JPH11217451A - Fluoro polymer coating film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluoro polymer coating film which can efficiently impart surface performances such as water/oil repellency and stainproofing properties to a substrate such as a synthetic resin material or an inorganic material. SOLUTION: The fluoro polymer coating film is one composed of the two layers of a layer of polymer segment (I) on the side of the substrate and a layer of a tluoro polymer segment (II) formed thereon. The layer (II) is bonded to the layer (I) through fragments of peroxy bonding groups. The segment (I) is formed from a monomer containing a peroxy bonding group, and the segment (II) is formed from a fluoro monomer. This film is produced by applying a solution of a fluoro monomer to the layer formed from the polymer having peroxy bonding groups and heating the applied solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing polymer film used as a functional film having special functions such as water repellency, oil repellency and antifouling property, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, surface protection or water / oil / oil repellency, antifouling, non-adhesion, abrasion resistance, abrasion resistance, and chemical resistance of various substrates such as synthetic resins, films, and inorganic materials. As a functional film having a special function such as anti-ice and snow fixation, a film of a silicone or fluorine resin compound is mainly used in many cases.

As a method for producing the functional film, for example, a paint in which a fluorocarbon fine powder such as polytetrafluoroethylene or the like is suspended in ethanol or the like is applied to a substrate, dried, and then dried at about 400 ° C. for about 1 hour. A method of performing a baking process and the like are known.

There is also known a method of imparting characteristics to a surface by chemically bonding a (per) fluoroalkyl group or a (per) fluoroalkylene group to a polymer material. In this method, for example, an attempt has been made to impart water- and oil-repellency, weather resistance and stain resistance to a coating film surface based on a (per) fluoroalkyl group or a (per) fluoroalkylene group. JP-A-57-3407 and JP-A-57-34
No. 08 discloses that a random copolymer formed from a fluoroolefin as a main component and a vinyl monomer copolymerizable with the fluoroolefin forms a coating film having excellent weather resistance. .

Further, JP-A-58-34866 and JP-A-58-34867 disclose an acrylic or methacrylic ester containing a (per) fluoroalkyl group as an essential component, which can be copolymerized therewith. It is disclosed that a random copolymer composed of various vinyl monomers forms a coating film having excellent weather resistance, water and oil repellency and stain resistance.

Further, a method has been proposed in which a fluorine-containing compound is added to the inside of a polymer material to impart a property based on the fluorine-containing compound to the surface of the polymer material. For example, in Polymer Bulletin, vol. 5,335 (1981) and JP-A-57-179246, a vinyl polymerizable double bond is provided to one end of polymethyl methacrylate (macromonomer), By copolymerizing the acrylate having a perfluoroalkyl group, a graft copolymer having a polymethyl methacrylate branch and an acrylate having a perfluoroalkyl group arranged at the back is obtained. By adding this graft copolymer to poly (methyl methacrylate), the surface is given water and oil repellency.

[0007]

However, the above-described method of baking at a high temperature of about 400 ° C. cannot be applied to wood, plastic, and the like, and is limited by the substrate to which it is applied. was there.

In the method described in Japanese Patent Application Laid-Open No. 57-3407, if the rate of the fluorine-containing monomer forming the polymer is small, the surface may have a (per) fluoroalkyl group or A property based on a (per) fluoroalkylene group cannot be imparted. On the other hand, as the proportion of the fluorine-containing monomer forming the polymer increases, the surface modification effect appears, and the persistence of the modification effect is improved, but the polymer becomes expensive, In addition, there is a problem that the properties of the fluorine-free monomer forming the polymer are hardly reflected on the polymer.

Furthermore, in the method of adding a fluorine-containing compound using a macromonomer to the inside of a polymer material, the synthesis method is complicated, and the molecular weight of the macromonomer is kept low to some extent (number average molecular weight: 1000 to 10,000). Because of the necessity, the polymethyl methacrylate portion, which is a branch portion in the graft copolymer, is an oligomer having a number average molecular weight of 10,000 or less. Therefore, when this graft copolymer is added to polymethyl methacrylate to be modified, it is not necessarily sufficiently captured by the polymer material because of its low molecular weight. There was a problem that the effect could not be maintained in some cases. Moreover,
There is a problem that the practical coating film strength is lacking and that the adhesion to a substrate to which a special function is to be imparted is insufficient.

As described above, in the conventional method, the surface of a polymer material or the like has not been industrially easily and sufficiently modified to be satisfactory. The present invention has been made by paying attention to the problems existing in the prior art as described above.
The purpose is to have good performance such as water repellency, oil repellency, and antifouling property, have practical coating strength, and have good adhesion to a substrate to which a special function is to be imparted. It is to provide a fluorine-containing polymer coating. Another object of the present invention is to provide a method for producing a fluorine-containing polymer film which can suppress the risk of being restricted by usable substrates and can be easily produced.

[0011]

Means for Solving the Problems The present inventors have made intensive studies in order to achieve the above-mentioned object, and as a result, have completed the present invention.

That is, the fluorine-containing polymer film according to the first invention is a fluorine-containing polymer film formed on a substrate, wherein the polymer segment having a peroxide bonding group is formed on the substrate. It comprises a layer of (I) and a layer of a fluorine-containing polymer segment (II) formed from a fluorine-containing monomer bonded via the above-mentioned peroxide bonding group.

[0013] The fluorine-containing polymer film of the second invention according to the first invention, wherein the fluorine-containing polymer segment (II) is represented by the following general formula (1), (2), (3) or (4).
And at least one fluorine-containing monomer selected from the group consisting of (5).

CH_Two= CR¹COOR^TwoRf (1) (where R¹Is a hydrogen atom or a methyl group, R^TwoIs -C_pH
_2p-, -C (C_pH_{2p + 1}) H-, -CH_TwoC (C_pH
_{2p + 1}) H- or -CH_TwoCH_TwoO- and Rf are -C_nF
_{2n + 1},-(CF_Two)_nH,-(CF_Two)_pOC_nH_2nC
_iF_{2i + 1},-(CF_Two)_pOC_mH_2mC_iF_2iH, -N
(C_pH_{2p + 1}) COC_nF_{2n + 1}, -N (C_pH _{2p + 1}) S
O_TwoC_nF_{2n + 1}It is. However, p is 1 to 10 and n is 1 to
16, m is an integer of 0 to 10, and i is an integer of 0 to 16. ) CF_Two= CFORg (2) (wherein Rg represents a fluoroalkyl group having 1 to 20 carbon atoms)
I forgot. ) CH_Two= CHRg (3) (wherein Rg represents a fluoroalkyl group having 1 to 20 carbon atoms)
I forgot. ) CH_Two= CR^ThreeCOOR^FiveRj R⁶OCOCR^Four= CH_Two ... (4) (where R^Three, R^FourIs a hydrogen atom or a methyl group, R^Five, R
⁶Is -C_qH_2q-, -C (C_qH_{2q + 1}) H-, -CH_Two
C (C_qH_{2q + 1}) H- or -CH_TwoCH_TwoO- and Rj are
-C_tF_2tIt is. Here, q is 1 to 10, and t is 1 to 16.
Is an integer. )

[0015]

Embedded image (Wherein R ⁷ and R ⁸ are hydrogen atoms or methyl groups, and R k is-
C _y F _{2y + 1} . Here, y is an integer of 1 to 16. The fluorine-containing polymer film according to the third invention is the fluorine-containing polymer film according to the first invention or the second invention, wherein the polymer segment (I) is formed from a monomer having a peroxide bonding group.

According to a fourth aspect of the present invention, there is provided a method for producing a fluorine-containing polymer film, comprising forming a polymer layer having a peroxide-bonding group on a base material, and coating a fluorine-containing monomer on the layer. Fifteen
This is a method for producing the fluorine-containing polymer coating of the first invention, wherein the coating is heated to 0 ° C.

According to a fifth aspect of the present invention, there is provided the method for producing a fluorine-containing polymer film according to the fourth aspect, wherein the polymer having a peroxide bonding group is represented by the following general formula (6), (7), (8) or ( It is formed from a monomer having at least one selected from the group consisting of peroxide bonding groups consisting of 9) and (10).

[0018]

Embedded image(Where R¹Is a hydrogen atom or a methyl group, R^TwoIs a hydrogen atom
Or a methyl group, R^Three, R ^FourIs an alkyl having 1 to 4 carbon atoms
Group, R^FiveIs an alkyl group having 1 to 12 carbon atoms, 3 to
12 cycloalkyl groups, phenyl groups, alkyl group substitution
Represents a phenyl group, and n represents 1 to 5. )

[0019]

Embedded image(Where R⁶Is a hydrogen atom or a methyl group, R⁷Is a hydrogen atom
Or a methyl group, R⁸, R ⁹Is an alkyl having 1 to 4 carbon atoms
Group, R^TenIs an alkyl group having 1 to 12 carbon atoms, 3 to
12 cycloalkyl groups, phenyl groups, alkyl group substitution
Represents a phenyl group, and n represents 0 to 4. )

[0020]

Embedded image (Wherein, R ¹¹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group,
The alkyl-substituted phenyl group, R ¹² and R ¹³ have 1 to 1 carbon atoms.
An alkyl group of 4, R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group,
Represents an alkyl-substituted phenyl group. )

[0021]

Embedded image (Wherein, R ¹⁵ is a hydrogen atom or a methyl group, R ¹⁶ and R ¹⁷ are an alkyl group having 1 to 4 carbon atoms, R ¹⁸ is an alkyl group having 1 to 12 carbon atoms, and cycloalkyl having 3 to 12 carbon atoms) Group, phenyl group, and alkyl-substituted phenyl group.)

[0022]

Embedded image (Wherein, R ¹⁹ is a hydrogen atom or a methyl group, R ²⁰ and R ²¹ are an alkyl group having 1 to 4 carbon atoms, R ²² is an alkyl group having 1 to 12 carbon atoms, and cycloalkyl having 3 to 12 carbon atoms. Group, phenyl group, and alkyl-substituted phenyl group.)

[0023]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. The fluorine-containing polymer film of the present invention is characterized by its structure, and comprises a layer comprising a polymer segment (I) formed on a substrate and a fluorine-containing polymer segment (II) formed thereon. Are chemically bonded via a peroxide bonding group fragment.
More specifically, the fluorine-containing polymer coating is composed of a graft copolymer comprising a polymer segment (I) and a fluorine-containing polymer segment (II) formed on a substrate. In this graft copolymer, a fluorine-containing polymer segment (II) as a side chain is bonded to a polymer segment (I) as a main chain via a peroxide bonding group fragment.

The layer composed of the polymer segment (I) and the layer composed of the fluorine-containing polymer segment (II) formed on the base material may each contain a homopolymer which is not bonded to each other. . That is, even if the graft efficiency is low, it is sufficient that the intended purpose can be achieved.

The polymer segment (I) formed on the base material is a polymer obtained by polymerizing a monomer having a peroxide bonding group, and a polymer having a fragment in which the peroxide bonding group is cleaved. Refers to union. Here, the monomer having a peroxide bonding group is a group capable of generating a radical by heating,
That is, it means a compound having one or more peroxide bonding groups and one or more polymerizable unsaturated double bonds in one molecule.

Specific examples of the monomer having a peroxide bonding group include monomers represented by the following general formulas (6) to (10).

[0027]

Embedded image(Where R¹Is a hydrogen atom or a methyl group, R^TwoIs a hydrogen atom
Or a methyl group, R^Three, R ^FourIs an alkyl having 1 to 4 carbon atoms
Group, R^FiveIs an alkyl group having 1 to 12 carbon atoms, 3 to
12 cycloalkyl groups, phenyl groups, alkyl group substitution
Represents a phenyl group, and n represents 1 to 5. )

[0028]

Embedded image(Where R⁶Is a hydrogen atom or a methyl group, R⁷Is a hydrogen atom
Or a methyl group, R⁸, R ⁹Is an alkyl having 1 to 4 carbon atoms
Group, R^TenIs an alkyl group having 1 to 12 carbon atoms, 3 to
12 cycloalkyl groups, phenyl groups, alkyl group substitution
Represents a phenyl group, and n represents 0 to 4. )

[0029]

Embedded image (Wherein, R ¹¹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group,
The alkyl-substituted phenyl group, R ¹² and R ¹³ have 1 to 1 carbon atoms.
An alkyl group of 4, R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group,
Represents an alkyl-substituted phenyl group. )

[0030]

Embedded image (Wherein, R ¹⁵ is a hydrogen atom or a methyl group, R ¹⁶ and R ¹⁷ are an alkyl group having 1 to 4 carbon atoms, R ¹⁸ is an alkyl group having 1 to 12 carbon atoms, and cycloalkyl having 3 to 12 carbon atoms) Group, phenyl group, and alkyl-substituted phenyl group.)

[0031]

Embedded image (Wherein, R ¹⁹ is a hydrogen atom or a methyl group, R ²⁰ and R ²¹ are an alkyl group having 1 to 4 carbon atoms, R ²² is an alkyl group having 1 to 12 carbon atoms, and cycloalkyl having 3 to 12 carbon atoms. Group, a phenyl group, or an alkyl-substituted phenyl group.) The types and carbon numbers of the functional groups of the monomers represented by the general formulas (6) to (10) are set from the viewpoint of practical availability. Have been.

