JP4529438B2 - Synthetic rubber latex - Google Patents
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本発明は、繊維用バインダーに用いられる合成ゴムラテックスに関するもので、さらに詳細には、パルプ繊維、合成繊維等の湿潤引っ張り強度を向上させ、且つホルマリンを全く遊離しない繊維用バインダー、パルプ不織布用途に好適な合成ゴムラテックスに関するものである。 The present invention relates to a synthetic rubber latex used as a binder for fibers, and more specifically, for fiber binders and pulp nonwoven fabrics that improve wet tensile strength of pulp fibers, synthetic fibers, etc., and do not release formalin at all. It relates to a suitable synthetic rubber latex.
従来、合成繊維、パルプ繊維等のバインダー用途には、合成ゴムラテックスが使用されているが、湿潤時の強度(湿潤強度)が不足する問題点があった。その改善策として、エチレン系不飽和カルボン酸アミドのメチロール誘導体を合成ゴムラテックスへ導入することよる湿潤強度の向上策が提案されていた(例えば、特許文献1参照)。しかし、前記の湿潤強度の向上策では、エチレン系不飽和カルボン酸アミドのメチロール誘導体から、遊離した多量のホルマリンが発生し、衛生上の問題がある。またホルマリンに対する規制は年々厳しくなるいっぽうであり、建築基準法の改正を受け、繊維業界においても、完全ノンホルマリン化が不可欠な要素になってきている。そういった背景があるため、前記方法では、エチレン系不飽和カルボン酸アミドのメチロール誘導体の導入量を低減するか、或いは、ホルマリンキャッチャーを多量に添加すること等対策が必要となった。しかし、何れの場合も、完全ノンホルマリン化は不可能であり、湿潤強度の低下も生じる。従って、湿潤時の強度(湿潤強度)低下の改善策と完全ノンホルマリン化の両方を満足する合成ゴムラテックスは、見出されていなかった。 Conventionally, synthetic rubber latex has been used for binder applications such as synthetic fibers and pulp fibers, but there has been a problem that strength (wet strength) when wet is insufficient. As an improvement measure, an improvement measure of wet strength by introducing a methylol derivative of an ethylenically unsaturated carboxylic acid amide into a synthetic rubber latex has been proposed (see, for example, Patent Document 1). However, the above-mentioned measures for improving the wet strength have a problem of hygiene because a large amount of free formalin is generated from the methylol derivative of the ethylenically unsaturated carboxylic acid amide. Also, regulations on formalin are becoming stricter year by year, and with the revision of the Building Standard Law, completely non-formalization has become an indispensable element in the textile industry. Because of such background, the above method requires measures such as reducing the introduction amount of the methylol derivative of ethylenically unsaturated carboxylic acid amide, or adding a large amount of formalin catcher. However, in any case, complete non-formalization is impossible and a decrease in wet strength occurs. Therefore, a synthetic rubber latex satisfying both a measure for improving strength when wet (wet strength) and complete non-formalization has not been found.
従って、本発明の課題は、エチレン系不飽和カルボン酸アミドのメチロール誘導体を使用しなくても、繊維バインダーとして、エチレン系不飽和カルボン酸アミドのメチロール誘導体を導入して得られる湿潤強度を同等のレベルの湿潤強度を有し、しかもホルマリンを遊離しない、繊維バインダー用合成ゴムラテックスを提供することである。 Therefore, the object of the present invention is to provide an equivalent wet strength obtained by introducing a methylol derivative of an ethylenically unsaturated carboxylic acid amide as a fiber binder without using a methylol derivative of an ethylenically unsaturated carboxylic acid amide. It is to provide a synthetic rubber latex for a fiber binder having a level of wet strength and not releasing formalin.
本発明者らは、上記課題を解決するために、鋭意検討した結果、エチレン系不飽和カルボン酸アミドを含有した単量体類を乳化重合してなる合成ゴムラテックスが、前記課題解決となることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a synthetic rubber latex obtained by emulsion polymerization of monomers containing an ethylenically unsaturated carboxylic acid amide can solve the above problems. And found the present invention.
