TWI505031B - Silane coupling agent, negative photosensitive resin composition, cured film and component for touch panel - Google Patents

Description

A decane coupling agent, a negative photosensitive resin composition, a cured film, and a member for a touch panel

The present invention relates to a decane coupling agent which is suitable for forming a planarization film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film or an insulating film of a touch panel sensing element, or the like, and a semiconductor. A resin composition for an interlayer insulating film of an element. Further, the negative photosensitive composition using the cured photosensitive film and the member for a touch panel having the cured film.

At present, the use of hard coating materials involves many aspects. For example, it is used to improve the surface hardness of containers, sheets, films, optical disks, thin displays, and the like of automobile parts, cosmetics, and the like. In addition to hardness and scratch resistance, the properties required for the hard coat material include 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 (see, for example, Non-Patent Document 1). The composition of the hard coat material is a polymerizable group-containing oligomer, a monomer, a photopolymerization initiator, and other additives.

The oligomer and the monomer are crosslinked by radical polymerization by UV irradiation to obtain a film having a high hardness. This hard coating material requires a short period of time due to hardening, and if it is used, productivity is improved. Further, since a negative photosensitive material of a general radical polymerization mechanism can be used, there is an advantage that the manufacturing cost becomes cheap.

In recent years, one of the applications of the electrostatic capacitive touch panel is a hard coating material. The capacitive touch panel has a pattern made of an ITO (Indium Tin Oxide) film on glass. In order to protect this ITO, a film having high hardness is required. However, it is difficult to cope with high hardness and good adhesion to ITO, and a hard coat material which solves this problem is required.

As a method of improving the adhesion, a method of adding a decane coupling agent is well known. For example, a decane coupling agent having a quinone imine group is proposed as a decane coupling agent (see Patent Document 1 and Patent Document 2). In these documents, in order to have good flatness and to improve adhesion, it is recommended to use a compound having a quinone imine group instead of a proline structure. In addition, as a decane coupling agent which is suitable for a composition of a heat resistant resin precursor, a compound having a carboxyl group and an ester group, or a carboxyl group and a guanamine group is proposed (see Patent Document 3).

However, when any of the decane coupling agents is used as a hard coating agent for a touch panel, the adhesion improving effect is insufficient.

Further, it has been proposed to add an organic hydrazine compound having a phthalic acid structure to a polyimide composition (Patent Document 4). However, this organic ruthenium compound is a structure in which an amine group-containing decane coupling agent is added to an anion of an aromatic ring. The organic bismuth compound is strong in coloring and is not suitable for use in a touch panel, and adhesion improvement and hardening are not sufficient.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] WO2008-065944

[Patent Document 2] WO2009-096050

[Patent Document 3] JP-A-2006-316032

[Patent Document 4] JP-A-9-222729

[Non-patent literature]

[Non-Patent Document 1] Ohara, et al., "Material Design of Hard Coating Film Centered on Plastic Substrate, Improvement of Coating Technology and Hardness", Technical Information Society, April 28, 2005, p. 301

An object of the present invention is to provide a cured film which is excellent in adhesion to a surface of a substrate made of a metal or an inorganic material, has high hardness, and is excellent in resolution. Further, another object of the present invention is to provide a cured film having a low curing shrinkage ratio and good flatness.

In order to solve the above problems, the present invention consists of the following constitutions. That is, the decane coupling agent represented by the following formula (1),

(R ¹ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms; the alkyl group may have a more substituent; n represents 0 or 1; and R ² represents a trivalent organic group having 3 to 30 carbon atoms; ³ may be the same or different, and 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; and, among these groups of R ³ , in addition to a hydroxyl group In addition, there may be more substituents).

The cured film containing a decane coupling agent of the present invention has an effect of being excellent in adhesion to a surface of a substrate made of a metal or an inorganic material, high in hardness, and excellent in resolution. Further, the cured film containing a decane coupling agent of the present invention has an effect of low curing shrinkage ratio and good flatness.

[Formation of the Invention]

The decane coupling agent of the present invention has a structure represented by the following formula (1).

(R ¹ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms; the alkyl group may have a more substituent; n represents 0 or 1; and R ² represents a trivalent organic group having 3 to 30 carbon atoms; ³ may be the same or different, and 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; and, among these groups of R ³ , in addition to a hydroxyl group In addition, there may be more substituents).

Here, R ^{1 is} preferably a methyl group, an ethyl group or a butyl group, and particularly preferably a methyl group or an ethyl group from the viewpoint of obtaining a raw material. R ¹ may have a substituent such as an alkoxy group, an aryl group, a phenoxy group or a halogen group. R ^{3 is} preferably a trivalent organic group having 3 to 30 carbon atoms, and more preferably a trivalent organic group having 3 to 10 carbon atoms from the viewpoint of solubility in an organic solvent.

The decane coupling agent represented by the formula (1) of the present invention includes, for example, 3-(t-butylaminocarbamyl)-6-(trimethoxydecyl)hexanoic acid, 2-(2- (Tertiary butylamino)-2-oxoethyl)-5-(trimethoxydecyl)pentanoic acid, 3-(isopropylaminemethanyl)-6-(trimethoxydecylalkyl) Caproic acid, 2-(2-(isopropylamino)-2-oxoethyl)-5-(trimethoxydecyl)pentanoic acid, 3-(isobutylaminecarbamyl)-6- (trimethoxydecyl)hexanoic acid, 2-(2-(isoxylamino)-2-oxoethyl)-5-(trimethoxydecyl)pentanoic acid, 3-(third pentyl) Aminomethyl) 6-(trimethoxydecyl)hexanoic acid, 2-(2-(tripentylamino)-2-oxoethyl)-5-(trimethoxydecyl)pentane Acid, 3-(t-butylaminocarbamimidyl)-6-(triethoxydecyl)hexanoic acid, 2-(2-(t-butylamino)-2-oxoethyl)- 5-(triethoxydecyl)pentanoic acid, 6-(dimethoxy(methyl)decyl)-3-(t-butylaminemethylmercapto)hexanoic acid, 5-(dimethoxy) (Methyl)decyl-2-(2-(t-butylamino)-2-oxoethyl)pentanoic acid, 3-(t-butylaminemethylmercapto)-6-(trimethoxy)矽alkyl)pentanoic acid, 2-(2-(t-butylamino)-2-oxo Ethyl ethyl)-5-(trimethoxydecyl)butyric acid, 2-(t-butylaminemethylmercapto)-4-(2-(trimethoxydecyl)ethyl)cyclohexanecarboxylic acid And 2-(t-butylaminecarbamyl)-5-(2-(trimethoxydecyl)ethyl)cyclohexanecarboxylic acid and the like.

