Non-adhesive composition

Abstract

To provide a non-adhesive composition having excellent mold releasability, and excellent water and oil repellency.SOLUTION: A non-adhesive composition includes: a rubber component or a resin; and 0.05 to 10 pts.mass of a fluorine-containing copolymer per 100 pts.mass of the rubber component or the resin, wherein the fluorine-containing copolymer is a copolymer of a fluoroalkyl alcohol (meth)acrylic acid derivative, and of a (meth)acrylic acid ester, a monoalkyl ester or dialkyl ester of fumaric acid, or a monoalkyl ester or dialkyl ester of maleic acid.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a non-adhesive composition. [Background technology]

[0002] Polymers containing perfluoroalkyl groups have long been considered promising for various applications due to their excellent properties.

[0003] Patent Document 1 (International Publication No. 2004 / 035708) discloses a water- and oil-repellent composition comprising a copolymer containing polymerization units of a monomer (a) having a polyfluoroalkyl group, wherein the microcrystals derived from the polyfluoroalkyl group of the monomer homopolymer have no melting point or are 55°C or lower, and the homopolymer has a glass transition point, which is 20°C or higher, and polymerization units of other monomers.

[0004] Patent Document 2 (International Publication No. 2009 / 034773) discloses a fluorine-containing copolymer of (a) a fluoroalkyl alcohol acrylic acid derivative or a corresponding methacrylic acid derivative and (b) an acrylic acid ester or methacrylic acid ester, a monoalkyl or dialkyl ester of fumaric acid or maleic acid, or a vinyl ester. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2004 / 035708 [Patent Document 2] International Publication No. 2009 / 034773 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] Among polymers having a perfluoroalkyl group, those having 6 or less carbon atoms in the perfluoroalkyl group have low bioaccumulation properties, and thus their usefulness has been attracting attention in various technical fields. Development of a composition containing a polymer having a perfluoroalkyl group with 6 or less carbon atoms and other components has been studied.

[0007] Therefore, the present inventors have found that a composition containing a copolymer having a specific structure with a perfluoroalkyl group having 6 or less carbon atoms and a rubber component or a resin has excellent mold release properties and water and oil repellency, and thus have arrived at the present invention. That is, the present invention provides a non-adhesive composition having excellent mold release properties and water and oil repellency.

Means for Solving the Problems

[0008] The gist of the present invention is as follows. [1] A rubber component or a resin, containing 0.05 to 10 parts by mass of a fluorine-containing copolymer with respect to 100 parts by mass of the rubber component or the resin, wherein the fluorine-containing copolymer is C n F 2n+1 (CH2CF2) a (CF2CF2) b (CH2CH2) c OCOCR 1 =CH2 (wherein R 1 represents a hydrogen atom or a methyl group, n represents an integer of 1 to 6, a represents an integer of 1 to 4, b represents an integer of 1 to 3, and c represents an integer of 1 to 3) and a fluoroalkyl alcohol (meth) acrylic acid derivative represented by R 2 OCOCR 1 =CH2 (wherein R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group), a monoalkyl ester or dialkyl ester of fumaric acid, or a monoalkyl ester or dialkyl ester of maleic acid A non-adhesive composition which is a copolymer of [a certain material]. [2] The non-stick composition according to [1] above, wherein the weight-average molecular weight of the fluorine-containing copolymer is 2,000 to 50,000. [Effects of the Invention]

[0009] This invention provides a non-adhesive composition with excellent release properties and water- and oil-repellent properties. [Modes for carrying out the invention]