即ち、本発明は、エチレン系不飽和カルボン酸アミド(a)1.5〜10重量%と脂肪族ジエン単量体(b)5〜50重量%と、エチレン系不飽和カルボン酸単量体(c)0.5〜10重量%と、スチレン(d)30〜93重量%を含有する不飽和単量体類を重合して得られる合成ゴムラテックスであって、前記合成ゴムラテックスが前記(b)と(c)と(d)とを含有し、且つ前記(a)を含有しない不飽和単量体類を乳化重合して、重合体(I)を得た後、前記重合体(I)の存在下で、前記(a)と(b)と(d)とを含有し、且つ(c)を含有しない単量体混合物を乳化重合して得られる重合体(II)であることを特徴とする合成ゴムラテックスを、紙に含浸して得られる含浸紙を提供する。
また、本発明は、エチレン系不飽和カルボン酸アミド(a)1.5〜10重量%と脂肪族ジエン単量体(b)5〜50重量%と、エチレン系不飽和カルボン酸単量体(c)0.5〜10重量%と、スチレン(d)30〜93重量%を含有する不飽和単量体類を重合して得られる合成ゴムラテックスであって、前記合成ゴムラテックスが前記(a)と(b)と(c)と(d)とを含有する不飽和単量体類を乳化重合して重合体(I)を得た後、前記重合体(I)の存在下で、前記(b)と(d)とを含有し、且つ(a)を含有しない単量体混合物を乳化重合して得られる重合体(II)であることを特徴とする合成ゴムラテックスを、紙に含浸して得られる含浸紙を提供する。
That is, the present invention comprises an ethylenically unsaturated carboxylic acid amide (a) 1.5 to 10% by weight, an aliphatic diene monomer (b) 5 to 50% by weight, an ethylenically unsaturated carboxylic acid monomer ( c) a synthetic rubber latex obtained by polymerizing unsaturated monomers containing 0.5 to 10% by weight and 30 to 93% by weight of styrene (d), wherein the synthetic rubber latex is (b) ), (C), and (d), and the unsaturated monomers not containing (a) are emulsion-polymerized to obtain a polymer (I), and then the polymer (I) A polymer (II) obtained by emulsion polymerization of a monomer mixture containing (a), (b) and (d) and not containing (c) in the presence of An impregnated paper obtained by impregnating a paper with the synthetic rubber latex is provided.
Further, the present invention relates to an ethylenically unsaturated carboxylic acid amide (a) 1.5 to 10% by weight, an aliphatic diene monomer (b) 5 to 50% by weight, an ethylenically unsaturated carboxylic acid monomer ( c) a synthetic rubber latex obtained by polymerizing unsaturated monomers containing 0.5 to 10% by weight and styrene (d) 30 to 93% by weight, wherein the synthetic rubber latex is ), (B), (c) and (d) are subjected to emulsion polymerization to obtain a polymer (I), and then in the presence of the polymer (I), Impregnated paper with synthetic rubber latex, which is a polymer (II) obtained by emulsion polymerization of a monomer mixture containing (b) and (d) and not containing (a) Thus obtained impregnated paper is provided.
本発明によれば、パルプ繊維、合成繊維等の湿潤引っ張り強度を著しく向上させ、且つ遊離ホルマリン量を低減した繊維用バインダー、パルプ不織布用途に使用される合成ゴムラテックスを提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the synthetic rubber latex used for the fiber binder and pulp nonwoven fabric use which improved wet tensile strength, such as a pulp fiber and a synthetic fiber, and reduced the amount of free formalins can be provided.
本発明の合成ゴムラテックスは、前記エチレン系不飽和カルボン酸アミド(a)と脂肪族ジエン系単量体(b)を不飽和単量体類の必須成分とし、必要に応じてエチレン系不飽和カルボン酸単量体(c)または、前記(a)〜(c)以外の1種類以上の共重合可能なビニル化合物(d)等の不飽和単量体類を、後述する方法で乳化重合して得た樹脂の水分散体である。 The synthetic rubber latex of the present invention comprises the ethylenically unsaturated carboxylic acid amide (a) and the aliphatic diene monomer (b) as essential components of unsaturated monomers, and if necessary, ethylenically unsaturated. Emulsion polymerization of unsaturated monomers such as the carboxylic acid monomer (c) or one or more copolymerizable vinyl compounds (d) other than the above (a) to (c) by the method described later. An aqueous dispersion of the resin obtained in this way.
