KR20120023540A - Photosensitive composition, cured film obtained therefrom, and display element which has the cured film - Google Patents

Abstract

PURPOSE: A photo-sensitive composition, a cured film obtained from the composition, and a display device including the cured film are provided to improve resistance characteristic with respect to ultraviolet-ray based ozone ashing treatment. CONSTITUTION: A photo-sensitive composition includes polymer with a siloxane structure and 1,2-quinonediazide compound. The polymer with the siloxane structure is the radical polymer of silicon compound represented by chemical formula 1 and monomer containing alkali soluble radical polymerizable monomer. The alkali soluble radical polymerizable monomer includes alkali solubility and radical polymerization characteristic. In chemical formula 1, the R1 to the R4 are respectively hydrogen element or C1 to C30 alkyl in which arbitrary hydrogen element is capable of being substituted with fluorine and non-continuous arbitrary methylene is capable of being substituted with oxygen; the A1 and the A2 are radical polymerizable functional group; the n is the integer of 1 to 1000.

Description

Photosensitive composition, the cured film obtained from this composition, and the display element which has this cured film {PHOTOSENSITIVE COMPOSITION, CURED FILM OBTAINED THEREFROM, AND DISPLAY ELEMENT WHICH HAS THE CURED FILM}

This invention relates to the photosensitive composition for manufacturing display elements, such as a liquid crystal display element and an EL display element, a cured film, such as a transparent film manufactured from the said composition, and a display element which has the said cured film.

The patterned transparent film is used in many parts of liquid crystal display elements, such as a spacer, an insulating film, and a protective film, and various photosensitive compositions have been used for display elements, such as a liquid crystal display element and an EL display element, until now (for example, See Patent Document 1). A patterned transparent film forms a patterned film by apply | coating a photocurable polymer composition to a board | substrate, irradiating light through a pattern to a coating film, washing the light irradiated film, and removing the uncured and uncured part. It can be formed by a positive photosensitive material which forms a patterned film by developing a negative photosensitive material or a film irradiated with light with an alkaline developer to remove a part solubilized by light irradiation. Many photocurable polymer compositions and photosensitive compositions for forming a patterned transparent film have also been proposed (see Patent Document 2, for example).

On the other hand, in recent years, various patterning by the inkjet system is proposed (for example, refer patent document 3). In addition, in patterning by the inkjet method, the partition (bank material) between pixels may be formed before application | coating by the inkjet method in order to perform precise inkjet patterning.

This bank material can be formed as a patterned film by the well-known method using the photocurable polymer composition and photosensitive composition which were mentioned above. In such a bank material, the characteristic that the liquid substance ejected from the head nozzle of an inkjet apparatus does not adhere, ie ink repellency, is calculated | required (for example, refer patent document 4 and 5). In addition, in a semiconductor manufacturing process, an LCD manufacturing process, etc., a UV ozone ashing process may be performed in order to improve the ink applicability | paintability and wettability of the opening part to which the said liquid substance is apply | coated. At this time, since the surface of the bank material is also treated, the liquid repellency of the bank material is lowered. However, a bank material that can withstand such a process and can reduce the surface liquid repellency is demanded.

Thus, the use of the photocurable polymer composition and the photosensitive composition is expanding not only to the material constituting the layer in the display element described above, but also to a film for an auxiliary role in the manufacture of the display element. In the photocurable polymer composition and the photosensitive composition, various performances are required from the prior art.

Japanese Patent Application Publication No. 2004-287232 Japanese Patent Application Publication No. 2001-261761 Japanese Patent Application Publication No. Hei 10-12377 Japanese Patent Application Publication No. Hei 11-281815 Japanese Patent Application Publication No. 2004-149699

An object of this invention is to provide the positive photosensitive composition which can form the cured film excellent in liquid repellency and resistance to UV ozone ashing. Moreover, this invention makes it a subject to provide the cured film by such a positive photosensitive composition, and the display element which has this film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the problem mentioned above, the present inventors used the polymer which copolymerized the monomer containing polyfunctional siloxane for the photosensitive composition, and especially the cured film excellent in liquid repellency and resistance to UV ozone ashing is produced. It discovered what was obtained and completed this invention shown below.

[1] A photosensitive composition containing a polymer (A) containing a siloxane structure and a 1,2-quinonediazide compound (B), wherein the polymer (A) containing a siloxane structure is represented by Formula (1) A photosensitive composition, which is a radical polymer of a monomer comprising an alkali-soluble radical polymerizable monomer having alkali solubility and radical polymerizability that imparts alkali solubility to the siloxane compound and the polymer (A):

[Formula 1]

In formula (1), each of R ^{1 to} R ⁴ independently represents hydrogen or alkyl having 1 to 30 carbons in which any hydrogen may be substituted with fluorine and any methylene that is not continuous may be replaced with oxygen. , A ¹ and A ² each represent a radical polymerizable functional group, and n represents an integer of 1 to 1,000.

[2] at least one member selected from the group consisting of a radically polymerizable monomer having an unsaturated carboxylic acid, a radically polymerizable monomer having an unsaturated carboxylic anhydride, and a radically polymerizable monomer having a phenolic hydroxyl group. The photosensitive composition as described in said [1] containing.

[3] The photosensitive composition according to the above [1] or [2], wherein the alkali-soluble radical polymerizable monomer contains a radical polymer monomer represented by Formula (2):

[Formula 2]

In formula (2), R <^5> -R <^7> represents hydrogen or C1-C3 alkyl which arbitrary hydrogen may substitute by fluorine, respectively, and R <^8> -R <^12> is hydrogen; halogen; -CN; -CF _3; -OCF ₃ ; Hydroxyl group; Alkyl having 1 to 5 carbons in which any methylene may be substituted with —COO—, —OCO—, —CO—, and in which any hydrogen may be substituted with halogen; Or alkoxy having 1 to 5 carbon atoms in which any hydrogen may be substituted with halogen. However, at least 1 of R <^8> -R <^12> is a hydroxyl group.

[4] The above-mentioned [1], wherein the polymer (A) having a siloxane structure is a radical polymer of a monomer further comprising a siloxane compound represented by the formula (1) and another radical polymerizable monomer other than the alkali-soluble radical polymerizable monomer. ? The photosensitive composition as described in any one of said [3].

[5] The photosensitive composition according to the above [4], wherein the other radical polymerizable monomer contains a siloxane compound represented by Formula (3):

(3)

In formula (3), R <^13> -R <^17> respectively independently represents the C1-C30 alkyl or the C1-C30 which arbitrary hydrogen may be substituted by fluorine, and arbitrary methylene may be substituted by oxygen. 500 tri (alkyl / alkoxy) siloxy is represented, A ³ represents a radical polymerizable functional group, and n represents an integer of 0 to 1,000.

[6] The photosensitive composition according to the above [5], wherein the other radical polymerizable monomer is a siloxane compound represented by formula (3) in which n is 0.

[7] The photosensitive composition as described in the above [6], wherein R ^{13 to} R ¹⁵ in the formula (3) are each represented by the following formula (5).

[Formula 4]

In formula (5), R <^21> -R <^23> is respectively independently hydrogen, C1-C20 alkyl, or C1-C20 alkoxy (However, at least 1 of terminal R <^21> -R <^23> is the said alkyl or M) represents an integer of 1 to 500.

[8] The above [4], wherein the other radical polymerizable monomer contains a (meth) acrylic acid derivative. The photosensitive composition as described in any one of said [7].

