JP2014118418A - Silsesquioxane derivative and negative photosensitive resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having high heat resistance, good alkali developability and superior physical properties of a coating film, which can be suitably used as a protective film, an insulating resin or a resist resin.SOLUTION: A silsesquioxane derivative having a monovalent group expressed by -X-NHCO-Y-COOH and a photo-curable functional group is provided; and a negative photosensitive resin composition including the above derivative is provided. In the above formula, X represents a single bond, an alkylene group or an arylene group having 1 to 6 carbon atoms, or -R5-NH-R6- (where R5 and R6 each represent an alkylene group having 1 to 3 carbon atoms, and R5 and R6 may be identical or different from each other); Y represents a divalent group obtained by removing each one hydrogen atom bonded to two cyclic carbon atoms from an aromatic cyclic group or an alicyclic group, or a divalent alkylene group having 1 to 4 carbon atoms which may have a branched chain and/or a double bond.

Description

  The present invention relates to a silsesquioxane derivative, and more particularly, to a silsesquioxane derivative that provides an alkali-developable resin composition that can be suitably used for a negative photosensitive resin composition having high heat resistance.

  Insulating resins and resist resins used in various electronic circuit devices including semiconductor devices are made of photosensitive resin. The photosensitive resin is required to have heat resistance for improving performance as well as alkali developability.

  A conventionally known alkali-developable resin composition using an organic resin does not have sufficient performance in heat resistance. On the other hand, photosensitive resin compositions using silsesquioxane are known (for example, Patent Document 1 and Patent Document 2).

  The photosensitive resin composition using the silsesquioxane derivative disclosed in Patent Document 1 is a positive type. However, this film has insufficient film properties and is not suitable for use as an insulating film, for example. Moreover, although the silsesquioxane containing photosensitive resin composition disclosed by patent document 2 uses the radically polymerizable monomer for photosensitive expression, it does not have high heat resistance.

JP 2001-100420 A JP 2012-088610 A

  Accordingly, the present invention provides a resin composition that has high heat resistance and good alkali developability, has excellent coating film properties, and can be suitably used as a protective film resin, insulating resin or resist resin. With the goal.

  The present invention is a structural unit represented by the following chemical formula (1):

[In the chemical formula (1), R is
-X-B-Y-COOH (wherein X is a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group, or -R5-NH-R6- (wherein R5 and R6 have 1 to 3 carbon atoms) R5 and R6 may be the same or different, and Y represents one hydrogen atom of each of two ring carbon atoms from an aromatic ring group or an alicyclic group. Represents a divalent group generated by removal or a divalent alkylene group having 1 to 4 carbon atoms which may have a branched chain and / or a double bond; B represents —NHCO— or —CONH—; Wherein X and / or Y may have at least one group selected from the group consisting of a (meth) acryl group, a vinyl group and an epoxy group as a substituent. Valent group (L), or -ZA (wherein Z is a single bond, 1 carbon atom) Represents a monovalent group (M represents an alkylene group or an arylene group of -6, and A represents at least one group selected from the group consisting of a (meth) acryl group, a vinyl group, and an epoxy group). ). ]
A silsesquioxane derivative containing the above (provided that the derivative contains at least one constituent unit having the group (L) among the constituent units contained therein, any constituent unit thereof) The group (L) in the inside does not necessarily have any group of (meth) acryl group, vinyl group and epoxy group, and the derivative contains at least one structural unit having the group (M).) ,
Negative photosensitive resin composition containing the silsesquioxane derivative as a resin component, and
In a semiconductor device containing an interlayer insulating film using the negative photosensitive resin composition, and a method of manufacturing an electronic component that is finely processed by a photolithography method, a photoresist film using the negative photosensitive resin composition A method for manufacturing an electronic component, comprising the step of forming

(1) The present invention provides an alkali developable resin composition having high heat resistance. That is, an alkali developable resin composition that eliminates the drawbacks of heat resistance due to the use of the organic resin component and can form a resin film having excellent performance in terms of colorability and remaining film ratio even when heated is provided.
(2) The negative photosensitive resin composition containing the silsesquioxane derivative of the present invention as a resin component is excellent in film formability as compared with conventional ones. That is, since a polymer of a silsesquioxane derivative is formed, a cured film having excellent pencil hardness can be formed.

