Fluor copolymers, their application to the hydrophobic and oleophobic treatment of different substrates, and substrates thus treated.

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

The present invention uses novel fluoropolymers to coat and impregnate various substrates such as textiles, leather, wood, non-woven materials, metals, concrete and especially paper and similar products. , A method of making a substrate oil repellent and water repellent.

【0002】

Many fluorine derivatives have already been proposed to obtain these properties. However, although these derivatives have good properties in textiles and leather, in order to obtain these same properties in paper and similar materials, there is a great deal of activity to obtain acceptable practical performance. It is necessary to use a substance (ie, the proportion of fluorine bound to carbon).

【0003】

French patents 1,172,664 and 2,022,351, as well as US patent 3,907,576, propose chromium complexes as products that are particularly compatible with paper. Although these complexes impart effective oil repellency to paper and similar products, they are green and have the drawback of coloring the substrate to which they are applied, thus limiting their use in polyfluoroalkyl. , Or cycloalkyl phosphate (French patents 1,305,612, 1,317,427, 1,388,621, 2,055,551, 2,057,793 and 2,374,327, US patents 3,083,224 and 3,817,958, and German patents 2,405,042. ) And hydroxypropyl polyfluoroalkyl phosphate (US Pat. No. 3,919,361) No.) is also proposed to be used in papermaking. While these products impart good oil repellency to the paper, on the other hand, they have the significant drawback of not imparting any waterproofness. For this reason, paper treated with these products has no protective effect on water-based products. Moreover, these products do not have sizing power and greatly reduce the efficiency of the sizing agent, thus hindering its adaptability to writing and printing.

【0004】

Moreover, salt formation of perfluoroaliphatic acrylic acid or methacrylic acid ester and dialkylaminoalkylacrylic acid or methacrylic acid ester (US Pat. No. 4,147,851), and treatment of paper and similar products with N-oxidized copolymers. Has been proposed. Nevertheless, in order to impart good oil repellency to the paper to which they are applied and similar products, these copolymers must be used with high amounts of active material. Moreover, they only impart extremely weak water repellency.

【0005】

Now, in our laboratory, when applied to paper and similar products, simply a small amount of adhering fluorine imparts both excellent sizing strength and extremely good water and oil repellency, thereby producing these products. Paper treated with and similar products show true "barrier effect to water" and "barrier effect to organic soluents", i.e. they are aqueous or oily progenitor liquids, fats. And found to prevent the penetration of many organic solvents. When applied to a wide variety of other substrates, such as those mentioned above, these novel products impart extremely good water and oil repellency to the substrates.

【0006】

The product of the present invention is (a) a general formula of 35 to 98% by weight, preferably 69 to 93% by weight.<img file="JPH0774331B2_D0001.tif" />(In the formula, R_fRepresents a linear or branched perfluoro group having 2 to 20, preferably 4 to 16 carbon atoms, Q represents an oxygen or sulfur atom, and B is bonded to Q by a carbon atom. Represents a divalent chain that can have one or more oxygen, sulfur and / or nitrogen atoms, one of the symbols R represents a hydrogen atom and the other represents a hydrogen atom or one to four. One or more polyfluorinated monomers having (representing an alkyl group having up to carbon atoms), (b) 1-15% by weight, preferably 5-11% by weight, and especially 7-10% by weight. General formula<img file="JPH0774331B2_D0002.tif" />(In the formula, R₁And R₂Is a methyl group or R₁Is a tert-butyl group and R₂Is hydrogen and R'is a hydrogen or methyl group), one or more monomers, (c) 1-50% by weight, preferably 2-20% by weight. [0007]

[Chemical 2]

<img file="JPH0774331B2_D0003.tif" />【0008】

N-vinylpyrrolidone having, and (d) optionally up to 10% by weight, preferably up to 5% by weight, water-mixed with a monomer other than the monomer of formula (I), (II) or (III). The obtained random copolymer obtained by copolymerizing together in a sex solvent or a water-miscible solvent mixture is a fluorine-containing random copolymer chlorided with acetic acid, formic acid or propionic acid.

【0009】

The polyfluorinated monomer of formula (I) is preferably of formula (I). [0010]

[Chemical 3]

<img file="JPH0774331B2_D0004.tif" />【0011】

(In the formula, R_fAnd R have the same meaning as above, p represents an integer from 1 to 20, preferably equal to 2 or 4, q represents an integer from 1 to 4, preferably equal to 1 or 2, and R.₆Has a hydrogen atom, or an alkyl group with 1 to 10 carbon atoms (preferably methyl), a cycloalkyl group with 5 to 12 carbon atoms, and 2 to 4 carbon atoms Represents a hydroxyalkyl group, or an aryl group that may be substituted with an alkyl group having 1 to 6 carbon atoms, where X, X', Y and Y'are the same or different, respectively. It corresponds to a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). These monomers are used in known methods, such as the formula described in French Patent No. 2,034,142.<img file="JPH0774331B2_D0005.tif" />Applicable alcohol, formula<img file="JPH0774331B2_D0006.tif" />Alkene monocarboxylic acids such as acrylic acid, monomethacrylic acid and crotonic acid may be esterified in the presence of an acid catalyst such as sulfuric acid or p-toluenesulfonic acid. Instead of the alkene monocarboxylic acid of formula (VI), its esters, anhydrides or halides may also be used. Different R for practical and economic reasons_fIt is particularly advantageous to use a mixture of monomers of formula (IV) with groups.

