JP4004687B2 - Glue - Google Patents

Description

【００１３】
【化２】

【００１４】
カチオン性モノマーは、酢酸ビニル重合体の重合に用いる全モノマー混合物中に好ましくは０．１〜２重量％、より好ましくは０．３〜１．５重量％の割合で用いられる。
【００１５】
不飽和カルボン酸としては、特にアクリル酸、メタクリル酸、クロトン酸が好ましい。
【００１６】
また、不飽和カルボン酸の低級アルコールエステルとしては、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチルが好ましい。
【００１７】
このような不飽和カルボン酸または不飽和カルボン酸の低級アルコールエステルは、酢酸ビニル重合体の重合に用いる全モノマー混合物中に好ましくは１〜３０重量％、より好ましくは２〜２０重量％の割合で配合され重合される。
【００１８】
不飽和カルボン酸アミドとしては、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎージメチルメタクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ，Ｎ−ジエチルメタクリルアミド、Ｎ−プロピルアクリルアミド、Ｎ−ヒドロキシエチルメタクリルアミド、ダイアセトンイソアクリルアミドが好ましい。
【００１９】
不飽和カルボン酸アミドは、酢酸ビニル重合体の重合に用いる全モノマー混合物中に好ましくは０．１〜３０重量％、より好ましくは１〜２０重量％の割合で配合され重合される。
【００２０】
本発明の酢酸ビニル重合体は酢酸ビニルモノマーを最も多く反応させることによって得られる重合体であり、酢酸ビニルモノマーの割合は、前記の重合に供せられる全モノマー重量当たり、７５〜９９．８重量％、好ましくは８２〜９９重量％の割合で用いられる。
【００２１】
本発明では酢酸ビニル系重合体を製造する際に乳化剤として非イオン界面活性剤を使用することが好ましく、ＨＬＢが１６〜１９、特に１６．５〜１８．８のものが良好である。このような非イオン界面活性剤としては、アルキル鎖またはアルケニル鎖の炭素数が８〜１８、好ましくは１０〜１８であり、エチレンオキサイド平均付加モル数が２０〜７０、好ましくは３０〜６０のポリオキシエチレンアルキルエーテルもしくはポリオキシエチレンアルケニルエーテルが挙げられる。非イオン界面活性剤濃度は糊剤中に、好ましくは０．０２〜２重量％、より好ましくは０．０２〜１重量％含有される。本発明では、特にこれら非イオン界面活性剤を、酢酸ビニル系重合体に用いるモノマー（但し、後述の陽イオン性高分子化合物及び／又は非イオン性高分子化合物を配合する場合は、これらも加えた量）１００重量部に対して、０．１〜５重量部、特に０．２〜３重量部の割合で、重合時に配合することが好ましい。
【００２２】
本発明では、乳化安定化剤として陽イオン性高分子化合物を含有することが好ましい。具体的には、カチオン化澱粉及び／又はカチオン化セルロースを挙げることができる。これらの中でも５重量％水溶液の５０℃における粘度が５０〜１００ｍＰａ・ s 、好ましくは６０〜９０ｍＰａ・ ｓであり、カチオン置換度が０．０２〜１．５、特に０．０３〜１．０のカチオン化澱粉及び／又はカチオン化セルロースが好適である。陽イオン性高分子化合物は、糊剤中に、好ましくは０．５〜６重量％含有される。本発明では、これら陽イオン性高分子化合物を、酢酸ビニル系重合体に用いるモノマーと陽イオン性高分子化合物の合計量（但し、後述の非イオン性高分子化合物を配合する場合は、これも加えた量）１００重量部に対して、１〜２５重量部、特に１〜２０重量部の割合で配合した系で乳化重合を行うことが最も好ましい。なお、本発明でのカチオン置換度とは、グルコース単位当りのカチオン化度であり、澱粉またはセルロースを構成している水酸基の数はグルコース単位あたり３個であり、これが総てカチオン置換されている場合を３．０とする時の値である。
【００２３】
本発明では分離安定性をさらに向上させるために、非イオン性高分子化合物を併用することができる。非イオン性高分子化合物としてはポリビニルアルコール、ポリビニルピロリドン、化工澱粉、水溶性セルロース誘導体を挙げることができる。非イオン性高分子化合物は、糊剤中に０．１〜５重量％含有されることが好ましい。本発明では特に、これら非イオン性高分子化合物を、酢酸ビニル系重合体に用いるモノマーと非イオン性高分子化合物の合計量（但し、後述の陽イオン性高分子化合物を配合する場合は、これも加えた量）１００重量部に対して、０．３〜２５重量部、特に１〜２０重量部の割合で配合した系で乳化重合を行うことが最も好ましい。
【００２４】
