TWI556061B - Negative photosensitive resin composition, cured film, and member for touch panel - Google Patents

Description

Negative photosensitive resin composition, cured film, and member for touch panel

The present invention relates to a flat film for forming a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic electroluminescence display element, a protective film or an insulating film of a touch panel sensor element, or the like, and an interlayer insulating film of a semiconductor element. The adhesion improver to which the resin composition used is applied. Further, the negative photosensitive composition using the same, a cured film formed therefrom, and a member for a touch panel having the cured film.

Currently, the use of hard coating materials is variable. For example, the surface hardness of containers, sheets, films, optical disks, thin displays, and the like used in automobile parts, cosmetics, and the like is increased. The properties required for the hard coating material include hardness and scratch resistance, and heat resistance, weather resistance, adhesion, and the like. A typical example of the hard coat material is a radically polymerizable UV curable hard coat material (Non-Patent Document 1). The composition of the hard coating material is a polymerizable group-containing oligomer, a monomer, a photopolymerization initiator, and other additives.

The oligomer and the monomer are subjected to radical polymerization by UV irradiation to crosslink to obtain a film having a high hardness. Since this hard coating material takes a short time due to hardening, if this material is used, productivity can be improved. Further, since a negative photosensitive material which utilizes a general radical polymerization mechanism can be used, it has an advantage of being inexpensive to manufacture.

When a negative photosensitive material is used for various display elements and a capacitive touch panel, the substrate has a pattern made of a metal film such as ITO (Indium Tin Oxide) film or Mo (Molybdenum). Therefore, the negative photosensitive resin has good adhesion to ITO and Mo, and is a property expected in various display elements and capacitive touch panels. In particular, in the capacitive touch panel that has received attention in recent years, the ITO film or the metal film occupies a large area on the substrate, and a hard coating material that solves this problem is required.

As a method of improving the adhesion, a method of adding a decane coupling agent is known (Patent Document 1). In particular, the aminoalkyl decane has a high adhesion improving effect and is useful.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-187321

[Non-patent literature]

[Non-Patent Document 1] Da Yuansheng et al. "Material Design in Hard Coatings Centered on Plastic Substrates ‧ Coating Technology and Improvement in Hardness", Technical Information Association, April 28, 2005, p. 301

As described above, the aminoalkyl decane has a high effect of improving the adhesion, and is useful. However, if the amount of addition is increased in order to improve the adhesion improving effect, it may be insoluble in the alkali developing solution due to prolonged placement after prebaking. . This phenomenon is considered a problem when mass production.

An object of the present invention is to provide a composition which is excellent in adhesion to a surface of a substrate made of a metal or an inorganic material, and which does not appear to be insoluble in an alkali developer even after standing for a long time after prebaking.

In order to solve the above problems, the inventors of the present invention have focused on a decane coupling agent and found that a decane coupling agent having a specific structure contributes to solving the problem. The present invention includes a negative photosensitive resin composition characterized by containing (A) a decane coupling agent represented by the general formula (1) or the general formula (2), and (B) an alkali-soluble resin. (C) a polyfunctional acrylic monomer and (D) a photoradical polymerization initiator.

(n represents an integer of 0 to 2. R ¹ represents a monovalent organic group or a fluorine group having 1 to 30 carbon atoms. R ¹ may have a substituent. R ² represents a divalent organic group having 1 to 6 carbon atoms. R ³ They may be the same or different and each represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group and a phenoxy group. At least one of R ³ is selected from the group consisting of carbon number 1 to 6 alkoxy, hydroxyl.) (R ⁴ represents a monovalent aryl group having 1 to 12 carbon atoms. R ⁴ may have a substituent. R ⁵ represents a divalent organic group having 1 to 6 carbon atoms. R ⁶ may be the same or different, and represents a carbon number of 1 An alkyl group of ~6, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, and a phenoxy group. At least one of R ⁶ is selected from alkoxy groups having 1 to 6 carbon atoms and a hydroxyl group.

The negative photosensitive composition of the present invention is excellent in adhesion to a surface of a substrate made of a metal or an inorganic material, and does not cause insoluble in an alkali developing solution even after standing for a long time after prebaking. Further, since the decane coupling agent of the present invention can be used in combination with a candid resin, it is also possible to provide a composition containing an enamel resin which is excellent in adhesion to a surface of a substrate made of a metal or an inorganic material.

[Formation of the Invention]

The negative photosensitive resin composition of the present invention is characterized by comprising at least: (A) a decane coupling agent represented by the formula (1) or the formula (2), (B) an alkali-soluble resin, and (C) a polyfunctional group. Acrylic monomer, (D) photoradical polymerization initiator.

Hereinafter, each constituent component of the negative photosensitive resin composition of the present invention will be described.

The negative photosensitive composition of the present invention has the following (A) a decane coupling agent represented by the formula (1) or the formula (2).

(n represents an integer of 0 to 2. R ¹ represents a monovalent organic group or a fluorine group having 1 to 30 carbon atoms. R ² represents a divalent organic group having 1 to 6 carbon atoms. R ³ may be the same or different, and represents The alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group and a phenoxy group. At least one of R ³ is selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms and a hydroxyl group. )

(R ⁴ represents a monovalent aryl group having 1 to 12 carbon atoms. R ⁴ may have a substituent. R ⁵ represents a divalent organic group having 1 to 6 carbon atoms. R ⁶ may be the same or different, and represents a carbon number of 1 An alkyl group of ~6, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, and a phenoxy group. At least one of R ⁶ is selected from alkoxy groups having 1 to 6 carbon atoms and a hydroxyl group.

