KR830000046B1 - Compositions of Waterproofing and Oil Repellents - Google Patents
Compositions of Waterproofing and Oil Repellents Download PDFInfo
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- KR830000046B1 KR830000046B1 KR1019790003395A KR790003395A KR830000046B1 KR 830000046 B1 KR830000046 B1 KR 830000046B1 KR 1019790003395 A KR1019790003395 A KR 1019790003395A KR 790003395 A KR790003395 A KR 790003395A KR 830000046 B1 KR830000046 B1 KR 830000046B1
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- 239000000203 mixture Substances 0.000 title claims description 25
- 238000004078 waterproofing Methods 0.000 title claims description 8
- 230000002940 repellent Effects 0.000 title claims description 4
- 239000005871 repellent Substances 0.000 title claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 44
- 239000000460 chlorine Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 12
- -1 2-hydroxy-3-chlorofluoropropyl acrylate Chemical compound 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 125000003709 fluoroalkyl group Chemical group 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005108 dry cleaning Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000002939 oilproofing Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- LDVVMCZRFWMZSG-OLQVQODUSA-N (3ar,7as)-2-(trichloromethylsulfanyl)-3a,4,7,7a-tetrahydroisoindole-1,3-dione Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)Cl)C(=O)[C@H]21 LDVVMCZRFWMZSG-OLQVQODUSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005745 Captan Substances 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229940117949 captan Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
내용 없음.No content.
Description
본 발명은 세탁 및 드라이크리닝에 대하여 내성에 강한 방수 및 방유제의 조성물에 관한 것이다.The present invention relates to a composition of a waterproofing and oil repellent that is resistant to washing and dry cleaning.
지금까지 아크릴에스테르, 메타크릴 에스테르, 크로로푸렌, 염화비닐, 마레익에스테르, 비닐에테르 등과 같은 기타 중합성 화합물을 갖거나 갖지 않은 플루오로 알킬기 함유 중합성화합물의 중합물은 방수 및 방유제로서 유용한 것으로 알려져 있다. 또한 플루오로 알킬기 함유 중합성 화합물과함께 중합될 화합물로서 수산기 함유 아크릴 또는 메타크릴에스테르의 선택은 세탁 및 드라이 크리닝에 대하여 그 생성된 중합물의 내성을 강화할 수 있다는 것도 알려진 사실이다. 〔일본국 특허공고(심사공고) 번호 3798-1975 참조〕 그러나 후자의 경우에서 세탁 및 드라이크리닝에 대한 내성의 강화는 만족스러운 정도로 높지가 않다. 수산기 함유 아크릴, 또는 메타크릴에스테르 대신에 기타 중합 화합물의 사용이 제안되어 왔지만 내성 강화에는 아직미흡하다.To date, polymers of fluoroalkyl group-containing polymerizable compounds with or without other polymerizable compounds such as acrylic esters, methacryl esters, chloropurenes, vinyl chloride, mareic esters, vinyl ethers and the like are known to be useful as waterproofing and oil-proofing agents. have. It is also known that the choice of hydroxyl-containing acrylic or methacrylic esters as a compound to be polymerized with a fluoroalkyl group-containing polymerizable compound can enhance the resistance of the resulting polymer to laundry and dry cleaning. [See Japanese Patent Publication No. 3798-1975] However, in the latter case, the strengthening of resistance to washing and dry cleaning is not high enough to be satisfactory. The use of other polymeric compounds in place of hydroxyl-containing acrylic or methacrylic esters has been proposed but is still insufficient to enhance resistance.
다각적 연구한 결과로서 최소한 하나의 플루오로 알킬기 함유 중합성 화합물 및 일반식As a result of multiple studies, at least one fluoroalkyl group-containing polymerizable compound and general formula
CH2=CRCOOCH2CH(OH)CH2ClCH 2 = CRCOOCH 2 CH (OH) CH 2 Cl
로 된 최소한 하나의 2-하이드록시-3-크로로푸로필 아크릴레이트 또는 메타크릴레이트의 단위체를 포함하는 공중합물은 세탁 및 드라이크리닝에 대하여 내성이 강한 탁월한 방수 및 방유성을 나타낸다는 것이 이제 발견 되었다.It is now found that copolymers comprising at least one monomer of 2-hydroxy-3-chlorofluoropropyl acrylate or methacrylate exhibit excellent water and oil resistance, which is resistant to washing and dry cleaning. It became.