[0010] (Non-adhesive composition) The non-adhesive composition of the present invention contains a rubber component or resin and 0.05 to 10 parts by mass of a fluorine-containing copolymer per 100 parts by mass of the rubber component or resin. This fluorine-containing copolymer is a copolymer of monomers (a) and (b) described below. (a)C n F 2n+1 (CH2CF2) a (CF2CF2) b (CH2CH2) c OCOCR 1 =CH2(wherein, R 1 Fluoroalkyl alcohol (meth)acrylic acid derivatives represented by (where is a hydrogen atom or methyl group, n is an integer from 1 to 6, a is an integer from 1 to 4, b is an integer from 1 to 3, and c is an integer from 1 to 3), (b)R 2 OCOCR 1 =CH2(wherein, R 1 R is a hydrogen atom or a methyl group. 2 (meth)acrylic acid esters represented by alkyl, alkoxyalkyl, cycloalkyl, aryl, or aralkyl groups, monoalkyl or dialkyl esters of fumaric acid, or monoalkyl or dialkyl esters of maleic acid. Note that the "fluoroalkyl alcohol (meth)acrylate" which is the monomer (a) represents a fluoroalkyl alcohol acrylate derivative or a fluoroalkyl alcohol methacrylate derivative. Also, the "(meth)acrylate ester" which is the monomer (b) represents an acrylate ester or a methacrylate ester.

[0011] The non-stick composition of the present invention contains a perfluoroalkyl group C having 6 or less carbon atoms in the fluorine-containing copolymer n F 2n+1 (where n is an integer from 1 to 6) and a rubber component or a resin. Since the perfluoroalkyl group having 6 or less carbon atoms has low bioaccumulation, the safety to the human body can be enhanced. Further, since the fluorine-containing copolymer contains a hydrocarbon portion, it has excellent compatibility with the rubber component and the resin, and even when contained in an amount of 0.05 to 10 parts by mass with respect to 100 parts by mass of the rubber component or the resin, it can be uniformly dispersed or dissolved in the rubber component or the resin. Therefore, for example, when a non-stick composition containing the rubber component and the fluorine-containing copolymer of the present invention is filled into a mold and then vulcanized and molded, the fluorine-containing copolymer leaks out onto the surface of the non-stick composition during the molding to form a low-energy surface. Similarly, when a non-stick composition containing the resin and the fluorine-containing copolymer of the present invention is filled into a mold and then crosslinked, polymerized, etc. and molded, the fluorine-containing copolymer leaks out onto the surface of the non-stick composition during the molding to form a low-energy surface. As a result, the molded product obtained by molding the non-stick composition can be easily taken out from the mold. Further, since the surface of the obtained molded product also has low adhesion to other materials, it can have properties such as non-adhesiveness, water repellency, oil repellency, etc. Therefore, the molded product can be used for objects that require these properties. More specifically, the molded product of the non-stick composition of the present invention can be used for applications such as rubber products such as fluororubber, natural rubber, EPDM rubber, acrylic rubber, etc., resin products such as acrylic resin, vinyl chloride resin, epoxy resin, polyurethane resin, phenol resin, etc., waterproof sealing materials (modified silicone), non-adhesiveness, water repellency, oil repellency of non-woven fabrics, imparting stain resistance, internal mold release agents during molding, etc.

[0012] Examples of the rubber component constituting the non-sticky composition of the present invention include fluororubber, natural rubber, EPDM rubber, urethane rubber, acrylic rubber, hydrin rubber, etc. The fluororubber is not particularly limited, and examples thereof include vinylidene fluoride-based fluororubber (FKM), tetrafluoroethylene-propylene-based fluororubber (FEPM), tetrafluoroethylene-perfluorovinyl ether-based fluororubber (FFKM), etc. The rubber component may be either an uncrosslinked or crosslinked rubber component, but it is preferably a crosslinked rubber component. The crosslinked rubber component may be a crosslinked rubber component after either primary crosslinking or secondary crosslinking. Note that fluororubber is distinguished from the fluorine-containing copolymer of the present invention in that it does not contain monomer (b). Further, examples of the resin constituting the non-sticky composition of the present invention include fluororesin, epoxy resin, phenolic resin, melamine resin, polyethylene resin, polypropylene resin, polyester resin, vinyl chloride resin, etc. Note that fluororesin is distinguished from the fluorine-containing copolymer of the present invention in that it does not contain monomer (b).

[0013] The content of the fluorine-containing copolymer in the non-sticky composition of the present invention is 0.05 to 10 parts by mass, preferably 0.05 to 5.0 parts by mass, more preferably 0.05 to 2.0 parts by mass, and even more preferably 0.05 to 1.0 parts by mass, based on 100 parts by mass of the rubber component or resin. By the content of the fluorine-containing copolymer being within the above range, the surface can be modified to be non-sticky. The weight average molecular weight of the fluorine-containing copolymer is preferably 2000 to 50000, more preferably 2000 to 20000, and even more preferably 3000 to 10000. By the weight average molecular weight of the fluorine-containing copolymer being within the above range, the non-sticky fluorine-containing copolymer can migrate to the surface of the rubber component or resin. Note that the weight average molecular weight Mw of the fluorine-containing copolymer can be measured by gel permeation chromatography (GPC).

[0014] The molar ratio of monomers (a) and (b) constituting the fluorine-containing copolymer is not particularly limited, but the molar ratio of monomers (a):(b) is preferably 10:1 to 1:100, more preferably 5:1 to 1:50, and even more preferably 2:1 to 1:40. By having the molar ratio of monomers (a) and (b) within the above range, the non-stick fluorine-containing copolymer can migrate to the surface of various rubber components or resins.

[0015] In monomer (a), n, a, b, and c are preferably n=2 to 4, more preferably 4, a=1 to 2, more preferably 2, b=1 to 2, and c=1 to 2. Specifically as monomer (a), examples include 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl acrylate, 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl methacrylate, and monomers with the following structural formulas. [ka]

[0016] R in the above monomer (b) in the fluorine-containing copolymer 2The group is an alkyl group, alkoxyalkyl group, cycloalkyl group, aryl group, or aralkyl group. Examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, n-hexyl, 2-ethylhexyl, n-octyl, lauryl, and stearyl; alkoxyalkyl groups such as methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, and 3-ethoxypropyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; and aralkyl groups such as benzyl. Examples of monoalkyl or dialkyl esters of fumaric acid include monomethyl, dimethyl, monoethyl, diethyl, monopropyl, dipropyl, monobutyl, dibutyl, mono-2-ethylhexyl, di-2-ethylhexyl, monooctyl, and dioctyl monoalkyl or dialkyl esters of fumaric acid. Examples of monoalkyl or dialkyl esters of maleic acid include monomethyl, dimethyl, monoethyl, diethyl, monopropyl, dipropyl, monobutyl, dibutyl, mono-2-ethylhexyl, di-2-ethylhexyl, monooctyl, dioctyl, and other monoalkyl or dialkyl esters of maleic acid. Specifically, monomers (b) include 2-ethylhexyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, behenyl methacrylate, cyclohexyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, behenyl acrylate, vinyl acetate, vinyl caprylate and other vinyl esters, and monomers with structural formulas represented by the following formulas. [ka]

[0017] The rubber component may contain additives other than rubber, such as crosslinking agents, crosslinking accelerators, acid acceptors, and fillers. The resin may contain polymerization initiators, fillers, and the like.

[0018] The above monomer (a) can be produced by esterifying a fluoroalkyl alcohol with acrylic acid or methacrylic acid. Alternatively, the fluoroalkyl alcohol can be produced from its corresponding fluoroalkyl iodide. The fluoroalkyl alcohol can be produced by first reacting the fluoroalkyl iodide with N-methylformamide HCONH(CH3) to obtain a mixture of the fluoroalkyl alcohol and its formic acid ester, and then hydrolyzing it in the presence of an acid catalyst.

[0019] The fluorine-containing copolymer of the present invention can be prepared, for example, as follows: a polymerization reaction between monomers (a) and (b) is carried out in the following solvents: fluorine-containing organic solvents such as 1,4-bis(trifluoromethyl)benzene, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, 1,1,1,2,3,4,4,5,5,5-decafluoropentane, and perfluorohexane; ester-based solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate acetate; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, and 2-hexanone; and solvents such as acetonitrile, dimethylformamide, diethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone.

[0020] When carrying out the polymerization reaction of a fluorine-containing copolymer, preferably 0.1 to 4 parts by mass, more preferably 1 to 2 parts by mass of a polymerization initiator can be used per 100 parts by mass of the total amount of monomers (a) and (b). Suitable polymerization initiators include diacyl peroxide, peroxycarbonate, peroxyester, etc. More specifically, suitable polymerization initiators include organic peroxides such as isobutyryl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, bis(heptafluorobutyryl) peroxide, pentafluorobutyroyl peroxide, bis(4-tertiary butylcyclohexyl) peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, azo compounds such as azobisisobutyronitrile, inorganic peroxides, or their redox systems. In addition, a polymerization initiator may be added during the polymerization reaction as needed.

[0021] To adjust the weight-average molecular weight of the fluorine-containing copolymer, a chain transfer agent may be used as needed. Examples of chain transfer agents include n-dodecyl mercaptan, dimethyl ether, methyl ter-butyl ether, C1-C6 alkanes, methanol, ethanol, 2-propanol, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, methane, ethyl acetate, ethyl malonate, and acetone.

[0022] The copolymerization reaction to obtain a fluorine-containing copolymer can preferably be carried out at a temperature of 0 to 100°C, more preferably 5 to 60°C, and even more preferably 40 to 50°C. Typically, after the polymerization reaction is complete, a copolymer solution with a solid content of 5 to 50% by mass is obtained, and the fluorine-containing copolymer can be obtained by removing the solvent from this copolymer solution. The fluorine-containing copolymer can be separated from the copolymer solution by methods such as evaporation to dryness or by adding a flocculant such as an inorganic salt to the copolymer solution to cause flocculation, and then purified by washing with a solvent.

[0023] (Method for producing non-adhesive compositions) The non-stick composition of the present invention can be obtained by mixing the fluorine-containing copolymer prepared as described above with a rubber component or resin. Alternatively, the non-stick composition of the present invention may be obtained by mixing the raw materials for the rubber component or resin with the fluorine-containing copolymer and then subjecting them to treatments such as vulcanization and heating.

[0024] Although embodiments of the present invention have been described above, the present invention is not limited to the embodiments described above, and includes all aspects included in the concept and claims of the present invention, and can be modified in various ways within the scope of the present invention. [Examples]

[0025] Next, examples will be described to further clarify the effects of the present invention, but the present invention is not limited to these examples.

[0026] <Preparation of fluorine-containing copolymers> A fluorine-containing copolymer was prepared as follows.

[0027] (Fluorine-containing copolymer 1) 1.7 g of DTFAC-103 (3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl acrylate; monomer (a)), 32.9 g of StAc (stearyl acrylate; monomer (b)), 46.8 g of MEK (methyl ethyl ketone; solvent), 1.5 g of AIBN (azobisisobutyronitrile; polymerization initiator), and 1.7 g of NDMC (n-dodecyl mercaptan; chain transfer agent) were charged into a 200 ml glass reactor equipped with a condenser and thermometer, and the polymerization reaction of DTFAC-103 and StAc was carried out at 68°C for 16 hours with stirring to obtain 81.5 g of a copolymer solution with a solid content of 40.5% by mass. The obtained copolymer solution was reprecipitation in methanol, and the solvent was removed in an oven at 120°C to obtain fluorine-containing copolymer 1 with DTFAC-103 and StAc as monomers. The weight-average molecular weight Mw of the obtained fluorine-containing copolymer 1 was measured by GPC and found to be 8200. Table 1 shows the amount of raw materials blended, the amount of copolymer solution recovered, the solid content concentration of the copolymer solution, and the weight-average molecular weight of fluorine-containing copolymer 1.

[0028] (Fluorine-containing copolymer 2~7) Fluorine-containing copolymers 2-7 were prepared in the same manner as fluorine-containing copolymer 1, except that the proportions and types of raw materials were changed as shown in Table 1. Table 1 shows the amount of copolymer solution recovered, the solid content concentration of the copolymer solution, and the weight-average molecular weight of fluorine-containing copolymers 2-7 during the preparation of fluorine-containing copolymers 2-7.

[0029] [Table 1] The symbols listed in Table 1 represent the following substances. DTFAC-103: 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl acrylate (monomer (a)), DTFMAC-103: 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl methacrylate (monomer (a)), StAc: Stearyl acrylate (monomer (b)), MEK: Methyl ethyl ketone (solvent) AIBN: Azobisisobutyronitrile (polymerization initiator) NDMC: n-dodecyl mercaptan (chain transfer agent).

[0030] (Examples 1-7 and Comparative Examples 1-2) The materials were kneaded in an open roll oven in the proportions shown in Table 2 below to obtain a compound. Mooney viscosity was measured for the obtained compound, and the scorch time (t5) at 125°C was measured in accordance with ISO 289. Next, press vulcanization (primary vulcanization) was performed at 180°C for 10 minutes, followed by oven vulcanization (secondary vulcanization) at 230°C for 22 hours. For each cross-linked molded product obtained in this way, the compression set at 200°C for 70 hours was measured using a P-24 O-ring in accordance with ASTM D395, Method B. Hardness, breaking strength, and elongation at break were also measured in accordance with ISO 37 and ISO 7619-1 Type 1A. The vulcanization conditions and the above measurement results are shown in Table 2.

[0031] Furthermore, after obtaining the compound for each example as described above, a mold release evaluation test was performed as follows. After placing the compound into the O-ring mold of the mold release evaluation machine, primary vulcanization was performed at 205°C for 3 minutes. The mold release properties of the cross-linked molded product when removing it from the mold after primary vulcanization were visually evaluated according to the following criteria. ○: There was no adhesion of the cross-linked molded product to the inside of the mold, and no damage to the cross-linked molded product, allowing for smooth release of the cross-linked molded product from the mold. △: Some adhesion of the cross-linked molded product to the mold was observed, but the cross-linked molded product could be released from the mold. ×: During demolding of the cross-linked molded product from the mold, significant damage occurred to the product, making demolding difficult. The results of the mold release evaluation are shown in Table 2 below.

[0032] [Table 2]

[0033] The results in Table 2 show that the non-stick composition of the present invention has excellent release properties. On the other hand, the composition of Comparative Example 1 did not contain the fluorine-containing copolymer of the present invention, so its release properties were "×". Furthermore, the composition of Comparative Example 2 contained a fluorine-based processing aid with a different chemical structure from the fluorine-containing copolymer of the present invention, so its release properties were "△".

[0034] (Example 8) A mixture was obtained by stirring and mixing 100 parts by mass of a polyurethane prepolymer (Coronate® C-4090 (trade name); manufactured by Nippon Polyurethane Industry Co., Ltd.) heated to 80°C, 12.8 parts by mass of a heated and melted methylene bis-o-chloroaniline curing agent (Ihara Cureamine MT (trade name); manufactured by Kumiai Chemical Industry Co., Ltd.), and 1.0 part by mass of the fluorine-containing copolymer 1 prepared above, while being careful not to entrain air bubbles. Next, the mixture was poured into an aluminum mold (45 mm in diameter, 50 mm in depth). A hook for removing the cured molded product was placed in the center of the cavity of the mold, and after the mixture was heated and cured at 120°C for 1 hour, the obtained molded product was removed from the mold by pulling the hook. The release load at this time was 15 N.

[0035] The mixture obtained by stirring and mixing each material in the same manner as in Example 8 was applied to a stainless steel plate (2 × 5 cm), and the mixture was heat-cured at 120°C for 1 hour. Static and dynamic contact angles, which are indicators of water- and oil-repellent performance, were measured (by the Cecil Drop method) on the obtained test specimens for water and hexadecane. The measurement results for water repellency and oil repellency are shown below. Water repellency: Static contact angle of water 112°, water fall angle (dynamic contact angle) 4° Oil repellency: Static contact angle of hexadecane: 40°, sliding angle (dynamic contact angle) of hexadecane: 2°.

