JP2017198841A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive composition which is excellent in sensitivity and process margin and is capable of giving a highly reliable cured film.SOLUTION: The positive photosensitive composition contains (A) a polysiloxane compound whose alkali solubility increases by the action of an acid, (B) a photoacid generator, and (C) a basic compound having a molecular weight of 220 or more and has sensitivity in a specific range. The photoacid generator (B) and the basic compound (C) are contained at a specific weight ratio.SELECTED DRAWING: None

Description

  The present invention relates to a positive photosensitive composition.

  In the display field such as a liquid crystal display and an organic EL display, there has been a demand for a positive photosensitive composition that can be positively patterned and can form a highly reliable insulating film.

  For example, Patent Documents 1 and 2 report a curable composition or a positive photosensitive composition containing a siloxane compound and a photoacid generator. Patent Document 1 describes the use of a basic compound.

JP 2010-235862 A (released on October 21, 2010) International Publication No. 2014/007231 (released on January 9, 2014)

  However, the prior art as described above has room for improvement in terms of compatibility between patterning sensitivity and process margin.

  The present invention has been made in view of the above problems, and an object of the present invention is to realize a positive photosensitive composition that is excellent in sensitivity and process margin and can provide a highly reliable cured film. .

  As a result of intensive studies to achieve the above object, the present inventors have used a basic compound having a specific molecular weight, and adjusted the weight ratio between the basic compound and the photoacid generator. The present inventors have found that a positive photosensitive composition that is excellent in sensitivity and process margin and can provide a highly reliable cured film can be realized, and the present invention has been completed. That is, the present invention includes the following configurations.

[1] (A) A polysiloxane compound whose alkali solubility is increased by the action of an acid, (B) a photoacid generator, and (C) a basic compound having a molecular weight of 220 or more. 2) Positive photosensitive composition characterized by satisfying:
(1) It has sensitivity in an exposure wavelength range of 365 nm to 425 nm;
(2) The weight ratio of the basic compound (C) having a molecular weight of 220 or more to the (B) photoacid generator is 0.02 to 0.5.

  [2] The positive photosensitive composition as described in [1], wherein the photoacid generator (B) is a compound having a structure represented by the following formula (I):

(In formula (I), X is an anion).

  [3] The positive photosensitive composition as described in [1], wherein the photoacid generator (B) is a compound having a substituted phenyl group.

  [4] The positive photosensitive composition as described in any one of [1] to [3], further comprising (D) a sensitizer.

  [5] The polysiloxane compound whose alkali solubility is increased by the action of the acid (A) has a SiH group, and the positive photosensitive composition contains a compound having an alkenyl group (E). The positive photosensitive composition as described in any one of [1] to [4].

  [6] A cured film obtained from the positive photosensitive composition according to any one of [1] to [5].

  According to the above configuration, the present invention has an effect of making it possible to obtain a positive photosensitive composition that is excellent in sensitivity and process margin and can provide a highly reliable cured film.

  An embodiment of the present invention will be described below, but the present invention is not limited to this. The present invention is not limited to each configuration described below, and various modifications can be made within the scope shown in the claims, and technical means disclosed in different embodiments and examples respectively. Embodiments and examples obtained by appropriately combining them are also included in the technical scope of the present invention. Moreover, all the academic literatures and patent literatures described in this specification are used as references in this specification. Unless otherwise specified, “A to B” representing a numerical range means “A or more (including A and greater than A) and B or less (including B and less than B)”. In the present specification, “wt%” means “wt%”.

[1. (Positive photosensitive composition)
This positive photosensitive composition contains (A) a polysiloxane compound whose alkali solubility is increased by the action of an acid, (B) a photoacid generator, and (C) a basic compound having a molecular weight of 220 or more. . The positive photosensitive composition has sensitivity in an exposure wavelength range of 365 nm to 425 nm. In the positive photosensitive composition, the ratio of the weight part of the basic compound (C) having a molecular weight of 220 or more to the weight part of the photoacid generator (B) is 0.02 to 0.5. is there.

  In the following, the polysiloxane compound whose alkali solubility is increased by the action of the acid (A) is simply referred to as “(A) polysiloxane compound”, and the basic compound (C) having a molecular weight of 220 or more is simply referred to as “ (C) Basic compound ". In the present specification, the “cured film” means “film obtained by curing a positive photosensitive composition”. In this specification, “reliability” intends reliability with respect to insulation (insulation reliability).

  Since this positive photosensitive composition has the above-described configuration, it can provide a cured film with excellent sensitivity and process margin and high reliability.

  That is, this positive photosensitive composition can provide a highly reliable cured film by using the (A) polysiloxane compound. Moreover, this positive photosensitive composition shows high sensitivity with respect to active energy (light) by use of (B) photo-acid generator. Further, the present positive photosensitive composition uses (B) a photoacid generator and (C) a basic compound in combination, and (C) the basic compound has a specific molecular weight, and (C) a base. By setting the content of the functional compound to a specific ratio, the contrast between the exposed part and the unexposed part becomes clear, and an excellent process margin is exhibited.

  The components of (A) polysiloxane compound, (B) photoacid generator, and (C) basic compound will be described below.

<1-1. (A) Polysiloxane compound>
This positive photosensitive composition contains a polysiloxane compound whose alkali solubility is increased by the action of an acid as the polysiloxane compound (A).

  In the present specification, the “polysiloxane compound” means a compound having a siloxane unit Si—O—Si.

  In addition, in this specification, “the alkali solubility is increased by the action of an acid” means “having a structure in which an acid group or a hydroxyl group is expressed by being decomposed by an acid generated from a photoacid generator”. By using such (A) polysiloxane compound in combination with (B) photoacid generator component, a positive pattern can be formed.

  In other words, (A) the polysiloxane compound is introduced with “a compound having a siloxane unit Si—O—Si” as a main skeleton, “a structure in which an acid group or a hydroxyl group is expressed by being decomposed by an acid generated from a photoacid generator”. Has been. (A) A polysiloxane compound is obtained by a reaction between a “compound having a siloxane unit Si—O—Si” and a “compound having a structure in which an acid group or a hydroxyl group is expressed by being decomposed by an acid generated from a photoacid generator”. It may be obtained. From the viewpoint of excellent stability due to the Si—C bond, the (A) polysiloxane compound is more preferably obtained by a hydrosilylation reaction.

  The structure that decomposes by the acid and expresses an acidic group or a hydroxyl group is not particularly limited, but from the viewpoint of excellent patternability and insulating properties of the cured film, the functional group-protected phenol structure and / or the functional group is protected. A carboxylic acid structure is preferred.

  In the present specification, the functional group-protected phenol structure refers to a structure in which a hydrogen atom of a hydroxyl group of the phenol structure is substituted with a compound residue.

  The functional group-protected phenol structure is more preferably a bisphenol structure protected with a functional group because it can more remarkably enjoy the effect of being excellent in patternability and insulation of a cured film, and is preferably a trialkylsilyl group or butoxy group. A bisphenol structure having a functional group protected with a carbonyl group is more preferable.

  Moreover, it is preferable that the said compound residue is a C1-C50 organic group or organosilicon group.

  The compound having a functional group-protected bisphenol structure having an organic group or organic silicon group having 1 to 50 carbon atoms as the compound residue is represented by the following general formula (II).

(In the general formula (II), R ⁶ represents an organic group or organic silicon group having 1 to 50 carbon atoms, and R ⁷ may be a structure that can be taken as a bisphenol structure. In addition, hydrogen on the aromatic ring is substituted. May be)
As a method for obtaining the above compound having a functional group-protected phenol structure (particularly, the compound having a functional group-protected bisphenol structure represented by the general formula (II)), for example, a compound rich in reactivity with active hydrogen is used. The method to be used and the method of protecting with a tert-butoxycarbonyl group using a Boc reagent can be used. In these methods, a solvent and / or a catalyst may be appropriately used in order to efficiently obtain the target compound.

  When the compound having a phenol structure with a functional group protected has a SiH group that is a hydrosilylation reactive group, a method using a compound highly reactive with active hydrogen is preferable from the viewpoint of stability.

  Examples of compounds rich in reactivity with active hydrogen include halides, carboxylic acids, and silylating agents.

  As a method of using a compound rich in reactivity with the active hydrogen, (B) a method of protecting a functional group with a trialkylsilyl group using a silylating agent from the viewpoint of easy deprotection by a photoacid generator Is preferred.

  Although it does not specifically limit as an alkyl group contained in the said trialkylsilyl group, From a viewpoint of the ease of deprotection by (B) photoacid generator, it is C1-C6 alkyl which does not have an unsaturated bond. It is preferably a group, and more preferably a methyl group.

