KR20160110067A - Photosensitive compositions - Google Patents

Abstract

The present invention relates to a photosensitive composition, comprising: an alkali-soluble polymer (A); a multi-functional epoxy compound (B); a compound having a polymerizable double bond (C); a photopolymerization initiator (D); a 1,2-quinonediazide compound (E); and a solvent (F). The photosensitive composition has good spreadability and can form a curing film having excellent adhesion, transparency, thermal resistance, surface smoothness, and especially, resolution with respect to an under-substrate such as glasses or the like.

Description

[0001] PHOTOSENSITIVE COMPOSITIONS [0002]

The present invention relates to a photosensitive composition for use in forming an insulating material in electronic parts, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film or a planarizing film, or an interlayer insulating film or a protective film for a color filter in a display element , A transparent film thereby, and an electronic part having the film.

In the manufacturing process of elements such as display elements, various chemical treatments such as organic solvents, acids, and alkaline solutions are performed, or when the wiring electrodes are formed by sputtering, the surface is locally heated to a high temperature . Therefore, a surface protective film may be formed for the purpose of preventing deterioration, damage, and alteration of the surface of various devices. These protective films are required to have properties that can withstand various treatments in the above-described manufacturing process. Specifically, it is required to have heat resistance, chemical resistance such as solvent resistance, acid resistance and alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, scratch resistance, coating property, flatness and light resistance. Further, while high performance such as high viewing angle, fast response, and high definition of display elements is being advanced, materials having improved reliability and planarization characteristics are desired when used as a color filter protective film.

The kinds of these protective films can be roughly classified into photosensitive compositions and thermosetting compositions. Since the thermosetting composition is completely cured by high-temperature heating at the time of film formation, even if it is heated at a high temperature in subsequent steps, volatile matter generated is small, and heat resistance is excellent. As a thermosetting protective film material having such excellent properties, there is a polyester amide composition (see, for example, Patent Document 1). However, since the thermosetting composition can not form a scribe line, a large amount of fine debris of the thermosetting composition is generated at the time of dividing the production panel, and then a highly advanced panel cleaning process is required.

On the other hand, the photosensitive composition is composed of a polymer, an oligomer or monomer having a photopolymerizable group and a photopolymerization initiator, and causes a chemical reaction by the energy of light including ultraviolet rays to cure. The photosensitive composition is advantageous in that fine scrap of the photosensitive composition is not generated since, for example, a scribe line used for dividing a production panel can be easily formed.

In recent years, there has been an increasing demand for a protective film which requires a fine pattern shape, and a photosensitive composition capable of forming these fine patterns is required.

As an example of using a photosensitive composition as a protective film of a color filter, there are Patent Documents 2 and 3. However, as a result of the present inventors attempting to form a protective film by using the photosensitive composition described above, an intended fine pattern can be formed There was no.

Japanese Laid-Open Patent Publication No. 2008-156546 Japanese Laid-Open Patent Publication No. 2014-074787 Japanese Patent Application Laid-Open No. 2009-286904

Disclosure of the Invention An object of the present invention is to provide a photosensitive composition which is capable of forming a cured film having good coatability and excellent adhesion to a base substrate such as glass, transparency, heat resistance, flatness, and particularly resolution. The present invention also provides a cured film formed by the photosensitive composition, and an electronic component having the cured film.

DISCLOSURE OF THE INVENTION As a result of various investigations to solve the above problems, the present inventors have found that a radically polymerizable monomer (a1) having a carboxyl group and another radically polymerizable monomer (a2) (all of which do not have an epoxy group and an oxetanyl group) (A), a polyfunctional epoxy compound (B), a compound having a polymerizable double bond (C), a photopolymerization initiator (D), and a 1,2-quinone A diazide compound (E), and a solvent (F), and filed a patent application. The inventors of the present invention, through further investigation, have found that, in the compound (C) having a polymerizable double bond in the above photosensitive composition, a compound having a carboxyl group together with a polymerizable double bond is replaced with a compound having a polymerizable double bond By weight based on the total weight of the composition, the present invention has been accomplished.

The present invention has the following configuration.

[1] A process for producing an alkali-soluble polymer (A), a multifunctional epoxy compound (B), a polymerizable double bond-containing compound (C), a photopolymerization initiator (D), a 1,2-quinonediazide compound (E) F) as a photosensitive composition,

The alkali-soluble polymer (A) is obtained by polymerizing a mixture of a radically polymerizable monomer having a carboxyl group (a1) and a radically polymerizable monomer containing another radically polymerizable monomer (a2)

The radically polymerizable monomer (a1) having a carboxyl group and the other radically polymerizable monomer (a2) do not have an epoxy group or an oxetanyl group,

The compound (C) having a polymerizable double bond contains a compound (C1) having a carboxyl group together with a polymerizable double bond, and the compound (C1) having a carboxyl group together with a polymerizable double bond, Is at least 10% by weight of the total weight of the compound having a heavy bond.

[2] The thermoplastic resin composition according to any one of [1] to [3], wherein the alkali-soluble polymer (A) is a copolymer of a radically polymerizable monomer (a1) having a carboxyl group and a radically polymerizable monomer (a1) having a carboxyl group, And a radical polymerizable monomer containing 40 to 90% by weight of a radically polymerizable monomer (a2) in an amount of 0.1 to 10% by weight based on the total weight of the composition.

[3] The photosensitive composition according to [1] or [2], wherein the radically polymerizable monomer (a1) having a carboxyl group is at least one selected from acrylic acid and methacrylic acid.

(Meth) acrylate having a dicyclopentanyl group, a (meth) acrylate having a dicyclopentenyl group and an N-substituted (meth) acrylate having a dicyclopentanyl group, wherein the other radically polymerizable monomer (a2) The photosensitive composition according to any one of [1] to [3], which contains at least one selected from maleimide.

[5] The composition according to any one of [1] to [4], wherein the other radically polymerizable monomer (a2) is at least one selected from the group consisting of benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) 1] to [4], wherein at least one member selected from the group consisting of cyclohexylmaleimide is contained in an amount of 50% by weight or more based on the total weight of the other radically polymerizable monomer (a2) Sensitive composition.

The polyfunctional epoxy compound (B) is at least one selected from a glycidyl ether type epoxy compound (Ba), an alicyclic aliphatic epoxy compound (Bb) and an epoxy group containing polymer (Bc)

The epoxy group-containing polymer (Bc) is obtained by polymerizing a mixture of a radically polymerizable monomer (b1) having an epoxy group and a radically polymerizable monomer containing another radically polymerizable monomer (b2)

The photosensitive composition according to item [1], wherein the radically polymerizable monomer (b1) having an epoxy group and the other radically polymerizable monomer (b2) do not have a carboxyl group.

[7] The epoxy resin composition according to [1], wherein the glycidyl ether type epoxy compound (Ba) is 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] Phenoxy] -2-propanol and 2- [4- (2,3-epoxypropoxy) phenyl] -2- Propyl] propane, and [4- [1,1-bis [4- (2,3-epoxypropoxy)

[6], wherein the alicyclic aliphatic epoxy compound (Bb) is a 1,2-epoxy-4- (2-oxyllanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) ≪ / RTI >

[8] A process for producing a polymerizable double bond, wherein the compound (C1) having a carboxyl group together with the polymerizable double bond in the compound (C) having a polymerizable double bond is selected from the group consisting of phthalic acid monohydroxyethyl acrylate, succinic acid modified pentaerythritol triacrylate, The photosensitive composition according to item 1, wherein the photosensitive composition is at least one selected from pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, phthalic acid-modified dipentaerythritol pentaacrylate, and polybasic acid-modified acrylic oligomer.

[9] The photosensitive composition according to item [1], wherein the photopolymerization initiator (D) contains a compound represented by the following formula (D-1) in an amount of 50% by weight or more based on the total weight of the photopolymerization initiator (D).

Wherein R ¹¹ , R ¹² and R ¹³ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms;

R ¹⁴ is an alkyl group of 1 to 15 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, or an alkynyl group of 2 to 15 carbon atoms, and n is an integer of 1 to 5,

[10] The photosensitive composition described in [9], wherein the compound represented by the formula (D-1) is 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- .

[11] The photosensitive composition as described in [1], wherein the 1,2-quinonediazide compound (E) is a 1,2-naphthoquinonediazide sulfonic acid ester.

[12] The process according to [1], wherein the 1,2-naphthoquinonediazide sulfonic acid ester is selected from the group consisting of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and 4,4 ' - [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester. Wherein the photosensitive composition is a photosensitive composition.

[13] A cured film obtained from the photosensitive composition according to any one of [1] to [12].

[14] A color filter using the cured film described in [13] as a protective film.

[15] A display element using the color filter described in [14].

[16] A solid-state imaging device using the color filter described in [14].

[17] A transparent insulating film formed between a TFT and a transparent electrode, comprising a cured film according to [13].

[18] A display device using the cured film described in [13], which is a transparent insulating film formed between a transparent electrode and an orientation film.

[19] A touch panel using the cured film described in [13], as a transparent insulating film formed between electrodes.

[20] An LED light-emitting body using the cured film described in [13] as a protective film.

According to the present invention, there is provided a photosensitive composition capable of forming a transparent body on a fine pattern.

In the present specification, the term " fine pattern " refers to a line & space pattern and a hole pattern of 20 mu m to 50 mu m. The term "pattern-based transparent body" refers to a cured body having a shape of irregularities, such as a membrane-like, perforated membrane-like, protruding, linear, etc. film thickness of 10 μm or less and a light transmittance of 80% Cured film). However, the cured film formed using the photosensitive composition of the present invention does not require the above-mentioned " pattern image ", and even a so-called " A film can be obtained. The cured film of the present invention can not prevent its use as a cured product of the " partial printing film process " by the above description.

In the present specification, in order to express one or both of acrylic acid and methacrylic acid, the term "(meth) acrylic acid" may be used. In the same manner, in order to express one or both of acrylate and methacrylate, there is a case where the term is expressed as " (meth) acrylate ".

In the present specification, the "alkenyl group" is a linear or branched alkenyl group having a double bond, and specific examples thereof include ethenyl, 1-propenyl, 2-propenyl, Propenyl, 2-pentenyl, 4-pentenyl, 3-methyl-2-butenyl, 1-hexenyl , 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, 1,3-octadienyl, 2-nonenyl, Chenyl. The "alkynyl group" is a straight chain or branched chain alkynyl group having a triple bond and specific examples thereof include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, Butynyl, 1-pentynyl, 2-pentynyl, 4-pentynyl, 1-octynyl, 6-methyl-1-heptynyl and 2-decynyl.

<1. Photosensitive composition of the present invention>

A first aspect of the present invention is a method for producing a photosensitive resin composition comprising an alkali-soluble polymer (A), a polyfunctional epoxy compound (B), a compound having a polymerizable double bond (C), a photopolymerization initiator (D), a 1,2-quinonediazide compound E) and a solvent (F).

(A), a polyfunctional epoxy compound (B), a compound having a polymerizable double bond (C), a photopolymerization initiator (D), a 1,2-quinonediazide compound (E) (A), a polyfunctional epoxy compound (B), a compound having a polymerizable double bond (C), a photopolymerization initiator (D) and a 1,2-quinonediazide The weight ratio of the compound (E) is 10 to 150 parts by weight for the polyfunctional epoxy compound (B) and 40 to 400 parts by weight for the compound (C) having the polymerizable double bond, based on 100 parts by weight of the alkali- 2 to 60 parts by weight of the photopolymerization initiator (D) and 0.1 to 50 parts by weight of the 1,2-quinonediazide compound (E). In addition, the photosensitive composition of the present invention preferably contains a solvent (F) so as to have a solid concentration of 10 to 50% by weight.

The photosensitive composition of the present invention is not limited to the following description, but improvement in resolution can be achieved by using a specific alkali-soluble polymer.

<1-1. The alkali-soluble polymer (A)

As described above, the alkali-soluble polymer (A) used in the present invention is a polymer obtained by copolymerizing a radical polymerizable monomer (a1) having a carboxyl group (hereinafter sometimes referred to as "component (a1)") (Hereinafter sometimes referred to as &quot; component (a2) &quot;) other than the radically polymerizable monomer (a1) capable of copolymerizing with the monomer (a1) Is a copolymer obtained by polymerizing a mixture of monomers. Here, the radical polymerizable monomer (a1) having a carboxyl group and the other radical polymerizable monomer (a2) other than the radical polymerizable monomer (a1) do not have an epoxy group and an oxetanyl group. The alkali-soluble polymer (A) may be one kind or two or more kinds.

In the polymerization of the alkali-soluble polymer (A) contained in the photosensitive composition of the present invention, the radically polymerizable monomer (a1) having a carboxyl group is copolymerized with the radically polymerizable monomer (a1) having a carboxyl group and the other radically polymerizable monomer ) Is preferably used in an amount of 10 to 60% by weight. Within this range, the resolution of the photosensitive composition of the present invention is improved, and a fine pattern tends to be formed. When the above range of the monomer is 15 to 40% by weight, it is more preferable to use a photosensitive composition of the present invention to produce a patterned transparent body having a high sensitivity (a desired patterned transparent body can be obtained at a low irradiation dose).

In the method of adding the alkali-soluble polymer (A) to the photosensitive composition of the present invention, the solution after the polymerization reaction may be used as it is, or the same solution may be concentrated to extract the solid component and add only the solid component.

<1-1-1. Radically polymerizable monomer (a1) having a carboxyl group>

The radically polymerizable monomer (a1) having a carboxyl group, which is one of raw materials for the alkali-soluble polymer (A), is not particularly limited so long as it satisfies the condition that it does not have an epoxy group and an oxetanyl group. Specific examples of the radically polymerizable monomer (a1) having a carboxyl group include (meth) acrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, Caprolactone mono (meth) acrylate, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl], cyclohexene-3,4-dicarboxyl Acid mono [2- (meth) acryloyloxyethyl].

Among them, (meth) acrylic acid and mono [2- (meth) acryloyloxyethyl succinate] are preferable, and the use of (meth) acrylic acid in particular makes it possible to improve the resolution of the photosensitive composition, Is more preferable.

As the radically polymerizable monomer (a1) having these carboxyl groups, the above-described compounds may be used alone, or two or more of them may be used in combination.

<1-1-2. Other radically polymerizable monomers (a2)>

Another radically polymerizable monomer (a2) which is another raw material of the alkali-soluble polymer (A) is a radical polymerizable monomer (a2) having no carboxyl group, epoxy group and oxetanyl group and capable of copolymerizing with a radically polymerizable monomer (a1) And is not particularly limited as long as it is a maleic monomer. Examples of such radically polymerizable monomers include (meth) acrylic acid ester, N-substituted maleimide, macromonomer, styrene, methylstyrene, vinyltoluene, chloromethylstyrene, indene, (meth) acrylamide and N- It is morpholine. Specific examples of the (meth) acrylic esters include methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, methoxypolyethylene glycol Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, m-phenoxybenzyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. Examples of N-substituted maleimides are N-phenylmaleimide and N-cyclohexylmaleimide. Examples of macromonomers are polystyrene macromonomers and polymethylmethacrylate macromonomers.

Among them, at least one selected from dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, N-phenylmaleimide, and N-cyclohexylmaleimide , A patterned transparent body produced by using a photosensitive composition containing the copolymerized alkali-soluble polymer (A) is preferable because of its high heat resistance. At least one selected from the dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, N-phenylmaleimide and N-cyclohexylmaleimide, It is more preferable that their (their) total weight is contained in an amount of 50% by weight or more based on the total weight of the other radically polymerizable monomer (a2).

These other radically polymerizable monomers (a2) may be used alone or in combination of two or more.

<1-2. The polyfunctional epoxy compound (B)

The polyfunctional epoxy compound (B) of the present invention is a compound having two or more epoxy groups per molecule and is not particularly limited as long as it has such a structure characteristic. The polyfunctional epoxy compound may be used singly or in combination of two or more thereof.

When the content of the polyfunctional epoxy compound (B) contained in the photosensitive composition of the present invention is 10 to 150 parts by weight per 100 parts by weight of the alkali-soluble polymer (A), the photosensitive composition of the present invention is preferably flat, If the amount is 20 to 100 parts by weight, the transparency of the patterned transparent body produced by using the photosensitive composition of the present invention is more preferable.

Examples of the polyfunctional epoxy compound (B) include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, glycidyl ether type epoxy compounds (Ba), phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A Novolak type epoxy compound, aliphatic polyglycidyl ether, alicyclic aliphatic epoxy compound (Bb) and epoxy group-containing polymer (Bc). Here, the epoxy group-containing polymer (Bc) is a copolymer obtained by polymerizing a mixture of a radically polymerizable monomer containing an epoxy group-containing radical polymerizable monomer (b1) and another radical polymerizable monomer (b2).

Among them, a glycidyl ether type epoxy compound (Ba), a bisphenol A novolak type epoxy compound, an alicyclic aliphatic epoxy compound (Bb) and an epoxy group containing polymer (Bc) are preferable, and a glycidyl ether type epoxy compound ), An alicyclic aliphatic epoxy compound (Bb) and an epoxy group-containing polymer (Bc) are more preferable. The pattern-wise transparent body produced by using the photosensitive composition using these polyfunctional epoxy compounds has high transparency.

<1-2-1. Glycidyl ether type epoxy compound (Ba)>

A preferred specific example of the glycidyl ether type epoxy compound (Ba) is 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [ 2-propanol and 2- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] - [4- [1,1-bis [4 - ([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane.

<1-2-2. Alicyclic aliphatic epoxy compound (Bb)>

A preferred specific example of the alicyclic aliphatic epoxy compound (Bb) is a 1,2-epoxy-4- (2-oxyllanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol.

As the polyfunctional epoxy compound (B), commercially available products such as the following may be used. Specific examples of the bisphenol A type epoxy compound are jER 828, 1004 and 1009 (all trade names, manufactured by Mitsubishi Chemical Corporation). Specific examples of the bisphenol F type epoxy compound are jER 806 and 4005P (all trade names, manufactured by Mitsubishi Chemical Corporation). Specific examples of the glycidyl ether type epoxy compound (Ba) are Techmor VG3101L (trade name: PRINTEC), EPPN-501H and 502H (all trade names, manufactured by Nippon Yakusho Co., Ltd.) and jER 1032H60 (trade name, Mitsubishi Chemical Corporation). Specific examples of the phenol novolak-type epoxy compound are EPPN-201 (trade name; manufactured by Nippon Yakusho Co., Ltd.), jER 152 and 154 (all trade names, manufactured by Mitsubishi Chemical Corporation). Specific examples of the cresol novolak type epoxy compound are EOCN-102S, 103S, 104S and 1020 (both trade names, manufactured by Nippon Yakusho Co., Ltd.). Specific examples of the bisphenol A novolak type epoxy compound are jER 157S65 and 157S70 (all trade names, manufactured by Mitsubishi Chemical Corporation). Specific examples of the alicyclic aliphatic epoxy compound (Bb) are Celloside 2021P and EHPE-3150 (all trade names, Daicel Co., Ltd.). Further, TECHMORE VG3101L, which is a glycidyl ether type epoxy compound (Ba), is obtained by reacting 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [ ([2,3-epoxypropoxy] phenyl]] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- [1- (4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol. EHPE-3150, which is an alicyclic aliphatic epoxy compound (Bb), is a 1,2-epoxy-4- (2-oxyllanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol.

<1-2-3. Epoxy group-containing polymer (Bc) &gt;

As described above, the epoxy group-containing polymer (Bc) used in the present invention can be obtained by copolymerizing a radically polymerizable monomer (b1) having an epoxy group and another radically polymerizable monomer (b2) copolymerizable with the radically polymerizable monomer Or a mixture of the radical-polymerizable monomers.

The radical polymerizable monomer (b1) having an epoxy group is preferably used in an amount of 20 to 95 (b1) relative to the total weight of the radical polymerizable monomer (b1) having an epoxy group and the other radical polymerizable monomer By weight. In such a range, the pattern size of the patterned transparent material produced using the photosensitive composition of the present invention approaches the mask size, and the chemical resistance is increased. When the above range of the monomer is 50 to 80% by weight, the heat-resistance of the patterned transparent body produced by using the photosensitive composition of the present invention is more preferable.

In the method of adding the epoxy group-containing polymer (Bc) to the photosensitive composition of the present invention, the solution after the polymerization reaction may be used as it is, or the same solution may be concentrated to extract the solid component and add only the solid component.

<1-2-3-1. Radically polymerizable monomer (b1) having an epoxy group>

The radically polymerizable monomer (b1) having an epoxy group as a raw material of the epoxy group-containing polymer (Bc) is not particularly limited as long as it has at least one epoxy group. Examples of the radically polymerizable monomer (b1) having an epoxy group are glycidyl (meth) acrylate and methylglycidyl (meth) acrylate. A photosensitive composition using an epoxy group-containing polymer (Bc) obtained by polymerizing at least one selected from these radically polymerizable monomers can form a small pattern, and the patterned transparent body produced by using the photosensitive composition has a chemical resistance Is high.

As the radically polymerizable monomer (b1) having an epoxy group, in particular, an epoxy group-containing polymer (Bc) obtained by copolymerizing at least one selected from glycidyl acrylate and glycidyl methacrylate is preferably used because of its high heat resistance Do.

The radically polymerizable monomer (b1) having an epoxy group may be used alone, or two or more thereof may be used in combination.

<1-2-3-2. Other radically polymerizable monomer (b2)>

The other radical polymerizable monomer (b2) copolymerizing with the radical polymerizable monomer (b1) having an epoxy group is a radical polymerizable monomer (b1) having no carboxyl group, epoxy group and oxetanyl group and capable of copolymerizing with the radical polymerizable monomer Is not particularly limited as long as it is a polymerizable monomer. Examples of such radically polymerizable monomers include the radically polymerizable monomers exemplified in the description of the other radically polymerizable monomer (a2) copolymerized with the above-mentioned radically polymerizable monomer (a1) having a carboxyl group.

Among them, at least one selected from benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N-phenylmaleimide and N-cyclohexylmaleimide The patterned transparent body produced by using the photosensitive composition using the epoxy group-containing polymer (Bc) obtained by copolymerization is preferable because of its high transparency and high heat resistance.

As the other radically polymerizable monomer (b2), the above-described compounds may be used alone, or two or more of them may be used in combination.

<1-3. The compound (C) having a polymerizable double bond>

The compound (C) having a polymerizable double bond contained in the photosensitive composition of the present invention is not particularly limited as far as it has a polymerizable double bond. It is to be noted that the compound (C1) having a carboxyl group together with the polymerizable double bond and the compound (C1) having a carboxyl group together with the polymerizable double bond is preferably a compound 10% by weight or more of the total weight.

Examples of the compound (C) having a polymerizable double bond contained in the photosensitive composition of the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, epichlorohydrin-modified ethylene glycol di (meth) acrylate, epichlorohydrin-modified diethylene glycol di (meth) acrylate, ethylene glycol di Epichlorohydrin modified diethylene glycol di (meth) acrylate, epichlorohydrin modified tetraethylene glycol di (meth) acrylate, epichlorohydrin modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) Acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (Meth) acrylate, epichlorohydrin-modified propylene glycol di (meth) acrylate, epichlorohydrin-modified dipropylene glycol di (meth) acrylate, epichlorohydrin-modified (Meth) acrylate, epichlorohydrin-modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin-modified polypropylene glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, ethylene oxide modified trimethylol propane tri (meth) acrylate, propylene oxide modified trimethylol propane tri (meth) acrylate, epichlorohydrin modified trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra Methacrylate, glycerol acrylate methacrylate (Meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, 1,6-hexanediol di Acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic neopentyl glycol di (meth) acrylate, caprolactone modified (meth) acrylate, methoxylated cyclohexyldi (Meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, allylated cyclohexyl (meth) acrylate, (Meth) acrylate, bis [(meth) acryloxy neopentyl glycol] adipate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, bisphenol F di Ethylene oxide modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) (Meth) acrylate, dicyclopentanyl diacrylate, ethylene oxide modified di (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate, (Meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, ethylene oxide modified di (Meth) acrylate, neopentyl glycol-modified trimethylolpropane di (meth) acrylate, isocyanuric acid ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified triacrylate, caprolactone-modified Tris [(meth) acryloxyethyl] isocyanurate, (meth) acrylated isocyanurate, omega -carboxypolycaprolactone mono (meth) acrylate, phthalic acid monohydroxyethyl acrylate, succinic acid modified pentaerythritol triacryl Phthalic acid-modified pentaerythritol triacrylate, succinic acid-modified diphen Pentaerythritol is pentaerythritol pentaacrylate, acid-modified dipentaerythritol pentaacrylate, polybasic acid-modified acrylic oligomers.

Among them, the compound (C1) having a carboxyl group together with the polymerizable double bond is preferably selected from ω-carboxypolycaprolactone mono (meth) acrylate, phthalic acid monohydroxyethyl acrylate, succinic acid modified pentaerythritol triacrylate, phthalic acid Modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, phthalic acid-modified dipentaerythritol pentaacrylate, and polybasic acid-modified acrylic oligomer.

As the compound (C) having a polymerizable double bond, the above-described compounds may be used alone, or two or more of them may be used in combination. With respect to the compound (C1) having a carboxyl group together with the polymerizable double bond, the above-described compounds may be used alone, or two or more of them may be used in combination.

Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, isocyanuric acid ethylene oxide modified diacrylate, isocyanate As the ethylene oxide-modified triacrylate, or a mixture thereof, the following commercially available products can be used. Specific examples of trimethylolpropane triacrylate are ARONIX M-309 (trade name, manufactured by TOA Corporation) and A-TMPT (trade name, Shin Nakamura Chemical Industry Co., Ltd.). Specific examples of mixtures of pentaerythritol triacrylate and pentaerythritol tetraacrylate include Aronix M-306 (65-70 wt%), M-305 (55-63 wt%), M-303 60% by weight), M-452 (25 to 40% by weight) and M-450 (less than 10% by weight) (both trade names; Toa Synthetic Co., Ltd., parentheses are contents of pentaerythritol triacrylate A-TMM-3L (57% by weight) and A-TMMT (all trade names, Shin Nakamura Chemical Industry Co., Of the content of the sample). Specific examples of mixtures of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate include Aronix M-403 (50-60 wt%), M-400 (40-50 wt%), M-402 30 to 40 wt%), M-404 (30 to 40 wt%), M-406 (25 to 35 wt%) and M-405 (10 to 20 wt% Is a catalog value of dipentaerythritol pentaacrylate content in the mixture), and a specific example of dipentaerythritol hexaacrylate is A-DPH (trade name; Shin Nakamura Chemical Co., Ltd.). A specific example of isocyanuric acid ethylene oxide-modified diacrylate is ARONIX M-215 (trade name, manufactured by TOA Corporation). A specific example of isocyanuric acid ethylene oxide-modified triacrylate is A-9300 (trade name; Shin Nakamura Chemical Co., Ltd.). Specific examples of the mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate include Aronix M-313 (30 to 40 wt%) and M-315 (3 to 13 wt% ) (All trade names; Toagosei Co., Ltd., content values in parentheses are catalog values of content of isocyanuric acid ethylene oxide-modified diacrylate in the mixture).

As the ω-carboxypolycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate and polybasic acid-modified acrylic oligomer, which is a compound (C1) having a carboxyl group together with a polymerizable double bond, the following commercially available products can be used. A specific example of? -carboxypolycaprolactone monoacrylate is Aronix M-5300 (trade name, Toagosei Co., Ltd.). A specific example of phthalic acid monohydroxyethyl acrylate is Aronix M-5400 (trade name, Toagosei Co., Ltd.). Specific examples of the polybasic acid-modified acrylic oligomer include M-510 (trade name, Toa Synthetic Co., Ltd.) and M-520 (trade name, Toa Synthetic Co., Ltd.).

When the content of the compound (C1) having a carboxyl group together with the polymerizable double bond is adjusted to be 10% by weight or more based on the total weight of the compound (C) having a polymerizable double bond, improvement in heat resistance And the resolution of the unexposed portion can be improved.

<1-4. Photopolymerization initiator (D)>

The photopolymerization initiator (D) contained in the photosensitive composition of the present invention starts to polymerize a composition containing an alkali-soluble polymer (A), a polyfunctional epoxy compound (B) and a compound (C) having a polymerizable double bond It is not particularly limited.

Examples of the photopolymerization initiator (D) contained in the photosensitive composition of the present invention include compounds represented by the following formula (D-1).

R ¹¹ , R ¹² and R ¹³ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. R ¹⁴ is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkynyl group having 2 to 15 carbon atoms. n is independently an integer of 1 to 5;

The compound represented by the formula (D-1) is particularly preferably 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime). This compound is commercially available as IRGACURE OXE01 (trade name; BASF Japan Co., Ltd.).

When the compound represented by the formula (D-1) is 20% by weight or more based on the total weight of the photopolymerization initiator (D), the pattern size of the patterned transparent substance produced using the photosensitive composition is preferably close to the mask size. It is more preferable that the content is 50% by weight or more. The photopolymerization initiator (D) may be composed only of the compound represented by the formula (D-1). As the photopolymerization initiator (D), the compound represented by the formula (D-1) may be used alone, or two or more thereof may be used in combination.

Examples of other photopolymerization initiators used in combination with the compound represented by the formula (D-1) include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, iso Ethyl xanthone, propyl xanthone, 2,4-diethyl thioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy- Benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzene 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- Di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, Butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphe (Trinomethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4, (Trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) Di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2 ' (Trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole , 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin) , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis Ethoxycarbonylphenyl) (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis Bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2 -methyl-2-morpholino-propionyl) -9-n- dodecyl carbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η ⁵ -2,4- cyclopentadiene-1-yl) -bis ( (2-methylbenzoyl) -9-ethyl-9H-carbazole-3 (1H-pyrrol-1-yl) - yl] ethanone oxime and Adeka Cruz NCI-930 (trade name; ADEKA Corporation).

These compounds may be used alone or in combination of two or more.

When the photopolymerization initiator (D) is a mixture of the compound represented by the formula (D-1) and another photopolymerization initiator, the other photopolymerization initiator is preferably 4,4'-bis (diethylamino) benzophenone, Diethylaminocoumarin, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl- ) -Butanone-1, it is preferable that the high sensitivity and the pattern size approach the mask size.

<1-5. 1,2-quinonediazide compound (E)

Examples of the compound used as the 1,2-quinonediazide compound (E) contained in the photosensitive composition of the present invention include 1,2-benzoquinone diazidesulfonic acid ester, 1,2-naphthoquinonediazide sulfonic acid ester, 1,2-benzoquinone diazidesulfonic acid amide and 1,2-naphthoquinonediazide sulfonic acid amide.

Specific examples of the 1,2-quinonediazide compound (E) are the following compounds.

2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5 -Sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone Diazide-5-sulfonic acid esters;

2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone- -Naphthoquinonediazide-5-sulfonic acid ester, 2,3,3 ', 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,3', 4 -Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid Ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester;

Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide (P-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide -5-sulfonic acid ester;

(P-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide- (P-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri -Naphthoquinonediazide-5-sulfonic acid ester;

Bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane- 2-naphthoquinone diazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane- 2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

(2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris 4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '- [1- [4- [ Phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 '- [1- [4- [1- [4- Phenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester;

Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5- ) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobindene- 7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'- tetramethyl-1,1'-spirobindene -5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester;

2,2,4-trimethyl-7,2 ', 4'-trihydroxyflagane-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,2,4-trimethyl- 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester.

These compounds may be used alone or in combination of two or more.

In particular, it is possible to use 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '- [1- [4- [1- [4- hydroxyphenyl] Sulfonic acid ester and 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide- -Sulfonic acid ester is preferably used because transparency of the photosensitive composition is enhanced.

<1-6. Solvent (F)>

The solvent (F) used in the present invention is preferably a mixed solvent containing at least one compound having a boiling point of 100 to 200 占 폚 or at least 20% by weight of the compound. Examples of the compound having a boiling point of 100 to 200 占 폚 include water, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxyacetate, Methyl methoxypropionate (hereinafter may be abbreviated as "MMP" in some cases), ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxyacetate, Ethoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Ethyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy- Ethoxy-2- Methyl propionate, ethyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene Propylene glycol monomethyl ether acetate (hereinafter abbreviated as &quot; PGMEA &quot;), ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, di Ethylene glycol monoethyl ether, di Ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether (hereinafter abbreviated as "EDM" ), Toluene, xylene,? -Butyrolactone and N, N-dimethylacetamide.

Among these solvents, propylene glycol monomethyl ether, PGMEA, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, di More preferably at least one selected from ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and ethyl lactate because the uniformity of application is enhanced. PGMEA, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methylethylether and ethyl lactate is used, the uniformity of application of the photosensitive composition is high and the safety for the human body is enhanced Therefore, it is more preferable.

The solvent (F) may be a solvent used for the polymerization reaction of the alkali-soluble polymer (A) or the epoxy group-containing polymer (Bc) as a solution in the photosensitive composition. In addition to the solvent contained in the solution, a diluting solvent Adjusting solvent) may be added. In the case where only the solids obtained by concentrating the solution after the polymerization reaction are used in the photosensitive composition for the polymer, the solvent (F) is used in combination with the components (A) to (E) Lt; / RTI &gt;

<1-7. Additives>

The thermosetting composition of the present invention may contain an additive in view of improving the properties of the photosensitive composition in the present invention such as resolution, uniformity of coating, developability and adhesiveness. Examples of the additive include polymer dispersing agents such as acrylic type, styrene type, polyethylene imine type and urethane type; Surfactants such as anionic, cationic, nonionic, and fluoric surfactants; Silicone polymerization system application property improving agent; Adhesion-improving agents such as silane-based coupling agents and aluminum-based coupling agents; Ultraviolet absorbers such as alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; A cyclic ether compound other than the polyfunctional epoxy compound (B); Thermal crosslinking agents such as melamine compounds and bisazide compounds; Epoxy curing agents such as carboxyl compounds, carboxylic acid anhydrides and phenol compounds other than the alkali-soluble polymer (A); And an antioxidant such as a hindered phenol.

If the addition amount of the additive is 10 parts by weight or less based on 100 parts by weight of the total of the alkali-soluble polymer (A), the polyfunctional epoxy compound (B) and the compound (C) having a polymerizable double bond, And improve the properties of the photosensitive composition.

Specific examples of the adhesion improver include a silane coupling agent such as 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, aluminum-based Acetoalkoxyaluminum diisopropylate as a coupling agent, and tetraisopropyl bis (dioctylphosphite) titanate as a titanate-based coupling agent.

Specific examples of the surfactant include polyfluorophosphate (hereinafter, referred to as polyfluorophosphate) such as polyfluorophosphate No. 45, polyfluorophosphate KL-245, polyfluorophosphate No. 75, polyfluorophosphate No. 90, polyfluorophosphate No. 95 Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 182, BYK 300, BYK 306 , BYK310, BYK320, BYK330, BYK342, BYK346 (all trade names, Big Chemie Japan KK), KP-341, KP-358, KP-368, KF-96-50CS and KF-50-100CS Sephron SC-101, Surfron KH-40 and Surflon S611 (all trade names, all of which are trade names; AGC SEIMI CHEMICAL Co., Ltd.), ftergent 222F, PROTOTON 208G, PROTOTON 251 DFX-18, and FTX-218 (all of which are trade names of Neos Co., Ltd., all of which are incorporated herein by reference in their entirety); ), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801 and EFTOP EF-802 (all trade names, manufactured by Mitsubishi Materials Corporation) F-552, Megafac F-553, Megafac F-474, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F- 554, Mega Park F-555, Mega Park F-556, Mega Park F-558, Mega Park R-08, Mega Park R-30, Mega Park R-94, Mega Park RS- (Manufactured by DIC Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N All the above; Ebonic Degussa Japan Co., Ltd.), fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoroalkyl polyoxyethylene ethers, fluoroalkylammonium iodides, fluoroalkylbetaines, fluoroalkylsulfonic acid salts, (Fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonic acid salt, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, poly Oxyethylene lauryl amine, sorbitan laurate, sorbitan palmitate, sorbitan Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl An ether, an alkylbenzenesulfonic acid salt, or an alkyl diphenyl ether disulfonic acid salt.

Examples of the antioxidant such as a hindered phenol include compounds which have t-butyl at the ortho position of the OH of phenol and which may have a substituent such as an alkyl group, and compounds which may be substituted at the para position via para- A known compound such as a quadruplet of a compound is used. An example of a commercially available product is adecastab AO-60 (trade name: ADEKA Co., Ltd.).

<1-8. Process for producing alkali-soluble polymer (A) or epoxy group-containing polymer (Bc)

The polymerization method of the alkali-soluble polymer (A) or the epoxy group-containing polymer (Bc) is not particularly limited, but radical polymerization in a solution using a solvent is preferred. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used, but is usually in the range of 50 to 150 占 폚. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. The polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

<1-8-1. Solvent used in the polymerization reaction of the alkali-soluble polymer (A) or the epoxy group-containing polymer (Bc)

The solvent used in the polymerization reaction of the alkali-soluble polymer (A) is preferably a solvent which dissolves the radical polymerizable monomer (a1) having a carboxyl group, other radically polymerizable monomer (a2) and the resulting alkali-soluble polymer (A) Solvents are preferred. The solvent used in the polymerization reaction of the epoxy group-containing polymer (Bc) is preferably a solvent which dissolves the radically polymerizable monomer (b1) having an epoxy group to be used, the other radically polymerizable monomer (b2) and the resulting epoxy group- Solvents are preferred. Hereinafter, the solvent used in the polymerization reaction may be referred to as a polymerization solvent.

Specific examples of the solvent to be used for the polymerization reaction of the alkali-soluble polymer (A) or the epoxy group-containing polymer (Bc) include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, Propylene glycol monomethyl ether, propylene glycol monomethyl ether, PGMEA, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, 3-methoxypropionate, 3-methoxypropionate, - ethyl ethoxypropionate, cyclopentanone, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylformamide. The polymerization solvent may be used alone, or two or more may be mixed and used.

Among these, propylene glycol monomethyl ether, PGMEA, methyl 3-methoxypropionate and diethylene glycol methyl ethyl ether are preferable.

<1-8-2. Polymerization initiator used in polymerization reaction of alkali-soluble polymer (A) or epoxy group-containing polymer (Bc)

For polymerization of the alkali-soluble polymer (A) or the epoxy group-containing polymer (Bc), known polymerization initiators can be used. Examples of the polymerization initiator used for polymerization of the polymerization initiator and the epoxy group-containing polymer (Bc) used in the polymerization of the alkali-soluble polymer (A) used in the present invention include compounds which generate radicals by heat, azobisisobutyronitrile At least one compound suitably selected from an azo-based initiator and a peroxide-based initiator such as benzoyl peroxide. In the radical polymerization, an appropriate amount of a chain transfer agent such as thioglycolic acid may be added to adjust the molecular weight of the resulting alkali-soluble polymer (A) and epoxy group-containing polymer (Bc).

<1-8-3. Weight average molecular weight of alkali-soluble polymer (A) or epoxy group-containing polymer (Bc)>

The weight average molecular weight of the obtained alkali-soluble polymer (A) or epoxy group-containing polymer (Bc) is preferably 1,000 to 100,000, more preferably 2,000 to 20,000. Within these ranges, uniformity of the film thickness after coating becomes better.

