JP2012082393A - Polysiloxane composition, cured film thereof and method of forming the same - Google Patents

Abstract

Disclosed is a polysiloxane composition capable of achieving a high level balance of required characteristics for a cured film of a display element such as a protective film and an interlayer insulating film.
The following components [A] to [D];
[A] (a1) a polysiloxane having a radical polymerizable organic group obtained by cohydrolytic condensation of a silane compound having a radical polymerizable organic group and (a2) a silane compound not having a radical polymerizable organic group A polysiloxane in which the proportion of the silane compound having a radically polymerizable organic group (a1) in the polysiloxane exceeds 15 mol%,
[B] Polysiloxane composition containing [C] radical polymerization initiator having no radical polymerizable organic group and [D] solvent.
[Selection figure] None

Description

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

  A display element such as a liquid crystal display element is subjected to an immersion treatment with a solvent, an acid or an alkali solution during the manufacturing process, and the surface of the element is locally exposed to a high temperature when a wiring electrode layer is formed by sputtering. Is done. In order to prevent the display element from being deteriorated or damaged by such immersion treatment or high temperature treatment, a protective film resistant to these treatments is provided on the surface of the device.

  Such a protective film has high adhesion to the substrate or lower layer on which the protective film is to be formed, and further to a layer formed on the protective film, the film itself is smooth and tough, Performance such as having transparency, maintaining transparency without discoloration even under high temperature conditions, having sufficient surface hardness, excellent scratch resistance, etc. is required. .

  An acrylic resin is mainly used as a component of the radiation-sensitive composition for forming the protective film in order to satisfy such required characteristics, but the polysiloxane type is superior in heat resistance and transparency than the acrylic resin. Attempts have been made to use the material as a component of the radiation-sensitive composition (Patent Documents 1 to 3). However, since the polysiloxane material does not have sufficient adhesion to an ITO (indium tin oxide) transparent conductive film and cracks are likely to occur in the cured film, there is an inconvenience that it cannot be practically used as a protective film. . Furthermore, when the adhesion on the molybdenum wiring in the display element is insufficient, the protective film may crack or peel off from the molybdenum wiring. Therefore, it is desired to develop a polysiloxane-based radiation-sensitive composition that is excellent in heat resistance and transparency and improved in adhesion to an ITO transparent conductive film or molybdenum wiring.

  In addition, there are input devices that operate devices by pressing on-screen displays called touch panels, touch screens, touch screens, etc. on automatic cash payment machines such as banks, vending machines, mobile phones, personal digital assistants, digital audio players, etc. in use. Since the touch panel is usually pressed directly with a finger or the like, a protective film is provided. The protective film is required to have high surface quality such as adhesion to the wiring of the touch panel element, and further, scratch resistance as a protective film.

  On the other hand, the interlayer insulating film is provided to insulate between wirings generally arranged in layers in a display element or the like. The interlayer insulating film of this display element needs to form a contact hole pattern for wiring. As a material for forming an interlayer insulating film of a liquid crystal display element, a negative radiation sensitive composition advantageous in cost has been developed (Patent Document 4). However, with such a negative radiation-sensitive composition, it is difficult to form a contact hole having a hole diameter that can be used practically. Therefore, at present, from the viewpoint of the superiority of contact hole formation, positive-type radiation-sensitive compositions are widely used to form interlayer insulating films of display elements (Patent Document 5).

  As described above, various radiation-sensitive compositions are used in the production of display elements and the like depending on the purpose and process. Recently, from the viewpoint of cost reduction, attempts have been made to unify the types of radiation-sensitive compositions, and it is desired that the protective film and the interlayer insulating film can be formed from one type 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 can be used practically. Development of a polysiloxane-based negative radiation-sensitive composition that expresses resolution capable of forming contact holes and has sufficient adhesion and scratch resistance as a protective film for a touch panel is strongly desired.

JP 2000-001648 A JP 2006-178436 A JP 2008-248239 A JP 2000-162769 A JP 2001-354822 A

  The present invention has been made on the basis of the circumstances as described above, and its purpose is to form a polysiloxane capable of forming a cured film such as a protective film or an interlayer insulating film that balances the above-mentioned required characteristics at a high level with a good balance. It is providing the composition and its manufacturing method. Another object of the present invention is to provide a protective film formed from the polysiloxane composition, a cured film such as an interlayer insulating film, and a method for forming the same.

In order to solve the above problems, the present invention firstly includes the following components [A] to [D];
[A] (a1) a polysiloxane having a radical polymerizable organic group obtained by cohydrolytic condensation of a silane compound having a radical polymerizable organic group and (a2) a silane compound not having a radical polymerizable organic group A polysiloxane in which the proportion of the silane compound having a radically polymerizable organic group (a1) in the polysiloxane exceeds 15 mol%,
[B] A polysiloxane composition containing a polysiloxane [C] radical polymerization initiator having no radically polymerizable organic group and [D] a solvent is provided.

The present invention is secondly a method for producing the polysiloxane composition,
At least the following components [A] to [D];
[A] (a1) a polysiloxane having a radical polymerizable organic group obtained by cohydrolytic condensation of a silane compound having a radical polymerizable organic group and (a2) a silane compound not having a radical polymerizable organic group A polysiloxane in which the proportion of the silane compound having a radically polymerizable organic group (a1) in the polysiloxane exceeds 15 mol%,
[B] A production method of mixing a polysiloxane [C] radical polymerization initiator having no radically polymerizable organic group and a [D] solvent is provided.

  Furthermore, the present invention thirdly provides a cured film of a display element formed from the polysiloxane composition.

Furthermore, the present invention fourthly includes the following steps (1) to (4);
(1) The process of forming the coating film of the said polysiloxane composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A method for forming a cured film of a display element, including a step of developing the coating film irradiated with radiation in step (2), and a step of (4) heating the coating film developed in step (3). It is to provide.

  Furthermore, fifthly, the present invention provides a cured film of a display element formed by the above method, and is useful as a protective film for a touch panel of a display element, for example.

  The polysiloxane composition of the present invention has a general balance of general required properties such as transparency, heat resistance, heat transparency, crack resistance, surface hardness and scratch resistance, and is transparent to ITO. Since the adhesion to the conductive film is improved, a cured film such as a protective film and an interlayer insulating film having a fine and elaborate pattern can be easily formed. Therefore, the thus formed cured film (protective film or interlayer insulating film) can be suitably used for display elements, and is particularly useful as a protective film for touch panel display elements. In addition, the polysiloxane composition of the present invention can exhibit sufficient resolution so that contact holes can be formed.

Polysiloxane Composition The polysiloxane composition of the present invention contains an [A] component, a [B] component, a [C] component, and a [D] component as essential components. Hereinafter, each component will be described in detail.

[A] component [A] component consists of (a1) a silane compound having a radical polymerizable organic group (hereinafter also referred to as (a1) compound) and (a2) a silane compound having no radical polymerizable organic group (hereinafter referred to as (a2). ) (Also referred to as a compound) having a radical polymerizable organic group obtained by cohydrolytic condensation, and the ratio of the compound (a1) in the polysiloxane exceeds 15 mol%.

  The compound (a1) is preferably a hydrolyzable silane compound represented by the following formula (1) or the following formula (2).

[In the formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² represents a single bond, a methylene group or an alkylene group, and X represents a vinyl group, an allyl group, a styryl group or (meth) acryloyl. Indicates an oxy group.
In the formula (2), R ³ represents an alkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ each independently represent a single bond, a methylene group or an alkylene group, and Y represents a vinyl group, an allyl group, or styryl. 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, or an amino group. , Vinyl group, styryl group or (meth) acryloyloxy group. p is an integer of 1 or 2. ]

Here, in the present specification, the “hydrolyzable silane compound” refers to a “silane compound having a hydrolyzable group”, and the “hydrolyzable group” referred to here is usually a silanol by reaction with water. It refers to a group capable of forming a group (—Si—OH). On the other hand, the “non-hydrolyzable group” refers to a group that stably exists without forming a silanol group by reaction with water. In addition, “hydrolytic condensation” refers to a dehydration condensation reaction between silanol groups generated by hydrolysis and / or a condensation reaction between a silanol group and a hydrolyzable group, resulting in a siloxane bond (—Si—O—Si—). ) Is formed. In the hydrolysis reaction, if a silanol group is generated from a part of the hydrolyzable group, an unhydrolyzed group (—OR ¹ or —OR ³ ) may remain, that is, one of the components [A]. The portion may have at least one selected from —OR ¹ and —OR ³ .
In the present invention, not only a hydrolyzable silane compound but also a partially hydrolyzed product thereof can be used, and the same applies to the [B] component described later. As used herein, the term “partially hydrolyzed product” refers to a siloxane compound (silicon atom) produced by hydrolysis condensation reaction of an alkoxy group and having at least one, preferably two or more alkoxy groups remaining in the molecule. A siloxane oligomer having a number of 2 to 100, preferably about 2 to 30.

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. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.

As the alkylene group for R ² , R ⁴ and R ^5, an alkylene group having 2 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is particularly preferable. The alkylene group may be linear or branched, and specific examples include an ethylene group, a trimethylene group, and a propylene group.

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

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

In the above 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 X is a vinyl group or (meth) acryloyl. An oxy group is preferred.
In the above formula (2), R ³ is preferably an alkyl group having 1 to 2 carbon atoms, R ⁴ and R ⁵ are preferably a single bond or an alkylene group having 2 to 3 carbon atoms, and Y is a vinyl group or ( A (meth) acryloyloxy group is preferable, and Z is preferably an alkyl group having 1 to 6 carbon atoms. Further, p is preferably 1.

  Specific examples of the compound represented by the above formula (1) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, o-styryltrimethoxysilane, o-styryltriethoxysilane, m-styryltrimethoxysilane. M-styryltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloyloxytrimethoxysilane, methacryloyloxytriethoxysilane, methacryloyloxytripropoxysilane, Acryloyloxytrimethoxysilane, acryloyloxytriethoxysilane, acryloyloxytripropoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 2-methyl Acryloyloxyethyltriethoxysilane, 2-methacryloyloxyethyltripropoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltripropoxysilane, 2-acryloyloxyethyltri Methoxysilane, 2-acryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltripropoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltripropoxysilane, etc. It is done. These may be used alone or in combination of two or more.

  Specific examples of the compound represented by the above formula (2) include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, allylmethyldimethoxy. Silane, allylmethyldiethoxysilane, allyldimethylmethoxysilane, allyldimethylethoxysilane, divinylmethylmethoxysilane, divinylmethylethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxy Propylphenyldimethoxysilane, 3-acryloyloxypropylphenyldimethoxysilane, 3,3′-dimethacryloyloxy Examples thereof include propyldimethoxysilane, 3,3′-diaacryloyloxypropyldimethoxysilane, 3,3 ′, 3 ″ -trimethacryloyloxypropylmethoxysilane, 3,3 ′, 3 ″ -triacryloyloxypropylmethoxysilane, and the like. These may be used alone or in combination of two or more.

  Among the compounds represented by the above formulas (1) and (2), it is possible to achieve a high level of crack resistance, surface hardness, adhesion to wiring, etc., and in particular, from the viewpoint of hydrolysis condensation reactivity, vinyltrimethoxy Silane, p-styryltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyl Methyldimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane and the like are preferable.

  The compound (a2) is preferably a hydrolyzable silane compound represented by the following formula (3).

(In the formula (3), R ⁶ represents an alkyl group having 1 to 4 carbon atoms, R ⁷ represents a single bond, a methylene group or an alkylene group, and W represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. A substituted or unsubstituted aryl group having 6 to 14 carbon atoms, an amino group, a mercapto group, an epoxy group, a glycidyloxy group, or a 3,4-epoxycyclohexyl group, and q is an integer of 0 to 3.)

The alkyl group in R ⁶ include the same as R ¹ in the formula (1), the alkyl group and the aryl group in W include the same Z in the formula (2), in R ⁷ Examples of the alkylene group include the same groups as R ^{5 in the} above formula (2). Examples of the substituent of the alkyl group and aryl group in W include the same substituents as the substituent of the aryl group in Z of the above formula (2).
R ⁷ is preferably a single bond or an alkylene group having 2 to 3 carbon atoms, and W is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 8 carbon atoms, or glycidyl. An oxy group is preferred. In addition, as a substituent of an alkyl group or an aryl group, a halogen atom is preferable. Moreover, as q, 0 or 1 is preferable.

  As the hydrolyzable silane compound represented by the above formula (3), a silane compound having four hydrolyzable groups, a silane compound having one non-hydrolyzable group and three hydrolyzable groups Mention may be made of silane compounds having two non-hydrolyzable groups and two hydrolyzable groups, 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 and the like;
As a silane compound having one non-hydrolyzable group and three hydrolyzable groups, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, aminotrimethoxysilane, amino Triethoxysilane, 3-mercaptopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy, γ-glycidoxypropyltrimethoxysilane and the like;
Examples of the silane compound having two non-hydrolyzable groups and two hydrolyzable groups include dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane. These may be used alone or in combination of two or more.

  Of 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 preferred. A silane compound having a non-hydrolyzable group and three hydrolyzable groups is particularly preferred. Specific examples of preferable hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane. Examples include ethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, decyltrimethoxysilane, and trifluoropropyltrimethoxysilane.

  The charging ratio of the (a1) compound in the total of the (a1) compound and the (a2) compound exceeds 15 mol%, but is preferably 16 mol% or more, particularly preferably 18 mol% or more. (A1) When the ratio of a compound is 15 mol% or less, exposure sensitivity falls and the heat resistance of the cured film obtained, adhesiveness, and resolution fall. In addition, it is preferable that the upper limit of the preparation ratio of (a1) compound is 50 mol%, 40 mol%, especially 30 mol% from a viewpoint of crack tolerance, heat resistance, and adhesiveness.

  The conditions for cohydrolyzing and condensing the compound (a1) and the compound (a2) include hydrolyzing at least a part of the compound (a1) and the compound (a2) to convert the hydrolyzable group into a silanol group. And as long as it causes a condensation reaction, although it does not specifically limit, the following method can be mentioned as an example.

A method in which the (a1) compound and the (a2) compound are mixed in a solvent, water is added to the mixed solution, and hydrolytic condensation is preferably employed.
As the water used for the cohydrolysis 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, or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably 0.1 to 3 mol, more preferably 0.3 to 2 mol, and still more preferably with respect to 1 mol of the total amount of hydrolyzable groups of the (a1) compound and (a2) compound. Is 0.5 to 1.5 mol. By using such an amount of water, the reaction rate of the hydrolysis condensation can be optimized.

  The solvent used in the cohydrolysis condensation reaction between the compound (a1) and the compound (a2) is not particularly limited, but is usually the same as the solvent used for preparing the polysiloxane composition described 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 alone or in combination of two or more. 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 is particularly preferable.

  The cohydrolysis condensation reaction between the (a1) compound and the (a2) compound is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, Acidic ion exchange resins, various Lewis acids), basic catalysts (eg, nitrogen-containing compounds such as ammonia, primary amines, secondary amines, tertiary amines, pyridine; basic ion exchange resins; sodium hydroxide, etc. It is carried out in the presence of a catalyst such as hydroxide; carbonate such as potassium carbonate; carboxylate such as sodium acetate; various Lewis bases] or alkoxide (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide). The amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001, based on the total of 1 mol of the compound (a1) and the compound (a2), from the viewpoint of promoting the hydrolysis condensation reaction. ~ 0.1 mol.

  Although the reaction temperature and reaction time in the cohydrolysis condensation reaction of the compound (a1) and the compound (a2) can be appropriately set, for example, the following conditions can be adopted. The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. By setting such reaction temperature and reaction time, the hydrolysis condensation reaction can be performed most efficiently. In this hydrolysis-condensation reaction, the hydrolyzable silane compound, water and catalyst may be added to the reaction system at once and the reaction may be performed in one step, or the hydrolyzable silane compound, water and catalyst may be added in several steps. The hydrolysis reaction and the condensation reaction may be performed in multiple stages by adding them into the reaction system in batches. After the hydrolysis condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then subjecting it to evaporation. The dehydrating agent used in this stage is generally consumed or adsorbed with excess water, or the dehydrating ability is completely consumed or removed by evaporation.

  The [A] component thus obtained includes the structural unit represented by the following formula (4) derived from the compound (a1) (hereinafter also referred to as the structural unit (4)) and the following derived from the compound (a2). Those containing a structural unit represented by the formula (5) (hereinafter also referred to as the structural unit (5)) and a structural unit represented by the following formula (6) (hereinafter also referred to as the structural unit (6)) are preferable. .

[In Formula (4), R < ² > and X are synonymous with the above,
In formula (6), R ⁸ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. ]

Examples of the substituent of the alkyl group in R ⁸ include the same substituents as the substituent of the aryl group in Z of the above formula (2).

  The content ratio (molar ratio) of each structural unit in the component (A) is as follows: structural unit (4) / structural unit (5) / structural unit (6) = 16 to 25/10 to 40/40 to 70, and further 18 It is preferable that it is -25 / 20-40 / 40-60.

The molecular weight of the component [A] obtained by the hydrolysis-condensation reaction can be measured as a weight average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase. [A] The weight average molecular weight (Mw) of the component is preferably in the range of 500 to 10,000, and more preferably in the range of 1000 to 5000. By setting the value of the weight average molecular weight of the component [A] to 500 or more, the film formability of the coating film of the polysiloxane composition can be improved. On the other hand, by setting the weight average molecular weight to 10,000 or less, it is possible to prevent a decrease in alkali developability of the polysiloxane composition.
The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured under the same conditions, that is, the degree of dispersion (Mw / Mn) is preferably 1.0 to 15.0, more preferably 1 .1 to 10.0, more preferably 1.1 to 5.0. By setting it within such a range, it is possible to achieve both alkali developability, adhesion, and crack resistance.

[B] component [B] component is polysiloxane which does not have a radically polymerizable organic group. By using the [A] component and the [B] component in combination, it is possible to achieve crack resistance, heat resistance, adhesion and resolution at a higher level than when only the [A] component is used.

  The component [B] can be obtained by (co) hydrolytic condensation of at least one hydrolyzable silane compound represented by (3) above under the same conditions as those for the component [A].

  [B] component obtained by (co) hydrolytic condensation reaction is represented by the structural unit represented by the following formula (7) (hereinafter also referred to as structural unit (7)) and the following formula (8). Those containing a structural unit (hereinafter also referred to as structural unit (8)) are preferred.

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

Examples of the substituent of the alkyl group in R ⁹ and the aryl group in R ¹⁰ include the same substituents as the aryl group in Z of the above formula (2).

  The content ratio (molar ratio) of each structural unit in the component [B] is structural unit (7) / structural unit (8) = 30 to 70/70 to 30, and further 40 to 60/60 to 40. preferable.

The weight average molecular weight (Mw) of the component [B] obtained by the hydrolytic condensation reaction can be measured under the same conditions as those of the component [A]. Therefore, it is preferably 500 to 10000, more preferably 1000 to 5000.
Further, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured under the same conditions, that is, the dispersity (Mw / Mn) is preferably from the viewpoint of alkali developability, adhesion, and crack resistance. Is 1.0 to 15.0, more preferably 1.1 to 10.0, and still more preferably 1.1 to 5.0.

The content ratio of the [A] component and the [B] component is preferably 80 to 400 parts by mass, and more preferably 100 to 200 parts by mass with respect to 100 parts by mass of the [A] component.
Moreover, the content ratio of the structural unit having a radical polymerizable organic group in all the structural units constituting the [A] component and the [B] component, that is, the total structural unit of the [A] component and the [B] component (a1 ) It is preferable to adjust appropriately so that the content ratio of the structural unit derived from the compound is 1 to 20 mol%, further 5 to 18 mol%, particularly 10 to 15 mol%. By containing a structural unit having a radically polymerizable organic group at such a ratio, it becomes possible to achieve a high level of adhesion, crack resistance, heat resistance, and scratch resistance, and also has radiation sensitivity. You can also
In addition, the content rate of the structural unit which has the radically polymerizable organic group which occupies for all the structural units which comprise a [A] component and a [B] component is ¹ H-NMR, ¹³ C-NMR, FT-IR, pyrolysis gas Qualitative and quantitative analysis is possible by chromatography mass spectrometry.

[C] component [C] component is a radical polymerization initiator. Examples of the radical polymerization initiator used in the present invention include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like.

  Specific examples of the O-acyloxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [ 9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like. These O-acyloxime compounds can be used alone or in admixture of two or more.

  Among these, preferable O-acyloxime compounds include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime).

  Examples of acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds.

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

  Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1- ON, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like. These acetophenone compounds can be used alone or in admixture of two or more.

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

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 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 etc. can be mentioned. These biimidazole compounds can be used alone or in admixture of two or more.

  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, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole Is particularly preferred.

  When a biimidazole compound is used as the [C] component in the polysiloxane composition of the present invention, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as “amino sensitizer”) Can be added.

  Examples of such amino sensitizers include 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone. Of these amino sensitizers, 4,4′-bis (diethylamino) benzophenone is particularly preferred. These amino sensitizers can be used alone or in admixture of two or more.

  Further, when a biimidazole compound and an amino sensitizer are used in combination, a thiol compound can be added as a hydrogen radical donor. A biimidazole compound is sensitized by an amino sensitizer and cleaved to generate an imidazole radical, but may not exhibit high polymerization initiation ability 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 the thiol compound to the imidazole radical. As a result, the imidazole radical is converted to neutral imidazole, and a component having a sulfur radical having a high polymerization initiating ability is generated, and a cured film having a high surface hardness can be formed even with a low radiation dose. .

Specific examples of such thiol compounds include
Aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole;
Aliphatic monothiol compounds such as 3-mercaptopropionic acid and methyl 3-mercaptopropionate;
Bifunctional or higher aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) can be exemplified. These thiol compounds can be used alone or in admixture of two or more.
Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

  When a biimidazole compound and an amino sensitizer are used in combination, the use amount of the amino sensitizer is preferably 0.1 to 50 parts by mass, more preferably 100 parts by mass of the biimidazole compound. Is 1-20 parts by mass. By making the usage-amount of an amino sensitizer into the said range, the cure reactivity at the time of exposure can improve and the surface hardness of the cured film obtained can be raised.

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

  In the present invention, the [C] component preferably contains at least one selected from the group consisting of an O-acyloxime compound and an acetophenone compound, and may further contain a biimidazole compound.

  The amount of the component [C] used is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass in total of the [A] component and the [B] component. By setting the amount of component [C] used within the above range, a cured film having high radiation sensitivity and sufficient surface hardness can be formed even in the case of a low exposure amount.

[D] Component [D] A component is a solvent. Although it does not specifically limit as a solvent, It is desirable to contain the alcohol solvent which is a protic solvent especially. By using an alcohol-based solvent, each component can be uniformly dissolved or dispersed. This makes it possible to improve the coating property of the composition solution on a large substrate, and further, coating unevenness (streaky unevenness, pin mark unevenness). ), And the film thickness uniformity can be further improved.

As such an alcohol solvent,
Long-chain alkyl alcohols such as 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol, 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, ethylene glycol monobutyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;
Examples include dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. These alcohol solvents can be used alone or in combination of two or more.

  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 coatability.

[D] A component may be used individually by 1 type, and 2 or more types may be mixed and used for it.
The amount of component [D] used is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, with respect to 100 parts by mass of component [A]. By making the use amount of the component [D] within the above range, it is possible to improve the coating property on the glass substrate and the like, and further suppress the occurrence of coating unevenness (such as streaky unevenness, pin mark unevenness, and moya unevenness). Thickness uniformity can be further improved.

  In the present invention, together with alcohol solvents, other solvents such as ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones, esters And the like.

Examples of solvents other than alcohol solvents include the following.
Ethers such as tetrahydrofuran;
Examples of diethylene glycol alkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate;
Examples of propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like;

Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, and the like;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxy Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxy Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 Examples thereof include propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate and the like. These solvents can be used alone or in admixture of two or more.

  The polysiloxane composition of the present invention may further contain the following components.

[E] Component The [E] component is an ethylenically unsaturated compound that is polymerized by irradiation with radiation in the presence of a [C] radical polymerization initiator. However, the [A] component is excluded.
As such a polymerizable unsaturated monomer, monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid ester is used from the viewpoint of good polymerizability and improved strength of the obtained cured film. preferable.

  Examples of monofunctional (meth) acrylic acid esters include 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, ω-carboxypolycaprolactone monoacrylate, and the like. As a commercial item, for example, Aronix M-101, M-111, M-114, M-5300 (above, Toagosei Co., Ltd.); KAYAARDTC-110S, TC-120S (above, Nippon Kayaku Co., Ltd.); Viscoat 158, 2311 (Osaka Organic Chemical Industry Co., Ltd.) and the like.

  Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol diacrylate. Examples include methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, and the like. Examples of commercially available products include Aronix M-210, M-240, and M-6200 (above, Toagosei Co., Ltd.); KAYARADHDDA, HX-220, R-604 (above, Nippon Kayaku Co., Ltd.); 312 and 335HP (Osaka Organic Chemical Co., Ltd.); light acrylate 1,9-NDA (Kyoeisha Chemical Co., Ltd.) and the like.

  Examples of the tri- or higher functional (meth) acrylic acid ester include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol penta Acrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tri (2-acryloyloxyethyl) Foss , Tri (2-methacryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, tris (acryloxyethyl) isocyanurate, linear alkylene group and alicyclic structure And a compound having two or more isocyanate groups and a compound having one or more hydroxyl groups in the molecule and having three, four or five (meth) acryloyloxy groups The polyfunctional urethane acrylate type compound etc. which are obtained by making it contain are mentioned. Examples of commercially available products include Aronix M-309, M-315, M-400, M-405, M-450, M-7100, M-8030, M-8060, and TO-1450. (Above, Toagosei Co., Ltd.); KAYAARADTMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-60, DPCA-12, DPEA-12 (above, Nippon Kayaku); Biscote 295, 300, the same 360, the same GPT, the same 3PA, the same 400 (Osaka Organic Chemical Industry Co., Ltd.); As a commercial product containing a polyfunctional urethane acrylate compound, New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (Nippon Kayaku Co., Ltd.) etc. are mentioned.

  Among these [E] components, ω-carboxypolycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, polyfunctional urethane acrylate A commercially available product containing a series compound is preferred. Among them, a tri- or higher functional (meth) acrylic acid ester is preferable, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is particularly preferable.

  [E] A component may be used independently and may be used in mixture of 2 or more types. The amount of component [E] used is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, and more preferably 20 to 100 parts by weight with respect to a total of 100 parts by weight of [A] and [B] components. Particularly preferred. By making the usage-amount of an [E] component into the said range, the sensitivity of the said composition, the surface height of the cured film obtained, and heat resistance become still better.

[F] Component The [F] component is at least one selected from organic particles and inorganic particles. By containing the [F] component, scratch resistance, crack resistance and the like can be enhanced. The average particle size of the organic particles and inorganic particles is preferably in the range of 0.005 to 0.5 μm.

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

  As the organic particles, acrylic fine particles and the like are preferably used. Examples of the acrylic fine particles include methyl methacrylate polymer. Examples of commercially available organic particles include Zefiac F-320, F-301, F-340, F-325, F-351 (manufactured by Ganz Kasei Co., Ltd.), acrylic fine particles MP-300 (manufactured by Soken Chemical Co., Ltd.). ) And the like.

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. Particles containing the main component are preferred.
The shape of the inorganic fine particles may be any of a spherical shape, a rod shape, a plate shape, a fiber shape, and an indeterminate shape, and these may be a solid shape, a hollow shape, or a porous shape.

  Examples of commercially available inorganic fine particles include, for example, Admafine SO-E1, SO-E2, SO-E3, SO-E4, SO-E5, SE3200-SEJ (manufactured by Admatechs Co., Ltd.), SS01, SS03. , SS15, SS35 (manufactured by Osaka Kasei Co., Ltd.) and the like. Specific examples of such inorganic fine particles include, as silica particles, methanol silica sol, 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.), HXU-110JC, HXU-210C, NZD-3101 (Sumitomo) as zirconia particles Osaka Cement Co., Ltd.), ID 191 (Taika Co., Ltd.), ZRPMA15WT% -E05 (CI Chemical Co., Ltd.), and titanium oxide particles MT-05, MT-100W, MT-100SA, MT -100HD, MT-300HD, MT-150A, ND138, ND139, ND140, ND154, ND165, ND177, T -063, TS-103, TS-159 (manufactured by Tayca Co., Ltd.).

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

  [F] A component may be used independently and may be used in mixture of 2 or more types. The amount of component [F] used is preferably 1 part by mass to 600 parts by mass, and more preferably 10 parts by mass to 200 parts by mass with respect to 100 parts by mass of component [A]. By making the usage-amount of a [F] component into the said range, the abrasion resistance etc. of the protective film and interlayer insulation film which are obtained can be improved further.

  In addition to the components [A] to [D] described above, the polysiloxane composition of the present invention includes [G] a radiation sensitive acid generator and a radiation sensitive base as needed within a range that does not impair the desired effect. Other optional components such as a generator and a [H] surfactant can be contained.

[G] component [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 a basic active substance that acts as a catalyst when polysiloxane is subjected to a condensation / curing reaction when irradiated with radiation.

  As the radiation sensitive acid generator, diphenyliodonium salt, triphenylsulfonium salt and tetrahydrothiophenium salt are preferable, and triphenylsulfonium salt and tetrahydrothiophenium salt are particularly preferable. Specific examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, Diphenyliodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoro Arsenate, bis (4-tert-butylphenyl) iodonium trifluoro Tansulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid, etc. Can be mentioned.

  Specific examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, Examples thereof include phenylsulfonium butyl tris (2,6-difluorophenyl) borate.

  Specific examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophene. Nimononafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2- (norbornan-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) tetrahydro Rothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1 -Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate and the like.

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

  Examples of the radiation sensitive base generator 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-carbamoyloxime, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, ( 4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, hexaamminecobalt (III) tris (triphenylmethylborate), etc. Is mentioned. Among these radiation-sensitive base generators, 2-nitrobenzylcyclohexyl carbamate and O-carbamoylhydroxyamide are particularly preferable from the viewpoint of improving radiation sensitivity.

  [G] A component may be used individually by 1 type and may be used in mixture of 2 or more types. The amount of component [G] used is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of component [A]. By setting the amount of the component [G] used to 20 parts by mass or less, a cured film product having excellent balance of radiation sensitivity, pencil hardness of the protective film and interlayer insulating film to be formed, and heat resistance (heat resistance transparency). Obtainable.

[H] component The [H] component is a surfactant. The component [H] can be added in order to improve the coating property of the polysiloxane composition, reduce coating unevenness, and improve the developability of the radiation irradiated part. As the component [H], nonionic surfactants, fluorine surfactants, and silicone surfactants are preferable.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and the like Polyoxyethylene aryl ethers; polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; and (meth) acrylic acid copolymers. As an example of (meth) acrylic acid-based copolymers, Polyflow No. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2, , 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2, 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexa Fluoroalkanes such as lurodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorine-based alkyl esters.

  Commercially available products of these fluorosurfactants include F-top EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F171, 172, 173 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), FTX-218 (manufactured by Neos Co., Ltd.) Etc.

  Examples of silicone-based surfactants are SH200-100cs, SH28PA, SH30PA, ST89PA, SH190 (manufactured by Toray Dow Corning Silicone), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) )) And the like.

  [H] component may be used independently and may be used in mixture of 2 or more types. The amount of component [H] used is preferably 10 parts by mass or less with respect to 100 parts by mass of component [A]. By making the usage-amount of a [H] component 10 mass parts or less, the applicability | paintability of a polysiloxane composition can be optimized.

  The polysiloxane composition of the present invention is, for example, a solution or dispersion by mixing and dispersing the [A] and [B] components, the [C] component, and optional components in a predetermined ratio in the [D] component. As prepared.

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

Formation of cured film of display element Next, a method for forming a cured film on a substrate to constitute a display element using the polysiloxane composition of the present invention will be described. The method includes the following steps (1) to (4). Note that examples of the cured film of the display element include a protective film and an interlayer insulating film.
(1) The process of forming the coating film of the polysiloxane composition of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with radiation in step (2), and (4) a step of heating the coating film developed in step (3).

Process (1)
In step (1), after applying the solution or dispersion of the polysiloxane composition of the present invention on the substrate, the solvent is removed preferably by heating (pre-baking) the coating surface to form a coating film. . Examples of the substrate material that can be used include glass, quartz, silicon, and resin. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof.

  The method for applying the solution or dispersion of the polysiloxane composition is not particularly limited. For example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like. Can be adopted. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. The pre-baking conditions vary depending on the type of each component, the blending ratio, and the like, but can preferably be about 70 to 120 ° C. for about 1 to 10 minutes.

Process (2)
In step (2), at least a part of the coating film formed in step (1) is exposed. Usually, when exposing a part of coating film, it exposes through the photomask which has a predetermined pattern. Examples of radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable.

The exposure dose in this step is preferably 10 to 1,000 mJ / cm ² , more preferably 20 to 700 mJ, as a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). / Cm ² .

Process (3)
In step (3), the coated film after exposure is developed to remove unnecessary portions (non-irradiated portions of radiation) and form a predetermined pattern. Thus, the polysiloxane composition of the present invention is a negative radiation sensitive composition since the non-irradiated portion of the radiation is removed. The developer used in the development step is preferably an aqueous solution of an alkali (basic compound). Examples of alkalis include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. be able to.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline aqueous solution. As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the polysiloxane composition, but is preferably about 10 to 180 seconds. Following such development processing, for example, after washing with running water for 30 to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

Step (4)
In the step (4), the patterned thin film is heated by using a heating device such as a hot plate or an oven, thereby promoting the condensation reaction of the components [A] and [B] and reliably forming a cured film. be able to. The heating temperature is, for example, 80 to 250 ° C. Although heating time changes with kinds of heating apparatus, for example, when performing a heating process on a hotplate, it can be set to 30 to 90 minutes when performing a heating process in an oven. The step baking method etc. which perform a heating process 2 times or more can also be used. In this manner, a patterned thin film corresponding to a cured film of the 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 insulation film)
The film thickness of the cured film thus formed is preferably 0.1 to 10 μm, more preferably 0.1 to 6 μm, and still more preferably 0.1 to 4 μm.

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

  The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolysis condensate of the hydrolyzable silane compound obtained from each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (made by 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] Synthesis example of component polysiloxane [Synthesis Example 1]
In a container equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was charged, followed by 39 parts by mass of methyltrimethoxysilane (MTMS) and 18 parts by mass of 3-methacryloxypropyltrimethoxysilane (MPTMS), and a solution. Heated until the temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (A-1) was obtained. Polysiloxane (A-1) had a solid content concentration of 35% by mass, a weight average molecular weight (Mw) of 1800, and a dispersity (Mw / Mn) of 2.2.

[Synthesis Example 2]
In a vessel equipped with a stirrer, 21 parts by mass of propylene glycol monomethyl ether was charged, followed by 55 parts by mass of tetramethoxysilane (TEOS) and 16 parts by mass of 3-methacryloxypropyltrimethoxysilane (MPTMS), and the solution temperature. Was heated to 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 23 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 33 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, methanol and ethanol generated by ion-exchanged water and hydrolysis condensation were removed by evaporating the solution at a temperature of 40 ° C. while maintaining the temperature. Thus, polysiloxane (A-2) was obtained. Polysiloxane (A-2) had a solid content concentration of 33% by mass, a weight average molecular weight (Mw) of 2500, and a dispersity (Mw / Mn) of 2.4.

[Synthesis Example 3]
In a container equipped with a stirrer, 23 parts by mass of propylene glycol monomethyl ether was charged, followed by 24 parts by mass of methyltrimethoxysilane (MTMS), 22 parts by mass of tetramethoxysilane (TEOS), and 3-methacryloxypropyltrimethoxysilane. (MPTMS) 17 parts by mass was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 21 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 2 hours. After cooling to 45 ° C., 30 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, methanol and ethanol generated by ion-exchanged water and hydrolysis condensation were removed by evaporating the solution at a temperature of 40 ° C. while maintaining the temperature. Thus, polysiloxane (A-3) was obtained. Polysiloxane (A-3) had a solid content concentration of 34% by mass, a weight average molecular weight (Mw) of 2600, and a dispersity (Mw / Mn) of 2.3.

[Synthesis Example 4]
In a vessel equipped with a stirrer, 23 parts by mass of propylene glycol monomethyl ether was charged, followed by 24 parts by mass of methyltrimethoxysilane (MTMS), 16 parts by mass of tetramethoxysilane (TMOS), and 3-methacryloxypropyltrimethoxysilane. (MPTMS) 17 parts by mass was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 21 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 2 hours. After cooling to 45 ° C., 30 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (A-4) was obtained. Polysiloxane (A-4) had a solid content concentration of 35% by mass, a weight average molecular weight (Mw) of 2500, and a dispersity (Mw / Mn) of 2.3.

[Synthesis Example 5]
In a container equipped with a stirrer, 27 parts by mass of propylene glycol monomethyl ether was charged, followed by 12 parts by mass of methyltrimethoxysilane (MTMS), 30 parts by mass of phenyltrimethoxysilane (PTMS), 3-methacryloxypropyltri 15 parts by mass of methoxysilane (MPTMS) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 16 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 30 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (A-5) was obtained. Polysiloxane (A-5) had a solid content concentration of 28% by mass, a weight average molecular weight (Mw) of 1800, and a dispersity (Mw / Mn) of 2.0.

[Synthesis Example 6]
In a vessel equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged, followed by 27 parts by mass of methyltrimethoxysilane (MTMS), 25 parts by mass of tetramethoxysilane (TEOS), and vinyltrimethoxysilane (VTMS). 12 parts by mass were charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 23 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 34 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, methanol and ethanol generated by ion-exchanged water and hydrolysis condensation were removed by evaporating the solution at a temperature of 40 ° C. while maintaining the temperature. Thus, polysiloxane (A-6) was obtained. Polysiloxane (A-6) had a solid content concentration of 28% by mass, a weight average molecular weight (Mw) of 2300, and a dispersity (Mw / Mn) of 2.2.

[Synthesis Example 7]
In a vessel equipped with a stirrer, 27 parts by mass of propylene glycol monomethyl ether was charged, followed by 20 parts by mass of methyltrimethoxysilane (MTMS) and 37 parts by mass of 3-methacryloxypropyltrimethoxysilane (MPTMS), and a solution. Heated until the temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 16 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 23 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (A-7) was obtained. Polysiloxane (A-7) had a solid content concentration of 36% by mass, a weight average molecular weight (Mw) of 1600, and a dispersity (Mw / Mn) of 2.0.

[Synthesis Example 8]
In a vessel equipped with a stirrer, 22 parts by mass of propylene glycol monomethyl ether was charged, followed by 52 parts by mass of methyltrimethoxysilane (MTMS) and 5 parts by mass of 3-methacryloxypropyltrimethoxysilane (MPTMS), and a solution. Heated until the temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 22 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 2 hours. After cooling to 45 ° C., 32 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (A-8) was obtained. Polysiloxane (A-8) had a solid content concentration of 33% by mass, a weight average molecular weight (Mw) of 2400, and a dispersity (Mw / Mn) of 2.4.

[Synthesis Example 9]
In a vessel equipped with a stirrer, 23 parts by mass of propylene glycol monomethyl ether was charged, followed by 42 parts by mass of methyltrimethoxysilane (MTMS) and 14 parts by mass of 3-methacryloxypropyltrimethoxysilane (MPTMS). Heated until the temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 20 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 2 hours. After cooling to 45 ° C., 32 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (A-9) was obtained. Polysiloxane (A-9) had a solid content concentration of 33% by mass, a weight average molecular weight (Mw) of 2100, and a dispersity (Mw / Mn) of 2.1.

[Synthesis Example 10]
In a container equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged, followed by 34 parts by mass of methyltrimethoxysilane (MTMS), 25 parts by mass of tetramethoxysilane (TEOS), 3-methacryloxypropyltrimethoxy. 5 parts by mass of silane (MPTMS) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 23 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 34 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, methanol and ethanol generated by ion-exchanged water and hydrolysis condensation were removed by evaporating the solution at a temperature of 40 ° C. while maintaining the temperature. Thus, polysiloxane (A-10) was obtained. Polysiloxane (A-10) had a solid content concentration of 32% by mass, a weight average molecular weight (Mw) of 2200, and a dispersity (Mw / Mn) of 2.2.

[Synthesis Example 11]
In a vessel equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was charged, followed by 30 parts by mass of methyltrimethoxysilane (MTMS), 9 parts by mass of trifluoropropyltrimethoxysilane (TFMS), and 3-methacryloxypropyl. 18 parts by mass of trimethoxysilane (MPTMS) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (A-11) was obtained. Polysiloxane (A-11) had a solid content concentration of 35% by mass, a weight average molecular weight (Mw) of 1800, and a dispersity (Mw / Mn) of 2.2.

[B] Synthesis Example of Component Polysiloxane [Synthesis Example 12]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, 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 the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 18 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 30 minutes. Next, 0.1 part by mass of triethylamine was charged and maintained at 75 ° C. for 1.5 hours. After cooling to 45 ° C., 27 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (B-1) was obtained. Polysiloxane (B-1) had a solid content concentration of 34% by mass, a weight average molecular weight (Mw) of 2400, and a dispersity (Mw / Mn) of 2.4.

[Synthesis Example 13]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 23 parts by mass of methyltrimethoxysilane (MTMS), 30 parts by mass of phenyltrimethoxysilane (PTMS), γ-glycidoxypropyltri 4 parts by mass of methoxysilane (GPTMS) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 18 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 30 minutes. Next, 0.1 part by mass of triethylamine was charged and maintained at 75 ° C. for 1.5 hours. After cooling to 45 ° C., 27 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (B-2) was obtained. Polysiloxane (B-2) had a solid content concentration of 34% by mass, a weight average molecular weight (Mw) of 2500, and a dispersity (Mw / Mn) of 2.4.

[Synthesis Example 14]
In a container equipped with a stirrer, 21 parts by mass of propylene glycol monomethyl ether was charged, followed by 40 parts by mass of methyltrimethoxysilane (MTMS), 17 parts by mass of tetramethoxysilane (TEOS), and decyltrimethoxysilane (DTMS). 5 parts by mass were charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 22 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 2 hours. After cooling to 45 ° C., 33 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, methanol and ethanol generated by ion-exchanged water and hydrolysis condensation were removed by evaporating the solution at a temperature of 40 ° C. while maintaining the temperature. Thus, polysiloxane (B-3) was obtained. Polysiloxane (B-3) had a solid content concentration of 34% by mass, a weight average molecular weight (Mw) of 2000, and a dispersity (Mw / Mn) of 2.3.

[Synthesis Example 15]
In a container equipped with a stirrer, 21 parts by mass of propylene glycol monomethyl ether was charged, followed by 40 parts by mass of methyltrimethoxysilane (MTMS), 12 parts by mass of tetramethoxysilane (TMOS), and decyltrimethoxysilane (DTMS). 5 parts by mass were charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 22 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 2 hours. After cooling to 45 ° C., 33 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (B-4) was obtained. Polysiloxane (B-4) had a solid content concentration of 34% by mass, a weight average molecular weight (Mw) of 2000, and a dispersity (Mw / Mn) of 2.3.

[Synthesis Example 16]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 18 parts by mass of methyltrimethoxysilane (MTMS), 29 parts by mass of phenyltrimethoxysilane (PTMS), trifluoropropyltrimethoxysilane ( TFMS) 10 parts by mass were charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 18 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 30 minutes. Next, 0.1 part by mass of triethylamine was charged and maintained at 75 ° C. for 1.5 hours. After cooling to 45 ° C., 27 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (B-5) was obtained. Polysiloxane (B-5) had a solid content concentration of 34% by mass, a weight average molecular weight (Mw) of 2400, and a dispersity (Mw / Mn) of 2.4.

[Synthesis Example 17]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 23 parts by mass of methyltrimethoxysilane (MTMS), 24 parts by mass of phenyltrimethoxysilane (PTMS), and 3-mercaptopropyltrimethoxysilane. 10 parts by mass of (γMPTMS) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of formic acid and 18 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 30 minutes. Next, 0.1 part by mass of triethylamine was charged and maintained at 75 ° C. for 1.5 hours. After cooling to 45 ° C., 27 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (B-6) was obtained. Polysiloxane (B-6) had a solid content concentration of 34% by mass, a weight average molecular weight (Mw) of 2800, and a dispersity (Mw / Mn) of 2.1.

Preparation of radiation-sensitive polysiloxane composition and formation of protective film and interlayer insulating film [Example 1]
The solution containing the polysiloxane (A-1) obtained in Synthesis Example 1 [the amount corresponding to 50 parts by mass (solid content) of the polysiloxane (A-1)] was obtained in Synthesis Example 12 as the [B] component. A solution containing polysiloxane (B-1) [an amount corresponding to 50 parts by mass (solid content) of polysiloxane (B-1)], and (C-1) ethanone-1- [9-ethyl as component [C] 6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 3 parts by mass, (D-1) propylene glycol monomethyl ether and (D-2) as component [D] ) Diethylene glycol ethyl methyl ether was added at a ratio shown in Table 1 to prepare a radiation sensitive polysiloxane composition.
Next, this radiation-sensitive polysiloxane composition was applied to a SiO ₂ dip glass substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film (ITO adhesion described later) In the evaluation, a substrate with ITO was used). Subsequently, the obtained coating film was exposed to ultraviolet rays at an exposure amount of 300 mJ / cm ² . Subsequently, after developing for 60 seconds at 25 ° C. with an aqueous solution of 0.4% by mass of tetramethylammonium hydroxide, the film was washed with pure water for 1 minute and further heated in an oven at 230 ° C. for 60 minutes. A 2.0 μm protective film was formed.
In addition, the spinner rotation speed during film formation is adjusted so that the film thickness after heating is 3.0 μm, and exposure is performed through a photomask having contact hole patterns of sizes of 20 μm, 30 μm, 40 μm, and 50 μm. An interlayer insulating film was formed in the same manner as in the above protective film formation except that the gap (interval between the substrate and the photomask) was exposed at 150 μm.

Evaluation of Physical Properties The transparency, heat-resistant transparency, pencil hardness, scratch resistance, cracks, heat-resistant cracks, ITO adhesion, sensitivity, and refractive index of the protective films formed in each Example and Comparative Example were evaluated.
In addition, in the interlayer insulating film, since the thickness (3.0 μm) of the interlayer insulating film is different from that of the protective film, the interlayer insulating film is transparent, heat-resistant transparency, pencil hardness, scratch resistance, crack, heat-resistant Evaluation of crack, ITO adhesion, sensitivity and refractive index was judged to be the same as that of the protective film. In addition, the evaluation of the resolution (resolution of the interlayer insulating film) of the radiation-sensitive polysiloxane composition is such that the “resolution” of the radiation-sensitive polysiloxane composition can form a precise contact hole of the interlayer insulating film. Since it can be regarded as performance, it can be evaluated as being equivalent to the “resolution” of the interlayer insulating film.

(1) Evaluation of transparency of protective film A spectrophotometer (150-20 type double beam manufactured by Hitachi, Ltd.) is used for a substrate having a protective film formed as described above in each Example and Comparative Example. The light transmittance (%) at a wavelength of 400 to 800 nm was measured. When the minimum value of the light transmittance (%) at a wavelength of 400 to 800 nm was 95% or more, it was judged that the transparency of the protective film was good.

(2) Evaluation of heat-resistant transparency of protective film A substrate having a protective film formed as described above in each Example and Comparative Example was heated in a clean oven at 250 ° C. for 1 hour, and transmitted light before and after heating. After measuring the rate by the method described in (1) “Evaluation of transparency of protective film”, heat-resistant transparency (%) was calculated according to the following formula (a). When this value was 4% or less, it was judged that the heat-resistant transparency of the protective film was good.

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

(3) Measurement of Pencil Hardness (Surface Hardness) of Protective Film About the substrate having the protective film formed as described above in each Example and Comparative Example, “8.4.1 Pencil scratching of JIS K-5400-1990” The pencil hardness (surface hardness) of the protective film was measured by “Test”. When this value was 4H or larger, it was judged that the surface hardness of the protective film was good.

(4) Evaluation of scratch resistance of protective film About the substrate having the protective film formed as described above in each Example and Comparative Example, using a Gakushin type abrasion tester, 200 g of steel film on steel wool # 0000 The load was applied 10 times. The condition of abrasion was evaluated with the naked eye according to the following criteria. When the score was ◎ or ○, it was judged to have good scratch resistance.

Judgment criteria ◎: No scratches ○: 1 to 3 scratches △: 4 to 10 scratches ×: 10 or more scratches

(5) Evaluation of cracks in protective film The substrate having the protective film formed as described above in each Example and Comparative Example was left at 23 ° C. for 24 hours, and whether or not cracks occurred on the surface of the protective film. This was confirmed using a laser microscope (VK-8500 manufactured by Keyence) according to the following criteria. When the score was ◎ or ○, the crack was judged to be good.

Criteria ◎: No crack at all ○: There are 1 to 3 cracks △: There are 4 to 10 cracks ×: There are 10 or more cracks

(6) Evaluation of heat-resistant crack of protective film For the substrate having the protective film formed as described above in each Example and Comparative Example, additional baking was performed at 300 ° C. for 30 minutes, and then left at 23 ° C. for 24 hours. Whether or not cracks occurred on the surface of the protective film was confirmed using a laser microscope (VK-8500 manufactured by Keyence) according to the following criteria. When the score was ◎ or ◯, the evaluation of the heat-resistant crack was judged to be good.

Criteria ◎: No crack at all ○: There are 1 to 3 cracks △: There are 4 to 10 cracks ×: There are 10 or more cracks

(7) Evaluation of ITO (Indium Tin Oxide) Adhesiveness of Protective Film A protective film was formed as described above in each Example and Comparative Example except that a substrate with ITO was used, and a pressure cooker test (120 ° C. , Humidity 100%, 4 hours). Thereafter, “8.5.3 Adhesive cross-cut tape method of JIS K-5400-1990” was performed to determine the number of cross-cuts remaining in 100 cross-cuts, and the ITO adhesion of the protective film was evaluated. When the number of grids remaining in 100 grids was 80 or less, the ITO adhesion was judged to be poor.

(8) Evaluation of the sensitivity of the protective film For the coating film obtained above, using a TOPCON exposure machine TME-400PRJ, through a mask having a 10 μm / 30 μm line and space pattern. After exposure by changing the exposure amount, development was performed by a dipping method at 25 ° C. for 60 seconds in a 0.4 mass% tetramethylammonium hydroxide aqueous solution. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the glass substrate. At this time, the minimum exposure amount required for the 10 μm / 30 μm line and space pattern 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 refractive index of protective film Using Abbe refractometer, refractive index at 25 ° C. and 633 nm of the protective film obtained by the method of “Evaluation of light transmittance (transparency) of protective film”. Was measured.

(10) Evaluation of resolution (resolution of interlayer insulating film) of radiation-sensitive polysiloxane composition The contact hole pattern size that could be resolved in the formation of the interlayer insulating film in each example and comparative example It was measured. If a contact hole pattern of 30 μm or less could be resolved, it was judged that the resolution was good.

[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 types and amounts of each component were as shown in Tables 1 to 5. Next, a protective film was formed in the same manner as in Example 1 using the obtained radiation-sensitive polysiloxane composition. In addition, each compounding quantity in Tables 1-5 is a mass part.

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

  In Tables 1 to 5, symbols in [C] radical photopolymerization initiator, [D] solvent, [E] acrylate, [F] organic particles or inorganic particles respectively represent the following.

C-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (trade name: Irgacure OXE02, Ciba Specialty・ Chemicals Co., Ltd.
C-2: 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (trade name: Irgacure OXE01, manufactured by Ciba Specialty Chemicals Co., Ltd.)
C-3: 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) C-4: 2-dimethyl Amino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: Irgacure 379EG, manufactured by Ciba Specialty Chemicals)

D-1: Propylene glycol monomethyl ether D-2: Diethylene glycol ethyl methyl ether D-3: Butyl cesorolbu

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 Chemical Co., Ltd.)
E-3: Succinic acid modified dipentaerythritol pentaacrylate (trade name: M-520, manufactured by Nippon Kayaku Co., Ltd.)
E-4: Tris (acryloxyethyl) isocyanurate (trade name: M-315, manufactured by Toa Gosei Co., Ltd.)

F-1: Polymethylmethacrylate-based fine particles (trade name MP-300, manufactured by Soken Chemical Co., Ltd.)
F-2: Organosilica sol (trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.)
F-3: ZrO2 sol (trade name ID191, manufactured by Teika Co., Ltd.)
F-4: TiO2 sol (trade name TS-103, manufactured by Teika Co., Ltd.)

Claims (9)

The following components [A] to [D];
[A] (a1) a polysiloxane having a radical polymerizable organic group obtained by cohydrolytic condensation of a silane compound having a radical polymerizable organic group and (a2) a silane compound not having a radical polymerizable organic group A polysiloxane in which the proportion of the silane compound having a radically polymerizable organic group (a1) in the polysiloxane exceeds 15 mol%,
[B] Polysiloxane composition containing [C] radical polymerization initiator having no radical polymerizable organic group and [D] solvent.   The polysiloxane composition according to claim 1, wherein the content ratio of the structural unit having a radical polymerizable organic group in all the structural units constituting the [A] and [B] components is 1 to 20 mol%.   The polysiloxane composition according to claim 1 or 2, further comprising [E] an ethylenically unsaturated compound (excluding the component [A]).   Furthermore, the polysiloxane composition of any one of Claims 1-3 containing at least 1 sort (s) selected from the group which consists of [F] organic particle | grains and an inorganic particle. It is a manufacturing method of the polysiloxane composition of any one of Claims 1-4,
At least the following components [A] to [D];
[A] (a1) a polysiloxane having a radical polymerizable organic group obtained by cohydrolytic condensation of a silane compound having a radical polymerizable organic group and (a2) a silane compound not having a radical polymerizable organic group A polysiloxane in which the proportion of the silane compound having a radically polymerizable organic group (a1) in the polysiloxane exceeds 15 mol%,
[B] A production method comprising mixing a polysiloxane [C] radical polymerization initiator having no radical polymerizable organic group and [D] a solvent.   The cured film of the display element formed from the polysiloxane composition of any one of Claims 1-4. Next steps (1) to (4);
(1) The process of forming the coating film of the polysiloxane composition of any one of Claims 1-4 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A method for forming a cured film of a display element, comprising: a step of developing the coating film irradiated with radiation in step (2); and a step of (4) heating the coating film developed in step (3).   A cured film of a display element formed by the method according to claim 7.   The cured film of the display element according to claim 8, which is a protective film for a touch panel.