JPH07100368B2 - Method for manufacturing composite sheet material - Google Patents
Method for manufacturing composite sheet materialInfo
- Publication number
- JPH07100368B2 JPH07100368B2 JP61217730A JP21773086A JPH07100368B2 JP H07100368 B2 JPH07100368 B2 JP H07100368B2 JP 61217730 A JP61217730 A JP 61217730A JP 21773086 A JP21773086 A JP 21773086A JP H07100368 B2 JPH07100368 B2 JP H07100368B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- acrylic
- water
- skin layer
- additive
- 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.)
- Expired - Lifetime
Links
Landscapes
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は建築用の室内装飾材又は車輌等の内装材、特に
溌水性，溌油性，耐水性並びに耐汚染性を必要とする分
野に特に優れた性能，効果を有する複合シート材の製造
方法である。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is particularly applicable to interior decoration materials for construction or interior materials such as vehicles, and particularly to fields requiring water repellency, oil repellency, water resistance and stain resistance. This is a method for producing a composite sheet material having excellent performance and effects.
従来水を多用するいわゆる水廻り用の室内内装材に溌水
性及び耐水性を付与する方法としては、（１）塩化ビニ
ル樹脂系内装材の表面層にツヤ消表面処理剤層を形成す
る方法、（２）該表面層にフツソ系又はシリコーン系添
加剤を混入する方法、（３）いわゆる耐水性壁紙として
浸水収縮性の少い基材（ガラス不織布，耐水原紙等）上
に軟質塩化ビニル樹脂発泡層を形成し表皮層として軟質
塩化ビニル樹脂シート層又はその他の熱可塑性樹脂シー
トを積層一体化して製造する方法等が一般的に用いられ
ている。As a method for imparting water repellency and water resistance to a so-called water-driving interior interior material that conventionally uses a lot of water, (1) a method of forming a matting surface treatment agent layer on the surface layer of a vinyl chloride resin interior material, (2) A method in which a fluorine-based or silicone-based additive is mixed into the surface layer, (3) A soft vinyl chloride resin foamed on a base material (glass non-woven fabric, water-resistant base paper, etc.) with little water-shrinkage as a so-called water-resistant wallpaper A method of forming a layer and laminating and integrating a soft vinyl chloride resin sheet layer or another thermoplastic resin sheet as a skin layer is generally used.
しかしながら上記（１）の方法においては表面層上にツ
ヤ消表面処理剤層を施すと著しく溌水性が低下し、又ツ
ヤ消表面処理剤層を施さないと軟質塩化ビニル樹脂層の
可塑剤がその表面にブリードするため一応の溌水効果を
有するものとなるが、表面に汚れが付着しやすくなる等
の欠点を生じ好ましくない。又（２）の方法では溌水性
並びに耐水性効果を付与することが出来るが、混入樹脂
との相溶性が悪く、該剤が表皮層の表面に滲出し、上記
効果の持続性に欠けるとともに、表皮層表面に対する該
剤の表面移行配列性も充分でない等の欠点を有する。又
（３）の方法の製品は表皮層が軟質塩化ビニルシートを
用いたものは汚れやすく、又層厚が厚いため製品が硬
く、かつ重くなり、施工性に劣る結果を来たす。又汚れ
防止効果を有するアクリル系樹脂，フツソ系樹脂等のフ
イルムを前記表皮層として軟質塩化ビニル樹脂発泡層
（中間層）上にラミネートすることにより積層する方法
もあるが、該法での製品も表皮層が硬くなり柔軟性に欠
け、施工上問題を生じる等の欠点を含有しているもので
ある。However, in the above method (1), when a matte surface treating agent layer is applied on the surface layer, the water repellent property is remarkably reduced, and when the matte surface treating agent layer is not applied, the plasticizer of the soft vinyl chloride resin layer is Since it bleeds to the surface, it has a temporary water repellent effect, but it is not preferable because it causes defects such as easy attachment of dirt to the surface. In addition, the method (2) can impart water repellent and water resistant effects, but the compatibility with the mixed resin is poor and the agent exudes to the surface of the skin layer, and the above effect is lacking in durability. There is a defect that the surface migration arrangement property of the agent to the surface of the epidermis layer is not sufficient. Further, in the product of the method (3), the product using the soft vinyl chloride sheet for the skin layer is easily soiled, and the thick layer makes the product hard and heavy, resulting in poor workability. There is also a method of laminating a film such as an acrylic resin or a fluorine resin having an antifouling effect on the soft vinyl chloride resin foam layer (intermediate layer) as the above-mentioned skin layer to form a laminate. It has drawbacks such that the skin layer becomes hard, lacks flexibility, and causes problems in construction.
