KR20100044700A - Positive photosensitive composition, cured film obtained therefrom, and display element which has the cured film - Google Patents

Abstract

PURPOSE: A positive photosensitive composition, a cured film obtained therefrom, and a display element including thereof are provided to obtain a cured film with superior water repelling property and pattern generating property. CONSTITUTION: A positive photosensitive composition contains a polymer including a siloxane structure and a 1,2- quinonediazide compound. The polymer includes a siloxane compound marked as the chemical formula 1 and a radical polymer monomer marked as the chemical formula 3. In the chemical formula 1, R1 and R2 refer to alkyl with the carbon number of 3~18, aryl with the carbon number of 6~40, or arylalkyl with the carbon number of 7~40 formed with alkylene capable of substituting methylene with oxygen or cycloalkenylene.

Description

Positive photosensitive composition, the cured film obtained from this composition, and the display element which has this cured film {POSITIVE 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, , Japanese Patent Application Publication No. 2004-287232). The patterned transparent film is a negative photosensitive material which forms a patterned film by applying a photocurable polymer composition to a substrate, irradiating the coating film with light according to a pattern, and washing and removing the uncured and uncured film. And a positive photosensitive material which forms a patterned film by removing the film irradiated with light and solubilized in an alkaline developer. Thus, many photocurable polymer compositions and photosensitive compositions for forming a patterned transparent film have also been proposed (see, for example, Japanese Patent Application Laid-open No. 2001-261761).

On the other hand, in recent years, various patterning by the inkjet method is proposed (for example, refer Unexamined-Japanese-Patent No. 10-12377). In addition, in the patterning by the inkjet method, in order to perform precise inkjet patterning, the partition (bank material) between pixels may be formed before application | coating by the inkjet method. This bank material can be formed as a film patterned by the well-known method using the photocurable polymer composition and photosensitive composition which were mentioned above. Such a bank material is required to have a property that the liquid substance ejected from the head nozzle of the ink jet apparatus does not adhere, that is, ink repellency (for example, Japanese Patent Application Laid-open No. Hei 11-281815 and Japanese Patent). See Application Publication No. 2004-149699. As such, the use of the photocurable polymer composition and the photosensitive composition is expanding not only to the materials constituting the layers in the display elements described above, but also to films for an auxiliary role in the manufacture of the display elements, with the expansion of such applications. In the photocurable polymer composition and the photosensitive composition, various performances are required from the prior art.

This invention makes it a subject to provide the positive photosensitive composition which can form the cured film excellent in liquid repellency. 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 This inventor discovered that the cured film excellent in liquid repellency can be obtained especially by using the polymer which copolymerized the monomer containing siloxane for the photosensitive composition as a result of research and research in order to solve the said problem. The invention was completed.

[1] A photosensitive composition containing a polymer (A) containing a siloxane structure and a 1,2-quinonediazide compound (B), wherein the polymer (A) containing the siloxane structure is represented by the following formula (1) A photosensitive composition which is a radical polymer of the monomer containing the siloxane compound represented and the radical polymer monomer represented by following formula (2):

In said formula (1), R <^1> and R <^2> is hydrogen; Arbitrary hydrogen may be substituted with fluorine, and arbitrary methylene may be substituted with oxygen or cycloalkylene having 3 to 18 carbon atoms; C6-C40 aryl which may be substituted by fluorine, a C1-C20 alkyl group, or a C1-C20 alkoxy group; Or an arylalkyl having 7 to 40 carbon atoms composed of the above-mentioned aryl and any alkylene optionally substituted with hydrogen and optionally methylene may be substituted with oxygen or the cycloalkylene;

R ³ and R ⁴ are each independently hydrogen; Arbitrary hydrogen may be substituted with fluorine, arbitrary methylene may be substituted with oxygen or cycloalkylene having 3 to 18 carbon atoms; C6-C40 aryl which may be substituted by fluorine, a C1-C20 alkyl group, or a C1-C20 alkoxy group; Or arylalkyl having 7 to 40 carbon atoms composed of the above-mentioned aryl and alkylene in which any hydrogen is substituted with fluorine and any methylene may be substituted with oxygen or the cycloalkylene; Or group represented by following formula (3) is shown,

R <^5> is C1-C20 linear or branched alkyl in which arbitrary hydrogen may be substituted by fluorine, and arbitrary methylene may be substituted by oxygen; Aryl having 6 to 20 carbon atoms, in which any hydrogen may be substituted with fluorine; Or arylalkyl having 7 to 20 carbon atoms, in which any hydrogen in aryl may be substituted with fluorine,

A ¹ represents a radical polymerizable functional group,

n represents the integer of 1-1,000.

However, when n is 1, R <^3> and R <^4> represents group of following formula (3), respectively.

In said formula (3), R <^6> and R <^7> is respectively independently hydrogen; Arbitrary hydrogen may be substituted with fluorine, and arbitrary methylene may be substituted with oxygen or cycloalkylene having 3 to 18 carbon atoms; C6-C40 aryl which may be substituted by fluorine, a C1-C20 alkyl group, or a C1-C20 alkoxy group; Or an arylalkyl having 7 to 40 carbon atoms composed of the aryl and alkylene optionally hydrogen may be substituted with fluorine and optionally methylene may be substituted with oxygen or the cycloalkylene;

R <^8> is C1-C20 linear or branched alkyl in which arbitrary hydrogen may be substituted by fluorine, and arbitrary methylene may be substituted by oxygen; Aryl having 6 to 20 carbon atoms, in which any hydrogen may be substituted with fluorine; Or arylalkyl having 7 to 20 carbon atoms, in which any hydrogen in aryl may be substituted with fluorine,

m represents the integer of 1-500.

In said formula (2), R <^9> -R <^11> represents hydrogen or C1-C3 alkyl which arbitrary hydrogen may be substituted by fluorine, respectively, R <^12> -R <^16> is hydrogen; halogen; -CN; -CF ₃ ; -OCF ₃ ; Hydroxyl group; Alkyl having 1 to 5 carbon atoms in which any methylene may be substituted with —COO—, —OCO—, —CO—, and optionally hydrogen may be substituted with halogen; Or C1-C5 alkoxy which arbitrary hydrogen may be substituted by halogen.

