JP5305502B2 - Functional element, negative photosensitive resin composition used therefor, and method for producing functional element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition hardly generating a scum, having excellent pattern resolution, and excellent in adhesiveness to an opposed substrate, in a functional element bonded with the two opposedly-arranged substrates via a structure obtained from the negative photosensitive resin composition. <P>SOLUTION: A resin composition for forming the structure is the negative photosensitive resin composition containing (A) an acrylic monomer, (B) an alkali-soluble phenol resin obtained by copolymerizing a hydroxy styrene and a styrene as essential components, (C) a photopolymerization initiator, and (D) an epoxy compound, in the functional element bonded with the two substrates, obtained by press-bonding the second substrate onto the first substrate via the patternized structure provided by photolithography. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a functional element to be an electronic component using a photosensitive resin composition and a method for manufacturing the functional element. More specifically, the present invention relates to a functional element useful as a liquid crystal display element, a negative photosensitive resin composition that can be used in the production thereof, and a method for producing a functional element using the negative photosensitive resin composition.

  The greatest feature of the photosensitive resin composition is that an arbitrary fine pattern can be formed on the substrate by using a photolithographic technique. Examples thereof include a solder resist for protecting the surface of a circuit board and a resist for MEMS (Micro Electro Mechanical System) for creating a fine structure sensor. In recent years, not only is it possible to form an arbitrary fine pattern photolithographically on a single substrate, but also after patterning by photolithography using a photosensitive composition, it is adhered to a counter substrate. There has been proposed a method used for the purpose of supporting or fixing between the two substrates. Examples thereof include a method for connecting electrode pads formed on an integrated circuit element (Patent Document 1), an adhesion method for a circuit board (Patent Document 2), a method for manufacturing a semiconductor package (Patent Document 3), and a liquid crystal element. The method (patent document 4) etc. are mentioned. Further, Patent Document 5 uses a positive photosensitive resin composition, and Patent Document 6 uses a photosensitive composition using a partially hydrogenated alkali-soluble polymer to improve adhesion for the above-mentioned use. Are considering.

Japanese Patent No. 3050345 Japanese Patent No. 2660943 JP 2003-347357 A Japanese Patent Laid-Open No. 2004-163459 JP 2005-181976 A JP 2007-304355 A

  However, when a conventionally known photosensitive resin composition is used for the adhesive application, it has been pointed out that a problem remains in the adhesive performance. In Patent Document 5, the positive photosensitive resin composition has an adhesive property. Although investigation has been carried out, the resolution of the photosensitive resin composition shows only a resolution of about 40 μm and has not been sufficiently studied. Furthermore, in Patent Document 6, although the resolution is improved, the satisfaction of patterning properties such as residue and scum is not obtained. Thus, examination of the negative photosensitive resin composition for the said application excellent in adhesiveness, heat resistance, and also in the resolution was still inadequate.

  The present invention is a functional element in which two substrates arranged opposite to each other are bonded via a structure obtained from a negative photosensitive resin composition, and hardly generates residue and scum, and has excellent pattern resolution. It is an object of the present invention to provide a negative photosensitive resin composition that has excellent properties and excellent adhesion to a counter substrate.

As a result of intensive studies to solve the above problems, the present inventors have found that a negative photosensitive resin composition having a specific composition solves the above problems, and completed the present invention. It is a thing. That is, the present invention
(1) In the functional element in which the second substrate is bonded by bonding the second substrate through the patterned structure provided by photolithography on the first substrate, the structure (A) an acrylic monomer, (B) an alkali-soluble phenol resin obtained by copolymerizing hydroxystyrenes and styrene as essential components, and (C) a photopolymerization initiator. And (D) a negative photosensitive resin composition containing an epoxy compound;

(2) The functional element according to (1), wherein the negative photosensitive resin composition further contains a solvent;
(3) The functional element according to (1) or (2), wherein the component (B) in the negative photosensitive resin composition is an alkali-soluble phenol resin obtained by copolymerizing hydroxystyrene and styrene;
(4) Any one of the above (1) to (3), wherein the molar blending ratio of hydroxystyrenes which are constituent components of the alkali-soluble phenol resin obtained by copolymerization is 60 mol% to 95 mol% Functional device according to

(5) The functional element according to any one of (1) to (4) above, wherein the softening point of the epoxy compound (D) in the negative photosensitive resin composition is 40 ° C. to 110 ° C .;
(6) (D) The epoxy compound is a polymer of 2,2-bis (hydroxymethyl) -1-butanol and 1,2-epoxy-4-vinylcyclohexane or an epoxy compound represented by the following formula (1) The functional element according to the above (5),

(7) The proportion of the (D) epoxy compound in the total amount of (A), (B), (C) and (D) in the negative photosensitive resin composition is 5% to 50% by weight. The functional element according to any one of (1) to (6), wherein
(8) The functional element according to any one of (1) to (7), wherein the functional element is an element used for a liquid crystal display element;

(9) (A) an acrylic monomer on the first substrate, (B) an alkali-soluble phenol resin obtained by copolymerizing hydroxystyrenes and styrenes as essential components, and (C) a photopolymerization initiator. And (D) a negative photosensitive resin composition containing an epoxy compound, a structure is provided by photolithography, and then a second substrate is pressure-bonded onto the structure. A method of manufacturing an integrated functional element;
(10) The production method according to (9), wherein the functional element is a liquid crystal display element;

(11) (A) an acrylic monomer, (B) an alkali-soluble phenol resin obtained by copolymerizing hydroxystyrenes and styrene as essential components, (C) a photopolymerization initiator and (D) an epoxy compound The second substrate is bonded to the first substrate through a patterned structure provided on the first substrate by photolithography, and the two substrates are bonded to each other. A negative photosensitive resin composition for forming the structure, which is used in the production of a functional element;
(12) The negative photosensitive resin composition according to the above (11), wherein the negative photosensitive resin composition further contains a solvent;