Specific examples of the monomer having a peroxide bonding group represented by the general formula (6) include t-butylperoxy (meth) acryloyloxyethyl carbonate,
t-butylperoxy (meth) acryloyloxyethoxyethyl carbonate, t-butylperoxy (meth) acryloyloxyisopropyl carbonate, t-amylperoxy (meth) acryloyloxyethyl carbonate, t-amylperoxy (meth) acryloyloxyisopropyl carbonate, t -Hexylperoxy (meth) acryloyloxyethyl carbonate, t-hexylperoxy (meth) acryloyloxyisopropyl carbonate, t-octylperoxy (meth) acryloyloxyethyl carbonate, cumylperoxy (meth) acryloyloxyethyl carbonate, p-isopropylc Milperoxy (meth) acryloyloxyethyl carbonate, p-menthylperoxy (meth) acryloyloxyethyl ester Boneto, 1-cyclohexyl
-1-methylethyl peroxy (meth) acryloyloxyethyl carbonate and the like.

Specific examples of the monomer having a peroxide bonding group represented by the general formula (7) include t-butylperoxy (meth) allylcarbonate and t-butylperoxy (meth) allyloxyethyl. Carbonate, t-butylperoxy (meth) allyloxyethoxyethyl carbonate, t-amylperoxy (meth) allyl carbonate, t-hexylperoxy (meth) allylcarbonate, t-octylperoxy (meth) allylcarbonate, cumyl (meth) allyl Carbonate and the like.

Specific examples of the monomer having a peroxide bonding group represented by the general formula (8) include t-butyl peroxymethyl fumarate, t-butyl peroxyethyl fumarate, and t-butyl peroxy fumarate. -n-propyl fumarate, t-butyl peroxyisopropyl fumarate, t-butyl peroxy-n-butyl fumarate, t-butyl peroxy-t-butyl fumarate, t-butyl peroxy-n-octyl fumarate, t- Butyl peroxy-2-ethylhexyl fumarate, t-butyl peroxyphenyl fumarate, t-butyl peroxy-m-toluyl fumarate, t-butyl peroxycyclohexyl fumarate, t-amyl peroxy-n-propyl fumarate, t-amyl Peroxyisopropyl fumarate, t-amyl peroxy-n-butyl fumarate, t-amyl peroxyphenyl Fumarate, t-hexyl peroxy-ethyl fumarate, t-hexyl peroxy isopropyl fumarate, t-hexyl peroxy -t- butyl fumarate, t-hexyl peroxy -2
-Ethylhexyl fumarate, t-octyl peroxymethyl fumarate, t-octyl peroxyisopropyl fumarate, t-octyl peroxy-n-octyl fumarate, t-octyl peroxycyclohexyl fumarate,
Cumyl peroxyisopropyl fumarate, p-menthyl peroxyisopropyl fumarate and the like can be mentioned.

Specific examples of the monomer having a peroxide bonding group represented by the general formula (9) include t-butylperoxy (meth) acrylate, t-amylperoxy (meth) acrylate, and t-amylperoxy (meth) acrylate. Hexylperoxy (meth) acrylate, t-octylperoxy (meth) acrylate, cumylperoxy (meth) acrylate, p-menthylperoxy (meth) acrylate, 1-cyclohexyl
-1-methylethylperoxy (meth) acrylate and the like.

Specific examples of the monomer having a peroxide bonding group represented by the general formula (10) include t-butylperoxy (meth) acryloyloxyethyl carbamate and t-amylperoxy (meth) acryloyl Oxyethyl carbamate, t-hexylperoxy (meth) acryloyloxyethyl carbamate, t-octylperoxy (meth) acryloyloxyethyl carbamate,
Cumyl peroxy (meth) acryloyloxyethyl carbamate, p-menthyl peroxy (meth) acryloyloxyethyl carbamate, 1-cyclohexyl-1-metalethyl peroxy (meth) acryloyloxyethyl carbamate and the like can be mentioned.

Among these monomers containing a peroxide-bonding group, preferred monomers are t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-hexylperoxymethacryloyloxyethyl carbonate , T-butyl peroxyallyl carbonate, t-butyl peroxyisopropyl fumarate and t-butyl peroxymethacryloyloxyethyl carbamate. These peroxide-containing monomers have a thermal decomposition temperature of 8
This is because it is easy to obtain at 0 ° C. or higher and is economical.

The polymer segment (I) is formed by combining one or more monomers having no peroxide bonding group in addition to the monomer having a peroxide bonding group. It may be. Such a monomer having no peroxide bonding group is not particularly limited, and specifically, alkyl (meth) acrylates such as methyl (meth) acrylate and butyl (meth) acrylate, and 2-hydroxyethyl (meth) A) acrylates and hydroxyl-containing (meth) acrylates such as 2-hydroxypropyl (meth) acrylate;
-(Meth) acrylamides such as -dimethyl (meth) acrylamide, N, N-dialkylaminoalkyl (meth) acrylates, fumaric esters, glycidyl (meth) acrylate, maleic esters, itaconic esters, ) Acrylic acid, maleic anhydride, styrene, vinyl acetate, N-vinylpyrrolidone, N
-Vinylpyrudin, fluorine-containing monomers, silicon-containing monomers, phosphorus-containing monomers and the like.

The amount of the monomer having no peroxide bonding group is preferably 95% by weight or less in order to maintain the polymerization efficiency of the fluorine-containing monomer by heating. The peroxide bonding group fragment is formed by radical cleavage of the peroxide bonding group bonded to the polymer segment (I) formed on the base material, and is bonded to the polymer segment (I). Group.

Next, the fluorine-containing polymer segment (II) is formed from a fluorine-containing monomer bonded via a peroxide bonding group fragment, and has the following general formula (1): Those formed from at least one fluorine-containing monomer selected from the group consisting of (2), (3), (4) and (5) are preferred.

CH_Two= CR¹COOR^TwoRf (1) (where R¹Is a hydrogen atom or a methyl group, R^TwoIs -C_pH
_2p-, -C (C_pH_{2p + 1}) H-, -CH_TwoC (C_pH
_{2p + 1}) H- or -CH_TwoCH_TwoO- and Rf are -C_nF
_{2n + 1},-(CF_Two)_nH,-(CF_Two)_pOC_nH_2nC
_iF_{2i + 1},-(CF_Two)_pOC_mH_2mC_iF_2iH, -N
(C_pH_{2p + 1}) COC_nF_{2n + 1}, -N (C_pH _{2p + 1}) S
O_TwoC_nF_{2n + 1}It is. However, p is 1 to 10 and n is 1 to
16, m is an integer of 0 to 10, and i is an integer of 0 to 16. ) R in the general formula (1)^TwoIs between the ethylenically unsaturated group and Rf
It is located in between and does not require any special functions,
More selected. Further, m, n and l are practically used.
It is set from the viewpoint of easy hand.

CF ₂ ＣＦCFORg (2) (wherein Rg represents a fluoroalkyl group having 1 to 20 carbon atoms) CH ₂ ＣＨCHRg (3) (where Rg represents 1 to carbon atoms) In general formulas (2) and (3), Rg is functionally better when the number of carbon atoms is larger, but when the number of carbon atoms exceeds 20, Rg is ethylenically unsaturated. There is a possibility that polymerization by the group may not be performed effectively.

CH ₂ ＣＲCR ³ COOR ⁵ Rj R ⁶ OCOCR ⁴ ＣＨCH ₂ (4) (where R ³ and R ⁴ are a hydrogen atom or a methyl group, R ⁵ and R
⁶ is _{-C q H 2q -, - C} (C q H 2q + 1) H -, - CH 2
_{C (C q H 2q + 1} ) H- or -CH ₂ CH ₂ O-, Rj is -C _t F _2t. Here, q is 1 to 10, and t is 1 to 16.
Is an integer. )

[0044]

Embedded image (Wherein R ⁷ and R ⁸ are hydrogen atoms or methyl groups, and R k is-
C _y F _{2y + 1} . Here, y is an integer of 1 to 16. Of the above general formulas (1) to (5), general formulas (1),
The fluorine-containing monomer represented by (4) or (5) is more preferable. The reason is that the reactivity of radical polymerization initiation from the peroxide bonding group is high, and the function of the fluorine-containing polymer is easily exhibited. One of these monomers is appropriately used alone or in combination of two or more.

The monomer represented by the general formula (1) includes
For example, CF_Three(CF_Two)₇CH_TwoCH_TwoOCOCH = C
H_Two, CF_ThreeCH_TwoOCOCH = CH_Two, CF_Three(CF
_Two) _FourCH_TwoCH_TwoOCOC (CH_Three) = CH_Two, C₇
F_FifteenCON (C_TwoH_Five) CH _TwoOCOC (CH_Three) = C
H_Two, CF_Three(CF_Two)₇SO_TwoN (CH_Three) CH_TwoC
H_TwoOCOCH = CH_Two, C_TwoF_FiveSO_TwoN (C
_ThreeH₇) CH_TwoCH_TwoOCOC (CH_Three) = CH_Two,
(CF_Three)_TwoCF (CF_Two)₆(CH_Two)_ThreeOCOCH
= CH_Two, (CF_Three)_TwoCF (CF_Two)_Ten(CH_Two)_Three
OCOC (CH_Three) = CH_Two, CF_Three(CF_Two)_FourCH
(CH_Three) OCOC (CH_Three) = CH_Two,

[0046]

Embedded imageCF_ThreeCH_TwoOCH_TwoCH_TwoOCOCH = CH_Two, C_Two
F_Five(CH_TwoCH_TwoO) _TwoCH_TwoOCOCH = CH_Two,
(CF_Three)_TwoCFO (CH_Two)_FiveOCOCH = CH_Two,
CF_Three(CF_Two)_FourOCH_TwoCH_TwoOCOC (CH_Three)
= CH_Two, C_TwoF _FiveCON (C_TwoH_Five) CH_TwoOCOC
H = CH_Two, CF_Three(CF_Two)_TwoCON (CH_Three) CH
(CH_Three) CH_TwoOCOCH = CH_Two, H (CF_Two)₆
C (C_TwoH _Five) OCOC (CH_Three) = CH_Two, H (CF
_Two)₈CH_TwoOCOCH = CH_Two, H (CF_Two)_FourCH
_TwoOCOCH = CH_Two, H (CF_Two) CH_TwoOCOC
(CH _Three) = CH_Two,

[0047]

Embedded imageCF_Three(CF_Two)₇SO_TwoN (CH_Three) CH_TwoCH_TwoO
COC (CH_Three) = CH _Two, CF_Three(CF_Two)₇SO_Two
N (CH_Three) (CH_Two)_TenOCOCH = CH_Two, C_TwoF
_FiveSO_TwoN (C_TwoH_Five) CH_TwoCH_TwoOCOC (C
H_Three) = CH_Two, CF _Three(CF_Two)₇SO_TwoN (C
H_Three) (CH_Two)_FourOCOCH = CH_Two, C_TwoF_FiveSO
_TwoN (C_TwoH_Five) C (C_TwoH_Five) HCH_TwoOCOCH =
CH_TwoAnd the like.

The fluoroalkylated olefins represented by the general formulas (2) and (3) include, for example, C ₃
F ₇ CH = CH ₂ , C ₄ F ₉ CH = CH ₂ , C ₁₀ F ₂₁ C
H = CH ₂ , C ₃ F ₇ OCF = CF ₂ , C ₇ F ₁₅ OCF
ＣＦCF ₂ and C ₈ F ₁₇ OCF ＝ CF ₂ .

The monomers represented by the general formulas (4) and (5) include, for example, CH ₂ 2CHCOOCH
_{2 (CF 2) 3 CH 2} OCOCH = CH 2, CH 2 = C
HCOOCH ₂ CH (CH ₂ C ₈ F ₁₇ ) OCOCH = C
H _{2 and the} like.

As the monomer forming the fluorine-containing polymer segment (II), a monomer having no fluorine can be blended in addition to the above-mentioned fluorine-containing monomer. Such a monomer is not particularly limited as long as it is capable of radical polymerization, and specific examples thereof include unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid, and alkyls thereof. Or glycidyl esters, styrene, vinyl esters of alkyl acids, silicon-containing monomers, and the like. The amount of such a monomer is
The content must be within a range not to lose the properties as a fluorine-containing polymer, and is preferably 50% by weight or less.

Next, a method for producing a fluorine-containing polymer film will be described. The fluorine-containing polymer film forms a layer made of a polymer having a peroxide bonding group on a substrate, coats the layer with a fluorine-containing monomer, and heats to 60 to 150 ° C. By subjecting it to thermal graft polymerization.

That is, the peroxide-bonded group bonded to the polymer generates a radical by heating, and a fluorine-containing monomer is graft-polymerized from the radical, whereby a fluorine-containing monomer is formed on the layer of the polymer segment (I). A layer of polymer segment (II) is formed. Accordingly, the resulting fluorine-containing polymer coating is a fluorine-containing polymer segment comprising a graft-polymerized chain of a fluorine-containing monomer bonded via a peroxide group fragment on a layer of a polymer having a peroxide group. It has a two-layer structure in which the layer (II) is formed.

