KR101287089B1 - Siloxane polymer composition, cured film and method for forming the cured film - Google Patents

Abstract

(Problem) The problem of the present invention is suitable for the discharge nozzle type coating method, which is excellent in appearance since there is no coating unevenness, and can achieve high flatness (film thickness uniformity) and high speed coating, and also transparency and scratch resistance It is to provide a siloxane polymer composition which can form an excellent protective film and a cured film as an interlayer insulating film.
(Solution means) The siloxane polymer which has a [A] radical reactive functional group, a [B] radical polymerization initiator, and [C] an organic solvent, and solid content concentration is 5 mass% or more and 30 mass% or less, and the viscosity in 25 degreeC The siloxane polymer composition which is 2.0 mPa * s or more and 10 mPa * s or less, and [C] contains an organic solvent whose vapor pressure in (C1) 20 degreeC is 0.1 mmHg or more and 1 mmHg or less as at least (C1) organic solvent.

Description

Siloxane polymer composition, cured film and method of forming a cured film {SILOXANE POLYMER COMPOSITION, CURED FILM AND METHOD FOR FORMING THE CURED FILM}

TECHNICAL FIELD This invention relates to the formation method of a siloxane polymer composition, a cured film, and a cured film.

An interlayer insulating film is formed in a display element for the purpose of insulating between wirings arrange | positioned generally in layer form. As a material for forming an interlayer insulating film, a positive radiation-sensitive composition is widely used in terms of a small number of steps for obtaining a required pattern shape and a high level of flatness is required for the obtained interlayer insulating film. Development of a composition is also performed (refer to Unexamined-Japanese-Patent No. 2000-162769).

Moreover, in manufacturing processes, such as a liquid crystal display element, a protective film may be formed in order to prevent deterioration of a liquid crystal display element from the point which the immersion process and high temperature process with a solvent are performed. Therefore, flatness, transparency, sufficient surface hardness (scratch resistance, etc.) are calculated | required by a protective film. As a material for forming the protective film, a technique using a siloxane polymer material having excellent transparency and the like is disclosed (see Japanese Patent Laid-Open No. 2000-001648, Japanese Patent Laid-Open No. 2006-178436, and Japanese Patent Laid-Open No. 2008-248239). . However, conventional siloxane polymer materials are not satisfactory in terms of flatness, surface hardness, and the like, and development of siloxane polymer radiation-sensitive compositions having improved performance has been desired.

On the other hand, touch panels are widely applied. A protective film for protecting the element and an insulating cured film for insulating between fine wirings are also required inside the touch panel. Although the various radiation sensitive compositions are used for manufacture of the above liquid crystal display element and a touchscreen according to the objective and process, the unity of a radiation sensitive composition is calculated | required from a cost reduction viewpoint.

In addition, Japanese Laid-Open Patent Publication No. 2002-131896 discloses a spin coating method as a method of applying a radiation-sensitive composition to a small substrate. According to this spin coating method, after a radiation sensitive composition is dripped at the center of a board | substrate, favorable coating uniformity is obtained as a coating method which spins a board | substrate. However, when applying to a large substrate by this spin coating method, it is necessary to ensure that the radiation-sensitive composition cut | disconnected and discarded by spin increases, the cracking of a board | substrate may occur by high speed rotation, and tact time. There is a problem such as that. Further, when applied to larger substrates, specially ordered motors are required to obtain the acceleration required for spin, which is disadvantageous in terms of manufacturing cost.

Therefore, as a coating method which replaces the spin coating method, the discharge nozzle type coating method which discharges a radiation sensitive composition from a nozzle and apply | coats on a board | substrate is employ | adopted. The discharge nozzle type coating method is a coating method for sweeping a coating nozzle in a predetermined direction to form a coating film on a substrate, which can reduce the amount of radiation-sensitive composition required for coating as compared with the spin coating method. The application time can be shortened, which is advantageous in terms of manufacturing cost. However, when applied by a discharge nozzle type coating method using a conventional radiation-sensitive composition, coating unevenness may occur, and it is difficult to realize high flatness required as characteristics of an interlayer insulating film and a protective film. It is becoming. For example, Japanese Patent Laid-Open No. 2009-98673 discloses that the radiation-sensitive composition described in this publication can be applied by a method other than the spin coating method, but suitable viscosity, solid content concentration, solvent, and the like. Is not specifically disclosed, and application | coating by the discharge nozzle type coating method etc. is not performed also in an Example.

In view of such a situation, it is suitable for the discharge nozzle type coating method, and is excellent in appearance since there is no coating stain, and can achieve high flatness (film thickness uniformity) and high speed coating, and excellent transparency and scratch resistance. There is a need for development of siloxane polymer compositions capable of forming films.

Japanese Laid-Open Patent Publication No. 2000-162769 Japanese Laid-Open Patent Publication No. 2000-001648 Japanese Patent Laid-Open No. 2006-178436 Japanese Laid-Open Patent Publication No. 2008-248239 Japanese Patent Application Laid-Open No. 2002-131896 Japanese Laid-Open Patent Publication No. 2009-98673

This invention is made | formed based on the above circumstances, The objective is that there is no application | coating stain, and it is excellent in an external appearance, and can achieve high flatness (film thickness uniformity) and high speed application | coating, and it is excellent in transparency and scratch resistance It is to provide a siloxane polymer composition capable of forming a cured film as a protective film and an interlayer insulating film.

According to an aspect of the present invention,

[A] siloxane polymer having a radical reactive functional group (hereinafter sometimes referred to as "[A] siloxane polymer"),

[B] a radical polymerization initiator, and

[C] contains an organic solvent,

Solid content concentration is 5 mass% or more and 30 mass% or less, the viscosity in 25 degreeC is 2.0 mPa * s or more and 10 mPa * s or less, and

(C) It is a siloxane polymer composition containing the organic solvent (Hereinafter, it may be called "(C1) organic solvent.") Whose vapor pressure in (C1) 20 degreeC is 0.1 mmHg or more and less than 1 mmHg at least.

Since the siloxane polymer composition of this invention contains the siloxane polymer which has [A] radical reactive functional group, when a cured film is formed, it is generally said that it is excellent in transparency. Moreover, since it contains the radical polymerization initiator [B], hardening by radical polymerization of the [A] siloxane polymer is possible, and the cured film which has sufficient scratch resistance even with a low exposure amount is obtained. Moreover, by making solid content concentration of the said siloxane polymer composition into the said range, generation | occurrence | production of a coating unevenness can be suppressed effectively, and as a result, the outstanding external appearance can be realized. Moreover, by making the viscosity of the said siloxane polymer composition into the said range, even if coating unevenness arises, maintaining the film thickness uniformity, the viscosity which can be spontaneously flattened can be achieved in a balanced manner, and high speed coatability can be achieved. have. Moreover, by using the (C1) organic solvent which has a vapor pressure of a specific range, high speed application | coating is possible, preventing further application | coating unevenness, and it is suitable also in the case of employ | adopting the discharge nozzle type coating method, for example.

[A] The siloxane polymer is a hydrolysis condensate of a hydrolyzable silane compound,

The hydrolyzable silane compound,

(a1) the hydrolyzable silane compound represented by the following formula (1) (hereinafter sometimes referred to as "(a1) compound"),

(a2) It is preferable that it is a hydrolysis-condensate containing at least the hydrolyzable silane compound represented by following formula (2) (Hereinafter, it may be called "(a2) compound.").

(In formula (1), R <^1> is a C1-C6 alkyl group; R <^2> is an organic group containing a radical reactive functional group; p is an integer of 1-3, provided that R <^1> and R <^2> are ^two or more When, a plurality of R ¹ and R ² are each independently;

In formula (2), R <^3> is a C1-C6 alkyl group; R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, an epoxy group, an amino group or an isocyanate group; n is an integer from 0 to 20; q is an integer from 0 to 3; Provided that when R ³ and R ⁴ become plural, a plurality of R ³ and R ⁴ are each independently).

Since the compound (a1) has a radical reactive functional group and the compound (a2) does not have a radical reactive functional group, when the [A] siloxane polymer is synthesized, by controlling the polymerization ratio of the (a1) compound to the (a2) compound , The content rate of the radical reactive functional group in a [A] siloxane polymer can be controlled, and the scratch resistance of the cured film formed as a result can be improved more.

