JPH02279737A - Fluorination of polyester surface - Google Patents

Abstract

PURPOSE:To give a function not deteriorating for a long term to the surface of a polyester with a fluorinating agent by aminating it, bonding a specified oligomer to the polyester and chemically combining this oligomer with a fluorinating agent. CONSTITUTION:A polyester (e.g. polyethylene terephthalate) is aminated by vapor phase treatment with a di- or poly-amine (e.g. ethylenediamine). The aminated polyester is treated with an oligomer having groups reactive with an amino group and a plurality of groups reactive with a fluorinating agent (e.g. formula I or II) to chemically bond the oligomer to the amino groups. The obtained polyester is treated with a reactive fluorinating agent (e.g. formula II or IV) in a liquid phase to chemically combine the oligomer with the fluorinating agent. In this way, the surface of the polyester is treated with the fluorinating agent to impart thereto permanently excellent water repellency, oil resistance, staining resistance, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for fluorine functionalizing polyester surfaces. For more details, see Fluorine-containing I! This invention relates to a method for fluorine functionalizing a polyester surface by chemically bonding a functional agent onto the polyester surface.

Conventional technology Traditionally, polyester has been widely used in products with barley areas such as fibers, films, paints, and coatings.
In many cases, the surface is subjected to surface treatment depending on the purpose. Surface treatments are effective in improving properties such as stain resistance against various stains, water and oil repellency in textile products, slipperiness (high wettability) in films, and moisture and stain resistance in paints. There is an extremely high demand for this.

For example, it is generally believed that the above properties can be modified by fluorine treatment of the surface layer.

Conventionally, surface modification of polyesters such as polyethylene terephthalate, polybutylene terephthalate, and unsaturated polyester resins has been carried out using fluorine-containing resins such as acrylic resin-based fluorine compounds, because direct fluorination cannot be performed using ordinary reactive reagents. This method was the only modification method that had been put to practical use.

As mentioned above, in the method of coating the surface of polyester with a fluorine-containing resin, the coating resin undergoes changes such as peeling, abrasion, and deterioration due to long-term use, and the fluorine-containing coating effect deteriorates. In the case of textile products, resin processing causes slight changes in practical properties such as texture and drapability, and furthermore, processing costs are high.

The present invention provides a method for obtaining surface functions unique to fluorine by directly chemically bonding a fluorine-containing compound to the surface of polyester, and forming a surface that can maintain these functions even after long-term use. With the goal.

Means for Solving the Problems The present invention involves treating the polyester surface with a divalent or polyvalent amine in a gas phase to form amine groups chemically bonded to the polyester chains, and grafting reactive oligomers onto the amine groups. A method of attaching a fluorine-containing functional agent to the graft by liquid phase geography to make the polyester surface fluorine functional, or a method of combining a reactive oligomer-like graft with a fluorine-containing functional agent arranged in a side chain in advance with an amine group. The present invention relates to a method for functionalizing a polyester surface by bonding to the polyester via a reaction.

The polyester to which the present invention is applicable refers to any polymer having an ester bond as the main bond of the main chain component, but particularly useful ones include terephthalic acid, such as polyester terephthalate and polybutylene terephthalate. Polycondensates of aromatic dicarboxylic acids such as isophthalic acid and glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, polytetramethylene ether glycol, or copolymers thereof , aromatic polyester consisting of a polymer alloy; a homopolymer of polyarylate mil-oxybenzoic acid whose main constituent is a polycondensate of the above aromatic dicarboxylic acid and dihydric phenol such as bisphenol A1 AP, bisphenol F1 S, etc. Aromatic dicarboxylic acids such as poly p-oxybenzoic acid, terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, p-oxybenzoic acid, 2,6-s7taleneoxycarboxylic acid, etc. Polycondensates of aromatic dihydric phenols such as oxycarboxylic acid, hydroquinone, 2゜6-dinaphthol, 4,4'-dioxydiphenyl, or copolymers of these with aromatic polyesters such as polyethylene terephthalate, or Liquid crystalline polyesters whose main components are these polymer alloys; polycondensates of polybasic acids such as maleic anhydride, fumaric acid, and phthalic anhydride and polyhydric alcohols such as ethylene glycol, propylene glycol, and neopentyl glycol; or Unsaturated polyester obtained from a copolymer with a polymerizable monomer such as styrene $11: Polybasic acids such as phthalic anhydride, fumaric acid, and terephthalic acid, and linoleic acid, oleic acid, lauric acid, stearic acid, benzoic acid, etc. Alkyd resin (glyphthalic acid) whose main constituent is a polycondensate of monobasic acid and polyhydric alcohol such as glycerin or penerythritol, or a composition modified by blending it with glyceride such as natural oil; epoxy Reaction between resin and (meth)acrylic acid, or (meth)acrylic unsaturated alcohol/polybasic acid anhydride adduct, or glycidyl methacrylate and polyhydric phenols, aromatic diamine, polyhydric carboxylic acid, or the same anhydride. Vinyl ester resins consisting of vinyl esters obtained by reaction with substances, etc., or copolymers of them and polymerizable monomers such as styrene; diallyl phthalate,
Diallyl phthalate resin whose main constituent is a polymer or copolymer of diallyl isophthalate; aliphatic dibasic acids such as adipic acid and cepacic acid, and ethylene glycol,
1.4-butanediol, 116-hexanediol,
Polycondensates with glycols such as neopentyl glycol and diethylene glycol, ring-opening polymers of lactones such as C-caprolactone, and ring-opening polyadducts of glycols such as 1,6-hexanediol with carbonates such as ethylene carbonate. Ester-type polyurethane resins obtained by polyaddition polymerization of polyester polyols such as and polyisocyanates such as toluene diisocyanate (TDI) and methylphenyl diisocyanate (MDI):
Examples include. The target surface may be in any form, but as mentioned above, surfaces with a large surface area such as fibers, films, sheet paint coatings, etc. are particularly effective.