Next, a specific method for producing a fluorine-containing polymer film will be described. First, a layer made of a polymer having a peroxide bonding group will be described. The layer made of this polymer can be obtained by the following methods. (I) A method in which a homopolymer of a monomer having a peroxide bonding group or a copolymer thereof is used, and a composition containing the homopolymer or both is applied to the surface of a substrate to form a layer. (Ii) A method in which a composition containing a monomer having a peroxide-bonding group is applied on the surface of a substrate and then polymerized by heating to form the composition. (Iii) A method in which a peroxide-bonding group is introduced by a chemical reaction on the surface of a polymer having no peroxide-bonding group and having a functional group.

Among these methods, the method (i) is preferred because it is simple. When applying the polymer composition to the surface of the substrate, the composition may be diluted with a solvent as necessary.

The polymer having a peroxide bonding group can be obtained by polymerization using a usual radical polymerization initiator. In this case, the polymer is obtained by polymerizing one or more monomers having a peroxide-bonding group alone, or one or two of the other monomers having no peroxide-bonding group described above. Obtained by copolymerization with more than one species.

The amount of the monomer component having a peroxide bonding group in the polymer having a peroxide bonding group is preferably 5 to 100% by weight, and if it is less than 5% by weight, the efficiency of polymerization of the fluorine-containing monomer by heating is increased. Gets worse.

In the layer composed of the polymer having a peroxide bonding group, a monomer having an unreacted peroxide bonding group and a usual coating film are formed in addition to the polymer having the peroxide bonding group. It may contain additives used at the time. Examples of such additives include, for example, other monofunctional or polyfunctional monomers and their polymers, thermal polymerization initiators, curing agents, ultraviolet absorbers, leveling agents, surfactants, and colloidal silica. Examples include inorganic fillers. In addition, a silane coupling agent, a titanate coupling agent, or the like, which is generally used, may be added to improve the adhesion to the substrate.

The thickness of the layer of the polymer segment (I) having a peroxide bonding group fragment formed from the monomer having a peroxide bonding group as described above depends on the adhesion of this layer to the substrate and the peroxide. From the viewpoint of the concentration of the linking group, from 0.01 μm to 1
A range of about mm is desirable.

Next, the layer of the fluorine-containing polymer segment (II) formed from the fluorine-containing polymer will be described. The fluorine-containing monomer for forming the layer of the polymer segment (II) contains the fluorine-containing monomer alone or another solvent or additive. The concentration of the fluorine-containing monomer in the composition containing this fluorine-containing monomer is 1
Although it may be 00%, the fluorine-containing monomer dissolves,
Further, it may be diluted with a solvent that does not dissolve the layer of the polymer having a peroxide bonding group. Such solvents are not particularly limited, but include methanol, acetone, methyl ethyl ketone, ethanol, hexane, heptane, benzene,
Toluene and the like are preferred. Further, the fluorine-containing monomer may contain other monofunctional or polyfunctional monomers, and additives such as a surfactant and a thickener. When the fluorine-containing monomer coats the polymer layer having the peroxide-bonding group, if the polymer layer having the peroxide-bonding group is dissolved in the fluorine-containing monomer, adverse effects may occur. There is. That is, the appearance of the obtained fluorine-containing polymer film may be deteriorated by whitening or the like, or the performance may be deteriorated because the layer of the fluorine-containing polymer is not uniform. For this reason, it is preferable that the fluorine-containing monomer does not dissolve the polymer having a peroxide bonding group.

As a method of coating a fluorine-containing monomer on a layer of a polymer having a peroxide-bonding group, a method of coating a fluorine-containing monomer on a layer of a polymer having a peroxide-bonding group is used. Alternatively, a substrate having on its surface a layer made of a polymer having a peroxide bonding group may be immersed in a fluorine-containing monomer. Further, in order to prevent damage due to oxygen, it is performed in an atmosphere of an inert gas such as nitrogen, or a material that transmits heat over a fluorine-containing monomer, for example, glass, quartz,
It may be covered with a transparent synthetic resin plate, film or the like.

This fluorine-containing monomer is at least one fluorine-containing monomer selected from the group consisting of the general formulas (1) to (5). Specifically, the above-mentioned fluorine-containing monomers may be mentioned, and one of these monomers may be used alone or as a mixture of two or more.

In the method for producing a fluorine-containing polymer film, if unreacted fluorine-containing monomers or homopolymers of the fluorine-containing monomers remain after heating, these may be removed with petroleum ether or the like as necessary. Washing is preferred.

If the thickness of the layer of the fluorine-containing polymer segment (II) is too small, the surface performance due to fluorine cannot be exhibited, and if it is too large, the appearance as a film is impaired. A range of 100 μm is desirable.

As the substrate on which the fluorine-containing polymer film is formed, a wide range of materials having various shapes such as synthetic resin molding materials, films, and inorganic materials are used.
The effects exerted by the above embodiment will be described below.

According to the fluorine-containing polymer coating of the embodiment, since the surface is provided with the layer of the fluorine-containing polymer segment (II) formed from the fluorine-containing monomer,
Good performance such as water repellency and oil repellency and antifouling property can be exhibited.

According to the fluorine-containing polymer coating of the embodiment, the layer of the fluorine-containing polymer segment (II) has a peroxide bonding group on the layer of the polymer segment (I) formed on the substrate. Since they are bonded via the same, practical coating film strength can be obtained. Further, by forming a crosslinked structure in the polymer segment (I), the coating strength of the fluorine-containing polymer coating can be improved.

According to the fluorine-containing polymer film of the embodiment, the adhesion to the substrate is favorably maintained by the layer of the polymer segment (I) having a peroxide bonding group formed on the substrate. be able to. Furthermore, by adding additives such as a silane coupling agent and a titanate coupling agent to the layer of the polymer segment (I), the adhesion to the substrate can be improved.

According to the method for producing a fluorine-containing polymer film of the embodiment, since it is not the conventional method of baking at a high temperature of about 400 ° C., it is possible to suppress the possibility that the usable base material is limited. it can.

According to the method for producing a fluorine-containing polymer film of the embodiment, a method of forming a polymer layer having a peroxide-bonding group on a base material, and applying a fluorine-containing monomer thereon, etc. And heating by heating, a fluorine-containing polymer film can be easily produced.

[0070]

EXAMPLES Next, the embodiments will be described more specifically with reference to examples, comparative examples, and reference examples, but the present invention is not limited thereto. In addition,% in a text and a table represents weight%. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

The abbreviations in the text and tables are as follows. PO1: t-butylperoxymethacryloyloxyethyl carbonate PO2: t-butylperoxyallylcarbonate PO3: t-butylperoxyisopropyl fumarate PO4: t-butylperoxymethacrylate PO5: t-butylperoxymethacryloyloxyethylcarbamate MMA: methyl methacrylate BMA: Butyl methacrylate LMA: lauryl methacrylate ST: styrene DBF: dibutyl fumarate GMA: glycidyl methacrylate MAA: methacrylic acid HEMA: 2-hydroxyethyl methacrylate DMAEMA: dimethylaminoethyl methacrylate KBM503: 3-methacryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) "KBM-50"
3)) PPZ: phosphazene-based 6-functional methacrylate (“Idemitsu PPZ” manufactured by Idemitsu Petrochemical Co., Ltd.) 3002A: Bifunctional epoxy acrylate (“Epolite 3002A” manufactured by Kyoeisha Chemical Co., Ltd.) FA1: 2- (perfluorooctyl) ethyl acrylate FA2: 2- (perfluorohexyl) ethyl acrylate FA3: 2- (perfluorobutyl) ethyl acrylate FA4: 2,2,2-trifluoroethyl acrylate FMA1: 2- (perfluorooctyl) ethyl methacrylate FMA2: 2,2,2 -Trifluoroethyl methacrylate EPSEA: 2- (N-ethyl perfluoropentane sulfonamido) ethyl acrylate POE: (perfluorooctyl) ethylene PPVE: perfluoropropyl vinyl ether HPDM : 2,2,3,3,4,4-hexafluoropentanediyl 1,5-bis (methacrylate) OPDA: 3- (perfluorooctyl) propanediyl 1,3-bis (acrylate) MEK: methyl ethyl ketone PGM: propylene Glycol monomethyl ether ACS: Colloidal silica ("Snowtex O" manufactured by Nissan Chemical Co., Ltd.) is converted to 3-methacryloyloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd.)
MEK of acrylic modified coidal silica treated with
Solution LPO: Lauroyl peroxide ("Perloyl L" manufactured by NOF Corporation) TTA: Triethylenetetramine (Reference Example 1, production of peroxide-bonding group-containing polymer) Stirrer,
In a 1 liter reaction vessel equipped with a thermometer, a purge gas inlet, and a water-cooled condenser, 50 g of MEK was charged, heated to 80 ° C. under nitrogen gas ventilation, and then stirred with MMA9.
0g, PO1 10g, MEK50g, and LPO5
g of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, stirring was continued for 4 hours to complete the polymerization. The obtained solution was poured into petroleum ether to precipitate a polymer, which was then dried to obtain a peroxide-bonding group-containing polymer a. The weight average molecular weight Mw of the polymer a was 20,000. From iodometry, it was confirmed that the same amount of peroxide bonding group as that charged was introduced into the polymer. (Reference Examples 2 to 12) Polymerization was carried out in the same manner as in Reference Example 1 except that the monomers were changed to the types and amounts shown in Tables 1 and 2, to obtain peroxide-bonding group-containing polymers bl.

[0072]

[Table 1]

[0073]

[Table 2] (Example 1, Production of Coating Film) As a coating liquid I, a 20% MEK solution of the polymer a obtained in Reference Example 1 was used, and 10 cm × 10
cm and a 2 mm thick polycarbonate plate using a bar coater so that the dry film thickness becomes 5 μm.
Dry at 10 ° C. for 10 minutes. Monomer solution II on the resulting coating film
After applying a 20% FA1 ethanol solution,
It was placed in a hot air circulation type thermostat, heated to 130 ° C., and kept for 60 minutes. After completion of the heating, the resultant was washed with petroleum ether and dried to obtain a fluorine-containing polymer film. (Evaluation of Physical Properties) Next, physical properties of the obtained fluorine-containing polymer film were evaluated by the following evaluation methods. Table 5 shows the results. (1) Graft thickness The thickness before and after the graft polymerization is measured by a digital thickness meter (Sheen).
Instrument Inc.) and the increase was expressed as a graft thickness (μm). (2) Coating film hardness A pencil scratch test was performed in accordance with JIS K-5400, and the coating film hardness was represented by pencil hardness. (3) Adhesion According to the cross cut tape method of JIS K-5400, cut the coating film in the vertical and horizontal directions with a cutter knife to make 100 cross cuts (cut pieces) reaching the base material, and adhere to cellophane. A tape (Nichiban Co., Ltd.) was attached. Then, the number of crosscuts that were peeled off in the direction perpendicular to the adhesive surface and remained without being peeled was represented by the following symbol.

：: 100/100, Δ: 80/100 or more, ×: less than 80/100 (4) Contact angle measurement The contact angle between water and dodecane was measured, and the water / oil repellency of the surface was evaluated. (5) Antifouling performance For cleaning of oil stains, a forefinger was pressed against the surface of the coating to transfer a fingerprint, which was wiped back and forth with a cotton cloth for 10 times, and then the appearance was observed. And it evaluated by the following reference | standards and represented by the symbol.

：: Oil dirt can be completely wiped off.
Δ: A little oil stain remains. ×: considerable oil stains remain. (6) Appearance of coating film The appearance was visually observed. The evaluation results were represented by the following symbols.

：: transparent, Δ: translucent, ×: whitening or peeling (Examples 2 to 10) As shown in Table 3, the polymers a to j obtained in Reference Examples 1 to 10 Various monomers,
A solution composed of an additive and a solvent was applied to a glass plate in Examples 6, 8, and 10, to an acrylic plate in Example 7, and to a polycarbonate plate in Examples 2 to 5, and 9 as a substrate to be coated. And dried at 50 ° C. for 10 minutes. After a 20% FA1 ethanol solution was applied as a monomer solution 11 on the obtained coating film, the solution was put into a hot-air circulating constant temperature bath, and was heated to 130 ° C. in Examples 2 to 6 and 8 to 10, and in Example 7 Heated to 80 ° C.

Then, a fluorine-containing polymer film was formed by the method described in Example 1 except that each was kept for 60 minutes.
Physical properties were evaluated in the same manner as in Example 1. Table 5 shows the evaluation results.
It was shown to.

[0078]

[Table 3] (Examples 11 to 20) Except for using those described in Table 4 as monomer solution II, a fluorine-containing polymer film was formed by the method described in Example 1, and the physical properties were evaluated in the same manner as in Example 1. . Table 6 shows the evaluation results.

