JP2012013962A - Photosensitive composition, pattern forming material, and photosensitive film, pattern forming method, patterned film, low refractive index film, optical device, and solid-state image pickup device using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition and a pattern forming material that enable formation of a pattern having high appropriate sensitivity, a low refractive index, little pattern chipping or residue after developed, and little change in the refractive index in a high temperature and high humidity environment, and exhibiting an excellent weather resistance property; and to provide a photosensitive film, a pattern forming method, a patterned film, a low refractive index film, an optical device and a solid-state image pickup element using the composition.SOLUTION: The photosensitive composition and the pattern forming material contain (A) hollow or porous particles, (B) a compound that generates an active species by irradiation with active rays or radiation, and the following resin (C1) or mixture resin (C2). The photosensitive film, pattern forming method, patterned film, low refractive index film, optical device, and solid-state image pickup element use the composition. The resin (C1) contains a silicon atom or a fluorine atom in a side chain and changes the solubility with an alkali developing solution by an action of the active species; and the mixture resin (C2) contains a resin (C2-1) having a silicon atom or fluorine atom in a side chain and a resin (C2-2) having the solubility with an alkali developing solution changed by an action of the active species.

Description

  The present invention relates to a photosensitive composition, a pattern forming material, a photosensitive film using the same, a pattern forming method, a pattern film, a low refractive index film, an optical device, and a solid-state imaging device.

  Low refractive index film is anti-reflection film, reflection film, semi-transmission semi-reflection film, visible light reflection infrared transmission film, infrared reflection visible light transmission film, blue reflection film, green reflection or red reflection film, bright line cut filter, color correction An optical functional film included in the film is formed on the optical member.

  Not only optical members with a flat surface shape, but also optical function members such as brightness enhancement lens films and diffusion films for liquid crystal backlights, Fresnel lenses, lenticular lenses, and microlenses used for video projection television screens are all made of resin. The desired geometrical optical performance is obtained because the material has a microstructure. An optical functional film including a low refractive index film is also required on the surface of these fine structures.

  When a low refractive index film is used as an antireflection film, the low refractive index film having a single layer structure becomes an antireflection film as it is. As the refractive index of the antireflection film having a single layer structure, when the substrate is a transparent material such as a resin material, a low refractive index in the range of 1.2 to 1.35 is desired.

  The typical material of the low refractive index film includes a fluorine polymer material having a refractive index of 1.35 to 1.4, and fine particles made of a polymer of a fluorine monomer having a refractive index of 1.37 to 1.46. Although there is a layer containing a porous material in which the material is fused (see, for example, Patent Document 1), a material having a refractive index of 1.3 or less has not been obtained.

  In addition to such reflectance characteristics, many problems such as complexity of the manufacturing process are desired to be solved. In Patent Documents 2 and 3, in order to eliminate the complexity of the manufacturing process, as a patterning method that does not use a photoresist, a silica-based material having photosensitivity is used to expose and develop itself to form a pattern. Although the method is described, the appropriate sensitivity in pattern formation is insufficient, and the refractive index property of the resulting pattern is also insufficient.

Japanese Patent No. 3718031 JP 2010-31222 A JP 2010-32996 A

  The present invention has been made in view of the above, and has high appropriate sensitivity, low refractive index, little chipping and residue of pattern after development, small change in refractive index under high temperature and high humidity, and excellent weather resistance. Composition, pattern forming material, and photosensitive film using the same, pattern forming method, pattern film, low refractive index film, optical device, and solid-state imaging device The purpose is to do.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means.
Specific means for solving the above problems will be described below.

[1] (A) hollow or porous particles;
(B) a compound that generates active species upon irradiation with actinic rays or radiation;
The photosensitive composition containing the following resin (C1) or mixed resin (C2).
(C1) Resin that contains silicon atoms or fluorine atoms in the side chain and changes in solubility in an alkali developer by the action of the active species (C2) Resin that contains silicon atoms or fluorine atoms in the side chain (C2-1) ) And a resin (C2-2) whose solubility in an alkali developer is changed by the action of the active species [2] The refractive index of the hollow or porous particles (A) is 1.10. The photosensitive composition as described in [1] above, which is 1.40.
[3] The photosensitive composition according to the above [1] or [2], wherein the resin (C1) or the resin (C2-2) is a resin whose solubility in an alkali developer decreases due to the action of the active species. object.
[4] The photosensitive composition according to any one of [1] to [3], which contains the resin (C1).
[5] The photosensitive composition according to any one of [1] to [4] above, wherein the active species generated by the compound (B) upon irradiation with actinic rays or radiation is a radical.
[6] Any one of [1] to [5] above, wherein the resin (C1) or the resin (C2-1) contains a repeating unit represented by the following general formula (1) or (2). The photosensitive composition as described in any one of.

In general formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group or an aryl group.
R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group or a siloxy group.
R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group or a siloxy group.
X ¹ represents a divalent linking group.
n ¹ represents an integer of 0 to 20.
In the general formula ^(2), R 1, ^{R 2} and ^{R 3} have the same meaning as ^R 1, ^{R 2} and ^{R 3} in the general formula (1).
X ² represents a divalent linking group.
R ⁹ represents an alkyl group substituted with a fluorine atom.
[7] The photosensitive composition according to [6], wherein the repeating unit represented by the general formula (1) or (2) is a repeating unit represented by the following general formula (3) or (4). object.

一般式（３）中、Ｒ^１０は水素原子又はアルキル基を表す。
Ｒ^１１、Ｒ^１２及びＲ^１３はそれぞれ独立に、アルキル基又はシロキシ基を表す。
Ａ^１１は酸素原子、硫黄原子又は−Ｎ（Ｒ^１５）−を表す。
Ｒ^１５は水素原子又はアルキル基を表す。
Ｙ^１１はアルキレン基、アルキレンオキシ基又はこれらの組み合わせを表す。
一般式（４）中、
Ａ^１２は酸素原子、硫黄原子又は−Ｎ（Ｒ^１５）−を表す。
Ｙ^１２はアルキレン基、アルキレンオキシ基又はこれらの組み合わせを表す。
Ｒ^１４はフッ素原子で置換されたアルキル基を表す。
Ｒ^１０及びＲ^１５は、一般式（３）におけるＲ^１０及びＲ^１５と同義である。
［８］ 前記樹脂（Ｃ１）が、（Ｉ）前記一般式（１）〜（４）のいずれかで表される、少なくとも一つの繰り返し単位、（ＩＩ）ラジカル又はカチオン重合性繰り返し単位、及び（ＩＩＩ）アルカリ可溶性繰り返し単位を含有する、上記［６］又は［７］に記載の感光性組成物。
［９］ 前記ラジカル又はカチオン重合性繰り返し単位（ＩＩ）が、下記一般式（５）〜（７）のいずれかで表される繰り返し単位であり、かつ前記アルカリ可溶性繰り返し単位（ＩＩＩ）が、（メタ）アクリル酸である、上記［８］に記載の感光性組成物。

In general formula (3), R ¹⁰ represents a hydrogen atom or an alkyl group.
R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group or a siloxy group.
A ¹¹ represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —.
R ¹⁵ represents a hydrogen atom or an alkyl group.
Y ¹¹ represents an alkylene group, an alkyleneoxy group, or a combination thereof.
In general formula (4),
A ¹² represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —.
Y ¹² represents an alkylene group, an alkyleneoxy group, or a combination thereof.
R ¹⁴ represents an alkyl group substituted with a fluorine atom.
R ¹⁰ and ^{R 15} have the same meanings as ^{R 10} and ^{R 15} in the general formula (3).
[8] The resin (C1) is (I) at least one repeating unit represented by any one of the general formulas (1) to (4), (II) a radical or cationic polymerizable repeating unit, and ( III) The photosensitive composition as described in said [6] or [7] containing an alkali-soluble repeating unit.
[9] The radical or cationic polymerizable repeating unit (II) is a repeating unit represented by any one of the following general formulas (5) to (7), and the alkali-soluble repeating unit (III) is ( The photosensitive composition as described in [8] above, which is meth) acrylic acid.

In general formulas (5) to (7), A ²¹ , A ²² and A ²³ each independently represents an oxygen atom, a sulfur atom or —N (R ⁴¹ ) —, and R ⁴¹ represents a hydrogen atom or an alkyl group. To express.
G ²¹ , G ²² and G ²³ each independently represent a divalent linking group.
X ²¹ and Z ²¹ each independently represent an oxygen atom, a sulfur atom or —N (R ⁴² ) —, and R ⁴² represents a hydrogen atom or an alkyl group.
Y ²¹ represents an oxygen atom, a sulfur atom, a phenylene group or —N (R ⁴³ ) —, and R ⁴³ represents a hydrogen atom or an alkyl group.
R ^{21 to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent organic group.
[10] The above-mentioned resin (C1) or resin (C2-2) has an unsaturated value of 0.5 mmol / g to 2.0 mmol / g and an acid value of 50 mgKOH / g to 200 mgKOH / g. The photosensitive composition as described in any one of [1]-[9].
[11] The photosensitive composition according to any one of [1] to [10], wherein the resin (C1) or the resin (C2-1) has a refractive index of 1.45 or more and less than 1.50. .
[12] The photosensitive composition according to any one of [1] to [11], wherein the hollow or porous particles (A) are silica particles.
[13] The photosensitive composition according to any one of [1] to [12], wherein the hollow or porous particles (A) are contained in an amount of 20% to 90% by mass in the total solid content excluding the solvent. object.
[14] The photosensitive composition according to any one of [1] to [13], further comprising (D) a polymerizable compound.
[15] The photosensitive composition according to any one of [1] to [14], further comprising (E) a developable binder resin.
[16] A pattern forming material which is the photosensitive composition according to any one of [1] to [15].
[17] A photosensitive film formed from the photosensitive composition according to any one of [1] to [15].
[18] A pattern including a step of forming the photosensitive film according to the above [17] on a support, a step of exposing the photosensitive film, and a development step of developing with an alkaline developer to obtain a pattern film Forming method.
[19] A pattern film obtained by the pattern forming method according to [18].
[20] A low refractive index film, which is the pattern film according to [19].
[21] An optical device having the low refractive index film according to [20].
[22] A solid-state imaging device including the optical device according to [21].

The present invention preferably further has the following configuration.
[23] The above-mentioned [1], [2], [4], [4], wherein the resin (C1) or the resin (C2-1) is a resin whose solubility in an alkali developer is increased by the action of the active species. 6], [7], [11]-[13] and the photosensitive composition as described in [15].
[24] The above-mentioned [1], [2], [4], [6], [7], [11] to [13], [15], wherein the compound (B) is a photoacid generator [23] The photosensitive composition according to [23].
[25] The photosensitive composition according to the above [1] to [15], [23] and [24], wherein the hollow or porous particles (A) are hollow particles.

  According to the present invention, a pattern having a high sensitivity, a low refractive index, little pattern chipping and residue after development, a small change in refractive index under high temperature and high humidity, and excellent performance in weather resistance. Formable photosensitive composition, pattern forming material, and photosensitive film using the same, pattern forming method, pattern film, low refractive index film, optical device, and solid-state imaging device can be provided.

The present invention will be described in detail below.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “active light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.

The photosensitive composition of the present invention comprises (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and the following resin (C1) or mixed resin (C2): Contains.
(C1) Resin that contains silicon atoms or fluorine atoms in the side chain and changes in solubility in an alkali developer by the action of the active species (C2) Resin that contains silicon atoms or fluorine atoms in the side chain (C2-1) And a resin (C2-2) whose solubility in an alkaline developer is changed by the action of the active species.

Although the reason why the effects of the present invention can be obtained by using the photosensitive composition of the present invention is not clear, hollow or porous particles (A) and silicon atoms or fluorine atoms having a function of reducing the refractive index are included. By using the resin (C1) contained in the side chain or the mixed resin (C2) containing the resin (C2-1) containing a silicon atom or a fluorine atom in the side chain, the refractive index of the obtained pattern can be determined. It can be sufficiently reduced and it is considered that the use of the compound (B) in combination greatly contributes to obtaining a pattern with high appropriate sensitivity. Specifically, a resin having a silicon atom or a fluorine atom has a low polarizability, and when such a resin is used, the refractive index of the photosensitive composition can be lowered. As a result, the resin obtained from the photosensitive composition can be obtained. The refractive index of the resulting pattern is also reduced. It is estimated that the factor obtained with high appropriate sensitivity is due to the high interaction property between the resin and the substrate and the high interaction property with the hollow or porous particles.
Furthermore, although its action is unclear, the combination of the hollow or porous particles (A) and the resin (C1) or the mixed resin (C2) may cause pattern defects and development residues due to some reason. It is assumed that it contributes to suppression and improvement of weather resistance. In particular, when the resin (C2-1) contained in the resin (C1) or the mixed resin (C2) contains silicon atoms in the side chain, the presence of silicon atoms, which are inorganic materials, significantly improves weather resistance. It is inferred that it has contributed.

The photosensitive composition according to the present invention is typically a negative composition (a composition that forms a negative pattern) or a positive composition (a composition that forms a positive pattern). A mold composition is preferred.
Moreover, this invention relates also to the pattern formation material which is the said photosensitive composition.

  Hereinafter, each component of the photosensitive composition of this invention is explained in full detail.

[1] (A) Hollow or porous particle The hollow particle has a structure having a cavity inside and refers to a particle having a cavity surrounded by an outer shell, and the porous particle is a porous substance having a large number of cavities. Refers to particles.
The porosity of such particles is preferably 10-80%, more preferably 20-60%, and most preferably 30-60%. The porosity of the hollow or porous particles is preferably in the above range from the viewpoint of reducing the refractive index and maintaining the durability of the particles.
The hollow or porous particles are more preferably hollow particles from the viewpoint of easily reducing the refractive index. For example, when the hollow particles are made of silica, the hollow silica particles have air with a low refractive index (refractive index = 1.0), and therefore the refractive index is normal silica (refractive index = Compared with 1.46), it is significantly lower.

  A method for producing hollow particles is described in, for example, JP-A-2001-233611. Moreover, the manufacturing method of porous particle | grains is described in each gazette, such as Unexamined-Japanese-Patent No. 2003-327424, 2003-335515, 2003-226516, 2003-238140, etc., for example.

The hollow or porous particles preferably have an average particle size of 1 to 200 nm, more preferably 10 to 100 nm.
The average particle diameter of the hollow or porous particles can be determined from a photograph obtained by observing the dispersed particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom to obtain the average particle size (usually, 300 or more particles are measured in order to obtain the average particle size).

The refractive index of the hollow or porous particles is preferably 1.10 to 1.40, more preferably 1.15 to 1.35, and most preferably 1.15 to 1.30.
The refractive index here represents the refractive index of the entire particle, and when the particle is a hollow particle, it does not represent the refractive index of only the outer shell forming the hollow particle. When the particles are porous particles, the refractive index of the porous particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

The hollow or porous particles are preferably hollow or porous inorganic particles from the viewpoint of lowering the refractive index. Examples of the inorganic low refractive index particles include magnesium fluoride and silica particles, and silica particles are more preferable from the viewpoint of low refractive index properties, dispersion stability, and cost.
The primary particle diameter of these inorganic particles is preferably 1 to 100 nm, and more preferably 1 to 60 nm.
The inorganic particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical shape, but may be a bead shape, a shape having a major axis / minor axis ratio of 1 or more, or an indefinite shape.

The specific surface area of the inorganic particles is preferably 10~2000m ² / g, more preferably from 20~1800m ² / g, and most preferably 50~1500m ² / g.

Inorganic particles are used in a dispersion or coating solution to stabilize the dispersion, or to increase the affinity and binding properties with the binder component, such as a physical surface such as plasma discharge treatment or corona discharge treatment. Chemical surface treatment with a treatment, a surfactant, a coupling agent, or the like may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
That is, when the inorganic particles are silica particles and the coupling agent is a silane compound, organosilyl groups (monoorganosilyl, diorganosilyl, triorganosilyl groups) are converted into silica particles by the reaction between the silane compound and the silanol group. It binds to the surface. Examples of the organic group that the surface-treated silica particles have on the surface include saturated or unsaturated hydrocarbon groups having 1 to 18 carbon atoms and halogenated hydrocarbon groups having 1 to 18 carbon atoms.
The above-mentioned coupling agent may be used as a surface treatment agent for inorganic particles in order to perform surface treatment in advance before the preparation of the coating solution for low refractive index film, or may be further added as an additive during the preparation of the coating solution.
The inorganic particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

Commercially available silica particles can be used.
For example, Julia Catalysts Co., Ltd. through rear series (isopropanol (IPA) dispersion, 4-methyl-2-pentanone (MIBK) dispersion, etc.), OSCAL series, Nissan Chemical Co., Ltd. Snowtex series (IPA dispersion, ethylene glycol) Dispersion, methyl ethyl ketone (MEK) dispersion, dimethylacetamide dispersion, MIBK dispersion, propylene glycol monomethyl acetate dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate dispersion, xylene-n-butanol dispersion, toluene dispersion, etc.) Sirenax manufactured by Nippon Steel Mining Co., Ltd., PL series manufactured by Fuso Chemical Industry Co., Ltd. (IPA dispersion, toluene dispersion, propylene glycol monomethyl ether dispersion, methyl ethyl ketone dispersion, etc.), manufactured by EVONIK Erotic Jill series (propylene glycol acetate dispersion, ethylene glycol dispersion, MIBK dispersion, etc.) can be used silica particles, such as.

  When silica particles are added to the photosensitive composition as a dispersion containing silica particles and a particle dispersant (details of the particle dispersant will be described later), the content of silica particles in the silica dispersion is 10 % By mass to 50% by mass is preferable, 15% by mass to 40% by mass is more preferable, and 15% by mass to 30% by mass is still more preferable.

  The hollow or porous particles may be used alone or in combination of two or more. When using 2 or more types together, you may use a hollow particle and a porous particle together, for example.

  The content of the hollow or porous particles with respect to the total solid content of the photosensitive composition is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and more preferably 20% by mass to 20% by mass. More preferably, it is 90 mass%.

When forming a film by using the photosensitive composition, coating amount of the hollow or porous particles is ^{preferably 1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , further preferably from ^{10mg / m 2 ~60mg / m 2} . When it is 1 mg / m ² or more, the effect of lowering the refractive index and the effect of improving scratch resistance can be reliably obtained, and when it is 100 mg / m ² or less, fine irregularities are formed on the surface of the film. It is possible to suppress deterioration of the integrated reflectance.

[2] (A ′) Particle Dispersant The photosensitive composition of the present invention preferably further contains (A ′) a particle dispersant from the viewpoint of improving the dispersibility of the hollow or porous particles.

Particle dispersants include polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic copolymers, naphthalene sulfone. Examples thereof include dispersion resins such as acid formalin condensates and compounds such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, and alkanol amines, and resins are preferable (hereinafter referred to as “dispersion resins”). ").
Dispersing resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

  The dispersion resin is adsorbed on the surface of the particles and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.

The weight average molecular weight of the dispersing resin (measured in terms of polystyrene by GPC method), more preferably from preferably from 1,000-2 × 10 ^5, a ^{2000~1 × 10 5, 5000~5 × 10} 4 It is particularly preferred that

  The dispersion resin is also available as a commercial product. As such a specific example, “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group) manufactured by BYK Chemie. ), 111, 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), “BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), EFKA Corporation “EFKA 4047, 4050-4010-4165 (polyurethane)”, EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (Fatty acid polyester), 6745 (phthalosy Nin derivative), 6750 (azo pigment derivative) "," Ajisper PB821, PB822 "manufactured by Ajinomoto Fan Techno Co.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co.," Polyflow No. 50E, No. 300 (acrylic). Copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, manufactured by Enomoto Kasei Co., Ltd. “DA-725”, “Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer) Polycarboxylic acid) "," Emulgen 920, 930, 935, 985 (polyoxyethylene nonyl sulfonate) Nyl ether) ”,“ Acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative) ”, 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (functional at the terminal) 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd. "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450" manufactured by Morishita Sangyo Co., Ltd. Examples thereof include dispersion resins such as suede 6, disperse aid 8, disperse aid 15, and disperse aid 9100.

The dispersion resin may have at least one selected from structural units represented by any one of the general formulas (21) to (23) described later in the developable binder resin (E).
Further, the dispersion resin may be a resin obtained by using, as a copolymer, a compound represented by the general formula (E-1) described later in the developing binder resin (E).

  As the particle dispersant, nonionic, anionic, and cationic sea surface active agents can be used. These surfactants are also available as commercial products, such as phthalocyanine derivatives (commercial products EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Nippon Lubrizol Corporation); organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) Manufactured by Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75, no. 90, no. 95 (above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, poly Nonionic surfactants such as oxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (above, manufactured by Yusho Co., Ltd.), etc. Anionic surfactants such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. (Nippon Lubrizol Corporation) ); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (above, manufactured by ADEKA Corporation) , And Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.). In addition, amphoteric dispersants such as Hinoact T-8000E manufactured by Kawaken Fine Chemical Co., Ltd. are also included.

Moreover, ELEBASE BA-100, BA-200, BCP-2, BUB-3, BUB-4, CP-800K, EDP-475, HEB-5, Finesurf 270, 7045, 7085, Braunon DSP-12.5, DT-03, L-205, LPE-1007, O-205, S-202, S-204, S-207, S-205T (Aoki Yushi Kogyo), EMULGEN A-500, PP-290, Amate 102, 105 , 302, 320, Aminone PK-02S, Emanon CH-25, Emulgen 104P, 108, 404, 408, A-60, A-90, B-66, LS-106, LS-114, Rheodor 430V, 440V, 460V , TW-S106, TW-S120V, Rheodor Super TW-L120 (Kao), Examples include Neukargen 3000S, Fu S-3PG, FE-7PG, Pionein D-6414 (Takemoto Yushi), DYNOL604, Orphine PD-002W, Surfynol 2502, 440, 465, 485, 61 (Nisshin Chemical Industry). it can.
Also, Phosphanol ML-200, Emar 20T, E-27, Neopelex GS, Perex NBL, SS-H, SS-L, Poise 532A, Ramtel ASK, E-118B, E-150 (Kao Corporation) , EMULSOGEN COL-020, 070, 080 (Clariant), Prisurf A208B, A210B, A210G, A219B, AL, Labelin FC-45 (Daiichi Kogyo Seiyaku), Pionein A-24-EA, A-28-B, A -29-M, A-44-B, A-44TW (Takemoto Yushi), AKYPO RLM100NV, RLM45, RLM45NV, ECT-3, ECT-3NEX, ECT-7, Phosten HLP, HLP-1, HLP-TEA (Japan) Surfactant Industry).
These particle dispersants may be used alone or in combination of two or more.

The content of the particle dispersant in the photosensitive composition is preferably 1 to 100% by mass, more preferably 5 to 80% by mass, and 10 to 60% by mass with respect to the hollow or porous particles. Further preferred.
Specifically, when the particle dispersant is a dispersion resin, the amount used is preferably 5 to 100% by mass and more preferably 10 to 80% by mass with respect to the hollow or porous particles. preferable.

[3] (B) Compound that generates active species upon irradiation with actinic rays or radiation The photosensitive composition of the present invention contains (B) a compound that generates active species upon irradiation with actinic rays or radiation.
The photosensitive composition of the present invention imparted with photosensitivity by containing the compound (B) can be suitably used for a photoresist, a color resist, an optical coating material, and the like.
Preferred examples of the compound (B) include a photopolymerization initiator when the photosensitive composition is a negative type, and a photoacid generator when the photosensitive composition is a positive type. That is, as the active species, radicals, cationic species or anionic species (more preferably radicals or cationic species) are used when the photosensitive composition is negative, and acids are used when the photosensitive composition is positive. , Respectively.
Hereinafter, the photopolymerization initiator and the photoacid generator will be described in detail.

[3-1] Photopolymerization initiator The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, it is sensitive to visible light from the ultraviolet region. It may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, or an initiator that initiates cationic polymerization according to the type of monomer. Good.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 200 to 800 nm (more preferably 300 to 450 nm).

  Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred. That is, the active species from which the compound (B) is generated by irradiation with actinic rays or radiation is preferably a radical.

(Photo radical polymerization initiator)
Examples of radical photopolymerization initiators include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), hexaarylbiimidazole compounds, lophine dimers, benzoins, ketals. , 2,3-dialkyldione compounds, organic peroxides, thio compounds, disulfide compounds, azo compounds, borates, inorganic complexes, coumarins, ketone compounds (benzophenones, thioxanthones, thiochromones, anthraquinones) ), Aromatic onium salts, fluoroamine compounds, ketoxime ethers, acetophenones (aminoacetophenone compounds, hydroxyacetophenone compounds), acylphosphine compounds such as acylphosphine oxides, oximes such as oxime derivatives Compounds, and the like.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. It is.

  Examples of borates include, for example, Japanese Patent Nos. 2764769 and 2002-116539, and “Rad Tech'98. Proceeding April” by Kunz, Martin et al., Pages 19-22 (1998, Chicago). ) And the like described in the organic borate. Examples thereof include compounds described in paragraph numbers [0022] to [0027] of JP-A-2002-116539. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples include organoboron transition metal coordination complexes and the like, and specific examples include ion complexes with cationic dyes.

  In addition, as radical polymerization initiators other than the above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′- Rubonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphos Fin oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) And compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

  The radical polymerization initiator is more preferably a compound selected from the group consisting of aminoacetophenone compounds, hydroxyacetophenone compounds, acylphosphine compounds, and oxime compounds. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969, an acylphosphine oxide initiator described in Japanese Patent No. 4225898, an oxime initiator, and an oxime initiator. As the agent, compounds described in JP-A No. 2001-233842 can also be used.

  As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by Ciba Japan) can be used. Moreover, IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by Ciba Japan), which are commercially available products, can be used as the acylphosphine initiator.

  The hydroxyacetophenone compound is preferably a compound represented by the following formula (V).

In Formula (V), R _V ¹ represents a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms), or a divalent group. Represents an organic group. When R _V ¹ is a divalent organic group, two photoactive hydroxyacetophenone structures (that is, a structure in which the substituent R _V ¹ is excluded from the compound represented by the general formula (V)) are R _V ¹ It represents a dimer formed by linking with each other. R _V ² and R _V ³ each independently represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms). R _V ² and R _V ³ may be bonded to form a ring (preferably a ring having 4 to 8 carbon atoms).
Alkyl and alkoxy groups as above _R ^{V _1,} the alkyl group as _R ^{V 2} and _R ^{V 3,} as _well, the ring and _R ^{V 2} and _R ^{V 3} is formed by bonding further have a substituent It may be.

Examples of the hydroxyacetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCURE 1173), 2-hydroxy-2-methyl-1-phenylbutan-1-one, and 1- (4 -Methylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2-hydroxy-2-methyl-1- (4-octylphenyl) propan-1-one, 1- (4-dodecylphenyl) -2-methylpropan-1-one, 1- (4-methoxyphenyl) -2-methylpropan-1-one, 1- (4-methylthiophenyl) -2-methylpropan-1-one, 1 -(4-Chlorophenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-bromophenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1- (4 -Hydroxyphenyl) -2-methylpropan-1-one, 1- (4-dimethylaminophenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-carboethoxyphenyl) -2-hydroxy 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- ON (IRGACURE 2959).
Also, as commercially available α-hydroxyacetophenone compounds, Irgacure 184 (IRGACURE 184), Darocur 1173 (DAROCURE 1173), Irgacure 127 (IRGACURE 127), Irgacure 2959 (IRGACURE 2959), Irgacure 1800 (Irgacure 1959), manufactured by Ciba Specialty Chemicals. Polymerization initiators available under the trade names IRGACURE 1800), Irgacure 1870 (IRGACURE 1870) and Darocur 4265 (DAROCURE 4265) can also be used.

  As the acylphosphine-based initiator, commercially available products IRGACURE-819, IRGACURE-819DW, DAROCUR-TPO (trade names: all manufactured by Ciba Japan) can be used. A phosphine initiator described in JP-A-2009-134098 can also be applied.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by Ciba Japan), IRGACURE-OXE02 (manufactured by Ciba Japan), CGI-124 (manufactured by Ciba Japan), and CGI-242 (manufactured by Ciba Japan) are also suitably used as commercial products.
Furthermore, the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be suitably used.
Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-269979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime compound is preferably a compound represented by the following formula (I). The NO bond of the oxime bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. Good.

(In formula (I), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the optionally substituted alkylthiocarbonyl group include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (II) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group having 6 to 12 carbon atoms, and an alkynylene group having 2 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned as specific examples of the aryl group which may have a substituent.
Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (I), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (II).

(In formula (II), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)
R, A, and Ar in formula (II) have the same meanings as R, A, and Ar in formula (I), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “*” represents a bonding position between Y and an adjacent carbon atom in the formula (II).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  Furthermore, the oxime compound is preferably a compound represented by the following formula (III).

