TWI557501B - Photosensitive polysiloxane composition, protecting film, and element having the protecting film - Google Patents

Description

Photosensitive polyoxyalkylene composition, protective film, and component having a protective film

The present invention relates to a photosensitive polyoxyalkylene composition, a protective film, and an element having a protective film. In particular, it relates to a photosensitive polyoxyalkylene composition having excellent sensitivity and stability, a protective film formed therefrom, and an element having a protective film.

In recent years, with the development of the semiconductor industry, liquid crystal display (LCD), and organic electro-luminescence display (OELD), the demand for size reduction has accompanied lithography (photolithography). The process has become a very important issue. In the photolithography process, it is necessary to fine-tune the desired pattern to achieve the purpose of downsizing. In general, the micronized pattern is formed by exposing and developing a positive photosensitive polysiloxane composition having high resolution and photosensitivity. It is worth mentioning that positive sensitivity The polyoxyalkylene composition is usually composed of polysiloxane as a main component.

In a liquid crystal display or an organic electroluminescent display, an interlayer insulating film is usually disposed between the layered wirings. The photosensitive material has a small number of steps necessary for obtaining a pattern shape, and at the same time, since the obtained insulating film has a good flatness, it is widely used as a material for forming an interlayer insulating film.

It is necessary to form a pattern of contact holes of fine wiring in the interlayer insulating film of the liquid crystal display. In fact, it is very difficult to achieve a usable aperture by a contact hole formed of a negative photosensitive composition. Therefore, a positive photosensitive composition is widely used in the industry to form an interlayer insulating film of a liquid crystal display element (e.g., JP-A-2001- Rev. 354822).

Japanese Laid-Open Patent Publication No. 2000-1648 discloses a photosensitive composition using a siloxane-based material, which is superior in heat resistance and transparency to a photosensitive composition of a conventional acrylic resin material. However, a polydecane-based material such as a decane compound or a polysiloxane is easily hydrolyzed and condensed by a compound of the same type or a different type. In the preparation of the photosensitive composition, the occurrence of these side reactions causes the storage stability of the photosensitive composition to be deteriorated, and the life of the product is also shortened.

In order to suppress the above hydrolysis and 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 JP-A-2003-163209 discloses various molecular weights of polyoxyalkylene, it does not take into consideration the photosensitive characteristics of the polyoxyalkylene; in addition to the dielectric constant, interlayer insulation is not considered. Various properties of the film.

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 photosensitive resin composition The sensitivity of the sensory is not good, so it cannot be accepted by the industry.

Therefore, how to meet the current requirements for sensitivity stability in the industry is an objective of research in the technical field to which the present invention pertains.

In view of the above, the present invention provides a photosensitive polyoxyalkylene composition having excellent sensitivity and stability, a protective film, and an element having a protective film.

The present invention provides a photosensitive polyoxyalkylene composition comprising polysiloxane (A), o-naphthoquinonediazide sulfonate (B), nitrogen-containing compound (C), and solvent (D).

The nitrogen-containing compound (C) includes the imidazole compound (C-1) represented by the formula (1), the pyrazole compound (C-2) represented by the formula (2), and the formula (3) or the formula (4). At least one of the triazole compound (C-3) and the tetrazole compound (C-4) represented by the formula (5).

The imidazole compound (C-1) represented by the formula (1) is shown below.

In the formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a hydroxyl group, an amine group, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number. a substituted or unsubstituted alicyclic group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group of 3 to 20, R ¹ and R ² may be condensed to form a substituted or unsubstituted a substituted benzene ring or a 6-membered heterocyclic ring; R ⁴ represents a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, a group represented by the formula (1-1), and a formula ( 1-2) a group represented by the formula, a group represented by the formula (1-3), a group represented by the formula (1-4) or a group represented by the formula (1-5), -(CH ₂ ) _a -X ¹ Formula (1-1)

In the formula (1-1), a represents an integer of 0 to 20, and X ¹ represents a hydroxyl group or a carboxyl group;

In the formula (1-2), b represents an integer of 0 to 20;

In the formula (1-3), d represents an integer of 0 to 20, and X ² and X ³ each independently represent a hydrogen atom or a hydroxyl group;

In the formula (1-4), e represents an integer of 0 to 20,

In the formula (1-5), f represents an integer of 0 to 6, and g represents an integer of 1 to 6.

The pyrazole compound (C-2) represented by the formula (2) is shown below.

In the formula (2), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydroxyl group, an amine group, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number. R ³ and R ⁶ and R ⁵ and R ⁷ may be condensed by a substituted or unsubstituted alicyclic group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group of 3 to 20 A substituted or unsubstituted benzene ring or a 6-membered heterocyclic ring is formed; R ^{8 is} synonymous with R ⁴ in the formula (1).

The triazole compound (C-3) represented by the formula (3) or the formula (4) is as follows.

In the formulae (3) and (4), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, an amine group, a carboxyl group, and a carbon number of 1 to 30. An alkyl group, an alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 30 carbon atoms, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group And R ⁹ and R ¹⁰ may be condensed to form a substituted or unsubstituted benzene ring or a 6-membered heterocyclic ring having one hetero atom.

The tetrazole compound (C-4) represented by the formula (5) is shown below.

In the formula (5), R ¹⁵ represents a hydrogen atom, a hydroxyl group, an amine group, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituted carbon number of 3 to 20 or Unsubstituted alicyclic group, substituted or unsubstituted phenyl group or substituted or unsubstituted benzyl group; R ^{16 is} synonymous with R ⁴ in the formula (1).

In an embodiment of the invention, the photosensitive polyoxyalkylene composition, wherein the polyoxyalkylene (A) is obtained by polycondensation of a decane monomer component, and the decane monomer component comprises the formula (I). Compound represented by -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 aryl group having 6 to 15 carbon atoms, and an acid anhydride group. alkyl group, an epoxy group-containing alkyl group or alkoxy group containing an epoxy group, at least one of R ^a is an alkyl group containing an acid anhydride group, epoxy group-containing alkyl or alkoxy group containing an epoxy group; R & lt ^b each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms; and w represents an integer of 1 to 3.

