KR20210064194A - Copolymer and water and oil repellent - Google Patents

Abstract

Provided are a copolymer and a water and oil repellent agent having excellent water repellency, oil repellency and abrasion resistance. A constituent monomer containing at least a (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms, (meth)acrylic acid (a2) and a (meth)acrylate compound (a3) having a hydrocarbon ring structure is polymerized It is a copolymer formed by

Description

Copolymer and water and oil repellent

The present invention relates to a copolymer containing fluorine.

Conventionally, _{a fluorine-containing polymer having a C 8} F ₁₇ group has been used for a water and oil repellent agent and the like. Since these _{fluorine-containing polymers having C 8} F ₁₇ groups are concerned about toxicity of decomposition products _{, replacement with C 6} F ₁₃ groups or C ₄ F ₉ groups-containing materials is demanded.

Japanese Laid-Open Patent Publication No. 2011-99077

However, it turned out that the abrasion resistance of the water and oil repellent agent described in patent document 1 is not enough. The present invention has been made in view of the above, and an object of the present invention is to provide a copolymer excellent in water repellency, oil repellency and abrasion resistance.

The copolymer of the present invention comprises a (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms, (meth)acrylic acid (a2) and a (meth)acrylate compound (a3) having a hydrocarbon ring structure. At least, the constituent monomers contained therein are polymerized.

It is preferable that the said structural monomer contains the (meth)acrylate compound (a4) which has an aliphatic hydrocarbon group further.

The content of the (meth)acrylate compound (a3) having a hydrocarbon ring structure is 40 to 100 parts by mass based on 100 parts by mass of the (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms. desirable.

The water and oil repellent agent of this invention contains the said copolymer.

It is preferable that the said water and oil repellent agent further contains a crosslinking agent (b).

The article of the present invention has been treated using the above water and oil repellent agent.

According to the copolymer of the present invention, a copolymer excellent in water repellency, oil repellency and abrasion resistance and a water and oil repellent agent are obtained.

The copolymer of the present invention comprises a (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms, (meth)acrylic acid (a2) and a (meth)acrylate compound (a3) having a hydrocarbon ring structure. It is formed by polymerizing the constituent monomers to be contained at least. In addition, in this invention, "(meth)acrylate" means an acrylate or a methacrylate.

As (meth)acrylate compound (a1) which has a C1-C6 fluoroalkyl group in this invention, C1-C6 fluoroalkyl (meth)acrylate, C1-C6 fluoro A roalkylalkylene (meth)acrylate, a C1-C6 fluoroalkyl polyoxyfluoroalkylene (meth)acrylate, etc. are mentioned. Among these, fluoroalkyl (meth)acrylates having 1 to 6 carbon atoms and fluoroalkylalkylene (meth) acrylates having 1 to 6 carbon atoms are preferable from the viewpoint of more excellent water repellency, oil repellency and abrasion resistance, and 1 to 6 carbon atoms. -6 fluoroalkylalkylene (meth)acrylates are more preferable. Moreover, it is preferable that it is a C2-C6 fluoroalkyl group, and it is more preferable that it is a C4-C6 fluoroalkyl group from the point which is more excellent in water repellency, oil repellency, and abrasion resistance. Moreover, it is preferable that the said fluoroalkyl group is a perfluoroalkyl group at the point which is more excellent in water repellency, oil repellency, and abrasion resistance. In addition, in this specification, "(per)fluoro" means perfluoro or fluoro.

As said fluoroalkyl (meth)acrylate, For example, (per)fluoromethyl (meth)acrylate, (per)fluoroethyl (meth)acrylate, (per)fluoropropyl (meth)acryl rate, (per)fluorobutyl (meth)acrylate, (per)fluoropentyl (meth)acrylate, (per)fluorohexyl (meth)acrylate, etc. are mentioned. In addition, a C1-C6 fluoroalkyl (meth)acrylate can also be represented by the following general formula (1).

Rf-X ...(1)

However, Rf is a C1-C6 fluoroalkyl group, and X is an acryloyl group or a methacryloyl group.

As the fluoroalkylalkylene (meth)acrylate, for example, (per)fluoromethylmethylene (meth)acrylate, (per)fluoromethylethylene (meth)acrylate, (per)fluoroethyl Methylene (meth)acrylate, (per)fluoroethylethylene (meth)acrylate, (per)fluoropropylmethylene (meth)acrylate, (per)fluoropropylethylene (meth)acrylate, (per)fluoro Lobutylmethylene (meth)acrylate, (per)fluorobutylethylene (meth)acrylate, (per)fluoromethylpentylene (meth)acrylate, (per)fluoropentylethylene (meth)acrylate, ( Per) fluorohexyl methylene (meth) acrylate, (per) fluorohexyl ethylene (meth) acrylate, etc. are mentioned. In addition, a C1-C6 fluoroalkylalkylene (meth)acrylate can also be represented by the following general formula (2).