Among these, a compound having n=0 in the above formula (1) is particularly preferable from the viewpoint that the effect of improving the ITO adhesion is high.

Specifically, 3-(t-butylaminocarbamido)-6-(trimethoxydecyl)hexanoic acid, 2-(2-(t-butylamino)-2-oxoethyl)- 5-(trimethoxydecyl)pentanoic acid, 3-(isopropylaminecarbamimidoyl)-6-(trimethoxydecyl)hexanoic acid, 3-(third amylaminecarbamyl)-6 -(trimethoxydecyl)hexanoic acid, 2-(2-(th-pentylamino)-2-oxoethyl)-5-(trimethoxydecyl)pentanoic acid, 3-(third Butylamine carbaryl)-6-(triethoxydecyl)hexanoic acid, 2-(2-(t-butylamino)-2-oxoethyl)-5-(triethoxy)矽alkyl)pentanoic acid, 6-(dimethoxy(methyl)decyl)-3-(t-butylaminemethylmercapto)hexanoic acid, 5-(dimethoxy(methyl)decyl- 2-(2-(Tertiary butylamino)-2-oxoethyl)pentanoic acid, 3-(t-butylaminemethylmercapto)-6-(trimethoxydecyl)pentanoic acid, 2 -(2-(Tertiary butylamino)-2-oxoethyl)-5-(trimethoxydecyl)butyric acid, 2-(t-butylaminemethylmercapto)-4-(2 -(trimethoxydecyl)ethyl)cyclohexanehexanecarboxylic acid, 2-(t-butylaminemethylmercapto)-5-(2-(trimethoxydecyl)ethyl)cyclohexane The hexane carboxylic acid is in accordance with.

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, a method of producing an acid anhydride-containing decane coupling agent and an alkylamine is preferred because of ease of manufacture. At this time, depending on the structure of the anhydride-containing decane coupling agent, the decane coupling agent of the present invention simultaneously produces two types. However, it is not necessary to separate and refine these, and it can be used as a mixture. Further, in the synthesis method, copying of a small amount of oligomers or the like is also considered, but the effect of improving the adhesion is not greatly affected, and it is not necessary to consider it.

The 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 is preferably from 1 to 15% by mass, more preferably 3 ～10% by mass. When the amount is less than 1% by mass, the effect of improving the adhesion is insufficient. When the amount is more than 15% by mass, the fine pattern is peeled off during alkali development, and the resolution is lowered.

The negative photosensitive resin composition using the decane coupling agent of the present invention is characterized by comprising at least (A) a decane coupling agent represented by the formula (1), (B) an alkali-soluble resin, and (C) a polyfunctional acrylic acid. Body, (D) photoradical polymerization initiator.

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

The negative photosensitive composition of the present invention contains (B) an alkali-soluble resin. By having an alkali-soluble resin, the negative-type photosensitive resin composition is excellent in alkali solubility (developing property), and the residue after development is suppressed, and a favorable pattern can be formed. Further, by having an ethylenically unsaturated double bond group, the crosslinking density can be increased and the hardness of the cured film can be improved.

Examples of the (B) alkali-soluble resin include polyoxyalkylene oxide, acrylic resin, vinyl ether resin, polyhydroxystyrene, novolac resin, polyimine, and polyamine. In the (B) alkali-soluble resin, it is preferred to introduce an ethylenically unsaturated double bond group in at least a part to increase the hardness of the cured film. Among these polymers, from the viewpoint of easiness of introduction of the ethylenically unsaturated double bond group, polypyroxane or acrylic resin is more preferable. Further, two or more kinds of these polymers may be contained. 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 exemplified below.

For example, methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, hexyltrimethoxydecane,octadecyltrimethoxydecane,phenyltrimethoxy 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-glycidoxypropyltriethoxyhydrazine , γ-glycidoxypropyl tripropoxy decane, γ-glycidoxypropyl triisopropoxy decane, γ-glycidoxypropyl tributoxy decane, α-ring Oxypropoxybutyltrimethoxydecane, α-glycidoxybutyltriethoxydecane, β-glycidoxybutyltrimethoxydecane, β-glycidoxybutylene Ethoxy decane, γ-glycidoxybutyltrimethoxydecane, γ-glycidoxybutyltriethoxydecane, δ-glycidoxybutyltrimethoxydecane, δ- Glycidoxy butyl triethoxy decane, (3,4-epoxycyclohexyl)methyltrimethoxy decane, (3,4-epoxycyclohexyl)methyltriethoxy decane, (3,4-Epoxycyclohexyl)methyltrimethoxydecane, (3,4-epoxycyclohexyl)methyltriethoxydecane, 2-(3,4-epoxycyclohexyl) Ethyltripropoxydecane, 2-(3,4-epoxycyclohexyl)ethyltributoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2 -(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxy Cyclohexyl) Triethoxy decane, 4-(3,4-epoxycyclohexyl)butyltrimethoxydecane, 4-(3,4-epoxycyclohexyl)butyltriethoxydecane, trifluoro Methyltrimethoxydecane, trifluoromethyltriethoxydecane, trifluoropropyltrimethoxydecane, trifluoropropyltriethoxydecane, and the like.

Further, by using a trifunctional alkoxysilane having an ethylenically unsaturated double bond group, an ethylenically unsaturated double bond group can be easily introduced into the polyoxyalkylene to improve the hardness of the cured film.

Specifically, vinyl trimethoxy decane, vinyl triethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-methyl propylene methoxy propyl triethoxy decane, γ - propylene methoxy propyl trimethoxy decane, γ-acryloxypropyl triethoxy decane, and the like.

As the acrylic resin, a (meth)acrylic acid or (meth) acrylate radical polymerizer is preferred. As the (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate , cyclohexyl (meth)acrylate, cyclohexenyl (meth)acrylate, 4-methoxycyclohexyl (meth)acrylate, 2-cyclopropoxycarbonylethyl (meth)acrylate, ( 2-cyclopentyloxycarbonylethyl (meth)acrylate, 2-cyclohexyloxycarbonylethyl (meth)acrylate, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, (meth)acrylic acid 2-(4-Methoxycyclohexyl)oxycarbonylethyl ester, borneol (meth)acrylate, isobornyl (meth)acrylate, tricyclodecyl (meth)acrylate, (meth)acrylic acid Tetracyclic decyl 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 the same as the above (meth)acrylic acid or (meth)acrylic acid ester. Copolymerization.