In one embodiment of the present invention, the amount of the o-naphthoquinonediazide sulfonate (B) is from 1 to 35 parts by weight, based on the polyoxymethane (A) used in an amount of 100 parts by weight, the nitrogen-containing compound The amount of (C) used is 0.1 to 10 parts by weight, and the solvent (D) is used in an amount of 100 to 1500 parts by weight.

The present invention further provides a protective film formed by applying the above-mentioned photosensitive polyoxyalkylene composition onto an element, pre-baked, exposed, developed, and post-baked.

The present invention also provides an element having a protective film comprising an element and the above-described protective film, wherein a protective film is overlaid on the element.

Based on the above, the nitrogen-containing compound contained in the photosensitive polyoxyalkylene composition of the present invention has a five-membered ring in which a five-membered ring has two or more nitrogen atoms and two double bonds, and contains a sulfonic acid group. The group is therefore excellent in sensitivity and is suitable for forming a protective film.

The above described features and advantages of the present invention will be more apparent from the following description.

<Photosensitive polyoxyalkylene composition>

The present invention provides a photosensitive polyoxyalkylene composition comprising polysiloxane (A), o-naphthoquinonediazide sulfonate (B), nitrogen-containing compound (C), and solvent (D). Further, the photosensitive polyoxyalkylene composition may further include the additive (E), if necessary.

The respective components used in the photosensitive polyoxyalkylene composition of 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.

Polyoxane (A)

The type of the polyoxyalkylene polymer (A) is not particularly limited, but it can achieve the object of the present invention. The polyoxyalkylene (A) is obtained by polycondensation (i.e., hydrolysis and partial condensation) of a decane monomer component, wherein the decane monomer component includes a decane monomer (a-1). In addition, the decane monomer component may further include However, it is not limited to the decane monomer (a-2) other than the decane monomer (a-1), the decane prepolymer (a-3), the cerium oxide particles (a-4), or a combination thereof. Hereinafter, the respective components of the decane monomer component and the reaction steps and conditions of the polycondensation will be further explained.

Decane monomer (a-1)

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 aryl group having 6 to 15 carbon atoms, and an acid anhydride group. alkyl group, an epoxy group-containing alkyl group or alkoxy group containing an epoxy group, at least one of R ^a is an alkyl group containing an acid anhydride group, epoxy group-containing alkyl or alkoxy group containing an epoxy group; R & lt ^b each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms; and w represents an integer of 1 to 3.

When More specifically, when the formula R ^{(I-1), a} represents an alkyl group having a carbon number of 1 to 10, in particular, R ^a, for example, methyl, ethyl, n-propyl, isopropyl, 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- Mercaptopropyl 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 aryl 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 aryl group having an aryl group having another substituent, and specifically, R ^a is, for example, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl (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 aryl group having 6 to 15 carbon atoms, 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 (TMS-GAA), 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-(triphenyloxyindenyl)propyl succinic anhydride, a city manufactured by Shin-Etsu Chemical Co., Ltd. Sold out: 3-(trimethoxyindenyl)propyl succinic anhydride (trade name X-12-967), a commercial product manufactured by WACKER: 3-(triethoxyindenyl)propyl butyl Diacid anhydride (trade name GF-20), 3-(trimethoxydecyl)propyl glutaric anhydride (TMSG), 3-(triethoxyindolyl)propyl glutaric anhydride 3-(triphenyloxyindenyl)propyl glutaric anhydride, diisopropoxy-di(2-oxetanylbutoxypropyl)silane, referred to as diisopropoxy-di(2-oxetanylbutoxypropyl)silane DIDOS), di(3-oxetanylpentyl)dimethoxy silane, (di-n-butoxycarbonyl)di(propyl succinic anhydride), (two) Methoxyindolyl) bis(ethyl succinic anhydride), 3-glycidoxypropyl 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyl dimethylethoxysilane, bis(2-epoxypropoxybutoxypentyl) 2-(2-oxetanylbutoxypentyl)-2-oxetanyl pentylethoxy silane, tri(2-oxetanylpentyl) Methoxy silane), (phenoxymercapto)tris(propyl succinic anhydride), (methylmethoxyindolyl) bis(ethyl succinic anhydride), or a combination of the above compounds.

The 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-(triethoxyindenyl)propyl succinic anhydride, 3-(trimethoxyindolyl)propyl glutaric anhydride, (dimethoxy) Bismuthyl) bis(ethyl succinic anhydride), 2-propylene oxide butyloxypropyl trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2- Propylene oxide butyloxypropyl triethoxy decane or a combination of the above compounds.

The decane monomer (a-1) is used in an amount of from 0.5 mole percent to 50 mole percent, preferably from 1 mole percent to 40 percent, based on the total amount of monomers in the decane monomer component of 100 mole percent. The percentage of moles, and more preferably from 1 mole percent to 30 mole percent. In the photosensitive polyoxane composition, when the decane monomer component forming the polyoxyalkylene (A) contains the decane monomer (a-1), the sensitivity of the photosensitive polyoxyalkylene composition is preferably stable. .

Decane monomer (a-2)

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 aryl group having 6 to 15; R ^d is independently It represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or an aryl 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 aryl group having 6 to 15 carbon atoms, specifically, R ^c is, for example, a phenyl group, a tolyl group or a naphthyl group. Further, R ^c may also be an aryl group having an aryl group having another substituent, and specifically, R ^c is, for example, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl (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 aryl 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 Tetraphenoxysilane or tetraphenoxy silane; (2) Trifunctional decane monomer: methyltrimethoxysilane (MTMS), methyltriethoxysilane, methyltriisopropoxysilane, methyl tri-n-butyl Tri methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyl tri-n-butoxy Ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, N-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, ethylene Triphenylmethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane (PTMS) ), phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxydecane (1-(p) -hydroxyphenyl)ethyltrimethoxysilane), 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxyl -5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyl Trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxy Decane or 3-methacryloxypropyltriethoxydecane; (3) Difunctional decane monomer: dimethyldimethoxysilane (DMDMS), dimethyldiethoxydecane (dimethyldiethoxysilane), dimethyldiacetyloxysilane, di-n-butyldimethoxysilane or diphenyldimethoxysilane; or (4) Monofunctional decane monomer: trimethyl Silane group (trimethylmethoxysilane) Silane ethoxy or n-butyl (tri-n-butylethoxysilane) and the like. The various decane monomers described may be used singly or in combination of two or more.

