阅读说明：本技术 含有含氟共聚物的组合物及消泡剂 (Composition containing fluorine-containing copolymer and defoaming agent ) 是由 岩木彻 池田元城 于 2020-03-12 设计创作，主要内容包括：本发明提供一种在各种溶剂中的溶解性优异,并且抑制涂布不均发生的技术。含有含氟共聚物的组合物包含：共聚物(A),是将包含具有碳数1～6的氟烷基的(甲基)丙烯酸酯化合物(a1)和具有聚氧亚烷基的(甲基)丙烯酸酯化合物(a2)的构成单体(a)聚合而形成；以及共聚物(B),是不同于共聚物(A)的共聚物,且是将包含具有碳数1～6的氟烷基的(甲基)丙烯酸酯化合物(a1)和具有烃环结构的(甲基)丙烯酸酯化合物(a3)的构成单体(b)聚合而形成。(The invention provides a technique for suppressing the occurrence of coating unevenness while having excellent solubility in various solvents. The composition containing a fluorocopolymer comprises: a copolymer (A) formed by polymerizing a constituent monomer (a) including a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a2) having a polyoxyalkylene group; and a copolymer (B) which is different from the copolymer (A) and is formed by polymerizing a constituent monomer (B) comprising a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a3) having a hydrocarbon ring structure.)

1. A fluorocopolymer-containing composition comprising:

a copolymer (A) formed by polymerizing a constituent monomer (a) including a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a2) having a polyoxyalkylene group; and

the copolymer (B) is different from the copolymer (A) and is formed by polymerizing a constituent monomer (B) containing a (meth) acrylate compound (a1) having a fluoroalkyl group with 1-6 carbon atoms and a (meth) acrylate compound (a3) having a hydrocarbon ring structure.

2. The fluorocopolymer-containing composition according to claim 1, wherein,

the constituent monomer (b) further contains a (meth) acrylate compound (a4) having an aliphatic hydrocarbon group.

3. The fluorocopolymer-containing composition according to claim 1 or 2,

at least one of the (meth) acrylate compound (a1) contained in the constituent monomer (a) and the (meth) acrylate compound (a1) contained in the constituent monomer (b) contains a methacrylate ester.

4. The fluorocopolymer-containing composition according to claim 1 or 2,

at least one of the (meth) acrylate compound (a1) contained in the constituent monomer (a) and the (meth) acrylate compound (a1) contained in the constituent monomer (b) contains perfluorohexylethyl methacrylate.

5. A defoaming agent, which is characterized in that,

the defoaming agent contains a copolymer formed by polymerizing a constituent monomer containing a (meth) acrylate compound having a fluoroalkyl group with 1-6 carbon atoms and a (meth) acrylate compound having a hydrocarbon ring structure.

Technical Field

The present invention relates to a composition containing a fluorocopolymer and an antifoaming agent.

Background

Conventionally, a method of forming a coating film by applying a fluorine-containing compound to the surface of a base material such as glass, metal, or fiber has been known (for example, patent document 1).

Patent document 1 discloses a coating composition containing a polymer obtained by polymerizing an ethylenically unsaturated monomer containing a perfluoroalkyl group having 6 or less carbon atoms as an essential component.

When the coating film is formed using a fluorine-containing compound, a composition which is dissolved in various solvents is preferable for use in a wide range of applications. As such a composition, patent document 2 discloses a polymer obtained by polymerizing 1 mol of an ethylenically unsaturated group in an ethylenically unsaturated monomer group containing a fluorinated alkyl group with 0.07 to 0.7 mol of a polymerization initiator.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2002-249706

Patent document 2: japanese laid-open patent publication No. 2006-249130

Disclosure of Invention

Technical problem to be solved by the invention

In the composition described in patent document 1, 35 parts by mass of an ethylenically unsaturated monomer containing a perfluoroalkyl group having 6 or less carbon atoms is blended at most in 100 parts by mass of the copolymer composition. However, the inventors have found that: when such a large amount of the monomer is blended, foaming is likely to occur, and unevenness is likely to occur when the coating is applied to the surface of a substrate.

