (i), the sum of the acryloyl group and the methacryloyl group is preferably 3 or 4, and more preferably 4.

m each represents an integer of 0 to 10, preferably 1 to 5; The sum of each m is an integer of 1 to 40, preferably 4 to 20.

In the formula (ii), the sum of the acryloyl group and the methacryloyl group is preferably 5 or 6, and more preferably 6.

n each represent an integer of 0 to 10, preferably 1 to 5; The sum of n is an integer of 1 to 60, preferably 4 to 30.

As the polymerizable compound, it is preferable to contain a polyfunctional monomer having a caprolactone-modified structure. The polyfunctional monomer having a caprolactone-modified structure is not particularly limited as long as it has a caprolactone-modified structure in its molecule. Examples of the polyfunctional monomer having a caprolactone-modified structure include, for example, trimethylol ethane, ditrimethylolethane, trimethylol propane, ditrimethylol propane, pentaerythritol, dipentaerythritol, Caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohols such as glycerin, glycerin, diglycerol, trimethylolmelamine and the like with (meth) acrylic acid and? -Caprolactone. Among them, a polyfunctional monomer having a caprolactone-modified structure represented by the following formula (1) is preferable.

[Chemical Formula 5]

(Wherein all six R ^x are groups represented by the following formula (2), or one to five of six R ^x are groups represented by the following formula (2), and the remaining groups are groups represented by the following formula (3) to be.)

[Chemical Formula 6]

(Wherein R ^y and R ^z each independently represent a hydrogen atom or a methyl group, and m represents a number of 1 or 2. "*" represents a bonding hand.)

Such a polyfunctional monomer having a caprolactone-modified structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., and DPCA-20 (m = 1, The number of groups represented by formula (2) = 2, R ^x , R ^y and R ^z are all hydrogen atoms), DPCA-30 (the same formula, m = , both R ^x, R ^y, R ^z is a hydrogen atom), DPCA-60 (the same formula, m = 1, equation (2) Radix = 6, all of R ^x, R ^y, R ^z is a represented by A compound in which R &^lt; ^x & gt ^; , R < ^y & gt ^; , R < ^z > are hydrogen atoms), and the like .

In the present invention, a polymerizable compound represented by the following formula (Y1) is also preferably used. Y ¹ and Y ² represent a hydrogen atom or a substituent. As the substituent, an alkyl group having 1 to 3 carbon atoms is preferable. p and q each represent an integer, and 0 to 20 are preferable.

(7)

Examples of the polymerizable compound include those described in JP-A-48-41708, JP-A-51-37193, JP-A-2-32293, and JP-A-2-16765 And the ethylene oxide described in JP-A-62-39418, JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, Also suitable are urethane compounds having a skeleton. Examples of the polymerizable compound include compounds having an amino or sulfide structure in the molecule, such as those described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 Polymerizable compounds may also be used.

UA-7200 (manufactured by Shin Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H (manufactured by Sanyo Chemical Industries, Ltd.) , UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyowa Chemical Industry Co., Ltd.).

As the polymerizable compound, an ethylenic unsaturated compound having an acid group is also suitable. The ethylenic unsaturated compounds having an acid group are obtained by (meth) acrylating a hydroxy group which is a part of the polyfunctional alcohol and adding an acid anhydride to the remaining hydroxyl group to form a carboxyl group. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers made by Toagosei Co., Ltd.

The details of the structure of the polymerizable compound, whether or not the polymerizable compound is used alone, whether or not the polymerizable compound is used alone, and the amount of addition can be arbitrarily set in accordance with the performance design of the curable resin composition.

The content of the polymerizable compound in the curable resin composition of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, and particularly preferably 2% by mass or more based on the solid content in the composition. The upper limit is preferably 90 mass% or less, more preferably 50 mass% or less, and particularly preferably 20 mass% or less.

The mass ratio of the colloidal silica particles and the polymerizable compound contained in the curable resin composition is preferably 2.5 parts by mass or more and more preferably 5 parts by mass or more based on 100 parts by mass of the colloidal silica particles And particularly preferably 10 parts by mass or more. When it is added in a generous manner, it may be 30 parts by mass or more. The upper limit is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, further preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less, desirable.

The polymerizable compound is preferably a compound that causes polymerization by the active species. Examples of the active species include radicals, acids and bases. When the radical is an active species, the above-mentioned compound having an ethylenically unsaturated bonding group is used. On the other hand, when an acid such as a sulfonic acid, a phosphoric acid, a sulfinic acid, a carboxylic acid, a sulfuric acid or a sulfuric acid monoester is generated as an active species, a cyclic ether such as an epoxy group, an oxetanyl group or a tetrahydrofuranyl group, Can be used. When a base such as an amino compound is generated as an active species, cyclic ethers such as an epoxy group, oxetane group, and tetrahydrofuranyl group, vinylbenzene group and the like can be used. The polymerizable compound may be used in combination as needed.

The polymerizable compound preferably has a molecular weight of 10,000 or less, more preferably 5,000 or less, more preferably 2,000 or less, and particularly preferably 1,000 or less. The lower limit value is practically 200 or more.

In the present specification, when it is referred to as "acrylic ", it broadly indicates a structural group having an acryloyl group, and includes, for example, a structure having a substituent on?. However, those having a methyl group on? Are referred to as methacryl and may be referred to as (meth) acryl or the like in the sense of including methacryl.

(Surfactants)

A surfactant is applied to the composition for forming an optical functional layer of the present invention. As the surfactant, any one of a nonionic surfactant, a cationic surfactant, and an anionic surfactant may be used. Of these, fluorine-based surfactants are preferred for nonionic surfactants. In particular, a fluorine-based surfactant, an anionic surfactant, or a cationic polymer surfactant is preferable.

In the present invention, it is preferable to contain a surfactant having a polyoxyalkylene structure. The polyoxyalkylene structure refers to a structure in which an alkylene group and a divalent oxygen atom are adjacent to each other. Specific examples thereof include an ethylene oxide (EO) structure and a propylene oxide (PO) structure. The polyoxyalkylene structure may constitute a graft chain of an acrylic polymer.

When the surfactant is a polymer compound, the molecular weight is preferably 1500 or more, more preferably 2500 or more, still more preferably 5000 or more, and particularly preferably 10000 or more. The upper limit is preferably 50000 or less, more preferably 25000 or less, and particularly preferably 17500 or less.

<Method of measuring molecular weight>

In the present invention, the molecular weight of the polymer compound (polymer or oligomer) refers to the weight average molecular weight unless otherwise described, and the value measured in gel permeation chromatography (GPC) in terms of standard polystyrene is adopted. The measurement apparatus and measurement conditions are based on the following condition 1, and the condition 2 is allowed by the solubility of the sample or the like. However, a more suitable carrier (eluent) and a column suitable therefor may be selected and used depending on the polymer species. For other matters, reference shall be made to JIS K7252-1 ~ 4: 2008.

(Condition 1)

Column: TOSOH TSKgel Super HZM-H,

 TOSOH TSKgel Super HZ4000,

 TOSOH TSKgel Super HZ2000

 Using the column connecting

Carrier: tetrahydrofuran

Measuring temperature: 40 ° C

Carrier flow rate: 1.0 ml / min

Sample concentration: 0.1 mass%

Detector: RI (Refractive Index) detector

Injection amount: 0.1ml

(Condition 2)

Column: Connect two TOSOH TSKgel Super AWM-H

Carrier: 10 mM LiBr / N-methylpyrrolidone

Measuring temperature: 40 ° C

Carrier flow rate: 1.0 ml / min

Sample concentration: 0.1 mass%

Detector: RI (Refractive Index) detector

Injection amount: 0.1ml

The fluorine-based surfactant is preferably a polymer (polymer) surfactant having a polyethylene main chain. Among them, a polymer (polymer) surfactant having a poly (meth) acrylate structure is preferable. Further, poly (meth) acrylate is a general term of polyacrylate and polymethacrylate. Among them, in the present invention, a copolymer of the above-mentioned (meth) acrylate constituent unit having a polyoxyalkylene structure and a fluoroalkyl acrylate constituent unit is preferable.

