JP3553653B2 - Fiber treatment agent mainly composed of acrylic emulsion - Google Patents
Fiber treatment agent mainly composed of acrylic emulsion Download PDFInfo
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- JP3553653B2 JP3553653B2 JP20410394A JP20410394A JP3553653B2 JP 3553653 B2 JP3553653 B2 JP 3553653B2 JP 20410394 A JP20410394 A JP 20410394A JP 20410394 A JP20410394 A JP 20410394A JP 3553653 B2 JP3553653 B2 JP 3553653B2
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- emulsion
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- 239000000839 emulsion Substances 0.000 title claims description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 22
- 239000000835 fiber Substances 0.000 title claims description 22
- 239000003795 chemical substances by application Substances 0.000 title claims description 13
- 239000000178 monomer Substances 0.000 claims description 40
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 21
- 239000000084 colloidal system Substances 0.000 claims description 19
- 230000001681 protective effect Effects 0.000 claims description 19
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 9
- 239000003505 polymerization initiator Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920003086 cellulose ether Polymers 0.000 claims description 4
- 238000007717 redox polymerization reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 11
- -1 alkoxyethyl acrylate Chemical compound 0.000 description 9
- 238000013508 migration Methods 0.000 description 9
- 230000005012 migration Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012966 redox initiator Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229920003169 water-soluble polymer Polymers 0.000 description 7
- 239000003999 initiator Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-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
- 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
- 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 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-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
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 description 1
- FALCQDAWENTNHF-UHFFFAOYSA-N ethenyl(2-methoxyethoxy)silane Chemical compound COCCO[SiH2]C=C FALCQDAWENTNHF-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は繊維を処理して、風合い、強度、耐水性、耐溶剤性、耐薬品性等の物性を向上させる繊維処理剤に関する。さらに詳しくは、乾燥時にエマルジョン粒子が局在化するマイグレーションが発生せず優れた風合いを与える繊維処理剤に関する。
【０００２】
【従来の技術】
従来より繊維の処理には合成樹脂の溶液やエマルジョンが用いられてきた。
繊維の処理で要求される最も重要な性能は、風合いである。保護コロイドを用いて得たエマルジョンを用いて繊維を処理すると界面活性剤を用いて得たエマルジョンを使用した場合に較べて繊維の風合いが向上する。
しかしながら、保護コロイドを用いて重合することの出来たエマルジョンとしては酢酸ビニル系のエマルジョンが主であったが、このエマルジョンは耐水性が悪く、しかも酢酸臭があるという欠点があった。
一方アクリル系エマルジョンは酢酸臭もなく、耐水性も良好であるが、重合性が悪く凝集し易いので保護コロイドではエマルジョン重合が出来なかった。
界面活性剤を用いて重合したアクリル系エマルジョンを用いて繊維を処理すると、風合いが悪く、特にバルキイ的風合いは得られない。
さらに、界面活性剤を用いて得たアクリル系エマルジョンは粒子径が大略０．５μｍ以下の小さい粒子であるためマイグレーションしやすい欠点を有している。
ここで言うマイグレーションとは、基材にエマルジョンを含浸後ドライヤー等で強制乾燥させる際、基材表面の温度が内部に較べて高く表面で水の蒸発が激しく起こるため、エマルジョン粒子が水の流れにつられて表面に移動し樹脂が局在化することでこのような現象により強度、触感、印刷適性、吸水性等に悪影響をおよぼす。
【０００３】
【発明が解決しようとする課題】
本発明は、従来の問題点の解決を図るとともに、風合いの良好な、マイグレーションのない、酢酸臭のない繊維処理剤を提供しようとするものである。
【０００４】
【課題を解決するための手段】
本発明による繊維処理剤は、アクリル系単量体と該単量体と共重合可能な単量体を、単量体に対し２〜１０重量％の保護コロイドの存在下でレドックス系重合開始剤を用い、重合温度６５℃以下で乳化重合して得た、粒子径１．０〜３．０μｍのアクリル系エマルジョンを主剤とするものである。
本発明の好ましい態様によれば、繊維処理剤において、アクリル系単量体と共重合する単量体として酢酸ビニルを全体量体の２５重量％以下使用することが好ましい。
本発明の別の好ましい態様によれば、前記保護コロイドはセルロースエーテル系および／またはポリビニルアルコール系である。
本発明のさらに別の好ましい態様によれば、繊維処理剤において、アクリル系単量体を全単量体の７０〜９９重量％使用することが好ましい。
【０００５】
【作用】
本発明の第１の特徴は保護コロイドを用いて重合した、粒子径１．０〜３．０μｍのアクリル系エマルジョンを用いることである。
本発明者は保護コロイドを用いて重合した酢酸ビニル系エマルジョンで処理した繊維は風合いが良いのに、界面活性剤を用いて重合したアクリル系エマルジョンで処理した繊維の風合いが悪いのかを研究した結果エマルジョン粒子の大きさが重大な影響を与えていることを解明した。つまりエマルジョン粒子の粒径が小さいと繊維の風合いは劣化する。
粒径が１．０〜３．０μｍの粒径でないと質感のあるバルキイな風合いは得られない。また１．０μｍ以下であるとマイグレーションが発生する傾向が大きい。粒径が３．０μｍ以上になるとエマルジョンの希釈安定性が劣化する傾向が大きい。
【０００６】
本発明の第２の特徴は、保護コロイドの使用量である。単量体に対し保護コロイドの量は２〜１０重量％でなければならない。２重量％より少ないとエマルジョンの粒子径が０．５μｍ以上の大きさにならない。そのため処理した繊維の風合いが良好とならず、またマイグレーションも発生する。保護コロイドが１０重量％以上になると増粘を生じ重合時の安定性を悪くし、エマルジョンの安定性も劣化し、さらに耐水性も低下する。
【０００７】
本発明の第３の特徴は重合開始剤としてレドックス系の開始剤を使用し０℃〜６５℃で重合することである。良好なエマルジョンを得るためには重合温度を６５℃以下にする必要があり、そのためには重合開始剤としてレドックス系開始剤を使用する必要がある。この重合条件でないと保護コロイドとアクリル系単量体がグラフト化してしまい、重合安定性が悪くなり良好なエマルジョンが得られない。
【０００８】
このように本発明は、保護コロイドを単量体の２〜１０重量％使用し、重合開始剤としてレドックス系開始剤を使用し、６５℃以下の重合温度でアクリル系単量体と該単量体と共重合可能な単量体を重合させると、これ等の条件が相乗的に作用して粒径０．５μｍ以上のアクリル系エマルジョンが得られ、このエマルジョンが処理した繊維の風合いを良好とし、マイグレーションを防止する作用を奏する。
注意しなければならないのは、アクリル系単量体と共重合させる単量体として酢酸ビニルを使用する場合である。酢酸ビニルの使用量は全単量体に対し２５重量％以下にしなければならない。酢酸ビニルを２５重量％以上使用すると耐水性が不充分となり、酢酸臭が発生するからである。
【０００９】
本発明で使用される原料物質について説明する。
本発明で使用されるアクリル系単量体としては、
アルキル基の炭素原子が１〜１２個のアクリル酸エステルおよびアルキル基の炭素原子が１〜１２個のメタアクリル酸エステルである。
本発明で使用されるアクリル系単量体と共重合体と共重合可能な単量体としては、
スチレン、メチルスチレン等の芳香族ビニル化合物、酢酸ビニル、ベオバ（シェル化学株式会社製のα位で分岐した飽和カルボン酸のビニルエステル）、アクリル酸、メタクリル酸、イタコン酸、クロトン酸等の不飽和カルボン酸、ビニルホスフェート、アクリロニトリル、アクリルアミド、Ｎ−メチロールアクリルアミド、グリシジルメタクリレート、２−ヒドロキシアルキルアクリレート、アクリル酸アルコキシエチル、ビニルトリエトキシシラン、ビニル（２−メトキシエトキシ）シラン、ビニルトリスアセトキシシラン、γ−メタアクリロプロピルトリメトキシシラン等の多官能シラン系単量体等の官能性単量体、その他エチレン、塩化ビニル、塩化ビニリデンなどがある。重合性不飽和基を２個以上有する単量体も使用でき、例えばジビニルベンゼン、ジビニルアジペート、エチレングリコールジ（メタ）アクリレート、１，３−ブチルジ（メタ）アクリレート、ジアリルフタレートなどが挙げられる。
【００１０】
本発明で使用される保護コロイドとしては、
カルボキシメチルヒドロキシエチルセルロース、ヒドロキシエチルセルロース、メチルセルロース、エチルセルロース、カルボキシメチルセルロース等のセルロースエーテル類、ポリビニルアルコール、アセトアセチル化ポリビニルアルコール等のポリビニルアルコール類、ポリビニルピロリドン、変性ポリアクリルアミド、等が挙げられ、重合安定性の面からセルロールエーテル類が好適に用いられる。
【００１１】
本発明で使用されるレドックス系開始剤としては、通常の乳化重合に使用されるもので良く、例えば過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素、ブチルパーオキサイドなどの過酸化物と還元剤を組み合わせたものが用いられる。
本発明においては、所望により保護コロイドの２重量倍以内で界面活性剤が併用でき、通常の乳化重合に使用されるアニオン性、非イオン性の界面活性剤が用いられ、例えばアニオン性の界面活性剤としてはアルキルベンゼンスルホン酸ソーダ、アルキルスルホン酸ソーダ、ポリオキシエチレンアルキルアリルエーテルスルホン酸ソーダ等が挙げられ、非イオン性の界面活性剤としては、ポリオキシエチレンアルキルアリルエーテル型、ポリオキシエチレンアルキルエーテル型、ポリオキシエチレン化ポリオキシプロピレングリコール型等が挙げられる。界面活性剤を保護コロイドの２重量部以上使用すると粒子径が所望の大きさにならない。
また所望により、防腐剤、消泡剤、顔料、連鎖移動剤、造膜助剤等を添加できる。
【００１２】
【実施例】
この際、水溶性高分子であるカルボキシメチルヒドロキシエチルセルロースの量は全単量体に対し２．０重量％である。
得られたエマルジョンは、粒子径１．６μｍ、ｐＨ５．０であった。
【００１３】
実施例２
重合缶に仕込む水を４０重量部、カルボキシメチルヒドロキシエチルセルロースの１０％水溶液の量を５０重量部に変えた以外は実施例１と同様にした。
この際、水溶性高分子であるカルボキシメチルヒドロキシエチルセルロースの量は全単量体に対し５．０重量％である。
得られたエマルジョンは、粒子径１．８μｍ、ｐＨ５．０であった。
【００１４】
実施例３
重合缶に仕込む水を２０重量部、カルボキシメチルヒドロキシエチルセルロースの１０％水溶液の量を８０重量部に変えた以外は実施例１と同様にした。
この際、水溶性高分子であるカルボキシメチルヒドロキシエチルセルロースの量は全単量体に対し８．０重量％である。
得られたエマルジョンは、粒子径１．９μｍ、ｐＨ５．０であった。
【００１５】
この際、水溶性高分子であるカルボキシメチルヒドロキシエチルセルロースの量は全単量体に対し２．０重量％である。
得られたエマルジョンは、粒子径１．６μｍ、ｐＨ５．０であった。
【００１６】
この際、水溶性高分子であるカルボキシメチルヒドロキシエチルセルロースの量は全単量体に対し０．１５重量％である。
得られたエマルジョンは、粒子径０．２０μｍ、ｐＨ５．０であった。
【００１７】
比較例２
（保護コロイドの量が過剰で重合安定性が悪い例）
重合缶に仕込む水を２０重量部、カルボキシメチルヒドロキシエチルセルロースの１０％水溶液の量を１２０重量部、及び水３０重量部に変えた以外は比較例１と同様にした。
この際、水溶性高分子であるカルボキシメチルヒドロキシエチルセルロースの量は全単量体に対し１２．０重量％である。
これは、凝集が著しくエマルジョンが得られなかった。
【００１８】
この際、水溶性高分子であるカルボキシメチルヒドロキシエチルセルロースの量は全単量体に対し２．０重量％である。
得られたエマルジョンは、粒子径１．４μｍ、ｐＨ５．０であった。
【００１９】
比較例４
（一般の開始剤を用い高温で重合した場合重合安定性が悪い例）
実施例１の開始剤を過硫酸アンモニウムに変更し、重合温度８０℃で重合を行った。
これは、凝集が著しくエマルジョンが得られなかった。
（６５℃以上では、グラフト化が著しく進むためと考えられる。）
【００２０】
≪風合い試験≫
レーヨンウェブを、固形分濃度３．７５％に調整したエマルジョン浴に１分間浸漬しマングルで絞る。これを８０℃×１０ｍｉｎ．乾燥させる。室温冷却後、得られた不織布の風合いを触感にて評価する。
バルキイで良好な風合いである………○
ペーパーライクの風合いである………×
【００２１】
≪耐マイグレーション性試験≫
東洋瀘紙Ｎｏ．２を１０ｃｍ×１０ｃｍに裁断したものを５枚とり、Ｎｏ１〜５と番号を付ける。これを固形分濃度５％に調整したエマルジョン浴に１分間浸漬しマングルで絞る。これをはがれないようにして２００℃×２０ｍｉｎ．乾燥させる。室温冷却後、各瀘紙の樹脂の着量を測定し５枚の平均着量を計算する。この平均着量に対する各瀘紙の着量の増減率を計算する。
評価
各瀘紙の増減率が２０％以内である………○
各瀘紙の増減率が２０％以上である………×
【００２２】
≪耐水性試験≫
風合い試験で得られた不織布の常態での引張強度と水浸漬後の引張強度を測定し、その保持率を計算する。
常態での引張強度：５０ｍｍ巾の試験片を２０℃×６５％ＲＨの恒温室中に１６時間以上放置後、株式会社島津製作所製 オートグラフにてつかみ巾１００ｍｍ、引張速度２００ｍｍ／ｍｉｎ．で測定する。（単位 ｋｇｆ／５０ｍｍ）
水浸漬後の引張強度：５０ｍｍ巾の試験片を２０℃水中に１時間浸漬し他は同様に測定する。（単位 ｋｇｆ／５０ｍｍ）
保持率：常態強度／水浸漬後の強度×１００（単位％）
評価
保持率が１５％以上である………○
保持率が１５％未満である………×
試験結果は表に示す。
【００２３】
【表１】
比較例１は、粒子径が小さく風合い及び耐マイマイグレーション性において不良だった。
比較例２、４は凝集してエマルジョンとならなかったため試験出来なかった。
比較例３は、風合い及び耐マイグレーション性は良好であったが、酢酸ビニルの共重合比率が高く耐水性が不良であり，また酢酸臭があった。
【００２５】
【発明の効果】
本発明は特定量の保護コロイドを用いて、特定の重合条件で重合した粒子径０．５μｍ以上のアクリル系エマルジョンを用いることにより風合いが良好でマイグレーシヨンも発生しない優れた効果を奏する。[0001]
[Industrial applications]
The present invention relates to a fiber treatment agent for treating fibers to improve physical properties such as hand, strength, water resistance, solvent resistance, and chemical resistance. More specifically, the present invention relates to a fiber treatment agent which gives an excellent texture without causing migration in which emulsion particles are localized upon drying.
[0002]
[Prior art]
Conventionally, a solution or emulsion of a synthetic resin has been used for treating fibers.
The most important performance required in fiber processing is the texture. When the fibers are treated with the emulsion obtained using the protective colloid, the texture of the fibers is improved as compared with the case where the emulsion obtained using the surfactant is used.
However, as the emulsion which can be polymerized by using a protective colloid, a vinyl acetate emulsion is mainly used, but this emulsion has a disadvantage that it has poor water resistance and has an acetic acid smell.
On the other hand, the acrylic emulsion had no odor of acetic acid and had good water resistance, but it was not polymerizable and easily aggregated, so that emulsion polymerization could not be carried out with a protective colloid.
When fibers are treated with an acrylic emulsion polymerized with a surfactant, the texture is poor, and in particular, a bulky texture cannot be obtained.
Further, the acrylic emulsion obtained by using a surfactant has a disadvantage that it is easily migrated because the particle size is small, approximately 0.5 μm or less.
The term “migration” used here means that when the substrate is impregnated with the emulsion and then forcedly dried with a drier or the like, the temperature of the substrate surface is higher than that of the inside and the water evaporates vigorously on the surface. As a result, such a phenomenon adversely affects the strength, the feel, the printability, the water absorption, and the like.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to solve the conventional problems and to provide a fiber treatment agent having a good texture, no migration, and no odor of acetic acid.
[0004]
[Means for Solving the Problems]
The fiber treating agent according to the present invention is a redox polymerization initiator comprising an acrylic monomer and a monomer copolymerizable with the monomer in the presence of 2 to 10% by weight of a protective colloid based on the monomer. And an acrylic emulsion having a particle diameter of 1.0 to 3.0 [mu] m obtained by emulsion polymerization at a polymerization temperature of 65 [deg.] C. or lower.
According to a preferred embodiment of the present invention, it is preferable that in the fiber treating agent, vinyl acetate is used as a monomer copolymerized with the acrylic monomer in an amount of 25% by weight or less based on the whole monomer.
According to another preferred embodiment of the present invention, the protective colloid is of a cellulose ether type and / or a polyvinyl alcohol type.
According to still another preferred embodiment of the present invention, in the fiber treatment agent, it is preferable that the acrylic monomer is used in an amount of 70 to 99% by weight based on all the monomers.
[0005]
[Action]
A first feature of the present invention is to use an acrylic emulsion polymerized with a protective colloid and having a particle size of 1.0 to 3.0 μm.
The present inventor studied whether fibers treated with a vinyl acetate-based emulsion polymerized using a protective colloid had a good feel, but fibers treated with an acrylic emulsion polymerized using a surfactant had a poor feel. It was found that the size of the emulsion particles had a significant effect. That is, if the particle size of the emulsion particles is small, the texture of the fiber deteriorates.
If the particle size is not from 1.0 to 3.0 μm, a bulky texture with a texture cannot be obtained. If the thickness is less than 1.0 μm, migration tends to occur. When the particle diameter is 3.0 μm or more, the dilution stability of the emulsion tends to deteriorate.
[0006]
A second feature of the present invention is the amount of protective colloid used. The amount of protective colloid, based on the monomers, must be between 2 and 10% by weight. If it is less than 2% by weight, the particle size of the emulsion does not become 0.5 μm or more. Therefore, the texture of the treated fiber is not good, and migration occurs. When the content of the protective colloid is 10% by weight or more, the viscosity increases and the stability at the time of polymerization deteriorates, the stability of the emulsion deteriorates, and the water resistance also decreases.
[0007]
A third feature of the present invention is that polymerization is carried out at 0 ° C to 65 ° C using a redox-based initiator as a polymerization initiator. In order to obtain a good emulsion, the polymerization temperature needs to be 65 ° C. or lower, and for that purpose, it is necessary to use a redox initiator as a polymerization initiator. If the polymerization conditions are not satisfied, the protective colloid and the acrylic monomer are grafted, and the polymerization stability is deteriorated, so that a good emulsion cannot be obtained.
[0008]
As described above, the present invention uses a protective colloid in an amount of 2 to 10% by weight of a monomer, a redox initiator as a polymerization initiator, and an acrylic monomer and the monomer at a polymerization temperature of 65 ° C. or lower. When a monomer copolymerizable with the body is polymerized, these conditions act synergistically to obtain an acrylic emulsion having a particle size of 0.5 μm or more, and this emulsion improves the texture of the treated fiber. This has the effect of preventing migration.
Care must be taken when using vinyl acetate as the monomer to be copolymerized with the acrylic monomer. The amount of vinyl acetate used must not exceed 25% by weight, based on the total monomers. If vinyl acetate is used in an amount of 25% by weight or more, the water resistance becomes insufficient and an acetic acid odor is generated.
[0009]
The raw material used in the present invention will be described.
As the acrylic monomer used in the present invention,
An alkyl acrylate having 1 to 12 carbon atoms and a methacrylate having 1 to 12 carbon atoms in the alkyl group.
