JP2010037440A - Resin composition, optical film, and optical member - Google Patents

Abstract

［Ｒ^１＝炭素数１〜３のアルキル基又はシアノ基；ａ＝０〜４の整数；Ｒ＝４価の有機基；ｎ＝１〜４の整数；ｍ＝１〜１０００００の整数］から選ばれる少なくとも１種、（Ｂ）周期律表第４族元素の酸化物を主成分とする、動的光散乱で測定した粒子径が１〜１００ｎｍの範囲内の粒子、（Ｃ）常温で液体であり、反応性基を有する化合物、並びに、（Ｄ）有機溶媒を含有し、前記成分（Ｃ）の割合が、組成物中の（Ｄ）有機溶剤を除く成分の合計量を１００重量％としたときに、３〜２０重量％の範囲内である樹脂組成物。
【選択図】図１The present invention provides a resin composition having excellent embedding coating properties on a substrate having holes and giving a cured film having a high refractive index.
(A) A group consisting of a polyamic acid having a structure represented by formula (1) and an imidized polymer thereof

[R ¹ = C 1-3 alkyl group or cyano group; a = 0 to 4 integer; R = tetravalent organic group; n = 1 to 4 integer; m = 1 to 100,000 integer] (B) particles having a particle diameter in the range of 1 to 100 nm as measured by dynamic light scattering, comprising (B) an oxide of a Group 4 element of the periodic table as a main component, and (C) liquid at room temperature. Yes, containing a compound having a reactive group, and (D) an organic solvent, and the proportion of the component (C) is 100% by weight of the total amount of the components excluding the organic solvent (D) in the composition. Sometimes the resin composition is in the range of 3-20% by weight.
[Selection] Figure 1

Description

  The present invention relates to a resin composition, an optical film obtained therefrom, and an optical member. More specifically, a photosensitive composition that can be uniformly embedded in a hole without a void or the like in a hole having a hole having a depth of about 1 to 2 μm and a diameter of about 0.5 to 1 μm, an optical film obtained therefrom, and The present invention relates to an optical member.

  In order to improve the light collection efficiency to the light receiving part of the solid-state imaging device, a resin composition in which metal oxide particles having a high refractive index are introduced into a highly transparent resin such as polyimide is used for the lens or optical waveguide of the solid-state imaging device. It is known.

The applicant of the present application has excellent transparency and a refractive index of more than 1.80 by using a high refractive index resin composition in which a positive photosensitive resin whose exposed portion is dissolved by alkali development and titanium oxide particles are used. And a patent application has been filed (Japanese Patent Application No. 2008-201509). However, when the positive photosensitive high refractive index resin composition is applied to a substrate having a hole having a depth of 1 to 2 μm and a diameter of 1 to 2 μm, voids or peeling occurs in the hole. It was found that the coating solution could not be uniformly embedded in the hole.
This invention is made | formed in view of the above-mentioned problem, and has the outstanding embedding coating property with respect to the base material which has a hole, and it aims at providing the resin composition which gives the cured film of high refractive index.
Furthermore, the present invention provides a high-refractive-index optical film and an optical member that are formed using a resin composition having excellent embedding coating properties for a substrate having holes and in which holes are uniformly embedded. Objective.

  In order to achieve the above-mentioned object, the present inventors have conducted intensive research and applied a polyamic acid and / or imidized polymer having a specific structure and metal oxide particles having high transparency and refractive index at a predetermined amount of room temperature. The present inventors have found that a composition containing a compound that is a liquid and has a reactive group can achieve the above object, and has completed the present invention.

［式（１）中、Ｒ^１はそれぞれ独立に炭素数１〜３のアルキル基又はシアノ基であり、ａはそれぞれ独立に０〜４の整数を示し、Ｒは４価の有機基を示し、ｎは１〜４の整数を示し、ｍは１〜１０００００の整数を示す。］及び、該ポリアミック酸のイミド化重合体からなる群から選ばれる少なくとも１種、
（Ｂ）周期律表第４族元素の酸化物を主成分とする、動的光散乱で測定した粒子径が１〜１００ｎｍの範囲内の粒子、
（Ｃ）常温で液体であり、反応性基を有する化合物、並びに、
（Ｄ）有機溶媒
を含有し、
前記成分（Ｃ）の割合が、組成物中の（Ｄ）有機溶剤を除く成分の合計量を１００重量％としたときに、３〜２０重量％の範囲内である樹脂組成物。
２．前記成分（Ｃ）の反応性基が、ビニル基、オキシラニル基、及びオキセタニル基からなる群から選ばれる少なくとも１種である上記１に記載の樹脂組成物。
３．前記成分（Ｃ）の反応性基が、1分子中に２個以上存在する上記１又は２に記載の樹脂組成物。
４．前記成分（Ａ）が、フェノール性水酸基又はカルボキシル基を有するポリマーである上記１〜３のいずれかに記載の樹脂組成物。
５．さらに、（Ｅ）キノンジアジド化合物を含有する上記１〜４のいずれかに記載の樹脂組成物。
６．前記一般式（１）中のＲが、４価の脂環族基からなる群から選択される上記４又は５に記載の樹脂組成物。
７．前記成分（Ｂ）が、ルチル型酸化チタン粒子である上記１〜６のいずれかに記載の樹脂組成物。
８．前記成分（Ｂ）が、酸化珪素被覆されたルチル型酸化チタン粒子である上記７に記載の樹脂組成物。
９．さらに、（Ｆ）界面活性剤を含有する上記１〜８のいずれかに記載の樹脂組成物。
１０．上記１〜９のいずれかに記載の樹脂組成物を基材に塗布した後、加熱して得られる光学膜。
１１．波長６３３ｎｍでの屈折率が１．７０以上である上記１０に記載の光学膜。
１２．上記１０又は１１に記載の光学膜からなる光学用部材。
１３．上記１〜８のいずれかに記載の感光性組成物を基材に塗布した後、マスクを介して露光、現像して形成される光学用部材。 That is, the present invention provides the following resin composition, optical film and optical member.
1. (A) a polyamic acid having a structure represented by the following general formula (1),