Oxane prepolymer (a-3)

The decane 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 aryl group of 15 wherein the alkyl group, the alkenyl group and the aryl 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 aryl group having 6 to 15 carbon atoms, wherein any one of the alkyl group, the fluorenyl group and the aryl group optionally has a substituent; s represents an integer of 1 to 1000.

In the formula (I-3), R ^e , R ^f , R ^g and R ^h each independently represent an alkyl group having 1 to 10 carbon atoms, and for example, R ^e , R ^f , R ^g and R ^h are each independently Methyl, ethyl or n-propyl. In the formula (I-3), R ^e , R ^g , R ^g and R ^h each independently represent an alkenyl group having 2 to 10 carbon atoms, and for example, R ^e , R ^f , R ^g and R ^h are each independently Vinyl, acryloxypropyl or methacryloxypropyl. In the formula (I-3), R ^e , R ^f , R ^g and R ^h each independently represent an aryl group having a carbon number of 6 to 15, and for example, R ^e , R ^f , R ^g and R ^h are each independently Phenyl, tolyl or naphthyl and the like. It is to be noted that any of the alkyl group, the alkenyl group and the aryl group may optionally have a substituent.

In the formula (I-3), R ⁱ and R ^j each independently represent an alkyl group having 1 to 6 carbon atoms, and for example, R ⁱ and R ^j are each independently a methyl group, an ethyl group, a n-propyl group or an isopropyl group. Base or n-butyl. In the formula (I-3), R ⁱ and R ^j each independently represent a fluorenyl group having a carbon number of 1 to 6, and is, for example, an oxime group. In the formula (I-3), R ⁱ and R ^j each independently represent an aryl group having a carbon number of 6 to 15, and is, for example, a phenyl group. It is to be noted that 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 1 to 1000, preferably an integer of 3 to 300, and more preferably an integer of 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 A commercially available product of Silanol terminated polydimethylsiloxane (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 decane prepolymer (a-3) may be used singly or in combination of two or more.

Cerium oxide particles (a-4)

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

Polycondensation reaction steps and conditions

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 component; and heating and stirring at 50 ° C to 150 ° C for 0.5 hour. By to 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 (D) included in the photosensitive polyoxyalkylene composition of the present invention. The total amount of the decane monomer component is 100 g, and the solvent is preferably used in an amount of 15 It is 1200 g; more preferably 20 g to 1100 g; and even more preferably 30 g to 1000 g.

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

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, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or an anhydride thereof, or an 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 g to 15 g; more preferably from 0.01 g to 12 g; and preferably from 0.05 g to 10 g, based on the total amount of the decane monomer component.

From the standpoint of stability, the polyoxyalkylene (A) is preferably free of by-products (such as alcohols or water) and catalysts. Therefore, the polyoxoxane (A) which can be obtained by purifying the reaction mixture after the polycondensation reaction can be selectively obtained. 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.

In the photosensitive polyoxyalkylene composition, when the decane monomer component forming the polyoxyalkylene (A) includes the decane monomer (a-1), the sensitivity stability of the photosensitive polyoxyalkylene composition can be made. Preferably.

O-naphthoquinonediazide sulfonate (B)

The type of the o-naphthoquinonediazide sulfonate (B) is not particularly limited, and the ortho-naphthoquinone diazide 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 o-naphthoquinonediazidesulfonic acid include, but are not limited to, o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide-5-sulfonic acid or o-naphthoquinonediazide-6-sulfonic acid. Wait. 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.

(1) Hydroxybenzophenone-based compound (hydroxybenzophenone-based) Specific examples of the 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 or the like.

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

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

Specifically, a specific example of the hydroxyaryl compound represented by the formula (II-1) Including but not limited to tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethyl Phenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylbenzene 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-di Methylphenyl)-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-cyclohexyl-4-hydroxy-6-methylphenyl)-3-hydroxybenzene Methane, bis(3-cyclohexyl- 4-hydroxy-6-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, bis ( 3-cyclohexyl-6-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyl) Phenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-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.

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

In the formula (II-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 (II-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.

(4) Specific examples of other aromatic hydroxy compounds include, but are not limited to, phenol, p-methoxy phenol, dimethyl phenol, hydroquinone, bisphenol A, naphthol, catechol, 1,2,3-benzenetriol methyl ether, 1,2,3-benzenetriol-1,3-dimethyl ether, 3,4,5-trihydroxybenzoic acid, or partially esterified or partially etherified (etherify) 3,4,5-trihydroxybenzoic acid, etc.

The hydroxy compound is preferably 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 2,3,4-trihydroxyl Benzophenone, 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 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, the total amount of hydroxyl groups in the hydroxy compound is 100 mol% (mol%), and the hydroxy compound More than 50 mol% of the hydroxyl groups 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.

The o-naphthoquinonediazide sulfonate (B) is used in an amount of 1 to 35 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the polyoxyalkylene (A); and more preferably It is 5 to 30 parts by weight.

Nitrogen-containing compound (C)

The nitrogen-containing compound (C) has a five-membered ring in which a five-membered ring has two or more nitrogen atoms and two double bonds, and contains a group other than a sulfonic acid group. Specifically, the nitrogen-containing compound (C) includes an imidazole compound (C-1), a pyrazole compound (C-2), a triazole compound (C-3), and a tetrazole compound represented by the formula (5) (C- At least one of 4).

Imidazole compound (C-1)

The imidazole compound (C-1) is a compound represented by the formula (1).

In the formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a hydroxyl group, an amine group, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number. a substituted or unsubstituted alicyclic group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group of 3 to 20, R ¹ and R ² may be condensed to form a substituted or unsubstituted a substituted benzene ring or a 6-membered heterocyclic ring; R ⁴ represents a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, a group represented by the formula (1-1), and a formula ( 1-2) a group represented by the formula, a group represented by the formula (1-3), a group represented by the formula (1-4) or a group represented by the formula (1-5), -(CH ₂ ) _a -X ¹ Formula (1-1)

In the formula (1-1), a represents an integer of 0 to 20, and X ¹ represents a hydroxyl group or a carboxyl group;

In the formula (1-2), b represents an integer of 0 to 20;

In the formula (1-3), d represents an integer of 0 to 20, and X ² and X ³ each independently represent a hydrogen atom or a hydroxyl group;

In the formula (1-4), e represents an integer of 0 to 20,

In the formula (1-5), f represents an integer of 0 to 6, and g represents an integer of 1 to 6.