위 일반식에서 R은 수소 또는 메틸이다. 그들은 물에서 높은 안전성을, 그리고 유기용제에서는 좋은 용해성을 나타내고 있다.In the above general formula, R is hydrogen or methyl. They have high safety in water and good solubility in organic solvents.
그 공중합물이 세탁 및 드라이크리닝에 대하여 강한 내성을 나타내는 이유는 아직 확실치 않다. 그러나 많은 활성수소를 센루 로오즈 섬유에 대한 그것들의 효과는 폴리에스텔섬유, 폴리아마이드 섬유에 대한 효과보다 매우더 현저하기 때문에 수산기 또는 단부의 염소원자와 처리될 물질간에 화학적 결합이 생성되는 것으로 추리된다.It is not yet clear why the copolymer exhibits strong resistance to washing and dry cleaning. However, because their effect on many activated hydrogens on senrurose fibers is much more pronounced than on polyester and polyamide fibers, it is inferred that chemical bonds are created between the hydroxyl group or the chlorine atom at the end and the material to be treated. .
본 발명에 따르면 최소한 하나의 플루오로 알킬기 함유중합 화합물 및 최소한 하나의 2-하이드록시-3According to the invention at least one fluoroalkyl group-containing polymerized compound and at least one 2-hydroxy-3
크로로푸로필 아크릴레이트 또는 2-하이드록시-3-크로로푸로필 메타크릴레이트를 포함하는 공중합체로 주로 구성되어 있는 방수 및 방유제의 조성물로 된다. 그 공중합물 내의 2-하이드록시-3-크로로푸로필 아크릴레이트 및 또는 2-하이드록시-3-크로로푸로필 메타크릴레이트 단위체의 함량은 보통중량으로 0.1 내지 10% 바람직 하기는 중량으로 0.5 내지 5%로 할수 있다. 함량이 중량으로 0.1% 미만일때는 세탁 및 드라이크리닝에 대한 내성의 향상에 대한 충분한 효과를 나타내지 않으며, 함량이 중량으로 10% 이상일 경우방수 및 방유성은 많이 저하한다.It consists of a composition of a waterproofing and oil repellent mainly composed of a copolymer comprising chlorofurophyll acrylate or 2-hydroxy-3- chloropurophyll methacrylate. The content of 2-hydroxy-3-chlorofluoropropyl acrylate and or 2-hydroxy-3-chlorofluoropropyl methacrylate monomer in the copolymer is 0.1 to 10% by weight, preferably 0.5 by weight. To 5%. When the content is less than 0.1% by weight, it does not show a sufficient effect on the improvement of resistance to washing and dry cleaning, and when the content is 10% or more by weight, the waterproofing and oil-proof properties are much lowered.
플루오로알킬기 함유 중합성 화합물들의 예들은 다음식으로된 C3-C15바람직 하기는 C5-C10의 과플루오르 알킬기 함유 아크릴레이트 및 메타크릴레이트이다.Examples of fluoroalkyl group-containing polymerizable compounds are C 3 -C 15, preferably C 5 -C 10 perfluoroalkyl group-containing acrylates and methacrylates.
RfBOCOCR=CH2 R f BOCOCR = CH 2
여기서 Rf는 C3-C15과 플루오르 알킬이며, B는 (CH2)m(여기서 m은 2 내지 11중의 하나의 정수 임),
이들 플루오로알킬기 함유 아크릴레이트 및 또는 메타크릴 레이트들은 보통 공중합물의 중량기준으로 25% 미만의 양으로 함유 되도록 사용한다.These fluoroalkyl group containing acrylates and / or methacrylates are usually used to be contained in an amount of less than 25% by weight of the copolymer.
