JP2018062563A - Composition containing silicone, film prepared therewith, and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition that can make a film that has high hydrophilicity and is not lost by washing.SOLUTION: The composition contains silicone having a specific repeating unit, and an organic silicon compound having the following structure .SELECTED DRAWING: None

Description

  The present invention relates to a composition containing silicone, a film produced using the same, and a method for producing them.

  A group of compounds called silicone or siloxane is used in various fields because it has characteristics such as high durability. However, since silicone or siloxane has high hydrophobicity, it needs to be subjected to a hydrophilic treatment when used in applications requiring hydrophilicity.

  Conventionally made hydrophilic methods of silicone or siloxane are generally classified into two types.

  The first method is a method of directly introducing a hydrophilic group into silicone or siloxane. For example, Patent Document 1 discloses a method for producing a silicone elastomer stamp having a hydrophilic surface by polymerizing an aminoalkylalkoxysilane, adding a hydrophilic group to an amino group in the polymer. Patent Document 2 discloses a technique of introducing a hydroxyl group to the surface of silicone rubber by plasma polymerization and adding a hydrophilic group.

The second method is a method using a monomer having a hydrophilic group as a monomer constituting silicone or siloxane. For example, Patent Document 3 discloses an amino acid-modified silane compound having a carboxylate by an ester hydrolysis reaction and a method for producing the same. Patent Documents 4 and 5 disclose a method for synthesizing a hydrophilic siloxane monomer by a ring-opening reaction of sultone or lactone with alkoxysilylalkylamine.
Patent Document 6 discloses a method for synthesizing silicone having sulfonic acid.

Japanese Patent No. 34968831 JP 2013-087238 A JP 2012-180334 A International Publication No. 2011-063625 Pamphlet International Publication No. 1995/010523 Pamphlet JP2015-140313A

  However, the hydrophilic polymers obtained by the methods described in Patent Documents 1 to 6 are not necessarily sufficient for bonding with the base material. In particular, in a film in which a hydrophilic polymer is formed on a glass substrate and is directly splashed with water, the film has low durability and may not be suitable for long-term use.

  In view of the above-described problems, the present invention provides a composition containing silicone, a process for producing the same, and a film produced using the composition, which can form a highly hydrophilic film that is not lost by washing. For the purpose.

  As a result of intensive studies to solve the above problems, the inventors of the present invention are highly hydrophilic from a composition containing a silicone containing a sulfonic acid group and an organosilicon compound containing an epoxy group, and The inventors have found that a film that is not lost by washing can be formed, and have completed the present invention.

That is, the present invention is as follows.
[1]
Silicone having a repeating unit represented by the following formula (1);
(In the above formula (1), R ¹ and R ² each independently have a hydrogen atom, a hydroxyl group, a C 1-20 alkyl group which may have a substituent, or a substituent. May be an alkoxy group having 1 to 20 carbon atoms, an unsaturated chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or 6 to 20 carbon atoms which may have a substituent. Each is independently an integer of 1 to 20, n is each independently an integer of 2 to 20, and X is independently a hydrogen atom or a sulfonic acid. And a group forming an organic salt, an alkali metal atom, an alkaline earth metal atom, or a transition metal atom.)
The composition containing the organosilicon compound containing the epoxy group represented by following formula (2).
(In said formula (2), R < ³ > -R < ⁶ > has a C1-C20 alkyl group and substituent which may have a hydrogen atom, a hydroxyl group, and a substituent each independently. Or an alkoxy group having 1 to 20 carbon atoms (R ^y ), an aryl group having 6 to 20 carbon atoms which may have a substituent, or R ^x represented by the following formula (3). , R ^{3 to} R ⁶ are one or more of R ^x and one or more of R ^y .
(In the above formula (3), R ⁷ is an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted oxyalkylene group having 1 to 20 carbon atoms, or a substituent. An arylene group having 6 to 20 carbon atoms which may have a group, and R ^{8 to} R ¹⁰ each independently have 1 to 20 carbon atoms which may have a hydrogen atom, a hydroxyl group or a substituent. Or an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and R ^{8 to} R ^10. May be combined to form a ring, and R ⁷ may be combined with any of R ^{8 to} R ¹⁰ to form a ring, and l is an integer of 0 to 20. ))
[2]
The composition according to [1], further comprising a solvent.
[3]
The composition according to [1] or [2], which is heated.
[4]
[1] A film comprising the composition according to any one of [3].
[5]
The method of apply | coating the composition as described in [1] or [2] on a base material, and producing a film | membrane.

  The composition of the present invention can provide a strong coating on the surface of a substrate, and can provide a substrate having high surface hydrophilicity.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.

The composition of the present embodiment includes a silicone having a repeating unit represented by the following formula (1),
And an organosilicon compound containing an epoxy group represented by the following formula (2).
The composition of this embodiment can be firmly applied to the surface of the substrate, and has the effect of a substrate having high surface hydrophilicity.

〔silicone〕
The silicone in this embodiment has a repeating unit represented by the following formula (1). Silicone is not particularly limited as long as it contains a repeating unit represented by the following formula (1), and even if it is a homopolymer consisting only of a repeating unit represented by the following formula (1), It may be a copolymer containing the repeating unit represented by 1) and other repeating units.

(In the above formula (1), R ¹ and R ² each independently have a hydrogen atom, a hydroxyl group, a C 1-20 alkyl group which may have a substituent, or a substituent. May be an alkoxy group having 1 to 20 carbon atoms, an unsaturated chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or 6 to 20 carbon atoms which may have a substituent. Each is independently an integer of 1 to 20, n is each independently an integer of 2 to 20, and X is independently a hydrogen atom or a sulfonic acid. And a group forming an organic salt, an alkali metal atom, an alkaline earth metal atom, or a transition metal atom.)

In the above formula (1), the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- Butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group, n-ethylhexyl group, n- Linear or branched alkyl group such as nonyl group, n-decyl group, 2-hexyl group, 2-octyl group, 2-decyl group, 2-dodecyl group, 2-hexadecyl group, 2-octadecyl group; cyclopropyl group , Cyclic alkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclohexadecyl group, cyclooctadecyl group, etc. Is mentioned.

