JP6428002B2 - Resin composition for antireflection film, method for producing antireflection film and method for producing pattern using the same, and solid-state imaging device - Google Patents

Description

  The present invention relates to a resin composition useful for forming an antireflection film, a method for forming the same, and a method for forming a pattern. More specifically, the present invention relates to a resin composition that is provided in a lower layer of a photosensitive composition and is useful for forming an antireflection film that contributes to improvement of resolution in photolithography.

  In the manufacture of fine electronic components, it is required to form fine patterns in order to obtain a higher degree of integration. For example, in a CMOS type solid-state imaging device, miniaturization of a photoelectric conversion layer progresses with rapid pixel increase, and accordingly, the size of a color conversion layer pixel formed on the photoelectric conversion layer also becomes finer. There is a need. The demand for such high miniaturization is increasing, and it has become difficult to obtain a necessary fine pattern even by a photolithography method using a photosensitive resin.

  One factor that hinders the improvement in the resolution of the photosensitive resin is that the portion that should not be exposed by the reflected light from the ground during exposure is exposed. As a method for preventing this, a method using a multilayer film including an antireflection film has been studied.

  For example, Patent Document 1 discloses a resist underlayer film containing a crosslinked aromatic polymer. The aromatic polymer specifically disclosed is an aromatic polymer having a hydrocarbon such as a naphthalene ring or a fluorene ring as a main skeleton and a hydroxyl group, an acetoxy group, a methoxy group or the like as a substituent. The aromatic polymer is said to function as an antireflection film that absorbs the radiation reflected from the substrate.

JP 2013-145368 A

  Although the composition in Patent Document 1 has a certain function as an antireflection film, an antireflection film having more excellent antireflection performance has been demanded. There is also a problem that a development residue is generated during patterning.

  This invention is made | formed in view of the said situation, and it aims at providing the resin composition for anti-reflective films which can form a pattern with high resolution without generating a residue.

  That is, the present invention is a resin composition for an antireflection film, comprising (A) a polyether sulfone resin, (B) a crosslinking agent, and (C) an ultraviolet absorbing compound.

  According to the composition of this invention, when patterning the photosensitive composition formed on it, a residue does not generate | occur | produce and the resolution of a pattern can be improved.

Sectional drawing which shows the outline of a solid-state image sensor

(Resin composition for antireflection film)
The resin composition for an antireflection film of the present invention comprises (A) a polyether sulfone resin, (B) a crosslinking agent, and (C) an ultraviolet absorbing compound.

  The (A) polyether sulfone resin used in the present invention is a generic term for a resin having a skeleton in which an aromatic group is bonded by a sulfone group and an ether group. For example, what contains at least 1 type of repeating unit chosen from the group which consists of following General formula (1)-(3) is mentioned.

(—Ar ¹ —SO ₂ —Ar ² —O—) (1)
_{^{(-Ar 3 -V-Ar 4 -O}} -Ar 5 -SO 2 -Ar 6 -O-) (2)
(—Ar ⁷ —SO ₂ —Ar ⁸ —O—Ar ⁹ —O—) (3)
In formula (1), Ar ¹ and Ar ² may be the same or different, and are organic groups containing an aromatic ring having 6 to 20 carbon atoms. In formula (2), Ar ^{3 to} Ar ⁶ may be the same or different, and an organic group containing an aromatic ring having 6 to 20 carbon atoms, V is a divalent hydrocarbon group having 1 to 15 carbon atoms. . In formula (3), Ar < ⁷ > -Ar < ⁹ > may be the same or different, and is an organic group containing an aromatic ring having 6-20 carbon atoms.

Here, Ar ¹ and Ar ² that are preferable in Formula (1) are arylene groups having 6 to 20 carbon atoms, and arylene groups having 6 to 12 carbon atoms are more preferable. Specifically, m-phenylene group, methyl-m-phenylene group, dimethyl-m-phenylene group, tetramethyl-m-phenylene group, ethyl-m-phenylene group, diethyl-m-phenylene group, hydroxy-m- Phenylene group, dihydroxy-m-phenylene group, tetrahydroxy-m-phenylene group, hydroxymethyl-m-phenylene group, dihydroxymethyl-m-phenylene group, methoxymethyl-m-phenylene group, dimethoxymethyl-m-phenylene group, Hydroxyethyl-m-phenylene group, dihydroxyethyl-m-phenylene group, carboxy-m-phenylene group, methoxy-m-phenylene group, dimethoxy-m-phenylene group, ethoxy-m-phenylene group, diethoxy-m-phenylene group , P-phenylene group, methyl-p-phen Len group, dimethyl-p-phenylene group, tetramethyl-p-phenylene group, ethyl-p-phenylene group, diethyl-p-phenylene group, hydroxy-p-phenylene group, dihydroxy-p-phenylene group, tetrahydroxy-p -Phenylene group, hydroxymethyl-p-phenylene group, dihydroxymethyl-p-phenylene group, methoxymethyl-p-phenylene group, dimethoxymethyl-p-phenylene group, hydroxyethyl-p-phenylene group, dihydroxyethyl-p-phenylene Group, carboxy-p-phenylene group, methoxy-p-phenylene group, dimethoxy-p-phenylene group, ethoxy-p-phenylene group, diethoxy-p-phenylene group, naphthylene group, biphenylylene group and the like. Among them, the case where both Ar ¹ and Ar ² are a p-phenylene group, a hydroxy-p-phenylene group or a hydroxymethyl-p-phenylene group is advantageous from the viewpoint of production and is particularly preferably used.

In the formula (2), suitable ^Ar 3 to Ar ⁶ is an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 12 carbon atoms. Specifically, methyl-m-phenylene group, dimethyl-m-phenylene group, tetramethyl-m-phenylene group, ethyl-m-phenylene group, diethyl-m-phenylene group, hydroxy-m-phenylene group, dihydroxy- m-phenylene group, tetrahydroxy-m-phenylene group, hydroxymethyl-m-phenylene group, dihydroxymethyl-m-phenylene group, methoxymethyl-m-phenylene group, dimethoxymethyl-m-phenylene group, hydroxyethyl-m- Phenylene group, dihydroxyethyl-m-phenylene group, carboxy-m-phenylene group, methoxy-m-phenylene group, dimethoxy-m-phenylene group, ethoxy-m-phenylene group, diethoxy-m-phenylene group, p-phenylene group , Methyl-p-phenylene group, dimethyl p-phenylene group, tetramethyl-p-phenylene group, ethyl-p-phenylene group, diethyl-p-phenylene group, propyl-p-phenylene group, dipropyl-p-phenylene group, butyl-p-phenylene group, hydroxy- p-phenylene group, dihydroxy-p-phenylene group, tetrahydroxy-p-phenylene group, hydroxymethyl-p-phenylene group, dihydroxymethyl-p-phenylene group, methoxymethyl-p-phenylene group, dimethoxymethyl-p-phenylene group Group, hydroxyethyl-p-phenylene group, dihydroxyethyl-p-phenylene group, carboxy-p-phenylene group, methoxy-p-phenylene group, dimethoxy-p-phenylene group, ethoxy-p-phenylene group, diethoxy-p- Phenylene group, propoxy-p Phenylene group, dipropoxy -p- phenylene group, a butoxy -p- phenylene group, a naphthylene group, such as biphenylene group. Particularly preferred examples include a p-phenylene group, a hydroxy-p-phenylene group or a hydroxymethyl-p-phenylene group.