R ¹ and R ⁴ may have a substituent such as an alkoxy group, an aryl group, a phenoxy group or a halogen group. Here, R ³ and R ^{6 are} preferably a methoxy group, an ethoxy group or a butoxy group, and a methoxy group or an ethoxy group is preferred from the viewpoint of obtaining a raw material.

The decane coupling agent represented by the formula (1) includes 3-(trimethoxyindenyl)propane-1-amine oxime sulfonate and 3-(trimethoxyindenyl) 10-camphorsulfonate. Propane-1-amine oxime, 10-camphorsulfonic acid 3-(triethoxyindolyl)propane-1-amine oxime, trifluoromethanesulfonic acid 3-(trimethoxyindolyl)propane-1-amine oxime, etc. .

The decane coupling agent represented by the formula (2) includes benzene. 3-(trimethoxyindolyl)propane-1-amine sulfonate, 3-(trimethoxyindolyl)propane-1-amine oxime 4-methylbenzenesulfonate, 4-methylbenzenesulfonic acid 3- (Triethoxycarbonyl)propane-1-amine oxime and the like.

When these decane coupling agents are added to the negative photosensitive resin, they may be used singly or in combination.

As a method for producing such a decane coupling agent, from the viewpoint of easiness of production, it is preferred to react and prepare an aminoalkyl decane and an alkyl (aryl) sulfonic acid in an organic solvent by room temperature. Methods. Although it is considered that a small amount of unreacted material remains in this synthesis method, it does not have a significant influence on the adhesion improving effect, and it can be used without being separately separated and purified. However, in order to reduce the residual amount of the amino decane, the molar ratio of the alkyl (aryl) sulfonic acid is preferably designed to be large.

The amount of the (A) decane coupling agent to be added is preferably based on the total amount of the resin component of the negative photosensitive resin composition, that is, the total amount of the (B) alkali-soluble resin and the (C) polyfunctional acrylic monomer. It is 0.5 to 10% by mass, more preferably 1 to 5% by mass. When the amount is less than 0.5% by mass, the effect of improving the adhesion is insufficient, and if it is more than 15% by mass, a fine pattern may be less likely to be dissolved during alkali development, and the resolution may be lowered.

Examples of the (B) alkali-soluble resin include polyoxyalkylene oxide, acrylic resin, vinyl ether resin, polyhydroxystyrene, novolak resin, polyimide, polyamine, oxime resin and the like. Among the (B) alkali-soluble resins, at least a part of the introduction of the ethylenically unsaturated double bond group is advantageous for increasing the hardness of the cured film. Among these polymers, from the viewpoint of easiness of introduction of the ethylenically unsaturated double bond group, polysiloxane, acrylic resin, and oxime resin are more preferable. Also, these polymers 2 may also be included More than one species. In order to improve chemical resistance or refractive index, it is more preferable to contain a fluorene resin.

Here, the inventors of the present invention have found that when an anthracene resin is used, if an aminoalkyl decane is added, the oxime resin is insoluble and precipitates, so that it may not be easily used, but the decane coupling by the present invention. There are new effects that can eliminate this phenomenon.

Preferred examples of the (B) alkali-soluble resin are as follows, but are not limited thereto.

As the polyoxyalkylene oxide, a reaction product obtained by subjecting a trifunctional alkoxydecane compound to hydrolysis and condensation reaction is particularly preferred. The trifunctional alkoxydecane compound is as follows.

For example: methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, hexyl trimethoxy decane, octadecyl trimethoxy decane, phenyl trimethoxy Base decane, phenyltriethoxy decane, naphthyltrimethoxy decane, decyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-(2-aminoethyl)-3- Aminopropyltrimethoxydecane, 3-(N,N-diepoxypropyl)aminopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, glycidoxy Methyltrimethoxydecane, glycidoxymethyltriethoxydecane, α-glycidoxyethyltrimethoxydecane, α-glycidoxyethyltriethoxydecane, β -glycidoxyethyltrimethoxydecane, β-glycidoxyethyltriethoxydecane, α-glycidoxypropyltrimethoxydecane, α-glycidoxypropane Triethoxy decane, β-glycidoxypropyltrimethoxydecane, β-glycidoxypropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, Γ-glycidoxypropyl triethyl Oxydecane, γ-glycidoxypropyltripropoxydecane, γ-glycidoxypropyltriisopropoxydecane, γ-glycidoxypropyl tributoxy decane, --glycidoxybutyltrimethoxydecane, α-glycidoxybutyltriethoxydecane, β-glycidoxybutyltrimethoxydecane, β-glycidoxy Butyl triethoxy decane, γ-glycidoxybutyl trimethoxy decane, γ-glycidoxybutyl triethoxy decane, δ-glycidoxy butyl trimethoxy decane , δ-glycidoxybutyltriethoxydecane, (3,4-epoxycyclohexyl)methyltrimethoxydecane, (3,4-epoxycyclohexyl)methyltriethoxydecane (3,4-epoxycyclohexyl)methyltrimethoxydecane, (3,4-epoxycyclohexyl)methyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyl Tripropoxydecane, 2-(3,4-epoxycyclohexyl)ethyltributoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3, 4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propyltriethyl Oxyquinone , 4-(3,4-epoxycyclohexyl)butyltrimethoxydecane, 4-(3,4-epoxycyclohexyl)butyltriethoxydecane, trifluoromethyltrimethoxydecane, three Fluoromethyltriethoxydecane, trifluoropropyltrimethoxydecane, trifluoropropyltriethoxydecane, and the like.

Further, by using a trifunctional alkoxydecane containing an ethylenically unsaturated double bond, it is preferred to introduce an ethylenically unsaturated double bond based on polyoxyalkylene to increase the hardness of the cured film.

