JPH02308844A - Heat-sensitive gelatinizable emulsion - Google Patents
Heat-sensitive gelatinizable emulsionInfo
- Publication number
- JPH02308844A JPH02308844A JP13018689A JP13018689A JPH02308844A JP H02308844 A JPH02308844 A JP H02308844A JP 13018689 A JP13018689 A JP 13018689A JP 13018689 A JP13018689 A JP 13018689A JP H02308844 A JPH02308844 A JP H02308844A
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- weight
- parts
- heat
- sensitive
- 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.)
- Granted
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 96
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 17
- 239000000057 synthetic resin Substances 0.000 claims abstract description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 7
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 239000011342 resin composition Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 19
- 239000011347 resin Substances 0.000 abstract description 19
- 239000003349 gelling agent Substances 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 6
- 239000000835 fiber Substances 0.000 abstract description 6
- 239000004745 nonwoven fabric Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 3
- 235000017550 sodium carbonate Nutrition 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 2
- 239000004744 fabric Substances 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 125000002947 alkylene group Chemical group 0.000 description 8
- 125000005395 methacrylic acid group Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- -1 Polysiloxane Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 241000195940 Bryophyta Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- DDZOQGUFSZLNIA-UHFFFAOYSA-N P(=O)(O)(O)O.[He] Chemical compound P(=O)(O)(O)O.[He] DDZOQGUFSZLNIA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004653 carbonic acids Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion 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
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- OVTFLGWEHKOCRX-UHFFFAOYSA-N helium sulfuric acid Chemical compound S(O)(O)(=O)=O.[He] OVTFLGWEHKOCRX-UHFFFAOYSA-N 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003146 methacrylic ester copolymer Polymers 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 235000011929 mousse Nutrition 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- RUJLHPZAKCVICY-UHFFFAOYSA-J thorium(4+);disulfate Chemical compound [Th+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUJLHPZAKCVICY-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規な感熱ゲル化エマルジョンに関するもので
ある。さらに訝しくは不織布、芯地をはしめとする各種
繊維等の樹脂加工の加熱乾燥時において生しる樹脂の移
行を防止できる感熱ゲル化エマルジョンに関するもので
ある。またこの感熱ゲル化エマルジョンは加熱乾燥時の
ワキ現象の防止、コーティング、バッキング［侍の浸透
防止及び不織布の着色時の顔料の歩留まり向上等にも利
用出来る。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel heat-sensitive gelling emulsion. More particularly, the present invention relates to a heat-sensitive gelling emulsion that can prevent the migration of resin generated during heat-drying of non-woven fabrics, various types of fibers with interlining, and the like during heat-drying. This heat-sensitive gelling emulsion can also be used to prevent wrinkles during heating and drying, to prevent the penetration of coatings and backing materials, and to improve the yield of pigments when coloring non-woven fabrics.
（従来技術）
不織布、芯地をはじめどする繊維等の樹脂加工時の加熱
乾燥において発生する樹脂の移行防に策として、樹脂加
工に用いられる樹脂分１１り液に感熱ゲル化性を与え、
樹脂の移行が発生する前に樹脂をゲル化させ、繊維素材
中での樹脂の移行を防止させることが行われている。樹
脂分散液が天然ゴムおよびＳ Ｂ Ｒ等の合成ゴムラテ
ックスの場合は感熱ゲル化剤として？ｉ、鉛アンモニウ
ムタ）ｉ塩、ポリビニルメチルエーテル、ポリプロピレ
ングリコール、シリコーンポリエーテル」１、重合体、
ポリシロキサンおよび一般のノニオン系界面活性剤等が
使用され、それにより感熱ゲル化性を付与させている。(Prior art) As a measure to prevent the transfer of resin that occurs during heating and drying during resin processing of fibers such as nonwoven fabrics and interlining, heat-sensitive gelling properties are imparted to the resin liquid used for resin processing.
The resin is gelled before resin migration occurs to prevent resin migration within the fiber material. If the resin dispersion is natural rubber or synthetic rubber latex such as SBR, can it be used as a heat-sensitive gelling agent? i, lead ammonium salt, polyvinyl methyl ether, polypropylene glycol, silicone polyether 1, polymer,
Polysiloxane and general nonionic surfactants are used to impart heat-sensitive gelling properties.
しかし、アクリル酸エステル共重合体、エチレン−酢ビ
共重合体およびポリ酢酸ビニル等の合成樹脂エマルジョ
ンには、上記の感熱ゲル化剤は効果がなくまた効果があ
るとしても大量の添加が必要であり、製品の耐水性等の
性能低下を招いてしまう。そのため合成樹脂エマルジョ
ンの使用による繊維等の樹脂加工においては、低温長時
間乾燥で樹脂の移行を防止しているのが現状である。し
かし、この方法は長時間を要する為工程上人きなロスを
生し、極めて不合理であるのが現状である。However, for synthetic resin emulsions such as acrylic ester copolymers, ethylene-vinyl acetate copolymers, and polyvinyl acetate, the above-mentioned heat-sensitive gelling agents are not effective, and even if they are effective, large amounts must be added. This results in a decline in product performance such as water resistance. Therefore, in the resin processing of fibers and the like using synthetic resin emulsions, the current practice is to prevent resin migration by drying at low temperatures and for long periods of time. However, this method requires a long time and causes considerable loss in the process, and is currently extremely unreasonable.
また、最近特許出願公開されたラテックス用感熱ゲル化
剤（特開昭６３−１９３９０１号公報）においても効果
のあるエマルジョンと全く効果のないエマルジョンが存
在し規則性がない。Furthermore, in the heat-sensitive gelling agent for latex that has recently been published as a patent application (Japanese Unexamined Patent Publication No. 63-193901), there are emulsions that are effective and emulsions that are completely ineffective, and there is no regularity.
（発明が解決しようとする課Ｍ）
不織布、芯地をはじめとする繊維等の樹脂加工に使用さ
れる樹脂として、アクリル酸エステル共重合体、スチレ
ン−アクリル酸エステル共重合体、エチレン−酢酸ビニ
ル共重合体およびポリ酢酸ビニル等の合成樹脂エマルジ
ョンは欠かすことのてきない樹脂である。しかし、１−
記した様な移行の問題がある」二、その防止策として最
も有効と考えられる感熱ゲル化システムも従来技術では
効果がなく、また前記特許（特開昭６３−１．９３９０
１号公報）によるゲル化剤では特定のエマルジョンしか
感熱ゲル化性を与えることが出来ない。−力低温長時間
乾燥による移行防止方法も１肪記のごどく極めて不合理
なうえ完全に防止することかできない。本発明の目的は
、上記各種合成樹脂エマルジョン系において規則正しい
Ｌ・δ熱ゲル化性を与える合成樹脂エマルジョン、およ
びこれとゲル化剤との組合せによる感熱ゲル化システム
の開発にある。(Problem M to be solved by the invention) Acrylic ester copolymers, styrene-acrylic ester copolymers, ethylene-vinyl acetate are used as resins for resin processing of fibers such as nonwoven fabrics and interlinings. Synthetic resin emulsions such as copolymers and polyvinyl acetate are indispensable resins. However, 1-
2. The heat-sensitive gelling system, which is considered to be the most effective way to prevent this problem, is ineffective with conventional technology,
With the gelling agent disclosed in Publication No. 1), only a specific emulsion can provide heat-sensitive gelling properties. - The method of preventing migration by drying at low temperature for a long time is extremely unreasonable and cannot be completely prevented. The object of the present invention is to develop a synthetic resin emulsion that provides regular L/δ heat gelling properties in the various synthetic resin emulsion systems mentioned above, and a heat-sensitive gelling system by combining this with a gelling agent.
（課題を解決するための手段）
本発明者らは、上記した問題点を解決するため鋭意研究
を重ねた結果、合成樹脂エマルジョンの樹脂組成中に一
般式（１）に示すアクリルアミＩ・およびまたはメタク
リルアミ１へ誘導体を０．３ ないし１０重量％を含
ませることにより、樹脂加−ＬＩ＋、１の乾燥温度で円
滑なゲル化性を示す感熱ゲル化工マルジョンを開発する
ことができ本発明に至ったものである。(Means for Solving the Problems) As a result of extensive research to solve the above-mentioned problems, the present inventors found that acrylamide I shown in general formula (1) and Alternatively, by incorporating 0.3 to 10% by weight of a derivative into methacrylamine 1, a heat-sensitive gel chemical emulsion that exhibits smooth gelling properties at the drying temperature of resin addition LI+, 1 can be developed. This is what we have come to.
すなわち、本発明は一般式（１）で示されるアクリルア
ミ１くおよび／またはメタクリルアミド誘導体を樹脂組
成中に０．３重量％ないし１０重量％を含む合成樹脂エ
マルジョンにノニオン系界面活性剤およびまたは無機質
塩を添加することを特徴とする感熱ゲル化エマルジョン
Ｒ□
式−（１） Ｈ□Ｃ＝Ｃ
１１Ｎｃ）Ｉ２０Ｒ２ｎ ＝ １〜４
に関するものである。That is, the present invention provides a synthetic resin emulsion containing 0.3% to 10% by weight of an acrylamide and/or methacrylamide derivative represented by the general formula (1) in the resin composition, and a nonionic surfactant and/or a nonionic surfactant. This relates to a heat-sensitive gelling emulsion R□ formula-(1) H□C=C 11Nc)I20R2n = 1 to 4, which is characterized by the addition of an inorganic salt.
（作用）
本発明による合成樹脂エマルジョンは一般式（１）に示
すアクリルアミドおよびまたはメタクリルアミド誘導体
をポリマー組成中に０．３ないし１０重量％を含むアク
リル酸エステルおよびまたはメタクリル酸エステル共重
合体、アクリル酸エステルおよびまたはメタクリル酸エ
ステルと不飽和カルボン酸およびまたはジカルボン酸の
多元共重合体、アクリロニトリルとアクリル酸エステル
およびまたはメタクリル酸エステルの多元共重合体、ア
クリロニトリルとアクリル酸エステル才９よびまたはメ
タクリル酸エステルと不飽和カルホン酸およびまたはジ
カルボン酸の多元共重合体、ノ、チレンとアクリル酸エ
ステルオ９よびｊ：たはメタクリル酸エステルの多元共
重合体、スチレンとアクリル酸エステルおよびまたはメ
タクリル酸エステルと不飽和カルボン酸およびまたはジ
カルボン酸の多元共重合体、塩化ビニリデンとアクリル
酸エステルおよびまたはメタクリルはエステルの多元共
重合体、塩化ビニリデンとアクリル酸エステルおよびま
たはメタクリル酸エステルと不飽和カルボン酸およびま
たはジカルボン酸の多元共重合体、塩化ビニルとアクリ
ル酸エステルおよびまたはメタクリル酸エステルの多元
共重合体、塩化ヒニルとアクリル酸エステルｊ３よびま
たはメタクリル酸エステルと不飽和カルホン酸才９よび
またはジカルボン酸の多元共重合体、エチ１ノンと酢酸
ヒニルとアクリル酸エステルおよびまたはメタクリル酸
エステルの多元共重合体、エチレンと酢酸ビニル共重合
体、エチｌノンと酢酸ビニルとアクリル酸エステルおよ
びまたはメタクリル酸エステルと不飽和カルボン酸およ
びまたはジカルボン酸の多元共重合体、エチレンと酢酸
ビニルと不飽和カルボン酸およびまたはジカルボン酸の
多元共重合体、ポリ酢酸ビニル等の合成樹脂エマルジョ
ンが代表的である。(Function) The synthetic resin emulsion according to the present invention is an acrylic ester and/or methacrylic ester copolymer containing 0.3 to 10% by weight of an acrylamide and/or methacrylamide derivative represented by general formula (1) in the polymer composition. Multi-component copolymers of acid esters and/or methacrylic esters and unsaturated carboxylic acids and/or dicarboxylic acids, multi-component copolymers of acrylonitrile and acrylic esters and/or methacrylic esters, acrylonitrile and acrylic esters and/or methacrylic esters and unsaturated carbonic acid and/or dicarboxylic acid, multi-component copolymer of styrene and acrylic ester, or methacrylic ester, styrene and acrylic ester and/or methacrylic ester and unsaturated Multi-component copolymers of carboxylic and/or dicarboxylic acids, multi-components of vinylidene chloride and acrylic esters and/or methacrylic esters, multi-component copolymers of vinylidene chloride and acrylic esters and/or methacrylic esters and unsaturated carboxylic and/or dicarboxylic acids. Multi-component copolymers, multi-component copolymers of vinyl chloride and acrylic esters and/or methacrylic esters, multi-component copolymers of vinyl chloride and acrylic esters and/or methacrylic esters and unsaturated carbonic acids and/or dicarboxylic acids. , multi-component copolymer of ethylone, vinyl acetate, acrylic ester and/or methacrylic ester, ethylene and vinyl acetate copolymer, ethylone, vinyl acetate, acrylic ester and/or methacrylic ester and unsaturated carboxylic acid Typical examples include a multi-component copolymer of and/or dicarboxylic acid, a multi-component copolymer of ethylene, vinyl acetate, unsaturated carboxylic acid and/or dicarboxylic acid, and a synthetic resin emulsion such as polyvinyl acetate.
合成樹脂エマルジョンは、一般の乳化重合で作成して得
るととがてきるが、一般式（］）で示すアクリルアミド
誘導体が○。３重量％以下の場合はゲル化剤を添加して
も感熱ゲル化性が小さく実用に耐えず、また１０重量％
以上共重合させると合成樹脂エマルジョンの重合中にゲ
ル化し安定なエマルジョンが得られない。Synthetic resin emulsions can be produced by general emulsion polymerization, but acrylamide derivatives represented by the general formula (]) are rated ○. If it is less than 3% by weight, even if a gelling agent is added, the heat-sensitive gelling property is too small to be practical;
If the above copolymerization is carried out, gelation will occur during polymerization of the synthetic resin emulsion, making it impossible to obtain a stable emulsion.
ノニオン系界面活性剤は、低曇点のものが好適であり、
例えば特開昭６３−１９３９０１に記載のゲル化剤であ
り、アルキルフェノール−ホルマリン縮合物のアルキレ
ンオキサド付加物などが挙げられる。無機質塩は、ノニ
オン乳化剤の曇点を低下させる一価から二価の金属塩が
よく、これらにはＮａ２ＣＯ３，Ｎａ２５ｏ、、ＣａＣ
Ｑ７．Ｎａ○ニー１゜ＣａＳ○、、、Ｎａ２ＣＯ３，Ｋ
Ｇ Ｑ 、に２Ｃｏ３゜ＮａＮＯ３，ＰＩ）（Ｎｏ３）
７．等がある。The nonionic surfactant preferably has a low clouding point,
Examples include gelling agents described in JP-A-63-193901, including alkylene oxide adducts of alkylphenol-formalin condensates. The inorganic salt is preferably a monovalent to divalent metal salt that lowers the cloud point of the nonionic emulsifier, and these include Na2CO3, Na25o, CaC
Q7. Na○knee 1゜CaS○,,,Na2CO3,K
G Q, 2Co3゜NaNO3, PI) (No3)
7. etc.
ゲル化システムは上記した合成樹脂エマルジョン１００
重量部に苅しゲル化剤として低曇点ノニオン系界面活性
剤０から３重量部およびまたは無機質塩Ｏから３重量部
を添加することにより合成樹脂エマルジョンに感熱ゲル
化性を付与するものである。The gelling system is the above-mentioned synthetic resin emulsion 100.
Heat-sensitive gelling properties are imparted to the synthetic resin emulsion by adding 0 to 3 parts by weight of a low cloud point nonionic surfactant and/or 3 parts by weight of an inorganic salt as a gelling agent to the weight part. .
これらのゲル化剤は単独でもよいが併用することにより
更に効果を高めることができる１、しかし、合成樹脂中
にそれぞれ３重量部以−［１併用使用した場合はゲル化
効果はあるものの１１）・られだ製品の耐水性等の性能
低下を招いてしまい実際の使用に耐えないものとなる。These gelling agents may be used alone, but the effect can be further enhanced by using them in combination1.・Performance such as water resistance of the product will deteriorate and it will not be able to withstand actual use.
（実施例） 次に実施例により、本発明をさらに詳細に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例１
第２リン酸す１ヘリウムの＋２含水塩０．０５畢量部と
ドテシルベンゼンスルホン酸すＩ−リウム０．１２重刑
部と蒸留水１７．８３５重砥重任撹拌機イ」き５つロセ
バラフラスコに仕込み窒素ガスを通気さぜろ。４Ｎｌ拌
は１５０ ｒｐｌｎて行いウォーターバスにより内温を
６０’Ｃに調整する。（窒素通気は熟成終了まで行う。Example 1 0.05 part of +2 hydrated salt of dibasic 1-helium phosphate, 0.12 parts of sodium dodecylbenzenesulfonate, 17.835 parts of distilled water, and 5 parts of diluted helium phosphate. Place the rose rosette in a flask and aerate it with nitrogen gas. Stirring for 4Nl was performed at 150 rpm, and the internal temperature was adjusted to 60'C using a water bath. (Nitrogen aeration is continued until the end of ripening.