[0079]

[Table 4]

[0080]

[Table 5]

[0081]

[Table 6] Example 21 A mixture of 20 g of Polymer a and 30 g of PGM was applied to a polycarbonate plate so that the dry film thickness was 5 μm, and heated at 60 ° C. for 10 minutes. Then, FA
After applying one solution, heating, washing with petroleum ether and drying were performed in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1. Table 7 shows the evaluation results. (Example 22) A mixture of 120 g of polymer and 20 g of MEK was applied to a glass plate so that the dry film thickness was 2 µm.
Heated at 80 ° C. for 30 minutes. Subsequently, after applying a 20% ethanol solution of FA2, heating, washing with petroleum ether and drying were performed as in Example 1, and the physical properties were evaluated as in Example 1. Table 7 shows the evaluation results. (Example 23) A mixture of 20 g of polymer a and 20 g of MEK was applied to a PET film ("Tetron HP7" manufactured by Teijin Limited, 100 µm in thickness) so that the dry film thickness became 2 µm, and heated at 80 ° C for 30 minutes. Then, after applying a 20% FA3 ethanol solution, heating, washing with petroleum ether and drying were performed in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1. Table 7 shows the evaluation results. Example 24 15 g of polymer k, 5 g of TTA, ME
The mixture of 20 g of K was applied to a polycarbonate plate so as to have a dry film thickness of 5 μm, and dried at 80 ° C. for 60 minutes. Then, a 20% FA1 ethanol solution was applied, put in a hot-air circulating thermostat, heated to 130 ° C. and kept for 60 minutes, washed with petroleum ether and dried, and the physical properties were evaluated as in Example 1. Table 7 shows the evaluation results. (Example 25) A mixture of 20 g of polymer b and 20 g of MEK was applied to an acrylic plate so as to have a dry film thickness of 5 µm, and dried at 60 ° C for 10 minutes. This was placed in a 20% FA1 ethanol solution, heated to 80 ° C. and kept for 60 minutes.
Thereafter, the resultant was washed with petroleum ether and dried, and the physical properties were evaluated in the same manner as in Example 1. Table 7 shows the evaluation results. (Example 26) A mixture of 20 g of polymer a and 30 g of MEK was applied to an acrylic plate so as to have a dry film thickness of 5 µm, and heated at 60 ° C for 10 minutes. Next, a 20% ethanol solution of FA1 was applied, heated to 80 ° C. in a nitrogen atmosphere, and kept for 60 minutes. Thereafter, washing with petroleum ether and drying were performed in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1. Table 7 shows the evaluation results. (Example 27) A mixture of 20 g of polymer a and 20 g of MEK was applied to an acrylic plate so as to have a dry film thickness of 5 µm, and dried at 60 ° C for 10 minutes. Then, a 20% ethanol solution of FA2 was applied, and a glass plate was directly placed thereon. Then, heating, washing with petroleum ether and drying were performed in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1. Table 7 shows the evaluation results.

[0082]

[Table 7] (Comparative Example 1) FA1 20 g, MMA 80 g, benzoyl peroxide (Nipper BW manufactured by NOF Corporation) 1 g,
A mixture of 30 g of MEK is dried on an acrylic plate to a dry film thickness of 5 μm.
After coating and drying, put in a hot-air circulation type thermostat,
The mixture was heated to 80 ° C. and kept for 60 minutes. This was evaluated for physical properties in the same manner as in Example 1. Table 8 shows the results. (Comparative Example 2) 80 g of FA1, 20 g of MMA, 1 g of benzoyl peroxide (Nipper BW manufactured by NOF Corporation),
A mixture of 30 g of MEK is dried on an acrylic plate to a dry film thickness of 5 μm.
After coating and drying, put in a hot-air circulation type thermostat,
The mixture was heated to 80 ° C. and kept for 60 minutes. This was evaluated for physical properties in the same manner as in Example 1. Table 8 shows the results. (Comparative Example 3) 60 g of FA1, 40 g of MMA, 1 g of benzoyl peroxide (Nipper BW manufactured by NOF Corporation),
A mixture of 30 g of MEK is dried on an acrylic plate to a dry film thickness of 5 μm.
After coating and drying, put in a hot-air circulation type thermostat,
The mixture was heated to 80 ° C. and kept for 60 minutes. This was evaluated for physical properties in the same manner as in Example 1. Table 8 shows the results. (Comparative Example 4) FA1 40 g, HPDMA 30 g, M
30 g of MA, 1 g of t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by NOF Corporation), MEK
30 g of the mixture is dried on a polycarbonate plate to a dry film thickness of 5 μm.
m, and then placed in a hot-air circulating thermostat, heated to 130 ° C. and kept for 60 minutes. This was evaluated for physical properties in the same manner as in Example 1. Table 8 shows the results.

[0083]

[Table 8] The following can be seen from the results of the above Examples and Comparative Examples.
The fluorine-containing copolymer cured product of Comparative Example 1 is insufficient in water / oil repellency and antifouling performance. In addition, the cured product of the fluorine-containing copolymer of Comparative Example 2 has relatively high water-repellent and oil-repellent performance and antifouling performance due to the large amount of the fluorine-containing component, but has insufficient adhesion to the substrate.

Furthermore, the cured product of the fluorine-containing copolymer of Comparative Example 3 has relatively good adhesion, but has insufficient water and oil repellency, stain resistance and coating film hardness. And Comparative Example 4
In this case, the hardness of the coating film is relatively good, but the water and oil repellency and antifouling performance are insufficient, and the appearance of the coating is white and the transparency is poor.

On the other hand, the fluorine-containing polymer coatings of Examples 1 to 20 all had good water and oil repellency, antifouling performance, adhesion to the substrate, hardness of the coating and appearance of the coating. Yes, it is superior to the conventional method for producing a functional film. (Example 28) The surface of the fluorine-containing polymer film obtained in Example 1 was analyzed with an X-ray photoelectron spectrometer ESCA-850 (manufactured by Shimadzu Corporation). As a result, fluorine (F)
Was 29.8% (theoretical 33.3%). From this, it was found that the surface of the fluorine-containing polymer film was a FA1 graft chain.

From the results of Example 28, it can be seen that the surface of the fluorine-containing polymer film is covered with the fluorine-containing polymer segment (II) bonded via a peroxide group fragment. For this reason, it is clear that the fluorine-containing polymer coatings of the examples have excellent performance.

The technical idea grasped from the above embodiment will be described below. The fluorine according to any one of claims 1 to 3, wherein the polymer is a graft copolymer having a polymer segment (I) as a main chain and a fluorine-containing polymer segment (II) as a side chain. Containing polymer film.

With such a constitution, it is possible to ensure that the fluorine-containing polymer film adheres to the substrate, exhibits surface functions such as water and oil repellency, and its performance such as its durability, transparency and film strength. it can.

The polymer segment (I) according to any one of claims 1 to 3, wherein the polymer segment (I) is formed from a monomer having a peroxide bonding group and a monomer having no peroxide bonding group. A fluorine-containing polymer film according to the above item.

In the case of such a constitution, the adhesion of the fluorine-containing polymer film to the substrate and other properties of the fluorine-containing polymer film can be adjusted so that each performance can be exhibited in a well-balanced manner.

After applying a polymer having a peroxide bonding group to the surface of a substrate, and then applying a fluorine-containing monomer to the surface or immersing the substrate in the fluorine-containing monomer, The method for producing a fluorine-containing polymer film according to claim 4 or 5, wherein the heating is performed.

