JP2002088349A - Water-repellent/oil-repellent agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agent having both a water-repellency and an oil- repellency exhibiting extremely high water repellency/oil repellency both of which are essentially required for fluororesins, and a water-repellent/oil-repellent agent composition which contains the water-repellent/oil-repellent agent and has high water repellency/oil repellency. SOLUTION: This water-repellent/oil-repellent agent comprises a polyether having a polymerization unit represented by formula (I) [Xs are the same or different and each hydrogen atom, fluorine atom or chlorine atom; Rf is a terminal fluorine atom-containing fluoroalkyl group or a group represented by the formula (AO)m-B-R1 (R1 is a perfluoroalkyl group; A is a 1-3C alkylene group; (m) is a number of 1-20; B is a 1-6C alkylene group; mA groups may be the same or different)]. The water-repellent/oil-repellent agent composition comprises the water-repellent/oil-repellent agent. The water-repellent/oil-repellent agent composition further may contain a polyether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water / oil repellent useful for industrial parts, construction materials, chemical materials and the like, and a water / oil repellent composition containing the same.

[0002]

BACKGROUND OF THE INVENTION Poly (tetrafluoroethylene) (hereinafter referred to as PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter referred to as FEP), tetrafluoroethylene-perfluoroalkylvinyl ether Copolymer (hereinafter referred to as PFA), tetrafluoroethylene-
Various fluororesins represented by ethylene copolymer (hereinafter, referred to as ETFE) and poly (vinylidene fluoride) (hereinafter, referred to as PVDF) have high water repellency,
Widely used industrially as a waterproof coating agent.

In order to provide water- and oil-repellent fluororesins, various fluoropolymers and compositions thereof are disclosed. For example, high-performance fluororesins by copolymerization of various monomers, polyisocyanate-based or melamine-based polymers are disclosed. A method of using a fluorine-containing resin which is crosslinked and cured by using a system compound or the like as a curing agent, a pyridinium quaternary salt type waterproofing agent, or a paraffinic waterproofing agent is used in combination.

[0004] Although these methods can achieve a certain degree of water and oil repellency, their effects have not been satisfactory. Water repellency (or oil repellency) had satisfactory performance, but oil repellency (or water repellency) did not always have satisfactory performance.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional drawbacks, and to provide a water-repellent / oil-repellent agent exhibiting extremely high water / oil repellency originally expected of a fluororesin, and a high repellency containing the same. An object of the present invention is to provide a water / oil repellent composition having water / oil repellency.

[0006]

The present invention provides a compound represented by the general formula (I):
A water / oil repellent comprising a polyether having a polymerized unit represented by the following formula (hereinafter referred to as polymerized unit (I)), a water / oil repellent composition containing the water / oil repellent, and containing the polyether To provide a water / oil repellent composition.

[0007]

Embedded image

[Wherein, X represents the same or different and represents a hydrogen atom, a fluorine atom or a chlorine atom. R _f represents a fluoroalkyl group having a fluorine atom at the terminal, or
(AO) represents a group represented by _m -BR ¹ . Here, R ¹ is a perfluoroalkyl group, A is an alkylene group having 1 to 3 carbon atoms, m is a number of 1 to 20 and B is an alkylene group having 1 to 6 carbon atoms. May be. ]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION [Water repellent / oil repellent]
In the oil repellent, when R _f is a fluoroalkyl group having a terminal fluorine atom, preferred examples include a branched or straight-chain fluoroalkyl group having 1 to 22 carbon atoms having a terminal fluorine atom. As more preferred examples, F (CF ₂ ) ₂ CH _2- , F (CF ₂ ) ₄ CH _2- , F
_{(CF 2) 6 CH 2 -} , F (CF 2) 8 CH 2 -, F (C
_{F 2) 10 CH 2 -,} F (CF 2) 12 CH 2 -, F (CF 2)
Examples thereof include fluoroalkyl groups such as ₁₄ CH ₂ — and F (CF ₂ ) ₁₆ CH ₂ —.

R_fIs the formula-(AO)_m-BR¹[Where,
R¹, A, B, m: have the above-mentioned meanings. A group represented by
In the case where¹Preferably has 1 to 2 carbon atoms
2 branched or linear perfluoroalkyl groups, more preferably
Preferably F (CF_Two)_Two−, F (CF_Two)_Four−, F (C
F_Two)₆−, F (CF_Two)₈−, F (CF_Two)_Ten−, F (C
F_Two) ₁₂−, F (CF_Two)₁₄−, F (CF_Two)₁₆−, (C
F_Three)_TwoCF-, (CF_Three)_TwoCF (CF_Two)_Two−, (C
F_Three)_TwoCF (CF_Two)_Four−, (CF_Three)_TwoCF (CF_Two)₆−
And the like, particularly preferred.
Is F (CF_Two)₈−, F (CF_Two)_Ten−, F (CF_Two)₁₂
−, F (CF_Two)₁₄−, F (CF_Two)₁₆-Perfluoro
Alkyl. A represents a methylene group, an ethylene
And m is preferably 1 to
10, more preferably 1 to 5. Combination of A and m
The combination of A is a methylene group and m is 1
Combinations are particularly preferred. B is preferably carbon
Examples are linear alkylene groups of numbers 1 to 6, more preferably
Is a methylene group, an ethylene group or a trimethylene group.

In the water / oil repellent of the present invention, the polymerization unit
The polyether having (I) is represented by R _fHave different weights
May have a combined unit.
The arrangement of these polymerized units in the
Lock, alternating, periodic, statistical (including random)
There may be.

The water / oil repellent of the present invention comprises a polymerized unit (I)
Not only a polyether consisting of only a polyether but also a copolymer with another polymerized unit as long as the water / oil repellency is not significantly impaired. In this case, the polymerized unit (I)
And other polymerized units (which may be plural types) are arranged in blocks, alternating, periodic, statistical (including random),
Any of a graft type may be used.

[0013] Alternating, periodic, statistical (including random) copolymers containing polymerized units (I) can be obtained by anionic or cationic copolymerization. Preferred other polymerization units include polymerization units derived from substituted epoxides other than the polymerization unit (I), monomers such as oxetane, (meth) acrylates, styrene, butadiene, isoprene, lactones, carbon dioxide, lactams, and the like. Polymerized units derived from these derivatives are mentioned, and particularly preferred examples include those derived from ethylene oxide, tetrafluoroethylene oxide, propylene oxide, hexafluoropropylene oxide, methyl methacrylate, hydroxyethyl methacrylate, fluoroalkyl methacrylate, styrene, and the like. Can be exemplified.

When the water- and oil-repellent agent of the present invention is a block or graft copolymer, the chain portion comprising only the other polymer units without the polymer unit (I) may contain an anion, a cation, a radical polymerization or a condensation polymerization. It may be obtained by any polymerization method such as polymerization. Preferred examples of such a polymer chain include poly [(meth) acrylate], polystyrene, polybutadiene, polyisoprene, amorphous polypropylene, polyallylamine, polyethyleneimine, epoxy resin, and derivatives thereof.

When the water / oil repellent of the present invention is a copolymer as described above, the mole fraction of the polymerized unit (I) in the copolymer is preferably 0.01 or more and less than 1.0, and more preferably. Is 0.05 or more and less than 1.0,
Especially preferably, it is 0.1 or more and less than 1.0.

[Water / oil repellent composition] In the water / oil repellent composition containing the water / oil repellent of the present invention (hereinafter simply referred to as "composition"), other components constituting the composition There is no particular limitation on them, they are existing resins other than the water / oil repellent of the present invention, rubber, aqueous or oily liquid medium,
Various powders or a mixture thereof may be used.

Other resins used in the composition of the present invention include polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, polycarbonate, ABS resin, AS resin, AES resin, polyamide 6, polyamide 66. , Polyetherimide, polyetheretherketone, polyphenylene oxide, PTFE, FEP, PFA, ETF
E, PVDF, silicone, thermoplastic resins such as wax and derivatives thereof, and copolymers containing them,
Epoxy resin, phenol resin, polyimide, polyurethane, melamine resin, urea resin, polyester resin,
Examples thereof include thermosetting resins such as unsaturated polyester resins and derivatives thereof. When a composition containing the thermoplastic resin and the water / oil repellent of the present invention is obtained, these are molded or melted and kneaded or molded / mixed in a solution and then molded / dried. The water / oil repellent is unevenly distributed in the vicinity of the surface layer of the molded article, and can impart water / oil repellency to the entire surface of the molded article efficiently with a small amount of addition. Further, when obtaining a composition containing the thermosetting resin and the water / oil repellent of the present invention, after previously mixing the precursor or prepolymer of the thermosetting resin and the water / oil repellent of the present invention, It can be polymerized / cured.

