JP2012053243A - Photosensitive composition, pattern forming material, and photosensitive film, pattern forming method, pattern film, antireflection film, insulating film, optical device and electronic device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition capable of forming a pattern film having low dielectric constant and high Young's modulus and heat resistance (which is, for example, performance suitable for an insulating film between layers in a semiconductor element device and the like) with high resolution and a pattern forming material and a photosensitive film, a pattern forming method and a pattern film using this; and further to provide an antireflection film and an insulating film produced using the photosensitive composition, and an optical device and an electronic device using these.SOLUTION: Provided are a photosensitive composition containing (A) a polymer having a polymerizable group and a cage-like silsesquioxane structure, (B) a compound having an SiH bond and (C) a photopolymerization initiator; a pattern forming material; and a photosensitive film, a pattern forming method, a pattern film, an antireflection film, an insulating film, an optical device and an electronic device using this.

Description

  The present invention relates to a photosensitive composition whose properties change upon reaction with irradiation of actinic rays or radiation, and a pattern forming method and a film using the photosensitive composition. More specifically, it is possible to form a coating film having an appropriate uniform thickness, which is useful as an interlayer insulating film material in a semiconductor element or the like, or an antireflection film in an optical device, and has resolution, dielectric constant characteristics, and refractive index characteristics. Photosensitive composition, photosensitive composition, pattern forming material, and photosensitive film, pattern forming method, pattern film, antireflection film, insulating film, The present invention relates to an optical device and an electronic device.

As an interlayer insulating film in a conventional semiconductor element or the like, a silica (SiO ₂ ) film formed by a vacuum process such as a vapor deposition (CVD) method is frequently used. In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating type insulating film called a SOG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has been used. It has become. In addition, with high integration of semiconductor elements and the like, an interlayer insulating film having a low dielectric constant, which is mainly composed of polyorganosiloxane called organic SOG, has been developed.

However, even the CVD-SiO ₂ film showing the lowest dielectric constant among the inorganic material films has a relative dielectric constant of about 4. The relative dielectric constant of the SiOF film, which has been recently studied as a low dielectric constant CVD film, is about 3.3 to 3.5. This film has high hygroscopicity, and the dielectric constant increases while being used. There is a problem of doing.

  Under such circumstances, a method of reducing the dielectric constant by forming pores by adding a high boiling point solvent or a thermally decomposable compound to organopolysiloxane has been proposed as an insulating film material excellent in insulation, heat resistance and durability. (See Non-Patent Document 1). However, in such a porous film, even if the dielectric constant characteristics are lowered due to the porous film, mechanical strength is lowered and the dielectric constant is increased due to moisture absorption. Further, since holes connected to each other are formed, there has been a problem that copper used for wiring diffuses into the insulating film.

  On the other hand, an attempt to obtain a film having a low dielectric constant and a low density by applying a solution obtained by adding a low molecular weight cage compound to an organic polymer is also known (see Patent Document 1). However, in the method of adding a cage compound monomer, the characteristics such as dielectric constant and Young's modulus of the obtained film are not always satisfactory from a practical viewpoint, and there are further problems such as deterioration of the coated surface condition. was there.

In addition to such dielectric characteristics, many problems such as complicated manufacturing processes 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 a method is described, there are still many insufficient points, and improvement is desired.
Specifically, Patent Document 2 describes a negative resist using a double-decker POSS polymer, but the resolution in pattern formation is insufficient and the dielectric constant of the resulting pattern is also insufficient.
Moreover, although the resist by a sol-gel polymer is described in patent document 3, while the resolution in pattern formation is inadequate, the low dielectric constant property of the pattern obtained is also inadequate.
Further, in Examples of Patent Document 4, a film is formed using a solution containing a polysilsesquioxane polymer derived from a cage-type silicon compound having a specific structure and a photosensitive metal complex, A technique for forming a pattern using a sol-gel condensation reaction by exposing and developing the film is known. However, the exposure dose is a very large and low-sensitivity photosensitive film, and the resulting pattern has insufficient refractive index and low dielectric constant. Furthermore, since a metal catalyst is used, applicable devices are greatly limited.

JP 2000-334881 A JP 2009-215423 A US Patent Publication No. 2009/291389 JP 2007-298841 A

Chem. Rev. 56, 2010, 110, 56-110

This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past, and to achieve the following objectives.
That is, the present invention is a photosensitivity capable of forming a pattern film having a low dielectric constant and a high Young's modulus and heat resistance (for example, performance suitable for an interlayer insulating film in a semiconductor element device, etc.) with high resolution. It is an object to provide a composition, a pattern forming material, a photosensitive film using the same, a pattern forming method, and a pattern film.
Furthermore, another object of the present invention is to provide an antireflection film and an insulating film produced using the photosensitive composition, and an optical device and an electronic device using the same.

  The present invention has the following configuration, whereby the above object of the present invention is achieved.

[1]
(A) a polymer having a polymerizable group and a cage silsesquioxane structure;
(B) a compound having a SiH bond;
(C) The photosensitive composition containing a photoinitiator.
[2]
The photosensitive composition as described in [1] above, wherein the photopolymerization initiator is a nonmetallic photopolymerization initiator.
[3]
The photosensitive composition as described in [1] or [2] above, wherein the photopolymerization initiator is a radical photopolymerization initiator.
[4]
The silsesquioxane which the polymer which has the said (A) polymeric group and cage silsesquioxane structure is comprised from the 1 type, or 2 or more types of cage silsesquioxane compound represented by following formula (1). The photosensitive composition of any one of said [1]-[3] which is a polymer obtained from oxanes.
(RSiO _1.5 ) _a formula (1)
(In formula (1), R represents an organic group each independently, and at least 2 of R represents a polymeric group. A represents an integer of 8 to 16. Several R are the same. It may or may not be.)
However, a polymerizable group derived from the cage silsesquioxane compound remains in the polymer.
[5]
The photosensitive composition according to any one of the above [1] to [4], which is a negative composition.
[6]
The photosensitive composition of any one of said [1]-[5] whose said photoinitiator is an oxime compound.
[7]
The cage silsesquioxane compound is one or more selected from the group consisting of cage silsesquioxane compounds represented by the following general formula (Q-1) to general formula (Q-7). The photosensitive composition according to any one of [4] to [6] above.

(In General Formula (Q-1) to General Formula (Q-7), each R independently represents an organic group. In each of General Formula (Q-1) to General Formula (Q-7), R represents At least two of them represent polymerizable groups.)
[8]
The photosensitive property according to any one of the above [4] to [7], wherein the content of the polymerizable group in the polymer is 10 to 90 mol% in the total organic groups bonded to the silicon atom. Composition.
[9]
The photosensitive composition of any one of said [4]-[8] whose weight average molecular weights of the said polymer are 10,000-500,000.
[10]
The pattern formation material which is the photosensitive composition of any one of said [1]-[9].
[11]
The photosensitive film | membrane formed with the photosensitive composition of any one of said [1]-[9].
[12]
The pattern formation method including the process of forming the photosensitive film as described in said [11], the process of exposing the said photosensitive film | membrane, and the image development process which develops and obtains a pattern film.
[13]
The pattern forming method as described in [12] above, wherein the developing step is a step of developing using a developer containing an organic solvent.
[14]
The developer containing the organic solvent is at least one solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents, according to [13] above. Pattern forming method.
[15]
A pattern film obtained by the pattern forming method according to any one of [12] to [14].
[16]
The pattern film according to [15], wherein the refractive index is 1.35 or less.
[17]
The pattern film according to [15] or [16], wherein the relative dielectric constant at 25 ° C. is 2.50 or less.
[18]
An antireflection film, which is the pattern film according to any one of [15] to [17].
[19]
An insulating film, which is the pattern film according to any one of [15] to [17].
[20]
An optical device having the antireflection film according to [18].
[21]
The electronic device which has an insulating film as described in said [19].

The present invention preferably further has the following configuration.
[22] The photosensitive composition according to any one of [1] to [8], wherein the compound having an SiH bond is a compound represented by the following general formula (B-1).
HSiR _B ¹ R _B ² R _B ³ (B-1)
In General Formula (B-1), R _B ¹ , R _B ^2, and R _B ³ each independently represent a hydrogen atom or a substituent. At least two of R _B ¹ , R _B ² , and R _B ³ may be bonded to each other to form a ring.
[23]
The photosensitive composition according to any one of [1] to [8] and [22] above, wherein the compound having an SiH bond is a compound having at least one siloxane bond.
[24]
The photosensitive composition as described in [23] above, wherein the compound having an SiH bond is a linear polysiloxane.
[25]
The photosensitive composition according to any one of [1] to [8] and [22] to [24], wherein a radical polymerization reaction or a cationic polymerization reaction proceeds by exposure.

According to the present invention, photosensitivity capable of forming a pattern film having a low dielectric constant and high Young's modulus and high heat resistance (in particular, performance suitable for an interlayer insulating film in a semiconductor element device, etc.) with high resolution. A composition, a pattern forming material, a photosensitive film using the same, a pattern forming method, and a pattern film can be provided.
Furthermore, according to the present invention, it is possible to provide an antireflection film and an insulating film produced using the photosensitive composition, and an optical device and an electronic device using these.

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 contains (A) a polymer having a polymerizable group and a cage silsesquioxane structure, (B) a compound having a SiH bond, and (C) a photopolymerization initiator. . (A) is a polymer containing a repeating unit having a cage silsesquioxane in the side chain and a polymerizable group, or a cage silsesquioxane in the main chain or side chain, A polymer having a polymerizable group as a substituent on the sun is preferred. More preferably, the photosensitive composition of the present invention is obtained from (S) silsesquioxanes composed of one or more cage silsesquioxane compounds represented by the average composition formula described later. And (B) a compound having a SiH bond, and (C) a photopolymerization initiator. However, a polymerizable group derived from a cage silsesquioxane compound remains in this polymer.

By using the photosensitive composition of the present invention, a polymer having a polymerizable group and a cage silsesquioxane structure (preferably a cage silsesquioxane compound) contained in the photosensitive composition of the present invention. It is considered that the structure of the polymer) greatly contributes to the formation of a patterned film having a good coated surface, a low dielectric constant, and a high Young's modulus.
The photosensitive composition of the present invention comprising a polymer having a polymerizable group and a cage silsesquioxane structure (preferably a polymer obtained from a cage silsesquioxane compound) and a photopolymerization initiator. After the film is formed by the above, the film is exposed, whereby a reaction due to the remaining polymerizable group in the polymer proceeds, and the exposed portion is cured. Next, by performing a development process using an organic solvent, the unexposed portion is removed and a pattern can be formed.