  When a functional group is protected by a trialkylsilyl group using a silylating agent, a general-purpose silylating agent can be used as the silylating agent. Specifically, for example, hexamethyldisilazane, trimethyl Chlorosilane, tert-butyldimethylchlorosilane, bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N-methyltrimethylsilylacetamide, N-methyltrimethylsilyltrifluoroacetamide, trimethylsilylimidazole, N, N′-bis (trimethylsilylurea), Examples include triethylchlorosilane, triisopropylchlorosilane, and triethylsilane. Among these silylating agents, hexamethyldisilazane, trimethylchlorosilane, or tert-butyldimethylchlorosilane is preferable from the viewpoint that it can be produced industrially at low cost.

  These silylating agents may be used alone or in combination of two or more.

  In the present specification, the functional group-protected carboxylic acid structure refers to a structure in which a hydrogen atom of a carboxyl group of a carboxylic acid structure is substituted with a compound residue.

  Since the functional group-protected carboxylic acid structure can more remarkably enjoy the effect of excellent patternability and cured film insulation, it contains a structure containing an acetal bond and / or a carboxylic acid tertiary ester bond. A structure is preferred.

  Examples of the compound having a structure containing an acetal bond include diallyl acetal, pentanal diallyl acetal, benzaldehyde diallyl acetal, 1,1,2,2-tetraallyloxyethane, 1,1,2,2-tetraallyl Examples thereof include oxypropane, 2,2-diallyl-1,3-dioxolane, methoxymethyl acrylate, ethoxymethyl acrylate, 4-vinylmethoxymethyl benzoate and 4-vinylethoxymethyl benzoate.

  In the structure containing the carboxylic acid tertiary ester structure, examples of the carboxylic acid tertiary ester structure include a structure in which a carboxyl group is protected with a p-tert butoxy group or a p-tert butoxycarbonyl group. The tertiary ester structure is not particularly limited, and known ones such as t-butyl ester can be used.

  The structure containing a carboxylic acid tertiary ester bond is preferably a carboxylic acid tertiary ester structure protected with an aliphatic ring structure from the viewpoint of excellent development contrast and heat resistance and insulation of the resulting thin film. . In this case, the tertiary carbon protecting the carboxyl group in the carboxylic acid tertiary ester structure may be a carbon that forms an aliphatic ring structure, or a carbon that does not form an aliphatic ring structure and exists independently. May be. The aliphatic ring structure is preferably an adamantane structure from the viewpoint of development contrast and exposure sensitivity.

In the present positive photosensitive composition, the content of the structure (A) above was decomposed in the presence of acid contained in the polysiloxane compound acid group or a hydroxyl group is expressed by the measurement of ^{1 H-NMR,} dibromo the standard It is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g, and further preferably 0.15 to 3 mmol / g, in terms of equivalent when converted to ethane.

  The (A) polysiloxane compound is preferably obtained by a hydrosilylation reaction between a compound (E) having an alkenyl group and a compound (F) having a SiH group, which will be described later. Thereby, the reliability of this positive photosensitive composition can further be improved.

  Here, at least one of the compound (E) having an alkenyl group and the compound (F) having an SiH group is a “compound having a siloxane unit Si—O—Si”. (E) When the compound having an alkenyl group is a “compound having a siloxane unit Si—O—Si”, <1-5. (E) A siloxane compound having an alkenyl group in the compound having an alkenyl group> is preferable.

  In addition, at least one of the compound (E) having an alkenyl group and the compound (F) having an SiH group is a “compound having a structure in which an acid group or a hydroxyl group is expressed by being decomposed by an acid generated from a photoacid generator”. .

For example, the (A) polysiloxane compound may be a compound obtained by the following reaction:
1. Hydrosilylation reaction between (E) a compound having an alkenyl group having a structure in which an acid group or a hydroxyl group is expressed by decomposition with an acid, and (F) a compound having a SiH group;
2. Hydrosilylation of a compound having an (E) alkenyl group having a structure in which an acid group or a hydroxyl group is expressed by decomposition with an acid and a compound having (F) SiH group having a structure in which the acid group or a hydroxyl group is expressed by being decomposed by an acid reaction;
3. (E) a hydrosilylation reaction between a compound having an alkenyl group and a compound having a structure (F) SiH group that is decomposed by an acid and expresses an acidic group or a hydroxyl group;
4). A hydrosilylation reaction of a compound having an (E) alkenyl group having an SiH group and a structure in which an acid group or a hydroxyl group is expressed by decomposition with an acid;
5. A hydrosilylation reaction between a compound having (E) an alkenyl group having a structure in which an acidic group or a hydroxyl group is expressed by decomposition with an acid and a SiH group, and (F) a compound having a SiH group;
6). (E) a compound having an alkenyl group having a structure in which an acidic group or hydroxyl group is decomposed by acid and a SiH group, and a compound having a structure (F) SiH group having a structure in which an acid group or hydroxyl group is decomposed by an acid Hydrosilylation reaction of
7). Hydrosilylation reaction between a compound having (E) an alkenyl group having SiH group and a compound having (F) SiH group having a structure in which an acid group or a hydroxyl group is expressed by decomposition with an acid;
8). Hydrosilylation reaction of (E) a compound having an alkenyl group having a structure in which an acid group or a hydroxyl group is expressed by decomposition with an acid and a compound having (F) SiH group having an alkenyl group;
9. A compound having (E) an alkenyl group having a structure in which an acid group or a hydroxyl group is expressed by being decomposed by an acid, and a compound having (F) SiH group having a structure in which an acid group or a hydroxyl group is decomposed by an acid and an alkenyl group is expressed. Hydrosilylation reaction of
10. (E) a hydrosilylation reaction between a compound having an alkenyl group and a structure having an alkenyl group and a structure having an acidic group or a hydroxyl group that is decomposed by an acid and having an alkenyl group;
11. A hydrosilylation reaction of a compound having an (F) SiH group having an alkenyl group and a structure in which an acidic group or a hydroxyl group is expressed by being decomposed by an acid;
12 A hydrosilylation reaction between a compound having (E) an alkenyl group having an SiH group and a structure in which an acid group or a hydroxyl group is expressed by being decomposed by an acid, and a compound having an (F) SiH group having an alkenyl group;
13. (E) a compound having an (E) alkenyl group having a structure in which an acidic group or a hydroxyl group is expressed by decomposition with an acid and a SiH group, and (F) SiH group having a structure and an alkenyl group in which an acid group or a hydroxyl group is decomposed by an acid A hydrosilylation reaction with a compound having:
14 Hydrosilylation reaction between a compound having (E) an alkenyl group having a SiH group and a structure having an acidic group or a hydroxyl group which is decomposed by an acid and an alkenyl group (F) having a SiH group.

  The catalyst used in the hydrosilylation reaction is not particularly limited, and a known hydrosilylation catalyst can be used. From the viewpoint of catalytic activity, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex, or the like can be used. It is preferable to use it.

  These hydrosilylation catalysts may be used alone or in combination of two or more.

  The (A) polysiloxane compound may contain one or more SiH groups and / or alkenyl groups that have not been used in the hydrosilylation reaction.

  The (A) polysiloxane compound preferably contains a bisphenol structure because it can improve the chemical resistance and insulation of the resulting cured film.

  Examples of the bisphenol structure include bisphenol A structure, bisphenol AP structure, bisphenol AF structure, bisphenol B structure, bisphenol BP structure, bisphenol E structure, bisphenol M structure, bisphenol F structure, bisphenol S structure, bisphenol PH structure, and bisphenol C. Examples include a structure, a bisphenol G structure, a bisphenol TMC structure, and a bisphenol Z structure.

  Among these, bisphenol A structure, bisphenol B structure, bisphenol C structure, bisphenol E structure, bisphenol F structure, bisphenol AF are preferred from the viewpoint that a pattern having excellent solubility in an alkali developer and excellent contrast can be obtained. A structure, a bisphenol S structure, a bisphenol AP structure or a bisphenol PH structure is preferred. In particular, a bisphenol A structure or a bisphenol S structure is preferable from the viewpoint of availability, and a bisphenol S structure or a bisphenol F structure is preferable from the viewpoint of ease of deprotection by a photoacid generator.

  The polysiloxane compound (A) is a compound having another structure as long as it does not impair the purpose and effect of the present invention, as long as it is a compound having a structure in which an acid group or a hydroxyl group is decomposed by an acid and a polysiloxane structure. There may be.

  In the present positive photosensitive composition, the polysiloxane compound (A) may be used alone or in combination of two or more.

<1-2. (B) Photoacid generator>
The present positive photosensitive composition contains (B) a photoacid generator. The photoacid generator is not particularly limited as long as it is a compound capable of decomposing the component (A) and expressing an acid group or a hydroxyl group by being exposed to light, and capable of releasing an acid. Since the component (A) in which an acidic group or a hydroxyl group is expressed is soluble in an alkali developer, a positive pattern can be formed.

  The photoacid generator (B) is not particularly limited as long as it generates a Lewis acid upon exposure, and known ones can be used, and arylsulfonium salts, halogen-containing complex ion aromatic sulfoniums can be used. Preference is given to salts or iodonium salts or aromatic onium salts of group II, group V or group VI elements.