[9] The above-mentioned [1], which is a radical polymer of monomers other than the siloxane compound represented by Formula (1), and further contains alkali-soluble polymer (C) which has alkali solubility. The photosensitive composition as described in any one of said [8].

[10] The alkali-soluble polymer (C) is one or more selected from the group consisting of a radical polymerizable monomer having an unsaturated carboxylic acid, a radical polymerizable monomer having an unsaturated carboxylic acid anhydride, and a radical polymerizable monomer having a phenolic hydroxyl group. The photosensitive composition as described in said [9] which is a radical polymer of the monomer containing.

[11] The above-mentioned [1], which further contains a solvent. The photosensitive composition as described in any one of said [10].

[12] The above [1]? Cured film obtained by baking the film | membrane of the photosensitive composition in any one of said [11].

[13] A display element having the cured film according to the above [12].

Since the photosensitive composition of this invention is an alkali-soluble radical polymer of the monomer containing the siloxane compound represented by Formula (1), it is excellent in liquid repellency before and after UV ozone ashing treatment by applying it to a positive type photoresist. A cured film can be formed.

1. Photosensitive composition of the present invention

The photosensitive composition of this invention contains the polymer (A) containing a siloxane structure, and a 1, 2- quinonediazide compound (B). The polymer (A) containing a siloxane structure may be one kind or two or more kinds, and the 1,2-quinone diazide compound (B) may be one kind or two or more kinds. The photosensitive composition is obtained by mixing a polymer (A) containing a siloxane structure and a 1,2-quinonediazide compound (B).

1-1. Polymer (A) containing a siloxane structure

The polymer (A) containing a siloxane structure is a siloxane compound represented by Formula (1) which has a linear siloxane structure of silicon number 2 or more, and two radically polymerizable functional groups (Hereinafter, "a radically polymerizable monomer ( a-1) "and an alkali-soluble radically polymerizable monomer (also referred to as" a radically polymerizable monomer (a-2) ") having alkali solubility and radical polymerizability to impart alkali solubility to the polymer (A). Radical polymer of a monomer containing).

The polymer (A) containing a siloxane structure has alkali solubility provided by the radically polymerizable monomer (a-2). The alkali solubility which the polymer (A) containing a siloxane structure means is a film of 0.01-100 micrometers in thickness formed by spin coating of the solution of the polymer (A) containing a siloxane structure, and heating at 100 degreeC for 2 minutes, for example. For example, when it is immersed in 2.38 weight% tetramethylammonium hydroxide aqueous solution about 25 degreeC for 5 minutes, and wash | cleaned with pure water, it means that a film | membrane does not remain.

The radically polymerizable monomers (a-1) and (a-2) may each be one kind or two or more kinds. It is preferable that content of the radically polymerizable monomer (a-1) in all the monomers which comprise the polymer (A) containing a siloxane structure is 0.1-50 weight% from a viewpoint of expressing the liquid repellency of a cured film, and is 0.5? It is more preferable that it is 30 weight%, and it is most preferable that it is 1-20 weight%. In addition, content of the radically polymerizable monomer (a-2) in all the monomers which comprise the polymer (A) containing a siloxane structure is 0.1-50 weight% from a viewpoint of expressing sufficient developability at the time of manufacture of a cured film. It is preferable, it is more preferable that it is 0.5-30 weight%, and it is most preferable that it is 1-20 weight%.

1-1-1. Radically polymerizable monomer (a-1)

A radically polymerizable monomer (a-1) is a compound which has a linear siloxane structure of silicon number 2 or more, and two radically polymerizable functional groups, and is represented by Formula (1).

[Chemical Formula 5]

In formula (1), R <^1> -R <^4> respectively independently represents hydrogen or C1-C30 alkyl which arbitrary hydrogen may be substituted by fluorine, and arbitrary methylene which is not continuous may be substituted by oxygen. . Such alkyl includes, for example, alkyl fluoride and alkoxy having 1 to 20 carbon atoms.

In Formula (1), A <^1> and A <^2> respectively represent a radically polymerizable functional group. A ¹ and A ² may be the same or different. As a radically polymerizable functional group, group which has a structure which can be radically polymerized by a radically polymerizable monomer (a-1) can be used. As such a radically polymerizable functional group, there exist a well-known radically polymerizable functional group, For example, vinyl, vinylene, vinylidene, (meth) acryloyl, styryl, etc. are mentioned.

The radically polymerizable functional group may further have a substituent in the range which can obtain radical polymerizability. As such a substituent, For example, C2-C10 alkylene; Alkoxy groups such as methoxy and ethoxy groups; And branched alkyl groups such as isopropyl group and isobutyl group.

In formula (1), n represents the integer of 1-1,000. From the viewpoint of obtaining good alkali developability, n is preferably 2 to 500, more preferably 5 to 300, and most preferably 10 to 150.

As a radically polymerizable monomer (a-1), there exists a siloxane monomer which has a methacryloyl group in the both terminal represented by Formula (1-1), for example. The use of the siloxane monomer in the radically polymerizable monomer (a-1) has high initial transparency, little deterioration in transparency due to calcination at high temperature, and high solubility in aqueous alkali solution during development ( That is, high developability), a patterned transparent film can be easily obtained, and also a photosensitive composition or cured film showing solvent resistance, high water resistance, acid resistance, alkali resistance, and heat resistance, and high adhesion to an under layer. It is preferable from a viewpoint of obtaining. In the formula (1-1), n represents an integer of 1 to 1,000.

[Formula 6]

Some commercially available as radically polymerizable monomer (a-1). As a compound represented by Formula (1-1), there exists a sila plain FM7711 (brand name, the Tosoh Corporation make), for example.

1-1-2. Radically polymerizable monomer (a-2)

The radically polymerizable monomer (a-2) has alkali solubility and radical polymerizability which gives alkali solubility to the polymer (A). Alkali solubility which a radically polymerizable monomer (a-2) has means that water-soluble salt is formed with alkali also in the form after radical polymerization of a radically polymerizable monomer (a-2). Such alkali solubility is provided by the structure which has a site | part which forms water-soluble salt in alkali independently of a radical polymerization site | part, for example, a carboxyl group or phenolic hydroxyl group. In addition, the radical polymerizability which a radically polymerizable monomer (a-2) has means the property of radically polymerizing with another monomer containing a radically polymerizable monomer (a-1). Such radical polymerizability is provided by the above-mentioned radically polymerizable functional group. Therefore, a radically polymerizable monomer (a-2) is comprised with the site | part which melt | dissolves in the alkali mentioned above, and a radically polymerizable functional group.

As such a radically polymerizable monomer (a-2), for example, a radically polymerizable monomer containing an unsaturated carboxylic acid, a radically polymerizable monomer containing an unsaturated carboxylic acid anhydride, and a radically polymerizable monomer containing a phenolic hydroxyl group include have. As a radically polymerizable monomer containing an unsaturated carboxylic acid, for example, there is (meth) acrylic acid, and as a radically polymerizable monomer containing an unsaturated carboxylic acid anhydride, for example, there is maleic anhydride and a radical containing a phenolic hydroxyl group. As a polymerizable monomer, there exist a vinyl ketone which has a phenolic hydroxyl group, and the styrene derivative which has a phenolic hydroxyl group, for example.

As a vinyl ketone which has a phenolic hydroxyl group, there exists a compound represented by Formula (2), for example.