【0012】

Other examples of the polyfluorinated monomer of formula (I) may be the acid of formula (VI) and the formula. R_f-(CH₂)_p-OH (VII) R_f-(CH₂)_p-SH (VIII) R_f-(CH₂)_p-O- (CH₂)_r-OH (IX) R_f-(CH₂)_p-S- (CH₂)_r-OH (X) R_f-(CH₂)_p-(OCH₂CH₂)_r-OH (XI) R_f-(CH₂)_p-SO₂-(CH₂)_r-OH (XII) R_f-CH = CH- (CH₂)_p-OH (XIII)<img file="JPH0774331B2_D0007.tif" /> R_f-COO- (CH₂)_p-OH (XV)<img file="JPH0774331B2_D0008.tif" />(In the formula, R_fAnd p have the same meaning as above, R₇Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and r is an integer from 1 to 20, preferably 1 to 4. ) Is an ester with an alcohol and a thiol.

【0013】

Examples of monomers of formula (II) that may be given in more detail are the following amino alcohols, 2-dimethylamino-ethanol, 2-diethylamino-ethanol, 2-dipropylamino-ethanol, 2-diisobutylamino-ethanol. , Nt-butyl-N-methylamino-ethanol, 2-morpholino-ethanol, N-methyl-N-dodecylamino-ethanol, N-ethyl-N-octadecylamino-ethanol, N-ethyl-N- (2-ethyl) -Hexyl) -2-amino-ethanol, 2-piperidino-ethanol, 2- (1-pyrrolidinyl) -ethanol, 3-diethylamino-1-propanol, 2-diethylamino-1-propanol, 1-dimethylamino-2-propanol , 4-Diethylamino-1-butanol, 4-diisobutylamino-1-butanol, 1-dimethylamino-2-butanol, 4-diethylamino-2-butanol, 2-t-butylamino-ethanol acrylate and methacrylate. These esters may be prepared, for example, by the method described in US Pat. No. 2,138,763.

【0014】

Examples of monomers of formula (III) that may be given in more detail are N-vinyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, There are N-vinyl-5-methyl-2-pyrrolidone and N-vinyl-3,3-dimethyl-2-pyrrolidone, with N-vinyl-2-pyrrolidone being preferred.

【0015】

Other monomers (d) that may be used within the scope of the present invention;<BAI>-</BAI>Lower olefin hydrocarbons that are or are not halogenated, such as ethylene, propylene, isobutene, 3-chloro-1-isobutene, butadiene, isoprene, chloro- and dichloro-butadiene, fluoro- and difluoro-butadiene, 2,5 -Dimethyl-1,5-hexadiene and diisobutylene,<BAI>-</BAI>Vinyl halide, allyl halide or vinylidene halide, such as vinyl chloride or vinylidene chloride, vinyl fluoride or vinylidene fluoride, allyl bromide and metallicyl chloride,<BAI>-</BAI>Styrene and its derivatives such as vinyltoluene, α-methyl-styrene, α-cyanomethyl-styrene, divinylbenzene and N-vinyl-carbazole,<BAI>-</BAI>Vinyl esters, such as vinyl acetate, vinyl propionate, vinyl esters of acids known on the market under the trade name Versatic acid, vinyl isobutyrate, vinyl sensioate, vinyl succinate, vinyl isodecano Esters, vinyl stearate and divinyl carbonate,<BAI>-</BAI>Allyl esters such as allyl acetate and allyl heptanoate,<BAI>-</BAI>Halogenated or unhalogenated alkyl vinyl, or alkyl-allyl ethers such as cetyl vinyl ethers, dodecyl vinyl ethers, isobutyl vinyl ethers, ethyl vinyl ethers, 2-chlorovinyl ethers, tetra-allyl oxyethanes,<BAI>-</BAI>Vinyl-alkyl-ketone, for example vinyl methyl-ketone,<BAI>-</BAI>Unsaturated acids such as acrylic acid, methacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and senecioic acid, their anhydrides and their esters, such as vinyl, Allyl, methyl, butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, cyclohexyl, lauryl, stearyl or cellosolve acrylate and methacrylate, dimethyl maleate, ethyl crotonate, acid methyl maleate, acid butyl itaconic acid, glycol or polyalkylene glycol Diacrylates and dimethacrylates, such as ethylene glycol dimethacrylate, or triethylene glycol dimethacrylate, dichloro-phosphate alkyl acrylates and methacrylates, such as dichloro-phosphate ethyl methacrylate, and bis (methacrylicloyloxyethyl) -acid phosphate,<BAI>-</BAI>Acrylonitrile, methacrylonitrile, 2-chloro-acrylonitrile, 2-cyano-ethylacrylate, methyleneglutaronitrile, vinylidene cyanide, alkylcyanoacrylates such as isopropylcyanoacrylate, trisacryloylhexahydro-S-triazine, vinyltrichlorosilane, There are vinyltrimethoxysilane and vinyltriethoxysilane.