  The silsesquioxane derivative of this invention contains the structural unit represented by the said Chemical formula (1). R in the structural unit of the chemical formula (1) represents a monovalent group (L) represented by —X—B—Y—COOH or a monovalent group (M) represented by —ZA.

  X in the group (L) represents a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group, or -R5-NH-R6- (wherein R5 and R6 represent an alkylene group having 1 to 3 carbon atoms). R5 and R6 may be the same or different.), Y represents an aromatic ring group or an alicyclic group formed by removing one hydrogen atom from each of two ring carbon atoms. A divalent group or a divalent alkylene group having 1 to 4 carbon atoms which may have a branched chain and / or a double bond is represented, and B represents —NHCO— or —CONH—. However, X and / or Y may have at least one group selected from the group consisting of a (meth) acryl group, a vinyl group and an epoxy group as a substituent.

Specifically as a C1-C6 alkylene group in said X, a methylene group, ethylene group, a propylene group, a butylene group etc. can be mentioned, for example. The arylene group for X is preferably one having 6 to 10 carbon atoms. As such a thing, a phenylene group (ortho, meta, para, etc.), a naphthylene group (1,4-, 1,5-, 2,6-etc.) Etc. can be mentioned, for example. The -R5-NH-R6- in the X, specifically, for _{example, -CH 2 -NH-CH 2 -} , - (CH 2) 2 -NH- (CH 2) 2 -, - (CH 2 ) ₃ -NH- (CH ₂ ) _3- , -CH ₂ -NH- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -NH-CH ₂ -,-(CH ₂ ) ₂ -NH- (CH ₂ ) ₃ —, — (CH ₂ ) ₃ —NH— (CH ₂ ) ₂ —, —CH ₂ —NH— (CH ₂ ) ₃ —, — (CH ₂ ) ₃ —NH—CH ₂ — and the like. it can.

  Examples of the aromatic ring in Y include an aromatic ring having 6 to 10 carbon atoms which may have a substituent having 1 to 2 carbon atoms (for example, a benzene ring, a naphthalene ring, a tolyl group, a xylyl group, etc.). be able to. Examples of the alicyclic ring in Y include an alicyclic group having 5 to 10 carbon atoms (for example, a monocyclic cycloalkyl group, a monocyclic cycloalkenyl group, a bicyclic alkyl group, a cage alkyl group, etc.). For example, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a dicyclopentadiene ring, a norbornane ring, a norbornene ring, a cubane ring, and a basuketan ring. Specific examples of the alkylene group having 1 to 4 carbon atoms which may have a branched chain and / or a double bond in Y include, for example, a methylene group, an ethylene group, a propylene group, a vinylene group, (2 -Octenyl) ethylene group, (2,4,6-trimethyl-2-nonenyl) ethylene group and other alkylene groups, double bond alkylene groups or alkylene groups having 1 to 9 carbon atoms. it can.

  Z in the group (M) represents a single bond, an alkylene group having 1 to 6 carbon atoms or an arylene group, and A represents at least one selected from the group consisting of a (meth) acryl group, a vinyl group and an epoxy group. Represents a group. The above-mentioned thing can be illustrated as said C1-C6 alkylene group and said arylene group.

  As specific examples of the monovalent group (L) represented by the above -X-B-Y-COOH, for example, combinations of X, B and Y are as shown in Table 1 below. Y in the table indicates two bonds, one of which is bonded to COOH and the other is bonded to B. Similarly, B in Table 1 is bonded to X and Y.

  Specific examples of the monovalent group (M) represented by -Z-A include, for example, combinations of Z and A as shown in Table 2 below.

