JPH05214678A - Warp-sizing agent - Google Patents
Warp-sizing agentInfo
- Publication number
- JPH05214678A JPH05214678A JP4046180A JP4618092A JPH05214678A JP H05214678 A JPH05214678 A JP H05214678A JP 4046180 A JP4046180 A JP 4046180A JP 4618092 A JP4618092 A JP 4618092A JP H05214678 A JPH05214678 A JP H05214678A
- Authority
- JP
- Japan
- Prior art keywords
- water
- carboxylic acid
- sizing agent
- aqueous solution
- ethylenically unsaturated
- 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.)
- Pending
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は繊維の経糸糊剤に関し、
更に詳しく言えば、本発明は接着性、耐ブロッキング
性、耐水性及び精練性に優れた性能を発揮する経糸糊剤
に関する。本発明の経糸糊剤は、有機高分子化合物の製
造、繊維用糊剤の製造及び繊維の製織等の分野において
利用される。FIELD OF THE INVENTION The present invention relates to a warp sizing agent for fibers,
More specifically, the present invention relates to a warp sizing agent that exhibits excellent adhesiveness, blocking resistance, water resistance and scouring performance. The warp sizing agent of the present invention is used in the fields of production of organic polymer compounds, production of sizing agents for fibers, and weaving of fibers.
【０００２】[0002]
【従来の技術】ポリエステル、ポリアミド或いはポリプ
ロピレン等の疎水性繊維の製織において、使用される経
糸糊剤には、接着力、耐水性、耐摩耗性、精練性等の性
能が要求される。これは、接着力が不十分な場合は、糊
剤の付着量を多くして製織効率を維持する必要が生じ、
不経済であるばかりでなく、付着量過多によるビームに
おけるブロッキング、落糊により糸切れ或いは織布の汚
れ等の問題が発生するからである。また、耐水性が劣る
と、高温多湿の条件下で糊剤が可塑化して、ビームでブ
ロッキングを生じ易くなり、特にウォータージェットル
ームで製織する場合には、糊皮膜が軟化してオサ羽にガ
ム状物が付着して、経糸の開口状態を阻害するからであ
る。更に、耐磨耗性は糊剤の接着力と皮膜物性が関与
し、接着力が良好なほど、また皮膜が強靱な程、耐磨耗
性が向上するからである。一方、従来の経糸糊剤として
は、例えば、特開昭６２−２２２３号公報に開示され
たアクリル系樹脂を主成分とするものや、特公昭４７
−４０８７３号公報或いは特開昭５９−１５０１７６号
公報に開示されているようなスルホン酸塩を有する水溶
性ポリエステル等が知られている。2. Description of the Related Art In weaving hydrophobic fibers such as polyester, polyamide or polypropylene, a warp sizing agent used is required to have performances such as adhesive strength, water resistance, abrasion resistance and scouring property. If the adhesive strength is insufficient, it is necessary to increase the amount of sizing agent attached to maintain weaving efficiency.
This is not only uneconomical, but also causes problems such as thread breakage or woven fabric stains due to blocking in the beam due to excessive adhesion, and falling glue. If the water resistance is poor, the sizing agent will plasticize under high temperature and high humidity conditions, and blocking will easily occur with the beam. This is because the particulate matter adheres and hinders the open state of the warp. Further, the abrasion resistance depends on the adhesive strength of the sizing agent and the physical properties of the coating, and the better the adhesive strength and the stronger the coating, the more the abrasion resistance is improved. On the other hand, as a conventional warp sizing agent, for example, those containing an acrylic resin as a main component disclosed in Japanese Patent Laid-Open No. 62-2223, and Japanese Patent Publication No. 47/1987.
Water-soluble polyesters having a sulfonate as disclosed in JP-A-40873 or JP-A-59-150176 are known.
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記のアク
リル系樹脂を含有する経糸糊剤は疎水性繊維に対する接
着力が十分でなく、また水溶性ポリエステルを含有す
る経糸糊剤は、接着力は優れているものの、耐水性及び
精練性が不十分である。一方、スルホン酸基を有する
ポリウレタンとアクリル系樹脂をブレンドすることを特
徴とした経糸糊剤（特公平３−９２３１号公報）やス
ルホン酸基を有するポリエステル水溶液中でアクリル単
量体を共重合する経糸糊剤（特開昭６１−２０１０７９
号公報）が開示されているが、アクリル樹脂とポリエス
テル若しくはポリウレタンとの相溶性が十分でなく、皮
膜が不均一で強靱な皮膜が得られず、接着力、耐水性及
び耐磨耗性が不十分である。従って、接着力、耐水性、
精練性及び耐磨耗性すべてを満足する経糸糊剤は見出さ
れていないのが実情である。However, the warp sizing agent containing the above-mentioned acrylic resin does not have sufficient adhesive force to the hydrophobic fiber, and the warp sizing agent containing the water-soluble polyester has excellent adhesive force. However, the water resistance and the scouring property are insufficient. On the other hand, the acrylic monomer is copolymerized in a warp sizing agent (JP-B-3-9231) characterized by blending a polyurethane having a sulfonic acid group and an acrylic resin, or an aqueous polyester solution having a sulfonic acid group. Warp sizing agent (Japanese Patent Laid-Open No. 61-201079)
However, the compatibility between the acrylic resin and the polyester or polyurethane is not sufficient, the coating is not uniform and a tough coating cannot be obtained, and the adhesive strength, water resistance and abrasion resistance are poor. It is enough. Therefore, adhesion, water resistance,
The fact is that no warp sizing agent satisfying all the scouring and abrasion resistance has been found.