In the above formula (1), the alkoxy group having 1 to 20 carbon atoms represented by R ¹ and R ² is not particularly limited. For example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, Examples include a hexyloxy group, an octyloxy group, a decyloxy group, a dodecyloxy group, a hexadecyloxy group, and an octadecyloxy group.

In the above formula (1), the unsaturated chain hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² is not particularly limited, and examples thereof include an ethenyl group, an allyl group, a butenyl group, and a pentenyl group. Hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group.

In the above formula (1), the aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² is not particularly limited, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group. It is done.

  In the above formula (1), the substituent of the alkyl group, alkoxy group, unsaturated chain hydrocarbon group, and aryl group is not particularly limited, and examples thereof include a hydroxy group, a halogen atom, a carbonyl group, an amino group, and an imino group. 1 type (s) or 2 or more types selected from the group which consists of group, a cyano group, an azo group, an azide group, a thiol group, a sulfo group, a nitro group, a hydroxy group, an acyl group, an epoxy group, and an aldehyde group is mentioned.

  In said formula (1), m is an integer of 1-20, Preferably it is 1-10, More preferably, it is 1-4. When m is 20 or less, the water solubility, hydrophilicity, proton donating property, acidity, conductivity, adhesiveness, or antifogging property of silicone tends to be further improved.

  In said formula (1), n is an integer of 2-20, Preferably it is 2-10, More preferably, it is 2-4, More preferably, it is 2. When n is 20 or less, the water solubility, hydrophilicity, proton donating property, acidity, conductivity, adhesiveness, or antifogging property of silicone tends to be further improved.

  In the above formula (1), X is a hydrogen atom, a group that forms an organic salt with a sulfonic acid, an alkali metal atom, an alkaline earth metal atom, or a transition metal atom. X forms an ionic bond with sulfonic acid.

  The group that forms an organic salt with a sulfonic acid is not particularly limited, and examples thereof include ammonium ions, protonated primary, secondary or tertiary amines, and quaternary ammonium ions.

  Although it does not specifically limit as an alkali metal atom, For example, Li, Na, and K are mentioned.

  Although it does not specifically limit as an alkaline-earth metal atom, For example, Be, Mg, and Ca are mentioned.

  The transition metal atom is not particularly limited, and examples thereof include Cu, Ag, Au, Pd, Pt, Ru, Tc, Cr, Mo, Nb, Sc, Y, Zr, V, Mn, Fe, Co, and Ni. Can be mentioned.

  In the case where the silicone in the present embodiment is a copolymer, the other repeating unit is not particularly limited. For example, the repeating unit is a repeating unit other than the repeating unit represented by the above formula (1), and the following formula ( And the repeating unit represented by 7).

(In the above formula (7), each R ¹⁸ is independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom. An alkoxy group having 1 to 20 carbon atoms, an unsaturated chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms.)

In the above formula (7), the alkyl group having 1 to 20 carbon atoms represented by R ¹⁸ is not particularly limited. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, linear or branched alkyl group such as n-decyl group, 2-hexyl group, 2-octyl group, 2-decyl group, 2-dodecyl group, 2-hexadecyl group, 2-octadecyl group; cyclopropyl group, cyclobutyl group , Cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclohexadecyl group, cyclooctadecyl group, etc. It is.

In the above formula (7), the alkoxy group having 1 to 20 carbon atoms represented by R ¹⁸ is not particularly limited. For example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group Octyloxy group, decyloxy group, dodecyloxy group, hexadecyloxy group, and octadecyloxy group.

In the above formula (7), the unsaturated chain hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁸ is not particularly limited. For example, ethenyl group, allyl group, butenyl group, pentenyl group, hexenyl group , Heptenyl group, octenyl group, decenyl group, dodecenyl group.

In the above formula (7), the aryl group having 6 to 20 carbon atoms represented by R ¹⁸ is not particularly limited, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group.

  In the above formula (7), the substituent of the alkyl group, alkoxy group, unsaturated chain hydrocarbon group, and aryl group is not particularly limited, and examples thereof include a hydroxy group, a halogen atom, a carbonyl group, an amino group, and an imino group. 1 type (s) or 2 or more types selected from the group which consists of group, a cyano group, an azo group, an azide group, a thiol group, a sulfo group, a nitro group, a hydroxy group, an acyl group, an epoxy group, and an aldehyde group is mentioned.

  In the case where the silicone in the present embodiment is a copolymer, the content of the repeating unit represented by the above formula (1) is determined based on the water solubility, hydrophilicity, proton donating property, acidity, conductivity of the silicone to be obtained. Can be appropriately determined according to various properties such as property, adhesiveness, or antifogging property. As the content of the repeating unit represented by the above formula (1) increases, the water solubility, hydrophilicity, proton donating property, acidity, conductivity, adhesiveness, or antifogging property of the silicone is improved. As the content of the repeating unit represented by 1) is smaller, the water solubility, hydrophilicity, proton donating property, acidity, conductivity, adhesiveness, or antifogging property of silicone tends to decrease.

  Naturally, silicone is a hydrophobic compound. However, the silicone in this embodiment has improved water solubility, hydrophilicity, proton donating property, acidity, conductivity, adhesiveness, or antifogging property. Therefore, the composition containing silicone in the present embodiment can be used for more applications.

  Further, the silicone in the present embodiment includes a coating agent having antifogging and antifouling properties, a stable electrolyte membrane having high proton mobility and ion exchange properties, additives such as conductive ink, hairdressing agents, automobiles, and building materials. Coating materials for electronic parts, sheets with excellent adhesion, paint additives, various oils, additives for rubber products, silane coupling agents, glass products, non-aqueous particles containing silica and metals, various materials such as metals Or it can use suitably as these hydrophilizing agents.

In the silicone having a repeating unit represented by the formula (1), R ^{1 in the} formula (1) is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n- Heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, n-decyl group, 2-hexyl group, 2-octyl group, 2-decyl group, 2-dodecyl group, 2-hexadecyl group, 2 -More preferred is an octadecyl group.
In the silicone having a repeating unit represented by the formula (1), R ^{2 in the} formula (1) is preferably a hydrogen atom.

The silicone having a repeating unit represented by the formula (1) preferably has a number average molecular weight of 100 to 10000000, more preferably 1000 to 8000000, and further preferably 2000 to 6000000.
In the silicone having a repeating unit represented by the formula (1), the number of repeating units represented by the formula (1) is preferably 1 to 10,000, more preferably 5 to 1,000, and 10 to 500. More preferably it is.

