JP5898887B2 - Composition, and transparent film, microlens, solid-state imaging device, method for manufacturing transparent film, method for manufacturing microlens, and method for manufacturing solid-state imaging device using the same - Google Patents

Description

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

High optical refractive index and fine transparent film and transparent wiring can be formed for use as an optical wiring alternative to micro lenses and copper wiring used in imaging optical systems for on-chip color filters such as electronic copying machines and solid-state image sensors. A transparent composition for forming a transparent member is desired.
In particular, microlenses used in solid-state imaging devices are required to be finer as solid-state imaging devices become more miniaturized, and higher refractive index is required to achieve more efficient light collection. It has become. For example, a high refractive index pattern-forming photopolymerizable composition using silica-coated titanium oxide particles has been disclosed (for example, see Patent Document 1). Further, a composition for a solid-state imaging device using a metal oxide in which the proportion of silicon atoms on the particle surface is 20% or more is disclosed, and it is shown that the pattern forming property is excellent with a high refractive index (for example, patents). Reference 2). Particularly in recent years, with the increase in the number of pixels, the size of one pixel is extremely small, and it has become essential to collect light more efficiently. For this reason, a micro lens having a higher refractive index is required. In addition, since a larger number of devices are produced in one manufacturing process, the wafer size used is also increased.
Further, as a composition for forming a transparent high refractive index film using titanium oxide particles, Example 3 of Patent Document 3 discloses a composition containing titanium oxide, a surfactant and a binder polymer.

JP 2009-179678 A JP 2008-185683 A JP-A-8-110401

However, the composition for forming a high refractive index material described in the patent document as described above has a large change with time in the coated surface state after application of the composition.For example, when the composition is applied for 24 hours at room temperature after application, There was a problem that uneven portions were generated on the film surface. It is presumed that the generation of such a non-uniform portion on the film surface is caused by aggregation due to poor compatibility between the metal oxide and the binder polymer.
In addition, the inventors have found that the following problems occur when a microlens is produced by etching using the composition for forming a high refractive index material described in the patent literature as described above. It was issued. That is, in order to form a microlens, a resist is applied on a high refractive material formed from the composition as described above, followed by pattern exposure and development. The surface on which the high refractive material in the lower layer appears) comes into contact with the developer and is affected by the developer, and the refractive index of the high refractive material is lowered. There is a problem that can not be.

  The present invention has been made in view of the above, and is a composition capable of forming a film having a high refractive index, a small change with time of the coated surface after application of the composition, and a small decrease in refractive index after development. It is another object of the present invention to provide a transparent film, a microlens, a solid-state imaging device, a transparent film manufacturing method, a microlens manufacturing method, and a solid-state imaging device manufacturing method using the same.

Specific means for solving the above problems are as follows.
[1]
Repeating units obtained by polymerizing titanium oxide particles or zirconium oxide particles as metal oxide particles (A), repeating units obtained by polymerizing benzyl (meth) acrylate, and alkyl (meth) acrylates containing ethylene oxide groups A composition containing a binder polymer (F) containing a unit and a repeating unit obtained by polymerizing isobutyl (meth) acrylate, and a surfactant (G), wherein the surfactant (G) is contained The composition whose quantity is 0.0010 mass%-3.0 mass% with respect to the total solid of the said composition.
[2]
Titanium oxide particles or zirconium oxide particles as metal oxide particles (A), a binder polymer (F) containing a repeating unit obtained by polymerizing benzyl (meth) acrylate, a surfactant (G) , p Dispersion resin which is a resin having a repeating unit having a group X having a functional group of Ka14 or less and an oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain and containing a basic nitrogen atom A composition containing (B), wherein the content of the surfactant (G) is 0.0010% by mass to 3.0% by mass with respect to the total solid content of the composition.
[ 3 ]
The composition according to [1] or [2], wherein the surfactant (G) is a fluorine-based surfactant or a nonionic surfactant.
[ 4 ]
Composition of any one of [1]-[ 3 ] whose content of the said surfactant (G) is 0.50 mass%-3.0 mass% with respect to the total solid of the said composition. object.
[ 5 ]
The composition according to any one of [1] to [ 4 ], which contains titanium oxide particles as the metal oxide particles (A).
[ 6 ]
The composition according to any one of [1] to [ 5 ], wherein the binder polymer (F) further contains a repeating unit obtained by polymerizing (meth) acrylate.
[ 7 ]
The composition according to [ 2], wherein the binder polymer (F) has an ethylene oxide group.
[ 8 ]
[ 2] The binder polymer (F) further contains both a repeating unit obtained by polymerizing an alkyl (meth) acrylate containing an ethylene oxide group and a repeating unit obtained by polymerizing isobutyl (meth) acrylate . The composition as described.
[ 9 ]
The composition according to any one of [1] to [ 8 ], which is used for forming a microlens.
[ 10 ]
A transparent film formed using the composition according to any one of [1] to [ 9 ].
[ 11 ]
The microlens formed using the transparent film as described in [ 10 ].
[ 12 ]
The microlens according to [ 11 ], which is formed by dry etching the transparent film.
[ 13 ]
A solid-state imaging device having the microlens according to [ 11 ] or [ 12 ].
[ 14 ]
[1] to [ 9 ] a step of coating the composition according to any one of [ 9 ] on a wafer;
A transparent film manufacturing method comprising: a subsequent first heating step; and a second heating step at a temperature higher than the heating temperature in the first heating step.
[ 15 ]
[ 10 ] A method for producing a microlens, comprising a step of post-baking and shaping the transparent film according to [ 10 ], and further a dry etching step.
[ 16 ]
Forming a red pixel, a blue pixel, and a green pixel on a solid-state imaging device substrate having at least a photodiode, a light shielding film, and a device protection film;
A step of applying and heating the composition according to any one of [1] to [ 9 ];
Forming a resist pattern;
A process of post-baking and shaping the formed resist pattern into a lens shape, and a dry etching process;
A method for manufacturing a solid-state imaging device.
The present invention relates to the above [1] to [1 6 ], but other matters (for example, the matters described in <1> to <15> below) are also described for reference.

<1>
Composition containing titanium oxide particles or zirconium oxide particles as metal oxide particles (A), a binder polymer (F) containing a repeating unit derived from benzyl (meth) acrylate, and a surfactant (G) It is a thing, Comprising: Content of the said surfactant (G) is 0.0010 mass%-3.0 mass% with respect to the total solid of the said composition.
<2>
The composition according to <1>, wherein the surfactant (G) is a fluorosurfactant or a nonionic surfactant.
<3>
The composition according to <1> or <2>, wherein the content of the surfactant (G) is 0.50% by mass to 3.0% by mass with respect to the total solid content of the composition.
<4>
The composition according to any one of the above items <1> to <3>, which contains titanium oxide particles as the metal oxide particles (A).
<5>
The composition according to any one of <1> to <4>, wherein the binder polymer (F) further contains a repeating unit derived from (meth) acrylate.
<6>
The composition according to any one of <1> to <5>, wherein the binder polymer (F) has an ethylene oxide group.
<7>
<1> to <6> above, wherein the binder polymer (F) further contains both a repeating unit derived from an alkyl (meth) acrylate containing an ethylene oxide group and a repeating unit derived from isobutyl (meth) acrylate. The composition of any one of these.
<8>
The composition according to any one of <1> to <7>, which is used for forming a microlens.
<9>
The transparent film formed using the composition of any one of said <1>-<8>.
<10>
A microlens formed using the transparent film according to <9>.
<11>
The microlens according to <10>, which is formed by dry etching the transparent film.
<12>
A solid-state imaging device having the microlens according to <10> or <11>.
<13>
Applying the composition according to any one of <1> to <8> above onto a wafer;
A transparent film manufacturing method comprising: a subsequent first heating step; and a second heating step at a temperature higher than the heating temperature in the first heating step.
<14>
A method for producing a microlens, comprising a step of post-baking and shaping the transparent film according to <9>, and a dry etching step.
<15>
Forming a red pixel, a blue pixel, and a green pixel on a solid-state imaging device substrate having at least a photodiode, a light shielding film, and a device protection film;
Applying and heating the composition according to any one of <1> to <8> above,
Forming a resist pattern;
A process of post-baking and shaping the formed resist pattern into a lens shape, and a dry etching process;
A method for manufacturing a solid-state imaging device.

If a specific amount of surfactant is not present in the composition of the present invention, the compatibility between the metal oxide particles and the binder polymer, which will be in close contact with the solvent after drying after coating, becomes unstable, Over time, the metal oxide particles are aggregated and the surface condition is deteriorated. However, a certain amount of surfactant is introduced between the metal oxide particles and the binder polymer, so that the compatibility is improved, and as a result, the coating surface shape change after application of the composition changes over time. Is estimated to be small.
Further, when a microlens is produced by etching using the composition of the present invention, a resist is applied on the high refractive material formed from the composition of the present invention, and pattern development and development are performed. Even when the surface from which the resist has been removed by the liquid (that is, the surface on which the high refractive material in the lower layer appears) is in contact with the developer, when a specific amount of the surfactant is not present in the composition of the present invention, As described above, the metal oxide particles and the binder polymer alone produce uneven portions on the surface, and the developer enters the gaps, resulting in a decrease in the refractive index. When the agent is present, the surface active agent enters the surface to prevent potential unevenness of the surface. As a result, the developer is prevented from entering, thereby reducing the refractive index. It is presumed that the film is small is provided.
That is, by using the composition of the present invention, it is possible to obtain a film having a high refractive index, a small change with time of the coated surface after application of the composition, and a small decrease in refractive index after development processing. it can.

  According to the present invention, there is provided a composition capable of forming a film having a high refractive index, a small change with time in the coated surface state after application of the composition, and a small decrease in refractive index after development, and the use thereof. A transparent film, a microlens, and a solid-state imaging device.

Hereinafter, the composition of the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acrylic and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a 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 refers to a group that participates in a polymerization reaction.
In this specification, “refractive index” refers to a refractive index with respect to light having a wavelength of 500 nm unless otherwise specified.

<Composition>
The composition of the present invention comprises titanium oxide particles or zirconium oxide particles as metal oxide particles (A), a binder polymer (F) containing a repeating unit derived from benzyl (meth) acrylate, a surfactant ( G), and the content of the surfactant (G) is 0.0010% by mass to 3.0% by mass with respect to the total solid content of the composition.
In the composition of the present invention, the titanium oxide particles or the zirconium oxide particles as the metal oxide particles (A) are preferably dispersed in the composition, and are contained in the composition as a dispersion composition described below. More preferably, it is dispersed.

<Dispersion composition>
The dispersion composition preferably contained in the composition of the present invention is a dispersion composition containing titanium oxide particles or zirconium oxide particles as metal oxide particles (A), a dispersion resin (B), and a solvent (C). It is a thing.

(A) Titanium oxide particles or zirconium oxide particles as metal oxide particles At least titanium oxide particles or zirconium oxide particles are used as the metal oxide particles (A) in the present invention. Titanium oxide particles and zirconium oxide particles are inorganic particles having a high refractive index. The titanium oxide particles include titanium dioxide (TiO ₂ ) particles, and the zirconium oxide particles include zirconium dioxide (ZrO ₂ ) particles. The composition of the present invention preferably contains at least titanium oxide particles as the metal oxide particles (A) because a higher refractive index is obtained. Among them, titanium dioxide particles (hereinafter simply referred to as “titanium dioxide”). More preferably).
The primary particle diameter of the titanium oxide particles and zirconium oxide particles in the present invention is preferably 1 nm to 100 nm. For example, they can be appropriately selected from commercially available titanium oxide particles and zirconium oxide particles.
The primary particle size of the titanium oxide particles and zirconium oxide particles is preferably 1 nm to 100 nm, more preferably 1 nm to 80 nm, and particularly preferably 1 nm to 50 nm. It is preferable that the primary particle diameter of the titanium oxide particles and the zirconium oxide particles is 100 nm or less because a decrease in refractive index and transmittance is suppressed. Moreover, since it is 1 nm or more, since the fall of the dispersibility and dispersion stability by aggregation is suppressed, it is preferable.
Moreover, in this invention, the primary particle diameter of a titanium oxide particle and a zirconium oxide particle is obtained as an average particle diameter of a titanium oxide particle and a zirconium oxide particle. The average particle diameter of the titanium oxide particles and zirconium oxide particles in the present invention is obtained by diluting a mixed solution or dispersion containing titanium oxide particles and / or zirconium oxide particles 80 times with propylene glycol monomethyl ether acetate. It means the value obtained by measuring the liquid using the dynamic light scattering method.
This measurement is the number average particle diameter obtained by using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd.

In the present invention, the refractive indexes of the titanium oxide particles and the zirconium oxide particles are not particularly limited, but are preferably 1.75 to 2.70 from the viewpoint of obtaining a high refractive index, and are 1.90 to 2.70. More preferably it is.
The specific surface area of the titanium oxide particles and the zirconium oxide particles is preferably 10 m ² / g to 400 m ² / g, more preferably 20 m ² / g to 200 m ² / g, and 30 m ² / g to 150 m. Most preferably, it is ² / g.
Moreover, there is no restriction | limiting in particular in the shape of a titanium oxide particle and a zirconium oxide particle. For example, it can be a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape.

The titanium oxide particles and zirconium oxide particles in the present invention may be those that have been 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. Of these, silane coupling agents are preferred.
The surface treatment may be carried out by using a single surface treatment agent or a combination of two or more surface treatment agents.
It is also preferable that the surfaces of the titanium oxide particles and the zirconium oxide particles are covered with an oxide such as aluminum, silicon, or zirconia. Thereby, a weather resistance improves more.

As a titanium oxide particle and a zirconium oxide particle in this invention, what is marketed can be used preferably.
Examples of commercially available titanium dioxide particles include TTO series (TTO-51 (A), TTO-51 (C), etc.), TTO-S, and V series (TTO-S-1, TTO-) manufactured by Ishihara Sangyo Co., Ltd. S-2, TTO-V-3, etc.), MT series (MT-01, MT-05, etc.) manufactured by Teika Corporation.
Examples of commercially available zirconium dioxide particles include UEP (Daiichi Rare Element Chemical Co., Ltd.), PCS (Nippon Denko Co., Ltd.), JS-01, JS-03, JS-04 (Nippon Denko ( Co., Ltd.), UEP-100 (Daiichi Rare Element Chemical Co., Ltd.) and the like.

In the present invention, the metal oxide particles (A) may be used alone or in combination of two or more, but at least one is the above-mentioned titanium oxide particles or zirconium oxide particles.
As metal oxide particles (A), when two or more metal oxide particles are used in combination, the metal oxide particles 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. Although there is no particular limitation, inorganic particles having a high refractive index are preferable. Examples thereof include silicon oxide particles, and examples of silicon oxide particles include silicon dioxide (SiO ₂ ) particles. The primary particle diameter, refractive index, specific surface area, shape, and surface treatment of the silicon oxide particles are the same as the ranges described above for the titanium oxide particles and the zirconium oxide particles.
Commercially available silicon oxide particles can be used, and examples of commercially available silicon dioxide particles include OG502-31 manufactured by Clariant Co.
In the present invention, the titanium oxide particles or the zirconium oxide particles are preferably 30 to 100% by mass, more preferably 60 to 100% by mass, and more preferably 80 to 100% with respect to the total mass of the metal oxide particles (A). More preferably, it is 100% by mass (that is, the metal oxide particles (A) are composed of only titanium oxide particles or zirconium oxide particles).

When constituting the dispersion composition or the composition of the present invention, in order to obtain a very high refractive index, the content of the metal oxide particles (A) in the composition is the total amount of the dispersion composition or the composition of the present invention. It is preferable that it is 10-90 mass% with respect to solid content, It is more preferable that it is 10-50 mass%, More preferably, it is 12-40 mass%, Most preferably, it is 15-35 mass%.
On the other hand, particularly for a high refractive index microlens, it is preferably 50 to 90 mass%, preferably 52 to 85 mass%, based on the total solid content of the dispersion composition or the composition of the present invention. More preferred is 55 to 80% by mass.

(B) Dispersion resin The dispersion composition preferably contained in the composition of the present invention contains a dispersion resin. The dispersion resin is not particularly limited as long as the metal oxide particles (A) are dispersed, but a copolymer having a graft chain is preferable, and a graft copolymer (hereinafter referred to as “specific resin 1”) described below is preferable. More preferred). The graft copolymer has a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000. The graft chain in this case indicates from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain. In the dispersion composition, the specific resin 1 is a dispersion resin that imparts dispersibility to the metal oxide particles, and has an affinity for the solvent due to the graft chain. Excellent dispersion stability afterwards. Moreover, when it is set as a dispersion composition, it is thought that it is suppressed that the uniformity of the film thickness in a coating film deteriorates because a graft chain and a solvent show favorable interaction.

The graft copolymer as the dispersion resin (B) preferably used in the present invention has 40 to 10,000 atoms excluding hydrogen atoms per graft chain, but hydrogen atoms per graft chain. The number of atoms excluding is more preferably from 100 to 500, and the number of atoms excluding hydrogen atoms per graft chain is more preferably from 150 to 260.
When the number of atoms excluding hydrogen atoms per graft chain is 40 or more, the graft chain is long, so that the steric repulsion effect is increased and the dispersibility and dispersion stability are improved. On the other hand, when the number of atoms excluding hydrogen atoms per graft chain is 10,000 or less, the graft chain does not become too long, and the decrease in the adsorptive power to the metal oxide particles is suppressed. This is preferable because a decrease in dispersion stability is suppressed.
The number of atoms excluding hydrogen atoms per graft chain is included from the base atom bonded to the polymer chain constituting the main chain to the end of the branch polymer branched from the main chain. The number of atoms other than hydrogen atoms. When the graft copolymer contains two or more types of graft chains, it is sufficient that the number of atoms excluding hydrogen atoms of at least one type of graft chain satisfies the above 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, etc. can be used, but the interaction between the graft chain and the solvent is improved. In order to increase the dispersibility and dispersion stability thereby, a graft chain having a poly (meth) acrylic structure, a polyester structure and a polyether structure is preferable, and a polyester structure and a polyether structure are more preferable.

  The graft copolymer preferably has a structural unit having a graft chain (repeating unit), and can be obtained, for example, by polymerizing a macromonomer having a polymer structure as a graft chain based on a conventional method, The structure of such a macromonomer is not particularly limited as long as it has a substituent capable of reacting with the polymer main chain portion and has a graft chain that satisfies the requirements of the present invention. A macromonomer having a double bond group can be preferably used.

  Commercially available macromonomers suitably used for the synthesis of the specific resin 1 include AA-6 (manufactured by Toagosei), AA-10 (manufactured by Toagosei), AB-6 (manufactured by Toagosei), AS-6 ( Toagosei), AN-6 (Toagosei), AW-6 (Toagosei), AA-714 (Toagosei), AY-707 (Toagosei), AY-714 (Toagosei) Toagosei Co., Ltd.), AK-5 (Toagosei Co., Ltd.), AK-30 (Toagosei Co., Ltd.), AK-32 (Toagosei Co., Ltd.), Blemmer PP-100 (manufactured by NOF Corporation), Blemmer PP- 500 (manufactured by NOF Corporation), Blemmer PP-800 (manufactured by NOF Corporation), Blemmer PP-1000 (manufactured by NOF Corporation), Blemmer 55-PET-800 (manufactured by NOF Corporation), Blemmer PME-4000 (manufactured by NOF Corporation) ), Blemmer PSE-400 (manufactured by NOF Corporation), Blen By chromatography (manufactured by NOF Corporation) PSE-1300, Brenmer 43PAPE-600B (manufactured by NOF Corporation), and the like. Among these, Preferably, AA-6 (made by Toagosei), AA-10 (made by Toagosei), AB-6 (made by Toagosei), AS-6 (made by Toagosei), AN-6 ( Toagosei Co., Ltd.), Blemmer PME-400 (manufactured by NOF Corporation), Blemmer PME-100 (manufactured by NOF Corporation), Blemmer PME-200 (manufactured by NOF Corporation), Blemmer PME-1000 (manufactured by NOF Corporation), etc. Is mentioned.

  The specific resin 1 preferably includes at least a structural unit represented by any one of the following formulas (1) to (4) as the structural unit having the graft chain, and includes at least the following formula (1A) and the following formula More preferably, it includes a structural unit represented by any one of (2A), the following formula (3), and the following formula (4).

In the 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 synthesis restrictions, 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 formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH, and particularly preferably an oxygen atom.

In the formula (3), R ′ represents a branched or straight chain alkylene group (the number of carbon atoms is preferably 1-10, more preferably 2 or 3), and —CH ₂ from the viewpoint of dispersion stability. A group represented by —CH (CH ₃ ) — or a group represented by —CH (CH ₃ ) —CH ₂ — is preferred.
Moreover, as R ′ in the formula (3), two or more types of R ′ having different structures in the specific resin 1 may be mixed and used.

In Formula (1) to Formula (4), Y ¹ , Y ² , Y ³ , and Y ⁴ are each independently a divalent linking group and are not particularly limited in structure. Specific examples include the following (Y-1) to (Y-21) linking groups. In the following structures, A and B each represent a bond with the left terminal group and the right terminal group in formulas (1) to (4). Of the structures shown below, (Y-2) and (Y-13) are more preferable from the viewpoint of ease of synthesis.

In Formula (1) to Formula (4), Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a hydrogen atom or a monovalent substituent, and the structure of the substituent is not particularly limited. Specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Among these, it is preferable to have a steric repulsion effect particularly from the viewpoint of improving dispersibility, and the monovalent substituents represented by Z ^{1 to} Z ³ are each independently an alkyl group having 5 to 24 carbon atoms or carbon. An alkoxy group having 5 to 24 carbon atoms is preferable, and among them, an alkoxy group having a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to 24 carbon atoms is particularly preferable. The monovalent substituent represented by Z ⁴ is preferably an alkyl group having 5 to 24 carbon atoms, and among them, each independently a branched alkyl group having 5 to 24 carbon atoms or a cyclic group having 5 to 24 carbon atoms. Alkyl groups are preferred.
In Formula (1)-Formula (4), n, m, p, and q are integers of 1 to 500, respectively.
In Formula (1) and Formula (2), j and k each independently represent an integer of 2 to 8. J and k in Formula (1) and Formula (2) are preferably integers of 4 to 6, and most preferably 5, from the viewpoint of dispersion stability.

In formula (4), R represents a hydrogen atom or a monovalent organic group and is not particularly limited in terms of structure, but is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom. An atom or an alkyl group. 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. A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
Moreover, as R in Formula (4), two or more types of R having different structures may be mixed and used in the specific resin 1.

  The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) or (2A) from the viewpoint of dispersion stability.

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are as defined ^{X 1,} Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same.
Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^{X 2,} Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.

  The specific resin 1 further preferably has a structural unit represented by the formula (1A).

  In the specific resin 1 preferably used in the present invention, the structural unit (repeating unit) having the graft chain is preferably contained in a range of 10% to 80% with respect to the total mass of the specific resin 1 in terms of mass. More preferably, it is contained in the range of 20 to 65%, and particularly preferably in the range of 35 to 60%. Within this range, the dispersibility and dispersion stability of the metal oxide particles are high, and the film thickness uniformity in the coating film formed using the composition containing the dispersion composition is further improved. The specific resin 1 used in the present invention may be a combination of two or more types of graft copolymers having different structures.

The specific resin 1 preferably used in the present invention is a polymer having a structural unit (repeating unit) having an acid group in an amount of 20% by mass to 90% by mass with respect to the total mass of the specific resin 1. preferable. The content of the structural unit having an acid group is more preferably 50% by mass or more and 80% by mass or less, and most preferably 60% by mass or more and 75% by mass or less with respect to the total mass of the specific resin 1.
When the content of the structural unit having an acid group is 20% by mass or more based on the total mass of the specific resin 1, the adsorptivity to the metal oxide particles of the specific resin 1 is sufficient and the dispersion stability is improved. When the composition of the present invention is applied to a large size (for example, 12 inches) wafer, it becomes easy to form a film having a small film thickness difference between the central portion and the peripheral portion of the wafer.
When the content of the structural unit having an acid group is 90% by mass or less with respect to the total mass of the specific resin 1, the amount of the graft chain introduced into the specific resin 1 is sufficient, and the dispersion stability is improved. Similarly, it is easy to form a film with a small difference in film thickness between the central part and the peripheral part of the wafer.
Moreover, when 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 adjusted within the following preferable range.

  The acid group can also function as a functional group capable of forming an interaction with the metal oxide particles in addition to 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. It is preferably at least one selected from a group, a sulfonic acid group, and a phosphoric acid group, and a carboxylic acid group is particularly preferable.

  Furthermore, the acid group structure is preferably a structure separated by 5 atoms or more from the main chain of the resin structure. Furthermore, as the acid group, a carboxylic acid bonded to an aromatic ring is most preferable.

  As said acid group, these can be used individually by 1 type or in combination of 2 or more types.

  The acid value of the specific resin 1 is preferably in the range of 70 mgKOH / g to 350 mgKOH / g, more preferably in the range of 80 mgKOH / g to 300 mgKOH / g, and still more preferably in the range of 80 mgKOH / g to 150 mgKOH / g. Range. By setting the acid value within the above range, even when the composition is applied to a large size wafer (for example, 12 inches), a film having a small difference in film thickness between the central portion and the peripheral portion of the wafer can be obtained more reliably. Can do.

  The acid value of the specific resin 1 can be calculated from, for example, the average content of acid groups in the specific resin 1. Moreover, the resin which has a desired acid value can be obtained by changing content of the monomer unit containing the acid group which comprises the specific resin 1. FIG.

  The specific resin 1 may further have a structural unit (repeating unit) having a functional group capable of forming an interaction with the metal oxide particles other than the graft chain and the acid group. Such a structural unit having a functional group capable of forming an interaction with other metal oxide particles is not particularly limited in terms of structure. For example, a structural unit having a basic group or a structural unit having a coordinating group And structural units having a reactive group.

Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide group. Particularly preferred is a tertiary amino group having good adsorption power to metal oxide particles and high dispersibility and dispersion stability. As said basic group, these can be used individually by 1 type or in combination of 2 or more types.
The specific resin 1 may or may not contain a structural unit (repeating unit) having a basic group, but when it is contained, the content of the structural unit having a basic group is based on the total mass of the specific resin 1. On the other hand, it is 0.1 mass% or more and 50 mass% or less, Most preferably, it is 0.1 mass% or more and 30 mass% or less.

Examples of the coordinating group and the reactive group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride residue, acid chloride residue and the like. Particularly preferred is an acetylacetoxy group having good adsorption power to metal oxide particles and high dispersibility and dispersion stability. As the coordinating group and the reactive group, these can be used alone or in combination of two or more.
The specific resin 1 may or may not contain a structural unit (repeating unit) having a coordinating group or a reactive group, but if included, has a coordinating group or a reactive group. Content of a structural unit is 0.1 mass% or more and 50 mass% or less with respect to the total mass of the specific resin 1, Most preferably, it is 0.1 mass% or more and 30 mass% or less.

  Further, the specific resin 1 is different from the structural unit having a graft chain and the structural unit having an acid group, and has the following general formula (i) as a structural unit having a functional group capable of interacting with metal oxide particles. ) To (iii) may have at least one repeating unit obtained from the monomer represented by any one of (iii) to (iii).

In the above formulas (i) to (iii), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or a carbon atom number of 1-6. An alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
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. R ² and R ³ are particularly preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene groups), divalent heterocyclic groups and their oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino groups (—NR ³¹ —, where R ³¹ may be a combination with an aliphatic group, aromatic group or heterocyclic group) or a carbonyl group (—CO—).

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of the said aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, 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.

  6-20 are preferable, as for the carbon atom number of the said bivalent aromatic group, 6-15 are more preferable, and 6-10 are the most preferable. 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 divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocycle. Another heterocyclic ring, aliphatic ring or aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid. Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) _n —, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

  In the above formulas (i) to (iii), Z represents a functional group that can form an interaction with the metal oxide particles, and is preferably an acid group, a basic group, or a reactive group as described above. , A carboxylic acid group or a tertiary amino group is more preferable, and a carboxylic acid group is still more preferable. Y represents a methine group or a nitrogen atom.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, , Methyl group, ethyl group, propyl group, etc.), Z, or -LZ. Here, L and Z are as defined above. As R < ⁴ >, R < ⁵ > and R < ⁶ >, a hydrogen atom or a C1-C3 alkyl group is preferable, and a hydrogen atom is more preferable.

In the present invention, as the monomer represented by the general formula (i), R ¹ , R ² , and R ³ are a hydrogen atom or a methyl group, and L includes an alkylene group or an oxyalkylene structure 2 A compound in which X is an oxygen atom or an imino group and Z is a carboxylic acid group is preferable.
Further, as the monomer represented by the general formula (ii), 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. Is preferred. As the monomer represented by the general formula (iii), a compound in which R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom or a methyl group and Z is a carboxylic acid group is preferable.

  Examples of typical compounds represented by formulas (i) to (iii) include methacrylic acid, crotonic acid, isocrotonic acid, compounds having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, methacrylic acid 2 -Hydroxyethyl) and succinic anhydride reaction product, compound having addition polymerizable double bond and hydroxyl group in the molecule and phthalic anhydride reaction compound, compound having addition polymerizable double bond and hydroxyl group in the molecule And a reaction product of tetrahydroxyphthalic anhydride, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule, and pyro Reaction with merit anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinyl phenol , 4-hydroxyphenyl methacrylamide.

  Furthermore, the specific resin 1 preferably contained in the dispersion composition of metal oxide particles is a structural unit having the graft chain as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength. In addition to the structural unit having an acid group and a structural unit having a functional group capable of interacting with the metal oxide particle, which is different from these structural units, other structural units having various functions, for example, Further, a structural unit having a functional group having an affinity for the dispersion medium used in the dispersion can be included as a structural unit derived from the copolymerization component.

  The copolymerizable component copolymerizable with the specific resin 1 according to the present invention is selected from, for example, acrylic esters, methacrylic esters, styrenes, acrylonitriles, methacrylonitriles, acrylamides, methacrylamides, and the like. And radically polymerizable compounds.

  Specifically, for example, acrylic acid esters such as alkyl acrylate (the alkyl group preferably 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 acrylate, 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-hydroxy Propyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate, etc.)

Methacrylic acid esters (eg, benzyl methacrylate, 4-biphenyl methacrylate, butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 4- t-butylphenyl methacrylate, 4-chlorophenyl methacrylate, pentachlorophenyl methacrylate, 4-cyanophenyl methacrylate, cyanomethyl methacrylate, cyclohexyl methacrylate, 2-ethoxyethyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate, hexyl methacrylate, isobol Nyl methacrylate, isopropyl methacrylate, methyl methacrylate, 3,5- Methyl 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 (for example, 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 (eg methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene etc.), halogen styrene (eg chlorostyrene, dichlorostyrene, trichlorostyrene, tetra Chlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluoros Ren, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene etc.), acrylonitrile, methacrylonitrile, and the like.

  Among these radically polymerizable compounds, methacrylic acid esters, acrylamides, methacrylamides, and styrenes are preferably used, and benzyl methacrylate, t-butyl methacrylate, 4-t-butylphenyl methacrylate, pentachlorophenyl methacrylate, 4-cyanophenyl methacrylate, cyclohexyl methacrylate, 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-methylacrylamide, N-isopropylacrylamide, morpholylacrylamide, piperidylacrylamide, Nt-butylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N-naphthylacrylamide, N-hydroxymethylacrylamide, N- Hydroxyethylacrylamide, N-allylacrylamide, 4-hydroxyphenylacrylamide, 2-hydroxyphenylacrylamide, N, N-dimethylacrylamide, N, N-diisopropylacrylamide, N, N-di-t-butylacrylamide, N, N- Dicyclohexylacrylamide, N, N-phenylacrylamide, N, N-dihydroxyethylacrylamide, N, N-diallylacryl Bromide,

Methacrylamide, N-methylmethacrylamide, N-isopropylmethacrylamide, morpholylmethacrylamide, piperidylmethacrylamide, Nt-butylmethacrylamide, N-cyclohexylmethacrylamide, N-phenylmethacrylamide, N-naphthylmethacrylamide N-hydroxymethylmethacrylamide, N-hydroxyethylmethacrylamide, N-allylmethacrylamide, 4-hydroxyphenylmethacrylamide, 2-hydroxyphenylmethacrylamide, N, N-dimethylmethacrylamide, N, N-diisopropylmethacrylamide N, N-di-t-butylmethacrylamide, N, N-dicyclohexylmethacrylamide, N, N-phenylmethacrylamide, N, N-dihydroxyethylmethacrylate Acrylamide, 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, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3 -Trifluoromethylstyrene.

  These radically polymerizable compounds can be used alone or in combination of two or more. The specific resin 1 may or may not contain the above-mentioned radical polymerizable compound, but when it is contained, the content of structural units corresponding to these radical polymerizable compounds is based on the total mass of the specific resin 1 It is 0.1 mass% or more and 50 mass% or less, Most preferably, it is 0.1 mass% or more and 30 mass% or less.

  The specific resin 1 can be synthesized by a conventionally known method. 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- Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.

  Specific examples of the specific resin 1 include the following exemplary compounds 1 to 34, but the present invention is not limited thereto. In the following exemplary compounds, the numerical value written together with each structural unit (the numerical value written together with the main chain repeating unit) represents the content of the structural unit [mass%: described as (wt%)]. The numerical value written together with the repeating part of the side chain indicates the number of repetitions of the repeating part.

  The weight average molecular weight (polystyrene equivalent value measured by GPC method) of the specific resin 1 is preferably 5,000 or more and 300,000 or less, more preferably 7,000 or more and 100,000 or less. It is especially preferable that it is 50,000 or more and 50,000 or less.

  As the dispersion resin (B), a resin described below (hereinafter, referred to as “specific resin 2” as appropriate) may be used. The specific resin 2 has a repeating unit having a group X having a functional group of pKa14 or less, an oligomer chain or a polymer chain Y having 40 to 10,000 atoms in the side chain, and contains a basic nitrogen atom. It is characterized by that.

  The dispersion composition in the present invention interacts with the metal oxide particles (A) at both the nitrogen atom in the specific resin 2 and the functional group of pKa14 or less that the group X has, as will be described in detail later. 2 has an oligomer chain or polymer chain Y having an atom number of 40 to 10,000, for example, the oligomer chain or polymer chain Y functions as a steric repulsion group, thereby exhibiting good dispersibility and high Metal oxide particles as refractive particles can be uniformly dispersed. Moreover, even when the dispersion composition is stored at room temperature or the like for a long time, the oligomer chain or polymer chain Y interacts with the solvent to suppress the precipitation of the metal oxide particles for a long time. . Furthermore, when a coating film is formed with this dispersion composition (more specifically, for example, a curable composition), the oligomer chain or polymer chain Y functions as a steric repulsion group, thereby aggregating metal oxide particles. Therefore, even if the content of the metal oxide particles is increased, the dispersibility and dispersion stability are not easily impaired as described above. That is, by using the dispersion composition of the present invention, a film having a very high refractive index can be obtained while achieving excellent dispersibility and dispersion stability.

Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom, but it is preferable that the specific resin 2 has a structure having a nitrogen atom of pKb14 or less, and a nitrogen atom of pKb10 or less is included. It is more preferable to contain the structure which has.
The base strength pK _b in the present invention means a pK _b at a water temperature 25 ° C., is one of the index for quantitatively indicating the strength of the base, is synonymous with basicity constants. The base strength pK _b and the acid strength pK _a described later have _a relationship of pK _b = 14−pK _a .
About group X which has a functional group below pKa14, it is synonymous with group X mentioned later about specific resin 2-1.
As the oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain of the specific resin 2, it is synonymous with the oligomer chain or polymer chain Y having 40 to 10,000 atoms to be described later for the specific resin 2-1. is there.
As the specific resin 2, a repeating unit having a group X having a functional group of pKa14 or less represented by the following formula, a repeating unit having a basic nitrogen atom represented by the following formula, and the number of atoms represented by the following formula Examples thereof include a resin containing a repeating unit having an oligomer chain or polymer chain Y of 40 to 10,000 (corresponding in order from the left of the structure of the following repeating unit).

In the above formula, x, y, and z each represent a polymerization molar ratio of repeating units, and x is preferably 5 to 50, y is 5 to 60, and z is 10 to 90. l represents the number of linked polyester chains, and is an integer capable of forming an oligomer chain or polymer chain having 40 to 10,000 atoms, preferably 70 to 2000.
The specific resin 2 is a resin having a repeating unit containing a nitrogen atom to which a group X having a functional group of pKa14 or less is bonded, and an oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain. Preferably there is.
The specific resin 2 is composed of (i) a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. At least one selected repeating unit containing a nitrogen atom, the repeating unit having a group X bonded to the nitrogen atom and having a functional group of pKa14 or less, and (ii) the number of atoms in the side chain A resin 2-1 having 40 to 10,000 oligomer chains or polymer chains Y (hereinafter referred to as “specific resin 2-1” as appropriate) is particularly preferable.

((I) at least one selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. Repeating unit containing a species of nitrogen atom)
The specific resin 2-1 of the present invention includes a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. A repeating unit (i) containing at least one nitrogen atom selected from: Thereby, the adsorption | suction force to the said metal oxide particle (A) surface improves, and the interaction between the said metal oxide particles can be reduced.
The poly (lower alkyleneimine) may be a chain or a network.
At least one nitrogen atom selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit The number average molecular weight of the main chain obtained by polymerizing the repeating unit (i) containing, that is, the number average molecular weight of the portion excluding the oligomer chain or polymer chain Y portion of the side chain from the specific resin 2-1, 100 to 10,000 are preferable, 200 to 5,000 are more preferable, and 300 to 2,000 are most preferable. The number average molecular weight of the main chain part is obtained from the ratio of the hydrogen atom integral value of the terminal group and main chain part measured by nuclear magnetic resonance spectroscopy, or by measuring the molecular weight of an oligomer or polymer containing an amino group as a raw material. Can be sought.

  The repeating unit (i) containing a nitrogen atom is particularly preferably a poly (lower alkyleneimine) -based repeating unit or a polyallylamine-based repeating unit. In the present invention, the term “lower” in poly (lower alkyleneimine) means 1 to 5 carbon atoms, and the term “lower alkyleneimine” means an alkyleneimine having 1 to 5 carbon atoms. If this structure is clearly shown, the specific resin 2-1 of the present invention has a structure having a repeating unit represented by the general formula (I-1) and a repeating unit represented by the general formula (I-2), or It preferably includes a structure having a repeating unit represented by the general formula (II-1) and a repeating unit represented by the general formula (II-2).

(Repeating unit represented by general formula (I-1) and repeating unit represented by general formula (I-2))
The repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2), which are preferable components of the specific resin 2-1 of the present invention, will be described in detail.

In the general formulas (I-1) and (I-2),
R ¹ and R ² each independently represents a hydrogen atom, a halogen atom or an alkyl group. a represents the integer of 1-5 each independently. * Represents a connecting part between repeating units.
X represents a group having a functional group of pKa14 or less.
Y represents an oligomer chain or a polymer chain having 40 to 10,000 atoms.

  The specific resin 2-1 of the present invention further includes a repeating unit represented by the general formula (I-3) in addition to the repeating unit represented by the general formula (I-1) or the general formula (I-2). It is preferable to have it as a copolymerization component. By using such a repeating unit in combination, the dispersion performance is further improved when this resin is used as a dispersant for the metal oxide particles (A).

In the general formula (I-3),
*, R ¹ , R ² and a are as defined in general formula (I-1).
Y ′ represents an oligomer chain or polymer chain having an anionic group and having 40 to 10,000 atoms.
The repeating unit represented by the general formula (I-3) is obtained by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. It can be formed by reacting.

In General Formula (I-1), General Formula (I-2), and General Formula (I-3), R ¹ and R ² are particularly preferably hydrogen atoms. a is preferably 2 from the viewpoint of obtaining raw materials.

  The specific resin 2-1 of the present invention contains a lower alkyleneimine as a repeating unit in addition to the repeating units represented by the general formula (I-1), the general formula (I-2) and the general formula (I-3). You may go out. As described above, the lower alkyleneimine represents an alkyleneimine having 1 to 5 carbon atoms. The specific resin 2-1 may or may not contain such a lower alkyleneimine repeating unit. However, when it is included, the lower alkyleneimine repeating unit is included in the specific resin 2-1. It is preferable to contain 1-70 mol% in all the repeating units, and it is most preferable to contain 3-50 mol%. In addition, the group shown by said X, Y, or Y 'may further couple | bond with the nitrogen atom in such a lower alkyleneimine repeating unit. Resins containing both the repeating unit to which the group represented by X is bonded to the main chain structure and the repeating unit to which Y is bonded are also 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 having a functional group of pKa14 or less is bonded, and such a repeating unit containing a nitrogen atom is preserved. From the viewpoints of stability and developability, the content is preferably 1 to 80 mol%, and most preferably 3 to 50 mol% in all repeating units contained in the specific resin 2-1.
The repeating unit represented by the general formula (I-2) is a repeating unit having an oligomer chain or a polymer chain having 40 to 10,000 atoms, and such a repeating unit is selected from the viewpoint of storage stability. It is preferable to contain 10-90 mol% in all the repeating units of the specific resin 2-1 of this invention, and it is most preferable to contain 30-70 mol%.
To examine the content ratio of the two, from the viewpoint of the balance between dispersion stability and hydrophilicity / hydrophobicity, the repeating unit (I-1) :( I-2) is in the range of 10: 1 to 1: 100 in molar ratio. It is preferable that the ratio is in the range of 1: 1 to 1:10.

In addition, the repeating unit represented by the general formula (I-3) used in combination has a partial structure containing an oligomer chain or a polymer chain having 40 to 10,000 atoms ionically bonded to a nitrogen atom of the main chain. In view of the effect, the content is preferably 0.5 to 20 mol%, and most preferably 1 to 10 mol% in all repeating units of the specific resin 2-1.
In addition, it can confirm that the polymer chain Y has couple | bonded ionically by infrared spectroscopy or base titration.

(Repeating unit represented by general formula (II-1) and repeating unit represented by (II-2))
The repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-2), which are other preferable components of the specific resin 2-1 of the present invention, will be described in detail.

In general formulas (II-1) and (II-2),
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom, a halogen atom or an alkyl group. *, X and Y have the same meanings as *, X and Y in formulas (I-1) and (I-2).

  The specific resin 2-1 is further represented by the general formula (II-3) in addition to the repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-2). It is preferable to include a repeating unit as a copolymerization component. By using such a repeating unit in combination, the dispersion performance is further improved when this resin is used as a dispersant for the metal oxide particles (A).

In general formula (II-3), *, R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as in general formula (II-1). Y ′ has the same meaning as Y ′ in formula (I-3).

In the general formulas (II-1), (II-2) and (II-3), R ³ , R ⁴ , R ⁵ and R ⁶ are preferably hydrogen atoms from the viewpoint of availability of raw materials.

The general formula (II-1) is a repeating unit containing a nitrogen atom to which a group X having a functional group of pKa14 or less is bonded, and such a repeating unit containing a nitrogen atom is a viewpoint of storage stability and developability. From 1 to 80 mol% is preferable in all the repeating units contained in the specific resin 2-1, and 3 to 50 mol% is most preferable.
The general formula (II-2) is a repeating unit having an oligomer chain or a polymer chain Y having 40 to 10,000 atoms. Such a repeating unit is selected from the specific resin 2- of the present invention from the viewpoint of storage stability. It is preferable to contain 10-90 mol% in all the repeating units of 1, and it is most preferable to contain 30-70 mol%.

In order to examine the content ratio of the two, from the viewpoint of the balance between dispersion stability and hydrophilicity / hydrophobicity, the repeating unit (II-1) :( II-2) is in the range of 10: 1 to 1: 100 in molar ratio. It is preferable that the ratio is in the range of 1: 1 to 1:10.
The repeating unit represented by the general formula (II-3) used in combination is preferably contained in an amount of 0.5 to 20 mol% in all repeating units of the specific resin 2-1, and contained in an amount of 1 to 10 mol%. Most preferred.
The specific resin 2-1 of the present invention includes both the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2) from the viewpoint of dispersibility. Is most preferred.

<Group X having functional group of pKa14 or less>
X has a functional group having a pKa of 14 or less at a water temperature of 25 ° C. Here, “pKa” has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
The “functional group of pKa14 or less” is not particularly limited as long as the physical properties satisfy this condition, and examples thereof include those having a pKa satisfying the above range with known functional groups. The following functional groups are preferred, and those having a pKa of 11 or less are most preferred. Specifically, for example, carboxylic acid (about pKa 3 to 5), sulfonic acid (about pKa -3 to -2), -COCH ₂ CO- (about pKa 8 to 10), -COCH ₂ CN (pKa 8 to 11), -CONHCO-, phenolic hydroxyl group, -R _F CH ₂ OH or-(R _F ) ₂ CHOH (R _F represents a perfluoroalkyl group; about pKa 9-11), sulfonamide group (pKa 9- 11 or so), and the like, in particular a carboxylic acid (about pKa 3 to 5), sulfonic acid (about _{pKa -3~-2), - COCH} 2 CO- ( about pKa 8 to 10) are preferred.
When the pKa of the functional group of the group X is 14 or less, interaction with the metal oxide particles (A) can be achieved.
The group X having a functional group of pKa14 or less is preferably directly bonded to the nitrogen atom in the repeating unit containing the nitrogen atom, but the nitrogen atom and X in the repeating unit containing the nitrogen atom are covalently bonded. Moreover, you may connect in the aspect which forms a salt by ionic bond.

  As group X containing a functional group of pKa14 or less in the present invention, those having a structure represented by general formula (V-1), general formula (V-2) or general formula (V-3) are particularly preferable. .

In the general formula (V-1) and general formula (V-2),
U represents a single bond or a divalent linking group.
d and e each independently represents 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 (n—C ₁₀ H ₂₁ ) —, etc.), oxygen-containing alkylene (more specifically, for example, —CH ₂ OCH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc.) , Arylene groups (for example, phenylene, tolylene, biphenylene, naphthylene, furylene, pyrrolylene, etc.), alkyleneoxy (for example, ethyleneoxy, propyleneoxy, phenyleneoxy, etc.), alkenylene groups (for example, vinylene group), etc. In particular, 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 is preferable. Alkylene, an arylene group having 6 to 15 2-20 alkenylene group or a carbon atoms most preferred. Further, 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. The alkoxycarbonyl group in Q is preferably an alkoxycarbonyl group having 2 to 30 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, etc.). Q is particularly preferably an acyl group, and an acetyl group is preferable from the viewpoint of ease of production and availability of a raw material (precursor X ′ of X).

  The group X in the present invention is preferably bonded to the nitrogen atom of a repeating unit containing a nitrogen atom. Thereby, the dispersibility and dispersion stability of the metal oxide particles (A) are greatly improved.

  Further, since the group X contains a functional group having a pKa of 14 or less as a partial structure, the group X also functions as an alkali-soluble group. Accordingly, when this resin is used for a curable composition, energy is applied to the coating film to be partially cured, and the unexposed part is dissolved and removed to form a pattern. It is considered that the developability of the toner in an alkaline developer is improved, and the dispersibility, dispersion stability and developability can be established.

  The content of the functional group having a pKa of 14 or less in X is not particularly limited, but is preferably 0.01 to 5 mmol and most preferably 0.05 to 1 mmol with respect to 1 g of the specific resin 21 of the present invention. Within this range, the dispersibility and dispersion stability of the metal oxide particles (A) are improved, and when the resin is used in the curable composition, the developability of the uncured portion is excellent. From the viewpoint of the acid value, when the specific resin 2 of the present invention is used in a pattern-forming curable composition, the acid value of the specific resin 2 is included in an amount that is about 5 to 50 mgKOH / g. From the viewpoint of developability, it is preferable.

(Oligomer chain or polymer chain Y having 40 to 10,000 atoms)
Examples of Y include known polymer chains such as polyester, polyamide, polyimide, and poly (meth) acrylate that can be connected to the main chain portion of the specific resin 2. The binding site of Y with the specific resin 2 is preferably an end of the oligomer chain or polymer chain Y.

Y is at least one selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. It is preferable that it is combined with the nitrogen atom of the repeating unit containing the nitrogen atom. At least one nitrogen atom selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit The bonding mode between the main chain portion such as a repeating unit containing bismuth and Y is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond. The ratio of the binding mode between Y and the main chain is covalent bond: ionic bond = 100: 0 to 0: 100, preferably 95: 5 to 5:95, and most preferably 90:10 to 10:90. . Outside this range, the dispersibility / dispersion stability deteriorates and the solvent solubility decreases.
Y is preferably ionically bonded to the nitrogen atom of the repeating unit containing the nitrogen atom as an amide bond or carboxylate.

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.
If the number of atoms per one oligomer chain or polymer chain Y is less than 40, since the graft chain is short, the steric repulsion effect may be reduced and the dispersibility may be lowered. On the other hand, when the number of atoms per one oligomer chain or polymer chain Y exceeds 10,000, the oligomer chain or polymer chain Y becomes too long, the adsorptive power to the metal oxide particles is reduced, and the dispersibility is lowered. There is.
Moreover, the number average molecular weight of Y can be measured by the polystyrene conversion value by GPC method. The number average molecular weight of Y is particularly preferably 1,000 to 50,000, and most preferably 1,000 to 30,000 from the viewpoints of dispersibility, dispersion stability, and developability.
It is preferable that two or more side chain structures represented by Y are connected to the main chain in one molecule of the resin, and most preferably five or more are connected.

  In particular, Y preferably has a structure represented by the general formula (III-1).

  In general formula (III-1), Z is a polymer or oligomer having a polyester chain as a partial structure, and a residue obtained by removing a carboxyl group from a polyester having a free carboxylic acid represented by the following general formula (IV): Represent.

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

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

  Polyester having a carboxyl group at one end (polyester represented by formula (IV)) is (IV-1) polycondensation of carboxylic acid and lactone, (IV-2) polycondensation of hydroxy group-containing carboxylic acid, (IV -3) It can be obtained by polycondensation of dihydric alcohol and divalent carboxylic acid (or cyclic acid anhydride).

(IV-1) The carboxylic acid used in the polycondensation reaction of carboxylic acid and lactone is preferably an aliphatic carboxylic acid (a linear or branched carboxylic acid having 1 to 30 carbon atoms, such as 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, cyclohexane acid, etc.), hydroxy group-containing carboxylic acid (C1-C30 direct) A chain or branched hydroxy group-containing carboxylic acid is preferable, for example, glycolic acid, lactic acid, 3-hydroxypropionic acid, 4-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid. Acid, 2,2-bis (hydroxymethyl) butyric acid, etc.), in particular, straight chain having 6 to 20 carbon atoms. Hydroxy group-containing carboxylic acid aliphatic carboxylic acid or 1 to 20 carbon atoms are preferred. These carboxylic acids may be used as a mixture. As the lactone, a known lactone can be used, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-valerolactone, δ-hexalanolactone. , Δ-octanolactone, ε-caprolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, and the like, and ε-caprolactone is particularly preferable from the viewpoint of reactivity and availability.
These lactones may be used as a mixture of plural kinds.
The charged molar ratio at the time of the reaction between the carboxylic acid and the lactone cannot be uniquely determined because it depends on the molecular weight of the target polyester chain, but is preferably carboxylic acid: lactone = 1: 1 to 1: 1,000, and 1: 3 to 1 : 500 is most preferable.

(IV-2) The hydroxy group-containing carboxylic acid in the polycondensation of the hydroxy group-containing carboxylic acid is the same as the hydroxy group-containing carboxylic acid in (IV-1), and the preferred range is also the same.
(IV-3) As the dihydric alcohol in the polycondensation reaction of the dihydric alcohol and the divalent carboxylic acid (or cyclic acid anhydride), a linear or branched aliphatic diol (a diol having 2 to 30 carbon atoms is preferable, For example, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, etc. In particular, aliphatic diols having 2 to 20 carbon atoms are preferred.
As the divalent carboxylic acid, a linear or branched divalent aliphatic carboxylic acid (preferably a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms is preferable. For example, succinic acid, maleic acid, adipic acid, sebacic acid, Dodecanedioic acid, glutaric acid, suberic acid, tartaric acid, oxalic acid, malonic acid, etc.), and in particular, a divalent carboxylic acid having 3 to 20 carbon atoms is preferred. Further, acid anhydrides equivalent to these divalent carboxylic acids (for example, succinic anhydride, glutaric anhydride, etc.) may be used.
The divalent carboxylic acid and the dihydric alcohol are preferably charged at a molar ratio of 1: 1. This makes it possible to introduce a carboxylic acid at the terminal.

The polycondensation during the production of the polyester is preferably performed by adding a catalyst. As the catalyst, a catalyst that functions as a Lewis acid is preferable. For example, a Ti compound (eg, Ti (OBu) ₄ , Ti (O—Pr) _4, etc.), a Sn compound (eg, tin octylate, dibutyltin oxide, dibutyltin laurate) , Monobutyltin hydroxybutyl oxide, stannic chloride, etc.), protonic acids (for example, sulfuric acid, paratoluenesulfonic acid, etc.) and the like. The catalyst amount is preferably from 0.01 to 10 mol%, most preferably from 0.1 to 5 mol%, based on the number of moles of all monomers. The reaction temperature is preferably 80 to 250 ° C, and most preferably 100 to 180 ° C. Although reaction time changes with reaction conditions, it is 1 to 24 hours in general.

  The number average molecular weight of the polyester can be measured as a polystyrene converted value by the GPC method. The number average molecular weight of the polyester is 1,000 to 1,000,000, preferably 2,000 to 100,000, and most preferably 3,000 to 50,000. When the molecular weight is in this range, both dispersibility and developability can be achieved.

  The polyester partial structure forming the polymer chain in Y is particularly a polyester obtained by (IV-1) polycondensation of carboxylic acid and lactone and (IV-2) polycondensation of hydroxy group-containing carboxylic acid. Is preferable from the viewpoint of ease of manufacture.

  Specific embodiments [(A-1) to (A-61)] of the specific resin 2 of the present invention are shown below by the specific structure of the repeating unit of the resin and the combination thereof, but the present invention is not limited to this. It is not something. In the following formula, k, l, m and n each represent a polymerization molar ratio of repeating units, k is 1 to 80, l is 10 to 90, m is 0 to 80, n is 0 to 70, and k + l + m + n = 100. p and q represent the number of linked polyester chains, and each independently represents 5 to 100,000. R 'represents a hydrogen atom or an alkylcarbonyl group.

In order to synthesize the specific resin 2 of the present invention, (1) a method of reacting a resin having a primary or secondary amino group with a precursor x of X and a precursor y of Y, (2) containing X Can be produced by a method such as polymerization of a monomer to be polymerized with a macromonomer containing Y. First, a resin having a primary or secondary amino group in the main chain is synthesized, and then X The precursor x and the precursor y of Y are preferably reacted and introduced into a nitrogen atom present in the main chain by a polymer reaction.
Examples of the resin having a primary or secondary amino group include an oligomer or a polymer containing a primary or secondary amino group constituting a main chain portion having a nitrogen atom. For example, poly (lower alkyleneimine), polyallylamine , Polydiallylamine, metaxylenediamine-epichlorohydrin polycondensate, polyvinylamine and the like. Of these, oligomers or polymers composed of poly (lower alkyleneimine) or polyallylamine are preferred.

The precursor x of the group X having a functional group of pKa14 or less represents a compound capable of reacting with the resin having the primary or secondary amino group and introducing X into the main chain.
Examples of x are cyclic carboxylic acid anhydrides (cyclic carboxylic acid anhydrides having 4 to 30 carbon atoms are preferred, such as succinic acid anhydride, glutaric acid anhydride, itaconic acid anhydride, maleic acid 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- (Hexene-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, acetylmalic anhydride, diacetyltartaric anhydride, het acid anhydride, cyclohexane-1,2-dicarboxylic acid Water, 3 or 4-methylcyclohexane-1,2-dicarboxylic anhydride, tetrafluorosuccinic anhydride, 3 or 4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1 , 2-dicarboxylic anhydride, phthalic 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-cyclopentanecarboxylic dianhydride Etc.), halogen atom-containing carboxylic acids (for example, chloroacetic acid, bromoacetic acid, iodoacetic acid, 4-chloro-n-butyric acid, etc.), sultone (for example, propane sultone, 1,4-butanthol) Etc.), diketene, cyclic sulfocarboxylic anhydride (for example, 2-sulfobenzoic acid anhydride, etc.), - COCH ₂ COCl compounds containing (e.g., ethyl malonyl chloride, etc.), or a cyano acetic acid chloride, and the like, In particular, cyclic carboxylic acid anhydride, sultone, and diketene are preferable from the viewpoint of productivity.

The precursor y of the oligomer chain or polymer chain Y having 40 to 10,000 atoms is a compound that can react with the resin having the primary or secondary amino group to introduce the oligomer chain or polymer chain Y. Represent.
y is preferably an oligomer or polymer having 40 to 10,000 atoms having a group capable of covalent bonding or ionic bonding with the nitrogen atom of the specific resin 2, and particularly 40 to 40 atoms having a free carboxyl group at one end. 10,000 oligomers or polymers are most preferred.
Examples of y include a polyester represented by the general formula (IV) having a free carboxylic acid at one end, a polyamide having a free carboxylic acid at one end, and a poly (meth) having a free carboxylic acid at one end. Examples thereof include acrylic resins, and polyesters containing a free carboxylic acid at one end represented by the general formula (IV) are most preferable.

  y can be synthesized by a known method. For example, a polyester containing a free carboxylic acid at one end represented by the general formula (IV) is, as described above, a combination of (IV-1) carboxylic acid and lactone. Examples thereof include polycondensation, (IV-2) polycondensation of hydroxy group-containing carboxylic acid, and (IV-3) polycondensation of dihydric alcohol and divalent carboxylic acid (or cyclic acid anhydride). A polyamide containing a free carboxylic acid at one end can be produced by self-condensation of an amino group-containing carboxylic acid (for example, glycine, alanine, β-alanine, 2-aminobutyric acid, etc.). A poly (meth) acrylic acid ester having a free carboxylic acid at one end is obtained by radical polymerization of a (meth) acrylic acid monomer in the presence of a carboxyl group-containing chain transfer agent (for example, 3-mercaptopropionic acid). Can be manufactured.

  The specific resin 2 of the present invention includes (a) a method of reacting a resin having a primary or secondary amino group with x and y simultaneously, and (b) a reaction of a resin having a primary or secondary amino group with x, It can be produced by a method of reacting with y and (c) a method of reacting y with a resin having a primary or secondary amino group and then reacting with x. In particular, (c) a method in which a resin having a primary or secondary amino group is reacted with y and then reacted with x is preferable.

  Although reaction temperature can be suitably selected according to conditions, 20-200 degreeC is preferable and 40-150 degreeC is the most preferable. The reaction time is preferably 1 to 48 hours, and more preferably 1 to 24 hours from the viewpoint of productivity.

The reaction may be performed in the presence of a solvent. Examples of the solvent include water, sulfoxide compounds (for example, dimethyl sulfoxide), ketone compounds (for example, acetone, methyl ethyl ketone, cyclohexanone, etc.), ester compounds (for example, ethyl acetate, butyl acetate, ethyl propionate, propylene glycol 1-monomethyl ether). 2-acetate, etc.), ether compounds (eg, diethyl ether, dibutyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbon compounds (eg, pentane, hexane, etc.), aromatic hydrocarbon compounds (eg, toluene, xylene, mesitylene, etc.) Nitrile compounds (eg, acetonitrile, propiononitrile, etc.), amide compounds (eg, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), carboxylated compounds (Eg, acetic acid, propionic acid, etc.), alcohol compounds (eg, methanol, ethanol, isopropanol, n-butanol, 3-methylbutanol, 1-methoxy-2-propanol, etc.), halogenated solvents (eg, chloroform, 1, 2-dichloroethane etc.).
When using a solvent, it is preferable to use 0.1-100 mass times with respect to a substrate, and it is most preferable to use 0.5-10 mass times.
The specific resin 2 of the present invention may be purified by a reprecipitation method. By removing the low molecular weight component by the reprecipitation method, the dispersion performance when the obtained specific resin 2 is used as a dispersant is improved. For reprecipitation, it is preferable to use a hydrocarbon meter solvent such as hexane and an alcohol solvent such as methanol.