[C] As the organic solvent, (C2) further contains an organic solvent (hereinafter sometimes referred to as "(C2) organic solvent") in which the vapor pressure at 20 ° C is 1 mmHg or more and 20 mmHg or less, and (C2) of the organic solvent It is preferable that content is 10 mass% or more and 50 mass% or less with respect to the total amount of (C1) organic solvent and (C2) organic solvent. By setting the mass ratio between the (C1) organic solvent having a low vapor pressure and the (C2) organic solvent having a high vapor pressure within the above specific range, the amount of the remaining solvent in the coating film after prebaking is particularly optimized and the fluidity of the coating film is balanced. As a result, generation of coating spots (stripes, pin traces, fog spots, etc.) can be suppressed, and the film thickness uniformity can be further improved.

The siloxane polymer composition further contains one or more surfactants (hereinafter sometimes referred to as "[D] surfactants") selected from [D] fluorine-based surfactants or silicone-based surfactants, and the [D] surfactants. It is preferable that content of is 0.01 mass part or more and 2 mass parts or less with respect to 100 mass parts of [A] siloxane polymers. When the siloxane polymer composition further contains a specific [D] surfactant, the surface smoothness of the coating film can be improved, and as a result, the film thickness uniformity of the interlayer insulating film formed can be further improved. Moreover, the surface smoothness of a coating film can be improved more by making content of [D] surfactant into the said range.

It is preferable that the said siloxane polymer composition further contains ethylenically unsaturated compounds (Hereinafter, it may be called "[E] ethylenically unsaturated compound") other than [E] [A] siloxane polymer. When the siloxane polymer composition further contains an [E] ethylenically unsaturated compound, the cured film formed from the siloxane polymer composition further improves scratch resistance and transparency.

The radiation-sensitive composition further contains a [F] radiation-sensitive acid generator or a radiation-sensitive base generator (hereinafter sometimes referred to as "[F] acid generator or base generator"). desirable. Polymerization becomes higher because the said siloxane polymer composition contains an [F] acid generator or a base generator, and the cured film excellent in scratch resistance etc. is obtained.

Since the said siloxane polymer composition can form the cured film excellent in transparency and scratch resistance, it is suitable as a material used for formation of the cured film as a protective film or an interlayer insulation film for display elements or a touch panel.

The cured film formed using the said siloxane polymer composition is also suitably contained in this invention.

Formation method of the cured film of this invention,

(1) a step of applying the siloxane polymer composition onto a substrate while relatively moving the discharge nozzle and the substrate to form a coating film,

(2) a step of irradiating at least a part of the coating film with radiation,

(3) a step of developing the coating film irradiated with the radiation, and

(4) heating the developed coating film.

In the said formation method, the said siloxane polymer composition which can not only apply | coat at high speed but can form the cured film excellent in film thickness uniformity is used. Therefore, even if the ejection nozzle type coating method is adopted, high speed coating can be performed while preventing uneven coating. Moreover, by forming a pattern by exposure, image development, and heating using radiation sensitivity, the cured film which has a fine and fine pattern can be formed easily. In addition, the cured film formed as a protective film and an interlayer insulation film thus formed does not have coating unevenness and has high flatness, and can be suitably used for display elements such as liquid crystal display elements, organic EL display elements, and touch panels.

In addition, the "discharge nozzle type coating method" as used in this specification means the method of apply | coating the siloxane polymer composition to a to-be-coated object through a nozzle, for example, and arrange | positions a some nozzle hole in a column shape, for example. The method of apply | coating the said siloxane polymer composition using the nozzle which has the discharge opening which were made, the method of apply | coating the said siloxane polymer composition using the nozzle which has a slit-shaped discharge opening, etc. are mentioned, The said siloxane polymer composition is apply | coated on a board | substrate. After this, the concept includes the operation of adjusting the film thickness by spinning the substrate. In addition, the "radiation" of the "radiation-sensitive resin composition" used in this specification is a concept containing visible light, an ultraviolet-ray, an ultraviolet-ray, X-ray, a charged particle beam, etc.

As described above, the present invention is excellent in appearance without coating stains, and can achieve high flatness (film thickness uniformity) and high speed coating, and form a protective film and a cured film as an interlayer insulating film excellent in transparency and scratch resistance. Possible siloxane polymer compositions can be provided. Since the said siloxane polymer composition exhibits effects, such as high speed applicability | paintability, it can apply suitably to a discharge nozzle type coating method etc .. Moreover, since the cured film formed from the said siloxane polymer composition shows outstanding transparency and abrasion resistance, it is not only for a display element but can be applied also as a protective film for interlayers, an interlayer insulation film, etc., and is advantageous also in cost.

(Mode for carrying out the invention)

<Siloxane polymer composition>

The siloxane polymer composition of this invention contains [A] siloxane polymer, [B] radical polymerization initiator, and [C] organic solvent. Moreover, you may contain a [D] surfactant, an [E] ethylenically unsaturated compound, an [F] acid generator, or a base generator as a suitable component. Moreover, you may contain other arbitrary components in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.

<[A] siloxane Polymer>

[A] siloxane polymer contained in the said siloxane polymer composition will not be specifically limited if it has a radical reactive functional group in the principal chain or side chain of the polymer of a compound which has a siloxane bond. Since the [A] siloxane polymer has a radical reactive functional group, it can harden | cure by radical polymerization, and it is possible to suppress hardening shrinkage to the minimum.

As a radical reactive functional group, unsaturated organic groups, such as a vinyl group, (alpha)-methyl vinyl group, acryloyl group, a methacryloyl group, a styryl group, are mentioned, for example. Among these, it is preferable to have acryloyl group or methacryloyl group from the point which hardening reaction advances smoothly.

The siloxane polymer is a hydrolytic condensate of a hydrolyzable silane compound, wherein the hydrolyzable silane compound is represented by (a1) a hydrolyzable silane compound represented by the formula (1), and (a2) in the formula (2). It is preferable that it is at least a hydrolysis condensate with the hydrolyzable silane compound shown.

The term “hydrolyzable silane compound” in the present specification is usually hydrolyzed to generate a silanol group by heating within a temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the absence of a catalyst and excess water. It refers to a compound having a group capable of forming a group or a siloxane condensate. In the hydrolysis reaction of the hydrolyzable silane compounds represented by the formulas (1) and (2), some of the hydrolyzable groups may remain unhydrolyzed in the siloxane polymer to be produced. Here, a "hydrolyzable group" means the group which can form the group which can hydrolyze and produce | generate a silanol group, or a siloxane condensate here. In addition, in the said siloxane polymer composition, some hydrolysable silane compounds may remain in the state of a monomer in the state in which some or all hydrolysable groups in the molecule are unhydrolyzed, and without condensation with other hydrolysable silane compounds. . In addition, "hydrolysis condensation product" means the hydrolysis condensation product which some silanol groups of the hydrolyzed silane compound condensed. Hereinafter, the compound (a1) and the compound (a2) will be described in detail.

[(a1) compound]

In said formula (1), R <^1> is a C1-C6 alkyl group. R ² is an organic group containing a radical reactive functional group. p is an integer of 1-3. However, when R <^1> and R <^2> become ^two or more, some R <^1> and R <^2> are respectively independent.

As a C1-C6 alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, a butyl group etc. are mentioned, for example. Of these, methyl and ethyl groups are preferred from the viewpoint of ease of hydrolysis. As p, 1 or 2 is preferable and 1 is more preferable from a viewpoint of progress of a hydrolysis condensation reaction.

As an organic group which has a radical reactive functional group, a linear, branched or cyclic C1-C12 alkyl group, C6-C12 aryl group, and C7-C12 which substituted one or more hydrogen atoms by the said radical reactive functional group Aralkyl group etc. are mentioned. When a plurality of R ² are present in the same molecule, they are each independently. In addition, the organic group which R <^2> represents may have a hetero atom. As such an organic group, an ether group, ester group, a sulfide group, etc. are mentioned, for example.

Examples of the compound (a1) in the case of p = 1 include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, o-styryltrimethoxysilane, and o-styryltri. Methoxysilane, m-styryltrimethoxysilane, m-styryltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane , Methacryloxytrimethoxysilane, methacryloxytriethoxysilane, methacryloxytripropoxysilane, acryloxytrimethoxysilane, acryloxytriethoxysilane, acryloxytripropoxysilane, 2-methacryl Oxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethyltripropoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane , 3-methacryloxypropyl tripropoxysilane, 2-acryloxyethyl Limethoxysilane, 2-acryloxyethyltriethoxysilane, 2-acryloxyethyltripropoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltri Trialkoxy silane compounds, such as a propoxy silane, a trifluoro propyl trimethoxysilane, a trifluoro propyl triethoxysilane, and a trifluoro butyl trimethoxysilane, are mentioned.

Examples of the compound (a1) in the case of p = 2 include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, allylmethyldimethoxysilane, and allylmethyldiethoxy. And dialkoxysilane compounds such as silane and phenyltrifluoropropyldimethoxysilane.

