JP2000095915A - Aqueous emulsion composition and expanded sheet - Google Patents
Aqueous emulsion composition and expanded sheetInfo
- Publication number
- JP2000095915A JP2000095915A JP10264587A JP26458798A JP2000095915A JP 2000095915 A JP2000095915 A JP 2000095915A JP 10264587 A JP10264587 A JP 10264587A JP 26458798 A JP26458798 A JP 26458798A JP 2000095915 A JP2000095915 A JP 2000095915A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous emulsion
- weight
- content
- vinyl
- emulsion composition
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水性エマルジョン
組成物及び発泡シートに関するものである。更に詳しく
は、本発明は、地球環境及び作業環境の観点から好まし
くない塩化ビニルを用いることなく、難燃性、機械的強
度、耐折性、耐ブロッキング性、発泡性及びエンボス特
性に優れ、しかもオープンタイムが長いため作業性に優
れ、よって壁紙等の用途に最適に使用される水性エマル
ジョン組成物及び該水性エマルジョン組成物を用いて得
られる発泡シートに関するものである。[0001] The present invention relates to an aqueous emulsion composition and a foamed sheet. More specifically, the present invention is excellent in flame retardancy, mechanical strength, folding resistance, blocking resistance, foaming and embossing properties without using vinyl chloride which is not preferable from the viewpoint of the global environment and working environment, and The present invention relates to an aqueous emulsion composition which is excellent in workability due to a long open time and is therefore optimally used for applications such as wallpaper, and a foam sheet obtained using the aqueous emulsion composition.
【０００２】[0002]
【従来の技術】従来から、壁紙用途として難燃性発泡シ
ート用水性エマルジョン組成物が用いられている。従来
のエマルジョンは、塩化ビニルを含有する共重合体をポ
リマー成分として用い、その難燃性を維持していた。と
ころが、塩化ビニルを含有する共重合体を用いた壁紙
は、焼却処分時に有害な塩素ガスを発生し、地球環境及
び作業環境の観点から不都合な点を有していた。かかる
問題を解決する方法として、特開平７−１０８６４０号
公報には、アクリル樹脂系の装飾シート材に係る発明が
開示されている。しかしながらこの方法は、十分な発泡
性及び耐折性を得るという点において不満足なものであ
った。2. Description of the Related Art Conventionally, aqueous emulsion compositions for flame-retardant foamed sheets have been used for wallpaper applications. Conventional emulsions use a copolymer containing vinyl chloride as a polymer component and maintain their flame retardancy. However, wallpaper using a copolymer containing vinyl chloride generates harmful chlorine gas during incineration, and has disadvantages in terms of the global environment and working environment. As a method of solving such a problem, Japanese Patent Application Laid-Open No. 7-108640 discloses an invention relating to an acrylic resin-based decorative sheet material. However, this method was unsatisfactory in obtaining sufficient foamability and folding resistance.
【０００３】ところで、シートを接着して用いる場合、
シートに接着剤を塗布して放置すると経時的に接着剤が
乾いてしまい、接着不能になる。つまり接着剤を塗布し
てから接着可能な時間をオープンタイムといい、オープ
ンタイムが長い程、作業性に優れることになる。[0003] By the way, when the sheets are bonded and used,
If the adhesive is applied to the sheet and left as it is, the adhesive dries over time, making it impossible to adhere. In other words, the time that can be bonded after the adhesive is applied is called open time, and the longer the open time, the better the workability.
【０００４】[0004]
【発明が解決しようとする課題】かかる現状に鑑み、本
発明が解決しようとする課題は、地球環境及び作業環境
の観点から好ましくない塩化ビニルを用いることなく、
難燃性、機械的強度、耐折性、耐ブロッキング性、発泡
性及びエンボス特性に優れ、しかもオープンタイムが長
いため作業性に優れ、よって壁紙等の用途に最適に使用
される水性エマルジョン組成物及び該水性エマルジョン
組成物を用いて得られる発泡シートに関するものであ
る。SUMMARY OF THE INVENTION In view of this situation, the problem to be solved by the present invention is to use vinyl chloride which is not preferable from the viewpoint of the global environment and working environment.
An aqueous emulsion composition that is excellent in flame retardancy, mechanical strength, folding resistance, blocking resistance, foaming properties and embossing properties, and has a long open time, so it has excellent workability, and is therefore optimally used for applications such as wallpaper. And a foamed sheet obtained by using the aqueous emulsion composition.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明のうち
一の発明は、下記（Ａ）〜（Ｃ）成分を含有し、（Ｂ）
の含有量は（Ａ）１００重量部（固形分基準）あたり５
〜５０重量部であり、（Ｃ）の含有量は（Ａ）１００重
量部（固形分基準）あたり５０〜３５０重量部である水
性エマルジョン組成物に係るものである。 （Ａ）：（ａ1）エチレン５〜３５重量％及び（ａ2）ビ
ニルエステル９５〜６５重量％からなるエチレン−ビニ
ルエステル系共重合体であって、該ビニルエステルとし
てバーサチック酸ビニル及び／又はアクリル酸−２−エ
チルヘキシルを含有し、共重合体中のバーサチック酸ビ
ニル及びアクリル酸−２−エチルヘキシルの共重合体中
の合計含有量は１０〜６０重量％であり、ガラス転移温
度が−２５〜＋１５℃であるエチレン−ビニルエステル
系共重合体を含有する水性エマルジョン （Ｂ）：熱膨張性中空微小球体 （Ｃ）：無機フィラーThat is, one aspect of the present invention comprises the following components (A) to (C), and (B)
Is 5 parts per 100 parts by weight (solid basis) of (A)
The content relates to an aqueous emulsion composition in which the content of (C) is 50 to 350 parts by weight per 100 parts by weight (based on solid content) of (A). (A): an ethylene-vinyl ester copolymer comprising (a 1 ) 5 to 35% by weight of ethylene and (a 2 ) 95 to 65% by weight of a vinyl ester, wherein the vinyl ester is vinyl versatate and / or It contains 2-ethylhexyl acrylate, the total content of vinyl versatate and 2-ethylhexyl acrylate in the copolymer is 10 to 60% by weight, and the glass transition temperature is -25 to 25%. Aqueous emulsion containing ethylene-vinyl ester copolymer at + 15 ° C. (B): heat-expandable hollow microspheres (C): inorganic filler
【０００６】また、本発明のうち他の発明は、上記の水
性エマルジョン組成物を用いて得られる発泡シートに係
るものである。Another aspect of the present invention relates to a foamed sheet obtained by using the above-mentioned aqueous emulsion composition.
【０００７】[0007]
【発明の実施の形態】本発明の（Ａ）成分は、（ａ1）
エチレン５〜３５重量％及び（ａ2）ビニルエステル９
５〜６５重量％からなるエチレン−ビニルエステル系共
重合体であって、該ビニルエステルとしてバーサチック
酸ビニル及び／又はアクリル酸−２−エチルヘキシルを
含有し、共重合体中のバーサチック酸ビニル及びアクリ
ル酸−２−エチルヘキシルの共重合体中の合計含有量は
１０〜６０重量％であり、ガラス転移温度が−２５〜＋
１５℃であるエチレン−ビニルエステル系共重合体を含
有する水性エマルジョンである。DETAILED DESCRIPTION OF THE INVENTION The component (A) of the present invention comprises (a 1 )
Ethylene 5-35% by weight and (a 2) vinyl ester 9
An ethylene-vinyl ester copolymer comprising 5 to 65% by weight, wherein the vinyl ester contains vinyl versatate and / or 2-ethylhexyl acrylate, and the vinyl versatate and acrylic acid in the copolymer are contained. The total content of -2-ethylhexyl in the copolymer is 10 to 60% by weight, and the glass transition temperature is -25 to +
It is an aqueous emulsion containing an ethylene-vinyl ester copolymer at 15 ° C.
【０００８】エチレン−ビニルエステル系共重合体中の
（ａ1）エチレンの含有量は５〜３５重量％であり、好
ましくは５〜３０重量％である。該含有量が過少な場合
は硬く、耐ひび割れ性、発泡性に劣り、一方該含有量が
過多な場合は機械的強度及び耐ブロッキング性に劣る。The content of (a 1 ) ethylene in the ethylene-vinyl ester copolymer is 5 to 35% by weight, preferably 5 to 30% by weight. When the content is too small, the composition is hard and has poor crack resistance and foaming property. On the other hand, when the content is too large, the composition has poor mechanical strength and blocking resistance.