[In Formula (1), R ¹ is each independently an alkyl group having 1 to 3 carbon atoms or a cyano group, a is each independently an integer of 0 to 4, R is a tetravalent organic group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100,000. And at least one selected from the group consisting of imidized polymers of the polyamic acid,
(B) Particles having a particle diameter of 1 to 100 nm as measured by dynamic light scattering, the main component of which is an oxide of a Group 4 element in the periodic table,
(C) a compound that is liquid at room temperature and has a reactive group, and
(D) contains an organic solvent,
The resin composition in which the proportion of the component (C) is in the range of 3 to 20% by weight when the total amount of the components excluding the organic solvent (D) in the composition is 100% by weight.
2. 2. The resin composition according to 1 above, wherein the reactive group of the component (C) is at least one selected from the group consisting of a vinyl group, an oxiranyl group, and an oxetanyl group.
3. 3. The resin composition according to 1 or 2 above, wherein two or more reactive groups of the component (C) are present in one molecule.
4). 4. The resin composition according to any one of 1 to 3, wherein the component (A) is a polymer having a phenolic hydroxyl group or a carboxyl group.
5). Furthermore, (E) The resin composition in any one of said 1-4 containing a quinonediazide compound.
6). 6. The resin composition according to 4 or 5 above, wherein R in the general formula (1) is selected from the group consisting of tetravalent alicyclic groups.
7). 7. The resin composition according to any one of 1 to 6, wherein the component (B) is rutile type titanium oxide particles.
8). 8. The resin composition as described in 7 above, wherein the component (B) is rutile titanium oxide particles coated with silicon oxide.
9. Furthermore, the resin composition in any one of said 1-8 containing (F) surfactant.
10. An optical film obtained by applying the resin composition according to any one of 1 to 9 above to a substrate and then heating it.
11. 11. The optical film as described in 10 above, wherein the refractive index at a wavelength of 633 nm is 1.70 or more.
12 An optical member comprising the optical film as described in 10 or 11 above.
13. An optical member formed by applying the photosensitive composition according to any one of 1 to 8 above to a base material, and then exposing and developing through a mask.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which has the outstanding embedding coating property with respect to the base material which has a hole, and gives the cured film of high refractive index can be provided.
ADVANTAGE OF THE INVENTION According to this invention, the high refractive index optical film and optical member with which the hole was uniformly embedded formed using the resin composition which has the outstanding embedding coating property with respect to the base material which has a hole can be provided.
According to the present invention, a further patterned optical member can be provided.

Hereinafter, the resin composition, optical film, and optical member of the present invention will be described in detail.
I. Resin Composition The resin composition of the present invention (hereinafter referred to as the composition of the present invention) may contain the following components (A) to (F). Among these components, components (A) to (D) are essential components, and components (E) to (G) are optional components that are added according to the purpose.
(A) a polymer having an alkali-soluble group,
(B) Particles having a particle diameter of 1 to 100 nm as measured by dynamic light scattering, the main component of which is an oxide of a Group 4 element in the periodic table,
(C) a compound that is liquid at room temperature and has a reactive group,
(D) Organic solvent (E) Quinonediazide compound (F) Surfactant (G) Additive

The composition of the present invention is (C) a liquid at room temperature, and contains a compound having a reactive group in a predetermined amount range, so that excellent embedding coating property and transparency for a substrate having holes are obtained. An excellent cured film can be formed.
In particular, the composition of the present invention contains (A) a polyamic acid and / or imidized polymer having a predetermined structure, which is a polymer having an alkali-soluble group, and (B) particles. A cured film having excellent transparency and a high refractive index can be formed.

Hereinafter, each component will be described.
(A) Polymer having alkali-soluble group Component (A) used in the present invention is a polymer having an alkali-soluble group. When the polymer of component (A) has an alkali-soluble group, the resin composition can be developed with an alkali.
Examples of the alkali-soluble group that the polymer of component (A) has include a phenolic hydroxyl group and a carboxyl group.
The polymer of component (A) is not particularly limited as long as it has the above alkali-soluble group, but polyamic acid (A-1) having a structure represented by the following general formula (1) and an imide of this polyamic acid It is preferable that it is at least 1 sort (s) chosen from the group which consists of a conversion polymer (A-2).

(A-1) Polyamic acid The polyamic acid used as the component (A) in the present invention has a structure represented by the following general formula (1), and its refractive index (25 ° C., wavelength 400 to 700 nm) is very high. In addition, a cured product having a high refractive index, excellent transparency and heat resistance can be formed.

In formula (1), R ¹ independently represents an alkyl group having 1 to 3 carbon atoms or a cyano group, a represents the number of substitutions of the group R ¹ , and represents an integer of 0 to 4. It is preferred that a is 0 (ie, no substituent) or R ¹ is a cyano group and a is 1.
R represents a tetravalent organic group, and specifically corresponds to a residue obtained by removing an anhydride group from an aliphatic, alicyclic or aromatic tetracarboxylic dianhydride, and the resulting cured product is transparent. Therefore, it is preferably a residue of an alicyclic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. Moreover, since R has a high refractive index, it preferably contains a sulfur atom.
n shows the integer of 1-4 and it is preferable that it is an integer of 2-4.
m represents an integer of 1 to 100,000, and is preferably an integer of 10 to 10,000.

上記式（３）及び（４）中、Ｒ^１、Ｒ、ａ及びｎは、一般式（１）で説明した通りであるため、ここでは省略する。 (A) Production of polyamic acid having structure represented by general formula (1) Component (A) of the present invention comprises a diamine represented by the following general formula (3) and a tetracarboxylic acid represented by the following general formula (4). Obtained by reacting acid dianhydride.

In the above formulas (3) and (4), R ¹ , R, a, and n are as described in the general formula (1), and thus are omitted here.

(B) Diamine represented by general formula (3) Examples of the diamine represented by general formula (3) include 4,4 ′-(p-phenylenedisulfanyl) dianiline, 1,3-bis (4- Aminophenylsulfanyl) benzene, 1,3-bis (4-aminophenolsulfanyl) 5-cyanobenzene, 4,4′-thiobis [(p-phenylenesulfanyl) aniline], 4,4′-bis (4-aminophenyl) Sulfanyl) -p-dithiophenoxybenzene and the like, and 4,4′-thiobis [(p-phenylenesulfanyl) aniline] and the like are preferable.

  The composition of the present invention may contain a polyamic acid other than the polyamic acid having the structure represented by the general formula (1). That is, in addition to the diamine represented by the general formula (3), a diamine that does not contain a sulfur atom can be used in combination as long as the effects of the present invention are not impaired. Examples of the diamine not containing a sulfur atom include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4, 4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 3,4'- Diaminodiphenyl ether, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-Aminophenoxy) phenyl] hexafluoropropyl Pan, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 9,9-bis (4-amino) Phenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4 '-Diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylenediisopropylidene) bisaniline , 4,4 '- (m- phenylene-isopropylidene) can be exemplified bisaniline.

