KR20060049045A - Silsesquioxane-containing compound and method for preparing the same - Google Patents

Abstract

Various desired functions such as photopolymerization, alkali solubility, and weather resistance can be imparted, and a silsesquioxane-containing compound suitable for radiation-sensitive resins having all the characteristics of silicon-based resins such as transparency and heat resistance is provided.

(Meth) acrylic acid ester (A) which has a trialkoxy silyl group in a molecule | numerator, (meth) acrylic acid ester which has a functional group which can provide alkali solubility as a substituent, and (meth) which has a functional group which can impart heat resistance as a substituent A silsesquioxane-containing compound formed by copolymerizing a trialkoxysilane compound (C ′) having a carbon-carbon double bond in a molecule with a copolymer of at least one acrylate ester, a radiation-sensitive resin composition using the compound, and vinyl A method for producing a compound wherein the radical copolymerization of monomers causes co-condensation of trialkoxysilanes.

Silsesquioxane, Photopolymerization, Alkali Solubility, Weatherability, Transparency, Heat Resistance, Radiation Resistant Resin

Description

Silsesquioxane-containing compound and method for preparing the same

The present invention relates to a silsesquioxane-containing compound having an acrylic copolymer chain, and in particular, it is possible to impart various desired functions such as photopolymerization, alkali solubility, heat resistance, weather resistance, and the like. Radical copolymerization of a silsesquioxane-containing compound and vinyl monomer suitable for all radiation-sensitive resins, and a method for producing a compound for co-condensation of a trialkoxysilane.

Recently, in the field of display devices such as liquid crystals and LEDs, there is an increasing need for radiation-sensitive resins having high transparency (i.e., high visible light transmittance, and the like) and having characteristics such as good heat resistance, radiation sensitivity, development resolution, and chemical resistance. . In particular, it has been difficult to meet the demand of conventional photosensitive resins such as phenol resins, novolak resins, acrylic copolymers, and alicyclic alkyl resins because of their high transparency. That is, in addition to the transparency at the time of coating film formation, securing high transparency which satisfies both the heat resistance transparency which is transparency after heating is insufficient with conventional resin. In order to solve this problem, some examples using silicon-based resins that are expected to have excellent transparency and heat resistance have been disclosed.

As a radiation sensitive resin containing a silsesquioxane structure, the resist resin containing the copolymer containing a ladder type silsesquioxane structure is disclosed (for example, refer patent document 1). The copolymer first condensates a trialkoxy silane having a side chain, synthesizes a silsesquioxane of a ladder structure containing a vinyl side chain, and then contains an acrylic monomer containing a side chain that is decomposed by an acid to generate an organic acid group. And it is obtained by copolymerizing the silsesquioxane containing the said vinyl type side chain, and aims at functioning as a positive photoresist. However, since this copolymer first synthesizes silsesquioxane by co-condensation and then radically copolymerizes the acrylic monomer, all ethylenic double bonds in the compound are consumed, and photopolymerization is not exhibited. It does not function as a resist. In addition, the ladder type silsesquioxane structure has high silicon content and excellent thermal stability and oxygen plasma resistance, but is advantageous as a positive photoresist, but high transparency and heat resistance are insufficient.

Alkali-soluble photosensitive resin using the (meth) acryloxy functional ladder type silsesquioxane is also known (for example, refer patent document 2). This silsesquioxane contains the side chains, such as an alkyl group, an aryl group, and a cyclohexyl group, and contains a (meth) acryloxy group, and the trialkoxysilane containing the (meth) acryloxy group and the side alkoxysilane It is made by co-condensation. However, this silsesquioxane itself does not have alkali solubility. Furthermore, no disclosure is made regarding silsesquioxane containing compounds having radical copolymer chains.

Resist compositions using silsesquioxanes containing carboxyl groups in the side chains are also known (see Patent Document 3, for example). This silsesquioxane, however, does not have photopolymerization. Further, no disclosure is made regarding the silsesquioxane-containing compound having a radical copolymer chain. As such, a silsesquioxane compound having high transparency, capable of satisfying basic physical properties as a resist, and suitable for radiation-sensitive resin is not known yet.

[Patent Document 1]

WO 99/09457, pp. 37-39.

[Patent Document 2]

Japanese Patent Laid-Open No. 10-161315, p. 4, etc.

[Patent Document 3]

Japanese Patent Laid-Open No. 11-60734, the scope of claims, and the like.

In view of the above phenomena, the present invention can impart various desired functions such as photopolymerization, alkali solubility, heat resistance and weather resistance, and moreover, a silsesquioxane suitable for radiation-sensitive resins having all the characteristics of silicon-based resins such as transparency and heat resistance. It is an object of the present invention to provide a method for producing a silsesquioxane-containing compound having high design freedom of the compound by performing co-condensation of the trialkoxysilane following the radical copolymerization of the compound and the vinyl monomer.