  In particular, an iodonium salt is preferable from the viewpoint that a highly sensitive positive photosensitive composition can be obtained with a small exposure amount, and a sulfonium salt is preferable from the viewpoint of storage stability of the positive photosensitive composition.

Examples of the anion contained in the (B) photoacid generator is not particularly limited, for ^{_{example, B (C 6 F 5)}} 4 -, PF 6 -, SbF 6 -, CF 3 SO 3 - and _C 4 _{F 9} SO _3- ^{and the} like can be mentioned.

  Commercially available products can also be used as the photoacid generator (B), and specific examples thereof include FX-512 (manufactured by 3M), UVR-6990 and UVR-6974 (both manufactured by Union Carbide). ), UVE-1014 and UVE-1016 (both manufactured by General Electric), KI-85 (manufactured by Degussa), SP-152 and SP-172 (both manufactured by Asahi Denka), Sun-Aid SI-60L, SI-80L And SI-100L (both manufactured by Sanshin Chemical Industry Co., Ltd.), WPI113 and WPI116 (both manufactured by Wako Pure Chemical Industries, Ltd.), RHODORSIL PI2074 (manufactured by Rhodia), and BBI-102, BBI-103, BBI-105, TPS -102, TPS-103, TPS-105, MDS-103, MDS- 05, DTS-102, DTS-103 and DTS-105 (all manufactured by Midori Kagaku Co., Ltd.).

  Moreover, it is preferable that the said (B) photo-acid generator is a compound which does not have an unsubstituted phenyl group. If the (B) photoacid generator is a compound having no unsubstituted phenyl group, no harmful benzene is generated during the process. An unsubstituted phenyl group intends a structure represented by the following formula (III).

  For example, triphenylsulfonium nonafluorobutane-1-sulfonate represented by the following formula (IV) (for example, product name: TPS-PFBS manufactured by Toyo Gosei Co., Ltd.) is “a compound having no unsubstituted phenyl group. Is excluded.

  The compound having no unsubstituted phenyl group may be a compound having a substituted phenyl group. Examples of such a compound include tris (4-tert-butylphenyl) sulfonium nonafluorobutane-1-sulfonate represented by the following formula (V) (for example, trade name: TTBPS-PFBS, manufactured by Toyo Gosei Co., Ltd.). ).

  The (B) photoacid generator is preferably a compound having a structure represented by the following formula (I). If the (B) photoacid generator is a compound having a structure represented by the following formula (I), a positive photosensitive composition having better sensitivity can be provided.

  Specific examples of the compound having the structure represented by the formula (I) include trifluoromethanesulfonic acid-2,3-norbornanecarboximide represented by the following formula (VI) (for example, manufactured by Toyo Gosei Chemical Co., Ltd. Name: NR-TF) and trifluoromethanesulfonic acid-1,8-naphthalimide represented by the following formula (VII) (for example, product name: NI-TF manufactured by Toyo Gosei Co., Ltd.).

  In the present positive photosensitive composition, the photoacid generator (B) may be used alone or in combination of two or more.

  The content of the (B) photoacid generator is not particularly limited, but is preferably 0.01 to 10 parts by weight, with the total amount of the positive photosensitive composition excluding the solvent being 100 parts by weight, More preferably, it is 0.1 to 5 parts by weight. By making content of the said (B) photo-acid generator into this range, patterning property and the heat resistance and light resistance of hardened | cured material can be improved.

<1-3. (C) Basic compound>
This positive photosensitive composition contains (C) a basic compound. In the present invention, the basic compound acts as a quencher for Lewis acid. The basic compound (C) prevents unwanted chemical reaction in the unexposed part by suppressing the diffusion of the Lewis acid generated from the photoacid generator (B) upon exposure to the unexposed part. Is possible. (C) By using a basic compound, when producing a cured film, it becomes possible to suppress a change in line width due to a change in time required from exposure to development, so that the present positive photosensitive composition is excellent. A process margin can be given. In addition, by using the basic compound (C), it is possible to clarify the contrast between the exposed portion and the unexposed portion, so that the resolution of the cured film can be improved. Furthermore, the storage stability of this positive photosensitive composition can also be improved by using (C) a basic compound.

  In the present positive photosensitive composition, the basic compound (C) has a molecular weight of 220 or more. (C) If the molecular weight of the basic compound is 220 or more, the basic compound exhibits remarkable performance as a quencher for Lewis acid, and thus the above-described effects can be obtained as a larger effect.

  The basic compound (C) is not particularly limited as long as the molecular weight is 220 or more, but primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, complex Examples thereof include cyclic amines, amide derivatives and imide derivatives. Among these, derivatives of aromatic amines and derivatives of heterocyclic amines can be suitably used as basic compounds from the viewpoint of acid scavenging ability.

  Examples of the aromatic amines and the heterocyclic amines include aniline derivatives, pyrrole derivatives, oxazole derivatives, thiazole derivatives, imidazole derivatives, pyrazole derivatives, furazane derivatives, pyrroline derivatives, pyrrolidine derivatives, imidazoline derivatives, imidazolidine derivatives, Pyridine derivatives, pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives, cinnoline derivatives, quinazoline derivatives , Quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives , Acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives and uridine derivatives, and the like. Examples of the derivatives of the heterocyclic amines include 2,6-lutidine derivatives.

  Especially, the morpholine derivative or piperidine derivative which is heterocyclic amines can be used conveniently as a basic compound. Specific examples of the morpholine derivative include bis (2-morpholinoethyl) ether (BME). Specific examples of piperidine derivatives include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (BPPS).

  As said (C) basic compound, 1 type may be used and 2 or more types may be used together.

  The weight ratio of the (C) basic compound to the (B) photoacid generator is 0.02 to 0.5, preferably 0.03 to 0.45, and preferably 0.04 to 0.4. It is more preferable that If the weight ratio is 0.02 or more, the above-described process margin, resolution, and storage stability can be sufficiently improved. On the other hand, if the said weight ratio is 0.5 or less, the fall of the physical property of a cured film can be prevented.

  Moreover, in this positive photosensitive composition, it is preferable that the compounding quantity of (C) basic compound is 0.001-5.0 weight part per 100 weight part of (A) polysiloxane compound, and storage stability From the viewpoint of the property and transparency of the cured film, it is more preferably 0.01 to 3.0 parts by weight. If the blending amount of the basic compound (C) is 0.001 part by weight or more with respect to 100 parts by weight of the polysiloxane compound (A), the effect as a quencher can be sufficiently exerted.

<1-4. (D) Sensitizer>
The positive photosensitive composition further comprises (D) a sensitizer in addition to the three components (A) polysiloxane compound, (B) photoacid generator and (C) basic compound. It is preferable to do. (D) By containing a sensitizer, it is possible to obtain a positive photosensitive composition having higher sensitivity than the positive photosensitive composition comprising the above three components.

  The (D) sensitizer has an effect of improving the sensitivity to light of the positive photosensitive composition, in particular, the sensitivity to light having a short wavelength such as h-line (405 nm) and i-line (365 nm). In the positive photosensitive composition, it is possible to adjust the curability of the cured film by using the (D) sensitizer together with the component (B).

  Examples of the sensitizer (D) include anthracene compounds and thioxanthone compounds. The (D) sensitizer is preferably an anthracene compound from the viewpoint of the photosensitization effect.

  Examples of the anthracene compound include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-di. Ethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene and 9,10-diphenyl-2,6-di- Examples include tert-butylanthracene.

  Among these, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene or 9,10-diethoxyanthracene is preferable from the viewpoint of availability.

  In addition, anthracene is preferable from the viewpoint of excellent transparency of the cured film, and 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, or 9,10-diethoxy from the viewpoint of excellent compatibility with other components. Anthracene is preferred.

  The (D) sensitizer is preferably a thioxanthone compound from the viewpoint of storage stability of the positive photosensitive composition.

  Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2,5-diethyldioxanthone, and isopropylthioxanthone. Among these, 2,5-diethyldioxanthone or isopropylthioxanthone is preferable from the viewpoint of availability.

  These (D) sensitizers may be used alone or in combination of two or more.

  When the present positive photosensitive composition contains (D) a sensitizer, the content of the (D) sensitizer is not particularly limited as long as it is an amount capable of exerting a sensitizing effect, but (A) The amount is preferably 0.5 to 50 parts by weight, more preferably 1 to 40 parts by weight, and further preferably 2 to 35 parts by weight per 100 parts by weight of the polysiloxane compound. In order to obtain a further sensitizing effect, the molar ratio of (D) sensitizer to (B) photoacid generator is preferably 0.01 to 300, preferably 0.1 to 100 mol. More preferably.