In addition to the above-mentioned diamines not containing sulfur atoms, aromatic diamines having heteroatoms such as diaminotetraphenylthiophene; 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine , Hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7 -Aliphatic or alicyclic diamines such as methanoin danylene dimethylene diamine and tricyclo [6,2,1,0 ^2.7 ] -undecylenedimethyl diamine may be used in combination.

  Of the diamines used for the production of the component (A) polyamic acid, the proportion of the diamine represented by the general formula (3) is preferably 50 mol% or more, more preferably 80 mol% or more, In order to achieve a high refractive index, it is particularly preferably 100 mol%.

(C) Tetracarboxylic dianhydride represented by the general formula (4) The acid anhydride used in the present invention is represented by the general formula (4). In the formula (4), R corresponds to a residue obtained by removing the anhydride group from tetracarboxylic dianhydride. Examples of such compounds include aliphatic, alicyclic or aromatic tetracarboxylic dianhydrides. Since the resulting cured film has excellent transparency, aliphatic and alicyclic tetracarboxylic dianhydrides. Anhydrides are preferred.

Examples of the aliphatic and alicyclic tetracarboxylic dianhydrides include, for example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4 -Cyclopentanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] dodecane-3,5,9,11-tetraone, 1,2,4,5- Cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dihydrate, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetra Carboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3- Zeon, -(2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5 And aliphatic and alicyclic tetracarboxylic dianhydrides such as 1,6-tetracarboxylic dianhydride. Among these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] dodecane- 3,5,9,11-tetraone, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Acid dianhydride and 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] dodecane-3,5,9,11-tetraone 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride is particularly preferred.

  Specific examples of the aromatic tetracarboxylic dianhydride include, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4 ′. -Biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4 '-Biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarbo) Ciphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 4,4 ′-(hexafluoroisopropylidene) bis (phthalic acid) dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis Aromatic tetra such as (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride Carboxylic dianhydrides can be mentioned. Among these, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 4 4,4 '-(Hexafluoroisopropylidene) bis (phthalic acid) dianhydride and 3,3', 4,4'-biphenyltetracarboxylic dianhydride are preferred.

  In addition, since a polyamic acid having a higher refractive index can be obtained, it is also preferable to use a tetracarboxylic dianhydride containing a sulfur atom. Examples of sulfur atom-containing acid anhydrides include 4,4 '-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride.

(D) Reaction of the diamine represented by the general formula (3) and the tetracarboxylic dianhydride represented by the general formula (4) In general, in the aprotic organic solvent such as N-methyl-2-pyrrolidone, the diamine By mixing the compound and acid dianhydride with stirring, the polyamic acid of component (A) can be obtained as a solution. For example, a diamine compound may be dissolved in an organic solvent, and acid dianhydride may be added thereto and mixed with stirring. Alternatively, a mixture of a diamine compound and acid dianhydride may be added to an organic solvent and mixed with stirring. May be. The reaction is usually performed at a temperature of 100 ° C. or lower, preferably 80 ° C. or lower, under normal pressure. However, the reaction may be performed under pressure or under reduced pressure as necessary. The reaction time varies depending on the diamine compound and acid dianhydride used, the organic solvent, the reaction temperature, etc., but is usually in the range of 4 to 24 hours.

式（２）中のＲ^１、ａ、Ｒ、ｎ及びｍは、一般式（１）と同様であるためここでは説明を省略する。 (A-2) Imidized polymer The imidized polymer used in the present invention has a structure represented by the following general formula (2), and a refractive index at a wavelength of 633 nm is usually 1.60 or more, preferably It is 1.68 or more, more preferably 1.70 or more.

Since R ¹ , a, R, n and m in the formula (2) are the same as those in the general formula (1), description thereof is omitted here.

  The imidized polymer (A-2) is heated to 1 to 5 hours at a temperature of 80 to 150 ° C. in a nitrogen atmosphere by adding acetic anhydride and pyridine as a catalyst to the polyamic acid (A-1) solution. Can be obtained.

The ratio of the imidized polymer (A-2) in the component (A) is represented by an imidization ratio (%), preferably in the range of 20 to 80%, and in the range of 50 to 70%. More preferably. If the imidation ratio is less than 20%, the pattern may be peeled off during alkali development, and if it exceeds 80%, the pattern may not be formed during alkali development.
Here, the imidation rate (%) is determined by measuring ¹ H-NMR and calculating from the integral value of protons at the aromatic ring site and protons at the amide site.

  The imidization rate (%) can be adjusted by the amount of imidation catalyst, heating temperature, reaction time, and the like.

The blending amount of the component (A) in the composition of the present invention is preferably in the range of 10 to 50% by weight when the total amount of the component excluding the organic solvent (D) is 100% by weight, More preferably, it is in the range of ˜50% by weight. If the blending amount of component (A) is less than 10% by weight, the refractive index of the cured film may be lowered or a pattern may not be formed during alkali development. If it exceeds 50% by weight, the transmittance of the cured film may be reduced. There is.
In addition, although a component (A) contains the organic solvent normally used for manufacture of a component (A), the organic solvent is not contained in the compounding quantity of a component (A).

(B) Particles having a particle diameter of 1 to 100 nm as measured by dynamic light scattering, the main component of which is an oxide of a Group 4 element in the periodic table. It is an oxide particle of a genus element. By adding a particle component having a high refractive index, the refractive index of the resulting cured product can be further increased.
The particle diameter of the component (B) particles needs to be in the range of 1 to 100 nm, preferably in the range of 1 to 50 nm, and more preferably in the range of 5 to 15 nm. If the particle diameter of the particles is less than 1 nm, secondary agglomeration is likely to occur and the cured film may be whitened. If it exceeds 100 nm, the surface uniformity at the time of thin film formation may be impaired. In the present invention, the particle diameter is a value measured by a dynamic light scattering method.

  Examples of oxide particles that can be used as the component (B) particles include titanium oxide, zirconium oxide, hafnium oxide, and composite particles of these metal oxides with silicon oxide or tin oxide. From the viewpoint of the effect of increasing the rate, titanium oxide and zirconium oxide are preferable.

Titanium oxide has an anatase type and a rutile type depending on the crystal type, but a rutile type is preferred because of its high refractive index and excellent light resistance.
Moreover, since titanium oxide has photocatalytic activity, it is difficult to use it as it is for optical purposes. Therefore, it is preferable that the particle surface is coated with silicon oxide.