Specific examples of the imidazole compound (C-1) include imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1-hydroxyimidazole, 1-hydroxymethylimidazole, and 1 -(2-hydroxyethyl)-imidazole, 1-(3-hydroxypropyl)-imidazole, 1-(4-hydroxybutyl)-imidazole, 1-(10-hydroxyindenyl)imidazole, 1-phenyl Imidazole, 1-benzylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, 1,2-di Methylimidazole, 1,2,4,5-tetramethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1 -imidazoleacetic acid, imidazole-4-carboxylic acid, 4-methyl-2-propyl-6-benzimidazolecarboxylic acid, 2-phenyl-4-methyl-5-benzylimidazole, 2,4-di Phenyl imidazole, 2,4-diphenyl-5-methylimidazole, 1-(3-aminopropyl)imidazole, benzimidazole, 1-methylbenzimidazole, 2-methylbenzo Imidazole, 5-methylbenzimidazole, 2-nonylbenzimidazole, 1,2-dimethylbenzimidazole, 5,6-dimethylbenzimidazole, 2-hydroxybenzo Imidazole, 2-(hydroxymethyl)benzimidazole, 2-(3-hydroxypropyl)benzimidazole, 2-amino-benzimidazole, 2-phenylbenzimidazole, 2-(4-pyridyl Benzimidazole, 5-benzimidazolecarboxylic acid, 2-isopropyl-4-methylimidazole, adenine, 9-(2-hydroxyethyl)adenine, 2-aminopurine, 2 - Amino-6-methoxyanthracene, 2-acetamidamine-6-hydroxyindole, or a combination of the above compounds.

Pyrazole compound (C-2)

The pyrazole compound (C-2) is a compound represented by the formula (2).

In the formula (2), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydroxyl group, an amine group, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number. R ³ and R ⁶ and R ⁵ and R ⁷ may be condensed by a substituted or unsubstituted alicyclic group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group of 3 to 20 A substituted or unsubstituted benzene ring or a 6-membered heterocyclic ring is formed; R ^{8 is} synonymous with R ⁴ in the formula (1), and will not be further described herein.

Specific examples of the pyrazole compound (C-2) include pyrazole, 1-methylpyrazole, 3-methylpyrazole, 4-methylpyrazole, 3,4-dimethylpyrazole, 3,5- Dimethylpyrazole, 3,5-diisopropylpyrazole, 3,5-dimethyl-5-phenylpyrazole, 3-aminopyrazole, 3-amino-1-methylpyrazole , 3-amino-4-methylpyrazole, 3-amino-5-methylpyrazole, 3-amino-5-t-butylpyrazole, 3-amino-5-phenylpyrazole , 3-amino-5-hydroxypyrazole, 5-amino-1-phenylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, indazole, 5- Amino oxazole, 5-nitrocarbazole, 6-nitrocarbazole, 7-nitrocarbazole, 6-aminocarbazole, carbazole-3-carboxylic acid, 3,5-pyrazoledicarboxylic acid , 1-phenyl-3-methyl-5-amino-pyrazole, allopurinol, 4-aminopyrazolo[3,4-d]pyrimidine, 1-benzyl-1H-indole Zyridin-3-ol, or a combination of the above compounds.

Triazole compound (C-3)

The triazole compound (C-3) is a compound represented by the formula (3) or the formula (4).

In the formulae (3) and (4), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, an amine group, a carboxyl group, and a carbon number of 1 to 30. An alkyl group, an alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 30 carbon atoms, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group And R ⁹ and R ¹⁰ may be condensed to form a substituted or unsubstituted benzene ring or a 6-membered heterocyclic ring having one hetero atom, wherein the hetero atom may be a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. .

In the triazole compound (C-3), R ⁹ and R ¹⁰ may be condensed to form a substituted or unsubstituted benzene ring or a 6-membered heterocyclic ring having one hetero atom. Specifically, the triazole compound (C-3) is, for example, a compound represented by the formula (3-1), the formula (3-2) or the formula (3-3).

In the formula (3-1), the formula (3-2) and the formula (3-3), R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a hydroxyl group, a mercapto group, an amine group, a carboxyl group, a nitro group, and a carbon number of 1 to An alkyl group of 10, an alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, a substituted or unsubstituted phenyl group or a substituted or unsubstituted R ^{11 is} synonymous with R ¹¹ in the formula (3), and will not be further described herein; k1, k2 and k3 each independently represent an integer of 0 to 3, and when k1, k2 and k3 each independently represent 2 or 3 A plurality of R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different.

