JPS6392687A - Water and oil repellent - Google Patents

Abstract

PURPOSE:To provide a water and oil repellent which is excellent in water and oil repellency and effect of preventing chalking and which comprises a copolymer composed of a (meth)acrylate having a perfluoroalkyl group, n-butyl methacrylate and a crosslinkable monomer. CONSTITUTION:A water and oil repellent comprising a copolymer composed of 70-90wt% acrylate or methacrylate (a) having a 4-20C perfluoroalkyl group, 10-30wt% n-butyl methacrylate (b) and 0.2-5wt% crosslinkable monomer (c). The melting point of the copolymer is pref. 0-70 deg.C, particularly pref. 30-60 deg.C. Suitable examples of the crosslinkable monomer (c) include polyethylene glycol diacrylate and polyethylene glycol dimethacrylate, among which a monomer of the formula (wherein R<5> and R<6> are each H or methyl; and r is 1-50) is particularly pref.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to water and oil repellents, and more specifically, to water and oil repellents, including fibers, natural fibers, and leather. This invention relates to an aerosol water and oil repellent used in water and oil repellent treatment of W products and the like.

(Prior Art) In recent years, latex-type and organic solvent solution-type fluorine-based water and oil repellents have become known as fluorine-based water and oil repellents that provide excellent water and oil repellency to synthetic A fibers, natural WL fibers, leather products, etc. There is. Many of the organic solvent solution types are coated or immersed, etc.
A solution of a polymer that exhibits water and oil repellency is applied to the surface of the object to be treated and is dried to impart water and oil repellency to the object. In the case of this mold, unlike the latex mold, a curing process is not necessarily required, and it is a simple water- and oil-repellent material.
is possible. Such a solution type can be processed even more simply by adding a propellant, sealing it in a container, and turning it into an aerosol.

However, conventionally commercially available solution type (Unexamined Japanese Patent Publication No. 53-5
0078, etc.) is made into an aerosol and sprayed onto the surface of the object to be treated, for example, the surface of cloth, whitening is visible on the surface.

In order to eliminate this whitening phenomenon, an organic solvent solution type fluorine-based water and oil repellent containing a surfactant having an II L II value of 8 or less has been developed in JP-A-59-74181. However, these have the disadvantage that if the amount of surfactant added is too small, the anti-whitening effect will not be sufficient, and if it is too large, water and oil repellency will be inhibited. Also, JP-A-59-25869, JP-A-5
No. 6-106987, a water and oil repellent composition for aerosol formulation has been developed which contains 0.2 to 25% by weight of a high boiling point solvent consisting of an ethylene glycol derivative. As the amount of the ethylene glycol derivative added increases, a sufficient whitening prevention effect can be obtained, but the high boiling point solvent is difficult to volatilize from the treated cloth. Therefore, the water- and oil-repellent effect is not sufficient for 4 hours after application until the high-boiling solvent evaporates, and there is also the drawback that the odor characteristic of ethylene glycol derivatives lingers.

(Problems to be Solved by the Invention) An object of the present invention is to provide a water and oil repellent that is excellent in both water and oil repellency and anti-whitening effect.

Another object of the present invention is to provide a water and oil repellent that has excellent quick-drying properties and does not degrade the working environment at least in terms of odor.

(Means for Solving the Problems) The present invention uses 70 to 90% by weight of an acrylic ester or methacrylic ester having a perfluoroalkyl group having 4 to 20 carbon atoms, 10 to 30% by weight of n-butyl methacrylate,
% by weight, and 0.2 to 5% by weight of crosslinkable 'ttffi body.
It relates to a water and oil repellent containing a copolymer as a structural unit in a proportion of .

The acrylic ester or methacrylic ester [component (a)] having a perfluoroalkyl group having 4 to 20 carbon atoms used in the present invention can be exemplified by various compounds, but specifically, for example, (+) RfSO2NR20COCR co=CH2(
2) Rr(CII2)nOCOCRj=Ctl
2F<1 (3) RfCONR"0COCRco=CH2i1 (4) RrCH2CHCH20COCRco=CH2
0COR' (5) RfCH2C)IC)1 20COCR)
=CH2(6)Rr(CI(2)+lICOOCH=C
H2(7) RfCH=CH(CI-12)n('
)COCR co=CH2 [However, Rr in the formula has 4 to 4 carbon atoms.
20 perfluoroalkyl group, R' is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is a fullkylene group having 1 to 10 carbon atoms, R3 is hydrogen or a methyl group, and R4 is an alkyl group having 1 to 17 carbon atoms. group, and the mouth is 1-io and m is 0 to 10].
Mention may be made of (meth)acrylic acid esters having 20 perfluoroalkyl groups.