Specifically, vinyl trimethoxy decane, vinyl triethoxy decane, γ-methyl propylene oxypropyl trimethoxy decane, γ-methyl propylene oxypropyl triethoxy decane, γ- Propylene oxiranyl trimethoxy decane, γ-propylene methoxypropyl triethoxy decane, and the like.

As the acrylic resin, it is preferred to carry out radical polymerization of (meth)acrylic acid or (meth)acrylic acid ester. (Meth) acrylates, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, Cyclohexyl (meth)acrylate, cyclohexene (meth)acrylate, 4-methoxycyclohexyl (meth)acrylate, 2-cyclopropoxycarbonylethyl (meth)acrylate, (A) 2-cyclopentyloxycarbonylethyl acrylate, 2-cyclohexyloxycarbonylethyl (meth)acrylate, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, (meth)acrylic acid 2 -(4-methoxycyclohexyl)oxycarbonylethyl ester, norbornyl (meth)acrylate, isodecyl (meth)acrylate, tricyclodecyl (meth)acrylate, tetra(meth)acrylate An oxime ester, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, adamantyl (meth)acrylate, 1-methyladamantyl (meth)acrylate, and the like. An aromatic vinyl compound such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene or α-methylstyrene may be added to the above (meth)acrylic acid or (meth)acrylate. Copolymerization.

Further, an ethylenically unsaturated double bond group can be introduced by subjecting an epoxy compound having an ethylenically unsaturated double bond group to an addition reaction of (meth)acrylic acid. Examples of the epoxy compound having an ethylenically unsaturated double bond group include the following compounds.

Specifically, for example, glycidyl (meth)acrylate, α-ethylglycidyl (meth)acrylate, α-n-propylglycidyl (meth)acrylate, (meth)acrylic acid α-Butylpropyl propyl acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxyheptyl (meth)acrylate, α-ethyl-6,7-(meth)acrylate Epoxy heptyl ester, allyl epoxidized ether, vinyl epoxy Propyl ether, o-vinylbenzyl epoxidized propyl ether, m-vinylbenzyl epoxidized propyl ether, p-vinylbenzyl epoxidized propyl ether, α-methyl-o-vinyl benzyl epoxidized propyl ether, α- Methyl-vinyl benzyl epoxidized propyl ether, α-methyl-p-vinylbenzyl epoxidized propyl ether, 2,3-diepoxypropoxymethyl styrene, 2,4-diepoxypropyl Oxymethylstyrene, 2,5-diepoxypropoxymethylstyrene, 2,6-diepoxypropoxymethylstyrene, 2,3,4-triepoxypropoxy Styrene, 2,3,5-triepoxypropoxymethylstyrene, 2,3,6-triepoxypropoxymethylstyrene, 3,4,5-triepoxypropoxy Methylstyrene, 2,4,6-triepoxypropoxymethylstyrene, and the like.

Commercially available products are preferably used as the oxime resin, and examples thereof include OGSOL (registered trademark) CR-TR1, same CR-TR2, same CR-TR3, same CR-TR4, same CR-TR5, and CR-TR6 (above). For Osaka Gas Chemical System).

In the negative photosensitive resin composition of the present invention, the content of the (B) alkali-soluble resin is not particularly limited, and may be arbitrarily selected depending on the desired film thickness or use. (B) The alkali-soluble resin is preferably added in an amount of 10 to 70% by mass based on the solid content of the negative photosensitive resin composition.

The negative photosensitive composition of the present invention contains (C) a polyfunctional monomer. A polyfunctional single system refers to a compound having at least two or more ethylenically unsaturated double bonds in a molecule. In view of the ease of radical polymerizability, a polyfunctional monomer having an acrylic group is preferred.

Specific examples include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate urethane, modified bisphenol A epoxy (meth) acrylate, and hexamethylene Acid 1,6-hexanediol (meth) acrylate, phthalic anhydride propylene oxide (meth) acrylate, trimellitic acid Diethylene glycol (meth) acrylate, rosin-modified epoxy di(meth) acrylate, oligomer such as alkyd modified (meth) acrylate, or tripropylene glycol di (meth) acrylate Ester, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tris (a) Acrylate, triacrylate, acetal, pentaerythritol tetra(meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate , pentaerythritol octa (meth) acrylate, [9,9-bis[4-(2-propenyloxyethoxy)phenyl] hydrazine, and the like.

The negative photosensitive resin composition of the present invention contains (D) a photoradical polymerization initiator. (D) The photoradical polymerization initiator may be any one which decomposes and/or reacts due to light (including ultraviolet rays or electron beams) to generate a radical. In order to increase the hardness of the cured film, an α-aminoalkylphenone, a mercaptophosphine oxide compound, an oxime ester compound, a diphenyl ketone compound having an amine group or a benzoate compound having an amine group is preferably used. Further, two or more kinds of these compounds may be contained.

Specific examples of the α-aminoalkylphenone compound include 2-methyl-[4-(methylthio)phenyl]-2- Olinone propan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Polin-4-yl-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4- Oleinophenyl)-butanone-1 and the like.

Specific examples of the fluorenylphosphine oxide include 2,4,6-trimethylbenzimidylphenylphosphine oxide and bis(2,4,6-trimethylbenzylidene)-phenyl oxide. Phosphine, bis(2,6-dimethoxybenzylidene)-(2,4,4-trimethylpentyl)-phosphine oxide, and the like.

Specific examples of the oxime ester compound include 1-phenyl-1,2-propene. Diketo-2-(o-ethoxycarbonyl)anthracene, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzylidenefluorene)], 1-benzene 1,2-butanedione-2-(o-methoxycarbonyl)anthracene, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)anthracene, ethyl ketone, 1- [9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) and the like.

Specific examples of the diphenyl ketone compound having an amine group include 4,4-bis(dimethylamino)diphenyl ketone and 4,4-bis(diethylamino)diphenyl ketone. Wait.