Rf-Y-X ...(2)

However, Rf is a C1-C6 fluoroalkyl group, Y is an alkylene group, X is an acryloyl group or a methacryloyl group.

Examples of the fluoroalkylpolyoxyfluoroalkylene (meth)acrylate include (per)fluoromethylpolyoxyfluoroethylene (meth)acrylate, (per)fluoroethylpolyoxyfluoroethylene (meth)acrylate, (per)fluoropropylpolyoxyfluoroethylene (meth)acrylate, (per)fluorobutylpolyoxyfluoroethylene (meth)acrylate, (per)fluoropentylpolyoxyfluoro Ethylene (meth)acrylate, (per)fluorohexylpolyoxyfluoroethylene (meth)acrylate, (per)fluorohexylpolyoxyfluoropropylene (meth)acrylate, etc. are mentioned. Moreover, a C1-C6 fluoroalkyl polyoxyfluoroalkylene (meth)acrylate can also be represented by the following general formula (3).

Rf-Z-X ...(3)

However, Rf is a C1-C6 fluoroalkyl group, Z is a polyoxyfluoroalkylene group, X is an acryloyl group or a methacryloyl group.

The (meth)acrylic acid (a2) in this invention is at least 1 sort(s) chosen from acrylic acid and methacrylic acid. The (meth)acrylic acid (a2) is 0.2 parts by mass or more based on 100 parts by mass of the (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms in view of more excellent water repellency, oil repellency and abrasion resistance. It is preferable that it is 0.5 mass part or more, and it is more preferable that it is 1 mass part or more. Moreover, it is preferable that it is 10 mass parts or less, It is more preferable that it is 5 mass parts or less, It is still more preferable that it is 3 mass parts or less.

As the (meth)acrylate compound (a3) having a hydrocarbon ring structure in the present invention, for example, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth) Aromatic hydrocarbon group containing (meth)acrylate compounds, such as alicyclic hydrocarbon group containing (meth)acrylate compounds, such as acrylate, benzyl (meth)acrylate, and phenoxyethyl (meth)acrylate, etc. are mentioned. Among these, an aromatic hydrocarbon group containing (meth)acrylate compound is preferable and benzyl (meth)acrylate is more preferable at the point which is more excellent in water repellency, oil repellency, and abrasion resistance. In addition, since water repellency and oil repellency are more excellent, and the sliding angle of water is smaller, an alicyclic hydrocarbon group-containing (meth)acrylate compound and an aromatic hydrocarbon group-containing (meth)acrylate compound It is preferable, and it is more preferable to contain isobornyl (meth)acrylate and benzyl (meth)acrylate.

The (meth)acrylate compound (a3) having a hydrocarbon ring structure is 100 parts by mass of the (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms in view of more excellent water repellency, oil repellency and abrasion resistance It is preferable that it is 5 mass parts or more with respect to it, It is more preferable that it is 15 mass parts or more, It is more preferable that it is 20 mass parts or more. Moreover, it is preferable that it is 200 mass parts or less, It is more preferable that it is 150 mass parts or less, It is still more preferable that it is 100 mass parts or less.

Moreover, the (meth)acrylate compound (a3) which has a hydrocarbon ring structure is more excellent in water repellency and oil repellency, and since the sliding angle of water becomes smaller, it has a C1-C6 fluoroalkyl group (meth). It is preferable that it is 25 mass parts or more with respect to 100 mass parts of acrylate compounds (a1), It is more preferable that it is 40 mass parts or more, It is still more preferable that it is 60 mass parts or more. Moreover, it is preferable that it is 200 mass parts or less, It is more preferable that it is 150 mass parts or less, It is still more preferable that it is 100 mass parts or less.

The (meth)acrylate compound (a3) having a hydrocarbon ring structure is more excellent in water repellency, oil repellency and abrasion resistance to 1 mole of the (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms. to 0.1 mol or more, more preferably 0.3 mol or more, and still more preferably 0.4 mol or more. Moreover, it is preferable that it is 5 mol or less, It is more preferable that it is 4 mol or less, It is still more preferable that it is 3 mol or less.