  V is preferably a group selected from a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group, and an araalkylene group. A group selected from a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group and an aralkylene group is preferable. Specifically, aliphatic hydrocarbon groups such as methylene group, 1,1-ethylene group, 2,2-propylene group, 2,2-butylene group, 4-methyl-2,2-pentylene group, 1,1- Examples thereof include alicyclic hydrocarbon groups such as cyclohexylene group, 3,3,5-trimethyl-1,1-cyclohexylene group, and aralkylene groups such as 1-phenyl-1,1-ethylene group and diphenylmethylene group. . Among these, 2,2-propylene group is more preferably used.

In the formula (2), Ar ^{3 to} Ar ⁶ are particularly preferably a p-phenylene group, a hydroxy-p-phenylene group or a hydroxymethyl-p-phenylene group, and V is a 2,2-propylene group.

In the formula (3), preferable Ar ⁷ and Ar ⁸ are an arylene group having 6 to 12 carbon atoms, and an arylene group having 6 to 10 carbon atoms is more preferable. Specifically, m-phenylene group, methyl-m-phenylene group, dimethyl-m-phenylene group, tetramethyl-m-phenylene group, ethyl-m-phenylene group, diethyl-m-phenylene group, hydroxy-m- Phenylene group, dihydroxy-m-phenylene group, tetrahydroxy-m-phenylene group, hydroxymethyl-m-phenylene group, dihydroxymethyl-m-phenylene group, methoxymethyl-m-phenylene group, dimethoxymethyl-m-phenylene group, Hydroxyethyl-m-phenylene group, dihydroxyethyl-m-phenylene group, carboxy-m-phenylene group, methoxy-m-phenylene group, dimethoxy-m-phenylene group, ethoxy-m-phenylene group, diethoxy-m-phenylene group , P-phenylene group, methyl-p-phen Len group, dimethyl-p-phenylene group, tetramethyl-p-phenylene group, ethyl-p-phenylene group, diethyl-p-phenylene group, hydroxy-p-phenylene group, dihydroxy-p-phenylene group, tetrahydroxy-p -Phenylene group, hydroxymethyl-p-phenylene group, dihydroxymethyl-p-phenylene group, methoxymethyl-p-phenylene group, dimethoxymethyl-p-phenylene group, hydroxyethyl-p-phenylene group, dihydroxyethyl-p-phenylene Group, carboxy-p-phenylene group, methoxy-p-phenylene group, dimethoxy-p-phenylene group, ethoxy-p-phenylene group, diethoxy-p-phenylene group, naphthylene group, biphenylylene group and the like. Of these, a p-phenylene group is more preferably used for both Ar ⁷ and Ar ⁸ .

Further, preferred Ar ⁹ is an arylene group having 6 to 12 carbon atoms, and an arylene group having 6 to 10 carbon atoms is more preferred. Specific examples include a p-phenylene group, a hydroxy-p-phenylene group, a hydroxymethyl-p-phenylene group, a naphthylene group, and a biphenylylene group. Among these, a p-phenylene group, a hydroxy-p-phenylene group, a hydroxymethyl-p-phenylene group, or a biphenylylene group is even more preferable.

In formula (3), Ar ⁷ , Ar ⁸ and Ar ⁹ are particularly preferably a p-phenylene group or a hydroxy-p-phenylene group.

  The above polyether sulfone can be polymerized by a known method. For example, it can be obtained by polycondensing a monomer having a hydroxyl group and a halogen group at the terminal in an aprotic polar solvent in the presence of an alkali metal carbonate. For example, this polyethersulfone is a trademark of “Sumika Excel®” from Solvay Advanced Polymers Inc. under the trademark “Radel®”, from BASF Corporation under the trademark “Ultrazone®”. And those commercially available from Sumitomo Chemical Co., Ltd. can be used.

  The polyether sulfone resin used in the present invention may be a polyether sulfone resin consisting only of at least one repeating unit selected from the group consisting of the aforementioned (1) to (3), or (1) to ( Repeating units other than 3) may be included. It is preferable that at least 50% by weight or more of at least one repeating unit selected from the group consisting of (1) to (3) is contained in the resin.

  (A) By using a polyether sulfone resin, when forming a pattern by exposing and developing the photosensitive material of an upper layer, a pattern shape can be made into a rectangle and a development residue can be suppressed.

  It is considered that the development residue is suppressed by the following actions. As a method for suppressing the development residue, it is possible to reduce the interaction between the antireflection film and the photosensitive material. Examples of the interaction between the antireflection film and the photosensitive material include hydrogen bonding, intermolecular force, and chemical bonding. In order to reduce these interactions, there is a demand for a resin having as little chemical functional groups as possible, and as few acidic and basic functional groups as possible. In consideration of solubility in an organic solvent, a polyether sulfone resin that is soluble in an organic solvent is suitable even if the aforementioned functional group is small.

  Further, since the polyether sulfone resin is a high refractive index resin, it is particularly suitably used for pattern formation with a photosensitive material having a high refractive index. Because the difference between the refractive index of the lower antireflection film and the refractive index of the photosensitive material is small, reflection of light at the interface between the antireflection film and the photosensitive material can be suppressed, and excessive exposure of the photosensitive material can be prevented. Because it can.

  (A) As a polyether sulfone resin, what contains the structure represented by the following general formula (4) is used especially preferable. In addition, (A) polyether sulfone resin may contain partial structures other than the said General formula (4) in the range which does not disturb the characteristic as an antireflection film. Moreover, the composition of this invention can also contain resin other than (A) polyether sulfone resin in the range which does not prevent the characteristic as an antireflection film.

In the general formula (4), R ¹ and R ² are each independently a hydrogen atom, a hydroxy group, a carboxyl group, a monovalent hydrocarbon group having 1 to 4 carbon atoms, or a monovalent hydrocarbon group having 1 to 4 carbon atoms. It is an oxyhydrocarbon group. n represents an integer of 5 to 500. A plurality of R ¹ and R ² may be the same or different.

  (B) Although it does not specifically limit as a crosslinking agent, The crosslinking agent which forms a polyether sulfone resin and a crosslinked structure is preferable, and the compound containing an alkoxymethyl group or a methylol group is especially preferable. In the present invention, the crosslinking agent (B) is used for the purpose of improving the chemical resistance of the antireflection film. Since application, exposure and development of the photosensitive resin composition are performed on the antireflection film, there is a concern about dissolution in a solvent or an alkali developer contained in the photosensitive resin composition. (B) By using a crosslinking agent, dissolution of the antireflection film can be suppressed.

  Especially, it is more preferable to use the compound represented by General formula (5).

In General Formula (5), R ^A represents a direct bond or a monovalent to tetravalent linking group. R ³ and R ⁴ each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ⁵ represents a hydrogen atom, a methyl group or an ethyl group. R ⁶ represents a monovalent organic group having 1 to 20 carbon atoms or a fluorine atom. l represents an integer of 0 to 2, and m represents an integer of 1 to 4. M is 2 when R ^A is a direct bond. when m is 2 to 4, a plurality of ^R 3 to R ⁶ may be the same or different, respectively, but if the same benzene ring has two ^{R 6, R 6} is the same.

  Since the compound represented by the general formula (5) has high compatibility with the polyether sulfone resin, the cross-linking reaction with the polyether sulfone resin can be promoted, and the chemical resistance can be improved more effectively.

Preferred specific examples of the linking group ^RA are shown below, but are not limited thereto.

In the above ^formulas, R 11 ^{to R 33} is a hydrogen atom, a monovalent organic group or a fluorine atom having 1 to 20 carbon atoms. As the monovalent organic group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a naphthyl group, and the like are preferable.

  In the compound represented by the general formula (5), the number of functional groups of the alkoxymethyl group or methylol group in one molecule is preferably 2-8. The number of functional groups is preferably 4 or more from the viewpoint of increasing the crosslinking density and improving the mechanical properties.

  The purity of the compound represented by the general formula (5) is preferably 75% or more, and more preferably 85% or more. If purity is 85% or more, it is excellent in storage stability and can fully perform the crosslinking reaction of a resin composition. Moreover, since the unreacted group used as a water absorbing group can be decreased, the water absorption of a resin composition can be made small. Examples of the method for obtaining a high-purity thermal crosslinking agent include recrystallization and distillation. The purity of the thermal crosslinking agent can be determined by a liquid chromatography method.

  Preferred examples of the compound represented by the general formula (5) are shown below.

  Moreover, the compound which has group represented by General formula (6) as a crosslinking agent other than the compound represented by General formula (5) is mentioned.

^{_{-N (CH 2 OR 34) g}} (H) i (6).

In the general formula (6), R ³⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. g represents 1 or 2, and i represents 0 or 1. However, g + i is 1 or 2.

In the general formula (6), R ³⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. Further, from the viewpoint of the stability of the compound and the storage stability in the resin composition, in the photosensitive resin composition containing a photoacid generator, R ³³ is preferably a methyl group or an ethyl group, and is contained in the compound (CH The number of ₂ OR ³⁴ ) groups is preferably 8 or less.

  Although the preferable specific example of a compound which has group represented by General formula (6) is shown below, it is not restricted to these.

  Although there is no restriction | limiting in particular in content of (B) crosslinking agent in the composition of this invention, Preferably it is the range of 5-40 weight part with respect to 100 weight part of (A) polyether sulfone resin, More preferably, it is 5 It is the range of -30 weight part. When the content of the thermally crosslinkable compound is within this range, the refractive index of the polyether sulfone resin can be maintained while improving the solvent resistance of the cured film.

  In the present invention, the ultraviolet absorbing compound (C) is used for the purpose of making the pattern shape of the upper photosensitive material rectangular and suppressing residues. When the upper photosensitive material is exposed, incident light may pass through the antireflection film, reach the interface between the substrate and the antireflection film, and be reflected there. By absorbing the reflected light by the ultraviolet absorbing compound, light can be prevented from leaking to the upper layer, the upper layer can be prevented from being exposed excessively, and the aforementioned object can be achieved.

  (C) Although it does not specifically limit as an ultraviolet-absorbing compound, For example, ultraviolet-absorbing compounds, such as a benzotriazole type compound, a benzophenone type compound, a triazine type compound, and (pi) conjugated compound, are preferable. In particular, a compound represented by any one of the general formulas (6) to (8) is more preferable.

In General Formula (6), R ^B and R ^B ′ are a hydroxy group, a sulfanyl group, a cyano group, a nitro group, or a monovalent hydrocarbon group having 1 to 30 carbon atoms. R ^B and R ^B ′ may be the same or different, and a plurality of R ^B and a plurality of R ^B ′ may be the same or different. R ⁷ and R ⁷ ′ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ⁷ and R ⁷ ′ may be the same or different, and a plurality of R ⁷ and a plurality of R ⁷ ′ may be the same or different. X is an integer from 0 to 4, h1 and h1 ′ are independently integers of 0 to 4, and h1 + h1 ′ ≧ 0. K1 and k1 ′ are independently integers of 0 to 4, and k1 + k1 ′> 0. H1 + k1 and h1 ′ + k1 ′ are integers of 0 to 4, respectively.

In the general formula (7), R ^C , R ^C ′ and R ^C ″ are a hydroxy group, a sulfanyl group, a cyano group, a nitro group or a monovalent hydrocarbon group having 1 to 30 carbon atoms. R ^C , R ^C ′ and R ^C ″ may be the same or different from each other, and a plurality of R ^C , a plurality of R ^C and a plurality of R ^C ″ are the same or different from each other. May be. R ⁸ , R ⁸ ′, and R ⁸ ″ each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ⁸ , R ⁸ ′, and R ⁸ ″ may be the same as or different from each other, and the plurality of R ⁸ , the plurality of R ⁸ ′, and the plurality of R ⁸ ″ may be the same. May be different. Y is an integer from 0 to 4, h2 and h2 ″ are independently integers of 0 to 4, h2 ′ is an integer of 0 to 2, and h2 + h2 ′ + h2 ″ ≧ 0. K2 and k2 ″ are independently integers of 0 to 4, k2 ′ is an integer of 0 to 2, and k2 + k2 ′ + k2 ″> 0. H2 + k2 and h2 ″ + k2 ″ are each an integer of 0 to 4, and h2 ′ + k2 ′ is an integer of 0 to 2.

In the general formula (8), R ^D , R ^D ′, R ^D ″ and R ^D ″ ″ are a hydroxy group, a sulfanyl group, a cyano group, a nitro group or a monovalent hydrocarbon group having 1 to 30 carbon atoms. is there. R ^D , R ^D ′, R ^D ″, and R ^D ″ ″ may be the same or different from each other, and a plurality of R ^D , a plurality of R ^D ′, a plurality of R ^D ″, and a plurality of R ^D ″ ^RD '''may be the same or different. R ⁹ , R ⁹ ′ R ⁹ ″ and R ⁹ ′ ″ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ⁹ , R ⁹ ′ R ⁹ ″ and R ⁹ ′ ″ may be the same as or different from each other, and a plurality of R ⁹ , a plurality of R ⁹ ′, a plurality of R ⁹ ″ and a plurality of R ⁹ ′ R ⁹ ′ ″ may be the same or different. Z is an integer from 0 to 4, h3 and h3 ′ ″ are independently integers from 0 to 4, h3 ′ and h3 ″ are independently integers from 0 to 2, and h3 + h3 ′ + h3 ″. + H3 ′ ″ ≧ 0. K3 and k3 ′ ″ are independently integers of 0 to 4, k3 ′ and k3 ″ are independently integers of 0 to 2, and k3 + k3 ′ + k3 ″ + k3 ′ ″> 0. H3 + k3 and h3 ′ ″ + k3 ′ ″ are each an integer from 0 to 4, and h3 ′ + k3 ′ and h3 ″ + k3 ″ are each an integer from 0 to 2.

  Among these, the compound represented by any one of the general formulas (6) to (8) is preferably a structure that easily forms a crosslinked structure with a crosslinking agent in order to suppress extraction into the upper layer of the ultraviolet absorber. . Specifically, a compound having a methylol group, an ethylol group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group or an ethoxyethyl group is more preferable, and a compound having a methylol group or an ethylol group is particularly preferable.

In general formula (6), X is preferably 1 or 2, h1 and h1 ′ are preferably 0 or 1, k1 and k1 ′ are preferably 0 or 1, and R ⁷ and R ⁷ ′ are a hydrogen atom, a methyl group, ethyl Group or propyl group is preferred. More preferably, h1 and h1 ′ are 0, and R ⁷ and R ⁷ ′ are hydrogen atoms.

In general formula (7), Y is preferably 1 or 2, h2, h2 ′ and h2 ″ are preferably 0 or 1, k2, k2 ′ and k2 ″ are preferably 0 or 1, and R ⁸ , R ⁸ ′. And R ⁸ ″ is preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group. More preferably, h2, h2 ′ and h2 ″ are 0, and R ⁸ , R ⁸ ′ and R ⁸ ″ are hydrogen atoms.

In the general formula (8), Z is preferably 1 or 2, h3, h3 ′, h3 ″ and h3 ′ ″ are preferably 0 or 1, and k3, k3 ′, k3 ″ and k3 ′ ″ are 0. Or 1 is preferable, and R ⁹ , R ⁹ ′, R ⁹ ″ and R ⁹ ″ ″ are preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group. More preferably, h3, h3 ′, h3 ″ and h3 ′ ″ are 0, and R ⁹ , R ⁹ ′, R ⁹ ″ and R ⁹ ′ ″ are hydrogen atoms.

  Preferred examples of these are:

Etc.

  Examples of ultraviolet absorbers for benzotriazole compounds include 2- (2Hbenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert-pentylphenol, 2- (2H Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- (2 '-Hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole, 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] ethyl Methacrylate, 4- [2- (6-Hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole -Yl] butyl methacrylate, 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] ethyl acrylate, 2- [2- (6-hydroxybenzo) [1,3] dioxol-5-yl) -2H-benzotriazol-5-yloxy] ethyl methacrylate, 4- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole -5-yloxy] butyl methacrylate, 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yloxy] ethyl acrylate, 2- [3- {2- (6-Hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl} prop Yloxy] ethyl methacrylate, 4- [3- {2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl} propanoyloxy] butyl methacrylate, 2- [3 -{2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl} propanoyloxy] ethyl acrylate, 2- (methacryloyloxy) ethyl, 2- (6- Hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-carboxylate, 4- (methacryloyloxy) butyl, 2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-carboxylate, 2- (acryloyloxy) ethyl, 2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-carboxylate and the like. Examples of ultraviolet absorbers for benzophenone compounds include 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4. , 4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzo Non, 2-ethylhexyl-4′-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone and the like. Examples of ultraviolet absorbers for triazine compounds include bisresorcinyltriazine, 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3 , 5-triazine, octyltriazone (2,4,6-tris {4- (2-ethylhexyloxycarbonyl) anilino} 1,3,5-triazine), 2- (4,6-diphenyl-1,3, 5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4-bis [2-hydroxy-4-butoxyphenyl] -8- (2,4-dibutoxyphenyl) -1,3 , 5-triazine and the like.

  Although there is no restriction | limiting in particular in content of the (C) ultraviolet-ray absorption compound in the composition of this invention, Preferably it is the range of 5-35 weight part with respect to 100 weight part of (A) polyether sulfone resin, More preferably (A) It is the range of 10-30 weight part with respect to 100 weight part of polyether sulfone resin.

  The resin composition for an antireflection film of the present invention may contain a solvent (D). (D) Although there is no restriction | limiting in particular as a solvent, Preferably the cyclic compound which has a carbonyl group represented by General formula (9) is used.

W represents a divalent hydrocarbon group having 1 to 4 carbon atoms, an oxygen atom or NR ¹⁰ , and R ¹⁰ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. j represents an integer of 1 to 5. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, and a butylene group.

When a cyclic compound having a carbonyl group represented by the general formula (9) is used as a solvent, even if the composition is applied to form a film, the film does not whiten and high transparency can be achieved. Although there is no restriction | limiting in particular, Preferably it is a compound whose boiling point under atmospheric pressure is 150 to 250 degreeC. When the boiling point is in the range of 150 to 250 ° C., good flatness can be obtained because the solvent is appropriately volatilized during baking.

Specific examples of the cyclic compound having a carbonyl group include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, and cycloheptanone. Among these, cyclohexanone and γ-butyrolactone are particularly preferably used.

  In addition, you may use the cyclic compound which has these carbonyl groups individually or in combination of 2 or more types.

Moreover, the resin composition for antireflection films of the present invention may contain other solvents as long as the effects of the present invention are not impaired. Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Esters such as monobutyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, isobutyl ketone, acetylacetone , Ethers such as diethyl ether, diisopropyl ether, di n-butyl ether, diphenyl ether and the like.

  Although there is no restriction | limiting in particular in (D) solvent content in the composition of this invention, Preferably it is the range of 1000-5000 weight part with respect to 100 weight part of (A) polyether sulfone resin.

  The composition of the present invention may contain a thermal acid generator as another component for the purpose of accelerating curing by heat. The thermal acid generator generates an acid by heating after development, and promotes a crosslinking reaction between the resin as the component (A) and the thermal crosslinking agent as the component (B). For this reason, the chemical resistance of the cured film is improved, and film loss can be reduced. The acid generated from the thermal acid generator is preferably a strong acid. For example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid are preferable.

  In the case of containing a thermal acid generator, the content is preferably 0.1 parts by weight or more, and 0.3 parts by weight or more with respect to 100 parts by weight of the component (A) resin from the viewpoint of further promoting the crosslinking reaction. Is more preferable, and 0.5 parts by weight or more is more preferable. On the other hand, from the viewpoint of electrical insulation of the cured film, 20 parts by weight or less is preferable, 15 parts by weight or less is more preferable, and 10 parts by weight or less is more preferable. In addition, when 2 or more types of thermal acid generators are contained, it is preferable that those total amount is the said range.

  Moreover, you may contain surfactant for the purpose of improving the striation at the time of application | coating, wettability, etc. In that case, the preferable content of the surfactant in the composition of the present invention is 1 part by weight or less, more preferably 0.2 parts by weight or less with respect to 100 parts by weight of the (A) polyether sulfone resin.

(Antireflection film)
The antireflection film of the present invention is formed by the above-described resin composition for an antireflection film.

  This antireflection film is suitable for the purpose of forming a lower layer film as an antireflection film on a substrate, improving the pattern shape in exposure and development of the photosensitive resin film formed thereon, and increasing the resolution of the pattern. used.

(Production method of antireflection film)
The method for forming an antireflection film of the present invention includes (a) a step of applying the above-described resin composition for an antireflection film on a substrate to form a film, and (b) a step of heating the film.

  The antireflection film is usually formed on the upper surface side of the substrate. As the substrate, for example, a silicon wafer, a wafer coated with aluminum, or the like can be used.

  Moreover, the application | coating method of the resin composition for anti-reflective films to a board | substrate is not specifically limited, For example, it can implement by appropriate methods, such as spin coating, cast coating, and roll coating.

  Moreover, heating of a coating film is normally performed in air | atmosphere.

  The heating temperature at this time is usually 200 ° C to 300 ° C, preferably 200 ° C to 250 ° C. When this heating temperature is less than 200 ° C., oxidative crosslinking does not proceed sufficiently, and there is a possibility that characteristics necessary for the lower layer film may not be exhibited.

  The heating time at this time is 30 to 1,200 seconds, preferably 60 to 600 seconds.

  Furthermore, the oxygen concentration at the time of curing the coating film is desirably 5% by volume or more. When the oxygen concentration at the time of coating film formation is low, the oxidation cross-linking of the resist underlayer film does not proceed sufficiently, and there is a possibility that the characteristics necessary for the resist underlayer film cannot be expressed.

  Moreover, before heating a coating film at the temperature of 200 to 300 degreeC, you may preheat at the temperature of 60 to 150 degreeC.

  The heating time in the preheating is not particularly limited, but is preferably 10 seconds to 300 seconds, and more preferably 30 seconds to 180 seconds.

  By performing this preheating, the dehydrogenation reaction can be efficiently advanced by vaporizing the solvent in advance and keeping the film dense.

(Pattern formation method)
The pattern forming method of the present invention includes the following steps (a ′) to (e ′) in this order.

(A ′) a step of coating the antireflective film resin composition described above on a substrate to form a film;
(B ′) heating the film;
(C ′) forming a film by applying a photosensitive resin composition to the surface of the film opposite to the substrate;
(D ′) exposing at least a part of the film;
(E ′) A step of developing a pattern of the exposed photosensitive resin composition to form a pattern.

[Steps (a ′) and (b ′)]
In steps (a ′) and (b ′), an antireflection film is formed on the upper surface side of the substrate. The specific formation method is as described above.

  In addition, it is preferable that the film thickness of an antireflection film is 0.01 micrometer-0.3 micrometer normally.

[Step (c ′)]
In the step (c ′), a photosensitive resin film is formed on the upper surface side of the antireflection film using the photosensitive resin composition. Specifically, after the photosensitive resin composition is applied so that the obtained photosensitive resin film has a predetermined film thickness, the solvent in the coating film is volatilized by pre-baking the photosensitive resin film. It is formed.

  Examples of the photosensitive resin composition include a negative photosensitive resin composition containing an alkali-soluble resin and a crosslinking agent, and a positive photosensitive resin composition containing an alkali-soluble resin and a quinonediazide-based photosensitive agent. Moreover, when applying the technique of this invention to a solid-state image sensor so that it may mention later, the pixel formation composition for forming the pixel pattern of a color filter can be used as a photosensitive resin composition. The pixel may be any of a red pixel, a green pixel, a blue pixel, and a white pixel.

The photosensitive resin composition used when forming the photosensitive resin film on the antireflection film has a solid content concentration of usually about 5 to 50% by mass, and generally has a pore diameter of about 0.2 μm, for example. Filtration with a filter is used for forming a photosensitive resin film.
The coating method of the photosensitive resin composition is not particularly limited, and for example, it can be performed by a spin coating method or the like.

  Moreover, although the temperature of prebaking is suitably adjusted according to the kind etc. of photosensitive resin composition to be used, it is about 30 to 200 degreeC normally, Preferably it is 50 to 150 degreeC.

  The film thickness of the photosensitive resin formed in this step (c ′) is preferably 0.3 μm to 2 μm.

[Step (d ′)]
In the step (d ′), a predetermined region of the obtained photosensitive resin film is irradiated with radiation and selectively exposed.

  The radiation used for exposure can be selected according to the photosensitive resin used, but ultraviolet rays, particularly i-line (365 nm) is preferable.

[Step (e ′)]
In the step (e ′), a photosensitive resin pattern is formed by developing the exposed photosensitive resin film with a developer.

  As the developer used in this step, an aqueous solution of tetramethylammonium hydroxide is mainly used. Furthermore, water-soluble organic solvents, for example, alcohols such as methanol and ethanol, and surfactants can be added in appropriate amounts.

  As the resolution of the obtained pattern, it is preferable to resolve a 1 μm square pattern. As the pattern shape, the cross section is preferably 85 to 90 ° (hereinafter referred to as a taper angle) with respect to the bottom surface. The development residue is preferably as little as possible.

  A predetermined photosensitive resin pattern is formed by washing and drying after development with the developer.

  If necessary, the photosensitive resin pattern can be further post-baked. The post-baking temperature is preferably 200 ° C to 300 ° C.

(Solid-state imaging device)
The composition of the present invention can be used without particular limitation as long as it is a use in which a pattern using a photosensitive resin composition is formed on an antireflection film comprising the composition. It is preferably used for forming a filter pixel pattern. That is, the photosensitive resin composition is preferably a pixel forming composition in a solid-state imaging device.

  The solid-state imaging device has at least a photoelectric conversion layer, an antireflection film, and pixels in this order. Specifically, as shown in FIG. 1, the antireflection film 4, the color filter 3, and the microlens 1 are provided on a silicon substrate 5 including a photoelectric conversion layer (not shown). Among them, each color pixel constituting the color filter 3 is formed on the antireflection film 4 by photolithography. The size per pixel is 0.5 μm to 0.8 μm in height and 0.9 μm to 1.4 μm in length and width. A pixel is composed of three colors, a red pixel (R), a green pixel (G), and a blue pixel (B), and a red pixel (R), a green pixel (G), a blue pixel (B), and a white pixel (W ) In four colors. From the viewpoint of obtaining an image with less noise than the three-color solid-state image sensor, the four-color solid-state image sensor including the white pixel (W) preferably has a four-color pixel configuration including the white pixel. FIG. 1 shows a four-color pixel configuration including a red pixel 2R, a green pixel 2G, a blue pixel 2B, and a white pixel 2W.

  The antireflection film obtained from the composition of the present invention is preferably used as an antireflection film of such a solid-state imaging device.

  An example of a color filter manufacturing process in the solid-state imaging device is shown below. The antireflection film 4 is formed with a thickness of 20 nm to 200 nm on the silicon substrate 5 including the photoelectric conversion element. On top of that, a photosensitive material for forming white pixels or green pixels is applied and patterned into a checkered shape having a size of 0.9 to 1.4 μm square, and then a blue pixel and a red pixel are formed. In general, a photosensitive material is applied, exposed, and developed to form a gap between white pixels or green pixels.

  Among them, white pixels or green pixels are required to have the finest resolution, and resolution with a pattern size of 0.9 to 1.1 μm square is required. The white pixel is preferably made of a material having a high refractive index of 1.7 or more from the viewpoint of improving the photosensitivity of the solid-state imaging device. The difference becomes large and the light is reflected. For this reason, when white pixels are formed by photolithography, the reflection of light during exposure causes the pattern shape to be lost and development residue, which causes noise in the image taken with the solid-state image sensor and decreases the color tone. There is a possibility of doing. Therefore, it is particularly preferable to use the resin composition of the present invention in the production of a solid-state imaging device including white pixels. Accordingly, when white pixels having a high refractive index are formed by photolithography, light reflection at the time of exposure is suppressed, so that the development residue can be suppressed without breaking the pixel shape. In addition, the solid-state imaging device thus obtained can capture an image layer having no noise and good color tone.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these ranges.

Abbreviations of the solvents used are as follows.
DAA: diacetone alcohol PGMEA: propylene glycol monomethyl ether acetate rBL: gamma butyrolactone CyHex: cyclohexanone TMAH: tetramethylammonium hydroxide.

<Measurement and evaluation>
(1) Film thickness measurement Film thickness was measured at a refractive index of 1.65 using Lambda Ace STM-602 (trade name, manufactured by Dainippon Screen). A total of three locations were measured, an average value, which was the center of an 8-inch silicon wafer, an arbitrary location 4 cm away from the center, and an arbitrary location 8 cm away from the center.

(2) Refractive Index Measurement An antireflection film-forming composition was spin-coated on an 8-inch silicon wafer, baked on a hot plate at 100 ° C. for 120 seconds, and then baked at 220 ° C. for 5 minutes. A 7 μm antireflection film was formed. About the obtained anti-reflective film, the refractive index in 633 nm in 22 degreeC was measured using Otsuka Electronics Co., Ltd. spectroscopic ellipsometer FE5000.

(3) Evaluation of chemical resistance The formed antireflection film was immersed in PGMEA and 2.38 wt% TMAH aqueous solution at 25 ° C for 2 minutes, respectively, and "S" when the remaining film ratio before and after that was 99% or more (Very good), it was judged as “A” (good) when it was 95% or more and less than 99%, and “B” (bad) when it was less than 95%. The remaining film ratio was calculated according to the following formula.
Remaining film ratio (%) = film thickness after immersion / film thickness before immersion × 100
About the film thickness, it measured by the method as described in said (1) film thickness measurement.

(4) Evaluation of photosensitive resin pattern ・ Resolution Regarding the cured film of the photosensitive material for white pixels obtained on the antireflection film, a square pattern was observed with the minimum exposure amount at which no film peeling occurred during development. The post-development resolution was used.

Shape evaluation: A 1 μm square pattern of the photosensitive material for white pixels formed on the antireflection film is observed. When the rectangular shape has a taper angle of 85 to 90 °, the shape is “S” (very good), and the taper angle is 80 The shape evaluation was “A” (good) when the angle was over 60 °, and the shape evaluation was “B” (bad) when the trapezoid had a taper angle of 80 ° or less.

Residue evaluation A 1 μm square pattern was observed with FE-SEM (Hitachi, S-4800) at a magnification of 30000 times, and when no foreign particles or resin deposits were observed around the pattern, residue evaluation was performed. When observed as “A” (good), the residue was evaluated as “B” (bad).

(5) Evaluation of mixing properties The film thickness of the antireflection film was measured with an optical film thickness meter. (The film thickness at this time is assumed to be m1.) Next, a white pixel photosensitive resin (NP) was applied, exposed, developed, and post-baked. After the post-baking, the film thickness of the unexposed part was measured with a film thickness meter (the film thickness of the antireflection film at this time is m2), and m2-m1 was calculated. When m2−m1 ≦ 5 nm and no change in appearance such as film unevenness or film peeling occurs, no intermixing is performed (mixing evaluation “A” (good)), and m2−m1> 5 nm or change in appearance occurs. In the case of intermixing (mixing evaluation “B” (bad)).

Synthesis Example 1 Synthesis of alkoxymethyl group-containing thermal crosslinking agent (B-1) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 103.2 g (0.4 mol) was added to sodium hydroxide 80 g (2. 0 mol) was dissolved in a solution of 800 g of pure water. After complete dissolution, 686 g of 36-38 wt% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Then, it stirred at 20-25 degreeC for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and allowed to stand for 2 days. Needle-like white crystals formed in the solution after standing were collected by filtration and washed with 100 mL of water. The white crystals were vacuum dried at 50 ° C. for 48 hours. When the dried white crystals were analyzed at 254 nm using high performance liquid chromatography manufactured by Shimadzu Corporation using ODS as the column and acetonitrile / water = 70/30 as the developing solvent, the starting material disappeared completely. The purity was found to be 92%. Furthermore, when it analyzed by NMR (the JEOL Co., Ltd. product, GX-270) using DMSO-d6 for a heavy solvent, it turned out that it is the trimethyl P-HAP hexamethylolated.

  Next, the compound thus obtained was dissolved in 300 mL of methanol, 2 g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours. To this solution, 15 g of an anionic ion exchange resin (Rumm and Haas, Amberlyst IRA96SB) was added and stirred for 1 hour, and the ion exchange resin was removed by filtration. Thereafter, 500 mL of ethyl lactate was added, and methanol was removed by a rotary evaporator to obtain an ethyl lactate solution. When this solution was allowed to stand at room temperature for 2 days, white crystals were formed. When the obtained white crystals were analyzed by a high performance liquid chromatography method, it was a 99% pure TrisP-HAP hexamethoxymethyl compound (alkoxymethyl group-containing thermal crosslinking agent (B-1)) represented by the following formula. I understood it.

<Synthesis Example 2 alkoxymethyl group-containing thermal crosslinking agent (B-2)>
190.1 g (0.33 mol) of TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) was dissolved in a solution of 80 g (2.0 mol) of sodium hydroxide in 800 g of pure water. After complete dissolution, 686 g of 36-38 wt% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Then, it stirred at 20-25 degreeC for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and allowed to stand for 2 days. Needle-like white crystals formed in the solution after standing were collected by filtration and washed with 100 mL of water. The white crystals were vacuum dried at 50 ° C. for 48 hours. When the dried white crystals were analyzed at 254 nm using high performance liquid chromatography manufactured by Shimadzu Corporation using ODS as the column and acetonitrile / water = 70/30 as the developing solvent, the starting material disappeared completely. The purity was found to be 92%. Furthermore, when it analyzed by NMR (the JEOL Co., Ltd. product, GX-270) using DMSO-d6 for a heavy solvent, it turned out that it is TekP-4HBPA made into hexamethylol.

  Next, the compound thus obtained was dissolved in 500 mL of methanol, 2 g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours. To this solution, 15 g of an anionic ion exchange resin (Rumm and Haas, Amberlyst IRA96SB) was added and stirred for 1 hour, and the ion exchange resin was removed by filtration. Thereafter, 500 mL of ethyl lactate was added, and methanol was removed by a rotary evaporator to obtain an ethyl lactate solution. When this solution was allowed to stand at room temperature for 2 days, white crystals were formed. When the obtained white crystals were analyzed by high performance liquid chromatography, it was a TekP-4HBPA hexamethoxymethyl compound (alkoxymethyl group-containing thermal crosslinking agent (B-2)) having a purity of 99% represented by the following formula. I understood it.

<Synthesis Example 3 alkoxymethyl group-containing thermal crosslinking agent (B-3)>
TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 139.9 g (0.33 mol) was dissolved in a solution obtained by dissolving 80 g (2.0 mol) of sodium hydroxide in 800 g of pure water. After complete dissolution, 686 g of 36-38 wt% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Then, it stirred at 20-25 degreeC for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and allowed to stand for 2 days. Needle-like white crystals formed in the solution after standing were collected by filtration and washed with 100 mL of water. The white crystals were vacuum dried at 50 ° C. for 48 hours. When the dried white crystals were analyzed at 254 nm using high performance liquid chromatography manufactured by Shimadzu Corporation using ODS as the column and acetonitrile / water = 70/30 as the developing solvent, the starting material disappeared completely. The purity was found to be 92%. Furthermore, when it analyzed by NMR (the JEOL Co., Ltd. product, GX-270) using DMSO-d6 for a heavy solvent, it turned out that it is a trimethyl P-PA hexahexylol-ized.

  Next, the compound thus obtained was dissolved in 500 mL of ethanol, 2 g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours. To this solution, 15 g of an anionic ion exchange resin (Rumm and Haas, Amberlyst IRA96SB) was added and stirred for 1 hour, and the ion exchange resin was removed by filtration. Thereafter, 500 mL of ethyl lactate was added, and methanol was removed by a rotary evaporator to obtain an ethyl lactate solution. When this solution was allowed to stand at room temperature for 2 days, white crystals were formed. When the obtained white crystals were analyzed by a high performance liquid chromatography method, it was a 99% pure TrisP-PA hexaethoxymethyl compound (alkoxymethyl group-containing thermal crosslinking agent (B-3)) represented by the following formula. I understood it.

<Synthesis Example 4 Synthesis of Acrylic Resin (R1) of Comparative Example>
A 500 ml flask was charged with 1 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, 23.0 g of methacrylic acid, 31.5 g of benzyl methacrylate, and 32.8 g of tricyclo [5.2.1.02,6] decan-8-yl methacrylate were charged, stirred at room temperature for a while and bubbled in the flask. After sufficiently purging with nitrogen, the mixture was stirred with heating at 70 ° C. for 5 hours. Next, 12.7 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours. After completion of the reaction, the reaction solution was subjected to liquid separation extraction treatment with a 1N aqueous formic acid solution to remove the addition catalyst, dried over magnesium sulfate, and then the solution was poured into 1 L of hexane, and a polymer solid precipitate was collected by filtration. Furthermore, it wash | cleaned 3 times by 1 L of hexane, and the collected polymer solid was dried with the 40 degreeC vacuum dryer for 24 hours, and the acrylic resin (R1) of the comparative example was obtained.

<Synthesis Example 5 Synthesis of Polyamic Acid Ester Resin (R2) of Comparative Example>
18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd.), 100 mL of acetone, propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) 17 It was dissolved in 0.4 g (0.3 mol) and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the obtained white solid was put in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the catalyst was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a diamine compound (α) represented by the following formula.

  Subsequently, 15.1 g (0.025 mol) of the obtained diamine compound (α) and 3.66 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0. 01 mol) and 0.62 g (0.0025 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 200 g of N-methyl-2-pyrrolidone. Here, 22.2 g (0.05 mol) of 6FDA (manufactured by Daikin Industries, Ltd.) was added together with 50 g of N-methyl-2-pyrrolidone and stirred at 40 ° C. for 1 hour. Thereafter, 2.73 g (0.025 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 40 ° C. for 1 hour. Further, a solution prepared by diluting 11.9 g (0.1 mol) of N, N-dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd.) with 5 g of N-methyl-2-pyrrolidone was added dropwise over 10 minutes. And stirring was continued at 40 ° C. for 2 hours. After the completion of stirring, the solution was poured into 2 L of water, and a precipitate of polymer solid was collected by filtration. Further, it was washed 3 times with 2 L of water, and the collected polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a polyamic acid ester resin (R2).

<Synthesis Example 6 Synthesis of Photosensitive Material (NP) for White Pixel>
In a 500 ml flask, 40.86 g (0.3 mol) of methyltrimethoxysilyl, 69.41 g (0.35 mol) of phenyltrimethoxysilane, 82.04 g (0.35 mol) of γ-acryloylpropyltrimethoxysilane, DAA (diacetone) 192.3 g of alcohol) is placed in an oil bath at 40 ° C. and stirred, and 54.0 g of water (theoretical amount required for hydrolysis) is added to 0.39 g of phosphoric acid (0.2 parts by weight relative to the charged monomer). An aqueous phosphoric acid solution in which was dissolved was added with a dropping funnel over 10 minutes. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour, and the oil bath was further heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 120 g of methanol and water as by-products were distilled out. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt% to obtain a photosensitive resin solution (PS) for white pixels.

  Subsequently, 6.375 g of the obtained photosensitive resin solution (PS) for white pixels, 0.3 g of Aronix M360 (manufactured by Toagosei Co., Ltd.), 0.125 g of Irgacure 819 (manufactured by BASF), t-butylcatechol (Pure Wako) Yakuhin Co., Ltd.) 0.05 g, DAA 1.075 g, PGMEA 2.1 g and DFX-18 (manufactured by Neos Co., Ltd.) 1% PGMEA diluted solution 0.1 g were mixed and stirred under a yellow light to obtain a homogeneous solution. Then, the mixture was filtered through a 0.20 μm filter to prepare a white pixel photosensitive material (NP).

<Example 1>
As shown in Table 1, preparation was performed at a ratio of composition 1 under a yellow lamp. Specifically, polyether sulfone resin (1) (Sumika Excel 4100P, manufactured by Sumitomo Chemical Co., Ltd.) 0.85 g, thermal cross-linking agent (B-1) (Nicarac MX-270, manufactured by Sanwa Chemical Co., Ltd.) 0 .10 g, UV absorbing compound (C-1) (manufactured by TINUVIN329 BASF) 0.05 g, (WPAG-315 Wako Pure Chemical Industries, Ltd.) 0.01 g, mixed solvent of cyclohexanone 22.63 g and γ-butyrolactone 9.70 g Then, a surfactant was added to prepare an antireflection film resin composition 1. Incidentally, BYK-352 (manufactured by Big Chemie Japan Co., Ltd.) was used as the surfactant.

  After the composition 1 was prepared, spin coating was performed on an 8-inch silicon wafer using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.), and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. The prebaked film with a film thickness of 80 nm was produced by heating at 0 ° C. for 3 minutes. Thereafter, it was post-baked at 220 ° C. for 5 minutes using a hot plate to produce an antireflection film. Using the obtained antireflection film, (1) film thickness measurement and (3) chemical resistance evaluation were performed.

  Subsequently, a photosensitive resin solution (NP) for white pixels is spin-coated on the antireflection film so as to have a film thickness of 0.5 μm, and then baked on a hot plate at 100 ° C. for 1 minute to form a photosensitive resin film. Formed. Next, using a Nikon i-line stepper NSR2005iqq (wavelength 365 nm), an exposure time for forming a line-and-space pattern having a width of 1.0 μm with a one-to-one line width (hereinafter referred to as “optimum exposure time”). Only exposure was performed. Next, using a 0.5% tetramethylammonium hydroxide aqueous solution, development was performed at 23 ° C. for 90 seconds, washed with water, dried, and then post-baked on a hot plate at 220 ° C. for 5 minutes to form a negative pattern. With respect to the obtained patterning substrate, (4) evaluation of the photosensitive resin pattern and (5) mixing property evaluation were performed, respectively. (2) About optical characteristic evaluation, since the film thickness of the target was different, a cured film was separately prepared and evaluated. These results are shown in Table 4.

<Examples 2 to 10>
In the same procedure as in Example 1, antireflection coating compositions 2 to 10 were prepared according to the compositions in Table 1, and (1) to (6) were evaluated. These results are shown in Table 4. The polyether sulfone resins (A-2) to (A-5) shown below were used.
(A-2) Sumika Excel 3600P (manufactured by Sumitomo Chemical Co., Ltd.)
(A-3) Sumika Excel 5400P (manufactured by Sumitomo Chemical Co., Ltd.)
(A-4) Ultrason E2020P SR (manufactured by BASF)
(A-5) Veradel 3000P (manufactured by Solvay Specialty Polymers).

  The structures of Nikarak MX-270, MW-100LM, TINUVIN329, and TINUVIN460 are as follows.

<Examples 11 to 17>
In the same procedure as in Example 1, antireflection film compositions 11 to 17 were prepared according to the compositions in Table 2, and (1) to (5) were evaluated. These results are shown in Table 5.

<Examples 18 to 25>
In the same procedure as in Example 1, antireflection film compositions 18 to 25 were produced according to the compositions in Table 3, and (1) to (5) were evaluated. In addition, the ultraviolet absorption compounds (C-1) to (C-6) in Table 3 were as shown below. These results are shown in Table 5.
(C-1) 9-hydroxymethylanthracene (manufactured by TCI)
(C-2) 2-hydroxymethylanthracene (manufactured by TCI)
(C-3) 9- (2-hydroxyethyl) anthracene (manufactured by TCI)
(C-4) 1,8-bis (hydroxymethyl) anthracene (manufactured by TCI)
(C-5) 9,10-dipropoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd.)
(C-6) 1,8,9-trihydroxyanthracene (manufactured by TCI)
<Comparative Examples 1-8>
In the same procedure as in Example 1, compositions of Comparative Examples (Comparative Examples 1 to 8) having the compositions shown in Table 6 were prepared, and (1) to (5) were evaluated. Table 7 shows the evaluation results.

1 Micro lens 2R Red pixel 2G Green pixel 2B Blue pixel 2W White pixel 3 Color filter 4 Antireflection film 5 Silicon substrate

Claims (10)

(A) Polyether sulfone resin, (B) cross-linking agent, and (C) UV-absorbing compound , wherein the (C) UV-absorbing compound comprises: A resin composition for an antireflection film, which is an ultraviolet absorbing compound represented by any one of the general formulas (6) to (8) .
(In General Formula (6), R ^B and R ^B ′ are a hydroxy group, a sulfanyl group, a cyano group, a nitro group, or a monovalent hydrocarbon group having 1 to 30 carbon atoms. R ^B and R ^B ′ are the same. Or a plurality of R ^B and a plurality of R ^B ′ may be the same or different from each other. R ⁷ and R ⁷ ′ are a hydrogen atom or a group having 1 to 6 carbon atoms. Represents a monovalent hydrocarbon group, R ⁷ and R ⁷ 'may be the same or different, and a plurality of R ⁷ and a plurality of R ⁷ ' may be the same or different; X is an integer from 0 to 4, h1 and h1 ′ are independently integers from 0 to 4, and h1 + h1 ′ ≧ 0, and k1 and k1 ′ are independently integers from 0 to 4. And k1 + k1 ′> 0, and h1 + k1 and h1 ′ + k1 ′ are respectively It is an integer from 0 to 4.)
(In the general formula ^{(7), R C, R} C ' and R ^C' 'is hydroxy group, sulfanyl group, a cyano group, a monovalent hydrocarbon group of a nitro group or a C1-30 ^.R C, R ^C ′ and R ^C ″ may be the same or different from each other, and a plurality of R ^C , a plurality of R ^C and a plurality of R ^C ″ may be the same or different from each other. R ⁸ , R ⁸ ′, and R ⁸ ″ each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ⁸ , R ⁸ ′, and R ⁸ ″ are the same as each other. And a plurality of R ⁸ , a plurality of R ⁸ ′ and a plurality of R ⁸ ″ may be the same or different. Y is an integer from 0 to 4, h2 And h2 ″ are independently an integer of 0 to 4, h2 ′ is an integer of 0 to 2, and h2 + h2 ′ + h2 ″ ≧ 0 K2 and k2 ″ are independently integers of 0 to 4, k2 ′ is an integer of 0 to 2, and k2 + k2 ′ + k2 ″> 0. H2 + k2 and h2 ″ + k2 ″ are Each is an integer from 0 to 4, and h2 ′ + k2 ′ is an integer from 0 to 2.)
(In the general formula (8), R ^D , R ^D ′, R ^D ″ and R ^D ″ are a hydroxy group, a sulfanyl group, a cyano group, a nitro group, or a monovalent hydrocarbon group having 1 to 30 carbon atoms. R ^D , R ^D ′, R ^D ″ and R ^D ″ may be the same as or different from each other, and a plurality of R ^D , a plurality of R ^D ′, and a plurality of R ^D ′ 'And a plurality of R ^D ''' may be the same or different from each other. R ⁹ , R ⁹ 'R ⁹ ', and R ⁹ '''may be a hydrogen atom or 1 to 6 carbon atoms. R ⁹ , R ⁹ ′ R ⁹ ″, and R ⁹ ′ ″ may be the same or different from each other , and a plurality of R ⁹ , a plurality of R ⁹ ′, good .Z be different even multiple R ^{9 ''} and a plurality of R 9 ^'' 'is respectively identical an integer from 0 to 4, h3 and h3''' is independently Integers of ˜4, h3 ′ and h3 ″ are independently integers of 0 to 2, and h3 + h3 ′ + h3 ″ + h3 ′ ″ ≧ 0. K3 and k3 ′ ″ are independently 0 Integers ˜4, k3 ′ and k3 ″ are independently integers 0-2 and k3 + k3 ′ + k3 ″ + k3 ′ ″> 0. H3 + k3 and h3 ′ ″ + k3 ′ ″ are Each is an integer from 0 to 4, and h3 ′ + k3 ′ and h3 ″ + k3 ″ are each an integer from 0 to 2.) The resin composition for an antireflection film according to claim 1, wherein (A) the polyether sulfone resin includes a structure represented by the following general formula (4).
(In the general formula ( 4 ), R ¹ and R ² are each independently a hydrogen atom, a hydroxy group, a carboxyl group, a monovalent hydrocarbon group having 1 to 4 carbon atoms, or a monovalent hydrocarbon group having 1 to 4 carbon atoms. (It is an oxyhydrocarbon group. N represents an integer of 5 to 500. A plurality of R ¹ and R ² may be the same or different.) 2. The resin composition for an antireflection film according to claim 1, wherein the crosslinking agent (B) is a crosslinking agent containing an alkoxymethyl group or a methylol group represented by the following general formula (5).
(In General Formula (5), R ^A represents a direct bond or a monovalent to tetravalent linking group. R ³ and R ⁴ each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ⁵ represents a hydrogen atom, a methyl group or an ethyl group, R ⁶ represents a monovalent organic group having 1 to 20 carbon atoms or a fluorine atom, l represents an integer of 0 to 2, and m represents an integer of 1 to 4. If when .R ^a is a direct bond and m is 2 .m is 2 to 4, a plurality of ^R 3 to R ⁶ may be the same or different, but the same benzene ring and ^{R 6} 2 R ⁶ is the same when there are two.) Furthermore (D) anti-reflective coating resin composition according to any one of claims 1 to 3, characterized in that it comprises a solvent represented by the following general formula (9).
(W represents a divalent hydrocarbon group having 1 to 4 carbon atoms, an oxygen atom or NR ¹⁰ ; R ¹⁰ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; j represents an integer of 1 to 5; Show.) A method for producing an antireflection film comprising the following steps (a) and (b) in this order;
(A) The process of apply | coating the resin composition for antireflection films in any one of Claims 1-4 on a board | substrate, and forming a film | membrane;
(B) A step of heating the film. A pattern production method comprising the following steps (a ′) to (e ′) in this order;
(A ′) a step of forming a film by applying the resin composition for an antireflection film according to any one of claims 1 to 3 on a substrate;
(B ′) heating the film;
(C ′) forming a film by applying a photosensitive resin composition to the surface of the film opposite to the substrate;
(D ′) a step of exposing at least a part of the film of the photosensitive resin composition;
(E ′) A step of developing the exposed photosensitive resin composition film to form a pattern. The pattern manufacturing method according to claim 6, wherein the photosensitive resin composition is a composition for forming a pixel in a solid-state imaging device. The solid-state image sensor which has an antireflection film obtained from the resin composition for antireflection films in any one of Claims 1-3 . The antireflection film obtained from the resin composition for an antireflection film according to any one of claims 1 to 3 , wherein the solid-state imaging device has at least a photoelectric conversion layer, an antireflection film, and pixels in this order. The solid-state imaging device according to claim 8 . The solid-state imaging device according to claim 9 , wherein the pixel includes a white pixel.