As the silsesquioxane derivative of the present invention, for example,
(A) a structural unit represented by the following chemical formula (2);
(B) The silsesquioxane derivative containing the structural unit represented by following Chemical formula (3) can be mentioned.

  In formula (2), R1 represents the monovalent group (L), and X and Y in the group (L) are substituted with any group of (meth) acrylic group, vinyl group and epoxy group. Does not have as a base. In formula (3), R2 represents the monovalent group (M).

Moreover, as the silsesquioxane derivative of the present invention, for example,
(C) The silsesquioxane derivative containing the structural unit represented by following Chemical formula (4) can be mentioned. In this case, it is not necessary to contain the structural units (a) and (b).

  In Formula (4), R3 represents the monovalent group (L), and X and / or Y in the group (L) is selected from the group consisting of a (meth) acryl group, a vinyl group, and an epoxy group. It has at least one selected group as a substituent.

  The silsesquioxane derivative of the present invention can further contain (d) a structural unit represented by the following chemical formula (5) in addition to the above-described structural unit.

  In formula (5), R 4 represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. As said alkyl group, a methyl group, an ethyl group, and n-propyl group are preferable, for example. Moreover, as said aryl group, a phenyl group, a benzyl group, a tolyl group, a xylyl group, and a naphthyl group are preferable, for example.

  The silsesquioxane derivative of the present invention contains at least one structural unit having the group (L) among the plurality of structural units contained therein, and the group (L in any structural unit thereof) ) And (meth) acrylic group, vinyl group and epoxy group are not necessarily contained, and the derivative contains at least one structural unit having the group (M). In the above derivative, the constituent unit containing at least one group selected from the group consisting of a (meth) acryl group, a vinyl group and an epoxy group is preferably 10 mol% or more, more preferably 30 mol% or more.

  In the silsesquioxane derivative of the present invention, as the content ratio of the structural unit, when the structural unit (a) and the structural unit (b) are contained, the molar ratio of (a) :( b) is 20:80. ~ 80: 20 is preferred. Moreover, as for the content, when containing a structural unit (d), 10-80 mol% is preferable.

The structure of the silsesquioxane skeleton in the silsesquioxane derivative is not particularly limited, and is generated through steps represented by hydrolysis and condensation reaction of trialkoxysilane (RSiO _3/2 ) _n general formula Polysiloxane having As the silsesquioxane skeleton, those having a cage type, an incomplete cage type, a ladder type, and a random type structure are known.

  The weight average molecular weight Mw of the silsesquioxane skeleton is a range in which 1000 to 10,000 is usually obtained. Preferably, it is 1500-5000.

  As a trialkoxysilane used as a raw material, if it has the structural units (a) to (d), a trialkoxysilane having a corresponding R substituent is used, or an appropriate material after forming a silsesquioxane skeleton is used. It may be modified with a reagent to form the desired R substituent.

  Specific examples of trialkoxysilanes having an R substituent include, for example, substituted trialkoxysilanes in which the R substituent is a (meth) acryl group, such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyl. Examples include triethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane. These may be used alone or in combination of two or more. Of these, 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane are preferable from the viewpoint of reactivity.

  Examples of the substituted trialkoxysilane in which the R substituent is an aryl group or an alkyl group having 1 to 12 carbon atoms include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and n-propyltrisilane. Methoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, p-methoxyphenyltrimethoxy Silane, p-methoxyphenyl triethoxysilane, etc. can be mentioned. These may be used alone or in combination of two or more. Of these, methyltrimethoxysilane, ethyltrimethoxysilane, and phenyltrimethoxysilane are preferable from the viewpoints of heat resistance and reactivity.

  In order to form a desired R substituent by forming a silsesquioxane skeleton with an appropriate reagent, for example, an amino group is introduced into the silsesquioxane in advance, and the amino group is modified to form an amic. An acid may be used. In order to introduce an amino group into silsesquioxane, a trialkoxysilane whose substituent is an amino group may be used.

  Examples of the production method of the silsesquioxane skeleton include a method of hydrolyzing and condensing the starting trialkoxysilane. For example, as the conditions for hydrolysis and cocondensation, known conditions can be used, At that time, a catalyst may be used. Examples of the catalyst include tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, hydrochloric acid, sulfuric acid. , Formic acid and oxalic acid. Moreover, as reaction conditions, 25 to 100 degreeC can be used for 1 to 10 hours, for example.

  The photosensitive resin composition of the present invention contains the silsesquioxane derivative of the present invention as a resin component. In the photosensitive resin composition of this invention, you may mix | blend a photoinitiator as needed. As the photopolymerization initiator, a radical photopolymerization initiator can be used. Alternatively, a thermal radical polymerization initiator may be used in combination with the photo radical polymerization initiator.

  Examples of the photo radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenyl-propane-1. -One, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy -2-methyl-propionyl) -benzyl] phenyl) -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxy Mention may be made of the id and the like.

  Examples of the thermal radical polymerization initiator include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl- 2,5-bis (t-butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) valerate, benzoyl peroxide, t -Butylperoxybenzoate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, m -Toluyl peroxide etc. can be mentioned.

  In the photosensitive resin composition of the present invention, the use of a photopolymerization initiator is not essential, but it can also be used. As a compounding quantity in the case of using a photoinitiator, Preferably it is 0.5-7 weight part with respect to 100 weight part of silsesquioxane derivatives, More preferably, it is 2-5 weight part.

  In the photosensitive resin composition of the present invention, other additives can be blended. Examples of the additive include an antioxidant and a surfactant.

  The antioxidant is not particularly limited, and examples thereof include 2,6-di-t-butyl-p-cresol, dibutylhydroxytoluene, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethyl. Monophenols such as phenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl Bisphenols such as 2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, , 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t- Butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris ( 3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol and other high molecular phenols, dilauryl- , 3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, Tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6 -Methyl-4- {2- (octadecyl Phosphites such as xylcarbonyl) ethyl} phenyl] hydrogen phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl- 4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Oxaphosphaphenanthrene oxide or the like can be used. These may be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, the amount of the antioxidant used is preferably 0.01 to 5 parts by weight, more preferably 100 parts by weight with respect to the silsesquioxane derivative. 0.1 to 3 parts by weight.

  The surfactant is not particularly limited, and examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Ftop EF301, Ftop 303, Ftop 352 (Manufactured by Shin-Akita Kasei Co., Ltd.); Megafuck F171, Megafuck F172, Megafuck F173 (manufactured by Dainippon Ink & Chemicals, Inc.); Florard FC-430, Florer FC-431 (manufactured by Sumitomo 3M); Asahi Guard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (Manufactured by Asahi Glass Co., Ltd.) commercially available fluorine-based surfactants; organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth) acrylic acid copolymer polyflow No. 57, 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), etc. These may be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, the amount of the surfactant used is preferably 0.01 to 5 parts by weight, more preferably 100 parts by weight based on the silsesquioxane derivative. 0.1 to 3 parts by weight.

  Examples of the method for applying the photosensitive resin composition of the present invention include spin coating, spraying, dip coating, bar coating, roll coating, and slit coating. As a preferable condition of the composition in this case, it is convenient for coating that the viscosity is about 1 to 10 mPa · s at 25 ° C. When using as a composition for coating film formation, it can apply | coat so that it may become a dry film thickness of 1-5 micrometers, for example, and can be hardened by UV irradiation, for example.

  It does not specifically limit as a radiation source used for hardening of the photosensitive resin composition of this invention, For example, an ultraviolet fluorescent lamp, a mercury lamp, an arc lamp, an electron beam (EB) etc. can be used. The irradiation dose can be appropriately set by those skilled in the art. Furthermore, an inert gas such as nitrogen or argon can be used as the curing atmosphere as necessary.

  Moreover, when further thermally curing the photosensitive resin composition of this invention as needed, 50-150 degreeC, the conditions for 10 to 60 minutes can be used, for example.

For alkali development of the photosensitive resin composition of the present invention, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di- n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, An alkaline solution such as 1,5-diazabicyclo [4,3,0] -5-nonane can be used as the developer. As treatment conditions, a pH of about 8 to 14, a condition of about 10 to 50 ° C. and about 0.1 to 10 minutes can be used. After the development processing, pure water rinsing can be performed as necessary.

  The photosensitive resin composition of this invention can be used for various uses as a negative photosensitive resin composition. For example, in a manufacturing method of an electronic component that is finely processed by a photolithography method, the photosensitive resin composition of the present invention is applied as a negative photoresist resin composition on a wafer or the like by spin coating or spraying, After pre-baking as necessary, a pattern is formed by exposure, development, and rinsing, an etching process is performed, and a residue is peeled and removed to manufacture an electronic component such as a semiconductor device.

  As said electronic component, an integrated circuit element, a solid-state image sensor, a printed wiring circuit element, a liquid crystal panel etc. can be mentioned, for example.

  In addition, the photosensitive resin composition of the present invention can be used as an insulating film such as an interlayer insulating film in a multilayer wiring electronic circuit of a semiconductor device, or a protective film for an electronic component or a substrate surface. Furthermore, the photosensitive resin composition of the present invention can be applied to alkali filters suitable for forming color spacers, color resist binder compositions, solder resists, columnar spacers that can be substituted for bead spacers in liquid crystal display elements. Solvent type photosensitive composition, materials for various optical components (lenses, LEDs, plastic films, substrates, optical disks, etc.), coating agents for forming protective films for optical components, adhesives for optical components (adhesives for optical fibers, etc.) ); A coating agent for producing a polarizing plate, a photosensitive resin composition for hologram recording, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, the following description is only for description and the present invention is not limited to these Examples.

The meanings of the abbreviations in the following synthesis examples, examples and comparative examples are as follows. In addition, the unit of the compounding quantity in a table | surface is a weight part.
Product A: Alkali-soluble acrylic resin obtained in Synthesis Example 1.
Product B: Alkali-soluble polyimide resin Unidic V-8002 (manufactured by DIC Corporation).
Irgacure 184: an alkylphenone photopolymerization initiator manufactured by BASF.

Synthesis example 1
Product A: Synthesis of alkali-soluble acrylic resin A In a 500 mL four-necked flask, 233 g of Ogsol PG (fluorene-containing epoxy resin, epoxy equivalent 233 g / eq) manufactured by Osaka Gas Chemical, 1.3 g of triethylbenzylammonium chloride, 2, 140 mg of 6-diisobutylphenol and 72 g of acrylic acid were charged, and dissolved by heating at 90 to 100 ° C. while blowing air at a rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. Although the solution became clear and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 15 hours for the acid value to reach the target. A pale yellow transparent and solid polyfunctional epoxy acrylate resin was obtained. After adding and dissolving 115 g of propylene glycol monomethyl ether acetate (PGMEA) in 100 g of the epoxy acrylate resin prepared above, 25.7 g of biphenyltetracarboxylic acid (s-BPDA) and 0.2 g of tetraethylammonium bromide are mixed. The temperature was gradually raised and reacted at 110-115 ° C. for 12 hours. Next, 12.5 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours to synthesize an alkali-soluble acrylic resin A.

Synthesis example 2
Synthesis of substituted trialkoxysilane (SC1) in which R substituent is the following formula (6) 3-aminopropyltrimethoxysilane (0.027 mol) and MH700G (mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. Nippon Rika Co., Ltd. (0.027 mol) was dissolved in MIBK (methyl isobutyl ketone) (24 g) and stirred at room temperature for 1 hour. The disappearance of MH700G was confirmed by gas chromatography, MIBK was distilled off, and SC1 was obtained.

Synthesis example 3
Synthesis of substituted trialkoxysilane (SC2) wherein R substituent is the following formula (7) 3-aminopropyltrimethoxysilane (0.027 mol) and ricacid HNA100 (alicyclic dicarboxylic acid anhydride, manufactured by Shin Nippon Rika Co., Ltd.) (0.027 mol) was dissolved in MIBK (24 g) and stirred at room temperature for 1 hour. The disappearance of HNA100 was confirmed by gas chromatography, MIBK was distilled off to obtain SC2.

Synthesis example 4
Synthesis of substituted trialkoxysilane (SC3) in which R substituent is the following formula (8) 3-aminopropyltrimethoxysilane (0.027 mol) and 3-trimethoxysilylpropyl succinic anhydride (0.027 mol) were converted into MIBK. (24 g) and stirred at room temperature for 1 hour. The disappearance of 3-trimethoxysilylpropyl succinic anhydride was confirmed by gas chromatography, MIBK was distilled off to obtain SC3.

Synthesis example 5
Synthesis of substituted trialkoxysilane (SC4) in which R substituent is the following formula (9) N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (0.027 mol) and MH700G (0.027 mol) were MIBK (24 g) and stirred at room temperature for 1 hour. The disappearance of MH700G was confirmed by gas chromatography, MIBK was distilled off, and SC4 was obtained.

Synthesis Example 6
Synthesis of substituted trialkoxysilane (SC5) in which R substituent is the following formula (10) N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (0.027 mol) and ricacid HNA100 (0.027 mol) It was dissolved in MIBK (24 g) and stirred at room temperature for 1 hour. The disappearance of HNA100 was confirmed by gas chromatography, MIBK was distilled off, and SC5 was obtained.

Synthesis example 7
Synthesis of substituted trialkoxysilane (SC6) in which R substituent is the following formula (11) N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (0.027 mol) and 3-trimethoxysilylpropyl succinic acid Anhydride (0.027 mol) was dissolved in MIBK (24 g) and stirred at room temperature for 1 hour. The disappearance of 3-trimethoxysilylpropyl succinic anhydride was confirmed by gas chromatography, MIBK was distilled off to obtain SC6.

Example 1
Synthesis of Silsesquioxane Derivative 1 (SQ Derivative 1) In a reaction vessel equipped with a stirrer and a thermometer, MIBK 100 g, tetramethylammonium hydroxide 20% aqueous solution 7.4 g (tetramethylammonium hydroxide 0.02 mol), After charging 20.8 g (1.49 mol) of distilled water, 51.5 g (0.15 mol) of SC1 obtained in Synthesis Example 2 was added so that the content ratio shown in Table 3 (30:70) was obtained. 86.9 g (0.35 mol) of roxypropyltrimethoxysilane was gradually added at 40 to 45 ° C. and left to stir for 3 hours. After completion of the reaction, 100 g of MIBK was added to the system, and then washed with 50 g of distilled water until the pH of the aqueous layer became neutral. The organic layer was dried over sodium carbonate and filtered, and then MIBK was distilled off under reduced pressure to obtain the target compound (SQ derivative 1). As a result of analysis by GPC, SQ derivative 1 was a silsesquioxane derivative mainly composed of a ladder type structure or a random type structure with Mw = 1,500 and dispersity Mw / Mn = 1.5.

Example 2
Synthesis of Silsesquioxane Derivative 2 (SQ Derivative 2) As trialkoxysilane, SC1 obtained in Synthesis Example 2 was 85.8 g (0.25 mol), and 3-methacryloxypropyltrimethoxysilane was 62.1 g (0. 25 mol) SQ derivative 2 was obtained in the same manner as in Example 1 except that it was used.

Example 3
Synthesis of Silsesquioxane Derivative 3 (SQ Derivative 3) As trialkoxysilane, 120.2 g (0.35 mol) of SC1 obtained in Synthesis Example 2 and 37.3 g (0.3.3 mol) of 3-methacryloxypropyltrimethoxysilane were obtained. SQ derivative 3 was obtained in the same manner as in Example 1 except that 15 mol) was used.