【0016】

A monomer is a compound having at least one ethylene chain and at least one reactive group, i.e., a group having a group capable of reacting with another monomer, another compound, or the substrate itself to form a network. It may be used as (d). These reactive groups are well known and are polar or functional groups such as OH, NH.₂, NH-alkyl, COOMe (Me = alkaline or alkaline earth metal), SO₃H,<img file="JPH0774331B2_D0009.tif" />-SO₂-CH = CH₂, -NH-CO-CH = CH₂It may be a group. This type of monomer may be mentioned as hydroxyalkyl acrylates and methacrylates, such as ethylene glycol monoacrylates, propylene glycol monomethacrylates, polyalkylene glycol acrylates and methacrylates, allyl alcohols, allyl glycolates, isobutene diols, allyl oxyethanol, o-allylphenol, divinylcarbinol, glycerol α-allyl ether, acrylic amide, methacrylic amide, maleamide and maleimide, N- (cyanoethyl) -acrylic amide, N-isopropylacrylic amide, diacetone acrylic amide, N- (hydroxymethyl) ) Acrylate and methacrylic acid, N- (alkoxymethyl) acrylic acid and methacrylic acid, glioxal-bis-acrylic amide, sodium acrylate or sodium methacrylate, vinyl sulfonic acid and styrene-p-sulfonic acid and their alkali salts, There are 3-aminocrotonitrile, monoallyl-amino, vinylpyridine, glycidyl acrylate or methacrylate, allyl glycidyl ether and achlorine.

【0017】

The products of the present invention are solvents or solvents solvents such as acetone, methyl ethyl ketone, γ-butyrolactone, methylcyclohexanone, N-methyl 2-pyrrolidone, methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, diacetone alcohol, phenylmethyl. Carbinol, isophorone, tetrahydrofuran, dioxane, ethyl acetate, glycol acetate, ethylene or polyethylene glycol Monomethyl or monoalkyl ether, formamide, dimethylformamide, acetonitrile, toluene, trifluorotoluene, trichlorotrifluoroethane solution. By polymerizing, they are produced by known methods. It is preferable to use a solvent that mixes with water, such as acetone and isopropyl alcohol.

【0018】

The procedure is suitable polymerization catalysts such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, succinyl peroxide, 2,2'-azo-bis-isobutyronitrile, 2,2'-azo-bis- (2, 4-Dimethyl-4-methoxyvaleronitrile), 4,4'-azo-bis- (4-cyano-pentanoic) acid, azodicarboxylic amide, t-butyl perpivalate. The amount of catalyst used may vary from 0.01 to 5%, preferably 0.1 to 1.5%, based on the total weight of the monomers used.

【0019】

UV radiation sources can also be used to react in the presence of photoinitiators such as benzophenone, 2-methylanthraquinone, or 2-chloro-thioxaanthrone.

【0020】

The reaction temperature may vary over a wide range, i.e. from room temperature to the boiling point of the reaction mixture. The operation is preferably performed at 50 ° to 90 ° C.

【0021】

If it is desired to control the molecular weight of the copolymer, chain transfer agents such as alkyl mercaptans such as tertiododecylmercaptan, n-dodecyl mercaptan, n-octyl mercaptan, carbon tetrachloride, triphenylmethane. Can also be used. The amount used, which is a factor of the value obtained with respect to the molecular weight, may be changed from 0.01% to 3%, preferably 0.05% to 0.5% based on the total weight of the monomers.

【0022】

The formation of possible salts of copolymers is strong or moderately strong mineral acids, or organic acids, i.e. dissociation constant or first dissociation constant of 10.^-5It can be made with a larger acid. For example, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, formic acid and propionic acid may be mentioned. Acetic acid is preferably used.

【0023】

Instead of converting the copolymer to a salt, it is quaternized with a suitable quaternizing agent such as methyl iodide, ethyl iodide, dimethyl sulphate, diethyl sulphate, benzyl chloride, trimethyl phosphate, methyl p-toluenesulfonate. You may.

【0024】

If desired, the resulting copolymer solution may be diluted with a polymerization solvent, or another solvent, or a mixture of solvent and water. If desired, the copolymer may be separated by removing the solvent or the plurality of solvents.

【0025】

Substrate that can be made oil-proof and waterproof by the products of the present invention are mainly paper, paperboard and comparable materials. Woven or non-woven products based on a wide variety of other materials such as cellulose or regenerated cellulose, natural, artificial or synthetic fibers such as cotton, cellulose acetate, wool, silk, polyamide, polyester, polyolefin, polyurethane or polyacrylonitrile fibers. , Leather, plastic materials, glass, wood, metal, porcelain, masonry, and painted surfaces.

【0026】

In the case of paper, paperboard, the solution of the copolymer of the present invention is applied in an aqueous medium, but if desired, in a solvent medium or a mixture of water and solvent, known techniques such as coating. Or mainly applied by covering), impregnation, dipping, spraying, brushing, solvent or lamination.

【0027】

An aqueous solution of the product of the invention on paper may be applied superficially or entirely to the already finished support, i.e. to paper paste or pulp.

【0028】

The thus treated support simply dries at room temperature or at a higher temperature and exhibits good oil resistance and water resistance after heat treatment, which can be raised to 250 ° C depending on the nature of the support if desired.

