WO2023127617A1

WO2023127617A1 - Dispersant for fluororesin, composition, dispersion liquid, article, and copolymer

Info

Publication number: WO2023127617A1
Application number: PCT/JP2022/047006
Authority: WO
Inventors: 徹岩木; 真奈田中
Original assignee: 第一工業製薬株式会社
Priority date: 2021-12-27
Filing date: 2022-12-21
Publication date: 2023-07-06
Also published as: JP7136994B1; JP2023096479A; TW202325759A

Abstract

The present invention provides a technology for improving the dispersibility of fluororesin in various solvents. This dispersant for fluororesin comprises a copolymer. The copolymer includes a copolymer obtained by polymerizing a constituent monomer (a) that contains a (meth)acrylate compound (a1) represented by Rf-Cb-R-O-X, and a (meth)acrylate compound (a2) represented by HO-(PO)p-Y, wherein Rf is a perfluoro (poly)ether group, Cb is one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, R is an alkylene group having 1 to 8 carbon atoms, X and Y are acryloyl groups or methacryloyl groups, PO is an oxypropylene group, and p is a number of 2 to 150.

Description

Dispersants for fluororesins, compositions, dispersions, articles and copolymers

The present invention relates to a fluororesin dispersant and copolymer.

　In general, fluororesins such as polytetrafluoroethylene (PTFE) are known to have excellent water repellency and oil repellency, but low dispersibility in solvents (for example, Patent Document 1). Patent Literature 1 discloses a fluororesin dispersant for improving the dispersibility of a fluororesin in a solvent.

JP 2015-110697 A

However, the dispersant for fluororesin described in Patent Document 1 cannot be said to have sufficient dispersibility of the fluororesin in the solvent, and there is room for improvement. Therefore, it is desired to develop a technique capable of improving the dispersibility of fluororesin in various solvents.

The present invention can be realized as the following forms.

(1) According to one aspect of the present invention, a dispersant for fluororesin is provided. This fluororesin dispersant is a fluororesin dispersant containing a copolymer, and the copolymer comprises a (meth)acrylate compound (a1) represented by the following general formula (1) and the following general formula: It is characterized by containing a copolymer obtained by polymerizing a constituent monomer (a) containing a (meth)acrylate compound (a2) represented by formula (2).
^Rf -Cb-R-O-X (1)
(Wherein, R ^f is a perfluoro (poly) ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, and R has 1 or more carbon atoms. 8 or less alkylene group, and X is an acryloyl group or a methacryloyl group.)
HO-(PO)pY (2)
(In the formula, PO is an oxypropylene group, p is a number of 2 or more and 150 or less, and Y is an acryloyl group or a methacryloyl group.)

(2) In the above aspect of the fluororesin dispersant, Cb may be an ester bond.

(3) In the fluororesin dispersant of the above aspect, the constituent monomer (a) may further contain a (meth)acrylate compound (a3) represented by the following general formula (3).
AO-(EO)qZ (3)
(wherein A is H or _CH3 , EO is an oxyethylene group, q is a number from 2 to 150, and Z is an acryloyl group or a methacryloyl group.)

(4) In the fluororesin dispersant of the above aspect, 30 parts by mass or more and 80 parts by mass or less of the (meth)acrylate compound (a1) may be contained in 100 parts by mass of the constituent monomer (a).

(5) In the fluororesin dispersant of the above aspect, the R ^f is CF ₃ CF ₂ CF ₂ O(CF(CF ₃ )CF ₂ O) _n CF(CF ₃ ), and n is a number of 0 or more. may be

(6) In the above aspect of the fluororesin dispersant, n may be 0.

(7) A composition containing the fluororesin dispersant of the above form and a surfactant may be used.

(8) A dispersion containing the fluororesin dispersing agent of the above-described form and the fluororesin may be used.

(9) It may be an article impregnated or coated with the above-described dispersion liquid.

(10) According to another aspect of the present invention, a copolymer is provided. This copolymer is a constituent monomer containing a (meth)acrylate compound (a1) represented by the following general formula (1) and a (meth)acrylate compound (a2) represented by the following general formula (2): Obtained by polymerizing (a).
^Rf -Cb-R-O-X (1)
(Wherein, R ^f is a perfluoro (poly) ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, and R has 1 or more carbon atoms. 8 or less alkylene group, and X is an acryloyl group or a methacryloyl group.)
HO-(PO)pY (2)
(In the formula, PO is an oxypropylene group, p is a number of 2 or more and 150 or less, and Y is an acryloyl group or a methacryloyl group.)

The present invention can be realized in various forms, for example, in the form of a method for producing a dispersant for fluororesin, a method for producing a copolymer, and the like.

According to this embodiment, the dispersibility of the fluororesin in various solvents can be improved.

A. Dispersant for fluororesin A dispersant for fluororesin (hereinafter also simply referred to as "dispersant") that is an embodiment of the present invention contains a copolymer (A). The copolymer (A) contains a (meth)acrylate compound (a1) represented by the following general formula (1) and a (meth)acrylate compound (a2) represented by the following general formula (2). It includes a copolymer obtained by polymerizing the constituent monomers (a).
^Rf -Cb-R-O-X (1)
(Wherein, R ^f is a perfluoro (poly) ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, and R has 1 or more carbon atoms. 8 or less alkylene group, and X is an acryloyl group or a methacryloyl group.)
HO-(PO)pY (2)
(In the formula, PO is an oxypropylene group, p is a number of 2 or more and 150 or less, and Y is an acryloyl group or a methacryloyl group.)

The fluororesin dispersant of this embodiment can improve the dispersibility of the fluororesin in various solvents. The mechanism that produces such an effect is not clear. However, as a presumed mechanism, the side chain derived from the (meth)acrylate compound (a1) represented by the general formula (1) makes it easier to adsorb to the fluororesin, and the (meth) ) It is believed that the oxypropylene group, which is a side chain derived from the acrylate compound (a2), facilitates solubility in solvents.

Moreover, it is preferable that the constituent monomer (a) further contains a (meth)acrylate compound (a3) represented by the following general formula (3).
AO-(EO)qZ (3)
(wherein A is H or _CH3 , EO is an oxyethylene group, q is a number from 2 to 150, and Z is an acryloyl group or a methacryloyl group.)

By including the (meth)acrylate compound (a3) represented by the general formula (3) in the constituent monomer (a), the water dispersibility of the fluororesin can be further improved. The mechanism that produces such an effect is not clear. However, as a presumed mechanism, it is considered that the oxyethylene group, which is a side chain derived from the (meth)acrylate compound (a3) represented by the general formula (3), enhances the affinity with water.

As used herein, the term "fluororesin" means a resin containing fluorine. Examples of the fluororesin include, but are not limited to, polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluorovinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene. -ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), chlorotrifluoroethylene-ethylene copolymer (FCTFE), polychlorotrifluoroethylene (PCTFE), and the like. PTFE and PFA are preferable as the fluororesin, and PTFE is more preferable, from the viewpoint of effectively imparting the dispersibility of the fluororesin by the dispersant.

<(Meth)acrylate compound (a1)>
The (meth)acrylate compound (a1) is represented by the following general formula (1).
^Rf -Cb-R-O-X (1)
In the formula, R ^f is a perfluoro (poly) ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, and R has 1 to 8 carbon atoms. and X is an acryloyl group or a methacryloyl group. As used herein, a perfluoro(poly)ether group means a perfluoropolyether group or a perfluoroether group. Also, in this specification, a perfluoroether group comprises a perfluoroalkyl group and an ether bond, and a perfluoropolyether group comprises a perfluoroalkyl group, a perfluoroalkylene group and an ether bond. The ester bond means "-C(=O)-O-", the amide bond means "-C(=O)-NH-", and the urethane bond means "-NH-C (=O) -O-".

From the viewpoint of improving dispersibility, Cb in general formula (1) preferably contains an ester bond. In addition, from the viewpoint of improving dispersibility, R ^f is CF ₃ CF ₂ CF ₂ O(CF(CF ₃ )CF ₂ O) _n CF(CF ₃ ), where n is a number of 0 or more. More preferably CF ₃ CF ₂ CF ₂ OCF (CF ₃ ), i.e. n=0. Further, from the viewpoint of improving dispersibility, R is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and is C ₂ H ₄ . is more preferred. Moreover, it is preferable that X in General formula (1) is a methacryloyl group from a viewpoint of improving dispersibility. The (meth)acrylate compound (a1) represented by the general formula (1) may be used singly or in combination of two or more.

Examples of the (meth)acrylate compound (a1) represented by the general formula (1) include a side-chain perfluoropolyether (PFPE) (meth)acrylate compound and a linear PFPE (meth)acrylate compound. mentioned. From the viewpoint of improving dispersibility, the (meth)acrylate compound (a1) represented by the general formula (1) is preferably a side chain type PFPE (meth)acrylate compound.

