JPS6399285A - Water and oil repellent - Google Patents

Abstract

PURPOSE:To provide a water and oil repellent capable of forming film which is uniform and tough and high in the adhesiveness to articles treated therewith, consisting of a fluorine-contg. polymer containing specified quantities of specific fluorine-contg. acrylate. CONSTITUTION:The objective water and oil repellent consisting of a fluorine- contg. polymer containing >=10wt% of a fluorine-contg. acrylate of formula [X is F, Cl or -CFX<1>X<2> (X<1> and X<2> are each H or F); Y is 1-3C alkylene, -CH2CH2N(R)SO2- (R is 1-4C alkyl), or -CH2CH(OZ)CH2- (Z is H or acetyl); Rf is 3-21C fluoroalkyl or 3-21C fluoroalkyl containing O1-10 in the carbon chain (but any of the Os are not mutually adjacent)]. Said polymer can be prepared by radical or anionic polymerization.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a fluorine-containing (a) hydraulic oil agent.

[Conventional technology]

It is known that fluorine-containing polymers such as fluoroalkyl methacrylate polymers can be used as 1a water IQ oil agents (see, for example, Japanese Patent Publication No. 47-40467).

However, conventionally known polymers having t8 water Iθ oiliness,
It has a problem that it is not compatible with the article to be treated and has a low film strength, so it easily peels off when rubbed a little.

[Purpose of the invention]

The present inventors produced various fluorine-containing acrylate polymers and investigated their film-forming properties, adhesion to objects to be treated, film strength, etc., and found that polymers containing specific fluorine-containing acrylates as constituent components The present invention has been achieved based on the discovery that these properties are excellent.

An object of the present invention is to provide a fluorine-containing water-repellent IB oil agent that can form a uniform, tough film with good adhesion to treated articles.

[Structure of the invention]

The present invention provides: 2: C11,・C-X (1) COO
-Y-Rf (wherein, X is a fluorine atom, a chlorine atom, or -CFX'X
``group [However, xl and X2 are the same or different hydrogen atoms or fluorine atoms], Y has 1 to 1 carbon atoms.
3 alkylene group, -CHzCHJ(R) Sow- group [wherein R is an alkyl group having 1 to 4 carbon atoms. ]
or -CIlxCtl(OZ)CHz- group [however, 2
is a hydrogen atom or an acetyl group. ), Rf is a fluoroalkyl group having 3 to 21 carbon atoms or a fluoroalkyl group having 3 to 21 carbon atoms containing 1 to 10 oxygen atoms in the carbon atom chain [however, oxygen atoms are not adjacent to each other] This is a water and oil repellent made of a fluorine-containing polymer containing at least 10% to 1% of a fluorine-containing acrylate represented by , ).

The number average molecular weight (by gel permeability chromatography) of the fluorine-containing polymer is 10,000 to 4,000,000 KN.
Intrinsic viscosity [l] (Solvent: meta-xylene hexafluoride, methyl ethyl ketone, chloroform, 1,1
．． 1-Trichloroethane, etc. (temperature: 35°C), preferably in the range of 0.25 to 3.0.0 If the molecular weight is too small, it will easily peel off from the article to be treated and the film strength will be low.
If it is too large, it will be difficult to apply it to the article to be treated.

The Rf group preferably has the formula: %formula%) from above the tθ water Iθ oiliness of the polymer (wherein the end is an integer of 1 to 5, n is 0 or 1, and q is 1 to
5 integer, Rf' represents a fluorine atom or a trifluoromethyl group), 2: (wherein p is 0 or an integer of 1 to 5, Rf' is the same as above) or formula: %formula% ( In the formula, pt+t is a phenylene group, and Rr'' is a perfluoroalkyl group having 5 to 15 carbon atoms.

Monomers that can be contained in the fluorine-containing polymer in addition to the fluorine-containing acrylate (1) include, for example, 2: C1,.C(2) 0O-8 (wherein A is a hydrogen atom or a chlorine atom) or a methyl group, B is an alkyl group having 1 to 10 carbon atoms, and 6 to 8 carbon atoms.
represents an alicyclic group or a fluoroalkyl group having 1 to 10 carbon atoms; ~8 alicyclic groups), ethylene, propylene, styrene, as well as vinyl groups, hydroxyl groups, carboxyl groups, glycidyl groups,
Ethylenically unsaturated monomers such as acrylates or methacrylates having functional groups such as dialkylamino groups or trialkoxysilyl groups can be mentioned.