【0029】

Certain auxiliaries, polymers, which can help network with the support in order to adhere the copolymers of the invention well to substrates to which the copolymers are applied and which further impart special effects. It is sometimes advantageous to add thermocondensable products and catalysts. Such are urea or melamine-formalin condensate or precondensate, methyloldihydroxyethyleneurea and derivatives thereof, urone, methylol-ethyleneurea, methylolpropylene urea, methylol-triazone, dicyandiamide-formalin condensate, methylol-carbamate, Methylol-acrylamide, or methacrylamide, their polymers, or copolymers, divinylsulfone, polyamide, epoxy derivatives such as diglycidyl glycerin, epoxypropyl-trialkyl (aryl) ammonium halides, for example (2,3-) Epoxy-propyl) -trimethylammonium chloride, N-methyl-N- (2,3-epoxy-propyl) morpholinium chloride, certain halogen derivatives such as chloro-epoxy-propane and dichloro-propanol, or polar compounds such as The sodium salt of trisulfate-oxyethyl sulfonium-betaine and the pyridinium salt of chloromethyl ether of ethylene glycol may be mentioned.

【0030】

In order to evaluate the performance of the substrate treated according to the present invention, the present inventor used the following test method.

【0031】

Oil resistance test or Kit value Tappy Vol. 50, No. 10, pp. 152A and 153A, Standard RC338 and UM511 describe this test, which measures the oil resistance of a substrate with a mixture of castor oil, toluene and heptane. These are contained in varying amounts of these three products.

【0032】

[table 1]

<img file="JPH0774331B2_D0010.tif" />【0033】

The test consists of gently adhering droplets of these mixtures to the treated paper. Leave the droplets on the paper for 15 seconds, observe the paper or paperboard, and record the wetting or penetration indicated by the surface turning brown. The number corresponding to the mixture containing the highest percentage of heptane that does not penetrate or wet the paper is considered to be the paper kit value and the oil resistance value of the treated paper. The higher the kit value, the better the oil-proof paper.

【0034】

Turpentine test This test is described in Tappy, Standard T454, ts66 (1966).

【0035】

5 g of acid-cleaned Fontaine bleau sand was attached to the paper to be tested placed on white fine paperboard, and then 1.1 ml of anhydrous television oil colored with Rouge Organol BS 0.5 g / l. Pour into the sand. When the oil injection is complete, start the chronometer and move the paper on the fine paperboard every 30 seconds. Record the time elapsed at the moment the fine paperboard is contaminated. After 30 minutes, the test is no longer meaningful and the substrate tested can be evaluated as exhibiting outstanding performance.

【0036】

The test is performed on 7 samples of the same paper. Record from the smallest value to the largest value among the obtained values, and use the fourth value as the average value.

【0037】

Method for measuring solvent-proof effect Immerse 1 cm in length of a rectangular test piece (10 cm x 1 cm) of the substrate to be tested in anhydrous turpentine oil colored with Rouge Organol BS 0.5 g / l. This immersion is performed in a closed cylindrical 500 ml bottle for 24 hours. The surface machine of the contaminated part formed by the colored liquid rising on the unimmersed part of the tested substrate mm²Measure with.

【0038】

How to measure the waterproof effect Immerse a 3 cm long rectangular test piece (10 cm x 1 cm) of the substrate to be tested in water colored with Rhodamine B 0.5 g / l. This immersion is performed in a closed cylindrical 500 ml bottle for 24 hours. Surface area mm of contaminated part formed by the colored liquid rising on the part of the test substrate that has not been immersed²To measure.

【0039】

COBB test The COBB and LOWE exams (Tappy Standard T441) edited by the Commission are papers that support a height of 1 cm, as opposed to the central laboratory exams of the Swedish Paper Industry [Project PCA 13-59]. It consists of measuring the weight (g) of water absorbed in 1 minute by 1 square m of.

【0040】

Oil resistance test For a support, oil resistance was measured by the method described in the "AATCC" Technical Manual, Test Methods 118-1972, which assesses the non-wetting properties of a substrate with a series of oily liquids with lower surface tension. [Textile Research Journal, p. 451 (March 1969)].

【0041】

Waterproof test For a support, the waterproofness was measured by the method described in the "AACTCC Technical Manual", Test Method 22-1971.

【0042】

The following examples illustrate the invention and are not intended to be limiting, with parts and% being parts and% by weight unless otherwise indicated. In the examples shown,% of the discharging rate or expression rate indicates the weight of the bath held by 100 parts of the substrate (x parts).

【0043】

[Example]

Example 1 Acetone 20.4 parts, isopropyl alcohol 45 parts, dimethylaminoethyl methacrylate 8 parts, N-vinylpyrrolidone 16 parts, 2,2'-azo-bis-isobutyronitrile 0.8 parts and formula [0044]

[Chemical 4]

<img file="JPH0774331B2_D0011.tif" />【0045】

(In the formula, n is equal to 3, 5, 7, 9, 11, 13 and 15 and the average weight ratio of each is 1: 50: 31: 10: 3: 1: 1). Place 81.6 parts of the body mixture into a reactor with a capacity of 1000 parts, equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube and a heating device. Heat at 75 ° C for 15 hours in a nitrogen stream, then add 160 parts water, 250 parts isopropyl alcohol and 8 parts acetic acid. The mixture is held at 75 ° C for 2 hours and then cooled to room temperature.

【0046】

Thus, a solution of the copolymer of the present invention (S)₁) 563 copies are obtained. This solution contains 18.8% non-volatile material and has a fluorine ratio of 6.6%.

【0047】

Example 2 2a / Acetone 19.2 parts, isopropyl alcohol 45 parts, dimethylaminoethyl methacrylate 8 parts, N-vinylpyrrolidone 21 parts, 2,2'-azo-bis-isobutyronitrile 0.8 parts and implementation in the same apparatus as in Example 1. Add 76.8 parts of the same polyfluoromonomer as in Example 1. The mixture is heated in a nitrogen stream at 75 ° C for 15 hours, then 160 parts of water, 250 parts of isopropyl alcohol and 8 parts of acetic acid are added, kept at 75 ° C for an additional 2 hours and then cooled to room temperature. Thus, the copolymer solution of the present invention (S)₂) 585 copies are obtained. This solution contains 18.2% non-volatile material and has a fluorine ratio of 6%.

【0048】

2b / This polymer and the polymer obtained in Example 1 are comparatively tested in equal amounts of fluorine with the next product.

【0049】

(A) A copolymer prepared according to Example 1 of US Pat. No. 4,147,851, which is based on 85% of the mixture of polyfluoromonomono shown in Example 1 and 15% of dimethylaminoethyl methacrylate. An N-oxidized copolymer obtained by salting the coalescence.

【0050】

(B) A copolymer prepared according to Example 2 of US Pat. No. 4,147,851, which is based on 70% of the mixture of polyfluoromonomono and 30% of dimethylaminoethyl methacrylate shown in Example 1. N-oxidized copolymer obtained by salt formation.

【0051】

(C) Equation described in Example 5 of US Pat. No. 1,317,427. [0052]

[Chemical 5]

<img file="JPH0774331B2_D0012.tif" />【0053】

Phosphate of polyfluorinated alcohol.

【0054】

Applying these products to non-sized paper, their properties are as follows:

【0055】

Fibrous composition: Bleached craft paste based on hard wood 60% Bleached craft paste based on soft wood 40% Purify to 35 ° SR with Hydrofiner, Auxiliary agent added: Tarku 15% Yield improver [Bayer's Ritaninol (Retaninol) E] 3% Paper weight: 70 ~ 71g / m² Paper humidity: 4-5% For this purpose, five size-press baths were prepared, each containing 0.7 g / l of fluorine and having the following composition (g / l):

【0056】

[Table 2]

<img file="JPH0774331B2_D0013.tif" />【0057】

Five sheets of non-sized paper are treated by size-press, each in these five baths with a discharging rat of 85%. After drying at 110 ° C for 90 seconds, it exhibits oil-proof, "waterproof" and "solvent-proof" effects, and a paper with slightly superior strength can be obtained. These properties are compared with those of untreated paper and reclassified in the following table.

【0058】

[Table 3]

<img file="JPH0774331B2_D0014.tif" />【0059】

Considering the results in this table, it is proved that the paper treated with the copolymer of the present invention not only has excellent oil resistance, but also exhibits excellent "waterproof" and "solventproof" effects.

【0060】

2c / size-Five baths for pressing are prepared, each containing 1 g / l of fluorine and having the following composition (g / l).

【0061】

[Table 4]

<img file="JPH0774331B2_D0015.tif" />【0062】

Weight 77g / m²Five sheets of non-sized AFNOR VII paper are processed with a size-press in each of these five baths at a squeeze rate of 95%. After drying at 110 ° C for 90 seconds, the treated paper and one sheet of untreated paper are COBB tested.

【0063】

The results are reclassified in the following table.

【0064】

[Table 5]

<img file="JPH0774331B2_D0016.tif" />【0065】

The results in the table show that the copolymer-treated papers of the present invention (baths No. 6 and 7) have an excellent degree of sizing.

【0066】

Example 3 25 parts of acetone, 45 parts of isopropyl alcohol, 12 parts of dimethylaminoethyl methacrylate, 3 parts of N-vinylpyrrolidone, 0.4 parts of 2,2'-azo-bis-isobutyronitrile and the same polyfluoromonomer mixture as in Example 1. Charge 100 copies into the same device as in Example 1. The preparation is heated in a nitrogen stream at 75 ° C for 17 hours, then 165 parts of water, 250 parts of isopropyl alcohol, and 8 parts of acetic acid are added, kept at 75 ° C for an additional 2 hours, and then cooled to room temperature. Solution of the copolymer of the present invention (S₃) 589 copies are obtained. This solution contains 19.1% non-volatile material and a fluorine content of 7.8%.

【0067】

On the same paper as in Example 2b, under the same conditions and in the same ratio (ie, solution S per liter of bath)₃When applied in 9g), this copolymer imparts the following properties to the paper:

【0068】

Oil resistance (kit value) .................. 9 Turpentine oil test .................................. 30 minutes or more Waterproof effect Wet surface area ................................. 40 mm²Solventproof effect Wet surface area ................................. 10 mm²Example 4 20.5 parts of acetone, 45 parts of isopropyl alcohol, 13 parts of dimethylaminoethyl methacrylate, 5 parts of N-vinylpyrrolidone, 0.8 parts of 4,4'-azo-bis- (4-cyano-pentanoic) acid and the same polyfluoro as in Example 1. 82 parts of the monomer mixture is charged in the same apparatus as in Example 1. The preparation is heated to 75 ° C for 4 hours in a nitrogen atmosphere, then 160 parts of water, 250 parts of isopropyl alcohol and 10 parts of acetic acid are added, kept at 75 ° C for another 2 hours and cooled to room temperature. Thus, the copolymer solution of the present invention (S)₄) 580 copies are obtained. This solution contains 17.2% of non-volatile material and 6.5% of fluorine.

【0069】

On the same paper as in Example 2b, the same conditions and ratio (ie, solution S per liter of bath)₄When applied at 10.8 g), this copolymer imparts the following properties to the paper:

【0070】

Oil resistance (kit value) .................. 9 Turpentine oil test .................................. 30 minutes or more Example 5 21.4 parts of acetone, 46 parts of isopropyl alcohol, 10 parts of dimethylaminoethyl methacrylate, 10 parts of N-vinylpyrrolidone, 0.8 parts of 2,2'-azo-bis-isobutyronitrile and the same polyfluorinated monomer as in Example 1. Add 85.6 parts of the mixture to the same apparatus as in Example 1. The preparation is heated at 70 ° C. for 22 hours in a nitrogen atmosphere, then 160 parts of water, 250 parts of isopropyl alcohol and 10 parts of acetic acid are added. Hold the charge at 70 ° C for an additional hour and then cool to room temperature.

【0071】

Solution of the copolymer of the present invention (S₅) 530 copies are obtained. This solution contains 19.1% non-volatile material and a fluorine content of 7.1%.

【0072】

Solution S₅, 4 g of dried "bleached bisulfite" paste and 156 g of water are mixed to prepare an aqueous paste containing 0.03 g of fluorine. The paste is then diluted with 4 liters of water in a pot of a "Rapid Kotten" machine. Stir this for 30 seconds and then filter under reduced pressure. The resulting paper assembly is vacuum dried at 90 ° C. on a rapid-cotten machine plate or planks for 10 minutes. A sheet of paper treated with the aggregate is finally obtained and has the performance shown in the following table compared to the properties of the untreated control sheet.

【0073】

[Table 6]

<img file="JPH0774331B2_D0017.tif" />【0074】

Example 6 Solution S of Example 1₁Prepare a fooling bath consisting of 40 parts, 40 parts of a 65% aqueous solution of a precondensate of trimethylolether of hexamethylolmelamine, 4 parts of lactic acid and 916 parts of water. Three fabrics of different composition, acrylic fiber [Dralon] cloth, polyester fiber [TERGAL] cloth, and polyester-cotton 66/33 blended cloth, 112%, 87% and 70 in this bath. Fullered to each display value of%. The cloth is treated with a thermocondenser BENZ at 165 ° C for 3 minutes.

【0075】

The properties of the thus treated cloth (T) are shown in the following table in comparison with the untreated control cloth (NT).

【0076】

[Table 7]

<img file="JPH0774331B2_D0018.tif" />【0077】

Considering the results in the above table, it is shown that the copolymer-treated cloth of the present invention is non-staining, that is, it can prevent lean and fatty stains.

【0078】

Example 7 Solution S of Example 2a₂100g / m²Brush on two different pieces of leather and leave them to dry at room temperature for 24 hours. A leather is obtained that exhibits remarkable oil resistance and waterproofness as shown by the properties shown in the following table.

【0079】

[Table 8]

<img file="JPH0774331B2_D0019.tif" />【0080】

Example 8 21.4 parts of acetone, 90 parts of isopropyl alcohol, 8 parts of dimethylaminoethyl methacrylate, 12 parts of N-vinylpyrrolidone, 0.8 parts of 4,4'-azo-bis- (4-cyano-pentanoic) acid and the following formula [0081]

[Chemical 6]

<img file="JPH0774331B2_D0020.tif" />【0082】

85.6 parts of the polyfluoromonomer having the above is charged in the same apparatus as in Example 1.

【0083】

The preparation is heated to 70 ° C for 10 hours in a nitrogen stream, then 160 parts of water, 205 parts of isopropyl alcohol and 5 parts of acetic acid are added. Hold the charge at 70 ° C for an additional 2 hours and allow to cool to room temperature. Solution of the copolymer of the present invention (S₆) 580 copies are obtained. This solution contains 17.6% non-volatile material and a fluorine content of 6.5%.

【0084】

Same conditions and ratio (ie, solution S per liter of bath) on the same paper as in Example 2b₆When applied at 10.8 g), this copolymer imparts the following properties to the paper:

【0085】

Oil resistance (kit value) .................. 9 Turpentine oil test .................................. 30 minutes or more Example 9 100 g / m of the solution described in Example 5 on a plank of oak tree²Is coated with a brush and dried at room temperature for 24 hours.

【0086】

The waterproof effect of the support thus treated is measured by adhering a few drops of each of the seven following solutions to the surface of the wood.

【0087】

[Table 9]

<img file="JPH0774331B2_D0021.tif" />【0088】

The rating corresponds to the number of the solution with the highest amount of isopropyl alcohol that does not moisten the support. This wetting is indicated by the complete penetration of the liquid or by the browning of the surface in contact with the liquid.

【0089】

Oil protection is measured by using a solution of standard AATCC 118-1972. A few drops of each solution are attached to the surface of the wood. The rating corresponds to the number of the solution with the lowest surface tension that does not penetrate into the support or does not show a brown surface in contact with the liquid.

【0090】

Compared with untreated wood, its properties are as follows.