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

Specifically, glycidyl (meth)acrylate, α-ethylglycidyl (meth)acrylate, α-n-propylglycidyl (meth)acrylate, α-positive (meth)acrylate Butyl g-propyl acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxyheptyl (meth)acrylate, α-ethyl-6,7 (meth)acrylate - epoxyheptyl heptyl ester, allylepoxypropyl ether, vinyl epoxypropyl ether, o-vinylbenzyl epoxypropyl ether, m-vinylbenzyl epoxypropyl ether, p-vinylbenzyl Epoxy epoxide, α-methyl-o-vinylbenzylepoxypropyl ether, α-methyl-m-vinylbenzylepoxypropyl ether, α-methyl-p-vinylbenzyl ring Oxypropyl propyl ether, 2,3-diepoxypropyloxymethylstyrene, 2,4-diepoxypropyloxymethylstyrene, 2,5-diepoxypropyloxymethyl Styrene, 2,6-diepoxypropyloxymethylstyrene, 2,3,4-triepoxypropyloxymethylstyrene, 2,3,5-triepoxypropyloxy Methylstyrene, 2,3,6-triepoxypropyloxymethylstyrene, 3,4,5-triepoxypropyloxymethylstyrene, 2,4,6-triepoxy Propyloxymethylstyrene and the like.

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 in accordance with the desired film thickness or use. (B) The alkali-soluble resin is preferably added in an amount of 10 to 60% 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. The term "multifunctional monomer" means a compound having at least two or more ethylenically unsaturated double bonds in a molecule. In view of easiness of radical polymerizability, a multi-energy monomer having an acrylic group is preferred.

Specific examples thereof include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate urethane, and modified bisphenol A epoxy (meth) acrylate. , adipic acid 1,6-hexanediol (meth) acrylate, phthalic anhydride propylene oxide (meth) acrylate, trimellitic acid diethylene glycol (meth) acrylate, rosin modification Epoxy di(meth) acrylate, alkyd modified (meth) acrylate-like oligomer, or tripropylene glycol di(meth) acrylate, 1,6-hexanediol di(methyl) Acrylate, bisphenol A diglycidyl ether di(meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tripropylene formaldehyde, pentaerythritol tetra (a) Acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, [9, 9- Bis[4-(2-acryloxyethoxy)phenyl]anthracene 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 as long as it is decomposed and/or reacted by light (including ultraviolet rays or electron rays) to generate a radical. In order to further increase the hardness of the cured film, it is preferred to use an α-aminoalkylphenone compound, a mercaptophosphine oxide compound, an oxime ester compound, a diphenyl ketone compound having an amine group, or a benzoic acid having an amine group. Ester compound. 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-morpholinylpropan-1-one and 2-dimethyl group. Amino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino- 1-(4-morpholinylphenyl)-butanone-1 and the like.

Specific examples of the mercaptophosphine oxide compound include 2,4,6-trimethylbenzimidylphenylphosphine oxide and bis(2,4,6-trimethylbenzylidene)- Phenylphosphine oxide, 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-propanedione-2-(o-ethoxycarbonyl)anthracene, 1,2-octanedione, and 1-[4-(phenylsulfonate). Base-2-(o-benzylidene hydrazide)], 1-phenyl-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-乙醯基肟) and so on.

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-diethylamine. Ethyl benzoate and the like.

The content of the (D) photo-radical 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-type photosensitive resin composition. Further, it is preferably 20% by mass or less, and more preferably 10% by mass or less. By being in the above range, radical curing can be sufficiently performed, and elution of the residual radical polymerization initiator can be prevented, and solvent resistance can be ensured.

The negative photosensitive resin composition of the present invention may further contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability of the composition is improved, and the resolution after development can be improved in applications requiring pattern processing. Specific examples of the polymerization inhibitor include phenol, catechol, resorcin, hydroquinone, 4-t-butylcatechol, and 2,6-di(t-butyl)-p-cresol. Thiophene , 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. On the other hand, from the viewpoint of maintaining the hardness of the cured film having a high hardness, it is preferably 5% by mass or less, more preferably 1% by mass or less.

The negative photosensitive resin composition of the present invention may further contain a thermal acid generator. By the thermal acid generator, the effect of increasing the adhesion of the decane coupling agent can be further enhanced. Specific examples of the preferred thermal acid generator include triphenylsulfonium, 4-hydroxyphenyldimethylhydrazine, benzyl-4-hydroxyphenylmethylhydrazine, and 2-methylbenzyl- 4-hydroxyphenylmethylhydrazine, 2-methylbenzyl-4-ethinylphenylmethylhydrazine, 2-methylbenzyl-4-benzylideneoxyphenylmethylhydrazine, etc. Methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, and the like.

Also, it is preferable to use SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-200, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L (All three new chemical industry (stock) system). It is also possible to contain two or more of these.

The content of the thermal acid generator is preferably from 0.1 to 3% by mass based on the total 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. When the amount is less than 0.1% by mass, the effect of improving the adhesion is small, and if it is more than 3% by mass, the pattern is larger than the mask pattern, and the resolution is lowered.

The hafnium oxide resin composition of the present invention may also contain an ultraviolet absorber. By including an ultraviolet absorber, the light resistance of the obtained cured film is improved, and the resolution after development is improved in applications requiring pattern processing. The ultraviolet absorber is not particularly limited, and those skilled in the art can be used.

From the viewpoints of transparency and non-coloring, it is preferred to use a benzotriazole compound, a diphenyl ketone compound, and three a compound.

Examples of the ultraviolet absorber of the benzotriazole-based compound include 2-(2H-benzotriazol-2-yl)phenol and 2-(2H-benzotriazol-2-yl)-4,6-. Third amyl phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazole- 2-yl)-6-dodecyl-4-methylphenol, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, and the like.

Examples of the ultraviolet absorber of the diphenylketone compound include 2-hydroxy-4-methoxydiphenyl ketone and the like.

As three The ultraviolet absorber of the compound, which is exemplified by 2-(4,6-diphenyl-1,3,5 three -2-yl)-5-[(hexyl)oxy]-phenol and the like.

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. It is also possible to contain two or more of these. Further, a compound having a boiling point of 110 to 250 ° C at atmospheric pressure is more preferable.

When the boiling point is 110° C. or more, the film can be appropriately dried at the time of coating, and a good coating film having no coating unevenness can be obtained. On the other hand, by setting the boiling point to 250 ° C or lower, the amount of residual solvent in the film can be lowered, and film shrinkage during 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 acetamethanol, 3-hydroxy-3-methyl-2-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 single Ethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, 3-methoxy-1-butanone, 3-methyl-3-methoxy-1- Butanone and the like. Among these, from the viewpoint of preservation stability, diacetone alcohol is preferred, and propylene glycol mono-tert-butyl ether is preferred from the viewpoint of the step coverage property.

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. Pyrrolidone, cyclohexanone, cycloheptanone, and the like. Among these, γ-butyrolactone is preferred.

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

The content of the solvent is not particularly limited, and any amount can be used in accordance with a coating method or the like. For example, when the film is formed 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 hardener is not particularly limited, and those skilled in the art can be used. Specific examples include nitrogen-containing organic compounds, polyoxynoxy resin hardeners, various metal alkoxides, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, and methylolated urea derivatives. Wait. It is also possible to contain two or more of these. 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 and the processability of the obtained coating film.

The negative photosensitive resin composition of the present invention may contain various surfactants such as a fluorine-based surfactant or a polyfluorene-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, a polyoxyn-based surfactant, a polyalkylene oxide-based surfactant, a poly(meth)acrylate-based surfactant, or the like can be used. Two or more of these 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, the Japanese ink chemistry) Industrial (share) system, NBX-15, FTX-218 ((share) NEOS system). As a commercial item of a polyoxynene surfactant, BYK-333, BYK-301, BYK-331, BYK-345, and BYK-307 (BYK Chemical Japan Co., Ltd.) are preferably used.

A method for producing a representative of the negative photosensitive resin composition of the present invention will be described. For example, (A) a decane coupling agent represented by the formula (1), (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, (D) a photoradical polymerization initiator, and other additives as needed After stirring in an arbitrary solvent, the obtained solution was filtered, and the negative photosensitive resin composition was obtained.

A method of forming a cured film using the negative photosensitive resin composition of the present invention will be described by way of example. The negative photosensitive resin composition of the present invention is applied onto a base substrate by a well-known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating, using heat A heating device such as a plate or an oven is prebaked. The prebaking is preferably 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 mask aligner (PLA). The exposure intensity is about 10 to 4000 J/m ² (in terms of wavelength 365 nm exposure), and the light is irradiated with or without a desired mask. The exposure light source is not limited, and ultraviolet rays such as i-line, g-line, and h-line, or KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, or the like can be used.

Next, a negative pattern can be obtained by dissolving the exposed portion by development. As the developing method, it is preferred to immerse in a developing solution for 5 seconds to 10 minutes by a method such as spraying, impregnation, or liquid coating. As the developing liquid, a well-known alkali developing solution can be used. Specific examples include inorganic bases such as hydroxides, carbonates, phosphates, citrates, and borates containing one or more kinds of alkali metals, 2-diethylaminoethanol, and monoethanolamine. An aqueous solution of an amine such as diethanolamine, a tetra-ammonium hydroxide such as tetramethylammonium hydroxide or choline, or the like. After development, it is preferably rinsed with water, and then dried and baked at a temperature of 50 to 150 °C.

Then, the film is heated in a range of 150 to 450 ° C for about 20 minutes to 1 hour by a heating device such as a hot plate or an oven.

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, it is applicable to a planarizing film for a liquid crystal or an organic EL display, an insulating film, an antireflection film, a cover layer for a color filter, a pillar, or the like, because of its negative photosensitive property. Among these, a touch panel protective film or a touch panel insulating film which is a substrate which does not have Si such as ITO or molybdenum and which requires adhesion after heat treatment and after drug treatment can be suitably used. Examples of the touch panel include a resistive film type, an optical type, an electromagnetic induction type, and an electrostatic capacity type. As the electrostatic capacitance type touch panel, since a particularly high hardness is required, the cured film of the present invention can be used.

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

[Examples]

The invention will now be described more specifically by way of examples. The invention is not limited by these examples. Among the compounds used in the synthesis examples and the examples, the abbreviations used are as follows.

PGMEA: propylene glycol monomethyl ether acetal

DAA: Diacetone alcohol.

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

41.97 g (160 mmol) of 3-trimethoxydecylpropyl succinic anhydride and 11.70 g (160 mmol) of tributylamine were added to 200 g of PGMEA, and after stirring at room temperature for a while, the mixture was stirred at 40 ° C for 2 hours. Then, the temperature was raised to 80 ° C, and the reaction was allowed to proceed for 6 hours. The resulting solution was diluted with PGMEA to have a solid content concentration of 20% to give 3-(t-butylaminocarbamyl)-6-(trimethoxydecyl)hexanoic acid, 2-(2-(third A mixed solution of butylamino)-2-oxoethyl)-5-(trimethoxydecylalkyl)pentanoic acid (a-1).

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

41.97 g (160 mmol) of 3-trimethoxydecylpropyl succinic anhydride and 9.45 g (160 mmol) of the third pentylamine were added to 200 g of PGMEA, and after stirring at room temperature for a while, the mixture was stirred at 40 ° C for 2 hours. Then, the temperature was raised to 80 ° C, and the reaction was allowed to proceed for 6 hours. The resulting solution was diluted with PGMEA to have a solid concentration of 20% to give 2-(2-(t-amylamino)-2-oxoethyl)-5-(trimethoxydecyl)pentanoic acid. A mixed solution of 3-(t-amylaminecarbamyl)-6-(trimethoxydecyl)hexanoic acid (a-2).

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

41.97 g (160 mmol) of 3-trimethoxydecylpropyl succinic anhydride and 9.45 g (160 mmol) of isopropylamine were added to 200 g of PGMEA, and after stirring at room temperature for a while, the mixture was stirred at 40 ° C for 2 hours. Then, the temperature was raised to 80 ° C, and the reaction was allowed to proceed for 6 hours. The resulting solution was diluted with PGMEA to have a solid concentration of 20% to obtain 2-(2-(isopropylamino)-2-oxoethyl)-5-(trimethoxydecyl)pentanoic acid, A mixed solution of 3-(triisopropylaminemethanyl)-6-(trimethoxydecyl)hexanoic acid (a-3).

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

41.97 g (160 mmol) of 3-trimethoxydecylpropyl succinic anhydride and 9.45 g (160 mmol) of n-propylamine were added to 200 g of PGMEA, and after stirring at room temperature for a while, the mixture was stirred at 40 ° C for 2 hours. Then, the temperature was raised to 80 ° C, and the reaction was allowed to proceed for 6 hours. The resulting solution was diluted with PGMEA to have a solid content concentration of 20% to obtain 2-(2-oxo-2-(propylamino)ethyl)-5-(trimethoxydecyl)pentanoic acid, 3 a mixed solution of (-propylamine-mercapto)-6-(trimethoxydecyl)hexanoic acid (a-4).

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

41.97 g (160 mmol) of 3-trimethoxydecylpropyl succinic anhydride and 14.90 g (160 mmol) of aniline were added to 200 g of PGMEA, and after stirring at room temperature for a while, the mixture was stirred at 40 ° C for 2 hours. Then, the temperature was raised to 80 ° C, and the reaction was allowed to proceed for 6 hours. The obtained solution was diluted with PGMEA to have a solid content concentration of 20% to obtain 2-(2-oxo-2-(phenylamino)ethyl)-5-(trimethoxydecyl)pentanoic acid, 3 a mixed solution of (-phenylamine-mercapto)-6-(trimethoxydecyl)hexanoic acid (a-5).

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

41.97 g (160 mmol) of 3-trimethoxydecylpropyl succinic anhydride and 7.37 g (160 mmol) of ethanol were added to 200 g of PGMEA, and after stirring at room temperature for a while, the mixture was stirred at 40 ° C for 2 hours. Then, the temperature was raised to 80 ° C, and the reaction was allowed to proceed for 6 hours. The resulting solution was diluted with PGMEA to have a solid concentration of 20% to give 4-ethoxy-4-oxo-2-(trimethoxydecyl)butyric acid, 4-ethoxy-4-oxo a mixed solution of -3-(trimethoxydecyl)butyric acid (a-6).

Synthesis Example 7 Synthesis of decane coupling agent solution (a-7)

41.97 g (160 mmol) of 3-trimethoxydecylpropyl succinic anhydride and 11.70 g (160 mmol) of tributylamine were added to 400 g of PGMEA, and after stirring at room temperature for a while, the mixture was stirred at 60 ° C for 2 hours. Then, the temperature was raised to 140 ° C, and the reaction was carried out for 6 hours while azeotroping PGMEA with water. The resulting solution was diluted with PGMEA to have a solid content concentration of 20% to obtain a 1-(t-butyl)-3-trimethoxydecylalkylpyrrolidine-2,5-dione solution (a-7).

Synthesis Example 8 Synthesis of a decane resin solution (b-1)

13.62 g (0.1 mol) methyltrimethoxydecane, 118.98 g (0.6 mol) phenyltrimethoxydecane, 39.39 g (0.15 mol) 3-trimethoxydecylpropyl succinic acid, 35.16 g Gamma-methacryloxypropyltrimethoxydecane and 140.87 g of DAA were placed in a 500 ml three-necked flask. Then, while stirring the mixture at room temperature, an aqueous phosphoric acid solution in which 0.106 g (0.05% by mass of the monomer charged) of phosphoric acid was dissolved was added to 59.4 g of water for 30 minutes. Then, the flask was immersed in an oil bath at 40 ° C, and after stirring 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). A total of 89 g of methanol and water of the by-product in the reaction were distilled off. To the DAA solution of the obtained polyoxyalkylene, DAA was added to have a polymer concentration of 40% by mass to obtain a decane resin solution (b-1). The resulting polymer had a weight average molecular weight of 7,500.

Synthesis Example 9 Synthesis of Acrylic Resin Solution (b-2)

3 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetal) were placed in a 500 ml flask. Then, 30 g of methacrylic acid, 22.48 g of styrene, and 25.13 g of cyclohexyl methacrylate were added. Thereafter, the mixture was temporarily stirred at room temperature, and the inside of the flask was replaced with nitrogen, followed by heating and stirring at 70 ° C for 5 hours. Next, 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 the 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 10 Synthesis of quinonediazide compound (q-1)

Under a dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 37.62 g (0.14 mol) of 5-naphthoquinonediazidesulfonium chloride were dissolved in 450 g of 1, 4-two In the alkane, it becomes room temperature. In this solution, it is dripped with 50g 1,4-two in a manner that does not become 35 ° C or more in the system. 15.58 g (0.154 mol) of alkane mixed triethylamine. After the completion of the dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Then, the precipitated precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (q-1).

The evaluation methods in each of the examples and the comparative examples are shown below.

(1) Determination of hardness

The pencil hardness of the cured film having a thickness of 1.5 μm produced on a glass substrate of 5 cm square was measured in accordance with "JIS K5600-5-4 (1999)". However, the load is increased to 500g.

(2) Evaluation of ITO adhesion

On an alkali-free glass substrate (glass thickness 0.7mm), ITO becomes a film thickness of 200 The substrate has a resistance value of 100 Ω/□. The cured film having a film thickness of 1.5 μm produced on the substrate (hereinafter referred to as an ITO substrate) was evaluated for adhesion between the ITO and the cured film in accordance with the JIS "K5400" 8.5.2 (1990) checkerboard tape method. In the surface of the cured film on the glass substrate, eleven parallel lines of the vertical and horizontal directions were drawn at intervals of 1 mm so that the cutter reached the texture of the glass plate, and 100 squares of 1 mm × 1 mm were produced. On the surface of the cured film to be cut, a cellophane adhesive tape (width = 18 mm, adhesion = 3.7 N/10 mm) was attached, and an eraser (JIS S6050 qualified product) was rubbed to make a close contact. Then, one end of the tape was grasped, and the number of remaining squares at the time of keeping the right angle at the right angle with the sheet was evaluated by visual observation. The peeling area of the square was determined as follows.

5: peeling area 0%

4: peeling area 0 to <5%

3: peeling area 5 to 15%

2: Peeling area 15 to 35%

1: peeling area 35 to 65%

0: Peeling area 65 to 100%.

(3) Resolution

The width of the mask pattern that can form the smallest pattern is measured using a one-to-one wide line and gap pattern mask.

(4) Evaluation of flattening performance

The cured shrinkage ratio before and after curing was calculated for the cured film produced on the tantalum wafer by the method described in the above (1). When the value is 0 to 15%, it can be said that the flattening performance is good. The hardening shrinkage ratio was calculated according to the following formula.

Hardening shrinkage ratio (%) = (1 - film thickness of cured film obtained by curing 膜 film thickness after development) × 100

However, when the hardening shrinkage ratio of the non-photosensitive resin composition is calculated, since the development step is not performed, the "film thickness after development" is calculated as "film thickness after prebaking". In the film thickness measurement, Lambda Ace STM-602 (trade name: manufactured by Dainippon SCREEN Co., Ltd.) was used. The refractive index was 1.52 regardless of the measurement, and the film thickness after prebaking, the film thickness after development, and the film thickness of the cured film obtained by curing were measured.

Example 1

Under a yellow light, make 1.557 g of 2-methyl-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one (trade name "Iigacure 907" Ciba Specialty Chemicals Co., Ltd.) The system (hereinafter referred to as IC907)) and 0.173 g of 4,4-bis(diethylamino)diphenyl ketone (hereinafter referred to as EK) were dissolved in 21.618 g of DAA and 34.489 g of PGMEA. To the solution, 10.382 g of dipentaerythritol hexaacrylate (trade name "Kayarad DPHA", manufactured by Nippon Chemical Co., Ltd. (hereinafter referred to as DPHA), 4.326 g of decane coupling agent mixed solution (a-1), 8.652 was added. g 4-1,4-butylcatechol 1% by mass PGMEA solution, 17.303 g of decane resin solution (b-1), 1.500 g of polyfluorene-based surfactant BYK-333 (BYK Chemical Japan) The 1% by mass PGMEA solution was stirred, and then filtered through a 0.45 μm filter to obtain a negative photosensitive resin composition (N-1).

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

For the film to be produced, a parallel mask aligner (PLA-501F manufactured by CANON Co., Ltd.) was used, and an ultrahigh pressure mercury lamp was used as a light source, and a pair of 1 having a width of 5, 10, 20, 30, 40, 50 μm was used. The wide mask was exposed with an exposure amount of 200 mJ (i line) and a mask gap of 100 μm. Then, using an automatic developing device (AD-2000, manufactured by Takizawa Seiki Co., Ltd.), the image was sprayed with a 0.4% by mass aqueous solution of tetramethylammonium hydroxide ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 90 seconds, followed by spraying for 90 seconds. Rinse with water for 30 seconds. Finally, an oven (ESPEC-222, manufactured by ESPEC) was used and cured in air at 220 ° C for 1 hour to prepare a cured film. With respect to the obtained cured film, hardness, adhesiveness, and resolution were evaluated by the aforementioned methods.

Example 2

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

Example 3

A negative photosensitive resin composition (N-3) was obtained in the same manner as in Example 1 except that the decane coupling agent mixed solution (a-1) was used instead of the decane coupling agent mixed solution (a-3). 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 was obtained in the same manner as in Example 1 except that the amount of the decane coupling agent mixed solution (a-1) was changed to 0.433 g, and the amount of PGMEA added was changed to 38.382 g. N-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 was obtained in the same manner as in Example 1 except that the amount of the decane coupling agent mixed solution (a-1) was changed to 1.730 g, and the amount of PGMEA added was changed to 37.085 g. N-5). The negative photosensitive resin composition (N-5) obtained was used for evaluation in the same manner as in Example 1.

Example 6

A negative photosensitive resin composition was obtained in the same manner as in Example 1 except that the amount of the decane coupling agent mixed solution (a-1) was changed to 10.382 g, and the amount of PGMEA added was changed to 28.433 g. N-6). The negative photosensitive resin composition (N-6) obtained was used for evaluation in the same manner as in Example 1.

Example 7

A negative photosensitive resin composition was obtained in the same manner as in Example 1 except that the amount of the decane coupling agent mixed solution (a-1) was changed to 14.708 g, and the amount of PGMEA added was changed to 24.107 g. N-7). The negative photosensitive resin composition (N-7) obtained was used for evaluation in the same manner as in Example 1.

Example 8

To 30.000 g of the negative photosensitive resin composition (N-1), 0.052 g of triphenylsulfonium trifluoromethanesulfonate (trade name "WPAG-281" BYK Chemical Japan Co., Ltd. (hereinafter referred to as WPAG-) was added. 281) The negative photosensitive resin composition (N-8) was obtained by stirring, and the negative photosensitive resin composition (N-8) obtained was used and evaluated similarly to Example 1.

Example 9

0.208 g of WPAG-281 was added to 30.000 g of the negative photosensitive resin composition (N-1), and stirred to obtain a negative photosensitive resin composition (N-9). The negative photosensitive resin composition (N-9) obtained was used for evaluation in the same manner as in Example 1.

Example 10

Under a yellow light, 1.557 g of IC907 and 0.173 g of EK were dissolved in 32.000 g of DAA and 21.629 g of PGMEA. To this solution, 8.652 g of DPHA, 4.326 g of a decane coupling agent mixed solution (a-1), 8.652 g of a 1% by mass PGMEA solution of 4-tert-butylcatechol, and 21.629 g of an acrylic resin solution (b-2) were added. 1 kg of a 1% by mass PGMEA solution of BYK-333 was stirred. Subsequently, the mixture was filtered through a 0.45 μm filter to obtain a negative photosensitive resin composition (N-10). 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 10 except that the decane coupling agent mixed solution (a-1) was used instead of the decane coupling agent mixed solution (a-2). 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 10 except that the decane coupling agent mixed solution (a-1) was used instead of the decane coupling agent mixed solution (a-3). The negative photosensitive resin composition (N-12) obtained was used for evaluation in the same manner as in Example 1.

Example 13

Under a yellow light, 1.557 g of IC907 and 0.173 g of EK were dissolved in 32.000 g of DAA and 24.108 g of PGMEA. To this solution, 10.382 g of DPHA, 4.326 g of a mixture solution of decane coupling agent (a-1), 8.652 g of a 1% by mass PGMEA solution of 4-tert-butylcatechol, and 17.303 g of an acrylic resin solution (b-2) were added. 1 kg of a 1% by mass PGMEA solution of BYK-333 was stirred. Subsequently, the mixture was filtered through a 0.45 μm filter to obtain a negative photosensitive resin composition (N-13). The negative photosensitive resin composition (N-13) obtained was used for evaluation in the same manner as in Example 1.

Example 14

A negative photosensitive resin composition (N-14) was obtained in the same manner as in Example 13 except that 0.052 g of WPAG-281 was added to 30.000 g of the negative photosensitive resin composition (N-13). The negative photosensitive resin composition (N-14) obtained was used for evaluation in the same manner as in Example 1.

Example 15

Under a yellow light, 1.557 g of IC907 and 0.173 g of EK were dissolved in 32.000 g of DAA and 18.917 g of PGMEA. To this solution, 6.921 g of DPHA, 4.326 g of a decane coupling agent mixed solution (a-1), 8.652 g of a 1% by mass PGMEA solution of 4-tert-butylcatechol, and 25.955 g of an acrylic resin solution (b-2) were added. 1 kg of a 1% by mass PGMEA solution of BYK-333 was stirred. Subsequently, the mixture was filtered through a 0.45 μm filter to obtain a negative photosensitive resin composition (N-15). The negative photosensitive resin composition (N-15) obtained was used for evaluation in the same manner as in Example 1.

Example 16

Under a yellow light, 1.730 g of the quinonediazide compound (q-1) was dissolved in 6.045 g of DAA and 43.141 g of PGMEA. To this solution, 4.326 g of a decane coupling agent mixed solution (a-1), 43.258 g of a decyl alkoxylate resin solution (b-1), and 1.500 g of a polyfluorene-based surfactant BYK-333 (BYK Chemical Japan ( The 1% by mass PGMEA solution of the product) was stirred. Subsequently, the mixture was filtered through a 0.45 μm filter to obtain a positive photosensitive resin composition (P-1).

Each of the obtained positive photosensitive resin composition (P-1) was spin-coated on a glass substrate and an ITO substrate at a random number of rotation using a spin coater (1H-360S manufactured by MIKASA Co., Ltd.). Then, these substrates were prebaked at 110 ° C for 2 minutes using a hot plate (SCW-636 manufactured by Nippon SCREEN Co., Ltd.) to prepare a film having a film thickness of 1.5 μm.

For the film to be produced, a parallel mask aligner (PLA-501F manufactured by CANON Co., Ltd.) was used, and an ultrahigh pressure mercury lamp was used as a light source, and a pair of 1 having a width of 5, 10, 20, 30, 40, 50 μm was used. The wide mask was exposed with an exposure amount of 200 mJ (i line) and a mask gap of 100 μm. At this time, an unexposed portion having a sufficient width is secured in the hardness and adhesion measurement. Then, using an automatic developing device (AD-2000, manufactured by Takizawa Seiki Co., Ltd.), the image was sprayed with a 0.4% by mass aqueous solution of tetramethylammonium hydroxide ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 90 seconds, followed by spraying for 90 seconds. Rinse with water for 30 seconds. Next, a parallel light ray aligner (PLA-501F manufactured by CANON Co., Ltd.) was used, and an ultrahigh pressure mercury lamp was used as a light source, and exposure was performed at an exposure amount of 6000 mJ (i line). Finally, an oven (ESPEC-222, manufactured by ESPEC) was used and cured in air at 220 ° C for 1 hour to prepare a cured film. With respect to the obtained cured film, hardness, adhesiveness, and resolution were evaluated by the aforementioned methods.

Example 17

It was dissolved in 6.045 g of DAA and 44.871 g of PGMEA. To this solution, 4.326 g of a decane coupling agent mixed solution (a-1), 43.258 g of a decyl alkoxylate resin solution (b-1), and 1.500 g of a polyfluorene-based surfactant BYK-333 (BYK Chemical Japan ( The 1% by mass PGMEA solution of the product) was stirred. Subsequently, the mixture was filtered through a 0.45 μm filter to obtain a thermosetting resin composition (U-1).

The obtained thermosetting resin composition (U-1) was spin-coated on a glass substrate and an ITO substrate at an arbitrary number of revolutions using a spin coater (1H-360S manufactured by MIKASA Co., Ltd.) to prepare a film thickness of 1.5. Μm film. Then, it was prebaked at 110 ° C for 2 minutes using a hot plate (SCW-636 manufactured by Nippon SCREEN Co., Ltd.). Finally, a cured film was produced by curing in air at 260 ° C for 1 hour using an oven (ESPEC-222, manufactured by ESPEC Co., Ltd.). The curing shrinkage ratio was calculated by the above method, and the hardness and adhesion were evaluated.

Comparative example 1

Under a yellow light, 1.557 g of IC907 and 0.173 g of EK were dissolved in 21.618 g of DAA and 38.815 g of PGMEA. To this solution, 10.382 g of DPHA, 8.652 g of 4-tert-butylcatechol 1% by mass PGMEA solution, 17.303 g of decane resin solution (b-1), and 1.500 g of polyoxynoxy surfactant were added. A 1% by mass PGMEA solution of BYK-333 (BYK Chemical Co., Ltd.) was stirred. Subsequently, the mixture was filtered through a 0.45 μm filter to obtain a negative photosensitive resin composition (N-16). The negative photosensitive resin composition (N-16) obtained was used for evaluation in the same manner as in Example 1.

Comparative example 2

A negative photosensitive resin composition (N-17) was obtained in the same manner as in Example 1 except that the decane coupling agent mixed solution (a-1) was used instead of the decane coupling agent mixed solution (a-4). The negative photosensitive resin composition (N-17) obtained was used for evaluation in the same manner as in Example 1.

Comparative example 3

A negative photosensitive resin composition (N-18) was obtained in the same manner as in Example 1 except that the decane coupling agent mixed solution (a-1) was used instead of the decane coupling agent mixed solution (a-5). The negative photosensitive resin composition (N-18) obtained was used for evaluation in the same manner as in Example 1.

Comparative example 4

0.208 g of WPAG-281 was added to 30.000 g of the negative photosensitive resin composition (N-17), and the mixture was stirred to obtain a negative photosensitive resin composition (N-19). The negative photosensitive resin composition (N-19) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 5

0.208 g of WPAG-281 was added to 30.000 g of the negative photosensitive resin composition (N-16), and the mixture was stirred to obtain a negative photosensitive resin composition (N-20). The negative photosensitive resin composition (N-20) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 6

Under a yellow light, 1.557 g of IC907 and 0.173 g of EK were dissolved in 32.000 g of DAA and 25.955 g of PGMEA. To this solution, 8.652 g of DPHA, 8.652 g of a 1% by mass PGMEA solution of 4-t-butylcatechol, 21.629 g of an acrylic resin solution (b-2), and 1.500 g of a BYK-333 1 mass% PGMEA solution were added. Stir. Subsequently, the mixture was filtered through a 0.45 μm filter to obtain a negative photosensitive resin composition (N-21). The negative photosensitive resin composition (N-21) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 7

Under a yellow light, 1.557 g of IC907 and 0.173 g of EK were dissolved in 32.000 g of DAA and 28.434 g of PGMEA. To this solution, 10.382 g of DPHA, 8.652 g of a 1% by mass PGMEA solution of 4-t-butylcatechol, 17.303 g of an acrylic resin solution (b-2), and 1.500 g of a 1% by mass PGMEA solution of BYK-333 were added. , stirring. Subsequently, the mixture was filtered through a 0.45 μm filter to obtain a negative photosensitive resin composition (N-22). The negative photosensitive resin composition (N-22) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 8

Under a yellow light, 1.557 g of IC907 and 0.173 g of EK were dissolved in 32.000 g of DAA and 23.243 g of PGMEA. To this solution, 6.921 g of DPHA, 8.652 g of a 1% by mass PGMEA solution of 4-t-butylcatechol, 25.955 g of an acrylic resin solution (b-2), and 1.500 g of a 1% by mass PGMEA solution of BYK-333 were added. , stirring. Subsequently, the mixture was filtered through a 0.45 μm filter to obtain a negative photosensitive resin composition (N-23). The negative photosensitive resin composition (N-23) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 9

A negative photosensitive resin composition (N-24) was obtained in the same manner as in Example 10 except that the decane coupling agent mixed solution (a-1) was used instead of the decane coupling agent mixed solution (a-4). The negative photosensitive resin composition (N-24) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 10

A negative photosensitive resin composition (N-25) was obtained in the same manner as in Example 10 except that the decane coupling agent mixed solution (a-1) was used instead of the decane coupling agent mixed solution (a-5). The negative photosensitive resin composition (N-25) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 11

A negative photosensitive resin composition (N-26) was obtained in the same manner as in Example 1 except that the decane coupling agent mixed solution (a-1) was used instead of the decane coupling agent mixed solution (a-1). The negative photosensitive resin composition (N-26) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 12

A negative photosensitive resin composition (N-27) was obtained in the same manner as in Example 1 except that the decane coupling agent mixed solution (a-1) was used instead of the decane coupling agent mixed solution (a-7). The negative photosensitive resin composition (N-27) obtained was used for evaluation in the same manner as in Example 1.