Provided that at least one of R ¹² to R ¹⁶ is a hydroxyl group.

[2] The polymer (A) containing the siloxane structure is a radical polymer of a monomer further comprising a radical polymerizable monomer other than the compound represented by the formulas (1) and (2). The photosensitive composition described.

[3] The photosensitive composition as described in [2], in which the other radical polymerizable monomer is at least one selected from the group consisting of hydroxy (meth) acrylate, (meth) acrylic acid derivative, and styrene derivative having a phenolic hydroxyl group.

[4] The photosensitive composition according to any one of [1] to [3], further containing an alkali-soluble polymer (C) having alkali solubility.

[5] The alkali-soluble polymer (C) is at least one 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 [4] which is a radical polymer of the monomer to contain.

[6] The photosensitive composition according to any one of [1] to [5], further containing a solvent.

[7] A cured film obtained by baking the film of the photosensitive composition according to any one of [1] to [6].

[8] A display element having a cured film according to [7].

Since the photosensitive composition of this invention is a radical polymer of the monomer containing the siloxane compound represented by Formula (1) and the radical polymer monomer represented by Formula (2), it is hardened | cured excellent in liquid repellency by applying it to a positive type photoresist. A film can be formed.

In addition to the above-described high liquid repellency, the photosensitive composition of the present invention has sufficient performance as a material of a photoresist also with respect to typical characteristics required as a material of a photoresist such as developability, chemical resistance, and adhesion. . 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.

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 the siloxane structure may be one kind or two or more kinds, and the 1,2-quinonediazide compound (B) may also be one kind or two or more kinds. The said photosensitive composition is obtained by mixing the 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 the siloxane structure is a siloxane compound represented by the following formula (1) having a linear siloxane structure having a silicon number of 3 or more and a radical polymerizable functional group (hereinafter referred to as "radically polymerizable monomer (a-1) It is a radical polymer of the monomer containing "and" and the radical polymer monomer represented by following formula (2) which is a vinyl ketone which has a phenolic hydroxyl group (henceforth a "radical polymerizable monomer (a-2)"). .

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

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

The said radically polymerizable monomer (a-1) is a compound which has a linear siloxane structure of 3 or more silicon numbers, and a radically polymerizable functional group, and is represented by following formula (1). In following formula (1), R <^3> and R <^4> can contain the group represented by following formula (3).

R ¹ and R ² in the formula (1) and R ⁶ and R ⁷ in the formula (3) are each independently hydrogen; Arbitrary hydrogen may be substituted with fluorine, arbitrary methylene may be substituted with oxygen or cycloalkylene having 3 to 18 carbon atoms; C6-C40 aryl which may be substituted by fluorine, a C1-C20 alkyl group, or a C1-C20 alkoxy group; Or an arylalkyl having 7 to 40 carbon atoms composed of alkylene in which the aryl and any hydrogen may be substituted with fluoro and any methylene may be substituted with oxygen or the cycloalkylene. R ¹ , R ² , R ⁶ and R ^{7 each} have 1 to 30 carbon atoms in consideration of the ease of obtaining the radical polymerization monomer (a-1) by synthesis, and optionally hydrogen is substituted with fluorine. It may be sufficient, and it is preferable that arbitrary methylene is alkyl which may be substituted by oxygen or the said cycloalkylene, and it is more preferable that it is C1-C30 alkyl.

In said formula (1), R <^3> and R <^4> is respectively independently hydrogen; Arbitrary hydrogen may be substituted with fluorine, and arbitrary methylene may be substituted with oxygen or cycloalkylene having 3 to 18 carbon atoms; C6-C40 aryl which may be substituted by fluorine, a C1-C20 alkyl group, or a C1-C20 alkoxy group; Or arylalkyl having 7 to 40 carbon atoms composed of alkylene in which the aryl and any hydrogen may be substituted with fluorine and any methylene may be substituted with oxygen or the cycloalkylene; Or the group represented by Formula (3) is shown. However, when n in said Formula (1) is 1, R <^3> and R <^4> respectively represents group represented by said Formula (3). When n in the said Formula (1) is 2 or more, R <^3> and R <^4> has C1-C30, considering the ease in obtaining a radical polymerization monomer (a-1) by synthesis | combination, and arbitrary Hydrogen may be substituted with fluorine, it is preferable that arbitrary methylene may be substituted by oxygen or the said cycloalkylene, and it is more preferable that it is alkyl of 1-30 carbon atoms.

R <^5> in said Formula (1) and R <^8> in said Formula (3) are respectively C1-C20 linear which arbitrary hydrogen may be substituted by fluorine, and arbitrary methylene may be substituted by oxygen. Chain or branched alkyl; Aryl having 6 to 20 carbon atoms, in which any hydrogen may be substituted with fluorine; Or arylalkyl having 7 to 20 carbon atoms, in which any hydrogen in aryl may be substituted with fluorine. In consideration of the ease of obtaining the radically polymerized monomer (a-1) by synthesis, R ⁵ and R ⁸ may be optionally substituted with hydrogen and optionally methylene may be substituted with oxygen. It is preferable that it is C1-C20 linear or branched alkyl, and it is more preferable that it is C1-C20 linear alkyl.

In said formula (1), A <^1> represents a radically polymerizable functional group. As said radically polymerizable functional group, group which has a structure which can be radically polymerized in a radically polymerizable monomer (a-1) can be used. As such a radically polymerizable functional group, a well-known radically polymerizable functional group is mentioned, For example, vinyl, vinylene, vinylidene, (meth) acryloyl, and styryl are mentioned.

In said formula (1), n represents the integer of 1-1,000. When n is 2 or more, it is preferable that it is 2-500 from a viewpoint of obtaining favorable alkali developability, It is more preferable that it is 5-300, It is further more preferable that it is 10-150.

In said formula (3), m shows the integer of 1-500. It is preferable that it is 2-500 from a viewpoint of obtaining favorable alkali developability, It is more preferable that it is 5-300, It is still more preferable that it is 10-150.

As said radically polymerizable monomer (a-1), the monomethacryl terminal dimethylsiloxane represented by following formula (1-1), and methacryloyloxypropyl represented by following formula (1-2), for example are shown. -Tris-trimethylsiloxysilane. The use of the monomethacryl terminal-dimethylsiloxane and methacryloyloxypropyl-tris-trimethylsiloxysilane in the radically polymerizable monomer (a-1) has a high initial transparency and is suitable for firing at a high temperature. Almost no deterioration of the transparency due to the transparency, the solubility in the aqueous alkali solution at the time of development is high (that is, the developability is high), and the patterned transparent film can be easily obtained, and also the solvent resistance, high water resistance, acid resistance, alkali resistance, heat resistance It is preferable from a viewpoint of obtaining the photosensitive composition or cured film with high adhesiveness with a base part.

Some commercially available as said radically polymerizable monomer (a-1). As a compound represented by Formula (1-1), silaprene FM0711 (brand name Tosoh Co., Ltd. product) is mentioned, for example. Examples of the compound represented by the formula (1-2) include silaprene TM0701T (trade name, manufactured by Tosso Co., Ltd.).

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

The said radically polymerizable monomer (a-2) is vinyl ketone which has a phenolic hydroxyl group, and is represented by following formula (2).

In said formula (2), R <^9> -R <^11> represents hydrogen or C1-C3 alkyl which arbitrary hydrogen may be substituted by fluorine, respectively, R <^12> -R <^16> is hydrogen; halogen; -CN; -CF ₃ ; -OCF ₃ ; Hydroxyl group; Alkyl having 1 to 5 carbon atoms in which any methylene may be substituted with —COO—, —OCO—, —CO—, and optionally hydrogen may be substituted with halogen; Or C1-C5 alkoxy which arbitrary hydrogen may be substituted by halogen. Provided that at least one of R ¹² to R ¹⁶ is a hydroxyl group. It is preferable that R <^12> -R <^16> except R <^9> -R <^11> and hydroxyl group is hydrogen from a viewpoint of improving alkali solubility.

As said radically polymerizable monomer (a-2), 4-hydroxyphenyl vinyl ketone is mentioned, for example.

The said radically polymerizable monomer (a-2) can be synthesize | combined and obtained by a well-known method, or can be obtained as a commercial item. For example, 4-hydroxyphenyl vinyl ketone is, as described in Japanese Patent Application Laid-open No. 2004-189715, by adding aluminum chloride to a methylene chloride solution of 2-chloroethyl 4-methoxyphenyl ketone, The obtained mixture can be obtained by refluxing, cooling, extracting the organic phase with ethyl acetate, extracting the obtained organic phase with aqueous NaOH solution, making it acidic with hydrochloric acid, and then extracting with ethyl acetate again.

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

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

As said radically polymerizable monomer (a-3), for example, it contains a radically polymerizable monomer containing an epoxy, a radically polymerizable monomer containing an unsaturated carboxylic acid, a radically polymerizable monomer containing an unsaturated carboxylic anhydride, and a phenolic hydroxyl group. And a radically polymerizable monomer containing a radically polymerizable monomer, an N-substituted maleimide, and dicyclopentanyl.

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

Moreover, as a radically polymerizable monomer containing the said unsaturated carboxylic acid, the radically polymerizable monomer containing an unsaturated carboxylic acid anhydride, and the radically polymerizable monomer containing a phenolic hydroxyl group, (meth) acrylic acid, maleic anhydride, And hydroxy styrene. These are preferable from the viewpoint of improving alkali solubility of the polymer (A) which has a siloxane structure, and are especially chosen from the group which consists of a hydroxy (meth) acrylate, a (meth) acrylic acid derivative, and a styrene derivative which has a phenolic hydroxyl group. It is preferred that there is at least one.

The (meth) acrylic acid derivative may be a derivative having a polymerizable double bond that (meth) acrylic acid has. Examples of the (meth) acrylic acid derivatives include 2-dodecanoyloxyethyl acrylate, 2-dodecanoyloxyethyl methacrylate, 2-dodecanoyloxy-1-methylethyl acrylate, and 2-dode Canoxy-1-methylethyl methacrylate, 2-dodecanoyloxypropyl acrylate, 2-dodecanoyloxypropyl methacrylate, 2-octadecanoyloxyethyl acrylate, 2-octadecanoyloxyethyl meth Acrylate, 2-octadecanoyloxy-1-methylethylacrylate, 2-octadecanoyloxy-1-methyl methacrylate, 2-octadecanoyloxypropylacrylate, 2-octadecanoyloxypropylmethacryl 2-docosanoyloxyethyl acrylate, 2-docosanoyloxyethyl methacrylate 2-docosanoyloxy-1-methylethyl acrylate, 2-docosanoyloxy-1-methylethyl methacrylate , 2-docosanoyloxypropylacrylate, and 2- Docosanoyloxypropyl methacrylate.

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

The radically polymerizable monomer (a-3) includes one or both of the radically polymerizable monomers containing N-substituted maleimide and dicyclopentanyl from the viewpoint of increasing the heat resistance of the cured film formed from the photosensitive composition. desirable.

As said 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-diethyl phenyl) maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N- (1-anilinonenaph Til-4) maleimide, N- [4- (2-benzoxazolyl) phenyl] maleimide, and N- (9-acridinyl) maleimide.

As a radically polymerizable monomer containing the said dicyclopentanyl, dicyclopentanyl acrylate and dicyclopentanyl methacrylate are mentioned, for example.

The polymer (A) containing the said siloxane structure adds the said radically polymerizable monomer (a-1) and (a-2) and also a radically polymerizable monomer (a-3) as needed, and these are radicals. It is obtained by superposing | polymerizing. This radical polymerization can be performed by a well-known method.

Although the polymerization method of the polymer (A) containing the said siloxane structure is not specifically limited, The 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 to 150 ° C. Although polymerization time is not specifically limited, either, It is the range of 1 to 24 hours normally. In addition, the said polymerization can be performed under any pressure of pressurization, reduced pressure, or atmospheric pressure.

As a solvent used by the said 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. As the solvent, for example, 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, ethyl 3-ethoxypropionate, N, N -Dimethylformamide, acetic acid, and water.

As a polymerization initiator used by the said radical polymerization, the compound which generate | occur | produces a radical by heat, azo initiators, such as azobisisobutyronitrile, and peroxide type initiators, such as benzoyl peroxide, are mentioned, for example. 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 addition, in the said 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, in which 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 From the viewpoint of minimizing the development residue, the weight average molecular weight is more preferably 1,500 to 50,000, and even more preferably 2,000 to 20,000.

The said weight average molecular weight can be calculated | required by GPC analysis based on polyethylene oxide, For example, polyethylene oxide (for example, TSK standard by Tosoh Corporation) whose molecular weight is 1,000-510,000 is used as a standard polyethylene oxide. And it can measure by GPC analysis of the conditions using Shodex KD-806M (made by Showa Denko Co., Ltd.) for a column, and using DMF as a mobile phase.

And the monomer of the polymer (A) containing the said siloxane structure can be estimated by measuring the gas produced by thermal decomposition by GC-MS, for example, when thermally decomposing the polymer (A) containing the said siloxane structure. .

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

As said 1,2-quinonediazide compound (B), the compound used as a photosensitizer in the resist field can be used, for example. As said 1, 2- quinone diazide compound (B), For example, ester of a phenol compound and a 1, 2- benzoquinone diazide- 4-sulfonic acid or a 1, 2- benzoquinone diazide- 5-sulfonic acid, Ester of a phenol compound with 1,2-naphthoquinone diazide-4-sulfonic acid or 1,2-naphthoquinone diazide-5-sulfonic acid; a compound in which a hydroxyl group of the phenol compound is substituted with an amino group, and 1,2-benzo Sulfonamide with quinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid, a compound in which a hydroxyl group of a phenol compound is substituted with an amino group, and 1,2-naphthoquinonediazide-4-sulfonic acid or And sulfonamides with 1,2-naphthoquinonediazide-5-sulfonic acid.

As said phenolic compound, 2,3,4- trihydroxy benzophenone, 2,4,6- trihydroxy benzophenone, 2,2 ', 4,4'- tetrahydroxy benzophenone, 2 , 3,3 ', 4-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 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'-tetra methyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol, and 2,2,4-trimethyl-7,2 ', 4' -Trihydroxyflavan is mentioned.

Said 1,2-quinonediazide compound (B) is ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinone diazide-4-sulfonic acid, 2,3,4-trile Ester of hydroxybenzophenone with 1,2-naphthoquinonediazide-5-sulfonic acid, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl ] Ethylidene] bisphenol and ester of 1,2-naphthoquinone diazide-4-sulfonic acid, and 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl It is preferable at least one selected from the group consisting of esters of] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid from the viewpoint of increasing the transparency of the photosensitive composition.

1-3. Other ingredients

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

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

The photosensitive composition further contains an alkali-soluble polymer (C), further improving 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 It is preferable from a viewpoint of improving the characteristic of the cured film obtained, such as high heat resistance. The alkali-soluble polymer (C) may be one kind or two or more kinds. In the alkali-soluble polymer (C), "alkali-soluble" means a film having a thickness of 0.01 to 100 µm formed by spin coating of a solution of the alkali-soluble polymer (C) and heating at 120 ° C for 30 minutes, for example, 25 ° C. When it is immersed for 5 minutes in 2.38 weight% tetramethylammonium hydroxide aqueous solution of the grade, and wash | cleaned with pure water, it means that the said film | membrane does not remain.

In the said alkali-soluble polymer (C), 2 or more types of radically polymerizable monomer contained in the said radically polymerizable monomer (a-2) and the said radically polymerizable monomer (a-3) so that the polymer obtained may have alkali solubility. Radical polymers can be used. For example, the various monomers used for the monomer of the said alkali-soluble polymer (C) are a polymer containing a siloxane structure, in order to express the function similar to the monomer in the polymer (A) containing the siloxane structure mentioned above. About the total amount of the monomer in (A) and the monomer in alkali-soluble polymer (C), it can use with content mentioned above in the polymer (A) containing a siloxane structure.

More specifically, the alkali-soluble polymer (C) includes a radical polymerizable monomer having an unsaturated carboxylic acid, a radical polymerizable monomer having an unsaturated carboxylic anhydride, a radical polymerizable monomer having a phenolic hydroxyl group, and a radical polymerizable monomer ( The radical polymer which contains a radically polymerizable monomer other than a-1) in a monomer can be used. In an alkali-soluble polymer (C), the said radically polymerizable monomer (a-2) can be used as a radically polymerizable monomer which has the said phenolic hydroxyl group. The alkali of the said photosensitive composition is that the monomer of an alkali-soluble polymer (C) contains 1 or more types chosen from the group which consists of (meth) acrylic acid, maleic anhydride, hydroxy styrene, and 4-hydroxyphenyl vinyl ketone. It is preferable from a viewpoint of improving solubility.

Even if the monomer of the said alkali-soluble polymer (C) further contains other radically polymerizable monomers, such as the radically polymerizable monomer containing the above-mentioned N-substituted maleimide and dicyclopentanyl in the range from which the effect of this invention is fully acquired. do.

As for the weight average molecular weight of the said alkali-soluble polymer (C), similar to the polymer (A) containing the said siloxane structure, developing time until an exposure part melt | dissolves with alkaline developing solution is suitable, and also It is preferable from a viewpoint that the surface of a film does not become rough easily at the time of image development, It is more preferable from a viewpoint that development residue is minimized, It is still more preferable that it is 2,000-20,000. The weight average molecular weight of the said alkali-soluble polymer (C) can be calculated | required by GPC analysis on the same conditions as the polymer (A) containing the said siloxane structure, for example.

The said alkali-soluble polymer (C) can be obtained according to the polymerization method similar to the polymer (A) containing the said siloxane structure, for example. In addition, the said monomer of the said alkali-soluble polymer (C) is similar to the polymer (A) containing the said siloxane structure, for example, by measuring the gas produced by thermal decomposition by GC-MS when thermally decomposing an alkali-soluble polymer. It can be estimated.

1-3-2. solvent

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

Examples of the solvent having a boiling point of 100 ° C to 300 ° C include water, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methoxyacetate, ethyl methoxyacetate and methoxy. Butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 Ethyl ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate Ethyl pyruvate, propyl pyruvate, methyl acetic acid, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene 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 glycol monobutyl Ethe , Diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, toluene, xylene, γ-butyrolactone, and N, N-dimethylacetamide. have.

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

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 mono At least one selected from the group consisting of butyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethyl lactate and butyl acetate is preferable from the viewpoint of increasing the coating uniformity when forming the film of the 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.

1-3-3. additive

It is preferable that the said photosensitive composition further contains an additive from a viewpoint of further improving the characteristics of the said 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 the said additive. The additive may be one kind or two or more kinds. As such additives, for example, acrylic, styrene, polyethyleneimine or urethane-based polymer dispersants, anionic, cationic, nonionic or fluorine-based surfactants, silicone resin coating improvers, silane coupling agents and the like And alkali solubility promoters such as adhesion improvers, ultraviolet absorbers such as alkoxybenzophenones, anti-aggregation agents such as sodium polyacrylate, thermal crosslinking agents such as epoxy compounds, melamine compounds or bisazide compounds, and organic carboxylic acids.

More specifically, as the additive, for example, Polyflop No. 45, Polyfloor KL-245, Polyfloor No. 75, Polyfloor No. 90, Polyfloor No. 95 (above, all trade names, Kyo) Eisha Chemical Co., Ltd.), Disperbake Disperbyk) 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperb Bake 181, disper bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK344, BYK346 (above, all brand names, BIC Chemie Japan Corporation), KP-341, KP-358, KP-368, KF -96-50CS, KF-50-100CS (above, all brand names, Shin-Etsu Chemical Co., Ltd.), sulfon RSC-101, sulfon RKH-40 (more, all brand names, Seimi Chemical Co., Ltd.) Manufacture), Pgentant 222F, Pgentant 251, FTX-218 (above, all brand names, product made by Neos), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (above, all trade names, manufactured by Mitsubishima Material Co., Ltd.), Megapack F-171, Megapack F-177, Megapack F-475, Megapack R- 08, Megapack R-30 (above, all trade names, manufactured by Dainippon Ink & Chemicals Co., Ltd.), fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkylammonium Iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonic acid salt, polyoxyethylene nonylphenyl ether, Polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethyl 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 sorbitanate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyldiphenyl And ether disulfonates. It is preferable that the said additive is 1 or more types chosen from these.

It is more preferable that the said additive is either or both of a fluorine type surfactant and a silicone resin coating property improving agent from a viewpoint of improving the coating uniformity of the photosensitive composition. More specifically, the additives include fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate and di Glycerine tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate salt, BYK306, BYK344, BYK346, KP-341, KP-358, and KP-368 It is more preferable that it is a kind or more from a viewpoint of raising the application uniformity of the photosensitive composition.

 1-3-4. Polyhydric carboxylic acid

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

1-4. Content of each component in the photosensitive composition

It is preferable that it is 20 to 80 weight%, and, as for content of the polymer (A) containing the siloxane structure in the said photosensitive composition, from the viewpoint of expressing liquid repellency in a cured film, it is more preferable that it is 30 to 70 weight% It is preferable and it is more preferable that it is 40 to 60 weight%.

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

In the said photosensitive composition, when content of the polymer (A) containing the said siloxane structure is made into 100 weight part from a viewpoint which fully expresses the improvement effect of alkali solubility, content of the said alkali-soluble polymer (C) is 20 It is preferable that it is -150 weight part, It is more preferable that it is 50-120 weight part, It is still more preferable that it is 70-100 weight part.

Content of the said solvent in the said photosensitive composition is preferable that content of the total solid in the said photosensitive composition is 5-50 weight% from a viewpoint of improving the uniformity of application | coating of a photosensitive composition, and a viewpoint of safety to a human body. It is more preferable that it is 10 to 40 weight%, and it is still more preferable that it is 15 to 35 weight%.

Content of the said additive in the said photosensitive composition is 100 mass parts of total amounts of the polymer (A) and alkali-soluble polymer (C) containing the said 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 0.01-1 weight part, It is more preferable that it is 0.03-0.7 weight part, It is still more preferable that it is 0.05-0.5 weight part.

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

1-5. Preservation of the Photosensitive Composition

It is preferable to block and store the said photosensitive composition at -30 degreeC-25 degreeC from a viewpoint of stably storing a photosensitive composition, and it is preferable that a storage temperature is -20 degreeC-10 degreeC from a viewpoint of preventing generation of a precipitate. More preferred.

2. Cured film of this invention

The cured film of this invention is obtained by baking the film | membrane of the photosensitive composition of this invention mentioned above. The said photosensitive composition is suitable for forming a transparent cured film, and since it is comparatively high in patterning, it is suitable for forming the insulating film which perforated the small hole of 10 micrometers or less. 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.

The said cured film, such as the said 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 of the said photosensitive composition is formed by apply | coating the said photosensitive composition on substrates, such as glass, by well-known methods, such as spin coating, roll coating, and slit coating. As a preferable coating method, spin coating, roll coating, slit coating is mentioned, for example. As a board | substrate, For example, transparent glass substrates, such as a white plate glass, a blue plate glass, a CRT blue plate glass, a polycarbonate, a polyether sulfone, polyester, an acrylic resin, a vinyl chloride resin, and an aromatic polyamide resin And metal substrates such as synthetic resin sheets such as polyamideimide and polyimide, films or substrates, aluminum plates, copper plates, nickel plates, and stainless plates, as well as semiconductor substrates having ceramic plates and photoelectric conversion elements. . 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 | membrane of the said photosensitive composition is dried. The film of the photosensitive composition is dried by, for example, heating the substrate having the film of the photosensitive composition with a hot plate or oven. Usually, it dries for 1 to 5 minutes at 60-120 degreeC.

Subsequently, the dried film of the photosensitive composition is irradiated with radiation through a mask having a desired pattern shape. Irradiation of the radiation to the film of the said photosensitive composition is performed by irradiating an ultraviolet-ray through the mask to the film of the said photosensitive composition dried on the board | substrate, for example. Irradiation conditions are suitable based on the kind of photosensitive agent in a photosensitive composition, for example, since the said photosensitive composition contains a 1, 2- quinonediazide compound (B), 5-1000 mJ / cm <2> is suitable for i line | wire. On the other hand, when forming the cured film which does not have a pattern, such a radiation irradiation process is unnecessary.

Subsequently, the film of the said photosensitive composition irradiated with radiation is developed by washing with a developing solution. 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 part to which the radiation in the said film | membrane irradiated melt | dissolves in a developing solution quickly. The developing method is not particularly limited, and any known method such as dipping development, paddle development, shower development, or the like can be used.

The developer is preferably an alkaline solution. As the developer, 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 hydroxide. Potassium. As a preferable developing solution, More specifically, the aqueous solution of organic alkalis, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and 2-hydroxyethyl trimethylammonium hydroxide, and inorganic alkalis, such as sodium carbonate, sodium hydroxide, or potassium hydroxide, Can be mentioned.

To the developing solution, methanol, ethanol, or a surfactant may be added for the purpose of reducing the development residue and the suitability of the pattern shape. As the surfactant, for example, a surfactant selected from anionic, cationic and nonionic systems can be used. Among these, the addition of nonionic polyoxyethylene alkyl ether is particularly preferable from the viewpoint of increasing the 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 applied to the entire surface of the cleaned membrane. By irradiation of this radiation, the residual 1,2-quinonediazide compound (B) is inactivated. Irradiation of this radiation is performed by irradiating the said film | membrane with the ultraviolet-ray whose intensity is 100-1,000 mJ / cm <2>, for example, when radiation is an ultraviolet-ray.

Subsequently, the film irradiated with radiation is fired to obtain a cured film. Baking of this film is performed by heating the board | substrate which has the said film, for example at 180-250 degreeC for 10 to 120 minutes. According to such a process, the said 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. In addition, a transparent electrode may be formed on the insulating film, and patterned by etching, followed by formation of a film for performing an alignment process. Since the said insulating film has high sputtering resistance, even if a transparent electrode is formed, wrinkles do not generate | occur | produce 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 said cured film in the said display element, the bulk film for preventing a liquid from adhering around a transparent film, an insulating film, and a pattern is mentioned, for example.

The said display element has the same structure as a well-known display element except having used the said cured film for the above-mentioned use, and can manufacture it similarly to a well-known display element. The display element is, for example, press-bonding an element substrate having a cured film patterned on the substrate as described above, and a color filter substrate serving as an opposing substrate in accordance with a display position previously given to each substrate, and then pressing It heat-processes, combines other members other than the said board | substrate, injects a liquid crystal between the opposing board | substrates, and seals an injection hole, and it manufactures as a liquid crystal display element.

In manufacture of the said liquid crystal display element, sealing of a liquid crystal can also be performed by spraying a liquid crystal on the said element substrate, overlapping an element substrate and a color filter substrate, and sealing so that a liquid crystal may not leak. The display element may be a liquid crystal display element produced in this way.

The said liquid crystal, ie, a liquid crystal compound and the composition containing it, is not specifically limited, Arbitrary liquid crystal compounds and a liquid crystal composition 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 base portion, and the like which are generally required for patterned transparent films and insulating films. In addition to having properties, a cured film excellent in liquid repellency can be formed.

Since the cured film of this invention is formed from the said photosensitive composition, surface roughness does not generate | occur | produce easily even after processing, such as immersion, contact, and heat processing, such as a solvent, an acid, and alkaline solution. Therefore, the display element of this invention has a high transmittance | permeability of the light in the said cured film, and can obtain a high display quality.

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

EXAMPLE

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

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

In a four-necked flask with a stirrer, monomethacryl terminal-dimethylsiloxane represented by the following formula (1-1) as a diethylene glycol methyl ethyl ether and a radically polymerizable monomer (a-1) as a polymerization solvent (Chipso, Inc.) Preparation, FM0711, number average molecular weight: 1,000, 3-methacryloxypropyltrimethoxysilane, 4-hydroxyphenylvinylketone as a radical polymerizable monomer (a-2), and glycidyl methacrylate, as a polymerization initiator 2,2'- azobis (isolactic acid) dimethyl was added to the following weight, and it superposed | polymerized by heating at 90 degreeC polymerization temperature for 2 hours.

Diethylene glycol methyl ethyl ether 67.5 g

Monomethacryl terminal-dimethylsiloxane 1.688 g

15.188 g of 3-methacryloxypropyltrimethoxysilane

4-hydroxyphenylvinyl ketone 3.375 g

Glycidyl methacrylate 13.5 g

2,2'-azobis (isolactic acid) dimethyl 5.063 g

The obtained reaction liquid was cooled to room temperature and the polymer (A1) containing a siloxane structure was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polyethylene oxide standard). As a result, the weight average molecular weight of the polymer (A1) containing a siloxane structure was 2,200.

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

In the same manner as in Synthesis example 1, the following components were added at the following weight, and polymerization was performed.

Diethylene glycol methyl ethyl ether 27.0 g

4.05 g of methacryloyloxypropyl tris-trimethylsiloxysilane (following formula (1-2))

2.7 g of 3-methacryloxypropyl trimethoxysilane (following formula (4))

4-hydroxyphenylvinyl ketone 1.35 g

Glycidyl methacrylate 5.4 g

2,2'-azobis (isolactic acid) dimethyl 2.025 g

The obtained reaction liquid was cooled to room temperature and the polymer (A2) containing a siloxane structure was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polyethylene oxide standard). As a result, the weight average molecular weight of the polymer (A2) containing a siloxane structure was 3,700.

Synthesis Example 3 Synthesis of Polymer (A3) Containing Siloxane Structure

In the same manner as in Synthesis example 1, the following components were added at the following weight, and polymerization was performed.

Diethylene glycol methyl ethyl ether 27.0 g

Methacryloyloxypropyltristrimethylsiloxysilane 4.05 g

1.35 g of N-cyclohexylmaleimide

4-hydroxyphenylvinyl ketone 2.7 g

Glycidyl methacrylate 5.4 g

0.054 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The obtained reaction liquid was cooled to room temperature and the polymer (A3) containing a siloxane structure was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polyethylene oxide standard). As a result, the weight average molecular weight of the polymer (A3) containing a siloxane structure was 3,600.

Synthesis Example 4 Synthesis of Alkali-Soluble Polymer (C1)

Except having superposed | polymerized by making superposition | polymerization temperature into 110 degreeC, the following component was thrown in the following weight by the method similar to the synthesis example 1, and superposition | polymerization was performed.

Diethylene glycol methyl ethyl ether 54.0 g

N-cyclohexylmaleimide 9.45 g

Dicyclopentanyl methacrylate 10.8 g

6.75 g of methacrylic acid

4.05 g of 2,2'- azobis (2-methylpropionate)

The obtained reaction liquid was cooled to room temperature, and alkali-soluble polymer (C1) was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polyethylene oxide standard). As a result, the weight average molecular weight of alkali-soluble polymer (C1) was 3,800.

Synthesis Example 5 Synthesis of Alkali-Soluble Polymer (C2)

Except having superposed | polymerized by making superposition | polymerization temperature into 110 degreeC, the following component was thrown in the following weight by the method similar to the synthesis example 1, and superposition | polymerization was performed.

Diethylene glycol methyl ethyl ether 54.0 g

9.72 g of N-cyclohexylmaleimide

Dicyclopentanyl methacrylate 9.72 g

Methacrylic acid 7.56 g

4.05 g of 2,2'- azobis (2-methylpropionate)

The obtained reaction liquid was cooled to room temperature, and alkali-soluble polymer (C2) was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polyethylene oxide standard). As a result, the weight average molecular weight of the copolymer (C2) was 3,000.

Comparative Synthesis Example 1 Synthesis of Comparative Polymer (D1)

Except having superposed | polymerized by making superposition | polymerization temperature into 80 degreeC, the following component was thrown in the following weight by the method similar to the synthesis example 1, and superposition | polymerization was performed.

20.0 g of methyl 3-methoxypropionate

Methacrylic acid 2.0 g

Glycidyl methacrylate 4.0 g

2.0 g of 3-ethyl-3- (meth) acryloxymethyloxetane

2.0 g of N-cyclohexylmaleimide

0.5 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The obtained reaction liquid was cooled to room temperature and the comparative polymer (D1) was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polyethylene oxide standard). As a result, the weight average molecular weight of the comparative polymer (D1) was 6,200.

Comparative Synthesis Example 2 Synthesis of Comparative Polymer (D2)

In the same manner as in Comparative Synthesis Example 1, the following components were added at the following weight and polymerization was performed.

20.0 g of methyl 3-methoxypropionate

Methacrylic acid 1.5 g

5.0 g of glycidyl methacrylate

Dicyclopentanyl methacrylate 2.5 g

1.0 g of N-cyclohexylmaleimide

0.5 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The obtained reaction liquid was cooled to room temperature and the comparative polymer (D2) was obtained. A portion of the reaction solution was sampled and the weight average molecular weight was measured by GPC analysis (polyethylene oxide standard). As a result, the weight average molecular weight of the comparative polymer (D2) was 7,900.

Example 1 Preparation of Positive Photosensitive Composition

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethyl, which is a copolymer (A1) or a 1,2-quinonediazide compound obtained in Synthesis Example 1 A condensate of lithium dendene] bisphenol and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (average esterification rate of 58%, hereinafter referred to as "PAD"), manufactured by Big Chemie Japan Co., Ltd. BYK344 (brand name: Big Chemie Japan Co., Ltd., hereafter abbreviated to "BYK344") and diethylene glycol methyl ethyl ether were mixed and dissolved as a solvent at the following weight, and the positive photosensitive composition was obtained.

Diethylene glycol methyl ethyl ether 0.953 g

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

PAD 0.15 g

BYK344 0.009g

[Evaluation Method of Positive Photosensitive Composition] Formation Method of Patterned Film

The positive photosensitive composition synthesized in Example 1 on the glass substrate was spin coated at 600 rpm for 10 seconds, and dried for 2 minutes with a hot plate at 100 ° C. The substrate was subjected to air through a photomask for hole pattern formation, and the light of 350 nm or less was filtered through a wavelength cut filter using TME-150PRC manufactured by Topcon. It removed and exposed at 100 micrometers of exposure gaps. The exposure amount was 150 mJ / cm 2. The exposure amount was measured with a cumulative photometer UIT-102 and a light receiver UVD-365PD manufactured by Ushio Denki Co., Ltd. to obtain 150 mJ / cm 2. The glass substrate after exposure was dipping and developed for 60 second with 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 with the 100 degreeC hotplate. After exposing this board | substrate to the whole surface at 300mJ / cm <2> without passing through a photomask, it post-baked for 30 minutes at 230 degreeC in oven, and formed the patterned transparent film with a film thickness of 3 micrometers. The film thickness measured three places using the stylus type film thickness gauge (alpha) step 200 by KLA-Tencor Japan Co., Ltd., and made the average value into the film thickness.

2) Residual rate after development

The film thickness was measured before and after image development, and it calculated from the following formula.

(Film thickness before development / film thickness before development) × 100 (%)

3) resolution

The board | substrate of the patterned transparent film | membrane after the post-baking obtained in said 1) was observed by 400 times with the optical microscope, and the mask size which glass is exposed at the bottom of a hole pattern was confirmed.

4) Adhesion

The board | substrate of the patterned transparent film obtained by said 1) was evaluated by the checkerboard scale peeling test (cross cut test). Evaluation was represented by the number of the checkerboard scales which remained after peeling of a tape among 100 checkerboard scales of 1 mm square.

5) contact angle

The contact angle of the pure water on the film | membrane after baking was measured in 25 degreeC environment with the DropMaster 500 by the Corporation. Pure water drops were dropped and the value after 1 second was used as the contact angle value.

Table 1 shows the results obtained by the above evaluation method with respect to the positive photosensitive composition and the patterned transparent film obtained in Example 1.

TABLE 1

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Residual rate after development [%] 90 88 87 88 92 92 94 Resolution [μm] 7 7 7 7 7 8 8 Adhesion [-] 100 100 100 100 100 100 100 Contact angle [°] 95 97 93 91 93 66 64

[Example 2]

A 1: 1 mixture of the polymer (A1) containing the siloxane structure obtained in Synthesis Example 1 and the alkali-soluble polymer (C1) obtained in Synthesis Example 4 instead of the polymer (A1) containing the siloxane structure used in Example 1 (weight ratio ), A positive photosensitive composition was produced in the same manner as in Example 1, and a patterned transparent film was formed and evaluated. The results are shown in Table 1.

Example 3

A positive photosensitive composition was prepared in the same manner as in Example 1 except that the polymer (A2) containing the siloxane structure obtained in Synthesis Example 2 was used instead of the polymer (A1) containing the siloxane structure used in Example 1 A type transparent film was formed and evaluated. The results are shown in Table 1.

Example 4

Instead of the polymer (A2) containing the siloxane structure used in Example 3, a 1: 1 mixture of the polymer (A2) containing the siloxane structure obtained in Synthesis Example 2 and the alkali-soluble polymer (C2) obtained in Synthesis Example 5 (weight ratio ), A positive photosensitive composition was produced in the same manner as in Example 1, and a patterned transparent film was formed and evaluated. The results are shown in Table 1.

Example 5

A positive photosensitive composition was prepared in the same manner as in Example 1 except that the polymer (A3) containing the siloxane structure obtained in Synthesis Example 3 was used instead of the polymer (A2) containing the siloxane structure used in Example 4 A type transparent film was formed and evaluated. The results are shown in Table 1.

Comparative Example 1

Instead of the polymer (A1) containing the siloxane structure used in Example 1, a 1: 1 mixture (weight ratio) of the comparative polymer (D1) obtained in Comparative Synthesis Example 1 and the alkali-soluble polymer (C1) obtained in Synthesis Example 4 was used. Except what was used, the positive photosensitive composition was produced like Example 1, the patterned transparent film was formed, and it evaluated. The results are shown in Table 1.

Comparative Example 2

Instead of the polymer (A1) containing the siloxane structure used in Example 1, a 1: 1 mixture (weight ratio) of the comparative polymer (D2) obtained in Comparative Synthesis Example 2 and the alkali-soluble polymer (C1) obtained in Synthesis Example 4 was used. A positive photosensitive composition was produced in the same manner as in Example 1 except that the patterned transparent film was formed and evaluated. The results are shown in Table 1.

[Industry availability]

The photosensitive composition of this invention can be used for a liquid crystal display element, for example.

Claims (8)

In the photosensitive composition containing the polymer (A) containing a siloxane structure, and a 1, 2- quinonediazide compound (B), The photosensitive composition whose polymer (A) containing the said siloxane structure is a radical polymer of the monomer containing the siloxane compound represented by following formula (1), and the radical polymer monomer represented by following formula (2):

In formula (1), R1 and R ² are each hydrogen; Arbitrary hydrogen may be substituted with fluorine, arbitrary methylene may be substituted with oxygen or cycloalkylene having 3 to 18 carbon atoms; C6-C40 aryl which may be substituted by fluorine, a C1-C20 alkyl group, or a C1-C20 alkoxy group; Or arylalkyl having 7 to 40 carbon atoms composed of alkylene in which the aryl and any hydrogen may be substituted with fluorine and any methylene may be substituted with oxygen or the cycloalkylene, R ³ and R ⁴ are each independently hydrogen; Arbitrary hydrogen may be substituted with fluorine, arbitrary methylene may be substituted with oxygen or cycloalkylene having 3 to 18 carbon atoms; C6-C40 aryl which may be substituted by fluorine, a C1-C20 alkyl group, or a C1-C20 alkoxy group; C7-C40 arylalkyl which consists of the said aryl and the alkylene which arbitrary hydrogen may be substituted by fluorine, and the arbitrary methylene may be substituted by the oxygen or the said cycloalkylene; Or group represented by following formula (3) is shown, R <^5> is C1-C20 linear or branched alkyl in which arbitrary hydrogen may be substituted by fluorine, and arbitrary methylene may be substituted by oxygen; Aryl having 6 to 20 carbon atoms, in which any hydrogen may be substituted with fluorine; Or arylalkyl having 7 to 20 carbon atoms, in which any hydrogen in aryl may be substituted with fluorine, A ¹ represents a radical polymerizable functional group, n represents an integer of 1 to 1,000, Provided that when n is 1, R ³ and R ⁴ each represent a group of formula (3):

In formula (3), R ⁶ and R ⁷ are each independently hydrogen; Arbitrary hydrogen may be substituted with fluorine, arbitrary methylene may be substituted with oxygen or cycloalkylene having 3 to 18 carbon atoms; C6-C40 aryl which may be substituted by fluorine, a C1-C20 alkyl group, or a C1-C20 alkoxy group; Or arylalkyl having 7 to 40 carbon atoms composed of alkylene in which the aryl and any hydrogen may be substituted with fluorine and any methylene may be substituted with oxygen or the cycloalkylene, R <^8> is C1-C20 linear or branched alkyl in which arbitrary hydrogen may be substituted by fluorine, and arbitrary methylene may be substituted by oxygen; Aryl having 6 to 20 carbon atoms, in which any hydrogen may be substituted with fluorine; Or arylalkyl having 7 to 20 carbon atoms, in which any hydrogen in aryl may be substituted with fluorine, m represents an integer from 1 to 500:

In formula (2), R <^9> -R <^11> represents hydrogen or C1-C3 alkyl which arbitrary hydrogen may be substituted by fluorine, respectively, R <^12> -R <^16> is hydrogen; halogen; -CN; -CF ₃ ; -OCF ₃ ; Hydroxyl group; Alkyl having 1 to 5 carbon atoms in which any methylene may be substituted with —COO—, —OCO—, —CO—, and optionally hydrogen may be substituted with halogen; Or C1-C5 alkoxy which may be optionally substituted with hydrogen, provided that at least one of R ¹² to R ¹⁶ is a hydroxyl group. The method of claim 1, The photosensitive composition whose polymer (A) containing the said siloxane structure is a radical polymer of the monomer which further contains other radically polymerizable monomers other than the compound represented by said Formula (1) and (2). The method of claim 2, The other radically polymerizable monomer is one or more selected from the group which consists of a styrene derivative which has a hydroxy (meth) acrylate, a (meth) acrylic acid derivative, and a phenolic hydroxyl group. The method according to any one of claims 1 to 3, The photosensitive composition which further contains the alkali-soluble polymer (C) which has alkali-soluble. The method of claim 4, wherein The monomer containing at least one of said alkali-soluble polymer (C) 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. 6. The method according to any one of claims 1 to 5, 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 1-6. The display element which has a cured film of Claim 7.