JP2002361800A - Surface hydrophilic member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface hydrophilic member provided with a surface hydrophilic layer with excellent hydrophilic properties and better wear resistance on surfaces of various base materials. SOLUTION: The surface hydrophilic member is characterized in that it is provided with a hydrophilic layer with a crosslinking structure formed by preparing a hydrophilic coating liquid composition comprising a polymer compound (A) of general formula (I) and a hydrolysable compound (B) of general formula (II), and by coating the composition on the base material. In the formula (I), R<1> to R<4> are a hydrogen atom and a 1-8C hydrocarbon group, respectively, and m is 0, 1 or 2 and n is an integer of 1-8 and L is a single bond or an organic connecting group. In the formula (II), R<5> and R<6> are each an alkyl group or an aryl group and X is Si, Al, Ti or Zr and m is an integer of 0-2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface hydrophilic member, and more particularly to a surface hydrophilic member having a hydrophilic surface layer having excellent hydrophilicity and durability.

[0002]

2. Description of the Related Art Although resin films are used for various purposes, their surfaces are generally hydrophobic. Also, few inorganic materials such as glass and metal have high hydrophilicity. When the surface of a substrate made of a resin film, inorganic material, or the like is hydrophilized, attached water droplets spread evenly on the substrate surface and form a uniform water film. Can be effectively prevented,
Useful for preventing devitrification due to moisture and ensuring visibility in rainy weather.
Furthermore, hydrophobic contaminants such as urban dust, combustion products such as carbon black contained in exhaust gas from automobiles, oil and fats, and sealant elution components are unlikely to adhere. This is useful for various applications.

According to the conventionally proposed surface treatment methods for hydrophilization, for example, etching treatment, plasma treatment, etc., although they are highly hydrophilized, the effect is temporary and the hydrophilization state becomes longer. Cannot be maintained for a period.
Further, a surface hydrophilic coating film using a hydrophilic graft polymer as one of the hydrophilic resins has also been proposed (newspaper "Chemical Industry Daily", January 30, 1995). According to this report, although this coating film has a certain degree of hydrophilicity, it cannot be said that the affinity with the substrate is sufficient, and higher durability is required.

As another film having excellent surface hydrophilicity, a film using titanium oxide is conventionally known. For example, in PCT / JP96 / 00733, when a photocatalyst-containing layer is formed on a substrate surface, It is disclosed that the surface is highly hydrophilized in response to the photoexcitation of the photocatalyst, and if this technology is applied to various composite materials such as glass, lenses, mirrors, exterior materials, and water surrounding members, it is disclosed that It has been reported that the material can be provided with excellent functions such as antifogging and antifouling. However, a hydrophilic film using titanium oxide does not have sufficient film strength, and a hydrophilic material having better abrasion resistance has been demanded.

[0005]

An object of the present invention is to provide a surface hydrophilic member having a surface hydrophilic layer having excellent hydrophilicity and better abrasion resistance on various substrate surfaces. It is in.

[0006]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted research with an emphasis on the properties of a hydrophilic graft polymer. As a result, the present inventors have hydrolyzed and polycondensed a hydrophilic polymer and a metal alkoxide. The above object can be achieved by a surface layer having a crosslinked structure formed by performing the above, further, the surface layer having such a crosslinked structure is a hydrophilic polymer having a silane coupling group at the terminal and a crosslinker The present invention was completed by finding that it can be easily obtained by combining the above. That is, the surface hydrophilic member of the present invention has a hydrophilic graft chain on the substrate surface, and
It is characterized by comprising a hydrophilic layer having a crosslinked structure formed by hydrolysis and condensation polymerization of a metal alkoxide selected from i, Ti, Zr, and Al. In addition, the hydrophilic layer having such a cross-linked structure is represented by the following general formula (A):
It is a preferred embodiment that the composition is formed by preparing and applying a hydrophilic coating solution composition containing a polymer compound represented by the following formula, and more preferably (B)
An embodiment includes a hydrophilic layer having a cross-linked structure formed by preparing and applying a hydrophilic coating solution composition containing a hydrolyzable compound represented by the following general formula (II).