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

  First, the compound (preferably silsesquioxane) which is the raw material of the polymer contained in the composition will be described. Then, the polymer manufactured from this compound (preferably silsesquioxane) and its manufacturing method are explained in full detail.

[1] Compound which is a raw material of a polymer having a polymerizable group and a cage silsesquioxane structure (A) The polymerizable group in the polymer having a polymerizable group and a cage silsesquioxane structure of the present invention The radical polymerizable group or the cationic polymerizable group is not particularly limited. More specifically, cationically polymerizable groups such as epoxy groups, oxetanyl groups, oxazolyl groups, vinyloxy groups, alkenyl groups, alkynyl groups, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, vinyl ethers, vinyl esters, etc. A radical polymerizable group is preferred. Of these, a radical polymerizable group is preferable and an alkenyl group or an alkynyl group is more preferable from the viewpoint that synthesis is easy and the polymerization reaction proceeds favorably.

In addition, as an alkenyl group, the group which has a double bond in the arbitrary positions of an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, and a silicon atom containing group is mentioned, for example. Especially, C2-C12 is preferable and C2-C6 is more preferable. For example, a vinyl group, an allyl group, etc. are mentioned, and a vinyl group is preferable from the viewpoint of ease of polymerization control and mechanical strength.
Examples of the alkynyl group include a group having a triple bond at an arbitrary position of an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, or a silicon atom-containing group. Especially, C2-C12 is preferable and C2-C6 is more preferable. From the viewpoint of ease of polymerization controllability, an ethynyl group is preferred.

A silsesquioxane structure is a structure in which each silicon atom is bonded to three oxygen atoms, and each oxygen atom is bonded to two silicon atoms (RSiO _1.5 , the number of oxygen atoms relative to the number of silicon atoms is 1.5, R represents an organic group. More _{specifically,} a _{structure RSiO 1.5} units are sharing the oxygen atoms in another _{RSiO 1.5} units connected to other units. The cage silsesquioxane structure of the polymer (A) of the present invention is a cage structure of the aforementioned silsesquioxane structure. The cage structure is a structure in which the volume is determined by a plurality of rings formed of covalently bonded atoms, and a point located in the volume cannot be separated from the volume without passing through the ring.

  The compound that is a raw material of the polymer having a polymerizable group and a cage silsesquioxane structure has a cage silsesquioxane structure and a polymerizable group so that the polymerizable group remains after the polymerization reaction. If it is a compound (i), it will not specifically limit. When the compound having a polymerizable group so that the polymerizable group remains after the polymerization reaction is a compound (ii) having no cage silsesquioxane structure, the polymerizable group and the cage silsesquioxane The compound (iii) having a structure is used as a raw material for polymerization. Here, the polymerizable group that the compound (iii) has may or may not remain after polymerization. In addition to the above-mentioned compounds (i) to (iii), the compound (iv) having a polymerizable group can be used as a raw material as long as the effects of the present invention are not impaired. In addition, the polymeric group which compound (iv) has does not remain after superposition | polymerization.

  From the composition, the compound that is a raw material of the polymer having a polymerizable group and a cage silsesquioxane structure, contained in the photosensitive composition of the present invention, is a silsesquioxane described below. From the viewpoint of low dielectric constant, Young's modulus, resolution, and heat resistance of the obtained film.

Silsesquioxane <Cage-like silsesquioxane compound>
Silsesquioxane is a compound having the aforementioned silsesquioxane structure. The cage structure refers to the structure described above.
Since the silsesquioxane of the present invention is composed of one or more cage silsesquioxane compounds represented by the following formula (1), a film using the polymer has a lower refractive index. And a low refractive index property, heat resistance, moisture resistance and the like. In addition, when using multiple types (two or more) of cage silsesquioxane compounds, two compounds having the same cage shape may be used, or one compound having a different cage shape may be used. May be.
(RSiO _1.5 ) _a formula (1)

In formula (1), R represents an organic group each independently, and at least two of R represent a polymerizable group. A plurality of R may be the same or different.
However, a polymerizable group derived from the cage silsesquioxane compound remains in the polymer.
In formula (1), a represents an integer of 8 to 16. a is more preferably an integer of 8, 10, 12, 14 or 16. It is preferable that a is 8, 10, and 12 from the point which the film | membrane obtained has the more excellent low refractive index property and heat resistance, and 8 is more preferable from a viewpoint of superposition | polymerization controllability.

  As a suitable aspect of the said cage silsesquioxane compound, the compound represented by the following general formula (Q-1)-general formula (Q-7) is mentioned. Among these, from the viewpoints of availability, polymerization controllability, and solubility, the compound represented by General Formula (Q-6) is most preferable.

(In General Formula (Q-1) to General Formula (Q-7), each R independently represents an organic group. In each of General Formula (Q-1) to General Formula (Q-7), R represents At least two of them represent polymerizable groups.)

Examples of the organic group for R include a polymerizable group and a non-polymerizable group.
The polymerizable group is not particularly limited, and examples thereof include the same as the polymerizable group in the polymer having the above-described (A) polymerizable group and a cage silsesquioxane structure, and the preferred range thereof is also the same. .

  The non-polymerizable group refers to a group that does not have the above-described polymerizability, and specifically includes an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a silicon atom-containing group, or a combination thereof. Group and the like. Among these, an alkyl group or a cycloalkyl group is preferable from the viewpoint that the photosensitive film exhibits excellent developability and the obtained pattern film exhibits excellent low refractive index and heat resistance.

The alkyl group may have a substituent, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. The alkyl chain may have an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n Examples include linear alkyl groups such as -octadecyl group, branched alkyl groups such as isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group.
In addition, as one of the preferable aspects of an alkyl group, the alkyl group which has a fluorine atom (fluorinated alkyl group) is preferable from the point that the film | membrane obtained has a lower refractive index property. Examples of the fluorinated alkyl group include those in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. Specific examples include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group.

  The cycloalkyl group may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, may be polycyclic, and may have an oxygen atom in the ring. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

  The aryl group may have a substituent and is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

  The aralkyl group may have a substituent and is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

  As an alkoxy group, it may have a substituent, Preferably it is a C1-C20 alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, n-butoxy group, pentyloxy group, hexyloxy Group, heptyloxy group and the like.

The silicon atom-containing group is not particularly limited as long as silicon is contained, but a group represented by the general formula (2) is preferable.
* -L ¹ -Si- (R ²⁰ ) ₃ (2)
In general formula (2), * represents a bonding position with a silicon atom. L ¹ represents an alkylene group, —O—, —S—, —Si (R ²¹ ) (R ²² ) —, —N (R ²³ ) —, or a divalent linking group obtained by combining these. L ¹ is preferably an alkylene group, —O—, or a divalent linking group obtained by combining these.
As an alkylene group, C1-C12 is preferable and C1-C6 is more preferable. R ²¹ , R ²² , R ²³ and R ²⁰ each independently represents an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group. The definitions of the alkyl group, cycloalkyl group, aryl group and alkoxy group represented by R ²¹ , R ²² , R ²³ and R ²⁰ are the same as those defined above, preferably a methyl group, an ethyl group, a butyl group, Examples include a cyclohexyl group.
As the silicon atom-containing group, a silyloxy group (trimethylsilyloxy, triethylsilyloxy, t-butyldimethylsilyloxy) is preferable.

The cage silsesquioxane compound represented by the formula (1) is preferably represented by the following average composition formula (3).
(R ¹ SiO _1.5 ) _x (R ² SiO _1.5 ) _y formula (3)
(In formula (1), R ¹ represents a polymerizable group. R ² represents a non-polymerizable group. Here, the polymerizable group and the non-polymerizable group have the same meanings as above. X is 2.0. Represents a number of ˜14.0 (2.0 ≦ x ≦ 14.0), and y represents a number of 0 to 14.0 (0 ≦ y ≦ 14.0), where x + y = 8 to 16 is satisfied The plurality of R ¹ and R ² may be the same or different.

In formula (3), x represents a number of 2.0 to 14.0, and x is 2. from the point that the obtained film exhibits more excellent low refractive index property, heat resistance, light resistance, and curability. 5 or more is preferable and 3.0 or more is more preferable.
In the formula (3), y represents a number of 0 to 14.0, and y is preferably 0 to 12.0 from the viewpoint that the obtained film exhibits more excellent low refractive index properties, heat resistance and coating properties. 0-10.0 are still more preferable, 0-7.5 are more preferable, and 0-5.0 are the most preferable.

In the formula (3), x + y = 8 to 16 is satisfied, and x + y = 8 to 14 is preferable from the viewpoint that the resulting film exhibits more excellent low refractive index, heat resistance, hygroscopicity, and storage stability, and x + y = 8-12 are more preferable and x + y = 8-10 is still more preferable.
Furthermore, in the formula (3), the ratio of x (x / x + y) preferably satisfies 0.1 ≦ (x / x + y) ≦ 1.0, and the resulting film has a better low refractive index property and heat resistance. In view of mechanical strength, 0.2 ≦ (x / x + y) ≦ 1.0 is more preferable, and 0.3 ≦ x / y ≦ 1.0 is still more preferable.

<Preferred embodiment of silsesquioxane>
As a preferred embodiment of the silsesquioxanes, x is in the range of 2.0 ≦ x ≦ 8.0 in the formula (3) from the viewpoint that the obtained film exhibits more excellent low refractive index and heat resistance. (Preferably 3.0 ≦ x ≦ 8.0), y represents a number in the range of 0 ≦ y ≦ 6.0 (preferably 0 ≦ y ≦ 5.0), and x + y = 8 And silsesquioxanes composed of a cage silsesquioxane compound represented by the general formula (Q-6).
The silsesquioxanes are composed of one or more cage silsesquioxane compounds (T8 type) represented by the general formula (Q-6). For example, a mixture of a cage silsesquioxane compound having 8 polymerizable groups and a cage silsesquioxane compound having 4 polymerizable groups and 4 non-polymerizable groups may be used.

In another preferred embodiment of the silsesquioxane, in formula (3), x represents a number in the range of 2.0 ≦ x ≦ 10.0 (preferably 3.0 ≦ x ≦ 10.0), and y is A cage-shaped silsesquioxane compound represented by a number in the range of 0 ≦ y ≦ 8.0 (preferably 0 ≦ y ≦ 7.0), x + y = 10 and represented by the above general formula (Q-2) And / or silsesquioxanes composed of a cage silsesquioxane compound represented by formula (Q-7).
The silsesquioxanes are composed of one or more kinds of cage silsesquioxane compounds (T10 type) represented by the above general formula (Q-2) or general formula (Q-7). The

In another preferred embodiment of the silsesquioxane, in formula (3), x represents a number in the range of 2.0 ≦ x ≦ 12.0 (preferably 3.0 ≦ x ≦ 12.0), and y is A cage-shaped silsesquioxane compound represented by a number in the range of 0 ≦ y ≦ 10.0 (preferably 0 ≦ y ≦ 9.0), x + y = 12, and represented by the above general formula (Q-1) And / or silsesquioxanes composed of a cage silsesquioxane compound represented by the general formula (Q-3).
The silsesquioxanes are composed of one or more kinds of cage silsesquioxane compounds (T12 type) represented by the above general formula (Q-1) or general formula (Q-3). The

In another preferred embodiment of the silsesquioxane, in formula (3), x represents a number in the range of 2.0 ≦ x ≦ 14.0, and y represents a number in the range of 0 ≦ y ≦ 12.0. X + y = 14, and silsesquioxanes composed of a cage silsesquioxane compound represented by the general formula (Q-4).
The silsesquioxanes are composed of one or more cage silsesquioxane compounds (T14 type) represented by the above general formula (Q-4).

As another preferred embodiment of the silsesquioxane, a cage silsesquioxane compound having at least three polymerizable groups and at least three non-polymerizable groups (hereinafter also referred to as compound (A)). And silsesquioxanes. That is, the compound (A) is a compound in which at least three of R in the formula (3) represent a polymerizable group, and at least three of R represent a non-polymerizable group. By containing the compound (A), a patterned film having a lower refractive index and excellent heat resistance can be obtained.
In this form, the cage silsesquioxane compound (A) may have three or more polymerizable groups and three or more non-polymerizable groups.
Although the structure of a compound (A) is not specifically limited, It is preferable that it is a compound represented by the general formula (Q-1)-general formula (Q-7) mentioned above.
For example, in the compound represented by the general formula (Q-6), a compound having 3 to 5 polymerizable groups and 3 to 5 non-polymerizable groups and the total number of both being 8 is compound (A). It corresponds to.
Moreover, in the compound represented by general formula (Q-2) or general formula (Q-7), it has 3-7 polymeric groups and 3-7 nonpolymerizable groups, and the total of both is The compound which is 10 corresponds to the compound (A).
In addition, in the compound represented by the general formula (Q-4), a compound having 3 to 11 polymerizable groups and 3 to 11 non-polymerizable groups, and the total number of both is 14 (A )

  The content of the above-mentioned compound (A) in all silsesquioxanes is not particularly limited, but is 10 mol% or more based on the total amount of silsesquioxanes from the viewpoint of more excellent characteristics of the resulting film. It is preferable that it is 20-100 mol%, and it is still more preferable that it is 60-100 mol% or more. In particular, it is preferable that the silsesquioxane is composed only of the compound (A) and does not substantially contain other cage silsesquioxane compounds.

  The silsesquioxanes described above are usually composed of a cage silsesquioxane compound, but other polysiloxane compounds (ladder-type silsesquioxane compounds, etc.) as long as the effects of the present invention are not impaired. ) May be included.

  Although the specific example of silsesquioxane is shown below, this invention is not limited to these. In addition, the substituent ratio in Table 1 corresponds to x / y in Formula (3).

  The cage silsesquioxane compound used in the present invention may be one that can be purchased from Aldrich, Hybrid Plastics, Polymers, 20, 67-85, 2008, Journal of Inorganic and Organometallic Polymers, 11 (3), 123-154, 2001, Journal of Organometallic Chemistry, 542, 141-183, 1997, Journal of Macromolecular Science A. Chemistry, 44 (7), 659-664, 2007, Chem. Rev., 95, 1409 -1430, 1995, Journal of Inorganic and Organometallic Polymers, 11 (3), 155-164, 2001, Dalton Transactions, 36-39, 2008, Macromolecules, 37 (23), 8517-8522, 2004, Chem. Mater., 8, 1250-1259, 1996 or the like.

[2] (A) Polymer having a polymerizable group and a cage silsesquioxane structure (A) The polymer having a polymerizable group and a cage silsesquioxane structure includes the aforementioned polymerizable group and cage shape. There is no particular limitation as long as it has a silsesquioxane structure.
(A) As a polymer having a polymerizable group and a cage silsesquioxane structure, a silyl compound composed of one or more cage silsesquioxane compounds represented by the above formula (1) is used. A polymer obtained from sesquioxanes is preferable from the viewpoint of low dielectric constant, Young's modulus, resolution, and heat resistance of a film obtained from the composition. Here, a polymerizable group derived from a cage silsesquioxane compound remains in the polymer.

Silsesquioxane Polymers Hereinafter, physical properties of polymers obtained using the above-mentioned silsesquioxanes as raw materials and the production method thereof will be described in detail.

The weight average molecular weight (M _w ) of the polymer is not particularly limited, but is preferably 1.0 × 10 ⁴ to 50 × 10 ⁴ , and more preferably 3.5 × 10 ⁴ to 40 × 10 ^4. 5.0 × 10 ^{4 to} 35 × 10 ⁴ is most preferable.
The number average molecular weight (M _n ) of the polymer is not particularly limited, but is preferably 1.5 × 10 ^{4 to} 35 × 10 ⁴ , and more preferably 1.5 × 10 ^{4 to} 20 × 10 ^4. 2.5 × 10 ⁴ to 15 × 10 ⁴ is most preferable.
The Z + 1 average molecular weight (M _{Z + 1} ) of the polymer is not particularly limited, but is preferably 1.5 × 10 ^{4 to} 65 × 10 ⁴ , and more preferably 2.5 × 10 ⁴ to 50 × 10 ^4. 3.5 × 10 ^{4 to} 35 × 10 ⁴ is most preferable.
By setting the weight average molecular weight and number average molecular weight within the above ranges, the solubility in organic solvents and filter filterability are improved, the generation of particles during storage can be suppressed, and the surface state of the coating film is improved. A film having a refractive index can be formed.

  From the viewpoint of solubility in organic solvents, filter filterability, and coating film surface, the polymer preferably does not substantially contain a component having a molecular weight of 3 million or more, and substantially does not contain a component having a molecular weight of 2 million or more. Is more preferable, and it is most preferable not to include one million or more components.

In the polymer, an unreacted polymerizable group derived from the cage silsesquioxane compound remains.
Of the polymerizable group derived from the cage silsesquioxane compound, 10 to 90 mol% is preferably left unreacted, and 20 to 90 mol% is preferably left unreacted, and 30 Most preferably, ˜90 mol% remains unreacted. If it is in the said range, while the developability of the film | membrane formed from the photosensitive composition of this invention will be fully obtained, the heat resistance of the pattern film obtained, sclerosis | hardenability, and mechanical strength will improve more.
About these, it can quantify from a < ¹ > H-NMR spectrum.

The above-described polymer is a polymer mainly composed of silsesquioxanes composed of one or more cage-shaped silsesquioxane compounds represented by the above formula (1). In the polymer, the content of the polymerizable group is not particularly limited, but is preferably 5 in all organic groups bonded to the silicon atom (that is, with respect to all the groups corresponding to R in the above formula (1)). It is -90 mol%, More preferably, it is 10-90 mol%, More preferably, it is 10-80 mol%. If it is in the said range, while the developability of the film | membrane formed from the photosensitive composition of this invention will fully be obtained, the heat resistance of the pattern film obtained and mechanical strength will improve more. These can also be quantified from a ¹ H-NMR spectrum or the like.

  In addition, it is preferable that 10-100 mass% of structures derived from a cage silsesquioxane compound are contained in the polymer, and it is more preferable that 20-100 mass% is contained. If it is in the said range, the heat resistance of the film obtained, low refractive index property, and transparency will improve more.

Moreover, it is preferable that a polymer does not have an aromatic group substantially, and this can express the outstanding low refractive index more reliably. Specifically, for all organic groups bonded to the silicon atom of the polymer (that is, for all of the groups corresponding to R in formula (1) above), the aromatic group content is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol% (that is, the polymer has no aromatic group).
A polymer may be used individually by 1 type, or may use 2 or more types together.

<Method for Producing Silsesquioxane Polymers>
The method for producing the polymer is not particularly limited as long as the polymerizable group derived from the cage silsesquioxane compound remains in the obtained polymer. For example, the polymerization reaction of the polymerizable group, the hydrolysis A relation reaction is mentioned.
The polymerization reaction of the polymerizable group may be any polymerization reaction, and examples thereof include radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polycondensation, polyaddition, addition condensation, and transition metal catalyst polymerization.

  The hydrosilylation reaction includes, for example, the above-described cage silsesquioxane compound and a compound containing two or more SiH groups in the molecule (for example, bis (dimethylsilyl) ethane, 1,1,3, 3-tetramethyldisiloxane, etc.) are dissolved in an organic solvent (eg, toluene, xylene, etc.) and a catalyst (eg, Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) is dissolved. And heating at 20 to 200 ° C. can be performed.

  As a method for producing the polymer, a polymerization reaction via a polymerizable group is preferable, and radical polymerization is most preferable. As a synthesis method, the above-described silsesquioxane and initiator are dissolved in a solvent and batch polymerization is performed by heating, the silsesquioxane is dissolved in a solvent and heated, and a solution of the initiator is 1 Examples thereof include a dropping polymerization method (continuous addition) that is dropped over 10 hours and a divided addition polymerization method (split addition) in which an initiator is divided into a plurality of times. Split addition and continuous addition are preferred in that the film strength and molecular weight reproducibility are further improved.

The reaction temperature of the polymerization reaction is usually 0 ° C to 200 ° C, preferably 40 ° C to 170 ° C, more preferably 80 ° C to 160 ° C.
Moreover, in order to suppress the inactivation of the polymerization initiator by an acid, it is preferable to make it react under inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.

  The concentration of silsesquioxane in the reaction solution during polymerization is preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 15% by mass or less, based on the total mass of the reaction solution. More preferably, it is most preferably 10% by mass or less. By setting the concentration range, the generation of impurities such as gelling components can be suppressed.

Any solvent can be used in the polymerization reaction as long as the silsesquioxane can be dissolved at a necessary concentration and does not adversely affect the properties of the film formed from the resulting polymer. May be used. In the following description, for example, an ester solvent is a solvent having an ester group in the molecule.
As the solvent, for example, the solvent described in paragraph [0038] of JP-A-2008-218639 can be used.
Among these, more preferred solvents are ester solvents, ether solvents and aromatic hydrocarbon solvents, and specifically include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, hexyl acetate, propion. Preferred are methyl acid, propylene glycol monomethyl ether acetate (PGMEA: alias 1-methoxy-2-acetoxypropane), tetrahydrofuran, diphenyl ether, chlorobenzene, dichlorobenzene, anisole, toluene, xylene, mesitylene, t-butylbenzene, particularly preferably acetic acid Ethyl, butyl acetate, diphenyl ether, chlorobenzene, dichlorobenzene, anisole, mesitylene, and t-butylbenzene. These may be used alone or in admixture of two or more.
The boiling point of the solvent is preferably 65 ° C. or higher so that the reaction solution can be heated to a temperature necessary for decomposing the polymerization initiator during the reaction.

Among the above solvents, the chain transfer constant (Cx) is 0 <Cx ≦ 5.0 × 10 ^{4 because the} polymerization of the obtained polymer is easy to control and the characteristics of the obtained film are more excellent. It is particularly preferred to use a solvent.
Further, the preferred SP (solvent degree parameter) value of the solvent is 10 to 25 (MPa ^1/2 ), from the viewpoint that the polymerization of the resulting polymer is easy to control and the properties of the resulting film are more excellent. Preferably, 15 to 25 (MPa ^1/2 ) is more preferable. Here, the SP value is, for example, Polymer Handbook Fourth Edition Volume 2 (A John Wiley & Sons, Inc., Publication) J. MoI. BRANDRUP, E.E. H. IMMERGUT and E.I. A. GRULKE (1999) p. It is a value obtained using the method described in 675-714.

The polymerization reaction of silsesquioxanes is preferably performed in the presence of a nonmetallic polymerization initiator. For example, the polymerization can be carried out in the presence of a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating.
As the polymerization initiator, an organic peroxide or an organic azo compound is particularly preferably used. As the organic peroxide and the organic azo compound, compounds described in paragraph numbers [0033] to [0035] of JP-A-2008-239865 can be used.

The polymerization initiator is preferably an organic azo compound from the standpoint of the safety of the reagent itself and the molecular weight reproducibility of the polymerization reaction. Among them, an azo ester compound such as V-601 that does not incorporate harmful cyano into the polymer is preferable.
The 10-hour half-life temperature of the polymerization initiator is preferably 100 ° C. or lower. If the 10-hour half-life temperature is 100 ° C. or lower, it is easy to prevent the polymerization initiator from remaining at the end of the reaction.
Only one polymerization initiator or a mixture of two or more polymerization initiators may be used.
The amount of the polymerization initiator used is preferably 0.0001 to 2 mol, more preferably 0.003 to 1 mol, and particularly preferably 0.001 to 0.5 mol with respect to 1 mol of the silsesquioxane. is there.

By synthesizing the polymer under the conditions as described above, a polymer in which the polymerizable group derived from the cage silsesquioxane compound remains can be suitably obtained.
Moreover, in the polymer obtained, among the polymerizable groups derived from the cage silsesquioxane compound, the content of the unreacted polymerizable group is the reaction temperature or polymerization of the polymerization reaction of the polymerizable group described above. It can be changed by appropriately changing various conditions such as the concentration of silsesquioxane in the reaction solution at the time.

A reaction solution obtained by subjecting a silsesquioxane polymerization reaction may be used as a coating solution as it is, but it is preferable to carry out a purification treatment after the reaction is completed. Purification methods include washing with water and a liquid-liquid extraction method that removes residual monomers and oligomer components by combining with an appropriate solvent, ultrafiltration, centrifugal separation, and column that extract and remove only those with a specific molecular weight or less. A purification method in a solution state such as chromatography, a reprecipitation method in which the polymer is coagulated in the poor solvent by dropping the polymer solution into the poor solvent, and the residual monomer is removed. A usual method such as a purification method in a solid state such as washing the combined slurry with a poor solvent can be applied.
For example, a solvent (poor solvent) in which the polymer is hardly soluble or insoluble is brought into contact with the polymer-containing solution in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution. The coalescence is precipitated as a solid. The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon or halogenated carbonization depending on the type of polymer. It can be appropriately selected from hydrogen, nitro compounds, ethers, ketones, esters, carbonates, alcohols, carboxylic acids, water, mixed solvents containing these solvents, and the like. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.

  In the polymer of silsesquioxane and its production process, a polymerization inhibitor may be added in order to suppress unnecessary polymerization. Examples of the polymerization inhibitor include 4-methoxyphenol, 2,6-bis (1,1-dimethylethyl) -4-methylphenol, catechol and the like.

[3] Photosensitive Composition The photosensitive composition of the present invention is a polymer having a polymerizable group and a cage silsesquioxane structure described above (preferably, one kind represented by the above-described predetermined average composition formula. Or a polymer obtained from silsesquioxanes composed of two or more kinds of silsesquioxane compounds (however, as described above, the polymer has a polymerizable group derived from the cage silsesquioxane compound). Remaining))).
From the viewpoint of curability and storage stability, the photosensitive composition of the present invention is preferably a composition that undergoes a radical polymerization reaction or a cationic polymerization reaction upon exposure.
In addition, the solution which the polymer melt | dissolved in the solvent (for example, organic solvent) may be sufficient as the composition of this invention, and the solid substance containing a polymer may be sufficient as it.
The composition of the present invention can be used for various applications, and the type of polymer content and additives to be added is determined according to the purpose. Applications include, for example, production of films (for example, insulating films), low refractive index films (for example, antireflection films), low refractive index materials, gas adsorption materials, resist materials, etc. An antireflection film is preferred.

  The content of the polymer in the composition is not particularly limited, but when used for film formation described below, it is preferably 50% by mass or more, more preferably 60% by mass with respect to the total solid content. % Or more, and most preferably 70% by mass or more. The maximum value is 98% by mass. The larger these contents in the solid content, the more the coating surface can be formed. In addition, solid content means the solid component which comprises the film | membrane mentioned later, and a solvent etc. are not contained.

The composition of the present invention may contain a solvent. That is, it is preferable to use the polymer by dissolving it in a suitable solvent and coating it on a support.
As a solvent, the solvent which melt | dissolves a polymer 5 mass% or more at 25 degreeC is preferable, and 10 mass% or more is more preferable. Specifically, the solvent described in paragraph No. [0044] of JP-A-2008-214454 can be used.
Among these, preferable solvents include propylene glycol monomethyl ether acetate (PGMEA: alias 1-methoxy-2-acetoxypropane), propylene glycol monomethyl ether (PGME: alias 1-methoxy-2-propanol), 2-heptanone, cyclohexanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene carbonate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, Ethyl ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, tetrahydrophenol Emissions, methyl isobutyl ketone, xylene, mesitylene, diisopropylbenzene.

  When the composition contains a solvent, the total solid content concentration in the composition is preferably 1 to 30% by mass with respect to the total amount of the composition, and is appropriately adjusted according to the purpose of use. If it is in the said range, the film thickness of a coating film will become an appropriate range, and the storage stability of a coating liquid will also become more excellent.

  In the composition, it is preferable that the metal content as an impurity is sufficiently low. The metal concentration in the composition can be measured with high sensitivity by the ICP-MS method or the like, and the metal content other than the transition metal in that case is preferably 300 ppm or less, more preferably 100 ppm or less.

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

[3-1] Compound having SiH bond The photosensitive composition of the present invention contains (B) a compound having SiH bond (hereinafter, also simply referred to as “compound (B)”).
The compound having a SiH bond is a compound having at least one silicon-hydrogen bond (SiH bond) in the compound, and is not particularly limited as long as it is a compound having at least one SiH bond.
Although the detailed mechanism is not clear, in the photosensitive composition of the present invention, active species such as active radicals generated by (C) the photopolymerization initiator described later act on the compound (B) having a SiH bond. Thus, it is considered that the chemically active SiH bond is activated, the SiH bond is cleaved, and the active species moves to the compound having the SiH bond. In the photosensitive composition of the present invention, the compound having a SiH bond is not inhibited by an inhibiting species such as oxygen, and efficiently transmits the active species to the remaining polymerizable group of the polymer (A). It is estimated that the polymerization reaction of the remaining polymerizable group of the polymer (A) is promoted compared to the photosensitive composition not containing a compound having SiH bond. Further, a compound having one SiH bond is incorporated at the end of polymerization by the residual polymerizable group of the (A) polymer, and a compound having two or more SiH bonds is determined by the residual polymerizable group of the (A) polymer. It is presumed to function as a crosslinking agent in the polymerization.
As described above, (B) the compound having a SiH bond efficiently transmits active species such as active radicals present in the photosensitive composition of the present invention to the remaining polymerizable group of the (A) polymer. By using a compound having a silicon atom that fulfills its function and is excellent in low dielectric constant and heat resistance, the Young's modulus and resolution are improved while maintaining the low dielectric constant and heat resistance of the resulting pattern. Is estimated to be possible.

The compound having a SiH bond is preferably a compound represented by the following general formula (B-1).
HSiR _B ¹ R _B ² R _B ³ (B-1)
In General Formula (B-1), R _B ¹ , R _B ^2, and R _B ³ each independently represent a hydrogen atom or a substituent. At least two of R _B ¹ , R _B ² , and R _B ³ may be bonded to each other to form a ring. When R _B ^{1 to} R _B ³ represent a substituent, the substituent represented by R _B ^{1 to} R _B ³ may have a SiH bond.

Specific examples of the substituent represented by R _B ¹ , R _B ² and R _B ³ include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an amino group, a halogen atom, and a silicon atom. Group, the group which combined them, etc. are mentioned.

The alkyl group may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl chain may have an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n Examples include linear alkyl groups such as -octadecyl group, branched alkyl groups such as isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group.
In addition, as one of the preferable aspects of an alkyl group, the alkyl group which has a fluorine atom (fluorinated alkyl group) is preferable from the point that the film | membrane obtained has a lower refractive index property. Examples of the fluorinated alkyl group include those in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. Specific examples include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and a nonafluorohexyl group.

  The cycloalkyl group may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms (more preferably 3 to 10 carbon atoms), may be polycyclic, and has an oxygen atom in the ring. You may have. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

  The aryl group may have a substituent and is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

  The aralkyl group may have a substituent and is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

As an alkoxy group, it may have a substituent, Preferably it is a C1-C20 alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, n-butoxy group, pentyloxy group, hexyloxy Group, heptyloxy group and the like.
The amino group may have a substituent and is preferably an amino group having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms), such as an unsubstituted amino group, a methylamino group, or dimethyl. Amino group, ethylamino group, diethylamino group, n-butyl group amino group, isobutylamino group, t-butylamino group, di-n-butylamino group, diisobutylamino group, di-t-butylamino group, dibenzylamino Group, diphenylamino group, ditolylamino group, methyl (trimethylsilyl) amino group, dimethylsilylamino group and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.

The silicon atom-containing group is not particularly limited as long as it contains a silicon atom, but a group represented by the general formula (B-2) is preferable, and the shape may be a chain, a ring, or a cage, as long as it is a group. is not.
_{^{* -L B 1 -Si- (R B}} 20) 3 (B-2)
In general formula (B-2), * represents a bonding position with a silicon atom. L _B ¹ is a single bond, an alkylene group, —O—, —S—, —Si (R _B ²¹ ) (R _B ²² ) —, —N (R _B ²³ ) —, or a divalent linkage in which these are combined. Represents a group. L _B ¹ is preferably an alkylene group, —O—, or a divalent linking group obtained by combining these. As an alkylene group, C1-C12 is preferable and C1-C6 is more preferable.
R _B ²¹ , R _B ²² , R _B ²³ and R _B ²⁰ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, or a silicon atom-containing group. The definitions of the alkyl group, cycloalkyl group, aryl group, alkoxy group, and silicon atom-containing group represented by R _B ²¹ , R _B ²² , R _B ²³ and R _B ²⁰ are as described above for R _B ¹ , R _B ² , And the same definition as the alkyl group, cycloalkyl group, aryl group, alkoxy group and silicon atom-containing group represented by R _B ³ , preferably methyl group, ethyl group, butyl group, phenyl group and the like.
As the silicon atom-containing group, a silyloxy group (dimethylsilyloxy group, trimethylsilyloxy group, triethylsilyloxy group, t-butyldimethylsilyloxy group, diphenylsilyloxy group) is preferable.

The substituent represented by R _B ¹ , R _B ² and R _B ³ may be a group formed by combining at least two selected from the group consisting of the aforementioned groups, and may be an alkyl group, an amino group, and A group formed by combining at least two selected from the group consisting of silicon atom-containing groups is preferred. The total number of carbon atoms in the group formed by combining at least two of these is preferably 0-20, more preferably 0-10.

From the viewpoint of suppressing volatilization, at least one of R _B ¹ , R _B ² and R _B ³ preferably represents a substituent, and at least two preferably represent a substituent, and R _B ¹ , R More preferably, _B ² and R _B ³ each independently represent a substituent. The substituent represented by R _B ¹ , R _B ² and R _B ³ preferably represents an alkyl group, an aryl group, an amino group, a halogen atom, a silicon atom-containing group, or a combination thereof, It is more preferable to represent a group, an aryl group, a silicon atom-containing group, or a group obtained by combining them.
Among them, as the substituent represented by R _B ¹ , R _B ² and R _B ³ , from the point that it does not volatilize by baking, and the obtained pattern film exhibits excellent low dielectric constant and heat resistance, A silicon atom-containing group is preferred, and a polymer containing a silicon atom-containing group is more preferred. The shape of the polymer containing a silicon atom-containing group is not limited even if it is a chain, a ring, or a cage.

At least two of R _B ¹ , R _B ² , and R _B ³ may be bonded to each other to form a ring, and the formed ring may be monocyclic or polycyclic. The ring formed is preferably a 3-30 membered ring, more preferably a 6-20 membered ring. From the viewpoint of low dielectric constant and heat resistance, the formed ring preferably includes at least one siloxane bond (Si—O—Si), and more preferably a ring composed of only a siloxane bond. Further, when all ^three of R _B ¹ , R _B ² , and R _B ³ are bonded to each other to form a ring, it is represented by the general formula (Q-1) to the general formula (Q-7). It is preferable to form a cage silsesquioxane structure such as

  Furthermore, the compound having an SiH bond is preferably a compound having at least one siloxane bond (Si—O—Si) from the viewpoint of low dielectric constant and heat resistance. Compounds having at least one of the partial structures represented by B-3) to (B-5) are preferred.

In the general formulas (B-3) to (B-5), * represents a bonding position with a silicon atom. R _B and _{R B} 'are each synonymous with _R ^B 1 _{to R} ^{B 3} in the general formula (B-1), is the same specific examples and preferred ranges.

  The compound having at least one of the partial structures represented by the general formulas (B-3) to (B-5) is preferably a polymer from the viewpoint of resolution and coatability. There is no restriction | limiting in particular as a form, For example, a well-known linear polymer, cage-type polysiloxane, ladder-type polysiloxane etc. can be mentioned. In particular, a resin containing a silicon atom in the main chain of the resin is preferable from the viewpoint of further lowering the dielectric constant and increasing heat resistance. Examples of the resin that is a linear polymer include linear polysiloxane, linear polycarbosilane, and the like. Among these, linear polysiloxane is more preferable from the viewpoint of raw material availability. . The linear polysiloxane preferably contains a repeating unit represented by the following general formula (B-6) from the viewpoint of low dielectric constant and Young's modulus.

In the general formula (B-6), R _B ″ represents a substituent.
Specific examples and preferred ranges of the substituent represented by R _B ″ are the same as R _B ^{1 to} R _B ^{3 in the} general formula (B-1), but from the viewpoint of low dielectric constant, R Most preferably, _B ″ is an alkyl group.
By using a polymer containing a large amount of SiH bonds as in the general formula (B-6), it is considered that the curing reaction of the film is promoted and contributes to a decrease in dielectric constant and an increase in Young's modulus.

  In the linear polysiloxane, the content of the repeating unit represented by the general formula (B-6) is preferably 5 to 100 mol% with respect to all the repeating units of the linear polysiloxane. More preferably, it is 10-80 mol%, and it is still more preferable that it is 10-60 mol%.

  The linear polysiloxane may further contain a repeating unit represented by the following general formula (B-7).

In the general formula (B-7), R _B ′ ″ and R _B ″ ″ each independently represent a substituent.
Specific examples and preferred range of the substituent of R B _'' 'and R _B''''is similar to R _B ¹ ~R _B ³ in the general formula (B-1), low in terms of permittivity properties, it is most preferred substituents represented by R B _'' 'and R _B''''is an alkyl group.

  The linear polysiloxane may or may not contain the repeating unit represented by the general formula (B-7), but when it is contained, the repeating unit represented by the general formula (B-7). The content of the unit is preferably 0.1 to 95 mol%, more preferably 20 to 90 mol%, more preferably 40 to 90 mol%, based on all repeating units of the linear polysiloxane. More preferably it is.

  The terminal of the polymer may be modified with dimethylsiloxane or trimethylsiloxane.

When the compound (B) having a SiH bond of the present invention is a polymer, the number average molecular weight ( _Mn ) in terms of polystyrene by gel permeation chromatography (GPC) method of the polymer may be 500 to 100,000. Preferably, 800 to 50,000 is more preferable. When the number average molecular weight is within the above numerical range, the polymer as the compound (B) of the present invention has good solubility and can be cured without being dissipated during heating. The degree of dispersion of the polymer is preferably in the range of 1-3.

  Specific examples of the compound (B) having a SiH bond of the present invention are shown below, but the present invention is not limited to these specific examples.

  As the compound (B) having a SiH bond of the present invention, various commercially available products can be used. It can also be synthesized by a sol-gel reaction or a coupling reaction.

(B) The compound which has a SiH bond may be used individually by 1 type, or may use 2 or more types together.
Although content in particular with respect to the photosensitive composition of this invention of the above-mentioned compound (B) is not restrict | limited, it is 20 with respect to the total solid in a photosensitive composition from the point which the various characteristics of the film | membrane obtained are more excellent. It is preferable that it is mass% or less, it is more preferable that it is 0.5-20 mass%, and it is still more preferable that it is 0.5-10 mass%.

[3-2] Photopolymerization initiator The photosensitive composition of the present invention contains (C) a photopolymerization initiator.
(C) The photosensitive composition of the present invention to which photosensitivity is imparted by containing a photopolymerization initiator can be suitably used for a photoresist, a color resist, an optical coating material, and the like. As the photopolymerization initiator, those known as photopolymerization initiators described below can be used.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the remaining polymerizable group of the polymer (A), and can be appropriately selected from known photopolymerization initiators. Those having photosensitivity to visible light from the ultraviolet region are preferable, and may be an activator that generates an active radical by generating an action with a photoexcited sensitizer. It may be an initiator that initiates polymerization.
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).

  The photopolymerization initiator is preferably a radical photopolymerization initiator from the viewpoints of curability and storage stability. In addition, since there is no limitation on applicable devices, a low dielectric constant film can be formed, and curability is good, the photopolymerization initiator is a nonmetallic photopolymerization initiator. It is also preferable. A nonmetallic photopolymerization initiator is a photopolymerization initiator that does not contain a metal. Examples of the metallic catalyst include titanium methacryl triisopropoxy, which catalyzes a sol-gel reaction, and such a metallic catalyst does not correspond to a nonmetallic photopolymerization 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 No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, 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, and the oxime initiator described above, As the oxime initiator, 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 BASF Japan Ltd.) can be used. Further, as the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF Japan Ltd.) can be used.

  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).
Further, as commercially available α-hydroxyacetophenone compounds, Irgacure 184 (IRGACURE 184), Darocur 1173 (DAROCURE 1173), Irgacure 127 (IRGACURE 127), Irgacure 2959 (IRGACURE 2959), Irgacure 1800 (IRGAC URE), manufactured by BASF Japan Polymerization initiators available under the trade names 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 BASF Japan Ltd.) can be used. A phosphine initiator described in JP-A-2009-134098 can also be applied.

The photopolymerization initiator in the present invention is most preferably an oxime compound such as an oxime derivative from the viewpoints of sensitivity and curing rate. The oxime compound can suppress the deactivation of active species due to recombination of radicals, and the film curing reaction proceeds smoothly. Therefore, the oxime compound is excellent in sensitivity and efficiently polymerizes the remaining polymerizable group of the polymer (A). The reaction can proceed. That is, under the conditions of the same exposure amount, when using an oxime compound, it is considered that the polymerization reaction can proceed better than when using other photopolymerization initiators. When the films obtained under the above conditions are compared, it is presumed that the oxime compound is excellent in low dielectric constant, Young's modulus and resolution. The oxime compound is not particularly limited. For example, JP 2000-80068 (paragraphs 0004-0296), WO 02/100903 A1, JP 2001-233842, JP 2006-342166 (paragraph 0004). ~ 0264) and the like.
Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) Such as 9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  Of these, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-, from the viewpoints of exposure dose, pattern shape, development residue, stability over time, and coloring during post-heating. Oxime-O-acyl compounds such as octanedione and 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone are particularly preferred, Specifically, CGI-124, CGI-242, IRGACURE OXE-01 (manufactured by BASF Japan Ltd.) and the like are preferable.

The photoinitiator in this invention may be used individually by 1 type, or may use 2 or more types together.
The content of the photopolymerization initiator in the solid content of the composition of the present invention is usually 1% by mass to 40% by mass, preferably 2% by mass to 30% by mass, and preferably 2% by mass to 15% by mass. % Is more preferable.

[3-3] Polymerizable compound The composition of the present invention may further contain a polymerizable compound different from the polymer (A).
When the composition of the present invention contains a polymerizable compound, the solvent resistance, dimensional uniformity, Young's modulus, resolution, heat resistance and hardness of the pattern film tend to be further improved.
The polymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more.
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 (ie, dimers, trimers, and oligomers), or mixtures or copolymers thereof. Examples of monomers and copolymers thereof include, for example, unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters or amides thereof. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group, or a mercapto group and a monofunctional or polyfunctional isocyanate or epoxy, and a hydroxy group, A dehydration condensation reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as an amino group or a mercapto group and a monofunctional or polyfunctional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and a monofunctional or polyfunctional alcohol, amine, or thiol is also suitable. Furthermore, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a halogen group or 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 group 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 ester, methacrylic acid ester, itaconic acid ester, and the like.
Examples of acrylic esters include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, and trimethylolpropane triacrylate. , Trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol diacryl Over DOO, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomers, and isocyanuric acid EO-modified triacrylate.

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

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. 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, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Furthermore, monomers containing acid groups can also be used, such as (meth) acrylic acid, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipenta Erythritol pentaacrylate maleic acid monoester, pentaerythritol triacrylate phthalic acid monoester, dipentaerythritol pentaacrylate phthalic acid monoester, pentaerythritol triacrylate tetrahydrophthalic acid monoester, dipentaerythritol pentaacrylate tetrahydrophthalic acid monoester It is done. In particular, pentaerythritol triacrylate succinic acid monoester is preferable from the viewpoint of developability and sensitivity.

  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-54-21726.

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

Formula ^{_{CH 2 = C (R 10)}} COOCH 2 CH (R 11) OH
(However, R ¹⁰ and R ¹¹ represent H or CH _3. )

  Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 Can obtain a photopolymerizable composition having an excellent photosensitive speed.

  Other examples include reacting polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. And polyfunctional acrylates and methacrylates such as epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. be able to. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of a 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 image portion, that is, the pattern film, those having three or more functionalities are preferable. Further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, the compound containing a carboxylic acid group or EO modified body structure is preferable from a viewpoint of curing sensitivity and developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  In addition, the compatibility and dispersibility with other components in the composition (for example, resin, photopolymerization initiator, pigment), the selection and use method of the polymerizable compound is an important factor. 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 the adhesion with a substrate or the like.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate modified EO, dipentaerythritol hexaacrylate EO modified, pentaerythritol triacrylate succinic acid monoester and the like are preferred, and commercially available products include urethane oligomer UAS-10. , UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) is preferable.

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Pentaerythritol hexaacrylate EO modified product, pentaerythritol triacrylate succinic acid monoester, etc. are commercially available products such as DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600. T-600 and AI-600 (manufactured by Kyoeisha) are more preferred.

  A polymeric compound may be used individually by 1 type, and may use 2 or more types together.

  The composition of the present invention may or may not contain a polymerizable compound, but when it is contained, the content of the polymerizable compound in the solid content of the composition is 1% by mass to 90% by mass. Preferably, it is 5 mass%-80 mass%, More preferably, it is 5 mass%-70 mass%.

[3-4] Alkali-soluble resin The composition of the present invention may further contain an alkali-soluble resin. By containing an alkali-soluble resin, it becomes possible to impart alkali developability.

  The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions are determined. It can also be done.
Moreover, in order to improve the crosslinking efficiency of the composition in the present invention, an alkali-soluble resin having a polymerizable group may be used.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

  The composition of the present invention may or may not contain an alkali-soluble resin, but when it is contained, the content of the alkali-soluble resin in the composition is 1 with respect to the total solid content of the composition. -15 mass% is preferable, More preferably, it is 2-12 mass%, Most preferably, it is 3-10 mass%. Thereby, water repelling property and development defect performance are improved.

[3-5] Additive Further, the composition includes a radical generator as long as the characteristics (heat resistance, dielectric constant, mechanical strength, coatability, adhesion, etc.) of the film obtained using the composition are not impaired. Additives such as colloidal silica, surfactants, adhesion promoters, pore-forming agents, antioxidants, ultraviolet absorbers, anti-aggregation agents, and sensitizers may be added.

  The method for producing the composition is not particularly limited. When a solvent is included, the composition can be obtained by adding a predetermined amount of polymer to the solvent and stirring.

  The above composition is preferably used for film formation after removing insolubles, gelled components and the like by filter filtration. The pore size of the filter used at that time is preferably 0.05 to 2.0 μm, more preferably 0.05 to 1.0 μm, and most preferably 0.05 to 0.5 μm. The material of the filter is preferably polytetrafluoroethylene, polyethylene, polypropylene, or nylon, and more preferably polytetrafluoroethylene, polyethylene, or nylon.

[4] Pattern Forming Method The pattern forming method of the present invention includes a step of forming a photosensitive film, a step of exposing the photosensitive film, and a developing step of developing 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 coating on a substrate such as a silicon wafer, SiO ₂ wafer, SiN wafer, glass, plastic film, microlens, etc. by any method such as the ink jet method or the ink jet method, the solvent is removed by heat treatment as necessary. It can be formed by forming a (photosensitive film) and performing a pre-bake treatment.

  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.

  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. Examples of the prebaking condition include a condition of heating at 70 ° C. to 150 ° 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 composition layer after exposure is developed with a developer (development process). Thereby, a negative pattern (resist pattern) can be formed.

When carrying out negative development, it is preferable to use a developer containing an organic solvent (organic developer).
As the organic developer, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, Examples include phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.
Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3- Examples include ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.
Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
In particular, the organic developer is preferably a developer containing at least one solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl Ketone solvents such as isobutyl ketone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Esters such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Agents, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, etc. Solvents, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Glycol ether solvents such as methoxymethylbutanol, solvents such as tetrahydrofuran Solvent, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide amide solvent, toluene, xylene and other aromatic hydrocarbon solvents, octane, decane and other aliphatic carbonization A hydrogen solvent is mentioned.
Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone. , Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate, n-butyl alcohol, alcohol solvents such as ec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol And glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, N-methyl-2 Amide solvents of pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Aromatic hydrocarbon solvents such as cyclohexylene, octane, aliphatic hydrocarbon solvents decane.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

  In the present invention, development with an alkaline developer may be performed before or after development with an organic developer.

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.
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 for adjusting the discharge pressure with a pump and the like, and a method for changing the pressure by adjusting the pressure by supplying from a pressurized tank.

  Moreover, you may implement the process of stopping image development, after the process of developing, substituting with another solvent.

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

  The rinsing solution used in the rinsing step after development is not particularly limited as long as the pattern film is not dissolved, and a solution containing a general organic solvent can be used. As the rinsing liquid, it is preferable to use a rinsing liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. . More preferably, after the development, a cleaning step is performed using a rinse solution containing at least one organic solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent. Even more preferably, after the development, a washing step is performed using a rinse solution containing an alcohol solvent or an ester solvent. Even more preferably, after the development, a washing step using a rinsing solution containing a monohydric alcohol is performed. Particularly preferably, after the development, a washing step is performed using a rinsing liquid containing a monohydric alcohol having 5 or more carbon atoms. Here, examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl- 1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol , 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It is possible.

  A plurality of these components may be mixed, or may be used by mixing with an organic solvent other than the above.

  The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

  The vapor pressure of the rinsing liquid used after development is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution.

  In the rinsing step, the developed wafer is cleaned using a rinsing solution containing the organic solvent. 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 is usually 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

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 and low dielectric constant 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 polymer 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 the dry film thickness, it is possible to form a coating film having a thickness of about 0.05 to 1.5 μm by one coating and a thickness of about 0.1 to 3 μm by two coatings.
Since the cage-like silsesquioxane structure of the polymer is not decomposed upon firing, it is preferable that groups (hydroxyl groups, silanol groups, etc.) that nucleophilically attack Si atoms during the production of the composition and film are substantially absent. .

The photosensitive composition of the present invention can be used for various applications as described above. For example, it is preferable to use it for producing an insulating film or an antireflection film.
Therefore, the present invention also relates to an antireflection film that is a pattern film obtained by the above-described pattern forming method of the present invention.
The present invention also relates to an insulating film which 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 antireflection film. The present invention also relates to an electronic device having the above insulating film.
Hereinafter, such an insulating film and 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 insulating film or the low refractive index film is a preferable range particularly in the application of the insulating film or the low refractive index film, but is not limited to the application.

<Insulating film>
The thickness of the insulating film obtained from the above-described composition is not particularly limited, but is preferably 0.005 to 10 μm, more preferably 0.01 to 5.0 μm, and 0.01 to 1. More preferably, it is 0 μm.
Here, the thickness of the insulating film of the present invention means a simple average value when three or more arbitrary positions are measured with an optical interference film thickness measuring instrument.

  Although the relative dielectric constant of the insulating film obtained by the above-described method of the present invention varies depending on the material used, the relative dielectric constant is preferably 2.50 or less at a measurement temperature of 25 ° C. More preferably, it is 40.

  The Young's modulus of the insulating film of the present invention varies depending on the material used, but is preferably 2.0 to 15.0 GPa at 25 ° C., more preferably 3.0 to 15.0 GPa.

The film obtained from the film-forming composition described above is preferably a porous film, and the pore diameter showing the maximum peak in the pore distribution curve of the pores in the porous film (hereinafter also referred to as the maximum distribution diameter) is It is preferable that it is 5 nm or less. When the maximum distribution diameter is 5 nm or less, it is possible to achieve both excellent mechanical strength and relative dielectric constant characteristics.
The maximum distribution diameter is more preferably 3 nm or less. The lower limit of the maximum distribution diameter is not particularly limited, but a lower limit that can be measured by a known measuring apparatus is 0.5 nm.
The maximum distribution diameter means a hole diameter showing a maximum peak in a hole distribution curve obtained by a nitrogen gas adsorption method.

  When the insulating film obtained by using the composition of the present invention is used as an interlayer insulating film for a semiconductor, in the wiring structure, a barrier layer for preventing metal migration may be provided on the wiring side surface. In addition, there may be an etching stopper layer, etc. in addition to a cap layer and interlayer adhesion layer that prevent peeling by CMP (Chemical Mechanical Polishing) on the bottom surface of the upper surface of the wiring and interlayer insulating film. The layer may be divided into a plurality of layers with other kinds of materials as required.

  The insulating film of the present invention may be used by forming a laminated structure with other Si-containing insulating films or organic films. It is preferable to use it laminated with a hydrocarbon film.

  The insulating film obtained using the film forming composition of the present invention can be etched for copper wiring or other purposes. Etching may be either wet etching or dry etching, but dry etching is preferred. For dry etching, either ammonia-based plasma or fluorocarbon-based plasma can be used as appropriate. For these plasmas, not only Ar but also gases such as oxygen, nitrogen, hydrogen, and helium can be used. Further, after the etching process, ashing can be performed for the purpose of removing the photoresist or the like used in the process, and further, cleaning can be performed to remove a residue at the time of ashing.

  The insulating film obtained by using the film-forming composition of the present invention can be subjected to CMP to planarize the copper plating portion after the copper wiring processing. As the CMP slurry (chemical solution), commercially available slurries (for example, manufactured by Fujimi, manufactured by Rodel Nitta, manufactured by JSR, manufactured by Hitachi Chemical, etc.) can be used as appropriate. Moreover, as a CMP apparatus, a commercially available apparatus (Applied Materials Co., Ltd., Ebara Corporation, etc.) can be used suitably. Further, cleaning can be performed to remove slurry residues after CMP.

<Application>
The insulating film of the present invention can be used for various purposes, and can be particularly suitably used for electronic devices. An electronic device means a wide range of electronic equipment including a semiconductor device and a magnetic recording head. For example, it is suitable as an insulating film in semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and electronic parts such as multichip module multilayer wiring boards, semiconductor interlayer insulating film, etching stopper film, surface In addition to protective films and buffer coat films, it is used as LSI passivation films, alpha ray blocking films, flexographic printing plate cover lay films, overcoat films, flexible copper-clad cover coats, solder resist films, liquid crystal alignment films, etc. be able to. It can also be used as a surface protective film, an antireflection film, or a retardation film for optical devices.

<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 1.27 to 1.35, and 1.27 to 1. .33 is particularly preferred. Within the above range, it is useful as an antireflection film described later.

Since the pattern film obtained using the composition has a large number of pores in the film, it exhibits excellent low refractive index properties. Specifically, the film density of the obtained film is 0.7 to 1.25 g / cm ³ , preferably 0.7 to 1.2 g / cm ³ , more preferably 0.8 to 1.2 g / cm ^3. It is. If the film density is less than 0.7 g / cm ³ , the mechanical strength of the resulting film may be inferior, whereas if it exceeds 1.25 g / cm ³ , the heat resistance may be inferior. The film density can be measured by a known measuring apparatus such as an X-ray reflectivity method (XRR).

<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 lower limit is preferably 0 as it is smaller.
The haze of the antireflection film is preferably 3% or less, more preferably 1% or less, and most preferably 0.5% or less. The lower limit is preferably 0 as it is smaller.

  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.

For the following GPC measurement, Waters 2695 and Shodex GPC column KF-805L (3 columns directly connected) were used, 50 μl of a terahydrofuran solution having a column temperature of 40 ° C. and a sample concentration of 0.5 mass% was injected, and the elution solvent As follows, tetrahydrofuran was flowed at a flow rate of 1 ml per minute, and the sample peak was detected by an RI detector (Waters 2414) and a UV detector (Waters 2996). M _w and M _n were calculated using a calibration curve prepared using standard polystyrene.

<Synthesis of Compound I-12>
A mixed solution of 2000 g of electronic grade concentrated hydrochloric acid, 12 L of n-butanol and 4000 g of ion-exchanged water was cooled to 10 ° C., and a mixed solution of 840 g of vinyltriethoxysilane and 786 g of methyltriethoxysilane was added dropwise thereto over 20 minutes. Thereafter, the mixture was further stirred at 25 ° C. for 18 hours. The precipitated crystals were collected by filtration and washed with 300 mL of electronic grade methanol. After washing, the crystals were dissolved in 4000 mL of tetrahydrofuran, and 4000 mL of electronic grade methanol and then 8000 mL of ion-exchanged water were added dropwise with stirring. The precipitated crystals were collected by filtration and dried to obtain 105 g of the desired product (Compound I-12) as a white solid. ^{As a result of 1} H-NMR measurement (300 MHz, CDCl ₃ ), multiple lines were observed at 6.08 to 5.88 and 0.28 to 0.18 ppm. From this integration ratio, the vinyl / methyl ratio = 3.9 / 4. .1 was calculated. In the above formula (3), x was 3.9, y was 4.1, and x + y = 8.0. The resulting silsesquioxane was a mixture of cage silsesquioxane compounds represented by the above general formula (Q-6).

<Synthesis of Compound I-32>
A mixed solution of 67 g of electronic grade concentrated hydrochloric acid, 305 g of n-butanol and 133 g of ion-exchanged water was cooled to 10 ° C., and 59 g of vinyltriethoxysilane was added dropwise thereto over 15 minutes. Thereafter, the mixture was further stirred at 25 ° C. for 18 hours. The precipitated crystals were collected by filtration and washed with 50 g of electronic grade methanol. This was dissolved in 42 g of tetrahydrofuran, and 42 g of electronic grade methanol and then 127 g of ion-exchanged water were added dropwise with stirring. The precipitated crystals were collected by filtration and dried to obtain 4.2 g of the desired product (Compound I-32) as a white solid. The results of ¹ H-NMR measurement were as follows. ¹ H-NMR (300 MHz, CDCl 3): 6.13-5.88 (m, 24H)

  Below, the synthesis | combining method of the polymer (resin A) using the silsesquioxane (compound I) synthesize | combined above is explained in full detail.

<Synthesis of Resin A-32>
5 g of the compound (I-32) synthesized above was added to 132 g of chlorobenzene. A solution prepared by dissolving 0.2 g of V-601 (10-hour half temperature 66 ° C.) manufactured by Wako Pure Chemical Industries, Ltd. in 80 g of chlorobenzene as a polymerization initiator while heating the obtained solution at an internal temperature of 120 ° C. in a nitrogen stream. 6.25 ml was added dropwise over 60.5 minutes. After completion of the dropwise addition, the mixture was further heated to reflux for 1 hour. After cooling the reaction solution to room temperature, 100 mL of electronic grade methanol and 5 mL of ion exchange water were added to the reaction solution, and the precipitated solid was collected by filtration and washed with 10 mL of electronic grade methanol. After washing, the solid was dissolved in 100 g of tetrahydrofuran, and 20 g of ion-exchanged water was added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation and 20 g of electronic grade methanol was added. The precipitated solid was collected by filtration and dried to obtain 2.3 g of the desired product (resin A-32) as a white solid.
When the obtained resin was analyzed by GPC, it was _Mw = 20.28 * 10 < ⁴ _> , _Mn = 9.63 * 10 < ⁴ _> . In the solid, the unreacted compound (I-32) was 1% by mass or less, and no component having a molecular weight of 3 million or more was observed. When ¹ H-NMR spectrum was measured using deuterated chloroform as a measurement solvent, an alkyl group-derived proton peak (0.5 to 3.0 ppm) generated by polymerization of a vinyl group and a remaining vinyl group proton peak ( 4.9-6.8 ppm) was observed at an integration ratio of 6.7 / 1.3. From the integral ratio, the content of the polymerizable group in the resin was 83.8 mol% with respect to the total organic groups bonded to the silicon atom in the resin.

<Synthesis of Resin A-12>
80 g of the compound (I-12) synthesized above was added to 2112 g of chlorobenzene. While heating and refluxing the obtained solution at an internal temperature of 120 ° C. in a nitrogen stream, 398 ml of a solution obtained by dissolving 500 mg of V-601 (10 hours half-temperature 66 ° C.) as a polymerization initiator in 200 g of chlorobenzene. Was added dropwise over 265.3 minutes. After completion of the dropping, the reaction solution was cooled to room temperature, 5200 g of electronic grade methanol and 520 mL of ion-exchanged water were added to the reaction solution, the precipitated solid was collected by filtration, washed with 100 mL of electronic grade methanol, and dried under reduced pressure for 12 hours. The solid was dissolved in 825 g of tetrahydrofuran, 110 g of ion-exchanged water and 110 g of electronic grade methanol were added dropwise with stirring, and the precipitated solid was collected by filtration and dried. The same operation was repeated three times to obtain 31 g of a white solid target product (Resin A-12).
When the obtained resin was analyzed by GPC, it was _Mw = 19.3 * 10 < ⁴ _{> and Mn} = 7.85 * 10 < ⁴ _> . In the solid, the unreacted compound (I-12) was 1% by mass or less, and no component having a molecular weight of 3 million or more was observed. When ¹ H-NMR spectrum was measured using deuterated chloroform as a measurement solvent, a proton peak derived from a methyl group (−0.5 to 0.5 ppm) and a proton peak derived from an alkyl group formed by polymerization of a vinyl group ( 0.5-3.0 ppm) and the remaining vinyl group proton peak (4.9-6.8 ppm) were observed at an integral ratio of 3.5 / 2.8 / 1.7. From the integration ratio, the content of the polymerizable group in the resin was 21.3 mol% with respect to the total organic groups bonded to the silicon atom in the resin.

<Resin for Comparative Example (R-1)>
A 50 ml three-necked flask was charged with 625 mg of tetraethoxysilane, 2.32 g of vinyltriethoxysilane, 100 mg of oxalic acid, 12 ml of isopropyl alcohol, 4 ml of butanol, and 3 ml of ion-exchanged water. Got. After cooling, the mixture was filtered with a tetrafluoroethylene filter having a pore size of 0.1 μm.

<Preparation of photosensitive composition>
The components shown in Table 2 below are dissolved in propylene glycol monomethyl ether acetate (PGMEA: also known as 1-methoxy-2-acetoxypropane) to give a total solid concentration of 10% by mass and filtered through a tetrafluoroethylene filter having a pore size of 0.1 μm. Then, photosensitive compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were prepared.
In Table 2, the contents of the resin, the compound having SiH bond (denoted as “SiH compound”), the compound having SH bond (denoted as “SH compound”), the photopolymerization initiator, and the polymerizable compound are as follows. It is expressed in mass% with respect to the total solids in the coating solution).
As SiH compounds, the following compounds purchased from Gelest and Aldrich were used. The structures of the SiH compounds (1) to (5) are shown below.
SiH compound (1): manufactured by Gelest (50-55 mol% Methylhydrosiloxane) -Dimethylsiloxane copolymer, Trimethylsiloxane Terminated Number average molecular weight about 1000
SiH compound (2): manufactured by Gelest (25-30 mol% Methylhydrosiloxane) -Dimethylsiloxane copolymer, Trimethylsiloxane Terminated Number average molecular weight of about 2000
SiH compound (3): manufactured by Gelest (15-18 mol% Methylhydrosiloxane) -Dimethylsiloxane copolymer, Trimethylsiloxane Terminate Number average molecular weight: about 2000
SiH compound (4): Triphenylsilane manufactured by Aldrich
SiH compound (5): Tris (dimethylsiloxy) phenylsilane manufactured by Aldrich
A commercial product was used as the polymerization initiator. The details are as described above. The structure of the polymerization initiator used is shown below.
As the polymerizable compound, DPHA: dipentaerythritol hexaacrylate was used.

[Compound having SiH bond]

  For comparison, a compound having the following structure having an SH bond was used.

(Photopolymerization initiator)

  The film formed by the following method was evaluated by the following method. The results are shown in Table 3.

The photosensitive composition solution prepared as described above was applied onto a 6-inch silicon wafer, the substrate was pre-dried at 110 ° C. for 1.0 minute on a hot plate, and a photosensitive film having a film thickness of 300 nm. A film was formed. Next, using a mercury lamp containing 365 nm light, exposure was performed at a dose of 1000 mJ / cm ² through a 365 nm band pass filter to obtain a fully cured film. The cured film was evaluated for relative dielectric constant, Young's modulus, heat resistance, and resolution.
<Relative permittivity (k value)>
Using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard, the capacity value at 1 MHz (cured film portion, measurement temperature 25 ° C.) was used for calculation. ◎ when the measured value is 2.1 or more and less than 2.3, ◯ when it is 2.3 or more and less than 2.5, △ when it is 2.5 or more and less than 2.7, × when it is 2.7 or more It was.

<Young's modulus>
Young's modulus at 25 ° C. was measured using MTS Nanoindenter SA2. The case where the measured value was 5.5 GPa or more was rated ◎, the case where it was 3.5 GPa or more and less than 5.5 GPa, ◯, the case where it was 0 GPa or more and less than 3.5 GPa, or the case where it was less than 2.0 GPa. From a practical viewpoint, it is necessary that x is not included.
<Heat resistance>
The heat resistance was evaluated by heating the obtained pattern film at 400 ° C. in air for 60 seconds and measuring the rate of change in film thickness. It can be said that a coating film having a value of the rate of change in film thickness close to 0% has better heat resistance. When the rate of change in film thickness is 0% or more and less than 5%, ◎ when 5% or more but less than 10%, △ when 10% or more but less than 20%, or when 20% or more but less than 30% It was.
<Resolution>
The photosensitive composition solution prepared as described above was applied onto a 6-inch silicon wafer, the substrate was pre-dried at 100 ° C. for 1.0 minute on a hot plate, and a photosensitive film having a film thickness of 300 nm. A film was formed. Next, using a mercury lamp containing 365 nm light, exposure is performed at a wavelength of 365 nm with an exposure dose of 500 mJ / cm ² , and a pattern exposure mask having a line width of 1: 1 with a line width of 0.5 μm is used. Exposure was performed.
About the exposure board | substrate which has the obtained exposure film | membrane, it develops by immersing an exposure board | substrate for 60 second in the tank filled with propylene glycol monomethyl ether acetate (PGMEA: alias 1-methoxy-2-acetoxypropane) as a developing solution, Thereafter, it was rinsed through another PGMEA solution and dried on a hot plate at 220 ° C. for 2 minutes to obtain a pattern film.
When the obtained pattern film is observed with a length measuring SEM (Hitachi, Ltd. S-8840), a pattern with a resolution limit line width of less than 0.5 μm is resolved, ◎, 0.5 μm to 1 μm A case where a pattern of less than 2 μm was resolved, a case where a pattern of 1 μm or more to less than 2 μm was resolved, and a case where a pattern of less than 2 μm could not be resolved were marked as x. From a practical viewpoint, it is necessary that x is not included.

  PGMEA: propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-acetoxypropane) was used as the developer and rinse solution in Table 3.

From the results of Table 3, it was found that when the photosensitive composition of the present invention was used, a pattern film having a low dielectric constant and a high Young's modulus and high heat resistance could be formed with high resolution.
On the other hand, when a polymer having no cage silsesquioxane structure was used, the above effects of the present invention could not be satisfied at the same time.
Furthermore, in Example 2, in place of the SiH compound (1), Comparative Example 2 using an SH compound that is considered to function as a chain transfer agent was carried out in all of dielectric constant, Young's modulus, resolution, and heat resistance. It was inferior to Example 2.
Further, in Example 1, the composition using Compound I-12 instead of Resin A-12 had poor solubility of Compound I-12, and when the composition was applied, a powder precipitated and a uniform film was formed. Could not be formed. From this, it can be seen that by using the polymer according to the present invention, the solubility and the coating property were improved as compared with the compound as the raw material.

Furthermore, the following items were also evaluated.
When the refractive index of the whole surface cured film used for the evaluation of the relative dielectric constant was measured, the cured film using the compositions of Examples 1 to 9 had a refractive index of 1.35 or less. Comparative Examples 1 and 2 The cured film using this composition had a refractive index of 1.45. The cured film of the cured composition of the present invention exhibits an excellent low refractive index, and is useful for antireflection film applications.

Claims (21)

(A) a polymer having a polymerizable group and a cage silsesquioxane structure;
(B) a compound having a SiH bond;
(C) The photosensitive composition containing a photoinitiator.   The photosensitive composition of Claim 1 whose said photoinitiator is a nonmetallic photoinitiator.   The photosensitive composition of Claim 1 or 2 whose said photoinitiator is radical photopolymerization initiator. The silsesquioxane in which the polymer (A) having a polymerizable group and a cage silsesquioxane structure is composed of one or more cage silsesquioxane compounds represented by the following formula (1): The photosensitive composition according to claim 1, which is a polymer obtained from oxanes.
(RSiO _1.5 ) _a formula (1)
(In formula (1), R represents an organic group each independently, and at least 2 of R represents a polymeric group. A represents an integer of 8 to 16. Several R are the same. It may or may not be.)
However, a polymerizable group derived from the cage silsesquioxane compound remains in the polymer.   The photosensitive composition of any one of Claims 1-4 which is a negative composition.   The photosensitive composition of any one of Claims 1-5 whose said photoinitiator is an oxime compound. The cage silsesquioxane compound is one or more selected from the group consisting of cage silsesquioxane compounds represented by the following general formula (Q-1) to general formula (Q-7). The photosensitive composition of any one of Claims 4-6 which is.

(In General Formula (Q-1) to General Formula (Q-7), each R independently represents an organic group. In each of General Formula (Q-1) to General Formula (Q-7), R represents At least two of them represent polymerizable groups.)   The photosensitive composition of any one of Claims 4-7 whose content of the said polymeric group in the said polymer is 10-90 mol% in all the organic groups couple | bonded with the silicon atom.   The photosensitive composition of any one of Claims 4-8 whose weight average molecular weights of the said polymer are 10,000-500,000.   The pattern formation material which is the photosensitive composition of any one of Claims 1-9.   The photosensitive film | membrane formed with the photosensitive composition of any one of Claims 1-9.   The pattern formation method including the process of forming the photosensitive film of Claim 11, the process of exposing the said photosensitive film, and the image development process which develops and obtains a pattern film.   The pattern forming method according to claim 12, wherein the developing step is a step of developing using a developer containing an organic solvent.   The pattern according to claim 13, wherein the developer containing the organic solvent is at least one solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Forming method.   The pattern film obtained by the pattern formation method in any one of Claims 12-14.   The pattern film according to claim 15, having a refractive index of 1.35 or less.   The pattern film according to claim 15 or 16, wherein a relative dielectric constant at 25 ° C is 2.50 or less.   An antireflection film, which is the pattern film according to claim 15.   The insulating film which is a pattern film of any one of Claims 15-17.   An optical device having the antireflection film according to claim 18.   An electronic device having the insulating film according to claim 19.