JPH01242652A - Fluorinated coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating composition excellent in smoothness, friction reduction and running durability, by mixing a fluorinated alkyl or alkenyl (meth) acrylate monomer with a specified vinyl monomer and a specified perfluoropolyether. CONSTITUTION:This fluorinated coating composition comprises the following components A, B and C, wherein the amount of B is 0.001-40wt.% and the amount of C is 0.1-50wt.% both based on component A. (A): a copolymer comprising 3-80wt.% 5C or higher fluorinated alkyl or alkenyl methacrylate or acrylate monomer (a), 1-30wt.% functional group-containing vinyl monomer (b), and 1-96wt.% vinyl monomer (c) having an unsaturated group on its end and (B): a perfluoropolyether of formula I or II.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides smoothness, low abrasion, wear resistance, running durability,
This relates to a fluorine-based coating composition that has extremely excellent properties such as water and oil resistance, moisture and rust resistance, weather resistance, and stain resistance, and is formed on solid surfaces such as metal, plastic, glass, and porcelain. Suitable for use in magnetic recording media, etc.

[Prior Art] Conventionally, various types of coating materials have been used for the purpose of protectively coating solid surfaces such as metals, porcelain, plastics, and glass. In particular, when surface smoothness is required, the coating material may contain additives such as higher fatty acids, higher fatty acid esters, paraffinic hydrocarbons, silicone oils, such as dimedylbolysiloxane, diphenylpolysiloxane, etc. Bar70roalkyl group at the end or
A method of using an oligoethylene oxide compound containing a perfluoroalkenyl group in combination with a known fluorosurfactant (Japanese Unexamined Patent Publication No. 1983-265), and a composition consisting of a perfluoropolyether and a nonionic surfactant. This is accomplished by a method of coating the material (Japanese Unexamined Patent Publication No. 59-116931).

In addition, a method of adding a fluorine-containing copolymer having a perfluoroalkyl group in the side chain to a coating material for the purpose of improving the smoothness of the solid surface (Japanese Patent Application Laid-Open No. 5-1-126220)
JP-A No. 54-43244), and a method of using a fluorine-containing copolymer having Bar 71 coloalkyl group in the side chain for paints has also been carried out.

On the other hand, recent advances in recording materials have been remarkable, particularly in the field of magnetic recording, where the recording wavelength has decreased to 2 μm or less, requiring a reduction in noise level and an increase in signal output. In addition to the composition of the magnetic layer, smoothness of the surface of the magnetic layer and back layer, runnability, friction reduction, and durability are particularly required.

In addition, from the viewpoint of magnetic properties, it is desired to make the coating film thinner because it is necessary to develop the magnetic properties more sharply.

[Problems to be Solved by the Invention] However, in various conventional coating materials and fluorine-containing copolymer paints to which various smoothness improvers are added,
Simply coating with a smoothness improver etc. will not be able to maintain stable running durability, and if a thin film is made using only a fluorine-containing copolymer, the uniformity and smoothness of the coating will drop significantly. It had the following problems.

The present invention aims to eliminate the drawbacks of the prior art, and aims to provide a fluorine-based coating composition that has excellent properties such as smoothness, friction reduction properties, and running durability.

[Means for Solving the Problems] In order to achieve the above object, the present invention has the following composition.

"Contains the following A, B, and C, and the blending amount of B to A is 0.001 to 40,000%, and 1 to A."
A fluorine-based coating composition characterized in that the content of C (♀) is 0.1 to 50% by weight.

A, a copolymer consisting of the following a, b, and c.

(a) 3 to 80% by weight of a methacrylic acid alkyl ester monomer or acrylic acid alkyl ester monomer having a fluorine-containing alkyl group or alkenyl group having 5 or more carbon atoms (b) 1 to 30% by weight of a functionalized robinyl monomer ( c) Vinyl heptanoa with an unsaturated group at the end
1 to 96% B, bar 70 polyether X-f+ OC2F4 +-F-+0CF27i lower OX represented by the following general formula (1) or (2)
(1>F3 X-H0CFCF2+T-fOCF27i lower OX...
- (2) (1), (2) In the formulas, X represents a substituent selected from carboxyl, hydroxyl, isocyanate, methylol, methylcarboxylate, epoxy, alkoxy, or perfluoro group. α and m are integers, m/D, -〇. It is 5 to 0.9. n represents an integer from 1 to 50. ) A curing agent having a functional group capable of reacting with at least one selected from C, A, 1'; and B. That is, in the present invention, a film having a fluorine concentration distribution in the thickness direction of the film is formed by a specific higher fluoroalkyl (meth)acrylate-1-copolymer A, and as a result, the fluorine concentration on the film surface is reduced. Furthermore, due to the synergistic effect with Bar 70 Roboliether B, it has excellent smoothness, abrasion resistance, running durability, and low abrasion properties over a long period of time.
and can be stably expressed.

Component a of A of the present invention is a methacrylic acid alkyl ester monomer or an acrylic acid alkyl ester monomer having a fluorine-containing alkyl group or alkenyl group having 5 or more carbon atoms.

If the number of carbon atoms is less than 5, the effect of the present invention of having a fluorine concentration distribution in the thickness direction of the film cannot be achieved.

As a preferable specific example, CH2= CRCO2(cH2) m Cn F2n+
1 (m is 1 to 2. n is an integer of 5 to 12) CH2=
CRCO2CH20(cF2) 20Cn F2n
+1 (n represents an integer of 3 to 4) CH2= CRC02CH2(cF2) m H(m
indicates an even number from 6 to 14) CI-12=cRcO2 (cHz) OCO building 0C9F
17CH2=CRCO2(cH2) m NR'SSO
2C3F17 (represents an integer from 1 to 10. R゛ represents C1 to
(represents C4 alkyl group) CH2=CRCO2(cHp) 2 NR'C0C7F
+5 (R' represents a C1 to C9 alkyl group) C1-1
2=cRcO2 (cH2') 2 Ry (Rj is CaF
13~C1°F25)C)(2=cRc02(c
I-12> 2 NSO2 (cF2 size CH2=CRCO
2CH2CHOHCH2C8F17CH2=CRCO2
(c1-12>2 NCH3C0(cF2CF20>3
Examples include C2F5.

These manufacturing methods include reacting fluorinated alcohols with linear, branched, or cyclic chains with unsaturated carboxylic acids such as acrylic acid or methacrylic acid or their acid chlorides; Fluorinated alkane carbon β-hydroxyethyl (meth)acrylate or β with a chain of
- Reaction with hydroxyl group-containing vinyl chloride such as hydroxypropyl (meth)acrylate, or ethylene chlorohydrin adduct of fluorinated alkanesulfonic acid amide and unsaturated carboxylic acid such as acrylic acid or methacrylic acid or their acid chlorides. Known synthetic methods such as reacting with
Publications, etc. will be listed. These monomers can be used alone or as a mixture of two or more.

In addition, the amount of the fluorine-containing monomer (a) used in A is required to be 3 to 80% by weight, more preferably 5 to 70% by weight, in the copolymer of A. Appropriate. If the amount is 3% by weight without swirling, the basic effects of fluorine cannot be exhibited, and if it exceeds 80%, the surface hardness, smoothness, etc. will decrease.

In A of the present invention, the functional group-containing vinyl monomer is β
-Hydroxyalkyl (meth)acrylate such as hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate
meth)acrylates; unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid; monoglycidyl esters of monovalent carboxylic acids such as octylic acid glycidyl ester or coconut oil fatty acid glycidyl ester; or adducts with monoepoxy compounds such as butyl glycidiethers; alkylene oxide adducts of unsaturated carboxylic acids; unsaturated carboxylic acid amides and their methylol compounds; low molecular weight polyesters with polymerizable unsaturated bonds Typical examples include resins.

If the amount of these used is less than 1%, sufficient coating film performance,
In particular, running durability cannot be obtained, and conversely, if the crosslinking density exceeds 30%, the crosslinking density becomes too high and the film becomes brittle, causing cracking and peeling, which is not preferable. Therefore, it is necessary that the copolymer A contains 1 to 30% by weight, preferably 3 to 28% by weight.

Typical examples of the vinyl monomer having a strongly unsaturated group at the C1 end of the present invention A include aromatic vinyl compounds such as styrene, vinyl]helene, or α-methylstyrene; vinyl acetate, and JM vinyl monomer. Vinyl ethers such as vinylidene chloride; methyl (meth)acrylate, ethyl (meth)acrylate, n (or t
)-(meth)acrylic acid esters such as butyl(meth)acrylate; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, or itaconic acid and 01 to C10
diesteric acid with a monohydric alcohol; (meth)acrylamides such as (meth)acrylamide, dimethyl (meth)acrylamide or N-alkoxymethylated (meth)acryl 7mide; N such as dimethylaminoethyl (meth)acrylate , N-dialkylaminoalkyl (meth)acrylates; gA acid group-containing (meth)acrylates such as β-7 phosphoxoxy (meth)acrylate; (meth)acrylic acid, maleic acid, fumaric acid or itaconic acid or hydroxyl group-containing Unsaturated carboxylic acids such as equimolar addition reaction products of diyl monoacetate and saturated polycarphonic acid; glycidyl (meth)acrylate, methylglycidyl (meth)acrylate-1 or ) Unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, itaconic acid
” (epoxy resin manufactured by Dainippon Ink Co., Ltd.), “Araldite 6071J (epoxy resin manufactured by Ciba Geigy Co., Ltd.)
, or an epoxy group-containing polymerizable addition obtained by adding equimolar amounts (=1) of a polyepoxy compound having at least two epoxy groups in one molecule, such as "Jissonox 221" (an epoxy resin manufactured by Jisso Co., Ltd.). A low molecular weight polyester resin having a polymerizable unsaturated bond and an epoxy group (e.g. Shell's "Peopa") is cyclopentyl, cyclohexyl, methylcyclohexyl,
2,2.5-trimethylcyclohexane, n-bornyl, 1so-bornyl, norbornyl, norbornylmethyl, Q-menthyl, α-phentyl, 1-adamantyl, 2-adamantyl, 3.5-dimethyl-1-adamandel, P-menthane, 2-methylcamphane, α-mendyl, cyclododecyl, tricyclo[5°2.1.0
2=6]dec-8-yl, tricyclo[5,2,1,0
2,6] deca-4-methyl, 3-methyl-1-adamantyl, 8-edyladamandyl, 8-methyl-5-ethyl-1-adamandel, 3.5.8-triethyl-1-
Adamandel, 3,5-dimethyl-8-ethyl-1-adamandel, norbornene, octahydro-4,7-menthanoindenyl, octahydro-4,7-menthanoinden-1-ylmedyl, P-Mendel 8, P- Mendel-2, B-hydroxy-2,6:6-trimedyru-bicyclo[8,1,1]hebutane, 8.7.71-trimedyru-4-hydroxy-bicyclo[4,1,O]hebutane- Typical examples of 4-yl or the alkyl group of an acrylic acid alkyl ester include tricyclo[5,2,1,02.6]dec-8-yl. However, the present invention is not limited to the above-mentioned compounds, and all seven copolymerizable radically polymerizable unsaturated bond groups can be used. And these seven pieces are the above-mentioned a
, b in the range of 1 to 96% by weight in relation to the use of ♀,
It may be determined according to the required characteristics. These monomers are
It is possible to improve the basic properties of a coating, such as the physical properties of the coating, such as tensile strength, hardness, bending resistance, surface electrical resistance, i♀ resistance, and adhesion to the object to be coated. However, among these, phosphoric acid group-containing (meth)acrylate-1, N.

N-dialkylaminoargyl (meth)acryle-1-
and unsaturated carboxylic acids act as internal catalysts during the curing reaction to promote the reaction. Therefore, if a large amount is used, the pot life, storage stability, and pigment dispersion stability of the paint will be adversely affected, and the remaining groups will cause deterioration of the physical properties of the coating, so it is usually not suitable for such purposes. For this purpose, the amount of these vinyl monomers used is 0.05 to 1
It is appropriate to keep it at 0%, preferably about 0.1 to 8%.

