TW201348269A - Fluorine-containing copolymer, and oil- and/or water-repellent coating agent - Google Patents

Abstract

The present invention is based on the purposes of providing a fluorine-containing copolymer containing both excellent oil-repellency and having high solubility towards universal solvents (organic solvents not containing fluorine), and a coating agent having the oil repellency and/or water repellency. The present invention provides a fluorine-containing copolymer represented by the formula (1), wherein R<a1> represents a group containing a perfluoropolyether group, X<a> represents -O-, phenylene, -N(-R<E>)- (-R<E> represents an organic group), or carbazolyl group; R<a2> represents a hydrogen atom or an alkyl group; R<a3> represents a hydrogen atom or an alkyl group; each Q, when present, independently represents a constitution unit containing a hardening part or not containing a hardening part; R<c> represents a group containing a perfluoropolyether group, or an organic group capable of containing a hardening part; X<c> represents -O-, -S-, -NH-, or -N(-CH3-)-; k represents 1 or 2; nl represents repeated numbers above 1; but at least one of R<a2> and R<a3> is an alkyl group; when the group represented by R<c> is an organic group not containing a hardening part, at least a Q is the constitution unit containing a hardening part.

Description

Fluorinated copolymer, and oil-repellent and/or water-repellent coating agent

The present invention relates to a fluorine-containing copolymer, particularly a fluorine-containing copolymer containing a curable portion, and an oil-repellent and/or water-repellent coating agent containing the same.

In the past, such as a touchpad or the like, a machine that is used to touch a finger on the surface of a display device. The surface of the display device is generally made of a material such as glass or an amorphous synthetic resin (for example, an acrylic resin). However, since such a material does not have oil repellency, there is a problem that grease on the surface of the display device adheres to the surface of the display device, which causes a decrease in display visibility.

Therefore, a fluorine-containing compound having excellent oil-repellency properties, particularly a fluorine-containing compound containing a perfluoropolyether group, is used as an oil-repellent coating agent for a display surface for the purpose of preventing adhesion of fats and oils (Patent Documents 1 to 3).

Since the fluorine-containing compound has low solubility in a general-purpose solvent (non-fluorine-containing organic solvent), it is necessary to dissolve it in an organic solvent containing a high fluorine content when applied to a display surface.

However, in recent years, due to the popularity of tablet PCs or Slate PCs, the area of the display surface that is touched by fingers has become larger, and the fluorine contained in the coating is necessary. The use of compounds and high-priced fluorine-containing solvents is also increasing.

Therefore, a fluorine-containing compound which is not fluorine-containing and inexpensive and has high solubility in a general-purpose solvent is required.

Moreover, the film to be formed on the surface of various kinds of substrates to be easily peeled off is, for example, a method of obtaining a surface film by polymerizing an acrylic monomer of a known acrylic hard coating agent. This method has versatility as a surface modification method. In other words, it is compatible with an acrylic hard coating agent, and only a fluorine-containing compound containing a copolymerizable perfluoropolyether group is prepared, and by combining the fluorine-containing compound and an acrylic hard coating agent, various types of fluorine-containing compounds can be obtained. The surface modifier of the substrate can also change the physical properties of the resulting polymer film. Further, since a known acrylic monomer is used as a main component of the film, the amount of the fluorine-containing compound containing a perfluoropolyether group which is expensive can be reduced, which is advantageous in terms of cost.

A fluorine-containing compound which is compatible with the acrylic hard coating agent and which contains a perfluoropolyether group which can be copolymerized by the curable portion is useful.

As the fluorine-containing compound containing a perfluoropolyether group and a curable portion, for example, the following ones are known.

Patent Document 4 discloses an ethyl ethyl group which is a protective coating and a perfluoropolyether having a hydroxyl group at the terminal. The methacrylate denatured product was added to bisphenol A-dihydroxyethyl acrylate, and copolymerized and immobilized (Patent Document 4, Examples 5 and 10).

Non-patent document 1 discloses ethyl isocyanate of a perfluoropolyether having a hydroxyl group at its terminal. a copolymer of a methacrylate denatured body and a methyl methacrylate.

Patent Document 5 discloses that the oil-repellent water-repellent film has a perfluorocarbon In the oligoamine of the polyether block, a method of introducing an addition polymerizable group having an active hydroxyl group for the purpose of modifying a crosslinking-forming functional group is introduced.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] JP-A-9-157582

[Patent Document 2] JP-A-9-157388

[Patent Document 3] International Publication No. 2003/002628

[Patent Document 4] Japanese Patent Laid-Open No. Hei 10-72568

[Patent Document 5] JP-A-2001-19736

[Non-patent literature]

[Non-Patent Document 1] Polymer, 42, 2001, pp. 2299-2305

As described above, the fluorine-containing compound having excellent oil-repellency in the past has low solubility in a general-purpose solvent (an organic solvent not containing fluorine), and on the other hand, it has a fluorine-containing compound having high solubility in a general-purpose solvent. The problem of low oiliness.

Further, in the technique proposed in Patent Document 4, the perfluoropolyether is added only to 1% by weight. Because of ethyl isocyanate. Since the methacrylic hydrocarbon group of the methacrylate-modified perfluoropolyether is smaller than the fluoroalkyl moiety, the fluorine-containing compound of Patent Document 4 is easily peeled off from the substrate, and is similar to the general-purpose non-fluorinated acrylate. The compatibility between the body and the hydrocarbon solvent is low. Therefore, the type of the monomer which can be dissolved is limited, and there is an optimum composition coating agent which cannot be added to each use, and when it is added at a high concentration, the solution before hardening is easily phase-separated, and it is not possible to obtain a uniform film or the like. Further, when the transparent protective layer used for optical use is used, the protective film must be thin, and in this case, it is necessary to add a relatively high concentration, otherwise it is difficult to visualize the surface modification effect.

The copolymer of Non-Patent Document 1 is an ethyl isocyanate of a perfluoropolyether. Since the methacrylate-denatured body cannot be dissolved in the hydrocarbon-based solvent, it is carried out in a specific chlorofluorocarbon of 1,1,2-trichlorotrifluoroethane or a chlorofluorocarbon solvent such as a high-valent trifluorotoluene. The polymerization is further reduced in the form of a copolymer in a non-fluorine-based medium, so that the degree of freedom of film physical properties is lacking. Therefore, the substrate of the coatable copolymer is limited. Moreover, since it is added only to the coating agent in the form of a copolymer, it is limited to a dissolvable coating agent, and it is difficult to obtain a strong and uniform film.

In the technique proposed in Patent Document 5, the main component of the surface protective film is an oligoaminoester (a urethane crosslinked product containing a perfluoropolyether), and has physical limitations such as discomfort in applications requiring hardness. This method is not added to a known addition polymerizable coating agent to impart a protective film.

Therefore, the present invention provides a mixture which has excellent oil repellency and/or water repellency, high solubility to a general-purpose solvent (non-fluorine-containing organic solvent), and can be added to a known hard coating agent. A fluorocopolymer, and an oil-repellent and/or water-repellent coating agent containing the same.

The inventors conducted detailed review and found that formula (1):

Wherein R ^a1 represents a monovalent or divalent group containing a perfluoropolyether group. K means 1, or 2.

X ^a represents -O-, phenyl, -N(-R ^E )- (R ^E represents an organic group), or carbazole group.

R ^a2 represents a hydrogen atom or an alkyl group.

R ^a3 represents a hydrogen atom or an alkyl group.

Each of the Qs independently represents a constituent unit containing the curable portion or a constituent unit not including the curable portion.

R ^c represents a group containing a perfluoropolyether group, or an organic group or a hydrogen atom which may contain a hardenable portion.

X ^c represents -O-, -S-, -NH-, or a single bond.

N1 represents a repetition number of 1 or more.

However, when at least one of R ^a2 and R ^a3 is an alkyl group and R ^{c does} not contain an organic group of a curable portion, at least one Q represents a constituent unit containing a curable portion. 〕

The fluorinated copolymer shown has excellent oil and water repellency, and is suitable for general use. The agent (non-fluorine-containing organic solvent) has high solubility, and the present invention has been completed.

That is, the present invention contains the following aspects.

Item 1.

Formula 1):

Wherein R ^a1 represents a monovalent or divalent group containing a perfluoropolyether group, X ^a represents -O-, phenylene, -N(-R ^E )- (R ^E represents an organic group) or A carbazolyl group, R ^a2 represents a hydrogen atom or an alkyl group, and R ^a3 represents a hydrogen atom or an alkyl group, and each Q, when present, independently represents a constituent unit containing a hardenable portion or a constituent unit not containing a hardenable portion, R ^c The group containing a perfluoropolyether group or an organic group or a hydrogen atom which may also contain a hardenable portion, X ^c represents -O-, -S-, -NH- or a single bond, and k represents 1 or 2.

N1 represents a repeating number of 1 or more. However, when at least one of R ^a2 and R ^a3 is an alkyl group, and R ^{c is} not an organic group containing a curable portion, at least one Q is a constituent unit containing a curable portion.

Fluorinated copolymer

Item 2.

Q is the formula:

Wherein each R ^b1 is independently represented by a hydrogen atom or an alkyl group, and each R ^b2 is independently represented by a hydrogen atom or an organic group which may also contain a hardening moiety, and R ^b3 represents a hydrogen atom or an alkane. a group, X ^b represents -O-, phenyl, -N(-R ^E )- (R ^E represents an organic group) or a carbazolyl group, but when R ^b2 is a hydrogen atom, X ^b is a phenyl group]

The fluorine-containing copolymer described in Item 1 of the constituent unit shown.

Item 3.

The number average molecular weight of the perfluoropolyether group in the monovalent or divalent group of the perfluoropolyether group represented by R ^a1 is a fluorinated copolymer of 1 or 2 each of about 1,000 or more.

Item 4.

The perfluoropolyether group in the perfluoropolyether group-containing group represented by R ^a1 has a partial formula represented by the following formula: -(C _p F _2p O) _n -

[wherein, each p is independently an integer of 1 to 6 when it appears.

n represents the number of repetitions. The fluorinated copolymer according to any one of items 1 to 3 above.

Item 5.

R ^a1 is a monovalent group represented by the following formula: X ^ra -(C _p F _2p O) _na -Y ^ra -L ^a - (a1)

[wherein, X ^ra represents fluorine or Rf-O- (Rf represents a perfluoroalkyl group having 1 to 8 carbon atoms), and each p is independently represented by an integer of 1 to 6, and na represents a repeat of 1 to 1000. The number, Y ^ra represents a perfluoroalkylene chain having 1 to 6 carbon atoms, and L ^a represents a fluorine-containing copolymer described in Item 4 of the linking group].

Item 6.

The formula of formula (a1): (C _p F _2p O) _na is represented by a moiety selected from -CF ₂ -CF ₂ -CF ₂ -O-, -CF(-CF ₃ )-CF ₂ -O- , -CF ₂ -O - fluorinated copolymer composed of 5 items CF ₂ -CF ₂ -O- and -CF (-CF ₃₎ -O- or more kinds of the constituting units of the groups described -, .

Item 7.

Formula: (C _p F _2p O) _na is a group of fluorine-containing copolymers represented by -CF ₂ -CF ₂ -CF ₂ -O-, and Y ^ra is -CF ₂ -CF ₂ - Things.

Item 8.

The formula: (C _p F _2p O) _{na is} represented by -CF ₂ -CF ₂ -O-, and -CF ₂ -O-, and Y ^ra is -CF ₂ - Fluorine copolymer.

Item 9.

The formula: (C _p F _2p O) _{na is} represented by -CF(-CF ₃ )-CF ₂ -O-, and Y ^ra is -CF(-CF ₃ )- Fluorine copolymer.

Item 10.

The formula: (C _p F _2p O) _{na is} represented by -CF(-CF ₃ )-CF ₂ -O-, and -CF ₂ -O-, and Y ^ra is -CF(-CF ₃ ) - the fluorine-containing copolymer according to item 6.

Item 11.

The fluorinated copolymer according to any one of items 5 to 10 of the above-mentioned item, wherein L ^a is -CH ₂ -O-CH ₂ -CH ₂ -.

Item 12.

The fluorinated copolymer according to any one of items 5 to 10, wherein L ^a is -CH ₂ -.

Item 13.

R ^a1 is a divalent group represented by the following formula; formula: -L ^a' -Y ^ra' -O-(C _p F _2p O) _na -Y ^ra -L ^a - (a2)

Wherein, L ^{a '} and L ^a each independently represent a linking group, and Y ^{ra '} and Y ^ra each independently represent a perfluoroalkylene chain having a carbon number of 1 to 6, and each p is independently represented by 1 to 1; The fluorinated copolymer described in item 4 of the integer of 6 and na represents the repeat number of 1 to 1000.

Item 14.

The formula of formula (a2): (C _p F _2p O) _na is represented by a group independently selected from -CF ₂ -CF ₂ -CF ₂ -O-, -CF(-CF ₃ )-CF ₂ containing CF ₂ -CF ₂ -O- and -CF (-CF ₃₎ -O- item composed of one or more types of constituting units of the groups described in 13 _{- -O -, - CF 2 -O} -, Fluorine copolymer.

Item 15.

Y ^ra' is -CF ₂ -CF ₂ -, and the formula: (C _p F _2p O) _na is represented by -CF ₂ -CF ₂ -CF ₂ -O-, and Y ^ra is -CF ₂ -CF ₂ - The fluorine-containing copolymer described in Item 13.

Item 16.

Y ^ra' is -CF ₂ -, and the formula: (C _p F _2p O) _na is represented by -CF ₂ -CF ₂ -O-, and -CF ₂ -O-, and Y ^ra is - The fluorine-containing copolymer described in Item 13 of CF ₂ -.

Item 17.

Y ^ra' is -CF(-CF ₃ )-, and the formula: (C _p F _2p O) _na is represented by -CF(-CF ₃ )-CF ₂ -O-, and Y ^ra is - The fluorine-containing copolymer described in Item 13 of CF(-CF ₃ )-.

Item 18.

Y ^ra' is -CF(-CF ₃ )-, and the formula: (C _p F _2p O) _na is represented by -CF(-CF ₃ )-CF ₂ -O-, and -CF ₂ -O- the configuration and Y ^ra is -CF (-CF ₃₎ - described in item 13, fluorinated copolymer.

Item 19.

The perfluoropolyether group in the perfluoropolyether group-containing group represented by R ^a1 is a divalent group represented by the following formula; and: -L ^a' -Y ^ra' -(OC _p' F _2p' ) _na' -O-Rf-O-(C _p F _2p O) _na -Y ^ra -L ^a - (a2')

In the formula, L ^{a '} and L ^a each independently represent a linking group, and Y ^{ra '} and Y ^ra each independently represent a perfluoroalkylene chain having a carbon number of 1 to 6, and the na' and na are independent of each other. The fluorinated copolymer described in item 4 of the repeating number of 1,000, Rf represents a perfluoroalkylene chain.

Item 20.

Y ^ra' is -CF(-CF ₃ )-, and the formula: (OC _p' F _2p' ) _na' is represented by -O-CF ₂ -CF(-CF ₃ )-, Rf is carbon a 1 to 8 perfluoroalkylene chain having the formula: (C _p F _2p O) _na is represented by -CF(-CF ₃ )-CF ₂ -O-, and Y ^ra is -CF(-CF ₃ ) The fluorinated copolymer according to item 19.

Item 21.

The fluorinated copolymer according to any one of items 13 to 20, wherein L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ -, and L ^a is -CH ₂ -O-CH ₂ -CH ₂ -.

Item 22.

The fluorinated copolymer according to any one of items 13 to 20, wherein L ^{a '} is -CH ₂ -, and L ^a is -CH ₂ -.

Item 23.

R ^{c is} not an organic group containing a curable portion, and one less Q is a fluorine-containing copolymer described in any one of items 1 to 22 which is a constituent unit of the curable portion.

Item 24.

The sclerosing moiety in Q is a fluorinated copolymer described in Item 23 of a (meth) acrylonitrile group or a decane coupling group.

Item 25.

The constituent unit containing the curable portion is a group in which the curable portion is bonded to X ^b via a linking group, and the linking group is -(CHR ^y ) _n -O- or -(CHR ^y ) _n -O-( CHR ^y ) _n -O- (each n is independently represented by a repeat number of integers from 1 to 40, and each R ^y is independently represented by hydrogen or a methyl group when present) Copolymer.

Item 26.

R ^c is a fluorinated copolymer as described in any one of items 23 to 25 of the methyl group.

Item 27.

R ^c is a fluorinated copolymer according to any one of items 1 to 25 which contains an organic group of a curable portion.

Item 28.

R ^c is a fluorinated copolymer according to Item 27 which contains a decane coupling group.

Item 29.

An oil-repellent and/or water-repellent coating agent containing the fluorinated copolymer according to any one of items 1 to 28.

Item 30.

Further containing a compound represented by the following formula; formula (2): R ^r1 -O-(C _r F _2r O) _nd -R ^r2

In the formula, each r is independently an integer from 1 to 6, and nd represents a repeat number, and R ^r1 and R ^r2 each independently represent a carbon number of 1 to 16, preferably a carbon number of 1 to 3 perfluoroalkane. The oil-repellent and/or water-repellent coating agent described in Item 29.

Item 31.

An article comprising the film formed of the oil-repellent and/or water-repellent coating agent described in Item 29 or 30.

Item 32.

formula:

Wherein PFPE represents F-(CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeating number), and Y ^a represents ^a compound represented by ^a decyloxy group or a halogen atom] A manufacturing method characterized by comprising a 2-poly(perfluoropropyloxy group) represented by the formula: PFPE-CH ₂ -OC ₂ H ₄ O-CH=CH ₂ (wherein the symbol is represented by the same meaning as defined above) A method for producing a step of reacting ^a methoxyethoxyvinyl ether with a compound represented by the formula: Y ^a -H (the symbol in the formula represents the same meaning as defined above).

Item 33

formula:

Wherein PFPE represents F-(CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeating number), and Y ^a represents ^a compound represented by ^a decyloxy group or a halogen atom] A manufacturing method characterized by comprising 2-poly(perfluoropropyloxy)methoxyethylene represented by the formula: PFPE-CH ₂ -O-CH=CH ₂ (the symbol in the formula is the same as defined above) A method for producing an ether and ^a step of reacting a compound represented by the formula: Y ^a -H (the symbol in the formula represents the same meaning as described above).

Item 34.

formula:

Wherein PFPE represents -CF(-CF ₃ )-(O-CF ₂ -CF(-CF ₃ )) _n -O-CF ₂ -Rf-CF ₂ -O-(CF(-CF ₃ )-CF ₂ -O-) _n' -CF(CF ₃ )-(Rf represents a perfluoroalkylene group, n and n' are each a repeating number), and Y ^a represents a decyloxy group or a halogen atom. 〕

A method for producing a compound represented by the formula: CH ₂ =CH-OC ₂ H ₄ -O-CH ₂ -PFPE-CH ₂ -OC ₂ H ₄ -O-CH =CH ₂ (wherein The symbol indicates a compound represented by the same meaning as defined above, and the formula: Y ^a -H (the symbol in the formula indicates the same meaning as described above)

A method of producing the step of reacting the indicated compound.

Item 35.

formula:

Wherein PFPE represents -CF ₂ CF ₂ -O-(CF ₂ -CF ₂ CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeating number), and Y ^a represents a decyloxy group or a halogen atom]

A method for producing a compound represented by the formula: CH ₂ =CH-OC ₂ H ₄ -O-CH ₂ -PFPE-CH ₂ -OC ₂ H ₄ -O-CH=CH ₂ (wherein The symbol is ^a method for producing a compound represented by the above-mentioned meaning and a step of reacting with ^a compound represented by the formula: Y ^a -H (wherein the symbol represents the same meaning as defined above).

Item 36

formula:

Wherein PFPE represents -CF ₂ CF ₂ -O-(CF ₂ -CF ₂ CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeating number), and Y ^a represents a decyloxy group or a halogen atom. 〕

The method for producing the compound represented by the method is characterized by comprising: CH ₂ =CH-O-CH ₂ -PFPE-CH ₂ -O-CH=CH ₂ (wherein the symbol is represented by the same meaning as defined above) A method for producing a compound and a step of reacting a compound represented by the formula: Y ^a -H (the symbol in the formula represents the same meaning as defined above).

Item 37.

The compound represented by the formula: Y ^a -H is a production method as described in any one of items 32 to 36 of CF ₃ COOH.

The fluorinated copolymer of the present invention has excellent oil repellency and/or water repellency, and high solubility to a general-purpose solvent (non-fluorine-containing organic solvent), and is suitable for use as an oil-repellent and/or water-repellent coating agent.

[Fig. 1] A chart of MALDI-TOF-MS.

1.

In the present specification, unless otherwise stated, the numerical value range "~" indicates that the numerical range also includes the numerical values at both ends.

In the present specification, the term "perfluoropolyether group" means a monovalent or divalent "perfluoropolyether group" unless otherwise specified. The "monovalent perfluoropolyether group" means that an etheric oxygen atom is inserted into one or more carbon-carbon bonds. Perfluoroalkyl. The "divalent perfluoropolyether group" means a perfluoroalkylene chain in which an etheric oxygen atom is inserted into one or more carbon-carbon bonds. In the present specification, the perfluoropolyether group is sometimes referred to simply as PFPE.

In the present specification, the "perfluoroalkyl group" is, for example, a perfluoroalkyl group having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 1 to 3 carbon atoms).

The "perfluoroalkyl group" may be linear or branched, and is preferably linear.

Further, the "perfluoroalkyl group" may be a group in which all hydrogen atoms of the alkyl group are substituted by a fluorine atom, or a group in which all hydrogen atoms other than one hydrogen atom at the alkyl group are replaced by a fluorine atom, but When specifically stated, it is preferred that all of the hydrogen atoms of the alkyl group are substituted by a fluorine atom.

In the present specification, the "perfluoroalkylene chain" means that the hydrogen atom is removed from a group in which all hydrogen atoms other than one hydrogen atom at the alkyl group are replaced by a fluorine atom in the above-mentioned "perfluoroalkyl group". Derived 2-valent base. Unless otherwise specified, the "perfluoroalkylene chain" may, for example, be a perfluoroalkylene chain having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 1 to 3 carbon atoms).

The "perfluoroalkylene chain" may be linear or branched, and is preferably linear.

In the present specification, the alkyl group is, for example, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1). Base, ethyl, propyl, isopropyl). The "alkyl group" may be linear or branched, but is preferably linear.

In this specification, unless otherwise specified, The base may, for example, be an alkyl fluorenyl group having 2 to 13 carbon atoms (preferably 2 to 7, preferably 2 to 4, more preferably 2).

The "alkyl group" is a general formula: RCO-(R represents an alkyl group).

The "alkyl fluorenyl group" may be linear or branched, but is preferably linear.

In the present specification, unless otherwise specified, the "decane coupling group" may, for example, be of the formula (a): Si(-R ^s ) _m (-OR ^s ) _3-m -

Wherein R ^s represents an alkyl group. And m represents an integer from 0 to 2. 〕

Alkoxyalkylene (anthracene ether group) shown; (b) formula: Si(-R ^s ) _m (-OCOR ^s ) _3-m -

Wherein R ^s represents an alkyl group. And m represents an integer from 0 to 2. 〕

The alkylcarboxyalkylalkyl group shown; (c) formula: Si(-R ^s ) _m (-X) _3-m -

Wherein X represents a halogen atom.

R ^s represents an alkyl group. And m represents an integer from 0 to 2. 〕

The alkyl halide alkyl group is shown; and the formula (d): Si(-R ^s ) _m (-R ^N ) _3-m -

Wherein R ^N represents -NR ^s ₂ or -NHR ^s .

R ^s represents an alkyl group. And m represents an integer from 0 to 2. 〕

The indole nitrogen group is shown. In the present specification, the decane coupling group is sometimes only represented by Z-.

In the present specification, "organic group" means a group containing carbon.

In the present specification, the "perfluoropolyether group-containing group" is removed from the "organic group capable of containing a curable portion".