Alternatively, as the fluorine-based surfactant, a compound having a fluoroalkyl or fluoroalkylene group (preferably having 1 to 24 carbon atoms and more preferably 2 to 12 carbon atoms) at any one site can be suitably used. Preferably, a polymer compound having the above fluoroalkyl or fluoroalkylene group in the side chain can be used. As the fluorine-based surfactant, those having a polyoxyalkylene structure are more preferable, and those having a polyoxyalkylene structure in a side chain are more preferable.

The fluorine-based surfactant is preferably a copolymer represented by the following formula (F1).

[Chemical Formula 8]

X ₁ to X ₄ each independently represent a hydrogen atom, an alkyl group or a fluoroalkyl group.

A represents an oxygen atom, a sulfur atom or -NR-. In the formulas, R represents a hydrogen atom or an alkyl group.

The alkyl group of X ₁ , X ₂ , X ₃ , X ₄ and R preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group and a t-butyl group.

m2 and m3 each independently represent an integer of 1 to 100;

n1 represents an integer of 1 to 20; If more than n1 is 2, X ₃ are preferably may be the same or different and, by the presence group ethyleneoxy group and propyleneoxy configuration. In addition, when the alkyleneoxy group is branched, the branching position may be branched at a carbon connected to the oxygen represented by the above formula, branched at a carbon off oxygen, and either may be branched. In practice, it is a mixture of alkyleneoxy groups having different branching positions.

Rf ₁ represents a fluoroalkyl group.

The fluoroalkyl groups represented by X ₁ to X ₄ and Rf ₁ preferably have 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms, and particularly preferably 2 to 12 carbon atoms. At this time, 1 to 6 oxygen atoms (oxy groups) may be present in the alkyl chain. For example, -CF ₃ , -C ₂ F ₅ , -C ₄ F ₉ , -CH ₂ CF ₃ , -CH ₂ C ₂ F ₅ , -CH ₂ C ₃ F ₇ , -CH ₂ C ₄ F ₉ , -CH ₂ C ₆ F ₁₃ , -C ₂ H ₄ CF ₃ , -C ₂ H ₄ C ₂ F ₅ , -C ₂ H ₄ C ₄ F ₉ , -C ₂ H ₄ C ₆ F ₁₃ , -C ₂ H _{4 C 8 F 17, -CH 2} CH (CH 3) CF 3, -CH 2 CH (CF 3) 2, -CH 2 CF (CF 3) 2, -CH 2 CH (CF 3) 2, -CF 2 _{CF (CF 3) OCF 3,} -CF 2 CF (CF 3) OC 3 F 7, -C 2 H 4 OCF 2 CF (CF 3) OCF 3, -C 2 H 4 OCF 2 CF (CF 3) OC 3 F ₇ , -C (CF ₃ ) = C (CF (CF ₃ ) ₂ ) ₂ , and the like.

Examples of the fluorine-based surfactant include Megapac F171, copper F172, copper F173, copper F176, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437, copper F479, copper F482, copper F554 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, S-141, and S-141 (manufactured by Sumitomo 3M Limited), F780 and F781F (manufactured by DIC Corporation), Fluorad FC430, (Above), SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and K- (Manufactured by OMNOVA), EF Top EF301, EF303, EF351 and EF352 (manufactured by Zemko Co., Ltd.), PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA).

The lower limit of the amount of the surfactant to be added is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and more preferably 2 parts by mass or more based on 100 parts by mass of SiO ₂ containing colloidal silica particles Is particularly preferable. The upper limit value is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and particularly preferably 10 parts by mass or less.

The content of the surfactant in the composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more, based on the solid content in the composition. The upper limit is preferably 1% by mass or less, more preferably 0.75% by mass or less, particularly preferably 0.5% by mass or less.

By setting the content of the surfactant to the lower limit value or more, it is possible to improve striped coating defects. By setting it to the upper limit value or less, compatibility can be improved, which is preferable.

The surfactant may be used alone or in combination of two or more.

It is preferable that the surfactant is present as a residual component in the form of maintaining the structure of the surfactant as it is when the composition is formed in the optical functional layer, or in a slightly decomposed state. The detection of the surfactant or its residue in the optical functional layer can be performed by methods such as TOF-SIMS, oblique cutting XPS, Raman spectroscopy, and FT-IR.

[bookbinder]

In the present invention, it is preferable to contain a binder in the curable composition. As the binder, an alkali-soluble resin is preferable, and an alkali-soluble polymeric polymer is particularly preferable. As the binder, it is particularly preferable to use a specific polymer having an acidic group (for example, a carboxyl group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, etc.) and a polymerizable group (for example, a vinyl group).

As the polymerizable group of the specific polymer, an ethylenically unsaturated bonding group is exemplified, and a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is more preferable. The acrylic polymer is preferably a vinyl polymer having a repeating unit derived from at least one of (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylamide.

The proportion of the polymerizable group contained in the specific polymer is preferably 5 to 50, and more preferably 10 to 40, in terms of the molar copolymerization ratio. By setting to such a range, compatibility between curability and developability can be achieved more effectively. As another structural unit, a structural unit containing an acid group is exemplified. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and a carboxyl group is preferable. The acid value of the specific polymer is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g. By setting such a range, the solubility of the unexposed portion at the time of pattern formation can be enhanced. Acid value refers to a value obtained by neutralization titration with a potassium hydroxide solution.

Specific examples of the specific polymer include a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate and allyl glycidyl ether, allyl alcohol, 2-hydroxyacrylate, 2-hydroxy A resin obtained by reacting an unsaturated carboxylic acid group-containing unsaturated compound and an unsaturated acid anhydride with a carboxyl group-containing resin having a hydroxyl group, and a resin obtained by reacting a polybasic acid anhydride with an addition reaction product of an epoxy resin and an unsaturated carboxylic acid A resin obtained by reacting a resin reacted with an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic anhydride with a polyfunctional monomer containing a hydroxyl group and a resin having a specific functional group which generates a desorption reaction by a base treatment to give an unsaturated group, A resin or the like that has been subjected to a base treatment to produce an unsaturated group It can be given as a target resin.

The specific polymer is preferably a resin containing at least one kind selected from the structural units (specific structural units) represented by any one of the following formulas (1) to (3).

[Chemical Formula 9]

A ¹ , A ² and A ³ each represent an oxygen atom, a sulfur atom, N (R ^N ), or a combination thereof. R ^N represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, particularly preferably 1 to 3), an aryl group (preferably having 6 to 14 carbon atoms, more preferably 6 To 10), or an aralkyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 15, particularly preferably 7 to 11).

X, Y and Z each represent a single bond, an oxygen atom, a sulfur atom, a phenylene group, N (R ^N ), or a combination thereof.

G ¹ , G ² and G ^{3 each} represent a divalent organic group and is preferably a group consisting of an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof . Specifically, a group consisting of a linear or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and a combination thereof is more preferable, and an alkylene group having 1 to 10 carbon atoms , A cycloalkylene group having 3 to 10 carbon atoms, and a group formed by a combination thereof are particularly preferable. These groups may further have a substituent, and the substituent is preferably a hydroxyl group. More preferred embodiments of G ¹ , G ² and G ³ are - (CH ₂ ) _n - (a cycloalkylene group which may have a substituent) - (CH ₂ ) _n -, n is an integer of 0 to 2 , The cycloalkylene group is a 5-membered ring or a 6-membered ring (more preferably a 6-membered ring).

Each of R ¹ to R ²⁰ independently represents a hydrogen atom or a monovalent organic group.

Each of R ¹ to R ⁴ , R ⁷ to R ¹⁰ and R ¹³ to R ¹⁸ represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ¹ and R ² are more preferably a hydrogen atom, and R ³ is more preferably a hydrogen atom or a methyl group.

