JP4696448B2 - Darkening agent, darkening method using the same, and article treated with the darkening agent - Google Patents
Darkening agent, darkening method using the same, and article treated with the darkening agent Download PDFInfo
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- JP4696448B2 JP4696448B2 JP2003427395A JP2003427395A JP4696448B2 JP 4696448 B2 JP4696448 B2 JP 4696448B2 JP 2003427395 A JP2003427395 A JP 2003427395A JP 2003427395 A JP2003427395 A JP 2003427395A JP 4696448 B2 JP4696448 B2 JP 4696448B2
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- Prior art keywords
- darkening
- polymer
- agent
- polymer layer
- aqueous dispersion
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- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-UHFFFAOYSA-N 0.000 description 1
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Coloring (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、紙や繊維、木、プラスティックなどの原材料からなる、例えば、印刷された紙面、染色された繊維製品、着色された木質材料製品、印刷もしくは着色されたプラスティック製品における表面の色の濃さ、深み、鮮明性などの意匠性を向上させる目的で使用する濃色化剤であり、また該濃色化剤を用いたこれら物品の表面の濃色化方法であり、更に該濃色化剤で処理してなる物品に関する。 The present invention is composed of raw materials such as paper, fiber, wood, plastic, etc., for example, printed paper, dyed fiber products, colored wood material products, surface darkness in printed or colored plastic products. A thickening agent used for the purpose of improving design properties such as depth, depth, sharpness, and the like, and a method for darkening the surface of these articles using the thickening agent. The present invention relates to an article processed with an agent.
従来から、繊維製品の濃色化剤及び濃色化方法として、種々のものが提案されてきた。
例えば、ワタ、トウ、スライバ、糸、布帛、フエルトなどのポリエステル系繊維構造物の表面に、屈折率が１．４５以下の含フッ素化合物などの重合体を吸着させて、乾熱又は湿熱処理を行う繊維構造物の発色性改善法（特許文献１。）が提案されている。
しかしながら、かかる方法で用いられる含フッ素化合物は、高価であるため加工コストの増加を招くという問題があった。
Conventionally, various things have been proposed as a darkening agent and a darkening method for a textile product.
For example, a polymer such as a fluorine-containing compound having a refractive index of 1.45 or less is adsorbed on the surface of a polyester fiber structure such as cotton, tow, sliver, yarn, fabric, felt, etc. A method for improving the color developability of a fiber structure (Patent Document 1) has been proposed.
However, since the fluorine-containing compound used in such a method is expensive, there is a problem that the processing cost is increased.
また、繊維製品の濃色化剤として、カチオン性界面活性剤の存在下に、不飽和結合を有する単量体を重合させて得られる水性樹脂組成物からなり、該水性樹脂組成物の乾燥皮膜のガラス転移点が２０〜１１０℃の範囲であり、且つ屈折率が１．５０以下である濃色化剤（特許文献２。）が提案されている。
しかしながら、かかる濃色化剤は、一般に用いられている静電気防止剤と併用し配合液を調整した場合に、調整後の配合液の安定性が極めて劣り、実用性に乏しいという問題があった。
Further, it comprises an aqueous resin composition obtained by polymerizing a monomer having an unsaturated bond in the presence of a cationic surfactant as a darkening agent for textile products, and a dry film of the aqueous resin composition A thickening agent (Patent Document 2) having a glass transition point of 20 to 110 ° C. and a refractive index of 1.50 or less has been proposed.
However, when such a thickening agent is used in combination with a commonly used antistatic agent and the blending solution is adjusted, there is a problem that the stability of the blended solution after adjustment is extremely poor and the practicality is poor.
更に、ポリエステル繊維やポリアミド、アクリル、トリアセテート、レーヨン、絹、木綿、羊毛等の繊維に用いる濃色化剤であり、カチオン性界面活性剤の存在下に、エチレン性不飽和単量体を重合させて得られる重合体の水性分散体からなり、該重合体が屈折率１．５０以下で且つガラス転移点が１１０℃を越える重合体と、屈折率１．５０以下で且つガラス転移点が２０℃未満の重合体とからなる濃色化剤（特許文献３。）が提案されている。
しかしながら、かかる濃色化剤においても前記のものと同様に、一般に用いられている静電気防止剤と併用し配合液を調整した場合に、調整後の配合液の安定性が極めて劣り、実用性に乏しいという問題があった。
Furthermore, it is a thickening agent used for fibers such as polyester fiber, polyamide, acrylic, triacetate, rayon, silk, cotton, wool, etc., and polymerizes an ethylenically unsaturated monomer in the presence of a cationic surfactant. A polymer having a refractive index of 1.50 or less and a glass transition point exceeding 110 ° C, and a refractive index of 1.50 or less and a glass transition point of 20 ° C. A darkening agent (Patent Document 3) composed of less than a polymer has been proposed.
However, in the case of such a darkening agent, as in the case described above, when the blending liquid is adjusted in combination with a commonly used antistatic agent, the stability of the blended liquid after adjustment is extremely poor and practical. There was a problem of being scarce.
特に、合成繊維の濃色化加工の場合、繊維の帯電による工程トラブルを防ぐ目的で濃色化剤に静電気防止剤を配合し、濃色化加工と同時に制電加工を行う方法が広く普及している。
従来から行われていたカチオン性重合体エマルジョンに、高級アルコールポリオキシエチレンエーテルのような非イオン性の静電気防止剤や第四級アンモニウム塩のようなカチオン性静電気防止剤を配合する濃色化方法では、濃色化効果が著しく低下してしまうという問題がある。
一方、酸性リン酸エステル塩のようなアニオン性の静電気防止剤を配合する濃色化方法の場合は、配合後数十分でカチオン性重合体エマルジョンが凝集するため、配合液の安定性の点で致命的問題を有していた。
In particular, in the case of darkening processing of synthetic fibers, a method of adding antistatic agent to the darkening agent for the purpose of preventing process troubles due to fiber charging, and performing antistatic processing simultaneously with darkening processing has become widespread. ing.
A method of darkening a conventional cationic polymer emulsion with a nonionic antistatic agent such as higher alcohol polyoxyethylene ether or a cationic antistatic agent such as a quaternary ammonium salt. Then, there exists a problem that the darkening effect will fall remarkably.
On the other hand, in the case of a darkening method in which an anionic antistatic agent such as an acidic phosphate ester salt is blended, the cationic polymer emulsion aggregates several tens of minutes after blending. Had a fatal problem.
本発明の目的は、紙や繊維、木、プラスティックなどの原材料からなる、例えば、印刷された紙面、染色された繊維製品、着色された木質材料製品、印刷もしくは着色されたプラスティック製品における表面の色の濃さ、深み、鮮明性などの意匠性を向上させ、且つ優れた制電性と耐擦過性を付与できる濃色化剤であり、また該濃色化剤を用いたこれら物品の表面の濃色化方法であり、更に該濃色化剤で処理してなる物品を提供することである。 The object of the invention consists of raw materials such as paper, fiber, wood, plastic, etc., for example, the color of the surface in printed paper, dyed textiles, colored wood products, printed or colored plastic products It is a thickening agent that can improve design properties such as darkness, depth, and sharpness, and can impart excellent antistatic properties and scratch resistance, and the surface of these articles using the thickening agent. It is a darkening method, and further provides an article processed with the darkening agent.
本発明者等は、上記課題を解決すべく鋭意研究を重ねた結果、カチオン性界面活性剤の存在下で、特定のエチレン性不飽和単量体をラジカル重合性させて得られる屈折率が１．５０以下の重合体粒子含有水分散体と、両性界面活性剤、及びアニオン性静電気防止剤からなる濃色化剤において、前記濃色化剤が前記カチオン性界面活性剤を前記重合体粒子に対し、特定の範囲内で含有することにより、上記課題が解決されることを見出し、本発明を完成するに至った。
また、カチオン性界面活性剤の存在下で、特定のエチレン性不飽和単量体をラジカル重合性させて得られる屈折率が１．５０以下の重合体粒子含有水分散体と、両性界面活性剤、アニオン性静電気防止剤、及びシリコーンエマルジョンからなる濃色化剤において、前記濃色化剤が前記カチオン性界面活性剤を前記重合体粒子に対し、特定の範囲内で含有することにより、上記課題が解決されることを見出し、本発明を完成するに至った。
As a result of intensive studies to solve the above problems, the present inventors have obtained a refractive index of 1 obtained by radical polymerization of a specific ethylenically unsaturated monomer in the presence of a cationic surfactant. A thickening agent comprising an aqueous dispersion containing 50 or less polymer particles, an amphoteric surfactant, and an anionic antistatic agent, wherein the thickening agent converts the cationic surfactant into the polymer particles. On the other hand, it has been found that the above-mentioned problems can be solved by containing within a specific range, and the present invention has been completed.
Further, a polymer particle-containing aqueous dispersion having a refractive index of 1.50 or less obtained by radical polymerization of a specific ethylenically unsaturated monomer in the presence of a cationic surfactant, and an amphoteric surfactant In the thickening agent comprising an anionic antistatic agent and a silicone emulsion, the darkening agent contains the cationic surfactant in a specific range with respect to the polymer particles. Has been found to be solved, and the present invention has been completed.
即ち、本発明は、カチオン性界面活性剤の存在下に、エチレン性不飽和単量体をラジカル重合させて得られる屈折率が１．５０以下の重合体粒子含有水分散体（Ａ）、両性界面活性剤（Ｂ）、アニオン性静電気防止剤（Ｃ）、及びシリコーンエマルジョン（Ｄ）からなる濃色化剤であり、前記重合体粒子が、少なくとも、ガラス転移温度が１１０℃以上である重合体層（Ａ−１）、及びガラス転移温度が−２０〜２０℃の範囲である重合体層（Ａ−２）から構成されるものであり、前記両性界面活性剤（Ｂ）がラウリルジメチルアミノ酢酸ベタインであり、前記両性界面活性剤（Ｂ）の含有量が前記重合体粒子の１〜５０重量％未満であり、前記シリコーンエマルジョン（Ｄ）が重合体粒子１００重量部に対して１〜５０重量部であり、かつ前記濃色化剤が前記カチオン性界面活性剤を前記重合体粒子に対して、０．１〜０．５重量％の範囲で含有することを特徴とする濃色化剤を提供するものである。 That is, the present invention provides a polymer particle-containing aqueous dispersion (A) having a refractive index of 1.50 or less obtained by radical polymerization of an ethylenically unsaturated monomer in the presence of a cationic surfactant. A thickening agent comprising a surfactant (B), an anionic antistatic agent (C), and a silicone emulsion (D), wherein the polymer particles have a glass transition temperature of at least 110 ° C. A layer (A-1) and a polymer layer (A-2) having a glass transition temperature in the range of −20 to 20 ° C., and the amphoteric surfactant (B) is lauryldimethylaminoacetic acid It is betaine, the content of the amphoteric surfactant (B) is less than 1 to 50% by weight of the polymer particles, and the silicone emulsion (D) is 1 to 50% by weight with respect to 100 parts by weight of the polymer particles. And The darkening agent contains the cationic surfactant in a range of 0.1 to 0.5% by weight with respect to the polymer particles. .
また、本発明は、請求項１〜４の何れかに記載の濃色化剤を用いて、濃色化加工された繊維製品を提供するものである。
Moreover, this invention provides the textiles darkened using the darkening agent in any one of Claims 1-4 .
本発明の濃色化剤は、紙、繊維、木、又はプラスティックなどの原材料からなる、例えば、印刷された紙面、染色された繊維製品、着色された木質材料製品、印刷もしくは着色されたプラスティック製品などの物品における、表面の色の濃さ、深み、鮮明性などの意匠性を向上させ、且つ優れた制電性と耐擦過性を付与することができる。
また、本発明の濃色化方法は、前記本発明の濃色化剤を用いた前記物品の表面の濃色化方法であり、また、本発明の濃色化剤にて処理してなる物品を提供するものであり、本発明の物品は、表面の色の濃さ、深み、鮮明性、質感などの意匠性に優れる。
The darkening agent of the present invention consists of raw materials such as paper, fiber, wood or plastic, for example, printed paper, dyed fiber products, colored wood material products, printed or colored plastic products In such articles, the surface color depth, depth, and sharpness can be improved, and excellent antistatic properties and scratch resistance can be imparted.
Further, the darkening method of the present invention is a method of darkening the surface of the article using the darkening agent of the present invention, and an article processed by the darkening agent of the present invention. The article of the present invention is excellent in design properties such as surface darkness, depth, clarity and texture.
本発明を実施するにあたり、必要な事項を以下に述べる。
先ず、本発明の濃色化剤とは、カチオン性界面活性剤の存在下に、エチレン性不飽和単量体をラジカル重合性させて得られる屈折率が１．５０以下の重合体粒子含有水分散体（Ａ）と、両性界面活性剤（Ｂ）、及びアニオン性静電気防止剤（Ｃ）とからなる濃色化剤であり、前記濃色化剤が前記カチオン性界面活性剤を前記重合体粒子に対して、０．１〜０．５重量％の範囲で含有することを特徴とする。
The matters necessary for carrying out the present invention are described below.
First, the thickening agent of the present invention is a polymer particle-containing water having a refractive index of 1.50 or less obtained by radical polymerization of an ethylenically unsaturated monomer in the presence of a cationic surfactant. A thickening agent comprising a dispersion (A), an amphoteric surfactant (B), and an anionic antistatic agent (C), wherein the thickening agent converts the cationic surfactant into the polymer. It is characterized by containing in the range of 0.1 to 0.5% by weight with respect to the particles.
また、本発明の濃色化剤は、カチオン性界面活性剤の存在下に、エチレン性不飽和単量体をラジカル重合性させて得られる屈折率が１．５０以下の重合体粒子含有水分散体（Ａ）と、両性界面活性剤（Ｂ）と、アニオン性静電気防止剤（Ｃ）、及びシリコーンエマルジョン（Ｄ）とからなる濃色化剤であり、前記濃色化剤が前記カチオン性界面活性剤を前記重合体粒子に対して、０．１〜０．５重量％の範囲で含有することを特徴とする。 Further, the thickening agent of the present invention is a polymer particle-containing water dispersion having a refractive index of 1.50 or less obtained by radical polymerization of an ethylenically unsaturated monomer in the presence of a cationic surfactant. A thickening agent comprising a body (A), an amphoteric surfactant (B), an anionic antistatic agent (C), and a silicone emulsion (D), wherein the thickening agent is the cationic interface. An activator is contained in the range of 0.1 to 0.5% by weight with respect to the polymer particles.
本発明の濃色化剤において、必須成分の一つである前記重合体粒子含有水分散体（Ａ）とは、ガラス転移温度（Ｔｇ）が異なる少なくとも２種の重合体層、即ち重合体層（Ａ−１）と重合体層（Ａ−２）から構成されており、特にその層構造を特定するものではないが、通常、重合体層（Ａ−２）をマトリックスとし、重合体層（Ａ−１）が前記マトリックスである重合体層（Ａ−２）内に１つの塊状となり存在し、或いは多数に分散し存在し、また或いは重合体層（Ａ−１）を形成する粒子と重合体層（Ａ−２）を形成する粒子がそれぞれ独立して存在するものである。 In the darkening agent of the present invention, the polymer particle-containing aqueous dispersion (A), which is one of the essential components, is at least two polymer layers having different glass transition temperatures (Tg), that is, polymer layers. (A-1) and a polymer layer (A-2), and the layer structure is not particularly specified. Usually, the polymer layer (A-2) is used as a matrix, and the polymer layer ( A-1) is present in the polymer layer (A-2) which is the matrix as one lump, or dispersed in a large number, or alternatively the particles and the particles forming the polymer layer (A-1). The particles forming the combined layer (A-2) are each independently present.
更に具体的に、重合体層（Ａ−１）と重合体層（Ａ−２）について説明すると、例えば、次のような構造が例示できる。即ち、
〔ａ〕重合体層（Ａ−１）をコアとし、重合体層（Ａ−２）をシェルとする「コア−シェル構造」、或いは、
〔ｂ〕重合体層（Ａ−１）が重合体層（Ａ−２）中に多数に分散しており、重合体層（Ａ−２）が重合体層（Ａ−１）を完全に又は不完全にカプセル化している構造、或いは、
〔ｃ〕重合体層（Ａ−１）と重合体層（Ａ−２）の重合体が多数の不連続なドメインを形成する相互貫入網目構造などの不均質な構造、或いは、
〔ｄ〕重合体層（Ａ−２）が水性媒体中に溶解ないしは非粒子状態で分散しており、重合体層（Ａ−１）が重合体層（Ａ−２）をマトリックスとして粒子状に分散している状態、或いは、
〔ｅ〕重合体層（Ａ−１）と重合体層（Ａ−２）がそれぞれ独立した粒子を形成している状態、など種々の構造が挙げられる。
More specifically, when the polymer layer (A-1) and the polymer layer (A-2) are described, for example, the following structures can be exemplified. That is,
[A] "core-shell structure" having the polymer layer (A-1) as a core and the polymer layer (A-2) as a shell, or
[B] The polymer layer (A-1) is dispersed in a large number in the polymer layer (A-2), and the polymer layer (A-2) completely or completely disperses the polymer layer (A-1). Incompletely encapsulated structure, or
[C] a heterogeneous structure such as an interpenetrating network in which the polymers of the polymer layer (A-1) and the polymer layer (A-2) form a number of discontinuous domains, or
[D] The polymer layer (A-2) is dissolved or dispersed in a non-particulate state in the aqueous medium, and the polymer layer (A-1) is in the form of particles using the polymer layer (A-2) as a matrix. In a distributed state, or
[E] Various structures such as a state in which the polymer layer (A-1) and the polymer layer (A-2) form independent particles are exemplified.
前記重合体粒子含有水分散体（Ａ）を構成する重合体層（Ａ−１）のＴｇは１１０℃以上が好ましく、且つ重合体層（Ａ−２）のＴｇは−２０〜２０℃の範囲であることが好ましい。
前記重合体粒子含有水分散体（Ａ）を構成する重合体層（Ａ−１）と重合体層（Ａ−２）のＴｇがかかる範囲であれば、耐擦過性に優れる濃色化剤が得られる。
The polymer layer (A-1) constituting the polymer particle-containing aqueous dispersion (A) preferably has a Tg of 110 ° C. or higher, and the polymer layer (A-2) has a Tg of −20 to 20 ° C. It is preferable that
If the Tg of the polymer layer (A-1) and the polymer layer (A-2) constituting the polymer particle-containing aqueous dispersion (A) is within such a range, a thickening agent having excellent scratch resistance is obtained. can get.
また、本発明の濃色化剤に使用する重合体粒子の水分散体（Ａ）を構成する重合体層（Ａ−１）及び重合体層（Ａ−２）は、Ｔｇが１１０℃以上の重合体層（Ａ−１）とＴｇが−２０〜２０℃の範囲の重合体層（Ａ−２）との混合物が好ましい。 In addition, the polymer layer (A-1) and the polymer layer (A-2) constituting the aqueous dispersion (A) of polymer particles used in the darkening agent of the present invention have a Tg of 110 ° C. or higher. A mixture of the polymer layer (A-1) and the polymer layer (A-2) having a Tg in the range of -20 to 20 ° C is preferred.
本発明の濃色化剤においては、エチレン性不飽和単量体をラジカル重合させて得られる重合体が、１．５０以下の屈折率を有し、且つ特定の範囲のＴｇを有することが、濃色化に重要であり、特にＴｇの異なる少なくとも２種の重合体を使用することにより、優れた濃色化性に加えて、更に耐擦過性をも得られることから、従来の濃色化剤では得られなかった濃色化効果の持続性を高めるという効果を得ることが可能となる。 In the darkening agent of the present invention, the polymer obtained by radical polymerization of an ethylenically unsaturated monomer has a refractive index of 1.50 or less and a specific range of Tg. It is important for darkening, and in particular, by using at least two polymers having different Tg, in addition to excellent darkening properties, scratch resistance can also be obtained. It is possible to obtain an effect of enhancing the sustainability of the darkening effect that could not be obtained with the agent.
本発明の濃色化剤の製造に使用する各原料について、以下に詳細に述べる。
第一に、本発明の濃色化剤に使用する重合体層（Ａ−１）及び重合体層（Ａ−２）に使用するエチレン性不飽和単量体（ａ−１）として、以下如き化合物が例示できる。即ち、
ＣＨ２＝ＣＨＣＯＯＣＨ２Ｃ３Ｆ７
ＣＦ３(ＣＦ２)６ＣＯＯＣＨ＝ＣＨ２
ＣＨ２＝ＣＨＯＣＨ２Ｃ２Ｆ５、
などで表されるフッ素含有エチレン性不飽和単量体、あるいは２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３，３−ペンタフルオロプロピル（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート、２，２，３，３−テトラフルオロプロピル（メタ）アクリレート、β−（パーフルオロオクチル）エチル（メタ）アクリレート等のフッ素含有エチレン性不飽和単量体、メチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、エチル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、ドデシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、等の（メタ）アクリル酸エステル類、ビニルアセテート、ビニルプロピオネート、ビニル−２−エチルヘキシルエーテル、ビニルヘキシルエーテル、ビニルエチルエーテル等のビニルエステル、ビニルエーテル化合物、（メタ）アクリロニトリル等の不飽和カルボン酸のニトリル類；イソプレン、クロロプレン、ブタジエン、エチレン、テトラフルオロエチレン、フッ化ビニリデン、Ｎ−ビニルピロリドン等が挙げられる。これらの群から選択される１種または２種以上の単量体が使用される。
Each raw material used for production of the darkening agent of the present invention will be described in detail below.
First, as the ethylenically unsaturated monomer (a-1) used for the polymer layer (A-1) and the polymer layer (A-2) used in the darkening agent of the present invention, A compound can be illustrated. That is,
CH 2 = CHCOOCH 2 C 3 F 7
CF 3 (CF 2 ) 6 COOCH═CH 2
CH 2 = CHOCH 2 C 2 F 5 ,
Fluorine-containing ethylenically unsaturated monomer or 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, perfluoro Fluorine-containing ethylenically unsaturated monomers such as cyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate, methyl (meth) Acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexadecyl (meth) acrylate, ethyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl ( (Meth) acrylate, 2-ethylhexyl ( ) Acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) acrylates, vinyl acetate, Vinyl esters such as vinyl propionate, vinyl-2-ethylhexyl ether, vinyl hexyl ether, vinyl ethyl ether, nitriles of unsaturated carboxylic acids such as vinyl ether compounds, (meth) acrylonitrile; isoprene, chloroprene, butadiene, ethylene, tetra Fluoroethylene, vinylidene fluoride, N-vinylpyrrolidone and the like can be mentioned. One or more monomers selected from these groups are used.
第二に、本発明の濃色化剤に使用する重合体層（Ａ−１）及び重合体層（Ａ−２）に使用する官能基を有するエチレン性不飽和単量体（ａ−２）としては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、グリセロールモノ（メタ）アクリレート等の水酸基含有重合性単量体；Ｎ−メチロール（メタ）アクリルアミド、Ｎ−イソプロポキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ−イソブトキシメチル（メタ）アクリルアミド等のメチロールアミド基及びそのアルコキシ化物含有重合性単量体；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等のグリシジル基含有重合性単量体；アミノエチル（メタ）アクリレート、Ｎ−モノアルキルアミノアルキル（メタ）アクリレート、Ｎ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレート等のアミノ基含有重合性単量体；ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン、γ−（メタ）アクリロキシプロピルトリイソプロポキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン及びその塩酸塩、２−（３、４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン等のシリル基含有重合性単量体；２−アジリジニルエチル（メタ）アクリレート等のアジリジニル基含有重合性単量体；２−イソプロペニル−２−オキサゾリン、２−ビニル−２−オキサゾリン等のオキサゾリン基含有重合性単量体；（メタ）アクリルアミド、Ｎ−モノアルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミド等のアミド基含有重合性単量体；ジシクロペンテニル（メタ）アクリレート等のシクロペンテニル基含有重合性単量体；アクロレイン、ジアセトン（メタ）アクリルアミド等のカルボニル基含有重合性単量体；アセトアセトキシエチルアクリレート、アセトアセトキシエチルメタクリレート、アセトアセトキシエチルクロトナート、アセトアセトキシプロピルアクリレート、アセトアセトキシプロピルメタクリレート、アセトアセトキシプロピルクロトナート、２−シアノアセトアセトキシエチルメタクリレート、Ｎ−（２−アセトアセトキシエチル）アクリルアミド、Ｎ−（２−アセトアセトキシエチル）メタクリルアミド、アセト酢酸アリル、アセト酢酸ビニルなどのアセトアセチル基含有エチレン性不飽和単量体；（メタ）アクリロイルイソシアナート、（メタ）アクリロイルイソシアナートエチルのフェノール或いはメチルエチルケトオキシム付加物等のイソシアナート基及び／またはブロック化イソシアナート基含有重合性単量体等が挙げられる。これらの群から選択される１種または２種以上の単量体が使用される。 Second, the ethylenically unsaturated monomer (a-2) having a functional group used in the polymer layer (A-1) and the polymer layer (A-2) used in the darkening agent of the present invention. Examples thereof include hydroxyl group-containing polymerizable monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and glycerol mono (meth) acrylate; N-methylol Methylolamide groups such as (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, and alkoxylated-containing polymerizable monomers thereof; glycidyl Glycidyl group-containing polymerizable monomer such as (meth) acrylate and allyl glycidyl ether Amino group-containing polymerizable monomers such as aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate and N, N-dialkylaminoalkyl (meth) acrylate; vinyltrichlorosilane, vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and its hydrochloride , 2- (3, -Epoxycyclohexyl) silyl group-containing polymerizable monomer such as ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; Aziridinyl group-containing polymerizable monomers such as 2-aziridinylethyl (meth) acrylate; oxazoline group-containing polymerizable monomers such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline; ) Amide group-containing polymerizable monomers such as acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide; Cyclopentenyl group-containing polymerizable monomers such as dicyclopentenyl (meth) acrylate ; Carbos such as acrolein and diacetone (meth) acrylamide Group-containing polymerizable monomers: acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl crotonate, acetoacetoxypropyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxypropyl crotonate, 2-cyanoacetoacetoxyethyl methacrylate, N -(2-acetoacetoxyethyl) acrylamide, N- (2-acetoacetoxyethyl) methacrylamide, acetoacetyl group-containing ethylenically unsaturated monomers such as allyl acetoacetate and vinyl acetoacetate; (meth) acryloyl isocyanate, Contains isocyanate groups such as phenol or methyl ethyl ketoxime adducts of (meth) acryloyl isocyanate ethyl and / or blocked isocyanate groups Examples thereof include a polymerizable monomer. One or more monomers selected from these groups are used.
本発明の濃色化剤で、重合体粒子含有水分散体（Ａ）において、重合体層（Ａ−１）及び重合体層（Ａ−２）に用いるエチレン性不飽和単量体（ａ−１）及び官能基を有するエチレン性不飽和単量体（ａ−２）との使用割合は、（ａ−１）／（ａ−２）＝６５〜９９．９／０．１〜３５重量％の範囲が好ましい。エチレン性不飽和単量体（ａ−１）及び官能基を有するエチレン性不飽和単量体（ａ−２）との使用割合がかかる範囲であれば、濃色化効果の耐擦過性に優れる濃色化剤が得られる。 In the darkening agent of the present invention, the ethylenically unsaturated monomer (a-) used in the polymer layer (A-1) and the polymer layer (A-2) in the polymer particle-containing aqueous dispersion (A). 1) and the ratio of use with the ethylenically unsaturated monomer (a-2) having a functional group is (a-1) / (a-2) = 65 to 99.9 / 0.1 to 35% by weight The range of is preferable. If the ratio of use with the ethylenically unsaturated monomer (a-1) and the ethylenically unsaturated monomer (a-2) having a functional group is within such a range, the scratch resistance of the darkening effect is excellent. A darkening agent is obtained.
本発明の濃色化剤で用いる、カチオン性界面活性剤の存在下に、エチレン性不飽和単量体をラジカル重合させて得られる屈折率が１．５０以下の重合体粒子含有水分散体（Ａ）は、公知慣用の方法で製造することができ、特に限定しない。
かかる製造法としては、例えば、均質重合体を水性媒体中で製造する方法としては、
〔ａ〕水、重合性単量体混合物、重合開始剤、（必要に応じて乳化剤及び／又は分散安定剤などを用いてもよい。）を一括混合して重合する方法、或いは、
〔ｂ〕水、重合性単量体、乳化剤を予め混合したものを滴下する所謂プレエマルジョン法、或いは、
〔ｃ〕モノマー滴下法等、種々の方法により製造することができ、
また、不均質重合体を水性媒体中で製造する方法としては、
〔ｄ〕前記製造方法等により重合体層（Ａ−１）と重合体層（Ａ−２）とを別々に製造し、これらを一旦混合した後に水性媒体中に分散させて重合体粒子含有水分散体（Ａ）を得る方法、或いは、
〔ｅ〕重合体層（Ａ−１）を製造し、これを水性媒体中に溶解、或いは分散させた後、該水性媒体中で重合体層（Ａ−２）を製造して重合体粒子含有水分散体（Ａ）を得る方法、或いは、
〔ｆ〕重合体層（Ａ−２）を製造し、これを水性媒体中に溶解、或いは分散させた後、該水性媒体中で重合体層（Ａ−１）を製造して重合体粒子含有水分散体（Ａ）を得る方法などが挙げられる。
Polymer particle-containing aqueous dispersion having a refractive index of 1.50 or less obtained by radical polymerization of an ethylenically unsaturated monomer in the presence of a cationic surfactant used in the darkening agent of the present invention ( A) can be produced by a known and commonly used method and is not particularly limited.
As such a production method, for example, as a method for producing a homogeneous polymer in an aqueous medium,
[A] A method in which water, a polymerizable monomer mixture, a polymerization initiator, and (if necessary, an emulsifier and / or a dispersion stabilizer, etc. may be used) are mixed and polymerized, or
[B] a so-called pre-emulsion method in which water, a polymerizable monomer, and an emulsifier previously mixed are dropped, or
[C] It can be produced by various methods such as a monomer dropping method,
As a method for producing a heterogeneous polymer in an aqueous medium,
[D] The polymer layer (A-1) and the polymer layer (A-2) are produced separately by the production method described above, and after mixing these, the polymer layer-containing water is dispersed in an aqueous medium. A method of obtaining the dispersion (A), or
[E] A polymer layer (A-1) is produced and dissolved or dispersed in an aqueous medium, and then the polymer layer (A-2) is produced in the aqueous medium to contain polymer particles. A method for obtaining an aqueous dispersion (A), or
[F] A polymer layer (A-2) is produced and dissolved or dispersed in an aqueous medium, and then the polymer layer (A-1) is produced in the aqueous medium to contain polymer particles. Examples thereof include a method for obtaining an aqueous dispersion (A).
本発明の濃色化剤に使用する重合体粒子含有水分散体（Ａ）に使用されるカチオン性界面活性剤は、特に限定されるものではなく、公知慣用のものが何れも使用可能であるが、特に代表的なカチオン性界面活性剤を例示すると以下のようなものが挙げられる。 The cationic surfactant used in the polymer particle-containing aqueous dispersion (A) used for the darkening agent of the present invention is not particularly limited, and any known and conventional one can be used. However, examples of typical cationic surfactants include the following.
前記カチオン性界面活性剤としては、例えば、アルキル第４級アンモニウム塩、 Examples of the cationic surfactant include alkyl quaternary ammonium salts,
或いはアルキル基の一部がエステル結合、アミド結合を含む一価有機基によって置換された第４級アンモニウム塩、 Alternatively, a quaternary ammonium salt in which a part of the alkyl group is substituted with a monovalent organic group containing an ester bond or an amide bond,
或いはアルキルヒドロキシエチル第４級アンモニウム塩、 Or alkylhydroxyethyl quaternary ammonium salt,
或いはアルキルベンジル第４級アンモニウム塩、 Or alkylbenzyl quaternary ammonium salt,
或いはアルキルピリジニウム塩、 Or alkylpyridinium salt,
或いはアルキルイミダゾリニウム塩、 Or alkyl imidazolinium salt,
或いはアルキルモルホリニウム塩、 Or an alkylmorpholinium salt,
或いは１級アミン塩、 Or primary amine salt,
或いは２級アミン塩、 Or secondary amine salt,
或いは３級アミン塩として、 Or as a tertiary amine salt,
及び、 as well as,
及び、 as well as,
及び、 as well as,
の如き、カチオン性基含有エチレン性不飽和単量体を挙げることができる。
尚、上記一連の一般式において、Ｒ１、Ｒ２、Ｒ３、及びＲ４は炭素数１〜２２の範囲のアルキル基、Ｒ５は炭素数１〜２２の範囲のアルキレン基であり、ＯＨ基を有していてもよく、例えば−ＣＨ２−ＣＨ（ＯＨ）−ＣＨ２−や−ＣＨ２−ＣＨ２−ＣＨ（ＯＨ）−ＣＨ２−などが挙げられ、ＸはＣｌ、Ｂｒ、Ｉ、ＣＨ３ＳＯ４、Ｃ２Ｈ５ＳＯ４、ＮＯ３、ＣｌＯ４、ＨＯＣＨ２ＣＯＯ等の一価の陰イオン性基を表す。
Examples thereof include cationic group-containing ethylenically unsaturated monomers.
In the above series of general formulas, R 1 , R 2 , R 3 , and R 4 are alkyl groups having 1 to 22 carbon atoms, R 5 is an alkylene group having 1 to 22 carbon atoms, and OH Group may be included, for example, —CH 2 —CH (OH) —CH 2 —, —CH 2 —CH 2 —CH (OH) —CH 2 —, etc., and X is Cl, Br, I Represents a monovalent anionic group such as CH 3 SO 4 , C 2 H 5 SO 4 , NO 3 , ClO 4 , or HOCH 2 COO.
本発明の濃色化剤に使用する重合体粒子の水分散体（Ａ）は、水中での分散安定性を高める等の目的で、必要に応じて非イオン性界面活性剤を併用することができる。かかる非イオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンアルキルアミンエーテル、脂肪酸ジエタノールアマイド、蔗糖エステル、ポリオキシエチレンラノリンアルコールエーテル、ポリオキシエチレンラノリン脂肪酸エステル等が挙げられる。 The aqueous dispersion (A) of polymer particles used in the darkening agent of the present invention may be used in combination with a nonionic surfactant as necessary for the purpose of enhancing dispersion stability in water. it can. Examples of such nonionic surfactants include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester. , Polyoxyethylene alkylamine ether, fatty acid diethanolamide, sucrose ester, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester and the like.
前記重合体粒子含有水分散体（Ａ）に用いるカチオン性界面活性剤の重合体粒子に対する使用比率は、重合体粒子の重量に対して、０．１〜０．５重量％の範囲が好ましい。重合体粒子の水分散体（Ａ）に用いるカチオン性界面活性剤の重合体粒子に対する使用比率がかかる範囲であれば、濃色効果と安定性に優れた濃色化剤が得られる。 The ratio of the cationic surfactant used in the polymer particle-containing aqueous dispersion (A) to the polymer particles is preferably in the range of 0.1 to 0.5% by weight based on the weight of the polymer particles. If the ratio of the cationic surfactant used in the aqueous dispersion (A) of the polymer particles to the polymer particles is within such a range, a darkening agent having excellent darkening effect and stability can be obtained.
前記重合体粒子含有水分散体（Ａ）の重合開始源は、特に制限しないが、例えば、アゾ化合物、有機過酸化物の如き各種重合開始剤、更には、紫外線あるいはγ線などの電離性放射線などが採用され得る。
フロック或いは沈殿物のない安定な水分散体を得るためには、重合開始源として、例えば、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二塩酸塩等の水溶性アゾ化合物を使用することが好ましい。
The polymerization initiation source of the polymer particle-containing aqueous dispersion (A) is not particularly limited. For example, various polymerization initiators such as azo compounds and organic peroxides, and further ionizing radiation such as ultraviolet rays or γ rays. Etc. may be employed.
In order to obtain a stable aqueous dispersion free from flocs or precipitates, for example, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- ( It is preferable to use water-soluble azo compounds such as 2-imidazolin-2-yl) propane] dihydrochloride.
本発明の濃色化剤に使用する重合体粒子含有水分散体（Ａ）を構成する重合体粒子の屈折率は、１．５０以下であることが好ましく、前記重合体粒子の屈折率がかかる範囲であれば濃色化効果に優れる濃色化剤を得ることができる。 The refractive index of the polymer particles constituting the polymer particle-containing aqueous dispersion (A) used for the darkening agent of the present invention is preferably 1.50 or less, and the refractive index of the polymer particles is applied. If it is in the range, a darkening agent having an excellent darkening effect can be obtained.
本発明において得られる重合体粒子の屈折率は、下記の計算式により推定値として求めることができる。
［重合体の屈折率の計算式］
ｎ＝Σ〔Ｗ（ｉ）ｎ（ｉ）〕
式中、Ｗ（ｉ）は「重合体粒子を構成する単量体（ｉ）の重量分率」を表し、ｎ（ｉ）は「重合体粒子を構成する単量体（ｉ）の単独重合体の屈折率」を表す。
The refractive index of the polymer particles obtained in the present invention can be obtained as an estimated value by the following calculation formula.
[Calculation formula for refractive index of polymer]
n = Σ [W (i) n (i)]
In the formula, W (i) represents “weight fraction of monomer (i) constituting polymer particles”, and n (i) represents “single weight of monomer (i) constituting polymer particles”. Represents the combined refractive index.
また、本発明でいう重合体粒子のガラス転移温度（Ｔｇ）は、示差熱分析法（ＤＳＣ法）により実測できる。 Further, the glass transition temperature (Tg) of the polymer particles referred to in the present invention can be measured by a differential thermal analysis method (DSC method).
本発明の濃色化剤において、Ｔｇが１１０℃以上の重合体層（Ａ−１）とＴｇが２０〜−２０℃の範囲である重合体層（Ａ−２）との使用比率は、特に制限はないが、固形分重量比で、（Ａ−１）／（Ａ−２）＝５／９５〜９０／１０の範囲が好ましく、１０／９０〜９０／１０の範囲がより好ましい。濃色化剤における重合体層（Ａ−１）と重合体層（Ａ−２）との使用比率がかかる範囲であれば、優れた濃色化効果と耐擦過性を発現できる。 In the darkening agent of the present invention, the use ratio of the polymer layer (A-1) having a Tg of 110 ° C. or more and the polymer layer (A-2) having a Tg in the range of 20 to −20 ° C. is particularly Although there is no restriction | limiting, The range of (A-1) / (A-2) = 5 / 95-90 / 10 is preferable at solid content weight ratio, and the range of 10 / 90-90 / 10 is more preferable. If the use ratio of the polymer layer (A-1) and the polymer layer (A-2) in the darkening agent is within such a range, an excellent darkening effect and scratch resistance can be expressed.
次に、本発明の濃色化剤の第２の必須成分である両性界面活性剤（Ｂ）としては、例えば、アルキルジメチルアミノ酢酸ベタイン、アルキルイミダゾリニウム酢酸ベタイン、アルキルアミノカルボン酸等が挙げられる。 Next, examples of the amphoteric surfactant (B) that is the second essential component of the darkening agent of the present invention include alkyldimethylaminoacetic acid betaine, alkylimidazolinium acetate betaine, and alkylaminocarboxylic acid. It is done.
本発明の濃色化剤において、重合体粒子含有水分散体（Ａ）と両性界面活性剤（Ｂ）との使用割合は、固形分重量比で、両性界面活性剤（Ｂ）を重合体粒子含有水分散体（Ａ）に対して、１〜５０重量％の範囲（即ち（Ａ）／（Ｂ）＝１００／１〜５０固形分重量比）であることが好ましい。重合体粒子の水分散体（Ａ）と両性界面活性剤（Ｂ）との使用割合がかかる範囲であれば、（Ａ）〜（Ｄ）の各成分からなる濃色化加工用組成物の混和安定性に優れ、且つ加工工程での泡立ち抑制効果、埃付着防止効果、加工効果の耐久性などに優れる。 In the thickening agent of the present invention, the proportion of the polymer particle-containing aqueous dispersion (A) and the amphoteric surfactant (B) used is a solid weight ratio, and the amphoteric surfactant (B) is polymer particles. It is preferable that it is the range of 1-50 weight% (namely, (A) / (B) = 100 / 1-50 solid content weight ratio) with respect to a containing water dispersion (A). If the use ratio of the aqueous dispersion (A) of the polymer particles and the amphoteric surfactant (B) is within such a range, the composition for darkening processing comprising the components (A) to (D) is mixed. It is excellent in stability and excellent in foaming suppression effect, dust adhesion prevention effect, processing effect durability, etc. in the processing step.
更に、本発明の濃色化剤は、濃色化水準の度合いを維持させながら、静電気防止性の付与を目的で、第３の必須成分であるアニオン性静電気防止剤（Ｃ）を添加してなる。
かかるアニオン性静電気防止剤（Ｃ）としては、公知慣用のものが使用可能であり、例えば、モノメチル及び／又はジメチル燐酸エステル、モノブチル及び／又はジブチル燐酸エステル等のモノ及び／又はジ低級アルキル燐酸エステル類のナトリウム塩などのアルカリ金属塩、アンモニウム塩の酸性燐酸エステル塩、更には、グルコン酸、グリコール酸、乳酸、酪酸、リンゴ酸等のヒドロキシカルボン酸類のナトリウム塩等のアルカリ金属塩が好ましいが、これらの中では、酸性燐酸エステル塩が特に好ましい。
Furthermore, the darkening agent of the present invention is added with an anionic antistatic agent (C), which is a third essential component, for the purpose of imparting antistatic properties while maintaining the level of darkening level. Become.
As the anionic antistatic agent (C), known and conventional ones can be used. For example, mono- and / or di-lower alkyl phosphate esters such as monomethyl and / or dimethyl phosphate ester, monobutyl and / or dibutyl phosphate ester, etc. Preferred are alkali metal salts such as sodium salts of acids, acidic phosphoric acid ester salts of ammonium salts, and alkali metal salts such as sodium salts of hydroxycarboxylic acids such as gluconic acid, glycolic acid, lactic acid, butyric acid, malic acid, Of these, acidic phosphate ester salts are particularly preferred.
前記アニオン性制電剤（Ｃ）の使用量は、濃色化剤の安定性の点から、重合体層（Ａ−１）及び重合体層（Ａ−２）の合計量に対し、〔（Ａ−１）＋（Ａ−２）〕／アニオン性制電剤（Ｃ）＝２０／１〜１／１の範囲が好ましい。 The amount of the anionic antistatic agent (C) used is [[((1)) with respect to the total amount of the polymer layer (A-1) and the polymer layer (A-2) from the viewpoint of the stability of the darkening agent. A-1) + (A-2)] / anionic antistatic agent (C) = 20/1 to 1/1 is preferable.
更に、本発明の濃色化剤は、耐擦過性を向上せしめる目的で、第４の成分であるシリコーンエマルジョン（Ｄ）を添加することができる。
かかるシリコーンエマルジョン（Ｄ）としては、公知慣用のものが使用可能であり、例えば、ポリジメチルシロキサン、アミノ変性シリコーン、カルボキシ変性シリコーン、カルビノール変性シリコーン、エポキシ変性シリコーン、ポリエーテル変性シリコーンなどの乳化物が使用できる。これらの中で、特に濃色化効果の維持に極めて有効に作用し濃色化効果の低下を抑制し、且つ耐擦過性を向上させる点から、カチオン性界面活性剤及び／又は非イオン性界面活性剤により乳化分散されたシリコーンエマルジョンが好ましく、この場合シリコーン樹脂に対するカチオン性界面活性剤及び／又は非イオン性界面活性剤の使用比率は１５重量％以下であることが好ましい。
Furthermore, the thickening agent of the present invention may contain a fourth component, silicone emulsion (D), for the purpose of improving the scratch resistance.
As the silicone emulsion (D), known and usual ones can be used. For example, emulsions such as polydimethylsiloxane, amino-modified silicone, carboxy-modified silicone, carbinol-modified silicone, epoxy-modified silicone, and polyether-modified silicone Can be used. Among these, cationic surfactants and / or nonionic interfaces are particularly effective in maintaining the darkening effect, suppressing a reduction in the darkening effect, and improving scratch resistance. A silicone emulsion emulsified and dispersed with an activator is preferable. In this case, the ratio of the cationic surfactant and / or nonionic surfactant to the silicone resin is preferably 15% by weight or less.
前記カチオン性界面活性剤及び／又は非イオン性界面活性剤により乳化分散されたシリコーンエマルジョンとは、例えば、ディックシリコンソフナー３００（大日本インキ化学工業（株）社製）、ディックシリコンソフナー３００ＣＳ（大日本インキ化学工業（株）社製）ディックシリコンソフナーＳ（大日本インキ化学工業（株）社製）、ディックシリコンソフナーＨ−ＫＫ（大日本インキ化学工業（株）社製）、ディックシリコンソフナーＡ−９００（大日本インキ化学工業（株）社製）、ディックシリコンソフナー３２０（大日本インキ化学工業（株）社製）、ディックシリコンソフナーＡ−１９５（大日本インキ化学工業（株）社製）、ディックシリコンソフナー２００（大日本インキ化学工業（株）社製）、ディックシリコンソフナー６００（大日本インキ化学工業（株）社製）等が挙げられる。 Examples of the silicone emulsion emulsified and dispersed with the cationic surfactant and / or nonionic surfactant include, for example, Dick Silicon Softener 300 (manufactured by Dainippon Ink & Chemicals, Inc.), Dick Silicon Softener 300CS (large Nippon Ink Chemical Co., Ltd.) Dick Silicon Softener S (Dainippon Ink Chemical Co., Ltd.), Dick Silicon Softener H-KK (Dainippon Ink Chemical Co., Ltd.), Dick Silicon Softener A -900 (Dainippon Ink Chemical Co., Ltd.), Dick Silicon Softener 320 (Dainippon Ink Chemical Co., Ltd.), Dick Silicon Softener A-195 (Dainippon Ink Chemical Co., Ltd.) , Dick Silicon Softener 200 (Dainippon Ink Chemical Co., Ltd.), Dick Silicon Soft Over 600 (Dainippon Ink & Chemicals Co., Ltd.), and the like.
以上のように、本発明の濃色化剤は、少なくとも、重合体粒子含有水分散体（Ａ）と両性界面活性剤（Ｂ）及びアニオン性静電気防止剤（Ｃ）、あるいは重合体粒子含有水分散体（Ａ）と両性界面活性剤（Ｂ）とアニオン性静電気防止剤（Ｃ）及びシリコーンエマルジョン（Ｄ）からなり、各々の必須成分の固形分重量比が、（Ａ）／（Ｂ）／（Ｃ）＝１００／１〜５０／１〜１００、あるいは（Ａ）／（Ｂ）／（Ｃ）／（Ｄ）＝１００／１〜５０／１〜１００／１〜５０の範囲であることが好ましい。 As described above, the thickening agent of the present invention contains at least the polymer particle-containing water dispersion (A), the amphoteric surfactant (B) and the anionic antistatic agent (C), or polymer particle-containing water. A dispersion (A), an amphoteric surfactant (B), an anionic antistatic agent (C), and a silicone emulsion (D), and the solid content weight ratio of each essential component is (A) / (B) / (C) = 100/1 to 50/1 to 100, or (A) / (B) / (C) / (D) = 100/1 to 50/1 to 100/1 to 50. preferable.
次に、本発明の繊維の濃色化加工方法について説明する。
上記で得られた本発明の濃色化剤は、被処理物である紙、繊維、木、又はプラスティックなどの原材料から選ばれる少なくとも一つを用いてなる物品（構造物）の種類または調整形態などに応じて、任意の方法で物品に適応され得る。例えば、必要に応じて希釈を行ない浸漬塗布あるいはスプレー等の如き被覆加工の既知の方法で被処理物の表面に付着させ熱処理する方法が採用される。
Next, the fiber darkening method of the present invention will be described.
The above-obtained darkening agent of the present invention is a kind or an adjusted form of an article (structure) using at least one selected from raw materials such as paper, fiber, wood, or plastic, which is an object to be processed. Can be adapted to the article in any way, depending on the For example, a method of performing heat treatment by diluting as necessary and adhering to the surface of the object to be treated by a known method of coating processing such as dip coating or spraying is employed.
かかる熱処理方法としては、特に限定しないが、例えば、本発明の濃色化剤固形分を０．５〜５．０％になるよう軟水で希釈し、ポリエステル織物に含浸させ、マングルで含浸率８０〜１００％に絞り、次いで熱風循環乾燥機中で１００〜１２０℃にて２〜３分間予備乾燥した後、１５０〜１６０℃にて３０秒〜１分間キュアリングする方法が挙げられる。
上記の熱処理の際の条件は特に限定されるものではなく、通常の熱処理条件、例えば加熱オーブン中８０〜１２０℃×３０秒〜３分で予備乾燥した後１３０〜１８０℃×３０秒〜３分キュアリングする条件が採用され得る。
Although it does not specifically limit as this heat processing method, For example, it dilutes with soft water so that the darkening agent solid content of this invention may be 0.5 to 5.0%, it is made to impregnate in polyester fabric, and the impregnation rate is 80 with a mangle. A method of squeezing to ˜100%, followed by preliminary drying at 100 to 120 ° C. for 2 to 3 minutes in a hot air circulating dryer, and then curing at 150 to 160 ° C. for 30 seconds to 1 minute can be mentioned.
The conditions at the time of the above heat treatment are not particularly limited, and after normal drying in normal heat treatment conditions, for example, 80 to 120 ° C. × 30 seconds to 3 minutes in a heating oven, 130 to 180 ° C. × 30 seconds to 3 minutes. Conditions for curing can be employed.
本発明の物品とは、印刷された紙面、染色された繊維製品、着色された木質材料製品、印刷もしくは着色されたプラスティック製品から選ばれる少なくとも一つであって、前記濃色化剤を使用して表面の濃色化方法により濃色化加工を行ったことを特徴とする物品である。
これら物品は単一素材からなるものであってもよく、複数の素材が複合化されたものであってもよく、特に制限しない。
The article of the present invention is at least one selected from a printed paper surface, a dyed fiber product, a colored wood material product, a printed or colored plastic product, and uses the above thickening agent. The article is characterized in that the surface is darkened by the method of darkening the surface.
These articles may be composed of a single material, or may be a composite of a plurality of materials, and are not particularly limited.
本発明の物品の中で、繊維製品としては、例えば、ポリエステル、ポリアミド、アクリル等の合成繊維類、ジアセテート、トリアセテート、レーヨン等の化学繊維類、絹、木綿、羊毛等の天然繊維類の染色繊維等が挙げられる。
前記繊維製品の形態としては、例えば、織物、編物、不織布、綿、長繊維糸状、短繊維糸状等が挙げられる。これらの繊維製品に本発明の濃色化剤を被覆することにより、極めて深みのある濃色と優れた耐擦過性を有する濃色化効果が得られる。
Among the articles of the present invention, as textiles, for example, synthetic fibers such as polyester, polyamide, and acrylic, chemical fibers such as diacetate, triacetate, and rayon, and dyeing of natural fibers such as silk, cotton, and wool Examples thereof include fibers.
Examples of the form of the fiber product include woven fabrics, knitted fabrics, nonwoven fabrics, cotton, long fiber yarns, short fiber yarns, and the like. By coating these fiber products with the darkening agent of the present invention, a darkening effect having an extremely deep dark color and excellent scratch resistance can be obtained.
本発明の物品の中で、紙製品あるいは紙面としては、特に限定しないが、例えば、ポスター、カレンダー、壁紙、カタログ、ちらし、カード類、遊具類等が挙げられる。
また、本発明の物品の中で、木質材料製品としては、特に限定しないが、例えば、椅子、机等の家具、家庭用品、玩具等が挙げられる。
また、本発明の物品の中で、プラスティック製品としては、特に限定しないが、例えば、電化製品の部品、家庭用品、玩具等が挙げられる。
Among the articles of the present invention, the paper product or paper surface is not particularly limited, and examples thereof include posters, calendars, wallpaper, catalogs, flyers, cards, playground equipment, and the like.
Moreover, although it does not specifically limit as a wooden material product in the articles | goods of this invention, For example, furniture, such as a chair and a desk, household goods, a toy, etc. are mentioned.
Further, among the articles of the present invention, the plastic product is not particularly limited, and examples thereof include appliance parts, household goods, toys and the like.
以下、本発明を実施例により一層具体的に説明するが、本発明の範囲はこれら実施例のみに限定されるものではない。以下において、特に断りがない限り、「％」は重量％、「部」は重量部をそれぞれ示すものとする。本発明で用いた測定方法及び評価方法は以下の通りである。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the scope of the present invention is not limited only to these Examples. In the following, unless otherwise specified, “%” represents “% by weight” and “part” represents “part by weight”. The measurement method and evaluation method used in the present invention are as follows.
［ガラス転移温度（Ｔｇ）の測定方法］
合成例の水分散体を６０℃で減圧乾燥して得られた固形分をＤＳＣ法［セイコーインストルメント（株）製、機種名；ＤＳＣ６２００、解析ソフト；エクスター６０００］にて測定した。
[Measurement method of glass transition temperature (Tg)]
The solid content obtained by drying the aqueous dispersion of the synthesis example at 60 ° C. under reduced pressure was measured by a DSC method [Seiko Instrument Co., Ltd., model name: DSC6200, analysis software: Extor 6000].
［濃色化加工布の作製方法］
実施例又は比較例に示した配合で調整した濃色化剤を含む処理液に黒色染ポリエステルサテンを含浸させ、マングルで含浸率１００％に絞り、次いで熱風循環乾燥機中で１１０℃にて３分間予備乾燥した後、１６０℃にて１分間熱処理した。
[Method for producing darkened fabric]
A treatment liquid containing a thickening agent prepared with the formulation shown in Examples or Comparative Examples was impregnated with black dyed polyester satin, narrowed to 100% with mangles, and then heated at 110 ° C. in a hot air circulating dryer. After preliminary drying for 1 minute, heat treatment was performed at 160 ° C. for 1 minute.
［濃色化効果の評価方法］
上記と同様の方法で加工した試料布の明度（以下、Ｌ値という）を分光式色差計ＳＥ２０００［日本電色工業（株）製］で測定した。尚、Ｌ値が小さいほど濃色であることを示し、原布と加工布のＬ値の差が３以上の場合を適格（○）とした。
[Evaluation method of darkening effect]
The lightness (hereinafter referred to as L value) of the sample cloth processed by the same method as above was measured with a spectroscopic color difference meter SE2000 [manufactured by Nippon Denshoku Industries Co., Ltd.]. In addition, it showed that it was dark color, so that L value was small, and the case where the difference of L value of a raw fabric and a processed cloth was 3 or more was made qualified ((circle)).
［加工効果の耐久性の評価方法］
学振型摩擦堅牢度試験機［スガ試験機（株）製］を用いて、試料布面同士を荷重５０ｇで１００回擦過した後、上記の分光式色差計でＬ値を測定した。擦過前後のＬ値の差が小さいほど加工効果の耐久性に優れることを示す。擦過前後のＬ値の差が１以内を適格（○）とした。
[Method for evaluating durability of processing effect]
Using a Gakushin type friction fastness tester [manufactured by Suga Test Instruments Co., Ltd.], the sample cloth surfaces were rubbed 100 times with a load of 50 g, and then the L value was measured with the spectral color difference meter described above. It shows that it is excellent in the durability of a processing effect, so that the difference of L value before and behind abrasion is small. A difference in L value before and after rubbing was within 1 (qualified).
［静電気防止性の評価方法］
上記と同様の方法で加工した試料布を２０℃、相対湿度６０％で４８時間調湿した後、摩擦帯電圧（ＫＶ）を京大化研式ロータリースタチックテスター ＲＳＴ３０１［（株）興亜商会］を用いて測定した。摩擦帯電圧が低いほど静電気傷害が少なく、１ＫＶ以下を適格（○）とした。
[Static evaluation method]
A sample cloth processed in the same manner as described above was conditioned for 48 hours at 20 ° C. and a relative humidity of 60%, and then the frictional voltage (KV) was changed to a Kyoto University rotary static tester RST301 [Koa Shokai Co., Ltd.] It measured using. The lower the frictional voltage, the less the electrostatic damage, and 1 KV or less was qualified (O).
［配合液の安定性の評価方法］
配合液の安定性は、下記の方法で測定したエマルジョンの凝集物生成率で評価した。
表２及び表３の配合液１リットルを直径１２ｃｍ、高さ２０ｃｍの透明容器に入れて、６枚タービン羽（直径４ｃｍ、幅７ｍｍ）、８００ｒｐｍ［特殊機化工（株）製、ＴＫホモディスパーＤＨＬ型］で５分間撹拌した後、３２０メッシュネットで濾過し、濾取した凝集物の乾燥重量（Ｓ）を秤量し、次式で凝集物生成率（％）を算出した。
凝集物生成率（％）＝（Ｓ÷ＳＸ）×（１２５００÷１０００）×１００
但し、上式中のＳＸは表２及び表３に記載の重合体粒子（Ａ）の部数を示す
配合液の安定性の判定
○：凝集物生成率０％の場合。
△：凝集物生成率０．２％未満の場合。
×：凝集物生成率０．２％以上の場合。
[Method for evaluating stability of compounded liquid]
The stability of the blended liquid was evaluated by the aggregate formation rate of the emulsion measured by the following method.
1 liter of the compounded liquid of Table 2 and Table 3 is put in a transparent container having a diameter of 12 cm and a height of 20 cm, and 6 turbine blades (diameter 4 cm, width 7 mm), 800 rpm [manufactured by Special Machinery Corporation, TK homodisper DHL The mixture was stirred for 5 minutes, filtered through a 320 mesh net, the dry weight (S) of the collected aggregate was weighed, and the aggregate production rate (%) was calculated by the following formula.
Aggregate production rate (%) = (S ÷ S X ) × (12500 ÷ 1000) × 100
However, S X in the above formula is the stability determination of the mixed solution indicating the number of parts of the polymer particles (A) described in Table 2 and Table 3: When the aggregate production rate is 0%.
(Triangle | delta): When the aggregate formation rate is less than 0.2%.
X: When the aggregate formation rate is 0.2% or more.
窒素導入管、滴下ロート、環流冷却管、撹拌装置を備えた１５００ｍｌの４つ口フラスコにイオン交換水４５０．０部、表１のエチレン性不飽和単量体混合物の乳化液〔重合体層（Ａ−２）〕６０．０部を仕込み、撹拌下系内を窒素置換しながら７５℃に昇温し、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩の１％イオン交換水溶液（以下重合開始剤水溶液）２０．０部を添加して重合を開始した。更に、７５℃に保ちながら重合体層（Ａ−２）の残量を９０分にわたり滴下した。重合体層（Ａ−２）滴下終了とともに重合開始剤水溶液８．０部を添加し、７５℃で２時間熟成後、表１のエチレン性不飽和単量体混合物〔重合体層（Ａ−１）〕６０部と重合開始剤水溶液１２．０部を７５℃で９０分かけて滴下した。重合体層（Ａ−１）及び重合開始剤水溶液滴下終了とともに重合開始剤水溶液２．０部を添加２時間熟成後、冷却しイオン交換水を加えて表１に示す固形分２０．０％の重合体粒子含有水分散体（Ａ）を得た。 In a 1500 ml four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a reflux condenser, and a stirrer, 450.0 parts of ion-exchanged water and an emulsion of the ethylenically unsaturated monomer mixture shown in Table 1 [polymer layer ( A-2)] 60.0 parts were charged, and the system was heated to 75 ° C. while the inside of the system was purged with nitrogen, and a 1% ion exchange aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride ( Then, 20.0 parts of a polymerization initiator aqueous solution) was added to initiate polymerization. Furthermore, the remaining amount of the polymer layer (A-2) was dropped over 90 minutes while maintaining at 75 ° C. Upon completion of dropping of the polymer layer (A-2), 8.0 parts of a polymerization initiator aqueous solution was added, and after aging at 75 ° C. for 2 hours, the ethylenically unsaturated monomer mixture shown in Table 1 [polymer layer (A-1 )] 60 parts and 12.0 parts of a polymerization initiator aqueous solution were added dropwise at 75 ° C. over 90 minutes. Upon completion of dropping of the polymer layer (A-1) and the polymerization initiator aqueous solution, 2.0 parts of the polymerization initiator aqueous solution was added, and after aging for 2 hours, the mixture was cooled and ion-exchanged water was added, and the solid content shown in Table 1 was 20.0%. A polymer particle-containing aqueous dispersion (A) was obtained.
［合成例２］、［合成例３］、及び［合成例６］
合成例１と同様の操作で、合成例２、合成例３、及び合成例６を表１に示す配合で行った結果、固形分２０．０％の重合体粒子含有水分散体（Ａ）を得た。
[Synthesis Example 2], [Synthesis Example 3], and [Synthesis Example 6]
As a result of performing Synthesis Example 2, Synthesis Example 3, and Synthesis Example 6 with the composition shown in Table 1 in the same manner as in Synthesis Example 1, polymer particle-containing aqueous dispersion (A) having a solid content of 20.0% was obtained. Obtained.
［合成例４］
窒素導入管、滴下ロート、環流冷却管、撹拌装置を備えた１５００ｍｌの４つ口フラスコにイオン交換水４５０．０部、表１のエチレン性不飽和単量体混合物の乳化液〔重合体層（Ａ−１）〕６０．０部を仕込み、撹拌下系内を窒素置換しながら７５℃に昇温し、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩の１％イオン交換水溶液（以下重合開始剤水溶液）２０．０部を添加して重合を開始した。更に、７５℃に保ちながら重合体層（Ａ−１）の残量を１２０分にわたり滴下した。重合体層（Ａ−１）滴下終了とともに重合開始剤水溶液１６．０部を添加し、７５℃で２時間熟成後、冷却しイオン交換水を加えて表１に示す固形分２０．０％の重合体粒子含有水分散体（Ａ）を得た。但し、合成例４では、重合体層（Ａ−２）は使用していない。
[Synthesis Example 4]
In a 1500 ml four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a reflux condenser, and a stirrer, 450.0 parts of ion-exchanged water and an emulsion of the ethylenically unsaturated monomer mixture shown in Table 1 [polymer layer ( A-1)] 60.0 parts were charged, and the system was heated to 75 ° C. while the inside of the system was purged with nitrogen, and a 1% ion exchange aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride ( Then, 20.0 parts of a polymerization initiator aqueous solution) was added to initiate polymerization. Furthermore, the remaining amount of the polymer layer (A-1) was dropped over 120 minutes while maintaining at 75 ° C. Upon completion of dropping of the polymer layer (A-1), 16.0 parts of a polymerization initiator aqueous solution was added. After aging at 75 ° C. for 2 hours, the mixture was cooled and ion-exchanged water was added, and the solid content shown in Table 1 was 20.0%. A polymer particle-containing aqueous dispersion (A) was obtained. However, in Synthesis Example 4, the polymer layer (A-2) is not used.
［合成例５］
窒素導入管、滴下ロート、環流冷却管、撹拌装置を備えた１５００ｍｌの４つ口フラスコにイオン交換水４５０．０部、表１のエチレン性不飽和単量体混合物の乳化液〔重合体層（Ａ−２）〕６０．０部を仕込み、撹拌下系内を窒素置換しながら７５℃に昇温し、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩の１％イオン交換水溶液（以下重合開始剤水溶液）２０．０部を添加して重合を開始した。更に、７５℃に保ちながら重合体層（Ａ−２）の残量を１２０分にわたり滴下した。重合体層（Ａ−２）滴下終了とともに重合開始剤水溶液１６．０部を添加し、７５℃で２時間熟成後、冷却しイオン交換水を加えて表１に示す固形分２０．０％の重合体粒子含有水分散体（Ａ）を得た。
[Synthesis Example 5]
In a 1500 ml four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a reflux condenser, and a stirrer, 450.0 parts of ion-exchanged water and an emulsion of the ethylenically unsaturated monomer mixture shown in Table 1 [polymer layer ( A-2)] 60.0 parts were charged, and the system was heated to 75 ° C. while the inside of the system was purged with nitrogen, and a 1% ion exchange aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride ( Then, 20.0 parts of a polymerization initiator aqueous solution) was added to initiate polymerization. Furthermore, the remaining amount of the polymer layer (A-2) was dropped over 120 minutes while maintaining at 75 ° C. Upon completion of dropping of the polymer layer (A-2), 16.0 parts of a polymerization initiator aqueous solution was added. After aging at 75 ° C. for 2 hours, the mixture was cooled and ion-exchanged water was added, and the solid content shown in Table 1 was 20.0%. A polymer particle-containing aqueous dispersion (A) was obtained.
［実施例１］
合成例１で得た重合体粒子含有水分散体（Ａ）を固形分換算で１００部と、両性界面活性剤（Ｂ）としてラウリルジメチルアミノ酢酸ベタインを固形分換算で１０部と、アニオン性制電剤（Ｃ）としてパーマスタットＷＦ−１８〔大日本インキ化学工業（株）製〕を固形分換算で３０部と、シリコーンエマルジョン（Ｄ）としてディックシリコーン３２０〔大日本インキ化学工業（株）製〕を固形分換算で１０部、及び水１２３５０部を含む処理浴、全量１２５００部を調整した。
この処理浴にポリエステルサテン黒色染色布を浸漬し、原布重量に対する処理液の含浸量が１００％になるようにマングルで絞り、１１０℃で３分間乾燥し、更に１６０℃で１分間熱処理を行った。
得られた処理布の濃色化効果、加工効果の耐久性、静電気防止性は、前述の評価方法を用い評価した。
評価結果を表２に示した。
[Example 1]
100 parts of the polymer particle-containing aqueous dispersion (A) obtained in Synthesis Example 1 in terms of solid content, 10 parts of lauryldimethylaminoacetic acid betaine as the amphoteric surfactant (B) in terms of solid content, an anionic system Permastat WF-18 (manufactured by Dainippon Ink & Chemicals, Inc.) as the electrical agent (C) is 30 parts in terms of solid content, and Dick silicone 320 (manufactured by Dainippon Ink & Chemicals, Inc.) as the silicone emulsion (D). A treatment bath containing 10 parts in terms of solid content and 12350 parts of water, and a total amount of 12,500 parts were prepared.
Immerse the polyester satin black dyed cloth in this treatment bath, squeeze with mangle so that the impregnation amount of the treatment liquid with respect to the weight of the raw cloth becomes 100%, dry at 110 ° C. for 3 minutes, and further heat-treat at 160 ° C. for 1 minute. It was.
The darkening effect, the durability of the processing effect, and the antistatic property of the obtained treated cloth were evaluated using the evaluation methods described above.
The evaluation results are shown in Table 2.
［実施例２〜５］
表２に示した配合に従い、実施例１と同様の方法で行った評価結果を表２に示す。
[Examples 2 to 5]
Table 2 shows the results of evaluation performed in the same manner as in Example 1 according to the formulation shown in Table 2.
［比較例１〜７］
表３に示した配合に従い、実施例１と同様の方法で行った評価結果を表３に示す。
何れの場合も充分な性能は発現できなかった。
[Comparative Examples 1 to 7]
Table 3 shows the results of evaluation performed in the same manner as in Example 1 in accordance with the formulation shown in Table 3.
In either case, sufficient performance could not be expressed.
尚、本発明に記載の表及び本文中の略称の化合物名は下記の通りである。
ＭＭＡ ；メチルメタクリレート
ＩＢＭＡ ；イソ−ブチルメタクリレート
ＴＢＭＡ ；ターシャリ−ブチルメタクリレート
ＩＢＡ ；イソ−ブチルアクリレート
ＭＡＭ ；メタアクリルアミド
Ｎ−ＭＡＭ；Ｎ−メチロールアクリルアミド
アーカード１６−５０（ライオン（株）製）；塩化ヘキサデシルトリメチルアンモニウム
The names of the abbreviated compounds in the tables and texts described in the present invention are as follows.
MMA; methyl methacrylate IBMA; iso-butyl methacrylate TBMA; tertiary-butyl methacrylate IBA; iso-butyl acrylate MAM; methacrylamide N-MAM; N-methylol acrylamide ARCARD 16-50 (manufactured by Lion Corporation); hexadecyltrimethyl chloride Ammonium
本発明は、紙や繊維、木、プラスティックなどの原材料からなる、例えば、印刷された紙面、染色された繊維製品、着色された木質材料製品、印刷もしくは着色されたプラスティック製品における表面の色の濃さ、深み、鮮明性などの意匠性を向上させ、且つ優れた制電性と耐擦過性を付与する目的で使用する濃色化剤であり、また該濃色化剤を用いたこれら物品の表面の濃色化方法であり、更に該濃色化剤で処理してなる物品の表面の質感の向上に極めて有効である。
The present invention is composed of raw materials such as paper, fiber, wood, plastic, etc., for example, printed paper, dyed fiber products, colored wood material products, surface darkness in printed or colored plastic products. A thickening agent used for the purpose of improving design properties such as depth, depth, and sharpness, and imparting excellent antistatic properties and scratch resistance, and of these articles using the thickening agent This is a surface darkening method, and is extremely effective for improving the surface texture of articles obtained by treatment with the darkening agent.
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| JP4554550B2 (en) * | 2006-04-28 | 2010-09-29 | 花王株式会社 | Textile treatment composition |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH093774A (en) * | 1995-06-19 | 1997-01-07 | Dainippon Ink & Chem Inc | Color deepening agent and deepening method |
| JPH09291486A (en) * | 1996-04-18 | 1997-11-11 | Dainippon Ink & Chem Inc | Color-deepening agent and deepening of color |
| JPH10237776A (en) * | 1996-12-27 | 1998-09-08 | Kao Corp | Color-deepening agent for colored solid and deepening of color |
| JPH1181147A (en) * | 1997-09-08 | 1999-03-26 | Shin Etsu Chem Co Ltd | Color-deepening agent for synthetic fiber |
| JPH11181680A (en) * | 1997-12-16 | 1999-07-06 | Kao Corp | Antistatic agent |
| JP2000265369A (en) * | 1999-03-19 | 2000-09-26 | Toray Ind Inc | Textile treatment agent and treatment of textile structure product |
| JP2002054074A (en) * | 2000-05-25 | 2002-02-19 | Kao Corp | Method for restoring color |
| JP2003213580A (en) * | 2002-01-21 | 2003-07-30 | Dainippon Ink & Chem Inc | Color-deepening agent and method for color deepening |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH093774A (en) * | 1995-06-19 | 1997-01-07 | Dainippon Ink & Chem Inc | Color deepening agent and deepening method |
| JPH09291486A (en) * | 1996-04-18 | 1997-11-11 | Dainippon Ink & Chem Inc | Color-deepening agent and deepening of color |
| JPH10237776A (en) * | 1996-12-27 | 1998-09-08 | Kao Corp | Color-deepening agent for colored solid and deepening of color |
| JPH1181147A (en) * | 1997-09-08 | 1999-03-26 | Shin Etsu Chem Co Ltd | Color-deepening agent for synthetic fiber |
| JPH11181680A (en) * | 1997-12-16 | 1999-07-06 | Kao Corp | Antistatic agent |
| JP2000265369A (en) * | 1999-03-19 | 2000-09-26 | Toray Ind Inc | Textile treatment agent and treatment of textile structure product |
| JP2002054074A (en) * | 2000-05-25 | 2002-02-19 | Kao Corp | Method for restoring color |
| JP2003213580A (en) * | 2002-01-21 | 2003-07-30 | Dainippon Ink & Chem Inc | Color-deepening agent and method for color deepening |
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