[0036] (Comparative Example 3) A mixture was obtained by stirring 100 parts by mass of a polyurethane prepolymer (Coronate® C-4090 (product name); manufactured by Nippon Polyurethane Industry Co., Ltd.) heated to 80°C and 12.8 parts by mass of a heated and melted methylene bis-o-chloroaniline curing agent (Ihara Cureamine MT (product name); manufactured by Kumiai Chemical Industry Co., Ltd.) while taking care not to incorporate air bubbles. This mixture was poured into an aluminum mold (45 mm in diameter, 50 mm in depth). A hook for removing the cured molded product was placed in the center of the mold's cavity, and the mixture was heated and cured at 120°C for 1 hour. After that, the molded product was removed from the mold by pulling the hook. The release load at this time was 100 N or more, and the molded product could not be removed from the mold.

[0037] In the same manner as in Example 8, the mixture of Comparative Example 3 was applied to a stainless steel plate (2 × 5 cm), and then the mixture was heat-cured at 120°C for 1 hour. The static and dynamic contact angles (using the Cecil Drop method), which are indicators of water and oil repellency, were measured on the resulting test specimens for water and hexadecane. The results of the water and oil repellency measurements are shown below. Water repellency: Static contact angle of water 69°, angle of water falling (dynamic contact angle) 54° Oil repellency: Static contact angle of hexadecane: 8°, Roll-off angle (dynamic contact angle) of hexadecane: Unable to measure due to hexadecane adhering to the surface of the test specimen.

[0038] From Example 8 and Comparative Example 3 described above, it can be seen that the non-adhesive composition of the present invention has a low release load and excellent release properties. Furthermore, compared to Comparative Example 3, Example 8 had a larger static contact angle for water, a smaller dynamic contact angle for water, a larger static contact angle for hexadecane, and no adhesion of hexadecane to the test piece was observed during dynamic contact angle measurement. Therefore, it can be seen that molded articles of the non-adhesive composition of the present invention have excellent water and oil repellency.

Claims

1. A rubber component or resin that is acrylic rubber, polyurethane resin, or polyethylene resin; The rubber component or resin contains 0.05 to 10 parts by mass of a fluorine-containing copolymer per 100 parts by mass of the resin, The fluorine-containing copolymer is Monomer (a), C ｎ F ２ｎ＋１ (CH ２ CF ２ ) ａ (CF ２ CF ２ ) ｂ (CH ２ CH ２ ) ｃ OCOCR １ =CH ２ (In the formula, R １ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 6, a represents an integer of 1 to 4, b represents an integer of 1 to 3, and c represents an integer of 1 to 3), Monomer (b), R ２ OCOCR １ =CH ２ (In the formula, R １ is a hydrogen atom or a methyl group, R ２ represents an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group), a (meth)acrylic acid ester, a monoalkyl ester or dialkyl ester of fumaric acid, or a monoalkyl ester or dialkyl ester of maleic acid; is a copolymer of The weight average molecular weight of the fluorine-containing copolymer is 3,000 to 10,000. Non-stick composition.

2. The non-sticky composition according to claim 1, wherein the molar ratio of the monomers (a) and (b) constituting the fluorinated copolymer, monomer (a):(b), is 2:1 to 1:

100.

3. A method for producing a non-stick composition, comprising mixing a rubber component or a resin raw material with a fluorine-containing copolymer, and then vulcanizing, crosslinking, or polymerizing the mixture, The fluorine-containing copolymer is a monomer (a) which is a fluoroalkyl alcohol (meth)acrylic acid derivative represented by CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOCOCR1=CH2 (wherein R1 represents a hydrogen atom or a methyl group, n represents an integer of 1 to 6, a represents an integer of 1 to 4, b represents an integer of 1 to 3, and c represents an integer of 1 to 3); Monomer (b) is a (meth)acrylic acid ester represented by R 2 OCOCR 1 ═CH 2 (wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group), a monoalkyl ester or dialkyl ester of fumaric acid, or a monoalkyl ester or dialkyl ester of maleic acid; is a copolymer of The weight average molecular weight of the fluorine-containing copolymer is 3,000 to 10,000. Manufacturing method.