^{R 5, R 6, R 11} , R 12, R 19, R 20 are each a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group, an aryl group, an alkoxy group , An aryloxy group, an alkylsulfonyl group and an arylsulfonyl group are exemplified, and a hydrogen atom, an alkoxycarbonyl group, an alkyl group and an aryl group are preferable, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.

The synthesis of the specific polymer can be carried out based on the synthesis method described in paragraphs [0027] to [0057] of Japanese Patent Application Laid-Open No. 2003-262958. Of these, the synthesis method 1) in the publication is preferable. Specific examples of the compound of the polymer having a specific structural unit include the following compounds. But the present invention is not limited to these compounds.

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

The curable resin composition of the present invention may contain the following alkali-soluble resin as a binder.

As the alkali-soluble resin, a linear organic polymer can be appropriately selected from an alkali-soluble resin having at least one group capable of promoting alkali solubility in a molecule (preferably an acrylic copolymer, a styrene-based copolymer as a main chain) . From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin and an acryl / acrylamide copolymer resin are preferable. From the viewpoint of development control, an acrylic resin, an acrylamide resin , An acrylic / acrylamide copolymer resin is preferable.

Examples of the group capable of promoting alkali solubility (hereinafter also referred to as acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and it is preferable that the group can be developed by a weakly alkaline aqueous solution , And (meth) acrylic acid are particularly preferable. These acid groups may be one kind or two or more kinds.

Examples of the monomer capable of imparting an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, And monomers having an isocyanate group such as cyanatoethyl (meth) acrylate. The monomers for introducing these acid groups may be one kind or two or more kinds. In order to introduce an acid group into an alkali-soluble binder, for example, a monomer having an acid group and / or a monomer capable of giving an acid group after polymerization (hereinafter sometimes referred to as " monomer for introducing an acid group & . When an acid group is introduced as a monomer component capable of imparting an acid group after polymerization, a treatment for imparting an acid group as described later, for example, is required after polymerization.

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

As the linear organic polymer used as an alkali-soluble resin, a polymer having a carboxylic acid in its side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, Maleic anhydride copolymers, maleic acid copolymers and novolac resins, and acidic cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to the polymer having a hydroxyl group. Particularly, a copolymer of (meth) acrylic acid and other monomers copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hexyl (meth) (Meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples of the vinyl compound include styrene, Vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate A N-substituted maleimide monomer to the above described monomers or the like, Japanese Unexamined Patent Publication No. Hei 10-300922, and the like can be mentioned N- phenyl maleimide, N- cyclohexyl maleimide.

The other monomer copolymerizable with (meth) acrylic acid is preferably a repeating unit represented by the following formula (A1).

[Chemical Formula 14]

In the formula (A1), R ^A1 represents a hydrogen atom or a methyl group. R ^A2 represents an alkylene group having 2 or 3 carbon atoms. R ^A3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10), or an aralkyl group having 7 to 22 carbon atoms (preferably 7 to 10). nA represents an integer of 1 to 15; mA represents an integer of 1 to 5, preferably 1 to 3, and more preferably 1. R ^A3 is preferably substituted at least on para. The repeating unit represented by the formula (A1) has good adsorption and / or orientation to the pigment surface due to the effect of the pi electrons of the benzene ring present in the side chain. Particularly, when the side chain portion has the ethylene oxide or propylene oxide structure of para-cumylphenol, the effect of the addition of the steric substance is further enhanced, so that a better adsorption and / or orientation plane can be formed on the pigment, High and desirable.

Among them, R ^A3 is preferably an alkyl group or an aralkyl group of the above-mentioned carbon number. This is because, in the case where R ^A3 is an alkyl group or an aralkyl group, this group becomes an obstacle and the approach between the resins is suppressed to promote orientation. However, if the number of carbon atoms is too large, the effect of steric hindrance of the alkyl group may be enhanced, and the adsorption and / or orientation of the benzene ring to the pigment surface may be hindered. This phenomenon becomes remarkable as the chain length (chain length) of the alkyl group of R ^A3 becomes longer, and when the number of carbon atoms becomes larger, the adsorption and / or orientation of the benzene ring is extremely lowered. Accordingly, the alkyl group or aralkyl group represented by R ^A3 preferably has a carbon number within the above range.

R ^A2 is preferably an alkylene group (ethylene group) having 2 carbon atoms, from the viewpoint of developability. nA is preferably in the range of 1 to 12 from the viewpoint of developability.

The repeating unit represented by the above formula (A1) can be introduced into an alkali-soluble resin using a compound (ethylenically unsaturated monomer) having an ethylene group as a vinyl group as a main chain thereof.

Examples of the ethylenically unsaturated monomer represented by the formula (A1) include phenol ethylene oxide modified (meth) acrylate, para-cumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol propylene oxide modified (Meth) acrylate, and the like.

These monomers copolymerizable with (meth) acrylic acid may be one type alone or two or more types.

As the alkali-soluble resin, it is also preferable to use a compound of the following formula (ED).

[Chemical Formula 15]

In the formula (ED), R ^E1 and R ^E2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. It is also preferable to include the polymer (a) obtained by polymerizing a monomer component essentially comprising a compound represented by the formula (ED) (hereinafter sometimes referred to as an "ether dimer") as a polymer component (A) as an essential component. Thus, the curable resin composition of the present invention can form a cured coating film having excellent heat resistance as well as transparency. The hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^E1 and R ^E2 in the above formula representing the ether dimer is not particularly limited and includes, for example, methyl, ethyl, n-propyl, isopropyl, straight-chain or branched alkyl groups such as n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl and 2-ethylhexyl; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Of these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a substituent of a primary or secondary carbon which is difficult to desorb by heat are preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- (Isopropyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, di (n-propyl) ] Bis-2-propenoate, di (n-butyl) -2,2 '- [oxybis (Methylene)] bis-2-propenoate, di (t-butyl) -2,2 '- [oxybis Di (lauryl) -2,2'- [oxybis (methylene)] bis-2-propenoate, di (lauryl) Bis (2-ethylhexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di- Methoxyethyl) Bis (2-propenyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, Bis [bis (2-methylbenzene)] bis-2-propenoate, dibenzyl-2,2 '- [oxybis Di (t-butylcyclohexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (Dicyclopentadienyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2' Bis (methylene)] bis-2-propenoate, diadamantyl-2,2 '- [oxybis (methylene)] - (2-methyl-2-adamantyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, and the like. Among these, dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- Propylene glycol dicyclohexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These ether dimers may be one kind or two or more kinds. The structure derived from the compound represented by the formula (ED) may be copolymerized with other monomers. As other monomers, the above-mentioned monomers can be mentioned.

The alkali-soluble phenol resin can be suitably used in the case of the composition of the present invention. Examples of the alkali-soluble phenol resin include novolak resins, vinyl polymers and the like.

Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenol include phenol, cresol, ethyl phenol, butyl phenol, xylenol, phenyl phenol, catechol, resorcinol, pyrogallol, naphthol, bisphenol A and the like.

The aldehydes include, for example, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and the like.

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

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

The molecular weight distribution of the novolak resin may be adjusted by means such as fractionation. A low molecular weight component having a phenolic hydroxyl group such as bisphenol C or bisphenol A may be mixed with the novolac resin.

In order to improve the crosslinking efficiency of the curable resin composition of the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-mentioned polymer containing a polymerizable group include DYNAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (manufactured by Diamond Shamrock Co., Ltd., containing COOH), BisCot R-264, 106 (all manufactured by Osaka Yuki Kagaku Kogyo K.K.), Cyclomer P series, Flackcell CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel Chemical Industries, Ltd.) . As the alkali-soluble resin containing these polymerizable groups, it is preferable that an isocyanate group and an OH group are previously reacted to leave an unreacted isocyanate group, and a compound containing a (meth) acryloyl group and a Acrylic resin containing an unsaturated group obtained by the reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule, a polymerizable double bond-containing acrylic resin obtained by a reaction of an acrylic resin, Acid pendant epoxy acrylate resin, a polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond, an acrylic resin containing an OH group, an isocyanate and a polymerizable group , A resin obtained by reacting a compound having an epoxy group-containing compound 207 and JP-A No. 2003-335814, resins obtained by subjecting a resin having an ester group on its side chain to an? -Position or an ester group having a halogen atom or a sulfonate group on? On the? Side is subjected to a basic treatment.

As the alkali-soluble resin, a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / other monomer is particularly suitable. In addition, a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate and a copolymer of 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylate described in JP-A No. 7-140654 Acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl Methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like.

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

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 or more, more preferably 5,000 or more, and particularly preferably 7,000 or more. The upper limit is preferably 50,000 or less, more preferably 30,000 or less, and particularly preferably 20,000 or less.

Specific examples of the alkali-soluble resin are shown below, but the present invention is not construed as being limited thereto.

[Chemical Formula 16]

[Chemical Formula 17]

The content of the alkali-soluble resin in the curable composition is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more based on the total solid content of the composition. The upper limit is preferably 70 mass% or less, more preferably 65 mass% or less, and particularly preferably 60 mass% or less. The amount of the alkali-soluble resin to 100 parts by mass of the colloidal silica particles is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more. The upper limit is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.

The above-mentioned binders may be used singly or in combination of two or more kinds.

[Photopolymerization initiator]

The curable resin composition of the present invention preferably contains a photopolymerization initiator. Among them, an oxime-based photopolymerization initiator and an? -Aminoketone-based photopolymerization initiator are preferably included. The mass ratio of the oxime-based photopolymerization initiator to the? -Aminoketone-based photopolymerization initiator is preferably 100 parts by mass or more, more preferably 120 parts by mass or more, and particularly preferably 150 parts by mass or more, based on 100 parts by mass of the oxime-based photopolymerization initiator Do. The upper limit is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, particularly preferably 300 parts by mass or less. By setting to such a range, the effect of improving the resolution upon curing of the curable resin composition can be more effectively achieved.

The total content of the photopolymerization initiator in the total solid content of the curable resin composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more. The upper limit is preferably 20 mass% or less, and more preferably 15 mass% or less.

The polymerization initiator preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a high absorbance at 365 nm. The oxime-based photopolymerization initiator preferably has a molar extinction coefficient at 365 nm or 405 nm of 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar extinction coefficient of the oxime-based photopolymerization initiator can be measured by a known method. For example, the molar extinction coefficient of 0.01 g / L of an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) It is preferable to measure the concentration.

· Oxime type photopolymerization initiator

The oxime-based photopolymerization initiator is preferably represented by the following formula (O1).

[Chemical Formula 18]

In the formulas, R ^O1 represents any one of a hydrogen atom, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. R ^O2 represents a substituent and may form a condensed ring with Ar ^O1 . R ^O3 represents any one of a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group. mo1 represents an integer of 0 to 4. When mo1 is 2 or more, R ^O3 may be the same or different. Ar ^O1 represents a group formed by a combination of an arylene group or an arylene group and -C (= O) -.

The acyl group of R ^O1 may be aliphatic, aromatic, or heterocyclic. More preferably 2 to 30 carbon atoms in total, more preferably 2 to 20 carbon atoms in total, and particularly preferably 2 to 16 carbon atoms in total. Examples of the substituent which the acyl group may have include an acetyl group, an n-propanoyl group, an i-propanoyl group, a methylpropanoyl group, a butanoyl group, a pivaloyl group, a hexanoyl group, a cyclohexanecarbonyl group, A 2-ethylhexanoyl group, a chloroacetyl group, a benzoyl group, a toluenecarbonyl group, a para-methoxybenzoyl group, a 2-ethylhexanoyl group, a 2-ethylhexanoyl group, , A 5-dibutoxybenzoyl group, a 1-naphthoyl group, a 2-naphthoyl group, a pyridylcarbonyl group, a methacryloyl group and an acryloyl group.

The alkyloxycarbonyl group preferably has 2 to 30 carbon atoms in total, more preferably 2 to 20 carbon atoms in total, and particularly preferably 2 to 16 carbon atoms in total. Examples of such an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonylbutoxycarbonyl group, an isobutyloxycarbonyl group, an allyloxycarbonyl group, an octyloxycarbonyl group, a dodecyloxycarbonyl group , And ethoxyethoxycarbonyl group.

The aryloxycarbonyl group is preferably an alkoxycarbonyl group having a total of 7 to 30 carbon atoms, more preferably a total of 7 to 20 carbon atoms, particularly preferably a total of 7 to 16 carbon atoms. Examples of such aryloxycarbonyl groups include phenoxycarbonyl, 2-naphthoxycarbonyl, paramethoxyphenoxycarbonyl, 2,5-diethoxyphenoxycarbonyl, para-chlorophenoxycarbonyl, A paranitrophenoxycarbonyl group, and a para-cyanophenoxycarbonyl group.

The acyl group, alkyloxycarbonyl group and aryloxycarbonyl group may further have a substituent, but are preferably amorphous. As the substituent, any one of an alkoxy group, an aryloxy group, and a halogen atom is preferable.

R ^O2 represents a substituent. R ^O2 is preferably an alkyl group having 1 to 10 carbon atoms or a group composed of a combination of an alkyl group having 1 to 10 carbon atoms and -O-. R ^{2 O 2} is preferably a ring. When R ^O2 forms a ring, any one of 4, 5, 6 and 7 member rings is preferable, and a 5 or 6 member ring is preferable. When R ^O2 forms a ring, it may form a condensed ring with Ar ^O1 . In addition, it is preferable that a condensed ring, two or three condensed rings which condensed Whanin formed by combining and Ar ^O1. When R &lt; ^{2 &gt;} is a ring, it is preferably a hetero ring, more preferably one to three of oxygen atoms and sulfur atoms in the ring structure, more preferably one oxygen atom Do.

R ^O3 is, mo1 and is two or more, are connected to each other when forming a ring, each independent R preferably forming a ring with ^O3 to each other and each is independently a R a ³ to each other an aryl group having 6 to 12 Is more preferable.

mo1 represents an integer of 0 to 4, and 0 or 1 is preferable.

Ar ^O1 represents a group formed by a combination of an arylene group or an arylene group and -C (= O) -. The carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 12. Particularly, a group comprising a phenylene group or a combination of a phenylene group and -C (= O) - is preferable, and a phenylene group is more preferable.

The oxime-based photopolymerization initiator is more preferably represented by the following formula (O2).

[Chemical Formula 19]

R ^O4 is in agreement with the above-mentioned R ^O1, and the preferable range is also the same. R ^O5 agrees with the above-mentioned R ^O3, and the preferable range is also the same. mo2 agrees with mo1 described above, and the preferable range is also the same. A ^O represents a condensed ring condensed with one ring or two rings condensed with an adjacent benzene ring, and each ring represents any one of 4, 5, 6 and 7-membered rings. Each ring is preferably a 5- or 6-membered ring. A ^O is preferably a hetero ring, more preferably one to three of oxygen atom and sulfur atom in the ring structure, and more preferably one oxygen atom.

The oxime-based photopolymerization initiator is more preferably represented by the following formula (O3).

[Chemical Formula 20]

R ^O4 agrees with the above-mentioned R ^O1, and the preferable range is also the same. R ^O5 agrees with the above-mentioned R ^O3, and the preferable range is also the same. mo2 agrees with mo1 described above, and the preferable range is also the same. X ^O represents any one of -CH ₂ -, an oxygen atom and a sulfur atom, and an oxygen atom is preferable. lo represents an integer of 1 to 3, preferably 1;

Examples of the oxime-based photopolymerization initiator include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan- 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-acetoxyimino- 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

As commercial products of oxime compounds, IRGACURE-OXE01 (trade name, manufactured by BASF) and IRGACURE-OXE02 (trade name, manufactured by BASF) are suitably used.

Specific examples of the oxime-based photopolymerization initiator usable in the present invention are shown below, but the present invention is not limited thereto.