[0007]

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In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, m represents 0, 1 or 2; Represents an integer of 1 to 8. L represents a single bond or an organic linking group, and Y is -NHC
_{^{OR 5, -CONH 2, -CON (}} R 5) 2, -COR 5,
—OH, —CO ₂ M or —SO ₃ M, wherein R ⁵
Represents an alkyl group having 1 to 8 carbon atoms, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal or onium.

[0009]

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In the formula (II), R ⁶ and R ⁷ may be the same or different and each represents an alkyl group or an aryl group; X represents Si, Al, Ti or Zr; 2
Represents an integer.

Although the function of the present invention is not clear, it has a hydrophilic graft chain and a crosslinked structure formed by hydrolysis and condensation polymerization of a metal alkoxide selected from Si, Ti, Zr and Al. The hydrophilic layer is an organic-inorganic composite having a high-density crosslinked structure due to the hydrolysis and condensation polymerization of metal alkoxides, while the hydrophilic functional groups introduced in the form of graft chains are unevenly distributed on the surface in a free state. Since the film is formed, the film has high hydrophilicity and high strength. Specifically, by dissolving (A) a hydrophilic polymer having a silane coupling group at a terminal in an appropriate solvent and stirring the mixture, hydrolysis / polycondensation proceeds in the system, and a sol-like hydrophilic coating is applied. A liquid composition is obtained, which is coated on a substrate and dried, whereby hydrophilic functional groups are unevenly distributed on the surface in a free state on the substrate, and silane coupling groups are formed by reaction with each other. Thus, an organic-inorganic composite film having a crosslinked structure is formed. Further, by adding (B) a hydrolyzable compound to the hydrophilic coating solution, the silane coupling group and the polymerizable functional group in the hydrolyzable compound in the hydrolysis / polycondensation in the system. The number of reaction sites for forming crosslinks increases, and an organic-inorganic composite film having a higher density and a stronger crosslink structure is formed, so that the resulting hydrophilic layer coating film has higher strength and excellent abrasion resistance. It is considered that abrasion is exhibited and high surface hydrophilicity can be maintained for a long time.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The surface hydrophilic member of the present invention, on a suitable substrate,
Having a hydrophilic graft chain, and Si, Ti, Zr, A
Hydrolysis of a metal alkoxide selected from l, a hydrophilic layer having a cross-linked structure formed by condensation polymerization, the hydrophilic layer having such a cross-linked structure,
It can be appropriately formed using the metal alkoxide structure exemplified above and a compound having a hydrophilic functional group capable of forming a hydrophilic graft chain. Among the metal alkoxides, alkoxides of Si are preferable in terms of reactivity and availability, and specifically, compounds used for a silane coupling agent can be suitably used.

In the present invention, the crosslinked structure formed by hydrolysis and polycondensation of the metal alkoxide as described above is hereinafter referred to as a sol-gel crosslinked structure. Such a hydrophilic layer having a free hydrophilic graft chain and a sol-gel crosslinked structure is, for example, (A) a polymer compound represented by the general formula (I) having a silane coupling group at a terminal, preferably, Further, a hydrophilic coating solution composition containing (B) a hydrolyzable compound represented by the general formula (II) is prepared, and then coated and dried to form a surface hydrophilic layer. Can be formed. Hereinafter, each component contained in the hydrophilic coating solution composition for forming the hydrophilic layer according to this preferred embodiment will be described.

[(A) Polymer compound represented by formula (I)] The polymer compound represented by formula (I) is a hydrophilic polymer having a silane coupling group at a terminal. , Where appropriate, referred to as a specific hydrophilic polymer. In the general formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 8 or less carbon atoms is preferable. Specifically, a methyl group, an ethyl group,
Propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl,
s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-
Examples include an ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group. R ¹ , R ² , R ³ and R ⁴ are preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoint of effects and availability.

