TW201732437A - Positive photosensitive polysiloxane composition and uses thereof - Google Patents

Abstract

The invention relates to a positive photosensitive polysiloxane composition is and an overcoat produced therefrom. The overcoat is for forming a planarization film of a TFT substrate in a liquid crystal display element or organic light-emitting display device, an interlayer insulating film or an overcoat of a core material or a protective material in a waveguide, and has good heat resistance. The positive photosensitive polysiloxane composition comprises a polysiloxane (A), an ortho-naphthoquinone diazide sulfonic acid ester (B), a solvent (C) and a phosphine compound (D).

Description

Positive photosensitive polyoxane composition and application thereof

The present invention relates to a positive photosensitive siloxane composition for a TFT substrate flattening film, an interlayer insulating film, or a core material or a cladding material of an optical waveguide, such as a liquid crystal display device or an organic EL display device. And a protective film formed therefrom and an element having the protective film. In particular, a positive-type photosensitive polyoxyalkylene composition having excellent heat resistance, a protective film formed therefrom, and an element having a protective film are provided.

In recent years, in the fields of the semiconductor industry, liquid crystal displays, or organic electroluminescent display devices, as the size has been increasingly reduced, the miniaturization of the patterns required for the lithography process has been demanded. In order to achieve a fine pattern, it is generally formed by exposure and development of a positive photosensitive material having high resolution and high sensitivity. Among them, a positive photosensitive material containing a polyoxyalkylene polymer is gradually used in the industry. The mainstream.

In a liquid crystal display or an organic electroluminescent display, an interlayer insulating film is usually disposed as an insulating layer in a layered wiring. Since the positive photosensitive material has a small number of steps necessary for obtaining a pattern shape, and the obtained insulating film has a good flatness, it is widely used as a material for forming an interlayer insulating film.

For example, an interlayer insulating film for a liquid crystal display, which forms a pattern of contact holes of fine wiring, is necessary. In fact, the contact hole formed by the negative photosensitive composition is difficult to use the aperture of the level. Therefore, the positive photosensitive composition is widely used in the industry to form an interlayer insulating film of a liquid crystal display element (for example, Japanese Patent Laid-Open) 2001-354822).

Generally, the main component of the positive photosensitive composition which forms the interlayer insulating film is an acrylic resin, but the photosensitive composition using a decane-based material has heat resistance and transparency higher than that of the acrylic resin material. The composition is good (as shown in Japanese Patent Laid-Open No. 2000-1648).

However, a polydecane-based material of a decane compound or a polyoxyalkylene is easily hydrolyzed and condensed with a compound of the same type or a different type by itself. When a positive photosensitive composition is prepared, the occurrence of these side reactions causes the storage stability of the positive photosensitive composition to be deteriorated, and the life of the product is also shortened.

In order to suppress the above condensation reaction, it has been developed in the industry to control the condensation reaction by controlling the molecular weight of the polyoxyalkylene and the branched structure. Japanese Laid-Open Patent Publication No. 2003-163209 discloses that polyoxyalkylene oxides having different molecular weights can be obtained by the action of an acid catalyst, a metal chelate compound and a base catalyst to control the structure of the polyoxyalkylene oxide. However, although the above publication discloses various molecular weights of polyoxyalkylene, it does not take into consideration the photosensitive characteristics of the polyoxyalkylene; in addition to the dielectric constant, various characteristics of the interlayer insulating film are not considered.

In this case, Japanese Laid-Open Patent Publication No. 2011-123450 discloses a positive photosensitive polyoxane composition which has excellent photosensitivity, storage stability, and melt flow resistance, however, the positive photosensitive resin The heat resistance of the composition is not good enough to be accepted by the industry.

Therefore, how to simultaneously meet the current requirements for heat resistance in the industry is an object of diligent research in the technical field to which the present invention pertains.

In the present invention, a composition of a specific polyoxyalkylene polymer, an o-naphthoquinonediazide sulfonate, and a phosphine is provided to obtain a positive-type photosensitive polyoxane composition having excellent heat resistance.

Accordingly, the present invention provides a positive photosensitive polyoxane composition comprising: Polyoxane (A); o-naphthoquinonediazide sulfonate (B); solvent (C); and phosphine compound (D); wherein the phosphine compound (D) comprises at least one selected from the group consisting of trioxane A group consisting of a phosphine compound, a triarylphosphine compound, and a phosphonium salt.

The present invention also provides a method of forming a film on a substrate comprising applying the positive photosensitive polyoxyalkylene composition described above to the substrate.

The invention further provides a film on a substrate produced by the method described above.

The invention further provides a device comprising the aforementioned film.

The present invention provides a positive photosensitive polyoxyalkylene composition comprising: polyoxyalkylene (A); o-naphthoquinonediazide sulfonate (B); solvent (C); and a phosphine compound (D) Wherein the phosphine compound (D) comprises at least one selected from the group consisting of a trialkylphosphine compound, a triarylphosphine compound, and a phosphonium salt.

The respective components of the positive photosensitive polyoxyalkylene composition used in the present invention will be described in detail below.

Here, the following description means that acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid, and acrylate and/or methacrylate is represented by (meth)acrylate; similarly, (meth) The acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group.

The type of polyoxyalkylene (A) according to the present invention is not particularly limited, only It is desirable to achieve the object of the present invention. The polyoxyalkylene (A) can be synthesized by polycondensation (i.e., hydrolysis and partial condensation) using a silane monomer, or can be synthesized by polycondensation using a decane monomer and other polymerizable compound.

The decane monomer includes a decane monomer (a-1) and a decane monomer (a-2); the other polymerizable compound comprises a decane prepolymer (a-3) and cerium oxide particles (a-4). , or a combination thereof. Hereinafter, the reaction steps and conditions of the respective components and the polycondensation will be further described.

The decane monomer (a-1) is a compound represented by the formula (I-1): Si(R ^a ) _w (OR ^b ) _4-w (I-1)

In the formula (I-1), R ^a each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aromatic group having 6 to 15 carbon atoms, and an acid anhydride group. An alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having an epoxy group, and at least one R ^a representing a carbon number of 1 to 10 having an acid anhydride group. An alkyl group, an alkyl group having an epoxy group having 1 to 10 carbon atoms or an alkoxy group having an epoxy group; and R ^b each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number of 1 to The fluorenyl group of 6 or an aromatic group having a carbon number of 6 to 15; and w represents an integer of 1 to 3.

In more detail, when R ^a in the formula (I-1) represents an alkyl group having ^a carbon number of 1 to 10, specifically, R ^a is, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group. N-butyl, tert-butyl, n-hexyl or n-decyl. Further, R ^a may also be an alkyl group having another substituent on the alkyl group, and specifically, R ^{a is,} for example, a trifluoromethyl group, a 3,3,3-trifluoropropyl group, a 3-aminopropyl group, or a 3- Test propyl or 3-isocyanate propyl.

When R ^a in the formula (I-1) represents an alkenyl group having 2 to 10 carbon atoms, specifically, R ^{a is,} for example, a vinyl group. Further, R ^a may be an alkenyl group having another substituent on the alkenyl group, and specifically, R ^{a is,} for example, 3-propenyloxypropyl group or 3-methylpropenyloxypropyl group.