  The oxide particles used as the component (B) may be in the form of a powder or a solvent-dispersed sol. Examples of the dispersion medium include methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether and the like.

  Examples of commercially available particles that can be used as the component (B) include, for example, silicon oxide-coated anatase-type titanium oxide-methanol dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., Optlake series), silicon oxide-coated tin oxide Examples include rutile type titanium oxide-methanol dispersion sol (manufactured by Teika, TS series), zirconium oxide-methyl ethyl ketone dispersion sol (manufactured by Osaka Cement, HXU-120JC), and the like.

The blending amount of component (B) in the composition of the present invention is preferably in the range of 30 to 80% by weight, assuming that (D) the total amount of components excluding the organic solvent is 100% by weight, 50 More preferably, it is in the range of -70% by weight. If the proportion of the component (B) is less than 30% by weight, a film having a high refractive index may not be obtained, and if it exceeds 80% by weight, the film forming property may be deteriorated.
In addition, when a component (B) is a solvent dispersion | distribution sol, a dispersion medium is not included in the compounding quantity of a component (B).

(C) Compound that is liquid at room temperature and has a reactive group Component (C) in the composition of the present invention is a compound that is liquid at room temperature and has a reactive group. The liquid at room temperature is necessary for uniformly embedding a substrate having holes, which is a feature of the composition of the present invention. That is, it is considered that by adding a liquid compound, liquid fluidity during spin coating is improved, and penetration and defoaming into the holes are accelerated, thereby exhibiting good hole embedding properties. Moreover, adhesiveness with a base material also improves after hardening by having a reactive group.
Here, “normal temperature” means a range of 15 to 35 ° C.
The “reactive group” is a group that forms a chemical bond with itself and / or polyamic acid by heating, and examples of the group include a vinyl group, an oxiranyl group, and an oxetanyl group.
Moreover, it is preferable that the compound of a component (C) has 2 or more reactive groups in 1 molecule.

Examples of the compound having a vinyl group that can be used as the component (C) include monofunctional vinyl compounds such as styrene, N-vinylpyrrolidone, acryloylmorpholine, benzyl (meth) acrylate, and isobornyl (meth) acrylate; Pentaerythritol monohydroxytri (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, tricyclo [5,2,1,0] A polyfunctional vinyl compound such as decane-3,8-diyldimethyldi (meth) acrylate is exemplified.
Examples of commercially available compounds having a vinyl group include DPHA (dipentaerythritol hexaacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.), biscoat # 700 (ethylene oxide-added bisphenol A diacrylate manufactured by Osaka Organic Industry Co., Ltd.), biscoat # 300 (Osaka Organic) Examples include pentaerythritol monohydroxytriacrylate manufactured by Kogyo Co., Ltd.

Examples of compounds having an oxiranyl group that can be used as component (C) include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and the like. Can be mentioned.
Examples of commercially available compounds having an oxiranyl group include Araldite MY721 (a tetrafunctional oxiranyl group-containing compound manufactured by Huntsman Advanced Materials), EX-1610-P (a tetrafunctional oxiranyl manufactured by Nagase ChemteX Corporation) Group-containing compounds).

Examples of the compound having an oxetanyl group that can be used as the component (C) include xylylene oxetane.
Examples of commercially available compounds having an oxetanyl group include XDO (Xylylene Dioxetane manufactured by Toagosei Co., Ltd.).

  In the composition of the present invention, the amount of component (C) must be within the range of 3 to 20% by weight when the total amount of component (D) excluding the organic solvent is 100% by weight. The content is preferably in the range of 5 to 15% by weight. If the ratio of the component (C) is less than 3% by weight, the hole filling property may be inferior at the time of coating, and if it exceeds 20% by weight, the refractive index of the film may be lowered.

(D) Organic solvent The composition of this invention normally contains the solvent used in the case of manufacture of the polyamic acid of a component (A). When a solvent dispersion sol of particles is used as the oxide particles of component (B), the dispersion medium is also contained in the composition of the present invention. In addition, in order to adjust the viscosity of the composition and improve the coating property of the composition for forming a uniform coating film, an organic solvent can be added separately.

  The organic solvent used in the present invention is not particularly limited, but an aprotic organic solvent is preferable. As the aprotic organic solvent, for example, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), cyclohexanone, N, N-dimethylacetamide (DMAc) and the like are preferable. Besides these, N, N-dimethylformamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, 1 , 2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyrroline, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresolic acid, p-chlorophenol, Anisole, benzene, toluene, xylene, etc. It can gel. These organic solvents are used alone or as a mixture of two or more.

The compounding amount of component (D) organic solvent in the composition of the present invention is usually 100 to 9900 parts by weight, preferably 300 to 1900 parts by weight, more preferably 100 parts by weight of the total solid content excluding the organic solvent. It is in the range of 400 to 1900 parts by weight. If the amount of the organic solvent is less than 100 parts by weight, spin coating may not be possible, and if it exceeds 9900 parts by weight, the required film thickness may not be exhibited.
The compounding amount of the component (D) includes a solvent derived from the polyamic acid and / or imidized polymer solution of the component (A) and a solvent brought in as a dispersion medium for the oxide particle dispersion sol of the component (B). Including.

(E) Quinonediazide compound Component (E) in the composition of the present invention is a quinonediazide compound. The quinonediazide compound is an optional component that is blended when the composition of the present invention is a positive photosensitive composition.
Although the quinonediazide compound is not required for the alkaline aqueous solution, it becomes an indenecarboxylic acid compound by being irradiated with ultraviolet rays and becomes soluble in the alkaline aqueous solution, so that positive patterning is possible.
As the quinonediazide compound, a quinonediazidesulfonic acid ester compound is preferable.
A quinonediazide compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the quinone diazide sulfonic acid ester compound include 1,2-benzoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide--a compound having a phenolic hydroxyl group. Examples thereof include 5-sulfonic acid ester and 1,2-naphthoquinonediazide-6-sulfonic acid ester, and 1,2-naphthoquinonediazide-5-sulfonic acid ester is particularly preferable.

  The quinonediazide sulfonic acid ester compound is obtained, for example, by reacting a polyhydroxy compound and quinonediazidesulfonyl chloride in the presence of a basic catalyst. Usually, the ratio (average esterification ratio) of the quinonediazide sulfonate to the total hydroxyl groups of the polyhydroxy compound is 20% to 100%, preferably 40% to 95%. If the average esterification rate is too low, pattern formation is difficult, and if it is too high, the sensitivity may be lowered. Here, the polyhydroxy compound used is not particularly limited, but specific examples include compounds represented by the following formula.