These hydrocarbon groups may further have a substituent. When the alkyl group has a substituent, the substituted alkyl group is constituted by a bond between the substituent and an alkylene group, and a monovalent nonmetallic atomic group other than hydrogen is used as the substituent. Preferred examples include a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, an amino group, N-alkylamino group, N, N-
Diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, Ν-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyl An oxy group, an N-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group, an acylthio group,
Acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-
Arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-
Alkyl ureido group,

N-arylureido, N'-alkyl-N-alkylureido, N'-alkyl-N-arylureido, N ', N'-dialkyl-N-alkylureido, N', N '-Dialkyl-N-arylureido group, N'-aryl -−- alkylureido group, N'-aryl-N-arylureido group, N',
An N′-diaryl-N-alkylureido group, N ′,
An N′-diaryl-N-arylureido group, an N′-alkyl-N′-aryl-N-alkylureido group,
N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group,

Alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, N-arylcarbamoyl, N, N-diarylcarbamoyl, N-alkyl-N-aryl Rucarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-
SO ₃ H) and its conjugate base group (hereinafter, referred to as sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N
-Arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N
- arylsulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group (-PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group) , dialkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono Group (—PO ₃ H (alkyl))
And its conjugated base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (-PO ₃ H (ar
yl)) and a conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (-OPO ₃ H ₂₎
And its conjugated base group (hereinafter, referred to as a phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (a
lkyl) ₂ ), a diarylphosphonooxy group (—O
PO ₃ (aryl) ₂ ), an alkylarylphosphonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alky)
1)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (-OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group). ), A morpholino group, a cyano group, a nitro group, an aryl group, an alkenyl group, and an alkynyl group.

In these substituents, specific examples of the alkyl group include the above-mentioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl2, xylyl, mesityl. Group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group,
Acetoxyphenyl, benzyloxyphenyl, methylthiophenyl, phenylthiophenyl, methylaminophenyl, dimethylaminophenyl, acetylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, ethoxyphenylcarbonyl, phenoxycarbonyl Examples include a phenyl group, an N-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, and a phosphonatophenyl group. Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, and a 2-chloro-1-ethenyl group. Examples of the alkynyl group include an ethynyl group, Propynyl group,
Examples thereof include a 1-butynyl group and a trimethylsilylethynyl group. Examples of G ¹ in the acyl group (G ¹ CO-),
Examples include hydrogen, and the above-described alkyl and aryl groups.

Of these substituents, more preferred are a halogen atom (-F, -Br, -Cl, -I),
An alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, an N, N-dialkylamino group, an acyloxy group, an N-alkylcarbamoyloxy group, an N-arylcabamoyloxy group, an acylamino group, a formyl group, Acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-
Dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonato group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-aryl Sulfamoyl group, N-alkyl-N
An arylsulfamoyl group, a phosphono group, a phosphonate group, a dialkylphosphono group, a diarylphosphono group, a monoalkylphosphono group, an alkylphosphonato group, a monoarylphosphono group, an arylphosphonato group, a phosphonooxy group, Examples include a phosphonatoxy group, an aryl group, and an alkenyl group.

On the other hand, the alkylene group in the substituted alkyl group may be a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Preferably, examples thereof include a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms and a cyclic alkylene group having 5 to 10 carbon atoms. Preferred specific examples of the substituted alkyl group obtained by combining the substituent with an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, and allyl. Oxymethyl group, phenoxymethyl group, methylthiomethyl, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy Carbonyl butyl group,

Chlorophenoxycarbonylmethyl, carbamoylmethyl, N-methylcarbamoylethyl, N, N-dipropylcarbamoylmethyl, N-
(Methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, Diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methyl Benzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2
-Methylpropenylmethyl group, 2-propynyl group, 2-
Butynyl group, 3-butynyl group and the like.

L represents a single bond or an organic linking group. Here, when L represents an organic linking group, L represents a polyvalent linking group comprising a non-metallic atom, specifically, 1 to 60 carbon atoms and 0 to 10 nitrogen atoms. Atoms, from 0 to 50 oxygen atoms, from 1 to 100 hydrogen atoms, and from 0 to 20 sulfur atoms. More specific examples of the linking group include the following structural units or those formed by combining them.