本発明の合成ゴムラテックスに使用されるエチレン系不飽和カルボン酸アミド(a)としては、アクリルアミド、メタアクリルアミド及びN−ブトキシメチルアクリルアミド等が挙げられるが、好ましくはアクリルアミドである。 Examples of the ethylenically unsaturated carboxylic acid amide (a) used in the synthetic rubber latex of the present invention include acrylamide, methacrylamide and N-butoxymethylacrylamide, and acrylamide is preferred.
エチレン系不飽和カルボン酸アミド(a)は、不飽和単量体類の総重量の1.5〜10重量%であることが必要であり、2〜5重量%であることが特に好ましい。ここで、エチレン系不飽和カルボン酸アミド(a)が1.5重量%未満の場合は、合成ゴムラテックスの湿潤強度が低下し好ましくない。また、(a)が10重量%を超える場合は、乳化重合中の凝集物量が著しく増加したり、ゲル化したりして、重合反応の面から好ましくない。 The ethylenically unsaturated carboxylic acid amide (a) is required to be 1.5 to 10% by weight, particularly preferably 2 to 5% by weight, based on the total weight of the unsaturated monomers. Here, when the ethylenically unsaturated carboxylic acid amide (a) is less than 1.5% by weight, the wet strength of the synthetic rubber latex is lowered, which is not preferable. On the other hand, when (a) exceeds 10% by weight, the amount of aggregate during emulsion polymerization is remarkably increased or gelled, which is not preferable from the viewpoint of polymerization reaction.
前記脂肪族ジエン系単量体(b)としては、例えば、1,3−ブタジエン、イソプレン、2−クロル−1,3−ブタジエンなどが挙げられるが、これらの中でも、1,3−ブタジエンが好ましく、その使用量は、単量体総重量の5〜50重量%の範囲が好ましい。5重量%未満の場合、バインダーとしての弾性がなくなり、50重量%を超えると、付着した繊維の剛性に欠けるためである。 Examples of the aliphatic diene monomer (b) include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, and among these, 1,3-butadiene is preferable. The amount used is preferably in the range of 5 to 50% by weight of the total weight of the monomers. When the amount is less than 5% by weight, the elasticity as a binder is lost, and when it exceeds 50% by weight, the rigidity of the attached fiber is lacking.
また、本発明の合成ゴムラテックスを製造する際には、不飽和単量体類として、エチレン系不飽和カルボン酸単量体(c)を用いることが好ましく、該エチレン系不飽和カルボン酸単量体(c)としては、例えば、アクリル酸、メタアクリル酸、イタコン酸、フマル酸、マレイン酸、メタアクリル酸、アクリル酸及びジカルボン酸のハーフエステル類等が挙げられるが、好ましくは、アクリル酸、メタアクリル酸、イタコン酸である。またこれらエチレン系不飽和カルボン酸単量体の1種類または複数使用しても構わず、その使用量は、ラテックスの機械的強度が充分発現すると共に、エチレン系不飽和カルボン酸アミドとの化学的作用が顕著であることから0.5重量%以上が好ましく、また合成ゴムラテックスの増粘しにくいことから10重量%以下が好ましい。 Moreover, when producing the synthetic rubber latex of the present invention, it is preferable to use the ethylenically unsaturated carboxylic acid monomer (c) as the unsaturated monomer, and the ethylenically unsaturated carboxylic acid monomer Examples of the body (c) include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, methacrylic acid, half esters of acrylic acid and dicarboxylic acid, and preferably acrylic acid, Methacrylic acid and itaconic acid. One or a plurality of these ethylenically unsaturated carboxylic acid monomers may be used, and the amount used is sufficient for the mechanical strength of the latex to be fully expressed, and the chemical properties with the ethylenically unsaturated carboxylic acid amide. 0.5% by weight or more is preferable because the action is remarkable, and 10% by weight or less is preferable because it is difficult for the synthetic rubber latex to thicken.