As the acrylic monomer and copolymerizable monomer used in the present invention,
Unsaturation such as aromatic vinyl compounds such as styrene and methylstyrene, vinyl acetate, veova (vinyl ester of saturated carboxylic acid branched at the α-position, manufactured by Shell Chemical Co., Ltd.), acrylic acid, methacrylic acid, itaconic acid, crotonic acid, etc. Carboxylic acid, vinyl phosphate, acrylonitrile, acrylamide, N-methylol acrylamide, glycidyl methacrylate, 2-hydroxyalkyl acrylate, alkoxyethyl acrylate, vinyl triethoxysilane, vinyl (2-methoxyethoxy) silane, vinyl trisacetoxy silane, γ- Examples include functional monomers such as polyfunctional silane monomers such as methacrylopropyltrimethoxysilane, and ethylene, vinyl chloride, and vinylidene chloride. A monomer having two or more polymerizable unsaturated groups can also be used, and examples thereof include divinylbenzene, divinyl adipate, ethylene glycol di (meth) acrylate, 1,3-butyldi (meth) acrylate, and diallyl phthalate.
[0010]
As the protective colloid used in the present invention,
Carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, cellulose ethers such as carboxymethyl cellulose, polyvinyl alcohol, polyvinyl alcohols such as acetoacetylated polyvinyl alcohol, polyvinyl pyrrolidone, modified polyacrylamide, and the like, polymerization stability From the viewpoint, cellulose ethers are preferably used.
[0011]
As the redox initiator used in the present invention, those used for ordinary emulsion polymerization may be used.For example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, and peroxides such as butyl peroxide may be used. A combination of reducing agents is used.
In the present invention, a surfactant can be used in combination within 2 times the weight of the protective colloid, if desired, and anionic and nonionic surfactants used in ordinary emulsion polymerization are used. Examples of the agent include sodium alkylbenzene sulfonate, sodium alkyl sulfonate, and sodium polyoxyethylene alkyl allyl ether sulfonate. Examples of the nonionic surfactant include polyoxyethylene alkyl allyl ether type and polyoxyethylene alkyl ether. And polyoxyethylenated polyoxypropylene glycol types. If the surfactant is used in an amount of 2 parts by weight or more of the protective colloid, the particle size does not become a desired size.
If desired, preservatives, defoamers, pigments, chain transfer agents, film-forming auxiliaries, and the like can be added.
[0012]
【Example】
At this time, the amount of carboxymethyl hydroxyethyl cellulose, which is a water-soluble polymer, is 2.0% by weight based on all monomers.
The obtained emulsion had a particle size of 1.6 μm and a pH of 5.0.
[0013]
Example 2
Example 1 was repeated except that the amount of water charged in the polymerization vessel was changed to 40 parts by weight and the amount of a 10% aqueous solution of carboxymethylhydroxyethylcellulose was changed to 50 parts by weight.
At this time, the amount of carboxymethylhydroxyethyl cellulose, which is a water-soluble polymer, is 5.0% by weight based on all monomers.
The obtained emulsion had a particle size of 1.8 μm and a pH of 5.0.
[0014]
Example 3
Example 1 was repeated except that the amount of water charged in the polymerization vessel was changed to 20 parts by weight, and the amount of a 10% aqueous solution of carboxymethylhydroxyethylcellulose was changed to 80 parts by weight.
At this time, the amount of carboxymethylhydroxyethylcellulose, which is a water-soluble polymer, is 8.0% by weight based on all monomers.
The obtained emulsion had a particle size of 1.9 μm and a pH of 5.0.
[0015]
At this time, the amount of carboxymethyl hydroxyethyl cellulose, which is a water-soluble polymer, is 2.0% by weight based on all monomers.
The obtained emulsion had a particle size of 1.6 μm and a pH of 5.0.
[0016]
At this time, the amount of carboxymethylhydroxyethyl cellulose, which is a water-soluble polymer, is 0.15% by weight based on all monomers.
The obtained emulsion had a particle size of 0.20 μm and a pH of 5.0.
[0017]
Comparative Example 2
(Example in which the amount of protective colloid is excessive and polymerization stability is poor)
Comparative Example 1 was carried out in the same manner as in Comparative Example 1 except that the amount of water charged in the polymerization vessel was changed to 20 parts by weight, the amount of a 10% aqueous solution of carboxymethylhydroxyethylcellulose was changed to 120 parts by weight, and to 30 parts by weight of water.
At this time, the amount of carboxymethyl hydroxyethyl cellulose, which is a water-soluble polymer, is 12.0% by weight based on all monomers.