Examples of the fluorine-containing acrylate (1) include CH
F-COOCII□CIIzCtF+s, CHt=
CF-COOCII□CzFs 1C1h=CP-CO
OCHtC*F+hCFCCFs')t, CHx=lC
F-COOCHt-CF (CFriOCF, CF(CF
ff) QC, Ft, CH! =CF-COOCR1-C
F(CF3)OCsFt, CHgICF-COOCHt
CHg-N(CH3)SOzCaF+t, C11! =
CF-COOC1lzCII(Off)CHzCJ+w
, Ct1g=CCI-COOC1lzCILxCsF
+t, CH2・CCl-C00CHzCF(CF3)
OC3Ft,CH,,C(CF+)-COOCIbCl
Examples include lzCJ+s.

Examples of monomer (2) include CHt=+, ClICOO
C1b, CL=CHCOOC+zllzs, C
IIz□Cl1COO-R' (However, R1 is a cyclohexyl group theal.), CHz・C(C)Iz)CO
OCHs, CIh=C(C)1C00CI. fli
t, CHIC(C1ls)COOCHtCIItC
tJs, CI(x=c(C1)COOCL, etc.).

Examples of monomer (3) include CIIz=CF-COOC
R13, CIIz□CF-COOR' (However, R1 is the same as above-), C11! =CF-C00C+el
lst etc. can be mentioned.

Examples of acrylates or methacrylates with functional groups include C11z=C(CHs)Coo(CHzC
HzO) +.

C0C(CHs)=CHt, C1la=C(CHs)
COO(CHz) +. C0C(C1l,)=CHz
, C11z=C(Clls) C00CHzCH(O
COC(CHi)-Clh)CHxOCQC(CIri)
1=CHt, CHz=CIICOOCHtCII□
OH, CHlCHCOO-R” (However, R1 is a glycidyl group.), CI+, =C(CHs)C0
Examples include 0CIltC11xCII□5i (OCH3)i.

A thin film made of a fluorine-containing polymer containing 10'It% or more of fluorine-containing acrylate (1), especially a polymer containing an acrylate in which X is a fluorine atom or a chlorine atom, has strong and good flexibility. It has good adhesion to objects to be treated.

Inexpensive monomers such as ethylene, propylene, and styrene as monomer (2) are effective in lowering the cost of fluorinated polymers, and functionally provide hardness, etc. to fluorinated polymers. have an effect. The amount of ethylene, propylene, styrene, etc. used as monomer (2) is usually 90! -11%
It is as follows.

When the fluorine-containing polymer contains a functional group, the adhesiveness of the fluorine-containing polymer to the article to be treated is improved. Moreover, the fluorine-containing polymer can be crosslinked using this functional group. As the crosslinking method, methods commonly employed in this technical field can be used (for example, Japanese Patent Publication No. 47-428
(See Publication No. 80).

The amount of acrylate or methacrylate having a functional group that is the source of the functional group of the fluorine-containing polymer is usually 30
It is 4%% or less.

The fluorine-containing polymer of the present invention can be obtained by radical polymerization (solution,
(bulk form, emulsification, etc.) or anionic polymerization.

Examples of solvents that can be used in solution polymerization include fluorinated solvents such as metaxylene hexafluoride and trichlorotrifluoroethane, chlorinated solvents such as 1,1゜1-trichloroethane, ethyl acetate, methyl isobutyl ketone, Examples include hydrocarbon solvents such as acetone, toluene, and xylene. The polymer prepared by solution polymerization can be separated from the solvent and dried and used again as a solution, or the solution can be simply diluted and used after the polymerization is completed.

A polymer prepared by bulk polymerization can be used as a solution after drying.

Examples of polymerization initiators that can be used in solution polymerization and bulk polymerization include azo compounds such as azobisisobutyronitrile, and peroxide compounds such as benzoyl peroxide.

In solution polymerization and bulk polymerization, mercaptans such as lauryl mercaptan and thiophenol can be used as chain transfer agents.

The polymerization temperature is preferably 30 to 100°C in any of the above methods.

Fluorine-containing polymers prepared by solution polymerization or bulk polymerization are
Usually, the fluoropolymer is dissolved in a dissolving solvent that can dissolve the fluoropolymer well, and then diluted with a diluting solvent that has a dissolving ability that does not precipitate the dissolved fluoropolymer, and then applied to the article to be treated. Application methods include dipping, brushing, spraying, etc., similar to the usual 18 water and oil repellent. The concentration is 0.1 to 30% by weight for the brush coating method, and 0.0 for the spray method.
The amount is preferably about 5 to 2% by weight, and after being applied to the article, it is dried at room temperature to 150°C.

Examples of dissolving solvents include fluorinated solvents such as metaxylene hexafluoride and trichlorotrifluoroethane;
Examples include chlorine-based solvents such as trichloroethane. Examples of diluent solvents include chlorine solvents such as tetrachlorethylene and trichlorethylene, ketone solvents such as acetone, ester solvents such as ethyl acetate, aromatic solvents such as toluene, and saturated aliphatic solvents such as n-pentane. can be mentioned. A dissolving solvent can also be used as a diluting solvent.

As the emulsifier used in emulsion polymerization, nonionic compounds are preferred, but cationic emulsifiers can also be used.

Polymerization initiators that can be used in emulsion polymerization include:
Water-soluble compounds are preferred, and include, for example, azo compounds such as azobisisobutyramidine hydrochloride, and peroxide compounds such as succinic acid peroxide.

The polymerization temperature is preferably 30 to 100°C.

The fluorine-containing copolymer prepared by emulsion polymerization can be used as an aqueous type 18 water (Ω oil agent).

Emulsifiers do not need to be omitted in normal cases. The aqueous type 18 water tΩ oil agent can be applied in the same manner as described above. Since water-based water and oil repellents contain water, it is preferable to heat them to 100 to 150°C when drying.

(1) The second χ contains a trifluoromethyl group.

When homopolymerizing elementary acrylates, anionic polymerization is preferred from the viewpoint of polymerization rate.

Examples of polymerization initiators that can be used in anionic polymerization include alkali metals, metal hydrides, sodium amide, Grignard reagents, metal alkyls, pyridine, and the like.

Examples of solvents that can be used in anionic polymerization include aromatic solvents such as toluene, ether solvents such as tetrahydrofuran, etc. Polymerization in anionic polymerization is usually carried out under a high vacuum of about I x 10-' mm 11 g. Alternatively, it is carried out under a dry inert gas atmosphere. The polymerization temperature is usually -100 to 70°C.

Polymers produced by anionic polymerization can be applied to articles to be treated in the same manner as the polymers produced by solution polymerization.

The water and oil repellent of the present invention is suitable for applications requiring abrasion resistance, such as tents, seat covers, umbrellas, raincoats, shoes, midgets, bags, jackets, jumpers, aprons, blazers, slacks, skirts, and kimonos. It can be used to treat various solid materials such as car vents, sofas, curtains, etc. to impart river water oil repellency.

(Example) Example 1 Into a 200cc glass ampoule: C1h=CF
-COOC11ffiCF (CFI) 50 g of fluorine expressed by OCjFヮ (hereinafter referred to as αF6FO), 4 g of glycidyl methacrylate (hereinafter referred to as GMA)
1 metaxylene hexafluoride (hereinafter m-XHF
That's what it means. ) 80g and azobisisobutyronitrile 0
．． 5 g was put therein, followed by repeating degassing and nitrogen purging three times using the freeze-thaw method using methanol/dry ice, and then melt-sealing.

The ampoule was immersed in a constant temperature bath at 50° C. for 30 hours.

Thereafter, the reaction mixture was poured into petroleum ether, and the precipitated fluorine-containing polymer was dried. 52 g of a fluorine-containing polymer was obtained.

[η] of the polymer measured at a temperature of 35° C. using m-XIIF as a solvent was 1.12.

The results of elemental analysis were 30.2% carbon and 54% fluorine.
It was found that at 4%, almost all of the monomers were polymerized.

The obtained polymer was mixed with 30% by weight m-XHF (dissolving solvent).
This solution was further diluted to 0.5% by weight with trichlorotrifluoroethane (dilution solvent).

The diluted solution was applied with a brush onto a synthetic leather made of polyurethane-coated nonwoven fabric (Colfam, manufactured by DuPont) with a thickness of 3 m+++, and then heated at 80° C. for 30 minutes to prepare an adhesion test sample.

The contact angles of water and n-hexadecane were measured immediately after the sample was prepared and after the sample was subjected to 120 bending and stretching operations 1o and oooo times. The results are shown in Table 2.

Examples 2 to 9 and Comparative Examples 1 to 3 Adhesion test samples were prepared in the same manner as in Example 1 using the monomer and polymer dissolving solvents and diluting solvents shown in Table 1. The test results are shown in Table 2.

Table 1 Table 1 (continued) In Table 1, each abbreviation indicating a tetramer means the following tetramer. Same meaning below.

MA: C) Ig=CIlC00CIIsαF
17F: CHt=CFCOOCHzCIIt(C
hCh)+CFzCFsCMS: CIIz=
CII-Ph-CHxCl (However, ph is a phenylene group.) SA: C111CHCOOC+ all□1
7FA: CHr=C)ICOOClhC)Ig
CsF+ffαFi19F: Cl1z+ICFCO
OCIIzCHz(ChCFz)tcF(CFt)zε
GMA: CL=C(CL)COO(CIItC
LO) xcOc(Cfh)=CIhSMA
: C1h=C(Clh)COOC+sllst1
7FMA: C1hIIC(CH3)COOC1
hCHzCsF+t19FA: C)lz=cH
cOOcHzclI□C9FI9αC117F: C
112=CGICOOCR, CII□(CPzCFz)
zchcFsαCl119F: C11□=CC]C
00C112CIl□(CFzCh)zcF(CF+h
LA: CIIg:ClIC0OC+ zHz
s Table 2 Example 13 and Comparative Example 4 After dissolving the same polymers as those prepared in Example 1 and Comparative Example 3 in m-XHF to a concentration of 5% by weight,
It was cast onto a Petri dish with a diameter of 9 cm and dried. r￥
A sheet of approximately 82 μm was obtained.

The breaking strength and elongation of these sheets were examined and found to be as follows.

Polymer of Example 1 (corresponding to Example 13): Breaking strength =
1.0 kgf/mw” Elongation rate -300% Polymer of Comparative Example 3 (corresponding to Comparative Example 4): Breaking strength -0
, 26 kgf/am" Elongation rate = 450% Example 14 In a H four-loaf flask equipped with a stirrer, thermometer, reflux device, and dropping funnel, 1.91 g of water, 400 g of acetone, and αF
6FO300g SM^19 gSEG? lA 1 g
and 40 g of an emulsifier (122O in a NOF type) were added, and nitrogen was blown into the system to remove oxygen. The mixture was placed in a constant temperature bath at 65°C, and when the temperature became constant, 0.11 g of water in which 1.6 g of azobisisobutyramidine hydrochloride was dissolved was added dropwise to initiate polymerization. After 4 hours, solid content 12%
obtained a dispersion of A portion was sampled to determine the monomer composition and [η].

Monomer composition (wt%): αF6FO/M^/EGMA
= 93.7/610.3 (Elemental analysis: Carbon 39
．． 6% and fluorine 55.0%), [η) −0,68
゜The obtained dispersion was diluted with water to 0.5% by weight in a puffing tank. After soaking the polyester cloth in the puffing bath and wringing out the water,
A test sample was prepared by drying at 80°C for 3 minutes and heat treating at 150°C for 3 minutes.

When this sample was subjected to the JIS L 1006 taa test and the AATCC118-1966T oil repellency test, results of 100° and No. 6 were obtained, respectively.

The same sample was washed in a household electric washing machine at a bath ratio of 1:50.
Detergent Zabu, after washing at a temperature of 40℃, air dry.
When the test was performed again with a light iron at 140°C, results of 100° and No. 5 were obtained.

Comparative Example 5 [η] of the 0 polymer, which was polymerized and prepared as a test sample under the same conditions as in Example 14, except that the monomers were changed to 17FA 300 g, SMMA 19 g, and Eko^1 g, was 0. It was 38.

Water repellency test before and after washing under the same conditions as Example 14 and ta
When I conducted the a property test, I found that 1a aqueous ranged from 100° to 70°.
To, t0 oiliness decreased from No.3 to No.O.

〔Effect of the invention〕

The water-repellent J8 oil agent of the present invention is made of a polymer containing a fluorine-containing acrylate having a fluorine atom, chlorine atom, or a fluorine atom-containing group in the α position, so it has excellent film strength and adhesion to the article to be treated. It has superior properties compared to conventional TA water, water, oil, and oil agents, and is durable against washing, etc.

that's all

Claims (1)

[Claims] 1. Formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is a fluorine atom, a chlorine atom, or a -CFX^1X^2 group [However, The same or different hydrogen atoms or fluorine atoms.], Y is an alkylene group having 1 to 3 carbon atoms, -CH_2CH_2N(R)SO_2- [However, R is an alkyl group having 1 to 4 carbon atoms; be.〕
or -CH_2CH(OZ)CH_2- group [however, Z
is a hydrogen atom or an acetyl group. ], Rf is a fluoroalkyl group having 3 to 21 carbon atoms or a fluoroalkyl group having 3 to 21 carbon atoms containing 1 to 10 oxygen atoms in the carbon atom chain [however, oxygen atoms are not adjacent to each other. . ]. ) A water and oil repellent comprising a fluoropolymer containing at least 10% by weight of a fluorine-containing acrylate represented by: