JP2014161766A - Method of manufacturing substrate with coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a substrate with a coating by using a hydrolyzable silane compound which can easily manufacture the same with high productivity while maintaining quality and a yield by efficiently preparing a coating film-forming composition while suppressing generation of precipitates or the like.SOLUTION: A method of manufacturing a substrate with a coating includes: an A liquid preparing process of preparing an A liquid containing a nonionic surfactant; a B liquid preparing process of preparing a B liquid which contains a hydrolyzable silane compound and/or partial hydrolytic condensate, and silica fine particles, but does not contain the nonionic surfactant; a mixing process of mixing the A liquid and the B liquid stored at a storage temperature of -5°C or lower immediately after the B liquid preparing process at a temperature which does not generate precipitation to obtain a coating film-forming composition; and a coating film-forming process of applying and curing the coating film-forming composition on a substrate to form a coating.

Description

  The present invention relates to a method for producing a coated substrate having a coating on a substrate.

  Conventionally, a coated substrate in which a coating is formed on a substrate such as glass or resin has been widely used for various purposes. As a method for forming a film, for example, a silane compound having a hydrolyzable functional group (hereinafter also referred to as “hydrolyzable group”) by a sol-gel method with mild conditions (hereinafter referred to as “hydrolyzable silane compound”). Also known is a method of forming a silica-based film using the hydrolysis reaction (see, for example, Patent Document 1). In the case of forming a silica-based film, a film-forming composition containing a hydrolyzable silane compound and preferably a catalyst is prepared, and the composition is applied to the substrate, and then the hydrolyzable in the composition on the substrate. A method of forming a film by reacting and curing a silane compound is generally employed.

  In addition, various properties are required for the coating of a substrate with a coating, and various functional additives are often added. For example, fillers such as silica fine particles for improving mechanical properties, ultraviolet absorbers, infrared absorbers such as ITO fine particles, and the like. In the silica-based film, these functional additives are added to the film-forming composition containing the hydrolyzable silane compound and used for film formation. In order to obtain a uniform film, these additives are required to be present in the composition in a uniformly dissolved or dispersed state.

  Furthermore, when forming a film on a substrate using such a film-forming composition, for the purpose of improving the coating property of the composition on the substrate, a surfactant, an antifoaming agent, a viscosity modifier, etc. An additive such as an adhesion-imparting agent is often blended with the composition for the purpose of blending the additive into the composition or improving the adhesion of the resulting coating to the substrate.

  Here, in the case of producing a substrate with a film using the composition for forming a film containing the hydrolyzable silane compound, in consideration of production efficiency, the composition contains the catalyst and the above-mentioned in addition to the hydrolyzable silane compound. It is preferable that a large amount of raw material components such as a functional additive and other additives are mixed and prepared, and necessary amounts are sequentially used for film formation. In this case, the film-forming composition containing all raw material components is preferably stored frozen so that the hydrolysis condensation reaction of the hydrolyzable silane compound does not proceed.

International Publication No. 2005/095101

The present inventor has found that silica particles are precipitated when stored in a frozen state in the presence of a nonionic surfactant and silica particles.
Such precipitation has been a problem in terms of quality and yield.
It is an object of the present invention to maintain quality and yield by preparing a film-forming composition in a method for producing a film-coated substrate using a hydrolyzable silane compound while efficiently suppressing the occurrence of precipitation and the like. An object of the present invention is to provide a method for producing a coated substrate that is simple and can be produced with high production efficiency.

The present invention provides a method for producing a coated substrate having the following configurations [1] to [11].
[1] A liquid preparation step of preparing A liquid containing a nonionic surfactant
A B liquid preparation step of preparing a B liquid containing a silane compound having a hydrolyzable functional group and / or a partial hydrolysis condensate thereof, and silica fine particles and not containing a nonionic surfactant;
The mixing step of mixing the liquid A and the liquid B stored at a storage temperature of −5 ° C. or less immediately after the step of preparing the liquid B at a temperature at which no precipitate is generated, and obtaining the film forming composition, and the film The manufacturing method of the board | substrate with a film which has a film formation process which apply | coats the composition for formation on a board | substrate, and makes it a film by making it harden | cure.

[2] The difference between the viscosity of the B liquid immediately after the B liquid preparing process and the viscosity of the B liquid used in the mixing process, and the viscosity of the film forming composition immediately after the mixing process and the coating forming composition used in the coating The production method according to [1], in which the difference in viscosity (all the viscosities are those at 25 ° C.) is less than 1.5 mPa · s.
[3] The production method according to [1] or [2], wherein the liquid B preparation step includes an operation of reacting the solution containing the silane compound and the silica fine particles under conditions in which the silane compound is partially hydrolyzed and condensed. .

[4] The production method according to any one of [1] to [3], wherein the silane compound is a silane compound mainly having an alkoxy group having 1 to 10 carbon atoms as the hydrolyzable functional group.
[5] The storage temperature is a temperature at which a change in viscosity of the B solution measured at 25 ° C. after storage for 2 months immediately after the B solution preparing step can be made less than 1.5 mPa · s [1] to [ [4] The production method according to any one of [4].
[6] The production method according to any one of [1] to [5], wherein the storage temperature is −40 to −5 ° C.

[7] The manufacturing method according to any one of [1] to [6], wherein the mixing temperature in the mixing step is 0 to 30 ° C.
[8] Any of [1] to [7], wherein the content of the nonionic surfactant in the film-forming composition is 0.001 to 1.0% by mass with respect to the total amount of the composition. The manufacturing method as described in.
[9] The content of the silane compound and / or the partial hydrolysis condensate thereof in the film forming composition is 5.0 to 50.0% by mass with respect to the total amount of the composition. [8] The production method according to any one of [8].
[10] The content of the silica fine particles in the film forming composition is 0.5 to 50 parts by mass with respect to 100 parts by mass of the silane compound and / or a partial hydrolysis-condensation product thereof. ] The manufacturing method in any one of.
[11] The production method according to any one of [1] to [10], wherein the silica fine particles have an average particle diameter of 1 to 100 nm.

  According to the present invention, in the method for producing a substrate with a film using a hydrolyzable silane compound, the quality and yield can be maintained by preparing the film forming composition efficiently while suppressing the occurrence of precipitation or the like. However, it is possible to provide a method for producing a coated substrate that is simple and can be produced with high production efficiency.

Embodiments of the present invention will be described below. In addition, this invention is limited to the following description and is not interpreted.
The manufacturing method of the present invention is a method for manufacturing a substrate with a coating film having a coating film on the substrate, and includes the following steps (1) to (4).
(1) Liquid A preparation step for preparing liquid A containing a nonionic surfactant (hereinafter also referred to as (1) step)
(2) A B liquid preparation step (hereinafter referred to as (( 2) Also called a process.)
(3) Mixing step of mixing the liquid A and the liquid B stored at a storage temperature of −5 ° C. or less immediately after the liquid B preparation step to obtain a film-forming composition by mixing at a temperature at which no precipitate is generated ( Hereinafter, also referred to as (3) step.)
(4) A film forming step (hereinafter also referred to as (4) step) in which the film-forming composition is applied onto a substrate and cured to form a film.

Here, the functional group used in this specification is a term comprehensively indicating a reactive group, which is distinguished from a mere substituent, and includes, for example, a non-reactive group such as a saturated hydrocarbon group. Is not included in this. An addition polymerizable unsaturated double bond (ethylenic double bond) that is not involved in the formation of the main chain of the polymer compound that the monomer has in the side chain is one kind of functional group. Further, the term “(meth) acryl ...” such as (meth) acrylic acid ester used in the present specification is a term meaning both “acryl” and “methacryl”.
In the present specification, the viscosity means a viscosity at 25 ° C. unless otherwise specified. Moreover, in this specification, a viscosity is a viscosity measured using RE-80L (rotary viscometer, the Toki Sangyo make).