  The specific resin 2 thus obtained in the present invention preferably has a weight average molecular weight measured by GPC method of 3,000 to 100,000, and more preferably 5,000 to 55,000. preferable. When the molecular weight is in the above range, there is an advantage that high developability and high storage stability can be achieved. Moreover, the presence of the nitrogen atom in the repeating unit (i) containing a nitrogen atom in the specific resin 2 of the present invention can be confirmed by a method such as acid titration, the presence of a functional group having a pKa of 14 or less, and That the functional group is bonded to the nitrogen atom of the repeating unit can be confirmed by methods such as base titration, nuclear magnetic resonance spectroscopy, and infrared spectroscopy. Further, (ii) the point having an oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain can be confirmed by a method such as nuclear magnetic resonance spectroscopy or GPC method.

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

  In the dispersion composition preferably contained in the composition of the present invention, each of the specific resins 1 and 2 can be used alone or in combination of two or more.

  The content of the dispersion resin (B) (for example, the specific resin 1 or 2) with respect to the total solid content of the dispersion composition or the composition of the present invention preferably contained in the composition of the present invention is such that the dispersibility and dispersion stability are high. From a viewpoint, the range of 10-50 mass% is preferable, the range of 11-40 mass% is more preferable, and the range of 12-30 mass% is still more preferable.

-Other dispersion resins-
The dispersion composition preferably contained in the composition of the present invention includes a dispersion resin other than the specific resin (hereinafter referred to as “other dispersion resin”) for the purpose of adjusting the dispersibility of the metal oxide particles. May be contained).
Other dispersion resins that can be used in the present invention include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly ( (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
Other dispersion resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

The other dispersion resin acts to adsorb on the surface of the metal oxide particles and optionally used pigment to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the surface of the metal oxide particles can be cited as preferred structures.
On the other hand, other dispersion resins have the effect of promoting the adsorption of the dispersion resin by modifying the surface of the metal oxide particles.

Specific examples of other dispersion resins include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, manufactured by BYK Chemie. 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type) manufactured by EFKA ), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo pigment derivative) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fintechno Co., Ltd.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”, manufactured by Enomoto Kasei Co., Ltd. “Dispalon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725”, “Demol RN manufactured by Kao Corporation” , N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), “homogenol L-18 (polymeric polycarboxylic acid)”, “Emulgen 920, 930” , 935, 985 (polyoxyethylene nonylphenyl ether) "," acetamine 86 (su Allylamine acetate) ”, Lubrizol Corporation“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.
These other resins may be used alone or in combination of two or more.

  The dispersion composition preferably contained in the composition of the present invention or the composition of the present invention may or may not contain other dispersion resins. However, if it is contained, the entire dispersion composition or the composition of the present invention is included. The content of the other dispersion resin relative to the solid content is preferably in the range of 1 to 20% by mass, and more preferably in the range of 1 to 10% by mass.

(C) Solvent Although the dispersion composition preferably contained in the composition of the present invention includes a solvent, the solvent can be composed of various organic solvents.
Organic solvents that can be used here 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 acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, Examples include ethyl lactate.
These organic solvents can be used alone or in combination. The concentration of the solid content in the dispersion composition preferably contained in the composition of the present invention is preferably 2 to 60% by mass.

  There is no restriction | limiting in particular as a manufacturing method of the dispersion composition preferably contained in the composition of this invention, The manufacturing method of the dispersion composition normally used can be applied. For example, the metal oxide particles (A), the dispersion resin (B), and the solvent (C) can be mixed and dispersed by using a circulation type dispersion device (bead mill) or the like.

<Composition>
The composition of the present invention comprises a binder polymer (F) containing a repeating unit derived from benzyl (meth) acrylate in addition to the above-mentioned titanium oxide particles or zirconium oxide particles as the metal oxide particles (A), and an interface. It is a composition containing an active agent (G), Comprising: Content of the said surfactant (G) is 0.0010 mass%-3.0 mass% with respect to the total solid of a composition.
With such a configuration, a film (typically a transparent film) having a high refractive index, a small change with time in the coating surface after application of the composition, and a small decrease in refractive index after development processing is formed. Composition.
The composition of the present invention is preferably a curable composition. As one form of the curable composition, the composition of the present invention further comprises a polymerizable compound (D) and a polymerization initiator (E), and includes other components as necessary. It is preferable that it is a curable composition.
Thus, in the present invention, since the “curable composition” is a form of the “composition”, as described above, the content of the metal oxide particles relative to the total solid content of the curable composition is: This is the same as the range of the content of the metal oxide particles in the above-described composition or dispersion composition.
By using the composition of the present invention as a curable composition, a film having a high refractive index, a small change with time in the coated surface state after application of the composition, and a small decrease in refractive index after development processing. (Typically, a transparent film) can be formed better.
The present invention also relates to a transparent film formed using the composition or curable composition of the present invention.

A film or a cured film obtained from the composition or curable composition of the present invention (a film formed by a curable composition and then subjected to a curing reaction) has a refractive index of 1.72 to 2.60. It is preferable that it is 1.80 to 2.60.
The physical property that the refractive index of the film or the cured film is 1.72 to 2.60 is that the composition of the present invention contains a repeating unit derived from the metal oxide particles (A) and benzyl (meth) acrylate. As long as it contains a binder polymer (F) and a surfactant (G) (in the curable composition of the present invention, the polymerizable compound (D) and the polymerization initiator (E)), this is achieved by any means. For example, the type and content of the polymerizable compound (D) and the binder polymer that can be further added, the metal oxide particles (A) are added to the composition, and the metal oxidation is performed. This is preferably achieved by adjusting the kind and content of the product particles.
In particular, the above physical properties can be achieved more easily by making the metal oxide particles into the above-described preferred examples.

The composition of the present invention is preferably a transparent composition, and more specifically, when a 1.0 μm-thick film or cured film is formed from the composition, the thickness of the film or cured film The composition has a light transmittance with respect to a direction of 90% or more over the entire wavelength region of 400 to 700 nm.
That is, the transparent film of the present invention is a film having a light transmittance of 90% or more over the entire wavelength region of 400 to 700 nm at a film thickness of 1.0 μm.
Such physical properties of light transmittance are such that the composition of the present invention comprises a binder polymer (F) containing a repeating unit derived from the metal oxide particles (A), benzyl (meth) acrylate and a surfactant ( G) (As long as it further contains a polymerizable compound (D) and a polymerization initiator (E) in the curable composition of the present invention), it may be achieved by any means. It is suitably achieved by adjusting the type and content of (D) or a binder polymer that can be further added. Moreover, the said physical property of the light transmittance can be suitably achieved also by adjusting the particle diameter of a metal oxide particle (A), the kind and addition amount of a dispersion resin (B).
Regarding the composition and the transparent film of the present invention, it is important that the light transmittance is 90% or more over the entire wavelength region of 400 to 700 nm, particularly for the microlens to exhibit its required characteristics. Is an element.

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

  In view of the above, the composition of the present invention substantially does not contain a colorant (the content of the colorant is preferably 0% by mass with respect to the total solid content of the composition).

(F) Binder polymer containing repeating units derived from benzyl (meth) acrylate The composition of the present invention contains a binder polymer (F) containing repeating units derived from benzyl (meth) acrylate. When the binder polymer contains a repeating unit derived from benzyl (meth) acrylate, the dispersion state of the metal oxide particles in the composition becomes stable, and it is presumed that it contributes to the manifestation of the effect of the present invention. .

The binder polymer (F) of the present invention is further 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 contain a repeating unit (hereinafter also referred to as “MAA” or “repeat unit MAA”), and in addition to these, a repeating unit derived from an alkyl (meth) acrylate Is more preferable. When the binder polymer (F) contains these repeating units, the effects of the present invention are more favorably expressed.
The repeating unit derived from (meth) acrylate (“repeat unit MAA”) is typically a repeating unit derived from (meth) acrylic acid.
Carbon number of the side chain alkyl group in the repeating unit derived from alkyl (meth) acrylate is preferably 1-30, more preferably 1-20.
Examples of the repeating unit derived from alkyl (meth) acrylate include a repeating unit derived from isobutyl (meth) acrylate (hereinafter sometimes referred to as “iBuMA” or “repeat unit iBuMA”), hydroxyethyl (meth) A repeating unit derived from an acrylate (hereinafter sometimes referred to as “HEMA” or “repeating unit HEMA”) and a repeating unit derived from an alkyl (meth) acrylate containing an ethylene oxide group (hereinafter referred to as “EOA”) Or “repeating unit EOA”). Among them, at least one repeating unit is preferably contained, and at least two repeating units are more preferably contained.
Here, the repeating unit derived from an alkyl (meth) acrylate containing an ethylene oxide group is a repeating unit derived from an alkyl (meth) acrylate, and a part or all of the alkylene chain in the side chain alkyl group Means a repeating unit having a structure substituted with an ethylene oxide group. Ethylene oxide group is _{- (C 2 H 4 O)} n - is preferably represented by. Here, n represents an integer, preferably an integer of 2 to 90, more preferably an integer of 4 to 23, and particularly preferably an integer of 6 to 15.

The binder polymer (F) preferably has an ethylene oxide group, more preferably contains a repeating unit EOA, and more preferably contains both a repeating unit EOA and a repeating unit iBuMA.
That is, as the binder polymer (F) of the present invention, a binder polymer containing all of the repeating unit BzMA, the repeating unit MAA, the repeating unit EOA, and the repeating unit iBuMA is particularly preferable, and the binder polymer composed of only these four repeating units is most preferable. preferable.
Although it is unclear why it is preferable to include both the repeating unit iBuMA and the repeating unit EOA in addition to the repeating unit BzMA as the repeating unit of the binder polymer (F), the solubility of the binder polymer (F) in the composition and the metal oxidation It is estimated that by balancing the compatibility with the product particles, the uniformity in the solution state and thus the uniformity of the film when it is formed into a coating film will be further increased.

The content of the repeating unit BzMA in the binder polymer (F) of the present invention is preferably in the range of 10 to 65 mol%, more preferably 10 to 50 mol, based on all repeating units of the binder polymer (F). %, More preferably in the range of 20 to 40 mol%.
The binder polymer (F) of the present invention may or may not contain the repeating unit MAA, but when it is contained, the content of the repeating unit MAA is preferably relative to all the repeating units of the binder polymer (F). Is in the range of 1 to 50 mol%, more preferably in the range of 5 to 40 mol%, still more preferably in the range of 10 to 35 mol%.
The binder polymer (F) of the present invention may or may not contain the repeating unit iBuMA, but when it is contained, the content of the repeating unit iBuMA is preferably relative to all the repeating units of the binder polymer (F). Is in the range of 1 to 50 mol%, more preferably in the range of 10 to 50 mol%, still more preferably in the range of 20 to 45 mol%.
The binder polymer (F) of the present invention may or may not contain the repeating unit HEMA, but when it is contained, the content of the repeating unit HEMA is preferably relative to all the repeating units of the binder polymer (F). Is in the range of 1 to 40 mol%, more preferably in the range of 3 to 30 mol%, still more preferably in the range of 5 to 25 mol%.
The binder polymer (F) of the present invention may or may not contain the repeating unit EOA, but when it is contained, the content of the repeating unit EOA is preferably relative to all the repeating units of the binder polymer (F). Is in the range of 0.5 to 40 mol%, more preferably in the range of 1 to 25 mol%, still more preferably in the range of 2 to 15 mol%.

The weight average molecular weight (polystyrene conversion value measured by GPC method) of the binder polymer (F) of the present invention is preferably 1,000 or more, more preferably 5,000 to 100,000, and still more preferably 5 The range is from 5,000 to 50,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.
The binder polymer (F) may be a random polymer, a block polymer, a graft polymer, or the like.

The binder polymer (F) of the present invention can be synthesized by a conventionally known method. Examples of the solvent used in 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. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing the binder polymer (F) used in the composition of the present invention include known compounds such as an azo initiator and a peroxide initiator.

Specific examples of the binder polymer (F) are shown below together with their weight average molecular weight (Mw) and copolymerization ratio (molar ratio), but the present invention is not limited thereto.

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

  The content of the binder polymer (F) in the composition of the present invention is preferably 1% by mass to 40% by mass, and preferably 3% by mass to 30% by mass with respect to the total solid content of the composition. More preferably, the content is 4% by mass or more and 20% by mass or less.

-Other binder polymers-
The composition of the present invention may contain a binder polymer other than the binder polymer (F). As the binder polymer other than the binder polymer (F), a linear organic polymer is preferably used. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. No. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a monomer having a carboxyl group alone or Copolymerized resin, acid anhydride monomer alone or copolymerized, acid anhydride unit hydrolyzed, half esterified or half amidated, epoxy resin unsaturated monocarboxylic acid and acid anhydride Examples include modified epoxy acrylate. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

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

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate Alkyl acrylates such as 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate, and the like.

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate , Alkyl methacrylates such as 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate, and the like.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(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) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl 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-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, the compounds described in JP-A-2002-309057, JP-A-2002-311569 and the like can be mentioned.

  The binder polymer other than the binder polymer (F) is obtained by polymerizing a monomer component essentially comprising a compound represented by the following general formula (ED) (hereinafter sometimes referred to as “ether dimer”). It is also preferable to include a repeating unit.

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

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

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be used alone or in combination of two or more. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

Also, Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication No. 63-287947. Urethane binder polymer containing an acid group described in JP-A No. 1-271741 and the like, and urethane binder having an acid group and a double bond in a side chain described in JP-A No. 2002-107918 Since the polymer is very excellent in strength, it is advantageous in terms of film strength.
Acetal-modified polyvinyl alcohol-based binder polymers having an acid group described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 are also preferable because of their excellent film strength.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight (polystyrene equivalent value measured by GPC method) of the binder polymer other than the binder polymer (F) that can be used in the composition of the present invention is preferably 5,000 or more, and more preferably 10,000. The number average molecular weight is preferably 1,000 or more, and more preferably 2,000 or more and 250,000 or less. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

Binder polymers other than the binder polymer (F) that can be used in the present invention can be synthesized by a conventionally known method. As the solvent used in the synthesis, the same solvent as that used in the synthesis of the binder polymer (F) is used.
Examples of the radical polymerization initiator used when synthesizing a binder polymer other than the binder polymer (F) that can be used in the composition of the present invention include known compounds such as an azo initiator and a peroxide initiator.

  In the composition of the present invention, binder polymers other than the binder polymer (F) can be used singly or in combination of two or more.

  The composition of the present invention may or may not contain a binder polymer other than the binder polymer (F), but when it is contained, the binder polymer other than the binder polymer (F) with respect to the total solid content of the composition. The content of is preferably 1% by mass to 40% by mass, more preferably 3% by mass to 30% by mass, and still more preferably 4% by mass to 20% by mass.

(G) Surfactant The composition of the present invention contains various surfactants in the range of 0.0010% by mass to 3.0% by mass with respect to the total solid content of the composition. By containing the 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 when the coating film is formed, and as a result, the problem of the present application Thus, it is possible to prevent deterioration of the coated surface state after lapse of time and a decrease in refractive index after etching development. Further, when the surfactant is added in an amount exceeding 3.0% by mass, the coated surface is deteriorated due to the repelling of the surfactant itself.
As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
Of these, fluorine-based surfactants or nonionic surfactants are preferable, and fluorine-based surfactants are most preferable.

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

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

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

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), Surfynol 465 (manufactured by Nissin Chemical), and the like.