(13) The negative according to (11) or (12), wherein the component (B) in the negative photosensitive resin composition is an alkali-soluble phenol resin obtained by copolymerizing hydroxystyrene and styrene. Type photosensitive resin composition;
(14) The molar blending ratio of hydroxystyrenes which are constituent components of the alkali-soluble resin obtained by copolymerization is 60 mol% to 95 mol% according to any one of (11) to (13) above The negative photosensitive resin composition as described;
(15) The negative photosensitive resin composition according to any one of the above (11) to (14), wherein the softening point of the epoxy compound (D) in the negative photosensitive resin composition is 40 ° C to 110 ° C. object;

(16) (D) The epoxy compound is a polymer of 2,2-bis (hydroxymethyl) -1-butanol and 1,2-epoxy-4-vinylcyclohexane or an epoxy compound represented by the above formula (1) The negative photosensitive resin composition according to (15), wherein
(17) The proportion of the (D) epoxy compound in the total amount of (A), (B), (C) and (D) in the negative photosensitive resin composition is 5% to 50% by weight. The negative photosensitive resin composition according to any one of (11) to (16) above,
About.

  Since the functional element using the negative photosensitive resin composition of the present invention has high pattern resolution, hardly generates residue and scum, and has excellent adhesion to the substrate, a liquid crystal display element and a plasma display element It is useful as a functional element such as an electronic circuit element, an optical semiconductor element (a light receiving element, a light emitting element, a CMOS, a CCD chip, etc.), an element for creating a MEMS.

Hereinafter, the present invention will be described in detail.
The functional element of the present invention is obtained by bonding two substrates by bonding a second substrate through a patterned structure provided on the first substrate by photolithography. And (A) an acrylic monomer, (B) an alkali-soluble phenolic resin obtained by copolymerizing hydroxystyrenes and styrene as essential components, (C) It is a negative photosensitive resin composition containing a photopolymerization initiator and (D) an epoxy compound.

  As the (A) acrylic monomer contained in the negative photosensitive resin composition used in the functional device of the present invention, a monomer having a methacrylic group or an acrylic group and having a polymerizable property is used without limitation. It can be arbitrarily selected from those usually used as a photosensitive resin composition. Examples of acrylic monomers that can be used include 2-acryloyloxyethyl 2-hydroxypropyl phthalate, 2-methacryloyloxyethyl 2-hydroxypropyl phthalate, 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl methacrylate, 3-methoxybutyl acrylate, 3- Methoxybutyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene group Cold dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1, 9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol Lutrimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate -G, dipenta Risurito - Le hexa methacrylate -, tri (2-acryloyloxyethyl) Hosufe -, tri (2-methacryloyloxyethyl) Hosufe - bets and the like. These are KAYARAD TC-110S, TC-120S, HDDA, HX-220, R-604, TMPTA, DPHA, DPHA-40H, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (all Japanized (Available from Yakuhin Co., Ltd.), etc., such as Viscotes 260, 312, 335HP, 295, 300, 360, GPT, 3PA, 400 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc. I can do it.

Of these acrylic monomers, (meth) acrylic acid esters having three or more methacrylic groups or acrylic groups are preferred, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, penta Preferred examples include erythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the like.
These acrylic monomers can be used alone or in combination of two or more.

  In consideration of developability and adhesiveness, the proportion of these (A) acrylic monomers in the total amount of (A), (B), (C) and (D) is 20% to 70% by weight. It is preferably 30% to 60%. If it is less than 20% or exceeds 70%, the developability in the photolithography process may be inferior.

The component (B) contained in the negative photosensitive resin composition used in the functional element of the present invention is an alkali-soluble phenol resin obtained by copolymerizing hydroxystyrenes and styrenes as essential components. Used.
Hydroxystyrenes may be substituted with 1 to 4 alkyl groups having 1 to 5 carbon atoms, such as o-hydroxystyrene, p-hydroxystyrene, m-hydroxystyrene, 3-methyl-4- Examples thereof include hydroxystyrene and 3-ethyl-4-hydroxystyrene, and p-hydroxystyrene is preferable.
Examples of styrenes include 1 to 5 carbon atoms having 1 to 5 alkyl groups which may have a substituent such as a halogen atom, 1 to 5 carbon atoms having 1 to 5 alkoxy groups, and 1 to 5 carbon atoms. May be substituted with a halogen atom such as chlorine atom or bromine atom, such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxy. Styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, m-trichloromethylstyrene and the like, and the side chain may be substituted with 1 to 3 alkyl groups having 1 to 5 carbon atoms. If, alpha-methyl styrene, and the like. Among these, styrene is more preferable.

The proportion of the hydroxystyrenes in the component (B) is 60 to 95 mol%, preferably 70 to 90 mol%.
The proportion of the styrenes in the component (B) is 5 to 40 mol%, preferably 10 to 30 mol%.

  In (B), in addition to the essential components, other arbitrary polymerizable monomers can be used as long as the physical properties are not adversely affected. Other optional polymerizable monomers include, for example, unsaturated carboxylic acids such as methacrylic acid, esters of unsaturated carboxylic acids such as methyl methacrylate, and alcohols such as 2-hydroxyethyl methacrylate (HEMA). -Monomers containing hydroxyl groups, acrylonitrile, ethyl vinyl ether, vinyl acetate, methyl vinyl ketone, N-vinyl pyrrolidone and other monomers.

  The polymerization reaction and copolymerization reaction using these monomers can be carried out according to conventional methods.

  As component (B) (alkali-soluble phenol resin) contained in the negative photosensitive resin composition used in the functional element of the present invention, a resin obtained by copolymerizing hydroxystyrenes and styrenes A resin obtained by copolymerizing hydroxystyrene and styrene is particularly preferable.

  The proportion of the component (B), which is an alkaline soluble resin, in the total amount of (A), (B), (C) and (D) is preferably 10% to 70% by weight, and further, Considering the subsequent adhesiveness, 30% to 60% is more preferable.

  As the (C) photopolymerization initiator contained in the negative photosensitive resin composition used in the functional element of the present invention, a functional compound that initiates polymerization by light irradiation can be used without limitation. Moreover, it is also possible to use together with photopolymerization initiation assistants such as amine compounds, alkoxyanthracene compounds, and thioxanthone compounds, chain transfer agents, and the like.

Examples of the photopolymerization initiator that can be used include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy- 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- Dimethylamino-2- (4-methylbenzyl) -1- Acetophenones such as 4-morpholin-4-ylphenyl) butan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethyl Thioxanthones such as thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketones such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4 Benzophenones such as 2,4'-bismethylaminobenzophenone; phosphines such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Xides etc. are mentioned. Among these, for example, Irgacure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, manufactured by Ciba Specialty Chemicals) can be obtained as a commercial product. .
These can be used alone or in combination of two or more.

  The proportion of the (C) photopolymerization initiator in the total amount of (A), (B), (C) and (D) is preferably from 0.5% to 30%, particularly preferably by weight. 1% to 10%.

Examples of the photopolymerization initiation aid that may be used in the present invention include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (Michler's ketone), 4 Amine compounds such as 4,4′-bis (diethylamino) benzophenone and 4,4′-bis (ethylmethylamino) benzophenone. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like. . Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
When a photopolymerization initiation assistant is used, the amount used in the composition of the present invention is preferably 0.2 parts by weight or more and 10 parts by weight or less per 1 part by weight of (C) photopolymerization initiator, and further 0.3 weights. More preferably, it is more than 5 parts by weight and more preferably less than 5 parts by weight.

Examples of the chain transfer agent that may be used in the present invention include polythiol or mercapto group-substituted alkyl compounds.
Examples of the polythiol include triethylene glycol dimercaptan, trimethylolpropane-tris (β-thiopropionate), tris (2-hydroxyethyl) isocyanurate tris (β-mercaptopropionate). Pentaerythritol tetrakis (β-thiopropionate), 1,8-dimercapto-3,6-dioxaoctane, and the like.
Examples of the mercapto group-substituted alkyl compound include dimercaptobutane and trimercaptohexane.
When a chain transfer agent is used, the amount used in the composition of the present invention is preferably 0.2 parts by weight or more and 10 parts by weight or less per 1 part by weight of (C) photopolymerization initiator, and more preferably 0.3 parts by weight or more. The amount is more preferably 5 parts by weight or less, and particularly preferably 0.5 part by weight or more and 3 parts by weight or less.

  As the epoxy compound (D) contained in the negative photosensitive resin composition used in the functional element of the present invention, a compound having an epoxy group is used. Examples of epoxy compounds that can be used include, for example, polyfunctional epoxy compounds that are glycidyl ethers of polyphenol compounds, polyfunctional epoxy compounds that are glycidyl ethers of various novolak resins, and alicyclic polyfunctional epoxies. Compounds, aliphatic polyfunctional epoxy compounds, heterocyclic polyfunctional epoxy compounds, glycidyl ester polyfunctional epoxy compounds, glycidyl amine polyfunctional epoxy compounds, polyfunctional epoxy compounds obtained by glycidylation of halogenated phenols, etc. Can be mentioned.

  As a polyfunctional epoxy compound which is a glycidyl ether compound of the polyphenol compound, 2- [4- (2,3-hydroxyphenyl) -2- [4- [1,1-bis [4- (2 , 3-hydroxy) phenyl] ethyl] phenyl] propane, bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethylbisphenol A, dimethyl bisphenol. A, tetramethylbisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4 ′ -Biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2'-methylene- (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallo- , Phloroglucinol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, polyphenol compounds such as phenolic polybutadiene And polyfunctional epoxy compounds which are glycidyl ethers such as allylated phenols.

  Polyfunctional epoxy compounds that are glycidyl ethers of the various novolak resins include phenol, cresols, ethyl phenols, butyl phenols, octyl phenols, bisphenol A, bisphenols. Novolak resin, xylylene skeleton-containing phenol novolak resin, dicyclopentadiene skeleton-containing phenol novolak resin, biphenyl, and the like, starting from various phenols such as bisphenols such as diol F and bisphenol S, and naphthols Examples thereof include glycidyl ethers of various novolak resins such as a skeleton-containing phenol novolak resin and a fluorene skeleton-containing phenol novolak resin.

Examples of the alicyclic polyfunctional epoxy compound include alicyclic polyfunctional epoxy compounds having an aliphatic ring skeleton such as cyclohexane.
Examples of the aliphatic polyfunctional epoxy compounds include 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, glycidyl ethers of polyvalent alcohol such as pentaerythritol, and the like. Can be mentioned.
Examples of the heterocyclic polyfunctional epoxy compound include heterocyclic polyfunctional epoxy compounds having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.

Examples of the glycidyl ester epoxy compound include epoxy compounds composed of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.
Examples of the glycidylamine polyfunctional epoxy compound include epoxy compounds obtained by glycidylation of amines such as aniline and toluidine.
Epoxy compounds obtained by glycidylating the halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolak, and chlorinated. Examples thereof include epoxy compounds obtained by glycidylation of halogenated phenols such as bisphenol S and chlorinated bisphenol A.
These epoxy compounds can be used alone or in combination of two or more.

  Of the various epoxy compounds described above, in consideration of resolution at the time of photolithography and subsequent adhesiveness, an epoxy compound that is solid at room temperature is preferable, and an epoxy compound having a softening point of 40 ° C to 110 ° C is more preferable. Epoxy compounds exhibiting a liquid state at room temperature tend to have poor adhesion, and among epoxy compounds that are solid at room temperature, those having a softening point exceeding 110 ° C tend to have residual residues that tend to remain in the photolithographic process. is there.

  Among the room temperature solid epoxy compounds having a softening point of 40 ° C. to 110 ° C., the polyfunctional epoxy compound represented by the above formula (1), which is a glycidyl ether compound of a polyphenol compound, also has an aliphatic ring skeleton. Among the alicyclic polyfunctional epoxy compounds, a polymer of 2,2-bis (hydroxymethyl) -1-butanol and 1,2-epoxy-4-vinylcyclohexane is particularly preferable. As the epoxy compound represented by the above formula (1), commercially available products such as NC6000 (manufactured by Nippon Kayaku Co., Ltd.) and VG-3101L (manufactured by Mitsui Chemicals, Inc.) can be easily obtained.

  The proportion of the (D) epoxy compound in the total amount of (A), (B), (C) and (D) is preferably 5% to 50% by weight, and further, photolithography Considering the developability in the process and the subsequent adhesiveness, the weight ratio is more preferably 5% to 30%.

In a preferred embodiment, the negative photosensitive resin composition used in the functional element of the present invention is a negative photosensitive resin composition obtained by dissolving the above-described components in a solvent appropriately selected from the following solvents. Prepared as a solution.
Examples of the solvent which can be used here include lower alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol and butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether. Carbon atoms of alkylene glycols having 1 to 4 carbon atoms such as -ter, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, etc. Lower ethers, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate 3-methyl-3-methoxybutyl acetate C1-C4 lower ether of C1-C4 alkylene glycol such as ethylethoxypropionate, C1-C4 acylate of lower ether, aromatic carbonization such as toluene, xylene, etc. Ketones such as hydrogen, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionate Propyl acid, butyl 3-hydroxypropionate, 2- Droxy-3-methylbutanoic acid propyl, ethyl methoxyacetate, propyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl acid, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxyprop Examples thereof include esters such as butyl pionate and ethers such as tetrahydrofuran.

  Among these solvents, solubility in each of the components ((A), (B), (C) and (D)), chemical stability of the solvent itself, small change with time due to volatilization, In consideration of toxicity and the like, the alkylene group having 1 to 3 carbon atoms such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, etc. It is preferable to select 4 lower ether acetates, propylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol or the above esters.

  In the present invention, the film thickness of the structure is usually in the range of 1 μm to 100 μm (film thickness after curing of the negative photosensitive resin composition). The film thickness changes depending on the conditions such as the types (A), (B), (C) and (D) and the mixing ratio, the types and mixing ratios of other additives described below, or the coating method (described later). Therefore, it is preferable to set these conditions so that the film thickness of the structure is in the above range.

  In the present invention, in preparing the negative photosensitive resin composition solution, in addition to the components (A), (B), (C) and (D), the solvent, and if necessary, the photopolymerization. Initiating aid, chain transfer agent, (D) curing agent reactive with epoxy compound, curing accelerator, sensitizer, coupling agent, surfactant, inorganic filler (silica, alumina, talc, calcium carbonate , Barium sulfate, etc.), antioxidants, light stabilizers, moisture resistance improvers, thixotropic agents, antifoaming agents, other various resins, tackifiers, antistatic agents, lubricants, UV absorbers, etc. An agent can also be blended.

  Examples of the curing agent reactive with the epoxy compound include an acid anhydride curing agent, a carboxylic acid curing agent, an amine curing agent, a hydrazide curing agent, and a phenol curing agent. These can be mixed and used in a solution of a negative photosensitive resin composition within a range that does not adversely affect the developability in the photolithography process and the subsequent adhesiveness.

  Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, biphenyltetracarboxylic anhydride. Aromatic carboxylic acid anhydrides such as acid anhydrides; anhydrides of aliphatic carboxylic acids such as azelaic acid, sebacic acid and dodecanedioic acid; tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic acid anhydride, head Examples thereof include alicyclic carboxylic acid anhydrides such as acid anhydrides and hymic acid anhydrides.

  Examples of the carboxylic curing agent include aliphatic polycarboxylic acids having 2 to 22 carbon atoms such as succinic acid, adipic acid, azelaic acid, and sebacic acid; phthalic acid, isophthalic acid, terephthalic acid, 1,2,4 -Aromatic polycarboxylic acids such as benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, naphthalenedi (or tetra) carboxylic acid; tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, etc. An alicyclic polycarboxylic acid etc. are mentioned.

  Examples of the amine curing agent include diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o- Aromatic amines such as phenylenediamine, 1,5-diaminonaphthalene, and m-xylylenediamine; aliphatic amines such as ethylenediamine, diethylenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, and polyetherdiamine Guanidines such as dicyandiamide and 1- (o-tolyl) biguanide;

  Examples of the hydrazide-based curing agent include carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide dihydrazide, Acid dihydrazide, hexadecanoic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4′-bisbenzenedihydrazide, 1,4-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,4 -Cyclohexane dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebissemicarbazide, itaconic acid dihydr Dihydrazide compounds such as Hydrazide; pyromellitic acid trihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, polyfunctional hydrazide compounds such as 1,2,4-benzenetricarboxylic hydrazide.

  Examples of the phenolic curing agent include bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, tetramethylbisphenol A, and dimethylbisphenol. A, tetramethylbisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4 ′ -Biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2'-methylene-bis (4- Methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, Phenol, hydroquinone, pyrogallol, phenol having a diisopropylidene skeleton, phenol having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, phenolized polybutadiene, phenol Various phenols such as bisphenol A, bisphenol F, bisphenol S, naphthols, benzene, cresol, ethylphenol, butylphenol, octylphenol; Examples include novolak resin, xylylene skeleton-containing phenol novolak resin, dicyclopentadiene skeleton-containing phenol novolak resin, biphenyl skeleton-containing phenol novolak resin, fluorene skeleton-containing phenol novolak resin, furan skeleton-containing phenol novolak resin, and the like. It is done.

  In the above, in the case of adding a curing agent that is reactive with (D) the epoxy compound, considering the reactivity with (D) the epoxy compound, the equivalent ratio to the epoxy group of (D) the epoxy compound is 0.4. It is preferable to use in the range of -1.5, preferably 0.6-1.2. If the amount used is outside this range, curing failure may occur.