［式中、Ｚ^１〜Ｚ^１５は、独立に、水素原子、Ｃ_１〜Ｃ_４のアルキル基、Ｃ_１〜Ｃ_４のアルコキシ基、又は水酸基である。但し、Ｚ^１〜Ｚ^５及びＺ^６〜Ｚ^１０の各群において少なくとも１つは水酸基である。また、Ａ^１は、水素原子又はＣ_１〜Ｃ_４のアルキル基である］

[Wherein, Z ^{1 to} Z ¹⁵ are each independently a hydrogen atom, a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group, or a hydroxyl group. However, at least one of each group of Z ^{1 to} Z ⁵ and Z ^{6 to} Z ¹⁰ is a hydroxyl group. A ¹ is a hydrogen atom or a C ₁ -C ₄ alkyl group]

［式中、Ｚ^１６〜Ｚ^３０は、前記Ｚ^１〜Ｚ^１５に関して定義した通りである。但し、Ｚ^１６〜Ｚ^２０、Ｚ^２１〜Ｚ^２５及びＺ^２６〜Ｚ^３０の各群において少なくとも１つは水酸基である。また、Ａ^２〜Ａ^４は、独立に、水素原子又はＣ_１〜Ｃ_４のアルキル基である］

[Wherein, Z ^{16 to} Z ³⁰ are as defined for Z ^{1 to} Z ¹⁵ above. Provided ^that at least one in each group of ^{Z 16 ~Z 20, Z 21 ~Z} 25 and ^Z 26 ^{to Z 30} is a hydroxyl group. A ^{2 to} A ⁴ are independently a hydrogen atom or a C _{1 to} C ₄ alkyl group.]

［式中、Ｚ^３１〜Ｚ^４４は、前記Ｚ^１〜Ｚ^１５に関して定義した通りである。。但し、Ｚ^３１〜Ｚ^３５及びＺ^３６〜Ｚ^３９の各群において少なくとも１つは水酸基である。また、Ａ^５〜Ａ^８は、独立に水素原子又はＣ_１〜Ｃ_４のアルキル基である］

[Wherein Z ^{31 to} Z ⁴⁴ are as defined for Z ^{1 to} Z ¹⁵ above. . Provided ^that at least one in each group of Z 31 ^{to Z 35} and ^Z 36 ^{to Z 39} is a hydroxyl group. A ^{5 to} A ⁸ are each independently a hydrogen atom or a C _{1 to} C ₄ alkyl group]

［式中、Ｚ^４５〜Ｚ^５８は、独立に、水素原子、ハロゲン原子、Ｃ_１〜Ｃ_４のアルキル基、Ｃ_１〜Ｃ_４のアルコキシ基、又は水酸基である。但し、Ｚ^４５〜Ｚ^４８及びＺ^５４〜Ｚ^５８の各群において少なくとも１つは水酸基である。また、Ａ^９及びＡ^１０は、独立に水素原子、Ｃ_１〜Ｃ_４のアルキル基である］

[Wherein, Z ^{45 to} Z ⁵⁸ are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group, or a hydroxyl group. However, at least one of each group of Z ^{45 to} Z ⁴⁸ and Z ^{54 to} Z ⁵⁸ is a hydroxyl group. A ⁹ and A ¹⁰ are independently a hydrogen atom or a C ₁ -C ₄ alkyl group]

［式中、Ｚ^５９〜Ｚ^８０は、前記Ｚ^１〜Ｚ^１５に関して定義した通りである。但し、Ｚ^５９〜Ｚ^６３、Ｚ^６４〜Ｚ^６７、Ｚ^７２〜Ｚ^７５及びＺ^７６〜Ｚ^８０の各群において少なくとも１つは水酸基である。また、Ａ^１１〜Ａ^１８は、独立に水素原子又はＣ_１〜Ｃ_４のアルキル基である］

[Wherein, Z ^{59 to} Z ⁸⁰ are as defined for Z ^{1 to} Z ¹⁵ above. Provided ^that at least one in each group of ^{Z 59 ~Z 63, Z 64 ~Z} 67, Z 72 ~Z 75 and ^Z 76 ^{to Z 80} is a hydroxyl group. A ^{11 to} A ¹⁸ are each independently a hydrogen atom or a C _{1 to} C ₄ alkyl group]

［式中、Ｚ^８１〜Ｚ^９８は、前記Ｚ^１〜Ｚ^１５に関して定義した通りである。但し、Ｚ^８１〜Ｚ^８５、Ｚ^８６〜Ｚ^８９、Ｚ^９０〜Ｚ^９３及びＺ^９４〜Ｚ^９８の各群において少なくとも１つは水酸基である。また、Ａ^１９〜Ａ^２４は、独立に水素原子又はＣ_１〜Ｃ_４のアルキル基である］

[Wherein, Z ^{81 to} Z ⁹⁸ are as defined for Z ^{1 to} Z ¹⁵ above. Provided ^that at least one in each group of ^{Z 81 ~Z 85, Z 86 ~Z} 89, Z 90 ~Z 93 and ^Z 94 ^{to Z 98} is a hydroxyl group. A ^{19 to} A ²⁴ are each independently a hydrogen atom or a C _{1 to} C ₄ alkyl group]

［式中、Ｚ^９９〜Ｚ^１２１は、前記Ｚ^１〜Ｚ^１５に関して定義した通りである。但し、Ｚ^９９〜Ｚ^１０３、Ｚ^１０４〜Ｚ^１０８、Ｚ^１１２〜Ｚ^１１６及びＺ^１１７〜Ｚ^１２１の各群において少なくとも１つは水酸基である］

[Wherein, Z ^{99 to} Z ¹²¹ are as defined for Z ^{1 to} Z ¹⁵ above. However, at least one in each group of Z ^{99 to} Z ¹⁰³ , Z ^{104 to} Z ¹⁰⁸ , Z ^{112 to} Z ¹¹⁶ and Z ^{117 to} Z ¹²¹ is a hydroxyl group]

  The blending amount of component (E) is preferably blended within the range of 5 to 40% by weight, with the total amount of component excluding (D) organic solvent being 100% by weight, It is more preferable to mix within the range. If the proportion of the component (E) is less than 10% by weight, there is a possibility that the positive patterning property may not be obtained. If it exceeds 40% by weight, the coating property of the composition is deteriorated and the film formation itself is difficult. There is a risk.

(F) Surfactant When the composition of the present invention is applied to a substrate or the like by spin coating, it is preferable to add a surfactant because a uniform coating film is obtained.
Examples of the surfactant that can be used in the present invention include polydimethylsiloxane surfactants, fluorine surfactants, polyoxyalkylene surfactants, and the like, and polydimethylsiloxane surfactants are preferred. .

  Examples of polydimethylsiloxane surfactants include, for example, SH28PA (Toray Dow Corning, dimethylpolysiloxane polyoxyalkylene copolymer), Paintad 19, 54 (Toray Dow Corning, dimethylpolysiloxane polyoxy). Alkylene copolymer), FM0411 (silaplane, manufactured by Chisso), SF8428 (manufactured by Toray Dow Corning, dimethylpolysiloxane polyoxyalkylene copolymer (containing side chain OH)), BYK UV3510 (manufactured by BYK Japan, Dimethylpolysiloxane-polyoxyalkylene copolymer), DC57 (manufactured by Toray Dow Corning Silicone Co., Ltd., dimethylpolysiloxane-polyoxyalkylene copolymer), DC190 (manufactured by Toray Dow Corning Silicone Co., Ltd.) Chill polysiloxane-polyoxyalkylene copolymer), Silaplane FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM-DA11, FM-DA21, FM-DA26, FM0711, FM0721, FM-0725, TM-0701, TM-0701T (manufactured by Chisso), UV3500, UV3510, UV3530 (manufactured by Big Chemie Japan), BY16-004, SF8428 (made by Toray Dow Corning Silicone), VPS-1001 (made by Wako Pure Chemical Industries), etc. are mentioned. In particular, Silaplane FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM0711, FM0721, FM-0725, VPS-1001, etc. can be mentioned. Moreover, as a commercial item of the said silicone compound which has an ethylenically unsaturated group, Tego Rad 2300, 2200N, Tego Chemie, etc. can be mentioned, for example.

  Examples of the fluorosurfactant include, for example, Megafac F-114, F410, F411, F450, F493, F494, F443, F444, F445, F446, F470, F471, F472SF, F474, F475, R30, F477, F478, F479, F480SF, F482, F483, F484, F486, F487, F172D, F178K, F178RM, ESM-1, MCF350SF, BL20, R08, R61, R90 (manufactured by Dainippon Ink & Chemicals, Inc.) can be mentioned.

  Examples of the polyoxyalkylene surfactant include Disperbyk-180 (manufactured by Big Chemie), TR-701 (manufactured by ADEKA), and the like.

  The blending amount of the component (F) in the composition of the present invention is preferably 0.01 to 5% by weight when the total amount of the component excluding the organic solvent (D) is 100% by weight, 0.05 More preferably, it is ˜1% by weight. When the amount of component (F) is less than 0.01% by weight, the effect of adding component (F) may not be obtained, and when it exceeds 5% by weight, the refractive index may decrease.

(G) Additives Various additives can be blended in the composition of the present invention within a range not impairing the effects of the present invention. Examples of such additives include curable compounds other than the above components, and antioxidants.

The curable compound includes a thermosetting compound and a photocurable compound. By blending these compounds, the hardness of the resulting cured product can be increased.
Examples of the thermosetting compound include melamine compounds and alkoxysilanes.

  The resin composition of the present invention can be prepared by a known method. A polyamic acid and / or imidized polymer solution, a compound having a reactive group, an organic solvent and, if necessary, a quinonediazide sulfonic acid ester compound and a surfactant are stirred and dissolved at room temperature and normal pressure. The resin composition can be obtained by stirring the mixture and mixing at room temperature and normal pressure. In addition, since the composition has photosensitivity, it is preferable to perform all work under ultraviolet light shielding.

The composition of the present invention is preferably preliminarily filtered with a filter having a pore diameter of about 0.05 to 1 μm, preferably with a 0.5 μm filter. The substrate to which the composition of the present invention is applied may be surface-treated with HMDS (hexamethyldisilazane). Examples of the HMDS treatment method include a method of dropping HMDS on a substrate and rotating the substrate with a spin coater to remove excess HMDS, a method of exposing the substrate to an atmosphere containing vaporized HMDS, and the like. Examples of the method for applying the composition of the present invention include spin coating, roll coating, bar coating, large coating, and gravure printing. Spin coating is preferred because it is easy to obtain film thickness uniformity. The coated substrate is preferably further baked with a hot plate or an oven. The baking conditions can be appropriately adjusted depending on the composition. For example, the coating is prepared by heating on a hot plate at 50 to 150 ° C., preferably 80 to 120 ° C. for 30 to 300 seconds, preferably 60 to 120 seconds. Can do. Furthermore, the exposure is performed under the conditions of an illuminance of 10 to 1000 mW / cm ² and an irradiation light amount of about 10 to 1000 mJ / cm ² , and then a hot plate at 80 to 300 ° C., preferably 100 to 280 ° C., for 30 to 500 seconds, preferably Can produce a cured film by heating for 120 to 300 seconds. The light source for exposure is not particularly limited as long as it contains light having a wavelength to which component (C) of the composition of the present invention is sensitive, and a high-pressure mercury lamp, an ultraviolet laser, or the like can be applied.

II. Optical film The optical film of the present invention is obtained by applying the composition of the present invention to a substrate and then heating.
Examples of the substrate include silicon oxide and silicon nitride substrates on which image sensors are manufactured.
Since the formation of the optical film of the present invention is as described above, it is omitted here.
The optical film of the present invention has a thickness of usually 0.1 to 2 μm, preferably 0.3 to 1 μm, and a refractive index at 633 nm is usually 1.65 or more, preferably 1.70 or more. More preferably, it is 1.80 or more.
When the composition of the present invention is applied to a substrate having holes, it gives a cured film in which no holes or the like are present in the holes and the holes are uniformly embedded. FIG. 1 shows a schematic diagram when a substrate having holes is uniformly embedded with the composition of the present invention, and FIG. 2 shows a schematic diagram when voids are generated in the holes.
Since the optical film of the present invention has a high refractive index and excellent transparency, it is useful as a high refractive index member for a solid-state imaging device.

III. Optical member The optical member of the present invention is a patterned member made of the optical film of the present invention, preferably formed by exposure and development through a desired pattern mask.
The composition of the present invention used in the production of the optical member of the present invention is a positive photocurable composition in which the unexposed portion is cured and the exposed portion is uncured.
The patterned optical member of the present invention is useful as, for example, a microlens array of a solid-state imaging device.

The patterned optical member of the present invention can be manufactured as follows.
The coating film formed in the same manner as in the production of the optical film is exposed through a mask having a desired pattern to form a pattern. For the exposure, a mask aligner, a reduced projection exposure apparatus, or the like can be used. The light source for exposure is not particularly limited as long as it contains light having a wavelength to which the component (C) of the composition of the present invention is sensitive, and a high-pressure mercury lamp, an ultraviolet laser, or the like can be applied. The exposed film is developed in a subsequent development step. Examples of the developing method include paddle development, dip development, and shower development. The unpatterned optical film obtained by development is further exposed under conditions of an illuminance of 10 to 1000 mW / cm ² and an irradiation light amount of about 10 to 1000 mJ / cm ² , and then 80 to 300 ° C., preferably 100 to 280. An optical member can be formed by heating with a hot plate at 0 ° C. for 30 to 500 seconds, preferably 120 to 300 seconds.

The developer used for patterning is preferably an alkaline aqueous solution in which sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, or the like is dissolved.
Examples of commercially available developers that can be used in the present invention include PD523, PD523AD, CD200CR (manufactured by JSR), and the like.
The concentration of the developer should be appropriately determined as necessary, but is usually in the range of 0.01 to 10% by weight, preferably in the range of 0.1 to 1% by weight.

攪拌機、還流冷却器及び窒素導入管を備えた反応容器に、４，４’−ビス（４−ニトロフェニルスルファニル）ジフェニルスルフィド（１３．７ｇ、０．０２８ｍｏｌ）と脱水エタノール（１００ｍＬ）、そして１０％パラジウム活性炭（１．２０ｇ）、を加え、加熱還流した。その後、ヒドラジン・一水和物（６０ｍＬ）と脱水エタノール（２０ｍＬ）を１．５時間かけ滴下し、反応液を６時間加熱還流した。反応液を熱濾過し、黄色の析出物を濾取しエタノールで洗浄した。得られた黄色の個体はエタノールを用いて再結晶し精製した。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
Synthesis example 1
Synthesis of 4,4′-thiobis [(p-phenylenesulfanyl) aniline] (3SDA)

In a reaction vessel equipped with a stirrer, reflux condenser and nitrogen inlet tube, 4,4′-bis (4-nitrophenylsulfanyl) diphenyl sulfide (13.7 g, 0.028 mol), dehydrated ethanol (100 mL), and 10% Palladium activated carbon (1.20 g) was added and heated to reflux. Thereafter, hydrazine monohydrate (60 mL) and dehydrated ethanol (20 mL) were added dropwise over 1.5 hours, and the reaction solution was heated to reflux for 6 hours. The reaction mixture was filtered hot, and the yellow precipitate was collected by filtration and washed with ethanol. The obtained yellow solid was recrystallized and purified using ethanol.

Yield: 10.2 g
Yield: 84.0%
Melting point: 142-143 ° C. (DSC)
FT-IR (KBr, cm ⁻¹ ): 3428.8, 3382.5, 1619.9, 1592.9, 1496.5, 1473.3, 1292.0, 1176.4, 1099.2, 1010.5 , 825.4
¹ H-NMR (300 MHz, DMSO-d ₆ , ppm): 5.46 (s, 4H), 6.62-6.64 (d, 4H), 6.98-7.01 (d, 4H), 7.15-7.19 (m, 8H)
Calcd _{C 24 H 20 N 2 S 3} : C, 66.63%; H, 4.66%; N, 6.48%
Measurement C, 66.59%; H, 4.77%; N, 6.34%

Synthesis example 2
4,4 ′-[1- [4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (48% by weight) and 6-diazo-5,6-dihydro-5-oxo -Preparation of an ester (component (E)) with naphthalene-1-sulfonic acid (52% by weight)

  In a container equipped with a stirrer, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (Tris-PPA, manufactured by Honshu Chemical Co., Ltd.) 42.4 g (0.1 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (Toyo Gosei Co., Ltd., NAC-5) 53.7 g (0.2 mol) were dissolved in 600 mL of acetone. This solution was ice-cooled, and a solution obtained by diluting 22.3 g (0.22 mol) of triethylamine in 100 mL of acetone was added dropwise over 30 minutes so that the internal temperature did not exceed 30 ° C. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Then, the hydrochloride of triethylamine was removed by filtration, and the filtrate was poured into 20 L of 0.1% aqueous hydrochloric acid solution to precipitate the reaction product, and then the precipitate was filtered and collected at 40 ° C. in a vacuum dryer. The quinonediazide compound was obtained by drying overnight.

Production Example 1
Production of polyamic acid / imidized polymer P-1 (component (A)) 3SDA (43.19 g, 99.8 mmol) and N-methyl-2-pyrrolidone (250 g) were added to a reaction vessel equipped with a nitrogen introduction tube. The mixture was stirred at room temperature and completely dissolved. Next, 1,2,3,4-butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd., BT-100) (19.81 g, 100 mmol) was added, and the mixture was stirred at 60 ° C. for 3 hours. An NMP solution of acid was obtained. Next, NMP (300 g), acetic anhydride (10.21 g, 100 mmol) and pyridine (7.91 g, 100 mmol) were added, and the mixture was stirred at 110 ° C. for 4 hours to prepare polyamic acid / imidized polymer P-1 (component (A )) NMP solution was obtained. Residual acetic anhydride, pyridine and NMP were removed under reduced pressure using an evaporator and concentrated to a solid content concentration of 20%, and then γ-butyrolactone was added to a solid content concentration of 10%. After concentration and dilution with γ-butyrolactone were repeated three times, the solid content concentration was adjusted to 25% to obtain a γ-butyrolactone solution of polyamic acid / imidized polymer P-1 (component (A)). This solution was added dropwise to methanol (6300 g) with stirring using a dropping funnel, and the precipitated white precipitate was filtered off and dried using a vacuum drier to prepare polyamic acid / imidized polymer P-1 (component) (A)) powder was obtained.
^{According to 1} H-NMR measurement, the imidization ratio calculated from the ratio of the integral values of the aromatic ring moiety (δ6.5 to 8.0) and the amide moiety (δ9.9 to 10.6) was 50%.