Specific examples of the benzoate compound having an amine group include ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, and p-diethylaminobenzoic acid. Ethyl ester and the like.

(D) The content of the photoradical polymerization initiator is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more, based on the solid content of the negative photosensitive resin composition. Further, it is preferably 20% by mass or less and more preferably 10% by mass or less. By setting it as the said range, radical hardening can fully be performed, and the solvent resistance which prevents the elution of the residual radical-polymerization initiator can be securable.

The negative photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability of the composition is improved, and in the application requiring pattern processing, the resolution after development is improved. Specific examples of the polymerization inhibitor include phenol, catechol, resorcin, hydroquinone, 4-t-butylcatechol, 2,6-di(t-butyl)-p-cresol, and brown. Thio , 4-methoxyphenol, and the like.

The content of the polymerization inhibitor is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more based on the solid content of the negative photosensitive resin composition. miss you. In addition, from the viewpoint of maintaining the hardness of the cured film to be high, it is preferably 5% by mass or less and more preferably 1% by mass or less.

The negative photosensitive resin composition of the present invention may contain a solvent. From the viewpoint of uniformly dissolving the components and improving the transparency of the obtained coating film, a compound having an alcoholic hydroxyl group or a cyclic compound having a carbonyl group is preferably used. Two or more kinds of these compounds may also be contained. Further, it is more preferably a compound having a boiling point of 110 to 250 ° C at atmospheric pressure.

When the boiling point is 110 ° C or more, the drying of the coating film proceeds moderately, and a good coating film having no coating unevenness can be obtained. On the other hand, when the boiling point is 250 ° C or lower, the amount of residual solvent in the film can be suppressed to a small amount, and film shrinkage at the time of thermal curing can be further reduced, so that more excellent flatness can be obtained.

Specific examples of the compound having an alcoholic hydroxyl group and having a boiling point of 110 to 250 ° C at atmospheric pressure include acetol, 3-hydroxy-3-methyl-butanone, and 4-hydroxy-3-methyl group. 2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol and the like. Among these, from the viewpoint of preservation stability, diacetone alcohol is preferable, and from the viewpoint of coating with respect to height difference, propylene glycol mono-tert-butyl ether is preferable.

Specific examples of the cyclic compound having a carbonyl group and having a boiling point of 110 to 250 ° C at atmospheric pressure include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propyl carbonate, and N-methyl group. Pyrrolidone, cyclohexanone, cycloheptanone, and the like. Among these, γ-butyrolactone is preferred.

Further, the negative photosensitive resin composition of the present invention may contain various solvents such as acetates, ketones, and ethers other than the above.

The content of the solvent is not particularly limited and may be any amount depending on the coating method. For example, in the case of forming a film by spin coating, the amount of the solvent is generally 50 to 95% by mass based on the entire negative photosensitive resin composition.

The negative photosensitive resin composition of the present invention may contain various curing agents which promote curing of the resin composition or facilitate curing. The curing agent is not particularly limited, and a known product can be used. Specific examples thereof include a nitrogen-containing organic substance, an anthrone-based resin curing agent, various metal alkoxides, various metal chelate compounds, an isocyanate compound and a polymer thereof, a methylolated melamine derivative, and a methylolated urea derivative. These two or more types may also be contained. Among them, a metal chelate compound, a methylolated melamine derivative, or a methylolated urea derivative is preferably used from the viewpoints of the stability of the curing agent, the processability of the obtained coating film, and the like.

The negative photosensitive resin composition of the present invention may contain various surfactants such as a fluorine-based surfactant and an anthrone-based surfactant in order to improve fluidity during coating. The type of the surfactant is not particularly limited, and for example, a fluorine-based surfactant, an anthrone-based surfactant, a polyalkylene oxide-based surfactant, a poly(meth)acrylate-based surfactant, or the like can be used. These two or more types can also be used.

As a commercial product of a fluorine-based surfactant, it is preferable to use "MEGAFAC" (registered trademark) F142D, the same F172, the same F173, the same F183, the same F445, the same F470, the same F475, the same F477 (above is the Dainippon ink chemical industry) (share) system, NBX-15, FTX-218 (NEOS (share) system). As a commercial product of an anthrone-based surfactant, BYK-333 should be used. BYK-301, BYK-331, BYK-345, BYK-307 (BYK (share) system).

A description will be given of a representative production method of the negative photosensitive resin composition of the present invention. For example, (A) a decane coupling agent represented by the general formula (1) or the general formula (2), (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, and (D) photoradical polymerization initiation The agent and other additives as needed are added to any solvent, stirred and dissolved, and the obtained solution is filtered to obtain a negative photosensitive resin composition.

A method of forming a cured product using the negative photosensitive resin composition of the present invention is exemplified. The negative photosensitive resin composition of the present invention is applied to a substrate by a known method such as a micro gravure coating method, a spin coating method, a dip coating method, a curtain coating method, a roll coating method, a spray coating method, or a slit coating method. The substrate is pre-baked by a heating device such as a hot plate or an oven. The prebaking is carried out in the range of 50 to 150 ° C for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.1 to 15 μm.

After prebaking, exposure is performed using an exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA). The light is or is not interposed between the masks at an exposure intensity of about 10 to 400 J/cm ² (in terms of a wavelength of 365 nm). The exposure light source is not limited, and ultraviolet rays such as i-line, g-line, and h-line can be used. Or KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like.