These polyester products can be used as they are, or after wet treatment with an aprotic polar solvent such as dimethylformamide, dimethyl sulfoxide, or N-methyl-2-pyrrolidone, primary or secondary amines can be added to these polyester products. Gas phase treatment is carried out using divalent or polyvalent amines consisting of groups.

The amines used here include hydrazine, ethylenediamine, diethylenetriamine, triethylenetetramine, piperazine, hexamethylenetetramine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1.2゜3-triamino Propane, Tris (2-
aminoethyl)amine, tetra(aminomethyl)methane%1I4-diazabicyclohebutane, cyclodi(trimethylene)diimine, N-methylethylenediamine, N-
Ethylethylene diamine, 2,2'-diaminoethyl ether, etc. are suitable.

As for the treatment method, it is preferable to perform the treatment in a vaporized or evaporated state as described above, but in the present invention, it is preferable to perform the treatment in a liquid state without using any other liquid such as a solvent or medium, or in a liquid state without using water or alcohol. The treatment can also be carried out by contacting the object with a solution using a solvent such as a polar solvent, or a dispersion in an incompatible medium, and heating it to a temperature from room temperature to 150°C. It is possible. During these reactions, the presence of a small amount of water generally has the effect of accelerating the reaction.

Through this treatment, part of the ester bonds in the polyester main chain undergoes amitolysis by the primary or secondary amino groups of the treated amine, resulting in the formation of amide bonds, and the remaining amino groups form anchors in the polyester main chain. It becomes a reactive group for use.

At this time, the main chain is broken along with the reaction, so in the case of processed materials such as fibers, films, and sheets, if the reaction is carried out at too high a density to reach the inside, physical properties such as mechanical properties will deteriorate. Therefore, it is necessary to complete the process under mild conditions and in a relatively short time.

Due to such constraints, the concentration of bonded amino groups formed is relatively low, and therefore, if a reactive fluorine-containing compound is reacted with the amino group as it is, the specific function of the fluorine compound will be extremely low.

In the present invention, the reactive groups on the polyester surface that can react with the reactive fluorine-containing functional agent are multiplied many times using the amino group as a core.

