JP2007009350A - Aqueous emulsion type resin composition for fabric, water-based ink composition used for fabric and using the resin composition and use - Google Patents

Aqueous emulsion type resin composition for fabric, water-based ink composition used for fabric and using the resin composition and use Download PDF

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JP2007009350A
JP2007009350A JP2005189084A JP2005189084A JP2007009350A JP 2007009350 A JP2007009350 A JP 2007009350A JP 2005189084 A JP2005189084 A JP 2005189084A JP 2005189084 A JP2005189084 A JP 2005189084A JP 2007009350 A JP2007009350 A JP 2007009350A
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fabric
resin component
self
fabrics
mass
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Takehide Misawa
毅秀 三澤
Aya Kokaya
亜矢 小萱
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Soken Kagaku KK
Soken Chemical and Engineering Co Ltd
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Soken Kagaku KK
Soken Chemical and Engineering Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous emulsion type resin composition which makes fabrics to exhibit self-transferring/self-coating properties and gives an oil-repelling function having excellent washing resistance and the like to the fabrics, to provide a water-based ink composition for fabrics by adding colorability to the resin component, and to provide a functional fabric and a printed fabric using the compositions. <P>SOLUTION: This aqueous emulsion type resin composition for the fabrics is characterized in that a resin component dispersed in an aqueous medium makes the fabrics to exhibit self-transferring/self-coating properties as a nanomaterial resin component which comprises the ultra fine particles of a low Tg acrylic copolymer obtained from 100 mass% of all polymerizable monomers and 10 to 70 mass% of a glycidyl group-having copolymerizable monomer and having an average particle diameter of 5 to 100 nm based on volume. The water-based ink composition for fabrics uses a colored resin component as the resin component. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、水性エマルジョン型樹脂組成物に関し、より詳細には、布地に対して自己転着性又は自己被覆コート性を発揮させ且つその樹脂成分に優れる耐洗濯性を有する撥油性や、防汚性等の機能を賦与させる布地用の水性エマルジョン型樹脂組成物及びその水性エマルジョン型樹脂組成物で被覆コートされている機能性布地に関する。   The present invention relates to an aqueous emulsion resin composition. More specifically, the present invention provides oil repellency and antifouling that exhibits self-transferability or self-coating coating properties on fabric and has excellent washing resistance for the resin component. TECHNICAL FIELD The present invention relates to a water-based emulsion resin composition for a fabric imparting functions such as properties and a functional fabric coated with the water-based emulsion resin composition.

また、本発明は、このように布地に耐洗濯性を有する撥油性や、防汚性等の機能を賦与させる水性エマルジョン型樹脂組成物に、更に着色性を持たせて自己転着性としての印刷性又は転写性を発揮させる布地用の水性インキ組成物及びその水性インキ組成物を用いて各種の印刷又は転写法で所望する図柄及び／又は文字が印刷又は転写されている印刷布地に関する。   In addition, the present invention provides a water-emulsion type resin composition that imparts functions such as oil repellency having washing resistance and antifouling property to the fabric as described above, and further imparts colorability as a self-transfer property. The present invention relates to a water-based ink composition for fabrics that exhibits printability or transferability, and a printed fabric on which desired patterns and / or characters are printed or transferred by various printing or transfer methods using the water-based ink composition.

天然繊維及び／又は合成繊維からなる布地に、各種の機能性樹脂又は各種の機能剤を被覆及び／又は含浸させて防水性、撥水性、速乾性、防汚性、帯電防止性等の機能や、また、近年、その機能も益々多様化され、例えば、しわ防止性、形態安定性、防花粉付着性、抗菌防臭性、たばこ防臭性等の機能や、更には、その機能も益々高度化・多機能化されて賦与されている機能性布地が種々検討・実用化されている。また、従来から、このように布地に賦与させた機能効果について、その耐洗濯性や、耐久・堅牢性を一層向上させる技術対処法も種々検討又は著しく待望されていることも事実である。   A fabric made of natural fibers and / or synthetic fibers is coated and / or impregnated with various functional resins or various functional agents to provide functions such as waterproofness, water repellency, quick drying, antifouling properties, antistatic properties, etc. In recent years, the functions have been diversified, for example, functions such as wrinkle prevention, form stability, pollen adhesion, antibacterial deodorization, tobacco deodorization, and so on. Various functional fabrics that have been provided with multiple functions have been studied and put into practical use. It is also true that various technical countermeasures for improving the washing resistance and durability / fastness of the functional effects imparted to the fabric in this way have been studied or have been highly anticipated.

また、このような機能性樹脂等を布地に転着及び／又は含浸させるに際して、これらの機能性樹脂に、例えば、着色性機能を持たせた機能性着色樹脂成分として熱圧着下に布地に転着及び／又は含浸させることができる。従来から、このような機能性着色樹脂成分を布地に転着及び／又は含浸させて、所望する図柄及び／又は文字付き布地として実用化されている。すなわち、図柄及び／又は文字を印刷又転写させた印刷布地が広く利用されている。   In addition, when transferring and / or impregnating such a functional resin or the like to the fabric, the functional resin is transferred to the fabric under thermocompression bonding as a functional colored resin component having a coloring function, for example. It can be deposited and / or impregnated. Conventionally, such a functional colored resin component is transferred to and / or impregnated into a fabric and put into practical use as a fabric having a desired pattern and / or letters. That is, printed fabrics on which designs and / or characters are printed or transferred are widely used.

そこで、例えば［特許文献１］には、布地に防汚性及び撥水性等の機能を発現させるために、乳化剤としてのアニオン、カチオン及びノニオン界面活性剤を用いて得られるフッ素系ポリマーエマルジョンを主剤に、アクリル樹脂等を含有するエマルジョン型樹脂組成物を機能性表面処理剤として織布又は不織布に塗布させた機能性布地が提案されている。   Thus, for example, in [Patent Document 1], a main component is a fluoropolymer emulsion obtained by using an anion, a cation and a nonionic surfactant as an emulsifier in order to develop functions such as antifouling property and water repellency in a fabric. Furthermore, functional fabrics have been proposed in which an emulsion-type resin composition containing an acrylic resin or the like is applied to a woven fabric or a nonwoven fabric as a functional surface treatment agent.

また、［特許文献２］には、湿式成膜法で、セルロース、ポリエステル、ナイロン等の織布又は不織布に塗工させて布地に透湿防水性機能を賦与させる樹脂組成物として、ポリウレタン樹脂溶液に、分子中に尿素結合及びオルガノポリシロキサン基を有するオリゴマー乃至はその粒子径サイズが５μｍ以下であるその微細粒ポリマー微粒子が分散する透湿防水布地用ポリウレタン樹脂組成物が提案されている。   [Patent Document 2] describes a polyurethane resin solution as a resin composition that is applied to a woven or non-woven fabric of cellulose, polyester, nylon, etc. by a wet film forming method to impart a moisture permeable waterproof function to the fabric. In addition, a polyurethane resin composition for moisture permeable and waterproof fabrics in which oligomers having urea bonds and organopolysiloxane groups in the molecule or fine polymer particles having a particle size of 5 μm or less are dispersed is proposed.

また、被転着体又は被被覆コート体又は被印刷体である布地に、このような機能を賦与させるに、従来から公知の噴霧塗布、スピンコート等の各種コート法や、スクリン印刷等の各種の印刷法の他に、近年においては、インクジェット塗工法（ＩＪ塗工法）で、このような機能性樹脂及び／又は機能性着色樹脂成分を転着又は被覆コート、または、印刷又は転写させる。そのために、転着媒体、被覆コート媒体、印刷媒体及び転写媒体とする布地用水性インキ組成物及び水性コーティング剤等が広く検討・実用化されている。   In addition, in order to impart such a function to the fabric to be transferred or coated to be coated or printed, various coating methods such as conventionally known spray coating and spin coating, and various types of screen printing, etc. In recent years, in addition to the printing method described above, such a functional resin and / or functional colored resin component is transferred or coated, or printed or transferred by an inkjet coating method (IJ coating method). Therefore, water-based ink compositions for fabrics, water-based coating agents, and the like that are used as transfer media, coating coating media, printing media, and transfer media have been widely studied and put into practical use.

例えば［特許文献３］には、印刷用インク、インクジェット（ＩＪ）記録用インク等に用いられる特定単量体を含有する単量体組成物と油溶性染料と有機珪素単量体とを、重合開始剤、反応性乳化剤（又は重合性乳化剤）及び非反応性乳化剤との併用下に乳化重合させた、例えば、平均粒子径が９２ｎｍの着色微細粒子を含有する着色樹脂エマルジョンが提案されている。   For example, in [Patent Document 3], a monomer composition containing a specific monomer used in printing ink, inkjet (IJ) recording ink, and the like, an oil-soluble dye, and an organosilicon monomer are polymerized. There has been proposed a colored resin emulsion containing colored fine particles having an average particle size of 92 nm, for example, emulsion polymerized in combination with an initiator, a reactive emulsifier (or polymerizable emulsifier) and a non-reactive emulsifier.

また、［特許文献４］には、水性媒体中に、インクジェット記録紙用の水性印刷インキとして、油溶性染料を含有する体積平均粒子径が７０ｎｍ以下で、親水性ポリマー部位が１０〜４０質量％で、且つＴｇ≦０℃で、特にＴｇ≦−１５℃の疎水性ポリマー部位が６０〜９０質量％を併せ持つ着色微粒子を分散させたＩＪ記録紙用の水性印刷インキが提案されている。   [Patent Document 4] discloses that, in an aqueous medium, as a water-based printing ink for ink jet recording paper, the volume average particle size containing an oil-soluble dye is 70 nm or less, and the hydrophilic polymer portion is 10 to 40% by mass. In addition, a water-based printing ink for IJ recording paper has been proposed in which colored fine particles having a hydrophobic polymer portion of 60 to 90% by mass with Tg ≦ 0 ° C. and particularly Tg ≦ −15 ° C. are dispersed.

更に、［特許文献５］には、Ｔｇ≦０℃で、ニトリル基、カルボキシル基及びビニル基等の官能基を有するモノマーを共重合させて得られる樹脂粒子及び顔料粒子を分散する水性エマルジョン型の布地用インキ組成物が提案され、天然繊維及び合成繊維からなる布地に固着力を発揮させ、耐洗濯性を有する布地用インキ組成物であると記載させている。   Furthermore, [Patent Document 5] describes an aqueous emulsion type in which resin particles and pigment particles obtained by copolymerizing monomers having functional groups such as a nitrile group, a carboxyl group, and a vinyl group are dispersed at Tg ≦ 0 ° C. A fabric ink composition has been proposed, and it is described as a fabric ink composition having a washing resistance by exerting an adhesive force on a fabric composed of natural fibers and synthetic fibers.

特開２０００−１１００６９号公報JP 2000-110069 A 特開平１１−１２４４９７号公報Japanese Patent Laid-Open No. 11-124497 特開２０００−２９７１２６号公報JP 2000-297126 A 特開２００４−３２３７２３号公報JP 2004-323723 A 特開平８−２０９０５２号公報JP-A-8-209052

以上のような状況下にあって、布地に機能性樹脂又は各種の機能剤を含浸、転着又は被覆コートさせて、「防水性、撥水性、速乾性、防汚性、帯電防止性、しわ防止性、形態安定性、防花粉付着性、抗菌防臭性、たばこ防臭性」等の機能を布地に賦与させる技術分野と、併せてこの機能性樹脂成分に着色機能を持たせて機能性着色樹脂成分として布地に転着又は被覆コートさせて、布地に所望する「図柄及び／又は文字」等を転着形成させて図柄付き布地にする技術分野とは、両者とも機能性樹脂成分又は機能性着色樹脂成分を布地に転着又は被覆コートさせて、様々な機能を賦与させる布地の表面処理加工であるとも言える。   Under the circumstances as described above, the fabric is impregnated with a functional resin or various functional agents, transferred, or coated, and “waterproof, water-repellent, quick-drying, antifouling, antistatic, wrinkle-proof” In addition to the technical field of imparting functions such as `` prevention, form stability, anti-pollen powder adhesion, antibacterial deodorization, and tobacco deodorization '' to the fabric, this functional resin component has a coloring function and is a functional coloring resin. The technical field is to transfer or coat coat the fabric as a component, transfer the desired "design and / or characters" etc. to the fabric to make the fabric with the design, both functional resin components or functional coloring It can also be said to be a surface treatment of a fabric that imparts various functions by transferring or coating a resin component to the fabric.

以上のような観点から、機能性着色樹脂を用いて、布地に図柄及び／又は文字を転着形成させる後者の処理技術は、布地に所望する図柄及び／又は文字等を印刷又は転写させる表面加工である。従って、布地に「機能性樹脂成分」を「転着又は被覆コート」させる前者の処理技術と、布地に「機能性着色樹脂成分」を「印刷又は転写」させる後者の処理技術とは、何れも布地表面を表面処理加工させる観点において、その技術的範囲を同じくすると理解される。   From the viewpoints described above, the latter processing technique for transferring and forming a pattern and / or characters on a fabric using a functional colored resin is a surface treatment for printing or transferring a desired pattern and / or characters on the fabric. It is. Therefore, both of the former processing technology for “transferring or coating” the “functional resin component” on the fabric and the latter processing technology for “printing or transferring” the “functional colored resin component” on the fabric. It is understood that the technical scope is the same in terms of surface treatment of the fabric surface.

また、既に説明する如く、布地に様々な機能を賦与させる表面処理加工は、益々高機能化、多機能化又は多様化の傾向にあって、その技術的課題も、益々微細・薄膜・高性能化の方向にある。また、その技術的課題を達成させるために、近年、「ナノマテリアル」なる素材を用いて対処させて成す「ナノテク」技術開発が不可欠である。すなわち、上記する媒体組成物中に含有させる機能性樹脂成分及び／又は着色機能成分は、例えば、その樹脂粒子径サイズ又は転着・被覆コート膜厚サイズが、数１００ｎｍ以下であって、特に１０ｎｍ〜数１０ｎｍの超微細粒子又は極薄膜をターゲットにしなければならない。そのために適材としての「ナノマテリアル」なる機能性樹脂素材又は機能性着色樹脂素材を探索しなければならない。   In addition, as already explained, surface treatment that imparts various functions to fabrics is becoming increasingly functional, multifunctional, or diversified, and its technical issues are also increasingly fine, thin, and high performance. In the direction of Moreover, in order to achieve the technical problem, in recent years, “nanotech” technology development that is dealt with using the material “nanomaterial” is indispensable. That is, the functional resin component and / or the coloring functional component contained in the medium composition described above has, for example, a resin particle size or a transfer / coating coat film thickness of several hundred nm or less, particularly 10 nm. It must target ultrafine particles or ultrathin films of ˜several tens of nm. Therefore, it is necessary to search for a functional resin material or a functional colored resin material called “nanomaterial” as an appropriate material.

そこで、既に上記した［特許文献３］又は［特許文献４］公報には、サブミクロン以下で数１０ｎｍ程度の超微細粒の着色樹脂微粒子が、また、［特許文献５］公報には、特に布地に固着力を発揮させて耐洗濯性に優れる水性エマルジョン型インキ組成物などが、従来技術として提案されている。   Therefore, in the above-mentioned [Patent Document 3] or [Patent Document 4], ultrafine colored resin fine particles of about several tens of nanometers with submicron or less are used, and in [Patent Document 5], a fabric is particularly provided. A water-based emulsion type ink composition that exhibits excellent adhesion and has excellent washing resistance has been proposed as a conventional technique.

しかしながら、その着色樹脂微細粒子が、布地に優れた転着及び被覆コート性を発揮させ、しかも、優れた耐洗濯性を有する樹脂成分として充分満足させる機能を布地に賦与させるか否か、また、その機能効果が充分な耐久性を発揮させる技術又は素材であるのか、必ずしも明確に言及又は開示されていないのが実状である。   However, whether or not the colored resin fine particles provide the fabric with excellent transferability and coating coatability, and give the fabric a function that is sufficiently satisfied as a resin component having excellent washing resistance, Whether the functional effect is a technique or a material that exhibits sufficient durability, it is not always explicitly stated or disclosed.

そこで、本発明の目的は、各種の天然繊維及び／又は合成繊維からなる織布又は不織布に、従来技術とは著しく相違して、格別の樹脂バインダーを用いずに、しかも、熱圧着を要せずに自己転着性又は自己被覆コート性を発揮させる「ナノマテリアル」樹脂成分を提供させることである。更には、その転着又は被覆コートさせた樹脂成分が、優れる耐洗濯性を有する撥油性や、防汚性等の機能を布地に賦与できて、しかも、その機能効果が著しく耐久・堅牢性である布地用の水性エマルジョン型樹脂組成物を提供させることである。   Therefore, the object of the present invention is to make a woven fabric or non-woven fabric made of various natural fibers and / or synthetic fibers remarkably different from the prior art, without using a special resin binder and requiring thermocompression bonding. It is to provide a “nanomaterial” resin component that exhibits self-transfer properties or self-coating coating properties. Furthermore, the resin component that is transferred or coated can impart functions such as oil repellency and antifouling properties with excellent washing resistance to the fabric, and the functional effects are extremely durable and robust. It is to provide an aqueous emulsion type resin composition for a certain fabric.

また、本発明の他の目的は、このような特徴を発揮させて、優れた耐洗濯性を有する撥油性や、防汚性等の機能を布地に賦与できる布地用の水性エマルジョン型樹脂組成物を、熱圧着を要せずに布地に自己転着又は自己被覆コートされている機能性布地を提供させることである。   Another object of the present invention is to provide an aqueous emulsion-type resin composition for fabrics that can exhibit such characteristics and impart functions such as oil repellency and antifouling properties having excellent washing resistance to fabrics. Is to provide a functional fabric that is self-transferred or self-coated on the fabric without the need for thermocompression bonding.

また、本発明の更なる目的は、このように布地に耐洗濯性を有する撥油性や、防汚性等の機能を賦与させる布地用の水性エマルジョン型樹脂組成物を用いて、更に追加機能として着色性を併せ持たせることで、熱圧着を要せずに自己転着性としての印刷性又は転写性を発揮させる布地用の水性インキ組成物を提供させることである。   In addition, a further object of the present invention is to use an aqueous emulsion resin composition for fabrics that imparts functions such as oil repellency having washing resistance and antifouling properties to fabrics, and as an additional function. It is to provide a water-based ink composition for fabrics that exhibits printability or transferability as self-transferability without requiring thermocompression bonding by having colorability.

また、本発明の更なる他の目的は、このような特徴及び機能を発揮させる水性インキ組成物を用いて、各種の印刷又は転写法で、様々な織布又は不織布に、熱圧着を要せずに所望する図柄及び／又は文字を印刷又は転写させた印刷布地を提供させることである。   Still another object of the present invention is to require thermocompression bonding to various woven or non-woven fabrics by various printing or transfer methods using a water-based ink composition that exhibits such characteristics and functions. And providing a printed fabric on which a desired pattern and / or character is printed or transferred.

そこで、本発明者らは、上記する課題を鋭意検討した結果、布地に転着させて様々な機能を賦与させる機能性樹脂成分に、特定の官能基を持たせて布地とのインタラクションを高めさせることに着目させて、従来の機能性樹脂成分に著しく相違して、特にバインダー樹脂成分を用いることなく、しかも、熱圧着させることなく効果的に布地に自発転着する機能性樹脂成分又は機能性着色樹脂成分を見出して、本発明を完成させるに至った。   Therefore, as a result of intensive studies on the above-described problems, the inventors have given specific functional groups to the functional resin component that is transferred to the fabric and imparts various functions to enhance the interaction with the fabric. In particular, the functional resin component or functionality that is remarkably different from the conventional functional resin component and that effectively spontaneously transfers to a fabric without using a binder resin component and without thermocompression bonding. The coloring resin component was found and the present invention was completed.

本発明によれば、水性媒体中に分散する樹脂成分が、布地に対して自己転着性又は自己被覆コート性を発揮させ、しかも、その布地に転着又は被覆コートさせた樹脂成分が、優れた耐洗濯性を有する撥油性や、防汚性等の機能を発揮させ、しかも、その機能効果が著しく耐久・堅牢性であることを特徴とする布地用の水性エマルジョン型樹脂組成物を提供する。   According to the present invention, the resin component dispersed in the aqueous medium exerts self-transferability or self-coating coatability on the fabric, and the resin component transferred or coated on the fabric is excellent. A water-based emulsion-type resin composition for fabrics that exhibits functions such as oil repellency having anti-washing properties and antifouling properties, and is highly durable and fast in its functional effects. .

すなわち、本発明による水性エマルジョン型樹脂組成物中に含有し上記するような特徴及び機能を発揮させる樹脂成分は、
（１）全重合性モノマー成分の１００質量％当たり、グリシジル基を有する共重合性モノマー成分が１０〜７０質量％の範囲で重合させて得られ、
（２）ガラス転移点Ｔｇ≧−５０で、且つＴｇ≦１０℃の範囲にあるアクリル系共重合体粒子である。
しかも、このグリシジル基を有するアクリル系共重合体粒子は、
（３）体積基準で表す平均粒子径が５〜１００ｎｍの超微細ポリマー粒子の「ナノマテリアル」樹脂成分である。
更には、このような粒子径サイズにある本発明によるアクリル系共重合体粒子の表面には、
（４）このグリシジル基が頭出しするように形成されている「ナノマテリアル」樹脂成分として、水性媒体中に分散する布地用水性エマルジョン型樹脂組成物である。 That is, the resin component that is contained in the aqueous emulsion resin composition according to the present invention and exhibits the above-described features and functions,
(1) The copolymerizable monomer component having a glycidyl group is polymerized in a range of 10 to 70% by mass per 100% by mass of the total polymerizable monomer component,
(2) Acrylic copolymer particles having a glass transition point Tg ≧ −50 and Tg ≦ 10 ° C.
Moreover, the acrylic copolymer particles having a glycidyl group are
(3) “Nanomaterial” resin component of ultrafine polymer particles having an average particle diameter of 5 to 100 nm expressed on a volume basis.
Furthermore, on the surface of the acrylic copolymer particles according to the present invention having such a particle size size,
(4) An aqueous emulsion-type resin composition for a fabric that is dispersed in an aqueous medium as a “nanomaterial” resin component formed so that the glycidyl group cue.

また、本発明によれば、このような特徴及び機能を発揮させる本発明による水性エマルジョン型樹脂組成物は、塗布後、特に熱圧着させることなく布地に自己被覆コート性を発揮させる。これによって、本発明による水性エマルジョン型樹脂組成物を、被被覆コート体である天然繊維、再生繊維、半合成繊維、合成繊維のそれぞれ単独及びこれらの少なくとも２種の複合繊維の群から選ばれる何れかの繊維からなる織布又は不織布に、塗布させて熱圧着させることなく、自己被覆コート性を発揮させ、且つその被覆コートされた樹脂成分に、優れる耐洗濯性を有する撥油性や、防汚性等の機能が賦与されていることを特徴とする機能性布地を提供する。   In addition, according to the present invention, the aqueous emulsion type resin composition according to the present invention that exhibits such features and functions exhibits self-coating coatability on the fabric without being particularly thermocompression bonded after application. Thus, the water-based emulsion resin composition according to the present invention can be selected from the group consisting of natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers, each of which is a coated body, and a group of at least two types of these composite fibers. Without being applied to a woven or non-woven fabric made of any of these fibers and thermocompression bonded, the self-coating coating property is exhibited, and the resin component coated with the coating is excellent in oil repellency and antifouling properties having excellent washing resistance. Provided is a functional fabric characterized by a function such as sex.

また、本発明によれば、布地にこのような自己転着性なる特徴及び撥油性や、防汚性等の機能を賦与させる布地用水性エマルジョン型樹脂組成物を用いて、更に、この樹脂成分に予め着色性機能を持たせた着色樹脂成分として布地に転着させると、自己転着性としての印刷性又は転写性が発揮される。しかも、その樹脂成分の耐洗濯性を有する撥油性や、防汚性が活かされて、その印刷又は転写着色樹脂成分にも優れた耐洗濯性を有する撥油性や、防汚性の機能を賦与させることを特徴とする布地用水性インキ組成物を提供する。   In addition, according to the present invention, the resin component is further used by using an aqueous emulsion resin composition for fabrics that imparts such self-transfer properties and functions such as oil repellency and antifouling properties to fabrics. When it is transferred to a fabric as a colored resin component having a coloring function in advance, printability or transferability as self-transferability is exhibited. In addition, the oil repellency and antifouling property of the resin component having washing resistance are utilized, and the printing or transfer colored resin component is also provided with the oil repellency and antifouling function having excellent washing resistance. A water-based ink composition for fabrics is provided.

すなわち、本発明による布地用の水性インキ組成物においては、自己転着性なる特徴を発揮させて、しかも、耐洗濯性を有する撥油性や、防汚性等の機能を賦与させる樹脂成分が、
（１）全重合性モノマー成分の１００質量％当たり、グリシジル基を有する共重合性モノマー成分が１０〜７０重量％の範囲で共重合させて得られ、
（２）ガラス転移点Ｔｇ≧−５０℃で、且つＴｇ≦１０℃の範囲にあるアクリル系共重合体粒子であって、
更には、
（３）予め油性染料の０．１〜５０質量％を内包着色する着色樹脂成分である。
しかも、
（４）このグリシジル基を含有するアクリル系共重合体粒子は、体積基準で表す平均粒子径が５〜１００ｎｍの超微細ポリマー粒子である。
従って、本発明による水性インキ組成物中に含有する樹脂成分は、
（５）平均粒子径≦１００ｎｍサイズの「着色ナノマテリアル」樹脂成分として含有し、しかも、その超微細ポリマー粒子表面には、グリシジル基が存在している。 That is, in the water-based ink composition for fabrics according to the present invention, the resin component that exhibits the self-transfer property and imparts functions such as oil repellency having washing resistance and antifouling property,
(1) A copolymerizable monomer component having a glycidyl group is copolymerized in a range of 10 to 70% by weight per 100% by mass of the total polymerizable monomer component,
(2) Acrylic copolymer particles having a glass transition point Tg ≧ −50 ° C. and Tg ≦ 10 ° C.
Furthermore,
(3) It is a colored resin component that encapsulates 0.1 to 50% by mass of the oily dye in advance.
Moreover,
(4) The acrylic copolymer particles containing a glycidyl group are ultrafine polymer particles having an average particle size expressed by volume of 5 to 100 nm.
Therefore, the resin component contained in the water-based ink composition according to the present invention is:
(5) It is contained as a “colored nanomaterial” resin component having an average particle size ≦ 100 nm, and glycidyl groups are present on the surface of the ultrafine polymer particles.

更には、本発明によれば、各種の布地に、様々な図柄及び／又は文字を印刷又は転写させる本発明による布地用水性インキ組成物を用いて、印刷又は転写着色樹脂成分が、耐洗濯性を有する撥油性や、防汚性や、防印刷滲み性の機能を賦与される所望する図柄及び／又は文字が印刷又は転写されていることを特徴とする印刷布地を提供する。   Furthermore, according to the present invention, using the water-based ink composition for fabrics according to the present invention that prints or transfers various designs and / or characters on various fabrics, the printed or transferred colored resin component is resistant to washing. There is provided a printed fabric characterized in that a desired pattern and / or characters imparted with functions of oil repellency, antifouling property, and anti-print bleeding property are printed or transferred.

すなわち、布地に対して自己転着性を発揮させる超微細粒子の「着色ナノマテリアル」なる樹脂成分を含有する本発明による布地用水性インキ組成物を、布地に転着させることで、含有する「ナノマテリアル」なる着色樹脂成分の自己転着性が活かされて、特に熱圧着させることなく布地に自己転着性としての印刷性又は転写性を発揮させる。   That is, the water-based ink composition for fabrics according to the present invention containing a resin component called “colored nanomaterial” of ultrafine particles that exhibit self-transferability to the fabric is contained by transferring it to the fabric. The self-transferability of the colored resin component called “nanomaterial” is utilized, and the printability or transferability as the self-transferability is exhibited on the fabric without particularly thermocompression bonding.

これによって、通常の各種の印刷法又はインクジェット法で、被印刷体である天然繊維、再生繊維、半合成繊維、合成繊維のそれぞれ単独及びこれらの少なくとも２種の複合繊維の群から選ばれる何れかの繊維からなる織布又は不織布に、熱圧着させることなく自己転着性としての印刷性又は転写性を発揮させ、この着色樹脂成分による所望する図柄及び／又は文字が、布地に印刷又は転写される。   Accordingly, any one of natural fibers, recycled fibers, semi-synthetic fibers, and synthetic fibers, each of which is a printing medium, and any one selected from the group of at least two types of composite fibers by various ordinary printing methods or ink-jet methods. A print or transfer property as a self-transfer property is exerted on a woven or non-woven fabric made of the above-mentioned fibers without being thermocompression bonded, and a desired pattern and / or character by this colored resin component is printed or transferred onto the fabric. The

更には、熱圧着せずに布地に印刷又は転写された図柄及び／又は文字の着色樹脂成分には、耐洗濯性を有する撥油性や、防汚性や、防印刷滲み性の機能が賦与されている印刷布地である。   Furthermore, the colored resin component of the pattern and / or characters printed or transferred to the fabric without thermocompression bonding is provided with functions of oil repellency, antifouling property, and anti-print bleeding property having wash resistance. Printing fabric.

以上から、本発明による水性エマルジョン型樹脂組成物を、布地に塗布させると、含有する平均粒子径が１００ｎｍ以下の超微細ポリマー粒子である「ナノマテリアル」樹脂成分が、布地の微細な繊維間隙にも効果的に浸透して布地繊維に効果的に馴染ませることができる。また、その「ナノマテリアル」樹脂成分のアクリル系共重合体粒子表面には、グリシジル基が、頭出し状になるように形成されている。このようなグリシジル基を介して、布地繊維に効果的にインタラクトさせる。   From the above, when the aqueous emulsion resin composition according to the present invention is applied to a fabric, the “nanomaterial” resin component, which is an ultrafine polymer particle having an average particle diameter of 100 nm or less, is contained in the fine fiber gaps of the fabric. Can also penetrate effectively and become familiar with fabric fibers. Further, glycidyl groups are formed on the surface of the acrylic copolymer particles of the “nanomaterial” resin component so as to form a cue. Through such a glycidyl group, the fabric fiber is effectively interacted.

しかも、この超微細ポリマー粒子のナノマテリアル樹脂成分のガラス転移点Ｔｇ≧−５０℃で、且つＴｇ≦１０℃の範囲にあることから、布地に塗布又は転着後、自然乾燥程度の温度雰囲気下においても、そのＴｇにより、この超微細ポリマー粒子は、布地に馴染み・浸透して転着又は被覆コートさせる。   Moreover, since the glass transition point Tg ≧ −50 ° C. and Tg ≦ 10 ° C. of the nanomaterial resin component of the ultrafine polymer particles, it is in a temperature atmosphere that is naturally dried after being applied or transferred to the fabric. However, due to the Tg, the ultrafine polymer particles become familiar and penetrate into the fabric to be transferred or coated.

このような超微細ポリマー粒子の「ナノマテリアル」樹脂成分が、発揮させるインタラクションから、本発明による布地用の水性エマルジョン型樹脂組成物中に含有する樹脂成分は、従来の転着樹脂成分とは著しく相違して、熱圧着を要せずに、布地に優れた自己転着性又は自己被覆コート性を発揮させる。しかも、このようなインタラクションによって、布地に転着又は被覆コートされる機能性樹脂成分には、優れる耐洗濯性が発揮される。   Because of the interaction exhibited by the “nanomaterial” resin component of such ultrafine polymer particles, the resin component contained in the aqueous emulsion resin composition for fabric according to the present invention is significantly different from the conventional transfer resin component. In contrast, it is possible to exhibit excellent self-transferability or self-coating coatability on a fabric without the need for thermocompression bonding. In addition, the functional resin component that is transferred or coated onto the fabric by such interaction exhibits excellent washing resistance.

また、本発明による樹脂成分が、このように自己転着性又は自己被覆コート性又は耐洗濯性なる特徴を発揮させることから、この樹脂成分に着色性、撥油性、防汚性等を含めた各種の機能を持たせることで、布地に転着又は被覆コート、または、印刷又は転写させて様々な機能性布地や、印刷布地にすることができる。   In addition, since the resin component according to the present invention exhibits such characteristics as self-transferability, self-coating coatability or washing resistance, the resin component includes coloring property, oil repellency, antifouling property and the like. By giving various functions, it can be transferred or coated on the fabric, or printed or transferred to form various functional fabrics or printed fabrics.

また、このように布地に印刷又は転写される着色樹脂成分中のインキ成分は、本発明においては、着色超微粒子内に内包されているインキ成分（又は油溶性染料）である。従って、布地に印刷後、本発明による自己印刷性又は自己転写性を有するインキ成分は、［印刷又は転写樹脂成分］→［布地の繊維間隙間］方向への移行（又は拡散流失）を著しく困難にさせる。印刷又は転写させた図柄及び／又は文字部位からのインキ成分の滲み出を困難にさて、所謂、防印刷滲み性、耐マーカー性を効果的に発揮させる。   In the present invention, the ink component in the colored resin component printed or transferred to the fabric in this way is an ink component (or oil-soluble dye) encapsulated in the colored ultrafine particles. Therefore, after printing on the fabric, the ink component having self-printing property or self-transferability according to the present invention is extremely difficult to shift (or diffuse flow away) in the direction of [printing or transfer resin component] → [gap between fabric fibers]. Let me. The so-called anti-print bleeding property and marker resistance are effectively exhibited by making it difficult for the ink component to bleed out from the printed and transferred pattern and / or character portion.

以下に、本発明による布地に自己転着性又は自己被覆コート性を発揮させる水性エマルジョン型樹脂組成物及び自己印刷性又は自己転写性の布地用水性インキ組成物について、その実施に係わる最良の形態について更に説明する。   BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the water-based emulsion resin composition and the self-printing or self-transferring water-based ink composition for fabrics that exhibit self-transferability or self-coating coatability on the fabric according to the present invention will be described. Will be further described.

既に説明する如く、布地に対して自己転着性又は自己被覆コート性及び自己印刷性又は自己転写性を発揮させる本発明による布地用の水性エマルジョン型樹脂組成物中に含有する樹脂成分は、
（イ）全重合性モノマー成分の１００重量％当たり、グリシジル基を有する共重合性モノマー成分が１０〜７０重量％の範囲で得られ、しかも、そのガラス転移点Ｔｇ≧−５０℃で、Ｔｇ≦１０℃の範囲にある低Ｔｇのアクリル系共重合体粒子である。
（ロ）そのアクリル系共重合体粒子の体積基準で表す平均粒子径が５〜１００ｎｍの超微細ポリマー粒子の「ナノマテリアル」樹脂成分であることを特徴としている。 As already explained, the resin component contained in the aqueous emulsion resin composition for fabric according to the present invention that exhibits self-transferability or self-coating coatability and self-printing or self-transferability to the fabric,
(A) A copolymerizable monomer component having a glycidyl group is obtained in a range of 10 to 70% by weight per 100% by weight of the total polymerizable monomer component, and at the glass transition point Tg ≧ −50 ° C., Tg ≦ Low Tg acrylic copolymer particles in the range of 10 ° C.
(B) It is characterized by being a “nanomaterial” resin component of ultrafine polymer particles having an average particle diameter of 5 to 100 nm expressed on a volume basis of the acrylic copolymer particles.

また、布地に対して自己印刷性又は自己転写性を発揮させる本発明による布地用水性インキ組成物中に含有する樹脂成分は、
（ハ）上記（イ）及び（ロ）に記載する特徴に加え、更なる特徴として、油性染料が０．１〜５０質量％の範囲で内包着色されている「着色ナノマテリアル」樹脂成分であることを特徴としている。 In addition, the resin component contained in the water-based ink composition for fabric according to the present invention that exhibits self-printing or self-transferability to the fabric,
(C) In addition to the features described in (i) and (b) above, as a further feature, the “colored nanomaterial” resin component in which the oil dye is colored in the range of 0.1 to 50% by mass It is characterized by that.

本発明において、樹脂成分として用いられるアクリル系共重合体粒子は、全重合性モノマー成分当たり、好ましくは、グリシジル基を有する共重合性モノマー成分が１０〜７０質量％の範囲で得られる共重合体ポリマー粒子であって、この共重合性モノマー成分量が、下限値の１０質量％未満では、グリシジル基の含有量が充分でなく自己転着性又は自己被覆コート性が低下することから好ましくなく、一方、上限値の７０質量％を超えると、繊維微細間隙や内部に浸透し難くなることから好ましくない。   In the present invention, the acrylic copolymer particles used as the resin component are preferably a copolymer in which the copolymerizable monomer component having a glycidyl group is obtained in a range of 10 to 70% by mass per total polymerizable monomer component. When the copolymerizable monomer component amount is less than 10% by mass of the lower limit, it is not preferable because the content of the glycidyl group is not sufficient and the self-transfer property or the self-coating coating property is lowered. On the other hand, if it exceeds 70% by mass of the upper limit value, it is not preferable because it is difficult to penetrate into the fine fiber gap or the inside.

また、本発明において、このような共重合下に得られる共重合体ポリマー粒子は、好ましくは、そのガラス転移点Ｔｇ≧−５０℃で、且つＴｇ≦１０℃の範囲にある低Ｔｇのアクリル系共重合体粒子である。このＴｇの下限値が−５０℃未満であると、粘着性が強すぎてべとつき感を呈することから好ましくなく、一方、このＴｇの上限値１０℃を超えると、自然温度雰囲気下に粘着性を著しく低下させることから好ましくない。Ｔｇは、ＦＯＸの式に基づき計算する。   In the present invention, the copolymer polymer particles obtained under such copolymerization preferably have a low Tg acrylic system having a glass transition point Tg ≧ −50 ° C. and Tg ≦ 10 ° C. Copolymer particles. If the lower limit of Tg is less than −50 ° C., the tackiness is too strong, and it is not preferable because it gives a sticky feeling. On the other hand, if the upper limit of 10 g of Tg is exceeded, the tackiness is not increased in a natural temperature atmosphere. It is not preferable because it significantly decreases. Tg is calculated based on the FOX equation.

また、本発明において、このような共重合下に得られる共重合体ポリマー粒子の平均粒子径は、体積基準で表して５〜１００ｎｍの超微細粒子で、好ましくは、１０〜６０ｎｍの範囲にあるナノマテリアル樹脂成分として適宜好適に用いられる。この平均粒子径が、下限値の５ｎｍ未満であると、粒子が布地の繊維間隙及び布地面に定着し難くなる等から好ましくなく、一方、この上限値１００ｎｍを超えると、布地の繊維微細間隙に浸透し難くなり好ましくない。   Moreover, in this invention, the average particle diameter of the copolymer polymer particle obtained under such copolymerization is a 5-100 nm ultrafine particle on a volume basis, Preferably, it exists in the range of 10-60 nm. It is suitably used as a nanomaterial resin component. If the average particle diameter is less than the lower limit of 5 nm, it is not preferable because the particles are less likely to be fixed on the fiber gap of the fabric and the fabric ground. On the other hand, if the upper limit exceeds 100 nm, the fiber fine gap of the fabric is not preferred. It is not preferable because it is difficult to penetrate.

そこで、本発明において、以上のような特徴を有する樹脂成分としてのアクリル系共重合体粒子を調製させるに際して、既に説明する理由から、「グリシジル基を有するモノマー」を適宜使用する。その具体的なグリシジル基を有するモノマーとして、例えば、グリシジル（メタ）アクリレート、アリルグリシジルエーテル、エチルアクリル酸グリシジル、クロトニルグリシジルエーテル、クロトン酸グリシジルなどのグリシジル基含有ビニル化合物；β−メチルグリシジル（メタ）アクリレート；エポキシ基を有するグリシジルビニルエーテル、グリシジルビニルエステル、３，４−エポキシシクロヘキシルビニルエーテル、グリシジル（メタ）アリルエーテル、３，４−エポキシシクロヘキシル（メタ）アリルエーテル、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート等を挙げることができる。中でも、本発明において、共重合性や重合反応率の高さから、グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート等のグリシジル基を有する（メタ）アクリル系モノマーが好ましい。   Therefore, in the present invention, when preparing the acrylic copolymer particles as the resin component having the above-mentioned characteristics, “monomer having a glycidyl group” is appropriately used for the reason already described. Specific examples of the monomer having a glycidyl group include glycidyl group-containing vinyl compounds such as glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, and glycidyl crotonic acid; β-methyl glycidyl (meta ) Acrylate; glycidyl vinyl ether having epoxy group, glycidyl vinyl ester, 3,4-epoxycyclohexyl vinyl ether, glycidyl (meth) allyl ether, 3,4-epoxycyclohexyl (meth) allyl ether, 3,4-epoxycyclohexylmethyl (meta) ) Acrylate and the like. Among these, in the present invention, (meth) acrylic monomers having a glycidyl group such as glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferred because of high copolymerizability and high polymerization reaction rate.

また、本発明におけるアクリル系共重合体粒子を調製させるに用いられる「官能基を有さないアクリル系モノマー」として、例えば、（メタ）アクリル酸メチル，（メタ）アクリル酸エチル，（メタ）アクリル酸プロピル，（メタ）アクリル酸イソプロピル，（メタ）アクリル酸ブチル，（メタ）アクリル酸イソブチル，（メタ）アクリル酸ペンチル，（メタ）アクリル酸ヘキシル，（メタ）アクリル酸２−エチルヘキシル，（メタ）アクリル酸オクチル，（メタ）アクリル酸ラウリル，（メタ）アクリル酸ノニル，（メタ）アクリル酸デシル，（メタ）アクリル酸ドデシル等のアクリル酸アルキルエステル；（メタ）アクリル酸フェニル等の芳香族（メタ）アクリル酸エステル；（メタ）アクリル酸メトキシエチル，（メタ）アクリル酸エトキシエチル，（メタ）アクリル酸プロポキシエチル，（メタ）アクリル酸ブトキシエチル，（メタ）アクリル酸エトキシプロピル等のアクリル酸アルコキシエステル；（メタ）アクリル酸シクロヘキシル等の脂環式アルコールの（メタ）アクリル酸エステル等を挙げることができる。   Examples of the “acrylic monomer having no functional group” used for preparing the acrylic copolymer particles in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic. Propyl acid, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) Acrylic acid alkyl esters such as octyl acrylate, lauryl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate; aromatics such as phenyl (meth) acrylate (meta ) Acrylic acid ester; (Meth) acrylic acid methoxyethyl, (meth) acrylic acid ester Acrylic acid alkoxy esters such as xylethyl, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, and ethoxypropyl (meth) acrylate; (meth) acrylic acid of alicyclic alcohol such as cyclohexyl (meth) acrylate Examples include esters.

また、必要に応じて、本発明による超微細アクリル系共重合体粒子に、その自己転着性又は自己被覆コート性等の特性を阻害させない限りにおいて、例えば、撥水性等の機能を賦与させるために、その他の撥水性樹脂成分を適宜添加させることができる。例えば、従来から周知のフッ素系化合物として、パーフロオロエチレン，パーフロオロプロピレン，フッ化ビニリデン等のフッ素含有ビニルモノマーや、例えば、（メタ）アクリル酸トリフルオロメチルメチル，（メタ）アクリル酸−２−トリフルオロメチルエチル，（メタ）アクリル酸−２−パ−フルオロメチルエチル，（メタ）アクリル酸−２−パ−フルオロエチル−２−パ−フルオロブチルエチル，（メタ）アクリル酸−２−パ−フルオロエチル，（メタ）アクリル酸パ−フルオロメチル，（メタ）アクリル酸ジパ−フルオロメチルメチル等のフッ素置換（メタ）アクリル酸系モノマーを挙げられる。   Further, if necessary, the ultrafine acrylic copolymer particles according to the present invention, for example, in order to impart functions such as water repellency, as long as the properties such as self-transfer property or self-coating coating property are not inhibited. In addition, other water-repellent resin components can be appropriately added. For example, conventionally known fluorine-based compounds include fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride, and, for example, trifluoromethyl methyl (meth) acrylate, (meth) acrylic acid-2- Trifluoromethylethyl, (meth) acrylic acid-2-perfluoromethylethyl, (meth) acrylic acid-2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid-2-par Fluorine-substituted (meth) acrylic acid-based monomers such as fluoroethyl, perfluoromethyl (meth) acrylate, and dipa-fluoromethylmethyl (meth) acrylate may be mentioned.

また、本発明において、後述する乳化重合法で、上記した超微細ポリマー粒子を樹脂成分として含有する水性エマルジョン型樹脂組成物又は油溶性染料を内包着色する超微細ポリマー粒子を着色樹脂成分として含有する水性インキ組成物を調製させるに際して、これらの超微細アクリル系共重合体粒子が発揮させる自己転着性又は自己被覆コート性等の特性を阻害させない限りにおいて、必要に応じて、この超微細アクリル系共重合体粒子に、架橋構造を適宜導入・形成させることができる。その架橋剤として、２官能性以上の多官能性モノマーを適宜好適に用いることができる。例えば、エチレングリコールジ（メタ）アクリレート，トリエチレングリコールジ（メタ）アクリレート，テトラエチレングリコールジ（メタ）アクリレート，ジエチレングリコールジ（メタ）アクリレート，ポリプロピレングリコールジ（メタ）アクリレート，ネオペンチルグリコールジ（メタ）アクリレート，トリメチロールプロパントリ（メタ）アクリレート，ペンタエリスリトールトリ（メタ）アクリレート，1,1,1−トリスヒドロキシメチルエタンジアクリレート，1,1,1−トリスヒドロキシメチルエタントリアクリレート等を挙げることができる。本発明において、このような多官能性モノマーは、既に上述した超微細ポリマー粒子の１００質量％当たり、好ましくは、０．１〜１０質量％範囲で適宜好適に使用することができる。   In the present invention, the emulsion polymerization method described later contains, as a colored resin component, an aqueous emulsion type resin composition containing the above-mentioned ultrafine polymer particles as a resin component or ultrafine polymer particles encapsulating an oil-soluble dye. In preparing the water-based ink composition, as long as the properties such as self-transferring property or self-coating coating property exhibited by these ultrafine acrylic copolymer particles are not hindered, the ultrafine acrylic polymer is used as necessary. A crosslinked structure can be appropriately introduced and formed in the copolymer particles. As the crosslinking agent, a bifunctional or higher polyfunctional monomer can be suitably used as appropriate. For example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethane triacrylate, etc. . In the present invention, such a polyfunctional monomer can be suitably used suitably within the range of 0.1 to 10% by mass, preferably 100% by mass of the ultrafine polymer particles already described above.

また、本発明による布地用水性インキ組成物中に分散する「着色ナノマテリアル」樹脂成分は、本発明による布地用水性エマルジョン型樹脂組成物に含有する超微細ポリマー粒子に、予め油性染料を内包着色させた着色超微細ポリマー粒子である。   In addition, the “colored nanomaterial” resin component dispersed in the water-based ink composition for fabric according to the present invention includes an oily dye encapsulated in advance in the ultrafine polymer particles contained in the water-based emulsion resin composition for fabric according to the present invention. Colored ultrafine polymer particles.

そこで、乳化重合法によって、この超微細ポリマー粒子に内包着色させる油溶性染料は、上記するアクリル系モノマーに溶解又は均一に分散する限りにおいて、好ましくは、モノマーより水に溶解し難い油溶性染料であれば特に限定することなく適宜選んで用いられる。その油溶性染料として、例えば、黒色のOlesolol Fast Black，BONJET BLACK CW−1，Solvent Black ２７Ｃｒ(３価)５%含有，Pigment Black７／水、赤色のVALIFAST ＲＥＤ３３０６，Olesolol Fast RED BＬ，Solvent RED８Cr(３価)５．８%含有、青色のカヤセットブルー，Solvent Blue ３５、黄色のALIFAST YELLOW４１２０，Oil Yellow１２９，Solvent Yellow１６，Solvent Yellow３３，Disperse Yellow ５４、レモン色のPiast Yellow ８００５、緑色のOil Green ５０２，Opias Green５０２，マゼンダのVALIFAST PINK２３１０N，Plast RED D−５４，Plast RED ８３５５，Plast RED ８３６０，Plast Vioiet８８５０，Disperse Violet ２８，Solvent RED１４９，Solvent ＲＥＤ４９，Solvent ＲＥＤ ５２，シアンのVALIFAST BLUE２６１０，VALIFAST BLUE ２６０６，Oil BLUE６５０，Plast BLUE８５８０，Plast BLUE８５４０，Oil BLUE ５５１１，オレンジのOil Orange２０１，VALIFAST ORANGE ３２１０，Solvent Orange ７０，カヤセットオレンジG、ブラウンのVALIFAST BROWN ２４０２，Solvent Yellow１１６，Kayaset Flavine ＦＧ等を挙げることができる。   Therefore, the oil-soluble dye to be included and colored in the ultrafine polymer particles by the emulsion polymerization method is preferably an oil-soluble dye that is less soluble in water than the monomer as long as it is dissolved or uniformly dispersed in the acrylic monomer. As long as there is no particular limitation, it is appropriately selected and used. As the oil-soluble dye, for example, black Olesolol Fast Black, BONJET BLACK CW-1, Solvent Black 27Cr (trivalent) containing 5%, Pigment Black 7 / water, red VALIFAST RED 3306, Olesolol Fast RED BL, Solvent RED8Cr (3 5.8% Contained, Blue Kayaset Blue, Solvent Blue 35, Yellow ALIFAST YELLOW 4120, Oil Yellow 129, Solvent Yellow 16, Solvent Yellow 33, Disperse Yellow 54, Lemon Piast Yellow 8005, Green Oil Green 502, Opias Green502, Magenta VALIFAST PINK2310N, Plast RED D-54, Plast RED 8355, Plast RED 8360, Plast Vioiet 8850, Disperse Violet 28, Solvent RED149, Solvent RED49, Solvent RED 52, Cyan VALIFAST BLUE2610, VALIFAST BLUE2610, VALIFAST BLUE26 Plast BLUE 8580, Plast BLUE 8540, Oil BLUE 5511, Orange Oil 01, VALIFAST ORANGE 3210, Solvent Orange 70, Kayaset Orange G, can be mentioned VALIFAST BROWN 2402, Solvent Yellow116, Kayaset Flavine FG like brown.

また、例えば、ソルベントブルー，ソルベントレッド，ソルベントオレンジ，ソルベントグリーン，ルモゲンＦオレンジー等が挙げられる。また、例えば、クラリン系、ペリレン系、ジシアノピニル系、アゾ系、キノフタロン系、アミノピラゾール系、メチン系、ジシアノイミダゾール系、インドアニリン系、フタロシアニン系等の筆記記録液に通常使用されている染料や、感熱記録紙や感温色材として用いられるロイコ染料や、また、例えば、ローダミンＢステアレート（赤色２１５号），テトラクロルテトラブロムフルオレセン（赤色２１８号），テトラブロムフルオレセン（赤色２２３号），スダンIII（赤色２２５号），ジブロムフルオレセイン（橙色２０１号），ジヨードフルオレセイン（橙色２０６号），フルオレセイン（黄色２０１号），キノリンエローＳＳ（黄色２０４号），キニザリングリーンＳＳ（緑色２０２号），アズリンパープルＳＳ（紫色２０１号），薬用スカーレット（赤色５０１号），オイルレッドＸＯ（赤色５０５号），オレンジＳＳ（橙色４０３号），エローＡＢ（黄色４０４号），エローＯＢ（黄色４０５号），スダンブルーB（青色４０３号）等の化粧品に使用されているタール系染料をも挙げることができる。   Moreover, for example, solvent blue, solvent red, solvent orange, solvent green, rumogen F orange and the like can be mentioned. In addition, for example, dyes commonly used in writing recording liquids such as clarine, perylene, dicyanopinyl, azo, quinophthalone, aminopyrazole, methine, dicyanoimidazole, indoaniline, phthalocyanine, A leuco dye used as a heat-sensitive recording paper or a temperature-sensitive color material, and, for example, rhodamine B stearate (red 215), tetrachlorotetrabromofluoresene (red 218), tetrabromofluorescene (red 223) No.), Sudan III (red No. 225), dibromofluorescein (orange No. 201), diiodo fluorescein (orange No. 206), fluorescein (yellow No. 201), quinoline yellow SS (yellow No. 204), quinizarin green SS ( Green 202), azurin purple SS (purple 201), medicine Cosmetics such as Scarlet (Red 501), Oil Red XO (Red 505), Orange SS (Orange 403), Yellow AB (Yellow 404), Yellow OB (Yellow 405), Sudan Blue B (Blue 403) The tar-type dye currently used for can also be mentioned.

また、本発明において、これらの染料の単独又は２種以上を混合させて使用することができる。また、必要に応じて各種の直接染料、酸性染料、塩基性染料、アゾイック染料、反応性染料、蛍光染料及び蛍光増白剤等を所望する色調等に応じて適宜選んで使用することができる。本発明において、質量基準で表わして、この超微細ポリマー粒子のナノマテリアル樹脂成分の１００質量％当たり、０．１〜５０質量％の範囲で、好ましくは、０．５〜２０質量％の範囲で適宜好適に内包着色させることができる。   Moreover, in this invention, these dyes can be used individually or in mixture of 2 or more types. In addition, various direct dyes, acid dyes, basic dyes, azoic dyes, reactive dyes, fluorescent dyes, fluorescent brighteners, and the like can be appropriately selected and used according to the desired color tone, if necessary. In the present invention, expressed in terms of mass, per 100% by mass of the nanomaterial resin component of the ultrafine polymer particles, in the range of 0.1 to 50% by mass, preferably in the range of 0.5 to 20% by mass. The inclusion color can be appropriately and suitably applied.

そこで、本発明による布地用水性エマルジョン型樹脂組成物又は布地用水性インキ組成物を転着又は被覆コート、または、印刷又は転写させる被転着体又は被被覆コート体、または、被印刷体又は被転写体である布地として、本発明においては、例えば、綿・コットン、麻、ウール、シルク、カシミヤ等の天然繊維；レーヨン、キュプラ、テンセル等の再生繊維；アセテート、トリアセテート等の半合成繊維；ナイロン、ポリエステル、アクリル、ポリオレフィン、ポリ塩化ビニル、ビニロン、ビニリデン、ポリウレタン、ポリアミド等合成繊維のそれぞれ単独繊維及びこれらの少なくとも２種の複合繊維の群から選ばれる何れかの繊維からなる織布又は不織布等を挙げることができる。中でも、従来の技術では、被覆コート又は印刷させるに種々障害を発生させる綿・コットン、ポリエステル等の布地に対しても、バインダーレスで、しかも、熱圧着させることなく、転着又は被覆コート、または、印刷又は転写させることができる。   Accordingly, a water-based emulsion-type resin composition for fabrics or a water-based ink composition for fabrics is transferred or coated, or transferred or coated to be printed or transferred, or to be printed or coated. In the present invention, for example, natural fibers such as cotton / cotton, hemp, wool, silk, and cashmere; regenerated fibers such as rayon, cupra, and tencel; semi-synthetic fibers such as acetate and triacetate; Polyester, acrylic, polyolefin, polyvinyl chloride, vinylon, vinylidene, polyurethane, polyamide, and the like, each of a single fiber of synthetic fibers, and a woven or non-woven fabric made of any fiber selected from the group of at least two types of these composite fibers. Can be mentioned. Among them, in the conventional technique, even a cloth such as cotton, cotton, polyester, etc. that causes various obstacles to the coating coat or printing, is binderless, and without being thermocompression bonded, the transfer or coating coat, or Can be printed or transferred.

また、上記する布地に本発明による水性エマルジョン型樹脂組成物又は水性インキ組成物を転着又は被覆コート、または、印刷又は転写させるには、従来から公知であるブレードコータ、エアーナイフコート、ロールコート、バーコータ、グラビヤコータ、ロッドブレードコータ、ダイコータ、インクジェット塗工、または、凸版印刷、グラビヤ印刷、スクリーン印刷、インクジェット印刷等を挙げることができる。   In order to transfer, coat, or print or transfer the water-based emulsion resin composition or water-based ink composition according to the present invention to the above-described fabric, a conventionally known blade coater, air knife coat, roll coat , Bar coater, gravure coater, rod blade coater, die coater, ink jet coating, letterpress printing, gravure printing, screen printing, ink jet printing and the like.

＜その他の添加剤及び機能剤＞
また、本発明による超微細ポリマー粒子又は着色超微細ポリマー粒子のナノマテリアル樹脂成分中には、このような超微細粒子径を有する粒子形成を阻害させたり、又は上記する如くのナノマテリアル樹脂成分が発揮する特徴及び機能発現を阻害させたりしない限りにおいて、必要に応じて、それ自体公知のその他の添加剤及び機能剤を添加又は配合させて、これらの添加・配合剤に基づく機能及び作用を反映させることができる。例えば、分散剤、分散安定剤、キレート化剤、防カビ剤、防腐剤、タレ止め防止剤、表面張力調整剤、ＰＨ調整剤、消泡剤、防錆剤、酸化防止剤、帯電防止剤、紫外線吸収剤、近赤外線吸収剤、抗菌・防カビ剤、蛍光剤、有機ＥＬ発光剤、香料、各種薬効成分等を適宜用いることができる。 <Other additives and functional agents>
Further, in the nanomaterial resin component of the ultrafine polymer particles or colored ultrafine polymer particles according to the present invention, the formation of particles having such an ultrafine particle diameter is inhibited, or the nanomaterial resin component as described above is present. As long as it does not inhibit the manifestation of the features and functions to be exhibited, other known additives and functional agents are added or blended as necessary to reflect the functions and actions based on these additives and blending agents. Can be made. For example, a dispersant, a dispersion stabilizer, a chelating agent, an antifungal agent, an antiseptic, an anti-sagging agent, a surface tension adjusting agent, a PH adjusting agent, an antifoaming agent, an antirust agent, an antioxidant, an antistatic agent, Ultraviolet absorbers, near infrared absorbers, antibacterial / antifungal agents, fluorescent agents, organic EL luminescent agents, fragrances, various medicinal components, and the like can be used as appropriate.

＜本発明による布地用水性エマルジョン型樹脂組成物の調製＞
そこで、自然乾燥下に布地に自己転着又は自己被覆コート性を発揮させ、しかも、優れる耐洗濯性を有して、布地に撥油性や、防汚性等の機能を賦与させる本発明による布地用水性エマルジョン型樹脂組成物の調製法について以下に説明する。 <Preparation of water-based emulsion resin composition for fabric according to the present invention>
Therefore, the fabric according to the present invention that exhibits self-transferability or self-coating coatability on the fabric under natural drying, and has excellent washing resistance and imparts functions such as oil repellency and antifouling properties to the fabric. A method for preparing the aqueous emulsion resin composition for use will be described below.

そこで、既に説明する如く、本発明による布地用水性エマルジョン型樹脂組成物は、通常の乳化重合法を用いて調製される平均粒子径が５〜１００ｎｍの超微細ポリマー粒子で、しかも、ガラス転移点Ｔｇ≧−５０℃で、Ｔｇ≦１０℃の低Ｔｇなる「ナノマテリアル樹脂成分」を含有する水性エマルジョン型樹脂組成物である。
本発明によれば、
（１）このナノマテリアル樹脂成分は、８００〜９５０質量部の水相中に、例えば、乳化剤としてドデシルベンゼンスルホン酸アンモニウム塩１０〜１６質量部と、例えば、メタノール１０〜１２質量部とを添加させて、撹拌下に７５〜９０℃に昇温させた後、所定量の過硫酸アンモニウムを添加させる。
（２）次いで、撹拌下の７０〜８０℃加温下に、官能基を持たない所定の重合性アクリル系モノマーの所定量と、グリシジル基を有する所定の重合性アクリル系モノマー（又は含グリシジル基モノマー）の所定量との全重合性モノマー成分１００質量％に対して、この含グリシジル基モノマー成分の１０〜７０質量％範囲の所定量と、追加所定量の乳化剤と共に、１．５〜３時間を要して注下乳化重合及び熟成させる。
（３）その結果、略１００％重合率下に超微細ポリマー粒子としての樹脂成分が、固形分濃度１０〜１６％である水性エマルジョン反応物として調製される。また、このように調製される本発明による超微細ポリマー粒子は、体積基準で表す平均粒子径が５〜１００ｎｍの範囲にあるナノマテリアル樹脂素材として適宜好適に調製される。また、本発明においては、略１００％の重合率で得られることから、適宜容易にＴｇ≧−５０℃で、且つＴｇ≦１０℃である所定の低Ｔｇを有する超微細ポリマー粒子を調製することができる。 Therefore, as already explained, the aqueous emulsion resin composition for fabrics according to the present invention is an ultrafine polymer particle having an average particle diameter of 5 to 100 nm prepared using a usual emulsion polymerization method, and has a glass transition point. It is an aqueous emulsion resin composition containing a “nanomaterial resin component” having a low Tg of Tg ≦ −50 ° C. and Tg ≦ 10 ° C.
According to the present invention,
(1) In this nanomaterial resin component, for example, 10 to 16 parts by mass of ammonium dodecylbenzenesulfonate and 10 to 12 parts by mass of methanol are added as an emulsifier in an aqueous phase of 800 to 950 parts by mass. Then, after raising the temperature to 75 to 90 ° C. with stirring, a predetermined amount of ammonium persulfate is added.
(2) Next, a predetermined amount of a predetermined polymerizable acrylic monomer having no functional group and a predetermined polymerizable acrylic monomer having a glycidyl group (or a glycidyl-containing group) are heated at 70 to 80 ° C. with stirring. Monomer) with a predetermined amount of 100% by mass of the total polymerizable monomer component and a predetermined amount in the range of 10 to 70% by mass of this glycidyl group monomer component and an additional predetermined amount of emulsifier for 1.5 to 3 hours. In this manner, emulsion polymerization and aging are carried out under pouring.
(3) As a result, the resin component as ultrafine polymer particles is prepared as an aqueous emulsion reaction product having a solid content concentration of 10 to 16% at a polymerization rate of approximately 100%. In addition, the ultrafine polymer particles according to the present invention prepared as described above are suitably suitably prepared as a nanomaterial resin material having an average particle diameter expressed by volume based on a range of 5 to 100 nm. In the present invention, since it is obtained at a polymerization rate of about 100%, it is possible to easily prepare ultrafine polymer particles having a predetermined low Tg with Tg ≧ −50 ° C. and Tg ≦ 10 ° C. as appropriate. Can do.

以上のような乳化重合法によって調製される本発明による水性エマルジョン型樹脂組成物は、布地に塗布させ自然乾燥温度雰囲気下である非熱圧着下に、自己転着性又は自己被覆コート性を発揮させて、その転着又は被覆コート樹脂成分によって、布地に各種の機能を賦与させる布地用水性エマルジョン型樹脂組成物として適宜好適に布地に転着又は被覆コートされる。   The aqueous emulsion resin composition according to the present invention prepared by the emulsion polymerization method as described above exhibits self-transferability or self-coating properties under non-thermocompression, which is applied to a fabric and is in an atmosphere of natural drying temperature. Then, the transfer or coating coat resin component appropriately transfers or coats the fabric as a water-based emulsion-type resin composition for fabrics that imparts various functions to the fabric.

以上のような乳化重合法によって調製される「ナノマテリアル樹脂成分」を含有する本発明による水性エマルジョン型樹脂組成物は、既に説明する如く、布地に塗布させた後、自然温度乾燥下に、良好な自己転着性又は自己被覆コート性を発揮させる。また、その転着又は被覆コート樹脂成分によって、布地に各種の機能を賦与させることができる。   The aqueous emulsion-type resin composition according to the present invention containing the “nanomaterial resin component” prepared by the emulsion polymerization method as described above is satisfactory after being applied to a fabric and then dried at natural temperature as described above. Self-transfer property or self-coating property is exhibited. Moreover, various functions can be imparted to the fabric by the transfer or coating coat resin component.

そこで、本発明において、上記する乳化重合に用いる乳化剤は、従来から、通常に、乳化剤として使用されているアニオン系界面活性剤、カチオン系界面活性剤又は必要に応じてノニオン系界面活性剤等から適宜選んで、その単独又は組合わせて使用することができる。例えば、アニオン系界面活性剤；ドデシルベンゼンスルホネート、ウンデシルベンゼンスルホネート、トリデシルベンゼンスルホネート、ノニルベンゼンスルホネート等が挙げられ、カチオン系界面活性剤；セチルトリメチルアンモニウムプロミド、塩化ヘキサデシルピリジニウム、塩化ヘキサデシルトリメチルアンモニウム等が挙げられ、また、ノニオン系界面活性剤；リピリジニウム等が挙げられる。さらに、アクリロイル基、メタクリロイル基等の重合性基を有する反応性乳化剤を使用することができる。これらの乳化剤は、特に限定することなく使用される。本発明において、これらの乳化剤は、上記するアクリル系モノマー等の重合性モノマー１００質量部に対して、０．１〜５０質量部で、好ましくは０．５〜２０質量部の範囲で適宜添加させることができる。   Therefore, in the present invention, the emulsifier used for the emulsion polymerization described above is conventionally an anionic surfactant, a cationic surfactant, or a nonionic surfactant as necessary, which is usually used as an emulsifier. They can be selected as appropriate and used alone or in combination. Examples include anionic surfactants; dodecyl benzene sulfonate, undecyl benzene sulfonate, tridecyl benzene sulfonate, nonyl benzene sulfonate, and the like. Cationic surfactants; cetyl trimethyl ammonium promide, hexadecyl pyridinium chloride, hexadecyl chloride Trimethylammonium etc. are mentioned, Nonionic surfactant; Lipidinium etc. are mentioned. Furthermore, a reactive emulsifier having a polymerizable group such as an acryloyl group or a methacryloyl group can be used. These emulsifiers are used without particular limitation. In the present invention, these emulsifiers are appropriately added in an amount of 0.1 to 50 parts by mass, preferably in the range of 0.5 to 20 parts by mass, with respect to 100 parts by mass of the polymerizable monomer such as the acrylic monomer described above. be able to.

また、この添加量に係わって従来の知見からすると、下限値方向の添加量では、得られる樹脂微粒子の粒子径が大き目の傾向に形成され、一方、上限値方向の添加量では、その粒子径が小さ目の傾向に形成される。本発明においても、所定の撹拌速度下に油溶性染料が内包着色固定する樹脂微粒子の平均粒子径は、体積基準で表して５〜１００ｎｍ範囲に適宜調製することができる。   Further, according to conventional knowledge related to this addition amount, the particle size of the resin fine particles obtained tends to be larger in the addition amount in the lower limit direction, while the particle size is larger in the addition amount in the upper limit direction. Is formed in a small tendency. Also in the present invention, the average particle diameter of the resin fine particles that are encapsulated and fixed by the oil-soluble dye under a predetermined stirring speed can be appropriately adjusted in the range of 5 to 100 nm on a volume basis.

また、本発明による水性エマルジョン型樹脂組成物中に含有する水性媒体としては、主水性成分の水相中に、メタノール、エタノール、プロパノール、イソプロパノール、アセトン、メチルエチルケトン及びテトラヒドロフラン等から適宜に選ばれる何れかの水溶性有機溶媒を含有させることができる。   Further, the aqueous medium contained in the aqueous emulsion resin composition according to the present invention is any one appropriately selected from methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, tetrahydrofuran and the like in the aqueous phase of the main aqueous component. The water-soluble organic solvent can be contained.

＜本発明による布地用水性インキ組成物の調製＞
本発明によれば、布地に塗布させた後、熱圧着させることなく、自己転着性としての印刷性又は転写性を発揮させる本発明による布地用水性インキ組成物は、既に上記した本発明による布地用水性エマルジョン型樹脂組成物中に、含有する「ナノマテリアル樹脂成分」の超微細ポリマー粒子に、油溶性染料を内包着色させてなる「着色ナノマテリアル樹脂成分」の着色超微細ポリマー粒子の樹脂成分がインキ成分となるものである。 <Preparation of water-based ink composition for fabric according to the present invention>
According to the present invention, the water-based ink composition for a fabric according to the present invention that exhibits printability or transferability as self-transferability without being thermocompression-bonded after being applied to the fabric is based on the above-described present invention. Resin of colored ultrafine polymer particles of “colored nanomaterial resin component” obtained by encapsulating oil-soluble dye in ultrafine polymer particles of “nanomaterial resin component” contained in aqueous emulsion-type resin composition for fabric The component is an ink component.

以上から、通常の乳化重合法で、非熱圧着下に、自己転着性としての印刷性又は転写性を発揮させ、しかも、その印刷又は転写着色樹脂成分には、優れる耐洗濯性を有する撥油性や、防汚性機能や、防印刷滲み性等を発揮させる本発明による水性インキ組成物の調製法について以下に説明をする。   As described above, the printing property or transferability as a self-transfer property is exhibited under non-thermocompression bonding by an ordinary emulsion polymerization method, and the printing or transfer coloring resin component has excellent washing resistance. A method for preparing a water-based ink composition according to the present invention that exhibits oiliness, antifouling function, anti-printing bleeding property and the like will be described below.

本発明によれば、
（１）「着色ナノマテリアル樹脂成分」は、８００〜９５０質量部の水相中に、例えば、乳化剤としてドデシルベンゼンスルホン酸アンモニウム塩１０〜１６質量部と、例えば、水溶性有機溶剤としてメタノール１０〜１２質量部とを添加させて、撹拌下に７５〜９０℃に昇温させた後、所定量の過硫酸アンモニウムを添加させる。
（２）次いで、撹拌下の７０〜８０℃加温下に、官能基を持たない所定の重合性アクリル系モノマーの所定量と、グリシジル基を有する所定の重合性アクリル系モノマー（又は含グリシジル基モノマー）の所定量との全重合性モノマー成分１００質量％に対して、この含グリシジル基モノマー成分の１０〜７０質量％範囲の所定量と、追加所定量の乳化剤と、更に、所定の油溶性染料を、共重合させて得られる共重合体ポリマー粒子の１００質量％当たり０．１〜５０質量％の範囲で内包着色させる所定の油溶性染料と共に、１．５〜３時間を要して注下乳化重合させた後、７０〜８０℃で２５〜４５分保持後、８５℃に昇温させて１〜２時間保持・熟成させる。
（３）その結果、着色超微細ポリマー粒子としての固形分濃度１０〜１５％である水性エマルジョン反応物が調製される。また、このように調製される着色超微細ポリマー粒子は、体積基準で表す平均粒子径が５〜１００ｎｍの範囲にある「着色ナノマテリアル」樹脂成分であって、この着色樹脂成分が、所謂インキ成分である。 According to the present invention,
(1) “Colored nanomaterial resin component” is, for example, 10 to 16 parts by mass of ammonium dodecylbenzenesulfonate as an emulsifier and 10 to 10 parts of methanol as a water-soluble organic solvent in an aqueous phase of 800 to 950 parts by mass. After adding 12 parts by mass and raising the temperature to 75 to 90 ° C. with stirring, a predetermined amount of ammonium persulfate is added.
(2) Next, a predetermined amount of a predetermined polymerizable acrylic monomer having no functional group and a predetermined polymerizable acrylic monomer having a glycidyl group (or a glycidyl-containing group) are heated at 70 to 80 ° C. with stirring. Monomer) with respect to 100% by mass of the total polymerizable monomer component with respect to the predetermined amount, a predetermined amount in the range of 10 to 70% by mass of this glycidyl group monomer component, an additional predetermined amount of emulsifier, and a predetermined oil solubility. It takes 1.5 to 3 hours together with a predetermined oil-soluble dye to be included and colored in a range of 0.1 to 50% by mass per 100% by mass of copolymer polymer particles obtained by copolymerizing the dye. After under-emulsion polymerization, after holding at 70-80 ° C. for 25-45 minutes, the temperature is raised to 85 ° C. and held / ripened for 1-2 hours.
(3) As a result, an aqueous emulsion reaction product having a solid content concentration of 10 to 15% as colored ultrafine polymer particles is prepared. Further, the colored ultrafine polymer particles prepared in this way are “colored nanomaterial” resin components having an average particle size in the range of 5 to 100 nm expressed on a volume basis, and these colored resin components are so-called ink components. It is.

また、本発明による水性エマルジョン型樹脂組成物中に含有する水性媒体としては、主水性成分の水相中に、メタノール、エタノール、プロパノール、イソプロパノール、アセトン、メチルエチルケトン及びテトラヒドロフラン等から選ばれる何れかの水溶性有機溶媒を含有させることができる。また、本発明においては、このような水性有機媒体は、内包着色させる油溶性染料を乳化重合下に効果的に内包固定させて染料着色樹脂粒子を形成させるに際して、所謂、染料親水化助剤として作用させる水性有機媒体でもある。
以下に、本発明を実施例により説明するが、本発明は、これらの実施例にいささかも限定されるものではない。 The aqueous medium contained in the aqueous emulsion resin composition according to the present invention includes any water-soluble substance selected from methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, tetrahydrofuran and the like in the aqueous phase of the main aqueous component. An organic solvent can be contained. Further, in the present invention, such an aqueous organic medium is used as a so-called dye hydrophilization aid in forming dye-colored resin particles by effectively encapsulating and fixing an oil-soluble dye to be encapsulated under emulsion polymerization. It is also an aqueous organic medium to act.
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

（実施例１）
本実施例において、水性媒体中に、その粒子表面にグリシジル基が頭出し状に形成され、しかも、ガラス転移点（Ｔｇ）；−５０℃≦Ｔｇ≦１０℃である体積基準で表す平均粒子径が１００ｎｍ以下の超微細ポリマー粒子の「ナノマテリアル樹脂成分」を分散する本発明による布地用水性エマルジョン型樹脂組成物を調製する。次いで、この用水性エマルジョン型樹脂組成物を、布地に被覆コートさせた後、ホットプレスすることなく、自己転着性又は自己被覆コート性を発揮させて、その転着又は被覆樹脂成分によって、布地に耐洗濯性を有する撥油性、防汚性の機能が賦与されている機能性布地について以下に説明する。 Example 1
In this example, in the aqueous medium, a glycidyl group is formed on the surface of the particle in the form of a head, and the glass transition point (Tg): −50 ° C. ≦ Tg ≦ 10 ° C. An aqueous emulsion type resin composition for fabric according to the present invention is prepared, in which the “nanomaterial resin component” of ultrafine polymer particles having a particle size of 100 nm or less is dispersed. Next, the water-based emulsion resin composition for use is coated on the fabric, and then exhibits self-transferability or self-coatability without hot pressing. A functional fabric to which oil-repellent and antifouling functions having wash resistance are added will be described below.

＜＜本発明による自己転着又は自己被覆コート性の布地用水性エマルジョン型樹脂組成物の調製＞＞
本発明によれば、
（１）温度計と窒素導入管とを装着した容量１リットルの四つ口フラスコに、イオン交換水９００質量部と乳化剤のドデシルベンゼンスルホン酸アンモニウム塩の１４質量部と、メタノール１１．２質量部を添加し、８５℃まで昇温し、過硫酸アンモニウムを０．５質量部添加した。
（２）次いで、温度を７６〜７８℃に保ちながら、
・アクリル酸ブチル（ＢＡ）の９０質量部と、
・メタクリル酸グリシジル（ＧＭＡ）の１０質量部と、
を乳化剤のドデシルベンゼンスルホン酸アンモニウム塩１重量部と共に、２時間かけて注下させて共重合させた後、更に、７６〜７８℃で３０分保持させた後、８５℃まで昇温させて１．５時間保持・熟成を行った。
（３）その結果、重合率は約１００％で、Ｔｇ＝−４８℃である平均粒子径が２３．６ｎｍの超微細ポリマー粒子の「ナノマテリアル樹脂成分」が固形分濃度として１４．５％の水性エマルジョン反応物が得られた。 << Preparation of Water-based Emulsion Resin Composition for Self-Transferred or Self-Coating Coatable Fabrics >>
According to the present invention,
(1) In a 4-liter flask having a capacity of 1 liter equipped with a thermometer and a nitrogen introduction tube, 900 parts by mass of ion-exchanged water, 14 parts by mass of ammonium salt of dodecylbenzenesulfonate as an emulsifier, and 11.2 parts by mass of methanol Was added, the temperature was raised to 85 ° C., and 0.5 parts by mass of ammonium persulfate was added.
(2) Next, while maintaining the temperature at 76-78 ° C,
-90 parts by weight of butyl acrylate (BA),
-10 parts by weight of glycidyl methacrylate (GMA),
Was added together with 1 part by weight of an emulsifier ammonium dodecylbenzenesulfonate for 2 hours to be copolymerized, and further maintained at 76 to 78 ° C. for 30 minutes, and then heated to 85 ° C. for 1 . Retained and aged for 5 hours.
(3) As a result, the polymerization rate is about 100%, and the “nanomaterial resin component” of the ultrafine polymer particles having an average particle diameter of 23.6 nm with Tg = −48 ° C. is 14.5% as a solid content concentration. An aqueous emulsion reaction was obtained.

＜＜機能性布地の調製＞＞
次いで、１０ｃｍ角の木綿製布地に噴霧器で上記する水性エマルジョン反応物を均一に塗布させ、室温温度雰囲気下に充分乾燥させた後、この布地を「洗濯用洗剤で手洗い」⇔「室温乾燥」の洗濯サイクルを１０回行った布地上の四箇所に、市販の油性インキ滴をスポットさせた。次いで、３時間放置後、薄い洗剤液中で軽く手洗いした布地には、全く油質の痕跡や、インキ滴による汚染の痕跡が見られなかった。以上から、本発明による超微細ポリマー粒子の「ナノマテリアル樹脂成分」を含有する布地用水性エマルジョン型樹脂組成物を、布地に被覆コートさせた後、ホットプレスさせることなく、自己転着又は自己被覆コートされて、布地に耐洗濯性を有する撥油性、防汚性の機能を賦与させることができた。 << Preparation of functional fabric >>
Next, the above-mentioned aqueous emulsion reaction product was uniformly applied to a 10 cm square cotton fabric with a sprayer and sufficiently dried in a room temperature atmosphere, and then this fabric was “washed with a laundry detergent” and “dried at room temperature”. Commercially available oil-based ink droplets were spotted at four locations on the fabric where the washing cycle was performed 10 times. Next, after leaving it for 3 hours, the fabric which was lightly hand-washed in a thin detergent solution did not show any traces of oil or contamination due to ink droplets. From the above, the aqueous emulsion-type resin composition for fabrics containing the “nanomaterial resin component” of the ultrafine polymer particles according to the present invention is coated on the fabric and then self-transferred or self-coated without hot pressing. As a result, it was possible to impart oil-repellent and antifouling functions having wash resistance to the fabric.

（実施例２）
実施例１において、アクリル酸ブチル（ＢＡ）の９０質量部及びメタクリル酸グリシジル（ＧＭＡ）の１０質量部とを、ＢＡの７０質量部と、ＧＭＡの３０質量部に変えた以外は、実施例１と同様にして、水性エマルジョン反応物を調製した。その結果、重合率は約１００％で、Ｔｇ＝−３２℃である平均粒子径が２４ｎｍの超微細ポリマー粒子の「ナノマテリアル樹脂成分」が固形分濃度として１４％の水性エマルジョン反応物が得られた。 (Example 2)
Example 1 except that 90 parts by mass of butyl acrylate (BA) and 10 parts by mass of glycidyl methacrylate (GMA) were changed to 70 parts by mass of BA and 30 parts by mass of GMA in Example 1. In the same manner, an aqueous emulsion reaction was prepared. As a result, an aqueous emulsion reaction product having a polymerization rate of about 100% and a “nanomaterial resin component” of ultrafine polymer particles having an average particle diameter of 24 nm and Tg = −32 ° C. as a solid content concentration of 14% is obtained. It was.

（実施例３）
実施例１において、アクリル酸ブチル（ＢＡ）の９０質量部及びメタクリル酸グリシジル（ＧＭＡ）の１０質量部とを、ＢＡの５０質量部と、ＧＭＡの５０質量部に変えた以外は、実施例１と同様にして、水性エマルジョン反応物を調製した。その結果、重合率は約１００％で、Ｔｇ＝−１４℃である平均粒子径が２５ｎｍの超微細ポリマー粒子の「ナノマテリアル樹脂成分」が固形分濃度として１４％の水性エマルジョン反応物が得られた。 (Example 3)
Example 1 Example 1 except that 90 parts by mass of butyl acrylate (BA) and 10 parts by mass of glycidyl methacrylate (GMA) were changed to 50 parts by mass of BA and 50 parts by mass of GMA. In the same manner, an aqueous emulsion reaction was prepared. As a result, an aqueous emulsion reaction product having a polymerization rate of about 100% and a “nanomaterial resin component” of ultrafine polymer particles having an average particle diameter of 25 nm and Tg = −14 ° C. as a solid content concentration is obtained. It was.

（実施例４）
実施例１において、アクリル酸ブチル（ＢＡ）の９０質量部及びメタクリル酸グリシジル（ＧＭＡ）の１０質量部とを、ＢＡの３５質量部と、ＧＭＡの６５質量部に変えた以外は、実施例１と同様にして、水性エマルジョン反応物を調製した。その結果、重合率は約１００％で、Ｔｇ＝２℃である平均粒子径が２５ｎｍの超微細ポリマー粒子の「ナノマテリアル樹脂成分」が固形分濃度として１３％の水性エマルジョン反応物が得られた。 Example 4
Example 1 Example 1 except that 90 parts by mass of butyl acrylate (BA) and 10 parts by mass of glycidyl methacrylate (GMA) were changed to 35 parts by mass of BA and 65 parts by mass of GMA. In the same manner, an aqueous emulsion reaction was prepared. As a result, an aqueous emulsion reaction product having a polymerization rate of about 100% and a “nanomaterial resin component” of ultrafine polymer particles having an average particle diameter of 25 nm at Tg = 2 ° C. as a solid content concentration was obtained as 13%. .

（比較例１）
実施例１において、アクリル酸ブチル（ＢＡ）の９０質量部及びメタクリル酸グリシジル（ＧＭＡ）１０質量部を、ＢＡの１００質量部に変えた以外は、実施例１と同様にして水性エマルジョン反応物を調製した。その結果、重合率は約１００％で、Ｔｇ＝−５５℃、平均粒子径が２４ｎｍ、固形分濃度１４％の水性エマルジョン反応物が得られた。 (Comparative Example 1)
In Example 1, except that 90 parts by mass of butyl acrylate (BA) and 10 parts by mass of glycidyl methacrylate (GMA) were changed to 100 parts by mass of BA, an aqueous emulsion reaction product was prepared in the same manner as in Example 1. Prepared. As a result, an aqueous emulsion reaction product having a polymerization rate of about 100%, Tg = −55 ° C., an average particle size of 24 nm, and a solid content concentration of 14% was obtained.

（比較例２）
実施例１において、アクリル酸ブチル（ＢＡ）の９０質量部及びメタクリル酸グリシジル（ＧＭＡ）１０質量部を、ＢＡの２３質量部及びＧＭＡの７７質量部に変えた以外は、実施例１と同様にして水性エマルジョン反応物を調製した。その結果、重合率は約１００％で、Ｔｇ＝１５℃、平均粒子径が２４ｎｍ、固形分濃度１２％の水性エマルジョン反応物が得られた。 (Comparative Example 2)
In Example 1, 90 parts by mass of butyl acrylate (BA) and 10 parts by mass of glycidyl methacrylate (GMA) were changed to 23 parts by mass of BA and 77 parts by mass of GMA. An aqueous emulsion reaction was prepared. As a result, an aqueous emulsion reaction product having a polymerization rate of about 100%, Tg = 15 ° C., an average particle size of 24 nm, and a solid content concentration of 12% was obtained.

（実施例５）
本実施例において、その粒子表面にグリシジル基が存在し、ガラス転移点（Ｔｇ）が−５０℃≦Ｔｇ≦１０℃である体積基準で表す平均粒子径が１００ｎｍ以下の超微細ポリマー粒子の「着色ナノマテリアル樹脂成分」を、水性媒体中に分散している本発明による布地用水性インキ組成物を調製する。 (Example 5)
In this example, “coloring” of ultrafine polymer particles having a glycidyl group on the particle surface and having an average particle diameter of 100 nm or less expressed on a volume basis with a glass transition point (Tg) of −50 ° C. ≦ Tg ≦ 10 ° C. A water-based ink composition for fabric according to the present invention in which the “nanomaterial resin component” is dispersed in an aqueous medium is prepared.

＜＜本発明による自己印刷又は自己転写性の布地用水性インキ組成物の調製＞＞
本発明によれば、
（１）温度計と窒素導入管とを装着した容量１リットルの四つ口フラスコに、イオン交換水９００質量部と乳化剤のドデシルベンゼンスルホン酸アンモニウム塩の１４質量部と、メタノール１１．２質量部を添加し、８５℃まで昇温し、過硫酸アンモニウムを０．５質量部添加した。
（２）次いで、温度を７６〜７８℃に保ちながら、
・アクリル酸ブチル（ＢＡ）９０質量部と、
・メタクリル酸グリシジル（ＧＭＡ）１０質量部と、
・油溶性染料Solvent RED ４９の５質量部と、
乳化剤のドデシルベンゼンスルホン酸アンモニウム塩の１重量部とを２時間かけて注下させて重合を行った。更に、７６〜７８℃で３０分保持した後、８５℃まで昇温しその温度で１．５時間保持・熟成を行った。
（３）その結果、重合率は約１００％であり、平均粒子径が２４ｎｍの超微細ポリマー粒子の「着色ナノマテリアル樹脂成分」が固形分濃度として１５％の水性エマルジョン反応物が得られた。なお、この「着色ナノマテリアル樹脂成分」のガラス点移転Ｔｇ＝−４８℃である。 << Preparation of water-based ink composition for self-printing or self-transferring fabric according to the present invention >>
According to the present invention,
(1) In a 4-liter flask having a capacity of 1 liter equipped with a thermometer and a nitrogen introduction tube, 900 parts by mass of ion-exchanged water, 14 parts by mass of ammonium salt of dodecylbenzenesulfonate as an emulsifier, and 11.2 parts by mass of methanol Was added, the temperature was raised to 85 ° C., and 0.5 parts by mass of ammonium persulfate was added.
(2) Next, while maintaining the temperature at 76-78 ° C,
-90 parts by weight of butyl acrylate (BA),
-10 parts by weight of glycidyl methacrylate (GMA),
-5 parts by mass of the oil-soluble dye Solvent RED 49,
Polymerization was carried out by pouring 1 part by weight of an emulsifier ammonium dodecylbenzenesulfonate over 2 hours. Furthermore, after 30 minutes hold | maintaining at 76-78 degreeC, it heated up to 85 degreeC, and hold | maintained and matured at that temperature for 1.5 hours.
(3) As a result, an aqueous emulsion reaction product having a polymerization rate of about 100% and a “colored nanomaterial resin component” of ultrafine polymer particles having an average particle diameter of 24 nm as a solid content concentration was obtained. In addition, it is glass point transfer Tg = -48 degreeC of this "coloring nanomaterial resin component."

＜＜綜研化学（株）のロゴ・マーク「Ｓ字図形」の印刷＞＞
次いで、この水性インキ組成物を、１０ｃｍ角のポリエステル製布地上に、綜研化学（株）のロゴ・マークである「Ｓ字図形」をくり抜いた１ｍｍ厚のＰＥＴマスク・フイルムを重ねた上から、この水性インキ組成物を筆で転着させた。次いで、ホットプレスすることなく、室温雰囲気下に３時間放置乾燥させた。
この布地を「洗濯用洗剤で手洗い」⇔「室温乾燥」の洗濯サイクルを１０回行った布地上のＳ字図形の色調変化評価法によって、印刷「Ｓ字図形」の印刷性又は転写性及びその耐洗濯性を評価してその結果を表１に示した。
また、サイクル洗濯する前の印刷「Ｓ字図形」上に、市販の青色の油性インキを２箇所スポットさせた後、室温下３時間放置させた後、薄い洗剤液中で手洗いした印刷「Ｓ字図形」上には、全く青色の油質痕跡や、青色インキの汚染痕跡が見られなかった。以上から布地の印刷「Ｓ字図形」には、耐撥油性及び防汚性が賦与されていることが理解される。 << Printing of the logo mark "S-shaped figure" of Soken Chemical Co., Ltd. >>
Next, this water-based ink composition was overlaid on a 10 cm square polyester fabric with a PET mask film having a thickness of 1 mm obtained by hollowing out an “S-shaped figure” which is a logo mark of Soken Chemical Co., Ltd. This aqueous ink composition was transferred with a brush. Subsequently, it was left to dry in a room temperature atmosphere for 3 hours without hot pressing.
The printability or transferability of the printed “S-shape” was evaluated by the color change evaluation method of the S-shape on the fabric, which was subjected to 10 washing cycles of “hand-washing with laundry detergent” and “room temperature drying”. The washing resistance was evaluated and the results are shown in Table 1.
Also, after printing two spots of commercially available blue oil-based ink on the printed “S-shape” before cycle washing, leaving it at room temperature for 3 hours, and then washing it in a thin detergent solution “S-shaped” On the figure, no blue oily trace or blue ink contamination trace was observed. From the above, it is understood that oil-repellency and antifouling properties are imparted to the printed “S-shape” of the fabric.

（比較例３）
実施例５において、アクリル酸ブチル（ＢＡ）の９０質量部を、メタクリル酸ブチル（ＢＭＡ）の９０質量部に変えて、得られる樹脂成分のとした以外は、実施例１と同様にして「着色ナノマテリアル樹脂成分」調製した。その結果、重合率は約１００％であり、Ｔｇ＝２２℃、平均粒子径が２０ｎｍの超微細ポリマー粒子の「着色ナノマテリアル樹脂成分」が固形分濃度として１２％の水性エマルジョン反応物が得られた。 (Comparative Example 3)
In Example 5, except that 90 parts by mass of butyl acrylate (BA) was changed to 90 parts by mass of butyl methacrylate (BMA) to obtain a resin component, “Coloring” was performed in the same manner as in Example 1. Nanomaterial resin component "was prepared. As a result, an aqueous emulsion reaction product having a polymerization rate of about 100%, Tg = 22 ° C., and “colored nanomaterial resin component” of ultrafine polymer particles having an average particle diameter of 20 nm as a solid content concentration is obtained. It was.

＜＜色調変化評価法による耐洗濯性等の評価法＞＞
実施例５及び比較例３で得られた水性インキ組成物の固形分をそれぞれ６％に調整しポリエステルの布地にそれぞれ転着させて乾燥させた。
・そのまま室温下に充分乾燥したものをブランクとし、
・洗濯用洗剤で手洗いしたもの、必要に応じて、アイロンで加熱したのち洗濯用洗剤で手洗いしたもの、
・「洗濯用洗剤で手洗い」⇔「室温乾燥」洗濯サイクルを１０回サイクルさせたもの、
の色調変化を測定機［カラーエースMODEL TC-PIII(東京電色（株）)により測定し、L*a*b*表色系の値（L*値、a*値、b*値）を求め、ブランクとの色差ΔE*=(ΔL*2+Δa*2+Δb*2)1/2により色落ちから、「印刷性又は転写性」及びその「耐洗濯性」を評価した。
なお、L*値は明度（黒、白）を表し、数値の増加方向は黒方向である。また、a*値及びb*値は色相及び彩度を表すものであり、a*値は赤、緑の指標あって、数値の増加方法は赤方向を示し、b*値は黄、青の指標であり数値の増加方向は黄色を示す。 <<"Evaluation method such as washing resistance by color tone change evaluation method">>
The solid contents of the water-based ink compositions obtained in Example 5 and Comparative Example 3 were adjusted to 6%, respectively, and transferred to a polyester fabric and dried.
・ As a blank that has been sufficiently dried at room temperature,
・ Hand-washed with laundry detergent, if necessary, heated with an iron and then hand-washed with laundry detergent,
-"Hand wash with laundry detergent" ⇔ "room temperature drying" 10 cycles of washing cycle,
The color change of the color is measured with a measuring instrument [Color Ace MODEL TC-PIII (Tokyo Denshoku Co., Ltd.), and the L * a * b * color system values (L * value, a * value, b * value) The color difference from the blank ΔE * = (ΔL * 2 + Δa * 2 + Δb * 2 ) 1/2 was evaluated from the color fading to evaluate “printability or transferability” and its “washing resistance”.
The L * value represents lightness (black, white), and the increasing direction of the numerical value is the black direction. The a * and b * values represent the hue and saturation, the a * value is a red and green index, the increasing method indicates the red direction, and the b * value is yellow and blue. It is an index and the increasing direction of the numerical value is yellow.

Figure 2007009350

表１に示す結果ら、本発明による布地用水性インキ組成物は、ホットプレスすることなく、布地に自己転着性としての優れた印刷又は転写性を呈し、また、その印刷樹脂成分が極めて耐洗濯性を有していることがよく理解される。
Figure 2007009350
The results shown in Table 1 show that the water-based ink composition for fabrics according to the present invention exhibits excellent printing or transferability as a self-transfer property on the fabric without hot pressing, and the printing resin component is extremely resistant. It is well understood that it has washability.

以上から、本発明による布地用水性エマルジョン型樹脂組成物、または、布地用水性インキ組成物は、それぞれ、超微細ポリマー粒子の「ナノマテリアル樹脂成分」及び着色超微細ポリマー粒子の「着色ナノマテリアル樹脂成分」の単独樹脂成分からなる水性エマルジョンであって、布地にホットプレスすることなく、しかも、特にバインダー樹脂成分を用いることなく、自己転着又は自己被覆コート、または、自己印刷又は自己転写させることができることを特徴としている。   From the above, the water-based emulsion-type resin composition for fabrics or the water-based ink composition for fabrics according to the present invention has the “nanomaterial resin component” of ultrafine polymer particles and the “colored nanomaterial resin” of colored ultrafine polymer particles, respectively. A water-based emulsion composed of a single component of “component”, which is self-transferred or self-coated, or self-printed or self-transferred without being hot-pressed on a fabric, and particularly without using a binder resin component. It is characterized by being able to.

以上から、本発明による布地用水性エマルジョン型樹脂組成物及び布地用水性インキ組成物を用いることで、従来の機能性被覆材や、水性インキには不可能であったホットプレスすることなく、各種の天然繊維及び／又は合成繊維からなる織布又は不織布に、様々な機能を賦与させた機能性布地や、様々な図柄及び文字を印刷させた印刷布地を提供することができた。
From the above, by using the water-based emulsion-type resin composition for fabrics and the water-based ink composition for fabrics according to the present invention, various functions can be achieved without hot pressing that has been impossible with conventional functional coating materials and water-based inks. It was possible to provide a functional fabric obtained by imparting various functions to a woven or non-woven fabric made of natural fibers and / or synthetic fibers, and a printed fabric obtained by printing various designs and characters.

Claims (4)

自然乾燥下に布地に自己転着性又は自己被覆コート性を発揮させ且つ転着又は被覆コートされた樹脂成分に、耐洗濯性を有する撥油性や、防汚性等の機能を賦与させる布地用の水性エマルジョン型樹脂組成物であって、
水性媒体中に分散する樹脂成分が、全重合性モノマー成分１００質量％当たり、グリシジル基を有する共重合性モノマー成分が１０〜７０質量％の範囲で共重合させて得られるガラス転移点Ｔｇ≧−５０℃で、且つＴｇ≦１０℃の範囲にあるアクリル系共重合体粒子であり、体積基準で表す平均粒子径が５〜１００ｎｍの超微細ポリマー粒子であるナノマテリアル樹脂成分として、熱圧着を要せずに布地に自己転着性又は自己被覆コート性を発揮させることを特徴とする布地用水性エマルジョン型樹脂組成物。 For fabrics that exhibit self-transferability or self-coating coatability on the fabric under natural drying and impart functions such as washing-resistant oil repellency and antifouling properties to the resin component that has been transferred or coated. An aqueous emulsion resin composition comprising:
The glass transition point Tg ≧ −obtained by copolymerizing the resin component dispersed in the aqueous medium in the range of 10 to 70% by mass of the copolymerizable monomer component having a glycidyl group per 100% by mass of the total polymerizable monomer component. Thermocompression bonding is required as a nanomaterial resin component that is an acrylic copolymer particle in the range of 50 ° C. and Tg ≦ 10 ° C., and is an ultrafine polymer particle having an average particle diameter expressed by volume of 5 to 100 nm. A water-based emulsion-type resin composition for fabrics, wherein the fabric exhibits self-transferability or self-coating coating properties without being applied. 請求項１に記載する布地用水性エマルジョン型樹脂組成物を、被覆コート体である天然繊維、再生繊維、半合成繊維、合成繊維のそれぞれ単独及びこれらの少なくとも２種の複合繊維の群から選ばれる何れかの繊維からなる織布又は不織布に塗布させ、熱圧着を要せずに自己被覆コート性を発揮させて、耐洗濯性を有する撥油性や、防汚性機能が賦与されていることを特徴とする機能性布地。   The aqueous emulsion resin composition for fabrics according to claim 1 is selected from the group consisting of natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers, each of which is a coating coat, and a group of at least two types of these composite fibers. It is applied to a woven or non-woven fabric made of any of the fibers, and self-coating coating properties are exhibited without the need for thermocompression bonding, and oil repellency and antifouling functions having washing resistance are imparted. Characteristic functional fabric. 自然乾燥下に布地に自己転着性又は自己被覆コート性を発揮させ且つ転着又は被覆コートされた樹脂成分に、耐洗濯性を有する撥油性や、防汚性等の機能を賦与させる布地用の水性エマルジョン型樹脂組成物であって、
水性媒体中に分散する樹脂成分が、全重合性モノマー成分１００質量％当たり、グリシジル基を有する共重合性モノマー成分の１０〜７０質量％の範囲で共重合させて得られるガラス転移点Ｔｇ≧−５０℃で、且つＴｇ≦１０℃の範囲にあるアクリル系共重合体粒子であり、体積基準で表す平均粒子径が５〜１００ｎｍの超微細ポリマー粒子であって、更に、油溶性染料０．１〜５０質量％を内包着色する着色ナノマテリアル樹脂成分として、熱圧着を要せずに布地に自己転着性としての印刷性又は転写性を発揮させる前記着色ナノマテリアル樹脂成分に、耐洗濯性を有する撥油性や、防汚性機能を賦与させることを特徴とする布地用水性インキ組成物。 For fabrics that exhibit self-transferability or self-coating coatability on the fabric under natural drying and impart functions such as washing-resistant oil repellency and antifouling properties to the resin component that has been transferred or coated. An aqueous emulsion resin composition comprising:
Glass transition point Tg ≧ −obtained by copolymerizing the resin component dispersed in the aqueous medium in the range of 10 to 70% by mass of the copolymerizable monomer component having a glycidyl group per 100% by mass of the total polymerizable monomer component. Acrylic copolymer particles in the range of 50 ° C. and Tg ≦ 10 ° C., ultrafine polymer particles having an average particle size of 5 to 100 nm on a volume basis, and further comprising an oil-soluble dye 0.1 As a colored nanomaterial resin component that colors up to 50% by mass, the colored nanomaterial resin component that exhibits printability or transferability as a self-transfer property to a fabric without the need for thermocompression bonding is provided with wash resistance. A water-based ink composition for fabrics, which has an oil repellency and an antifouling function. 請求項３に記載する布地用水性インキ組成物を用いて、被印刷体又は被転写体である天然繊維、再生繊維、半合成繊維、合成繊維のそれぞれ単独及びこれらの少なくとも２種の複合繊維の群から選ばれる何れかの繊維からなる織布又は不織布上に、所望する図柄及び／又は文字が印刷又は転写されていることを特徴とする印刷布地。
Using the water-based ink composition for fabric according to claim 3, natural fibers, recycled fibers, semi-synthetic fibers, and synthetic fibers, each of which is a printing body or a transfer body, and at least two kinds of these composite fibers A printed fabric, wherein a desired pattern and / or character is printed or transferred onto a woven or non-woven fabric made of any fiber selected from the group.
JP2005189084A 2005-06-29 2005-06-29 Aqueous emulsion type resin composition for fabric, water-based ink composition used for fabric and using the resin composition and use Pending JP2007009350A (en)

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JP2020023663A (en) * 2018-07-26 2020-02-13 サカタインクス株式会社 Flexographic printing ink composition, ink layer, and printed matter
CN110845925A (en) * 2018-08-20 2020-02-28 天津大学 Silver-containing nano composite antibacterial coating and preparation method thereof
JP2020200543A (en) * 2019-06-07 2020-12-17 セイコーエプソン株式会社 Manufacturing method of fiber molded body and fiber binding treatment liquid
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017538048A (en) * 2014-12-02 2017-12-21 シントマー ドイチェラント ゲゼルシャフト ミット ベシュレンクテル ハフツング Polymer latex composition for fiber bonding
JP2020023663A (en) * 2018-07-26 2020-02-13 サカタインクス株式会社 Flexographic printing ink composition, ink layer, and printed matter
JP7199308B2 (en) 2018-07-26 2023-01-05 サカタインクス株式会社 FLEXOGRAPHIC PRINTING INK COMPOSITION, INK LAYER, AND PRINT
CN110845925A (en) * 2018-08-20 2020-02-28 天津大学 Silver-containing nano composite antibacterial coating and preparation method thereof
JP2020200543A (en) * 2019-06-07 2020-12-17 セイコーエプソン株式会社 Manufacturing method of fiber molded body and fiber binding treatment liquid
WO2022270091A1 (en) * 2021-06-21 2022-12-29 三菱鉛筆株式会社 Antimicrobial particle dispersion

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