JPH01115911A - Production of n-methylol compound-ethylene-vinyl acetate three-component copolymer and binder for nonwoven fabric containing same - Google Patents
Production of n-methylol compound-ethylene-vinyl acetate three-component copolymer and binder for nonwoven fabric containing sameInfo
- Publication number
- JPH01115911A JPH01115911A JP62273274A JP27327487A JPH01115911A JP H01115911 A JPH01115911 A JP H01115911A JP 62273274 A JP62273274 A JP 62273274A JP 27327487 A JP27327487 A JP 27327487A JP H01115911 A JPH01115911 A JP H01115911A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- acrylamide
- ethylene
- binder
- copolymer
- 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
- 239000011230 binding agent Substances 0.000 title claims abstract description 24
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 title claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims description 4
- 229920001577 copolymer Polymers 0.000 title abstract description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000084 colloidal system Substances 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 11
- 229920006322 acrylamide copolymer Polymers 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- DUZXVLRTMFAOLX-UHFFFAOYSA-N ethenyl acetate;prop-2-enamide Chemical compound NC(=O)C=C.CC(=O)OC=C DUZXVLRTMFAOLX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007127 saponification reaction Methods 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 229920001897 terpolymer Polymers 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006136 alcoholysis reaction Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical group OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- -1 etc.) Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XTWOERQZSBJRGB-UHFFFAOYSA-N S(=O)(=O)([O-])[O-].[NH4+].C(C=C)(=O)N.[NH4+] Chemical compound S(=O)(=O)([O-])[O-].[NH4+].C(C=C)(=O)N.[NH4+] XTWOERQZSBJRGB-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- NWDCGICEHJVOPW-UHFFFAOYSA-N acetic acid;prop-2-enamide Chemical compound CC(O)=O.NC(=O)C=C NWDCGICEHJVOPW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 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
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Nonwoven Fabrics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、不織布の製造に用いられる、自己架橋性バイ
ンダーに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a self-crosslinking binder used in the production of nonwoven fabrics.
−Ｎ−メチロール化合物を乳化共重合して得られる自ど
架橋性共重合体をバインダーとして使用することは公知
である。It is known that an autocrosslinkable copolymer obtained by emulsion copolymerization of a -N-methylol compound is used as a binder.
しかしながら、上記架橋剤は架橋反応の際に遊離ホルム
アルデヒドを発生し、特に不織布を衣料材料として使用
する場合は安全上好ましくない。However, the above-mentioned crosslinking agent generates free formaldehyde during the crosslinking reaction, which is unfavorable from a safety standpoint, especially when the nonwoven fabric is used as a clothing material.
これまでホルムアルデヒド対策としてアクリルアミドを
共重合する方法（特開昭５９−１’８７＜５５８号公報
）が提案されているが、その効果は十分でなかった。ま
た捕集剤を併用する方ｆ：（特公昭５９−３０８２４号
公報）も提案されているが、ジシアンジアミド、尿素、
グアニジン塩等を使用するため、その用途に制限があっ
た。A method of copolymerizing acrylamide (Japanese Unexamined Patent Publication No. 59-1'87<558) has been proposed as a countermeasure against formaldehyde, but the effect was not sufficient. In addition, a method f: (Japanese Patent Publication No. 59-30824) has been proposed in which a scavenger is used in combination, but dicyandiamide, urea,
Since it uses guanidine salt, etc., its uses are limited.
本発明者等は、不織布用バインダーに係る問題点を解決
すべく鋭意検討を重ねた結果、アクリルアミド変性ポリ
ビニルアルコール（酢酸ビニル−アクリルアミド共重合
体けん化物）を保護コロイドとして使用すると遊離ホル
ムアルデヒド発生量が低くなることも見出し本発明を完
成した。The inventors of the present invention have conducted extensive studies to solve problems related to binders for nonwoven fabrics, and have found that using acrylamide-modified polyvinyl alcohol (saponified vinyl acetate-acrylamide copolymer) as a protective colloid reduces the amount of free formaldehyde generated. The present invention was completed based on the discovery that the temperature can be lowered.
