TW201211072A - Surface modifier - Google Patents

Abstract

Disclosed are: a surface modifier which has two opposite properties such as hydrophilicity and lipophilicity and hydrophilicity and oil-repellency and can be fixed onto a base material; a process for producing the surface modifier; and a base material having a surface modified with the surface modifier. Specifically disclosed are: a surface modifier which comprises a (meth)acrylic polymer having an alkoxysilyl group; a two-part surface modifier which comprises a liquid preparation (I) comprising a polymer having a alkoxysilyl group and a silane coupling agent having a thiol group and a liquid preparation (II) comprising a (meth)acrylic monomer; and a surface-hydrophilizing agent characterized by comprising a (meth)acrylic polymer which is produced by polymerizing a monomer component comprising a silicon-atom-containing monomer and a nitrogen-atom-containing monomer.

Description

201211072 VI. Description of the invention: [Technical field to which the invention pertains] The invention relates to a surface modifier. More specifically, the present invention relates to a surface modifying agent and a surface hydrophilizing agent which impart both aqueous and hydrophobic properties to the surface of the substrate, such as hydrophilic or hydrophobic. :: Bright surface modifier and surface hydrophilizing agent are expected to be used, for example, in 2 surface treatment agents, surface treatment agents for painting, surface treatment agents for printing, materials, biocompatible materials, optical materials, resins A wide range of applications such as films and resin sheets. [Prior Art] Antifogging property, charge prevention property, anti-three property, and the like are known for surface characteristics required for a hydrophilic substrate. These surface characteristics are generally imparted by imparting hydrophilicity to the substrate. For the polymer which can impart hydrophilicity to the substrate, it is known, for example, that the grafting of the (meth) acrylate and the acrylamide copolymer uses a hydrophilic graft polymer of a hydrophilic acrylamide polymer (refer to For example, the patent document 丨). However, since the hydrophilic graft polymer is anionic in the use of the carboxylate as a raw material, the hydrophilicity of the hydrophilic graft polymer is greatly changed due to the pH of the water contacted therewith. Disadvantages. A hydrophilic layer which is adhered to the surface of a hydrophobic resin substrate, and a hydrophilic layer obtained by applying a mixture of hydrophilic cerium oxide and titanium oxide to a film substrate and drying it. The hydrophilic layer can be applied to the surface of a plastic molded article by transferring it onto the surface of the molded article (see, for example, Japanese Patent Publication No. 201211072). However, when the resin substrate used for the plastic molded article has flexibility, when the party is subjected to external stress, the hydrophilic layer may be broken or peeled off. In the prior art, the surface of the substrate is coated with a surfactant to impart antifogging property to the surface of the substrate (see, for example, Patent Document 3 and Patent Literature. However, when the surfactant is applied to the surface of the substrate, there is a surface of the substrate. When the moisture adheres, the surfactant is dissolved in water and is detached from the surface of the substrate. Further, the modifier which can modify the surface characteristics in the past has a property of either hydrophilic or hydrophobic. In recent years, it is expected to develop a versatile surface modifier and a surface hydrophilizing agent which are both hydrophilic and lipophilic, hydrophilic and oil-repellent, and can be immobilized on a substrate. [Progressive technical literature] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2006-231. 243207. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The first group of the present invention is to provide a hydrophilic, water-repellent, lipophilic portion that can be formed to be detachable from a substrate even when it is in contact with water. The surface modification of the film of the desired properties such as oil repellency (4); the surface modification substrate modified with the surface modifier surface; A has a (meth) group having alkoxy fluorene for the surface modifier A method for producing a propylene-based polymer. 8 4 201211072 The second group of the present invention aims to provide two properties which are opposite to each other in hydrophilicity, lipophilicity, hydrophilicity, oil repellency, and the like, and can be immobilized on a substrate. Surface Modifications The object of the second group of the present invention is to provide two properties which are both opposite in hydrophilicity and lipophilicity, hydrophilicity and oil repellency, and can be immobilized on a substrate. A method for producing a substrate modified by a surface. A further object of the second group of the present invention is to provide a surface modifying agent to be immobilized on the surface thereof, and the surface of the surface modifying agent can be modified to A substrate having two properties opposite to hydrophilicity, lipophilicity, hydrophilicity, oil repellency, etc. The third group of the present invention aims to provide that it is not easily detached from the substrate even when it is in contact with water. Excellent on the surface of the substrate a hydrophilizing agent on the surface of the film of the hydrophilic It, and a surface hydrophilizing substrate formed on the surface of the substrate by the surface hydrophilizing agent. [Means for Solving the Problem] The first group to the third group will be described. [Group 1 of the present invention] The first group of the present invention relates to (1) a surface modifying agent having a repetitive unit represented by the formula (I), at least It is obtained by containing an alkoxyfluorenyl (fluorenyl) acrylic polymer represented by formula (II) at one end: 201211072 R1

I —tC-CH23— c=o

I 0 1 R2 wherein a hydrophobic group, R represents a hydrogen atom or a methyl group, and R2 represents a hydrophilic group, a cationic group or an anionic group;

I (II) R4-Si-R6-

I R5 wherein m R5' each independently represents at least one alkoxy group having a carbon number of decyl or a carbon number of alkoxy m R5, and R6 is a carbon number. The surface modifying agent according to the above (1), wherein R2 is an alkyl group having a hydrogen atom, a hydroxyl group or a fluorine atom and having a carbon number of 2 to 2 Å. An alkyl group having a carbon number of 6 to 20 aryl groups having a trans group or a fluorine atom and having a hydrogen atom or a carbon number at one end may have an oxiranyl group having a hydroxyl group or a fluorine atom, and having a hydrogen atom at one end or The group having a carbon number of 1 to 4 may have a polyoxyethylene group having an oxiranyl group having a hydroxyl group or a fluorine atom and having a molar number of 2 to 20, and having a hydrogen atom or a carbon number at one end. The alkyl group may have an oxypropylene group having a trans group or a fluorine atom, a hydrogen atom at one end or a propylene oxide group having a carbon number of 1 to 4, or an oxypropylene group having a hydroxyl group or a fluorine atom. a number of 2 to 20 polypropylene oxide groups, a group represented by the formula (m), or a group represented by the formula (IV) · 6 8 (III) 201211072 R9 R7 10 R8-c〇〇. R10 , R7 and y\ K Each independently represents an alkylene group having a carbon number of R9 and R1 1~4. Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R12 -~Ru-NiRM . R. R13 (IV) wherein R is an alkylene group representing a carbon number of 4, R> And the Ru system independently represents a hydrogen atom or a carbon number 四 (tetra) group, R, an organic group, or a χ-line represents an anion; (3) The surface modifier as described in the above (1) or (2), wherein !) The surface of the surface modification agent according to any one of the above (1) to (3) is modified by the surface modification unit according to any one of the above (1) to (3). (5) A method for producing a (meth)acrylic polymer, which comprises a (meth)acrylic monomer represented by the formula (Va) and an alkane represented by the formula (via) A repeating unit represented by the formula (1) in the presence of a compound of an oxyindenyl group having an alkoxyfluorenyl group represented by the formula (u) at least at one end: ch2=cco-r2 I, II R ' a (Va) Dredging s I 6 R 3 «5 .RlsllR I R4 基via 201211072 where R, R and R5 are each independently represent an alkyl group of carbon number 4 or an alkyl number of 1 to 4 carbon atoms. An oxy group, at least one of R3 and R5 The alkyl group having a carbon number of 1 to 4 'R is a subring group having a carbon number of 1 to 12; R1 (I) c=o

I 〇

I R2 wherein R1 and R2 are the same as above; R3 R4-Si-R6- (II) R5 wherein R3, R4, R5 and R6 are the same as defined above; and (6) as defined in the above (5) A method for producing an acrylic polymer, which is a compound of the formula (I), which may have a hydrogen atom, a hydroxyl group or a fluorine atom, and has a carbon number of from 2 to 20, and may have a carbon number of the radical or i atom. The alkyl group having a hydrogen atom or a carbon number at one end may have an oxiranyl group having a trans group or a fluorine atom, an alkyl group having a hydrogen atom or a carbon number id at one end, and may have a hydroxyl group or a fluorine group. a propylene oxide group having an atomic oxiranyl group having a molar number of 2 to 20, a propylene oxide group having a hydrogen atom or a carbon number at one end, and a hydroxy group or a fluorine atom. An alkyl group having a hydrogen atom or a carbon number of 1 to 4 at one end or a propylene oxide group having a hydroxyl group or a fluorine atom, and a polyepoxy group having a molar number of 2 to 20, and a formula (III) ) the base shown, or the base of formula (IV): (III) 201211072

Rs

-R 〒R8-c00_

In the formula Rw, R7, R9 and R1 ° are each independently represented by K series, and -R11 R12 N - rm I R13 stands for an alkylene group having 1 to 4 carbon atoms, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Χ-(IV) an alkylene group of 1 to 4, an alkyl group of 1 to 12 and a Ru group of 1 to 4, an R14 organic group, and an oxime system, wherein the R system represents a carbon number independently representing hydrogen. The atom or carbon number represents an anion. [Group 2 of the present invention] Group 2 (1) of the present invention is a two-component surface modifier which comprises a polymer having an alkoxyfluorenyl group and a decane coupling agent WI solution containing a 4-alcohol group. And a two-component surface modifier according to the above (1), wherein the polymer having an alkoxyfluorenyl group has the formula (I) The above-mentioned repeating unit is a (flat-based) acrylic acid polymer having at least one terminal having an alkoxy group represented by the formula (II): 201211072 wherein R1 represents a hydrogen atom or a methyl group, and R2 represents Hydrophilic group hydrophobic group, cationic group or anionic group; R3

I (II) R4-Si-R6-

In the formula, R3, R4 and R5 each independently represent an alkyl group having a carbon number of i to 4 or an alkoxy group having a carbon number of 4, and R3, R4 and at least one of the alkyl groups having a carbon number of 1 to 4; The oxy 'R6 is an alkylene group having a carbon number of 1 to 12; (3) The two-component surface modifier according to the above (2), wherein the R system may have a hydrogen atom or a hydroxyl group. Or a carbon atom having 2 to 2 carbon atoms of a fluorine atom, a group having a carbon number of 6 to 20 aryl groups having a control group or an atom, and having a hydrogen atom or a carbon number of 1 to 4 at the one end may also have a mercapto group. Or an epoxy group of a fluorine atom, an alkyl group having a hydrogen atom or a carbon number at one end, or an epoxy group having a trans group or a fluorine atom may have an addition molar number of 2 to 2 Å. a poly(ethylene oxide) group having an alkyl group having a hydrogen atom or a carbon number at the terminal also having a hydrogen atom or a carbon atom at the terminal end. The alkyl group may have a propylene oxide group having a hydroxyl group or a fluorine atom, a polyepoxy group having a molar number of 2 to 20, a group represented by the formula (111), or a group represented by the formula (IV): R9

U—R7—N—R8~ C 00~ (III) R10 wherein R7 and R8 each independently represent an alkylene group of carbon number 4, and R9 and R1 ° are each independently represented by a hydrogen atom or a carbon number. Alkyl group of 4; 201211072 R1

RINIR 12 13

14 JR

In the formula, R represents an alkylene group having a carbon number of 1 to 4, ... and a Ru group each independently represents a hydrogen atom or a carbon number of a burnt group, an organic group, or a sulfonium-based anion; (4) as described above ( 2) The two-component surface modifier according to (3), wherein the number of the repeating units represented by the formula (I) is ^000. (2) The two-component surface modifier according to any one of the above-mentioned items (1) to (4), wherein the lithium-based lithium coupling agent is an alkoxy group represented by the formula (VIb) Base group compound: R15 (VIb)

Rl6-Si-Rl8-SH R17 wherein each of the alkoxy groups of the carbon number 或 or the number of carbon atoms of the alkoxy group m R17 of 4 is independently a calcined oxy group 'R18' represents a carbon number (2) The 2-liquid surface modifying agent as described in any one of the above items (1) to (5), wherein the (meth)acrylic monomer is represented by the formula (10) (Acene monomer: (Vb) CH2=C—CO-R20 R19 In the formula, R represents a hydrogen atom or a methyl group, and #ττκ is not hydrophilic. Hydrophobic group, cationic group or anion (2) The two-liquid type surface modifying agent according to the above (6), wherein in the case of 201220122 (Vb), the carbon number of the hydrogen atom, the hydroxyl group or the fluorine atom may be 2 to 2 in the r2° system. The alkyl group, which may have a hydroxyl group or a fluorine atom, has a carbon number of 6 to 2 fluorene. The alkyl group having a hydrogen atom or a carbon number of 1 to 4 at one end may have an oxiranyl group having a hydroxyl group or a fluorine atom. The alkyl group having a hydrogen atom or a carbon number of 丨4 is also a polyethylene oxide group having an alkylene group having a trans group or an I atom, and having a molar number of 2 to 2 Å, and hydrogen at one end. Atomic or carbon number The alkyl group may have an oxypropylene group having a hydroxyl group or a fluorine atom, an alkyl group having a hydrogen atom or a carbon number of 1 to 4 at one end, or an oxiran group having a hydroxyl group or a fluorine atom. a polyepoxypropane group of 2 to 20, a group represented by the formula (111), or a group represented by the formula (IV): R9

U -R7-N-R8-COO~ (in) R10 where 'R7 and R8 each independently represent a sub-dottyl group having a carbon number of 1 to 4, and R and R" are independently represented by a hydrogen atom or a carbon number. Alkyl group of 1 to 4; R12 η I + -Ru-N-R14 · χ- (ιν) R13 wherein 'R" means a alkylene group having a carbon number of 1 to 4, and R12 and R13 each independently represent hydrogen. The atomic or carbon number 4 alkyl group, the R14 organic group, and the fluorene-based system represent an anion; (8) A method for producing a surface-modified substrate, characterized in that the substrate is coated with an alkoxy group. After the thiol-based polymer and the thiol group-containing silane coupling agent liquid I, the surface of the substrate coated with the liquid I is coated with a π liquid containing 12 201211072 (fluorenyl) acryl monomer to have a thiol The method for producing a surface-modified substrate according to the above (8), wherein the polymer having an alkoxyfluorenyl group has the formula (1) The above-mentioned repeating unit, having at least one end of the formula (1)), is a compound of the formula (1)):

I (I) 〇

In the formula I R2, the R hydrogen atom or a thiol group, a hydrophilic group, a hydrophobic group, a cationic group or an anionic group is represented by a unit, at least one side of the terminal formula (11): R3 R4~f ~R6~ (II) R5 wherein R3, R4 and R5 independently represent at least one of the carbon number i ~ 4 alkyl group or the carbon number 院 of the oxy group m R5 - a base carbon number of 1 to 4 (A) The method for producing a surface-modified base material according to the above (9), wherein the R2 system may have a hydrogen atom, An alkyl group having 2 to 20 carbon atoms of a hydroxyl group or a fluorine atom, a 6 to 2 aryl group having a hydroxyl group or a fluorine atom, and a hydrogen atom or a carbon number at the terminal end may have a base group or a gas group. The oxirane group of the genomic group has a hydrogen atom at one end or a carbon number of 1 to 4; 201211072 alkyl group may also have an oxiranyl group having a hydroxyl group or a fluorine atom, and the molar number is 2 to 20 The poly(ethylene oxide) group having a hydrogen atom or a carbon number at one end may have an oxypropylene group having a hydroxyl group or a fluorine atom, a germanium atom at one end or a carbon number of 1 to 4. The alkyl group may have a propylene oxide group having a hydroxyl group or a fluorine atom, a polyepoxy group having a molar number of 2 to 20, a group represented by the formula (111), or a group represented by the formula (IV). : R9

R (III) r - N - R 8 ~ CO 〇 - R10 9 wherein & R8 each independently represents an alkylene group having a carbon number of 1 to 4 and a ^1 ° system independently representing a hydrogen atom or carbon In the formula, R11 represents an alkylene group having 1 to 4 carbon atoms, and a Ru system independently represents a hydrogen atom or (11) The method for producing a surface-modified substrate according to the above (9) or (10), wherein the base of the carbon number of the carbon number, the R1, 4, and 10, The method for producing a surface-modified substrate according to any one of the above-mentioned items (8) to (11), wherein the decane coupling agent having a thiol group is used. , a compound containing an alkoxy fluorenyl group represented by the formula (v丨b ):

R 16.

R15 Si-R18-SH R17 (VIb) 14 201211072 In the formula, R, R and R each independently represent a carbon group of carbon number 4 or an alkoxy group of carbon number 1 to 4 'R15, V6 and r" At least one of the bases is an alkoxy group having 1 to 4 carbon atoms, and R18 is an alkylene group having a carbon number of i to 12; (13) The surface modification according to any one of the above (8) to (11) A method for producing a substrate, wherein the (meth)acrylic monomer is a (meth)acrylic monomer represented by s(Vb): CC—*C — Ο — R20 U (Vb) wherein R19 represents The hydrogen atom, the methyl group, and the R2 are a hydrophilic group, a hydrophobic group, a cationic group, or an anionic group. (14) A method for producing a surface-modified substrate according to the above (13), wherein (Vb), R" may have a hydrogen atom, a hydroxyl group or a fluorine atom having a carbon number of 2 to 20, a carbon group having a transradical or a fluorine atom of 6 to 2 fluorene, a hydrogen atom at one end or The fluorenyl group of the carbon number 4 may also have an oxiranyl group having a trans group or a t* atom, an alkyl group having a hydrogen atom or a carbon number at one end, and an oxyethylene group having a hydroxyl group or a fluorine atom. Cheng Mo a poly(ethylene oxide) group having 2 to 20 carbon atoms and a hydrogen atom or a carbon number at the terminal end may have an oxypropylene group having a hydroxyl group or a fluorine atom, and a hydrogen atom or carbon at the terminal end. The alkyl group having 1 to 4 may have a propylene group having a hydroxyl group or a gas atom, and a group having a molar number of 2 to 20, a group represented by a gas (III), or a formula ( IV) Base: R9

U -R7-N-R8-CO〇_ (Ιπ) 15 201211072 wherein R7 and R8 each independently represent an alkylene group R9 and R" of carbon number 4, respectively, independently represent 'hydrogen atom or carbon number Alkyl group of 1 to 4; R12 (IV) 11 丨+ lil -Rn-N-R14 · X- 13

In the formula, Rn represents an alkylene group having a carbon number of 4, and a group of 1^2 and r!3 each independently represents a hydrogen atom or an alkyl group having a carbon number of 4, an R14 organic group, and an anthracene system representing an anion; And (15) a surface-modified substrate obtained by modifying the surface of the two-component surface modifier described in any one of the above (1) to (?). Further, by using the above-described two-liquid type surface modifying agent, a coating solution comprising a polymer having an alkoxyfluorenyl group and a decane coupling agent containing a thiol group is applied to the substrate. The surface of the liquid substrate is coated with a solution containing (methyl; acrylic acid monomer, and reacting a thiol group-containing coupling agent with a (meth)acrylic monomer to change the surface of the substrate by m. The surface modification method of the substrate can also be provided by using the two-component surface modifier of the present invention. [Group 3 of the present invention] The third group (1)-type surface hydrophilizing agent of the present invention is characterized by: The acrylic polymer is obtained by polymerizing a monomer component containing a nitrogen atom and a monomer having a nitrogen atom represented by the formula (1): atomic abundance R3 I • Si-R < I R6 (IX) R1

I

HjC = C — C—Y—R*

II 〇 8 16 201211072 wherein R1 represents a hydrogen atom or a methyl group, and R3, R4 and R5 each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, R3, R4 and R5. One of the bases is an alkoxy group of carbon number 4, and the ring group of R6 represents a carbon number H. The Y group represents an oxygen atom or _NH; R1 R9 H2C = CCY-R6-n-R8-c〇 〇· (X) 〇41° wherein R, R and Υ are the same as above, and r8 represents an alkylene group having 1 to 4 carbon atoms, R9 and R1. (2) The surface hydrophilizing agent according to the above (1), wherein the monomer having a ruthenium atom represented by the formula (1x) and the formula (X) The weight of the monomer containing a nitrogen atom (a monomer containing a halogen atom / a monomer containing a nitrogen atom) is 3/97 to 95/5; (3) as described in the above (1) or (2) a surface hydrophilizing agent, wherein the monomer-forming process comprises a monomer copolymerizable with a monomer containing a dream atom represented by the formula (IX) and a monomer having a nitrogen atom represented by the formula (X); The surface hydrophilizing agent according to the above (3), wherein a monomer which is copolymerizable with a monomer having a ruthenium atom represented by the formula οχ) and a monomer having a nitrogen atom represented by the formula (x)m is selected A surface-hydrophilizing agent according to the above (3) or (4), wherein at least one of the group consisting of a free styrene monomer, a few acid vinegar monomer, and an amine monomer; a monomer having a ruthenium atom-containing monomer represented by the formula (IX) and a monomer containing a nitrogen atom represented by the formula (X), and a monomer having a zea atom represented by the formula ΠΧ) Containing nitrogen as shown in formula (X) The total of the atomic monomers is 4 1 〇〇 the weight portion 17 201211072 equivalent 0 to 100 parts by weight; and (6) the surface (1) to (5) of any one of the 0 hydrophilized substrate 'is attached to the base The surface of the material is formed into a film composed of the surface hydrophilizing agent described in the above item. [Effect of the Invention] According to the first group of the present invention, it is possible to provide a hydrophilic material which is not easily detached from the substrate even when it is in contact with water. Properties, water repellency, lipophilicity, oil repellency, etc. The surface modifier of the 4th film of the desired properties; the surface of the surface modifier is modified to temporarily Au. A method for producing a (meth) propylene-based polymer of the alkoxy oxime of the surface modifier. According to the second group of the present invention, for example, a surface modifying agent which can be immobilized on the substrate and which has two properties opposite to hydrophilicity and lipophilicity, hydrophilicity and oil repellency, and the like can be provided; Two properties opposite to hydrophilicity, lipophilicity, hydrophilicity and oil repellency, etc., can be immobilized on a surface-modified substrate of a substrate; and, for example, a surface modifier can be provided on the surface thereof. The surface of the surface modifier can be modified into a substrate having two properties which are opposite in hydrophilicity and lipophilicity, hydrophilicity and oil repellency. According to the third group of the present invention, it is possible to provide a surface hydrophilizing agent which can form a surface having excellent hydrophilicity on the surface of the substrate from the substrate even when it is in contact with water. A surface hydrophilizing substrate comprising a superficial film composed of the surface hydrophilizing agent is formed on the surface. [Embodiment] 8 201211072 [Group 1 of the present invention] The surface modifier of the first group of the present invention contains the formula (II) at least at one end including the "repetitive unit represented by the formula (I)" as described above. ) of the fluorenyl fluorenyl (fluorenyl) acrylate polymer shown: R1

I fC-CH23—

I 〒=〇 (I) 〇

In the formula I R2, R1 and R2 are the same as above; R3 R4 to Si-Re-(Π) R5 wherein 'R3, R4 and R5 are the same as described above. The repeating unit represented by the formula (I) is a hydrogen atom or a methyl group. R2 is a hydrophilic group, a hydrophobic group, a cationic group or an anionic group. The properties imparted to the substrate by the surface modification agent can be adjusted by selecting the type of the hydrophilic group U group, the cationic group or the anionic group. For example, when hydrophilicity is imparted to the substrate, when a hydrophilic organic group is selected to impart hydrophobicity to the substrate, a hydrophobic organic group is selected. For example, an alkyl group which may have a hydrogen atom 'passage group or a fluorine atom', an alkyl group which may have a hydroxyl group or a fluorine atom, an aryl group, a terminal side having a hydrogen atom or a carbon number of 14 may be mentioned. The alkyl group may also have a hydroxyl group or an oxirane group of the mat, and the side has a wind atom or a carbon number of 1 to 4 4 and may also have a hydroxyl group or a fluorine sheet. The addition of the epoxy ethyl group to the molar number # 19 201211072 2, the polyepoxide (4), the terminal at the end of the hydrogen atom or carbon number 4 can also have a hydroxy group or a fluoropropane group of a fluorine atom a propylene group having a hydrogen atom or a carbon number enthalpy at one end or a propylene oxide group having a trans group or a fluorine atom, and a polyglycidyl group having a molar number of 2 to 2 Å, and a formula (1) ) the base shown in the formula ' or formula (IV):

7 R

Οο C I 8 R 9+110 R·-Ν·-R 9 wherein R represents independently an alkylene group having a carbon number of 1 to 4, and R1. Each independently represents a hydrogen atom or an alkyl group of carbon number 4; R12,, I + (IV) — R11—N—R!4 . y-

In the formula, R is an alkylene group having a carbon number of 4, a group of Rlz and a group of RU, a thio group having a hydrogen atom or a carbon number of 4, an organic group of an R14 group, and an anion of X. It is not limited to this illustration. In the basis of these: from the viewpoint of the strength of the coating film, the base represented by the formula (III) is preferred. 7 is in the formula (111), and R7 and R8 are each independently an alkylene having a carbon number of 丨~4. The group R is preferably a methylene group, an ethylene group, a n-propylene group or an isopropylidene group, and more preferably a sub-group or an ethylene group. R8 is preferably a methylene group or an ethylene group. In the formula (IV), the alkylene group of the R 1 -carbon number 4 is preferably an anthracenylene group, an n-propylene group or an isopropylidene group, and a methylene group or an ethylene group; R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a lanthanoid organic group. Specific examples of the organic group include an alkyl group of carbon number 22, an aryl group of carbon | 20 201211072 6] 2, a (four) group of carbon number 2, and the like, but the present invention is not limited to the preferred example of m ion. The carbon number of the sulphur-based chloride ion-burning group is a sulphur-based sulphate ion having a valence of 4, a carboxyl group ion having a carbon number of 68, and an alkyl group having an alkyl group having a carbon number of η. Sulfate ion ion _ 素 ion, acetic acid ion, acid ion, bar acid ion / 酉; 5 acid ion, hydrogen hydride, heavy sulfite +, sulfate ion, sulphuric acid ion, etc. It is not limited to this illustration. The above-mentioned functional group of the sulfuric acid ion of the compound is a gas atom, a gas atom, and an iodine atom. The halogen atom of the above-mentioned sulfonate ion may, for example, be a fluorine atom, a gas atom, a bromine atom or an iodine atom. Among the ruthenium, an alkyl hydride ion having a carbon number, an alkyl group having a carbon number of the alkyl group, and an aryl vapor ion having a carbon number of 6 to 8 are preferred. Specific examples of the monomer having a group represented by the formula (IV) include <N-dimethylaminoethyl (meth) acrylate gas methane salt, N, N-dimethylamino group B Base (mercapto) acrylate dimercapto sulfate, N,N-dimethylaminoethyl (meth) acrylate diethyl sulfate, N,N-dimethylaminoethyl (methyl Benzyl methoxide of acrylate ester, N,N-dimethylaminopropyl (meth) acrylate gas methane salt, N,N-dimethylaminopropyl (meth) acrylate Base sulfate, N,N-dimethylaminopropyl (meth) acrylate diethyl sulfate, benzyl chloride of hydrazine, hydrazine-didecylaminopropyl (hydrazino) acrylate, Ν, Ν-diethylaminoethyl (meth) acrylate chloromethane salt, ν, Ν-diethylaminoethyl (meth) acrylate dimethyl sulfate, hydrazine, hydrazine - diethyl Benzyl, hydrazine, hydrazine-diethylaminopropyl propylaminoethyl (meth) acrylate diethyl sulphate, hydrazine, hydrazine-diethylaminoethyl (meth) acrylate (methyl) 21 201211072 Acrylate methyl chloride salt, N,N-diethylaminopropyl (meth) acrylate dimethyl sulfate, N,N-diethylaminopropyl (meth) acrylate diethyl sulphate, N, N- A benzyl chloride salt of diethylaminopropyl (meth) acrylate or the like, but the invention is not limited to the exemplification. Among these monomers, it is inexpensive and can be easily obtained as N,N-didecylaminoethyl (meth) acrylate gas methane salt, N,N-dimethylaminoethyl (A Acrylate diethyl sulfate or the like is preferred. In the case of R, the hydrophilic group is, for example, a carbon number of at least one hydrogen atom, a hydroxyl group having 1 to 4 carbon atoms, and a hydrogen atom or a C 1 to 4 alkyl group at one end. a polyethylene glycol group having a hydrogen atom or a carbon number of 1 to 4 at one end and a polypropylene glycol group having a carbon number of 1 to 4, a group represented by the formula (III), etc., but the present invention is not Limited to this illustration. In the basis of these, the formula (1) is used from the viewpoint of enhancing the strength of the coating film. The base shown is preferred. The R2'-hydrophobic group may, for example, be an alkyl group having 2 to 20 carbon atoms of a fluorine atom, an aryl group having 6 or a carbon number of a fluorine atom, and the like, but the invention is not limited to the examples. Among these groups, from the viewpoint of oil repellency, it is preferred that the number of fluorine atoms is 3 or more and the carbon number is 2, and the number of the base group and the complex atom number is 3 or more and the carbon number is 6 to 20. The present invention is not limited to the R, an anionic group, and examples thereof include, for example, an ethylene phenoxy decyl group, a stilbene oxiranyl ethyl group, and the like. However, the present invention is not limited to this example. From the viewpoint of imparting hydrophilicity, water repellency, and cationicity to the surface of the substrate, the lower limit of the number of the reverse units represented by the formula (1) is preferably only 8 22 201211072 or more, more preferably 10 or more. The upper limit of the number of the repetitive units represented by the formula (1) is preferably 1 000 or less, more preferably 500 or less. In the alkoxyfluorenyl group represented by the formula (U), R3 and RS are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having a carbon number of 4, and at least one of RS, R4 and A carbon number alkoxy group. At least one of R3, V and fluorene is an alkoxy group having a carbon number of Η, which is obtained by chemically bonding a surface modifying agent to a substrate. Therefore, among R3, R4 and y, at least one group is preferably an alkoxy group having 1 to 4 carbon atoms, and R3, & RS is

Further, R5 is further preferably two groups of alkoxy groups having a carbon number of 4, and preferably an alkoxy group having 1 to 4 carbon atoms. Among the alkyl groups having a carbon number of 44, a methyl group and an ethyl group are preferred, and a methyl group is more preferred. Among the alkoxy groups having a carbon number, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred. The alkoxy fluorenyl group represented by the formula (II) is an alkylene group having a carbon number of 12. Among R6, an alkylene group having 1 to 6 carbon atoms is preferred, and a sub-alkyl group having 2 to 6 carbon atoms is more preferred. The alkoxy group represented by the formula (II) has a (meth)acrylic polymer at least at one end, and the viewpoint of the properties of the (meth)acrylic polymer is sufficiently exhibited. It is preferably present only at the - edge of the (fluorenyl) acrylic polymer. When the alkoxyfluorenyl group represented by the formula (1)) is present only at the terminal end of the (meth)acrylic acid-based polymer, from the viewpoint of sufficiently exhibiting the properties of the (meth)acrylic polymer, The other end is preferably a group such as a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a residue of a polymerization initiator. / (M) is a (meth)acrylic polymer having an alkoxyfluorenyl group represented by the formula 23 201211072 (11) at least at one end, for example, by the formula ( The (meth)acrylic monomer shown in Va) is polymerized in the presence of a compound containing an alkoxyfluorenyl group represented by the formula (VIa): C H2 = C - C _ Ο _ R2 (Va) (Via)

I, II R丨〇 where R1 and R2 are the same as above R3

I R4—Si-R6- SH R5 wherein R3, R4, R5 and R6 are the same as above. The (meth)acrylic monomer represented by the formula (Va) may, for example, be N-(methyl)acryloyloxyethyl-N,N-dimethylammonium monodecylcarboxybetaine, fluorene-(fluorenyl) Ethyl acrylamide ethyl-ν, ν-dianonyl ammonium _α_ carboxycarboxybetaine, decyloxytriethylene glycol (meth) acrylate, 22,2-trifluoroethyl methacrylate Etc., the invention is not limited to this illustration. These (meth)acrylic monomers may be used alone or in combination of two or more. In addition, Ν-mercapto propylene oxime oxime Ν Ν Ν 曱 曱 曱 _ 甲基 甲基 甲基 9 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 9 9 9 9 9 9 9 9 9 9 9 9 9 The method described is easily modulated in high purity. The alkoxyfluorenyl group-containing compound represented by the formula (Via) may, for example, be a 1 thiopropyl 3 dimethoxy fluorene, 1-thiopropyl-3-triethoxy oxime, 1-thiopropyl 3--3-isopropoxy decane, thiopropyl-3-methylmethoxy decane, 1-thiopropyl I methyldiethoxy oxacyclohexane, thiopropyl-3-methyl 24 201211072 Dipropoxy stone court, etc., but the invention *North-汾_I is not limited to this illustration. These compounds containing the oxime group can be used s. J knife alone or in combination of two or more. The amount of the alkoxyfluorenyl group-containing compound which is not represented by the formula (Via) is not particularly limited, and is usually preferably from 0.01 to 10 parts by weight based on the total amount of the monomer to be polymerized. Further, the (meth)acrylic monomer represented by the formula (Va) may be used in combination with another polymerizable monomer as long as it does not inhibit the object of the present invention. Other polymerizable monomers include, for example, styrene, hydroxyethylidene, p-hydroxystyrene, methyl (meth) acrylate, ethyl ketone (meth) acrylate, n-butyl (meth) acrylate, (a) Isobutyl acrylate, (butyl) butyl butyl acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, octyl (meth) acrylate , (methyl) propylene roasting acid laurel vinegar, (mercapto) styrene stearyl sulphate, (meth) propyl benzoic acid ester, ethyl carbitol (meth) acrylate, (mercapto) Hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, Ν-methyl ( Methyl) acrylamide, hydrazine-ethyl (meth) acrylamide, hydrazine-propyl (decyl) acrylamide, hydrazine-isopropyl (decyl) acrylamide, hydrazine-methyl (A) Base acrylamide, hydrazine-tert-butyl (meth) acrylamide, fluorene-octyl (meth) acrylamide, hydrazine, hydrazine-dimethyl ( Base acrylamide, hydrazine, hydrazine-diethyl (meth) acrylamide, (meth) propylene hydrazine, diacetone acrylamide, styrene, itaconate, ethyl itaconate , vinyl acetate, vinyl propionate, Ν-vinyl pyrrolidone, 25 201211072 N-ethylene caprolactam, etc., but the invention is not limited to this example. These other polymeric early forms can be divided into two types: one can be used separately from the field + the knife can be used alone. In the case where a (meth)acrylic monomer represented by the formula (Va) is polymerized in the presence of a compound containing an alkoxyfluorenyl group which is not represented by the formula (Va), a polymerization initiator is preferably used. The polymerization initiator may, for example, be azoisobutyronitrile, azoisobutyrate methyl acetonate, azobisdimethylvaleronitrile, benzene peroxide, persulfate _, persulfate, benzophenone derivative, A phosphine oxide derivative, a benzo-derivative, a phenyl sulfide light derivative, a stacked II compound derivative, a diazo derivative, a disulfide derivative, etc. 'But the present invention is not limited to this example. These polymerization initiators may be used alone or in combination of two or more. The starting amount of the polymerization is not particularly limited, and it is usually a part by weight of the monomer to be polymerized of the (fluorenyl)acrylic monomer represented by the formula, preferably from 0.01 to 5 parts by weight. The method of polymerizing the (meth)acrylic monomer represented by the formula (Va) can be exemplified by a solution polymerization method or the like, but the invention is not limited to the examples. When the (meth)acrylic monomer represented by the formula (Va) is polymerized by a solution polymerization method, for example, a (meth)acrylic monomer represented by the formula (Va) can be dissolved in a solvent by stirring. A polymerization initiator is added to the solution to polymerize it. Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and propylene glycol; ketones such as propyl and methyl ethyl ketone; ethers such as diethyl ether, benzene, toluene, and toluene; An aromatic hydrocarbon compound; an aliphatic hydrocarbon compound ring such as n-hexane; an alicyclic hydrocarbon compound such as hexane; an acetate f such as methyl decanoate or ethyl acetate; however, the present invention is not limited to the examples. These may be used alone or in combination of two or more. The amount of the mixture is adjusted to 10 to 80 by weight of the monomer solution containing the (meth)acrylic monomer represented by the formula (Va) for polymerization by the solution of the body dissolved in the solvent. The degree of % is better. The polymerization conditions such as the polymerization temperature and the polymerization time when the (meth)acrylic monomer is not polymerized in the formula (Va), the type of the monomer, the amount thereof, the type of the polymerization initiator, and the amount thereof to be used, etc. Suitable adjustment is better. The atmosphere in the case where the (meth)acrylic monomer is not polymerized in the formula (Va) is preferably an inert gas. The inert gas 'is, for example, nitrogen gas, argon gas or the like, but the invention is not limited to the examples. The end of the polymerization reaction and the presence or absence of unreacted monomers in the reaction system can be confirmed, for example, by a general analytical method such as gas chromatography. By polymerizing a non-(meth)acrylic acid monomer of the formula (Va) with another monomer which is used as required, a (meth)acrylic acid polymer having an epoxy group can be obtained. Further, the viscosity average molecular weight of the (meth)acrylic polymer having an alkoxy second group can be measured by, for example, a Ubbelde viscometer or the like. The viscosity average molecular weight of the (meth)acrylic polymer having an alkoxyfluorenyl group is preferably from i 〇〇 or more, more preferably 500 or more, and has an alkoxy group from the viewpoint of sufficiently exhibiting the effect of surface modification. The solubility of the (meth)acrylic polymer of the fluorenyl group is preferably 1 Å or less, more preferably 50,000 or less. The surface modifying agent of the present invention comprises a (meth)acrylic polymer having the above alkoxyfluorenyl group, and may be only a (meth) propylene having the alkoxy hydrazine 27 201211072 group. The acid polymer may be composed of a solvent β solvent, and examples thereof include alcohols such as decyl alcohol, ethanol, isopropanol, ethylene glycol, and propylene glycol; and ethyl hydrazines such as C- and f-ethyl ketone; and (four) Anthracene compounds such as benzene, toluene, xylene, etc.; aliphatic hydrocarbon compounds such as hexagram; cyclohexane and other fats such as fine-grained hydrocarbon compounds, acetic acid acetate, ethyl acetate and other acetic acid materials, but The invention is not limited to the examples. These solvents may be used alone or in combination of two or more. The amount of the solvent is not particularly limited, and the concentration of the (meth)acrylic polymer having an alkoxy group, which is usually obtained by dissolving a (meth)acrylic polymer having an alkoxyfluorenyl group in a solvent, is adjusted. The degree of weight % is preferred. The surface-modified substrate to which the surface modifier of the present invention is surface-modified can be produced by applying the surface modifying agent of the present invention to a substrate. As a substrate, a (meth)acrylic polymer having an alkoxy group contained in the present invention is chemically fixed to a substrate, and can be favorably used on the surface thereof. The substrate, the substrate of the steamed cerium oxide, and the like. The material of the substrate may, for example, be polyethylene, polypropylene, polystyrene, polyurethane, polyamine represented by nylon, polyaniline 'polyurethane, urea resin, polylactic acid, polyvinyl alcohol. , polyvinyl acetate, acrylic resin, polysulfone, polycarbonate, ABS resin, AS resin, silicone resin, glass ceramic, metal, etc. 'By the present invention is not limited to this example. Since the surface modifier of the present invention can be more firmly fixed to a substrate having a hydroxyl group on its surface, it is preferred to use a substrate having a hydroxyl group on its surface. 28 201211072 When using a substrate having no hydroxyl group on its surface, it is preferred to have a hydroxyl group on its surface by surface modification. Further, for example, when a substrate composed of glass has a sufficient hydroxyl group on its surface, it is needless to modify its surface so that a hydroxyl group exists on the surface thereof. Further, when the surface modifying agent of the present invention is used as a base material for vapor-depositing cerium oxide, the surface modifying agent of the present invention can be firmly fixed to the surface of the base material. A substrate for vapor-depositing a substrate of cerium oxide, for example, polyethylene, polypropylene, polystyrene, #vinyl chloride, polyamine represented by nylon, polyacrylonitrile polyethylene, polypropylene, poly Benzene ##, polyethylene, polyamine represented by nylon, polyimine, polyurethane, urea resin, polylactic acid, polyvinyl alcohol, polyvinyl acetate, acrylic resin, polysulfone, polycarbonate When a resin such as an ABS resin, an AS resin, or a silicone resin is formed, since the resin is generally hydrophobic, it is considered that it is difficult to firmly fix the surface modifier to the substrate composed of the resin (hereinafter, also referred to as The surface of the resin substrate). In the present invention, the surface modifying agent of the present invention can be firmly fixed to the resin substrate of the vaporized cerium oxide when the surface of the resin substrate is subjected to oxidative dicing. The method of vapor-depositing the cerium oxide on the surface of the resin substrate may, for example, be a vacuum evaporation method, a (four) method, a chemical vapor deposition method, or the like, but the invention is not limited to the examples. For example, when the surface of the resin substrate is steamed by a vacuum evaporation method, the resin substrate is placed in a vacuum capacity (four), and after degassing under heating, by using a methoxy field such as tetramethoxy sulphate The eve is introduced into the vacuum container to evaporate the dream of oxidizing on the surface of the resin substrate. Depending on the amount of oxidizing agent used on the surface of the resin substrate in the steaming clock, the resin type of the resin substrate is different from the 2012 20127272 resin, and the method is determined by the method of the method. In general, the shape of the "5J*" base material to which the surface of the present invention can be fixed to the surface of the resin substrate of the steamed silica dioxide is not particularly limited, for example, a film, a sheet, and a sheet. 'The molded body of a specific shape is formed, but the present invention is not limited to the example 4 in which the surface modifying agent of the present invention is applied to a substrate, and examples thereof include a flow coating method, a spray coating method, and a dipping method. The embossing method, the roll coating method, and the like, but the invention is not limited to the illustration. The atmosphere when the surface modifier of the present invention is applied to a substrate is usually an atmosphere. In addition, the temperature at which the surface modifier of the present invention is applied to the material is usually at room temperature, and is also a force. When the surface quality agent of the present invention is applied to a substrate, the amount of the surface modifier to be coated according to the present invention differs depending on the use of the substrate, so that no heat and heat are generally determined. The use is suitable for adjustment. It is preferable to apply the surface modifier of the present invention to the substrate 2 from the viewpoint of improving production efficiency. The addition of the 'blade' of the substrate is different, so it cannot be decided in general terms.

Generally, the temperature at which the A residual substrate brings the dip in the range of 50 to 15 (Tc is preferable. As described above), the surface modifying agent of the present invention can be applied to the surface of the present invention by applying the surface modifying agent of the present invention to the substrate. The (meth)acrylic polymer having the alkoxyfluorenyl group and the modifier is fixed to the substrate. The surface-modified substrate of the present invention is modified by the surface-modified surface on the surface thereof. The (meth)acrylic acid 30 201211072 having an alkoxyfluorenyl group can have properties such as (meth)acrylic acid of the substrate (tetra)oxy #, which can prevent the use of the former The surfactant is lost due to moisture adhesion. b, the substrate of the surface modifier of the present invention is modified, and the base of the (meth)acrylic polymer having an alkoxyfluorenyl group can be adjusted. The material T is, for example, a desired property such as hydrophilicity, hydrophobicity, lipophilicity, oil repellency, etc. Further, the surface modifier of the present invention does not require the invention described in the above Patent Document 5 to be made on the surface of the substrate. The monomer composition is polymerized, and the surface of the substrate can be modified by coating it on the surface. There is a point that the surface-modified substrate which has been modified to the surface of the substrate can be easily produced in a short time. [Group 2 of the present invention] The two-component surface modifier of the second group of the present invention is as described above. It consists of a liquid I containing a polymer having a base for burning oxygen and a money coupling agent containing a base; and a liquid containing a (meth)acrylic monomer. [I liquid] First, the liquid I is described. A polymer having an alkoxyfluorenyl group and a decane coupling agent containing a thiol group. A preferred example of the polymer having an alkoxyfluorenyl group is a repeating unit represented by the formula (I), and has at least one terminal end. (Alkyl)acrylic polymer of the alkoxyfluorenyl group represented by the formula (11): 31 (I) 201211072 R1

I —Ec — c h2 3— c=o

I 0 1 R2 wherein 'R1 represents a hydrogen atom or a methyl group, and r2 represents a hydrophilic group, a hydrophobic group, a cationic group or an anionic group; R: (II) R4-Si-R (

I

In the formula, R3, R4 and R5 each independently represent an alkyl group having a carbon number of 丨4 or an alkoxy group having a carbon number of ,, and at least one of the base groups of R3 and R5 is an alkoxy group of 1 to 4, R6 represents an alkylene group having a carbon number of 12. Formula (I) represents a repeating unit, and R1 is a hydrogen atom or a methyl group. R2 is a hydrophilic group, a hydrophobic group, a cationic group or an anionic group. The (meth)acrylic polymer having an alkoxyfluorenyl group may be a work of only a hydrophilic group, a hydrophobic group, a cationic group, or an anionic group, or two or more kinds thereof. By selecting the type of the hydrophilic group hydrophobic group, the cation group or the anionic group, the properties of the surface modifier substrate are integrated. For example, when gland jfel J* is hydrophilic, 'selective hydrophilicity', when hydrophobicity is imparted, a hydrophobic group is selected. Further, for example, when an aqueous group or a hydrophobic group is selected, a hydrophilic (meth)acrylic polymer having a oxyxanthene group can be used. The R2 may be, for example, a carbon atom having a carbon atom, a trans group or a gas atom of 32 201211072 2 to 20, a 62Q aryl group having a carbon atom of a meridine or a ι atom, and a hydrogen at the terminal of the - side. The atomic or carbon number of the alkyl group may have an epoxy group having a trans group or a fluorine atom, a hydrogen atom at the end of the side or a carbon number, or an epoxy group having a trans group or a fluorine atom. The base group has a poly(ethylene oxide) group having a molar number of 2' and a hydrogen atom or a carbon number of ruthenium at one end. The alkyl group having a hydrogen atom or a carbon number enthalpy may also have a polyepoxypropyl group having a molar number of 2 to 2 Å, which is represented by the formula ((1)). Base, or a group of formula (IV): R£ (III) R7-N-R8-COO' R10 g formula. The intermediate Hr8 system independently represents the sub-hospital base of the carbon number w', which independently represents a hydrogen atom or an alkyl group having a carbon number of 4;

R12 Rn-N-R14 -X (IV) 13

In the formula, Rn represents a pyridyl group of carbon number 4, and R12 and r13 are each a group of a hydrogen atom or a carbon number 烧 group, an r14 type organic group, and an X. anion. This example. Among these, the base of the formula (1) (10) is preferred from the viewpoint of enhancing the strength of the coating film. 7. The formula (III)' R7 and R« are independently carbon number 4 # 亚烧基. The methylene group is preferably an ethylene group, an n-propylene group or an isopropylidene group, and more preferably a methylene or ethylene group. R8 is preferably a methylene group or an ethylene group. 33 201211072 lies in the sub-alkyl group of formula (IV), R11, carbon number. Rii is a methylene group, an ethylene 2 JL propylene group or an isopropylidene group, preferably a fluorenylene group or an ethylene group, and an R group is independently a hydrogen atom or an alkyl group having a carbon number of 1 to 4. Specific examples of the organic group/organic group include a group of carbon number 22, an aryl group having 6 to 12 carbon atoms, and a carboxyalkyl group having 2 to 6 carbon atoms. The present invention is not limited to the exemplary m ions. (4), the alkyl sulfonate ion having a carbon number of 1 to 4, an aryl vapor ion having a carbon number of 6 to 8, an alkane The carbon number of the base is η alkyl sulfate functional ion, _ 素 ion, acetic acid ion, shed acid ion, lemon acid ion, tartaric acid ion, hydrogen sulfate ion, bisulfite ion, sulfate ion, sulphate ion, etc. However, the invention is not limited to the examples. The halogen atom of the above alkylsulfate halide ion may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The atomic element of the dentate ion may be a fluorine atom, a gas atom, a bromine atom or an iodine atom. Among the oxime, the alkyl chloride ion of the carbon number 4, the carbon number of the alkyl group is preferably an alkyl sulfonate ion of 丨 4 and an aryl chloride ion having a carbon number of 6 to 8. Specific examples of the monomer having a group represented by the formula (iv) include a gas methane salt of N,N-dimethylaminoethyl (meth)acrylate, and N,N-didecylamino group B. Base (meth) acrylate dimethyl sulfate, N,N-dimethylaminoethyl (meth) acrylate diethyl sulfate, N,N-dimethylaminoethyl ( Benzyl methoxide of methyl acrylate, N,N-dimethylaminopropyl (meth) acrylate, gas, salt, N,N-monomethylaminopropyl (fluorenyl) Acetate dimethyl sulfate, N,N-dimethylaminopropyl (meth) acrylate diethyl sulfate, N,N-dimethylaminopropyl (meth) acrylate Benzyl gas salt, 34 201211072 N,N-diethylaminoethyl (mercapto) acrylate gas methane salt, N,N-diethylaminoethyl (mercapto) acrylate dimethyl sulfate Salt, N,N-diethylaminoethyl (meth) acrylate diethyl sulfate, N, N-diethylaminoethyl (meth) acrylate benzyl, N, N -diethylaminopropyl (meth) acrylate methyl chloride salt, N, N- Ethylaminopropyl (meth) acrylate dimethyl sulfate, N, N-diethylaminopropyl (meth) acrylate diethyl sulfate, N, N-diethylamino Benzyl chloride salt of propyl (meth) acrylate, etc. 'But the invention is not limited to this exemplification. Among these monomers, N,N-didecylaminoethyl (meth) acrylate chloroformate, N,N-didecylaminoethyl (e.g., inexpensive and readily available) Methyl acrylate diethyl sulfate or the like is preferred. In the case of R, the hydrophilic group may, for example, have a carbon number of at least one hydrogen atom, an alkyl group having 1 to 4 carbon atoms in the group, and an alkyl group having a hydrogen atom or a carbon number of 1 to 4 at one end. a polyethylene glycol group of ～20, a polypropylene glycol group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end, a base of the formula (III), etc., but the present invention It is not limited to this illustration. Among these, the base represented by the formula (111) is preferred from the viewpoint of enhancing the strength of the coating film. In the case of R2, the hydrophobic group may, for example, be an alkyl group having 2 to 20 carbon atoms of a fluorine atom, an aryl group having 6 to 2 carbon atoms which may have a fluorine atom, and the like, but the invention is not limited to the examples. Among these groups, from the viewpoint of oil repellency, an alkyl group having 3 or more carbon atoms and 2 to 20 carbon atoms and a group having 3 or more carbon atoms and 6 to 20 carbon atoms are preferred. In the case of R2, the oxime ion group may, for example, be a group represented by the formula (IV), but the invention is not limited to the examples. 35 201211072 In the case of R, an anionic group may, for example, be a vinylidene phenoxy dodecyl group or a carboxyethylaminoethyl group, but the invention is not limited to the examples. From the viewpoint of imparting hydrophilicity, water repellency, cationicity or anionic property to the surface of the substrate, the lower limit of the number of the reversing units represented by the formula (I) is preferably 1 or more, more preferably 10 or more, and the formula ( 1) The upper limit value of the number of the repeated units indicated is preferably 1 000 or less, and more preferably 500 or less. In the alkoxyfluorenyl group represented by the formula (11), R3, R4 and R5 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, among R3, R and R5. At least one group is an alkoxy group having 1 to 4 carbon atoms. At least one of R3, R4 and R5 is an alkoxy group having 1 to 4 carbon atoms, which is obtained by chemically bonding a surface modifying agent to a substrate. Therefore, at least one of R3, R4 and R5 is preferably an alkoxy group having a carbon number of 4, and at least two of R3, R and R5 are more preferably an alkoxy group having a carbon number of 4, R3 Further, all of the alkoxy groups having a carbon number of 1 to 4 are preferred. Among the alkyl groups having 1 to 4 carbon atoms, the mercapto group and the ethyl group are preferred, and the mercapto group is more preferable. Among the alkoxy groups of carbon number 4, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred. The alkoxyfluorenyl group R6 represented by the formula (II) is an alkylene group having a carbon number of 丨12. Among R6, an alkylene group having a carbon number of 6 is preferred, and a sub-alkyl group having a carbon number of 2 to 6 is more preferred. The alkoxyfluorenyl group represented by the formula (II) is based on the fact that the (meth)acrylic polymer is present at least at one end, from the viewpoint of sufficiently exhibiting the properties of the (meth)acrylic polymer. It is preferably only present at one end of the (meth)acrylic polymer. When the alkoxyfluorenyl group represented by the formula (II) is present only at one end of the (fluorenyl)acrylic polymer, the viewpoint of the properties of the acrylic polymer (Fig. 201211072) is sufficiently exhibited. The other end is preferably a group such as a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a residue of a polymerization initiator. The (meth)acrylic polymer represented by the formula (I) is represented by the formula (I), and the (meth)acrylic polymer having the alkoxyfluorenyl group represented by the formula (II) at least at one end is, for example, In the presence of a compound containing an alkoxyfluorenyl group as shown in VII), a (mercapto)acrylic monomer represented by the formula (VIII) is polymerized to prepare: R3 (VII) R4—Si—r6—sh

Rs where R3, R4' R5 and R6 are the same as above; C H2 = C H — C — O — R2 (VIII)

丨, II R1 〇 where R1 and R2 are the same as above. The alkoxyfluorenyl group-containing compound represented by the formula (VII) may, for example, be a guanidinyl group, a decyloxy group, a 1-thiopropyl-3-(3-ethoxy) calcined product, or a 1-thiopropyl group. 3--3-isopropoxydecane, thiopropyl-3-methyldimethoxydecane, thiopropyl-3-methyldiethoxydecane, thiopropyl-3-methyl Dipropoxylate, etc. 'But the invention is not limited to this illustration. These compounds containing a thioxanthene group may be used singly or in combination of two or more. The amount of the alkoxyfluorenyl group-containing compound represented by the formula (VII) is not particularly limited. Usually, the total amount of the monomer to be polymerized is 100 parts by weight, and preferably 37 201211072 0.01 to 10 parts by weight. The (fluorenyl) acrylic monomer represented by the formula (VIII) may, for example, be N-(indenyl)acryloyloxyethyl_N,N-dimethylammonium-α_N_methylcarboxybetaine, N -(Meth)acryloylamino-ethyl*_NN_dimethylammonium_〇_didecylcarboxybetaine, decyloxytriethylene glycol (meth)acrylate, 2,2,2-trifluoroethyl A acrylate or the like, but the invention is not limited to the exemplification. These (meth)acrylic monomers may be used alone or in combination of two or more. Further, N-methyl propylene oxiranyl-N,N-dimethylammonium _N_methylcarboxybetaine can be, for example, JP-A-9-95474, JP-A-9-95586, and JP-A-N-22247 The method described in the publication or the like is easily prepared in high purity. In addition, as long as the object of the present invention is not inhibited, the (mercapto)acrylic monomer represented by the formula (VI11) may be used in combination with another polymerizable monomer, for example, as another polymerizable monomer. Styrene, α-hydroxystyrene, p-benzoic ethylene, decyl (meth)acrylate, methoxyethyl (meth)acrylate methoxybutyl (meth)acrylate, fluorene-fluorenyl (fluorenyl) acrylamide, hydrazine-ethyl (fluorenyl) acrylamide, hydrazine-propyl (decyl) acrylamide, hydrazine-isopropyl (decyl) acrylamide, hydrazine-methyl ( Indenyl amide, hydrazine-tert-butyl (fluorenyl) acrylamide, fluorenyl-octyl (meth) acrylamide, hydrazine, fluorenyl-diyl (mercapto) acrylamide, hydrazine, Ν-Diethyl (meth) acrylamide, (meth) propylene morpholine, diacetone acrylamide, methyl itaconate, ethyl itaconate, ethyl acetate, ethyl propionate Vinegar, bismuth - ethylene. Bihafenone, oxime-ethylhexene, etc. The invention is not limited to this example. These other polymerizabilities 38 201211072 monomers may be used alone or in combination of two or more. When a (meth)acrylic monomer which is not a compound of the formula (VIII) is polymerized in the presence of a compound containing an alkoxyfluorenyl group represented by the formula (VII), a polymerization initiator is preferably used. The polymerization initiator may be the same as the user of the first group of the present invention. Usually, the total amount of the monomer to be polymerized by the (meth)acrylic monomer represented by the formula (VIII) is 100 parts by weight, preferably 0.01 to 5 parts by weight. The method of polymerizing the (meth)acrylic monomer represented by the formula (VIII) may, for example, be a solution polymerization method, but the invention is not limited to the examples. When the (meth)acrylic monomer of the formula (VIII) is polymerized by a solution polymerization method, for example, a (mercapto)acrylic monomer represented by the formula (νίπ) can be dissolved in a solvent, and stirred by stirring. A polymerization initiator is added to the solution to polymerize it. The solvent may be the same as that of the user of the third group of the present invention. It is preferable to adjust the monomer concentration of the solution in which the monomer is dissolved in the solvent to 1010% by weight, usually by containing the (meth)acrylic monomer represented by the formula (VIII). The polymerization conditions such as the polymerization temperature and the polymerization time in the polymerization of the (fluorenyl)acrylic monomer represented by the formula (VIII), the type of the monomer, the amount thereof, the type of the polymerization initiator, and the amount thereof to be used, etc. Suitable adjustment is better. The atmosphere at the time of polymerizing the (meth)acrylic monomer represented by the formula (VIII) is preferably an inert gas. The inert gas may, for example, be nitrogen gas, argon gas or the like, but the invention is not limited to the examples. The end of the polymerization reaction and the presence or absence of unreacted monomers in the reaction system can be confirmed, for example, by a general analytical method such as gas chromatography. 39 201211072 A polymer having an alkoxyfluorenyl group can be obtained by polymerizing a (meth)acrylic monomer represented by the formula (VIII) with another monomer as required. Further, the viscosity average molecular weight of the polymer having an alkoxyfluorenyl group can be measured by, for example, a Ubbelde viscometer or the like. The viscosity average molecular weight of the polymer having an alkoxyfluorenyl group is preferably 100 or more, more preferably 500 or more, from the viewpoint of sufficiently exhibiting the effect of surface modification, and is improved by a polymer having an alkoxyfluorenyl group. The viewpoint of solubility is preferably 1,000,000 or less, and more preferably 5 Å or less. The liquid I used in the present invention comprises a polymer having an alkoxyfluorenyl group and a decane coupling agent containing a thiol group. The decane coupling agent having a thiol group' may, for example, be a compound containing an alkoxyfluorenyl group represented by the formula (Vb):

R16 R16-Si-Rl8~SH R17 (VIb) wherein R15, R16 and Rn each independently represent an alkyl group having a carbon number or an alkoxy group having a carbon number of 4, and at least R15, ^6 and R" One base is an alkoxy group having 1 to 4 carbon atoms, and R18 is a sub-group having a carbon number of 1 to 12; however, the invention is not limited to the examples. In the alkoxyfluorenyl group-containing compound represented by the formula (Vb), RU, Rle and R17 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, R, R and R. At least one of the bases is an alkoxy group having 1 to 4 carbon atoms. At least one of the bases 15, R16 and R" is an alkoxy group having a carbon number of 1 to 4, which is a surface modifying agent fixed by chemical bonding. Therefore, at least 40 of the Ri5 and r" 201211072 The alkoxy group is preferably alkoxy, and at least two of r15, r16&r, and the carbon number of the group are more preferably alkoxy groups, and the steps are r15, r6, and F are all carbon numbers. The oxy group is better. Among the alkyl groups of the carbon number, the methyl group and the ethyl group are preferred, and the methyl group is more preferable. Among the methoxy groups of the carbon number 4, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred. R18 is a sub-shallow group of carbon number. In the case of π, the residue of carbon number 8 is preferred, and the sub-base of carbon number 6 is more preferable, and the sub-base of carbon number 2 to 6 is better. The I liquid system can be easily prepared by mixing a polymer having a oxyl group and a thiol group containing a thiol group. When preparing the I solution, a solvent can be used as needed. Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and propylene glycol; ketones such as methyl net and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; and benzene, methyl bromide, xylene, and the like. The aromatic hydrocarbon compound; an aliphatic hydrocarbon compound such as iL hexane; an alicyclic hydrocarbon compound such as cyclohexane; an acetate such as methyl acetate or ethyl acetate; but the present invention is not limited to the exemplification. These solvents may be used singly or in combination of two or more kinds of hydrazine solvents, and the total amount of the alkoxy fluorenyl group-containing polymer and the thiol group decane coupling agent is usually 1 〇〇 by weight. For the part, it is preferably 300 to 1 000 parts by weight, and more preferably 5 to 9 parts by weight. The I liquid, the alkoxyfluorenyl group-containing polymer and the thiol group-containing oxime coupling agent are not particularly limited. When the liquid I is applied to the substrate, both the polymer having an alkoxyfluorenyl group and the decane coupling agent having a thiol group are fixed to the substrate. Among these, the "having a thiol spur coupling agent" will bond with the (meth)acrylic monomer contained in the liquid II. Therefore, considering the properties of the (mercapto)acrylic monoester 41 201211072 and the balance of the properties of the alkoxyfluorenyl-containing polymer, it is suitable to adjust the polymer having an alkoxyfluorenyl group and having a thiol group. The proportion of the decane coupling agent is preferably. For example, when the properties of a polymer having an alkoxyfluorenyl group are strongly exhibited, the molar ratio of a polymer having an alkoxyfluorenyl group to a decane coupling agent having a thiol group (having an alkoxy group dream) The polymer of the base / the decane coupling agent having a thiol group) is preferably 6/4 or more, and more preferably 7/ is 3 or more. The properties of the (fluorenyl) acrylic monomer contained in the π liquid are strong. Mohs ratio of a polymer having an alkoxyfluorenyl group to a decane coupling agent having a thiol group (a polymer having an alkoxyfluorenyl group or a decane coupling agent having a thiol group) at 4/6 The following is better, preferably 3/7 or less. Further, when the properties of the polymer having an alkoxyfluorenyl group are exhibited to the same extent as those of the (meth)acrylic acid monomer contained in the n-liquid, the polymer having an alkoxy group and a thiol group are obtained. The molar of the decane coupling agent of the base (the polymer having an alkoxy group or the sulphur group having a thiol group) is preferably 3/7 to 7/3, and more preferably 4/6 to 6/4. good. [Sputum] Next, it is explained that the II liquid "II liquid contains a (fluorenyl) acrylic monomer. The (fluorenyl) acrylic monomer may, for example, be a (fluorenyl)acrylic monomer represented by the formula (Vb): (Vb) CH^CCO-R20 I II R19 式 where R19 represents a hydrogen atom or a methyl group, R2. The hydrophilic group, the hydrophobic group, the cationic group or the anionic group is used. However, the present invention is not limited to the above-mentioned acrylic monomer, and it may be used in combination, or two kinds of 42 8 201211072 or more may be used in combination. In the formula (Vb), R19 is a hydrogen atom or a methyl group. R2° is a hydrophilic group, a hydrophobic group, a cationic group or an anionic group. The (meth)acrylic polymer having a oxyalkyloxy group may have only one type of a hydrophilic group, a hydrophobic group, a cationic group, or an anionic group, or two or more kinds thereof. The nature imparted to the substrate by the surface (four) agent can be adjusted by selecting the type of the hydrophilic group, the hydrophobic group 'cationic group or the astringent group. For example, when hydrophilicity is imparted to the substrate, when a hydrophilic group is selected and hydrophobicity is imparted to the substrate, a hydrophobic group is selected. Further, for example, when a hydrophilic group and a hydrophobic group are selected, hydrophilicity and hydrophobicity can be imparted to the (sub-group) acrylic polymer having an alkoxyfluorenyl group. Further, a hydrophilic group of acrylic monomer and R2 are used in combination. The surface-modified agent of the present invention which is a hydrophobic group can also impart hydrophilicity and hydrophobicity. R2. For example, an alkyl group having a hydrogen atom or a carbon number of 2 to 20 atoms, a carbon number of 6 to 20 aryl groups having a hydroxyl group or a fluorine atom, and a hydrogen atom or a carbon number at the terminal end may be mentioned. The alkyl group may also have an alkyl group having a gas atom or a carbon number at the end of the epoxy group of the epoxy group, or an addition mole number of the oxiran group having a hydroxyl group or a fluorine atom. The epoxy group having 2 to 2 Å, having a hydrogen atom or a carbon number of 4 at one end may have an oxypropylene group having a hydroxyl group or a fluorine atom, and having a hydrogen atom or a carbon number at one end. The alkyl group of 4 may have a hydroxyl group or a fluorine atom, and the addition molar number of the propylene group is 2 to 2 Å. The epoxy group (4) group, the group represented by the above formula (1) 1), and the formula (UV) The basis of the invention, but the invention is not: 43 Ε; 201211072 lies in R20, a hydrophilic group, for example, an alkyl group having a carbon number of 1 to 4 to a hydroxy group, or a hydrazine having a hydrogen atom or The carbon number of the alkyl group of the number 4 is 2. a polyethylene glycol group, a terminal hydrogen atom or a carbon number of a carbon number of 4, a polypropylene glycol group, a group represented by the formula (III), etc., but the invention is not limited thereto. Illustrative. From the viewpoint of improving the strength of the coating film, the formula (1) is based on the R' hydrophobic group, and may, for example, have a gas atom: a number of 2 to 20, and may have an atomic group. The aryl group having a carbon number of 6 to 2 () is not limited to this example. Among these groups, from the viewpoint of oil repellency, an alkyl group having a fluorine atom number of 3 or more and a carbon number of 2 to 2 Å and a group having a fluorine atom number of 3 or more and a carbon number of 6 to 20 are preferable. In the case of R, the cationic group may, for example, be a group represented by the formula (IV), but the invention is not limited to the examples. In the case of R2°, the anionic group may, for example, be an methylene phenoxy oxime group or a thioglycosylamino group, but the invention is not limited to the exemplification. The liquid II may be composed only of a (mercapto)acrylic monomer, and may contain a catalyst as needed. The catalyst may, for example, be triethylamine, tributylamine, triamylamine, N,N-dimethylaniline, N'N-diethylaniline, pyridine or quinoline, but the invention is not limited to the illustration. . Among these catalysts, since it has a high boiling point, workability is improved, and triethylamine is preferred. The amount of the catalyst is not particularly limited, and from the viewpoint of increasing the reaction rate, it is preferred that the weight of the (meth)acrylic monomer is 100 parts by weight. Further, the (A 201211072-based) propionate monomer may be used in combination with another polymerizable monomer as long as it does not inhibit the object of the present invention. Other polymerizable monomers include, for example, styrene, fluorene-hydroxystyrene, p-hydroxystyrene, methyl (meth)acrylate, methoxyethyl (meth)acrylate, and (meth)acrylic acid. Oxybutyl butyl ester, N-methyl (meth) acrylamide, N-ethyl (fluorenyl) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (fluorenyl) Acrylamide, N_mercapto (meth) acrylamide, N-t-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N-dimethyl ( Methyl) acrylamide, N,N-diethyl(meth)acrylamide, (meth) propylene morpholine, diacetone acrylamide, itaconate, ethyl itaconate, Vinyl acetate, vinyl propionate, N_vinylpyrrolidone, N-ethylene caprolactam, etc. 'But the present invention is not limited to this example. These other polymerizable monomers ' may be used alone or in combination of two or more. Further, when the 11 liquid is prepared, a solvent can be used as needed. Examples of the solvent include alcohols such as decyl alcohol, ethanol, isopropanol, ethylene glycol, and propylene glycol; ketones such as propyl hydrazine and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; and benzene, methyl strepethion, xylene, and the like. An aromatic hydrocarbon compound; an aliphatic hydrocarbon compound such as n-hexane; an alicyclic hydrocarbon compound such as a hexazone; a hydrazine acetate such as methyl acetate or ethyl acetate; and the present invention is not limited to the examples. These solvents may be used singly or in combination of two or more kinds. The amount of the solvent is not particularly limited. Usually, the weight of the (meth)acrylic monomer is preferably from 3 to 2 parts by weight, and more preferably from 50 to 1 part by weight. [2-Liquid Surface Modifier] The two-component surface modifier of the present invention is composed of the I liquid and the 11 liquid prepared as described above, and the combination of the liquid I and the liquid 11 is used. 45 201211072 The ratio of liquid I to liquid II is the reaction of a thiol coupling agent containing a thiol group in a sputum with a (meth)acrylic acid monomer contained in liquid II. In theory, both are stoichiometric, but It is not necessary to be stoichiometric, and the molar ratio of the decane coupling agent having a thiol group contained in the sputum to the (meth)acrylic acid monomer contained in the π liquid (the decyl group having a thiol group contained in the liquid I) The coupling agent/(meth)acrylic acid monomer contained in the II liquid can be adjusted to 4/6 to 6/4. The two-component surface modifier of the present invention is, for example, coating a liquid II after coating a J liquid on a substrate, by using a thiol group-containing ceramin coupling agent and a thiol based acrylic acid contained in the II liquid. The monomer reacts to modify the surface of the substrate. Hereinafter, a method of producing a surface-modified substrate by the two-component surface-modified agent of the present invention will be described. [Method for Producing Surface-Modified Substrate] The above-described two-liquid type surface modifier is used in the method for producing a surface-modified substrate of the present invention. The method for producing a surface-modified substrate according to the present invention is characterized in that the substrate is coated with a polymer having a oxyalkylene group and a thiol group-containing decane coupling agent. On the surface of the liquid substrate, 11 liquid containing a (meth)acrylic monomer is applied, and a thiol coupling agent having a thiol group present on the surface of the substrate is reacted with a (meth)acrylic monomer. As a substrate, a polymer having an alkoxyfluorenyl group and a thiol group-containing coupling agent having a thiol group are chemically fixed to a substrate, and a substrate having a hydroxyl group on the surface thereof is used satisfactorily. The material of the substrate may be the same as the user of the third group of the present invention, and the alkoxyfluorenyl group-containing polymer and the octa-thiol group-containing decane coupling agent may be used for the two-component surface modifier. A substrate having a hydroxyl group on the surface, can be 8 201211072

It is more firmly fixed, and when the surface of the substrate is modified by the A surface, it is preferable to have a hydroxyl group on the surface and the surface. Further, the substrate 'is sufficiently present on the surface thereof. The composition of the glass is such that the base group exists on the surface of the surface n/H (four) Mm. The shape of the substrate is particularly limited, and is used in the present invention. The same group can be used. The method of applying the liquid I to the substrate, the method, the m & the flow coating method, the spray method, the brush coating method, the roll coating method, etc. However, the present invention is not limited to the case where the liquid I is applied, as long as it is H, s + s 疋 large milk. In addition, the coating is applied at the time of coating = ^ 'Μ heating. The liquid at the time of coating is different depending on the use of the substrate, so it cannot be determined in a general manner, and it is preferably adjusted according to the use thereof. After the liquid is applied to the substrate, it is determined from the viewpoint of == efficiency. The substrate is preferably heated. The heating temperature of the substrate varies depending on the heat-resistant temperature of the substrate, and therefore cannot be determined in a general manner. Generally, a temperature which does not adversely affect the substrate in the range of 15 (rc) is preferable. Applying a ί liquid to a substrate, the polymer having a thioxanthene group and a stone having a thiol group The hospital coupling agent is fixed to the substrate 0 and coated with 11 liquids. The method of using the first liquid 1 liquid can be similarly applied to the brush coating method, the affinity coating method, etc., and then the application of the substrate sheet coated with the liquid I is applied. The substrate method and the substrate coating are, for example, a flow coating method, a spray coating method, or a dipping method, but the present invention is not limited to the examples. Further, the sputum (four) is applied to the base (four) by the dipping method, and the production is improved. The viewpoint of efficiency is to adjust the liquid temperature of the π liquid to a good degree. In addition, 47 201211072 The time for immersing the substrate in the mash is not particularly limited, and the reaction of the (meth)acrylic monomer contained in the sputum is enhanced. The viewpoint of the degree of fascination and the viewpoint of production efficiency are preferably in the range of 30 to 120 minutes. As described above, the sulphur-based coupling agent and the thiol group are immobilized on the substrate by coating the liquid I. a (meth)acrylic acid monomer bond, which imparts properties to a polymer having a siloxane group, which is immobilized to a substrate in advance, and a (meth)acrylic monomer Having the properties. After the reaction of the (meth)acrylic monomer with the decane coupling agent having a thiol group, It is necessary to wash and dry the substrate. 'The surface-modified substrate of the present invention obtained as above has a polymer having an alkoxyfluorenyl group contained in the liquid I on the surface thereof. The (meth)acrylic monomer can be simultaneously imparted to the polymer having an alkoxyfluorenyl group, and the (meth)acrylic acid which is fixed to the substrate by the reaction of the sigma compound coupling agent t The nature of the monomer, and can prevent the loss of moisture due to the use of the previous surfactant. Therefore, by appropriately adjusting the properties of the polymer having an alkoxyfluorenyl group, and (methyl The properties possessed by the acrylic monomer can impart desired properties such as hydrophilicity, hydrophobicity, oil repellency, and lipophilicity to the substrate. [Group 3 of the present invention] The surface of the third group of the present invention is hydrophilic. The chemical agent is characterized by comprising: a (fluorenyl) acrylic polymer containing a monomer having a broken atom represented by the formula (Ιχ) and a nitrogen atom represented by the formula (X). Polymerization of monomer components: 48 (IX)201211072 ψ R3

I I

HjC = C ~ C-Y ~ R e-si - R4

II I ° R5 wherein R1 represents a hydrogen atom or a methyl group, and R3, R4 and R5 each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having a carbon number of 4, among R3, ^ and R5. At least one group is an alkoxy group having a carbon number of 4, R6 is a mercapto group having a carbon number of 1 to 6, and γ is an oxygen atom or -NH;

R1 R9 coo· (X) H2C=.C_C—Y—Re— In the formula, R, R and y are the same as above, and r8 means that the alkylene κ and R series having a carbon number of i to 4 each independently represent a hydrogen atom. Or an alkyl group of carbon number i. The monomer which does not contain a ruthenium atom in the formula (IX), the RI-based hydrogen atom or the 6-alkyl R-based carbon number-alkylene group ' is preferably a carbon number Η alkylene group. Specific examples of the positive R include a methylene group, an ethylene group, an n-propylene group, an isopropylidene group, a benzylidene group, a second butylene group, and the like, but the invention is not limited to the examples. R3, R4, and R5 are each independently cotton, and ^^^ 俐 is an alkyl group having 1 to 4 alkyl groups or a carbon number of 1 to 4, R3, ! Among the ^ and R5, ^ ^ is the base, which is a emulsified base of 1 to 4 carbon atoms. Among the V and R5, a base of T, which is a carbon number of 4, is a solid surface of the present invention in which the surface _: 7k il coat hydrophilizing agent of the present invention is firmly fixed. Therefore, among R3, R4 and R5, m«. is an alkane I having a carbon number of 1 to 4, but R3, and a 5 φ group A, and two alkoxy oximes having a carbon number of 4 Preferably, the alkoxy groups of R3, R4 and +~4 are more preferred. Among the alkyl groups having a carbon number of 49 201211072, a methyl group and an ethyl group are preferred, and a methyl group is more preferred. Among the epoxy groups having a carbon number of 14, the methoxy group and the ethoxy group are preferred, and the methoxy group is more preferred. Y is an oxygen atom or a NU- group. The monomer having a ruthenium atom represented by the formula (IX) may, for example, be (meth) propylene oxypropyltrimethoxy oxalate, or (meth) propyl oxypropyltriethoxy decane, or (fluorenyl) propylene oxypropyl triisopropoxy decane, (fluorenyl) propylene oxypropyl decyl dimethoxy decane, (meth) propylene oxypropyl methyl ethoxy decane, ( Methyl)propenyloxypropylmethyldipropoxydecane, etc., but the invention is not limited to the examples. These monomers containing germanium atoms may be used singly or in combination of two or more. In addition, in this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic acid". In the monomer containing a nitrogen atom represented by the formula (X), R1, R6 and γ may be the same as described above. More specifically, R1 is a hydrogen atom or a methyl group. R6 is a carbon number of 1 to 6 alkylene groups, preferably a carbon number of 4 alkylene groups. Specific examples of R6 include a methylene group, an ethylene group, an n-propylene group, an isopropylidene group, an n-butylene group, an isobutylene group, and a second butylene group. A γ-based oxygen atom or an NH— group. R8 is an alkylene group having 1 to 4 carbon atoms. The alkylene group of carbon number 4 may, for example, be a methylene group, an ethylene group, a n-propylene group, an isopropylidene group, a n-butylene group, an isobutylene group or a third butylene group. However, the invention is not limited thereto. This example. R9 and R10 are each independently a hydrogen atom or a carbon number of 4, preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group of the carbon number 4 may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a t-butyl group, but the invention is not limited to the examples. 8 50 201211072 The precursor containing a nitrogen atom represented by the formula (x) may, for example, be N-(methyl)acryloyloxyethyl-N,N-dimethyl-deficient α-Ν-methylcarboxybetaine , Ν-(methyl) propylene phthalamide ethyl hydrazine, hydrazine-methyl ammonium hydrazine-methyl carboxy beet, etc., but the invention is not limited to _ 该 该 该 该 该 。 。 These soap-containing soaps may be used singly or in combination of two or more. The monomer having 3 nitrogen atoms represented by the formula (X) may also be a water and a substance. Further, N-methyl propylene oxime-ethyl N,N- 曱 录 · · 'α-Ν-methyl T-carboxycarboxybetaine can be, for example, JP-A-9-95474, JP-A-10-29- The versatile glutinous rice described in the publication No. 95586 and JP-A No. 1-222470 is prepared in high purity. The weight ratio of the precursor containing the oxime represented by the formula (IX) to the monomer containing the atom represented by the formula (monomer containing a dream atom / containing a nitrogen atom = monomer) is improved by the substrate The viewpoint of the adhesion is preferably 3/97 or more, preferably 5/95 or more, and is based on the hydrophilicity of the smear of the sulphate hydrophilizer. The sweet spot is preferably 95/5 or less, preferably 85/15 or less, and further preferably 75/25 or less. The monomer composition used in the present invention contains a monomer having an atomic group represented by the formula (1) and a nitrogen atom-containing monomer represented by the formula (1), but may be further improved as required. a monomer having a germanium atom-containing monomer and a monomer having a nitrogen atom-free monomer which is not represented by (X). Representative examples of the above copolymerizable monomer include a monomer having a carbon-carbon unsaturated double bond. a monomer in which a human y is copolymerized with a monomer having a ruthenium atom represented by the formula (IX) and a monomer having a nitrogen atom represented by the formula (χ), for example, a styrene monomer, a carboxylic acid s- Monomers having a carbon-carbon unsaturated double bond, such as a body, an amine system, or a monomer, etc., but the present month is not limited to this example. The monomer which can be copolymerized with the above may be used separately as 51 201211072. When the monomer component contains a styrene monomer, the heat resistance of the surface hydrophilizing agent of the present invention may be improved. The stupid monomer may, for example, be styrene or α-. Mercaptostyrene...hydroxystyrene, p-hydroxystyrene, etc., but the invention is not limited to the examples. The styrene monomers can be divided into When it is used alone or in combination, when the monomer component contains a carboxylate monomer, there is a point of improving the lipophilicity of the surface hydrophilizing agent of the present invention. The carboxylate monomer is, for example, Base) methyl acrylate, ethyl (meth) acrylate, propyl (mercapto) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, (fluorenyl) neopentyl acrylate, cyclohexyl (meth) acrylate, octyl acrylate, lauric (meth) acrylate, stearyl (meth) acrylate, hexadecyl (meth) acrylate , (meth)acrylic acid ethyl carbitol, (meth) acrylate acid ethyl ester, (meth) acrylic acid propyl propyl ester, (mercapto) hydroxy butyl acrylate, (Methoxyethyl acrylate, (mercapto) methic acid methoxy butyl sulfonium, (mercapto) acrylic acid vinegar, etc. (mercapto) propyl decyl sulphuric acid vinegar, (meth) acrylic acid It can be exemplified by a base alkyl ester, a (meth)acrylic acid alkoxy ester, an (aryl) aryl acrylate. Methyl ester, ethyl itaconate, ethyl acetate, ethyl acetate, etc., but the invention is not limited to the examples. The carboxylic acid ester monomers may be used alone or in combination of two. When the monomer component contains an amine-based monomer, the hydrolysis resistance of the surface hydrophilizing agent of the present invention is improved. The amine-based monomer may, for example, be fluorene-methyl(meth)acrylamide. Ν-Ethyl (meth) acrylamide, Ν-propyl (meth) acrylamide, Ν-isopropyl (meth) acrylamide, Ν-mercapto (meth) acrylamide, 52 201211072 N-Terbutyl (meth) propylamine, N-octyl (methyl) acrylamide, nn dimethyl (methyl) acrylamide, N, N-diethyl ( Methyl) acrylamide, diacetone, acrylamide amine monomer such as acrylamide, (meth) propylene oxime, N-vinyl pyrrolidone, N-vinyl caprolactam, etc., but the invention is not limited thereto This example. These amine monomers may be used alone or in combination of two or more. a monomer which can be copolymerized with a monomer having a ruthenium atom represented by the formula (IX) and a monomer having a gas atom represented by the formula (χ), and a monomer having a ruthenium atom represented by the formula (Ιχ) 100 parts by weight of the total amount of the nitrogen atom-containing monomer represented by the formula (X) is preferably from 0 to 100 parts by weight, more preferably from 50 parts by weight or less, from the viewpoint of enhancing hydrophilicity. More preferably, it is more preferably 10 parts by weight or less, and is not more than 0.3 parts by weight from the viewpoint of sufficiently exhibiting properties imparted by using the copolymerizable monomer, depending on the amount of the monomer which can be copolymerized with the monomer. Preferably, it is more preferably i weight or more, and further preferably 3 parts by weight or more. By polymerizing a monomer having a ruthenium atom represented by the formula (IX), a monomer having a nitrogen atom represented by the formula (χ), and, if necessary, a monomer component copolymerizable with the monomer. A (fluorenyl) acrylic polymer is obtained. When the monomer component is polymerized, a polymerization initiator is preferably used. The polymerization initiation =, for example, azobisisobutyronitrile, azoisobutyronitrile, azoisobutyric acid azobisdimethyl valeronitrile, benzene peroxide, potassium persulfate, ammonium persulfate, A Ketone derivatives, phosphine oxide derivatives, benzophenone derivatives, phenyl sulfides, azide derivatives, dinitride derivatives, disulfides "", etc., but the invention is not limited thereto This example. These polymerization initiators, 53 201211072, may be used alone or in combination of two or more. The weight of the 100-weight polymerization is not particularly limited, and it is usually a part of the monomer component, preferably 0. 01~1 〇. Further, in the present invention, a chain transfer agent can also be used in the polymerization of a monomer. The bond transfer agent is usually used by mixing with the Tianxing soap component. The chain transfer agent may, for example, be a thiol group-containing compound such as lauryl mercaptan, +-eleven thiol or thioglycerol; an inorganic salt such as sodium hypophosphite or sodium hydrogen sulfite, but the present invention is not Limited to this illustration. These chain transfer agents may be used singly or in combination of two or more. The weight of the chain transfer is not particularly limited, and the weight of the monomer component is usually 0. 01 to 1 〇. The method of polymerizing the monomer component may, for example, be a solution polymerization method, but the invention is not limited to the examples. When the monomer component is polymerized by a solution polymerization method, for example, the monomer component can be dissolved in a solvent, and a polymerization initiator can be added while mixing the obtained solution to polymerize. An ester such as hexane or propylene dihydrofuran or acetic acid. The monopolymerization conditions/glutosity of the solution solutions may be exemplified by alcohols such as alcohols; ketones such as acetone and methyl ethyl ketone; and aromatic hydrocarbon compounds such as squeaky, stupid, and stupid; An alicyclic hydrocarbon compound such as a sulphate compound, an alicyclic hydrocarbon compound such as hexyl sulphate, or an acetate ester such as acetonitrile acetate, etc., but the invention is not limited to the exemplified agent', and may be used alone or in combination of two or more. The amount of the refrigerant is usually adjusted to a level of from 10 to 80% by weight based on the concentration of the monomer dissolved in the solvent. The polymerization temperature, the polymerization time, and the like for the polymerization of the monomer component are preferably adjusted according to the monomer composition, the type of the polymerization initiator, and the amount of the polymerization initiator. The atmosphere at the time of polymerization of the monomer is preferably an inert gas. The inert gas may, for example, be nitrogen gas, argon gas or the like, but the invention is not limited to the examples. The end of the polymerization reaction and the presence or absence of unreacted monomers in the reaction system can be confirmed, for example, by a general analysis method such as gas chromatography. By polymerizing the monomer component as described above, a (meth)acrylic acid-based polymer can be obtained. The viscosity average molecular weight of the (meth)acrylic polymer is sufficient to exhibit surface affinity: effect. The above is better than 50. From the viewpoint of the solubility of the (meth)acrylic polymer, it is preferably 100,000 or less, more preferably 5 Å or less. Further, the viscosity average molecular weight of the (meth) acrylic acid polymer can be measured by, for example, a Ubbelde viscosity meter or the like. The surface hydrophilizing agent of the present invention may contain the above-mentioned acrylic polymer, but may contain other polymers, solvents, various additives, and the like, within the range not inhibiting the object of the present invention. The agent may be the same as the solvent used in the polymerization of the above monomer components. Examples of the solvent include g| such as methanol, ethanol, #propanol, and ethyl alcohol propylene glycol; ketones such as acetone and methyl ethyl ketone; and aromatics such as diethyl ether and tetramethyl ortho toluene. Hydrocarbon compound; an aliphatic hydrocarbon compound such as a positive appearance; an alicyclic hydrocarbon compound such as cyclohexyl; an acetate such as methyl acetate or ethyl acetate; however, the present invention is not limited to the examples. These solvents ' may be used alone or in combination of two or more. 55 201211072 The amount of the solvent is not particularly limited, and the concentration of the (meth)acrylic polymer in which the (meth)acrylic polymer is dissolved in a solvent is usually adjusted to a concentration of 10 to 80% by weight. The surface hydrophilized substrate of the present invention can be obtained by forming a film composed of a surface hydrophilizing agent on the surface of the substrate. The material of the substrate may be the same as that of the user of the third group of the present invention. Among the base materials, a base material having a hydroxyl group on its surface is preferred from the viewpoint of firmly fixing the (meth)acrylic polymer contained in the surface hydrophilizing agent of the present invention to a substrate. When a substrate having no hydroxyl group on its surface is used, from the viewpoint of firmly fixing the surface hydrophilizing agent of the present invention to a substrate, it is preferable to hydrophilize the surface by having a hydroxyl group on its surface. Further, for example, when a substrate composed of glass has a sufficient warp group on its surface, it is not necessary to hydrophilize its surface to allow a hydroxyl group to exist on its surface. The shape of the substrate may be the same as that of the user of the first group of the present invention. The method of applying the surface hydrophilizing agent of the present invention to a substrate may be the same as that of the first group of the present invention. The atmosphere at the time of applying the surface hydrophilizing agent of the present invention to a substrate is usually as long as it is at atmosphere. Further, the temperature at the time of coating is usually normal temperature, and may be heated. When the surface hydrophilizing agent of the present invention is applied to a substrate, the coating amount of the surface hydrophilizing agent of the present invention varies depending on the use of the substrate, and therefore cannot be determined in a general manner, and it is preferably adjusted according to the use thereof. . After the surface hydrophilizing agent of the present invention is applied to a substrate, it is preferred to heat the substrate from the viewpoint of improving production efficiency. The heating temperature of the substrate is not determined in a general manner depending on the heat resistance of the substrate of 8 56 201211072, and it is usually preferable that the temperature does not adversely affect the substrate in the range of 50 to 1501. Further, the surface hydrophilized substrate of the present invention may be produced by applying a monomer component onto a surface of a substrate to irradiate light or heating to polymerize a monomer component to form a film. The thickness (thickness after drying) of the film formed on the surface of the surface hydrophilized substrate of the present invention varies depending on the type or use of the surface hydrophilized substrate, and cannot be determined in a general manner, but usually is 1 〇 nm~ 1〇"m degree is better. As described above, the surface hydrophilizing agent of the present invention can be obtained by applying the surface hydrophilizing agent of the present invention to the surface of a substrate. In the surface-modified substrate of the present invention, since the (meth)acrylic polymer contained in the surface hydrophilizing agent of the present invention is immobilized on the surface thereof, the (meth)acrylic polymer can be imparted to the substrate. It has hydrophilicity and can be prevented from being lost due to moisture adhesion when the previous surfactant is used. [Examples] Next, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples. The invention of the invention! Group ~ Invented Group 3, each group is independent. Therefore, the example numbers of the examples described in the respective groups are independent of each group. [Examples of the first group of the present invention] Example 1 has a nitrogen gas introduction tube, a condenser and a mixer. A 500 mL-capacity flask was charged with N-mercaptopropenyloxyethyl-N,N-dimethylammonium_α_Ν_methylcarboxybetaine (Osaka Organic Chemical Industry Co., Ltd., trade name. 57 201211072 GLBT) 32. 31 g, 3-mercaptopropyltrimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-8 03) 1. 55 g and ethanol 146·20 g. Degassing by reducing the pressure inside the flask Thereafter, nitrogen gas was introduced to return to normal pressure, and the oxygen in the flask was removed as much as possible. Next, the contents of the flask were heated to 65 ° C by an oil bath attached to the flask, and then azobisisobutyronitrile was added 1.83 g' while maintaining the temperature of the contents of the flask at 7 (TC was matured for 4 hours. Thereafter, 0.37 g of azobisisobutyronitrile was further added to the flask by maintaining the reaction temperature at 7 (rc for 4 hours). , obtaining a polymer solution. The obtained polymer solution was cooled to 30 t in a water bath to A 182.76 g of alcohol was diluted to obtain a (meth)acrylic acid polymer solution having a sulfonium group. The viscosity of the obtained (meth)acrylic polymer solution having an alkoxyfluorenyl group was obtained in Uber-Look Type viscometer [(share) 理 硝 硝 ' ' ' 品 品 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 The (meth)acrylic polymer solution having an alkoxy group is used as a surface modifier. Example 2 A 5 mL mL flask having a nitrogen gas introduction tube, a condenser, and a stirrer. Add N-methyl propylene oxiranyl ethyl-N,N-dimethylammonium _α_Ν_ methylcarboxybetaine [Osaka Organic Chemical Industry Co., Ltd., trade name: GLBT] 35.00g, 3-mercaptopropyl Base tris-oxydecane [Shin-Etsu Chemical Industry Co., Ltd.'s trade name: KBM-803] 3.27g and ethanol I53.10g. After degassing the internal pressure of the burned 8 58 201211072 bottle, the introduction of nitrogen is repeated. Press and remove the oxygen in the flask as much as possible. After the flask was placed in an oil bath, the contents of the flask were warmed to 65 ° C, and then azobisisobutyronitrile was added in 38 g, while the temperature of the contents of the flask was maintained at 70 ° C for 4 hours. Further, 0.38 g of azobisisobutyronitrile was further added to the flask while maintaining the reaction temperature at 7 Torr. The mash was aged for 4 hours to obtain a polymer solution. The obtained polymer solution was cooled to 3 Torr in a water bath. A solution of a (meth)acrylic polymer having an alkoxyfluorenyl group was obtained by diluting with ethanol 191.37 g. The use of the (meth)acrylic polymer solution having an alkoxyfluorenyl group was used as a surface modification. Quality agent. The viscosity of the obtained (meth)acrylic polymer solution having an alkoxyfluorenyl group is determined by a Ubbelde type viscometer (manufactured by Mutual Chemicals, product number: U-0327-26). 25. (Measurement, viscosity average molecular weight was found), and the viscosity average molecular weight was 3000. Example 3 In a 500 mL-capacity flask having a nitrogen gas introduction tube 'condenser and a stirrer', N-methyl propylene oxiranyl group was placed. n,N-dimethyl saddle-anthracene; an N-methyl basal betaine [Osaka Organic Chemical Industry Co., Ltd., trade name: 00g, 3-mercaptopropyltrimethoxydecane [Shin-Etsu Chemical Industry ( Co., Ltd., trade name: KBM-803] 〇.75g and ethanol 143.02g. After degassing the internal pressure of the combustion, introduce nitrogen gas back to normal pressure, and remove the oxygen in the flask as much as possible. The contents of the flask were heated by an oil bath installed in a flask at 59 ° 20117272, and after adding 85 μg of azobisisobutyronitrile, the rnt degree of the contents of the flask was maintained at 7 ° C. After that, 0.36 g of azobisisobutyronitrile was further added to the flask, and the polymer solution was obtained by maintaining the reaction temperature at 7 (rc for 4 hours). The obtained polymer solution was cooled to 3 Torr in a water bath. 〇C, diluted with ethanol 1 78. 78g 'obtained with alkoxy a thiol-based (meth)acrylic polymer solution. The viscosity of the obtained (meth)acrylic polymer solution having an alkoxyfluorenyl group is determined by a Ubbel-type viscosity meter. Manufactured by the manufacturer, item No. U-0327-26] measured at 25 ° C to obtain a viscosity average molecular weight 'resulting in a viscosity average molecular weight of 5000. The (meth)acrylic polymer having an alkoxymethyl group The solution was used as a surface modifier. Example 4 In a 5 〇〇 mL capacity flask with a nitrogen gas introduction tube, a condenser and a stirrer, methoxy triethylene glycol acrylate was added [Osaka Organic Chemical Industry Co., Ltd. Manufactured, product number: V-MTG] 30. 00g, 3-mercaptopropyltrimethoxy oxalate (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) 1.44g and ethanol 125.68g. After depressurization was carried out in the flask, nitrogen gas was introduced to return to atmospheric pressure to remove as much oxygen as possible from the flask. Next, by heating the contents of the flask to 651 by means of an oil bath installed in the flask, azo double was added. Isobutyronitrile 1. 57g, while the contents of the flask The mixture was aged at 70 ° C for 4 hours. Thereafter, 0.13 g of azobisisobutyronitrile was further added to the flask, and the mixture was aged for 4 hours while maintaining the reaction temperature at 7 ° C to obtain a polymer solution. The obtained polymer solution was cooled to 30 ° C in a water bath, and diluted with ethanol 157.10 g to obtain a (meth)acrylic acid polymer solution having an alkoxyfluorenyl group. The viscosity of the (meth)acrylic polymer solution was 25 by a Uber-Look-type viscometer (product number: U-0327-26) manufactured by Mutual Chemicals Co., Ltd. (: Measurement, viscosity average molecular weight was obtained, and the viscosity average molecular weight was 5 Å. The (meth)acrylic polymer solution having an alkoxy group was used as a surface modifier. Example 5 Nitrogen introduction tube, condenser and stirrer 5 〇〇 mL capacity flask, and put 2, 2, 2-trifluoroethyl decyl acrylate [Osaka Organic Chemical Industry Co., Ltd.] Item No.: V-3FM 35.00 g, 3-phosphinopropyltrimethoxy oxime (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) 2.35 g and 149.39 g of ethanol. After degassing the pressure inside the flask, Introduce nitrogen back to normal pressure 'to remove as much oxygen as possible from the flask. Next' by adding the azobisisobutyronitrile LWg after heating the contents of the flask to 65 ° C by means of an oil bath installed in the flask The temperature of the contents of the flask was maintained at 70 ° C for 4 hours. Thereafter, 0.37 g of azobisisobutyronitrile was further added to the flask, and the reaction temperature was maintained for 4 hours to obtain a polymer. Solution. The resulting polymer solution was cooled to 3 Torr in a water bath. c, diluted with 186_74g of ethyl yeast to obtain a (meth)acrylic polymer solution having an alkoxyfluorenyl group. The viscosity of the (meth)acrylic polymer solution 61 201211072 obtained with an alkoxyfluorenyl group is The Bollard-type viscometer (manufactured by Mutual Chemicals Co., Ltd., product number: U-0327-26) is measured at 25 ° C to obtain a viscosity average molecular weight 'resulting in a viscosity average molecular weight of 4000. The oxetane-based (mercapto) acrylic polymer solution was used as a surface modifier. Example 6 In a 500 mL flask equipped with a nitrogen gas introduction tube, a condenser and a stirrer, 2-(perfluorohexyl) was placed. Ethyl decyl acrylate [manufactured by Daikin Industries Co., Ltd., article number: M-1620] 12.00g, 3-mercaptopropyltrimethoxy 矽 矽 〔 [Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM-803] 〇. 29g and 2'2,2-trifluoroethanol 49.15g. After degassing the pressure inside the flask, introduce nitrogen gas back to normal pressure to remove as much oxygen as possible from the flask. The contents of the flask were heated to 65 by an oil bath installed in the flask. After C, azobisisobutyronitrile 0 61 g ' was added while maintaining the temperature of the contents of the flask at 70 ° C for 4 hours. Thereafter, azobisisobutyronitrile 〇.12 g was further added to the flask, and the reaction was carried out by the side. The temperature was maintained at 7 &>c for 4 hours to obtain a polymer solution. The obtained polymer solution was cooled to 3 ° C in a water bath and diluted with 2, 2 2- = gas ethanol 61 · 44 g to obtain an alkane. a solution of a (meth)acrylic polymer of oxyindenyl group. The viscosity of the obtained (meth)acrylic polymer solution having an alkoxyfluorenyl group is unilaterally viscous by a Ubbel-type viscosity meter. Made by the manufacturer of the nitrocellulose, the product number: ϋ-0327-26] is 25. (Measurement, the viscosity average molecular weight was determined, and as a result, the viscosity average molecular weight was 1,000,000. The (meth)acrylic polymer solution having an alkoxyfluorenyl group was used as a surface modifier. 8 62 201211072 Example 7 ~12 The surface modifier obtained in the example was flow-coated on a glass plate (length: braided, width: 1 〇 °, thickness: 1 (four)) 'after the remaining surface modifier was removed by washing with ethanol' The glass plate is placed in a warm air dryer, and dried at a temperature of mi for 3 G minutes to obtain a surface-modified substrate. Next, the physical properties of the surface-modified substrate obtained above, hot water resistance, contact angle with water, and The thickness of the overcoat was evaluated as follows. The results are shown in Table 1. [Heat-resistant water] 』 Drops of water on the surface-modified substrate, using a contact angle meter [leg A (stock)] in a 25 〇C atmosphere The contact angle with water was measured. Thereafter, the surface modified substrate was immersed in hot water heated at 8 G ° C for 5 hours to carry out a hot water test. Next, the surface modified substrate was subjected to the test. Removed from hot water, washed with water, attached to the surface After the water of the substrate was dried by gas, water droplets were dropped on the surface-modified substrate, and a contact angle meter (ERMA) was used to measure the contact angle with water in the atmosphere. The evaluation was evaluated according to the following evaluation criteria. Hot water resistance. (Evaluation criteria) 〇: The absolute value of the contact angle difference with respect to water before and after the hot water resistance test is less than 10 degrees X: The absolute value of the contact angle difference with respect to water before and after the hot water resistance test is i 〇 or more [contact angle with water] 〕 Water droplets were dropped on the surface-modified substrate, and the contact angle with water was measured in a 25 ° C atmosphere using a contact angle meter (ERMA (fraction) 63 201211072). [Thickness of the film] was formed by surface modification. The thickness of the cover film composed of the surface modifying agent of the material is measured using a stylus type differential meter [manufactured by KLA.TENK0R (product number: p_1〇). Further, in each of the examples, the surface modifier flow is performed. After coating on a glass plate and drying with hot air at 120 ° C for 30 minutes, the glass plate coated with the above surface modifier was exposed to water vapor at 90 ° C for 5 minutes. The antifogging property of the glass plate was visually observed. , evaluated by the following evaluation criteria. Evaluation criteria) 〇: The glass plate is not fogged X: The glass plate is fogged. The example number in Table 1 in the column of “Type of glass plate” refers to the surface obtained by using the number of this example. The modifier-flow-coated glass plate was used to investigate the physical properties. Comparative Example 1 In Example 7, a glass plate which was replaced with a surface modifier was used, and a glass plate which was not modified with a surface modifier was used. The contact angle with water and the antifogging property were similarly investigated. The results are shown in Table 1. ^Comparative Example 2 A 1% sodium laurate aqueous solution was applied to a glass plate, and the glass plate was placed in a warm air dryer at 120 ° C. The temperature was dried by warm air for 30 minutes to obtain a substrate treated with a surfactant. The physical properties of the obtained substrate were examined in the same manner as in Example 7. The results are shown in Table 1. 64 201211072 Comparative Example 3 A 1% aqueous solution of sodium tetradecanoate was applied to a glass plate, and the glass plate was placed in a warm air dryer and dried at a temperature of 12 Torr for 3 minutes to obtain a surfactant treatment. The substrate. The physical properties of the obtained substrate were investigated in the same manner as in Example 7. The results are shown in Table 1. Comparative Example 4 A 1% aqueous solution of sodium palmitate was applied onto a glass plate, and the glass plate was placed in a warm air dryer and dried by air at a temperature of 12 °C for 30 minutes to obtain a substrate treated with a surfactant. The physical properties of the obtained substrate were examined in the same manner as in Example 7. The results are shown in Table i. Further, the comparative example numbers described in "Types of Glass Plates" (4) in Table 1 are the properties of the glass sheets which were flow-coated with the surface modifier obtained by the comparative example numbers. Next, the observation results when the film of the character "_" is superimposed on the back surface of the glass substrate obtained in the seventh embodiment and the glass plate of the comparative example are shown in Figs. 1(a) and (b)e, respectively. Figure! (〇 and (1)) are pictorial substitute photographs showing the results of investigating the antifogging properties of the surface-modified substrate obtained in Example 7 and the glass plate of Comparative Example, respectively. From the results shown in Fig. 1, the surface-modified substrate obtained in Example 7 was able to clearly recognize the letter of r〇〇c" through the glass plate, and the glass plate of Comparative Example 1 was fogged, and "ooc" The text recognition has become blurred. 65 201211072 Table 1 Example No. Surface-modified glass substrate type of physical glass sheet Contact angle (degree) of hot water resistance to water Thickness (nm) of film (film) Antifogging property 7 Example 1 〇 4 20 〇 8 Example 2 〇4 20 〇9 Example 3 〇4 20 〇10 Example 4 〇9 20 〇11 Example 5 〇88 20 X 12 Example 6 〇107 20 〇Comparative Example 1 Untreated - 42 - X 2 Comparative Example 2 X 2 Since the film could not be measured 〇3 Comparative Example 3 X 3 Since the film could not be measured 〇4 Comparative Example 4 X 3 Since the film could not be measured 〇 From the results shown in Table 1, according to the respective examples, it is apparent that the alkane was changed by The properties of the (indenyl) acrylic polymer of oxyindenyl group impart hydrophilicity and hydrophobicity to the substrate. Further, in each of the examples, it was apparent that the substrate was provided with excellent water-purifying properties as compared with Comparative Examples 1 to 4. Therefore, it was found that a film which is not easily detached from the substrate even when it comes into contact with water can be formed. Example 1 3 A resin plate (length: 80 mm, width: 25 mm, thickness: 1.5 mm) made of ABS resin was used as a substrate. The resin plate was placed in a vacuum vessel, and after degassing, vapor of trimethoxydecane (vapor pressure: about 400 Pa) was introduced, and cerium oxide was vapor-deposited on the resin plate for 3 hours. The surface modifier obtained in Example 1 was applied to the above-mentioned vapor-deposited cerium oxide resin plate, and the remaining surface modifier was removed by washing with ethanol, and then the resin plate was placed in a warm air dryer at 80 ° C. The temperature was air-dried at 66 8 201211072 for 1 hour to obtain a surface-modified substrate. The surface-modified substrate obtained above was exposed to water vapor of 9 ° C for 5 minutes to visually observe the antifogging property of the glass plate, and it was confirmed that there was no fogging on the surface of the modified substrate. Thus, it can be seen that the surface modifying agent of the present invention can be fixed to the surface of the resin substrate by vapor-depositing the oxidizing dream on the surface of the resin substrate. [Example of Group 2 of the Present Invention] Production Example 1 In a flask of 5 〇〇 mL having a nitrogen gas introduction tube, a condenser and a stirrer, N-mercapto propylene oxyethyl-v, ν - Dimethylammonium _α_Ν_ methyl thiobetaine (made by Osaka Organic Chemical Industry Co., Ltd., trade name: GUT) 32·31g, 3-mercaptopropyltrimethoxy decane [Shin-Etsu Chemical Industry Co., Ltd. , trade name: KBM-803] 1. 55g and ethanol 146. 20g » After degassing the pressure inside the flask, the nitrogen gas was introduced to return to normal pressure, and the oxygen in the flask was removed as much as possible. Next, the contents of the flask were heated to 65 C by means of an oil bath attached to the flask, and then 183 g of azobisisobutyronitrile was added, and the temperature of the contents of the flask was maintained at 70 ° C for 4 hours. Thereafter, 374 mg of azobisisobutyronitrile was further added to the flask, and the polymer solution was obtained by maintaining the reaction temperature at 7 Torr for 4 hours. The obtained polymer solution was cooled to 3 〇 〇c with a water bath, and diluted with ethanol 182.76 g to obtain a polymer solution having an alkoxy fluorenyl group. The viscosity of the obtained polymer solution having an alkoxyfluorenyl group is determined by a Ubbelde type viscosity meter (manufactured by Mutual Chemicals, manufactured by U.S. Patent No. U-0327-26) at 25t to obtain a viscosity. The average molecular weight, as a result, was 67.201211072 The viscosity average molecular weight was 15,000. Production Example 2 In a 500 inL capacity flask with a nitrogen gas introduction tube, a condenser and a stirrer, N-mercaptopropene oxiranyl-N,N-dimethylmethylcarboxybetaine (Osaka Organic Chemical Industry (Osaka Organic Chemical Industry) Co., Ltd., trade name: GLBT] 35·00 g, 3-mercaptopropyltrimethoxydecane [Shin-Etsu Chemical Co., Ltd. product name: KBM-803] 3.27 g and ethanol 153.10 g. The oxygen in the flask was removed as much as possible by returning the inside of the flask to degassing and then introducing nitrogen gas to the normal pressure. Next, the contents of the flask were heated to 65 ° C by an oil bath attached to the flask, and then azobisisobutyronitrile (0 38 g) was added thereto while maintaining the temperature of the contents of the flask at 7 (TC ripening for 4 hours). After that, further add azobisisobutyronitrile 〇.38g to the flask, while maintaining the reaction temperature at 7 边. <t The mixture was aged for 4 hours to obtain a polymer solution. The obtained polymer solution was cooled to 3 Torr in a water bath, and diluted with ethanol 191.37 g to obtain a polymer solution having an alkoxy fluorenyl group. The viscosity of the obtained polymer solution having an alkoxyfluorenyl group is determined by a Ubbelde type viscosity meter (manufactured by Mutual Chemicals, manufactured by U.S. Patent No. U-0327-26) at 25 ° C. The viscosity average molecular weight was obtained, and as a result, the viscosity average molecular weight was 3,000. Production Example 3 In a 5-inch flask having a nitrogen gas introduction tube, a condenser, and a stirrer, N-methyl propylene oxiranyl ethyl group N-N, dimethylammonium _ 〇 ^ _ methyl group was placed. Carboxyl betaine (product of Osaka Organic Chemical Industry Co., Ltd., trade name · 68 201211072 GLBT) 35.0 Og, 3-mercaptopropyltrimethoxy decane (Shin-Etsu Chemical Co., Ltd., trade name: KBM-803 0.75 g and 143.02 g of ethanol. After degassing the internal pressure of the flask, the nitrogen gas was introduced to return to normal pressure, and the oxygen in the flask was removed as much as possible. Next, the contents of the flask were heated to 65 ° C by an oil bath attached to the flask, and then azobisisobutyronitrile (89 g) was added thereto, while maintaining the temperature of the contents of the flask at 7 Torr. (: aging for 4 hours. Thereafter, azobisisobutyronitrile ruthenium.36 g was further added to the burnt-out while maintaining the reaction temperature for 4 hours to obtain a polymer solution. The obtained polymer solution was cooled in a water bath. To 30. (:, diluted with 178.78 g of ethanol to obtain a polymer solution having an alkoxy fluorenyl group. The viscosity of a polymer solution having a thiol group having a thiol group is known as a Ubbel-type viscosity meter [ (Stock) Manufactured by mutual chemical chemistry, product number: U-0327-26] The average molecular weight of the viscosity was determined by 25t: and the viscosity average molecular weight was 5000. Production Example 4 Having a nitrogen gas introduction tube, condensation 5 〇〇mL capacity flask of the mixer and mixer was placed in methoxydiethyl acrylate (Osaka Organic Chemical Industry Co., Ltd.): V-MTG 3UGg, 3_mercaptopropyltrimethoxysilane Xiyuan [Shin-Etsu Chemical Industry Co., Ltd., trade name: KM_8〇3] 14 snake and ethanol 125. 68g. After degassing the pressure inside the flask, introduce nitrogen gas back to normal pressure 'as much as possible inside the flask Oxygen elimination. The oil is installed in the flask by the person After bathing, the contents of the flask were heated to λ, and then 1.57 g of azobisisobutyronitrile was added, and the temperature (4) of the contents of the flask 69 201211072 was aged at 7 〇t: for 4 hours. The propylene diisobutyronitrile o.31g was added to the reaction solution while maintaining the reaction temperature for 4 hours to obtain a polymer solution. The obtained polymer solution was cooled to 3 Torr with a water bath, 157. 10 g diluted The viscosity of the polymer solution having the alkoxy fluorenyl group/the obtained polymer solution having the oxalate group is prepared by the Ubbelde type viscosity meter (manufactured by the mutual chemical chemistry). U-0327-26] Determined at 25 ° C, the viscosity average molecular weight average molecular weight is 5 〇〇h. Production Example 5 In a 5 〇〇 mL volume flask with a nitrogen gas introduction tube, a condenser and a stirrer, 2, 2, 2-trifluoroethyl methacrylate [Osaka Organic Chemical Industry Co., Ltd. 'Item No.: V-3FM] 35.00 g, 3-mercaptopropyltrimethoxydecane [Shin-Etsu Chemical Industry Co., Ltd. ), trade name: KBM_8〇3] 2.34 and ethanol 149. 39g. After the internal pressure was reduced by degassing, nitrogen gas was introduced to return to normal pressure, and the oxygen in the flask was removed as much as possible. Next, the contents of the flask were heated to 65 ° C by an oil bath attached to the flask, and then azo was added. 187 g of diisobutyronitrile, and the temperature of the contents of the flask was maintained at 70 ° C for 4 hours. Thereafter, azobisisobutyronitrile 〇.37 g was further added to the flask, and the reaction temperature was maintained at 7 Torr. t The mixture was aged for 4 hours to obtain a polymer solution. The obtained polymer solution was cooled to 30 Torr in a water bath, and diluted with ethanol 18 6.74 g to give a polymer solution having an alkoxyfluorenyl group. The viscosity of the obtained polymer solution having an alkoxyfluorenyl group is determined by a Uber House 201211072 German-type viscometer (manufactured by Mutual Chemicals, manufactured by U.S. Patent No. U-0327-26) at 25 ° C. The viscosity average molecular weight was determined, and as a result, the viscosity average molecular weight was 4,000. Production Example 6 In a flask of 5 〇〇 mL capacity with a nitrogen gas introduction tube, a condenser and a stirrer, 2-(perfluorohexyl)ethyl decyl acrylate (Daikin Industry Co., Ltd., article number: M) was placed. -1620g, 12.00g, 3_mercaptopropyltrimethoxydecane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 0·29g and 2, 2' 2-trifluoroethanol 49. 15g. After degassing the pressure inside the flask, nitrogen gas was introduced to return to normal pressure, and the oxygen in the flask was removed as much as possible. Next, by heating the contents of the flask to 65 ° C by installing the oil bath in the flask, 61 g of azobisisobutyronitrile was added, and the temperature of the contents of the flask was maintained at 7 (TC ripening 4). After that, further, azobisisobutyronitrile (12 g) was further added to the flask, and the mixture was aged for 4 hours while maintaining the reaction temperature at 70 ° C to obtain a polymer solution. The obtained polymer solution was cooled to 3 in a water bath. 〇乞, 2, 2, 2 - trifluoroethanol 61. 44g diluted to obtain a polymer solution having an alkoxy fluorenyl group. The viscosity of a polymer solution having an alkoxy fluorenyl group is known as a Ubbelde type. The viscosity meter [manufactured by Mutual Chemicals Co., Ltd., product number: U 0327-26] was measured at 251 to obtain a viscosity average molecular weight, and as a result, the viscosity average molecular weight was 1 〇〇〇〇. Example 1 in a 100 mL valley The sample vial was placed in the polymer solution of the oxysulfanyl group obtained in the production example 1 & 4.5 Gg' 3 拂 propyl propyl trimethoxy hydroxy [ letter 71 201211072 越化学工业有限公司) :ΚΒΜ-803〕〇.15g and ethanol 55. 35g 'mix it by stirring thoroughly Then, 0.1N hydrochloric acid O.Olg was added to the vial, and the mash was prepared by thorough stirring and mixing. On the other hand, in the sample bottle of l〇〇mL capacity, 2_(perfluorooctyl)ethyl group was placed. 50 00 g of (meth) acrylate and 25 〇g of triethylamine were prepared by thoroughly mixing and mixing the liquid 11. As described above, a two-component surface modifier composed of the I liquid and the liquid u was prepared. Next, 5 mL of the above-mentioned I solution was applied onto a glass plate (length: 1 mm, width: 100 mm, thickness: imm), and the remaining liquid was removed by washing with ethanol, and then the glass plate was placed in a warm air drying. In the machine, the substrate was heated at a temperature of 12 (rc for 30 minutes), and a substrate modified with a polymer having an alkoxyfluorenyl group was first obtained. The human was treated with the above-mentioned polymer having a thioxanthene group. The substrate was immersed in a preheated A 6 (rc & u liquid 1 〇 mL + 6 〇 minutes. Then the effluent was removed from the II liquid to remove the excess sputum, and the acetone remaining on the substrate was The air is dried to obtain a substrate modified with a surface modifier.

A 100 mL-volume sample vial was placed in the pull-up I obtained in Production Example 1.

2, ( perfluorooctyl, by agitating and mixing the sputum l〇〇mL volume of the sample vial, adding [liquid. 72 201211072 base) ethyl acrylate 50. 00g and triethylamine 2. 50g, The 11 liquid was prepared by thoroughly stirring and mixing. As described above, a 2-liquid type surface modifying agent composed of a liquid I and a liquid II is prepared. Next, 5 mL of the above-obtained mash was applied to a glass plate (length: 丨〇〇mm, width: 100 mm, thickness: imm), and the remaining one was removed by washing with ethanol! After the solution, the glass plate was placed in a warm air dryer and dried at a temperature of 12 ° C for 30 minutes to obtain a substrate modified with a polymer having an alkoxy group. Next, the substrate treated with the alkoxyfluorenyl group-derived polymer obtained above was immersed in a preheating temperature of 60. 〇 π liquid l〇mL in 6 〇 minutes. Thereafter, the solution was taken out from the II solution, and the glass plate was washed with acetone to remove excess II liquid. The acetone remaining on the substrate was dried with an air gun to obtain a substrate modified with a surface modifier. Example 3 In a sample vial of a capacity of 100 mL, a polymer solution of alkoxyfluorenyl group obtained in Production Example i was placed in an amount of 1-5 g, 3-mercaptopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) : KBM-803] 0. 45g and ethanol 58. 05g 'mixed by thorough stirring. Thereafter, 0.1 N hydrochloric acid (K〇lg was added to the vial, and the liquid I was prepared by thorough stirring. On the other hand, in a 100 mL-volume sample vial, 2-(perfluorooctyl)ethyl acrylate was placed. 50. 00g and triethylamine 2. 50g 'The 11 liquid is prepared by mixing with sufficient agitation. As described above, a 2-liquid surface modifier composed of I liquid and II liquid is prepared. 10 mL flow is applied to the glass plate ( Length: l〇〇mm, width: 100mm, thickness: lmm) 73 t 201211072, after washing with ethanol to remove the remaining liquid i, the glass plate is placed in a warm air-drying inorganic solution. The temperature is maintained at 120 °C for 30 minutes. Air drying, first obtaining a substrate modified with a polymer having an alkoxyfluorenyl group. Next, the substrate treated with the alkoxyfluorenyl group obtained as described above is impregnated with a preheating temperature of 60 ° C. The liquid of the second liquid was taken in 10 mL for 60 minutes. Then, the second liquid was taken out, and the glass plate was washed with acetone to remove excess sputum. The acetone remaining on the substrate was air-dried to obtain a substrate modified with a surface modifier. Example 4 The alkoxy group obtained in Production Example 1 was placed in a vial of 10 OmL capacity. Base polymer solution 0·60g, 3-mercaptopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM_8〇3) 〇. 54g and ethanol 58.86g, by thorough stirring After mixing, 0.1N hydrochloric acid O.Olg was added to the vial, and the prepared solution was mixed by thorough stirring. On the other hand, in a sample bottle of l〇〇mL capacity, 2_(perfluorooctyl) was placed. 50.00 g of ethyl acrylate and 25 μg of triethylamine were mixed and prepared by thoroughly stirring and mixing. As described above, a two-component surface modifier composed of a liquid I and a mash was prepared. The obtained liquid 1 was applied to a glass plate (length: 100 mm, width: l_m, thickness: lram). After washing with ethanol to remove the remaining # 丨 liquid, the glass plate was placed in a warm air dryer at 12 Torr. The temperature of the crucible was dried by warm air for 30 minutes, and firstly, a substrate modified with a polymer having an alkoxyfluorenyl group was obtained. Next, 74 treated with the polymer obtained by the above-described alkoxy group. 201211072 The substrate was immersed in a pre-heating temperature of 6 (TC II solution 10 mL·60 minutes).

Thereafter, the liquid was taken out from the liquid, and the glass plate was washed with acetone to remove excess liquid II, and the acetone remaining on the substrate was air-dried to obtain a substrate modified with a surface modifier. Example 5 In a 100 mL-volume sample vial, a polymer solution of the alkoxyfluorenyl group obtained in Production Example 1 was placed in a 〇.3〇g'3-mercaptopropyltrimethoxy decane [Shin-Etsu Chemical Industry Co., Ltd. The product name: KBM-803] 0. 57g and ethanol 59·13g were mixed by thorough stirring. Thereafter, 0.1N hydrochloric acid 〇. 〇ig ' was added to the sample bottle to prepare the I liquid by thorough stirring. On the other hand, in a sample vial of 1 〇〇mL capacity, 2_(perfluorooctyl)ethyl acrylate 50. 〇〇g and triethylamine 2.5 〇g, prepared by thorough stirring and mixing 11 liquid. As described above, a two-component surface modifier composed of a liquid and a mash is prepared. Next, 5 mL of the above-mentioned I solution was applied to a glass plate (length: 1 mm, width: 100 mm, thickness: 1 mm), and the remaining one was removed by washing with ethanol! After the liquid, the glass plate was placed in a warm air dryer, and dried at a temperature of rc for 30 minutes, and a substrate modified with a polymer having an alkoxyfluorenyl group was first obtained. The polymer-treated substrate having an alkoxyfluorenyl group was immersed in 1 〇 mL of the n-liquid which was previously heated to 6 Torr for 6 。 minutes. Then, the II liquid was taken out, and the glass plate was washed with acetone to remove excess. In the liquid u, the acetone remaining on the substrate was air-dried to obtain a substrate modified with a surface modifier. 75 201211072 Example 6 The alkoxide obtained in Production Example 1 was placed in a sample vial of 100 mL·capacity.夕 的 的 的 〇 〇 〇 〇 g 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〔 〔 〔 〔 信 信 信 信 信 信 信 信 信 信 信 信 信 信 信 信 信 信The mixture was mixed well with agitation. After that, 0.1 N hydrochloric acid was added to the vial. 〇1 g 'The liquid I was prepared by thoroughly stirring and mixing. On the other hand, the sample vial of the volume of l〇〇mL was placed. 2-(perfluorooctyl)ethyl acrylate 50. 〇〇g and triethylamine 2.50g by charging Stir and mix and mix 11 liquids. As described above, prepare a 2-liquid surface modifier consisting of liquid I and liquid II. Secondly, 5 mL of the above-mentioned liquid I is applied to a glass plate (length: 丨〇〇mm, width) .100mm, thickness: 1)), after washing with ethanol to remove the remaining liquid, the glass plate is placed in a warm air dryer, and dried at a temperature of 12 (rc temperature for a minute to obtain an alkoxy alkoxide). Base polymer treated substrate.

Next, the substrate treated with the alkoxyfluorenyl group-derived polymer obtained above was impregnated for 6 minutes in a pre-heated state of 6 (rc liquid of rc). After that, it was taken out from the liquid II and washed with acetone. The glass plate removes the excess U liquid', and the silicon remaining on the substrate is dried by air to obtain a substrate modified with a surface modifier. Comparative Example 1 A 1% sodium laurate aqueous solution is applied to a glass plate, and the solution is applied. The glass plate was placed in several dryers and dried at a temperature of 12 ° C for 3 minutes to obtain a substrate treated with the previous surfactant. 76 201211072 Comparative Example 2 Flow of 1% sodium tetradecanoate on a glass plate The aqueous solution was placed in a warm air dryer, and dried at a temperature of 12 (rc) for 3 minutes, and a substrate treated with the previous surfactant was obtained. Comparative Example 3 Flow of 1% palmitic acid on a glass plate The aqueous solution of sodium was placed in a warm air dryer, and dried at a temperature of 12 (rc for 3 minutes at room temperature to obtain a substrate treated with the previous surfactant. Next, the surface obtained by each example was modified by surface. Modified substrate and The physical properties of the surfactant-treated substrate obtained in the comparative example were investigated by the following method by the contact angle with water or n-decane, the thickness of the overcoat formed of the surface modifier or the surfactant, and the water resistance. Shown in the table [contact angle with water or brothel] on a substrate modified with a surface modifier and a substrate treated with a surfactant, droplets of water droplets or n-decane are dropped, and water or positive The contact angle of decane was measured by contact angle (manufactured by ERMA) in an atmosphere of 25 ° C. [Thickness of the film] It was formed on a substrate modified with a surface modifier and treated with a surfactant. The thickness of the cover film composed of the surface modifier or the surfactant on the substrate is measured by a stylus type differential meter [KLA. TENK〇R (product), article number: ρ_ι〇]. The above-mentioned "contact angle with water or Zhengxuan" substrate modified with a surface modifier and a substrate treated with a surfactant, with water or n-decane in the contact angle of 77 201211072 25C atmosphere [ERMA ( After the measurement, the base will be modified with a surface modifier. And the substrate treated with the surfactant is immersed in water heated to 80 ° C for 5 hours. The person, the substrate is taken out from the water, washed with water, and the water adhering to the substrate is dried by air, after 25 The contact angle with water is measured in the atmosphere. The difference between the contact angle between the substrate and water after the water test and the contact angle between the substrate and the water before the water resistance test is used for the absolute difference. Further, the smaller the absolute value, the better the water resistance of the substrate. Example No. 1 2 3 4 5 6 Comparative Example 1 2 3 Contact angle with water (Tang) 4 4 6 8 111 111 2 3 3 Surface modified substrate" contact angle with n-decane [庶] 1 2 4 40 54 64 1 2 2 Thickness of the film (nm) 20 20 20 20 20 20 Since the film cannot be measured due to the film Unable to measure soil-based film. Water resistance could not be measured. 0 0 0 0 0 25 23 25 Results from Example 3 shown in Table 2 'The surface of the substrate modified with water, contact angle with water and contact with n-decane The angles are very low, and thus it is known that both hydrophilic and lipophilic. From &, it is understood that the use of the two-component surface modifier of the present invention can impart properties opposite to hydrophilicity and lipophilicity to the substrate at the same time. Further, the substrate which was surface-modified by the result of Example 4 had a small contact angle with water, and the contact angle A with the positive broth was such that hydrophilicity and oil repellency were imparted. "It is understood that the use of the two-component surface modifier of the present invention can impart hydrophilicity and oil repellency to the substrate at 78 201211072. Further, by the results of Examples 5 to 6, the surface-modified substrate is in contact with water. Both the angle and the contact angle with n-decane are both high, and it is understood that both the water repellency and the oil repellency are obtained. It is understood that the two-component surface modifier of the present invention can be used to impart water repellency and oil repellency to the substrate. In the above, it is known that the two-component surface modifier of the present invention can simultaneously impart properties such as wateriness and water repellency to the substrate, and properties relating to oily components such as lipophilicity and oil repellency. The surface-modified substrate obtained in each of the examples was excellent in water resistance even when it was immersed in water of 80 C for 5 hours, and it was found that the polymer having an alkoxyfluorenyl group contained in the surface modifier was strong. The substrate is fixed to the substrate, and the (meth)acrylic monomer is firmly fixed to the substrate via a decane coupling agent having a thiol group. Therefore, the two-component surface modifier of the present invention can be used continuously. Substrate assignment (After the third group of the present invention) Example 1 In a flask equipped with a nitrogen gas introduction tube, a condenser, and a stirrer, N-methyl group was placed. Propylene oxiranyl ethyl-N,N_:methylammonium _α_Ν_methylcarboxybetaine monohydrate and water [Osaka Organic Chemical Industry Co., Ltd., trade name: GLBT] 25.0g, r_methacrylofluorene Propyltrimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM_5〇3) 3〇. 4 and ethanol 500. 3g. After degassing the pressure inside the flask, the nitrogen gas is introduced to return to the constant 79. 201211072 Next, 2.8 g of azobisisobutyronitrile was added to the flask, and the temperature of the contents of the flask was maintained at 7 (the rc was aged for 8 hours, and then cooled to 3 ° C in a water bath to obtain a (meth)acrylic acid system. The polymer solution. The viscosity of the obtained (meth)acrylic polymer solution is 25° by Uberland-type viscometer (product number: U-0327-26) manufactured by Mutual Chemicals Co., Ltd. When C was measured, the viscosity average molecular weight was determined, and as a result, the viscosity average molecular weight was 39 Å. The (meth)acrylic polymer solution was used as a surface hydrophilizing agent. Example 2 In a flask equipped with a nitrogen gas introduction tube, a condenser, and a stirrer, N-methyl propylene oxide oxyethyl group was placed. N,N-diguanidinyl-qj-N-methylcarboxybetaine monohydrate and water (Osaka Organic Chemical Industry Co., Ltd., trade name: GLBT) 25.0g, r-methacryloxypropyltrimethyl Oxy decane [trade name: KBM-503] manufactured by Shin-Etsu Chemical Co., Ltd. 11.4 g and ethanol 327. 7 g. After degassing the pressure inside the flask, nitrogen gas was introduced to return to normal pressure. After adding 1.8 g of azobisisobutyronitrile, the temperature of the inner grain of the flask was maintained at 70 C for 8 hours, and then cooled to 3 〇C ' in a water bath to obtain a (meth)acrylic acid polymer solution. The viscosity of the obtained (meth) acryl-based polymer solution was determined by a Ubbel-type viscometer (manufactured by Mutual Chemicals Co., Ltd., product number: U-0 32 7-26). (: Measurement, viscosity average molecular weight was obtained, and the viscosity average molecular weight was 1 Å. The (meth)acrylic polymer solution was used as a surface hydrophilizing agent. Example 3 was provided with a nitrogen introduction tube, and condensed. 1L capacity of the machine and mixer 80 201211072 bottle, put N-mercapto propylene oxiranyl _N,N-dimethylammonium-〇:1_methylcarboxybetaine-water and substances [Osaka Organic Chemistry Industrial (stock), trade name: GLBT] 30.0g, τ-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: 〇M-503) 3.6g and ethanol 3〇 2 〇g. After degassing the pressure inside the flask, the nitrogen gas was introduced to return to normal pressure. Next, 1.7 g of azobisisobutyronitrile was added to the flask while maintaining the temperature of the contents of the flask at 701: ripening. After 8 hours, the solution was cooled to 3 ° C by water bath to obtain a (meth)acrylic polymer solution. The viscosity of the obtained (meth)acrylic acid polymer solution was determined by a Uber-Lloyd type viscosity meter. Manufactured by mutual chemical chemistry, product number: U-0327-26] measured at 25 ° C The viscosity average molecular weight was determined, and as a result, the viscosity average molecular weight was 1. The (meth)acrylic polymer solution was used as a surface hydrophilizing agent. Example 4 was provided with a nitrogen gas introduction tube, a condenser, and a stirrer.丨 [Capacity flask] is placed in N-methyl propylene oxiranyl-n, N-dimercaptoammonium-α_Ν_methylcarboxybetaine monohydrate and product (Osaka Organic Chemical Industry Co., Ltd.) Name: GLBT] 25.0g, r-methacryloxypropyltrimethoxydecane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 4.4g, butyl propyl acrylate 7.6g and ethanol 333.5 g. After the pressure in the flask was degassed, the nitrogen gas was introduced to return to normal pressure. Next, argon diisobutyronitrile h9g was added to the flask, and the temperature of the contents of the flask was maintained at 70 C for 8 hours. The solution was cooled to 3 〇C ' in a water bath to obtain a (meth)acrylic polymer solution. The viscosity of the obtained (mercapto)acrylic polymer solution was determined by a Ubbel-type viscosity meter. Made by chemical glass manufacturer, article number: U-0327-26] to 25 The viscosity average molecular weight was determined by ° C, and the viscosity average molecular weight was 24,000. The (mercapto)acrylic acid polymer solution was used as a surface hydrophilizing agent. Example 5 was provided with a nitrogen gas introduction tube and a condenser. A 1 L-capacity flask of a blender was charged with N-methylpropenyloxyethyl-N,N-dimethyl-α-N-decylcarboxybetaine-water (Osaka Organic Chemical Industry Co., Ltd., Trade name: GLBT] 25. Og, r-methyl propylene oxypropyl trimethoxy decane [Shin-Etsu Chemical Co., Ltd.'s trade name: KBM-503] 4.4g, styrene 5.6g and ethanol 315. 2g « After degassing the pressure inside the flask, nitrogen gas was introduced to return to normal pressure. Next, 1.88 g of azobisisobutyronitrile was added to the flask, and the temperature of the contents of the flask was maintained at 70 ° C for 8 hours, and then cooled to 30 ° C in a water bath to obtain (meth)acrylic acid. Polymer solution. The viscosity of the obtained (meth) acryl-based polymer solution was determined by a Ubbelde type viscometer (manufactured by Mutual Chemicals, manufactured by U.S. Patent No. U-0327-26). (Measurement, viscosity average molecular weight was obtained, and the viscosity average molecular weight was 26 Å. The (meth)acrylic polymer solution was used as a surface hydrophilizing agent. Example 6 was provided with a nitrogen introduction tube, and condensed. a 1 L capacity flask of a stirrer and a mixture of N-methyl propylene oxiranyl-n,N-dimethylammonium-cn-N-methylcarboxybetaine monohydrate and water (Osaka Organic Chemical Industry Co., Ltd. Product Name: GLBT] 25.0g' 7*-Methyl propylene oxime propyl trimethoxy decane [Shin-Etsu Chemical Co., Ltd.'s trade name: KBM-503] 4.4g, butyl butyl butyl 82 8 201211072 Enamine 7. 6g and ethanol 333. Og. After degassing the pressure in the flask, the nitrogen gas was introduced to return to normal pressure. Next, 1.9 g of azobisisobutyronitrile was added to the flask while the flask was placed. The temperature of the contents was maintained at 70 ° C for 8 hours, and then cooled to 3 ° C by a water bath to obtain a (meth)acrylic polymer solution. The viscosity of the obtained (meth)acrylic polymer solution was obtained. Made by Uber Loude type viscometer [(shares) mutual chemical chemistry manufacturing, product number :U-0327-26] The viscosity average molecular weight was determined by 25 eC, and the viscosity average molecular weight was 22,000. The (meth)acrylic polymer solution was used as a surface hydrophilizing agent. Example 7 was introduced with nitrogen gas. 1L capacity flask of tube, condenser and agitator 'into N-mercapto propylene oxyethyl-N,N-dimethyl-α-Ν-methylcarboxy beet test water and substance [Osaka Organic Chemical industry (share), trade name: GLBT] 25.0g, mercapto propylene oxypropyl methyl dimethoxy stone Xiyuan (Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM-502) 30. 6g 5克。 While the internal pressure of the flask was reduced by degassing, the introduction of nitrogen was added to the normal pressure. Next, the azobisisobutyronitrile was added to the flask 2. 8g, while maintaining the temperature of the contents of the flask After aging at 8 °C for 8 hours, the solution was cooled to 3 °C by a water bath to obtain a (meth)acrylic acid polymer solution. The viscosity of the obtained (mercapto)acrylic polymer solution was obtained in Uber House. German-type viscometer [(share) made by mutual chemical chemistry, manufactured by U-0327-26] 2 The viscosity average molecular weight was determined at 5 ° C, and the viscosity average molecular weight was 34000. The (fluorenyl) acrylic polymer solution was used as a surface hydrophilizing agent. 83 201211072 Example 8 A nitrogen gas introduction tube and a condenser were provided. In the flask of the mixer, the N-mercapto acrylamidoethyl hydrazine, bisdimethylammonium _α_Ν_mercaptocarboxybetaine monohydrate and water (Osaka Organic Chemical Industry Co., Ltd.) 25 Og, r-methacryloyloxypropyltrimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) 30.6 g and ethanol 500 3 g. After degassing the pressure inside the flask, nitrogen gas was introduced to return to normal pressure. Next, 2 8 g of azobisisobutyronitrile was added to the flask, and the temperature of the contents of the flask was maintained at 70 ° C for 8 hours, and then cooled to 3 ° C in a water bath to obtain (meth)acrylic polymerization. Solution. The viscosity of the obtained (meth)acrylic polymer solution was 25 by a Ubbelde type viscometer (manufactured by Mutual Chemicals, manufactured by U.S. Patent No. U-0327-26). The enthalpy was measured to obtain a viscosity average molecular weight, and as a result, the viscosity average molecular weight was 35 Å. This (meth)acrylic polymer solution was used as a surface hydrophilizing agent. Comparative Example 1 In a 1 L-capacity flask equipped with a nitrogen gas introduction tube, a condenser, and a stirrer, N-methyl propylene oxiranyl-N,N-dimethylmethyl ketone beet was used to test the water and the substance [Osaka Organic chemical industry (trade name), trade name. GLBT] 21.5g, butyl methacrylate 28.5g and ethanol 45〇〇g. After degassing the pressure inside the flask, nitrogen gas was introduced to return to normal pressure. Next, '2,5 g of azobisisobutyronitrile was added to the flask, and the temperature of the contents of the flask was maintained at 70 ° C for 8 hours, and then cooled to 3 ° C ' in a water bath to obtain (fluorenyl) acrylic polymerization. Solution. The viscosity of the obtained (mercapto) acrylic acid polymer solution is Ubbelde type viscometer [(shares) 8 84 201211072 chemical glass manufacturing system, article number: U-0327-26] to 25 <> c measurement, to obtain the viscosity average knife amount 'results, the viscosity average molecular weight is Μ 。. This (meth)acrylic polymer solution was used as a surface hydrophilizing agent. Comparative Example 2 In a flask having a volume of a nitrogen gas introduction tube, a condenser, and a stirrer, a gas methane salt of N,N-dimethylammonium methacrylate 2i 5 g, methacryloxypropyltrimethoxydecane [ Shin-Etsu Chemical Co., Ltd., product j: KBM-503] 28.5 g and ethanol 450.0 g. After degassing the pressure inside the flask, the introduction of nitrogen was repeated to normal pressure. Next, 25 g of azobisisobutyronitrile was added to the flask, and the temperature of the contents of the flask was maintained at 7 (the rc was aged for 8 hours, and then cooled to 3 ° C in a water bath to obtain a (meth)acrylic polymer. The viscosity of the obtained (meth)acrylic polymer solution is determined by a Ubbelde type viscometer (manufactured by Mutual Chemicals, product number: u_0327_26) to determine the viscosity average molecular weight. As a result, the viscosity average molecular weight was 29 Å. The (meth)acrylic polymer solution was used as a surface hydrophilizing agent. Comparative Example 3 In a flask having a nitrogen gas introduction tube, a condenser, and a stirrer, methacrylic acid 21. 5g, methacrylic acid methoxypropyl trimethoxy decane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM_5〇3] 28 5g and ethanol 450. Og. After degassing the pressure inside the flask, The nitrogen was introduced to the normal pressure. Next, the azobisisobutyronitrile was added to the flask at 2.5 g, and the temperature of the contents of the flask was maintained at 7 (the TC was aged for 8 hours, and then cooled in a water bath to £85 201211072 °c. 'Get (曱Acrylic polymer solution. The viscosity of the obtained (meth)acrylic polymer solution is determined by a Ubbelde type viscometer [product number: U-0327-26] 25. (: Measurement, viscosity average molecular weight was obtained, and the viscosity average molecular weight was 22,000. The (mercapto) acrylic polymer solution was used as a surface hydrophilizing agent. Comparative Example 4 was provided with a nitrogen gas introduction tube, a condenser, and 1 L capacity flask of a stirrer, 21.5 g of butyl methacrylate, r-methyl propylene oxypropyl trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) 28.5 g and ethanol 450 0g» After degassing the pressure in the flask, the nitrogen gas was introduced to return to normal pressure. Next, '2,5 g of azobisisobutyronitrile was added to the flask while maintaining the temperature of the inner grain of the flask at 70 C. After 8 hours of aging, the solution was cooled to 3 〇C by a water bath to obtain a (meth)acrylic acid polymer solution. The viscosity of the obtained (meth)acrylic acid polymer solution was determined by a Ubbelde type viscometer. 〔(股) mutual chemical chemistry manufacturing The product number: U-0327-26 was measured at 25 t to obtain a viscosity average molecular weight, and as a result, the viscosity average molecular weight was 36 A. The (meth)acrylic polymer solution was used as a surface hydrophilizing agent. Experimental Example The surface hydrophilizing agent obtained in each of the examples or the comparative examples was applied onto a glass plate (length: 100 nm, width: 10 mm, thickness lmm), and after washing with ethanol to remove the remaining surface hydrophilizing agent, The glass plate was placed in a warm air dryer, and dried at a temperature of 120 ° C for 30 minutes to obtain a surface hydrophilized substrate. 8 86 201211072 u ', the surface of the hydrophilized substrate was transferred The physical properties were evaluated in the following manner with respect to water, contact angle rubbing resistance, water resistance, solvent property, and thickness of the overcoat. The results are shown in Table 3. [Contact angle to water], water droplets were dropped on the surface hydrophilized substrate, and the contact angle with respect to water was measured at 25 C using a contact angle meter (ERMA), and evaluated by the following evaluation criteria. (Evaluation criteria) Ο : The contact angle with water is less than 1 degree X. The contact angle with water is 10 degrees or more (friction resistance). Rubbing cloth [made by Japan Paper CRECIA Co., Ltd., trade name: KIMWIPE s 20 0] After the surface of the hydrophilized substrate was wiped 3 times with a load, water droplets were dropped on the surface at 25. (4) The contact angle with respect to water was measured in the atmosphere and evaluated by the following evaluation criteria. (Evaluation criteria) 〇: The contact angle with water is less than 1 〇 X. The contact angle with water is 10 degrees or more [Water resistance] The surface hydrophilized substrate is immersed in heated hot water for 5 hours. The surface hydrophilized substrate was taken out from the hot water, and the contact angle of water was measured to investigate whether the (meth)acrylic polymer contained in the surface hydrophilizing agent on the surface hydrophilizing substrate was dissolved. In hot water, it is evaluated on the basis of the following evaluation criteria. (Evaluation Criteria) 87 201211072 〇: The contact angle with water after the water resistance test is less than 10 degrees X: The contact angle with water after the water resistance test is 1 〇 or more [solvent resistance] by hydrophilizing the surface The material was immersed in acetone heated to 4 Torr for 1 hour. 'A solvent resistance test was carried out 'The surface hydrophilized substrate was taken out from the acetone'. The surface of the hydrophilic substrate was investigated by measuring the contact angle with water. Whether or not the (meth)acrylic polymer contained in the surface hydrophilizing agent is dissolved in the acrylic acid is evaluated by the following evaluation criteria. (Evaluation Criteria) 〇: The contact angle with water after the solvent resistance test is less than 1 〇 degree x: The contact angle to water after the solvent resistance test is 1 〇 or more (thickness of the film) will be formed on the surface hydrophilic substrate The thickness of the film composed of the surface hydrophilizing agent was measured by a stylus type step meter (manufactured by KLA·TENK0R (stock), article number: P-10). Table 3 Example No. ------- Properties of water base & surface IL hydration base 4 i -J 1 〇〇 abrasion resistance 〇 water resistance 〇 solvent resistance 〇 film thickness ( Um) 3 LQ 〇〇〇〇3 ό λ 〇〇〇〇3 4 C 〇〇〇〇3 D 0 〇〇〇〇3 0 7 〇〇〇〇3 1 0 〇〇〇〇3 〇Ο 〇〇〇3 Comparative Example 1 0 〇 XXX 3 LQX 〇〇〇 3 0 AX 〇〇〇 3 ft X 〇〇〇 3 88 8 201211072 From the results shown in Table 3, it can be seen that the surface hydrophilizing agent obtained in each example can be used for the substrate. Gives hydrophilicity. Further, since the surface hydrophilizing agent obtained in each of the examples was superior to Comparative Examples 1 to 4, it was possible to impart superior financial friction, water resistance and financial solvent property to the substrate. Thus, it was found that even if it was in contact with water. It is also difficult to remove the hydrophilic film from the substrate. [Industrial Applicability] The surface modifier of the first group of the present invention can be applied to a surface thereof by coating a substrate composed of various materials such as glass, metal, and organic materials. In view of the nature, it is expected to be a technique for hydrophilizing a surface of a silicone resin such as a sophisticated medical device or an artificial organ, or a technique for preventing adhesion of proteins, cells, or the like. Further, since the surface modifier of the first group of the present invention can easily hydrophilize the surface of an automobile glass, a mirror or the like, it is also useful for imparting antifogging to a mirror, a glass surface of a solar panel, a window of a house, or the like. The self-cleaning function "protects against the adhesion of dust, dust, etc. by charging the liquid crystal display or the like." In the two-component surface modifier of the second group of the present invention, a substrate having a hydroxyl group or the like can be applied to the surface of various materials such as glass, metal, or organic material, and the surface thereof can be imparted to the surface. In view of the nature, it is expected to be used in a hydrophilization technique on the surface of a silicone resin such as a sharp medical device or an artificial organ, or a technique for preventing adhesion of proteins and cells. Further, the two-component surface modifier of the second group of the present invention can be easily used for the mirror or the solar panel because it can easily hydrophilize the surface of the glass, the mirror, or the like of the automobile. The glass surface, the window of the house, etc., are provided with anti-fog property or self-cleaning function, and the liquid crystal display or the like is prevented from being changed by the belt to prevent adhesion of dust, dust, dust, dust, and the like. The surface hydrophilizing agent of the third group of the present invention can be used for cutting-edge medical treatment by applying a hydrophilic material to the surface of the substrate by coating a substrate composed of various materials such as glass, metal, and organic materials. A technique for hydrophilizing the surface of a stone resin such as an instrument or an artificial organ, or a technique for preventing adhesion of proteins, cells, and the like. Further, when the surface hydrophilizing agent of the present invention is applied to a packaging material for foods, the bacteria and bacteria are not easily adhered, so that food hygiene can be expected to be improved. Further, since the surface hydrophilizing agent of the third group of the present invention can easily hydrophilize the surface of a glass, a mirror or the like of an automobile and is fixed to the surface thereof, it is also used for a glass surface of a mirror or a solar panel. In addition, the window of the house or the like is provided with an anti-fogging property or a self-cleaning function, and the liquid crystal display or the like is prevented from being changed by the tape to prevent the adhesion of dust or dust, etc. Further, the surface hydrophilizing agent of the third group of the present invention is coated. When it is placed on the surface of the bottom of the ship, it can give the bottom of the ship hydrophilicity, so it can be expected to contribute to reducing the fuel consumption of the ship. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (a) and (b) show the first group of the present invention, and the surface temporary effect # aa & y obtained in Example 7, respectively, the unmodified substrate and the comparative example 1 The glass plate is used to investigate the anti-fog results. [Main component symbol description] Benefit 8 90

Claims (1)

201211072 VII. Patent application scope: 1. A surface modifying agent having a repeating unit represented by formula (1) and containing at least one side of the alkoxyfluorenyl group represented by formula (II). Polymer: 'R1 I Γ〇(I) ο I R2 where 't represents a hydrogen atom or a methyl group, and R2 represents a hydrophilic group, a hydrophobic group, a cationic group or an anionic group; R3 (ID R4-Si-R (RE where R', R and R5 independently represent the carbon number of the alkyl group or the carbon number of the group 4, and at least one of the base groups of R, 4 and R5 The alkoxy group of 1 4, R is an alkylene group of the carbon number. 2. The surface modifier according to claim 4, wherein the formula (1) 'R2 may have a hydrogen atom, a base or a The base of the atom having 2 to 20 carbon atoms may have a carbon number of 6 to 20 aryl groups of a radical or a gas atom, and may have a hydrogen atom or a carbon number of 4, and may have a radical or a fluorine atom. The king's enamel enamel base, on the one side of the ancient 曰 'has a hydrogen atom at the end or a carbon number of 1 to 4, also has a hydroxyl or fluorine atom of ethylene oxide The addition of the base has a molar number of 2 to another polyepoxy group, a hydrogen atom at the end of the edge or a fluorene group of the fluorene group, or a propylene group having a trans group or a fluorine atom. Having: 91 201211072 A hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a propylene group having a hydroxyl group or a fluorine atom may be added to a polypropylene oxide group having a molar number of 2 to 20, and a formula (111) The base of the formula or the formula (IV): R9 - R7 - N-R8-CO〇- R10 (III) wherein R7 and R8 each independently represent an alkylene group R9 of carbon number 4 and R1 (l is independently represented by a hydrogen atom or a carbon number of 4 alkyl groups; R12 χ-(IV)-Ru-N-R14 R13 wherein R represents an alkylene group of carbon number 4, and 12 And Ru are each independently represented by a hydrogen atom or an alkyl group having a carbon number U, an RH-based organic group, and an X-form is an anion. The surface modifier according to claim 1 or 2, wherein 1) The number of the repetitive units indicated is 1200. 4. A surface-modified substrate obtained by modifying the surface modifier according to any one of claims 3 to 5. One type A method for producing an acrylic polymer, which comprises polymerizing a (meth)acrylic monomer described in the formula (Va) in the presence of a compound containing an alkoxymethyl group represented by the formula (Via). The repeating unit shown in the formula (1) has an alkoxy fluorenyl group represented by the formula (II) at the end of the fluorene: CH2=C - C - Ο - R2 R - I (Va) 92 201211072 wherein R1 represents a hydrogen atom or a methyl group, R2 represents a hydrophilic group hydrophobic group, a cationic group or an anionic group; R3 (Via) R4-Si-R6-SH R5 wherein R3, R4 and R5 are each independently represented a carbon number i ~ 4 alkyl or carbon number ruthenium, R3, r5 of at least one base carbon number of 1-4 alkoxy, R6 means a carbon number 丨 ~ 12 alkylene; R1 I (I) -tC-CH23-C ^ 〇I 〇I R2 wherein R1 and R2 are the same as above; R3 I (II) R4-Si-R6-I R5 wherein R3, R4, R5 and r6 are the same as above. 6. The method for producing a (meth)acrylic polymer according to claim 5, wherein the formula (1) 1 is a hospital group having a hydrogen atom, a hydroxyl group or a fluorine atom of 2 to 20 carbon atoms, The alkyl group having a carbon number of 6 to 20 groups on the side of a fluorine atom or a fluorine atom and having a hydrogen atom or a carbon number η at one end may have a mercapto group or a fluorine atom. A hospital base having a hydrogen atom or a carbon number 亦可 may also have an epoxy group having a radical or a gas atom. 92 201211072 Adding a mole having a molar number of 2 to 20 per 7 or a carbon number a propylene oxide having a hydrogen atomic group at one end, or a propylene oxide having a hydroxyl group or a fluorine atom, may have a gas atom or a carbon number, and may have a base or a gas atom. η, addition molar number is a 2-core polyepoxy pit group, a group represented by formula (1) 1), or a group represented by formula UV): -R7~ht R10 R8-C〇〇· (III) R12 ( IV) -Ru--N~RM . χ- 13 R The independent two 11 series represents the residue of the carbon number w, and the R, 1R13 system stands on the surface, respectively, or the carbon number is 1 ρΐ4. Child. The county, the R system, the organic group, and the X-based poly 2nd 2-type surface modifier of the money 14 include a polysiloxane having a oxyalkyl group. And a liquid of the (IV) coupling agent having a thiol group; and a liquid containing a liquid of a (meth)acrylic acid monomer. [2] The liquid-type surface modifier described in the seventh aspect of the patent, wherein the polymer having the oxime group has the repetitive unit represented by the formula (1), and has at least the end of the - side ((1) Alkoxylate-based (meth)acrylic acid polymer: 8 94 201211072 R1 I G = 〇I o R where R1 represents an argon atom or a methyl group, R2 represents a hydrophilic group hydrophobic group, a cationic group or an anionic group; R3 (II) R4-Si-Rf I R5 wherein R , R and R ' are each independently represented by an alkyl group having 1 to 4 carbon atoms or an alkoxy group having a carbon number of 4, and R3' is at least one alkoxy group having 1 to 4 carbon atoms, R6 A 2-liquid surface modifier as described in claim 8 of the invention, wherein the R2 system may have a hydrogen atom, a trans group or a fluorine atom. An alkyl group having 2 to 20 carbon atoms, a carbon number of 6 to 2 aryl groups having a hydroxyl group or a fluorine atom, or a group having a hydrogen atom or a carbon number W at one end may have an epoxy group having a base group or a hydrocarbon atom. An ethane group having an alkyl group having a hydrogen atom or a carbon number at one end may have a polyethylene oxide group having a hydroxyl group or a gas atom, and a polyethylene oxide group having a molar number of 2 to 20, on one side. The alkyl group having a hydrogen atom or a carbon number at the terminal may have an oxypropylene group having a hydroxyl group or a fluorine atom, a hydrogen atom at one terminal or an alkyl group having a carbon number of 1 to 4, or may have a hydroxyl group or The propylene oxide group of a fluorine atom is added to a polypropylene oxide group having a molar number of 2 to 20, a group represented by the formula (ΙΠ), or a group represented by the formula (IV): 95 (III) 201211072 R. R7—N—R8—C 〇〇· R10 wherein R 7 and R 8 each independently represent the alkylene group R 9 and R lf of the carbon number i are independently represented by an argon atom or an alkyl group having 1 to 4 carbon atoms: R12 (IV) -Ru-N-R14 · X' R13 % A' R is an alkylene group having a carbon number of 4, and R12 and R13 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R14 The organic group and the χ-sun represent an anion. ' 10. The two-liquid type agent described in the 8th or gth of the patent scope of Shen Qing, wherein the number of the units of the uf 'A to the formula (I) is 1~ The two-hip type surface modifier according to any one of claims 7 to 10, wherein the decane coupling agent having a thiol group is represented by the formula (Vl) Alkoxyfluorenyl compound: b) RiB, r I (VIb) R16-Si-Rl8-SH R,7 wherein R15, R16 and R17 each independently represent a carbon number 4, a base or a carbon number of 1 ~4 alkoxy, R15, R&quot; and f At least one alkoxy group having a carbon number of from 1 to 4, and R.sup.18, an alkylene group having a carbon number of from 1 to 2, which is a type 2 surface according to any one of claims 7 to 5 a modifier, wherein the (meth)acrylic monomer is a (meth)acrylic acid monomer of the formula (Vb): represents 96 201211072 CH, C —c-R19 〇OR 20 (Vb), R represents a hydrogen atom or a fluorenyl group, and R<2> represents a hydrophilic group, a hydrophobic 'group, a cationic group or an anionic group. The two-component surface modifier according to claim 12, wherein the formula (Vb)' has an alkyl group having a hydrogen atom, a hydroxyl group or a fluorine atom of 2 to 20 in the f system. The carbon group having a hydroxyl group or a fluorine atom having 6 to 2 fluorene groups and having a hydrogen atom at one terminal or a carbon number of 1 to 4 may have an oxiranyl group having a hydroxyl group or a fluorine atom and having a hydrogen atom at one end. Or an alkyl group having 1 to 4 carbon atoms or a oxirane group having a hydroxyl group or a fluorine atom, and a polyepoxy group having a molar number of 2 to 20, having a hydrogen atom or a carbon number at one end. The alkyl group of 4 may have an oxypropylene group having a hydroxyl group or a fluorine atom, an alkyl group having a hydrogen atom or a carbon number at one end, or an oxiran group having a hydroxyl group or a fluorine atom. 2~2〇 of the polypropylene oxide group, the group represented by formula (III), or the group represented by formula (IV): R9 - R7 - NR{ R10 coo_ (III) where 'R7 and R8 are independent The alkylene groups R9 and R1 0 which represent a carbon number are each independently represented by a hydrogen atom or an alkyl group having a carbon number of 1 to 4, R12 - Rn-NlRi4. 13. R13 (IV) wherein 'R is a table An alkylene group of 1 ~ 4 carbon atoms, R12 and R13 each independently represent lines is not a hydrogen atom or an alkyl group of 1 ~ 4 carbon atoms, an organic-based group, Χ · 97201211072 table not based anion. A method for producing a surface-modified substrate, comprising: coating a substrate comprising a polymer having an alkoxyfluorenyl group and a thiol group-containing decane coupling agent #I solution; The surface of the liquid substrate is coated with a liquid containing a (meth)acrylic monomer, and a decane coupling agent having a thiol group is reacted with a (meth)acrylic monomer. 15. The method for producing a surface-modified substrate according to claim 14, wherein the polymer having an alkoxyfluorenyl group has a repeating unit represented by the formula (I) and has a formula at least at one end ( II) Alkoxyfluorenyl (fluorenyl) acrylic polymer: R1 I —fC-CH2l·- (I) 〇I R2 wherein 'R1 hydrogen atom or fluorenyl group, R2 represents hydrophilic group, hydrophobic The radicals, cationic or anionic groups are represented by repeating units, at least one side of the formula (II); R3 I R4-Si-R6- (II) R5 where the 'R3, R4 and R5' systems are independent The ground indicates the base of the number 4 or the alkoxy group of the carbon number 4, at least one of the groups R3 ' and R5 is an alkoxy group having 1 to 4 carbon atoms, and R6 means an alkylene group having a carbon number of 1 to 12 base. The method of manufacturing a surface-modified substrate according to claim 15, wherein the formula (i), the R2 system may have a carbon number of 2 to 20 of an argon atom, a hydroxyl group or a fluorine atom. The alkyl group having 6 to 2 aryl groups having a hydroxyl group or a fluorine atom and having a hydrogen atom or a carbon number at one end may also have an oxiran group of a trans group or a fluorine atom. The terminal having a hydrogen atom or a carbon number of 1 to 4 may have an epoxy group having a hydroxyl group or a fluorine atom, and a poly(ethylene oxide group) having a molar number of 2 to 20 and having a hydrogen atom at one end. Or a propylene oxide group having a carbon number of 1 to 4 or an oxypropylene group having a hydroxyl group or a fluorine atom, an alkyl group having a hydrogen atom or a carbon number at one end, or an oxypropylene group having a hydroxyl group or a fluorine atom. a polypropylene oxide group having a molar number of 2 to 20, a group represented by the formula (III), or a group represented by the formula (IV): R9 1 + -R7-N-R8-C00· (III) R10 Wherein R 7 and R 8 each independently represent an alkylene group of carbon number 4, and R 9 and R 1 () each independently represent an 'argon atom or an alkyl group having 1 to 4 carbon atoms; R 12 I + -Ru-N-R14 · χ-(IV) R13 wherein 'R series means that the alkylene group having a carbon number of 1 to 4, the riz and the ru system each independently represent a hydrogen atom or an alkyl group having a carbon number of 4; The R14 organic group and the fluorene system represent an anion. 17. The method for producing a surface-modified substrate according to the invention of claim i or 5, wherein the number of the repetitive units represented by the formula (I) is 1000. The method for producing a surface-modified substrate according to any one of claims 14 to 17, wherein the decane coupling agent having a thiol group is represented by the formula (VIb) Compound of the oxetane group: R15 (VIb) R16-Si-Rl8~SH R17 wherein R15, R16 and R17 each independently represent an alkyl group having a carbon number of 4 or an alkoxy group having a carbon number of 1 to 4, At least one of R15, R!6 and R" is an alkoxy group having 1 to 4 carbon atoms, and R18 is an alkylene group having a carbon number of W2. 19. Any one of claims 14 to 17 of the patent application. The method for producing a surface-modified substrate, wherein the (meth)acrylic monomer is a (meth)acrylic monomer represented by the formula (Vb): (Vb) CC - C - R20 I II R19 式 where R19 represents a hydrogen atom or a methyl group, and R2 represents a hydrophilic group, a hydrophobic group, a cationic group or an anionic group. 20. Surface modification as described in claim 19 The method for producing a substrate, wherein the formula (Vb) is an alkyl group having a hydrogen atom, a hydroxyl group or a carbon atom of 2 to 20, which may have a carbon atom The alkyl group having 6 to 20 carbon atoms of a hydroxyl group or a fluorine atom and having a hydrogen atom or a carbon number at one terminal may have an oxiranyl group having a hydroxyl group or a fluorine atom, and having a hydrogen atom or a carbon number at one end. The alkyl group of 1 to 4 may have an epoxy group having a hydroxyl group or a fluorine atom, and a polyethylene oxide group having a molar number of 2 to 20, a hydrogen atom at one end or a carbon number of 1 to 4. The alkyl group may also have a hydroxyl group or a fluorine atom. The propylene group has a hydrogen atom or a hydrogen atom or a ketone group at the end of the ring. a polyepoxypropane group of ~20, a group represented by the formula (III) or a group represented by the formula (IV): Ra ~R7-N-R8-C Ο ο- T?9 (III) Ι10. R and R8 each independently represent an alkylene group having a carbon number of 1 to 4 independently, a hydrogen atom or an alkyl group having a carbon number of 4 to 4; R12 (IV) — RU-N-R14 · X· R13 The alkylene group having no carbon number of 1 to 4, and the R12 and R13 groups are each independently represented by an alkyl group or an alkyl group having an atomic group or a sulfonium group. 21 — A surface-modified substrate which is modified from the surface of the 2-liquid surface modifier described in any one of claims 7 to 13. 2 2 A surface hydrophilizing agent' characterized by comprising: (meth)acrylic acid group 1 ^. And a monomer composition containing a ruthenium atom of the formula (IX) and a monomer component of the formula &gt;&gt; not containing a nitrogen atom: R1 I R3 H2C = CCY-R6-Si-R4 A (IX) Rs where 1 &quot; R1 represents a hydrogen atom or a fluorenyl group, and R3 'R4 and R5 each independently represent an alkyl group or an alkoxy group having a carbon number of 1 to 4, R3, R4 and At least one of r5 101 £ 201211072 is a carbon-based sub-alkyl group, Y-terminus represents oxygen: sub- 4: alkoxy groups, R6 represents a carbon number BK atom or -NH; R1 I R9 | H2C-Cc-Y_Re * + I 1 尺—N-R8~c〇〇-〇i, 〇00 where R1, R6 and γ盥, + 〃 are the same as 'R8 alkyl, R9 and R1. The surface hydrophilizing agent is a non-hydrogen atom or an alkyl group having a carbon number of 1 to 4, which is represented by the formula (IX). The weight of a monomer containing a right-handed jst ^ D 3 ruthenium atom and a monomer containing a shoulder nitrogen atom represented by the formula (X) (a monomer having a ω atom having a right ω 3 / a writing body containing a nitrogen atom) is 3/97~95/5. , Μ々π concave tax is not 4 匕 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共body. The surface hydrophilizing agent according to claim 24, wherein the monomer which can be copolymerized with the monomer having a cut atom and the monomer having a nitrogen atom represented by the formula (1) represented by the formula (1) It is at least one selected from the group consisting of a stupid vinyl monomer, a carboxylic acid ester monomer, and an amine monomer. The surface hydrophilizing agent according to claim 24 or 25, wherein the monomer having a ruthenium atom represented by the formula (IX) and a monomer having a nitrogen atom represented by the formula (χ) are copolymerized. The amount of the monomer is 0 to 100 parts by weight based on 100 parts by weight of the total amount of the monomer containing a halogen atom represented by the formula (?) and the monomer containing a nitrogen atom represented by the formula (X). A surface hydrophilizing substrate comprising a surface hydrophilizing agent comprising the surface hydrophilizing agent according to any one of the preceding claims, wherein the surface hydrophilizing agent according to any one of the above-mentioned claims. 103