[0023]

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Y is -NHCOR ⁵ , -CONH ₂ ,
—CON (R ⁵ ) ₂ , —COR ⁵ , —OH, —CO ₂ M or —SO ₃ M, wherein R ⁵ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Represent. Also, -CON
When the compound has a plurality of R ⁵ such as (R ⁵ ) ₂ , R ⁵ may be bonded to each other to form a ring, and the formed ring may be a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may be a heterocycle containing atoms. R ⁵ may further have a substituent. Examples of the substituent that can be introduced here include the aforementioned R 5
^{In the case where 1} , R ² , R ³ and R ⁴ are alkyl groups, the same substituents as those which can be introduced can also be used.

Specific examples of R ⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isopropyl group, an isobutyl group, an s-butyl group and a t-butyl group. Butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group,
Preferable examples include a cyclopentyl group. Examples of M include a hydrogen atom; an alkali metal such as lithium, sodium and potassium; an alkaline earth metal such as calcium and barium; and an onium such as ammonium, iodonium and sulfonium. The Y, _{specifically, -NHCOCH 3, -CONH 2, -COOH} , -S
O ₃ ^- NMe ₄ ^+, a morpholino group, etc. are preferable.

Specific examples (exemplified compound 1 to exemplified compound 12) of the specific hydrophilic polymer (A) which can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

[0027]

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The specific hydrophilic polymer according to the present invention comprises a radically polymerizable monomer represented by the following general formula (i) and a silane cup having a chain transfer ability in radical polymerization represented by the following general formula (ii). It can be synthesized by radical polymerization using a ring agent. Since the silane coupling agent (ii) has a chain transfer ability,
In the radical polymerization, a polymer having a silane coupling group introduced into the terminal of the polymer main chain can be synthesized.

[0029]

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In the above formulas (i) and (ii), R ¹
To R ⁴ , L, Y, n and m are as defined in the above formula (I). These compounds are commercially available and can be easily synthesized.

As a radical polymerization method for synthesizing the hydrophilic polymer represented by the general formula (I), any of conventionally known methods can be used. Specifically, general radical polymerization methods include, for example, New Polymer Experimental Science 3, Polymer Synthesis and Reaction 1 (edited by the Society of Polymer Science, Kyoritsu Shuppan), New Experimental Chemistry Course 19, Polymer Chemistry (I) (Edited by The Chemical Society of Japan, Maruzen), Materials Engineering Course, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., and these can be applied.

[(B) Hydrolyzable compound represented by the general formula (II)] The hydrolyzable compound represented by the general formula (II) used herein (hereinafter referred to simply as the hydrolyzable compound Is a hydrolyzable polymerizable compound having a polymerizable functional group in its structure and functioning as a crosslinking agent, and by condensation polymerization with the specific hydrophilic polymer,
A strong film having a crosslinked structure is formed. In the general formula (II), R ⁶ represents a hydrogen atom, an alkyl group or an aryl group, R ⁷ represents an alkyl group or an aryl group, X represents Si, Al, Ti or Zr, and m represents 0 to 2 Represents an integer. When R ⁶ and R ⁷ represent an alkyl group, the number of carbon atoms is preferably 1 to 4. The alkyl group or the aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group. This compound is a low molecular compound, and preferably has a molecular weight of 1,000 or less.

The following are specific examples of the hydrolyzable compound (B) represented by the general formula (II), but the present invention is not limited thereto. When X is Si, that is, when the hydrolyzable compound contains silicon, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane Silane, ethyltriethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltri Methoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane,
Examples include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like. Of these, particularly preferred are tetramethoxysilane, tetraethoxysilane, methyltolumethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane. Examples include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

When X is Al, that is, when the hydrolyzable compound contains aluminum, for example, trimethoxyaluminate, triethoxyaluminate, tripropoxyaluminate, tetraethoxyaluminate, etc. Can be mentioned. When X is Ti, that is, as a compound containing titanium, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl trititanate Examples include methoxy titanate, methyl triethoxy titanate, ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate, phenyl triethoxy titanate, and the like. When X is Zr, that is, when the compound contains zirconium, for example, zirconate corresponding to the compound exemplified as the compound containing titanium can be used.