  A compound that functions as a catalyst for accelerating the curing reaction may be used as a curing accelerator. Examples of such curing accelerators include imidazole curing accelerators, phosphines, tertiary amines, metal compounds such as tin octylate, quaternary phosphonium salts, and the like.

  Examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenyl-4-methylimidazole. 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- 2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole) (1 ′)) Ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino 6 (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, Imidazole, 2-ethyl-4-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-benzyl-2-ethylimidazole Various imidazoles such as 1-cyanoethyl, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole; Salts of imidazoles with polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid; amides such as dicyandiamide; 1,8- Diaza compounds such as diazabicyclo (5.4.0) undecene-7 or phenols thereof; salts thereof with the above polycarboxylic acids or phosphinic acids; tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethyl Ammonium salts such as ammonium bromide; phosphines such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate; phenols such as 2,4,6-trisaminomethylphenol; or amine adducts These are mixed May be used.

Among these curing accelerators, liquid imidazole compounds are preferred, such as imidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and 1-benzyl-2. -Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-phenyl-4,5 -Di- (cyanoethoxymethyl) imidazole, 1,8-diazabicyclo (5.4.0) undecene-7 and the like can be preferably used.
Among these, for example, 1B2PZ (1-benzyl-2-phenylimidazole, manufactured by Shikoku Kasei Co., Ltd.) is a commercially available product.

  These curing accelerators are usually used in an amount of about 0.1 to 5 parts by weight, preferably about 0.3 to 4 parts by weight, per 100 parts by weight of the (D) epoxy compound.

Examples of the sensitizer that may be added to the negative photosensitive resin composition solution include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, and pentyl 4-dimethylamino. Tertiary amines such as benzoate, triethylamine and triethanolamine are used, and these can be used alone or in combination of two or more. Among these, as a commercially available product, for example, DETX-S (aminobenzoic acid sensitizer manufactured by Nippon Kayaku Co., Ltd.) is available.
When these sensitizers are used, the amount used is 0.05 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the (A) acrylic monomer. .

Examples of the coupling agent that may be added to the negative photosensitive resin composition solution include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyl. Dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) -3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyl Trimethoxysilane, 3-chlorop Silane coupling agents such as pyrmethyldimethoxysilane and 3-chloropropyltrimethoxysilane, isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) G) Titanium coupling agents such as oxyacetate, tetraisopropyldi (dioctyl phosphite) titanate, neoalkoxy tri (pN- (β-aminoethyl) aminophenyl) titanate, Zr-acetylacetate Net, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodecanoylzirconate, neoalkoxytris (dodecanoyl) benzenesulfonylzirconate, neoalkoxytris (Ethylenediamine Noethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Al-propionate, etc. An aluminum-based coupling agent or the like is used as necessary. By using a coupling agent, the adhesiveness with a base material improves and the cured film excellent in moisture-proof reliability is obtained.
When these coupling agents are used, the amount used is preferably about 0.1 to 5 parts by weight, preferably 100 parts by weight of the total amount of (A), (B), (C) and (D). Is about 0.5 to 3 parts by weight.

  The surfactant that may be added to the negative photosensitive resin composition solution is used as necessary for the purpose of improving the coating suitability of the composition. For example, a silicon surfactant or a fluorosurfactant is used. As a commercial product, there is MegaFuck F-470 (manufactured by Dainippon Ink & Chemicals, Inc.). When the surfactant is added, the addition amount is about 0.01 to 1 part by weight, preferably 100 parts by weight of the total amount of (A), (B), (C) and (D). Is about 0.05 to 0.8 parts by weight.

  Next, using the above-mentioned negative photosensitive resin composition, the second substrate is pressure-bonded via a patterned structure provided on the first substrate by photolithography to form both substrates. A method for manufacturing a functional element to which is bonded will be described based on an example of the functional element shown in FIG.

  In the method for producing a functional element of the present invention, the substrate that can be used is not particularly limited, and any substrate can be used as long as the structure can be constructed using a negative photosensitive resin composition. It may be a part of a part or the like. Examples of the substrate material (reference numeral 1 in FIG. 1) include, for example, a glass substrate, a plastic film substrate, an electric / electronic circuit substrate, a component substrate for a semiconductor device, a semiconductor wafer substrate, a MEMS creation substrate, and others. The component base material of these is mentioned.

Examples of the glass substrate include a non-alkali glass substrate for a display represented by a liquid crystal display device, a plasma display device, a cathode ray tube and the like.
Examples of the plastic film base material include polyimide films, polyester films, polyethersulfone films, polycarbonate films, and simple plastic films such as cycloolefin films, other retardation films, diffusion films, antireflection films, and the like. Examples include functional plastic films.
Examples of the electric / electronic circuit substrate include commonly used glass epoxy electric circuit boards and flexible circuit boards.

Examples of the component substrate for the semiconductor device include a component substrate for a semiconductor device mounted with a device mounted with a semiconductor chip, an optical semiconductor element (light receiving element, light emitting element, CMOS, CCD, etc.), and the like. .
Examples of the semiconductor wafer substrate include a Si wafer substrate, and can be applied to a semiconductor substrate in a semiconductor manufacturing process.
Examples of the MEMS production substrate or other component substrates include biochip-related substrates represented by separation valves and the like, inkjet head component substrates, and the like.

The negative photosensitive resin composition (reference numeral 2 in FIG. 1) used in the present invention is applied as a solution on the first substrate by a normal spin coating method, but the application method is particularly limited. It is selected as appropriate according to the substrate, parts, etc. to be applied, and roll coating method, spray method, curtain coating method, slit coating method, bar coating method, inkjet method A coating method such as the above can also be used.
The film thickness of the structure is not particularly limited. For example, the negative photosensitive resin composition solution whose concentration is adjusted under the conditions of 1 μm to 100 μm, preferably 5 μm to 50 μm after curing, The coating method can be used.

  For drying after coating on the first substrate, it is necessary to select the optimum conditions depending on the blending ratio of each component in the negative photosensitive composition solution and the type of solvent. -Remove the solvent. The drying time is preferably adjusted to a time at which tack does not occur on the surface when pre-baking is completed.

  Next, since it is a negative photosensitive composition, it is irradiated with active energy rays with an exposure machine through a predetermined pattern mask (reference numeral 3 in FIG. 1), and developed with an alkali developer to remove unnecessary portions (uncured portions). ) Is removed, and then a structure provided on the first substrate can be obtained through a drying process. At this time, a PEB (Post Exposure Bake) step may be provided after exposure as necessary.

  The active energy ray used for the exposure is not particularly limited, and it is preferable to use an active energy ray in the absorption wavelength region of the photopolymerization initiator, for example, using visible light, ultraviolet light, or the like. I can do it. A wavelength range of 190 nm to 440 nm is preferable, and an ultraviolet ray of 365 nm is particularly preferable. Further, the irradiation energy is preferably 50 to 1000 mJ.

The exposure method is not particularly limited to these, but known direct contact exposure or proximity-exposure can be applied.
The developing method is not particularly limited, and it is carried out by a method known per se using a developer that can remove the uncured portion. Examples of the developer that can be used include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia, aliphatic primary amines such as ethylamine and n-propylamine, diethylamine and di-n-propyl. Aliphatic secondary amines such as amines, aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, alicyclic tertiary amines such as N-methylpiperidine, N-methylpyrrolidine, pyridine, quinoline An aqueous solution of an alkaline compound such as an aromatic tertiary amine such as quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used.
A surfactant may be added as appropriate to the aqueous solution of the alkaline compound. The concentration of the developer can usually be 0.1% to 5% by weight.

The developing method may be any of publicly known paddle development, dip development, shower development, etc., and the development time is usually about 10 to 600 seconds at room temperature. After development, after a washing step, it can be air dried with compressed air or compressed nitrogen.
As described above, an arbitrary structure (reference numeral 4 in FIG. 1) corresponding to the pattern mask used on the first substrate can be formed using the negative photosensitive resin composition.

Next, a process of bonding a second substrate (reference numeral 5 in FIG. 1) on the structure provided on the first substrate and bonding the two substrates will be described. Usually, the second substrate is pressure-bonded in a state where the structure is formed on the first substrate, and then both the substrates or the single substrate is heated to bond the two substrates. With respect to this step, it is preferable to appropriately change the method of pressing and heating both substrates depending on the type of substrate.
This adhesion process is based on the thermal polymerization reaction of the (D) epoxy compound contained in the negative photosensitive resin composition.

For example, in the case of bonding / bonding a glass substrate, the first substrate on which the structure is formed is placed on a heated hot plate, the second substrate is immediately bonded, heated and left to stand. It is possible to bond the substrates. It is also possible to place a second substrate in advance on the first substrate on which the structure is formed, and to perform pressure bonding through a subsequent heating step. These are performed under atmospheric pressure or reduced pressure depending on the function of the functional element.
As the temperature in the heating step, a temperature at which sufficient adhesiveness is developed in consideration of the reactivity of the epoxy compound (D) is appropriately selected. For example, in the case of a solid epoxy compound, the adhesiveness is usually expressed by heating and bonding in the range of 100 ° C to 200 ° C. In consideration of the deformation of the structure during heating, it is more preferable to bond at a heating temperature of 180 ° C. or less.

  In the case of pressure bonding / bonding the plastic film substrate, the second substrate film may be pressure bonded to the first substrate film on which the structure has been created in advance using a roll bonding apparatus. It is possible to bond the two substrates by applying heat immediately after the bonding. It is also possible to heat the first substrate film and the second substrate film in which the structure is prepared in advance immediately before the bonding, and perform the pressure bonding and the heating step almost simultaneously. In the heating step, a temperature range that does not damage the substrate plastic film is preferable, and it is necessary to appropriately control the heating conditions (heating temperature, holding time) depending on the type of the plastic film. These are performed under atmospheric pressure or reduced pressure depending on the function of the functional element.

  Although the above description is an example of a functional element in which two substrates are bonded via a structure, a second structure is provided on the second substrate according to the above, and a third substrate is provided thereon. It is also possible to manufacture a functional element having a multilayer structure by adhering.

  In this manner, the first substrate provided with an arbitrary structure according to the pattern mask and the second substrate are bonded and bonded / adhered via the structure by appropriately adjusting the bonding conditions. Thus, a desired functional element can be formed. A liquid crystal display element is mentioned as a particularly preferable functional element in the present invention.

When the functional element of the present invention is applied to a liquid crystal display element, for example, it is prepared as follows (see FIG. 2).
First, a structure (reference numeral 4 in FIG. 2) is provided on the first substrate (reference numeral 1 in FIG. 2) in accordance with the above-described method, and a sealant (reference numeral 6 in FIG. 2) is applied. A substrate (reference numeral 2 in FIG. 2) is pressure-bonded, then liquid crystal is injected from a liquid crystal inlet (reference numeral 7 in FIG. 2), and the inlet is sealed to obtain the liquid crystal display element of the present invention. In the liquid crystal display element of the present invention, the structure prepared from the negative photosensitive resin composition has a function of adhering both substrates, and a certain amount of liquid crystal (reference numeral 8 in FIG. 2) is provided between the substrates. It also has a function of a spacer for providing a gap for holding.
The method for producing the functional element of the present invention is also included in the present invention.

The functional element of the present invention has high resolution and excellent adhesion to the substrate. Therefore, it is useful as a liquid crystal display element, a plasma display element, an electronic circuit element, an optical semiconductor element (light receiving element, light emitting element, CMOS, CCD chip, etc.), an element for producing MEMS, and the like.
The said negative photosensitive resin composition used for the functional element of this invention is also contained in this invention.

  Next, although the functional element of this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples. In the following, “%” and “part” mean “% by weight” and “part by weight”, respectively, unless otherwise specified.

Example 1 to Example 3, Comparative Example 1 to Comparative Example 2
Preparation of negative photosensitive resin composition solution Each composition was prepared according to the composition shown in Table 1 below to obtain a negative photosensitive resin composition.

Table 1 (Composition table, units are parts)

Note (A) component DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
TMPTA (Trimethylolpropane triacrylate Nippon Kayaku Co., Ltd.)
Component (B) Alkali-soluble phenol resin (A); Copolymer of parahydroxystyrene and styrene (80:20 in weight ratio, weight average molecular weight 10,000)

Alkali-soluble resin (I); parahydroxystyrene polymer (weight average molecular weight 10,000)
(U): PHM-C (partially hydrogenated parahydroxystyrene polymer, manufactured by Maruzen Petrochemical Co., Ltd., weight average molecular weight 5500, hydrogenation rate 11.8%)

Component (C) Irgacure 907 (Photopolymerization initiator Ciba Specialty Chemicals)
(D) Component (A); (Epoxy compound represented by the above formula (1): NC6000 (softening point 63 ° C., epoxy equivalent 222) manufactured by Nippon Kayaku Co., Ltd.)
(A); (2,2-bis (hydroxymethyl) -1-butanol and 1,2-epoxy-4-vinylcyclohexane polymer (softening point 77 ° C., epoxy equivalent 181)

Other curing accelerator: 1B2PZ (1-benzyl-2-phenylimidazole, manufactured by Shikoku Kasei Co., Ltd.)
Curing agent: Ricacid TH-W (tetrahydrodicarboxylic acid anhydride, manufactured by Shin Nippon Rika Co., Ltd.)
Surfactant: Megafac F-470 (Fluorosurfactant, Dainippon Ink & Chemicals, Inc.)
Photopolymerization initiation aid: EAB-F (4,4′-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.)
Chain transfer agent: PEMP (pentaerythritol tetrakis (β-thiopropionate) manufactured by Sakai Chemical Industry Co., Ltd.)
Solvent: Propylene glycol monomethyl ether acetate

Examples 4 to 6, Comparative Example 3 to Comparative Example 4
Preparation of functional element The process shown in FIG. 1 using non-alkali glass as the first substrate using the solution of each negative photosensitive resin composition obtained in Table 1 according to the coating conditions in Table 2. (Second substrate = non-alkali glass) to obtain each functional element.

Table 2 (Coating conditions)

  Note: Example numbers of the negative photosensitive resin compositions used are shown.

  As the developer, a 2.38% aqueous solution of tetramethylammonium hydroxide was used.

Next, evaluation of adhesiveness and resolution of the negative photosensitive resin composition of the present invention will be described.
○ Adhesive evaluation (Process for creating first substrate for adhesive evaluation)
Each negative resin composition solution obtained in Table 1 was applied onto a 60 mm square, 0.7 mm thick alkali-free glass substrate (borosilicate glass) using a spin coating method. Thereafter, pre-baking was performed on a hot plate at 100 ° C. for 180 seconds. The coating film thus obtained was exposed in an air atmosphere under the condition that the ultraviolet irradiation energy at 365 nm was 500 mJ without a pattern mask. Thereafter, development was performed under the conditions described in Table 2, rinsed and air-dried.

(Creation of adhesive evaluation element)
On each of the first substrates obtained as described above, 10 pieces of 1.75 mm square alkali-free glass (borosilicate glass) chips were placed at equal intervals as the second substrate (see FIG. 3). . Thereafter, the first substrate on which the second substrate is mounted is placed on a hot plate heated to 150 ° C., and a glass substrate similar to the base material of the first substrate is placed on the second substrate. Further, 5 weights of 100 g were placed thereon and left for 30 minutes. After leaving for 30 minutes, the pressure-bonding glass substrate placed on the second substrate and the weight were removed, and the first substrate to which the second substrate chip was bonded was removed from the hot plate. In this way, a functional element for adhesion evaluation was obtained.

(Adhesion evaluation)
The adhesion of each functional element for adhesion evaluation obtained above was measured as follows. For adhesion evaluation, a bond tester (SS-30W manufactured by Seishin Shoji Co., Ltd.) was used. Each functional element was installed on the evaluation table of the bond tester, and the resistance force was measured by applying an external force from the lateral direction (see FIG. 4). The results are shown in Table 3. Functional elements for adhesion evaluation (Examples 7 to 9, Comparative Examples 5 to 6) obtained using negative photosensitive resin compositions (Examples 1 to 3 and Comparative Examples 1 and 2). ) Showed high adhesion.

Table 3 Measurement results of adhesion
Example 7 Example 8 Example 9 Comparative Example 5 Comparative Example 6
(Note) (Example 1) (Example 2) (Example 3) (Comparative Example 1) (Comparative Example 2)
Adhesive strength (MPa) 23.1 21.9 22.4 21.4 20.9

  Note: Example numbers of the negative photosensitive resin compositions used are shown.

○ Resolution evaluation The resolution of the structure prepared on the first substrate was evaluated as follows. The first substrate is exposed through a predetermined mask to produce φ10 μm, φ20 μm, and φ30 μm structures (first substrate for resolution evaluation), and the shape and patterning properties of these structures are optical. Observed with a microscope.

(Process for creating first substrate for resolution evaluation)
Each negative resin composition solution obtained in Table 1 was applied onto a 60 mm square, 0.7 mm thick non-alkali glass substrate (borosilicate glass) using a spin coat method. Thereafter, pre-baking was performed on a hot plate at 100 ° C. for 180 seconds. Using a predetermined pattern mask on the film thus obtained, exposure was performed under the condition of an exposure illuminance of 500 mJ at 365 nm in an air atmosphere by a direct exposure method. Then, according to the conditions of Table 2, after carrying out the development process, it was rinsed and air dried. The film thickness after curing at this time was 7 μm each. In this way, a first substrate for resolution evaluation (Example 10 to Example 12, Comparative Example 7 to Comparative Example 8) was obtained.

(Resolution evaluation by microscopic observation)
About the 1st board | substrate obtained by the above, the patterning property of the cylindrical pattern (structure) of (phi) 10micrometer, (phi) 20micrometer, and (phi) 30micrometer was observed using the optical microscope. The results are shown in Table 4.

About the evaluation standard structure ○: A sharp structure is observed.
Δ: Slightly sagging
X: There is a pattern fatness.

Residue / Scum ○: None.
Δ: There is a little.
X: Many.

Table 4 Evaluation results of resolution
Example 10 Example 11 Example 12 Comparative Example 7 Comparative Example 8
(Note) (Example 1) (Example 2) (Example 3) (Comparative Example 1) (Comparative Example 2)
φ10μm ○ ○ ○ △ ○
φ20μm ○ ○ ○ ○ ○
φ30μm ○ ○ ○ ○ ○
Residue ○ ○ ○ △ ×
Scum ○ ○ ○ △ ×
Note: Example numbers of the negative photosensitive resin compositions used are shown.

The composition of Comparative Example 2 is a negative photosensitive resin composition containing the constituents described in Patent Document 6.
As is clear from the above results, each resolution obtained using Comparative Example 1 which is a composition containing an alkali-soluble polymer composed only of hydroxystyrene and Comparative Example 2 which is a composition of Patent Document 6. In the first substrate for evaluation (Comparative Example 7 and Comparative Example 8), although there was no problem in the shape of the structure, residue and scum were observed, whereas Example 1 which is the negative photosensitive resin composition of the present invention. Each of the first substrates for evaluation of resolution (Examples 10 to 12) obtained by using Example 3 has a cylindrical structure having no residue or scum and having a good sharpness and contrast. Observed. That is, the negative photosensitive resin composition of the present invention gives a structure having excellent adhesive strength, heat resistance and the like, and has an excellent pattern forming ability without residue and scum. It was confirmed that a structure having pattern resolution was obtained.
By using the negative photosensitive resin composition of the present invention, an excellent functional element can be obtained.

Schematic of the process in creating the functional element of the present invention Schematic of a liquid crystal display element to which the functional element of the present invention is applied Schematic diagram of substrate with adhesive glass chip Schematic diagram of bond tester

Explanation of symbols

1-4, 1-11 mean the following.
DESCRIPTION OF SYMBOLS 1 1st board | substrate 2 Negative photosensitive resin composition coating layer 3 Pattern mask 4 Structure 5 2nd board | substrate 6 Seal agent layer 7 Liquid crystal inlet 8 Liquid crystal 9 Glass chip 10 Scratch 11 Bond tester Evaluation stand

Claims (15)

The structure is formed in a functional element in which the second substrate is bonded by bonding the two substrates through a patterned structure provided by photolithography on the first substrate. Resin composition for (A) acrylic monomer, (B) alkali-soluble phenol resin obtained by copolymerizing hydroxystyrene and styrene, (C) photopolymerization initiator and (D) epoxy compound A functional element, which is a negative photosensitive resin composition. The functional element according to claim 1, wherein the negative photosensitive resin composition further contains a solvent. The functional element according to claim 1 or 2 , wherein a molar blending ratio of hydroxystyrene which is a constituent component of the alkali-soluble phenol resin obtained by copolymerization is 60 mol% to 95 mol%. The functional element according to any one of claims 1 to 3 , wherein a softening point of the epoxy compound (D) in the negative photosensitive resin composition is 40 ° C to 110 ° C. (D) The epoxy compound is a polymer of 2,2-bis (hydroxymethyl) -1-butanol and 1,2-epoxy-4-vinylcyclohexane or an epoxy compound represented by the following formula (1): Item 5. A functional element according to Item 4 .

The proportion of the (D) epoxy compound in the negative photosensitive resin composition in the total amount of (A), (B), (C) and (D) is 5% to 50% by weight. The functional device according to any one of claims 1 to 5 . The functional element according to any one of claims 1 to 6 , wherein the functional element is an element used for a liquid crystal display element. Contains (A) an acrylic monomer, (B) an alkali-soluble phenol resin obtained by copolymerizing hydroxystyrene and styrene, (C) a photopolymerization initiator and (D) an epoxy compound on the first substrate. A functional element in which two substrates are integrated, wherein a structure is provided by photolithography using a negative photosensitive resin composition to be bonded, and then a second substrate is pressure-bonded onto the structure. Method. The manufacturing method according to claim 8 , wherein the functional element is a liquid crystal display element. A resin composition containing (A) an acrylic monomer, (B) an alkali-soluble phenol resin obtained by copolymerizing hydroxystyrene and styrene, (C) a photopolymerization initiator and (D) an epoxy compound. Then, it is used to create a functional element in which the second substrate is bonded by bonding the second substrate through a patterned structure provided on the first substrate by photolithography. A negative photosensitive resin composition for forming the structure. The negative photosensitive resin composition according to claim 10 , wherein the negative photosensitive resin composition further contains a solvent. The negative photosensitive resin composition according to claim 10 or 11 , wherein a molar blending ratio of hydroxystyrene which is a constituent component of the alkali-soluble phenol resin obtained by copolymerization is 60 mol% to 95 mol%. . The negative photosensitive resin composition according to any one of claims 10 to 12 , wherein a softening point of the epoxy compound (D) in the negative photosensitive resin composition is 40 ° C to 110 ° C. (D) The epoxy compound is a polymer of 2,2-bis (hydroxymethyl) -1-butanol and 1,2-epoxy-4-vinylcyclohexane or an epoxy compound represented by the above formula (1). Item 14. The negative photosensitive resin composition according to Item 13 . The proportion of the (D) epoxy compound in the negative photosensitive resin composition in the total amount of (A), (B), (C) and (D) is 5% to 50% by weight. The negative photosensitive resin composition as described in any one of Claims 10 thru | or 14 .

Images