Examples of the compound (a1) in the case of p = 3 include allyldimethylmethoxysilane, allyldimethylethoxysilane, divinylmethylmethoxysilane, divinylmethylethoxysilane, and 3-methacryloxypropyldimethylmethoxysilane. , 3-acryloxypropyldimethylmethoxysilane, 3-methacryloxypropyldiphenylmethoxysilane, 3-acryloxypropyldiphenylmethoxysilane, 3,3'-dimethacryloxypropyldimethoxysilane, 3, 3'-diacryloxypropyldimethoxysilane, 3,3 ', 3 "-trimethacryloxypropylmethoxysilane, 3,3', 3" -triacryloxypropylmethoxysilane, dimethyltrifluoropropylmethoxy Monoalkoxysilane compounds, such as oxysilane, are mentioned.

Among these (a1) compounds, not only the scratch resistance and the like can be achieved at a high level, but also the condensation reactivity is increased, such as vinyltrimethoxysilane, p-styryltriethoxysilane and 3-methacryloxypropyltri. A methoxysilane, 3-acryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-acryloxypropyl triethoxysilane are preferable.

[(a2) compound]

In said formula (2), R <^3> is a C1-C6 alkyl group. R <^4> is a hydrogen atom, a C1-C20 alkyl group, a C1-C20 fluorinated alkyl group, a phenyl group, a naphthyl group, an epoxy group, an amino group, or an isocyanate group. n is an integer of 0-20. q is an integer of 0-3. However, when R <^3> and R <^4> become two or more, some R <^3> and R <^4> is respectively independent.

As said C1-C6 alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, a butyl group etc. are mentioned, for example. Of these, methyl and ethyl groups are preferred from the viewpoint of ease of hydrolysis. As q, 1 or 2 is preferable and 1 is more preferable from a viewpoint of progress of a hydrolysis condensation reaction.

As said C1-C20 alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert- butyl group, n-pentyl group, 3-methylbutyl, for example Group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group , 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1 , 1-dimethylbutyl group, n-heptyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group, 1-methylhexyl group, 4,4-dimethylpentyl group, 3,4-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3-dimethylpentyl group, 1,3-dimethylpentyl group, 2, 2-dimethylpentyl group, 1,2-dimethylpentyl group, 1,1-dimethylpentyl group, 2,3,3-trimethylbutyl group, 1,3,3-trimethylbutyl group, 1,2,3-trimethylbutyl Group, n-octyl group, 6-methylheptyl group, 5-methylheptyl group, 4 -Methylheptyl group, 3-methylheptyl group, 2-methylheptyl group, 1-methylheptyl group, 2-ethylhexyl group, n-nonanyl group, n-decyl group, n-undecyl group, n-dodecyl group, n -Tridecyl group, n- tetradecyl group, n-heptadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, etc. are mentioned. Preferably it is a C1-C10 alkyl group, More preferably, it is a C1-C3 alkyl group.

Examples of the (a2) compound in the case of q = 0 include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra-n-propoxysilane, and the like as a silane compound substituted with four hydrolyzable groups. Tetra-i-propoxysilane and the like.

As the compound (a2) in the case of q = 1, a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups is methyltrimethoxysilane, methyltriethoxysilane, methyltri-i Propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, Naphthyltrimethoxysilane, phenyltriethoxysilane, naphthyltriethoxysilane, aminotrimethoxysilane, aminotriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy, γ-glyci Doxypropyl trimethoxysilane, 3-isocyanopropyl trimethoxysilane, 3-isocyanopropyl triethoxysilane, etc. are mentioned.

Examples of the silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups as the compound (a2) in the case of q = 2 include dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane, and the like. Can be.

Examples of the silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group as the compound (a2) in the case of q = 3 include trimethylmethoxysilane, triphenylmethoxysilane, tributylmethoxysilane, and the like. Can be.

Of these (a2) compounds, silane compounds substituted with four hydrolyzable groups, silane compounds substituted with one non-hydrolyzable group and three hydrolyzable groups are preferable, and silanes substituted with one non-hydrolyzable group and three hydrolyzable groups More preferred are compounds. Particularly preferred hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane and ethyltrimethoxy Silane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, naphthyltrimethoxysilane, γ-aminopropyltrimeth And oxysilane and γ-isocyanatepropyltrimethoxysilane. You may use such a hydrolysable silane compound individually or in combination of 2 or more types.

About the mixing ratio of the said (a1) compound and (a2) compound, it is preferable that (a1) compound exceeds 5 mol%. When the compound (a1) is 5 mol% or less, the exposure sensitivity at the time of forming a cured film is low, and there is a tendency to lower the scratch resistance and the like of the resulting cured film.

The conditions for hydrolytically condensing the compound (a1) and the compound (a2) include hydrolyzing at least a portion of the compound (a1) and the compound (a2), converting the hydrolyzable group to a silanol group, and causing a condensation reaction. As long as it is not specifically limited, As an example, it can carry out as follows.

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

Examples of the solvent provided for the hydrolysis condensation include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyls. Ether propionate, aromatic hydrocarbons, ketones, other esters, etc. are mentioned. These solvent can be used individually or in combination of 2 or more types.

Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

As the ethers, for example, tetrahydrofuran and the like can be mentioned.

As the glycol ether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like can be given.

Examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like.

Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like.

Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.

Examples of the propylene glycol monoalkyl ether propionate include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, and the like. It can be mentioned.

As aromatic hydrocarbons, toluene, xylene, etc. are mentioned, for example.

As ketones, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, etc. are mentioned, for example.

As other esters, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl hydroxyacetic acid, ethyl hydroxyacetic acid, hydroxyacetic acid butyl, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionic acid propyl, 3- Butyl hydroxypropionate, methyl 2-hydroxy-3-methylbutanoic acid, methyl methoxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid propyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, ethoxyacetic acid Propyl, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxyacetate Propyl acid, butyl propoxyacetic acid, methyl butoxyacetic acid, ethyl butoxyacetic acid, butoxyacetic acid propyl, butyl butoxyacetic acid, 2-methoxypropionate, ethyl 2-methoxypropionic acid, 2-methoxypropionic acid propyl, 2 Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2- Propyl butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionic acid, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-E Ethyl oxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Field, and 3-propoxy propionate, butyl propionate, methyl 3-butoxy, 3-butoxy-ethyl, 3-butoxy propyl propionate, butyl propionate, 3-butoxy.

Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl acetate are preferable, and in particular, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl acetate butyl are preferable.

The hydrolysis condensation reaction 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, etc.). ), A base catalyst (for example, nitrogen-containing compounds such as ammonia, primary amines, secondary amines, tertiary amines and pyridine); basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate; sodium acetate and the like Carbonic acid salts, various Lewis bases and the like, or alkoxides (for example, zirconium alkoxides, titanium alkoxides, aluminum alkoxides, and the like). For example, tri-i-propoxy aluminum can be used as aluminum alkoxide. As the usage-amount of a catalyst, it is 0.2 mol or less, More preferably, it is 0.00001 mol-0.1 mol with respect to 1 mol of monomers of a hydrolyzable silane compound from a viewpoint of promotion of a hydrolysis condensation reaction.

Although reaction temperature and reaction time in hydrolysis condensation are set suitably, reaction temperature becomes like this. Preferably it is 40 degreeC-200 degreeC, More preferably, it is 50 degreeC-150 degreeC. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 hour to 12 hours. By setting it as such reaction temperature and reaction time, hydrolytic condensation reaction can be performed efficiently. In this hydrolysis condensation, the hydrolyzable silane compound, water, and catalyst may be added to the reaction system at one time, and the reaction may be performed in one step, or the hydrolyzable silane compound, water, and catalyst may be added several times in the reaction system, Hydrolysis and condensation reaction may be performed in multiple stages. After the hydrolytic condensation reaction, water and the resulting alcohol can be removed from the reaction system by adding a dehydrating agent and then evaporating. The dehydrating agent used in this step is generally either adsorbed or entrapped with excess water so that the dehydrating capacity is either consumed completely or removed by evaporation.

As polystyrene conversion weight average molecular weight (henceforth "Mw") by GPC (gel permeation chromatography) of the said hydrolysis-condensation product, 500-5,000 are preferable and 1,000-3,000 are more preferable. By making Mw 500 or more, the film-forming property of the said siloxane polymer composition can be improved. On the other hand, when Mw is 5,000 or less, the fall of developability of a siloxane polymer composition can be prevented.

As polystyrene conversion number average molecular weight (henceforth "Mn") by GPC of the said hydrolysis-condensation product, 300-1,500 are preferable and 500-1,200 are more preferable. By making Mn of a siloxane polymer into the said range, hardening reactivity at the time of hardening of the coating film of the said siloxane polymer composition can be improved.