In the present invention, n-butyl methacrylate is used as component (b).

In the present invention, the crosslinking monomer [component (C)] is a monomer having a functional group capable of forming a covalent bond with the object to be treated through an addition or condensation reaction, such as an alphoxysilyl group, or a curing catalyst. l having a functional group, such as an epoxy group, that can three-dimensionally cure the copolymer by the action of
A wide range of jl i-bodies can be illustrated. for example,
Polyethylene glycol noacrylate, polyethylene glycol dimethacrylate, N-methylol acrylamide, N-methylol methacrylamide, glycidyl acrylate, glycitul methacrylate, trimethoxysilylethyl methacrylate, azilinonyl acrylate, anolinonyl methacrylate, diacetone acrylamide, Examples include diacetone methacrylamide, methylolated diacetone acrylamide, methylolated noacetone methacrylamide, (poly)ethylene methacrylate, and (poly)ethylene dimethacrylate. Among these, polyethylene glycol noacrylate and polyethylene glycol noacrylate, especially Cll□”
CR5C00(CI(2Clf, 0)rcOcR6=
A monomer represented by c11□ [wherein R5 and R' represent hydrogen or a methyl group, and r represents a number from 1 to 50, preferably from 14 to 23] is preferably used.

In the present invention, 70 to 90% (lf
i%, the same applies hereinafter), 10 to 30% of component (b) and (c
) A copolymer containing 0.2 to 5% of component C as a structural unit is used as a water and oil repellent. The above copolymer is produced by polymerizing these monomers according to a known method. For example, bulk polymerization, solution polymerization,
Any of various polymerization methods such as suspension polymerization, emulsion polymerization, radiation polymerization, and photopolymerization can be employed. For example, a method may be adopted in which a mixture of compounds to be copolymerized is dissolved in the presence of a solvent and the mixture is copolymerized with stirring. As the polymerization initiator, various polymerization initiators such as organic peroxides, 7zo compounds, persulfates, and electrolytic radiation such as γ-rays can be employed. Furthermore, in the case of emulsion polymerization, almost all of the various anionic, cationic, or nonionic emulsifiers can be used as surfactants. In the present invention, in addition to the above, ethylene, vinyl acetate, vinyl fluoride, vinyl chloride, acrylic amide, methacrylic amide, styrene, α-methylstyrene, p-methylstyrene, alkyl esters of acrylic acid or methacrylic acid (methacrylic acid), (excluding n-butyl acids), bennolacrylate or methacrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone,
It is possible to copolymerize one or more of various polymerizable compounds such as cyclohexyl acrylate or methacrylate, maleic anhydride, butanene, isoprene, and chloroprene as constituent units of the copolymer.

By selecting and copolymerizing these appropriate polymerizable compounds, properties such as dry soil resistance, abrasion resistance, selective solubility, flexibility, and texture can be improved in addition to water and oil repellency and durability. be able to.

The above copolymer used in the present invention has a melting point of 0 to 70.
゛C is preferred, and 30 to 60C is particularly preferred.

Water and oil repellency is poor when α is 0'C and 70℃.
If it exceeds this amount, bleaching phenomenon is likely to occur.

The water- and oil-repellent agent made of the above-mentioned copolymer of the present invention is prepared in the form of a stock solution for aerosol according to a conventional method. For example, as a method for preparing an aerosol stock solution, 1
A solvent solution containing 0 to 40 wt% of the copolymer can be directly prepared. Further, for copolymers obtained by various polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization, only the polymer can be separated and dissolved in a solvent to prepare a solvent solution.

The polymerization solvent and solvent used therein are preferably fluorinated solvents such as trichlorotrifluoroethane and nofluoroethane, or acetone, methylchloroform,
One of the leading suitable solvents such as trichlorethylene and tetrachlorethylene is a mixture of two or more thereof. In addition, the aerosol type uses a solvent solution such as a polymer with a polymer concentration of 0.2.
~5 wt %, and then a propellant such as dichlorofluoromethane, monofluorotrichloromethane, dichlorotetrafluoroethane, etc. is added thereto, and the mixture is irradiated with a suitable particle. Generally, 40 to 80 parts of solvent melting and 60 to 20 parts of propellant are used. Aerosol water and oil repellents whose solvent solution and propellant are made of only fluorine-based solvents are odorless, nonflammable, and have low toxicity. Furthermore, the water and oil repellent of the present invention may be prepared by combining Ike's Polymerized Honburengu with 711,
Of course, it is also possible to add appropriate additives such as other water repellents, oil repellents, insect repellents, NA agents, anti-electrification agents, dye stabilizers, anti-wrinkle agents, perfumes, etc. for use in combination.

There are various examples of articles that can be treated with the water and oil repellent of the present invention without particular limitation. For example, textile fabrics,
Mention may be made of glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces and plasters.

(Example) Next, reference examples, examples, and comparative examples of the present invention will be described in more detail, but these are not intended to limit the present invention in any way. The water repellency and oil repellency shown below were measured by the following methods. That is, the water repellency is JIS L- shown in Table 1.
Water repellency No. 1005 was determined by the spray method, and oil repellency was determined by placing several drops (diameter approximately 411 III) of the test solution shown in Table 2 on two locations on the sample cloth and determining the state of penetration after 30 seconds ( ^^TCC-T old 18-1966
).

Table 1 ttTable S2 Note that the water repellency No. marked with a cross indicates that the respective performance is slightly better. The degree of whitening was determined visually by spraying on a black nylon cloth. tlI constant is -
The standards of R. were followed. The results are shown in Table 3.

○ No whitening △ Slight whitening × Significant whitening Reference Example 1 In this example, a typical method of solution polymerization for producing the copolymer of the present invention is described. 11-Butyl acrylate-crosslinkable precipitate J (described on the body side).

Glass autoclave equipped with a stirrer (inner volume 10
00IIIl), CIl□=ClIC0OC112
C112CIIF 2+1+.

(n=6-12, average 9) 84g, methacrylic acid summer]
-Butyl 15bi, C11,, = C(C113'1C0
0(C112CIl, O'1.C0C(C11,)=C
11□ 1g, tetrachlorodifluoroethane 587g
After adding 65 g of acetone and purging with nitrogen for about 20 minutes while stirring, when the temperature became constant at 65° C., 2.3 g of butyl peroxybeverley was added and copolymerized for 8 hours. 〃The conversion rate of the copolymerization reaction determined by chromatography was 98.5% for F monomer and 10% for CH monomer.
The resulting solution contained 98% copolymer solids. Elemental analysis values for the copolymer were: F51.0%, (1(i, 4%).

H2.8%, and the measured value of the reaction raw material is F1a.4
%, C10.8%, 112.7%. Note that the melting point 7α of this copolymer was 46°C.

Examples 1 to 6 and Comparative Examples 1 to 11 A produced polymer solution containing a copolymer having the composition shown in Table 3 below was heated to a polymer concentration of 0.51. , diluted to ff11%, and this solution! :H5g+ 135g of dichloronofluoromethane was poured into an aerosol can.

Various aerosols are coated with polyester cotton cloth ('/C)
The solution was applied to a polyamide taffeta cloth (N) and left for 20 minutes in a room Tj, and then the whitening phenomenon and water oil repellency were measured.

In Table 3, FA is CI+2= C11C00CII2CI
l□CnF2Oya, (n=6-12, average 9), FMA
is C11゜=C(CI+, )C00C112C112
N(C211,)SQ□(CF, ), CF,, nBu
MA is methacrylic acid + 1-butyl, n 13 u A
is n-butyl acrylate, if3uMA is isobutyl methacrylate, tf3uMA is methacrylic 1li2 tert-butyl, M M A is methyl methacrylate, E M
A is ethyl methacrylate, L, M A is lauryl methacrylate, S t M A is stearyl methacrylate, VdC12 is vinylidene chloride, NK2:I is dimethacrylate f-lyethylene glycol ($1000)
), ABO3 is polyethylene glycol diacrylate (
#600), D tl A 3 C1l: =Example 7
-10 and Comparative Examples 12-15 Produced polymer containing a copolymer having the composition shown in Table 4 below; The polymer concentration was diluted with chloroethane (chlorocene) to a polymer concentration of 0. After drying at room temperature,
The whitening phenomenon and water and oil repellency of the resulting cloth were measured. The measurement results are shown in Table 4 below.

Claims (4)

[Claims] (1) Acrylic ester or methacrylic ester having a perfluoroalkyl group having 4 to 20 carbon atoms
A water and oil repellent containing a copolymer containing 0 to 90% by weight, n-butyl methacrylate 10 to 30% by weight, and a crosslinking monomer as a structural unit in a proportion of 0.2 to 5% by weight. (2) The water and oil repellent according to claim 1, wherein the copolymer has a melting point of 0 to 70°C. (3) The water and oil repellent according to claim 1, wherein the crosslinkable monomer is polyethylene glycol di(meth)acrylate. (4) The water and oil repellent according to claim 1, which is a water and oil repellent for fluorine-based solution-type aerosols.