本発明は上記の如き諸欠点がなく、長期間にわたる持続
効果を有する優れた溌水性，溌油性と耐水性並びに耐汚
染性を有ししかも良好な施工性をも供有具備し、水を多
用する分野の室内内装材、その他素材として秀でた上記
効果を具現する複合シート材の製造方法を提供するもの
である。The present invention does not have the above-mentioned drawbacks, has excellent water-repellent, oil-repellent, water-resistant and stain-resistant properties that have a long-lasting effect, and also has good workability. It is intended to provide a method for producing a composite sheet material that realizes the above-mentioned effects, which are excellent as an interior / interior material in the field of
本発明は耐水性と難燃性を有する基材上に中間層として
塩化ビニル系樹脂の非発泡体もしくは発泡体を積層し、
更に該層上に極く薄い表皮層として熱可塑性合成樹脂
で、かつ該合成樹脂中に、表皮層に対して優れた表面移
行性と相溶性を併有する添加剤を0.1〜３重量％混入し
たものを積層し、加熱、乾燥して一体化する複合シート
材であつて、表皮層は（イ）層厚が10μ〜200μであ
り、該表面が平滑面もしくは絞模様の凹凸面であり、
（ロ）グラフトポリマーはアクリル系化合物のマクロモ
ノマーとアクリル系フツソ化合物もしくはアクリル系シ
リコーン化合物との共重合体であり、（ハ）ブロツクポ
リマーはアクリル系化合物とアクリル系フツソ化合物と
の共重合体である複合シート材を製造する方法である。The present invention laminates a non-foamed or foamed vinyl chloride resin as an intermediate layer on a substrate having water resistance and flame retardancy,
Further, a thermoplastic synthetic resin is used as an extremely thin skin layer on the layer, and 0.1 to 3% by weight of an additive having both excellent surface migration and compatibility with the skin layer is mixed in the synthetic resin. A composite sheet material in which objects are laminated, heated, dried and integrated, wherein the skin layer (a) has a layer thickness of 10 μ to 200 μ, and the surface is a smooth surface or an uneven surface of a drawn pattern,
(B) The graft polymer is a copolymer of an acrylic compound macromonomer and an acrylic fluorine compound or an acrylic silicone compound, and (c) a block polymer is a copolymer of an acrylic compound and an acrylic fluorine compound. A method for manufacturing a composite sheet material.
以下本発明の製造方法について詳細に説明する。 The manufacturing method of the present invention will be described in detail below.
本発明の基材としては特に耐水性と難燃性を有する基材
を用いる。その理由としては本発明で製造する製品は特
に水を多用する分野に用いることを目的としているため
特に基材も耐水性を有し、しかも内装材として使用する
ため難燃性を保有せしめることにより本発明の目的とす
る基材としての機能性を十分発揮し得るものである。該
基材としては紙，不織布，編織布等を用いこれに難燃性
を付与するために含ハロゲン有機燐酸系エステル，チオ
尿素系化合物，グアナジン系化合物等の難燃剤により難
燃加工を施すか、ガラス繊維等の不燃性繊維を混入して
用い、又耐水性を付与するためにはフツソ系もしくはシ
リコーン系化合物等の溌水剤で処理するか、もしくは耐
水性を有するポリエステル系樹脂繊維，ポリオレフイン
系樹脂繊維，レーヨン繊維，ガラス繊維を単独もしくは
混入、又は混編織したものを使用する。As the base material of the present invention, a base material having water resistance and flame retardancy is particularly used. The reason is that the product manufactured by the present invention is particularly intended to be used in a field where water is frequently used, so that the base material also has water resistance, and in addition, it has flame retardancy for use as an interior material. It is possible to sufficiently exhibit the functionality as a substrate, which is the object of the present invention. As the base material, paper, non-woven fabric, knitted fabric, or the like is used. Is flame-retardant treatment with a flame retardant such as a halogen-containing organic phosphoric acid ester, a thiourea compound, or a guanazine compound in order to impart flame retardancy thereto? , Mixed with non-combustible fibers such as glass fiber, or treated with a water repellent such as fusso-based or silicone-based compound to impart water resistance, or water-resistant polyester-based resin fiber, polyolefin A resin fiber, rayon fiber, or glass fiber may be used alone or mixed, or a mixed knitted fabric may be used.
次に上記基材上に中間層として塩化ビニル系樹脂の非発
泡体又は発泡体をシート状に積層形成する。該層に用い
る樹脂組成物のポリ塩化ビニル系樹脂としては塩化ビニ
ルのホモポリマー以外に塩化ビニルと酢酸ビニル等との
共重合体、塩化ビニルとエチレン一酢酸ビニルとの共重
合体、塩化ビニルと各種モノマーとのグラフト共重合体
を含くみ、さらにこれ等共重合体と塩化ビニルホモポリ
マーとの混合物、および塩化ビニルホモポリマーと他の
熱可塑性樹脂との混合物も用いることができる。又これ
らのポリマーは懸濁重合，乳化重合等の何れの重合法の
ものも使用できる。Next, a non-foamed body or a foamed body of vinyl chloride resin is laminated and formed as a sheet on the above base material as an intermediate layer. Examples of the polyvinyl chloride resin of the resin composition used for the layer include a homopolymer of vinyl chloride, a copolymer of vinyl chloride and vinyl acetate, a copolymer of vinyl chloride and ethylene monovinyl acetate, and vinyl chloride. It is also possible to use graft copolymers with various monomers, and also mixtures of these copolymers and vinyl chloride homopolymers, and mixtures of vinyl chloride homopolymers with other thermoplastic resins. Further, as these polymers, any polymerization method such as suspension polymerization and emulsion polymerization can be used.
該層の非発泡体には上記樹脂に可塑剤，安定剤，滑剤，
ケレーター，染料，顔料等の着色剤，難燃剤の他、必要
に応じて充填剤等を混合して使用する。又発泡体では上
記非発泡体の組成物に化学発泡剤を混入して使用する。
該中間層を形成する方法としては非発泡体においてはカ
レンダー法，押出法又はコーテイング法等の各種の方法
を用いることが出来るが、量産性，生産コストの点から
してカレンダー法が好ましい。いずれの方法を用いるに
しても、該シートの形成厚は約0.1〜1mmであることが好
ましく、0.1mm以下では物性強度的に問題が発生しやす
く、又1mm以上では強靭で物性強度上の問題はないが、
重量的に重く、風合が硬くなり該内装材として使用する
場合施工上に問題を生ずる。For the non-foamed material of the layer, a plasticizer, a stabilizer, a lubricant,
In addition to kerators, dyes, colorants such as pigments, flame retardants, and the like, fillers and the like are mixed and used. In the case of foam, a chemical foaming agent is mixed with the above non-foamed composition.
As a method for forming the intermediate layer, various methods such as a calendering method, an extrusion method or a coating method can be used for the non-foamed body, but the calendering method is preferable from the viewpoints of mass productivity and production cost. Whichever method is used, it is preferable that the formed thickness of the sheet is about 0.1 to 1 mm, and if 0.1 mm or less, problems in physical strength tend to occur, and if it is 1 mm or more, it is tough and problems in physical strength. But not
Since it is heavy in weight and hard in texture, it causes a problem in construction when used as the interior material.
又上記発泡体においては上記塩化ビニル系樹脂組成物の
軟化温度で発泡剤の分解温度以下の加工温度を用いて、
上記のいずれかの加工方法によりシート状に積層する。
この場合も上記と同様にカレンダー法を用いることが好
ましい。いずれの方法を用いるにしても該シートの適用
厚は約0.1〜0.4mmであることが好ましい。次いで該積層
体を発泡炉を用いて上記シート層を加熱発泡し、厚みが
0.3〜3mmの発泡体を形成せしめる。この場合0.3mm以下
及び3mm以上では上記の非発泡体の場合と同様の理由を
生じ好ましくない。Further, in the above foam, by using a processing temperature below the decomposition temperature of the foaming agent at the softening temperature of the vinyl chloride resin composition,
A sheet is laminated by any of the above processing methods.
Also in this case, it is preferable to use the calendar method as in the above. Whichever method is used, the applied thickness of the sheet is preferably about 0.1 to 0.4 mm. Then, the above-mentioned sheet layer is heat-foamed using a foaming furnace to obtain a laminate having a thickness of
Form a foam of 0.3 to 3 mm. In this case, if it is 0.3 mm or less and 3 mm or more, the same reason as in the case of the above non-foamed body occurs, which is not preferable.
又該発泡体を別に0.3〜3mmの層厚を有する発泡シート単
体を製造しこれをラミネート法を用いて上記基材と積層
一体化しても良い。Alternatively, the foam may be separately manufactured into a foam sheet having a layer thickness of 0.3 to 3 mm, and the foam sheet may be laminated and integrated with the above-mentioned substrate by using a laminating method.
次いで溌水性，耐水性，溌油性並びに耐汚染性の諸機能
性を有する表皮層を上記中間層上に極く薄い層厚に塗工
する。本発明の表皮層に使用する熱可塑性合成樹脂組成
物はポリアクリル計樹脂，ポリウレタン系樹脂等の単独
もしくは共重合体又はこれらの混合物を溶剤系の塗料の
形態とし、これに上記の諸効果性能を具現する添加剤を
混入して用いる。該添加剤は、表皮層の合成樹脂に対し
て優れた表面移行性と相溶性とを併有するものであっ
て、グラフトポリマーとしてはアクリル系化合物のマク
ロモノマーとアクリル系フッソ化合物もしくはアクリル
系シリコーン化合物との共重合体であり、また、ブロッ
クポリマーとしてはアクリル系化合物とアクリル系フッ
ソ化合物との共重合体である。即ち、前記添加剤中の一
方のアクリル系フッソ化合物又はアクリル系シリコーン
化合物は表皮層の合成樹脂に対しきわめて優れた界面移
行性を有する機能性セグメントとしての役割を果たし、
表皮層表面に優れた溌水性、溌油性、耐水性並びに耐汚
染性を付与すると共に、該添加剤中の他方のアクリル系
化合物のマクロモノマー若しくはアクリル系化合物は前
記表皮層たる樹脂に対し相溶性を有する相溶性セグメン
トとしての役割を果たし、表皮樹脂層に対しいわゆるア
ンカー効果を発揮し充分に相溶すると共に、両者の効果
が相乗されて改質効果の持続性に富んだものを生成で
き、しかも該表皮層の樹脂組成物本来の硬さ、抗張力、
伸び等の諸物性を変えることなく秀でた溌水性、溌油
性、耐水性並びに耐汚染性を有するものが得られる。か
ゝる優れた改質効果の持続性，耐久性は従来より使用さ
れているフツソ系添加剤やシリコーン系添加剤には見出
し得ないものである。該添加剤の上記表皮層樹脂組成物
に対する添加量は、その樹脂固型分に対し、0.1〜３％
であることが好ましく、該範囲の添加量により、該表皮
層と液体（水，油等）との接触角は約100〜120゜とな
り、物理的な界面における「ぬれの現象」が低下し、上
記の諸性能効果を発現できる。この場合0.1％未満では
接触角が90゜以下となり、上記の諸性能の改質効果を具
現出来ず、また３％を超える量を添加してもその効果は
それ以上向上しない。Next, a skin layer having various functions such as water repellent property, water repellent property, oil repellent property and stain resistant property is coated on the above-mentioned intermediate layer in a very thin layer thickness. The thermoplastic synthetic resin composition used for the skin layer of the present invention is a polyacrylic meter resin, a homopolymer or copolymer of a polyurethane resin or the like, or a mixture thereof in the form of a solvent-based paint, which has the above-mentioned various effect performances. The additive which embodies the above is mixed and used. The additive has both excellent surface migration and compatibility with the synthetic resin of the skin layer, and the graft polymer is a macromonomer of an acrylic compound and an acrylic fluorine compound or an acrylic silicone compound. And a block polymer is a copolymer of an acrylic compound and an acrylic fluorine compound. That is, one of the acrylic fluorine compound or acrylic silicone compound in the additive serves as a functional segment having extremely excellent interfacial migration to the synthetic resin of the skin layer,
It imparts excellent water-repellency, oil-repellency, water resistance and stain resistance to the surface of the skin layer, and the macromonomer or acrylic compound of the other acrylic compound in the additive is compatible with the resin which is the skin layer. Plays a role as a compatible segment having a so-called anchor effect with respect to the skin resin layer and is sufficiently compatible, and the effects of both are synergized to produce a product having a long-lasting modification effect, Moreover, the original hardness of the resin composition of the skin layer, tensile strength,
It is possible to obtain those having excellent water repellency, oil repellency, water resistance and stain resistance without changing physical properties such as elongation. Such excellent durability and durability of the modification effect cannot be found in the conventionally used fluorine-based additives and silicone-based additives. The amount of the additive added to the skin layer resin composition is 0.1 to 3% with respect to the resin solid content.
It is preferable that the contact angle between the skin layer and the liquid (water, oil, etc.) is about 100 to 120 °, and the "wetting phenomenon" at the physical interface is reduced by the addition amount within the range. The above various performance effects can be exhibited. In this case, if the content is less than 0.1%, the contact angle becomes 90 ° or less, and the effect of modifying the various performances described above cannot be realized, and even if the content exceeds 3%, the effect is not further improved.
該表皮層を形成する方法は、上記の構成組成物の塗料を
グラビヤ方式，ロールコーター方式，ロータリースクリ
ーン方式等の一般的な塗工方式を用いて、塗工し加熱乾
燥し、皮膜厚が10μ〜200μの極く薄い表皮層を形成す
る。層厚が10μ以下では物性強度的に問題が生じやす
く、又200μ以上では強度的には問題がないが、風合が
硬く、重量的に重くなり施工性に支障を来たし本発明の
目的とする製品が得られない。該表皮層がかくの如く極
めて薄いものであつても上記本発明の混入添加剤の優れ
た性質諸作用により上記の諸性能効果を十分に発現し得
るものである。The method for forming the skin layer is such that the coating composition having the above composition is applied by a general coating method such as a gravure method, a roll coater method, or a rotary screen method, followed by heating and drying to obtain a film thickness of 10 μm. Form a very thin skin layer of ~ 200μ. When the layer thickness is 10μ or less, problems in physical strength tend to occur, and when it is 200μ or more, there is no problem in strength, but the texture is hard and the weight is heavy, which causes an obstacle to workability and is an object of the present invention. I can't get the product. Even if the skin layer is extremely thin as described above, the above-mentioned various performance effects can be sufficiently exhibited by the various properties and effects of the additive additive of the present invention.
該表皮層の表面は塗工時のまゝの平滑面を使用しても良
いが、更に一般に用いられているロールエンボス方式を
適用して該表面に凹凸模様を形成せしめてもよい。かく
することにより前記溌水，溌油性，耐水性を更に増大せ
しめることが出来る。その理由は表皮層中に添加されて
いる添加剤中の表面移行性セグメントであるアクリル系
フッソ化合物又はアクリル系シリコーン化合物の配向の
結果、該樹脂表面に接触する液体（水，油等）と該樹脂
層との接触角が平滑面より大となり、いわゆる物理的な
「ぬれの現象」が更に低下するためである。The surface of the skin layer may be an ordinary smooth surface at the time of coating, but a roll embossing method which is generally used may be applied to form an uneven pattern on the surface. By doing so, the water repellent property, oil repellent property, and water resistance can be further increased. The reason is that as a result of the orientation of the acrylic fluorine-containing compound or the acrylic silicone compound, which is the surface transferable segment in the additive added to the skin layer, the liquid (water, oil, etc.) contacting the resin surface and the liquid This is because the contact angle with the resin layer is larger than that on a smooth surface, and the so-called physical "wetting phenomenon" is further reduced.
以上詳述した如く、本発明によつて得られた複合シート
材は、長期間にわたる持続効果を有する優れた溌水性，
溌油性，耐水性並びに耐汚染性を有するとともに、良好
な施工性をも併有しているため、水を多用する分野の室
内内装材その他の素材として優れた上記諸効果を発現し
うるものである。As described in detail above, the composite sheet material obtained according to the present invention has an excellent water repellent property that has a long-lasting effect.
It has oil-repellent, water-resistant and stain-resistant properties, and also has good workability, so that it can exhibit the above-mentioned effects that are excellent as an interior material and other materials in the water-intensive field. is there.
以下各種実施例をもつて本発明を具体的に説明する。 The present invention will be specifically described below with reference to various examples.
実施例１ 壁紙裏打用として含ハロゲン有機燐酸エステル系難燃剤
を用いて処理したパルプ繊維にガラス繊維を混入し耐水
性を具備せしめた難燃，耐水紙を基材とし、その上に中
間層とし下記配合組成を有するポリ塩化ビニル樹脂組成
物をカレンダー法を用いて0.18mm厚のアイボリー色の着
色層を積層形成し、更にその上面に通常の塩化ビニルレ
ザー用印刷塗料を用いてグラビア印刷機でグレー色の雲
柄のプリント模様を施し乾燥した後、表皮層として下記
配合組成を有するグラフトポリマータイプとアクリル系
フツソ化合物との共重合体よりなる機能性添加材を混入
せる表皮用塗料をグラビア印刷機を用い全面に塗布し加
熱乾燥して約20μの層厚を有する表皮層を積層形成し、
複合シート材を得た。次いで得られた製品の各性能テス
トを別紙の方法で実施し、その溌水効果，耐汚染効果は
別紙の如く優れたものであり、又柔軟性に富み、軽量で
施工性が良好な耐水性を有し、壁装内装材として優れた
製品であることを確認した。Example 1 A flame-retardant and water-resistant paper having a water resistance obtained by mixing glass fibers into pulp fibers treated with a halogen-containing organic phosphate ester-based flame retardant for wallpaper lining, and an intermediate layer formed thereon. A polyvinyl chloride resin composition having the following composition is laminated to form an ivory colored layer having a thickness of 0.18 mm using a calendering method, and a gravure printing machine is further formed on the upper surface thereof using a conventional vinyl chloride leather printing paint. After applying a gray cloud pattern print pattern and drying it, gravure printing a skin paint that incorporates a functional additive made of a copolymer of a graft polymer type and an acrylic fuso compound having the following composition as a skin layer Coat the entire surface using a machine and heat dry to form a skin layer having a layer thickness of about 20μ.
A composite sheet material was obtained. Next, each performance test of the obtained product is carried out by the method of the attached sheet, and its water repellent effect and stain resistance effect are as excellent as the attached sheet, and it is also flexible, lightweight, and has good workability and water resistance. Therefore, it was confirmed that the product was excellent as a wall interior material.
ポリ塩化ビニル樹脂（＝1100） 100 重量部 DOP 50 〃 Ca−Ba−Zn系安定剤 ２ 〃 チタン白顔料 15 〃 ベンジジンイエロー顔料 ３ 〃 弁柄顔料 1.5 〃 炭酸カルシウム 30 〃 三酸化アンチモン ５ 〃 ケレーター ２ 〃 〔表皮層用塗料配合〕 溶剤型アクリル系表面処理用塗料 （固形樹脂分15重量％） 100 重量部 （添加剤） アクリル系化合物のグラフトポリマー 0.6重量部 〔東亜合成化学工業（株）製：アロンGF300〕 実施例２ 実施例１と同様の基材，中間層を用い、表皮層配合組成
物中の添加剤をグラフトポリマータイプとアクリル系シ
リコーン化合物の共重合体よりなる機能性添加剤に置換
えて使用し、その他の材料、並びに加工方法は実施例１
と全く同一同様にして製品を得た。得られた製品は実施
例１と同様に別紙に示す如き優れた諸効果と軽量で柔軟
な風合を有する良好な施工性を有する製品であつた。Polyvinyl chloride resin (= 1100) 100 parts by weight DOP 50 〃 Ca-Ba-Zn stabilizer 2 〃 Titanium white pigment 15 〃 Benzidine yellow pigment 3 〃 Red pigment 1.5 〃 Calcium carbonate 30 〃 Antimony trioxide 5 〃 Kelator 2 〃 [Skin layer coating mixture] Solvent-based acrylic surface treatment coating (solid resin content 15% by weight) 100 parts by weight (additive) Graft polymer of acrylic compound 0.6 parts by weight [Toagosei Chemical Industry Co., Ltd .: Aron GF300] Example 2 The same base material and intermediate layer as in Example 1 were used, and the additive in the composition for skin layer substitution was replaced with a functional additive composed of a copolymer of a graft polymer type and an acrylic silicone compound. Other materials and processing methods are used in Example 1.
A product was obtained in exactly the same manner as. The obtained product was a product having excellent effects as shown in a separate sheet as in Example 1 and having light weight and soft texture and good workability.
溶剤型アクリル系表面処理用塗料 （固形樹脂分15重量％） 100 重量部 （添加剤） アクリル系化合物のグラフトポリマー 0.75重量部 〔東亜合成化学工業（株）製：アロンGS30〕 実施例３ 実施例２と同様に表皮層配合組成物中の添加剤をブロツ
クポリマータイプのアクリル系フツソ系化合物との共重
合体よりなる機能性添加剤に置換えた以外は実施例１と
全く同一同様、材料並び方法を用いて製品を得た。得ら
れた製品は別紙に示す如く実施例１と同様に優れたもの
であつた。Solvent-based acrylic surface treatment coating (solid resin content 15% by weight) 100 parts by weight (additive) Graft polymer of acrylic compound 0.75 parts by weight [Toagosei Kagaku Kogyo Co., Ltd .: Aron GS30] Example 3 Example As in Example 2, except that the additive in the composition for forming the skin layer was replaced with a functional additive consisting of a copolymer of a block polymer type acrylic fluorine-based compound, the same method of material arrangement as in Example 1 was used. To obtain the product. The obtained product was excellent as in Example 1 as shown in the attached sheet.
溶剤型アクリル系表面処理用塗料 （固形樹脂分15重量％） 100 重量部 （添加剤） アクリル系化合物のブロックポリマー 0.5重量部 〔日本油脂（株）製：モディパーF210〕 実施例４ 実施例１で得られた製品の表皮層表面を加熱し、ロール
エンボス機を用いて布目調の柄模様を有する凹凸絞模様
を賦形し複合シート材を得た。得られた製品は別紙に示
す如く、実施例１より更に優れた溌水効果を有する製品
であつた。Solvent-based acrylic surface treatment coating (solid resin content 15% by weight) 100 parts by weight (additive) Block compound of acrylic compound 0.5 parts by weight [NOF CORPORATION: MODIPER F210] Example 4 In Example 1 The surface layer surface of the obtained product was heated, and a concavo-convex pattern having a texture pattern was formed using a roll embossing machine to obtain a composite sheet material. As shown in the attached sheet, the obtained product had a water repellent effect superior to that of Example 1.
実施例５ 実施例４の基材を、目付100g/m2の耐水性に優れたポリ
エステル不織布に含ハロゲン有機燐酸エステル難燃剤を
用いて難燃処理を施したものを基材として置換え、中間
層の塩化ビニル樹脂シート厚を0.25mmとした以外は全く
同一の素材、同様の方法を用いて表面に布目調の凹凸絞
模様を有する複合シート材を得た。得られた製品は実施
例４と同様の優れた効果を有し、車両用ドアトリム内装
材並びに建築用内装材として秀でた製品であつた。Example 5 The base material of Example 4 was replaced with a base material which was made by subjecting a polyester nonwoven fabric having a basis weight of 100 g / m 2 and having excellent water resistance to a flame-retardant treatment using a halogen-containing organic phosphate ester flame retardant, as a base material. A composite sheet material having a texture-like uneven squeezing pattern on the surface was obtained by using the same material and using the same method except that the thickness of the vinyl chloride resin sheet was set to 0.25 mm. The obtained product had the same excellent effects as in Example 4, and was an excellent product as a vehicle door trim interior material and a building interior material.
実施例６ 耐水性と難燃性を有する目付80g/m2のガラス繊維から成
る不織布上に中間発泡体層として下記配合組成を有する
塩化ビニル樹脂発泡体組成物を含有発泡剤の分解温度以
下である160℃の加工温度でカレンダー機を用いて白色
の着色層を0.15mmの厚さでシート状に積層形成し、次い
で該積層体を発泡炉を用い210℃の温度で３分間処理し
て該シート層を1.1mm厚に加熱発泡せしめて発泡体層を
形成し、続いて表皮層として下記配合組成を有するグラ
フトポリマータイプとアクリル系フツソ化合物との共重
合体よりなる機能性添加剤を混入した表皮用塗料をグラ
ビア印刷機を用いて全面に塗布し加熱乾燥して約20μの
層厚の表皮層を積層形成し複合シート材を得た。得られ
た製品は柔軟かつ軽量で施工に優れ、又秀でた溌水効果
と耐汚染効果を有し建築用内装材として有用なものであ
つた。Example 6 Containing a vinyl chloride resin foam composition having the following composition as an intermediate foam layer on a non-woven fabric made of glass fiber having a basis weight of 80 g / m 2 having water resistance and flame retardancy at a decomposition temperature of a foaming agent or lower. Using a calender at a certain processing temperature of 160 ° C., a white colored layer was laminated to form a sheet having a thickness of 0.15 mm, and then the laminated body was treated at a temperature of 210 ° C. for 3 minutes using a foaming furnace, A foam layer was formed by heat-foaming the sheet layer to a thickness of 1.1 mm, and subsequently a functional additive composed of a copolymer of a graft polymer type having the following composition and an acrylic fuso compound was mixed as a skin layer. The surface coating material was applied to the entire surface by using a gravure printing machine, and heated and dried to laminate and form a surface layer having a layer thickness of about 20μ to obtain a composite sheet material. The obtained product was flexible and lightweight, was excellent in construction, and had excellent water repellent effect and anti-staining effect, and was useful as an interior material for construction.
ポリ塩化ビニル樹脂（＝1100） 100 重量部 DOP 70 〃 発泡剤（ADCA） ５ 〃 チタン白 20 〃 Ca−Ba−Zn安定剤 2.5 〃 炭酸カルシウム 15 〃 三酸化アンチモン ５ 〃 ケレーター ２ 〃 〔表皮層用塗料配合〕 溶剤型アクリル系表面処理用塗料 （固形樹脂分15重量％） 100 重量部 （添加剤） アクリル系化合物のグラフトポリマー 1.8重量部 〔東亜合成化学工業（株）製：アロンGF300〕 比較例１ 実施例１と全く同一素材と同様の方法を用い表皮層配合
組成物中の添加剤を添加しないで複合シート材を得た。
得られた製品は全く溌水効果と耐汚染効果を有しないも
のであつた。Polyvinyl chloride resin (= 1100) 100 parts by weight DOP 70 〃 Foaming agent (ADCA) 5 〃 Titanium white 20 〃 Ca-Ba-Zn stabilizer 2.5 〃 Calcium carbonate 15 〃 Antimony trioxide 5 〃 Kelator 2 〃 [For skin layer Paint formulation] Solvent-based acrylic surface treatment paint (solid resin content 15% by weight) 100 parts by weight (additive) Graft polymer of acrylic compound 1.8 parts by weight [Toa Gosei Chemical Industry Co., Ltd .: Aron GF300] Comparative example 1 A composite sheet material was obtained in the same manner as in Example 1, except that the additives in the skin layer composition were not added.
The obtained product had no water repellent effect and stain resistant effect.
比較例２ 実施例１と全く同一素材と同様の方法を用い表皮層配合
組成物中の添加剤のみを市販フツソ系添加剤に置換え、
同一配合量を用いて複合シート材を得た。得られた製品
は製造直後においては溌水効果と耐汚染効果を有するも
のであつたが、これを洗剤により洗つたところ該添加剤
が洗い流され第１表に示す如く極端に溌水効果が低下消
失し、表面改質効果による耐久性を有するものではなか
つた。Comparative Example 2 Using the same method as in Example 1 except that the additives in the skin layer composition were replaced with commercially available fusso type additives,
A composite sheet material was obtained using the same compounding amount. The product obtained had a water-repellent effect and a stain-proofing effect immediately after the production, but when the product was washed with a detergent, the additive was washed off and the water-repellent effect was extremely lowered as shown in Table 1. It disappeared and was not durable due to the effect of surface modification.
比較例３ 実施例と全く同一素材と同様の方法を用い表皮層配合組
成物中の添加剤のみを市販のシリコーン系添加剤に置換
え、同一配合量を用いて複合材を得た。得られた製品は
製造直後においては溌水効果と耐汚染効果を有するもの
であつたが、これを洗剤により洗つたところ該添加剤が
洗い流され別表１に示す如く極端に溌水効果が低下消失
し、表面改質効果による耐久性を有するものではなかつ
た。Comparative Example 3 Using the same method as in the case of the example, only the additive in the skin layer composition was replaced with a commercially available silicone additive, and a composite material was obtained using the same amount. The obtained product had a water-repellent effect and a stain-proofing effect immediately after the production, but when this was washed with a detergent, the additive was washed off and the water-repellent effect was extremely reduced and disappeared as shown in Appendix 1. However, it did not have durability due to the surface modification effect.
以上実施例１乃至比較例３によつて得られた複合シート
材を比較すれば第１表の通りである。Table 1 shows a comparison of the composite sheet materials obtained in Examples 1 to 3 as described above.
〔１〕〔溌水性並びに溌油性テスト〕 （イ） （溌水性テスト）ゴニオメーターを用いて室温
25℃に於ける水と実施例１〜比較例３の表皮層表面に対
する「ぬれ」の程度を、水に対する接触角θを測定して
溌水性の評価の値を得た。[1] [Water-repellency and oil-repellency test] (a) (Water-repellency test) Room temperature using a goniometer
The degree of "wetting" between water at 25 ° C and the surface of the skin layers of Examples 1 to 3 was measured, and the contact angle θ with water was measured to obtain a value for evaluation of water repellency.
（ロ） （溌油性テスト）ゴニオメーターを用いて室温
25℃に於けるｎ−デカンに対する実施例１〜比較例３の
表皮層表面の接触角θを測定し、溌油性の評価の値を得
た。(B) (Responsiveness test) Room temperature using a goniometer
The contact angle θ of the skin layer surface of Example 1 to Comparative Example 3 with respect to n-decane at 25 ° C. was measured to obtain a value for evaluation of oil repellency.
〔２〕〔耐汚染性テスト〕 実施例１〜比較例３の表皮層表面に活性炭の５％水スラ
リーを滴下し、１日風乾後、ハケを用いて水洗するとき
の活性炭のとれぐあいを次の三段階で表示した。[2] [Staining resistance test] A 5% water slurry of activated carbon was dropped on the surface of the skin layer of Examples 1 to 3 and air-dried for one day, and then washed with water using a brush. It was displayed in three stages.
○：活性炭が全く残らない。◯: No activated carbon remains.
△： 〃 が少し付着し、少し黒くなつている。△: A little bit of 〃 is attached and it becomes a little black.
×： 〃 が付着し、黒くなる。×: 〃 adheres and turns black.
〔３〕〔耐久性テスト〕 （イ） （洗剤洗浄テスト）実施例１〜比較例３の表皮
層表面を30℃のママレモン（ライオン株式会社製，商品
名）１％水溶液に５時間浸漬後、充分に水洗し、１日風
乾後上記と同一の方法で溌水性を測定し、その評価の値
を得た。[3] [Durability Test] (a) (Detergent Cleaning Test) After dipping the skin layer surface of Examples 1 to Comparative Example 3 in a 1% aqueous solution of Mama Lemon (manufactured by Lion Corporation, trade name) at 30 ° C. for 5 hours, After sufficiently washing with water and air-drying for 1 day, the water repellency was measured by the same method as above, and the evaluation value was obtained.
（ロ） （耐候試験）実施例１〜比較例３の表皮層表面
をQUV試験機を用いて紫外線を温度60℃×４時間照射
後、湿度100％×40℃×４時間のサイクルで330時間繰返
しテストした後、上記と同一の方法で該表面の溌水性を
測定し、その評価の値を得た。(B) (Weather resistance test) After irradiating the surface of the skin layers of Examples 1 to 3 with ultraviolet rays using a QUV tester at a temperature of 60 ° C for 4 hours, a cycle of humidity 100% × 40 ° C for 4 hours for 330 hours After repeated tests, the water repellency of the surface was measured by the same method as above, and the evaluation value was obtained.
