KR20120030012A - Polysiloxane composition and process for producing the same, and cured film and process for forming the same - Google Patents

Abstract

PURPOSE: A polysiloxane composition is provided to form a hardened film like a protection film, an insulation film uniformly combining demand characteristics at high level. CONSTITUTION: A polysiloxane composition comprises polysiloxane having a radically polymerizable organic group, polysiloxane not having a radically polymerizable organic group, a radical polymerization initiator, and a solvent. The radically polymerizable organic group is obtained through cohydrolysis condensation of a silane compound having a radically polymerizable organic group and a silane compound not having a radically polymerizable organic compound. The ratio of the silane compound having a radically polymerizable organic group is over than 15 mol%.

Description

Polysiloxane composition, its manufacturing method, cured film, and its formation method {POLYSILOXANE COMPOSITION AND PROCESS FOR PRODUCING THE SAME, AND CURED FILM AND PROCESS FOR FORMING THE SAME}

The present invention relates to a polysiloxane composition suitable as a material for forming a cured film such as a protective film of a display element, an interlayer insulating film, a cured film formed of the composition, and a method of forming the cured film.

Display elements, such as a liquid crystal display element, are immersed by a solvent, an acid or an alkaline solution, etc. during the manufacturing process, and when forming a wiring electrode layer by sputtering, a surface of an element is locally exposed to high temperature. In order to prevent deterioration or damage of a display element by such an immersion process or a high temperature process, forming the protective film which is resistant to these processes on the surface of an element is performed.

Such a protective film should have high adhesion to the substrate or lower layer on which the protective film should be formed, and also the layer formed on the protective film, the film itself should be smooth and strong, have transparency, and will not be discolored even under high temperature conditions. It is required to be able to preserve transparency, to maintain transparency, to have sufficient surface hardness, to be excellent in scratch resistance, and the like.

In order to satisfy such a required characteristic, although acrylic resin is mainly used as a component of the radiation sensitive composition for protective film formation, the attempt to use as a component of a radiation sensitive composition the polysiloxane material which is more excellent in heat resistance and transparency than acrylic resin is made | formed. (Patent Documents 1 to 3). However, the polysiloxane-based material does not have sufficient adhesiveness with an ITO (indium tin oxide) transparent conductive film, and cracks easily occur in the cured film, and thus there is a problem in that it does not endure practical use as a protective film. In addition, when the adhesiveness on the molybdenum wiring in a display element is inadequate, the crack or peeling of a protective film may arise from a molybdenum wiring on a starting point. Therefore, development of the polysiloxane radiation sensitive composition which is excellent in heat resistance and transparency, and improved adhesiveness with an ITO transparent conductive film and molybdenum wiring is desired.

In addition, an input device for operating a device by pressing a display on a screen called a touch panel, a touch screen or a touch screen or the like is used in an automatic teller machine, a vending machine, a mobile phone, a portable information terminal, a digital audio player, or the like. Since the touch panel is usually pressed directly with a finger or the like, a protective film is provided. The protective film requires surface hardness such as adhesion to the wiring of the touch panel element and scratch resistance as a protective film.

On the other hand, an interlayer insulation film is formed in order to insulate between the wiring arrange | positioned generally in layer shape in display elements etc. The interlayer insulating film of this display element requires pattern formation of contact holes for wiring. As a material for interlayer insulation film formation of a liquid crystal display element, development of the negative radiation sensitive composition which is advantageous in cost is performed (patent document 4). However, in such a negative radiation sensitive composition, it is difficult to form the contact hole which has a hole diameter of the level which can be used practically. Therefore, in order to form the interlayer insulation film of a display element at present, the positive radiation sensitive composition is used widely from a viewpoint of the advantage of contact hole formation (patent document 5).

Thus, various kinds of radiation sensitive compositions are used for manufacture of display elements, etc. according to the objective and process. In recent years, in view of cost reduction, unification of the kind of radiation sensitive composition has been tried, and it is desired that a protective film and an interlayer insulation film can be formed by one kind of radiation sensitive composition. Specifically, a protective film and an interlayer insulating film excellent in transparency, heat resistance, adhesion, crack resistance, sensitivity, refractive index, surface hardness and scratch resistance can be easily formed, and the resolution capable of forming a practically usable contact hole. The development of the polysiloxane negative radiation sensitive composition which has sufficient adhesiveness and abrasion resistance as a protective film for touch panels is strongly desired.

Japanese Laid-Open Patent Publication No. 2000-001648 Japanese Patent Laid-Open No. 2006-178436 Japanese Laid-Open Patent Publication No. 2008-248239 Japanese Laid-Open Patent Publication No. 2000-162769 Japanese Laid-Open Patent Publication No. 2001-354822

The present invention has been made on the basis of the above circumstances, and an object thereof is to provide a polysiloxane composition capable of forming a cured film such as a protective film or an interlayer insulating film in which the above-described desired characteristics are well-balanced at a high level, and a manufacturing method thereof. It is in doing it. Another object of the present invention is to provide a cured film formed of the polysiloxane composition, a cured film such as an interlayer insulating film, and a method of forming the same.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, this invention is 1st the following component [A]? [D]:

[A] A polysiloxane having a radically polymerizable organic group obtained by cohydrolytic condensation of a silane compound having a (a1) radically polymerizable organic group with a silane compound having no (a2) a radically polymerizable organic group, wherein the polysiloxane Polysiloxane in which the ratio of the silane compound which has a (a1) radically polymerizable organic group in it exceeds 15 mol%,

[B] a polysiloxane having no radically polymerizable organic group,

[C] a radical polymerization initiator, and

[D] solvent

It is to provide a polysiloxane composition containing.

Moreover, this invention is 2nd as a manufacturing method of the said polysiloxane composition,

At least, the following components [A]? [D]:

[A] A polysiloxane having a radically polymerizable organic group obtained by cohydrolytic condensation of a silane compound having a (a1) radically polymerizable organic group and a silane compound having no (a2) radically polymerizable organic group, wherein (a1) in the polysiloxane Polysiloxane in which the ratio of the silane compound which has a radically polymerizable organic group exceeds 15 mol%,

[B] a polysiloxane having no radically polymerizable organic group,

[C] a radical polymerization initiator, and

[D] solvent

It is to provide a manufacturing method for mixing.

Moreover, this invention provides 3rd the cured film of the display element formed from the said polysiloxane composition.

Furthermore, this invention is 4th and the following process (1)-(4):

(1) forming a coating film of the polysiloxane composition on a substrate;

(2) irradiating at least a part of the coating film formed in step (1) with radiation;

(3) developing the coating film irradiated with radiation in step (2), and

(4) Step of heating the coating film developed in Step (3)

It is to provide a method for forming a cured film of a display element comprising a.

Furthermore, this invention is 5th, and provides the cured film of the display element formed by the said method, and is useful as a protective film for touch panels of a display element, for example.

Since the polysiloxane composition of this invention balances the general required characteristics, such as transparency, heat resistance, heat resistance transparency, crack resistance, surface hardness, and abrasion resistance to a high level, and also improves adhesiveness with respect to an ITO transparent conductive film, It is possible to easily form a cured film such as a protective film and an interlayer insulating film having a fine and sophisticated pattern. Therefore, the cured film (protective film or interlayer insulation film) formed in this way can be used suitably for a display element, and it is especially useful as a protective film of a touch panel display element. Moreover, the polysiloxane composition of this invention can express sufficient resolution of the grade which can form a contact hole.

(Form to carry out invention)

Polysiloxane  Composition

The polysiloxane composition of this invention contains [A] component, [B] component, [C] component, and [D] component as an essential component. Hereinafter, each component is demonstrated in detail.

[A] component

The component (A) is a silane compound having a radical polymerizable organic group (hereinafter also referred to as (a1) compound) and a silane compound having no radical polymerizable organic group (hereinafter referred to as (a2) compound). Polysiloxane which has a radically polymerizable organic group obtained by hydrolytic condensation, It is polysiloxane in which the ratio of the compound (a1) in the said polysiloxane exceeds 15 mol%.

It is preferable that it is a hydrolyzable silane compound represented by following formula (1) or following formula (2) as a compound (a1).

　

　

[In formula (1), R <^1> represents a C1-C4 alkyl group, R <^2> represents a single bond, a methylene group, or an alkylene group, X is a vinyl group, an allyl group, a styryl group, or (meth) acryloyl jade. Indicate timing;

In formula (2), R <^3> represents a C1-C4 alkyl group, R <^4> and R <^5> represents a single bond, a methylene group, or an alkylene group independently of each other, Y is a vinyl group, an allyl group, a styryl group, or ( A meta) acryloyloxy group, Z represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, a halogen atom, an epoxy group, an isocyanate group, an amino group, a vinyl group, Styryl group or (meth) acryloyloxy group; p is an integer of 1 or 2].

Here, in this specification, a "hydrolyzable silane compound" means the "silane compound which has a hydrolyzable group", and a "hydrolyzable group" here is a silanol group (-Si-OH) by reaction with water normally. Indicates a group capable of forming On the other hand, a "non-hydrolyzable group" refers to the group which exists stably, without forming a silanol group by reaction with water. In addition, "hydrolysis condensation" means that a siloxane bond (-Si-O-Si-) is formed by a dehydration condensation reaction between silanol groups generated by hydrolysis and / or a condensation reaction between silanol groups and hydrolyzable groups. It means to be formed. In the hydrolysis reaction, when a silanol group is formed from a part of the hydrolyzable group, the microhydrolysis group (-OR ¹ or -OR ³ ) may remain, that is, in a part of component [A]- OR ^1, and may have at least one member selected from -OR ^3.

In addition, in this invention, not only a hydrolyzable silane compound but its partial hydrolyzate can also be used, and it is the same also in [B] component mentioned later. Here, in this specification, a "partial hydrolyzate" means the siloxane compound (2 number of silicon atoms in which at least 1, preferably 2 or more alkoxy groups remain in the molecule | numerator produced by the hydrolysis condensation reaction of an alkoxy group. 100, preferably about 2 to 30 siloxane oligomers).

The alkyl group in R ¹ , R ³ and Z may be linear or branched. As an alkyl group in R <^1> and R <^3> , a C1-C2 alkyl group is preferable from a reactive viewpoint of hydrolysis condensation. Moreover, as an alkyl group in Z, a C1-C6, especially 1-4 alkyl group is preferable. Specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, etc. are mentioned.

As an alkylene group in R <^2> , R <^4> and R <^5> , a C2-C6 alkylene group is preferable and a C2-C3 alkylene group is especially preferable. The alkylene group may be linear or branched, and examples thereof include an ethylene group, trimethylene group, and propylene group.

The (meth) acryloyloxy group in X, Y, and Z is a concept containing an acryloyloxy group and a methacryloyloxy group. In addition, the substitution position of the aromatic ring-shaped vinyl group of a styryl group is not specifically limited, An ortho position, a meta position, or a para position may be sufficient.

As an aryl group in Z, a monocyclic tricyclic aromatic hydrocarbon group is mentioned. The aryl group may have a substituent as long as it has 6 to 14 carbon atoms, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group and an alkoxy group. have. As an aryl group, a phenyl group and a naphthyl group are mentioned, for example, As a substituted aryl group, a tolyl group is mentioned, for example.

In the formula (1), R ¹ is preferably an alkyl group having 1 to 2 carbon atoms, R ² is preferably a single bond or an alkylene group having 2 to 3 carbon atoms, and as X, a vinyl group or a (meth) acryloyloxy group Is preferred.

In said Formula (2), as R <^3> , a C1-C2 alkyl group is preferable, As R <^4> and R <^{5>, a} single bond or a C2-C3 alkylene group is preferable, and as Y, a vinyl group or (meth) acryl Royloxy group is preferable and as Z, a C1-C6 alkyl group is preferable. Moreover, 1 is preferable for p.

As a specific example of the compound represented by said Formula (1), vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tripropoxysilane, o-styryl trimethoxysilane, o-styryl triethoxysilane, m- Styryltrimethoxysilane, m-styryltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloyl Oxytrimethoxysilane, Methacryloyloxytriethoxysilane, Methacryloyloxytripropoxysilane, Acryloyloxytrimethoxysilane, Acryloyloxytriethoxysilane, Acryloyloxytripro Foxysilane, 2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-methacryloyloxyethyltripropoxysilane, 3-methacryloyloxypropyl Trimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyl Cipropyltripropoxysilane, 2-acryloyloxyethyltrimethoxysilane, 2-acryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltripropoxysilane, 3-acryloyloxypropyl Trimethoxysilane, 3-acryloyloxypropyl triethoxysilane, etc. are mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more type.

As a specific example of the compound represented by said Formula (2), vinylmethyldimethoxysilane, vinylmethyl diethoxysilane, vinylphenyldimethoxysilane, vinylphenyl diethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, allylmethyl Dimethoxysilane, allylmethyldiethoxysilane, allyldimethylmethoxysilane, allyldimethylethoxysilane, divinylmethylmethoxysilane, divinylmethylethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3 -Acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylphenyldimethoxysilane, 3-acryloyloxypropylphenyldimethoxysilane, 3,3'-dimethacryloyloxypropyldimethoxy Silane, 3,3'-diacryloyloxypropyldimethoxysilane, 3,3 ', 3 "-trimethacryloyloxypropylmethoxysilane, 3,3', 3" -triacryloyloxypropyl Methoxysilane, etc. are mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more type.

Among the compounds represented by the above formulas (1) and (2), adhesion to crack resistance, surface hardness, wiring, and the like can be achieved at a high level, and vinyltrimethoxy is particularly preferred from the viewpoint of reactivity of hydrolysis condensation. Silane, p-styryltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3 -Acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, etc. are preferable.

Moreover, it is preferable that it is a hydrolysable silane compound represented by following formula (3) as a compound (a2).

　

　

(In formula (3), R <^6> represents a C1-C4 alkyl group, R <^7> represents a single bond, a methylene group, or an alkylene group, W is a C1-C20 substituted or unsubstituted alkyl group, C6-C14 A substituted or unsubstituted aryl group, amino group, mercapto group, epoxy group, glycidyloxy group or 3,4-epoxycyclohexyl group, and q is an integer of 0 to 3).

As an alkyl group in R <^6> , the thing similar to R <^1> of said Formula (1) is mentioned, As an alkyl group and an aryl group in W, the same thing as Z of said Formula (2) is mentioned, and in R <^7> As an alkylene group, the thing similar to R <^5> of the said Formula (2) is mentioned. Moreover, as a substituent of the alkyl group and aryl group in W, the thing similar to the substituent of the aryl group in Z of said Formula (2) is mentioned.

As R <^{7>, a} single bond or a C2-C3 alkylene group is preferable, and as W, a C1-C10 substituted or unsubstituted alkyl group, a C6-C8 substituted or unsubstituted aryl group or glycidyloxy group is preferable. Moreover, as a substituent of an alkyl group or an aryl group, a halogen atom is preferable. In addition, as q, 0 or 1 is preferable.

As the hydrolyzable silane compound represented by Formula (3), a silane compound having four hydrolyzable groups, a silane compound having one non-hydrolyzable group and three hydrolyzable groups, a silane having two non-hydrolyzable groups and two hydrolyzable groups Compounds, or mixtures thereof.

As a specific example of such a hydrolyzable silane compound,

As a silane compound having four hydrolyzable groups, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane Etc;

As a silane compound having one non-hydrolyzable group and three hydrolyzable groups, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, phenyltrimethoxysilane, phenyltrie Methoxysilane, aminotrimethoxysilane, aminotriethoxysilane, 3-mercaptopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy, γ-glycidoxypropyltrimethoxy Silanes and the like;

Examples of the silane compound having two non-hydrolyzable groups and two hydrolyzable groups include dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type.

Among these hydrolyzable silane compounds, a silane compound having four hydrolyzable groups and a silane compound having one non-hydrolyzable group and three hydrolyzable groups are preferable, and a silane compound having one non-hydrolyzable group and three hydrolyzable groups is Particularly preferred. Specific examples of preferred hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane and ethyltrimeth Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltri Methoxysilane is mentioned.

The addition ratio of the compound (a1) in the total of the compound (a1) and the compound (a2) exceeds 15 mol%, but it is preferably 16 mol% or more, particularly 18 mol% or more. When the ratio of the compound (a1) is 15 mol% or less, the exposure sensitivity is lowered, and the heat resistance, the adhesiveness, and the resolution of the resulting cured film are lowered. Moreover, it is preferable that the upper limit of the addition ratio of a compound (a1) is 50 mol%, Furthermore, 40 mol%, especially 30 mol% from a crack resistance, heat resistance, and an adhesive viewpoint.

As conditions for cohydrolytic condensation of the compound (a1) and the compound (a2), at least a part of the compound (a1) and the compound (a2) are hydrolyzed, and the hydrolyzable group is converted into a silanol group to generate a condensation reaction. Although it does not specifically limit as long as it is, As an example, the following method is mentioned.

In a solvent, the method of mixing a (a1) compound and a (a2) compound, adding water to a mixed solution, and hydrolyzing condensation is employ | adopted preferably.

As water used for the cohydrolytic condensation reaction of the compound (a1) and the compound (a2), it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, distillation or the like. . By using such purified water, side reaction can be suppressed and the reactivity of hydrolysis can be improved. The amount of water to be used is preferably 0.1 to 3 moles, more preferably 0.3 to 2 moles, even more preferably 0.5 to 1.5 moles with respect to 1 mole of the total amount of the hydrolyzable groups of the (a1) compound and the (a2) compound. . By using this amount of water, the reaction rate of hydrolysis condensation can be optimized.

Although it does not specifically limit as a solvent used for the cohydrolytic condensation reaction of a compound (a1) and a compound (a2), Usually, the same thing as the solvent used for preparation of the polysiloxane composition mentioned later can be used. Preferable examples of such a solvent include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. These may be used individually by 1 type, or may be used in combination of 2 or more type. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or methyl 3-methoxypropionate are particularly preferable.

The cohydrolytic condensation reaction of the compound (a1) with the compound (a2) is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid). , Nitrogen-containing compounds such as phosphoric acid, acidic ion exchange resins, various Lewis acids, base catalysts (eg, ammonia, primary amines, secondary amines, tertiary amines, pyridine, etc.); basic ion exchange resins; Hydroxides such as sodium, carbonates such as potassium carbonate, carbonates such as sodium acetate, various Lewis salt groups, or alkoxides (for example, zirconium alkoxides, titanium alkoxides, aluminum alkoxides). As a usage-amount of a catalyst, it is 0.2 mol or less with respect to a total of 1 mol of a compound (a1) and a compound (a2) from a viewpoint of the acceleration of a hydrolysis condensation reaction, More preferably, it is 0.00001-0.10 mol.

Although the reaction temperature and reaction time in the cohydrolytic condensation reaction of (a1) compound and (a2) compound can be set suitably, the following conditions can be employ | adopted, for example. Reaction temperature becomes like this. Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC. Reaction time becomes like this. Preferably it is 30 minutes-24 hours, More preferably, it is 1-12 hours. By setting it as such reaction temperature and reaction time, a hydrolysis condensation reaction can be performed most efficiently. In this hydrolysis condensation reaction, even if a hydrolyzable silane compound, water, and a catalyst are added to a reaction system at once, and a reaction is performed in one step, or a hydrolyzable silane compound, water, and a catalyst are divided into several times, and it adds in a reaction system. By doing this, you may perform a hydrolysis reaction and a condensation reaction in multiple steps. In addition, after the hydrolysis condensation reaction, water and the resulting alcohol can be removed from the reaction system by adding a dehydrating agent and then evaporating. The dehydrating agent used in this step is generally removed by adsorption or inclusion of excess water to ensure that the dehydrating capacity is consumed completely, or by evaporation.

Thus, as [A] component obtained, it is a structural unit (henceforth a structural unit (4) represented by following formula (4) derived from a compound (a1), and following formula (5) derived from a compound (a2)). It is preferable to include the structural unit (henceforth also called a structural unit (5)), and the structural unit (henceforth called a structural unit (6)) represented by following formula (6).

[In formula (4), R <^2> and X are the same meaning as the above,

In formula (6), R ⁸ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

Moreover, as a substituent of the alkyl group in R <^8> , the thing similar to the substituent of the aryl group in Z of said Formula (2) is mentioned.

The content ratio (molar ratio) of each structural unit in [A] component is a structural unit (4) / structural unit (5) / structural unit (6) = 16-25 / 10-40 / 40-70, Furthermore, 18-25 It is preferable that it is / 20-40 / 40-60.

The molecular weight of the [A] component obtained by the hydrolysis condensation reaction can be measured as a weight average molecular weight of polystyrene conversion using GPC (gel permeation chromatography) using mobile phase tetrahydrofuran. It is preferable to carry out in the range of 500-10000, and, as for the weight average molecular weight (Mw) of (A) component, it is more preferable to carry out in the range of 1000-5000. The film-forming property of the coating film of a polysiloxane composition can be improved by making the value of the weight average molecular weight of (A) component into 500 or more. On the other hand, the fall of alkali developability of a polysiloxane composition can be prevented by making a weight average molecular weight 10000 or less.

Moreover, ratio with the number average molecular weight (Mn) measured by the same conditions as weight average molecular weight (Mw), ie, dispersion degree (Mw / Mn), Preferably it is 1.0-15.0, More preferably, it is 1.1-10.0, More preferably, it is 1.1-5.0. By setting it in this range, alkali developability, adhesiveness, and crack resistance can be compatible.

[B] component

Component [B] is a polysiloxane which does not have a radically polymerizable organic group. By using the component [A] and the component [B] in combination, it becomes possible to achieve crack resistance, heat resistance, adhesiveness and resolution at a high level as compared with the case where only the component [A] is used.

[B] component can be obtained by (co) hydrolytic condensation of at least 1 sort (s) of the hydrolyzable silane compound represented by said (3) on the conditions similar to [A] component.

As the [B] component obtained by the (co) hydrolysis condensation reaction, a structural unit represented by the following formula (7) (hereinafter also referred to as a structural unit (7)) and a structural unit represented by the following formula (8) (hereinafter, Also referred to as structural unit (8)).

[In Formula (7), R ⁹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and in Formula (8), R ¹⁰ represents a substituted or unsubstituted aryl group having 6 to 14 carbon atoms.

Moreover, as a substituent of the alkyl group in R <^9> and the aryl group in R <^10> , the same thing as the substituent of the aryl group in Z of said Formula (2) is mentioned.

It is preferable that the content rate (molar ratio) of each structural unit in (B) component is a structural unit (7) / structural unit (8) = 30-70 / 70-30, Furthermore, it is 40-60 / 60-40.

The weight average molecular weight (Mw) of the component [B] obtained by the hydrolysis condensation reaction can be measured under the same conditions as the component [A], and is preferably 500 to 10000 from the viewpoint of film forming properties and developability of the coating film. More preferably, it is 1000-5000.

In addition, the ratio with the number average molecular weight (Mn) measured under the same conditions as the weight average molecular weight (Mw), that is, the degree of dispersion (Mw / Mn), is preferably from the standpoint of alkali developability, adhesion, and crack resistance. 1.0-15.0, More preferably, it is 1.1-10.0, More preferably, it is 1.1-5.0.

It is preferable that the content rate of a component [A] and a component [B] is 80-400 mass parts and 100-200 mass parts of [B] components with respect to 100 mass parts of [A] components.

Moreover, the content rate of the structural unit which has a radically polymerizable organic group which occupies for all the structural units which comprise [A] component and [B] component, ie, it occupies in the whole structural unit of [A] component and [B] component, (a1) It is preferable to adjust suitably so that the content rate of the structural unit derived from a compound may be 1-20 mol%, Furthermore, it is 5-18 mol%, Especially 10-15 mol%. By containing the structural unit which has a radically polymerizable organic group in such a ratio, it becomes possible to achieve adhesiveness, crack resistance, heat resistance, and abrasion resistance at a high level, and can also be equipped with radiation sensitivity.

Furthermore, [A] component and the content of the structural unit having a radically polymerizable organic occupies the whole structural units constituting the [B] ^{component, 1 H-NMR, 13 C} -NMR, FT-IR, pyrolysis gas chromatography By mass spectrometry, qualitative and quantitative analysis is possible.

[C] component

The component [C] is a radical polymerization initiator. As a radical polymerization initiator used by this invention, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, etc. are mentioned.

Specific examples of the O-acyl oxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [ 9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one Oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime ), Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone- 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9- Ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybene Yl) -9H- carbazole-3-yl], and the like -1- (O- acetyl oxime). These O-acyl oxime compounds can be used individually or in mixture of 2 or more types.

Among them, preferred O-acyl oxime compounds include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and ethane On-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyl Oxime).

As an acetophenone compound, the (alpha)-amino ketone compound and the (alpha)-hydroxy ketone compound are mentioned, for example.

Specific examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1 -(4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, etc. are mentioned.

Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1 -One, 4- (2-hydroxy ethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like. These acetophenone compounds can be used individually or in mixture of 2 or more types.

Of these acetophenone compounds, α-aminoketone compounds are preferable, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2 Especially preferred is -methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl ) -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. These biimidazole compounds can be used individually or in mixture of 2 or more types.

Among these biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2 , 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl- 1,2'-biimidazole is particularly preferred.

In the polysiloxane composition of this invention, when using a biimidazole compound as a [C] component, in order to sensitize it, the aliphatic or aromatic compound which has a dialkylamino group (henceforth "amino type sensitizer") is added. can do.

As such an amino type sensitizer, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, etc. are mentioned, for example. Among these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferable. These amino sensitizers can be used individually or in mixture of 2 or more types.

In addition, when using a biimidazole compound and an amino sensitizer together, a thiol compound can be added as a hydrogen radical donor. The biimidazole compound is sensitized and cleaved by an amino sensitizer to generate an imidazole radical, but a high polymerization initiation capacity may not be expressed as it is. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, a hydrogen radical is donated from a thiol compound to an imidazole radical. As a result, while the imidazole radical is converted into neutral imidazole, the component which has the sulfur radical with a high polymerization start ability generate | occur | produces, and even the low radiation dose can form the cured film with a high surface hardness.

As a specific example of such a thiol compound,

Aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, and 2-mercapto-5-methoxybenzothiazole;

Aliphatic monothiol compounds such as 3-mercaptopropionic acid and methyl 3-mercaptopropionic acid;

And bifunctional or higher aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate). These thiol compounds can be used individually or in mixture of 2 or more types.

Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

When using a biimidazole compound and an amino sensitizer together, as an usage-amount of an amino sensitizer, it is 0.1-50 mass parts with respect to 100 mass parts of biimidazole compounds, More preferably, it is 1-20 mass It is wealth. By making the usage-amount of an amino sensitizer into the said range, the curing reactivity at the time of exposure improves and the surface hardness of the cured film obtained can be raised.

Moreover, when using a biimidazole compound, an amino type sensitizer, and a thiol compound together, as a usage-amount of a thiol compound, it is 0.1-50 mass parts with respect to 100 mass parts of biimidazole compounds, More preferably, 1 ? 20 parts by mass. By making the usage-amount of a thiol compound into the said range, the surface hardness of the cured film obtained can be improved.

In this invention, it is preferable to contain at least 1 sort (s) chosen from the group which consists of an O-acyl oxime compound and an acetophenone compound as [C] component, and may also contain a biimidazole compound.

As a commercial item of the [C] radical polymerization initiator, it is ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), for example. (Irgacure OXE02), 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyloxime)] (Irgacure OXE01), 2-methyl- [4- (methyl Thio) phenyl] -2-morpholino-1-propane (irgacure 907), 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (irgacure 379EG) (above, Chiba Specialty Chemicals Co., Ltd.) etc. are mentioned.

The usage-amount of [C] component becomes like this. Preferably it is 0.05-30 mass parts, More preferably, it is 0.1-15 mass parts with respect to 100 mass parts of total of the [A] component and the [B] component. By using the usage-amount of component (C) in the said range, even in the case of a low exposure amount, the cured film which shows high radiation sensitivity and has sufficient surface hardness can be formed.

[D] component

[D] component is a solvent. Although it does not specifically limit as a solvent, It is preferable to contain the alcohol type solvent which is especially a protic solvent. By using an alcoholic solvent, each component can be dissolved or dispersed uniformly, thereby making it possible to improve the coatability of the composition solution to a large substrate, and also to apply coating stains (stripe-shaped stains, pin trace stains, mist stains). Etc.) can be suppressed and the film thickness uniformity can be further improved.

As such an alcoholic solvent,

Long-chain alkyl alcohols such as 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol, and 1,8-octanediol;

Aromatic alcohols such as benzyl alcohol;

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;

Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and the like. These alcohol solvents can be used individually or in combination of 2 or more types.

Among these alcohol solvents, benzyl alcohol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether are particularly preferable from the viewpoint of improving coating properties.

As the component [D], one type may be used alone, or two or more types may be mixed and used.

The amount of the component [D] used is preferably 5 parts by mass to 300 parts by mass, and more preferably 10 parts by mass to 200 parts by mass with respect to 100 parts by mass of the component [A]. By using the amount of the [D] component in the said range, coating property improvement with respect to a glass substrate etc. is enabled, the generation | occurrence | production of application | coating stains (stripe-shaped stain, pin trace stain, fog stain, etc.) is suppressed, and film thickness uniformity is carried out. Can be further improved.

In the present invention, along with the alcohol solvent, other solvents, for example, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones And esters.

As a solvent other than the alcohol solvent, the following may be mentioned.

As ethers, For example, tetrahydrofuran etc .;

As diethylene glycol alkyl ether, For example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As ethylene glycol alkyl ether acetates, For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .;

As propylene glycol monoalkyl ether acetates, For example, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, a propylene glycol monopropyl ether acetate, a propylene glycol monobutyl ether acetate, etc .;

As propylene glycol monoalkyl ether propionates, a propylene glycol monomethyl ether propionate, a propylene glycol monoethyl ether propionate, a propylene glycol monopropyl ether propionate, a propylene glycol monobutyl ether propionate, etc. are mentioned, for example. ;

As aromatic hydrocarbons, For example, toluene, xylene, etc .;

As ketones, For example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl- 2-pentanone, etc .;

As esters, for example, methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2- Ethyl methyl propionate, methyl hydroxyacetic acid, ethyl hydroxyacetic acid, hydroxyacetic acid butyl, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionic acid methyl, 3-hydroxypropionic acid, 3-hydroxypropionic acid Propyl, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoic acid, methyl methoxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid propyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl Propyl ethoxyacetic acid, butyl ethoxyacetic acid, methyl propoxyacetate, ethyl propoxyacetate, Lopoxyacetic acid propyl, butyl propoxyacetic acid, methyl butoxyacetic acid, ethyl butoxyacetate, butoxyacetic acid propyl, butyl butoxyacetic acid, 2-methoxypropionate methyl, 2-methoxypropionic acid propyl, 2-methoxypropionic acid propyl And butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, and the like. These solvents can be used individually or in mixture of 2 or more types.

The polysiloxane composition of this invention can contain the following component further.

[E] component

[E] component is an unsaturated compound which superposes | polymerizes by irradiating a radiation in presence of [C] radical polymerization initiator. However, component [A] is excluded.

As such a polymerizable unsaturated monomer, a monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid ester is preferable from a viewpoint that a polymerizability is favorable and the intensity | strength of the cured film obtained improves.

As monofunctional (meth) acrylic acid ester, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2 -Acryloyloxyethyl) (2-hydroxypropyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, (omega)-carboxy polycaprolactone monoacrylate, etc. are mentioned. As a commercial item, For example, Aronix M-101, M-111, M-114, M-5300 (above, Toagosei Co., Ltd.); KAYARAD TC-110S, TC-120S (above, Nippon Kayaku Co., Ltd.); Viscoat 158, East 2311 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), etc. are mentioned.

As a bifunctional (meth) acrylic acid ester, for example, ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimetha, Acrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanedioldiacrylate, 1,6-hexanedioldimethacrylate, 1,9-nonanedioldiacrylate, 1 And 9-nonanediol dimethacrylate. As a commercial item, For example, Aronix M-210, M-240, M-6200 (above, Toagosei Co., Ltd.); KAYARAD HDDA, HX-220, R-604 (above, Nippon Kayaku Co., Ltd.); Biscot 260, 312, 335HP (above, Osaka Yuki Kagaku Kogyo Co., Ltd.); Light acrylate 1, 9-NDA (Kyoeisha Chemical Co., Ltd.) etc. are mentioned.

As (meth) acrylic acid ester more than trifunctional, for example, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate Mixture, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid modified penta Erythritol triacrylate, succinic acid modified dipentaerythritol In addition to the acrylate and the tris (acryloxyethyl) isocyanurate, a compound having a linear alkylene group and an alicyclic structure and having at least two isocyanate groups, at least one hydroxyl group in the molecule, and 3, 4 The polyfunctional urethane acrylate type compound etc. which are obtained by making it react with the compound which has a dog or five (meth) acryloyloxy group are mentioned. As a commercial item, for example, Aronix M-309, East M-315, East M-400, East M-405, East M-450, East M-7100, East M-8030, East M-8060, East TO- 1450 (above, Toagosei Co., Ltd.); KAYARAD TMPTA, copper DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120, copper DPEA-12 (above, Nippon Kayaku Co., Ltd.); Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.); As a commercial item containing a polyfunctional urethane acrylate type compound, New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (Nippon Kayaku Co., Ltd.), etc. are mentioned.

Ω-carboxy polycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and di of such [E] component Pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate mixture, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaeryte Commercially available products containing litolitriacrylate, succinic acid modified dipentaerythritol pentaacrylate, and polyfunctional urethane acrylate compounds are preferable. Especially, trifunctional or more than (meth) acrylic acid ester is preferable and the mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is especially preferable.

The component [E] may be used alone or in combination of two or more thereof. As for the usage-amount of [E] component, 5-300 mass parts is preferable with respect to a total of 100 mass parts of [A] component and [B] component, 10-200 mass parts is more preferable, 20-100 mass parts is especially preferable. . By using the usage-amount of the component (E) in the said range, the sensitivity of the said composition, the surface height of the cured film obtained, and heat resistance become further more favorable.

[F] component

The component [F] is at least one selected from organic particles and inorganic particles. By containing the component [F], scratch resistance, crack resistance and the like can be enhanced. As for the average particle diameter of organic particle | grains and an inorganic particle, the range of 0.005-0.5 micrometer is preferable.

The component [F] may be added or mixed directly with other components in the form of a powder, or may be added to or mixed with other components with a solvent dispersion to distill off the solvent.

As organic particle | grains, acrylic type microparticles | fine-particles etc. are used suitably. As acryl-type microparticles | fine-particles, the methyl methacrylate polymer etc. are mentioned, for example. As a commercial item of organic particle | grains, Zefiac copper F-320, copper F-301, copper F-340, copper F-325, copper F-351 (above, Kantsukasei Co., Ltd. make), Acrylic fine particle MP-300 (made by Soken Chemical Co., Ltd.), etc. are mentioned.

Examples of the inorganic fine particles include particles mainly composed of silica, alumina, zirconium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate, talc, montmorillonite, and the like, and silica and alumina as main components. Preferred particles are preferred.

The shape of the inorganic fine particles may be any of a spherical shape, a rod shape, a plate shape, a fibrous shape, and an indeterminate shape, and these may be solid, hollow, or porous. It may be a shape.

As an example of the commercial item of an inorganic fine particle, Admafine SO-E1, copper SO-E2, copper SO-E3, copper SO-E4, copper SO-E5, copper SE3200-SEJ (the Adad company) Mattex manufacture), SS01, SS03, SS15, SS35 (made by Osaka Kasei Co., Ltd.), etc. are mentioned. As specific examples of such inorganic fine particles, as silica particles, methanol silicazol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40 , ST-C, ST-N, ST-O, ST-50, ST-OL (manufactured by Nissan Chemical Industries, Ltd.), zirconia particles, HXU-110 JC, HXU-210C, NZD-3101 (Sumitomo Osaka Chemical MT-05, MT-100W, MT-100SA, MT-100HD, MT, as ID191 (made by Teika Co., Ltd.), ZRPMA15WT% -E05 (manufactured by Seaikasei Co., Ltd.), titanium oxide particles -300HD, MT-150A, ND138, ND139, ND140, ND154, ND165, ND177, TS-063, TS-103, TS-159 (made by Teika Co., Ltd.), etc. are mentioned.

The inorganic fine particles may be surface treated with a silane coupling agent or the like. By performing such surface treatment, compatibility with other components can be improved and dispersibility and mechanical strength in a composition can be improved.

[F] component may be used independently and may mix and use 2 or more types. The usage-amount of [F] component becomes like this. Preferably it is 1 mass part-600 mass parts, More preferably, it is 10 mass parts-200 mass parts with respect to 100 mass parts of [A] component. By setting the usage-amount of the [F] component in the said range, the scratch resistance of the protective film and interlayer insulation film obtained etc. can be improved further.

The polysiloxane composition of the present invention is added to the above-mentioned [A]-[D] components and, if necessary, in a range not impairing the desired effects, a [G] radiation-sensitive acid generator, a radiation-sensitive base generator, [H] It may contain other optional components, such as surfactant.

[G] Ingredients

[G] component is a radiation sensitive acid generator and a radiation sensitive base generator. The component [G] is defined as a compound capable of releasing an acidic active substance or an alkaline active substance which acts as a catalyst when the polysiloxane is condensed or cured by irradiation with radiation.

As the radiation-sensitive acid generator, diphenyl iodonium salt, triphenylsulfonium salt and tetrahydrothiophenium salt are preferable, and triphenylsulfonium salt and tetrahydrothiophenium salt are particularly preferable. As a specific example of diphenyl iodonium salt, diphenyl iodonium tetrafluoro borate, diphenyl iodonium hexafluoro phosphonate, diphenyl iodonium hexafluoro arsenate, diphenyl iodonium trifluoro Romethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium butyltris (2,6-difluorophenyl) borate, 4-methoxy Phenylphenyl iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4- t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate And bis (4-t-butylphenyl) iodonium camphor sulfonic acid.

Specific examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, and triphenylsulfonium-p. -Toluene sulfonate, triphenyl sulfonium butyl tris (2, 6- difluorophenyl) borate, etc. are mentioned.

Specific examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiopheniumtrifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl Tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2 -(Norbornane-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo [ 2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- ( 6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1- Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, etc. are mentioned.

Among these radiation-sensitive acid generators, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, 1- (4,7-dibutoxy-1-naphthalenyl) from the viewpoint of improving radiation sensitivity Tetrahydrothiophenium trifluoromethanesulfonate is particularly preferred.

Examples of radiation-sensitive base generators include 2-nitrobenzylcyclohexylcarbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, N- (2-nitrobenzyloxycarbonyl) Pyrrolidine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyl oxime, 4- (methyl Thiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1- (4-morpholi Nophenyl) -butanone, hexaamine cobalt (III) tris (triphenylmethylborate), and the like. Among these radiation-sensitive base generators, 2-nitrobenzylcyclohexylcarbamate and O-carbamoylhydroxyamide are particularly preferable from the viewpoint of improving radiation sensitivity.

A component [G] may be used individually by 1 type, and may mix and use 2 or more types. The usage-amount of the [G] component becomes like this. Preferably it is 20 mass parts or less, More preferably, it is 10 mass parts or less with respect to 100 mass parts of [A] components. By setting the usage-amount of the component [G] to 20 parts by mass or less, a cured film product having a good balance of radiation sensitivity, the pencil hardness of the protective film to be formed, and the interlayer insulating film and the heat resistance (heat resistance and transparency) can be obtained.

[H] component

[H] component is surfactant. [H] component can be added in order to improve the applicability | paintability of a polysiloxane composition, the reduction of application | coating stain, and the developability of a radiation irradiation part. As the [H] component, nonionic surfactants, fluorine-based surfactants and silicone-based surfactants are preferable.

As a nonionic surfactant, For example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; (Meth) acrylic acid type copolymers etc. are mentioned. Examples of the (meth) acrylic acid copolymers include Polyflow No. 57, Copper No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like as commercially available trade names.

As the fluorine-based surfactant, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 Fluoroethers such as 1,2,2-tetrafluorobutyl) ether and hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether; Sodium perfluorododecylsulfonate; Fluoroalkanes such as 1,1,2,2,8,8,9,9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane; Sodium fluoroalkylbenzenesulfonic acid; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodides; Fluoroalkyl polyoxyethylene ethers; Perfluoroalkyl polyoxyethanols; Perfluoroalkylalkoxylates; Fluorine-based alkyl esters and the like.

Commercially available products of these fluorine-based surfactants include Ftop EF301, Copper EF303, Copper EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megaface F171, Copper F172, and Copper F173 (manufactured by Dainippon Inky Co., Ltd.). ), Fluorad FC430, Copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), AsahiGuard AG710, Surflon S-382, Copper SC-101, Copper SC-102, Copper SC-103 And SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), FTX-218 (manufactured by Neos Co., Ltd.), and the like.

Examples of the silicone-based surfactant include commercially available trade names such as SH200-100cs, SH28PA, SH30PA, ST89PA, SH190 (manufactured by Torreda Corning Silicon Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). Can be mentioned.

[H] component may be used independently and may be used in mixture of 2 or more type. The usage-amount of [H] component becomes like this. Preferably it is 10 mass parts or less with respect to 100 mass parts of [A] components. By setting the amount of the component [H] to 10 parts by mass or less, the coatability of the polysiloxane composition can be optimized.

The polysiloxane composition of this invention is prepared as a solution or dispersion liquid by mixing and disperse | distributing [A] and [B] component, [C] component, and arbitrary components in a predetermined ratio among the [D] components, for example.

The ratio of components other than the [D] component (that is, the total amount of [A], [B] and [C] components, and other optional components) in the polysiloxane composition can be arbitrarily set according to the purpose of use, the desired film thickness, and the like. , Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%, More preferably, it is 15-35 mass%.

Of display elements Cured film  formation

Next, the method of forming a cured film on the board | substrate which should comprise a display element using the polysiloxane composition of this invention is demonstrated. The method includes the following steps (1) to (4). Moreover, a protective film, an interlayer insulation film, etc. are mentioned as a cured film of a display element.

(1) forming the coating film of the polysiloxane composition of the present invention on a substrate,

(2) irradiating at least a part of the coating film formed in step (1) with radiation;

(3) developing the coating film irradiated with radiation in step (2), and

(4) A step of heating the coating film developed in the step (3).

Process (1)

In process (1), after apply | coating the solution or dispersion liquid of the polysiloxane composition of this invention on a board | substrate, Preferably, a solvent is removed and a coating film is formed by heating (prebaking) an application surface. As a material of the board | substrate which can be used, glass, quartz, silicone, resin, etc. are mentioned, for example. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, ring-opening polymers of cyclic olefins, and hydrogenated products thereof.

It does not specifically limit as a coating method of the solution or dispersion of a polysiloxane composition, For example, a suitable method, such as a spray method, a roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, is employ | adopted. Can be. Among these coating methods, the spin coating method or the slit die coating method is particularly preferable. Although the conditions of prebaking differ also according to the kind, compounding ratio, etc. of each component, Preferably it can be made into about 1 to 10 minutes at 70-120 degreeC.

Process (2)

In process (2), it exposes to at least one part of the coating film formed in process (1). Usually, when exposing to a part of coating film, it exposes through the photomask which has a predetermined pattern. As radiation used for exposure, visible light, an ultraviolet-ray, far ultraviolet rays, an electron beam, X-rays, etc. can be used, for example. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferred, and particularly radiation containing 365 nm ultraviolet rays.

The exposure amount in the said process is the value which measured the intensity | strength in the wavelength of 365 nm of a radiation with the illuminometer (OAI 'model 356, OAI'Optical'Associates Inc. make), Preferably it is 10-1,000mJ / cm <2>, More preferable. Preferably 20-700 mJ / cm 2.

Process (3)

In step (3), by developing the coating film after exposure, an unnecessary part (non-irradiation part of a radiation) is removed and a predetermined pattern is formed. Thus, since the non-irradiated part of radiation is removed, the polysiloxane composition of this invention is a negative radiation sensitive composition. As a developing solution used for a developing process, the aqueous solution of alkali (alkaline compound) is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia; And quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

Moreover, an appropriate amount of water-soluble organic solvents and surfactants, such as methanol and ethanol, can also be used for such aqueous alkali solution. As the developing method, for example, a suitable method such as a puddle method, a dipping method, a rocking dipping method or a shower method can be used. Although developing time changes with the composition of a polysiloxane composition, Preferably it is about 10 to 180 second. Subsequent to such development treatment, for example, flowing water washing is performed for 30 to 90 seconds, followed by air drying with, for example, compressed air or compressed nitrogen, whereby a desired pattern can be formed.

Process (4)

In the step (4), by heating the patterned thin film using a heating device such as a hot plate or an oven, the condensation reaction of the [A] and [B] components can be promoted, and a cured film can be formed reliably. Heating temperature is 120-250 degreeC, for example. Although heating time changes with kinds of a heating apparatus, it can be set as 5 to 30 minutes, for example, when performing a heating process on a hotplate, and 30 to 90 minutes when performing a heating process in an oven. The step baking method etc. which perform two or more heating processes can also be used. In this manner, a patterned thin film corresponding to a cured film of a target display element, for example, a protective film or an interlayer insulating film, can be formed on the surface of the substrate.

Cured film (Protective film or interlayer insulating film)

The film thickness of the cured film formed in this way becomes like this. Preferably it is 0.1-10 micrometers, More preferably, it is 0.1-6 micrometers, More preferably, it is 0.1-4 micrometers.

The cured film formed of the polysiloxane composition of the present invention has a high resolution, as well as excellent properties of ITO adhesion, surface hardness, transparency, heat resistance transparency, scratch resistance, crack resistance and flatness to the substrate, as will be apparent from the following examples. It is possible to form a pattern having high accuracy. Therefore, the said cured film is used suitably for display elements, such as a touch panel of a liquid crystal display element.

(Example)

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolyzed condensate of the hydrolyzable silane compound obtained from each synthesis example below were measured by gel permeation chromatography (GPC) according to the following specification.

Device: GPC-101 (Showa Denko KK)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko KK)

Mobile phase: tetrahydrofuran

[A] component Polysiloxane Synthetic example

Synthesis Example 1

In a container with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was added, followed by 39 parts by mass of methyltrimethoxysilane (MTMS) and 18 parts by mass of 3-methacryloxypropyltrimethoxysilane (MPTMS). It heated until the temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 19 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 2 hours. After cooling to 45 ° C, 28 parts by mass of methyl orthoformate was added as a dehydrating agent, followed by stirring for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. By the above, polysiloxane (A-1) was obtained. Solid content concentration of polysiloxane (A-1) was 35 mass%, the weight average molecular weight (Mw) was 1800, and dispersion degree (Mw / Mn) was 2.2.

Synthesis Example 2

21 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, 55 mass parts of tetramethoxysilanes (TEOS) and 16 mass parts of 3-methacryloxypropyl trimethoxysilanes (MPTMS) were put, and solution temperature It heated until it became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 23 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 2 hours. After cooling to 45 ° C, 33 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol and ethanol which generate | occur | produced by ion-exchange water and hydrolysis condensation were removed. By the above, polysiloxane (A-2) was obtained. Solid content concentration was 33 mass%, polysiloxane (A-2) was 2500, and the weight average molecular weight (Mw) was 2500, and dispersion degree (Mw / Mn) was 2.4.

Synthesis Example 3

23 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, Then, 24 mass parts of methyl trimethoxysilane (MTMS), 22 mass parts of tetramethoxysilane (TEOS), and 3-methacryloxypropyl trimeth 17 mass parts of oxysilanes (MPTMS) were put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 21 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 2 hours. After cooling to 45 ° C, 30 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol and ethanol which generate | occur | produced by ion-exchange water and hydrolysis condensation were removed. By the above, polysiloxane (A-3) was obtained. Solid content concentration of the polysiloxane (A-3) was 34 mass%, the weight average molecular weight (Mw) was 2600, and dispersion degree (Mw / Mn) was 2.3.

Synthesis Example 4

23 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, Then, 24 mass parts of methyl trimethoxysilane (MTMS), 16 mass parts of tetramethoxysilane (TMOS), 3-methacryloxypropyl trimeth 17 mass parts of oxysilanes (MPTMS) were put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 21 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 2 hours. After cooling to 45 ° C, 30 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. By the above, polysiloxane (A-4) was obtained. Solid content concentration of polysiloxane (A-4) was 35 mass%, the weight average molecular weight (Mw) was 2500, and dispersion degree (Mw / Mn) was 2.3.

Synthesis Example 5

27 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, Then, 12 mass parts of methyl trimethoxysilane (MTMS), 30 mass parts of petyl trimethoxysilane (PTMS), and 3-methacryloxypropyl tree 15 mass parts of methoxysilane (MPTMS) was put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 16 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 2 hours. After cooling to 45 ° C, 30 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. By the above, polysiloxane (A-5) was obtained. Solid content concentration of polysiloxane (A-5) was 28 mass%, the weight average molecular weight (Mw) was 1800, and dispersion degree (Mw / Mn) was 2.0.

[Synthesis Example 6]

In a container with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was placed, followed by 27 parts by mass of methyltrimethoxysilane (MTMS), 25 parts by mass of tetramethoxysilane (TEOS), and vinyltrimethoxysilane (VTMS). 12 mass parts was put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 23 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 2 hours. After cooling to 45 ° C, 34 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol and ethanol which generate | occur | produced by ion-exchange water and hydrolysis condensation were removed. By the above, polysiloxane (A-6) was obtained. Solid content concentration of polysiloxane (A-6) was 28 mass%, the weight average molecular weight (Mw) was 2300, and dispersion degree (Mw / Mn) was 2.2.

[Synthesis Example 7]

27 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, and then 20 mass parts of methyl trimethoxysilane (MTMS) and 37 mass parts of 3-methacryloxypropyl trimethoxysilane (MPTMS) were put into a solution, It heated until the temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 16 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 2 hours. After cooling to 45 ° C., 23 parts by mass of methyl orthoformate was added as a dehydrating agent, followed by stirring for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. Polysiloxane (A-7) was obtained by the above. Solid content concentration of polysiloxane (A-7) was 36 mass%, the weight average molecular weight (Mw) was 1600, and dispersion degree (Mw / Mn) was 2.0.

[Synthesis Example 8]

22 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, 52 mass parts of methyl trimethoxysilanes (MTMS), 5 mass parts of 3-methacryloxypropyl trimethoxysilanes (MPTMS), and a solution It heated until the temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 22 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and it preserve | saved for 2 hours. After cooling to 45 ° C, 32 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. By the above, polysiloxane (A-8) was obtained. Solid content concentration was 33 mass%, the weight average molecular weight (Mw) was 2400, and dispersion degree (Mw / Mn) was 2.4 in polysiloxane (A-8).

Synthesis Example 9

In a container with a stirrer, 23 parts by mass of propylene glycol monomethyl ether was placed, followed by 42 parts by mass of methyltrimethoxysilane (MTMS) and 14 parts by mass of 3-methacryloxypropyltrimethoxysilane (MPTMS). It heated until the temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 20 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 2 hours. After cooling to 45 ° C, 32 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. By the above, polysiloxane (A-9) was obtained. Solid content concentration of polysiloxane (A-9) was 33 mass%, the weight average molecular weight (Mw) was 2100, and dispersion degree (Mw / Mn) was 2.1.

Synthesis Example 10

20 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, 34 mass parts of methyl trimethoxysilane (MTMS), 25 mass parts of tetramethoxysilane (TEOS), and 3-methacryloxypropyl trimeth 5 mass parts of oxysilanes (MPTMS) were put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 23 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 2 hours. After cooling to 45 ° C, 34 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol and ethanol which generate | occur | produced by ion-exchange water and hydrolysis condensation were removed. By the above, polysiloxane (A-10) was obtained. Solid content concentration of polysiloxane (A-10) was 32 mass%, the weight average molecular weight (Mw) was 2200, and dispersion degree (Mw / Mn) was 2.2.

Synthesis Example 11

In a container with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was placed, followed by 30 parts by mass of methyltrimethoxysilane (MTMS), 9 parts by mass of trifluoropropyltrimethoxysilane (TFMS), and 3-methacryl 18 mass parts of oxypropyl trimethoxysilane (MPTMS) was put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 19 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 2 hours. After cooling to 45 ° C, 28 parts by mass of methyl orthoformate was added as a dehydrating agent, followed by stirring for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. By the above, polysiloxane (A-11) was obtained. Solid content concentration of polysiloxane (A-11) was 35 mass%, the weight average molecular weight (Mw) was 1800, and dispersion degree (Mw / Mn) was 2.2.

Component [B] Polysiloxane Synthetic example

[Synthesis Example 12]

In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by 23 parts by mass of methyltrimethoxysilane (MTMS) and 34 parts by mass of phenyltrimethoxysilane (PTMS), and the solution temperature was 60 ° C. Heated until. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 18 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 30 minutes. Subsequently, 0.1 mass part of triethylamines were put, and it preserve | saved 1.5 hours at 75 degreeC. After cooling to 45 ° C, 27 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. By the above, polysiloxane (B-1) was obtained. Solid content concentration of the polysiloxane (B-1) was 34 mass%, the weight average molecular weight (Mw) was 2400, and dispersion degree (Mw / Mn) was 2.4.

[Synthesis Example 13]

25 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, and then, 23 mass parts of methyl trimethoxysilane (MTMS), 30 mass parts of phenyl trimethoxysilane (PTMS), (gamma)-glycidoxy propyl tree 4 mass parts of methoxysilanes (GPTMS) were put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 18 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 30 minutes. Subsequently, 0.1 mass part of triethylamines were put, and it preserve | saved 1.5 hours at 75 degreeC. After cooling to 45 ° C, 27 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. By the above, polysiloxane (B-2) was obtained. Solid content concentration of the polysiloxane (B-2) was 34 mass%, the weight average molecular weight (Mw) was 2500, and dispersion degree (Mw / Mn) was 2.4.

[Synthesis Example 14]

21 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, and then 40 mass parts of methyl trimethoxysilane (MTMS), 17 mass parts of tetramethoxysilane (TEOS), and decyl trimethoxysilane (DTMS) 5 mass parts was put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 22 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and it preserve | saved for 2 hours. After cooling to 45 ° C, 33 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol and ethanol which generate | occur | produced by ion-exchange water and hydrolysis condensation were removed. By the above, polysiloxane (B-3) was obtained. Solid content concentration of the polysiloxane (B-3) was 34 mass%, the weight average molecular weight (Mw) was 2000, and dispersion degree (Mw / Mn) was 2.3.

Synthesis Example 15

21 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, and then 40 mass parts of methyl trimethoxysilane (MTMS), 12 mass parts of tetramethoxysilane (TMOS), and decyl trimethoxysilane (DTMS) 5 mass parts was put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 22 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and it preserve | saved for 2 hours. After cooling to 45 ° C, 33 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. By the above, polysiloxane (B-4) was obtained. Solid content concentration of the polysiloxane (B-4) was 34 mass%, the weight average molecular weight (Mw) was 2000, and dispersion degree (Mw / Mn) was 2.3.

Synthesis Example 16

In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was placed, followed by 18 parts by mass of methyltrimethoxysilane (MTMS), 29 parts by mass of phenyltrimethoxysilane (PTMS), and trifluoropropyltrimethoxy 10 mass parts of silane (TFMS) was put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 18 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 30 minutes. Subsequently, 0.1 mass part of triethylamines were put, and it preserve | saved 1.5 hours at 75 degreeC. After cooling to 45 ° C, 27 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. By the above, polysiloxane (B-5) was obtained. Solid content concentration of the polysiloxane (B-5) was 34 mass%, the weight average molecular weight (Mw) was 2400, and dispersion degree (Mw / Mn) was 2.4.

Synthesis Example 17

In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was placed, followed by 23 parts by mass of methyltrimethoxysilane (MTMS), 24 parts by mass of phenyltrimethoxysilane (PTMS), and 3-mercaptopropyltrime 10 mass parts of oxysilanes ((gamma) MPTMS) were put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 18 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and hold | maintained for 30 minutes. Subsequently, 0.1 mass part of triethylamines were put, and it preserve | saved 1.5 hours at 75 degreeC. After cooling to 45 ° C, 27 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol produced | generated by ion-exchange water and hydrolysis condensation was removed. By the above, polysiloxane (B-6) was obtained. Solid content concentration of polysiloxane (B-6) was 34 mass%, the weight average molecular weight (Mw) was 2800, and dispersion degree (Mw / Mn) was 2.1.

Radiation Polysiloxane  Preparation of composition and formation of protective film and interlayer insulating film

Example 1

Polysiloxane (B-1) obtained by the synthesis example 12 as a component [B] to the solution containing the polysiloxane (A-1) obtained by the synthesis example 1 [a quantity equivalent to 50 mass parts (solid content) of polysiloxane (A-1)]. ) (The amount equivalent to 50 parts by mass (solid content) of polysiloxane (B-1)) and (C-1) ethanone-1- [9-ethyl-6- (2-methyl) as the component [C] 3 parts by mass of benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), (D-1) propylene glycol monomethyl ether and (D-2) diethylene glycol ethyl as components [D] Methyl ether was added in the ratio of Table 1, and the radiation sensitive polysiloxane composition was prepared.

Next, in the radiation sensitive polysiloxane composition, and then by using a spinner, it applied to the SiO ₂ Dip a glass substrate, 90 ℃ on a hot plate to form a coating film by baking free for 2 minutes (the ITO adhesion rating of below ITO adhesion Substrate was used). Next, the ultraviolet-ray was exposed to the obtained coating film by the exposure amount of 300mJ / cm <2>. Subsequently, after developing for 60 second at 25 degreeC with the 0.4 mass% tetramethylammonium hydroxide aqueous solution, it wash | cleans for 1 minute with pure water, and also it heats for 60 minutes in 230 degreeC oven, and is a protective film with a film thickness of 2.0 micrometers. Formed.

Furthermore, the rotation speed of the spinner at the time of forming a coating film is adjusted so that the film thickness after heating may be set to 3.0 micrometers, and exposure gap is provided through the photomask which has a contact hole pattern of the size of 20 micrometers, 30 micrometers, 40 micrometers, and 50 micrometers. An interlayer insulating film was formed in the same manner as the above protective film formation except that the distance between the substrate and the photomask was exposed at 150 μm.

Property evaluation

The transparency, heat resistance transparency, pencil hardness, scratch resistance, crack, heat crack, ITO adhesiveness, sensitivity, and refractive index of the protective film formed in each Example and the comparative example were evaluated.

In the interlayer insulating film, since the film thickness of the interlayer insulating film is only different from the protective film, the transparency, heat resistance transparency, pencil hardness, scratch resistance, cracks, heat cracking, ITO adhesion, sensitivity and refractive index of the interlayer insulating film The evaluation was judged to be the same as the protective film. Moreover, since evaluation of the resolution (resolution of an interlayer insulation film) of a radiation sensitive polysiloxane composition can grasp | ascertain that "resolution" of a radiation sensitive polysiloxane composition is a performance which can form the precise contact hole of an interlayer insulation film, it is an interlayer It can evaluate as what is equivalent to the "resolution" of an insulating film.

(1) Evaluation of transparency of protective film

The light transmittance of 400-800 nm of wavelengths was used for the board | substrate which has the protective film formed as mentioned above in each Example and the comparative example using the spectrophotometer (150-20 type double beam by Hitachi Seisakusho Co., Ltd.). (%) Was measured. When the minimum value of the light transmittance (%) of wavelength 400-800 nm is 95% or more, it was judged that transparency of a protective film was favorable.

(2) Evaluation of heat resistance transparency of protective film

About each board | substrate which has a protective film formed as mentioned above in each Example and a comparative example, it heats in a clean oven at 250 degreeC for 1 hour, and the light transmittance before and behind heating is described in said (1) "evaluation of transparency of a protective film". After measuring by one method, heat resistance transparency (%) was computed according to following formula (a). When this value was 4% or less, it was judged that the heat resistance transparency of a protective film was favorable.

Heat resistance transparency (%) = light transmittance before heating (%)-light transmittance after heating (%) (a)

(3) Measurement of pencil hardness (surface hardness) of protective film

About the board | substrate which has a protective film formed as mentioned above in each Example and the comparative example, the pencil hardness (surface hardness) of the protective film was measured by "8.4.1 pencil scraping test of JISK-5400-1990." When this value was 4H or larger, it was judged that the surface hardness of a protective film was favorable.

(4) Evaluation of the scratch resistance of the protective film

The board | substrate with the protective film formed as mentioned above in each Example and the comparative example was reciprocated 10 times by applying the load of 200g on steel wool # 0000 using the Hakjin type abrasion tester. The situation of abrasion was visually evaluated by the following criteria. When the rating was ◎ or 찰, it was judged to have good scratch resistance.

Criteria

◎: no scratch

○: 1 to 3 flaws

△: 4 to 10 flaws

×: 10 or more scratches

(5) Evaluation of cracks in protective film

In the Examples and Comparative Examples, the substrate having the protective film formed as described above was left to stand at 23 ° C. for 24 hours, and a crack was generated on the surface of the protective film according to the following criteria. VK-8500). When the rating was ◎ or ,, the evaluation of the crack was judged to be good.

Criteria

◎: No crack at all

○: 1 to 3 cracks

△: 4 to 10 cracks

×: 10 or more cracks

(6) Evaluation of heat-resistant crack of protective film

In each Example and the comparative example, the board | substrate which has a protective film formed as mentioned above is baked further at 300 degreeC for 30 minutes, and it is left to stand at 23 degreeC after that for 24 hours, and whether the crack has generate | occur | produced on the surface of this protective film. According to the following criteria, it confirmed using the laser microscope (VK-8500 by Keyence). When the rating was 평가 or 내, the evaluation of the heat resistant crack was judged to be good.

Criteria

◎: No crack at all

○: There are 1 to 3 cracks

(Triangle | delta): There are 4-10 cracks.

X: There are ten or more cracks

(7) Evaluation of ITO (Indium Tin Oxide) Adhesion of Protective Film

Except using the board | substrate with ITO, in each Example and the comparative example, the protective film was formed as mentioned above and the pressure cooker test (120 degreeC, 100% of humidity, 4 hours) was done. Subsequently, the 8.5.3 adherent checkerboard eye tape method of JIS K-5400-1990 was performed to determine the number of checkerboard eyes remaining in 100 checkerboard eyes to evaluate ITO adhesion of the protective film. It was judged that ITO adhesiveness was bad when the number of remaining checkerboard eyes out of 100 checkerboard eyes is 80 or less.

(8) Evaluation of the sensitivity of the protective film

About the coating film obtained above, exposure was performed by changing exposure amount through the mask which has a line-and-space pattern of 10 micrometers / 30 micrometers using the exposure machine TME-400 PRJ by Topcon Co., Ltd., 0.4. It developed by 25 degreeC and 60 second immersion in the mass% tetramethylammonium hydroxide aqueous solution. Subsequently, flowing water washing was performed for 1 minute with ultrapure water, and it dried and formed the pattern on the glass substrate. At this time, the minimum exposure amount required for the pattern of the line and space of 10 micrometers / 30 micrometers to remain without peeling was measured. This minimum exposure amount was evaluated as radiation sensitivity. When the minimum exposure amount was 50 mJ / cm 2 or less, the sensitivity was judged to be good.

(9) Evaluation of the refractive index of the protective film

Using the Abbe refractometer, the refractive index in 25 degreeC and 633 nm light of the protective film obtained by the said "evaluation of the light transmittance (transparency) of a protective film" method was measured.

(10) Evaluation of the resolution (resolution of interlayer insulation film) of radiation-sensitive polysiloxane composition

In formation of said interlayer insulation film in each Example and a comparative example, the contact hole pattern size which was resolvable was measured. It was judged that resolution was favorable as long as the contact hole pattern of 30 micrometers or less could be resolved.

[Examples 2 to 26 and Comparative Examples 1 to 6]

A radiation sensitive polysiloxane composition was prepared in the same manner as in Example 1 except that the kind and the blending amount of each blending component were as described in Tables 1 to 5. Next, using the obtained radiation sensitive polysiloxane composition, it carried out similarly to Example 1, and formed the protective film. In addition, each compounding quantity in Tables 1-5 is a mass part.

The evaluation results of Examples 1 to 7 are shown in Table 1, the evaluation results of Examples 8 to 13 are shown in Table 2, the evaluation results of Examples 14 to 20 are shown in Table 3, and the evaluation results of Examples 21 to 26 are shown in Table 4 In Table 5, evaluation results of Comparative Examples 1 to 6 are shown, respectively.

In addition, in Tables 1-5, the symbol in a [C] radical photopolymerization initiator, a [D] solvent, an [E] acrylate, [F] organic particle | grains, or an inorganic particle represents the following, respectively.

C-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl oxime) (brand name: Irgacure) OXE02, Chiba Specialty Chemicals Co., Ltd.

C-2: 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyl oxime)] (brand name: Irgacure OXE01, Chiba specialty Chemicals Corporation make)

C-3: 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (brand name: Irgacure 907, Chiba? Specialty Chemicals Co., Ltd. product)

C-4: 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morphonyl) phenyl] -1-butanone (brand name: Irgacure 379EG, Chiba? Chemicals Co., Ltd.)

D-1: Propylene Glycol Monomethyl Ether

D-2: diethylene glycol ethyl methyl ether

D-3: Ethylene Glycol Monobutyl Ether

E-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: MAX-3510, manufactured by Nippon Kayaku Co., Ltd.)

E-2: pentaerythritol triacrylate (trade name: A-TMM-3LMN, manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.)

E-3: succinic acid modified dipentaerythritol pentaacrylate (trade name: M-520, manufactured by Nippon Kayaku Co., Ltd.)

E-4: tris (acryloxyethyl) isocyanurate (brand name: M-315, manufactured by Toagosei Co., Ltd.)

F-1: Polymethyl methacrylate-based fine particles (trade name MP-300, manufactured by Soken Kagaku Co., Ltd.)

F-2: organosilica sol (brand name IPA-ST, Nissan Kagaku Kogyo Co., Ltd. make)

F-3: ZrO ₂ sol (trade name ID191, manufactured by Teika Co., Ltd.)

F-4: TiO ₂ sol (trade name TS-103, manufactured by Teika Co., Ltd.).

Claims (9)

Component [A]? [D] as follows:
[A] A polysiloxane having a radically polymerizable organic group obtained by cohydrolytic condensation of a silane compound having (a1) a radically polymerizable organic group and a silane compound having no (a2) radically polymerizable organic group, in the polysiloxane. (a1) polysiloxane in which the ratio of the silane compound which has a radically polymerizable organic group exceeds 15 mol%,
[B] a polysiloxane having no radically polymerizable organic group,
[C] a radical polymerization initiator, and
[D] solvent
Polysiloxane composition containing. The method of claim 1,
The polysiloxane composition whose content rate of the structural unit which has a radically polymerizable organic group which occupies for all the structural units which comprise the said [A] and [B] component is 1-20 mol%. The method according to claim 1 or 2,
Furthermore, the polysiloxane composition containing [E] ethylenically unsaturated compound (except the said [A] component). The method according to claim 1 or 2,
Furthermore, [F] polysiloxane composition containing at least 1 sort (s) chosen from the group which consists of organic particle | grains and an inorganic particle. As a manufacturing method of the polysiloxane composition of Claim 1 or 2,
At least, the following components [A]? [D]:
[A] A polysiloxane having a radically polymerizable organic group obtained by cohydrolytic condensation of a silane compound having a (a1) radically polymerizable organic group and a silane compound having no (a2) radically polymerizable organic group, wherein (a1) in the polysiloxane Polysiloxane in which the ratio of the silane compound which has a radically polymerizable organic group exceeds 15 mol%,
[B] a polysiloxane having no radically polymerizable organic group,
[C] a radical polymerization initiator, and
[D] solvent
Manufacturing method for mixing. The cured film of the display element formed from the polysiloxane composition of Claim 1 or 2. Following steps (1) to (4);
(1) forming a coating film of the polysiloxane composition according to claim 1 or 2 on a substrate;
(2) irradiating at least a part of the coating film formed in step (1) with radiation;
(3) developing the coating film irradiated with radiation in step (2), and
(4) Step of heating the coating film developed in Step (3)
Formation method of the cured film of a display element containing the. The cured film of the display element formed by the method of Claim 7. The method of claim 8,
Cured film of the display element which is a protective film for touch panels.