As molecular weight distribution "Mw / Mn" of the said hydrolysis-condensation product, 3.0 or less are preferable and 2.6 or less are more preferable. The developability of the cured film obtained can be improved by making Mw / Mn of the hydrolysis-condensation product of the (a1) compound and (a2) compound into 3.0 or less. The said siloxane polymer composition containing the (A) siloxane polymer has little development residue when developing, and can form a desired pattern shape easily.

<[B] radical polymerization initiator>

Since the said siloxane polymer composition contains the radical polymerization initiator [B], hardening by radical polymerization of the [A] siloxane polymer is possible, and the cured film which has sufficient scratch resistance even in a low exposure amount is obtained. Moreover, it is preferable that [B] radical polymerization initiator is a radiation sensitive polymerization initiator.

[B] As a radical polymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, etc. are mentioned. These [B] radical polymerization initiators can be used individually or in mixture of 2 or more types.

As the O-acyl oxime compound, for example, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1- Onoxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl Oxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone -1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9 -Ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) , Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy One trillion days) -9H- carbazole-3-yl] -1- (O- acetyl oxime), and the like.

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

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

Examples of the? -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- 1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one .

As an α-hydroxy ketone compound, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1 -One, 4- (2-hydroxy ethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like.

Among these, as a preferable acetophenone compound, the (alpha)-amino ketone compound is preferable and 2-dimethylamino- 2- (4-methylbenzyl)-1- (4-morpholin-4-yl-phenyl) -butane-1 -One and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one can be mentioned.

As a biimidazole compound, it is a 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetrakis (4-ethoxycarbonylphenyl) -1,2' ratio, for example. Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole is mentioned.

Of these, preferred biimidazole compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl)- 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5 ' More preferred is -tetraphenyl-1,2'-biimidazole.

[B] When using a biimidazole compound as a radical polymerization initiator, in order to sensitize this, the aliphatic or aromatic compound which has a dialkylamino group (henceforth "amino type sensitizer") can be added.

As an amino-type sensitizer, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, etc. are mentioned, for example. Among these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is preferable. The amino-based sensitizers may be used alone or in combination of two or more.

In addition, when using a biimidazole compound and an amino sensitizer together in the said siloxane polymer composition, a thiol compound can be added as a hydrogen radical donor. The biimidazole compound is sensitized and cleaved with an amino sensitizer to generate imidazole radicals, but the high polymerization initiation capacity may not be expressed as it is. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, a hydrogen radical is donated from a thiol compound to imidazoradical. As a result, not only the imidazole radical is converted into neutral imidazole, but also a component having sulfur radicals having a high polymerization initiation capacity is generated, whereby a cured film having high scratch resistance and the like can be formed even at a low radiation dose.

As such a thiol compound, for example

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

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

And bifunctional or higher aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate). Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

When using a biimidazole compound and an amino sensitizer together, as an usage-amount of an amino sensitizer, it is 0.1 mass part-50 mass parts with respect to 100 mass parts of biimidazole compounds, More preferably, it is 1 mass It is 20 mass parts. By setting the usage-amount of an amino sensitizer into 0.1 mass part-50 mass parts, the hardening reactivity at the time of exposure of the said siloxane polymer composition improves, and the scratch resistance of the cured film obtained etc. can be improved.

In addition, when using a biimidazole compound, an amino sensitizer, and a thiol compound together, as a usage-amount of a thiol compound, it is 0.1 mass part-50 mass parts more preferably with respect to 100 mass parts of biimidazole compounds, More preferably, Is 1 mass part-20 mass parts. By setting the usage-amount of a thiol compound to 0.1 mass part-50 mass parts, the scratch resistance of the cured film obtained, etc. can be improved.

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

As the usage-amount of the radical polymerization initiator [B] in the said siloxane polymer composition, Preferably it is 0.05 mass part-30 mass parts, More preferably, 0.1 mass part-15 mass parts with respect to 100 mass parts of [A] siloxane polymers. to be. By making the usage-amount of the radical polymerization initiator (B) into the said range, the said siloxane polymer composition shows high radiation sensitivity and can form the cured film which has higher scratch resistance etc.

<[C] organic solvent>

The said siloxane polymer composition contains the organic solvent whose vapor pressure in at least (C1) 20 degreeC is 0.1 mmHg or more and less than 1 mmHg as [C] organic solvent. Moreover, it is preferable to contain the organic solvent whose vapor pressure in (C2) 20 degreeC is 1 mmHg or more and 20 mmHg or less. By using the [C] organic solvent which has a vapor pressure of a specific range, even if a discharge nozzle type | mold coating method is employ | adopted, high speed application | coating is attained, preventing the application | coating stain. The vapor pressure can be measured by a known method, but in this specification refers to a value measured by the transfer method (gas flow method).

As the organic solvent (C), those which dissolve or disperse the above components uniformly and do not react with each component are suitably used. As such [C] organic solvent, For example, alcohol, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether , Diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, lactic acid esters, aliphatic carboxylic acid esters, amides, lac Tones, ketones, etc. are mentioned. These may be used individually by 1 type, and may mix and use 2 or more types.

As the organic solvent (C1), for example,

Alcohols such as benzyl alcohol;

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

Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether;

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

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

Diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether;

Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate;

Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether;

Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether;

Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate;

Lactic acid esters such as n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, and isoamyl lactate;

Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methyllactic acid, ethyl ethoxyacetate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutylate, acetoacetic acid methyl, Aliphatic carboxylic acid esters such as ethyl acetoacetic acid, methyl pirbate and ethyl pirbate;

Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, and N, N-dimethyl acetamide;

Lactones such as N-methylpyrrolidone and γ-butyrolactone;

Ketones, such as dipropyl ketone, etc. are mentioned. These may be used independently and may mix and use 2 or more types.

As the organic solvent (C2), for example, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether And propylene glycol monomethyl ether acetate, cyclohexanone, ethyl acetate, propyl acetate, n-butyl acetate, methylpropyl ketone, methyl isobutyl ketone, methyl 3-methoxypropionate, methyl lactate, ethyl lactate, and the like. These may be used individually by 1 type, and may mix and use 2 or more types.

When using by mixing (C1) an organic solvent and (C2) an organic solvent,

Diethylene glycol ethyl methyl ether / diethylene glycol dimethyl ether,

Diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate,

Diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether,

Diethylene glycol ethyl methyl ether / cyclohexanone,

Diethylene glycol diethyl ether / diethylene glycol dimethyl ether,

Diethylene glycol diethyl ether / propylene glycol monomethyl ether acetate,

Diethylene glycol diethyl ether / cyclohexanone,

Diethylene glycol diethyl ether / 3-methoxypropionate methyl,

Diethylene glycol diethyl ether / methyl isobutyl ketone,

Diethylene glycol diethyl ether / acetic acid n-butyl,

Ethylene glycol monobutyl ether / propylene glycol monomethyl ether,

Ethylene glycol monobutyl ether / propylene glycol monomethyl ether acetate,

Combinations of ethylene glycol monobutyl ether / cyclohexanone and the like are preferable. In addition, you may use (C1) organic solvent or (C2) organic solvent in mixture of 2 or more types, For example, diethylene glycol diethyl ether / propylene glycol monomethyl ether acetate / cyclohexanone / 3-meth Methyl oxypropionate etc. are mentioned.

As content of (C2) organic solvent, 10 mass% or more and 50 mass% are preferable with respect to the total amount of (C1) organic solvent and (C2) organic solvent. By setting the mass ratio between the (C1) organic solvent having a low vapor pressure and the (C2) organic solvent having a high vapor pressure within the above range, the amount of the remaining solvent in the coating film after prebaking is particularly optimized, and the fluidity of the coating film is balanced. As a result, occurrence of coating spots (stripes, pin traces, fog spots, etc.) can be suppressed, and the film thickness uniformity can be further improved.

<[D] Surfactant>

It is preferable that the said siloxane polymer composition further contains 1 or more types of surfactant chosen from the group which consists of a [D] fluorine-type surfactant and a silicone type surfactant in order to improve the film formation property of the said siloxane polymer composition further. When the said siloxane polymer composition contains surfactant [D], the surface smoothness of a coating film can be improved and as a result, the film thickness uniformity of the cured film formed can be improved further.

As a fluorine-type surfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in at least any part of a terminal, a main chain, and a side chain is preferable. As the fluorine-based surfactant, for example, 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2- Tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1, 2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1, 2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2 , 2,3,3,9,9,10,10-decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carbonate, diglycerin tetrakis Low alkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, purple To kill roal polyoxyethylene ethanol, alkyl alkoxylate, a carbonic acid-fluoro-perfluoroalkyl, and the like esters.

