WO1996012775A1 - Composition et procede antisalissure - Google Patents

Composition et procede antisalissure Download PDF

Info

Publication number
WO1996012775A1
WO1996012775A1 PCT/JP1995/002174 JP9502174W WO9612775A1 WO 1996012775 A1 WO1996012775 A1 WO 1996012775A1 JP 9502174 W JP9502174 W JP 9502174W WO 9612775 A1 WO9612775 A1 WO 9612775A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer
antifouling
weight
composition
solvent
Prior art date
Application number
PCT/JP1995/002174
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Motonobu Kubo
Takashi Enomoto
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.
Priority to JP51378096A priority Critical patent/JP3700179B2/ja
Publication of WO1996012775A1 publication Critical patent/WO1996012775A1/ja

Links

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
    • 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
    • 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
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof

Definitions

  • the present invention relates to an antifouling composition and an antifouling method, and more particularly, to an antifouling composition and an antifouling composition for imparting excellent antifouling properties and water / oil repellency to cellulosic fiber products. Related to processing method.
  • Furuoroarukiru group-containing monomer binding ⁇ ⁇ Rei_1 Ji 0 0 ((: 1 ⁇ 2 ⁇ 1 2 0) 1 ⁇ '
  • Japanese Unexamined Patent Publication (Kokai) No. 6-180606 discloses a test result of soil release properties as an index of antifouling property against cotton, but results are inferior to those of polyester and nylon. I have.
  • Japanese Unexamined Patent Publication (Kokai) No. 59-981113 discloses a fluorochemical copolymer which is effective for cellulosic materials, but relates to a food paper container having excellent water and oil repellency, and becomes dirty. No function is described that can be easily removed by washing. It also describes spun fibers and describes the effects of oil repellency and water repellency, but does not describe the removal of attached dirt by washing. Further, Japanese Patent Publication No. 53-18346 discloses an organic solution composition of a soil-removing type water / oil repellent, but uses a high dielectric constant organic solvent as a medium, and only polyester cloth is used in Examples. Not listed.
  • An object of the present invention is to provide a very good stain release property to a cell mouth-based fiber product which has not been able to provide a sufficient stain release property until now.
  • R 1 is a hydrogen atom or a methyl group
  • X is one CH 2 CH 2 —, one C (CH 3 ) H—CH 2 — or
  • R 2 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • n is a number from 1 to 50.
  • composition for antifouling processing comprising:
  • the present invention also provides an antifouling method comprising treating a cellulosic fiber product with the antifouling composition.
  • the removability of the attached dirt by washing is excellent.
  • the fluoroalkyl group-containing monomer (a-1) is preferably a (meth) acrylate ester having a fluoroalkyl group.
  • Preferred specific examples of the fluoroalkyl group-containing monomer (a-1) are as follows.
  • n is 1 to 50, preferably 1 ⁇ 35, more preferably 1 ⁇ 25.
  • the non-fluorinated monomer (a-2) may be a combination of one or more kinds.
  • Each X in one (XO) n— may be the same or different, and when different, — (XO) n— is a block copolymer, an alternating copolymer, or a random copolymer. Either form is acceptable.
  • CH 2 C (CH 3) COO (CH 2 CH 2 0) 18 - 23 H ( preferred weight ratio of 5: 9 5-95: 5) a combination of that it is preferable.
  • the weight ratio of the fluoroalkyl group-containing monomer (a-1) / non-fluorinated monomer (a-2) is 5/95 to 955, preferably 30 to 80 to 20. And more preferably 40 to 60 to 30. If the amount of the fluoroalkyl group-containing monomer (a-1) exceeds 95% by weight, the soil release property is insufficient. On the other hand, if it is less than 5% by weight, the oil repellency is insufficient.
  • the average molecular weight of the copolymer (a) is usually 1,000 to 100,000, preferably 2000 to 100,000.
  • the average molecular weight is measured by gel permeation chromatography (GPC) (in terms of polystyrene).
  • the solubility parameter is 5.5-12.0, preferably 6.0-11.5, more preferably 7.0-10.0, and the dielectric constant (20 ° C) is less than 20, It is preferably 19.0 to 2. ⁇ , more preferably 19.0 to 4.0.
  • solvent (b) examples include:
  • Chlorinated compounds such as trichloroethane and black form; Ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone Aromatic compounds such as toluene and benzene;
  • Esters such as ethyl acetate and butyl acetate
  • 1,1-dichloro-1-1-fluoro-ethane (141b), 1.1-dichloro-2,2,3,3,3-pentafluoro-oral bread (225ca), 1,3-dichloro-1,1,2,2,3-pentafluoro- Propane (225cb).
  • Petroleum such as hexane, heptane, and mineral terpen.
  • isopropyl alcohol with a relatively small solubility parameter solubility parameter: 11.5 can be used. These can be used not only alone but also by mixing several liquids.
  • the solvent (b) may be used alone, but a solvent having a solubility parameter other than 5.5 to 12.0 or having a dielectric constant of 20 or more is used in an amount of about 20 parts by weight or less per 100 parts by weight of the solvent (b) in the antifouling composition. May be present.
  • Such solvents are, for example, methanol, ethanol, ethylene glycols, diethylene glycols, propylene glycols, dipropylene glycol and the like.
  • the value of the solubility parameter (SP) is determined by a method of measuring latent heat of vaporization and a method described in Small, Journal of Applied Chemisty, 3..71-80. Feb (l9 ⁇ 3). It is a value calculated according to the described definition.
  • the value of the dielectric constant is determined by A. Weissborger; Organic Solvents, 3rd Ed. And the values described in JA Riddick, et al; Organic Solvents, 2nd Ed., Or by the general method described in New Experimental Chemistry Course, October 2, 1977, published by The Chemical Society of Japan, vol. 5, p. 265 Value.
  • the amount of the crosslinkable monomer is generally 0 to 10% by weight, preferably 0 to 5% by weight, more preferably 0.1 to 5% by weight, based on the copolymer (a).
  • (meth) acrylonitrile, vinyl chloride, vinylidene chloride, alkyl (di! -Di) ester of (meth) acrylic acid, styrene, benzyl (meth) acrylate, vinyl alkyl ketone, vinyl alkyl ether, Ethylenically unsaturated monomers such as isoprene, butadiene, and chloroprene can also be copolymerized with the copolymer (a). These amounts are 0 to 40% by weight, preferably 0 to 20% by weight, based on the copolymer (a).
  • a water repellent and oil repellent can be used in combination.
  • commercially available TG-652 manufactured by Daikin Industries, Ltd.
  • the active ingredient (weight ratio) of the copolymer Z / water / oil repellent of the present invention is 10Z0 to 1Z5.
  • the composition of the present invention may contain the isocyanate compound (c).
  • the isocyanate compound (c) includes a block isocyanate.
  • the antifouling property and the durability of the soil release property are improved.
  • Specific examples of isocyanate compounds Polyisocyanates such as lendiisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, lysine ester triisocyanate, and hexamethylene triisocyanate.
  • the amount of the isocyanate compound (C) is from 0 to 100 parts by weight, preferably from 10 to 80 parts by weight, more preferably from 20 to 80 parts by weight, based on 100 parts by weight of the copolymer (a). Parts by weight.
  • various polymerization reaction systems and conditions can be arbitrarily selected, and various polymerization systems such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be used. Either can be adopted.
  • a method in which a mixture of compounds to be copolymerized is copolymerized in the presence of a suitable organic solvent can be adopted.
  • a peroxide As a polymerization initiation source, a peroxide, an azo compound or ionizing radiation which is soluble in an organic solvent to be used is used.
  • the copolymer (a) thus obtained can be prepared in any form such as a solvent solution, an emulsion or an aerosol according to a conventional method, and can be used as an antifouling composition.
  • the copolymer (a) of the present invention can be used as an antifouling agent by any method depending on the type of the object to be treated and the preparation form (solvent solution type, aerosol type, etc.) on the article to be treated. Can be applied.
  • the antifouling composition of the present invention is usually of a solvent solution type. A method in which a copolymer is adhered to the surface of the object to be treated and dried by a known method of coating such as immersion coating can be adopted. If necessary, curing may be carried out by applying with an appropriate crosslinking agent.
  • the azole type antifouling agent is simply sprayed and sprayed on the object to be treated. After drying immediately, it can exhibit sufficient water and oil repellency and soil release properties.