[Preparation of Hydrophilic Coating Solution] In preparing the hydrophilic coating solution composition containing (A) the specific hydrophilic polymer, the content of (A) the specific hydrophilic polymer is 10% in terms of solid content. It is preferable that the content be not less than 50% by weight and not less than 50% by weight. When the content is 50% by weight or more, the film strength tends to decrease, and when the content is less than 10% by weight, the film properties are reduced, and the possibility of cracks in the film is increased. Absent.

In the case of adding the hydrolyzable compound (B) to the preparation of the hydrophilic coating solution composition which is a preferred embodiment,
(B) The amount of the hydrolyzable compound added is such that the polymerizable group in the (B) hydrolyzable compound is at least 5 mol% based on the silane coupling group in the specific hydrophilic polymer (A)
The amount is preferably 0 mol% or more. The upper limit of the amount of the cross-linking agent is not particularly limited as long as it is within a range capable of sufficiently cross-linking with the hydrophilic polymer, but when added in a large excess, the cross-linking agent not involved in the cross-linking causes the produced surface hydrophilic member to become sticky. May cause problems.

By dissolving a hydrophilic polymer having a silane coupling group at a terminal, preferably a hydrolyzable compound (crosslinking agent) in a solvent and stirring the mixture well, these components are hydrolyzed to obtain polycondensation. By doing so, the organic-inorganic composite sol solution produced becomes the hydrophilic coating solution according to the present invention, whereby a surface hydrophilic layer having high hydrophilicity and high film strength is formed. In the preparation of the organic-inorganic composite sol liquid, in order to promote hydrolysis and polycondensation reaction,
It is preferable to use an acidic catalyst or a basic catalyst in combination,
In order to obtain a reaction efficiency that is practically preferable, a catalyst is essential.

As the catalyst, an acid or a basic compound may be used as it is, or a catalyst dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst or a basic catalyst, respectively). The concentration at the time of dissolution in the solvent is not particularly limited, and may be appropriately selected depending on the characteristics of the acid or basic compound to be used, the desired content of the catalyst, and the like. The condensation rate tends to be faster. However, when a basic catalyst having a high concentration is used, a precipitate may be formed in a sol solution. Therefore, when a basic catalyst is used, its concentration is desirably 1 N or less in terms of a concentration in an aqueous solution.

The type of the acidic catalyst or the basic catalyst is not particularly limited, but when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element which hardly remains in the coating film after drying is preferable. Specifically, acidic catalysts are represented by hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, and their RCOOH. Substituted carboxylic acids in which R in the structural formula is substituted with other elements or substituents, sulfonic acids such as benzenesulfonic acid, and the like. Examples of the basic catalyst include ammoniacal bases such as aqueous ammonia and amines such as ethylamine and aniline. And the like.

The hydrophilic coating solution is prepared by dissolving (B) a hydrolyzable compound and (A) a hydrophilic polymer having a silane coupling group at a terminal in a solvent such as ethanol, adding the above catalyst, and stirring. Can be implemented. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time during which stirring is continued is preferably in the range of from 1 to 72 hours. A composite sol solution can be obtained.

The solvent used for preparing the hydrophilic coating liquid composition containing (A) the hydrophilic polymer and preferably (B) the hydrolyzable compound can be uniformly dissolved and dispersed. There is no particular limitation as long as it is
For example, aqueous solvents such as methanol, ethanol, and water are preferable.

As described above, the preparation of the organic-inorganic composite sol liquid (hydrophilic coating liquid composition) for forming the hydrophilic layer according to the present invention utilizes the sol-gel method. For the sol-gel method, see Sakuhana Saio, "Sol-gel Method Science", Inc.
Agne Shofusha (published) (1988), Inkira Hirashima, "Technology for preparing functional thin films by the latest sol-gel method", General Technology Center (published) (1992), etc. The method described can be applied to the preparation of the hydrophilic coating solution composition according to the present invention.

Various additives can be used in the hydrophilic coating solution composition according to the present invention according to the purpose as long as the effects of the present invention are not impaired. For example, a surfactant or the like can be added to improve the uniformity of the coating solution.

The surface hydrophilic member of the present invention can be obtained by applying the hydrophilic coating solution composition on an appropriate substrate, heating and drying to form a surface hydrophilic layer. The heating temperature and the heating time for forming the hydrophilic layer are not particularly limited as long as the solvent in the sol solution is removed and a temperature and time at which a strong film can be formed. The temperature is preferably 200 ° C. or lower, and the crosslinking time is preferably within 1 hour. As a substrate that can be used in the present invention,
For example, when an anti-fogging effect is expected, the substrate is a transparent substrate, and glass, plastic, or the like can be suitably used as the material. Examples of applications to which a member having an anti-fog effect can be applied include mirrors such as rearview mirrors for vehicles, bathroom mirrors, toilet mirrors, dental mirrors, road mirrors; spectacle lenses, optical lenses, camera lenses, and endoscopes. Lenses such as mirror lenses, illumination lenses, semiconductor lenses, and copier lenses; prisms; windows of buildings and towers; automobiles, railway vehicles, aircraft, ships, submersibles, snowmobiles, ropeway gondola, and amusement parks. Window glass for vehicles such as earth gondola and spacecraft; cars,
Railway vehicles, aircraft, ships, submersibles, snowmobiles, snowmobiles, motorcycles, ropeway gondolaes, amusement park gondolaes, windshields for vehicles such as spaceships; protective goggles, sports goggles, shields for protective masks Shields for sports masks, shields for helmets, glass for frozen food display cases; cover glasses for measuring instruments; and films for attaching to the surface of the articles.

When the surface-cleaning member of the present invention is expected to have a surface cleaning effect, the substrate may be made of, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, cloth , Their combinations,
Any of those laminates can be suitably used. Applications to which members having a surface cleaning effect can be applied include building materials, building exteriors, building interiors, window frames, window glasses, structural members,
Exterior and painting of vehicles, exterior of machinery and goods, dust cover and painting, traffic signs, various display devices, advertising towers, sound barriers for roads, sound barriers for railways, bridges, exterior and painting of guardrails, tunnel interiors and painting , Insulator, solar cell cover,
Solar water heater heat collection cover, greenhouse, vehicle lighting cover, housing equipment, toilet bowl, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, dishwasher, dish dryer, sink, cooking range , A kitchen hood, a ventilation fan, and a film to be attached to the surface of the article.

When the surface hydrophilic member of the present invention is expected to have an antistatic effect, the material may be, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, cloth, or a combination thereof. And their laminates can be suitably used. Applicable applications include cathode ray tubes, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, housing and parts for household electrical appliances, exterior and coating, housing for OA equipment products, Parts and exterior and painting, building materials, building exterior, building interior, window frames, window glass,
Includes structural members, exterior and coating of vehicles, exterior of mechanical devices and articles, dustproof covers and coatings, and films for attaching to the surface of the articles.

As the substrate, any of inorganic substrates such as glass and ceramic and substrates having a surface made of a polymer resin are preferably used, and the resin substrate itself is coated with the resin. Both the base material and the composite material whose surface layer is composed of a resin layer are included. Typical examples of the resin itself include film base materials such as a shatterproof film, a design film, and a corrosion-resistant film; and resin base materials such as signboards and soundproof walls of expressways. Examples of the base material having a resin-coated surface include an automobile housing, a painted plate such as a painted building material, a laminated plate having a resin film adhered to the surface thereof, a primer-treated base material, and a hard-coated base material. A representative example is given. Representative examples of the composite material in which the surface layer is formed of a resin layer include a resin sealing material having an adhesive layer provided on the back surface, a reflection mirror, and the like.

[0048]

EXAMPLES The present invention will be described below in detail with reference to examples, but the scope of the present invention is not limited by these examples.

(Synthesis Example 1: (A) Synthesis of Specific Hydrophilic Polymer) A 500 ml three-necked flask was charged with 50 g of acrylamide,
3.4 g of mercaptopropyltrimethoxysilane and 220 g of dimethylacetamide were added, and 0.5 g of 2,2-azobis (2,4-dimethylvaleronitrile) was added under a nitrogen stream at 65 ° C. After maintaining the same temperature with stirring for 6 hours, the mixture was cooled to room temperature. The mixture was poured into 2 liters of ethyl acetate, and the precipitated solid was collected by filtration and washed with water to obtain a hydrophilic polymer (1). The weight after drying was 52.4 g.
Weight average molecular weight 30 by GPC (polystyrene standard)
00 polymer and ¹³ C-NMR (DMSO-
d ₆ ) to terminate the trimethoxysilyl group (50.0p
pm) was confirmed to be a polymer having the structure of Exemplified Compound 1 described above.

(Example 1) [Preparation of hydrophilic coating solution composition (sol-gel solution)] The following components were uniformly mixed, and the mixture was stirred at 20 ° C for 2 hours to carry out hydrolysis to obtain a sol-like hydrophilic composition. A coating liquid composition was obtained. -(A) 0.21 g of hydrophilic polymer (1)-(B) 0.62 g of tetramethoxysilane-4.7 g of ethanol-4.7 g of water-0.1 g of nitric acid aqueous solution (1N) [catalyst] 0.1 g

[Preparation of Surface Hydrophilic Member] The above hydrophilic coating composition was applied to a glass plate (manufactured by Endo Kagaku) so that the coated amount after drying was 2 g / m ² ,
The resultant was dried by heating at a temperature of 10 ° C. for 10 minutes to form a hydrophilic layer on the substrate, whereby a surface hydrophilic member of Example 1 was obtained.

[Evaluation of Surface Hydrophilic Member] The surface of the obtained hydrophilic member was rubbed 100 times with a non-woven fabric (BEMCOT, manufactured by Asahi Chemical Fiber Co., Ltd.), and the contact angle before and after the rubbing (contact angle of water drop in the air).
Was measured using CA-Z manufactured by Kyowa Interface Science Co., Ltd. After rubbing, the surface of the member was observed, but the hydrophilic layer on the surface was not peeled off or visibly scratched even after rubbing, and the hydrophilic layer of Example 1 was resistant to abrasion. It was found to have sufficient strength. The contact angle was 6.5 ° before rubbing and 6.9 ° after rubbing.
Sufficient hydrophilicity was exhibited not only before rubbing but also after rubbing, and it was confirmed that the surface hydrophilic member of the present invention had good abrasion resistance.

[0053]

According to the present invention, it is possible to provide a surface hydrophilic member having excellent hydrophilicity and good abrasion resistance, which is provided with a hydrophilic layer on various substrate surfaces.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09K 3/00 C09K 3/00 R F term (Reference) 4F100 AB10B AB11B AB12B AB19B AH08B AL06B AR00B AT00A BA02 EH46 EH462 EJ05B EJ422 EJ86 EJ862 GB07 GB31 JB05B 4J038 CE021 CE051 CG141 CG171 CR071 DL151 GA02 GA03 GA06 GA09 GA13 GA15 JA23 JC32 KA03 NA06 NA11

Claims (3)

[Claims] 1. A substrate having a hydrophilic graft chain on the surface of a substrate,
A surface hydrophilic member having a hydrophilic layer having a crosslinked structure formed by hydrolysis and condensation polymerization of a metal alkoxide selected from Si, Ti, Zr, and Al. 2. The method according to claim 1, wherein the hydrophilic layer having a crosslinked structure is
2. The surface hydrophilicity according to claim 1, wherein the composition is formed by preparing and applying a hydrophilic coating solution composition containing a polymer compound represented by the following general formula (I). Element. Embedded image In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, m represents 0, 1 or 2; Represents an integer of 8. L represents a single bond or an organic linking group, Y is -NHCOR ^5, -
^{_{CONH 2, -CON (R 5)}} 2, -COR 5, -OH, -
Represents CO ₂ M or —SO ₃ M, wherein R ⁵ has 1 carbon atom
And M represents a hydrogen atom, an alkali metal, an alkaline earth metal or onium. 3. The hydrophilic coating liquid composition further comprises:
The surface hydrophilic member according to claim 2, further comprising (B) a hydrolyzable compound represented by the following general formula (II). Embedded image In the formula (II), R ⁶ and R ⁷ each independently represent an alkyl group or an aryl group, X represents Si, Al, Ti or Zr, and m represents an integer of 0 to 2.