Next, the exposed portion is dissolved by development to obtain a negative pattern. As the developing method, it is preferred to immerse in the developing solution for 5 seconds to 10 minutes by a method such as showering, dipping, or paddle. Display A well-known alkali developer can be used for the liquid solution. Specific examples thereof include an inorganic base such as an alkali metal hydroxide, a carbonate, a phosphate, a citrate or a borate; an amine such as 2-diethylaminoethanol, monoethanolamine or diethanolamine; One or two or more aqueous solutions of a four-stage ammonium salt such as ammonium hydroxide or choline. After development, it is preferably rinsed with water, and then dried and baked at a temperature of 50 to 140 °C.

Thereafter, the film is heated in a heating plate of a hot plate or an oven at a temperature of 140 to 320 ° C for about 15 minutes to 1 hour.

The cured film obtained by curing the negative photosensitive resin composition of the present invention can be used as a touch panel protective film, a touch panel insulating film, various hard coating materials, an antireflection film, and an optical filter. Moreover, since it has a negative-type photosensitive property, it is suitable for the flattening film for TFTs of an liquid crystal or an organic electroluminescent display, an insulating film, an anti- Among them, a touch panel protective film or a touch panel insulating film which is not particularly suitable for substrates such as ITO or molybdenum and which requires adhesion after heat treatment and drug treatment is preferable. Examples of the touch panel method include a resistive film type, an optical type, an electromagnetic induction type, and an electrostatic capacitance type. In particular, the capacitive touch panel is required to have chemical treatment resistance, so that the cured film of the present invention can be suitably used.

When the cured film of the present invention is used as a protective film for a touch panel, the hardness at a film thickness of 1.5 μm is 4H or more, the transmittance is 95% or more, and the resolution is preferably 20 μm or less. The hardness or the transmittance can be adjusted by the selection of the exposure amount and the heat hardening temperature.

[Examples]

The invention is more specifically illustrated by the following examples. The invention does not These embodiments are limited. Among the compounds used in the synthesis examples and the examples, the abbreviations for use are as follows.

PGMEA: propylene glycol monomethyl ether acetate

DAA: Diacetone alcohol

MB: 3-methoxy-1-butanol

Synthesis Example 1 Synthesis of decane coupling agent solution (a-1)

1.501 g (10 mmol) of trifluoromethanesulfonic acid and 1.793 g (10 mmol) of 3-aminopropyltrimethoxydecane were added to MB 62.586 g, and stirred at room temperature for 15 minutes to obtain 3-(trimethoxymethanesulfonate). A 5% MB solution (a-1) of propanyl-1-amine oxime.

Synthesis Example 2 Synthesis of decane coupling agent solution (a-2)

1.92 g (10 mmol) of p-toluenesulfonic acid monohydrate and 1.793 g (10 mmol) of 3-aminopropyltrimethoxydecane were added to MB 64.983 g, and stirred at room temperature for 15 minutes to obtain 4-methylbenzenesulfonic acid 3 - 5% MB solution of (trimethoxyindenyl)propan-1-amine oxime (a-2).

Synthesis Example 3 Synthesis of decane coupling agent solution (a-3)

2.23 g (10 mmol) of 10-camphorsulfonic acid and 1.793 g (10 mmol) of 3-aminopropyltrimethoxydecane were added to MB 77.944g, and stirred at room temperature for 15 minutes to obtain 3-camphorsulfonic acid 3-(trimethoxy). A 5% MB solution (a-3) of propanyl-1-amine oxime.

Synthesis Example 4 Preparation of decane coupling agent solution (a-4)

1.93 g (10 mmol) of 3-aminopropyltrimethoxydecane was added to MB 34.067 g, and stirred at room temperature for 15 minutes to obtain a 5% MB solution (a-4) of 3-aminopropyltrimethoxydecane.

Synthesis Example 5 Synthesis of decane coupling agent solution (a-5)

0.981 g (10 mmol) of concentrated sulfuric acid and 1.793 g (10 mmol) of 3-aminopropyltrimethoxydecane were added to MB 52.706 g, and stirred at room temperature for 15 minutes to obtain 3-(trimethoxydecyl)propane hydrogensulfate- 1-amine 5% 5% MB solution (a-5).

Synthesis Example 6 Synthesis of decane coupling agent solution (a-6)

0.961 g (10 mmol) of methanesulfonic acid and 1.793 g (10 mmol) of 3-aminopropyltrimethoxydecane were added to MB 52.326 g, and stirred at room temperature for 15 minutes to obtain 3-(trimethoxydecyl) methanesulfonate. Propane-1-amine 5% 5% MB solution (a-6).

Synthesis Example 7 Synthesis of a decane resin solution (b-1)

13.62 g (0.1 mol) of methyltrimethoxydecane, 118.98 g (0.6 mol) of phenyltrimethoxydecane, 39.39 g (0.15 mol) of 3-trimethoxydecylpropylsuccinic acid, γ- 35.16 g of methacrylic acid methoxypropyltrimethoxydecane and 140.87 g of DAA were placed in a 500 ml three-necked flask. Thereafter, while stirring the mixture at room temperature, an aqueous phosphoric acid solution in which 0.106 g of phosphoric acid (0.05% by mass based on the monomer added) was dissolved in 59.4 g of water was added dropwise over 30 minutes. After the flask was immersed in an oil bath at 40 ° C and stirred for 30 minutes, the oil bath was heated to 115 ° C for 30 minutes. One hour after the start of the temperature rise, the internal temperature of the solution reached 100 ° C, and the mixture was further heated and stirred for 45 minutes (the internal temperature was 100 to 110 ° C). In the reaction, a total of 89 g of by-product methanol and water were distilled off, and DAA was added thereto to obtain a polymer concentration of 40% by mass based on the DAA solution of the obtained polyoxyalkylene to obtain a decane resin solution (b-1). The weight average molecular weight of the obtained polymer was 7,500.