The composition described in patent document 2 has excellent solubility in various solvents, but has a problem that unevenness is likely to occur when the composition is applied to the surface of a substrate. Therefore, it is desired to develop a technique that has excellent solubility in various solvents and suppresses the occurrence of coating unevenness.

Means for solving the problems

The present invention has been made to solve the above problems, and can be realized as the following embodiments.

(1) According to one embodiment of the present invention, there is provided a composition containing a fluorocopolymer. The composition containing a fluorocopolymer comprises:

a copolymer (A) formed by polymerizing a constituent monomer (a) including a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a2) having a polyoxyalkylene group; and

the copolymer (B) is different from the copolymer (A) and is formed by polymerizing a constituent monomer (B) containing a (meth) acrylate compound (a1) having a fluoroalkyl group with 1-6 carbon atoms and a (meth) acrylate compound (a3) having a hydrocarbon ring structure.

The composition containing the fluorocopolymer of this embodiment is excellent in solubility in various solvents and can suppress the occurrence of coating unevenness.

(2) In the composition containing a fluorocopolymer in the above embodiment, the constituent monomer (b) may further contain a (meth) acrylate compound (a4) having an aliphatic hydrocarbon group.

The composition containing the fluorocopolymer of this embodiment is more excellent in solubility in various solvents and can further suppress the occurrence of coating unevenness.

(3) In the fluorocopolymer-containing composition of the above embodiment, at least one of the (meth) acrylate compound (a1) contained in the constituent monomer (a) and the (meth) acrylate compound (a1) contained in the constituent monomer (b) may contain a methacrylate ester.

The composition containing the fluorocopolymer of this embodiment is excellent in stain resistance.

(4) In the fluorocopolymer-containing composition of the above embodiment, at least one of the (meth) acrylate compound (a1) contained in the constituent monomer (a) and the (meth) acrylate compound (a1) contained in the constituent monomer (b) may contain perfluorohexylethyl methacrylate.

The composition containing the fluorocopolymer of this embodiment is more excellent in solubility in various solvents and can further suppress the occurrence of coating unevenness.

(5) According to another aspect of the present invention, there is provided a defoaming agent. The defoaming agent contains a copolymer obtained by polymerizing a constituent monomer containing a (meth) acrylate compound having a fluoroalkyl group with 1-6 carbon atoms and a (meth) acrylate compound having a hydrocarbon ring structure.

The defoaming agent according to this embodiment can suppress the generation of foam.

Detailed Description

A. Composition containing fluorine-containing copolymer

A composition containing a fluorocopolymer (hereinafter, also simply referred to as "composition") according to an embodiment of the present invention includes (i) a copolymer (a) obtained by polymerizing a constituent monomer (a) including a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a2) having a polyoxyalkylene group. The composition of the present embodiment includes (ii) a copolymer (B) obtained by polymerizing a constituent monomer (B) including a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a3) having a hydrocarbon ring structure. Here, the copolymer (a) and the copolymer (B) mean different copolymers. In the present specification, "(meth) acrylate" means acrylate or methacrylate.

The composition of the present embodiment has excellent solubility in various solvents and excellent leveling properties. In the present specification, "leveling" means a degree at which coating unevenness is not likely to occur. Leveling is mainly affected by viscosity, defoaming property, solubility, or the like. As a mechanism for estimating excellent leveling, it is considered that the orientation of the copolymer (a) in the gas-liquid interface can be inhibited by including the copolymer (B) having a structure different from that of the copolymer (a) in the composition, and thus the generation of bubbles can be suppressed.

A1. Copolymer (A)

The composition of the present embodiment is a copolymer obtained by polymerizing a constituent monomer (a) including a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a2) having a polyoxyalkylene group.

< (meth) acrylate Compound (a1) >

Examples of the (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms in the present embodiment include: fluoroalkyl (meth) acrylate, fluoroalkyl alkyl (meth) acrylate, fluoroalkyl polyoxyalkylene (meth) acrylate, and the like. Of these, fluoroalkyl (meth) acrylates and fluoroalkyl (meth) acrylates are preferable, and fluoroalkyl (meth) acrylates are more preferable, because of their excellent solubility and leveling property. The fluoroalkyl group is preferably a fluoroalkyl group having 2 to 6 carbon atoms, and more preferably a fluoroalkyl group having 4 to 6 carbon atoms, for excellent antifouling property, solubility and leveling property. Here, in the present specification, "fluorine" includes perfluoro. The fluoroalkyl group is preferably a perfluoroalkyl group.

Examples of the fluoroalkyl (meth) acrylate include: fluoromethyl (meth) acrylate, fluoroethyl (meth) acrylate, fluoropropyl (meth) acrylate, fluorobutyl (meth) acrylate, fluoropentyl (meth) acrylate, fluorohexyl (meth) acrylate, and the like.

Here, the fluoroalkyl (meth) acrylate may be represented by the following general formula (1).

Rf-O-X (1)

Wherein Rf is fluoroalkyl, and X is acryloyl or methacryloyl.

Examples of fluoroalkyl alkyl (meth) acrylates include: fluoromethyl methyl (meth) acrylate, fluoromethyl ethyl (meth) acrylate, fluoroethyl methyl (meth) acrylate, fluoroethyl ethyl (meth) acrylate, fluoropropyl methyl (meth) acrylate, fluoropropyl ethyl (meth) acrylate, fluorobutyl methyl (meth) acrylate, fluorobutyl ethyl (meth) acrylate, fluoropentyl methyl (meth) acrylate, fluoropentyl ethyl (meth) acrylate, fluorohexyl methyl (meth) acrylate, fluorohexyl ethyl (meth) acrylate, and the like. The fluoroalkyl alkyl (meth) acrylate may be represented by the following general formula (2).

Rf-Y-O-X (2)

Wherein Rf is fluoroalkyl, Y is alkylene, and X is acryloyl or methacryloyl.

Examples of the fluoroalkyl polyoxyalkylene (meth) acrylate include: fluoromethylpolyoxyfluoroethylene (meth) acrylate, fluoroethylpolyoxyfluoroethylene (meth) acrylate, fluoropropylpolyethyleneoxyfluoroethylene (meth) acrylate, fluorobutylpolyethyleneoxyfluoroethylene (meth) acrylate, fluoropentylpolyoxyfluoroethylene (meth) acrylate, fluorohexylpolyethyleneoxyfluoride (meth) acrylate, fluorohexylpolypropyleneoxide (meth) acrylate, and the like. The fluoroalkyl polyoxyalkylene (meth) acrylate may be represented by the following general formula (3).

Rf-Z-O-X (3)

Wherein Rf is fluoroalkyl, Z is polyoxyfluoroalkylene, and X is acryloyl or methacryloyl.

< (meth) acrylate Compound (a2) >

Examples of the (meth) acrylate compound having a polyoxyalkylene group (a2) in the present embodiment include those represented by the following general formula (4). The term "corresponds to the component (a 1)" is excluded.

R¹-O-(YO)_n-X (4)

Wherein R is¹Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Y is an alkylene group, n is an integer of 2 or more, and X is an acryloyl group or a methacryloyl group.

R in the above general formula (4) is excellent in solubility and leveling property¹Preferably an alkyl group having 1 to 6 carbon atoms. The compound of the general formula (4) is preferably polyoxyalkylene glycol monoalkyl ether (meth) acrylate for excellent solubility and leveling property.

The alkylene group in the general formula (4) is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and particularly preferably 2 to 4 carbon atoms, from the viewpoint of more excellent solubility. Specifically, examples of the alkylene group in the general formula (4) include a methylene group, an ethylene group, a propylene group, and a butylene group, and these alkylene groups may have a substituent other than halogen. Among these, ethylene and propylene are preferable, and ethylene is more preferable, from the viewpoint of more excellent solubility. The polyoxyalkylene group may be one of these alkylene groups, or two or more of these alkylene groups may be polymerized. When two or more kinds of alkylene groups are polymerized, the polymerization may be random polymerization or block polymerization.

The average number n of repeating units of the oxyalkylene group in the general formula (4) is not particularly limited, but is preferably 8 or more and 150 or less in terms of more excellent solubility. The lower limit of the average number of repeating units n is more preferably 10 or more, still more preferably 15 or more, and still more preferably 20 or more. The upper limit of the average repeating unit number n is more preferably 120 or less, still more preferably 100 or less, yet more preferably 70 or less, and particularly preferably 40 or less.

The constituent monomer (a) constituting the copolymer (a) of the present embodiment may include monomers other than the above-mentioned components (a1) to (a2) within a range not departing from the object of the invention.

The content of the component (a1) in the monomer (a) is not particularly limited, but is preferably 5 to 90% by mass in order to achieve excellent solubility and leveling property. The lower limit of the content of the component (a1) in the constituent monomer (a) is more preferably 10% by mass or more, still more preferably 30% by mass or more, and still more preferably 50% by mass or more. The upper limit of the content of the component (a1) in the monomer (a) is more preferably 80% by mass or less, and still more preferably 70% by mass or less.

The content of the component (a2) in the monomer (a) is not particularly limited, but is preferably 5 to 90% by mass in order to achieve excellent solubility and leveling properties. The lower limit of the content of the component (a2) in the constituent monomer (a) is more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, and particularly preferably 35% by mass or more. The upper limit of the content of the component (a2) in the constituent monomer (a) is more preferably 70% by mass or less, still more preferably 50% by mass or less, and particularly preferably 45% by mass or less.

The content ratio of the component (a1) and the component (a2) in the constituent monomer (a) is not particularly limited, but for excellent solubility, the content ratio of the component (a1) is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and particularly preferably 55 parts by mass or more, when the total of the component (a1) and the component (a2) is 100 parts by mass. On the other hand, in order to have excellent solubility, when the total of the component (a1) and the component (a2) is 100 parts by mass, the content of the component (a1) is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 65 parts by mass or less.

The copolymer (a) used in the present embodiment is not particularly limited, and preferably has a weight average molecular weight of 2000 to 100000, more preferably 2500 to 50000, and still more preferably 3000 to 20000. When the weight average molecular weight is within the above range, a composition having excellent leveling property and solubility can be easily obtained. In the present specification, the weight average molecular weight can be measured using GPC (gel permeation chromatography) column chromatography under the following conditions, and calibrated using polyethylene glycols having molecular weights of 300, 2000, 8000 and 20000 as standard samples.

An apparatus: LC-10AD (manufactured by Shimadzu corporation)

The detector: RID-10A (manufactured by Shimadzu corporation)

Column: those obtained by joining Shodex GPC KF-G, KF-803, KF802.5, KF-802, and KF-801 (all manufactured by Showa Denko K.K.)

Eluent: tetrahydrofuran (THF)

Sample injection: 0.5 wt.% solution, 100. mu.L

Flow rate: 0.8mL/min

Temperature: 25 deg.C

A2. Copolymer (B)

The copolymer (B) of the present embodiment is a copolymer obtained by polymerizing a constituent monomer (B) including a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a3) having a hydrocarbon ring structure.

< the (meth) acrylic acid ester Compound (a1) > (of the copolymer (B)

The (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms in the copolymer (B) of the present embodiment may be the same compound as the (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms in the copolymer (a) of the present embodiment, or may be a different compound. Specific examples of the (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms are the same as those of the (meth) acrylate compound (a1) of the copolymer (a), and thus the description thereof is omitted.

< (meth) acrylate Compound (a3) >

The (meth) acrylate compound (a3) having a hydrocarbon ring structure in the copolymer (B) of the present embodiment is not particularly limited, and examples thereof include: alicyclic hydrocarbon group-containing (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and 1-adamantyl (meth) acrylate, (meth) acrylate compounds containing an aromatic hydrocarbon group such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, and the like. For excellent foam suppressing properties, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate are more preferable as the (meth) acrylate compound (a3) having a hydrocarbon ring structure.

< (meth) acrylate Compound (a4) >

The (meth) acrylate compound (a4) having an aliphatic hydrocarbon group in the copolymer (B) of the present embodiment is not particularly limited, and examples thereof include: 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, isoamyl (meth) acrylate, and the like. The aliphatic hydrocarbon group-containing (meth) acrylate compound (a4) is preferably 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, or stearyl (meth) acrylate, and more preferably stearyl (meth) acrylate, for excellent solubility and leveling properties.

The constituent monomer (B) constituting the copolymer (B) of the present embodiment may contain monomers other than the above-mentioned components (a1), (a3), and (a4) within a range not prejudicial to the object of the invention.

The content of the component (a1) in the monomer (b) is not particularly limited, but is preferably 5 to 90% by mass in order to achieve excellent solubility, foam inhibition, and leveling properties. The lower limit of the content of the component (a1) in the constituent monomer (b) is more preferably 10% by mass or more, still more preferably 30% by mass or more, and still more preferably 50% by mass or more. The upper limit of the content of the component (a1) in the constituent monomer (b) is more preferably 80% by mass or less, and still more preferably 70% by mass or less.

The content of the component (a3) in the constituent monomer (b) is not particularly limited, but is preferably 5 to 90% by mass in order to achieve excellent solubility and leveling property. The lower limit of the content of the component (a3) in the constituent monomer (b) is more preferably 5% by mass or more, still more preferably 10% by mass or more, and still more preferably 13% by mass or more. The upper limit of the content of the component (a3) in the constituent monomer (b) is more preferably 70% by mass or less, still more preferably 50% by mass or less, particularly preferably 40% by mass or less, still more preferably 30% by mass or less, and still more preferably 25% by mass or less.

The content of the component (a4) in the constituent monomer (b) is not particularly limited, but is preferably 5 to 90% by mass in order to achieve excellent solubility and leveling property. The lower limit of the content of the component (a4) in the constituent monomer (b) is more preferably 5% by mass or more, still more preferably 10% by mass or more, and still more preferably 20% by mass or more. The upper limit of the content of the component (a4) in the constituent monomer (b) is more preferably 70% by mass or less, still more preferably 50% by mass or less, particularly preferably 40% by mass or less, and still more preferably 30% by mass or less.

The copolymer (B) used in the present embodiment is not particularly limited, and preferably has a weight average molecular weight of 2000 to 100000, more preferably 3000 to 50000, and still more preferably 5000 to 20000. When the weight average molecular weight is within the above range, a composition having excellent leveling property and solubility can be easily obtained.

The mass ratio ((B)/(a)) of the copolymer (B) to the copolymer (a) in the composition of the present embodiment is not particularly limited, but is preferably 2.00 or less, more preferably 1.50 or less, further preferably 1.00 or less, and still further preferably 0.50 or less, for excellent solubility. In order to have excellent foam suppression, the mass ratio ((B)/(a)) is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.10 or more.

The solvent used in the present embodiment may be water or an organic solvent. 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; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, and propylene glycol diacetate; glycol ether ester solvents such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl acetate, and 3-methoxy-3-methylbutyl acetate; glycol ether solvents such as ethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol dibutyl ether, triethylene glycol Dimethyl ether (diethylene triglycol), diethylene glycol methyl ethyl ether, and diethylene glycol Dimethyl propylene ether; dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, etc., and among them, acetone, methyl ethyl ketone, ethyl acetate, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, methyl ethyl diethylene glycol, propylene glycol monomethyl ether acetate, 3-methoxy-3-methylbutyl acetate, and dimethylpropylene diethylene glycol are preferable.

Next, a method for producing the composition of the present embodiment will be described. The method for producing the composition is not particularly limited, and examples thereof include the following methods. First, a copolymer (a) is obtained by mixing a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a2) having a polyoxyalkylene group with a solvent and heating the mixture. Then, the copolymer (B) is obtained by mixing a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a3) having a hydrocarbon ring structure with a solvent and heating the mixture. Then, the copolymer (A) and the copolymer (B) are mixed with a solvent.

The polymerization method is not particularly limited, and solution polymerization is preferable. The polymerization temperature is not particularly limited, but is preferably in the range of 40 ℃ to 120 ℃. The polymerization time is not particularly limited, but is preferably about 4 to 15 hours.

A polymerization initiator may be used for the polymerization. The polymerization initiator is not particularly limited, and examples thereof include peroxides such as benzoyl peroxide, t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, and 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate; azo compounds such as azobisisobutyronitrile and 2,2' -azobis-2-methylbutyronitrile. The amount of the polymerization initiator used is not particularly limited, and is generally preferably 0.1 to 5 parts by mass per 100 parts by mass of the constituent monomer.

The composition of the present embodiment may further contain, for example, other hydrophilic agents, other oil repellent agents, water repellent agents, insect repellents, flame retardants, wrinkle preventing agents, antistatic agents, softening agents, preservatives, fragrances, antioxidants, emulsifiers, dispersants, resin additives, and the like, as long as the object of the present invention is not violated.

The composition of the present embodiment can be used as a coating agent for various articles including glass, plastic, metal, electronic substrates, textile products, leather, stone, wood, paper, and the like. A method of appropriately selecting a coating method such as spray coating, spin coating, or dipping depending on the object to be treated, and drying or crosslinking the coating by heat treatment as necessary can be used. The composition of the present embodiment may be used for an emulsifier, a dispersant, a resin additive, and the like, without being limited thereto.

B. Defoaming agent

The defoaming agent according to another embodiment of the present invention includes a copolymer obtained by polymerizing constituent monomers including a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a (meth) acrylate compound (a3) having a hydrocarbon ring structure. According to the defoaming agent of the present embodiment, the generation of foam can be suppressed, and therefore, the generation of coating unevenness can be suppressed. In particular, the defoaming agent of the present embodiment can effectively suppress the generation of foam by being used in combination with the copolymer (a).

The amount of the defoaming agent added in the present embodiment is not particularly limited, and for example, when used in combination with a composition containing the copolymer (a), the amount of the copolymer (B) contained in the defoaming agent is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more, per 100 parts by mass of the copolymer (a). Further, the amount of the copolymer (B) contained in the defoaming agent is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 90 parts by mass or less, yet more preferably 80 parts by mass or less, and particularly preferably 50 parts by mass or less, per 100 parts by mass of the copolymer (a).

The defoaming agent of the present embodiment may further contain, for example, other defoaming agents, other oil-repellent agents, water-repellent agents, insect-proofing agents, flame retardants, wrinkle-proofing agents, antistatic agents, softening agents, preservatives, fragrances, and antioxidants, within a range not departing from the object of the invention.

[ examples ]

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.

(use of raw materials)

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

(a1-1) perfluorohexylethyl methacrylate

(a1-2) Perfluorobutyl Ethyl methacrylate

(a1-3) Perfluorohexylethyl acrylate

(meth) acrylate Compound having polyoxyalkylene group (a2)

(a2-1) polyoxyethylene glycol monomethyl ether methacrylate (average number of repeating units of oxyethylene group: 9)

(a2-2) polyoxyethylene glycol monomethyl ether methacrylate (average number of repeating units of oxyethylene group: 23)

(a2-3) polyoxyethylene glycol monomethyl ether methacrylate (average number of repeating units of oxyethylene group: 90)

(meth) acrylate Compound (a3) having Hydrocarbon Ring Structure

(a3-1) cyclohexyl methacrylate

(a3-2) isobornyl acrylate

(a3-3) benzyl methacrylate

(meth) acrylate Compound having aliphatic Hydrocarbon group (a4)

(a4-1) stearyl methacrylate

Solvent(s)

(c-1) 3-methoxy-3-methylbutyl acetate (SOLFIT AC manufactured by Kuraray, Ltd.)

(c-2) ethylene glycol dimethyl Ether (DMG)

(c-3) Methyl Ethyl Ketone (MEK)

(c-4) Ethyl acetate

(c-5) diethylene glycol methyl ethyl ether (MEDG)

(c-6) Dimethylpropylenediglycol (DMFDG)

(c-7) Propylene Glycol Diacetate (PGDA)

(example 1)

In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux tube, 300 parts of the compounds (a1) to (a3) and 3-methoxy-3-methylbutylacetate as a solvent were added at the mass ratio described in table 1 below, and nitrogen substitution was performed. Then, tert-butyl peroxypivalate (trade name: PERBUTYL (registered trademark) PV, manufactured by Nichigan oil (stock Co., Ltd.)) was added in an amount of 3 parts by mass based on 100 parts by mass of the total amount of the compounds (a1) to (a3), and the mixture was reacted at 65 ℃ for 8 hours, followed by distilling off the solvent to obtain a copolymer (A).

Then, in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux tube, 300 parts of the compounds of (a1), (a3) to (a4) and ethyl acetate as a solvent were added at the ratio described in table 2 described later, and nitrogen substitution was performed. Then, tert-butyl peroxypivalate (trade name: PERBUTYL (registered trademark) PV, manufactured by Nichisu oil Co., Ltd.) was added in an amount of 3 parts by mass based on 100 parts by mass of the total amount of the compounds (a1) and (a3) to (a4), and the mixture was reacted at 65 ℃ for 8 hours, followed by distilling off the solvent to obtain a copolymer (B).

Then, the copolymer (a), the copolymer (B) and the solvent (c) were mixed in the proportions shown in table 3, and mixed at 70 ℃ for 2 hours to obtain a composition.

(examples and comparative examples other than example 1)

Compositions were obtained by using materials and mass ratios described in tables 1 to 5 described later in the same manner as in example 1 for examples and comparative examples other than example 1. In examples 16 to 18, the copolymer (a), the copolymer (B) and the solvent (c) were mixed at the ratio shown in table 3 under reflux conditions and mixed at 70 ℃ for 2 hours.

Using the prepared composition, the following evaluations were performed. Specifically, the following properties were evaluated when various solvents were used.

(solubility 1)

90 parts by mass of dimethylformamide was added to 10 parts by mass of the composition, and the mixture was mixed, and the resultant was put into a screw tube having a diameter of 3cm so that the height was 1 cm. The screw tube was placed on paper printed with text (MS Gothic, 12 lbs) and visually confirmed to evaluate solubility at 25 ℃ on the following 2 grades.

A: can clearly see the characters recorded under the screw pipe

B: the characters recorded under the screw pipe can not be seen clearly

(solubility 2)

To 10 parts by mass of the composition, 90 parts by mass of N-methyl-2-pyrrolidone was added and mixed, and the resultant mixture was put into a screw tube having a diameter of 3cm so that the height became 1 cm. The screw tube was placed on paper printed with text (MS Gothic, 12 lbs) and visually confirmed to evaluate solubility at 25 ℃ on the following 2 grades.

A: can clearly see the characters recorded under the screw pipe

B: the characters recorded under the screw pipe can not be seen clearly

(foam suppressing property 1)

90 parts by mass of dimethylformamide was added to 10 parts by mass of the composition, and the mixture was mixed, and 30 parts by mass of the obtained solution was put into a screw tube having a diameter of 3cm and a height of 8cm, and adjusted to 25 ℃. Then, the screw tube was oscillated 30 times within 15 seconds so that the vertical amplitude became 30 cm. Then, the amount of foaming after standing for 30 seconds was evaluated on the following 4 scales. The less foaming, the more excellent the foam suppressing property, and thus is preferable.

A: 1/4 less than comparative example 1

B: 1/4 or more and less than 1/2 of comparative example 1

C: 1/2 or more and less than 3/4 of comparative example 1

D: 3/4 or more in comparative example 1

(foam suppressing property 2)

To 10 parts by mass of the composition, 90 parts by mass of N-methyl-2-pyrrolidone was added and mixed, and 30 parts by mass of the obtained solution was put into a screw tube having a diameter of 3cm and a height of 8cm, and adjusted to 25 ℃. Then, the screw tube was oscillated 30 times within 15 seconds so that the vertical amplitude became 30 cm. Then, the amount of foaming after standing for 30 seconds was evaluated on the following 4 scales. The less foaming, the more excellent the foam suppressing property, and thus is preferable.

A: 1/4 less than comparative example 1

B: 1/4 or more and less than 1/2 of comparative example 1

C: 1/2 or more and less than 3/4 of comparative example 1

D: 3/4 or more in comparative example 1

(leveling property 1)

90 parts by mass of dimethylformamide was added to 10 parts by mass of the composition, and the mixture was mixed, and then the solution was applied onto a glass plate (7.5 cm in length, 2.5cm in width, 1mm in thickness) by a spin coating method so that the thickness was 10 μm. The coating liquid was dried at 105 ℃ for 10 minutes to prepare an evaluation sample, and leveling property was evaluated by visual observation on 4 ranks as follows. A is the most excellent leveling property, and D is the least excellent leveling property.

A: without uneven coating

B: the total of the uneven streaks, pinholes and irregularities is 1-2

C: the total of the uneven streaks, pinholes and irregularities is 3 to 4

D: the total number of the streaky unevenness, the pinholes and the unevenness is 5 or more

(leveling property 2)

After 90 parts by mass of N-methyl-2-pyrrolidone was added to 10 parts by mass of the composition, the mixture was mixed, and the resulting solution was applied onto a glass plate (7.5 cm in length, 2.5cm in width, 1mm in thickness) by spin coating to a thickness of 10 μm. The coating liquid was dried at 105 ℃ for 10 minutes to prepare an evaluation sample, and leveling property was evaluated by visual observation on 4 ranks as follows. A is the most excellent leveling property, and D is the least excellent leveling property.

A: without uneven coating

B: the total of the uneven streaks, pinholes and irregularities is 1-2

C: the total of the uneven streaks, pinholes and irregularities is 3 to 4

D: the total number of the streaky unevenness, the pinholes and the unevenness is 5 or more

(antifouling Property)

The contact angle of hexadecane on the coated surface of the evaluation sample was measured using a contact angle measuring apparatus (trade name: contact angle meter Drop Master 500, manufactured by Kyowa Kagaku Kogyo Co., Ltd.) and evaluated on the following 5 scales. The higher the contact angle, the more excellent the antifouling property.

A: over 60 degrees

B: more than 50 DEG and less than 60 DEG

C: 40 degrees or more and less than 50 degrees

D: more than 30 degrees and less than 40 degrees

E: less than 30 °

[ Table 1]

	A-1	A-2	A-3	A-4	A-5	A-6	A-7	A-8
									(a1-1)	40	60	80			60	60	60
(a1-2)				60
									(a1-3)					60
(a2-1)						40
									(a2-2)	60	40	20	40	40			34
(a2-3)							40
									(a3-2)								3
(a3-3)								3

[ Table 2]

	B-1	B-2	B-3	B-4
					(a1-1)	60	60	60	60
(a3-1)		15
					(a3-2)			15	20
(a3-3)	15			20
					(a4-1)	25	25	25

[ Table 3]

[ Table 4]

[ Table 5]

The following contents can be found from tables 1 to 5. That is, examples 1 to 21 including the copolymer (B) are excellent in the foam suppressing property and the leveling property, as compared with comparative examples 1 and 2 not including the copolymer (B).

From the results of comparative example 2, it is also clear that: even if the (meth) acrylate compound (a3) having a hydrocarbon ring structure is contained in the constituent monomer (a) of the copolymer (a), the foam suppressing property is not excellent and the leveling property is not excellent in the case where the copolymer (B) is not contained.

Further, by comparing example 2 and examples 8 to 10, it is understood that: the constituent polymer (B) of the copolymer (B) was superior in leveling property to those of examples 2, 8 and 9, which contained the (meth) acrylate compound having an aliphatic hydrocarbon group (a4), as compared to example 10, which contained no (meth) acrylate compound having an aliphatic hydrocarbon group (a 4).

Further, by comparing examples 11 to 15, it is understood that: the smaller the mass ratio ((B)/(a)) of the copolymer (B) to the copolymer (a), the more excellent the leveling property tends to be. On the other hand, it is known that: the larger the mass ratio ((B)/(a)) is, the more excellent the foam suppressing property tends to be.

Further, by comparing example 2, example 6 and example 7, it is understood that: when the average number of repeating units of oxyethylene groups in the (meth) acrylate compound (a2) having a polyoxyalkylene group is used as the copolymer (a), the antifouling property is excellent as compared with when the average number of repeating units is short.

Further, by comparing example 2, example 4 and example 5, it is understood that: the (meth) acrylate compound (a1) of the copolymer (a) has excellent antifouling properties when perfluorohexylethyl methacrylate is used, compared with when perfluorobutylethyl methacrylate or perfluorohexylethyl acrylate is used.

The present invention is not limited to the above-described embodiments, and can be realized in various configurations without departing from the spirit and scope thereof. For example, in order to solve a part or all of the above-described problems or to achieve a part or all of the above-described effects, technical features in embodiments and examples corresponding to technical features in the respective aspects described in the summary of the invention may be appropriately replaced or combined. In addition, if a technical feature is not described as an essential technical feature in the present specification, it can be deleted as appropriate.