Specifically, (i) the amine-treated polyester surface is coated with at least one amine-reactive group that is reactive with the newly formed amino group and with a reactive fluorine-containing functional agent; The amino group and the amine-reactive group are chemically bonded by treatment with an oligomer (graft) having at least two fluorine-containing functional agent reactive groups to form an anchor (wedge bond) between the polyester surface and the graft. And the pairing fluorine Il of this graft! Method for chemically bonding a reactive fluorine-containing functional agent to a functional agent reactive group: (Li) The amine-treated polyester surface contains at least one anti-amine reactive group that is reactive with the newly formed amino group. By acting with an oligomer (fluorine-containing graft) having at least two fluorine functional side chains,
A method of bonding the fluorine-containing graft to the polyester surface by a chemical bond (anchor) between the amino group on the surface and the amine-reactive group; (iii) bonding the newly formed amino group and the graft to the amine-treated polyester surface; a coupler that chemically connects the two, at least one pair of coupler-reactive groups that are reactive with the coupler, and at least two pairs of fluorine-containing functional agent-reactive groups that are reactive with the reactive fluorine-containing functional agent. Bonded oligomer (coupler base graft)
are treated sequentially or simultaneously to bond the graft to the polyester surface via an amino group/coupler/pair-coupler reactive group linkage (anchor), and to bind the graft to the polyester surface via an amino group/coupler/pair-coupler reactive group linkage (anchor), and to attach a reactive group to the fluorine-containing functional agent-reactive group of the kuggler-type graft. A method of chemically bonding by acting on a fluorine functional agent; (iv) A coupler that chemically connects the newly formed amino group and the fluorine-containing graft on the amine-treated polyester surface and a coupler that is reactive with the simple coupler. An oligomer having at least one coupler-reactive group and at least two fluorine-containing functional side chains (coupler-type fluorine-containing graft) is treated sequentially or simultaneously to convert the coupler-type fluorine-containing graft into an amino group/coupler/pair. Examples include a method of bonding to a polyester surface by a coupler reactive group bond (anchor).

In each method, the various grafts are oligomers having two functional groups with different functions: a reactive group to the amino group on the polyester surface, a reactive group to the coupler, and a reactive group to the reactive fluorine-containing functional agent. , these six groups may be different types of groups, or may be completely the same group.

For example, in the case of method (i) above, a polyvinyl alcohol oligomer substituted with several glycidyl groups is selected as the graft, a perfluoroalkyl compound having carboxylic acid chloride as a reactive group is selected as the fluorine-containing functional agent, and these are applied to the amine-treated polyester surface. When treated sequentially, an anchor bond is formed between the epoxide of the glycidyl group and the amine on the polyester surface, and the fluorine-containing functional agent is chemically bonded to the graft by the reaction of the remaining hydroxyl group of the polyvinyl alcohol with the carboxylic acid chloride. , a durable fluorine-containing functional surface can be obtained.

In addition, an oligomer in which all hydroxyl groups of polyvinyl alcohol are replaced with glycidyl groups is used for grafting, a part of the epoxide on the graph is reacted with amine-treated polyester to form an anchor, and then the remaining epoxide is Also effective is a method in which a fluorine-containing functional agent having a compound as a reactive group is made to act together with a catalyst to bond to the graft.

When the same group is used as both reactive groups, the advantage is that the ratio of the anchor to the fluorine-containing functional agent binding group can be freely changed by selecting the reaction conditions during the treatment reaction on the polyester surface of the graft. .

In the case of the method (ii) above, fluorine-containing functionalization can also be performed using an oligomer having a single type of reactive group for grafting. That is, a group capable of rapidly reacting with an amine is used as the single type of reactive group, an oligomer having three or more of the groups is used as a substrate for the fluorine-containing oligomer, and at least one of the reactive groups is left, and other groups are A method that can be effectively used is to prepare a fluorine-containing oligomer in which at least two fluorine-containing functional side chains are formed by reacting a reactive fluorine-containing functional agent, and to apply this to the amine-treated polyester surface.

In the case of methods (i ii) and (iv) above,
When the anti-amine reactive group of the graft and the fluorine-containing graft is replaced with the anti-coupler reactive group, fluorine-containing functionality can be achieved with a single reactive group in the same manner as described above.

Examples of substrates for these grafts or fluorine-containing grafts before formation of functional side chains include molecular weights of 200 to 30.00.
0, polyols such as polyvinyl alcohol and polyallyl alcohol, polyaldehydes such as polyacrolein and polycrotonaldehyde, polyacrylic acid chloride,
Polycarboxylic acid halides such as polymethacrylic acid chloride, polycarboxylic acid anhydrides such as vinyl ether/maleic anhydride copolymer, styrene/maleic anhydride copolymer, polyvalent epoxy resins such as polyglycidyl methacrylate, glycidyl novolac, etc. Examples include polyamines such as arylamine, polyethyleneimine, polyvinylamine, and oligomers such as polyisocyanate prepolymers such as TDI/TMP adducts.

The manner of bonding between the reactive group of these grafts or the fluorine-containing graft substrate and the reactive group of the fluorine-containing functional agent thereto, and the manner of bonding of both grafts to the polyester surface are as illustrated in Table 1. Further, similar examples regarding coupler-type grafts using couplers are listed in Table 2.