Claims (4)
して塩化ビニル系樹脂の非発泡体もしくは発泡体を積層
し、更に該層上に極く薄い表皮層として熱可塑性合成樹
脂で、かつ該合成樹脂中に、表皮層に対して優れた表面
移行性と相溶性を併有する添加剤を0.1〜３重量％混入
したものを積層し、加熱、乾燥して一体化することを特
徴とする複合シート材の製造方法。1. A non-foamed or foamed vinyl chloride resin is laminated as an intermediate layer on a base material having water resistance and flame retardancy, and a thermoplastic synthetic resin as an extremely thin skin layer is further formed on the layer. In addition, 0.1 to 3% by weight of an additive having both excellent surface migration property and compatibility with the skin layer is mixed in the synthetic resin, and the mixture is laminated by heating and drying. A method for manufacturing a characteristic composite sheet material.
が平滑面若しくは絞模様の凹凸面からなることを特徴と
する特許請求の範囲第１項記載の複合シート材の製造方
法。2. The method for producing a composite sheet material according to claim 1, wherein the skin layer has a layer thickness of 10 to 200 μm and the surface is a smooth surface or an uneven surface having a drawing pattern. .
マーとアクリル系フッソ化合物若しくはアクリル系シリ
コーン化合物とのグラフトポリマーであることを特徴と
する特許請求の範囲第１項記載の複合シート材の製造方
法。3. The production of a composite sheet material according to claim 1, wherein the additive is a graft polymer of a macromonomer of an acrylic compound and an acrylic fluorine compound or an acrylic silicone compound. Method.
フッソ化合物とのブロックポリマーであることを特徴と
する特許請求の範囲第１項記載の複合シート材の製造方
法。4. The method for producing a composite sheet material according to claim 1, wherein the additive is a block polymer of an acrylic compound and an acrylic fluorine compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61217730A JPH07100368B2 (en) | 1986-09-16 | 1986-09-16 | Method for manufacturing composite sheet material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61217730A JPH07100368B2 (en) | 1986-09-16 | 1986-09-16 | Method for manufacturing composite sheet material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6372527A JPS6372527A (en) | 1988-04-02 |
| JPH07100368B2 true JPH07100368B2 (en) | 1995-11-01 |
Family
ID=16708842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61217730A Expired - Lifetime JPH07100368B2 (en) | 1986-09-16 | 1986-09-16 | Method for manufacturing composite sheet material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07100368B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6531419B1 (en) | 1999-07-01 | 2003-03-11 | R. H. Wyner Associates, Inc. | Multi-layer protective fabrics |
| WO2002022691A2 (en) * | 2000-09-14 | 2002-03-21 | Rohm And Haas Company | Segmental copolymers and aqueous dispersions and films therefrom |
| US20050130521A1 (en) | 2003-12-10 | 2005-06-16 | Wyner Daniel M. | Protective laminates |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59127755A (en) * | 1983-01-12 | 1984-07-23 | 三菱レイヨン株式会社 | Laminated structure having weatherproofing |
-
1986
- 1986-09-16 JP JP61217730A patent/JPH07100368B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6372527A (en) | 1988-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0018847B1 (en) | Polyolefins having addition polymer adherent thereto, their preparation and articles comprising them | |
| CN102822414B (en) | Multi-layer sheet material and method for the production thereof | |
| US4507342A (en) | Polymers adherent to polyolefins | |
| US4424240A (en) | Polymers adherent to polyolefins | |
| RU2691030C1 (en) | Floor tile including fabric material, and method of its production | |
| JPH07100368B2 (en) | Method for manufacturing composite sheet material | |
| JP2003221888A (en) | Soundproof sheet having daylighting property | |
| US20210046728A1 (en) | Discoloration resistant fabric | |
| DE2047048A1 (en) | Process for the treatment of molded articles made of plasticized polyvinyl chloride | |
| DE202017005179U1 (en) | Coating composition, in particular for producing a coated wall, floor and ceiling clothing, in particular for producing a coated wallpaper | |
| US3666545A (en) | Method of producing an opaque,light weight fabric and resultant fabric | |
| US5230942A (en) | Birefringent inlaid sheet | |
| JP2721836B2 (en) | Mesh screen | |
| JP3045565B2 (en) | Film with excellent transparency and slip properties | |
| JPH06198820A (en) | Conductive vinyl chloride resin laminated sheet | |
| JPH08118553A (en) | Interior decorative sheet | |
| EP0020125A1 (en) | Polyolefins having addition polymer adherent thereto, their preparation and articles comprising them | |
| JP2944835B2 (en) | Manufacturing method of antifouling flame retardant polyester fiber products | |
| JPH04108182A (en) | Flameproofing shade curtain and production thereof | |
| JPS5841972A (en) | Fire retardant backing composition for carpet | |
| JPS60215878A (en) | Flame-retardant artificial leather structure | |
| JPS6237156A (en) | Antifouling sheet material | |
| JPH0335332B2 (en) | ||
| JPH1096170A (en) | Vinyl chloride-based resin-coated sheet | |
| DE102009029153A1 (en) | Washable wall coverings |