The rubbers usable in the composition of the present invention include natural rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, butyl rubber, ethylene-propylene copolymer (EPM), ethylene-propylene-diene terpolymer (EPDM), and nitrile- Examples thereof include synthetic rubbers such as butadiene rubber, chloroprene rubber, urethane rubber, epichlorohydrin rubber, silicone rubber, and thermoplastic elastomer. When a composition containing a rubber and the water / oil repellent of the present invention is obtained, these rubber and the water / oil repellent of the present invention, a crosslinking agent, and other components can be kneaded, molded, and then crosslinked.

When a composition containing the water / oil repellent of the present invention and the above resin and / or rubber is obtained, the amount of the water / oil repellent of the present invention used is 100 parts by weight of the above resin and / or rubber. On the other hand, the amount is preferably 0.001 to 100 parts by weight, but is preferably 0.05 to 20 parts by weight, more preferably 0.5 to 15 parts by weight to maintain good water repellency.

The liquid medium that can be used in the composition of the present invention is not particularly limited, but fluorine oil such as fomblin is preferred.
The amount of the water / oil repellent used when obtaining the composition containing the water / oil repellent of the present invention and the liquid medium is preferably 0.05 to 500 parts by weight, more preferably 100 parts by weight of the liquid medium. Is 3 to 300 parts by weight, but when the liquid medium used is volatile, the water / oil repellent of the present invention and the volatile liquid medium may be used in any mixing ratio.

As the powder usable in the composition of the present invention,
(A) Inorganic compounds such as silica, titanium oxide, alumina, iron oxide, tin oxide, aluminum hydroxide, magnesium hydroxide, and calcium carbonate; metals such as iron, silver, copper, and aluminum; and various organic polymers. (B) inorganic pigments such as red iron, lead white, graphite, navy blue, titanium white and various organic pigments, (c) carbon black, graphite, carbon whiskers, carbon fiber, glass Fillers such as fibers and various clay minerals, (2) biological materials such as chitosan, starch, cellulose, glucose, amino acids, and proteins, and (e) various composite material particles can be exemplified. In this case, the particle size of these powders is appropriately selected depending on the purpose of use.

The amount of the water / oil repellent of the present invention used to obtain a composition containing the water / oil repellent of the present invention and the powder is 0.001 to 100 parts by weight of the powder. 100
00 parts by weight is preferred. In particular, when the water / oil repellent of the present invention is used as the water repellency imparting agent for the powder, the powder 1
The water / oil repellent of the present invention is 0.05 to 20 parts by weight based on 00 parts by weight.
By weight is more preferable, and particularly when the powder is used as a reinforcing or modifying agent for the water / oil repellent of the present invention,
The water / oil repellent 100 to 100 parts by weight of the powder of the present invention
5000 parts by weight is more preferred.

In the composition of the present invention, the water / oil repellent may be used alone or in combination of two or more.

The composition of the present invention may contain an antioxidant, an antioxidant or other stabilizers, a preservative, a viscosity modifier, a flame retardant, An additive such as an agent or a surfactant can be used in combination.

The method for preparing the composition of the present invention is not particularly limited. That is, the water repellent / oil repellent of the present invention may be added to and mixed with the resin, rubber, liquid medium, or powder, or the resin, rubber, liquid medium, or powder may be added to the water / oil repellent of the present invention. May be added.

[Water / oil repellency] The water / oil repellent of the present invention and the composition containing the same have high water / oil repellency, and the contact angle of water on the smooth surface of the resin. Preferably 10
It shows a high value of 0 ° or more, more preferably 110 ° or more, and the contact angle of liquid paraffin on the smooth surface preferably shows a high value of 60 ° or more, more preferably 70 ° or more.

[0027]

The water / oil repellent of the present invention and the water / oil repellent composition containing the same are heat-resistant, chemical-resistant, oxidation-resistant, flame-retardant, etc. based on high water- and oil-repellency. , Filters, porous membranes, films, sheets, fibers, rubber, tubes, piping, bearings, housings, coating materials, electronic materials, building materials, automotive parts, printer parts, paints, Sealants, coating agents, release agents, linings, containers, inks, cosmetics, cleaning agents, body soaps, shampoos, rinses, surface water repellents, hair setting agents, face wash agents, clothing detergents, surface modifiers, finishes It can be used effectively in various industrial fields such as agents, bio-related products, car wax and the like. Further, the water / oil repellent of the present invention and the composition containing the same can maintain high performance for a long period of time.

[0028]

EXAMPLES Examples 1 to 3 and Comparative Examples 1 to 3 The water and oil repellents A to C and the comparative polymers DF of the present invention shown below were tested for water and oil repellency by the following method. evaluated. Table 1 shows the results.

<Water- and oil-repellent and comparative polymer> Water- and oil-repellent A poly (1H, 1H, 2H, 2H-heptadecafluorodecylglycidyl ether synthesized according to Example 8 of the specification of WO 99/42513) ); in the general formula (I), X = H, R f = - in ^{_{(AO) m -B-R 1}} , A = methylene, m = 1, B = ethylene _{^{group, R 1 = - (CF 2}} ) ₈
F.

Water / oil repellent B 1H, 1H, 2H, 2H Instead of 1H, 1H, 2H, 2H-heptadecafluorodecylglycidyl ether, 1H, 1H, 2H, 2H
1H, 1H, 2H, 2H-hepta synthesized in the same manner as for the water / oil repellent A except that a mixture of heptadecafluorodecyl glycidyl ether and octyl glycidyl ether is used as a 10/90 (weight ratio is shown below) mixture. Decafluorodecyl glycidyl ether-octyl glycidyl ether copolymer (10/90); In the general formula (I), X = H, R _f = — (AO) _m —BR ¹ , A = methylene group, m = 1, B = ethylene group, R ¹ = — (CF ₂ ) ₈
A random (10/90) copolymer of a polymerization unit represented by F and octyl glycidyl ether.

Water / oil repellent C 1H, 1H, 2H, 2H Instead of 1H, 1H, 2H, 2H-heptadecafluorodecyl glycidyl ether, 1H, 1H, 2H, 2H
Poly (1H, 1H, 2H, 2H-tridecafluorooctyl glycidyl ether) synthesized by the same method as that of the water / oil repellent A except that tridecafluorooctyl glycidyl ether is used; X in the general formula (I) =
H, R _f =-(AO) _m -BR ¹ , A = methylene group,
m = 1, B = ethylene group, R ¹ = — (CF ₂ ) ₆ F.

Comparative polymer D PTFE resin: 7 available from DuPont Fluorochemicals, Mitsui
-J Comparative Polymer E PFA resin: 34, manufactured by DuPont Fluorochemicals, Mitsui
0-J Comparative polymer F PVDF resin: VP-800 manufactured by Daikin Industries, Ltd.

<Evaluation method of water / oil repellency> Water / oil repellent A
-C and comparative polymers DF were pressed in a Teflon (registered trademark) plate to produce a smooth resin. On the smooth surface, the contact angle of water and liquid paraffin was measured using CA-A type manufactured by Kyowa Interface Science Co., Ltd.

[0034]

[Table 1]

Example 4 20 parts by weight of a water / oil repellent A was added to a polypropylene resin 10
In addition to 0 parts by weight, they were mixed with a twin-screw extruder set at 210 ° C. The obtained composition was press-molded at 170 ° C. for 10 minutes. The water contact angle of the surface of this press-formed product is 120
゜, the contact angle of liquid paraffin was 80 °.

Comparative Example 4 A press-formed product was obtained from Comparative Polymer F and a polypropylene resin in the same manner as in Example 4, but the water contact angle on the surface was 9%.
It was 3 ゜.

Example 2 A molded article was obtained by thinly coating the surface of a polypropylene resin with a water / oil repellent A. The water contact angle of the surface of this molded article is 140
゜, the contact angle of liquid paraffin was 90 °. After immersing it in water for one month, the contact angles of water and liquid paraffin on the surface were measured and found to be 111 ° and 82 °, respectively.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4H020 BA12 4J002 AC011 AC031 AC071 AC081 AC091 AE001 BB031 BB121 BB151 BC031 BC051 BC061 BD031 BD121 BD151 BF021 BG061 BN061 BN151 CC041 CC161 CC181 CD001 CF001 CH21 001 001 001 001 4J005 AA04 AA09

Claims (3)

[Claims] 1. A water / oil repellent comprising a polyether having a polymerized unit represented by the general formula (I). Embedded image [In the formula, X represents the same or different and represents a hydrogen atom, a fluorine atom or a chlorine atom. R _f represents a fluoroalkyl group having a fluorine atom at the terminal, or a compound represented by the formula-(AO) _m -B
A group represented by -R ^1. Here, R ¹ is a perfluoroalkyl group, A is an alkylene group having 1 to 3 carbon atoms, and m is 1 to
The number 20 and B represent an alkylene group having 1 to 6 carbon atoms;
A may be the same or different. ] 2. A water / oil repellent composition comprising the water / oil repellent according to claim 1. 3. A water / oil repellent composition comprising the polyether according to claim 1.