KR20140023969A - Dispersion composition, curable composition, composition, transparent film, microlens, solid-state image sensing device, method for manufacturing transparent film, method for manufacturing microlens and method for manufacturing solid-state image sensing device - Google Patents

Abstract

The present invention relates to a metal oxide particle (A-1) having a primary particle diameter of 1 nm to 100 nm, and a graft copolymer (B-1) having a graft chain having 40 to 10,000 atoms of graft chains other than hydrogen atoms , And a dispersion composition containing a solvent (C-1), wherein the content of the metal oxide particles (A-1) is 50% by mass to 90% by mass relative to the total solids content of the dispersion composition, and the graft copolymer (B-1) has a structural unit which has an acidic radical in the quantity of 25 mass%-90 mass% with respect to the total mass of the said graft copolymer (B-1).

Description

Dispersion composition, curable composition, composition, transparent film, microlens, solid-state imaging device, method for producing transparent film, method for producing microlens and method for producing solid-state imaging device {DISPERSION COMPOSITION, CURABLE COMPOSITION, COMPOSITION, TRANSPARENT FILM, MICROLENS, SOLID-STATE IMAGE SENSING DEVICE, METHOD FOR MANUFACTURING TRANSPARENT FILM, METHOD FOR MANUFACTURING MICROLENS AND METHOD FOR MANUFACTURING SOLID-STATE IMAGE SENSING DEVICE}

The present invention relates to a dispersion composition, a curable composition, a composition, a transparent film, a microlens, a solid-state imaging device, a manufacturing method of a transparent film, a manufacturing method of a microlens, and a manufacturing method of a solid-state imaging device.

An optical wiring that replaces a microlens or copper wiring used for imaging optics of an on-chip color filter such as an electronic radiation machine and a solid-state imaging device, and has a high refractive index, and has a high refractive index, There is a need for a composition for forming a transparent member that can be formed.

In particular, the microlenses used in the solid-state imaging device are required to have a smaller size as the miniaturization of the solid-state imaging device proceeds and to have a high refractive index in order to achieve a more efficient optical focus. For example, a photopolymerizable composition capable of forming a high refractive index pattern using silica coated titanium oxide particles is disclosed (see, for example, Japanese Patent Application Laid-Open No. 2009-179678). A composition for a solid-state imaging device using a metal oxide having 20% or more silicon atoms on a particle surface is disclosed, and high refractive index and excellent pattern formability are obtained (for example, Japanese Patent Application Laid-Open No. 2008). -185683). In particular, with the recent increase in resolution, it is necessary to reduce the size of the pixels correspondingly and to collect light more efficiently. Therefore, there is a need for a microlens having a higher refractive index. Increasingly, the size of wafers used to produce more devices in one manufacturing process is increasing.

As a composition for forming a transparent high refractive index coating using titanium oxide particles, a composition containing titanium oxide, a surfactant and a binder polymer is disclosed in Example 3 of Japanese Patent Application Laid-open No. H8-110401.

However, when the size of the wafer is increased, the film formed to obtain the microlens has a performance in a plurality of solid-state image pickup chips obtained by cutting from the wafer because the difference in film thickness between the center portion and the peripheral portion of the wafer increases. Has the problem that fluctuations in can occur.

The present invention has been made in consideration of the above-described situation, and a first object of the present invention is to form a film having a small difference in film thickness between the central portion and the peripheral portion even when the composition is applied onto a large size wafer. It is to provide a dispersion composition having excellent dispersion stability that can be achieved and also having a very high refractive index when produced as a curable composition, a curable composition, a transparent film, a microlens, and a solid-state imaging device using the same.

The composition for forming the high refractive index material described in the above-mentioned patent document causes a significant change in the shape of the coated surface over time after the application of the composition, and also on the film surface when the film is left at room temperature for 24 hours after the application. Problems such as the generation of non-uniform sites. The generation of such non-uniform sites on the film surface is presumed to be due to the generation of cohesion caused by poor compatibility of the binder polymer with the metal oxide.

When the microlenses are manufactured by etching with the composition for forming the high refractive index material described in the above-mentioned patent document, the following problems have been found by the inventors. That is, in order to form a microlens, when a resist is applied on a high refractive index material formed of the above-described composition, and then subjected to pattern exposure and development, the surface from which the resist is removed by the developer (that is, the high refractive index material of the lower layer is exposed). Surface) is affected by contact with the developer, resulting in a decrease in the refractive index of the high refractive index material, leading to a problem that a microlens having a high refractive index of the desired performance cannot be obtained.

In addition, the present invention has been made in consideration of the above-described situation, and a second object of the present invention is a coated surface having a high refractive index capable of forming a film having a low drop in refractive index after development treatment, and over time after application of the composition. The composition which has little modification | denaturation in shape, and the transparent film, a microlens, a solid-state image sensor, the manufacturing method of a transparent film, the manufacturing method of a microlens, and the manufacturing method of a solid-state image sensor using this are provided.

A specific method for solving the first problem of the present invention is as follows.

Metal oxide particles (A-1) having a primary particle diameter of <1> 1 nm to 100 nm;

Graft copolymer (B-1) which has the graft chain of 40-10,000 atoms of graft chains other than a hydrogen atom; And

As a dispersion composition containing a solvent (C-1),

The content of the metal oxide particles (A-1) is 50% by mass to 90% by mass relative to the total solids content of the dispersion composition,

The graft copolymer (B-1) has a structural unit having an acid group in an amount of 25% by mass to 90% by mass relative to the total mass of the graft copolymer (B-1).

&Lt; 2 > The method according to < 1 &

The graft copolymer (B-1) has a dispersing composition, characterized in that it has an acid value of 70 mgKOH / g ~ 350 mgKOH / g.

<3> In <1> or <2>,

The graft chain of the graft copolymer (B-1) is at least one structure selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylic structure.

<4> In any one of <1>-<3>,

The graft copolymer (B-1) is a graft copolymer containing a structural unit represented by at least one of the following general formulas (1) to (4).

[In General Formula (1)-(4), X <^1> , X <^2> , X <^3> , X <^4> and X <^5> represent a hydrogen atom or a monovalent organic group each independently;

W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH;

R represents a hydrogen atom or a monovalent organic group, and R having another structure may exist in the copolymer;

R 'represents a branched alkylene group or a straight chain alkylene group, and R' having another structure may be present in the copolymer;

Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group;

Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a hydrogen atom or a monovalent substituent;

j and k each independently represent an integer of 2 to 8;

n, m, p and q each independently represent an integer of 1 to 500.]

<5> In any one of <1>-<4>,

The graft copolymer (B-1) is a graft copolymer containing a structural unit having a graft chain in the range of 10% by mass to 75% by mass relative to the total mass of the graft copolymer (B-1). Dispersion composition characterized by.

<6> In any one of <1>-<5>,

The acid group of the structural unit having an acid group is at least one group selected from the group consisting of a carboxylic acid group, a sulfonic acid group and a phosphoric acid group.

<7> As a curable composition containing the dispersion composition in any one of <1>-<6>,

The said dispersion composition contains a polymeric compound (D-1) and a polymerization initiator (E-1) further, The curable composition characterized by the above-mentioned.

<8> In <7>,

Curable composition further containing binder polymer (F-1).

<9> In <7> or <8>,

The said polymerization initiator (E-1) is an oxime system photoinitiator, The curable composition characterized by the above-mentioned.

<10> In any one of <7>-<9>,

A curable composition, which is used to form a microlens.

<11> In any one of <7>-<9>,

A curable composition, which is used to form an undercoat film of a color filter.

<12> The transparent film formed using the curable composition in any one of <7>-<11>.

<13> The microlens formed using the transparent film obtained by the curable composition as described in <10>.

<14> In <13>,

A microlens formed by dry etching the transparent film.

<15> The solid-state image sensor containing the transparent film as described in <12> and the microlens as described in <13> or <14>.

A specific method for solving the second problem of the present invention is as follows.

[1] titanium oxide particles or zirconium oxide particles as metal oxide particles (A-2);

Binder polymer (F-2) containing a repeating unit derived from benzyl (meth) acrylate; And

As a composition containing surfactant (G-2),

The content of the surfactant (G-2) is 0.0010% by mass to 3.0% by mass relative to the total solids content of the composition.

[2] The method according to [1]

The surfactant (G-2) is a composition, characterized in that the fluorine-based surfactant or nonionic surfactant.

[3] The method according to [1] or [2]

The content of the surfactant (G-2) is 0.50% by mass to 3.0% by mass based on the total solids content of the composition.

[4] The method according to any one of [1] to [3]

A composition comprising titanium oxide particles as the metal oxide particles (A-2).

[5] any one of [1] to [4],

The binder polymer (F-2) further comprises a repeating unit derived from (meth) acrylate.

[6] any one of [1] to [5],

The binder polymer (F-2) has an ethylene oxide group.

[7] any one of [1] to [6],

The binder polymer (F-2) further comprises both a repeating unit derived from an alkyl (meth) acrylate having an ethylene oxide group and a repeating unit derived from isobutyl (meth) acrylate.

[8] any one of [1] to [7],

Composition for use in forming microlenses.

[9] A transparent film formed by using the composition according to any one of [1] to [8].

[10] A microlens formed by using the transparent film as described in [9].

[11] The method of [10],

A microlens formed by dry etching the transparent film.

[12] A solid-state imaging device comprising the microlens according to [10] or [11].

[13] a step of applying the composition according to any one of [1] to [8] on a wafer; next,

A first heating step of heating the composition; next,

And a second heating step of heating the composition at a temperature higher than the heating temperature in the first heating step.

[14] a step of subjecting the transparent film of [9] to post-baking to form a transparent film; And

A method of manufacturing a microlens, comprising the step of dry etching the transparent film.

[15] forming a red pixel, a blue pixel and a green pixel on a substrate for a solid-state imaging device having at least a photodiode, a light blocking film, and a device protective film;

Applying the composition according to any one of [1] to [8] and performing heating;

Forming a resist pattern;

Molding the formed resist pattern into a lens type shape by performing a post bake treatment; And

A method of manufacturing a solid-state imaging device, comprising the step of performing dry etching.

Dispersion composition of the present invention (hereinafter sometimes referred to as the first invention) for solving the first problem of the present invention is a graft copolymer having a graft chain having a number of atoms other than hydrogen atoms in the range of 40 to 10,000 ( B-1) is contained as a dispersant. Thus, for example, the graft chain plays a role of a three-dimensional repulsive group to exhibit excellent dispersibility, so that the metal oxide particles can be uniformly dispersed as high refractive index particles. Even if the dispersion composition is stored at room temperature or the like for a long time, the graft chains may inhibit the metal oxide particles from being precipitated for a long time by interacting with the solvent. When a coating film is formed with the dispersion composition (more specifically, for example, a curable composition), the graft chain acts as a three-dimensional repulsion to prevent agglomeration of metal oxide particles, and thus Increasing the content may not easily reduce the dispersion stability. That is, the dispersion composition of the present invention can be used to achieve excellent dispersion stability and to obtain a film having a very high refractive index.

The graft copolymer (B-1) (particularly, the graft copolymer including the structural unit represented by any one of the general formulas (1) to (5) which is a preferred embodiment) constitutes a dispersion composition. When the dispersion composition is used to constitute a curable composition, the uniformity of the film thickness of the coating film obtained by the curable composition is excellent, and as a result, even when applied onto a large size wafer, A film having a small difference in film thickness between the central portion and the peripheral portion (for example, an undercoat film of a color filter or a film forming a microlens, etc.) can be obtained. This is presumably because the graft chain and the solvent of the graft copolymer (B-1) of the present invention exhibit excellent interaction with each other in, for example, a coating film.

In order to solve the second problem of the present invention, when a specific amount of the surfactant is not present in the composition of the present invention, the solvent is removed by drying after application, and thus the compatibility of the metal oxide particles in close contact with the binder polymer is timely. Over time, it becomes unstable and causes aggregation with metal oxide particles, leading to deterioration of the surface shape. However, it is assumed that a certain amount of surfactant is combined between the metal oxide particles and the binder polymer to improve compatibility, and as a result, changes in the shape of the coated surface can be reduced over time after application of the composition.

In the case where the microlenses are manufactured by etching with the composition of the present invention, the surface of the resist from which the resist is removed by the developer and the developer by applying a resist on the high refractive index material formed of the composition of the present invention (that is, the Even when the exposed surface is contacted, and then the pattern is exposed to light and developed, a non-uniform portion is generated only on the surfaces of the metal oxide particles and the binder polymer as described above, and therefore, a specific amount of surfactant in the composition of the present invention. Is present, the developer sometimes enters between the gaps, causing a decrease in refractive index. However, if a certain amount of surfactant is present, it is presumed to provide a film having a low drop in refractive index by preventing the surfactant from entering the gap and preventing the unevenness of the surface that appears potentially, and preventing the developer from entering the gap.

That is, the composition of the present invention can be used to obtain a film having a high refractive index, a small change in the shape of the coated surface with time after application of the composition, and a low drop in the refractive index after the development treatment.

Hereinafter, the dispersion composition according to the first invention of the present invention and the composition according to the second invention will be described in detail.

In addition, in showing a group (atom group) in this specification, the arbitrary expression which is not describing substitution and unsubstitution includes having a substituent and having no substituent. For example, an "alkyl group" includes an alkyl group having a substituent (substituted alkyl group) and an alkyl group having no substituent (unsubstituted alkyl group).

Although the description of the constituent factors described below can be made based on representative exemplary embodiments of the present invention, the present invention is not limited to these exemplary embodiments. Here, in this specification, the range of the numerical value represented by using "-" shows the range containing the value of the numerical value described before and after "-" as a lower limit and an upper limit.

Here, in this specification, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acryl and methacryl, and "meth (acryloyl)" is acryloyl. And methacryloyl. In the present specification, "monomer" and "monomer" are the same as each other. In the present specification, the monomer is different from the oligomer and the polymer, and the monomer means a compound having a mass average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group means a group associated with a polymerization reaction.

In the present invention, "refractive index" means a refractive index with respect to light having a wavelength of 500 nm unless otherwise specified.

First, the first invention of the present invention will be described.

<Dispersion Composition>

The dispersion composition according to the first invention of the present invention is a graft air having a graft chain having a metal oxide particle (A-1) having a primary particle diameter of 1 nm to 100 nm and a number of atoms other than hydrogen atoms in the range of 40 to 10,000. A dispersion composition containing copolymer (B-1) and a solvent (C-1), wherein the content of the metal oxide particles (A-1) is 50% by mass to 90% by mass with respect to the total solids content of the dispersion composition. (In this specification, mass ratio is equivalent to weight ratio).

By having the above structure, even when the composition is applied onto a large size wafer, a film (typically a transparent film) having a small difference in film thickness between its central portion and its peripheral portion can be formed as described later. It is possible to provide a dispersion composition having the same excellent dispersion stability and also having a very high refractive index when prepared as a curable composition.

(A-1) metal oxide particles

In the present invention, the metal oxide particles are inorganic particles having a high refractive index, and examples of the metal oxide particles are titanium dioxide (Ti0 ₂ ) particles, zirconium dioxide (Zr0 ₂ ) particles, and silicon dioxide (Si0 ₂ ). Particles are included, but among these, titanium dioxide particles (hereinafter sometimes simply referred to as "titanium dioxide") are preferable.

In the present invention, the metal oxide particles are not particularly limited as long as the particles have a primary particle diameter of 1 nm to 100 nm, and are preferably selected from commercially available metal oxide particles.

The metal oxide particles have a primary particle diameter of 1 nm to 100 nm, preferably 1 nm to 80 nm, particularly preferably 1 nm to 50 nm. When the primary particle diameter of the metal oxide particles exceeds 100 nm, the refractive index and transmittance may be reduced. If the diameter is less than 1 nm, dispersibility or dispersion stability may be reduced by aggregation.

In the present invention, the primary particle diameter of the metal oxide particles is obtained as the average particle diameter of the metal oxide particles. In the present invention, the average particle diameter of the metal oxide particles is measured by using a dynamic light scattering method on the dilution obtained by diluting a mixed solution or dispersion containing metal oxide particles by 80 times with propylene glycol monomethyl ether acetate. It means the value obtained.

This measurement is calculated as a number average particle diameter obtained by performing a measurement using MICROTRAC UPA-EX150 (manufactured by NIKKISO Co., Ltd.).

In the present invention, the refractive index of the metal oxide particles is not particularly limited, but is preferably 1.75 to 2.70, more preferably 1.90 to 2.70 from the viewpoint of obtaining a high refractive index.

The metal oxide particles preferably have a specific surface area of 10 m 2 / g to 400 m 2 / g, more preferably 20 m 2 / g to 200 m 2 / g, and most preferably 30 m 2 / g to 150 m 2 / g. .

There is no particular limitation on the shape of the metal oxide particles. For example, it may be a rice-grain shape, spherical shape, cubic shape, fusiform shape, or irregular shape.

In the present invention, the metal oxide particles may be surface treated with an organic compound. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents and titanate coupling agents. Among these, the said silane coupling agent is preferable.

The surface treatment may be performed alone or in combination of two or more surface treating agents.

In addition, the surface of the metal oxide particles is preferably coated with oxides such as aluminum, silicon, and zirconia. Therefore, weather resistance is further improved.

As a metal oxide particle of this invention, a commercial item can be used preferably.

Examples of commercially available products of the titanium dioxide particles include ISHIHARA SANGYO KAISHA, LTD. TTO series (TTO-51 (A), TTO-51 (C), etc.), TTO-S and V series (TTO-S-1, TTO-S-2, TTO-V-3, etc.), TAYCA CORP . MT series (MT-01, MT-05, etc.) etc. are included.

Examples of commercially available products of the zirconium dioxide particles include UEP (manufactured by Daiichi Kigenso Kagaku Kogyo Ltd.), PCS (NIPPON DENKO CO., LTD.), JS-01, JS-03 and JS-04 (NIPPON DENKO CO. , LTD.), UEP-100 (made by Daiichi Kigenso Kagaku Kogyo Ltd.), and the like.

Examples of commercially available products of the silicon dioxide particles include Clariant Co. Agent OG502-31, etc. are included.

In the present invention, the metal oxide particles may be used alone or in combination of two or more thereof.

When the dispersion composition (or curable composition described later) of the present invention is configured to obtain a very high refractive index, the content of metal oxide particles in the composition is 50 mass based on the total solid content of the dispersion composition (or curable composition described later). It is%-90 mass%, 52 mass%-85 mass% are more preferable, and 55 mass%-80 mass% are the most preferable.

As described above, as the resolution becomes higher in recent years, microlenses having a very small size and a higher refractive index are required in order to collect light more efficiently. When the content of the metal oxide particles is less than 50 mass% with respect to the total solids content of the dispersion composition, it is difficult to obtain such microlenses.

When the content of the metal oxide particles is 90% by mass or more based on the total solids content of the dispersion composition (or the curable composition described later), it is difficult to present the graft copolymer (B-1) in a sufficient amount. Acidic and dispersion stability is easily degraded. When the dispersion composition (curable composition) is applied on a large size (e.g., 12 inch) wafer, it is difficult to form a film having a small difference in film thickness between the center portion and the peripheral portion of the wafer.

(B-1) Graft Copolymer

The dispersion composition of the present invention contains a graft copolymer (hereinafter sometimes referred to as "specific resin"). The graft copolymer of the present invention has a graft chain in the range of 40 to 10,000 atoms other than hydrogen atoms. In this case, the graft chains represent the chains from the source of the main chain of the copolymer (the atoms bonded with the main chain to the groups branched from the main chain) to the ends of the branched groups from the main chain. In the above dispersion composition, the specific resin is a dispersion resin which imparts dispersibility to the metal oxide particles, and has affinity with a solvent due to the graft chains, so that the dispersibility and dispersion of the metal oxide particles even after elapse of time. Excellent stability When the specific resin is made of the dispersion composition, the graft chain shows excellent interaction with the solvent. Therefore, it is thought to suppress that the uniformity of the film thickness of a coating film deteriorates.

The graft copolymer (B-1) used in the present invention preferably has 40 to 10,000 atoms per graft chain in addition to hydrogen atoms, and more preferably 100 to 500 atoms per graft chain in addition to hydrogen atoms. It is more preferable to have the number of 150-260 atoms per graft chain other than an atom.

When the number of atoms other than the hydrogen atoms is less than 40 per graft chain, the graft chain is short, so that the steric repulsion effect is reduced, and thus dispersibility or dispersion stability may be reduced. When the dispersion composition (curable composition) is applied on a large sized wafer (for example, 12 inches), it is difficult to form a film having a small difference in film thickness between the center portion and the peripheral portion of the wafer. On the other hand, when the number of atoms other than hydrogen atoms is more than 10,000 per graft chain, the graft chain is long, and thus the adsorptive force with the metal oxide particles is reduced, resulting in a decrease in dispersibility or dispersion stability.

On the other hand, the number of atoms per graft chain in addition to the hydrogen atoms means the number of atoms other than the hydrogen atoms contained in the chain from the atoms of the source bonded to the polymer chain constituting the main chain to the terminal of the branched polymer branched from the main chain. When the graft copolymer includes two or more graft chains, the number of atoms of the at least one graft chain in addition to the hydrogen atoms is sufficient to meet the requirements.

As the polymer structure of the graft chain, a poly (meth) acrylic structure, a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, a polyether structure, or the like can be used. However, in order to improve the interactivity of the graft chain with a solvent and to increase dispersibility or dispersion stability, it is preferable that it is a graft chain including a poly (meth) acrylic structure, a polyester structure or a polyether structure, and a polyester structure Or it is more preferable that it is a graft chain containing a polyether structure.

It is preferable that the graft copolymer has a structural unit (repeating unit) having a graft chain, and the graft copolymer can be obtained by polymerizing, for example, a macromonomer having a polymer structure as a graft chain according to a conventional method. have. The structure of the macromonomer is not particularly limited as long as it has a substituent capable of reacting with the polymer backbone moiety and also has a graft chain that satisfies the needs of the present invention. However, it is preferable to use a macromonomer having a reactive double bond group suitably.

On the other hand, the structural unit having the graft chain may be a structural unit that does not correspond to a structural unit having an acid group described later, and may be a structural unit corresponding to the structural unit having an acid group.

Examples of commercially available macro monomers which are preferably used for the synthesis of the specific resins include AA-6 (manufactured by TOAGOSEI Co., Ltd.), AA-10 (manufactured by TOAGOSEI Co., Ltd.), AB-6 (TOAGOSEI Co.). , Ltd.), AS-6 (made by TOAGOSEI Co., Ltd.), AN-6 (made by TOAGOSEI Co., Ltd.), AW-6 (made by TOAGOSEI Co., Ltd.), AA-714 ( TOAGOSEI Co., Ltd.), AY-707 (manufactured by TOAGOSEI Co., Ltd.), AY-714 (manufactured by TOAGOSEI Co., Ltd.), AK-5 (manufactured by TOAGOSEI Co., Ltd.), AK- 30 (made by TOAGOSEI Co., Ltd.), AK-32 (made by TOAGOSEI Co., Ltd.), BLEMMER PP-100 (made by NOF Corporation), BLEMMER PP-500 (made by NOF Corporation), BLEMMER PP-800 (NOF Corporation), BLEMMER PP-1000 (product of NOF Corporation), BLEMMER 55-PET-800 (product of NOF Corporation), BLEMMER PME-4000 (product of NOF Corporation), BLEMMER PSE-400 (product of NOF Corporation), BLEMMER PSE-1300 (Made by NOF Corporation), BLEMMER 43PAPE-600B (made by NOF Corporation), etc. are mentioned. Among these, AA-6 (made by TOAGOSEI Co., Ltd.), AA-10 (made by TOAGOSEI Co., Ltd.), AB-6 (made by TOAGOSEI Co., Ltd.), AS-6 (TOAGOSEl Co., Ltd.) )) AN-6 (product of TOAGOSEl Co., Ltd.), BLEMMER PME-4000 (product of NOF Corporation), BLEMMER PME-400 (product of NOF Corporation), BLEMMER PME-100 (product of NOF Corporation), BLEMMER PME- 200 (made by NOF Corporation), BLEMMER PME-1000 (made by NOF Corporation), etc. are preferable.

It is preferable that the specific resin used for this invention contains at least 1 structural unit represented by either of following General formula (1)-General formula (4) as a structural unit which has a graft chain, and is following General formula (1A) It is more preferable to include at least one structural unit represented by any one of the following general formula (2A), the following general formula (3) and the following general formula (4).

In General Formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of limitation on the synthesis, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.

In the general formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH, and an oxygen atom is particularly preferable.

In general formula (3), R 'represents a branched or straight-chain alkylene group (1-10 carbon atoms are preferable, and 2 or 3 carbon atoms are more preferable), and -CH <_2> - Groups represented by CH (CH ₃ ) — or groups represented by —CH (CH ₃ ) —CH ₂ — are preferred.

As R 'of General formula (3), 2 or more types of R' which have a different structure in specific resin can be mixed and used.

In General Formulas (1) to (4), Y ¹ , Y ² , Y ^3, and Y ⁴ each independently represent a divalent linking group, and the structure is not particularly limited. Specifically, examples thereof include a linking group from the following (Y-1) to (Y-21). In the following structures, A and B represent the bond with the left terminal group and the bond with the right terminal group in the general formulas (1) to (4), respectively. Among the following structures, it is more preferable to use (Y-2) and (Y-13) because of the ease of synthesis.

In the general formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a hydrogen atom or a monovalent substituent. The structure of the substituent is not particularly limited, but specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group or a heteroaryloxy group, an alkyl thioether group, an aryl thioether group or a heteroaryl thioether group, Amino groups and the like. Among these, from the viewpoint of improving dispersibility, it is particularly preferable that the group has a steric repulsion effect, and as a monovalent substituent represented by Z ¹ to Z ³ , the groups are each independently an alkyl group having 5 to 24 carbon atoms or 5 It is preferable that it is an alkoxy group having ˜24 carbon atoms, and among these groups, each of these groups independently contains an alkoxy group containing a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to 24 carbon atoms. It is especially preferable that it is an alkoxy group. The monovalent substituent represented by Z ⁴ is preferably an alkyl group having 5 to 24 carbon atoms, and among these groups, each of these groups independently has a branched alkyl group having 5 to 24 carbon atoms or 5 to 24 carbon atoms. It is preferable that it is a cyclic alkyl group.

In the general formulas (1) to (4), n, m, p and q are each an integer of 1 to 500.

In General formula (1) and General formula (2), j and k are the integers of 2-8 each independently. In General Formula (1) and General Formula (2), j and k are preferably integers of 4 to 6, and most preferably 5 from the viewpoint of dispersion stability.

In the general formula (4), R represents a hydrogen atom or a monovalent organic group, and its structure is not particularly limited, but examples thereof include a hydrogen atom, an alkyl group, an aryl group and a heteroaryl group, and hydrogen More preferred are atoms and alkyl groups. When R is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, 1 The linear alkyl group having ˜20 carbon atoms is more preferable, and the linear alkyl group having 1 to 6 carbon atoms is particularly preferable.

As R of General formula (4), 2 or more types of R which have a different structure in specific resin can be mixed and used.

As a structural unit represented by General formula (1), the structural unit represented by following General formula (1A) or following General formula (2A) from a viewpoint of dispersion stability is more preferable.

In the formula ^{(1A), X 1, Y} 1, Z 1 and n are the same as X ^1, Y ^1, Z ¹ and n in the formula (1), and is also equal to each other preferred range of it.

In the formula ^{(2A), X 2, Y} 2, Z 2 and m are represented by the general formula ^{(2) X 2, Y 2} , Z 2 , and the same as m, and is also equal to each other preferred range of it.

As for the said specific resin, it is more preferable to have a structural unit represented by General formula (1A).

The specific resin may have one structural unit or a plurality of structural units having a graft chain.

In specific resin used for this invention, it is preferable that the structural unit (repeating unit) which has the said graft chain is contained in the range of 10 mass%-75 mass% with respect to the total mass of the said specific resin, 12 mass%- It is more preferable that it is the range of 50 mass%, and it is especially preferable that it is the range of 15 mass%-40 mass%. When the content of the structural unit is within these ranges, the dispersibility or dispersion stability of the metal oxide particles is high, and thus the uniformity of the film thickness of the coating film formed using the dispersion composition is better. The specific resin used in the present invention may be a combination of two or more graft copolymers having different structures.

The said specific resin in this invention is a polymer containing the structural unit (repeating unit) which has an acidic radical in the quantity of 25 mass%-90 mass% with respect to the total mass of the said specific resin. It is more preferable that it is 50 mass%-80 mass% with respect to the total mass of the said specific resin, and, as for content of the structural unit which has the said acidic radical, it is most preferable that it is 60 mass%-75 mass%.

When the content of the structural unit having an acid group is less than 25% by mass based on the total mass of the specific resin, the adsorptivity of the specific resin and the metal oxide particles of the present invention becomes insufficient, resulting in a decrease in dispersion stability. When the said dispersion composition (curable composition) is apply | coated on the wafer of large size (for example, 12 inches), it is difficult to form the film with a small difference in the film thickness between the center part and the periphery part of the wafer.

When the content of the structural unit having an acid group exceeds 90% by mass relative to the total mass of the specific resin, the amount of introduction of the graft chain into the specific resin is insufficient, resulting in a decrease in dispersion stability. Similarly, it is difficult to form a film having a small difference in film thickness between the center portion and the peripheral portion of the wafer.

When content of the structural unit which has the said acidic radical exists in the said range, the acid value of the said specific resin can be suitably adjusted in the following preferable ranges.

The acid groups serve as functional groups capable of forming interactions with other metal oxide particles other than the graft chain.

Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like, and are selected from a carboxylic acid group, a sulfonic acid group and a phosphoric acid group in view of adsorptivity, dispersibility and dispersion stability with the metal oxide particles. It is preferable that it is at least one, and a carboxylic acid group is especially preferable.

The acid group structure is preferably a structure in which the acid groups are separated by 5 atoms or more from the main chain of the resin structure. As said acid group, the carboxylic acid couple | bonded with an aromatic ring is the most preferable.

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

It is preferable that the acid value of the said specific resin exists in the range of 70 mgKOH / g-350 mgKOH / g, It is more preferable to exist in the range of 80 mgKOH / g-300 mgKOH / g, and 100 mgKOH / g More preferably, it is in the range of -250 mgKOH / g. Even when the dispersion composition is applied on a wafer of a large size (e.g., 12 inches), by adjusting the acid value within the above-described range, a film having a small difference in film thickness between the center portion and the peripheral portion of the wafer is more reliably. You can get it.