）次にエチルアクリレート２１．６重量部とブチルアク
リレート［９，１重量部とメタクリル１％ｊ０．８５
重量部とＮ−メチロールメタクリルアミ］へ１．２ 重
量部にドデシルベンセンスルホン酸すトリウム０，２２
重量部とエチレンオキサイ１ヘイ１加モル数１２モル
のポリオキシエチ１ノンノニルフェノールエーテル１．
０ 重量部とエチレンオキサイド伺加モル数４０モルの
ポリオキシエチ］ノンノニルフェノールエーテル １．
０重量部と蒸留水３０ 、８ 重量部を混合し強制乳化
させモノマー乳化液を作る。このモノマー乳化液の５重
量％をセバラフラスコ内に添加し更に過硫酸カリウｌ、
０．０５重量部と亜硫酸水素すｌ−リウム０．０２重量
部を添加して％’Ｈ合を開始させる。) Next, 21.6 parts by weight of ethyl acrylate, 9.1 parts by weight of butyl acrylate and 1% methacrylate j0.85
1.2 parts by weight and N-methylol methacrylamide] 0.22 parts by weight of thorium dodecylbenzene sulfonate
parts by weight and 1 ethylene oxide, 1 hey, and 12 moles of polyoxyethyl 1 nonnonylphenol ether.
0 parts by weight and 40 moles of ethylene oxide in polyoxyethyl nonnonylphenol ether 1.
0 parts by weight and 30.8 parts by weight of distilled water were mixed and forcedly emulsified to prepare a monomer emulsion. 5% by weight of this monomer emulsion was added to a Severa flask, and potassium persulfate was added.
0.05 parts by weight and 0.02 parts by weight of sl-lium bisulfite are added to initiate the %'H combination.
重合開始１０分後より温度をＣ： ５ ＋ ２ ’Ｃに
保ち／ｊ）が）ら残っているモノマー乳化７段を：ｑ
ＩＩ、５間で連続添加する。またモノマー乳化液の添加
と同時に過硫酸カリウム０．０９ 重量部を、・；へ留
水３重量部に溶解させたものと亜硫酸水素す１ヘリウｌ
ｘ ０ 、０４ 重量部を蒸留水３重量部に溶解した
ものを同しく３時間で連続添加する。、モノマー乳化港
添加終Ｙ後同温度で］時間熟成を行ったｉ糸冷却する。10 minutes after the start of polymerization, the temperature was kept at C: 5 + 2'C/j) and the remaining 7 stages of monomer emulsification from:q
II, continuous addition for 5 minutes. At the same time as adding the monomer emulsion, 0.09 parts by weight of potassium persulfate was dissolved in 3 parts by weight of distilled water and 1 helium of hydrogen sulfite was added.
A solution of x 0 , 04 parts by weight in 3 parts by weight of distilled water was added continuously over the same 3 hours. After the addition of the monomer emulsification port, the yarn was aged at the same temperature for an hour and then cooled.
）’ｌ ／ｒｉが３０°Ｃ以下になった時点でアンモニ
ア水 ０．○２５ ’Ｊ’、 Ｒ部＆ ｍ 力１１ Ｌ
／、ヘースエマルジョンを／、ｌｊた。)'l When /ri is below 30°C, add ammonia water 0. ○25 'J', R part & m Force 11 L
/, Heath emulsion /, lj.
得られたヘースエマルジョンは、濃度・１５−中け％、
粘度８０ｃｐｓ、 ｐＨ６、５てあった。このヘースエ
マルジョン１００重量部ｉ、こ対し２０重」１Ｖ％にイ
、釈したアルキルフェノール−ホルマリン縮合物のアル
キレンオキサイド付加物（花１．（株）製うテ１３刀川
ぐＰ−５１５０）を５重量部（ｂど硫酸すトリウ１１の
１０重量％水溶液１０重量部を添加し！・δ熱ゲル化エ
マルジョンを得た。この感熱ゲル化エマルシ三ンは□ｉ
ｉｔ′温（０〜３０°Ｃ）で安定であったか、〔３５°
（゛に昇温させると直ちにゲル化（凝集）した。ゲル化
物は再び温度を下げても再分散しなかった。The obtained hese emulsion has a concentration of 15-medium%,
The viscosity was 80 cps and the pH was 6.5. To 100 parts by weight of this Hess emulsion was added an alkylene oxide adduct of an alkylphenol-formalin condensate (Hana 1. Ute 13 Katagawa P-5150 manufactured by Hana 1 Co., Ltd.) diluted to 1 V% by 20 parts by weight. 5 parts by weight (b) 10 parts by weight of a 10% aqueous solution of sodium sulfate 11 was added to obtain a δ heat-gelled emulsion.This heat-sensitive gelled emulsion was □i
It was stable at temperatures (0 to 30°C) or [35°
(When the temperature was raised to ゛, it gelled (agglomerated) immediately. Even when the temperature was lowered again, the gelled product did not redisperse.
実施例２
実施例１に準じてペースエマルジョンを作成したが、混
合上ツマー組成を次の様に変えて重合を行った。Example 2 A pace emulsion was prepared according to Example 1, but polymerization was carried out by changing the composition of the emulsions as follows.
混合モノマー組成
メチルメタクリレート ２４．８ 重量部ブ
チルアクリレ−１−１６，９５重量部Ｎ−メチロールメ
タクリルアミド １．０ 重量部重合、冷却後アンモ
ニア水０．００９ 重量部を添加してペースエマルジョ
ンを得た。得られたペースエマルジョンは、濃度４５重
量％、粘度１２０ ｃｐｓ、 ＰＨ６、５であった。こ
のペースエマルジョン１００重量部に対し２０重量％に
希釈したアルキルフェノール−ホルマリン縮合物のアル
キレンオキサイ）・付加物（花王（株）製うテムルＮＰ
−５１５０）を２重量部と硫酸す１ヘリウムの１０重量
％水溶液４重量部を添加して感熱ゲル化エマルジョンを
得た。この感熱ゲル化エマルジョンは常温（０〜３０°
Ｃ）で安定であったが、６０°Ｃに昇温させると直ちに
ゲル化（疑り↓）した。ゲル化物は再び温度を下げても
再分散しなかった。Mixed monomer composition Methyl methacrylate 24.8 parts by weight Butyl acrylate 1-16.95 parts by weight N-methylolmethacrylamide 1.0 parts by weight After polymerization and cooling, 0.009 parts by weight of aqueous ammonia was added to obtain a paste emulsion. The resulting pace emulsion had a concentration of 45% by weight, a viscosity of 120 cps, and a pH of 6.5. An alkylphenol-formalin condensate diluted to 20% by weight with respect to 100 parts by weight of this pace emulsion (alkylene oxy) adduct (Utemul NP manufactured by Kao Corporation)
-5150) and 4 parts by weight of a 10% by weight aqueous solution of helium sulfate were added to obtain a heat-sensitive gelling emulsion. This heat-sensitive gel emulsion is heated at room temperature (0 to 30°C).
