JP4554550B2 - Textile treatment composition - Google Patents
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- JP4554550B2 JP4554550B2 JP2006125211A JP2006125211A JP4554550B2 JP 4554550 B2 JP4554550 B2 JP 4554550B2 JP 2006125211 A JP2006125211 A JP 2006125211A JP 2006125211 A JP2006125211 A JP 2006125211A JP 4554550 B2 JP4554550 B2 JP 4554550B2
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Description
本発明は、繊維処理剤組成物及び繊維製品の処理方法に関する。 The present invention relates to a fiber treating agent composition and a method for treating a fiber product.
衣類等の繊維製品は着用、洗浄を繰り返すうちに次第にハリ・コシがなくなり、肌触りが悪くなり着用時のシルエットが崩れる傾向にある。従来、この様な衣類の変化した風合いを回復するために、通常の衣料用洗剤で洗浄後に衣類に糊剤等を用いて高分子により繊維表面をコートすることで、ハリ・コシを回復させていた。 Textile products such as clothing gradually lose their firmness and stiffness as they are repeatedly worn and washed, and the touch tends to deteriorate and the silhouette at the time of wear tends to collapse. Conventionally, in order to recover such a changed texture of clothing, after washing with a normal garment detergent, the surface of the clothing is recovered by coating the fiber surface with a polymer using a paste or the like. It was.
また、多価アルコール（例えば、特許文献１参照）や重合度２ないし３のオリゴ糖（例えば、特許文献２参照）を衣類表面に付着させる繊維製品用仕上げ剤が知られている。 Further, a finishing agent for textiles is known in which a polyhydric alcohol (for example, see Patent Document 1) or an oligosaccharide having a polymerization degree of 2 to 3 (for example, see Patent Document 2) is attached to a clothing surface.
また、洗浄と同時に衣類にハリを与える、特定構造のポリマーとアミノ変性シリコーンを含有する洗浄剤組成物（例えば、特許文献３参照）が知られている。 Further, a cleaning composition containing a polymer having a specific structure and amino-modified silicone that gives elasticity to clothing simultaneously with cleaning (for example, see Patent Document 3) is known.
これらは、繊維製品の繊維それ自体を改質するのではなく、繊維表面に付着し効果を発現するものであり、同じ処理を持続しなければ効果を喪失することになる。 These do not modify the fiber itself of the textile product, but adhere to the fiber surface and develop an effect. If the same treatment is not continued, the effect is lost.
一方、布帛にハリ・コシを付与する耐久性のある処理として、ポリビニルアルコールとエポキシ樹脂等の架橋剤を布帛に施与する方法（例えば、特許文献４参照）が知られているが、１２０℃以上でのキュアリングが必要であり、一般家庭での処理に適さない。
本発明の課題は、一般家庭における通常の洗濯工程において、被洗浄物を繊維の内部から改質し、繊維製品に持続性のあるハリ・コシを付与する繊維処理組成物及びその処理方法を提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to provide a fiber treatment composition and a treatment method thereof for modifying the object to be washed from the inside of the fiber in a normal washing process in a general household and imparting a lasting elasticity to the fiber product. There is to do.
本発明は、下記一般式（Ｉ）で表される基及び／又は下記一般式（II）で表される基を有するアクリル樹脂（Ａ）と、アルコキシシリル基を有するアクリル樹脂（Ｂ）とを含有する繊維処理剤組成物に関する。 The present invention comprises an acrylic resin (A) having a group represented by the following general formula (I) and / or a group represented by the following general formula (II), and an acrylic resin (B) having an alkoxysilyl group. It is related with the fiber treatment agent composition to contain.
（式中、Ｒ1〜Ｒ5は同一でも異なっていても良い炭素数１〜４の炭化水素基を示す。） (Wherein, a hydrocarbon group of R 1 to R 5 is from 1 to 4 carbon atoms which may be the same or different.)
また、本発明は、上記本発明の繊維処理剤組成物を繊維製品と接触させた後、アクリル樹脂（Ｂ）のアルコキシシリル基を加水分解してシラノール化合物とし、該繊維製品に浸透させ、繊維内部でシラノール化合物を重合させる繊維製品の処理方法に関する。 Further, in the present invention, after the fiber treatment agent composition of the present invention is brought into contact with a fiber product, the alkoxysilyl group of the acrylic resin (B) is hydrolyzed to form a silanol compound, which is infiltrated into the fiber product. The present invention relates to a method for treating a textile product in which a silanol compound is polymerized.
また、本発明は、上記本発明の繊維処理剤組成物を繊維製品と接触させた後水洗する繊維製品の処理方法に関する。 Moreover, this invention relates to the processing method of the textiles which make the textile processing agent composition of the said invention contact the textiles, and then wash with water.
本発明により、一般家庭における通常の洗濯工程において、繊維製品を繊維の内部から改質し、繊維製品に持続性のあるハリ・コシを付与する繊維処理組成物及び繊維製品の処理方法が得られる。 According to the present invention, in a normal washing process in a general household, a fiber treatment composition for modifying a fiber product from the inside of the fiber and imparting a lasting elasticity to the fiber product and a method for treating the fiber product can be obtained. .