【０００４】本発明は、上記欠点を解消して、接着力、
耐水性、精練性及び耐磨耗性のいずれにも優れる経糸糊
剤を提供することを目的とする。The present invention solves the above-mentioned drawbacks by improving the adhesive strength,
It is an object of the present invention to provide a warp sizing agent which is excellent in water resistance, scouring property and abrasion resistance.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記中和
物を必須成分とする組成物が、接着力、耐水性、精練性
及び耐磨耗性のいずれにも優れた性能を発揮することを
見出し、本発明を完成したのである。本第１発明の経糸
糊剤は、エチレン性不飽和基を有する水溶性ポリエステ
ル若しくは水溶性ポリウレタンの水溶液中で、エチレン
性不飽和カルボン酸と該カルボン酸以外のエチレン性不
飽和単量体とを共重合させて得られる共重合体を、アン
モニア、アミン及びアルカリ金属の水酸化物からなる塩
基性物質の１種又は２種以上で中和して得られる中和物
を含有することを特徴とする。The inventors of the present invention have found that the composition containing the above neutralized product as an essential component exhibits excellent performances in all of adhesive strength, water resistance, scouring property and abrasion resistance. The present invention has been completed and the present invention has been completed. The warp sizing agent of the first invention comprises an ethylenically unsaturated carboxylic acid and an ethylenically unsaturated monomer other than the carboxylic acid in an aqueous solution of a water-soluble polyester or water-soluble polyurethane having an ethylenically unsaturated group. It is characterized by containing a neutralized product obtained by neutralizing a copolymer obtained by copolymerization with one or more basic substances consisting of ammonia, amine and hydroxide of alkali metal. To do.
【０００６】上記「エチレン性不飽和基を有するポリエ
ステル」とは、エチレン性不飽和基を含む多価カルボン
酸と多価アルコールとの縮合物である。このエチレン性
不飽和基を含む多価カルボン酸としては、イタコン酸、
マレイン酸、フマール酸等を例示できる。また、このポ
リエステルに使用するカルボン酸としては、その他に、
フタル酸、イソフタル酸、テレフタル酸、アジピン酸、
コハク酸、無水トリメリット酸等のエチレン性不飽和基
を有しない多価カルボン酸を併せて使用してもよい。一
方、多価アルコールとしては、エチレングリコール、
１，３−ブタンジオール、ジエチレングリコール、ジメ
チロールプロピオン酸等を挙げることができる。尚、上
記ポリエステルを、水溶性とするためには、無水トリメ
リット酸又はジメチロールプロピオン酸等の側鎖のカル
ボン酸をアルカリで中和する方法及び５−ソジオイソフ
タル酸を多価カルボン酸の一部として使用する方法等を
挙げることができる。The above "polyester having an ethylenically unsaturated group" is a condensate of a polyvalent carboxylic acid containing an ethylenically unsaturated group and a polyhydric alcohol. As the polyvalent carboxylic acid containing an ethylenically unsaturated group, itaconic acid,
Examples include maleic acid and fumaric acid. In addition, as the carboxylic acid used for this polyester, in addition,
Phthalic acid, isophthalic acid, terephthalic acid, adipic acid,
You may use together polyhydric carboxylic acid which does not have an ethylenically unsaturated group, such as succinic acid and trimellitic anhydride. On the other hand, as the polyhydric alcohol, ethylene glycol,
1,3-butanediol, diethylene glycol, dimethylol propionic acid, etc. can be mentioned. Incidentally, in order to make the above-mentioned polyester water-soluble, a method of neutralizing a side chain carboxylic acid such as trimellitic anhydride or dimethylolpropionic acid with an alkali, and 5-sodioisophthalic acid as a polyvalent carboxylic acid. The method used as a part can be mentioned.
【０００７】上記「エチレン性不飽和基を有するポリウ
レタン」は、糊剤組成物中において分散剤として作用す
るものである。例えば、上記ポリエステルポリオールを
トリレンジイソシアナートやヘキサメチレンジイソシア
ナート等のジイソシアナートと反応させて高分子量化さ
せ水溶性にしたもの（特公平３−９２３１号公報、ＵＳ
４１５０９４６）等が例示できる。また、本第３発明に
示す様に、上記水溶性ポリエステル若しくは上記水溶性
ポリウレタンの有効固形分量（Ｃ）と、上記２種類の不
飽和単量体の合計量（Ｄ）との重量比（Ｃ／Ｄ）を、５
／９５〜５０／５０とするのが好ましい。この比が５未
満では糊剤の接着力が不十分であり、逆に５０を越える
と耐水性及び精練性が低下するからである。The above-mentioned "polyurethane having an ethylenically unsaturated group" functions as a dispersant in the paste composition. For example, one obtained by reacting the above polyester polyol with a diisocyanate such as tolylene diisocyanate or hexamethylene diisocyanate to have a high molecular weight so as to be water-soluble (Japanese Patent Publication No. 3-9231, US Pat.
4150946) and the like. Further, as shown in the third aspect of the present invention, the weight ratio (C) of the effective solid content (C) of the water-soluble polyester or the water-soluble polyurethane and the total amount (D) of the two kinds of unsaturated monomers is / D) to 5
It is preferably / 95 to 50/50. This is because if the ratio is less than 5, the adhesive strength of the sizing agent is insufficient, and if it exceeds 50, the water resistance and the scouring property deteriorate.
