JPH0238478A - Emulsion adhesive composition - Google Patents
Emulsion adhesive compositionInfo
- Publication number
- JPH0238478A JPH0238478A JP18926188A JP18926188A JPH0238478A JP H0238478 A JPH0238478 A JP H0238478A JP 18926188 A JP18926188 A JP 18926188A JP 18926188 A JP18926188 A JP 18926188A JP H0238478 A JPH0238478 A JP H0238478A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- adhesive composition
- weight
- conjugated diene
- emulsion adhesive
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000000853 adhesive Substances 0.000 title claims abstract description 57
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 57
- 239000000839 emulsion Substances 0.000 title claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 42
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 19
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 19
- 229920000126 latex Polymers 0.000 claims abstract description 17
- 239000004816 latex Substances 0.000 claims abstract description 11
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 150000001993 dienes Chemical class 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 abstract 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 238000009408 flooring Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000010454 slate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 229920006173 natural rubber latex Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- -1 tufted carpet Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 238000007868 post-polymerization treatment Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は新規なエマルジョン接着剤組成物に関し、さら
に詳しくは、初期接着性及び施工後の接着性に優れたエ
マルジョン接着剤組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel emulsion adhesive composition, and more particularly to an emulsion adhesive composition with excellent initial adhesion and post-application adhesion.
（従来の技術）
コンクリート建築物の床材としては、磨き花崗岩、タフ
テッドカーペットあるいはポリ塩化ビニル製の床材など
が一般に使用されているが、なかでもポリ塩化ビニル製
の床材は、その施工が容易であることや、色彩や意匠の
選択が自由であるなどの理由から、床材の主流として広
く用いられている。そしてポリ塩化ビニル製の床材のう
ちでも、ポリ塩化ビニルの発泡層と軟質ポリ塩化ビニル
層から構成される、いわゆるクツションフロアが、歩行
時の足されりの良さと美観上の好ましさから、とりわけ
賞月されるようになってきた。(Prior art) Polished granite, tufted carpet, or polyvinyl chloride flooring are generally used as flooring materials for concrete buildings. It is widely used as a mainstream flooring material because it is easy to apply, and colors and designs can be freely selected. Among flooring materials made of polyvinyl chloride, so-called cushion floors, which are composed of a foamed polyvinyl chloride layer and a soft polyvinyl chloride layer, are comfortable to walk on and are aesthetically pleasing. Since then, it has been particularly prized.
ポリ塩化ビニル製床材の施工は、通常、共役ジエン系ゴ
ムラテックスに粘着付与剤として炭化水素樹脂エマルジ
ョンを配合し、さらにプロセスオイルのような可塑剤と
炭酸カルシウムのような充填剤を加え、必要ならば分散
剤、消泡剤、防腐剤、増粘剤などをも加えて成るエマル
ジョン接着剤組成物を用いて、直接、コンクリート床面
にポリ塩化ビニル製床材を接着することによって実施さ
れる。The construction of PVC flooring is usually done by blending a conjugated diene rubber latex with a hydrocarbon resin emulsion as a tackifier, and adding plasticizers such as process oil and fillers such as calcium carbonate. In this case, it is carried out by directly bonding the PVC flooring material to the concrete floor surface using an emulsion adhesive composition that also contains a dispersant, antifoaming agent, preservative, thickener, etc. .
しかし、従来用いられてきたエマルション接着剤組成物
は、必ずしも接着力が十分てないという欠点のほかに、
最終的な接着力か得られるまてに長時間を要するので、
床材の施工後しばらくの開は、施工現場への立ち入りを
制限しなけれはならず、他の工事の実施に影響を与える
という問題があった。However, conventionally used emulsion adhesive compositions have the disadvantage that they do not necessarily have sufficient adhesive strength.
It takes a long time to achieve the final adhesive strength, so
There was a problem in that access to the construction site had to be restricted for a while after the flooring was installed, which affected the implementation of other construction works.