また、本発明の合成ゴムラテックスを製造する際には、必要に応じて、前記(a)〜(c)以外の共重合可能なビニル化合物(d)が1種類以上使用できる。前記ビニル化合物(d)としては、例えば、スチレン、α−メチルスチレン、クロルスチレン、ビニルトルエン、メタアクリロニトリル、アクリロニトリル、メタアクリル酸メチル、メタアクリル酸プロピル、ヒドロキシエチルメタアクリレート、メタアクリル酸−2−エチルヘキシル、メタアクリル酸ラウリル、アクリル酸メチル、アクリル酸エチル、アミノエチルメタアクリレート、ジメチルアミノエチルメタアクリレート、ジエチルアミノエチルメタアクリレート、アクリル酸ブチル、アクリル酸2−エチルヘキシル、アクリル酸2−エチルヘキシルヒドロキシエチルアクリレート、アミノエチルアクリレート、ジメチルアミノエチルアクリレート、ジエチルアミノエチルアクリレート等が挙げられ、最も好ましくはスチレンであり、その使用量は、単量体類の総重量の30〜93重量%が好ましく、特に50〜70重量%が好ましい。 Moreover, when manufacturing the synthetic rubber latex of this invention, the vinyl compound (d) other than the said (a)-(c) other than the said (a)-(c) can use 1 or more types. Examples of the vinyl compound (d) include styrene, α-methylstyrene, chlorostyrene, vinyl toluene, methacrylonitrile, acrylonitrile, methyl methacrylate, propyl methacrylate, hydroxyethyl methacrylate, and methacrylate-2- Ethylhexyl, lauryl methacrylate, methyl acrylate, ethyl acrylate, aminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl hydroxyethyl acrylate, Aminoethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate and the like, and most preferably styrene, The amount of the 30 to 93% by weight of the total weight of the monomers are preferred, in particular 50 to 70% by weight.
本発明の合成ゴムラテックスを乳化重合して得る際に使用する重合開始剤としては、特に限定されないが、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等の過硫酸塩系開始剤、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、ベンゾイルパーオキサイド等の有機過酸化物、過酸化水素等を挙げられる。 The polymerization initiator used when the synthetic rubber latex of the present invention is obtained by emulsion polymerization is not particularly limited, and examples thereof include persulfate-based initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate, cumene hydro Examples thereof include organic peroxides such as peroxide, diisopropylbenzene hydroperoxide and benzoyl peroxide, and hydrogen peroxide.
また、乳化重合を促進させるために、亜硫酸ナトリウム、亜硫酸水素ナトリウム、硫酸第一鉄、グルコース、ホルムアルデヒド、L−アスコルビン酸、ナトリウムスルホキシレート等の還元剤、グリシン、アラニン、エチレンジアミン四酢酸アンモニウム塩等のキレート剤を併用しても良い。 In order to promote emulsion polymerization, reducing agents such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, glucose, formaldehyde, L-ascorbic acid, sodium sulfoxylate, glycine, alanine, ammonium ethylenediaminetetraacetate, etc. These chelating agents may be used in combination.
乳化重合に使用する乳化剤としては、反応性界面活性剤を含めた通常のアニオン性界面活性剤、ノニオン性界面活性剤等であり、何ら限定するものではない。 The emulsifier used in the emulsion polymerization is a normal anionic surfactant including a reactive surfactant, a nonionic surfactant, or the like, and is not limited at all.
本発明の合成ゴムラテックスは、前記の単量体組成をベースとするが、任意の分子量にするために、重合時に連鎖移動剤及び重合停止剤等の分子量調整剤または重合率調整剤を適宜使用することができる。更に冷却による反応中断により分子量のコントロールを行っても良い。また粒子径をコントロールすべく、適当なラテックスを用いてシード重合を行っても構わない。 The synthetic rubber latex of the present invention is based on the above monomer composition, but in order to obtain an arbitrary molecular weight, a molecular weight regulator or a polymerization rate regulator such as a chain transfer agent and a polymerization terminator is appropriately used during polymerization. can do. Further, the molecular weight may be controlled by interrupting the reaction by cooling. In order to control the particle diameter, seed polymerization may be performed using an appropriate latex.
また、連鎖移動剤としては、例えば、通常の重合で使用されるものを使用することができる、たとえばt−ドデシルメルカプタン、n−トデシルメルカプタン、オクチルメルカプタン、n−テトラデシルメルカプタン、n−ヘキシルメルカプタン等のメルカプタン類、ターピノーレン、t−テルピネン、α−メチルスチレンダイマー、エチルキサントゲンジスルフィド、ジイソプロピルキサントゲンスルフィド、アミノフェニルスルフィド、テトラエチルチウラムジスルフィド等が挙げられ、これらの1種又は2種以上を使用することができる。 Moreover, as a chain transfer agent, what is used by normal polymerization can be used, for example, t-dodecyl mercaptan, n-todecyl mercaptan, octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan Such as mercaptans, terpinolene, t-terpinene, α-methylstyrene dimer, ethyl xanthogen disulfide, diisopropyl xanthogen sulfide, aminophenyl sulfide, tetraethyl thiuram disulfide, etc., and one or more of these may be used. it can.