本発の酢酸ビニル系重合体の製造方法としては、重合開始剤として２、２‘−アゾビス（２−アミジノプロパン）、過酸化水素、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、過酢酸、過安息香酸、過硫酸塩を使用することができる。開始剤の添加量は酢酸ビニルモノマーに対して０．０１〜５重量％の範囲で使用することが好ましい。
【００２５】
重合反応の温度は４０〜１２０℃、好ましくは５０〜９０℃であり、重合時のｐＨは３〜９、好ましくは４〜８の範囲で行う。この際緩衝剤として炭酸ナトリウム、重炭酸ナトリウム、オルソリン酸ナトリウム、第１リン酸ナトリウム、塩化ナトリウム、硫酸ナトリウムのような無機塩を０〜２重量％、好ましくは０．１〜１重量％用いるのが良い。また、本発明に係わるエマルジョンを得るための重合時における各成分の添加方法は、全ての成分を同時に添加して反応させても良く、酢酸ビニル溶液以外の成分を仕込んだ容器に、酢酸ビニル溶液を徐々に添加する方法で行ってもよい。
【００２６】
本発明では、このようにして製造した酢酸ビニル系重合体を糊剤に配合するが、酢酸ビニル系重合体の濃度は、前記陽イオン性高分子化合物及び／又は非イオン性高分子化合物を含有する場合は、それらも含めた濃度が、好ましくは糊剤中に２０〜４０重量％、より好ましくは２５〜３５重量％である。また、本発明の糊剤の粘度は３０℃で１００〜３５０ｍＰａ・ ｓ、好ましくは２００〜３００ｍＰａ・ ｓが好ましい。本発明は、濃度が低く、粘度が低い糊剤において、特に効果的であり、従来の糊剤と比較して安定性の向上が明らかである。
【００２７】
本発明の最終的な糊剤は、重合後のエマルジョンにその他任意成分を配合するか、水等で希釈することによって得られるが、本発明では糊剤と分けて説明するために、重合後のエマルジョン溶液を糊料基剤とする。
【００２８】
本発明では上記酢酸ビニル系重合体以外に、一般に糊剤に使用される成分を配合しても差し支えない。例えばジブチルフタレート、ジブチルアジペート、ジオクチルアジペート、トリアセチンなどのような可塑剤、エチレングリコール、プロピレングリコール、エタノールなどの凍結防止剤、殺菌剤、蛍光染料、顔料、香料などを添加することができる。
【００２９】
【発明の効果】
本発明によれば貯蔵中に凝集物が形成しない安定性に優れる糊剤を提供することができる。
【００３０】
【実施例】
合成例１．糊料基剤Ａの合成
５つ口フラスコに、カチオン性澱粉〔コーンスターチと３−（Ｎ，Ｎ，Ｎ−トリメチルアンモニウムクロリド）−１，２−プロピレンオキサイドとの反応で得られたもの。カチオン置換度は０．０６、５％水溶液の５０℃における粘度は７０ｍＰａ・ ｓである。〕６重量部及びイオン交換水１００重量部を９０℃にて均一溶解した後６０℃まで冷却し、酢酸ビニル溶液１０重量部、ポリビニルアルコール（重合度１５００）３重量部、非イオン界面活性剤（ポリオキシエチレンラウリルエーテル、エチレンオキシド平均付加モル数４０、ＨＬＢ１８．３）１．０重量部を加え、さらに、炭酸ナトリウム０．５重量部、２．２’−アゾビス（２−アミジノプロパン）塩酸塩０．１重量部、イオン交換水２０重量部を加え、７５℃に加熱して重合を開始した。重合開始後、１時間かけて、酢酸ビニル、アクリル酸、Ｎ，Ｎ−ジメチルアクリルアミドの最終比率が９０／７／３（重量比）になるように予め混合しておいたもの１００重量部を、反応溶液中に連続して滴下した。滴下終了後、８０℃に昇温し、１時間熟成した。冷却後、１／１０Ｎの硫酸水溶液でｐＨ５に調整し、固形分約５０％の糊料基剤Ａを得た。なお、合成例１で使用した酢酸ビニル溶液のオリゴマー含有量は２ｐｐｍであった。
比較合成例１．糊料基剤Ｂの合成
合成例１においてオリゴマー含有量が８ｐｐｍの酢酸ビニル溶液を使用した以外は同様の方法で糊料基剤Ｂを製造した（固形分約５０％）。
実施例
上記で合成した糊料基剤と表１に示す化合物を用いて、表１に示す糊剤を得た。それらを、直径２０ｍｍ、高さ２５０ｍｍの密閉できる円柱状のガラス製沈降管に５０ｍｌ入れたものを１０本用意し、４０℃の恒温室に３ヶ月間静置貯蔵した。貯蔵後、目視により凝集物の形成を評価した。その結果、実施例１はすべての沈降管で分離や凝集物の形成が見られないのに対して、比較例１は４本の沈降管に凝集物の形成が確認された。
【００３１】
【表１】

【００３２】
＊シリコーンエマルジョン：シリコーンＫ−９７Ｋ（信越化学工業社製）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a paste for a textile product containing an emulsion type polymer (hereinafter abbreviated as vinyl acetate polymer) having a structure derived from vinyl acetate as a main skeleton.
[0002]
