JP5343738B2 - Resin composition, optical film and optical member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive composition for a solid state imaging device which is superior in developability and in pattern formation, produces highly refractive cured film, and forms a pattern with ease. <P>SOLUTION: The resin composition includes: (A) at least one selected from a polyamic acid with a predetermined structure and an imidized polymer of the polyamic acid with the predetermined structure; (B) particles including an oxide of an element of the fourth group of the periodic table as a main component and having a particle size of 1-100 nm measured with dynamic light scattering; (C) a quinone diazide compound; and (D) an organic solvent, wherein the content of (C) the quinone diazide compound is in the range of 10-40 wt.% when the sum total of components in the composition excluding (D) the organic solvent is set to 100 wt.%. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a resin composition, an optical film obtained therefrom, and an optical member. More specifically, the present invention relates to a positive photosensitive resin composition that allows easy pattern formation, an optical film obtained therefrom, and an optical member.

  It is known to use a resin composition in which metal oxide particles with a high refractive index are introduced into a highly transparent resin such as polyimide for the lens of a solid-state image sensor in order to improve the light collection efficiency to the light receiving part of the solid-state image sensor. It has been. For example, Patent Document 1 describes an example 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 combined. However, the positive photosensitive high-refractive index resin composition can form a lens shape for a solid-state imaging device, but the refractive index is not sufficiently high. The problem is that the efficiency is not sufficient (for example, see Patent Document 1).

Table 2005/088396

The present invention has been made in view of the above-mentioned problems, and provides a positive photosensitive composition that is easy to form a pattern and provides a cured film having a high refractive index that is excellent in developability and pattern formation. For the purpose.
A further object of the present invention is to provide a high refractive index optical film and an optical member that are excellent in developability and excellent in pattern formation.

  In order to achieve the above-mentioned object, the present inventors have conducted intensive research and added a predetermined amount of a quinonediazide compound to a polyamic acid and / or imidized polymer having a specific structure and metal oxide particles having high transparency and refractive index. The present invention has been completed by finding that a composition formulated with can achieve the above-mentioned object.

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 type (B) periodic table group 4 element oxide selected from the imidized polymer of the polyamic acid as a main component and having a particle diameter of 1 to 100 nm as measured by dynamic light scattering Containing particles (C) quinonediazide compound (D) organic solvent in the range,
The resin composition in which the proportion of the (C) quinonediazide compound is in the range of 10 to 40% 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 ratio of the component (B) is 10 to 80% by weight when the total amount of the components excluding the component (D) in the composition is 100% by weight.
3. 3. The resin composition according to 1 or 2 above, wherein R is selected from the group consisting of tetravalent aliphatic groups.
4). 4. The resin composition according to any one of 1 to 3, wherein the component (B) is rutile type titanium oxide particles.
5. 4. The resin composition according to any one of 1 to 3 above, wherein the component (B) is rutile type titanium oxide particles coated with silicon oxide.
6). Furthermore, the resin composition in any one of said 1-5 containing (E) surfactant.
7). The optical film obtained by apply | coating the resin composition in any one of said 1-6 to a base material, and heating.
8). 8. The optical film as described in 7 above, wherein the refractive index at a wavelength of 633 nm is 1.65 or more.
9. 9. An optical member comprising the optical film as described in 7 or 8 above.
10. The optical member formed by apply | coating the resin composition in any one of said 1-6 to a base material, and then exposing and developing through a mask.

ADVANTAGE OF THE INVENTION According to this invention, the composition of this invention can provide the resin composition which is useful as a manufacturing raw material of the high refractive index member of a solid-state image sensor, and gives the cured film excellent in transparency and high refractive index.
According to the present invention, an optical film having excellent transparency and a high refractive index can be provided.
According to the present invention, a further patterned optical member can be provided.

It is an electron micrograph of a 50 μm, 1L1S pattern of a patterned cured film prepared using the composition of Example 2. It is an electron micrograph which shows the 1.2 micrometer dot and 0.4 micrometer space pattern of the patterned cured film produced using the composition of Example 4. FIG.

Hereinafter, the composition for a solid-state imaging device, the optical film, and the optical member of the present invention will be described in detail.
I. The composition for solid-state image sensors The composition for solid-state image sensors of this invention (henceforth the composition of this invention) may contain the following component (A)-(F). Among these components, components (A) to (D) are essential components, and components (E) to (F) are optional components added according to the purpose.
(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 the particle diameter measured by the dynamic light scattering which has as a main component the oxide of the group 4 element of at least 1 sort (B) periodic table chosen from the imidation polymer of this polyamic acid is 1-100 nm Particles inside,
(C) Quinonediazide compound (D) Organic solvent (E) Surfactant (F) Additive

The composition of this invention can form the cured film which is excellent in applicability | paintability and transparency, and can be patterned by containing (C) quinonediazide compound in the range of predetermined amount.
The composition of the present invention contains (A) a polyamic acid and / or imidized polymer having a predetermined structure, and (B) particles, so that the composition has excellent transparency and has a high refractive index. A film can be formed.

Hereinafter, each component will be described.
(A) At least one selected from a polyamic acid having a structure represented by the general formula (1) and an imidized polymer of the polyamic acid, the component (A) in the present invention is a polyamic acid having a specific structure (A- 1) and / or an imidized polymer (A-2) having a specific structure.
In addition, each of the polyamic acid (A-1) and the imidized polymer (A-2) may be a single type or two or more types.

(A-1) Polyamic acid The polyamic acid used in the present invention has a structure represented by the following general formula (1), and has a very high refractive index (25 ° C., wavelength of 400 to 700 nm) and high refraction. With this ratio, a cured product having 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.

(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 sulfur atoms include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 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 aliphatic and alicyclic tetracarboxylic dianhydrides include, for example, 1,2,3,4-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-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] -Fran- , 3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene Examples include aliphatic and alicyclic tetracarboxylic dianhydrides such as -2,3,5,6-tetracarboxylic dianhydride. Among these, 1,2,3,4-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-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxo-tetrahydrofuranyl Le) -3-methyl-3 -Cyclohexene-1,2-dicarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -Furan-1,3-dione is preferred, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] dodecane-3 , 5,9,11-Tetrao 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.

(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.

  For example, the imidized polymer (A-2) is obtained by adding acetic anhydride and pyridine as a catalyst to the solution of the polyamic acid (A-1) at a temperature of 80 to 150 ° C. for 1 to 5 hours in a nitrogen atmosphere. Obtained by heating.

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 ratio (%) is determined by measuring ¹ H-NMR and calculating from the integrated 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.
Moreover, the obtained polyamic acid or the solution of the imidized polymer of polyamic acid can also be used by substituting with the organic solvent different from the organic solvent used at the time of a synthesis | combination by the vacuum concentration method as needed. The organic solvent may be removed by reprecipitation or the like.

  The proportion of the component (A) in the composition of the present invention is preferably in the range of 10 to 70% by weight when the solid content in the composition is 100% by weight, and is preferably 20 to 60% by weight. More preferably within the range. If the proportion of the 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 70% by weight, the transmittance of the cured film is reduced. There is a fear.

(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 measured by dynamic light scattering 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 in the range of 5 to 15 nm. It is more preferable that If the particle diameter is less than 1 nm, secondary aggregation is likely to occur, and the cured film may be whitened. If it exceeds 100 nm, the surface uniformity during thin film formation may be impaired.

  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 proportion of component (B) in the composition of the present invention is preferably in the range of 10 to 80% by weight when the total solid content in the composition is 100% by weight, and preferably 20 to 70% by weight. It is more preferable to be within the range. If the ratio of the component (B) is less than 10% by weight, the refractive index of the cured film may be lowered, and if it exceeds 80% by weight, a pattern may not be formed during alkali development.
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) Quinonediazide compound Component (C) in the composition of the present invention is a quinonediazide compound. The quinonediazide compound is blended for imparting pattern forming properties to the composition of the present invention and making the composition of the present invention positive photosensitive.
The quinonediazide compound itself does not have alkali solubility and has an effect of reducing alkali solubility even when a composition is formed. By exposing the composition containing a quinonediazide compound, the quinonediazide compound is decomposed to generate a carboxylic acid and become alkali-soluble, which has an effect of increasing the dissolution rate of the exposed portion with respect to alkali. This difference in solubility can impart positive photosensitivity to the composition of the present invention.

The component (C) needs to be blended within a range of 10 to 40% by weight when the total solid content in the composition is 100% by weight. If the proportion of the component (C) is less than 10% by weight, patterning properties may not be obtained, and if it exceeds 40% by weight, the applicability of the composition may be deteriorated and film formation itself may be difficult. is there.
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 quinonediazide sulfonic acid ester compound include 1,2-benzoquinone diazide-4-sulfonic acid ester of a polyhydroxy compound, 1,2-naphthoquinone diazide-4-sulfonic acid ester, and 1,2-naphthoquinone diazide-5-sulfone. Examples include acid esters and 1,2-naphthoquinonediazide-6-sulfonic acid esters, and 1,2-naphthoquinonediazide-4-sulfonic acid esters and 1,2-naphthoquinonediazide-5-sulfonic acid esters are 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.

[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]

[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.]

[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]

[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]

[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]

[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]

[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]

  As described above, the proportion of component (C) in the composition of the present invention needs to be in the range of 10 to 40% by weight when the total solid content in the composition is 100% by weight. The content is preferably within the range of 10 to 30% by weight, and more preferably within the range of 10 to 20% by weight.

(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) Surfactant When the composition of the present invention is applied to a substrate or the like by spin coating, it is preferable to incorporate a surfactant because a uniform coating film is obtained.
As the surfactant that can be optionally used in the present invention, those commercially available can be used as they are.

  Examples of the surfactant include, for example, SH28PA, SF8428, DC57, DC190, BY16-004 (manufactured by Toray Dow Corning), Paintad 19, 54 (manufactured by Toray Dow Corning, dimethylpolysiloxane polyoxyalkylene copolymer) , BYK UV3500, UV3510, UV3530, Disperbyk-180 (manufactured by Big Chemie), 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 Corporation), VPS-1001 (manufactured by Wako Pure Chemical Industries), Tego R ad 2300, 2200N (manufactured by Tego Chemie), Megafuck 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 DIC) can be mentioned.

  The compounding amount of component (E) in the composition of the present invention is usually 0 to 10% by weight, preferably 0.01 to 5% by weight, when the total solid content excluding the organic solvent is 100% by weight. Preferably it exists in the range of 0.05 to 1 weight%. When the amount of component (E) exceeds 10% by weight, the refractive index may be lowered.

(F) 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.

Preparation of Resin Composition The resin composition of the present invention can be prepared by a known method. Polyamic acid or polyamic acid and imidized polymer solution, quinonediazide sulfonic acid ester compound, γ-butyrolactone, propylene glycol monomethyl ether and other solvents and surfactants are stirred and dissolved at room temperature and normal pressure, and this solution is titania particles. The resin composition can be obtained by adding the mixture to the propylene glycol dispersion with stirring and mixing under normal temperature and pressure. In addition, since the composition has photosensitivity, it is preferable that all operations are performed under ultraviolet light shielding.
The solid content concentration of the resin composition of the present invention can be appropriately determined in consideration of the coating film thickness, the coating apparatus and the like, but is preferably 10 to 30%.

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. Further, the illuminance is 10 to 1,000 / cm ^2, the irradiation light amount is exposed with 10~1000mJ / cm ² about conditions, then 80 to 300 ° C., preferably a hot plate at 100 to 280 ° C., 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 the component (C) of the composition of the present invention is sensitive.

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.
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. Further, the optical film of the present invention has a transmittance at 400 nm of usually 70% or more, preferably 80% or more, more preferably 90% or more.
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 for, 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 the production of the optical film is exposed through a mask having a desired 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. The exposed film is developed in a subsequent development step. Examples of the developing method include paddle development, dip development, and shower development. The development time is preferably 30 to 300 seconds, more preferably 60 to 180 seconds, although it depends on the developer concentration. Usually, in the development step, rinsing is performed for about 30 to 120 seconds with running water in order to wash away the developer. The patterned 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 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. The developer may further contain a surfactant.
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 is appropriately determined according to the composition of the composition, but is usually in the range of 0.01 to 10% by weight, preferably in the range of 0.1 to 1% by weight.

The resolution of the patterned optical member obtained above can be confirmed by, for example, an L / S pattern. The resolution of the 1L / 1S pattern is usually 0.2 to 1000 μm, preferably 0.2 to 100 μm, and more preferably 0.2 to 10 μm without residue.
As an example of 1L / 1S pattern resolution evaluation, FIG. 1 shows an electron micrograph of a 50 μm, 1L1S pattern produced using the composition of Example 2 described later.
Further, FIG. 2 shows an electron micrograph of an example of producing an optical member having a 1.2 μm dot and 0.4 μm space pattern, which was produced using the composition of Example 4 described later.

  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%

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, butanetetracarboxylic dianhydride (BT-100) (19.81 g, 100 mmol) was added and stirred at 60 ° C. for 3 hours to obtain an NMP solution of polyamic acid. 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, the precipitated white precipitate was filtered off, dried using a vacuum dryer and dried to polyamic acid / imidized polymer P-1 ( A powder of component (A)) 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%.

Production Example 2
Production of polyamic acid / imidized polymer P-2 (component (A)) As in Production Example 1, except that 4,4′-thiodianiline (SDA; 21.58 g, 99.8 mmol) was used as the diamine component. Thus, a powder of polyamic acid / imidized polymer P-2 (component (A)) was obtained.

  The combinations of diamines and acid anhydrides of P-1 and P-2 produced in Production Examples 1 to 3 and the imidization ratio are shown in Table 1 below.

Abbreviations in Table 1 indicate the following.
BT-100: 1,2,3,4-butanetetracarboxylic dianhydride; manufactured by Shin Nippon Rika Co., Ltd., trade name: BT-100

ODPA: 4,4'-oxydiphthalic dianhydride

  3SDA: 4,4'-thiobis [(p-phenylenesulfanyl) aniline], synthesized in Synthesis Example 1

SDA: 4,4'-thiodianiline

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 ester (component (C)) 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. Thereafter, 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. Then, the precipitate was filtered and collected, and it was collected overnight at 40 ° C. in a vacuum dryer. The quinonediazide compound was obtained by drying.

Example 1
After dissolving the powder (23 g) of the polyamic acid / imidized polymer P-1 (component (A)) obtained in Production Example 1 in γ-butyrolactone (152.8 g), 4,4 ′-[1- [4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (48 wt%) and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid ( 52 wt.%) Ester (14 g) was added and dissolved. Next, a propylene glycol monomethyl ether dispersion (solid content concentration 20.3%) (TS-103) (310.2 g) of silicon oxide-coated tin oxide-containing rutile titanium oxide was added and dispersed uniformly. .

Examples 2-9 and Comparative Examples 1-4
Each composition was obtained in the same manner as in Example 1 except that the composition shown in Table 2 below was added, and propylene glycol monomethyl ether was added as necessary.

<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 2.
When the composition was spin-coated on a silicon wafer, the case where it could be uniformly applied was evaluated as “◯”, and the case where defects such as striation and repelling occurred was evaluated as “x”.

<Preparation of cured film and characteristic evaluation>
About the cured film obtained as mentioned above, the refractive index, the transmittance | permeability, and the patterning property were evaluated by the following method. The results are shown in Table 2.

(1) Refractive index The composition was spin-coated on a silicon wafer, heated and dried at 120 ° C. for 1 minute, then exposed under the conditions of an illuminance of 20 mW / cm ² and an irradiation light amount of 1 J / cm ² , and then 5 at 280 ° C. It heated for minutes and the measurement sample (cured film) with a film thickness of 0.6 micrometer was obtained.
About the said measurement sample, the refractive index in wavelength 633nm was measured using the metricon prism coupler.

(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”. .

(3) Patterning property The composition was spin-coated on a silicon wafer and dried by heating at 120 ° C. for 1 minute. Then illuminance 20 mW / cm ^2, under the conditions of the irradiation light quantity 100 mJ / cm ^2, were exposed through a photomask L / S = 10μm / 10μm.
When developed for 2 minutes using an alkali developer, the case where the L / S pattern was obtained without residue or the like was evaluated as “◯”, and the case where it was not evaluated as “X”.
The alkaline developer used was a CD200CR manufactured by JSR, diluted 10 times with pure water.

The components in Table 2 are as follows.
Ingredient (A):
P-1: produced in Production Example 1 P-2: produced in Production Example 2 Component (B):
Silicon oxide coating-tin oxide-containing rutile titanium oxide: manufactured by Teica, TS-103, particle size: 5 to 15 nm
Component (C):
Quinodine diazide compound: 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (48% by weight) and 6-diazo-5,6-dihydro- Esters with 5-oxo-naphthalene-1-sulfonic acid (52% by weight): Synthesis component (E) in Synthesis Example 2:
DC-190: trade name, manufactured by Toray Dow Corning Silicone Co., Ltd., dimethylpolysiloxane-polyoxyalkylene copolymer Disperbyk-180: trade name, manufactured by Big Chemie Co., alkylol ammonium salt of a copolymer having an acid group

  From the results of Table 2, the compositions of Examples containing a quinonediazide compound in a predetermined amount range have excellent coating properties, a high refractive index of 1.83 to 1.87, excellent transparency, and patterning properties. It turns out that a favorable cured film is given.

The composition of the present invention can provide a resin composition that provides a cured film having excellent transparency and a high refractive index, and is useful as a raw material for producing a high refractive index member of a solid-state imaging device.
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, for example, as a microlens material.

Claims (10)

(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 type (B) periodic table group 4 element oxide selected from the imidized polymer of the polyamic acid as a main component and having a particle diameter of 1 to 100 nm as measured by dynamic light scattering Containing particles (C) quinonediazide compound (D) organic solvent in the range,
The resin composition in which the proportion of the (C) quinonediazide compound is in the range of 10 to 40% by weight when the total amount of the components excluding the organic solvent (D) in the composition is 100% by weight.   2. The resin composition according to claim 1, wherein the ratio of the component (B) is 10 to 80 wt% when the total amount of the components excluding the component (D) in the composition is 100 wt%.   The resin composition according to claim 1 or 2, wherein R is selected from the group consisting of tetravalent aliphatic groups.   The resin composition according to claim 1, wherein the component (B) is rutile titanium oxide particles.   The resin composition according to any one of claims 1 to 3, wherein the component (B) is rutile-type titanium oxide particles coated with silicon oxide.   Furthermore, the resin composition of any one of Claims 1-5 containing (E) surfactant.   The optical film obtained by heating, after apply | coating the resin composition of any one of Claims 1-6 to a base material.   The optical film according to claim 7, wherein the refractive index at a wavelength of 633 nm is 1.65 or more.   An optical member comprising the optical film according to claim 7. An optical member formed by applying the resin composition according to any one of claims 1 to 6 to a base material, and then exposing and developing through a mask.