JPH1150378A - Production of printed fabric with permeability, moisture resistance, photo-accumulative property and recurrent reflection - Google Patents
Production of printed fabric with permeability, moisture resistance, photo-accumulative property and recurrent reflectionInfo
- Publication number
- JPH1150378A JPH1150378A JP20419797A JP20419797A JPH1150378A JP H1150378 A JPH1150378 A JP H1150378A JP 20419797 A JP20419797 A JP 20419797A JP 20419797 A JP20419797 A JP 20419797A JP H1150378 A JPH1150378 A JP H1150378A
- Authority
- JP
- Japan
- Prior art keywords
- resin layer
- glass beads
- photo
- weight
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は，透湿防水性能およ
び夜間の蓄光再帰反射性能に優れた雨衣，スポーツ衣料
等に用いられる透湿防水性蓄光再帰反射性プリント布の
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a moisture-permeable waterproof luminous retroreflective printed cloth used for rain clothing, sports clothing, etc., which is excellent in moisture-permeable waterproofness and night-time retroreflective performance. .
【０００２】[0002]
【従来の技術】従来から，夜間作業の安全性を確保する
ために，夜間の視認性に優れた再帰性反射材が広く使用
されている。この種の再帰性反射材には，ガラスビーズ
型とノンビーズ型があるが，ガラスビーズの良好な再帰
反射性能を有するガラスビーズ型が主流となっている。
ガラスビーズ型には，ガラスビーズが樹脂層に埋没した
クローズドタイプと，ガラスビーズの約半分が空気中に
露出したオープンタイプとがあり，再帰性反射材に車の
ヘッドライト等の光が入射したときには優れた反射輝度
を呈するが，暗闇等の光の存在がまったくないとき，自
ら光ることはないという問題点を有している。これらの
再帰性反射材の主用途としては，裏面に粘着剤層等を設
けて他物に貼りつけて使用する再帰性反射シートが道路
標識類に使用されている一方，裏面に繊維布帛をバッキ
ングして使用する再帰性反射布帛が警察，工事関係者の
安全服等に使用されている。2. Description of the Related Art Conventionally, retroreflective materials having excellent nighttime visibility have been widely used to ensure the safety of nighttime work. This type of retroreflective material includes a glass bead type and a non-bead type, and a glass bead type having good retroreflective performance of glass beads is mainly used.
The glass bead type includes a closed type in which the glass beads are buried in the resin layer and an open type in which about half of the glass beads are exposed to the air. Light such as car headlights enters the retroreflective material. Sometimes it exhibits excellent reflection luminance, but has a problem that it does not shine on its own when there is no light such as darkness. The main use of these retroreflective materials is as a retroreflective sheet, which is provided with an adhesive layer or the like on the back surface and attached to other objects for use in road signs, while a backing of fiber fabric on the back surface is used. Retroreflective fabrics are used for safety clothing for police and construction workers.
【０００３】最近，安全に対する意識の高まりから，透
湿防水性素材としてのウィンドブレーカー，スキーウェ
ア等のスポーツ衣料に再帰性反射布帛を縫いつけて使用
されはじめており，今後一層の需要増加が予想されてい
るが，縫いつけでは衣料としての一体感に欠け，ファッ
ション上好まれていないのが現状であり，また，縫いつ
けた部分の風合が硬くなるという問題もあった。一方，
蓄光性材料は，例えば，合成樹脂に混入し，成形品の形
で衣料品の附属品として，また，ペイント化，インク化
し，繊維布帛等にプリント加工を行うことにより，夜間
時の危険防止や装飾品等として有用されており，暗闇中
では大きな効果を発揮するが，周囲に光の存在があると
きは効果を発揮できないという問題点を有している。[0003] Recently, with increasing awareness of safety, retroreflective cloth has been sewn on sports clothing such as windbreakers and ski wear as a moisture-permeable and waterproof material, and the use thereof has been started. However, sewing does not have a sense of unity as clothing and is not favored in fashion at present, and there is also a problem that the texture of the sewn part becomes hard. on the other hand,
Luminescent materials are mixed with synthetic resins, for example, as accessories to clothing in the form of molded products, or by painting, ink-forming, and printing on fiber fabrics to prevent danger at night. It is useful as a decorative article, etc., and exhibits a great effect in the dark, but has a problem that it cannot exert an effect when there is light around.
【０００４】[0004]
【発明が解決しようとする課題】本発明は，上述の現状
に鑑みて行われたもので，優れた蓄光再帰反射性能と優
れた透湿防水性能を有する透湿防水性蓄光再帰反射性プ
リント布を製造することを目的とするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and is directed to a moisture-permeable waterproof luminous retroreflective printed cloth having excellent luminous retroreflection performance and excellent moisture-permeable and waterproof performance. Is intended to be manufactured.
【０００５】[0005]
【課題を解決するための手段】本発明は上記目的を達成
するもので，次の構成よりなるものである。すなわち本
発明は「繊維布帛の表面に，アルミニウム，銀等の光反
射性物質を５〜５０重量％含有するポリウレタン樹脂主
体の合成重合体からなる樹脂層を乾式コーティング法で
形成する第１工程，該樹脂層上に蓄光性微粉末を５〜５
０重量％，屈折率1.７以上，平均球径２０〜１００μｍ
の真球状透明ガラスビーズを２０〜８０重量％含有する
アクリル樹脂および／またはポリウレタン樹脂を主体と
する合成重合体からなる樹脂層をプリント法にてガラス
ビーズの直径かまたはこれより薄く形成する第２工程か
らなることを特徴とする透湿防水性蓄光再帰反射性プリ
ント布の製造方法」を要旨とするものである。The present invention attains the above object and has the following constitution. That is, the present invention provides "a first step of forming a resin layer made of a synthetic polymer mainly composed of a polyurethane resin containing 5 to 50% by weight of a light reflective substance such as aluminum or silver on the surface of a fiber fabric by a dry coating method, 5 to 5 luminous fine powders are placed on the resin layer.
0% by weight, refractive index 1.7 or more, average sphere diameter 20-100 μm
Forming a resin layer composed of a synthetic polymer mainly composed of an acrylic resin and / or a polyurethane resin containing 20 to 80% by weight of the spherical transparent glass beads by a printing method so as to have a diameter equal to or smaller than the diameter of the glass beads. A method for producing a moisture-permeable waterproof luminous retroreflective printed cloth characterized by comprising a process.
【０００６】[0006]
【発明の実施の形態】以下，本発明について詳細に説明
する。本発明で用いられる繊維布帛としては，ナイロン
６やナイロン６６で代表されるポリアミド系合成繊維，
ポリエチレンテレフタレートで代表されるポリエステル
系合成繊維，ポリアクリロニトリル系合成繊維，ポリビ
ニルアルコール系合成繊維，トリアセテート等の半合成
繊維またはナイロン６／木綿，ポリエチレンテレフタレ
ート／木綿等の混合繊維からなる織物，編物，不織布等
を挙げることができる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Examples of the fiber cloth used in the present invention include polyamide synthetic fibers represented by nylon 6 and nylon 66,
Fabrics, knits, and nonwoven fabrics composed of polyester synthetic fibers represented by polyethylene terephthalate, semi-synthetic fibers such as polyacrylonitrile synthetic fibers, polyvinyl alcohol synthetic fibers, and triacetate, or mixed fibers of nylon 6 / cotton, polyethylene terephthalate / cotton, and the like. And the like.
【０００７】本発明では，上記の繊維布帛に必要に応じ
て撥水剤処理を施したものを用いてもよい。これは樹脂
溶液の布帛内部への浸透を防ぐための一手段である。こ
の場合の撥水剤としては，パラフィン系撥水剤やポリシ
ロキサン系撥水剤，フッ素系撥水剤等の公知のものでよ
く，その処理も，一般に行われているパディング法，ス
プレー法等の公知の方法で行えばよい。特に良好な撥水
性を必要とする場合にはフッ素系撥水剤を使用し，例え
ば，アサヒガード７３０（旭硝子株式会社製，フッ素系
撥水剤エマルジョン）５％の水分散液でパディング（絞
り率３５％）した後，１６０℃で１分間の熱処理を行う
方法等によって行えばよい。In the present invention, the above-mentioned fiber cloth may be subjected to a water repellent treatment as required. This is one means for preventing the permeation of the resin solution into the fabric. The water repellent in this case may be a known water repellent such as a paraffin water repellent, a polysiloxane water repellent, a fluorine water repellent, etc., and the treatment is also performed by a commonly used padding method, spray method, or the like. May be performed by a known method. When particularly good water repellency is required, a fluorine-based water repellent is used. For example, padding (squeezing ratio) with a 5% aqueous dispersion of Asahigard 730 (a fluorine-based water-repellent emulsion manufactured by Asahi Glass Co., Ltd.) 35%) and then heat-treated at 160 ° C. for 1 minute.
【０００８】本発明では，上記繊維布帛上に第１工程と
してアルミニウム，銀等の光反射性物質を５〜５０重量
％含有するポリウレタン樹脂を主体とする合成重合体の
溶液を塗布し，乾燥して樹脂膜を形成する，いわゆる乾
式コーティング法による製膜を行う。In the present invention, as a first step, a solution of a synthetic polymer mainly composed of a polyurethane resin containing 5 to 50% by weight of a light-reflective substance such as aluminum or silver is applied to the above-mentioned fiber cloth and dried. To form a resin film by a so-called dry coating method.
【０００９】ここでいう光反射性物質としては，アルミ
ニウム，銀，金，白金等の金属微粉末またはこれらの金
属微粉末をミネラルターペン，ポリウレタン樹脂等に練
り込んだペースト状物，アルミニウム箔片，二酸化チタ
ン，薄板状雲母粉末を二酸化チタンで被覆したパール顔
料等の光反射性に優れた物質であればよく，これらの光
反射性物質は，単独でも，混合でも使用できる。使用量
は，後述の樹脂層に対して均一に５〜５０重量％必要で
あり，５重量％未満では，光を透過させてしまい，得ら
れる布帛の再帰反射性能が劣り，また，５０重量％を超
えて用いても，再帰反射性能の向上が少なく，かつ得ら
れる樹脂層の風合が硬くなる上に脆くなるので好ましく
ない。The light-reflecting material used herein includes fine metal powders of aluminum, silver, gold, platinum and the like, or pastes obtained by kneading these metal fine powders in mineral terpenes, polyurethane resins, etc., aluminum foil pieces, Titanium dioxide, a pearl pigment obtained by coating a thin plate-like mica powder with titanium dioxide, and the like may be used as long as they are excellent in light reflectivity. These light-reflective substances can be used alone or in combination. The amount used must be 5 to 50% by weight uniformly with respect to the resin layer described below. If the amount is less than 5% by weight, light is transmitted, and the retroreflective performance of the obtained fabric is inferior. It is not preferable to use the resin layer in excess of the above because the improvement of the retroreflection performance is small and the feeling of the obtained resin layer becomes hard and brittle.
【００１０】本発明で用いるポリウレタン樹脂は，ポリ
イソシアネートとポリオールを反応せしめて得られる共
重合体であり，イソシアネート成分として，芳香族ジイ
ソシアネート，脂肪族ジイソシアネート，脂環族ジイソ
シアネートの単独またはこれらの混合物を用い，例え
ば，トリレン2,４−ジイソシアネート，４，4'−ジフェ
ニルメタンジイソシアネート，1,６−ヘキサンジイソシ
アネート，1,４−シクロヘキサンジイソシアネート等を
用い，また，ポリオール成分としては，ポリエーテルポ
リオール，ポリエステルポリオールを用い，ポリエーテ
ルポリオールは，ポリエチレングリコール，ポリプロピ
レングリコール，ポリテトラメチレングリコール等を用
い，ポリエステルポリオールは，エチレングリコール，
プロピレングリコール等のジオールとアジピン酸，セバ
チン酸等の２塩基酸との反応生成物やカプロラクトン等
の開環重合物を用いる。The polyurethane resin used in the present invention is a copolymer obtained by reacting a polyisocyanate and a polyol. As the isocyanate component, an aromatic diisocyanate, an aliphatic diisocyanate, an alicyclic diisocyanate alone or a mixture thereof is used. For example, tolylene 2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, 1,4-cyclohexane diisocyanate, etc. are used, and as a polyol component, polyether polyol and polyester polyol are used. The polyether polyol used was polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. The polyester polyol was ethylene glycol,
A reaction product of a diol such as propylene glycol with a dibasic acid such as adipic acid or sebacic acid or a ring-opening polymer such as caprolactone is used.
【００１１】本発明でいうポリウレタン樹脂を主体とす
る合成重合体とは，上述のポリウレタン樹脂を５０％以
上含む合成重合体をいい，その他の合成重合体としてア
クリル樹脂を含んでいてもよく，ここで用いるアクリル
樹脂は主としてアクリル酸，メタクリル酸またはこれら
の誘導体の重合体からなっていれば何れでもよく，一般
には，アクリル酸メチル，アクリル酸エチル，アクリル
酸ブチル等のアクリル酸エステル，メタクリル酸メチ
ル，メタクリル酸エチル，メタクリル酸ブチル等のメタ
クリル酸エステルを主成分とした重合体を用いる。The synthetic polymer mainly composed of a polyurethane resin in the present invention means a synthetic polymer containing 50% or more of the above-mentioned polyurethane resin, and may contain an acrylic resin as another synthetic polymer. The acrylic resin used in the present invention may be any resin mainly composed of a polymer of acrylic acid, methacrylic acid or a derivative thereof. In general, acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, etc., and methyl methacrylate , A polymer containing methacrylate as a main component such as ethyl methacrylate and butyl methacrylate is used.
【００１２】上述のポリウレタン樹脂を主体とする合成
重合体の溶媒としてはメチルエチルケトン，酢酸エチ
ル，トルエン，Ｎ，Ｎ−ジメチルホルムアミド，ジオキ
サン，イソプロピルアルコール，水等を適宜用いればよ
いが，基布内部への樹脂溶液の浸透性，加工コスト，さ
らに，得られる布帛の再帰反射性能から見て，揮発性の
高いメチルエチルケトン，酢酸エチル，トルエン，イソ
プロピルアルコール等を主溶媒とした溶剤型の樹脂で，
樹脂層が無孔タイプのものを用いる方が有利である。As a solvent for the above-mentioned synthetic polymer mainly composed of a polyurethane resin, methyl ethyl ketone, ethyl acetate, toluene, N, N-dimethylformamide, dioxane, isopropyl alcohol, water and the like may be appropriately used. In view of the resin solution's permeability, processing cost, and the retroreflective performance of the resulting fabric, it is a solvent-type resin with highly volatile methyl ethyl ketone, ethyl acetate, toluene, isopropyl alcohol, etc. as the main solvent.
It is more advantageous to use a non-porous resin layer.
【００１３】本発明における第１工程の乾式コーティン
グ加工では，乾燥樹脂膜重量が２０ｇ／ｍ2 以下，好ま
しくは１５ｇ／ｍ2 以下になるようにコーティングを行
う。第１工程での樹脂塗布量が多いと，防水性能は優れ
るが，極端な透湿性能の低下を招くとともに，風合が硬
くなるので好ましくない。コーティングに際しては，ナ
イフコーター，コンマコーター，リバースコーター等を
用いて適宜行えばよいが，樹脂塗布量から見て，ナイフ
コーターを用いるのが最も適している。In the dry coating of the first step in the present invention, the coating is performed so that the dry resin film weight is 20 g / m 2 or less, preferably 15 g / m 2 or less. If the amount of the resin applied in the first step is large, the waterproof performance is excellent, but the moisture permeability is extremely lowered and the feeling becomes hard, which is not preferable. The coating may be appropriately performed using a knife coater, a comma coater, a reverse coater, or the like, but the use of a knife coater is most suitable in view of the amount of resin applied.
【００１４】上述の第１工程の後，本発明では，第２工
程として，その樹脂層上に蓄光性微粉末を５〜５０重量
％，屈折率1.７以上，平均球径２０〜１００μｍの真球
状透明ガラスビーズを２０〜８０重量％含有するアクリ
ル樹脂および／またはポリウレタン樹脂を主体とする合
成重合体からなる樹脂層をプリント法にてガラスビーズ
の直径かまたはこれより薄く形成する。本発明で“およ
び／または”なる語句は，双方のうちの一方または両方
を意味するものとする。After the above-mentioned first step, in the present invention, as a second step, 5 to 50% by weight of a luminous fine powder, a refractive index of 1.7 or more and an average sphere diameter of 20 to 100 μm are formed on the resin layer. A resin layer composed of a synthetic polymer mainly composed of an acrylic resin and / or a polyurethane resin containing 20 to 80% by weight of true spherical transparent glass beads is formed by a printing method to have a diameter equal to or smaller than the diameter of the glass beads. In the present invention, the phrase "and / or" shall mean one or both of the two.
【００１５】本発明で用いる蓄光性微粉末とは，紫外線
等で刺激しその刺激を停止した後も残光が数１０分〜数
時間にわたって肉眼で認められる効果を有する公知の微
粉末のことであり，例えば，ＺｎＳ：Ｃｕ，ＺｎＣｄ
Ｓ：Ｃｕ，ＣａＳ：Ｂｉ，ＣａＳｒＳ：Ｂｉ等の硫化亜
鉛系蓄光性微粉末やＳｒＡｌ2 Ｏ4 ，ＣａＡｌ2 Ｏ4 等
のアルミン酸系蓄光性微粉末，Ａｌ2 Ｏ3 ，ＳｒＣ
ｌ2 ，ＢａＣＯ3 などの酸化物，塩類を主成分とする蓄
光性微粉末等が挙げられ，その使用量は，後述の樹脂層
に対して５〜５０重量％必要であり，５重量％未満で
は，得られる布帛の蓄光性能に乏しく，５０重量％を超
えると，後述のガラスビーズに対する光の入射および反
射に対して障害となり，結果として得られる布帛の再帰
反射性能に悪影響を及ぼすことになる。The phosphorescent fine powder used in the present invention is a known fine powder having an effect that the afterglow can be visually recognized for several tens of minutes to several hours even after the stimulation is stopped by ultraviolet rays or the like. Yes, for example, ZnS: Cu, ZnCd
S: Cu, CaS: Bi, CaSrS: Bi, etc., zinc sulfide-based luminous fine powders, SrAl 2 O 4 , CaAl 2 O 4, etc., aluminate-based luminous fine powders, Al 2 O 3 , SrC
luminous fine powder mainly composed of oxides such as l 2 and BaCO 3 , salts and the like. The amount of the powder used is 5 to 50% by weight based on the resin layer described below, and is less than 5% by weight. In this case, the obtained fabric has poor light storage performance, and if it exceeds 50% by weight, it impedes the incidence and reflection of light on the glass beads described later, which adversely affects the retroreflective performance of the resulting fabric. .
【００１６】蓄光性微粉末の粒径は１〜１００μｍであ
ればよいが，５〜４０μｍ径を主体として用いる方が，
後述の真球状透明ガラスビーズの中心径から見て好まし
い。粒径が１μｍ未満では，得られる布帛の蓄光性能に
乏しく，また，１００μｍより大きいと，得られる布帛
の厚みが大きくなり，風合が硬くなるばかりか，再帰反
射性能を低下させることになるので好ましくない。The particle size of the luminous fine powder may be 1 to 100 μm.
It is preferable in view of the center diameter of the spherical transparent glass beads described later. If the particle size is less than 1 μm, the resulting fabric has poor light storage performance. If the particle size is greater than 100 μm, the thickness of the resulting fabric increases, not only the feel becomes hard, but also the retroreflective performance decreases. Not preferred.
【００１７】本発明の真球状透明ガラスビーズは，Ｔｉ
Ｏ2 ，ＳｉＯ2 ，ＢａＯ，ＺｎＯ，ＣａＯ，Ｋ2 Ｏ，Ｐ
ｂＯ，Ｎａ2 Ｏ等の１種以上からなる屈折率1.７以上の
ガラス塊状物を，噴出球状化法，ロータリーキルン球状
化法等により真球化した多数の透明ガラスビーズであれ
ばよく，この透明ガラスビーズとしては，好ましくはＴ
ｉＯ2 ，ＢａＯ，ＺｎＯを主成分とする屈折率1.７０〜
2.２０のガラスビーズを主体として用いる。屈折率が1.
７未満の場合は，ガラスビーズを含有する樹脂層の屈折
率が一般的には約1.５程度なので，樹脂層の厚みにも依
存するが，優れた再帰反射性能を得ることが困難とな
る。また，現状では，屈折率が2.２０を超えるガラスビ
ーズを得ようとすれば，失透率が高くなってしまい，製
法上非常に難しい。The spherical transparent glass beads of the present invention are made of Ti
O 2 , SiO 2 , BaO, ZnO, CaO, K 2 O, P
A large number of transparent glass beads obtained by spheroidizing a glass lump composed of at least one of bO, Na 2 O, and the like having a refractive index of 1.7 or more by a spheroidizing method, a rotary kiln spheroidizing method, or the like may be used. As the transparent glass beads, preferably, T
Refractive index of 1.70 or more containing iO 2 , BaO, and ZnO as main components
2. Mainly use the glass beads of 20. Refractive index is 1.
If it is less than 7, since the refractive index of the resin layer containing the glass beads is generally about 1.5, it depends on the thickness of the resin layer, but it is difficult to obtain excellent retroreflective performance. . Further, at present, if glass beads having a refractive index of more than 2.20 are to be obtained, the devitrification rate becomes high, which is very difficult in terms of the production method.
【００１８】ガラスビーズの球径は，２０〜１００μ
ｍ，好ましくは４０〜８０μｍを主体とする方がよく，
２０μｍ未満では，得られる布帛の再帰反射性能に乏し
く，また１００μｍを超えると，得られる布帛の厚みが
大きくなり，風合が硬くなる。その使用量は，後述の樹
脂層に対し２０〜８０重量％必要であり，２０重量％未
満では，得られる布帛の再帰反射性能に乏しく，８０重
量％を超えても，再帰反射性能の向上が少なく，かつ風
合が硬くなるとともに，樹脂層が脆くなる。The spherical diameter of the glass beads is 20 to 100 μm.
m, preferably 40-80 μm,
If it is less than 20 μm, the retroreflective performance of the obtained fabric is poor, and if it exceeds 100 μm, the thickness of the obtained fabric becomes large and the feeling becomes hard. The used amount is 20 to 80% by weight with respect to the resin layer described below. If the amount is less than 20% by weight, the retroreflective performance of the obtained fabric is poor. Less, the feel becomes hard, and the resin layer becomes brittle.
【００１９】ここで用いる樹脂層の合成重合体は，前述
の第１工程と同様の合成重合体であればよいが，光透過
性に優れたアクリル樹脂および／またはポリウレタン樹
脂を８０重量％以上有している方が，得られる布帛の蓄
光再帰反射性能から見て好ましく，合成重合体の形態と
しては，後述のプリントの加工性，作業性の点から，エ
マルジョン型溶液が好適に用いられ，第１工程の樹脂層
に対する接着力向上，得られる樹脂層の耐久性向上のた
めに，イソシアネート系架橋剤，エポキシ系架橋剤等を
併用してもよい。The synthetic polymer of the resin layer used here may be the same synthetic polymer as in the first step described above, but contains at least 80% by weight of an acrylic resin and / or a polyurethane resin having excellent light transmittance. This is preferable in view of the luminous and retroreflective performance of the obtained fabric, and the form of the synthetic polymer is preferably an emulsion type solution from the viewpoint of print processing and workability described below. An isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, or the like may be used in combination in order to improve the adhesion to the resin layer in one step and to improve the durability of the obtained resin layer.
【００２０】本発明では，上述の樹脂層をプリント法に
て形成するが，プリント方法としては，一般に公知のプ
リント装置を用いればよく，具体的には，フラットスク
リーン捺染機，ロータリースクリーン捺染機，グラビア
ロールコーター等を挙げることができる。樹脂層の膜厚
は，使用するガラスビーズの平均球径と同等またはそれ
より小さい方が望ましい。ガラスビーズの平均球径より
膜厚が大きいと，ガラスビーズとその樹脂層の表面との
間に蓄光性微粉末が入り込みやすくなり，再帰反射性能
を阻害することになるので好ましくない。In the present invention, the above-mentioned resin layer is formed by a printing method. As a printing method, a generally known printing apparatus may be used. Specifically, a flat screen printing machine, a rotary screen printing machine, A gravure roll coater can be used. The thickness of the resin layer is desirably equal to or smaller than the average sphere diameter of the glass beads used. If the film thickness is larger than the average sphere diameter of the glass beads, the luminous fine powder easily enters between the glass beads and the surface of the resin layer, which impairs the retroreflective performance, which is not preferable.
【００２１】また本発明では，撥水性能と防水性能およ
びそれらの耐久性を向上させるために，樹脂層に対して
浸透性に優れた溶剤型フッ素系撥水剤を付与してもよ
い。ここで用いられる溶剤型フッ素系撥水剤とは，パー
フルオロアルキル基含有アクリレート，パーフルオロア
ルキル基含有メタクリレートなどをトリクロロエタン，
ミネラルターペン等の溶剤に溶解させた公知のものでよ
い。その処理も，一般に行われているパディング法，ス
プレー法等の公知の方法で行えばよく，例えば，アサヒ
ガードＡＧ−５７０（旭硝子株式会社製）の５％ミネラ
ルターペン溶液をパディング（絞り率４０％）し，乾燥
後，１６０℃で１分間の熱処理を行う方法等によって行
えばよい。本発明は，以上の構成よりなるものである。In the present invention, a solvent-type fluorine-based water repellent having excellent permeability to the resin layer may be provided in order to improve the water repellency, the waterproof performance and the durability thereof. The solvent-type fluorine-based water repellent used herein includes perfluoroalkyl group-containing acrylate, perfluoroalkyl group-containing methacrylate, and the like, as trichloroethane,
A known material dissolved in a solvent such as a mineral terpene may be used. The treatment may also be performed by a commonly known method such as a padding method or a spraying method, for example, padding a 5% mineral terpene solution of Asahigard AG-570 (manufactured by Asahi Glass Co., Ltd.) (aperture ratio of 40%). After drying, a heat treatment at 160 ° C. for 1 minute may be performed. The present invention has the above configuration.
【００２２】[0022]
【作用】一般的なガラスビーズ型の再帰性反射材や再帰
性反射布帛は，透明ガラスビーズを細密充填状に敷き詰
めてあるので，樹脂層中のガラスビーズの後方に蓄光性
微粉末を存在させても蓄光性能が発現せず，また，ガラ
スビーズの前方に存在させた場合，透明性を大きく減少
させるので，再帰反射性能が大きく低下する。本発明の
ごとく，まず，透湿性能および防水性能を有する光反射
層を形成させてから，その上層部に真球状透明ガラスビ
ーズと蓄光性微粉末を樹脂層に混在させ，しかも透明ガ
ラスビーズを樹脂層表面から突出した状態に配置してお
くと，樹脂層の蓄光性微粉末が蓄光して発光するととも
に，樹脂層から突出したガラスビーズが光をよく反射す
るので，優れた透湿防水性能と同時に優れた蓄光再帰反
射性能を得ることが可能となる。[Function] In a general glass bead-type retroreflective material or retroreflective cloth, transparent glass beads are laid in a close-packed manner, so that the phosphorescent fine powder exists behind the glass beads in the resin layer. However, when the phosphorescent performance is not exhibited, and when it is present in front of the glass beads, the transparency is greatly reduced, so that the retroreflective performance is greatly reduced. As in the present invention, first, a light reflecting layer having moisture permeability and waterproofing properties is formed, and then spherical transparent glass beads and luminous fine powder are mixed in a resin layer on the upper layer thereof, and the transparent glass beads are formed. When placed in a state protruding from the surface of the resin layer, the luminous fine powder of the resin layer luminesces and emits light, and the glass beads protruding from the resin layer reflect light well. At the same time, excellent phosphorescent retroreflection performance can be obtained.
【００２３】[0023]
【実施例】以下，本発明を実施例によってさらに具体的
に説明するが，実施例における布帛の性能の測定，評価
は，次の方法で行った。 （１）再帰反射性能 ＪＩＳ Ｚ−９１１７により反射輝度（観測角0.２°，
入射角５°）を測定した。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The measurement and evaluation of the performance of the fabric in the examples were performed by the following methods. (1) Retroreflective performance Reflection luminance (observation angle 0.2 °, JIS Z-9117)
Incident angle 5 °).
【００２４】（２）蓄光性能 ２０℃の室内で布帛から３０cmの距離をおき，１５Ｗの
蛍光灯で１０分間照射後，暗室で光って見える視認時間
により，蓄光性を次の４段階で評価した。 ◎ ： ６０分以上明らかに光って見える ○ ： ３０〜６０分間明らかに光って見える △ ： ５〜３０分間明らかに光って見える × ： まったく光って見えないか，また，光って見え
ても，５分以内でほとんど光が視認できなくなる。 （３）透湿性能 ＪＩＳ Ｌ−１０９９（Ａ−１法）により透湿度を測定
した。 （４）防水性能 ＪＩＳ Ｌ−１０９６（低水圧法）により耐水圧を測定
した。(2) Luminescent performance After illuminating with a 15 W fluorescent lamp for 10 minutes at a distance of 30 cm from the cloth in a room at 20 ° C., and then observing the visible light shining in a dark room, the luminous ability was evaluated in the following four steps. . ◎: clearly visible for 60 minutes or more ○: clearly visible for 30 to 60 minutes △: clearly visible for 5 to 30 minutes ×: 5 or not visible at all Within minutes, light is almost invisible. (3) Moisture permeability The moisture permeability was measured according to JIS L-1099 (A-1 method). (4) Waterproofing performance Water resistance was measured according to JIS L-1096 (low water pressure method).
【００２５】実施例１ 経糸，緯糸の双方にナイロンハイマルチフィラメント７
０デニール／６８フィラメントを用いた経糸密度１２０
本／インチ，緯糸密度９０本／インチの平織物を用意
し，これに通常の方法にて精練および染色（日本化薬株
式会社製，酸性染料のKayacyl Sky Blue Ｒ １％owf)
を行い，アサヒガードＬＳ−３１７（旭硝子株式会社
製，フッ素系エマルジョン撥水剤）５％水分散液でパデ
ィング（絞り率４０％）し，乾燥後，１７０℃で４０秒
間の熱処理を行った。続いて，鏡面ロールをもつカレン
ダー加工機を用いて，温度１７０℃，圧力３０kg／c
m2 ，速度２０ｍ／分の条件でカレンダー加工を行い，
コーティング用の基布を得た。Example 1 Nylon high multifilament 7 was used for both the warp and the weft.
Warp density 120 using 0 denier / 68 filaments
A plain woven fabric having a yarn density of 90 yarns / inch and a weft density of 90 yarns / inch is prepared, and scouring and dyeing are performed on the woven fabric in the usual manner (Kayacyl Sky Blue R 1% owf, manufactured by Nippon Kayaku Co., Ltd.)
The resultant was padded with a 5% aqueous dispersion of Asahigard LS-317 (manufactured by Asahi Glass Co., Ltd., fluorine-based emulsion water repellent) (squeezing ratio: 40%), dried, and then heat-treated at 170 ° C. for 40 seconds. Then, using a calendering machine with a mirror roll, the temperature was 170 ° C and the pressure was 30 kg / c.
calendering under the conditions of m 2 and speed 20m / min,
A base fabric for coating was obtained.
【００２６】次に，上記カレンダー加工面に下記処方１
の固形分２２％の塗布液をナイフコーターを用いて塗布
量４０ｇ／ｍ2 にて塗布した後，１００℃で３分間の乾
燥を行い，アルミニウム微粉末を２６重量％含有する樹
脂層を形成した。 処方１ ラックスキン Ｕ−２０１５−１ １００部 （セイコー化成株式会社製，溶剤型無孔タイプポリウレ
タン樹脂） レザミン Ｘ １部 （大日精化工業株式会社製，イソシアネート系架橋剤） Ｓａｐ ４１２０ １０部 （昭和電工株式会社製，平均粒径７μｍのアルミニウム
微粉末をミネラルターペンに練り込んだ固形分７２％の
アルミニウムペースト） メチルエチルケトン １０部 トルエン １０部Next, the following formula 1 was applied to the calendered surface.
Was applied using a knife coater at a coating amount of 40 g / m 2 and dried at 100 ° C. for 3 minutes to form a resin layer containing 26% by weight of aluminum fine powder. . Formulation 1 Lac Skin U-2015-1 100 parts (Seiko Chemical Co., Ltd., solvent type non-porous polyurethane resin) Resamine X 1 part (Dainichi Seika Industry Co., Ltd., isocyanate-based cross-linking agent) Sap 4120 10 parts (Showa) Aluminum paste with a 72% solid content obtained by kneading aluminum fine powder having an average particle diameter of 7 μm into a mineral turpent manufactured by Denko Corporation) Methyl ethyl ketone 10 parts Toluene 10 parts
【００２７】次に，フラットスクリーン捺染機を用い
て，上記樹脂層上に５mm角単位の市松模様にて下記処方
２に示す樹脂溶液をプリントし，１００℃で２分間の乾
燥により，膜厚が約５０μｍで，蓄光性微粉末を２０重
量％，透明ガラスビーズを４９重量％含有する樹脂層を
形成後，アサヒガードＡＧ−５６５０（旭硝子株式会社
製，溶剤型フッ素系撥水剤）５％ミネラルターペン溶液
にてパディング（絞り率３０％）し，乾燥後，１７０℃
で１分間のキュアリングを行い，本発明の透湿防水性蓄
光再帰反射性プリント布を得た。Next, using a flat screen printing machine, a resin solution represented by the following formula 2 was printed on the resin layer in a checkerboard pattern of 5 mm square unit, and dried at 100 ° C. for 2 minutes to obtain a film thickness. After forming a resin layer of about 50 μm, containing 20% by weight of luminous fine powder and 49% by weight of transparent glass beads, 5% Asahigard AG-5650 (a solvent-type fluorine-based water repellent, manufactured by Asahi Glass Co., Ltd.) Padded with a turpen solution (30% squeezing rate), dried, 170 ° C
For 1 minute to obtain a moisture-permeable waterproof luminous retroreflective printed cloth of the present invention.
【００２８】処方２ ニュープレックス Ｍ−７３ＮＦ １００部 （林化学工業株式会社製，アクリル系エマルジョン樹脂
溶液） ＨＩ−５３−８８Ｓ ５０部 （日本電気硝子株式会社製，ＴｉＯ2 ，ＢａＯ，ＺｎＯ
を主成分とする屈折率1.９，平均球径約６０μｍの真球
状透明ガラスビーズ） ケミテックピカリコ ＣＰ−０４ ２０部 （ケミテック株式会社製，Ａｌ2 Ｏ3 ，ＢａＣＯ3 ，Ｓ
ｒＣｌ2 を主成分とする粒径約１０μｍの蓄光性微粉
末） オキザール Ｅ コンク ２部 （林化学工業株式会社製，エポキシ系架橋剤） 水 １０部Formulation 2 Newplex M-73NF 100 parts (manufactured by Hayashi Chemical Co., Ltd., acrylic emulsion resin solution) HI-53-88S 50 parts (manufactured by NEC Corporation, TiO 2 , BaO, ZnO)
Transparent glass beads with a refractive index of 1.9 and an average sphere diameter of about 60 μm) Chemitech Picarico CP-04 20 parts (manufactured by Chemitech Co., Ltd., Al 2 O 3 , BaCO 3 , S)
Luminous fine powder having a particle diameter of about 10 μm containing rCl 2 as a main component) Oxal E Conc. 2 parts (manufactured by Hayashi Chemical Industry Co., Ltd., epoxy-based crosslinking agent) Water 10 parts
【００２９】本発明との比較のため，下記比較例１〜９
により比較用のプリント布を製造し本発明との比較に供
した。For comparison with the present invention, the following Comparative Examples 1 to 9
Was manufactured for comparison with the present invention.
【００３０】比較例１ 本実施例において用いた処方１のＳａｐ４１２０ １０
部を1.２部に変えて，アルミニウム微粉末を４重量％含
有する樹脂層を形成する他は，本実施例とまったく同一
の方法により比較用のプリント布を得た。 比較例２ 本実施例において用いた処方１のＳａｐ４１２０ １０
部を３０部に変えて，アルミニウム微粉末を５２重量％
含有する樹脂層を形成する他は，本実施例とまったく同
一の方法により比較用のプリント布を得た。Comparative Example 1 Sap4120 10 of Formulation 1 used in this example
A printed cloth for comparison was obtained in exactly the same manner as in this example, except that the resin layer containing 4% by weight of aluminum fine powder was formed by changing the part to 1.2 parts. Comparative Example 2 Sap4120 10 of Formulation 1 used in this example
Part was changed to 30 parts and aluminum fine powder was 52% by weight
A printed cloth for comparison was obtained in exactly the same manner as in this example except that a resin layer to be contained was formed.
【００３１】比較例３ 本実施例において用いた処方２のケミテックピカリコＣ
Ｐ−０４ ２０部を４部に変えて，蓄光性微粉末を4.７
重量％含有する樹脂層を形成する他は，本実施例とまっ
たく同一の方法により比較用のプリント布を得た。 比較例４ 本実施例で用いた処方２のケミテックピカリコＣＰ−０
４ ２０部を８４部に変えて，蓄光性微粉末を５１重量
％含有する樹脂層を形成する他は，本実施例とまったく
同一の方法により比較用のプリント布を得た。Comparative Example 3 Chemitech Picarico C of Formulation 2 used in this example
20 parts of P-04 was changed to 4 parts, and the phosphorescent fine powder was changed to 4.7 parts.
A printed cloth for comparison was obtained in exactly the same manner as in this example, except that a resin layer containing a weight% was formed. Comparative Example 4 Chemitech Picarico CP-0 of Formulation 2 used in this example
A printed cloth for comparison was obtained in exactly the same manner as in this example, except that 420 parts was changed to 84 parts and a resin layer containing 51% by weight of the luminous fine powder was formed.
【００３２】比較例５ 本実施例で用いた処方２のＨＩ−５３−８８Ｓに代えて
ＳｉＯ2 ，ＢａＯを主成分とする屈折率1.６，平均球径
約６０μｍの真球状透明ガラスビーズを用いる他は，本
実施例とまったく同一の方法により比較用のプリント布
を得た。 比較例６ 本実施例において用いた処方２のＨＩ−５３−８８Ｓと
まったく同一組成で，平均球径が１５μｍのものを用い
る他は，本実施例とまったく同一の方法により比較用の
プリント布を得た。The refractive index of 1.6 mainly composed of SiO 2, BaO instead of Formulation 2 of HI-53-88S used in Comparative Example 5 In this example, the spherical transparent glass beads having an average sphere diameter of about 60μm A printed cloth for comparison was obtained in exactly the same manner as in the present example except that it was used. Comparative Example 6 A print cloth for comparison was produced in exactly the same manner as in this example, except that a composition having exactly the same composition as HI-53-88S of Formulation 2 used in this example and having an average sphere diameter of 15 μm was used. Obtained.
【００３３】比較例７ 本実施例において用いた処方２のＨＩ−５３−８８Ｓと
まったく同一組成で，平均球径が１０５μｍのものを用
いる他は，本実施例とまったく同一の方法により比較用
のプリント布を得た。 比較例８ 本実施例において用いた処方２のＨＩ−５３−８８Ｓ
５０部を１０部に変えて，透明ガラスビーズを１６重量
％含有する樹脂層を形成する他は，本実施例とまったく
同一の方法により比較用のプリント布を得た。 比較例９ 本実施例において用いた処方２のＨＩ−５３−８８Ｓ
５０部を２２０部に変えて，透明ガラスビーズを８１重
量％含有する樹脂層を形成する他は，本実施例とまった
く同一の方法により比較用のプリント布を得た。Comparative Example 7 A comparative sample was prepared in exactly the same manner as in this example, except that it had exactly the same composition as HI-53-88S of Formulation 2 used in this example, and had an average sphere diameter of 105 μm. A printed cloth was obtained. Comparative Example 8 Formulation 2 HI-53-88S used in this example
Comparative print cloth was obtained by the exact same method as in this example except that a resin layer containing 16% by weight of transparent glass beads was formed by changing 50 parts to 10 parts. Comparative Example 9 Formula 2 HI-53-88S used in this example
A comparative printed cloth was obtained in exactly the same manner as in this example except that a resin layer containing 81% by weight of transparent glass beads was formed instead of changing 50 parts to 220 parts.
【００３４】本発明および比較用の蓄光再帰反射性布の
性能を測定，評価し，その結果を合わせて表１に示し
た。The performance of the present invention and the comparative phosphorescent retroreflective cloth were measured and evaluated. The results are shown in Table 1.
【００３５】[0035]
【表１】 [Table 1]
【００３６】表１より明らかなごとく，本発明方法によ
る透湿防水性蓄光再帰反射性プリント布は，優れた透湿
防水性能と蓄光性能，再帰反射性能を有していた。As is clear from Table 1, the moisture-permeable waterproof luminous retroreflective printed cloth according to the method of the present invention had excellent moisture-permeable waterproof property, luminous ability and retroreflective performance.
【００３７】[0037]
【発明の効果】本発明方法によれば，優れた透湿防水性
能と優れた蓄光性能，再帰反射性能を有した透湿防水性
蓄光再帰反射性プリント布を得ることができる。また，
本発明方法では，１回のコーティング加工と１回のプリ
ント加工により製造することができるので，コスト的に
非常に有利となる。本発明の透湿防水性蓄光再帰反射性
プリント布は，上記の優れた性能から，安全衣料，スポ
ーツ衣料等の素材として最適である。According to the method of the present invention, it is possible to obtain a moisture-permeable waterproof luminous retroreflective printed cloth having excellent moisture-permeable and waterproof performance, excellent luminous performance and retroreflective performance. Also,
The method of the present invention can be manufactured by one coating process and one printing process, which is very advantageous in terms of cost. The moisture-permeable waterproof luminous retroreflective printed cloth of the present invention is most suitable as a material for safety clothing, sports clothing and the like due to the above excellent performance.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ａ４１Ｄ 31/00 ５０２ Ｄ０６Ｍ 11/00 Ｚ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification symbol FI // A41D 31/00 502 D06M 11/00 Z
Claims (1)
の光反射性物質を５〜５０重量％含有するポリウレタン
樹脂主体の合成重合体からなる樹脂層を乾式コーティン
グ法にて形成する第１工程，該樹脂層上に蓄光性微粉末
を５〜５０重量％，屈折率1.７以上，平均球径２０〜１
００μｍの真球状透明ガラスビーズを２０〜８０重量％
含有するアクリル樹脂および／またはポリウレタン樹脂
を主体とする合成重合体からなる樹脂層をプリント法に
てガラスビーズの直径かまたはこれより薄く形成する第
２工程からなることを特徴とする透湿防水性蓄光再帰反
射性プリント布の製造方法。1. A first step of forming a resin layer of a synthetic polymer mainly composed of a polyurethane resin containing 5 to 50% by weight of a light-reflective substance such as aluminum or silver on the surface of a fiber fabric by a dry coating method. 5 to 50% by weight of a luminous fine powder, a refractive index of 1.7 or more, and an average sphere diameter of 20 to 1 on the resin layer.
20-80% by weight of 00 μm spherical transparent glass beads
A second step of forming a resin layer made of a synthetic polymer mainly containing an acrylic resin and / or a polyurethane resin to have a diameter equal to or smaller than the diameter of glass beads by a printing method. A method for producing a phosphorescent retroreflective printed cloth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20419797A JPH1150378A (en) | 1997-07-30 | 1997-07-30 | Production of printed fabric with permeability, moisture resistance, photo-accumulative property and recurrent reflection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20419797A JPH1150378A (en) | 1997-07-30 | 1997-07-30 | Production of printed fabric with permeability, moisture resistance, photo-accumulative property and recurrent reflection |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1150378A true JPH1150378A (en) | 1999-02-23 |
Family
ID=16486447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20419797A Pending JPH1150378A (en) | 1997-07-30 | 1997-07-30 | Production of printed fabric with permeability, moisture resistance, photo-accumulative property and recurrent reflection |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1150378A (en) |
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| US6777356B2 (en) | 2000-09-05 | 2004-08-17 | Japan Gore-Tex, Inc. | Luminous composite fabric and garment |
| US6908954B2 (en) | 2000-08-09 | 2005-06-21 | Brushstrokes Fine Art Inc. | Coating composition for artistic reproductions |
| US6931665B2 (en) | 2001-07-30 | 2005-08-23 | 3M Innovative Properties Company | Vapor permeable retroreflective garment |
| EP1283295A4 (en) * | 2000-08-09 | 2007-07-18 | Toray Industries | Waterproof-finished fabric and waterproof clothing |
| JP2009108445A (en) * | 2007-10-31 | 2009-05-21 | Teijin Fibers Ltd | Wind and snow-protection sheet |
| JP2009151210A (en) * | 2007-12-21 | 2009-07-09 | Teikoku Sen I Co Ltd | Sign plate for fire extinguishing, disaster prevention and safety, and sign plate making kit for fire extinguishing, disaster prevention and safety |
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- 1997-07-30 JP JP20419797A patent/JPH1150378A/en active Pending
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|---|---|---|---|---|
| EP1283295A4 (en) * | 2000-08-09 | 2007-07-18 | Toray Industries | Waterproof-finished fabric and waterproof clothing |
| US6908954B2 (en) | 2000-08-09 | 2005-06-21 | Brushstrokes Fine Art Inc. | Coating composition for artistic reproductions |
| US6777356B2 (en) | 2000-09-05 | 2004-08-17 | Japan Gore-Tex, Inc. | Luminous composite fabric and garment |
| US8256025B2 (en) | 2001-07-30 | 2012-09-04 | 3M Innovative Properties Company | Vapor permeable retroreflective garment |
| US7107622B2 (en) | 2001-07-30 | 2006-09-19 | 3M Innovative Properties Company | Vapor permeable retroreflective garment |
| US7600269B2 (en) | 2001-07-30 | 2009-10-13 | 3M Innovative Properties Company | Vapor permeable retroreflective garment |
| US8015620B2 (en) | 2001-07-30 | 2011-09-13 | 3M Innovative Properties Company | Vapor permeable retroreflective garment |
| US6931665B2 (en) | 2001-07-30 | 2005-08-23 | 3M Innovative Properties Company | Vapor permeable retroreflective garment |
| JP2009108445A (en) * | 2007-10-31 | 2009-05-21 | Teijin Fibers Ltd | Wind and snow-protection sheet |
| JP2009151210A (en) * | 2007-12-21 | 2009-07-09 | Teikoku Sen I Co Ltd | Sign plate for fire extinguishing, disaster prevention and safety, and sign plate making kit for fire extinguishing, disaster prevention and safety |
| USD758744S1 (en) | 2012-09-14 | 2016-06-14 | Under Armour, Inc. | Upper body garment with outer surface ornamentation |
| US10563349B2 (en) | 2012-09-14 | 2020-02-18 | Under Armour, Inc. | Apparel with heat retention layer and method of making the same |
| US9719206B2 (en) | 2012-09-14 | 2017-08-01 | Under Armour, Inc. | Apparel with heat retention layer and method of making the same |
| USD765427S1 (en) | 2013-03-11 | 2016-09-06 | Under Armour, Inc. | Upper body garment with areas of interior surface ornamentation |
| USD758745S1 (en) | 2013-03-11 | 2016-06-14 | Under Armour, Inc. | Lower body garment with outer surface ornamentation |
| USD766599S1 (en) | 2013-03-11 | 2016-09-20 | Under Armour, Inc. | Lower body garment with inner surface ornamentation |
| US10492550B2 (en) | 2014-01-28 | 2019-12-03 | Under Armour, Inc. | Article of apparel including thermoregulatory textile |
| WO2015141900A1 (en) * | 2014-03-18 | 2015-09-24 | 박희대 | Compound composition for coated yarn having pores |
| KR101530149B1 (en) * | 2014-03-18 | 2015-06-19 | 박희대 | compound composition for coating yarn |
| KR101447647B1 (en) * | 2014-05-29 | 2014-10-07 | 송민호 | Fabrication method of loess non-woven fabric and using the same bedding |
| KR20170131230A (en) * | 2016-05-20 | 2017-11-29 | 주식회사 덕성 | Retroreflective yarns and the preparation method thereof |
| KR101874844B1 (en) * | 2016-08-23 | 2018-07-06 | 신동수 | Polyester composite fiber having retroreflection function |
| JP2020193412A (en) * | 2019-05-28 | 2020-12-03 | 株式会社マック | Photoluminescent fabric, its textile product and method of imparting photoluminescent properties |
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