[Prior Art and Problems to be Solved by the Invention]
Conventionally, starch has been used as the base of paste, but because of its poor dissolution and dispersibility, it is now an emulsion based on vinyl acetate polymer as a paste that can be easily dissolved and dispersed in cold water. Mold liquid pastes are developed and marketed. The paste base as the main component of the emulsion type paste comprises vinyl acetate, a nonionic surfactant, a cationic polymer compound such as cationized starch, and a nonionic polymer compound such as polyvinyl alcohol as an emulsifier and Emulsion stabilizer is a system used as an emulsion stabilizer. It can be obtained by emulsion polymerization, but the emulsion may separate and settle due to long-term storage, and these problems are particularly noticeable when the emulsifier content is reduced. . On the other hand, the present inventors have first noticed that the emulsifier in the emulsion contributes to the stability of the polymer, but reduces the adhesion of the polymer to clothing, and restricts the use of the emulsifier. Thus, it was found that sufficient pasting property can be obtained even if the blending amount of the vinyl acetate polymer is reduced. From these viewpoints, there has been a strong demand for a solution to the above problems.
[0003]
An object of the present invention is to provide a paste containing a vinyl acetate polymer that does not cause aggregation or separation / settling during storage.
[0004]
[Means for Solving the Problems]
The present invention provides an emulsion type paste containing a polymer having a constituent skeleton derived from a vinyl acetate monomer obtained by emulsion polymerization of a vinyl acetate solution comprising a vinyl acetate monomer and 0.01 to 5 ppm vinyl acetate oligomer. .
[0005]
In the present invention, the vinyl acetate solution refers to a system including a vinyl acetate monomer and an oligomer derived from vinyl acetate, and the vinyl acetate oligomer has a molecular weight (polystyrene as an internal standard) measured under the following conditions. 200-2000.
<Analysis conditions>
-Column: Polysylene gel column [Tosoh G2000HXL (inner diameter 7.8 mm, length 30 cm) and G1000HXL (inner diameter 7.8 mm, length 30 cm) connected in series]
-Mobile phase: Tetrahydrofuran-Flow rate: 1 ml / min
・ Detector: RI
・ Quantity: Area [0006]
DETAILED DESCRIPTION OF THE INVENTION
As a result of many polymerization experiments, the present inventors have noticed that the storage stability differs depending on the vinyl acetate solution used when the polymerization is carried out with the amount of the emulsifier reduced. Usually, the vinyl acetate solution contains about 10 ppm of oligomers obtained by polymerizing vinyl acetate monomers. The present inventors have provided an emulsion type paste using a paste base obtained by emulsion polymerization using an oligomer having a concentration of 0.01 to 5 ppm, preferably 0.1 to 3 ppm in the vinyl acetate solution. It was found that the agent exhibits excellent storage stability even when the blending amount of the emulsifier is small.
[0007]
In order to obtain such a vinyl acetate solution, a known purification method may be used. Specifically, it is purified by a method such as distillation or thin-film distillation, and produced by emulsion polymerization immediately after purification, or a vinyl acetate solution containing a polymerization inhibitor such as hydroquinone, butylhydroxytoluene, butylhydroxyanisole, etc. The method of suppressing superposition | polymerization can be mentioned by adding 1-50 ppm with respect to this, and storing in a cool dark place. A large amount of a polymerization inhibitor is inconvenient because it adversely affects the production of a suitable paste, and is limited to a low concentration, but even if a polymerization inhibitor is blended, in a vinyl acetate solution, Since oligomers are produced, it is desirable to avoid the long-term storage of the vinyl acetate solution and to check and use the oligomer amount during polymerization.
[0008]
In addition, the fixed_quantity | quantitative_assay of the said oligomer can be measured by GPC (gel permeation chromatography).
[0009]
The vinyl acetate polymer may be a copolymer of vinyl acetate and a monomer other than vinyl acetate.
[0010]
Such monomers include cationic monomers, unsaturated carboxylic acids, lower alcohol esters of unsaturated carboxylic acids and unsaturated carboxylic acid amides.
[0011]
Examples of the cationic monomer include cationic monomer compounds of the following general formulas (1) to (7), and among these, those of general formulas (3) to (5) are particularly preferable.
[0012]
[Chemical 1]

[0013]
[Chemical 2]

[0014]
The cationic monomer is preferably used in a proportion of 0.1 to 2% by weight, more preferably 0.3 to 1.5% by weight in the total monomer mixture used for the polymerization of the vinyl acetate polymer.
[0015]
As the unsaturated carboxylic acid, acrylic acid, methacrylic acid, and crotonic acid are particularly preferable.
[0016]
Moreover, as a lower alcohol ester of unsaturated carboxylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate are preferable.
[0017]
The unsaturated carboxylic acid or the lower alcohol ester of the unsaturated carboxylic acid is preferably 1 to 30% by weight, more preferably 2 to 20% by weight in the total monomer mixture used for the polymerization of the vinyl acetate polymer. Blended and polymerized.
[0018]
As unsaturated carboxylic acid amides, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N-propylacrylamide, N-hydroxyethylmethacrylamide, Diacetone isoacrylamide is preferred.
[0019]
The unsaturated carboxylic acid amide is preferably blended and polymerized in a proportion of 0.1 to 30% by weight, more preferably 1 to 20% by weight, in the total monomer mixture used for the polymerization of the vinyl acetate polymer.
[0020]
The vinyl acetate polymer of the present invention is a polymer obtained by reacting the most vinyl acetate monomer, and the ratio of the vinyl acetate monomer is 75 to 99.8 wt.% Based on the total monomer weight to be subjected to the polymerization. %, Preferably 82-99% by weight.
[0021]
In the present invention, it is preferable to use a nonionic surfactant as an emulsifier when producing a vinyl acetate polymer, and those having an HLB of 16 to 19, particularly 16.5 to 18.8 are preferable. As such a nonionic surfactant, a polyalkylene having an alkyl chain or alkenyl chain having 8 to 18 carbon atoms, preferably 10 to 18 carbon atoms, and an average ethylene oxide addition mole number of 20 to 70, preferably 30 to 60. Examples thereof include oxyethylene alkyl ether and polyoxyethylene alkenyl ether. The nonionic surfactant concentration is preferably 0.02 to 2% by weight, more preferably 0.02 to 1% by weight in the paste. In the present invention, in particular, these nonionic surfactants are added to the monomers used for the vinyl acetate polymer (however, when a cationic polymer compound and / or a nonionic polymer compound described later are added) The amount is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight, based on 100 parts by weight.
[0022]
In the present invention, it is preferable to contain a cationic polymer compound as an emulsion stabilizer. Specific examples include cationized starch and / or cationized cellulose. Among these, the viscosity at 50 ° C. of a 5% by weight aqueous solution is 50 to 100 mPa · s, preferably 60 to 90 mPa · s, and the degree of cation substitution is 0.02 to 1.5, particularly 0.03 to 1.0. Cationized starch and / or cationized cellulose are preferred. The cationic polymer compound is preferably contained in an amount of 0.5 to 6% by weight in the paste. In the present invention, these cationic polymer compounds are added to the total amount of the monomer and the cationic polymer compound used in the vinyl acetate polymer (however, when the nonionic polymer compound described later is added) It is most preferable to carry out emulsion polymerization in a system in which the amount is 1 to 25 parts by weight, particularly 1 to 20 parts by weight, based on 100 parts by weight. The degree of cation substitution in the present invention is the degree of cationization per glucose unit. The number of hydroxyl groups constituting starch or cellulose is 3 per glucose unit, and all of them are cation-substituted. This is the value when the case is 3.0.
[0023]
In the present invention, a nonionic polymer compound can be used in combination in order to further improve the separation stability. Nonionic polymer compounds include polyvinyl alcohol, polyvinyl pyrrolidone, modified starch, and water-soluble cellulose derivatives. The nonionic polymer compound is preferably contained in an amount of 0.1 to 5% by weight in the paste. In the present invention, in particular, these nonionic polymer compounds are added to the total amount of the monomer and nonionic polymer compound used in the vinyl acetate polymer (however, in the case where a cationic polymer compound described later is blended) It is most preferable to carry out the emulsion polymerization in a system blended at a ratio of 0.3 to 25 parts by weight, particularly 1 to 20 parts by weight with respect to 100 parts by weight.
[0024]
As a method for producing the vinyl acetate polymer of the present invention, 2,2′-azobis (2-amidinopropane), hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide are used as polymerization initiators. , Cyclohexanone peroxide, peracetic acid, perbenzoic acid, and persulfate can be used. It is preferable to use the initiator in an amount of 0.01 to 5% by weight based on the vinyl acetate monomer.
[0025]
The temperature of the polymerization reaction is 40 to 120 ° C., preferably 50 to 90 ° C., and the pH during the polymerization is 3 to 9, preferably 4 to 8. In this case, 0-2% by weight, preferably 0.1-1% by weight of an inorganic salt such as sodium carbonate, sodium bicarbonate, sodium orthophosphate, primary sodium phosphate, sodium chloride, sodium sulfate is used as a buffer. Is good. Moreover, the addition method of each component at the time of superposition | polymerization for obtaining the emulsion concerning this invention may add all the components simultaneously, and may make it react, A vinyl acetate solution is put into the container charged with components other than a vinyl acetate solution. You may carry out by the method of adding gradually.
[0026]
In the present invention, the vinyl acetate polymer produced in this way is blended in the paste, and the concentration of the vinyl acetate polymer contains the cationic polymer compound and / or the nonionic polymer compound. When it does, the density | concentration also including them becomes like this. Preferably it is 20 to 40 weight% in a paste, More preferably, it is 25 to 35 weight%. The viscosity of the paste of the present invention is 100 to 350 mPa · s at 30 ° C., preferably 200 to 300 mPa · s. The present invention is particularly effective in a paste having a low concentration and a low viscosity, and an improvement in stability is apparent as compared with a conventional paste.
[0027]
The final paste of the present invention can be obtained by blending other optional components in the emulsion after polymerization or by diluting with water or the like. In the present invention, in order to explain separately from the paste, The emulsion solution is used as a paste base.
[0028]
In the present invention, in addition to the above-mentioned vinyl acetate polymer, a component generally used for a paste may be blended. For example, plasticizers such as dibutyl phthalate, dibutyl adipate, dioctyl adipate, and triacetin, antifreezing agents such as ethylene glycol, propylene glycol, and ethanol, bactericides, fluorescent dyes, pigments, and fragrances can be added.
[0029]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the paste which is excellent in stability which does not form an aggregate during storage can be provided.
[0030]
【Example】
Synthesis Example 1 Synthesis of Paste Base A A five-neck flask with cationic starch [obtained by reaction of corn starch and 3- (N, N, N-trimethylammonium chloride) -1,2-propylene oxide. The degree of cation substitution is 0.06, and the viscosity of a 5% aqueous solution at 50 ° C. is 70 mPa · s. ] 6 parts by weight and 100 parts by weight of ion-exchanged water were uniformly dissolved at 90 ° C. and then cooled to 60 ° C., 10 parts by weight of vinyl acetate solution, 3 parts by weight of polyvinyl alcohol (degree of polymerization 1500), nonionic surfactant ( Polyoxyethylene lauryl ether, ethylene oxide average addition mole number 40, HLB18.3) 1.0 part by weight, sodium carbonate 0.5 part by weight, 2.2'-azobis (2-amidinopropane) hydrochloride 0 .1 part by weight and 20 parts by weight of ion-exchanged water were added, and the mixture was heated to 75 ° C. to initiate polymerization. 100 parts by weight of premixed vinyl acetate, acrylic acid, N, N-dimethylacrylamide so that the final ratio is 90/7/3 (weight ratio) over 1 hour after the start of polymerization, The reaction solution was continuously added dropwise. After completion of dropping, the temperature was raised to 80 ° C. and aged for 1 hour. After cooling, the pH was adjusted to 5 with a 1/10 N aqueous sulfuric acid solution to obtain a paste base A having a solid content of about 50%. The oligomer content of the vinyl acetate solution used in Synthesis Example 1 was 2 ppm.
Comparative Synthesis Example 1 Synthetic Example 1 of Paste Base B Paste base B was produced in the same manner except that a vinyl acetate solution having an oligomer content of 8 ppm was used (solid content: about 50%).
Examples Using the paste base synthesized above and the compounds shown in Table 1, pastes shown in Table 1 were obtained. Ten of them were put in a cylindrical glass sedimentation tube having a diameter of 20 mm and a height of 250 mm that could be sealed, and stored in a constant temperature room at 40 ° C. for 3 months. After storage, the formation of aggregates was evaluated visually. As a result, in Example 1, no separation or aggregate formation was observed in all the sedimentation tubes, whereas in Comparative Example 1, formation of aggregates was confirmed in the four sedimentation tubes.
[0031]
[Table 1]

[0032]
* Silicone emulsion: Silicone K-97K (manufactured by Shin-Etsu Chemical Co., Ltd.)

Claims (1)

An emulsion-type paste containing a polymer having a constituent skeleton derived from a vinyl acetate monomer obtained by emulsion polymerization of a vinyl acetate solution comprising a vinyl acetate monomer and a 0.01 to 5 ppm vinyl acetate oligomer.