Synthesis Example 8 Synthesis of Acrylic Resin Solution (b-2)

2 g of 2,2'-azobis(isobutyronitrile) was added to a 500 ml flask. PGMEA (propylene glycol monomethyl ether acetate) 50 g. Thereafter, 30 g of methacrylic acid, 22.48 g of styrene, and 25.13 g of cyclohexyl methacrylate were added. Thereafter, the mixture was stirred at room temperature for a while, and after the inside of the flask was replaced with nitrogen, the mixture was heated and stirred at 70 ° C for 5 hours. Then, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was stirred under heating at 90 ° C for 4 hours. PGMEA was added so that the solid content concentration of the obtained acrylic resin solution was 40% by mass, and an acrylic resin solution (b-2) was obtained. The acrylic resin had a weight average molecular weight of 13,500 and an acid value of 100 mgKOH/g.

Synthesis Example 9 Preparation of bismuth resin solution (b-3)

OGSOL (registered trademark) CR-TR5 (manufactured by Osaka Gas Chemical Co., Ltd.), which is a resin PGMEA solution, is a product having a solid content of 52.7% and a solid content of 135. 100 g of CR-TR5 was weighed, and 33.75 g of PGMEA was added and stirred. In this way, a ruthenium resin solution (b-3) having a solid content concentration of 40% by mass was obtained.

(1) Evaluation of MAM adhesion

On the alkali-free glass substrate (glass thickness: 0.7 mm), the MAM was formed into a substrate so as to have a film thickness of 2,500 Å and a resistance of 0.3 Ω/□. The cured film having a film thickness of 1.5 μm produced on the substrate (hereinafter referred to as MAM substrate) was evaluated for adhesion between the MAM substrate and the cured film in accordance with JIS "K5400" 8.5.2 (1990) checkerboard tape method. . On the surface of the cured film on the glass substrate, a parallel line of 11 vertical and horizontal lines perpendicularly intersecting was cut at intervals of 1 mm so that the cutting blade cut the bottom surface of the glass plate, and 100 squares of 1 mm × 1 mm were produced. Attach a transparent adhesive tape to the surface of the cured film (width = 18mm, adhesion = 3.7N/10mm), with an eraser (JIS S6050 qualified product) rubbed to make it tight. Then, one end of the tape was gripped, and the remaining number of squares when the film was peeled off at right angles to the plate was visually evaluated. The peeling area of the square was determined in the following manner.

5: peeling area 0%

4: peeling area 0~<5%

3: peeling area 5~<15%

2: Stripping area 15~<35%

1: peeling area 35~<65%

0: peeling area 65~<100%

(2) Chemical resistance (TOK106 resistance)

On the alkali-free glass substrate (glass thickness: 0.7 mm), the substrate was formed so that the ITO film thickness was 200 Å and the resistance value was 100 Ω/□. A cured film having a film thickness of 1.5 μm was formed on this substrate (hereinafter referred to as an ITO substrate). After immersing in TOK-106 which is a resist stripper under the following conditions, the adhesion between the ITO substrate and the cured film was evaluated in accordance with JIS "K5400" 8.5.2 (1990) checkerboard tape method. When the peeling area of the square is 5% or less, it is judged that the condition is resistant.

Condition 1: 60 ° C, 80 seconds

Condition 2: 60 ° C, 5 minutes

Condition 3: 85 ° C, 5 minutes

Based on the condition-free conditions of drug resistance, drug resistance was evaluated in the following four stages.

3: Conditions 1, 2, and 3 are resistant

2: Conditions 1, 2 have resistance

1: Only condition 1 has resistance

0: No resistance to all conditions

(3) Developmental change caused by placement after prebaking (development margin after prebaking)

The ITO substrate was spin-coated at any number of revolutions using a spin coater (1H-360S manufactured by MIKASA Co., Ltd.), and the substrate was prebaked at 110 ° C for 2 minutes using a hot plate (SCW-636 manufactured by DAINIPPON SCREEN Co., Ltd.). Four films having a film thickness of 1.5 μm were produced.

The time to transfer to the subsequent exposure step was divided into 30 minutes, 6 hours, 12 hours, and 24 hours. The film to be produced is a parallel light mask aligner (PLA-501F manufactured by Canon), and an ultrahigh pressure mercury lamp is used as a light source. A mask having a width of 50 μm and a width of 1 to 1 is used for an exposure amount of 200 mJ. (i line), mask gap 100 μm exposure. After that, an automatic developing device (AD-2000, manufactured by Ryuza Seiki Co., Ltd.) was used to carry out a shower development for 90 seconds with a 0.4% by mass aqueous solution of tetramethylammonium hydroxide ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.). Then, rinse with water for 30 seconds. If the pattern having a width of 50 μm can be imaged even after being placed after prebaking, the margin after prebaking is evaluated.

Example 1

Under a yellow light, 2-methyl-[4-(methylthio)phenyl]-2- Olefin propan-1-one (trade name "IRGACURE (registered trademark) 907" Ciba Specialty Chemicals Co., Ltd. (hereinafter referred to as IC907)) 1.557g, 4,4-bis(diethylamino)di 0.173 g of phenyl ketone (hereinafter referred to as EK) was dissolved in 15.000 g of DAA, 5.99 g of MB, and 30.000 g of PGMEA. In this solution, dipentaerythritol hexaacrylate (trade name "KAYARAD (registered trademark) DPHA", manufactured by Nippon Chemical Co., Ltd. (hereinafter referred to as DPHA), 8.652 g, and decane coupling agent solution (a-1) 6.922 were added. g, 4-p-butyl catechol PGMEA1 mass% solution 8.652g, helium oxide resin solution (b-1) 21.630g, BYK-333 which is an anthrone-based surfactant (BYK JAPAN) The PGMEA1 mass% solution was 1.500 g and stirred, and then filtered through a 0.45 μm filter to obtain a negative photosensitive resin composition (N-1).