[Chemical Formula 21]

[Chemical Formula 22]

(23)

Examples of the oxime-based polymerization initiator include TRONLY TR-PBG-304, TRONLY TR-PBG-309 and TRONLY TR-PBG-305 (produced by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS Co., Ltd.) Can be used. Further, reference may be made to the description of the polymerization initiator described in column 009 of the Japanese Patent Laid-Open Publication No. 2012-113104, column 0092, the content of which is incorporated herein by reference. By using such a oxime-based polymerization initiator, it is possible to provide a resin composition having high curing sensitivity and good developing property. The oxime-based polymerization initiator is a compound described in Japanese Patent Laid-Open Publication No. 2012-113104, The general formula is represented by the general formula (I) described in claim 1 of Japanese Laid-Open Patent Publication No. 2012-113104, more preferably represented by the general formula (IA) described in claim 3, The contents are incorporated herein by reference.

It is also possible to use a fluorine atom-containing oxime initiator. Specific examples of such initiators include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Publication No. 2014-500852, paragraph 0345, and Japanese Patent Application Laid-Open No. 2013-164471 And the compound (C-3) described in the paragraph [0101].

The total content of the oxime-based polymerization initiator is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. The upper limit is preferably 8 mass% or less, more preferably 5 mass% or less, and particularly preferably 4 mass% or less. The oxime-based photopolymerization initiator may be used singly or in combination of two or more.

· Α-Aminoketone type photopolymerization initiator

As the? -aminoketone-based photopolymerization initiator, a compound represented by the following formula (P1) can be preferably used.

&Lt; EMI ID =

X ¹ and X ² each independently represent an alkyl group, an aryl group, or a group formed by a combination of an alkylene group and an aryl group. It is preferable that any one of X ¹ and X ² is a group formed by a combination of an alkylene group and an aryl group and the other is an alkyl group. The number of carbon atoms of the alkyl group is preferably from 1 to 3, more preferably 1 or 2. The carbon number of the aryl group is preferably 6 to 12, and more preferably 6. The number of carbon atoms of the alkylene group is preferably from 1 to 6, more preferably from 1 to 3, and still more preferably, a methylene group. The aryl group may or may not have a substituent, but is preferably not.

X ³ and X ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or a phenylalkyl group having 7 to 9 carbon atoms. X ³ and X ⁴ may be bonded to each other to form a ring. The alkyl group may be any of linear, branched and cyclic. The alkyl group, alkenyl group and phenylalkyl group may have a substituent. Examples of the substituent include an OH group, an alkoxy group having 1 to 4 carbon atoms, -CN or -COOR (R represents an alkyl group having 1 to 4 carbon atoms). In particular, -NX ³ X ⁴ is preferably a dimethylamino group, a diethylamino group or a morpholino group, more preferably a dimethylamino group or a morpholino group, and more preferably a dimethylamino group.

X ⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a dimethylamino group or a morpholino group. It is preferably a morpholino group.

The? -aminoketone-based photopolymerization initiator is more preferably represented by the following formula (P2).

(25)

R ¹¹ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. When R ¹¹ represents an alkyl group, the alkyl group preferably has 1 to 3 carbon atoms, more preferably 1 or 2. R ¹² is synonymous with X ^5, and the preferred range is also the same. Ar ² represents an arylene group. The carbon number of the arylene group is preferably from 6 to 12, and more preferably 6. [ X ³ and X ⁴ are in agreement with the above-mentioned X ³ and X ⁴ , and the preferable range is also the same.

As the? -aminoketone-based photopolymerization initiator, commercially available IRGACURE-369, 819 and DAROCUR-TPO (all trade names, all manufactured by BASF) can be used.

As the? -aminoketone-based photopolymerization initiator, specifically, the following compounds can be exemplified. 2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholin- 2-methyl-1- (4-methylphenyl) propan-1-one, 2-dimethylamino- Methylpropan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2- Methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthio- 1-one (IRGACURE 907), 2-benzyl-2-dimethylamino-1- (4-methylthiophenyl) (4-morpholinophenyl) -butan-1-one (IRGACURE 369), 2-benzyl-2- dimethylamino- (4-morpholinyl) phenyl] -1-butanone (IRGACURE 379), and the like.

The? -aminoketone photopolymerization initiator may be used singly or in combination of two or more.

[Dispersant]

In the present invention, it is also preferable to use a dispersant in the curable resin composition.

Examples of the dispersing agent include polymer dispersing agents such as polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, Acrylic copolymer, naphthalenesulfonic acid-formalin condensate), polyoxyethylene alkylphosphoric acid ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer based on the structure.

The polymer dispersant adsorbs on the surface of the silica particles and acts to prevent re-aggregation. Accordingly, a terminal modified polymer having an anchor site on the surface of silica particles, a graft polymer, and a block polymer can be given as preferable structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the surface of the silica particles.

Specific examples of the dispersant usable in the present embodiment include Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001 ", EFKA" EFKA4047, 4050, 4010, 4165 (polyurethane resin) ), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (Azo pigment), 6750 (azo pigment derivative) manufactured by Ajinomoto Fine Techno Co., Ajisper PB821, PB822 manufactured by Ajinomoto Fine Techno Co., Ltd., fluorene TG-710 (uretene oligomer) manufactured by Kyoeisha Chemical Co., No. 300 (acrylic copolymer) ", Dysparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid) manufactured by Kusumoto Chemical Co., (N-dodecanedioic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 " (Polyoxyethylene nonylphenyl ether) ", "acetamin 86 (stearic acid) ", " 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (a polymer having a functional part at the terminal part), " 24000, 28000, 32000, and 38500 (graft type polymers), NIKKOL T106 (polyoxyethylene sorbitan monooleate) and MYS-IEX (polyoxyethylene monostearate) manufactured by Nikko Chemicals.

These dispersants may be used alone or in combination of two or more.

The concentration of the dispersant is preferably 1 to 100 parts by mass, more preferably 3 to 100 parts by mass, and still more preferably 5 to 80 parts by mass, relative to 1 part of the colloidal silica particles. Further, it is preferably 10 to 30% by mass relative to the total solid content of the composition.

[Organic solvents]

In the curable resin composition of the present invention, an organic solvent may be further added in addition to those described as the solvent of the colloidal silica particle solution. Alternatively, the preparation solvent may be changed to include the following solvent. The organic solvent preferably has a CLogP value of 0.5 or less, more preferably 0.3 or less. There is no lower limit, but -2 or more is real.

Examples of the solvent used in the above reaction include aliphatic compounds, halogenated hydrocarbon compounds, alcohol compounds, ether compounds, ester compounds, ketone compounds, nitrile compounds, amide compounds, sulfoxide compounds, aromatic compounds, and water These solvents may be used in combination. Each example is listed below.

· Aliphatic compounds

Hexane, heptane, cyclohexane, methylcyclohexane, octene, pentene, cyclopentane, etc.

· Halogenated hydrocarbons

Dichloroethane, tetrachlorethylene, epichlorohydrin, monochlorobenzene, orthodichlorobenzene, allyl chloride, HCFC, monochloroacetate, methylene chloride, dichloromethane, dichloromethane, dichloromethane, dichloromethane, carbon tetrachloride, Ethyl chloroformate, ethyl chloroformate, ethyl chloroformate, ethyl chloroformate, monochloroacetate, monochloroacetic acid trichloroacetic acid, methyl bromide, methyl iodide, tri (tetra)

· Alcohol compounds

But are not limited to, alcohols such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, , Xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, etc.

· Ether compounds (including hydroxyl group-containing ether compounds)

Diethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, alkylene glycol alkyl ether Ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, diethylene glycol monomethyl ether, Glycols, polyethylene glycols, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol Glycol monobutyl ether, etc.), etc.

· Ester compound

Ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate, propylene glycol 1-monomethyl ether 2-acetate, ethyl 3-ethoxypropionate and the like

· Ketone compounds

Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc.

· Nitrile compound

Acetonitrile etc.

Amide compound

N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, N, N-dimethylacetamide, N-methylpropaneamide, hexamethylphosphoric triamide, and the like can be used.

· Sulfoxide compound

Dimethyl sulfoxide etc.

· Aromatic compounds

Benzene, toluene, etc.

Preferred examples of the solvent include methyl alcohol, ethyl alcohol, propyl alcohol, propylene glycol monomethyl ether, ethyl lactate, propylene glycol 1-monomethyl ether 2-acetate, ethyl lactate, 3- Ethyl propionate, and cyclohexanone.

The amount of the solvent to be used is not particularly limited, but is preferably 1 time (v / w) or more, more preferably 2.5 times (v / w) or more, with respect to the colloidal silica particles. The upper limit is preferably 5 times (v / w) or less, more preferably 30 times (v / w) or less.

As another embodiment of the present invention, a composition containing the above colloidal silica particles and an organic solvent may be used. This composition can be applied, for example, as a buried composition applied on the surface of a substrate having unevenness. In the embedding composition, the concentration of the colloidal silica particles is, for example, 3% by mass or more and 20% by mass or less. After the coating, the cured film of the colloidal silica particles can be formed by heating and drying.

In the present invention, it is also preferable to use a high boiling point solvent. The boiling point of the high boiling point solvent is preferably 240 to 310 ° C (1 atm). Specific examples of the high boiling point solvent include triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, ethylene glycol monophenyl ether, diethylene glycol Monohexyl ether, diethylene glycol monobenzyl ether, tripropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, and polyethylene glycol dimethyl ether are preferable. By using a high boiling point solvent, drying can be suppressed, and workability and quality at the time of production can be increased. As the high boiling point solvent, triethylene glycol monobutyl ether is preferably used.

In the present specification, an indication of a compound (for example, when the compound is added to the end of the compound) is used to mean the compound itself, its salt, and its ion. It is meant to include a derivative in which a part of it is changed, for example, by introducing a substituent in a range showing a desired effect.

In the present specification, the substituent which does not specify substitution or non-substitution (the same applies also to a linking group) means that an arbitrary substituent may be contained in the substituent. This is also true for compounds that do not specify substitution or non-substitution. As the preferable substituent, the following substituent T can be mentioned.

As the substituent T, the following may be mentioned.

(Preferably an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, An alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, (Preferably, a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.) (Preferably an aryl group having 6 to 26 carbon atoms such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl and 3-methylphenyl), a heterocyclic group Is a heterocyclic group having 2 to 20 carbon atoms, preferably at least one oxygen atom, sulfur atom and nitrogen atom Is preferably a 5- or 6-membered heterocyclic group such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzoimidazolyl, 2-thiazolyl, 2- , An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy), an aryloxy group (preferably an aryl group having 6 to 26 carbon atoms An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an ethoxycarbonyl group, an ethoxycarbonyl group, For example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl and the like), an amino group (preferably containing an amino group, an alkylamino group and an arylamino group having 0 to 20 carbon atoms, such as amino, N, Amino, N, N-diethylamino, N-ethylamino, anilino), a sulfamoyl group (preferably a sulfamoyl group having 0 to 20 carbon atoms such as N, N (Preferably an acyl group having 1 to 20 carbon atoms such as acetyl, propionyl, butyryl, benzoyl and the like), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms such as a methylsulfamoyl group, An acyloxy group having 1 to 20 carbon atoms such as acetyloxy and benzoyloxy), a carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms such as N, N-di Methylcarbamoyl and N-phenylcarbamoyl), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms such as acetylamino and benzoylamino), a sulfonamido group (preferably having a carbon number of 0 (Preferably having 1 to 20 carbon atoms, such as methanesulfonamido, benzenesulfonamide, N-methylmethanesulfonamide, N-ethylbenzenesulfonamide, etc.) Alkyl thio groups such as methyl thio, ethyl thio, isopropyl thio, benz Thio), an arylthio group (preferably an arylthio group having 6 to 26 carbon atoms such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio Etc.), an alkyl or aryl sulfonyl group (preferably an alkyl or aryl sulfonyl group having 1 to 20 carbon atoms such as methylsulfonyl, ethylsulfonyl, benzenesulfonyl, etc.), a hydroxyl group, a cyano group, A halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.).

Further, each of the groups represented by these substituents T may be further substituted by the above substituent T. The above alkyl group, alkenyl group, alkynyl group (including the group containing them) may be in the form of a branched or straight chain. In addition, it may be either a ring shape or a non-ring shape. The adjacent substituents and linking groups may be bonded to each other to form a ring within a range that does not impair the effect of the present invention.

In the present specification, each description of the compound, such as the substituent and the linkage group, as well as the temperature and the thickness, may be combined with each other even if the lists are independently described.

[Low refractive index film (antireflection film)]

· Prebaking process

The curable resin composition of the present invention is preferably a low refractive index film applied to an antireflection film or the like by using the curable resin composition. As a method of applying the curable resin composition onto a support, various coating methods such as slit coating, ink jetting, spin coating, casting, roll coating, screen printing and the like can be applied. Drying (prebaking) of the layer of the curable resin composition applied on the support can be carried out at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds in a hot plate, an oven or the like.

· Exposure process

In a preferred embodiment of the present invention, a coating film of the curable resin composition is irradiated with exposure energy, and the exposed portion is developed to form a pattern of a resin cured product. In the present embodiment, prior to the exposure, a curable resin composition is provided on a support or the like to form a layer of the curable resin composition. As the support, there can be used a substrate for a solid-state imaging element provided with an imaging element (light-receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) on a substrate (for example, a silicon substrate) have. The pattern of the cured film may be formed on the imaging element formation surface side (surface) of the substrate for a solid-state imaging element, or on the imaging element formation surface side (back surface). A light shielding film may be provided between each imaging element in the substrate for the solid-state imaging element or on the back surface of the substrate for the solid-state imaging element. If necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate.

In the exposure step, the layer of the curable resin composition is pattern-exposed through a mask having a predetermined mask pattern by using an exposure apparatus such as a stepper. The irradiation of the exposure energy is preferably performed by irradiation of an active energy ray selected from g line, h line, i line, KrF line (excimer laser line), and ArF line (excimer laser line). It is desirable that the exposure illumination energy of less than 5000W / m ^2, and more preferably at least 7000W / m ^2, particularly preferably not less than 8000W / m ^2. And defined as the upper side, 18000W / m ² or less is preferable, more preferably 15000W / m ² or less, 10000W / m ² or less is especially preferred. By setting the irradiation energy in this range, a resolution of a good pattern can be obtained.

For example, a reduction projection exposure apparatus can be used. In a projection exposure apparatus, for example, an active energy ray emitted from a specific light source is incident on a projection lens (projection lens) through a condenser lens. In this projection optical system, a mask having a predetermined pattern is provided before or after the condenser lens so that an active energy ray of a predetermined pattern reaches the projection lens. At this time, it is preferable to set the conditions such as the numerical aperture (NA ₁ ) on the condenser lens side and the numerical aperture (NA ₂ ) on the projection lens side appropriately within a desired range. The active energy rays transmitted through the reduction projection optical system are emitted from the opposite side and irradiated with the exposure substrate (work). By irradiation of this active energy ray, the layer of the curable resin composition on the substrate is exposed and is preferably a negative type (exposure curable), and the exposed portion is cured. To properly set a desired range even in the numerical aperture of the emission side of the projection lens (NA ₃₎ is preferred.

· Development process

Subsequently, by performing development such as alkali development treatment, the curable resin composition layer of the tail-irradiated portion in the exposure step is eluted into the aqueous alkaline solution, leaving only the photo-cured portion. As the developing solution, an organic alkali developing solution which does not cause damage to the imaging element, circuit, etc. on the ground (base) is preferable. The development temperature is usually 20 ° C to 30 ° C, and the development time is, for example, 20 seconds to 90 seconds. In order to remove the residues, it is sometimes carried out 120 to 180 seconds in recent years. Further, in order to further improve the removability of the residue, the step of removing the developer every 60 seconds and supplying the fresh developer may be repeated a number of times.

As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving the alkaline compound in an amount of 0.001 to 10 mass%, preferably 0.01 to 5 mass%, is suitable.

The alkaline compound may be, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide , Tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7- (Of these, an organic alkali is preferable).

When an alkaline aqueous solution is used as a developing solution, cleaning treatment is generally performed with water after development.

· Post-baking

Next, it is preferable to carry out a heat treatment (post-baking) after drying. The post-baking is post-development heat treatment to make the curing complete. The heating temperature is preferably 250 占 폚 or lower, more preferably 240 占 폚 or lower, and still more preferably 230 占 폚 or lower, from the viewpoint of suppressing damage to the organic photoelectric conversion portion. Although there is no particular lower limit, in consideration of efficient and effective treatment, it is preferable to conduct a heat curing treatment of 50 占 폚 or more, more preferably 100 占 폚 or more.

The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), a high-frequency heater or the like so as to achieve the above-

The post-baking by heating may be changed to cure the antireflection film by UV (ultraviolet) irradiation. At this time, it is preferable that the UV curing agent can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of the initiator added for the lithography process by ordinary I-line exposure. As the UV curing agent, for example, Cibaigakure 2959 (trade name) can be mentioned. As the specific wavelength of the UV irradiation light, it is preferable to use a material which is cured at 340 nm or less. The lower limit of the wavelength is not particularly limited, but is generally 220 nm or more. The exposure dose of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and even more preferably 800 to 3500 mJ. The UV curing process is preferably performed after the lithography process because it enables more effective curing at low temperatures. It is preferable to use an ozone mercury lamp as the exposure light source.

The refractive index of the low refractive index film (antireflection film) formed of the curable resin composition of the present invention is preferably 1.5 or less, more preferably 1.45 or less, and particularly preferably 1.42 or less. The lower limit is practically 1.1 or more. In this specification, the refractive index of the film is a value measured at 633 nm and 25 ° C unless otherwise specified.

The low refractive index film formed from the curable resin composition of the present invention can be used as an antireflection film used for preventing reflection of incident light in a display panel such as a cathode ray tube, liquid crystal, or organic EL, a solar cell, a glass for a showcase, It can be suitably used for the formation of an interlayer or the like using a difference in refractive index used in a camera module or the like.

[Microlens unit]

A microlens unit, which is a preferred embodiment of the present invention, has a laminated structure including a low refractive index film (light transmissive cured film) and a microlens coated thereon. This lens unit is used for a solid-state image pickup device (optical device).

[Solid-state image pickup device]

In the solid-state imaging device according to the preferred embodiment of the present invention, the low refractive index film formed of the curable resin composition can be applied to the antireflection film, the intermediate film, or the partition wall of the color filter. The structure of the solid-state image pickup device is composed of, for example, a light receiving element (photodiode) provided on a silicon substrate, a lower planarization film, a color filter, an upper planarization film, a microlens and the like. The color filter is composed of color filter pixel portions of red (R), green (G), and blue (B). The color filter is composed of a plurality of two-dimensionally arranged green pixel portions. In the present embodiment, it is preferable to have a partition wall formed of the curable resin composition therebetween. Each coloring pixel portion is formed at a position above the light receiving element. The green pixel portion is formed of a Bayer pattern (checker board shape), and the blue pixel portion and the red pixel portion are formed between the green pixel portion.

The flattening film is formed so as to cover the upper surface of the color filter, and the surface of the color filter is flattened. The microlens is a condensing lens arranged with its convex surface facing upward, and is provided above the planarizing film and above the light receiving element. That is, the micro-lens, the color filter pixel portion, and the light-receiving element are arranged in series along the incident direction of light, thereby efficiently guiding light from the outside to each light-receiving element. Further, the detailed description of the light receiving element and the microlens is omitted, but those generally applicable to this type of product can be suitably used.

The low refractive index film formed from the curable resin composition of the present invention can be applied to the surface of the pixel portion to form an anti-reflection film. Alternatively, a flattening film or the like may be disposed under the film.

The thickness of the low refractive index film (antireflection film) is preferably 5 占 퐉 or less, more preferably 3 占 퐉 or less, and particularly preferably 1.5 占 퐉 or less in view of the effect of the present invention being remarkable. Although there is no particular lower limit value, it is practical that it is 50 nm or more.

The curable resin composition of the present invention is preferably a cured film corresponding to the dimensions of the pixel portion. For example, an antireflection film partitioned by a dimension corresponding to the pixel portion is preferable because it can cope with a specific product design and manufacturing process.

The curable resin composition of the present invention is suitably used for a display panel, a solar cell, an optical lens, a camera module, and a sensor module. More specifically, the present invention is useful as a curable resin composition for forming an antireflection film for preventing reflection of incident light, an interlayer film using a refractive index difference used for a sensor, a camera module, or the like, in the above solar cell and the like.

Example

Next, the present invention will be described by way of examples, but the present invention is not limited thereto. The amounts and ratios specified in the examples are on a mass basis unless otherwise specified.

&Lt; Example 1, Comparative Example 1 >

(1) Preparation of colloidal silica particle liquid

First, tetraethoxysilane (TEOS) was used as the silicon alkoxide (A), and trifluoropropyltrimethoxysilane (TFPTMS) was used as the silicon alkoxide (B) containing the fluoroalkyl group. The silicon alkoxide (A) (Mass ratio) of the fluoroalkyl group-containing silicon alkoxide (B) was 0.6 when the mass of the fluoroalkyl group was 1, and these were put into a separable flask and mixed to obtain a mixture. An amount of propylene glycol monomethyl ether (PGME) in an amount of 1.0 part by mass based on 1 part by mass of the mixture was added as an organic solvent (E), and the mixture was stirred at a temperature of 30 캜 for 15 minutes to prepare a first solution.

Separately from this first liquid, an amount of ion-exchanged water (C) in an amount of 1.0 part by mass based on 1 part by mass of the mixture and an amount of formic acid (D) in an amount of 0.01 part by mass were put into a beaker and mixed. And the mixture was stirred at a temperature for 15 minutes to prepare a second solution. Next, the prepared first liquid was maintained at a temperature of 55 캜 in a water bath, then the second liquid was added to the first liquid, and the mixture was stirred for 60 minutes while maintaining the temperature. Thus, the silicon alkoxide (A) and the hydrolyzate (F) of the silicon alkoxide (B) containing the fluoroalkyl group were obtained.

The solid content concentration of this liquid was 10% by mass in terms of SiO ₂ .

Next, a mixed solution obtained by adding 30 parts by mass of a 30% by mass aqueous solution of calcium nitrate to an aqueous dispersion (commercially available from Grace Japan, trade name: LUDOX HSA) containing 30% by mass of colloidal silica having an average diameter of 10 nm on the market was added to a stainless steel autoclave Lt; 0 &gt; C for 5 hours. For this dispersion, the solvent was replaced with propylene glycol monomethyl ether by ultrafiltration, and further stirred for 30 minutes at a rotational speed of 14000 rpm using a homomixer (manufactured by Freimix Co., Ltd.) Propylene glycol monomethyl ether was added to obtain a colloidal silica particle liquid (G) having a solid content concentration of 15 mass%.

30 parts by mass of the hydrolyzate (F) of the silicon alkoxide and 70 parts by mass of the colloidal silica particle liquid (G) were mixed and further heated at 40 DEG C for 10 hours, centrifuged at 1000G for 10 minutes to remove the precipitate, To obtain colloidal silica particle liquid 1-1.

The particle diameters of the silica particles contained in the obtained particle liquid were as follows.

DO: 10 nm

D1 / D2: 4.5

D1: 80 nm

D0: number average particle diameter of spherical particles (diameter of particles observed by TEM)

D1: the number average particle diameter of the colloidal silica particles measured by the dynamic light scattering method

D2: average particle diameter of the colloidal silica particles obtained from the specific surface area

(2) Preparation of curable resin composition

Using the colloidal silica particle liquid 1-1 thus obtained, the respective components were mixed so as to have the following composition to obtain a curable resin composition. Other curable resin compositions were obtained in the same manner except that the components in the composition were changed as shown in the following table.

<Composition>

The colloidal silica liquid prepared in the above : 59.9 parts by mass of the total solid content

Polymerizable compound (M1) (trade name: M305, manufactured by Toagosei Co., Ltd.)

: Mass of total solid content 12.5 parts

Oxime photopolymerization initiator (O1)

(Trade name: IRGACURE OXE-02, manufactured by BASF)

: 6.0 parts by mass of total solids

Resin (R1) (manufactured by Daicel Chemical Industries, Ltd.,

Trade name: Cyclomer P (ACA) 230AA)

: 24.4 parts by mass of the total solid content

· Polymerization inhibitor (para-methoxyphenol) : 0.01 parts by mass of the total solid content

Surfactant F (the following fluorine surfactant, 1% PGMEA solution)

: 0.5 parts by mass of the total solid content

· Organic solvents (cyclohexanone (XAN))

: 85 parts by mass relative to the total solid content of the curable resin composition

(26)

Polymerizable compound (M1): 55 to 63% of triacrylate

(27)

Oxime-based photopolymerization initiator (O1):

Product name: IRGACURE OXE-02, manufactured by BASF

(28)

Surfactant F: Megafac F-781F, manufactured by DIC Corporation

In the above structure, EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

[Chemical Formula 29]

Oxime photopolymerization initiator (O2):

Product name: IRGACURE OXE-01, manufactured by BASF

(30)

Oxime-based photopolymerization initiator (O3) (oxime compound having the above structure,

Synthesized by the method of Synthesis Example 7 of JP-A-2007-316451)

(31)

The? -aminoketone photopolymerization initiator (A1) (compound of the above structure,

Trade name: IRGACURE 369, manufactured by BASF)

Polymerizable compound (M2) (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

Polymerizable compound (M3) (trade name: KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd.)

Polymerizable compound (M4) (trade name: KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.)

Polymerizable compound (M5) (Aronix TO-2349, product of Toagosei Co., Ltd.)

Polymerizable compound (M6) (trade name: NK Ester A-DPH-12E manufactured by Shin Nakamura Kagaku Co., Ltd.)

[evaluation]

Using the respective curable resin compositions of the examples and comparative examples obtained above, the following evaluations were carried out.

&Lt; Evaluation of resolution >

The curable resin compositions of the examples and comparative examples obtained above were applied to a silicone wafer with an undercoat layer by a spin coat method so that the film thickness after coating was 0.8 占 퐉 and then heated on a hot plate at 100 占 폚 for 2 minutes Thereby obtaining a curable resin composition layer.

Subsequently, the obtained curable resin composition layer was exposed (exposure amount: 400 mJ / cm ² ) through a mask using a i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) with a 10 μm square Bayer pattern.

Next, to the curable resin composition layer after exposure, a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used to perform a puddle development at 23 占 폚 for 60 seconds. Thereafter, rinsing was carried out with a spin shower, and further washed with pure water to obtain a pattern. Further, the substrate was heated on a hot plate at 230 DEG C for 10 minutes to form a curable resin composition layer.

The amount of the residue remaining on the base of the obtained pattern was evaluated by image binarization. The results are shown in Table 1 below.

4: Less than 1% of total area of residue

3: 1% or more but less than 3% of total area of residue

2: 3% or more but less than 5% of total area of residue

1: 5% or more of total area of residue

0: Could not develop

[Table 1]

<Note in the table>

Particle liquid: colloidal silica particle liquid

Initiator I: Oxime-based photopolymerization initiator

Initiator II: alpha aminoketone photopolymerization initiator

Mass ratio: oxime type photopolymerization initiator: the weight ratio of? -Aminoketone type photopolymerization initiator

The total amount of initiator was 6.0 parts by mass.

Monomer: Polymerizable compound

ClogP: ClogP value of polymerizable compound

It was confirmed that the transparent cured films prepared by the above Tests 101 to 110 had no fogging and were excellent in transparency and that the refractive index was in a good range of 1.2 to 1.4 (633 nm, 25 DEG C).

Further, a compound having R = R1, T = T6, N = 1 in the above formulas MO-1 to MO-2 and MO-4 to MO-7 was used for the polymerizable compound (M3) The same experiment was carried out. All had a resolution of 2 to 4.

An experiment was conducted in the same manner as in Test 102 except that the polymerizable compound was changed from M2 to M6 (ClogP = 1.99). As a result, the development of the coating film was possible, but the result was slightly poor in the resolution.

An experiment was conducted in the same manner as in Tests 101 to 110 except that the polymerizable compound was changed to Shin Nakamura Kagaku Co., Ltd., trade name: NK Ester A-TMMT (ClogP value 2.78). All had a resolution of 4. In addition, in Test 102, the resolution was evaluated in the same manner except that the α-amino ketone polymerization initiator was changed to IRGACURE-819 and DAROCUR-TPO. The result was a result of resolution "3" to "4". As is evident from the above evaluation, it was found that the cured resin composition of the present invention had excellent transparency, realized a desired low refractive index, and good resolution at the time of molding.

&Lt; Example 2 >

Triethylene glycol monobutylether (boiling point 271 DEG C) was added to the curable resin composition (Particle Liquid 1-1) of Tests 101 to 110 in 15 parts by mass. As a result, it was confirmed that the dryness of the particle liquid 1-1 was suppressed, and both the production suitability and the production quality were improved.

While the present invention has been described in conjunction with the embodiments thereof, it is to be understood that the invention is not to be limited to any details of the description thereof except as otherwise specified, I think it is natural to be.

This application claims priority based on patent application number 2014-024830, filed February 12, 2014, which is incorporated herein by reference in its entirety.

Claims (17)

A curable resin composition comprising colloidal silica particles and a polymerizable compound. The method according to claim 1,
Wherein the polymerizable compound has a ClogP value of 2 or more. The method according to claim 1 or 2,
Wherein the polymerizable compound has a ClogP value of 2 to 10. The method according to any one of claims 1 to 3,
A curing resin composition further containing a polymerization initiator. The method according to any one of claims 1 to 4,
A curable resin composition comprising a solvent. The method according to any one of claims 1 to 5,
And further contains an alkali-soluble resin as a binder. The method according to any one of claims 1 to 6,
Wherein the colloidal silica particles take a form in which the spherical silica particles are connected in the form of a bead. The method according to any one of claims 1 to 7,
Wherein the colloidal silica particles comprise a plurality of spherical silica particles having an average particle diameter of 5 to 50 nm and a bonding portion for bonding the plurality of spherical particles to each other. The method according to any one of claims 1 to 8,
Wherein said colloidal silica particles have the following properties.
The number average particle diameter D1 measured by the dynamic light scattering method is 30 to 300 nm.
The ratio of the average particle diameter D2 determined from the specific surface area to the above-mentioned D1, D1 / D2, is 3 or more. The method of claim 7,
And the spherical silica particles are connected in a planar manner. The method according to any one of claims 1 to 10,
A curable resin composition containing a polysiloxane component. The method according to any one of claims 1 to 11,
Wherein the polymerizable compound is a compound represented by any one of the following formulas (MO-1) to (MO-7).
[Chemical Formula 1]

T is a connector. R is a group having a hydroxyl group, an alkyl group or a vinyl group at the terminal. Provided that at least one group in the molecule has a vinyl group. Z is a linking group. The method according to any one of claims 1 to 12,
Wherein the polymerizable compound is contained in an amount of 5 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the colloidal silica particles. The method according to any one of claims 1 to 13,
A curable resin composition for forming a low refractive index film. An antireflection film obtained by curing the curable resin composition according to claim 14. A solid-state imaging device comprising the antireflection film according to claim 15. A camera module incorporating the solid-state image pickup device according to claim 16.