【０００９】（ａ2）ビニルエステルとしては、バーサ
チック酸ビニル及びアクリル酸−２−エチルヘキシルの
少なくとも一種を必須の成分として含有し、その他たと
えば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ピ
バリン酸ビニル、ラウリン酸ビニル、などをあげること
ができる。好ましくは、バーサチック酸ビニル及びバー
サチック酸ビニルとアクリル酸−２−エチルヘキシルの
併用である。(A 2 ) The vinyl ester contains at least one of vinyl versatate and 2-ethylhexyl acrylate as essential components, and further includes, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, and lauric acid. Acid vinyl, and the like. Preferred are vinyl versatate and a combination of vinyl versatate and 2-ethylhexyl acrylate.
【００１０】本発明においては、（ａ2）ビニルエステ
ルとしてバーサチック酸ビニル及び／又はアクリル酸−
２−エチルヘキシルを含有し、該バーサチック酸ビニル
及びアクリル酸−２−エチルヘキシルの共重合体中の合
計含有量は１０〜６０重量％であり、好ましくは１５〜
５０重量％である。該含有量が過少であると、オープン
タイムが短く、作業性に劣り、一方該該含有量が過多で
あると、耐ブロッキング性や機械的強度に劣る。[0010] In the present invention, (a 2) vinyl versatate and / or acrylic acid as the vinyl ester -
It contains 2-ethylhexyl, and the total content of the vinyl versatate and 2-ethylhexyl acrylate in the copolymer is from 10 to 60% by weight, preferably from 15 to 60% by weight.
50% by weight. If the content is too low, the open time is short and workability is poor, while if the content is too high, blocking resistance and mechanical strength are poor.
【００１１】エチレン−ビニルエステル系共重合体中の
（ａ2）ビニルエステルの含有量は９５〜６５重量％で
あり、好ましくは９０〜７０重量％である。該含有量が
過少な場合は機械的強度及び耐ブロッキング性に劣り、
一方該含有量が過多な場合は耐折性及び発泡性に劣る。The content of the (a 2 ) vinyl ester in the ethylene-vinyl ester copolymer is from 95 to 65% by weight, preferably from 90 to 70% by weight. If the content is too low, the mechanical strength and the blocking resistance are inferior,
On the other hand, when the content is excessive, the folding resistance and the foaming property are poor.
【００１２】（Ａ）成分のエチレン−ビニルエステル系
共重合体は、上記の（ａ1）及び（ａ2）並びに（ａ3）
官能性ビニル単量体を含有し、共重合体中の（ａ3）の
含有量が１０重量％以下である共重合体であってもよ
い。かかる共重合体を用いることにより、フィラーの分
散性の改良、組成物の安定性の改良、さらに耐ひび割れ
性及び耐ブロッキング性を改良することができる。[0012] The ethylene-vinyl ester copolymer of the component (A) is selected from the above-mentioned (a 1 ), (a 2 ) and (a 3 )
A copolymer containing a functional vinyl monomer and having a content of (a 3 ) in the copolymer of 10% by weight or less may be used. By using such a copolymer, it is possible to improve the dispersibility of the filler, the stability of the composition, and the crack resistance and the blocking resistance.
【００１３】（ａ3）官能性ビニル単量体としては、た
とえばアクリル酸、メタクリル酸、クロトン酸、イタコ
ン酸（半エステルを含む）、マレイン酸（半エステルを
含む）などのカルボキシル基含有モノマー及びその無水
物；Ｎ−メチロールアクリルアミド、Ｎ−ブトキシメチ
ルアクリルアミドなどのＮ−メチロール誘導体モノマ
ー；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、多価アルコ
ールのモノ（メタ）アクリレートや多価アルコールのモ
ノアリルエーテルなどのヒドロキシ基含有モノマー；ジ
メチルアミノエチルメタクリレート、ジメチルアミノプ
ロピルアクリルアミドなどのアミノ基含有モノマー；グ
リシジル（メタ）アクリレートなどのエポキシ基含有モ
ノマー；アクリルアミド、メタアクリルアミド、マレイ
ンアミドなどのアミド基含有モノマー；ビニルスルホン
酸ソーダ、メタリルスルホン酸ソーダ、２−アクリルア
ミド−２−メチルプロパンスルホン酸ソーダなどのスル
ホン基含有モノマーなどをあげることができる。Examples of the (a 3 ) functional vinyl monomer include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid (including a half ester) and maleic acid (including a half ester). N-methylol derivative monomers such as N-methylol acrylamide and N-butoxymethyl acrylamide; 2-hydroxyethyl (meth) acrylate;
Hydroxy group-containing monomers such as hydroxypropyl (meth) acrylate, polyhydric alcohol mono (meth) acrylate and polyhydric alcohol monoallyl ether; amino group-containing monomers such as dimethylaminoethyl methacrylate and dimethylaminopropyl acrylamide; glycidyl (meth) ) Epoxy group-containing monomers such as acrylate; amide group-containing monomers such as acrylamide, methacrylamide and maleamide; sulfone group-containing such as sodium vinyl sulfonate, sodium methallyl sulfonate, and sodium 2-acrylamido-2-methylpropane sulfonate And monomers.
【００１４】（Ａ）成分のエチレン−ビニルエステル系
共重合体は、重合性二重結合を二個以上有する共重合可
能な架橋モノマーを含有してもよい。このことにより、
機械的強度が向上する。重合性二重結合を二個以上有す
る共重合可能な架橋性モノマーとしては、たとえばジア
リルフタレート、トリアリルシアヌレート、トリアリル
イソシアヌレート、エチレングリコールジアクリレー
ト、アリルメタクリレート、アジピン酸ジアクリレー
ト、トリメチロールプロパンジメタクリレートなどをあ
げることができる。含有量は５重量％以下、好ましくは
３重量％以下である。The ethylene-vinyl ester copolymer as the component (A) may contain a copolymerizable crosslinking monomer having two or more polymerizable double bonds. This allows
The mechanical strength is improved. Examples of copolymerizable crosslinkable monomers having two or more polymerizable double bonds include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol diacrylate, allyl methacrylate, adipic acid diacrylate, trimethylolpropane Dimethacrylate and the like can be given. The content is 5% by weight or less, preferably 3% by weight or less.
【００１５】（Ａ）成分のエチレン−ビニルエステル系
共重合体は、上記のいずれの場合においても、ガラス転
移温度が−２５〜＋１５℃であり、好ましくは−２０〜
＋１０℃である。ガラス転移温度が低過ぎる場合は耐ブ
ロッキング性に劣り、一方該温度が高過ぎる場合は機械
的強度及び耐折性に劣る。In any of the above cases, the ethylene-vinyl ester copolymer (A) has a glass transition temperature of −25 to + 15 ° C., preferably −20 to + 15 ° C.
+ 10 ° C. If the glass transition temperature is too low, the blocking resistance is poor, while if the temperature is too high, the mechanical strength and folding resistance are poor.
【００１６】（Ａ）成分は、通常、乳化重合により得ら
れる。ここで、乳化分散剤中の保護コロイドとして平均
重合度２００〜３０００、好ましくは２５０〜２５００
のポリビニルアルコールを用いて乳化重合することが好
ましい。このことにより、壁紙用途とした場合の耐水
性、耐アルカリ性及び機械的強度を一層高い水準に維持
することができる。The component (A) is usually obtained by emulsion polymerization. Here, the protective colloid in the emulsifying dispersant has an average degree of polymerization of 200 to 3000, preferably 250 to 2500.
It is preferable to carry out emulsion polymerization using polyvinyl alcohol. This makes it possible to maintain water resistance, alkali resistance and mechanical strength at higher levels when used for wallpaper.
【００１７】本発明の（Ｂ）成分は、熱膨張性中空微小
球体である。熱膨張性中空微小球体とは、加熱により膨
張・発泡させることができる微小球体からなる発泡剤で
あり、たとえばポリ塩化ビニリデン、塩化ビニリデンと
アクリロニトリルの共重合体、ポリアクリロニトリル、
アクリロニトリルとアクリル酸メチルの共重合体などか
らなる殻部分の内部にエタン、プロパン、ブタン、ペン
タン、ヘキサン、ヘプタンなどの低沸点炭化水素を含有
する粒径１〜５０μの球体である。かかる（Ｂ）成分と
しては、市販品（たとえば松本油脂社製 商品名「マイ
クロスフェア」）を用いることができる。The component (B) of the present invention is a heat-expandable hollow microsphere. The heat-expandable hollow microspheres are foaming agents composed of microspheres that can be expanded and foamed by heating, for example, polyvinylidene chloride, a copolymer of vinylidene chloride and acrylonitrile, polyacrylonitrile,
It is a sphere having a particle diameter of 1 to 50 μm containing a low-boiling hydrocarbon such as ethane, propane, butane, pentane, hexane or heptane inside a shell portion made of a copolymer of acrylonitrile and methyl acrylate. As the component (B), a commercially available product (for example, trade name “Microsphere” manufactured by Matsumoto Yushi Co., Ltd.) can be used.
【００１８】本発明の（Ｃ）成分は、無機フィラーであ
り、その具体例としては水酸化アルミニウム、水酸化マ
グネシウム、水酸化バリウム、炭酸カルシウム、炭酸マ
グネシウム、硫酸カルシウム、硫酸バリウム、水酸化第
１鉄、塩基性炭酸亜鉛、塩基性炭酸鉛、珪砂、クレー、
タルク、シリカ類、二酸化チタン、ケイ酸マグネシウム
などをあげることができる。好ましくは水酸化アルミニ
ウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグ
ネシウム、水酸化第１鉄、塩基性炭酸亜鉛、二酸化チタ
ンである。The component (C) of the present invention is an inorganic filler, and specific examples thereof include aluminum hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and hydroxide hydroxide. Iron, basic zinc carbonate, basic lead carbonate, silica sand, clay,
Examples include talc, silicas, titanium dioxide, magnesium silicate and the like. Preferred are aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, ferrous hydroxide, basic zinc carbonate, and titanium dioxide.
【００１９】本発明における（Ａ）〜（Ｃ）成分を含有
量については、次のとおりである。The contents of the components (A) to (C) in the present invention are as follows.
【００２０】（Ｂ）成分の含有量は、（Ａ）１００重量
部（固形分基準）あたり５〜５０重量部であり、好まし
くは５〜４０重量部である。（Ｂ）成分が過少な場合は
発泡性に劣り、一方（Ｂ）成分が過多な場合は機械的強
度に劣ると共に、不経済でもある。The content of the component (B) is 5 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight (based on solid content) of the component (A). When the amount of the component (B) is too small, the foaming property is inferior. On the other hand, when the amount of the component (B) is excessive, the mechanical strength is inferior and it is uneconomical.
【００２１】（Ｃ）の含有量は（Ａ）１００重量部（固
形分基準）あたり５０〜３５０重量部であり、好ましく
は８０〜３００重量部である。（Ｃ）成分が過少な場合
は難燃性に劣り、一方（Ｃ）成分が過多な場合は発泡
性、機械的強度及び耐折性に劣る。The content of (C) is 50 to 350 parts by weight, preferably 80 to 300 parts by weight, per 100 parts by weight (based on solid content) of (A). When the amount of the component (C) is too small, the flame retardancy is poor. On the other hand, when the amount of the component (C) is too large, the foaming property, mechanical strength and folding resistance are poor.
【００２２】本発明の難燃性発泡シート用エマルジョン
組成物は、上記の（Ａ）〜（Ｃ）成分の所定量を混合す
ることにより得られる。The emulsion composition for a flame-retardant foamed sheet of the present invention can be obtained by mixing a predetermined amount of the above components (A) to (C).
【００２３】本発明の難燃性発泡シート用エマルジョン
組成物を壁紙として用いるには、たとえば、該組成物を
ロールコーター、リバースロールコーター、ドクターコ
ーター等のコーティング方式やスクリーン印刷、グラビ
ア印刷、彫刻ロール印刷、フレキソ印刷等の凹凸印刷方
式を用いて紙に塗布または印刷し、乾燥後、発泡処理、
エンボス加工を施こせばよい。In order to use the emulsion composition for a flame-retardant foam sheet of the present invention as wallpaper, for example, the composition is coated with a roll coater, reverse roll coater, doctor coater, etc., screen printing, gravure printing, engraving roll. Printing, printing or coating on paper using a concavo-convex printing method such as flexographic printing, drying, foaming,
Embossing may be applied.