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

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

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

  In the composition of the present invention, the content of the surfactant needs to be adjusted to 0.0010% by mass to 3.0% by mass with respect to the total solid content of the composition. In order to minimize the decrease in refractive index after etching development processing, which is a problem to be solved by the present application, the content of the surfactant is 0.010% by mass to 3% with respect to the total solid content of the composition. It is preferably 0.0% by mass, more preferably 0.10% by mass to 3.0% by mass, still more preferably 0.50% by mass to 3.0% by mass, and particularly preferably 1%. 0.0 mass% to 3.0 mass%.

  The composition of the present invention contains titanium oxide particles as the metal oxide particles (A), the binder polymer J-1 as the binder polymer (F), and a fluorosurfactant as the surfactant (G). It is a composition containing this, Comprising: It is a coating surface after application | coating that content of the said fluorosurfactant is 0.50 mass%-3.0 mass% with respect to the total solid of the said composition It is preferable because a film with a smaller change in shape with time and a lower refractive index after development can be formed.

(D) Polymerizable compound When the composition of the present invention is a curable composition and contains a polymerizable compound (D), the polymerizable compound (D) contains at least one ethylenically unsaturated double bond. The addition-polymerizable compound is preferably selected from compounds having at least one terminal ethylenically unsaturated bond, more preferably two or more. Such compounds are widely known in the technical field, and can be used without particular limitation in the present invention.
These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and A dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having an electrophilic substituent such as an isocyanate group or an epoxy group and a monofunctional or polyfunctional alcohol, amine, or thiol; Furthermore, a substitution reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a leaving group such as a halogen group or a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. It is. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, 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, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanur Examples include acid EO-modified triacrylate.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer having a hydroxyl group represented by the following formula (V) to a polyisocyanate compound having two or more isocyanate groups: Etc.
In the following formula (V), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group.

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Furthermore, by using polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a curable composition having a very high photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reaction. Also, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, 300-308 (1984), photocurable monomers and oligomers can also be used.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
As other preferable polymerizable compounds, compounds having a fluorene ring and having two or more functional ethylenic polymerizable groups described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and cardo resins. Can also be used.

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

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or represents an _{-OC (= O) C (CH} 3) = groups represented by CH _2.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraph numbers 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

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

Among them, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co. Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.
As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is essential.
Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a polymerizable monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone structure represented by the following formula (1) is preferable.

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

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

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)
Such a polyfunctional monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)). , Number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ is all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the formula, the number of groups represented by formula (2) = 6, and R ¹ is all hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

  The specific monomer in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

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

In the general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In addition,-((CH2) yCH2O)-or-((CH2) yCH (CH3) O)-in general formula (i) or general formula (ii) has a form in which the terminal on the oxygen atom side is bonded to X. preferable.

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

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

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

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

  Examples of commercially available products of the specific monomers represented by the general formulas (i) and (ii) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and pliers manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six lenoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide-based skeleton described in 58-49860, JP-B 56-17654, JP-B 62-39417, and JP-B 62-39418. Further, as polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are exemplified. By using it, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
As the polymerizable compound, ethylenically unsaturated compounds having an acid group are also suitable. The ethylenically unsaturated compounds having an acid group can be obtained by, for example, converting (meth) acrylate a part of the hydroxy group of the polyfunctional alcohol and adding an acid anhydride to the remaining hydroxy group to form a carboxy group. can get. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a curable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
In addition, the selection and use of the polymerizable compound is also an important factor for compatibility and dispersibility with other components (for example, polymerization initiator, metal oxide particles, etc.) contained in the curable composition. For example, the compatibility may be improved by using a low-purity compound or using two or more other components in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a substrate.

  When the composition of the present invention is a curable composition and contains a polymerizable compound (D), the polymerizable compound (D) may be a polymerizable compound having at least one epoxy group (hereinafter referred to as “epoxy compound”). Can also be used. Such epoxy compounds are widely known in the technical field, and these can be used without particular limitation in the present invention.

The composition of the present invention may or may not contain the polymerizable compound (D), but when it is contained, the content of the polymerizable compound (D) is 1 with respect to the total solid content of the composition. The range is preferably from 50% by mass to 50% by mass, more preferably from 3% by mass to 40% by mass, and still more preferably from 5% by mass to 30% by mass.
Within this range, the curability is good and preferable without lowering the refractive index.

(E) Polymerization initiator The polymerization initiator (E) used when the composition of the present invention is a curable composition and contains a polymerizable compound (D) starts polymerization of the polymerizable compound (D). From the viewpoint of improving the curing in the heating step such as steps (d) and (b) in the microlens manufacturing method described later, it is stable up to 45 ° C., but at the time of high-temperature heating. It is preferable that the polymerization initiating ability is good.
In addition, in the microlens manufacturing method described later, from the viewpoint of improving the curing in the exposure step by radiation irradiation such as steps (b), (b), and (d), it is sensitive to visible light from the ultraviolet region. Those having properties are preferred. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The polymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
Moreover, a polymerization initiator can be used individually or in combination of 2 or more types.

  Examples of the polymerization initiator (E) include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, Examples include hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, 48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241 JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, M.K. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

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

  Examples of oxydiazole compounds include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole and the like Can be mentioned.

  Examples of carbonyl compounds include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone, 2,2-dimethoxy 2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1 -Hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 2- (dimethylamino) -2-[(4-methylpheny ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4-morpholino Acetophenone derivatives such as butyrophenone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, p- Examples thereof include benzoic acid ester derivatives such as ethyl dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of ketal compounds include benzylmethyl ketal and benzyl-β-methoxyethylethyl acetal.

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

  Examples of acridine compounds include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- ( t-he Sylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylper) Oxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

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

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,853, 2,6-bis (4-azidobenzylidene) -4. -Ethylcyclohexanone (BAC-E) etc. are mentioned.

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dicyclopenta Dienyl-Ti-bis-2,4-difluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, dicyclopentadienyl-Ti- Bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl Nyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl Dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-penta Examples thereof include fluorophenyl-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

As the biimidazole compound, for example, a hexaarylbiimidazole compound (rophine dimer compound) is preferable.
Examples of the hexaarylbiimidazole compound include lophine dimers described in JP-B-45-37377 and JP-B-44-86516, JP-B-6-29285, U.S. Pat. No. 3,479,185, and the like. Various compounds described in each specification such as 4,311,783 and 4,622,286, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) vididazole, 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 Examples include '-tetraphenylbiimidazole.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Laid-Open No. 2001116539, and the like, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. Organoborates, organoboron sulfonium complexes or organoboron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554, Described in JP-A-6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527 Specific examples include organoboron transition metal coordination complexes and the like disclosed in JP-A-7-292014.

  Examples of the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2002-328465.

The (E) polymerization initiator used in the present invention is preferably an oxime compound from the viewpoints of curability, stability over time, and difficulty in coloring during post-heating.
Examples of oxime compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Publication No. 2004-534797 Compounds and the like.

  The oxime compound has a function as a thermal polymerization initiator that decomposes by heat to start and accelerate polymerization.

The oxime compound used in the present invention preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and has a wavelength of 365 nm and 455 nm. Those having high absorbance are particularly preferred.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

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

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, The phosphonium salts described in the specifications of Nos. 055 and 4,069,056, the specifications of European Patent No. 104,143, and the specifications of JP-A-2-150848 and JP-A-2-296514 And iodonium salts.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and from the viewpoint of stability, it may be substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group. preferable.

Examples of the sulfonium salt suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. No. 4,933. 377, 4,760,013, 4,734,444, 2,833,827, German Patents 2,904,626, 3,604,580, 3, Examples thereof include sulfonium salts described in each specification of No. 604,581, and from the viewpoints of stability and sensitivity, those substituted with an electron withdrawing group are preferable. The electron withdrawing group preferably has a Hammett value greater than zero. Examples of preferable electron withdrawing groups include halogen atoms and carboxylic acid groups.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin structure or an anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Examples of onium salt compounds include those described in J. Org. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, and Darocur TPO manufactured by BASF.

  As the polymerization initiator (E) used in the curable composition of the present invention, from the viewpoint of curability, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound Compounds, 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 salts thereof And a compound selected from the group consisting of a halomethyloxadiazole compound and a 3-aryl-substituted coumarin compound.

  More preferably, they are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  In particular, when the curable composition of the present invention is provided on a color filter of a solid-state imaging device to form a microlens, the coloring is particularly small during post-heating and the curability is good. It is most preferable to use an oxime compound as the polymerization initiator.

  The composition of the present invention may or may not contain a polymerization initiator (E), but when it is contained, the content of the polymerization initiator (E) (in the case of two or more types) is: It is preferable that it is 0.1 mass% or more and 10 mass% or less with respect to the total solid of a composition, More preferably, it is 0.3 mass% or more and 8 mass% or less, More preferably, it is 0.5 mass% or more and 5 mass% or less. It is as follows. Within this range, good curability can be obtained.

  When the composition of this invention is a curable composition, the curable composition may further contain the arbitrary components explained in full detail as needed further. Hereinafter, optional components that the curable composition may contain will be described.

[Sensitizer]
The curable composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator (E) and increasing the photosensitive wavelength.
As the sensitizer that can be used in the present invention, those that sensitize the polymerization initiator (E) with an electron transfer mechanism or an energy transfer mechanism are preferable.

Examples of the sensitizer include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
That is, for example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), Thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squarily (Eg, squarylium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzene , Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, etc. And aromatic ketone compounds, and heterocyclic compounds such as N-aryloxazolidinones.

  More preferred examples of the sensitizer that can be used in the present invention include compounds represented by the following general formulas (e-1) to (e-4).

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

In formula (e-2), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ² —. Here -L ² - represents -O- or -S-. Moreover, W is synonymous with what was shown to Formula (e-1).

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

In formula (e-4), A ³ and A ⁴ each independently represent —S— or —NR ⁶² , and R ⁶² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. , L ⁴ represents a non-metallic atomic group that forms a basic nucleus of the dye together with adjacent A ³ and a carbon atom, and L ⁵ represents a basicity of the dye combined with adjacent A ⁴ and a carbon atom. Represents a nonmetallic atomic group forming a nucleus, and R ⁶⁰ and R ⁶¹ each independently represent a monovalent nonmetallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring. it can.

The curable composition may or may not contain a sensitizer, but when it is contained, the content of the sensitizer in the curable composition is such that the light absorption efficiency to the deep part and the decomposition efficiency of the initiator are From the viewpoint, the solid content is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 15% by mass or less.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

Moreover, as a preferable sensitizer that can be contained in the curable composition, in addition to the sensitizer, a compound represented by the following general formula (II) and a compound represented by the general formula (III) are selected. At least one kind.
These may be used alone or in combination of two or more.

In general formula (II), 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. Represent. n represents an integer of 0 to 5, n ′ represents an integer of 0 to 5, and n and n ′ are not both 0. When n is 2 or more, a plurality of R ¹¹ may be the same or different. When n ′ is 2 or more, a plurality of R ¹² may be the same or different. In the general formula (II), the isomer with a double bond is not limited to either.

The compound represented by the general formula (II) preferably has a molar extinction coefficient ε at a wavelength of 365 nm of 500 mol ⁻¹ · L · cm ⁻¹ or more, and ε at a wavelength of 365 nm of 3000 mol ⁻¹ · L · cm ^{−. 1} or more is more preferable, and ε at a wavelength of 365 nm is most preferably 20000 mol ⁻¹ · L · cm ⁻¹ or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.

Although the preferable specific example of a compound represented by general formula (II) is illustrated below, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group.

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

In the general formula (III), R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. When R ²¹ , R ²² , and R ²³ represent a monovalent nonmetal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted fragrance It is preferably a group heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or 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 decomposition efficiency of the photopolymerization initiator. R ²³ represents a hydrogen atom or a monovalent nonmetallic atomic group. Further, Y is most preferably —N (R ²³ ) —.

  Hereinafter, although the preferable specific example of a compound represented by general formula (III) is shown, this invention is not limited to this. Further, it is not clear about an isomer by a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

[Co-sensitizer]
The curable composition of the present invention preferably further contains a co-sensitizer.
In the present invention, the co-sensitizer has effects such as further improving the sensitivity of the polymerization initiator (E) and the sensitizer to actinic radiation, or suppressing polymerization inhibition of the polymerizable compound (D) by oxygen. .

  Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The curable composition may or may not contain a co-sensitizer. However, when it is contained, the content of these co-sensitizers is from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The range of 0.1% by mass to 30% by mass is preferable with respect to the total solid content of the curable composition, the range of 1% by mass to 25% by mass is more preferable, and the range of 1.5% by mass to 20% is preferable. A range of less than or equal to mass% is more preferred.

[Polymerization inhibitor]
In the present invention, it is preferable to add a polymerization inhibitor in order to prevent unnecessary polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during production or storage of the curable composition.
Examples of the polymerization inhibitor that can be 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-nitrosophenylhydroxylamines, diazonium. Examples include compounds, and cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, and transition metal compounds such as FeCl ₃ and CuCl ₂ .

Further preferred embodiments are as follows.
The phenolic hydroxyl group-containing compound is hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol), It is preferably a compound selected from the group consisting of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), phenolic resins, and cresol resins.

  N-oxide compounds are 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picoline A compound selected from the group consisting of acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide is preferred.

  Piperidine 1-oxyl free radical compounds include piperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1 -Oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimide A compound selected from the group consisting of -2,2,6,6-tetramethylpiperidine 1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical Is preferred.

  The pyrrolidine 1-oxyl free radical compounds are preferably 3-carboxyproxyl free radicals (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).

  The N-nitrosophenylhydroxylamines are preferably compounds selected from the group consisting of N-nitrosophenylhydroxylamine primary cerium salts and N-nitrosophenylhydroxylamine aluminum salts.

  A compound in which the diazonium compounds are selected from the group consisting of 4-diazophenyldimethylamine hydrogen sulfate, 4-diazodiphenylamine tetrafluoroborate, and 3-methoxy-4-diazodiphenylamine hexafluorophosphate Is preferred.

  Although the suitable polymerization inhibitor which can be used for this invention is illustrated below, this invention is not restrict | limited to these. In addition, as a phenol type polymerization inhibitor, the following exemplary compound (P-1)-(P-24) is mentioned.

  Examples of the amine polymerization inhibitor include the following exemplary compounds (N-1) to (N-7).

  Examples of the sulfur polymerization inhibitor include the following exemplary compounds (S-1) to (S-5).

  Examples of the phosphite polymerization inhibitor include the following exemplary compounds (R-1) to (R-5).

  Furthermore, each compound shown below can also be used as a suitable polymerization inhibitor.

  Among the above exemplified compounds, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-) are preferable. Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol) phenolic hydroxyl group-containing compounds, piperidine 1-oxyl free radical compounds, or 2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido- 2,2,6,6-tetramethylpiperidine 1-oxylfuryl Piperidine 1-oxyl free of radicals, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical A radical compound, or an N-nitrosophenylhydroxylamine compound of N-nitrosophenylhydroxylamine primary cerium salt and N-nitrosophenylhydroxylamine aluminum salt, more preferably 2,2,6,6-tetramethylpiperidine 1 -Oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 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-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1- Piperidine 1-oxyl free radical compound of oxyl free radical, or N-nitrosophenylhydroxylamine compound of N-nitrosophenylhydroxylamine cerium salt and N-nitrosophenylhydroxylamine aluminum salt, more preferably -nitrosophenyl N-nitrosophenylhydroxylamine compounds of hydroxylamine primary cerium salt and N-nitrosophenylhydroxylamine aluminum salt.

A preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by weight or more and 10 parts by weight or less, and more preferably 0.01 parts by weight or more and 8 parts by weight or less with respect to 100 parts by weight of the polymerization initiator (E). It is preferable that it is in the range of 0.05 parts by mass or more and 5 parts by mass or less.
By setting it as the said range, the curing reaction suppression in a non-image part and the curing reaction acceleration in an image part are fully performed, and image forming property and a sensitivity become favorable.

[Other additives]
Furthermore, in order to improve the physical properties of the cured film, a known additive such as a plasticizer or a sensitizer may be added to the curable composition.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added with respect to the total mass of the polymerizable compound and the binder polymer.

[Ultraviolet absorber]
The curable composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a compound represented by the following general formula (I) which is a conjugated diene compound is particularly preferable.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² May be the same as or different from each other, but do 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 a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-hexyl group, a cyclohexyl group, and n-decyl. Group, n-dodecyl 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 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 and the like, and methyl group, ethyl group, propyl group, n-butyl group and n-hexyl group are preferred. Arbitrariness.
The alkyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent of the alkyl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, Halogen atom, acylamino group, acyl group, alkylthio group, arylthio group, hydroxy group, cyano group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, An arylsulfonyl group etc. are mentioned.

The aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² may be a single ring or a condensed ring, and is any of a substituted aryl group having a substituent or an unsubstituted aryl group. There may be. For example, a phenyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group, fluorenyl group, etc. can be mentioned. Examples of the substituent of the substituted aryl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, an acylamino group, an acyl group, an alkylthio group, an arylthio group, a hydroxy group, and a cyano group. Group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, arylsulfonyl group and the like. Of these, a substituted or unsubstituted phenyl group, 1-naphthyl group, and 2-naphthyl group are preferable.

R ¹ and R ² may form a cyclic amino group together with the nitrogen atom to which R ¹ and R ² are bonded. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.

Among the above, R ¹ and R ² are each a lower alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl). , 2-ethylhexyl, tert-octyl, etc.) or a substituted or unsubstituted phenyl group (for example, tolyl group, phenyl group, anisyl group, mesityl group, chlorophenyl group, 2,4-di-tert-amylphenyl group, etc.) Is preferred. It is also preferred that R ¹ and R ² are combined to form a ring (for example, a piperidine ring, a pyrrolidine ring, a morpholine ring) containing the nitrogen atom represented by N in the formula.

In the general formula (I), R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant σ _p value (hereinafter simply referred to as “σ _p value”) of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σ _p value of 0.30 or more and 0.8 or less.
Hammett's rule was found in 1935 by L. L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σ _p value and σ _m value, and these values are described in many general books. A. Dean ed. “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemical Domains Extra”, 122, 96-103, 1979 (Nan-Edo), Chemical Reviews, 91, 165-195, detailed in 1991. In the present invention, it does not mean that the values known in the literature described in these documents are limited to only certain substituents, but within the range when measured based on Hammett's law even if the value is unknown. Of course, it is included as long as it is included.

Specific examples of the electron withdrawing group having a σ _p value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, and a nitro group. Dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, An alkyl group substituted with at least two or more halogen atoms, an alkoxy group substituted with at least two or more halogen atoms, an aryloxy group substituted with at least two or more halogen atoms, or at least two or more halogen atoms Alkyl substituted with Amino group, at least two an alkylthio group substituted with a halogen atom, sigma _p value of 0.20 or more other electron-withdrawing aryl group substituted by group, a heterocyclic group, a chlorine atom, a bromine atom, an azo Group, or selenocyanate group. Of these substituents, the group that can further have a substituent may further have a substituent as described above.

Among these, as R ³ and R ⁴ , an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferable. In particular, an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferable.
Among the above, in the present invention, R ³ is preferably a group selected from a cyano group, —COOR ⁵ , —CONHR ⁵ , —COR ⁵ , —SO ₂ R ⁵ , and R ⁴ is a cyano group. A group selected from the group, —COOR ⁶ , —CONHR ⁶ , —COR ⁶ , —SO ₂ R ⁶ is preferred. R ⁵ and R ⁶ each independently represents 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 those in R ¹ and R ² , and the preferred embodiments are also the same.
R ³ and R ⁴ may be bonded to each other to form a ring.

Moreover, at least one of the above R ¹ , R ² , R ³ , and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer. In the case of the copolymer, other monomers include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (for example, esters derived from acrylic acids such as methacrylic acid, preferably lower alkyl esters and amides such as Acrylamide, methacrylamide, t-butyl acrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate , Lauryl methacrylate, methylenebisacrylamide, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl laurate, etc.), acrylonitrile, methacryloni Tolyl, aromatic vinyl compounds (for example, styrene and its derivatives, such as vinyltoluene, divinylbenzene, vinylacetophenone, sulfostyrene, and styrenesulfinic acid), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether ( For example, vinyl ethyl ether), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine, and the like.
Of these, acrylic acid esters, methacrylic acid esters, and aromatic vinyl compounds are particularly preferable.
Two or more of the other monomer compounds can be used together. For example, n-butyl acrylate and divinylbenzene, styrene and methyl methacrylate, methyl acrylate and methacrylate acid, or the like can be used in combination.

  Hereinafter, preferable specific examples [Exemplary compounds (1) to (14)] of the compound represented by the general formula (I) are shown. However, the present invention is not limited to these.

  The ultraviolet absorbers represented by the general formula (I) are disclosed in JP-B-44-29620, JP-A-53-128333, JP-A-61-169831, JP-A-63-53543, JP-A-63-53544. In addition, it can be synthesized by the methods described in JP-A 63-56651 and other publications and WO 2009/123109 pamphlet. Specifically, the exemplified compound (1) can be synthesized by the method described in paragraph No. 0040 of WO2009 / 123109 pamphlet.

  The curable composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.1% by mass relative to the total solid content of the composition. 10 mass% is preferable, 0.1 mass%-5 mass% is more preferable, 0.1 mass%-3 mass% is especially preferable.

The composition or curable composition of the present invention contains a solvent, and the solvent can be composed of various organic solvents. As an organic solvent which can be used, the same organic solvent as the solvent (C) in the above-mentioned dispersion composition is mentioned.
These organic solvents can be used alone or in combination. It is preferable that the density | concentration of solid content in the composition of this invention or a curable composition is 2-60 mass%.

[Method for producing transparent film]
As a method for producing the transparent film of the present invention, a step of applying the above-described composition or curable composition on a wafer by a spray method, a roll coating method, a spin coating method (spin coating method), a bar coating method,
And a second heating step at a temperature higher than the heating temperature in the first heating step.
The conditions in the first heating step are the same as the conditions described later as the pre-bake conditions in the step (a) in the microlens manufacturing method.
The conditions in the second heating step are the same as those described later as the post-bake conditions in the step (d) in the microlens manufacturing method.

<Micro lens>
Since the composition or curable composition of the present invention can form a transparent film having a high refractive index and a high transmittance, it can be very suitably 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.

[Microlens manufacturing method]
The method for producing a microlens using the composition or the curable composition of the present invention is not particularly limited, and a commonly used method can be applied. For example, a step of post-baking and shaping the transparent film described above And a manufacturing method having a dry etching step.
The step of post-baking and shaping the transparent film is the same as that described later in detail as step (f).
The dry etching process is the same as that described later in detail as the process (g).
As a preferred embodiment of the method for producing a microlens using the curable composition of the present invention, a production method including at least the following steps (A) to (D) can be mentioned.
(A) The process of forming the coating film of the curable composition of this invention on a board | substrate.
(B) A step of irradiating at least a part of the coating film with radiation.
(C) A step of developing the coated film after irradiation.
(D) A step of heating the coated film after development.

Hereinafter, these steps will be described.
Step (a) In this step, the curable composition is preferably applied as a liquid composition to the substrate surface, and the solvent is removed by pre-baking to form a coating film on the substrate.
Examples of the substrate include a glass substrate, a silicon wafer, a substrate on which various metal layers are formed, a substrate on which an on-chip color filter for an image sensor is applied, and the like.
The coating method is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method, or a bar coating method can be employed.
Prebaking conditions vary depending on the type and amount of each component used, but are usually about 60 to 120 ° C. for about 30 seconds to 15 minutes. The thickness of the coating film to be formed is preferably about 0.5 to 20 μm as a value after pre-baking.

(B) Step In this step, radiation is applied to at least a part of the formed coating film.
When irradiating only a part of the coating film with radiation, it is irradiated through a mask having a predetermined pattern.
As radiation to be irradiated, for example, 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, charged particle beams such as electron beams, etc. may be used. Of these, ultraviolet rays are preferred.
Although an exposure amount can be suitably selected according to the structure of a curable composition, etc., about 50-2,000 J / m < ² > is preferable.

(C) Step In this step, the exposed coating film is developed with a developer, preferably an alkali developer, and a pattern having a predetermined shape is formed by removing the unirradiated portion of the radiation.
Examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, and triethylamine. , Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [ 4.3.0] -5-nonene and other aqueous solutions. Further, a water-soluble organic solvent such as methanol and ethanol, a surfactant, and various organic solvents can be added to the alkali developer.
As a developing method, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method or the like can be employed. In addition, after developing with an alkali developing solution, it is usually washed, for example, with running water.
The development time varies depending on the composition of the curable composition and the composition of the developer, but is usually about 30 to 120 seconds at room temperature.

(D) Process In this process, the said coating film is hardened by heating (post-baking) the coating film after image development with heating apparatuses, such as a hotplate and oven.
In this post-baking, the heating temperature is usually 120 to 250 ° C, preferably 160 to 230 ° C. The heating time varies depending on the heating means, but is usually about 5 to 30 minutes when heated on a hot plate, and usually about 30 to 90 minutes when heated in an oven.
Further, in the post-baking, a step baking method in which heating is performed twice or more can be adopted.
Another preferred embodiment of the method for producing a microlens using the curable composition of the present invention includes a forming method including at least the following steps (a) to (g).

(A) Step of forming a coating film on a substrate such as a color filter using the curable composition of the present invention (b) Heating the coating film to dry the coating film (or drying and curing) Or a step of obtaining a high refractive index film (transparent film) by performing at least one of exposure and curing of the coating film with a light source of appropriate wavelength (g-line, i-line, etc.) ( c) Step of forming a resist coating film on the high refractive index film after the heating (d) Step of exposing the resist coating film with a light source of appropriate wavelength (g-line, i-line, etc.) (e) The exposure Step (f) of developing the resist film and forming a resist pattern after the step (f) Step of shaping the resist into a lens by heating (g) Part of the high refractive index film and the resist pattern by dry etching Removing the high refractive index film. Process of shaping to's like

Hereinafter, these steps will be described.
-(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 application method include the same method as in the step (A).

-(B) Process-
In this step, a preferable embodiment of heating the coating film includes a two-step heat treatment of pre-baking and post-baking.
Prebaking conditions vary depending on the type and amount of each component used, but are usually about 60 to 120 ° C. for about 30 seconds to 15 minutes. The thickness of the coating film to be formed is preferably about 0.5 to 20 μm as a value after pre-baking. This pre-baking step may be omitted.
Next, the coating film is cured by heating (post-baking) with a heating device such as a hot plate or an oven. The post-baking conditions are usually 120 ° C. to 300 ° C. for about 30 seconds to 60 minutes. In addition, you may accelerate | stimulate hardening by performing exposure before a post-baking process.
In the case where the coating film is exposed and cured with a light source having an appropriate wavelength (g-line, i-line, etc.), the radiation to be irradiated includes the same radiation type and exposure amount as in the step (b).

-(C) Process-
In this step, a resist coating film is formed on the high refractive index film. As this resist, a commercially available resist that can be patterned by ultraviolet exposure can be used. The resist coating film is pre-baked in the same manner as in the step (a).
-(D) Process-
In this step, the coating film is exposed in a pattern using a mask. Examples of the radiation to be irradiated include the same radiation types and exposure amounts as those in the step (b).
-(E) Process-
In this step, the resist coating film after exposure is developed with a developer, preferably an alkali developer, and a pattern having a predetermined shape is formed by removing an unirradiated part or an irradiated part of the radiation.
Examples of the alkali developer include alkali developers similar to those in the step (c).
Examples of the developing method include the same methods as those described above for step (c).
The development time is the same as that described above for the step (c).

-(F) Process-
In this step, the resist after forming the pattern is shaped into a lens by post-heating (post-baking) with a heating device such as a hot plate or oven. The post-baking conditions are usually 120 ° C. to 300 ° C. for about 30 seconds to 60 minutes. Moreover, in order to shape into a lens shape, the step baking method etc. which heat 2 times or more can also be employ | adopted.

-(G) Process-
Dry etching can be performed by a known method (for example, JP 2010-204154 A).

In this way, a target microlens can be manufactured.
According to the method for manufacturing a microlens of the present invention, a high-definition microlens and a microlens array having excellent characteristics (for example, high refractive index and high transparency) can be easily formed with a high product yield.

  The microlens in the present invention is formed from the composition or curable composition of the present invention, has an excellent balance of characteristics, and is a liquid crystal such as various OA devices, liquid crystal televisions, mobile phones, projectors, etc. It can be used very suitably for an imaging optical system of an on-chip color filter such as a display element, a facsimile machine, an electronic copying machine, a solid-state image sensor, an optical fiber connector, or the like.

<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.
Since the solid-state imaging device of the present invention includes a microlens having a high refractive index and high transparency, noise can be reduced and excellent color reproducibility is exhibited.
The solid-state imaging device of the present invention is a configuration including a microlens formed using the composition or curable composition of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. The substrate has a light receiving element made of a plurality of photodiodes and polysilicon forming a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.), and the microlens is provided on a color filter. Examples include the configuration.
Although there is no restriction | limiting in particular as a manufacturing method of the solid-state image sensor of this invention, As one preferable aspect, a red pixel, a blue pixel, a solid-state image sensor substrate which has at least a photodiode, a light shielding film, and a device protective film, And forming a green pixel,
Applying and heating the aforementioned composition or curable composition;
Forming a resist pattern;
A step of post-baking and shaping the formed resist pattern into a lens shape, and a dry etching step.
As the step of applying and heating the composition or the curable composition, the step of forming the coating film on the substrate in the steps (a) and (b) in the above-described microlens manufacturing method and the coating film are heated. Then, it is the same as the process of drying (or drying and curing) the coating film.
The step of forming the resist pattern is the same as the step (d) and the step (e) in the above-described microlens manufacturing method.
The step of post-baking and shaping the formed resist pattern into a lens shape is the same as the step (f) in the above-described microlens manufacturing method.
The dry etching process is the same as the process (g) in the above-described microlens manufacturing method.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

<Preparation Example 1>
[Preparation of titanium dioxide dispersion 1 (dispersion composition)]
Dispersion treatment is performed as follows using a Ultra Apex mill (trade name) manufactured by Kotobuki Kogyo Co., Ltd. as a circulation type dispersion device (bead mill) for a mixed liquid having the following composition, and titanium dioxide dispersion as a dispersion composition Liquid 1 was obtained.
~composition~
-Titanium dioxide (Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C)): 180 parts-Resin of "Exemplary Compound 33" (dispersion resin (B)): 48.6 parts-Propylene glycol monomethyl ether acetate (PGMEA): 300 parts

  The weight average molecular weight of the resin of Exemplary Compound 33 is 38000.