また、重合停止剤としては、例えばハイドロキノン(フェノール)系、アミン系、硫黄系、硫酸ヒドロキシルアミン、アンモニア、苛性ソーダ、苛性カリ等が挙げられ、またその他重合停止効果のあるものが使用でき、更にこれらを複数併用しても良い。その使用量は重合禁止剤の種類及び単量体との反応性比により異なる。 Examples of the polymerization terminator include hydroquinone (phenol) -based, amine-based, sulfur-based, hydroxylamine sulfate, ammonia, caustic soda, caustic potash, and the like. Two or more may be used together. The amount used varies depending on the type of polymerization inhibitor and the reactivity ratio with the monomer.
本発明の合成ゴムラテックスの重合方法としては、たとえば、前記単量体(a)、(b)、(c)及び(d)を一括添加して、1段の乳化重合反応を行って樹脂を得る方法、或いは前記単量体(b)、(c)及び(d)を乳化重合して得られる重合体(I)の存在下で、(a)を必須成分として、必要に応じて(b)及び(d)の混合物を重合して樹脂(II)を得る方法、または(a)、(b)及び(C)からなる重合体(I)の存在化、(b)及び(d)の混合物を重合して樹脂(II)を得る方法等が挙げられる。 As a polymerization method of the synthetic rubber latex of the present invention, for example, the monomers (a), (b), (c) and (d) are added all at once, and a one-stage emulsion polymerization reaction is performed to obtain a resin. In the presence of the polymer (I) obtained by emulsion polymerization of the monomers (b), (c) and (d), with (a) as an essential component and (b ) And (d) to obtain a resin (II), or the presence of a polymer (I) comprising (a), (b) and (C), (b) and (d) The method etc. which superpose | polymerize a mixture and obtain resin (II) are mentioned.
前記2種類の方法のうちでは、アミド基がラテックス粒子表面に局在化し、湿潤強度への寄与が多くなることから、1段重合よりも2段重合の方が、好ましい。 Of the two methods, the amide group is localized on the surface of the latex particles, and the contribution to the wet strength is increased. Therefore, the two-stage polymerization is preferable to the one-stage polymerization.
前記乳化重合方法では、前記の単量体混合物を、乳化剤、重合開始剤、重合促進剤、連鎖移動剤、塩基性化合物の存在下で、45℃〜90℃で重合を行う。この際、前記の1段の乳化重合反応、2段重合についても、条件については同様である。 In the emulsion polymerization method, the monomer mixture is polymerized at 45 ° C. to 90 ° C. in the presence of an emulsifier, a polymerization initiator, a polymerization accelerator, a chain transfer agent, and a basic compound. At this time, the conditions are the same for the one-stage emulsion polymerization reaction and the two-stage polymerization.
また、乳化重合は、上記重合乳化剤、連鎖移動剤、重合開始剤、重合禁止剤等の他、必要に応じて各種電解質、pH調整剤等を併用して種々の方法で行えば良い。 Emulsion polymerization may be carried out by various methods using the above-mentioned polymerization emulsifier, chain transfer agent, polymerization initiator, polymerization inhibitor, etc., as well as various electrolytes, pH adjusters and the like as required.
本発明の合成ゴムラテックスは、不揮発分30〜70重量%であることが、取り扱いの点から好ましいが、必要に応じ、水、水溶性の溶媒等で希釈して使用することができる。 The synthetic rubber latex of the present invention preferably has a nonvolatile content of 30 to 70% by weight from the viewpoint of handling, but can be used by diluting with water, a water-soluble solvent or the like, if necessary.
また本発明の合成ゴムラテックスには、尿素、エチレン尿素、ジシアンジアミド、塩酸ヒドロキシルアミン等のホルマリンキャッチャーを重合時添加または重合終了後に適量加えることができる。その他、その使用目的に応じて以下の配合資材を加えても構わない。 In addition, a formalin catcher such as urea, ethylene urea, dicyandiamide, and hydroxylamine hydrochloride can be added to the synthetic rubber latex of the present invention at the time of polymerization or after completion of the polymerization. In addition, you may add the following compounding materials according to the purpose of use.