  • the copolymer of the present invention may be used as an antifouling agent by mixing another polymer blender. Of course, it is also possible to obtain an antifouling agent by appropriately using other water repellents, oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers, screen inhibitors and the like as additives.
  • a copolymer of the present invention a copolymer
  • the amount of (a) is 50 to 0.01 parts by weight, preferably 30 to 0.5 parts by weight, per 100 parts by weight of the antifouling composition.
  • the antifouling method of the present invention is particularly effective for cellulosic fiber products.
  • Textile products include fibers, yarns and fabrics formed from fibers.
  • the object to be treated may be any of a fiber, a yarn, and a cloth.
  • Cellulosic fibers include cotton, hemp, viscose rayon and cuprammonium rayon.
  • the antifouling method of the present invention is also effective for a mixture of cellulose fibers mixed with other fibers.
  • the term “treatment” refers to an operation of adhering an active ingredient (for example, a copolymer (a) and an isocyanate compound (c)) in an antifouling composition to a textile, for example, Coating, spray coating, etc.
  • an active ingredient for example, a copolymer (a) and an isocyanate compound (c)
  • the water repellency and oil repellency shown in the following Examples and Comparative Examples are represented by the following scale. That is, the water repellency is represented by the water repellency No. (see Table 1) by the spray method of JISL-1092. mm) and judge by the permeation state after 30 seconds (AATCC-TM118-19666). Water repellency No.
  • the test of the soil release performance was performed as follows. That is, spread the test cloth on blotting paper laid horizontally, drop 5 drops of dirty motor oil (SAE 20W-40, put in the engine of a small passenger car, discharged after running 400 OKm), and put polyethylene on it. Spread the sheet, put a 2kg weight, remove the weight and the polyethylene sheet after 60 seconds, wipe off any excess oil, leave it at room temperature for 1 hour, add ballast cloth to the test cloth and add 1 Using a 25 g detergent (Super Zab (trade name), manufactured by Kao Corporation), treat with an electric washing machine for 10 minutes at a bath volume of 35 liters and a liquid temperature of 40, and rinse. Air dry. The residual stain condition of the dried test cloth is compared with that of the standard photographic plate, and the soil release performance is indicated by the corresponding judgment grade (see Table 3).
  • the standard photographic plate used was AAT CC-Test method 130-1970.
  • the resulting copolymer solution contained 18.5% by weight of a copolymer solid.
  • the copolymer According to gel permeation chromatography (GPC), the molecular weight was 1500 (converted to styrene).
  • This copolymer solution was diluted with methyl ethyl ketone so as to have a copolymer solid content of 0.75% to obtain a diluent.
  • a cotton broad cloth was dipped in the diluent, squeezed with a roll, and the wet pickup was adjusted to 40%. Then, it was air-dried for 4 hours and heat-treated at 160 ° C for 1 minute to complete the water / oil / oil repellent / antifouling treatment. The thus treated fabric was measured for initial water repellency, oil repellency and soil release performance. Table 4 shows the results.
  • Example 4 shows the results.
  • Example 4 shows the results.
  • Example 10 After dissolving the copolymer dispersion of Example 1 in methyl ethyl ketone, the isocyanate [IPDI (Example 10), MDI (Example 11), coronate L (Example 12)] was added to the copolymer. After adding 27% by weight to the polymer and then diluting with methyl ethyl ketone, the cotton broad was treated as in Example 1. Washing of this cloth at the beginning and at the same time (as in the soil removal performance test) The water repellency, the oil repellency and the soil release performance after performing the test five times were measured. Table 5 shows the results. The results when no isocyanate is used (ie, Example 1) are also shown.
  • Coronate L Nippon Polyurethane Industry Co., Ltd.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Paints Or Removers (AREA)
PCT/JP1995/002174 1994-10-24 1995-10-23 Composition et procede antisalissure WO1996012775A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP51378096A JP3700179B2 (ja) 1994-10-24 1995-10-23 防汚加工用組成物および防汚加工方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP25799894 1994-10-24
JP6/257998 1994-10-24

