TW201224060A - Polysiloxane composition, production method for polysiloxane composition, cured film of display element and forming method for cured film of display element - Google Patents

Abstract

The present invention provides a polysiloxane composition providing high level and balance for the needed properties of the cured film of protective film and interlaminar insulated film, etc. The polysiloxane composition comprises the following components [A] to [D]: [A] polysiloxane having radical polymerizable organic group, and the polysiloxane is obtained by hydrolysis condensation of (a1) silane composition having radical polymerizable organic group and (a2) silane composition without radical polymerizable organic group. The ratio of (a1) silane composition having radical polymerizable organic group in the polysiloxane is over 15 molecular%; [B] polysiloxane without radical polymerizable organic group; [C] radical polymerization initiator; and [D] solvent.

Description

201224060 VI. [Technical Field] The present invention relates to a polyoxyalkylene composition suitable as a material for forming a cured film such as a protective film or an interlayer insulating film of a display element, and a cured film formed of the composition. And a method of forming the cured film. [Prior Art] As a display element such as a liquid crystal display element, in the manufacturing step, a solvent, an acid or an alkali solution or the like is used for the impregnation treatment, and when the wiring electrode layer is formed by a money shot, the surface of the element is partially exposed to At high temperatures. In order to prevent such impregnation treatment and high-temperature treatment from deteriorating or damaging the display element, it is necessary to provide a protective film which is resistant to these treatments on the surface of the element. For such a protective film, it is required to have a property that the substrate or the lower layer on which the protective film is to be formed and the layer formed on the protective film have high adhesion, the film itself is smooth and strong, and has transparency even if It does not discolor under the temperature conditions, and can maintain transparency, surface hardness, and scratch resistance. In order to satisfy such a desired property, a bupropion acid-based resin is mainly used as a component of a radiation-sensitive linear composition for forming a protective film, and an attempt has been made to use a polyoxygenated gas which is superior in heat resistance and transparency to an acrylic resin. The material is a component of the radiation sensitive composition (Patent Document 丨~3). However, the adhesion of the polyoxyalkylene-based material to the ITO (indium tin oxide) transparent conductive film is insufficient. The cured film is liable to be cracked (cracked). Therefore, it is not practical as a film. Moreover, when the adhesion on the key wiring in the display element is insufficient, the protective film may be made on the molybdenum wiring.

S -4- 201224060 is the starting point, cracking or peeling occurs. Therefore, there is still a need to develop a polyoxyalkylene-based radiation-sensitive linear composition which is excellent in heat resistance and transparency and which has improved adhesion to an ITO transparent conductive film and a molybdenum wiring. In addition, 'automatic teller machines, vending machines, mobile phones, portable information terminals, digital audio players, etc., such as banks, use touch panels, touch screens, and touch screens. The display on the screen is pressed to operate the input device of the device. Since the touch panel is usually pressed directly with a finger or the like, a protective film is required. The protective film needs to have a surface adhesion such as adhesion to the wiring of the touch panel element and scratch resistance as a protective film. On the other hand, in a display element or the like, the interlayer insulating film is generally provided to insulate between wirings arranged in a layer shape. The interlayer insulating film of the display element needs to form a pattern of wiring contact holes. As a material for forming an interlayer insulating film of a liquid crystal display element, a negative-sensitive radiation-sensitive composition which is advantageous in terms of cost has been developed (Patent Document 4). However, as such a negative-type radiation-radiating composition, it is difficult to form a practical level. The contact hole of the hole technology. Therefore, from the viewpoint of the superiority of the formation of the contact hole, the positive-type radiation-sensitive composition is widely used for forming the interlayer insulating film of the display element (Patent Document 5). Thus, in the manufacture of a display element or the like, a plurality of radiation sensitive compositions are used in accordance with the purpose and steps. Recently, from the point of view of cost reduction, 'there is attempting to unify the types of radiation-sensitive linear compositions, and it is expected to form a protective film and an interlayer insulating film with a radiation-sensitive composition. Specifically, it is strongly hoped. Developed a protective film and an interlayer insulating film that are excellent in transparency, heat resistance, adhesion, crack resistance, sensitivity, refractive index, 201224060 surface hardness and scratch resistance, and can be formed. The resolution of the contact hole which can be used practically is a polyoxyalkylene negative-type radiation linear composition which has sufficient adhesiveness and scratch resistance as a protective film for a touch panel. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-0 0 1 64 No.专利 _ _ 62 62 62 62 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 Based on the above situation, the purpose of the invention is to provide a polysulfide oxide composition which can form a cured film such as a protective film and an interlayer insulating film which can form the above-mentioned desired special 4 to the level of balance and manufacture thereof. method. Another object of the present invention is to provide a protective film, an interlayer insulating (tetra) cured film, and a method for forming the same. [Means for Solving the Problem] Renting Problem The present invention first provides a composition of a poly-stone-oxygen-burning composition containing the components [A] to [D] of ^ T 3 θ M:

[A] Co-polymerization by (ai) a decane compound having a free A soil organic group and (a2) a compound having no radical polymerization obtained by radical polymerization decondensation The organic group-based polyoxetane, the ratio of (al) having a right έb to the 4 合 由 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 Poly-Keong oral organic-based polyoxyalkylene; [C] free radical polymerization hair-curing agent, and [DJ solvent. Further, the first aspect of the present invention is a method for producing the above polyoxane composition, which comprises mixing at least the following components [A], [A] by (iv) having radical polymerization. Organic group (4) hydrazine compound (a2) has no radical polymerizability and is replaced by a decane compound of a memorized organic group to carry out the decondensation of the fluorene obtained from the group A. Oxyalkane, the proportion of the (al) and right-only t-radical polymerizable organic group in the polyoxoxime is more than 15 moles. /〇; [B] w oxime without a radical polymerizable organic group; [C] a radical polymerization hair styling agent, and [D] solvent. The step of providing the above-mentioned polyoxane group, the third aspect of the invention is a cured film of a substantially formed article. Further, the fourth aspect of the present invention provides a method for forming a cured film of a display element. And comprising the following steps (4): (1) forming a coating film of the above polyoxane composition on the substrate; ^ partially irradiating the enemy (2) with at least the rays of the coating film formed by the step (1) (3) a step of heating the coating film developed in the step (3) by the step (4) of developing the coating film of the radiation irradiated by the step (2). Further, the fifth aspect of the present invention provides a cured film of a display element formed by the above method 201224060, for example, a protective film for a touch panel which can be used as a display element. [Effects of the Invention] The polyoxazine composition of the present invention has a high level of general characteristics in terms of transparency, heat resistance, transparency, transparency, surface hardness, and scratch resistance. Since the adhesion to the ITO transparent conductive film is improved, it is easy to form a cured film such as a protective film or an interlayer insulating film having a fine and delicate pattern. Therefore, the cured film (protective film or interlayer insulating film) thus formed can be suitably used as a display element, in particular, as a protective film for a touch panel display element. Further, the polyoxyxylene composition of the present invention can exhibit sufficient resolution to the extent that contact holes can be formed. [Embodiment] [Formation for Carrying Out the Invention] [Polyoxane Composition] The polyoxyalkylene composition of the present invention contains the [A] component, the [B] component, the [C] component, and the [D] component as Essential components>> The various components are described in detail below. [A] Component [A] is a decane compound (a) which has a radical polymerizable organic group (hereinafter also referred to as (al) compound) and (a2) a decane compound which does not have a radical polymerizable organic group (hereinafter) Also known as the (a2) compound), the polyazepine having a radical polymerizable organic group obtained by co-hydrolysis condensation has a ratio of the (al) compound in the polyoxyl combustion exceeding 15 mol%. The compound (8) is preferably a hydrolyzable decane compound of 201224060 represented by the following formula (1) or the following formula (7).

(1) (2) [In the formula (1), 'R represents a group having 1 to 4 carbon atoms, R2 represents a single bond, a methylene group or an alkylene group, and X represents a vinyl group, an allyl group, a stupid vinyl group or (fluorenyl) propylene oxime. In the formula (2), 'R3 represents an alkyl group having 1 to 4 carbon atoms, and R5 independently of each other represents a single bond, a methylene group or an alkylene group, and γ represents a vinyl group, an allyl group, a styryl group or (Meth) propylene decyloxy group, Z represents a hydrogen atom, a group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, a crypto atom, an epoxy group, an isocyanate Alkyl, amine, vinyl, ethylidene or (indenyl) propylene oxide. P is an integer of 1 or 2. Here, the "hydrolyzable decane compound" in the present specification means "a decane compound having a hydrolyzable group", and the "hydrolyzable group" as used herein means that a sterol group can be usually formed by reacting with water ( The base of _Si-〇H). On the other hand, the "non-hydrolyzable group" means a group which cannot form a sterol group by reaction with water and is stably present. Further, "hydrolysis condensation" means a dehydration condensation reaction between sterol groups formed by hydrolysis, and/or a condensation reaction of a sterol group with a hydrolyzable group to form a siloxane chain (-Si-0-Si) -). Further, in the hydrolysis reaction, if a sterol group is formed from a part of the hydrolyzable group, the unhydrolyzed group (_〇R1 or _〇r3) may remain, that is, a part of the [A] component has a selected from the group consisting of _〇R3 At least one of the groups. In the present invention, 'not only a hydrolyzable decane compound, but also a partial hydrolyzate thereof may be used, and the same is true for the component [B] to be described later. Here, the "partial hydrolyzate" in the present specification means an alkane. a hydrazine condensation reaction of an oxy group, and at least one alkoxy group compound preferably having two or more alkoxy groups remaining in the molecule (the number of cesium atoms is 2 to 1 Å, preferably 2 to 3 0) The alkylene oxide oligomers R1, !3, and the alkyl group in the oxime may be linear or branched. The alkyl groups in R and R are derived from the viewpoint of reactivity of hydrolysis condensation. Preferably, it is preferably an alkyl group having 1 to 2 carbon atoms. Further, the alkyl group in z is preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably ～4 groups. Examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, etc. As the alkylene group in R2, R4 and R5, a carbon atom number 2 is preferred. ~6 alkylene groups, particularly preferably an alkylene group having 2 to 3 carbon atoms. The alkylene group may be linear or branched, specifically Examples thereof include an ethyl group, a trimethylene group, and a propyl group. The (meth) acryloxy group in the XY and Z is a propylene oxy group, a fluorenyl propylene group, and a styrene. The substitution positions of the ethyl group on the aromatic ring of the group are Jin, and 5σ t have long been particularly limited, and the ortho, meta and para positions are acceptable. As the Z in Z, the -k _ soil is listed from the single ring. ～3 cyclic aromatic hydrocarbon group. The aryl group may have 6 to 14 carbon atoms, and may have a substituent, and as a substituent, for example, 5丨丨I π m 歹An alkyl group having 1 to 6 atoms, a halogen atom, a hydroxyl group, an amine group, a nitrate, a sulfhydryl group, a carboxyl group, or an alkoxy group. As a square storm, for example, an I 婪 本 base '% group can be listed as a substitution. Aryl group, for example

-10- S 201224060, can be listed as a stupid base. In the above formula, Μ λ I , a pyridyl group, as R 2 , R is preferably a carbon atom having 1 to 2 carbon atoms, preferably = or 2 or 3 carbon atoms. Vinyl or (meth) propyl decyloxy. In the case of =^(2), 'as R3' is preferably a group having 1 to 2 carbon atoms and a size of 5, preferably a single bond or an alkylene group having 2 to 3 carbon atoms. The vinyl group or the (meth) propylene decyloxy group is preferably an alkyl group having 1 to 6 carbon atoms. Further, preferred examples of the compound represented by the above formula (1) include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tripropoxy decane, and o-benzene. Vinyl trimethoxy decane 'o-styryl triethoxy decane, m-styryl tridecyl decane, m-styryl triethoxy decane, p-styryl trimethoxy decane 'p-styrene Triethoxy sulphur, dipropyltrimethoxy shixi', propyl triethoxy oxalate, methacryloxy methoxy decane, methacryloxy triethoxy decane , methacryloxy methoxy tripropoxy decane, propylene oxy methoxy methoxy sinter, propylene oxy ethoxy triethoxy sulphide, propylene decyloxy tripropoxy decane, 2-methyl Acryloxyethyltrimethoxy zeoxime, 2-methylpropenyloxyethyltriethoxydecane, 2-methylpropenyloxyethyltripropoxydecane, 3-methyl Propylene methoxy propyl trimethoxy decane, 3-mercapto propylene methoxy propyl triethoxy decane, 3 mercapto propylene oxime Propyltripropoxydecane, 2-propenyloxyethyltrimethoxyxanthene>, 2-propenyloxyethyltriethoxylate, 2-propanyloxyethyl Propoxy decane, 3-propenyl methoxypropyl trimethoxy oxime, 3-propanyloxypropyl triethoxy sulphur s- 3 - propylene succinyl propyl - 11 - .201224060 Oxydecane, 3·mercapto propylene methoxy propyl trimethoxy decane: 3-methyl propylene methoxy propyl triethoxy decane, methacryl methoxy propyl tripropoxy oxa alkane, etc. . These compounds may be used singly or in combination of two or more kinds. Vinyl phenyl dimethoxydecane vinyl dimethyl methoxy decyl allyl methyl dimethoxy decyl allyl dimethyl methoxy decane monovinyl methyl methoxy sulphur as the above Specific examples of the compound represented by the formula (2) include ethylene methyl dimethoxy oxalate, ethylene methyl diethoxy oxa alkane, vinyl phenyl diethoxy decane, and vinyl two. Methyl ethoxy decane, propyl propyl diethoxy decane, propyl propyl decyl ethoxy decane, diethylene methyl ethoxy decane, 3-methyl propyl (tetra) oxy propyl Methyl: foxyl, 3 propylene oxypropyl methyl dimethoxy sulphur, 3 - methyl propylene oxypropyl phenyl monomethoxy decane, 3-propenyl methoxy Propyl phenyl dimethoxy oxime, 3,3'-dimethyloxypropyl dioxime oxime 6, 33 bis methoxypropyl dimethoxy decane, 3 3, ' '3 _Dimethyl propylene methoxy propylene carbaryl decane, 3,3', 3''-trienyl methoxy methoxy methoxy oxime: These compounds may be used singly or in combination. Use two The cleavage resistance and the surface hardness of the chemical substances represented by the above formulas (1) and (2) are as follows: from the ability to be high water, and the reactivity of hydrolysis condensation is 密Opinions of trimethoate, p-phenylethenyl, triethyl ethoxylate, methoxypropyltrimethoxy, m-oxygen: propane, 3-mercaptopropenyloxypropyl, sulphate, ethoxylate Decane, 3-propene oxime