In the method for producing a film-coated substrate using a hydrolyzable silane compound, the present invention provides at least a nonionic surface active by the above-mentioned steps (1) and (2) when preparing a film-forming composition. A liquid containing an agent, a hydrolyzable silane compound and / or a partially hydrolyzed condensate thereof, and a B liquid containing silica fine particles are prepared separately, and the B liquid stored at least at a predetermined temperature in step (3) And liquid A are mixed while adjusting the temperature to obtain a film-forming composition, and this is applied onto the substrate in step (4), thereby efficiently preparing the film-forming composition while suppressing the occurrence of precipitation and the like. Thus, it has been found that a substrate with a film can be produced.
Therefore, if the composition for film formation is prepared in this way according to the present invention, a substrate with a film can be produced using a hydrolyzable silane compound with ease and production efficiency while maintaining quality and yield.

Hereinafter, each step will be described.
(1) A liquid preparatory process A liquid is a liquid composition containing a nonionic surfactant, and it is preferable to consist only of a nonionic surfactant and a solvent.
(Nonionic surfactant)
The nonionic surfactant is not particularly limited as long as it is blended with a film-forming composition used when a film is usually formed on a substrate using a hydrolyzable silane compound. For example, various organically modified polysiloxanes, fluorine-based surfactants, acrylic surfactants, etc. used for the purpose of improving coating properties such as flow properties, defoaming properties, leveling properties, repellency prevention and surface smoothness. Can be mentioned.

  As the organically modified polysiloxane, those that are soluble in a polar solvent are preferable, and specifically, polyether-modified polysiloxane is preferable. The polysiloxane is preferably polydimethylsiloxane. The degree of polymerization of the polysiloxane, the type of polyether group, and the number per molecule are appropriately adjusted according to the application. As the fluorine-based surfactant, perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, and fluorine telomer alcohol are preferable.

  Acrylic surfactants include acrylic (co) polymers and methacrylic (co) polymers. In the acrylic surfactant, polarity, substrate wettability, and the like are adjusted by introducing various substituents into the side chain via the carboxy group of (meth) acrylic acid. As the acrylic surfactant, an acrylic surfactant having a polyether group or a perfluoroalkyl group as the substituent is preferable. The degree of polymerization of the (meth) acrylic (co) polymer, the types of the polyether groups and perfluoroalkyl groups as the substituents, and the number per molecule are appropriately adjusted according to the application. A nonionic surfactant may be used independently or 2 or more types may be used together.

  A commercially available product can be used as the nonionic surfactant. Specifically, as for the following, trade names of BYK-Chemie Corporation include BYK-307, BYK-331, BYK-333 and the like for polyether-modified polysiloxane. Moreover, as a fluorine-type surfactant, BYK-340 (solid content: 10 mass%, solvent: dipropylene glycol monomethyl ether) and as an acrylic surfactant, BYK-355 (solid content: 52 mass%, solvent) : Propylene glycol monomethyl ether acetate) and the like.

  In addition, when a commercial item is a liquid composition containing a nonionic surfactant and a solvent, it is also possible to use a commercial item as A liquid as it is. As needed, you may add a solvent to the commercial item of a liquid composition further.

(solvent)
As the solvent used for the preparation of the liquid A, the same solvent as that used for the liquid B or a solvent compatible with the solvent is preferable. Specifically, the solvent used in the B liquid is as described later, and the solvent used in the A liquid is also a nonionic system contained in the A liquid from the solvent specifically shown as the solvent used in the B liquid. It is preferable to select appropriately according to the surfactant.

  The content of the nonionic surfactant in the liquid A is 5 to 50% by mass with respect to the total amount of the liquid A from the viewpoint of improving workability in the mixing step (3) and the film forming step (4). Preferably, 10 to 30% by mass is more preferable.

  The A liquid is mixed with the B liquid prepared in the following step (2) and at a predetermined ratio in the (3) step to form a film forming composition. As content of a nonionic surfactant when it is set as the film formation composition, 0.001-1.0 with respect to the film formation composition whole quantity as content which the function fully exhibits. % By mass is preferable, and 0.05 to 0.5% by mass is more preferable. Further, the content of the nonionic surfactant in the film forming composition is preferably 0.01 to 50.0% by mass relative to the total solid content of the film forming composition. .1 to 10.0% by mass is more preferable.

  A nonionic surfactant is mixed in a preferable range with respect to the total amount of the liquid A, that is, 5% to 50% by mass with the liquid B, so that the nonionic surfactant is mixed with the total amount of the film-forming composition. In the case of obtaining a film forming composition in which the content of the system surfactant is 0.001 to 1.0% by mass, the mixing ratio of the A liquid and the B liquid is 0 for the A liquid with respect to 100 parts by mass of the B liquid. The range of 0.01 to 25 parts by mass is preferable. A more preferable mixing ratio of the liquid A and the liquid B is such that the liquid A is in the range of 2 to 25 parts by mass with respect to 100 parts by mass of the liquid B.

  The method for preparing the liquid A is not particularly limited, and a general method is a method in which a nonionic surfactant and a solvent are charged at a predetermined ratio and mixed by an ordinary method. The temperature during mixing is not particularly limited, and is usually mixed at room temperature.

  The liquid A may be used for the mixing step (3) immediately after preparation, or may be used for the mixing step (3) after being stored for a predetermined period. In the mixing step (3), it is essential to mix at a temperature at which no precipitate is generated when the A liquid and the B liquid are mixed, in particular, the silica fine particles derived from the B liquid are not precipitated. Specifically, the mixing temperature is preferably 0 to 30 ° C, more preferably 10 to 25 ° C. The “temperature” at which the precipitate is not generated indicates the liquid temperature of the mixed liquid (including the mixed liquid in the middle of the mixing process) in which the liquid A and the liquid B are mixed. That is, the liquid temperature of the mixed liquid is preferably a temperature at which no precipitate is generated, specifically 0 to 30 ° C., and more preferably 10 to 25 ° C. The temperature at which the liquid A is subjected to the mixing step (3) is preferably adjusted to the same range as the mixing temperature.

  In the preparation of the liquid A, when the mixing step (3) is performed immediately after the nonionic surfactant and the solvent are mixed, for example, when the liquid A is mixed at room temperature, After adjusting the temperature of the liquid A to a preferred temperature, the liquid A is used for mixing.

  In the preparation of the liquid A, after the nonionic surfactant and the solvent are mixed, when there is a certain storage period until the mixing step (3), the liquid A is stored at room temperature for the storage period. What is necessary is just to adjust the temperature of A liquid to the preferable temperature in the said mixing immediately before the mixing process of 3).

  Alternatively, preparation of liquid A and liquid B is performed at the same time, liquid A and liquid B are stored together, and setting of the mixing temperature in (3) is performed simultaneously with liquid A and liquid B, liquid A May be set to the same temperature as the storage temperature of the B liquid, for example, −40 to −5 ° C.

(2) B liquid preparatory process B liquid is a liquid composition containing a hydrolysable silane compound and / or its partial hydrolysis-condensation product, and a silica fine particle, and normally contains a solvent similarly to A liquid.

(Hydrolyzable silane compound and / or partially hydrolyzed condensate thereof)
A hydrolyzable silane compound and / or a partial hydrolysis condensate thereof hydrolyzes a hydrolyzable group bonded to a silicon atom in the presence of a catalyst and water to form a hydroxyl group (silanol group) bonded to the silicon atom. Subsequently, silanol groups are dehydrated and condensed to form a siloxane bond represented by -Si-O-Si-, thereby increasing the molecular weight. Further, when a silane compound having a chlorine atom as a hydrolyzable group, that is, chlorosilane is used, in many cases, a chlorine atom and a silanol group of chlorosilane generate a siloxane bond by a dehydrochlorination reaction.

  Depending on the number of hydrolyzable groups bonded to the silicon atom by hydrolytic condensation of the hydrolyzable silane compound and / or its partial hydrolyzed condensate, linear polysiloxane or polysiloxane having a three-dimensional network structure Is formed into a film. The kind of the hydrolyzable silane compound and / or its partial hydrolysis condensate to be used is appropriately selected depending on the properties of the desired coating.