This resulted in significant aggregation and no emulsion was obtained.
[0018]
At this time, the amount of carboxymethyl hydroxyethyl cellulose, which is a water-soluble polymer, is 2.0% by weight based on all monomers.
The obtained emulsion had a particle diameter of 1.4 μm and a pH of 5.0.
[0019]
Comparative Example 4
(Example of poor polymerization stability when polymerized at high temperature using a general initiator)
The polymerization in Example 1 was changed to ammonium persulfate, and polymerization was carried out at a polymerization temperature of 80 ° C.
This resulted in significant aggregation and no emulsion was obtained.
(It is considered that the grafting proceeds remarkably at a temperature of 65 ° C. or higher.)
[0020]
≪Hand test≫
The rayon web is immersed in an emulsion bath adjusted to a solid concentration of 3.75% for 1 minute and squeezed with a mangle. This is 80 ° C. × 10 min. dry. After cooling at room temperature, the texture of the obtained nonwoven fabric is evaluated by touch.
Barkii with good texture ......... ○
It has a paper-like texture .......... ×
[0021]
マ イ グ レ ー シ ョ ン Migration resistance test≫
Toyo Roshi no. No. 2 is cut into 10 cm × 10 cm, and five sheets are taken and numbered No. 1 to No. 5. This is immersed in an emulsion bath adjusted to a solid content concentration of 5% for 1 minute and squeezed with a mangle. 200 ° C. × 20 min. dry. After cooling at room temperature, the amount of resin applied to each filter paper is measured, and the average amount of resin applied to five sheets is calculated. The increase / decrease rate of the applied amount of each filter paper relative to the average applied amount is calculated.
Evaluation The rate of change of each filter paper is within 20%.
The rate of change of each filter paper is 20% or more.
[0022]
水性 Water resistance test≫
The tensile strength in the normal state and the tensile strength after immersion in water of the nonwoven fabric obtained in the hand test are measured, and the retention is calculated.
Tensile strength under normal conditions: A test piece having a width of 50 mm was left in a constant temperature room at 20 ° C. and 65% RH for 16 hours or more, and then gripped with an autograph manufactured by Shimadzu Corporation at a width of 100 mm and a pulling speed of 200 mm / min. Measure with (Unit kgf / 50mm)
Tensile strength after immersion in water: A test piece having a width of 50 mm is immersed in water at 20 ° C. for 1 hour, and the other parts are measured similarly. (Unit kgf / 50mm)
Retention: normal strength / strength after immersion in water x 100 (unit%)
The evaluation retention rate is 15% or more.
Retention rate is less than 15% .... ×
The test results are shown in the table.
[0023]
[Table 1]
Comparative Example 1 had a small particle size and was poor in texture and mimigration resistance.
Comparative Examples 2 and 4 could not be tested because they did not aggregate into an emulsion.
In Comparative Example 3, the hand and the migration resistance were good, but the copolymerization ratio of vinyl acetate was high, the water resistance was poor, and the odor of acetic acid was found.
[0025]
【The invention's effect】
According to the present invention, by using an acrylic emulsion having a particle diameter of 0.5 μm or more which is polymerized under specific polymerization conditions using a specific amount of protective colloid, an excellent effect is obtained in which the feeling is good and migration does not occur.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20410394A JP3553653B2 (en) | 1994-07-27 | 1994-07-27 | Fiber treatment agent mainly composed of acrylic emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20410394A JP3553653B2 (en) | 1994-07-27 | 1994-07-27 | Fiber treatment agent mainly composed of acrylic emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0841784A JPH0841784A (en) | 1996-02-13 |
| JP3553653B2 true JP3553653B2 (en) | 2004-08-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20410394A Expired - Fee Related JP3553653B2 (en) | 1994-07-27 | 1994-07-27 | Fiber treatment agent mainly composed of acrylic emulsion |
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| Country | Link |
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| JP (1) | JP3553653B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5958735B2 (en) * | 2011-12-27 | 2016-08-02 | 三菱レイヨン株式会社 | Method for producing emulsion and coating composition containing emulsion |
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1994
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH0841784A (en) | 1996-02-13 |
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