Example 1
Production of Resin Composition Powder (26.0 g) of polyamic acid / imidized polymer P-1 (component (A)) obtained in Production Example 1 and PETA (5.0 g) were converted to γ-butyrolactone (175.3 g). ), Propylene glycol monomethyl ether (67.4 g), dimethylpolysiloxane-polyoxyalkylene copolymer (DC-190 manufactured by Toray Dow Corning) (0.1 g), quinonediazide obtained in Synthesis Example 3 The compound (14.0 g) was added, and the mixture was stirred and mixed at room temperature and normal pressure to obtain a uniform solution. Next, a propylene glycol monomethyl ether dispersion (solid content concentration 20.5%) (TS-103) (267.8 g) of silicon oxide-coated tin oxide-containing rutile titanium oxide was added and stirred at room temperature and normal pressure. And uniformly dispersed.

Examples 2-9 and Comparative Examples 1-2
Each composition was obtained in the same manner as in Example 1 except that the composition shown in Table 1 was used.

<Characteristic evaluation of composition>
The applicability of the compositions obtained in the above examples and comparative examples was evaluated as follows. The results are shown in Table 1.
(1) Hole filling application property A substrate having a hole pattern with a depth of 2 μm and a diameter of 0.5 μm was prepared on a silicon wafer using tetraethoxysilane. When the liquid composition was spin-coated on this substrate, it was evaluated as “◯” when there was no void or the like in the hole and could be uniformly embedded, and “x” when it could not be embedded uniformly.

<Preparation of cured film and characteristic evaluation>
About the cured film obtained as follows, refractive index and transmittance were evaluated by the following methods. The results are shown in Table 1.

(1) Refractive index The liquid composition was spin coated on a silicon wafer, heated and dried at 120 ° C. for 1 minute, and then exposed under the conditions of an illuminance of 20 mW / cm ² and an irradiation light amount of 1 J / cm ² . Subsequently, it heated at 250 degreeC for 5 minute (s), and the measurement sample with a film thickness of 0.6 micrometer was obtained. The sample was measured for refractive index at a wavelength of 633 nm using a prism coupler manufactured by Metricon.

(2) Transmittance A measurement sample was prepared in the same manner as (1) except that the composition was applied onto a glass wafer.
The transmittance of the measurement sample was measured using a spectrophotometer manufactured by JASCO Corporation, and the case where the transmittance at a wavelength of 400 nm was 90% or more was evaluated as “◯”, and the case where it was less than 90% was evaluated as “X”. .

The components in Table 1 are as follows.
Ingredient (A):
P-1: Production component (B) in Production Example 1:
Silicon oxide coating-tin oxide-containing rutile titanium oxide: manufactured by Teica, TS-103, particle size: 5 to 15 nm
Component (C):
PETA: Pentaerythritol monohydroxytriacrylate DPHA: Dipentaerythritol hexaacrylate Divinyl sulfone: Araldite MY721 manufactured by Tokyo Chemical Industry Co., Ltd. Tetrafunctional oxiranyl group-containing compound EX-1610-P: Nagase ChemteX, manufactured by Huntsman Advanced Materials Tetrafunctional oxiranyl group-containing compound xylylene oxetane: Toagosei Co., Ltd. component (E):
Quinodine diazide sulfonic acid ester compound: 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (48% by weight) and 6-diazo-5 , 6-Dihydro-5-oxo-naphthalene-1-sulfonic acid (52% by weight) ester, Synthesis Example 2 with synthesis component (F):
Dimethylpolysiloxane-polyoxyalkylene copolymer: DC-190 manufactured by Toray Dow Corning
Disperbyk-180: manufactured by Big Chemie, polyoxyalkylene surfactant

  From the results of Table 1, the composition of the example containing the compound of component (C) in a predetermined amount range has excellent hole filling coating properties, a high refractive index of 1.80 to 1.83, and transparency. It turns out that an excellent cured film is given.

The composition of the present invention can be uniformly embedded and applied to a substrate having holes without voids, and is suitable for various optical members produced using a substrate having holes. Can be used.
The composition of the present invention is excellent in transparency, has a very high refractive index of more than 1.80, can provide a curable composition that gives a cured film that can be patterned, and can produce a high refractive index member for a solid-state imaging device. Useful as a raw material.
The optical film of the present invention is excellent in transparency, has a high refractive index, and is useful as a member for a solid-state imaging device.
The optical member of the present invention can be patterned into a desired shape, and is useful as, for example, a microlens material.

It is a schematic diagram which shows the case where the base material which has a hole is uniformly embedded with the liquid composition. It is a schematic diagram which shows the case where the base material which has a hole is not uniformly embedded with a liquid composition, but the void has arisen in the hole.

Claims (13)

(A) a polyamic acid having a structure represented by the following general formula (1),

[In Formula (1), R ¹ is each independently an alkyl group having 1 to 3 carbon atoms or a cyano group, a is each independently an integer of 0 to 4, R is a tetravalent organic group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100,000. And at least one selected from the group consisting of imidized polymers of the polyamic acid,
(B) Particles having a particle diameter of 1 to 100 nm as measured by dynamic light scattering, the main component of which is an oxide of a Group 4 element in the periodic table,
(C) a compound that is liquid at room temperature and has a reactive group, and
(D) contains an organic solvent,
The resin composition in which the proportion of the component (C) is in the range of 3 to 20% by weight when the total amount of the components excluding the organic solvent (D) in the composition is 100% by weight.   The resin composition according to claim 1, wherein the reactive group of the component (C) is at least one selected from the group consisting of a vinyl group, an oxiranyl group, and an oxetanyl group.   The resin composition according to claim 1 or 2, wherein two or more reactive groups of the component (C) are present in one molecule.   The resin composition according to any one of claims 1 to 3, wherein the component (A) is a polymer having a phenolic hydroxyl group or a carboxyl group.   Furthermore, the resin composition of any one of Claims 1-4 containing (E) quinonediazide compound.   The resin composition according to claim 4 or 5, wherein R in the general formula (1) is selected from the group consisting of tetravalent alicyclic groups.   The said component (B) is a rutile type titanium oxide particle, The resin composition of any one of Claims 1-6.   The resin composition according to claim 7, wherein the component (B) is rutile-type titanium oxide particles coated with silicon oxide.   Furthermore, the resin composition of any one of Claims 1-8 containing (F) surfactant.   The optical film obtained by heating, after apply | coating the resin composition of any one of Claims 1-9 to a base material.   The optical film according to claim 10, which has a refractive index of 1.70 or more at a wavelength of 633 nm.   An optical member comprising the optical film according to claim 10. The optical member formed by apply | coating the photosensitive composition of any one of Claims 1-8 to a base material, and then exposing and developing through a mask.

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