これに対して、接着力の向上を図るために、例えば、接
着剤の樹脂成分としてＣ５留分及びスチレン類を共重合
した炭化水素樹脂とエチレン性不飽和カルボン酸又はそ
の無水物との付加物を用いる方法（特公昭５９−２６９
７）や、接着剤中の可塑剤量を減らす方法などが提案さ
れている。On the other hand, in order to improve adhesive strength, for example, adducts of hydrocarbon resins copolymerized with C5 fraction and styrenes and ethylenically unsaturated carboxylic acids or their anhydrides as resin components of adhesives have been developed. method using
7) and methods of reducing the amount of plasticizer in the adhesive have been proposed.
しかしながら、これらの方法では、十分な初期接着力が
得られない。すなわち、これらの方法において用いられ
る接着剤組成物は、コンクリート床面に塗布したのち床
材を接着させるまでの一定時間内にわたって十分な接着
性を保持するという性能に欠け、床材の接着が少しでも
遅れると接着が不十分となって期待する接着力が得られ
なくなるという問題点を有している。このとき、初期接
着力を改良するために可塑剤を増やすことは可能である
が、今度は接着力が不十分となってしまう。However, these methods do not provide sufficient initial adhesive strength. In other words, the adhesive compositions used in these methods lack the ability to maintain sufficient adhesion for a certain period of time after being applied to a concrete floor surface until the flooring material is bonded, and the adhesive compositions used in these methods lack the ability to maintain sufficient adhesion for a certain period of time until the flooring material is bonded. However, if it is delayed, the adhesion becomes insufficient and the expected adhesion force cannot be obtained. At this time, it is possible to increase the amount of plasticizer in order to improve the initial adhesive strength, but this time the adhesive strength becomes insufficient.
（発明が解決しようとする課題）
本発明の目的は、初期接着力を損なうことなく、接着力
に優れ、また、施工後の接着力の発現が速い接着剤組成
物を得ることにある。本発明者らは、鋭意研究の結果、
接着剤の樹脂成分として、特定の組成を有する単量体混
合物を重合して得られる炭化水素樹脂を使用すれは、前
記目的が達成されることを見出し、この知見に基いて本
発明を完成するに至った。(Problems to be Solved by the Invention) An object of the present invention is to obtain an adhesive composition that has excellent adhesive strength without impairing the initial adhesive strength and exhibits rapid adhesive strength after application. As a result of intensive research, the present inventors found that
It has been discovered that the above object can be achieved by using a hydrocarbon resin obtained by polymerizing a monomer mixture having a specific composition as a resin component of an adhesive, and based on this knowledge, the present invention has been completed. reached.
（課題を解決するための手段）
かくして本発明によれは、（Ａ）共役ジエン系ゴムラテ
ックスに、（Ｂ）粘着付与剤として、（イ）シクロペン
タジェン系単量体３０〜８５重量％、（ロ）芳香族ビニ
ル単量体５〜４０％及び（ハ）鎖状共役ジエン系単量体
５〜４０重量％を含有する単量体混合物を重合して得ら
れる、炭化水素樹脂を配合して成ることを特徴とするエ
マルジョン接着剤組成物が提供される。(Means for Solving the Problems) Thus, according to the present invention, in (A) a conjugated diene rubber latex, (B) as a tackifier, (a) 30 to 85% by weight of a cyclopentadiene monomer, (b) A hydrocarbon resin obtained by polymerizing a monomer mixture containing 5 to 40% by weight of an aromatic vinyl monomer and (c) 5 to 40% by weight of a chain conjugated diene monomer. An emulsion adhesive composition is provided comprising:
本発明において用いられる共役ジエン系ゴムラテックス
は、共役ジエン単量体から誘導される単位を主構成成分