即ち本発明の第１の発明は、アクリルアミド含有量１〜
１０１菫％、けん化度８５モル％以上の酢酸ビニル−ア
クリルアミド共重合体けん化物を保論コロイドとして存
在させ、エチレン５〜３ＯＩＩＩ％、Ｎ−メチロール化
合物０．５〜１０：ｌＩｔ％及び酢酸ビニル６０〜９４
．５ｍｆ％を乳化共重合させることを特徴とするＮ−メ
チロール化合物−エチレン−酢酸ビニル三元共重合体の
製造方法である。That is, the first invention of the present invention has an acrylamide content of 1 to
A saponified vinyl acetate-acrylamide copolymer with a saponification degree of 85 mol% or more is present as a colloid, and 5 to 3 OIII% of ethylene, 0.5 to 10:1 It% of an N-methylol compound and 60% of vinyl acetate are present as colloids. ~94
．． This is a method for producing an N-methylol compound-ethylene-vinyl acetate terpolymer, which comprises emulsion copolymerizing 5mf%.
第２の発明は、アクリルアミド含有量１〜１０１量％、
けん化度８５モル係以上の酢酸ビニル−アクリルアミド
共重合体けん化物を保護コロイドとして存在させ、エチ
レン５〜３０！Ｊ１％、Ｎ−メチロール化合物０．５〜
１０！ｉ％及び酢酸ビニル６０〜９４．５ｍ景％を乳化
共重合させてなるＮ−メチロール化合物−エチレン−酢
酸ビニル三元共重合体を有する不織布用バインダーであ
る。The second invention has an acrylamide content of 1 to 101% by weight,
A saponified vinyl acetate-acrylamide copolymer with a saponification degree of 85 molar or higher is present as a protective colloid, and ethylene is 5 to 30 molar. J1%, N-methylol compound 0.5~
10! This is a binder for nonwoven fabric having an N-methylol compound-ethylene-vinyl acetate terpolymer obtained by emulsion copolymerizing 1% and 60 to 94.5% of vinyl acetate.
本発明の不織布用バインダーは自己架橋性共重合体であ
ってエチレン含量は５〜３０ｍ１ｔ％である。エチレン
含量が５重量％未満では柔軟性が不足し、不織布製品に
適度な風合いが得られない。The binder for nonwoven fabrics of the present invention is a self-crosslinking copolymer and has an ethylene content of 5 to 30 m1t%. If the ethylene content is less than 5% by weight, the flexibility will be insufficient and the nonwoven fabric will not have a suitable texture.
一方３０重量％を越すと、不織布製品の強度が低下する
。On the other hand, if it exceeds 30% by weight, the strength of the nonwoven fabric product will decrease.
Ｎ−メチロール化合物の含量は０．５〜１０ｍ１ｔ％で
ある。０．５１１１％未満では、不織布製品の十分な強
度が得られず、一方１０ｍｒｊｌｔ％を越すと遊離ホル
ムアルデヒド発生量が多くなる。The content of the N-methylol compound is 0.5-10 ml t%. If it is less than 0.5111%, sufficient strength of the nonwoven fabric product cannot be obtained, while if it exceeds 10 mrjlt%, the amount of free formaldehyde generated increases.
−膜内に使用されるＮ−メチロール化合物は、Ｎ−メチ
ロールアクリルアミドやＮ−メチロールメタアクリルア
ミドである。- The N-methylol compound used in the membrane is N-methylol acrylamide or N-methylol methacrylamide.
保護コロイドとしての酢酸ビニル−アクリルアミド共重
合体けん化物（アクリルアミド変性ポリビニルアルコー
ル）の使用量は１〜５重量％（対共重合体固型分）が好
ましい。１重量％未満ではホルマリン発生抑制効果が十
分でなく、一方Ｓｘｔ係を越すと自己架橋性共重合体の
粘度上昇が著しい。The amount of saponified vinyl acetate-acrylamide copolymer (acrylamide-modified polyvinyl alcohol) used as a protective colloid is preferably 1 to 5% by weight (based on the solid content of the copolymer). If it is less than 1% by weight, the effect of inhibiting formalin generation will not be sufficient, while if it exceeds the Sxt ratio, the viscosity of the self-crosslinking copolymer will increase significantly.