Examples of side chain type PFPE (meth)acrylate compounds include compounds represented by the following general formulas (4) to (7). The average repeating unit number n in the following formula is a number of 0 or more, preferably 30 or less, more preferably 25 or less, further preferably 20 or less, particularly preferably 15 or less, more preferably 10 or less, 8 The following are more preferable, particularly preferably 5 or less, more preferably 3 or less, still more preferably 1 or less, and even more preferably 0. The average repeating unit number m in the following formula is a number of 0 or more, preferably 20 or less, more preferably 10 or less, further preferably 8 or less, particularly preferably 5 or less, more preferably 3 or less, 1 More preferred are: In addition, in the following general formulas (4) to (7), compounds having a methacryloyl group are all listed, but compounds having an acryloyl group instead of a methacryloyl group are also side chain-type PFPE (meth)acrylate compounds. included.

Examples of linear PFPE (meth)acrylate compounds include compounds represented by the following general formulas (8) to (11). The average repeating unit number n in the following formula is a number of 0 or more, preferably 30 or less, more preferably 25 or less, further preferably 20 or less, particularly preferably 15 or less, more preferably 10 or less, 8 The following are more preferable, and 0 is even more preferable. The average repeating unit number m in the following formula is a number of 0 or more, preferably 20 or less, more preferably 15 or less, further preferably 10 or less, particularly preferably 8 or less, more preferably 5 or less, 3 More preferred are: In addition, in the following general formulas (8) to (11), compounds having a methacryloyl group are all listed, but a compound having an acryloyl group instead of a methacryloyl group is also a linear PFPE (meth)acrylate compound. included.

<(Meth)acrylate compound (a2)>
The (meth)acrylate compound (a2) is represented by the following general formula (2).
HO-(PO)pY (2)
In the formula, PO is an oxypropylene group, p is a number of 2 or more and 150 or less, and Y is an acryloyl group or a methacryloyl group.

The average repeating unit number p of the oxypropylene group in general formula (2) is not particularly limited, but is preferably 3 or more and 150 or less from the viewpoint of further improving dispersibility. The lower limit of the average repeating unit number p is more preferably 4 or more, more preferably 8 or more, particularly preferably 10 or more, and more preferably 12 or more. The upper limit of the average repeating unit number p is more preferably 120 or less, more preferably 100 or less, even more preferably 70 or less, more preferably 50 or less, and 20 or less. 15 or less is particularly preferable. Moreover, from the viewpoint of improving dispersibility, Y in the general formula (2) is preferably a methacryloyl group. The (meth)acrylate compound (a2) represented by formula (2) may be used singly or in combination of two or more.

<(Meth)acrylate compound (a3)>
The (meth)acrylate compound (a3) is represented by the following general formula (3).
AO-(EO)qZ (3)
In the formula, A is H or _CH3 , EO is an oxyethylene group, q is a number from 2 to 150, and Z is an acryloyl group or a methacryloyl group.

Although the average number of repeating units q of the oxyethylene group in general formula (3) is not particularly limited, it is preferably 3 or more and 150 or less from the viewpoint of further improving dispersibility. The lower limit of the average repeating unit number q is more preferably 5 or more, more preferably 10 or more, particularly preferably 15 or more, and more preferably 20 or more. The upper limit of the average repeating unit number q is more preferably 120 or less, still more preferably 100 or less, even more preferably 70 or less, and particularly preferably 40 or less. Moreover, Z in the general formula (3) is preferably a methacryloyl group from the viewpoint of improving dispersibility. The (meth)acrylate compound (a3) represented by the general formula (3) may be used singly or in combination of two or more.

The constituent monomer (a) constituting the copolymer (A) of the present embodiment may contain monomers other than the above components (a1), (a2) and (a3) within the scope of the object of the invention. good. Further, the dispersing agent for fluororesin of the present embodiment may contain a copolymer other than the copolymer (A) as long as it does not contradict the object of the invention.

In the constituent monomer (a), the content of the (meth)acrylate compound (a1) represented by the general formula (1) is not particularly limited, but from the viewpoint of improving dispersibility, the constituent monomer (a) is 100 parts by mass. WHEREIN: It is preferable to contain 5 to 95 mass parts. The lower limit of the content of the (meth)acrylate compound (a1) represented by the general formula (1) with respect to 100 parts by mass of the constituent monomer (a) is more preferably 10 parts by mass or more, and 30 parts by mass. It is more preferable that it is above. The upper limit of the content of the (meth)acrylate compound (a1) represented by the general formula (1) with respect to 100 parts by mass of the constituent monomer (a) is more preferably 80 parts by mass or less, and 70 parts by mass. It is more preferably 50 parts by mass or less, and even more preferably 50 parts by mass or less.

In the constituent monomer (a), the content of the (meth)acrylate compound (a2) represented by the general formula (2) is not particularly limited, but from the viewpoint of improving dispersibility, the constituent monomer (a) is 100 parts by mass. WHEREIN: It is preferable to contain 5 to 95 mass parts. The lower limit of the content of the (meth)acrylate compound (a2) represented by the general formula (2) with respect to 100 parts by mass of the constituent monomer (a) is more preferably 10 parts by mass or more, and 15 parts by mass. It is more preferably 20 parts by mass or more, and even more preferably 20 parts by mass or more. The upper limit of the content of the (meth)acrylate compound (a2) represented by the general formula (2) with respect to 100 parts by mass of the constituent monomer (a) is more preferably 80 parts by mass or less, and 50 parts by mass. It is more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less.

In the constituent monomer (a), the content ratio of the (meth)acrylate compound (a3) represented by the general formula (3) is not particularly limited, but from the viewpoint of improving the dispersibility in water, the constituent monomer (a) In 100 parts by mass, the content is preferably 5 parts by mass or more and 90 parts by mass or less. The lower limit of the content of the (meth)acrylate compound (a3) represented by the general formula (3) with respect to 100 parts by mass of the constituent monomer (a) is more preferably 10 parts by mass or more, and 15 parts by mass. It is more preferably at least 25 parts by mass, even more preferably at least 25 parts by mass, and particularly preferably at least 35 parts by mass. The upper limit of the content of the (meth)acrylate compound (a3) represented by the general formula (3) with respect to 100 parts by mass of the constituent monomer (a) is more preferably 80 parts by mass or less, and 60 parts by mass. It is more preferably 45 parts by mass or less, and even more preferably 45 parts by mass or less.

In the constituent monomer (a), the mass ratio (a2/a1) of the (meth)acrylate compound (a2) represented by the general formula (2) to the (meth)acrylate compound (a1) represented by the general formula (1) is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more, from the viewpoint of improving dispersibility. Further, in the constituent monomer (a), the mass ratio (a2/ From the viewpoint of improving dispersibility, a1) is preferably 170% or less, more preferably 130% or less, even more preferably 80% or less, and particularly preferably 60% or less. preferable.

The copolymer (A) used in the present embodiment is not particularly limited, but preferably has a weight average molecular weight of 2,000 to 200,000, more preferably 5,000 to 100,000. ,000 to 50,000. When the weight-average molecular weight is within the above range, it is easy to obtain a dispersant for fluororesin having excellent dispersibility. As used herein, the weight average molecular weight can be measured using GPC column chromatography under the following conditions, and polyethylene glycols having molecular weights of 300, 2,000, 8,000, and 20,000 are used as standard samples. A calibrated one was used.

・ Apparatus: LC-10AD (manufactured by Shimadzu Corporation)
・ Detector: RID-10A (manufactured by Shimadzu Corporation)
・Column: Shodex GPC KF-G, KF-803, KF802.5, KF-8
02 and KF-801 (both manufactured by Showa Denko Co., Ltd.)
- Eluent: tetrahydrofuran - Sample injection: 0.5 wt% solution, 100 μL
・Flow rate: 0.8 mL/min
・Temperature: 25℃

Next, a method for producing the fluororesin dispersant of this embodiment will be described. The method for producing the fluororesin dispersant is not particularly limited, but for example, a (meth)acrylate compound (a1) represented by the general formula (1) and a (meth)acrylate compound represented by the general formula (2) A method of heating after mixing (a2) and a solvent can be mentioned.

The solvent used in the production of the fluororesin dispersant may be water or an organic solvent. Examples of organic solvents include aromatic solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane and isophorone, and ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone. , ethyl acetate, butyl acetate, ester solvents such as propylene glycol diacetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl acetate, 3-methoxy-3-methylbutyl Glycol ether ester solvents such as acetate, glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol dibutyl ether, dimethyl triglycol, methyl ethyl diglycol, dimethyl propylene diglycol, dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, etc. Among them, acetone, methyl ethyl ketone, ethyl acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methyl ethyl diglycol, propylene glycol monomethyl ether acetate, 3 -Methoxy-3-methylbutyl acetate, dimethylpropylene diglycol are preferred. Two or more of the above solvents may be used in combination.

Although the polymerization method is not particularly limited, it is preferably solution polymerization. Although the polymerization temperature is not particularly limited, it is usually preferably in the range of 40 to 120°C. Although the polymerization time is not particularly limited, it is usually preferably about 4 to 15 hours.

A polymerization initiator may be used when performing polymerization. Examples of polymerization initiators include, but are not limited to, benzoyl peroxide, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, 1,1 , 3,3-tetramethylbutylperoxy-2-ethylhexanoate and other peroxides, azo compounds such as azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, and the like. be done. The amount of the polymerization initiator to be used is not particularly limited, but generally it is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the constituent monomer (a).

The fluororesin dispersing agent of the present embodiment is, within a range not contrary to the object of the invention, for example, other hydrophilic agents, other oil repellent agents, water repellent agents, insect repellents, flame retardants, anti-wrinkle agents, antistatic agents, It may further contain softeners, preservatives, fragrances, antioxidants, surfactants, emulsifiers, dispersants, resin additives and the like. Examples of surfactants include, but are not particularly limited to, nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

The dispersion medium used for the fluororesin dispersant of this embodiment is not particularly limited. Examples of dispersion media include alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, iso-butanol, sec-butyl alcohol, tert-butanol and terpineol. Examples of dispersion media include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, 2-heptanone, cycloheptanone, γ-butyrolactone, cyclohexanone, methylcyclohexanone, ethylcyclohexanone, methyl-n-pentyl ketone, methyl isobutyl ketone, Examples include ketones such as pentyl ketone. Examples of the dispersion medium include esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, methyl lactate, ethyl lactate, butyl lactate, and cyclohexyl acetate. Examples of the dispersion medium include methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate. , propyl 2-methoxypropionate, butyl 2-methoxypropionate, and ethyl 3-ethoxypropionate. Examples of the dispersion medium include polar solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide and N-methylpyrrolidone. Examples of dispersion media include ethylene glycol, diethylene glycol, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol monoacetate, ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, Ethylene glycols such as diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol dimethyl ether, and esters thereof can be mentioned. Examples of dispersion media include propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monoacetate, and propylene glycol diacetate. Propylene glycols such as acetate, dipropylene glycol methyl ether acetate, dipropylene glycol dimethyl ether, and esters thereof can be mentioned. Examples of the dispersion medium include solvents such as 3-methoxy-3-methyl-1-butanol and 3-methoxy-3-methyl-1-butyl acetate. Examples of the dispersion medium include halogen solvents such as chloroform, methylene chloride and 1,1,1-trichloroethane, and ethers such as tetrahydrofuran and dioxane. Examples of the dispersion medium include aromatics such as benzene, toluene, xylene, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene and diethylbenzene. Moreover, as a dispersion medium, water is mentioned, for example. Two or more of the above dispersion media may be used in combination. Among the above dispersion media, N-methylpyrrolidone, cyclohexanone, toluene, dimethylformamide, ethanol, dimethylacetamide, methyl ethyl ketone, propylene glycol methyl ether acetate, ethyl acetate, and water are preferred from the viewpoint of dispersibility.

The fluororesin dispersant of the present embodiment can impart excellent dispersibility to the fluororesin. Therefore, the fluororesin dispersant of the present embodiment is a coating agent for various articles including, for example, glass, plastic, metal, electronic substrates, textiles, leather, stone, wood, paper, etc. It can be used for coating agents containing. This coating agent may be applied, for example, to cooking utensils such as frying pans, or to automobile bodies.

B. Other Embodiments Another embodiment of the present invention includes, for example, a composition containing the above-described fluororesin dispersant and a surfactant. The surfactant is not particularly limited, but nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and the like can be used, for example. Other embodiments of the present invention include, for example, a dispersion containing the above-described fluororesin dispersant and fluororesin, and an article impregnated or coated with this dispersion. A resin other than the fluororesin may be dissolved in the dispersion liquid of the present embodiment. In addition, the dispersion liquid of the present embodiment can be used by impregnating or coating various articles. For example, by impregnating a cloth with the dispersion liquid of the present embodiment, the cloth may be used for a tent or the like. Also, the dispersion liquid of the present embodiment may be applied to a beaker or the like to be used for printing on the beaker or the like. Further, as another embodiment of the present invention, a (meth)acrylate compound (a1) represented by the general formula (1) and a (meth)acrylate compound (a2) represented by the general formula (2) are Examples thereof include copolymers (A) obtained by polymerizing constituent monomers (a) containing. Applications of this copolymer (A) and the above-mentioned dispersion include, for example, electronic equipment, OA equipment, home appliances, mechanical sliding parts such as automobile interior parts, gears, fitting parts, etc. Lubricating properties or the like may be imparted, and an effect of suppressing noise caused by creaking may be imparted. Moreover, the copolymer (A) may be used as a leveling agent. When the copolymer (A) is applied to the article as a leveling agent, it is possible to suppress the occurrence of pinholes and coating unevenness, thereby improving homogeneity and smoothness.

