EP0368338B1 - Wasser und Öl abweisende Zusammensetzung - Google Patents

Wasser und Öl abweisende Zusammensetzung Download PDF

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Publication number
EP0368338B1
EP0368338B1 EP19890120887 EP89120887A EP0368338B1 EP 0368338 B1 EP0368338 B1 EP 0368338B1 EP 19890120887 EP19890120887 EP 19890120887 EP 89120887 A EP89120887 A EP 89120887A EP 0368338 B1 EP0368338 B1 EP 0368338B1
Authority
EP
European Patent Office
Prior art keywords
water
oil
glycerol
repellent
repellency
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19890120887
Other languages
English (en)
French (fr)
Other versions
EP0368338A3 (en
EP0368338A2 (de
Inventor
Yoshio Amimoto
Takashi Enomoto
Kazunori Hayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of EP0368338A2 publication Critical patent/EP0368338A2/de
Publication of EP0368338A3 publication Critical patent/EP0368338A3/en
Application granted granted Critical
Publication of EP0368338B1 publication Critical patent/EP0368338B1/de
Anticipated expiration legal-status Critical
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine

Definitions

  • the present invention relates to an economical water- and oil-repellent composition having good water- and oil-repellency.
  • a water- and oil- repellent having a fluoroalkyl group has better properties than other conventional water-and oil-repellent, and is widely used. However, it is relatively expensive. In order to decrease the cost, it is proposed to replace a part of the water- and oil repellent having the fluoroalkyl group with a cheap acrylic acid base polymer or polyhydric alcohol such as sorbitol and lactose while keeping the water- and oil-repellency (cf. Japanese Patent Publication Nos. 22487/1963, 8579/1966 and 4160/1978). Although reduction of the cost is achieved to some extent while keeping the water- and oil- repellency, the above proposal is not satisfactory.
  • FR-A-22 56 281 discloses an oil and water repellent composition containing a fluoroalkyl polymer and glycerol compounds as surfactants.
  • GB-A-1 222 614 discloses a combination of fluorocarbons with an organic glycol as surfactant.
  • An object of the present invention is to provide an economical water- and oil-repellent composition having sufficient water- and oil-repellency.
  • a water- and oil-repellent composition which comprises a water- and oil-repellent composition which comprises a water- and oil-repellent which is a homopolymer of an acrylate or methacrylate having a fluoroalkyl group having 4 to 21 carbon atoms or a copolymer thereof with a monomer having no fluoroalkyl group and a glycerol compound selected from glycerol, an ester derivative of glycerol prepared by esterifying a hydroxyl group at the alpha-position with a monoalkane acid having 1 to 6 carbon atoms, an ether derivative of glycerol prepared by substituting a hydrogen of a hydroxyl group at the alpha-position with an alkyl group having 1 to 6 carbon atoms and polyglycerol, said polyglycerol having a melting point of lower than 70°C.
  • the ester derivative of glycerol is an ester prepared by esterifying a hydroxyl group at the ⁇ -position with a monoalkane acid having 1 to 6 carbon atoms, for example, glycerol ⁇ -monoacetate, glycerol ⁇ -monoformate and glycerol ⁇ -mono-n-hexanoate.
  • the ether derivative of glycerol is an ether prepared by substituting a hydrogen of a hydroxyl group at the ⁇ -position with an alkyl group having 1 to 6 carbon atoms, for example, glycerol ⁇ -monomethyl ether, glycerol ⁇ -monoethyl ether and glycerol ⁇ -monoisopropyl ether.
  • a ratio of the glycerol compound to the water- and oil-repellent is not critical and varies in a wide range dependent on other conditions such as the kinds of the water- and oil-repellent and the glycerol compound.
  • the amount of the glycerol compound is too large, the water-and oil-repellent composition has deteriorated properties.
  • the amount of the glycerol compound is too small, the cost is not reduced and the water- and oil-repellency is not improved.
  • the glycerol compound is usually used in an amount of 0.05 to 7 parts by weight, preferably 0.1 to 4 parts by weight per one part by weight of the water- and oil-repellent.
  • the amount of the water- and oil-repellent having the fluoroalkyl group is not limited.
  • the water- and oil-repellent having the fluoroalkyl group is usually used in an amount of 0.1 to 1.0 per 100 parts by weight of a medium.
  • the water- and oil-repellents are a homopolymer of an acrylate or methacrylate having a fluoroalkyl group having 4 to 21 carbon atoms and a copolymer thereof with a monomer having no fluoroalkyl group (cf. for example, Japanese Patent Publication 8068/1985).
  • the monomer having no fluoroalkyl group examples include ethylene, vinyl acetate, vinyl fluoride, vinyl chloride, vinylidene fluoride, vinylidene chloride, acrylonitrile, styrene, ⁇ -methylstyrene, p-methylstyrene, acrylic acid and alkyl esters thereof, methacrylic acid and alkyl esters thereof, acrylamide, diacetone acrylamide, methylol diacetone acrylamide, methylol diacetone methacrylamide, vinyl alkyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, glycidyl acrylate and maleic anhydride.