상기의 2개의 기본적 성분에 첨가하여 높은 용해성과 양호한 방수성과 같은 개량된 물리적 성질을 가진 합성 공중합물을 얻는 목적으로 그 공중합물은 플루오로알킬기를 갖지 않은 기타 중합성 화합물 예로서 에티렌, 염화비닐, 비니리덴 할라이드, 스티렌, 아크릴산 및 그것의 알킬에스테르, 메타크릴산 및 그것의 알킬에스테르, 벤질메타크릴레이트, 싸이크로 헥실메타크릴레이트, 비닐알킬케톤, 비닐알킬에텔, 부타디엔, 이소푸렌, 크로로푸렌, 마레인산 들중의 어느 단위체를 선택적으로 함유 할수도 있다. 예를들면, 플루오로알킬기를 갖지 않는 기타 중합성 화합물로서 스테아릴 아크릴레이트 또는 메타크릴레이트의 사용은 방수성과 신축성, 말랐을 때의 접착 방지성 및 유기용제에서의 용해성등을 향상시키는데 효과적이다.In order to obtain a synthetic copolymer having improved physical properties such as high solubility and good water resistance by adding to the two basic components, the copolymer is used as other polymerizable compounds having no fluoroalkyl group, such as ethylene and vinyl chloride. , Vinylidene halide, styrene, acrylic acid and alkyl esters thereof, methacrylic acid and alkyl esters thereof, benzyl methacrylate, cyclohexyl methacrylate, vinyl alkyl ketones, vinyl alkyl ethers, butadiene, isoprene, chloro It may optionally contain any of monomers of furene and maleic acid. For example, the use of stearyl acrylate or methacrylate as another polymerizable compound having no fluoroalkyl group is effective in improving water resistance and elasticity, anti-drying adhesion and solubility in organic solvents.
이 경우에서 가장 바람직한 것은 플루오로알킬기 함유 중합성 화합물 및 2-하이드록시-3-크로로푸로필 아크릴레이트 또는 메타크릴레이트와 스테아릴아크릴레이트 또는 메타크릴레이트의 단위체를 중량기준으로 각각 25% 미만 및 0.1 내지 10%(바람직 하기는 0.2 내지 5%) 및 5 내지 74.9%의 함량으로 함유하는 공중합물이다.Most preferred in this case is less than 25% by weight of monomers of the fluoroalkyl group-containing polymerizable compound and 2-hydroxy-3-chlorofluoropropyl acrylate or methacrylate and stearylacrylate or methacrylate, respectively. And copolymers containing 0.1 to 10% (preferably 0.2 to 5% below) and 5 to 74.9%.
본 발명의 공중합물을 생산하기 위하여 각종 재래식 중합방법 및 조건을 채택할 수 있다. 괴상 중합 및 용액 중합 및 유화중합 및 방사 중합등의 어느 것도 사용할 수 있다.Various conventional polymerization methods and conditions may be employed to produce the copolymers of the present invention. Any of bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be used.
전형적인 중합 방법중에 하나는 계면활성제를 첨가하여 공중합 하도록 단량체 성분의 혼합물을 유화 하는 것과 그 생성 유화물을 교반 하면서 중합되게 하는 것을 포함한다. 반응 과정에 과산화물 및 아조화합물과유산염 등과 같은 중합개시제를 첨가한다. 계면활성제로서는 온이온과 양이온 및 비이온 계면활성제 중에서 선택한 어느것도 사용할 수 있으며, 바람직 하기는 양이온 계면활성제와 비이온 계면활성제의 혼합물을 사용한다.One typical polymerization process involves emulsifying a mixture of monomeric components to add a surfactant to copolymerize and allowing the resulting emulsion to polymerize while stirring. A polymerization initiator such as peroxide, azo compound and lactate is added to the reaction process. As the surfactant, any one selected from an ion, a cationic and a nonionic surfactant can be used, and preferably, a mixture of a cationic surfactant and a nonionic surfactant is used.
또 하나의 전형적인 중합방법은 공중합될 단량체 성분을 적당한 유기용제에 분해 시키는 것과 그 생성된 용해액을 유기용제에서 또는 이온발생 조사에서 용해될 수 있는 과산화물 또는 아조화합물과 같은 중합 개시제 존재하에 중합되게 하는 것을 포함한다. 이렇게 하여 조제된 공중합물은 유액, 용액 또는 에어로졸과 같은 재래식 형태로 있는 방수 및 방유제로 사용할 수 있다.Another typical polymerization process is to decompose the monomer component to be copolymerized into a suitable organic solvent and to cause the resulting solution to be polymerized in the presence of a polymerization initiator such as a peroxide or azo compound which can be dissolved in an organic solvent or in ionogenic irradiation. It includes. The copolymers thus prepared can be used as waterproofing and oilproofing agents in conventional forms such as emulsions, solutions or aerosols.
본 발명의 실제적이고 구체적인 실시예는 다음 설명으로 표시한 바와 같이 여기서 방수성은 JIS(일본공업 규격표준) L-1005에서 설명된 살포 방법에 따라 결정된 방수성번호(표 1참조)로 표현되며, 방유성은 사전에 수험재료로 처리한 헝겊 표면에 n-헵탄 및 누졸(NUJOL)의 혼합물을 방울로 떨어 뜨리고, 그 방울의 지속을 3분동안 관찰 함으로서 결정되는 방유성 번호(표 2 참조)로 표현된다.As shown in the following description, a practical and specific embodiment of the present invention, where waterproofness is expressed by a waterproofing number (see Table 1) determined according to the spraying method described in JIS (Japanese Industrial Standards) L-1005, Is represented by an oil-proof number (see Table 2) determined by dropping a mixture of n-heptane and NUJOL onto a cloth surface previously treated with the test material and observing the duration of the drop for 3 minutes. .
[표 1]TABLE 1
[표 2]TABLE 2
세탁에 대한 내성은 시료를 사전에 처리한 헝겊을 세척제(“Zabu Koso XK”, 주성분으로서 쏘디움 하이어 알코 유산염 및 쏘디움 도데실 벤젠 설포네이트 혼합물을 함유하는 세척제, 가오비누 주식회사제품)를 1대 40의 비율로담그고(중량기준 헝겊대 세척제 포함물 비율)로 40℃ 온도에서 중량기준 0.3%의 농도로 포함하는 물로 가정용세탁기로 5분간에 걸쳐서 세척하고, 그 헝겊을 15분간 물로 헹구고 또한 그 행군 헝겊을 80℃ 온도에서 3분간 건조시키는 것으로 결정된다. 상기 작업을 1주기로 하여 3회 반복하고, 그런연후에 측정된 방수성 및 방유성을 세탁에 대한 내성을 표시하는 것으로서 취하였다.Tolerant to washing, use a pre-treated cloth with a cleaning agent (“Zabu Koso XK”, a cleaning agent containing a mixture of Sodium Heyer Alcoate and Sodium Dodecyl Benzene Sulfonate as a main ingredient, manufactured by Gao Soap). Dip at a rate of 40 (percent by weight of cloth cloth cleaner) and wash at a temperature of 0.3% by weight at 40 ° C. for 5 minutes with a household washing machine, rinse the cloth with water for 15 minutes, and then march The cloth is determined to dry at 80 ° C. for 3 minutes. The operation was repeated three times with one cycle, and the waterproofness and oil resistance measured after that were taken as an indication of the resistance to washing.
드라이크리닝에 대한 내성을 사전에 시료로 처리한 헝겊을 30℃ 온도로 칼륨올레인산염을 포함하는 퍼크로로에티렌 속에서 세탁 시험기를 사용하여 1시간동안 교반한 것과 대기에서 그 헝겊을 건조하고 나서 3분간 80℃ 온도에서 건조하는 것으로 결정된다. 위에 작업은 한주기로서 3회반복되며, 그후에 측정된 방수성 및 방유성은 드라이크리닝에 대한 내성을 나타내는 것으로 취해졌다.A sample that was previously sampled for dry cleaning resistance was stirred at 30 ° C. in a perchlorethylene containing potassium oleate for 1 hour using a laundry tester, and the cloth was dried in air. It is determined to dry at 80 ° C. for 3 minutes. The above operation was repeated three times in one cycle, after which the measured water and oil resistance were taken to indicate resistance to dry cleaning.