【0091】

[Table 10]

<img file="JPH0774331B2_D0022.tif" />【0092】

Example 10 14.2 parts of acetone, 45 parts of isopropyl alcohol, 3 parts of dimethylaminoethyl methacrylate, 40 parts of N-vinylpyrrolidone, 0.8 parts of 4,4'-azo-bis- (4-cyano-pentanoic) acid and the same polyfluoride as in Example 1. Charge 56.8 parts of the mixture of chemicalized monomers into the same apparatus as in Example 1. The preparation is heated at 80 ° C. for 4 hours in a nitrogen atmosphere, then 160 parts of water, 160 parts of isopropyl alcohol and 2 parts of acetic acid are added. Hold the charge at 80 ° C for an additional hour and allow to cool to room temperature. Solution of the copolymer of the present invention (S₇) 460 copies are obtained. This solution contains 21.2% non-volatile material and 5.5% fluorine content.

【0093】

0.8 g of fluorine per liter of bath (solution S per liter of bath₇When applied to the same paper as in Example 2b under the same conditions, except for a ratio of 14.5 g), this copolymer imparts the following properties to the paper:

【0094】

Oil resistance (kit value) .................. 9 Turpentine oil test .................................. 30 minutes or more Example 11 45 parts of isopropyl alcohol, 4 parts of dimethylaminoethyl methacrylate, 6 parts of N-vinyl-pyrrolidone, 0.4 parts of 4,4'-azo-bis- (4-cyano-pentanoic) acid and formula C₈F₁₇-C₂H₄-O-CO-CH = CH₂40 parts of the polyfluorinated monomer having the above is charged in the same apparatus as in Example 1.

【0095】

The charge is heated to 70 ° C for 24 hours in a nitrogen atmosphere, then 80 parts of water, 100 parts of isopropyl alcohol and 2 parts of acetic acid are added, the preparation is kept at 80 ° C for an additional hour and then cooled to room temperature. To do. Thus, the copolymer solution of the present invention (S)₈) 275 copies are obtained. This solution contains 17.8% non-volatile material and a fluorine content of 8.8%.

【0096】

Solution (S₈) Weight 200g / m in a fullering bath consisting of 10 parts and 990 parts of water²Foolad polyester non-woven material (dry) at a squeeze rate of 250% and then dry at 165 ° C for 3 minutes with a BENZ thermocondenser.

【0097】

The properties of the unwoven material thus treated are shown in the following table in comparison with the unwoven control material.

【0098】

[Table 11]

<img file="JPH0774331B2_D0023.tif" />【0099】

Example 12 Acetone 21.3 parts, isopropyl alcohol 45 parts, dimethylaminoethyl methacrylate 14 parts, N-vinylpyrrolidone 1 part, 4,4'-azo-bis- (4-cyano-pentanoic) acid 0.8 parts and formula<img file="JPH0774331B2_D0024.tif" />85 parts of the polyfluorinated monomer having the above is charged in the same apparatus as in Example 1.

【0100】

The preparation is heated in a nitrogen atmosphere at 70 ° C. for 6 hours, then 160 parts of water, 160 parts of isopropyl alcohol and 8 parts of acetic acid are added. Hold the charge at 70 ° C for an additional hour and then cool to room temperature. Thus, the copolymer solution of the present invention (S)₉) 490 copies are obtained. This solution contains 20% non-volatile material and a fluorine content of 7.8%.

【0101】

S₉Weight 46g / m in a full-loading bath consisting of 10 parts and 990 parts of water²Cellulosic non-woven material (wet) is Fooladed at a squeeze rate of 150% and then dried in a BENZ thermocondenser at 165 ° C for 3 minutes.

【0102】

The properties of the non-woven material thus treated are shown in the following table in comparison with the non-woven untreated control material.

【0103】

[Table 12]

<img file="JPH0774331B2_D0025.tif" />【0104】

Example 13 20.4 parts of acetone, 45 parts of isopropyl alcohol, 6 parts of dimethylaminoethyl methacrylate, 16 parts of N-vinylpyrrolidone, 2 parts of ethylene glycol monomethacrylate, 0.8 parts of 4,4'-azo-bis- (4-cyano-pentanoic) acid and Add 81.6 parts of the same polyfluorinated monomer as in Example 1 to the same apparatus as in Example 1. The preparation is heated to 80 ° C. for 4 hours in a nitrogen atmosphere, then 160 parts of water, 250 parts of isopropyl alcohol and 6 parts of acetic acid are added. Hold the charge at 80 ° C for an additional 2 hours and then cool to room temperature. Solution of the copolymer of the present invention (S₁₀) 583 copies are obtained. This solution contains 18.1% non-volatile material and a fluorine content of 6.4%.

【0105】

On the same paper as in Example 2b, the same conditions and ratio (ie, solution S per liter of bath)₁₀When applied in 11g), this copolymer imparts the following properties to the paper:

【0106】

Oil resistance (kit value) .................. 9 Turpentine oil test .................................. 30 minutes or more Example 14 Same as Example 1 with 18.4 parts of acetone, 50 parts of isopropyl alcohol, 8 parts of t-butylaminoethyl methacrylate, 16 parts of N-vinylpyrrolidone, 0.8 parts of 4,4'-azo-bis- (4-cyano-pentanoic) acid. 73.6 parts of the mixture of polyfluorinated monomers is charged in the same apparatus as in Example 1. The preparation is heated at 80 ° C for 6 hours in a nitrogen atmosphere, then 160 parts of water, 250 parts of isopropyl alcohol and 4 parts of acetic acid are added, then held at 80 ° C for an additional hour and then cooled to room temperature. Thus, the copolymer solution of the present invention (S)₁₁) 560 copies are obtained. This solution contains 17.3% non-volatile material and a fluorine content of 6%.