として含有するゴムのラテックスであり、具体的には、
天然コム、合成シス−■、４−ポリイソプレンゴム、ス
チレン−フタジエン共重合体ゴム、スチレン−イソプレ
ン共重合体ゴム、スチレン−ブタジェンブロック共重合
体ゴム、スチレン−イソプレンブロック共重合体ゴムな
どのラテックスである。これらのゴムラテックスは、乳
化重合で直接合成したものでも、また、溶液重合で得ら
れたゴムを転相して得たものであってもよい。これらの
ゴムラテックスのなかでは、性能上、天然ゴムラテック
ス及び乳化重合により得られる結合スチレン量が２０〜
７０重量％、好ましくは３０〜６０重量％のスチレン−
ブタジェン共重合体ゴムラテックスが賞月される。The conjugated diene rubber latex used in the present invention is a rubber latex containing units derived from a conjugated diene monomer as a main component, and specifically,
natural comb, synthetic cis-■, 4-polyisoprene rubber, styrene-phtadiene copolymer rubber, styrene-isoprene copolymer rubber, styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, etc. It's latex. These rubber latexes may be directly synthesized by emulsion polymerization, or may be obtained by phase inversion of rubber obtained by solution polymerization. Among these rubber latexes, in terms of performance, the amount of bound styrene obtained by natural rubber latex and emulsion polymerization is 20 to 20%.
70% by weight, preferably 30-60% by weight of styrene
Butadiene copolymer rubber latex was awarded.
次に、本発明で粘着付与剤として用いられる炭化水素樹
脂は、（イ）シクロペンタジェン系単量体３０〜８５重
量％、（ロ）芳香族ヒニル単量体５〜４０％、及び（ハ
）鎖状共役ジエン系単量体５〜４０重量％を含有する単
量体混合物を重合して得られる炭化水素樹脂である。Next, the hydrocarbon resin used as a tackifier in the present invention contains (a) 30 to 85% by weight of a cyclopentadiene monomer, (b) 5 to 40% of an aromatic hinyl monomer, and (a) ) A hydrocarbon resin obtained by polymerizing a monomer mixture containing 5 to 40% by weight of a chain conjugated diene monomer.
本発明において用いられるシクロペンタジェン系単量体
は、シクロペンタジェン又はその誘導体であり、その具
体例としては、シクロペンタジェン；例えはメチルシク
ロペンタジェンなどの置換シクロペンタジェン；これら
の二量体、共二量体：及びこれらの混合物が挙げられる
。The cyclopentadiene monomer used in the present invention is cyclopentadiene or a derivative thereof, and specific examples thereof include cyclopentadiene; substituted cyclopentadiene such as methylcyclopentadiene; and codimers; and mixtures thereof.
本発明において用いられる単量体混合物中のシクロペン
タジェン系単量体の含有率は３０〜８５重量％、好まし
くは４０〜７０重量％である。この含有率が前記上限を
超えると、樹脂の軟化点が過度に上昇し、エマルジョン
接着剤組成物の初期接着力が不十分となり、また、接着
力も低いものとなってしまう。逆に、前記下限未満では
、樹脂の生成率が大幅に低下するとともに樹脂の軟化点
が著しく低くなって（この傾向は熱重合において著しい
）、この樹脂をエマルジョン接着剤組成物に配合した際
に十分な接着力及び剥離強度を得ることができない。The content of the cyclopentadiene monomer in the monomer mixture used in the present invention is 30 to 85% by weight, preferably 40 to 70% by weight. If this content exceeds the above upper limit, the softening point of the resin will rise excessively, and the initial adhesive strength of the emulsion adhesive composition will be insufficient, and the adhesive strength will also be low. On the other hand, below the above lower limit, the resin production rate will drop significantly and the softening point of the resin will drop significantly (this tendency is significant in thermal polymerization), and when this resin is blended into an emulsion adhesive composition, It is not possible to obtain sufficient adhesion and peel strength.
本発明において用いられる芳香族ビニル単量体は、重合
性のビニル基を有する芳香族化合物であれは特に限定さ
れるものではないが、その具体例として、スチレン、労
メチルスチレン、β−メチルスチレン、ビニルトルエン
などのスチレン誘導体とインデン、メチルインテンなど
のインデン類を挙げることができる。The aromatic vinyl monomer used in the present invention is not particularly limited as long as it is an aromatic compound having a polymerizable vinyl group, but specific examples include styrene, methylstyrene, and β-methylstyrene. , styrene derivatives such as vinyltoluene, and indenes such as indene and methylintene.
本発明において、芳香族ビニル単量体は、もちろん純粋
なものを混合して用いることもできるが、例えはベンゼ
ン； トルエン、キシレンなどのアルキルベンゼン；ナ
フタリンなどの非重合性芳香族炭化水素との混合物の形
で用いてもよい。このような混合物の例としては、工業
的に容易に人手できる、いわゆるＣ９留分（石油類の熱
分解により得られる分解油留分のうち１４０〜２４０℃
の沸点範囲を有する留分）を示すことができる。In the present invention, aromatic vinyl monomers can of course be used as a mixture of pure ones, but for example, mixtures with benzene; alkylbenzenes such as toluene and xylene; and non-polymerizable aromatic hydrocarbons such as naphthalene are used. It may also be used in the form of Examples of such mixtures include the so-called C9 fraction (140 to 240°C of the cracked oil fraction obtained by thermal decomposition of petroleum), which can be easily produced manually industrially.
(a fraction with a boiling point range of ).
本発明において用いられる単量体混合物中の芳香族ビニ
ル単量体の含有率は、５〜４０％、好ましくは１０〜３
５重量％である。この含有率が前記上限を超えると、樹
脂の収率が著しく低下し、また、樹脂の色相が悪化して
床材の色相に悪影響を与えることが多いので好ましくな
い。逆に前記下限未満では、エマルジョン接着剤組成物
の接着力及び剥離強度が損なわれる。The content of aromatic vinyl monomer in the monomer mixture used in the present invention is 5 to 40%, preferably 10 to 3%.
It is 5% by weight. If this content exceeds the above upper limit, the yield of the resin will drop significantly, and the hue of the resin will deteriorate, often having an adverse effect on the hue of the flooring material, which is not preferred. Conversely, below the lower limit, the adhesive force and peel strength of the emulsion adhesive composition will be impaired.
本発明において用いられる鎖状共役ジエン系単量体は、
特に限定されるものではなく、その具体例としては、１
．３−ペンタジェン、イソプレン、１゜３−ブタジェン
を挙げることができる。本発明において、鎖状共役ジエ
ン系単量体は高純度に精製して用いる必要はなく、他の
飽和炭化水素又は不飽和炭化水素を含むような炭化水素
混合物の形で用いてもよい。The linear conjugated diene monomer used in the present invention is
There are no particular limitations, and specific examples include 1.
．． Mention may be made of 3-pentadiene, isoprene, and 1°3-butadiene. In the present invention, the chain conjugated diene monomer does not need to be purified to a high degree of purity before use, and may be used in the form of a hydrocarbon mixture containing other saturated hydrocarbons or unsaturated hydrocarbons.
本発明において、鎖状共役ジエン系単量体は、樹脂の分
子量分布を調整し、樹脂の色相を損なうことなくエマル
ジョン接着剤組成物の初期接着力を改良するうえで、顕
著な効果をもたらすが、本発明において用いられる単量
体混合物中の含有率が５〜４０重量％、好ましくは１０
〜３０重量％であることが必要である。この含有率が前
記上限を超えると樹脂の収率が大きく低下し、また、軟
化点が著しく低下してエマルジョン接着剤組成物に十分
な接着力を付与することができない。逆に前記下限未満
では、樹脂の軟化点が過度に上昇し、エマルジョン接着
剤組成物の初期タックが不十分となり、又接着力も低い
ものとなってしまう。In the present invention, the chain conjugated diene monomer has a remarkable effect in adjusting the molecular weight distribution of the resin and improving the initial adhesive strength of the emulsion adhesive composition without impairing the hue of the resin. , the content in the monomer mixture used in the present invention is 5 to 40% by weight, preferably 10
~30% by weight is required. If this content exceeds the above upper limit, the yield of the resin will decrease significantly, and the softening point will also decrease significantly, making it impossible to impart sufficient adhesive strength to the emulsion adhesive composition. On the other hand, below the lower limit, the softening point of the resin will rise excessively, the initial tack of the emulsion adhesive composition will be insufficient, and the adhesive strength will also be low.
本発明においては、単量体混合物中に合計２０重量％ま
での範囲で、その他の重合性不飽和炭化水素を含有する
ことができる。In the present invention, other polymerizable unsaturated hydrocarbons can be contained in the monomer mixture in a total amount of up to 20% by weight.
本発明において、これらの単量体混合物は、通常は、ベ
ンゼン、トルエン、キシレン、テトラリン、ケロシンな
どのような公知の不活性溶剤の存在又は不存在下で、２
００〜３００℃、好ましくは２３０〜２８０℃において
、０．５〜２０時間にわたって、バッチ式で又は連続的
に熱重合する方法が採用される。また、カチオン重合法
によることも可能であるが、重合の後処理等の面から熱
重合が好ましい。重合反応によって得られた反応液中の
飽和炭化水素成分、未反応の不飽和炭化水素成分及び副
生ずる低揮発性留分を留去することにより、目的とする
炭化水素樹脂が得られる。In the present invention, these monomer mixtures are usually mixed with 2
A method is employed in which thermal polymerization is carried out batchwise or continuously at 00 to 300°C, preferably 230 to 280°C, for 0.5 to 20 hours. Although cationic polymerization is also possible, thermal polymerization is preferred from the viewpoint of post-polymerization treatment. The desired hydrocarbon resin is obtained by distilling off the saturated hydrocarbon components, unreacted unsaturated hydrocarbon components, and by-produced low-volatility fractions in the reaction solution obtained by the polymerization reaction.
本発明において使用される炭化水素樹脂は、通常、エマ
ルジョン状に加工されて共役ジエン系ゴムラテックスと
混合される。その混合比率は、共役ジエン系ゴムラテッ
クス中のゴム分１００重量部に対して、炭化水素樹脂２
０〜５００重量部、好ましくは４０〜３５０重量部であ
る。混合比率がこの範囲を外れると、十分な接着性能を
有するエマルジョン接着剤組成物を得ることができない
。The hydrocarbon resin used in the present invention is usually processed into an emulsion and mixed with a conjugated diene rubber latex. The mixing ratio is 100 parts by weight of rubber in the conjugated diene rubber latex to 2 parts by weight of hydrocarbon resin.
The amount is 0 to 500 parts by weight, preferably 40 to 350 parts by weight. If the mixing ratio is outside this range, an emulsion adhesive composition with sufficient adhesive performance cannot be obtained.
（発明の効果）
本発明によって得られるエマルジョン接着剤組成物は、
接着力に優れ、施工後の接着力の発現が速いという利点
を有する。(Effect of the invention) The emulsion adhesive composition obtained by the present invention is
It has the advantage of excellent adhesive strength and rapid development of adhesive strength after installation.
（実施例）
以下に実施例を挙げて本発明をさらに具体的に説明する
。なお、実施例、比較例及び参考例において、部及び％
は特に断りのないかきり、重量基準である。(Example) The present invention will be described in more detail with reference to Examples below. In addition, in Examples, Comparative Examples, and Reference Examples, parts and %
Unless otherwise specified, figures are based on weight.
なお、本実施例において、樹脂の収率は、単量体混合物
合計重量に対する得られた樹脂重量の割合である。樹脂
の軟化点はＪ Ｉ Ｓ Ｉ（−２！５３１に規定され
た環球法で測定した。さらに、樹脂の色相はＡＳＴＭ
Ｄ−１５４４−６３Ｔによって測定してガードナー色
度で表示した。In this example, the resin yield is the ratio of the weight of the obtained resin to the total weight of the monomer mixture. The softening point of the resin was measured by the ring and ball method specified in JIS I (-2!531).Furthermore, the hue of the resin was measured according to ASTM
D-1544-63T and expressed in Gardner chromaticity.
参考例１
耐圧オートクレーブ中に、第１表に示す組成の単量体混
合物（Ａ−Ｇ）を仕込み、窒素雰囲気下に２６０℃で３
．５時間熱重合したのち、２５０°Ｃ１５ｍｇＨｇで減
圧蒸留することにより未反応単量体と油状生成物とを留
去し、それぞれ対応する炭化水素樹脂（Ａｌ〜ＣＩ）を
得た。樹脂の収率及び性状を測定し、結果を第１表に示
した。Reference Example 1 A monomer mixture (A-G) having the composition shown in Table 1 was placed in a pressure-resistant autoclave and heated at 260°C under a nitrogen atmosphere for 30 minutes.
．． After thermal polymerization for 5 hours, unreacted monomers and oily products were distilled off under reduced pressure at 250° C. and 15 mgHg to obtain corresponding hydrocarbon resins (Al to CI). The yield and properties of the resin were measured and the results are shown in Table 1.
参考例２
耐圧オートクレーブ中にベンゼン１００部及び塩化アル
ミニウム１．２部を仕込んだ後に、第１表に示す組成の
単量体混合物（Ｈ）を徐々に加え、６５℃で重合した後
、参考例１と同様の後処理をして、炭化水素樹脂（Ｈｌ
）を得た。樹脂の収率及び性状を測定し、結果を第１表
に示した。Reference Example 2 After 100 parts of benzene and 1.2 parts of aluminum chloride were charged into a pressure-resistant autoclave, a monomer mixture (H) having the composition shown in Table 1 was gradually added, and after polymerization at 65°C, Reference Example After the same post-treatment as in 1, hydrocarbon resin (Hl
) was obtained. The yield and properties of the resin were measured and the results are shown in Table 1.
第
表
実施例１
第１表に掲げた各炭化水素樹脂（Ａｌ〜Ｈ１）１００部
に対してミネラルスピリット２５部、アロマ系オイル（
フジアロマックス、富士興産（株））２０部を加え、得
られる混合物を撹拌して溶解させた。次に、撹拌下にノ
ニオン系界面活性剤（エマルゲン９１３、花王（株））
１．６部を加え、さらに撹拌を続けながら水２００部を
徐々に加えて転相させたのち、ゴム分３３部を含む天然
ゴムラテックス１００部、重質炭酸カルシウム４５０部
を加え、それぞれ対応する固形分濃度７５％のエマルジ
ョン接着剤組成物（Ａ２〜Ｈ２）を得た。Table Example 1 For 100 parts of each hydrocarbon resin (Al to H1) listed in Table 1, 25 parts of mineral spirit, aroma oil (
20 parts of Fuji Aromax (Fuji Kosan Co., Ltd.) was added, and the resulting mixture was stirred to dissolve. Next, while stirring, add a nonionic surfactant (Emulgen 913, Kao Corporation) to
After adding 1.6 parts of water and gradually adding 200 parts of water while stirring to invert the phase, add 100 parts of natural rubber latex containing 33 parts of rubber and 450 parts of heavy calcium carbonate, each corresponding to the mixture. Emulsion adhesive compositions (A2 to H2) having a solid content concentration of 75% were obtained.
得られたエマルション接着剤組成物を櫛ゴテを用いて３
．ｍｍ厚のスレート板に一定量塗布し、５分後に厚さ２
ｍｒｒＩ、幅２５闘の床材（フロアリューム、東洋リノ
リウム（株）製）を接着させ、気温２０℃、相対湿度６
５％の雰囲気下で所定時間養生したのちに、９０６剥離
試験（引張速度２００ ｍｍ／分）を行なって、その接
着力を評価した。The obtained emulsion adhesive composition was mixed using a comb trowel.
．． Apply a certain amount to a slate board with a thickness of 2 mm, and after 5 minutes it will become 2 mm thick.
mrrI, 25mm wide flooring material (Floorium, manufactured by Toyo Linoleum Co., Ltd.) was glued, and the temperature was 20℃ and the relative humidity was 6.
After curing for a predetermined time in a 5% atmosphere, a 906 peel test (pulling speed 200 mm/min) was conducted to evaluate the adhesive strength.
また、エマルジョン接着剤組成物を塗布したスレート板
を気温２０℃、相対湿度６５％の雰囲気下で６０分間放
置した後に厚さ２ｍｍ、幅２５開の床材（上記に同じ）
を接着させ、直ちに１８０°剥離試験（引張速度３００
ｍｍ／分）を実施して、その初期タックを評価した。In addition, after leaving the slate board coated with the emulsion adhesive composition in an atmosphere of 20°C and 65% relative humidity for 60 minutes, it becomes a flooring material with a thickness of 2 mm and a width of 25 mm (same as above).
was adhered and immediately subjected to a 180° peel test (tensile speed 300
mm/min) to evaluate its initial tack.
さらに、エマルジョン接着剤組成物を塗布したスレート
板に直ちに厚さ２ｍｍ、幅５０ｍｍの床材（上記に同じ
）を接着させ、これを気温２０℃、相対湿度６５％の雰
囲気下で所定時間養生したのちに１８０°剥離試験（引
張速度３００ ｍｍ／分）を実施して、その剥離強度を
評価した。Furthermore, a flooring material (same as above) with a thickness of 2 mm and a width of 50 mm was immediately adhered to the slate board coated with the emulsion adhesive composition, and this was cured for a predetermined period of time in an atmosphere with a temperature of 20°C and a relative humidity of 65%. Later, a 180° peel test (pulling speed: 300 mm/min) was conducted to evaluate the peel strength.
実施例２
共役ジエン系ゴム成分としてスチレン−ブタジェン共重
合体ラテックス（結合スチレン量４５％、ゲル含量３０
％）を用いるほかは実施例１と同様にして、炭化水素樹
脂Ａ１〜Ｈ１にそれぞれ対応するエマルジョン接着剤組
成物Ａ３〜Ｈ３を調製し、接着力、初期タック及び剥離
強度を評価した。Example 2 Styrene-butadiene copolymer latex (bonded styrene content 45%, gel content 30%) as a conjugated diene rubber component
Emulsion adhesive compositions A3 to H3 corresponding to the hydrocarbon resins A1 to H1, respectively, were prepared in the same manner as in Example 1 except that %) were used, and the adhesive strength, initial tack, and peel strength were evaluated.
結果を第４表に示す。The results are shown in Table 4.
第３表及び第４表から、本発明のエマルジョン接着剤組
成物が接着力の発現に優れているのに対して、芳香族ビ
ニル単量体を含まない単量体混合物から得られる炭化水
素樹脂を用いた場合（エマルジョン接着剤組成物Ｅ２及
びＥ３）は、接着力及び剥離強度が大きく低下し、特に
エマルジョン接着剤組成物のゴムラテックス成分として
スチレン−ブタジェン共重合体ラテックスを用いたとき
（エマルジョン接着剤組成物Ｅ３）は、初期タックも低
下すること、鎖状共役ジエン系単量体を含まない単量体
混合物から得られる炭化水素樹脂を用いた場合（エマル
ジョン接着剤組成物Ｆ２及びＦ３）は、初期タック及び
剥離強度が大幅に低下すること、シクロペンタジェン系
単量体の含有率が本発明の範囲を外れる単量体混合物か
ら得られる炭化水素樹脂を用いた場合（エマルジョン接
着剤組成物Ｇ２及び０３）も、接着力及び剥離強度が大
きく低下することが分かる。Tables 3 and 4 show that the emulsion adhesive composition of the present invention exhibits excellent adhesive strength, whereas the hydrocarbon resin obtained from the monomer mixture containing no aromatic vinyl monomer (emulsion adhesive compositions E2 and E3), the adhesive strength and peel strength were significantly reduced, especially when styrene-butadiene copolymer latex was used as the rubber latex component of the emulsion adhesive composition (emulsion adhesive compositions E2 and E3). Adhesive composition E3) also has a lower initial tack when using a hydrocarbon resin obtained from a monomer mixture that does not contain a chain conjugated diene monomer (emulsion adhesive compositions F2 and F3). However, when using a hydrocarbon resin obtained from a monomer mixture with a cyclopentadiene monomer content outside the range of the present invention (emulsion adhesive composition), the initial tack and peel strength are significantly reduced. It can be seen that the adhesive strength and peel strength of products G2 and 03) also decreased significantly.
特許出願人 日本ゼオン株式会社 −１９〜Patent applicant: Zeon Corporation -19～
Claims (1)
着付与剤として、（イ）シクロペンタジエン系単量体３
０〜８５重量％、（ロ）芳香族ビニル単量体５〜４０重
量％及び（ハ）鎖状共役ジエン系単量体５〜４０重量％
を含有する単量体混合物を重合して得られる、炭化水素
樹脂を配合して成ることを特徴とするエマルジョン接着
剤組成物。(1) (A) conjugated diene rubber latex, (B) as a tackifier, (a) cyclopentadiene monomer 3
0 to 85% by weight, (b) 5 to 40% by weight of aromatic vinyl monomer, and (c) 5 to 40% by weight of chain conjugated diene monomer.
An emulsion adhesive composition comprising a hydrocarbon resin obtained by polymerizing a monomer mixture containing:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63189261A JPH0721133B2 (en) | 1988-07-28 | 1988-07-28 | Emulsion adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63189261A JPH0721133B2 (en) | 1988-07-28 | 1988-07-28 | Emulsion adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0238478A true JPH0238478A (en) | 1990-02-07 |
| JPH0721133B2 JPH0721133B2 (en) | 1995-03-08 |
Family
ID=16238344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63189261A Expired - Lifetime JPH0721133B2 (en) | 1988-07-28 | 1988-07-28 | Emulsion adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0721133B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003000817A1 (en) * | 2001-06-21 | 2003-01-03 | Tesa Ag | Adhesive tape especially for packaging purposes |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5192842A (en) * | 1975-02-13 | 1976-08-14 | ||
| JPS59152970A (en) * | 1983-02-21 | 1984-08-31 | Mitsui Petrochem Ind Ltd | Pressure-sensitive adhesive composition |
| JPS60177011A (en) * | 1984-02-22 | 1985-09-11 | Nippon Zeon Co Ltd | Preparation of graft polymer |
-
1988
- 1988-07-28 JP JP63189261A patent/JPH0721133B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5192842A (en) * | 1975-02-13 | 1976-08-14 | ||
| JPS59152970A (en) * | 1983-02-21 | 1984-08-31 | Mitsui Petrochem Ind Ltd | Pressure-sensitive adhesive composition |
| JPS60177011A (en) * | 1984-02-22 | 1985-09-11 | Nippon Zeon Co Ltd | Preparation of graft polymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003000817A1 (en) * | 2001-06-21 | 2003-01-03 | Tesa Ag | Adhesive tape especially for packaging purposes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0721133B2 (en) | 1995-03-08 |
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