[참고예 1]Reference Example 1
다음식의 화합물 : (CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH2(5:3:1의 중량비로된 n=3, n=4, n=5의 혼합물)(60g), C18H37OOCCHCH2(38g), CH2=CHCOOCH2CH (OH)-CH2Cl(2g) 탈산소 및 탈이온된 물(250g), 아세톤(50g), N-도데실데르캅탄 (0.2g), 디메틸알킬아민아세테이트(3g), 포리옥시에티렌알킬페놀(3g)을 플라스크에 충전하여 60℃ 온도에서 1시간 동안 질소 흐름하에 교반하였다. 거기에다 물(10g)내에 있는 아조비스이소부틸 아미딘 하이드로 클로라이드(1g)를 첨가한 후 교반을 60℃ 온도에서 질소흐름하에 5시간동안 계속하여 중합을 진행시켰다. 전환은 가스 크로마토그라피법으로 99% 이상된 것이 확인 되었다. 얻어진 유액은 중량 기준으로 25%의 공중합물을 함유하고 있었다.A compound of the formula: (CF 3 ) 2 CF (CF 2 CF 2 ) nCH 2 CH 2 OOCCH = CH 2 (a mixture of n = 3, n = 4, n = 5 in a weight ratio of 5: 3: 1) ( 60 g), C 18 H 37 OOCCHCH 2 (38 g), CH 2 = CHCOOCH 2 CH (OH) -CH 2 Cl (2 g) deoxygenated and deionized water (250 g), acetone (50 g), N-dodecylder Captan (0.2 g), dimethylalkylamine acetate (3 g), and polyoxyethylene alkylphenol (3 g) were charged to the flask and stirred under nitrogen flow for 1 hour at 60 ° C. Thereto, azobisisobutyl amidine hydrochloride (1 g) in water (10 g) was added, followed by stirring for 5 hours under nitrogen flow at 60 ° C. It was confirmed that the conversion was more than 99% by gas chromatography. The resulting emulsion contained 25% copolymer by weight.
[참고예 2]Reference Example 2
다음식의 화합물 : (CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH2(중량비 5:3:1로된 n=3, n=4, n=5의 혼합물)(60g), C18H37OOCCH=CH2, (38g), CH2=CHCOOCH2CH (OH)-CH2Cl(2g), 1,1,1-트리크로로에탄(550g)을 플라스크에 충전하여 60℃ 온도에서 질소 흐름하에 30분간 교반 하였다. 거기에다 아조비스 이소부틸로 니트릴 1g을 첨가한 후에 교반을 질소 흐름하에서 12시간동안 계속하여 중합을 진행 시켰다. 전환은 가스 크로마토그라피법으로 99% 이상인 것으로 확인 되었다. 얻어진 용액은 중량기준 15%의 공중합물을 함유 하였다.Compound of the formula: (CF 3 ) 2 CF (CF 2 CF 2 ) nCH 2 CH 2 OOCCH = CH 2 (a mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1) (60 g ), C 18 H 37 OOCCH = CH 2 , (38g), CH 2 = CHCOOCH 2 CH (OH) -CH 2 Cl (2g), 1,1,1-trichloroethane (550g) It was stirred for 30 minutes under nitrogen flow at a temperature of 60 ℃. After adding 1 g of nitrile with azobis isobutyl, stirring was continued for 12 hours under a nitrogen flow. The conversion was found to be greater than 99% by gas chromatography. The resulting solution contained 15% copolymer by weight.
[예 1 내지 9 및 비교예 1 내지 6 :][Examples 1-9 and Comparative Examples 1-6:]
참고예 1에서와 같은 방식으로 각예 또는 비교예에서 설명한 바와 같은 배합을 가진 공중합물은 유액의 형태로 조제되었다. 생성된 유액은 중량기준 0.5%의 고형 성분을 갖는 희석액을 만들도록 물로 희석 되었다. 그 희석액에 중량비 35:65로된 면섬유 및 폴리에스테르 섬유로 구성된 헝겊을 담구었다. 그 담군 헝겊을 마름으로 짜고, 80℃ 온도에서 3분간 말리고 그후에 150℃ 온도로 3분간 말렸다.In the same manner as in Reference Example 1, the copolymer having the formulation as described in each example or the comparative example was prepared in the form of an emulsion. The resulting emulsion was diluted with water to make a diluent with a solid content of 0.5% by weight. A cloth composed of cotton fibers and polyester fibers in a weight ratio of 35:65 was dipped in the dilution. The soaked cloth was squeezed dry, dried at 80 ° C. for 3 minutes and then dried at 150 ° C. for 3 minutes.
이렇게 처리된 헝겊을 방수성 및 방유성의 결정을 위하여 시험을 하였다. 또한 그것을 세탁 및 드라이크리닝에 대한 내성 시험을 하였다.The cloth thus treated was tested for determination of water and oil resistance. It was also tested for resistance to washing and dry cleaning.
결과는 표 3에서 본 바와 같다.The results are shown in Table 3.
예 1 중량기준 부분Example 1 Part by weight
(CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH = CH 2 60
(중량비 5:3:1로된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH239C 18 H 37 OOCCH = CH 2 39
CH2CHCOOCH2CH(OH)CH2Cl 1CH 2 CHCOOCH 2 CH (OH) CH 2 Cl 1
예 2 중량기준 부분Example 2 Part by weight
(CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH = CH 2 60
(중량비 5:3:1로된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH238C 18 H 37 OOCCH = CH 2 38
CH2=CHCOOCH2CH(OH)CH2Cl 2CH 2 = CHCOOCH 2 CH (OH) CH 2 Cl 2
예 3 중량기준 부분Example 3 Part by weight
(CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH = CH 2 60
(중량비 5:3:1로된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH236C 18 H 37 OOCCH = CH 2 36
CH2=CHCOOCH2CH(OH)CH2Cl 4CH 2 = CHCOOCH 2 CH (OH) CH 2 Cl 4
예 4 중량기준 부분Example 4 Part by weight
(CF3)2CF(CF2CF2)nCH2CH2OOCCH(CH3)=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH (CH 3 ) = CH 2 60
(중량비 5:3:1로된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH238C 18 H 37 OOCCH = CH 2 38
CH2=CHCOOCH2CH(OH)CH2Cl 2CH 2 = CHCOOCH 2 CH (OH) CH 2 Cl 2
예 5 중량기준 부분Example 5 Weight part
(CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH = CH 2 60
(중량비 5:3:1로된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCC(CH3)=CH238C 18 H 37 OOCC (CH 3 ) = CH 2 38
CH2=CHCOOCH2CH(OH)CH2Cl 2CH 2 = CHCOOCH 2 CH (OH) CH 2 Cl 2
예 6 중량기준 부분Example 6 Part by weight
(CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH = CH 2 60
(중량비 5:3:1로된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH238C 18 H 37 OOCCH = CH 2 38
CH2=C(CH3)COOCH2CH(OH)CH2Cl 2CH 2 = C (CH 3 ) COOCH 2 CH (OH) CH 2 Cl 2
예 7 중량기준 부분Example 7 Part by weight
CF3CF2(CF2CF2)nCH2CH2OOCCH(CH3)=CH260CF 3 CF 2 (CF 2 CF 2 ) n CH 2 CH 2 OOCCH (CH 3 ) = CH 2 60
(중량비 5:3:1로된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH238C 18 H 37 OOCCH = CH 2 38
CH2=CHCOOCH2CH(OH)CH2Cl 2CH 2 = CHCOOCH 2 CH (OH) CH 2 Cl 2
예 8 중량기준 부분Example 8 Part by weight
OOCCH3 OOCCH 3
(CF3)2CF(CF2CF2)nCH2CHCH2OOCC(CH3)=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CHCH 2 OOCC (CH 3 ) = CH 2 60
(중량비 5:3:1로된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH238C 18 H 37 OOCCH = CH 2 38
CH2=C(CH3)COOCH2CH(OH)CH2Cl 2CH 2 = C (CH 3 ) COOCH 2 CH (OH) CH 2 Cl 2
예 9 중량기준 부분Example 9 Part by weight
C8F17SO2N(C2H5)C2H4OOCCH=CH260C 8 F 17 SO 2 N (C 2 H 5 ) C 2 H 4 OOCCH = CH 2 60
C18H37OOCC(CH3)=CH238C 18 H 37 OOCC (CH 3 ) = CH 2 38
CH2=CHCOOCH2CH(OH)CH2Cl 2CH 2 = CHCOOCH 2 CH (OH) CH 2 Cl 2
비교예 1 중량기준 부분Comparative Example 1 Part by weight
(CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH = CH 2 60
(중량비 5:3:1로된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH240C 18 H 37 OOCCH = CH 2 40
비교예 2 중량기준 부분Comparative Example 2 Part by weight
(CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH = CH 2 60
(중량비 5:3:1로 된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH238C 18 H 37 OOCCH = CH 2 38
CH2=C(CH3)COOCH2CH(OH)CH2Cl 2CH 2 = C (CH 3 ) COOCH 2 CH (OH) CH 2 Cl 2
비교예 3 중량기준 부분Comparative Example 3 Part by Weight
(CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH = CH 2 60
(중량비 5:3:1로 된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH238C 18 H 37 OOCCH = CH 2 38
CH2=C(CH3)COOCH2CH(OH)CH32CH 2 = C (CH 3 ) COOCH 2 CH (OH) CH 3 2
비교예 4 중량기준 부분Comparative Example 4 Part by Weight
(CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH = CH 2 60
(중량비 5:3:1로 된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH238C 18 H 37 OOCCH = CH 2 38
CH2=CH2=CHCOOCH2CH(OH)CH32CH 2 = CH 2 = CHCOOCH 2 CH (OH) CH 3 2
비교예 5 중량기준 부분Comparative Example 5 Part by Weight
(CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH = CH 2 60
(중량비 5:3:1로 된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH238C 18 H 37 OOCCH = CH 2 38
CH2=C(CH3)COOC2H4Cl 2CH 2 = C (CH 3 ) COOC 2 H 4 Cl 2
비교예 6 중량기준 부분Comparative Example 6 Part by Weight
(CF3)2CF(CF2CF2)nCH2CH2OOCCH=CH260(CF 3 ) 2 CF (CF 2 CF 2 ) n CH 2 CH 2 OOCCH = CH 2 60
(중량비 5:3:1로 된 n=3, n=4, n=5의 혼합물)(Mixture of n = 3, n = 4, n = 5 with weight ratio 5: 3: 1)
C18H37OOCCH=CH238C 18 H 37 OOCCH = CH 2 38
CH2=C(CH3)COOC2H4OH 1CH 2 = C (CH 3 ) COOC 2 H 4 OH 1
CH2=C(CH3)COOC2H4Cl 1CH 2 = C (CH 3 ) COOC 2 H 4 Cl 1
[표 3]TABLE 3
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019790003395A KR830000046B1 (en) | 1979-10-02 | 1979-10-02 | Compositions of Waterproofing and Oil Repellents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019790003395A KR830000046B1 (en) | 1979-10-02 | 1979-10-02 | Compositions of Waterproofing and Oil Repellents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR830000046B1 true KR830000046B1 (en) | 1983-02-03 |
Family
ID=19213091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019790003395A KR830000046B1 (en) | 1979-10-02 | 1979-10-02 | Compositions of Waterproofing and Oil Repellents |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR830000046B1 (en) |
-
1979
- 1979-10-02 KR KR1019790003395A patent/KR830000046B1/en active
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