The weight average molecular weight in the present specification is a value calculated by polystyrene conversion determined by GPC method (column temperature: 35 캜, flow rate: 1 ml / min). Standard polystyrenes include polystyrene having a molecular weight of 645 to 132,900 (e.g., Agilent S-M2-10 polystyrene calibration kit PL2010-0102 (trade name, Agilent Technologies, Inc.)), PLgel MIXED-D (trade name; Agilent Technologies Co., Ltd.) and THF as a mobile phase. The weight average molecular weights of commercially available products in this specification are the catalog values.

<2. Transparent pattern on a pattern prepared by using the photosensitive composition of the present invention>

A second aspect of the present invention relates to a patterned transparent body produced by using the photosensitive composition of the present invention. The patterned transparent body of the present invention has a high resolution at the time of patterning and is optimal for forming a fine pattern shape. The transparent body on the pattern is formed as follows. First, the photosensitive composition is applied on a substrate such as glass by spin coating, roll coating, slit coating or the like. Examples of the substrate include transparent glass substrates such as white plate glass, chewing sheet glass and silica-coated chelate glass, polycarbonate, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide and polyimide A metal sheet such as a synthetic resin sheet, a film or a substrate, an aluminum plate, a copper plate, a nickel plate and a stainless steel plate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. These substrates can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, and vacuum deposition according to requirements. The application of the photosensitive resin composition to the substrate can be carried out by a conventionally known method such as a spin coating method, a roll coating method and a dipping method.

Next, it is dried in a hot plate or an oven at 60 to 130 ° C for 1 to 5 minutes. The dried substrate is irradiated with ultraviolet rays through a mask having a desired pattern. The irradiation dose is suitably 5 to 1000 mJ / cm 2 by i-line. When the photosensitive composition is a negative type, the portion irradiated with ultraviolet rays becomes a three-dimensionally crosslinked product by polymerization of the compound (C) having a polymerizable double bond, and is insoluble in an alkali developing solution. When the photosensitive composition is a positive type, the portion irradiated with ultraviolet rays has improved solubility in an alkali developing solution by the production of a carboxylic acid from the 1,2-quinonediazide compound (E). Specific examples of the alkali developing solution include aqueous solutions of inorganic alkalis such as sodium carbonate, sodium hydrogencarbonate, sodium hydroxide and potassium hydroxide, and aqueous solutions of organic alkalis such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. It is also possible to add an appropriate amount of methanol, ethanol and a surfactant to the alkali developing solution.

Subsequently, the substrate is immersed in an alkaline developing solution by a shower phenomenon, a spray phenomenon, a puddle phenomenon, a dip phenomenon, or the like to dissolve and remove an unnecessary portion. Lastly, if baking is performed at 150 to 250 ° C for 10 to 120 minutes, a patterned transparent body of a desired pattern can be obtained.

Example

EXAMPLES Next, the present invention will be described concretely with Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited at all by these Examples.

[Synthesis Example 1] Synthesis of alkali-soluble polymer solution (A-1)

(Hereinafter abbreviated as EDM), methacrylic acid as a component (a1), dicyclopentanyl methacrylate as a component (a2) and N-cyclohexylmethacrylate as a component (a2) were added to a four- Hexyl maleimide and 2,2'-azobis (isobutyric acid) dimethyl (hereinafter abbreviated as V-601, V-601, trade name: Wako Pure Chemical Industries, Ltd.) And heated for 3 hours.

73.33 g of methacrylic acid (a1)

143.33 g of dicyclopentyl methacrylate (a2)

116.67 g of N-cyclohexylmaleimide (a2)

V-601 50.00 g

EDM 666.67 g

After completion of the reaction, the solution was cooled to room temperature to obtain a 33.3 wt% solution of the alkali-soluble polymer (A-1). The weight average molecular weight determined by GPC analysis was 3,100.

Here, the &quot; 33.3 wt% solution of the alkali-soluble polymer (A-1) &quot; refers to a solution obtained by considering all the compounds injected as described above, %. The same applies to the following examples.

[Synthesis Example 2] Synthesis of alkali-soluble polymer solution (A-2)

In a four-necked flask equipped with a stirrer, EDM, methacrylic acid as component (a1), dicyclopentanyl methacrylate as component (a2), methoxypolyethylene glycol # 400 methacrylate and N-cyclohexylmaleimide, polymerization initiator V-601 was injected into the following composition and heated at 115 캜 for 3 hours.

83.33 g of methacrylic acid (a1)

166.67 g of dicyclopentyl methacrylate (a2)

6.67 g of methoxypolyethylene glycol # 400 methacrylate (a2)

76.67 g of N-cyclohexylmaleimide (a2)

V-601 50.00 g

EDM 666.67 g

After completion of the reaction, the solution was cooled to room temperature to obtain a 33.3% by weight solution of the alkali-soluble polymer (A-2). The weight average molecular weight determined by GPC analysis was 3,300.

[Example 1]

500 ml of a separable flask equipped with a stirrer was purged with nitrogen, and 111.45 g of the alkali-soluble polymer solution (A-1) obtained in Synthesis Example 1 and 111.45 g of a compound (C) having a polymerizable double bond , 40.12 g of M-402, 4.46 g of M-5400 as a compound (C1) having a carboxyl group with a polymerizable double bond, 4.46 g of OXE-01 as a photopolymerization initiator (D) 33.44 g of VG3101L and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester (hereinafter referred to as NT-200) as the 1,2-quinonediazide compound 0.37 g of NT-200 (trade name, manufactured by Toyobo Co., Ltd.)) and 205.70 g of methyl 3-methoxypropionate dehydrated and purified as a diluting solvent (hereinafter abbreviated as MMP) The mixture was stirred for a time and uniformly dissolved. Subsequently, 0.10 g of Megafac F-556 (trade name: DIC Co., Ltd.) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 탆) to prepare a coating liquid. Further, the alkali-soluble polymer solution (A-1) contains a reaction solvent. The solvent (F) of this embodiment is the total of the reaction solvent and the diluting solvent. This specification also applies to the following examples and comparative examples.

The photosensitive composition was spin-coated on a glass substrate at 640 rpm for 10 seconds, and prebaked on a hot plate at 130 캜 for 3 minutes. Subsequently, a proximity photolithograph TME-150PRC (trade name; TOPCON Co., Ltd.) was used with a mask having a line and space pattern of 20 mu m in the air and a hole pattern of 30 mu m in the air, G, h and i lines were taken out by cutting off light, and exposed at an exposure gap of 100 mu m. The exposure dose was 10 mJ / cm &lt; 2 &gt; as measured with a UV meter UIT-102 (trade name, manufactured by Ushio Co., Ltd.) and UVD-365PD (trade name; The coated film after exposure was paddled with 0.04% by weight aqueous potassium hydroxide solution for 60 seconds, and then the coated film was washed with pure water for 20 seconds and then dried with a hot plate at 100 DEG C for 2 minutes. Post baking was performed at 230 캜 for 30 minutes in an oven to obtain a cured film having a thickness of 1.5 탆.

The properties of the cured film thus obtained were evaluated with respect to the resolution.

[Evaluation method of resolution]

The obtained glass substrate with the transparent body on the pattern was observed with a 1,000-fold optical microscope to confirm the resolution of a line and space pattern of 20 mu m and a hole pattern of 30 mu m. &Quot; o &quot;, and &quot; x &quot;, respectively.

[Examples 2 to 5]

Each component was mixed and dissolved in accordance with the method of Example 1 at the ratio shown in Table 1 (unit: g) to obtain a photosensitive composition.

Evaluation of the resolution of Examples 2 to 5 was carried out. The evaluation results are shown in Table 1.

[Comparative Examples 1 to 4]

Each component was mixed and dissolved in the ratio (unit: g) described in Table 2 in accordance with the method of Example 1 to obtain a photosensitive composition.

The evaluation of the resolution of Comparative Examples 1 to 4 was carried out. The evaluation results are shown in Table 2.

As is evident from the results shown in Tables 1 and 2, it can be seen that Examples 1 to 5 are excellent in resolution and the cured films of Comparative Examples 1 to 4 are inferior in resolution.

The cured film obtained from the photosensitive composition of the present invention has excellent properties as optical materials such as resolution, transparency, heat resistance and flatness, and is useful as a protective film for various optical materials such as color filters, LED light emitting devices and light receiving devices, A transparent insulating film formed between the transparent electrodes and between the transparent electrode and the orientation film, and a transparent insulating film formed between the electrodes.

Claims (20)

(A), a polyfunctional epoxy compound (B), a compound having a polymerizable double bond (C), a photopolymerization initiator (D), a 1,2-quinonediazide compound (E) As the photosensitive composition,
The alkali-soluble polymer (A) is obtained by polymerizing a mixture of a radically polymerizable monomer having a carboxyl group (a1) and a radically polymerizable monomer containing another radically polymerizable monomer (a2)
The radically polymerizable monomer (a1) having a carboxyl group and the other radically polymerizable monomer (a2) do not have an epoxy group or an oxetanyl group,
The compound (C) having a polymerizable double bond contains a compound (C1) having a carboxyl group together with a polymerizable double bond, and the compound (C1) having a carboxyl group together with a polymerizable double bond, Is at least 10% by weight of the total weight of the compound having a heavy bond. The method according to claim 1,
Wherein the alkali-soluble polymer (A) contains 10 to 60% by weight of a radically polymerizable monomer (a1) having a carboxyl group, based on the total weight of the radically polymerizable monomer (a1) having a carboxyl group and the other radically polymerizable monomer (a2) And another radically polymerizable monomer (a2) in an amount of 40 to 90% by weight based on the total weight of the composition. 3. The method according to claim 1 or 2,
The photosensitive composition according to Claim 1, wherein the radically polymerizable monomer (a1) having a carboxyl group is at least one selected from acrylic acid and methacrylic acid. 4. The method according to any one of claims 1 to 3,
(Meth) acrylate having an aromatic ring, (meth) acrylate having a dicyclopentanyl group, (meth) acrylate having a dicyclopentenyl group and N-substituted maleimide having a radial polymerizable monomer (a2) And at least one selected from the group consisting of silicon oxide and silicon oxide. 5. The method according to any one of claims 1 to 4,
(Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N-phenylmaleimide and N-cyclohexylmaleimide (meth) acrylate, wherein the other radically polymerizable monomer (Meth) acrylate and (meth) acrylate, wherein the total weight of the compound is 50% by weight or more based on the total weight of the other radically polymerizable monomer (a2). The method according to claim 1,
Wherein the polyfunctional epoxy compound (B) is at least one selected from a glycidyl ether type epoxy compound (Ba), an alicyclic aliphatic epoxy compound (Bb) and an epoxy group containing polymer (Bc)
The epoxy group-containing polymer (Bc) is obtained by polymerizing a mixture of a radically polymerizable monomer (b1) having an epoxy group and a radically polymerizable monomer containing another radically polymerizable monomer (b2)
The radically polymerizable monomer (b1) having an epoxy group and the other radically polymerizable monomer (b2) do not have a carboxyl group. The method according to claim 6,
Wherein the glycidyl ether type epoxy compound (Ba) is at least one compound selected from the group consisting of 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- Phenoxy] -2-propanol and 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1, 1 -bis [4 - ([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane,
Wherein the alicyclic aliphatic epoxy compound (Bb) is a 1,2-epoxy-4- (2-oxyllanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol. The method according to claim 1,
(C1) having a carboxyl group together with a polymerizable double bond in the compound (C) having a polymerizable double bond is at least one compound selected from the group consisting of phthalic acid monohydroxyethyl acrylate, succinic acid-modified pentaerythritol triacrylate, phthalic acid-modified pentaerythritol Triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, phthalic acid-modified dipentaerythritol pentaacrylate, and polybasic acid-modified acrylic oligomer. The method according to claim 1,
The photopolymerization initiator (D) contains a compound represented by the following formula (D-1) in an amount of 50% by weight or more based on the total weight of the photopolymerization initiator (D);

Wherein R ¹¹ , R ¹² and R ¹³ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms;
R ¹⁴ is an alkyl group of 1 to 15 carbon atoms, an alkenyl group of 2 to 15 carbon atoms, or an alkynyl group of 2 to 15 carbon atoms, and n is an integer of 1 to 5, 10. The method of claim 9,
Wherein the compound represented by the formula (D-1) is 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime). The method according to claim 1,
Wherein the 1,2-quinonediazide compound (E) is a 1,2-naphthoquinonediazide sulfonic acid ester. 12. The method of claim 11,
Wherein the 1,2-naphthoquinonediazide sulfonic acid ester is selected from the group consisting of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and 4,4 '- [1- [4 - [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester. A cured film obtained from the photosensitive composition according to any one of claims 1 to 12. A color filter using the cured film according to claim 13 as a protective film. A display device using the color filter according to claim 14. A solid-state imaging device using the color filter according to claim 14. A display element using the cured film according to claim 13 as a transparent insulating film formed between a TFT and a transparent electrode. A display element using the cured film according to claim 13 as a transparent insulating film formed between a transparent electrode and an orientation film. A touch panel using the cured film according to claim 13 as a transparent insulating film formed between electrodes. An LED light source using the cured film according to claim 13 as a protective film.