The (meth)acrylate compound (a3) which has a hydrocarbon ring structure is more excellent in water repellency and oil repellency, and since the sliding angle of water becomes smaller, the (meth)acrylate which has a C1-C6 fluoroalkyl group. It is preferable that it is 0.1 mol or more with respect to 1 mol of compound (a1), It is more preferable that it is 0.3 mol or more, It is still more preferable that it is 0.4 mol or more. Moreover, it is preferable that it is 5 mol or less, It is more preferable that it is 4 mol or less, It is still more preferable that it is 3 mol or less.

The (meth)acrylate compound (a3) having a hydrocarbon ring structure is preferably 3 parts by mass or more based on 1 part by mass of (meth)acrylic acid (a2) from the viewpoint of more excellent water repellency, oil repellency and abrasion resistance, 5 It is more preferable that it is mass part or more, and it is still more preferable that it is 10 mass parts or more. Moreover, it is preferable that it is 100 mass parts or less, It is more preferable that it is 70 mass parts or less, It is still more preferable that it is 50 mass parts or less.

Moreover, the (meth)acrylate compound (a3) which has a hydrocarbon ring structure is more excellent in water repellency and oil repellency, and since the sliding angle of water becomes smaller, with respect to 1 mass part of (meth)acrylic acid (a2), It is preferable that it is 15 mass parts or more, It is more preferable that it is 25 mass parts or more, It is still more preferable that it is 35 mass parts or more. Moreover, it is preferable that it is 100 mass parts or less, It is more preferable that it is 70 mass parts or less, It is still more preferable that it is 50 mass parts or less.

It is preferable that the structural monomer used for the copolymer of this invention contains the (meth)acrylate compound (a4) which has an aliphatic hydrocarbon group at the point which is more excellent in abrasion resistance. As the (meth)acrylate compound (a4) having an aliphatic hydrocarbon group, for example, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl ( Meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, isostearyl (meth)acrylate, and isoamyl (meth)acrylate. Among these, in terms of better abrasion resistance, lauryl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, isostearyl (meth) acrylate is preferable, and stearyl (meth)acrylate is more preferable.

The (meth)acrylate compound (a4) having an aliphatic hydrocarbon group is more excellent in water repellency, oil repellency and abrasion resistance, in 100 parts by mass of the (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms. To this, it is preferable that it is 5 mass parts or more, It is more preferable that it is 10 mass parts or more, It is still more preferable that it is 20 mass parts or more. Moreover, it is preferable that it is 100 mass parts or less, It is more preferable that it is 70 mass parts or less, It is still more preferable that it is 50 mass parts or less.

The (meth)acrylate compound (a4) having an aliphatic hydrocarbon group is more excellent in water repellency and oil repellency and abrasion resistance with respect to 1 mole of the (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms. , it is preferably 0.06 mol or more, more preferably 0.1 mol or more, and still more preferably 0.25 mol or more. Moreover, it is preferable that it is 1.3 mol or less, It is more preferable that it is 0.9 mol or less, It is still more preferable that it is 0.6 mol or less.

The (meth)acrylate compound (a4) having an aliphatic hydrocarbon group is preferably 5 parts by mass or more, and 10 parts by mass based on 1 part by mass of (meth)acrylic acid (a2) from the viewpoint of more excellent water repellency, oil repellency and abrasion resistance. It is more preferable that it is a part or more, and it is still more preferable that it is 20 mass parts or more. Moreover, it is preferable that it is 100 mass parts or less, It is more preferable that it is 70 mass parts or less, It is still more preferable that it is 50 mass parts or less.

The (meth)acrylate compound (a4) having an aliphatic hydrocarbon group is 30 parts by mass based on 100 parts by mass of the (meth)acrylate compound (a3) having a hydrocarbon ring structure from the viewpoint of more excellent water repellency, oil repellency and abrasion resistance. It is preferable that it is more than it, It is more preferable that it is 50 mass parts or more, It is still more preferable that it is 100 mass parts or more. Moreover, it is preferable that it is 300 mass parts or less, It is more preferable that it is 250 mass parts or less, It is still more preferable that it is 200 mass parts or less.

Since the (meth)acrylate compound (a4) having an aliphatic hydrocarbon group is more excellent in water repellency and oil repellency and wear resistance, it is 0.15 mol or more with respect to 1 mol of the (meth)acrylate compound (a3) having a hydrocarbon ring structure It is preferable, and it is more preferable that it is 0.26 mol or more, and it is still more preferable that it is 0.5 mol or more. Moreover, it is preferable that it is 1.5 mol or less, It is more preferable that it is 1.3 mol or less, It is still more preferable that it is 1.0 mol or less.

The copolymer of this invention can contain (meth)acrylate compounds other than said (a1)-(a4) in the range which does not impair the effect of this invention. As such a compound, for example, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acryl Rate, (meth) acrylic acid, (meth) acrylic acid amide, N-methylol (meth) acrylic acid amide, diacetone (meth) acrylic acid amide, isocyanate ethyl (meth) acrylate, (meth) acrylate having polysiloxane, 2- Methacroyloxyethyl acid phosphate, a dimethylaminomethyl (meth)acrylate oxyalkylene group containing (meth)acrylate monomer, etc. are mentioned.

Although the copolymer used by this embodiment is not specifically limited, It is preferable that weight average molecular weights are 2,000-100,000, It is more preferable that it is 3,000-50,000, It is still more preferable that it is 4,000-20,000. When the weight average molecular weight is within the above range, it is easy to obtain a water and oil repellent agent excellent in water repellency, oil repellency, and oil removability. In addition, the weight average molecular weight can be measured under the following conditions using the GPC column chromatography method, and what was calibrated with polyethyleneglycol of molecular weight 300, 2000, 8000, and 20000 was used as a standard sample.

·GPC device: System controller: CBM-20A (manufactured by Shimadzu Corporation)

・Detector: RID-10A (manufactured by Shimadzu Corporation)

·Column: Shodex GPC KF-G, KF-803, KF-802.5, KF-802, KF-801 connected (all manufactured by Showa Denko)

·Eluent: tetrahydrofuran

・Sample injection: 5 wt% solution, 50 μl

Flow rate: 0.8 ml/min

·Temperature: 25 ℃

As the method for producing the copolymer of the present invention, for example, (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms, (meth)acrylic acid (a2), (meth) having a hydrocarbon ring structure ) A step of mixing the acrylate compound (a3), a (meth)acrylate compound (a4) having an aliphatic hydrocarbon group or (meth)acrylate compound other than (a1) to (a4), an organic solvent and a polymerization initiator if necessary and heating the obtained mixture at 40 to 120°C to carry out a polymerization reaction.

As for the polymerization method, solution polymerization is preferable. Although polymerization temperature is not specifically limited, Usually, the range of 40-120 degreeC is preferable. Although polymerization time is not specifically limited, Usually, it is about 4 to 15 hours.

It will not specifically limit as an organic solvent if reaction is not inhibited, For example, water may be sufficient as a solvent (c), and an organic solvent may be sufficient as it. Examples of the organic solvent include aromatic solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane and isophorone, acetone, methyl ethyl ketone, cyclohexanone, etc. ketone solvents, ester solvents such as ethyl acetate and butyl acetate, glycol ether ester solvents such as ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene Glycol ether solvents, such as glycol diethyl ether, diethylene glycol dibutyl ether, and propylene glycol dibutyl ether, dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, etc. are mentioned, Among these, It is preferable that they are acetone, methyl ethyl ketone, ethyl acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

As the polymerization initiator, a conventionally known one can be used, for example, benzoyl peroxide, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, 1,1,3,3-tetra Peroxides, such as methylbutylperoxy-2-ethylhexanoate and t-hexylperoxyisopropyl monocarbonate, azobisisobutyronitrile, 2,2'- azobis-2-methylbutyronitrile, etc. Azo compounds, etc. are mentioned. Although the usage-amount is not specifically limited, Usually, 0.1-5 mass parts is preferable with respect to 100 mass parts of total amounts of a constituent monomer.

The water and oil repellent agent of the present invention contains the above copolymer and may further contain a solvent. As such a solvent, water, the organic solvent illustrated above, etc. are mentioned, for example. In addition, as a solvent, the solvent used at the time of manufacture of a copolymer may be used as it is, may be diluted with a solvent as needed, and may substitute with another organic solvent.

Although content of the copolymer in a water and oil repellent agent is not specifically limited, It is preferable that it is 1-50 mass %.

It is preferable that the water and oil repellent agent of this invention contains a crosslinking agent (b) at the point which is more excellent in abrasion resistance. As such a crosslinking agent, a carbodiimide type crosslinking agent, an oxazoline type crosslinking agent, an epoxy type crosslinking agent, etc. are mentioned, for example. Moreover, a silane coupling agent can also be used as a crosslinking agent (b).

Examples of the carbodiimide-based crosslinking agent include Nisshinbo Co., Ltd. Carbodilite V-02, Carbodilite V-04, Carbodilite V-05, Carbodilite V-07, Carbodilite V -02-L2, carbodilite E-01, carbodilite E-02, carbodilite E-03A, carbodilite E-04, and the like.

Examples of the oxazoline-based crosslinking agent include Epocross K-2010E, Epocross K-2020E, Epocross K-2030E, Epocross WS-500, and Epocross WS-700 manufactured by Nippon Catalyst. have.

Examples of the epoxy-based crosslinking agent include Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622, and Denacol EX-622 manufactured by Nagase Chemtex Co., Ltd. Call EX-512, Denacol EX-521, Denacol EX-411, Denacol EX-421, Denacol EX-301, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX -211, Denacol EX-810, Denacol EX-811, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861 , Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-921, Denacol EX-931, Denacol EX-145, Denacol EX-171, Denacol EX-701, Kyo Epolite 40E, Eporite 100E, Eporite 200E, Eporite 400E, Eporite 70P, Eporite 200P, Eporite 400P, Eporite 1500NP, Epolite 80MF, Eporite 100MF, Sakamoto Pharmaceuticals manufactured by Aisha Chemical Co., Ltd. SR-NPG, SR-16H, SR-TMP, SR-TPG, SR-4PG, SR-2EG, SR-8EG, SR-8EGS, SR-GLG, SR-DGE, SR-4GL manufactured by Industrial Co., Ltd. SR-4GLS, Nihon Oil Co., Ltd. Epiol BE-200, Epiol G-100, Epiol E-100, Epiol E-400, Epiol E-1000, Epiol P-200, Epiol NPG -100, epiol TMP-100, epiol OH, and the like.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ- aminopropylethoxysilane, N-[2-(vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane; γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyl Trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ -Aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyl Trimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, dimethoxydiphenylsilane, n-propyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, 1,6-bis(trime) Toxysilyl) hexane, trifluoropropyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltriethoxysilane, hexyltriethoxysilane, Octyltriethoxysilane, hexamethyldisilazane, etc. are mentioned.

As for the said crosslinking agent (b), an epoxy type crosslinking agent, an oxazoline type crosslinking agent, a silane coupling agent, and a carbodiimide type crosslinking agent are preferable at the point which is more excellent in abrasion resistance.

Although the content rate of the said crosslinking agent (b) is not specifically limited, It is preferable that it is 1-30 mass parts with respect to 100 mass parts of constituent monomers, It is preferable that it is 1-20 mass parts, It is more preferable that it is 1-15 mass parts. . The said crosslinking agent (b) may be used independently and may use 2 or more types together.

To the water and oil repellent agent of the present invention, other water repellent agents, other oil repellent agents, crosslinking agents, insect repellents, flame retardants, wrinkle inhibitors, antistatic agents, softening finishing agents, preservatives, air fresheners, antioxidants, You may contain a pigment, a leveling agent, a plasticizer, and a dispersing agent.

The article of the present invention has been treated using the water and oil repellent agent of the present invention. It does not specifically limit as a processing method, A coating method, a spray method, a immersion method, etc. can be selected suitably. The article to be treated with the water and oil repellent agent is not particularly limited, and examples thereof include fiber, leather, stone, wood, paper, glass, plastic, metal, and electronic substrate. In addition, as for the method of processing these articles|goods, the processing method according to each article can be selected suitably.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to the following Example. In addition, in the following Examples and Comparative Examples, "part" or "%" is based on mass unless otherwise specified.

(raw material used)

(meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms

(a1-1) perfluorohexyl ethyl methacrylate

(a1-2) perfluorobutyl ethyl methacrylate

(meth)acrylic acid (a2)

(a2-1) acrylic acid

(a2-2) methacrylic acid

(meth)acrylate compound (a3) having a hydrocarbon ring structure

(a3-1) isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light acrylate IB-XA)

(a3-2) benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Ester BZ)

(meth)acrylate compound (a4) having an aliphatic hydrocarbon group

(a4-1) stearyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Ester S)

crosslinking agent (b)

(b-1) Silane coupling agent (trade name: KBM-903, 3-aminopropyltrimethoxysilane)

(b-2) Epoxy-based crosslinking agent (brand name: Denacol EX-313)

(b-3) Oxazoline-based crosslinking agent (trade name: Epocross WS-500, 39% by mass solution)

(b-4) Carbodiimide-based crosslinking agent (trade name: Carbodilite V-02-L2, 40% by mass solution)

solvent (c)

(c-1) ethyl acetate

(c-2) diethylene glycol diethyl ether

(c-3) methyl ethyl ketone

(Examples 1 to 15, Comparative Example 2)

To a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux tube, (a1) to (a4) and a solvent (c) were added in the proportions shown in Table 1, and nitrogen substitution was performed. Then, t-butylperoxypivalate (manufactured by Nichi Oil Co., Ltd., brand name: perbutyl PV) is 3 mass parts by mass with respect to 100 mass parts of the total amount of the (meth)acrylate compound of the above (a1) to (a4). It added so that it might be added and made it react at 65 degreeC for 8 hours, and the copolymer (concentration of a copolymer 25 mass %) was obtained.

A water and oil repellent agent was prepared by adding a crosslinking agent (b) to the obtained copolymer solution and further diluting it with ethyl acetate so that the concentration of the copolymer was 1 mass%. The test piece was produced by apply|coating this water and oil repellent agent by the spin coating method so that it might become a film thickness of 20 micrometers on a glass plate (76 mm x 26 mm), and drying it in 105 degreeC oven for 10 minutes.

(Comparative Example 1)

A test piece was prepared in the same manner as in Example 1 except that methyl ethyl ketone was used instead of the copolymer solution.

Using the above test pieces, the contact angle (water and hexadecane), abrasion resistance and sliding angle were evaluated by the following method. Table 1 shows the results.

(contact angle)

Using a contact angle measuring apparatus (manufactured by Kyowa Interface Science, trade name: Contact Angle Meter Drop Master 500), the contact angles of water and hexadecane on the coated surface were measured and evaluated according to the following criteria. In addition, the droplet volume of 2 microliters and the droplet volume of hexadecane were 4 microliters, and the contact angle 30 second after dripping was measured.

<Water contact angle>

A : More than 110°

B : More than 100° and less than 110°

C : More than 90° and less than 100°

D : More than 70° and less than 90°

E : More than 50° and less than 70°

F : less than 50°

<Contact angle of hexadecane>

A : 60° or more

B : More than 50° and less than 60°

C : 40° or more and less than 50°

D : More than 30° and less than 40°

E: less than 30°

(wear resistance)

The coated surface of the test piece was subjected to 30 reciprocating rubbing at a weight of 100 g/cm 2 using tissue paper (Ittoko Tissue: manufactured by Itoman). Using the test piece after friction, the contact angle of water and hexadecane was evaluated in the same manner as the contact angle.

(Glide angle)

Using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., trade name: Contact Angle Meter Drop Master 500), 20 μl of water was dripped onto the applied surface in a horizontal state, the inclination angle of the test piece was gradually increased, and the sap began to slip. was measured as the sliding angle, and evaluated according to the following criteria.

A: less than 30°

B : More than 30° and less than 40°

C : 40° or more but less than 70°

D : More than 70° and less than 90°

E: Does not glide even at 90°

As is clear from Table 1, it is understood that the water and oil repellent agents containing the copolymers of Examples 1 to 15 are excellent in water repellency, oil repellency and abrasion resistance. Further, as is clear from Examples 1 and 2, as the (meth)acrylate compound (a3) having a hydrocarbon ring structure, an alicyclic hydrocarbon group-containing (meth)acrylate compound and an aromatic hydrocarbon group-containing (meth)acrylate compound It turns out that a sliding angle becomes smaller by containing. Moreover, it turns out that abrasion resistance is more excellent by containing the (meth)acrylate compound (a4) which has an aliphatic hydrocarbon group as a structural monomer evidently from Examples 3-7.

Industrial applicability

The copolymer of the present invention can be preferably used as a water and oil repellent agent.

Claims (6)

A constituent monomer containing at least a (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms, (meth)acrylic acid (a2) and a (meth)acrylate compound (a3) having a hydrocarbon ring structure is polymerized A copolymer made by The method of claim 1,
The copolymer in which the said structural monomer further contains the (meth)acrylate compound (a4) which has an aliphatic hydrocarbon group. The method according to claim 1 or 2,
The content of the (meth)acrylate compound (a3) having a hydrocarbon ring structure is 40 to 100 parts by mass based on 100 parts by mass of the (meth)acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms, coalescence. A water and oil repellent agent comprising the copolymer according to any one of claims 1 to 3. The method of claim 4,
A water and oil repellent agent further comprising a crosslinking agent (b). An article treated with the water and oil repellent agent according to claim 4 or 5.