  If the amount of the sensitizer contained in the positive photosensitive composition is not less than the above lower limit value, a sufficient sensitizing effect can be obtained, and when a cured film is formed, it takes a long time for curing. , It does not adversely affect the developability. Further, if the amount of the sensitizer is not more than the above upper limit value, the color remains on the cured film, the cured film is colored due to rapid curing, or the cured film impairs heat resistance or light resistance. There is no.

<1-5. (E) Compound having alkenyl group>
The positive photosensitive composition may contain (E) a compound having an alkenyl group. In addition, this positive photosensitive composition may contain the compound which has (E) alkenyl group separately from (A) polysiloxane compound, (E) By hydrosilylation reaction using the compound which has alkenyl group The obtained (A) polysiloxane compound may be included.

  In view of obtaining a cured film with higher reliability, the (A) polysiloxane compound has a SiH group, and the positive photosensitive composition contains (E) a compound having an alkenyl group. Is preferred.

(E) As the compound having an alkenyl group, an organic compound having an alkenyl group or a siloxane compound having an alkenyl group can be used. Specific examples include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, Trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1,1,2,2-tetraallyloxyethane, diarylidene pentaerythritol, triallyl cyanurate, 1,2,4-trivinylcyclohexane, 1,4-butanediol diallyl ether, nonanediol diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, Ethylene glycol diallyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, diallyl ether of bisphenol S, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3- Bis (allyloxy) adamantane, 1,3-bis (vinyloxy) adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, dicyclopentadiene, cyclopentadiene, cyclohexadiene, Cyclooctadiene, tricyclopentadiene, norbornadiene, vinylnorbornene, vinylcyclohexene, vinylcyclopentene, butadiene, isoprene, octadiene 1,5-hexadiene, 1,9-decadiene, diallyl ether, bisphenol A diallyl ether, 2,5-diallylphenol allyl ether, triallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate , Diallyl monopropyl isocyanurate, monoallyl dibenzyl isocyanurate, diallyl monomethyl isocyanurate and monoallyl dimethyl isocyanurate, and polysiloxane compounds having a vinyl group (Si—CH═CH ₂ group) bonded to a silicon group. It is done.

  Examples of the polysiloxane compound having a vinyl group bonded to a silicon group include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1-propyl-3,5. , 7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 Trivinyl-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane and 1,3,5,7,9,11-hexavinyl-1, 3,5,7,9,11-hexamethylcyclosiloxane and the like.

  From the viewpoint that the compound (C) having an alkenyl group can form a cured product excellent in transparency, heat resistance, light resistance and insulation, the structure and alkenyl represented by the following formula (VIII) A compound having a group is preferable.

  Examples of the compound having a structure represented by the above formula (VIII) and an alkenyl group include triallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monopropyl isocyanurate, mono Examples include allyl dibenzyl isocyanurate, diallyl monomethyl isocyanurate and monoallyl dimethyl isocyanurate. Among these, triallyl isocyanurate, diallyl isocyanurate or diallyl monomethyl isocyanurate is preferable from the viewpoint of availability.

  (E) The compound having an alkenyl group is preferably a siloxane compound having an alkenyl group from the viewpoint of transparency and curability of the cured film.

  The alkenyl group-containing siloxane compound is preferably a siloxane compound having two or more vinyl groups bonded to a silicon group from the viewpoint of compound availability, and has 2 to 6 vinyl groups bonded to a silicon group. The siloxane compound is more preferable.

  Examples of the siloxane compound having two or more vinyl groups bonded to the silicon group include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1-propyl-3. , 5,7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3 , 5-trivinyl-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane and 1,3,5,7,9,11-hexavinyl- 1,3,5,7,9,11-hexamethylcyclosiloxane and the like.

  The number of alkenyl groups in one molecule of the compound having the (E) alkenyl group is preferably 2 or more from the viewpoint of increasing the crosslinking density and obtaining a tougher thin film.

  (E) When (A) a polysiloxane compound is obtained using a compound having an alkenyl group, (A) the polysiloxane compound has a structure in which an acid group or a hydroxyl group is expressed by decomposition with an acid. A compound having a group and / or a compound having (F) SiH group described later needs to have a structure in which an acid group or a hydroxyl group is expressed by being decomposed by an acid.

  When the compound (E) having an alkenyl group has a structure in which an acid group or a hydroxyl group is expressed by being decomposed by an acid, the structure in which the acid group or the hydroxyl group is expressed by being decomposed by an acid is described in (A) The structure demonstrated in the polysiloxane compound> is mentioned.

  Further, when the compound (E) having an alkenyl group contains a carboxylic acid tertiary ester structure as the functional group-protected carboxylic acid structure, the compound is not particularly limited. For example, t-butyl acrylate , T-butyl methacrylate, t-butyl 3-butenoate, 2-methyl 2-adamantyl acrylate, 2-ethyl 2-adamantyl acrylate, 2-methyl 2-adamantyl methacrylate, 2-ethyl 2-adamantyl methacrylate, 1 1,3-adamantanediol diacrylate, 1,3-adamantanediol dimethacrylate, and the like. Among these, from the viewpoint of excellent heat resistance, a compound having two or more (meth) acryl groups is preferable, and 1,3-adamantanediol diacrylate or 1,3-adamantanediol dimethacrylate is preferable.

  The compound (E) having an alkenyl group may be a compound further having a SiH group in addition to the alkenyl group. (A) In obtaining a polysiloxane compound, when using the compound which has (E) alkenyl group which has SiH group, (F) The compound which has SiH group may be used and it is not necessary to use it. (A) In obtaining a polysiloxane compound, a compound having (E) an alkenyl group having a SiH group is used, and if a compound having (F) a SiH group is not used, the compound having the (E) alkenyl group having the SiH group is used. The compound has a structure in which an acidic group or a hydroxyl group is expressed by being decomposed by an acid.

  For example, the compound (E) having an alkenyl group is a compound represented by the following general formula (IX) or the compound described below from the viewpoint of ease of deprotection with a photoacid generator and availability. (F) A compound obtained by reacting with a compound having a SiH group is preferable.

(In General Formula (IX), R ⁴ represents an alkyl group having 1 to 6 carbon atoms having no unsaturated bond, and each R ⁴ may be the same or different. R ⁵ is a structure that can be taken as a bisphenol structure. If any).

  In obtaining the (A) polysiloxane compound, the compound (E) having an alkenyl group may be used alone or in combination of two or more.

<1-6. (F) Compound having SiH group>
This positive photosensitive composition may contain the compound which has (F) SiH group. In addition, this positive photosensitive composition may contain the compound which has (F) SiH group separately from (A) polysiloxane compound, (F) By hydrosilylation reaction using the compound which has SiH group The obtained (A) polysiloxane compound may be included.

  (F) The compound having a SiH group is preferably a compound having two or more SiH groups in one molecule.

  The compound having two or more SiH groups in one molecule is not particularly limited, and examples thereof include siloxanes whose ends are blocked with dimethylhydrosilyl groups, cyclic siloxanes having SiH groups in the side chains, chain siloxanes, and cages. Examples thereof include siloxane. Among these, a cyclic siloxane compound having a SiH group in the side chain is particularly preferable from the viewpoint of obtaining a thin film having excellent insulating properties.

  Examples of the cyclic siloxane compound having a SiH group in the side chain include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-methyl-3,5, 7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-dimethyl-5,7-dihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1- Propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-dipropyl-5,7-dihydrogen-1,3,5,7-tetramethyl Cyclotetrasiloxane, 1,3,5-trihydrogen-7-hexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen- , 7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3 , 5,7,9-pentamethylcyclosiloxane and 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane. Among these, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane is particularly preferable from the viewpoint of availability.

  (F) When (A) a polysiloxane compound is obtained using a compound having a SiH group, the (A) polysiloxane compound has a structure in which an acidic group or a hydroxyl group is expressed by decomposition with an acid. The compound having a group and / or the compound having (F) SiH group must have a structure in which an acid group or a hydroxyl group is expressed by being decomposed by an acid.

  When the compound (F) having a SiH group has a structure in which an acidic group or a hydroxyl group is expressed by being decomposed by an acid, the structure in which the acidic group or the hydroxyl group is expressed by being decomposed by an acid is <1-1. (A) The structure demonstrated in the polysiloxane compound> is mentioned.

  The compound (F) having a SiH group may be a compound having an alkenyl group in addition to the SiH group. (A) In obtaining a polysiloxane compound, when using the compound which has (F) SiH group which has an alkenyl group, the compound which has (E) alkenyl group may be used and it is not necessary to use it.

  When (A) a polysiloxane compound is obtained, a compound having (F) SiH group having an alkenyl group is used, and when (E) a compound having alkenyl group is not used, (F) having an SiH group having the alkenyl group. The compound has a structure in which an acidic group or a hydroxyl group is expressed by being decomposed by an acid.