The negative photosensitive resin composition (N-1) obtained was spin-coated at a random number of revolutions on a MAM substrate and an ITO substrate using a spin coater (1H-360S manufactured by MIKASA Co., Ltd.), and then the substrates were used for hot plates. (SCW-636 manufactured by DAINIPPON SCREEN Co., Ltd.) was prebaked at 110 ° C for 2 minutes to prepare a film having a film thickness of 1.5 μm.

The prepared film was subjected to a parallel light mask aligner (PLA-501F manufactured by Canon Co., Ltd.), and an ultrahigh pressure mercury lamp was used as a light source, and exposed at an exposure amount of 200 mJ (i line). After that, an automatic developing device (AD-2000, manufactured by Ryuza Seiki Co., Ltd.) was used to carry out a shower development for 90 seconds with a 0.4% by mass aqueous solution of tetramethylammonium hydroxide ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.). Then, rinse with water for 30 seconds. Finally, an oven (ESPEC-222, manufactured by ESPEC) was used and hardened in air at 220 ° C for 1 hour to prepare a cured film. The MAM adhesion and TOK106 resistance were evaluated by the methods described above for the obtained cured film. Further, the development margin after prebaking was evaluated by the aforementioned method.

Example 2

A negative photosensitive resin composition (N-) was obtained in the same manner as in Example 1 except that 6.722 g of the decane coupling agent solution (a-1) was replaced with 1.731 g of the decane coupling agent solution (a-2). 2). The negative photosensitive resin composition (N-2) obtained was used for evaluation in the same manner as in Example 1.

Example 3

Replace the decane coupling agent solution (a-1) 6.922g with decane coupling A negative photosensitive resin composition (N-3) was obtained in the same manner as in Example 1 except that the amount of the solution (a-2) was 6.922 g. The negative photosensitive resin composition (N-3) obtained was used for evaluation in the same manner as in Example 1.

Example 4

A negative photosensitive resin composition (N-) was obtained in the same manner as in Example 1 except that 6.722 g of the decane coupling agent solution (a-1) was replaced with 20.766 g of the decane coupling agent solution (a-2). 4). The negative photosensitive resin composition (N-4) obtained was used for evaluation in the same manner as in Example 1.

Example 5

A negative photosensitive resin composition (N-) was obtained in the same manner as in Example 1 except that 6.922 g of the decane coupling agent solution (a-1) was replaced with 6.922 g of the decane coupling agent solution (a-3). 5). The negative photosensitive resin composition (N-5) obtained was used for evaluation in the same manner as in Example 1.

Example 6

Under a yellow light, 1.557 g of IC907 and 0.173 g of EK were dissolved in DAA 17.597 g, MB 5.914 g, and PGMEA 30.000 g. To this solution, 10.382 g of DPHA, decane coupling agent solution (a-2) 6.922 g, 4-tributylcatechol PGMEA 1 mass% solution 8.652 g, and acrylic resin solution (b-2) 17.303 were added. g, 1.000 g of PGMEA1 mass% solution of BYK-333 (BYK JAPAN Co., Ltd.) which is an anthrone-based surfactant, and stirred. Then, it was filtered with a 0.45 μm filter to obtain a negative photosensitive resin composition (N-6). The negative photosensitive resin composition (N-6) obtained was used for evaluation in the same manner as in Example 1.

Example 7

The amount of the decane coupling agent solution (a-2) added to 6.922 g was changed to A negative photosensitive resin composition (N-7) was obtained in the same manner as in Example 6 except for the above. The negative photosensitive resin composition (N-7) obtained was used for evaluation in the same manner as in Example 1.

Example 8

IC907, 1.257 g of IC907, and 0.173 g of EK were dissolved in DAA 15.000 g, MB 5.914 g, and PGMEA 27.405 g under a yellow lamp. To this solution, 6.922 g of DPHA, decane coupling agent solution (a-2) 6.922 g, 4-tributylcatechol PGMEA 1 mass% solution 8.652 g, and acrylic resin solution (b-2) 17.303 were added. g, 8.052 g of a bismuth resin solution (b-3), 1.000 g of a PGMEA1 mass% solution of BYK-333 (manufactured by BYK JAPAN Co., Ltd.) which is an anthrone-based surfactant, and stirred. Then, it was filtered with a 0.45 μm filter to obtain a negative photosensitive resin composition (N-8). The negative photosensitive resin composition (N-8) obtained was used for evaluation in the same manner as in Example 1.

Example 9

Under a yellow light, 1.557 g of IC907 and 0.173 g of EK were dissolved in DAA 25.000 g, MB 5.914 g, and PGMEA 20.000 g. To this solution, 8.652 g of DPHA, decane coupling agent solution (a-1) 6.922 g, 4-tributylcatechol PGMEA 1 mass% solution 8.652 g, and an anthraquinone resin solution (b-3) were added. 21.630 g of 1.00 g of PGMEA 1 mass% solution of BYK-333 (BYK JAPAN Co., Ltd.) which is an anthrone-based surfactant and stirred. Then, it was filtered with a 0.45 μm filter to obtain a negative photosensitive resin composition (N-9).

Example 10

Replace the decane coupling agent solution (a-1) 6.922g with decane coupling A negative photosensitive resin composition (N-10) was obtained in the same manner as in Example 9 except that the amount of the agent (a-2) was 6.922 g. The negative photosensitive resin composition (N-10) obtained was used for evaluation in the same manner as in Example 1.