Specific examples of the triazole compound (C-3) include 1,2,3-triazole, 1,2,4-triazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipropyl- 4H-1,2,4-triazole, 3-amino-5-isopropyl-1,2,4-triazole, 4-amino-3-indolyl-5-methyl-4H-1,2 , 4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3-amino-5-methyl-4H-1, 2,4-triazole, 4-amino- 1,2,4-triazole, 4-amino-3,5-dimethyl-1,2,4-triazole, 4-amino-5-methyl-4H-1,2,4-tri Oxazole-3-thiol, 3,5-diamino-1H-1,2,4-triazole, 1,2,3-benzotriazole, 1-aminobenzotriazole, 1-hydroxybenzene And triazole, 4-hydroxy-1H-benzotriazole, 1-(hydroxymethyl)benzotriazole, 2-aminobenzotriazole, 5-amino-1H-benzotriazole, 4- Methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, 1H-benzotriazole-4-carboxylic acid, 1H-benzotriazole-5-carboxylic acid, 4-nitro -1H-benzotriazole, 5-nitro-1H-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, 1-[(2-ethylhexylamino) )methyl]-benzotriazole, 1-(1',2'-dicarboxyethyl)benzotriazole, 1-(2,3-dicarboxypropyl)benzotriazole 1-[N,N-bis(2-ethylhexyl)aminomethyl]tolyltriazole, 1-[N,N-bis(hydroxyethyl)aminomethyl]tolyltriazole, 1- [N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-[N,N-bis(2-hydroxyethyl)aminomethyl]benzotriazole, 1- [N-2-hydroxyethylaminomethyl]benzene Triazole, 1-[N,N-bis(2-hydroxyethyl)aminomethyl]-4-carboxybenzotriazole, 1-[N,N-bis(2-hydroxyethyl)amine Methyl]-5-carboxybenzotriazole, 1-[N,N-bis(2-hydroxyethyl)aminomethyl]-4-methylbenzotriazole, 1-[N,N-double (2-hydroxyethyl)aminomethyl]-5-methylbenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-4-methylbenzotriene Iridazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-5-methylbenzotriazole, 1H-1,2,3-triazole[4,5-b]pyridine , 2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzo Triazole, 2-(2-hydroxy-5-th-octylphenyl)-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H -benzotriazol-2-yl)-4,6-di-third amyl phenol, 2-(3,5-di-t-butyl 2-hydroxyphenyl)-1-benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-1-benzotriazole, 2-(2-hydroxy-5-th-octylphenyl)-1-benzotriazole, 2- (benzotriazol-1-yl)-p-cresol, 2-(benzotriazol-1-yl)-4,6-di-third amyl phenol, 4-azabenzotriazole, 1 -hydroxy-7-azabenzotriazole, 1-ethylindenyl-1H-1,2,3-three Zoledolo[4,5-b]pyridine, or a combination of the above compounds.

Tetrazolium compound (C-4)

The tetrazole compound (C-4) is a compound represented by the formula (5).

In the formula (5), R ¹⁵ represents a hydrogen atom, a hydroxyl group, an amine group, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituted carbon number of 3 to 20 or Unsubstituted alicyclic group, substituted or unsubstituted phenyl group or substituted or unsubstituted benzyl group; R ^{16 is} synonymous with R ⁴ in the formula (1), and will not be further described herein.

Specific examples of the tetrazole compound (C-4) include 1H-tetrazole, 1-methyltetrazole, 1-ethyltetrazole, 1-propyltetrazole, 1-phenyltetrazole, 1-benzyltetra Azole, 5-methyltetrazole, 5-ethyltetrazole, 5-propyltetrazole, 5-cyclohexyltetrazole, 5-phenyltetrazole, 5-benzyltetrazole, 5-aminotetrazole , 5-(p-tolyl)-tetrazole, 1,5-dimethyltetrazole, 1-methyl-5-hydroxytetrazole, 1-ethyl-5-hydroxytetrazole, 1-propyl-5 - hydroxytetrazole, 1-phenyl-5-hydroxytetrazole, or a combination of the above compounds.

The nitrogen-containing compound (C) is used in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 10 parts by weight, and more preferably 02 to 8 parts by weight, based on 100 parts by weight of the polysiloxane (A). .

When the photosensitive polyoxyalkylene composition does not contain the nitrogen-containing compound (C), the sensitivity stability is poor.

Solvent (D)

The kind of the solvent (D) is not particularly limited. The solvent (D) is, for example, a compound containing an alcoholic hydroxy group or a cyclic compound containing a 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-hydroxy- 3-hydroxy-3-methyl-2-butanone, 5-hydroxy-2- 5-hydroxy-2-pentanone, 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 (propylene glycol) Monomethyl ether acetate,PGMEA), propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-butyl ether T-butyl ether), 3-methoxy-1-butanol, 3-methyl-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 carbonyl-containing cyclic compound include, but are not limited to, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and 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 combined with a carbonyl group-containing cyclic compound. It is used, and its weight ratio is not particularly limited. The weight ratio of the alcoholic hydroxyl group-containing compound to the carbonyl group-containing 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 (D), 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 (D) may contain other solvents insofar as the effects of the present invention are not impaired. Other solvents are, for example: (1) Esters: 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: methyl isobutyl ketone, diisopropanone or diisobutyl ketone; or (3) ethers : diethyl ether, diisopropyl ether, di-n-butyl ether or diphenyl ether.

The solvent (D) is used in an amount of from 100 to 1,500 parts by weight, based on the polysiloxane (A), in an amount of from 100 to 1,500 parts by weight; preferably from 200 to 1200 parts by weight; and more preferably from 300 to 1,000 parts by weight.

Additive (E)

The photosensitive polysiloxane composition of the present invention can be selectively further added with the additive (E). Specifically, the additive (E) is, for example, a sensitizer, an adhesion auxiliary agent, a surfactant, and a dissolution promotion. Solubility promoter, defoamer or a combination thereof.

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.

(1) Specific examples of the trisphenol type compound include, but are not limited to, tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, Bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, Bis(4-hydroxy-3,5-dimethylphenyl)-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-hydroxyl -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-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane or Double (5-ring Hexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane.

(2) 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'-hydroxybenzene) 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-trihydroxyl) Phenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane, and the like.

(3) Specific examples of polynuclear branched compounds include, but are not limited to, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxybenzene) Ethyl]benzene or 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl) Base] benzene and so on.

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

(5) Specific examples of 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.

The sensitizer is used in an amount of 5 to 50 parts by weight, preferably 8 to 40 parts by weight, and more preferably 10 to 35 parts by weight, based on 100 parts by weight of the polysiloxane (A).

Specific examples of the adhesion promoter include melamine compounds and hydrazine An alkyl compound or the like. The role of the adhesion aid is to increase the adhesion between the protective film formed of the photosensitive polyoxyalkylene composition and the member to be protected.

Specific examples of commercial products of melamine include those manufactured by Mitsui Chemicals under the trade name of Cymel-300 or Cymel-303; or those manufactured by Sanwa Chemical under the trade names of MW-30MH, MW-30, MS-11, MS- 001, MX-750 or MX-706.

When the melamine compound is used as the adhesion aid, the amount of the melamine compound used is 0 to 20 parts by weight, preferably 0.5 to 18 parts by weight, based on 100 parts by weight of the polyoxyalkylene (A); More preferably, it is 1.0 to 15 parts by weight.