[Organic silicon compound containing epoxy group]
The composition of this embodiment contains the organosilicon compound containing the epoxy group represented by following formula (2).

(In said formula (2), R < ³ > -R < ⁶ > has a C1-C20 alkyl group and substituent which may have a hydrogen atom, a hydroxyl group, and a substituent each independently. Or an alkoxy group having 1 to 20 carbon atoms (R ^y ), an aryl group having 6 to 20 carbon atoms which may have a substituent, or R ^x represented by the following formula (3). , R ^{3 to} R ⁶ are one or more of R ^x and one or more of R ^y .

(R ^x represents any of R ^{3 to} R ^{6. In} the above formula (3), R ⁷ has an optionally substituted alkylene group having 1 to 20 carbon atoms and a substituent. Or an arylene group having 6 to 20 carbon atoms which may have a substituent, and R ^{8 to} R ¹⁰ are each independently a hydrogen atom, a hydroxyl group, The C1-C20 alkyl group which may have a substituent, the C1-C20 alkoxy group which may have a substituent, or the C6-C6 which may have a substituent. And R ^{8 to} R ¹⁰ may be combined together to form a ring, and R ⁷ is combined with any of R ^{8 to} R ¹⁰ to form a ring. L is an integer from 0 to 20.)

In the above formula (2), the alkoxy group having 1 to 20 carbon atoms represented by R ^y is not particularly limited. For example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group Octyloxy group, decyloxy group, dodecyloxy group, hexadecyloxy group, and octadecyloxy group.

In the above formula (2) and (3), the alkyl group of ^{R 3, R 4, R 5} , R 6, R 8, R 9, and having 1 to 20 carbon atoms represented by R ^10, not particularly limited For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl. Group, n-heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, n-decyl group, 2-hexyl group, 2-octyl group, 2-decyl group, 2-dodecyl group, 2- Straight or branched alkyl groups such as hexadecyl group, 2-octadecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclohexadecyl group Group, cyclic alkyl group such as a cycloalkyl octadecyl group.

In the above formulas (2) and (3), the alkoxy group having 1 to 20 carbon atoms represented by R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , and R ¹⁰ is not particularly limited. Are, for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, hexadecyloxy and octadecyloxy.

In the above formulas (2) and (3), the aryl group having 6 to 20 carbon atoms represented by R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , and R ¹⁰ is not particularly limited. Are, for example, phenyl group, tolyl group, xylyl group, cumenyl group and naphthyl group.

In the above formula (3), the alkylene group having 1 to 20 carbon atoms represented by R ^7, is not particularly limited, for example, methylene group, ethylene group, n- propylene, n- butylene, to n- A xylene group, an n-heptylene group, an n-octylene group, and an n-dodecylene group may be mentioned.

In the above formula (3), the oxyalkylene group having 1 to 20 carbon atoms represented by R ⁷ is not particularly limited, and examples thereof include an oxymethylene group, an oxyethylene group, an oxy n-propylene group, and an oxyisopropylene group. Oxy n-butylene group, oxy n-pentylene group, oxy n-hexylene group, oxy n-heptylene group, oxy n-octylene group and oxy n-decalene group.

In the above formula (3), the arylene group having 6 to 20 carbon atoms represented by R ⁷ is not particularly limited, and examples thereof include a phenylene group, a tolylene group, a xylylene group, a cumenylene group, and a naphthylene group.
In the above formulas (2) and (3), the substituent of the alkyl group, alkoxy group, alkylene group, aryl group, oxyalkylene group, and arylene group is not particularly limited, and examples thereof include a hydroxy group, a halogen atom, and a carbonyl group. , One or more selected from the group consisting of amino group, imino group, cyano group, azo group, azide group, thiol group, sulfo group, nitro group, hydroxy group, acyl group, epoxy group, and aldehyde group Is mentioned.

In the formula (3), when R ^{8 to} R ¹⁰ are combined to form a ring, and R ⁷ is combined with any of R ^{8 to} R ¹⁰ to form a ring, Examples thereof include cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclohexadecyl group, and cyclooctadecyl group.

In the organosilicon compound containing an epoxy group represented by the formula (2), R ^{3 to} R ⁶ in the formula (2) are optionally substituted alkoxy groups having 1 to 20 carbon atoms (R ^y ), preferably methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, hexadecyloxy, octadecyloxy Is more preferable.
In the formula (3), R ⁷ is preferably an alkylene group having 1 to 20 carbon atoms which may have a substituent, or an oxyalkylene group having 1 to 20 carbon atoms which may have a substituent. .
R ⁷ preferably forms a ring together with any of R ^{8 to} R ¹⁰ ,
As such a ring, the above-mentioned cyclic alkyl group is preferable.
In formula (3), l is preferably an integer of 0 to 10, and more preferably an integer of 1 to 5.

The number of R ^x in the above formula (2) is not particularly limited as long as it is 1 or more, and the organosilicon compound represented by the formula (2) may contain 2 or more R ^x .
Among these, the number of carbon atoms per R ^x represented by the above formula (3) is preferably 2 to 14, more preferably 2 to 12, and further preferably 2 to 10. . Since the hydrophobicity of the organosilicon compound itself represented by the formula (2) increases as the number of carbon atoms increases, the upper limit value of the carbon number is preferably 14.
Similarly, the number of carbon atoms per substituent other than the epoxy moiety, that is, the number of carbon atoms per substituent other than R ^x is preferably 1 to 14, more preferably 1 to 12, and more preferably 1 to 10. More preferably.

  The organosilicon compound containing an epoxy group represented by the formula (2) may be synthesized by a known method, or a commercially available product may be used. Specific examples of the organosilicon compound containing an epoxy group represented by the formula (2) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane. 2- (2,3-epoxycyclopentyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) methyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2- (2 , 3-epoxycyclopentyl) methyltrimethoxysilane, 2- (2,3-epoxycyclopentyl) propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltripropoxysilane, 3-glycidoxymethyl Limethoxysilane, 3-glycidoxyethyltrimethoxysilane, 3-glycidyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Can be mentioned. Among these organosilicon compounds, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxy are preferable. Propylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane are preferable, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane are more preferable.