  • the monomer having no fluoroalkyl group is usually used in an amount of 0 to 75, preferably 20 to 65 parts by weight per 100 parts by weight of the polymer.
  • the homopolymer and copolymer of the above acrylate and methacrylate nay be prepared by bulk polymerization, solution polymerization or emulsion polymerization.
  • the emulsion polymerization is usually preferable. Accordingly, the medium is usually water.
  • the emulsion polymerization uses no specific procedure. For example, as described in Japanese Patent Publication No. 8068/1985, a mixture of monomers is emulsified in the presence of a surfactant and a polymerization initiator, and then polymerized at 50 to 100°C with stirring.
  • the initiator includes a peroxide, an azo compound and a persulfate.
  • the surfactant any of anionic, cationic and nonionic surfactants can be used. A mixture of at least one cationic surfactant and at least one nonionic surfactant is preferable.
  • composition of the present invention may include conventionally used additives, for example, a crosslinking agent, an antistatic agent, a dye fixing agent, an anticrease agent, a flame retardant, a mothproofing agent and the like, and it may include general-purpose organic solvents, for example, isopropanol and the like.
  • the water- and oil-repellent composition of the present invention may be applied on a material to be treated by conventionally known methods such as spraying or dipping.
  • the materials to be treated include natural and synthetic fibers and textiles.
  • the adsorption amount of the water- and oil-repellent to the material to be treated is preferably 0.01 to 2% by weight based on the material to be treated.
  • the ester or ether derivative of a polyhydric alcohol having more carbon atoms or hydroxyl groups than glycerol remains in a cloth in a large amount after the water- and oil-repellency treatment, and the water- and oil-repellency property decreases due to hydrophilic hydroxyl groups and lipophilic alkyl groups.
  • the treated cloth has deteriorated feeling.
  • An ester or ether derivative of a polyhydric alcohol or alcohol having fewer carbon atoms or hydroxyl groups than glycerol cannot increase the water- and oil-repellency.
  • the polyglycerol having the melting point of not lower than 70°C has the same defects as above.
  • the water- and oil-repellent composition according to the present invention is economical since the glycerol compound used as the blending component is more easily available than the conventional blending component which comprises the acrylic resin.
  • the water- and oil-repellency is usually insufficient. But, according to the present invention, the water- and oil-repellency is sufficient because of the use of the glycerol compound even if the water- and oil-repellent adheres to a cloth in a small amount.
  • the water- and oil-repellent composition was evaluated as follows:
  • the water repellency is expressed by the water repellency No. of Table 1 determined by the spray method according to JIS (Japanese Industrial Standard) L-1092.
  • Oil repellency is expressed by the oil repellency No. of Table 2 determined by dropping several drops (diameter: about 4 mm) of a test solvent on two positions of a surface of a test cloth and observing whether the drops are held on the surface for 30 seconds or not.
  • the superscript "+" to the water repellency No. represents that the result is slightly better than said water repellency No.
  • Resistance to washing is expressed by the water-and oil-repellency Nos. which are determined after carrying out five cycles each consisting of washing a cloth treated with the water- and oil-repellent composition at 40°C in water containing 0.3 % by weight of detergent (Zabu-koso XK, manufactured by Kao) with a bath ratio of 1:40 (cloth:washing liquid (g:g)) for 5 minutes by using a domestic washing machine followed by rinsing the cloth for 15 minutes, dehydrating it and drying it at room temperature.
  • detergent Zabu-koso XK, manufactured by Kao
  • Water- and oil-repellency Nos. which are determined by washing a cloth treated with the water- and oil-repellent composition at 30°C in tetrachloroethylene by using a Launder-O-meter followed by drying at room temperature and then measuring the water- and oil-repellency.
  • a water- and oil-repellent used in the water- and oil-repellent composition of the present invention was prepared as follows:
  • the emulsion was mixed with the blending components as shown in Table 3 to prepare water- and oil-repellent compositions.
  • Test cloths were a polyester finished yarn woven fabric (hereinafter referred to as PE) and a nylon taffeta fabric (hereinafter referred to as N), and were dipped in the above composition for one minute and squeezed between two rolls so as to adjust the water content at 90 % and 50 %, respectively. Then, they were dried at 110°C for three minutes, PE was thermally treated at 180°C for 40 seconds and N was thermally treated at 170°C for one minute to impart the water- and oil-repellency. The water- and oil-repellency of the treated cloths were measured. The results are shown in Table 4.
  • PE polyester finished yarn woven fabric
  • N nylon taffeta fabric

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (2)

  1. Wasser- und Öl-abstoßende Zusammensetzung, umfassend ein Wasser- und Ölabstoßungsmittel, welches ein Homopolymer ist aus einem Acrylat oder Methacrylat mit einer Fluoralkylgruppe mit 4 bis 21 Kohlenstoffatomen oder ein Copolymer davon mit einem Monomer ohne Fluoralkylgruppe, und eine Glyzerinverbindung, ausgewählt aus Glyzerin, einem Esterderivat von Glyzerin, hergestellt duch Verestern einer Hydroxylgruppe an der alpha-Stellung mit einer Monoalkansäure mit 1 bis 6 Kohlenstoffatomen, einem Etherderivat des Glyzerins, hergestellt durch Substituieren eines Wasserstoffs oder einer Hydroxylgruppe an der alpha-Stellung mit einer Alkylgruppe mit 1 bis 6 Kohlenstoffatomen und Polyglyzerin, wobei das Polyglyzerin einen Schmelzpunkt von weniger als 70°C hat.
  2. Wasser- und Öl-abstoßende Zusammensetzung gemäß Anspruch 1, bei der die Zusammensetzung die Glyzerinverbindung in einer Menge von 0,05 bis 7 Gew.-Teilen pro einem Gewichtsteil des Wasser- und Ölabstoßungsmittels enthält.
EP19890120887 1988-11-11 1989-11-10 Wasser und Öl abweisende Zusammensetzung Expired - Lifetime EP0368338B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP286376/88 1988-11-11
JP28637688 1988-11-11
JP31913088A JP2503612B2 (ja) 1988-11-11 1988-12-16 撥水撥油剤組成物
JP319130/88 1988-12-16

Publications (3)

Publication Number Publication Date
EP0368338A2 EP0368338A2 (de) 1990-05-16
EP0368338A3 EP0368338A3 (en) 1990-08-08
EP0368338B1 true EP0368338B1 (de) 1995-02-22

Family

ID=26556289

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890120887 Expired - Lifetime EP0368338B1 (de) 1988-11-11 1989-11-10 Wasser und Öl abweisende Zusammensetzung

Country Status (3)

Country Link
EP (1) EP0368338B1 (de)
JP (1) JP2503612B2 (de)
DE (1) DE68921289T2 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3935859A1 (de) * 1989-10-27 1991-05-02 Bayer Ag Dispersionen von perfluoralkylgruppen enthaltende copolymerisate
DE4113894A1 (de) * 1991-04-27 1992-10-29 Bayer Ag Waessrige dispersionen von perfluoralkylgruppen enthaltenden copolymerisaten, ihre herstellung und verwendung
JPWO2021235452A1 (de) * 2020-05-20 2021-11-25

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6815430A (de) * 1967-11-02 1969-05-06
US3960797A (en) * 1973-12-28 1976-06-01 Pennwalt Corporation Water-in-oil emulsions of fluoroalkyl polymer, chlorinated alkane solvent and non-ioinic surfactant

Also Published As

Publication number Publication date
JP2503612B2 (ja) 1996-06-05
DE68921289T2 (de) 1995-07-27
DE68921289D1 (de) 1995-03-30
JPH02229879A (ja) 1990-09-12
EP0368338A3 (en) 1990-08-08
EP0368338A2 (de) 1990-05-16

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