As a commercial item of a fluorine-type surfactant, BM-1000, BM-1100 (above, BM CHEMIE company), Megapack F142D, Megapack F172, Megapack F173, Megapack F183, Megapack F178, Megapack, for example F191, Megapack F471, Megapack F476 (above, Dainippon Inking Chemical Co., Ltd.), Fluorad FC-170C, Fluorad FC-171, Fluorad FC-430, Fluorad FC-431 ( Sumitomo 3M, Suplon S-112, Suplon S-113, Suplon S-131, Suplon S-141, Suplon S-145, Suplon S-382, Suplon SC-101, Suplon SC-102, Suplon SC-103, Suplon SC-104, Suplon SC-105, Suplon SC-106 (above, Asahi Glass Co., Ltd.), Ftop EF301 F-top EF303, F-top EF352 250, aftergent FT-251, aftergent FT-300, FT-310 Gentry printers, printers Gentry FT-400S, printers Gentry FTX-218, printers Gentry FT-251 (above, whether or manufactured by Neos), and the like.

As silicone type surfactant, Toray silicone DC3PA, Torre silicone DC7PA, Torre silicone SH11PA, Torre silicone SH21PA, Torre silicone SH28PA, Torre silicone SH29PA, Torre silicone SH30PA, Torre silicone SH-190, Torre silicone SH- 193, Torre silicon SZ-6032, Torre silicon SF-8428, Torre silicon DC-57, Torre silicon DC-190, SH 8400 FLUID (above, Torre Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300 And TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicone Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), and the like.

These [D] surfactants may be used alone or in combination of two or more thereof. As content of the [D] surfactant in the said siloxane polymer composition, Preferably it is 0.01 mass part or more and 2 mass parts or less with respect to 100 mass parts of [A] siloxane polymers, More preferably, it is 0.05 mass part or more and 1 mass part. Or less. By making content of a surfactant (D) into the said range, the surface smoothness of a coating film can be improved more.

<[E] ethylenically unsaturated compound>

It is preferable that the said siloxane polymer composition further contains [E] ethylenically unsaturated compound. When the said siloxane polymer composition contains [E] ethylenically unsaturated compound further, a radiation sensitivity improves and sublimation property falls. Therefore, the cured film formed from the said siloxane polymer composition improves scratch resistance and transparency further.

As the ethylenically unsaturated compound (E), a monofunctional, bifunctional or trifunctional or higher (meth) acrylic acid ester is preferable from the viewpoint of having good polymerizability and improving the strength of the resulting cured film. When the said radiation sensitive composition contains these compounds, the cured film with which transparency, abrasion resistance, etc. are highly balanced can be formed.

As monofunctional (meth) acrylic acid ester, it is 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether, for example. Methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxy propyl) phthalate, ω-carboxypolycaprolactone monoacrylate Etc. can be mentioned. As a commercial item, For example, Aronix M-101, M-111, M-114, M-5300 (above, Toagosei Co., Ltd.); KAYARAD TC-110S, TC-120S (above, Nippon Kayaku Co., Ltd.); Viscoat 158, East 2311 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), etc. are mentioned.

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

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

Ω-carboxy polycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethol propane triacrylate, pentaerythritol triacrylate, and pentaerythritol tetra among these [E] ethylenically unsaturated compounds Acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, Commercial products containing succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, and polyfunctional urethane acrylate compounds are preferred.

Said [E] ethylenically unsaturated compound may be used independently, or may mix and use 2 or more types. As a use ratio of the [E] ethylenically unsaturated compound in the said composition, 5 mass parts-80 mass parts are preferable with respect to 100 mass parts of [A] siloxane polymers, and 10 mass parts-30 mass parts are more preferable. By making the usage-amount of an ethylenically unsaturated compound (E) into the said range, the radiation sensitivity of the said composition, the scratch resistance of the cured film obtained, etc. become more favorable.

<[F] acid generator or base generator>

[F] A radiation sensitive acid generator or a radiation sensitive base generator is defined as a compound which can release an acidic active substance or a basic active substance by irradiating radiation. The siloxane polymer (A) is cured by the catalytic action of the [F] acid generator or the base generator, resulting in higher polymerizability, thereby obtaining a cured film excellent in scratch resistance and the like.

[F] The radiation irradiated to decompose an acid generator or a base generator to generate a cation or anion of an acidic active substance or a basic active substance includes visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ-rays and the like. Among these radiations, it is preferable to use ultraviolet rays because they have a constant energy level and can achieve a high curing rate, and the irradiation apparatus is relatively inexpensive and compact.

As a radiation sensitive acid generator, a diphenyl iodonium salt, a triphenylsulfonium salt, and a tetrahydrothiophenium salt are preferable, and a triphenylsulfonium salt and a tetrahydrothiophenium salt are more preferable.

Examples of the diphenyl iodonium salt include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroarsenate, diphenyl iodonium tri Diphenyl iodonium trifluoroacetate, diphenyl iodonium-p-toluene sulfonate, diphenyl iodonium butyl tris (2,6-difluorophenyl) borate, 4- Bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p- (4-t-butylphenyl) iodonium camphorsulfonic acid, and the like.

Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, and triphenylsulfonium. -p-toluenesulfonate, a triphenylsulfonium butyl tris (2, 6- difluorophenyl) borate, etc. are mentioned.

As the tetrahydrothiophenium salt, for example, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalene-1- Yl) tetrahydrothiophenium nonafluoro-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-butoxycarbonyl oxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1 -Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, etc. are mentioned.

Among these radiation-sensitive acid generators, from the viewpoint of improving radiation sensitivity of the radiation-sensitive composition, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonate, 1- (4,7-dibutoxy- Particular preference is given to 1-naphthalenyl) tetrahydrothiopheniumtrifluoromethane sulfonate.

Examples of the radiation sensitive base generator include 2-nitrobenzylcyclohexylcarbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, and N- (2-nitrobenzyloxycarbo Nil) 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, hexaamine cobalt (III) tris (triphenylmethylborate), and the like.

Among these radiation-sensitive base generators, 2-nitrobenzylcyclohexylcarbamate and O-carbamoylhydroxyamide are more preferable from the viewpoint of improving radiation sensitivity of the radiation-sensitive composition.

[F] The acid generator or the base generator may be used alone or in combination of two or more thereof. As the usage-amount of the [F] acid generator or base generator, it is 0.01-20 mass parts or less with respect to 100 mass parts of [A] siloxane polymers, More preferably, it is 0.1-10 mass parts or less. By setting the amount of the acid generator or base generator used to 0.01 to 20 parts by mass, a cured film excellent in radiation sensitivity, scratch resistance, transparency, and the like can be obtained in a balanced manner.

&Lt; Other optional components >

In addition to the above-mentioned [A]-[F] components, the said siloxane polymer composition may contain other arbitrary components, such as an adhesion | attachment adjuvant, a basic compound, a quinonediazide compound, as needed in the range which does not impair a desired effect. Can be. Hereinafter, these components are explained in full detail. In addition, each other arbitrary component may be used individually, or may mix and use 2 or more types.

[Adhesive Supplements]

In the siloxane polymer composition, an adhesion agent may be used to improve the adhesion between the inorganic material serving as the substrate, for example, silicon compounds such as silicon, silicon oxide, silicon nitride, and metals such as gold, copper, aluminum, and the insulating film. have. As this adhesion | attachment adjuvant, a functional silane coupling agent is used preferably. As a functional silane coupling agent, the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), a thiol group, is mentioned, for example.

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? - Glycidoxypropyltrimethoxysilane, gamma -glycidoxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl tri Methoxysilane and the like. Among these, (gamma)-glycidoxy propyl alkyl dialkoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, and (gamma)-methacryloxypropyl trimethoxysilane are preferable.

In the said siloxane polymer composition, 0.5 mass part or more and 20 mass parts or less are preferable with respect to 100 mass parts of [A] siloxane polymers, and 1 mass part or more and 10 mass parts or less are more preferable. By making the quantity of an adhesion | attachment adjuvant into the said range, adhesiveness of the cured film formed and a board | substrate improves.

[Basic compound]

As a basic compound, it can select arbitrarily and can use from what is used by chemically amplified resist. Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and carboxylic acid quaternary ammonium salts. By containing a basic compound in the said siloxane polymer composition, the diffusion length of the acid generated from the acid generator by exposure can be controlled suitably, and pattern developability can be made favorable.

Examples of the aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanol amine, Triethanolamine, dicyclohexylamine, dicyclohexyl methylamine, etc. are mentioned.

Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.

As the heterocyclic amine, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4 -Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy Quinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] -5-nonene And 1,8-diazabicyclo [5,3,0] -7 undecene.

Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide and tetra-n-hexylammonium hydroxide.

Examples of the carbonic acid quaternary ammonium salt include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate and tetra-n-butylammonium benzoate.

The content of the basic compound in the siloxane polymer composition is preferably 0.001 parts by mass to 1 parts by mass, and more preferably 0.005 parts by mass to 0.2 parts by mass with respect to 100 parts by mass of the [A] siloxane polymer. Pattern developability becomes favorable by making content of a basic compound into the said range.

[Quinonediazide compounds]

A quinonediazide compound is a compound which produces | generates a carboxylic acid by irradiation of a radiation. As a quinone diazide compound, the condensate of a phenolic compound or an alcoholic compound (henceforth "mother nucleus"), and 1,2-naphthoquinone diazide sulfonic-acid halide can be used.

Examples of the mother core include trihydroxybenzophenone, tetrahydroxy benzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother cores.

As trihydroxy benzophenone, 2, 3, 4- trihydroxy benzophenone, 2, 4, 6- trihydroxy benzophenone etc. are mentioned, for example.

As tetrahydroxy benzophenone, it is 2,2 ', 4,4'- tetrahydroxy benzophenone, 2,3,4,3'- tetrahydroxy benzophenone, 2,3,4,4'-, for example. Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, and the like. have.

As pentahydroxy benzophenone, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc. are mentioned, for example.

As hexahydroxy benzophenone, it is 2,4,6,3 ', 4', 5'-hexahydroxy benzophenone, 3,4,5,3 ', 4', 5'-hexahydroxy benzo, for example. Phenone etc. are mentioned.

Examples of the (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1 -Tris (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3 -Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenyl propane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] Ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5 , 6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like.

Examples of other parent nuclei include 2- [2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7- Methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) ) -1- methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) - dihydroxybenzene, and the like.

Among these nuclei, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 '- [1- [4- [1- [ 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferable.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. As 1, 2- naphthoquinone diazide sulfonic-acid chloride, a 1, 2- naphthoquinone diazide- 4-sulfonic acid chloride and a 1, 2- naphthoquinone diazide- 5-sulfonic acid chloride are mentioned, for example. . Among these, 1,2-naphthoquinone diazide-5-sulfonic acid chloride is preferable.

As a condensate of a phenolic compound or an alcoholic compound with 1,2-naphthoquinone diazide sulfonic acid halide, 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinone diazide- Condensates with 5-sulfonic acid chloride, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinone Preference is given to condensates with diazide-5-sulfonic acid chlorides.

Condensation reaction of a phenolic compound or an alcoholic compound (parent nucleus) with 1,2-naphthoquinonediazidesulfonic acid halide is preferably 30 mol% to 85 mol with respect to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably, 1, 2- naphthoquinone diazide sulfonic-acid halide corresponding to 50 mol%-70 mol% can be used. Condensation reaction can be performed by a well-known method.

As the quinone diazide compound, 1,2-naphthoquinone diazide sulfonic acid amides in which the ester bond of the above-described parent nucleus is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1, 2-naphthoquinone diazide-4-sulfonic acid amide etc. are also used suitably.

<Preparation of siloxane polymer composition>

The said siloxane polymer composition is prepared in the state which melt | dissolved or disperse | distributed the [A] siloxane polymer, the [B] radical polymerization initiator, and arbitrary components uniformly at a predetermined ratio as needed in the organic solvent [C].

When preparing the said siloxane polymer composition in a solution state, it is 10 mass% or more and 30 mass% or less as solid content (total amount of [A] siloxane polymer, [B] radical polymerization initiator, and optional components contained as needed) concentration. . 15 mass%-30 mass% are preferable, and 20 mass%-28 mass% are more preferable. In addition, the viscosity in 25 degreeC of the said siloxane polymer composition is 2.0 mPa * s or more and 10 mPa * s or less. By making the viscosity of the said siloxane polymer composition into the said range, while maintaining the film thickness uniformity, the viscosity which can be spontaneously flattened even if a coating unevenness generate | occur | produces can be achieved in a balanced manner, and high speed applicability | paintability can be realized. . The solution of the prepared said siloxane polymer composition can also be used for use, after filtering using a Millipore filter etc. of about 0.2 micrometer-about 0.5 micrometers in pore size.

<Cured film>

The cured film formed using the said siloxane polymer composition is also suitably contained in this invention. The "cured film" in this invention is a generic term of the thermosetting material formed using the said siloxane polymer composition. Since the said siloxane polymer composition can form the cured film excellent in transparency and scratch resistance, such a cured film can be applied to the technical use which requires high scratch resistance, transparency, etc., For example, such as a liquid crystal display element, a touch panel, etc. It can use suitably as a protective film, an interlayer insulation film, etc. of various devices.

<Formation method of hardened film>

Formation method of the cured film of this invention,

(1) a step of applying the siloxane polymer composition onto a substrate while relatively moving the discharge nozzle and the substrate to form a coating film,

(2) a step of irradiating at least a part of the coating film with radiation,

(3) a step of developing the coating film irradiated with the radiation, and

(4) heating the developed coating film. Hereinafter, each process is explained in full detail.

[Step (1)]

This process is corresponded to the process of apply | coating a radiation sensitive resin composition on a board | substrate, and forming a coating film. When apply | coating the conventional radiation sensitive resin composition, as the method, the discharge nozzle type coating methods, such as the spray method, the roll coating method, the rotary coating method (spin coating method), the slit coating method (slit die coating method), for example Although appropriate methods, such as the bar coating method and the inkjet coating method, are employ | adopted, the siloxane polymer composition of this invention can employ | adopt a discharge nozzle type coating method from the point which can apply | coat at high speed without application | coating unevenness. In the discharge nozzle type coating method in the step (1), a transparent conductive film is formed on one side of the substrate, and the siloxane polymer composition is applied onto the transparent conductive film while relatively discharging the discharge nozzle and the substrate, and then preferably Removes the organic solvent [C] by prebaking the coated surface to form a coating film.

As a board | substrate which can be used, glass, quartz, silicone, resin, etc. are mentioned, for example. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfones, polycarbonates, polyimides, ring-opening polymers of cyclic olefins, and hydrogenated substances thereof. Examples of the transparent conductive film include an NESA film made of tin oxide (SnO ₂ ) (registered trademark of US PPG), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. Although the conditions of prebaking differ also according to the kind, compounding ratio, etc. of each component, Preferably, it can be made into about 1 minute-10 minutes at 70 degreeC-120 degreeC.

[Step (2)]

In this process, it exposes at least one part of the formed said coating film. When exposing to a part of coating film, it exposes normally through the photo mask which has a predetermined pattern. As radiation used for exposure, the radiation in the range whose wavelength is 190 nm-450 nm is preferable, and the radiation which contains the ultraviolet-ray of 365 nm is especially preferable. The exposure amount in this process means the value which measured the intensity | strength in the wavelength of 365 nm of radiation with the illuminometer (OAI model 356, OAI Optical Associates company), 500J / m <2> -10,000J / m <2> is preferable, and 1,500 is preferable. J / m <2> -7,000J / m <2> is more preferable.

[Step (3)]

In this process, by developing the coating film after exposure, an unnecessary part (non-irradiation part of a radiation) is removed and a predetermined pattern is formed. As the developing solution used in the developing step, an alkaline aqueous solution is preferable. Examples of the alkali 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, and the like.

In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to such an aqueous alkali solution. As for the density | concentration of alkali in aqueous alkali solution, 0.1 mass% or more and 5 mass% or less are preferable from a viewpoint of obtaining suitable developability. As the developing method, for example, a suitable method such as a puddle method, a dipping method, a rocking dipping method or a shower method can be used. Although image development time changes with the composition of the said siloxane polymer composition, Preferably it is about 10 second-180 second. Subsequent to such developing treatment, for example, flowing water washing is performed for 30 seconds to 90 seconds, and then, for example, by air drying with compressed air or compressed nitrogen, a desired pattern can be formed.

[Step (4)]

In this process, hardening reaction of the said siloxane polymer composition can be accelerated | stimulated and a hardened | cured material can be obtained by heating a patterned thin film using heating apparatuses, such as a hotplate and oven. As heating temperature in this process, they are 120 degreeC-250 degreeC, for example. Although heating time changes with kinds of a heating apparatus, it can be set as 5 minutes-30 minutes, for example, when performing a heating process on a hotplate, and 30 minutes-90 minutes when performing a heating process in oven. A step baking method in which two or more heating steps are performed, or the like may be used.

The film thickness of the cured film thus formed is preferably 0.1 µm to 8 µm, more preferably 0.1 µm to 6 µm, and still more preferably 0.1 µm to 4 µm.

In the said formation method, the said siloxane polymer composition which can not only apply | coat at high speed but can form the cured film excellent in film thickness uniformity is used. Therefore, even if the ejection nozzle type coating method is adopted, high speed coating can be performed while preventing uneven coating. Moreover, by forming a pattern by exposure, image development, and heating using radiation sensitivity, the cured film which has a fine and fine pattern can be formed easily. In addition, the cured film formed as a protective film and an interlayer insulation film thus formed does not have coating unevenness and has high flatness, and can be suitably used for display elements such as liquid crystal display elements, organic EL display elements, and touch panels.

(Example)

Hereinafter, although this invention is explained based on an Example, this invention is not limitedly interpreted based on description of this Example.

Mw and Mn of the polymer were measured by gel permeation chromatography (GPC) under the following conditions.

Device: GPC-101 (Showa Denko KK)

Column: combine GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0mL / min

Sample concentration: 1.0 mass%

Sample injection volume: 100 μL

Detector: differential refractometer

Standard material: monodisperse polystyrene

The viscosity measured the viscosity of the said siloxane polymer composition at 25 degreeC using the E-type viscosity meter (VISKIIC ELD.R, Toki Sangyo Co., Ltd.). In addition, solid content concentration weighs 0.3 g of the said siloxane polymer compositions to an aluminum dish finely, adds about 1 g of diethylene glycol dimethyl ether, and after drying at 175 degreeC for 60 minutes on a hotplate, the mass before and after drying Obtained from

<[A] siloxane Polymer>

Synthesis Example 1

24 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, 39 mass parts of phenyl trimethoxysilanes, and 18 mass parts of 3-methacryloxypropyl trimethoxysilanes are made, and solution temperature will be 60 degreeC. Until heated. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 19 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and it preserve | saved for 2 hours. After cooling to 45 ° C, 28 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol which generate | occur | produced in water and hydrolysis condensation was removed. The hydrolysis-condensation product (A-1) was obtained by the above (solid content concentration = 35 mass%, Mw = 1,800, Mw / Mn = 2.2).

[Synthesis Example 2]

In a container with a stirrer, 23 parts by mass of propylene glycol monomethyl ether was added, followed by 24 parts by mass of methyltrimethoxysilane, 16 parts by mass of tetramethoxysilane, and 17 parts by mass of 3-methacryloxypropyltrimethoxysilane. It heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 21 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and it preserve | saved for 2 hours. After cooling to 45 ° C, 30 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol which generate | occur | produced in water and hydrolysis condensation was removed. The hydrolysis-condensation product (A-2) was obtained by the above (solid content concentration = 35 mass%, Mw = 2,500, Mw / Mn = 2.3)

[Synthesis Example 3]

27 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, and then 6 mass parts of methyl trimethoxysilanes, 20 mass parts of phenyl trimethoxysilanes, and 16 mass parts of (gamma)-glycidoxy propyl trimethoxysilane And 15 parts by mass of 3-methacryloxypropyltrimethoxysilane were added and heated until the solution temperature reached 60 ° C. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 16 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and it preserve | saved for 2 hours. After cooling to 45 ° C, 30 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol which generate | occur | produced in water and hydrolysis condensation was removed. The hydrolysis-condensation product (A-3) was obtained by the above (solid content concentration = 28 mass%, Mw = 1,800, Mw / Mn = 2.0).

[Synthesis Example 4]

27 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, and then 16 mass parts of methyl trimethoxysilanes, 20 mass parts of phenyl trimethoxysilanes, 6 mass parts of n-decyl trimethoxysilanes, 3- 15 mass parts of methacryloxypropyl trimethoxysilane was put, and it heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 16 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and it preserve | saved for 2 hours. After cooling to 45 ° C, 30 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol which generate | occur | produced in water and hydrolysis condensation was removed. The hydrolysis-condensation product (A-4) was obtained by the above (solid content concentration = 28 mass%, Mw = 1,800, Mw / Mn = 2.0).

Synthesis Example 5

27 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, Then, 16 mass parts of methyl trimethoxysilanes, 20 mass parts of phenyl trimethoxysilanes, 6 mass parts of trifluoropropyl trimethoxysilanes, 3 -15 parts by mass of methacryloxypropyl trimethoxysilane were added and heated until the solution temperature reached 60 ° C. After solution temperature reached 60 degreeC, 0.1 mass part of formic acid and 16 mass parts of ion-exchange water were put, it heated until it became 75 degreeC, and it preserve | saved for 2 hours. After cooling to 45 ° C, 30 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol which generate | occur | produced in water and hydrolysis condensation was removed. The hydrolysis-condensation product (A-5) was obtained by the above (solid content concentration = 28 mass%, Mw = 1,800, Mw / Mn = 2.0).

<Siloxane polymer composition>

Example 1

A solution containing the hydrolysis-condensation product (A-1) obtained in Synthesis Example 1 (amount corresponding to 100 parts by mass (solid content) of the hydrolysis-condensation product (A-1)) described later as a [B] radical polymerization initiator. (B-1) 3 mass parts and (C-1-1) and (C-1-2) which are mentioned later as an [C] organic solvent are added so that it may become desired solid content concentration, and it mentions later as [D] surfactant (D-1) The said siloxane polymer composition was prepared by mixing 0.20 mass part and filtering by the membrane filter of 0.2 micrometer of pore diameters.

[Examples 2 to 11 and Comparative Examples 1 to 4]

The compositions of Examples 2 to 11 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1, except that the type and the blending amount of each component were as described in Table 1. In addition, the numerical value of the [C] organic solvent shown in Table 1 is the mass% ratio of the (C1) organic solvent and (C2) organic solvent.

The other component used by the Example and comparative example shown in Table 1 is explained in full detail below.

[B] radical polymerization initiator

B-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (irgacure OXE02, Chiba Specialty Chemicals Co., Ltd.

B-2: 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyloxime)] (irgacure OXE01, Chiba Specialty Chemicals Co., Ltd.)

B-3: 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (irgacure 907, Chiba Specialty Chemicals Co., Ltd.)

B-4: 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morphonyl) phenyl] -1-butanone (irgacure 379EG, Chiba specialty chemical S Kabushi Kaisha)

[C] Organic solvent

(C1) organic solvent (an organic solvent having a vapor pressure of at least 0.1 mmHg and less than 1 mmHg at 20 ° C)

C-1-1: diethylene glycol ethyl methyl ether (20 degreeC, 0.75 mmHg)

C-1-2: ethylene glycol monobutyl ether (20 ° C, 0.76 mmHg)

(C2) organic solvent (an organic solvent having a vapor pressure of 1 mmHg or more and 20 mmHg or less at 20 ° C)

C-2-1: propylene glycol monomethyl ether (20 ° C, 6.7 mmHg)

C-2-2: Propylene glycol monomethyl ether acetate (20 ° C, 3.75 mmHg)

C-2-3: cyclohexanone (20 ° C, 3.4mmHg)

Solvent Used in Comparative Example

1,4-dioxane (20 DEG C, 29 mmHg)

Ethylene glycol (20 DEG C, 0.08 mmHg)

[D] surfactant

D-1: Silicone Surfactant (SH 8400 FLUID, Torre Dow Corning Silicon Co., Ltd.)

D-2: fluorine-based surfactant (aftergent FTX-218, Neos Co., Ltd.)

[E] ethylenically unsaturated compounds

E-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.)

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

E-3: Succinic acid modified dipentaerythritol pentaacrylate

[F] Acid or base generators

F-1: 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiopheniumtrifluoro methanesulfonate

F-2: 2-nitrobenzylcyclohexylcarbamate

&Lt; Formation of cured film &

Hexamethyldisilazane was apply | coated on the glass substrate of 550x650 mm, and it heated at 60 degreeC for 1 minute. The siloxane polymer composition of Examples 1-11 and Comparative Examples 1-4 was apply | coated on the chromium film-forming glass after this hexamethyldisilazane treatment using the slit-die coater (TOKAOKKA, TR632105-CL). After removing the solvent under vacuum by setting the attained pressure to 100 Pa and further prebaking at 90 ° C. for 2 minutes, a coating film having a film thickness of 3.0 μm was formed. Subsequently, it exposed by the exposure amount of 5,000 J / m <2> using the exposure machine (Canon Corporation, MPA-600FA). Subsequently, it develops at 25 degreeC with 0.05 mass% potassium hydroxide aqueous solution, wash | cleans water for 1 minute with ultrapure water, and heats for 60 minutes in 230 degreeC after that, and forms the protective film as a cured film of a film thickness (2.0 micrometers). did.