With this structure, a fluorine-containing polymer film can be easily produced by a simple operation.

[0093]

As described above in detail, according to the present invention, the following excellent effects can be obtained. According to the first fluorine-containing polymer coating, the layer of the fluorine-containing polymer segment (II) is oriented on the surface side, and the layer of the fluorine-containing polymer segment (II) is aligned with the polymer segment (I) on the substrate side. ), The surface properties such as water repellency, oil repellency, and antifouling property can be satisfactorily exhibited, and the performance can be maintained for a long time.

Further, since the surface of the fluorine-containing polymer film is a film having good uniformity of the fluorine-containing polymer segment (II), the performance can be sufficiently exhibited with a thin film.
It has good transparency and can exhibit practical coating film strength, and also has good adhesion to a substrate.

As described above, the fluorine-containing polymer film is industrially useful because it can be suitably applied to the surface of a substrate such as a synthetic resin material or an inorganic material and can exert the above-mentioned special functions.

According to the fluorine-containing polymer film of the second invention, the surface performance such as water and oil repellency, its durability, transparency,
The performance of the fluorine-containing polymer film such as the film strength is excellent, and the effect of the first invention can be enhanced.

According to the fluorine-containing polymer film of the third invention, in addition to the effects of the first or second invention, the polymer segment (I) can be easily formed. According to the method for producing a fluorine-containing polymer film of the fourth invention, the first
It is possible to easily produce a fluorine-containing polymer film having excellent performance according to the invention of (1). In addition, since heat treatment at a high temperature is unnecessary, the possibility that the applicable base material is limited can be suppressed.

According to the method for producing a fluorine-containing polymer film of the fifth invention, a fluorine-containing polymer film having better performance can be easily produced.

Claims (5)

[Claims] 1. A fluorine-containing polymer film formed on a substrate, comprising: a layer of a polymer segment (I) having a peroxide bonding group formed on the substrate; A fluorine-containing polymer film comprising a layer of a fluorine-containing polymer segment (II) formed from a fluorine-containing monomer bonded through an oxidative bonding group. 2. The fluorine-containing polymer segment (II)
Has the following general formulas (1), (2), (3), (4) and
(5) at least one fluorine selected from the group consisting of
2. The composition according to claim 1, which is formed from a monomer.
Fluorine-containing polymer film. CH_Two= CR¹COOR^TwoRf (1) (where R¹Is a hydrogen atom or a methyl group, R^TwoIs -C_pH
_2p-, -C (C_pH_{2p + 1}) H-, -CH_TwoC (C_pH
_{2p + 1}) H- or -CH_TwoCH_TwoO- and Rf are -C_nF
_{2n + 1},-(CF_Two)_nH,-(CF_Two)_pOC_nH_2nC
_iF_{2i + 1},-(CF_Two)_pOC_mH_2mC_iF_2iH, -N
(C_pH_{2p + 1}) COC_nF_{2n + 1}, -N (C_pH _{2p + 1}) S
O_TwoC_nF_{2n + 1}It is. However, p is 1 to 10 and n is 1 to
16, m is an integer of 0 to 10, and i is an integer of 0 to 16. ) CF_Two= CFORg (2) (wherein Rg represents a fluoroalkyl group having 1 to 20 carbon atoms)
I forgot. ) CH_Two= CHRg (3) (wherein Rg represents a fluoroalkyl group having 1 to 20 carbon atoms)
I forgot. ) CH_Two= CR^ThreeCOOR^FiveRj R⁶OCOCR^Four= CH_Two ... (4) (where R^Three, R^FourIs a hydrogen atom or a methyl group, R^Five, R
⁶Is -C_qH_2q-, -C (C_qH_{2q + 1}) H-, -CH_Two
C (C_qH_{2q + 1}) H- or -CH_TwoCH_TwoO- and Rj are
-C_tF_2tIt is. Here, q is 1 to 10, and t is 1 to 16.
Is an integer. )(Where R⁷, R⁸Is a hydrogen atom or a methyl group, and Rk is-
C_yF_{2y + 1}It is. Here, y is an integer of 1 to 16.
You. ) 3. The fluorine-containing polymer film according to claim 1, wherein the polymer segment (I) is formed from a monomer having a peroxide bonding group. 4. A polymer layer having a peroxide-bonding group is formed on a substrate, and a fluorine-containing monomer is coated thereon.
The method for producing a fluorine-containing polymer coating according to claim 1, wherein the coating is heated to a temperature of 150 to 150 ° C. 5. A polymer having a peroxide bonding group,
From general formulas (6), (7), (8), (9) and (10)
At least one member selected from the group consisting of peroxide bonding groups
5. The method according to claim 4, wherein the monomer is formed from
A method for producing a fluorine-containing polymer film. Embedded image(Where R¹Is a hydrogen atom or a methyl group, R^TwoIs a hydrogen atom
Or a methyl group, R^Three, R ^FourIs an alkyl having 1 to 4 carbon atoms
Group, R^FiveIs an alkyl group having 1 to 12 carbon atoms, 3 to
12 cycloalkyl groups, phenyl groups, alkyl group substitution
Represents a phenyl group, and n represents 1 to 5. )(Where R⁶Is a hydrogen atom or a methyl group, R⁷Is a hydrogen atom
Or a methyl group, R⁸, R ⁹Is an alkyl having 1 to 4 carbon atoms
Group, R^TenIs an alkyl group having 1 to 12 carbon atoms, 3 to
12 cycloalkyl groups, phenyl groups, alkyl group substitution
Represents a phenyl group, and n represents 0 to 4. )(Where R¹¹Is a hydrogen atom or an alkyl having 1 to 12 carbon atoms
A cycloalkyl group having 3 to 12 carbon atoms, a phenyl group,
Alkyl-substituted phenyl group, R¹², R¹³, Has 1 to 1 carbon atoms
An alkyl group of 4, R¹⁴Is an alkyl having 1 to 12 carbons
A cycloalkyl group having 3 to 12 carbon atoms, a phenyl group,
Represents an alkyl-substituted phenyl group. )(Where R^FifteenIs a hydrogen atom or a methyl group, R¹⁶, R¹⁷,
An alkyl group having 1 to 4 carbon atoms, R¹⁸Has 1 to 12 carbon atoms
An alkyl group, a cycloalkyl group having 3 to 12 carbon atoms,
Represents a phenyl group substituted with an alkyl group or an alkyl group. )(Where R¹⁹Is a hydrogen atom or a methyl group, R²⁰, R^{twenty one},
An alkyl group having 1 to 4 carbon atoms, R^{twenty two}Has 1 to 12 carbon atoms
An alkyl group, a cycloalkyl group having 3 to 12 carbon atoms,
Represents a phenyl group substituted with an alkyl group or an alkyl group. )