As a result of earnestly examining in order to solve the said subject, the present invention is insightful that high degree of freedom in designing a silsesquioxane-containing compound can be secured by performing radical copolymerization of vinyl monomers followed by trialkization of a trialkoxysilane. Based on these findings, the present inventors discovered a manufacturing method for freely providing various functions to silsesquioxane, and completed the present invention. That is, this invention is an ethylenic carbon-carbon in a molecule | numerator in copolymer (I) of the (meth) acrylic acid ester (A) which has a trialkoxy silyl group in a molecule | numerator, and the (meth) acrylic acid ester (B) which may have a substituent. It is a silsesquioxane containing compound formed by cocondensing the trialkoxysilane compound (C ') which has a double bond.

The present invention is also a radiation sensitive resin composition containing the compound which is alkali-soluble.

The present invention is also a substrate for an electronic component or an optical component having a cured layer of the composition.

The present invention also provides a step of copolymerizing the (meth) acrylic acid ester (A) having a trialkoxysilyl group in the molecule (1) and the (meth) acrylic acid ester (B) which may have a substituent, and (2) the obtained copolymer. It is also a method for producing a silsesquioxane-containing compound having a step of cocondensing a trialkoxysilane compound (C) which may have an ethylenic carbon-carbon double bond in the molecule.

The present invention has the following effects by the above configuration.

(1) The silsesquioxane-containing compound of the present invention can be given various desired functions such as photopolymerization, alkali solubility, heat resistance and weather resistance.

(2) The silsesquioxane-containing compound of the present invention is excellent in transparency and heat resistance.

(3) The silsesquioxane-containing compound of the present invention provides a radiation-sensitive resin composition excellent in transparency and heat resistance.

(4) The radiation-sensitive resin composition of the present invention has characteristics such as good heat resistance, high transparency, radiation sensitivity, development resolution and chemical resistance.

Next, the present invention will be described in detail.

In this invention, as (meth) acrylic acid ester (A) which has a trialkoxy silyl group in a molecule | numerator, for example, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryl Oxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and the like.

As (meth) acrylic acid ester (B) which may have a substituent, it contains (meth) acrylate which does not have a substituent, and (meth) acrylate which has a substituent, It does not specifically limit as said substituent, Contains silsesquioxane It can have a substituent corresponding to the function to provide to a compound. For example, a functional group capable of imparting alkali solubility to the silsesquioxane-containing compound, a functional group capable of imparting at least one property of heat resistance and weather resistance to the silsesquioxane-containing compound, and the like can be selected. As (meth) acrylate which has such a substituent, For example, As (meth) acrylic acid ester (b-1) which has a functional group which can provide alkali solubility to a silsesquioxane containing compound as a substituent, For example, 2 -(Meth) acryloyloxy ethyl phthalate, 2- (meth) acryloyloxy ethyl hexahydrophthalate, β-carboxyethyl acrylate, ω-carboxypolycaprolactone monoacrylate, ethylene oxide modified succinic acid acrylate, etc. Can be mentioned. These may use one type or may use two or more types together.

As (meth) acrylic acid ester (b-2) which has a functional group which can provide at least one property of heat resistance and weather resistance to a silsesquioxane containing compound as a substituent, For example, dicyclopentanyl (meth) acrylate, a dish Clofenthenyl oxyethyl (meth) acrylate, isobonyl (meth) acrylate, 9-methacryloxymethyl fluorene, tetrahydrofurpr (meth) acrylate, etc. are mentioned. These may use one type or may use two types together.

As (meth) acrylic acid ester (B) which may have a substituent, Others, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-2-ethylhexyloxypropyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, caprolactone acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, hydroxy (Meth) acrylic acid ester (b-3), cyclohexyl (meth) acrylate, benzyl (meth) arcrelate having a functional group which can impart adhesion such as ethyl vinyl ether to the silsesquioxane-containing compound as a substituent, Butoxyethyl (meth) acrylate, cetyl methacrylate, nitrile (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, hexafluoropropyl (meth) arc 3-ethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, isobutyl (meth) acrylate, isodecyl (meth) acrylate, Rauloxy Polyethylene glycol (meth) acrylate, lauryl (meth) acrylate, methoxypolyethylene (meth) acrylate, methyl methacrylate, pentamethylpiperidyl (meth) acrylate, phenoxyethyl (meth) acrylate, Stearyl (meth) acrylate, isostearyl (meth) acrylate, t-butyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, behenyl (meth) acrylate, triethylene glycol divinyl (Meth) acrylic acid ester (b-4) having a functional group which can impart at least one of compatibility and hydrophobicity such as ether and octadecyl vinyl ether to the silsesquioxane-containing compound as a substituent, Libromophenyl (meth) a There can be a relay agent, EO-modified tribromo phenyl acrylate, flame retardancy can be imparted to the yarn sesquioleate dioxane containing compound (meth) acrylate (b-5) having a functional group as a substituent, such as that. Each of these may be one type, or may use two or more types together, and may use the said ester (b-3)-(b-5) together. Moreover, you may use together the said ester (b-1)-(b-5).

Copolymerization of (meth) acrylic acid ester (A) and (meth) acrylic acid ester (B) can be performed by a conventional method, and well-known methods, such as solution polymerization, suspension polymerization, and emulsion polymerization, are possible. However, solution polymerization is preferred for ease of handling. When the copolymer of the present invention is produced by solution polymerization, first, a polymerization initiator and a chain transfer agent are dissolved in the (meth) acrylic acid ester (A) and (meth) acrylic acid ester (B) monomer mixture. Subsequently, the obtained uniform liquid mixture is maintained at a predetermined polymerization temperature for a certain time to complete the polymerization, thereby obtaining a copolymer.

As a polymerization initiator which can be used at this time, a 10-hour half-life temperature is 60-120 degreeC

The thing within the range of is preferable. As such a polymerization initiator, for example, 2, 2'- azobisisobutylonitrile, 2, 2'- azobis (2, 4- dimethylbarellonitrile), 2, 2'- azobis (2-methyl Butylonitrile), 2, 2'-azobis (2-methylpropionate), 2, 2'-azobis (N-cyanohexyl-2-methylpropionamide), 2, 2'-azobis [ Azo such as N- (2-propenyl) -2-methylpropionamide, 1, 1, 3, 3-tetramethylbutylperuoxy 2-ethylhexanoate, 1-cyclohexyl-1-methylethylperuoxy 2-ethylhexanoate, t-hexyl peruoxy 2-ethylhexanoate, t-amylperuoxy 2-ethylhexanoate, t-butylperuoxy 2-ethylhexanoate, t-butylperuoxy isobutyl T-butylperuoxymaleic acid, t-amylperuoxy 3, 5, 5-trimethylhexanoate, t-butylperuoxy 3, 5, 5-trimethylhexanoate, t-butylperuoxylaurate, t Hexyl peruoxybenzoate, t- Peruoxy esters, such as tilferuoxy acetate, t-butyl-peruoxy m- toluoyl benzoate, and t-butyl-peruoxy benzoate, t-hexyl peruoxy isopropyl monocarbonate, t-butyl-peruoxy isopropyl monocarbonate Peruoxy monocarbonates, such as t-butyl peruoxy 2-ethylhexyl monocarbonate, bis-3, 5, 5-trimethylhexanoyl peroxide, an octanoyl peroxide, a lauloyl peroxide, and a stearo Diacyl peroxides such as yl peroxide, succinate peroxide, m-toluoyl oxide, benzoyl peroxide and p-chlorobenzoyl peroxide, dichyl peroxide, t-butyl xyl peroxide and the like And dialkyl peruoxides. These may use one type and may use two or more types together.

It is preferable that the compounding quantity of the (meth) acrylic acid ester (A) component in copolymer (I) is 5-95 mass%. If the compounding quantity of (meth) acrylic acid ester (A) component is the said range, it is advantageous at the point of the heat resistance, transparency, and mechanical strength of a silsesquioxane containing compound. More preferably, it is 5-50 mass%.

Moreover, as for the compounding quantity of the (meth) acrylic acid ester (B) component in copolymer (I), 5-95 mass% of carboxylic acid containing monomer is preferable, More preferably, it is 50-70 mass%, and other monomers It is preferable that it is 0-50 mass%.

It is preferable that the weight average molecular weight of copolymer (I) is 1000-50000. When the weight average molecular weight exceeds 50000, the possibility of gelation in the co-condensation reaction with the trialkoxysilane compound (C) increases. On the contrary, when the weight average molecular weight is less than 1000, the developing speed of the silsesquioxane-containing compound is too high. There is a tendency that control is difficult or sufficient heat resistance cannot be obtained. More preferably, it is 4000-40000, More preferably, it is 7000-30000.

In the present invention, as the trialkoxysilane compound (C) which may have an ethylenic carbon-carbon double bond in the molecule, the trialkoxysilane compound (C ′) having an ethylenic carbon-carbon double bond in the molecule and ethylene in the molecule Trialkoxysilane compounds having no carbon-carbon double bonds are included. Examples of the trialkoxysilane compound (C ′) having an ethylenic carbon-carbon double bond in the molecule include 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyl. (Meth) acryloxytrialkoxysilanes, such as a trimethoxysilane, vinyl trimethoxysilane, p-styryl trimethoxysilane, etc. are mentioned. These may use one type or may use two or more types together.

Examples of the trialkoxysilane compound having no ethylenic carbon-carbon double bond in the molecule include phenyltrimethoxysilane, methyltrimethoxysilane, 2- (3,4 epoxy) cyclohexylethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxy Silyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-uladepropyltriethoxysilane, 3-chloropropyltrimethoxysilane, Alkyl, such as 3-mercapto propyl trimethoxysilane and 3-isocyanate propyl triethoxysilane, the monomer which consists of an allyl-type functional group, etc. are mentioned, At least 1 type can be selected and used.

Co-condensation of the copolymer (I) and the trialkoxysilane compound (C) can be carried out by a conventional method, and in the presence of an acidic catalyst, the alkoxysilyl group is hydrolyzed to form a siloxane bond by the dehydration condensation reaction of the silanol group. As for the quantity of the water mix | blended at that time, 1.0-3.0 are preferable with respect to the mole number of an alkoxysilyl group. When the number of moles is within this range, a silsesquioxane-containing compound can be obtained as a mixture with a structure such as a ladder type or a random type mainly containing a cage structure.

Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, boric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and P-toluenesulfonic acid.

 Moreover, fluorine-based compounds, such as tetrabutyl ammonium fluoride, potassium fluoride, and sodium fluoride, etc. can also be used. As for the compounding quantity, 0.01 to 0.1 weight% is preferable.

The reaction temperature of the cocondensation reaction is 40 to 80 ℃, the reaction time is preferably 3 to 12 hours.

In the method for producing a silsesquioxane-containing compound of the present invention, copolymerization of an acrylic monomer is first performed as described above, followed by cocondensation by hydrolysis and dehydration condensation of an alkoxysilyl group, (i) The carbon-carbon double bond can be easily introduced into the target compound, and (ii) it is easy to impart desired properties to the target compound by using those having various substituents in the copolymerization monomer, thereby providing freedom of design of the target compound. It is a very large manufacturing method. For example, (meth) acrylic acid ester (B) is a (meth) acrylic acid ester (b-1) which has a functional group which can give alkali solubility to a silsesquioxane containing compound as a substituent, and at least among heat resistance and weather resistance. By using a (meth) acrylic acid ester (b-2) having a functional group as a substituent which can impart one of the properties to the silsesquioxane-containing compound, impart at least one of alkali solubility, heat resistance and weather resistance to the target compound. In addition, by photocondensation of the trialkoxysilane compound (C ′) having an ethylenic carbon-carbon double bond in the molecule, photopolymerization can be imparted to the target compound. Such alkali-soluble silsesquioxane-containing compounds can be suitably used as a negative radiation-sensitive resin composition. In addition, when the monomer consisting of the alkyl and allyl functional groups described above is used as the trialkoxysilane compound (C), it can be suitably used as a positive radiation-sensitive resin composition.

A photoinitiator (E), a crosslinking agent (F), and surfactant (G) can be mix | blended with the said radiation sensitive resin composition. Examples of the photopolymerization initiator (E) include thioxanthones such as thioxanthone and 2,4-diethyl thioxanthone, 4,4'-dimethylaminobenzophenone, and 4-4'-diethylaminobenzophenone. Benzophenones such as 2,2-diethoxyacetphenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propaneone , Acetophenones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-methoxy-1-naphthyl) -4, 6-bis ( Halogen compounds such as trichloromethyl) -s-triazine, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 3,3 ', 4,4'-tetra (t-butyl Peroxides, such as paoxycarbonyl) benzophenone, etc. are mentioned.

As for the compounding quantity of the said photoinitiator (E), 0.5-10 weight% of the whole radiation sensitive resin composition is preferable, More preferably, it is 1-5 weight%.

As said crosslinking agent (F), for example, 1, 6-hexanediol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol (meth) Acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, poly (butanediol) di (meth) acrylate, 1,3-butylene Glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, triisopropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A Di (meth) acrylate, trimetholpropane tri (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, trimetholpropane triethoxytri (meth) acrylate, penta Thritol tetra (meth) acrylate, ditrimetholpropane tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanurate ethylene Oxide (hereinafter EO) modified tri (meth) acrylate, trimetholpropane EO modified triacrylate, trimetholpropane propylene oxide modified tri (meth) acrylate, various urethane polyvalent (meth) acrylates and various ester polyvalents ( Meth) acrylate, etc. are mentioned. As these polyfunctional (meth) acrylate monomers or oligomers, those sold by Toagosei Co., Ltd. and Nippon Kayaku Co., Ltd. can also be used.

As for the compounding quantity of the said crosslinking agent (F), 20 weight% or less of the whole radiation sensitive resin composition is preferable, More preferably, the amount of 10 weight% or less is contained.

As said surfactant (G), For example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene allyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; F-top EF301, F-top 303, and F-top 352 (made by Shin-Kita Chemical Co., Ltd.); Mega Pack F171, Mega Pack F172, Mega Pack F173 (manufactured by Dainippon Ink & Chemicals Co., Ltd.); Flora FC-430 and Flora FC-431 (manufactured by Sumitomo Industries Co., Ltd.); Acai Guard AG710, Saffron S-382, Saffron SC-101, Saffron SC-102, Saffron SC-103, Saffron SC-104, Saffron SC-105, Saffron SC-106 (Asahigaras ( Fluorine-based surfactants commercially available under the names such as Note); Organosiloxane polymer-KP341 (manufactured by Singase Chemical Industries, Ltd.); (Meth) acrylic-acid copolymer polyprop No 57.95 (made by Kyoeisha Chemical Co., Ltd.) etc. These are used individually or in combination of 2 or more types.

The surfactant of the above-mentioned (G) is contained in order to improve the applicability | paintability of the radiation sensitive resin composition of this invention containing a solvent, for example.

As for the compounding quantity of the said surfactant (G), 2 weight% or less of the whole radiation sensitive resin composition is preferable, More preferably, it is contained in the amount of 1 weight% or less.

Other components can be added to the radiation-sensitive resin composition in a range that does not impair the object of the present invention. Examples of the other components include solvent antistatic agents, storage stabilizers, antifoaming agents, pigments, dyes, and the like.

Examples of the solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether and diethylene glycol monomethyl Glycol ethers such as ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol monobutyl ether; methyl vertical sol acetate, ethyl vertical sol acetate, butyl vertical sol acetate, propylene Alkylene glycol monoalkyl ether acetates such as glycol methyl ether acetate and 3-methoxybutyl-1-acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone Ketones such as 4-hydroxy-4-methyl-2-pentanone and the like; And ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-2-methylbutanoic acid. Esters such as methyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate. These solvents may be used individually by 1 type, and may mix and use two or more types.

The radiation-sensitive resin composition is applied to the substrate surface, and the coating film can be formed by removing the solvent by heating. Application of the photosensitive resin composition to the substrate surface can be carried out by conventionally known methods such as spin coating, roll coating, and dipping. Subsequently, this coating film is heated (prebaked) with a hotplate, oven, etc.

The substrate is not particularly limited, and examples thereof include substrates such as various electronic components and optical components. Specifically, for example, a transparent insulating film formed between a TFT and a transparent electrode, a liquid crystal display device using the same, and a PDP. Display elements, such as display elements, a board | substrate in optical components, an optical element, etc. are mentioned.

Thereafter, the prebaked coating film is irradiated with ultraviolet rays through a mask of a predetermined pattern, and then developed using a developing solution, and unnecessary portions are removed to form a film having a predetermined pattern shape. As a developing solution, aqueous solutions, such as inorganic alkalis, such as sodium carbonate, sodium hydroxide, potassium hydroxide, and organic alkalis, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, are mentioned. Moreover, methanol, ethanol, surfactant, etc. can also be added and used to the said aqueous alkali solution. The developing method may be any of a dipping method, a shower method, a spray method, and the like. The developing time is usually 30 to 240 seconds, and a pattern can be formed by rinsing and drying with running water after development.

Thereafter, the pattern is heated (post-baked) with a hot plate, an oven, or the like to further advance crosslinking of the unreacted components and to completely remove the solvent to obtain a predetermined coating pattern. Post-baking conditions differ depending on the type of each component and the mixing ratio, but are usually 180 to 220 ° C, 5 to 30 minutes for a hot plate and 30 to 90 minutes for an oven.

This obtains the electronic component or optical component base material which has the hardened layer of the said radiation sensitive resin composition.

EXAMPLES Next, an Example is shown and this invention is demonstrated in more detail, but this invention is not limited to this.

Example

Example 1

Synthesis of Alkali-soluble Silsesquioxane-containing Compound D-1

6.1 g of 2-acryloyloxyethyl hexahydrobutyrate, 4.7 g of 3-methacryloxypropyltrimethoxysilane, 20.0 g of benzyl methacrylate, 1.3 g of 2,2'-azobisisobutylonitrile, β- 1.3 g of mercaptopropionic acid and 137 g of toluene are placed in a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, purged with nitrogen for 30 minutes, and the flask is immersed in an oil bath, at an internal temperature of 80 ° C. The polymerization reaction was carried out for 5 hours. Then, it cooled to room temperature and obtained the copolymer solution. In addition, 100 g of the obtained copolymer solution, 12.9 g of 3-acryloxypropyltrimethoxysilane, 7.1 g of methyltrimethoxysilane, and 30 g of isopropyl alcohol were placed in a flask with a stirrer, a cooling tube, a dropping funnel, and a thermometer, and 5 g of distilled water. , 36% hydrochloric acid 0.3g, and isopropyl alcohol 5g was added dropwise for 30 minutes at 70 ℃ internal temperature, the reaction was carried out for 3 hours. After cooling to room temperature, 3 g of Adsorbent Kyowa 500 (same as the brand name or less) was added thereto, followed by stirring for 15 minutes to neutralize. This was filtered and concentrated to give 46.4 g of an alkali-soluble silsesquioxane-containing compound D-1. The weight average molecular weight (henceforth Mw) of obtained resin was 17200.

Example 2

Synthesis of Alkali-soluble Silsesquioxane-containing Compound D-2

6.1 g of 2-acryloyloxyethyl hexahydrobutyrate, 4.7 g of 3-methacryloxypropyl trimethoxysilane 20.0 g of isobornyl acrylate, 1.3 g of 2,2'- azobisisobutylonitrile, (beta) -mer 1.3 g of captopropionic acid and 137 g of toluene are placed in a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, purged with nitrogen for 30 minutes, and the flask is immersed in an oil bath for 5 hours at an internal temperature of 80 ° C. The polymerization reaction was carried out. Then, it cooled to room temperature and obtained the copolymer solution. In addition, 100 g of the obtained copolymer solution, 6.5 g of 3-acryloxypropyltrimethoxysilane, 13.5 g of methyltrimethoxysilane, and 30 g of isopropyl alcohol were placed in a flask with a stirrer, a cooling tube, a dropping funnel, and a thermometer, and distilled water. The aqueous solution which combined 5g, 36% hydrochloric acid 0.3g, and isopropyl alcohol 5g was dripped at the internal temperature of 70 degreeC for 30 minutes, and reaction was performed for 3 hours. After cooling to room temperature, 3 g of adsorbent Kyowa 500 was added and stirred for 15 minutes to neutralize. This was filtered and concentrated to give 38.0 g of an alkali-soluble silsesquioxane-containing compound D-2. Mw of the obtained resin was 15500.

Example 3

Synthesis of Alkali-soluble Silsesquioxane-containing Compound D-3

6.1 g of 2-acryloyloxyethyl hexahydrophthalate, 4.5 g of 3-methacryloxypropyltrimethoxysilane, 20.0 g of cyclohexyl methacrylate, 1.3 g of β-mercaptopropionic acid, 2,2'-azobisiso Put 1.3 g of butylonitrile and 137 g of toluene into a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, purge with nitrogen for 30 minutes, and immerse the flask in an oil bath. Time polymerization was carried out. Then, it cooled to room temperature and obtained the copolymer solution. In addition, 100 g of the obtained copolymer solution, 1.0 g of methyltrimethoxysilane, 19.0 g of 3-acryloxypropyltrimethoxysilane, and 30 g of isopropyl alcohol were placed in a flask with a stirrer, a cooling tube, a dropping funnel, and a thermometer, 5 g of distilled water, The aqueous solution which combined 0.3 g of 36% hydrochloric acid and 5 g of isopropyl alcohols was dripped at the internal temperature of 70 degreeC for 30 minutes, and reaction was performed for 3 hours. After cooling to room temperature, 3 g of adsorbent Kyowa 500 was added and stirred for 15 minutes to neutralize. This was filtered and concentrated to give 44.0 g of an alkali-soluble silsesquioxane-containing compound D-3. Mw of the obtained resin was 16800.

Example 4

Synthesis of Alkali Soluble Silsesquioxane-containing Compound D-4

4.0 g of 2-acryloyloxyethyl hexahydrophthalate, 4.5 g of 3-methacryloxypropyltrimethoxysilane, 23.0 g of dicyclopentanyl methacrylate, 1.3 g of β-mercaptopropionic acid, 2,2'-azobis 1.3 g of isobutylonitrile and 137 g of toluene are placed in a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer, purged with nitrogen for 30 minutes, and the flask is immersed in an oil bath for polymerization at an internal temperature of 80 ° C. for 5 hours. The reaction was carried out. Then, it cooled to room temperature and obtained the copolymer solution. In addition, 100 g of the obtained copolymer solution, 7.1 g of methyltrimethoxysilane, 12.9 g of 3-acryloxypropyltrimethoxysilane, and 30 g of isopropyl alcohol were placed in a flask with a stirrer, a cooling tube, a dropping funnel, and a thermometer, and 5 g of distilled water. , 36% hydrochloric acid 0.3g, isopropyl alcohol 5g combined aqueous solution was added dropwise for 30 minutes at 70 ℃ internal temperature, the reaction was carried out for 3 hours. After cooling to room temperature, 3 g of an adsorbent Kyowa 500 was added, followed by stirring for 15 minutes. This was filtered and concentrated to give 38.0 g of an alkali-soluble silsesquioxane-containing compound D-4. Mw was 15300 in the obtained resin.

Example 5

Synthesis of Alkali Soluble Silsesquioxane-containing Compound D-5

9.0 g of 2-acryloyloxyethyl hexahydrophthalate, 4.7 g of 3-methacryloxypropyltriethoxysilane, 18 g of t-butylcyclohexyl methacrylate, 1.3 g of β-mercaptopropionic acid, 2,2'-azo 1.3 g of bisisobutyronitrile and 137 g of toluene are placed in a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer, purged with nitrogen for 30 minutes, and the flask is immersed in an oil bath for 5 hours at an internal temperature of 80 ° C. The polymerization reaction was carried out. Then, it cooled to room temperature and obtained the copolymer solution. In addition, 100 g of the obtained copolymer solution, 7.1 g of phenyltrimethoxysilane, 12.9 g of 3-acryloxypropyltrimethoxysilane, and 30 g of isopropyl alcohol were placed in a flask with a stirrer, a cooling tube, a dropping funnel, and a thermometer, and distilled water. The aqueous solution which combined 5 g, 36% hydrochloric acid 0.3g, and 5 g of isopropyl alcohols was dripped at the internal temperature of 70 degreeC for 30 minutes, and reaction was performed for 3 hours. After cooling to room temperature, 3 g of an adsorbent Kyowa 500 was added, followed by stirring for 15 minutes. This was filtered and concentrated to give 38.0 g of alkali-soluble silsesquioxane-containing compound D-5. Mw of the obtained resin was 16600.

Example 6

100 parts by weight of the alkali-soluble silsesquioxane-containing compound D-1 obtained in Example 1, 7 parts by weight of Irugacure 907, 4 parts by weight of DPHA (Dipentaerythritol hexaacrylate, manufactured by Nihon Kayaku Corporation) and mega 0.01 parts by weight of Pack 172 was dissolved in propylene glycol monomethyl ether acetate so that the solid concentration was 30% by weight. This was filtered with a Millipore filter having a pore diameter of 0.2 µm to obtain a radiation sensitive resin composition.

Example 7

The radiation-sensitive resin composition was prepared in the same manner as in Example 6 except that the alkali-soluble silsesoxane-containing compound (D-2) obtained in Example 2 was replaced with the alkali-soluble silsesquioxane-containing compound (D-1). Got it.

Example 8

A radiation sensitive resin composition was obtained in the same manner as in Example 6 except that the alkaline soluble silsesquioxane-containing compound (D-1) was used and the alkali-soluble silsesquioxane-containing compound (D-3) obtained in Example 3 was used. .

Example 9

A radiation sensitive resin composition was obtained in the same manner as in Example 6 except that the alkaline soluble silsesquioxane-containing compound (D-1) was used and the alkali-soluble silsesquioxane-containing compound (D-4) obtained in Example 4 was used. .

Example 10

The radiation-sensitive resin composition was obtained in the same manner as in Example 6 except that the alkaline-soluble silsesquioxane-containing compound (D-1) was used and the alkali-soluble silsesquioxane-containing compound (D-5) obtained in Example 5 was used. .

Comparative Example 1

A radiation sensitive resin composition was obtained in the same manner as in Example 6 except that the compound was replaced with an alkali-soluble silsesquioxane-containing compound (D-1), and used with novolac epoxy acrylate C-0011 (manufactured by Nihon Kayaku Co., Ltd.).

Comparative Example 2

A radiation-sensitive resin composition was obtained in the same manner as in Example 6 except that bis-A-epoxy acrylate TCR-1122 (manufactured by Nihon Kayaku Co., Ltd.) was used instead of the alkali-soluble silsesquioxane-containing compound (D-1). .

Evaluation of radiation sensitive resin composition

Examples 6-10 The radiation sensitive resin composition obtained by the comparative examples 1-2 was evaluated about the following item, and the result was shown in Table 1.

1. Patterning Characteristics of Thin Films

The radiation-sensitive resin composition obtained in Examples 6 to 10 and Comparative Examples 1 to 2 was coated on a glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 120 seconds to obtain a 0.5 μm thick film. Subsequently, a mask having a predetermined pattern was set on a glass substrate having a coating film, and an ultraviolet ray having a light intensity of 9.5 mW / cm 2 at a wavelength of 405 nm was irradiated with an energy amount of 1000 mJ / cm 2 using a 250 W high-pressure mercury lamp. Subsequently, the development process was performed at 23 degreeC for 60 second using the 2.38% tetramethylammonium hydroxide aqueous solution, the unexposed part of the coating film was removed, and the board | substrate with the pattern which consists of a remaining coating film was obtained. Evaluation was expressed by the following criteria. Corning 7059 (manufactured by Corning) was used as the glass substrate.

(Pattern Shape Evaluation)

(Double-circle): No change is seen before and after heating.

O: A slight change is seen before and after heating.

(Triangle | delta): A slight change is seen.

2. Light transmittance

About the coating film obtained by the said prebaking, the spectral transmittance was measured using the Hitachi spectrophotometer U-2000. Evaluation was expressed by the following criteria.

(Light transmittance evaluation)

O: The minimum transmittance is 95% or more.

 X: The minimum transmittance is 95% or less.

3. Heat resistance

The board | substrate with the pattern obtained by said 1 was heated at 230 degreeC for 60 minutes, the pattern state (shape, surface state) was observed, and the thermal deformation of the pattern was observed. The cross-sectional shape of the line pattern before and after heating was compared.

O: No change was seen before and after heating.

X: The change was seen before and after heating.

4. Heat discoloration resistance

The board | substrate with the pattern obtained by said 1 was heated at 230 degreeC for 60 minutes, and the transmittance | permeability of the glass substrate was measured by the wavelength of 400-700 nm using the spectrophotometer "U-2000 (made by Hitachi Seisakusho)." The change in transmittance was calculated by the following equation.

Change of transmittance = [(heat transmittance-heat transmittance 9) / heat transmittance] × 100 (%)

O: The change in transmittance is less than 5%.

 X: The change of transmittance exceeded 5%.

5. Pencil Hardness

The pencil hardness of the cured film obtained by heating the coating film obtained by the said prebaking at 230 degreeC for 60 minutes was measured according to the test method of JIS-K-5400. The highest hardness that the cured film was not scratched when multiplied by a load of 9.8 N using a pencil hardness tester was the pencil hardness.

6. Sensitivity

Sensitivity was expressed as the number of stages cured at 1000 mJ / cm 2 by Grayscale (Kodak Photographic Step Tablet No. 2). The larger the number, the higher the sensitivity.

7. Developability

A rectangular cross section of L / S having a line width of 0.5 µm formed on a silicon wafer was observed using a scanning electron microscope, and evaluated according to the following criteria.

O: The rest of the development could not be seen between the patterns.

(Triangle | delta): The remainder of some phenomenon was seen between patterns.

X: The rest of the phenomenon between patterns is many.

Patterning characteristics Developability Sensitivity Transmittance (%) Heat resistance Heat discoloration resistance Pencil hardness Example 6 ◎ O 8 O O O 4H Example 7 ◎ O 5 O O O 4H Example 8 ◎ O 11 O O O 4H Example 9 ◎ △ 8 O O O 4H Example 10 ◎ O 8 O O O 4H Comparative Example 1 O △ 5 × O × 4H Comparative Example 2 △ △ 5 × × × 4H

The radiation-sensitive resin composition using the alkali-soluble silsesquioxane-containing compound of the present invention in Examples 6 to 10 is particularly excellent in light transmittance, heat resistance, patterning characteristics, and heat discoloration resistance. It was evident that the compositions of Comparative Examples 1 and 2 according to the prior art exhibited the above performance.

The silsesoxane-containing resin composition of the present invention not only has excellent transparency and heat resistance.

It is suitable as a radiation-sensitive resin composition which is suitably used as a transparent insulating film formed between the TFT and the transparent electrode with good sensitivity, resolution, and the like, and is used for displaying liquid crystal display devices and plasma display panels (PDP). Applied suitably for the device, it is very advantageous to improve the performance of the display device. In addition, the production method of the present invention by the co-condensation of the trialkoxy silane followed by the radical copolymerization of vinyl monomer, the various properties such as alkali solubility, weather resistance, adhesion, compatibility, flame retardancy, photopolymerization to the silsesquioxane-containing compound It can be given easily, and it is very advantageous because it can synthesize | combine the silsesquioxane containing compound which has a desired function.

Claims (14)

A tree having an ethylenic carbon-carbon double bond in a molecule thereof in a copolymer (I) of a (meth) acrylic acid ester (A) having a trialkoxysilyl group in the molecule and a (meth) acrylic acid ester (B) which may have a substituent Silsesquioxane-containing compound, characterized by cocondensing an alkoxysilane compound (C ′) (Meth) acrylic acid ester (B) is a (meth) acrylic acid ester (b-1) which has a functional group which can provide alkali solubility to a silsesquioxane containing compound as a substituent, and heat resistance and weather resistance. Silsesquioxane-containing compound, characterized in that at least one selected from the group consisting of (meth) acrylic acid ester (b-2) having at least one property as a functional group which can impart to the silsesquioxane-containing compound. . The silsesquioxane-containing compound according to claim 2, wherein the (meth) acrylic acid ester (b-1) contains a carboxyl group. The said (meth) acrylic acid ester (b-1) is a 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, (beta) -carboxyethyl acrylate. ,? -carboxypolycaprolactone monoacrylate, or an ethylene oxide-modified amber acid acrylate. Silsesquioxane-containing compound, characterized in that. The said (meth) acrylic acid ester (b-2) is a dicyclopentanyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, and 9-. A silsesquioxane-containing compound, characterized in that it is methacryloxymethyl fluorene or tetrahydroflupryl (meth) acrylate. The (meth) acrylic acid ester (B) according to claim 1, wherein the (meth) acrylic acid ester (B) is a (meth) acrylic acid ester (b-3) having a functional group as a substituent that can impart adhesiveness to the silsesquioxane-containing compound, and is compatible. And (meth) acrylic acid ester (b-4) having a functional group capable of imparting at least one of hydrophobicity to the silsesquioxane-containing compound as a substituent and a functional group capable of imparting flame retardancy to the silsesquioxane-containing compound. A silsesquioxane-containing compound characterized by at least one kind selected from the group consisting of (meth) acrylic acid ester (b-5) having a substituent as the substituent. The silsesquioxane-containing compound according to claim 1, wherein the trialkoxysilane compound (C ') is (meth) acryloxytrialkoxysilane, vinyltrimethoxysilane, or p-styryltrimethoxysilane. The silsesquioxane-containing compound according to claim 1, which is a compound containing silsesquioxane having a cage structure. The silsesquioxane-containing compound according to claim 1, wherein the amount of the (meth) acrylic acid ester (A) component in the copolymer (I) is 5 to 95 mass%. The silsesquioxane-containing compound according to claim 1, wherein the weight average molecular weight of the copolymer (I) is 1000 to 50000. A radiation sensitive resin composition comprising an alkali soluble compound of claim 2. The radiation sensitive resin composition according to claim 11, wherein the photopolymerization initiator (E), the crosslinking agent (F), and the surfactant (G) are contained. An electronic part or optical part base material having a cured layer of the composition of claim 11. (1) Process of copolymerizing (meth) acrylic acid ester (A) which has a trialkoxy silyl group in a molecule, and (meth) acrylic acid ester (B) which may have a substituent, and (2) Process of co-condensing the trialkoxysilane compound (C) which may have ethylenic carbon-carbon double bond in the molecule | numerator in the obtained copolymer Method for producing a silsesquioxane-containing compound, characterized in that having.