<Evaluation>

The following characteristics were evaluated about the siloxane polymer composition of Examples 1-11 and Comparative Examples 1-4, and the cured film formed from this siloxane polymer composition. The evaluation results are shown in Table 1 together. Moreover, the viscosity and solid content concentration of the said siloxane polymer composition are also shown in Table 1 at the point with the high correlation with an evaluation result.

[Appearance of Coating Film]

The siloxane polymer compositions of Examples 1 to 11 and Comparative Examples 1 to 4 were applied onto a 550 × 650 mm chromium film-forming glass using a slit die coater (TR632105-CL, Tokyo, Japan) and reduced to 0.5 Torr. After drying, the film was prebaked at 100 ° C. for 2 minutes on a hot plate to form a coating film, followed by exposure at an exposure dose of 2,000 J / m 2, thereby forming a film having a film thickness of 4 μm from the upper surface of the chromium film-forming glass. Under the sodium lamp, the appearance of the coating film was visually observed. At this time, streaks (stains of one or a plurality of straight lines occurring in the coating direction or the direction intersecting the coating), mist spots (cloud spots), pin trace spots (dot shapes occurring on the substrate support pin) Of the appearance of stains). The case where all of these stains are hardly seen was "A" (determined as good), and the case where a little was seen was made as "B" (determined to be a little defective), and the case where it was clearly seen was made into "C" (defect as bad).

[Film Thickness Uniformity]

The film thickness of the coating film on the chromium film-forming glass produced as mentioned above was measured using the needle contact measuring device (KLA Tencor company, AS200). Film thickness uniformity measured the film thickness in nine measuring points, and calculated it from the following formula. (X [mm], Y [mm]) satisfy the following equations: (275,20), (275,30), (275,60) 275, 100), (275, 325), (275, 550), (275, 590), (275, 620), (275, 630). When film thickness uniformity was 3% or less, it was judged that film thickness uniformity was favorable.

Film thickness uniformity (%) = {FT (X, Y) max-FT (X, Y) min} x 100 / {2 x FT (X, Y) avg.}

In the above formula, FT (X, Y) max is the maximum value in the film thicknesses at nine measurement points, and FT (X, Y) min is the minimum value in the film thicknesses at nine measurement points, and FT (X, Y) avg. Is an average value in the film thickness at nine measurement points.

[High speed applicability]

Applying a slit coater onto an alkali-free glass substrate of 550 mm x 650 mm, discharging the coating liquid from the nozzle so that the distance between the base and the nozzle is 150 m and the film thickness after exposure is 2.5 m as the coating condition. The moving speed of was varied in the range of 120 mm / sec-220 mm / sec, and the maximum speed | rate in which the irregularity of the strip | belt shape by a lack of liquid does not arise was calculated | required. It was judged that it was possible to cope with high speed application | coating when the stripe-shaped unevenness | production did not generate | occur | produce even at the speed of 180 mm / sec or more.

[Transparency]

About the board | substrate which has a cured film as a protective film formed as mentioned above, the light transmittance (%) of wavelength 400nm-800nm was measured using the spectrophotometer (Hitachi Seisakusho, 150-20 type double beam). The minimum value of the light transmittance (%) of wavelength 400nm-800nm was made into transparency. When this value was 95% or more, it was judged that the transparency of the protective film was good. In the case of the cured film serving as an interlayer insulating film, the film thickness thereof is 3.0 占 퐉, and only the film thickness differs from the cured film (2.0 占 퐉) serving as the protective film. Therefore, the evaluation of the transparency of the interlayer insulating film is the same as the evaluation of the transparency of the protective film. Judged.

[Scratch resistance]

The board | substrate which has a cured film as a protective film formed as mentioned above was reciprocated 10 times by applying the load of 200g on steel wool (# 0000) using the Hakjin type | mold abrasion tester. The situation of abrasions was visually confirmed, and the following references | standards evaluated.

A: No scratch at all

B: 1 to 3 flaws occur

C: 4 to 10 flaws

D: More than 11 flaws

It was judged that it was satisfactory scratch resistance if it was A or B. In addition, similarly to the evaluation of transparency, in the case of the interlayer insulating film, since the protective film and the film thickness were only different, it was judged that the evaluation of the scratch resistance of the interlayer insulating film was the same as the evaluation of the scratch resistance of the protective film.

From the result of Table 1, the said siloxane polymer composition of Examples 1-11 has less application | coating unevenness compared with the siloxane polymer composition of Comparative Examples 1-4, and it is possible to apply | coat high speed, and to the film thickness uniformity and appearance of the coating film obtained It became clear that it was good, too. Moreover, it became clear that it was excellent in transparency and scratch resistance about the cured film obtained as the protective film or interlayer insulation film obtained from the said siloxane polymer. Therefore, such a cured film is also suggested to be useful for a display element or a touch panel.

The present invention provides a siloxane polymer composition which is free of coating stains, which is excellent in appearance and which can achieve high flatness (film thickness uniformity) and high speed coating, and which can form a cured film as a protective film and an interlayer insulating film excellent in transparency and scratch resistance. Can provide. Since the said siloxane polymer composition exhibits effects, such as high speed applicability | paintability, it can apply suitably to a discharge nozzle type coating method etc .. Moreover, since the cured film formed from the said siloxane polymer composition shows outstanding transparency and abrasion resistance, it is not only for a display element but can be applied also as a protective film for interlayers, an interlayer insulation film, etc., and is advantageous also in cost.

Claims (11)

[A] siloxane polymer having a radical reactive functional group,
[B] a radical polymerization initiator, and
[C] contains an organic solvent,
Solid content concentration is 5 mass% or more and 30 mass% or less, the viscosity in 25 degreeC is 2.0 mPa * s or more and 10 mPa * s or less, and
[C] An organic solvent comprising (C1) an organic solvent having a vapor pressure of at least 0.1 mmHg and less than 1 mmHg at 20 ° C, and (C2) an organic solvent having a vapor pressure of at least 1 mmHg and at most 20 mmHg at 20 ° C. The siloxane polymer composition whose content is 10 mass% or more and 50 mass% or less with respect to the total amount of (C1) organic solvent and (C2) organic solvent. The method of claim 1,
[A] The siloxane polymer is a hydrolysis condensate of a hydrolyzable silane compound,
The hydrolyzable silane compound,
(a1) the hydrolyzable silane compound represented by the following formula (1),
(a2) A siloxane polymer composition comprising at least a hydrolyzable silane compound represented by the following formula (2):

(In formula (1), R <^1> is a C1-C6 alkyl group; R <^2> is an organic group containing a radical reactive functional group; p is an integer of 1-3, provided that R <^1> and R <^2> are ^two or more When, a plurality of R ¹ and R ² are each independently;
In formula (2), R <^3> is a C1-C6 alkyl group; R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, an epoxy group, an amino group or an isocyanate group; n is an integer from 0 to 20; q is an integer from 0 to 3; Provided that when R ³ and R ⁴ become plural, a plurality of R ³ and R ⁴ are each independently). delete The method of claim 1,
(C1) The organic solvent is at least 1 selected from the group consisting of diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, benzyl alcohol, dipropylene glycol monomethyl ether, and ethylene glycol monobutyl ether. A siloxane polymer composition that is an organic solvent of the species. The method of claim 1,
(C2) The organic solvent is diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone And at least one organic solvent selected from the group consisting of n-butyl acetate, methyl isobutyl ketone and methyl 3-methoxypropionate. The method of claim 1,
[D] further contains at least one surfactant selected from the group consisting of fluorine-based surfactants and silicone-based surfactants,
(D) The siloxane polymer composition whose content of surfactant is 0.01 mass part or more and 2 mass parts or less with respect to 100 mass parts of [A] siloxane polymers. The method of claim 1,
[E] A siloxane polymer composition further containing ethylenically unsaturated compounds other than the [A] siloxane polymer. The method of claim 1,
[F] A siloxane polymer composition further comprising a radiation sensitive acid generator or a radiation sensitive base generator. The method according to any one of claims 1, 2 and 4 to 8,
The siloxane polymer composition used for formation of the cured film as a protective film or an interlayer insulation film for display elements or a touch panel. The cured film formed using the siloxane polymer composition of any one of Claims 1, 2, and 4-8. (1) Process of applying the siloxane polymer composition of any one of Claims 1, 2, 4-8 on a board | substrate, moving a discharge nozzle and a board | substrate relatively, and forming a coating film,
(2) a step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation, and
(4) A method of forming a cured film comprising the step of heating the developed coating film.