(In formula (III), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5.)
R, X, A, Ar, and n in the formula (III) are respectively synonymous with R, X, A, Ar, and n in the formula (II), and preferred examples are also the same.

  Specific examples (B-1) to (B-10) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.

From the viewpoint of sensitivity, the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 3,000 to 300,000, more preferably 5,000 to 300,000, and 10,000 to 200,000. It is particularly preferred that
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

(Photocationic polymerization initiator)
The cationic photopolymerization initiator may be any compound that generates a substance that initiates cationic photopolymerization by receiving energy rays such as ultraviolet rays, preferably an onium salt, more preferably an aromatic onium salt, and an arylsulfonium. Further preferred are salts and aryliodonium salts.

Specific examples of the onium salt include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, triphenylsulfonium, diphenyl- 4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, η5-2,4 -(Cyclopentadienyl) [1,2,3,4,5,6-η]-(methylethyl) -benzene] -iron (1+) and the like. Specific examples of anions include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl). ₆ ^-), perchlorate ion (ClO ₄ ^-), trifluoromethanesulfonate ion _(CF 3 SO ₃ ^-), fluorosulfonic acid ion (FSO ₃ ^-), toluenesulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene Examples include sulfonate anions.

  In particular, specific examples of the aromatic onium salt include aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, JP-A-50-151997, JP Group VIA aromatic onium salts described in JP-A-52-30899, JP-A-56-55420, JP-A-55-125105, etc., Group VA-aromatics described in JP-A-50-158698, etc. Onium salts, oxosulfoxonium salts described in JP-A-56-8428, JP-A-56-149402, JP-A-57-192429, etc., described in JP-A-49-17040, etc. Aromatic diazonium salts, thiobililium salts, iron / allene complexes, aluminum complexes / photolytic silicon compound systems described in US Pat. No. 4,139,655 Initiator, halides that photogenerate a hydrogen halide, o- nitrobenzyl ester compounds, imide sulfonate compound, bissulfonyldiazomethane compounds, mention may be made of an oxime sulfonate compound.

  As the photocationic polymerization initiator that can be used in the present invention, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization can be widely used (edited by Organic Electronics Materials Research Group, “Organization for Imaging”). Materials, "Bunshin Publishing (1993), pages 187-192). These compounds are described in THE CHEMICAL SOCIETY OF JAPAN Voi. 71 no. 11, 1998, as well as the photocationic polymerization initiator described in “Organic Materials for Imaging”, edited by Organic Electronics Materials Study Group, Bunshin Publishing (1993), can be easily synthesized by known methods. .

  Commercially available photocationic polymerization initiators include UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above, Union Carbide), Adekaoptomer SP-150, SP-151. , SP-170, SP-171, SP-172 (above, manufactured by ADEKA Corporation), Irgacure 261, IRGACURE OXE01, IRGACURE CGI-1397, CGI-1325, CGI-1380, CGI-1311, CGI-263, CGI -268, CGI-1397, CGI-1325, CGI-1380, CGI-1311 (above, manufactured by Ciba Specialty Chemicals), CI-2481, CI-2624, CI-2638, CI-2039 (above, Nippon Soda ( CD-1) 10, CD-1011, CD-1012 (manufactured by Sartomer), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (and above) , Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (Nippon Kayaku Co., Ltd.), PHOTOINITIATOR 2074 (Rhodia Co., Ltd.), UR-1104, UR- 1105, UR-1106, UR-1107, UR-1113, UR-1114, UR-1115, UR-1118, UR-1200, UR-1201, UR-1202, UR-1203, UR-1204, UR-1205, UR-1207, UR-1401, UR-1402, UR-1403, UR -M1010, UR-M1011, UR-M10112, UR-SAIT01, UR-SAIT02, UR-SAIT03, UR-SAIT04, UR-SAIT05, UR-SAIT06, UR-SAIT07, UR-SAIT08, UR-SAIT09, UR-SAIT10 UR-SAIT11, UR-SAIT12, UR-SAIT13, UR-SAIT14, UR-SAIT15, UR-SAIT16, UR-SAIT22, UR-SAIT30 (manufactured by URAY). Among these, UVI-6970, UVI-6974, Adekaoptomer SP-170, SP-171, SP-172, CD-1012 and MPI-103 have higher photocuring sensitivity due to the composition containing them. Can be expressed. Said photocationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

  A radical photopolymerization initiator or a cationic photopolymerization initiator may be used alone, or two or more kinds may be freely combined.

[3-2] Photoacid Generator As the photoacid generator, the above-mentioned photocationic polymerization initiator can be used, and preferably the onium salt counter anion is a sulfonate.

  The amount of compound (B) added to the total solid content of the photosensitive composition of the present invention is preferably 0.1 to 50% by mass, preferably 0.5 to 20% by mass, and 1 to 5%. More preferably, it is mass%.

[4] (C1) Resin or (C2) Mixed Resin The photosensitive composition of the present invention contains the following resin (C1) or mixed resin (C2) as an essential component from the viewpoint of lowering the refractive index.
(C1) Resin containing silicon atoms or fluorine atoms in the side chain and changing solubility in an alkali developer by the action of active species (C2) Resin containing silicon atoms or fluorine atoms in the side chain (C2-1) And a mixed resin containing a resin (C2-2) whose solubility in an alkaline developer is changed by the action of the active species. As the resin (C1) or the resin (C2-2), the photosensitive composition is a negative type In some cases, a resin whose solubility in an alkaline developer is reduced by the action of active species, and in the case where the photosensitive composition is positive, a resin whose solubility in an alkali developer is increased by the action of active species, Each can be mentioned. The active species is an active species from which the aforementioned compound (B) is generated. The resin (C1) or the resin (C2-2) is preferably a resin whose solubility in an alkaline developer is reduced by the action of active species, that is, the photosensitive composition is negative.

  Hereinafter, the resin (C1) or the mixed resin (C2) will be described in detail. In addition, it is preferable that the photosensitive composition of this invention contains resin (C1).

  [4-1] (C1) A resin containing a silicon atom or a fluorine atom in the side chain, and having a solubility in an alkali developer changed by the action of active species

  The main chain having the longest chain length in the resin (C1) is composed of only carbon atoms or has a structure connected by oxygen atoms or nitrogen atoms.

Polymerization of the resin (C1) is classified from the reaction point, such as chain polymerization, sequential polymerization, and living polymerization. From the classification of reaction mechanism to addition polymerization, polycondensation, polyaddition, addition condensation, etc. Polymerization, cationic polymerization, anionic polymerization, coordination polymerization, ring-opening polymerization and the like are known, and generally known ones can be applied.
When the resin (C1) forms a copolymer, random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, and the like can be arbitrarily selected.

  The resin containing a fluorine atom in the side chain is not particularly limited as long as it is a resin containing a repeating unit having a fluorine atom in the side chain, but those shown below can be preferably used.

  In order to reduce the refractive index, it is effective to use a fluorine-containing monomer. In order to realize a low refractive index, it is preferable to use a homopolymer or copolymer of a fluorine-containing monomer, or a copolymer of a fluorine-containing monomer and a non-fluorine monomer.

  The following are mentioned as a fluorine-containing monomer.

  In the above formula, n represents an integer.

  Although the polymer structure obtained from the said fluorine monomer is shown below, this invention is not limited to this.

(Where l + m + n is 1 to 6, l is an integer from 0 to 5, m is an integer from 1 to 4, n is an integer from 0 to 1, and R is F or CF ₃ . is there.)

(However, R ₁ and R ₂ are each independently F or CF _3. )

  The resin containing a silicon atom in the side chain is not particularly limited as long as it is a resin containing a repeating unit having a silicon atom in the side chain.

  The repeating unit containing a silicon atom or a fluorine atom in the side chain contained in the resin (C1) is preferably a repeating unit represented by the following general formula (1) or (2).

In general formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group or an aryl group.
R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group or a siloxy group.
R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group or a siloxy group.
X ¹ represents a divalent linking group.
n ¹ represents an integer of 0 to 20.
In the general formula ^(2), R 1, ^{R 2} and ^{R 3} have the same meaning as ^R 1, ^{R 2} and ^{R 3} in the general formula (1).
X ² represents a divalent linking group.
R ⁹ represents an alkyl group substituted with a fluorine atom.

The alkyl group represented by R ¹ , R ² and R ³ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.
The aryl group represented by R ¹ , R ² and R ³ is preferably an aryl group having 5 to 30 carbon atoms, and more preferably an aryl group having 6 to 8 carbon atoms.
These alkyl groups and aryl groups may have a substituent such as a hydroxyl group, a halogen atom, or a carboxyl group.
Most preferred is when R ¹ and R ² represent a hydrogen atom and R ³ is a hydrogen atom or an alkyl group.

R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group or a siloxy group. The siloxy group is a monovalent substituent in which a silicon atom of a silyl group having an arbitrary substituent is bonded through an oxygen atom.
The alkyl group represented by R ⁴ and R ⁵ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.
The siloxy group represented by R ⁴ and R ⁵ is a structure represented by —OSi (R ⁵¹ ) (R ⁵² ) (R ⁵³ ), and R ⁵¹ , R ⁵² and R ⁵³ are each independently an alkyl group or Represents an alkenyl group. The alkyl group represented by R ⁵¹ , R ⁵² and R ⁵³ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. The alkenyl group represented by R ⁵¹ , R ⁵² and R ⁵³ is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 4 carbon atoms, and most preferably a vinyl group.

R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group or a siloxy group. The alkyl group represented by R ⁶ , R ⁷ and R ⁸ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.
The siloxy group represented by R ⁶ , R ⁷ and R ⁸ is a structure represented by —OSi (R ⁵¹ ) (R ⁵² ) (R ⁵³ ), and the definition and preferred range thereof are the aforementioned R ⁴ and R This is the same as the siloxy group represented by ⁵ .

X ¹ and X ² represent a divalent linking group. Examples of the divalent linking group represented by X ¹ and X ² include an oxygen atom, a sulfur atom, an alkylene group, a cycloalkylene group, a phenylene group, —OC (O) —, —C (O) O—, —C (O) N (R ¹⁵ ) — and a linking group formed by a combination thereof (total carbon number is preferably 1 to 20, more preferably 1 to 15 carbon atoms, more preferably 2 to 10 is more preferable). R ¹⁵ represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms), and is preferably a hydrogen atom.
The divalent linking group represented by X ¹ and X ² is preferably an alkylene group, a —COO—Rt— group, an —O—Rt— group, or a group formed by combining two or more thereof.
Rt represents an alkylene group or a cycloalkylene group, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.
The alkylene group contained in the divalent linking group as X ¹ and X ² may be substituted with a hydroxyl group or a trialkylsilyl group (preferably a trimethylsilyl group).

n ¹ represents an integer of 0 to 20, preferably an integer of 0, more preferably an integer of 0 to 5.

R ⁹ represents an alkyl group substituted with a fluorine atom, preferably an alkyl group substituted with a fluorine atom having 1 to 20 carbon atoms, and is an alkyl group substituted with a fluorine atom having 1 to 10 carbon atoms. It is more preferable. The number of fluorine atoms in the alkyl group substituted with the fluorine atom represented by R ⁹ is preferably 3 to 20, and more preferably 3 to 15.

  Furthermore, the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) are respectively represented by the repeating unit represented by the following general formula (3) and the general formula (4). A repeating unit is preferred from the viewpoint of the ease of synthesis.

In general formula (3), R ¹⁰ represents a hydrogen atom or an alkyl group.
R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group or a siloxy group.
A ¹¹ represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —.
R ¹⁵ represents a hydrogen atom or an alkyl group.
Y ¹¹ represents an alkylene group, an alkyleneoxy group, or a combination thereof.
In general formula (4),
A ¹² represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —.
Y ¹² represents an alkylene group, an alkyleneoxy group, or a combination thereof.
R ¹⁴ represents an alkyl group substituted with a fluorine atom.
R ¹⁰ and ^{R 15} have the same meanings as ^{R 10} and ^{R 15} in the general formula (3).

In general formula (3), R ¹⁰ represents a hydrogen atom or an alkyl group. The alkyl group represented by R ¹⁰ may have a substituent such as a hydroxyl group, a halogen atom, or a carboxyl group. The alkyl group represented by R ¹⁰ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group, an ethyl group, or a propyl group. And most preferably a methyl group.

R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group or a siloxy group. The preferred ranges of the alkyl group and siloxy group represented by R ¹¹ , R ¹² and R ¹³ are the same as the preferred ranges of the alkyl group and siloxy group represented by R ⁶ , R ⁷ and R ⁸ described above.

A ¹¹ represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —. R ¹⁵ represents a hydrogen atom or an alkyl group, and a preferred range is the same as described above. A ¹¹ is preferably an oxygen atom or —N (R ¹⁵ ) —, and more preferably an oxygen atom.

Y ¹¹ represents an alkylene group, an alkyleneoxy group, or a combination thereof. Y ¹¹ is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms. Specific examples include a methylene group, an ethylene group, and a propylene group. The alkylene group contained in Y ¹¹ may be substituted by a hydroxyl group.

In the general formula ^{(4), A 12} represents an oxygen atom, a sulfur atom or -N ^{(R 15)} - represents a. A ¹² is preferably an oxygen atom or —N (R ¹⁵ ) —, and more preferably an oxygen atom.
Y ¹² represents an alkylene group, an alkyleneoxy group, or a combination thereof. Y ¹² is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. Specific examples include a methylene group, an ethylene group, and a propylene group. The alkylene group contained in Y ¹² may be substituted with an alkyl group (preferably a trifluoromethyl group) substituted with a fluorine atom.
R ¹⁴ represents an alkyl group substituted with a fluorine atom. The preferred range of the alkyl group substituted with a fluorine atom represented by R ¹⁴ is the same as the alkyl group substituted with the fluorine atom represented by R ⁹ described above.
R ¹⁰ and ^{R 15} are synonymous with ^{R 10} and ^{R 15} in the general formula (3), and preferred ranges are also the same.

  Specific examples of the repeating unit represented by the general formula (1) include the following repeating units.

  Specific examples of the repeating unit represented by the general formula (2) include the following repeating units.

Resin (C1) is a resin whose solubility in an alkaline developer is changed by the action of (B) a compound that generates active species upon irradiation with actinic rays or radiation.
The change in the solubility in the alkali developer may be a case where the solubility in the alkali developer is decreased or a case where the solubility is increased.

  Examples of the decrease in solubility in an alkali developer include a curing reaction in which a radical polymerizable group or a cationic polymerizable group in the resin (C1) undergoes polymer crosslinking by radical or cationic polymerization and becomes insoluble in alkali.

  As an example of increasing the solubility in an alkali developer, an alkali-soluble group protected by a leaving group in the resin (C1) is deprotected by an acid generated from a photoacid generator, and an alkali-soluble group appears. The polarity conversion by this is mentioned.

  From the viewpoint of high sensitivity and high resolution, radical or cation polymerization is used, and radical or cation polymerization reaction of resin (C1) proceeds by radicals or cations generated by irradiation with actinic rays or radiation. It is preferred that the solubility in an alkaline developer is reduced.

  Further, the resin (C1) comprises (I) at least one repeating unit represented by any one of the general formulas (1) to (4), (II) a radical or cationic polymerizable repeating unit, and (III) an alkali. It is preferable to contain a soluble repeating unit in order to achieve both high sensitivity curability and alkali developability with little residue.

At least one repeating unit (I) represented by any one of the general formulas (1) to (4) contributes to a reduction in the refractive index of the resin (C1). Further, from the viewpoint of weather resistance, the resin (C1) more preferably contains a silicon atom in the side chain, that is, contains a repeating unit represented by the general formula (1) or (3).
The content of the repeating unit (I) in the resin (C1) is preferably 1 mol% to 90 mol%, more preferably 10 mol% to 70 mol%, based on all the repeating units in the resin (C1). 20 mol% to 60 mol% is most preferable.

  The radical or cation polymerizable repeating unit (II) is cross-linked between polymer molecules by the action of an acid or radical and gels, thereby contributing to a decrease in solubility in an alkali developer.

  As a radically polymerizable repeating unit, a resin having a fluorine atom or a silicon atom in the side chain and reacting with a compound having a radically polymerizable group and reacting with the compound can react with the compound having the radically polymerizable group. It is preferable to introduce into the resin. For example, a resin obtained by reacting a carboxyl group-containing resin with a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate or allyl glycidyl ether, or an unsaturated alcohol such as allyl alcohol, 2-hydroxy acrylate, or 2-hydroxy methacrylate, Polybasic acid anhydride is allowed to react with a resin obtained by reacting a carboxyl group-containing resin having a hydroxyl group with a free isocyanate group-containing unsaturated compound and an unsaturated acid anhydride, or an addition reaction product between an epoxy resin and an unsaturated carboxylic acid. Resin, a resin obtained by reacting an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic acid anhydride with a hydroxyl group-containing polymerizable monomer, a specific functional group that causes an elimination reaction by base treatment to give an unsaturated group A radically polymerizable repeating unit by synthesizing a resin having It is possible to obtain a resin (C1) having.

  Among them, a resin obtained by reacting a carboxyl group-containing resin with a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate or allyl glycidyl ether, or a resin obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester compound ( ) Resin obtained by reacting a (meth) acrylic acid ester having a free isocyanate group such as acrylic acid-2-isocyanatoethyl, a resin having a structural unit represented by the following general formulas (21) to (23), base treatment It is more preferable to obtain a resin (C1) having a radically polymerizable repeating unit by synthesizing a resin having a specific functional group that generates an unsaturated group by elimination reaction and subjecting the resin to a base treatment.

  As the cationically polymerizable repeating unit, a cationically polymerizable group may be included in the side chain. For example, a polymer containing an epoxy group, an oxetane group or the like in the side chain is also useful.

  In order to obtain the resin (C1) having a cationic polymerizable group, for example, a monomer having an epoxy group (hereinafter sometimes referred to as “monomer for introducing an epoxy group”) is used as a monomer component. What is necessary is just to superpose | polymerize. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types. When the monomer component in obtaining the alkali-soluble binder also includes a monomer for introducing the epoxy group, the content ratio is not particularly limited, but is 5 to 70% by mass in the total monomer component, Preferably it is 10-60 mass%.

  Specifically, the radically or cationically polymerizable repeating unit (II) is preferably represented by any one of the following general formulas (5) to (7).

In the general formulas (5) to (7), A ²¹ , A ²² and A ²³ each independently represents an oxygen atom, a sulfur atom or —N (R ⁴¹ ) —, and R ⁴¹ represents a hydrogen atom or an alkyl group. Represents.
G ²¹ , G ²² and G ²³ each independently represent a divalent linking group.
X ²¹ and Z ²¹ each independently represent an oxygen atom, a sulfur atom or —N (R ⁴² ) —, and R ⁴² represents a hydrogen atom or an alkyl group.
Y ²¹ represents an oxygen atom, a sulfur atom, a phenylene group or —N (R ⁴³ ) —, and R ⁴³ represents a hydrogen atom or an alkyl group.
R ^{21 to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent organic group.

In the general formula (5), R ^{21 to} R ²³ each independently represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group represented by R ^{21 to} R ²³ include an optionally substituted alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms). Examples of the substituent that the alkyl group may have include a hydroxyl group and a halogen atom. Among these, R ²¹ and R ²² are preferably hydrogen atoms, and R ²³ is preferably a hydrogen atom or a methyl group.
R ²⁴ to R ²⁶ are each independently represent a hydrogen atom or a monovalent organic group. Examples of R ²⁴ include a hydrogen atom or an alkyl group which may have a substituent (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms). Examples of the preferable substituent include a hydroxyl group and a halogen atom. Among them, R ²⁴ is preferably a hydrogen atom, a methyl group, or an ethyl group. R ²⁵ and R ²⁶ may each independently have a hydrogen atom, a halogen atom, an alkoxycarbonyl group (preferably having a carbon number of 2 to 15), a sulfo group, a nitro group, a cyano group, or a substituent. An alkyl group (preferably having 1 to 20 carbon atoms), an aryl group which may have a substituent (preferably having 6 to 20 carbon atoms), an alkoxy group which may have a substituent (preferably having 1 carbon atom) To 15), an aryloxy group which may have a substituent (preferably 6 to 20 carbon atoms), an alkylsulfonyl group which may have a substituent (preferably 1 to 20 carbon atoms), a substituent An arylsulfonyl group (preferably having 6 to 20 carbon atoms) which may have a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, or a substituent. Have Preferably also aryl group, more preferably alkyl group which may have a hydrogen atom or a substituent, more preferably a hydrogen atom or a methyl group. Here, examples of the substituent that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

A ²¹ represents an oxygen atom, a sulfur atom, or —N (R ⁴¹ ) —, and X ²¹ represents an oxygen atom, a sulfur atom, or —N (R ⁴² ) —. Here, the definition and preferred range of R ⁴¹ and R ⁴² are the same as the definition and preferred range of R ¹⁵ described above. A ²¹ and X ²¹ are preferably oxygen atoms.
G ²¹ represents a divalent linking group. Examples of the divalent linking group represented by G ²¹ include an alkylene group that may have a substituent, a cycloalkylene group that may have a substituent, and a divalent that may have a substituent. Aromatic group, —OC (O) —, —C (O) O—, —N (R ⁴⁴ ) — and a linking group formed by combining these (total carbon number is preferably 1-20, It is more preferable that the number is 1 to 15, and it is more preferable that the number of carbon atoms is 2 to 10. The definition and preferred range of R ⁴⁴ are the same as the definition and preferred range of R ¹⁵ described above. More preferred as G ^21, alkylene group which may have a substituent having 1 to 20 carbon atoms, the substituents may cycloalkylene group which may have a 3 to 20 carbon atoms, 6 to 20 carbon atoms A divalent aromatic group which may have a substituent, —OC (O) —, —C (O) O—, —N (R ⁴⁴ ) — and a linking group formed by combining these; Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, a cycloalkylene group which may have a substituent having 3 to 10 carbon atoms, or a 6 to 12 carbon atom. The divalent aromatic group which may have a substituent, —OC (O) —, —C (O) O—, —N (R ⁴⁴ ) — and a linking group formed by combining these have strength, development It is preferable in terms of performance such as property.

Here, the substituent in G ²¹ is preferably a group in which a hydrogen atom is bonded to a hetero atom except a hydroxyl group, for example, a group not containing an amino group, a thiol group, or a carboxyl group, and preferably a hydroxyl group.

In the general formula (6), R ^{27 to} R ²⁹ each independently represent a hydrogen atom or a monovalent organic group. A preferred range of R ²⁷ to R ²⁹ are the same as the preferred ranges of the above ^R 21 ^{to R 23.}
R ^{30 to} R ³² each independently represent a hydrogen atom or a monovalent organic group. Specific examples of R ^{30 to} R ³² include a hydrogen atom, a halogen atom, a dialkylamino group (preferably having 2 to 20 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 15 carbon atoms), a sulfo group, and a nitro group. A group, a cyano group, an optionally substituted alkyl group (preferably having 1 to 20 carbon atoms), an optionally substituted aryl group (preferably having 6 to 20 carbon atoms), and a substituent group. An optionally substituted alkoxy group (preferably having a carbon number of 1 to 15), an optionally substituted aryloxy group (preferably having a carbon number of 6 to 20), and an optionally substituted alkyl Examples include a sulfonyl group (preferably having a carbon number of 1 to 20), an arylsulfonyl group optionally having a substituent (preferably having a carbon number of 6 to 20), etc. Among them, a hydrogen atom, an alkoxycarbonyl group, Alkyl group which may have a substituent, aryl group which may have a substituent is preferable.
Examples of the substituent that may be introduced include the same manner as in the formula (5) mentioned as the substituent which may be introduced into R ²¹ to R ^23.

A < ²² > represents an oxygen atom, a sulfur atom, or -N (R < ⁴¹ >)-each independently. Here, the definition and preferred range of R ⁴¹ are the same as the definition and preferred range of R ¹⁵ described above.
G ²² represents a divalent linking group. Specific examples and preferred ranges of the divalent linking group represented by G ²² are the same as the specific examples and preferred ranges of the divalent linking group represented by G ²¹ described above.
Y ²¹ represents an oxygen atom, a sulfur atom, —N (R ⁴³ ) — or a phenylene group. Here, R ⁴³ represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) which may have a substituent. The phenylene group represented by Y ²¹ may have a substituent, and examples of the substituent include an alkyl group and a halogen atom.

In the general formula (7), R ^{33 to} R ³⁵ each independently represents a hydrogen atom or a monovalent organic group. The preferred range of R ^{33 to} R ^{35 is the same as} the preferred range of R ^{21 to} R ²³ described above.
R ^{36 to} R ⁴⁰ each independently represents a hydrogen atom or a monovalent organic group. Specific examples and preferred ranges of R ^{36 to} R ⁴⁰ are the same as the specific examples and preferred ranges of R ^{30 to} R ³² .
A ²³ represents an oxygen atom, a sulfur atom, or —N (R ⁴¹ ) —, and Z ²¹ represents an oxygen atom, a sulfur atom, or —N (R ⁴² ) —. The R ⁴¹ and ^{R 42,} are the same as those for ^{R 41} and ^{R 42} in the general formula (5).

G ²³ represents a divalent linking group. Specific examples and preferred ranges of the divalent linking group represented by G ²³ are the same as the specific examples and preferred ranges of the divalent linking group represented by G ²² described above.

  The repeating units represented by the general formulas (5) to (7) are 1 mol% or more and 70 mol% or less with respect to all repeating units in the resin (C1) from the viewpoints of improvement in curability and pattern formation. It is preferably included in the range, more preferably in the range of 5 mol% to 60 mol%, and still more preferably in the range of 10 mol% to 60 mol%.

  The synthesis of the polymer having the repeating units represented by the general formulas (5) to (7) is performed based on the synthesis method described in paragraph numbers [0027] to [0057] of JP-A No. 2003-262958. Can do. Among these, it is preferable to use the synthesis method 1) in the publication.

  The content of the radically or cationically polymerizable repeating unit (II) in the resin (C1) is 1 mol% with respect to all the repeating units in the resin (C1) in order to increase sensitivity and suppress chipping of the cured pattern. It is preferably ˜70 mol%, more preferably 5 mol% to 60 mol%, and most preferably 10 mol% to 60 mol%.

  As the alkali-soluble repeating unit (III), conventionally known ones can be used as long as they have a substituent that forms an anion by the action of alkali.

Although it does not restrict | limit especially as said substituent, For example, an acid group, alcoholic hydroxyl group, a pyrrolidone group, an alkylene oxide group etc. can be mentioned, More preferably, it is an acid group.
The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more. In order to introduce an acid group into an alkali-soluble binder, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.
Examples of the monomer having an acid group include a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid, a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, and itaconic anhydride. Monomers having a carboxylic acid anhydride group, ethylene glycol monoacetoacetate monomethacrylate having an active methylene group having high acidity, and the like. Among these, (meth) acrylic acid, ethylene glycol monoacetoacetate Monomethacrylate is preferred, and (meth) acrylic acid is more preferred.
Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types.
In the case of using a monomer capable of imparting an acid group after polymerization, the treatment for imparting the acid group after polymerization includes a treatment of modifying a part of the polar group of the polymer side chain by a polymer reaction.

  Further, a lactone that is hydrolyzed by the action of an alkali to generate an acid group, and a 1,3-dicarbonyl compound that can form an anion by extracting active hydrogen by an alkali can also be used.

The content of the alkali-soluble repeating unit (III) in the resin (C1) enables alkali developability, and the resin (C1) is used to suppress residues due to the attachment of hollow or porous particles to unexposed areas. It is preferably 1 mol% to 60 mol%, more preferably 5 mol% to 50 mol%, and most preferably 10 mol% to 40 mol%, based on all repeating units.
Resin (C1) consists of only three components of the repeating units (I) to (III) (that is, the total content of the repeating units (I) to (III) with respect to all the repeating units in the resin (C1). Is preferably 100 mol%).

  The unsaturated value of the resin (C1) is preferably 0.1 mmol / g to 7.0 mmol / g, more preferably 0.2 mmol / g to 5.0 mmol / g, most preferably 0.5 mmol. / G to 2.0 mmol / g. By setting it as this range, both curability and developability can be achieved. The unsaturated value means the number of millimolar number of polymerizable unsaturated bonds contained in 1 g of polymer.

  The acid value of the resin (C1) is preferably 10 mgKOH / g to 300 mgKOH / g, more preferably 20 mgKOH / g to 250 mgKOH / g, and most preferably 50 mgKOH / g to 200 mgKOH / g. By setting it as this range, developability becomes favorable and the residue by the hollow or porous particle | grain to an unexposed part can be suppressed.