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

(Raw materials used)
(Meth)acrylate compound (a1) represented by general formula (1)
(a1-1)
A compound represented by the following general formula (12) (manufactured by SINOCHEM LANTIAN, trade name: AC-500)

(a1-2)
A compound represented by the following general formula (13) (manufactured by SINOCHEM LANTIAN, trade name: AC-1000, average repeating unit number n: 4)

(Meth)acrylate compound (a2) represented by general formula (2)
(a2-1) Polypropylene glycol monomethacrylate (average number of repeating units of oxypropylene group: 4 to 6, manufactured by NOF Corporation, trade name: Blemmer (registered trademark) PP-1000)
(a2-2) Polypropylene glycol monomethacrylate (average number of repeating units of oxypropylene group: 9, manufactured by NOF Corporation, trade name: Blemmer (registered trademark) PP-500)
(a2-3) Polypropylene glycol monomethacrylate (average number of repeating units of oxypropylene group: 13, manufactured by NOF Corporation, trade name: Blemmer (registered trademark) PP-800)

(Meth)acrylate compound (a3) represented by general formula (3)
(a3-1) Methoxypolyethylene glycol methacrylate (average number of repeating units of oxyethylene group: 23, manufactured by NOF Corporation, trade name: Blemmer (registered trademark) PME-1000)
(a3-2) polyethylene glycol acrylate (average number of repeating units of oxyethylene group: 10, manufactured by NOF Corporation, trade name: Blemmer (registered trademark) AE-400)

Solvent (c-1) methyl ethyl ketone (MEK)
(c-2) ethylene glycol dimethyl ether (DMG)
(c-3) 3-Methoxy-3-methylbutyl acetate (manufactured by Kuraray Co., Ltd., trade name: Solfit AC)
(c-4) propylene glycol methyl ether acetate (PGMEA)
(c-5) diethylene glycol diethylene ether (DEDG)
(c-6) methyl ethyl diglycol (MEDG)
(c-7) ethyl acetate (c-8) ethanol

(Examples 1 to 18, Comparative Examples 1 to 4)
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux tube, the compounds (a1) to (a3) and a solvent are added at the mixing ratios shown in Tables 1 and 2 below, and nitrogen is replaced. gone. Subsequently, t-butyl peroxypivalate (manufactured by NOF Corporation, trade name: Perbutyl (registered trademark) PV) is added to 3 parts by mass per 100 parts by mass of the total amount of the compounds (a1) to (a3). A copolymer solution (dispersing agent) was obtained by adding so as to be a mass part and reacting at 65° C. for 8 hours.

(Example 19)
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux tube, the compounds (a1) and (a2) and 230 parts of MEK as a solvent are added at the mixing ratios shown in Table 2 below, and nitrogen is replaced. gone. Subsequently, t-butyl peroxypivalate (manufactured by NOF Corporation, trade name: Perbutyl (registered trademark) PV) is added to 3 parts by mass per 100 parts by mass of the total amount of the compounds (a1) and (a2). The reaction solution was obtained by adding so that it might become a mass part and making it react at 65 degreeC for 8 hours. After removing MEK in this reaction solution by distillation under reduced pressure, 230 parts of ethyl acetate was added and mixed at 60° C. for 1 hour to obtain a copolymer solution (dispersant).

(Example 20)
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux tube, the compounds (a1) and (a2) and 230 parts of MEK as a solvent are added at the blending ratios shown in Table 2 below, and replaced with nitrogen. did Subsequently, t-butyl peroxypivalate (manufactured by NOF Corporation, trade name: Perbutyl (registered trademark) PV) is added to 3 parts by mass per 100 parts by mass of the total amount of the compounds (a1) and (a2). The reaction solution was obtained by adding so that it might become a mass part and making it react at 65 degreeC for 8 hours. After removing MEK from the reaction solution by distillation under reduced pressure, 230 parts of ethanol was added and mixed at 60° C. for 1 hour to obtain a copolymer solution (dispersant).

The following evaluations were performed using the prepared dispersant. Specifically, the following performances were evaluated when various solvents were used.

(Appearance (transparency))
The prepared dispersant was poured into two screw tube bottles (No. 8, manufactured by Maruem Co., Ltd.) with an outer diameter of 3.5 cm so that one had a height of 10 cm and the other had a height of 1 cm. is. Each screw-capped bottle was placed on paper on which characters (MS Gothic, 12 points) were printed, and the appearance was evaluated according to the following three grades by viewing the characters from above. When the fluorine-containing copolymer solution turned into a gel, the evaluation result was given as D, and the transparency was not checked.
A: Transparent (The characters written below can be read in both 10 cm and 1 cm screw-tube bottles.)
B: Slightly turbid (The letters written under the screw bottle with a height of 10 cm cannot be read, but the letters written under the screw bottle with a height of 1 cm can be read)
C: Cloudy (The letters written below cannot be read in both 10 cm and 1 cm screw-tube bottles)

(NMP dispersibility evaluation)
1.67 g (charged amount) of a dispersant and 8.33 g (charged amount) of N-methylpyrrolidone (NMP) (dispersion medium) were placed in a screw tube bottle (No. 7 manufactured by Maruem Co., Ltd.) having an outer diameter of 3.0 cm. After mixing, polytetrafluoroethylene (PTFE) (trade name: TFW-2000 (average particle size 6 μm), manufactured by Seishin Enterprise Co., Ltd.) was added (amount charged). After that, the PTFE was dispersed by shaking the screw tube bottle up and down 30 times. When the PTFE was not dispersed by shaking alone, the PTFE was scraped off to the solution with a spatula and then dispersed by shaking. Then, after standing overnight, the PTFE was re-dispersed by stirring with a spatula so as not to create unnecessary bubbles. After filtering through a mesh (0.05 mm in wire diameter), the liquid was left to stand for 20 minutes to remove unnecessary liquid from the plain-woven wire mesh. After that, the plain weave wire mesh was dried on aluminum foil at 150° C. for 20 minutes. Then, the mass of the PTFE residue was calculated by subtracting the total mass of the aluminum foil and the plain-woven wire mesh, which had been measured in advance, from the total mass.

(Toluene dispersibility evaluation)
After mixing 1.67 g (charged amount) of a dispersant and 8.33 g (charged amount) of toluene (dispersion medium) in a screw tube bottle (No. 7 manufactured by Maruem Co., Ltd.), polytetrafluoroethylene (PTFE ) (manufactured by Seishin Enterprise Co., Ltd., trade name: TFW-2000 (average particle diameter 6 μm)) 10 g (amount charged) was added. After that, the PTFE was dispersed by shaking the screw tube bottle up and down 30 times. When the PTFE was not dispersed by shaking alone, the PTFE was scraped off to the solution with a spatula and then dispersed by shaking. Then, after standing overnight, the PTFE was re-dispersed by stirring with a spatula so as not to create unnecessary bubbles. After filtering through a mesh (0.05 mm in wire diameter), the liquid was left to stand for 20 minutes to remove unnecessary liquid from the plain-woven wire mesh. After that, the plain weave wire mesh was dried on aluminum foil at 150° C. for 20 minutes. Then, the mass of the PTFE residue was calculated by subtracting the total mass of the aluminum foil and the plain-woven wire mesh, which had been measured in advance, from the total mass.

For NMP dispersibility evaluation and toluene dispersibility evaluation, a value (%) obtained by dividing the mass of the PTFE residue by the charged amount of PTFE was used. The smaller the value, the better the dispersibility, which is preferable. Specifically, NMP dispersibility and toluene dispersibility were evaluated in the following five stages.
A: Less than 4% B: 4% or more and less than 9% C: 9% or more and less than 40% D: 40% or more and less than 70% E: 70% or more

(Water dispersibility evaluation)
0.67 g (charged amount) of dispersant, 8.33 g (charged amount) of water (dispersion medium), and 1.00 g (charged amount) of nonionic surfactant are placed in a screw tube bottle (No. 7 manufactured by Maruem Co., Ltd.). After mixing, polytetrafluoroethylene (PTFE) (trade name: TFW-2000 (average particle size 6 μm), manufactured by Seishin Enterprise Co., Ltd.) was added (amount charged). Here, polyoxyalkylene branched decyl ether (“Noigen XL-70” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as the nonionic surfactant. After that, the PTFE was dispersed by shaking the screw tube bottle up and down 30 times. When the PTFE was not dispersed by shaking alone, the PTFE was scraped off to the solution with a spatula and then dispersed by shaking. Then, after standing overnight, the PTFE was re-dispersed by stirring with a spatula so as not to create unnecessary bubbles. After filtering through a mesh (0.05 mm in wire diameter), the liquid was left to stand for 20 minutes to remove unnecessary liquid from the plain-woven wire mesh. After that, the plain weave wire mesh was dried on aluminum foil at 150° C. for 20 minutes. Then, the mass of the PTFE residue was calculated by subtracting the total mass of the aluminum foil and the plain-woven wire mesh, which had been measured in advance, from the total mass.

A value (%) obtained by dividing the mass of the PTFE residue by the charged amount of PTFE was used for the evaluation of water dispersibility. The smaller the value, the better the dispersibility, which is preferable. Specifically, the water dispersibility was evaluated in the following five stages.
A: Less than 4% B: 4% or more and less than 9% C: 9% or more and less than 40% D: 40% or more and less than 70% E: 70% or more

From the results in Tables 1 and 2 above, we learned the following. That is, the constituent monomer (a) containing the (meth)acrylate compound (a1) represented by the general formula (1) and the (meth)acrylate compound (a2) represented by the general formula (2) is polymerized. The dispersant containing the obtained copolymer has a (meth)acrylate compound (a1) represented by the general formula (1) or a (meth)acrylate compound represented by the general formula (2) in the constituent monomer (a). It was found that the NMP dispersibility and the toluene dispersibility are significantly superior to the case where (a2) is not included. Although not shown in the table, dispersibility in MEK was similar to toluene dispersibility.

Further, the dispersant containing the copolymer obtained by polymerizing the constituent monomer (a) further containing the (meth)acrylate compound (a3) represented by the above general formula (3) is the constituent monomer (a) It has been found that the water dispersibility is remarkably excellent as compared with the case where the (meth)acrylate compound (a3) represented by the general formula (3) is not included. Although not shown in the table, the (meth)acrylate compound (a2) represented by the general formula (2) is used rather than the (meth)acrylate compound (a3) represented by the general formula (3). There was a tendency for foaming to be less in the case where

〈Impossible and impractical circumstances〉
The fluororesin dispersant of the present embodiment contains the (meth)acrylate compound (a1) represented by the general formula (1) and the (meth)acrylate compound (a2) represented by the general formula (2). It contains a copolymer (A) obtained by polymerizing constituent monomers. Since the structure of this copolymer is complicated, it is difficult to express it with a general formula. Furthermore, if the structure is not specified, the properties of the material that are determined accordingly cannot be easily determined. That is, it is impossible to directly specify the copolymer contained in the fluororesin dispersant of the present embodiment by its structure or properties.

The present invention is not limited to the above-described embodiments, and can be implemented in various configurations without departing from the spirit of the present invention. For example, the technical features in the embodiments and examples corresponding to the technical features in each form described in the Summary of the Invention are used to solve some or all of the above problems, or In order to achieve some or all of the effects, it is possible to appropriately replace or combine them. Also, if the technical features are not described as essential in this specification, they can be deleted as appropriate.

Claims

A fluororesin dispersant containing a copolymer,
The copolymer is
a (meth)acrylate compound (a1) represented by the following general formula (1);
a (meth)acrylate compound (a2) represented by the following general formula (2);
A dispersant for a fluororesin, comprising a copolymer obtained by polymerizing a constituent monomer (a) containing
Rf -Cb-R-O-X (1)
(Wherein, R f is a perfluoro (poly) ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, and R has 1 or more carbon atoms. 8 or less alkylene group, and X is an acryloyl group or a methacryloyl group.)
HO-(PO)pY (2)
(In the formula, PO is an oxypropylene group, p is a number of 2 or more and 150 or less, and Y is an acryloyl group or a methacryloyl group.)
The dispersant for fluororesin according to claim 1, wherein said Cb is an ester bond.
3. The fluororesin dispersion according to claim 1, wherein the constituent monomer (a) further contains a (meth)acrylate compound (a3) represented by the following general formula (3): agent.
AO-(EO)qZ (3)
(wherein A is H or CH3 , EO is an oxyethylene group, q is a number from 2 to 150, and Z is an acryloyl group or a methacryloyl group.)
Any one of claims 1 to 3, wherein the (meth)acrylate compound (a1) is contained in 30 parts by mass or more and 80 parts by mass or less in 100 parts by mass of the constituent monomer (a). Dispersant for fluororesin according to .
3. The Rf is CF3CF2CF2O (CF( CF3 ) CF2O ) nCF ( CF3 ), where n is a number greater than or equal to 0. Item 5. The dispersing agent for fluororesin according to any one of Items 4-4.
The dispersant for fluororesin according to claim 5, wherein said n is 0.
A composition comprising the fluororesin dispersant according to any one of claims 1 to 6 and a surfactant.
A dispersion containing the fluororesin dispersant according to any one of claims 1 to 6 and a fluororesin.
An article impregnated or coated with the dispersion liquid according to claim 8.
Polymerizing a constituent monomer (a) containing a (meth)acrylate compound (a1) represented by the following general formula (1) and a (meth)acrylate compound (a2) represented by the following general formula (2) A copolymer obtained by
Rf -Cb-R-O-X (1)
(Wherein, R f is a perfluoro (poly) ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, and R has 1 or more carbon atoms. 8 or less alkylene group, and X is an acryloyl group or a methacryloyl group.)
HO-(PO)pY (2)
(In the formula, PO is an oxypropylene group, p is a number of 2 or more and 150 or less, and Y is an acryloyl group or a methacryloyl group.)