【０００８】上記「エチレン性不飽和カルボン酸」とし
ては、アクリル酸、メタクリル酸、イタコン酸、フマー
ル酸、クロトン酸等を挙げることができる。また、上記
「エチレン性不飽和単量体（即ち、上記のエチレン性不
飽和カルボン酸以外のエチレン性不飽和単量体を意味す
る。）」としては、アクリル酸エステル、メタクリル酸
エステル、スチレン、アクリロニトリル、メタクリロニ
トリル、アクリルアミド、メタクリルアミド、酢酸ビニ
ル、エチレン等を例示することができる。更に、上記
「エチレン性不飽和カルボン酸」（Ａ）と上記「エチレ
ン性不飽和単量体」（Ｂ）の重量比（Ａ／Ｂ）は、本第
２発明に示す様に、５／９５〜２０／８０であることが
望ましい。この重量比が５未満では、得られる糊剤が水
溶性に乏しくなり、且つ精練性も劣る。一方、この比が
２０を越えれば、得られる糊剤のブロッキングが激しく
なり実用性を欠くようになるからである。Examples of the above-mentioned "ethylenically unsaturated carboxylic acid" include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid and the like. In addition, as the above-mentioned "ethylenically unsaturated monomer (that is, an ethylenically unsaturated monomer other than the above ethylenically unsaturated carboxylic acid)", acrylic acid ester, methacrylic acid ester, styrene, Examples thereof include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, ethylene and the like. Further, the weight ratio (A / B) of the “ethylenically unsaturated carboxylic acid” (A) and the “ethylenically unsaturated monomer” (B) is 5/95 as shown in the second invention. It is desirable that it is ˜20 / 80. When this weight ratio is less than 5, the obtained sizing agent has poor water solubility and poor scouring property. On the other hand, if this ratio exceeds 20, blocking of the obtained sizing agent will be severe and it will be impractical.
【０００９】上記の如く、本発明では、アンモニア、ア
ミン、アルカリ金属の酸化物及びアルカリ金属の水酸化
物からなる塩基性物質の１種又は２種以上が、中和剤と
して用いられる。このうち、耐水性及び耐ブロッキング
性が要求されるフィラメント用糊剤、特にウォータージ
ェットルーム用においては揮発性アミン又はアンモニア
が好適である。尚、本発明の経糸糊剤の製造は、一般的
な乳化重合の方法と同様な条件で行われるので、特別な
操作は必要でない。即ち、不飽和基を有する水溶性ポリ
ウレタン樹脂又は水溶性ポリエステル樹脂の水溶液を７
０〜８０℃に加熱したところへ、重合触媒の存在下でエ
チレン性不飽和単量体の１種又は２種以上を混合後に滴
下し、共重合を行わせた後、中和剤で中和して目的とす
る糊剤を得ることができる。As described above, in the present invention, one or more basic substances consisting of ammonia, amine, oxide of alkali metal and hydroxide of alkali metal are used as the neutralizing agent. Of these, a sizing agent for filaments, which is required to have water resistance and blocking resistance, particularly a volatile amine or ammonia is preferable for a water jet loom. Since the production of the warp sizing agent of the present invention is performed under the same conditions as in a general emulsion polymerization method, no special operation is required. That is, an aqueous solution of a water-soluble polyurethane resin or a water-soluble polyester resin having an unsaturated group is used.
After heating to 0 to 80 ° C, one or more ethylenically unsaturated monomers are mixed in the presence of a polymerization catalyst and then added dropwise to cause copolymerization and then neutralized with a neutralizing agent. Then, the desired sizing agent can be obtained.
【００１０】[0010]
【作用】本発明は、ポリエステル樹脂等の中にエチレン
性不飽和基を有する。従って、エチレン性不飽和単量体
とのグラフト化が進行するので、得られる皮膜は透明で
耐水性、接着性、耐磨耗性に優れたものとなる。更に、
水溶性ポリエステル又は水溶性ポリウレタンを用い、且
つ所定の共重合体を中和させた塩を用いるので、本経糸
糊剤は適度な水溶性を有する。従って、従来のポリエス
テル、ポリウレタンの欠点である精練性をも向上させる
ことができる。In the present invention, the polyester resin or the like has an ethylenically unsaturated group. Therefore, since the grafting with the ethylenically unsaturated monomer proceeds, the obtained film is transparent and has excellent water resistance, adhesiveness and abrasion resistance. Furthermore,
Since a water-soluble polyester or water-soluble polyurethane is used and a salt obtained by neutralizing a predetermined copolymer is used, the warp sizing agent of the present invention has appropriate water solubility. Therefore, the scouring property, which is a drawback of conventional polyester and polyurethane, can be improved.
【００１１】[0011]
【実施例】以下、実施例及び比較例により本発明を具体
的に説明する。 （１）ポリエステル樹脂の水溶液、ポリウレタン樹脂の
水溶液の調製 本実施例及び比較例に於いて使用した水溶液は、以下の
様にして調製されたものである。 水溶液Ｎｏ．１（ポリエステル水溶液、本発明品） 先ず、イソフタル酸３３２ｇ、１，３ブタンジオール３
６７ｇを４つ口フラスコに仕込み、窒素ガスを導入しな
がら撹拌下に徐々に昇温した。そして、１８０℃まで昇
温した所で、脱水反応が始まった為、生成した水を系外
に取り除いた。次いで、２００℃まで昇温した後、４時
間反応を行い、酸価３２の縮合物を得た。その後、１５
０℃まで冷却し、無水フタル酸２９６ｇ、イタコン酸１
５８ｇ及びジメチロールプロピオン酸２６８ｇを仕込
み、１７０℃で１４時間反応を行い、酸価９０、水酸基
価９０の生成物を得た。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. (1) Preparation of Polyester Resin Aqueous Solution and Polyurethane Resin Aqueous Solution The aqueous solutions used in the examples and comparative examples were prepared as follows. Aqueous solution No. 1 (Polyester aqueous solution, product of the present invention) First, 332 g of isophthalic acid and 1,3 butanediol 3
67 g was placed in a four-necked flask and gradually heated with stirring while introducing nitrogen gas. Then, when the temperature was raised to 180 ° C., the dehydration reaction started, so the generated water was removed to the outside of the system. Then, after raising the temperature to 200 ° C., the reaction was carried out for 4 hours to obtain a condensate having an acid value of 32. Then 15
After cooling to 0 ° C, 296 g of phthalic anhydride and 1 of itaconic acid
58 g and 268 g of dimethylolpropionic acid were charged and reacted at 170 ° C. for 14 hours to obtain a product having an acid value of 90 and a hydroxyl value of 90.