上記のアクリルアミド変性ポリビニルアルコール中のア
クリルアミド含有量は１〜１０重量係である。１重量％
未満ではホルムアルデヒド発生抑制効果が十分でなく、
一方１０重量係を越すと保護コロイド性が良くない。ま
たけん化度は８５モル係以上である。８５モル係未満で
は保護コロイド性が悪い。本アクリルアミド変性ポリビ
ニルアルコールは、乳化重合で一般的に用いられる保賎
コロイド（例、とドロキシエチルセルロース、メチルセ
ルロース等）、非イオン性界面活性剤（例ホリオキシエ
チレン縮合体等）およびアニオン性界面活性剤（例、ア
ルキルベンゼンスルホン°酸塩等）の一種以上との併用
も可能である。The acrylamide content in the acrylamide-modified polyvinyl alcohol is 1 to 10% by weight. 1% by weight
If it is less than that, the effect of suppressing formaldehyde generation is not sufficient,
On the other hand, if the weight exceeds 10, the protective colloid properties are not good. Moreover, the saponification degree is 85 molar coefficient or more. If the molar ratio is less than 85, the protective colloid properties are poor. This acrylamide-modified polyvinyl alcohol contains adhesive colloids commonly used in emulsion polymerization (e.g., droxyethyl cellulose, methyl cellulose, etc.), nonionic surfactants (e.g., polyoxyethylene condensates, etc.), and anionic surfactants. It is also possible to use it in combination with one or more types of agents (eg, alkylbenzene sulfonate salts, etc.).
アクリルアミド変性ポリビニルアルコールは、市販品を
入手することもまた公知の方法によりａ造することも可
能である。たとえば、酢酸ビニル及びアクリルアミドを
、アゾビスインブチロニトリル等を開始剤として共重合
せしめて酢酸ビニル−アクリルアミド共重合体を得るか
、この際任意量のアクリルアミドをメタノールに溶解し
、１合中連続的に添加し均一に共重合せしめる。得られ
たポリ酢酸ビニル−アクリルアミド共重合物のメタノー
ル浴液中の未反応モノマーを除去後、アクリルアミドを
けん化しない程度のアルカリを加え加アルコール分解に
よりアクリルアミド変性ポリビニルアルコールを得るこ
とができる。Acrylamide-modified polyvinyl alcohol can be obtained commercially or can be produced by a known method. For example, a vinyl acetate-acrylamide copolymer is obtained by copolymerizing vinyl acetate and acrylamide using azobisin butyronitrile or the like as an initiator, or in this case, an arbitrary amount of acrylamide is dissolved in methanol, and acrylamide is continuously copolymerized during one reaction. and uniformly copolymerize. After removing unreacted monomers from the methanol bath of the resulting polyvinyl acetate-acrylamide copolymer, alkali to an extent that does not saponify the acrylamide is added and alcoholytic decomposition is performed to obtain acrylamide-modified polyvinyl alcohol.
乳化重合方法は公知の方法を使用することが出来る。重
合条件に特に制限はないが、−膜内には重合温度２０〜
８０°ＣＳＸ合圧力１０〜９０１０１／ＧＩＩＬ２が利
用される。A known emulsion polymerization method can be used. There are no particular restrictions on the polymerization conditions, but - the polymerization temperature within the membrane is 20~20°C.
80° CSX combined pressure 10-90101/GIIL2 is utilized.
以上の方法で得られた自己架橋性共重合体の不織布用バ
インダーを使用して不織布ｔ−製造するには、湿式およ
び乾式等の方法によって得られた未結合あるいは予備結
合されたクエツブを上記バインダー中に浸漬するか、ま
たは上記バインダーをスプレー等の方法によって付着さ
せ、乾燥、熱処理する。To produce a nonwoven fabric using the self-crosslinking copolymer nonwoven fabric binder obtained by the above method, unbonded or prebonded quetubes obtained by wet or dry methods are added to the above binder. The above binder is applied by immersion in the resin or by spraying, followed by drying and heat treatment.
上記バインダーには、必要に応じて消泡剤・顔料・撥水
剤・起泡剤・分散剤を添加することができ、またＳＢＲ
等の他の公知のバインダーとの併用も可能である。Antifoaming agents, pigments, water repellents, foaming agents, and dispersants can be added to the above binder as necessary, and SBR
It is also possible to use it in combination with other known binders such as.
熱処理は１００〜２００°Ｃ１好ましくは１６０〜１６
０°Ｃの温度で１〜１５分の処理が好ましく、必要に応
じて架橋助剤を併用してもよい。架橋助剤は鉱酸類、有
機酸類、酸塩類が使用され、具体的には塩化アンモニク
ム、塩化マグネシクム、硝酸アンモニクム、無水マレイ
ン酸、アルカノールアミン等がよく使用される。Heat treatment at 100-200°C, preferably 160-16
The treatment is preferably carried out at a temperature of 0°C for 1 to 15 minutes, and a crosslinking aid may be used in combination if necessary. Mineral acids, organic acids, and acid salts are used as crosslinking aids, and specifically, ammonicum chloride, magnesium chloride, ammonicum nitrate, maleic anhydride, alkanolamines, and the like are often used.
以下実施例で具体的に説明する。This will be explained in detail in Examples below.
実施例１
不織布用バインダーの製造例
内容積ＩＣｌのステンレス製電磁攪拌機付オートクレー
ブに次の原料を仕込んだ。Example 1 Production Example of Binder for Nonwoven Fabric The following raw materials were charged into a stainless steel autoclave equipped with an electromagnetic stirrer and having an internal volume of ICl.
純 水 ２６５０．９酢酸ビニル
２８５０ ｇ
ゾルロニツク （加電化工業社製 ボＦ−
８８，Ｆ−６８，各６０９ リオキシエチレン、ボＬ−
６４リオキシゾロビレンブ
ロック共重合体）
ハイドロキシエチル ４５ｇ （フジ化学工業社製
）セルロース
ハイテノール ２２．５．！ｉ’（第一工業製薬社
製Ｎ−１７ポリオギシアルキル
（又はアリル）サルフ
エートのアンモニクム
塩
アクリルアミド変性 ９０ｇ （アクリルアミ ド含
有ポリビニルアルコール 景５Ｎ量％ 、
けん化度９０モル％）
酢酸ソーダ １２．Ｓｌ’
内温を７０°Ｃまで上げてエチレンを５０ ｋｌ？／Ｇ
ｘ”になるまで導入した。過硫酸アンモニクム０．６
ｇを添加し１合を開始した。内温はジャケットの温度を
ｖ４整して一定に保った。Pure water 2650.9 Vinyl acetate
2850 g Zorronik (manufactured by Kadenka Kogyo Co., Ltd. BoF-
88, F-68, each 609 Lioxyethylene, Bo L-
64 lioxyzolobylene block copolymer) Hydroxyethyl 45g (manufactured by Fuji Chemical Industry Co., Ltd.) Cellulose Hitenol 22.5. ! i' (Daiichi Kogyo Seiyaku Co., Ltd. N-17 polyoxyalkyl (or allyl) sulfate ammonium salt acrylamide modified 90 g (acrylamide-containing polyvinyl alcohol 5N amount %,
Saponification degree 90 mol%) Sodium acetate 12. Sl' Raise the internal temperature to 70°C and add 50 kl of ethylene? /G
Ammonic persulfate 0.6
1 cup was started. The internal temperature was kept constant by adjusting the jacket temperature to V4.
Ｎ−メチロールアクリルアミド（１５０，Ｆ）？３５０
−の水に溶解し、重合開始時より６時間にわたって連続
的に分添した。１０時間の後、冷却し内容物を１１出し
た。内容物は粗粒の少い安定なエマルジョンで固型分ｓ
ｉ、６ｘ景％、粘度２１２０ ｃｐｓで、そのポリマー
組成は酢酸ビニルユニット７６重量％、エチレンユニッ
ト１１！Ｊ１％、Ｎ−メチロールアクリルアミドユニッ
ト５重量係であった。N-methylolacrylamide (150,F)? 350
- was dissolved in water and added continuously over 6 hours from the start of polymerization. After 10 hours, it was cooled and the contents were poured out. The content is a stable emulsion with few coarse particles and solid content.
It has a viscosity of 2120 cps and a polymer composition of 76% vinyl acetate units and 11 ethylene units! J1%, N-methylolacrylamide units 5% by weight.
比較例１
純水及び酢酸ビニルの仕込み量が各々２４４０．９，２
７６０．Ｆ、保護コロイドとしてアクリルアミド変性ポ
リビニルアルコールを使用せず、Ｎ−メチロールアクリ
ルアミド１５０ｇおよびアクリルアミド９０ｇを５６０
ＩＬｌの水に溶解し、１合開始時よシロ時間にわたって
連続的に分添した以外は、実施例１と同様ｌＣ，ｉ１合
した。Comparative Example 1 The amounts of pure water and vinyl acetate were 2440.9 and 2440.9, respectively.
760. F, without using acrylamide-modified polyvinyl alcohol as a protective colloid, 150 g of N-methylol acrylamide and 90 g of acrylamide were added to 560 g of acrylamide.
1C and 1C were combined in the same manner as in Example 1, except that IL1 was dissolved in water and added continuously from the beginning of 1C over a period of time.
１０時間の後、冷却し内容物を収り出したところ、粗粒
の少ない安定なエマルションであり、固型分５０．５］
！量％、粘度２８００ ｃｐｓで、そのポリマー組成は
酢酸ビニルユニット７４］［３１％、エチレンユニット
１８１ｔ％、アクリルアミ「ユニット３１（量％、Ｎ−
メチロールアクリルアミドユニット５重１係であった。After 10 hours, it was cooled and the contents were collected, and it was found to be a stable emulsion with few coarse particles, solid content 50.5]
! %, viscosity 2800 cps, and its polymer composition was vinyl acetate units 74% [31%], ethylene units 181t%, acrylamide units 31% (% N-
It had 5 methylol acrylamide units and 1 unit.
実施例２
実施例１の方法で作製したバインダーを、東洋ろ紙ｔ’
＆＞２ （１２（］！９／ｍ” ）Ｋ含浸率２５Ｘ量％
になるよう含浸し、風乾後１４０°Ｃ１５分の熱処理を
行なった。この含浸紙の性能？ｆｆに示す。Example 2 The binder produced by the method of Example 1 was coated with Toyo Roshi T'
&>2 (12(]!9/m”) K impregnation rate 25X amount%
After air drying, heat treatment was performed at 140° C. for 15 minutes. What is the performance of this impregnated paper? It is shown in ff.
実施例６．４および比較例２．６
Ｎ−メチロールアクリルアミｒ菫を変えた他は実施例１
と同様の方法で作製した表の組成のバインダーを、評価
した。Example 6.4 and Comparative Example 2.6 Example 1 except that N-methylolacrylamide violet was changed
A binder having the composition shown in the table prepared in the same manner as above was evaluated.
実施例５．６．７
Ｎ−メチロールアクリルアミドの代わシに、Ｎ−メチロ
ールメタアクリルアミドを使用した他は各々実施例２．
３．４と同様に製造し、評価した。Example 5.6.7 The same as Example 2 except that N-methylolmethacrylamide was used instead of N-methylolacrylamide.
It was manufactured and evaluated in the same manner as in 3.4.
実施例８．９．１０
アクリルアミド含有１１９］Ｌ量％、けん化度９５モル
係のアクリルアミド変性ポリビニルアルコ−ルを用いた
他は各々実施例２．３．４と同様に製造し評価した。Example 8.9.10 Each sample was produced and evaluated in the same manner as in Example 2.3.4, except that acrylamide-modified polyvinyl alcohol containing 119]L of acrylamide and having a saponification degree of 95 mol was used.
実施例１１．１２
実施例２及び実施例５でそれぞれ使用したバインダーと
同一のバインダーをレーヨン１００％のクエブ（目付１
００ 、！ｉ’／ｍ” ）に含浸率３５重Ｊ１％になる
ように含浸し、風乾後１４０℃で５分熱処理した。Example 11.12 The same binder as used in Example 2 and Example 5 was added to 100% rayon Kueb (fabric weight 1
00,! i'/m'') at an impregnation rate of 35% by weight J1%, air-dried, and then heat-treated at 140°C for 5 minutes.
比較例４，５
エチレン圧を変えエチレン含量を変えた他は、実施例１
と同様の方法で作製した衣の組成のバインダーを評価し
た。Comparative Examples 4 and 5 Example 1 except that the ethylene pressure was changed and the ethylene content was changed.
The binder composition of the batter prepared in the same manner as above was evaluated.
比較例６．７
アクリルアミド変性ポリビニルアルコール使用ｔを変え
たほかは、実施例１と同様の方法で作製した表の組成の
バインダーを評価した。Comparative Example 6.7 A binder having the composition shown in the table was prepared in the same manner as in Example 1 except that t of acrylamide-modified polyvinyl alcohol was used.
比較例８
比較例１の方法で作製したバインダーを、実施例２と同
様の方法で評価した。Comparative Example 8 The binder produced by the method of Comparative Example 1 was evaluated in the same manner as in Example 2.
比較例９
Ｎ−メチロールアクリルアミドｔを変えたほかは、比較
例１と同様の方法で作製したバインダーを評価した。Comparative Example 9 A binder prepared in the same manner as Comparative Example 1 except that N-methylolacrylamide t was changed was evaluated.
測定法
（１）乾燥時引張強度
含浸紙を１５×１５０朋の大きさに切シ、島津製作所製
引張試験機１ｓ−５００を用いて引張速度２００ｍ／分
、チャック間距離１００酊で測定。Measurement method (1) Tensile strength when dry Cut the impregnated paper into a size of 15 x 150 mm and measure using a Shimadzu tensile tester 1s-500 at a tensile speed of 200 m/min and a distance between chucks of 100 mm.
（２）湿潤時引張強度
含浸紙を２０℃の水に２時間浸漬後、（１）と同様の方
法で強度を測定した。(2) Tensile strength when wet After soaking the impregnated paper in water at 20° C. for 2 hours, the strength was measured in the same manner as in (1).
（３）風合い
ハンドリングテストによって測定した。試験片がほとん
ど抵抗なく曲げられる場合を「良」とした。(3) Texture Measured by handling test. A case where the test piece could be bent with almost no resistance was considered "good".
（４）遊離ホルムアルデヒド量
厚生省令第６４号に基づきホルムアルデヒド量を定量し
た（検出限界０．１ ｐｐｍ ）。(4) Amount of free formaldehyde The amount of formaldehyde was quantified based on Ministry of Health and Welfare Ordinance No. 64 (detection limit 0.1 ppm).
（５）バインダーの状態
バインダーをビーカーに１００ｇとり、がラス棒で攪拌
して状態を観察した。抵抗がほとんどなく攪拌できる場
合を「良」、−？や抵抗のある場合を「やや増粘」、抵
抗の大きい場合を「増粘大」とした。(5) Condition of binder 100 g of binder was placed in a beaker, stirred with a ratchet rod, and the condition was observed. If stirring is possible with little resistance, it is "good", -? A case where there was resistance or resistance was defined as "slightly thickening", and a case where resistance was large was defined as "largely thickening".
本発明によシ、遊離ホルムアルデヒド量の低い不織布用
バインダーを得ることができる。According to the present invention, a binder for nonwoven fabrics with a low amount of free formaldehyde can be obtained.
特許出願人 電気化学工業株式会社Patent applicant Denki Kagaku Kogyo Co., Ltd.
Claims (2)
８５モル％以上の酢酸ビニル−アクリルアミド共重合体
けん化物を保護コロイドとして存在させ、エチレン５〜
３０重量％、Ｎ−メチロール化合物０．５〜１０重量％
及び酢酸ビニル６０〜９４．５重量％を乳化共重合させ
ることを特徴とするＮ−メチロール化合物−エチレン−
酢酸ビニル三元共重合体の製造方法。(1) A saponified vinyl acetate-acrylamide copolymer with an acrylamide content of 1 to 10% by weight and a saponification degree of 85 mol% or more is present as a protective colloid, and ethylene is
30% by weight, N-methylol compound 0.5-10% by weight
and N-methylol compound-ethylene- which is characterized by emulsion copolymerization of 60 to 94.5% by weight of vinyl acetate.
A method for producing a vinyl acetate terpolymer.
８５モル％以上の酢酸ビニル−アクリルアミド共重合体
けん化物を保護コロイドとして存在させ、エチレン５〜
３０重量％、Ｎ−メチロール化合物０．５〜１０量％及
び酢酸ビニル６０〜９４．５重量％を乳化共重合させて
なるＮ−メチロール化合物−エチレン−酢酸ビニル三元
共重合体を含有する不織布用バインダー。(2) A saponified vinyl acetate-acrylamide copolymer with an acrylamide content of 1 to 10% by weight and a saponification degree of 85 mol% or more is present as a protective colloid, and ethylene is
A nonwoven fabric containing an N-methylol compound-ethylene-vinyl acetate terpolymer obtained by emulsion copolymerization of 30% by weight, 0.5 to 10% by weight of an N-methylol compound, and 60 to 94.5% by weight of vinyl acetate. Binder for.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62273274A JP2599733B2 (en) | 1987-10-30 | 1987-10-30 | Process for producing terpolymer of N-methylol compound-ethylene-vinyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62273274A JP2599733B2 (en) | 1987-10-30 | 1987-10-30 | Process for producing terpolymer of N-methylol compound-ethylene-vinyl acetate |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25175296A Division JP2821444B2 (en) | 1996-09-24 | 1996-09-24 | Non-woven fabric binder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01115911A true JPH01115911A (en) | 1989-05-09 |
| JP2599733B2 JP2599733B2 (en) | 1997-04-16 |
Family
ID=17525556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62273274A Expired - Fee Related JP2599733B2 (en) | 1987-10-30 | 1987-10-30 | Process for producing terpolymer of N-methylol compound-ethylene-vinyl acetate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2599733B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1375542A1 (en) * | 2002-06-17 | 2004-01-02 | Air Products Polymers, L.P. | Vinyl chloride/vinyl acetate/ethylene/self-crosslinking polymers for non-cellulosic based substrates |
| JP2008126800A (en) * | 2006-11-20 | 2008-06-05 | Valeo Thermal Systems Japan Corp | Car air conditioner |
| US8254683B2 (en) | 2005-03-18 | 2012-08-28 | Fujitsu Limited | Code image processing method |
| JP2013095868A (en) * | 2011-11-02 | 2013-05-20 | Kuraray Co Ltd | Modified vinyl alcohol polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS507192A (en) * | 1973-05-23 | 1975-01-24 | ||
| JPS5027104A (en) * | 1973-04-30 | 1975-03-20 | ||
| JPS6010138A (en) * | 1983-06-30 | 1985-01-19 | Toshiba Corp | Heat flux measuring apparatus |
| JPS62127335A (en) * | 1985-11-26 | 1987-06-09 | Sumitomo Chem Co Ltd | Highly expandable binder composition |
-
1987
- 1987-10-30 JP JP62273274A patent/JP2599733B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5027104A (en) * | 1973-04-30 | 1975-03-20 | ||
| JPS507192A (en) * | 1973-05-23 | 1975-01-24 | ||
| JPS6010138A (en) * | 1983-06-30 | 1985-01-19 | Toshiba Corp | Heat flux measuring apparatus |
| JPS62127335A (en) * | 1985-11-26 | 1987-06-09 | Sumitomo Chem Co Ltd | Highly expandable binder composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1375542A1 (en) * | 2002-06-17 | 2004-01-02 | Air Products Polymers, L.P. | Vinyl chloride/vinyl acetate/ethylene/self-crosslinking polymers for non-cellulosic based substrates |
| US8254683B2 (en) | 2005-03-18 | 2012-08-28 | Fujitsu Limited | Code image processing method |
| JP2008126800A (en) * | 2006-11-20 | 2008-06-05 | Valeo Thermal Systems Japan Corp | Car air conditioner |
| JP2013095868A (en) * | 2011-11-02 | 2013-05-20 | Kuraray Co Ltd | Modified vinyl alcohol polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2599733B2 (en) | 1997-04-16 |
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