(Hereinafter, blank space) Reactive fluorine-containing functional agents include perfluoroalkyl groups having 3 or more carbon atoms (formula Rfl below), perfluoroalkenyl groups (formula Rfn below), or perfluoro groups such as perfluoroallyl groups (formula below). Contains Rfl[+], and alcohol, thiol, phenol, methylol (nuclear substitution), methylene halide (nuclear substitution), epoxy, carboxylic acid (salt), carboxylic acid halide, carboxylic acid anhydride, sulfonic acid (salt) ), sulfonic acid halide, phosphonic acid (salt), phosphonic acid dihalide, phosphorus dihalide, aldehyde, amine, methylolamine, methylolamide, hydrazine, dichlorotriazine, dialkoxytriazine, dithiotriazine, melamine, ethylene urea, incyanate , nitrile, oxazole, thiazole, imidazole, vinyl, vinyl ether, (
Compounds having reactive groups such as meth)acrylic, maleimide anhydride, acetylenyl, (mono, di, tri)chlorosilane, and (mono, di, tri)alkoxysilane are suitable.

Specific examples of the perfluoroalkenyl group (RfI) are as follows:

It is.

-(CFx)a+-CF3 (m-2~15) [wherein, Rj=CnjF*nj++(nj-0~6), and 0
≦Σn4≦20] -(CFxCFs)m-H(m-2 to 8) perfluoroalkenyl group (Examples of R groups include the following formula.

R3 [wherein, Rj-CnjFinj++(nj-1 to 6.1
．． 2 or 3)] The coupler that connects the amino group of the amine-treated polyester and the counter-coupler reactive group of the coupler-type graft or the coupler-type fluorine-containing graft is a single group that exhibits reactivity with both reactive groups in common. There may be,
It may have two types of groups each having different reactivity. For example, as illustrated in Table 2, examples of the former include formamide and succinic acid chloride, and examples of the latter include silane coupling agents and acrolein.

Methods for using these couplers include (1) sequential processing method and (2) simultaneous processing method.

In the sequential geography method, a coupler is applied to the amine group formed on the polyester surface to form an amino group/coupler reactive group bond, and then the coupler is grafted, or a fluorine-containing graft of the coupler base is attached to the reactive group to be bound by the coupler. is reacted in the liquid phase to form a coupler-reactive group/counter-coupler-reactive group bond between the coupler and each graft to complete the anchor (in the case of coupler-type grafts, this anchor-forming graft is also provided with a reactive impurity). All processing is completed with further binding of fluorofunctional agents).

In the simultaneous treatment method, a coupler and a coupler-type graft or a fluorine-containing coupler graft are simultaneously applied to the amine groups formed on the surface of the polyester.
Amino group/coupler reactive group bond and coupler reactive group/
Form a reactive group bond to the coupler.

Which of the above should be selected after considering the combination of coupler and graft, required specifications of the target polymer product, economic efficiency, etc.
decide.

In any of the methods described above, each graft is performed by a liquid phase reaction. The liquid phase reaction refers to a process in which the object to be treated is made into a dispersion liquid such as a solution or an emulsion and brought into contact with the liquid by a method such as impregnation or spray coating under appropriate reaction temperature conditions to cause a reaction.

In each of the above geographical methods, amine treatment, graft treatment,
Appropriate selection of each processing condition for reactive fluorine-containing functional agent treatment will bring out the effects of the fluorine-containing functional agent and provide various functions unique to fluorine that can be used permanently, but the balance between these is important. If it goes awry, you may not get the desired effect. The biggest problem in this case is the presence of an amino group having a reactive activity that remains without reacting with the reactive group to be treated during each of the above steps.

The amino group not only suppresses the functional expression of the fluorine-containing functional agent, but also may cause discoloration, deterioration of mechanical properties, etc. when exposed to air for a long period of time.

Therefore, the amino acid is treated with a fluorine-containing functional agent in the methods (i) and (i i) above, or after the treatment with a fluorine-containing functional agent in the method (i
), after the grafting treatment of the fluorine-containing graft or coupler-type fluorine-containing graft in the method of (iV), low molecular-functional counteramines such as acetyl chloride, benzoyl chloride, methyl chloride, methyl iodide, benzyl chloride, acetic anhydride, etc. It is preferable to act with a reactant to inactivate the remaining amine.

Comparative Example A polyethylene phthalate (hereinafter referred to as PET) film (for 100 μ plate making) and a PET processed yarn fabric (twill) were heat-treated in 75°C saturated steam of 10% ethylenediamine water solution for 4 minutes to quickly transform the system. Take it outside, wash it several times with acetone, and let it air dry.