Example 11

A negative photosensitive resin composition (N-11) was obtained in the same manner as in Example 9 except that 6.922 g of the decane coupling agent solution (a-1) was replaced with 6.922 g of a decane coupling agent (a-3). ). The negative photosensitive resin composition (N-11) obtained was used for evaluation in the same manner as in Example 1.

Example 12

A negative photosensitive resin composition (N-12) was obtained in the same manner as in Example 9 except that 6.722 g of the decane coupling agent solution (a-1) was replaced with 20.766 g of a decane coupling agent (a-2). ). The negative photosensitive resin composition (N-12) obtained was used for evaluation in the same manner as in Example 1.

Comparative example 1

A negative photosensitive resin composition (N-13) was obtained in the same manner as in Example 1 except that 6.72 g of the decane coupling agent solution (a-1) was not added. The negative photosensitive resin composition (N-13) obtained was used for evaluation in the same manner as in Example 1.

Comparative example 2

A negative photosensitive resin composition (N-14) was obtained in the same manner as in Example 1 except that 6.922 g of the decane coupling agent solution (a-1) was replaced with 6.922 g of a decane coupling agent (a-4). ). The negative photosensitive resin composition (N-14) obtained was used for evaluation in the same manner as in Example 1.

Comparative example 3

Replace the decane coupling agent solution (a-1) 6.922g with decane coupling A negative photosensitive resin composition (N-15) was obtained in the same manner as in Example 1 except that the amount of the agent (a-4) was 20.766 g. The negative photosensitive resin composition (N-15) obtained was used for evaluation in the same manner as in Example 1.

Comparative example 4

A negative photosensitive resin composition (N-16) was obtained in the same manner as in Example 1 except that 6.922 g of the decane coupling agent solution (a-1) was replaced with 6.922 g of a decane coupling agent (a-5). ). The negative photosensitive resin composition (N-16) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 5

A negative photosensitive resin composition (N-17) was obtained in the same manner as in Example 1 except that 6.922 g of the decane coupling agent solution (a-1) was replaced with 6.922 g of a decane coupling agent (a-6). ). The negative photosensitive resin composition (N-17) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 6

A negative photosensitive resin composition (N-18) was obtained in the same manner as in Example 6 except that 6.72 g of the decane coupling agent solution (a-3) was not added. The negative photosensitive resin composition (N-18) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 7

A negative photosensitive resin composition (N-19) was obtained in the same manner as in Example 6 except that 6.722 g of the decane coupling agent solution (a-3) was replaced with 20.766 g of a decane coupling agent (a-4). ). The negative photosensitive resin composition (N-19) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 8

No addition of decane coupling agent solution (a-1) 6.922g, in addition to Example 9 was carried out in the same manner to obtain a negative photosensitive resin composition (N-20). The negative photosensitive resin composition (N-20) obtained was evaluated in the same manner as in Example 1.

Comparative Example 9

A negative photosensitive resin composition (N-21) was prepared in the same manner as in Example 9 except that 6.922 g of the decane coupling agent solution (a-1) was replaced with 6.922 g of a decane coupling agent (a-4). ). However, it was found that the solution was cloudy and could not be filtered with a 0.45 μm filter. If the solution was allowed to stand at room temperature for 1 day, it was confirmed that some precipitate occurred. Therefore, the evaluation of MAM adhesion, TOK106 resistance, and development margin after prebaking was not performed.

Comparative Example 10

A negative photosensitive resin composition (N-22) was prepared in the same manner as in Example 9 except that 6.922 g of the decane coupling agent solution (a-1) was replaced with 6.922 g of a decane coupling agent (a-5). ). However, it was found that the solution was cloudy and could not be filtered with a 0.45 μm filter. If the solution was allowed to stand at room temperature for 1 day, it was confirmed that some precipitate occurred. Therefore, the evaluation of MAM adhesion, TOK106 resistance, and development margin after prebaking was not performed.

Comparative Example 11

A negative photosensitive resin composition (N-23) was prepared in the same manner as in Example 9 except that 6.922 g of the decane coupling agent solution (a-1) was replaced with 6.922 g of a decane coupling agent (a-6). ). However, it was found that the solution was cloudy and could not be filtered with a 0.45 μm filter. If the solution was allowed to stand at room temperature for 1 day, it was confirmed that some precipitate occurred. Therefore, the evaluation of MAM adhesion, TOK106 resistance, and development margin after prebaking was not performed.

[Industrial availability]

The present invention can be suitably used for a negative photosensitive resin composition, a cured film using the composition, and a touch panel device having the cured film.

Claims (4)

A negative photosensitive resin composition characterized by comprising at least: (A) a decane coupling agent represented by the general formula (1) or the general formula (2), (B) an alkali-soluble resin, and (C) a polyfunctional acrylic resin Monomer, (D) photoradical polymerization initiator; (n represents an integer of 0 to 2; R ¹ represents a monovalent organic group or a fluorine group having 1 to 30 carbon atoms; and R ² represents a divalent organic group having 1 to 6 carbon atoms; and R ³ may be the same or different, respectively, An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group and a phenoxy group; at least one of R ³ is selected from alkoxy groups having 1 to 6 carbon atoms; (R ⁴ represents a monovalent aryl group having 1 to 12 carbon atoms; R ⁴ may have a substituent; R ⁵ represents a divalent organic group having 1 to 6 carbon atoms; and R ⁶ may be the same or different, and represents a carbon number of 1; An alkyl group of ~6, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, and a phenoxy group; at least one of R ⁶ is selected from an alkoxy group having 1 to 6 carbon atoms and a hydroxyl group). The negative photosensitive resin composition of claim 1, wherein the (B) alkali-soluble resin is a cardo resin having an ethylenically unsaturated group. A cured film obtained by hardening a negative photosensitive resin composition according to claim 1 or 2. A member for a touch panel having a cured film as in item 3 of the patent application.