Comparative Example 13

A positive photosensitive resin composition (P-2) was obtained in the same manner as in Example 16 except that the decane coupling agent mixed solution (a-1) was used instead of the decane coupling agent mixed solution (a-7). The obtained positive photosensitive resin composition (P-2) was evaluated in the same manner as in Example 16.

Comparative Example 14

A thermosetting resin composition (U-2) was obtained in the same manner as in Example 17 except that the decane coupling agent mixed solution (a-1) was used instead of the decane coupling agent mixed solution (a-7). The obtained thermosetting resin composition (U-2) was used for evaluation in the same manner as in Example 17.

In order to compare the type of the resin composition to which the decane coupling agent of the present invention is added, how the difference between the curing shrinkage ratio and the flattening ability is made, the following reference experiment was conducted.

Reference example 1

A negative photosensitive resin composition (N-1 (using a decane coupling agent (a-1))) was spin-coated on a tantalum wafer at an arbitrary number of revolutions using a spin coater (1H-360S manufactured by MIKASA Co., Ltd.) On the substrate. Then, it was prebaked at 110 ° C for 2 minutes using a hot plate (SCW-636 manufactured by Nippon SCREEN Co., Ltd.) to prepare a film having a film thickness of 1.5 μm. For the film to be produced, a parallel light ray aligner (PLA-501F manufactured by CANON Co., Ltd.) was used, and an ultrahigh pressure mercury lamp was used as a light source, and exposure was performed at an exposure amount of 200 mJ (i line). Then, using an automatic developing device (AD-2000, manufactured by Takizawa Seiki Co., Ltd.), the image was sprayed with a 0.4% by mass aqueous solution of tetramethylammonium hydroxide ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 90 seconds, followed by spraying for 90 seconds. Rinse with water for 30 seconds. Finally, an oven (ESPEC-222, manufactured by ESPEC) was used and cured in air at 220 ° C for 1 hour to prepare a cured film. The curing shrinkage ratio was calculated by the above method, and the flattening ability was evaluated. As a result, the hardening shrinkage ratio was 11%, and the flattening ability was good.

The evaluation was carried out in the same manner as above except that the negative photosensitive resin composition (N-1) was used instead of (N-27). As a result, the hardening shrinkage ratio was 9%, and the flattening ability was good.

In other words, by adding the decane coupling agent (a-1) of the present invention to the negative photosensitive resin composition instead of the conventional decane coupling agent, the curing shrinkage ratio and the flattening ability are hardly lowered.

Reference example 2

A positive photosensitive resin composition (P-1 (using a decane coupling agent (a-1))) was spin-coated on a tantalum wafer at an arbitrary number of revolutions using a spin coater (1H-360S manufactured by MIKASA Co., Ltd.). A film having a film thickness of 1.5 μm was formed on the substrate. Then, it was prebaked at 110 ° C for 2 minutes using a hot plate (SCW-636 manufactured by Nippon SCREEN Co., Ltd.). Using an automatic developing device (AD-2000, manufactured by Takizawa Seiki Co., Ltd.), a 40% by mass aqueous solution of tetramethylammonium hydroxide ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used for showering for 90 seconds, followed by water. Rinse for 30 seconds. Next, using a parallel light ray aligner (PLA-501F manufactured by CANON Co., Ltd.), an ultrahigh pressure mercury lamp was used as a light source, and exposure was performed at an exposure amount of 6000 mJ (i line). Finally, an oven (ESPEC-222, manufactured by ESPEC) was used and cured in air at 220 ° C for 1 hour to prepare a cured film. The curing shrinkage ratio was calculated by the above method, and the flattening ability was evaluated. As a result, the hardening shrinkage ratio was 16%, and the flattening ability was poor.

The evaluation was carried out in the same manner as above except that the positive photosensitive resin composition (P-1) was used instead of the (P-2). As a result, the hardening shrinkage ratio was 13%, and the flattening ability was good.

In other words, by adding the decane coupling agent (a-1) of the present invention to the positive photosensitive resin composition instead of the conventional decane coupling agent, it is particularly preferable to lower the planarization performance.

Reference example 3

A spin coater (1H-360S manufactured by MIKASA Co., Ltd.) was used to spin-coat a thermosetting resin composition (U-1 (using a decane coupling agent (a-1))) to a tantalum wafer substrate at an arbitrary number of revolutions. The film was formed to have a film thickness of 1.5 μm. Then, it was prebaked at 110 ° C for 2 minutes using a hot plate (SCW-636 manufactured by Nippon SCREEN Co., Ltd.). Finally, an oven (ESPEC-222, manufactured by ESPEC) was used and cured in air at 260 ° C for 1 hour to prepare a cured film. The curing shrinkage ratio was calculated by the above method, and the flattening ability was evaluated. As a result, the hardening shrinkage ratio was 18%, and the flattening ability was poor.

The evaluation was carried out in the same manner as above except that the thermosetting resin composition (U-1) was used instead of (U-2). As a result, the hardening shrinkage ratio was 14%, and the flattening ability was good.

In other words, by adding the decane coupling agent (a-1) of the present invention to the thermosetting resin composition instead of the conventional decane coupling agent, it is seen that the curing shrinkage ratio and the planarization performance tend to be lowered.

[Industry use possibility]

The present invention is applicable to a decane coupling agent, a negative photosensitive resin composition containing the same, a cured film using the same, and a touch panel device having the same.

Claims (7)

a decane coupling agent represented by the formula (1), (R ¹ may each be the same or different and represent an alkyl group having 1 to 6 carbon atoms; the alkyl group may further have an alkoxy group, an aryl group, a phenoxy group, a halogen group; n represents 0 or 1; and R ² represents carbon The trivalent organic group having 3 to 10; R ³ may be the same or different and each represents 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). The decane coupling agent of claim 1, wherein n = 0 in the formula (1). A negative photosensitive resin composition characterized by containing at least (A) a decane coupling agent as claimed in claim 1 or 2, (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, (D) Photoradical polymerization initiator. The negative photosensitive resin composition of claim 3, wherein the (B) alkali-soluble resin is a nonanecene resin having an ethylenically unsaturated group. The negative photosensitive resin composition of claim 3, wherein the (B) alkali-soluble resin is an acrylic resin having an ethylenically unsaturated group. A cured film which is as claimed in any of claims 3 to 5 The negative photosensitive resin composition of the item is cured. A member for a touch panel having a cured film as in item 6 of the patent application.