In the present invention, the acid value of the specific resin can be calculated, for example, from the average content of acid groups in the specific resin. By changing the content of the monomer unit containing the acid group constituting the specific resin, a resin having a desired acid value can be obtained.

The specific resin may further include a structural unit (repeating unit) having a functional group capable of forming interaction with metal oxide particles in addition to the graft chain and the acid group. The structural unit having a functional group capable of forming interaction with other metal oxide particles is not particularly limited in structure, but examples thereof include structural units having basic groups, structural units having coordinating groups, structural units having reactive groups, and the like. Included.

Examples of the basic group include primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing N atoms, amide groups and the like. Particular preference is given to tertiary amino groups having good adsorptivity with the metal oxide particles and having high dispersibility and dispersion stability. The basic groups may be used alone or in combination of two or more.

Although the specific resin of this invention may or may not contain the structural unit (repeating unit) which has a basic group, when the said specific resin contains the structural unit which has a basic group, the content of the structural unit which has the said basic group is said specificity. It is especially preferable that it is 0.1 mass%-50 mass% with respect to the total mass of resin, and they are 0.1 mass%-30 mass%.

Examples of such coordinating groups or reactive groups include acetyl acetoxy groups, trialkoxysilyl groups, isocyanate groups, acid anhydride residues, acid chloride residues and the like. Particularly preferred is an acetylacetoxy group having good adsorption power with the metal oxide particles and high dispersibility and dispersion stability. The ligand or reactive group may be used alone or in combination of two or more.

The specific resin of the present invention may or may not contain a structural unit (repeating unit) having a coordinating group or a reactive group, but when the specific resin contains a structural unit having the coordinating group or a reactive group, It is especially preferable that content of the structural unit which has a reactive group is 0.1 mass%-50 mass% with respect to the total mass of the said specific resin, and is 0.1 mass%-30 mass%.

The specific resin in this invention is a structural unit which has a functional group which can form interaction with the said structural unit which has the said graft chain and the structural unit which has an acidic radical, and another said metal oxide particle, and is following General formula (i)-general It may have at least one of the repeating units obtained from the monomer represented by any one of formula (iii).

In formulas (i) to (iii), each of R ¹ , R ^2, and R ³ independently represents a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, or the like) or 1 to 6 carbons. The alkyl group (for example, methyl group, ethyl group, propyl group, etc.) which has an atom is shown.

R ¹ , R ² and R ³ are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group. It is particularly preferred that R ² and R ³ are hydrogen atoms.

X represents an oxygen atom (-O-) or an imino group (-NH-), and an oxygen atom is preferable.

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group and a substituted alkynylene group), and a divalent aromatic group (for example , Arylene group and substituted arylene group), divalent heterocyclic group, and these groups and oxygen atom (-0-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ^31- , Wherein R ³¹ is an aliphatic group, aromatic group or heterocyclic group) or a combination of carbonyl group (—CO—).

The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group and a heterocyclic group.

It is preferable that the said divalent aromatic group has 6-20 carbon atoms, It is more preferable to have 6-15 carbon atoms, It is most preferable to have 6-10 carbon atoms. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group and a heterocyclic group.

The bivalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocycle may be condensed with other heterocycles, aliphatic rings or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= 0), a thioxo group (= S), an imino group (= NH), a substituted imino group (= NR ³² , wherein R ³² is an aliphatic group, an aromatic Group or heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

L is preferably a single bond, an alkylene group containing a oxyalkylene structure or a divalent linking group. As for the said oxyalkylene structure, it is more preferable that it is an oxyethylene structure or an oxypropylene structure. L may comprise a polyoxyalkylene structure in which two or more oxyalkylene structures are repeated. As said polyoxyalkylene structure, it is preferable that it is a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) _n- , where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In general formula (i)-(Z), Z represents the functional group which can form interaction with a metal oxide particle, It is preferable that it is an acidic group, basic group, or reactive group mentioned above, A carboxylic acid group or tertiary group An amino group is more preferable, and a carboxylic acid group is more preferable. Y represents a methine group or a nitrogen atom.

In the general formula (R), R ⁴ , R ⁵ And Each R ⁶ independently represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms, Z, or -LZ (e.g., methyl, ethyl, propyl); Group). Where L and Z are the same as described above. It is preferable that R <^4> , R <^5> and R <^6> are a hydrogen atom or the alkyl group which has 1-3 carbon atoms, and a hydrogen atom is more preferable.

In the present invention, the monomer represented by the general formula (i) is R ¹ , R ² and R ³ are each a hydrogen atom or a methyl group, L is a divalent linking group containing an alkylene group or an oxyalkylene structure, and X is It is preferable that it is an oxygen atom or an imino group, and Z is a compound which is a carboxylic acid group.

The monomer represented by the general formula (ii) is preferably a compound in which R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, Z is a carboxylic acid group, and Y is a methine group. It is preferable that the monomer represented by the said general formula (VIII) is a compound in which R <^4> , R <^5> and R <^6> is a hydrogen atom or a methyl group, respectively, and Z is a carboxylic acid group.

As an example of the typical compound represented by general formula (i)-general formula (i), methacrylic acid, crotonic acid, isocrotonic acid; Reactant of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a phthalic acid Reactants of anhydrides, compounds having addition polymerizable double bonds and hydroxyl groups in the molecule and tetrahydroxyphthalic anhydride, reactants of compounds and trimellitic anhydride having addition polymerizable double bonds and hydroxyl groups in the molecule, molecules Compounds having addition polymerizable double bonds and hydroxyl groups in them, pyromellitic anhydride, acrylic acid, acrylic acid pigments, acrylic acid oligomers, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid, vinyl phenol, 4-hydroxyphenyl meta Reactants of krillamide and the like.

The specific resin contained in the dispersion composition of the metal oxide particles of the present invention is a structural unit derived from a copolymerization component in order to improve various performances, such as image intensity, unless the effect of the present invention is reduced, and a structural unit having the graft chain. In addition to the structural units having the acid groups and the structural units having functional groups capable of forming interactions with the metal oxide particles, other structural units having more various functions different from these structural units, for example, dispersion media used for dispersion and And a structural unit including a functional group having affinity.

Examples of the copolymerization component capable of copolymerizing with a specific resin according to the present invention include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, and the like. do.

Specifically, examples thereof include an acrylic acid ester such as alkyl acrylate (preferably, the alkyl group has 1 to 20 carbon atoms) (specifically, for example, benzyl acrylate, 4-biphenyl acrylate, Butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 4-t-butylphenyl acrylate, 4-chlorophenyl acrylate, pentachlorophenyl acrylate, 4-cyanobenzyl acrylate, cyanomethyl acrylic Latex, cyclohexyl acrylate, 2-ethoxyethyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, hexyl acrylate, isobornyl acrylate, isopropyl acrylate, methyl acrylate, 3 , 5-dimethyl adamantyl acrylate, 2-naphthyl acrylate, neopentyl acrylate, octyl acrylate, phenethyl acrylate , Phenyl acrylate, propyl acrylate, tolyl acrylate, amyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 4- Hydroxybutyl acrylate, 5-hydroxypentyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate, etc.),

Methacrylic acid esters (e.g., benzyl methacrylate, 4-biphenyl methacrylate, butyl methacrylate, sec) such as alkyl methacrylates (the alkyl group preferably having 1 to 20 carbon atoms) -Butyl methacrylate, t-butyl methacrylate, 4-t-butylphenyl methacrylate, 4-chlorophenyl methacrylate, pentachlorophenyl methacrylate, 4-cyanophenyl methacrylate, cyanomethyl Methacrylate, cyclohexyl methacrylate, 2-ethoxy ethyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate, hexyl methacrylate, isobornyl methacrylate, iso Propyl methacrylate, methyl methacrylate, 3,5-dimethyl adamantyl methacrylate, 2-naphthyl methacrylate, neopentyl methacrylate, octyl methacrylate, phenethyl Methacrylate, phenyl methacrylate, propyl methacrylate, tolyl methacrylate, amyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate, 2- Diethylaminoethyl methacrylate, 2-dimethylamino methacrylate, etc.),

Styrenes such as styrene and alkyl styrene (e.g., methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl Styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (e.g., methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc.), halogenated styrene ( For example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4- Trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene and the like), acrylonitrile, methacrylonitrile and the like.

Among these radically polymerizable compounds, it is preferable to use methacrylic acid ester, acrylamide, methacrylamide and styrene. Examples of compounds which are particularly preferably used include benzyl methacrylate, t-butyl methacrylate, 4-t-butylphenyl methacrylate, pentachlorophenyl methacrylate, 4-cyanophenyl methacrylate, cyclohexyl meta Acrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, isopropyl methacrylate, methyl methacrylate, 3,5-dimethyladamantyl methacrylate, 2-naphthyl Methacrylate, neopentyl methacrylate, phenyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, Allyl methacrylate,

Acrylamide, N-methyl acrylamide, N-isopropyl acrylamide, morpholinyl acrylamide, piperidyl acrylamide, Nt-butyl acrylamide, N-cyclohexyl acrylamide, N-phenyl acrylamide, N-naphthyl Acrylamide, N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, N-allyl acrylamide, 4-hydroxyphenyl acrylamide, 2-hydroxyphenyl acrylamide, N, N-dimethyl acrylamide, N , N-diisopropyl acrylamide, N, N-di-t-butyl acrylamide, N, N-dicyclohexyl acrylamide, N, N-phenyl acrylamide, N, N-dihydroxyethyl acrylamide, N, N-diallyl acrylamide,

Methacrylamide, N-methyl methacrylamide, N-isopropyl methacrylamide, morpholyl methacrylamide, piperidyl methacrylamide, Nt-butyl methacrylamide, N-cyclohexyl methacrylamide, N-phenyl Methacrylamide, N-naphthyl methacrylamide, N-hydroxymethyl methacrylamide, N-hydroxyethyl methacrylamide, N-allyl methacrylamide, 4-hydroxyphenyl methacrylamide, 2-hydroxy Phenyl methacrylamide, N, N-dimethyl methacrylamide, N, N-diisopropyl methacrylamide, N, N-di-t-butyl methacrylamide, N, N-dicyclohexyl methacrylamide, N , N-phenyl methacrylamide, N, N-dihydroxyethyl methacrylamide, N, N-diallyl methacrylamide,

Styrene, methyl styrene, dimethyl styrene, trimethyl styrene, isopropyl styrene, butyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, 4-methoxy -3-methyl styrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo- 4-trifluoromethyl styrene and 4-fluoro-3-trifluoromethyl styrene are included.

The radically polymerizable compounds may be used alone or in combination of two or more. The said specific resin may or may not contain the radically polymerizable compound mentioned above. However, when the said resin contains a compound, the content of the structural unit corresponding to the said radically polymerizable compound is 0.1 mass%-50 mass% with respect to the total mass of the said specific resin, and 0.1 mass%-30 mass% especially desirable.

Certain resins in the present invention can be synthesized by methods well known in the art. Examples of the solvent used for the synthesis include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, l-methoxy-2-propyl acetate, N, N-dimethyl formamide, N, N-dimethyl acetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lac Tate and the like. These solvents may be used alone or in combination of two or more.

Specific examples of the specific resin in the present invention include the following Exemplary Compounds 1 to 34, but the present invention is not limited thereto. Among the following exemplary compounds, the numerical value attached to each structural unit (the numerical value attached to the main chain repeating unit) indicates the content of the structural unit (expressed in mass%: (wt%)). The numerical value attached to the repeating site of the side chain indicates the number of repetitions of the repeating site.

It is preferable that the weight average molecular weight (polystyrene conversion value measured by GPC method) of specific resin in this invention is 5,000-300,000, 7,000-100,000 are more preferable, 10,000-50,000 are especially preferable.

In the dispersion composition of the present invention, the specific resins may be used alone or in combination of two or more thereof.

From the viewpoint of dispersibility and dispersion stability, the content of the specific resin is preferably in the range of 10% by mass to 50% by mass relative to the total solids content of the dispersion composition (or curable composition described later) of the present invention, and is preferably 11% by mass. It is more preferable to exist in the range of -40 mass%, and it is still more preferable to exist in the range of 12 mass%-30 mass%.

-Other Dispersion Resin-

In order to control the dispersibility of metal oxide particle | grains, the dispersion composition of this invention may contain dispersion resin (henceforth "other dispersion resin" may be called) etc. other than a specific resin.

Examples of other dispersing resins that may be used in the present invention include polymer dispersants [e.g., polyamideamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified Poly (meth) acrylates, (meth) acrylate copolymers and naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkylamines, alkanol amines, pigment derivatives and the like.

In addition, the other dispersing resins may be classified into linear polymers, terminal modified polymers, graft polymers, and block polymers depending on the structure.

The other dispersed resin is attached to the surface of the metal oxide particles and the pigment used in combination with a specific resin, if necessary, to function to suppress reagglomeration. Thus, preferred examples of the structure of the resin include terminal modified polymers, graft polymers, and block polymers, which each have anchor sites on the surface of the metal oxide particles.

On the other hand, the other dispersing resin has an effect of modifying the surface of the metal oxide particles to promote the adsorption of the dispersing resin.

Specific examples of other dispersion resins include "Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing acid groups), 130 (polyamide), 161, 162, 163, 164 , 165, 166 and 170 (polymer copolymer) "," BYK-P104 and P105 (high molecular weight unsaturated polycarboxylic acid) "(by BYK Chemie GmbH)," EFKA 4047, 4050, 4010, 4165 (polyurethane-based), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo Pigment Derivatives) "(manufactured by EFKA); "AJISPER PB821, PB822" (manufactured by Ajinomoto Fine-Techno Co., Inc.), "FLOWLEN TG-710 (urethane oligomer)", "Polyflow No. 50E, No. 300 (acrylic copolymer)" (KYOEISHA CHEMICAL Co. , Ltd.), "Disparlon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725" (Kusumoto Chemicals Ltd.), DEMOL RN, N (naphthalenesulfonic acid formalin polycondensate), "MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)", "HOMOGENOL L-18 (polymer polycarboxylic acid) "," EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," ACETAMIN 86 (stearylamine acetate) "(manufactured by Kao Corporation)," Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative) ), 13240 (polyester amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (grafted polymer) "(manufactured by The Lubrizol Corporation)," NIKKOL T106 (polyoxyethylene Sorbitan monoolei ) And MYS-IEX (polyoxyethylene monostearate) "(manufactured by Nikko Chemicals Co., Ltd.) and the like.

These other dispersion resins may be used alone or in combination of two or more thereof.

Although the dispersion composition (or the curable composition described later) of the present invention may or may not contain other dispersion resins, when the composition contains other dispersion resins, the content of the other dispersion resins may be It is preferable to exist in the range of 1 mass%-20 mass% with respect to the total solid content of the curable composition) mentioned later, and it is more preferable to exist in the range which is 1 mass%-10 mass%.

(C-1) Solvent

The dispersion composition of the present invention contains a solvent, the solvent may be composed of various organic solvents.

Examples of organic solvents that can be used herein include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether Three lactate, and the like, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N- dimethylformamide, dimethyl sulfoxide, γ- butyrolactone, methyl lactate, ethyl lactate.

These solvents may be used alone or in combination. It is preferable that the density | concentration of solid content in the dispersion composition of this invention is 2 mass%-60 mass%.

The method for preparing the dispersion composition of the present invention is not particularly limited, and a method for preparing a dispersion composition that is usually used may be applied. For example, the preparation may be performed by mixing the metal oxide particles, the graft copolymer and the solvent to disperse the mixture using a circulating dispersion device (bead mill) or the like.

&Lt; Curable composition >

It is preferable that the dispersible composition of this invention is a curable composition comprised so that the dispersion composition of this invention may contain a polymeric compound (D-1), a polymerization initiator (E-1), and other components as needed.

As described above, the "curable composition" in the present invention is a type of "dispersion composition", and as described above, the content of the metal oxide particles is 50% by mass to 90% by mass relative to the total solid content of the curable composition. It is more preferable that they are 52 mass%-85 mass%, and it is most preferable that they are 55 mass%-80 mass%.

Even when the curable composition is applied on a large size wafer, the dispersion composition is composed of a curable composition which has excellent dispersibility and dispersion stability, a very high refractive index, and a film having a small difference in film thickness between the central part and the peripheral part ( Typically, a transparent film) can be formed.

Moreover, this invention relates to the transparent film formed using the curable composition of this invention.

It is preferable that refractive index is 1.72-2.60, and, as for the cured film obtained from the said curable composition (film formed with a curable composition, and then hardening reaction is performed), it is more preferable that it is 1.80-2.60.

Physical properties of the cured film having the refractive index of 1.72 to 2.60 can be achieved by any method as long as the curable composition contains the dispersion composition, the polymerizable compound (D-1) and the polymerization initiator (E-1) of the present invention. However, the physical properties control, for example, the type and content of the polymerizable composition (D-1) or binder polymer (F-1) which may be further added, or the metal oxide particles (A-1) in the curable composition. It is preferably achieved by controlling the type and content of the metal oxide at the same time.

In particular, the above-described physical properties can be more easily achieved by using the metal oxide particles as a preferred example of the above.

It is preferable that the composition of this invention is a transparent composition, More specifically, when the cured film with a film thickness of 1.0 micrometer is formed from the said composition, the composition has a light transmittance of 400 nm-with respect to the thickness direction of the said cured film. 90% or more over the entire wavelength range of 700 nm.

That is, the transparent film of this invention means the film whose light transmittance with respect to the thickness direction of a film is 90% or more over the whole wavelength range of 400 nm-700 nm in the film thickness of 1.0 micrometer.

Such physical properties of light transmittance can be achieved by any method as long as the curable composition contains the dispersion composition, the polymerizable compound (D-1) and the polymerization initiator (E-1) of the present invention, and may be further added. It is preferable to achieve by controlling the kind and content of the active compound (D-1) or the binder polymer (F-1). The physical properties of the light transmittance can also be preferably achieved by controlling the particle diameter of the metal oxide particles (A-1) or the type and amount of the graft copolymer (B-1).

For the curable compositions and transparent films of the invention, the fact that the light transmittance is 90% or more over the entire wavelength region of 400 nm to 700 nm is an important factor for showing the required properties, in particular the under of a microlens or color filter. Coat film is an important factor.

The light transmittance is preferably 95% or more, more preferably 99% or more, and most preferably 100% over the entire wavelength range of 400 nm to 700 nm.

In view of the above, the curable composition of the present invention is substantially free of a colorant (the content of the colorant is preferably 0% by mass based on the total solids content of the composition).

(D-1) Polymerizable Compound

The polymerizable compound (D-1) of the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one and preferably two or more terminal ethylenically unsaturated bonds. Such compounds are well known in the art and these compounds can be used in the present invention without particular limitation.

These compounds have, for example, chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of such monomers and copolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof, and unsaturated carboxylic acids. It is preferable to use esters of acids and aliphatic polyhydric alcohol compounds and amides of unsaturated carboxylic acids and aliphatic polyamine compounds. Addition reactions of unsaturated carboxylic esters or unsaturated carboxylic acid amides with mononuclear or polyfunctional isocyanates or epoxys, unsaturated carboxylic esters or unsaturated carboxylic acids having nucleophilic substituents such as hydroxyl groups, amino groups and mercapto groups It is preferable to use a dehydration condensation reaction product of an amide and a monofunctional or polyfunctional carboxylic acid, and the like. Furthermore, addition reaction products of unsaturated carboxylic esters or unsaturated carboxylic acid amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines or thiols; And substitution reactants of unsaturated carboxylic esters or unsaturated carboxylic acid amides having a releasing substituent such as halogen groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines or thiols. Moreover, as another example, the group of the compound obtained by substituting the said unsaturated carboxylic acid with unsaturated phosphoric acid, styrene, vinyl ether, etc. can be used.

Specific examples of monomers of aliphatic polyhydric alcohol compounds and esters of unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol di Acrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1 , 4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorb ratio Triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO modified triacrylate and the like do.

Examples of the methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylol propane trimethacrylate, triethylolethane trimethacrylate, ethylene Glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate Latex, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis- [p- (Methacryloxyethoxy) phenyl] dimethyl methane and the like.

Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, Sorbitol tetraitaconate and the like.

Examples of the crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetracrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like.

In addition, the aliphatic alcohol esters described in, for example, Japanese Patent Publication No. S51-47334 and Japanese Patent Application Publication No. S57-196231; Esters having an aromatic skeleton described in Japanese Patent Application Laid-Open No. S59-5240, Japanese Patent Application Laid-Open No. S59-5241 and Japanese Patent Application Laid-open No. H2-226149; And esters containing amino groups described in Japanese Patent Application Laid-open No. H-165613 are preferably used as examples of other esters. The above-mentioned ester monomer can be used as a mixture.

Specific examples of the monomer of the amide of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, and 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.

Examples of other preferred amide monomers include monomers having a cyclohexylene structure described in Japanese Patent Publication No. S54-21726.

Further, urethane-based addition polymerizable compounds prepared by addition reaction of isocyanate and hydroxyl groups are preferable, and specific examples thereof include two or more isocyanate groups in a molecule as described in Japanese Patent Publication No. S48-41708. The vinyl urethane compound containing two or more polymerizable vinyl groups in the molecule | numerator obtained by adding the vinyl monomer containing a hydroxyl group represented by the following general formula (V) to a polyisocyanate compound is contained.

In formula (V), R <^7> and R <^8> represents a hydrogen atom or a methyl group each independently.

Further, urethane acrylates described in Japanese Patent Application Laid-Open No. S51-37193, Japanese Patent Publication H2-32293, and Japanese Patent Publication H2-16765; Or a urethane compound having an ethylene oxide-based skeleton described in Japanese Patent Publication S58-49860, Japanese Patent Publication S56-17654, Japanese Patent Publication S62-39417 and Japanese Patent Publication S62-39418. . Curable compositions having excellent photosensitivity are polymerizable compounds having an amino structure or a sulfide structure in the molecules described in Japanese Patent Application Laid-Open No. S63-277653, Japanese Patent Application Laid-open No. S63-260909, and Japanese Patent Application Laid-open No. H-105238. It can be obtained by using.

Other examples thereof include polyfunctional acrylates or methacrylates such as polyester acrylates described in Japanese Patent Application Laid-Open No. S48-64183, Japanese Patent Publication No. S49-43191 and Japanese Patent Publication No. S52-30490; Epoxy acrylate obtained by making an epoxy resin react with (meth) acrylic acid is contained. Examples thereof include specific unsaturated compounds described in Japanese Patent Publication No. S46-43946, Japanese Patent Publication No. Hl-40337, and Japanese Patent Publication No. HI-40336, and vinyl described in Japanese Patent Application Publication No. H2-25493. Phosphoric acid compounds and the like. In this case, it is preferable to use the structure containing the perfluoroalkyl group of Unexamined-Japanese-Patent No. S61-22048. Journal of the Adhesion Society of Japan Vol. 20, No. 7, pp. The photocurable monomer or oligomer described in 300-308 (1984) can be used.

For these polymerizable compounds, a detailed description of the method of use, such as the structure of the compound, whether it is used alone or in combination, and the amount of addition, may be further determined according to the final performance design of the curable compound. For example, the method is selected from the following point of view.

It is preferable that it is the structure which has a high content of unsaturated group per molecule from a viewpoint of the said sensitivity, and in many cases, bifunctional or higher functionality is preferable. In order to raise the intensity | strength of the said cured film, trifunctional or higher functionality is preferable. A method of controlling both sensitivity and strength by using a combination of compounds having different functional groups and / or other polymerizable groups (e.g., acrylic esters, methacrylic esters, styrene-based compounds and vinyl ether-based compounds) It is efficient to use.

In addition, the method of selecting and using the polymerizable compound is an important factor for compatibility and dispersibility with other components (eg, polymerization initiator, metal oxide particles, etc.) contained in the curable composition. For example, the compatibility can be increased by using low purity compounds, or by the use of two or more other ingredients. In some cases, certain structures may be selected to improve adhesion with hard surfaces, such as substrates.

It is preferable that content of the said polymeric compound (D-1) exists in the range of 1 mass%-50 mass% with respect to the total solid content of the said curable composition, The range of 3 mass%-40 mass% is more preferable, The range of 5 mass%-30 mass% is more preferable.

Since it is excellent in sclerosis | hardenability without the said refractive index falling, it is preferable that it is content in the said range.

(E-1) polymerization initiator

The polymerization initiator (E-1) used in the present invention is a compound that initiates and promotes the polymerization of the polymerizable compound (D-1), and the polymerization initiator (E-1) is stable up to 45 ° C, but at a high temperature. The ability to initiate polymerization during heating is excellent. The polymerization initiator may be used alone or in combination of two or more.

Examples of the polymerization initiator (E-1) include an organic halide compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide compound, an azo compound, a coumarin compound, an azide compound , Metallocene compounds, hexaaryl biimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime compounds, onium salt compounds and acyl phosphine (oxide) compounds.

Specific examples of the organic halide compound include "Bull Chem. Soc Japan", 42, 2924 (1969), Wakabayashi et al., US Patent No. 3,905,815, Japanese Patent Publication No. S46-4605, Japanese Patent Application Publication No. S48 -36281, Japanese Patent Application Publication No. S55-32070, Japanese Patent Application Publication No. S60-239736, Japanese Patent Application Publication No. S61-169835, Japanese Patent Application Publication No. S61-169837, Japanese Patent Application Publication No. S62 -58241, Japanese Patent Application Laid-Open No. S62-212401, Japanese Patent Application Laid-Open No. S63-70243 and Japanese Patent Application Laid-Open No. S63-298339, and "Journal of Heterocyclic Chemistry, 1 (No 3), (1970) ", Compounds described in MP Hutt are included, in particular oxazole compounds substituted with trihalomethyl groups and s-triazine compounds.

As the s-triazine compound, more preferably an s-triazine derivative in which at least one monohalogen, dihalogen or trihalogen-substituted methyl group is bonded to the s-triazine ring, and a specific example of the s-triazine compound As for 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl)- s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- ( α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- ( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [l- (p-methoxyphenyl) -2,4-butadienyl] -4,6 -Bis (Triclaw) Methyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl ) -s-triazine, 2- (4-nathoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl)- s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6 -Tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl ) -s-triazine and the like.

Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxo Diazole, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 , 4-oxodiazole and the like.

Examples of the carbonyl compound include benzoyl ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone and 4-bromobenzophenone, and 2-carboxybenzophenone. Phenone, benzophenone derivatives; 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenyl propanone, 1-hydroxy-1-methyl Ethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1- Propanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 1,1,1-trichloromethyl acetophenone derivatives such as (p-butylphenyl) ketone and 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone; Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone and 2,4-diethyl thioxanthone, 2,4-di Thioxanthone derivatives such as isopropyl thioxanthone; Benzoate derivatives such as ethyl-p-dimethylaminobenzoate or ethyl-p-diethylaminobenzoate.

Examples of the ketal compound include benzyl methyl ketal, benzyl-β-methoxyethyl ethyl acetal, and the like.

Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl-o-benzoyl benzoate and the like.

Examples of the acridine compound include 9-phenylacridine, l, 7-bis (9-acridinyl) heptane and the like.

Examples of the organic peroxide compound include trimethyl cyclohexanone peroxide, acetylacetone peroxide, l, l-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert -Butyl peroxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butylhydroperoxide, cumene hydroperoxide, diisopropyl benzene hydroperoxide, 2,5-dimethylhexane-2 , 5-dihydroperoxide, 1,1,3,3-tetra-methylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert- Butylperoxy) hexane, 2,5-oxanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydica Carbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate Tert-butyl peroxyacetate, tert-butyl peroxy pivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxyoctanoate, tert-butylperoxylaurate, 3,3 ', 4 , 4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4 '-Tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyl-di (t-butylperoxydihydrogen diphthalate), carbonyl-di (t-hexylperoxy dihydrogen diphthalate) Etc. are included.

Examples of the azo compound include the azo compound described in Japanese Patent Application Laid-open No. H8-108621.

Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenyl coumarin, 3-chloro-5-diethylamino-((s-triazine- 2-yl) amino) -3-phenyl coumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenyl coumarin and the like.

Examples of the azide compound include organic azide compounds described in US Pat. No. 2,848,328, US Pat. No. 2,852,379, and US Pat. No. 2,940,853; 2,6-bis (4-azidobenzylidene) -4-ethylcyclohexanone (BAC-E) and the like.

Examples of the metallocene compound include Japanese Patent Application Publication No. S59-152396, Japanese Patent Application Publication No. S61-151197, Japanese Patent Application Publication No. S63-41484, Japanese Patent Application Publication No. H2-249, and Japanese Patent Various titanocene compounds described in Japanese Patent Application Laid-Open No. H2-4705 and Japanese Patent Application Laid-open No. H5-83588 are included, and specific examples thereof include dicyclopentadienyl-titanium-bis-phenyl and dicyclopentadienyl. -Titanium-bis-2,6-difluorophenyl-1-yl, dicyclopentadienyl-titanium-bis-2,4-difluorophenyl-1-yl, dicyclopentadienyl-titanium-bis -2,4,6-trifluorophenyl-1-yl, dicyclopentadienyl-titanium-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-titanium -Bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-titanium-bis-2,6-difluorophenyl-1-yl, dimethylcyclopenta Dienyl-titanium-bis-2,4,6-trifluoro Phenyl-1-yl, dimethylcyclopentadienyl-titanium-bis-2,3,5,6-tetrafluorophenyl-1-yl, dimethylcyclopentadienyl-titanium-bis-2,3,4,5 And iron-arene complexes described in 6-pentafluorophenyl-1-yl, Japanese Patent Application Laid-open No. H-30-3053 and Japanese Patent Application Laid-open No. H-152109.

As said biimidazole compound, a hexaaryl biimidazole compound (ropin dimer compound) etc. are preferable, for example.

Examples of the hexaaryl biimidazole compound include the lophine dimers described in Japanese Patent Publication Nos. S45-37377 and Japanese Patent Publication S44-86516, and Japanese Patent Publication H6-29285, US Patent No. 3,479,185, and US Patent No. 4,311,783 and US Pat. No. 4,622,286 and the like, and various examples thereof, including 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole , 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2 '-Bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5 '-Tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, etc. Included.

Examples of the organic boric acid compound include Japanese Patent Application Laid-Open No. S62-143044, Japanese Patent Application Laid-Open No. S62-150242, Japanese Patent Application Laid-open No. H9-188685, Japanese Patent Application Laid-open No. H9-188686, and Japanese Patent Application Japanese Patent Application Laid-Open No. H9-188710, Japanese Patent Application Laid-Open No. 2000-131837, and Japanese Patent Application Laid-open No. 2002-107916, Japanese Patent No. 2764769, and Japanese Patent Application Laid-Open No. 2001-16539, and "Rad Tech '98. Organic boric acid described in Proceeding, in Chicago Apr. 19-22, 1998 ", Kunz, Martin; Free boron sulfonium complexes or organic boron oxosulfonium complexes described in Japanese Patent Application Laid-Open No. H6-157623, Japanese Patent Application Laid-Open No. H6-175564, and Japanese Patent Application Laid-Open No. H6-175561; Organoboron iodonium complexes described in Japanese Patent Application Laid-Open No. H6-175554 and Japanese Patent Application Laid-Open No. H6-175553; Organoboron phosphonium complexes described in Japanese Patent Application Laid-Open No. H9-188710; In Japanese Patent Application Laid-Open No. H6-348011, Japanese Patent Application Laid-Open No. H7-128785, Japanese Patent Application Laid-Open No. H7-140589, Japanese Patent Application Laid-Open No. H7-306527, and Japanese Patent Application Laid-Open No. H7-292014 Organic boric acid transition metal coordination complexes described and the like.

Examples of the disulfone compound include compounds described in Japanese Patent Application Laid-Open No. S61-166544 and Japanese Patent Application Laid-Open No. 2002-328465 and the like.

An oxime compound is preferable as the polymerization initiator (E-1) used in the present invention from the viewpoint of the curability, stability with time, and difficulty in coloring during post-heating.

Examples of such oxime compounds are described in JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and Japanese Patent Application Publication No. 2000-66385. Described compounds; And the compounds described in Japanese Patent Application Laid-Open No. 2000-80068, and Japanese Patent Application Laid-Open No. 2004-534797.

As a oxime compound used for this invention from a viewpoint of the said sensitivity and time stability, the compound represented by following General formula (a) is more preferable.

In general formula (a), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5. When a plurality of X's are present, X's may be the same as or different from all the other X's.

Examples of the monovalent substituent represented by R in the general formula (a) include monovalent nonmetallic atom groups as shown below.

Examples of the monovalent nonmetallic atom group represented by R in the general formula (a) include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent Alkylsulfinyl group which may have, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, the alkoxycarbonyl group which may have a substituent , Aryloxycarbonyl group which may have a substituent, phosphinoyl group which may have a substituent, heterocyclic group which may have a substituent, alkylthiocarbonyl group which may have a substituent, arylthiocarbonyl group which may have a substituent, which may have a substituent Dialkylamino carbonyl group, dialkylamino thiocarbonyl group which may have a substituent, and the like .

As the alkyl group which may have the substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and examples thereof include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group and octade Real group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphena The group, 3-fluoro phenacyl group, 3-trifluoromethyl phenacyl group, 3-nitro phenacyl group, etc. are contained.

As the aryl group which may have the substituent, an aryl group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9- group. Phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 9-fluorenyl group, terphenyl group, quarter phenyl group, o-tolyl group, m-tolyl group and p- Tolyl group, xylyl group, o-cumenyl group, m-cumenyl group and p-cumenyl group, mesityl group, pentalenyl group, vinaphthalenyl group, ternaphthalenyl group, quarter naphthalenyl group, heptalenyl group, biphenyl Renyl group, indasenyl group, fluoranthhenyl group, acenaphthylenyl group, aceanthrylenyl group, penalenyl group, fluorenyl group, anthryl group, bianthrasenyl group, teranthracenyl group, quarter anthracenyl group, anthra Quinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, playadenyl group, picenyl group, perylenyl group, Pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptathenyl group, pyrantrenyl group, obvalenyl group and the like .

As the alkenyl group which may have the substituent, an alkenyl group having 2 to 10 carbon atoms is preferable, and examples thereof include vinyl group, allyl group, styryl group and the like.

As the alkynyl group which may have the substituent, an alkynyl group having 2 to 10 carbon atoms is preferable, and examples thereof include an ethynyl group, propynyl group, propargyl group and the like.

As the alkylsulfinyl group which may have the substituent, an alkylsulfinyl group having 1 to 20 carbon atoms is preferable, and examples thereof include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, and butylsulfinyl group. , Hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, decanoylsulfinyl, dodecanolylsulfinyl, octadecanolylsulfinyl, cyanomethylsulfinyl, methoxymethylsulfinyl, etc. This includes.

As the arylsulfinyl group which may have the substituent, an arylsulfinyl group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group and 2- Chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group , 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group, and the like.

As the alkylsulfonyl group which may have the substituent, an alkylsulfonyl group having 1 to 20 carbon atoms is preferable, and examples thereof include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, and butylsulfonyl group. , Hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanolylsulfonyl group, dodecanolylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, Perfluoroalkylsulfonyl groups and the like.

As the arylsulfonyl group which may have the substituent, an arylsulfonyl group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, and 2- Chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group , 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group, and the like.

As the acyl group which may have the substituent, an acyl group having 2 to 20 carbon atoms is preferable, and examples thereof include an acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1 -Naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2- Methylbenzoyl group, 2-methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluoro Benzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl group and the like.

As the alkoxycarbonyl group which may have the substituent, an alkoxycarbonyl group having 2 to 20 carbon atoms is preferable, and examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group and octyloxy Carbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group and the like.

Examples of the aryloxycarbonyl group which may have the substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4 -Dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxy Carbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group, etc. This includes.

As the phosphinoyl group which may have the substituent, a phosphinoyl group having 2 to 50 total carbon atoms is preferable, and examples thereof include dimethyl phosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group and diphenyl. Phosphinoyl groups, dimethoxyphosphinoyl groups, diethoxyphosphinoyl groups, dibenzoylphosphinoyl groups, bis (2,4,6-trimethylphenyl) phosphinoyl groups and the like.

As a heterocyclic group which may have the said substituent, the aromatic heterocyclic ring or aliphatic heterocycle containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is preferable. Examples thereof include thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, pehen Noxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolinyl group, isoindolinyl group, 3H-indole Aryl group, indolyl group, lH-indazolyl group, purinyl group, 4H-quinolinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnaolinyl group , Pterridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenantridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group , Isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromenyl group, chromanyl group, pyrrolidinyl group, pyrrole Nyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinucridinyl group, morpholinyl group, tee An oxantholyl group and the like.

Examples of the alkylthiocarbonyl group which may have the substituent include methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, trifluoromethyl thiocarbonyl group, and the like. do.

Examples of the arylthiocarbonyl group which may have the substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethylaminophenylthio Carbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group, 3-tri Fluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group, 4-methoxyphenylthiocarbonyl group, and the like.

Examples of the dialkylaminocarbonyl group which may have the substituent include dimethylaminocarbonyl group, diethylaminocarbonyl group, dipropylaminocarbonyl group, dibutylaminocarbonyl group and the like.

Examples of the dialkylaminothiocarbonyl group which may have the substituent include dimethylaminothiocarbonyl group, dipropylaminothiocarbonyl group, dibutylaminothiocarbonyl group and the like.

Among them, from the viewpoint of increasing the sensitivity, R is more preferably an acyl group, and specifically, an acetyl group, ethyloyl group, propioyl group, benzoyl group, and tolyl group are preferable.

Examples of the divalent organic group represented by A in formula (a) include alkylene having 1 to 12 carbon atoms which may have a substituent, cyclohexylene which may have a substituent, and alkynylene which may have a substituent Included.

Examples of the substituent which can be introduced into these groups include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom; An alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; Acyl groups such as acetyl group, benzoyl group, isobutylyl group, acryloyl group, methacryloyl group and methoxalyl group; An alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; An arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkylamino groups such as methylamino group and cyclohexylamino group; Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group; Arylamino groups such as phenylamino group and p-tolylamino group; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; Aryl groups such as a phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; And hydroxyl group, carboxyl group, formyl group, mercapto group, sulfo group, mesyl group, p-toluene sulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico And other groups such as groups, phosphono groups, trimethylammoniumyl groups, dimethylsulfoniumyl groups, and triphenylphenacylphosphoniumyl groups.

Among them, A is substituted with an unsubstituted alkylene group or an alkyl group (for example, methyl group, ethyl group, tert-butyl group and dodecyl group) in general formula (a) in view of the increase of sensitivity for suppressing coloration with heating time. Substituted alkylene groups, alkylene groups substituted with alkenyl groups (e.g., vinyl and allyl groups), and aryl groups (e.g., phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups Group, phenanthryl group and styryl group).

The aryl group represented by Ar in the general formula (a) is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.

Specific examples thereof include phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2 -Azulenyl, 9-fluorenyl, terphenyl, quarter phenyl, o-tolyl, m-tolyl, and p-tolyl, xylyl, o-cumenyl, m-cumenyl, and p- Cumenyl group, mesityl group, pentalenyl group, vinaphthalenyl group, ternaphthalenyl group, quarter naphthalenyl group, heptalenyl group, biphenylenyl group, indasenyl group, fluoranthenyl group, acenaphthylenyl group, acetonitrile Renyl group, penalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group , Naphthacenyl group, playadenyl group, pisenyl group, perylenyl group, pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, Coronyl group, trinaphthyleneyl group, heptaphenyl group, heptasenyl group, pyranthrenyl group, ovalenyl group, etc. are contained. Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing the sensitivity in order to suppress coloring with heating time.

When the phenyl group has a substituent, examples of the substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom; An alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkylthio groups such as methylthio group, ethylthio group and tert-butylthio group; Arylthio groups such as phenylthio group and p-tolylthio group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; Acyl groups such as acetyl group, benzoyl group, isobutylyl group, acryloyl group, methacryloyl group and methoxalyl group; An alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; An arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkylamino groups such as methylamino group and cyclohexylamino group; Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group; Arylamino groups such as phenylamino group and p-tolylamino group; Alkyl groups such as ethyl group, tert-butyl group and dodecyl group; And hydroxyl group, carboxyl group, formyl group, mercapto group, sulfo group, mesyl group, p-toluene sulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico Group, phosphono group, trimethylammoniumyl group, dimethylsulfoniumyl group, triphenyl phenacylphosphoniumyl group, and the like.

In formula (a), it is preferable that the structure of "SAr" formed from Ar and S adjacent to said Ar from a viewpoint of a sensitivity is arbitrary structures shown below.

Examples of the monovalent substituent represented by X in general formula (a) include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, Arylsulfanyl group which may have a substituent, alkylsulfinyl group which may have a substituent, arylsulfinyl group which may have a substituent, alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, and which may have a substituent Acyl group, alkoxycarbonyl group which may have a substituent, carbamoyl group which may have a substituent, sulfamoyl group which may have a substituent, and a substituent Which may have include an amino group, a phosphino group which may have a substituent, a heterocyclic group which may have a substituent, a halogen group, and the like.

As the alkyl group which may have the substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and examples thereof include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group and octade Real group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphena The group, 3-fluoro phenacyl group, 3-trifluoromethyl phenacyl group, 3-nitro phenacyl group, etc. are contained.

As the aryl group which may have the substituent, an aryl group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9- group. Phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 9-fluorenyl group, terphenyl group, quarter phenyl group, o-tolyl group, m-tolyl group, and p -Tolyl group, xylyl group, o-cumenyl group, m-cumenyl group, and p-cumenyl group, mesityl group, pentalenyl group, binaphthalenyl group, ternaphthalenyl group, quarter naphthalenyl group, heptalenyl group, Biphenylenyl group, indasenyl group, fluoranthhenyl group, acenaphthylenyl group, aceanthrylenyl group, penalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group , Anthraquinolyl, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, playadenyl group, picenyl group, perrylenyl group , Pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptathenyl group, pyrantrenyl group, ovalenyl group and the like do.

As the alkenyl group which may have the substituent, an alkenyl group having 2 to 10 carbon atoms is preferable, and examples thereof include vinyl group, allyl group, styryl group and the like.

As the alkynyl group which may have the substituent, an alkynyl group having 2 to 10 carbon atoms is preferable, and examples thereof include an ethynyl group, propynyl group, propargyl group and the like.

As the alkoxy group which may have the substituent, an alkoxy group having 1 to 30 carbon atoms is preferable, and examples thereof include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec -Butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, Ethoxycarbonylmethyl group, 2-ethylhexyloxycarbonyl methyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N- Ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethyloxy group, N-methyl-N-benzylaminocarbonylmethyloxy group, benzyloxy group, cyanomethyloxy group and the like.

As the aryloxy group which may have the substituent, an aryloxy group having 6 to 30 carbon atoms is preferable, and examples thereof include phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, and 2-chlorophenyl ox. Period, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3- Nitrophenyloxy group, 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxy phenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsul A panylphenyloxy group and the like.

As the alkylthio group which may have the substituent, a thioalkoxy group having 1 to 30 carbon atoms is preferable, and examples thereof include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, Isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, isopentylthio group, hexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, decylthio group, dode Silthio groups, octadecylthio groups, benzylthio groups and the like.

As the arylthio group which may have the substituent, an arylthio group having 6 to 30 carbon atoms is preferable, and examples thereof include phenylthio group, 1-naphthylthio group, 2-naphthylthio group, and 2-chlorophenyl thi. Ogi, 2-methylphenylthio group, 2-methoxyphenylthio group, 2-butoxyphenylthio group, 3-chlorophenylthio group, 3-trifluoromethylphenylthio group, 3-cyanophenylthio group, 3- Nitrophenylthio group, 4-fluorophenylthio group, 4-cyanophenylthio group, 4-methoxyphenylthio group, 4-dimethylaminophenylthio group, 4-methylsulfanylphenylthio group, 4-phenylsul A panylphenylthio group and the like.

As the acyloxy group which may have the substituent, an acyloxy group having 2 to 20 carbon atoms is preferable, and examples thereof include an acetyloxy group, propanoyloxy group, butanoyloxy group, pentanoyloxy group, and trifluoromethyl Carbonyloxy group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

As the alkylsulfanyl group which may have the substituent, an alkylsulfanyl group having 1 to 20 carbon atoms is preferable, and examples thereof include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, isopropylsulfanyl group, and butylsulfanyl group. , Hexylsulfanyl group, cyclohexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group, etc. This includes.

As the arylsulfanyl group which may have the substituent, an arylsulfanyl group having 6 to 30 carbon atoms is preferable, and examples thereof include phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, and 2- Chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group , 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfanyl group, 4-dimethylaminophenylsulfanyl group, and the like.

As the alkylsulfinyl group which may have the substituent, an alkylsulfinyl group having 1 to 20 carbon atoms is preferable, and examples thereof include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, and butylsulfinyl group. , Hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, decanoylsulfinyl, dodecanolylsulfinyl, octadecanolylsulfinyl, cyanomethylsulfinyl, methoxymethylsulfinyl, etc. This includes.

As the arylsulfinyl group which may have the substituent, an arylsulfinyl group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group and 2- Chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group , 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group, and the like.

As the alkylsulfonyl group which may have the substituent, an alkylsulfonyl group having 1 to 20 carbon atoms is preferable, and examples thereof include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, and butylsulfonyl group. , Hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanolylsulfonyl group, dodecanolylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, etc. This includes.

As the arylsulfonyl group which may have the substituent, an arylsulfonyl group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2 -Chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfo Neyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group , 4-dimethylaminophenylsulfonyl group and the like.

As the acyl group which may have the substituent, an acyl group having 2 to 20 carbon atoms is preferable, and examples thereof include an acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1 -Naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2- Methylbenzoyl group, 2-methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluoro Benzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl group and the like.

As the alkoxycarbonyl group which may have the substituent, an alkoxycarbonyl group having 2 to 20 carbon atoms is preferable, and examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group and octyloxy Carbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyl When a carbonyl group, and the like 3-nitro-phenyl-oxy group, a 4-fluoro-phenyl-oxy group, a 4-cyanophenyl-oxy group, a 4-methoxy phenyloxy group.

As the carbamoyl group which may have the substituent, a carbamoyl group having 1 to 30 total carbon atoms is preferable, and examples thereof include N-methylcarbamoyl group, N-ethylcarbamoyl group, and N-propylcarbamo Diary, N-butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarba Barmoyl group, N-2-methylphenylcarbamoyl group, N-2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N -3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamo Diary, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N- Dibutyl Carbamoyl groups, N, N-diphenylcarbamoyl groups and the like.

As the sulfamoyl group which may have the substituent, a sulfamoyl group having 0 to 30 total carbon atoms is preferable, and examples thereof include a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, and N , N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specific examples thereof include N-methyl sulfamoyl group, N-ethyl sulfamoyl group, N-propyl sulfamoyl group, N-butyl sulfamoyl group, N-hexyl sulfamoyl group, N-cyclohexyl sulfamoyl group, N -Octyl sulfamoyl group, N-2-ethylhexyl sulfamoyl group, N-decyl sulfamoyl group, N-octadecyl sulfamoyl group, N-phenyl sulfamoyl group, N-2-methylphenyl sulfamoyl group, N-2 -Chlorophenyl sulfamoyl group, N-2-methoxyphenyl sulfamoyl group, N-2-isopropoxyphenyl sulfamoyl group, N-3-chlorophenyl sulfamoyl group, N-3-nitrophenyl sulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsul Fanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenyl sulfamoyl group, etc. are contained.

An amino group which may have the substituent, an amino group is preferable, and its example having 0 to 50 of the total carbon atom is -NH _2, N- alkylamino, N- arylamino group, N- acylamino group, N- sulfonyl Amino groups, N, N-dialkylamino groups, N, N-diarylamino groups, N-alkyl-N-arylamino groups, N, N-disulfonylamino groups and the like. More specific examples thereof include N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino group, N-2-chlorophenylamino group, N -2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3 -Cyanophenylamino group, N-3-trifluoromethylphenylamino group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsul Panylphenylamino group, N-4-phenylsulfanylphenylamino group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino Group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcar Bonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group , Morpholino group, 3,5-dimethylmorpholino group, carbazole group and the like.

As the phosphinoyl group which may have the substituent, a phosphinoyl group having 2 to 50 total carbon atoms is preferable, and examples thereof include dimethyl phosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group and diphenyl. Phosphinoyl groups, dimethoxyphosphinoyl groups, diethoxyphosphinoyl groups, dibenzoylphosphinoyl groups, bis (2,4,6-trimethylphenyl) phosphinoyl groups and the like.

As a heterocyclic group which may have the said substituent, the aromatic or aliphatic heterocycle containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is preferable. Examples thereof include thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, pehen Noxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolinyl group, isoindolinyl group, 3H-indole Aryl group, indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnaolinyl group , Pterridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenantridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group , Isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromenyl group, chromanyl group, pyrrolidinyl group, pyrrole Nyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinucridinyl group, morpholinyl group, tee An oxantholyl group and the like.

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

The alkyl group which may have the substituent, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, the alkoxy group which may have a substituent, the aryloxy group which may have a substituent, and a substituent Alkylthio group which may have, an arylthio group which may have a substituent, an acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, an alkyl which may have a substituent A sulfinyl group, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, may have a substituent Carbamoyl group, a sulfamoyl group which may have a substituent, an amino group which may have a substituent, and a substituent may have Heterocyclic group may be substituted by another substituent described above.

Examples of such a substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom; An alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; Acyl groups such as acetyl group, benzoyl group, isobutylyl group, acryloyl group, methacryloyl group and methoxalyl group; An alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; An arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkylamino groups such as methylamino group and cyclohexylamino group; Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group; Alkyl groups, such as an arylamino group, such as a phenylamino group and p-tolylamino group, a methyl group, an ethyl group, a tert- butyl group, and a dodecyl group; Aryl groups such as a phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; And hydroxyl group, carboxyl group, formyl group, mercapto group, sulfo group, mesyl group, p-toluene sulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico And other groups such as groups, phosphono groups, trimethylammoniumyl groups, dimethylsulfoniumyl groups, and triphenylphenacylphosphoniumyl groups.

Among these, in view of increasing solubility in a solvent and increasing light absorption efficiency in a long wavelength region, X in general formula (a) is an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, Alkynyl group which may have a substituent, Alkoxy group which may have a substituent, Aryloxy group which may have a substituent, Alkylthio group which may have a substituent, Arylthio group which may have a substituent, and Amino group which may have a substituent Is preferably.

In formula (a), n represents the integer of 0-5, and the integer of 0-2 is preferable.

Hereinafter, although the specific example of an oxime compound is shown, this invention is not limited to this.

The oxime compound decomposes by heat and functions as a thermal polymerization initiator for initiating and promoting polymerizability. In particular, the oxime compound represented by the general formula (a) has a lower coloration at the time of post-heating and has excellent curability.

As the oxime compound, commercially available products such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF Corporation) can be preferably used.

Examples of the onium salt compound include S. I. Schlesinger, Photogr. Sci. Diazonium salts described in Eng., 18, 387 (1974), and in T. S. Bal et al., Polymer, 21, 423 (1980); Ammonium salts described in US Pat. No. 4,069,055, Japanese Patent Application Laid-Open No. H4-365049, and the like; Phosphonium salts described in US Pat. No. 4,069,055 and US Pat. No. 4,069,056; Iodonium salts described in European Patent No. 104,143, Japanese Patent Application Laid-Open No. H2-150848, and Japanese Patent Application Laid-Open No. H2-296514, and the like.

The iodonium salt which can be preferably used in the present invention is a diaryl iodonium salt, and from the viewpoint of stability, the iodonium salt is preferably substituted with two or more electron donor groups such as an alkyl group, an alkoxy group and an aryloxy group.

Examples of sulfonium salts that can be preferably used in the present invention include European Patent 370,693, European Patent 390,214, European Patent 233,567, European Patent 297,443 and European Patent 297,442, US Patent 4,933,377, Sulfonium salts described in US Pat. No. 4,760,013, US Pat. No. 4,734,444, and US Pat. No. 2,833,827, and German Pat. No. 2,904,626, German Pat. No. 3,604,580 and German Pat. No. 3,604,581. The sulfonium salt is preferably substituted with an electron withdrawing group. The Hamet value of the electron withdrawing group is preferably greater than zero. Preferred examples of the electron withdrawing group include a halogen atom, a carboxylic acid group and the like.

Other preferred examples of the sulfonium salt include sulfonium salts in which one of the substituents of the triaryl sulfonium salt is a coumarin structure or an anthraquinone structure and has an absorbance of 300 nm or more. Other preferred examples of the sulfonium salt include a sulfonium salt having an allyloxy group or an arylthio group as a substituent and an absorbance of 300 nm or more.

Examples of such onium salts include J. V. Crivello et al., Macromolecules, 10 (6), 1307 (1977) and J. V. Crivello et al., J. Polymer Sci., Polymer Chem. Selenium salts described in Ed., 17, 1047 (1979), and C. S. Wen et al., Teh, Proc. Conf. Rad. curing ASIA, p. Onium salts, such as the arsonium salt described in 478, Tokyo, October (1988), are included.

Examples of the acyl phosphine (oxide) compounds include IRGACURE 819, DAROCURE 4265, DAROCURE TPO, and the like, manufactured by BASF Corporation.

From the viewpoint of curability, the polymerization initiator (E-1) used in the curable composition of the present invention is a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acyl phosphine compound , Phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes And a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound.

Trihalomethyl triazine compounds, α-aminoketone compounds, acyl phosphine compounds, phosphine oxide compounds, oxime compounds, triallyl imidazole dimers, onium compounds, benzophenone compounds and acetophenone compounds are more preferred, and It is most preferable that it is at least 1 compound chosen from the group which consists of a halomethyl triazine compound, the (alpha)-amino ketone compound, an oxime compound, a triallyl imidazole dimer, and a benzophenone compound.

In particular, in the case where the curable composition of the present invention is formed on a color filter of a solid-state imaging device and is made of a microlens, in particular, the composition has poor coloration upon post-heating, has excellent curability, and the polymerization initiator (E-1 Most preferably, an oxime compound is used).

It is preferable that content (the total content in 2 or more cases) of the said polymerization initiator (E-1) contained in the curable composition of this invention is 0.1 mass%-10 mass% with respect to the total solid content of the said curable composition, 0.3 Mass%-8 mass% are more preferable, 0.5 mass%-5 mass% are more preferable. Good curability can be obtained within these ranges.

The curable composition of this invention may further contain arbitrary components as needed in detail below. Hereinafter, arbitrary components which the said curable composition may contain are demonstrated.

[Polymerization inhibitor]

In the present invention, it is preferable to add a polymerization inhibitor in order to suppress unnecessary polymerization of a compound having a polymerizable ethylenically unsaturated double bond in preparing or storing the curable composition.

Examples of the polymerization inhibitor used in the present invention include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine-1-oxyl free radical compounds, pyrrolidine-1-oxyl free radical compounds, N-nitroso Transition metal compounds such as phenyl hydroxylamine, diazonium compound, cationic die, sulfide group containing compound, nitro group containing compound, FeCl ₃ or CuCl ₂ .

More preferable embodiment is as follows.

The phenolic hydroxyl group-containing compound is hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4-thiobis (3-methyl- It is preferably a compound selected from the group consisting of 6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), a phenol resin and a cresol resin.

The N-oxide compound is 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydrate It is preferable that it is a compound chosen from the group which consists of oxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide, and isnicotinic acid N-oxide.

The piperidine-1-oxyl free radical compound is a piperidine-1-oxyl free radical, 2,2,6,6-tetramethyl piperidine-1-oxyl free radical, 4-oxo-2,2, 6,6-tetramethyl piperidine-1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethyl piperidine-1-oxyl free radical, 4-acetamide-2,2, 6,6-tetramethyl piperidine-1-oxyl free radical, 4-maleimide-2,2,6,6-tetramethyl piperidine-1-oxyl free radical and 4-phosphonoxy-2,2 It is preferred that the compound is selected from the group consisting of 6,6-tetramethyl piperidine-1-oxyl free radicals.

It is preferable that the said pyrrolidine-1-oxyl free radical compound is a 3-carboxyoxyl free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl free radical).

The N-nitrosophenylhydroxylamine is preferably a compound selected from the group consisting of N-nitrosophenylhydroxylamine cerium (I) salt and N-nitrosophenylhydroxylamine aluminum salt.

The diazonium compound is a compound selected from the group consisting of 4-diazophenyldimethylamine hydrogensulfate, 4-diazophenylphenyl tetrafluoroborate and 3-methoxy-4-diazophenylphenyl hexafluorophosphate. desirable.

Preferred polymerization inhibitors that can be used in the present invention are described below, but the present invention is not limited thereto. In addition, a phenol polymerization inhibitor contains the following exemplary compound (P-1)-exemplary compound (P-24).

An amine polymerization inhibitor contains the following exemplary compound (N-1)-exemplary compound (N-7).

Sulfur type polymerization inhibitors include the following exemplary compound (S-1) to exemplary compound (S-5).

The phosphorous acid-based polymerization inhibitor includes the following exemplary compound (R-1) to exemplary compound (R-2).

In addition, the following compounds can each be used as a preferable polymerization inhibitor.

Among the exemplary compounds described above, preferred examples thereof include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4-thiobis (3- Phenolic hydroxyl group-containing compounds such as methyl-6-t-butylphenol) and 2,2'-methylene-bis (4-methyl-6-t-butylphenol); Piperidine-1-oxyl free radical compounds; Or 2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-oxo-2,2,6,6-tetramethyl piperidine-1-oxyl free radical, 4-hydroxy- 2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-acetamide-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-maleimide- Piperidine such as 2,2,6,6-tetramethylpiperidine-1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical -1-oxyl free radical compound; Or N-nitrosophenylhydroxylamine compounds such as N-nitrosophenylhydroxylamine cerium (I) salt and N-nitrosophenylhydroxylamine aluminum salt, and the like, and more preferred examples thereof include 2,2,6 , 6-tetramethylpiperidine-1-oxyl free radical, 4-oxo-2,2,6,6-tetramethyl piperidine-1-oxyl free radical, 4-hydroxy-2,2,6, 6-tetramethylpiperidine-1-oxyl free radical, 4-acetamide-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-maleimide-2,2,6, Piperidine-1-oxyl free radicals such as 6-tetramethylpiperidine-1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical compound; Or N-nitrosophenylhydroxylamine compounds such as N-nitrosophenylhydroxylamine cerium (I) salt and N-nitrosophenylhydroxylamine aluminum salt, and more preferred examples thereof include N-nitrosophenylhydride. N-nitrosophenyl hydroxylamine compounds, such as a hydroxylamine cerium (I) salt and N-nitrosophenylhydroxylamine aluminum salt, are contained.

It is preferable that the addition amount of the said polymerization inhibitor is 0.01 mass part-10 mass parts with respect to 100 mass parts of the said polymerization initiator (E-1), 0.01 mass part-8 mass parts are more preferable, 0.05 mass part-5 mass parts are further desirable.

By setting the amount within the above-mentioned range, suppression of the curing reaction in the non-image region and promotion of the curing reaction in the image region can be sufficiently achieved, so that image formability and sensitivity can be improved.

[Binder Polymer (F-1)]

It is preferable that the curable composition of this invention contains a binder polymer (F-1) further from a viewpoint of a coating film characteristic.

As said binder polymer (F-1), it is preferable to use a linear organic polymer. As the linear organic polymer, any known polymer can be optionally used. In order to enable water development or weakly alkaline water development, it is preferable to select straight organic polymers which can be dissolved or swelled in water or weakly alkaline water. The linear organic polymer may be additionally used depending on the use of water, weak alkaline water or organic solvent developer as well as a film forming agent. For example, when water-soluble organic polymers are used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in its side chain, for example, Japanese Patent Application Laid-Open No. S59-44615, Japanese Patent Application S54-34327, and Japanese Patent Publication No. S58-12577. And the polymers described in Japanese Patent Publication S54-25957, Japanese Patent Application Publication S54-92723, Japanese Patent Application Publication S59-53836 and Japanese Patent Application Publication S59-71048, that is, monomers having a carboxyl group alone. Resins formed by polymerization or copolymerization; Formed by hydrolyzing, semi-esterifying or semi-amidating an acid anhydride unit formed by homopolymerization or copolymerization of a monomer having an epoxy acrylate formed by denaturation with an unsaturated monocarboxylic acid and an acid anhydride. Resins and the like. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylic styrene, and the like. Examples of the monomer having an acid anhydride include maleic anhydride and the like. do.

Similarly, acidic cellulose derivatives having a carboxylic acid group in the side chain are included. Also useful are polymers formed by the addition of cyclic acid anhydrides to polymers having hydroxyl groups and the like.

In the present invention, when a copolymer is used as the binder polymer (F-1), monomers other than the monomers described above can be used as the compound to be copolymerized. Examples of other monomers include the compounds described in the following (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl meta Acrylic esters and methacrylic esters having aliphatic hydroxyl groups such as acrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate.

(2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloro Ethyl acrylate, glycidyl acrylate, 3,4-epoxycyclohexyl methyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate And alkyl acrylates such as propargyl acrylate.

(3) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate Methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1- Alkyl methacrylates, such as propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.

(4) acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide , N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N, N-diallyl acrylamide, N, N-diallyl methacrylamide, allyl acrylamide and Acrylamide or methacrylamide, such as allyl methacrylamide.

(5) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.

(6) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(7) Styrene, such as styrene, (alpha) -methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxy styrene.

(8) ether ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone.

(9) olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(10) N-vinyl pyrrolidone, acrylonitrile, methacrylonitrile and the like.

(11) unsaturated imides such as maleimide, N-acryloyl acrylamide, N-acetyl methacrylamide, N-propionyl methacrylamide and N- (p-chlorobenzoyl) methacrylamide.

(12) Methacrylic acid monomer having a hetero atom bonded to the α-position. For example, the compound described in Unexamined-Japanese-Patent No. 2002-309057, Unexamined-Japanese-Patent No. 2003-311569, etc. can be included.

In the binder polymer (F-1), it is preferable to further include a repeating unit (hereinafter sometimes referred to as "ether dimer") formed by polymerizing a compound represented by the following general formula (ED).

(In General Formula (ED), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

Thus, the curable composition of the present invention can form a cured coating film having very good heat resistance and very good transparency. In the general formula (ED) representing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms having substituents represented by R ₁ and R ₂ is not particularly limited, but examples thereof include methyl, ethyl and n-propyl. Linear or branched alkyl groups such as isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl and 2-ethylhexyl; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, t-butyl cyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; Alkoxy substituted alkyl groups such as 1-methoxyethyl and 1-ethoxyethyl; Aryl group substituted alkyl groups, such as benzyl, etc. are contained.

Among these, primary carbon substituents or secondary carbon substituents, such as methyl, ethyl, cyclohexyl and benzyl, which are not easily removed by acid or heat, are preferable in terms of heat resistance.

Specific examples of the ether dimer include dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate and diethyl-2,2'-[oxybis (methylene)] bis-2-prop Phenoate, di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis- 2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene) ] Bis-2-propenoate, di (t-butyl) -2,2 '-[oxybis (methylene) bis-2-propenoate, di (t-amyl-2,2'-[oxybis ( Methylene)] bis-2-propenoate, di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxy Bis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl)- 2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxye Tyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, biphenyl-2 , 2 '-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl ) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate , Di (tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis- 2-propenoate, diamantyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxy Bis (methylene)] bis-2-propenoate, etc. Among these, dimethyl-2,2 '-[oxybis (methylene) bis-2-propenoate, diethyl-2,2'-[ Oxybis (methylene)] bis-2-prope Ate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate are preferred Do. These ether dimers may be used alone or in combination of two or more. The structure derived from the compound represented by the said general formula (ED) can be copolymerized with another monomer.

Among these, (meth) acrylic resin which has an allyl group or a vinyl ester group, and a carboxyl group in the side chain described in Unexamined-Japanese-Patent No. 2000-187322 and 2002-62698, Alkali-soluble resin which has a double bond in a side chain. Or an alkali-soluble resin having an amide group in the side chain described in Japanese Patent Application Laid-Open No. 2001-242612 is preferable due to the excellent balance of film strength, sensitivity and developability.

Japanese Patent Publication H7-12004, Japanese Patent Publication H7-120041, Japanese Patent Publication H7-120042, Japanese Patent Publication H8-12424 and Japanese Patent Publication S63-287944, Japanese Patent Application Publication S63 Acid groups and double bonds in the urethane-based binder polymer having an acid group described in -287947, Japanese Patent Application Laid-Open No. S63-287947 and Japanese Patent Application Laid-Open No. H-2-2741, or the side chain described in Japanese Patent Application Laid-Open No. 2002-107918. Since the urethane-based binder polymer having a very high strength in terms of film strength is advantageous.

Acetal-modified polyvinyl alcohol-based binder polymers described in European Patent No. 993966, European Patent No. 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like are preferred because they have excellent film strength.

In addition, polyvinyl pyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. Alcohol soluble nylons, polyethers of 2,2-bis (4-hydroxyphenyl) -propane with epichlorohydrin and the like are useful for increasing the strength of the cured film.

It is preferable that the weight average molecular weight (polystyrene conversion value measured by GPC method) of the binder polymer (F-1) which can be used for the curable composition of this invention is 5,000 or more, The range of 10,000-300,000 is more preferable, It It is preferable that the number average molecular weight of is 1,000 or more, and the range of 2,000-250,000 is more preferable. It is preferable that it is 1 or more, and, as for the said polydispersity (weight average molecular weight / number average molecular weight), the range of 1.1-10 is more preferable.

The binder polymer may be any one of random polymers, block polymers, graft polymers, and the like.

The binder polymer (F-1) which can be used in the present invention can be synthesized by methods known in the art. Examples of the solvent used for the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, Diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N-dimethyl formamide, N, N-dimethyl acetamide, toluene, ethyl acetate, methyl lactate, Ethyl lactate, dimethyl sulfoxide, water and the like. These adhesives may be used alone or in combination of two or more.

Examples of the radical polymerization initiator used in the synthesis of the binder polymer (F-1) that can be used in the curable composition of the present invention include compounds known in the art such as azo initiators and peroxide initiators.

In the curable composition of the present invention, the binder polymer (F-1) may be used alone or in combination of two or more kinds.

Although the curable composition of the present invention may or may not contain a binder polymer (F-1), when the composition contains a binder polymer (F-1), the content of the binder polymer (F-1) is It is preferable that it is 1 mass%-40 mass% with respect to the total solid content of a curable composition, 3 mass%-30 mass% are more preferable, 4 mass%-20 mass% are more preferable.

Surfactant (G-1)

Various surfactant (G-1) can be added to the curable composition of this invention from a viewpoint of improving applicability | paintability. Various surfactants, such as a fluorine type surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon type surfactant, can be used as surfactant (G-1).

In particular, when the curable composition of the present invention is formulated into a coating liquid containing a fluorine-based surfactant, the liquid properties (particularly, fluidity) may be further improved, which may result in further improvement in uniformity of coating thickness or saving of liquid. .

That is, when the film is formed using a coating liquid for applying a photosensitive transparent composition containing a fluorine-based surfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid. Improves applicability to Therefore, even when a thin film having a thickness of several micrometers is formed with a small amount of liquid, it is efficient that formation of a uniform thickness film having less thickness nonuniformity can be performed more preferably.

In the said fluorine-type surfactant, it is preferable that content% of fluorine is 3 mass%-40 mass%, 5 mass%-30 mass% are more preferable, 7 mass%-25 mass% are especially preferable. The fluorine-based surfactant having the above fluorine content% in the above-described range is efficient in view of thickness uniformity and liquid saving of the coating film, and exhibits good solubility in the curable composition.

Examples of the fluorine-based surfactant include MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437, MEGAFAC F475, MEGAFAC F475, MEGAFAC F475 F554, MEGAFAC F780 and MEGAFAC F781 (all made by DIC corporation), Fluorad FC430, Fluorad FC431, and Fluorad FC171 (all made by Sumitomo 3M Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon SC393 and Surflon KH-40 (all manufactured by ASAHI GLASS CO. LTD.) And the like.

Specific examples of the nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and ethoxylate, propoxylate (eg, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether , Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, Pluronic L31, Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, and Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1 (manufactured by BASF Corporation), SOLSPERSE 20000 (manufactured by The Lubrizol Corporation), And Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.)).

Specific examples of the cationic surfactant include phthalocyanine derivatives (product name: EFKA-745, manufactured by Morishita & Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) Acrylic acid copolymer Polyflow No. 75, Polyflow No. 90 and Polyflow No. 95 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), WOO1 (manufactured by YUSHO CO., LTD.), And the like.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by YUSHO CO., LTD.), And the like.

Examples of the silicon-based surfactants include "Toray silicone DC3PA", "Toray silicone SH7PA", "Toray silicone DC11PA", "Toray silicone SH21PA", "Toray silicone SH28PA", "Toray silicone SH29PA", "Toray silicone SH30PA" and "Toray silicone SH8400" (manufactured by Dow Corning Toray Co., Ltd.), "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460" and "TSF-4452" (Momentive Performance Materials Inc.), "KP341", "KF6001" and "KF6002" (manufactured by Shin-Etsu Silicone Co., Ltd.), "BYK307", "BYK323" and "BYK330" (by BYK Chemie GmbH), and the like. .

The surfactant (G-1) may be used alone or in combination of two or more thereof.

Although the said curable composition may or may not contain surfactant (G-1), when the said composition contains surfactant, the addition amount of the said surfactant is 0.001 mass%-2.0 with respect to the total mass of the said curable composition. It is preferable that it is mass%, and 0.005 mass%-1.0 mass% are more preferable.

[UV absorbers]

The curable composition of this invention may contain a UV absorber. As said UV absorber, it is especially preferable that it is a compound represented with the following general formula (I) conjugated with a diene compound.

In formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² are the same as each other Although it may be different, it does not represent a hydrogen atom at the same time.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include methyl, ethyl, propyl, N-butyl, n-hexyl, cyclohexyl, N-decyl and N-dodec Real group, N-octadecyl group, eicosyl group, methoxyethyl group, ethoxypropyl group, 2-ethylhexyl group, hydroxyethyl group, chloropropyl group, N, N-diethylaminopropyl group, cyanoethyl group, phenethyl group , Benzyl group, pt-butylphenethyl group, pt-octylphenoxyethyl group, 3- (2,4-di-t-amylphenoxy) propyl group, ethoxycarbonylmethyl group, 2- (2-hydroxyethoxy ) Ethyl group, 2-furylethyl group, etc. are contained, and a methyl group, an ethyl group, a propyl group, N-butyl group, and n-hexyl group are preferable.

The alkyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent of the alkyl group having the substituent include alkyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, halogen atom, acylamino group, ac Real group, alkylthio group, arylthio group, hydroxyl group, cyano group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, arylsulfonyl group Included.

The aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² may be a monocyclic or condensed cyclic ring, and may be any one of a substituted aryl group and an unsubstituted aryl group having a substituent. Examples thereof include a phenyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group, fluorenyl group and the like. Examples of the substituent of the substituted aryl group having the substituent include alkyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, halogen atom, acylamino group, acyl group, alkylthio group, arylthio group, hydroxyl group, sia No group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, arylsulfonyl group and the like. Among these, a substituted or unsubstituted phenyl group, 1-naphthyl group and 2-naphthyl group are preferable.

R ¹ and R ² are R ¹ And a cyclic amino group with the nitrogen atom to which R ² is bonded. Examples of the cyclic amino group include a piperidino group, a morpholino group, a pyrrolidino group, a hexahydroazino group, a piperazino group, and the like.

Among these, R ¹ and R ² each represent 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, ultra-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl, 2-ethyl A lower alkyl group having a hexyl, tert-octyl or the like, or a substituted or unsubstituted phenyl group (e.g., tolyl group, phenyl group, anylyl group, mesityl group, chlorophenyl group, 2,4-di-t-amylphenyl group, etc.) It is preferable. Moreover, it is preferable that R <^1> and R <^2> combine with each other and form the ring containing the nitrogen atom represented by N in the said general formula (for example, a piperidine ring, a pyrrolidine ring, a morpholine ring, etc.).

In general formula (I), R <^3> and R <^4> represents an electron withdrawing group, respectively. Herein, the electron withdrawing group is an electron withdrawing group having a Hammett substituent constant, sigma _p value of 0.20 to 1.0. The electron withdrawing group is preferably an electron withdrawing group having a sigma _p value of 0.30 to 0.8.

Hammet's rule is an experimental rule proposed by LP Hammett in 1935 to quantitatively explain the effect of substituents on the reaction and equilibrium of benzene derivatives, the effectiveness of which is now well known. The substitution constants determined by Hammet's rule include σ _p values and σ _m values, which are described in general textbooks, the details of which are described, for example, in JA Dean, Ed., "Lange's Handbook". of Chemistry ", 12th Edition, 1979 (McGraw-Hill) or" Realms of Chemistry ", No. 122, pp. 96 to 103, 1979 (Nankodo Co., Ltd.), and Chemical Reviews, Vol. 91, pp. 165 to 195, 1991. In the present invention, the values described in these textbooks and already known in the literature do not mean not limited to only specific substituents, and are measured based on the rules of Hammet even if the values are not known in the literature. As long as the value is within the range when it is, it is clear that the value is included in the present invention.

Specific examples of the electron withdrawing groups having σ _p values of 0.20 to 1.0 include acyl groups, acyloxy groups, carbamoyl groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, cyano groups, nitro groups, dialkylphosphono groups, Diaryl phosphono group, diaryl phosphino group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, at least 2 An alkyl group substituted with at least two halogen atoms, an alkoxy group substituted with at least two halogen atoms, an aryloxy group substituted with at least two halogen atoms, an alkylamino group substituted with at least two halogen atoms, substituted with at least two halogen atoms alkylthio group, an aryl group substituted with other electron withdrawing property having a σ _p value of 0.20 or more, a heterocyclic group, a chlorine atom, a bromine atom, an azo group, or a seleno cyanate It is included. Among these substituents, the group which may further have a substituent may further have substituents such as those described above.

Among these, R ³ and R ⁴ are preferably acyl, carbamoyl, alkyloxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfonyl, arylsulfonyl, sulfonyloxy and sulfamoyl groups. Particularly preferred are a real group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group and sulfamoyl group.

Among the above, in the present invention, R ³ is preferably a group selected from cyano group, -COOR ⁵ , -CONHR ⁵ , -COR ⁵ and -S0 ₂ R ⁵ , and R ⁴ is cyano group, -COOR ⁶ , A group selected from -CONHR ⁶ , -COR ⁶ and -S0 ₂ R ⁶ . R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R ⁵ and R ⁶ have the same meanings as R ¹ and R ² , respectively, and preferably have the same characteristics.

R ³ and R ⁴ may combine with each other to form a ring.

At least one of R ¹ , R ² , R ³ and R ⁴ may be a type of polymer derived from a monomer which is bonded to a vinyl group via a linking group. Copolymers with other monomers can be used. In the case of the copolymer, examples of the other monomers include esters derived from acrylic acid such as acrylic acid, α-chloroacrylic acid and α-aracrylic acid (eg methacrylic acid, eg acrylamide, methacrylamide). , t-butylacrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, Lower alkyl esters such as octyl methacrylate and lauryl methacrylate, methylenebisacrylamide and amides are preferred), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl laurate, etc.), acryl Ronitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and derivatives thereof, e.g. vinyltoluene, di Nielbenzene, vinylacetophenone, sulfostyrene, styrenesulfonic acid, etc.), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g., vinyl ethyl ether, etc.), maleic esters, N- Vinyl-2-pyrrolidone, N-vinylpyridine, 2-vinylpyridine, 4-vinylpyridine and the like.

Among these, acrylic ester, methacrylic ester and aromatic vinyl compound are particularly preferable.

Two or more different monomer compounds can be used in combination. For example, n-butyl acrylate and divinylbenzene, styrene and methyl methacrylate, methyl acrylate and methacrylic acid and the like can be used in combination.

Hereinafter, the specific example [Example compound (1)-Example compound (14)] of the compound represented by the said General formula (I) is specified. However, the present invention is not limited thereto.

The UV absorber represented by the general formula (I) is Japanese Patent Publication No. S44-29620, Japanese Patent Application Publication No. S53-128333, Japanese Patent Application Publication No. S61-169831, Japanese Patent Application Publication No. S63-53543 , Japanese Patent Application Laid-Open No. S63-53544, Japanese Patent Application Laid-Open No. S63-56651, and the like, and the methods described in the pamphlet of WO2009 / 123109. Specifically, the exemplary compound (1) can be synthesized by the method described in paragraph No. 0040 of the pamphlet of WO2009 / 123109.

Although the curable composition of the present invention may or may not contain a UV absorber, when the composition contains a UV absorber, the content of the UV absorber is 0.1% by mass to 10% by mass relative to the total solids content of the composition. It is preferable, It is more preferable that it is 0.1 mass%-5 mass%, It is especially preferable that it is 0.1 mass%-3 mass%.

[Other additives]

In order to improve the physical properties of the cured film, known additives such as plasticizers and sensitizers may be added to the curable composition.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerine, and the like. When used, a plasticizer can be added in the quantity of 10 mass% or less with respect to the total mass of the said polymeric compound and binder polymer.

<Microlens>

The curable composition of the present invention can form a transparent film having a high refractive index and a high transmittance, and thus can be used very well for forming microlenses, microlens arrays, and the like, for example.

That is, the curable composition of the present invention is preferable for forming microlenses.

Moreover, this invention relates to the microlens formed using the transparent film formed using the curable composition of this invention.

[Formation method of microlens]

The formation method of a microlens using the curable composition of this invention is not specifically limited, The method normally used is applied. Among these, the formation method containing the following process at least is preferable.

(I-1) Process of forming coating film on board | substrates, such as a color filter using curable composition of this invention

(II-1) Process of obtaining a high refractive index film (transparent film) by heating the coating film mentioned above and drying (or drying and hardening) a coating film

(III-1) Process of forming a resist coating film on the said high refractive index film after heating

(IV-1) Process of exposing the said resist coating film by the light source (g line | wire, i line | wire etc.) which have a suitable wavelength.

(V-1) Process of developing the resist coating film after the exposure to form a resist pattern

(VI-1) Process of transforming the resist into lens type by post heating

(Iii-1) a step of forming the high refractive index film into a lens type by removing the resist pattern and a part of the high refractive index film described above by dry etching

Hereinafter, these processes are demonstrated.

-(I-1) process-

In the present step, the curable composition of the present invention is applied onto a substrate such as a color filter to form a coating film.

The coating method is not particularly limited and, for example, a suitable method such as a spray method, a roll coating method, a spin coating method and a bar coating method may be employed.

-(II-1) process-

In this process, it is preferable that embodiment of the heating of the said coating film includes the two-step heating process of a prebaking process and a postbaking process.

The pre-baking process conditions may vary depending on the type or amount of each component used, but usually for 30 seconds to 15 minutes at 60 ℃ ~ 120 ℃. The film thickness of the coating film formed is the value after a prebaking process, and it is preferable that they are 0.5 micrometer-20 micrometers. The prebaking step may be omitted.

Subsequently, the coating film is cured by heating (post-baking process) the coating film using a heating device such as a hot plate and an oven. Usually, the post-baking process conditions are for 30 seconds to 60 minutes at 120 ℃ to 300 ℃. On the other hand, curing can be promoted by performing exposure before the post-baking process.

As the radiation to be irradiated, ultraviolet rays such as g-rays and i-rays, far ultraviolet rays such as KrF excimer lasers and ArF excimer lasers, X-rays such as synchrotron radiation, and charged particle radiation such as electron radiation can be used. Among them, ultraviolet rays are preferred.

Although it is preferable to select the said exposure amount according to structures, such as a photosensitive resin composition, it is preferable that they are 50mJ / cm <2> -2,000mJ / cm <2>.

-(III-1) process-

In this process, a resist coating film is formed on a high refractive index film. As the resist, a commercially available resist which can be formed by ordinary ultraviolet exposure can be used. About the said resist coating film, the said prebaking process is performed similarly to the (I-1) process.

-(IV-1) process-

In this process, the coating film is exposed in a pattern type using a mask. As the radiation to be irradiated, ultraviolet rays such as g-rays and i-rays, far ultraviolet rays such as KrF excimer lasers and ArF excimer lasers, X-rays such as synchrotron radiation, and charged particle radiation such as electron radiation can be used, respectively. Selective light suitable for the photosensitive wavelength of the resist is required.

-(V-1) process-

In this step, the resist coated film after the exposure is developed with a developer, preferably an alkaline developer, and a pattern of a predetermined shape is formed by removing the non-irradiated portion or the irradiated portion of radiation.

Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylamino ethanol, di-n -Propylamine, triethyl amine, methyldiethyl amine, dimethyl ethanolamine, triethanol amine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, pyrrole, piperidine, l, 8-diazabicyclo [5 Aqueous solutions, such as, 4,0] -7-undecene and l, 5-diazabicyclo [4.3.0] -5-nonene, are included. A water-soluble organic solvent such as methanol and ethanol, a surfactant, or various organic solvents may be added to the alkaline developer and used.

As the developing method, appropriate methods such as an adhesion method, an immersion method, a locking immersion method, and a showering method can be adopted. On the other hand, after developing with the alkaline developer, the coating film is usually washed with running water, for example.

Although image development time changes with the composition of the photosensitive resin composition and the developing solution, it is 30 to 120 second normally at room temperature.

-(VI-1) process-

In this step, the post heating (post baking step) is performed by a heating apparatus such as a hot plate and an oven so that the resist is transformed into a lens type after the pattern is formed. Usually, the post-baking process conditions are for 30 seconds to 60 minutes at 120 ℃ to 300 ℃. In order to deform into a lens type, a stepwise baking method may be employed which comprises performing two or more heat treatment times.

-(X-1) process-

Dry etching can be performed by a well-known method (for example, Unexamined-Japanese-Patent No. 2010-204154).

In this way, the desired microlenses can be formed.

According to the method of forming the microlenses of the present invention, high precision microlenses and microlens arrays having excellent characteristics (for example, high refractive index and high transmittance) can be simply formed with high yield.

<Undercoat film of the color filter>

The curable composition of the present invention can be used as an undercoat film of a color filter. Since the curable composition of this invention can also form a transparent film and a coating film, the said film can be used suitably as an undercoat film.

That is, it is preferable that the curable composition of this invention is for undercoat of a color filter.

It is preferable that the said undercoat film is an undercoat film of the color filter formed in the following process.

(I'-1) Process of forming a coating film with the apparatus formed on it using the curable composition of this invention

(II'-1) The process of obtaining a transparent film by heating the above-mentioned coating film and drying (or drying and hardening) the said coating film.

(III'-1) The process of forming a color filter by a well-known method on the above-mentioned transparent film

Formation of the coating film and the transparent film may be performed according to the method described in the <microlens>.

In the present invention, the undercoat film of the microlens and the color filter is formed of the curable composition of the present invention, and has excellent balance in characteristics, so that liquid crystal display devices for various office automation devices, liquid crystal TVs, mobile phones, projectors, and the like; It can be used suitably for the image of optical on-chip color filters, such as a facsimile, an electronic copier, a solid-state image sensor, and an optical fiber connector.

<Solid State Imaging Device>

The solid-state imaging device of the present invention includes at least one of a transparent film and a microlens formed using the curable composition of the present invention.

The solid-state imaging device of the present invention includes at least one of a transparent film and a microlens having a high refractive index and a high transmittance, and noise can be reduced to exhibit excellent color reproduction.

The solid-state imaging device of the present invention is not particularly limited as long as the device has a configuration including at least one of a transparent film and a microlens formed by using the curable composition of the present invention and a function functioning as a solid-state imaging device, and its For example, a light receiving element consisting of a plurality of photodiodes, polysilicon constituting a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) are formed on a substrate, and the undercoat film is disposed under a color filter. A configuration, a configuration in which the microlens is provided on a color filter, and the like.

Then, 2nd invention of this invention is demonstrated.

<Composition>

The composition according to the second invention of the present invention is a binder polymer (F-2) containing a repeating unit derived from titanium oxide particles or zirconium oxide particles, benzyl (meth) acrylate as metal oxide particles (A-2). And a surfactant (G-2), wherein the content of the surfactant (G-2) is 0.0010% by mass to 3.0% by mass relative to the total solids content of the composition.

In the composition of the present invention, it is preferable that titanium oxide particles or zirconium oxide particles are dispersed in the composition as the metal oxide particles (A-2), and more preferably contained and dispersed in the composition as a dispersion composition described later. Do.

<Dispersion Composition>

The dispersion composition contained in the composition according to the second invention of the present invention comprises titanium oxide particles or zirconium oxide particles, dispersion resin (B-2) and solvent (C-2) as metal oxide particles (A-2). It is preferable that it is a dispersion composition containing.

(A-2) Titanium oxide particles or zirconium oxide particles as metal oxide particles

As the metal oxide particles (A-2) of the present invention, at least titanium oxide particles or zirconium oxide particles are used. The titanium oxide particles and zirconium oxide particles are inorganic particles having a high refractive index. Examples of the titanium oxide particles include titanium dioxide (Ti0 ₂ ) particles, and examples of the zirconium oxide particles include zirconium dioxide (Zr0 ₂ ) particles. Since the composition of the present invention can obtain a higher refractive index, it is preferable to contain at least titanium oxide particles as the metal oxide particles (A-2), and among these, titanium dioxide particles (hereinafter simply referred to as "titanium dioxide"). More often).

The titanium oxide particles and zirconium oxide particles of the present invention preferably have a primary particle diameter of 1 nm to 100 nm, for example, appropriately selected from commercially available titanium oxide particles and zirconium oxide particles. It is preferable.

It is preferable that the said titanium oxide particle and zirconium oxide particle have a primary particle diameter of 1 nm-100 nm, 1 nm-80 nm are more preferable, 1 nm-50 nm are especially preferable. The titanium oxide particles and zirconium oxide particles preferably have a primary particle diameter of 100 nm or less because the decrease in refractive index and transmittance is suppressed. It is preferable that the said primary particle diameter is 1 nm or more, since the fall of the dispersibility or dispersion stability by aggregation is suppressed.

In the present invention, the primary particle diameters of the titanium oxide particles and zirconium oxide particles are obtained as average particle diameters of the titanium oxide particles and zirconium oxide particles. In the present invention, the average particle diameter of the titanium oxide particles and zirconium oxide particles is obtained by diluting a mixture or dispersion containing titanium oxide particles and / or zirconium oxide particles by 80 times with propylene glycol monomethyl ether acetate. It means the value obtained by making a measurement using a dynamic light scattering method with respect to a dilution liquid.

This measurement is calculated as a number average particle diameter obtained by measuring using MICROTRAC UPA-EX150 (manufactured by NIKKISO Co., Ltd.).

Although the refractive index of the said titanium oxide particle and zirconium oxide particle in particular in this invention is not restrict | limited, It is preferable that it is the range mentioned above about the refractive index of the said metal oxide particle (A-1) in a similar manner.

It is preferable that it is the range mentioned above about the specific surface area of the said metal oxide particle (A-1) about the specific surface area of the said titanium oxide particle and a zirconium oxide particle.

The shape of the titanium oxide particles and zirconium oxide particles is not particularly limited. For example, the shape may be the shape described above with respect to the shape of the metal oxide particles (A-1).

In the present invention, the titanium oxide particles and zirconium oxide particles may be particles that have been surface-treated with the organic compound described above for the metal oxide particles (A-1). In addition, preferable embodiment with respect to the said surface treatment is the same as that mentioned above with respect to the said metal oxide particle (A-1).

In the titanium oxide particles and zirconium oxide particles of the present invention, commercially available products can be preferably used. Examples of the commercially available products include the same ones as those exemplified in the metal oxide particles (A-1).

Although the metal oxide particle (A-2) of this invention can use a metal oxide particle individually or in combination of 2 or more types, at least 1 type thereof is the above-mentioned titanium oxide particle or zirconium oxide particle.

When two or more kinds of metal oxide particles are used in combination as the metal oxide particles (A-2), metals that can be used in combination with the above-described titanium oxide particles or zirconium oxide particles as long as the effects of the present invention are not impaired. The oxide particles are not particularly limited, but inorganic particles having a high refractive index are preferable. Examples thereof include silicon oxide particles, and examples of the silicon oxide particles include silicon oxide (Si0 ₂ ) particles. Embodiments of the primary particle diameter, refractive index, specific surface area, shape, and surface treatment of the silicon oxide particles are the same as those of the ranges described above for the titanium oxide particles and the zirconium oxide particles.

A commercial item may be preferably used as the silicon oxide particles, and a commercially available product of the silicon dioxide particles is Clariant Co. Agent OG502-31, etc. are included.

In this invention, it is preferable that the said titanium oxide particle or zirconium oxide particle is 30 mass%-100 mass% with respect to the total mass of a metal oxide particle (A-2), and it is 60 mass%-100 mass% More preferably, it is more preferable that it is 80 mass%-100 mass%, and it is most preferable that it is 100 mass% (namely, metal oxide particle (A-2) consists only of a titanium oxide particle or a zirconium oxide particle).

When the dispersion composition or the composition of the present invention is configured to obtain a very high refractive index, the content of the metal oxide particles (A-2) of the composition is from 10% by mass to 10% by weight based on the total composition of the dispersion composition or the composition of the present invention. It is preferable that it is 90 mass%, 10 mass%-50 mass% are more preferable, 12 mass%-40 mass% are more preferable, 15 mass%-35 mass% are especially preferable.

On the other hand, in particular with respect to the microlens having a high refractive index, the content of the metal oxide of the composition is preferably 50% by mass to 90% by mass with respect to the dispersion composition of the present invention or the total solids content of the composition, and preferably 52% by mass to 85 mass% is more preferable, and 55 mass%-80 mass% are the most preferable.

(B-2) Dispersion Resin

It is preferable that the dispersion composition contained in the composition of this invention contains a dispersion resin. The dispersion resin is not particularly limited as long as the dispersion resin disperses the metal oxide particles (A-2), but is preferably a copolymer having a graft chain, and is referred to as a graft copolymer (hereinafter referred to as "specific resin 1"). More often). The graft copolymer has a graft chain having 40 to 10,000 atoms other than hydrogen atoms. In this case, the graft chain is the same as the graft chain described above of the graft copolymer (B-1), and is preferably used for the same reason.

As the dispersing resin (B-2) preferably used in the present invention, the graft copolymer preferably has 40 to 10,000 atoms per graft chain other than hydrogen atoms, and the number of atoms other than hydrogen atoms is 100 per graft chain. It is more preferable that it is -500, and it is still more preferable that the number of atoms other than a hydrogen atom is 150-260 per graft chain.

If the number of atoms per graft chain other than the hydrogen atom is 40 or more, the graft chain is long, which is preferable because it means that the steric repulsion effect is increased and dispersibility or dispersion stability is improved. On the other hand, when the number of atoms per graft chain other than a hydrogen atom is 10,000 or less, the graft chain is not too long, and the decrease in adsorption force with the metal oxide particles is suppressed, thereby suppressing a decrease in dispersibility or dispersion stability.

In addition, the number of atoms per graft chain other than a hydrogen atom is the same as that described in the said graft copolymer (B-1).

As the polymer structure of the graft chain, the same structure as that described above in the graft copolymer (B-1) can be used, and its preferred range is also the same.