【００２４】[0024]
【実施例】次に、本発明を実施例により説明する。評価
法は以下のとおりである。 （１）発泡性 発泡倍率（＝発泡体の厚さ／乾燥塗膜の厚さ）で評価し
た。 （２）耐ブロッキング性 二つの発泡体の塗膜面同士を重ねて合わせ、４５℃、９
０％ＲＨ（相対湿度）の条件下、５ｋｇ／ｃｍ2の荷重
をかけて２４時間放置した。その後、発泡体同士を剥が
し、○（抵抗なし）、△（抵抗あり）及び×（材破）の
基準にて評価した。 （３）耐折性 発泡体を１８０度だけ曲げ、曲げ部分の外観を観察し、
○（異常なし）、△（一部ひび割れあり）及び×（全面
的ひび割れあり）の基準にて評価した。 （４）機械的強度 発泡体の外観を指で摩擦し、外観を観察し、○（異常な
し）、△（一部傷あり）及び×（塗膜の表面剥離あり）
の基準にて評価した。 （５）難燃性 長さ３００ｍｍ、巾３０ｍｍの発泡体を垂直に吊るし、
下部からバーナーにて５秒間あぶり、１分間あたりの燃
焼距離（燃焼速度）を測定した。 （６）作業性（オープンタイム） 発泡体の非塗工面にデンプン糊を塗り付け、２３℃・６
５％ＲＨの条件下で放置し、糊が乾いて接着不能になる
までの時間を測定した。Next, the present invention will be described with reference to examples. The evaluation method is as follows. (1) Foamability Evaluated by foaming ratio (= foam thickness / dry film thickness). (2) Blocking resistance The coating surfaces of the two foams were superimposed on each other,
Under a condition of 0% RH (relative humidity), a load of 5 kg / cm 2 was applied and left for 24 hours. Thereafter, the foams were peeled off from each other and evaluated according to the criteria of ○ (no resistance), Δ (with resistance), and × (breakage of material). (3) Folding resistance Bending the foam by 180 degrees, observing the appearance of the bent portion,
（(No abnormality), △ (partially cracked) and × (entirely cracked) were evaluated. (4) Mechanical strength The appearance of the foam was rubbed with a finger, and the appearance was observed. ○ (no abnormality), Δ (partially scratched), and × (surface peeling of coating film)
Was evaluated based on the following criteria. (5) Flame retardancy A foam having a length of 300 mm and a width of 30 mm is suspended vertically,
Burning was performed for 5 seconds from the bottom with a burner, and the burning distance (burning speed) per minute was measured. (6) Workability (open time) Apply starch paste to the non-coated surface of the foam,
It was left under the condition of 5% RH, and the time required for the paste to dry and become unable to adhere was measured.
【００２５】実施例１〜４及び比較例１〜４ 表１及び表２に示す成分及び水３０重量部をホモミキサ
ーにて混合分散させた。得られた混合液に少量の増粘剤
（東亜合成化学工業（株）アロンＡ−２０Ｌ）を添加
し、粘度を６０００ｃｐｓに調整し、難燃性発泡シート
用エマルジョン組成物（固形分６６重量％）とした。該
組成物を、乾燥後の厚さが０．１５ｍｍとなるように壁
紙用基紙（防湿加工未処理紙）に塗布し、１００℃で１
０分間乾燥させ、更に１８０℃で１分間加熱することに
より発泡させた。得られた発泡体について次のとおり評
価を行った。結果を表１及び表２に示した。Examples 1 to 4 and Comparative Examples 1 to 4 The components shown in Tables 1 and 2 and 30 parts by weight of water were mixed and dispersed by a homomixer. A small amount of a thickener (Toa Gosei Chemical Industry Co., Ltd., Alon A-20L) was added to the obtained mixture to adjust the viscosity to 6000 cps, and the emulsion composition for a flame-retardant foamed sheet (solid content 66% by weight) was added. ). The composition is applied to a wallpaper base paper (moisture-proof unprocessed paper) so that the thickness after drying is 0.15 mm.
It was dried for 0 minutes and further foamed by heating at 180 ° C. for 1 minute. The obtained foam was evaluated as follows. The results are shown in Tables 1 and 2.
【００２６】結果から次のことがわかる。本発明の条件
を満足するすべての実施例においては、すべての評価項
目において満足すべき結果を示している。一方、本発明
の規定を欠く各比較例は、次のとおり不満足な結果を示
している。（Ａ）成分における必須の構成単位であるバ
ーサチック酸ビニル及びアクリル酸−２−エチルヘキシ
ルの共重合体中の含有量が１０重量％未満である比較例
１及び２はオープンタイムが短く、作業性に劣ってい
る。（Ａ）成分における必須の構成単位であるバーサチ
ック酸ビニルの含有量が過多であり、かつガラス転移温
度が低すぎる比較例３は耐ブロッキング性、機械的強度
に劣っている。バーサチック酸ビニル及びアクリル酸−
２−エチルヘキシルの共重合体中の含有量が１０重量％
未満であり、かつガラス転移温度が高すぎる比較例４は
オープンタイムが短く、作業性に劣っており、かつ耐折
性に劣っている。The following can be understood from the results. In all examples satisfying the conditions of the present invention, satisfactory results are shown in all evaluation items. On the other hand, each comparative example lacking the definition of the present invention shows an unsatisfactory result as follows. In Comparative Examples 1 and 2, in which the content of the copolymer of vinyl versatate and 2-ethylhexyl acrylate, which are essential constitutional units in the component (A), is less than 10% by weight, the open time is short and workability is low. Inferior. Comparative Example 3 in which the content of vinyl versatate, which is an essential constituent unit in the component (A), is too large and the glass transition temperature is too low is inferior in blocking resistance and mechanical strength. Versatic acid and acrylic acid
The content of 2-ethylhexyl in the copolymer is 10% by weight.
Comparative Example 4 in which the glass transition temperature was too low and the glass transition temperature was too high, the open time was short, the workability was poor, and the folding resistance was poor.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【表２】 [Table 2]
【００２９】［表の説明］ a 1 ：エチレン a 2 ：酢酸ビニル ＶＶ：バーサチック酸ビニル ＥＨＡ：アクリル酸−２−エチルヘキシル Ｔｇ：ガラス転移温度 保護コロイド ＰＶＡ：平均重合度１０００のポリビニルアルコール ＮＯＮ：ノニオン系界面活性剤（ポリオキシエチレンノ
ニルフェニルエーテル）[Explanation of Table] a 1 : Ethylene a 2 : Vinyl acetate VV: Vinyl versatate EHA: 2-ethylhexyl acrylate Tg: Glass transition temperature Protective colloid PVA: Polyvinyl alcohol having an average polymerization degree of 1000 NON: Nonionic Surfactant (polyoxyethylene nonyl phenyl ether)
【００３０】[0030]
【発明の効果】以上説明したとおり、本発明により、地
球環境及び作業環境の観点から好ましくない塩化ビニル
を用いることなく、難燃性、機械的強度、耐折性、耐ブ
ロッキング性、発泡性及びエンボス特性に優れ、しかも
オープンタイムが長いため作業性に優れ、よって壁紙等
の用途に最適に使用される水性エマルジョン組成物及び
該水性エマルジョン組成物を用いて得られる発泡シート
を提供することができた。As described above, according to the present invention, flame retardancy, mechanical strength, folding resistance, blocking resistance, foaming property and the like can be obtained without using vinyl chloride which is not preferable from the viewpoint of the global environment and working environment. It is possible to provide an aqueous emulsion composition which is excellent in embossing properties and excellent in workability due to a long open time, and thus is optimally used for applications such as wallpaper, and a foamed sheet obtained using the aqueous emulsion composition. Was.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 33/08 Ｃ０８Ｌ 33/08 Ｄ２１Ｈ 27/20 Ｄ２１Ｈ 27/20 Ａ Ｆターム(参考） 4F074 AA41 AA42 AA48 AA98 AB04 AG01 AG15 AH04 BA91 CA29 CC04X CC04Y DA02 DA52 4J002 BD102 BF021 BF031 BG041 BG102 DE067 DE077 DE117 DE147 DE237 DE267 DG047 DG057 DJ007 DJ017 DJ037 DJ047 EA016 FD017 FD202 FD326 GL00 HA07 4L055 AG17 AG57 AG59 AG64 AG71 AG89 AG94 AH33 AH34 AJ08 AJ10 BE08 BE20 EA20 EA30 EA32 FA13 FA19 FA30 GA23──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08L 33/08 C08L 33/08 D21H 27/20 D21H 27/20 A F term (Reference) 4F074 AA41 AA42 AA48 AA98 AB04 AG01 AG15 AH04 BA91 CA29 CC04X CC04Y DA02 DA52 4J002 BD102 BF021 BF031 BG041 BG102 DE067 DE077 DE117 DE147 DE237 DE267 DG047 DG057 DJ007 DJ017 DJ037 DJ047 EA016 FD017 FD202 FD326 GL00 AG07 AG08A08 AG17 AG08 EA32 FA13 FA19 FA30 GA23
Claims (7)
（Ｂ）の含有量は（Ａ）１００重量部（固形分基準）あ
たり５〜５０重量部であり、（Ｃ）の含有量は（Ａ）１
００重量部（固形分基準）あたり５０〜３５０重量部で
ある水性エマルジョン組成物。 （Ａ）：（ａ1）エチレン５〜３５重量％及び（ａ2）ビ
ニルエステル９５〜６５重量％からなるエチレン−ビニ
ルエステル系共重合体であって、該ビニルエステルとし
てバーサチック酸ビニル及び／又はアクリル酸−２−エ
チルヘキシルを含有し、共重合体中のバーサチック酸ビ
ニル及びアクリル酸−２−エチルヘキシルの共重合体中
の合計含有量は１０〜６０重量％であり、ガラス転移温
度が−２５〜＋１５℃であるエチレン−ビニルエステル
系共重合体を含有する水性エマルジョン （Ｂ）：熱膨張性中空微小球体 （Ｃ）：無機フィラー1. It contains the following components (A) to (C),
The content of (B) is 5 to 50 parts by weight per 100 parts by weight (based on solid content) of (A), and the content of (C) is 1 (A) 1
An aqueous emulsion composition which is 50 to 350 parts by weight per 00 parts by weight (based on solid content). (A): an ethylene-vinyl ester copolymer comprising (a 1 ) 5 to 35% by weight of ethylene and (a 2 ) 95 to 65% by weight of a vinyl ester, wherein the vinyl ester is vinyl versatate and / or It contains 2-ethylhexyl acrylate, the total content of vinyl versatate and 2-ethylhexyl acrylate in the copolymer is 10 to 60% by weight, and the glass transition temperature is -25 to 25%. Aqueous emulsion containing ethylene-vinyl ester copolymer at + 15 ° C. (B): heat-expandable hollow microspheres (C): inorganic filler
系共重合体が、請求項１記載の（ａ1）及び（ａ2）並び
に（ａ3）官能性ビニル単量体を含有し、共重合体中の
（ａ3）の含有量が１０重量％以下である請求項１記載
の水性エマルジョン組成物。Wherein component (A) of ethylene - vinyl ester copolymer contains a claim 1, wherein (a 1) and (a 2) and (a 3) functional vinyl monomer, co the aqueous emulsion composition of claim 1, wherein the content is 10 wt% or less in the polymer (a 3).
イドとして平均重合度２００〜３０００のポリビニルア
ルコールを用い、乳化重合により得られるエチレン−ビ
ニルエステル系共重合体を含有する水性エマルジョンで
ある請求項１記載の水性エマルジョン組成物。3. An aqueous emulsion containing an ethylene-vinyl ester copolymer obtained by emulsion polymerization using polyvinyl alcohol having an average degree of polymerization of 200 to 3000 as a protective colloid in the emulsifying dispersant. An aqueous emulsion composition according to claim 1.
項１記載の水性エマルジョン組成物。4. The aqueous emulsion composition according to claim 1, which is used for producing a foamed sheet.
水性エマルジョン組成物。5. The aqueous emulsion composition according to claim 4, wherein the foam sheet is wallpaper.
を用いて得られる発泡シート。6. A foamed sheet obtained by using the aqueous emulsion composition according to claim 1.
を用いて得られる壁紙。7. Wallpaper obtained using the aqueous emulsion composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26458798A JP3629369B2 (en) | 1998-09-18 | 1998-09-18 | Aqueous emulsion composition and foam sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26458798A JP3629369B2 (en) | 1998-09-18 | 1998-09-18 | Aqueous emulsion composition and foam sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000095915A true JP2000095915A (en) | 2000-04-04 |
| JP3629369B2 JP3629369B2 (en) | 2005-03-16 |
Family
ID=17405376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26458798A Expired - Fee Related JP3629369B2 (en) | 1998-09-18 | 1998-09-18 | Aqueous emulsion composition and foam sheet |
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| Country | Link |
|---|---|
| JP (1) | JP3629369B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002019050A (en) * | 2000-07-04 | 2002-01-22 | Toppan Printing Co Ltd | Foamed decorative material |
| KR101223613B1 (en) | 2009-10-16 | 2013-01-17 | 황규성 | Aqueous expansion solution, expanded coating method and sheet product using the same |
-
1998
- 1998-09-18 JP JP26458798A patent/JP3629369B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002019050A (en) * | 2000-07-04 | 2002-01-22 | Toppan Printing Co Ltd | Foamed decorative material |
| KR101223613B1 (en) | 2009-10-16 | 2013-01-17 | 황규성 | Aqueous expansion solution, expanded coating method and sheet product using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3629369B2 (en) | 2005-03-16 |
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