  The silicone having a repeating unit represented by the formula (1) in the present embodiment is a compound obtained by oligomerizing and polymerizing an organosilicon compound containing a sulfonic acid group represented by the following formula (4).

(In the above formula (4), R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently a hydrogen atom, a hydroxyl group, a C 1-20 alkyl group optionally having a substituent, It may have a C1-C20 alkoxy group which may have a substituent, a C1-C20 unsaturated chain hydrocarbon group which may have a substituent, or a substituent A good aryl group having 6 to 20 carbon atoms, wherein at least one of R ¹¹ , R ¹² and R ¹³ is the alkoxy group, m is an integer of 1 to 20 and n is an integer of 2 to 20 X is a hydrogen atom, a group that forms an organic salt with sulfonic acid, an alkali metal atom, an alkaline earth metal atom, or a transition metal atom.)

In the above formula (4), the alkyl group having 1 to 20 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ is not particularly limited, and examples thereof include a methyl group, an ethyl group, and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, n-decyl group, isopropyl group, 2-hexyl group, 2-octyl group, 2-decyl group, 2-dodecyl group, 2-hexadecyl group, 2-octadecyl group, etc. Chain or branched alkyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclohexadecyl group, cycl And cyclic alkyl groups such as octadecyl.

In the above formula (4), the alkoxy group having 1 to 20 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, Examples include butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, hexadecyloxy, and octadecyloxy groups.

In the above formula (4), the unsaturated chain hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ is not particularly limited. Group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group.

In the above formula (4), the aryl group having 6 to 20 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ is not particularly limited, and examples thereof include a phenyl group, a tolyl group, a xylyl group, Examples thereof include cumenyl group and naphthyl group.

  In the above formula (4), the substituent of the alkyl group, alkoxy group, unsaturated chain hydrocarbon group, and aryl group is not particularly limited, and examples thereof include a hydroxy group, a halogen atom, a carbonyl group, an amino group, and an imino group. 1 type (s) or 2 or more types selected from the group which consists of group, a cyano group, an azo group, an azide group, a thiol group, a sulfo group, a nitro group, a hydroxy group, an acyl group, an epoxy group, and an aldehyde group is mentioned.

In the above formula (4), at least one of R ¹¹ , R ¹² and R ¹³ is an alkoxy group. When one of R ¹¹ , R ¹² , and R ¹³ is an alkoxy group, the compound represented by the formula (4) can form a dimer. In addition, when two of R ¹¹ , R ¹² , and R ¹³ are alkoxy groups, the compound represented by the formula (4) can form a linear polymer. In addition, when three of R ¹¹ , R ¹² and R ¹³ are alkoxy groups, the compound represented by the formula (4) can form a crosslinked polymer.

  In said formula (4), m is an integer of 1-20, Preferably it is 1-10, More preferably, it is 1-4. When m is 20 or less, the water solubility, hydrophilicity, proton donating property, acidity, conductivity, adhesiveness, or antifogging property of silicone tends to be further improved.

  In said formula (4), n is an integer of 2-20, Preferably it is 2-10, More preferably, it is 2-4, More preferably, it is 2. When n is 20 or less, the water solubility, hydrophilicity, proton donating property, acidity, conductivity, adhesiveness, or antifogging property of silicone tends to be further improved.

  In the above formula (4), X is a hydrogen atom, a group that forms an organic salt with sulfonic acid, an alkali metal atom, an alkaline earth metal atom, or a transition metal atom.

  The group that forms an organic salt with a sulfonic acid is not particularly limited, and examples thereof include ammonium ions, protonated primary, secondary or tertiary amines, and quaternary ammonium ions.

  Although it does not specifically limit as an alkali metal atom, For example, Li, Na, and K are mentioned.

  Although it does not specifically limit as an alkaline-earth metal atom, For example, Be, Mg, and Ca are mentioned.

  The transition metal atom is not particularly limited, and examples thereof include Cu, Ag, Au, Pd, Pt, Ru, Tc, Cr, Mo, Nb, Sc, Y, Zr, V, Mn, Fe, Co, and Ni. Can be mentioned.

Compared to organic silicon compound containing an amino group described below (B), the amino group of the organosilicon compound containing an amino group (B) - in (CH _{2) n} the embodiment -SO ₃ X was added Silicone obtained by polymerization of a compound represented by formula (4) containing a sulfonic acid group has improved water solubility, hydrophilicity, proton donating property, acidity, conductivity, adhesiveness, or antifogging property. sell.

  Further, by using an oligomer and a polymer of the compound represented by the formula (4), that is, a silicone having a repeating unit represented by the formula (1), a stable polymer and a copolymer having a sulfonic acid group introduced therein can be used. Coalescence can be obtained. Such polymers and copolymers have high water solubility, high hydrophilicity, high proton donating properties, high acidity, high conductivity, high adhesion, or high antifogging properties. Further, by copolymerizing the compound represented by the formula (4) and other monomers, the water solubility, hydrophilicity, proton donating property, acidity, conductivity, adhesiveness, or antifogging property of the copolymer. Can also be controlled.

  The monomer in the present embodiment, that is, the compound represented by the formula (4) is a coating agent having antifogging properties and antifouling properties, a stable electrolyte membrane having high proton mobility and ion exchange properties, conductive ink, and the like. Additives, hair styling agents, coating agents for automobiles, building materials, electronic parts, etc., sheets with excellent adhesive properties, paint additives, various oils, additives for rubber products, silane coupling agents, glass products, silica and metals It can be suitably used as various materials such as non-aqueous particles, metals, etc., or hydrophilizing agents.

(Method for producing compound represented by formula (4))
The method for producing the compound represented by the formula (4) includes the vinyl group of the vinyl sulfonic acid (A) having a vinyl group and a sulfonic acid group, the amino group of the organosilicon compound (B) having an amino group, It has the reaction process which reacts.

  The said reaction process can be obtained by mixing and heating vinylsulfonic acid (A) and organosilicon compound (B). The reaction temperature is not particularly limited, but is preferably 60 ° C. or higher and lower than the boiling point of the reaction solution, more preferably 70 ° C. or higher and lower than the boiling point of the reaction solution, and further preferably 80 ° C. or higher and lower than the boiling point of the reaction solution. When the reaction temperature in the reaction step is 60 ° C. or higher, the addition reaction rate between the vinyl group of the vinyl sulfonic acid (A) and the amino group of the amino group-containing compound (B) tends to be further improved.

  The reaction step may be performed in a solvent, in a two-phase state of an organic solvent and water, or may be performed without a solvent. Although it does not specifically limit as a solvent which can be used, For example, organic solvents, such as 1-butanol, N, N- dimethylformamide, a dimethylsulfoxide, water, an ionic fluid, etc. are mentioned. The boiling point of the solvent used is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 150 ° C. or higher.

  After the reaction step, the monomer contained in the obtained reaction solution may be isolated or may be used for the next step without isolation. In addition, after the reaction step, the H atom of the sulfonic acid group of the compound represented by formula (4) is replaced with a group that forms an organic salt with sulfonic acid, an alkali metal atom, an alkaline earth metal atom, or a transition metal atom Also good. The substitution method is not particularly limited, and can be performed by a known method.

  In the reaction step, the addition amount of the organosilicon compound (B) with respect to the addition amount of the vinyl sulfonic acids (A) is preferably 0.1 to 100 times, more preferably 1 to 50 times, and still more preferably 1 .5 to 20 times. When the addition amount of the organosilicon compound (B) is within the above range with respect to the addition amount of the vinyl sulfonic acids (A), the reaction efficiency tends to be further improved.

(Vinyl sulfonic acids (A))
The vinyl sulfonic acid (A) is not particularly limited as long as it has a vinyl group and a sulfonic acid group. The sulfonic acid group is a group represented by —SO ₃ H. By using such vinyl sulfonic acids (A), it is possible to reduce the content of metals contained as impurities in the resulting sulfonic acid group-containing compound as compared with the case of using vinyl sulfonate as a raw material. it can. Moreover, since the desalting process by an ion exchange resin or electrodialysis becomes unnecessary, manufacturing cost can be suppressed and the fall of the yield of the sulfonic acid group containing compound by an ion exchange resin or electrodialysis can also be suppressed.

  Although it does not specifically limit as vinyl sulfonic acid (A), The vinyl sulfonic acid represented by following formula (5) is preferable, and a vinyl sulfonic acid is more preferable from a reactive viewpoint among these. By using such vinyl sulfonic acids (A), a compound represented by the formula (4) having a high sulfonic acid density can be obtained. In addition, vinylsulfonic acid (A) may be used individually by 1 type, or may use 2 or more types together.

(In said formula (5), R <^15> , R < ¹⁶ > and R <^17> are respectively independently a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 unsaturated chain hydrocarbon group. .)

In R ¹⁵ , R ¹⁶ and R ¹⁷ in the above formula (5), the alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group, n-ethylhexyl group, linear or branched alkyl group such as n-nonyl group, n-decyl group, 2-hexyl group, 2-octyl group, 2-decyl group, 2-dodecyl group, 2-hexadecyl group, 2-octadecyl group; Rings such as propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, cyclohexadecyl, cyclooctadecyl, etc. Alkyl group and the like.

In R ¹⁵ , R ¹⁶ , and R ¹⁷ in the above formula (5), the unsaturated chain hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include ethenyl group, allyl group, and butenyl. Group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group and the like.

(Organic silicon compound (B))
The organosilicon compound (B) is not particularly limited as long as it has an amino group and a silicon atom. The amino group is added to the vinyl group of the vinyl sulfonic acids (A). The silicon atom is preferably contained as an alkoxysilane group, silanol group or the like. In addition, an organosilicon compound (B) may be used individually by 1 type, or may use 2 or more types together.

  Although it does not specifically limit as an organosilicon compound (B), For example, the compound shown by following formula (6) is mentioned.

(In the above formula (6), R ^{11 ′} , R ^{12 ′} , R ^{13 ′} , R ^{14 ′} , and R ^{14 ″} may each independently have a hydrogen atom, a hydroxyl group, or a substituent. An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an unsaturated chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, Or an aryl group having 6 to 20 carbon atoms which may have a substituent, at least one of R ^{11 ′} , R ^{12 ′} and R ^{13 ′} is the alkoxy group, and m ′ is 1 to 20 (It is an integer.)

In the above formula (6), the alkyl group having 1 to 20 carbon atoms represented by R ^{11 ′} , R ^{12 ′} , R ^{13 ′} , R ^{14 ′} and R ^{14 ″} is not particularly limited. Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n- Heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, n-decyl group, 2-hexyl group, 2-octyl group, 2-decyl group, 2-dodecyl group, 2-hexadecyl group, 2 -Linear or branched alkyl group such as octadecyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclohexadecyl group, cyclooctyl group Examples thereof include cyclic alkyl groups such as a tadecyl group.

In the above formula (6), the alkoxy group having 1 to 20 carbon atoms represented by R ^{11 ′} , R ^{12 ′} , R ^{13 ′} , R ^{14 ′} and R ^{14 ″} is not particularly limited. Examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, hexadecyloxy group, and octadecyloxy group.

In the above formula (6), the unsaturated chain hydrocarbon group having 1 to 20 carbon atoms represented by R ^{11 ′} , R ^{12 ′} , R ^{13 ′} , R ^{14 ′} and R ^{14 ″} is particularly limited. Although not, for example, ethenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group can be mentioned.

In the above formula (6), the aryl group having 6 to 20 carbon atoms represented by R ^{11 ′} , R ^{12 ′} , R ^{13 ′} , R ^{14 ′} , and R ^{14 ″} is not particularly limited. A phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are mentioned.

  In the above formula (6), the substituent of the alkyl group, alkoxy group, unsaturated chain hydrocarbon group, and aryl group is not particularly limited, and examples thereof include a hydroxy group, a halogen atom, a carbonyl group, an amino group, and an imino group. 1 type (s) or 2 or more types selected from the group which consists of group, a cyano group, an azo group, an azide group, a thiol group, a sulfo group, a nitro group, a hydroxy group, an acyl group, an epoxy group, and an aldehyde group is mentioned.

In the above formula (6), at least one of R ^{11 ′} , R ^{12 ′} and R ^{13 ′} is an alkoxy group. When at least one of R ^{11 ′} , R ^{12 ′} and R ^{13 ′} is an alkoxy group, a compound represented by the formula (4) having polymerizability can be obtained.

  In said formula (6), m 'is an integer of 1-20, Preferably it is 1-10, More preferably, it is 1-4. When m ′ is 20 or less, the water solubility, hydrophilicity, proton donating property, acidity, conductivity, adhesion, or antifogging property of silicone tends to be further improved.

  The organosilicon compound (B) is not particularly limited. For example, 3- (trimethoxysilyl) -1-propanamine, 3- (dimethoxymethylsilyl) -1-propanamine, 3- (methoxydimethylsilyl) -1-propanamine, 3- (ethyldimethoxysilyl) -propanamine, 3- (diethylmethoxysilyl) -propanamine, 3- (triethoxysilyl) -propanamine, 3- (diethoxymethylsilyl) -propanamine 3- (ethoxydimethylsilyl) -propanamine, 3- (diethoxyethylsilyl) -propanamine, 3- (ethoxydiethylsilyl) -propanamine, 3- (tripropoxysilyl) -1-propanamine, 3- (Methyldipropoxysilyl) -1-propanamine, 3- (dimethyl (Lopoxysilyl) -1-propanamine, 1- (3-aminopropyl) -silanetriol, 1- (3-aminopropyl) -1-methyl-silanediol, 1- (3-aminopropyl) -1-dimethyl-silanol Is mentioned.

[Method for producing silicone]
The method for producing silicone in the present embodiment is a polymerization step in which the monomer represented by the formula (4) is polymerized, or the monomer represented by the formula (4) and an organosilicon compound other than the monomer are copolymerized. Have

  In the polymerization step, it is possible to obtain silicone by heating the monomer in water or mixing the monomer and acid. Although it does not specifically limit as an acid which can be used, For example, hydrochloric acid, methanesulfonic acid, and the monomer in this embodiment are mentioned.

  The polymerization step may be performed in a solvent, in a two-phase state of an organic solvent and water, or may be performed in the absence of a solvent. Although it does not specifically limit as a solvent which can be used, For example, organic solvents, such as butanol, water, an ionic fluid, etc. are mentioned.

  The polymerization temperature in the polymerization step is not particularly limited, but is preferably 80 ° C. or higher and lower than the boiling point of the reaction solution, more preferably 90 ° C. or higher and lower than the boiling point of the reaction solution, and still more preferably 95 ° C. or higher and lower than the boiling point of the reaction solution. It is. When the polymerization temperature in the polymerization step is 80 ° C. or higher, the polymerization rate tends to be further improved.

  In addition, the reaction step in the monomer production method and the polymerization step in the silicone production method may be performed in multiple stages or in a single stage in a single container. In particular, by mixing the vinyl sulfonic acid (A) and the organosilicon compound (B) and heating in water, an addition reaction and a polymerization reaction can be performed simultaneously, and silicone can be obtained in a single stage.

  Although it does not specifically limit as an organosilicon compound other than the monomer represented by the said Formula (4), For example, the compound represented by following formula (8) is mentioned.

(In the above formula (8), R ^{18 ′} , R ^{18 ″} , R ^{18 ′ ″} and R ^{18 ″ ″} each independently have a hydrogen atom, a hydroxyl group or a substituent. Or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, or an unsaturated chain hydrocarbon having 1 to 20 carbon atoms which may have a substituent. Or an aryl group having 6 to 20 carbon atoms, and at least one of R ^{18 ′} , R ^{18 ″} , R ^{18 ′ ″} and R ^{18 ″ ″} is the alkoxy group.)

In the above formula (8), the alkyl group having 1 to 20 carbon atoms represented by R ^{18 ′} , R ^{18 ″} , R ^{18 ′ ″} and R ^{18 ″ ″} is not particularly limited. , Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n -Heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, n-decyl group, 2-hexyl group, 2-octyl group, 2-decyl group, 2-dodecyl group, 2-hexadecyl group, Linear or branched alkyl group such as 2-octadecyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclohexadecyl group, cyclooctadecyl group Examples thereof include a cyclic alkyl group such as a syl group.

In the above formula (8), the alkoxy group having 1 to 20 carbon atoms represented by R ^{18 ′} , R ^{18 ″} , R ^{18 ′ ″} and R ^{18 ″ ″} is not particularly limited. Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, hexadecyloxy group, and octadecyloxy group.

In the above formula (8), the unsaturated chain hydrocarbon group having 1 to 20 carbon atoms represented by R ^{18 ′} , R ^{18 ″} , R ^{18 ′ ″} and R ^{18 ″ ″} is particularly preferable. Although not limited, for example, an ethenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a decenyl group, and a dodecenyl group can be mentioned.

In the above formula (8), the aryl group having 6 to 20 carbon atoms represented by R ^{18 ′} , R ^{18 ″} , R ^{18 ′ ″} and R ^{18 ″ ″} is not particularly limited. , Phenyl group, tolyl group, xylyl group, cumenyl group, and naphthyl group.

  In the above formula (8), the substituent of the alkyl group, alkoxy group, unsaturated chain hydrocarbon group, and aryl group is not particularly limited, and examples thereof include a hydroxy group, a halogen atom, a carbonyl group, an amino group, and an imino group. 1 type (s) or 2 or more types selected from the group which consists of group, a cyano group, an azo group, an azide group, a thiol group, a sulfo group, a nitro group, a hydroxy group, an acyl group, an epoxy group, and an aldehyde group is mentioned.

In the above formula (8), at least one of R ^{18 ′} , R ^{18 ″} , R ^{18 ′ ″} and R ^{18 ″ ″} is the alkoxy group. One of R ^{18 ′} , R ^{18 ″} , R ^{18 ′ ″} , and R ^{18 ″ ″} can be an alkoxy group to form a dimeric silicone. Further, when two of R ^{18 ′} , R ^{18 ″} , R ^{18 ′ ″} , and R ^{18 ″ ″} are alkoxy groups, a linear silicone can be formed. In addition, when three or four of R ^{18 ′} , R ^{18 ″} , R ^{18 ′ ″} , and R ^{18 ″ ″} are alkoxy groups, a crosslinked polymer silicone can be formed.

[Composition of composition]
In the composition of the present embodiment, the mixing ratio of the silicone having the repeating unit represented by the formula (1) and the organosilicon compound containing the epoxy group (2) is the repeating unit represented by the formula (1). The organosilicon compound (2) containing the epoxy group is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the silicone having -15 mass parts is further more preferable.

It is preferable that the composition of this embodiment contains a solvent further from a viewpoint of workability | operativity of coating-film formation. Moreover, when the composition of this embodiment contains a solvent, it is preferable that it is a solution. Examples of the solvent include alcohols such as methanol, ethanol, propanol and isopropanol, ketones such as acetone and ethyl methyl ketone, ethers such as diethyl ether and tetrahydrofuran, nitriles such as acetonitrile and benzonitrile, dichloromethane, chloroform, Listed are halogenated hydrocarbons such as dichloroethane, water and the like. Among these solvents, water and alcohol are preferable, and ethanol is more preferable.
When the composition of this embodiment contains a solvent, the quantity of the solvent in this composition is 1,000-10,000 with respect to 100 mass parts of silicone which has a repeating unit represented by said Formula (1). It is preferably a part by mass, more preferably 1,500 to 8,000 parts by mass, and even more preferably 2,000 to 6,000 parts by mass.

  Moreover, it is preferable to mix a suitable additive with the composition containing the silicone (1) which has a repeating unit represented by Formula (1), and the organosilicon compound (2) containing an epoxy group. As an additive, the organosilicon compound represented by Formula (9) is mentioned, for example.

(In said formula (9), R <^19> , R <^20> , R < ²¹ > and R <^22> are respectively independently a C1-C20 alkoxy group which may have a hydrogen atom, a hydroxyl group, and a substituent. is there.)

In the above formula (9), the alkoxy group having 1 to 20 carbon atoms represented by R ¹⁹ , R ²⁰ , R ²¹ , and R ²² is not particularly limited, but for example, methoxy group, ethoxy group, propoxy group, Examples include butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, hexadecyloxy, and octadecyloxy groups.
In the above formula (9), the substituent of the alkoxy group is not particularly limited, and examples thereof include a hydroxy group, a halogen atom, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azide group, a thiol group, and a sulfo group. 1 type (s) or 2 or more types selected from the group which consists of group, a nitro group, a hydroxy group, an acyl group, an epoxy group, and an aldehyde group is mentioned.
Among these, the alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.

  Specific examples of the organosilicon compound represented by the formula (9) include tetraethoxysilane and tetramethoxysilane.

By adding an organosilicon compound represented by the formula (9) as an additive, an organosilicon compound (2) containing an epoxy group bonded to the substrate and a repeating unit represented by the formula (1) It is possible to form a bond with the silicone (1), and more silicone (1) can be fixed on the substrate.
When the composition of this embodiment contains the said additive, the addition amount of the said additive in this composition is 0.1 with respect to 100 mass parts of silicone which has a repeating unit represented by the said Formula (1). It is preferable that it is -100 mass parts, It is more preferable that it is 1-50 mass parts, 2-20 mass parts is further more preferable.

  In the composition of this embodiment, each component in the composition reacts by heating to form a covalent bond. The composition of this embodiment can be coated on a substrate to form a film.

[Coating method of composition]
The composition of this embodiment can be used suitably in the coating to a base material. Typical coating methods are not particularly limited, but include, for example, a casting method or a spin coating method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, and a spray. Examples thereof include a coating method, a screen printing method, a flexographic printing method, an offset printing method, and an inkjet printing method.
The composition of this embodiment can be formed into a film by apply | coating on a base material and drying. Examples of drying conditions when the composition of the present embodiment is applied to a substrate to form a film include a temperature of 20 to 250 ° C. and a drying condition of 0.01 seconds to 1 week. be able to.

[Method of bonding composition to substrate]
When the dried film is heated, the alkoxy group of the organosilicon compound (2) containing an epoxy group forms a hydrogen bond or a covalent bond with the base material, and the remaining alkoxy group and / or epoxy group is converted into silicone (1 ) And a covalent bond. As heating conditions at this time, for example, the reaction temperature may be 20 to 250 ° C., and heating may be performed for 0.01 seconds to 1 week. In addition, the reaction temperature is more preferably 30 ° C. to 200 ° C., from the viewpoint of proceeding two reactions of a covalent bond forming reaction with the base material and a covalent bond forming reaction with the silicone (1), and 40 ° C. -150 degreeC is further more preferable. From the same viewpoint, the reaction time is preferably 1 second to 1 day, more preferably 10 seconds to 5 hours.
This step may be performed in combination with the above-described drying step at the time of coating, and the heating condition in that case is 20 to 250 ° C., for example, from 0.01 second to 1 week. In addition, the reaction temperature is more preferably 30 ° C. to 200 ° C., and further preferably 40 ° C. to 150 ° C., from the viewpoint of causing the above two reactions to proceed. From the same viewpoint, the reaction time is preferably 1 second to 1 day, more preferably 10 seconds to 5 hours.

〔Base material〕
The substrate is not particularly limited as long as the organosilicon compound (2) containing an epoxy group can form a hydrogen bond or a covalent bond. For example, a hydroxyl group, a carbonyl group, a carboxyl group, a sulfonic acid, amino A substrate having one or more groups selected from the group consisting of a group and an amide bond, a substrate whose surface is coated with siloxane, and obtaining the above groups by processing the surface of the substrate Can be mentioned. Examples of the method for obtaining the above group by processing the surface of the substrate include a method in which a hydroxyl group is present by oxidizing the surface of a metal or the like.
Since the organosilicon compound (2) containing an epoxy group can form a hydrogen bond or a covalent bond with Si-OH of the glass by reaction of the alkoxy group part of the compound, the substrate is preferably glass.

The film formed from the composition of this embodiment has high hydrophilicity and exhibits excellent antifogging properties and antifouling properties.
The degree of hydrophilicity can be evaluated by measuring the contact angle of a water droplet dropped on the surface of a substrate on which a film is formed. The contact angle is an index representing the degree of hydrophilicity, and the smaller the contact angle, the better the hydrophilicity. The contact angle of the film of this embodiment is preferably smaller than 50 °, more preferably smaller than 40 °, and further preferably 20 ° or less.
In addition, since a large number of sulfonic acids can be introduced onto the surface of the substrate by the film of the present embodiment, the composition of the present embodiment is a material having a high proton donating property, a conductive material having an antistatic ability, and a strong adhesive property. A substance with can be provided.
The contact angle can be measured, for example, by taking a photograph of a water droplet dropped on the surface of the substrate on which the film is formed, and measuring the contact angle from the photograph.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

[Production Example 1: Preparation of silicone]
In an insulator-type flask, 5.19 g (48.0 mmol) of vinyl sulfonic acid was dissolved in 495 mL of distilled water, and 5 equivalents of 3- (diethoxymethylsilyl) -propanamine was added to vinyl sulfonic acid. After refluxing for 35 hours, it was dried under reduced pressure. As a result, a methylsiloxane monomer in which vinylsulfonic acid was introduced into the amino group of 3- (diethoxymethylsilyl) -propanamine and 3- (diethoxymethylsilyl) -propanamine monomer were converted to a 1: 4 mole. A silicone containing ratio was obtained as a colorless liquid.

[Example 1]
By dissolving the silicone produced in Production Example 1 with ethanol, a solution containing 5 wt% silicone component was obtained. 2.48 g of this solution, 0.006 g of 3-glycidoxypropyltrimethoxysilane and 2.52 g of ethanol were mixed to obtain a composition solution. This composition solution was dropped on a glass substrate and dried by heating at 100 ° C. for 30 minutes. The obtained film was wiped with Kimwipe moistened with water, and then again dried by heating at 100 ° C. for 5 minutes.

[Example 2]
By dissolving the silicone produced in Production Example 1 with ethanol, a solution containing 5 wt% silicone component was obtained. 2.47 g of this solution, 0.006 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2.52 g of ethanol were mixed to obtain a composition solution. This composition solution was dropped on a glass substrate and dried by heating at 100 ° C. for 30 minutes. The obtained film was wiped with Kimwipe moistened with water, and then again dried by heating at 100 ° C. for 5 minutes.

Example 3
By dissolving the silicone produced in Production Example 1 with ethanol, a solution containing 5 wt% silicone component was obtained. 2.17 g of this solution, 0.011 g of 3-glycidoxypropyltrimethoxysilane, 0.011 g of tetraethoxysilane, and 2.81 g of ethanol were mixed to obtain a mixed composition solution. This composition solution was dropped on a glass substrate and dried by heating at 100 ° C. for 30 minutes. The obtained film was wiped with Kimwipe moistened with water, and then again dried by heating at 100 ° C. for 5 minutes.

Example 4
By dissolving the silicone produced in Production Example 1 with ethanol, a solution containing 5 wt% silicone component was obtained. A composition solution was prepared by mixing 2.17 g of this solution, 0.011 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 0.011 g of tetraethoxysilane, and 2.81 g of ethanol. This composition solution was dropped on a glass substrate and dried by heating at 100 ° C. for 30 minutes. The obtained film was wiped with Kimwipe moistened with water, and then again dried by heating at 100 ° C. for 5 minutes.

[Comparative Example 1]
By dissolving the silicone produced in Production Example 1 with ethanol, a solution containing 5 wt% silicone component was obtained. The solution was dropped onto the glass substrate and heat-dried at 100 ° C. for 30 minutes. The obtained film was wiped with Kimwipe moistened with water, and then again dried by heating at 100 ° C. for 5 minutes.

  The hydrophilicity was evaluated by measuring the contact angle. Immediately after producing a film by drying at 100 ° C. for 30 minutes, the first evaluation was performed, wiped with a Kimwipe moistened with water, and again heat-dried at 100 ° C. for 5 minutes. Carried out.

  The case where the contact angle was 20 ° or less was judged as “◯”, and the case where it was larger than 20 ° was judged as “X”. Moreover, the contact angle was measured also about the glass plate which has not applied anything as the comparative example 2. As for the contact angle, a photograph of a water droplet dropped on the surface of the substrate on which the film was formed was taken, and the contact angle was measured from the photograph.

  The composition of this embodiment is a coating agent having antifogging and antifouling properties, a stable electrolyte membrane having high proton mobility and ion exchange properties, additives such as conductive ink, hairdressing agents, automobiles, building materials, Coating agents for electronic parts, sheets with excellent adhesion, paint additives, various oils, additives for rubber products, silane coupling agents, glass products, non-aqueous particles containing silica and metals, various materials such as metals, or These hydrophilizing agents have industrial applicability.

Claims (5)

Silicone having a repeating unit represented by the following formula (1);
(In the above formula (1), R ¹ and R ² each independently have a hydrogen atom, a hydroxyl group, a C 1-20 alkyl group which may have a substituent, or a substituent. May be an alkoxy group having 1 to 20 carbon atoms, an unsaturated chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or 6 to 20 carbon atoms which may have a substituent. Each is independently an integer of 1 to 20, n is each independently an integer of 2 to 20, and X is independently a hydrogen atom or a sulfonic acid. And a group forming an organic salt, an alkali metal atom, an alkaline earth metal atom, or a transition metal atom.)
The composition containing the organosilicon compound containing the epoxy group represented by following formula (2).
(In said formula (2), R < ³ > -R < ⁶ > has a C1-C20 alkyl group and substituent which may have a hydrogen atom, a hydroxyl group, and a substituent each independently. Or an alkoxy group having 1 to 20 carbon atoms (R ^y ), an aryl group having 6 to 20 carbon atoms which may have a substituent, or R ^x represented by the following formula (3). , R ^{3 to} R ⁶ are one or more of R ^x and one or more of R ^y .
(In the above formula (3), R ⁷ is an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted oxyalkylene group having 1 to 20 carbon atoms, or a substituent. An arylene group having 6 to 20 carbon atoms which may have a group, and R ^{8 to} R ¹⁰ each independently have 1 to 20 carbon atoms which may have a hydrogen atom, a hydroxyl group or a substituent. Or an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and R ^{8 to} R ^10. May be combined to form a ring, and R ⁷ may be combined with any of R ^{8 to} R ¹⁰ to form a ring, and l is an integer of 0 to 20. ))   The composition according to claim 1, further comprising a solvent.   The composition according to claim 1 or 2, which is heated.   The film | membrane containing the composition of any one of Claims 1-3.   The method of apply | coating the composition of Claim 1 or 2 on a base material, and producing a film | membrane.