〔繊維処理組成物〕
本発明の繊維処理組成物は、洗剤による洗浄工程後に用いる仕上げ剤の形態でも良いが、簡便性の観点から、洗浄成分を含有する洗浄剤の形態が好ましい。また、本発明の繊維処理組成物が仕上げ剤の形態である場合、洗濯における使用のみならず、繊維製品にスプレー等を用いて接触させても良い。
[Fiber treatment composition]
Although the form of the finishing agent used after the washing | cleaning process by a detergent may be sufficient as the fiber treatment composition of this invention, the form of the washing | cleaning agent containing a washing | cleaning component is preferable from a viewpoint of simplicity. In addition, when the fiber treatment composition of the present invention is in the form of a finishing agent, the fiber product may be brought into contact using a spray or the like as well as being used in washing.
＜アクリル樹脂（Ａ）＞
本発明の繊維処理組成物は、下記一般式（Ｉ）で表される基及び／又は下記一般式（II）で表される基を有するアクリル樹脂（Ａ）を含有する。
<Acrylic resin (A)>
The fiber treatment composition of the present invention contains an acrylic resin (A) having a group represented by the following general formula (I) and / or a group represented by the following general formula (II).
（式中、Ｒ1〜Ｒ5は同一でも異なっていても良い炭素数１〜４の炭化水素基、好ましくは、メチル基、エチル基を示す。） (In the formula, R 1 to R 5 may be the same or different and each represents a C 1-4 hydrocarbon group, preferably a methyl group or an ethyl group.)
前記アクリル樹脂（Ａ）としては、貯蔵安定性の理由から、前記一般式（Ｉ）で表される基を有するアクリル樹脂の酸による部分中和物（Ａ１）、及びエポキシ基を有するアクリル樹脂の４級アンモニウム塩化物（Ａ２）から選ばれる樹脂であることが好ましい。（Ａ１）において、中和度は安定性の観点から70〜90％が好ましい。 As the acrylic resin (A), for the reasons of storage stability, a partially neutralized product (A1) of an acrylic resin having a group represented by the general formula (I) with an acid and an acrylic resin having an epoxy group A resin selected from quaternary ammonium chlorides (A2) is preferable. In (A1), the neutralization degree is preferably 70 to 90% from the viewpoint of stability.
また、前記アクリル樹脂（Ａ）としては、貯蔵安定性の理由から、前記一般式（Ｉ）で表される基を有するアクリル樹脂（Ａ’）と、前記一般式（II）で表される基を有するアクリル樹脂（Ａ''）とを含有することが好ましく、その場合、両者を（Ａ’）／（Ａ''）＝１／０〜１／１の質量比で含有することが好ましい。 Moreover, as said acrylic resin (A), the group represented by the acrylic resin (A ') which has group represented by the said general formula (I), and the said general formula (II) from the reason of storage stability It is preferable to contain the acrylic resin (A '') which has these, and in that case, it is preferable to contain both by the mass ratio of (A ') / (A' ') = 1/0 to 1/1.
一般式（Ｉ）で表される基は、必ずしも明らかではないが、アクリル樹脂（Ｂ）のアルコキシシリル基の加水分解触媒として作用する一方、一般式（II）で表される基は、触媒活性点である窒素原子上の非共有電子対が４級化反応で失われているものと考えられる。 Although the group represented by the general formula (I) is not necessarily clear, the group represented by the general formula (II) acts as a catalyst for hydrolysis of the alkoxysilyl group of the acrylic resin (B). It is considered that the unshared electron pair on the nitrogen atom, which is a point, is lost in the quaternization reaction.
アクリル樹脂（Ａ）の数平均分子量は、５，０００〜２００，０００、更に１０，０００〜１００，０００が好ましい。この分子量は、ＧＰＣ−光散乱法により測定されたものである。 The number average molecular weight of the acrylic resin (A) is preferably 5,000 to 200,000, more preferably 10,000 to 100,000. This molecular weight is measured by GPC-light scattering method.
＜アクリル樹脂（Ｂ）＞
本発明の繊維処理組成物は、アルコキシシリル基を有するアクリル樹脂（Ｂ）を含有する。アクリル樹脂（Ｂ）としては、下記一般式（III）で表される基及び／又は下記一般式（IV）で表される基を有するα，β−エチレン性不飽和モノマーの重合化物であることが好ましい。
<Acrylic resin (B)>
The fiber treatment composition of the present invention contains an acrylic resin (B) having an alkoxysilyl group. The acrylic resin (B) is a polymerized product of an α, β-ethylenically unsaturated monomer having a group represented by the following general formula (III) and / or a group represented by the following general formula (IV). Is preferred.
（式中、Ｒ6とＲ7は、それぞれ分岐鎖を有していても良い炭素数１〜６のアルキレン基、好ましくは、エチレン基、ｍとｎはそれぞれ０又は１の数、Ｘ1〜X6は同一でも異なっていても良い−Ｒ8又は−ＯＲ9（但し、Ｘ1〜X6の内少なくとも１つは−ＯＲ9である）を示し、Ｒ8及びＲ9はそれぞれ炭素数１〜６の炭化水素基、好ましくは、メチル基及びエチル基を示す。） (Wherein R 6 and R 7 are each an optionally substituted alkylene group having 1 to 6 carbon atoms, preferably an ethylene group, and m and n are each a number of 0 or 1, X 1 to X 6 may be the same or different —R 8 or —OR 9 (wherein at least one of X 1 to X 6 is —OR 9 ), and R 8 and R 9 each have 1 carbon atom. ˜6 hydrocarbon groups, preferably methyl and ethyl groups.)
アクリル樹脂（Ｂ）としては、加水分解によるシラノール縮合反応の進行の理由から、アルコキシシリル基としてメトキシシリル基、エトキシシリル基を有するアクリル樹脂（Ｂ１）が好ましい。 As the acrylic resin (B), an acrylic resin (B1) having a methoxysilyl group or an ethoxysilyl group as an alkoxysilyl group is preferable because of the progress of silanol condensation reaction by hydrolysis.
アクリル樹脂（Ｂ）の数平均分子量は、５，０００〜２００，０００、更に１０，０００〜１００，０００が好ましい。この分子量は、ＧＰＣ−光散乱法により測定されたものである。 The number average molecular weight of the acrylic resin (B) is preferably 5,000 to 200,000, more preferably 10,000 to 100,000. This molecular weight is measured by GPC-light scattering method.
本発明では、前記アクリル樹脂（Ａ）と前記アクリル樹脂（Ｂ）の質量比は、貯蔵安定性の理由から、（Ａ）／（Ｂ）＝９／１〜６／４であることが好ましい。 In the present invention, the mass ratio of the acrylic resin (A) and the acrylic resin (B) is preferably (A) / (B) = 9/1 to 6/4 for reasons of storage stability.
＜コアシェルエマルション＞
本発明の繊維処理剤組成物においては、貯蔵安定性の理由から、前記アクリル樹脂（Ａ）と前記アクリル樹脂（Ｂ）とが、前記アクリル樹脂（Ａ）をシェル相、前記アクリル樹脂（Ｂ）をコア相とするコアシェルエマルションを形成していることが好ましい。
<Core shell emulsion>
In the fiber treatment agent composition of the present invention, for reasons of storage stability, the acrylic resin (A) and the acrylic resin (B) have the acrylic resin (A) as a shell phase and the acrylic resin (B). It is preferable to form a core-shell emulsion having a core phase.
コアシェルエマルションは、前記アクリル樹脂（Ａ）の存在下に、前記アクリル樹脂（Ｂ）の構成モノマーを重合して得ることができる。 The core-shell emulsion can be obtained by polymerizing the constituent monomer of the acrylic resin (B) in the presence of the acrylic resin (A).
一般に、水系でのアルコキシシリル基の反応制御は、その加水分解性のため困難であるが、本発明では安定となる。その理由は必ずしも明らかではないが、アルコキシシリル基とその加水分解触媒となる水和官能基（アミノ基、カルボキシル基）をそれぞれコア／シェル相に分離することにより、エマルション形態を安定にすることができると考えられる。得られたコアシェルエマルションの平均粒子径はレーザー光散乱法により測定することができる。 In general, the reaction control of an alkoxysilyl group in an aqueous system is difficult due to its hydrolyzability, but is stable in the present invention. The reason is not necessarily clear, but the emulsion form can be stabilized by separating the alkoxysilyl group and the hydration functional group (amino group, carboxyl group) serving as a hydrolysis catalyst into a core / shell phase, respectively. It is considered possible. The average particle diameter of the obtained core-shell emulsion can be measured by a laser light scattering method.
＜その他成分＞
抗菌剤（イソチアゾリン骨格を有するものが好ましい）、有機酸（コハク酸及びクエン酸が好ましい）、溶媒（エチレングリコール、プロピレングリコール及び重量平均分子量が５０００以下のポリエチレングリコールが好ましい）、無機塩（食塩、塩化アンモニウム、塩化カルシウムが好ましい）、その他（香料、色素）を配合することができる。
<Other ingredients>
Antibacterial agent (preferably having an isothiazoline skeleton), organic acid (preferably succinic acid and citric acid), solvent (preferably ethylene glycol, propylene glycol and polyethylene glycol having a weight average molecular weight of 5000 or less), inorganic salt (salt, Ammonium chloride and calcium chloride are preferred) and other (fragrances, pigments) can be blended.
＜繊維処理方法＞
本発明は、上述した本発明の繊維処理剤組成物を繊維製品を接触させた後、繊維処理組成物に含有されているアクリル樹脂（Ｂ）のアルコキシシリル基を加水分解してシラノール化合物とし、該繊維製品に浸透させ、繊維内部でシラノール化合物を重合させる繊維製品の処理方法に関するものである。
<Fiber treatment method>
In the present invention, after bringing the fiber treatment agent composition of the present invention described above into contact with a fiber product, the alkoxysilyl group of the acrylic resin (B) contained in the fiber treatment composition is hydrolyzed into a silanol compound, The present invention relates to a method for treating a fiber product that penetrates the fiber product and polymerizes a silanol compound inside the fiber.
本発明の処理に適する繊維製品としては、綿、麻等の植物繊維、ウール、絹等の動物繊維である天然繊維からなる繊維製品が挙げられる。また、これら天然繊維と化学繊維の混紡繊維製品が挙げられる。 Examples of the fiber products suitable for the treatment of the present invention include fiber products made of natural fibers such as vegetable fibers such as cotton and hemp, and animal fibers such as wool and silk. Moreover, the mixed fiber product of these natural fiber and a chemical fiber is mentioned.
本発明では、前記アクリル樹脂（Ａ）と前記アクリル樹脂（Ｂ）とが、前記アクリル樹脂（Ａ）をシェル相、前記アクリル樹脂（Ｂ）をコア相とするコアシェルエマルションを含む繊維処理組成物を用いることが好ましく、その場合、乾燥や過熱により、含有されているエマルションのコアシェル粒子におけるアクリル樹脂（Ｂ）のアルコキシシリル基は加水分解し、シラノール化合物となる。シラノール化合物は水溶性であるため容易に繊維内部に侵入する。シラノール化合物を繊維に十分に浸透させるために、繊維に接触させておく時間は、５〜９０分、特に１０〜６０分が好ましく、１５〜５０分がより好ましく、２０〜４０分が更に好ましい。接触後一定時間放置することで、シラノール化合物は繊維内部まで浸透する。この間、攪拌を行っても良いし、静置しても良い。 In the present invention, a fiber treatment composition comprising a core-shell emulsion in which the acrylic resin (A) and the acrylic resin (B) have the acrylic resin (A) as a shell phase and the acrylic resin (B) as a core phase. In this case, the alkoxysilyl group of the acrylic resin (B) in the core-shell particles of the contained emulsion is hydrolyzed to a silanol compound by drying or overheating. Since the silanol compound is water-soluble, it easily penetrates into the fiber. In order to allow the silanol compound to sufficiently permeate into the fiber, the time of contact with the fiber is preferably 5 to 90 minutes, particularly preferably 10 to 60 minutes, more preferably 15 to 50 minutes, and still more preferably 20 to 40 minutes. By allowing the silanol compound to stand for a certain period of time after contact, the silanol compound penetrates into the fiber. During this time, stirring may be performed, or the solution may be allowed to stand.
繊維内部に侵入したシラノール化合物は、乾燥や、過熱、或いは液のｐＨを５〜８に調整することによって重合を促進することができる。これにより、繊維内部に重合物を形成し持続性のあるハリ・コシを付与することができる。重合工程後、さらに水洗することで過剰の重合物が除去され、より生来の繊維の風合いを保つことができる。よって、本発明によれば、本発明の繊維処理剤組成物を繊維製品と接触させた後水洗する繊維製品の処理方法が提供され、このような方法は一般家庭での通常の洗濯工程に適用することが好適である。 The silanol compound that has penetrated into the fiber can promote polymerization by drying, overheating, or adjusting the pH of the liquid to 5-8. As a result, a polymer can be formed inside the fiber to provide a lasting elasticity. After the polymerization step, excess polymer is removed by further washing with water, and the natural fiber texture can be maintained. Therefore, according to the present invention, there is provided a method for treating a textile product in which the textile treatment composition of the present invention is brought into contact with the textile product and then washed with water, and such a method is applied to a normal washing process in a general household. It is preferable to do.
＜参考例１：アクリル樹脂１の合成法＞
反応容器にブチルセルソルブ120部を入れ、120℃に加熱攪拌した。ここにt-ブチルパーオキシ-2-エチルヘキサノエート2部及びブチルセルソルブ10部を混合した開始剤溶液と、N,N-ジエチルアミノエチルメタクリレート20部及びメチルメタクリレート80部からなるモノマーとを同時に3時間で滴下した。30分間エージングした後、t-ブチルパーオキシ-2-エチルヘキサノエート0.5部及びブチルセルソルブ5部を混合した溶液を30分で滴下し、2時間のエージングを行った後、冷却した。ポリスチレン換算のGPCにより求められた、このエポキシ基を有するアクリル樹脂の数平均分子量は6300、分子量分布は2.1であった。ここに50％酢酸水溶液30部を加え、3級アミノ基を80％中和することで目的のアクリル樹脂１を得た。
<Reference Example 1: Synthesis method of acrylic resin 1>
120 parts of butyl cellosolve was placed in a reaction vessel, and heated and stirred at 120 ° C. Here, an initiator solution in which 2 parts of t-butylperoxy-2-ethylhexanoate and 10 parts of butyl cellosolve were mixed with a monomer comprising 20 parts of N, N-diethylaminoethyl methacrylate and 80 parts of methyl methacrylate simultaneously. It was dripped in 3 hours. After aging for 30 minutes, a solution in which 0.5 parts of t-butylperoxy-2-ethylhexanoate and 5 parts of butyl cellosolve were added dropwise over 30 minutes, and after aging for 2 hours, the mixture was cooled. The number average molecular weight of the acrylic resin having an epoxy group determined by GPC in terms of polystyrene was 6300, and the molecular weight distribution was 2.1. The target acrylic resin 1 was obtained by adding 30 parts of 50% acetic acid aqueous solution and neutralizing the tertiary amino group by 80%.
＜参考例２：アクリル樹脂２の合成法＞
反応容器にブチルセルソルブ120部を入れ、120℃に加熱攪拌した。ここにt-ブチルパーオキシ-2-エチルヘキサノエート2部及びブチルセルソルブ10部を混合した開始剤溶液と、グリシジルメタクリレート20部及びメチルメタクリレート80部からなるモノマーとを同時に3時間で滴下した。30分間エージングした後、t-ブチルパーオキシ-2-エチルヘキサノエート0.5部及びブチルセルソルブ5部を混合した溶液を30分で滴下し、2時間のエージングを行った後、冷却した。ポリスチレン換算のGPCにより求められた、このエポキシ基を有するアクリル樹脂の数平均分子量は8500、分子量分布は2.1であった。ここにトリエチルアミン7部及び50％酢酸水溶液15部を加え、80℃で加熱攪拌することにより4級化を行った。酸化が1以下になり、粘度上昇が止まった時点で加熱を停止することで、目的のアクリル樹脂２を得た。
<Reference Example 2: Synthesis method of acrylic resin 2>
120 parts of butyl cellosolve was placed in a reaction vessel, and heated and stirred at 120 ° C. Here, an initiator solution in which 2 parts of t-butylperoxy-2-ethylhexanoate and 10 parts of butyl cellosolve were mixed, and a monomer consisting of 20 parts of glycidyl methacrylate and 80 parts of methyl methacrylate were simultaneously added dropwise over 3 hours. . After aging for 30 minutes, a solution in which 0.5 parts of t-butylperoxy-2-ethylhexanoate and 5 parts of butyl cellosolve were added dropwise over 30 minutes, and after aging for 2 hours, the mixture was cooled. The number average molecular weight of the acrylic resin having an epoxy group determined by GPC in terms of polystyrene was 8500, and the molecular weight distribution was 2.1. 7 parts of triethylamine and 15 parts of 50% acetic acid aqueous solution were added thereto, and quaternization was performed by heating and stirring at 80 ° C. The target acrylic resin 2 was obtained by stopping the heating when the oxidation became 1 or less and the increase in viscosity stopped.
＜参考例３：コアシェルエマルション(1)の合成法＞
反応容器に、上記アクリル樹脂１を20部と脱イオン水を270部加え、75℃で加熱攪拌した。ここに2,2'-アゾビス（2-（2-イミダゾリン-2-イル）プロパン）1.5部の酢酸100％中和水溶液を5分かけて滴下した。5分間エージングした後、メチルメタクリレート30部を5分かけて滴下した。さらに5分間エージングした後、先の70部と脱イオン水250部とを混合した溶液に、メチルメタクリレート240部及びγ-メタクリロキシプロピルトリエトキシシラン30部からなるアルコシキシシリル基を有するα,β-エチレン性不飽和モノマーを含むモノマー混合物を加えて攪拌して得られたプレエマルションを40分かけて滴下した。60分間エージングした後、冷却し、目的のコアシェルエマルション(1)を得た。得られたコアシェルエマルション(1)のpHは5.0、レーザー光散乱法により測定された平均粒子径は90nmであった。
<Reference Example 3: Synthesis method of core-shell emulsion (1)>
20 parts of the acrylic resin 1 and 270 parts of deionized water were added to the reaction vessel, and the mixture was heated and stirred at 75 ° C. Thereto was added dropwise 1.5 parts of 2,2′-azobis (2- (2-imidazolin-2-yl) propane) 100% acetic acid in aqueous solution over 5 minutes. After aging for 5 minutes, 30 parts of methyl methacrylate was added dropwise over 5 minutes. After aging for another 5 minutes, in the mixed solution of the above 70 parts and 250 parts deionized water, α, having an alkoxysilyl group composed of 240 parts methyl methacrylate and 30 parts γ-methacryloxypropyltriethoxysilane, A pre-emulsion obtained by adding and stirring a monomer mixture containing a β-ethylenically unsaturated monomer was added dropwise over 40 minutes. After aging for 60 minutes, the mixture was cooled to obtain the target core-shell emulsion (1). The obtained core-shell emulsion (1) had a pH of 5.0 and an average particle size of 90 nm as measured by a laser light scattering method.
＜参考例４：コアシェルエマルション(2)の合成法＞
反応容器に、上記アクリル樹脂２を20部と脱イオン水を270部加え、75℃で加熱攪拌した。ここに2,2'-アゾビス（2-（2-イミダゾリン-2-イル）プロパン）1.5部の酢酸100％中和水溶液を5分かけて滴下した。5分間エージングした後、メチルメタクリレート30部を5分かけて滴下した。さらに5分間エージングした後、先のアクリル樹脂２を70部と脱イオン水を250部混合した溶液に、メチルメタクリレート240部及びγ-メタクリロキシプロピルトリエトキシシラン30部からなるアルコシキシシリル基を有するα,β-エチレン性不飽和モノマーを含むモノマー混合物を加えて攪拌して得られたプレエマルションを40分かけて滴下した。60分間エージングした後、冷却し、目的のコアシェルエマルション(2)を得た。得られたコアシェルエマルション(2)のpHは5.0、レーザー光散乱法により測定された平均粒子径は89nmであった。
<Reference example 4: Synthesis method of core-shell emulsion (2)>
20 parts of the acrylic resin 2 and 270 parts of deionized water were added to the reaction vessel, and the mixture was heated and stirred at 75 ° C. Thereto was added dropwise 1.5 parts of 2,2′-azobis (2- (2-imidazolin-2-yl) propane) 100% acetic acid in water over 5 minutes. After aging for 5 minutes, 30 parts of methyl methacrylate was added dropwise over 5 minutes. After aging for 5 minutes, an alkoxysilyl group consisting of 240 parts of methyl methacrylate and 30 parts of γ-methacryloxypropyltriethoxysilane was added to a solution obtained by mixing 70 parts of the acrylic resin 2 and 250 parts of deionized water. A pre-emulsion obtained by adding and stirring a monomer mixture containing an α, β-ethylenically unsaturated monomer was added dropwise over 40 minutes. After aging for 60 minutes, the mixture was cooled to obtain the target core-shell emulsion (2). The obtained core-shell emulsion (2) had a pH of 5.0 and an average particle size measured by a laser light scattering method of 89 nm.
＜参考例５：コアシェルエマルション(3)の合成法＞
反応容器に、上記アクリル樹脂１を10部、上記アクリル樹脂２を10部と脱イオン水を270部加え、75℃で加熱攪拌した。ここに2,2'-アゾビス（2-（2-イミダゾリン-2-イル）プロパン）1.5部の酢酸100％中和水溶液を5分かけて滴下した。5分間エージングした後、メチルメタクリレート30部を5分かけて滴下した。さらに5分間エージングした後、先のアクリル樹脂１を35部、アクリル樹脂２を35部と脱イオン水を250部混合した溶液に、メチルメタクリレート240部及びγ-メタクリロキシプロピルトリエトキシシラン30部からなるアルコシキシシリル基を有するα,β-エチレン性不飽和モノマーを含むモノマー混合物を加えて攪拌して得られたプレエマルションを40分かけて滴下した。60分間エージングした後、冷却し、目的のコアシェルエマルション(3)を得た。
<Reference Example 5: Synthesis method of core-shell emulsion (3)>
10 parts of the acrylic resin 1, 10 parts of the acrylic resin 2 and 270 parts of deionized water were added to the reaction vessel, and the mixture was heated and stirred at 75 ° C. Thereto was added dropwise 1.5 parts of 2,2′-azobis (2- (2-imidazolin-2-yl) propane) 100% acetic acid in aqueous solution over 5 minutes. After aging for 5 minutes, 30 parts of methyl methacrylate was added dropwise over 5 minutes. After aging for another 5 minutes, add 35 parts of acrylic resin 1, 35 parts of acrylic resin 2 and 250 parts of deionized water to 240 parts of methyl methacrylate and 30 parts of γ-methacryloxypropyltriethoxysilane. A pre-emulsion obtained by adding and stirring a monomer mixture containing an α, β-ethylenically unsaturated monomer having an alkoxysilyl group was added dropwise over 40 minutes. After aging for 60 minutes, the mixture was cooled to obtain the target core-shell emulsion (3).
＜参考例６：コアシェルエマルション(4)の合成法＞
反応容器に、アクリル樹脂１を5部、アクリル樹脂２を15部と脱イオン水を270部加え、75℃で加熱攪拌した。ここに2,2'-アゾビス（2-（2-イミダゾリン-2-イル）プロパン）1.5部の酢酸100％中和水溶液を5分かけて滴下した。5分間エージングした後、メチルメタクリレート30部を5分かけて滴下した。さらに5分間エージングした後、先のアクリル樹脂１を20部、アクリル樹脂２を50部と脱イオン水を250部混合した溶液に、メチルメタクリレート240部及びγ-メタクリロキシプロピルトリエトキシシラン30部からなるアルコシキシシリル基を有するα,β-エチレン性不飽和モノマーを含むモノマー混合物を加えて攪拌して得られたプレエマルションを40分かけて滴下した。60分間エージングした後、冷却し、目的のコアシェルエマルション(4)を得た。
<Reference Example 6: Synthesis method of core-shell emulsion (4)>
To the reaction vessel, 5 parts of acrylic resin 1, 15 parts of acrylic resin 2 and 270 parts of deionized water were added, and the mixture was heated and stirred at 75 ° C. Thereto was added dropwise 1.5 parts of 2,2′-azobis (2- (2-imidazolin-2-yl) propane) 100% acetic acid in water over 5 minutes. After aging for 5 minutes, 30 parts of methyl methacrylate was added dropwise over 5 minutes. After aging for another 5 minutes, add 20 parts of acrylic resin 1, 50 parts of acrylic resin 2 and 250 parts of deionized water to a solution of 240 parts of methyl methacrylate and 30 parts of γ-methacryloxypropyltriethoxysilane. A pre-emulsion obtained by adding and stirring a monomer mixture containing an α, β-ethylenically unsaturated monomer having an alkoxysilyl group was added dropwise over 40 minutes. After aging for 60 minutes, the mixture was cooled to obtain the target core-shell emulsion (4).
＜実施例1＞
コアシェルエマルション(3)を繊維処理剤組成物１としてそのまま使用した。
＜実施例2＞
コアシェルエマルション(4)を繊維処理剤組成物２としてそのまま使用した。
＜実施例3＞
コアシェルエマルション(1)を繊維処理剤組成物３としてそのまま使用した。
＜実施例4＞
コアシェルエマルション(2)を繊維処理剤組成物４としてそのまま使用した。
<Example 1>
The core-shell emulsion (3) was used as the fiber treating agent composition 1 as it was.
<Example 2>
The core-shell emulsion (4) was used as the fiber treating agent composition 2 as it was.
<Example 3>
The core-shell emulsion (1) was used as the fiber treating agent composition 3 as it was.
<Example 4>
The core-shell emulsion (2) was used as the fiber treating agent composition 4 as it was.
＜比較例１＞
実施例1において、α、β-エチレン性不飽和モノマー混合物の組成を、アルコキシシリル基を含まないメチルメタクリレート270部に変更した以外は同様にして、コアシェルエマルション(5)を得た。得られたコアシェルエマルション(5)のpHは5.0、レーザー光散乱法により測定された平均粒子径は90nmであった。このようにして得られたコアシェルエマルション(5)を繊維処理剤組成物５としてそのまま使用した。
<Comparative Example 1>
A core-shell emulsion (5) was obtained in the same manner as in Example 1, except that the composition of the α, β-ethylenically unsaturated monomer mixture was changed to 270 parts of methyl methacrylate containing no alkoxysilyl group. The obtained core-shell emulsion (5) had a pH of 5.0 and an average particle size of 90 nm as measured by a laser light scattering method. The core-shell emulsion (5) thus obtained was used as it was as the fiber treating agent composition 5.
＜評価方法＞
得られた繊維処理剤組成物１〜５について、以下の方法でハリ・コシ及び耐久性を評価した。結果を表1に示す。
<Evaluation method>
About the obtained fiber treatment agent compositions 1-5, the elasticity and durability were evaluated with the following method. The results are shown in Table 1.
＜ハリ・コシ評価方法＞
ターゴトメーター型洗浄試験機を使用し、水道水500mL、繊維処理剤組成物100mLを洗浄槽（内容積1000mL）に入れ良く分散した後、木綿ブロード＃60布100gを入れ50回転／分の攪拌速度で15分間攪拌した。その後、下記の方法A又はBにより乾燥した。
乾燥方法A：20℃、65％相対湿度の条件下、24時間乾燥を行う。
乾燥方法B：ドラム式洗濯乾燥機を用いて乾燥を行う。
上記処理布をJIS L 1096：1999 8.19 剛軟性 8.19. 1A法（45°カンチレバー法）に従い剛軟性を測定し、以下の評価基準により評価した。
・評価基準
１：10mm以上15mm以下
２：8mm以上10mm未満、又は15mm超17mm以下
３：8mm未満、又は17mm超
<Hari / Koshi Evaluation Method>
Using a tartometer-type cleaning tester, 500 mL of tap water and 100 mL of fiber treatment composition are placed in a cleaning tank (with an internal volume of 1000 mL) and dispersed well. Then, 100 g of cotton broad # 60 cloth is added and stirred at 50 rpm. Stir at speed for 15 minutes. Then, it dried by the following method A or B.
Drying method A: Drying is performed for 24 hours under the conditions of 20 ° C. and 65% relative humidity.
Drying method B: Drying is performed using a drum type laundry dryer.
The treated fabric was measured for stiffness according to JIS L 1096: 1999 8.19 Bendability 8.19. 1A method (45 ° cantilever method) and evaluated according to the following evaluation criteria.
・ Evaluation criteria 1: 10 mm or more and 15 mm or less 2: 8 mm or more and less than 10 mm, or more than 15 mm and less than 17 mm 3: less than 8 mm or more than 17 mm
＜耐久性試験＞
ハリ・コシ評価方法で乾燥した木綿ブロード＃60布100を、ターゴトメーター型洗浄試験機を使用し、水道水1000mL、JIS K3362：1998記載の洗浄力判定用指標洗剤（蛍光増白剤無配合）を標準量使用し、100回転／分の攪拌速度で15分間攪拌し、濯ぎ、乾燥する洗浄工程を5回繰り返した。この処理布をJIS L 1096：1999 8.19 剛軟性 8.19. 1A法（45°カンチレバー法）に従い剛軟性を測定し、以下の評価基準により評価した。
・評価基準
Ｉ：10mm以上15mm以下
II：8mm以上10mm未満、又は15mm超17mm以下
III：8mm未満、又は17mm超
<Durability test>
100 broad cotton dry # 60 cloth 100 dried by the firmness and stiffness evaluation method using a tartometer type cleaning tester, 1000 mL of tap water, index detergent for determining cleaning power described in JIS K3362: 1998 (without optical brightener) ) Was used at a standard amount, and the washing step of stirring, rinsing and drying at a stirring speed of 100 revolutions / minute for 15 minutes was repeated 5 times. The treated fabric was measured for stiffness according to JIS L 1096: 1999 8.19 Flexibility 8.19.1A method (45 ° cantilever method) and evaluated according to the following evaluation criteria.
・ Evaluation criteria I: 10mm to 15mm
II: 8mm or more and less than 10mm or more than 15mm and 17mm or less
III: Less than 8mm or more than 17mm
Claims (6)
前記アクリル樹脂（Ａ）と前記アクリル樹脂（Ｂ）とが、前記アクリル樹脂（Ａ）をシェル相、前記アクリル樹脂（Ｂ）をコア相とするコアシェルエマルションを形成している、繊維処理剤組成物。
（式中、Ｒ1〜Ｒ5は同一でも異なっていても良い炭素数１〜４の炭化水素基を示す。） Fiber treatment containing an acrylic resin (A) having a group represented by the following general formula (I) and / or a group represented by the following general formula (II) and an acrylic resin (B) having an alkoxysilyl group a composition,
The fiber treatment agent composition in which the acrylic resin (A) and the acrylic resin (B) form a core-shell emulsion having the acrylic resin (A) as a shell phase and the acrylic resin (B) as a core phase. .
(Wherein, a hydrocarbon group of R 1 to R 5 is from 1 to 4 carbon atoms which may be the same or different.)
（式中、Ｒ6とＲ7はそれぞれ分岐鎖を有していてもよい炭素数１〜６のアルキレン基、ｍとｎはそれぞれ０又は１の数、Ｘ1〜X6は同一でも異なっていても良い−Ｒ8又は−ＯＲ9（但し、Ｘ1〜X6の内少なくとも１つは−ＯＲ9である）を示し、Ｒ8及びＲ9はそれぞれ炭素数１〜６の炭化水素基を示す。） Polymer of monomer in which the acrylic resin (B) contains an α, β-ethylenically unsaturated monomer having a group represented by the following general formula (III) and / or a group represented by the following general formula (IV) The fiber treatment agent composition according to any one of claims 1 to 3.
(In the formula, R 6 and R 7 are each an optionally substituted alkylene group having 1 to 6 carbon atoms, m and n are each 0 or 1, and X 1 to X 6 are the same or different. good -R 8 or -OR 9 be (provided that at least one of X 1 to X 6 is -OR 9) indicates each R 8 and R 9 are a hydrocarbon group having 1 to 6 carbon atoms Show.)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269874A (en) * | 1995-03-31 | 1996-10-15 | Sanyo Chem Ind Ltd | Binder composition for fiber processing |
| JP2004210962A (en) * | 2002-12-27 | 2004-07-29 | Lion Corp | Water-repelling agent composition |
| JP2005089882A (en) * | 2003-09-12 | 2005-04-07 | Lion Corp | Water-absorbing and quick drying property-imparting composition for fiber and aerosol type water-absorbing and quick drying property-imparting agent for fiber |
| JP2005187957A (en) * | 2003-12-24 | 2005-07-14 | Dainippon Ink & Chem Inc | Color deepening agent, method for deepening color using the same and article treated with the color deepening agent |
| JP2005290569A (en) * | 2004-03-31 | 2005-10-20 | Dainippon Ink & Chem Inc | Glass fiber-treating agent, method for producing the same and glass paper |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269874A (en) * | 1995-03-31 | 1996-10-15 | Sanyo Chem Ind Ltd | Binder composition for fiber processing |
| JP2004210962A (en) * | 2002-12-27 | 2004-07-29 | Lion Corp | Water-repelling agent composition |
| JP2005089882A (en) * | 2003-09-12 | 2005-04-07 | Lion Corp | Water-absorbing and quick drying property-imparting composition for fiber and aerosol type water-absorbing and quick drying property-imparting agent for fiber |
| JP2005187957A (en) * | 2003-12-24 | 2005-07-14 | Dainippon Ink & Chem Inc | Color deepening agent, method for deepening color using the same and article treated with the color deepening agent |
| JP2005290569A (en) * | 2004-03-31 | 2005-10-20 | Dainippon Ink & Chem Inc | Glass fiber-treating agent, method for producing the same and glass paper |
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