本発明の合成ゴムラテックスに加えても良い添加剤としては、例えば、吸水剤、無機顔料、有機顔料等の着色剤、キレート剤、分散剤、酸化防止剤、紫外線吸収剤、界面活性剤、圧縮回復剤、消泡剤、殺菌剤、防腐剤、湿潤剤、メラミン系を除く架橋剤、酸化亜鉛・硫黄・加硫促進剤等の加硫剤、タック防止剤、起泡剤、整泡剤、浸透剤、撥水・撥油剤・ブロッキング防止剤、難燃剤、充填剤、増粘剤等を挙げることができ。前記ホルマリンキャッチャー或いは前記添加剤の選択、添加量、添加順序等は、SBRラテックス100重量部に対して0.0001〜10重量部の範囲添加することが好ましいが、ラテックスの製造条件、作業性、安定性、更に加工適性、塗布量等を考慮して、適宜に決定されれば良い。 Additives that may be added to the synthetic rubber latex of the present invention include, for example, colorants such as water-absorbing agents, inorganic pigments, organic pigments, chelating agents, dispersants, antioxidants, ultraviolet absorbers, surfactants, compression agents. Recovery agent, antifoaming agent, bactericidal agent, preservative, wetting agent, cross-linking agent excluding melamine, vulcanizing agent such as zinc oxide, sulfur, vulcanization accelerator, tack prevention agent, foaming agent, foam stabilizer, Examples include penetrants, water / oil repellents, antiblocking agents, flame retardants, fillers, and thickeners. The selection of the formalin catcher or the additive, the addition amount, the order of addition, etc. are preferably added in the range of 0.0001 to 10 parts by weight with respect to 100 parts by weight of the SBR latex. It may be determined appropriately in consideration of stability, processability, coating amount, and the like.
以下に実施例を挙げて本発明を説明するが、実施例及び表中における部及び%は特に断らない限り、重量基準である。 Hereinafter, the present invention will be described with reference to examples, but parts and% in the examples and tables are based on weight unless otherwise specified.
比較例7〜12
蒸留水130部、重合乳化剤1.5部、t−ドデシルメルカプタン0.2部及びブタジエン、スチレン、アクリルアミド及びアクリル酸またはイタコン酸の単量体を表1に示す様、オートクレーブ内に仕込み、60℃に昇温後、過硫酸アンモニウム0.3部を仕込み10時間反応を行った。反応終了後、アンモニアでpHを8.0以上に調整、ストリッピングを行い、アンモニアでpH7.5〜8.0に調整し、合成ゴムラテックス1〜6を得た。このラテックスを5%に希釈し、No.2濾紙(東洋濾紙製)に樹脂付着量が17%になる様、含浸後、マングルロールで付着量を調整した。得られた含浸濾紙を140℃で10分間乾燥し、幅1.5cm×長さ15cmの試片に切り取り、常態及び湿潤時の引っ張り強度測定用試片とした。湿潤引っ張り強度は、25℃の水中に1時間浸漬後測定した。また、残りの試片を2.5g精秤し、JIS L 1041(A法:アセチルアセトン法)に従い、遊離ホルマリン量(吸光度)の測定を行った。但し吸光度0.05以下は検出限界とする。
Comparative Examples 7-12
As shown in Table 1, 130 parts of distilled water, 1.5 parts of polymerization emulsifier, 0.2 part of t-dodecyl mercaptan and butadiene, styrene, acrylamide, and acrylic acid or itaconic acid monomers were charged in an autoclave at 60 ° C. After raising the temperature, 0.3 part of ammonium persulfate was added and reacted for 10 hours. After completion of the reaction, the pH was adjusted to 8.0 or higher with ammonia and stripping was performed, and the pH was adjusted to 7.5 to 8.0 with ammonia to obtain synthetic rubber latexes 1 to 6. This latex was diluted to 5%. After impregnation, the adhesion amount was adjusted with a mangle roll so that the resin adhesion amount was 17% on 2 filter papers (manufactured by Toyo filter paper). The obtained impregnated filter paper was dried at 140 ° C. for 10 minutes, cut into a specimen having a width of 1.5 cm and a length of 15 cm, and used as a specimen for measuring tensile strength at normal and wet conditions. The wet tensile strength was measured after immersion in water at 25 ° C. for 1 hour. In addition, 2.5 g of the remaining specimen was precisely weighed, and the amount of free formalin (absorbance) was measured according to JIS L 1041 (Method A: acetylacetone method). However, the absorbance of 0.05 or less is the detection limit.