Example 4
Synthesis of Silsesquioxane Derivative 4 (SQ Derivative 4) As trialkoxysilane, SC1 obtained in Synthesis Example 2 was 68.7 g (0.20 mol), and 3-acryloxypropyltrimethoxysilane was 46.9 g (0. 20 mol), and SQ derivative 4 was obtained in the same manner as in Example 1 except that 29.7 g (0.10 mol) of phenyltrimethoxysilane was used.

Example 5
Synthesis of Silsesquioxane Derivative 5 (SQ Derivative 5) As trialkoxysilane, SC1 obtained in Synthesis Example 2 was 68.7 g (0.20 mol), and 3-methacryloxypropyltrimethoxysilane was 49.7 g (0. 20 mol), and SQ derivative 5 was obtained in the same manner as in Example 1 except that 22.5 g (0.10 mol) of ethyltrimethoxysilane was used.

Example 6
Synthesis of Silsesquioxane Derivative 6 (SQ Derivative 6) As trialkoxysilane, SC4 obtained in Synthesis Example 5 was 75.2 g (0.20 mol), and 3-methacryloxypropyltrimethoxysilane was 49.7 g (0. 20 mol), and SQ derivative 6 was obtained in the same manner as in Example 1 except that 22.5 g (0.10 mol) of ethyltrimethoxysilane was used.

Example 7
Synthesis of Silsesquioxane Derivative 7 (SQ Derivative 7) As trialkoxysilane, SC3 obtained in Synthesis Example 4 was 88.3 g (0.20 mol) and 3-methacryloxypropyltrimethoxysilane was 49.7 g (0. 20 mol), and SQ derivative 7 was obtained in the same manner as in Example 1 except that 22.5 g (0.10 mol) of ethyltrimethoxysilane was used.

Comparative Example 1
Synthesis of Silsesquioxane Derivative 8 (SQ Derivative 8) SQ Derivative 8 was prepared in the same manner as in Example 1 except that 171.6 g (0.50 mol) of SC1 obtained in Synthesis Example 2 was used as trialkoxysilane. Obtained.

Comparative Example 2
Synthesis of Silsesquioxane Derivative 9 (SQ Derivative 9) SQ Derivative 9 was prepared in the same manner as in Example 1 except that 124.2 g (0.50 mol) of 3-methacryloxypropyltrimethoxysilane was used as a trialkoxysilane. Got.

  Table 3 shows the substituent content ratios of the silsesquioxane derivatives (SQ derivatives 1 to 9) obtained in Examples 1 to 7 and Comparative Examples 1 and 2. In Table 3, an amic acid group in SC1 is referred to as an amic acid group 1, an amic acid group in SC4 as an amic acid group 2, and an amic acid group in SC3 as an amic acid group 3.

Examples 8-14, Comparative Examples 3-6
Each component was mix | blended with the mixing | blending (weight part) shown in Table 4, and the photosensitive resin composition was obtained, respectively. The obtained composition was applied to a glass substrate with a film thickness of 1 μm, and was exposed to light and cured. About the obtained cured film, the performance was evaluated as follows. The results are shown in Table 4, respectively.

[Evaluation method]
The evaluation method in an Example and a comparative example is demonstrated below.
1. Patterning property A pattern mask is applied to the coating film (drying condition 90 ° C. for 2 minutes) of the photosensitive resin composition, and after exposure (condition metal halide lamp 1000 mJ), development with alkaline solution (pH 12) (condition 25 ° C., 1 minute) The patterning property was evaluated visually or with a microscope.
The evaluation criteria are as follows.
A: There is no resist chipping or unmelted residue.
○: There is a slight lack of resist or unmelted resist.
X: There are many resist chips and unmelted residues.

2. Heat resistance (colorability)
After heating at 250 ° C. for 1 hour with a dryer, the yellow index YI was determined using a spectrophotometer UV-2450 manufactured by Shimadzu Corporation.
3. Heat resistance (remaining film rate)
The film thickness before and after heating at 250 ° C. for 1 hour was measured with a stylus type surface shape measuring instrument manufactured by Keyence Corporation, and calculated as a residual film ratio (%).
4). Heat resistance (5% weight loss temperature)
Using TG-DTA manufactured by SII, the temperature at the time when the weight was reduced by 5% from the initial weight was determined under the condition of a nitrogen atmosphere and a heating rate of 10 ° C./min.

5. Pencil hardness Pencil hardness was measured according to JIS K5600.
6). Total light transmittance (%)
The total light transmittance was determined with a haze meter manufactured by Suga Test Instruments Co., Ltd.

  Since the coating film using the composition of the present invention from Examples used SQ derivative resin, the total light transmittance was high. The comparative examples 3 and 4 using the SQ derivative resin were similarly high. On the other hand, the total light transmittances of Comparative Examples 5 and 6 using conventional organic resins were not higher than this. The patterning property of the coating film using the composition of the present invention was as good as or better than that of Comparative Examples 5 and 6 of the conventional product. On the other hand, the patterning properties of Comparative Examples 3 and 4 not using the composition of the present invention were poor. The heat resistance was good in both Examples and Comparative Examples using SQ derivative resins. From the above results, it was shown that the coating film using the composition of the present invention has good patterning properties and also has the performance of total light transmittance, heat resistance and pencil hardness.

Claims (8)

A structural unit represented by the following chemical formula (1):

[In the formula (1), R is
-X-B-Y-COOH (wherein X is a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group, or -R5-NH-R6- (wherein R5 and R6 have 1 to 3 carbon atoms) R5 and R6 may be the same or different, and Y represents one hydrogen atom of each of two ring carbon atoms from an aromatic ring group or an alicyclic group. Represents a divalent group generated by removal or a divalent alkylene group having 1 to 4 carbon atoms which may have a branched chain and / or a double bond; B represents —NHCO— or —CONH—; Wherein X and / or Y may have at least one group selected from the group consisting of a (meth) acryl group, a vinyl group and an epoxy group as a substituent. Valent group (L), or -ZA (wherein Z is a single bond, 1 carbon atom) Represents a monovalent group (M represents an alkylene group or an arylene group of -6, and A represents at least one group selected from the group consisting of a (meth) acryl group, a vinyl group, and an epoxy group). ). ]
A silsesquioxane derivative containing the above (provided that the derivative contains at least one constituent unit having the group (L) among the constituent units contained therein, any constituent unit thereof) The group (L) in the inside does not necessarily have any group of (meth) acryl group, vinyl group and epoxy group, and the derivative contains at least one structural unit having the group (M).) . Silsesquioxane derivatives are
(A) a structural unit represented by the following chemical formula (2);
(B) Structural unit represented by the following chemical formula (3):

(In the formula (2), R1 represents the monovalent group (L), and X and Y in the group (L) are any groups of (meth) acrylic group, vinyl group and epoxy group). The silsesquioxane derivative according to claim 1, which does not have a substituent.In formula (3), R 2 represents the monovalent group (M). Silsesquioxane derivatives are
(C) Structural unit represented by the following chemical formula (4):

(In Formula (4), R3 represents the monovalent group (L), and X and / or Y in the group (L) is a group consisting of a (meth) acryl group, a vinyl group, and an epoxy group). The silsesquioxane derivative according to claim 1, comprising at least one group selected from the group consisting of a substituent. Furthermore, (d) a structural unit represented by the following chemical formula (5):

(In Formula (5), R4 represents a C1-C12 alkyl group or a C6-C12 aryl group.) The silsesquioxane derivative in any one of Claims 1-3 containing. .   The negative photosensitive resin composition which contains the silsesquioxane derivative in any one of Claims 1-4 as a resin component.   Furthermore, the negative photosensitive resin composition of Claim 5 containing a photoinitiator.   The semiconductor device containing the interlayer insulation film using the negative photosensitive resin composition of Claim 5 or 6.   A method of manufacturing an electronic component that is finely processed by a photolithography method, comprising the step of forming a photoresist film using the negative photosensitive resin composition according to claim 5 or 6. Production method.