5 g of these samples were mixed with 1 g each of reactive fluorine-containing functional agents A and B described below in a xylene/dioxane (7/3) mixed solution 2.
It was immersed in a solution dissolved in 00 mff and heat-treated at 60° C. for 30 minutes. The results are shown in Table 3.

This sample was washed several times with acetone 50011112, air dried, and then dried in a constant temperature oven at 50°C. The following physical properties were measured for each treated sample.

Water repellency: JIS L-1092 spray method...fabric only Wetting characteristics: contact angle with water, liquid application method...film only (goniometer type) Reactive fluorine-containing functional agent A) p-(perfluoroalkenylene) (abbreviated as PFBC) B) p-(perfluoroalkenyloxy)glycidyl benzoate (abbreviated as PFGB) Table 3 The same sample as the Aishozuki reference example was treated with amine in the gas phase in exactly the same manner. , the following grafting agents and reactive fluorine-containing functional agents; Grafting agent a) Methyl vinyl ether Q maleic anhydride copolymer (
G, A, F, Corp.: GANTREZ AN
119 Low differentiated product) Cellophane film and cotton cloth are coated with a polyacrylamine methanol solution (epichlorohydrin formulation), heated and cross-linked.

b) Glycidyl methacrylate copolymer (manufactured by NOF Corporation: Bremmer 〇P-205A) C) Epoxy modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd. 1KF105) D) p-(perfluoroalkenyloxy>sodium benzoate (abbreviated as PFBA) ) d) Polyallylamine (manufactured by Nittobo Co., Ltd., FAA-H (1-L alkaline de-HCl2 product) was used in the combinations shown in Table 4, and the grafting treatment and fluorine-containing functional agent were performed under the conditions listed in Table 5. processed.

Similar physical properties (water repellency, wetting properties) in the comparative example were measured, and the results are shown in Table 5.

(Hereafter, blank space) A) PFBC B) PFGB C) p-(perfluoroalkenyloxy)aniline (P
(abbreviated as FA) From the above results, it can be seen that the method of directly acting a reactive fluorine-containing functional agent on the amine-treated material as in the comparative example cannot achieve a practical effect because the concentration of amino groups is insufficient. As shown in the example, when the reactive fluorine-containing functional agent is applied through a graft (or coupler base graft) having a reactive group to the fluorine-containing functional agent, the surface coated with a resin film formed by a conventional coating method is It was revealed that a highly durable water-repellent surface was obtained which had much better washing resistance than that of I.

Effects of the Invention According to the present invention, a fluorine-containing functional agent is chemically bonded to the surface of polyester, making it possible to apply a permanent coating consisting of a thin layer on the order of molecules, thereby improving the water and oil repellency characteristic of perfluoro groups. Functions such as antifouling, non-coating, high lubrication (low coefficient of friction, wear resistance), and chemical resistance are permanently imparted. Moreover, the present invention does not impair the mechanical properties such as feel and flexibility inherent to polyester.

Claims (1)