The graft copolymer preferably has a structural unit (repeating unit) having a graft chain, and can be obtained, for example, by polymerizing a macromonomer having a polymer structure as a graft chain according to a conventional method. The structure of the macromonomer is not particularly limited as long as the macromonomer has a substituent capable of reacting with the polymer backbone moiety and also has a graft chain that satisfies the needs of the present invention. However, preference is given to using macromonomers having reactive double bond groups.

Examples of commercially available macromonomers that can be preferably used for the synthesis of the specific resin 1 include the commercially available macromonomers described above in the graft copolymer (B-1).

It is preferable that the said specific resin 1 contains at least 1 structural unit represented by any one of general formula (1)-general formula (4) of a graft copolymer (B-1) as a structure which has a graft chain, and is general It is more preferable to include at least one structural unit represented by any one of formula (1A), formula (2A), formula (3) and formula (4).

In specific resin 1 used preferably for this invention, it is preferable that the structural unit (repeating unit) which has the said graft chain is contained in 10 mass%-80 mass% with respect to the total mass of the said specific resin 1, The range of 20 mass%-65 mass% is more preferable, and 35 mass%-60 mass% are especially preferable. When the content of the structural unit is within these ranges, the dispersibility or dispersion stability of the metal oxide particles is high, and the uniformity of the film thickness of the coating film formed by using the composition containing the dispersion composition is further improved. Specific resin 1 used in the present invention may combine two or more graft copolymers having different structures.

It is preferable that the specific resin 1 used preferably by this invention is a polymer containing the structural unit (repeating unit) which has an acidic radical in the quantity of 20 mass%-90 mass% with respect to the total mass of the specific resin 1. As for content of the structural unit which has the said acidic radical, it is more preferable that it is 50 mass%-80 mass% with respect to the total mass of the said specific resin 1, and 60 mass%-75 mass% are the most preferable.

When the content of the structural unit having an acid group is 20% by mass or more, the adsorptivity of the specific resin 1 to the metal oxide particles becomes sufficient, so that the dispersion stability is improved. When the composition of the present invention is applied onto a wafer of large size (eg, 12 inches), it is easy to form a film having a film having a small difference in film thickness between the center portion and the peripheral portion of the wafer.

When content of the structural unit which has the said acidic radical is 90 mass% or less with respect to the total mass of the said specific resin 1, the quantity which the said chain chain introduce | transduces into the specific resin 1 becomes enough, and dispersion stability is improved. When the composition of the present invention is applied onto a large size (eg, 12 inch) wafer, it is easy to form a film with a small difference in film thickness between the center portion and the peripheral portion of the wafer.

Since the content of the structural unit having an acid group is within the above range, the acid value of the specific resin 1 can be suitably controlled within the following preferred range.

The acid groups serve as functional groups capable of forming interactions with metal oxide particles other than the graft chain.

The acid group and acid group structure are the same as the acid group and acid group structure described above in the graft copolymer (B-1), and the preferred range thereof is also the same.

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

It is preferable that the acid value of the said specific resin 1 exists in the range of 70 mgKOH / g-350 mgKOH / g, The range of 80 mgKOH / g-300 mgKOH / g is more preferable, 80 mgKOH / g- More preferred is the range of 150 mgKOH / g. Even when the composition is applied on a large size (eg, 12 inch) wafer, the film having a small difference in film thickness between the center portion and the peripheral portion of the wafer is obtained by controlling the acid value to the above-mentioned range. It is clear.

The specific resin 1 may further include a structural unit (repeating unit) having a functional group capable of forming interaction with the metal oxide particles in addition to the graft chain and the acid group. The structural unit having a functional group capable of forming interaction with other metal oxide particles is not particularly limited in structure, but examples thereof include the same structure as the structure described above in the graft copolymer (B-1) and And its preferred range is also the same.

Specific resin 1, which is preferably included in the dispersion composition of the metal oxide particles, is another structure having further various functions as a structural unit derived from the copolymerization component in order to improve various performances such as image intensity, so long as the effects of the present invention are not impaired. Dispersion medium used for dispersing other than these structural units in addition to the structural units having the graft chain, the structural unit having the acid group, and the functional unit capable of forming interaction with the metal oxide particles, for example It may include a structural unit comprising a functional group having affinity with.

Examples of the copolymerizable component that can be copolymerized include the polymerizable component described above in the graft copolymer (B-1), and the preferred range thereof is also the same.

The radically polymerizable compounds may be used alone or in combination of two or more. The said specific resin 1 may or may not contain the radically polymerizable compound mentioned above. However, when the said resin contains a compound, the content of the structural unit corresponding to the said radically polymerizable compound is 0.1 mass%-50 mass% with respect to the total mass of the said specific resin 1, and 0.1 mass%-30 mass% Particularly preferred.

It is preferable that the weight average molecular weight (polystyrene conversion value measured by GPC method) of the said specific resin 1 is 5,000-300,000, 7,000-100,000 are more preferable, 10,000-50,000 are especially preferable.

As the dispersion resin (B-2), a resin described below (hereinafter, appropriately referred to as "specific resin 2") may be used. The said specific resin 2 has a repeating unit containing the group X which has a functional group of pKa14 or less, and the oligomer chain or polymer chain Y which has 40-10,000 atom number in a side chain, and contains a basic nitrogen atom.

The dispersion composition of the present invention interacts with the metal oxide particles (A-2) at both a nitrogen atom and a pKa 14 or less functional group having the group X in the specific resin 2, and the specific resin 2 is 40 The metal oxide particles are represented as high refractive index particles because they have an oligomer chain or polymer chain Y having a number of 10,000 atoms, for example, the oligomer chain or polymer chain Y can serve as a steric repulsion and exhibit excellent dispersibility. Disperse evenly. Even when the dispersion composition is stored at room temperature or the like for a long time, the oligomer chain or the polymer chain Y may interact with a solvent to suppress precipitation of metal oxide particles for a long time. When the coating film is formed of a dispersion composition (more specifically, for example, a curable composition), the oligomer chain or polymer chain Y acts as a three-dimensional repulsive group to suppress aggregation of metal oxide particles. As described above, even if the content of the metal oxide particles is increased, dispersibility or dispersion stability is not easily impaired. That is, the dispersion composition of the present invention can be used to achieve excellent dispersibility and dispersion stability and to obtain a film having a very high refractive index.

Here, the basic nitrogen atom is not particularly limited as long as the basic nitrogen atom is a basic nitrogen atom, but the specific resin 2 preferably contains a structure having a nitrogen atom of pKb 14 or less, and preferably has a nitrogen atom of pKb 10 or less. It is more preferable to contain a structure.

Basic strength pK _b in the present invention refers to the pK _b of from 25 ℃ temperature and is one of indexes representing the strength of the base to quantitatively the same as a basic constant. The basic strength pK _b and acidic strength pK _a described later have a relationship of pK _b = 14-pK _a .

The pK _a of less than 14 group X having a functional group is the same as the group X to be described later with respect to the specific resin 2-1.

The oligomer chain or polymer chain Y having 40 to 10,000 atoms in number having the specific resin 2 in the side chain is the same as the oligomer chain or polymer chain Y having 40 to 10,000 atoms in number described later with respect to the specific resin 2-1.

Examples of the specific resin 2 include a repeating unit containing a group X having a functional group of pKa 14 or less represented by the following general formula, a repeating unit having a basic nitrogen atom represented by the following general formula, and 40 represented by the following general formula. Listed are resins containing repeating units (corresponding to the order of the left side of the structure of the repeating unit below) comprising an oligomer chain or a polymer chain Y having ˜10,000 atomic numbers.

In the formula, x, y and z each represent a polymerization molecular ratio of the repeating unit, x is 5 to 50, y is 5 to 60, and z is preferably 10 to 90. l represents the connection number of a polyester chain, it is an integer which can form the oligomer chain or polymer chain which has 40-10,000 atom number, and 70-2,000 are preferable.

It is preferable that the said specific resin 2 is resin which has the nitrogen atom couple | bonded with the group X which has a functional group of pKa14 or less, and the repeating unit containing the oligomer chain or polymer chain Y which has 40-10,000 atom number in a side chain.

The specific resin 2 includes (i) a poly (lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, wherein a group X having a pKa 14 or less functional group is bonded to a nitrogen atom; At least one repeating unit containing a nitrogen atom selected from a metha xylenediamine-epichlorohydrin polycondensation repeating unit and a polyvinylamine repeating unit, and (ii) an oligomer chain having 40 to 10,000 atoms in the side chain, or It is especially preferable that it is resin 2-1 (Hereinafter, it calls suitably "specific 2-1") containing polypolymer chain Y.

(i) selected from poly (lower alkyleneimine) repeating units, polyallylamine repeating units, polydiallylamine repeating units, metaxylenediamine epichlorohydrin polycondensation repeating units and polyvinylamine repeating units At least one repeating unit containing a nitrogen atom)

Particular resins 2-1 of the present invention include (i) poly (lower alkyleneimine) -based repeat units, polyallylamine-based repeat units, polydiallylamine-based repeat units, metaxylenediamine epichlorohydrin multi-condensed repeat units, and At least one repeating unit containing a nitrogen atom selected from polyvinylamine-based repeating units. Therefore, the adsorption force with the surface of the metal oxide particles (A-2) can be improved, and the interaction between the metal oxide particles can be reduced.

The poly (lower alkyleneimine) may be in the shape of a chain or a mesh.

In the (i) poly (lower alkyleneimine) -based repeat unit, polyallylamine-based repeat unit, polydiallylamine-based repeat unit, metha xylenediamine- epichlorohydrin multi-condensation repeat unit and polyvinylamine repeat unit The number average molecular weight of the main chain obtained by polymerizing at least one repeating unit containing a nitrogen atom selected, that is, the number average molecular weight of the portion excluding a part of the oligomer chain or the polypolymer chain Y of the side chain from the specific resin 2-1 is 100 to It is preferable that it is 10,000, 200-5,000 are more preferable, and 300-2,000 are the most preferable. The number average molecular weight of the main chain portion may be determined from the ratio of the end group and the integer number of hydrogen atoms of the main chain portion measured by nuclear magnetic resonance spectroscopy, or may be determined by measuring the molecular weight of an oligomer or polymer containing an amino group as a raw material. .

It is particularly preferable that the repeating unit (i) containing the nitrogen atom is a poly (lower alkyleneimine) based repeating unit or a polyallylamine based repeating unit. In the present invention, the expression "lower" used for the poly (lower alkyleneimine) indicates that the carbon atom is 1 to 5, and the lower-alkyleneimine is an alkylene having 1 to 5 carbon atoms. Represents immigration. When specifying such a structure, specific resin 2-1 of this invention has a structure or general formula (II-) which has a repeating unit represented by general formula (I-1), and a repeating unit represented by general formula (I-2). It is preferable to include the structure which has a repeating unit represented by 1) and a repeating unit represented by general formula (II-2).

(Repeating unit represented by general formula (I-1) and repeating unit represented by general formula (I-2))

As a preferable structural component of specific resin 2-1 of this invention, the repeating unit represented by general formula (I-1) and the repeating unit represented by general formula (I-2) are demonstrated in detail.

In the above general formula (I-1) and general formula (I-2),

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group. a independently represents an integer of 1 to 5; * Indicates a linking site between repeating units.

X represents a group containing a functional group of pKa 14 or less.

Y represents an oligomer chain or a polymer chain having 40 to 10,000 atoms.

Specific resin 2-1 of the present invention, as a copolymerization component, further has a repeating unit represented by the general formula (I-3) in addition to the repeating unit represented by the general formula (I-1) or (I-2). desirable. When the resin is used as a dispersant for the metal oxide particles (A-2), the dispersion performance can be further improved by using these repeating units in combination.

In general formula (I-3),

*, R ¹ , R ² and a are the same as in general formula (I-1).

Y 'represents an oligomer chain or a polymer chain containing an anionic group having 40-10,000 atoms.

Forming a repeating unit represented by the general formula (I-3) by adding an oligomer or a polymer having a group which reacts with an amine to form a salt to the resin having a primary amino group or a secondary amino group in the main chain portion to react. It is possible.

In the general formulas (I-1), (I-2) and (I-3), R ¹ and R ² are particularly preferably hydrogen atoms. a is preferably 2 from the viewpoint of raw material availability.

Certain resins 2-1 of the present invention may include lower alkyleneimines as repeating units in addition to the repeating units represented by formulas (I-1), (I-2) and (I-3). . As mentioned above, the lower alkyleneimine represents an alkyleneimine having 1 to 5 carbon atoms. Although the specific resin 2-1 may or may not contain such a lower alkyleneimine repeating unit, when the specific resin 2-1 contains a lower alkyleneimine repeating unit, the lower alkyleneimine repeating unit It is preferable to be contained in the quantity of 1 mol%-70 mol% with respect to all the repeating units contained in the said specific resin 2-1, and 3 mol%-50 mol% are more preferable. On the other hand, the group represented by X, Y, or Y 'may be bonded to the nitrogen atom of such a lower alkyleneimine repeating unit. In addition, a resin including both a repeating unit having a group represented by X bonded to the main chain structure and a repeating unit having bonded Y may be included in the specific resin 2-1 of the present invention.

The repeating unit represented by the general formula (I-1) is a repeating unit containing a nitrogen atom to which a group X containing a functional group of pKa 14 or less is bonded, and the repeating unit containing the nitrogen atom is a storage stability and development. It is preferable to contain in the quantity of 1 mol%-80 mol% with respect to all the repeating units contained in the said specific resin 2-1 from a viewpoint of sex, and it is preferable to contain in 3 mol%-50 mol%.

The repeating unit represented by the general formula (I-2) is a repeating unit containing an oligomer chain or a polymer chain having 40 to 10,000 atoms, and the repeating unit is the specific resin 2 of the present invention in view of storage stability. It is preferable to contain in the quantity of 10 mol%-90 mol% with respect to all the repeating units of -1, and it is most preferable to contain in the quantity of 30 mol%-70 mol%.

Examining these content ratios, the molecular ratio of the repeating unit (I-1): repeating unit (I-2) is in the range of 10: 1 to 1: 100 in terms of dispersion stability and balance of hydrophilicity and hydrophobicity. It is preferable that it is preferable, and it is more preferable to exist in the range of 1: 1-1: 10.

On the other hand, the repeating unit represented by the general formula (I-3) used in combination as necessary has a partial structure containing an oligomer chain or a polymer chain having 40 to 10,000 atoms, and ionically bonds with nitrogen atoms of the main chain. From the viewpoint of the effect, it is preferably contained in an amount of 0.5 mol% to 20 mol% with respect to the total repeating units of the specific resin 2-1, and most preferably contained in an amount of 1 mol% to 10 mol%. desirable.

On the other hand, the ionic bond of the polymer chain Y can be confirmed by infrared spectroscopy or base titration.

(Repeating unit represented by general formula (II-1) and repeating unit represented by general formula (II-2))

As another preferable structural component of specific resin 2-1 of this invention, the repeating unit represented by general formula (II-1) and the repeating unit represented by general formula (II-2) are demonstrated in detail.

In general formula (II-1) and general formula (II-2),

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. *, X and Y are the same as *, X and Y of General Formula (I-1) and General Formula (I-2).

The said specific resin 2-1 is a repeating unit represented by general formula (II-3) as a copolymerization component other than the repeating unit represented by the said general formula (II-1), and the repeating unit represented by the said general formula (II-2). It may include. When the resin is used as a dispersant for the metal oxide particles (A-2), the dispersing performance can be further improved by using these repeating units in combination.

In general formula (II-3), *, R <^3> , R <^4> , R <^5> and R <^6> are It is the same as those in general formula (II-1). Y 'is the same as Y' in general formula (I-3).

In general formula (II-1), general formula (II-2), and general formula (II-3), it is preferable that R <^3> , R <^4> , R <^5> and R <^6> are hydrogen atoms from a raw material availability.

The general formula (II-1) is a repeating unit containing a nitrogen atom to which a group X containing a functional group of pKa 14 or less is bonded, and in view of storage stability and developability, the repeating unit containing such a nitrogen atom is a specific resin. It is preferable to be contained in the quantity of 1 mol%-80 mol% with respect to all the repeating units contained in 2-1, and it is more preferable to contain in the quantity of 3 mol%-50 mol%.

The general formula (II-2) is a repeating unit having an oligomer chain or a polymer chain Y having 40 to 10,000 atoms, and the repeating unit is the total repeating unit of the specific resin 2-1 of the present invention in view of storage stability. It is preferably contained in an amount of 10 mol% to 90 mol%, and most preferably in an amount of 30 mol% to 70 mol%.

When examining these content ratios, it is preferable that the molecular ratio (II-1) :( II-2) of a repeating unit exists in the range of 10: 1-1: 100 from a dispersion stability and a balance of hydrophilicity and hydrophobicity. More preferably in the range of 1: 1 to 1:10.

As needed, it is preferable that the repeating unit represented by general formula (II-3) used by a combination is contained in 0.5 mol%-20 mol% with respect to the total repeating unit of specific resin 2-1, and 1 mol Most preferably, it is contained in the amount of%-10 mol%.

In particular resin 2-1 of this invention, it is most preferable to include both the repeating unit represented by general formula (I-1) and the repeating unit represented by general formula (I-2) especially from a dispersible viewpoint.

<group X containing a functional group of pKa 14 or less>

X has a pKa 14 or less functional group at a water temperature of 25 ° C. Here, the "pKa" is as defined in Chemical Handbook (II) (4 ^th Revised Edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).

The "functional group of pKa 14 or less" is not particularly limited in structure and the like as long as its physical properties satisfy these conditions, and examples thereof include known functional groups having pKa in the above-mentioned range, and functional groups of pKa 12 or less Is particularly preferred, and groups up to pKa 11 are most preferred. Specifically, examples thereof include carboxylic acid (pKa is approximately 3 to 5), sulfonic acid (pKa is approximately -3 to -2), -COCH ₂ CO- (pKa is approximately 8 to 10),- COCH ₂ CN (pKa 8 to 11 Im), -CONHCO-, a phenolic hydroxyl group, -R _F CH ₂ OH or _{-. (R F) 2 CHOH} (R F represents a perfluoroalkyl group pKa is approximately 9-11), sulfonamide groups (pKa are approximately 9-11), and the like, carboxylic acids (pKa are approximately 3-5), sulfonic acids (pKa are approximately -3-2), and- COCH ₂ CO- (pKa is approximately 8-10) is particularly preferred.

Since the pKa of the functional group having the group X is 14 or less, interaction with the metal oxide particles (A-2) can be achieved.

The group X containing the pKa 14 or less functional group is preferably bonded directly to the nitrogen atom of the repeating unit containing the nitrogen atom, but the nitrogen atom and the group X of the repeating group containing the nitrogen atom are not covalent or ionic. Can be linked to form a salt.

It is especially preferable that group X containing the functional group of pKa14 or less of this invention has a structure represented by general formula (V-1), general formula (V-2), or general formula (V-3).

In general formula (V-1) and general formula (V-2),

U represents a single bond or a divalent linking group.

d and e independently represent 0 or 1;

In the general formula (V-3), Q represents an acyl group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include alkylene (more specifically, for example, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CHMe—, — (CH ₂ ) ₅ —, —CH ₂ CH (nC ₁₀ H ₂₁ )-, etc.), oxygen-containing alkylene (more specifically, for example, -CH ₂ OCH _2- , -CH ₂ CH ₂ OCH ₂ CH _2- , etc.), an arylene group (Example For example, phenylene, tolylene, biphenylene, naphthylene, furanylene, pyrroylene, etc.), alkyleneoxy (for example, ethyleneoxy, propyleneoxy, phenyleneoxy, etc.), alkenylene group (for example, Vinylene group) and the like, but are preferably an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 30 carbon atoms, or an arylene group having 6 to 20 carbon atoms, 1 Most preferred are alkylene groups having ˜20 carbon atoms, alkenylene groups having 2 to 20 carbon atoms, and arylene groups having 6 to 15 carbon atoms. From the viewpoint of productivity, d is preferably 1, and e is preferably 0.

Q represents an acyl group or an alkoxycarbonyl group. As the acyl group in Q, an acyl group having 1 to 30 carbon atoms (for example, formyl, acetyl, n-propanoyl, benzoyl, etc.) is preferable, and acetyl is particularly preferable. As the alkoxycarbonyl group in Q, an alkoxycarbonyl group having 2 to 30 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, etc.) is preferable. As Q, an acyl group is especially preferable, and an acetyl group is preferable from a viewpoint of ease of manufacture and raw material availability (precursor X 'of X).

Group X of the present invention is preferably combined with a nitrogen atom of a repeating unit containing a nitrogen atom. Thus, the dispersibility and dispersion stability of the metal oxide particles (A-2) are remarkably improved.

The group X functions as an alkali soluble group including a pKa 14 or less functional group as a partial structure. Therefore, when the resin is used in a curable composition or the like to impart energy on the coating film to partially cure the coating film, dissolve the unexposed portion to remove the portion, and form a pattern, the resin is converted into an alkaline developer in the uncured region. It is thought that the developability is improved and dispersibility, dispersion stability and developability are established.

Although the content of the functional group of pKa 14 or less in X is not specifically limited, It is preferable that it is 0.01 mmol-5 mmol, and it is most preferable that it is 0.05 mmol-1 mmol with respect to 1 g of specific resin 2 of this invention. Within these ranges, the dispersibility and dispersion stability of the said metal oxide particle (A-2) improve, and when the said resin is used for a curable composition, developability of an unhardened part becomes excellent. From the viewpoint of the acid value, when used in the curable composition having the specific resin divalent pattern formability of the present invention, the functional group is an acid value of the specific resin 2 is 5 mgKOH / g ~ 50 mgKOH / g from the developable viewpoint It is preferably included in the amount.

(Oligomer chain or polymer chain Y having 40 to 10,000 atoms)

Examples of Y include known polymer chains, such as polyesters, polyamides, polyimides and poly (meth) acrylic acid esters, which may be linked to the backbone portion of certain resins 2. It is preferable that the bonding part of Y with respect to the said specific resin 2 is the terminal of the said oligomer chain or the polymer chain Y.

Y is selected from poly (lower alkyleneimine) -based repeat units, polyallylamine-based repeat units, polydiallylamine-based repeat units, metaxylenediamine-epichlorohydrin multi-condensed repeat units and polyvinylamine-based repeat units It is preferred to combine with nitrogen atoms of at least one repeating unit containing nitrogen atoms. Nitrogen atom selected from a poly (lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, a metaxylenediamine-epichlorohydrin multicondensation repeating unit and a polyvinylamine repeating unit The bond form between the main chain portion and Y, such as at least one repeating unit containing, is a covalent bond, an ionic bond, or a combination of covalent bonds and ionic bonds. The ratio of the bond form of the Y and the main chain portion is in the range of covalent bond: ion bond = 100: 0 to 0: 100, 95: 5 to 5:95 are preferred, and 90:10 to 10:90 are most preferred. Do. When the said ratio is out of the said range, dispersibility and dispersion stability will fall and solvent solubility will also decrease.

It is preferable that Y is an amide bond or an ionic bond as a carboxylate to the nitrogen atom of the repeating unit containing the said nitrogen atom.

The number of atoms of the oligomer chain or polymer chain Y is preferably 50 to 5,000, more preferably 60 to 3,000, from the viewpoint of dispersibility, dispersion stability and developability.

When the number of atoms per oligomer chain or polymer chain Y is less than 40, the graft chain is short, resulting in a decrease in steric repulsion effect and a decrease in dispersibility. On the other hand, when the number of atoms per oligomer chain or polymer chain Y exceeds 10,000, the oligomer chain or polymer chain Y is too long, resulting in a decrease in adsorptive power with metal oxides and a decrease in dispersibility.

The number average molecular weight of the Y may be measured in terms of polystyrene by the GPC method. From the viewpoint of dispersibility, dispersion stability and developability, the number average molecular weight of Y is preferably 1,000 to 50,000, and most preferably 1,000 to 30,000.

Preferably at least two, most preferably at least five side chain structures represented by Y are bonded to the main chain linking group in one molecule of the resin.

In particular, Y preferably has a structure represented by General Formula (III-1).

In general formula (III-1), Z is a polymer or oligomer which has a polyester chain as a partial structure, and represents the residue remove | excluding the carboxyl group from the polyester which has the free carboxylic acid represented by the following general formula (IV).

In general formula (IV), Z is the same as Z in general formula (III-1).

When the said specific resin 2-1 contains the repeating unit represented by general formula (I-3) or general formula (II-3), it is preferable that Y 'is represented by general formula (III-2).

In General Formula (III-2), Z is the same as Z in General Formula (III-1).

A polyester having a carboxyl group at one terminal (polyester represented by formula (IV)) is a polycondensate of carboxylic acid and lactone (IV-1) and a polycondensate of hydroxy group-containing carboxylic acid (IV-2). ), Polycondensates of dihydric alcohols and divalent carboxylic acids (or cyclic acid anhydrides) (IV-3) and the like.

The carboxylic acid used in the polycondensation reaction (IV-1) of the carboxylic acid and lactone is an aliphatic carboxylic acid (preferably a straight or branched carboxylic acid having 1 to 30 carbon atoms, for example formic acid). , Acetic acid, propionic acid, butyric acid, valeric acid, n-hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, palmitic acid, 2-ethylhexanoic acid, cyclohexanoic acid, etc.), hydroxy group-containing carboxyl Acids (preferably straight-chain or branched hydroxy groups containing 1-30 carbon atoms, for example glycolic acid, lactic acid, 3-hydroxypropionic acid, 4-hydroxydodecanoic acid, 5-hydroxy Dodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid, 2,2-bis (hydroxymethyl) butyric acid, etc.), and have a straight chain having 6 to 20 carbon atoms Aliphatic carboxylic acid or hydroxy group-containing carboxylic acid having 1 to 20 carbon atoms Hi is preferred. These carboxylic acids are used in the mixture. As the lactone, known lactones can be used, examples of which are β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-valero Lactones, δ-hexanolactone, δ-octanolactone, ε-caprolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, and the like. Particularly preferred.

These lactones can be used in combination of several types.

The supply molar ratio of the carboxylic acid and the lactone at the time of reaction depends on the molecular weight of the desired polyester chain, and thus the ratio cannot be determined alone, but is preferably carboxylic acid: lactone = 1: 1 to 1: 1,000, 1: 3-1: 500 are the most preferable.

The hydroxyl group containing carboxylic acid in the polycondensate (IV-2) of the said hydroxyl group containing carboxylic acid is the same as the hydroxyl group containing carboxylic acid in (IV-1), and its preferable range is also the same.

The dihydric alcohol (IV-3) of the polycondensation reaction of the dihydric alcohol and divalent carboxylic acid (or cyclic acid anhydride) has a linear or branched aliphatic diol (preferably having 2 to 30 carbon atoms). Diols such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 8-octanediol and the like), and aliphatic diols having 2 to 20 carbon atoms are particularly preferred.

Examples of the divalent carboxylic acid are linear or branched divalent aliphatic carboxylic acids (preferably divalent aliphatic carboxylic acids having 1 to 30 carbon atoms, for example, succinic acid, maleic acid, ammonia). Dicarboxylic acid, sebacic acid, dodecane diacid, glutaric acid, suberic acid, tartaric acid, oxalic acid, malonic acid, and the like), and divalent carboxylic acid having 3 to 20 carbon atoms is particularly preferred. In addition, acid anhydrides (e.g., succinic anhydride, glutaric anhydride, etc.) equivalent to these divalent carboxylic acids can be used.

The divalent carboxylic acid and the dihydric alcohol are preferably supplied in a molar ratio of 1: 1. Thus, it is possible to introduce carboxylic acids to the ends.

It is preferable that the polycondensate at the time of preparation of the said polyester is performed by addition of a catalyst. The catalyst is preferably a catalyst that functions as a Lewis acid, and examples thereof include Ti compounds (eg Ti (OBu) ₄ , Ti (0-Pr) _4, etc.), Sn compounds (eg tin octyl). Laterates, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyl oxide, stan chloride, and the like), protonic acid (eg, sulfuric acid, paratoluenesulfonic acid, and the like), and the like. It is preferable that the quantity of the said catalyst is 0.01 mol%-10 mol% with respect to the mole number of all monomers, and it is most preferable that it is 0.1 mol%-5 mol%. It is preferable that it is 80 degreeC-250 degreeC, and, as for the said reaction temperature, it is most preferable that it is 100 degreeC-180 degreeC. Although the said reaction time changes with reaction conditions, it is preferable that it is 1 hour-24 hours normally.

The number average molecular weight of the polyester can be measured in terms of polystyrene by the GPC method. The number average molecular weight of the said polyester is 1,000-1,000,000, 2,000-100,000 are preferable and 3,000-50,000 are the most preferable. The molecular weight within this range can achieve both dispersibility and developability.

The polyester partial structure forming the polymer chain in Y is obtained by the polycondensate (IV-1) of carboxylic acid and lactone and the polycondensate (IV-2) of hydroxy group-containing carboxylic acid from the viewpoint of ease of production. It is especially preferable that it is polyester.

Although specific embodiment [(A-1)-(A-61)] of specific resin 2 of this invention is shown below by the specific structure of the repeating unit which resin has, and its combination, this invention is not limited to this. In the following general formula, k, l, m, and n respectively show the polymerization molar ratio of a repeating unit, k represents 1-80, l represents 10-90, m represents 0-80, n is 0 ˜70, and k + l + m + n = 100. p and q show the number of connections of a polyester chain, and they represent 5-100,000 each independently. R 'represents a hydrogen atom or an alkylcarbonyl group.

In order to synthesize the specific resin 2 of the present invention, the specific resin comprises (1) a method of reacting a resin having a primary or secondary amino group, a precursor x of X and a precursor y of Y, and (2) containing X It can be prepared by a method of polymerizing a monomer and a macromonomer containing Y and the like, wherein the specific resin first synthesizes a resin having a primary amino group or a secondary amino group in the main chain, and the resin is a precursor of X and precursors of Y react with y to provide the reactants to the nitrogen atoms present in the main chain by polymer reaction.

Examples of the resin having a primary amino group or a secondary amino group include oligomers or polymers containing a primary amino group or a secondary amino group constituting a main chain portion containing a nitrogen atom, for example poly (lower alkyleneimine), polyallyl. Amines, polydiallylamines, metaxylenediamine epichlorohydrin polycondensates, polyvinylamines and the like. Among these, oligomers or polymers composed of poly (lower alkyleneimine) or polyallylamine are preferable.

The precursor x of the group X having a functional group of pKa 14 or less represents a compound capable of reacting with a resin having a primary amino group or a secondary amino group to introduce X into the main chain.

Examples of x are cyclic carboxylic anhydrides (cyclic carboxylic anhydrides having 4 to 30 carbon atoms), and for example, succinic anhydride, glutaric anhydride, itaconic anhydride, maleic anhydride, allyl succinic acid Anhydride, butyl succinic anhydride, n-octyl succinic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-docosenyl succinic anhydride, (2-hexen-1-yl) succinic anhydride , (2-methylpropen-1-yl) succinic anhydride, (2-dodecen-1-yl) succinic anhydride, n-octenyl succinic anhydride, (2,7-octanedien-1-yl) succinic anhydride, Acetyl malic anhydride, diacetyl tartaric anhydride, het acid anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, 3 or 4-methyl cyclohexane-1,2-dicarboxylic acid anhydride, tetrafluoro succinic anhydride, 3 or 4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclo Hexene-1,2-dicarboxylic anhydride, phthalic acid anhydride, tetrachlorophthalic anhydride, naphthalic anhydride, naphthalic anhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6- Tetracarboxylic dianhydride, pyromellitic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentane carboxylic dianhydride), Halogen atom-containing carboxylic acids (e.g., chloroacetic acid, bromoacetic acid, iodic acid, 4-chloro-n-butyric acid, etc.), sultones (e.g. propane sultone, 1,4-butanesultone, etc.), dike Ten, cyclic sulfocarboxylic acid anhydride (e.g., _2- sulfobenzoic anhydride, etc.), -COCH ₂ COCl- containing compounds (e.g., ethylmalonyl chloride, etc.), cyano acetate chloride, and the like, Particular preference is given to cyclic carboxylic anhydride, sultone and diketene from the viewpoint of productivity.

The precursor y of oligomer chain or polymer chain Y having 40 to 10,000 atoms represents a compound capable of introducing oligomer chain or polymer chain Y by reacting with a resin having a primary amino group or a secondary amino group.

The y is preferably an oligomer or a polymer having a number of 40 to 10,000 atoms having a group capable of covalently or ionically bonding to a nitrogen atom of a specific resin 2 at the terminal, 40 to 10,000 having a free carboxyl group at one terminal Most preferred are oligomers or polymers having an atomic number.

Examples of y include polyesters represented by the general formula (IV) having free carboxylic acid at one end, polyamide having free carboxylic acid at one end, and poly having free carboxylic acid at one end. Although (meth) acrylic-acid resin etc. are contained, The polyester represented by general formula (IV) which contains a free carboxylic acid at one terminal especially is the most preferable.

Y is represented by the general formula (IV) by a known method, for example, an oligomer or polymer containing a polycondensate (IV-1) of a carboxylic acid and a lactone, a primary amino group or a secondary amino group as described above. It can be synthesize | combined by the method of preparing the polyester containing free carboxylic acid in one terminal shown. The polyamide containing the free carboxylic acid at one terminal may be formed by self condensation such as amino group-containing carboxylic acid (for example, glycine, alanine, β-alanine, 2-amino butyric acid, etc.). The poly (meth) acrylic acid ester containing free carboxylic acid at one end thereof is subjected to radical polymerization of a (meth) acrylic acid monomer in the presence of a carboxyl group-containing chain transfer agent (for example, 3-mercaptopropionic acid, etc.). Can be formulated.

Specific resin 2 of the present invention comprises (a) a method in which a resin having a primary amino group or a secondary amino group reacts simultaneously with x and y, (b) a resin having a primary amino group or a secondary amino group first reacts with x, Subsequently, the reaction with y, or (c) a resin having a primary amino group or a secondary amino group may be prepared by the reaction with y and then with x. In particular, (c) a method in which a resin having a primary amino group or a secondary amino group first reacts with y and then with x is preferred.

Although it is preferable that the said reaction temperature is selected according to conditions, 20 to 200 degreeC is preferable and 40 to 150 degreeC is the most preferable. It is preferable that it is 1 hour-48 hours from a viewpoint of productivity, and, as for the said reaction time, it is more preferable that it is 1 hour-24 hours.

The reaction may be carried out in the presence of a solvent. Examples of the solvent include water, sulfoxide compounds (e.g., dimethyl sulfoxide, etc.), ketone compounds (e.g., acetone, methyl ethyl ketone, cyclohexanone, etc.), ester compounds (e.g., ethyl acetate, Butyl acetate, ethyl propionate, propylene glycol 1-monomethyl ether 2-acetate, and the like, ether compounds (e.g., diethyl ether, dibutyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbon compounds (e.g., Pentane, hexane, etc.), aromatic hydrocarbon compounds (e.g., toluene, xylene, mesitylene, etc.), ditolyl compounds (e.g., acetonitrile, propionitrile, etc.), amide compounds (e.g., N, N -Dimethyl formamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc., carboxylic acid compounds (e.g. acetic acid, propionic acid, etc.), alcohol compounds (e.g. methanol, ethanol, isopropane) Ol, n-butanol, 3-methyl butanol, 1-methoxy-2-propanol and the like), and a halogen solvent (for example, chloroform, 1,2-dichloroethane and the like).

When the said solvent is used, it is preferable that a solvent is used by 0.1 mass times-100 mass times with respect to a board | substrate, and it is most preferable that they are 0.5 mass times-10 mass times.

Certain resins 2 of the present invention can be purified by a reprecipitation method. When the said specific resin 2 obtained by removing a low molecular weight component by the reprecipitation method is used as a dispersing agent, the said dispersing performance improves. It is preferable that alcohol solvents, such as a hexane hydrocarbon solvent and methanol, are used with respect to the said reprecipitation method.

Therefore, it is preferable that specific resin 2 obtained by this invention has a weight average molecular weight of 3,000-100,000 as measured by the GPC method, and 5,000-55,000 are more preferable. The molecular weight in the above-described range has the advantage of achieving high developability and high storage stability. In the specific resin 2 of the present invention, (i) the presence of nitrogen atoms in the repeating unit containing nitrogen atoms can be confirmed by a method such as acid titration, and (ii) the presence of a functional group of pKa 14 or less and the functional groups The binding of nitrogen atoms of the repeating unit can be confirmed by methods such as base titration, nuclear magnetic resonance spectroscopy and infrared spectroscopy. It can be confirmed by methods such as nuclear magnetic resonance spectroscopy and GPC that the oligomer chain or polymer chain having the number of 40 to 10,000 atoms is contained in the side chain.

Hereinafter, the specific example of specific resin 2 of this invention is demonstrated with molecular weight. R 'represents an alkyl group.

In the dispersion composition preferably contained in the composition of the present invention, the specific resin 1 and the specific resin 2 may be used alone or in combination of two or more thereof.

In view of the dispersibility and dispersion stability, the content of the dispersion resin (B-2) (for example, specific resin 1 or specific resin 2) is preferably contained in the total solid content or the composition of the present invention. It is preferable to exist in the range of 10 mass%-50 mass% with respect to it, It is more preferable that it is 1 mass%-40 mass%, The range of 12 mass%-30 mass% is further more preferable.

-Other Dispersion Resin-

The dispersion composition preferably contained in the composition of the present invention may include a dispersion resin (hereinafter sometimes referred to as "other dispersion resin") in addition to the specific resin in order to control the dispersibility of the metal oxide particles and the like. Examples of other dispersion resins other than the specific resins include the dispersion resins described above in the graft copolymer (B-1), and the preferred ranges are also the same.

The dispersion composition preferably contained in the composition of the present invention may or may not contain other dispersion resins. However, when the composition contains other dispersion resins, the content of the other dispersion resins is preferably used in the composition of the present invention. It is preferable to exist in the range of 1 mass%-20 mass% with respect to the total solid content contained or the composition of this invention, and the range of 1 mass%-10 mass% is more preferable.

(C-2) Solvent

The dispersion composition preferably contained in the composition of the present invention includes a solvent, and the solvent may be composed of various organic solvents.

The organic solvent which can be used here is the same as the solvent (C-1) mentioned above.

These organic solvents may be used alone or in combination. It is preferable that the density | concentration of solid content of the dispersion composition contained preferably in the composition of this invention is 2 mass%-60 mass%.

Although the preparation method of the dispersion composition preferably contained in the composition of this invention is not restrict | limited, Usually, the preparation method of the dispersion composition used can be applied. For example, preparation can be performed by mixing the metal oxide particles (A-2), the dispersion resin (B-2), and the solvent (C-2), and the mixture can be prepared using a circulating dispersion device (bead mill). Distributed processing can be performed.

<Composition>

The composition of the present invention is a binder polymer (F-2) and a surfactant containing a repeating unit derived from benzyl (meth) acrylate in addition to the titanium oxide particles or zirconium oxide particles as the metal oxide particles (A-2) described above. It is a composition containing (G-2), and content of the said surfactant (G-2) is 0.0010 mass%-3.0 mass% with respect to the total solid content of the said composition.

With such a configuration, a composition having a high refractive index and capable of forming a film (typically a transparent film) having a small change in the shape of the coated surface over time even after application of the composition and a decrease in refractive index after the development treatment is produced. It is possible.

It is preferable that the composition of this invention is a curable composition. As an embodiment of the said curable composition, the composition of this invention is comprised so that the composition of this invention may further contain a polymeric compound (D-2) and a polymerization initiator (E-2), and also contains another component as needed. It is preferable that it is a curable composition.

In this way, since the "curable composition" of the present invention is of "composition" type as described above, the content of the metal oxide relative to the total solid content of the curable composition is in the range of the content of the metal oxide particles in the above-described composition or dispersion composition. Is the same as

By making the composition of the present invention into a curable composition, a film (typically a transparent film) having a high refractive index and having a small change in the shape of the coated surface over time even after application of the composition and a decrease in refractive index after development treatment is more preferable. Can be formed.

Furthermore, this invention relates to the transparent film formed using the composition or curable composition of this invention.

It is preferable that the film obtained from the composition or curable composition of this invention or the cured film (film formed by the curable composition, and then hardening reaction) has a refractive index of 1.72-2.60, and 1.80-2.60 are more preferable.

The physical property that the film or cured film has a refractive index of 1.72 to 2.60 is a binder polymer (F-2) in which the composition of the present invention contains a repeating unit derived from metal oxide particles (A-2) and benzyl (meth) acrylate. And surfactant (G-2) (also, polymerizable composition (D-2) and polymerization initiator (E-2) in the curable composition of the present invention) can be achieved in any manner. The physical properties control, for example, the type and content of the polymerizable composition (D-2) or a binder polymer which may be further added, or contain metal oxide particles (A-2) in the composition, and then the metal oxide It is preferable to achieve by controlling the type and content of.

In particular, the above-described physical properties can be more easily achieved by using metal oxide particles as the preferred examples above.

It is preferable that the composition of this invention is a transparent composition, More specifically, when the film or cured film with a film thickness of 1.0 micrometer is formed by the said composition, the composition has a light transmittance of 400 with respect to the thickness direction of a film or cured film. It is a composition which is 90% or more over the wavelength range of nm-700 nm.

That is, the transparent film of the present invention means a film having a light transmittance of 90% or more over a wavelength range of 400 nm to 700 nm at a film thickness of 1.0 μm with respect to the thickness direction of the film.

The binder polymer (F-2) containing the repeating unit derived from a metal oxide particle (A-2), a benzyl (meth) acrylate, and surfactant (G-2) (The composition of this invention is also of the present invention. Although the physical properties of such light transmittance can be achieved in any manner as long as it contains the polymerizable compound (D-2) and the polymerization initiator (E-2)) in the curable composition, for example, the polymerizable compound (D-2) Or by controlling the type and content of binder polymer that can be further added. In addition, the physical properties of the light transmittance can be preferably achieved by controlling the particle diameter of the metal oxide particles (A-2) or the type and amount of the dispersion resin (B-2).

For the compositions and transparent films of the present invention, the fact that the light transmittance is 90% or more for the entire wavelength region of 400 nm to 700 nm is an important factor for exhibiting the properties required especially for microlenses.

It is preferable that it is 90% or more with respect to the all wavelength range of 400 nm-700 nm, It is more preferable that it is 99% or more, 100% is the most preferable.

In view of the above, the composition of the present invention is substantially free of a colorant (the content of the colorant is preferably 0% by mass based on the total solids content of the composition).

(F-2) Binder polymer containing a repeating unit derived from benzyl (meth) acrylate

The composition of the present invention contains a binder polymer (F-2) containing a repeating unit derived from benzyl (meth) acrylate. It is assumed that the binder polymer contains a repeating unit derived from benzyl (meth) acrylate to stabilize the dispersion state of the metal oxide particles in the composition, thereby exhibiting the effect of the present invention.

The binder polymer (F-2) of the present invention is derived from (meth) acrylate in addition to a repeating unit derived from benzyl (meth) acrylate (hereinafter sometimes referred to as "BzMA" or "repeating unit BzMA"). It is preferable to further include a repeating unit (hereinafter sometimes referred to as "MAA" or "repeating unit MAA"), and further to contain a repeating unit derived from alkyl (meth) acrylate in addition to the repeating unit. desirable. The effect of the present invention is more successfully shown by the binder polymer (F-2) containing these repeating units.

Usually, the repeating unit ("repeat unit MAA") derived from the said (meth) acrylate is a repeating unit derived from (meth) acrylic acid.

It is preferable that the alkyl group of the side chain in the repeating unit derived from the said alkyl (meth) acrylate has 1-30 carbon atoms, and 1-20 carbon atoms are more preferable.

Examples of the repeating unit derived from the alkyl (meth) acrylate include repeating units derived from isobutyl (meth) acrylate (hereinafter sometimes referred to as "iBuMA" or "repeating unit iBuMA"), hydroxyethyl Repeating units derived from (meth) acrylates (hereinafter sometimes referred to as "HEMA" or "repeating units HEMA"), repeating units derived from alkyl (meth) acrylates containing ethylene oxide groups and the like ( The following may be referred to as "EOA" or "repeating unit EOA", and at least one of these repeating units is preferable, and at least two repeating units are particularly preferable.

Here, the repeating unit derived from the alkyl (meth) acrylate containing the said ethylene oxide group is substituted part or all of the alkylene chain in the alkyl group of the side chain of the repeating unit derived from the alkyl (meth) acrylate by the ethylene oxide group. It means a repeating unit having a structure. The ethylene oxide group-is preferably represented by _{- n (C 2 H 4 0} ). Here, n represents an integer, the integer of 2-90 is preferable, the integer of 4-23 is more preferable, the integer of 6-15 is especially preferable.

The binder polymer (F-2) preferably has an ethylene oxide group, more preferably contains a repeating unit EOA, and more preferably contains both the repeating unit EOA and the repeating unit iBuMA.

That is, it is preferable that the binder polymer (F-2) of this invention contains all the said repeating unit BzMA, the repeating unit MAA, the repeating unit EOA, and the repeating unit iBuMA, and is a binder polymer comprised only of these four repeating units. Most preferred.

It is not clear why the repeating unit iBuMA and the repeating unit EOA are included as the repeating unit of the binder polymer (F-2) in addition to the repeating unit BzMA, but the uniformity of the solution state when the film is prepared as a coating film And the uniformity of the film can be further promoted by balancing the solubility of the binder polymer (F-2) in the composition and compatibility with the metal oxide particles.

In the binder polymer (F-2) of the present invention, the content of the repeating unit BzMA is preferably in the range of 10 mol% to 65 mol% with respect to the total repeating units of the binder polymer (F-2), and 10 mol% 50 mol% is more preferable, and 20 mol%-40 mol% are more preferable.

The binder polymer (F-2) of the present invention may or may not contain the repeating unit MAA. However, when the binder polymer contains the repeating unit, the content of the repeating unit MAA is determined by the amount of the binder polymer (F-2). It is preferable to exist in the range of 1 mol%-50 mol% with respect to all the repeating units, It is more preferable that it is 5 mol%-40 mol%, The range of 10 mol%-35 mol% is further more preferable.

The binder polymer (F-2) of the present invention may or may not contain the repeating unit iBuMA. However, when the binder polymer contains the repeating unit, the content of the repeating unit iBuMA is equal to that of the binder polymer (F-2). It is preferable that it is the range of 1 mol%-50 mol% with respect to all the repeating units, The range of 10 mol%-50 mol% is more preferable, The range of 20 mol%-45 mol% is further more preferable.

The binder polymer (F-2) of the present invention may or may not contain the repeating unit HEMA, but in the case where the binder polymer contains the repeating unit, the content of the repeating unit HEMA is determined by the binder polymer (F-2). It is preferable to exist in the range of 1 mol%-40 mol% with respect to all the repeating units, The range of 3 mol%-30 mol% is more preferable, The range of 5 mol%-25 mol% is further more preferable.

The binder polymer (F-2) of the present invention may or may not contain the repeating unit EOA. However, when the binder polymer contains the repeating unit, the content of the repeating unit EOA is determined by the amount of the binder polymer (F-2). It is preferable to exist in the range of 0.5 mol%-40 mol% with respect to all the repeating units, The range of 1 mol%-25 mol% is more preferable, The range of 2 mol%-15 mol% is further more preferable.

It is preferable that the weight average molecular weight (polystyrene conversion value measured by the GPC method) of the binder polymer (F-2) of this invention is 1,000 or more, 5,000-100,000 are more preferable, 5,000-50,000 are more preferable. It is preferable that it is 1 or more, and, as for its polydispersity (weight average molecular weight / number average molecular weight), 1.1-10 are more preferable.

The binder polymer (F-2) may be any one of a random polymer, a block polymer, and a graft polymer.

The binder polymer (F-2) of the present invention can be synthesized by methods known in the art. Examples of the solvent used for the synthesis include tetrahydrofuran, ethylene chloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, di Ethylene glycol dimethyl ether, l-methoxy-2-propanol, l-methoxy-2-propylacetate, N, N-dimethyl formamide, N, N-dimethyl acetamide, toluene, ethyl acetate, methyl lactate, ethyl Lactate, dimethyl sulfoxide, water and the like. These solvents may be used alone or in combination of two or more thereof.

Examples of the radical polymerization initiator used in the synthesis of the binder polymer (F-2) used in the composition of the present invention include compounds known in the art such as azo initiators and peroxide initiators.

Although the specific example of the said binder polymer (F-2) shows a weight average molecular weight (Mw) and a copolymerization ratio (molar ratio) below, this invention is not limited to this.

In the composition of the present invention, the binder polymer (F-2) may be used alone or in combination of two or more thereof.

In the composition of the present invention, the content of the binder polymer (F-2) is preferably 1% by mass to 40% by mass, more preferably 3% by mass to 30% by mass, based on the total solids content of the composition, 4 mass%-20 mass% are more preferable.

-Other Binder Polymers-

The composition of this invention can contain binder polymers other than the said binder polymer (F-2). As the binder polymer other than the binder polymer (F-2), the binder polymer described above in the binder polymer (F-1) (but not the binder polymer (F-2)) is preferably used.

In the composition of the present invention, binder polymers other than the binder polymer (F-2) may be used alone or in combination of two or more thereof.

Although the composition of this invention may contain or may not contain binder polymers other than the said binder polymer (F-2), when the said composition contains the said binder polymer, binder polymers other than the said binder polymer (F-2) It is preferable that content of is 1 mass%-40 mass% with respect to the total solid content of the said composition, 3 mass%-30 mass% are more preferable, 4 mass%-20 mass% are more preferable.

(G-2) surfactant

The composition of this invention can contain various surfactant in the range of 0.0010 mass%-3.0 mass% with respect to the total solid content of the said composition. When the coating film is formed by containing a surfactant in an amount of 0.0010% by mass or more, the surfactant is uniformly present between the metal oxide particles and the binder polymer, and as a result, the coated surface over time, which becomes a problem of the present invention. Deterioration of the shape of or the decrease of the refractive index after the etching phenomenon can be prevented. When the surfactant is added in an amount of more than 3.0% by mass, the shape of the coated surface itself is rather deteriorated by the repellency of the surfactant.

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

Among these, it is preferable to use a fluorine-type surfactant or a nonionic surfactant, and it is most preferable to use the said fluorine-type surfactant.

In particular, since the composition of the present invention contains a fluorine-based surfactant, when the composition is made of a coating liquid, the liquid properties (particularly, fluidity) can be further improved, so that the uniformity of the coating thickness is further improved or the liquid is Results in savings.

That is, when the film is formed by using the coating liquid to which the transparent composition containing the fluorine-based surfactant is applied, the surface to be coated by reducing the interfacial tension between the coated surface and the coating liquid to improve the wettability to the coated surface. The applicability of the is improved. Therefore, even when a thin film having a thickness of several micrometers is formed with a small amount of liquid, formation of a uniform thickness film with smaller thickness unevenness is more preferably carried out and is effective.

It is preferable that content% of fluorine in the said fluorine-type surfactant is 3 mass%-40 mass%, 5 mass%-30 mass% are more preferable, 7 mass%-25 mass% are especially preferable. Fluorine-based surfactants having a fluorine content% contained within the above-mentioned ranges are efficient in view of thickness uniformity and liquid saving of the coating film, and exhibit good solubility of the composition.

The fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicon-based surfactants are fluorine-based surfactants, nonionic surfactants, and cationic surfactants as described above in the surfactant (G-1). Active agents, anionic surfactants, silicon-based surfactants, and the like.

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

In the composition of the present invention, the content of the surfactant is required to be controlled to 0.0010% by mass to 3.0% by mass relative to the total solids content of the composition. In order to reduce the decrease in the refractive index after the etching phenomenon, which is a problem to be solved by the present invention, the content of the surfactant is preferably 0.010% by mass to 3.0% by mass relative to the total solids content of the composition, and is preferably 0.10% by mass to 3.0 mass% is more preferable, 0.50 mass%-3.0 mass% are more preferable, 1.0 mass%-3.0 mass% are especially preferable.

The composition of the present invention comprises titanium oxide particles as the metal oxide particles (A-2), a binder polymer (J-1) as the binder polymer (F-2), and a fluorine-based surfactant as the surfactant (G-2). It is preferable that the composition contains the fluorine-based surfactant, and the content of the fluorine-based surfactant may be formed because a film having a small change in the shape of the coated surface with time after application and a film having a low drop in refractive index after development treatment may be formed. It is preferable that they are 0.50 mass%-3.0 mass% with respect to total solid content.

(D-2) Polymerizable Compound

When the composition of the present invention is a curable composition and contains a polymerizable composition (D-2), the polymerizable composition (D-2) is preferably an addition polymerizable compound having at least one ethylenically unsaturated double bond, at least It is more preferable to select from compounds having one terminal ethylenically unsaturated bond, and more preferably two or more terminal ethylenically unsaturated bonds. Such compounds are well known in the art and any of these compounds may be used in the present invention without particular limitation. For example, the above-mentioned polymerizable compound (D-1) can be used.

Moreover, the urethane type addition polymeric compound manufactured by using addition reaction of an isocyanate and hydroxyl group is preferable, As the specific example thereof, the vinyl urethane compound containing 2 or more polymerizable vinyl groups in a molecule | numerator is included, Japanese patent It is obtained by adding the vinyl monomer containing a hydroxyl group represented by following General formula (V) to the polyisocyanate compound which has two or more isocyanate groups in a molecule | numerator as described in publication S48-41708.

In the following general formula (V), R <^7> and R <^8> represents a hydrogen atom or a methyl group each independently.

Further, the urethane acrylates described in Japanese Patent Application Laid-Open No. S51-37193, Japanese Patent Publication H2-32293 and Japanese Patent Publication H2-16765, or Japanese Patent Publication No. S58-49860, Japanese Patent Publication The urethane compound which has the ethylene oxide frame | skeleton of S56-17654, Unexamined-Japanese-Patent S62-39417, and S62-39418 is preferable. Curable compositions having excellent photosensitivity are disclosed in the molecules described in Japanese Patent Application Laid-Open No. S63-277653, Japanese Patent Application Laid-Open No. S63-260909 and Japanese Patent Application Laid-Open No. H-105238. It can be obtained by using a polymerizable compound having a.

Other examples thereof include polyester acrylates and epoxy resins as described in Japanese Patent Application Laid-Open No. S48-64183 and Japanese Patent Publication Nos. S49-43191 and Japanese Patent Publication No. S52-30490. Polyfunctional acrylates or methacrylates, such as the epoxy acrylate obtained by making it react, are contained. Examples thereof include specific unsaturated compounds described in Japanese Patent Publication No. S46-43946, Japanese Patent Publication Hl-40337, and Japanese Patent Publication Hl-40336, and Japanese Patent Application Publication No. H2-25493. Vinyl phosphate compounds and the like. In some cases, it is preferable to use the structure containing the perfluoroalkyl group of Unexamined-Japanese-Patent No. S61-22048. In some cases, the Journal of Japan Adhesion Society, Vol. 20, No. Photocurable monomers or oligomers described in 7, pages 300 to 308 (1984) can be used.

Moreover, as said polymeric compound, the compound containing the ethylenically unsaturated group which has a boiling point of 100 degreeC or more under the normal pressure which has at least 1 addition polymeric ethylene group is preferable. Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxyethyl) ether, tri (acryloyloxyethyl) isocyanurate , Polyglycerides such as urethane (meth) acrylates described in (meth) alkylated Japanese Patent Publications S48-41708 and Japanese Patent Publication S50-6034 and Japanese Patent Application Publication S51-37193, such as glycerin or trimethylol ethane Alcohol; Polyester acrylates described in Japanese Patent Application Laid-Open No. S48-64183, Japanese Patent Application Laid-Open No. S49-43191 and Japanese Patent Application Laid-Open No. S52-30490; As a reactant, polyfunctional acrylate or methacrylate, such as epoxy acrylate obtained by reacting an epoxy resin with (meth) acrylic acid, and a mixture thereof are included.

Examples thereof include a polyfunctional (meth) acrylate obtained by reacting a cyclic ether group such as glycidyl (meth) acrylate with a compound containing an ethylenically unsaturated group in the polyfunctional carboxylic acid.

In addition, as the other preferred polymerizable compound, the fluorene ring and the two or more functional groups described in Japanese Patent Application Laid-Open No. 2010-160418 and Japanese Patent Application Laid-Open No. 2010-129825 and Japanese Patent No. 4364216 C are ethylenic polymerizable groups. Compound having, and cardo resin can be used.

Moreover, as a compound which is addition polymerization property and has at least 1 ethylenically unsaturated group which has a boiling point of 100 degreeC or more under normal pressure, the compound of Paragraph [0254]-[0257] of Unexamined-Japanese-Patent No. 2008-292970 is preferable. Do.

Moreover, it is preferable to use the radically polymerizable monomer represented by the following general formula (MO-1)-general formula (MO-5) other than the above-mentioned. On the other hand, in the general formula, when T is an oxyalkylene group, R is bonded to the terminal on the carbon atom side.

In the general formula, n is 0 to 4, and m is 1 to 8. The plurality of R and T present in the molecule may be the same as or different from the other R and T, respectively.

In each of the radically polymerizable monomers represented by general formulas (MO-1) to (MO-5), at least one of the plurality of R's is -OC (= 0) CH = CH ₂ or -OC (= A group represented by 0) C (CH ₃ ) = CH ₂ is represented.

Specific examples of the radical polymerizable monomer represented by General Formulas (MO-1) to (MO-5) include the compounds described in paragraphs [0248] to [0251] of Japanese Patent Application Laid-Open No. 2007-269779. It is included and can be preferably used in the present invention.

In addition, Japanese Patent Application Laid-open No. H10-62986 is described as a compound of formulas (1) and (2) together with specific examples thereof, and ethylene oxide or propylene oxide is added to the polyhydric alcohol. The compound obtained by (meth) acrylation can be used as a polymeric compound.

Among these, as the polymerizable compound, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by NIPPON KAYAKU Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; NIPPON; KAYAKU Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by NIPPON KAYAKU Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available) It is preferable to use the structure which KAYARAD DPHA; the product made by NIPPON KAYAKU Co., Ltd.), and a (meth) acryloyl group have ethylene glycol or a propylene glycol residue. In addition, the oligomer type may be used.

The said polymeric compound is a compound which has a polyfunctional monomer, and can have acidic groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Thus, if the compound is a mixture as described above, the ethylene compound may be used on its own as long as the compound has an unreacted carboxyl group, but if necessary the acid group is an ethylene compound in which the non-aromatic carboxylic anhydride is described above. It can be introduced by reacting with a hydroxyl group of. In this case, specific examples of the non-aromatic carboxylic anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride and maleic anhydride.

In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound having an unsaturated carboxylic acid and has an acid group obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. It is preferable that it is a polyfunctional monomer which can be used, and it is especially preferable that the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol of an ester. Examples of commercially available products include TOAGOSEI CO., LTD., Such as M-5120 and M-520. Polybasic acid-modified acrylic oligomers.

These monomers may be used alone, but since it is difficult to use a single compound in the preparation, they may be used in combination of two or more kinds. As needed, the polyfunctional monomer which does not have an acidic radical as a monomer can be used in combination with the polyfunctional monomer which has an acidic radical.

It is preferable that the polyfunctional monomer which has the said acid group has an acid value of 0.1 mgKOH / g-40 mgKOH / g, and 5 mgKOH / g-30 mgKOH / g are more preferable. When the acid value of the said polyfunctional monomer is too low, image development dissolution characteristic will fall. When the acid value is too high, it is difficult to manufacture or handle the monomer and the photopolymerization performance is lowered. Thus, curability such as surface flatness of the pixel is deteriorated. Therefore, when the polyfunctional monomer which has another acid group is used by 2 or more types of combination, or when the polyfunctional monomer which does not have an acid group is used by combination, it is essential to control the said acid group as all the polyfunctional monomers in the above-mentioned range.

It is preferable that the polyfunctional monomer which has the said caprolactone structure is contained as a polymerizable monomer.

The polyfunctional monomer having the caprolactone structure is not particularly limited as long as the monomer has a caprolactone structure in the molecule, but examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterification of polyhydric alcohols such as dipentaerythritol, tripentaerythritol, glycerin, diglycerol and trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Included. Among these, the polyfunctional monomer which has a caprolactone structure represented by following General formula (1) is preferable.

(In general formula, all 6 R's are group represented by following General formula (2), or 1-5 of 6 R's are group represented by following General formula (2), and the remainder of it is Is a group represented by General Formula (3).)

(In general formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding hand.)

(In general formula, R <^1> represents a hydrogen atom or a methyl group, and "*" represents a bonding hand.)

The polyfunctional monomer having the caprolactone structure is NIPPON KAYAKU Co., Ltd. It is marketed as a KAYARAD DPCA series, and an example thereof is KAYARAD DPCA-20 (the number of groups represented by general formula (2) in which m = 1 and general formula (2) = 2). R ¹ is a compound which all represent a hydrogen atom, KAYARAD DPCA-30 (in the same general formula, m = 1, the number of groups represented by General formula (2) = 3, and R ¹ is all hydrogen atoms) KAYARAD DPCA-60 (in the same general formula, m = 1, the number of groups represented by General formula (2) = 6, and R <^1> is a compound which all represent a hydrogen atom.), KAYARAD DPCA- 120 (in the same general formula, m = 2, the number of groups represented by General formula (2) = 6, R <^1> is a compound which all represent a hydrogen atom), etc. are contained.

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

Moreover, it is preferable that it is at least 1 chosen from the compound group represented by the following general formula (i) or general formula (ii) as a specific monomer of this invention.

In the formulas (i) and (ii), each E independently represents-((CH ₂ ) _y CH ₂ 0)-or-((CH ₂ ) _y CH (CH ₃ ) 0)- and y each independently represent an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom or a carboxyl group.

In the said general formula (i), the sum of acryloyl group and methacryloyl group is 3 or 4, m respectively independently represents the integer of 0-10, and the sum of each m is an integer of 0-40. . However, when the sum of each m is 0, any one of X is a carboxyl group.

In the said General formula (ii), the sum of acryloyl group and methacryloyl group is 5 or 6, n respectively independently represents the integer of 0-10, and the sum of each n is an integer of 0-60. . However, when the sum of each n is 0, any one of X is a carboxyl group.

In said general formula (i), it is preferable that m is an integer of 0-6, and it is more preferable that it is an integer of 0-4. It is preferable that the sum total of each m is an integer of 2-40, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable.

In said general formula (ii), it is preferable that n is an integer of 0-6, and its integer of 0-4 is more preferable. It is preferable that the sum total of each n is an integer of 3-60, It is more preferable that it is an integer of 3-24, The integer of 6-12 is especially preferable.

In the general formula (i) or the general formula (ii),-((CH ₂ ) _y CH ₂ 0)-or-((CH ₂ ) _y CH (CH ₃ ) 0)-is X on the oxygen atom side. It is preferable that it is in the form combined with the terminal.

The compounds represented by the general formula (i) or the general formula (ii) may be used alone or in combination of two or more thereof. In particular, in general formula (ii), it is preferable that all 6 X is a form which is acryloyl group.

It is preferable that it is 20 mass% or more, and, as for the total content of the compound represented by general formula (i) or general formula (ii) in the said specific monomer, it is more preferable that it is 50 mass% or more.

The compound represented by the general formula (i) or (ii) is a step in which the ring-opening skeleton of ethylene oxide or propylene oxide is bound to pentaerythritol or dipentaerythritol by a ring-opening addition reaction, for example in the art It can be synthesize | combined from the process of introduce | transducing a (meth) acryloyl group by reacting the (meth) acryloyl chloride which has the terminal hydroxyl group of the said ring-opening skeleton which is a process known to the. Each process is a well-known process, and the compound represented by general formula (i) or general formula (ii) can be easily synthesized by those skilled in the art.

Among the compositions represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

Specific examples thereof include compounds represented by the following general formulas (a) to (f) (hereinafter referred to as "exemplified compounds (a) to exemplified compounds (f)"), and among these, exemplary compounds ( a), exemplary compound (b), exemplary compound (e) and exemplary compound (f) are preferable.

Examples of commercially available products of the specific monomers represented by the above general formulas (i) and (ii) include Sartomer Company Inc. SR-494, NIPPON KAYAKU Co., Ltd., which is a tetrafunctional acrylate having four ethyleneoxy chains DPCA-60 which is a 6 functional acrylate which has 6 pentyleneoxy chains, TPA-330 which is a trifunctional acrylate which has 3 isobutylene oxy chains, etc. are mentioned.

Moreover, urethane acrylate as described in Unexamined-Japanese-Patent No. S48-41708, Unexamined-Japanese-Patent S51-37193, Unexamined-Japanese-Patent No. H2-32293, and Unexamined-Japanese-Patent No. H2-16765, or a polymeric compound, or The urethane compound which has the ethylene oxide type | system | group frame | skeleton of Unexamined-Japanese-Patent No. S58-49860, Unexamined-Japanese-Patent S56-17654, S62-39417, and S62-39418 is preferable. As the polymerizable compound, a curable composition having excellent photosensitivity is amino in the molecules described in Japanese Patent Application Laid-Open No. S63-277653, Japanese Patent Application Laid-Open No. S63-260909 and Japanese Patent Application Laid-Open No. H-105238. It can be obtained by using an addition polymerizable compound having a structure or sulfide structure.

Examples of commercially available products of the polymerizable compounds include urethane oligomer UAS-10 and urethane oligomer UAB-140 (manufactured by Sanyo-Kokusaku Pulp Co., Ltd.) and urethane polyomer UA-7200 (SHIN-NAKAMURA CHMICAL CO., LTD. Urethane oligomer DPHA-40H (manufactured by NIPPON KAYAKU Co., Ltd.), urethane oligomer UA-306H, urethane oligomer UA-306T, urethane oligomer UA-306I, urethane oligomer AH-600, urethane oligomer T-600 and Urethane oligomer AI-600 (made by KYOEISHA CHEMICAL CO., LTD.) Is included.

As the polymerizable compound, an ethylenically unsaturated compound having an acid group is preferable. The ethylenically unsaturated compound which has the said acid group is obtained by the method of (meth) acrylating some hydroxyl groups of the said polyfunctional alcohol, the method of addition reaction of an acid anhydride to the said hydroxyl residue, and the method of obtaining a carboxyl group. Examples of commercially available products include polybasic acid modified acrylic oligomers such as M-5120 and M-520 (manufactured by TOAGOSEI CO., LTD.).

For these polymerizable compounds, the detailed description of the use method such as structure, single use or combination, addition amount of the compound may be arbitrarily determined according to the final performance design of the curable compound. For example, the above detailed description may be selected in view of the above-described polymerizable compound (D-1).

When the composition of this invention is a curable composition and contains a polymeric compound (D-2), the polymeric compound (henceforth an "epoxy compound") which has at least 1 epoxy group is said polymeric compound (D-2). ) Can be used. Such epoxy compounds are well known in the art, and any of these compounds may be used in the present invention without any particular limitation.

The compound of the present invention may or may not contain the polymerizable compound (D-2). However, when the compound contains the polymerizable compound (D-2), the compound of the polymerizable compound (D-2) It is preferable that content is in the range of 1 mass%-50 mass% with respect to the total solid content of the said composition, It is more preferable to exist in the range of 3 mass%-40 mass%, The range of 5 mass%-30 mass% More preferably.

It is preferable that it is content in the said range because it is excellent in sclerosis | hardenability without a fall of refractive index.

(E-2) polymerization initiator

The polymerization initiator (E-2) used when the composition of the present invention is a curable composition and contains the polymerizable compound (D-2) is used to initiate and promote the polymerizability of the polymerizable compound (D-2). Compound, and the polymerization initiator (E-2) is stable up to 45 ° C from the viewpoint of improving curing in heating steps such as step (IV-2) and (b) a method for producing a microlens described later, but at a high temperature. It is preferable to be excellent in the ability to start polymerization at the time of heating.

In the method for producing a microlens described later, light is emitted from an ultraviolet region in view of improving curing in exposure fixing by irradiation of radiation such as step (II-2), step (b), step (d), and the like. It is preferable to acknowledge. The polymerization initiator may be an activator which generates an active radical by causing any reaction with the photoexcited sensitizer, and may be an initiator that initiates cationic polymerization depending on the type of monomer.

The polymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

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

Examples of the polymerization initiator (E-2) include an organic halide compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide compound, an azo compound, a coumarin compound, an azide compound , Metallocene compound, hexaaryl biimidazole compound, organic boric acid compound, disulfonic acid compound, oxime ester compound, onium salt compound and acyl phosphine (oxide) compound, and specific examples thereof include the polymerization initiator It is the same as those mentioned in (E-1), and its preferable range is also the same.

The oxime compound is decomposed by the action of heat and functions as a thermal polymerization initiator for initiating and promoting polymerizability.

It is preferable that the oxime compound used for the said 2nd invention has a maximum absorption wavelength in the wavelength range of 350 nm-500 nm, The absorption wavelength in the wavelength range of 360 nm-480 nm is more preferable, 365 nm-455 nm It is especially preferable that it is an oxime compound which has the high absorbance of.

It is preferable that the said oxime compound has a molar extinction coefficient of 1,000-300,000 in 365 nm or 405 nm from a viewpoint of a sensitivity, 2,000-300,000 are more preferable, 5,000-200,000 are especially preferable.

The molar extinction coefficient of the compound may be measured using a known method, but specifically, an ultraviolet and visible spectrophotometer (CARY-5 spectrophotometer) at a concentration of 0.01 g / L, for example, using an ethyl acetate solvent. (Manufactured by Varian Inc.) is preferable.

As the oxime compound, commercially available products such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF Corporation) are preferably used, and IRGACURE OXE01 is more preferable.

Examples of the onium salt compound include the onium salt compound and the like described above in the polymerization initiator (E-1), and the preferred range thereof is also the same.

The composition of the present invention may or may not contain the polymerization initiator (E-2). However, when the composition contains an initiator, the content of the polymerization initiator (E-2) (total content in two or more cases) ) Is preferably 0.1% by mass to 10% by mass, more preferably 0.3% by mass to 8% by mass, and still more preferably 0.5% by mass to 5% by mass with respect to the total solid content of the composition.

In the case where the composition of the present invention is a curable composition, the curable composition may further contain an optional component, as described in detail below. Hereinafter, arbitrary components which the said curable composition can contain are demonstrated.

[Sensitizer]

The curable composition of the present invention may contain a sensitizer to further shift the sensitization wavelength to a longer wavelength in order to improve the radical generation efficiency of the polymerization initiator (E-2).

The sensitizer which can be used in the present invention preferably increases or decreases the polymerization initiator (E-2) by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer are included in the compounds described below, and include sensitizers having an absorption wavelength in the wavelength range of 300 nm to 450 nm.

That is, examples thereof include polynuclear aromatic groups (e.g., phenanthrene, anthracene, pyrene, perylene, triphenylene and 9,10-dialkoxy anthracene), xanthene (e.g., fluorescein, eosin, Erythrosine, rhodamine B and rose bengal), thioxanthone (isopropyl thioxanthone, diethyl thioxanthone and chlorothioxanthone), cyanine (eg thiacarbocyanine and oxacarbocyanine), Merocyanine (e.g. merocyanine and carbomerocyanine), phthalocyanine, thiazine (e.g. thionine, methylene blue and toluidine blue), acridine (e.g. acridine orange , Chloroflavin and acriflavin), anthraquinone (eg anthraquinone), squarylium (eg squarylium), acridine orange, coumarin (eg 7-diethylamino -4-methylcoumarin), ketocoumarin, phenothiazine, phenazine, styryl benzene, azo compound, diphenylmethane, tetra Riphenylmethane, distyryl benzene, carbazole, porphyrin, spiro compound, quinacridin, indigo, styryl, pyryllium compound, pyrromethene compound, pyrazolotriazole compound, benzothiazole compound, barbituric acid derivative, thio Barbituric acid derivatives; Aromatic ketone compounds such as acetophenone, benzophenone, thioxanthone and Michler's ketone; Heterocyclic compounds, such as N-aryl oxazolidinone, are included.

As an example of the sensitizer which can be used for this invention, it is more preferable that the compound represented by the following general formula (e-1)-general formula (e-4) is contained.

In the formula ^(e-1), A 1 denotes a sulfur atom or NR ^50, R ⁵⁰ represents an alkyl group or an aryl group, L ¹ is to form the A ¹ and a basic nucleus of a carbon atom with the dye is adjacent to L ¹ Represents a nonmetallic atom group, R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a monovalent nonmetallic atom group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus of the dye. W represents an oxygen atom or a sulfur atom.

In General Formula (e-2), Ar ¹ and Ar ² each independently represent an allyl group, and Ar ¹ and Ar ² are connected to each other via a bond —L ² —. Here, -L ² -represents -O- or -S-. W is the same as described in general formula (e-1).

In the formula (e-3), A ² represents a sulfur atom or NR ^59, L ³ represents a non-metallic atomic group forming the A ² and a basic nucleus of a carbon atom with the dye is adjacent to L ^3, R ^53, R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atom group, and R ⁵⁹ represents an alkyl group or an aryl group.

In general formula (e-4), A <^3> and A <^4> respectively independently represent -S- or -NR <^62> , R <^62> represents a substituted alkyl group or an unsubstituted alkyl group, or a substituted aryl group or an unsubstituted aryl group, L ⁴ represents a nonmetallic atom group in which A ³ and carbon atoms adjacent to L ⁴ together form a basic nucleus of the pigment, L ⁵ represents a nonmetallic atom group in which A ⁴ and carbon atoms adjacent to L ⁵ together form the basic nucleus of the pigment, R ⁶⁰ and R ⁶¹ each independently represent a monovalent nonmetallic atom group, and may be bonded to each other to form an aliphatic ring or an aromatic ring.

The curable composition may or may not contain a sensitizer. However, when the composition contains a sensitizer, the content of the sensitizer in the curable composition is solid in view of the light absorption efficiency of the core and the dispersion efficiency of the initiator. It is preferable that it is 0.1 mass%-20 mass% with respect to content, and 0.5 mass%-15 mass% are more preferable.

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

Examples of preferred sensitizers that may be contained in the curable composition include, in addition to the sensitizers, at least one selected from compounds represented by the following general formula (II) and compounds represented by the general formula (III).

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

In General Formula (III), R ¹¹ and R ¹² each independently represent a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. n represents the integer of 0-5, n 'represents the integer of 0-5, but neither n and n' represent 0 at the same time. When n is 2 or more, plural R ¹¹ are each the same or different may be with any other R ^11. If more than n 'is 2, a plurality of R ¹² are each the same or different may be with any other R ^12. The general formula (II) is not limited to any one of isomers composed of double bonds.

The general formula (Ⅱ) molar absorption efficiency (ε) is expressed by, and preferably not less than 500mol ^-1 · L · ㎝ ^-1 at a wavelength of 365㎚, more preferably not less than 300mol ^-1 · L · ㎝ ^-1 at a wavelength of 365㎚ Preferably, it is most preferable that it is 20,000 mol <^-1> L * cm <^-1> or more in wavelength 365nm. The value of the molar absorption efficiency epsilon at each wavelength is preferably in the above-described range because the effect of increasing sensitivity is increased in view of the optical absorption efficiency.

Preferred specific examples of the compound represented by the general formula (II) are described below, but the present invention is not limited thereto.

In the present specification, the chemical formula may be described by a simple structural formula, and the solid line represents a hydrocarbon group unless an element or a substituent is specified.

In the general formula (III), A ⁵ represents an aromatic ring or a heterocycle which may have a substituent, X ⁴ represents an oxygen atom, a sulfur atom or -N (R ²³ )-, and Y represents an oxygen atom or sulfur An atom or -N (R ²³ )-. R ²¹ , R ^22, and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atom group, and A ⁵ , R ²¹ , R ^22, and R ²³ may be bonded to each other to form an aliphatic ring or an aromatic ring.

In the general formula (III), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atom group. When R ²¹ , R ²² and R ²³ each represent a monovalent nonmetallic atom group, R ²¹ , R ²² and R ²³ each represent a substituted or unsubstituted alkyl group, a substituted aryl group or an unsubstituted aryl group, a substituted alkenyl group or an unsubstituted group. It is preferable that they are an alkenyl group, a substituted aromatic heterocyclic residue, or an unsubstituted aromatic heterocyclic residue, a substituted alkoxy group, or an unsubstituted alkoxy group, a substituted alkylthio group, or an unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

In the compound represented by the general formula (III), Y is preferably an oxygen atom or -N (R ²³ )-from the viewpoint of improving the dispersion efficiency of the photopolymerization initiator. And R ²³ represents a hydrogen atom or a monovalent non-metallic atomic group. Most preferably Y is -N (R ²³ )-.

Hereinafter, although the preferable specific example of a compound represented by the said general formula (III) is demonstrated, this invention is not limited to this. Without specifying an isomer by a double bond connecting the acidic nucleus and the basic nucleus, the present invention is not limited to any one of the isomers.

[Notary sensitizer]

Moreover, it is preferable that the curable composition of this invention contains a sensitizer.

In the present invention, the co-sensitizer has a function of further increasing the sensitivity of the polymerization initiator (E-2) and the sensitizer to actinic light that inhibits the polymerization inhibition of the polymerizable compound (D-2) due to oxygen. .

Examples of such sensitizers include amines such as "Joumal of Polymer Society", Vol. 10, p.3173 (1972), by MR Sander et al., Japanese Patent Publication No. S44-20189, Japanese Patent Application Publication No. S51-82102, Japanese Patent Application Publication No. S52-134692, Japanese Patent Application Publication No. S59- 138205, Japanese Patent Application Laid-Open No. S60-84305, Japanese Patent Application Laid-Open No. S62-18537 and Japanese Patent Application Laid-Open No. S64-33104, and Japanese Patent Application Publication No. 3825, are included. Specific examples thereof include triethanol amine, ethyl-p-dimethylaminobenzoate, p-formyldimethylaniline, p-methylthiodimethylaniline, and the like.

Other examples of such a sensitizer include thiols and sulfides, for example thiol compounds described in Japanese Patent Application Laid-Open No. S53-702, Japanese Patent Application Laid-Open No. S55-500806 and Japanese Patent Application Laid-open No. H5-142772, Japanese Patent Application Disulfide compounds described in Publication S56-75643 are included. Specific examples thereof include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazolin, β-mercaptonaphthalene, and the like. Included.

Other examples of the co-sensitizer include amino acid compounds (e.g., N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. S48-42965, hydrogen donors described in Japanese Patent Publication No. S55-34414, and Japanese Patents. Sulfur compounds described in Application Publication No. H6-308727 (eg, trithiane and the like).

The curable composition may or may not contain a co-sensitizer, but when the composition contains a co-sensitizer, the content of the co-sensitizer is increased in terms of the curing rate due to the balance of the polymerization increase rate and the chain transition. It is preferable to exist in the range of 0.1 mass%-30 mass% with respect to the total solid content mass of the said curable composition, It is more preferable to exist in the range of 1 mass%-25 mass%, It is 1.5 mass%-20 mass% of It is more preferable to be in a range.

[Polymerization inhibitor]

In this invention, in order to suppress unnecessary superposition | polymerization of the compound which has a polymeric ethylene unsubstituted double bond at the time of manufacturing or storing the said curable composition, it is preferable to add a polymerization inhibitor.

As the polymerization inhibitor, the polymerization inhibitor described above in the first invention can be used as the addition amount of the polymerization inhibitor described above. Moreover, its preferable embodiment is the same as that of the said 1st invention.

(UV absorbent)

The curable composition of the present invention may contain a UV absorber. As the UV absorber, the UV absorber described above in the first invention may be used as the content of the UV absorber described above. Moreover, its preferable range is also the same.

[Other additives]

In order to improve the physical properties of the cured film, any one of known additives such as a plasticizer and a sensitizer may be added to the curable composition.

As the plasticizer, the plasticizer described in the first invention can be used as the amount of the plasticizer mentioned above.

The composition or the curable composition of the present invention contains a solvent, the solvent may be composed of various organic solvents. Examples of the organic solvent that can be used include organic solvents such as solvent (C-2) in the above-mentioned dispersion composition.

These organic solvents may be used alone or in combination. It is preferable that the density | concentration of solid content in the composition or curable composition of this invention is 2 mass%-60 mass%.

[Method for Producing Transparent Film]

The manufacturing method of the transparent film of this invention is a process of coating the above-mentioned composition or curable composition on a wafer by a spray method, a roll coating method, a spin coating method, a bar coating method, etc., a subsequent 1st heating process, and a 1st heating process A subsequent second heating process at a temperature above the heating temperature in is included.

The conditions of the said 1st heating process are the same as the conditions mentioned later like the prebaking process conditions in the (I-2) process in the manufacturing method of a microlens.

The conditions of the said 2nd heating process are the same as the conditions mentioned later like the post-baking process conditions in the (IV-2) process in the manufacturing method of a microlens.

<Microlens>

The composition or curable composition of the present invention can form a transparent film having a high refractive index and a high transmittance, and can also be very preferably used for forming microlenses and microlens arrays, for example.

That is, the composition or curable composition of the present invention is preferably for forming a microlens.

The present invention also relates to a microlens formed using a transparent film formed using the composition or curable composition of the present invention.

[Formation method of microlens]

As a method for producing a microlens by using the composition or the curable composition of the present invention, a method commonly used may be applied without particular limitation, and examples thereof include a post-baking treatment on the transparent film to form a transparent film. The manufacturing method further includes the process of making it, a dry etching process, etc. are contained.

The process of forming a transparent film by performing a post-baking process to the said transparent film is the same as the process demonstrated in detail like the (f) process.

The said dry etching process is the same as the process demonstrated in detail like the (g) process.

As a preferable embodiment of the method of manufacturing a microlens by using the curable composition of this invention, the example includes the manufacturing method containing the following (I-2) process-(IV-2) process at least.

(I-2) Process of forming the coating film of the curable composition of this invention on a board | substrate

(II-2) Process of irradiating at least part of the coating film with radiation

(III-2) Process of developing the coating film after irradiation

(IV-2) Process of heating the coating film after development

Hereinafter, these processes are demonstrated.

(I-2) process

In this process, it is preferable that the curable composition is applied as a liquid composition on the surface of the substrate, and a coating film is formed on the substrate by performing a prebaking process to remove the solvent.

Examples of the substrate include a glass substrate, a silicon wafer, a substrate having various metal layers formed on the surface, a substrate coated with an on-chip color filter for an image sensor, and the like.

The coating method is not particularly limited, and for example, a suitable method such as a spray method, a roll coating method, a spin coating method, a bar coating method and the like can be adopted.

The prebaking process conditions may be changed depending on the type and amount of each component, but usually for 30 seconds to 15 minutes at 60 ℃ ~ 120 ℃. The film thickness of the coating film formed is the value after a prebaking process, and it is preferable that they are 0.5 micrometer-20 micrometers.

(II-2) process

In this step, radiation is irradiated to at least a portion of the formed coating film.

When only a part of the coating film is irradiated with radiation, the radiation is irradiated through a mask having a predetermined pattern.

As the radiation to be irradiated, ultraviolet rays such as g-rays and i-rays, far ultraviolet rays such as KrF excimer lasers and ArF excimer lasers, X-rays such as synchrotron radiation, and charged particle radiation such as electron radiation can be used. Among them, ultraviolet rays are preferred.

Although it is preferable to select the said exposure amount according to structures, such as a curable composition, it is preferable that they are 50mJ / cm <2> -2,000mJ / cm <2>.

(III-2) process

In the present step, the coated film after the exposure is developed by a developer, preferably an alkaline developer, and a pattern of a predetermined shape is formed by removing the non-irradiated portion.

The alkaline developing solution, the developing method and the developing time are the same as the alkaline developing solution, the developing method and the developing time described above in the step (V-1) of the first invention.

(IV-2) Process

In this process, the coating film is cured by heating (post-baking process) the coating film after development by a heating apparatus such as a hot plate and an oven.

In the said post-baking process, heating temperature is 120 degreeC-250 degreeC normally, and 160 degreeC-230 degreeC is preferable. The heating time may vary depending on the heating method, but when heating is performed on a hot plate, the heating time is usually 5 minutes to 30 minutes, and when heating is performed in an oven, the heating time is usually 30 minutes to 90 minutes. .

In carrying out the post-baking step, a stepwise baking method including performing two or more heat treatments may be employed.

As another preferable embodiment of the method of manufacturing a microlens by using the curable composition of this invention, the example includes the formation method containing the following (a) process-(b) process at least.

(a) Process of forming coating film on board | substrates, such as a color filter by using curable composition of this invention

(b) the coating film is exposed by heating at least one of the above-described coating films to dry (or drying and curing) the coating film or by exposing the above-mentioned coating film with a light source (g-ray, i-ray, etc.) having an appropriate wavelength. Process of obtaining a high refractive index film (transparent film) by performing at least one of the processes to harden

(c) forming a resist coating film on the high refractive index film after heating;

(d) Process of exposing resist by using light source (g line | wire, i line | wire, etc.) which have a suitable wavelength

(e) developing the resist film by forming a resist pattern after exposure;

(f) a step of molding the resist into a lens type by heating after

(g) forming a high refractive index film into a lens type by removing a portion of the resist pattern and the high refractive index film by dry etching;

Hereinafter, these processes are demonstrated.

(a) process-

In this step, the curable composition of the present invention is applied onto a substrate such as a color filter to form a coating film.

Examples of the coating method include the same method as in the step (I-2).

(b) process-

In this process, a preferred embodiment of heating the coating film may include a two-stage heat treatment of a prebaking process and a postbaking process.

The prebaking process conditions may be changed depending on the type and amount of each component, but usually for 30 seconds to 15 minutes at 60 ℃ ~ 120 ℃. The film thickness of the coating film formed is a value after a prebaking process, and 0.5 micrometer-20 micrometers are preferable. The prebaking process may be omitted.

Subsequently, the coating film is cured by heating (post-baking process) the coating film using a heating device such as a hot plate and an oven. Usually, the post-baking process is for 30 seconds to 60 minutes at 120 ℃ to 300 ℃. On the other hand, the curing can be promoted by performing exposure before the post bake process.

When the above-mentioned coating film is exposed and cured by a light source (g-ray, i-ray, etc.) having an appropriate wavelength to be cured, the same kind of radiation as in the step (II-2) and the exposure amount can be applied to the radiation to be irradiated. have.

(c) process-

In this process, a resist coating film is formed on the high refractive index film. As the resist, a commercially available resist capable of forming a pattern by ordinary ultraviolet exposure can be used. The said prebaking process is performed at the process (a) about the said resist coating film.

(d) process-

In this process, the coating film is exposed to the pattern type by using a mask. The same kind of radiation and the exposure amount as in the step (II-2) can be applied to the irradiated radiation.

(e) process-

In this step, the resist coated film after the exposure is developed by a developer, preferably an alkaline developer, and a pattern of a predetermined shape is formed by removing the non-irradiated portion or the irradiated portion of the radiation.

Examples of the alkali developer include an alkali developer as in step (III-2).

Examples of the developing method include the same method as described above for the step (III-2).

The developing time is the same as described above in the step (III-2).

(f) process-

In this step, the post heating (post-baking step) is performed by a heating apparatus such as a hot plate and an oven so that the resist is molded into a lens type after the pattern is formed. Usually, the post-baking process conditions are for 30 seconds to 60 minutes at 120 ℃ to 300 ℃. In addition, a stepwise baking method may be employed that includes performing two or more heat treatments to form a lens type.

(g) process-

Dry etching can be performed by a well-known method (for example, Unexamined-Japanese-Patent No. 2010-204154).

In this way, the desired microlenses can be produced.

According to the manufacturing method of the microlenses of the present invention, high precision microlenses and microarrays having excellent characteristics (for example, high refractive index and high transmittance) can be simply formed with high yield.

The microlens of the present invention is formed of the composition or curable composition of the present invention, has an excellent balance in characteristics, and includes a liquid crystal display device for various office automation devices, liquid crystal TVs, mobile phones, projectors, and the like; It can be used very favorably for the image of optical on-chip color filters, such as a facsimile, an electronic copier, a solid-state image sensor, and an optical fiber connector.

<Solid State Imaging Device>

The solid-state imaging device of the present invention includes a microlens formed using the above-described composition or curable composition of the present invention.

The solid-state imaging device of the present invention includes a microlens having a high refractive index and a high transmittance, and thus can reduce noise and exhibit excellent color reproducibility.

The solid-state imaging device of the present invention is not particularly limited as long as the device has a configuration including a microlens formed by using the composition or the curable composition of the present invention and a configuration that functions as the solid-state imaging device. A light receiving element composed of a photodiode, a polysilicon constituting the light receiving region of a solid state imaging element (CCD image sensor, a CMOS image sensor, etc.) is disposed on a substrate, the configuration in which the microlens is included on a filter Etc. are included.

The method of manufacturing the solid-state imaging device of the present invention is not particularly limited, but as one preferred embodiment, the method is a red pixel, blue pixel, and green pixel for a solid-state imaging device having at least a photodiode, a light shielding film, and a device protective film. Forming a resist pattern formed by applying a composition to the substrate, applying the above-described composition or curable composition, heating, forming a resist pattern, performing a post-baking process, and forming a lens pattern; The process of performing dry etching is included.

The step of applying the composition or curable composition and heating is carried out to form a coating film on the substrate in the steps (a) and (b) of the method for manufacturing a microlens and the coating film by heating the coating film. It is performed by the same method as the process of drying.

The step of forming the resist pattern is carried out in the same manner as in the steps (d) and (e) of the method for manufacturing the microlenses described above.

The step of molding the resist pattern formed by performing the above-described post-baking process into a lens type shape is performed in the same manner as in the step (f) of the method for manufacturing a microlens described above.

The step of performing the dry etching is carried out in the same manner as in the step (g) of the method for producing a microlens described above.

Example

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to Examples. On the other hand, "part" and "%" are with respect to mass unless there is particular notice.

&Lt; Example 1-1 >

[Preparation of Titanium Dioxide Dispersion (Dispersion Composition)]

The mixed liquid having the following composition was subjected to dispersion treatment in the following manner to obtain a titanium dioxide dispersion liquid as a dispersion composition by using ULTRA APEX MILL manufactured by KOTOBUKI INDUSTRIES Co., Ltd. as a circulating dispersion device (bead mill).

Composition

Titanium dioxide (manufactured by ISHIHARA SANGYO KAISHA, LTD., TTO-51 (C-l): 150 parts

Resin of "Example Compound 3" (graft copolymer (B-1)): 40.5 parts

Propylene glycol monomethyl ether acetate: 462 parts

The graft chain of the resin of Exemplary Compound 3 has 253 atoms (excluding hydrogen atoms) and a weight average molecular weight of 30,000.

The dispersing device is operated under the following conditions.

Bead diameter: φ0.05 mm

Bead filling rate: 75% by volume

Peripheral Speed: 8m / sec

Pump supply amount: 10㎏ / hour

· Cooling water: Tap water

Internal volume of the bead mill annular passage: 0.15 l

Quantity of mixed solution for dispersion treatment: 0.44 kg

After the start of the dispersion, the average particle diameter was measured at 30 minute intervals (one pass time).

The average particle diameter decreased with dispersion time (passage number), but the change amount gradually decreased. When the dispersion time was increased by 30 minutes, the change in the primary particle diameter became 5 nm or less, and the dispersion was completed. On the other hand, the titanium dioxide particles in the dispersion had a primary particle diameter of 40 nm.

In addition, the primary particle diameter of the said titanium oxide in a present Example is the measurement using the dynamic light scattering method with respect to the dilution obtained by diluting the mixed liquid or dispersion containing titanium oxide by 80 times with propylene glycol monomethyl ether acetate. The value obtained by performing this is meant.

These measurements are available from NIKKISO Co., Ltd. It calculates as a number average particle diameter obtained by measuring using the agent MICROTRAC UPA-EX150.

[Preparation of Curable Composition]

The said titanium dioxide dispersion liquid (dispersion composition) obtained is used, and each component mixes with each other and has the following composition, and a curable composition is obtained.

Composition of Curable Composition

78.26 parts of the titanium dioxide dispersion (dispersion composition) prepared above.

4.Acrylate monomer (polymerizable compound, "KAYARAD DPHA" (made by NIPPON KAYAKU Co., Ltd.))

0.30 part of oxime system photoinitiator

(Polymerization Initiator, K-1 below)

2.18 parts of binder polymer (F-1)

(The following J-1: weight average molecular weight (Mw) and copolymerization ratio (molar ratio) are as follows.)

0.30 part of surfactant (G-1) MEGAFAC F-781 (manufactured by DIC Corporation)

Propylene glycol monomethyl ether acetate 14.60 parts

(Manufacture of a transparent film)

The curable composition obtained is coated with a 12 inch silicon wafer by spin coating, followed by heating at 100 ° C. for 2 minutes on a hot plate to obtain a coating film having a film thickness of 1.05 μm. The coating film was heated on a hot plate at 200 ° C. for 5 minutes to obtain a cured film (film thickness: 1.0 μm) as a transparent film.

[Measurement of Refractive Index and Light Transmittance of Transparent Film]

With respect to the obtained substrate, the refractive index of the transparent film with respect to light at a wavelength of 500 nm is J.A. Woollam JAPAN Co., Inc. It was measured by using the first polarization analysis method. The light transmittance of the transparent film is Otsuka Electronics Co., Ltd. It measured over the wavelength range of 400 nm-700 nm by using MCMC series.

The results are shown in Table 1-1 below. On the other hand, since the transmittance at 400 nm in the region of 400 nm to 700 nm is the lowest value, the transmittance at 400 nm has been described.

[Evaluation of Dispersion Stability]

The viscosity of the obtained titanium dioxide dispersion (dispersion composition) is TOKI SANGYO CO., LTD. Measured by the "RE-85L", the dispersion was then left under conditions of 45 ° C. for 3 days, and the viscosity was measured again to reevaluate the difference in viscosity before and after idle.

[Measurement of difference in film thickness between the center and the periphery of the wafer]

With respect to the wafer substrate having the transparent film formed on the obtained wafer substrate, the thickness of the transparent film at the center of the wafer and the thickness of the transparent film of the portion recessed at 3 cm in the direction of the center of the wafer from the periphery of the wafer The difference between was measured by Dekrak (manufactured by Veeco Instruments Inc.). Table 1-1 shows the numerical results.

<Example 1-2-Example 1-27, Reference Example 1-1-Reference Example 1-4, and Comparative Example 1-1 and Comparative Example 1-2>

The curable compositions in Examples 1-2 to 1-22, Reference Examples 1-1 to Reference Examples 1-4, and Comparative Examples 1-1 and Comparative Examples 1-2 are titanium based on the total solid content of the curable composition. It was prepared according to Example 1-1 except that the content of oxide and the kind of the graft copolymer and the polymerization initiator were changed as shown in Table 1-1 below.

That is, in an embodiment in which the graft copolymer is changed from the exemplary compound used in Example 1-1, the titanium dioxide dispersion obtained by using the graft copolymer shown in Table 1-1 instead of the exemplary compound 3 It was used for the preparation of the titanium dioxide dispersion liquid used in Example 1-1. In addition, "the number of atoms of the said graft chain" shown in Table 1-1 means the number of atoms other than a hydrogen atom.

In the Examples where the polymerization initiator was changed from the compound K-1 used in Example 1-1, the polymerization initiator shown in Table 1-1 instead of the compound K-1 produced the curable composition in Example 1-1. Was used to. In addition, manufacture was performed separately about Example 1-2, Example 1-3, Reference Example 1-1, and Reference Example 1-2 as follows.

Examples 1-2

The titanium dioxide dispersion liquid (dispersion composition) obtained above was used, and the curable composition was obtained by mixing each component and having the following compositions.

Composition of Curable Composition

65.22 parts of the titanium dioxide dispersion (dispersion composition) prepared above.

4.Acrylate monomer (polymerizable compound, "KAYARAD DPHA" (made by NIPPON KAYAKU Co., Ltd.))

0.30 part of oxime system photoinitiator

(Polymerization Initiator, K-1)

5.99 parts of binder polymer (F-1)

(J-1; weight average molecular weight (Mw) and copolymerization ratio (molar ratio) are the same as described above)

Surfactant (G-1) MEGAFAC F-781 0.30 parts

Propylene glycol monomethyl ether acetate 23.83 parts

Reference Example 1-1

The titanium dioxide dispersion liquid (dispersion composition) obtained above was used, and the curable composition was obtained by mixing each component and having the following compositions.

Composition of Curable Composition

63.91 parts of the prepared titanium dioxide dispersion (dispersion composition)

4.Acrylate monomer (polymerizable compound, "KAYARAD DPHA" (made by NIPPON KAYAKU Co., Ltd.))

0.30 part of oxime system photoinitiator

(Polymerization Initiator, K-1)

6.37 parts of binder polymer (F-1)

(J-1; weight average molecular weight (Mw) and copolymerization ratio (molar ratio) are the same as described above)

Surfactant (G-1) MEGAFAC F-781 0.30 parts

Propylene glycol monomethyl ether acetate 24.76 parts

Example 1-3

Titanium dioxide dispersions (titanium dioxide particles having a primary particle diameter of 40 nm) were prepared with the following composition in the same manner as described above.

Composition

Titanium dioxide (manufactured by ISHIHARA SANGYO KAISHA, LTD., TTO-51 (C-l)):

                                                                  150 parts

Resin of "Example Compound 3" (graft copolymer B-1): 12.0 parts

Propylene glycol monomethyl ether acetate: 490.5 parts

The titanium dioxide dispersion liquid (dispersion composition) obtained above was used, and the curable composition was obtained by mixing each component and having the following compositions.

Composition of Curable Composition

117.39 parts of the prepared titanium oxide dispersion (dispersion composition)

0.73 parts of acrylate monomer (polymerizable compound, "KAYARAD DPHA" (manufactured by NIPPON KAYAKU Co., Ltd.))

0.10 part of oxime system photoinitiator

(Polymerization Initiator, K-1)

0.01 part of surfactant (G-1) MEGAFAC F-781

10.0 parts of propylene glycol monomethyl ether acetate

Reference Example 1-2

Composition of Curable Composition

Titanium dioxide dispersion (dispersion composition) described in Example 1-3

                                                               Part 118.69

0.44 parts of acrylate monomer (polymerizable compound, "KAYARAD DPHA" (manufactured by NIPPON KAYAKU Co., Ltd.))

0.08 part of oxime system photoinitiator

(Polymerization Initiator, K-1)

0.01 part of surfactant (G-1) MEGAFAC F-781

10.0 parts of propylene glycol monomethyl ether acetate

After using the obtained curable composition in the same manner as in Example 1-1 to prepare a transparent film, respectively, it was measured in the same manner as in Example 1-1. The results are shown in Table 1-1.

(Table 1-1)

From Table 1-1, it can be seen that the curable composition of the present invention has a slight difference in film thickness between the central portion and the peripheral portion of the wafer. It can be confirmed that the transparent film formed using the curable composition of the present invention has a high refractive index.

Although the above embodiment describes an embodiment in which a transparent film is formed on silicon, in the case of manufacturing a solid-state imaging device, the silicon wafer is a substrate for a solid-state imaging device together with a photodiode, a light shielding film, a device protective film, and the like formed thereon. Can only be changed.

The light blocking film formed of tungsten is formed on the silicon wafer together with the photodiode and the transition electrode formed thereon so that only the light receiving portion of the photodiode is opened, and the entire surface of the formed light blocking film and the photodiode light receiving portion (opening of the light blocking film) are coated. A device protective layer formed of silicon nitride was formed as possible.

Subsequently, the curable composition prepared as the undercoat layer as described above in the above example was applied to have a film thickness of 0.50 탆 on the device protective layer to be formed, and then heated with a hot plate at 100 ° C. for 2 minutes. Subsequently, the film was heated and cured at 230 ° C. for 10 minutes by using a hot plate. On top of that, red pixels, blue pixels and green pixels each having a length of 1.4 mu m were formed by the method described in Example 16 of Japanese Patent Application Laid-Open No. 2010-210702 to produce a color filter.

Thereon, the curable composition prepared as described above in the above example was applied to have a film thickness of 1.5 μm, heated at 100 ° C. for 2 minutes by using a hot plate, and then 10 at 230 ° C. by using a hot plate. The film was cured by heating for minutes.

HPR-204ESZ-9-5 mPa · s (resist liquid made from FUJIFILM Electronic Materials Co., Ltd.) was applied thereon, and then heated at 90 ° C. for 1 minute by using a hot plate. The coating film was exposed at 100 mJ / cm 2 by an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) through a mask having a plurality of square patterns having a length of 1.4 µm. Here, the mask is arranged such that the plurality of rectangular patterns of the mask have positions corresponding to the red pixels, the blue pixels, and the green pixels of the color filter, respectively. The film was subjected to puddle development using alkaline developer HPRD-429E (manufactured by FUJIFILM Electronic Materials Co., Ltd.) for 60 seconds at room temperature, and then washed with pure water for 20 seconds by spin shower. The film was then further washed with pure water, and the substrate was dried at high speed to form a resist film. The film was subjected to a post bake treatment at 200 ° C. for 300 seconds on a hot plate to form a resist in a lens type shape.

The substrate thus obtained was subjected to dry etching by using a dry etching apparatus (manufactured by Hitachi High-Technologies Corporation: U-621) under the following conditions, and a high refractive index transparent film having a high refractive index of the present invention was treated as a microlens. Was used.

RF power: 800W

Antenna bias: 100 W

Wafer bias: 500 W

Chamber internal pressure: 0.5Pa

· Substrate temperature: 50 ° C

, The type and flow rate of the mixed _{gas: CF 4 / C 4 F 6} /0 2 / Ar = 175/25/50 / 200㎖ / min

Photoresist etching rate: 140 nm / min

When the obtained device is used to photograph an image, an image having excellent sensitivity can be obtained even in a dark room.

<Manufacture example 2-1>

[Production of Titanium Dioxide Dispersion Liquid 1 (Dispersion Composition)]

The mixed liquid having the following composition was used as a circulating dispersion device (bead mill) by KOTOBUKI INDUSTRIES Co., Ltd. in the following manner. Dispersion was performed by using the ULTRA APEX MILL (brand name) of the first agent to obtain titanium dioxide dispersion 1 as a dispersion composition.

Composition

Titanium dioxide (ISHIHARA SANGYO KAISHA, LDT., Trade Name: TTO-51 (C-2)):

                                                                  180 parts

Resin of the "Example Compound 33" (dispersion resin (B-2)): 48.6 parts

Propylene glycol monomethyl ether acetate (PGMEA) 300 parts

The resin of Exemplary Compound 33 has a weight average molecular weight of 38,000.

The dispersing device is operated under the following conditions.

Bead diameter: φ0.05 mm

Bead filling rate: 75% by volume

Peripheral Speed: 8m / sec

Pump supply amount: 10㎏ / hour

· Cooling water: Tap water

Internal volume of the bead mill annular passage: 0.15 l

Quantity of mixed solution for dispersion treatment: 0.44 kg

After the start of the dispersion, the average particle diameter was measured at 30 minute intervals (one pass time).

The average particle diameter decreased with dispersion time (passage number), but the change amount gradually decreased. When the dispersion time was increased by 30 minutes, the change in the primary particle diameter became 5 nm or less, and the dispersion was completed. On the other hand, the titanium oxide particles in the dispersion had a primary particle diameter of 40 nm.

On the other hand, the primary particle diameter of the titanium dioxide in the present Example was measured by the dynamic light scattering method for the dilution obtained by diluting the mixed solution or dispersion containing titanium oxide up to 80 times with propylene glycol monomethyl ether acetate. It means the value obtained by performing.

These measurements are available from NIKKISO Co., Ltd. It calculates as a number average particle diameter obtained by measuring using the agent MICROTRAC UPA-EX150.

<Manufacture example 2-2>

[Preparation of Zirconium Oxide Dispersion (Dispersion Composition)]

An aqueous solution of zirconium oxychloride at a concentration of 50 g / l was neutralized with an aqueous 48 mass% sodium hydroxide solution to obtain a hydrated zirconium liquid suspension. The dispersion was filtered and then washed with ion exchanged water to obtain a hydrated zirconium cake. The cake was controlled to a concentration of 15% relative to zirconium oxide with ion-exchanged water as a solvent, put into an autoclave and subjected to hydrothermal treatment for 24 hours at a pressure of 150 atm at 150 ° C. to prepare a zirconium oxide fine particle suspension. The fine particles (average particle diameter 5 nm) of zirconium oxide were obtained by drying and removing water.

The zirconium oxide dispersion was prepared in the same manner except that the titanium dioxide of the titanium dioxide dispersion prepared in Preparation Example 2-1 was changed to the zirconium oxide. The primary particle diameter of the zirconium oxide particles of the zirconium oxide dispersion liquid obtained in the same manner as in Preparation Example 2-1 was 10 nm.

<Manufacture example 2-3>

[Preparation of Titanium Dioxide Dispersion 2 (Dispersion Composition)]

The mixed liquid having the following composition was circulated as a circulating dispersion device (bead mill) by KOTOBUKI INDUSTRIES Co., Ltd. The dispersion process was performed by using the ULTRA APEX MILL (brand name) of the agent, to obtain a titanium dioxide dispersion 2 as a dispersion composition.

Composition

Titanium dioxide (ISHIHARA SANGYO KAISHA, LDT., Trade Name: TTO-51 (C-2)):

                                                                  180 parts

The following dispersion resin (dispersion resin (B-2)): 48.6 parts

Propylene glycol monomethyl ether acetate (PGMEA) 300 parts

The dispersion apparatus was operated under the same conditions as in Preparation Example 2-1. The primary particle diameter of the titanium dioxide particles of the obtained titanium dioxide dispersion 2 was measured in the same manner as in Production Example 2-1, and was 40 nm.

<Example 2-1>

[Preparation of composition]

The obtained titanium dioxide dispersion liquid 1 (dispersion composition) was used, and each component was mixed with each other so that it might have the following composition, and the composition (curable composition) was obtained.

Composition of Curable Composition

52.86 parts of the prepared titanium dioxide dispersion 1 (dispersion composition)

Binder polymer (J-1) 3.27 parts

(J-1; weight average molecular weight (Mw) and copolymerization ratio (molar ratio) are the same as described above)

0.30 part surfactant (G-1)

(MEGAFAC F-781 Fluorine-based Surfactant (manufactured by DIC Corporation)

4.36 parts of dipentaerythritol hexaacrylate

(Polymerizable Compound, T-1 below)

0.30 part of oxime polymerization initiator

(Photoinitiator, IRGACURE OXE-Ol (K-l below) manufactured by BASF Corporation

Propylene glycol monomethyl ether acetate (PGMEA) 40.0 parts

(Manufacture of a transparent film)

The curable composition thus obtained was applied onto a 12 inch silicon wafer by spin coating, and then heated on a hot plate at 100 ° C. for 2 hours to obtain a coating film having a film thickness of 1.05 μm. The coating film was heated on a hot plate at 200 ° C. for 5 minutes to obtain a cured film (film thickness: 1.0 μm) as a transparent film.

[Measurement of Refractive Index and Light Transmittance of Transparent Film]

With respect to the obtained substrate, the refractive index of the transparent film with respect to light at a wavelength of 500 nm is J.A. Woollam JAPAN Co., Inc. It was measured by using the first polarization analysis method. The light transmittance of the transparent film is Otsuka Electronics Co., Ltd. It measured over the wavelength range of 400 nm-700 nm by using MCMC series.

The results of the refractive index of the transparent film are shown in Table 2-1. On the other hand, the light transmittance of the transparent film was measured at a wavelength of 400nm ~ 700nm, immediately after coating showed a light transmittance of 92% or more in any of the measurement range immediately.

[Evaluation of Shape of Coating Surface with Time after Application]

After leaving the sample on which the above-mentioned curable composition was apply | coated for 24 hours at room temperature, transparency was visually confirmed and the range of 5-1 was evaluated. The results are shown in Table 2-1 below.

5: no problem with transparency

4: There is a slight change in transparency at the periphery but no change at the center

3: slight change on periphery and central part is perceived, but practically no problem

2: uneven part on periphery and central part is perceived to be unsatisfactory problem

1: Clearly unacceptable level due to uneven parts on the entire surface

[Evaluation of Refractive Index of Transparent Film After Developing Treatment of Etching Resist]

As a transparent film formed as described above, a positive type photoresist "FHi622BC" (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied by spin coating on a cured film, and subjected to heat treatment at 100 ° C for 1 minute. The photoresist layer was formed to have a film thickness of 0.8 μm. Subsequently, the layer was entirely exposed in an amount of 300 mJ / cm 2 by using an i-ray stepper (FPA-3000i5 manufactured by Canon Inc.), heat-treated at 110 ° C. for 1 minute, and the developer FHD-5 (FUJIFILM Developed by Electronic Materials Co., Ltd. for 1 minute to peel off all of the photoresist layer on the transparent film (cured film). The refractive index of the transparent film (cured film) after the said process was measured in accordance with the method mentioned above.

The results are shown in Table 2-1 together with the values of the change in the refractive index after development obtained from [Refractive index after development treatment]-[Refractive index before development treatment].

<Example 2-2-Example 2-43, Comparative Example 2-1-Comparative Example 2-9>

In the curable composition in Examples 2-2 to Example 2-43 and Comparative Examples 2-1 to Comparative Example 2-9, the type of dispersion liquid, the kind of binder polymer, the kind of surfactant, and the curable composition of the curable composition It was prepared according to Example 2-1 except that the content of the surfactant to the total solid content was changed as shown in Table 2-1, and the results are shown in Table 2-1. In this case, when the content of the surfactant is changed, the content is increased according to the increase and decrease of the amount of the surfactant and at the same time increase or decrease the amount of the surfactant to maintain the total solid content of the composition. It was altered by increasing and decreasing the addition amount of F-2) (ie, the concentration of the solid content was maintained continuously).

On the other hand, the light transmittance of these transparent films was measured at the wavelength of 400 nm-700 nm, and immediately after coating, the light transmittance of 92% or more appeared in any of the measurement ranges.

<Example 2-44 to Example 2-46>

[Preparation of composition]

The obtained titanium dioxide dispersion liquid 2 (dispersion composition) was used, and each component was mixed with each other so that it might have the following composition, and the composition (curable composition) of Example 2-44 was obtained.

Composition of Curable Composition

52.86 parts of the prepared titanium dioxide dispersion 2 (dispersion composition)

Binder polymer (J-5) 3.27 parts

(J-5; the weight average molecular weight (Mw) and the copolymerization ratio (molar ratio) are the same as described above)

0.30 part surfactant

(MEGAFAC F-781 Fluorine-based Surfactant (manufactured by DIC Corporation)

Epoxy compound 4.36 parts

(Polymeric compound, brand name: EHPE3150 (made by Daicel Corporation)

0.30 part of oxime polymerization initiator

(Photoinitiator, IRGACURE OXE-Ol manufactured by BASF Corporation (K-1 above)

Propylene glycol monomethyl ether acetate (PGMEA) 40.0 parts

0.001 part of p-methoxyphenol (polymerization initiator)

In the curable composition in Example 2-44, the curable composition in Example 2-45 and Example 2-46 has a surfactant content as shown in Table 2-1 with respect to the total solid content of the curable composition Prepared according to Example 2-44 except as changed. Here, when the content of the surfactant is changed, the content is increased according to the increase and decrease of the amount of the surfactant to increase and decrease the amount of the surfactant and simultaneously maintain the total solid content of the composition. It was changed by increasing and decreasing the amount of -2) added (ie, the concentration of the solid content was kept constant). Curable compositions in Examples 2-44 to Example 2-46 were evaluated according to Example 2-1, and the results are shown in Table 2-1.

Meanwhile, the light transmittance of the transparent film was measured at a wavelength of 400 nm to 700 nm, and immediately after coating, light transmittance of 92% or more appeared in any of the measurement ranges.

Meanwhile, the expression "TiO ₂ -1" in the paragraph of the metal oxide particles (A-2) means that the titanium dioxide dispersion liquid 1 controlled in Preparation Example 2-1 was used as the dispersion composition, and the expression "ZrO ₂ "Means that the zirconium oxide dispersion controlled in Preparation Example 2-2 was used as the dispersion composition, and the expression" TiO ₂ -2 "was used as the titanium dioxide dispersion divalent dispersion composition controlled in Preparation Example 2-3. It means.

In the paragraph of the binder polymer (F-2), J-2 to J-6 are binder polymers having the above-described structure, weight average molecular weight (Mw) and copolymerization ratio (molar ratio).

"Surfynol 465" in the paragraph of the surfactant (G-2) means Surfynol 465 (nonionic surfactant, Nissin Chemical Industry Co., Ltd.), "KF-6001" KF-6001 (Shin-Etsu Silicon-based surfactant made by Silicone Co., Ltd.).

J-7 of the binder polymer used in Comparative Example 2-9 has a structure described below, a weight average molecular weight (Mw) and a polymerization ratio (molar ratio), and does not contain a repeating unit derived from benzyl (meth) acrylate. Comparative binder polymer.

Table 2-1

From Table 2-1, the film formed using the composition of the present invention has a small change in the shape of the coated surface with time after the coating of the composition, and a small drop in the refractive index after the development treatment. The transparent film formed using the composition (curable composition) of this invention has a high refractive index.

Embodiments in which a transparent film is formed on silicon are described in the above embodiments, but in the case of manufacturing a solid-state imaging device, the silicon wafer is subjected to solid-state imaging with a photodiode, a light shielding film, a device protective film, etc. formed thereon. It can be changed only to the substrate for the device.

The light blocking film formed of tungsten is formed on the silicon wafer together with the photodiode and the transition electrode formed thereon so that only the light receiving portion of the photodiode is opened, and the entire surface of the formed light blocking film and the photodiode light receiving portion (opening of the light blocking film) are coated. A device protective layer formed of silicon nitride was formed as possible.

Subsequently, red pixels, blue pixels and green pixels each having a length of 1.4 mu m were formed by the method described in Example 16 of Japanese Patent Application Laid-open No. 2010-210702 to produce a color filter.

Thereon, the curable composition controlled as described above in the above example was applied to have a film thickness of 1.5 μm, heated at 100 ° C. for 2 minutes by using a hot plate, and then 5 at 230 ° C. by using a hot plate. The film was cured by heating for minutes.

HPR-204ESZ-9-5 mPa · s (resist liquid manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied thereon, and then heated at 90 ° C. for 1 minute by using a hot plate. The coating film was exposed at 100 mJ / cm 2 by an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) through a mask having a plurality of square patterns having a length of 1.4 µm. Here, the mask is arranged such that the plurality of rectangular patterns of the mask have positions corresponding to the red pixels, the blue pixels, and the green pixels of the color filter, respectively.

The film was subjected to puddle development using alkaline developer HPRD-429E (manufactured by FUJIFILM Electronic Materials Co., Ltd.) for 60 seconds at room temperature, and then washed with pure water for 20 seconds by spin shower. The film was then further washed with pure water, and the substrate was dried at high speed to form a resist film. The film was subjected to a post bake treatment at 200 ° C. for 300 seconds on a hot plate to form a resist in a lens type shape.

The substrate thus obtained was subjected to a dry etching process by using a dry etching apparatus (manufactured by Hitachi High-Technologies Corporation: U-621) under the following conditions, and a transparent film having a high refractive index of the present invention was treated to be used as a microlens. .

RF power: 800W

Antenna bias: 100 W

Wafer bias: 500 W

Chamber internal pressure: 0.5Pa

· Substrate temperature: 50 ° C

, The type and flow rate of the mixed _{gas: CF 4 / C 4 F 6} /0 2 / Ar = 175/25/50 / 200㎖ / min

Photoresist etching rate: 140 nm / min

When the obtained device is used to photograph an image, an image having excellent sensitivity can be obtained even in a dark room.

(Industrial applicability)

According to the present invention (first invention), even when the composition is applied on a large size wafer, when produced as a curable composition capable of forming a film having a slight difference in film thickness between the central portion and the peripheral portion It is possible to provide dispersion compositions and curable compositions having excellent dispersion stability and very high refractive index, transparent films, microlenses and solid-state imaging devices using the same.

According to the present invention (second invention), it has a high refractive index capable of forming a film having a slight drop in the refractive index after the development treatment, and also has a slight change in the shape of the coated surface with time after the application of the composition. It is possible to provide a composition having a composition, a transparent film, a microlens, a solid-state imaging device, a manufacturing method of a transparent film, a manufacturing method of a microlens and a manufacturing method of a solid-state imaging device using the same.

This specification is Japanese Patent Application No. JP 2011-103877, filed May 6, 2011, Japanese Patent Application No. JP 2011-111734, filed May 18, 2011, filed August 31, 2011. Based on Japanese Patent Application No. JP 2011-190180 and Japanese Patent Application No. JP 2011-251118 filed on November 16, 2011, the entire contents of the present application are incorporated by reference as specifically stated.

Claims (30)

Metal oxide particles (A-1) having a primary particle diameter of 1 nm to 100 nm;
Graft copolymer (B-1) which has the graft chain of 40-10,000 atoms of graft chains other than a hydrogen atom; And
As a dispersion composition containing a solvent (C-1),
The content of the metal oxide particles (A-1) is 50% by mass to 90% by mass relative to the total solids content of the dispersion composition,
The graft copolymer (B-1) has a structural unit having an acid group in an amount of 25% by mass to 90% by mass relative to the total mass of the graft copolymer (B-1). The method of claim 1,
The graft copolymer (B-1) has a dispersing composition, characterized in that it has an acid value of 70 mgKOH / g ~ 350 mgKOH / g. 3. The method according to claim 1 or 2,
The graft chain of the graft copolymer (B-1) is at least one structure selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylic structure. The method according to any one of claims 1 to 3,
The graft copolymer (B-1) is a graft copolymer containing a structural unit represented by at least one of the following general formulas (1) to (4).

[In General Formula (1)-(4), X <^1> , X <^2> , X <^3> , X <^4> and X <^5> represent a hydrogen atom or a monovalent organic group each independently;
W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH;
R represents a hydrogen atom or a monovalent organic group, and R having another structure may exist in the copolymer;
R 'represents a branched alkylene group or a straight chain alkylene group, and R' having another structure may be present in the copolymer;
Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group;
Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a hydrogen atom or a monovalent substituent;
j and k each independently represent an integer of 2 to 8;
n, m, p and q each independently represent an integer of 1 to 500.] The method according to any one of claims 1 to 4,
The graft copolymer (B-1) is a graft copolymer containing a structural unit having a graft chain in the range of 10% by mass to 75% by mass relative to the total mass of the graft copolymer (B-1). Dispersion composition characterized by. 6. The method according to any one of claims 1 to 5,
The acid group of the structural unit having an acid group is at least one group selected from the group consisting of a carboxylic acid group, a sulfonic acid group and a phosphoric acid group. As a curable composition containing the dispersion composition as described in any one of Claims 1-6,
The said dispersion composition contains a polymeric compound (D-1) and a polymerization initiator (E-1) further, The curable composition characterized by the above-mentioned. The method of claim 7, wherein
Curable composition further containing binder polymer (F-1). 9. The method according to claim 7 or 8,
The said polymerization initiator (E-1) is an oxime system photoinitiator, The curable composition characterized by the above-mentioned. 10. The method according to any one of claims 7 to 9,
A curable composition, which is used to form a microlens. 10. The method according to any one of claims 7 to 9,
A curable composition, which is used to form an undercoat film of a color filter. It is formed using the curable composition in any one of Claims 7-11, The transparent film characterized by the above-mentioned. It is formed using the transparent film obtained by the curable composition of Claim 10, The microlens characterized by the above-mentioned. The method of claim 13,
A microlens formed by dry etching the transparent film. A solid-state imaging device comprising at least one of the transparent film according to claim 12 and the microlenses according to claim 13 or 14. Titanium oxide particles or zirconium oxide particles as the metal oxide particles (A-2);
Binder polymer (F-2) containing a repeating unit derived from benzyl (meth) acrylate; And
As a composition containing surfactant (G-2),
The content of the surfactant (G-2) is 0.0010% by mass to 3.0% by mass relative to the total solids content of the composition. 17. The method of claim 16,
The surfactant (G-2) is a composition, characterized in that the fluorine-based surfactant or nonionic surfactant. 18. The method according to claim 16 or 17,
The content of the surfactant (G-2) is 0.50% by mass to 3.0% by mass based on the total solids content of the composition. 19. The method according to any one of claims 16 to 18,
A composition comprising titanium oxide particles as the metal oxide particles (A-2). 20. The method according to any one of claims 16 to 19,
The binder polymer (F-2) further comprises a repeating unit derived from (meth) acrylate. 21. The method according to any one of claims 16 to 20,
The binder polymer (F-2) has an ethylene oxide group. 22. The method according to any one of claims 16 to 21,
The binder polymer (F-2) further comprises both a repeating unit derived from an alkyl (meth) acrylate having an ethylene oxide group and a repeating unit derived from isobutyl (meth) acrylate. The method according to any one of claims 16 to 22,
Composition for use in forming microlenses. It is formed using the composition in any one of Claims 16-23, The transparent film characterized by the above-mentioned. It is formed using the transparent film of Claim 24, The microlens characterized by the above-mentioned. The method of claim 25,
A microlens formed by dry etching the transparent film. A solid-state imaging device comprising the microlens according to claim 25 or 26. The process of apply | coating the composition of any one of Claims 16-23 on a wafer; next,
A first heating step of heating the composition; next,
And a second heating step of heating the composition at a temperature higher than the heating temperature in the first heating step. A step of forming a transparent film by performing a post-baking treatment to the transparent film of claim 24; And
A method of manufacturing a microlens, comprising the step of dry etching the transparent film. Forming a red pixel, a blue pixel and a green pixel on a substrate for a solid-state imaging device having at least a photodiode, a light blocking film, and a device protective film;
Process of apply | coating the composition of any one of Claims 16-23, and heating;
Forming a resist pattern;
Molding the formed resist pattern into a lens type shape by performing a post bake treatment; And
A method of manufacturing a solid-state imaging device, comprising the step of performing dry etching.