  When the amount of SiH group contained in the compound having (E) alkenyl group and / or the compound having (F) SiH group is X and the amount of alkenyl group is Y, the value of X / Y is 0.2 ≦ X / Y ≦ 5.0 is preferable, and from the viewpoint that a tough thin film can be obtained, 0.3 ≦ X / Y ≦ 3.0 is more preferable.

  In obtaining the (A) polysiloxane compound, the compound (F) having a SiH group may be used alone or in combination of two or more.

  In the positive photosensitive composition, at least one of the (E) compound having an alkenyl group and the (F) compound having an SiH group is preferably a siloxane compound. Of the compounds having the (E) alkenyl group and the compounds having the (F) SiH group, at least the compound having the (F) SiH group is a siloxane compound and more preferably has a cyclic siloxane structure. preferable. The reason is that the cured product has excellent heat resistance.

  Further, in the present positive photosensitive composition, when at least one of the compound having the (E) alkenyl group and the compound having the (F) SiH group is a siloxane compound, the siloxane compound is from 6 to It is preferable to contain a polysiloxane structure having a polyhedral skeleton formed from 24 Si atoms because the cured product is excellent in heat resistance, insulation, and the like. Hereinafter, the polysiloxane structure having a polyhedral skeleton formed from 6 to 24 Si atoms will be described in detail.

(Polysiloxane structure with polyhedral skeleton)
Examples of the polysiloxane structure having a polyhedral skeleton formed from 6 to 24 Si atoms include a polysiloxane structure having a polyhedral skeleton represented by the following formula (X) (here, 8 A polysiloxane structure having a polyhedral skeleton formed from Si atoms is exemplified as a representative example).

As a method for obtaining a polysiloxane structure having a polyhedral skeleton formed from 6 to 24 Si atoms, for example, general formula RSiX ₃ (wherein R is a polyhedral skeleton formed from 6 to 24 Si atoms) A method of hydrolyzing and condensing a silane compound represented by the following general formula RSiX: a group bonded to a silicon atom in a polysiloxane structure having a hydrogen atom, and X is a hydrolyzable functional group such as a halogen atom or an alkoxy group) after synthesizing the trisilanol compound having three silanol groups ₃ to hydrolysis and condensation reaction with the molecule further method for ring closure, and the like by reacting the same or different trifunctional silane compound.

  The polysiloxane structure having a polyhedral skeleton formed from 6 to 24 Si atoms includes a polysiloxane compound having a polyhedral skeleton formed from 6 to 24 Si atoms and an alkenyl group, and a siloxane compound having a SiH group. Is preferably obtained by hydrosilylation reaction, since it is highly compatible with other components, and a transparent and uniform film can be obtained.

  Examples of the siloxane compound having a SiH group include chain siloxane and cyclic siloxane. Specifically, a compound having two or more SiH groups in one molecule (excluding cage-like siloxane) described in the explanation of the compound having (F) SiH group can be used. A reticulated siloxane can also be used. Among these, it is preferable to use a cyclic siloxane having two or more SiH groups in one molecule because a tough film having excellent heat resistance can be obtained.

  The polysiloxane structure having a polyhedral skeleton formed from 6 to 24 Si atoms is preferably a structure typified by a polysiloxane structure represented by the following formula (XI) (here, 8 A polysiloxane structure having a polyhedral skeleton formed from a single Si atom is exemplified as a representative example). In a structure represented by the polysiloxane structure represented by the following formula (XI), a Si atom located at the apex of the polyhedral skeleton and a group having at least one SiH group or alkenyl group are bonded via a siloxane bond. In the case where at least one of the compound having the (E) alkenyl group and the compound having the (F) SiH group contained in the positive photosensitive composition is a siloxane compound. By using a compound having a structure represented by the polysiloxane structure represented by the following formula (XI) as the siloxane compound, a tough film can be obtained.

  A method for synthesizing a compound having a structure represented by the polysiloxane structure represented by the above formula (XI) is not particularly limited, and a known method can be used. For example, tetraalkoxysilane is converted to quaternary ammonium hydroxy. And a method of reacting with a silylating agent such as an alkenyl group-containing silyl chloride after hydrolytic condensation in the presence of a base such as alkenyl. In this synthesis method, a polysiloxane compound having a polyhedral skeleton is obtained by hydrolytic condensation reaction of tetraalkoxysilane, and the obtained polysiloxane compound is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride. It is possible to obtain a polysiloxane compound in which a silyl group having an alkenyl group is bonded to a Si atom located at the apex of the polyhedral skeleton through a siloxane bond.

  Moreover, it is possible to obtain a polysiloxane compound having a similar polyhedral skeleton from a substance containing silica such as silica or rice husk instead of tetraalkoxysilane.

  Examples of the tetraalkoxysilane include tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane. These tetraalkoxysilanes may be used alone or in combination of two or more.

  Examples of the quaternary ammonium hydroxide include 2-hydroxyethyltrimethylammonium hydroxide and tetramethylammonium hydroxide. These quaternary ammonium hydroxides may be used alone or in combination of two or more.

  The polysiloxane structure having a polyhedral skeleton formed from 6 to 24 Si atoms has the following general formula (XII):

(In General Formula (XII), R ¹ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and at least one of R ¹ is a hydrogen atom or an alkenyl group. Each R ¹ is the same or different. A polysiloxane compound having a polyhedral skeleton represented by the following general formula (XIII),

(In General Formula (XIII), R ² is an organic group having 1 to 6 carbon atoms, and R ³ is a hydrogen atom or an alkenyl group. Each R ² and R ³ may be the same or different. Can be obtained by hydrosilylation reaction with a cyclic siloxane compound represented by the formula: 0-10, m represents the number of 1-10), to obtain a strong and heat-resistant film It is preferable because it is possible.

  In addition, when the polysiloxane compound having a polyhedral skeleton represented by the general formula (XII) is a compound having an alkenyl group, the cyclic siloxane compound represented by the general formula (XIII) is a compound having a SiH group. In addition, when the polysiloxane compound having a polyhedral skeleton represented by the general formula (XII) is a compound having a SiH group, the cyclic siloxane compound represented by the general formula (XIII) is alkenyl. It must be a compound having a group.

  When the polysiloxane structure having a polyhedral skeleton formed from 6 to 24 Si atoms is a polysiloxane structure represented by the above formula (X), the content of the polysiloxane structure in the positive photosensitive composition is It is preferably 2 to 40% by weight, more preferably 3 to 30% by weight, still more preferably 4 to 20% by weight, more preferably 4 to 10% by weight based on 100 parts by weight of the component excluding the solvent. % Is particularly preferred. By setting the content within this range, it is possible to obtain an insulating film that is strong and excellent in heat resistance, has a low dielectric constant, and has a small leakage current and an excellent electrical insulation characteristic.

<1-7. Other additives>
(Alkali-soluble component)
Since this positive photosensitive composition further contains an alkali-soluble component, the solubility of the positive photosensitive composition in an alkaline developer is improved, and a highly sensitive positive photosensitive composition is obtained. preferable.

  Examples of the alkali-soluble component include a compound having a structure represented by the following formula (X1) or (X2), a phenol resin having a phenol group, an acrylic resin having a carboxyl group, an amide resin, and an imide resin. .

  The said alkali-soluble component may be used independently and may use 2 or more types together.

  The alkali-soluble component is a compound having a structure represented by the following formula (X1) or (X2) from the viewpoint that a thin film excellent in insulation, heat resistance and solvent resistance can be obtained after baking. Is preferable, and a polysiloxane compound having a structure represented by the following formula (X1) or (X2) is more preferable.

  As a method for obtaining a polysiloxane compound having a structure represented by the above formula (X1) or (X2), for example, a method having a structure and an alkenyl group represented by the above (X1) or (X2) can be used. Examples thereof include a method in which a compound is partially hydrosilylated with a siloxane compound having a SiH group.

  Examples of the compound having a structure and an alkenyl group represented by the above formula (X1) or (X2) include diallyl isocyanuric acid and monoallyl isocyanuric acid.

  Examples of the siloxane compound having a SiH group include the above <1-6. (F) The compound etc. which were demonstrated by description of the compound which has SiH group> as a compound which has two or more SiH groups in 1 molecule are mentioned.

  When the positive photosensitive composition contains the alkali-soluble component, the upper limit of the content of the alkali-soluble component is 80 parts by weight with respect to 100 parts by weight of the component obtained by removing the solvent from the positive photosensitive composition. It is preferable that the amount is 75 parts by weight. On the other hand, the lower limit of the content is preferably 15 parts by weight, more preferably 20 parts by weight, and even more preferably greater than 50 parts by weight. By setting the content of the alkali-soluble component in this range, a positive photosensitive composition excellent in alkali developability can be obtained.

(Hydrosilylation reaction inhibitor)
In the present positive photosensitive composition, a hydrosilylation reaction inhibitor may be used to ensure storage stability.

  Examples of the hydrosilylation reaction inhibitor include compounds containing aliphatic unsaturated bonds, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides.

  Examples of the compound containing an aliphatic unsaturated bond include propylene such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 1-ethynyl-1-cyclohexanol. Examples include gill alcohols, ene-yne compounds, and maleic acid esters such as dimethyl malate.

  Examples of the organophosphorus compounds include triorganophosphines such as triphenylphosphine, diorganophosphines, organophosphines, and triorganophosphites.

  Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole and benzothiazole disulfide.

  Examples of the tin compound include stannous halide dihydrate and stannous carboxylate.

  Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  These hydrosilylation reaction inhibitors may be used alone or in combination of two or more.

  Among these hydrosilylation reaction inhibitors, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1 are preferable from the viewpoint of good delayed activity and easy availability of raw materials. -Cyclohexanol or triphenylphosphine is preferred.

(solvent)
The positive photosensitive composition preferably contains a solvent. By containing the solvent, when the positive photosensitive composition is cured to obtain a cured film, the viscosity of the positive photosensitive composition can be lowered, and as a result, uniform application can be achieved. It is.

  Examples of the solvent include, but are not limited to, hydrocarbon solvents such as ethylcyclohexane and trimethylpentane, ether solvents such as 1,4-dioxane and 1,3-dioxolane, and ketone solvents such as methyl isobutyl ketone and cyclohexanone. Solvents, ester solvents such as isobutyl isobutyrate and isobutyl butyrate, glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), ethylene glycol dimethyl ether and ethylene glycol diethyl ether, and halogens such as trifluorotoluene System solvents and the like.

  These solvents may be used alone or as a mixed solvent of two or more kinds.

  From the viewpoint of easily forming a uniform film, the solvent is preferably 1,4-dioxane, isobutyl isobutyrate, propylene glycol-1-monomethyl ether-2-acetate, methyl isobutyl ketone, ethylene glycol dimethyl ether or ethylene glycol diethyl ether. It is preferable that

  When the present positive photosensitive composition contains a solvent, the content thereof is not particularly limited and can be appropriately set. However, the lower limit is 10 parts by weight with respect to 100 parts by weight of the total amount of the positive photosensitive composition excluding the solvent. Preferably, it is 30 parts by weight, more preferably 50 parts by weight. On the other hand, the upper limit of the content is preferably 800 parts by weight, more preferably 400 parts by weight, and even more preferably 300 parts by weight.

  If content of the said solvent is 10 weight part or more, effects, such as low viscosity by a solvent, will be acquired. On the other hand, if the content of the solvent is 800 parts by weight or less, it is possible to prevent thermal cracks and the like due to the solvent remaining when the cured film is produced, and there is no disadvantage in cost. Industrial use value does not decrease.

(Adhesion improver)
It is also possible to add an adhesion improver to the positive photosensitive composition. Examples of the adhesion improver include, in addition to commonly used adhesives, various coupling agents, epoxy compounds, oxetane compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methyl. Examples thereof include styrene-vinyltoluene copolymer, polyethylmethylstyrene, and aromatic polyisocyanate.

  An example of the coupling agent is a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handleability. From the viewpoint of the curability and adhesiveness of the film, an epoxy group, a methacryl group or an acrylic group is particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group or an ethoxysilyl group is particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4- (Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane and acryloxymethyltriethoxysilane Alkoxysilanes having a drill group can be exemplified.

  The addition amount of the silane coupling agent can be variously set, but it is preferably 0.1 to 20 parts by weight, and 0.3 to 10 parts by weight with respect to 100 parts by weight of the (A) polysiloxane compound. Is more preferably 0.5 to 5 parts by weight. If the addition amount is 0.1 parts by weight or more, the effect of improving adhesiveness is sufficiently exhibited. Moreover, if the addition amount is 20 parts by weight or less, adverse effects on the physical properties of the cured film can be prevented.

(Thermoplastic resin)
Various thermoplastic resins can be added to the positive photosensitive composition for the purpose of modifying the characteristics. Various thermoplastic resins can be used. For example, a homopolymer of methyl methacrylate or a polymethyl methacrylate resin such as a random, block or graft polymer of methyl methacrylate and other monomers (for example, Hitachi Chemical) Optretz, etc.), acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3, A polycarbonate resin such as a polycarbonate resin containing 3,5-trimethylcyclohexylidenebisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), a norbornene derivative, a vinyl monomer, or the like is copolymerized alone or copolymerized. Cycloolefin resins such as fat, norbornene derivative ring-opening metathesis polymer, or hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), ethylene and Olefin-maleimide resins such as copolymers with maleimide (eg, TI-PAS manufactured by Tosoh Corporation), bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene, and diols such as diethylene glycol Polyesters such as polyesters obtained by polycondensation of phthalic acids such as terephthalic acid and isophthalic acid, and aliphatic dicarboxylic acids (for example, O-PET manufactured by Kanebo Co., Ltd.), polyethersulfone resins, polyarylate resins, Polyvinyl acetate Resins, polyethylene resins, polypropylene resins, polystyrene resins, polyamide resins, silicone resins, as well as other such fluororesin is not intended but rubber resin such as natural rubber and EPDM are illustrated as being limited thereto.

  The thermoplastic resin may have an alkenyl group and / or a SiH group in the molecule. From the viewpoint that the obtained cured product tends to be tougher, it is preferable that the molecule has at least one alkenyl group and / or SiH group in the molecule.

  The thermoplastic resin may have other crosslinkable groups. Examples of the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the resulting cured film is likely to be high, it is preferable to have one or more crosslinkable groups per molecule on average.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10,000 or less, preferably 5000 or less, in view of easy compatibility with the (A) polysiloxane compound. It is more preferable. On the contrary, the number average molecular weight is preferably 10,000 or more, and more preferably 100,000 or more in that the obtained cured product tends to be tough. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, in that the viscosity of the mixture tends to be low and the moldability tends to be good. More preferably, it is as follows. Although there is no limitation in particular as a compounding quantity of a thermoplastic resin, it is preferable that it is 5 to 50 weight% of the whole positive photosensitive composition, and it is more preferable that it is 10 to 30 weight%. If the amount added is small, the resulting cured film tends to be brittle. If the amount added is large, the heat resistance (elastic modulus at high temperature) of the cured film tends to be low.

  A single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.

  The thermoplastic resin may be dissolved in the (A) polysiloxane compound and mixed in a uniform state, pulverized and mixed in a particle state, or dissolved in a solvent and mixed to be dispersed. It is good. In the point that the hardened | cured material obtained becomes easy to become more transparent, it is preferable to melt | dissolve in (A) polysiloxane compound and to mix in a uniform state. Also in this case, the thermoplastic resin may be directly mixed with the (A) polysiloxane compound, or may be uniformly mixed using a solvent or the like, and then the solvent is removed and the dispersion is uniformly dispersed and / or mixed. It is good also as a state.

  When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle diameters, but from the viewpoint that the positive photosensitive composition has a low viscosity and tends to have good moldability. The particle diameter variation coefficient is preferably 10% or less.

(Filler)
If necessary, a filler may be added to the positive photosensitive composition. Various fillers are used as the filler. For example, silica, fume silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, silica fine filler such as amorphous silica, silicon nitride, Inorganic fillers such as silver powder, alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, white clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate and inorganic balloon First, as fillers for conventional sealing materials such as epoxy-based fillers, fillers that are generally used and / or proposed can be mentioned.

(Anti-aging agent)
An anti-aging agent may be added to the positive photosensitive composition in order to ensure storage stability. Examples of the anti-aging agent include citric acid, phosphoric acid, and sulfur-based anti-aging agents, in addition to the anti-aging agents generally used such as hindered phenols.

  As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.

  Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds Thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides and sulfoxides.

  These anti-aging agents may be used alone or in combination of two or more.

(Radical inhibitor)
In order to ensure storage stability, a radical inhibitor may be added to the positive photosensitive composition. Examples of radical inhibitors include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol) and tetrakis (methylene- 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) phenolic radical inhibitors such as methane, and phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondarybutyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine and N, N′-diphenyl-p-phenylenediamine.

  These radical inhibitors may be used alone or in combination of two or more.

(Other additives)
The positive photosensitive composition includes other ions such as a colorant, a release agent, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, a repellent, and antimony-bismuth. Trapping agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity The purpose of the present invention is to provide an imparting agent, an antistatic agent, a radiation shielding agent, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity imparting agent and / or a physical property modifier. It can add in the range which does not impair an effect.

[2. Method for preparing positive photosensitive composition and method for producing cured film]
<2-1. Method for preparing positive photosensitive composition>
The method for preparing the present positive photosensitive composition is not particularly limited, and various methods can be used. [1. Various components described in “Positive photosensitive composition” may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance.

<2-2. Method for producing cured film>
The present invention also includes a cured film obtained from the present positive photosensitive composition. As a method of curing the positive photosensitive composition to obtain a cured film, for example, after coating the positive photosensitive composition on various substrates, the positive photosensitive composition is used using a mask having a desired shape. The method etc. which obtain the cured film formed in the pattern shape by exposing to a property composition and melt | dissolving and removing an exposed part can be used.

  The method of coating the positive photosensitive composition on various substrates is not particularly limited as long as it can be uniformly applied, and generally used coating methods can be used. For example, methods such as spin coating, slit coating, dip coating, roll coating, screen coating, spray coating, spin casting, flow coating, screen printing, ink jet or drop casting can be used.

  Moreover, you may perform the viscosity adjustment by a solvent, and / or the surface tension adjustment by surfactant, etc. suitably according to the state of various base materials.

  The thickness of the cured film is not particularly limited, but is preferably 0.05 μm to 100 μm, more preferably 0.1 μm to 80 μm, and further preferably 0.2 μm to 50 μm from the viewpoint of reliability. preferable.

  After coating the positive photosensitive composition on various substrates, a pre-bake and / or vacuum devolatilization process may be performed before exposure for the purpose of solvent removal. However, the temperature of the pre-bake is preferably 100 ° C. or less, and more preferably 80 ° C. or less because there is a possibility that problems such as deterioration of developability may occur due to the application of heat.

  In addition, you may perform a vacuum devolatilization process and prebaking simultaneously.

  As a light source for exposing the present positive photosensitive composition, a light source that emits an absorption wavelength of (B) photoacid generator and (D) sensitizer to be used may be used, and the range is 365 nm to 425 nm. For example, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, a carbon arc lamp, or a light emitting diode can be used.

At this time, the exposure is not particularly limited, is preferably 1~5000mJ / cm ^2, more preferably 1~3000mJ / cm ^2, further preferably 1~1000mJ / cm ² .

  You may heat after exposing this positive photosensitive composition. By heating, the unexposed part is cured and the contrast becomes clear.

  As heating temperature, it is preferable that it is 50-120 degreeC, and since contrast becomes clearer, it is more preferable that it is 55-110 degreeC, and it is further more preferable that it is 60-100 degreeC.

  A method for forming the pattern by dissolving and removing the exposed portion after exposure to the present positive photosensitive composition is not particularly limited, and a commonly used development method such as a dipping method or a spray method may be used. it can.

  In this case, the developer can be used without particular limitation as long as it is generally used. Specific examples thereof include, for example, organic alkali aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution and choline aqueous solution, Inorganic alkaline aqueous solutions such as potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution, and alcohol and / or surfactant etc. were added to these aqueous solutions to adjust the dissolution rate etc. And various organic solvents.

  Further, after the exposed portion is dissolved and removed, post-baking may be performed to improve the strength and reliability of the cured film.

  The post-baking temperature is preferably 100 to 300 ° C, more preferably 120 to 270 ° C, and further preferably 150 to 250 ° C.

  In addition, when using a plastic substrate as a base material, it is preferable to post-bake at the lowest possible temperature. However, since this positive photosensitive composition can be post-baked at 150 ° C. to 200 ° C., in such a case. Even if it exists, it can post-bake without adversely affecting the substrate.

  When the positive photosensitive composition is cured to obtain a cured film, the curing reaction can be advanced by heating and post-baking after dissolving and removing the exposed portion, thereby producing a highly insulating cured film. Can be obtained.

  Examples of the curing reaction include a sol-gel reaction and a hydrosilylation reaction. The curing reaction is preferably a hydrosilylation reaction from the viewpoint of obtaining a cured film having particularly excellent insulating properties at a lower temperature. The hydrosilylation reaction proceeds by the presence of a compound having an alkenyl group, a compound having a SiH group, and a hydrosilylation catalyst in the positive photosensitive composition.

  By the above method, the cured film formed in the pattern form which consists of this positive photosensitive composition can be obtained.

[3. Characteristics of positive photosensitive composition)
In the present specification, indices used to express the characteristics of the positive photosensitive composition will be described below.

<3-1. Sensitivity of positive photosensitive composition>
The positive photosensitive composition has excellent sensitivity due to the various components described above.

  In this specification, when the cured film can be obtained with a smaller exposure amount, that is, the “exposure amount” when obtaining the cured film from the positive photosensitive composition by the method for producing a cured film, the sensitivity is obtained. When the value of is small, it is expressed as “sensitive”.

  The advantage that the positive photosensitive composition has an excellent sensitivity is not only the advantage that the manufacturing cost can be reduced, but also it can suppress an unwanted reaction in an unexposed portion and obtain a positive patterning with an excellent resolution. It also has the advantage of being possible.

  In this specification, in producing a cured film having a width of 10 μm, exposure was performed while changing the exposure amount by 2 mJ, and the exposure amount at which the line width of the cured film line was 10 μm was defined as “sensitivity”. A specific measuring method will be described in Examples described later.

The sensitivity is preferably 50 mJ / cm ² or less, more preferably 40 mJ / cm ² or less, further preferably 30 mJ / cm ² or less, particularly preferably 15 mJ / cm ² or less .

<3-2. Process margin when producing a cured film from a positive photosensitive composition>
Since this positive photosensitive composition has the above-described various components, it has an excellent process margin when producing a cured film.

  In the present specification, the above-mentioned “process margin when producing a cured film” refers to the stability when the “time from the end of exposure to the start of development” varies in the method for producing a cured film. Is sometimes referred to simply as “process margin”.

  In producing a cured film, when a positive photosensitive composition is exposed using a mask having a desired shape, acid is generated in the exposed portion due to the action of (B) photoacid generator and (D) sensitizer. To do. By the action of the acid, the alkali solubility of the polysiloxane compound (A) is increased, and the positive photosensitive composition is removed from the exposed portion by development. The acid generated in the exposed part also diffuses into the unexposed part. However, the effect of the diffused acid is canceled by the action of the basic compound present in the unexposed part, and a cured film is produced in the unexposed part after development. Since the diffusion spreads with time, the longer the time until development, or if the acid effect cannot be sufficiently canceled due to the physical properties or content of the basic compound, even in the unexposed part. The alkali solubility of the polysiloxane compound (A) is increased by the action of the acid, and the positive photosensitive composition is removed by development. Therefore, if the physical property or content of the basic compound is suitable, the process margin is excellent. In addition, an excellent process margin is important in producing a cured film excellent in patterning. A specific measurement method and definition of the process margin will be described in an example described later.

  In the present specification, when a cured film having a width of 10 μm is produced by setting the time from the end of exposure to the start of development to 15 minutes, the amount of change from 10 μm in the width (μm) of the produced cured film The amount of change was defined as “line width stability”, and a small value of the line width stability was defined as “good process margin”.

  The line width stability value is preferably less than 1.0 μm, more preferably less than 0.7 μm, further preferably less than 0.5 μm, and particularly preferably less than 0.3 μm. preferable.

<3-3. Insulation of cured film>
The cured film obtained by the above method functions as an excellent insulating film. An insulating film used for an LSI, TFT, touch panel or the like is required to have a small leakage current. Specific measurement methods and definitions will be described in the examples described later.

If the thickness of the cured film is 1 [mu] m, the leak current is preferably at 10 nA / cm ² or less, more preferably 5 nA / cm ² or less, still more preferably less 4nA, 3 nA / cm Particularly preferred is ² or less.

[4. (Use)
This positive photosensitive composition and cured film can be used for various applications. It can be applied to various uses where conventional acrylic resin and epoxy resin adhesives are used. Hereinafter, applications of the present positive curable composition and cured film will be exemplified.

  Applications of the positive photosensitive composition and the cured film of the present invention include, for example, transparent materials, optical materials, optical lenses, optical films, optical sheets, adhesives for optical components, optical adhesives for coupling optical waveguides, and optical waveguides. Peripheral member fixing adhesive, DVD bonding adhesive, pressure-sensitive adhesive, dicing tape, electronic material, insulating material (including printed circuit board, wire coating, etc.), high voltage insulating material, interlayer insulating film, TFT passivation film, Gate insulation film for TFT, interlayer insulation film for TFT, transparent flattening film for TFT, packing for insulation, insulation coating material, adhesive, high heat-resistant adhesive, high heat dissipation adhesive, optical adhesive, adhesion of LED element Agent, adhesive for various substrates, heat sink adhesive, paint, UV powder paint, ink, colored ink, UV inkjet ink, coating material (hard coat, sheet Film, release paper coat, optical disc coat, optical fiber coat, etc.), molding materials (including sheets, films, FRP, etc.), sealing materials, potting materials, sealing materials, light emitting diode sealing materials, Optical semiconductor encapsulant, liquid crystal sealant, display device sealant, electrical material encapsulant, various solar cell encapsulant, high heat resistant encapsulant, resist material, liquid resist material, colored resist, dry film resist material , Solder resist material, color filter binder resin, color filter transparent flattening material, black matrix binder resin, liquid crystal cell photo spacer material, OLED element transparent sealing material, stereolithography, solar cell material, fuel cell Materials, display materials, recording materials, anti-vibration materials, waterproof materials, moisture-proof materials, heat shrinkage Muchubu, O-ring, copier photosensitive drums, can be applied to the solid electrolyte and the gas separation membrane for a battery. In addition to concrete protective materials, linings, soil injection agents, cold storage heat materials, sealing materials for sterilization apparatuses, contact lenses, oxygen permeable membranes, additives to other resins, and the like.