The dispersing device was operated under the following conditions.
・ Bead diameter: φ0.05mm
・ Bead filling rate: 75% by volume
・ Peripheral speed: 8m / sec
・ Pump supply amount: 10Kg / hour
・ Cooling water: Tap water ・ Bead mill annular passage volume: 0.15L
・ Amount of liquid mixture to be dispersed: 0.44 Kg

After the start of dispersion, the average particle size was measured at 30 minute intervals (one pass time).
The average particle diameter decreased with the dispersion time (pass number), but the amount of change gradually decreased. Dispersion was terminated when the change in the primary particle size when the dispersion time was extended by 30 minutes became 5 nm or less. The primary particle diameter of the titanium dioxide particles in this dispersion was 40 nm.

The primary particle diameter of titanium dioxide in this example was obtained by diluting a mixed liquid or dispersion containing titanium dioxide 80 times with propylene glycol monomethyl ether acetate, and using the dynamic light scattering method for the obtained diluted liquid. It means the value obtained by measuring.
This measurement is the number average particle diameter obtained by using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd.

<Preparation Example 2>
[Preparation of zirconium oxide dispersion (dispersion composition)]
An aqueous zirconium oxychloride solution having a concentration of 50 g / L was neutralized with an aqueous 48 mass% sodium hydroxide solution to obtain a hydrated zirconium suspension. The suspension was filtered and then washed with ion exchanged water to obtain a hydrated zirconium cake. The cake was adjusted to a concentration of 15% by mass in terms of zirconium oxide using ion-exchanged water as a solvent, placed in an autoclave, hydrothermally treated at 150 atm and 150 ° C for 24 hours to obtain a zirconium oxide fine particle suspension, and dried. Water was removed to obtain zirconium oxide fine particles. (Average particle diameter 5 nm).
A zirconium oxide dispersion was prepared in the same manner except that titanium dioxide in the titanium dioxide dispersion prepared in Preparation Example 1 was replaced with the zirconium oxide. The primary particle diameter of the zirconium oxide particles in the zirconium oxide dispersion obtained by measurement in the same manner as in Preparation Example 1 was 10 nm.

<Preparation Example 3>
[Preparation of titanium dioxide dispersion 2 (dispersion composition)]
Dispersion treatment is performed as follows using a Ultra Apex mill (trade name) manufactured by Kotobuki Kogyo Co., Ltd. as a circulation type dispersion device (bead mill) for a mixed liquid having the following composition, and titanium dioxide dispersion as a dispersion composition Liquid 2 was obtained.
~composition~
-Titanium dioxide (Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C)): 180 parts-The following dispersion resin (dispersion resin (B)): 48.6 parts-Propylene glycol monomethyl ether acetate (PGMEA): 300 copies

  The dispersing device was operated under the same conditions as in the adjustment example 1. The primary particle diameter of the titanium dioxide particles in the titanium dioxide dispersion 2 obtained by measurement in the same manner as in Preparation Example 1 was 40 nm.

<Example 1>
[Preparation of composition]
Using the titanium dioxide dispersion 1 (dispersion composition) obtained above, each component was mixed so as to obtain the following composition to obtain a composition (curable composition).
-Composition of curable composition-
-Titanium dioxide dispersion 1 prepared above (dispersion composition) ... 52.86 parts-Binder polymer (J-1) ... 3.27 parts (J-1 mentioned above; weight average molecular weight (Mw) and copolymerization ratio) (Molar ratio) is as described above)
・ Surfactant: 0.30 part (Megafac F781 Fluorosurfactant (manufactured by DIC Corporation)
Dipentaerythritol hexaacrylate: 4.36 parts (polymerizable compound, T-1 below)
・ Oxime polymerization initiator: 0.30 part (photopolymerization initiator, IRGACURE OXE-01 (K-1 below) manufactured by BASF)
Propylene glycol monomethyl ether acetate (PGMEA) 40.0 parts

(Preparation of transparent film)
The curable composition obtained above was applied onto a 12-inch silicon wafer by spin coating, and then heated at 100 ° C. for 2 minutes on a hot plate to obtain a coating film having a thickness of 1.05 μm. Further, this 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]
The refractive index with respect to the light of wavelength 500nm of a transparent film was measured with respect to the board | substrate obtained above using the ellipsometry by JA Woollam Japan. Moreover, regarding this transparent film, the light transmittance over the entire wavelength region of 400 nm to 700 nm was measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
The results of the refractive index of the transparent film are shown in Table 1 below. In addition, when the light transmittance of this transparent film was measured from 400 nm to 700 nm, it showed a light transmittance of 92% or more in any of the measurement range immediately after coating.

[Evaluation of the coated surface after coating over time]
The sample coated with the curable composition as described above was allowed to stand at room temperature for 24 hours, and the transparency was visually evaluated as 5 to 1. The results are shown in Table 1 below.
5: Level without any change in transparency and no problem.
4: Transparency in the peripheral part slightly changes, but there is no change in the central part, and there is no problem in practical use. Level 3: slight change is recognized in the peripheral part and in the central part, but there is no problem in practical use. : Peripheral part and center part have non-uniform parts, and there is a problem in practical use. Level 1: There are non-uniform parts on the entire surface, clearly unacceptable level.

[Evaluation of refractive index of transparent film after development of etching resist]
A positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) is further applied on the cured film as a transparent film formed as described above by a spin coater, and heat treatment is performed at 100 ° C. for 1 minute. The photoresist layer was formed so that the film thickness was 0.8 μm. Next, an entire exposure of 300 mJ / cm ² was performed with an i-line stepper (FPA 3000i5, manufactured by Canon Inc.), and a heat treatment was performed at 110 ° C. for 1 minute, followed by developing solution FHD-5 (Fuji Film Electronics Materials). The photoresist layer on the transparent film (cured film) was peeled off. The refractive index of the transparent film (cured film) after the treatment was measured according to the above method.
The results are shown in Table 1 below together with the value of the change in refractive index after the development processing obtained from [refractive index after development processing]-[refractive index before development processing].

<Examples 2 to 43, Comparative Examples 1 to 9>
Except for changing the type of dispersion in the curable composition, the type of binder polymer, the type of surfactant, and the surfactant content relative to the total solid content in the curable composition as shown in Table 1 below, Table 1 shows the results of preparing and evaluating the curable compositions of Examples 2 to 43 and Comparative Examples 1 to 9 according to Example 1. Here, when changing the content of the surfactant, the addition amount of the surfactant is increased or decreased, and the total solid content in the composition is constant (that is, the solid content concentration is constant). According to increase / decrease of the addition amount of the said surfactant, it changed by increasing / decreasing the addition amount of a binder polymer (F). In addition, when the light transmittance of these transparent films was measured from 400 nm to 700 nm, a light transmittance of 92% or more was exhibited in any of the measurement ranges immediately after coating.

<Examples 44 to 46>
[Preparation of composition]
Using the titanium dioxide dispersion 2 (dispersion composition) obtained above, each component was mixed so as to obtain the following composition, whereby a composition (curable composition) of Example 44 was obtained.
-Composition of curable composition-
-Titanium dioxide dispersion 2 prepared above (dispersion composition) ... 52.86 parts-Binder polymer (J-5) ... 3.27 parts (J-5 mentioned above; weight average molecular weight (Mw) and copolymerization ratio) (Molar ratio) is as described above)
・ Surfactant: 0.30 part (Megafac F781 Fluorosurfactant (manufactured by DIC Corporation)
-Epoxy compound: 4.36 parts (polymerizable compound, product name: EHPE 3150 (manufactured by Daicel Chemical Industries, Ltd.))
Oxime polymerization initiator: 0.30 part (photopolymerization initiator, IRGACURE OXE-01 (K-1) manufactured by BASF)
Propylene glycol monomethyl ether acetate (PGMEA) 40.0 parts p-methoxyphenol (polymerization inhibitor) 0.001 part In the curable composition of Example 44, the interface with respect to the total solid content in the curable composition Except changing the content of the activator as shown in Table 1 below, the curable compositions of Examples 45 and 46 were prepared according to Example 44. Here, when changing the content of the surfactant, the amount of the surfactant added is increased or decreased, and the total solid content in the composition is constant (that is, the solid content concentration is constant). According to increase / decrease of the addition amount of the said surfactant, it changed by increasing / decreasing the addition amount of a binder polymer (F). Table 1 shows the results of evaluating the curable compositions of Examples 44 to 46 according to Example 1.
In addition, when the light transmittance of these transparent films was measured from 400 nm to 700 nm, a light transmittance of 92% or more was exhibited in any of the measurement ranges immediately after coating.

The notation “TiO ₂ −1” in the column of metal oxide particles (A) means that the titanium dioxide dispersion 1 prepared in Preparation Example 1 was used as the dispersion composition, and “ZrO ₂ ”. The notation means that the zirconium oxide dispersion prepared in Preparation Example 2 was used as the dispersion composition, and the expression “TiO ₂ -2” was adjusted in Preparation Example 3 as the dispersion composition. This means that the titanium dioxide dispersion 2 was used.
J-2 to J-6 in the column of the binder polymer (F) are binder polymers having the above-described structure, weight average molecular weight (Mw) and copolymerization ratio (molar ratio).
“Surfinol 465” in the surfactant (G) column is Surfinol 465 (nonionic surfactant manufactured by Nissin Chemical), and “KF-6001” is KF-6001 (silicone surfactant Shin-Etsu Silicone). ).
J-7 of the binder polymer used in Comparative Example 9 has the structure, weight average molecular weight (Mw) and copolymerization ratio (molar ratio) described below, and is a repetition derived from benzyl (meth) acrylate. It is a comparative binder polymer containing no units.

  From Table 1, the film formed using the composition of the present invention (curable composition) has a small change with time of the coated surface state after application of the composition, and a decrease in the refractive index after development processing. I understand that it is small. Moreover, the transparent film formed using the composition (curable composition) of the present invention had a high refractive index.

In the above embodiment, an example in which a transparent film is formed on a silicon wafer has been described. However, when a solid-state imaging device is manufactured, a photodiode, a light shielding film, a device protection film, and the like are formed on the silicon wafer. It may be replaced with a solid-state image sensor substrate.
On the silicon wafer on which the photodiode and the transfer electrode are formed, a light shielding film made of tungsten having an opening only in the light receiving portion of the photodiode is formed, and the entire surface of the formed light shielding film and the photodiode light receiving portion (opening in the light shielding film) A device protective layer made of silicon nitride is formed so as to cover the substrate.

Next, a red pixel, a blue pixel, and a green pixel having a side length of 1.4 μm are formed on the formed device protection layer by the method described in Example 16 of Japanese Patent Application Laid-Open No. 2010-210702. Each was formed to create a color filter.
On top of this, the curable compositions of the examples prepared as described above were applied to a film thickness of 1.5 μm, heated at 100 ° C. for 2 minutes, heated on a hot plate, and then heated at 200 ° C. for 5 minutes. The plate was heated and cured.
Further, HPR-204ESZ-9-5 mPa · s (resist solution manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied thereon and heated on a hot plate at 90 ° C. for 1 minute. This coating film was exposed at 100 mJ / cm ² by an i-line stepper (product name: FPA-3000i5 +, manufactured by Canon Inc.) through a mask having a large number of square patterns with sides of 1.4 μm. Here, the mask was arranged so that a large number of square patterns in the mask were at positions corresponding to the red pixel, blue pixel, and green pixel in the color filter, respectively.

  This was subjected to paddle development for 60 seconds at room temperature using an alkaline developer HPRD-429E (Fuji Film Electronics Materials Co., Ltd.), and then rinsed with pure water for 20 seconds in a spin shower. Thereafter, the substrate was washed with pure water, and then the substrate was dried at high speed to form a resist pattern. Post-baking was performed with a hot plate at 200 ° C. for 300 seconds, and the resist was shaped into a lens shape.

The substrate obtained as described above was subjected to a dry etching process under the following conditions using a dry etching apparatus (manufactured by Hitachi High-Technologies: U-621), and the transparent film of the present invention having a high refractive index was obtained. It was processed so that it could be used as a microlens.
・ RF power: 800W
・ Antenna bias: 100W
・ Wafer bias: 500W
-Chamber internal pressure: 0.5 Pa
-Substrate temperature: 50 ° C
Mixed gas type and flow rate: CF ₄ / C ₄ F ₆ / O ₂ / Ar = 175/25/50/200 ml / min Photoresist etching rate: 140 nm / min

  When an image was taken using the obtained device, an image with good sensitivity could be obtained even in a dark room.

Claims (16)

  Repeating units obtained by polymerizing titanium oxide particles or zirconium oxide particles as metal oxide particles (A), repeating units obtained by polymerizing benzyl (meth) acrylate, and alkyl (meth) acrylates containing ethylene oxide groups A composition containing a binder polymer (F) containing a unit and a repeating unit obtained by polymerizing isobutyl (meth) acrylate, and a surfactant (G), wherein the surfactant (G) is contained The composition whose quantity is 0.0010 mass%-3.0 mass% with respect to the total solid of the said composition. Titanium oxide particles or zirconium oxide particles as metal oxide particles (A), a binder polymer (F) containing a repeating unit obtained by polymerizing benzyl (meth) acrylate, a surfactant (G) , p Dispersion resin which is a resin having a repeating unit having a group X having a functional group of Ka14 or less and an oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain and containing a basic nitrogen atom A composition containing (B), wherein the content of the surfactant (G) is 0.0010% by mass to 3.0% by mass with respect to the total solid content of the composition.   The composition according to claim 1 or 2, wherein the surfactant (G) is a fluorine-based surfactant or a nonionic surfactant. A composition according content in any one of claims 1 to 3, which is 0.50 wt% to 3.0 wt% based on the total solids of the composition of the surfactant (G). The composition according to any one of claims 1 to 4 , comprising titanium oxide particles as the metal oxide particles (A). The composition according to any one of claims 1 to 5 , wherein the binder polymer (F) further contains a repeating unit obtained by polymerizing (meth) acrylate. The composition according to claim 2, wherein the binder polymer (F) has an ethylene oxide group. To claim 2 which contains both of the repeating unit obtained by polymerization of the binder polymer (F) is further repeat unit and isobutyl (meth) acrylate obtained by polymerizing an alkyl (meth) acrylate containing an ethylene oxide group The composition as described. It is an object for micro lens formation, The composition of any one of Claims 1-8 . Transparent film formed from the composition according to any one of claims 1-9. A microlens formed using the transparent film according to claim 10 . The microlens according to claim 11 , wherein the microlens is formed by dry etching the transparent film. Solid-state imaging device having a micro-lens according to claim 11 or 12. Applying the composition according to any one of claims 1 to 9 on a wafer;
A transparent film manufacturing method comprising: a subsequent first heating step; and a second heating step at a temperature higher than the heating temperature in the first heating step. A method for producing a microlens, comprising a step of post-baking and shaping the transparent film according to claim 10 and a dry etching step. Forming a red pixel, a blue pixel, and a green pixel on a solid-state imaging device substrate having at least a photodiode, a light shielding film, and a device protection film;
Applying and heating the composition according to any one of claims 1 to 9 ,
Forming a resist pattern;
A process of post-baking and shaping the formed resist pattern into a lens shape, and a dry etching process;
A method for manufacturing a solid-state imaging device.