When R ^a in the formula (I-1) represents an aromatic group having ^a carbon number of 6 to 15, specifically, R ^a is, for example, a phenyl group, a tolyl group or a naphthyl group. Further, R ^a may also be an aromatic group having an alternative substituent on the aromatic group, and specifically, R ^a is, for example, an o-hydroxyphenyl group or a 1-(p-hydroxyphenyl)ethyl group (1). -(o-hydroxyphenyl)ethyl), 2-(o-hydroxyphenyl)ethyl or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl ( 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl).

Further, R ^a in the formula (I-1) represents an alkyl group having an acid anhydride group, and the alkyl group is preferably an alkyl group having a carbon number of 1 to 10. Specifically, the acid group-containing alkyl group is, for example, ethyl succinic anhydride represented by the formula (I-1-1), propyl succinic anhydride represented by the formula (I-1-2) or a formula ( The propyl glutaric anhydride shown by I-1-3). It is worth mentioning that the acid anhydride group is a group formed by intramolecular dehydration of a dicarboxylic acid such as succinic acid or glutaric acid.

Further, R ^a in the formula (I-1) represents an alkyl group having an epoxy group, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, the epoxy group-containing alkyl group is, for example, oxetanylpentyl or 2-(3,4-epoxycyclohexyl)ethyl (2-(3,4-epoxycyclohexyl)ethyl). ). It is worth mentioning that the epoxy group is a group formed by intramolecular dehydration of a diol, such as propylene glycol, butylene glycol or pentanediol.

R ^a in the formula (I-1) represents an alkoxy group having an epoxy group, and the alkoxy group is preferably an alkoxy group having a carbon number of 1 to 10. Specifically, the epoxy group-containing alkoxy group is, for example, glycidoxypropyl or 2-oxetanylbutoxy.

Further, when R ^{b of the} formula (I-1) represents an alkyl group having a carbon number of 1 to 6, specifically, R ^b is, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. When R ^b in the formula (I-1) represents a fluorenyl group having a carbon number of 1 to 6, specifically, R ^{b is,} for example, an acetamidine group. When R ^b in the formula (I-1) represents an aromatic group having a carbon number of 6 to 15, specifically, R ^{b is,} for example, a phenyl group.

In the formula (I-1), w represents an integer of 1 to 3. When w represents 2 or 3, a plurality of R ^a may be the same or different; when w represents 1 or 2, a plurality of R ^b may be the same or different.

Specific examples of the decane monomer (a-1) include 3-glycidoxypropyltrimethoxysilane (GPTMS), 3-glycidoxypropyltriethoxydecane (3-glycidoxypropyltriethoxysilane), 2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane, 2-epoxypropoxybutoxypropyl 2-oxetanylbutoxypropyl triphenoxysilane, commercially available from East Asia Synthetic: 2-oxetanylbutoxypropyltrimethoxysilane (trade name: TMSOX-D), 2 -2-oxetanylbutoxypropyltriethoxysilane (trade name: TESOX-D), 3-(triphenyloxene) Mercapto) propyl succinic anhydride, a commercial product manufactured by Shin-Etsu Chemical Co., Ltd.: 3-(trimethoxyindenyl) propyl succinic anhydride (trade name X-12-967), manufactured by WACKER Commercial product: 3-(triethoxyindolyl)propyl succinic anhydride (trade name GF-20), 3-(trimethoxymethyl) propyl glutaric anhydride (TMSG), 3- (three Ethoxymercapto)propyl glutaric anhydride, 3-(triphenyloxyindenyl)propyl glutaric anhydride, diisopropoxy-bis(2-epoxypropoxybutoxypropyl)decane ( Diisopropoxy-di(2-oxetanylbutoxypropyl)silane, referred to as DIDOS), di(3-oxetanylpentyl)dimethoxy silane, (di-n-butoxycarbonyl) ) bis (propyl succinic anhydride), (dimethoxy fluorenyl) bis (ethyl succinic anhydride), 3-glycidoxy propyl dimethyl methoxysilane, 3 3-glycidoxypropyl dimethylethoxysilane, bis(2-propylene oxide butyloxypentyl)-2-epoxypropane pentyl ethoxy decane ( Di(2-oxetanylbutoxypentyl)-2-oxetanyl pentylethoxy silane), three (2 -(2-oxetanylpentyl)methoxysilane, (phenoxymercapto)tris(propyl succinic anhydride), (methylmethoxyindenyl) di Ethyl succinic anhydride), or a combination of the above compounds.

The aforementioned decane monomer (a-1) may be used singly or in combination of two or more.

Specific examples of the decane monomer (a-1) preferably include 3-(triethoxyindolyl)propyl succinic anhydride, 3-(trimethoxyindolyl)propyl succinic anhydride, 3-ring Oxypropoxypropyltrimethoxydecane, 3-(trimethoxyindolyl)propylglutaric anhydride, (dimethoxyindenyl)bis(ethyl succinic anhydride), 2-epoxypropane butyl Oxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-propylene oxide-butoxypropyltriethoxydecane or a combination of the above compounds.

When the polydecane monomer (a-1) represented by the formula (I-1) is used in the polycondensation reaction of the polyoxyalkylene (A), the positive photosensitive polyoxane composition can be further improved. Resistance Heat.

The decane monomer (a-2) is a compound represented by the formula (I-2): Si(R ^c ) _u (OR ^d ) _4-u (I-2)

Of formula (I-2) in a, R ^c each independently represents a hydrogen atom, alkyl having 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbon atoms, an aromatic group having 6 to 15; R ^d is independently A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 15 carbon atoms; and u represents an integer of 0 to 3.

In more detail, when R ^c in the formula (I-2) represents an alkyl group having a carbon number of 1 to 10, specifically, R ^c is, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group. N-butyl, tert-butyl, n-hexyl or n-decyl. Further, R ^c may also be an alkyl group having another substituent on the alkyl group, and specifically, R ^{c is,} for example, a trifluoromethyl group, a 3,3,3-trifluoropropyl group, a 3-aminopropyl group, or a 3- Mercaptopropyl or 3-isocyanate propyl.

When R ^c in the formula (I-2) represents an alkenyl group having 2 to 10 carbon atoms, specifically, R ^{c is,} for example, a vinyl group. Further, R ^c may be an alkenyl group having another substituent on the alkenyl group, and specifically, R ^{c is,} for example, 3-propenyloxypropyl group or 3-methylpropenyloxypropyl group.

When R ^c in the formula (I-2) represents an aromatic group having a carbon number of 6 to 15, specifically, R ^c is, for example, a phenyl group, a tolyl group or a naphthyl group. Further, R ^c may also be an aromatic group having an alternative substituent on the aromatic group, and specifically, R ^c is, for example, an o-hydroxyphenyl group or a 1-(p-hydroxyphenyl)ethyl group (1). -(o-hydroxyphenyl)ethyl), 2-(o-hydroxyphenyl)ethyl or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl ( 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl).

Further, when R ^{d of the} formula (I-2) represents an alkyl group having a carbon number of 1 to 6, specifically, R ^d is, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. When R ^d in the formula (I-2) represents a fluorenyl group having a carbon number of 1 to 6, specifically, R ^{d is,} for example, an acetamidine group. When R ^d in the formula (I-2) represents an aromatic group having a carbon number of 6 to 15, specifically, R ^{d is,} for example, a phenyl group.

In the formula (I-2), u is an integer of 0 to 3. When u represents 2 or 3, a plurality of R ^c may be the same or different; when u represents 0, 1, or 2, a plurality of R ^d may be the same or different.

In the formula (I-2), when u=0, it means that the decane monomer is a tetrafunctional decane monomer (that is, a decane monomer having four hydrolyzable groups); when u=1, it represents decane. The monomer is a trifunctional decane monomer (that is, a decane monomer having three hydrolyzable groups); when u=2, it means that the decane monomer is a difunctional decane monomer (that is, having two hydrolyzable monomers) The decane monomer of the group); and when u=3, it means that the decane monomer is a monofunctional decane monomer (that is, a decane monomer having one hydrolyzable group). It is worth mentioning that the hydrolyzable group refers to a group which can undergo a hydrolysis reaction and is bonded to a hydrazine. For example, the hydrolyzable group is, for example, an alkoxy group, an acyloxy group or a benzene group. A phenoxy group.

Specific examples of the decane monomer represented by the formula (I-2) include, but are not limited to: (1) a tetrafunctional decane monomer: tetramethoxysilane, tetraethoxysilane, tetraethylidene Tetraphenoxy silane or tetraphenoxy silane; (2) trifunctional decane monomer: methyltrimethoxysilane (MTMS), methyltriethoxy decane (methyltriethoxysilane) Methyltriethoxysilane), methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane ), ethyltriisopropoxysilane, ethyltri-n-butoxysilane (ethyltri-n-) Butoxysilane), n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane N-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane ), vinyltriethoxysilane, phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxydecane (p-) Hydroxyphenyltrimethoxysilane), 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxydecane (2-(p-) Hydroxyphenyl)ethyltrimethoxysilane), 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoro Trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropane 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methacryloxypropyltrimethoxydecane or 3-methylpropenyloxypropyltriethoxydecane;

(3) Difunctional decane monomer: dimethyl dimethoxy decane (dimethyldimethoxysilane, hereinafter referred to as DMDMS), dimethyldiethoxysilane, dimethyldiacetyloxysilane, di-n-butyldimethoxysilane or Diphenyldimethoxysilane; or

(4) Monofunctional decane monomer: trimethylmethoxysilane or tri-n-butylethoxysilane.

The various decane monomers described may be used singly or in combination of two or more.

The alkane prepolymer (a-3) is a compound represented by the formula (I-3).

In the formula (I-3), R ^e , R ^f , R ^g and R ^h each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or a carbon number of 6 to An aromatic group of 15, wherein the alkyl group, the alkenyl group and the aromatic group optionally have a substituent; R ⁱ and R ^j each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number of a fluorenyl group of 1 to 6 or an aromatic group having 6 to 15 carbon atoms, wherein any one of the alkyl group, the fluorenyl group and the aromatic group may optionally have a substituent; and s represents an integer of 1 to 1000.

In more detail, when R ^e , R ^f , R ^g and R ^h in the formula (I-3) each independently represent an alkyl group having a carbon number of 1 to 10, specifically, R ^e , R ^f , R ^g and R ^h are each independently, for example, methyl, ethyl or n-propyl. When R ^e , R ^f , R ^g and R ^h in the formula (I-3) each independently represent an alkenyl group having 2 to 10 carbon atoms, specifically, R ^e , R ^f , R ^g and R ^{h are,} for example, Each is independently a vinyl group, a propylene methoxypropyl group or a methacryloxypropyl group. When R ^e , R ^f , R ^g and R ^h in the formula (I-3) each independently represent an aromatic group having a carbon number of 6 to 15, specifically, R ^e , R ^f , R ^g and R ^{h are,} for example, Each is independently a phenyl group, a tolyl group or a naphthyl group. Further, any of the alkyl group, the alkenyl group and the aromatic group may have another substituent.

Further, when R ⁱ and R ^{j of the} formula (I-3) each independently represent an alkyl group having a carbon number of 1 to 6, specifically, R ⁱ and R ^j are each independently a methyl group, an ethyl group, a n-propyl group. Base, isopropyl or n-butyl. When R ⁱ and R ^{j of the} formula (I-3) each independently represent a fluorenyl group having a carbon number of 1 to 6, specifically, R ⁱ and R ^{j are,} for example, an ethyl fluorenyl group. When R ⁱ and R ^j in the formula (I-3) each independently represent an aromatic group having a carbon number of 6 to 15, specifically, R ⁱ and R ^{j are,} for example, a phenyl group. Among them, any of the above alkyl group, mercapto group and aryl group may optionally have a substituent.

In the formula (I-3), s may be an integer of from 1 to 1000, preferably an integer of from 3 to 300, more preferably an integer of from 5 to 200. When s is an integer from 2 to 1000, each of R ^e is the same or different group, and each of R ^f is the same or different group.

Specific examples of the decane prepolymer (a-3) include, but are not limited to, 1,1,3,3-tetramethyl-1,3-dimethoxydioxane, 1,1,3 , 3-tetramethyl-1,3-diethoxydioxane, 1,1,3,3-tetraethyl-1,3-diethoxydioxane or by Gilles Commercial product of Silanol terminated polydimethylsiloxane manufactured by Gelest) (trade name such as DMS-S12 (molecular weight 400 to 700), DMS-S15 (molecular weight 1500 to 2000), DMS-S21 (molecular weight 4200), DMS-S27 (molecular weight 18000), DMS-S31 (molecular weight 26000), DMS-S32 (molecular weight 36000), DMS-S33 (molecular weight 43500), DMS-S35 (molecular weight 49000), DMS-S38 (molecular weight 58000), DMS-S42 (molecular weight 77000) or PDS-9931 (molecular weight 1000 to 1400)).

The alkane prepolymer (a-3) may be used singly or in combination of two or more.

The average particle diameter of the cerium oxide particles (a-4) is not particularly limited. The average particle diameter ranges from 2 nm to 250 nm, preferably from 5 nm to 200 nm, and more preferably from 10 nm to 100 nm.

Specific examples of the cerium oxide particles (a-4) include, but are not limited to, commercially available products manufactured by Catalyst Chemical Co., Ltd., and trade names such as OSCAR 1132 (particle size: 12 nm; dispersant) Methanol), OSCAR 1332 (particle size 12 nm; dispersant is n-propanol), OSCAR 105 (particle size 60 nm; dispersant is γ-butyrolactone), OSCAR 106 (particle size 120 nm; dispersant is diacetone alcohol) A commercial product manufactured by Fuso Chemical Co., Ltd., trade name such as Quartron PL-1-IPA (particle size 13 nm; dispersant is isopropanone), Quartron PL-1-TOL (particle size 13 nm; dispersant toluene) , Quartron PL-2L-PGME (particle size 18nm; dispersant is propylene glycol monomethyl ether) or Quartron PL-2L-MEK (particle size 18nm; dispersant is methyl ethyl ketone), or a commercial product manufactured by Nissan Chemical Co., Ltd. , trade name such as IPA-ST (particle size 12nm; dispersant is isopropanol), EG-ST (particle size 12nm; dispersant is ethylene glycol), IPA-ST-L (particle size 45nm; dispersant is different Propanol) or IPA-ST-ZL (particle size 100 nm; dispersant is isopropanol). The cerium oxide particles may be used singly or in combination of plural kinds.

The polyoxyalkylene (A) can be synthesized by polycondensation using a decane monomer or by polycondensation using a decane monomer and other polymerizable compounds. In general, the above polycondensation reaction is carried out by adding a solvent, water, or a catalyst may be optionally added to the decane monomer; and heating and stirring at 50 ° C to 150 ° C for 0.5 hour to For 120 hours, by-products (alcohols, water, etc.) can be further removed by distillation.

The solvent used in the polycondensation reaction is not particularly limited, and the solvent may be the same as or different from the solvent (C) included in the positive photosensitive polyoxane composition of the present invention. The solvent is preferably used in an amount of 15 parts by weight to 1200 parts by weight, more preferably 20 parts by weight to 1100 parts by weight, even more preferably 30 parts by weight to 1000 parts by weight, based on 100 parts by weight of the total of the decane monomers.

The hydrolyzable group based on the decane monomer is 1 mol, and the water used for the polycondensation reaction (i.e., water for hydrolysis) is preferably from 0.5 mol to 2 mol.

The catalyst used in the polycondensation reaction is not particularly limited, and is preferably selected from an acid catalyst or a base catalyst. Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, nitric acid, sulfur Acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroester acid, formic acid, polycarboxylic acid or its anhydride or ion exchange resin. Specific examples of the base catalyst include, but are not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide. And potassium hydroxide, an alkoxy group-containing decane or an ion exchange resin containing an amine group.

The catalyst is preferably used in an amount of from 0.005 parts by weight to 15 parts by weight, based on the total amount of the decane monomer, of 100 parts by weight; more preferably from 0.01 part by weight to 12 parts by weight; still more preferably from 0.05 part by weight to 10 parts by weight. .

The polyoxyalkylene (A) is preferably free of by-products (such as alcohols or water) and a catalyst based on the viewpoint of stability. Therefore, the reaction mixture after the polycondensation reaction can be selectively subjected to purification to obtain the polyoxyalkylene (A). The method of purification is not particularly limited, and it is preferred to dilute the reaction mixture using a hydrophobic solvent. Next, the hydrophobic solvent and reaction mixture are transferred to a separation funnel. Then, the organic layer was washed several times with water, and then the organic layer was concentrated with a rotary evaporator to remove alcohol or water. Alternatively, the catalyst can be removed using an ion exchange resin.

The polyoxyalkylene (A) may be used in combination with other alkali-soluble resins. The kind of the other alkali-soluble resin is not particularly limited and may include, but is not limited to, a resin containing a carboxylic acid group or a hydroxyl group. Specific examples of the other alkali-soluble resin include an acrylic (Acrylic) resin, a fluorene resin, a urethane resin, or a novolac resin.

The acrylic resin is preferably obtained by copolymerization of one or more unsaturated carboxylic acids or unsaturated carboxylic anhydride compounds and/or other unsaturated compounds in a solvent in the presence of a suitable polymerization initiator.

Specific examples of the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound include acrylic acid (AA), methacrylic acid, crotonic acid, 2-chloroacrylic acid, ethacrylic acid, and cinnamon. An unsaturated monocarboxylic acid such as an acid, 2-propene oxime ethoxy succinate, 2-methyl propylene ethoxy succinate (HOMS) or 2-isobutenyl ethoxy succinate; Maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid or citraconic anhydride, unsaturated dicarboxylic acids (anhydrides), trivalent or higher unsaturated polycarboxylic acids ( Anhydrides; preferably, the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound is acrylic acid, methacrylic acid, 2-propenyl ethoxy succinate, 2-methyl propylene ethoxy succinate Ester or 2-isobutylene ethoxy succinate. The above-mentioned one or more unsaturated carboxylic acid or unsaturated carboxylic anhydride compounds may be used singly or in combination of two kinds in order to improve pigment dispersibility, increase development speed, and reduce residue generation.

Specific examples of the other unsaturated compound include aromatic vinyl compounds such as styrene (SM), α-methylstyrene, vinyl toluene, p-chlorostyrene, methoxystyrene, etc.; N-phenyl group Maleate, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-A Phenyl-maleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenyl malayan Amine, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, N-cyclohexylmaleimide, etc.; maleic acid; acrylic acid Methyl ester, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, methyl N-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2-hydroxy acrylate Ester, A 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, methacrylic acid 2-hydroxybutyl ester, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, Benzyl acrylate, benzyl methacrylate (BzMA), phenyl acrylate, phenyl methacrylate, Triethylene glycol methacrylate, triethylene glycol methacrylate, dodecyl methacrylate, tetradecyl methacrylate, cetyl methacrylate, methacrylic acid An octadecyl ester, an eicosyl methacrylate, a behenyl methacrylate, an unsaturated carboxylic acid ester such as dicyclopentenyloxyethyl acrylate (DCPOA); , N-dimethylaminoethyl ester, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminopropyl acrylate, N,N-dimethylamine methacrylate Propyl propyl ester, N,N-dibutylaminopropyl acrylate, N,iso-butylaminoethyl methacrylate; glycidyl acrylate, glycidyl methacrylate (GMA), etc. Unsaturated carboxylic acid glycidyl esters; vinyl acetates such as vinyl acetate, vinyl propionate, vinyl butyrate; vinyl methyl ether, vinyl ethyl ether, allyl epoxypropyl ether, Unsaturated ethers such as methallyl-epoxypropyl ether; cyanidation vinylation of acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, vinyl cyanide, etc. Alkyl amide, methacrylamide, 2-chloropropenylamine, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, etc.; An aliphatic conjugated diene such as a diene, isopentene or chlorinated butadiene.

Specific examples of the lanthanoid resin include V259ME, V259MEGTS, or V500MEGT (manufactured by Nippon Steel Chemical Co., Ltd.), and the lanthanide resins may be used singly or in combination of two or more.

Specific examples of the urethane-based resin include UN-904, UN-952, UN-333, or UN1255 (manufactured by Kokusai Kogyo Co., Ltd.), and the urethane-based resin may be used singly or in combination of two or more.

Specific examples of the novolac type resin include EP4020G, EP4080G, TR40B45G, or EP30B50 (as manufactured by Asahi Organic Materials Co., Ltd.), and the novolac type resins may be used singly or in combination of two or more.

The polyoxyalkylene (A) has a weight average molecular weight of from 3,000 to 15,000, preferably from 3,500 to 12,000, more preferably from 4,000 to 10,000.

The kind of the o-naphthoquinonediazide sulfonate (B) according to the present invention is not particularly limited, and the ortho-naphthoquinonediazide sulfonate which is generally used can be used, but it can achieve the object of the present invention. . The o-naphthoquinonediazide sulfonate (B) may be a fully esterified or partially esterified ester-based compound.