【００１２】更に、この生成物を水溶性にする場合に
は、この生成物を１２０℃まで冷却し、２５重量％のア
ンモニア水１９２ｇと水１２７７ｇの混合物で中和す
る。そして、水２３６２ｇを加えて希釈し、固形分濃度
（水溶液全体を１００としたときの固形分の割合）２５
重量％のポリエステル水溶液Ｎｏ．１を得た。尚、この
水溶液の外観は淡黄色透明で、ｐＨは７．１であった。Further, when the product is made water-soluble, it is cooled to 120 ° C. and neutralized with a mixture of 192 g of 25% by weight ammonia water and 1277 g of water. Then, 2362 g of water was added to dilute it, and the solid content concentration (the ratio of the solid content when the total amount of the aqueous solution was 100) was set to 25.
Wt% polyester aqueous solution No. Got 1. The appearance of this aqueous solution was light yellow and transparent, and the pH was 7.1.
【００１３】水溶液Ｎｏ．２（ポリエステル水溶液、
本発明品） 先ず、イソフタル酸３３２ｇと１，３ブタンジオール５
４９ｇとを、水溶液Ｎｏ．１を調製した場合と同様に、
２００℃で４時間反応させて酸価３４の縮合物とし、そ
の後、無水フタル酸２９６ｇ、無水トリメリット酸３８
４ｇ、イタコン酸１５８ｇを仕込み１８０℃で３時間反
応を行って酸価１１０、水酸基価４０の生成物を得た。
次いで、この生成物を１２０℃に冷却し、２５重量％ア
ンモニア水２２９ｇ、水１４２９ｇの混合液を加えて中
和して、固形分濃度２５重量％のポリエステル水溶液Ｎ
ｏ．２を得た。尚、得られた水溶液の外観は淡黄色透明
で、ｐＨは６．６であった。Aqueous solution No. 2 (polyester aqueous solution,
Inventive product) First, 332 g of isophthalic acid and 5,3-butanediol 5
49 g and the aqueous solution No. As in the case of preparing 1,
The mixture is reacted at 200 ° C. for 4 hours to give a condensate having an acid value of 34, and then 296 g of phthalic anhydride and 38 of trimellitic anhydride.
4 g and 158 g of itaconic acid were charged and reacted at 180 ° C. for 3 hours to obtain a product having an acid value of 110 and a hydroxyl value of 40.
Next, this product is cooled to 120 ° C. and neutralized by adding a mixed solution of 229 g of 25% by weight ammonia water and 1429 g of water, and a polyester aqueous solution N having a solid content concentration of 25% by weight.
o. Got 2. The appearance of the obtained aqueous solution was light yellow and transparent, and the pH was 6.6.
【００１４】水溶液Ｎｏ．３（ポリエステル水溶液、
本発明品） 先ず、５−ソジオイソフタル酸ジメチル２９６ｇ、ジメ
チルイソフタル酸１６２０ｇ、イタコン酸ジメチル１４
４ｇ、１，３ブタンジオール２１６０ｇ及びテトライソ
プロピルチタネート４ｍｌを仕込み、窒素ガスを導入し
ながら１５０〜２２０℃で３０分間脱メタノール反応を
行い、理論量のメタノールを系外に除去し、生成物を得
た。次いで、３〜５ｍｍＨｇの減圧下、１００〜２５０
℃で１２０分間脱グリコール反応を行い、淡黄色透明の
ポリエステル水溶液を得た。更に、このポリエステル水
溶液を水で希釈して固形分濃度２５重量％のＮｏ．３の
水溶液を得た。Aqueous solution No. 3 (polyester aqueous solution,
The product of the present invention) First, 296 g of dimethyl 5-sodioisophthalate, 1620 g of dimethylisophthalic acid, and 14 of dimethyl itaconate.
4 g, 1,3 butanediol (2160 g) and tetraisopropyl titanate (4 ml) were charged, and a methanol removal reaction was carried out at 150 to 220 ° C. for 30 minutes while introducing nitrogen gas to remove the theoretical amount of methanol outside the system to obtain a product. It was Then, under reduced pressure of 3 to 5 mmHg, 100 to 250
The glycol removal reaction was carried out at 120 ° C. for 120 minutes to obtain a pale yellow transparent polyester aqueous solution. Further, this polyester aqueous solution was diluted with water to give a No. An aqueous solution of 3 was obtained.
【００１５】水溶液Ｎｏ．４（ポリウレタン水溶液、
本発明品） 上記水溶液Ｎｏ．１の製造過程で得られた酸価３２の生
成物６９３ｇを減圧下１００℃で脱水した後、５０℃ま
で冷却しメチルエチルケトン３５０ｇを加え、十分に撹
拌混合した。次いで、４−４′ジフェニルメタンジイソ
シアネート２５０ｇを加えて７０℃に加熱し、この温度
で２時間反応させて末端にＮＣＯ基を有するプレポリマ
ー水溶液を得た。更に、このプレポリマー水溶液を４０
℃まで冷却し、メチルエチルケトン４６０ｇを加えて希
釈した。その後、ピペラジン・６Ｈ2 Ｏ、８７ｇとトリ
エチルアミン４６０ｇを予め水２９２ｇに溶解させたア
ミン水溶液に、上記プレポリマー水溶液を徐々に加え
て、鎖延長と中和を同時に行った。この際１０℃の温度
上昇と増粘が見られ、粘稠で透明な生成物が得られた。
更に、この生成物を６５℃で減圧下にメチルエチルケト
ンを除去した後、水を加えて濃度調整し、固形分濃度２
５重量％、粘度１００ｍＰａ・ｓ、ｐＨ７．０の微黄色
のＮｏ．４の水溶液を得た。Aqueous solution No. 4 (polyurethane aqueous solution,
Inventive product) The above aqueous solution No. 693 g of a product having an acid value of 32 obtained in the production process of 1 was dehydrated at 100 ° C. under reduced pressure, cooled to 50 ° C., 350 g of methyl ethyl ketone was added, and the mixture was sufficiently stirred and mixed. Next, 250 g of 4-4 ′ diphenylmethane diisocyanate was added and heated to 70 ° C., and reacted at this temperature for 2 hours to obtain a prepolymer aqueous solution having an NCO group at the terminal. Furthermore, this prepolymer aqueous solution is added to 40
The mixture was cooled to ° C, and 460 g of methyl ethyl ketone was added for dilution. Then, 87 g of piperazine · 6H 2 O and 460 g of triethylamine were dissolved in 292 g of water in advance, and the above prepolymer aqueous solution was gradually added to the amine aqueous solution to simultaneously perform chain extension and neutralization. At this time, a temperature rise of 10 ° C. and thickening were observed, and a viscous and transparent product was obtained.
Furthermore, after removing methyl ethyl ketone from this product under reduced pressure at 65 ° C., water was added to adjust the concentration, and the solid content concentration was adjusted to 2
5% by weight, viscosity 100 mPa · s, pH 7.0, slightly yellowish No. An aqueous solution of 4 was obtained.
【００１６】水溶液Ｎｏ．５（ポリエステル水溶液、
比較例品） 上記水溶液Ｎｏ．１の調製に用いたイタコン酸の代わり
に、等モルの無水フタル酸を用いること以外は同様の方
法にて、固形分濃度２５重量％のＮｏ．５の水溶液を得
た。 水溶液Ｎｏ．６（ポリエステル水溶液、比較例品） 上記水溶液Ｎｏ．２の調製に用いたイタコン酸の代わり
に、等モルの無水フタル酸を用いること以外は同様の方
法にて、固形分濃度２５重量％のＮｏ．６の水溶液を得
た。Aqueous solution No. 5 (polyester aqueous solution,
Comparative Example Product) The above aqueous solution No. The same method was used except that an equimolar amount of phthalic anhydride was used in place of the itaconic acid used in the preparation of No. 1 in No. 1 having a solid content concentration of 25% by weight. An aqueous solution of 5 was obtained. Aqueous solution No. 6 (polyester aqueous solution, comparative example product) No. 2 having a solid content concentration of 25% by weight was prepared by the same method except that an equimolar amount of phthalic anhydride was used in place of the itaconic acid used in the preparation of 2. An aqueous solution of 6 was obtained.
【００１７】水溶液Ｎｏ．７（ポリエステル水溶液、
比較例品） 上記水溶液Ｎｏ．３の調製に用いたイタコン酸の代わり
に、等モルのイソフタル酸ジメチルを用いること以外は
同様の方法にて、固形分濃度２５重量％のＮｏ．７の水
溶液を得た。 水溶液Ｎｏ．８（ポリウレタン水溶液、比較例品） 上記水溶液Ｎｏ．１の調製に用いたイタコン酸の代わり
に等モルの無水フタル酸を用い、且つ上記水溶液Ｎｏ．
４と同様の反応を行って固形分濃度２５重量％のＮｏ．
８の水溶液を得た。Aqueous solution No. 7 (polyester aqueous solution,
Comparative Example Product) The above aqueous solution No. In the same manner as in Example 3, except that the itaconic acid used in the preparation of Example 3 was replaced by an equimolar amount of dimethyl isophthalate, No. An aqueous solution of 7 was obtained. Aqueous solution No. 8 (polyurethane aqueous solution, comparative example product) In place of the itaconic acid used in the preparation of Example 1, equimolar phthalic anhydride was used, and the above aqueous solution No.
The same reaction as in No. 4 was carried out to obtain No. 4 having a solid content of 25% by weight.
An aqueous solution of 8 was obtained.
【００１８】（２）経糸糊剤の調製 上記水溶液Ｎｏ．１〜８を用い、以下の様にして、実施
例品Ｎｏ．１〜４及び比較例品Ｎｏ．１〜４に係わる経
糸糊剤を調製した。 実施例品Ｎｏ．１ 水溶液Ｎｏ．１（固形分濃度；２５重量％）を３０重量
部（以下、「部」という。）、過硫酸アンモニウム０．
１部、水５２．５部を仕込み、窒素ガス雰囲気下で７５
℃に保持し、アクリル酸ｎ−ブチル７．５部、メタクリ
ル酸メチル３．８部、メタクリル酸２．８部及びアクリ
ロニトリル３．５部よりなる単量体混合物を５〜６時間
を要して連続滴下して共重合させた後、更に８０℃で２
時間熟成し共重合を終了させた。次いで、６５℃まで冷
却し、アンモニア水（濃度２８重量％）０．８部を０．
５時間を要して滴下して中和し、実施例１に係わる糊剤
を調製した。(2) Preparation of warp sizing agent Examples Nos. 1 to 8 were used in the following manner. 1-4 and comparative example product No. Warp sizing agents relating to 1 to 4 were prepared. Example product No. Aqueous solution No. 1 1 (solid content concentration; 25% by weight) 30 parts by weight (hereinafter referred to as "part"), ammonium persulfate 0.
Charge 1 part and 52.5 parts of water, and in a nitrogen gas atmosphere 75
The temperature is maintained at 0 ° C., and a monomer mixture consisting of 7.5 parts of n-butyl acrylate, 3.8 parts of methyl methacrylate, 2.8 parts of methacrylic acid and 3.5 parts of acrylonitrile is required for 5 to 6 hours. After continuous dropping and copolymerization, 2 more at 80 ° C.
Aging was carried out for a period of time to terminate the copolymerization. Then, the mixture was cooled to 65 ° C., and 0.8 part of ammonia water (concentration 28% by weight) was added to 0.8.
The sizing agent according to Example 1 was prepared by dropwise addition for 5 hours for neutralization.
【００１９】実施例品Ｎｏ．２ 水溶液Ｎｏ．２（固形分濃度；２５重量％）を用いるこ
と以外は実施例１と同様の方法にて、実施例２に係わる
糊剤を調製した。 実施例品Ｎｏ．３ 水溶液Ｎｏ．３（固形分濃度；２５重量％）を用いるこ
と以外は、実施例１と同様の方法にて、実施例３に係わ
る糊剤を調製した。 実施例品Ｎｏ．４ 水溶液Ｎｏ．４（固形分濃度；２５重量％）を用いるこ
と以外は、実施例１と同様の方法にて、実施例４に係わ
る糊剤を調製した。Example product No. 2 Aqueous solution No. A sizing agent according to Example 2 was prepared in the same manner as in Example 1 except that 2 (solid content concentration: 25% by weight) was used. Example product No. Aqueous solution No. 3 A sizing agent according to Example 3 was prepared in the same manner as in Example 1 except that 3 (solid content concentration: 25% by weight) was used. Example product No. Aqueous solution No. 4 A sizing agent according to Example 4 was prepared in the same manner as in Example 1 except that 4 (solid content concentration: 25% by weight) was used.
【００２０】比較例品Ｎｏ．１〜４ 水溶液Ｎｏ．５〜８の不飽和基を含まないポリエステル
若しくはポリウレタンと、実施例１で用いた単量体混合
物を同様の方法にて共重合させ、更に同様なアンモニア
水による中和を行い、比較例品Ｎｏ．１〜４に係わる糊
剤をそれぞれ調製した。Comparative Example No. 1-4 aqueous solution No. 5 to 8 unsaturated group-free polyester or polyurethane and the monomer mixture used in Example 1 were copolymerized by the same method and further neutralized with the same ammonia water, and Comparative Example product No. ． The sizing agents relating to 1 to 4 were prepared respectively.
【００２１】ここで、以上の実施例及び比較例の糊剤の
性状を表１に示す。尚、エチレン性不飽和カルボン酸
（Ａ）と上記カルボン酸以外のエチレン性不飽和単量体
（Ｂ）の重量比（Ａ／Ｂ）は、いずれの試験品も、１６
／８０である。また、上記水溶性ポリエステル若しくは
上記水溶性ポリウレタンの有効固形分量（Ｃ）と、上記
エチレン性不飽和カルボン酸（Ａ）と該カルボン酸以外
のエチレン性不飽和単量体（Ｂ）との合計量（Ｄ）の重
量比（Ｃ／Ｄ）は、いずれの試験品も、３０／７０であ
る。Table 1 shows the properties of the sizing agents of the above Examples and Comparative Examples. The weight ratio (A / B) of the ethylenically unsaturated carboxylic acid (A) to the ethylenically unsaturated monomer (B) other than the above carboxylic acid was 16 for all test products.
/ 80. Further, the effective solid content (C) of the water-soluble polyester or the water-soluble polyurethane, the total amount of the ethylenically unsaturated carboxylic acid (A) and the ethylenically unsaturated monomer (B) other than the carboxylic acid. The weight ratio (C / D) of (D) is 30/70 for all the test products.
【００２２】[0022]
【表１】 [Table 1]
【００２３】（３）性能試験 本発明の経糸糊剤の性能を明らかにする為、上記各経糸
糊剤に対して、以下に述べる各項目の性能試験を行っ
た。性能評価試験及びその評価方法を以下に示す。 接着性 糊剤水溶液を乾燥時の膜厚が５０μｍになるようにポリ
エステルフィルム上に流し、その上にポリエステルタフ
タを乗せ、７０〜８０℃で９０分間、続いて１１０〜１
２０℃で３０分間乾燥後、２５℃、８０％ＲＨで２４時
間調湿した。次いで、２０×１０ｍｍの試験片を切り出
し、ポリエステルフィルムとポリエステルタフタ間のＴ
剥離強度（ｇｆ／ｃｍ）を、島津製作所製「ＩＳ−５０
０」測定器にて測定した。尚、引っ張り速度は１００ｍ
ｍ／分である。(3) Performance Test In order to clarify the performance of the warp sizing agent of the present invention, a performance test of each item described below was performed on each of the above warp sizing agents. The performance evaluation test and its evaluation method are shown below. Adhesion An aqueous paste solution is poured onto a polyester film so that the film thickness when dried is 50 μm, and polyester taffeta is placed on the polyester film, and the mixture is heated at 70 to 80 ° C. for 90 minutes, and then 110 to 1
After drying at 20 ° C. for 30 minutes, the humidity was adjusted at 25 ° C. and 80% RH for 24 hours. Then, a test piece of 20 × 10 mm was cut out, and T between the polyester film and the polyester taffeta was cut out.
The peel strength (gf / cm) is "IS-50" manufactured by Shimadzu Corporation.
It was measured with a "0" measuring instrument. The pulling speed is 100m
m / min.
【００２４】耐水性 縦２０ｍｍ、横１０ｍｍ、厚さ１００μｍの糊皮膜を作
製し、２５℃、８０％ＲＨで２４時間調湿した後、皮膜
を２５℃の水に１０分間浸漬して水中から取り出し、濾
紙で水を切り、直ちに重量を測定して、次式により吸水
率を算出した。 吸水率（重量％）＝（試験前の重量−試験後の重量）×
１００／試験前の重量 精練性 ポリエステルタフタに１０重量％の糊剤を塗布して風乾
し、１９０℃で３０秒間熱処理した後、下記の精練条件
で糊抜きを行い、ローダミンＢ染料での残糊の状態を観
察評価した。但し、精練条件は、以下の通りである。 精練剤；苛性ソーダ２ｇ／リットル、非イオン系界面活
性剤１．５ｇ／リットル、温度；８０℃、時間；６０秒Water resistance A glue film having a length of 20 mm, a width of 10 mm and a thickness of 100 μm was prepared, and the humidity was adjusted at 25 ° C. and 80% RH for 24 hours, and then the film was immersed in water at 25 ° C. for 10 minutes and taken out from water. The water was drained with a filter paper, the weight was immediately measured, and the water absorption rate was calculated by the following formula. Water absorption rate (% by weight) = (weight before test−weight after test) ×
100 / weight before test Refining property Polyester taffeta was coated with 10% by weight of sizing agent, air-dried, heat-treated at 190 ° C. for 30 seconds, desizing was performed under the following scouring conditions, and residual paste with Rhodamine B dye Was observed and evaluated. However, the refining conditions are as follows. Scouring agent; caustic soda 2 g / liter, nonionic surfactant 1.5 g / liter, temperature; 80 ° C, time; 60 seconds
【００２５】皮膜の強靱性 膜厚０．１６ｍｍの皮膜を作製し、２５℃、８０％ＲＨ
で７日間調湿した後、皮膜の強伸度を測定した時の、面
積（即ち、エネルギー値）を、皮膜の強靱性の目安とし
た。尚、エネルギー値が大きいほど皮膜の強靱性が大で
ある。 皮膜の透明度 膜厚０．１６ｍｍの皮膜を作製し、この皮膜を目視で観
察し、皮膜の透明度の評価を行った。Toughness of film A film having a film thickness of 0.16 mm was prepared at 25 ° C. and 80% RH.
After controlling the humidity for 7 days, the area (that is, energy value) when the strength and elongation of the coating was measured was used as a measure of the toughness of the coating. The higher the energy value, the higher the toughness of the film. Transparency of coating A coating having a thickness of 0.16 mm was prepared, and this coating was visually observed to evaluate the transparency of the coating.
【００２６】（４）性能試験の結果 以上の性能試験の結果を表２に示す。(4) Results of Performance Test Table 2 shows the results of the above performance test.
【００２７】[0027]
【表２】 [Table 2]
【００２８】尚、表２中の「精練性」に関する評価の表
示の意義は、以下の通りである。 ◎：残糊なし、○：やや残糊あり、△：かなり残糊あ
り、×：残糊著しい。 また、同表中の「皮膜の透明度」に関する評価の表示の
意義は、以下の通りである。 ◎：皮膜が透明、○：皮膜にやや濁りあり、△：皮膜に
かなり濁りあり、×：皮膜の濁り著しいを表す。The significance of the display of the evaluation regarding the "scouring property" in Table 2 is as follows. ⊚: No residual paste, ○: Some residual paste, Δ: Significant residual paste, ×: Significant residual paste. Further, the significance of the display of the evaluation regarding the "transparency of the film" in the table is as follows. ⊚: The film is transparent, ∘: the film is slightly cloudy, Δ: the film is considerably cloudy, and x: the film is significantly cloudy.
【００２９】本実施例品Ｎｏ．１〜４の糊剤では、接着
性（剥離強度）において特に優れた値（比較例品の約７
〜１３倍）を示し、また皮膜の強靱性においても著しい
向上（比較例品の糊剤の約２倍〜１３倍）を示した。更
に、吸水率、精錬性及び皮膜の透明度についても、好ま
しい結果を示した。従って、本実施例の糊剤では全ての
試験項目において満足する結果を示した。尚、本発明に
おいては、前記具体的実施例に示すものに限られず、目
的、用途に応じて本発明の範囲内で種々変更した実施例
とすることができる。In this example, the product No. With the sizing agents 1 to 4, the adhesiveness (peeling strength) was particularly excellent (about 7% for the comparative example).
.About.13 times) and markedly improved the toughness of the coating (about 2 to 13 times that of the sizing agent of the comparative example product). Furthermore, favorable results were also shown with respect to water absorption, refining properties and transparency of the film. Therefore, the sizing agent of this example showed satisfactory results in all test items. The present invention is not limited to the specific examples described above, and various modifications may be made within the scope of the present invention depending on the purpose and application.
【００３０】[0030]
【発明の効果】以上のように、本発明の経糸糊剤では、
接着性、耐水性、皮膜の強靱性及び精練性の各要求性能
を、全て満足している。また、耐ブロッキング性も良好
で、落糊が少なくなるため製織効率が向上し、高品位の
織布を生産することが可能となる。また、本経糸糊剤
は、すべての性能に優れた効果が認められるため、ウォ
ータージェットルーム用糊剤として優れた効果を発揮す
る。更に、本経糸糊剤は、天然繊維にも合成繊維にも好
適に使用でき、また、フィラメント糸とスパン糸の区別
なく使用でき、更にサイジング方式にも関係なく使用で
き、その使用範囲が極めて広い。As described above, in the warp sizing agent of the present invention,
It satisfies all the required performances such as adhesion, water resistance, film toughness and scouring. In addition, the blocking resistance is good, and the falling glue is reduced, so that the weaving efficiency is improved, and it becomes possible to produce a high-quality woven fabric. Further, the present warp yarn sizing agent exhibits excellent effects on all performances, and therefore exhibits excellent effects as a sizing agent for water jet loom. Furthermore, the present warp sizing agent can be suitably used for both natural fibers and synthetic fibers, and can be used without distinction between filament yarn and spun yarn. Further, it can be used regardless of the sizing method, and its use range is extremely wide. ..
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 125/08 ＪＣＮ 9166−4Ｊ 131/04 ＪＣＸ 6904−4Ｊ Ｄ０６Ｍ 15/21 Continuation of front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location C09J 125/08 JCN 9166-4J 131/04 JCX 6904-4J D06M 15/21
Claims (3)
エステル若しくは水溶性ポリウレタンの水溶液中で、エ
チレン性不飽和カルボン酸と該カルボン酸以外のエレチ
ン性不飽和単量体とを共重合させて得られる共重合体
を、 アンモニア、アミン及びアルカリ金属の水酸化物からな
る塩基性物質の１種又は２種以上で中和して得られる中
和物を含有することを特徴とする経糸糊剤。1. Obtained by copolymerizing an ethylenically unsaturated carboxylic acid and an eletinically unsaturated monomer other than the carboxylic acid in an aqueous solution of a water-soluble polyester or water-soluble polyurethane having an ethylenically unsaturated group. A warp sizing agent containing a neutralized product obtained by neutralizing the obtained copolymer with one or more basic substances consisting of ammonia, amine and a hydroxide of an alkali metal.
と上記カルボン酸以外のエチレン性不飽和単量体（Ｂ）
の重量比（Ａ／Ｂ）が、５／９５〜２０／８０である請
求項１記載の経糸糊剤。2. The ethylenically unsaturated carboxylic acid (A)
And an ethylenically unsaturated monomer (B) other than the above carboxylic acid
The warp size agent according to claim 1, wherein the weight ratio (A / B) is 5/95 to 20/80.
溶性ポリウレタンの有効固形分量（Ｃ）と、上記エチレ
ン性不飽和カルボン酸と該カルボン酸以外のエチレン性
不飽和単量体との合計量（Ｄ）の重量比（Ｃ／Ｄ）が、
５／９５〜５０／５０である請求項１記載の経糸糊剤。3. The effective solid content (C) of the water-soluble polyester or the water-soluble polyurethane, and the total amount (D) of the ethylenically unsaturated carboxylic acid and an ethylenically unsaturated monomer other than the carboxylic acid. The weight ratio (C / D) of
The warp sizing agent according to claim 1, which is 5/95 to 50/50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4046180A JPH05214678A (en) | 1992-01-31 | 1992-01-31 | Warp-sizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4046180A JPH05214678A (en) | 1992-01-31 | 1992-01-31 | Warp-sizing agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05214678A true JPH05214678A (en) | 1993-08-24 |
Family
ID=12739839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4046180A Pending JPH05214678A (en) | 1992-01-31 | 1992-01-31 | Warp-sizing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05214678A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104947423A (en) * | 2015-07-13 | 2015-09-30 | 湖州宏鑫绸厂 | Novel synthetic fiber sizing agent |
| CN104988733A (en) * | 2015-07-29 | 2015-10-21 | 湖北佳特纺织浆料有限公司 | Water-soluble polyester slurry for FDY filament sizing water-jet weaving and preparation method thereof |
| CN105803778A (en) * | 2016-04-05 | 2016-07-27 | 吴江福汇缘家纺有限公司 | Nano textile size and preparation method thereof |
| CN114032689A (en) * | 2021-12-15 | 2022-02-11 | 温州百德富新材料有限公司 | Water-based woven tape sizing slurry and preparation method thereof |
-
1992
- 1992-01-31 JP JP4046180A patent/JPH05214678A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104947423A (en) * | 2015-07-13 | 2015-09-30 | 湖州宏鑫绸厂 | Novel synthetic fiber sizing agent |
| CN104988733A (en) * | 2015-07-29 | 2015-10-21 | 湖北佳特纺织浆料有限公司 | Water-soluble polyester slurry for FDY filament sizing water-jet weaving and preparation method thereof |
| CN105803778A (en) * | 2016-04-05 | 2016-07-27 | 吴江福汇缘家纺有限公司 | Nano textile size and preparation method thereof |
| CN114032689A (en) * | 2021-12-15 | 2022-02-11 | 温州百德富新材料有限公司 | Water-based woven tape sizing slurry and preparation method thereof |
| CN114032689B (en) * | 2021-12-15 | 2023-12-26 | 温州百德富新材料有限公司 | Aqueous braid sizing slurry and preparation method thereof |
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