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-amine Propyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 2-(3,4-epoxycyclohexyl Ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-mercaptopropyl Trimethoxy decane or a commercial product (trade name such as KBM403) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

When a decane-based compound is used as the adhesion aid, the amount of the decane-based compound used is 0 to 2 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the polyoxyalkylene (A); More preferably, it is 0.1 to 0.8 part by weight.

Specific examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and polyoxyl An alkane 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, etc.; (2) polyethylene oxide alkyl Polyoxyethylene phenyl ethers: polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, etc.; (3) polyethylene glycol diesters: poly Ethylene glycol dilaurate, polyethylene glycol distearate, etc.; (4) sorbitan fatty acid esters; (5) fatty acid modified polyester (fatty acid modified Polyesters; 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 .

The surfactant is used in an amount of 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably 3 to 30 parts by weight, based on 100 parts by weight of the polysiloxane (A).

Specific examples of antifoaming agents 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 (manufactured by Air Products), and the like. The antifoaming agent is used in an amount of 1 to 10 parts by weight; preferably 2 to 9 parts by weight; and more preferably 3 to 8 parts by weight based on 100 parts by weight of the total of the polysiloxane (A).

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 dissolution promoter is used in an amount of 1 to 20 parts by weight, preferably 2 to 15 parts by weight, and more preferably 3 to 10 parts by weight, based on 100 parts by weight of the polysiloxane (A).

<Method for Preparing Photosensitive Polyoxane Composition>

The photosensitive polyoxyalkylene composition of the present invention is a positive photosensitive composition. A method which can be used to prepare a photosensitive polyoxyalkylene composition, for example, by placing polyoxazane (A), o-naphthoquinonediazide sulfonate (B), nitrogen-containing compound (C), and solvent (D) The mixture is stirred in a stirrer to be uniformly mixed into a solution state, and if necessary, an additive (E) may be added, and after uniformly mixing, a photosensitive polyoxane composition in a solution state may be obtained.

<Protective film and method of forming an element having a protective film>

The present invention further provides a protective film which is the above-mentioned photosensitive polyoxygen The alkane composition is applied to the component and then pre-baked, exposed, developed, and post-baked.

The present invention also provides an element having a protective film comprising an element and the above-described protective film, wherein a protective film is overlaid on the element. Specifically, the element having the protective film is, for example, a flattening film used in a liquid crystal display element or an organic electroluminescence display, an interlayer insulating film or a core material of an optical waveguide, or a cladding material.

Hereinafter, a method of forming a protective film will be described in detail, which comprises sequentially forming a prebaked coating film using a photosensitive polyoxyalkylene composition, patterning exposure of the prebaked coating film, and removing unexposed regions by alkali development. Forming a pattern; and performing a post-baking treatment to form a protective film.

Forming a pre-baked film

The photosensitive polysiloxane 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 photosensitive polyoxyalkylene composition is removed by vacuum drying, and then the residual organic solvent is completely removed by pre-bake to form a pre-baked coating 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, decompression drying is carried out at pressures from 0 Torr to 200 Torr. The line is from 1 second to 60 seconds, and the pre-baking 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 pre-baked coating film is immersed in a developing solution having a temperature of 23±2° C. for development for about 15 seconds to 5 minutes to remove unnecessary portions of the exposed pre-baked coating film. A semi-finished product having a protective film of a predetermined pattern is formed on a 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 a olefin.

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 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% From wt% to 5 wt%; still more preferably from 0.01 wt% to 1 wt%. An embodiment of the present invention is a developer using 2.38 wt% of tetramethylammonium hydroxide. It is worth mentioning that the photosensitive polyoxyalkylene composition of the present invention can form a fine refinement pattern even when a developer having a lower concentration is used.

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.

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

Synthesis examples and comparative synthesis examples of polyoxyalkylene (A)

Hereinafter, Synthesis Example A-1 to Synthesis Example A-8 of polyoxyalkylene (A) will be described:

Synthesis Example A-1

In a three-necked flask having a volume of 500 ml, 0.05 mol of 3-(triethoxyindolyl)propyl succinic anhydride (hereinafter abbreviated as GF-20) and 0.3 mol of methyltrimethoxydecane were added. (hereinafter referred to as MTMS), 0.65 mol of phenyltrimethoxydecane (hereinafter abbreviated as PTMS) and 200 g of propylene glycol monoethyl ether (hereinafter abbreviated as PGEE), and added at room temperature for 30 minutes while stirring. An aqueous solution of oxalic acid (0.40 g of oxalic acid dissolved in 75 g of water). 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 105 ° C (that is, the reaction temperature), the polymerization was continued by heating and stirring for 6 hours (that is, the polycondensation time). Further, the solvent and by-products are removed by distillation to obtain polyoxyalkylene A-1. The composition of the polyoxyalkylene A-1 and its use amount are shown in Table 1.

Synthesis Example A-2 to Synthesis Example A-8

The polysiloxane (A) of Synthesis Example A-2 to Synthesis Example A-8 (i.e., polyoxyalkylene A-2 to polyoxyalkylene A-8) was carried out in the same manner as in Synthesis Example A-1. Preparation, and the difference is that the decane monomer component, solvent, catalyst, and amount thereof, reaction temperature, and polycondensation time of the polyoxyalkylene (A) are changed (as shown in Table 1).

The compounds corresponding to the abbreviations in Table 1 are as follows.