The o-naphthoquinonediazide sulfonate (B) is preferably prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydroxy compound. The o-naphthoquinonediazide sulfonate (B) is more preferably prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a polyhydroxy compound.

Specific examples of the o-naphthoquinonediazidesulfonic acid (B) include, but are not limited to, o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide-5-sulfonic acid or o-naphthoquinonediazide- 6-sulfonic acid and the like. Further, the salt of o-naphthoquinonediazidesulfonic acid is, for example, diazonaphthoquinone sulfonyl halide.

Specific examples of the hydroxy compound include, but are not limited to, a hydroxybenzophenone compound, a hydroxyaryl compound, a (hydroxyphenyl) hydrocarbon compound, another aromatic hydroxy compound, or a combination of the above compounds.

Specific examples of the hydroxybenzophenone-based compound include, but are not limited to, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2, 4,6-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4,2',4'-tetrahydroxybenzophenone, 2,4,6, 3',4'-pentahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone 2,4,5,3',5'-pentahydroxybenzophenone or 2,3,4,3',4',5'-hexahydroxybenzophenone, and the like.

Specific examples of the hydroxyaryl-based compound include, but are not limited to, a hydroxyaryl compound represented by the formula (b-1).

In the formula (b-1), B ¹ and B ² each independently represent a hydrogen atom, a halogen atom or a C 1 to 6 alkyl group; and B ³ , B ⁴ and B ⁷ each independently represent a hydrogen atom or have a carbon number of 1 to 6 alkyl; B ⁵ , B ⁶ , B ⁸ , B ⁹ , B ¹⁰ and B ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. An alkenyl group or a cycloalkyl group having a carbon number of 1 to 6; and h, i and j each independently represent an integer of 1 to 3; k represents 0 or 1.

Specifically, specific examples of the hydroxyaryl compound represented by the formula (b-1) include, but are not limited to, tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl) )-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)- 2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3- Hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4- Dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)- 2,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy 4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane , bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-2-hydroxyphenylmethane, bis ( 3-ring Hexyl-4-hydroxy-6-methylphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-4-hydroxybenzene Methane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-3-hydroxybenzene Methane, bis(3-cyclohexyl-6-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-ring Hexyl-6-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, bis (3) -cyclohexyl-6-hydroxy-4-methylphenyl)-3,4-dihydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1- Bis(4-hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4) -Hydroxyphenyl)ethyl]benzene, or a combination of the above compounds.

Specific examples of the (hydroxyphenyl)hydrocarbon compound include, but are not limited to, a (hydroxyphenyl) hydrocarbon compound represented by the formula (b-2).

In the formula (b-2), B ¹² and B ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and m and n each independently represent an integer of 1 to 3.

Specifically, specific examples of the (hydroxyphenyl) hydrocarbon compound represented by the formula (b-2) include, but are not limited to, 2-(2,3,4-trihydroxyphenyl)-2-(2',3 ',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl) -2-(4'-hydroxyphenyl)propane, bis(2,3,4-trihydroxyphenyl)methane or bis(2,4-dihydroxyphenyl)methane.

Specific examples of the other aromatic hydroxy compound include, but are not limited to, phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, catechol, 1, 2,3-benzenetriol methyl ether, 1,2,3-benzenetriol-1,3-dimethyl ether, 3,4,5-trihydroxybenzoic acid, 4,4'-[1-[4 [-1-(4-hydroxyphenyl)-1-methylethyl]phenyl] Ethylene] bisphenol, or partially esterified or partially etherified 3,4,5-trihydroxybenzoic acid, and the like.

The hydroxy compound is preferably 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 2,3,4- Trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone or a combination thereof. The hydroxy compound may be used singly or in combination of two or more.

The reaction of the o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydroxy compound is usually carried out in an organic solvent such as dioxane, N-pyrrolidone or acetamide. . Further, the above reaction is preferably carried out in an alkali condensing agent such as triethanolamine, an alkali metal carbonate or an alkali metal hydrogencarbonate.

The degree of esterification of the o-naphthoquinonediazide sulfonate (B) is preferably 50% or more, that is, based on the total amount of hydroxyl groups in the hydroxy compound, 100 mol% (mol%), hydroxyl group More than 50 mol% of the hydroxyl groups in the compound are esterified with o-naphthoquinonediazidesulfonic acid or a salt thereof. The degree of esterification of the o-naphthoquinonediazide sulfonate (B) is more preferably 60% or more.

A specific example of the o-naphthoquinonediazide sulfonate (B) is preferably 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl]benzene O-naphthyl diazide sulfonate, 2,3,4-trihydroxybenzophenone and o-naphthoquinone formed by bisphenol and o-naphthoquinonediazide-5-sulfonic acid O-naphthoquinonediazide sulfonate formed by azide-5-sulfonic acid and 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxybenzene And the o-naphthoquinone diazide sulfonate formed by propane and o-naphthoquinonediazide-5-sulfonic acid, but not limited thereto.

The o-naphthoquinonediazide sulfonate (B) is used in an amount of 5 parts by weight to 50 parts by weight, based on 100 parts by weight of the polyoxyalkylene (A); preferably 8 to 45 parts by weight. More preferably, it is 10 to 40 parts by weight.

The kind of the solvent (C) according to the present invention is not particularly limited. The solvent (C) is, for example, a compound containing an alcoholic hydroxy group or a carbonyl group-containing compound A cyclic compound of (carbonyl group).

Specific examples of the alcoholic hydroxyl group-containing compound include, but are not limited to, acetol, 3-hydroxy-3-methyl-2-butanone, 4- 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl 4-hydroxy-4-methyl-2-pentanone (also known as diacetone alcohol (DAA)), ethyl lactate, butyl lactate, Propylene glycol monomethyl ether), propylene glycol monoethyl ether (PGEE), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol mono-n-propyl Propyl ether), propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, 3-methoxy-1-butanol (3- Methoxy-1-butanol), 3-methyl-3-methoxy-1-butanol, or a combination thereof. It is to be noted that the alcoholic hydroxyl group-containing compound is preferably diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or a combination thereof. The alcoholic hydroxyl group-containing compound may be used singly or in combination of two or more.

Specific examples of the cyclic compound containing a carbonyl group include, but are not limited to, γ - butyrolactone (γ -butyrolactone), γ - valerolactone (γ -valerolactone), δ- valerolactone (δ-valerolactone), propylene carbonate Propylene carbonate, N-methyl pyrrolidone, cyclohexanone or cycloheptanone. It is to be noted that the carbonyl group-containing cyclic compound is preferably γ -butyrolactone, nitrogen-methylpyrrolidone, cyclohexanone or a combination thereof. The carbonyl group-containing cyclic compound may be used singly or in combination of two or more.

The alcoholic hydroxyl group-containing compound can be used in combination with a carbonyl group-containing cyclic compound, and the weight ratio thereof is not particularly limited. a compound containing an alcoholic hydroxyl group and a carbonyl group-containing compound The weight ratio of the cyclic compound is preferably from 99/1 to 50/50; more preferably from 95/5 to 60/40. It is worth mentioning that when the weight ratio of the alcoholic hydroxyl group-containing compound to the carbonyl group-containing cyclic compound is from 99/1 to 50/50 in the solvent (C), the polyoxane (A) is not reacted. The silanol (Si-OH) group is less susceptible to condensation reactions and reduces storage stability. Further, since the alcoholic hydroxyl group-containing compound and the carbonyl group-containing cyclic compound have good compatibility with the o-naphthoquinonediazide sulfonate (B), it is less likely to be whitened during coating film formation and can be maintained. The transparency of the protective film.

The solvent (C) may contain other solvents insofar as the effects of the present invention are not impaired. The other solvent is, for example: (1) an ester: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy- 1-butyl acetate or 3-methyl-3-methoxy-1-acetic acid butyl acetate; (2) ketones: acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone , methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, Cyclohexanone, acetamidine acetone, diacetone alcohol or cyclohexen-1-one; or (3) ethers: diethyl ether, diisopropyl ether, di-n-butyl ether or diphenyl ether.

The solvent (C) may be used singly or in combination of two or more.

The solvent (C) is used in an amount of 100 to 600 parts by weight, preferably 120 to 550 parts by weight, and more preferably 150 to 500 parts by weight, based on 100 parts by weight of the polyoxyalkylene (A). .

The phosphine compound (D) according to the present invention comprises at least one selected from the group consisting of a trialkylphosphine compound, a triarylphosphine compound and a phosphonium salt.

Specific examples of the phosphine compound (D) according to the present invention include trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, tripentylphosphine, trihexylphosphine, triheptylphosphine, and trioctyl Trialkylphosphine compounds such as phosphine, tricyclohexylphosphine; triphenylphosphine, tritolylphosphine, trixylyl phosphine, tribiphenylphosphine, trinaphthylphosphine ), Sancha Triarylphosphine compounds such as trianthrylphosphine and triphenanthrylphosphine; ethyl triphenylphosphonium bromide, tetraphenyl phosphonium bromide and benzyltriphenyl a phosphonium salt such as benzyl triphenyl-phosphonium chloride.

The phosphine compound (D) is used in an amount of 0.1 part by weight to 3.0 parts by weight, based on the amount of the polyoxyalkylene (A) used, preferably 0.15 to 2.5 parts by weight; more preferably 0.2. To 2.0 parts by weight. When the phosphine compound (D) is not used, there is a problem that heat resistance is not good.

In a preferred embodiment of the present invention, the positive photosensitive polyoxyalkylene composition further comprises an inorganic particle (E) mainly composed of an oxide of a Group IV element. The kind of the inorganic particles (E) mainly composed of the oxide of the Group IV element according to the present invention is not particularly limited, and the oxide in the inorganic particles (E) includes titanium oxide, zirconium oxide, cerium oxide, and oxidation. Furnace or composite particles formed from these metal oxides with cerium oxide or tin oxide. The oxide is preferably titanium oxide or zirconium oxide, that is, the fourth group element of the inorganic particle (E) mainly composed of the oxide of the fourth group element, from the viewpoint of heat resistance of the protective film to be formed. It is preferably titanium or zirconium.

The titanium oxide has both an anatase type and a rutile type (Rutile), and it is preferable because the rutile type has a high refractive index and excellent light resistance.

As the titanium oxide, commercially available titanium oxide particles such as NanoTek TiO ₂ (dispersing agent is methyl isobutyl ketone, anatase type, manufactured by CIKasei, Japan), batch number: S111109 (dispersing agent is ethoxyethanol, gold) can be used. Redstone type, manufactured by Korea NanoCMS), Red Lake series (dispersant is methanol, anatase type, manufactured by Nippon Radiation Co., Ltd.), TS series (dispersant is methyl ethyl ketone, rutile type, by Tayca Manufacturing). As the zirconia, commercially available zirconia particles such as HXU-120JC (dispersant is methyl ethyl ketone, manufactured by Osaka Cement Co.) can be used.

The inorganic particles (E) mainly composed of the oxide of the Group IV element may be in the form of a powder or a dispersed sol form in which the oxide particles are dispersed in a dispersion medium. The dispersion medium is, for example, methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether or ethoxyethanol.

The inorganic particles (E) having an oxide of a Group IV element as a main component have a particle diameter distribution of from 1 nm to 75 nm. When the particle diameter is less than 1 nm, the formed protective film is liable to undergo secondary aggregation and may cause whitening; when the particle diameter is larger than 75 nm, the uniformity of the surface of the formed protective film may be affected. The particle size distribution of the inorganic particles (E) is preferably from 3 nm to 50 nm; more preferably from 5 nm to 30 nm. The method of measuring the particle size may be a conventional measurement method, for example, by photon correlation spectroscopy (PCS).

The inorganic particles (E) are used in an amount of 30 to 300 parts by weight, preferably 40 parts by weight to 280 parts by weight, and more preferably 50 parts by weight based on 100 parts by weight of the polyoxyalkylene (A). Parts to 250 parts by weight. When the inorganic particles (E) are used, heat resistance can be further improved.

The additive (F) can be selectively further added according to the positive photosensitive polyoxoxane composition of the present invention. Specifically, the additive (F) is, for example, a sensitizer, an adhesion auxiliary agent, a surfactant, a solubility promoter, a defoamer or a defoamer. Its combination.

The type of the sensitizer is not particularly limited. The sensitizer is preferably a compound containing a phenolic hydroxy group, and specific examples of the compound having a phenolic hydroxyl group include, but are not limited to, a trisphenol type compound, a bisphenol type compound, a multinuclear branched type compound, and a condensation type. A phenol compound, a polyhydroxybenzophenone or a combination of the above compounds.

Specific to the trisphenol type compound Examples include, but are not limited to, tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethyl Phenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylbenzene 3-hydroxyphenylmethane, bis(4-hydroxy-3,5-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)- 4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2- Hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3 , 4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy 4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylbenzene 3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane or bis(5-cyclohexyl-4-hydroxy-2-methyl Phenyl)-3,4-dihydroxyphenylmethane

Specific examples of the bisphenol type compound include, but are not limited to, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4 -trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2- (2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2 -(3-fluoro-4-hydroxyphenyl)-2-(3'-fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(4' -hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane or 2-(2,3,4-trihydroxyphenyl)-2 -(4'-Hydroxy-3',5'-dimethylphenyl)propane, and the like.

Specific examples of the polynuclear branched compound include, but are not limited to, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl). Ethyl]benzene or 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl] Benzene, etc.

Specific examples of the condensation type phenol compound include, but are not limited to, 1,1-bis(4-hydroxyphenyl)cyclohexane.

Specific examples of the polyhydroxy benzophenone include, but are not limited to, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4,2' , 4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2 ,3,4,2',5'-pentahydroxybenzophenone, 2,4,6,3',4',5'-hexahydroxybenzophenone or 2,3,4,3',4 ', 5'-hexahydroxybenzophenone and the like.

Specific examples of the adhesion aid include a melamine compound, a decane compound, and the like. The role of the adhesion aid is to increase the adhesion between the protective film formed of the positive photosensitive polyoxyalkylene composition and the member to be protected.

Specific examples of the commercial product of the melamine include a trade name of Cymel-300 or Cymel-303 manufactured by Mitsui Chemicals, or a trade name of MW-30MH, MW-30, MS-11, MS manufactured by Sanwa Chemical. -001, MX-750 or MX-706, etc.

Specific examples of the decane-based compound include vinyltrimethoxydecane, vinyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, and vinyltris(2-methoxyethoxy)decane. , nitrogen-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3- Aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 2-(3,4-epoxy ring Hexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-anthracene A trimethoxy decane or a commercially available product (trade name such as KBM403) manufactured by Shin-Etsu Chemical Co., Ltd., or the like.

Specific examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a polyoxyalkylene surfactant, a fluorine surfactant, or a combination thereof.

Specific examples of the surfactant include, but are not limited to, (1) polyoxyethylene alkyl ethers: polyethylene oxide dodecyl ether, and the like; (2) polyethylene oxide alkane Polyoxyethylene phenyl ethers: polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, etc.; (3) polyethylene glycol diesters: Polyethylene glycol dilaurate, polyethylene glycol distearate, etc.; (4) sorbitan fatty acid esters; (5) fatty acid modified polyester (fatty acid Modified poly esters; and (6) tertiary amine modified polyurethanes, etc., modified by tertiary amines. Specific examples of commercial products of the surfactant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), and Polyflow (manufactured by Dow Corning Toray Silicone Co., Ltd.). F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by Dainippon Ink Chemical Industry (DIC)), Fluorade (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass), SINOPOL E8008 (manufactured by Sino-Japanese Synthetic Chemicals), F-475 (manufactured by Dainippon Ink Chemical Industries), or a combination thereof .

Specific examples of the antifoaming agent include Surfynol MD-20, Surfynol MD-30, EnviroGem AD01, EnviroGem AE01, EnviroGem AE02, Surfynol DF110D, Surfynol 104E, Surfynol 420, Surfynol DF37, Surfynol DF58, Surfynol DF66, Surfynol DF70, and Surfynol DF210 (made by Air products), etc.

Specific examples of the dissolution promoter include a nitrogen-hydroxydicarboxylic imide compound and a phenolic hydroxyl group-containing compound. The dissolution promoter is, for example, a phenolic hydroxyl group-containing compound used in o-naphthoquinonediazide sulfonate (B).

The preparation method of the positive photosensitive polyoxyalkylene composition of the present invention is as follows: The polyaluminoxane (A), the o-naphthoquinone diazide sulfonate (B), the solvent (C), the catalyst (D), and optionally the inorganic particles (E) are placed in a stirrer to be stirred and homogenized. The mixture is mixed into a solution state, and if necessary, an additive (F) may be added, and after uniformly mixing, a positive photosensitive polyoxane composition in a solution state can be obtained.

The present invention also provides a method of forming a film on a substrate comprising applying the positive photosensitive polyoxyalkylene composition described above to the substrate.

The invention further provides a film on a substrate produced by the method described above.

The film according to the present invention is preferably a flat film of a TFT substrate, an interlayer insulating film or a protective film of a core material or a cladding material for a TFT substrate in a liquid crystal display element or an organic electroluminescence display.

The invention further provides a device comprising the aforementioned film.

Hereinafter, a method of forming a protective film will be described in detail, which includes sequentially forming a pre-baked coating film using a positive photosensitive polysiloxane composition, patterning exposure of the prebaked coating film, and removing exposure by alkali development. a region to form a pattern; and a post-baking treatment to form a protective film.

Forming a pre-baked film

A positive-type photosensitive polyoxane composition in a solution state is applied onto a protected element (hereinafter referred to as a substrate) by a coating method such as spin coating, cast coating, or roll coating to form a coating film.

The substrate may be an alkali-free glass, a soda-lime glass, a hard glass (Pyrus glass), a quartz glass, a glass to which a transparent conductive film is attached, or a photoelectric conversion device (for example, for a liquid crystal display device). A substrate (such as a tantalum substrate) of a solid-state imaging device.

After the coating film is formed, most of the organic solvent of the positive photosensitive polyoxyalkylene composition is removed by vacuum drying, and then the residual is pre-bake. The organic solvent is completely removed to form a pre-baked film.

The operating conditions of the above-described reduced-pressure drying and pre-baking may vary depending on the type and blending ratio of each component. In general, the drying under reduced pressure is carried out at a pressure of from 0 torr to 200 Torr for 1 second to 60 seconds, and the prebaking is carried out at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes.

Patterned exposure

The prebaked coating film is exposed in a mask having a specific pattern. The light used in the exposure process is preferably ultraviolet rays such as g-line, h-line or i-line, and the device for providing ultraviolet rays may be a (ultra) high pressure mercury lamp or a metal halide lamp.

development

The exposed prebaked coating film is immersed in a developing solution having a temperature of 23±2° C. for about 15 seconds to 5 minutes to remove unnecessary portions of the exposed prebaked coating film, that is, The exposed area is dissolved in the developer, and the unexposed areas are retained, whereby a semi-finished product having a protective film of a predetermined pattern can be formed on the substrate. Specific examples of the developer include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methylsilicate, ammonia, ethylamine, Diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (THAM), tetraethylammonium hydroxide, choline, pyrrole, acridine or 1,8-diazabicyclo[5.4.0]-7- A basic compound such as an alkene.

It is worth mentioning that if the concentration of the developer is too high, the specific pattern may be damaged or the resolution of the specific pattern may be deteriorated; if the concentration is too low, the development may be poor, resulting in the failure of the specific pattern to be formed or the composition of the exposed portion remaining. Therefore, the amount of concentration affects the formation of a specific pattern of the subsequent positive photosensitive polyoxyalkylene composition after exposure. The concentration of the developer is preferably in the range of 0.001% by weight to 10% by weight; more preferably 0.005% by weight to 5% by weight; still more preferably 0.01% by weight to 1% by weight. An embodiment of the present invention is a developer using 2.38 wt% of tetramethylammonium hydroxide. It is worth mentioning that even with a lower concentration developer, this The positive-type photosensitive polyoxane composition of the invention can also form a good fine pattern.

Post-bake treatment

The substrate (the semi-finished product of the protective film having a predetermined pattern on the substrate) is washed with water to remove unnecessary portions of the exposed pre-baked film. Then, the semi-finished product of the above protective film having a predetermined pattern is dried with compressed air or compressed nitrogen. Finally, the semi-finished product of the above-mentioned protective film having a predetermined pattern is subjected to a post-bake treatment by a heating means such as a hot plate or an oven. The heating temperature is set between 100 ° C and 250 ° C, the heating time when using the hot plate is 1 minute to 60 minutes, and the heating time when using the oven is 5 minutes to 90 minutes. Thereby, the pattern of the semi-finished product of the protective film having the predetermined pattern described above can be fixed to form a protective film.

For example, the protective film is formed, for example, in the following steps. First, a positive-type photosensitive polyoxane composition was formed into a coating film of about 2 μm on a plain glass substrate (100 × 100 × 0.7 mm) by spin coating. Subsequently, after prebaking at 110 ° C for 2 minutes, the coating film was placed under an exposure machine. Next, a positive photoresist mask was placed between the exposure machine and the coating film, and the prebaked coating film was irradiated with ultraviolet light of the exposure machine at an energy of 100 mJ/cm ² . The exposed prebaked coating film was immersed in a 2.38% aqueous solution of TMAH at 23 ° C for 60 seconds to remove the exposed portion. Then, after washing with water, the developed coating film was directly irradiated with an exposure machine at an energy of 200 mJ/cm ² . Finally, after baking at 230 ° C for 60 minutes, a plain glass substrate on which a protective film was formed was obtained.

The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention.

Preparation of polyoxyalkylene (A)

<Preparation Example 1>

In a three-necked flask having a volume of 500 ml, 0.02 mol of 3-(trimethoxyindolyl)propylglutaric anhydride (hereinafter referred to as TMSG), 0.01 mol of 2-epoxypropanebutoxypropane was added. Trimethoxy hydrazine (hereinafter referred to as TMSOX-D), 0.20 molar Methyl trimethoxy decane (hereinafter referred to as MTMS), 0.50 mol of dimethyl dimethoxy decane (hereinafter referred to as DMDMS), 0.27 mol of phenyl triethoxy decane (hereinafter referred to as PTES), and 200 g 4-Hydroxy-4-methyl-2-pentanone (hereinafter abbreviated as DAA), and an aqueous oxalic acid solution (0.35 g of oxalic acid / 75 g of water) was added over 30 minutes while stirring at room temperature. Next, the flask was immersed in an oil bath at 30 ° C and stirred for 30 minutes. The oil bath was then warmed to 120 ° C in 30 minutes. When the temperature of the solution was lowered to 110 ° C (that is, the reaction temperature), the polymerization was continued by heating and stirring for 5 hours (that is, the polycondensation time). Further, the solvent is removed by distillation to obtain a polyoxyalkylene (A-1). The component types of the polyoxyalkylene (A-1) and the amounts thereof used are shown in Table 1.

<Preparation Example 2 to Preparation Example 6>

The polyfluorene oxide (A) of Preparation Example 2 to Preparation Example 6 was prepared in the same manner as in Preparation Example 1, and was distinguished by changing the kind of the component of the polyoxane (A), the amount thereof, and the reaction. Temperature and polycondensation time (as shown in Table 1).

Preparation of positive photosensitive polyoxane composition

<Example 1>

100 parts by weight of the polyoxyalkylene (A-1) of Preparation Example 1, 5 parts by weight of 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl) Orthophenylnaphthalene diazide sulfonate (B-1) formed by phenyl]ethylidene]bisphenol and o-naphthoquinonediazide-5-sulfonic acid, 0.1 part by weight of tributylphosphine (D) -1) and 100 parts by weight of the inorganic particles (E-1) are added to 100 parts by weight of propylene glycol methyl ether acetate (C-1), and stirred uniformly with a shaking type stirrer. The positive photosensitive polyoxane composition of Example 1 was obtained. The evaluation method of the positive photosensitive polyoxyalkylene composition of Example 1 described later was evaluated, and the results are shown in Table 2.

<Example 2 to Example 12>

The positive photosensitive polyoxyalkylene compositions of Examples 2 to 12 were separately prepared in the same manner as in Example 1, and were different in that the kinds of the components and the amounts thereof were changed, as shown in Table 2. . The positive photosensitive polysiloxane compositions obtained in Examples 2 to 12 were evaluated in the manner described later, and the results are shown in Table 2.

<Comparative Example 1 to Comparative Example 2>

The positive photosensitive polyoxyalkylene compositions of Comparative Examples 1 to 2 were separately prepared in the same manner as in Example 1, and were different in that the kinds of the components and the amounts thereof were changed, as shown in Table 2. . The positive photosensitive polysiloxane compositions obtained in Comparative Examples 1 to 2 were evaluated in the evaluation methods described later, and the results are shown in Table 2.

<Evaluation method>

Heat resistance:

The film thickness α _{1 of the} protective film was measured with a Tencor α- step stylus type measuring instrument (manufactured by American Kelei Co., Ltd.). Next, the protective film was baked at 230 ° C for 180 minutes, and then the film thickness α ₂ was measured with a Tencor α- step stylus type measuring instrument. The residual film ratio can be obtained by calculating the obtained film thickness α ₁ and film thickness α _{2 by the} following formula.

Residual film rate (%) = ( α ₂ / α ₁ ) × 100

The heat resistance of the protective film was evaluated according to the criteria shown below. The higher the residual film rate, the better the heat resistance of the protective film.

◎: residual film rate ≧ 98%

○: 98%> residual film rate ≧ 95%

△: 95%> residual film rate ≧ 93%

X: residual film rate <93%

The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

Claims (11)

A positive photosensitive polyoxane composition comprising: polyoxyalkylene (A); o-naphthoquinonediazide sulfonate (B); solvent (C); and a phosphine compound (D); The phosphine compound (D) includes at least one selected from the group consisting of a trialkylphosphine compound, a triarylphosphine compound, and a phosphonium salt. The positive photosensitive polyoxyalkylene composition according to Item 1, wherein the polyoxyalkylene (A) is at least polycondensed from the decane monomer (a-1) represented by the formula (I-1). And: Si(R ^a ) _w (OR ^b ) _4-w (I-1) wherein: R ^a each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 2 to 10 carbon atoms. a group having an aromatic group having 6 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms containing an acid anhydride group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having an epoxy group; And at least one R ^a represents an alkyl group having an acid number of 1 to 10, an alkyl group having an epoxy group having 1 to 10 carbon atoms or an alkoxy group having an epoxy group; and R ^b each independently represents hydrogen An atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 15 carbon atoms; and w represents an integer of 1 to 3. The positive photosensitive polyoxyalkylene composition according to claim 1, wherein the photosensitive polyoxyalkylene composition further comprises an inorganic particle (E) which is oxidized by a fourth group element The main component. The positive photosensitive polyoxyalkylene composition according to claim 3, wherein the inorganic particles The Group IV element in (E) is titanium or zirconium. The positive photosensitive polyoxyalkylene composition according to claim 3, wherein the inorganic particles (E) have a particle size of from 1 nm to 60 nm. The positive photosensitive polyoxyalkylene composition according to the third aspect of the invention, wherein the inorganic particles (E) are used in an amount of 30 to 300 based on 100 parts by weight of the polyoxyalkylene (A). Parts by weight. The positive photosensitive polyoxyalkylene composition according to Item 1, wherein the ortho-naphthoquinone diazide sulfonate (B) is used based on 100 parts by weight of the polyoxyalkylene (A). The amount used is 5 to 50 parts by weight; the solvent (C) is used in an amount of 100 to 600 parts by weight; and the phosphine compound (D) is used in an amount of 0.1 to 3 parts by weight. A method of forming a film on a substrate comprising applying the positive photosensitive polyoxyalkylene composition according to any one of claims 1 to 7 to the substrate. A film on a substrate produced by the method of claim 8. The film according to claim 9 which is a protective film for a flattening film for a TFT substrate, an interlayer insulating film or a core material of an optical waveguide or a cladding material in a liquid crystal display element or an organic electroluminescence display. A device comprising a film according to claim 9 or 10.