C) was stable, but when the temperature was raised to 60°C, it immediately gelled (suspect ↓). The gelled product did not redisperse even when the temperature was lowered again.
実施例３
実施例１に準じてペースエマルジョンを作成したが、混
合モノマー組成を次の様に変えて重合を行った。Example 3 A pace emulsion was prepared according to Example 1, but polymerization was carried out with the mixed monomer composition changed as follows.
混合モノマー組成
メチルメタクリレ−１−２／１ 、８ 型部一部ブチ
ルアクリレート １６．９５重量部Ｎ
Ｎツメヘオキシメチルアクリルアミ１： １．ｏ
重量部重合、冷却後アンモニア水○、０００ 重量部
を添加してペースエマルジョンを得た。得られたペース
エマルジョンは、濃度４５重量％、粘度Ｌ５０ｃｐｓ、
ＰＨ６、５であった。このペースエマルジョン１００
重量部に対し２０重屈％に希釈したアルキルフェノール
−ホルマリン縮合物のアルキレンオキサイド付加物（花
王（ａ）製うテ１３ルＮ Ｐ −５１５０）を５重量部
と硫酸すＩ−リウ１１の１０重量％水溶液１０重量部を
添加して感熱ゲル化エマルジョンを得た。この感熱ゲル
化エマルジョンは常温（○〜３０’Ｃ）で安定であった
が、７５°Ｃに昇温させると直ちにゲル化（凝集）した
。ゲル化物は再び温度を下げても再分散しなかった。Mixed monomer composition Methyl methacrylate-1-2/1, 8 Mold part: Butyl acrylate 16.95 parts by weight N
N-Tumeheoxymethylacrylamide 1: 1. o
After polymerization and cooling, 0.000 parts by weight of aqueous ammonia was added to obtain a pace emulsion. The obtained pace emulsion had a concentration of 45% by weight, a viscosity of L50 cps,
The pH was 6.5. This pace emulsion 100
5 parts by weight of an alkylene oxide adduct of an alkylphenol-formalin condensate (Ute 13 NP-5150 manufactured by Kao (a)) diluted to 20% by weight based on 10 parts by weight of sulfuric acid I-RIU 11. % aqueous solution was added to obtain a heat-sensitive gelling emulsion. This heat-sensitive gelling emulsion was stable at room temperature (○ to 30'C), but immediately gelled (agglomerated) when the temperature was raised to 75°C. The gelled product did not redisperse even when the temperature was lowered again.
実施例４
実施例１に準してペースエマルジョンを作成したが、混
合モノマー組成を次の様に変えて重合を行った。Example 4 A pace emulsion was prepared according to Example 1, but polymerization was carried out with the mixed monomer composition changed as follows.
混合モノマー組成
メチルメタクリレ−ｈ ２４．８
重量部ブチルアクリレ−ｌ−１６，９５重量部Ｎ−イソ
ブ］〜キシメチルアクリルアミ＋： １．０重量部重
合、冷却後アンモニア水０．００９ 重量部を添加して
ペースエマルジョンを得た。得られたペースエマルジョ
ンは、濃度４５重量％、粘度２００ ｃｐｓ、 ｐＨ６
、５であった。このペースエマルジョン１００重量部に
対し２０重量％に希釈したアルキルフェノール−ホルマ
リン縮合物のアルキレンオキサイトイ」加物（花王（株
）製うテムルＮ Ｐ −５１５０）を５重量部と硫酸ナ
トリウムの１０重量％水溶液１０重量部を添加して感熱
ゲル化エマルジョンを得た。この感熱ゲル化エマルジョ
ンは常温（０〜３０９Ｃ）で安定であったか、７５°Ｃ
に昇温させると直ちにゲル化（凝集）した。ゲル化物は
再び温度を下げても再分散しなかった。Mixed monomer composition Methyl methacrylate-h 24.8
Part by weight butyl acrylate-l-16,95 parts by weight N-isobu] - oxymethylacrylamide+: 1.0 part by weight After polymerization and cooling, 0.009 part by weight of aqueous ammonia was added to obtain a pace emulsion. The resulting pace emulsion had a concentration of 45% by weight, a viscosity of 200 cps, and a pH of 6.
, 5. To 100 parts by weight of this pace emulsion, 5 parts by weight of an alkylphenol-formalin condensate diluted to 20% by weight (Utemur NP-5150 manufactured by Kao Corporation) and 10% by weight of sodium sulfate were added. A heat-sensitive gelling emulsion was obtained by adding 10 parts by weight of an aqueous solution. This heat-sensitive gelling emulsion was stable at room temperature (0-309C) or at 75°C.
When the temperature was raised to , gelation (agglomeration) occurred immediately. The gelled product did not redisperse even when the temperature was lowered again.
実施例５
実施例２て得たペースエマルジョン１００重量部に対し
２０重量％に希釈したアルキルフェノール−ホルマリン
縮合物のアルキレンオキサイド付加物（花王（株）製う
テ１１ルＮＰ−５−１５０）を０．５重量部を添加して
感熱ゲル化エマルジ３ンを得た。この感熱ゲル化エマル
ジョンは常温（０〜３０℃）で安定であったか、７８°
Ｃに賓温させると直ちにゲル化（凝集）した。ゲル化物
は再び温度を下げても再分散しなかった。Example 5 To 100 parts by weight of the pace emulsion obtained in Example 2, 0% of an alkylene oxide adduct of an alkylphenol-formalin condensate (Ute 11 NP-5-150 manufactured by Kao Corporation) diluted to 20% by weight was added. 0.5 parts by weight was added to obtain a heat-sensitive gelling emulsion. This heat-sensitive gelling emulsion was stable at room temperature (0 to 30°C) or 78°C.
When heated to temperature C, gelation (agglomeration) occurred immediately. The gelled product did not redisperse even when the temperature was lowered again.
実施例６
実施例２て得たペースエマルジョン］、 Ｏ０重足部に
対し２０重量％に希釈したアルキルフェノール−ホルマ
リン縮合物のアルキレンオキサイ１へ付加物（花王（株
）製うテムルＮ Ｐ −５１５０）を１．５重量部を添
加して感熱ゲル化エマルジョンを得た。この感熱ゲル化
エマルジョンは常温（０〜３００Ｃ）で安定であったが
、７７℃に昇温させると直ちにゲル化（ＩＩ）した。ゲ
ル化物は再び温度を下げても再分散しなかった。Example 6 Pace emulsion obtained in Example 2], an adduct of an alkylphenol-formalin condensate diluted to 20% by weight with respect to the O0 heavy foot part to alkylene oxy-1 (Utemul NP-5150 manufactured by Kao Corporation) ) was added to obtain a heat-sensitive gelling emulsion. This heat-sensitive gelling emulsion was stable at room temperature (0 to 300C), but immediately gelled (II) when the temperature was raised to 77C. The gelled product did not redisperse even when the temperature was lowered again.
実施例７
実施例２で得たペースエマルジョン１００重量部に対し
２０重量％に希釈したアルキルフェノール−ホルマリン
縮合物のアルキ１ノンオキサイド付加物（花王（株）製
うテムルＮ Ｐ −５１５０）を２．５重量部を添加し
て感熱ゲル化エマルジョンを得た。この感熱ゲル化エマ
ルジョンは常温（０〜３０°Ｃ）で安定であったが、７
４°Ｃに昇温させると直ちにゲル化（凝集）した。ゲル
化物は再び温度を下げても再分散しなかった。Example 7 To 100 parts by weight of the pace emulsion obtained in Example 2, an alkyl 1 non oxide adduct (Utemul NP-5150 manufactured by Kao Corporation) of an alkylphenol-formalin condensate diluted to 20% by weight was added to 2. A heat-sensitive gelling emulsion was obtained by adding 5 parts by weight. This heat-sensitive gelled emulsion was stable at room temperature (0 to 30°C), but
When the temperature was raised to 4°C, gelation (agglomeration) occurred immediately. The gelled product did not redisperse even when the temperature was lowered again.
実施例８
実施例２て得たペースエマルジョン１００重量部に対し
硫酸すＩ・リウムの１０重量％水溶液３重量部を協力］
１して感熱ゲル化エマルジョンを得た。Example 8 3 parts by weight of a 10% by weight aqueous solution of I.lium sulfate was added to 100 parts by weight of the pace emulsion obtained in Example 2]
1 to obtain a heat-sensitive gelling emulsion.
この感熱ゲル化エマルジョンは常温（０〜３０℃）で安
定であったが、７６°Ｃに昇温させると直ぢにゲル化（
凝集）した。ゲル化物は再び温度を下げても再分散しな
かった。This heat-sensitive gelling emulsion was stable at room temperature (0 to 30°C), but when the temperature was raised to 76°C, it immediately gelled (
agglomerated). The gelled product did not redisperse even when the temperature was lowered again.
実施例９
実施例２で得たペースエマルジョン１００重量部に対し
硫酸すトリウムの１０隼飛％水溶液５重量部を添加して
感熱ゲル化エマルジョンを得た。Example 9 To 100 parts by weight of the pace emulsion obtained in Example 2, 5 parts by weight of a 10% aqueous solution of thorium sulfate was added to obtain a heat-sensitive gelling emulsion.
この感熱ゲル化エマルジョンは常温（Ｏ〜３０’Ｃ）で
安定であったが、７５°Ｃに、ｊ：’ｌ、渇さぜると直
ちにゲル化（凝集）した１、ゲル化物は再び温度を下げ
ても再分散しなかった。This heat-sensitive gelling emulsion was stable at room temperature (0~30'C), but when heated to 75°C, it immediately gelled (agglomerated). It did not redisperse even when the temperature was lowered.
比較例１
実施例１に準してペースエマルジョンを作成したが、混
合モノマー組成中のＮ−メチロールメタクリルアミドを
用いずに重合を行った。畏られたエマルジョンは、濃度
４４重量％、粘度５０ＣｐＳ、ＰＨ６、５であった。
このｌ＼−スエマルジョン」００重Ｒ部に対し２０重量
％に希釈したアルキルフェノール−ホルマリン縮合物の
アルキ１ノンオキサイド付加物（花王（株）製うテ１１
ルＮＰ−５１，５０）を５重量部と硫酸す１〜リウムの
１０里量％水溶液１０重量部を添加したエマルジョンを
得たがこれは９５°Ｃに昇温しでもゲル化せず安定であ
った。Comparative Example 1 A pace emulsion was prepared according to Example 1, but polymerization was carried out without using N-methylolmethacrylamide in the mixed monomer composition. The emulsion in question had a concentration of 44% by weight, a viscosity of 50 CpS, and a pH of 6.5.
An alkyl 1 non-oxide adduct of an alkylphenol-formalin condensate diluted to 20% by weight based on 00 parts R of this l\-sue emulsion (Ute 11 manufactured by Kao Corporation)
An emulsion was obtained by adding 5 parts by weight of NP-51, 50) and 10 parts by weight of a 10% aqueous solution of sodium to lithium sulfate, but this emulsion remained stable without gelation even when heated to 95°C. there were.
比較例２
実施例１に準してペースエマルジョンを作成したが、見
合モノマー組成中のＮ−メチロールメタクリルアミドを
０．０８７ 重量部として重合を行った。得られたエマ
ルジョンは、濃度４４重量％、粘度６０ＣＰＳ、円４６
．５であった。このペースエマルジョン１００重量部に
刻し２０重量％に希釈したアルキルフェノール−ホルマ
リン綜合物のアルキレンオキサイド付加物（花王（株）
製うテムルＮＰ−５１５０）を５重量部と硫酸す１−リ
ウムの１０重量％水溶液１０重量部を添加したエマルジ
ョンを得たがこれは９５°Ｃにｙ１温しても増粘はした
もののゲル化はしなかった。また、冷却することにより
元の粘度に戻った。Comparative Example 2 A pace emulsion was prepared according to Example 1, but polymerization was carried out using 0.087 parts by weight of N-methylolmethacrylamide in the monomer composition. The obtained emulsion had a concentration of 44% by weight, a viscosity of 60CPS, and a circle of 46%.
．． It was 5. Alkylene oxide adduct of alkylphenol-formalin composite (Kao Corporation), which was chopped into 100 parts by weight of this paste emulsion and diluted to 20% by weight.
An emulsion was obtained by adding 5 parts by weight of Temul NP-5150) and 10 parts by weight of a 10% aqueous solution of 1-lium sulfate, but the emulsion remained a gel even though it thickened even after heating to 95°C. It did not change. Moreover, the original viscosity was restored by cooling.
比較例３
実施例１に準じてペースエマルジョンを作成したが、混
合モノマー組成を一ト記の様にして重合を行った。Comparative Example 3 A pace emulsion was prepared according to Example 1, but polymerization was carried out using the mixed monomer composition as described above.
混合モノマー組成
スチレン ３８．／］重量部ブチルアクリ
レー１へ ９．６重置部重合、冷却後アンモニア水
を０．０８ ル量部添加してペースエマルジョンを得た
。得らオしたエマルジョンは、濃度５０重重量、、粘度
５００ｃ１〕ｓ、ＰＩ（６，５であった。 このペース
エマルジョン１００重量部に対し２０重量％に希釈した
アルキルフェノール−ホルマリン縮合物のアルキ１ノン
オギサイド付加物（花王（株）製うテ１１ルＮ Ｐ −
５１，５０）を５重量部と硫酸す１ヘリウ１３の１０畢
１％水溶液１０重量部を添加したエマルジョンを得たか
これは９５°Ｃに昇温しでも増粘はしたもののゲル化は
しなかった。また、冷却することにより元の粘度に戻っ
た。Mixed monomer composition styrene 38. 9.6 parts by weight to butyl acrylate 1 After polymerization and cooling, 0.08 parts of ammonia water was added to obtain a paste emulsion. The obtained emulsion had a concentration of 50% by weight, a viscosity of 500c1]s, and a PI (6,5). An alkylphenol-formalin condensate diluted to 20% by weight with respect to 100 parts by weight of this pace emulsion. Adduct (manufactured by Kao Corporation)
An emulsion was obtained in which 5 parts by weight of 51,50) and 10 parts by weight of a 1% aqueous solution of sulfuric acid, 1 helium 13, and 10 parts by weight were added.The emulsion thickened but did not gel even when heated to 95°C. Ta. Moreover, the original viscosity was restored by cooling.
比較例４
実施例５にｒ（ＩＩシてペースエマルジョンを作成した
が、混合モノマー中のＮ−メチロールアクリルアミ１へ
を抜いて重合した。１Ｈられたエマルジョンは、濃度４
１．５重量％、粘度３０００ ｃｐｓ、 ＰＨ８，５で
あった。 このムースエマルジョン１００重量部に対し
２０重量％に希釈したアルキルフェノール−ホルマリン
縮合物のアルキレンオキサイド付加物（花王（株）製う
テムルＮＰ−５１５０）を５重量部と硫酸すｉ・リウム
の１０重量％水溶液１０重量部を添加したエマルジョン
を得たがこれは９５°Ｃに昇温しでもゲル化せず安定で
あった。Comparative Example 4 A paste emulsion was prepared using r(II) in Example 5, but N-methylolacrylamide 1 in the mixed monomer was removed and polymerized.
The content was 1.5% by weight, the viscosity was 3000 cps, and the pH was 8.5. To 100 parts by weight of this mousse emulsion, 5 parts by weight of an alkylene oxide adduct of an alkylphenol-formalin condensate (Utemul NP-5150 manufactured by Kao Corporation) diluted to 20% by weight and 10% by weight of sodium and lium sulfate. An emulsion was obtained by adding 10 parts by weight of the aqueous solution, which did not gel and remained stable even when the temperature was raised to 95°C.
比較例５
実施例５に準じてペースエマルジョンを作成したが、混
合モノマー組成を次の様にして重合した。Comparative Example 5 A pace emulsion was prepared according to Example 5, but polymerization was carried out using the following mixed monomer composition.
混合モノマー組成
メチルメタクリレ−１−２２，３重量部ブチルメタクリ
レ−１−１８，３重量部アクリロニトリル
］、７７重量部２ヒドロキシエチルメタクリ
レート１０重量部イタコン酸
０．５重量部アクリルアミド
０．７重量部得られたエマルジョンは、濃度４５重
量％、粘度５０００ｃｐｓ、 ＰＩＩ８．５であった。Mixed monomer composition Methyl methacrylate - 1-22.3 parts by weight Butyl methacrylate - 1-18.3 parts by weight Acrylonitrile
], 77 parts by weight 2-hydroxyethyl methacrylate 10 parts by weight itaconic acid
0.5 parts by weight acrylamide
The emulsion obtained at 0.7 parts by weight had a concentration of 45% by weight, a viscosity of 5000 cps, and a PII of 8.5.