Examples and comparative examples of photosensitive polyoxyalkylene composition and protective film

Hereinafter, Examples 1 to 12 and Comparative Examples 1 to 3 of the photosensitive polyoxyalkylene composition and the protective film are described:

Example 1 a. Preparation of photosensitive polyoxane composition

100 parts by weight of polyoxyalkylene A-1, 1 part by weight of 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)B O-naphthoquinonediazide sulfonate (B-1) formed by benzene and o-naphthoquinonediazide-5-sulfonic acid and 0.1 part by weight of 2-hydroxybenzimidazole (C) -1-1) Add 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) (D-1), and stir evenly with a shaking type stirrer. The photosensitive polyoxyalkylene composition of Example 1 was obtained. The evaluation method of the photosensitive polyoxyalkylene composition of Example 1 described later was evaluated, and the results are shown in Table 2.

b. Formation of protective film

The photosensitive polyoxyalkylene composition was applied by spin coating to a glass substrate of a size of 100 × 100 × 0.7 mm ³ to form a coating film having a thickness of about 2 μm. Next, the coating film was prebaked at 110 ° C for 2 minutes to form a prebaked coating film. Then, a positive photoresist mask was placed between the exposure machine and the pre-baked film, and the pre-baked film was patterned by ultraviolet light of 100 mJ/cm ² (exposure machine model AG500-4N, by M&R nm) Technology (M&R Nanotechnology) manufacturing). Next, the exposed pre-baked substrate was exposed to a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds at 23 ° C to remove the unexposed portion of the glass substrate. . Then, the glass substrate was washed with water. Then, the exposed and developed prebaked coating film was irradiated with an energy of 200 mJ/cm ² by an exposure machine. Then, the prebaked coating film was baked in an oven at 230 ° C for 60 minutes to form a protective film on the glass substrate.

Embodiment 2 to Embodiment 12

The photosensitive polyoxyalkylene composition and the protective film of Example 2 to Example 12 were separately prepared in the same manner as in Example 1, and the difference was that the kind of the component and the amount thereof were changed, as shown in Table 2. Show. The photosensitive polysiloxane compositions obtained in Examples 2 to 12 were evaluated in the evaluation methods described later, and the results are shown in Table 2.

Comparative Example 1 to Comparative Example 3

The photosensitive polyoxyalkylene compositions of Comparative Examples 1 to 3 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 photosensitive polyoxoxane compositions prepared in Comparative Examples 1 to 3 were evaluated in the following evaluation manners, and the results are shown in Table 2.

The compounds corresponding to the abbreviations in Table 2 are as follows.

[Evaluation method] Sensitivity stability

The photosensitive polyoxyalkylene composition was applied by spin coating to a glass substrate of a size of 100 × 100 × 0.7 mm ³ to form a coating film having a thickness of about 2 μm. Next, the coating film was prebaked at 110 ° C for 2 minutes to form a prebaked coating film. Then, a suitable mask is placed between the exposure machine and the pre-baked film, and the pre-baked film is subjected to pattern exposure by ultraviolet light (exposure model AG500-4N, manufactured by M&R Nanotechnology), wherein ultraviolet The irradiation energy of light is S ₁ mJ/cm ² . Next, the exposed pre-baked substrate was exposed to a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds at 23 ° C to remove the unexposed portion of the glass substrate. .

Further, the same photosensitive polyoxyalkylene composition as described above was placed in an environment of 45 ° C for three days, and then applied to a glass substrate of 100 × 100 × 0.7 mm ³ by spin coating. To form a coating film having a thickness of about 2 μm. Next, the coating film was prebaked at 110 ° C for 2 minutes to form a prebaked coating film. Then, a suitable mask is placed between the exposure machine and the pre-baked film, and the pre-baked film is subjected to pattern exposure by ultraviolet light, wherein the irradiation energy of the ultraviolet light is S ₂ mJ/cm ² . Next, the exposed pre-baked substrate was exposed to a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds at 23 ° C to remove the unexposed portion of the glass substrate. .

The sensitivity change rate is calculated by the irradiation energy S ₁ of the ultraviolet light and the irradiation energy S _{2 of the} ultraviolet light according to the following formula. The lower the sensitivity change rate, the better the sensitivity stability of the photosensitive polyoxane composition.

The evaluation criteria of the sensitivity change rate are as follows.

◎: 0% ≦ sensitivity change rate <10; ○: 10 ≦ sensitivity change rate <20; ×: sensitivity change rate ≧20.

Comparative example 4

The photosensitive polyoxyalkylene composition of Comparative Example 4 was a positive photosensitive composition. Specifically, the photosensitive polyoxyalkylene composition composition of Comparative Example 4 was obtained by using 100 parts by weight of polyoxyalkylene A-1 and 5 parts by weight of 1-[1-(4-hydroxyphenyl). O-naphthoquinonediazide sulfonate formed from isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene and o-naphthoquinonediazide-5-sulfonic acid (B -1) and 1 part by weight of 1H-benzotriazole-4-sulfonic acid is added to 100 parts by weight of propylene glycol monomethyl ether acetate (D-1), and shaken After the stirrer was uniformly stirred, the photosensitive polyoxyalkylene composition of Comparative Example 4 was obtained. The photosensitive polyaluminoxane composition thus obtained was also evaluated by the above evaluation method, and its sensitivity stability was expressed as ×.

Comparative Example 5

The photosensitive polyoxyalkylene composition of Comparative Example 5 is a negative photosensitive composition. Specifically, the photosensitive polyoxyalkylene composition of Comparative Example 5 was obtained by using 100 parts by weight of polyoxyalkylene A-1 and 3 parts by weight of 1-[9-ethyl-6-(2-A). Benzobenzhydryl)-9H-carbazol-3yl]-ethanone-1-(O-acetamidopurine) (trade name: IRGACURE OXE-02, manufactured by Asahi Kasei Chemicals Co., Ltd., as a radical polymerization Starting agent), 30 parts by weight of dipentaerythritol hexaacrylate, 1 part by weight of 5-methyl-1H-benzotriazole (C-3-1), 200 parts by weight of diethylene glycol ethyl methyl ether (as a solvent), 100 parts by weight of ethylene glycol monobutyl ether (as a solvent), 0.2 parts by weight of a polyoxyalkylene surfactant SH8400 (manufactured by Dow Corning Dongli Polyxan Co., Ltd.) uniformly mixed To prepare. The obtained photosensitive polyoxane composition is also evaluated as above. After the price method is evaluated, the performance of the sensitivity stability is ×.