The copolymer (A>
can be obtained by a known polymerization method using the vinyl monomers listed above, such as solution polymerization using a radical generator, bulk polymerization, emulsion polymerization, suspension polymerization, etc. . Among these, the solution polymerization method is preferably used, and any radical generator used in the polymerization of acrylic yarn tops can be used. Representative examples include azobisisobutyronitrile (AIBN), di-t-butyl peroxide (DTBPO), and benzoyl peroxide (BP).
O), t-butyl perbenzoate (TBPB>, t-
Examples include butyl peroctoate (BPO) and cumene hydroperoxide (cHP).

Organic solvents that can be used include aromatic hydrocarbons such as toluene and xylene; acetate esters such as ethyl acetate, butyl acetate, or cellosolve acetate; and ketones such as methyl ethyl ketone and methyl isobutyl ketone, which are commonly used in urethane paints. If the solvent used is the same, it can be used as is. Also, if necessary, n-
dodecyl mercaptan, octyl mercaptan or t
- Chain transfer agents such as butyl mercaptan (Nippon Terpene Chemical) can also be used.

The following general formula (1) or (2) which is a daily ingredient of the present invention
The perfluoropolyether represented by plays a very important role in stably expressing properties such as smoothness and low friction on the surface of the coating.

B. Perfluoropolyether X-E+ DC2 F4 "F7,suOCF2 5-goOX (1>CF3
2> (where 1), in the formula (2), X is carboxyl,
Indicates a substituent selected from hydroxyl, isocyanate, methylol, methylcarboxylate, epoxy, alkoxy or perfluoro group. α, m are integers,
m/α-0.5 to 0.9. n represents an integer from 1 to 50. ) To give specific typical examples, Ct-h++OcF2- CF2 +T-(OCF2
5-Lower OCF3 (product name, FO) IBLIN-Z
Manufactured by Montegisson>, HOCHp-CF20 [(DC
F2C F2 U-7-1000C F2 )-1l
[-←)-One stone 10CF2--CHriOH (Product name, FO) IBLIN -Z-DOL Montegison company) OCNCeHz (cH3)-HNCO-C
F2[(OCF2CF2tr-+OCF2←"Nancho C
F2CONH-(c H1+-cs)-h-NGO (product name, FOHBLIN-Z-DISOC manufactured by Monte Chizoson) CH300C-C F20-HOCF2C F2
+-F+OC F2+-F+T-C-F2 COOCH
3 (Product name, FOHBLIN-Z-DEAL Manufactured by Montegisson), CF3 CFa++ OCFCF2t7+ OCF2 Kasu-ryoCF
3 (Product name, FOHBLIN-Y manufactured by Montegisson) F (cFCF3-CF2 0JCF- CF3 C
OON (trade name, KRYTOX, manufactured by DuPont) can be exemplified.

The blending amount of perfluoropolyether B is 0.01 to 40% by weight based on the component A. 0.

If it is less than 0.001%, sufficient low friction properties cannot be obtained, and if it exceeds 40%, there are problems such as staining of the magnetic head and so-called squealing phenomenon on the tape. Therefore 0
．． A range of 0.001 to 40%, preferably 0.005 to 30% is suitably used.

In addition, Q in formulas (1) and (2) of perfluoropolyether
:m ratio is out of the range of 1:0.5 to 0.9, or n
If it exceeds 50, the effects of the present invention cannot be achieved.

The curing agent C of the present invention reacts with the component A and/or component B to form a crosslinked structure. The hardening agent is
The copolymer reacts with the functional groups of perfluoropolyether B to construct a crosslinked structure. By using a curing agent, the film forming properties and abrasion resistance of the coating can be improved, and the characteristics of the present invention can be stably exhibited. Any curing agent may be used as long as it has a functional group that can react with the copolymer or with the functional group of perfluoropolyether B. ) Nomino resins include co-condensates of urea, thiourea, ethylene urea, melamine benzoguanamine, etc. with formaldehyde, and their lower alcohol-treated products: aromatic, aliphatic, and alicyclic diisocyanates. Polyisocyanates such as hyulettubes, adducts and 1-lima derivatives, etc.
"Burnock D-750, DN-950, -970 or D-800j (manufactured by Dainippon Ink Co., Ltd.), [Takenate B-82ONS, D-11ON, D 123N
or D-14ONJ (manufactured by Narita Pharmaceutical Co., Ltd.), [Coronatere, [H or 20311 (manufactured by Nippon Polyurethane Co., Ltd.)] [Desmodur 1-1N or HLJ]
(manufactured by Bayer) etc. are preferably used. Further examples include (poly)amines, acid anhydrides, epoxy resins, heat-reactive phenolic resins, and the like. The curing reaction of the coating includes
Commercially available catalysts such as reaction accelerators such as dibutyltin dilaurate may also be used. In addition, the blending amount of the curing agent C is 0.1 to 50% relative to the surface layer A component.
Weight%. If it is less than 0.1% by weight, a sufficiently cured film cannot be obtained and is not practical.
If it exceeds 50%, there will be problems such as a decrease in the fluorine concentration in the cured film and plasticization of the film due to the remaining curing agent. (2) Among these curing agents, when polyisocyanate is used as curing agent C, the blending ratio of copolymer A and perfluoropolyether B is OH/NGO=110°2-1. /1.5 (equivalent ratio), or it is preferably used in a range of 11 to 40% O based on the copolymer Δ,
For the curing strip 1, arbitrary conditions can be selected from room temperature to heating.

The fluorine-based composition of the present invention can be used in combination with other resins, or can be added to other resins.

Other resins Toshi-C, Arahadite-6084,60
99 (manufactured by Ciba Gaiki Co., Ltd.), Epicor 1-1004
．． 1007 (made by Shell Co., Ltd.) TF Which epoxy resins: 5TX-04,05 (hereinafter called Tobu Kasei Co., Ltd.), PK
Phenoxy resins such as HH (manufactured by Ancarbyte Co., Ltd.); urethane resins such as Soflanne-1-M S-23 (manufactured by Toyo Tire & Rubber Industries, Ltd.), Niboran-2301, 3022 (manufactured by Nippon Polyurethane Co., Ltd.); Thermoplastic resins such as vinyl chloride/vinyl acetate copolymer, acrylic acid ester/vinylidene chloride copolymer, polyamide resin, polyalkylene adipate resin, poly1 stell resin, various synthetic rubbers: alkyd resin, silicone resin, polyamine Examples include thermosetting resins such as resins, and commercially available resins with good compatibility such as reactive resins, and one or more of them may be used.

It can also be used by adding it to coatings such as acrylic, melamine, epoxy, alkyd, and urethane paints.

Furthermore, JP-A-59-116921 and JP-A-6
The dispersant, lubricant, antistatic agent, cation, anion, nonion, amphoteric surfactant, fluorine-containing surfactant, etc. disclosed in Japanese Patent No. 1-265 may be included.

Application methods for applying the fluorine-based composition of the present invention to a solid support to form a film include air doctor coating, blade coating, air knife coating, squeeze coating, impregnation]-1, reverse roll coating, Preferred examples include coat 1, transfer coat, gravure coat, cast coat, spray coat, spinner coat, gravure offset coat and curtain flow coat.

As mentioned above, the composition of the present invention can be used as a protective coating layer on various solid surfaces, such as antirust agents, antifouling agents, lubricants,
It can be used as an antistatic agent, an antifriction agent, a release agent, a mold release agent, etc., but it is particularly suitable for coating the magnetic layer of magnetic recording products in the field of recording materials, taking advantage of the thinness and smoothness of the coating.

Examples of solids to be coated include non-magnetic metals such as copper and aluminum; polyester acids such as polyethylene terephthalate and polyethylene-2,6-naphthalate; polyolefins such as polypropylene; cellulose derivatives such as cellulose acetate; plastics such as polycarbonate, etc. can be mentioned. By using it as a protective coating for magnetic layers made of ferromagnetic alloys or ferromagnetic metal oxides deposited on glass or ceramics, it can improve the surface smoothness of magnetic tapes and magnetic disks containing them. In addition, the magnetic properties can be sharpened more sharply by using a thin coating film.

In addition, the composition of the present invention can form a transparent, smooth thin film on the surfaces of glass, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polyester, etc., so it can be used as an antifouling agent for various optical devices, touch panels, and displays. It can also be used in applications that require oil resistance and cleanability, such as as an oil stain preventive agent for antireflection filters.

[Examples] Next, Examples and Comparative Examples of the present invention will be specifically described, but the present invention is not limited thereto. Unless otherwise specified, "1 part" in the text "4%f" indicates "1 part" and "% by weight" unless otherwise specified.

The evaluation items and evaluation methods performed in the following Examples and Comparative Examples are shown below.

Pencil hardness: 45 degrees extrusion by Mitsubishi Uni Contact angle: Measure the advancing contact angle with water at 25°C (Kyowa Interface Science CA-
Type D) Stain resistance: Apply red, black, and blue markers three times each, leave at 23°C for 24 hours, then wipe off with Robetanol. The degree of contamination was evaluated on a 5-point scale from 5 to 1 (5 good to 1 bad).

Smoothness: The state of the coating surface was observed using an optical microscope with a magnification of 160 times and evaluated on a 5-point scale of 5 to 1 (5 good to 1 poor). The base material used was glass measuring 75 x 75 x 3 m.

Porosity coefficient (μd): American Society for Testing and Materials Standard D-18
94, μd measurement between the treated surface and the PET film was performed using a slip tester (manufactured by our company). (!!Load 236g, tensile strength 100#/min, sample size 1
100X100, base material 25 μm, (7), j? l, I
A coating was formed on a glass plate with a wear resistance of 5 x 75
While rotating at 0 times/min, place 1 on a 30 cocoon diameter cloth.
Rubbing was performed for 30 minutes while applying a load of Kg and reciprocating at a rate of 30 times/min, and then the surface of the coating was evaluated in the same manner as smoothness. Evaluation was made on a 5-point scale with 5 to 1 scratch on one side with no scratches at all.

Synthesis Example 1 20. equipped with a stirrer, condenser, dropping funnel, thermometer and nitrogen gas blowing tube. In a four-eye flask, add acetic acid n
- 225 parts of butyl and 225 parts of xylene were charged, and the system was replaced with nitrogen gas, and the temperature was raised to 90±2°C. While stirring at the same temperature, 1st, IH, 2H12th-hebutadecafluorodecyl methacrylate (cI-1z=CCHsCO2(cH2) 2 (cF
2) 17 parts below B F > 50 parts, 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) > 100 parts, methyl methacrylate (hereinafter abbreviated as MMA) 250 parts, n-butyl methacrylate (hereinafter abbreviated as B)
A mixture consisting of 95 parts of acrylic acid (hereinafter abbreviated as AA), 5 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) as a polymerization initiator was added dropwise over 3 hours. did. Stirring was continued for 1 hour after the completion of the dropwise addition, and then 5 parts of AIBNO, 05 parts of BA, and 5 parts of xylene were added every hour 5 times. After stirring for a further 3 hours, the reaction was completed. A resin solution having a nonvolatile content of 50%, a Gardner-Holdt viscosity (hereinafter abbreviated as viscosity) Z2, water, and an acid value of 44 was obtained.

Synthesis Example 2 When obtaining the fluorine-containing copolymer in Synthesis Example 1, the monomer composition was 17 parts M50 parts, HEMA 50 parts, MMA
A resin solution having a nonvolatile content of 50%, a viscosity of 7 to Z1, and a hydroxyl value of 22 was obtained in the same manner as in Synthesis Example 1, except that 300 parts of BA, 95 parts of BA, and 5 parts of AA were used.

Synthesis Example 3 When obtaining the fluorine-containing copolymer in Synthesis Example 1,
The same procedure was used as in Synthesis Example 1, except that 350 parts of 17FM, 75 parts of HE MA, 60 parts of MM△, 5 parts of BAIO, and 5 parts of AA were used as the Nanatsuma composition, with a non-volatile content of 50% and a viscosity of Y to Z.
A resin solution having a hydroxyl value of 33 was obtained.

Synthesis Example 4 The same procedure as Synthesis Example 1 was carried out, except that 50 parts of ethyl acrylate (hereinafter abbreviated as "YA") was used instead of 50 parts of 17FM in Synthesis Example 1, with a non-volatile content of 50% and a viscosity of Z1.
, a resin solution with a hydroxyl value of 44 is 14.

Synthesis Example 5 Instead of 50 parts of 17FM in Synthesis Example 2, EA50
The non-volatile content was 50% in the same manner as in Synthesis Example 1, except that
%, viscosity X, resin with hydroxyl IB value 22) H solution is 17.

Synthesis Example 6 When preparing the fluorine-containing copolymer in Synthesis Example 1,
A resin solution having a nonvolatile content of 50%, a viscosity of U to V, and a hydroxyl value of 11 was obtained in the same manner as in Synthesis Example 1, except that 450 parts of 17FM, 25 parts of MA, and 25 parts of MMA were used as the monomer composition.

Synthesis Example 7 When obtaining the fluorine-containing copolymer in Synthesis Example 1, 50 parts of 17FM and I-I E M A22 were used as a seven-piece composition.
A resin solution having a nonvolatile content of 50%, a viscosity of 75 to Z6, and a hydroxyl value of 97 was obtained in the same manner as in Synthesis Example 1, except that 5 parts of HMA, 155 parts of BA, and 5 parts of AA were used.

Example 1 100 parts of the varnish obtained in Synthesis Example], perfluoropolyether having hydroxyl groups at both ends ([0MB1.IN-Z
-0.01 part manufactured by DOL Montageson Co., Ltd., 15 parts of Coronate Fl-1 (manufactured by Nippon Polyurethane Co., Ltd.) as a curing agent, 102 parts of methyl isobutyl ketone as a thinner, and 1 to 1×10' parts of dibutyl diurene as a curing catalyst. 17] to form a fluorine-based coating composition.

This fluorine-based coating composition was applied onto a polyester film and a glass plate using a bar coater, and the dry film thickness was 5.
A cured film of ~10 μm was formed. Drying at 140'C
It was set as 10 minutes.

This hardened film was peeled off from the glass plate and FSCA-75
0 (manufactured by Shimadzu Corporation), the number of fluorine atoms at a depth of approximately 26 cm from the air surface was extremely high, and when combined with analysis by SIMS, it was approximately 50.
Fluorine decreased continuously up to a depth of 0, after which it showed a concentration close to the brightness value. On the contrary, the glass surface showed a low fluorine concentration.

As shown in the analysis results, the fluorine-based coating material of the present invention was able to increase the fluorine concentration on the surface and exhibited excellent wear resistance, smoothness, and low friction. The results are shown in Table 1.

Examples 2 to 5 Using the varnish of Synthesis Example 1, cured films were obtained in the same manner as in Example 1, except that the type of perfluoropolyether added was changed. When this cured film was evaluated, it showed excellent smoothness, abrasion resistance, low friction, etc. as in Example 1.

The results are shown in Table 1.

Example 6.7 Using the varnishes of Synthesis Examples 2 and 3, F l to Ronnay 1
The coating, painting, and drying were carried out in accordance with Example 1, except that the content of -1 was as shown in Table 1, and as shown in the table, all exhibited excellent surface characteristics and readability. .

Comparative Example], 2 Using the varnishes of Synthesis Examples 4 and 5, coating, painting, and drying were carried out according to Example 1 except that perfluoropolyether was not added, and as shown in the table, it was clearly different from the present invention. Different cured coatings were obtained.

Comparative Examples 3 and 4 Using the varnishes of Synthesis Examples 6 and 7, Coronate El-1
The coating, painting, and drying were carried out in the same manner as in Example 1, except that the content of 1 was changed as shown in Table 1, and a cured film clearly different from that of the present invention as shown in Table 1 was obtained.

Comparative Example 5 The varnish of Synthesis Example 1 was used and the amount of perfluoropolyether added was 50 parts.
After painting and drying, a cured film (No. 19), which is clearly different from that of the present invention as shown in Table 1, was obtained.

[Effects of the Invention] The fluorine-based coating composition of the present invention has the characteristics of using a fluorine-containing copolymer and Bar 70 robolyether in combination, so that it is possible to have more fluorine present in the surface layer of the coating. can. Therefore, it can be used as a moisture- and rust-preventing agent, lubricant, anti-friction agent, mold release agent, etc., and by taking advantage of the thinness and smoothness of the film, it is used as a binder for the magnetic layer of magnetic recording products, especially in the field of recording materials. give advantages.

Patent applicant Higashi Shi Co., Ltd. Company name: Showa 6, May 13, 2013 1, Indication of the incident 1988 Patent Application No. 71178 2, Name of the invention Fluorine coating Composition 3, Relationship with the case of the person making the amendment Patent applicant address 2-2 Hikibashi Muromachi, Chuo-ku, Tokyo] - No. 5, Number of inventions increased by the amendment None 6, Patent in the specification subject to the amendment "Scope of Claims" and [(1) "Scope of Claims" in the description of the invention are amended as attached.

(2) Correct “methacrylic acid” on page 5, line 13 to “methacrylic acid.”

(3) Correct “methacrylic acid” in line 4 of page 7 to “methacrylic acid.”

(4) On page 19, line 10, change “Puretsu” to “
buret” and correct it.

(5) On page 19, lines 1-6, change “Coronatere” to “
Correct it to "Coronate L".

(6) On page 21, line 11, "araldite" is corrected to [-araldite].

(7) Correct “minutes” in line 11 of page 25 to “minutes”.

8) Page 26, lines 1-3 rAI BNOJ [
First, correct it with AI l3NJ.

(9) Page 28, line 12 r )-I M A J r
Correct with MMAJ.

Attachment Claims (1) Consisting of the following A, B, and C, the blending amount of B with respect to A is 0.001 to 40% by weight, and the blending amount of C with respect to A is 0.1 to 50% by weight. % by weight of a fluorine-based coating composition.

A, a copolymer consisting of the following a, b, and c.

(a) Polymer 9') Lyric acid alkyl ester monomer or acrylic acid alkyl ester monomer having a fluorine-containing alkyl group or alkenyl group having 5 or more carbon atoms (3 to 80%) (b) Functional group-containing vinyl monomer 1 ~30 weight? ≦ (c) Vinyl monomer having an unsaturated group at the end
1 to 96% B, perfluoropolyether X++0C2F4+T-+0CF2h→ROX <1>
CF3 X÷OCFeF2 +-I-f:0CF2 h-TOX
(2) (1), (2) In the formulas, X represents a substituent selected from carboxyl, hydroxyl, isocyanate, methylol, methylcarboxylate, epoxy, alkoxy, or a four-fold group. α and m are integers, and m/Q = 0, 5-0, 9.

n represents an integer from 1 to 50. ) A curing agent having a functional group capable of reacting with at least one selected from C, A and B.

Claims (1)

[Claims] (1) It consists of the following A, B, and C, and the blending amount of B to A is 0.001 to 40% by weight, and the blending amount of C to A is 0.1 to 50% by weight. A fluorine-based coating composition characterized by: A, a copolymer consisting of the following a, b, and c. (a) 3 to 80% by weight of a methacrylic acid alkyl ester monomer or acrylic acid alkyl ester monomer having a fluorine-containing alkyl group or alkenyl group having 5 or more carbon atoms (b) 1 to 30% by weight of a functional group-containing vinyl monomer (c) Vinyl monomer having an unsaturated group at the end 1 to 96% by weight B, perfluoropolyether represented by the general formula (1) or (2) below ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc.▼...(2) (However, in formulas (1) and (2), X is selected from carboxyl, hydroxyl, isocyanate, methylol, methylcarboxylate, epoxy, alkoxy, or perfluoro group. Indicates a substituent. l and m are integers, and m/
l=0.5 to 0.9. n represents an integer from 1 to 50. ) A curing agent having a functional group capable of reacting with at least one selected from C, A and B.