2. Fluorinated copolymer

The fluorinated copolymer of the present invention is of the formula (1):

The compound shown.

The symbols in the formula (1) are explained below.

R ^a1 represents a monovalent or divalent group containing a perfluoropolyether group. k is 1, or 2.

In the "perfluoropolyether group-containing group" represented by R ^a1 , a monovalent "perfluoropolyether group" preferably has a monovalent group bonded to one linking group or a divalent "perfluoropolyether group". Each of them has a divalent group in which one linking group is bonded.

The lower limit of the number average molecular weight of the "perfluoropolyether group" is preferably about 1,000, more preferably about 1,500, still more preferably about 2,000, from the viewpoint of obtaining high oil repellency and water repellency.

The upper limit of the number average molecular weight of the "perfluoropolyether group" is preferably about 100,000, preferably about 50,000, from the viewpoint of obtaining high solubility in a general-purpose solvent (non-fluorine-containing organic solvent). More preferably, it is about 10,000.

The "perfluoropolyether group" preferably has the formula: -(C _p F _2p O) _na -

[wherein, each p is independently an integer of 1 to 6 when it appears.

Na indicates the number of repetitions]

The part shown.

The formula: C _p F _2p O is shown to be independent in the repetition of the na times, in other words, the same or different.

The number of repetitions indicated by na is 1 to 1000. Further, the number of repetitions indicated by na is the average of the numbers in the fluorinated copolymer.

The preferred one of the "monovalent group containing a perfluoropolyether group" represented by R ^{a1 is a group} represented by the following formula (a1).

Formula: X ^ra -(C _p F _2p O) _na -Y ^ra -L ^a - (a1)

Wherein X ^ra represents fluorine or Rf-O- (Rf represents a perfluoroalkyl group having 1 to 8 carbon atoms).

Each p is an integer representing 1 to 6 when it appears.

Na represents the number of repetitions from 1 to 1000.

Y ^ra represents a perfluoroalkylene chain having a carbon number of 1 to 6.

L ^a represents a linking group]

The symbols in the above formula (a1) will be described below.

X ^{ra is} preferably fluorine or CF ₃ -O-.

It is preferable that each p is an integer representing 2 to 3 independently when it appears.

The moiety represented by the formula: (C _p F _2p O) _na is preferably selected from the group consisting of -CF ₂ -CF ₂ -CF ₂ -O-, -CF(-CF ₃ )-CF ₂ -O-, -CF ₂ - One or more constituent units of O-, -CF ₂ -CF ₂ -O-, and -CF(-CF ₃ )-O- are grouped.

Na is preferably from 1 to 500, more preferably from 5 to 150.

Y ^{ra is} preferably of the formula: -(CF ₂ ) _fa -CF(-Z ^a )-(CF ₂ ) _ga -

[wherein, fa and ga each independently represent the number of repetitions of an integer of 0 or more. Further, the total of fa and ga is an integer of 0 to 5.

Z ^a represents fluorine or -CF ₃ . Yl] illustrated, preferably _{-CF 2 -, - CF 2 -CF} 2 -, or -CF (-CF ₃₎ -.

Formula: -(C _p F _2p O) _na - Preferably, the formula (1): (C _p F _2p O) _{na is} represented by -CF ₂ -CF ₂ -CF ₂ -O- And na is from 1 to 1000, preferably from 5 to 100; (2) Formula: (C _p F _2p O) _na is -CF ₂ -O-, and -CF ₂ -CF ₂ -O-, and na is from 2 to 1000, preferably from 5 to 150; (3): (C _p F _2p O) _na is -CF(-CF ₃ )-CF ₂ -O-, and na is from 1 to 1000, preferably from 5 to 100; or (4): (C _p F _2p O) _na is -CF(-CF ₃ )-CF ₂ -O- and -CF ₂ -O-, and na is 2 to 1000, preferably 5 to 150.

The moiety: X ^ra -(C _p F _2p O) _na -Y ^ra - is preferably (1) X ^ra is fluorine or Rf-O- (Rf is a perfluoroalkyl group having 1 to 8 carbon atoms) Preferably, it is fluorine, and the formula: (C _p F _2p O) _na is formed by -CF ₂ -CF ₂ -CF ₂ -O-, and na is from 1 to 1000, preferably from 5 to 100. And Y ^ra is -CF ₂ -CF ₂ -; (2) X ^ra is fluorine, or Rf-O- (Rf is a perfluoroalkyl group having 1 to 8 carbon atoms), preferably CF ₃ -O-, The formula: (C _p F _2p O) _na is formed by -CF ₂ -O-, and -CF ₂ -CF ₂ -O-, and na is from 2 to 1000, preferably from 5 to 150, And Y ^ra is -CF ₂ -; (3) X ^ra is fluorine, or Rf-O- (Rf is a perfluoroalkyl group having 1 to 8 carbon atoms), preferably CF ₃ -O-, formula: (C _The portion indicated by _p F _2p O) _na is -CF(-CF ₃ )-CF ₂ -O-, na is from 1 to 1000, preferably from 5 to 100, and Y ^ra is -CF(- CF ₃ )-; or (4) X ^ra is fluorine, or Rf-O- (Rf is a perfluoroalkyl group having 1 to 8 carbon atoms), preferably CF ₃ -O-, and: (C _p F _2p The part indicated by O) _na is -CF(-CF ₃ )-CF ₂ -O-, and -CF ₂ -O-, and na is 2 to 1000, preferably a repeating number of 5 to 150, and Y ^ra For -CF ₂ -.

L ^{a is} preferably a single bond or a linking group having 1 to 6 (preferably 1 to 5, 2 to 5, 1 to 4, or 2 to 4) atoms in the main chain.

Examples of such a linking group include a single bond, -CH ₂ -, -CH ₂ -O-, -CH ₂ -O-CH ₂ -, -O-CH ₂ -CH ₂ -, -C(=O). -O-, -C(=O)-NH-, -CH ₂ -OC(=O)-, and -CH ₂ -(O-CH ₂ -CH ₂ ) _nk1 - (nk1 is 1 to 10.).

Of these, -CH ₂ -O-CH ₂ -CH ₂ -, or -CH ₂ - is preferred. Preferably, the left end atom of the description of these partial structures is bonded to the perfluoropolyether group.

^Particularly preferred as the "monovalent group containing a perfluoropolyether group" represented by R ^a1 is (1) in the formula (a1), X ^ra is fluorine, and the moiety represented by the formula: (C _p F _2p O) _na is - CF ₂ -CF ₂ -CF ₂ -O- formed by, na is 1 to 1000, preferably from 5 to 100 repeating number of, Y ^ra is -CF ₂ -CF ₂ -, and L ^a is -CH ₂ -O -CH ₂ -CH ₂ - group; (2) In the formula (a1), X ^ra is CF ₃ -O-, and the formula: (C _p F _2p O) _na is -CF ₂ -O-, and -CF ₂ -CF ₂ -O- formed by, na is 1 to 1000, preferably from 5 to 150 repeating number of, Y ^ra is -CF ₂ -, and L ^a is -CH ₂ -O-CH ₂ -CH ₂ - of the group; (3) in (a1), X ^ra is CF ₃ -O-, the _{formula: (C p F 2p O)} na is shown in part -CF (-CF ₃₎ -CF ₂ -O- Thus, na is from 1 to 1000, preferably from 5 to 100, Y ^ra is -CF(-CF ₃ )-, and La is ^{a group} of -CH ₂ -O-CH ₂ -CH ₂ -; (4) In the formula (a1), X ^ra is CF ₃ -O-, and the formula: (C _p F _2p O) _na is -CF(-CF ₃ )-CF ₂ -O- and -CF ₂ - O-formed, na is from 1 to 1000, preferably from 5 to 150, Y ^ra is -CF ₂ -, and La is ^{a group} of -CH ₂ -O-CH ₂ -CH ₂ -; In the formula (a1), X ^ra is fluorine, and the formula: (C _p F _2p O) _{na is} represented by -CF ₂ -CF ₂ -CF ₂ -O-, and na is 1 to 1000. Preferably, the number is a repeat of 5 to 100, Y ^ra is -CF ₂ -CF ₂ -, and L ^a is ^{a group} of -CH ₂ -; (6) in the formula (a1), X ^ra is CF ₃ -O-, :(C _p F _2p O) _{na is a} group of -CF ₂ -O- and -CF ₂ -CF ₂ -O-, and na is 1 to 1000, preferably a repeating number of 5 to 150, Y ^Ra is -CF ₂ -, and L ^a is ^{a group} of -CH ₂ -; (7) In the formula (a1), X ^ra is CF ₃ -O-, and the formula: (C _p F _2p O) _na is -CF (-CF ₃₎ -CF ₂ -O- formed by, na is 1 to 1000, preferably from 5 to 100 repeating number of, Y ^ra is -CF (-CF ₃₎ -, and L ^a is -CH ₂ - of the group; or (8) formula (a1) of, X ^ra is CF ₃ -O-, the _{formula: (C p F 2p O)} na is shown in part -CF (-CF ₃₎ -CF ₂ -O - and -CF ₂ -O-, na is from 1 to 1000, preferably from 5 to 150, Y ^ra is -CF ₂ -, and L ^a is -CH ₂ -.

The "divalent group containing a perfluoropolyether group" represented by R ^a1 is preferably a group represented by the following formula (a2) or a group represented by the formula (a2').

Formula: -L ^a' -Y ^ra' -O-(C _p F _2p O) _na -Y ^ra -L ^a - (a2)

[wherein, L ^{a '} and L ^a each independently represent a linking group.

Y ^ra' and Y ^ra each independently represent a perfluoroalkylene chain having 1 to 6 carbon atoms.

Each p is an integer representing 1 to 6 when it appears.

Na represents the number of repetitions from 1 to 1000. 〕

Base shown

The symbols in the above formula (a2) will be described below.

L ^{a '} and L ^a each independently represent a single bond or a linking group having 1 to 6 (preferably 1 to 5, 2 to 5, 1 to 4, or 2 to 4) atoms in the main chain. Examples of the linking group represented by L ^a' include a single bond, -CH ₂ -, -CH ₂ -CH ₂ -O-, -OC(=O)-, -NH-C(=O)-, -C(=O)-O-CH ₂ -, and -(O-CH ₂ -CH ₂ ) _nk1 -CH ₂ - (nk1 is 1 to 10). Of these, -CH ₂ -CH ₂ -O-CH ₂ -, or -CH ₂ - is preferred. Preferably, the right-end atom described in these partial structures is bonded to the perfluoropolyether group.

Examples of the linking group represented by L ^a include a single bond, -CH ₂ -, -O-CH ₂ -CH ₂ -, -C(=O)-O-, -C(=O)-NH-. -CH ₂ -OC(=O)-, and -CH ₂ -(O-CH ₂ -CH ₂ ) _nk1 - (nk1 is 1 to 10). Of these, -CH ₂ -O-CH ₂ -CH ₂ -, or -CH ₂ - is preferred. Preferably, the left end atom described in the structure of the moiety is bonded to the perfluoropolyether group.

Y ^ra' and Y ^ra are independent representations

Formula: -(CF ₂ ) _fa -CF(-Z ^a )-(CF ₂ ) _ga -

[wherein, fa and ga each independently represent the number of repetitions of an integer of 0 or more. And the total of fa and ga is an integer of 0-5.

Z represents fluorine or -CF ₃ . ] Better, preferably _{-CF 2 -, - CF 2 -CF} 2 -, or -CF (-CF ₃₎ -.

Formula: The portion indicated by C _p F _2p O is independent for the repetition of the na times, in other words, may be the same or different.

It is preferable that each p is an integer representing 2 to 4 when it appears.

The formulas represented by the formula: (C _p F _2p O) _na are independently selected from -CF ₂ -CF ₂ -CF ₂ -O-, -CF(-CF ₃ )-CF ₂ -O-, -CF ₂ -O It is preferable that one or more constituent units of -, -CF ₂ -CF ₂ -O-, and -CF(-CF ₃ )-O- are grouped.

The na is independently from 1 to 500, preferably from 5 to 150.

The formula: -(C _p F _2p O) _na - is preferably a formula (1): (C _p F _2p O) _{na is a} moiety represented by -CF ₂ -CF ₂ -CF ₂ -O- And na is from 1 to 1000, preferably from 5 to 100; (2): (C _p F _2p O) _na is -CF ₂ -O-, and -CF ₂ -CF ₂ - O-, and na is 2~1000, preferably 5~150 repeats; (3): (C _pa F _2pa O) _na is -CF(-CF ₃ )-CF ₂ - O-, and na is from 1 to 1000, preferably from 5 to 100; or (4): (C _p F _2p O) _na is -CF(-CF ₃ )-CF ₂ -O- and -CF ₂ -O-, and na is from 2 to 1000, preferably from 5 to 150.

Formula: -Y ^ra' -O-(C _p F _2p O) _na -Y ^ra - Preferably, (1) Y ^ra' is -CF ₂ -CF ₂ -, and: (C _p F _2p O) _{na is} represented by -CF ₂ -CF ₂ -CF ₂ -O-, na is from 1 to 1000, preferably from 5 to 100, and Y ^ra is -CF ₂ -CF ₂ -; (2) Y ^{ra '} is -CF ₂ -.

The formula: (C _p F _2p O) _na is formed by -CF ₂ -O-, and -CF ₂ -CF ₂ -O-, and na is from 2 to 1000, preferably from 5 to 100, And Y ^ra is -CF ₂ -; (3) Y ^{ra '} is -CF(-CF ₃ )-, and the formula: (C _p F _2p O) _na is -CF(-CF ₃ )-CF ₂ - O-formed, na is 1~1000, preferably a repeating number of 5~100, and Y ^ra is -CF(-CF ₃ )-; or (4)Y ^ra' is -CF ₂ -, formula: ( The portion indicated by C _p F _2p O) _na is -CF(-CF ₃ )-CF ₂ -O-, and -CF ₂ -O-, and na is from 2 to 1000, preferably from 5 to 100. And Y ^ra is -CF ₂ -.

Formula: -L ^a' -Y ^ra' -(OC _p' F _2p' ) _na' -O-Rf-O-(C _p F _2p O) _n -Y ^ra -L ^a - (a2')

[wherein, L ^{a '} and L ^a each independently represent a linking group.

Y ^ra' and Y ^ra each independently represent a perfluoroalkylene chain having 1 to 6 carbon atoms.

p', and each p, when present, independently represent an integer from 1 to 6.

Na, and na' represent the number of repetitions from 1 to 1000.

Rf represents a perfluoroalkylene chain]

The symbols in the above formula (a2') will be described below.

L ^{a '} and L ^a each independently represent a single bond or a linking group having 1 to 6 (preferably 1 to 5, 2 to 5, 1 to 4, or 2 to 4) atoms in the main chain.

Examples of the linking group represented by L ^a' include a single bond, -CH ₂ -, -CH ₂ -CH ₂ -O-, -OC(=O)-, -NH-C(=O)-. -C(=O)-O-CH ₂ -, and -(O-CH ₂ -CH ₂ ) _nk1 -CH ₂ - (nk1 is 1 to 10). Among them, -CH ₂ -CH ₂ -O-CH ₂ - or -CH ₂ - is preferred. Preferably, the right-end atom described in these partial structures is bonded to a perfluoropolyether group.

As shown in the linking group L ^a of, for example, include a single _{bond, -CH 2 -, - O-} CH 2 -CH 2 -, - C (= O) -O -, - C (= O) -NH -, -CH ₂ -OC(=O)-, and -CH ₂ -(O-CH ₂ -CH ₂ ) _nk1 - (nk1 is 1 to 10). Of these, -CH ₂ -CH ₂ -O-CH ₂ -, or -CH ₂ - is preferred. Preferably, the left end atom described in the partial structure is bonded to the perfluoropolyether group.

Y ^ra' and Y ^ra are independent representations

Formula: -(CF ₂ ) _fa -CF(-Z ^a )-(CF ₂ ) _ga -

[wherein, fa and ga each independently represent the number of repetitions of an integer of 0 or more. And the total of fa and ga is an integer of 0-5.

Z ^a represents fluorine, or -CF ₃ ]

Preferably, preferably _{-CF 2 -, - CF 2 -CF} 2 -, or -CF (-CF ₃₎ -.

The formula: OC _p' F _2p' is repeated for the repetition of na', in other words, it can be the same or different.

It is preferred that each p' is independently represented by an integer of 2 to 4 when it appears.

The formulas of (OC _p' F _2p' ) _na' are each independently selected from -O-CF ₂ -CF ₂ -CF ₂ -, -O-CF ₂ -CF(-CF ₃ )-, -O- It is preferable that one or more constituent units of CF ₂ -, -O-CF ₂ -CF ₂ -, and -O-CF(-CF ₃ )- are grouped.

The na's each independently represent 1 to 500, preferably 5 to 150.

Formula: The portion indicated by C _p F _2p O is independent for the repetition of the na times, in other words, may be the same or different.

It is preferable that each p is an integer representing 2 to 4 when it appears.

The formulas represented by the formula: (C _p F _2p O) _na are independently selected from -CF ₂ -CF ₂ -CF ₂ -O-, -CF(-CF ₃ )-CF ₂ -O-, -CF ₂ -O It is preferable that one or more constituent units of -, -CF ₂ -CF ₂ -O-, and -CF(-CF ₃ )-O- are grouped.

Each of na stands for 1 to 500, preferably 5 to 150.

Rf is preferably a perfluoroalkylene chain having 1 to 8 carbon atoms.

Formula: -Y ^ra' -(OC _p' F _2p' ) _na' -O-Rf-O-(C _p F _2p O) _na -Y ^ra - Preferably, Y ^ra' is -CF (in the indicated portion) -CF ₃ )-; Formula: (OC _p' F _2p' ) The portion shown by _na' is -O-CF ₂ -CF(-CF ₃ )-; Rf is a perfluoroalkylene having 1-8 carbon number Base chain; formula: (C _p F _2p O) _na is -CF(-CF ₃ )-CF ₂ -O-; and Y ^ra is -CF(-CF ₃ )-.

^Particularly preferred as the "divalent group containing a perfluoropolyether group" represented by R ^a1 is (1) in the formula (a2), and L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ -, or -CH ₂ -, Y ^ra' is -CF ₂ -CF ₂ -, and the formula: (C _p F _2p O) _{na is} represented by -CF ₂ -CF ₂ -CF ₂ -O-, and na is 1 to 1000. Preferably, it is a repeating number of 5 to 100, Y ^ra is -CF ₂ -CF ₂ -, and La is ^{a group} of -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -; (2) In (a2), L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ -, or -CH ₂ -, Y ^ra' is -CF ₂ -, and the formula: (C _p F _2p O) _na is -CF ₂ -O-, -CF ₂ -CF ₂ -O-, and formed by, na is 1 to 1000, preferably from 5 to 100 repeating number of, Y ^ra is -CF ₂ -, and L ^a is - a group of CH ₂ -O-CH ₂ -CH ₂ -, or -CH ₂ -; (3) In the formula (a2), L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ -, or -CH ₂ -, Y ^ra' is -CF(-CF ₃ )-, and the formula: (C _p F _2p O) _na is formed by -CF(-CF ₃ )-CF ₂ -O-, na is 1~1000 , preferably a repeating number of 5 to 100, Y ^ra is -CF(-CF ₃ )-, and L ^a is ^{a group} of -CH ₂ -O-CH ₂ -CH ₂ -, or -CH ₂ -; 4) In the formula (a2), L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ -, or -CH ₂ -, Y ^ra' is -CF ₂ -, and: (C _p F _2p O) _na The part shown is -CF(-CF ₃ )-CF ₂ -O -, and -CF ₂ -O-, na is from 1 to 1000, preferably from 5 to 100, Y ^ra is -CF ₂ -, and L ^a is -CH ₂ -O-CH ₂ -CH ₂ -, or -CH ₂ - group; or (5) in formula (a2'), L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ -, Y ^{ra '} is -CF(-CF ₃ ) -, Formula: (OC _p' F _2p' ) The portion shown by _na' is -O-CF ₂ -CF(-CF ₃ )-, and na' is a repeat number of 1 to 1000, preferably 5 to 100. , Rf is a perfluoroalkylene chain having a carbon number of 1 to 8, and the formula: (C _p F _2p O) _{na is} represented by -CF(-CF ₃ )-CF ₂ -O-, and na is 1~ 1000, preferably a repeating number of 5 to 100, Y ^ra is -CF(-CF ₃ )-, and L ^a is ^{a group} of -CH ₂ -O-CH ₂ -CH ₂ -, or -CH ₂ -.

X ^a is -O-, phenyl group, -N(-R ^E )- (R ^E represents an organic group), or a carbazole group.

In this specification, phenyl (sometimes abbreviated as -Ph-) is a subtype: As shown, preferably

The organic group represented by R ^E may, for example, be an alkyl group.

In this specification, the exocarbazolyl is of the subtype: As shown, preferably . Wherein the nitrogen atom in the structural formula is bonded to the carbon atom in the formula (1).

X ^a is preferably -O-, -Ph- or oxazolyl, preferably -O- or -Ph-, more preferably -O-.

R ^a2 represents a hydrogen atom or an alkyl group.

R ^a2 represents an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group.

R ^a3 represents a hydrogen atom or an alkyl group.

R ^a3 is preferably a hydrogen atom or a methyl group, preferably a hydrogen atom.

However, at least one of R ^a2 and R ^a3 is an alkyl group.

When each Q appears, each of the components including the curable portion (hereinafter sometimes referred to as a constituent unit Q ^b ) or a constituent unit not including the curable portion (hereinafter sometimes referred to as a constituent unit Q ^m ) is independently indicated.

N1 is a repeating number of constituent units represented by Q, and is an integer of 1 or more.

The n1 is preferably from 1 to 200, more preferably from 5 to 100, still more preferably from 5 to 35.

In the formula (1): The illustrated portion may be composed only of the constituent unit Q ^b , or may be composed only of the constituent unit Q ^m , or may be composed of the constituent unit Q ^b and the constituent unit Q ^m .

However, when R ^c described later does not contain an organic group of a curable portion, the above portion must contain one or more constituent units Q ^b . In other words, at least one Q at this time is a constituent unit Q ^b containing a curable portion.

The constituent unit Q ^b and the constituent unit Q ^m may each form a block or may be randomly combined.

Q is preferably of the formula: The constituent units shown.

Each R ^b1 , when present, independently represents a hydrogen atom or an alkyl group.

R ^{b1 is} preferably a hydrogen atom.

Each of R ^b2 may independently represent a hydrogen atom or may also represent an organic group containing a curable portion.

That is, R ^b2 independently represents a hydrogen atom, an organic group containing a curable portion, or an organic group having no curable portion.

Hereinafter, R ^b2 is an organic group containing a curable portion: The constituent units shown are sometimes simply referred to as constituent units B.

On the other hand, the following R ^b2 is a hydrogen atom or an organic group having no curable portion, and is: The constituent unit shown is sometimes simply referred to as a constituent unit M.

The "organic group containing a curable portion" represented by R ^{b2 is} preferably a group in which a sclerosing portion is bonded to a bond or directly bonded to X ^b .

Examples of the curable portion in the "organic group containing a curable portion" represented by R ^b2 include an allyl group, a cinnamic acid group, a sorbic acid group, a (meth)acryl fluorenyl group, and a decane coupling group. Among them, a (meth) acrylonitrile group or a decane coupling group is preferred, and a fluorenyl alkyl group and a methacryl fluorenyl group are particularly preferred.

The preferred hardenable portion differs depending on the material to be coated.

When the material is an amorphous synthetic resin (for example, an acrylic resin), the "hardening portion is preferably an allyl group, a cinnamic acid group, a sorbic acid group, or a CH ₂ =CR ^x -C (=O). —(R ^x represents hydrogen, methyl, chlorine, or fluorine) (for example, (meth)acrylylene), preferably (meth)acrylonitrile.

Further, when the material is glass, the "hardenable portion" is preferably a decane coupling group, and more preferably a decylalkyl group.

The above-mentioned "linking group" is preferably a linking group having a main chain atomic number of from 1 to 16 (preferably from 2 to 12, more preferably from 4 to 10).

For example, when the "hardening portion" is an allyl group, a cinnamic acid group, a sorbic acid group or a (meth)acryl fluorenyl group, the "linking group" is preferably (a)-(CH ₂ -CH ₂ -O). _n - (n represents an integer of 2 to 10), (b) - (CHR ^y ) _n -O-, or - (CHR ^y ) _n -O-(CHR ^y ) _n -O- (each n is present at the time of appearance Each independently represents a repeating number of integers from 1 to 40. R ^y each independently represents hydrogen, or methyl), (c)-(CH ₂ -CH ₂ -O) _n -CO-NH-CH ₂ -CH ₂ -O - (n represents an integer of 2 to 10), (d) -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -(e)-(CH ₂ ) _n - (n represents an integer of 1 to 6), or (f)-(CH ₂ ) _nk1 -O-CONH-(CH ₂ ) _nk2 - (nk1 represents an integer of 1 to 8, preferably 2 or 4. nk2 represents an integer of 1 to 6, preferably 3) Or (g)-O- (but, X ^b non-O-), preferably -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-, or -CH ₂ -CH ₂ -O- .

Further, for example, when the "curable portion" is a decane coupling group, the "linking group" is preferably -(CH ₂ ) _n - (n is an integer of 1 to 6), or -(CH ₂ ) _nk1 -O- CONH-(CH ₂ ) _nk2 - (nk1 represents an integer of 1 to 8. nk2 represents an integer of 1 to 6), more preferably -(CH ₂ ) ₂ -, or -(CH ₂ ) ₃ -.

The "organic group not containing a curable portion" represented by R ^b2 is a group in which a group R ^m described later is bonded to a group or directly bonded to X ^b .

The linking group is preferably (a)-(CH ₂ -CH ₂ -O) _n - (n represents an integer of 2 to 10), (b)-(CHR ^y ) _n -O-, or -(CHR ^y _n -O-(CHR ^y ) _n -O- (each n is independently represented by a repeating number of integers from 1 to 40. Each R ^y is independently represented by hydrogen, or methyl), c) -(CH ₂ -CH ₂ -O) _n -CO-NH-CH ₂ -CH ₂ -O- (n represents an integer from 2 to 10), (d)-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, (e)-(CH ₂ ) _n - (n represents an integer from 1 to 6), or (f)-(CH ₂ ) _nk1 -O-CONH-(CH ₂ ) _nk2 - (nk1 is An integer of 1 to 8, preferably 2 or 4. nk2 represents an integer of 1 to 6, preferably 3), or (g)-O- (however, X ^{b is} not -O-).

R ^{m is} preferably the following group.

(i) alkyl

Example: methyl, ethyl

(ii) a chain group containing an alkyl group substituted by fluorine

example:

(iii) a group containing one or more ring portions selected from the group consisting of a monocyclic carbocyclic ring, a bicyclic carbocyclic ring, a tricyclic carbocyclic ring, and a tetracyclic carbocyclic ring

example:

(iv) a group of a hydrocarbon group substituted with one or more (preferably 1 or 2) carboxyl groups

example:

(v) a group containing one or more (preferably one) of an amine group

(vi) hydrogen

(vii) base containing imidazolium salt

example:

R ^m is a hydrogen atom or may be fluorinated, and an alkyl group may be bonded via an ethyl group, and more preferably a hydrogen atom, a methoxyethyl group, an isobutyl group, or an R ^x -CF _{2 group.} -(CF ₂ ) _nk1 -(CH ₂ ) _nk2 -O-(CH ₂ ) ₂ - (R ^x is a fluorine atom or a hydrogen atom, nk1 is an integer from 0 to 6, and nk2 is an integer from 1 to 6), Preferably, 3-(perfluoroethyl)propoxyethyl (form: CF ₃ -(CF ₂ )-(CH ₂ ) ₃ -O-(CH ₂ ) ₂ -).

Each R ^b3 when present is independently represented by a hydrogen atom or an alkyl group.

R ^{b3 is} preferably a methyl group or a hydrogen atom, more preferably a hydrogen atom.

X ^b represents -O-, -Ph-, -N(-R ^E )-, or carbazole. Wherein R ^E represents an organic group.

However, when R ^b2 is a hydrogen atom, X ^b is -Ph-.

X ^b is preferably -O-, -Ph- or oxazolyl, preferably -O- or -Ph-, more preferably -O-.

Further, examples of Q ^b include the following constituent units.

(a):

[in the formula, n represents the number of repetitions of integers from 1 to 6.

R ^x represents hydrogen, or methyl]

Constituent unit having a (meth) acrylonitrile group

example:

(b):

[wherein, n represents the number of repetitions of an integer from 1 to 6.

R ^x represents hydrogen, or methyl]

The constituent unit having a (meth) acrylonitrile group

example:

(c) a constituent unit having a decane coupling group

example:

(wherein Z represents a decane coupling group)

As an example of Q ^m , the following constituent units are further mentioned.

(a) a constituent unit having an annular portion

example:

Preferred examples of Q ^b include the following constituent units.

(a1)

[wherein, n represents an integer of 1 to 6.

R ^b2 represents (meth)acrylylene]

(a2)

[wherein, each n is an integer representing 1 to 6 when it appears.

R ^b2 represents (meth)acrylylene]

(eg -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-COC(CH ₃ )=CH ₂ )

(b)

[wherein, n represents an integer of 1 to 6.

R ^b2 represents a decane coupling group]

Preferred examples of Q ^m include the following constituent units.

[wherein, n represents an integer of 1 to 6.

R ^b2 represents an alkyl group]

R ^c represents a group containing a perfluoropolyether group or an organic group or a hydrogen atom which may contain a hardenable portion.

For one aspect of the invention, R ^c is a monovalent group containing a monovalent perfluoropolyether group.

In this aspect, the fluorinated copolymer of the present invention contains perfluoropoly at both ends Ether-based, so excellent water repellency can be obtained.

The "monovalent group containing a monovalent perfluoropolyether group" represented by R ^c may be a group in which a "monovalent perfluoropolyether group" is bonded by one linking group.

The lower limit of the number average molecular weight of the "monovalent perfluoropolyether group" is preferably about 1,000, more preferably about 1,500, still more preferably about 2,000, from the viewpoint of obtaining high oil repellency and/or water repellency.

The upper limit of the number average molecular weight of the "monovalent perfluoropolyether group" is preferably about 100,000, more preferably about from the viewpoint of obtaining high solubility in a general-purpose solvent (an organic solvent not containing fluorine). 50,000, more preferably about 10,000.

The "monovalent group containing a monovalent perfluoropolyether group" is preferably a group represented by the following formula (c1).

Formula: R ^c' -(C _q F _2q O) _nc -Y ^c -L ^c - (c1)

Wherein R ^{c '} represents fluorine or Rf ^c -O- (Rf ^c represents a perfluoroalkyl group having 1 to 8 carbon atoms).

Each Q appears as an integer representing 1 to 6 when it appears.

Nc represents the number of repetitions from 1 to 1000.

Y ^c represents a perfluoroalkylene chain having 1 to 6 carbon atoms.

L ^c represents a group represented by a linking group].

The symbols in the above formula (c1) will be described below.

R ^{c ' is} preferably fluorine or CF ₃ -O-.

Formula: The portion indicated by C _q F _2q O is independent for the repetition of nc times, in other words, may be the same or different.

It is preferable that each Q is independently represented by an integer of 2 to 3 when it appears.

The moiety represented by the formula: (C _q F _2q O) _nc is preferably selected from the group consisting of -CF ₂ -CF ₂ -CF ₂ -O-, -CF(-CF ₃ )-CF ₂ -O-, -CF ₂ -O -, -CF ₂ -CF ₂ -O-, and -CF(-CF ₃ )-O- are formed by one or more constituent units.

The Nc is preferably from 1 to 500, more preferably from 5 to 150.

Y ^{c is} preferably of the formula: -(CF ₂ ) _fc -CF(-Z ^c )-(CF ₂ ) _gc -

[wherein, fc and gc each independently represent the number of repetitions of an integer of 0 or more. And the total of fc and gc is an integer of 0-5.

Z ^c represents fluoro, or -CF _3-yl] illustrated, preferably _{-CF 2 -, - CF 2 -CF} 2 -, or -CF (-CF ₃₎ -.

Formula: -(C _q F _2q O) _nc - Preferably, the formula (1): (C _q F _2q O) _{nc is a} moiety of -CF ₂ -CF ₂ -CF ₂ -O- And nc is from 1 to 1000, preferably from 5 to 100; (2): (C _q F _2q O) The portion indicated by _nc is -CF ₂ -O-, and -CF ₂ -CF ₂ -O-, and nc is from 2 to 1000, preferably from 5 to 150; (3): (C _q F _2q O) The portion indicated by _nc is -CF(-CF ₃ )-CF ₂ -O-, and nc is from 1 to 1000, preferably from 5 to 100; or (4): (C _q F _2q O) _nc is -CF(-CF ₃ )-CF ₂ -O- and -CF ₂ -O-, and nc is 2 to 1000, preferably 5 to 150.

The formula: R ^{c '} - (C _q F _2q O) _{nc -} Y ^c - is preferably (1) R ^{c '} is fluorine, and the formula: (C _q F _2q O) _nc is -CF ₂ -CF ₂ -CF ₂ -O-, nc is from 1 to 1000, preferably from 5 to 100, and Y ^c is -CF ₂ -CF ₂ -; (2) R ^c is CF ₃ - O-, formula: (C _q F _2q O) The portion indicated by _nc is -CF ₂ -O-, and -CF ₂ -CF ₂ -O-, nc is 2 to 1000, preferably 5 to 150. The number of repetitions, and Y ^c is -CF ₂ -; (3) R ^{c '} is CF ₃ -O-, and the moiety: (C _q F _2q O) _nc is -CF(-CF ₃ )-CF ₂ - O-, nc is from 1 to 1000, preferably from 5 to 100, and Y ^c is -CF(-CF ₃ )-; or (4) R ^c' is CF ₃ -O-, formula: (C _q F _2q O) The portion indicated by _nc is -CF(-CF ₃ )-CF ₂ -O-, and -CF ₂ -O-, and nc is 2 to 1000, preferably 5 to 150. Number, and Y ^c is -CF ₂ -.

L ^{c is} preferably a linking group having 1 to 6 (preferably 1 to 5, more preferably 1) atoms in the main chain.

The linking group is preferably -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -, preferably -CH ₂ -.

The most preferable one of the "monovalent group containing a perfluoropolyether group" represented by R ^{c is} in the formula (c1), (1) R ^{c '} is fluorine, and the formula: (C _q F _2q O) _nc It is formed by -CF ₂ -CF ₂ -CF ₂ -O-, nc is from 1 to 1000, preferably from 5 to 100, Y ^c is -CF ₂ -CF ₂ -, and L ^c is -CH ₂ -O-CH ₂ -CH ₂ - group; (2) R ^{c '} is CF ₃ -O-, and the formula: (C _q F _2q O) _nc is -CF ₂ -O-, and -CF ₂ -CF ₂ -O-, nc is from 1 to 1000, preferably from 5 to 150, Y ^c is -CF ₂ -, and L ^c is -CH ₂ -O-CH ₂ -CH ₂ - (3) R ^{c '} is CF ₃ -O-, and the formula: (C _q F _2q O) _{nc is} represented by -CF(-CF ₃ )-CF ₂ -O-, nc is 1~1000 Preferably, the repeat number is from 5 to 100, Y ^c is -CF(-CF ₃ )-, and L ^c is a group of -CH ₂ -O-CH ₂ -CH ₂ -; or (4) R ^c' is CF ₃ -O-, formula: (C _q F _2q O) _{nc is} represented by -CF(-CF ₃ )-CF ₂ -O- and -CF ₂ -O-, nc is 1~1000, compared Preferably, the number is a repeat of 5 to 150, Y ^c is -CF ₂ -, and L ^c is a group of -CH ₂ -O-CH ₂ -CH ₂ -.

In another aspect of the invention, R ^{c is} preferably an organic group which may contain a hardenable portion.

When R ^c is an organic group which does not contain a hardening part, the "organic group which does not contain a hardening part" is, for example, an alkyl fluorenyl group and an alkyl group. Among them, an alkyl group is preferred, and a methyl group is particularly preferred.

When R ^c is an organic group containing a curable portion, the "organic group having a curable portion" is preferably a group in which the curable portion is bonded to X ^c via a linking group.

Examples of the "hardening portion" include an allyl group, a cinnamic acid group, a sorbic acid group, a (meth)acryl fluorenyl group, and a decane coupling group. Among them, a decane coupling group is preferred.

The "linking group" is preferably a linking group having 1 to 6 atoms in the main chain.

When the "curable portion" is a (meth) acrylonitrile group, the "linking group" is preferably -(CH ₂ ) _n - (n is 1 to 6), preferably -CH ₂ CH ₂ -.

On the other hand, when the "curable portion" is a decane coupling group, the "linking group" is preferably -(CH ₂ ) _n - (n is 1 to 6), preferably -(CH ₂ ) ₃ -.

When the material to be coated is an amorphous synthetic resin (for example, an acrylic resin), the "hardening portion" is preferably an allyl group or a cinnamic acid. The group, the sorbic acid group or the (meth) acrylonitrile group is more preferably a (meth) acrylonitrile group.

On the other hand, when the material to be coated is glass, the "curable portion" is preferably a decane coupling group.

X ^c represents -O-, -S-, -NH-, or a single bond. Preferred are -O-, -NH-.

A preferred aspect of the fluorinated copolymer of the present invention is that, in the formula (1), each R ^b2 is independently represented by a hydrogen atom or an organic group which may contain a hardenable portion, and R ^c represents no hardenability. The organic base of the Ministry.

However, at least one of the groups represented by R ^b2 is an organic group containing a curable portion, and the curable portion is a (meth)acryl fluorenyl group-containing fluorinated copolymer.

Another preferred aspect of the fluorinated copolymer of the present invention is that in the formula (1), each R ^b2 is independently represented by a hydrogen atom or an organic group which does not contain a hardenable portion, and R ^c is used as a hardening. The fluorochemical copolymer containing an organic group of a decane coupling group.

3. Method for producing fluorinated copolymer

The fluorocopolymer of the present invention can be produced by a method having the following steps.

(1) The cationically polymerizable monomer is separated from the perfluoropolyether group The step of cationic polymerization (step 1) and (2) the step of stopping the cationic polymerization reaction using the cationic polymerization initiator in the presence of the sub-polymerization initiator and the Lewis acid (step 2).

3.1. Step 1 3.1.1. Cationic polymerization initiators containing perfluoropolyether groups

The "perfluoropolyether group-containing cationic polymerization initiator" (starting species) used in the step 1 is a cationic polymerization initiator containing a monovalent or divalent perfluoropolyether group.

The "cationic polymerization initiator containing a monovalent perfluoropolyether group" may, for example, be of the formula (a): R ^a1 -X ^a -C(-R ^a2 )(-R ^a3 )-O-CO- R ^a4

Wherein R ^a1 represents a monovalent group containing a monovalent perfluoropolyether group.

X ^a represents -O-, -Ph-, -N(-R ^E )- (R ^E represents an organic group).

R ^a2 represents a hydrogen atom or an alkyl group.

R ^a3 represents a hydrogen atom or an alkyl group.

R ^a4 represents an alkyl group or a perfluoroalkyl group.

However, at least one of R ^a2 and R ^a3 is an alkyl group]

The compound shown, or (b): R ^a1 -X ^a -C(-R ^a2 )(-R ^a3 )-X ^c

Wherein R ^a1 represents a monovalent group containing a monovalent perfluoropolyether group.

X ^a represents -O-, -Ph-, -N(-R ^E )- (R ^E represents an organic group).

R ^a2 represents a hydrogen atom or an alkyl group.

R ^a3 represents a hydrogen atom or an alkyl group, but at least one of R ^a2 and R ^a3 is an alkyl group, and X ^c represents a compound represented by a halogen atom.

The "cationic polymerization initiator containing a divalent perfluoropolyether group" may, for example, be of the formula (c): R ^a4 -CO-OC(-R ^a2 )(-R ^a3 )-X ^a -R ^a1 -X ^a -C(-R ^a2 )(-R ^a3 )-O-CO-R ^a4

Wherein R ^a1 represents a divalent group containing a divalent perfluoropolyether group.

X ^a represents -O-, -Ph-, -N(-R ^E )- (R ^E represents an organic group).

R ^a2 represents a hydrogen atom or an alkyl group. And R ^a3 represents a hydrogen atom, or an alkyl group.

However, at least one of R ^a2 and R ^a3 is an alkyl group, and R ^a4 represents an alkyl group or a monovalent perfluoroalkyl group]

The compound shown, or (d): X ^c -C(-R ^a2 )(-R ^a3 )-X ^a -R ^a1 -X ^a -C(-R ^a2 )(-R ^a3 )-X ^c

Wherein R ^a1 represents a divalent group containing a divalent perfluoropolyether group.

X ^a represents -O-, -Ph-, -N(-R ^E )- (R ^E represents an organic group).

R ^a2 represents a hydrogen atom or an alkyl group.

R ^a3 represents a hydrogen atom or an alkyl group. And X ^c represents a halogen atom.

However, at least one of R ^a2 and R ^{a3 is} a compound represented by an alkyl group.

Specific examples of the "cationic polymerization initiator containing a monovalent perfluoropolyether group" include the following compounds.

[In these formulas, PFPE represents a monovalent perfluoropolyether lock

(preferably F-(CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeat number)). X represents a halogen atom. Other symbols indicate the same meaning as the above]

Specific examples of the "cationic polymerization initiator containing a divalent perfluoropolyether group" include the following compounds.

[In these formulas, PFPE represents a divalent perfluoropolyether group.

(preferably (i)-CF(-CF ₃ )-(O-CF ₂ -CF(-CF ₃ )) _n' -O-CF ₂ -Rf-CF ₂ -O-(CF(-CF ₃ ) -CF ₂ O-) _n -CF(-CF ₃ )- (Rf represents a perfluoroalkylene chain. n and n' each represent a repeat number), or (ii) -CF ₂ CF ₂ O-(CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF ₂ - (n represents the number of repetitions)).

Other symbols indicate the same meaning as described above. 〕

The above "perfluoropolyether group-containing cationic polymerization initiator" is preferably (The symbols in these formulas mean the same meaning as described above), and more preferably (The symbols in these formulas mean the same meaning as described above).

When the above "perfluoropolyether group-containing cationic polymerization initiator" is a cationic polymerization initiator containing a monovalent perfluoropolyether group, the compound can be obtained by the formula: F-(CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ -CH ₂ OC ₂ H ₄ O-CH=CH ₂ (n represents the number of repeats) [3-poly(perfluoropropoxy)-2,2,3, 3-tetrafluoropropoxy]ethoxyvinyl ether is produced by reacting an organic carboxylic acid (preferably acetic acid, trifluoroacetic acid, more preferably trifluoroacetic acid) or a hydrogen halide.

For example, the formula:

Wherein PFPE represents F-(CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (n is a repeat number).

Y ^a represents ^a method for producing a compound represented by a decyloxy group (for example, CF ₃ COO) or a halogen atom, and can be obtained by containing a formula: PFPE-CH ₂ -OC ₂ H ₄ O-CH=CH ₂ (wherein The symbol indicates 2-poly(perfluoropropoxy)methoxyethoxyvinyl ether (vinyl ether compound a) and the formula: Y ^a -H shown in the same meaning as described above (the symbol in the formula is represented by the foregoing A method of producing a compound (preferably CF ₃ COOH) in the same sense as the step of carrying out the reaction.

Similarly, the formula:

Wherein PFPE represents F-(CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeat number).

The compound represented by Y ^a represents a decyloxy group or a halogen atom] can be represented by a 2-poly group represented by the formula: PFPE-CH ₂ -O-CH=CH ₂ (wherein the symbolic meaning of the formula is as defined above) Perfluoropropoxy)methoxyvinyl ether and formula: Y ^a -H (the symbol in the formula means the same meaning as described above)

The method of producing a compound (preferably CF ₃ COOH) is carried out by a method of producing a reaction.

On the other hand, when the "perfluoropolyether group contains a cationic polymerization initiator" is a cationic polymerization initiator containing a divalent perfluoropolyether group, the compound can be obtained by the formula: CH ₂ =CH-O -CH ₂ -CH ₂ -O-CH ₂ -CF(-CF ₃ )-(O-CF ₂ -CF(-CF ₃ )) _n -O-CF ₂ -Rf-CF ₂ -O-(CF(- CF ₃ )-CF ₂ -O-) _n' -CF(-CF ₃ )-CH ₂ OC ₂ H ₄ O-CH=CH ₂ (wherein Rf represents a perfluoroalkylene chain. n, and n' Each compound represented by the number of repeats is produced by reacting an organic carboxylic acid (preferably acetic acid, trifluoroacetic acid (CF ₃ COOH), more preferably trifluoroacetic acid) or a hydrogen halide.

For example:

Wherein PFPE represents -CF(-CF ₃ )-(O-CF ₂ -CF(-CF ₃ )) _n -O-CF ₂ -Rf-CF ₂ -O-(CF(-CF ₃ )-CF ₂ -O-) _n' -CF(CF ₃ )-(Rf represents a perfluoroalkylene group. n and n' each represent a repeating number).

Y ^a represents ^a method for producing a compound represented by a decyloxy group (for example, CF ₃ COO) or a halogen atom, which can be obtained by containing a formula: CH ₂ =CH-OC ₂ H ₄ -O-CH ₂ -PFPE-CH ₂ -OC ₂ H ₄ -O- CH=CH ₂ (the symbol in the formula means the same meaning as described above)

The vinyl compound (vinyl ether compound b) and the formula: Y ^a -H are shown (the symbol in the formula represents the same meaning as described above)

The method of producing a compound (preferably CF ₃ COOH) is carried out by a method of producing a reaction.

Also, for example:

Wherein PFPE represents -CF ₂ CF ₂ -O-(CF ₂ -CF ₂ CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeat number).

Y ^a represents ^a method for producing a compound represented by a decyloxy group or a halogen atom, and can be obtained by containing a formula: CH ₂ =CH-OC ₂ H ₄ -O-CH ₂ -PFPE-CH ₂ -OC ₂ H ₄ - O- CH=CH ₂ (the symbol in the formula means the same meaning as described above)

The compound shown, and the formula: Y ^a -H (the symbol in the formula represents the same meaning as described above)

The method of producing a compound (preferably CF ₃ COOH) is carried out by a method of producing a reaction.

Similarly, the formula:

Wherein PFPE represents -CF ₂ CF ₂ -O-(CF ₂ -CF ₂ CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeat number).

The compound represented by Y ^a represents a decyloxy group or a halogen atom] can be represented by a formula: CH ₂ =CH-O-CH ₂ -PFPE-CH ₂ -O-CH=CH ₂ ^a compound of the same meaning as defined above, and a formula: Y ^a -H (the symbol in the formula represents the same meaning as described above)

The method of the step of carrying out the reaction of the indicated compound (preferably CF ₃ COOH) is carried out.

These production methods are novel production methods of the compounds of the formula (Ia), the formula (Ia), the formula (Ib), the formula (Ib') or the formula (Ib").

The reaction is preferably carried out in the presence of an acid in a solvent which does not adversely affect the reaction.

As such an acid, a mineral acid such as hydrochloric acid is preferred. The amount of the acid used is generally 0.01 to 1000 moles for the vinyl ether compound a or the vinyl ether compound b 1 mole.

As such a solvent, a fluorine-containing solvent such as HCFC-225 is preferred.

The reaction temperature is usually -78 to 50 ° C, preferably -10 to 10 ° C.

The reaction time is generally from 1 minute to 60 minutes.

Such a cationic polymerization initiator corresponds to the formula of the formula (1) representing the fluorinated copolymer of the present invention: [The symbols in the formulae indicate the same meaning as described above].

And when R ^a1 is a divalent group, the moiety is actually of the formula: The structure shown.

The concentration of the perfluoropolyether group-containing cationic polymerization initiator in the reaction system of the step 1 is preferably from 0.1 to 1,000 mM, more preferably from 1 to 100 mM.

3.1.2. Cationic polymerizable monomer

The cationically polymerizable single system used in the step 1 corresponds to a monomer constituting the unit Q.

For example, in the fluorine-containing copolymer produced by the production method, the formula: The portion (hereinafter sometimes referred to as part (b)) is a fluoropolymer which is composed of the above-mentioned constituent unit B, and is used as a cationically polymerizable monomer:

In the formula, R ^b2 represents an organic group containing a curable portion, and the symbol in the other formula represents a compound represented by the above meaning (hereinafter sometimes referred to as a cationically polymerizable monomer B).

Preferred examples of the monomer corresponding to the constituent unit Q ^b include the following compounds having a (meth)acryl fluorenyl group as the curable group.

(a):

[wherein, n represents the number of repetitions of an integer from 2 to 10.

R ^x represents a vinyl ether compound represented by hydrogen, methyl, chlorine or fluorine.

Specific examples of the vinyl ether compound:

(b) Formula: CH ₂ =CH-O-(CHR ^y ) _n -OC(=O)-CR ^x =CH ₂

[In the formula, N represents the number of repetitions of an integer from 1 to 40.

R ^y represents hydrogen or a methyl group.

R ^x represents a vinyl ether compound represented by hydrogen, methyl, chlorine or fluorine.

Specific examples of the vinyl ether compound:

(c):

[wherein, n represents the number of repetitions of an integer from 1 to 10.

R ^x represents a vinyl ether compound represented by hydrogen, methyl, chlorine or fluorine.

Specific examples of the vinyl ether compound:

(d) Formula: CH ₂ =CH-O-(CH ₂ ) _n -OC(=O)-NH-CH ₂ CH ₂ -OC(=O)-CX=CH ₂

[wherein, n represents the number of repetitions of an integer from 1 to 40.

X represents a vinyl ether compound represented by hydrogen, methyl, chlorine or fluorine.

Specific examples of the vinyl ether compound:

(e):

[wherein, n represents the number of repetitions of an integer from 1 to 10.

R ^x represents hydrogen, methyl, chlorine, or fluorine.

R ^y represents a styrene compound represented by hydrogen or methyl].

Specific examples of the styrene compound:

(f):

[wherein, n represents the number of repetitions of an integer from 1 to 6.

R ^x represents an epoxy compound represented by hydrogen or methyl].

Specific examples of the epoxy compound:

(g):

[wherein, n represents the number of repetitions of an integer from 1 to 6.

R ^x represents an epoxy compound represented by hydrogen or methyl] (2)

Specific examples of the epoxy compound:

As another preferable example of the monomer B corresponding to the constituent unit Q ^b , the curable group may be the following compound having a decane coupling group.

(a) Formula: CH ₂ =CH-O-(CH ₂ ) _n -Z

[wherein, n represents the number of repetitions of an integer from 1 to 40.

Z represents a vinyl ether compound represented by a decane coupling group.

(b) Specific examples of the vinyl ether compound: a compound represented by the formula: CH ₂ =CH-O-(CH ₂ ) ₃ -Z (wherein the symbol represents the same meaning as defined above).

(c) Formula: CH ₂ =CH-ORO-(CH ₂ ) _n -Z

Wherein R represents an ethyl group or a phenyl group.

n represents an integer from 1 to 6.

Z represents a vinyl ether compound represented by a decane coupling group.

(d) Specific examples of vinyl ether compounds:

(Z represents a decane coupling group.)

(e):

[wherein, n represents the number of repetitions of an integer from 1 to 10.

Z represents a urethane coupling compound represented by a decane coupling group].

Preferred specific examples of the urethane compound are:

(Z represents a decane coupling group.)

(f):

[wherein, n represents the number of repetitions of an integer from 1 to 12.

Z represents a decane coupling group. 〕

The styrene compound (2) is shown.

Preferred specific examples of the styrene compound are:

(Z represents a decane coupling group.)

(g) an epoxy compound having one epoxy group and one decane coupling group.

Preferred specific examples of the foregoing epoxy compound:

(wherein Z represents a decane coupling group.)

(h):

[wherein, n represents the number of repetitions of an integer from 0 to 10.

Z represents a styrene compound represented by a decane coupling group].

Preferred specific examples of the aforementioned styrene compound:

(wherein Z represents a decane coupling group.)

For example, when the above-mentioned part (b) is a fluorine-containing copolymer composed of only the above-mentioned constituent unit M, a cationically polymerizable monomer can be used.

[In the formula, R ^b2 represents a hydrogen atom or an organic group which does not contain a curable portion, and other symbols represent compounds represented by the above-mentioned meanings] (hereinafter sometimes referred to as a cationically polymerizable monomer M).

Preferred examples of the monomer corresponding to the constituent unit Q ^m include the following compounds having no curable group.

(a) formula: CH ₂ =CH-OR

Wherein R represents a monovalent organic group. However, the monovalent organic group is a compound which does not contain any of an -OH group, a -COOH group, and a -NH ₂ group.

The following compounds are mentioned as this compound.

(i):

[in the formula, n represents an integer from 1 to 10.

R ¹ represents a vinyl ether compound represented by an alkyl group].

Specific examples of the vinyl ether compound:

(ii):

[wherein, n represents an integer of 1 to 10.

R ¹ represents a vinyl ether compound represented by an alkyl group substituted by one or more fluorines.

Specific examples of the vinyl ether compound:

(iii) a vinyl ether compound containing one or more cyclic moieties selected from the group consisting of a monocyclic carbocyclic ring, a bicyclic carbocyclic ring, a tricyclic carbocyclic ring, and a tetracyclic carbocyclic ring.

Specific examples of the vinyl ether compound:

(iv):

[in the formula, n represents an integer from 1 to 10.

R ¹ represents a vinyl ether compound represented by a hydrocarbon group substituted by one or more (preferably 1 or 2) alkoxycarbonyl groups.

Specific examples of the "hydrocarbon group" include, for example, the vinyl ether compound:

When the vinyl ether compound is used, a carboxyl group can be introduced into the fluorinated copolymer of the present invention by hydrolyzing an alkoxycarbonyl group as needed after the polymerization reaction.

(v) A vinyl ether compound containing one or more (preferably one) amine groups protected by ruthenium imidization or guanidation.

Specific examples of the vinyl ether compound:

When the vinyl ether compound is used, an amine group can be introduced into the fluorinated copolymer of the present invention after the polymerization reaction, if desired, by deprotecting the protected amine group.

(vi) a vinyl ether compound containing one or more (preferably one) hydroxyl groups protected.

Specific examples of the vinyl ether compound:

When the vinyl ether compound is used, after the polymerization reaction, the fluorine-containing copolymer of the present invention can be obtained by deprotecting the protected hydroxyl group as needed. The substance is introduced into a hydroxyl group.

(vii) A vinyl ether compound containing an imidazolium salt.

Specific examples of the vinyl ether compound:

(viii):

[wherein, X represents hydrogen or a methyl group.

Ring A represents benzene or naphthalene.

R represents hydrogen, a halogen, or a monovalent organic group. However, the monovalent organic group does not contain an arylethylene derivative represented by any of an -OH group, a -COOH group, and a -NH ₂ group.

Specific examples of the arylethylene derivative:

(ix) other compounds

For example, when the fluorocopolymer composed of the constituent units B and M is synthesized in the above portion (b), the cationically polymerizable monomer B and the cationically polymerizable monomer M are used as the cationically polymerizable monomer.

In the above-mentioned part (b), when each of the constituent units B and M is a fluorine-containing copolymer which is formed into a block, the cationically polymerizable monomers B and M are successively subjected to cationic polymerization.

Specifically, only the first cationically polymerizable monomer (cationic polymerizable monomer B or M) is added to the reaction system to start the polymerization reaction, and the second cationic polymerizable single is added to the reaction liquid after the completion of the polymerization reaction. In the case of the bulk (cationic polymerizable monomer M or B), the polymerization of the second cationically polymerizable monomer is carried out for the progress of the living cationic polymerization, since the cation is often present at the end of the polymer.

On the other hand, in the fluorinated copolymer of the present invention, in the part (b), when the constituent units B and M are a fluorine-containing copolymer which is randomly combined, the cationically polymerizable monomers B and M are added to each other. The polymerization reaction is started in the reaction system.

Thus, the cationically polymerizable monomers B and M can be produced by a commercial product or by a known method.

The amount of the cationically polymerizable monomer to be used can be appropriately determined depending on the structure of the intended fluorinated copolymer.

In the production method, the number of repetitions of the constituent units derived from the cationically polymerizable monomer can be highly accurately controlled by using living cationic polymerization.

3.1.3. Lewis acid

Examples of the Lewis acid used in the step 1 include a compound represented by the following formula (A1) and a compound represented by the following formula (A2).

AlY ¹ Y ² Y ³ (A1)

(wherein, Y ¹ , Y ² and Y ³ each independently represent a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group).

Examples of the "halogen atom" represented by Y ¹ , Y ² and Y ³ include chlorine, bromine, and iodine.

Examples of the "alkyl group" represented by Y ¹ , Y ² and Y ³ include an alkyl group having 1 to 10 carbon atoms.

Examples of the "aryl group" represented by Y ¹ , Y ² and Y ³ include an aryl group having 6 to 10 carbon atoms.

Examples of the "alkoxy group" represented by Y ¹ , Y ² and Y ³ include an alkoxy group having 1 to 10 carbon atoms.

Examples of the "aryloxy group" represented by Y ¹ , Y ² and Y ³ include an aryloxy group having 6 to 10 carbon atoms.

Specific examples of the aluminum compound represented by the formula (A1) include diethyl aluminum chloride, diethyl aluminum bromide, and diethyl aluminum fluoride. , diethyl aluminum iodide, diisopropyl aluminum chloride, diisopropyl aluminum bromide, diisopropyl aluminum fluoride, diisopropyl aluminum iodide, dimethyl aluminum semi-chloride, Methyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum difluoride, ethyl aluminum diiodide, isobutyl aluminum dichloride, octyl aluminum dichloride, B Aluminium oxychloride dichloride, ethylene aluminum dichloride, phenyl aluminum dichloride, ethyl aluminum semi-chloride, ethyl aluminum half bromide, aluminum trichloride, aluminum tribromide, ethyl aluminum b An organoaluminum halide compound such as oxychloride, butyl aluminum butoxychloride or ethylaluminum ethoxy bromide; and a dialkoxyalkyl aluminum such as diethoxyethylaluminum or a double (2,6) Bis(alkyl-substituted allyloxy)alkyl aluminum such as di-t-butylphenoxy)methylaluminum or bis(2,4,6-tri-t-butylphenoxy)methylaluminum Wait. These aluminum compounds may be used alone or in combination of two or more.

With MZ ¹ Z ² Z ³ Z ⁴ (A2)

(wherein M represents tetravalent Ti or Sn. Each of Z ¹ , Z ² , Z ³ and Z ⁴ represents a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group). Tetravalent titanium or tetravalent tin compounds.

Examples of the "halogen atom", "alkyl group", "aryl group", "alkoxy group", and "aryloxy group" represented by each of Z ¹ , Z ² , Z ³ and Z ⁴ include The same as exemplified for each of Y ¹ , Y ² , and Y ³ .

Specific examples of the tetravalent titanium compound represented by the formula (A2) include titanium tetrachloride, titanium tetrabromide, and titanium halide such as titanium tetraiodide; titanium triethoxy chloride; and titanium trioxide. a titanium halide alkoxide such as a butoxide compound chloride; and a titanium tetraethoxide, and a titanium alkoxide such as a titanium n-butoxide Oxygen and the like.

Specific examples of the tetravalent tin compound represented by the formula (A2) include a tin halide such as tin tetrachloride, tin tetrabromide, and tin tetraiodide.

These tetravalent titanium compounds and tetravalent tin compounds may be used alone or in combination of two or more.

Further, examples of the Lewis acid include iron (Fe), gallium (Ga), indium (In), zinc (Zn), zirconium (Zr), hafnium (Hf), bismuth (Bi), and bismuth (Si). a halide of germanium (Ge) or germanium (Sb); a phosphonium salt (for example, an ammonium salt, a phosphonium salt); a metal oxide (for example, Fe ₂ O ₃ , Fe ₃ O ₄ , In ₂ O ₃ , Ga ₂ O) ₃ , ZnO, and Co ₃ O _4, etc.).

The amount of the Lewis acid to be used is preferably such that the cationically polymerizable monomer/Lloyd's acid (Mole ratio) is from 2 to 1,000, and preferably from 10 to 1,000.

3.1.4. Growth species stabilizer

Further, for the purpose of stabilizing the growth species in the living cationic polymerization in the step 1, an oxygen-containing or nitrogen-containing compound can be used.

Here, the growth species means an active species (cation) existing at the terminal end of the polymer which is elongated.

Examples of the oxygen-containing or nitrogen-containing compound include esters, ethers, ketones, quinone imines, phosphoric acid compounds, pyridine derivatives, and amines. Specific examples of the ester include ethyl acetate, butyl acetate, phenyl acetate, methyl chloroacetate, methyl dichloroacetate, ethyl butyrate, ethyl stearate, ethyl benzoate, and benzoic acid. Phenyl ester, diethyl citrate, and diisodecanoic acid ester.

Examples of the ether include a chain ether such as diethyl ether and ethylene glycol; and a cyclic ether such as dioxane or tetrahydrofuran.

Examples of the ketone include acetone and methyl ethyl ketone.

Examples of the quinone imine include ethyl phthalimide.

Examples of the phosphoric acid compound include triethyl phosphate.

The pyridine derivative may, for example, be 2,6-lutidine.

As said amine, a tributylamine is mentioned, for example.

These compounds may be used alone or in combination of two or more.

The amount of the oxygen-containing or nitrogen-containing compound to be used is preferably from 0.1 to 2000 mol, preferably from 1 to 2000 mol, for the Lewis acid 1 mol.

The reaction can be carried out in large quantities, but it is preferred to use a solvent.

Examples of the solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; carbon tetrachloride, dichloromethane, and dichloride. a halogenated hydrocarbon such as ethane; an ether such as dimethyl ether. Particularly preferred is a non-polar solvent. These solvents may be used alone or in combination of two or more.

The solvent is usually used in the form of a solvent: ethylene compound (capacity ratio) = 1:1 to 100:1, preferably 5:1 to 30:1.

The reaction temperature is usually -80 ° C to 150 ° C, preferably -78 to 80 ° C.

The reaction time is generally from 1 minute to 1 month, preferably 1 minute. Clock ~ 100 hours.

3.2. Step 2 3.2.1. Cationic polymerization stop agent

The "cationic polymerization stopper" used in the step 2 is a compound represented by the formula: R ^c -X ^c -H (wherein the symbols represent the same meanings as defined above).

When R ^c is a hydrogen atom, the cationic polymerization stopper is preferably water.

When R ^c is an organic group having no hardenable portion, the cationic polymerization stopping agent is preferably an alkyl alcohol represented by the formula: R-OH (wherein R is an alkyl group), preferably a methyl group.

When R ^c is an organic group containing a curable portion, it is preferred that the curable portion differs depending on the material to be coated. Therefore, it is preferred that the cationic polymerization terminator is different depending on the material.

When the material to be coated is an amorphous synthetic resin (for example, an acrylic resin), the cationic polymerization stopper is preferably a reducing agent, LiBH ₄ or an alkyl alcohol, preferably methanol.

On the other hand, when the material to be coated is glass, the cationic polymerization stopping agent is preferably of the formula: HX ^{c -} L ^{s -} R ^cs

(X ^c represents -O-, -S-, -NH-, or a single bond. Preferably -O-, -NH-. L ^s represents a linking group. Preferably -(CH ₂ ) _n8 -(n8 is 1 to 6), more preferably -(CH ₂ ) _{3 -.} R ^cs represents a compound represented by a decane coupling group, more preferably NH ₂ -(CH ₂ ) ₃ -Si(-OEt) ₃ .

The amount of the cationic polymerization stopper used is in the reaction solution, and only the reaction agent can be sufficiently contacted with the reaction end of the polymer, and the amount used is not strictly defined.

Generally, it is 0.01 to 10 times the capacity of the reaction solvent, preferably 0.1 to 1 times the capacity.

3.3. Other steps

The fluorinated copolymer of the present invention thus obtained can be purified by a usual method as necessary.

The fluorinated copolymer of the present invention produced by the production method has a high molecular weight uniformity, for example, a degree of dispersion (weight average molecular weight / number average molecular weight) in the range of about 2.5 to 1.0.

4. Oil-repellent and / or water-repellent coating agent

The oil-repellent and/or water-repellent coating agent of the present invention contains the fluorine-containing copolymer of the present invention.

The oil-repellent and/or water-repellent coating agent of the present invention may contain the fluorine-containing copolymer of the present invention as a main component or an active ingredient. The term "main component" means a component in which the content of the oil-repellent and/or water-repellent coating agent exceeds 50% by weight. The "active ingredient" is a component which forms a film (surface treatment layer) on the surface-treated substrate and exhibits the effects (water repellency, oil repellency, antifouling property, surface lubricity, friction durability, etc.) of the present invention. .

The fluorinated copolymer of the present invention is formed by coating a surface of a target to form a film, and imparts oil repellency to the surface. Further, the fluorinated copolymer of the present invention can form a film by applying it to the surface of the object, and then impart water repellency to the surface. Therefore, the oil-repellent and/or water-repellent coating agent of the present invention is used for the application of the surface of the object for the purpose of preventing water, oil, antifouling, and/or fingerprint adhesion.

The composition of the oil-repellent and/or water-repellent coating agent (or surface treatment composition) of the present invention can be suitably determined in accordance with the desired function.

Further, the oil-repellent and/or water-repellent coating agent of the present invention may contain, in addition to the fluorinated copolymer of the present invention, a fluoropolyether compound which is understood to be a fluorine-containing oil, preferably a perfluoropolyether compound. (The following is intended to be distinguished from the fluorinated copolymer of the present invention, and is sometimes referred to as "fluorine-containing oil"). The fluorine-containing oil does not have a reactive site (for example, a mercapto group) with the substrate. The fluorine-containing oil can improve the surface lubricity of the obtained film.

In the oil-repellent and/or water-repellent coating agent, 100 parts by mass of the perfluoropolyether group-containing decane compound (for the total of two or more, the same applies hereinafter), and the content of the fluorine-containing oil is, for example, 0. ~300 parts by mass, preferably 50 to 200 parts by mass.

The fluorine-containing oil may, for example, be a compound represented by the following formula (2) (perfluoropolyether compound).

R ²¹ -(OC _r F _2r ) _nd -OR ²² . . . (2)

In the formula, R ²¹ and R ²² each independently represent a perfluoroalkyl group having 1 to 16 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

Each r is an integer representing 1 to 3 when it appears.

The portion represented by the formula: -(OC _r F _2r ) _nd - is composed of at least one or more constituent units selected from the group consisting of OC ₃ F ₆ , OC ₂ F ₄ , and OCF ₂ . That is, the formula: -(C _r F _2r O) _nd - is represented by the formula: -(OC ₃ F ₆ ) _a' -(OC ₂ F ₄ ) _b' -(OCF ₂ ) _c' -.

Wherein, a', b' and c' represent all repeating numbers of perfluoropolyethers constituting the main skeleton of the polymer, and are independently an integer of 0 or more and 300 or less, and a sum of a', b' and c', that is, The nd is at least 1, preferably from 1 to 100.

Further, in the present specification, the order of existence of the repeating unit in the complex parentheses adjacent to the note number indicating the number of repetitions is arbitrary. That is, the combination pattern of these repeating units may be random or block. Among these repeating units, it may be -(OC ₃ F ₆ )-, -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )-, and -(OCF ₂ CF(CF ₃ ) Any one of them is preferably -(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- may be any of -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-, more preferably -(OCF ₂ CF ₂ )-.

Examples of the perfluoropolyether compound represented by the above formula (2) include compounds represented by any one of the following formulas (2a), (2b) and (2c).

R ²¹ -(OCFCFCF) _a" -OR ²² ...(2a)

R ²¹ -(OCF ₂ CF ₂ ) _b" -(OCF ₂ ) _c" -OR ²² . . . (2b)

R ²¹ -(OCF(CF ₃ )CF ₂ ) _d" -OR ²² ...(2c)

In the above formula, R ²¹ and R ^{22 are} as described above, a" is an integer of 1 or more and 100 or less, and b" and c" each independently represent an integer of 1 or more and 300 or less, and d" is an integer of 1 or more and 100 or less.

a compound represented by the formula (2a) and a compound represented by the formula (2b) They can be used individually or in combination. When these combinations are used, it is preferred to use the compound represented by the formula (2a) and the compound represented by the formula (2b) at a mass ratio of 1:1 to 1:30. A film having excellent balance between surface lubricity and friction durability can be obtained by the mass ratio.

The fluorine-containing oil may have an average molecular weight of from 1,000 to 30,000. Thereby, the film formed by the oil-repellent and/or water-repellent coating agent of the present invention (the surface treatment layer of the article coated with the oil-repellent and/or water-repellent coating agent of the present invention) can have a high surface Lubricity. The representative compound of the formula (2a) preferably has a number average molecular weight of from 2,000 to 6,000, and the compound of the formula (2b) preferably has a number average molecular weight of from 8,000 to 30,000. Under the range of these number average molecular weights, a film having a high surface lubricity can be obtained.

Further, the oil-repellent and/or water-repellent coating agent of the present invention may contain, in addition to the fluorinated copolymer of the present invention, an oxime compound (hereinafter referred to as "anthracene oil") which is understood to be eucalyptus oil. Emu oil can improve the aforementioned surface lubricity.

In the oil-repellent and/or water-repellent coating agent, the content of the eucalyptus oil is, for example, from 0 to 300 parts by mass, preferably from 50 to 200 parts by mass, per 100 parts by mass of the perfluoropolyether group-containing decane compound.

As the eucalyptus oil, for example, a linear or cyclic eucalyptus oil having a siloxane coupling of 2,000 or less is used. The linear eucalyptus oil may be a so-called linear eucalyptus oil and a denatured eucalyptus oil. Examples of the linear eucalyptus oil include dimethyl hydrazine oil, methyl phenyl hydrazine oil, and methyl hydrogen hydrazine oil. As the denatured eucalyptus oil, a linear type eucalyptus oil can be exemplified by an alkyl group, an aralkyl group, a polyether, a higher fatty acid ester, or a fluorocarbon. Modified by a base, an amine group, an epoxy group, a carboxyl group, an alcohol or the like. Examples of the cyclic eucalyptus oil include cyclic dimethyl siloxane oil and the like.

The film formed by the oil-repellent and/or water-repellent coating agent of the present invention is a solution obtained by dissolving a oil-repellent and/or water-repellent coating agent in a solvent, for example, by a roll coating method, a gravure coating method, or a micro method. After the gravure coating method, the flow coating method, the bar coating method, the spray coating method, the die coating method, the spin coating method, the dip coating method, the vapor deposition method, or the like, the surface of the object is coated and dried, It is carried out by UV irradiation as necessary.

When the hardness of the film is increased or not, the monofunctional and polyfunctional (meth) acrylate monomer may be appropriately added for the purpose of improving the adhesion to the substrate and the like. The fluorinated copolymer of the present invention exhibits high compatibility with monofunctional and polyfunctional (meth) acrylate monomers, so that the appearance is not impaired, and the added monomer can function as a crosslinking agent to harden The film can achieve moderate hardness, improve substrate adhesion and cure speed.

The fluorinated copolymer of the present invention exhibits high solubility not only for an organic solvent containing fluorine but also for a non-fluorine-containing organic solvent of a general-purpose solvent, so that it can be dissolved in an organic solvent containing fluorine or an organic solvent containing no fluorine. Apply to the surface of the coated object.

Examples of the organic solvent containing fluorine include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkylethanol, perfluorobenzene, and perfluorotoluene. , perfluoroalkylamine (Fluorinert (trade name), etc.), perfluoroalkyl ether, perfluorobutyl tetrahydrofuran, hydrofluoroether (Novec (trade name), HFE-7100, etc.), perfluoroalkyl bromide, Perfluoroalkyl iodide, perfluoropolyether (Krytox (trade name), DEMNUM (trade name), Fomblin (trade name), etc.) 2-(perfluoroalkyl)ethyl methacrylate, 2-(acrylic acid) Fluoroalkyl)ethyl, perfluoroalkylethyl, chlorofluorocarbon 134a, and hexafluoropropylene oligomer.

Further, examples of the organic solvent not containing fluorine include methyl isobutyl ketone, propylene glycol monomethyl ether, pentane, hexane, heptane, octane, dichloromethane, chloroform, and carbon tetrachloride. , dichloroethane, carbon disulfide, benzene, toluene, xylene, nitrobenzene, diethyl ether, dimethoxyethane, diglyme, triethylene glycol, ethyl acetate, butyl acetate, Dimethylformamide, dimethylhydrazine, acetone, 2-butanone, acetonitrile, benzonitrile, butanol, 1-propanol, 2-propanol, ethanol, methanol, triethylamine, and aniline .

The solvent in which the fluorinated copolymer of the present invention is dissolved is preferably methyl isobutyl ketone, propylene glycol monomethyl ether, hexadecane, butyl acetate, acetone, ethyl acetate or 2-propanol.

These solvents may be used alone or in combination of two or more.

The fluorinated copolymer of the present invention also exhibits high solubility in a non-fluorine-containing organic solvent of a general-purpose solvent.

Examples of the material (substrate) to be coated include inorganic materials such as glass; polyolefin resins such as polyethylene and polystyrene; acrylic resins such as polymethyl methacrylate, polyacrylates, and poly Polyester resin such as ethylene terephthalate, polycarbonate resin, and A synthetic resin such as a phenol resin; a metal such as iron, aluminum, or copper, but is not limited thereto.

Among them, glass, or amorphous synthetic resin (such as acrylic tree) Fat or high heat resistant cyclic polyolefin resin (COP) or polyester resin (such as polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin), polycarbonate Resin is preferred.

Further, the fluorinated copolymer of the present invention can be used in a hard coating agent for sale.

Since the fluorinated copolymer of the present invention exhibits high compatibility, it does not impair the physical properties of the commercially available hard coating agent, and imparts high water repellency and antifouling properties to the surface.

The film formed by the oil-repellent and/or water-repellent coating agent of the present invention has excellent water repellency, oil repellency, antifouling property, fingerprint adhesion prevention property, and durability, and can be strongly bonded to an object to be coated, and For clarity, the oil-repellent and/or water-repellent coating of the present invention can be applied to the application of various articles (products, devices, or components).

Articles containing a film formed from the oil-repellent and/or water-repellent coating agent of the present invention are also within the scope of the invention.

Hereinafter, an article having a film formed of such an oil-repellent and/or water-repellent coating agent will be described in detail.

The article of the present invention comprises a substrate and a fluorocopolymer or oil-repellent and/or water-repellent coating agent of the present invention on the surface of the substrate (hereinafter referred to as "oil-repellent and/or water-repellent coating" The layer formed by the coating ") (surface treatment layer).

Such an article can be manufactured, for example, as follows.

For example, when the article to be manufactured is an optical member, the substrate is a material for an optical member, and may be, for example, glass or transparent plastic. Further, in the surface region where the surface treatment layer is formed of the oil-repellent and/or water-repellent coating agent, a layer such as a hard coat layer and/or an antireflection layer may be formed. Any one of the single-layer reflection preventing layer and the multilayer reflection preventing layer can be used for the antireflection layer. Examples of the inorganic substance which can be used for the antireflection layer include SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO ₃ and the like, these inorganic substances may be used singly or in combination of two or more kinds (for example, as a mixture). In the case of the multilayer reflection preventing layer, it is preferred to use SiO ₂ and/or SiO in the outermost layer. When the article to be manufactured is an optical glass element for a touch panel, a transparent electrode such as a film of indium tin oxide (ITO) or indium zinc oxide may be provided on a part of the surface of the substrate (glass). Further, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative enamel layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a retardation film, or the like in accordance with the specific specifications. And liquid crystal display modules.

The shape of the substrate is not particularly limited. Further, the surface area of the substrate on which the surface treatment layer is formed may be at least a part of the surface of the substrate, and may be appropriately determined in accordance with the use and specific specifications of the article to be manufactured.

As the substrate, those having a hydroxyl group in the surface portion may be used. Examples of the material include glass, and a metal (particularly a base metal), a ceramic, a semiconductor, or the like which forms a natural oxide film or a thermal oxide film on the surface. When a resin or the like is not sufficient even if it has a hydroxyl group, or when a hydroxyl group is not originally provided, a hydroxyl group is introduced or added to the surface of the substrate by appropriately pretreating the substrate. Examples of the pretreatment include plasma treatment (for example, corona discharge) or ion beam irradiation. Plasma treatment can be used to purify the substrate table while introducing or adding hydroxyl groups on the surface of the substrate. Face (remove foreign matter, etc.). Further, as another example of the pretreatment, an interface sorbent having a carbon-carbon unsaturated bond group may be used in advance by a LB method (Langmuir-Blodgett method) or a chemical adsorption method. A method in which a surface is formed as a monomolecular film, and then an unsaturated bond is cleaved in an environment containing oxygen or nitrogen.

Further, as the substrate, any other reactive group (for example, Si-H group) may be present on the surface portion. As such an example, a base material formed of a material having one Si-H group or an alkoxy decane may be mentioned.

Next, a film of the oil-repellent and/or water-repellent coating agent is formed on the surface of the substrate, and the film is post-treated as necessary to form a surface-treated layer.

The film of the oil-repellent and/or water-repellent coating agent is formed by coating the surface of the substrate with the oil-repellent and/or water-repellent coating agent described above. The coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.

Examples of the wet coating method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and the like.

Examples of the dry coating method include vacuum deposition, sputtering, CVD, and the like. Specific examples of the vacuum vapor deposition method include resistance heating, electron beam, high-cycle heating, ion beam, and the like. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and the like.

It can also be coated by an atmospheric pressure plasma method.

When the wet coating method is used, the oil-repellent and/or water-repellent coating agent must be diluted with a solvent and used on the surface of the substrate. From the viewpoint of the stability of the oil-repellent and/or water-repellent coating agent and the volatility of the solvent, the following solvents can be preferably used.

Perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (for example, double ( Trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbon; hydrofluoroether (HFE) (eg perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ An alkyl perfluoroalkyl ether such as perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) or perfluorohexyl methyl ether (C ₂ F ₅ CF(OCH ₃ ) C ₃ F ₇ ) The perfluoroalkyl group and the alkyl group may be linear or branched) and the like. These solvents may be used singly or as a mixture of two or more. Among them, hydrofluoroether is preferred, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and/or perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) is particularly preferred.

Hereinafter, the fluorinated copolymer of the present invention used in the oil-repellent and/or water-repellent coating agent of the present invention will be described in more detail when it has a decane coupling group.

The film is formed so that the oil-repellent and/or water-repellent coating agent in the film is preferably used in combination with a catalyst used in hydrolysis and dehydration condensation. When the wet coating method is used in a simple manner, the oil-repellent and/or water-repellent coating agent may be diluted with a solvent and used in the dilution of the oil-repellent and/or water-repellent coating agent before being applied to the surface of the substrate. Media. When using the dry coating method, the oil-repellent and/or water-repellent coating agent added with a catalyst is directly subjected to vacuum evaporation. Alternatively, it may be used in a metal porous body such as iron or copper to impregnate the particulate matter of the oil-repellent and/or water-repellent coating agent of the catalyst to perform vacuum evaporation treatment.

Any suitable acid or base can be used as the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid or the like can be used. Further, as the alkali catalyst, for example, ammonia, an organic amine or the like can be used.

Second, the film can be post-treated as necessary. The post-treatment is not particularly limited. For example, water supply and drying heating can be performed one by one, and more specifically, the following can be carried out.

After the oil-repellent and/or water-repellent coating agent is formed into a film on the surface of the substrate, water is supplied to the film (hereinafter also referred to as "precursor film"). The method of supplying the water is not particularly limited. For example, a method of dew condensation or steam blowing by a temperature difference between the precursor film (and the substrate) and the surrounding environment can be used.

This is considered to be that when water is supplied to the precursor film, water acts on the decane coupling group in the fluorinated copolymer of the present invention to hydrolyze.

The supply of water can be carried out, for example, in an environment of 0 to 500 ° C, preferably 100 ° C or higher, and 300 ° C or lower. Hydrolysis may occur when water is supplied at this temperature range. The pressure at this time is not particularly limited, but is generally normal pressure.

Next, the precursor film was heated on the surface of the substrate in a dry environment exceeding 60 °C. The drying and heating method is not particularly limited, and the precursor film and the substrate together have a temperature of more than 60 ° C, preferably more than 100 ° C, for example, 500 ° C or less, preferably 300 ° C or less. It can be placed under the environment of unsaturated water vapor pressure. The pressure at this time is not particularly limited, but is generally normal pressure.

Under such circumstances, between the fluorinated copolymers of the present invention, the hydrolyzed decane coupling groups are rapidly dehydrated and condensed with each other. Further, between the compound and the substrate, the decane coupling group after hydrolysis of the compound rapidly reacts with the reactive group present on the surface of the substrate, and the reactive group present on the surface of the substrate is a hydroxyl group. Dehydration condensation is carried out (and, if such a bond is present between the compounds, the fluorine-containing oil and/or the eucalyptus oil may be in a mixed form). As a result, a bond is formed between the fluorinated copolymers of the present invention, and a bond is also formed between the fluorinated copolymer of the present invention and the substrate.

The water supply and the drying and heating can be continuously performed by using superheated water vapor.

The superheated steam is a gas obtained by heating saturated steam at a temperature higher than a boiling point, and is more than 100 ° C under normal pressure, generally 500 ° C or lower, for example, a temperature lower than 300 ° C, and by a temperature exceeding a boiling point The heating is a gas that becomes an unsaturated water vapor pressure. When the substrate forming the precursor film is exposed to the superheated water vapor, condensation is first generated on the surface of the precursor film by the temperature difference between the superheated water vapor and the relatively low temperature precursor film, thereby supplying water to the substrate. Precursor film. Then, as the temperature difference between the superheated steam and the precursor film becomes smaller, the moisture on the surface of the precursor film can be vaporized in a dry environment by the superheated steam, and the moisture content on the surface of the precursor film is lowered. During the period when the moisture content on the surface of the precursor film is lowered, that is, during the drying environment of the precursor film, the surface of the substrate is driven by the superheated water. The vapor is contacted and heated to the temperature of the superheated steam (temperature exceeding 100 ° C under normal pressure). Therefore, only the superheated water vapor is used, and the substrate on which the precursor film is formed is exposed to the superheated steam, whereby the water supply and the drying and heating can be continuously performed.

The implementation of the post-treatment as described above. This post-treatment is carried out in order to further improve the friction durability. Please note that the steps are not necessary when manufacturing the articles of the present invention. For example, after the oil-repellent and/or water-repellent coating agent is applied to the surface of the substrate, it can be directly left standing.

As described above, a surface treatment layer of a film derived from an oil-repellent and/or water-repellent coating agent is formed on the surface of the substrate to produce an article of the present invention. The surface treatment layer thus obtained has water repellency, oil repellency, antifouling property (for example, prevention of adhesion of dirt such as fingerprints), surface lubricity (or lubricity, wiping of dirt such as fingerprints, or gentle touch to fingers) Sense), friction durability, etc., can be suitably used as a functional film.

That is, the present invention also relates to an optical material in which the outermost layer further has the aforementioned cured product.

Examples of the optical material include an optical material such as a display which will be exemplified later, and a preferable diversified optical material.

For example, cathode wire tube (CRT; for example, TV, computer screen), liquid crystal display, plasma display, organic EL display, inorganic thin film EL dot matrix display, rear projection type display, fluorescent display tube (VFD), electric discharge display (FED; Field Emission Display) and other displays or protective plates to these displays, or those who apply anti-reflection film treatment to these surfaces.

The article having the surface-treated layer thus obtained is not particularly limited, and an optical member can be obtained. Examples of the optical member are as follows: lenses such as glasses; PDP, LCD and other display front protection plates, reflection preventing plates, polarizing plates, anti-glare plates; mobile phone, mobile information terminal and other machine touch panels; Blu-ray), DVD, CD-R, MO, etc.; optical fiber.

The thickness of the surface treatment layer is not particularly limited. The thickness of the surface treatment layer in the case of the optical member is preferably from 1 to 30 nm, preferably from 1 to 15 nm, but is preferably from the viewpoint of optical properties, surface lubricity, friction durability, and antifouling property.

The articles obtained by using the oil-repellent and/or water-repellent coating agent of the present invention are described in detail above. Further, the use, the method of use, the method of producing the article, and the like of the oil-repellent and/or water-repellent coating agent of the present invention are not limited to those exemplified above.

[Examples]

The symbols in the examples indicate the following meanings.

s: singlet state

t: triplet state

TLC: thin layer chromatography

TMS: tetramethyl decane

THF: tetrahydrofuran

Me: methyl

Et: ethyl

MIBK: methyl isobutyl ketone

MEK: methyl ethyl ketone

MOVE: 2-methoxyethyl vinyl ether [chemical formula: CH ₂ =CH-O-(CH ₂ ) ₂ -O-CH ₃ ]

AcVE: 2-(vinyloxy)ethyl acrylate [chemical formula: CH ₂ =CH-O-(CH ₂ ) ₂ -O-CO-CH=CH ₂ ]

AcVEE: 2-(vinyloxy)ethoxyethyl acrylate [chemical formula: CH ₂ =CH-O-(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -O-CO-CH=CH ₂ ]

McVE: 2-(vinyloxy)ethyl methacrylate [chemical formula: CH ₂ =CH-O-(CH ₂ ) ₂ -O-CO-C(-CH ₃ )=CH ₂ ]

McVEE: 2-(vinyloxy)ethoxyethyl methacrylate [chemical formula: CH ₂ =CH-O-(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -O-CO-C(-CH ₃ )=CH ₂ 〕

IBVE: isobutyl vinyl ether [chemical formula: CH ₂ =CH-O-CH ₂ -CH(-CH ₃ ) ₂ ]

5FVE: 3-(perfluoroethyl)propoxyethyl vinyl ether [chemical formula: CH ₂ =CH-O-(CH ₂ ) ₂ -O-(CH ₂ ) ₃ -C ₂ F ₅ ]

PFPE (base): F-(CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (when PFPE is monovalent), or -CF ₂ -CF ₂ -O-(CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (when PFPE is 2 valence)

(where n is the number of repetitions)

PFPE-Z (base): -CF ₂ -(OCF ₂ ) _m -(OCF ₂ CF ₂ ) _n -OCF ₂ - (where m and n each represent a repeat number)

PFPE-Z-diol: HOCH ₂ -CF ₂ -(OCF ₂ ) _m -(OCF ₂ CF ₂ ) _n -OCF ₂ -CH ₂ -OH (wherein m and n each independently represent the number of repeats)

As HCFC-225, AK-225 (trade name, Asahi Glass Co., Ltd.) was used.

Synthesis Example 1

Synthesis of 2-[3-poly(perfluoropropoxy)-2,2,3,3-tetrafluoropropoxy]ethoxy vinyl ether

In a 1L eggplant-shaped beaker, the following structural formula: PFPE-CH ₂ OH, perfluoropolyether-containing alcohol (DEMNUMSA (number average molecular weight 4000), Daikin Industries Co., Ltd.) 60 g (15 mmol), hydrogen sulfate 3.5 g (103 mmol) of tetrabutylammonium, 120 mL of a 40% aqueous sodium hydroxide solution, and 250 mL of m-hexafluoroxylene were stirred in a nitrogen atmosphere at room temperature for 30 minutes. To the above mixture, 120 mL of 2-chloroethyl vinyl ether was added, and a Dimroth condenser was placed in an eggplant-shaped beaker, and stirred at 70 ° C for 48 hours under a nitrogen atmosphere. After cooling, the reaction solution was distilled in a distiller to almost completely dry. The residual reactant was dissolved in a fluorine-based inert liquid (Fluorinert FC-72, Sumitomo 3M). The solution was extracted three times with dichloromethane to remove common impurities. Here, the removal of the common impurities is determined when the extract is tested by TLC (developing solvent: HCFC-225, detection method: spraying and heating of potassium permanganate solution, determination criteria: disappearance of spots at the origin). The solvent was distilled off under reduced pressure to give the desired 2-[3-poly(perfluoropropoxy)-2,2,3,3-tetrafluoropropoxy]ethyl vinyl ether.

The structure of the target was confirmed by NMR spectroscopy.

The NMR spectrum was determined by JEOL model JNM-ECS400 (measurement solvent: CDCl ₃ -hexafluorobenzene (1:5)).

The chemical shift used TMS as a reference material in ¹ H-NMR, and CFCl ₃ as a reference material in ¹⁹ F-NMR, and a low magnetic field side.

¹ H-NMR (CDCl ₃ -C ₆ F ₆ ): δ 3.86-3.91 (2H, m), 3.91-3.96 (3H, m), 4.08 (2H, t, J = 13.5 Hz), 4.13 (1H, dd , J = 14.7, 1.8 Hz), 6.40 (1H, dd, J = 14.7, 6.6 Hz).

¹⁹ F-NMR (CDCl ₃ -C ₆ F ₆ ): δ -83.12 (s), -84.27 (s), -8.4.52 (s), -84.82 (s), -85.06 (s), -85.50 (s) , -87.36 (t, J = 12.5 Hz), -125.65 (t, J = 13.5 Hz), -130.61 (s), -130.69 (s), -130.79 (s), -131.57 (s).

The peak of the CF ₂ group at the β position of the raw material alcohol (the triplet peak of -128.33 ppm) disappeared, and the triplet peak of -125.65 ppm was detected, so that the formation of the ether group was confirmed.

Hereinafter, the 2-[3-poly(perfluoropropoxy)-2,2,3,3-tetrafluoropropoxy]ethyl vinyl ether is abbreviated as PFPE4000VE.

Synthesis Example 2

Synthesis of cationic polymerization initiators containing PFPE groups (1)

The glassware used for the synthesis and polymerization was dried for 3 hours by a forced air dryer (130 ° C).

The glass reaction vessels A and B containing the three-way stopcock were each heated under a nitrogen stream, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and sufficiently dried in the vessel.

In a dry nitrogen atmosphere, 19.7 mL of HCFC-225 and 0.3 mL (4 mmol) of trifluoroacetic acid were placed in a container A, and after careful stirring, 20 mL (200 mol/l) of solution A was obtained. In another glass vessel B, 5.9 mL of HCFC-225 and 4.1 mL (2 mmol) of PFPE4000VE were added, and after stirring well, 10 mL (200 mol/l) of solution B was obtained. The diluted solution A and solution B are each cooled in an ice water bath at 0 ° C for about 15 minutes, and then cooled. The solution A was added to the solution B under a nitrogen stream for about 5 minutes, and stirred for 10 minutes to synthesize a cationic polymerization initiator containing a PFPE group. (Yield 19.5 ml, yield 99.5% or more.)

Hereinafter, the cationic polymerization initiator containing a PFPE group is sometimes simply referred to as PFPE4000VETFA.

When PFPE4000VETFA was stored, the purified PFPE4000VETFA was diluted to 0.1 M with HCFC-225, placed in a brown glass ampule under dry nitrogen, and stored in a cool dark place.

Synthesis Example 3

Synthesis of PFPE-based cationic polymerization initiators (2)

In a glass reaction vessel equipped with an Eileen condenser and a three-way stopcock, PFPE4000VE (4.1 mmol) (2 mmol) was diluted with HCFC-225 to make the whole 10 mL. 11 mL (200 mmol) of acetic acid and a small amount of hydrochloric acid were added thereto, and the reaction was carried out at 50 ° C for 6 hours. The obtained crude product was distilled under reduced pressure at 60 ° C or lower, and then dried under reduced pressure for 10 hours or more to obtain a product of a colorless transparent liquid (cationic polymerization initiator). (yield 19.5ml, yield More than 99.5%. )

Hereinafter, the cationically polymerizable initiator is sometimes simply referred to as PFPE4000VEAC.

Synthesis Example 4

Synthesis of poly(perfluoropropoxy)-1,ω-bis(vinyloxyethyl)ether

In a 20 mL eggplant-shaped beaker, the following structural formula: HOCH ₂ -PFPE-CH ₂ OH (wherein, n represents the number of repeats) contains a perfluoropolyether-based diol (number average molecular weight of 4000, Daikin) Industrial Co., Ltd. 1 g (0.25 mmol), 850 mg (2.5 mmol) of tetrabutylammonium hydrogen sulfate, 2 mL of a 40% aqueous sodium hydroxide solution, and 5 mL of m-hexafluoroxylene were stirred at room temperature for 30 minutes under a nitrogen atmosphere. 2 mL of 2-chloroethyl vinyl ether was added to the above mixture, and a Dimroth condenser was placed in an eggplant-shaped beaker, and stirred at 70 ° C for 72 hours under a nitrogen atmosphere. After cooling, the reaction solution was distilled in a distiller to almost completely dry. The residual reactant was dissolved in a fluorine-based inert liquid (Fluorinert FC-72, Sumitomo 3M). The solution was extracted three times with acetone and then with dichloromethane to remove common impurities. Among them, the determination of the common foreign matter was obtained by measuring the extract by TLC (developing solvent: HCFC-225, detection method: spraying and heating of potassium permanganate solution, and determining the standard: disappearance of the spot of the origin). The solvent was distilled off under reduced pressure to give the title compound (yield: 650 mg, yield: 63%).

Hereinafter, this compound is sometimes simply referred to as DEMNUM diol divinyl ether.

The NMR spectrum was determined by JEOL model JNM-ECS400 (measurement solvent: CDCl ₃ -hexafluorobenzene (1:5)).

In the case of ¹ H-NMR, TMS was used as a reference material, and in ¹⁹ F-NMR, CFCl _{3 was} used as a reference material, and a low magnetic field side was added.

¹ H-NMR (CDCl ₃ -C ₆ F ₆ ): δ 3.84-3.98 (5H, m), 4.08 (2H, t, J = 13.5 Hz), 4.10 (1H, dd, J = 14.7, 1.8 Hz), 6.39 (1H, dd, J = 14.7, 13.5 Hz).

¹⁹ F-NMR (CDCl ₃ -C ₆ F ₆ ): δ -83.12 (s), -84.27 (s), -8.4.52 (s), -84.82 (s), -85.06 (s), -85.50 (s) , -87.36 (t, J = 12.5 Hz), -125.65 (t, J = 13.5 Hz), -130.61 (s), -130.69 (s), -130.79 (s), -131.57 (s).

The peak of the F ₂ group at the β position of the raw material alcohol (the triplet peak of -128.33 ppm) disappeared, and since the triplet peak of -125.65 ppm was detected, the formation of the ether group was confirmed.

Synthesis Example 5a

Synthesis of PFPE group containing cationic polymerization initiator (DEMNUM diol divinyl ether acetate adduct)

218 mg (0.054 mmol) of the above-obtained DEMNUM diol divinyl ether and 10 μL of acetic acid were heated under nitrogen for 1 hour at 90 ° C in 1 mL of m-hexafluoroxylene. The reaction was traced to ethylene H (CH ₂ =CH-O) observed at 6.4 ppm of ¹ H-NMR and methicyl H (-CH(-O-CO-CH ₃ ) of acetal ester observed at 5.9 ppm. The peak area ratio of -O-CH ₂ -) is judged.

After cooling, the solvent was evaporated under reduced pressure to give the title compound. It can be used for polymerization without further purification.

DEMNUM diol divinyl ether acetate adduct

¹ H-NMR (CDCl ₃ -C ₆ F ₆ ): δ 1.40 (3H, d, J = 5.1 Hz), 2.07 (3H, s), 3.73-3.92 (4H, m), 4.03 (2H, t, J =13.2 Hz), 5.94 (1H, q, J = 5.1 Hz).

Synthesis Example 5b

Synthesis of 2-[3-poly(perfluoropropoxy)-2,2,3,3-tetrafluoropropoxy]vinyl ether

The object was synthesized by the method described in the Journal of American Chemical Society, 2002, Vol. 124, p. 1590 (American Chemical Society).

PFPE-CH ₂ OH (DEMNUMSA (number average molecular weight 4000), Daikin Industries) 4.0 g (1 mmol), vinyl acetate 276 μL (3 mmol), sodium carbonate 106 mg (1 mmol) in a 10 mL eggplant beaker under nitrogen atmosphere ), suspension of di-μ-chlorobis(1,5-cyclooctadiene) diterpene (I) complex ({IrCl(COD)} ₂ ) 22 mg (0.03 mmol) of m-hexafluoroxylene 4 mL The solution was heated and stirred at 100 ° C for 15 hours.

After the solvent was distilled off, the reaction product was subjected to column chromatography (developing solvent: AK-225) using a triethylamine-treated (one-time hexane in 1% hexane and then dried). After purification, the desired product (quantitative) was obtained.

¹ H-NMR (C ₆ F ₆ ): δ 3.80 (2H, t, J = 12.4 Hz), 3.82 (1H, dd, J = 2.7, 6.4 Hz), 3.96 (1H, dd, J = 2.7, 14.2 Hz) ), 6.10 (1H, dd, J = 6.4, 14.2 Hz).

Further, for the ¹⁹ F-NMR measurement, the peak of the CF ₂ group at the β position of the starting alcohol (the triplet peak of -128.33 ppm) disappeared, and the triplet peak of -124.99 ppm was detected, so that the formation of the ether group was confirmed. .

Synthesis Example 5c

The polymerization initiator 5c shown in the above structural formula was prepared in the same manner as in Synthesis Example 2 by the compound obtained in Synthesis Example 5b. The progress of the reaction was confirmed by the disappearance of 6.10 ppm of olefin H and the methine H from 5.90 ppm of the produced acetal in ¹ H-NMR.

Synthesis Example 6

Synthesis of vinyl ether having a decane coupling group as a hardening portion (1)

According to Crivello, J.V., Mao, Z., Chemistry of of The method described in Materials, 1997, Vol. 9, p. 1554 (American Chemical Society), synthesizes the target.

1-(1-Propoxy)-2-(vinyloxy)ethane (25.6 g, 200 mmol), triethoxydecane (32.8 g, 200 mmol), Rh(I)Cl(PPh ₃ ) ₃ ( 30 mg (0.03 mmol) of a toluene solution (50 mL) was stirred under reflux for 72 hours, and after cooling, the solvent was distilled off under reduced pressure, and distillation was continued to obtain the object (yield: 25.0 g, yield: 43%). Boiling point: 95 ° C (100 pa)

1-(1-propenyloxy)-2-(2-triethoxydecyloxyethoxy)ethane

¹ H-NMR (CDCl ₃ ): δ 1.02-1.10 (2H, m), 1.16-1.23 (9H, m), 1.49-1.56 (3H, m), 3.54-3.62 (4H, m), 3.71-3.86 ( 8H,m), 3.95 (1H, dd, J=14.2, 2.3 Hz), 4.16 (1H, dd, J=6.9, 2.3 Hz), 4.29-4.43 (cis vinyl H, m), 4.68-4.81 (trans vinyl H, m), 5.94 (cis vinyl H, dq, J = 4.6, 1.8 Hz), 6.22 (trans vinyl H, dq, J = 12.4, 1.4 Hz), 6.46 (1H, dd, J = 14.2, 6.9 Hz) .

Synthesis Example 7a

Synthesis of vinyl ether having a decane coupling group as a curable portion (2)

3-(triethoxydecyl) was added dropwise at 0 ° C in 2-diethyloxyethanol (3.56 g, 40 mmol), triethylamine (4.09 g, 40 mmol) in anhydrous dichloromethane (30 mL) A solution of propyl isocyanate (10 g, 40 mmol) in anhydrous dichloromethane (10 mL). After the reaction mixture was stirred at room temperature for 20 hours, the solvent was distilled off under reduced pressure, and the residue was evaporated under reduced pressure to yield (yield: 8.5 g, yield: 63%). Boiling point: 150 ° C (100 pa)

¹ H-NMR (CDCl ₃ ): δ 0.57-0.64 (2H, m), 1.21 (9H, t, J = 6.9 Hz), 1.56-1.66 (2H, m), 3.12-3.21 (2H, m), 3.80 (6H,q,J=6.9Hz),3.83-3.89(2H,m),4.02(1H,dd,J=6.4,1.8Hz), 4.19(1H,dd,J=14.7,1.8Hz), 4.26- 4.32 (2H, m), 5.02 (1H, bs), 6.43 (1H, dd, J = 14.7, 6.4 Hz).

Example 1

Synthesis of copolymers containing PFPE and hardenable parts (A-M-B-N type) (1)

For the representation of the copolymer version, A represents a moiety having a PFPE group. B represents a block formed by a constituent unit having a hardenable portion. The M meter is a block formed by a constituent unit that does not contain a hardenable portion. And N means no The terminal group containing the hardenable portion.

The glassware used for the synthesis and polymerization was dried for 3 hours by a forced air dryer (130 ° C).

The glass reaction vessel containing the three-way stopcock was heated under a nitrogen stream, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and sufficiently dried in the vessel.

In a dry nitrogen atmosphere, a container of FPE4000VETFA 2.0 ml (diluted to 0.1 mol/L in HCFC-225) (corresponding to 0.2 mmol) in the form of a cationic polymerization initiator containing a PFPE group was placed in a container, and the HCFC was used as a polymerization solvent. -225 5.82 mL, and 1.0 mL of 1,4-dioxane as a base added. Furthermore, 0.18 mL (1.6 mmol) of MOVE which is a monomer which does not contain a hardening part was added, and the whole was made into 9.0 mL, and it cooled to 0 degreeC, and it stirred on nitrogen- 0 ° C. Here, 1 mL (0.2 mmol) of ethyl aluminum hemichloride (Et _1.5 AlCl _1.5 ) diluted in a polymerization solvent of HCFC-225 was placed in advance, and rapidly added under dry nitrogen and polymerization was started. After a minute, as a monomer containing a curable portion, 0.12 mL (1 mmol) of McVE diluted twice with HCFC-225 (0.24 mL of HCFC-225 solution) was added, and after 60 minutes, 1% ammonia methanol (MeOH) was added. The solution stops the reaction.

In this step, a copolymer of the desired type A-M-B-N is obtained.

The resulting polymer was purified as follows. First, after the reaction solution after the polymerization is stopped is diluted with HCFC-225, the catalyst is removed. A small amount of methanol was added to the residue, and the mixture was washed six times with 0.6 N aqueous HCl solution, washed three times with ion-exchanged water, and washed until the washing water was neutral. This solution was transferred to an eggplant type beaker, and the solvent, the unreacted monomer, and the added alkali were distilled off under reduced pressure using a rolling distiller. After that, it is shielded from light and stored in a refrigerator

¹ H-NMR (CDCl ₃ ): δ 0.75-0.95 (m), 1.00-2.10 (m), 2.15-2.40 (m), 3.25-3.40 (m), 3.40-4.00 (m), 4.15-4.40 (m) ), 4.60-4.70 (m), 5.25-5.45 (m), 5.45-5.80 (m), 6.00-6.15 (m).

Since olefin protons derived from methacrylate were observed at 5.45-5.80 ppm and 6.00-6.15 ppm, and olefin protons derived from vinyl ether were not observed at 4 ppm and 6.5 ppm, the vinyl ether unit was subjected to cationic polymerization, and the hardenable portion was obtained. The methacrylate unit remains in an unreacted manner. From the above, it was confirmed that a polymer having a desired structure was obtained.

For the polymer produced, the conversion ratio (polymerization ratio, conversion) of the monomer and the number average molecular weight (Mn) and molecular weight distribution of the polymer were determined by gel permeation chromatography (GPC). (Mw/Mn). The results are summarized in Table 7.

Further, it was confirmed by NMR measurement that the polymer-free starter was not present, and the peak of the C=C bond based on the (meth)acrylic group was observed, and it was confirmed that the produced polymer contained the curable portion.

Thermal analysis (TGA, DSC) of the obtained polymer was carried out. The results are summarized in Table 7.

Further, the polymer produced was tested for solubility in each of methyl isobutyl ketone (MIBK), acetone, propylene glycol monomethyl ether (PGME), ethyl acetate, butyl acetate, and chloroform.

(method)

A sample of 1 g of the whole solution was taken out, and the state of the solution after 12 hours was visually observed at room temperature.

The results are shown in Table 8. The symbols in Table 8 indicate the following evaluations.

(assessment)

○ Dissolved transparently and uniformly.

△ Although there is turbidity, it dissolves.

× No dissolution.

Example 2~9

Synthesis of copolymers containing PFPE and hardenable parts (A-M-B-N type) (2)

In the same procedure as in Example 1, except that the monomers and types used were changed, a copolymer of the A-M-B-N type was synthesized by cationic polymerization using PFPE4000VETFA as a cationic polymerization initiator.

The monomers, types and the like used are shown in Table 1.

Moreover, the physical properties of the obtained polymer were measured in the same manner as in Example 1. The results are summarized in Tables 7 and 8.

Example 10

Synthesis of copolymers containing PFPE-based and hardenable parts (A-M/B-N type)

For the representation of the copolymer version, A represents a moiety having a PFPE group. B represents a portion containing a hardenable portion. And M/B represents a portion in which the constituent unit M of the curable portion and the constituent unit B containing the curable portion are randomly copolymerized.

The glassware used for the synthesis and polymerization was dried for 3 hours by a forced air dryer (130 ° C).

The glass reaction vessel containing the three-way stopcock was heated under a nitrogen stream, cooled to room temperature under nitrogen pressure, and returned to normal pressure with dry nitrogen to sufficiently dry the inside of the vessel.

In a container under a dry nitrogen atmosphere, 2.0 mL of PFPE 4000 VETFA (diluted to 0.1 mol/L in HCFC-225) (corresponding to 0.2 mmol) in the form of a cationic polymerization initiator containing a PFPE group was added as a polymerization solvent. 225 5.7 mL, and 1.0 mL of 1,4-dioxane. Further, (1) MOVE 0.18 mL (1.6 mmol) as a monomer not containing a curable portion, and (2) diluted to a 2-fold dilution with HCFC-225 as a monomer having a curable portion, were added under dry nitrogen. AcVE 0.12 mL (1 mmol) was made 9.0 m in total, and after cooling to 0 ° C, it was stirred under nitrogen pressure on an ice bath using a magnetic stirrer, and kept at 0 °C. Here, it was diluted with HCFC-225 of a polymerization solvent in advance, and 1 mL (0.2 mmol) of ethyl aluminum hemichloride (Et _1.5 AlCl _1.5 ) at 0 ° C was thermostated, and rapidly added under dry nitrogen to start polymerization. After 60 minutes, a 1% solution of ammonia in methanol was added and the reaction was stopped.

In this step, a copolymer of the desired type A-M/B-N is obtained.

Purification of the produced polymer was carried out in the same manner as in Example 1. It was confirmed by NMR that the polymer formed contained the curable portion from the presence of the non-starting species and the presence of a peak of the C=C bond of the acrylic group.

The physical properties of the polymer produced were measured in the same manner as in Example 1.

The results are summarized in Tables 7 and 8.

Example 11

a copolymer containing a PFPE group and a hardenable portion (A-B-N type) Synthesis (1)

For the representation of the copolymer version, A represents a moiety having a PFPE group. B represents a block formed by a constituent unit having a hardenable portion. And N represents an end group having no curable portion.

The glassware used for the synthesis and polymerization was dried for 3 hours in a blower-temperature constant temperature dryer (130 ° C).

The glass reaction vessel containing the three-way stopcock was heated under a nitrogen stream, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and sufficiently dried in the vessel.

In a dry nitrogen atmosphere, 2.0 mL of PFPE 4000 VETFA as a cationic polymerization initiator containing a PFPE group (diluted to 0.1 mol/L with HCFC-225) (corresponding to 0.2 mmol) and HCFC as a polymerization solvent were added to the vessel. 225 5.88 mL, and 1.0 mL of 1,4-dioxane. Further, under reduced nitrogen, HCFC-225, which is a monomer containing a curable portion, was diluted to a 2-fold diluted AcVE 0.12 mL (1 mmol) (0.24 mL as a HCFC-225 solution), and the whole was 9.0 mL, and cooled to 9.0 mL. After 0 ° C, the mixture was stirred under a nitrogen pressure and on an ice bath using a magnetic stirrer, and the temperature was adjusted at 0 ° C. 1 mL (0.2 mmol) of ethyl aluminum hemichloride (Et _1.5 AlCl _1.5 ) diluted with HCFC-225 in a polymerization solvent and constant temperature at 0 ° C was quickly added under dry nitrogen and polymerization was started.

After 60 minutes, the reaction was stopped by the addition of 1% ammonia in methanol.

In this step, the desired A-B-N type copolymer is obtained.

Purification of the produced polymer was carried out in the same manner as in Example 1. Row. It was confirmed by NMR that the polymer formed contained the curable portion from the presence of the non-starting species and the presence of a peak of the C=C bond of the acrylic group.

The physical properties of the polymer produced were measured in the same manner as in Example 1.

The results are summarized in Tables 7 and 8.

Example 12~17

Synthesis of copolymers containing PFPE-based and hardenable parts (A-B-N type) (2)

In the same manner as in Example 11, except that the monomer used was changed, a copolymer of the A-B-N type was synthesized by cationic polymerization using PFPE4000VETFA as a polymerization initiator.

The monomers, types and the like used are shown in Table 2.

Further, various physical properties of the polymer obtained were measured in the same manner as in Example 1. The results are summarized in Tables 7 and 8.

Example 18

Synthesis of copolymers containing PFPE-based and hardenable parts (A-M-C type) (1)

For the representation of the copolymer version, A represents a moiety having a PFPE group. M represents a block formed by a constituent unit having no curable portion, and C represents a terminal group containing a curable portion.

The glassware used for the synthesis and polymerization was dried for 3 hours by a forced air dryer (130 ° C).

The glass reaction vessel containing the three-way stopcock was heated under a nitrogen stream, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and sufficiently dried in the vessel.

PBSPE4000VETFA 2.0 mL (diluted to 0.1 mol/L in HCFC-225) (corresponding to 0.2 mmol) in advance as a cationic polymerization initiator containing PFPE in a dry nitrogen atmosphere, and HCFC-225 5.70 as a polymerization solvent was added to the vessel. mL, and 1,4-dioxane 1.0 mL. Further, 0.3 mL (2.6 mmol) of MOVE as a monomer having no curable portion was added under dry nitrogen, and the whole was 9.0 mL, and the mixture was cooled to 0 ° C, and then a magnetic stirrer was used under ice pressure and on an ice bath. Stirring was carried out and kept cold at 0 °C. After 3 minutes, quickly move to a low temperature bath of -30 ° C, and after reacting for 60 minutes, add NH ₂ -(CH ₂ ) ₃ -Si(-OEt) ₃ :THF = 1:1 cooled to -30 °C. 2 mL of the mixed solution was allowed to stop the reaction.

The resulting polymer was purified as follows. First, the reaction solution after the polymerization was stopped was diluted with HCFC-225, and after removing the catalyst residue, unreacted monomers, and adding a base, a dialysis membrane having a molecular weight of 6000 was used, and dialysis was carried out for 3 days in a methanol solution. The resulting polymer was stored in a 20% HCFC-225 solution without contact with water.

It was confirmed by NMR measurement that the residue of the starting species was not present, and the presence of the ethyl group of the triethoxyfluorenyl group confirmed that the polymer formed contained the curable portion.

In this step, a copolymer of the desired type A-M-C is obtained.

The physical properties of the polymer produced were measured in the same manner as in Example 1.

The results are summarized in Tables 7 and 8

Example 19

Synthesis of copolymers containing PFPE-based and hardenable parts (A-M-C type) (2)

In the same order as in Example 18, but changing the monomers used, by using the PFPE4000VETFA as a polymerization initiator Ion polymerization to synthesize a copolymer of the A-M-C type.

The monomers and types used are shown in Table 3.

Further, various physical properties of the polymer obtained were measured in the same manner as in Example 1. The results are summarized in Tables 7 and 8.

Example 20

Synthesis of copolymers containing PFPE-based and hardenable parts (A-M-B-N type) (3)

For the representation of the copolymer version, A represents a moiety having a PFPE group. B represents a block formed by a constituent unit having a hardenable portion. M represents a block formed by a constituent unit having no curable portion. N represents an end group having no curable portion.

The glassware used for the synthesis and polymerization was dried for 3 hours in a blower-temperature constant temperature dryer (130 ° C).

The glass reaction vessel containing the three-way stopcock was heated under a nitrogen stream, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and sufficiently dried in the vessel.

PFPE4000VETFA 2.0 mL (diluted to 0.1 mol/L in HCFC-225) (equivalent to 0.2 mmol) and HCFC-225 5.68 as a polymerization solvent were added to the vessel under a dry nitrogen atmosphere as a cationic polymerization initiator containing PFPE. mL, 1,4-dioxane 1.0 mL. Further, IBVE 0.32 mL (0.5 M) was added under dry nitrogen, and the whole amount was 9.0 mL, and after cooling to 0 ° C, the mixture was stirred under a nitrogen pressure and on an ice bath using a magnetic stirrer, and the mixture was thermostated at 0 ° C. . Here, 1 mL (0.2 mmol) of ethyl aluminum hemichlorochloride (Et _1.5 AlCl _1.5 ) which was previously diluted with a polymerization solvent of HCFC-225 at 0 ° C was rapidly added, and the polymerization was started rapidly under dry nitrogen. After 5 minutes, 0.1% (1.2 mmol) of AcVE diluted to 2-fold dilution was added to HCFC-225 as a monomer containing a curable portion, and after 60 minutes, a 1% ammonia solution in methanol was added to terminate the reaction.

In this step, a copolymer of the desired type A-M-B-N is obtained.

Purification of the produced polymer was carried out in the same manner as in Example 1. It was confirmed by NMR that the presence of the starting species and the presence of a peak of the C=C bond of the acrylic group confirmed that the produced polymer contained a curable portion.

The physical properties of the polymer produced were measured in the same manner as in Example 1.

The results are summarized in Tables 7 and 8.

Example 21~23

Synthesis of copolymers containing PFPE-based and hardenable parts (A-M-B-N type) (4)

The same procedure as in Example 20 was carried out, but the change was used. The monomer is a copolymer of the A-M-B-N type by cationic polymerization using PFPE4000VETFA as a cationic polymerization initiator.

The monomers, types, and the like used are shown in Table 4.

Further, various physical properties of the polymer obtained were measured in the same manner as in Example 1. The results are summarized in Tables 7 and 8.

Example 24

Synthesis of copolymers containing PFPE-based and hardenable parts (A-M-B-N type) (5)

For the representation of the copolymer version, A represents a moiety having a PFPE group. B represents a block formed by a constituent unit having a hardenable portion. M represents a block formed by a constituent unit having no curable portion. N represents an end group having no curable portion.

The glassware used for the synthesis and polymerization was dried for 3 hours in a blower-temperature constant temperature dryer (130 ° C).

The glass reaction vessel containing the three-way stopcock is heated under a nitrogen stream, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and placed in a container. Dry thoroughly.

In a dry nitrogen atmosphere, 2.0 mL of PFPE 4000 VETFA as a cationic polymerization initiator containing PFPE (diluted to 0.1 mol/L with HCFC-225) (corresponding to 0.2 mmol) and HCFC-225 5.8 as a polymerization solvent were added to the vessel. mL, and 1,4-dioxane 1.0 mL. Further, (1) 0.16 mL (1.2 mmol) of isobutyl vinyl ether [IBVE, CH ₂ =CH-O-CH ₂ CH(CH ₃ ) ₂ ] as a monomer having no curable portion, was added under dry nitrogen. And (2) 0.12 mL (1 mmol) of AcVE diluted to 2-fold dilution by HCFC-225 which is a monomer containing a hardenable part, and it made 9.0 mL whole, and after cooling to 0 degreeC, and the ice bath under nitrogen pressure The mixture was stirred using a magnetic stirrer and kept at 0 °C. Here, 1 mL (0.2 mmol) of ethyl aluminum hemichlorochloride (Et _1.5 AlCl _1.5 ) diluted with HCFC-225 as a polymerization solvent in advance at 0 ° C was rapidly added under dry nitrogen to start polymerization, and 60 minutes passed. The reaction was stopped by the addition of 1% ammonia in methanol.

In this step, a copolymer of the A-M-B-N type containing a PFPE group and a curable portion was obtained.

Purification of the produced polymer was carried out in the same manner as in Example 1. It was confirmed by NMR that the polymer formed contained the curable portion from the presence of the non-starting species and the presence of a peak of the C=C bond of the acrylic group.

The physical properties of the polymer produced were measured in the same manner as in Example 1.

The results are summarized in Tables 7 and 8.

Example 25

Synthesis of copolymers containing PFPE-based and hardenable parts (A-M-B-N type) (6)

Here, A represents a portion having a PFPE group. B represents a block formed by a constituent unit having a hardenable portion. M represents a block formed by a constituent unit having no curable portion, and N represents a terminal group having no curable portion.

The glassware used for the synthesis and polymerization was dried for 3 hours by a forced air dryer (130 ° C).

The glass reaction vessel containing the three-way stopcock was heated under a nitrogen stream, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and sufficiently dried in the vessel.

In a dry nitrogen atmosphere, 2.0 mL of PFPE 4000 VETFA as a cationic polymerization initiator containing a PFPE group (diluted to 0.1 mol/L with HCFC-225) (corresponding to 0.2 mmol) and HCFC as a polymerization solvent were added to the vessel. 225 5.68 mL, and 1,4-dioxane 1.0 mL. Further, 0.32 mL (1.5 mmol) of 5FVE, which is a monomer not containing a curable portion, was added under dry nitrogen to make 9.0 mL of the whole, and after cooling to 0 ° C, magnetic pressure was applied to the ice bath under nitrogen pressure. The stirrer was stirred and kept cold at 0 °C. Here, 1 mL (0.2 mmol) of ethyl aluminum hemichlorochloride (Et _1.5 AlCl _1.5 ) diluted with HCFC-225 in a polymerization solvent and previously made at 0 ° C was rapidly added under dry nitrogen and polymerization was started. After a minute, HCFC-225, which is a monomer containing a hardenable portion, was added to dilute 2-fold diluted AcVE 0.12 mL (1 mmol) (as 0.24 mL of HCFC-225 solution), and after 60 minutes, a 1% ammonia methanol solution was added. The reaction stopped.

In this step, a block copolymer of the A-M-B-N type containing a PFPE group and a curable portion was obtained.

Purification of the produced polymer was carried out in the same manner as in Example 1. It was confirmed by NMR that the polymer formed contained the curable portion from the presence of the non-starting species and the presence of a peak of the C=C bond of the acrylic group.

The physical properties of the polymer produced were measured in the same manner as in Example 1.

The results are summarized in Tables 7 and 8.

Example 26

Synthesis of copolymers containing PFPE-based and hardenable parts (A-M-B-N type) (7)

The procedure was carried out in the same manner as in Example 25 except that the monomer used was changed, and a copolymer of the A-M-B-N type was synthesized by cationic polymerization using PFPE4000VETFA as a cationic polymerization initiator.

The monomers, types, and the like used are shown in Table 5.