  Among these, the positive photosensitive composition is a material that can be used as an alkali-developable transparent resist, and is particularly suitable as an FPD material. More specifically, a passivation film for TFT, a gate insulating film for TFT, an interlayer insulating film for TFT, a transparent planarizing film for TFT, a binder resin for color filter, a transparent planarizing material for color filter, a binder resin for black matrix, Examples thereof include a photospacer material for liquid crystal cells and a transparent sealing material for OLED elements.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example.

  First, a method for producing a positive photosensitive composition will be described.

(Synthesis of functional group-protected bisphenol S compound)
In a 100 mL eggplant flask, 20 g of tetrahydrofuran (THF) and 5 g of diallyl bisphenol S were added and stirred at room temperature. After becoming a uniform solution, 2.5 g of hexamethyldisilazane was added to the eggplant flask and allowed to react at room temperature for 2 hours. THF and the reaction residue were distilled off under reduced pressure, and the presence of a peak derived from a trimethylsilyl group and the disappearance of the peak derived from a hydroxyl group were confirmed using ¹ H-NMR (manufactured by Bruker, Avance III). By the above operation, 6.5 g of diallyl bisphenol S (reaction product 1) having a hydroxyl group protected with a trimethylsilyl group was obtained.

(Synthesis Example 1)
In a 100 mL four-necked flask, 20 g of toluene and 3 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane were added, and the gas phase portion was purged with nitrogen. The inside of the four-necked flask was heated to 100 ° C. and stirred at the same time. 5 g of the above reaction product 1, 1.5 g of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) A mixed solution containing 0.7 mg and 5 g of toluene was dropped into the four-necked flask.

After dropping, disappearance of the peak derived from the allyl group was confirmed using ¹ H-NMR. And toluene was depressurizingly distilled from the said 4 necked flask, and the "reactant A" which is a colorless and transparent liquid was obtained. ^According to the measurement using ¹ H-NMR, the reactant A has a bisphenol S structure protected with a trimethylsilyl group, and has an SiH group of 3.0 mmol / g in terms of equivalent when the standard substance is dibromoethane. It was confirmed that it was a polysiloxane compound.

(Examples 1-4 and Comparative Examples 1-3)
Reactant A, photoacid generator (manufactured by Toyo Gosei Chemical Co., Ltd., trade name: NR-TF or Toyo Gosei Chemical Co., Ltd., trade name: TTBPS-PFBS), sensitizer (DBA (9 , 10-dibutoxyanthracene), manufactured by Kawasaki Kasei Kogyo Co., Ltd.), basic compound (BME (bis (2-morpholinoethyl) ether) having a molecular weight of 244, BPPS (bis (1,2, sebacate) having a molecular weight of 508) 2,6,6-pentamethyl-4-piperidyl)) or DCHA (dicyclohexylamine) having a molecular weight of 181), a compound having an alkenyl group (TAIC (triallyl isocyanurate)) and a solvent (PGMEA (propylene glycol-1-monomethyl) Ether-2-acetate)) in the proportions (parts by weight) listed in Table 1. Type photosensitive composition was prepared.

  As shown in Table 1, the positive photosensitive composition of Comparative Example 1 does not contain a basic compound. In the positive photosensitive composition of Comparative Example 2, the ratio of the weight part of the basic compound to the weight part of the photoacid generator exceeds 0.5. In the positive photosensitive composition of Comparative Example 3, the basic compound added has a molecular weight of less than 220.

  Next, a method for producing a cured film using the positive photosensitive composition will be described.

(Thin film formation and patterning)
The positive photosensitive compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were applied on an alkali-free glass substrate 50 mm × 50 mm by spin coating. Then, the said glass substrate was prebaked for 2 minutes at 100 degreeC using the hotplate, and the photosensitive thin film with a film thickness of 2.5 micrometers was formed into a film on the said alkali free glass substrate. The photosensitive thin film was exposed (10 to 50 mJ / cm ² ) through a photomask using a mask aligner (manufactured by Dainippon Kaken, MA-1300). Thereafter, the alkali-free glass substrate coated with the photosensitive thin film was immersed in an alkali developer (manufactured by Tama Chemical Industry Co., Ltd., TMAH 2.38% aqueous solution) at 23 ° C. for 70 seconds for development treatment. Further, a non-alkali glass substrate coated with the photosensitive thin film was post-baked at 230 ° C. for 30 minutes using an oven to form a cured film.

  Next, the sensitivity of the photosensitive thin film formed by the positive photosensitive compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3, the process margin in the process of producing a cured film from the photosensitive thin film, and Each evaluation method regarding the insulating property of the cured film will be described.

(Sensitivity measurement and process margin)
When each cured film is produced on an alkali-free glass substrate by the above method using the positive photosensitive compositions of Examples 1 to 4 and Comparative Examples 1 to 3, a 10 μm wide line and space pattern exists. Using the photomask, the exposure was performed while changing the exposure amount by ² mJ, and the exposure amount at which the line width was 10 μm was defined as sensitivity (mJ / cm ² ). At this time, the time from exposure to the start of development was 2 minutes. Furthermore, development is started from exposure when each cured film is produced on an alkali-free glass substrate by the above method using each of the positive photosensitive compositions of Examples 1 to 3 and Comparative Examples 1 to 3. The cured time was 15 minutes, and a cured film was produced with the above-mentioned sensitivity and the exposure amount specified. From the change amount of the line width (change amount from 10 μm), the process margin was evaluated according to the following criteria. A laser microscope (manufactured by Olympus, LEXT 4000) was used for observing the amount of change in line width.
○: Change in line width is less than 0.5 μm.
(Triangle | delta): The variation | change_quantity of line | wire width is 0.5 micrometer or more and less than 1.0 micrometer.
X: The variation | change_quantity of line | wire width is 1.0 micrometer or more.

(Insulation evaluation)
Each cured film is obtained by the same method as described above using the positive photosensitive compositions of Examples 1 to 4 and Comparative Examples 1 to 50 on an alkali-free glass substrate 50 mm × 50 mm on which Mo is deposited. Further, an Al electrode (6 mmφ) was formed on the cured film by sputtering.

For insulation, a precision semiconductor parameter analyzer measuring device (manufactured by Agilent, 4156C) is used, and a voltage of 0 V to 50 V is stepped in steps of 0.5 V between the electrodes sandwiching the cured film (between Mo and Al). The amount of leakage current per unit electrode area (nA / cm ² ) when 30 V was applied was measured, and the insulation was evaluated.

  Table 2 shows the results of sensitivity measurement, process margin and insulation evaluation.

  A photosensitive thin film formed from the present positive photosensitive composition can be formed into a positive pattern. Further, the positive photosensitive compositions shown in Examples 1 to 4 have good sensitivity as compared with the photosensitive thin film formed by the positive composition in Comparative Examples 1 to 3. It exhibits excellent characteristics in the process margin when forming a cured film from these photosensitive thin films, and the insulation reliability of the formed cured film is also good.

  In addition, in Example 1 which added NR-TF as a photo-acid generator, the result that the sensitivity was further excellent was obtained compared with Example 2 which added TTBPS-PFBS as a photo-acid generator.

  Since the present invention is a positive photosensitive composition that can be positively patterned and can form a highly reliable insulating film, it can be used in display fields such as liquid crystal displays and organic EL displays.

Claims (6)

(A) a polysiloxane compound whose alkali solubility is increased by the action of an acid, (B) a photoacid generator and (C) a basic compound having a molecular weight of 220 or more, and the following (1) and (2): A positive photosensitive composition characterized by satisfying:
(1) It has sensitivity in an exposure wavelength range of 365 nm to 425 nm;
(2) The weight ratio of the basic compound (C) having a molecular weight of 220 or more to the (B) photoacid generator is 0.02 to 0.5. 2. The positive photosensitive composition according to claim 1, wherein the photoacid generator (B) is a compound having a structure represented by the following formula (I).

(In formula (I), X is an anion).   The positive photosensitive composition according to claim 1, wherein the photoacid generator (B) is a compound having a substituted phenyl group.   Furthermore, (D) sensitizer is included, The positive photosensitive composition of any one of Claims 1-3 characterized by the above-mentioned. The polysiloxane compound whose alkali solubility is increased by the action of the acid (A) has a SiH group,
The positive photosensitive composition according to any one of claims 1 to 4, wherein the positive photosensitive composition contains (E) a compound having an alkenyl group.   The cured film obtained from the positive photosensitive composition of any one of Claims 1-5.