Publications (1)

Publication Number Publication Date
WO1996012775A1 true WO1996012775A1 (fr) 1996-05-02

Family

ID=17314121

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1995/002174 WO1996012775A1 (fr) 1994-10-24 1995-10-23 Composition et procede antisalissure

Country Status (3)

Country Link
JP (1) JP3700179B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
TW (1) TW302407B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1996012775A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6207777B1 (en) 1997-06-30 2001-03-27 Asahi Glass Company Ltd. Antifouling composition, method for its production and product treated therewith
JP2012012718A (ja) * 2010-06-30 2012-01-19 Toyobo Specialties Trading Co Ltd 作業服用織編物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53134787A (en) * 1977-04-28 1978-11-24 Asahi Glass Co Ltd Stain-removing agent containing fluoroalkyl radical
JPH0468006A (ja) * 1990-07-09 1992-03-03 Daikin Ind Ltd 新規共重合体および防汚加工剤
JPH05222149A (ja) * 1992-02-12 1993-08-31 Asahi Glass Co Ltd 撥水撥油剤組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53134787A (en) * 1977-04-28 1978-11-24 Asahi Glass Co Ltd Stain-removing agent containing fluoroalkyl radical
JPH0468006A (ja) * 1990-07-09 1992-03-03 Daikin Ind Ltd 新規共重合体および防汚加工剤
JPH05222149A (ja) * 1992-02-12 1993-08-31 Asahi Glass Co Ltd 撥水撥油剤組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6207777B1 (en) 1997-06-30 2001-03-27 Asahi Glass Company Ltd. Antifouling composition, method for its production and product treated therewith
JP2012012718A (ja) * 2010-06-30 2012-01-19 Toyobo Specialties Trading Co Ltd 作業服用織編物

Also Published As

Publication number Publication date
TW302407B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1997-04-11
JP3700179B2 (ja) 2005-09-28

Similar Documents

Publication Publication Date Title
US5578688A (en) Antifouling agent
JP3906506B2 (ja) 防汚加工剤
KR102262233B1 (ko) 불소 함유 중합체 및 표면 처리제 조성물
JP2000154474A (ja) 水分散型防汚加工剤組成物
JP4206767B2 (ja) 撥水撥油剤水性組成物
JP3944922B2 (ja) 防汚加工用組成物および防汚加工方法
EP3792328A1 (en) Water and oil repellent and textile product
KR20100090693A (ko) 친수성 플루오르화된 방오성 공중합체
JP3744035B2 (ja) 安定性に優れる水分散型撥水撥油剤組成物
JP3820593B2 (ja) 防汚加工剤
CN100509989C (zh) 防水防油剂的水性分散液组合物
KR20100044221A (ko) 발알코올성 및 오염 탈리성을 갖는 불소 함유 섬유 가공제
WO1996012775A1 (fr) Composition et procede antisalissure
JPH0768511B2 (ja) 撥水撥油剤
JP4677983B2 (ja) 含フッ素重合体を含む汚れ脱離剤
JPS636676B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP3941146B2 (ja) 撥水撥油剤組成物
JPH10251693A (ja) ドライクリーニング用撥水撥油組成物及びそれを用いた処理方法
JPS63474B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JPH02214792A (ja) 撥水撥油剤
KR102856595B1 (ko) 발수제 조성물
KR970011245B1 (ko) 섬유처리용 공중합체
JP3861473B2 (ja) 撥水撥油加工剤組成物
JPH02277887A (ja) 防汚性布帛
JPH10325079A (ja) 防汚加工方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase