JPWO2018168487A1 - Aqueous resin composition for flocking processing and flocked product - Google Patents
Aqueous resin composition for flocking processing and flocked product Download PDFInfo
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
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Abstract
カルボキシル基を有する重合体（Ａ）が、金属水酸化物（ｂ１）を必須成分とする塩基性化合物（Ｂ）で中和されたアクリル樹脂（Ｃ）と、ポリオキサゾリン化合物（Ｄ）と、水性媒体（Ｅ）とを含有することを特徴とする植毛加工用水性樹脂組成物を提供する。この植毛加工用水性樹脂組成物は、経時安定性に優れるとともに、植毛強度及び基材密着性に優れる植毛加工品が得られることから、種々の植毛加工品に好適に用いることができる。 An acrylic resin (C) in which a polymer (A) having a carboxyl group is neutralized with a basic compound (B) containing a metal hydroxide (b1) as an essential component, a polyoxazoline compound (D), and an aqueous solution An aqueous resin composition for flocking processing comprising a medium (E) is provided. This aqueous resin composition for flocking processing is excellent in stability over time and can be used suitably for various flocking processed products because a flocking processed product having excellent flocking strength and substrate adhesion can be obtained.
Description
本発明は、植毛加工品に用いられる水性樹脂組成物に関する。 The present invention relates to an aqueous resin composition used for a flocked product.
植毛加工は、バインダーを塗布した基材に短繊維を静電気の力で付着させる加工方法であり、断熱性や風合い付与のため、家庭用品を中心に様々な用途に使用されている。バインダーには、水性樹脂を用いることが一般的であり、これらの中でもアクリルエマルジョンの使用が多い。しかし、自己架橋型アクリルエマルジョンでは、短繊維との接着強度が低く、十分な植毛強度が得られないため、水溶性架橋剤の添加による強度向上や耐久性の向上が検討されている。 The flocking process is a processing method in which short fibers are attached to a base material coated with a binder by electrostatic force, and is used for various applications mainly for household goods for heat insulation and texture. As the binder, an aqueous resin is generally used, and among these, an acrylic emulsion is often used. However, since the self-crosslinking acrylic emulsion has low adhesive strength with short fibers and a sufficient flocking strength cannot be obtained, improvement in strength and durability by adding a water-soluble crosslinking agent has been studied.
このような中、水分散性のアクリル系共重合体、水溶性もしくは水分散性の高分子化合
物、及びオキサゾリン基を含有する水溶性高分子化合物を含むアクリル系樹脂水性組成物が提案されている（例えば、特許文献１参照。）。しかしながら、このアクリル系樹脂水性組成物は、植毛加工用基材に多く用いられる塩化ビニルに対して密着性が十分に得られないと共に、経時安定性が不十分であり、増粘や物性変化等の問題があった。Under such circumstances, an aqueous acrylic resin composition comprising a water-dispersible acrylic copolymer, a water-soluble or water-dispersible polymer compound, and a water-soluble polymer compound containing an oxazoline group has been proposed. (For example, refer to Patent Document 1). However, this acrylic resin aqueous composition does not provide sufficient adhesion to vinyl chloride, which is often used as a base material for flocking, and has insufficient stability over time, such as thickening and changes in physical properties. There was a problem.
本発明が解決しようとする課題は、経時安定性に優れ、植毛強度及び基材密着性に優れる植毛加工品が得られる植毛加工用水性樹脂組成を提供することである。 The problem to be solved by the present invention is to provide an aqueous resin composition for flocking processing that provides a flocked product having excellent stability over time, flocking strength and substrate adhesion.
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、特定の中和されたアクリル樹脂、オキサゾリン基を有する樹脂、及び水性媒体を含有する植毛加工用水性樹脂組成物が、上記課題を解決できることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that the aqueous resin composition for flocking processing containing a specific neutralized acrylic resin, a resin having an oxazoline group, and an aqueous medium is the above. The present inventors have found that the problems can be solved and completed the present invention.
すなわち、本発明は、カルボキシル基を有する重合体（Ａ）が、金属水酸化物（ｂ１）を必須成分とする塩基性化合物（Ｂ）で中和されたアクリル樹脂（Ｃ）と、ポリオキサゾリン化合物（Ｄ）と、水性媒体（Ｅ）とを含有することを特徴とする植毛加工用水性樹脂組成物に関する。 That is, the present invention relates to an acrylic resin (C) in which a polymer (A) having a carboxyl group is neutralized with a basic compound (B) containing a metal hydroxide (b1) as an essential component, and a polyoxazoline compound. The present invention relates to an aqueous resin composition for flocking processing comprising (D) and an aqueous medium (E).
本発明の植毛加工用水性樹脂組成物は、植毛強度及び基材密着性に優れる植毛加工品が得られることから、例えば、手袋、自動車の内装材、電気部品等をはじめとする様々な用途で使用することができる。 The aqueous resin composition for flocking processing according to the present invention provides a flocked processed product having excellent flocking strength and substrate adhesion, and thus can be used in various applications including, for example, gloves, automobile interior materials, electric parts and the like. Can be used.
本発明の植毛加工用水性樹脂組成物は、カルボキシル基を有する重合体（Ａ）が、金属水酸化物（ｂ１）を必須成分とする塩基性化合物（Ｂ）で中和されたアクリル樹脂（Ｃ）と、ポリオキサゾリン化合物（Ｄ）と、水性媒体（Ｅ）とを含有するものである。 The aqueous resin composition for flocking processing of the present invention comprises an acrylic resin (C) in which a polymer (A) having a carboxyl group is neutralized with a basic compound (B) containing a metal hydroxide (b1) as an essential component. ), A polyoxazoline compound (D), and an aqueous medium (E).
前記カルボキシル基を有する重合体（Ａ）は、カルボキシル基を有する単量体（ａ１）及びその他の単量体（ａ２）を共重合することにより得られる。 The polymer (A) having a carboxyl group can be obtained by copolymerizing a monomer (a1) having a carboxyl group and another monomer (a2).
前記カルボキシル基を有する単量体（ａ１）としては、（メタ）アクリル酸、クロトン酸等の不飽和モノカルボン酸；イタコン酸（無水物）、マレイン酸（無水物）、フマル酸等の不飽和ジカルボン酸などが挙げられる。これらの単量体（ａ１）は、単独で用いることも２種以上併用することもできる。 Examples of the monomer (a1) having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; unsaturated acids such as itaconic acid (anhydride), maleic acid (anhydride), and fumaric acid. And dicarboxylic acid. These monomers (a1) can be used alone or in combination of two or more.
なお、本発明において、「（メタ）アクリル酸」とは、アクリル酸とメタクリル酸の一方又は両方をいい、「（メタ）アクリレート」とは、アクリレートとメタアクリレートの一方又は両方をいい、「酸（無水物）」とは、酸及び酸無水物の一方又は両方をいう。 In the present invention, “(meth) acrylic acid” refers to one or both of acrylic acid and methacrylic acid, “(meth) acrylate” refers to one or both of acrylate and methacrylate, and “acid “(Anhydride)” refers to one or both of an acid and an acid anhydride.
前記その他の単量体（ａ２）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（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）アクリレート等のアルキル（メタ）アクリレート；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、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート等の水酸基を有する（メタ）アクリレート；Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリレート等のアミノ基を有する(メタ)アクリレート；ポリエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、ポリブチレングリコール（メタ）アクリレート、メトキシポリブチレングリコール（メタ）アクリレート等の（アルコキシ）ポリアルキレングリコール（メタ）アクリレート；（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド等のアミド基を有する単量体、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルメチルジメトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、（メタ）アクリロイルオキシメチルトリメトキシシラン、（メタ）アクリロイルオキシメチルトリエトキシシラン、２−（メタ）アクリロイルオキシエチルトリメトキシシラン、２−（メタ）アクリロイルオキシエチルトリエトキシシラン、３−（メタ）アクリロイルオキシプロピルトリメトキシシラン、３−（メタ）アクリロイルオキシプロピルトリエトキシシラン、３−（メタ）アクリロイルオキシプロピルメチルジメトキシシラン等のアルコキシシリル基を有する単量体；スチレン、α−メチルスチレン、パラメチルスチレン、クロロメチルスチレン、酢酸ビニル等のビニル単量体；アクリロニトリル、テトラヒドロフルフリル（メタ）アクリレート、ベンジル（メタ）アクリレート、グリシジル（メタ）アクリレートなどが挙げられる。これらのその他の単量体（ａ２）は、単独で用いることも２種以上併用することもできるが、基材密着性、植毛強度及び基材密着性がより向上することから、アクリロニトリルを含むことが好ましい。 Examples of the other monomer (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t- Alkyl (meth) acrylates such as butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate; 2-hydroxyethyl ( (Meth) acrylate having a hydroxyl group such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; N, N-dimethylaminoethyl (Meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, (meth) acrylate having an amino group such as N, N-diethylaminopropyl (meth) acrylate; polyethylene glycol (Alkoxy) poly such as (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polybutylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, etc. Monomers having an amide group such as alkylene glycol (meth) acrylate; (meth) acrylamide, N-methylol (meth) acrylamide, vinyl trime Toxisilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltris (2-methoxyethoxy) silane, (meth) acryloyloxymethyltrimethoxysilane, (meth) acryloyloxymethyltriethoxysilane, 2- (meth) acryloyloxyethyltri Methoxysilane, 2- (meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane Monomers having an alkoxysilyl group such as styrene; α-methylstyrene, paramethylstyrene, chloromethylstyrene, vinyl acetate and other vinyl monomers; acrylonitrile, teto Tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate and glycidyl (meth) acrylate. These other monomers (a2) can be used alone or in combination of two or more, but contain acrylonitrile because the substrate adhesion, flocking strength and substrate adhesion are further improved. Is preferred.
前記単量体（ａ１）の使用量は、植毛強度及び皮膜の柔軟性がより向上することから、前記重合体（Ａ）の原料となる単量体成分中、０．３〜５質量％の範囲が好ましく、０．５〜３質量％の範囲がより好ましい。 The monomer (a1) is used in an amount of 0.3 to 5% by mass in the monomer component as the raw material of the polymer (A) because the flocking strength and the flexibility of the film are further improved. The range is preferable, and the range of 0.5 to 3% by mass is more preferable.
また、基材密着性がより向上することから、前記重合体（Ａ）の原料となる単量体成分中、アクリロニトリルを４〜１０質量％の範囲で使用することが好ましい。 Moreover, since the base-material adhesiveness improves more, it is preferable to use acrylonitrile in 4-10 mass% in the monomer component used as the raw material of the said polymer (A).
前記重合体（Ａ）の酸価としては、植毛強度及び皮膜の柔軟性がより向上することから、２〜４０の範囲が好ましく、２〜２０の範囲がより好ましい。 The acid value of the polymer (A) is preferably in the range of 2 to 40 and more preferably in the range of 2 to 20 because the flocking strength and the flexibility of the film are further improved.
前記重合体（Ａ）の製造方法としては、水を溶媒として用いる乳化重合法、有機溶剤を溶媒として用いる溶液重合法等が挙げられるが、より簡便に前記重合体（Ａ）の水分散体が得られることから、乳化重合法が好ましい。 Examples of the method for producing the polymer (A) include an emulsion polymerization method using water as a solvent, a solution polymerization method using an organic solvent as a solvent, and the like. An aqueous dispersion of the polymer (A) is more simply used. The emulsion polymerization method is preferred because it is obtained.
前記乳化重合法としては、例えば、水性媒体中で、重合開始剤及び界面活性剤存在下、前記単量体（ａ１）及び前記単量体（ａ２）を４０〜１００℃の温度でラジカル重合する方法が挙げられる。 Examples of the emulsion polymerization method include radical polymerization of the monomer (a1) and the monomer (a2) at a temperature of 40 to 100 ° C. in the presence of a polymerization initiator and a surfactant in an aqueous medium. A method is mentioned.
前記重合開始剤としては、例えば、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、アゾビスシアノ吉草酸等のアゾ化合物；ｔｅｒｔ−ブチルパーオキシピバレート、ｔｅｒｔ−ブチルパーオキシベンゾエート、ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート、ジ−ｔｅｒｔ−ブチルパーオキサイド、クメンハイドロパーオキサイド、ベンゾイルパーオキサイド、ｔｅｒｔ−ブチルハイドロパーオキサイド等の有機過酸化物；過酸化水素、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の無機過酸化物などが挙げられる。これらの重合体開始剤は、単独で用いることも２種以上併用することもできる。また、前記重合開始剤は、前記重合体（Ａ）の原料となる単量体の合計に対して、０．１〜１０質量％の範囲内で使用することが好ましい。 Examples of the polymerization initiator include azo compounds such as 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), azobiscyanovaleric acid; tert-butylperoxy Organic peroxides such as pivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, tert-butyl hydroperoxide Oxides; inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate and the like. These polymer initiators can be used alone or in combination of two or more. Moreover, it is preferable to use the said polymerization initiator within the range of 0.1-10 mass% with respect to the sum total of the monomer used as the raw material of the said polymer (A).
また、前記重合開始剤は還元剤と併用することもできる。前記還元剤としては、例えば、重亜硫酸ナトリウム、メタ重亜硫酸ナトリウム、ホルムアルデヒドスルホオキシレート、塩化第一鉄、アスコルビン酸、エリソルビン酸及びその塩等が挙げられる。 Moreover, the said polymerization initiator can also be used together with a reducing agent. Examples of the reducing agent include sodium bisulfite, sodium metabisulfite, formaldehyde sulfooxylate, ferrous chloride, ascorbic acid, erythorbic acid, and salts thereof.
前記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エーテル、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多環フェニルエーテル、ポリオキシエチレン−ポリオキシプロピレンブロック共重合体、ソルビタン脂肪酸エステル等のノニオン界面活性剤；高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩、ポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩、ポリオキシエチレンアルキルスルホン酸塩、アルキルエーテル燐酸塩、アルケニルスルホコハク酸塩、ジアルキルスルホコハク酸塩、モノアルキルスルホコハク酸塩等のアニオン界面活性剤；Ｎ，Ｎ−ジメチルラウリルアミン、Ｎ，Ｎ−ジメチルオクタデシルアミン等の長鎖アルキル基を有する３級アミンのカルボン酸塩や４級アンモニウム塩等のカチオン界面活性剤；カルボン酸塩基、硫酸塩基、スルホン酸塩基、燐酸塩基等のアニオン性基と二重結合を併有する化合物、ノニオン性基と重合性二重結合を併有する化合物、４級アンモニウム塩基等のカチオン性基と重合性二重結合を併有する化合物等の反応性界面活性剤等が挙げられる。これらの界面活性剤は、単独で用いることも２種以上併用することもできる。また、前記界面活性剤は、前記重合体（Ａ）の原料となる単量体の合計に対して、１５質量％以下の範囲で使用するのが好ましく、１０質量％以下の範囲がより好ましい。 Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxyethylene-polyoxypropylene block copolymer, and sorbitan fatty acid ester. Agent: Higher alcohol sulfate ester, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene polycyclic phenyl ether sulfate, Polyoxyethylene alkyl sulfonate, alkyl ether phosphate, alkenyl sulfosuccinate, dialkyl sulfosuccinate, monoalkyl sulfosuccinate Anionic surfactants such as acid salts; Cationic surfactants such as carboxylic acid salts of tertiary amines having a long-chain alkyl group such as N, N-dimethyllaurylamine, N, N-dimethyloctadecylamine, and quaternary ammonium salts A compound having both an anionic group such as a carboxylate group, a sulfate group, a sulfonate group and a phosphate group and a double bond, a compound having both a nonionic group and a polymerizable double bond, and a cationic property such as a quaternary ammonium base And reactive surfactants such as compounds having both a group and a polymerizable double bond. These surfactants can be used alone or in combination of two or more. Moreover, it is preferable to use the said surfactant in 15 mass% or less with respect to the sum total of the monomer used as the raw material of the said polymer (A), and the range of 10 mass% or less is more preferable.
前記塩基性化合物（Ｂ）は、前記重合体（Ａ）の有するカルボキシル基の中和剤として使用されるが、得られる植毛加工品に優れた基材密着性を付与する上で、金属水酸化物（ｂ１）を含有することが重要である。さらに、基材密着性と植毛強度とのバランスがより向上することから、前記金属水酸化物（ｂ１）の含有量は、前記重合体（Ａ）の有するカルボキシル基の１０〜８０モル％を中和する量が好ましく、３０〜７０モル％を中和する量がより好ましく、４０〜６０モル％を中和する量がさらに好ましい。 The basic compound (B) is used as a neutralizing agent for the carboxyl group of the polymer (A), but for imparting excellent substrate adhesion to the obtained flocked product, metal hydroxide is used. It is important to contain the product (b1). Furthermore, since the balance between the substrate adhesion and the flocking strength is further improved, the content of the metal hydroxide (b1) is 10 to 80 mol% of the carboxyl group of the polymer (A). The amount to be summed is preferred, the amount to neutralize 30 to 70 mol% is more preferred, and the amount to neutralize 40 to 60 mol% is more preferred.
前記金属水酸化物（ｂ１）としては、例えば、水酸化ナトリウム、水酸化カリウム等が挙げられるが、基材密着性がより向上することから、水酸化ナトリウムが好ましい。これらの金属水酸化物（ｂ１）は、単独で用いることも２種以上併用することもできる。 Examples of the metal hydroxide (b1) include sodium hydroxide and potassium hydroxide. Sodium hydroxide is preferable because the adhesion to the substrate is further improved. These metal hydroxides (b1) can be used alone or in combination of two or more.
前記塩基性化合物（Ｂ）としては、前記金属水酸化物（ｂ１）以外のその他の塩基性化合物（ｂ２）を併用することができるが、その他の塩基性化合物（ｂ２）としては、例えば、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノプロピルアミン、ジプロピルアミン、トリプロピルアミン等のアルキルアミン；モノエタノールアミン、ジエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、Ｎ−メチルエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ，Ｎ−ジエチルエタノールアミン、２−アミノ−２−メチルプロパノール、２−（ジメチルアミノ）−２−メチルプロパノール、Ｎ−メチルジエタノールアミン等のアルカノールアミン；エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン等の多価アミン等の有機アミンやアンモニア（水）などが挙げられる。これらの中和剤（ｂ２）は、単独で用いることも２種以上併用することもできる。 As the basic compound (B), other basic compounds (b2) other than the metal hydroxide (b1) can be used in combination. As the other basic compounds (b2), for example, monomethyl Alkylamines such as amine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine; monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, N-methylethanolamine, Alkanol amines such as N, N-dimethylethanolamine, N, N-diethylethanolamine, 2-amino-2-methylpropanol, 2- (dimethylamino) -2-methylpropanol, N-methyldiethanolamine Ethylenediamine, diethylenetriamine, triethylenetetramine, organic amine or ammonia (water), such as a polyvalent amine such as tetraethylene pentamine and the like. These neutralizing agents (b2) can be used alone or in combination of two or more.
前記アクリル樹脂（Ｃ）は、前記カルボキシル基を有する重合体（Ａ）が、塩基性化合物（Ｂ）で中和されたものであるが、例えば、前記重合体（Ａ）の水分散体と前記塩基性化合物（Ｂ）とを混合することで容易に得ることができる。 The acrylic resin (C) is obtained by neutralizing the polymer (A) having the carboxyl group with a basic compound (B). For example, the aqueous dispersion of the polymer (A) and the polymer It can be easily obtained by mixing with the basic compound (B).
前記ポリオキサゾリン化合物（Ｄ）としては、水性媒体に容易に溶解又は分散するものが好ましく、例えば、株式会社日本触媒製の「エポクロス ＷＳ−３００」（水溶性タイプ）、「エポクロス ＷＳ−５００」（水溶性タイプ）、「エポクロス ＷＳ−７００」（水溶性タイプ）、「エポクロス Ｋ−２０１０Ｅ」（水分散タイプ）、「エポクロス Ｋ−２０２０Ｅ」（水分散タイプ）、「エポクロス Ｋ−２０３０Ｅ」（水分散タイプ）等が挙げられる。これらのポリオキサゾリン化合物（Ｄ）は、単独で用いることも２種以上併用することもできる。 As the polyoxazoline compound (D), those easily dissolved or dispersed in an aqueous medium are preferable. For example, “Epocross WS-300” (water-soluble type), “Epocross WS-500” (manufactured by Nippon Shokubai Co., Ltd.) Water-soluble type), "Epocross WS-700" (water-soluble type), "Epocross K-2010E" (water dispersion type), "Epocross K-2020E" (water dispersion type), "Epocross K-2030E" (water dispersion) Type). These polyoxazoline compounds (D) can be used alone or in combination of two or more.
前記水性媒体（Ｅ）としては、水、水と混和する有機溶剤、及び、これらの混合物が挙げられる。水と混和する有機溶剤としては、例えば、メタノール、エタノール、ｎ−プロパノール及びイソプロパノール等のアルコール；アセトン、メチルエチルケトン等のケトン；エチレングリコール、ジエチレングリコール、プロピレングリコール等のポリアルキレングリコール；ポリアルキレングリコールのアルキルエーテル；Ｎ-メチル−２−ピロリドン等のラクタム等が挙げられる。本発明では、水のみを用いても良く、また水及び水と混和する有機溶剤との混合物を用いても良く、水と混和する有機溶剤のみを用いても良い。安全性や環境に対する負荷の点から、水のみ、または、水及び水と混和する有機溶剤との混合物が好ましく、水のみを使用することが特に好ましい。 Examples of the aqueous medium (E) include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycols And lactams such as N-methyl-2-pyrrolidone. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and it is particularly preferable to use only water.
本発明の植毛加工用水性樹脂組成物は、前記アクリル樹脂（Ｃ）と、前記ポリオキサゾリン化合物（Ｄ）と、前記水性媒体（Ｅ）とを含有するものであるが、例えば、前記アクリル樹脂（Ｃ）の水分散体と前記ポリオキサゾリン化合物（Ｄ）とを混合することで容易に得ることができる。 The aqueous resin composition for flocking processing of the present invention contains the acrylic resin (C), the polyoxazoline compound (D), and the aqueous medium (E). For example, the acrylic resin ( It can be easily obtained by mixing an aqueous dispersion of C) and the polyoxazoline compound (D).
前記ポリオキサゾリン化合物（Ｄ）の使用量は、経時安定性、植毛強度及び基材密着性、柔軟性のバランスがより向上することから、前記アクリル樹脂（Ｃ）の有するカルボキシル基１モルに対し、前記ポリオキサゾリン化合物（Ｄ）の有するオキサゾリン基が０．１〜５モルの範囲が好ましく、０．３〜２モルの範囲がより好ましい。 The amount of the polyoxazoline compound (D) used is more stable over time, flocking strength and substrate adhesion, and the balance of flexibility is further improved, so that 1 mol of the carboxyl group of the acrylic resin (C), The range of 0.1-5 mol is preferable and, as for the oxazoline group which the said polyoxazoline compound (D) has, the range of 0.3-2 mol is more preferable.
また、本発明の植毛加工用水性樹脂組成物は、作業性、及び植毛強度がより向上することから、前記アクリル樹脂（Ｃ）、前記ポリオキサゾリン化合物（Ｄ）、前記水性媒体（Ｅ）以外の成分として、アクリル系増粘剤（Ｆ）を含有していることが好ましい。 Moreover, since the workability | operativity and the flocking strength improve more, the water-based resin composition for hair transplantation processing of this invention is other than the said acrylic resin (C), the said polyoxazoline compound (D), and the said aqueous medium (E). It is preferable to contain an acrylic thickener (F) as a component.
前記アクリル系増粘剤（Ｆ）は、作業性、植毛強度及び基材密着性がより向上することから、酸価が１５０〜５００ｍｇＫＯＨ／ｇの範囲のものが好ましく、２００〜４００ｍｇＫＯＨ／ｇの範囲のものがより好ましい。 The acrylic thickener (F) preferably has an acid value in the range of 150 to 500 mgKOH / g and more preferably in the range of 200 to 400 mgKOH / g because workability, flocking strength and substrate adhesion are further improved. Are more preferred.
また、本発明の植毛加工用水性樹脂組成物は、上記した以外の成分として、その他の増粘剤、顔料、充填剤、難燃剤、レベリング剤、分散剤、湿潤剤、消泡剤、老化防止剤、紫外線吸収剤、防腐剤等の添加剤を混合することもできる。 In addition, the aqueous resin composition for flocking processing of the present invention includes other thickeners, pigments, fillers, flame retardants, leveling agents, dispersants, wetting agents, antifoaming agents, and anti-aging components other than those described above. Additives such as additives, ultraviolet absorbers and preservatives can also be mixed.
本発明の植毛加工用水性樹脂組成物を塗布する基材としては、特に限定されないが、密着性がより向上することから、塩化ビニル基材が好ましい。 Although it does not specifically limit as a base material which apply | coats the aqueous resin composition for hair transplantation processing of this invention, Since a contact | adherence improves more, a vinyl chloride base material is preferable.
本発明の植毛加工用水性樹脂組成物の塗膜を有する植毛加工品としては、植毛強度及び基材密着性に優れることから、例えば、手袋、パッケージ材、衣料品、靴、エアコンやコタツ等の冷暖房機器部品、カメラ等の電気機器部品、自動車内装材、タイルカーペットなどに好適に使用される。 As a flocked product having a coating film of the aqueous resin composition for flocking processing of the present invention, it is excellent in flocking strength and substrate adhesion, and thus, for example, gloves, packaging materials, clothing items, shoes, air conditioners, kotatsu, etc. It is suitably used for air conditioning equipment parts, electrical equipment parts such as cameras, automobile interior materials, tile carpets and the like.
次に、本発明を、実施例及び比較例により具体的に説明する。 Next, the present invention will be specifically described with reference to examples and comparative examples.
（合成例１：アクリル樹脂（Ｃ−１）の合成）
攪拌機、温度計、還流冷却器および窒素ガス導入管および滴下槽を備えた反応容器に、ポリオキシエチレンアルキルエーテル硫酸ナトリウム３．０質量部、イオン交換水２６３質量部を仕込み、８０℃まで昇温した。この温度を保持しつつ、滴下槽から、ｎ−ブチルアクリレート４４２．５質量部、アクリロニトリル４０．０質量部、メタクリル酸５．０質量部、アクリルアミド５．０質量部、イタコン酸２．５質量部、ポリオキシエチレン−１−（アリルオキシメチル）アルキル硫酸エステルアンモニウム塩 ５．０質量部、イオン交換水１２５質量部からなるモノマー混合物を、４時間かけて連続滴下した。これと合わせて、過硫酸アンモニウム １．３質量部、イオン交換水 ５．０質量部からなる水溶液を４時間かけて連続滴下した。滴下終了の３０分後に過硫酸アンモニウム １．３質量部、イオン交換水 ３０質量部からなる水溶液を１時間かけて連続滴下し、さらに１時間反応させた。次いで、１０質量％水酸化ナトリウム水溶液１８．０質量部及び２５質量％アンモニア水１．５質量部で中和することで、不揮発分が５０．０％のアクリル樹脂（Ｃ−１）の水分散体を得た。中和剤として使用した塩基性化合物中の水酸化ナトリウムは６７質量％であった。また、水酸化ナトリウムの含有量は、重合体の有するカルボキシル基の４７モル％を中和する量であった。(Synthesis Example 1: Synthesis of acrylic resin (C-1))
A reactor equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping tank was charged with 3.0 parts by mass of sodium polyoxyethylene alkyl ether sulfate and 263 parts by mass of ion-exchanged water, and the temperature was raised to 80 ° C. did. While maintaining this temperature, 442.5 parts by mass of n-butyl acrylate, 40.0 parts by mass of acrylonitrile, 5.0 parts by mass of methacrylic acid, 5.0 parts by mass of acrylamide, 2.5 parts by mass of itaconic acid from the dropping tank. A monomer mixture consisting of 5.0 parts by mass of polyoxyethylene-1- (allyloxymethyl) alkylsulfate ammonium salt and 125 parts by mass of ion-exchanged water was continuously added dropwise over 4 hours. Along with this, an aqueous solution composed of 1.3 parts by mass of ammonium persulfate and 5.0 parts by mass of ion-exchanged water was continuously dropped over 4 hours. 30 minutes after the completion of dropping, an aqueous solution composed of 1.3 parts by mass of ammonium persulfate and 30 parts by mass of ion-exchanged water was continuously added dropwise over 1 hour, and further reacted for 1 hour. Next, the aqueous dispersion of the acrylic resin (C-1) having a nonvolatile content of 50.0% was neutralized with 18.0 parts by mass of a 10% by mass aqueous sodium hydroxide solution and 1.5 parts by mass of 25% by mass ammonia water. Got the body. Sodium hydroxide in the basic compound used as a neutralizing agent was 67% by mass. The content of sodium hydroxide was an amount that neutralized 47 mol% of the carboxyl group of the polymer.
（合成例２：アクリル樹脂（ＲＣ−１）の合成）
合成例１で用いた１０質量％水酸化ナトリウム水溶液１８．０質量部及び２５質量％アンモニア水１．５質量部を、２５質量％アンモニア水３．０質量部に変更した以外は、合成例１と同様にして、不揮発分が５０．０％のアクリル樹脂（ＲＣ−１）の水分散体を得た。中和剤として使用した塩基性化合物中に、金属水酸化物は含まれなかった。(Synthesis Example 2: Synthesis of acrylic resin (RC-1))
Synthesis Example 1 except that 18.0 parts by mass of the 10% by mass aqueous sodium hydroxide solution used in Synthesis Example 1 and 1.5 parts by mass of 25% by mass ammonia water were changed to 3.0 parts by mass of 25% by mass ammonia water. Similarly, an aqueous dispersion of acrylic resin (RC-1) having a nonvolatile content of 50.0% was obtained. The basic compound used as a neutralizing agent did not contain a metal hydroxide.
（合成例３：アクリル系増粘剤（Ｆ−１）の合成）
攪拌機、温度計、還流冷却器および窒素ガス導入管および滴下槽を備えた反応容器に、ポリオキシエチレンアルキルエーテル硫酸ナトリウム３０．０質量部、イオン交換水９４５質量部を仕込み、８０℃まで昇温した。この温度を保持しつつ、滴下槽から、エチルアクリレート２１０．０質量部、メタクリル酸７２質量部からなるモノマー混合物を、４時間かけて連続滴下した。これと合わせて、過硫酸アンモニウム １．８質量部、イオン交換水 ６０．０質量部からなる水溶液を４時間かけて連続滴下した。さらに１時間反応させることで、不揮発分が２３．０％のアクリル系増粘剤（Ｆ−１）を得た。(Synthesis Example 3: Synthesis of acrylic thickener (F-1))
A reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping tank was charged with 30.0 parts by mass of sodium polyoxyethylene alkyl ether sulfate and 945 parts by mass of ion-exchanged water, and the temperature was raised to 80 ° C. did. While maintaining this temperature, a monomer mixture consisting of 210.0 parts by mass of ethyl acrylate and 72 parts by mass of methacrylic acid was continuously added dropwise from the dropping tank over 4 hours. Along with this, an aqueous solution composed of 1.8 parts by mass of ammonium persulfate and 60.0 parts by mass of ion-exchanged water was continuously dropped over 4 hours. Furthermore, the acrylic thickener (F-1) whose non volatile matter is 23.0% was obtained by making it react for 1 hour.
（実施例１：植毛加工用水性樹脂組成物（１）の調製及び評価）
攪拌機を備えた容器に、合成例１で得たアクリル樹脂（Ｃ−１）の水分散体１００質量部、イオン交換水 ４０．０質量部を仕込み、均一になるまで攪拌した。次いで、アクリル系増粘剤（Ｆ−１）２．５質量部を添加し、２５質量％アンモニア水でｐＨ８．０に調整した。その後、ポリオキサゾリン化合物（日本触媒株式会社製「エポクロス ＷＳ−７００」、水溶性タイプ、不揮発分２５質量％、オキサゾリン基量４．５ｍｍｏｌ／ｇ（ｓｏｌｉｄ））６．０質量部を添加し、均一になるまで攪拌した。得られた水性樹脂組成物を２００メッシュ金網で濾過し、植毛加工用水性樹脂組成物（１）を得た。(Example 1: Preparation and evaluation of aqueous resin composition (1) for flocking)
A container equipped with a stirrer was charged with 100 parts by mass of an aqueous dispersion of the acrylic resin (C-1) obtained in Synthesis Example 1 and 40.0 parts by mass of ion-exchanged water, and stirred until uniform. Next, 2.5 parts by mass of an acrylic thickener (F-1) was added, and the pH was adjusted to 8.0 with 25% by mass ammonia water. Thereafter, 6.0 parts by mass of a polyoxazoline compound (“Epocross WS-700” manufactured by Nippon Shokubai Co., Ltd., water-soluble type, non-volatile content 25% by mass, oxazoline group amount 4.5 mmol / g (solid)) was added uniformly. Stir until. The obtained aqueous resin composition was filtered through a 200 mesh wire net to obtain an aqueous resin composition (1) for flocking.
（比較例１：植毛加工用水性樹脂組成物（Ｒ１）の調製及び評価）
実施例１で添加したオキサゾリン基を有する樹脂を添加しなかった以外は、実施例１と同様にして、植毛加工用水性樹脂組成物（Ｒ１）を得た。(Comparative Example 1: Preparation and evaluation of aqueous resin composition (R1) for flocking)
An aqueous resin composition (R1) for flocking processing was obtained in the same manner as in Example 1 except that the resin having an oxazoline group added in Example 1 was not added.
（比較例２：植毛加工用水性樹脂組成物（Ｒ２）の調製及び評価）
実施例１で用いたアクリル樹脂（Ｃ−１）を、アクリル樹脂（ＲＣ−１）に変更した以外は、実施例１と同様にして、植毛加工用水性樹脂組成物（Ｒ２）を得た。(Comparative Example 2: Preparation and evaluation of aqueous resin composition (R2) for flocking)
An aqueous resin composition (R2) for flocking processing was obtained in the same manner as in Example 1, except that the acrylic resin (C-1) used in Example 1 was changed to an acrylic resin (RC-1).
（比較例３：植毛加工用水性樹脂組成物（Ｒ３）の調製及び評価）
実施例１で添加したオキサゾリン基を有する樹脂を、ポリカルボジイミド化合物（日清紡ケミカル株式会社「カルボジライトＥ−０２」に変更した以外は、実施例１と同様にして、植毛加工用水性樹脂組成物（Ｒ３）を得た。(Comparative Example 3: Preparation and evaluation of aqueous resin composition (R3) for flocking)
An aqueous resin composition for flocking processing (R3) in the same manner as in Example 1 except that the resin having an oxazoline group added in Example 1 was changed to a polycarbodiimide compound (Nisshinbo Chemical Co., Ltd. “Carbodilite E-02”). )
［経時安定性の評価］
上記で得た植毛加工用水性樹脂組成物を２３℃にて１ヶ月静置した後、樹脂組成物を２５℃に調整し、そのときの粘度（東機産業株式会社製「ＴＶＢ１０形粘度計」）が調製直後の粘度（初期粘度）と比べて、変化率が１０％未満であるものを「〇」、１０％以上であるものを「×」と評価した。
粘度変化率（％）＝１００×（Ｖ２−Ｖ１）／Ｖ１
Ｖ１：初期粘度（ｍ・Ｐａｓ）
Ｖ２：２３℃で１ヶ月間静置した後の粘度（ｍ・Ｐａｓ）[Evaluation of stability over time]
After leaving the aqueous resin composition for flocking treatment obtained above at 23 ° C. for 1 month, the resin composition was adjusted to 25 ° C., and the viscosity at that time (“TVB10 type viscometer” manufactured by Toki Sangyo Co., Ltd.) ) Was evaluated as “◯” when the change rate was less than 10% compared to the viscosity immediately after preparation (initial viscosity), and “X” when the change rate was 10% or more.
Viscosity change rate (%) = 100 × (V2−V1) / V1
V1: Initial viscosity (m · Pas)
V2: Viscosity after standing for 1 month at 23 ° C. (m · Pas)
［植毛加工品の作製］
上記で得た植毛加工用水性樹脂組成物を、塩化ビニル基材上に膜厚１００μｍとなるように塗布し、静電植毛加工機（株式会社グリーンテクノ製「小型高電圧電源ＧＴ８０Ｎ」、簡易静電植毛実験装置）を用いて、植毛加工を施した。その後、１６０℃で１０分間乾燥し、植毛加工品を得た。[Fabrication processing]
The aqueous resin composition for flocking processing obtained above was applied on a vinyl chloride substrate so as to have a film thickness of 100 μm, and an electrostatic flocking machine (“Small and High Voltage Power Supply GT80N” manufactured by Green Techno Co., Ltd.) Using an electric flocking experiment apparatus), flocking was performed. Then, it dried at 160 degreeC for 10 minute (s), and the flocked product was obtained.
［植毛強度の評価］
上記で得た植毛加工品について、学振型磨耗試験機を用い、磨耗試験（荷重；２００ｇ、磨耗回数；２５００）を行った。磨耗後の植毛加工品の短繊維が脱落していないものを「〇」、脱落しているものを「×」と評価した。[Evaluation of flocking strength]
The flocked product obtained above was subjected to an abrasion test (load: 200 g, number of abrasions: 2500) using a Gakushin type abrasion tester. Evaluation was made as “◯” when the short fibers of the flocked product after wear were not removed, and “×” when the short fibers were removed.
［基材密着性の評価］
上記で得た植毛加工用水性樹脂組成物を塩化ビニル基材上に膜厚１００μｍとなるように塗布し、１６０℃で１０分間乾燥し、基材密着性評価用の試験片を得た。この試験片上に接着剤（東亜合成株式会社製「アロンアルファ」）を用いて、チェック端子を貼り付けた。接着剤が固化した後、オートグラフ（株式会社島津製作所製「ＡＧ−Ｘ ｐｌｕｓ １ｋＮ」）を用いて、１８０°方向に引張試験を行い、剥離強度を測定した。[Evaluation of substrate adhesion]
The aqueous resin composition for flocking processing obtained above was applied on a vinyl chloride substrate so as to have a film thickness of 100 μm and dried at 160 ° C. for 10 minutes to obtain a test piece for evaluating substrate adhesion. A check terminal was affixed on the test piece using an adhesive (“Aron Alpha” manufactured by Toa Gosei Co., Ltd.). After the adhesive was solidified, a tensile test was performed in a 180 ° direction using an autograph (“AG-X plus 1 kN” manufactured by Shimadzu Corporation) to measure the peel strength.
上記の実施例及び比較例で得られた植毛加工用水性樹脂組成物の評価を表１に示す。 Table 1 shows the evaluation of the aqueous resin composition for flocking processing obtained in the above Examples and Comparative Examples.
実施例１の本発明の植毛加工用水性樹脂組成物は、経時安定性に優れ、植毛強度及び基材密着性に優れる植毛加工品が得られることが確認された。 It was confirmed that the aqueous resin composition for flocking processing of Example 1 of the present invention was excellent in temporal stability, and a flocked product excellent in flocking strength and substrate adhesion was obtained.
一方、比較例１は、架橋剤を用いなかった例であるが、植毛加工品の植毛強度に劣ることが確認された。 On the other hand, although the comparative example 1 is an example which did not use a crosslinking agent, it was confirmed that it is inferior to the flocking strength of a flocking processed product.
比較例２は、塩基性化合物として、金属水酸化物を用いなかった例であるが、植毛加工品の植毛強度及び基材密着性に劣ることが確認された。 Although the comparative example 2 is an example which did not use a metal hydroxide as a basic compound, it was confirmed that it is inferior to the flocking strength and base-material adhesiveness of a flocking processed product.
比較例３は、ポリオキサゾリン化合物の代わりに、ポリカルボジイミド化合物を用いた例であるが、経時安定性に劣ることが確認された。 Comparative Example 3 was an example using a polycarbodiimide compound instead of the polyoxazoline compound, but it was confirmed that the stability over time was inferior.
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| JPH10251474A (en) * | 1997-03-07 | 1998-09-22 | Nippon Carbide Ind Co Inc | Water-based acrylic resin composition |
| JP2002302876A (en) * | 2001-04-06 | 2002-10-18 | Nippon Carbide Ind Co Inc | Water-dispersible resin composition for fiber processing |
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| WO2015186733A1 (en) * | 2014-06-03 | 2015-12-10 | ユニチカ株式会社 | Aqueous dispersion, and laminate |
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| JP3875760B2 (en) * | 1997-03-10 | 2007-01-31 | 株式会社クラレ | Method for producing chlorinated aromatic compound |
| US20090143524A1 (en) * | 2005-09-29 | 2009-06-04 | Yoshifumi Nakayama | Fiber-Reinforced Thermoplastic Resin Composition, Method for Producing the Same, and Carbon Fiber for Thermoplastic Resin |
| JP5123539B2 (en) * | 2007-03-06 | 2013-01-23 | 大日精化工業株式会社 | Copolymer and use thereof |
| EP2591010B1 (en) * | 2010-07-09 | 2014-12-03 | Lubrizol Advanced Materials, Inc. | Blends of acrylic copolymer thickeners |
| IN2014MN01422A (en) * | 2011-12-16 | 2015-07-03 | Mitsui Chemicals Tohcello Inc | |
| CN102827518A (en) * | 2012-06-01 | 2012-12-19 | 安徽省金盾涂料有限责任公司 | Water paint composition |
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| JPH01292179A (en) * | 1988-05-16 | 1989-11-24 | Nippon Shokubai Kagaku Kogyo Co Ltd | Resin for yarn fabrication |
| JPH10251474A (en) * | 1997-03-07 | 1998-09-22 | Nippon Carbide Ind Co Inc | Water-based acrylic resin composition |
| JP2002302876A (en) * | 2001-04-06 | 2002-10-18 | Nippon Carbide Ind Co Inc | Water-dispersible resin composition for fiber processing |
| JP2003096148A (en) * | 2001-09-27 | 2003-04-03 | Dainippon Ink & Chem Inc | Polymer aqueous dispersion and its production process |
| JP2011526953A (en) * | 2008-06-30 | 2011-10-20 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Golf balls containing ionomers and polyamines or tertiary polyamides |
| WO2015186733A1 (en) * | 2014-06-03 | 2015-12-10 | ユニチカ株式会社 | Aqueous dispersion, and laminate |
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