  Examples of the hydrolyzable silane compound include a tetrafunctional hydrolyzable silane compound in which four hydrolyzable groups are bonded to a silicon atom, and three hydrolyzable groups and one non-hydrolyzable group to a silicon atom. Examples thereof include a bonded trifunctional hydrolyzable silane compound and a bifunctional hydrolyzable silane compound in which two hydrolyzable groups and two non-hydrolyzable groups are bonded to a silicon atom. These may form a partial hydrolysis-condensation product by 1 type (s) or 2 or more types. In this specification, the term of a partial hydrolysis-condensation product includes not only a partial hydrolysis-condensation product by one hydrolyzable silane compound but also a partial hydrolysis co-condensation product by two or more hydrolyzable silane compounds. Used as a thing. Hereinafter, the hydrolyzable silane compound and / or the partial hydrolysis condensate thereof are also referred to as “hydrolyzable silane compounds”.

  Specific examples of hydrolyzable groups possessed by hydrolyzable silane compounds include alkoxy groups (including substituted alkoxy groups such as alkoxy-substituted alkoxy groups), alkenyloxy groups, acyl groups, acyloxy groups, oxime groups, and amide groups. Amino group, iminoxy group, aminoxy group, alkyl-substituted amino group, isocyanate group, chlorine atom and the like. Among these, organooxy groups such as an alkoxy group, alkenyloxy group, acyloxy group, iminoxy group, and aminoxy group are preferable, and an alkoxy group is particularly preferable. As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, an alkoxy group having 4 or less carbon atoms is more preferable, and a methoxy group and an ethoxy group are particularly preferable. When the hydrolyzable silane compound has a plurality of hydrolyzable groups, they may be the same as or different from each other.

  Specific examples of the tetrafunctional hydrolyzable silane compound include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetra n-butoxysilane, tetrasec-butoxysilane, and tetratert-butoxysilane. . In the present invention, tetraethoxysilane, tetramethoxysilane or the like is preferably used. These may be used alone or in combination of two or more.

  The non-hydrolyzable group possessed by the trifunctional hydrolyzable silane compound is preferably a monovalent organic group having a non-hydrolyzable functional group or having no functional group. It is more preferable that it is a monovalent organic group. The non-hydrolyzable monovalent organic group refers to an organic group in which the organic group and a silicon atom are bonded by a carbon-silicon bond, and a bond terminal atom is a carbon atom.

  Among the non-hydrolyzable monovalent organic groups, the non-hydrolyzable monovalent organic group having no functional group includes carbonization not having an addition polymerizable unsaturated double bond such as an alkyl group or an aryl group. A halogenated hydrocarbon group having no addition polymerizable unsaturated double bond such as a hydrogen group or a halogenated alkyl group is preferred. The number of carbon atoms of the non-hydrolyzable monovalent organic group having no functional group is preferably 20 or less, and more preferably 10 or less. The non-hydrolyzable monovalent organic group having no functional group is preferably an alkyl group having 4 or less carbon atoms or a phenyl group.

  Specific examples of the trifunctional hydrolyzable silane compound having a non-hydrolyzable monovalent organic group having no functional group include methyltrimethoxysilane, methyltriethoxysilane, methyltris (2-methoxyethoxy) silane, Examples include methyltriacetoxysilane, methyltripropoxysilane, methyltriisopropenoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltriacetoxysilane. . These may be used alone or in combination of two or more.

  Examples of the functional group in the non-hydrolyzable monovalent organic group having a functional group include an epoxy group, a (meth) acryloxy group, a primary or secondary amino group, an oxetanyl group, a vinyl group, a styryl group, a ureido group, and a mercapto group. Group, isocyanate group, cyano group, halogen atom and the like, and epoxy group, (meth) acryloxy group, primary or secondary amino group, oxetanyl group, vinyl group, ureido group, mercapto group and the like are preferable. In particular, an epoxy group, a primary or secondary amino group, and a (meth) acryloxy group are preferable. The monovalent organic group having an epoxy group is preferably a monovalent organic group having a glycidoxy group or a 3,4-epoxycyclohexyl group, and the organic group having a primary or secondary amino group is an amino group or a monoalkyl group. Monovalent organic groups having an amino group, a phenylamino group, an N- (aminoalkyl) amino group, and the like are preferable.

  Two or more functional groups in the monovalent organic group may exist, but a monovalent organic group having one functional group is preferable except for a primary or secondary amino group. In the case of a primary or secondary amino group, it may have two or more amino groups, in which case a monovalent organic group having one primary amino group and one secondary amino group For example, N- (2-aminoethyl) -3-aminopropyl group and 3-ureidopropyl group are preferable. The total number of carbon atoms of the monovalent organic group having these functional groups is preferably 20 or less, and more preferably 10 or less.

Specific examples of the trifunctional hydrolyzable silane compound having a non-hydrolyzable monovalent organic group having a functional group include the following compounds.
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropenoxysilane, p-styryltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 9,10-epoxydecyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane , 3-A Nopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, di- (3- (meth) acryloxy) propyltri Ethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltripropoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3- Examples include mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 2-cyanoethyltrimethoxysilane.

  Among these, preferable compounds include a glycidoxy group, a 2,3-epoxycyclohexyl group, an amino group, and an alkylamino group at the terminal of the alkyl group having 2 or 3 carbon atoms (the number of carbon atoms of the alkyl group is 4 or less). , A phenylamino group, an N- (aminoalkyl) amino group (the number of carbon atoms of the alkyl group is 4 or less), and a monovalent organic group having a functional group of any one of (meth) acryloxy group, and a carbon atom A trifunctional hydrolyzable silane compound in which three of the alkoxy groups having a number of 4 or less are bonded to a silicon atom.

  Specific examples of such a compound include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, di- (3- (meth) acryloxy) propyltriethoxysilane, and the like. From the viewpoint of reactivity with silane compounds, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltriethoxysilane and the like are particularly preferred. These may be used alone or in combination of two or more.

  The non-hydrolyzable group possessed by the bifunctional hydrolyzable silane compound is preferably a non-hydrolyzable monovalent organic group. The non-hydrolyzable monovalent organic group may have a functional group similar to that of the trifunctional hydrolyzable silane compound, if necessary.

  Specific examples of the bifunctional hydrolyzable silane compound include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi (2-methoxyethoxy) silane, dimethyldiacetoxysilane, dimethyldipropoxysilane, dimethyldiisopropenoxysilane, Dimethyldibutoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldi (2-methoxyethoxy) silane, vinylmethyldiisopropenoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, Phenylmethyldiacetoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropylmethyldipropoxysilane, 3, , 3-trifluoropropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercapto Examples include propylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and 2-cyanoethylmethyldimethoxysilane. These may be used alone or in combination of two or more.

  In the liquid B, the hydrolyzable silane compound is preferably present as a partially hydrolyzed condensate obtained by partial hydrolytic condensation of at least a part of the hydrolyzable silane compound. For example, a partially hydrolyzed condensate obtained by partially hydrolyzing and condensing a hydrolyzable silane compound in advance is mixed with components contained in the B liquid in addition to the hydrolyzable silane compounds described below, and the B liquid It is good. Alternatively, together with the hydrolyzable silane compound, after blending all the components contained in the B liquid in addition to the hydrolyzable silane compounds, the hydrolyzable silane compound is partially hydrolyzed and condensed to obtain the B liquid. Also good. The method of partially hydrolyzing and condensing the latter all components is preferred in that the hydrolyzable silane compound and the surface of the silica fine particles react to obtain a stronger coating.

  The content of the hydrolyzable silane compounds in the liquid B is 5 to 50% by mass with respect to the total amount of the liquid B from the viewpoint of improving the workability in the mixing step (3) and the film forming step (4). Preferably, 10 to 40% by mass is more preferable.

  The liquid B is mixed with the liquid A prepared in the step (1) and at a predetermined ratio in the step (3) to form a film forming composition. As described above, the mixing ratio of the A liquid and the B liquid is preferably in the range of 0.01 to 25 parts by mass, more preferably in the range of 2 to 25 parts by mass with respect to 100 parts by mass of the B liquid.

  As content of a hydrolysable silane compound when it is set as the film formation composition, 5.0-50.0 mass% is preferable with respect to the film formation composition whole quantity, and 10.0-40.0 is preferable. The mass% is more preferable. In addition, the content of the hydrolyzable silane compounds when used as the film forming composition is preferably 30 to 98% by mass, and preferably 70 to 95% by mass with respect to the total solid content of the film forming composition. Is more preferable.