Comparative Example 6

The photosensitive novolac resin composition of Comparative Example 6 was a positive photosensitive composition. Specifically, the photosensitive novolac resin composition of Comparative Example 6 is obtained by using 100 parts by weight of a novolak resin (weight-average molecular weight (MW) obtained in terms of polystyrene is 10,600, manufactured by Asahi Organic Materials Co., Ltd. , trade name EP-4080G), 10 parts by weight of 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene and adjacent O-naphthoquinonediazide sulfonate (B-1) formed by naphthoquinonediazide-5-sulfonic acid, 1 part by weight of 1-[N,N-bis(2-hydroxyethyl)amino group A 4-methylbenzotriazole (C-3-2) is added to 250 parts by weight of propylene glycol monomethyl ether acetate (D-1), and is uniformly stirred by a shaker to obtain The photosensitive novolak resin composition of Comparative Example 6. The photosensitive novolak resin composition thus obtained was also evaluated by the above evaluation method, and its sensitivity stability was expressed as ×.

<evaluation result>

It is understood from Table 2 that the photosensitive polyoxynitride containing no nitrogen-containing compound (C) is contained as compared with the photosensitive polyoxyalkylene composition containing the nitrogen-containing compound (C) (Examples 1 to 12). The composition (Comparative Example 1 to Comparative Example 3) had poor sensitivity stability.

When the decane monomer component of the polyoxyalkylene (A) includes an acid group-containing alkyl group, an epoxy group-containing alkyl group or an epoxy group-containing alkoxy group, the photosensitive polyoxyalkylene composition (implementation) Sensitivity stability of Example 1 to Example 5, Example 7 to Example 12) Better sex.

In addition, according to the evaluation results of Comparative Example 4 to Comparative Example 6, it is found that compared with the photosensitive polyoxyalkylene composition (positive photosensitive composition) containing the nitrogen-containing compound (C) having a specific structure of the present invention, A photosensitive polyoxyalkylene composition containing a sulfonic acid group (-SO ₃ H)-containing benzotriazole as a nitrogen-containing compound (Comparative Example 4), and a negative-type photosensitive composition using a nitrogen-containing compound (Comparative Example 5) The photosensitive novolak resin composition (Comparative Example 6) had poor sensitivity stability.

As described above, the photosensitive polyoxyalkylene composition of the present invention is a positive photosensitive composition containing a nitrogen-containing compound having a specific structure and a specific functional group. Specifically, the nitrogen-containing compound has a five-membered ring in which the five-membered ring has two or more nitrogen atoms and two double bonds, and contains a group other than the sulfonic acid group. Since the photosensitive polyoxyalkylene composition of the present invention has excellent sensitivity stability, it is suitable for forming a protective film such as a flattening film, an interlayer insulating film or an optical waveguide used in a liquid crystal display element and an organic electroluminescence display. Core material, or cladding material, etc.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

Claims (5)

A photosensitive polyoxyalkylene composition comprising: polyoxyalkylene (A); o-naphthoquinonediazide sulfonate (B); nitrogen-containing compound (C); and solvent (D), wherein said The nitrogen compound (C) includes the imidazole compound (C-1) represented by the formula (1), the pyrazole compound represented by the formula (2) (C-2), and the three represented by the formula (3) or the formula (4). At least one of the azole compound (C-3) and the tetrazole compound (C-4) represented by the formula (5), In the formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a hydroxyl group, an amine group, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number. a substituted or unsubstituted alicyclic group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group of 3 to 20, R ¹ and R ² may be condensed to form a substituted or unsubstituted a substituted benzene ring or a 6-membered heterocyclic ring; R ⁴ represents a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, a group represented by the formula (1-1), and a formula ( 1-2) a group represented by the formula, a group represented by the formula (1-3), a group represented by the formula (1-4) or a group represented by the formula (1-5), -(CH ₂ ) _a -X ¹ In the formula (1-1) (1-1), a represents an integer of 0 to 20, and X ¹ represents a hydroxyl group or a carboxyl group; In the formula (1-2), b represents an integer of 0 to 20; In the formula (1-3), d represents an integer of 0 to 20, and X ² and X ³ each independently represent a hydrogen atom or a hydroxyl group; In the formula (1-4), e represents an integer of 0 to 20, In the formula (1-5), f represents an integer of 0 to 6, and g represents an integer of 1 to 6; In the formula (2), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydroxyl group, an amine group, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number. R ³ and R ⁶ and R ⁵ and R ⁷ may be condensed by a substituted or unsubstituted alicyclic group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group of 3 to 20 Forming a substituted or unsubstituted benzene ring or a 6-membered heterocyclic ring; R ^{8 is} synonymous with R ⁴ in the formula (1), In the formulae (3) and (4), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, an amine group, a carboxyl group, and a carbon number of 1 to 30. An alkyl group, an alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 30 carbon atoms, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group a group, R ⁹ and R ¹⁰ may be condensed to form a substituted or unsubstituted benzene ring or a 6-membered heterocyclic ring having one hetero atom. In the formula (5), R ¹⁵ represents a hydrogen atom, a hydroxyl group, an amine group, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituted carbon number of 3 to 20 or Unsubstituted alicyclic group, substituted or unsubstituted phenyl group or substituted or unsubstituted benzyl group; R ^{16 is} synonymous with R ⁴ in the formula (1). The photosensitive polyoxyalkylene composition according to claim 1, wherein the polyoxyalkylene (A) is obtained by polycondensation of a decane monomer component, the decane monomer component comprising 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 and has a carbon number of 1 to An alkyl group of 10, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkyl group having an acid anhydride group, an alkyl group having an epoxy group or an alkoxy group having an epoxy group, at least One R ^a is an acid group-containing alkyl group, an epoxy group-containing alkyl group or an epoxy group-containing alkoxy 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 An fluorenyl group to 6 or an aryl group having 6 to 15 carbon atoms; w represents an integer of 1 to 3. The photosensitive polyoxyalkylene composition according to claim 1, wherein the o-naphthoquinonediazide sulfonate is used based on 100 parts by weight of the polyoxyalkylene (A). (B) is used in an amount of 1 to 35 parts by weight, the nitrogen-containing compound (C) is used in an amount of 0.1 to 10 parts by weight, and the solvent (D) is used in an amount of 100 to 1500 parts by weight. A protective film which is applied to a component by a photosensitive polyoxyalkylene composition according to any one of claims 1 to 3, which is pre-baked, exposed, developed, and baked. Formed afterwards. An element having a protective film comprising the element and the protective film of claim 4, wherein the protective film covers the element.