  The refractive index of the resin (C1) is 1.30 or more and less than 1.50, preferably 1.40 or more and less than 1.50, more preferably 1.45 or more and less than 1.50. It is preferable from the viewpoint that the refractive index can be reduced. In order to realize such a refractive index, it is preferable that the polymer does not have an aromatic ring or a cyclic structure.

  The resin (C1) preferably has a mass average molecular weight of 3,000 to 100,000, more preferably 5,000 to 50,000, and most preferably 7,000 to The range is 35,000.

  Although the specific compound example of resin (C1) is described below, this invention is not limited to this.

  [4-2] (C2) Contains a resin (C2-1) containing a silicon atom or a fluorine atom in the side chain, and a resin (C2-2) whose solubility in an alkali developer is changed by the action of active species Mixed resin

  The resin (C2-1) containing a silicon atom or a fluorine atom in the side chain is not particularly limited as long as it is a resin containing a repeating unit having a silicon atom or a fluorine atom in the side chain, but the above-mentioned resin (C1) It is preferable that it is resin containing the repeating unit (namely, above-mentioned repeating unit (I)) represented by either of General formula (1)-(4) demonstrated by (1). The content of the repeating unit (I) in the resin (C2-1) is the same as the content of the repeating unit (I) in the resin (C1), and other known repeating units can be used. is there. The resin (C2-1) is preferably a resin further containing the above-mentioned radical or cationic polymerizable repeating unit (II), and the content of the repeating unit (II) in the resin (C2-1) is the repeating unit ( The content in the resin (C1) of II) is the same. The refractive index range of the resin (C2-1) is the same as the refractive index range of the resin (C1).

  The resin (C2-2) whose solubility in an alkaline developer is changed by the action of the active species is not particularly limited as long as it is a resin whose solubility in the alkali developer is changed by the action of the active species. Or it is resin containing cationically polymerizable repeating unit (II) and alkali-soluble repeating unit (III). The content of the repeating unit (II) and the repeating unit (III) in the resin (C2-2) is the same as the content of the repeating unit (II) and the repeating unit (III) in the resin (C1). Known repeating units can be used as the repeating unit. The unsaturated value and the acid value in the resin (C2-2) are the same as the unsaturated value and the acid value in the resin (C1) described above.

  The mass average molecular weights of the resin (C2-1) and the resin (C2-2) are the same as the mass average molecular weight of the resin (C1). The blend ratio of the resin (C2-1) and the resin (C2-2) in the mixed resin (C2) is preferably 10/90 to 70/30 by mass ratio, and is 15/85 to 60/40. It is more preferable.

[5] (D) Polymerizable compound The photosensitive composition of the present invention preferably further contains a polymerizable compound, particularly from the viewpoint of improving the appropriate sensitivity. Since the compound (B) that generates active species upon irradiation with actinic rays or radiation has a polymerization initiating ability, the photosensitive composition of the present invention generates (B) active species upon irradiation with actinic rays or radiation. Depending on the function of the compound, the polymerizable compound (D) can be polymerized and cured to form a cured film.
The polymerizable compound that can be used in the photosensitive composition of the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably 2 It is selected from compounds having at least one. Such compounds are widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.

The (D) polymerizable compound suitably used in the present invention will be described more specifically.
Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound in which an unsaturated phosphonic acid, styrene, vinyl ether or the like is substituted for the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

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

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

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

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.
Especially, the polyfunctional polymerizable compound used in the Example mentioned later, such as dipentaerythritol hexaacrylate and pentaerythritol triacrylate, can be mentioned as a preferable thing.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (I) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 31)}} COOCH 2 CH (R 32) OH (I)
(However, in the general formula (I), R ³¹ and R ³² each represent H or CH _3. )

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

Among these, as the polymerizable compound, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, hexanediol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, In addition, a structure in which these (meth) acryloyl groups are via ethylene glycol and propylene glycol residues is preferred, and pentaerythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate are more preferred. These oligomer types can also be used.
The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound.

Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, as polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. By using a curable composition, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Examples of commercially available polymerizable compounds include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), A-TMM-3LM-N (Shin-Nakamura Chemical). DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
As the polymerizable compound, ethylenically unsaturated compounds having an acid group are also suitable.
The ethylenically unsaturated compounds having an acid group can be obtained by, for example, converting (meth) acrylate a part of the hydroxy group of the polyfunctional alcohol and adding an acid anhydride to the remaining hydroxy group to form a carboxy group. can get. Examples of commercially available products include TO-756, which is a carboxy group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and TO-1382 including a carboxy group-containing pentafunctional acrylate.

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

A polymeric compound may be used individually by 1 type, and may use 2 or more types together.
The content of the polymerizable compound (D) in the photosensitive composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, based on the solid content of the composition. 3-15 mass% is still more preferable.

[6] (E) Developable binder resin The photosensitive composition of the present invention may further contain (E) a developable binder resin. The photosensitive composition of the present invention has at least one resin (hereinafter, developable binder resin) for dispersing hollow or porous particles on a coating film and developing hollow or porous particles in an unexposed portion. It is preferable to contain.
As the developable binder resin (E), when the photosensitive composition is a negative type, a developable binder resin whose solubility in an alkaline developer is reduced by the action of the active species, the photosensitive composition is a positive type. In some cases, a developing binder resin whose solubility in an alkaline developer is increased by the action of active species can be mentioned.
Hereinafter, the developable binder resin whose solubility in an alkaline developer is reduced by the action of active species and the developable binder resin whose solubility in an alkali developer is increased by the action of active species will be described in detail.

[6-1] Developable binder resin whose solubility in alkaline developer is reduced by the action of active species The developable binder resin (E) whose solubility in alkali developer is reduced by the action of active species is alkali-soluble. In addition, the resin is not particularly limited as long as it is a resin whose solubility in an alkaline developer is reduced by the action of active species, but it is preferably selected from the viewpoints of heat resistance, developability, curability, availability, and the like. Here, “alkali-soluble” includes not only being soluble in an alkali developer but also exhibiting swellability in an alkali developer.

That is, the developable binder resin (E) is used not only for further improving the film-forming property but also for further improving the developability for an alkaline developer.
Such a developable binder resin (E) is preferably a binder resin having an alkali-soluble group.

Examples of the alkali-soluble group include an acid group, an alcoholic hydroxyl group, a pyrrolidone group, and an alkylene oxide group, and an acid group is more preferable. As the acid group, a carboxyl group, an active methylene group, a phosphoric acid group, and a sulfonic acid group are preferable, a carboxyl group and an active methylene group are more preferable, and a carboxyl group is particularly preferable.
Specific examples of the acid group and the method for introducing the acid group into the developing binder resin are the same as those described for the alkali-soluble repeating unit (III) of the resin (C1).

  The developable binder resin (E) is preferably a linear organic high molecular polymer. As such a “linear organic high molecular polymer”, in order to enable better alkali development of a film obtained from the photosensitive composition of the present invention, first, an alkali developer (typically, A linear organic polymer that is soluble or swellable in weak alkaline water) is selected.

  Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful. Moreover, as a linear organic high molecular polymer, the polymer as described in paragraph number [0227]-[0234] paragraph of Unexamined-Japanese-Patent No. 2008-292970 is mentioned.

  The linear organic polymer can be obtained by radical polymerization or cationic polymerization of a polymerizable monomer as shown below by a conventionally known method.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. Is mentioned.
Moreover, as developable binder resin (E), the acidic cellulose derivative which has a carboxylic acid group in a side chain can also be used. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  As described above, when the linear organic high molecular weight polymer is a copolymer, the following monomers (1) to (12) are copolymerized with the monomer having a carboxyl group or the monomer having an acid anhydride. ).

  (1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as

  (2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

  (3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, methacryl Acid hexyl, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, Alkyl methacrylates such as allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate;

  (4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

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

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

  (7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.

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

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

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

  (11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.

  (12) Methacrylic acid monomers having a hetero atom bonded to the α-position, for example, compounds described in JP-A No. 2002-309057, JP-A No. 2002-311569 and the like can be mentioned.

Among these, alkali-soluble resins having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.
In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups described in No. 271741, JP-A-11-352691 and the like, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 are It is preferable because of its excellent strength.

  In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 has an excellent balance of film strength and developability. It is preferable.

In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer.
In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among the above, (meth) acrylic resins having an allyl group, a vinyl ester group, and a carboxyl group in the side chain, and side chains described in JP-A Nos. 2000-187322 and 2002-62698. Since the double bond functions as a polymerizable group, the alkali-soluble resin having a double bond is preferable as the developing binder resin (E) as described later.

  These binder resins may be random polymers, block polymers, graft polymers or the like.

The binder resin as described above can be synthesized by a conventionally known method.
Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, 2-methoxyethyl acetate, Diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water, etc. Is mentioned.
These solvents are used alone or in combination of two or more.

The radical polymerization initiator used when synthesizing the binder resin includes benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, t-butyl peroxide. Examples thereof include organic peroxides such as oxybenzoate, and azo compounds such as 2,2′-azobisisobutyronitrile.
These radical polymerization initiators are preferably used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the monomer.

  In addition to the above, the alkali-soluble linear organic polymer used as the premise of the developable binder resin (E) includes those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and polyhydroxystyrene resins. Polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful. Further, such a linear organic polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

  Among these various alkali-soluble binder resins, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. From the viewpoint, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.

  Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a commercially available KS resist 106 ( Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (Daicel Chemical Industries, Ltd.) are preferred.

  The developable binder resin (E) may or may not have a polymerizable group. However, in order to further reduce the solubility of the resin in an alkaline developer by the action of the active species, the polymerizable binder resin (E) may have a polymerizable property. It preferably has a group.

  Although it does not restrict | limit especially as a polymeric group, An unsaturated group (unsaturated double bond etc.), an epoxy group, an oxetane group etc. can be mentioned, It is preferable that it is an unsaturated group.

  In order to introduce a polymerizable group into the binder resin, for example, the above-described alkali-soluble binder resin is polymerized using a monomer capable of adding a polymerizable group after polymerization, and the polymerizable group is added after polymerization. This can be done by applying a process to do this.

  Examples of the alkali-soluble binder resin having a polymerizable group include carboxyl group-containing resins, glycidyl group-containing unsaturated compounds such as glycidyl (meth) acrylate and allyl glycidyl ether, allyl alcohol, 2-hydroxyacrylate, and 2-hydroxy. Resin obtained by reacting unsaturated alcohol such as methacrylate, carboxyl group-containing resin having hydroxyl group, free isocyanate group-containing unsaturated compound, resin obtained by reacting unsaturated acid anhydride, addition of epoxy resin and unsaturated carboxylic acid Resins obtained by reacting polybasic acid anhydrides with reactants, resins obtained by reacting hydroxyl-containing polymerizable monomers with addition reaction products of conjugated diene copolymers and unsaturated dicarboxylic acid anhydrides, and elimination by base treatment Synthesizing a resin having a specific functional group that gives rise to an unsaturated group by causing a reaction; It was generated unsaturated groups by applying resin to the base treatment resins Typical resins.

  Among them, a resin obtained by reacting a carboxyl group-containing resin with a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate or allyl glycidyl ether, or a resin obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester compound ( ) Resin obtained by reacting a (meth) acrylic acid ester having a free isocyanate group such as acrylic acid-2-isocyanatoethyl, a resin having a structural unit represented by the following general formulas (21) to (23), base treatment A resin having a specific functional group that gives rise to an unsaturated group by elimination reaction is synthesized, and a resin or the like that generates an unsaturated group while maintaining an alkali-soluble group by subjecting the resin to a base treatment. More preferred.

  The alkali-soluble binder resin having a polymerizable group preferably contains at least one selected from structural units represented by any of the following general formulas (21) to (23).

In the general formulas (21) to (23), A ¹ , A ² , and A ³ each independently represent an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and R ²¹ represents a substituent. It represents an alkyl group that may have. G ¹ , G ² , and G ³ each independently represent a divalent linking group. X and Z each independently represent an oxygen atom, a sulfur atom, or —N (R ²² ) —, and R ²² represents an alkyl group which may have a substituent. Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent, or —N (R ²³ ) —, and R ²³ represents an alkyl group which may have a substituent. R ^{1 to} R ²⁰ each independently represents a hydrogen atom or a monovalent substituent.

In the general formula (21), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. R ¹ and R ² are preferably a hydrogen atom, and R ³ is preferably a hydrogen atom or a methyl group.
R ^{4 to} R ⁶ each independently represent a hydrogen atom or a monovalent substituent. Examples of R ⁴ include a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom, A methyl group and an ethyl group are preferred. R ⁵ and R ⁶ each independently have a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, or a substituent. A good aryl group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable. Here, examples of the substituent that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

A ¹ represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and X represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. Here, examples of R ²¹ and R ²² include an alkyl group which may have a substituent.
G ¹ represents a divalent linking group, but an alkylene group which may have a substituent is preferable. More preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, or a substituent having 6 to 20 carbon atoms. An aromatic group that may be present may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms that may have a substituent, or cyclo that may have a substituent having 3 to 10 carbon atoms. An alkylene group and an aromatic group which may have a substituent having 6 to 12 carbon atoms are preferable in terms of performance such as strength and developability.

Preferable examples of the substituent in G ^1, which except for the hydroxyl group hydrogen atoms among the groups bonded to a hetero atom, for example, an amino group, a thiol group, those containing no carboxyl group.

In the general formula (22), R ^{7 to} R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. R ⁷ and R ⁸ are preferably a hydrogen atom, and R ⁹ is preferably a hydrogen atom or a methyl group.
R ^{10 to} R ¹² each independently represents a hydrogen atom or a monovalent substituent. Specific examples of R ^{10 to} R ¹² include a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, and a substituent. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent An arylsulfonyl group may be mentioned. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.
Here, examples of the substituent that can be introduced include those listed in the general formula (21).

A ² each independently represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, where R ²¹ is a hydrogen atom, an alkyl group that may have a substituent, or the like. Can be mentioned.
G ² represents a divalent linking group, but an alkylene group which may have a substituent is preferable. Preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Aromatic group etc. may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cycloalkylene which may have a substituent having 3 to 10 carbon atoms. Group, and an aromatic group which may have a substituent having 6 to 12 carbon atoms is preferable in terms of performance such as strength and developability.
Here, the substituent for G ^2, those except the hydroxyl group hydrogen atoms among the groups bonded to a hetero atom, for example, an amino group, a thiol group, those containing no carboxyl group.
Y represents an oxygen atom, a sulfur atom, -N ^{(R 23)} - represents a or phenylene group which may have a substituent. Here, examples of R ²³ include a hydrogen atom and an alkyl group which may have a substituent.

In the general formula (23), R ^{13 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. R ¹³ and R ¹⁴ are preferably a hydrogen atom, and R ¹⁵ is preferably a hydrogen atom or a methyl group.
R ^{16 to} R ²⁰ each independently represents a hydrogen atom or a monovalent substituent, and R ^{16 to} R ²⁰ are, for example, a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, A group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, Examples include an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, a substituent An aryl group which may have is preferred. Examples of the substituent that can be introduced include those listed in the general formula (1).
A ³ represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and Z represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. Examples of R ²¹ and R ²² include the same as those in general formula (21).

G ³ represents a divalent linking group, but an alkylene group which may have a substituent is preferable. Preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Aromatic group etc. may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cycloalkylene which may have a substituent having 3 to 10 carbon atoms. Group, and an aromatic group which may have a substituent having 6 to 12 carbon atoms is preferable in terms of performance such as strength and developability.
Here, the substituent in G ³ is preferably a group in which a hydrogen atom is bonded to a heteroatom, excluding a hydroxyl group, for example, a group not containing an amino group, a thiol group, or a carboxyl group.

  The structural unit represented by the general formulas (21) to (23) is preferably a compound contained in one molecule in a range of 20 mol% or more and less than 95 mol% from the viewpoint of improving curability and reducing development residue. More preferably, it is 25 mol% to less than 90 mol%. More preferably, it is the range of 30 mol% or more and less than 85 mol%.

  The synthesis of the polymer having the structural units represented by the general formulas (21) to (23) is performed based on the synthesis method described in paragraph numbers [0027] to [0057] of JP-A No. 2003-262958. Can do. Among these, it is preferable to use the synthesis method 1) in the publication.

  The developable binder resin (E) may have a cationic polymerizable group in the side chain as a polymerizable group in order to improve the crosslinking efficiency, and includes, for example, an epoxy group, an oxetane group or the like in the side chain. Polymers and the like are also useful.

  In order to introduce an epoxy group into an alkali-soluble binder resin, for example, a monomer having an epoxy group (hereinafter also referred to as “monomer for introducing an epoxy group”) is polymerized as a monomer component. do it. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types. When the monomer component in obtaining the alkali-soluble binder resin also includes a monomer for introducing the epoxy group, the content ratio is not particularly limited, but is 5 to 70 mass in the total monomer components. %, Preferably 10 to 60% by mass.

The binder resin having an alkali-soluble group as a preferred form of the developable binder resin (E) in the present invention has been described above. When the alkali-soluble group is an acid group, the acid value of the developable binder resin (E) Is preferably 30 to 300 mgKOH / g, more preferably 50 to 200 mgKOH / g, and particularly preferably 70 to 160 mgKOH / g. When the acid value is within this range, the development residue is less likely to remain during pattern formation, and the coating uniformity is further improved.
In the case where the developing binder resin has a polymerizable group and the polymerizable group is an unsaturated group, the unsaturated value of the developing binder resin (E) is 0. 5 mmol / g or more is preferable, 0.7 mmol / g or more is more preferable, and 1.0 mmol / g or more is most preferable.
Here, the unsaturated value means the number of millimole of the unsaturated bond per 1 g of the binder polymer.
By setting the unsaturated equivalent of the developing binder resin (E) to 0.5 mmol / g or more, that is, by increasing the number of unsaturated double bonds in the resin, photopolymerization and sensitivity are improved. Furthermore, the improvement in the polymerizability also improves the adhesion to a solid surface such as a support and the fixability of the contained hollow or porous particles, resulting in defects in the hollow or porous particles in the pattern film during development. Therefore, a pattern having a tapered or rectangular cross-sectional shape tends to be obtained, which is preferable.

  The developable binder resin (E) may have a cyano group, and specifically may have a repeating unit containing a cyano group. In this case, the developable binder resin (E) preferably has a repeating unit containing a cyano group represented by the following general formula (III).

In general formula (III):
R _c31 represents a hydrogen atom, an alkyl group, a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group. These groups may be substituted with a cyano group.
However, at least one of R _c31 and R _c32 contains a cyano group.
L _c3 represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
R _c32 is preferably an unsubstituted alkyl group.
The divalent linking group of L _c3 is preferably an ester group, an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, or an ester bond (a group represented by —COO—).

  The repeating unit represented by the general formula (III) is preferably a repeating unit represented by the following general formula (CIII-1).

In general formula (CIII-1), R ₅ represents a hydrocarbon group. R _{c 31} has the same meaning as _{R c 31} of the general formula (CIII). However, at least one of R _c31 and R ₅ contains a cyano group.

Examples of the hydrocarbon group for R ₅ include a chain or cyclic structure. Specific examples in the case of having a cyclic structure include a monocyclic or polycyclic cycloalkyl group (preferably having 3 to 12 carbon atoms, more preferably 3 to 7 carbon atoms), a monocyclic or polycyclic cycloalkenyl group (carbon number). 3 to 12 are preferable), more preferably 6 to 12 carbon atoms, and an aralkyl group (preferably 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms).

The cycloalkyl group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. The bridged cyclic hydrocarbon ring includes a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. Etc. The bridged cyclic hydrocarbon ring also includes, for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.
Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These hydrocarbon groups may have a substituent, and preferred substituents include bromine atom, chlorine atom, alkyl group, hydroxyl group substituted with hydrogen atom, amino group substituted with hydrogen atom, cyano Groups. Preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and the substituent that may further have a bromine atom, a chlorine atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, or a hydrogen atom substituted An amino group formed can be mentioned.

  Examples of the substituent for the hydrogen atom include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

Specific examples of the repeating unit containing a cyano group represented by the general formula (III) are shown below, but are not limited thereto (in the specific examples, Ra is a hydrogen atom, an alkyl group, cyano A group or —CH ₂ —O—Rac ₂ group, wherein Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group.

  The content of the repeating unit containing a cyano group is preferably 10 to 80 mol%, more preferably 10 to 60 mol%, based on all repeating units of the developing binder resin (E).

  The developable binder resin may be a resin obtained by using a compound represented by the following general formula (E-1) (hereinafter sometimes referred to as “ether dimer”) as a copolymer. .

In formula (E-1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group as R ¹ and R ² is preferably a hydrocarbon group having 1 to 15 carbon atoms, and may further have a substituent.

The photosensitive composition of the present invention contains a resin obtained by using the compound represented by the general formula (E-1) as a copolymer, thereby forming a cured coating formed using the composition. The heat resistance and transparency of the film are further improved.
In the general formula (E-1) representing the ether dimer, the hydrocarbon group represented by R ¹ and R ² is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and isopropyl. A linear or branched alkyl group such as a group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl group; an aryl group such as a phenyl group; An alicyclic group such as cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group, etc .; 1-methoxyethyl group, An alkyl group substituted with alkoxy such as 1-ethoxyethyl group; an alkyl group substituted with aryl group such as benzyl; and the like.
Among these, a group containing a primary or secondary carbon which is difficult to be removed by an acid or heat, such as a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group, is particularly preferable in terms of heat resistance.
Note that R ¹ and R ² may be the same type of substituents or different substituents.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds.

The developable binder resin may or may not have a repeating unit corresponding to the compound represented by the general formula (E-1). The content of the repeating unit corresponding to the compound shown is preferably 0.1 to 50 mol%, more preferably 0.1 to 30 mol%, based on all repeating units of the developing binder resin. preferable.
[6-2] Developable binder resin whose solubility in an alkali developer is increased by the action of active species The developable binder resin (E) whose solubility in an alkali developer is increased by the action of active species is alkali-insoluble. In addition, a resin whose solubility in an alkaline developer is increased by the action of active species, and any known resin can be used.

As described above, the developing binder resin whose solubility in an alkaline developer is reduced by the action of the active species and the developing binder resin whose solubility in the alkali developer is increased by the action of the active species have been described. the weight average molecular weight of (E) is (in terms of polystyrene measured by GPC method) is preferably from 1000 to 2 × 10 ^5, more preferably in a 2000~1 × 10 ^5, 5000~5 × 10 ⁴ is particularly preferred.

  The content in the case of using the developable binder resin (E) is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and further preferably 1 to 5% by mass with respect to the total solid content of the photosensitive composition. preferable.

  The developing binder resin preferably has a refractive index of 1.55 or less, more preferably 1.50 or less, and most preferably 1.48 or less. Thereby, the refractive index of the pattern obtained can be reduced more reliably.

  Specific examples of the developable binder resin include the following binder resins (E-1) to (E-7), but the present invention is not particularly limited thereto. The numerical value shown in each unit represents each unit molar fraction in the resin molecule.

<Other ingredients>
As long as the effect of this invention is not impaired, the photosensitive composition may further contain the arbitrary components explained in full detail as needed.
Hereinafter, optional components that the photosensitive composition may contain will be described.

[7] (F) Sensitizer The photosensitive composition of the present invention is used for the purpose of improving radical generation efficiency such as a photopolymerization initiator or an acid generator, improving acid generation efficiency, and increasing the photosensitive wavelength. It may contain a sensitizer.
The sensitizer that can be used in the present invention is preferably a sensitizer that sensitizes the compound (B) that generates active species by irradiation with actinic rays or radiation by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer used in the photosensitive composition include compounds described in paragraph numbers [0101] to [0154] of JP-A-2008-32803.
The content of the sensitizer in the photosensitive composition is 0.1% by mass to 20% by mass with respect to the total solid content in the photosensitive composition from the viewpoint of light absorption efficiency into the deep part and initiation decomposition efficiency. It is preferable that 0.5 mass%-15 mass% are more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

[8] (H) Polymerization inhibitor In the photosensitive composition of the present invention, a small amount of (D) is used to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the photosensitive composition. H) A polymerization inhibitor may be added.
As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like can be mentioned.

(H) It is preferable that the addition amount of a polymerization inhibitor is 0.0005 mass%-5 mass% with respect to the total solid in a photosensitive composition.
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the coating film during the drying process after coating. . It is preferable that the addition amount of a higher fatty acid derivative is 0.5 mass%-10 mass% with respect to the total solid in a photosensitive composition.

[9] (J) Organic solvent The photosensitive composition of the present invention generally contains an organic solvent.
The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the photosensitive composition, and is particularly selected in consideration of the solubility, applicability, and safety of the binder. It is preferable. Examples of the organic solvent include various solvents described in paragraph [0187] of JP-A-2008-32803.

  Specific examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and methyl lactate. , Ethyl lactate, alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc. And 3-oxypropionic acid alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate) , Methyl 3-ethoxypropionate, 3 Ethyl ethoxypropionate, etc.)), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (specifically, And methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), 2-oxy-2-methylpropion Acid methyl, ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, aceto Ethyl, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether. (PGME: alias 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA: alias 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene and xylene.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-described components, and the solubility of the above-mentioned components and the improvement of the coating surface when a binder is included. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  As content in the photosensitive composition of an organic solvent, it is preferable to set it as the quantity from which a total solid content concentration in a composition will be 5-80 mass% from a viewpoint of applicability | paintability, 5 mass%-60 mass%. More preferable is an amount of 10% by mass to 50% by mass.

[10] (K) Adhesion promoter In the photosensitive composition of the present invention, an adhesion promoter can be added to improve adhesion to a hard surface such as a support of the formed cured film. . Examples of the adhesion promoter include silane coupling agents and titanium coupling agents.

Examples of the silane coupling agent include compounds described in paragraph [0185] of JP-A-2008-32803.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-amino Propyltriethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.
The photosensitive composition of the present invention may or may not contain an adhesion promoter, but when it is contained, the addition amount of the adhesion promoter is 0. 5 mass%-30 mass% are preferable, and 0.7 mass%-20 mass% are more preferable.

[11] (L) Surfactant Various surfactants may be added to the photosensitive composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

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

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

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), Solsperse 20000 (Japan Rouble) Zole Co., Ltd.).

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

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

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

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The photosensitive composition may or may not contain a surfactant, but when it is contained, the content of the surfactant is 0.001 mass relative to the total solid mass of the photosensitive composition of the present invention. % To 1% by mass, more preferably 0.01% to 0.1% by mass.

[12] (M) Other Additives Furthermore, in order to improve the physical properties of the cured film, a known additive such as an inorganic filler or a plasticizer may be added to the photosensitive composition of the present invention. Good.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added with respect to the total mass of the polymerizable compound and the binder polymer.

  As described above, the photosensitive composition of the present invention comprises (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and a resin (C1) or mixed resin. By containing (C2), the silicon atom or fluorine atom is present in the side chain of the resin, and the solubility in an alkali developer is changed by the action of an active species (preferably an acid or a radical). Low refractive index that can be patterned, with low refractive index, sufficient reactivity even at low exposure, few defects such as chipped patterns, little development residue, and no increase in refractive index even at high temperature and high humidity Rate material can be provided. In particular, the low refractive index material of the present invention is preferably used in patterning with an alkaline developer.

[13] Pattern Formation Method The pattern formation method of the present invention includes a step of forming a photosensitive film, a step of exposing the photosensitive film, and a development step of developing with an alkaline developer to obtain a pattern film.
Here, the photosensitive film is formed from the photosensitive composition of the present invention.
The present invention also relates to a pattern film obtained by this pattern forming method.
The method for forming the photosensitive film formed from the photosensitive composition of the present invention is not particularly limited. For example, the photosensitive composition is spin coated, roller coated, dip coated, scanned, sprayed, and bar coated. After applying to the substrate (support) by any method such as the method, the solvent is removed by heat treatment as necessary to form a coating film (photosensitive film), and pre-baking treatment is performed. Can do.
Examples of substrates include silicon wafer substrates, SiO ₂ wafer substrates, SiN wafer substrates, glass substrates, substrates on which various metal layers are formed, plastic films, microlenses, and on-chip color filters for image sensors. Examples include a coated substrate.

  As a method of applying to the substrate, a spin coating method and a scanning method are preferable. Particularly preferred is a spin coating method. A commercially available apparatus can be used for the spin coating method. For example, a clean track series (manufactured by Tokyo Electron), a D-spin series (manufactured by Dainippon Screen), an SS series or a CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used.

  The spin coating conditions may be any rotational speed, but from the viewpoint of in-plane uniformity of the film, a rotational speed of about 1300 rpm is preferable for a 300 mm diameter silicon substrate. In addition, the method for discharging the composition solution may be either dynamic discharge for discharging the composition solution onto a rotating substrate or static discharge for discharging the composition solution onto a stationary substrate. From the viewpoint of performance, dynamic ejection is preferable. In addition, from the viewpoint of suppressing the consumption of the composition, it is also possible to use a method in which only the main solvent of the composition is preliminarily discharged onto the substrate to form a liquid film, and then the composition is discharged from there. it can. The spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate.

  The photosensitive composition of the present invention can be easily cleaned and removed using a known cleaning liquid even when it adheres to, for example, a nozzle of a coating apparatus discharge section, a piping section of a coating apparatus, or the inside of a coating apparatus. . In this case, in order to perform more efficient cleaning and removal, it is preferable to use the solvent described above as the solvent contained in the photosensitive composition of the present invention as the cleaning liquid.

JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP 2007-2101 A, JP 2007-2102 A, JP 2007-281523 A and the like can also be suitably used as cleaning liquids for cleaning and removing the photosensitive composition of the present invention. .
As the cleaning liquid, it is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether.
These solvents that can be used as the cleaning liquid may be used alone or in combination of two or more.
When mixing 2 or more types of solvent, the mixed solvent formed by mixing the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group is preferable. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. The mixed solvent is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the ratio is particularly preferably 60/40.
In addition, in order to improve the permeability of the cleaning liquid to the photosensitive composition, the surfactant described above as a surfactant that can be contained in the photosensitive composition may be added to the cleaning liquid.

  The pre-bake treatment method is not particularly limited, and generally used hot plate heating, heating method using a furnace, light irradiation heating using a xenon lamp by RTP (Rapid Thermal Processor), etc. are applied. be able to. A heating method using hot plate heating or furnace is preferable. A commercially available apparatus can be preferably used as the hot plate, and a clean track series (manufactured by Tokyo Electron), D-spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used. As the furnace, Cx series (manufactured by Tokyo Electron) and the like can be preferably used. Examples of the prebaking condition include a condition of heating at 60 ° C. to 150 ° C. (preferably 60 ° C. to 120 ° C.) for about 0.5 minutes to 15 minutes using a hot plate or an oven.

The step of exposing the photosensitive film is performed through a mask as necessary.
Examples of actinic rays or radiation that can be applied to this exposure include infrared light, g-rays, h-rays, i-rays, KrF light, ArF light, X-rays, and electron beams. From the viewpoint of exposure amount, sensitivity, and resolution, i-line, KrF light, ArF light, and electron beam are preferable, and from the viewpoint of versatility, i-line and KrF light are most preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of ^{100mJ / cm 2 ~10000mJ / cm 2} . When using KrF light, it is preferable to irradiate with an exposure dose of 30 mJ / cm ^{2 to} 300 mJ / cm ² .
In addition, the exposed composition layer can be heated at 70 ° C. to 180 ° C. for about 0.5 minutes to 15 minutes using a hot plate or oven before the next development processing, if necessary.

  Subsequently, the exposed portion of the photosensitive film is developed on the exposed composition layer to obtain a pattern film (development process), and development is performed with a developer (development process). Thereby, a negative or positive pattern (resist pattern) can be formed.

Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, fourth amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Alkalinity such as 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, etc. Aqueous solution can be used .
Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
In particular, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide is desirable.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied. The development time varies depending on the composition of the photosensitive composition, but is usually about 30 to 120 seconds at 25 ° C.
When the above-mentioned various development methods include a step of discharging the developer from the developing nozzle of the developing device toward the photosensitive film, the discharge pressure of the discharged developer (flow rate per unit area of the discharged developer) preferably 2mL / sec / mm ² or less, more preferably 1.5mL / sec / mm ^2, more preferably not more than 1mL / sec / mm ^2. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the photosensitive film is reduced, and the photosensitive film / pattern film is carelessly cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

  Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.

  After the development, it is preferable to include a step of washing with a rinse solution.

  As the rinsing liquid in the rinsing treatment, pure water can be used, and an appropriate amount of a surfactant can be added and used.

In the rinsing step, the developed wafer is cleaned using a rinsing liquid. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step can be performed by heating the pattern film with a heating device such as a hot plate or oven. In this post-baking, the heating temperature is usually 120 to 250 ° C., preferably 160 to 250 ° C. 230 ° C. The heating time varies depending on the heating means, but is usually about 5 to 30 minutes when heated on a hot plate, and is usually about 30 to 90 minutes when heated in an oven.
Further, in the post-baking, a step baking method in which heating is performed twice or more can be adopted.

After the development process, if necessary, post-heating and / or post-exposure may be performed on the formed pattern film to further accelerate the curing of the pattern film (post-curing process by hardening process).
Thereby, light resistance, climate resistance, and film strength can be improved, and low refractive index properties can also be improved.

  The hardening process means that the pattern film on the substrate is further cured to give the film more solvent resistance and the like. As the method of hardening, it is preferable to perform heat treatment (firing). For example, a polymerization reaction during post-heating of the polymerizable group remaining in the resin can be used. The conditions for the post-heat treatment are preferably 100 to 600 ° C., more preferably 200 to 500 ° C., particularly preferably 200 ° C. to 450 ° C., preferably 1 minute to 3 hours, more preferably 1 minute to 2 hours, Especially preferably, it is the range of 1 minute-1 hour. The post-heating treatment may be performed in several times.

Further, in the present invention, not by heat treatment but by irradiating with high energy rays such as light irradiation and radiation irradiation, the polymer may still cause a polymerization reaction between the remaining polymerizable groups to be hardened. Good. Examples of high energy rays include electron beams, ultraviolet rays, and X-rays, but are not particularly limited to these methods.
The energy when an electron beam is used as the high energy beam is preferably 0.1 to 50 keV, more preferably 0.2 to 30 keV, and particularly preferably 0.5 to 20 keV. The total dose of the electron beam is preferably 0.01 to 5 μC / cm ² , more preferably 0.01 to ² μC / cm ² , and particularly preferably 0.01 to 1 μC / cm ² . The substrate temperature at the time of irradiation with an electron beam is preferably 0 to 500 ° C, more preferably 20 to 450 ° C, and particularly preferably 20 to 400 ° C. The pressure is preferably 0 to 133 kPa, more preferably 0 to 60 kPa, and particularly preferably 0 to 20 kPa.
From the viewpoint of preventing oxidation of the polymer, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, a gas such as oxygen, hydrocarbon, or ammonia may be added for the purpose of reaction with plasma, electromagnetic waves, or chemical species generated by interaction with an electron beam. The electron beam irradiation may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same each time, and may be performed under different conditions each time.

Ultraviolet rays may be used as the high energy rays. The irradiation wavelength region when ultraviolet rays are used is preferably 160 to 400 nm, and the output is preferably 0.1 to 2000 mWcm ⁻² immediately above the substrate. The substrate temperature at the time of ultraviolet irradiation is preferably 250 to 450 ° C., more preferably 250 to 400 ° C., and particularly preferably 250 to 350 ° C. From the viewpoint of preventing oxidation of the polymer of the present invention, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, the pressure at that time is preferably 0 to 133 kPa.

  The film may be hardened by performing heat treatment and high energy ray treatment irradiation such as light irradiation and radiation irradiation simultaneously or sequentially.

  As a dry film thickness, a coating film having a thickness of about 0.05 to 1.5 μm can be formed by a single coating and a thickness of about 0.1 to 3 μm can be formed by a second coating.

Although the use of the photosensitive composition of this invention is not specifically limited, As mentioned above, it is preferable to use in order to produce a low refractive index film | membrane.
Therefore, the present invention also relates to a low refractive index film that is a pattern film obtained by the above-described pattern forming method of the present invention.
Furthermore, the present invention also relates to an optical device having the low refractive index film.
The present invention also relates to a solid-state imaging device including such an optical device.
Hereinafter, such a low refractive index film (for example, an antireflection film) will be described in detail. However, the preferable range of the following various physical properties in the low refractive index film is a preferable range particularly in the application of the low refractive index film, but is not limited to the application.

<Low refractive index film>
The pattern film obtained using the composition described above exhibits excellent low refractive index properties. Specifically, the refractive index (wavelength 633 nm, measurement temperature 25 ° C.) of the pattern film is preferably 1.35 or less, more preferably 1.23-1.34, and 1.24-1 .30 is particularly preferred. Within the above range, it is useful as an antireflection film described later.

<Antireflection film>
As a suitable usage mode of the pattern film obtained by using the composition of the present invention described above, an antireflection film can be mentioned. In particular, it is suitable as an antireflection film for optical devices (for example, microlenses for image sensors, plasma display panels, liquid crystal displays, organic electroluminescence, etc.).
The lower the reflectance when used as an antireflection film, the better. Specifically, the specular average reflectance in the wavelength region of 450 to 650 nm is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The reflectance is preferably as small as possible, and most preferably 0.
The haze of the antireflection film is preferably 3% or less, more preferably 1% or less, and most preferably 0.5% or less. The reflectance is preferably as small as possible, and most preferably 0.

  When the above-described film is used as a single-layer type antireflection film, if the refractive index of the transparent substrate is nG, the refractive index n of the antireflection film is √nG, that is, 1/2 of the refractive index of the transparent substrate. Preferably it is a power. For example, since the refractive index of optical glass is 1.47 to 1.92 (wavelength 633 nm, measurement temperature 25 ° C.), n of the single-layer antireflection film formed on the optical glass is 1.21 to 1. .38 is preferred. In addition, it is preferable that the film thickness of the antireflection film in that case is 10 nm-10 micrometers.

When the above-described film is used as a multilayer antireflection film, the film is used as a low refractive index layer, and includes, for example, a high refractive index layer, a hard coat layer, and a transparent substrate under the film. be able to. At this time, the high refractive index layer may be formed directly on the substrate without providing the hard coat layer. Further, an intermediate refractive index layer may be further provided between the high refractive index layer and the low refractive index layer, or between the high refractive index layer and the hard coat layer.
Below, each layer in the case of a multilayer type is explained in full detail.

(1) Low refractive index layer
A low refractive index layer is comprised from the pattern film obtained using the composition of this invention as mentioned above. The refractive index and thickness of the low refractive index layer will be described.

(I) Refractive index The refractive index (wavelength 633 nm, measurement temperature 25 ° C.) of the pattern film obtained using the composition of the present invention, that is, the refractive index of the low refractive index film (also referred to as a low refractive index layer) is 1. It is preferable to be 35 or less. The reason for this is that when the low refractive index film has a refractive index of 1.35 or less, the antireflective effect can be reliably exhibited when combined with a high refractive index film (also referred to as a high refractive index layer). Because.
The refractive index of the low refractive index film is more preferably 1.34 or less, and further preferably 1.33 or less. When a plurality of low refractive index films are provided, at least one of them may have a refractive index value within the above-described range.

  Moreover, when providing a low refractive index layer, since the more excellent antireflection effect is acquired, it is preferable to make the refractive index difference between high refractive index layers into 0.05 or more values. Since the difference in refractive index between the low refractive index layer and the high refractive index layer is 0.05 or more, a synergistic effect in these antireflection film layers can be easily obtained, and the antireflection effect can be obtained more reliably. It is easy to be done. Therefore, it is more preferable to set the refractive index difference between the low refractive index layer and the high refractive index layer to a value within the range of 0.1 to 0.8, and within the range of 0.15 to 0.7. More preferably, it is a value.

(Ii) Thickness The thickness of the low refractive index layer is not particularly limited, but is preferably 20 to 300 nm, for example. When the thickness of the low refractive index layer is 20 nm or more, adhesion to the high refractive index film as a base is surely obtained. It is easy to get reliably. Therefore, the thickness of the low refractive index layer is more preferably 20 to 250 nm, and still more preferably 20 to 200 nm. In order to obtain higher antireflection properties, when a plurality of low refractive index layers are provided to form a multilayer structure, the total thickness may be set to 20 to 300 nm.

(2) High refractive index layer Although it does not restrict | limit especially as a curable composition for forming a high refractive index layer, As a film formation component, an epoxy resin, a phenol resin, a melamine resin, an alkyd system It is preferable to include one kind or a combination of two or more kinds of resin, cyanate resin, acrylic resin, polyester resin, urethane resin, siloxane resin and the like. With these resins, a strong thin film can be formed as the high refractive index layer, and as a result, the scratch resistance of the antireflection film can be remarkably improved.
However, the refractive index of these resins alone is usually 1.45 to 1.62, which may not be sufficient to obtain high antireflection performance. Therefore, it is preferable to make refractive index 1.70-2.20 by mix | blending a high refractive index inorganic particle, for example, metal oxide particle. Moreover, as a hardening form, although the curable composition which can be thermosetting, ultraviolet curing, and electron beam curing can be used, the ultraviolet curable composition with favorable productivity is used more suitably.

  The thickness of the high refractive index layer is not particularly limited, but is preferably 20 to 30,000 nm, for example. When the thickness of the high refractive index layer is 20 nm or more, when combined with the low refractive index layer, the antireflection effect and the adhesion to the substrate can be more reliably obtained, while the thickness is 30,000 nm or less. In addition, optical interference is unlikely to occur, and the antireflection effect is easily obtained more reliably. Therefore, the thickness of the high refractive index layer is more preferably 20 to 1,000 nm, and further preferably 50 to 500 nm. In order to obtain higher antireflection properties, when a plurality of high refractive index layers are provided to form a multilayer structure, the total thickness may be set to 20 to 30,000 nm. In addition, when providing a hard-coat layer between a high refractive index layer and a board | substrate, the thickness of a high refractive index layer can be 20-300 nm.

(3) Hard coat layer The constituent material of the hard coat layer used in the antireflection film of the present invention is not particularly limited. Examples of such a material include one kind of siloxane resin, acrylic resin, melamine resin, epoxy resin, or a combination of two or more kinds.

  Moreover, although it does not restrict | limit especially also about the thickness of a hard-coat layer, it is preferable to set it as 1-50 micrometers, and it is more preferable to set it as 5-10 micrometers. When the thickness of the hard coat layer is 1 μm or more, the adhesion of the antireflection film to the substrate can be more reliably improved. On the other hand, when the thickness is 50 μm or less, it can be easily formed uniformly.

(4) Substrate The type of the substrate used for the low refractive index film of the present invention is not particularly limited. For example, glass, polycarbonate resin, polyester resin, acrylic resin, triacetyl cellulose resin (TAC), etc. And a transparent substrate and a silicon wafer. By using an antireflection film including these substrates, it is excellent in the field of application of a wide range of antireflection films such as a lens part of a camera, a screen display part of a television (CRT), a color filter or a photographing element in a liquid crystal display device. An antireflection effect can be obtained.

  The pattern film obtained using the composition of the present invention can also be used as a surface protective film or retardation film for optical devices (for example, microlenses).

  The composition of the present invention can be preferably used particularly as a coating application for microlenses (herein, the concept of microlenses includes the concept of microlens arrays).

  The pattern film obtained from the pattern forming method of the present invention is formed using the photosensitive composition of the present invention, has a low refractive index, few pattern defects and development residues, and is formed with high weather resistance. Therefore, it is preferably used for other uses other than for microlenses and solid-state imaging devices. Other applications include, for example, various OA equipment, liquid crystal display elements such as liquid crystal televisions, mobile phones, projectors, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and optical fiber connectors. Films, molding resins, casting resins, stereolithography resins, sealants, dental polymer materials, printing inks, paints, photosensitive resins for printing plates, for printing, especially in areas where light reflection is to be suppressed Color proof, printed circuit board resist, semiconductor manufacturing resist, microelectronics resist, micromachine component manufacturing resist, etc., insulating material, hologram material, wafer level lens body or lens light shielding film forming material, waveguide material, Overcoat agents, adhesives, pressure-sensitive adhesives, adhesives, release coating agents, etc., can be used for these various applications Rukoto can.

  In particular, by forming the pattern film of the present invention on the surface of the microlens using the pattern forming method of the present invention, a high-definition microlens coated with the film having the above characteristics can be easily produced with a high product yield. Can be formed.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited by these examples.

1. Synthesis of Resin 1 as Resin (C1) To a 300 mL three-necked flask, 5.30 g of propylene glycol monomethyl ether (PGME) was added and heated at 80 ° C. in a nitrogen atmosphere. A uniform solution of 5.2 g of methyl methacrylate (trimethylsilyl), 8.1 g of methacrylic acid, 0.23 g of azo-based thermal polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries) and 47.7 g of PGME was added dropwise over 4 hours. . After further heating and stirring at 80 ° C. for 2 hours, the nitrogen flow was stopped and stirring was further performed at 90 ° C. for 2 hours. The polymer had a mass average molecular weight of 20337 and a number average molecular weight of 9823 by GPC measurement (polystyrene conversion).
After leaving overnight under air, 4.9 g of glycidyl methacrylate, 0.54 g of dimethyldodecylamine and 0.036 g of p-methoxyphenol were added to the polymer solution, and the mixture was heated and stirred at 90 ° C. for 10 hours. It was confirmed by 1HNMR that glycidyl methacrylate was consumed. The polymer had a mass average molecular weight of 32155 and a number average molecular weight of 11113 as measured by GPC (polystyrene conversion).
The acid value was determined by acid value titration, and the acid value in terms of KOH of this polymer was 88.7 mgKOH / g. The unsaturated value of this polymer was 1.75 mmol / g, and the refractive index was 1.490. The refractive index of the polymer was measured by the following method. A polymer solution having a polymer concentration of 10% by mass dissolved in propylene glycol methyl ether acetate (PGMEA) was applied onto a silicon wafer, and then heated at 100 ° C. for 2 minutes on a hot plate to obtain a polymer film. The refractive index of the substrate was measured at a wavelength of 633 nm in this polymer film using ellipsometry (VASE) manufactured by JA Woollam Japan.

  Resins 2 to 14 were synthesized in the same manner. Table 1 below shows the structures of resins 1 to 14, the molar fraction of each unit, the mass average molecular weight, the number average molecular weight, the acid value, the unsaturated value, and the refractive index.

  Moreover, the following resin A was used in the mixed resin (C2) as a resin corresponding to the above-mentioned resin (C2-1), and the following resin a as a resin corresponding to the above-mentioned resin (C2-2).

  The following polymers were used as comparative resins.

  As the photopolymerization initiator, the following compound manufactured by Ciba Japan was used.

  The following compounds were used as the polymerizable compound.

  The following developable binder resin was used.

2. Preparation of Photosensitive Composition Components of the following component amounts were mixed, and the mixed solution was filtered through a tetrafluoroethylene filter having a pore size of 0.2 μm to prepare the photosensitive composition of Example 1-1.
・ Hollow or porous particles (hollow silica (refractive index: 1.20): thruria 2320 (product of JGC Catalysts & Chemicals Co., Ltd., 20 mass% methyl isobutyl ketone dispersion)) 262.5 parts by mass B) -1 3.8 parts by mass Resin 1 (20% by mass PGME solution) 93.8 parts by mass Solvent: Propylene glycol methyl ether acetate (PGMEA) 140 parts by mass

3. Preparation of low refractive index transparent pattern The photosensitive composition obtained above was applied onto a silicon wafer by spin coating, and then heated on a hot plate at 100 ° C. for 2 minutes to give a film thickness of 0.3 μm. A membrane was obtained.
Next, using the i-line stepper FPA-3000i5 + (manufactured by Canon Inc.), the obtained photosensitive film is a dot array having different wavelengths from 0.5 micron square to 100 micron square at a wavelength of 365 nm. Exposed through a pattern mask.
The exposed photosensitive film was subjected to paddle development for 60 seconds at 23 ° C. using a 0.3 mass% tetramethylammonium hydroxide aqueous solution. Thereafter, rinsing was performed using water in a spin shower, followed by washing with pure water to obtain a transparent pattern having a thickness of 0.1 μm.

4). Evaluation 4-1. Appropriate Sensitivity Sensitivity capable of faithfully forming a 1.0 μm square pattern from a 1.0 μm square pattern mask was defined as appropriate sensitivity.

4-2. Pattern Defect and Residue Evaluation The shape of the transparent pattern obtained with appropriate sensitivity was observed at 30000 times from above the silicon wafer using a length measuring SEM (S-7800H, manufactured by Hitachi, Ltd.). The obtained dot pattern was observed, and pattern defects were evaluated according to the following evaluation criteria.
There is no missing pattern: ○
Slight chipping of patterns is observed (1-2 per pattern): Δ
Marked chipping is noticeable (3 or more per pattern): ×
Moreover, the residue around the pattern was measured according to the following evaluation criteria.
Not seen at all: ○
A little seen (1-10 pieces / μm ² ): Δ
Remarkably seen (11 or more / μm ² ): ×

4-3. Measurement of Refractive Index of Low Refractive Index Transparent Pattern The photosensitive composition obtained in 4-2 above was applied on a silicon wafer, and then heated at 100 ° C. for 2 minutes on a hot plate to obtain a transparent film. The value measured for this substrate at a wavelength of 633 nm and 25 ° C. in this transparent film using ellipsometry (VASE) manufactured by JA Woollam Japan was used as the refractive index.
The respective results are shown in Table 2.

4-4. Weather resistance The pattern obtained in the above 4-2 was allowed to stand for 3 days in a thermocelco controlled at 60 ° C. and 85% RH, and the refractive index was measured in the same manner as in 4-3.
○ when the refractive index change is less than 0.5% compared to fresh
△, when 0.5% or more and less than 1%
1% or more ×
It was.

<Example 1-1 to Example 1-18, Comparative Example 1-1 to Comparative Example 1-5>
The compositions of Examples 1-2 to 1-18 and Comparative Examples 1-1 to 1-5 were used in the same manner as in Example 1-1 except that the components of the types and component amounts shown in Table 2 were used. Prepared. These compositions were also evaluated in the same manner as in Example 1-1, and the results are summarized in Table 2.

<Example 2-1 to Example 2-16, Comparative Example 2-1 to Comparative Example 2-5>
In the preparation of the photosensitive composition of Example 1-1, PMA-ST (manufactured by Nissan Chemical Co., Ltd., 30 mass% dispersion of porous silica (refractive index: 1.27)) was used instead of thruria 2320. Except for this, the composition of Example 2-1 was prepared in the same manner as Example 1-1. Moreover, the composition of Examples 2-2 to 2-16 and Comparative Examples 2-1 to 2-5 was the same as Example 2-1, except that each component of the type and component amount shown in Table 3 was used. Was prepared. These compositions were also evaluated in the same manner as in Example 1-1, and the results are summarized in Table 3.
In the above Examples and Comparative Examples, the resin A, the resin a, and the comparative resins 1 to 3 were used as a 20% by mass PGME solution in the same manner as the resin (C1).

  Note that “development flow” in the result of appropriate sensitivity means that all the films on the silicon wafer are dissolved during development, and “development impossible” means that all the films on the silicon wafer remain during development. Means. Regarding pattern defects, residues and weather resistance of Comparative Example 1-2, Comparative Example 1-4, Comparative Example 1-5, Comparative Example 2-2, Comparative Example 2-4, and Comparative Example 2-5, pattern formation Because it was not possible, it was not possible to measure.

  In addition to the hollow or porous particles used in the above examples, Snowtex MIBK-SD-L (30% by mass dispersion of porous silica (refractive index 1.26) manufactured by Nissan Chemical Co., Ltd.), PL-2L -PGME (20% by mass dispersion of porous silica (refractive index: 1.26) manufactured by Fuso Chemical Co., Ltd.) can also be used, and the same effect as described above was obtained.

  From the results shown in Tables 2 and 3, when the photosensitive composition according to the present invention is used, the appropriate sensitivity is high, the refractive index is low, the chipping and residue of the pattern after development are few, and the refractive index under high temperature and high humidity. It can be seen that it is possible to form a pattern that shows small performance and excellent weather resistance. Moreover, compared with Example 1-11 using the resin 11 containing a fluorine atom in a side chain, the other examples using a resin containing a silicon atom in a side chain were excellent in weather resistance.

Claims (22)

(A) hollow or porous particles;
(B) a compound that generates active species upon irradiation with actinic rays or radiation;
The photosensitive composition containing the following resin (C1) or mixed resin (C2).
(C1) Resin that contains silicon atoms or fluorine atoms in the side chain and changes in solubility in an alkali developer by the action of the active species (C2) Resin that contains silicon atoms or fluorine atoms in the side chain (C2-1) And a resin (C2-2) whose solubility in an alkaline developer is changed by the action of the active species.   The photosensitive composition of Claim 1 whose refractive index of the said hollow or porous particle (A) is 1.10-1.40.   The photosensitive composition of Claim 1 or 2 whose said resin (C1) or resin (C2-2) is resin in which the solubility with respect to an alkali developing solution reduces by the effect | action of the said active species.   The photosensitive composition as described in any one of Claims 1-3 containing the said resin (C1).   The photosensitive composition as described in any one of Claims 1-4 whose active species which the said compound (B) generate | occur | produces by irradiation of actinic light or a radiation is a radical. The photosensitive composition as described in any one of Claims 1-5 in which the said resin (C1) or resin (C2-1) contains the repeating unit represented by the following general formula (1) or (2). object.

In general formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group or an aryl group.
R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group or a siloxy group.
R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group or a siloxy group.
X ¹ represents a divalent linking group.
n ¹ represents an integer of 0 to 20.
In the general formula ^(2), R 1, ^{R 2} and ^{R 3} have the same meaning as ^R 1, ^{R 2} and ^{R 3} in the general formula (1).
X ² represents a divalent linking group.
R ⁹ represents an alkyl group substituted with a fluorine atom. The photosensitive composition of Claim 6 whose repeating unit represented by the said General formula (1) or (2) is a repeating unit represented by the following general formula (3) or (4).

In general formula (3), R ¹⁰ represents a hydrogen atom or an alkyl group.
R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group or a siloxy group.
A ¹¹ represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —.
R ¹⁵ represents a hydrogen atom or an alkyl group.
Y ¹¹ represents an alkylene group, an alkyleneoxy group, or a combination thereof.
In general formula (4),
A ¹² represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —.
Y ¹² represents an alkylene group, an alkyleneoxy group, or a combination thereof.
R ¹⁴ represents an alkyl group substituted with a fluorine atom.
R ¹⁰ and ^{R 15} have the same meanings as ^{R 10} and ^{R 15} in the general formula (3).   The resin (C1) is (I) at least one repeating unit represented by any one of the general formulas (1) to (4), (II) a radical or cationic polymerizable repeating unit, and (III) an alkali. The photosensitive composition of Claim 6 or 7 containing a soluble repeating unit. The radical or cation polymerizable repeating unit (II) is a repeating unit represented by any one of the following general formulas (5) to (7), and the alkali-soluble repeating unit (III) is (meth) acrylic. The photosensitive composition of Claim 8 which is an acid.

In general formulas (5) to (7), A ²¹ , A ²² and A ²³ each independently represents an oxygen atom, a sulfur atom or —N (R ⁴¹ ) —, and R ⁴¹ represents a hydrogen atom or an alkyl group. To express.
G ²¹ , G ²² and G ²³ each independently represent a divalent linking group.
X ²¹ and Z ²¹ each independently represent an oxygen atom, a sulfur atom or —N (R ⁴² ) —, and R ⁴² represents a hydrogen atom or an alkyl group.
Y ²¹ represents an oxygen atom, a sulfur atom, a phenylene group or —N (R ⁴³ ) —, and R ⁴³ represents a hydrogen atom or an alkyl group.
R ^{21 to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent organic group.   The unsaturated value of the resin (C1) or the resin (C2-2) is 0.5 mmol / g to 2.0 mmol / g, and the acid value is 50 mgKOH / g to 200 mgKOH / g. 10. The photosensitive composition as described in any one of 9.   The photosensitive composition as described in any one of Claims 1-10 whose refractive index of the said resin (C1) or resin (C2-1) is 1.45 or more and less than 1.50.   The photosensitive composition as described in any one of Claims 1-11 whose said hollow or porous particle (A) is a silica particle.   The photosensitive composition as described in any one of Claims 1-12 which contains the said hollow or porous particle (A) 20 mass%-90 mass% in the total solid except a solvent.   Furthermore, (D) The photosensitive composition as described in any one of Claims 1-13 containing a polymeric compound.   Furthermore, the photosensitive composition as described in any one of Claims 1-14 containing (E) developable binder resin.   The pattern formation material which is the photosensitive composition as described in any one of Claims 1-15.   The photosensitive film | membrane formed with the photosensitive composition as described in any one of Claims 1-15.   A pattern forming method comprising a step of forming a photosensitive film according to claim 17 on a support, a step of exposing the photosensitive film, and a developing step of developing with an alkaline developer to obtain a pattern film.   A pattern film obtained by the pattern forming method according to claim 18.   A low refractive index film, which is the pattern film according to claim 19.   An optical device having the low refractive index film according to claim 20.   A solid-state imaging device comprising the optical device according to claim 21.