【0107】

On the same paper as in Example 2b, the same conditions and ratio (ie, solution S per liter of bath)₁₁When applied at 11.6 g), this copolymer imparts the following properties to the paper:

【0108】

Oil resistance (kit value) .................. 9 Turpentine oil test .................................. 30 minutes or more Example 15 Acetone 18.7 parts, isopropyl alcohol 50 parts, dimethylaminoethyl methacrylate 12 parts, N-vinylpyrrolidone 10 parts, vinyl acetate 6 parts, 4,4'-azo-bis- (4-cyano-pentanoic) acid 0.8 parts and Examples 74.7 parts of the same mixture of polyfluorinated monomers as in 1 is charged in the same apparatus as in Example 1. The preparation is heated at 80 ° C for 6 hours in a nitrogen atmosphere, 160 parts of water, 250 parts of isopropyl alcohol and 12 parts of acetic acid are added, kept at 80 ° C for an additional hour and then cooled to room temperature. Solution of the copolymer of the present invention (S₁₂) 572 copies are obtained. This solution contains 17.6% non-volatile material and a fluorine content of 5.9%.

【0109】

On the same paper as in Example 2b, the same conditions and ratio (ie, solution S per liter of bath)₁₂When applied in 11.8 g), this copolymer imparts the following properties to the paper:

【0110】

Oil resistance (kit value) .................. 9 Turpentine oil test .................................. 30 minutes or more Example 16 Acetone 5 parts, isopropyl alcohol 40 parts, dimethylaminoethyl methacrylate 4 parts, N-vinylpyrrolidone 8 parts, ethyl acrylate 5 parts, 4,4'-azo-bis- (4-cyanopentanoic acid) 0.4 parts and formula<img file="JPH0774331B2_D0026.tif" />(In the formula, n is equal to 3, 5, 7, 9, 11, 13 and 15 and the average weight ratio of each is 1: 50: 31: 10: 3: 1: 1). 33 parts of the mixture is charged into the same reactor as in Example 1. Heat at 70 ° C for 5 hours in a nitrogen stream, then add 62.5 parts water, 62.5 parts isopropyl alcohol and 4 parts acetic acid. The mixture is held at 70 ° C for 2 hours and then cooled to room temperature. Thus, a solution of the copolymer of the present invention (S)₁₃) 220 copies are obtained. This solution contains 21.8% non-volatile material and a fluorine content of 9%.

【0111】

On the same paper as in Example 2b, the same conditions and ratio (ie, solution S per liter of bath)₁₃When applied in 15.5 g), this copolymer imparts the following properties to the paper:

【0112】

Oil resistance (kit value) ........................ 10 Turpentine oil test .................................. 30 minutes or more Example 17 Acetone 5 parts, isopropyl alcohol 40 parts, dimethylaminoethyl methacrylate 4 parts, N-vinylpyrrolidone 9 parts, ethyl acrylate 5 parts, 4,4'-azo-bis- (4-cyanopentanonic acid) 0.4 parts and formula<img file="JPH0774331B2_D0027.tif" />32 parts of the polyfluoromonomer having the above are charged into the same reactor as in Example 1. Heat at 70 ° C for 5 hours in a nitrogen stream, then add 62.5 parts water, 62.5 parts isopropyl alcohol and 4 parts acetic acid. The mixture is held at 70 ° C for 2 hours and then cooled to room temperature. Thus, a solution of the copolymer of the present invention (S)₁₄) 219 copies are obtained. This solution contains 22% non-volatile material and a fluorine content of 6.3%.

【0113】

On the same paper as in Example 2b, under the same conditions, a ratio of 1.4 g of fluorine per liter of bath (ie, solution S per liter of bath).₁₄When applied in 22g), this copolymer imparts the following properties to the paper:

【0114】

Oil resistance (kit value) ........................ 10 Turpentine oil test .................................. 30 minutes or more Example 18 Acetone 10 parts, isopropyl alcohol 40 parts, dimethylaminoethyl methacrylate 7 parts, N-vinylpyrrolidone 8 parts, 4,4'-azo-bis- (4-cyanopentanonic acid) 0.4 parts and formula<img file="JPH0774331B2_D0028.tif" />35 parts of the polyfluoromonomer having the above is charged into the same reactor as in Example 1. Heat at 70 ° C for 6 hours in a nitrogen stream, then add 62.5 parts water, 62.5 parts isopropyl alcohol and 5 parts acetic acid. The mixture is held at 70 ° C for 2 hours and then cooled to room temperature. Thus, a solution of the copolymer of the present invention (S)₁₅) 225 copies are obtained. This solution contains 21.4% non-volatile material and a fluorine content of 7.5%.

【0115】

To the same cellulosic non-woven material as in Example 12, under the same conditions, but at a ratio of 0.8 g of fluorine per liter of bath (ie, solution S per liter of bath).₁₅When applied in 10.7 g), this copolymer imparts the following properties to the non-woven material:

【0116】

Oil resistance (kit value) ........................ 8 Turpentine oil test .................................. 30 minutes or more