S 12-201224060 oxypropyltriethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-propylenemethoxypropylmethyldimethoxyoxydecane, and the like. Further, the compound (a2) is preferably a hydrolyzable calcined compound represented by the following formula (3). (R6〇fcSi—(R7-W)q (3) (In the formula (3), R6 represents an alkyl group having a carbon number of i to 4, R7 represents a single bond 'indenylene or alkylene, and W represents carbon. a substituted or unsubstituted alkyl group having 1 to 20 atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, an amine group, an anthracenyl group, an epoxy group, a glycidoxy group or a 3,4- The epoxycyclohexyl group, q represents an integer of 0 to 3.) The alkyl group of R6 is the same as the Ri of the above formula (丨), and the alkyl group and the aryl group of Wt include the above formula ( 2) The same group as z, and the alkyl group in R7 may be the same as the above formula R5. Further, as the substituent of the alkyl group and the aryl group in w, the above formula (2) may be mentioned. The substituent of the aryl group in Z is the same group. As R, a single bond or a group having 2 to 3 carbon atoms is preferable, and as W, a substitution of 碳~丨〇 is preferred. Or an unsubstituted substituent, a substituted or unsubstituted aryl or glycidoxy group having 6 to 8 carbon atoms. Further, as the substituent of the alkyl group or the aryl group, a γ atom is preferred. As q, preferably 0 1. The hydrolyzable decane compound represented by the above formula (3) includes a decane compound having four hydrolyzable groups, a residual compound having one non-hydrolyzable group and three hydrolyzable groups, and two non-hydrolyzable groups. And a hydrolyzable group of a decane compound, or a mixture thereof. As a specific example of such a hydrolyzable decane compound,

-13 - S 201224060 The dream compound having four hydrolyzable groups may, for example, be tetramethoxydecane, tetraethoxydecane, tetrabutoxydecane, tetraphenoxysulphate, tetrabenzyloxydecane, tetra-positive a propoxy decane, a tetraisopropoxy oxime, or the like; a pyroxene compound having one non-hydrolyzable group and three hydrolyzable groups; Institute, methyl triisopropoxy oxime, methyl tributoxy decane, ethyl trimethoxy sulphur, ethyl diethoxy sulphur, ethyl triisopropoxy sulphate, ethyl tri Butoxy decane, butyl trimethoxy decane, decyl trimethoxy decane, trifluoropropyl dimethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, amine trimethoxy decane , Aminotriethoxydecane, 3-Mercaptopropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltridecyloxydecane, γ-glycidoxypropyltrioxane a decane compound having two non-hydrolyzable groups and two hydrolyzable groups; monomethyl decyl decane, diphenyl Methoxy Silane, dibutyltin dimethoxide money, propyl methyl dimethoxy 3_ sparsely cornerstone Xi homes. These compounds may be used alone or in combination of two or more. Among these hydrolyzable alkane compounds, preferably four hydrolyzable decane compounds, and having i non-hydrolyzable groups and three hydrolysiss The Shishiyuan compound of the nature is particularly preferably a compound having a non-hydrolyzable group of ^^~11U and three hydrolyzable groups. As the specific example of the preferred hydrolyzable ruthenium compound, heptulop a 4 Μ is exemplified by tetraethoxy Α 7 _ . Ruthenane, methyltrimethoxydecane, methane-ethyllacyldecane 'methyltriisodecane,, inner-rolled decane, methyltributyloxy/gas, benzyltrimethoxy-decaneethyltrimethyl Oxydecane, ethyl: ethoxy decane, acetamidine ** 丞, propyl decyl decane, ethyl tributoxy decane. 14- 201224060, butyl dimethoxy sulphur, Γ_glycidoxypropyltrimethoxyxanthene, decyltris-f-oxydecane, trifluoropropyltrisyloxy oxime. In the total of the (al) compound and the (a2) compound, the proportion of the (al) compound to be added exceeds 15 mol%, preferably 丨6 mol% or more, particularly preferably 18 mol% or more^ When the ratio of the (al) compound is 15 mol% or less, the heat resistance, adhesion, and resolution of the cured film obtained by the 'difference in exposure sensitivity' are lowered. Further, the upper limit of the ratio of addition of the (al) compound is preferably from 5 〇 mol% to 40 mol%, from the viewpoint of crack resistance, heat resistance, and adhesion. 30 moles %. The condition for co-hydrolysis condensation of the compound (4)) and the compound (a2) is as long as at least a part of the compound of the (8) compound and the (a2) compound is hydrolyzed to convert the hydrolyzable group into a gas group, and a condensation reaction occurs. The restrictions, for rabbits _ Am j% \ _ von von examples, can be listed below.乂 乂 为 为 用 用 溶 溶 溶 溶 丨 丨 丨 丨 丨 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 。 。 。 。 。 。 。 。 。 。 In the co-hydrolysis condensation reaction using the I (")-based compound and the (a2) compound == It is preferable to use the reverse osmosis membrane treatment and ion exchange to suppress the water purified by the hydrazine. The amount of water, the uk eye uk asks for the reactivity of the hydrolysis. As the use of water, relative to the (al) compound and 1 mole, preferably (M~3 mole: the hydrolyzable group of the compound is good ( ΜΗ.5莫耳., by your t good is 〇.3~2 moer, the reaction speed of the step-by-step is better. The amount of water can be used to make the hydrolysis as (al) compound and use. The solvent is not produced in the co-hydrolysis condensation reaction of the special (tetra) compound, and a preferred example of such a solvent which is used in the preparation of the polyurea 201224060 oxime-burning composition described later, an acid ester or a diethylene glycol Alkyl ether, base-acetic acid vinegar, propionic acid s-type, or two types of diethylene glycol dimethyl ether, diethyl hydrazine, propylene glycol monoethyl sulphate, methoxy Methyl propionate. The use of gluten is the same type. It can be exemplified by ethylene glycol monoalkyl ether acetoacetin monoalkyl.趟 'Propylene glycol mono-k compounds can be used alone. Among these solvents, especially good diol ethyl methyl ether, propylene glycol monopropylene glycol monomethyl ether acetate or 3- for (al) compounds and (a2) The cohydrolysis condensation reaction of the compound is preferably carried out on an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, citric acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluorodecanesulfonic acid, phosphoric acid, acidic ion exchange resin, various Lewis Acid), alkali catalyst (for example, amines, primary amines, secondary amines, tertiary amines, pyridine and other nitrogen-containing compounds; basic ion father for tree 爿 a, sodium hydroxide and other hydroxides; potassium carbonate, etc. The use of a catalyst such as a carbonate; a carboxylate such as sodium acetate; a variety of Lewis bases; or an alkoxide (for example, zirconium alkoxide, titanium alkoxide, or alkane oxide). From the viewpoint of the hydrolysis condensation reaction, the total amount of 1 mol of the (a) compound and the (a2) compound is preferably 0'2 mol or less, more preferably 〇〇〇〇〇1 to 〇1 mol. (al) compound and (a2) compound and The reaction temperature and the reaction time in the co-hydrolysis condensation reaction can be appropriately set, and for example, the following conditions can be employed. The reaction temperature is preferably 4 Torr to 2 Torr, more preferably 50 to 150 ° C. Preferably, it is 3 minutes to 24 hours, more preferably 1 to 12 hours. By setting the reaction temperature and the reaction time, the hydrolysis condensation reaction can be carried out most efficiently. anti-

-16- S 201224060 The hydrolyzable decane compound, water and catalyst should be added in one step in the system, or the hydrolyzable decane compound, water and catalyst can be added to the reaction system in multiple times, according to the multi-step method. The hydrolysis reaction and the condensation reaction are carried out. Further, after the hydrolysis condensation reaction, a dehydrating agent may be added and then evaporated to remove water and the produced alcohol from the reaction system. The dehydrating agent used in this stage is generally obtained by adsorbing or coating excess water to completely dehydrate the dehydration ability or by evaporation. As a component [A] obtained in this manner, it is preferred to contain a derivative derived from The structural unit represented by the following formula (4) of the compound (al) (hereinafter, also referred to as structural unit (4)), and the structural unit represented by the following formula (5) derived from the compound (a2) (hereinafter also referred to as The structure element (5)) and the structure early element represented by the following formula (6) (hereinafter referred to as structure early element (6)). X a R2—Si03/2 (4)

Si04/2 (5) R8~Si〇3/2 (6) [In the formula (4), R2 and X have the same meanings as defined above. In the formula (6), R8 represents a substituted or unsubstituted carbon number of 1 to 20 Burning base. Further, the substituent of the alkyl group in R8 may be the same as the substituent of the aryl group in Z of the above formula (2). The content ratio (mole ratio) of various structural units in the component [A] is preferably structural unit (4) / structural unit (5) / structural unit ^ 16 to 25/10 to 40/40 to 70, more Good for 18~25/20~40/40~60. The molecular weight of the component obtained by the hydrolysis condensation reaction can be measured by GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase as a polystyrene-equivalent weight average molecular weight] A]

S -17- 201224060 The average of the weight of the knives is preferably in the range of 5 〇〇 to 1 ,, and more preferably in the range of 1000 5,000 to 5,000. By setting the value of the weight average molecular weight of the component (4) to 5 Torr or more, the film formability of the coating film of the polysiloxane composition can be improved. On the other hand, the 蕤 λ fineness makes the average molecular weight of the heavy enthalpy of 1 〇 or less, and it is possible to prevent deterioration of the testability of the composition of the poly oxysulfuric acid. The average molecular weight (MW) of the powder denier 1 t and the number average molecular weight μ vu measured according to the same conditions, the ratio of the smash (), that is, the degree of dispersion (Mw/Mn) is preferably 1.0 to 15_0, more preferably ??? ! 〇 〇, 牛 / Better is 1,1~5_〇. By setting it within such a range, it is possible to record alkali developability, adhesion, and crack resistance. What is the [Β] component: the component is a non-radical polymerizable organic compound, which is more resistant to cracking, heat resistance, adhesion and analysis than the [A] component alone. The degree [B] component can be obtained by the gentleman's day under the same conditions as the [A] component and one of the above (3) dry & u & J conditions. The delayed (co)hydrolysis condensation is obtained by (co)hydrolysis condensation reaction, and the structural unit containing the following formula (7) is dry-coated from the "knives of the knife" (hereinafter, preferably) (hereinafter, also (7) And the following formula (8) - Qin Wei,,, 〇 unit (8)). L聃 is a structural unit R9-Si03/2 (7)

Rl〇~Si〇3/2 (8) [In the formula (7), R9矣-mountain does not have a number of atoms, and 10 is replaced by a 201224060 alkyl group. In the formula (8), R1Q represents a carbon number of 6~ 14 substituted or unsubstituted aryl groups. In addition, examples of the substituent of the alkyl group in R9 and the aryl group in R10 include the same substituents as those of the aryl group in Z of the above formula (2). The content ratio (mol ratio) of various structural units in the [B] component is preferably structural unit (7) / structure early (8) = 30 to 70 / 70 to 3 Å, more preferably 40 to 60 The weight average molecular weight (Mw) of the component [B] obtained by the hydrolysis condensation reaction can be measured from the viewpoint of the film forming property and developability of the coating film under the same conditions as those of the component [A]. It is preferably 5 Å to 1 Torr, more preferably 1000 5,000 to 5,000. Further, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured under the same conditions, that is, the degree of dispersion (Mw/) Mn), from the viewpoints of alkali developability, adhesion, and crack resistance, it is preferably 1 ❶ to 丨 5 〇 'more preferably 1.1 to 1 〇. 〇 ' Further more preferably LU 0. As [A] The content ratio of the component and the component [B] is preferably from 80 to 400 parts by mass, more preferably from 100 to 200 parts by mass, per 100 parts by mass of the component [B]. Further, it is preferably adjusted appropriately. 'Including the structural unit having a radical polymerizable organic group in all the structural units constituting the [A] component and the [B] component The ratio of the structural unit derived from the U1) compound in all the structural units of the [A] component and the [B] component is 1 to 20 mol%, more preferably 5 to 18 mol%, Very good for 1 〇 ~ 1 5 mol%. By including a structural unit having a radical polymerizable organic group in such a ratio, adhesion and cracking property can be achieved at a high level. 19- £201224060, heat resistance, scratch resistance, and radiation sensitivity can also be obtained. In addition, the content ratio of the structural unit having a radical polymerizable organic group in all the structural units constituting the [A] component and the [B] component can be determined by W-NMR, 13C-NMR, FT-IR. The qualitative analysis of the thermal decomposition gas chromatograph was carried out for qualitative and quantitative analysis. [C] component [C] component is a radical polymerization initiator. The radical polymerization initiator used in the present invention may, for example, be a fluorenyl-fluorenyl compound, an acetophenone compound or a biimidazole compound. Specific examples of the 0-fluorenyl hydrazine compound include ethyl ketone-1-[9-ethyl-6-(2-methylbenzylmethyl)-9H-carbazol-3-yl]-1-( 0-acetamidine), 1-[9-ethyl-6-benzylidene-oxazol-3-yl]-oct-1-one oxime-0-acetate, 1-[9-ethyl- 6-(2-Methylbenzylidene)-9.H.-carbazol-3-yl]-ethan-1-one oxime-0-benzoate, 1-[9-n-butyl-6 -(2-ethylphenylhydrazino)-9.Η·-carbazole_3_yl]-ethan-1-one oxime-indole-benzoate, ethyl ketone-1-[9-ethyl- 6-(2-mercapto-4-tetrahydrofuranylphenyl)-9.Η_-咔〇?-3-yl]-1·(0-ethylen), acetam-1-[9-ethyl -6-(2-methyl-4-tetrahydropyranylphenyl)-9·Η·-oxazol-3-yl]-1-(0-acetamidine), ethyl ketone-1- [9-Ethyl-6-(2-indolyl-5-tetrahydrofuranylphenyl)-9.Η--oxazol-3-yl]-1-(0-acetamidine), ethyl ketone- 1-[9-Ethyl-6- {2-indolyl-4-(2,2-dimercapto-1,3-dioxolanyl)nonyloxyphenylhydrazino} -9· Η· - Leica. Sitting on -3 -yl]-1-(〇-B-flavor), acetam-1 - [9-ethyl-6-(2-indolyl-4_tetrahydrofuranyloxyphenyl)--9. Η·_oxazol-3-yl]-1-(0-acetamidine) and the like. These fluorene-fluorenyl hydrazine compounds may be used alone or in combination of two or more. -20- 201224060 Among these, as a preferred ruthenium-indenyl ruthenium compound, ethyl ketone-1-[9-ethyl-6-(2-mercaptobenzylidene)-9Η-carbazole can be cited. -3-yl]-1-(0-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-indolyl-4-tetrahydrofurylmethoxybenzylidene)-9· Η·-carbazol-3-yl]-1-(0-acetamidine), ethyl ketone-1-[9-ethyl-6-{2-mercapto-4-(2,2-dimethyl -1,3-dioxolanyl) decyloxybenzhydryl} -9. Η--oxazol-3-yl]-1-(0-acetamidine). The acetophenone compound may, for example, be an α-amino ketone compound or an α-pyridyl ketone compound. Specific examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1-(4-carbolinylphenyl)-butan-1-one and 2-dimethylamine. 2-(4-mercaptobenzyl)-1-(4-yrosolin-4-yl-phenyl)-butan-1-one, 2-mercapto-1-(4-sulfonylphenyl) )-2-glyphosylpropan-1-one and the like. Specific examples of the α-hydroxyketone compound include 1-phenyl-2-alkyl-2-methylpropan-1 - fluorene, 1-(4-isopropyl basic)-2-yl-2-(2)- Mercaptopropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, and the like. These acetophenone compounds may be used singly or in combination of two or more. Among these acetophenone compounds, an α-amino ketone compound is preferred, and particularly preferably 2-didecylamino-2-(4-methylbenzyl)-1-(4-isoline-4-yl) -Phenyl)-butan-1 -anthracene, 2-methyl-1 -(4-oxothio basic)-2 - miso-propylpropan-1 -anthracene. Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'. -biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4 -diphenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'·bis(2,4,6-trichlorophenyl)-4, 4',5,5'-tetraphenyl-1,2'-biimidazole and the like. This 201224060 may be used alone or in combination of two or more. Among these biimidazole compounds, preferred are 2,2,-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl.^, biimidazole, 2,2,·bis ( 2,4_二气笨基)-4,4',5,5'-tetraphenyl-u-biimidazole, 2,2,·bis(2,4,6_trisole)-4, 4,5,5 _tetraphenylbiimidazole, particularly preferably 2,2,_double two-gas base)-4,4,5,5'-tetraphenyl 丨, 2, _ _ _. sit. When a biimidazole compound is used as the [C] component in the polyoxyalkylene composition of the present invention, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as "amine" may be added in order to sensitize the composition. Base sensitizer"). The amine-based sensitizer may, for example, be 4,4,-bis(didecylamino)benzophenone or 4,4,bis(diethylamino)benzophenone. Among these amine sensitizers, particularly preferred is 4,4, bis(diethylamino)benzophenone. k These amine-based sensitizers may be used alone or in combination of two or more. Further, when a biimidazole compound and an amine-based sensitizer are used in combination, a thiol compound may be added as a hydrogen radical providing agent. When the biimidazole compound is sensitized by an amine-based sensitizer, it splits to produce an imidazole radical, and its direct use may not exhibit high polymerization initiating ability. However, in a system in which a biimidazole compound and an amine-based sensitizer coexist, a thiol compound can be added to provide an imidazole radical with a wind radical generated by a thiol compound. As a result, the toxin radical is converted into a neutral σ rice bran, and a component having a sulfur radical having a high polymerization initiation ability is produced, and a cured film having a high surface hardness can be formed even if the radiation amount is lowered. Specific examples of the thiol compound include,

-22- S 201224060 2- w basic open thiazole '2-巯 base stupid. β ^ + open saliva, 2-mercaptobenzimidazole, 2-carbyl-5-methoxybenzindole. Sitting | Temple Fangxiang thiol compound; 3-mercaptopropionic acid, 3·mercaptopropionic acid.. Wenzhi knows the aliphatic monothiol compound, neopentyl alcohol tetrakis(mercaptoacetate), final, 玺ο - 2, more than 2 g of aliphatic sulfur v 00 ^ L private compound, such as neodymidine tetrakis(3-sodium propionic acid 8). These thiol compounds may be used alone or in combination of two or more. Among these thiol compounds, the pull of 4, T will preferably be 2-mercaptobenzothiazole. When the compound and the amine-based sensitizer are used in combination, the amount of the amine-based sensitizer used is preferably 0.1 to 50 parts by mass based on 100 parts by mass of the ruthenium compound. Better for 丨~,..,, quality damage. When the amount of the amine-based sensitizer used is in the above range, T is long: the hardening reactivity at the time of exposure is increased, and the surface hardness of the obtained cured film is improved. Further, when a biimidazole compound, an A + amine ruthenium sensitizer, and a thiol compound are used in combination, it is preferably used as a thiol compound, and preferably 1 part by mass relative to the biimidazole compound. ~5〇曾香》·ν * f丄1 Μ buy a portion, preferably 1 to 20 parts by mass. The surface hardness of the obtained cured film can be improved by allowing the amount of the thiol compound to be used in a free manner; In the present invention, it is preferred that the [J] component L J is at least one selected from the group consisting of a 0-branched compound and an acetophenone compound J σ籾, and may further contain a biimidazole compound. The amount of use of the component [C] is preferably 0.05 to 30 parts by mass, more preferably 1 to 15 parts by mass, based on the total of 100 parts by mass of the [Α] component and the component. When the amount of use is within the above range, even at a low exposure amount, high radiation sensitivity can be exhibited.

S -23- 201224060 A cured film with sufficient surface hardness. [D] component [D] component is a solvent. As the solvent, it is not particularly preferable to contain an alcohol solvent as a protic solvent. By means of the agent, the various components can be uniformly dissolved or dispersed, and the coating property of the composition solution on the large substrate can also suppress the occurrence of unevenness of stripes, uneven pinholes, uneven brightness, etc., and the film thickness uniformity β is used as the Examples of the alcohol-based solvent include long-chain alkyl alcohols such as 1-hexanol, 1-octanol, decyl decyl alcohol, decyl dodecyl alcohol, and 1,8-octanediol; and aromatic alcohols such as benzyl alcohol. Ethylene glycol monoalkyl ethers such as ethyl alcohol monomethyl ether, ethylene glycol monoethyl ether, diethyl ether, ethylene glycol monobutyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropyl ether Propylene glycol monoalkyl ethers such as propylene glycol monobutyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether monoalkyl ether; monopropanol monomethyl scale, dipropylene glycol single A dipropylene glycol monovalent such as an early propyl bond or a dipropylene glycol monobutyl ether. These alcohol-based solvents may be used singly or in combination with two or more alcohol solvents, particularly from the coating 5, preferably benzyl alcohol, ethylene glycol monopropyl ether, ethylene glycol propylene glycol monodecyl ether, propylene glycol. Monoethyl ether. The component [D] may be used singly or in combination, but the ester is dissolved in an alcohol. This may result in uneven coating (further increase > 1,6-hexanediol diol monopropyl The monobutylene ether and the two types of monobutyl ether are used in the case of alcohols such as diethylene glycol and dipropylene glycol alkyl ether, and the two are used in 201224060. The amount of [D] component used is relative to [A]. 100 parts by mass of the component is preferably 5 parts by mass to 300 parts by mass, and more preferably 1 part by mass to 200 parts by mass. By using the amount of the component [D] in the above range, the glass substrate or the like can be improved. The coating property can also suppress the occurrence of coating unevenness (strip unevenness, pinhole unevenness, unevenness of light and darkness, etc.), and further improve film thickness uniformity. In the present invention, it is compatible with an alcohol-based solution such as a diethylene glycol-based base. Examples of the N-propylene glycol monoalkyl propionate and the like as a solvent other than the alcohol-based solvent can be exemplified as diethylene glycol alkyl ether methyl ketone diethyl alcohol diethyl hydrazine. Ethylene glycol alkyl ether acetate fiber acetate ethyl ester cellosolve acetate ethylene glycol monoethyl ether acetate vinegar as propylene glycol monoalkyl vinegar alcohol sulfhydryl ether acetic acid 3 propylene glycol propyl acetate propylene glycol single As the propylene glycol monoalkyl ether propanol hydrazine, decyl propyl propyl acrylate propylene glycol propyl ether propionic acid la propylene propylene glycol monobutyl, as an aromatic hydrocarbon, may be exemplified as an example 5, and other solvent ethers may be mentioned. The ethylene glycol base is called a vinegar, an aromatic hydrocarbon, an anthracene, a t, and a hydrazine, and the following solvents may be mentioned, such as tetrahydrofuran, etc.; 'for example, diethylene glycol diethylene glycol or diethylene glycol may be mentioned. Examples of the ethyl esters include, for example, a T-soluble acid ester, a polyethylene glycol monobutyl ether acetate, and the like; and an acid ester, for example, an internal monoethyl ether acetate. Propylene glycol monoether ether acetate; etc.; and esters, for example, propylene-monoethyl ether propionic acid g, propylene glycol monoether ether Esters;. Yue include benzene, xylene and the like, such as leather, Yue ethyl ketone, methyl isobutyl

S-25-201224060 ketone, cyclohexanyl, 2-g-glycol, 4-pyridyl-4-mercapto-2-pentene i, etc.; as the ester, for example, methyl acetate, ethyl acetate, acetic acid Propyl ester, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-yl-based 2-methylpropionate, 2-hydroxy-2-methylpropionate, base Ethyl acetate, ethyl hydroxyacetate, butyl hydroxyacetate, lactic acid lactic acid, ethyl lactate, propyl lactate, butyl lactate, 3-propionic acid vinegar, 3 · propyl propyl acetate, 3 - propyl propyl acrylate, butyl 3-propionate, decyl 2-hydroxy-3-mercaptobutyrate, decyl decyl acetate, ethyl decyl acetate, propyl decyl acetate 'N-butyl oxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate butyl ethoxyacetate, decyl propyl acetate, ethyl propoxyacetate, Propyl propyl acetate, butyl propyl acetate, decyl acetoacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2-methoxypropionic acid Vinegar, 2-methoxypropionic acid ethyl acetate, 2-methoxypropyl Prop @ purpose, 2 - methoxy propionate, butyl 2-ethoxy-methyl, 2-ethoxy ethyl propionate and the like stuffed. These solvents may be used singly or in combination of two or more. The composition of the present invention may further contain a subgingival component. The [Ε] component is excluded from the component in the unsaturation of the polymerization of [C] radical radiation. From the viewpoint of the strength of the cured film of the polymerizable unsaturated monomer, the (meth) acrylate having a functional or higher functional group is used as a monofunctional (meth) propylene g polymerization initiator in the presence of a conjugate. However, the component [A] contained in the component [A] is excellent in polymerizability, and is preferably a monofunctional, bifunctional or 3> t vinegar, and examples thereof include a 2-base group B.

-26- S 201224060 acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-propenyloxy group) Ethyl)(2-hydroxypropyl)phthalate, (2-methacryloxyethyl)(2-hydroxypropyl)phthalate, ω-carboxypolycaprolactone Monoacrylate and the like. Examples of the commercially available product include ARONIX®-101, M-ll, Μ-114, Μ-5300 (above, East Asia Synthetic Company); KAYARAD TC-1 10S, TC-120S (above, Nippon Kayaku Co., Ltd.); Examples of the bifunctional (fluorenyl) acrylate such as Viscoat 158 and 2311 (above, Osaka Organic Chemical Industry Co., Ltd.) include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimercapto acrylate, and B. Diol dimercapto acrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimercapto acrylate, 1,6 - Hexanediol diacrylate, 1,6-hexanediol dimercaptopropionate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, etc. . As a commercially available product, for example, ARONIX M-210, M-240, M-6200 (above, East Asia Synthetic Company); KAYARAD HDDA, HX-220, R-604 (above, Nippon Kayaku Co., Ltd.); Viscoat 260, 312, 335HP (above, Osaka Organic Chemical Industry Co., Ltd.); LIGHT-ACRYLATE 1, 9-NDA (Kyoeisha Chemical Co., Ltd.). Examples of the trifunctional or higher (fluorenyl) acrylate include, for example, trimethyl methacrylate triacrylate, trimethyl methacrylate trimethyl propyl acrylate, and neopentyl alcohol triacrylate 'new pentylene Alcohol tridecyl acrylate, neopentyl alcohol tetraacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dioxane

S -27- 201224060 Tetraol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethylene acrylate, epoxy epoxide modification Neopentyl alcohol hexapropyl acrylate, tris(2-acetoxyethyl) phosphate vinegar, tris(2-methoxypropenyloxyethyl) phosphate, succinic acid modified pentaerythritol Triacrylate, succinic acid modified dipentaerythritol pentaacrylate, tris(propylene oxyethyl) isocyanurate, and also has a linear chain extension and alicyclic structure, and has A compound having two or more isocyanate groups and a polyfunctional amine group obtained by reacting a compound having one or more hydroxyl groups in the molecule and having three, four or five (meth) propylene fluorenyloxy groups An acid ester acrylate compound or the like. As a commercially available product, for example, ARONIX M-309, M-315, M_400, M-405, M-450, M-7l, M-8030, M-8060, ΤΟ·1450 (above, East Asia Synthesis Corporation) ); KAYARAD ΤΜΡΤΑ, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA-12 (above, Nippon Kagaku); Viscoat 295, 300, 360, GPT, 3PA, 400 (above' Daban Organic Chemical Industry Co., Ltd.; as a commercially available product containing a polyfunctional amine-based carbendazole 8-acrylic acid-based compound, New Frontier R 1150 (co-industrial pharmaceutical company), kayaraD DPHA-40H (sakamoto) Chemical companies) and so on. Among these [E] components, preferred are carboxypolycaprolactone monoacrylic acid = 1,9-nonanediol dimethacrylate, trimethylolpropane tripropylene IS, and pentaerythritol triacrylate. Ester, neopentyl alcohol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentane: a mixture of alcohol acrylate and dipentaerythritol pentaacrylate, epoxy B Alkyl modified dipentaerythritol hexaacrylate, succinic acid modified neopentyl

-28- S 201224060 Alcohol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, and commercially available products containing polyfunctional urethane acrylate compounds. Among them, a trifunctional or higher (fluorenyl) acrylate is preferable, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is particularly preferred. The component [E] may be used singly or in combination of two or more. The amount of use of the component [E] is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, based on 100 parts by mass of the total of the components [A] and [B], and particularly preferably 20 to 100 parts by weight. Parts by mass. By using the amount of the component [E] in the above range, the sensitivity of the composition, the surface height of the obtained hardened film, and heat resistance can be further improved. [F] component [F] component is at least one selected from the group consisting of organic particles and inorganic particles. By containing the [F] component, scratch resistance, crack resistance, and the like can be improved. The average particle diameter of the organic particles and the inorganic particles is preferably in the range of 〇 5 to 〇 5 μmη. The component [F] may be directly added to the other components in the form of a powder, or may be added as a solvent dispersion to the other components and mixed. As the organic particles, acrylic particles or the like are preferably used. As a C

Oxidation error, titanium oxide, zinc oxide, and examples thereof include cerium oxide, zinc oxide, magnesium oxide, calcium carbonate, and carbonic acid.

S -29- 201224060 Magnesium sulphate, talc, smectite, etc., which are mainly composed of oxidized ♦ and alumina. The shape of the inorganic particles may be spherical, rod-shaped, plate-like, fibrous, or irregular, and the particles may be solid, hollow, or porous. Examples of commercially available products of inorganic particles include, for example, ADMAFINE SO-E1, SO-E2, SO-E3, SO-E4, SO-E5, SE320 0-SEJ (manufactured by Admatechs Co., Ltd.), and SS (H). SS03, SS15, SS35 (made by Osaka Chemicals Co., Ltd.), etc. As specific examples of such inorganic particles, the cerium dioxide particles include methanol cerium oxide sol, IPA_ST, MEK-ST, NBA-ST, and XBA-. ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST_40, ST-C, ST-N, ST-0, ST-50, ST-OL (Made in Chemical Industry) Examples of the zirconia particles include HXU-1 10JC, HXU-210C, NZD-3101 (manufactured by Sumitomo Osaka CEMENT Co., Ltd.), ID191 (made by Ding Ba丫 Into), and 21^]^八15\^%- £05 ((:.1. Chemical system), titanium oxide particles can be listed as MT-05, MT-100W, MT-100SA, MT-100HD, MT-300HD, MT-150A, ND138, ND139, ND140, ND154, ND165, ND177, TS-063, TS-103, TS-159 (manufactured by TAYCA Co., Ltd.), etc. The inorganic particles can be surface-treated with a decane coupling agent or the like. By performing such surface treatment, it is possible to improve with other surfaces. Compatibility of ingredients can be improved in groups The component [F] may be used singly or in combination of two or more. The amount of use of the component [F] is preferably 1 part by mass based on 100 parts by mass of the component [A]. ~6〇〇 parts by mass, more preferably 10 parts by mass to 200 parts by mass.

S -30- 201224060 When the amount of the component [F] used is in the above range, the scratch resistance of the obtained protective film and interlayer insulating film can be further improved. In the addition of the above-mentioned [A^[D] component, the composition of the present invention can contain the [G] sensitizing radioactive acid initiator and the sensitizing radiation in a range that does not impair the intended effect as needed. Alkaloid initiator, [Η] surfactant and other optional components. [G] component [G] component is a radiation-sensitive linear acid initiator and a radiation-sensitive linear alkali initiator [G] component is defined as a catalyst which can be released from the condensation and hardening reaction of polyoxyalkylene by irradiation with radiation. Acting acidic active substance or compound of basic active substance. - as a radiation sensitive acid initiator, preferably diphenyl iodine salt, diphenyl salt and four gases. It is a diphenyl sulfonium salt and a tetrahydro thiophene salt. Specific examples of the diphenyl iodine rust salt include diphenyl iodine rust tetrafluoroborate 'diphenyl iodine hexafluorophosphate, diphenyl iodonium difluorolithoate, and diphenyl moth rust. Trifluoromethyl carboxate, diphenyl iron triterpene acetate, diphenyl iodonium _ p-toluene sulfonate, diphenyl iodine butyl butyl (2,6-difluorophenyl) borate, 4-methoxyphenylphenyl iodonium tetrafluoro^ I salt, bis(4-butybutylphenyl) iodine tetrafluoroborate, bis(4_t-butylphenyl)iodonium hexafluorophosphate Arsenate, bis(4_t-butylphenyl)iodonium trifluoromethanesulfonate (IV) 'bis(4-t-butylphenyl-tert-butylphenyl)iodonium-p-toluenesulfonate, Bis(4·t-butylbenzyl iodide camphorsulfonic acid, etc. ^ ] Specific examples of triphenylsulfonium tris-trisuccinyldifluorobutanoic acid as diphenyl salt can be cited, fluoroindole sulfonate , triphenyl shovel camphor rhemin 201224060 salt, triptypic trifluoroacetate, triphenyl sulfonium-p-toluene sulfonate, triphenyl sulfonium butyl tris (2,6-difluorophenyl) a borate or the like. As a specific example of the tetrahydrothiophene salt, a _(4_n-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate, 丨_(4•n-butoxyindol-1-yl)tetrahydrothiophene nonafluoro-n-butanesulfonate , 1-(4•n-butoxynaphthyl)tetrahydrothiophene-1,1,2,2·tetrafluoro-2-(norbornane-2-yl)ethanesulfonate, 1_(4-n-butyl Oxynaphthalene-indole-yl)tetrahydrothiophene-2-(5t-butoxy-oxybisbicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate , 1_(4_n-butoxycain-1-yl)tetrahydropyrrol-2-(6·t-butoxycarbonyloxybicyclo[2.2.1]hept-2-yl)_1,1,2 , 2-tetrafluoroethyl acid salt, 1-(4,7-dibutoxy-1-naphthyl)tetrahydrothiophene trifluorosulfonate, etc. Among these radiation-sensitive linear acid initiators, radiation is increased. From the point of view of sensitivity, 'excellent is tris-triphenylsulfonium sulfonate, triphenyl epoxide, helium 4,7·dibutoxy-1-naphthyl)tetrahydrothiophene trifluoride Sulfonium sulfonate. Examples of the radiation-sensitive alkali initiator include 2-nitrophenylcyclohexylamino phthalate, [[(2,6-dimercaptobenzyl)oxy]yl]cyclohexylamine, hydrazine- (2. Nitrobenzyloxycarbonyl) °pyrrolidine, bis[[(2-nitrobenzyl)oxy]carbonyl]hex-1,6-diamine, triphenylmethanol, hydrazine-amine carbhydryl Hydroxylactam, 0-amine fluorenyl hydrazide, 4-(nonylthiobenzimidyl)-1-mercapto-1-indolylethane, (4-tyrosyl alum) Benzyl-1-diamidinopropylpropane, 2-benzyl-2,dimethylamino-by- morpholinylphenyl)·butanone, hexammine (trimium) tris(triphenylmethyl) Boronate) and the like. Among these sensitizing radioactive alkali generators, from the viewpoint of improving the radiation sensitivity, the specific ones are 2-nitrobenzylcyclohexylamino decanoate and hydrazine-amine hydrazino hydroxy decylamine.

S -32- 201224060 As the [G] component, one type may be used alone or two or more types may be used in combination. The amount of the component [G] to be used is preferably 20 parts by mass or less, more preferably i parts by mass or less, based on the [a] component 1 enamel. By using the amount of the [G] component in an amount of 2 parts by mass or less, it is possible to obtain an excellent cured film having excellent radiation sensitivity, a pencil hardness of the formed protective film and the interlayer insulating film, and a balance between heat resistance (heat and transparency). product. [H] component '[H] component is a surfactant. The component [H] is added for the purpose of improving the coatability of the polysiloxane, improving the coating property, reducing coating unevenness, and improving the developability of the radiation-irradiated portion. As the [H] component, a nonionic surfactant, a fluorine-based surfactant, and an organic lanthanoid surfactant are preferable. Examples of the nonionic surfactant include polyoxyethylene lauryl sulfonate, polyoxyethylene stearyl bond, polyoxyethylene oleyl ether, and the like; and polyoxyethylene octylphenyl; Polyoxyethylene aryl ethers such as saki, polyoxyethylene decyl phenyl ether; polyethylene glycol dilaurate, polyethylene glycol, etc.; (meth)acrylic acid ^, 4 "Items, etc. Examples of the (meth)acrylic copolymers are 00, and may be exemplified by POLYFLOW No. 57, Νο. 95 (manufactured by Bajiro Chemical Co., Ltd.). As an emergency preparation, 'surfactant, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetramine; ^, ^ propyl) ether, hydrazine , 2,2·tetrafluorooctylhexyl ether, octaethylene glycol di(I d ? , Α,, -tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3- Fluoroethers such as hexafluorocyclohexane (. Λ _ _ _ 酵 丨 (1, 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di-n-helium pentyl) ether; perfluorododecyl sulfonic acid , 2'8'8,9,9,1〇,1〇_decafluorododecane, 1122,3,3 hexafluoro

S-33- 201224060 Fluoroalkanes such as decane; sodium fluoroalkylbenzenesulfonates; fluoroalkyl oxyethylene ethers; fluoroalkyl ammonium iodides; fluoroalkyl polyoxyethylene ethers; perfluoroalkyl Polyoxyethylenes; perfluoroalkyl alkoxides; fluoroalkyl esters. As a commercially available product of these fluorine-based surfactants, EFTOP EF3 01, 3 0 3, 3 5 2 (manufactured by Shinki Ueda Chemical Co., Ltd.), MegAFACE F171, 172, and 173 (manufactured by Dainippon INK Co., Ltd.) can be cited. , Fluorad FC430, 431 (Sumitomo 3M (share) system), AsahiGuard AG710, Surflon S-382, SC-101, 102, 103, 104, 105, 106 (as described by Asahi Shikoko), FTX-218 (NEOS) (share) system, etc. As an example of an organic lanthanide surfactant, according to a commercial name

Examples thereof include SH20〇-l〇〇cs 'SH28PA, SH30PA, ST89PA, SH190 (manufactured by Dow Corning Toray Co., Ltd.), and an organic oxirane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). [Η] The components may be used singly or in combination of two or more. The amount of use of the [Η] component is preferably 10 parts by mass or less based on 1 part by mass of the component [a]. By using the [Η] component in an amount of 1 part by mass or less, the coating property of the polyoxo-oxygen composition can be optimized. The polyoxime composition of the present invention can be formed into a solution or dispersed by, for example, mixing and dispersing [Α] and [Β] components, [C] components, and arbitrary components in a predetermined ratio in the [D] component. Liquid to prepare. The ratio of the components other than the component [D] in the polyoxane composition (that is, the total amount of [Α], [Β], and [C] components] and other optional components) may be arbitrarily determined depending on the purpose of use, the intended film thickness, and the like. The setting is preferably 5 to 5 % by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass - 34 to 201224060 [Formation of cured film of display element] A method of forming a cured film on a substrate on which a display element is to be formed will be described. The method includes the following steps (1) to (4). Further, as the cured film of the display element, a protective film, an interlayer insulating film, or the like can be given. (1) a step of forming a coating film of the polyfluorene oxide composition of the present invention on a substrate; (2) a step of irradiating at least a part of the coating film formed by the step; (3) a step (2) a step of developing a coating film of the irradiated radiation; and (4) a step of heating the enamel developed by the step (3). Step (1) In the step (1), after applying the solution or dispersion of the polyoxyalkylene composition of the present invention on the substrate, it is preferred to remove the solvent by heating (prebaking) the coated surface. Coating film. Examples of the material of the substrate that can be used include glass, quartz, shi, and resin. Examples of the oxime of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimine, cyclic olefin, and a vapor thereof. Wait. The composition of the polyoxane is not particularly limited. For example, a spray coating method, a co-coating method (spin coating method), a slit die coating method, or a bar coating method can be employed. Among these coating methods, the conditions of the singular A % coating method or the slit coating coating pre-baking are particularly the same depending on the type of each component, the ratio of the lion and the shell, etc., but it is preferably set to 70. (: ~120. (''11^ L under 1~10 minutes or so.

S • 35- 201224060 Step (2) In step (2), at least a part of the coating film formed by the step (1) is exposed. When a portion of the coating film is exposed, it is exposed through a reticle having a prescribed pattern. As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, neon light or the like can be used. Among these radiations, radiation having a wavelength in the range of 19 Å to 45 Å is preferable, and radiation containing 365 nm ultraviolet rays is particularly preferable. The value obtained by measuring the intensity at a radiation wavelength of 365 nm by an illuminometer (〇AI m〇del356 'OAI Optical Associates Inc.) is preferably 1 〇 to 1 〇〇〇 mJ/cm 2 as the exposure amount in the step. More preferably, it is 20 to 700 mJ/cm2. Step (3) In the step (3), by developing the exposed coating film, unnecessary portions (radiation unirradiated portions) are removed to form a predetermined pattern. Thus, the polyoxyalkylene composition of the present invention is removed from the radiation-irradiated portion, and thus is a negative-type radiation-sensitive composition. As the developing solution used in the developing step, an aqueous solution of an alkali (alkaline compound) is preferred. Examples of the base include a quaternary ammonium salt such as an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate or ammonia, and an alicyclic ammonium salt such as tetramethylammonium chloride or tetraethylammonium hydroxide. Wait. Further, an appropriate amount of a water-soluble organic solvent ash surfactant such as methanol or ethanol may be added to the aqueous alkali solution for use. As the method of the shirting method, an appropriate method such as a liquid-filling method (spinning immersion method), a bubble method, a shaking method, or a shower method can be used. As the development time, it differs depending on the combination of the composition of the polyoxetane, but it is 10 seconds.

S -36- 201224060 ~ 180 seconds or so. After such development processing is carried out, followed by, for example, running water washing for 30 seconds to 90 seconds, and then air drying by, for example, compressed air or compressed nitrogen, the intended pattern can be formed. Step (4) In the step (4), the patterned film is heated by a heating means such as a hot plate or an oven to promote the condensation reaction of the components [A] and [B], and the cured film is reliably formed. The heating temperature is, for example, 1 2 〇〇c to 25 〇. (: The heating time ' varies depending on the type of the heating device, for example, 5 minutes to 30 minutes when the heating step is performed on the hot plate, and 3 minutes to 9 minutes when the heating step is performed in the oven. A step-by-step baking method or the like which performs the heating step twice or more may be employed. In this manner, a cured film of the target display element, for example, a patterned film corresponding to the protective film or the interlayer insulating film, may be formed on the surface of the substrate. [Cured film (protective film or interlayer insulating film)] 〇1 = The film thickness of the cured film formed in this manner is preferably more preferably G.Um~hm, particularly preferably a polyoxygenated composition as follows The cured film formed of the material is excellent in various properties such as 1T 〇 adhesion, surface permeable to the moon, heat-resistant transparency, and scratch-resistant property of the substrate, such as hardness and transparency. A pattern having good crack resistance and flatness. Therefore, the hard second layer has a high resolution fine display panel for display elements such as a touch panel. 4. "Deuterated display element [Examples] Synthesis examples are listed below. The examples are against the invention, but The present invention is not limited to the following embodiments:

S-37-201224060 The number average molecular weight (Mn) and the weight average molecular weight of the hydrolysis-condensation product of the hydrolyzable decane compound obtained by each of the following synthesis examples were determined by gel permeation chromatography (GPC) as follows. of. Device · GPC-101 (made by Showa Denko Co., Ltd.) f column. GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (Showa Electric Co., Ltd.) are connected. Mobile phase: Synthesis example of tetrahydroorbamine [A] component polyoxoxime [Synthesis Example 1] In a vessel equipped with a stirrer, 24 mass groups were added, followed by addition of 39 parts by mass of methyltrimethoxydi : 2 dimethyl propylene methoxy propyl trimethoxy decane in two early days, heated to a solution temperature of 6 (TC. After the solution temperature reached 6 〇 t:, add 〇i parts of formic acid, 19 parts by mass Ion-exchanged water was heated until it was kept for 2 hours. After cooling to 451, 28 parts by mass of decyl orthoformate as a dehydrating agent was added and stirred for 1 hour, and then the temperature of the solution was 4 (rc) while evaporating while maintaining the temperature. Thus, the ion-exchanged water and the sterol produced by the hydrolysis condensation are removed. By the above operation, a polyoxyalkylene (A_丨) is obtained. The solid concentration of the polyoxyalkylene (A-1) is 35% by mass 'the weight average molecular weight ( Mw) was 1 800, and the degree of dispersion (Mw/Mn) was 2.2. [Synthesis Example 2] In a container equipped with a stirrer, 21 was added. The propylene glycol monodecyl ether was added in an amount of 55 parts by mass of tetramethoxynonane (TE〇s), 16 parts by mass of 3-methylpropenyloxypropyltrimethoxydecane (MpTMS), and heated to a solution temperature of 6 (TC. After the solution temperature reaches 6 (rc, add 〇丨 quality)

S -38- 201224060 parts of formic acid, 23 parts by mass of ion-exchanged water, heated to . Cool to the heart, add the tender... ester and stir for 1 hour. Further, the solution temperature was 4 Torr < t, and evaporation was carried out while maintaining the temperature to remove ion-exchanged water and methanol and ethanol produced by hydrolysis condensation. II From the above operation, polyoxyalkylene (eight-2) was obtained. The polyoxyalkylene (A-2) had a solid concentration of 33% by mass and a weight average molecular weight (Mw) of 2,500'. The degree of dispersion (Mw/Mn) was 24%. [Synthesis Example 3] In a container equipped with a stirrer, 23 parts by mass of propylene glycol monodecyl ether was added, followed by 24 parts by mass of methyltrimethoxy decane (MTMS) and 22 parts by mass of tetramethoxy fever (TE〇). s), 17f parts of 3-methylpropenyloxypropyltrimethoxydecane (MPTMS), heated to the solution temperature. After the solution temperature reached 6 (TC, add hydrazine in mass parts of formic acid, 2 i parts by mass of ion-exchanged water, heat it to 75 for 2 hours, and cool to 45 (after adding 30 parts by mass of decyl orthoformate as a dehydrating agent, After stirring for 1 hour, the temperature of the solution was adjusted to 40 ° C, and the temperature was maintained while evaporating to remove the ion-exchanged water and the sterol and ethanol produced by the hydrolysis condensation. By the above operation, poly-stone-oxygen (A_3) was obtained. The solid content/density of polyoxymethane (A_3) was 34% by mass, the weight average molecular weight (Mw) was 26 Å, and the degree of dispersion (Mw/Mn) was 2.3. [Synthesis Example 4] In a container, 23 parts by mass of a propylene glycol monothiol bond was added, followed by 24 parts by mass of methyltrimethoxy decane (Mtms), and 16 parts by mass of tetradecyloxydecane (TM 〇s) '17 parts by mass of 3 曱Acryloxypropyltrimethoxy decane (MPTMS), heated to a solution temperature of 60. (:

S -39- 201224060. After the solution temperature reached 60 ° C, 1 part by mass of formic acid and 21 parts by mass of ion-exchanged water were added to be heated to 75. Oh, keep it for 2 hours. After cooling to 45 t, 30 parts by mass of methyl ortho-decanoate as a dehydrating agent was added, and the mixture was stirred for 1 hour. Further, the temperature of the solution was adjusted to 4 (TC, - while maintaining the temperature, and evaporation was carried out to remove ion-exchanged water and methanol produced by hydrolysis condensation. By the above operation, a polyoxane (A-4) was obtained. The solid content of (A-4) was 35 mass%, the weight average molecular weight (Mw) was 2,500, and the degree of dispersion (Mw/Mn) was 2.3. [Synthesis Example 5] 27 parts by mass were placed in a container equipped with a stirrer Propylene glycol monomethyl ether' followed by addition of 12 parts by mass of methyltrimethoxy decane (MTMS), 3-phenylindole phenyl dimethoxy decane (PTMS), 15 parts by mass of 3-methylpropenyloxypropane Base trimethoxy stone court (MPTMS), heated to a solution temperature of 60 ° C. / Fen liquid temperature reached 6 〇. After 〇, add 〇 mass part of formic acid, ^ 6 parts by mass of ion-exchanged water, heated to 75 it, Hold for 2 hours. After cooling to CC, add 30 parts by mass of decanoic acid decanoate as a dehydrating agent, and stir for J hours. Then let the temperature of the solution be 4 generations, while maintaining the temperature - while advancing (four), removing from Ion-exchanged water and methanol produced by hydrolysis condensation. A - S, · Β · α y milk (a 5). The concentration of solids of polyoxyalkylene (Α_5) is 28% by mass, the average weight; the number of tens of diced J (Mw) is 1,800, dispersed The degree (Mw/Mn) was 2.0. [Synthesis Example 6] In a vessel equipped with a stirrer, 2 parts by mass of propylene glycol monomethyl ether was added, followed by addition of 27 parts by mass of methyltrimethoxy money (mtms), 25 Parts by mass of tetramethoxy dream (T-cut), 12 parts by mass of vinyl trimethoxy

S -40- 201224060 decane (vtms), heated to a solution temperature of 6 (rc. After the solution temperature reached 6 ° C, 'add 0.1 parts by mass of citric acid, 23 parts by mass of ion-exchanged water, heat to 7 5 C '2 After cooling to 45 ° C, 34 parts by mass of decanoic acid decanoate as a dehydrating agent was added and stirred for 1 hour. The temperature of the solution was further adjusted to 4 ° C, and evaporation was carried out while maintaining the temperature to remove ion-exchanged water. And sterol and ethanol produced by hydrolytic condensation. By the above operation, a polysiloxane (A-6h polyoxy siloxane (A_6) has a solid concentration of 28% by mass and a weight average molecular weight (Mw) of 2,300. The degree of dispersion (Mw/Mn) was 2.2. [Synthesis Example 7] In a vessel equipped with a stirrer, 27 parts by mass of propylene glycol monomethyl ether was added, followed by 20 parts by mass of methyltrimethoxy decane (MTMS), 37. Parts by mass of 3-methylpropenyloxypropyltrimethoxydecane (MpTMs), heated to a solution temperature of 6 ° C C ^ solution temperature reached 6 ° C, added mass damage toluene '16 parts by mass ion exchange Water, heated to 7 5 ^, after cooling to 4 5 C at 2 J, add 23 mass parts as The methyl orthoformate of the dehydrating agent was stirred for 1 hour, and the temperature of the solution was adjusted to 40 ° C, and the temperature was maintained while evaporating to remove ion-exchanged water and methanol produced by hydrolysis condensation. Alkane (A_7). The solid concentration of polyoxyalkylene (A-7) was 36% by mass, and the weight average molecular weight (Mw) was 1600'. The degree of dispersion (Mw/]y[n) was 2 〇. [Synthesis Example 8 In a vessel equipped with a stirrer, 22 parts by mass of propylene glycol monomethyl 2 was added, followed by 52 parts by mass of methyltrimethoxydecane (MTMS), 5 bernips, 3 methacryloxypropyltrimethoxydecane Heat to the temperature of the solution (10). After the temperature of the solution reaches the scratch, add -41-201224060 parts by mass of formic acid, 22 mass of noisy; six 4A ^ negative ionic ion replacement water, heat to 75 ° C, hour. Cool to 45 After 〇c, add the 32-day-long, succulent methic acid as a dehydrating agent, and give it for 1 hour. Then pass it, θ electricity & ', in — & liquid temperature is 4GC, while maintaining Warming and ordering heat to remove ion-exchanged water and methanol produced by hydrolysis condensation By the above operation, the solid concentration of polyoxazine (Α_8) β polyoxane (Α-8) was 33% by mass, the weight average molecular weight was 2,400, and the dispersion (Mw/Mn) was 2.4. [Synthesis Example 9] In a vessel equipped with a stirrer, 23 parts by mass of propylene glycol monodecyl ether was added, followed by 42 parts by mass of methyltrimethoxy decane (MTMs), and 14 parts by mass of 3-mercaptopropene oxime Propyltrimethoxydecane (MpTMs), heated to a solution temperature of 60 °C. After the temperature of the solution reached 6 ° C, the mass fraction of formic acid, 20 parts by mass of ion-exchanged water was added, and it was heated to 75 for 2 hours. After cooling to 45 ° C, 32 parts by mass of methyl orthocarbonate as a dehydrating agent was added and stirred for 1 hour. Further, the temperature of the solution was changed to 4 liters, and evaporation was carried out while maintaining the temperature, thereby removing ion-exchanged water and a leaven produced by hydrolysis condensation. By the above operation, polyoxyalkylene (A-9) was obtained. The polyfluorene appearance (A-9) had a solid concentration of 33% by mass, a weight average molecular weight (Mw) of 2,100, and a degree of dispersion (Mw/Μη) of 2.1. [Synthesis Example 1] In a vessel equipped with a stirrer, 20 parts by mass of propylene glycol monodecyl ether was added, followed by 34 parts by mass of mercaptotridecyloxydecane (MTMS), and 25 parts by mass of tetradecyloxydecane (TEOS). 5 parts by mass of 3-methylpropenyloxypropyltrimethoxyhydrazine (MPTMS), heated to a solution temperature of 60 °C. After the solution temperature reached 60 ° C, 1 part by mass of formic acid '23 parts by mass of -42-201224060 sub-exchanged water was added, and heated to 7 5 ° Γ, at 4* 1 t + for 2 hours. After cooling to 45 ° C, 34 parts by mass of s βm & methyl orthoformate as a dehydrated hydrazine was added and stirred for 1 hour. The solution temperature was then made 40. 〇, a j〇 4* .© λ: The evaporation is carried out while removing the ion-exchanged water and the methanol and ethanol produced by the condensation of A by the hydrolysis. By staying above, you get the poly-hard oxygen ^ ^ A Λ, χ χ & 匕 courtesy (A_10). The concentration of the solid concentration of the polyoxyalkylene (A-10) was 32% by mass, and the concentration of the molecular weight (Mw) was 2,200, and the degree of dispersion (Mw/Mn) was 2.2. [Synthesis Example 11] In a vessel equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was added followed by 30 parts by mass of methyltrimethoxydecane (MTMS), 9 parts of 1 part of trifluoropropyltrimethoxydecane ( TFMS), 18 parts by mass of 3 methacryloxypropyltrimethoxydecane (MPTMS), heated to a solution temperature of 60 °C. After the solution temperature reached 6 〇 < t, 〇 mass parts of formic acid, 19 ft. of wound ion exchange water were added, and the mixture was heated to 7 5 for 2 hours. After cooling to 4 5 C, 28 parts by mass of decyl orthoformate as a dehydrating agent was added and stirred for 1 hour. Further, the temperature of the solution was adjusted to 4 Torr, and evaporation was carried out while maintaining the temperature to remove ion-exchanged water and methanol produced by hydrolysis condensation. By the above operation, polyoxyalkylene (A-11) was obtained. The polysiloxane (A-11) had a solid concentration of 35 mass%, a weight average molecular weight (Mw) of 18 Å, and a degree of dispersion (Mw/Mn) of 2.2. Synthesis Example of Polyoxane of Component [B] [Synthesis Example 1 2] In a vessel equipped with a stirrer, '25 parts by mass of propylene glycol monomethyl group was added' followed by addition of 23 parts by mass of methyltrimethoxy decane (MtmS) ), 34 parts by mass of phenyltrimethoxy decane (PTMS), heated to a solution temperature of 6 〇

S -43- 201224060 °C. After the solution temperature reached 6 passages, hydrazine was added in an amount of citric acid, i8 parts by mass of ion-exchanged water, and heated to 75 〇c for 3 minutes. Then, 〇 ^ parts by mass of triethylamine was added and kept at 75 ° C for 1.5 hours. After cooling to the price, 27 parts by mass of the original formic acid methyl vinegar as a dehydrating agent was added and stirred for 2 hours. Further, the temperature of the solution was changed to a thief, and the curtain was sent while maintaining the temperature, thereby removing ion-exchanged water and methanol produced by hydrolysis condensation. By the above operation, polyoxyalkylene (B-i) was obtained. The polysiloxane (the solid concentration of Β_υ is 34 里/〇, the weight average molecular weight (Mw) is, and the degree of dispersion (Mw/Mn) is 2.4 〇 [Synthesis Example 13] In a vessel equipped with a stirrer, 25 is added. Parts by mass of propylene glycol monodecyl ether, followed by addition of 23 parts by mass of decyltrimethoxydecane (MTMS), 3 parts by mass of phenyltrimethoxy decane (PTMS), 4 parts by mass of γ-glycidoxypropyl The decyloxydecane (GPTMS) was heated to a solution temperature of 6 Torr. After the temperature of the liquid reached 60 C, 1 part by mass of formic acid and 8 parts by mass of ion-exchanged water were added and heated to 75 t for 30 minutes. Then, the mass-damaged diethylamine was added and kept at 75 C for 1.5 hours. After cooling to 45 ° C, 27 parts by mass of methyl orthoformate as a dehydrating agent was added and stirred for 1 hour, and then the temperature of the cold liquid was 40. °C ' while evaporating while maintaining the temperature, thereby removing ion-exchanged water and sterol produced by hydrolysis condensation. By the above operation 'to get the polyoxane (B-2). Polyoxane (B_2). The solid concentration was 34% by mass, the weight average molecular weight (Mw) was 2,500, and the degree of dispersion (Mw/Mn) was 2.4. [Synthesis Example 1 4] In a vessel equipped with a stirrer, '21 parts by mass of propylene glycol monoterpene-44-s 201224060-based styrene mass methoxy decane (MTMS), 17 parts by weight of decyltrimethoxydecane' was added. Add 40 parts by mass of methyltri-tetramethoxydecane (TEOS), 5 mass (DTMS), and heat to a solution temperature of (4). The solution temperature is (10)^ after 'adding hydrazine' mass parts of formic acid, 22 parts by mass of ion-exchanged water , and added to 75 ° C for 2 hours. After cooling to 4 passages, 33 parts by mass of orthoformate methyl vinegar as a dehydrating agent was added to stir H, and the temperature of the solution was 4 (rc while maintaining the temperature). Evaporation to remove ion-exchanged water and sterol and ethanol produced by hydrolysis condensation. By the above operation, polyoxazane (B-3) is obtained. The solid concentration of polyoxydecan (B_3) is "% by mass, The weight average molecular weight (Mw) was 2000, and the degree of dispersion (Mw/Mn) was 2.3. [Synthesis Example 15] 21 parts by mass of propylene glycol monomethyl ether was added to a vessel equipped with a stirrer, followed by the addition of 40 parts by mass of methyltrimethyl Oxydecane (MTMS), 12 parts by mass of tetradecyloxydecane (TM〇s) 5 parts by mass of decyltrimethoxy oxime (DTMS), heated to a solution temperature of 6. The solution temperature reached 6 Torr. After the addition, '0.1 parts by mass of formic acid and 22 parts by mass of ion-exchanged water were added and heated for 2 hours. After cooling to 45, 33 parts by mass of methyl ortho-decanoate as a dehydrating agent was added, and the mixture was stirred for 1 hour, and the temperature of the solution was further adjusted to 4 Torr. Evaporation was carried out while maintaining the temperature, thereby removing ion-exchanged water and condensing by hydrolysis. Methanol produced. By the above operation, polyoxyalkylene (B-4) was obtained. The polysiloxane (B_4) had a solid concentration of 34% by mass, a weight average molecular weight (Mw) of 2,000, and a degree of dispersion (Mw/Mn) of 2.3. [Synthesis Example 16] In a container equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl group was added, followed by addition of 18 parts by mass of methyltrimethoxydecane, 29

S-45 - 201224060 parts by mass of phenyltrimethoxydecane (PTMS), 10 parts by mass of trifluoropropyltri-foxylate (TFMS) was heated to a solution temperature of 60 °C. After the solution temperature reached 60 ° C, 0.1 part by mass of formic acid and 18 parts by mass of ion-exchanged water were heated to 7 5 C ' for 30 minutes. Then, 0.1 part by mass of triethylamine was added and kept at 75 ° C for 1.5 hours. After cooling to 45 ° C, 27 parts by mass of methyl orthoformate as a dehydrating agent was added and stirred for 1 hour. Further, the solution was allowed to have a temperature of 40 ° C and evaporated while maintaining the temperature to remove ion exchange water and methanol produced by hydrolysis condensation. By the above operation, polysiloxane (B-5) was obtained. The polyoxyalkylene (B-5) had a solid concentration of 34% by mass, a weight average molecular weight (Mw) of 2,400, and a degree of dispersion (Mw/Mn) of 2.4. [Synthesis Example 17] In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by addition of 23 parts by mass of methyltrimethoxydecane (MTMS), and 24 parts by mass of phenyltrimethoxydecane (PTMS). 10 parts by mass of 3-mercaptopropyltrimethoxy-infraline (YMPTMS), heated to a solution temperature of 60 °C. After the solution temperature reached 60 ° C, '〇·丨 parts by mass of formic acid, 丨 8 parts by mass of ion-exchanged water' was heated to 75 ° C and held for 30 minutes. Then, 0.1 part by mass of triethylamine was added and kept at 75 ° C for 1.5 hours. After cooling to 45 ° C, 27 parts by mass of decyl orthoformate as a dehydrating agent was added and stirred for 1 hour. Further, the solution was allowed to evaporate while maintaining the temperature at 4 ° C ' to remove ion-exchanged water and sterol produced by hydrolysis condensation. By the above operation, polyoxymethane (B-6) was obtained. The polyoxydecan (B_6) had a solid concentration of 34% by mass, a weight average molecular weight (Mw) of 2,800, and a degree of dispersion (Mw/Mn) of 2.1. Preparation of a radiation-sensitive linear polyoxane composition and formation of a protective film and an interlayer insulating film

S -46 * 201224060 [Example 1] A solution of polysiloxane (A-1) obtained by δ Example 1 in 3 (corresponding to 50 parts by mass (solid matter) of polyoxyalkylene (Al) In the amount], a solution containing the polyfluorene oxide (Β-1) obtained in Synthesis Example 12 as a component of [Β] is added in accordance with the ratio of [Β] to the mass of the polyoxane (Β1) 5〇. (amount of solid matter), 3 parts by mass of (C1) ethyl ketone-1 [9·ethyl-6-(2-methylbenzoinyl)_9H-ncarbazole_3 as component [c] _基]_ι_(〇_乙躬:), as a [D] component of (D-1) propylene glycol monoterpene and (D_2) diethylene glycol ethyl methyl ether, for the preparation of radiation-induced linear polyoxyl Alkane composition. Then, the radiation-sensitive polyoxophobic composition was applied onto a glass substrate impregnated with SiO 2 using a spin coater, and then prebaked on a hot plate at 9 ° C for 2 minutes to form a coating film (described later) The substrate with ITO in the evaluation of ITO adhesion). Then, the obtained coating film was exposed to ultraviolet light at an exposure amount of 300 mJ/cm 2 . Subsequently, it was developed with a 0.4 mass% aqueous tetradecyl ammonium hydroxide solution at 25 Torr for 60 seconds, then washed with pure water for 1 minute, and further heated in an oven at 230 ° C for 60 minutes to form a protective film having a film thickness of 2.0 μm. Further, the number of revolutions of the spin coater at the time of forming the coating film was adjusted so that the film thickness after heating was 3.0 μm, and the mask having the contact hole pattern of 20 Km, 30 μm, 40 μm, and 50 μm was passed through the exposure gap (interval between the substrate and the mask). The exposure was performed at 150 μm, except that the same operation as the formation of the above protective film was performed to form an interlayer insulating film. Physical property evaluation The transparency, heat-resistant transparency, erroneous pen hardness, scratch resistance, cracking, heat-resistant cracking of the protective film formed by each of the examples and the comparative examples were evaluated.

S -47- 201224060 ιτο adhesion, sensitivity and refractive index. Further, in the interlayer insulating film, since the interlayer insulating film has only a film thickness (3 _0 μm) different from the protective film, the interlayer insulating film has transparency, heat-resistant transparency, pencil hardness, scratch resistance, cracking, heat-resistant cracking, The evaluation of the adhesion, the sensitivity, and the refractive index was determined to be the same as that of the protective film. In addition, 'the evaluation of the resolution of the radiation-sensitive polyaluminoxane composition (the resolution of the interlayer insulating film)' can be considered as the formation of interlayer insulation due to the "resolvability" of the radiation-induced linear polyoxane composition. The performance of the precision contact hole of the film can be evaluated as a project equivalent to the "resolution" of the interlayer insulating film. (1) Evaluation of the transparency of the protective film. For the substrate having the protective film formed by the above-described embodiments and the comparative examples, a spectrophotometer (150-20 type double beam made by Hitachi, Ltd.) was used. The light transmittance (%) at a wavelength of 400 nm to 800 nm was measured. When the maximum value of the light transmittance (%) of the wavelength of 400 to 800 nm is 95% or more, it is judged that the transparency of the protective film is good. (2) Evaluation of heat-resistant transparency of protective film For the substrate 'with a protective film prepared by the above-described embodiments according to the above-described embodiments, when heated at 250 ° C in a cleaning oven, 'Using the above (1)' After the light transmittance before and after heating was measured in the evaluation of the transparency of the protective film, the heat resistance (%) was calculated according to the following formula (a). When the value is 4% or less, it is judged that the heat resistance of the protective film is heat-resistant and transparent (%) = the light transmittance of the light transmittance before heating (%) (a) ° 201224060 (3) Protective film pencil hardness (Surface hardness) Measurement of the pencil hardness of the protective film by the "JIS 〖5400_199 〇 8 4 1 pencil scratch test" on the substrate having the protective film formed by the above-described respective examples and comparative examples (surface) hardness). When the value is or greater, it is judged that the surface hardness of the protective film is good. (4) Evaluation of the scratch resistance of the protective film The substrate having the protective film formed by the above-described embodiments and the comparative examples was applied on a #〇〇〇〇〇〇〇〇 steel wool using a vibration-type abrasion tester. The load of 20 〇g was performed 10 times back and forth. The scratches were visually observed and evaluated according to the following criteria. When it was evaluated as ◎ or 〇, it was judged to have good scratch resistance. Judgment Criteria ◎: No abrasion at all 〇: 1 to 3 scratches remaining Δ: Residual 4 to 1 擦 abrasions X: 10 or more scratches remaining (5) Evaluation of protective film cleavage for the basis of each example and comparative example The substrate having the protective film formed by the above-described method was placed under 231 for 24 hours, and it was confirmed that the surface of the protective film was cracked by using a laser microscope (VK-8500 manufactured by KEYENCE). When the evaluation was ◎ or 〇, the evaluation of cracking was judged to be good. Judging criteria ◎: There is no cracking at all. There are 1~3 cracks open 201224060 △: There are 4~10 splits X: There are more than 10 cracks (6) Evaluation of heat-resistant cracking of protective film for each EXAMPLES AND COMPARATIVE EXAMPLES A substrate having a protective film formed in the above manner was additionally calcined at 300 ° C for 30 minutes, and then left at 23 ° C for 24 hours, and a laser microscope (VK manufactured by KEYENCE) was used according to the following criteria. -8500) Confirm whether the surface of the protective film is cracked. When the evaluation was ◎ or 〇, the evaluation of cracking was judged to be good. Judging criteria ◎ There is no cracking 〇 There are 1~3 cracking Δ There are 4~10 cracking X There are more than 10 cracking (7) ITO (Indium Tin Oxide) adhesion evaluation of protective film except In addition to the substrate with IΤ, a protective film was formed in accordance with the above embodiments by the respective examples and comparative examples, and a pressure cooker test (丨2〇t, humidity 100% '4 hours) was performed. Then, the "JIS K-5400-1 9 90 8.5.3 Attached Checkerboard Tape Method" test was conducted to determine the number of checkerboards remaining in the 100 checkerboards, and the IT0 adhesion of the protective film was evaluated. 1 When the number of checkerboards remaining in one of the checkerboards is 80 or less, it is judged that the adhesion is poor. (8) Evaluation of the sensitivity of the protective film For the coating film obtained above, the exposure machine TME-400PRJ' manufactured by TOPCON was used to change the exposure amount through a mask having a pattern of a pitch ratio of ι〇μηι/3〇μηη. After the exposure, development was carried out by dipping at 60 ° C for 60 seconds using a 4% by mass aqueous solution of tetramethylphosphoric acid. Then use

S -50- 201224060 Ultrapure water was washed with water for 1 minute, dried, and patterned on a glass substrate. At this time, the minimum exposure amount required for the pattern retention of 10 μm / 30 μm pitch ratio without peeling was measured. This minimum exposure amount was evaluated as the radiation sensitivity. When the minimum exposure amount is 50 mJ/cm2 or less, it is judged that the sensitivity is good. (9) Evaluation of refractive index of protective film The refractive index of the obtained protective film at 25 to 633 nm light was measured by the above-mentioned "evaluation of light transmittance (transparency) of protective film" using an Abbe refractometer. (10) Evaluation of Resolving Property of Radiosensitive Polyoxane Composition (Resolution of Interlayer Insulating Film) The contact hole pattern which can be resolved when the above-described interlayer insulating film is formed in each of Examples and Comparative Examples size. If it is possible to distinguish the contact hole pattern of 300 μm or less, it is judged that the resolution is good. [Examples 2 to 26 and Comparative Examples 1 to 6] The types and amounts of the respective components are as shown in Table 丨5. In addition to the description, a radiation-sensitive polyoxymethane composition was prepared in the same manner as in Example 1. Then, using the obtained radiation-sensitive polyaluminoxane composition, a protective film was formed in the same manner as in Example 1. Further, the respective amounts in Tables 1 to 5 are parts by mass. The evaluation results of the examples 1 to 7 are shown in Table 1, the evaluation results of the examples 8 to 13 are shown in Table 2, and the evaluation results of the examples 1 to 20 are listed in Table 3, and Examples 21 to 26 The evaluation results are shown in Table 4, and the evaluation results of Comparative Examples 1 to 6 are shown in Table 5. 201224060 Further, in Tables 1 to 5, the following symbols are indicated for the [C] photoradical polymerization initiator, [D] solvent, [E] acrylate, [F] organic particles or inorganic particles, respectively. C-1 : Ethyl ketone-ethyl-6-(2-methylbenzhydryl)_9H-indazol-3-yl]-1-(0-acetamidine) (trade name: IRGACURE OXE02, Ciba S Pecia 11 y C hemica 1 s (manufactured by the company) C-2 : 1,2 octodione-bu [4-(phenylthio)phenyl]-2-(0-benzamide) (business) Product Name: IRGACURE OXEOl, manufactured by Ciba Specialty Chemicals Co., Ltd.) C_3 : 2-Methyl-[4-(methylthio)phenyl]-2 - miso-based-1·propanil (trade name: IRGACURE 907, Ciba Specialty Chemicals Co., Ltd.) C-4 : 2-Dimethylamino-2-[(4-indolylphenyl)indenyl]-1-[4-(4-imilinyl)phenyl] 1-butanone (trade name: IRGACURE 379EG, manufactured by Ciba Specialty Chemicals Co., Ltd.) Dl: propylene glycol monomethyl ether D-2: diethylene glycol ethyl methyl ether D-3 : butyl cellosolve E-1 : a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: MAX-35 10, manufactured by Sakamoto Chemical Co., Ltd.) E-2: pentaerythritol triacrylate ( Product name: A-TMM-3LMN, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) E-3: succinic acid-modified dipentaerythritol pentaacrylate (trade name: M-520, 曰本Drugs (shares), Ltd.) E-4: Tris (Bing Xixi oxyethyl) isocyanurate (trade name: M-3 15, Toagosei (shares) Ltd.)

S -52- 201224060 Fl : Polymethyl methacrylate-based particles (trade name: MP_3 〇〇 研 化学 化学 )) F-2: Organic sulphur dioxide sol (product name. IPA-ST' Nissan Chemical Industrial (share) system) F-3 F-4

Zr〇2 sol (trade name: Ti〇2 sol (trade name: ID191, manufactured by TAYCA): TS-103, TAYCA (share) system >

S-53-201224060 [Table i] Example 1 2 3 4 5 6 7 (A) Polyoxyalkylene A-1 having a radical polymerizable organic group (MTMS/MPTMS=80/20) 50 A-2 ( TEOS/MPTMS=80/20) 50 A-3 (MTMS/TEOS/MPTMS=50/30/20) 50 A-4 (MTMS/TMOS/MPTMS=50/30/20) 50 A-5 (MTMS/PTMS /MPTMS=50/30/20) 50 A-6 (MTMS/TEOS/VTMS=50/30/20) 50 A-7 (MTMS/MPTMS=50/50) 20 A-8 (MTMS/MPTMS=95/ 5) A-9 (MTMS/MPTMS=85/15) A-10 (MTMS/TEOS/MPTMS=65/30/5) Al l (MTMS/TFMS/MPTMS=70/10/20) (B) does not have Free radically polymerizable polyoxyalkylene B-KMTMS/PTMS) 50 50 50 50 50 50 80 B-2 (MTMS/PTMS/GPTMS) B-3 (MTMS/TEOS/DTMS) B-4 (MTMS/TMOS /DTMS) B-5(MTMS/PTMS/TFMS) B-6(MTMS/PTMS/yMPTMS) (C) Radical polymerization initiator Cl 3 1 1 1 2 2 3 C-2 2 1 C-3 2 1 C -4 2 (D) Solvent Dl (propylene glycol monodecyl ether) 40 40 100 100 160 160 200 D-2 (diethylene glycol ethyl decyl ether) 160 100 100 40 D-3 (butyl cellosolve) 160 40 (E) Ethylene unsaturation Compound E-1 (dipentaerythritol hexaacrylate) E-2 (neopentitol tetraacrylate) E-3 (succinic acid modified dipentaerythritol pentaacrylate) E-4 (three ( Propylene oxime ethyl) isocyanurate) 00 particles F-1 [MP-300 (PMMA particles)] F-2 (SiO 2 particles) F-3 (Zr02 particles) F~4 (Ti02 particles) Composition (A The content ratio of the structural unit having a radical polymerizable organic group in the entire structural unit of the component (B) (mol%) 10.5 10.8 10.6 10.6 9.5 11.9 8.3 Transparency (%) 98 98 98 98 98 98 98 Heat-resistant transparency (%) 4 5 4 4 5 4 4 Pencil hardness 5H 5H 5H 5H 5H 5H 5H Scratch resistance Δ △ △ △ Δ Δ Δ Split Δ 〇〇 Δ Δ 〇〇 Heat cracking 〇 Δ 〇 〇 〇Δ Δ ITO adhesion evaluation 100 100 100 100 100 100 100 Sensitivity (mJ/cm2) 50 50 50 50 50 50 50 Refractive index 1.51 1.51 1.51 1.51 1.53 1.51 1.51 Resolution (μηι) 30 30 30 30 30 30 30 -54- 201224060 [Table 2] Example 8 9 10 11 12 13 (A) Polychlorinated oxygen having a radical polymerizable organic group A-1 (MTMS/MPTMS=80/20) A-2 (TEOS/MPTMS=80/20) A-3 (MTMS/TEOS/MPTMS=50/30/20) 50 50 50 50 50 50 AWflVITMSA'MOS/ MPTMSsSO/SOOO) A-5 (MTMS/PTMS/MPTMS=50/30/20) A-6 (MTMS/TEOSA^TMS=50/30/20) A-7 (MTMS/MPTMS=50/50) A- 8(MTMS/MPTMS=95/5) A-9(MTMS/MPTMS=85/15) A-10(MTMS/TEOS/MPTMS=65/30/5) Al l(MTMS/TFMS/MPTMS=70/10 /20) (B) Polyoxane B-KMTMS/PTMS without radical polymerizable group 50 50 50 B-2 (MTMS/PTMS/GPTMS) 50 B-3 (MTMS/TEOS/DTMS) 50 B -4(MTMS/TMOS/DTMS) 50 B-5(MTMS/PTMS/TFMS) B-6(MTMS/PTMS/yMPTMS) (C) Radical polymerization initiator Cl 3 3 3 3 3 3 C-2 C- 3 C-4 (D) Solvent Dl (propylene glycol monomethyl ether) 200 200 150 100 160 160 D-2 (diethylene glycol ethyl methyl ether) 50 D-3 (butyl cellosolve) 100 40 40 (E Ethylene unsaturated compound E-1 (dopentyl alcohol hexaacrylate) 30 10 10 10 E-2 (neopentitol; acrylate) 10 30 E-3 (succinic acid modified dipentaerythritol) Fives Ether ester) E-4 (tris(propylene oxyethyl) isocyanurate) 30 30 (F) particles F-1 [MP-300 (PMMA particles)] F-2 (SiO 2 particles) F-3 (Zr02 particles) F4 (Ti02 particles) The content ratio of the structural unit having a radical polymerizable organic group in all the structural units of the component (A) and the component (B) (% by mole) 10.7 9.0 11.3 10.6 10.6 10.6 Transparency (%) 98 98 98 99 99 99 Heat-resistant transparency (%) 5 4 3 2 2 2 Pencil hardness 5H 5H 6H 6H 6H 6H Scratch resistance Δ Δ 〇〇〇〇 split Δ 〇〇〇〇〇 heat Cracking 〇Δ 〇〇〇〇ITO adhesion evaluation 100 100 100 100 100 100 Sensitivity (mJ/cm2) 50 50 40 30 30 30 Refractive index 1.50 1.49 1.49 1.49 1.49 1.48 Resolution (μπι) 30 20 20 20 20 20 201224060 [Table 3] Example 14 15 16 17 18 19 20 (A) Polyoxane A-1 having a radical polymerizable organic group (MTMS/MPTMS=80/20) A-2 (TEOS/MPTMS=80 /20) A-3 (MTMS/TEOS/MPTMS=50/30/20) 50 50 50 50 50 50 50 A-4 (MTMS/TMOS/MPTMS=50/30/20) A-5 (MTMS/PTMS/ MPTMS=50/ 30/20) A-6 (MTMS/TEOS/VTMS=50/30/20) A-7 (MTMS/MPTMS=50/50) A-8 (MTMS/MPTMS=95/5) A-9 (MTMS/ MPTMS=85/15) A-10 (MTMS/TEOS/MPTMS-65/30/5) Al l (MTMS/TFMS/MPTMS=70/10/20) (B) Polyfluorene without radical polymerizable group Oxytomane B-KMTMS/PTMS) 50 50 50 50 50 50 50 B-2 (MTMS/PTMS/GPTMS) B-3 (MTMS/TEOS/DTMS) B-4 (MTMS/TMOS/DTMS) B-5 (MTMS /PTMS/TFMS) B-6(MTMS/PTMS/yMPTMS) (C) Radical polymerization initiator Cl 3 3 3 3 3 3 5 C-2 3 C-3 3 C-4 3 (D) Solvent Dl (propylene glycol Monomethyl ether) 150 100 100 100 345 345 460 D-2 (diethylene glycol ethyl methyl ether) 50 10 115 D-3 (butyl cellosolve) 50 100 50 90 115 ¢) Ethylene unsaturated compound E -1 (dipentaerythritol hexaacrylate) 10 50 10 10 10 E-2 (neopentitol tetraacrylate) 10 30 30 E-3 (succinic acid modified dipentaerythritol pentaacrylate) 10 10 E-4 (tris(propylene oxyethyl) isocyanurate) 30 10 30 (F) particles F-1 [MP-300 (PMMA particles)] 100 F-2 (SiO 2 particles) 100 F-3 (Zr02 particles) 100 F-4 (Ti02 particles) The radical polymerizable organic group constituting all the structural units of the component (A) and the component (B) Content ratio of structural unit (% by mole) 10.6 10.6 10*6 10.6 10.6 10.6 10.6 Transparency (%) 99 99 99 99 99 99 99 Heat resistance transparency (%) 2 2 2 2 2 2 2 Pencil hardness 6H 6H 6H 6H 7H 7H 5H Scratch resistance 〇〇〇〇〇〇〇 cracking 〇〇〇〇〇〇 Δ Sealing heat cracking 〇〇〇〇〇〇〇 ITO adhesion evaluation 100 100 100 100 100 100 100 Sensitivity (mJ/cm2) 50 40 30 30 30 30 30 Refractive index 1.50 1.48 1.48 1.48 1.48 1.46 1.46 Resolution (μηι) 30 20 20 20 30 30 30 -56- 201224060 [Table 4] Example 21 22 23 24 25 26 (A) Free radicals Polymerizable organic polyoxyalkylene Al (MTMS/MPTMS=80/20) 50 A-2 (TEOS/MPTMS=80/20) A-3 (MTMS/TEOS/MPTMS=50/30/20) 50 50 50 50 A-4 (MTMS/TMOS/MPTMS=50/30/20) A-5 (MTMS/PTMS/MPTMS=50/30/20) A-6 (MTMS/TEOS/VTMS=50/30/20) A-7 (MTMS/MPTM S=50/50) A-8 (MTMS/MPTMS=95/5) A-9 (MTMS/MPTMS=85/15) A-10 (MTMS/TEOS/MPTMS=65/30/5) Al l (MTMS /TFMS/MPTMS=70/10/20) 50 (B) Polyoxane B-KMTMS/PTMS without radical polymerizable group 50 50 50 50 B-2 (MTMS/PTMS/GPTMS) B-3 (MTMS/TEOS/DTMS) B-4 (MTMS/TMOS/DTMS) B-5 (MTMS/PTMS/TFMS) 50 B-6 (MTMS/PTMS/yMPTMS) 50 (C) Radical polymerization initiator Cl 3 3 3 5 3 5 C-2 C-3 C-4 (D) Solvent Dl (propylene glycol monodecyl ether) 460 150 150 200 200 150 D-2 (diethylene glycol ethyl decyl ether) 50 50 D-3 (butyl cellosolve) 50 ¢) Ethylene and compound El (dipentaerythritol hexaacrylate S) E-2 (neopentitol triacrylate) E-3 (succinic acid modified two new Pentaerythritol pentaacrylate) Ε·4 (tris(propylene oxyethyl)isocyanurate) (F) particles F-1 [MP-300 (PMMA particles)] F-2 (SiO 2 particles) F- 3 (Zr02 particle) F4 (Ti02 particle) 100 constitutes the structural list of (A) component and (B) component The content ratio of the structural unit having a radical polymerizable organic group (mol%) 10.6 10.6 10.6 10.0 10.9 10.9 Transparency (%) 99 98 98 98 98 98 Heat-resistant transparency (%) 2 3 3 3 3 3 Pencil hardness 5H 5H 5H 5H 5H 7H Scratch resistance 〇〇〇〇〇 Δ Split Δ Δ 〇 Δ Δ Δ Heat cracking 〇〇 Δ 〇〇〇 ITO adhesion evaluation 100 100 100 100 100 100 Sensitivity (mJ /cm2) 30 50 50 50 50 20 Refractive index 1.46 1.48 1.48 1.51 1.51 1.51 Resolution (μπι) 30 30 30 30 30 30

S-57-201224060 [Table 5] Comparative Example 1 2 3 4 5 6 (A) Polyoxane A-1 having a radical polymerizable organic group (MTMS/MPTMS=80/20) 100 A-2 (TEOS) /MPTMS=80/20) A-3 (MTMS/TEOS/MPTMS=50/30/20) A4 (MTMS/TMOS/MPTMS=50/30/20) A-5 (MTMS/PTMS/MPTMS=50/30 /20) A-6 (MTMS/TEOS/VTMS=50/30/20) A-7 (MTMS/MPTMS=50/50) A-8 (MTMS/MPTMS=95/5) 100 50 A-9 (MTMS /MPTMS=85/15) 100 A-10 (MTMS/TEOS/MPTMS=65/30/5) 100 Al l (MTMS/TFMS/MPTMS=70/10/20) (B) No radical polymerizable group Polyoxane B-KMTMS/PTMS) 100 50 B-2 (MTMS/PTMS/GPTMS) B-3 (MTMS/TEOS/DTMS) B-4 (MTMS/TMOS/DTMS) B-5 (MTMS/PTMS) /TFMS) B-6 (MTMS/PTMS/yMPTMS) (C) Radical polymerization initiator Cl 3 3 3 3 3 3 C-2 C-3 C-4 (D) Solvent Dl (propylene glycol monomethyl ether) 200 200 2(8) 200 200 200 D-2 (diethylene glycol ethyl methyl ether) D-3 (butyl cellosolve) (E) ethylenically unsaturated compound E-1 (dipentaerythritol hexaacrylate) E- 2 (new Pentaerythritol triacrylate) E-3 (succinic acid modified dipentaerythritol pentaacrylate) Ε·4 (tris(propylene oxyethyl) isocyanurate) (F) particle F-1 [ MP_300 (PMMA particles)] F-2 (SiO2 particles) F-3 (Zr02 particles) F-4 (Ti02 particles) The radical polymerizable properties of all the structural units constituting the components (A) and (B) Content ratio of organic-based structural unit (% by mole) 20.0 5.0 15.0 5.0 0.0 2.9 Transparency (%) 98 98 97 9Ί 96 98 Heat-resistant transparency (%) 5 5 5 5 7 5 Pencil hardness 6H 5H 5H 5H 3H 5H Scratch resistance X Δ Δ Δ Δ Δ Split XXXX Δ Δ Heat cracking XXX Δ △ Δ ITO adhesion evaluation 0 0 0 0 80 80 Sensitivity (mJ/cm2) 50 50 50 50 50 150 Refractive index 1.47 1.47 1.47 1.47 1.47 1.48 Resolution _) 80 80 70 80 50 60 [Simple description of the diagram] None. [Main component symbol description] 〇 • 58-

Claims (1)

201224060 VII. Patent application scope: L A poly-stone composition containing the following components [a] to [d]: [A] having a radical polymerizable organic group (tetra) burning compound and (a2) (a) a decane having a radically polymerizable organic group in the oxime-burning process of the arsenic compound having a radically polymerizable organic group and having a radically polymerizable organic group The ratio of the compound exceeds 15 mTorr/〇; [B] polyoxyalkylene having no radical polymerizable organic group; [c] a radical polymerization initiator; and [D] solvent. 2. The composition of the polyoxane in the first application of the patent application is occupied by all the structural units constituting the above [A] component and component. The content ratio of the structural unit derived from the group-based organic group is 〇2〇莫耳/〇〇3·, as in the case of the poly-stone-oxygen-burning composition in the scope of the patent application, the addition::: contains not included in the foregoing [e] A compound of the [A] component. I, such as Hi: the poly-"combustion composition in the first or second range, more work = F] is selected from the group consisting of organic particles and inorganic particles. 5. As in the scope of claims 1 to 4 ^ — ^ ^ . χ 任 任 项 项 constituting the composition of the polyoxane composition, the method is at least, a: ~ he combines the following components [A] ~ [D] [A] from (a 1) has free radicals a radically polymerizable organic group obtained by polymerizing a decane compound of τ 曰 〇 有机 曰 和 和 和 和 和 曰 曰 曰 曰 曰 曰 S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S Polyoxane, the ratio of (al) a decane compound having a radical polymerizable organic group in the polyoxyalkylene exceeds 丨5 mol 0/〇; soil [B] has no radical polymerizable organic group Polyoxane: [C] Free radical polymerization initiator; and [D] solvent. 6_---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- The polyoxane composition is formed, and the method for forming a cured film of the display element is as follows: (1)~(4) (1) a step of forming a coating film of a polyoxyalkylene composition as described in the scope of claims of the patent application on the substrate; "Step of partial irradiation development (2) Coating film formed by the step (1) At least the step of radiating; (3) the step of coating the film of the film irradiated with the radiation irradiated by the step (2) into a step of heating as in the middle. 6 Green Patent Range Item 7 (4) 3) The method of forming a cured film of a display element is formed. In the eighth item... the element-hardened film is a touch. 201224060 4. The designated representative figure: (1) The representative figure of the case is: None (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: