JPS598777A - Aqueous resin dispersion composition - Google Patents

Abstract

PURPOSE:The titled composition, prepared by incorporating a specific aqueous tackifier resin dispersion and an aqueous dispersion of a thermoplastic resin and a plasticizer in a specific proportion, nontacky at ordinary temperature, exhibiting the tackiness by heating, and retaining the tackiness even at room temper- ature. CONSTITUTION:An aqueous resin dispersion composition, prepared by incorporating (A) an aqueous dispersion of a tackifier resin having 50-130 deg.C softening point, e.g. abietic acid rosin, preferably obtained by dispersing 100pts.wt. tachifier in 80-1000pts.wt water with 2-30pts.wt. dispersing agent such as a surfactant, with(B) an aqueous dispersion of a uniform mixture of 30-80wt% thermoplastic resin, e.g. ethylene-vinyl acetate copolymer, with 70-20wt% plasticizer, e.g. dicyclohexyl phthalate, at (1/9)-(9/1) solid ratio between the components (A) and (B), and having 50-135 deg.C minimal film forming temperature. USE:Heat sensitive adhesive labels, backing materials for carpets, etc.

Description

【発明の詳細な説明】 本発明は、室温（２０℃）では粘着性を示さないが、加
熱によって粘着性が発現し、一旦、粘着性が発現される
と再び室温に戻されてもその粘着性を長時間持続する感
熱型粘着性皮膜を与える樹脂水性分散液組成物に関する
。Detailed Description of the Invention The present invention does not exhibit tackiness at room temperature (20°C), but develops tackiness when heated, and once tackiness is developed, the tackiness remains even when returned to room temperature. The present invention relates to an aqueous resin dispersion composition that provides a heat-sensitive adhesive film that maintains its properties for a long time.

従来の粘着ラベル、シール、ステッカ−等は、印刷され
たアート紙、アルミニウム箔、ポリエチレンテレフタレ
ートフィルムの裏面に感圧型粘着剤を塗工し、この粘着
剤層の表面を剥離紙で覆ったものである。この剥離紙は
使用に先立って剥離され、棄てられるので材料コストの
面および省資源の面から好寸しくない。Conventional adhesive labels, stickers, stickers, etc. are made by coating a pressure-sensitive adhesive on the back side of printed art paper, aluminum foil, or polyethylene terephthalate film, and then covering the surface of this adhesive layer with release paper. be. This release paper is peeled off and discarded prior to use, which is undesirable in terms of material cost and resource conservation.

一方、ホットメルト接着剤を使ったラベル、シール、あ
るいはシートは常温で非粘着性であるが、加熱活性化し
熱源を取り去ると接着性の持続時間が例えば数秒と短か
いので作業性に問題がある。On the other hand, labels, stickers, or sheets using hot melt adhesives are non-adhesive at room temperature, but when activated by heat and the heat source is removed, the adhesiveness lasts only a few seconds, which poses problems in workability. .

上記の欠点を解決するための接着剤として例えば特開昭
５１−８１８３２号公報に記載の感熱性材料に粘着附与
剤を配合してなる感熱性粘着剤の例があるが加熱活性化
するのに例えば数分と時間がかかりすぎるのが欠点であ
る。鷹だ特開昭５１−１１１２４６号公報に記載のスチ
レンとブタジェンまたはスチレンとイソプレンのブロッ
ク共重合体に粘着附与剤と結晶性可塑剤とを配合してな
る熱活性粘着組成物があるがこの粘着組成物を塗布した
基拐をラベル、シールあるいはシートを作１ｊｙ：する
ため打抜き加工する際に切断面が再付着するなど作柴性
が悪いという欠点がある。As an adhesive to solve the above-mentioned drawbacks, there is an example of a heat-sensitive adhesive prepared by blending a heat-sensitive material with a tackifying agent, as described in JP-A-51-81832. The disadvantage is that it takes too long, for example, several minutes. There is a heat-activated adhesive composition prepared by blending a block copolymer of styrene and butadiene or styrene and isoprene with a tackifying agent and a crystalline plasticizer, as described in Takada JP-A-51-111246. Since the substrate coated with the adhesive composition is used to make labels, stickers, or sheets, there is a drawback that the cut surface re-adheres when punching, resulting in poor cutting properties.

かかる欠点を改良する方法として、 ■エチレン・酢酸ビニル共重合体　　１００重址部（Ｂ
）粘着性樹脂　　　　　　　　　１０〜１５０重畦部（
Ｃ）結晶性可塑剤　　　　　　　　：３０〜２５０重址
部０）ワックス　　　　　　　　　　０へ−７０重級部
上記■及至０成分を上記割合で配合した組成物をソート
状基材に溶融塗布し冷却して、あるいけ該組成物を有機
溶剤に溶解した液を塗布し乾燥させて常温では非粘着性
であり、加熱により活性化１、加熱源をとり去った後に
も粘着性が暫時持続する感熱接着シートが提案された（
特開昭５６−１０６９８４号公報）。As a method to improve this drawback, ■ 100 parts of ethylene/vinyl acetate copolymer (B
) Adhesive resin 10 to 150 layers (
C) Crystalline plasticizer: 30 to 250 parts by weight 0) Wax 0 to 70 parts by weight A composition containing the above components 1 to 0 in the above proportions is melt-coated onto a sorted substrate, cooled, and then A heat-sensitive adhesive sheet is proposed that is non-tacky at room temperature by applying a solution of the composition dissolved in an organic solvent and drying, and that is activated by heating (1) and remains sticky for a while even after the heat source is removed. was done (
JP-A No. 56-106984).

この感熱接着シーｌ−は常温では粘着性を示さないので
剥離紙が不用であり、捷だ、ラベル、シール等の用途の
ために打抜加■：する際に切断面が打抜刃に付着しない
利点を有する。This heat-sensitive adhesive sticker does not exhibit adhesiveness at room temperature, so no release paper is required, and the cut surface adheres to the punching blade during punching for purposes such as folding, labels, and stickers. It has no advantage.

Ｅ〜か１〜ながら、該感熱接着ソートが常温で粘着性を
示さなくなるには、前記組成物の溶融物をソート基材に
塗布した後、１〜２週間経過する必要があり、また組成
物の溶解液をシート基材に塗布した場合には塗布後１週
間経過する必要があり、出荷前の保管が面倒である。更
に後者の溶剤を用いる方法は環境安全面一ヒ、衛生面上
好捷しくない。E~(1) However, in order for the heat-sensitive adhesive sort to stop exhibiting tackiness at room temperature, it is necessary for 1 to 2 weeks to elapse after the melt of the composition is applied to the sorting substrate, and the composition When the solution is applied to a sheet base material, it is necessary to wait one week after application, and storage before shipping is troublesome. Furthermore, the latter method using a solvent is unsatisfactory in terms of environmental safety and hygiene.

一般に軟化点が５０〜１３５℃の粘着性樹脂（ａ）はそ
れ自体常温（２０℃）で粘着性を示さないが、結晶性ｄ
■塑剤（１））と均一な組成物を形成すると常温でも粘
着性を示す。上記粘着シートにおいて、基材に粘着性樹
脂組成物を塗布後、１−２週間後に粘着シートが常温で
粘着性を示さなくなるがこれは結晶性可塑剤の結晶化が
進行するにつれて均一な組成物が粘着性樹脂と結晶性可
塑剤に分離することに起因する。In general, the adhesive resin (a) with a softening point of 50 to 135°C does not exhibit adhesiveness itself at room temperature (20°C), but has crystalline d
■When a homogeneous composition is formed with plasticizer (1)), it exhibits tackiness even at room temperature. In the above-mentioned pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet stops exhibiting tackiness at room temperature 1 to 2 weeks after the adhesive resin composition is applied to the base material, but this is because the composition becomes uniform as the crystallization of the crystalline plasticizer progresses. This is due to the separation of adhesive resin and crystalline plasticizer.

本発明者等は、従来の塗布物が常温で非粘着性を示さな
くなる迄に１〜２週間要する欠点を改良する目的で神々
の樹脂組成物を検討したところ、粘着性樹脂の水性分散
液と可塑剤の水性分散液を混合し２だ水性分散液組成物
を塗布剤として用いれば水を乾燥により飛散して得た塗
膜は、常温では粘着性を示さないが、加熱することによ
り粘着性を示し、一旦、粘着性を示した後は、室温迄冷
却しても長時間その粘着性を持続することを晃い出１２
、本発明に到達した。The present inventors investigated a divine resin composition for the purpose of improving the drawback that conventional coatings require 1 to 2 weeks to become non-adhesive at room temperature, and found that an aqueous dispersion of a tacky resin. If an aqueous dispersion of a plasticizer is mixed and the aqueous dispersion composition is used as a coating agent, the coating film obtained by scattering water by drying will not exhibit tackiness at room temperature, but will become tacky when heated. It has been shown that once it exhibits tackiness, it maintains its tackiness for a long time even if it is cooled to room temperature12.
, arrived at the present invention.

即ち、本発明は、 第［１］液： 軟化点が５０〜１３０℃の粘着性樹脂の水性分散液 第囲液： （Ａ）、熱可塑性樹脂　　　　　　３０〜８０重量係（
Ｂ）、可塑剤　　　　　　　　　７０〜２０重着係固型
分比が上記割合の水性分散液 第（１１液と第１旧液が固型分比で１／９〜９／１の割
合で配合されている最低造膜温度が５０〜１３５℃の樹
脂水性分散液組成物を提供するものである。That is, the present invention includes: [1] Liquid: An aqueous dispersion of a sticky resin having a softening point of 50 to 130°C Surrounding liquid: (A) Thermoplastic resin 30 to 80% by weight (
B) Plasticizer: 70 to 20 Aqueous dispersion with the above-mentioned solids ratio (liquid 11 and old liquid 1 are blended at a solids ratio of 1/9 to 9/1) The present invention provides an aqueous resin dispersion composition having a minimum film forming temperature of 50 to 135°C.

本発明の実施において、第（ＩＩＭの粘着性樹脂の水性
分散液は、粘着性樹脂組成物重量部を分散剤２〜３０重
吋部用いて水８０〜１０００重駄部に分散させたもので
ある。In the practice of the present invention, the aqueous dispersion of the adhesive resin (IIM) is prepared by dispersing parts by weight of the adhesive resin composition in 80 to 1000 parts by weight of water using 2 to 30 parts by weight of a dispersant. be.

軟化点が５０〜１３０℃の粘着性樹脂としてｄ１アビエ
チン酸ロジン、その水添加物およびこれら（７）−７１
／　イン酸付加物、金属塩、グリセリン、ペンタエリス
リト−ル、エチレングリコール、ジエチレングリコール
等のアルコールとのエステル化物等のロジン誘導体、あ
るいは、α−ピネン、β−ピネン、ジペンテン等のホモ
重合体またにこれらの共重合体、テルペンフェノール共
重合体、およびこれらの水添加物などのテルペン及びそ
の誘導体あるいけ、石油樹脂、水添石油樹脂、クマロン
−インデン樹脂等の軟化点が５０〜１３０℃、好まし７
〈は７０〜１２０℃のものが使用される。d1 abietic acid rosin, its water additives, and these (7)-71 as adhesive resins with a softening point of 50 to 130°C
/ Rosin derivatives such as inic acid adducts, metal salts, glycerin, pentaerythritol, esters with alcohols such as ethylene glycol and diethylene glycol, or homopolymers such as α-pinene, β-pinene, dipentene, etc. Terpenes and their derivatives such as these copolymers, terpene-phenol copolymers, and water additives thereof, petroleum resins, hydrogenated petroleum resins, coumaron-indene resins, etc. have a softening point of 50 to 130°C, Preferable 7
< is used at a temperature of 70 to 120°C.

軟化点が５０℃未満では得られる塗膜がプロソギング１
．やすい。If the softening point is less than 50℃, the resulting coating film will be Prosogging 1.
．． Cheap.

分散剤とし２ては、界面活性剤、カルボギ７メヂルセル
ロース、部分ケン化ポリビニルアルコール、ポリアクリ
ル酸の部分中和塩等が挙げられる。Examples of the dispersant 2 include surfactants, carboxy 7-methyl cellulose, partially saponified polyvinyl alcohol, and partially neutralized salts of polyacrylic acid.

肘粘着性樹脂の水性分散液の製造は、例えば次の方法に
より行うことができる。すなわち粘着性樹脂を攪拌装置
と加熱装算を設けた容器中で融解するまで加熱ｌ、溶融
状態の粘着性樹脂を得る。この時の温度は通常９０〜１
９０℃の範囲である。The aqueous dispersion of elbow adhesive resin can be produced, for example, by the following method. That is, the adhesive resin is heated in a container equipped with a stirring device and a heating device until it melts, thereby obtaining a molten adhesive resin. The temperature at this time is usually 90-1
It is in the range of 90°C.

このようにして得られた熱溶融粘着性樹脂を攪拌［−な
がら、分散剤の水溶液を添加（〜、水が分散相で粘着性
樹脂が連続相であるエマルジョンを應る。While stirring the hot-melt adhesive resin thus obtained, an aqueous solution of a dispersant is added (~, and the emulsion in which water is the dispersed phase and the adhesive resin is the continuous phase is sifted).

この段階で使用される水の量は粘着性樹脂が７０〜８５
重量％となる量である。次に激しく攪拌しながら温水を
添加する。温水の添加量は、粘着性樹脂の濃度が５〜７
０重都チ、好壕しくけ１０〜５５重量％になるように適
宜定める。この段階でエマルジョンが反転し、水が連続
相になり粘着性樹脂が分散相になる。これを冷却すると
微細に分散された固体粘着性樹脂の水性分散体が得られ
る（特開昭５７−９８５５８号公報）。The amount of water used at this stage is 70-85% of the adhesive resin.
This is the amount in weight%. Then add warm water with vigorous stirring. The amount of hot water added is such that the concentration of adhesive resin is 5 to 7.
It is determined as appropriate to have a weight of 0% and a suitable depth of 10 to 55% by weight. At this stage, the emulsion is inverted, with water becoming the continuous phase and the sticky resin becoming the dispersed phase. When this is cooled, an aqueous dispersion of finely dispersed solid adhesive resin is obtained (Japanese Unexamined Patent Publication No. 57-98558).

また、特開昭５６−２１４９号公報に開示される二軸押
出機を用い、上記の工程を後記の製造例に示す如く連続
的に行うことも１丁能である。It is also possible to carry out the above steps continuously using a twin-screw extruder disclosed in JP-A-56-2149 as shown in the production example below.

次に第（ｌＩ）液の可塑剤を含有する樹脂の水性分散液
は、 ■、熱可塑性樹脂　　　３０〜８０劃ｌ％、好ましくは
４０〜７０劃ｌ ０３）、可塑剤　　　　　　７０〜２０重量％、好ま［
７〈は６０〜３０重量％ の均一混合物１００重量部を分散剤２〜３０重量部を用
いて水８０〜１０００重量部に分散させたものである。Next, the aqueous dispersion of a resin containing a plasticizer as the liquid (lI) is as follows: Like [
7 is obtained by dispersing 100 parts by weight of a homogeneous mixture of 60 to 30% by weight in 80 to 1000 parts by weight of water using 2 to 30 parts by weight of a dispersant.

この第［１１’ｌ液は、第［Ｔ］液の製造法において、
粘着性樹脂の代りに上記■成分と（Ｂ）成分の均一溶融
混合物を用いることにより製造される。This [11'l liquid] is used in the manufacturing method of the [T] liquid.
It is produced by using a homogeneous molten mixture of component (1) and component (B) above in place of the adhesive resin.

上記（４）成分の熱可塑性樹脂としては、エチレン−酢
酸ビニル共重合体、エチレン−アクリル酸エステル共重
合体、エチレン−メタクリル酸エステル共重合体、エチ
レン−プロピ１／ンランダム共重合体、エチレン−ブテ
ンランダム共重合体、エチレン−プロピレン−ブテン共
重合体、エチレン−アクリル酸共重合体、エチレン−メ
タクリル酸共重合体およびこれらの金属（Ｎａ、　Ｋ、
　Ｌｉ、　Ｚｎ）塩等のエチレン系樹脂ニアタクチック
ポリプロピレン、プロピレン−ブテン共重合体等の非晶
性プロピレン系重合体；スチレンーブタジエンースチｌ
／ン共重合体、スチレンーイソゾレンースチレン共重合
体等のスチレン系ブロック共重合体あるいはそれらの水
素添加物；ポリ塩化ビニル等があげられる。The thermoplastic resin of the above component (4) includes ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, ethylene-methacrylic ester copolymer, ethylene-propylene 1/2 random copolymer, ethylene -butene random copolymer, ethylene-propylene-butene copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer and these metals (Na, K,
Ethylene-based resins such as Li, Zn) salts, near-tactic polypropylene, amorphous propylene-based polymers such as propylene-butene copolymers; styrene-butadiene-based polymers;
Examples include styrenic block copolymers such as /N copolymers, styrene-isozolene-styrene copolymers, and hydrogenated products thereof; polyvinyl chloride, and the like.

（Ｂ’ｌ成分の可塑剤は、前記粘着性樹脂を可塑化する
液状の可塑剤または結晶性可塑剤である。ここで結晶性
可塑剤とけ軟化点以下の温度では固形結晶状態であり、
一旦溶融された後熱を取り去ってもすぐには結晶化せず
ゆっくりと結晶化するものである。(The plasticizer of component B'l is a liquid plasticizer or a crystalline plasticizer that plasticizes the adhesive resin. Here, the crystalline plasticizer is in a solid crystal state at a temperature below the melting point,
Once melted, even if the heat is removed, it does not crystallize immediately but slowly.

前記液状の可塑剤としては、アマニ油、大豆油、ひ捷し
油、トール油等の食物油；プロセス油；フタル酸ジエチ
ル、フタル酸ジーｎ・ブチル、フタル酸ジヘキンル、フ
タル酸ジオクチル等のフタル酸エステル系可塑剤；アジ
ピン酸ジーｉ・ブチル、アジピン酸ジオクチル、セパチ
ン酸ジブチル、セパチン酸ジオクチル、アゼライン酸ジ
ーｎ−ヘキシル等Ω脂肋族二塩基酸エステル類；リン酸
ジフェニル−２・エチルヘキシル等のリン酸エステル類
；酒石酸ジエチル、アセチルクエン酸トリエチル、アセ
チルクエン酸トリブチル、クエン酸トリブチル、クエン
酸七ノステアリル等のヒドロキシ多価カルボン酸ニスデ
ル類、アセチルリノシール酸メチル、パルミチン酸エチ
ル、ステアリン酸ｎ−ブチル等の脂肪酸エステル類；グ
リセリントリアセテート、グリセリントリプロピオネー
ト、グリセリン）・リブチレート、グリセリントリヘプ
タノエート等の多価アルコールエステル類；さらには、
エボキン化すフラワー油、エポキシ化大豆油、エポキシ
化ヒマシ油、エポキシ化アマニ油等のエポキシ系可塑剤
等が挙げらねる。The liquid plasticizers include food oils such as linseed oil, soybean oil, strained oil, and tall oil; process oils; phthalates such as diethyl phthalate, di-n-butyl phthalate, dihexyl phthalate, and dioctyl phthalate; Acid ester plasticizers; di-butyl adipate, dioctyl adipate, dibutyl sepatate, dioctyl sepatate, di-n-hexyl azelaate, etc. Omega fatty acid esters; diphenyl-2-ethylhexyl phosphate, etc. Phosphate esters; Nisderic hydroxy polycarboxylic acids such as diethyl tartrate, triethyl acetyl citrate, tributyl acetyl citrate, tributyl citrate, heptanostearyl citrate, methyl acetyl linosylate, ethyl palmitate, stearic acid Fatty acid esters such as n-butyl; polyhydric alcohol esters such as glycerin triacetate, glycerin tripropionate, glycerin) butyrate, and glycerin triheptanoate;
Examples include epoxy plasticizers such as epoxidized flower oil, epoxidized soybean oil, epoxidized castor oil, and epoxidized linseed oil.

また、後者の結晶性可塑剤としては、フタル酸ジシクロ
ヘキシル、フタル酸ジフェニルエステル、フタル酸ジ−
α−ナフチルエステルステアリン酸グリコール、リン酸
トリフェニル、アゼライン酸ジフエナシルエステル等が
あケラれる。The latter crystalline plasticizers include dicyclohexyl phthalate, diphenyl phthalate, and di-phthalate.
α-Naphthyl ester glycol stearate, triphenyl phosphate, azelaic acid diphenacyl ester, etc.

第開液において、可塑剤とともに熱可塑性樹脂を併用す
るのけ、可塑剤のみでは溶剤の助は全借りないと貯献安
定な水分散液を得ることができない。捷だ、熱可塑性樹
脂の存在により水性分散液組成物より得られる塗膜の抗
プロツギング性が向上する。In the first solution opening, even if a thermoplastic resin is used in combination with a plasticizer, it is not possible to obtain a storage-stable aqueous dispersion using only a plasticizer without the assistance of a solvent. However, the presence of the thermoplastic resin improves the anti-progging properties of the coating film obtained from the aqueous dispersion composition.

第（Ｉｌ］液における可塑剤と熱可塑性樹脂の成分和に
対して可塑剤は２０〜７０重＃係、好ｉｔ、＜け３０〜
６０重量多用いられる〇 第ｍ液と第四］液の混合は攪拌下に行われる。なお、第
［＋］液と第［Ｉｌ］液のイオン性が異なる場合は［〜
ばしはゲル化が起るので、粘着剤、分散剤、熱可塑性樹
脂を選択する必要があることは当然である。The plasticizer is 20 to 70% by weight relative to the sum of the components of the plasticizer and thermoplastic resin in the liquid No. (Il).
60 The mixing of liquid m and liquid 4, which are used in large amounts by weight, is carried out with stirring. In addition, if the ionicity of the [+] solution and the [Il] solution are different, [~
Since gelation occurs in brush, it is natural that adhesives, dispersants, and thermoplastic resins must be selected.

第（１１液と第［旧液が１／９〜９／１、好−ｉ　Ｌ　
＜は２／８〜？／３（［＋］液／（旧液）に均一に混合
された樹脂水性分散液の最低造膜温度（ＭＦＴ）は少な
くとも５０℃以十であり、好ましくけ５５〜１３０℃で
ある。ＭＦＴが５０℃未満であると該組成物を紙、アル
ミニウム箔等の基材上に塗布して得た皮膜が夏場にブロ
ッキングを生じたり、加熱前に粘着性を示す。11th liquid and 1st liquid [old liquid is 1/9~9/1, good-i L
<is 2/8~? /3 ([+] liquid/(old liquid) The minimum film forming temperature (MFT) of the resin aqueous dispersion uniformly mixed is at least 50°C or higher, preferably 55 to 130°C. If the temperature is lower than 50°C, a film obtained by applying the composition onto a substrate such as paper or aluminum foil may cause blocking in summer or exhibit stickiness before heating.

かかる水性分散液組成物は紙、アルミニウム箔、樹脂フ
ィルム等の基材に塗布され、ＭＦＴより低い温度で乾燥
され、あるいはＭＦＴ以上の温度であっても連続皮膜が
形成されない時間加熱され不連続皮膜が形成される。Such an aqueous dispersion composition is applied to a substrate such as paper, aluminum foil, or resin film, and dried at a temperature lower than the MFT, or heated at a temperature higher than the MFT for a time that does not form a continuous film to form a discontinuous film. is formed.

該不連続皮膜が形成された紙、合成紙、アルミニウム箔
等のシー）［物は型抜され、ステッカ−ハラベル等と［
７て使用される。The sheet of paper, synthetic paper, aluminum foil, etc. on which the discontinuous film is formed is cut out, and then stamped with a sticker, halo label, etc.
7 is used.

この不連続皮膜は常温では粘着性を示さないが、前記Ｍ
ＦＴ以−トート度に加熱されると粘着性樹脂−＼可塑剤
が移行し均一な組成物となって透明な連続皮膜が形成さ
れる。この連続皮膜は粘着性を示す。次いで室温迄冷却
さ力ても該皮膜は１０〜２０日間粘着性を持続する。This discontinuous film does not show tackiness at room temperature, but the M
When heated to a temperature higher than FT, the adhesive resin/plasticizer migrates and becomes a uniform composition, forming a transparent continuous film. This continuous film exhibits tackiness. The film remains tacky for 10 to 20 days upon subsequent cooling to room temperature.

本発明の樹脂水性分散液組成物は、」−１記のように感
熱粘着性ラベル用の粘着剤の他に、カーペット用バッキ
ング材；壁紙、皮革用粘着剤とし、でも利用可能である
。The aqueous resin dispersion composition of the present invention can be used not only as an adhesive for heat-sensitive adhesive labels as described in item 1-1, but also as an adhesive for carpet backing materials, wallpaper, and leather.

次に、実施例及び比較例をあげて本発明をきらに詳述す
る。なお、例中の係および部は特に倒起しない限り重量
基準である。Next, the present invention will be explained in detail with reference to Examples and Comparative Examples. In addition, the terms and parts in the examples are based on weight unless otherwise specified.

Ｎ、Ｎ−ジメチルアミンエチルメタクリｌ／−）６２．
９部（０，４モル）、ブチルメタアクリレ−ドア１部（
０，５モル）、ラウリルメタアクリレート２５．４　部
（ｏ、ｔモル）およびインプロピルアルコール２００部
を攪拌機、還流冷却管、温度計、滴下ロートを装置した
４ツロフラスコ内に仕込み、窒素ガス置換後、２．２’
−アゾビスイソブチロニトリル０．９部を重合開始剤と
して添加し、８０℃にて４時間重合反応を行った。次い
で、酢酸２４部（０，４モル）で中和１７た後、イソプ
ロピルアルコールを留去しながら、水を添加し、最終的
に固型分３５チの粘稠な分散剤の水溶液を得た。N,N-dimethylamine ethyl methacrylate l/-)62.
9 parts (0.4 mol), 1 part of butyl methacrylate (
0.5 mol), 25.4 parts (o, t mol) of lauryl methacrylate, and 200 parts of inpropyl alcohol were charged into a 4-volume flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, and after purging with nitrogen gas. , 2.2'
-0.9 part of azobisisobutyronitrile was added as a polymerization initiator, and a polymerization reaction was carried out at 80°C for 4 hours. Next, after neutralizing with 24 parts (0.4 mol) of acetic acid, water was added while distilling off the isopropyl alcohol, and finally a viscous aqueous dispersant solution with a solid content of 35 was obtained. .

実施例１ ０ジンのグリセリンエステル（荒用化学製エステルガム
ＡＡＶ）を１００重量部／時間の割合で二軸押出機（池
貝鉄Ｔ社製ＰＣＭ４５（ＩＪ）のホッパーより供給し、
１１０℃で混練し、一方、該押出機のメタリングゾーン
に設けた第１の供給口から前記例で得た分散剤水溶液を
ギヤポンプにより２０重Ｉ部／時間の割合で連続的に供
給した。引き続いて該押出機のよりダイ側に設けた第２
の供給口より７０重量部／時間の割合で熱水全プランジ
ャーポンプにより連続的に供給し、押出温ＩＷ１１０℃
、２５０　ｒｐｍ　で押出１７、白色の水性分散液を連
続的に製造ｌ〜、第（１１液とした。Example 1 0 Glycerin ester (Ester Gum AAV manufactured by Arayo Kagaku) was supplied at a rate of 100 parts by weight/hour from the hopper of a twin screw extruder (PCM45 (IJ) manufactured by Ikegai Tetsu T Co., Ltd.).
While kneading was carried out at 110° C., the aqueous dispersant solution obtained in the above example was continuously fed through a first feed port provided in the metering zone of the extruder at a rate of 20 parts by weight/hour using a gear pump. Subsequently, a second
Hot water was continuously supplied from the supply port at a rate of 70 parts by weight/hour using a plunger pump, and the extrusion temperature IW was 110°C.
, Extrusion 17 at 250 rpm, a white aqueous dispersion was continuously produced (1 to 11 liquids).

この分散液のＭＦＴは６５℃であり、その固型分の平均
粒径は約０．５　ミクロンであった。The MFT of this dispersion was 65°C, and the average particle size of its solids was about 0.5 microns.

同様にしてエチレン・酢酸ビニル共重合体〔三井石油化
学工業製エプアフレックス２２０（商品名）；酢酸ビニ
ル含量２８チ、融点７４℃、ＭＦＲ＝１５０ｙ／１０分
〕５０壬とジシクロへキシルフタレ−ト〔和光紬薬■製
結晶性可塑剤〕５０φの混合物を１００部／時間の割合
で同方向回転噛合型二軸スクリュー押出機（池貝鉄丁社
商品名ＰＣＭ４５、三条ネジ浅溝型、Ｌ／Ｄ＝３０）の
ホッパーより連続的に供給した。Similarly, 50 ml of ethylene/vinyl acetate copolymer [EPAFFLEX 220 (trade name) manufactured by Mitsui Petrochemical Industries, Ltd.; vinyl acetate content 28 t, melting point 74°C, MFR = 150 y/10 min] and dicyclohexyl phthalate were added. [Crystalline plasticizer made by Wako Tsumugi Co., Ltd.] A 50φ mixture was fed at a rate of 100 parts/hour using a co-rotating intermeshing type twin screw extruder (Ikegai Tetcho Co., Ltd. product name: PCM45, triple thread shallow groove type, L/D =30) was continuously supplied from a hopper.

また同押出機のペント部に設けた供給口より前記分散剤
水溶液２２．９部（固型分８部）を更に熱水１４７．１
部で希釈した水溶液’１１７０部／時の割合でギヤーポ
ンプ（吐出圧力３ｈ　／　ａｄ　Ｇ　）で加圧して連続
的に供給しながら、加熱温度（シリンダー温間、以下同
じ）１３０℃、スクリュー回転数１０　Ｏｒｐｍ　で連
続的に押出し、乳白色のポリマー水性分散液（第［前液
、固型分濃度４０係）を得た。このものの平均粒径は約
０．５　ミクロンであり、ＭＦＴは６２℃であった。Further, 22.9 parts of the dispersant aqueous solution (solid content: 8 parts) was added to 147.1 parts of hot water through the supply port provided in the pent part of the same extruder.
While continuously supplying an aqueous solution diluted with 1,170 parts/hour under pressure with a gear pump (discharge pressure 3 h/ad G), the heating temperature (cylinder warm, hereinafter the same) was 130°C and the screw rotation speed was 10. Continuous extrusion was performed using Orpm to obtain a milky white polymer aqueous dispersion (first liquid, solid content concentration: 40 parts). The average particle size of this material was approximately 0.5 micron, and the MFT was 62°C.

この第［口］液と前記の第（１１液を固型分比で表１と
なる割合で室温で混合し、同表に示すＭＦＴの水性分散
液組成物を得た。This No. 1 liquid and the aforementioned No. 11 liquid were mixed at room temperature in a solid content ratio shown in Table 1 to obtain an aqueous dispersion composition of MFT shown in the same table.

この水性分散液組成物を坪量１６０ｆ／−のアー４紙に
塗工量が乾燥時２０ｆ／ｎ？になるように塗工［〜、２
０℃で１日乾燥させ不連続皮膜を得た。This aqueous dispersion composition was coated on A4 paper with a basis weight of 160 f/n at a dry coating weight of 20 f/n? Coating so that [~, 2
It was dried at 0° C. for one day to obtain a discontinuous film.

この皮膜は何ら粘着性を示さなかった。This film did not exhibit any stickiness.

この皮膜を有するアート紙を縦５０（１＋＋＋ｎ＋、横
３００霜に鋏でシート状に切り出し、試料片とした。こ
の試料片を１００℃に１０秒間加熱して、２３℃、６５
　％　ＲＨの恒温恒侵室に１昼夜放冷し、低密度ポリエ
チレンフィルムイルみ５０μ）とヒートシーラーを用い
て圧力２　ｈ／ｌｒ／Ｉ、　　２３℃、６５係Ｒ）Ｔの
条件で１秒間感圧接着させた。This film-bearing art paper was cut into a sheet with scissors, 50 mm lengthwise and 300 mm width.This sample piece was heated to 100℃ for 10 seconds,
% RH for one day and night, and then sealed for 1 second at a pressure of 2 h/lr/I, 23°C, and a coefficient of 65 R) using a low-density polyethylene film (illuminated 50μ) and a heat sealer. It was pressure bonded.

この感圧接着させたサンプルを１５部幅に切出し、オー
　トゲラフ（高滓製作所製ｌ５−２０００型）にてＪＩ
Ｓ　Ｋ−６８５４記載の方法に準拠して引張速度３００
ｍ／分ではぐり試験を行なった。１だ、塗布乾燥したテ
ストピースを加熱１７ないで同一の条件で感圧接着させ
た結果もあわせて表１に示した。This pressure-sensitive adhesive sample was cut into 15 width pieces, and JI was performed using an autogelaf (Model 15-2000 manufactured by Takasu Seisakusho).
Tensile speed 300 according to the method described in S K-6854
A gouge test was carried out at m/min. Table 1 also shows the results of pressure-sensitive bonding of coated and dried test pieces under the same conditions without heating for 17 days.

（以下余白） 比較例１ 実施例１−ｄで用いたロジンのグリセリンエステル５０
部、エチレン−酢酸ビニル共重合体２５部およびジシク
ロへキシルフタレート２５部の混合物に、トルエン９０
０部を加え、次いで５０℃に２時間加熱し、均一な樹脂
溶解液を得た。(Left below) Comparative Example 1 Glycerin ester of rosin used in Example 1-d 50
90 parts of toluene was added to a mixture of 25 parts of ethylene-vinyl acetate copolymer and 25 parts of dicyclohexyl phthalate.
0 parts was added and then heated to 50° C. for 2 hours to obtain a uniform resin solution.

この溶解液をアート紙に塗布量（固型分）が２ｏｙ／ｌ
ｒ？となるように２０℃で塗布し、６時間乾燥さぜた後
、２昼夜１０　ｗｎ　Ｈｇの減圧室に保存して連続塗膜
を有するアート紙を得た。The coating amount (solid content) of this solution on art paper is 2 oy/l.
r? The mixture was coated at 20° C., dried for 6 hours, and then stored in a vacuum chamber at 10 wn Hg for 2 days and nights to obtain art paper with a continuous coating film.

この連続皮膜は粘着性を有し、粘着性を示さなくなるま
でに更に５日要した。This continuous film was tacky and required an additional 5 days to become tacky.

また、ｉｏｏ℃に１０秒間加熱した後、２３℃、６５％
ＲＨで１昼夜放冷し、低密度ポリエチレンフィルムを用
いて圧力２Ｋｆ／ｆｆｌ、２３℃、６５％ＲＨの条件で
１秒間感圧接着させたときの接着強度は５７０ｆ／１５
咽幅であった。また、１００℃の加熱を省いたときの接
着強度は５５０　？、／Ｉ５咽幅であった。Also, after heating to ioo℃ for 10 seconds, 23℃, 65%
The adhesive strength was 570f/15 when left to cool at RH for one day and then pressure sensitively bonded for 1 second at a pressure of 2 Kf/ffl, 23°C, and 65% RH using a low density polyethylene film.
It was the width of the throat. Also, the adhesive strength when heating to 100℃ is omitted is 550? , /I5 pharynx width.

実施例２ エチレン−酢酸共重合体（酢酸ビニル含量２０％、ＭＦ
’Ｒ４００ｆ、／１０分）７０部とパラフィン系プロセ
スオイル″ＰＷ−９０″（出光興産製商品名）３０部の
混合物を１００部／時間の割合で同方向回転噛合型二軸
スクリュー押出機（池貝鉄工社商品名　ＰＣＭ４５、三
条ネジ浅溝型、Ｌ／Ｄ＝３０）のホッパーより連続的に
供給した。Example 2 Ethylene-acetic acid copolymer (vinyl acetate content 20%, MF
A mixture of 70 parts of 'R400f, /10 minutes) and 30 parts of paraffinic process oil 'PW-90' (trade name, manufactured by Idemitsu Kosan) was heated at a rate of 100 parts/hour using a co-rotating intermeshing twin screw extruder (Ikegai It was continuously supplied from a hopper of Tekko Co., Ltd. (trade name: PCM45, triple thread shallow groove type, L/D=30).

また同押出機の第１のベント部に設けた供給口より、前
記製造例で得たアクリル系共重合体の中和物の水溶液を
２２．９部／時間（分散剤の固型分としては８部／時間
）の割合でギヤーポンプ（吐出圧力３　ｈ／ｃｄＧ　）
で加圧して連続的に供給し、また第２のベント部に設け
た供給口より熱水を７０部／時間の割合でトロコイドポ
ンプによね連続的に供給しながら、加熱温度（シリンダ
一温度、以下同じ）１１０℃で連続的に押出し、乳白色
の水性分散液を得た。In addition, from the supply port provided in the first vent part of the same extruder, 22.9 parts/hour of the aqueous solution of the neutralized acrylic copolymer obtained in the above production example was added (as the solid content of the dispersant). Gear pump (discharge pressure 3 h/cdG) at the rate of 8 parts/h)
The heating temperature (cylinder temperature, The same applies hereinafter) was continuously extruded at 110°C to obtain a milky white aqueous dispersion.

この水性分散液のＭＦＴは５８℃であった。この水性分
散液を第（ＩＩ）液とする。The MFT of this aqueous dispersion was 58°C. This aqueous dispersion is referred to as liquid (II).

この第（ＩＩ）液５０部と、前記実施例１の第（１）液
５０部とを２０℃で混合して樹脂水性分散液組成物（Ｍ
ＦＴ６０℃）を調製した。50 parts of this liquid (II) and 50 parts of liquid (1) of Example 1 were mixed at 20°C to form a resin aqueous dispersion composition (M
FT60°C) was prepared.

この組成物を実施例１−ｄと同様にして評価し／′Ｃ，
０ 得た不連続塗膜を有するアート紙は２０℃で粘着性を有
していなかった。This composition was evaluated in the same manner as in Example 1-d.
0 The art paper with the discontinuous coating obtained had no tackiness at 20°C.

また、１００℃、１０秒間加熱後、室温で１日保存後の
接着強度は８３０　？　／　１５　ｗｎ幅であり、加熱
がないときの接着強度はＯｒ７１５ｍ幅であった。Also, after heating at 100℃ for 10 seconds and storing at room temperature for 1 day, the adhesive strength was 830? /15 wn width, and the adhesive strength without heating was Or715 m width.

比較例２ 実施例２で用いたエチレン・酢酸ビニル共重合体３５部
、プロセスオイル１５部およびロジンのグリセリンエス
テル５０部の混合物を１００　部／時間の割合で同方向
回転噛合型二軸スクリュー押出機（池貝鉄工社商品名　
ＰＣＭ４５、三条ネジ浅溝型、Ｌ／Ｉ）＝３０）のホッ
パーより連続的に供給した。Comparative Example 2 A mixture of 35 parts of the ethylene/vinyl acetate copolymer used in Example 2, 15 parts of process oil, and 50 parts of rosin glycerin ester was heated at a rate of 100 parts/hour in a co-rotating intermeshing twin screw extruder. (Ikegai Iron Works product name)
It was continuously supplied from a hopper of PCM45, triple thread shallow groove type, L/I) = 30).

まだ同押出機の第１のベント部に設けた供給口より、前
記製造例で得だアクリル系共重合体の中和物の水溶液を
２２．９部／時間（分散剤の固型分としては８部／時間
）の割合でギヤーポンプ（吐出圧力３Ｋｚ／ｃｆＩＧ）
で加圧して連続的に供給し、また第２のベント部に設け
た供給口より熱水を７０部／時間の割合でトロコイドポ
ンプにより連続的に供給しながら、加熱温度（シリンダ
一温度、以下同じ）１１０℃で連続的に押出し、乳白色
の水性分散液（ＭＦＴｌａ℃）を得た。The aqueous solution of the neutralized acrylic copolymer obtained in the above production example was added at 22.9 parts/hour (in terms of the solid content of the dispersant) through the supply port provided in the first vent part of the same extruder. Gear pump (discharge pressure 3Kz/cfIG) at the rate of 8 parts/hour)
The heating temperature (cylinder temperature, below The same) was continuously extruded at 110°C to obtain a milky white aqueous dispersion (MFTla°C).

この水性分散液を用いて実施例１と同様にアート紙上に
塗布し、２０℃で１昼夜乾燥させて連続塗膜を得た。こ
の塗膜は粘着性を有していた。This aqueous dispersion was applied onto art paper in the same manner as in Example 1, and dried at 20° C. for one day to obtain a continuous coating film. This coating film was sticky.

これとポリエチレンフィルムを実施例１と同様にして接
着させたときの接着強度は、１００℃、１０秒間の加熱
履歴を得たものは５２０　ｒ／１５咽幅、加熱履歴を受
けないものは４７０　ｙ／１５馴幅であった。When this and a polyethylene film were adhered in the same manner as in Example 1, the adhesive strength was 520 r/15 width for the film that had been heated at 100°C for 10 seconds, and 470 y for the film that had not been heated. /15 standard width.

比較例３ 実施例２において、ロジンのグリセリンエステルの代り
に部用化学製水添ロジンのジエチレングリコールエステ
ル１エステルガム［■Ｄ″（商品名、軟化点５℃）を用
いて水性分散液（ＭＦＴ３０℃）を得た。これを第（１
）液とし、これ５０部と実施例２の第（ｎ）液５０部と
を２０℃で均一に混合し、樹脂水性分散液組成物（ＭＦ
Ｔ１ｓ℃）を得たつこの組成物を用いて実施例１と同様
にアート紙上に塗布、乾燥を行い、塗膜を得た。この塗
膜は粘着性を有していた。Comparative Example 3 In Example 2, an aqueous dispersion (MFT 30°C) was prepared by using diethylene glycol ester 1 ester gum [■D'' (trade name, softening point: 5°C) of hydrogenated rosin made by Kagaku Kagaku Co., Ltd. in place of the glycerin ester of rosin. ) was obtained.
) solution, 50 parts of this and 50 parts of the (n) solution of Example 2 were uniformly mixed at 20°C to prepare an aqueous resin dispersion composition (MF
Using this composition, it was applied onto art paper and dried in the same manner as in Example 1 to obtain a coating film. This coating film was sticky.

これとポリエチレンフィルムとを実施例１と同様に接着
させたときの接着強度は、１００℃、１０秒間の履歴を
経たものは９３０　？　／　１５　ｗａ幅、加熱履歴を
受けないものは９１０９／１５．幅であった〕 実施例３ 部用化学製不均化ロジン゛・・イベール”（商品名）を
１００部／時間の割合で同方向回転噛合型二軸スクリュ
ー押出機（池貝鉄工社商品名ＰＣＭ４５、三条ネジ浅溝
型、Ｌ／Ｄ＝３０）のホッパーより連続的に供給した。When this and a polyethylene film were bonded together in the same manner as in Example 1, the adhesive strength was 930? after a history of 10 seconds at 100°C. / 15 wa width, those not subject to heating history are 9109/15. [Example 3] A chemically made disproportionated rosin for parts "Iber" (trade name) was fed at a rate of 100 parts/hour using a co-rotating meshing type twin screw extruder (Ikegai Tekko Co., Ltd. trade name PCM45). , triple thread shallow groove type, L/D=30) hopper.

また同押出機の第１のベント部に設けた供給口ヨリ、ク
ラレ製部分ケン化ポリビニルアルコール”ＰＶＡ４２０
″３０％水溶液を１７部／時間の割合でギヤーポンプ（
吐出圧力３　Ｋ５＋　／　ｃａ　Ｇ　）で加圧して連続
的に供給し、また第２のベント部に設けた供給口より水
を９０部／時間の割合でトロコイドポンプにより連続的
に供給しながら、加熱温度（シリンダ一温度、以下同じ
）１００℃で連続的に押出し、平均粒径帆２μの乳白色
の水性分散液を得た。In addition, the supply port installed in the first vent part of the same extruder was filled with Kuraray's partially saponified polyvinyl alcohol "PVA420".
``30% aqueous solution at a rate of 17 parts/hour with a gear pump (
The water is continuously supplied under pressure at a discharge pressure of 3 K5+ / ca G), and water is continuously supplied from the supply port provided in the second vent part by a trochoid pump at a rate of 90 parts/hour while heating. Continuous extrusion was carried out at a temperature of 100° C. (cylinder temperature, same hereinafter) to obtain a milky white aqueous dispersion with an average particle size of 2 μm.

この水性分散液（ＭＦＴｓｓ℃）を第（Ｄ液としたＯ 次に、不均化ロジン１００部の代りに、スチレ７−イソ
プレンースチレンブロツク共重合体４゜部とジシクロへ
キシルフタレート６０部の混合物１００部を用いる他は
上記と同様にして、平均粒径２．５μの乳白色の水性分
散液を得た。これを第（［１）液とする。This aqueous dispersion (MFTss°C) was used as a liquid (D). Next, in place of 100 parts of disproportionated rosin, 4 parts of styrene 7-isoprene-styrene block copolymer and 60 parts of dicyclohexyl phthalate were added. A milky white aqueous dispersion having an average particle size of 2.5 μm was obtained in the same manner as above except that 100 parts of the mixture was used.This is referred to as the liquid ([1)].

上記第（１）液８０部と第（Ｉｔ）液２０部とを２０℃
で混合し、ＭＦＴ７２℃の水性分散液組成物を得た。80 parts of the above liquid (1) and 20 parts of liquid (It) at 20°C.
and mixed to obtain an aqueous dispersion composition with an MFT of 72°C.

この組成物を用い、実施例１と同様にアート紙上に塗布
し、２０℃で１昼夜乾燥させて不連続塗膜を形成させた
。この塗膜は粘着性を有していなかった。Using this composition, it was applied onto art paper in the same manner as in Example 1 and dried at 20° C. for one day and night to form a discontinuous coating film. This coating had no tack.

この塗膜とポリエチレンフィルムとを実施例１と同様に
して接着させ、接着強度を測定し酬。This coating film and a polyethylene film were adhered in the same manner as in Example 1, and the adhesive strength was measured.

１００℃、１０秒間の加熱履歴を受けたものの接着強度
は７３０９　／　１５　ｍｍ幅であり、熱履歴を受けて
いないもののそれはＯｒ／１５＋＋ｍ幅であった。The bonding strength of the material subjected to a heating history of 100° C. for 10 seconds was 7309/15 mm width, and that of the material subjected to no heat history was Or/15++m width.

特許出願人　　三菱油化株式会社 代理人　弁理士　占　川　秀　利 代理人　弁理士　長　谷　正　久Patent applicant: Mitsubishi Yuka Co., Ltd. Agent: Patent attorney Hidetoshi Utsukawa Agent: Patent Attorney Masahisa Nagatani

Claims (1)

【特許請求の範囲】 １）、第１１）液： 軟化点が５０〜１３０℃の粘着性樹脂 の水性分散液 第［１１１液： （３）、熱可塑性樹脂　　３０〜８０重量係（Ｂ）、可
塑剤　　　　　７０〜２０重惜チ固型分比が上記割合の
水性分散液 第ｍ液と第［ＩＩ］液が固型分比で１／９〜９／１の割
合で配合されている最低造膜温度が５０〜１３５℃の樹
脂水性分散液組成物。[Claims] 1), 11th liquid: aqueous dispersion of adhesive resin with a softening point of 50 to 130°C [111 liquid: (3), thermoplastic resin 30 to 80 weight ratio (B), Plasticizer 70 to 20% Aqueous dispersion having the above-mentioned solid content ratio A minimum formulation in which the mth liquid and the [II] liquid are blended in a solid content ratio of 1/9 to 9/1. An aqueous resin dispersion composition having a film temperature of 50 to 135°C.