[Claims] 1. The polyester surface is treated with a divalent or polyvalent amine in a gas phase to form a primary or secondary amino group bonded to the polyester chain through an amide bond, and then the amino group is treatment with an oligomer (graft) having at least one amine-reactive group that is reactive with the fluorine-containing functional agent and at least two fluorine-containing functional agent reactive groups that are reactive with the reactive fluorine-containing functional agent, The amino group and the reactive group of the counter amine are chemically bonded to form an anchor between the polyester surface and the graft, and further,
A method for imparting a fluorine-containing function to the surface of a polyester, the method comprising performing a liquid phase treatment using the reactive fluorine-containing functional agent to chemically bond the fluorine-containing functional agent to the graft. 2. The polyester surface is treated with a divalent or polyvalent amine in a gas phase to form a primary or secondary amino group bonded to the polyester chain through an amide bond, and then a pair reactive with the amino group is formed. A liquid-phase treatment is performed using an oligomer (fluorine-containing graft) having at least one amine-reactive group and at least two fluorine-containing functional side chains, and the fluorine-containing graft is treated in a chemical manner between the amino group and the counter-amine reactive group. A method for functionalizing a polyester surface with fluorine, which is characterized by bonding to the polyester surface through a bond (anchor). 3. The surface of the polyester is treated in a gas phase with a divalent or polyvalent amine to form a primary or secondary amino group bonded to the polyester chain through an amide bond, and then the amino group and the graft described below are combined. A chemically linked coupler, at least one coupler-reactive group that is reactive with the coupler, and at least two fluorine-containing functional agent-reactive groups that are reactive with the reactive fluorine-containing functional agent. Oligomers (grafts) are treated sequentially or simultaneously to bond the grafts to the polyester surface via amino group/coupler/pair-coupler reactive group bonds (anchors), followed by liquid phase treatment with reactive fluorine-containing functional agents. A method for imparting a fluorine-containing function to a polyester surface, which comprises chemically bonding a fluorine-containing functional agent to the graft. 4. The surface of the polyester is treated in a gas phase with a divalent or polyvalent amine to form a primary or secondary amino group bonded to the polyester chain through an amide bond, and then the amino group is combined with the fluorine-containing graft described below. and an oligomer (fluorine-containing graft) having at least one pair-coupler reactive group reactive with the coupler and at least two fluorine-containing functional side chains, either sequentially or simultaneously. A method for fluorine-containing functionalization of a polyester surface, characterized in that the fluorine-containing graft is linked to the polyester surface via an amino group/coupler/pair-coupler reactive group bond (anchor) through liquid phase treatment. 5. The method according to claim 1, wherein the amine-reactive group and the fluorine-containing functional agent-reactive group of the graft are the same group. 6. The amine-reactive group and the fluorine-containing functional agent-reactive group of the graft are the same group, have three or more of them, and leave one or more of the reactive groups reactive to other reactive groups. A fluorine-containing functional agent is subjected to a liquid phase reaction to form at least two fluorine-containing functional side chains.
3. The method according to claim 2, characterized in that an individually formed oligomer (fluorine-containing graft) is used. 7. The method according to claim 3, wherein the reactive group for the coupler and the reactive group for the fluorine-containing functional agent of the graft are the same group. 8. The fluorine-containing graft has the same group as the reactive group for the coupler and the reactive group for the fluorine-containing functional agent, and has three or more of them, leaving one or more of the reactive groups to react with other functional groups. Oligomer (fluorine-containing graft) in which at least two fluorine-containing functional side chains are formed by liquid-phase reaction of a functional fluorine-containing functional agent
5. The method according to claim 4, characterized in that: 9. The substrate before functional side chain formation of graft or fluorine-containing graft is an oligomer with a molecular weight of 200 to 30,000, polyol such as polyvinyl alcohol and polyallyl alcohol, polyaldehyde such as polyacrolein and polycrotonaldehyde, polyacrylic acid chloride, poly Polycarboxylic acid halides such as methacrylic acid chloride, polycarboxylic acid anhydrides such as vinyl ether/maleic anhydride copolymers, styrene/maleic anhydride copolymers, polyvalent epoxy resins such as polyglycidyl methacrylate, glycidyl novolac, and polyaryls. Amine, polyamine such as polyethyleneimine, toluene diisocyanate (TD
I)/(methylphenyl diisocyanate (TMP) adduct or the like), the method according to any one of claims 5 to 8. 10. The reactive fluorine-containing functional agent has 3 or more carbon atoms. Contains perfluoro groups such as perfluoroalkyl group, perfluoroalkenyl group, perfluoroallyl group, and alcohol, thiol, phenol, epoxy, carboxylic acid (salt), carboxylic acid halide, carboxylic acid anhydride, sulfonic acid (salt), sulfonic acid halide, phosphonic acid (salt), phosphonic acid dihalide, phosphonylic acid dihalide,
Aldehyde, amine, methylolamine, methylolamide, hydrazine, cyanuric chloride, melamine, ethylene urea, isocyanate, nitrile, oxazoline, anhydrous maleimide, vinyl, vinyl ether, (meth)acrylic, (mono, di, tri)chlorosilane, (mono, 5. The method according to claim 1, wherein the compound is a compound having a reactive group such as di,tri)alkoxysilane. 11.A reactive fluorine-containing functional agent is applied to each graft-bonded polyester surface, and after the reaction is completed, a fluorine-containing graft having a fluorine-containing functional agent in a side chain, or a coupling type fluorine-containing graft is applied to the polyester surface. After the reaction is complete, a low molecular weight functional anti-amine reagent such as acetyl chloride, benzoyl chloride, methyl chloride, methyl iodide, benzyl chloride, acetic anhydride, etc. is applied to the polyester surface or the remaining amine in each graft. , wherein the amine is inactivated.
The method according to any one of ~4.