実施例7〜12
蒸留水130部、重合乳化剤1.5部、t−ドデシルメルカプタン0.2部及びブタジエン、スチレン、アクリルアミド及びアクリル酸またはイタコン酸の単量体を表2に示す様、オートクレーブ内に仕込み、60℃に昇温後、過硫酸アンモニウム0.3部を仕込み8〜10時間反応を行う。得られたラテックスに、表3に示す様、アクリルアミド、スチレン、ブタジエン及び過硫酸アンモニウム0.2部を加え、更に65℃で6〜8時間反応を行った。反応終了後、アンモニアでpHを8.0以上に調整、ストリッピングを行い、アンモニアでpH7.5〜8.0に調整し、合成ゴムラテックス7〜12を得た。このラテックスを5%に希釈し、No.2濾紙(東洋濾紙製)に樹脂付着量が17%になる様、含浸後、マングルロールで付着量を調整した。得られた含浸濾紙を140℃で10分間乾燥し、幅1.5cm×長さ15cmの試片に切り取り、常態及び湿潤時の引っ張り強度測定用試片とした。湿潤引っ張り強度は、25℃の水中に1時間浸漬後測定した。また残りの試片を2.5g精秤し、JIS L 1041(A法:アセチルアセトン法)に従い、遊離ホルマリン量(吸光度)の測定を行った。但し、吸光度0.05以下は検出限界とする。
Examples 7-12
Distilled water 130 parts, polymerization emulsifier 1.5 parts, t-dodecyl mercaptan 0.2 part and monomers of butadiene, styrene, acrylamide and acrylic acid or itaconic acid were charged in an autoclave as shown in Table 2, After raising the temperature, 0.3 part of ammonium persulfate is charged and the reaction is carried out for 8 to 10 hours. As shown in Table 3, acrylamide, styrene, butadiene and ammonium persulfate 0.2 part were added to the obtained latex, and the reaction was further performed at 65 ° C. for 6 to 8 hours. After completion of the reaction, the pH was adjusted to 8.0 or higher with ammonia and stripping was performed, and the pH was adjusted to 7.5 to 8.0 with ammonia to obtain synthetic rubber latices 7 to 12. This latex was diluted to 5%. After impregnation, the adhesion amount was adjusted with a mangle roll so that the resin adhesion amount was 17% on 2 filter papers (manufactured by Toyo filter paper). The obtained impregnated filter paper was dried at 140 ° C. for 10 minutes, cut into a specimen having a width of 1.5 cm and a length of 15 cm, and used as a specimen for measuring tensile strength at normal and wet conditions. The wet tensile strength was measured after immersion in water at 25 ° C. for 1 hour. Further, 2.5 g of the remaining specimen was precisely weighed, and the amount of free formalin (absorbance) was measured according to JIS L 1041 (Method A: acetylacetone method). However, the absorbance of 0.05 or less is the detection limit.
比較例1〜5
蒸留水130部、重合乳化剤1.5部、t−ドデシルメルカプタン0.2部及びブタジエン、スチレン、N−メチロールアクリルアミド、またはアクリルアミド及びアクリル酸の単量体を表3に示す様、オートクレーブ内に仕込み、60℃に昇温後、過硫酸アンモニウム0.3部を仕込み10時間反応を行った。反応終了後、アンモニアでpHを8.0以上に調整、ストリッピングを行い、(N―メチロールアクリルアミドを使用した場合は、尿素2部を添加)、アンモニアでpH7.5〜8.0に調整し、合成ゴムラテックス(比較例1〜5)を得た。このラテックスを5%に希釈し、No.2濾紙(東洋濾紙製)に樹脂付着量が17%になる様、含浸後、マングルロールで付着量を調整した。得られた含浸濾紙を140℃で10分間乾燥し、幅1.5cm×長さ15cmの試片に切り取り、常態及び湿潤時の引っ張り強度測定用試片とした。湿潤引っ張り強度は、25℃の水中に1時間浸漬後測定した。また、残りの試片を2.5g精秤し、JIS L 1041(A法:アセチルアセトン法)に従い、遊離ホルマリン量(吸光度)の測定を行った。但し吸光度0.05以下は検出限界とする。
Comparative Examples 1-5
130 parts of distilled water, 1.5 parts of polymerization emulsifier, 0.2 part of t-dodecyl mercaptan and butadiene, styrene, N-methylolacrylamide, or monomers of acrylamide and acrylic acid are charged into the autoclave as shown in Table 3. After raising the temperature to 60 ° C., 0.3 part of ammonium persulfate was added and the reaction was carried out for 10 hours. After completion of the reaction, the pH is adjusted to 8.0 or higher with ammonia, stripping is performed (2 parts of urea is added when N-methylolacrylamide is used), and the pH is adjusted to 7.5 to 8.0 with ammonia. Synthetic rubber latex (Comparative Examples 1 to 5) was obtained. This latex was diluted to 5%. After impregnation, the adhesion amount was adjusted with a mangle roll so that the resin adhesion amount was 17% on 2 filter papers (manufactured by Toyo filter paper). The obtained impregnated filter paper was dried at 140 ° C. for 10 minutes, cut into a specimen having a width of 1.5 cm and a length of 15 cm, and used as a specimen for measuring tensile strength at normal and wet conditions. The wet tensile strength was measured after immersion in water at 25 ° C. for 1 hour. In addition, 2.5 g of the remaining specimen was precisely weighed, and the amount of free formalin (absorbance) was measured according to JIS L 1041 (Method A: acetylacetone method). However, the absorbance of 0.05 or less is the detection limit.
なお、表中の含浸紙の判定は、含浸紙の常態強度が17MPa以上、かつ湿潤強度が8Mpa以上を合格(○)とし、含浸紙の常態強度が17MPa未満であるもの及び/または湿潤強度が8MPa未満のものを不合格(×)とした。また、ホルマリン遊離量の判定は、遊離ホルマリン量(吸光度)0.05以下の場合に合格(○)、0.05超を不合格(×)とした。 The determination of the impregnated paper in the table indicates that the normal strength of the impregnated paper is 17 MPa or more and the wet strength is 8 Mpa or higher, and the normal strength of the impregnated paper is less than 17 MPa and / or the wet strength is Those less than 8 MPa were regarded as rejected (x). In addition, the formalin release amount was determined to be acceptable (O) when the amount of free formalin (absorbance) was 0.05 or less, and unacceptable (x) when it exceeded 0.05.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5458789A (en) * | 1977-10-19 | 1979-05-11 | Nippon Zeon Co Ltd | Novel conjugated diolefin copolymer latex |
JPS63264958A (en) * | 1987-04-20 | 1988-11-01 | 旭化成株式会社 | Binder for fibrous sheet |
JPH03227302A (en) * | 1989-11-24 | 1991-10-08 | Japan Synthetic Rubber Co Ltd | Production of copolymer latex and composition using same latex |
JPH0559693A (en) * | 1991-08-26 | 1993-03-09 | Japan Synthetic Rubber Co Ltd | Paper coating composition for offset printing |
JPH11148060A (en) * | 1991-09-27 | 1999-06-02 | Sumika Abs Latex Kk | Composition containing copolymer latex |
JP2001019705A (en) * | 2000-01-01 | 2001-01-23 | Asahi Chem Ind Co Ltd | Production of polymer latex |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5458789A (en) * | 1977-10-19 | 1979-05-11 | Nippon Zeon Co Ltd | Novel conjugated diolefin copolymer latex |
JPS63264958A (en) * | 1987-04-20 | 1988-11-01 | 旭化成株式会社 | Binder for fibrous sheet |
JPH03227302A (en) * | 1989-11-24 | 1991-10-08 | Japan Synthetic Rubber Co Ltd | Production of copolymer latex and composition using same latex |
JPH0559693A (en) * | 1991-08-26 | 1993-03-09 | Japan Synthetic Rubber Co Ltd | Paper coating composition for offset printing |
JPH11148060A (en) * | 1991-09-27 | 1999-06-02 | Sumika Abs Latex Kk | Composition containing copolymer latex |
JP2001019705A (en) * | 2000-01-01 | 2001-01-23 | Asahi Chem Ind Co Ltd | Production of polymer latex |
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