このベースエマルジョン１００重量部に対し２０重量％
［こ界暇くしたアルキルフェノール−ホルマリン縮合物
のアルキレンオキサイド付加物（花王（株）製うテｌ＼
／ｌ／ＮＰ−５１５０）を５型皿部と硫酸ナトワウ１−
１０重量％水溶液１０重量部を添加したエマルジョンを
得たがこれは９５°Ｃに肩温してもゲル化せず安定であ
った・
実施例および比較例をまとめると第１表の様しこなった
・
（発明の効果）
本発明による感熱ゲル化エマルジョンは、合成樹脂エマ
ルジョンに該所定量のゲル化刑を添加する事により規則
正しい感熱ゲル化性を与える事が出来、合成樹脂本来の
性能を低下させる事なく不織布、芯地をはじめとする各
種繊維等の樹脂加工における乾燥時の樹脂の移行防止に
有効なエマルジョンを与えるものである。20% by weight based on 100 parts by weight of this base emulsion
[Alkylene oxide adduct of alkylphenol-formalin condensate (manufactured by Kao Corporation)]
/l/NP-5150) with the type 5 dish part and Natowa sulfate 1-
An emulsion was obtained by adding 10 parts by weight of a 10% aqueous solution, which was stable without gelation even when heated to 95°C. Table 1 summarizes the examples and comparative examples. (Effects of the Invention) The heat-sensitive gelling emulsion according to the present invention can impart regular heat-sensitive gelling properties by adding a predetermined amount of the gelling agent to the synthetic resin emulsion, thereby enhancing the inherent performance of the synthetic resin. It provides an emulsion that is effective in preventing resin migration during drying in resin processing of various fibers such as nonwoven fabrics and interlinings without degrading the quality.
Claims (1)
タクリルアミド誘導体を樹脂組成中に０．３重量％ない
し１０重量％を含む合成樹脂エマルジョンにノニオン系
界面活性剤および／または無機質塩を添加することを特
徴とする感熱ゲル化エマルジョン。 一般式（１） ▲数式、化学式、表等があります▼ Ｒ＿１；Ｈ又はＣＨ＿３ Ｒ＿２；Ｈ又はＣｎＨ＿２＿ｎ＿＋＿１ ｎ＝１〜４[Scope of Claims] A nonionic surfactant and/or inorganic salt is added to a synthetic resin emulsion containing 0.3% to 10% by weight of an acrylamide and/or methacrylamide derivative represented by general formula (1) in the resin composition. A heat-sensitive gelling emulsion characterized by the addition of. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_1; H or CH_3 R_2; H or CnH_2_n_+_1 n=1 to 4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1130186A JP2668580B2 (en) | 1989-05-25 | 1989-05-25 | Heat-sensitive gelled emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1130186A JP2668580B2 (en) | 1989-05-25 | 1989-05-25 | Heat-sensitive gelled emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02308844A true JPH02308844A (en) | 1990-12-21 |
| JP2668580B2 JP2668580B2 (en) | 1997-10-27 |
Family
ID=15028135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1130186A Expired - Fee Related JP2668580B2 (en) | 1989-05-25 | 1989-05-25 | Heat-sensitive gelled emulsion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2668580B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06285422A (en) * | 1992-06-05 | 1994-10-11 | Kikusui Kagaku Kogyo Kk | Formation of coating film |
| JP2007524773A (en) * | 2003-12-22 | 2007-08-30 | ビーエーエスエフ アクチェンゲゼルシャフト | Compositions for impregnating fibers, fabrics and nettings that provide protective activity against pests |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7408018B1 (en) | 2022-03-01 | 2024-01-04 | 日本エイアンドエル株式会社 | Method for producing a laminated object, heat-sensitive gelling agent, and composition for laminated manufacturing |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5013308A (en) * | 1973-06-11 | 1975-02-12 | ||
| JPS59187658A (en) * | 1983-04-01 | 1984-10-24 | エア−・プロダクツ・アンド・ケミカルス・インコ−ポレ−テツド | Nonwoven product with reduced residual free formaldehyde |
| JPS63193901A (en) * | 1987-02-09 | 1988-08-11 | Kao Corp | Heat-sensitive gelling agent for latex |
| JPS6443589A (en) * | 1987-07-31 | 1989-02-15 | Reichhold Chemicals Inc | Binder composition substantially leaving no folmaldehyde |
| JPH0229407A (en) * | 1988-06-03 | 1990-01-31 | Basf Ag | Dispersion of non-tertiary butyl(meth)acrylate copolymer having glass transition temperature of -10 degree or less |
-
1989
- 1989-05-25 JP JP1130186A patent/JP2668580B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5013308A (en) * | 1973-06-11 | 1975-02-12 | ||
| JPS59187658A (en) * | 1983-04-01 | 1984-10-24 | エア−・プロダクツ・アンド・ケミカルス・インコ−ポレ−テツド | Nonwoven product with reduced residual free formaldehyde |
| JPS63193901A (en) * | 1987-02-09 | 1988-08-11 | Kao Corp | Heat-sensitive gelling agent for latex |
| JPS6443589A (en) * | 1987-07-31 | 1989-02-15 | Reichhold Chemicals Inc | Binder composition substantially leaving no folmaldehyde |
| JPH0229407A (en) * | 1988-06-03 | 1990-01-31 | Basf Ag | Dispersion of non-tertiary butyl(meth)acrylate copolymer having glass transition temperature of -10 degree or less |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06285422A (en) * | 1992-06-05 | 1994-10-11 | Kikusui Kagaku Kogyo Kk | Formation of coating film |
| JP2007524773A (en) * | 2003-12-22 | 2007-08-30 | ビーエーエスエフ アクチェンゲゼルシャフト | Compositions for impregnating fibers, fabrics and nettings that provide protective activity against pests |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2668580B2 (en) | 1997-10-27 |
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