Further, various physical properties of the polymer obtained were measured in the same manner as in Example 1. The results are summarized in Tables 7 and 8.

Example 27

Synthesis of copolymers containing PFPE-based and hardenable parts (A-M-B-N type) (8)

For the representation of the copolymer version, A represents a moiety having a PFPE group. B represents a block formed by a constituent unit having a hardenable portion. M represents a block formed by a constituent unit having no curable portion, and N represents a terminal group having no curable portion.

Glassware for synthesis and polymerization was used for drying for 3 hours in a forced air dryer (130 ° C).

The glass reaction vessel containing the three-way stopcock was heated under a nitrogen stream, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and sufficiently dried in the vessel.

PBSPE4000VETFA 2.0 mL (diluted to 0.1 mol/L in HCFC-225) (equivalent to 0.2 mmol) in the container as a cationic polymerization initiator containing PFPE based in a dry nitrogen atmosphere, and HCFC-225 5.8 as a polymerization solvent. mL, and 1,4-dioxane 1.0 mL. Further, under dry nitrogen, (1) 0.32 mL (1.5 mmol) of 5FVE which is a monomer having no curable portion, and (2) diluted to a 2-fold dilution with HCFC-225 which is a monomer having a hardenable portion. AcVE 0.12 mL (1 mmol) (0.24 mL as HCFC-225 solution), the whole was 9.0 mL, cooled to 0 ° C, and then stirred under nitrogen pressure on an ice bath using a magnetic stirrer to keep cold at 0 ° C. . Here, 1 mL (0.2 mmol) of ethylaluminum hemichloride (Et _1.5 AlCl _1.5 ) diluted with HCFC-225 in a polymerization solvent and made 0 ° C in advance was rapidly added under dry nitrogen and polymerization was started. After 60 minutes, a 1% ammonia solution in methanol was added to stop the reaction.

In this step, a block copolymer of the A-M/B-N type containing a PFPE group and a curable portion was obtained.

Purification of the produced polymer was carried out in the same manner as in Example 1. It was confirmed by NMR that the polymer formed contained the curable portion from the presence of the non-starting species and the presence of a peak of the C=C bond of the acrylic group.

The physical properties of the polymer produced were measured in the same manner as in Example 1.

The results are summarized in Tables 7 and 8.

Example 32

Synthesis of a copolymer containing a hardening portion at both ends of a PFPE group

The glass reaction vessel containing the three-way stopcock was heated under a nitrogen stream, cooled to room temperature under nitrogen pressure, and returned to normal pressure with dry nitrogen to sufficiently dry the inside of the vessel.

In a dry nitrogen atmosphere, 2.0 mL of DEMNUM diol divinyl ether acetate adduct as a cationic polymerization initiator containing a PFPE group (diluted to 0.1 mol/L by HCFC-225 in advance) (equivalent to 0.2 mmol) was added to the vessel. ) 5.7 mL of HCFC-225 and 1.0 mL of 1,4-dioxane as a polymerization solvent. Further, (1) MOVE 0.18 mL (1.6 mmol) as a monomer not containing a curable portion, and (2) diluted to a 2-fold dilution with HCFC-225 as a monomer having a curable portion, were added under dry nitrogen. McVE 0.12 mL (1 mmol) was adjusted to 9.0 mL in total, and after cooling to 0 ° C, the mixture was stirred under a nitrogen pressure on an ice bath using a magnetic stirrer, and kept at 0 ° C.

Here, 1 mL (0.2 mmol) of ethyl aluminum hemichloride (Et _1.5 AlCl _1.5 ) diluted with a polymerization solvent of HCFC-225 and constant temperature at 0 ° C was rapidly added under dry nitrogen to start polymerization. After 60 minutes, a 1% ammonia solution in methanol was added and the reaction was stopped.

The reaction solution was placed in methanol, and the resulting precipitate was taken in chloroform-methanol. Purification by reprecipitation. The dried object was obtained under reduced pressure.

¹ H-NMR (CDCl ₃ ): δ 0.75-0.95 (m), 1.00-2.10 (m), 2.15-2.40 (m), 3.30 (bs), 3.40-4.00 (m), 4.15-4.40 (m), 4.60-4.70 (m), 5.25-5.45 (m), 5.45-5.80 (m), 6.00-6.15 (m).

The methoxy group from MOVE was observed at 3.30 ppm. Olefin protons from methacrylate were observed at 5.45-5.80 ppm and 6.00-6.15 ppm. Since no olefin protons derived from vinyl ether were observed at 4 ppm and 6.5 ppm, the vinyl ether unit was subjected to cationic polymerization, and the methacrylate unit of the curable portion remained unreacted.

From the above, it was confirmed that a polymer having a desired structure was obtained.

Synthesis Example 7b Synthesis of Vinyl Ether Containing PFPE

In a 50 mL eggplant-shaped beaker, the following structural formula: PFPE-CH ₂ OH, a perfluoropolyether-containing alcohol (number average molecular weight 7470) 1 g (0.13 mmol), and hydrogen tetrahydrochloride ammonium 1 g (2.9 mmol) were added. 2 mL of a 40% aqueous sodium hydroxide solution and 10 mL of m-hexafluoroxylene were stirred at room temperature for 30 minutes under a nitrogen atmosphere. 2 mL of 2-chloroethyl vinyl ether was added to the above mixture, and a Dimroth condenser was attached, and the mixture was stirred at 85 ° C for 72 hours under a nitrogen atmosphere. After cooling, the reaction solution was distilled off in a distiller to almost completely dry. The residual reactant was dissolved in FC-72. The solution was extracted three times with dichloromethane to remove the common impurities (the end point was to test the extract by TLC. The solvent HCFC225 was developed; the detection method was sprayed with potassium permanganate solution and heated to determine that the spots of the origin disappeared. ). The solvent was distilled off under reduced pressure to give the object.

The yield was 0.94 g (93%).

The structure of the target was confirmed by NMR spectroscopy.

¹ H-NMR (CDCl ₃ -C ₆ F ₆ ): δ 3.86-3.96 (5H, m), 4.08-4.13 (3H, m), 6.38-6.42 (1H, m).

¹⁹ F-NMR (CDCl ₃ -C ₆ F ₆ ): δ -82.90 - -83.10 (m), -83.35 - -83.50 (m), -84.40 (bs), -84.65 (bs), -84.90 (bs) , -85.15(bs), -85.60- -85.80(m), -87.50- -87.65(m), -89.00(s), -89.90- -90.02(m), -124.05- -124.20(m),- 125.68 (t, J = 13.8 Hz), -126.50 - -126.80 (m), -128.00 (bs), -130.40 (s), -130.60 (bs), -131.10 (s), -131.60 (s).

The peak of the CF ₂ group -128.74 (t) ppm at the β position of the starting alcohol disappeared, and the peak of -125.68 (t) ppm was detected, so that the formation of the ether group was confirmed.

Synthesis Example 8

Synthesis of vinyl ether trifluoroacetic acid adducts containing PFPE (PFPE-based cationic polymerization initiator)

The HCFC-225 solution (1 mL) dissolved in an equivalent amount of trifluoroacetic acid was dissolved at 0 ° C in a solution of the PFPE-containing vinyl ether (0.9 g) in HCFC-225 (5 mL) obtained in Synthesis Example 7b. Drop in. Stir at this temperature for 10 minutes to synthesize PFPE-containing Cationic polymerization initiator.

The formation of the target product was confirmed by H-NMR, and the disappearance of ethylene H (6.4 ppm) and the methine H (5.9 ppm) of the acetic acid adduct.

This compound was used directly in the polymerization without purification.

Comparative example 1

Synthesis of copolymers containing PFPE (A-M-N type) (1)

The glassware used for the synthesis and polymerization was dried for 3 hours by a forced air dryer (130 ° C).

The glass reaction vessel containing the three-way stopcock was heated under a nitrogen stream, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and sufficiently dried in the vessel.

In a dry nitrogen atmosphere, a PFPE4000VETFA 2.0 mL (previously diluted to 0.1 mol/L with HCFC-225) as a cationic polymerization initiator (sometimes abbreviated as Rf initiator) containing a PFPE group is added to the vessel (equivalent to 0.2) Methyl), 5.68 mL of HCFC-225 (AK225, Asahi Glass Co., Ltd.) as a polymerization solvent, and 1.0 mL of 1,4-dioxane as a base. Further, 0.32 mL (1.5 mmol) of 5FVE, which is a monomer having no curable portion, was added under dry nitrogen to make 9.0 mL of the whole, and after cooling to 0 ° C, magnetic stirring was carried out under nitrogen pressure and on an ice bath. The device was stirred and kept cold at 0 °C. Here, 1 mL (0.2 mmol) of ethyl aluminum hemichloride (Et _1.5 AlCl _1.5 ) diluted with HCFC-225 as a polymerization solvent of a catalyst and made to be 0 ° C was rapidly added under dry nitrogen. The polymerization was started, and after 60 minutes, a 1% ammonia solution in methanol was added to stop the reaction.

In this step, a block copolymer of the A-M-N type containing a PFPE group was obtained.

Purification of the produced polymer was carried out in the same manner as in Example 1. It was confirmed by NMR measurement that the residue of the starting species and the peak of the C=C bond were not present, and it was confirmed that the polymer formed did not contain the curable portion.

The conversion ratio was calculated in the same manner as in Example 1 for the produced polymer, and GPC measurement was performed.

The results are summarized in Table 7.

Comparative example 2~8

Synthesis of copolymers containing PFPE groups (A-M-N type) (2~8)

The monomers and types used were changed in the same manner as in Comparative Example 1, and a copolymer of the A-M-N type was synthesized by cationic polymerization using PFPE4000VETFA as a cationic polymerization initiator.

The monomers, types, and the like used are shown in Table 6.

Further, with respect to the produced polymer, the conversion ratio and the GPC measurement were calculated in the same manner as in Example 1. The results are summarized in Table 7.

In the "Structure" column in Table 7, the structure of each copolymer is indicated by a symbol. Here, the following numerals, which are noted from the constituent units of the monomers, indicate the number of repetitions. -b- indicates that the constituent unit forms a block, and -r- indicates a constituent unit to be randomly bonded. In this specification, the same symbols are used except for Table 7.

Test example 1

(1)

The commercially available hard coater kit 575CB (manufactured by Arakawa Chemical Industries Co., Ltd.) was dissolved in MIBK, and the contents obtained in each of Examples 1, 10, 11, 14, 20, 24, 25, and 27 were further added to the solution. The copolymer of PFPE was added to the solid content of the hard coating agent resin, and the solid content concentration was 1%, and a hard coating agent containing PFPE having a total solid concentration of about 0.4% was obtained.

The commercially available polycarbonate substrate (50 mm × 50 mm, manufactured by Mitsubishi Plastics Co., Ltd.) was subjected to dip coating (lifting speed: 4.0 mm/sec) of the PFPE-containing hard coating agent at 70 ° C for 5 minutes. After drying, a hardened film is obtained after irradiation with ultraviolet rays. The ultraviolet irradiation was a belt conveyor type ultraviolet irradiation device, and the irradiation amount was 600 mJ/cm ² .

Regarding the obtained cured film, the appearance was visually evaluated, and the contact angle with respect to water and the contact angle with respect to HD (n-hexadecane) were measured. The results are shown in Table 9.

The following test was conducted for the oily ink wiping property (ease of wiping of the oily ink). First, an oily ink was applied to the surface of the hardened film with a Sakura pen touch, and visually evaluated by appearance. Next, after drying, it was wiped with a Kimwipe S-200, and the appearance was visually evaluated. The results are shown in Table 9.

(2)

A cured film was obtained in the same manner as in the above (1) except that DEMNUMS-20 (number average molecular weight: 2,600, Daikin Industries Co., Ltd.) of the perfluoropolyether oil was used as the polymer containing PFPE.

However, since the cured film itself was white turbid and the oily liquid was separated from the surface, only the appearance was observed as an experiment.

(3)

In place of S-20 of Comparative Example 1, a cured film was obtained in the same manner as in S-65 (average molecular weight 4500, Daikin Industries Co., Ltd.). Since the cured film itself was white turbid and the oily liquid was separated from the surface, only the appearance was observed as an experiment.

(4)

A cured film was obtained in the same manner as in the above (1) except that the copolymer obtained in each of Comparative Examples 1 to 8 was used as the copolymer containing PFPE. The same evaluation as in the above (1) was carried out. The results are shown in Table 9.

〔Exterior〕

○: transparent

△: Translucent

×: white turbid

[Oil ink - pop-up]

◎: The ink is ejected with almost no residue.

○: The ink is ejected and cannot be a line

△: The ink is ejected, but the line has a residue.

×: The ink is ejected and the line can be drawn.

[oily ink - wipe]

◎: The ink can be wiped very lightly, with no residue at all.

○: The ink can be wiped off and there is no residue on the surface.

△: The ink cannot be wiped and remains on the surface.

×: The ink cannot be wiped and remains on the surface.

Example 33

PFPE4000VETFA (0.2 mmol) as a cationic polymerization initiator containing PFPE (MW: 4000), and HCFC-225 5.82 mL as a polymerization solvent were added to a glass vessel with a shut-off valve in a dry nitrogen atmosphere, and as an addition. Alkali 1,4-dioxane 1.0 mL. Further, 3-(triethoxyindenyl)propylvinyl ether (4 mmol) was added to make 9.0 mL of the whole, and the mixture was cooled to 0 °C. To the reaction solution, an ethylaluminum hemichloride (Et _1.5 AlCl _1.5 : 0.2 mmol) solution of HCFC-225 was added under stirring, and polymerization was started. After stirring at this temperature for 5 minutes, anhydrous ethanol:HCFC-225 (1:1) was added to stop the polymerization. The reaction solution was diluted with HFE7200 and perfluorohexane, and the chlorofluorocarbon solution-ethanol phase was separated by standing to remove the ethanol phase. The residual chlorofluorocarbon solution was dried under reduced pressure to obtain a polymer of the above structure. [In the formula, m and n each represent the number of repetitions]

¹ H-NMR (C ₆ F ₆ -D ₂ O): δ 0.10-0.45 (m), 0.50-1.05 (m), 1.05-1.80 (m), 2.90-3.65 (m), 3.65-3.90 (m) .

MALDI-TOF-MS (KRATOS AXIMA-CFR type); positive ion mode, no matrix.

The chart is shown in Figure 1.

From this data, it is known that n=2 and m=3.

Example 34

[In the formula, m and n each represent the number of repetitions]

PFPE vinyl ether trifluoroacetic acid adduct (0.2 mmol) as a cationic polymerization initiator containing PFPE (MW: 4000), and HCFC as a polymerization solvent were added to a glass vessel with a shut-off valve in a dry nitrogen atmosphere. -225 5.82 mL, and 1.0 mL of 1,4-dioxane as a base added. Further, 3-(trimethoxyindenyl)propylvinyl ether (4 mmol) was added to make 9.0 mL of the whole, and the mixture was cooled to 0 °C. To the reaction solution, an ethylaluminum hemichloride (Et _1.5 AlCl _1.5 : 0.2 mmol) solution of HCFC-225 was added under stirring and polymerization was started. After stirring at this temperature for 5 minutes, anhydrous methanol:HCFC-225 (1:1) was added to stop the polymerization. The reaction solution was diluted with HFE7200 and perfluorohexane, and the mixture was separated into a chlorofluorocarbon solution-methanol phase to remove the methanol phase. The residual chlorofluorocarbon solution was dried under reduced pressure to obtain a polymer (Polym1) of the above structure.

¹ H-NMR (C ₆ F ₆ -D ₂ O): δ 0.10-0.45 (m), 1.05-1.80 (m), 2.90 - 3.65 (m), 3.65 - 3.90 (m).

Example 35

[In the formula, m and n each represent a repeat number. 〕

1-(1-Propoxyoxy)-2-(2-triethoxydecylethoxy)ethane is synthesized according to known literature (Crivello, JV, Chem. Mater., 1997, Vol. 9, 1554 pages).

In a dry nitrogen atmosphere, a PFPE vinyl ether trifluoroacetic acid adduct (0.375 mmol) as a cationic polymerization initiator containing a PFPE (MW: 4000) group was added as a polymerization solvent to a glass vessel with a shut-off valve. 5.7 mL of HCFC-225 and 1.0 mL of 1,4-dioxane as a base added. Add 1-(1-propenyloxy)-2-(2-triethoxydecylethoxy)ethane [MW: 292, CH ₃ CH=CHO(CH ₂ ) ₂ O) at 0 ° C 292 mg (0.3 mL, 1 mmol) of (CH ₂ ) ₂ Si(OCH ₂ CH ₃ ) ₃ ]. The reaction vessel was further immersed in a low temperature tank at -30 ° C for 24 hours. After maintaining this temperature, 2 mL of a solution of anhydrous ethanol:HCFC-225 (1:1) cooled to -30 ° C was added to stop the reaction. The reaction solution was diluted with HFE7200 and perfluorohexane, and the chlorofluorocarbon solution-ethanol phase was separated by standing to remove the ethanol phase. The residual chlorofluorocarbon solution was washed with absolute ethanol, and then dried under reduced pressure to obtain a polymer of the above structure.

¹ H-NMR (C ₆ F ₆ -D ₂ O): δ 0.40-1.60 (m), 2.60-3.70 (m), 3.70-4.10 (m).

Example 36

[In the formula, m and n each represent a repeat number. 〕

In a dry nitrogen atmosphere, a PFPE vinyl ether trifluoroacetic acid adduct (0.375 mmol) as a cationic polymerization initiator containing a PFPE (MW: 4000) group was added to a glass vessel with a shut-off valve as a polymerization solvent. HCFC-225 5.7 mL, and 1.0 mL of 1,4-dioxane as a base added. Add 2-(ethyleneoxy)ethyl 3-(triethoxyindenyl)propylaminocarboxylate [CH ₂ =CHO(CH ₂ ) ₂ OCONH(CH ₂ ) ₃ Si at 0 ° C) 279 mg (1 mmol) of (OCH ₃ ) ₃ ] was stirred at this temperature for 24 hours. After maintaining at this temperature, 2 mL of an anhydrous methanol:HCFC-225 (1:1) solution was added to stop the reaction. The reaction solution was diluted with HFE7200 and perfluorohexane, and the chlorofluorocarbon solution-methanol phase was separated by standing to remove the methanol phase. The residual chlorofluorocarbon solution was washed with anhydrous methanol, and dried under reduced pressure to obtain a polymer of the above structure.

¹ H-NMR (C ₆ F ₆ -D ₂ O): δ 0.60-0.80 (m), 0.80-2.20 (m), 3.00-3.20 (m), 3.20-4.05 (m), 4.05 - 4.20 (m) ).

Examples 37a and 37b

[In the formula, m and n each represent a repeat number. 〕

Example 37a structure: PFPE4000-McVE ₉ -OMe

2-(Vinyloxy)ethanol methacrylate was synthesized by known literature (Sugawara, Macromolecules, 2007, Vol. 40, p. 3394).

In a dry nitrogen atmosphere, a PFPE vinyl ether trifluoroacetic acid adduct (0.2 mmol) as a cationic polymerization initiator containing a PFPE (MW: 4000) group was added as a polymerization solvent to a glass vessel with a shut-off valve. 5.82 mL of HCFC-225 and 1.0 mL of 1,4-dioxane as a base added. Further, a solution of 2-(vinyloxy)ethanol ester methacrylate CH ₂ =CHOCH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (302 mg, ₂ mmol) in HCFC-225 (0.6 mL) was added, and the whole was cooled to 0 ° C. . To the reaction solution, an ethylaluminum hemichloride (Et _1.5 AlCl _1.5 : 0.2 mmol) solution of HCFC-225 was added under stirring and polymerization was started. After stirring at this temperature for 60 minutes, a 1% ammonia solution in methanol was added to stop the polymerization. The solvent was distilled off under reduced pressure to give a polymer of the above structure.

¹ H-NMR (C ₆ F ₆ -D ₂ O): δ 1.00-1.10 (m), 1.40-2.00 (m), 2.00-2.50 (m), 3.10 (bs), 3.15-3.95 (m), 4.00 - 4.20 (m), 5.40 (bs), 5.90 (bs).

The integrated value of the methyl group and ethylene H from the initiator was estimated to be m=9 due to the detection of 1.00-1.10.

Example 37b structure: PFPE4000-McVE ₂₀ -OMe

A solution of PFPE vinyl ether trifluoroacetic acid (0.2 mmol) and McVE (CH ₂ = CHOCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ : 602 mg, 4 mmol) in HCFC-225, as in Example 37a, In HCFC-225, polymerization was carried out using ethylaluminum hemichloride (Et _1.5 AlCl _1.5 : 0.2 mmol) (reaction temperature 0 ° C; reaction time 60 minutes). After the solvent was distilled off, ¹ H- was determined by NMR, and it was confirmed that the polymer of the above formula having the number of m of 20 was obtained.

Synthesis Example 9

Synthesis of PFPE-Z-diol-1, ω-bis(ethyleneoxyethoxy)ether

CH ₂ =CH-OC ₂ H ₅ -OCH ₂ -CF ₂ -(OCF ₂ ) _m -(OCF ₂ CF ₂ ) _n -OCF ₂ -CH ₂ OC ₂ H ₅ O-CH=CH ₂

[In the formula, m and n each represent a repeat number. 〕

PFPE-Z-diol (Fomblin Z-dol (trade name); number average molecular weight 4000, Solvay) 1 g (0.25 mmol) and tetrabutylammonium hydrogen sulfate 850 mg (2.5 mmol) were added to a 20 mL eggplant-shaped beaker. 2 mL of a 40% aqueous sodium hydroxide solution and 5 mL of m-hexafluoroxylene were stirred at room temperature for 30 minutes under a nitrogen atmosphere. 2 mL of 2-chloroethyl vinyl ether was added to the above mixture, and a Dimroth condenser was placed in an eggplant-shaped beaker, and stirred at 70 ° C for 72 hours under a nitrogen atmosphere. After cooling, the reaction solution was distilled in a distiller to almost completely dry. The residual reactant was dissolved in a fluorine-based inert liquid (Fluorinert FC-72 (trade name), Sumitomo 3M). The solution was extracted three times with acetone and then with dichloromethane to remove common impurities. Here, the determination that the common impurity is tested by the TLC by the extract (developing solvent: HCFC-225, detection method: spraying and heating of the potassium permanganate solution, determination criteria: disappearance of the spot of the origin). The solvent is distilled off under reduced pressure to obtain the purpose Things.

Hereinafter, this compound is simply referred to as PFPE-Z-diol divinyl ether. Further, the yield was 650 mg (63%).

The structure of the target was confirmed by NMR spectroscopy.

¹ H-NMR (C ₆ F ₆ -D ₂ O): δ 3.40-3.57 (5H, m), 3.59-3.74 (3H, m), 5.88-5.96 (1H, m).

¹⁹ F-NMR (C ₆ F ₆ -D ₂ O): δ -51.5 (bs), -53.1 (bs), -54.8 (bs), -77.2 (bs), -79.2 (bs), -88.5 (bs) ), -90.1 (bs).

The peak of the CF ₂ group at the β position of the raw material alcohol (peaks of -80.4 ppm and -82.4 ppm) disappeared, and the formation of the ether group was confirmed by the detection of the peaks of -77.2 ppm and -79.2 ppm.

Synthesis Example 10

Synthesis of PFPE-Z base containing cationic polymerization initiator

CH ₃ CH(OCOCF ₃ )-OCH ₂ CH ₂ -OCH ₂ CF ₂ -(OCF ₂ ) _m -(OCF ₂ CF ₂ ) _n -OCF ₂ CH ₂ -OCH ₂ CH ₂ -OCH(OCO-CF ₃ )CH ₃

[In the formula, m and n each represent a repeat number. 〕

In the same manner as in Synthesis Example 2, a polymerization initiator having the above structure was synthesized from TFA and PFPE-Z-diol divinyl ether.

The structure was confirmed by the disappearance of ethylene H in the vicinity of 6 ppm in ¹ H-NMR and the appearance of methine H from the acetal ester in the vicinity of 5.5 ppm.

Synthesis Example 11

Synthesis of vinyl ether having a decane coupling group as a hardening portion (3)

In triethoxy decane (20.99g, 128mmol), hexachloroplatinum (IV) acid. In an anhydrous toluene solution (220 mL) of 6 hydrate (55 mg, 0.11 mmol), allyl vinyl ether (9.0 g, 107 mmol) was gradually added dropwise at room temperature. After stirring for 18 hours at room temperature, the reaction mixture was filtered through celite, and the obtained filtrate was concentrated under reduced pressure, and the residue was evaporated under reduced pressure (bp 70 ° C, 1 mmHg) Yield 74%).

¹ H-NMR (CDCl ₃ ): δ 0.60-0.68 (2H, m), 1.18 (9H, t, J = 6.8 Hz), 1.68-1.78 (2H, m), 3.35 (2H, t, J = 6.4 Hz ), 3.78 (6H, q, J = 6.8 Hz), 3.93 (1H, d, J = 6.9 Hz), 4.00 (1H, d, J = 14.2 Hz), 6.28 (1H, dd, J = 14.2, 6.9 Hz) ).

Synthesis Example 12

Synthesis of vinyl ether having a decane coupling group as a hardening portion (4)

The synthesis of trimethoxydecane was carried out in the same manner as in Synthesis Example 11. Vinyl ether 4 of the alkene coupling group (bp 56 ° C, 100 Pa).

¹ H-NMR (CDCl ₃ ): δ 0.48-0.60 (2H, m), 1.55-1.75 (2H, m), 3.31 (9H, s), 3.30-3.55 (2H, m), 3.78-3.85 (1H, m), 3.90-4.10 (1H, m), 6.23-6.35 (1H, m).

Example 38

[In the formula, m, n, p, and q each represent a repeating number. 〕

A PFPE (FomblinZ)-based cationic polymerization initiator (0.2 mmol) prepared in Synthesis Example 10 as a cationic polymerization initiator containing a PFPE group was added to a glass vessel with a shut-off valve in a dry nitrogen atmosphere. As a polymerization solvent, 5.82 mL of HCFC-225 and 1.0 mL of 1,4-dioxane as a base to be added. Further, 3-(triethoxyindenyl)propyl vinyl ether (4 mmol) was added to make 9.0 mL of the whole, and the mixture was cooled to 0 °C. To the reaction solution, an ethylaluminum hemichloride (Et _1.5 AlCl _1.5 : 0.2 mmol) solution of HCFC-225 was added under stirring and polymerization was started. After stirring at this temperature for 5 minutes, anhydrous ethanol:HCFC-225 (1:1) was added to stop the polymerization. The reaction solution was diluted with HFE7200 and perfluorohexane, and the chlorofluorocarbon solution-ethanol phase was separated by standing to remove the ethanol phase. The residual chlorofluorocarbon solution was dried under reduced pressure to obtain a polymer of the foregoing structure.

In the ¹ H-NMR, since the methine H of the ethylene H and the acetal ester was not confirmed, it was confirmed that the object was obtained.

Synthesis Example 13

Synthesis of vinyl ether having a decane coupling group as a hardening portion (5)

In the same manner as in Synthesis Example 11, a vinyl ether 5 having a trichloropurin group (bp 56 ° C, 100 Pa) was synthesized using trichloromethane.

¹ H-NMR (CDCl ₃ ): δ 0.99-1.08 (2H, m), 1.80-1.98 (2H, m), 3.40-3.55 (2H, m), 3.80-3.85 (1H, m), 3.88-4.05 ( 1H, m), 6.25-6.30 (1H, m).

Example 39

[In the formula, m represents the number of repetitions]

In the same manner as in Example 33, a PFPE vinyl ether trifluoroacetic acid adduct (0.2 mmol) as a cationic polymerization initiator containing a PFPE (MW: 4000) group, HCFC-225 5.82 mL as a polymerization solvent, and the like were added. 1.0 mL of base 1,4-dioxane was added. Further, 3-(trichloroindenyl)propylvinyl ether (4 mmol) was added to make 9.0 mL of the whole, and the mixture was cooled to 0 °C. To the reaction solution, an ethylaluminum hemichloride (Et _1.5 AlCl _1.5 : 0.2 mmol) solution of HCFC-225 was added under stirring and polymerization was started. After stirring at this temperature for 5 minutes, the reaction liquid was cooled to 0 ° C, dimethylamine:HCFC-225 (1:1) was added, and the mixture was further stirred at room temperature for 15 hours. The reaction solution was diluted with perfluorohexane and tetrahydrofuran (THF), and the THF phase was removed by separating the two phases of perfluorohexane solution-THF by standing. The residual perfluorohexane solution was dried under reduced pressure to obtain a polymer (Polym 2) of the foregoing structure.

The reaction product was compared with the ¹ H-NMR of the product in the middle of the reaction, and the product was detected in a singlet state of 2.9 ppm from N-CH ₃ to confirm the structure of the target.

Test example 2

In Example 40, the polymer (Polym1) obtained in Example 34 and the perfluoropolyether compound (a, b) having the following two types of structures were mixed at 50:20:30, and applied as a solution of HFE7200. A glass substrate (chemically strengthened glass manufactured by Corning Incorporated, Gorilla (trade name) glass, thickness: 0.7 mm) was dried to form a film.

a: CF ₃ O(CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₃ average molecular weight 12,500

b: CF ₃ O(CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₃ average molecular weight 8000 [In the formula, p and q each represent a repeating number. 〕

Further, in the same manner as in Example 40, as in Example 41, a film of Polym1 was formed on a glass substrate.

Further, as Comparative Examples 11 and 12, a film of each compound a or compound b was formed on a glass substrate in the same manner as in Example 40.

Further, as Example 42, a film of the polymer (Polym 2) obtained in the above Example 39 was formed on a glass substrate in the same manner as in Example 40.

(1) Appearance (appearance, haze), (2) feeling of use of fingers (surface lubricity), (3) dynamic friction coefficient (surface lubricity), and (4) abrasion of the above-mentioned compound film obtained after drying The endurance number (wear durability) is evaluated or measured.

Benchmark in each project As shown below.

(1) Appearance

(Visual): Evaluation was performed on the basis of the following criteria.

○: There is no particle in the surface of the coating after drying.

×: There are particles in the surface of the coating film after drying and drying.

(Haze): fog value (%: measured by the fog value detector)

(2) Sense of use of the fingers (surface lubricity): The sensor evaluator touches the surface of the film with a finger, and the feeling of use is evaluated based on the following criteria. estimate.

1: very good

2: Good

3: ordinary

4: Poor

(3) Dynamic friction coefficient (surface lubricity)

A surface measuring machine ("Toraibogia type 14FW type" manufactured by Shinto Scientific Co., Ltd.) was used, and a steel ball was used as a friction member, and a dynamic friction coefficient (-) was measured in accordance with ASTM D1894.

(4) Durability of wear (wear durability)

Steel wool (line number #0000, size 10 mm x 10 mm x 5 mm) was brought into contact with the surface of the film, and reciprocally wiped at a speed of 140 mm/sec at a load of 1000 gf.

After 500 times of reciprocating, the static contact angle of water was measured (using "DropMaster" manufactured by Kyowa Interface Science Co., Ltd., and the water contact angle of the liquid amount of 1 μL of water was measured). The contact angle is a frictional number of 100 degrees or less as the abrasion durability.

The results obtained in Examples 40 to 42 and Comparative Examples 11 and 12 are summarized in the sub-table.

Examples 43 to 54

Synthesis of copolymers containing PFPE-based and hardenable parts (A-B-N type) (3)

Example 43

In the same manner as in Example 1, a PFPE 4000 VETFA solution (HCFC-225; equivalent to 0.2 mmol) as a cationic polymerization initiator containing a PFPE group and a monomeric McVEE solution (HCFC-225; 4.0 mmol) containing a curable portion were used. A solution of HCFC-225-1,4-dioxane (5.26 mL-1.0 mL) was used at 0 ° C under dry nitrogen using 1 mL of ethyl aluminum semi-chloride solution (HCFC-225; Et _1.5 AlCl _1.5 : 0.2 mmol). Polymerization (8 minutes). After the post-treatment, the structure was confirmed by NMR and GPC.

Mnx10 ^-3 = 5.6 Mw / Mn = 1.21

¹ H-NMR (CDCl ₃ ): δ 1.05-1.20 (m), 1.40-2.00 (m), 1.95 (bs), 3.30 (bs), 3.35-3.80 (m), 3.80-4.0 (m), 4.20- 4.40 (m), 5.50-5.60 (m), 6.05-6.15 (m).

The block ratio of the terminal PFPE group to the hardenable portion is determined by the proton integral value of the end OCH ₃ group observed at 3.3 ppm and the olefin proton observed at 5.50-5.60 ppm and 6.05-6.15 ppm (the number of m of the above structural formula) ) is 20.

The compounds of Examples 44 to 54 were synthesized in the same manner as in Example 43 under the materials and conditions shown in Table 11, and the number of m of each structural formula was estimated.

For each of these, various physical properties were measured in the same manner as in Example 1. The results are summarized in Tables 12 and 13.

Example 55

In the same manner as in Example 1, the PFPE group contained a cationic polymerization initiator (polymerization initiator 5c) solution (HCFC-225; equivalent to 0.2 mmol) and a monomeric McVEE solution of the curable portion (HCFC-225; 2.0 mmol). a solution of HCFC-225-1,4-dioxane (5.63 mL-1.0 mL) using 1 mL of ethylaluminum semi-chloride solution at 0 ° C under dry nitrogen (HCFC-225; Et _1.5 AlCl _1.5 :0.2) Methyl) was polymerized (30 minutes). After work-up, the structure was confirmed by NMR.

¹ H-NMR (CDCl ₃ ): δ 1.10 (bs), 1.40-2.00 (m), 1.95 (bs), 3.30 (bs), 3.35-3.80 (m), 3.80-4.0 (m), 4.20-4.40 ( m), 5.50-5.60 (m), 6.05-6.15 (m).

The terminal PFPE group and the hardenable portion were estimated from the terminal CH ₃ group observed at 1.1 ppm and the terminal OCH ₃ group observed at 3.3 ppm and the proton integral value of the olefin proton observed at 5.50-5.60 ppm and 6.05-6.15 ppm. The block ratio is 10.

○ It can be dissolved transparently and uniformly.

△ Although it is turbid, it is soluble.

× no dissolution

[Oil ink - pop-up]

The ink is ejected with almost no residue

○: The ink is ejected and cannot be a line

△: The ink is ejected, but the line has a residue.

×: The ink is ejected and the line can be drawn.

[oily ink - wiping]

◎: The ink can be wiped very lightly, with no residue at all.

○: The ink can be wiped off and there is no residue on the surface.

△: The ink cannot be wiped and remains on the surface.

×: The ink cannot be wiped and remains on the surface.

From the above results, it has been found that the perfluoropolyether compound having no binder of the substrate has a feeling of use with high lubricity, but the durability as a surface-treated film is extremely low. On the other hand, the compound of the present invention having a bonding group with a substrate has excellent durability, and the feeling of use has an impression of deterioration when compared with a perfluoropolyether compound. On the other hand, it has been determined that by combining a compound having the binding group and a compound having no binding group, it is possible to obtain an excellent surface treatment film which has both a feeling of use and durability.

And as a binding group to the substrate, it is judged that the oxime ether group is used as the decazane At the base time, the durability can be further improved. This is considered to be an effect from a hydrazine alkyl group as a binding group.

[Industrial availability]

The fluorinated copolymer of the present invention can be suitably used as an oil-repellent and/or water-repellent coating agent having both oil repellency and water repellency and high solubility to a general-purpose solvent (non-fluorine-containing organic solvent).

Claims (37)

a fluorine-containing copolymer represented by the formula (1); ^Wherein R ^a1 represents a monovalent or divalent group containing a perfluoropolyether group, X ^a represents -O-, a phenyl group, a -N(-R ^E )- (R ^E represents an organic group) or a hydrazine An azole group, R ^a2 represents a hydrogen atom or an alkyl group, and R ^a3 represents a hydrogen atom or an alkyl group, and each Q is independently represented as a constituent unit containing a curable portion or a constituent unit not containing a curable portion, and R ^c represents a perfluoropolyether group-containing group or an organic group or a hydrogen atom which may also contain a hardenable portion, X ^c represents -O-, -S-, -NH- or a single bond, k represents 1 or 2, and n1 represents 1 or more. The number of repetitions, but at least one of R ^a2 and R ^a3 is an alkyl group, and when R ^{c is} not an organic group containing a curable portion, at least one Q is a constituent unit containing a curable portion. The fluorocopolymer of claim 1, wherein Q is a constituent unit represented by the following formula; ^Wherein each R ^b1 is independently represented by a hydrogen atom or an alkyl group, and each R ^b2 is independently represented by a hydrogen atom or an organic group which may also contain a hardenable moiety, and R ^b3 represents a hydrogen atom or an alkyl group. X ^b represents -O-, phenyl group, -N(-R ^E )-(R ^E represents an organic group) or an extended carbazole group. However, when R ^b2 is a hydrogen atom, X ^b is a stretching phenyl group. The fluorinated copolymer according to claim 1 or 2, wherein the number average molecular weight of the perfluoropolyether group in the monovalent or divalent group of the perfluoropolyether group represented by R ^a1 is about 1,000 or more. The fluorinated copolymer according to any one of claims 1 to 3, wherein the perfluoropolyether group in the perfluoropolyether group represented by R ^a1 has a moiety represented by the following formula; _{(C p F 2p O) n} - wherein each p is independently based on the event is an integer of 1 to 6, n-represents the number of repetitions. The fluorocopolymer of claim 4, wherein R ^a1 is a monovalent formula represented by the formula: X ^ra -(C _p F _2p O) _na -Y ^ra -L ^a - (a1) X ^ra represents fluorine or Rf-O- (Rf represents a perfluoroalkyl group having 1 to 8 carbon atoms), and each p is independently represented by an integer of 1 to 6, and na represents a repeat number of 1 to 1000, Y ^ra It represents a perfluoroalkylene chain having ^a carbon number of 1 to 6, and La represents a linking group. The fluorocopolymer of claim 5, wherein the moiety represented by the formula: (C _p F _2p O) _na in the formula (a1) is selected from the group consisting of -CF ₂ -CF ₂ -CF ₂ -O-, - _{CF (-CF 3) -CF 2 -O} -, - CF 2 -O -, - CF 2 -CF 2 -O- and -CF (-CF ₃₎ -O- least one of the groups of the constituent units Composition. The fluorocopolymer of claim 6, wherein the moiety represented by the formula: (C _p F _2p O) _na is composed of -CF ₂ -CF ₂ -CF ₂ -O-, and Y ^ra is -CF ₂ -CF ₂ -. The fluorocopolymer of claim 6, wherein the moiety represented by the formula: (C _p F _2p O) _na is composed of -CF ₂ -CF ₂ -O- and -CF ₂ -O-, and Y ^ra For -CF ₂ -. The fluorocopolymer of claim 6, wherein the moiety represented by the formula: (C _p F _2p O) _na is composed of -CF(-CF ₃ )-CF ₂ -O-, and Y ^ra is -CF (-CF ₃ )-. The fluorocopolymer of claim 6, wherein the moiety represented by the formula: (C _p F _2p O) _na is composed of -CF(-CF ₃ )-CF ₂ -O- and -CF ₂ -O- And Y ^ra is -CF(-CF ₃ )-. The fluorine-containing copolymer according to any one of items 5 to 10, such as a request, where L ^a is _{-CH 2 -O-CH 2 -CH 2} -. The requested item fluorine-containing copolymer according to any one of 5 to 10, wherein L ^a is -CH ₂ -. The fluorinated copolymer according to claim 4, wherein R ^a1 is a divalent group represented by the following formula; and: -L ^a' -Y ^ra' -O-(C _p F _2p O) _na -Y ^ra - In the formula L ^a - (a2), L ^{a '} and L ^a each independently represent a linking group, and Y ^{ra '} and Y ^ra each independently represent a perfluoroalkylene chain having 1 to 6 carbon atoms, and each p is present. Each represents an integer from 1 to 6, and na represents a repetition of 1 to 1000. The fluorocopolymer of claim 13, wherein the moiety represented by the formula (a2): (C _p F _2p O) _na is independently selected from the group consisting of -CF ₂ -CF ₂ -CF ₂ -O- _{, -CF (-CF 3) -CF 2} -O -, - CF 2 -O -, - CF 2 -CF 2 -O- and -CF (-CF ₃₎ -O- least one of the groups of The constituent units are composed. The fluorocopolymer of claim 13, wherein Y ^ra' is -CF ₂ -CF ₂ -, and the moiety represented by the formula: (C _p F _2p O) _na is -CF ₂ -CF ₂ -CF ₂ -O - constituted, and Y ^ra is -CF ₂ -CF ₂ -. The fluorocopolymer of claim 13, wherein Y ^ra' is -CF ₂ -, and the moiety represented by the formula: (C _p F _2p O) _na is -CF ₂ -CF ₂ -O-, and -CF ₂ -O- is formed, and Y ^ra is -CF ₂ -. The fluorocopolymer of claim 13, wherein Y ^ra' is -CF(-CF ₃ )-, and the moiety represented by the formula: (C _p F _2p O) _na is derived from -CF(-CF ₃ )-CF ₂ -O- is formed, and Y ^ra is -CF(-CF ₃ )-. The fluorocopolymer of claim 13, wherein Y ^ra' is -CF(-CF ₃ )-, and the moiety represented by the formula: (C _p F _2p O) _na is derived from -CF(-CF ₃ )-CF ₂ -O-, and -CF ₂ -O-, and Y ^ra is -CF(-CF ₃ )-. The fluorinated copolymer according to claim 4, wherein the perfluoropolyether group in the perfluoropolyether group represented by R ^a1 is a divalent group represented by the following formula; and: -L ^a' - Y ^ra' -(OC _p' F _2p' ) _na' -O-Rf-O-(C _p F _2p O) _na -Y ^ra -L ^a - (a2') where L ^{a '} and L ^a are Each of them independently represents a linking group, and Y ^ra' and Y ^ra each independently represent a perfluoroalkylene chain having a carbon number of 1 to 6, and na' and na each independently represent a repeating number of 1 to 1000, and Rf represents a perfluoroalkylene group. Base chain. The fluorocopolymer of claim 19, wherein Y ^ra' is -CF(-CF ₃ )-, and the moiety represented by the formula: (OC _p' F _2p' ) _na' is -O-CF ₂ -CF ( -CF ₃ )-, Rf is a perfluoroalkylene chain having a carbon number of 1 to 8, and the moiety represented by the formula: (C _p F _2p O) _na is -CF(-CF ₃ )-CF ₂ -O -, and Y ^ra is -CF(-CF ₃ )-. The request to any of item 13 to 20 - of the fluorine-containing copolymer, wherein L ^{a 'is} _{-CH 2 -CH 2 -O-CH 2} -, and L ^a is _{-CH 2 -O-CH 2 -CH 2} - . The requested item 13 to 20 according to any one of the fluorine-containing copolymer, wherein L ^{a 'is} -CH ₂ -, and L ^a is -CH ₂ -. The fluorinated copolymer according to any one of claims 1 to 22, wherein R ^{c is} not an organic group containing a curable portion, and at least one Q is a constituent unit containing a curable portion. The fluorinated copolymer according to claim 23, wherein the hardenable portion in Q is a (meth) acrylonitrile group or a decane coupling group. The fluorinated copolymer according to claim 23 or 24, wherein the constituent unit containing the curable portion is a group in which the curable portion is bonded to X ^b via a linking group, and the linking group is -(CHR ^y ) _n - O- or -(CHR ^y ) _n -O-(CHR ^y ) _n -O- (each n is independently represented by a repeating number of integers from 1 to 40, and each R ^y is independently represented by hydrogen Or methyl). The fluorocopolymer of any one of claims 23 to 25, wherein R ^c is a methyl group. The fluorinated copolymer according to any one of claims 1 to 25, wherein R ^c is an organic group containing a hardenable portion. The fluorocopolymer of claim 27, wherein R ^c is a group containing a decane coupling group. An oil-repellent and/or water-repellent coating agent comprising the fluorine-containing copolymer according to any one of claims 1 to 28. The oil-repellent and/or water-repellent coating agent of claim 29, which further comprises a compound represented by the following formula; formula (2): R ^r1 -O-(C _r F _2r O) _nd -R ^r2 Each of the r is independently an integer of 1 to 6, and nd represents a repeating number, and R ^r1 and R ^r2 each independently represent a carbon number of 1 to 16, preferably a perfluoroalkyl group having 1 to 3 carbon atoms. An article comprising a film formed from the oil-repellent and/or water-repellent coating agent of claim 29 or 30. A manufacturing method which is a method for producing a compound represented by the following formula: Wherein PFPE represents F-(CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeat number), and Y ^a represents a decyloxy group or a halogen atom], which is characterized by 2-Poly(perfluoropropyloxy)methoxyethoxy group represented by the formula: PFPE-CH ₂ -OC ₂ H ₄ O-CH=CH ₂ (wherein the symbol represents the same meaning as defined above) A step of reacting ^a vinyl ether with a compound represented by the formula: Y ^a -H (the symbol in the formula represents the same meaning as defined above). A manufacturing method which is a method for producing a compound represented by the following formula: [Wherein, the PFPE represents _{F- (CF 2 -CF 2 -CF 2} -O) n -CF 2 -CF 2 - (n represents the number of repetitions), Y ^a represents acyl group or a halogen atom], characterized by comprising ₂ -P-(perfluoropropyloxy)methoxyvinyl ether represented by the formula: PFPE-CH ₂ -O-CH=CH ₂ (the symbol in the formula is the same as defined above), and the formula: Y ^a The step of reacting a compound represented by -H (the symbol in the formula represents the same meaning as described above). A manufacturing method which is a method for producing a compound represented by the following formula: [Wherein, PFPE represents a _{-CF (-CF 3) - (O} -CF 2 -CF (-CF 3)) n -O-CF 2 -Rf-CF 2 -O- (CF (-CF 3) -CF ₂ -O-) _n' -CF(CF ₃ )-(Rf represents a perfluoroalkylene group, n and n' are each a repeating number, and Y ^a represents a decyloxy group or a halogen atom], which is characterized by containing :CH ₂ =CH-OC ₂ H ₄ -O-CH ₂ -PFPE-CH ₂ -OC ₂ H ₄ -O-CH=CH ₂ (the symbol in the formula represents the same meaning as described above), and A step of reacting a compound represented by the formula: Y ^a -H (the symbol in the formula represents the same meaning as described above). A manufacturing method which is a method for producing a compound represented by the following formula: Wherein PFPE represents -CF ₂ CF ₂ -O-(CF ₂ -CF ₂ CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeating number), and Y ^a represents a decyloxy group or a halogen atom] , which is characterized by containing the formula: CH ₂ =CH-OC ₂ H ₄ -O-CH ₂ -PFPE-CH ₂ -OC ₂ H ₄ -O-CH=CH ₂ (the symbol in the formula represents the same meaning as described above) The compound represented by the compound is reacted with a compound represented by the formula: Y ^a -H (the symbol in the formula represents the same meaning as defined above). A manufacturing method which is a method for producing a compound represented by the following formula: Wherein PFPE represents -CF ₂ CF ₂ -O-(CF ₂ -CF ₂ CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeating number), and Y ^a represents a decyloxy group or a halogen atom] And characterized by comprising a compound represented by the formula: CH ₂ =CH-O-CH ₂ -PFPE-CH ₂ -O-CH=CH ₂ (the symbol in the formula represents the same meaning as described above), and the formula: Y The step of reacting a compound represented by ^a -H (the symbol in the formula represents the same meaning as described above). Item 32 The method according to any one of a request to 36, wherein the formula: Y ^a -H The compound represented by CF ₃ COOH.