[Formula 7]

In formula (2), R <^5> -R <^7> respectively represents hydrogen or C1-C3 alkyl which arbitrary hydrogen may substitute by fluorine, and R <^8> -R <^12> respectively represents hydrogen, halogen,- CN, -CF ₃ , -OCF ₃ , a hydroxyl group, alkyl having 1 to 5 carbons, in which any methylene may be substituted with -COO-, -OCO-, -CO-, and any hydrogen may be substituted with halogen, or Arbitrary hydrogen represents the C1-C5 alkoxy which may be substituted by halogen. However, at least 1 of R <^8> -R <^12> is a hydroxyl group.

It is preferable that R <^8> -R <^12> except R <^5> -R <^7> and a hydroxyl group is hydrogen from a viewpoint of improving alkali solubility. As a compound represented by Formula (2), there exists 4-hydroxyphenyl vinyl ketone, for example.

The vinyl ketone which has a phenolic hydroxyl group can be synthesize | combined and obtained according to a well-known method, or can be used as a commercial item. For example, 4-hydroxyphenyl vinyl ketone is added aluminum chloride to a methylene chloride solution of 2-chloroethyl-4-methoxyphenyl ketone as described in Japanese Patent Application Laid-open No. 2004-189715. The obtained mixture is refluxed, cooled, an organic phase is extracted with ethyl acetate, the obtained organic phase is extracted with an aqueous NaOH solution, made acidic with hydrochloric acid, and then extracted again with ethyl acetate.

The styrene derivative which has a phenolic hydroxyl group has the polymeric double bond which styrene has other than a phenolic hydroxyl group. As a styrene derivative which has a phenolic hydroxyl group, o-hydroxy styrene, m-hydroxy styrene, and p-hydroxy styrene are mentioned, for example.

1-1-3. Other radically polymerizable monomer (a-3)

The polymer (A) containing a siloxane structure is a radically polymerizable monomer other than the radically polymerizable monomer (a-1) and (a-2) (hereinafter also referred to as "radical polymerizable monomer (a-3)"). It is preferable that it is a radical polymer of the monomer further containing from a viewpoint of improving or increasing the characteristic which the polymer (A) containing a siloxane structure has. The radically polymerizable monomer (a-3) may be one kind or two or more kinds. Content of the radically polymerizable monomer (a-3) among the all monomers which comprise the polymer (A) containing a siloxane structure is the improvement of the characteristic which the polymer (A) containing a siloxane structure has, or the polymer containing a siloxane structure. From the viewpoint of imparting new properties to (A), it is preferably 50.0 to 99.9% by weight, more preferably 70.0 to 99.5% by weight, most preferably 80.0 to 99.9% by weight.

As a radically polymerizable monomer (a-3), for example, a siloxane compound represented by the formula (3), a radically polymerizable monomer containing an epoxy, a (meth) acrylic acid derivative, an N-substituted maleimide, and dicyclopentanyl There is a radically polymerizable monomer containing.

[Formula 8]

In formula (3), each of R ^{13 to} R ¹⁷ independently represents an alkyl having 1 to 30 carbons, or an alkyl having 1 to 30 carbon atoms, in which any hydrogen may be substituted with fluorine, and any methylene may be substituted with oxygen. 1-500 tri (alkyl / alkoxy) siloxy having 1 to 20 is represented, A ³ represents a radical polymerizable functional group, and n represents an integer of 0 to 1,000. However, when n is 0, it is preferable that R <^13> -R <^15> is group represented by Formula (5), respectively. Then, the radical polymerizable functional group A ³ are the same meanings as the radical polymerizable functional group of the aforementioned formula (1). In addition, "tri (alkyl / alkoxy)" means three groups comprised by either or both of an alkyl group and an alkoxy group.

[Formula 9]

In formula (5), R <^21> -R <^23> is respectively independently hydrogen, C1-C20 alkyl, or C1-C20 alkoxy (However, at least 1 of terminal R <^21> -R <^23> is the said alkyl or the said Alkoxy). m represents the integer of 1-500.

As the siloxane compound represented by the formula (3), for example, α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane represented by the formula (3-1) (trade name: FM0711, manufactured by Chisso Corporation) There is this. This is preferable from the viewpoint of improving the surface liquid repellency by the silicon to contain.

[Formula 10]

Moreover, as represented by Formula (3), as a siloxane compound which n is 0, for example, 3-methacryloxypropyl trimethoxysilane (brand name: S710, the product made by Chisso Corporation), 3-methacryloxypropyl tris (Trimethylsiloxy) silane (trade name: TM0701T, manufactured by Chisso Corporation), and 3-methacryloxypropylmethyldimethoxysilane (trade name: KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd.). Especially, 3-methacryloxypropyl trimethoxysilane is preferable from a viewpoint of the improvement of the solubility to alkaline developing solution.

As a radically polymerizable monomer containing an epoxy, for example, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) acrylate, and 3- Ethyl-3- (meth) acryloxymethyloxetane. These are easy to obtain and are preferable from the viewpoint of improving the solvent resistance, water resistance, acid resistance, alkali resistance, heat resistance and transparency of the patterned transparent film obtained.

The (meth) acrylic acid derivative may be a derivative having a polymerizable double bond that (meth) acrylic acid has. As the (meth) acrylic acid derivative, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl Alkyl methacrylates such as methacrylate, hexyl methacrylate and ethylhexyl methacrylate; Alkyl methacrylates containing aromatic rings such as benzyl methacrylate and phenoxyethyl methacrylate; Hydroxyl groups such as hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, hydroxypentyl methacrylate, hydroxyhexyl methacrylate Alkyl methacrylate having; Dialkylaminoalkyl methacrylates such as dimethylaminoethyl methacrylate; Aryl methacrylates such as phenyl methacrylate.

As N substituted maleimide, N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide, N- ( 4-acetylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N- (1-anilinonaphthyl -4) maleimide, N- [4- (2-benzoxazolyl) phenyl] maleimide, and N- (9-acridinyl) maleimide.

As a radically polymerizable monomer containing dicyclopentanyl, there exist dicyclopentanyl acrylate and dicyclopentanyl methacrylate, for example.

It is preferable from a viewpoint of raising the heat resistance of the cured film formed from the photosensitive composition that radically polymerizable monomer (a-3) contains either or both of the radically polymerizable monomer containing N substituted maleimide and dicyclopentanyl.

About the monomer of the polymer (A) containing a siloxane structure, 1 or more types chosen from the group which consists of hydroxyethyl (meth) acrylate, a (meth) acrylic acid derivative, and a styrene derivative which has a phenolic hydroxyl group are contained in the said monomer. It is preferable to be contained from a viewpoint of raising alkali solubility of the polymer (A) containing a siloxane structure.

The polymer (A) containing a siloxane structure adds a radically polymerizable monomer (a-1) and (a-2) further as needed, and also a radically polymerizable monomer (a-3), and makes it radical-polymerize these. Obtained by This radical polymerization can be performed by a well-known method.

Although the polymerization method of the polymer (A) containing a siloxane structure is not specifically limited, Radical polymerization in the solution using a solvent is preferable. The polymerization temperature is not particularly limited as long as the radical is sufficiently generated from the polymerization initiator to be used, but is usually in the range of 50 ° C to 150 ° C. Although polymerization time is not specifically limited, either, Usually, it is the range of 1 to 24 hours. In addition, the said polymerization can be performed under any pressure of pressurization, reduced pressure, or atmospheric pressure.

As a solvent used by radical polymerization, the solvent which melt | dissolves the radically polymerizable monomer to be used and a product is preferable. The solvent may be one kind or two or more kinds. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, 3-methoxypropionate methyl, 3-ethoxypropionate, and N, N -Dimethylformamide.

Examples of the polymerization initiator used in the radical polymerization include compounds that generate radicals by heat, azo initiators such as azobisisobutyronitrile, and peroxide initiators such as benzoyl peroxide. It is preferable that it is 1-30 weight part with respect to 100 weight part of monomer total amounts used as a raw material, and, as for the usage-amount of a polymerization initiator, it is more preferable that it is 5-25 weight part.

In radical polymerization, in order to adjust molecular weight, you may add chain transfer agents, such as thioglycolic acid. It is preferable that it is 0.001-0.05 weight part with respect to 100 weight part of monomer total amounts used as a raw material, and, as for the addition amount of a chain transfer agent, it is more preferable that it is 0.005-0.03 weight part.

The weight average molecular weight of the polymer (A) containing the siloxane structure is 1,000 to 100,000, and the development time until the exposed portion is dissolved in the alkaline developer is appropriate, and the surface of the film is not easily roughened during development. Preferred at The weight average molecular weight is further preferably 1,500 to 50,000, and most preferably 2,000 to 20,000, since the development residues are extremely small.

The weight average molecular weight can be obtained by GPC analysis based on polystyrene, for example, using polystyrene having a molecular weight of 500 to 150,000 (for example, PL2010-0102 (S-M2-10) standard manufactured by Polymer Laboratories). As a column at the time of a measurement, Shodex PLgel MIXED-D (made by Polymer Laboratories) can be used, and THF can be used as a mobile phase at the time of the said measurement. Under such conditions, the weight average molecular weight can be measured.

And the well-known analysis which the monomer of the polymer (A) containing a siloxane structure can confirm the specific structure containing the silicon atom in the polymer (A) containing a siloxane structure, and the structure derived from a radically polymerizable functional group is known. can be checked by a method, for example, it can be confirmed by detection of a peak of the Si-CH ₃ in the peak detection and an ethylene group or a propylene group by the ¹ H-NMR.

1-2. 1,2-quinonediazide compound (B)

As the 1,2-quinonediazide compound (B), for example, a compound used as a photosensitizer in the resist field can be used. As a 1, 2- quinone diazide compound (B), for example, a hydroxy benzophenone compound and a 1, 2- benzoquinone diazide- 4-sulfonic acid or a 1, 2- benzoquinone diazide- 5-sulfonic acid Esters, esters of hydroxybenzophenone compounds with 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid, phenolic compounds and 1,2-benzoquinonediazide Ester of 4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid, phenolic compounds with 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5- Hydroxyl group of the sulfonamide and phenol compound of the compound which substituted ester with sulfonic acid and the hydroxyl group of a phenolic compound with an amino group, and 1,2-benzoquinone diazide- 4-sulfonic acid or 1,2-benzoquinone diazide-5-sulfonic acid Sulfonic acid of 1,2-naphthoquinone diazide-4-sulfonic acid or 1,2-naphthoquinone diazide-5-sulfonic acid There Degas.

As the hydroxybenzophenone compound, for example, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone , 2,3,3 ', 4-tetrahydroxybenzophenone, and 2,3,4,4'-tetrahydroxybenzophenone.

Examples of the phenol compound include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p -Hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2 , 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol , Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7 , 5 ', 6', 7'-hexanol, and 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan.

The 1,2-quinone diazide compound (B) is ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinone diazide-4-sulfonic acid, and 2,3,4-trihydride Ester of oxybenzophenone with 1,2-naphthoquinone diazide-5-sulfonic acid, with 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-4-sulfonic acid Ester of 2,3,4,4'-tetrahydroxybenzophenone with 1,2-naphthoquinonediazide-5-sulfonic acid, 4,4 '-[1- [4- [1- [ 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol with 1,2-naphthoquinonediazide-4-sulfonic acid, and 4,4 '-[1- [4- [1 The photosensitive composition is one or more selected from the group consisting of esters of-[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid. It is preferable from a viewpoint of improving transparency.

1-3. Other ingredients

The photosensitive composition can further contain components other than the polymer (A) and 1,2-quinonediazide compound (B) containing the siloxane structure mentioned above within the range which can fully acquire the effect of this invention. . As such another component, alkali-soluble polymer (C), a solvent, an additive, and polyhydric carboxylic anhydride are mentioned, for example.

1-3-1. Alkali Soluble Polymer (C)

The photosensitive composition further contains an alkali-soluble polymer (C) from the viewpoint of further increasing alkali solubility of the photosensitive composition to easily obtain a patterned transparent film, and solvent resistance, high water resistance, high acid resistance, high alkali resistance, and high heat resistance. It is preferable from a viewpoint of improving the characteristic of the cured film obtained, etc. The alkali-soluble polymer (C) may be one kind or two or more kinds. In addition, "alkali solubility" in an alkali-soluble polymer (C) means the film of 0.01-100 micrometers in thickness formed by spin coating of the solution of an alkali-soluble polymer (C), and heating at 100 degreeC for 2 minutes, for example, When it is immersed in the 2.38 weight% tetramethylammonium hydroxide aqueous solution about 25 degreeC for 5 minutes, and wash | cleaned with pure water, it means that a film | membrane does not remain.

An alkali-soluble polymer (C) is contained in a radically polymerizable monomer (a-2) or a radically polymerizable monomer (a-2) and a radically polymerizable monomer (a-3) so that the polymer obtained may have alkali solubility. A radical polymer obtained by radical polymerization of two or more kinds of radically polymerizable monomers can be used. Such radically polymerizable monomer can be used in alkali-soluble polymer (C) in the photosensitive composition of this invention in consideration of the usage-amount in the polymer (A) which has a siloxane structure, and can acquire a desired function. .

As the monomer of the alkali-soluble polymer (C), a radical polymerizable monomer (a-2) can be used as the radical polymerizable monomer having a phenolic hydroxyl group. The monomer of the alkali-soluble polymer (C) includes at least one member selected from the group consisting of (meth) acrylic acid, maleic anhydride, hydroxystyrene, and 4-hydroxyphenylvinyl ketone, and the alkali-soluble polymer of the photosensitive composition. It is preferable from a viewpoint of improving the.

As for the weight average molecular weight of an alkali-soluble polymer (C), like the polymer (A) containing a siloxane structure, developing time until the exposure part melt | dissolves with alkaline developing solution is suitable for 1,000-100,000, and at the time of image development It is preferable from the viewpoint that the surface of the film is not easily roughened, preferably 1,500 to 50,000, more preferably from the viewpoint of extremely low development residues, and most preferably 2,000 to 20,000. The weight average molecular weight of an alkali-soluble polymer (C) can be calculated | required by GPC analysis on the same conditions as the polymer (A) containing a siloxane structure, for example.

An alkali-soluble polymer (C) can be obtained by the same polymerization method as the polymer (A) containing a siloxane structure, for example. In addition, the monomer of an alkali-soluble polymer (C) can be estimated by measuring the gas produced by thermal decomposition by GC-MS, for example when thermally decomposing an alkali-soluble polymer (C).

1-3-2. solvent

It is preferable that a photosensitive composition contains a solvent further. The solvent is preferably a solvent in which a polymer (A), a 1,2-quinonediazide compound (B), and an alkali-soluble polymer (C) containing a siloxane structure blended with the photosensitive composition are dissolved. Moreover, the solvent whose boiling point is 100 degreeC-300 degreeC is preferable. The solvent may be one kind or two or more kinds.

As a solvent whose boiling point is 100 degreeC-300 degreeC, for example, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, oxyacetic acid butyl, methoxyacetic acid methyl, methoxyacetic acid ethyl, methoxyacetic acid butyl , Methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate , Methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-e Ethyl oxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionic acid , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetic acid, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, di Propylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, 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, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene Glycolmo Butyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, γ-butyrolactone, and N, N-dimethylacetamide have.

The solvent is propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl It is preferable at least 1 type chosen from the group which consists of ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethyl lactate, and butyl acetate from a viewpoint of improving the coating uniformity in forming the film | membrane of a photosensitive composition. In addition, the human body is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methylethyl ether, ethyl lactate, and butyl acetate. It is more preferable from the viewpoint of safety.

The solvent may be a mixed solvent containing 20% by weight or more of a solvent having a boiling point of 100 ° C to 300 ° C. In a mixed solvent, as solvent other than the solvent whose boiling point is 100 degreeC-300 degreeC, 1, 2 or more types can be used in a well-known solvent.

1-3-3. additive

It is preferable that a photosensitive composition contains an additive from a viewpoint of further improving the characteristic of the photosensitive composition, such as a resolution, application | coating uniformity, developability, and adhesiveness, and the cured film formed. In the field of photoresist, various additives used for the improvement of the characteristic of a photosensitive composition and a cured film can be used for an additive. The additive may be one kind or two or more kinds. As such additives, for example, adhesion properties such as acrylic, styrene, polyethyleneimine-based or urethane-based polymer dispersants, anionic, cationic, nonionic or fluorine-based surfactants, silicone resin-based coating agents, silane coupling agents, and the like There exist an alkali solubility promoter, such as an improving agent, ultraviolet absorbers, such as alkoxy benzophenones, aggregation inhibitors, such as sodium polyacrylate, an epoxy compound, a melamine compound, or a bisazide compound, and an organic carboxylic acid.

More specifically, as an additive, for example, polyflow No. 45, polyflow KL-245, polyflow No. 75, polyflow No. 90, polyflow No. 95 (all of the above are brand names and Kyoeisha Chemical Co., Ltd.). Co., Ltd.), Disperbyk 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181, Disperbake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK344, BYK346 (all of the above brand names, Big Chemi Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50 CS, KF-50 -100 CS (all brand names, Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all brand names, AGC Seiko Chemical Co., Ltd.), Pgentant 222F, Pgentant 251, FTX-218 ( All of the above are brand names, product of Neos), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all of the above Subishi Material Co., Ltd.), Mega Pack F-171, Mega Pack F-177, Mega Pack F-475, Mega Pack R-08, Mega Pack R-30 (all of the above trade names, manufactured by DIC Corporation), Fluoroalkylbenzene Sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoro Roalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tri Decyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene Stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitanate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate , Polyoxyethylene sorbitan stearate, polyoxyethylene sorbitanolate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferable that an additive is 1 or more types chosen from these.

It is more preferable that an additive is one or both of a fluorine-type surfactant and a silicone resin coating property improving agent from a viewpoint of raising the application uniformity of the photosensitive composition. More specifically, the additive is fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, iodide fluoroalkylammonium, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetra One kind selected from the group consisting of Keith (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate salt, BYK306, BYK344, BYK346, KP-341, KP-358, and KP-368. It is more preferable from the viewpoint of improving the coating uniformity of the photosensitive composition.

1-3-4. Polyhydric carboxylic anhydride

The photosensitive composition further contains polyhydric carboxylic anhydride in view of enhancing heat resistance and chemical resistance of the cured film formed from the photosensitive composition having epoxy, and decomposition of the 1,2-quinonediazide compound (B) during storage. It is preferable from a viewpoint of preventing coloring of the photosensitive composition by this. Polyhydric carboxylic anhydride reacts with the epoxy in the photosensitive composition which has an epoxy by heating. The polyhydric carboxylic acid anhydride may be one kind or two or more kinds. Examples of the polyhydric carboxylic anhydride include trimellitic anhydride, phthalic anhydride, and 4-methylcyclohexane-1,2-dicarboxylic anhydride. Among the polyhydric carboxylic anhydrides, trimellitic anhydride is preferred.

1-4.Content of each component in photosensitive composition

From the viewpoint of expressing the liquid repellency of the cured film, the content of the polymer (A) having a siloxane structure in the photosensitive composition is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and 40 to 60%. Most preferred is weight percent.

Content of a 1, 2- quinonediazide compound (B) in a photosensitive composition forms a fine pattern in a cured film with respect to 100 weight part of total amounts of the polymer (A) and alkali-soluble polymer (C) containing a siloxane structure. From a viewpoint, it is preferable that it is 5-50 weight part, It is more preferable that it is 10-40 weight part, It is most preferable that it is 15-30 weight part.

In the photosensitive composition, the content of the alkali-soluble polymer (C) is 20 to 150 parts by weight when the content of the polymer (A) containing the siloxane structure is 100 parts by weight from the viewpoint of fully expressing the alkali-soluble improving effect. It is preferable, it is more preferable that it is 50-120 weight part, and it is most preferable that it is 70-100 weight part.

The content of the solvent in the photosensitive composition is preferably an amount such that the total solid content in the photosensitive composition is 5 to 50% by weight, from the viewpoint of increasing the coating uniformity of the photosensitive composition and from the viewpoint of safety to the human body. The amount is more preferably 45% by weight, most preferably 15-40% by weight.

Content of the additive in the photosensitive composition is 0.01-1 weight with respect to 100 weight part of total amounts of the polymer (A) and alkali-soluble polymer (C) containing a siloxane structure from a viewpoint of provision and improvement of the characteristic of a photosensitive composition and a cured film. It is preferable that it is denier, It is more preferable that it is 0.03-0.7 weight part, It is most preferable that it is 0.05-0.5 weight part.

Content of polyhydric carboxylic anhydride in the photosensitive composition is 100 weight part of total amounts of the polymer (A) and alkali-soluble polymer (C) containing a siloxane structure from a viewpoint of the improvement of the characteristic of the cured film mentioned above, and the coloring prevention of a photosensitive composition. It is preferable that it is 1-30 weight part, It is more preferable that it is 2-20 weight part, It is most preferable that it is 3-15 weight part.

1-5. Preservation of the Photosensitive Composition

It is preferable to block and store a photosensitive composition at -30 degreeC-25 degreeC from a viewpoint of stably storing a photosensitive composition, and that a storage temperature is -20 degreeC-10 degreeC prevents generation | occurrence | production of a precipitate. It is more preferable from the viewpoint.

2. Cured film of this invention

The cured film of this invention can be obtained by baking the film | membrane of the photosensitive composition of this invention mentioned above. The photosensitive composition is suitable for forming a transparent cured film, and is suitable for forming an insulating film having a small hole of 10 μm or less because the resolution at the time of patterning is relatively high. Here, an insulating film means the film | membrane (interlayer insulation film) etc. which are provided in order to insulate between the wiring arrange | positioned in layer form, for example.

Cured films, such as a transparent film and an insulating film, can be formed by the conventional method of forming a cured film in the resist field, For example, it is formed as follows.

First, a film of the photosensitive composition is formed. The film | membrane of the photosensitive composition is formed by apply | coating a photosensitive composition on substrates, such as glass, by well-known methods, such as spin coating, roll coating, and slit coating. Preferable application methods include spin coating, roll coating, and slit coating, for example. As a board | substrate, For example, transparent glass substrates, such as a white plate glass, a blue plate glass, and a silica coated blue plate glass, polycarbonate, polyether sulfone, polyester, an acrylic resin, a vinyl chloride resin, an aromatic polyamide resin, a polyamideimide, and a polyimide Metal substrates, such as a synthetic resin sheet, a film, or a board | substrate, such as a mead, an aluminum plate, a copper plate, a nickel plate, and a stainless plate, and the like, and also a semiconductor substrate which has a ceramic plate and 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, vapor phase reaction, vacuum deposition, or the like as desired.

Next, the film of the photosensitive composition is dried. The film of the photosensitive composition is dried by, for example, heating a substrate having the film of the photosensitive composition in a hot plate or oven. Usually, it is dried at 60 to 120 degreeC for 1 to 5 minutes.

Subsequently, radiation is irradiated to the film | membrane of the dry photosensitive composition through the mask of a desired pattern shape. Irradiation of the radiation to the film of the photosensitive composition is performed by irradiating an ultraviolet-ray through the mask to the film of the dry photosensitive composition on a board | substrate, for example. According to the kind of photosensitive agent in a photosensitive composition, irradiation conditions are 5-1,000 mJ / cm <^2> suitable for i line | wire because a photosensitive composition contains a 1, 2- quinonediazide compound (B), for example. And when forming the cured film which does not have a pattern, the irradiation process of this radiation is unnecessary.

Next, the film of the photosensitive composition irradiated with radiation is washed with a developer and developed. The 1, 2- quinonediazide compound (B) in the film | membrane of the photosensitive composition by which the radiation was irradiated becomes indencarboxylic acid, and will be in the state melt | dissolved in a developing solution quickly. By this phenomenon, the portion to which the radiation is irradiated from the film quickly dissolves in the developer. The image development method is not specifically limited, Any of well-known methods, such as a dipping development, a paddle development, a shower development, can be used. And when developing the cured film which does not have a pattern, this developing process is also unnecessary.

As the developing solution, an alkaline solution is preferable. As the developing solution, an aqueous alkali solution is preferably used. Examples of the alkali contained in the alkaline solution include tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, And potassium hydroxide. As a preferable developing solution, More specifically, organic alkalis, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and 2-hydroxyethyl trimethylammonium hydroxide, and inorganic, such as sodium carbonate, sodium hydroxide, or potassium hydroxide, etc. The aqueous solution of alkalis is mentioned, for example.

You may add methanol, ethanol, and surfactant to a developing solution for the purpose of reducing image development residue, and the suitability of a pattern shape. As the surfactant, for example, a surfactant selected from anionic, cationic and nonionic systems can be used. Among these, addition of nonionic polyoxyethylene alkyl ether is especially preferable from a viewpoint of raising a resolution.

The developed film is then washed. The washing of the film is performed by sufficiently washing the film with pure water for each substrate, for example.

Subsequently, radiation is irradiated to the entire surface of the cleaned film. By irradiation of this radiation, the remaining 1,2-quinonediazide compound (B) is inactivated. Irradiation of this radiation is performed by irradiating an ultraviolet-ray to a film | membrane in the exposure amount of 100-1,000 mJ / cm <^2> , when radiation is an ultraviolet-ray, for example.

Subsequently, the film irradiated with radiation is baked to obtain a cured film. Baking of this film is performed by heating the board | substrate which has a film, for example for 10 to 120 minutes at 180 degreeC-250 degreeC. By such a process, a cured film can be obtained as a desired patterned transparent film.

The patterned transparent film thus obtained can also be used as a patterned insulating film. The shape of the hole formed in the insulating film is preferably square, rectangular, circular or elliptical when viewed directly from above. Moreover, after forming a transparent electrode on the said insulating film, and patterning by etching, you may perform an orientation process. Since the said insulating film has high sputter resistance, even if a transparent electrode is formed, wrinkles do not arise in an insulating film, and high transparency can be kept constant.

3. Display element of the present invention

The display element of this invention has the cured film of this invention mentioned above. As a use of the cured film in a display element, a transparent film, an insulating film, and the bank film for preventing adhesion of the liquid to the circumference | surroundings of a pattern are mentioned.

A display element has the same structure as a well-known display element except having used the cured film of this invention for the use mentioned above, and can manufacture it similarly to a well-known display element. The display element is crimped, for example, by aligning an element substrate having a cured film patterned on the substrate and a color filter substrate, which is an opposing substrate, in accordance with a display position previously given to each substrate in advance as described above. By assembling other members other than the substrate, injecting the liquid crystal between the opposing substrates, and sealing the injection port, thereby producing the liquid crystal display element.

In manufacture of a liquid crystal display element, sealing of a liquid crystal can also be performed by overlapping an element substrate and a color filter substrate, and sealing so that a liquid crystal may not leak, after spreading a liquid crystal on an element substrate. The display element may be a liquid crystal display element thus produced.

A liquid crystal, ie, a liquid crystal compound and a composition containing the same, is not particularly limited, and all liquid crystal compounds and liquid crystal compositions can be used.

The photosensitive composition of the present invention is, for example, various solvents such as high solvent resistance, high water resistance, high acid resistance, high alkali resistance, high heat resistance, high transparency, adhesion to the underlying layer, and the like, which are generally required for patterned transparent films and insulating films. The cured film which has the characteristic and is excellent in liquid repellency can be formed.

In addition to the above-described high liquid repellency and resistance to UV ozone ashing, the photosensitive composition of the present invention is also suitable for the conventional properties required as the material of the photoresist, such as developability, chemical resistance, and adhesion. It has at least enough performance as a material. Therefore, the photosensitive composition of this invention can form the cured film excellent in pattern formation property in addition to liquid repellency. In addition, since the film can be used as a transparent film, an insulating film or a protective film, it can be used as a display element.

Since the cured film of this invention is formed from the photosensitive composition of this invention, even if it is processed by immersion, contact, heat processing etc. with a solvent, an acid, an alkaline solution, etc., surface roughness does not produce easily. Therefore, the display element of this invention has a high transmittance | permeability of the light in a cured film, and can obtain a high display quality.

Moreover, since the cured film of this invention is formed from the photosensitive composition, it is excellent in liquid repellency and prevents the liquid material supplied to the pattern (opening part) of a cured film from adhering to parts other than a pattern in the manufacturing process of a display element. And the liquid of the intended bar thus attached is easily moved to the opening. Therefore, it is expected that a display element having a desired performance can be efficiently obtained, and the productivity of the display element can be further improved.

[Example]

Hereinafter, although an Example further demonstrates this invention, this invention is not limited by these.

Synthesis Example 1 Synthesis of Polymer (A1) Containing a Siloxane Structure

Into a four-necked flask equipped with a stirrer, 16 g of diethylene glycol methyl ethyl ether was added as a solvent, and 11 g of diethylene glycol methyl ethyl ether was used as a radical polymerizable monomer (a-1). Α-, ω-bis (3-methacryloxypropyl) polydimethylsiloxane (manufactured by Chisso Corp., FM7711, number average molecular weight: 1,000), 4-hydroxyphenylvinyl as a radical polymerizable monomer (a-2) Glycidyl methacrylate, 3-methacryloxypropyl trimethoxysilane as a ketone, a radically polymerizable monomer (a-3), and 2,2'- azobis (2-methylpropionate) dimethyl as a polymerization initiator It mixed at the weight shown below, and the obtained mixed solution was dripped at the solvent in the 4 neck flask maintained at 110 degreeC for 1 hour, and after dripping, it heated at 110 degreeC for 2 hours further.

Diethylene glycol methyl ethyl ether 11.0 g

Α, ω-bis (3-methacryloxypropyl) polydimethylsiloxane of formula (1-1)

0.675 g

3-Methacryloxypropyltrimethoxysilane 6.075 g

4-hydroxyphenylvinyl ketone 2.025 g

? 4.725 g glycidyl methacrylate

2,2'-azobis (2-methylpropionate) dimethyl 2.025 g

[Formula 11]

The obtained reaction liquid was cooled to room temperature, and the 33.3 weight% solution of the polymer (A1) containing a siloxane structure which did not contain 2,2'- azobis (2-methylpropionate) dimethyl was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (A1) containing a siloxane structure was 4,000.

Synthesis Example 2 Synthesis of Polymer (A2) Containing Siloxane Structure

The mixed solution was prepared using the following component by the following weight, and it superposed | polymerized similarly to the synthesis example 1.

Diethylene glycol methyl ethyl ether 11.0 g

Α, ω-bis (3-methacryloxypropyl) polydimethylsiloxane of formula (1-1)

0.675 g

N-cyclohexylmaleimide 4.725 g

4.725 g of dicyclopentanyl methacrylate

3.375 g of methacrylic acid

2,2'-azobis (2-methylpropionate) dimethyl 2.025 g

The obtained reaction liquid was cooled to room temperature, and the 33.3 weight% solution of the polymer (A2) containing a siloxane structure which did not contain 2,2'- azobis (2-methylpropionate) dimethyl was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (A2) containing a siloxane structure was 3,100.

Synthesis Example 3 Synthesis of Alkali-Soluble Polymer (C1)

α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane represented by formula (3-1) instead of α, ω-bis (3-methacryloxypropyl) polydimethylsiloxane (manufactured by Chisso Corp., FM0711) And number average molecular weight: 1,000) using the following components by the following weights, the mixed solution was prepared, and it superposed | polymerized similarly to the synthesis example 1.

Diethylene glycol methyl ethyl ether 11.0 g

Α-Butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane of formula (3-1)

0.27 g

3-methacryloxypropyltrimethoxysilane 6.48 g

4-hydroxyphenylvinyl ketone 1.35 g

5.40 g glycidyl methacrylate

2,2'-azobis (2-methylpropionate) dimethyl 2.025 g

[Chemical Formula 12]

The obtained reaction liquid was cooled to room temperature, and the 33.3 weight% solution of the alkali-soluble polymer (C1) which does not contain 2,2'- azobis (2-methylpropionate) dimethyl was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C1) was 2,800.

Synthesis Example 4 Synthesis of Alkali-Soluble Polymer (C2)

The mixed solution was prepared using the following component by the following weight, and it superposed | polymerized similarly to the synthesis example 1.

Diethylene glycol methyl ethyl ether 11.0 g

Α-Butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane of formula (3-1)

0.675 g

3-Methacryloxypropyltrimethoxysilane 6.075 g

4-hydroxyphenylvinyl ketone 2.025 g

? 4.725 g glycidyl methacrylate

2,2'-azobis (2-methylpropionate) dimethyl 2.025 g

The obtained reaction liquid was cooled to room temperature, and the 33.3 weight% solution of the alkali-soluble polymer (C2) which does not contain 2,2'- azobis (2-methylpropionate) dimethyl was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of alkali-soluble polymer (C2) was 3,500.

Synthesis Example 5 Synthesis of Alkali-Soluble Polymer (C3)

The mixed solution was prepared using the following component by the following weight, and it superposed | polymerized similarly to the synthesis example 1.

Diethylene glycol methyl ethyl ether 11.0 g

Α-Butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane of formula (3-1)

0.675 g

N-cyclohexylmaleimide 4.725 g

4.725 g of dicyclopentanyl methacrylate

3.375 g of methacrylic acid

2,2'-azobis (2-methylpropionate) dimethyl 2.025 g

The obtained reaction liquid was cooled to room temperature, and the 33.3 weight% solution of the alkali-soluble polymer (C3) which did not contain 2,2'- azobis (2-methylpropionate) dimethyl was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of alkali-soluble polymer (C3) was 2,800.

Synthesis Example 6 Synthesis of Alkali-Soluble Polymer (C4)

The mixed solution was prepared by using the following ingredients in the following weights,

The polymerization was carried out in the same manner as in Synthesis example 1.

Diethylene glycol methyl ethyl ether 11.0 g

N-cyclohexylmaleimide 4.725 g

5.400 g of dicyclopentanyl methacrylate

3.375 g of methacrylic acid

2,2'-azobis (2-methylpropionate) dimethyl 2.025 g

The obtained reaction liquid was cooled to room temperature, and the 33.3 weight% solution of the alkali-soluble polymer (C4) which does not contain 2,2'- azobis (2-methylpropionate) dimethyl was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of alkali-soluble polymer (C4) was 2,800.

Comparative Synthesis Example 1 Synthesis of Polymer (D1) Containing a Siloxane Structure

The above-mentioned mixed solution was prepared using the following components by the following weight, and it carried out similarly to the synthesis example 1 except having made the temperature of the solvent in the 4-neck flask at the time of dripping of the mixed solution, and in subsequent reaction to 90 degreeC. The polymerization was carried out.

Diethylene glycol methyl ethyl ether 11.0 g

3-Methylacryloxypropyltrimethoxysilane 6.75 g

4-hydroxyphenylvinyl ketone 1.35 g

5.40 g glycidyl methacrylate

2,2'-azobis (2-methylpropionate) dimethyl 2.025 g

The obtained reaction liquid was cooled to room temperature, and the 33.3 weight% solution of the polymer (D1) containing the siloxane structure which did not contain 2,2'- azobis (2-methylpropionate) dimethyl was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (D1) containing a siloxane structure was 2,700.

Example 1

[Preparation of Positive Photosensitive Composition]

4,4 '-[1- [4- [1- [4-hydroxy which is a copolymer (A1) obtained in the synthesis example 1, the copolymer (C4) obtained in the synthesis example 6, and a 1, 2- quinonediazide compound Phenyl] -1-methylethyl] phenyl] ethylidene] biscondensate with 1,2-naphthoquinonediazide-5-sulfonic acid chloride (average esterification rate 58%, hereinafter referred to as "PAD"), as an additive BYK344, a silicone-based surfactant (trade name: BIC Chemie Japan Co., Ltd., hereinafter abbreviated as `` BYK344 ''), was mixed and dissolved in diethylene glycol methylethyl ether as a solvent in the following weight, and the solid content concentration was 35% by weight Photosensitive composition 1 was obtained.

0.451 g of diethylene glycol methyl ethyl ether

3.00 g of a 33.3 wt% solution of polymer (A1) comprising a siloxane structure

3.00 g of a 33.3 wt% solution of an alkali soluble polymer (C4)

? PAD 0.400g

? BYK344 0.007g

[Evaluation Method of Positive Photosensitive Composition]

1) Formation method of pattern type transparent film

The photosensitive composition 1 was spin-coated at 600 rpm for 10 seconds on the glass substrate, and dried for 2 minutes on a 100 degreeC hotplate. The substrate was cut in the air with a photomask for forming a hole pattern and cut 350 nm or less of light through a wavelength cut filter using Proximity Exposure Machine TME-150PRC manufactured by Topcon Corporation. The i-line was taken out and exposed to 100 micrometers of exposure gaps. The exposure amount was 150 mJ / cm ² . The exposure amount was measured by the integrated photometer UIT-102 and the light receiver UVD-365PD manufactured by Ushio Electric Co., Ltd. The glass substrate after exposure was dipping for 60 second with 0.4weight% of tetramethylammonium hydroxide aqueous solution, and the resin composition of the exposure part was removed. The board | substrate after image development was wash | cleaned for 60 seconds with pure water, and it dried for 2 minutes on the 100 degreeC hotplate. After exposing the whole surface to 300 mJ / cm <^2> without using a photomask with this board | substrate, the board | substrate was post-baked at 230 degreeC in oven for 30 minutes, and the patterned transparent film with a film thickness of 3 micrometers was formed.

2) Residual rate after development

The film thickness was measured before and after development and calculated according to the following formula.

(Film thickness after development / film thickness before development) * 100 (%)

The film thickness was measured in three places using the stylus type film thickness gauge P-15 by KLA-Tencor Japan Co., Ltd., and made it the average value.

3) resolution

The board | substrate of the patterned transparent film obtained by said 1) was observed by 400 times with the optical microscope, and the mask size which glass was exposed at the bottom of a hole pattern was confirmed. When the hole pattern was not formed, it was set as defect (NG).

4) Adhesion

The board | substrate of the patterned transparent film obtained by said 1) was evaluated by the lattice peeling test (crosscutting test). Evaluation was carried out by the adhesive tape [Sumitomo 3M Co., Ltd. product, "polyester tape No. 56: adhesive force; 5.5 N / cm "] and the number of scales of the remaining lattice after tape peeling was shown.

5) UV / O ₃ ashing treatment

A transparent film was formed in the same manner as in 1) above except that no pattern was formed, that is, no exposure using a photomask was performed, and the obtained transparent film was treated under the following conditions with the following apparatus.

? Device: PL2003N-12 (Sen Special Light Source Co., Ltd., PHOTO SURFACE PROCESSOR)

Each setting value: UV wavelength (254 nm), exposure amount (525 mJ / cm ² )

And the exposure amount of 254 nm was measured using UVC-254 which is a custom product.

6) contact angle

The contact angle of pure water in the transparent film before and after the UV / O ₃ ashing treatment of 5) was measured under a 25 ° C. environment using Drop Master 500 manufactured by Kyowa Interface Chemical Co., Ltd. The value after 1 second of pure deposition was taken as the contact angle value.

Table 1 shows the composition obtained by the composition of the photosensitive composition 1 and the above-mentioned evaluation method.

[Table 1]

[Examples 2-5 and Comparative Examples 1-4]

Photosensitive compositions 2-5 and comparative soluble compositions 1-4 which were solutions of a polymer were prepared and evaluated similarly to Example 1 by the combination and the quantity shown in Table 1. Table 1 shows the compositions and evaluation results of these photosensitive compositions.

As is apparent from Table 1, Examples 1? 5 In Comparative Example 1? Than 4, UV / O ₃ ashing treatment after it is possible to obtain a high contact angle.

As explained above, the photosensitive composition of this invention can be handled by the existing photolithographic method, and the obtained cured film has sufficient liquid repellency as a bank material. Further, the circuit board manufacturing, and it is performed to inhibit the UV / O ₃ ashing lowering of liquid repellency of the bank material surface due to the wetting to improve the process, etc., the process and maintaining sufficient liquid repellency after.

Claims (13)

In the photosensitive composition containing the polymer (A) containing a siloxane structure, and a 1, 2- quinonediazide compound (B),
The polymer (A) containing a siloxane structure is an alkali-soluble radically polymerizable monomer having alkali solubility and radical polymerizability which imparts alkali solubility to the siloxane compound represented by the formula (1) and the polymer (A). A photosensitive composition, which is a radical polymer of a monomer comprising:
[Formula 1]

In formula (1), each of R ^{1 to} R ⁴ independently represents hydrogen or alkyl having 1 to 30 carbons in which any hydrogen may be substituted with fluorine and any methylene that is not continuous may be replaced with oxygen. , A ¹ and A ² each represent a radical polymerizable functional group, and n represents an integer of 1 to 1,000. The method of claim 1,
The alkali-soluble radically polymerizable monomer includes at least one member selected from the group consisting of a radical polymerizable monomer having an unsaturated carboxylic acid, a radical polymerizable monomer having an unsaturated carboxylic anhydride, and a radical polymerizable monomer having a phenolic hydroxyl group, Photosensitive composition. The method according to claim 1 or 2,
The photosensitive composition in which an alkali-soluble radically polymerizable monomer contains the radical polymer monomer represented by Formula (2):
(2)

In formula (2), R <^5> -R <^7> represents hydrogen or C1-C3 alkyl which arbitrary hydrogen may substitute by fluorine, respectively, and R <^8> -R <^12> is hydrogen; halogen; -CN; -CF _3; -OCF ₃ ; Hydroxyl group; Alkyl having 1 to 5 carbons in which any methylene may be substituted with —COO—, —OCO—, —CO—, and in which any hydrogen may be substituted with halogen; Or alkoxy having 1 to 5 carbon atoms in which any hydrogen may be substituted with halogen, provided that at least one of R ^{8 to} R ¹² is a hydroxyl group. 4. The method according to any one of claims 1 to 3,
The photosensitive composition whose polymer (A) containing a siloxane structure is a radical polymer of the monomer which further contains other radically polymerizable monomers other than the siloxane compound represented by Formula (1), and an alkali-soluble radically polymerizable monomer. The method of claim 4, wherein
The said photosensitive composition in which the said other radically polymerizable monomer contains the siloxane compound represented by Formula (3):
(3)

In formula (3), R <^13> -R <^17> respectively independently represents the C1-C30 alkyl or the C1-C30 which arbitrary hydrogen may be substituted by fluorine, and arbitrary methylene may be substituted by oxygen. 500 tri (alkyl / alkoxy) siloxy is represented, A ³ represents a radical polymerizable functional group, and n represents an integer of 0 to 1,000. The method of claim 5,
The said other radically polymerizable monomer is a photosensitive composition whose n is a siloxane compound represented by Formula (3) which is 0. The method of claim 6,
A photosensitive composition in which R ^{13 to} R ¹⁵ in the formula (3) are each represented by the following formula (5):
[Chemical Formula 4]

In formula (5), R <^21> -R <^23> is respectively independently hydrogen, C1-C20 alkyl, or C1-C20 alkoxy (However, at least 1 of terminal R <^21> -R <^23> is the said alkyl or M) represents an integer of 1 to 500. 8. The method according to any one of claims 4 to 7,
The photosensitive composition in which the said other radically polymerizable monomer contains a (meth) acrylic acid derivative. The method according to any one of claims 1 to 8,
It is a radical polymer of monomers other than the siloxane compound represented by Formula (1), and further contains the alkali-soluble polymer (C) which has alkali solubility. 10. The method of claim 9,
Monomer which an alkali-soluble polymer (C) contains 1 or more types chosen from the group which consists of a radically polymerizable monomer which has unsaturated carboxylic acid, the radically polymerizable monomer which has unsaturated carboxylic anhydride, and the radically polymerizable monomer which has phenolic hydroxyl group. The photosensitive composition which is a radical polymer of. The method according to any one of claims 1 to 10,
The photosensitive composition containing a solvent further. The cured film obtained by baking the film | membrane of the photosensitive composition of any one of Claims 1-11. The display element which has a cured film of Claim 12.