(Silica fine particles)
The silica fine particles contained in the liquid B are components that improve the wear resistance of the resulting coating. The silica fine particles are preferably blended as colloidal silica. Colloidal silica refers to silica fine particles dispersed in water or an organic solvent such as methanol, ethanol, isobutanol, or propylene glycol monomethyl ether.

  The average particle diameter of the silica fine particles is preferably 1 to 100 nm as the average particle diameter measured by the BET method. If the average particle diameter is less than 1 nm, handling may not be easy, and if it exceeds 100 nm, the particles may diffusely reflect light, which may be undesirable in terms of the optical quality of the coating. The average particle diameter of the silica fine particles is particularly preferably 5 to 40 nm. Moreover, although colloidal silica can use both a water dispersion type and an organic solvent dispersion type, it is preferable to use an organic solvent dispersion type. Further, the colloidal silica may contain inorganic fine particles other than silica fine particles such as alumina sol, titania sol, and ceria sol.

  The content of the silica fine particles in the B liquid is preferably 0.5 to 50 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the hydrolyzable silane compounds. If the content is within the above range, in the resulting coating, the film-forming property is maintained while ensuring sufficient wear resistance, and the colorless transparency of the coating is reduced due to the occurrence of cracks and aggregation of silica fine particles. Can be prevented.

(solvent)
As the solvent of the liquid B, a solvent capable of dissolving hydrolyzable silane compounds and further dispersing silica fine particles is used. From this viewpoint, the solvent used for the liquid B preferably contains alcohol at a ratio of at least 20% by mass, more preferably at least 50% by mass with respect to the total amount of the solvent.

  Such alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 4- Methyl-2-pentanol, 2-butoxyethanol and the like are preferable. Among these, the boiling point is low because of the good solubility of the hydrolyzable silane compounds and the good coating property to the substrate. An alcohol of 80 to 160 ° C. is preferred. Specifically, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 4-methyl-2- Pentanol and 2-butoxyethanol are preferred. A solvent containing one or more selected from these alcohols is preferred, and in the case of a mixed solvent, a small amount of methanol may be contained.

  In addition, as a solvent used in the B liquid, when the hydrolyzable silane compound is partially hydrolyzed and condensed in advance to be contained in the B liquid, the raw material hydrolyzable silane compound is hydrolyzed in the production process. In the case of using lower alcohol or the like generated in the above, or colloidal silica dispersed in an organic solvent, the dispersed organic solvent is also included.

  Furthermore, as a solvent used for the liquid B, a solvent other than the above may be used in combination with a solvent other than alcohol that can be mixed with water / alcohol. Examples of such a solvent include acetone and acetylacetone. Ketones; esters such as ethyl acetate and isobutyl acetate; ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and diisopropyl ether.

  100-1900 mass parts is preferable with respect to 100 mass parts of total solids in B liquid, and, as for the quantity of the solvent in B liquid, 250-1000 mass parts is more preferable. In addition, in the film forming composition obtained by mixing the liquid B and the liquid A, the amount of the solvent is preferably 100 to 1900 parts by weight with respect to 100 parts by weight of the total solid content in the film forming composition, 250 -1000 mass parts is more preferable. If the content rate of the solvent in the composition for film formation is the said range, formation of a uniform coating film will be easy and there will also be no possibility that processing nonuniformity will generate | occur | produce in the obtained film.

(water)
The B liquid may contain water for hydrolyzing and condensing the hydrolyzable silane compounds contained therein. When the B liquid contains water, the content is preferably about 50 to 350 parts by mass with respect to 100 parts by mass of the total mass of the hydrolyzable silane compounds. In addition, in the film forming composition obtained by mixing the liquid B and the liquid A, a hydrolyzable silane compound using water in the atmosphere in the state of the film from the following film without containing water. Hydrolysis condensation can be carried out.

(Acid catalyst)
In the composition for forming a film obtained by mixing the B liquid and the A liquid, a film is formed by curing hydrolyzable silane compounds contained therein as described later. The liquid B preferably contains an acid catalyst for promoting the curing.

  Specific examples of the acid catalyst include inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid and phosphoric acid, formic acid, acetic acid, propionic acid, lactic acid, glycolic acid, oxalic acid, malonic acid, succinic acid, maleic acid, phthalic acid, citric acid. Examples thereof include carboxylic acids such as acid and malic acid, and sulfonic acids such as methanesulfonic acid. When the obtained film needs to be colorless and transparent, an acid having a pKa of the first proton (hereinafter also referred to as “pKa1”) of 1.0 to 5.0 is preferable as the acid catalyst. Specific examples of such acids include acetic acid (pKa1 = 4.76), lactic acid (pKa1 = 3.64), maleic acid (pKa1 = 1.84), malonic acid (pKa1 = 2.60), shu An acid (pKa1 = 1.04) etc. are mentioned. Among these, acetic acid is particularly preferable. One acid catalyst may be used alone, or two or more acid catalysts may be used in combination.

  The addition amount of the acid can be set without any limitation as long as it can function as a catalyst. Specifically, the amount of the acid is about 0.001 to 3.0 mol / L with respect to the total volume of the B liquid. . In the film forming composition obtained by mixing the B liquid and the A liquid, an amount of about 0.002 to 2.8 mol / L can be mentioned as the amount with respect to the total capacity. If the amount of the acid used exceeds the upper limit, the hydrolysis rate increases and the long-term storage property of the B liquid may not be sufficient.

  Liquid B may contain a curing catalyst as required in addition to the acid catalyst. Curing catalysts include aliphatic carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, succinic acid, etc.), alkali metal salts such as lithium salt, sodium salt, potassium salt; benzyltrimethylammonium salt, tetramethylammonium salt Quaternary ammonium salts such as salts and tetraethylammonium salts; metal alkoxides and chelates such as aluminum, titanium and cerium; ammonium perchlorate, ammonium chloride, ammonium sulfate, sodium acetate, imidazoles and their salts, ammonium trifluoromethylsulfonate, Bis (tolufluoromethylsulfonyl) bromomethylammonium and the like can be mentioned.

(Other ingredients)
The liquid B may optionally contain an additive that the film-forming composition normally contains depending on the purpose. As additives, organic ultraviolet absorbers such as benzophenones, triazines, benzotriazoles, cyanoacrylates, azomethines, indoles, salicylates, anthracene, indium tin oxide, antimony tin oxide, alumina, Preferred examples include ultrafine particles of metal oxides such as zirconia and titania, coloring materials such as dyes or pigments, antifouling materials, light stabilizers, flexibility imparting components such as various resins, and the like. Liquid B does not contain a nonionic surfactant. That the B liquid does not contain a nonionic surfactant means that the content of the nonionic surfactant with respect to the total amount of the B liquid is less than 0.001% by mass.

  The flexibility-imparting component is a component that imparts flexibility to a coating obtained by curing hydrolyzable silane compounds, and is a component that contributes to preventing cracks in the coating. The addition of the flexibility imparting component is particularly effective when a tetrafunctional hydrolyzable silane compound is used. Examples of the flexibility-imparting component include silicone resins, acrylic resins, polyester resins, polyurethane resins, hydrophilic organic resins containing polyoxyalkylene groups, various organic resins such as epoxy resins, and organic compounds such as glycerin. it can.

  The amount of the additive added is 0.01 to 20 parts by mass for each additive with respect to 100 parts by mass of the total solid content when the composition for forming a film obtained by mixing the B liquid and the A liquid is used. Is preferred. Excessive addition of the additive may cause a decrease in the performance of the resulting film.

  The method for preparing the liquid B is not particularly limited, and a predetermined amount of hydrolyzable silane compounds and silica fine particles as essential components, an arbitrary amount of the optional components described above, and an appropriate amount of solvent are charged and mixed by a normal method. The method to do is common.

  The liquid B may contain a hydrolyzable silane compound as a hydrolyzable silane compound, may contain a partially hydrolyzed condensate thereof, or may contain both. In any case, in the mixing for preparing the liquid B, the hydrolysis condensation reaction proceeds if an acid catalyst is present. Therefore, when the hydrolyzable silane compounds contained in the B liquid are subjected to the mixing step (3) in the state of the hydrolyzable silane compound, the addition of the acid catalyst to the B liquid prepares the B liquid. Preferably at the end of the mixing. Moreover, it is preferable to make the temperature in the case of mixing for preparing B liquid into the low temperature of 10-35 degreeC.

  When liquid B contains a partially hydrolyzed condensate of a hydrolyzable silane compound as a hydrolyzable silane compound, a reaction in which a hydrolyzable silane compound is added in advance by a conventional method, for example, an acid catalyst, water, a solvent, etc. The partial hydrolysis-condensation product may be separated from the reaction liquid obtained by partial hydrolysis-condensation at 10 to 35 ° C. for 1 to 3 hours in the liquid, or may be used for preparation of the B liquid as it is. When using a partial hydrolysis-condensation product, B liquid is obtained by mixing a partial hydrolysis-condensation product and components, such as silica fine particles which B liquid contains other than that. When using a reaction solution, components such as acid catalyst, water, and solvent that are already contained are added as necessary, and other components such as silica fine particles contained in solution B are added. Mix. Further, a hydrolyzable silane compound can be added thereto.

As a method for preparing the liquid B containing a hydrolyzable silane compound partially hydrolyzed condensate, a solution containing a hydrolyzable silane compound and silica fine particles is reacted under conditions where the hydrolyzable silane compound is partially hydrolyzed and condensed. You may take the method including operation to make.
Specifically, all the components including silica fine particles finally contained in the liquid B together with the hydrolyzable silane compound that is the raw material of the partial hydrolysis-condensation product are charged into a container, and this is a condition that enables partial hydrolysis-condensation reaction. For example, you may employ | adopt the method of mixing on the conditions of temperature and time similar to the above. According to this method, operations such as mixing for preparing the liquid B can be performed at a time, which is preferable in terms of productivity. Moreover, the stability of the silica fine particles in the B liquid is also increased, which is preferable.

  In the B liquid thus obtained, the viscosity immediately after being prepared is preferably 1.0 to 4.5 mPa · s at 25 ° C., more preferably 2.0 to 3.5 mPa · s. In addition, the viscosity immediately after preparation means the viscosity measured within 3 hours after completion | finish of operation for preparation of B liquids, such as mixing. Here, in the step (2), the viscosity of the B liquid measured within 1 hour, 10 minutes or 5 minutes after the completion of the operation for preparing the B liquid may be within the above viscosity range. In addition, after the operation for preparing the liquid B is completed and before the viscosity is reached, the conditions described below for storage without substantially changing the viscosity, specifically, −5 ° C. or lower. It is preferable to place the liquid B under temperature conditions.

  In the production method of the present invention, the solution B is stored at a storage temperature of −5 ° C. or less from immediately after the preparation step until it is subjected to the mixing step (3). The liquid B is stored in the temperature condition for a predetermined period and then subjected to the mixing step (3). Depending on the storage period and environment, the hydrolyzable silane compounds contained in the liquid B undergo a partial hydrolysis condensation during the storage period. In order to stably store the liquid B, the hydrolyzable silane compounds should be partially hydrolyzed and condensed to some extent in advance as described above, rather than being present in the liquid B as the hydrolyzable silane compound itself. Is preferred. Here, the storage temperature means the liquid temperature of the B liquid.

  By storing the B liquid under the above temperature conditions, it can be stored without substantially changing the viscosity during a predetermined storage period. Thereby, for example, if the liquid A and the liquid B are separately produced in large quantities and then the necessary amount can be used when necessary, the productivity can be improved. In consideration of storage costs, it is preferable that both the liquid A and the liquid B are provided to the mixing step (3) within 2 months after preparation, and a film is preferably formed in the step (4). Within is more preferable.

  As described above, the viscosity rises when the hydrolyzable silane compounds contained in the liquid B undergo a partial hydrolysis condensation during the storage period. In the method of the present invention, the liquid B is in a state in which the viscosity is not substantially changed after preparation and when it is subjected to the mixing step (3). “There is substantially no change in viscosity” means that the change in viscosity is less than 1.5 mPa · s.

  The difference between the viscosity immediately after the preparation of the B liquid and the viscosity of the B liquid when it is used in the mixing step (3) is preferably less than 1.0 mPa · s and less than 0.5 mPa · s. More preferred. In addition, the viscosity of B liquid at the time of using for the mixing process of (3) means the viscosity measured within 3 hours before this mixing. Here, the viscosity of the liquid B when subjected to the mixing step (3) is the difference between the viscosity immediately after preparation of the liquid B as the viscosity of the liquid B measured within 1 hour before the mixing. Preferably, the difference between the viscosity of B liquid measured within 10 minutes before mixing and the viscosity immediately after preparation of B liquid is within the above range, It is particularly preferable that the difference between the viscosity of the liquid B measured within 5 minutes and the viscosity immediately after the preparation of the liquid B is in the above range.

  In order to store B liquid from immediately after the preparation step (2) to immediately before the mixing step (3) without substantially changing the viscosity, the storage temperature of B liquid is changed as described above. Is maintained at a temperature of −5 ° C. or lower. The term “immediately after the preparation step for the B liquid” means up to 3 hours after the completion of the operation for preparing the B liquid. The time required from the end of the operation for preparing the B liquid to the start of storage when the storage period of −5 ° C. or less is started is preferably within 1 hour, more preferably within 10 minutes, particularly preferably 5 Within minutes. Further, “immediately before the mixing step (3)” means up to 3 hours before the start of the mixing operation. The time required from the end of the storage period for storing the B liquid at −5 ° C. or less until the start of the operation of mixing the A liquid and the B liquid is preferably within 1 hour, more preferably within 10 minutes, particularly Preferably it is within 5 minutes.

  The storage temperature of the B liquid is preferably a temperature at which the change in the viscosity of the B liquid can be made less than 1.5 mPa · s by storage for 2 months immediately after the B liquid preparation step. Although it depends on the composition of the B liquid, specifically, the storage temperature of the B liquid is preferably −40 to −5 ° C., more preferably −25 to −10 ° C.

  Here, in the mixing step (3), it is essential to mix at a temperature at which no precipitate is generated when the A liquid and the B liquid are mixed, in particular, the silica fine particles derived from the B liquid are not precipitated. Specifically, the mixing temperature is preferably 0 to 30 ° C, more preferably 10 to 25 ° C. The temperature at which the liquid B is subjected to the mixing step (3) is preferably adjusted to the same range as the mixing temperature.

  In the preparation of the liquid B, after the liquid B is mixed, the liquid B is stored at a temperature of −5 ° C. or lower until the mixing step (3). And just before the mixing process of the following (3), what is necessary is just to adjust the temperature of B liquid to the preferable temperature at the time of the mixing of (3) process.

(3) Mixing step In this step, the liquid A prepared in the step (1) and the liquid prepared in the step (2) (2) so that the viscosity does not substantially change immediately after the step (2) The composition for forming a film is prepared by mixing the liquid B stored at a storage temperature of −5 ° C. or less immediately after the process at a mixing temperature at which no precipitate is generated, in particular, the silica fine particles brought from the liquid B are not precipitated. obtain.

  As the mixing temperature, specific temperatures are as already shown above. In addition, the temperature of mixing in this step, that is, the mixing temperature refers to the temperature of the liquid material in which the liquid A and the liquid B are mixed during the mixing operation. The mixing operation of the A liquid and the B liquid is performed by a normal method. A predetermined amount of the A liquid and a predetermined amount of the B liquid may be charged simultaneously and mixed, or the predetermined amount of the other may be gradually added to one of the predetermined amounts or added in several times. .

  Temperature control during the mixing operation is performed by monitoring with a thermocouple. Alternatively, since the liquid A and the liquid B do not enter and exit during mixing, the mixing operation can be completed without particularly controlling the temperature of the mixed liquid if the both are adjusted within the range of the mixing temperature.

  Here, among the A liquid and B liquid used in the mixing step (3), at least the B liquid is stored at a storage temperature of −5 ° C. or lower. In order to adjust the B liquid having a temperature of −5 ° C. or lower to a preferable mixing temperature of 0 to 30 ° C., for example, the B liquid taken out from a storage or the like of −5 ° C. or lower is set to a predetermined mixing temperature. It is preferable to leave it in a constant temperature bath for 3 hours or less until the mixing temperature is reached. When the A liquid is stored in the same manner as the B liquid, the temperature of the A liquid may be adjusted in the same manner as the B liquid.

  As the mixing ratio of the liquid A and the liquid B, the nonionic surfactant is preferably 0.001 to 0.1% by mass relative to the total amount of the film forming composition in the film forming composition to be obtained. The amount is preferably 0.05 to 0.5% by mass, and the content of the hydrolyzable silane compounds is preferably 5 to 30% by mass, more preferably, based on the total amount of the film-forming composition. The quantity used as 10-25 mass% is mentioned. As a mixing ratio of such A liquid and B liquid, the range of 0.01-25 mass parts of A liquid is mentioned with respect to 100 mass parts of B liquid, The range of 2-25 mass parts is more preferable.

  In the film-forming composition thus obtained, the viscosity immediately after mixing is preferably 1.5 to 4.0 mPa · s at 25 ° C., more preferably 2.0 to 3.0 mPa · s. The viscosity immediately after mixing refers to the viscosity measured within 3 hours after completion of the mixing operation. Here, in the step (3), the viscosity of the film-forming composition measured within 1 hour, within 10 minutes or within 5 minutes after completion of the mixing operation may be within the above viscosity range. Moreover, it is preferable to start the operation of applying the film-forming composition on the substrate in the step (4) described below after the mixing operation is completed until the viscosity is reached.

(4) Film Forming Process This process is a process in which the film forming composition obtained in the process (3) is applied on a substrate and cured to form a film. Preferably, after the step (3), the obtained film-forming composition is maintained at a temperature at which no precipitate is generated, in particular, the silica fine particles brought from the liquid B are not precipitated, compared to immediately after the mixing step. This is a step of coating on a substrate in a state where the viscosity is not substantially changed, and further curing to form a film.

  (3) The film-forming composition obtained in the step can be maintained at a temperature at which the precipitate is not generated until the silica fine particles brought in from the liquid B are not precipitated until the composition is applied onto the substrate. preferable. When the film-forming composition is held at such a temperature, the partial hydrolytic condensation of hydrolyzable silane compounds proceeds at a certain rate with the passage of time. Therefore, it is preferable that the film-forming composition is applied in a state where the viscosity is not substantially changed when applied onto the substrate as compared to immediately after the step (3).

  The fact that there is substantially no change in viscosity means that the change in viscosity is less than 1.5 mPa · s as described above. (3) The viscosity of the composition for forming a film immediately after the step and the composition for forming a film used for coating The difference in viscosity between the objects is preferably less than 1.0 mPa · s. In addition, the viscosity of the composition for film formation when it is used for coating refers to the viscosity measured within 3 hours before coating. Here, the viscosity of the composition for forming a film when it is used for coating is the viscosity of the composition for forming a film measured within 1 hour before the coating, as the viscosity of the composition for forming a film immediately after the step (3). The difference from the viscosity is preferably within the above range, and as the viscosity of the film-forming composition measured within 10 minutes before the coating, the difference from the viscosity of the film-forming composition immediately after the step (3) Is more preferably within the above range, and the difference between the viscosity of the film forming composition immediately after the step (3) and the viscosity of the film forming composition measured within 5 minutes before the coating is within the above range. It is particularly preferred that From this point of view, although depending on the holding temperature of the film-forming composition, it is preferable to start application of the step (4) within 3 hours after the completion of the step (3), and more preferably within 2 hours. Within 1 hour is particularly preferred.

  The film-forming composition obtained in the above steps (1) to (3) is a film-forming composition that is efficiently prepared with generation of precipitation and the like suppressed. Using this film-forming composition while maintaining a prepared good state, a normal method of forming a cured film on a substrate with a composition containing a hydrolyzable silane compound, for example, by the method shown below If a substrate with a coating is manufactured, the substrate with a coating can be manufactured easily and efficiently while maintaining quality and yield.

  The substrate used for the coated substrate to which the production method of the present invention is applied is not particularly limited as long as it is a substrate made of a material that is generally required to be coated, and is a metal, resin, glass, ceramic, or a combination thereof ( A substrate made of a composite material, a laminated material or the like is preferably used. A transparent substrate such as glass or resin is particularly preferable. Examples of the glass include ordinary soda lime glass, borosilicate glass, non-alkali glass, and quartz glass. Among these, soda lime glass is particularly preferable. Examples of the resin include acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as polyphenylene carbonate, and aromatic polyester resins such as polyethylene terephthalate (PET).

  The shape of the substrate may be a flat plate, or the entire surface or a part thereof may have a curvature. Although the thickness of a board | substrate can be suitably selected by the use of a board | substrate with a film, generally it is preferable that it is 1-10 mm.

  The method for coating the film-forming composition on the substrate is not particularly limited as long as it is a method capable of forming a uniform coating film. For example, methods such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, die coating, and hand coating can be used. By these methods, the composition for forming a coating film is applied onto a substrate after adjusting the thickness of the coating film so that the finally obtained coating film has a predetermined thickness. The thickness of the coating to which the production method of the present invention is applied is not particularly limited. It is appropriately selected according to the application.

  After forming the coating film, the solvent is usually removed from the coating film. The solvent is preferably removed by heating and / or drying under reduced pressure. After forming the coating film on the substrate, it is preferable to perform temporary drying at a temperature of about room temperature to 120 ° C. from the viewpoint of improving the leveling property of the coating film. Usually, during the temporary drying operation, the solvent is removed in parallel with the temporary drying operation, so that the solvent removal operation is included in the temporary drying. The time for temporary drying, that is, the time for removing the solvent, is preferably about 3 seconds to 2 hours, although it depends on the film-forming composition.

  At this time, it is preferable that the solvent is sufficiently removed, but it may not be completely removed. That is, a part of the solvent can remain in the film as long as the performance of the finally obtained film is not affected. In addition, when heating for removing the solvent, heating for curing the hydrolyzable silane compounds, which is performed as necessary, and heating for removing the solvent, which are generally temporary Drying may be performed continuously.

  After removing the solvent from the coating film as described above, the hydrolyzable silane compounds are cured. This reaction can be carried out at room temperature or under heating. When a cured product (polysiloxane film) is formed under heating, the upper limit of the heating temperature is preferably 200 ° C., and particularly preferably 190 ° C., because the cured product contains an organic component. Since the cured product can be generated even at normal temperature, the lower limit of the heating temperature is not particularly limited. However, when the promotion of the reaction by heating is intended, the lower limit of the heating temperature is preferably 60 ° C, more preferably 80 ° C. Therefore, this heating temperature is preferably 60 to 200 ° C, more preferably 80 to 190 ° C. The heating time is preferably from several minutes to several hours, although it depends on the composition of the film-forming composition.

  Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Examples 1, 8, 10, and 12 described below are examples, and examples 2 to 7, 9, 11, and 13 are comparative examples. In addition, the constituent compounds of drugs described by trade names in each example are shown below.

<Commercial product used in the example (product name)>
Solmix AP-1; mixed alcohol of ethanol: 2-propanol: methanol = 85.5: 13.4: 1.1 (mass ratio) manufactured by Nippon Alcohol Sales Co., Ltd .; methanol silica sol; manufactured by Nissan Chemical Industries, average Colloidal silica / nonionic surfactant in which silica fine particles having a primary particle size of 10 to 20 nm are dispersed in methanol at a solid content concentration of 30% by mass;

(Example 1)
32.5 g of Solmix AP-1, 17.8 g of tetramethoxysilane, 1.2 g of methanol silica sol as colloidal silica, 16.9 g of acetic acid and 31.6 g of ion-exchanged water were charged and stirred at 25 ° C. for 1 hour. B1 liquid was obtained. The viscosity of the B1 liquid obtained immediately after the completion of stirring was measured. Further, 0.06 g of BYK-307 and 0.44 g of Solmix AP-1 were stirred at 25 ° C. for 30 minutes to obtain A1 solution.
B1 liquid and A1 liquid were put in a freezer at -20 ° C. and stored for 2 months immediately after stirring.

After storage for 2 months, the B1 liquid and the A1 liquid were taken out from the freezer and visually checked for precipitation. About B1 liquid and A1 liquid taken out from the freezer, temperature was adjusted to 25 degreeC within 3 hours. Viscosity was measured about B1 liquid. Immediately after the measurement, the B1 liquid and the A1 liquid were mixed and stirred at a temperature of 25 ° C. for 10 minutes to obtain a film-forming composition 1.
The presence or absence of precipitation in the obtained film-forming composition 1 was confirmed visually.
The difference between the viscosity immediately after preparation of the B1 solution and the viscosity after storage was determined. The evaluation results are shown in Table 2 together with the production conditions and the presence or absence of precipitation. In addition, all the viscosity was measured using RE-80L (rotary viscometer, the Toki Sangyo make).

  2 g of the film-forming composition 1 immediately after obtained above is applied to a glass substrate (10 cm square, 3.5 mm thickness) by spin coating, and heated in a drying oven at 180 ° C. for 30 minutes to provide a substrate with a film 1 was obtained. In addition, since the composition 1 for film formation was applied immediately after preparation, the viscosity change is 0. Hereinafter, in the example in which the coating film-forming composition was applied immediately after preparation, the viscosity change is similarly 0. The resulting coating was transparent with no foreign matter.

(Example 2)
A film-forming composition 2 was obtained in the same manner as in Example 1, except that the mixing temperature of the B1 liquid and the A1 liquid was changed to -10 ° C. The presence or absence of precipitation in the obtained film-forming composition 2 was visually confirmed. The results are shown in Table 2 together with the production conditions and the presence or absence of precipitation.
Moreover, the board | substrate 2 with a film was obtained like Example 1 except having used 2g of the composition 2 for film formation immediately after obtained. The obtained film was cloudy.

(Example 3)
After obtaining the B1 solution in the same manner as in Example 1, 0.06 g of BYK-307 and 0.44 g of Solmix AP-1 were further added thereto, and the mixture was stirred at 25 ° C. for 10 minutes, followed by coating composition 3 Got. In addition, since the nonionic surfactant etc. were added to the B1 liquid immediately after preparation, the viscosity change is zero. The viscosity of the film-forming composition 3 obtained immediately after the stirring was measured. Moreover, the presence or absence of precipitation was confirmed visually.
Immediately after completion of stirring, the film-forming composition 3 was placed in a freezer at -20 ° C. and stored for 2 months. After storage for 2 months, the film-forming composition 3 was taken out of the freezer and visually checked for precipitation. About the composition 3 for film formation taken out from the freezer, temperature was adjusted to 25 degreeC within 3 hours, the viscosity was measured, and the difference of the viscosity immediately after preparation and the viscosity after storage was calculated | required. The evaluation results are shown in Table 2 together with the production conditions and the presence or absence of precipitation.

  Further, after storing at the above temperature for 2 months, a coated substrate 3 was obtained in the same manner as in Example 1 except that 2 g of the film-forming composition 3 taken out from the freezer and adjusted to 25 ° C. was used. The obtained film was cloudy.

(Examples 4 to 6)
Example 3 was produced except that the film-forming composition 3 was produced in the same manner as Example 3 and then the storage temperature was changed to −10 ° C. (Example 4), −5 ° C. (Example 5), and 5 ° C. (Example 6). Similarly, the film-forming composition 3 was stored in a storage such as a freezer.
After storage for 2 months, each of the film-forming compositions 3 was taken out from a storage such as a freezer and visually checked for precipitation. About the composition 3 for film formation taken out from the freezer, temperature was adjusted to 25 degreeC within 3 hours, the viscosity was measured, and the difference of the viscosity immediately after preparation and the viscosity after storage was calculated | required. The evaluation results are shown in Table 2 together with the production conditions and the presence or absence of precipitation.

  Moreover, after storing at the said temperature for 2 months, it took out from storages, such as a freezer, and obtained the board | substrates 4-6 with a film similarly to Example 1 except having used 2g of the composition 3 for film formation which was 25 degreeC. It was. The resulting coating was cloudy in all cases.

(Example 7)
After obtaining the B1 solution in the same manner as in Example 1, 0.01 g of BYK-307 and 0.83 g of Solmix AP-1 were further added thereto, and the mixture was stirred at 25 ° C. for 10 minutes, followed by coating forming composition 4 Got. The viscosity of the film-forming composition 4 obtained immediately after the stirring was measured. Moreover, the presence or absence of precipitation was confirmed visually.
Immediately after the completion of stirring, the film-forming composition 4 was placed in a freezer at −20 ° C. and stored for 2 months. After storage for 2 months, the film-forming composition 4 was taken out of the freezer and visually checked for precipitation. About the film forming composition 4 taken out from the freezer, the temperature was adjusted to 25 ° C. within 3 hours, and the viscosity was measured to determine the difference between the viscosity immediately after preparation and the viscosity after storage. The evaluation results are shown in Table 2 together with the production conditions and the presence or absence of precipitation.

  Further, after storing at the above temperature for 2 months, a coated substrate 7 was obtained in the same manner as in Example 1 except that 2 g of the film-forming composition 4 taken out from the freezer and adjusted to 25 ° C. was used. The obtained film was cloudy.

(Example 8)
In the same manner as in Example 1, a B1 solution was obtained. The viscosity of the B1 liquid obtained immediately after the completion of stirring was measured. Further, 0.10 g of BYK-331 and 0.73 g of Solmix AP-1 were stirred at 25 ° C. for 30 minutes to obtain A2 liquid.
B1 liquid and A2 liquid were put into a -20 ° C. freezer immediately after stirring and stored for 2 months.

After storage for 2 months, the B1 liquid and the A2 liquid were taken out from the freezer and visually checked for the presence of precipitation. About B1 liquid and A2 liquid which were taken out from the freezer, temperature was adjusted to 25 degreeC within 3 hours. Viscosity was measured about B1 liquid. Immediately after the measurement, the liquid B1 and the liquid A2 were mixed and stirred at a temperature of 25 ° C. for 10 minutes to obtain a film-forming composition 5.
The presence or absence of precipitation in the obtained film-forming composition 5 was visually confirmed.
The difference between the viscosity immediately after preparation of the B1 solution and the viscosity after storage was determined. The evaluation results are shown in Table 2 together with the production conditions and the presence or absence of precipitation.

  2 g of the film-forming composition 5 just obtained as described above was applied to a glass substrate (10 cm square, 3.5 mm thickness) by a spin coating method, and heated in a drying furnace at 180 ° C. for 30 minutes to provide a substrate with a film 8 was obtained. The resulting coating was transparent with no foreign matter.

(Example 9)
After obtaining the B1 solution in the same manner as in Example 1, 0.10 g of BYK-331 and 0.73 g of Solmix AP-1 were further added thereto, and the mixture was stirred at 25 ° C. for 10 minutes, followed by coating forming composition 6 Got. The viscosity of the film-forming composition 6 obtained immediately after the stirring was measured. Moreover, the presence or absence of precipitation was confirmed visually.
The film-forming composition 6 was placed in a freezer at −20 ° C. and stored for 2 months immediately after stirring. After storage for 2 months, the film-forming composition 6 was taken out of the freezer and visually checked for the presence of precipitation. About the film forming composition 6 taken out from the freezer, the temperature was adjusted to 25 ° C. within 3 hours, and the viscosity was measured to determine the difference between the viscosity immediately after preparation and the viscosity after storage. The evaluation results are shown in Table 2 together with the production conditions and the presence or absence of precipitation.

  Further, after storing at the above temperature for 2 months, a coated substrate 9 was obtained in the same manner as in Example 1 except that 2 g of the film-forming composition 6 was removed from the freezer and adjusted to 25 ° C. The obtained film was cloudy.

(Example 10)
In the same manner as in Example 1, a B1 solution was obtained. The viscosity of the B1 liquid obtained immediately after the completion of stirring was measured. Moreover, 0.5 g of BYK-340 was directly prepared as an A3 solution.
Liquid B1 and liquid A3 were placed in a freezer at −20 ° C. and stored for 2 months immediately after completion of stirring or immediately after preparation.

After storage for 2 months, the B1 liquid and the A3 liquid were taken out from the freezer and visually checked for the presence of precipitation. About B1 liquid and A3 liquid taken out from the freezer, temperature was adjusted to 25 degreeC within 3 hours. Viscosity was measured about B1 liquid. Immediately after the measurement, the solution B1 and the solution A3 were mixed and stirred at a temperature of 25 ° C. for 10 minutes to obtain a film-forming composition 7.
The presence or absence of precipitation in the obtained film-forming composition 7 was visually confirmed.
The difference between the viscosity immediately after preparation of the B1 solution and the viscosity after storage was determined. The evaluation results are shown in Table 2 together with the production conditions and the presence or absence of precipitation.

  2 g of the film-forming composition 7 just obtained as described above was applied to a glass substrate (10 cm square, 3.5 mm thickness) by spin coating, and heated in a drying furnace at 180 ° C. for 30 minutes for coating-coated substrate. 10 was obtained. The resulting coating was transparent with no foreign matter.

(Example 11)
After obtaining B1 liquid like Example 1, 0.5g of BYK-340 was further added to this, and it stirred at 25 degreeC for 10 minute (s), and obtained the film forming composition 8. The viscosity (25 ° C.) of the film-forming composition 8 obtained immediately after the stirring was measured. Moreover, the presence or absence of precipitation was confirmed visually.
Immediately after the stirring, the film-forming composition 8 was placed in a freezer at −20 ° C. and stored for 2 months. After storage for 2 months, the film-forming composition 8 was taken out of the freezer and visually checked for the presence or absence of precipitation, and the viscosity (25 ° C.) was measured to determine the difference between the viscosity immediately after preparation and the viscosity after storage. The evaluation results are shown in Table 2 together with the production conditions and the presence or absence of precipitation.

  Further, after storing at the above temperature for 2 months, a coated substrate 11 was obtained in the same manner as in Example 1 except that 2 g of the film forming composition 8 taken out from the freezer and adjusted to 25 ° C. was used. The obtained film was cloudy.

(Example 12)
In the same manner as in Example 1, a B1 solution was obtained. The viscosity of the B1 liquid obtained immediately after the completion of stirring was measured. Further, 1.0 g of BYK-355 was prepared as it is as A4 liquid.
Liquid B1 and liquid A4 were placed in a freezer at −20 ° C. and stored for 2 months immediately after completion of stirring or immediately after preparation.

After storage for 2 months, the B1 liquid and the A4 liquid were taken out from the freezer and visually checked for the presence of precipitation. About B1 liquid and A4 liquid taken out from the freezer, temperature was adjusted to 25 degreeC within 3 hours. Viscosity was measured about B1 liquid. Immediately after the measurement, the B1 liquid and the A4 liquid were mixed and stirred at a temperature of 25 ° C. for 10 minutes to obtain a film forming composition 9.
The presence or absence of precipitation in the obtained film forming composition 9 was visually confirmed.
The difference between the viscosity immediately after preparation of the B1 solution and the viscosity after storage was determined. The evaluation results are shown in Table 2 together with the production conditions and the presence or absence of precipitation.

  2 g of the film-forming composition 9 immediately after obtained above was applied to a glass substrate (10 cm square, 3.5 mm thickness) by spin coating, and heated in a drying oven at 180 ° C. for 30 minutes to provide a film-coated substrate. 12 was obtained. The resulting coating was transparent with no foreign matter.

(Example 13)
After obtaining B1 liquid like Example 1, 1.0g of BYK-355 was further added to this, and it stirred at 25 degreeC for 10 minutes, and obtained the composition 10 for film formation. The viscosity of the film-forming composition 10 obtained immediately after the completion of stirring was measured. Moreover, the presence or absence of precipitation was confirmed visually.
Immediately after completion of stirring, the film-forming composition 10 was placed in a freezer at −20 ° C. and stored for 2 months. After storage for 2 months, the film-forming composition 10 was taken out of the freezer and visually checked for precipitation. About the film forming composition 10 taken out from the freezer, the temperature was adjusted to 25 ° C. within 3 hours, the viscosity was measured, and the difference between the viscosity immediately after preparation and the viscosity after storage was determined. The evaluation results are shown in Table 2 together with the production conditions and the presence or absence of precipitation.

  Further, after storing at the above temperature for 2 months, a coated substrate 13 was obtained in the same manner as in Example 1 except that 2 g of the film forming composition 10 taken out from the freezer and adjusted to 25 ° C. was used. The obtained film was cloudy.

  The content of the nonionic surfactant shown in Table 2 is mass% with respect to the total amount of the film-forming composition. In addition, a viscosity change is a viscosity change before and behind the storage period of the composition for film formation, and the thing made into 1 liquid is a B liquid, respectively. Further, the mixing temperature and the presence or absence of precipitation during mixing are the temperature during mixing and the presence or absence of precipitation for the film-forming composition stored in one liquid.

In Examples 1, 8, 10, and 12, which are examples of the present invention, by using a film-forming composition that was stored separately for liquid A and liquid B and mixed immediately before application to the substrate. A good film was obtained.
In Comparative Examples 2 to 7, 9, 11, and 13, any one of storage temperature, mixing temperature of liquid A, liquid B, etc. is not appropriate, and precipitation or thickening occurs in the film forming composition. It was a problem that cloudiness was observed.

  According to the present invention, in the method for producing a substrate with a film using a hydrolyzable silane compound, the quality and yield can be maintained by preparing the film forming composition efficiently while suppressing the occurrence of precipitation or the like. However, it is useful because it can produce a silicon oxide-based substrate with a simple and efficient production.

Claims (11)

A solution preparation process for preparing solution A containing a nonionic surfactant,
A B liquid preparation step of preparing a B liquid containing a silane compound having a hydrolyzable functional group and / or a partial hydrolysis condensate thereof, and silica fine particles and not containing a nonionic surfactant;
The mixing step of mixing the liquid A and the liquid B stored at a storage temperature of −5 ° C. or less immediately after the step of preparing the liquid B at a temperature at which no precipitate is generated, and obtaining the film forming composition, and the film The manufacturing method of the board | substrate with a film which has a film formation process which apply | coats the composition for formation on a board | substrate, and makes it a film by making it harden | cure.   The difference between the viscosity of the B liquid immediately after the B liquid preparation process and the viscosity of the B liquid used in the mixing process, and the viscosity of the film forming composition immediately after the mixing process and the viscosity of the film forming composition used in the application The manufacturing method according to claim 1, wherein both the differences (however, the viscosities are all at 25 ° C.) are less than 1.5 mPa · s.   The manufacturing method of Claim 1 or 2 with which the said B liquid preparation process includes operation which reacts the solution containing the said silane compound and the said silica fine particle on the conditions on which the said silane compound partially hydrolyzes and condenses.   The method according to any one of claims 1 to 3, wherein the silane compound is a silane compound mainly having an alkoxy group having 1 to 10 carbon atoms as the hydrolyzable functional group.   5. The temperature according to claim 1, wherein the storage temperature is a temperature at which a change in viscosity of the B liquid measured at 25 ° C. can be less than 1.5 mPa · s after storage for 2 months immediately after the B liquid preparation step. 2. The production method according to item 1.   The said storage temperature is -40--5 degreeC, The manufacturing method of any one of Claims 1-5.   The manufacturing method according to any one of claims 1 to 6, wherein a mixing temperature in the mixing step is 0 to 30 ° C.   The content of the nonionic surfactant in the composition for forming a film is 0.001 to 1.0 mass% with respect to the total amount of the composition, according to any one of claims 1 to 7. Production method.   The content of the said silane compound and / or its partial hydrolysis-condensation product in the said film formation composition is any one of Claims 1-8 which are 5.0-50.0 mass% with respect to the said composition whole quantity. 2. The production method according to item 1.   The content of the silica fine particles in the film forming composition is 0.5 to 50 parts by mass with respect to 100 parts by mass of the silane compound and / or a partial hydrolysis condensate thereof. The production method according to item.   The manufacturing method of any one of Claims 1-10 whose average particle diameter of the said silica fine particle is 1-100 nm.