JP5787175B2 - Tackifier for water-based adhesive / adhesive, tackifier resin emulsion, water-based adhesive / adhesive composition, and method for bonding to rough surface - Google Patents
Tackifier for water-based adhesive / adhesive, tackifier resin emulsion, water-based adhesive / adhesive composition, and method for bonding to rough surface Download PDFInfo
- Publication number
- JP5787175B2 JP5787175B2 JP2012081238A JP2012081238A JP5787175B2 JP 5787175 B2 JP5787175 B2 JP 5787175B2 JP 2012081238 A JP2012081238 A JP 2012081238A JP 2012081238 A JP2012081238 A JP 2012081238A JP 5787175 B2 JP5787175 B2 JP 5787175B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- tackifier
- water
- polymerized rosin
- rosin ester
- 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.)
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- 238000000034 method Methods 0.000 title claims description 51
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、水系粘・接着剤用の粘着付与剤、粘着付与樹脂エマルジョン、水系粘・接着剤組成物、及び、粗面への接着方法に関する。 TECHNICAL FIELD The present invention relates to a tackifier for an aqueous sticky / adhesive, a tackifier resin emulsion, an aqueous sticky / adhesive composition, and a method for bonding to a rough surface.
一般に、ウレタンフォームのような発泡体は、断熱材や構造材として建築用途、冷蔵庫などの家電製品や自動車などに広く使用されている。発泡体は、粘着剤層と接触する表面が凹凸を有していたり、孔を有していたりするので、実質的な接触面積が小さくなる。その結果、平滑な表面を有する基材に比べて、基材と粘着剤層との間での剥離が生じやすい傾向にある。そのため、自動車や建材の分野で用いられる粘・接着剤には、ウレタンフォームのような表面に凹凸を有する粗面への充分な接着力を有することが求められている。 In general, foams such as urethane foam are widely used as a heat insulating material or a structural material in architectural applications, household appliances such as refrigerators, automobiles, and the like. Since the surface of the foam that is in contact with the pressure-sensitive adhesive layer has irregularities or has pores, the substantial contact area is reduced. As a result, compared with a substrate having a smooth surface, peeling between the substrate and the pressure-sensitive adhesive layer tends to occur. For this reason, adhesives and adhesives used in the field of automobiles and building materials are required to have sufficient adhesion to rough surfaces such as urethane foam having uneven surfaces.
一方、食品包装や電子電気製品の外装に用いられているポリエチレン、ポリプロピレンなどのポリオレフィン系樹脂は、官能基を持たず非極性のため、極性分子との親和性が乏しく、粘着剤との密着性や濡れ性が非常に弱く剥がれやすい。そのため、接着面にプライマーを塗布して接着表面を改質する方法が一般に用いられているが、製造工程やコストを削減するため、プライマーを用いることなく、ポリオレフィン系樹脂に対する充分な接着力を有する粘・接着剤が強く求められている。 On the other hand, polyolefin resins such as polyethylene and polypropylene used for the packaging of food packaging and electronic and electrical products have no functional groups and are not polar. Therefore, they have poor affinity with polar molecules, and adhesion with adhesives. And wettability is very weak and easy to peel off. For this reason, a method of modifying the adhesive surface by applying a primer to the adhesive surface is generally used. However, in order to reduce the manufacturing process and cost, it has sufficient adhesion to polyolefin resin without using a primer. There is a strong demand for adhesives and adhesives.
更に、近年、環境・人体の安全性に対する配慮から揮発性有機溶剤等の含有量が少ない環境負荷が低減された水系の粘・接着剤が求められるようになっている。しかしながら、有機溶剤系の粘・接着剤を水系に変更しようとすると、粗面やポリオレフィン系樹脂に対する接着力が不充分になるという問題があった。更に、水系に変更すると、水分や湿気の多い条件下で粘着剤皮膜が白化してしまい、耐水性の点でも改善の余地があった。 Further, in recent years, there has been a demand for water-based adhesives / adhesives with a low content of volatile organic solvents and the like, with reduced environmental loads, in consideration of the environment and the safety of the human body. However, when the organic solvent-based adhesive / adhesive is changed to water-based, there is a problem that the adhesive force to the rough surface or the polyolefin-based resin becomes insufficient. Furthermore, when the water system is changed, the pressure-sensitive adhesive film is whitened under conditions with much moisture and moisture, and there is room for improvement in terms of water resistance.
粗面に対しては、例えば、重合開始剤の使用量に基づき計算されるラジカル発生量を特定の範囲に制御し、分岐構造の少ない直鎖構造のアクリル系重合体にエポキシ化合物を架橋したアクリル系水性粘着剤等が提案されている（特許文献１参照）。これは、粗面に対して優れた接着力を有するが、ポリオレフィン系樹脂に対する接着力については、不充分であった。 For rough surfaces, for example, the amount of radicals calculated based on the amount of polymerization initiator used is controlled within a specific range, and an acrylic polymer in which an epoxy compound is cross-linked to a linear acrylic polymer with few branched structures. A water-based aqueous pressure-sensitive adhesive has been proposed (see Patent Document 1). This has an excellent adhesion to rough surfaces, but is insufficient for adhesion to polyolefin resins.
また、粗面に対しては、特定の高シェア粘度、低シェア粘度等とした水分散型アクリル系粘着剤も提案されている（特許文献２参照）。これは、ウレタンフォームのような表面の凸凹に従った変形が起り易く、初期接着性が良好で、耐剥がれ性や保持性に優れるとのことであるが、これについても、ポリオレフィン系樹脂に対する接着力については、充分とはいえなかった。 Also, water-dispersed acrylic pressure-sensitive adhesives having a specific high shear viscosity, low shear viscosity and the like have been proposed for rough surfaces (see Patent Document 2). This means that deformation according to surface irregularities such as urethane foam is likely to occur, initial adhesion is good, and peeling resistance and retention are excellent, but this also applies to polyolefin resins. The power was not enough.
一方、ポリオレフィン系樹脂に対しては、例えば、特定の酸価を有するロジン類のエステル化物であって酸価が２〜３４０であるもののカルボキシル基を金属化合物により金属塩化した構造の化合物を、乳化剤の存在下で乳化して得られる粘着付与樹脂エマルジョンが提案されている（特許文献３参照）。これは、耐熱性が良好で、かつポリオレフィンに対する接着性も良好であるが、ウレタンフォームのような粗面に対する接着力については、更なる改善が必要であった。 On the other hand, for polyolefin resins, for example, a compound having a structure in which a carboxyl group of a rosin having a specific acid value and an acid value of 2 to 340 is metallated with a metal compound is emulsified. A tackifying resin emulsion obtained by emulsification in the presence of is proposed (see Patent Document 3). Although this has good heat resistance and good adhesion to polyolefin, further improvement is necessary for the adhesion to rough surfaces such as urethane foam.
更に、アルキル鎖の炭素数１〜１４である（メタ）アクリル酸アルキルエステル（ａ）７０〜９９．８重量％、アルキル鎖の炭素数１〜８である（メタ）アクリル酸ヒドロキシアルキル（ｂ）等を含む樹脂組成物水性分散体が提案されている（特許文献４参照）。この水性分散体は、ポリオレフィン被着体に対する高い接着力を有し、タック、耐熱性、曲面接着性に優れ、かつシート状基材との良好な基材密着性を有する水性粘着剤を与えるが、粗面に対する充分な接着力があるとはいえず、またアクリルの種類が限定されてしまうというデメリットがあった。 Furthermore, (meth) acrylic acid alkyl ester (a) having 1 to 14 carbon atoms in the alkyl chain (a) 70 to 99.8% by weight, hydroxyalkyl (meth) acrylate having 1 to 8 carbon atoms in the alkyl chain (b) An aqueous dispersion of a resin composition containing the above has been proposed (see Patent Document 4). This aqueous dispersion has a high adhesion to polyolefin adherends, provides an aqueous pressure-sensitive adhesive having excellent tack, heat resistance, curved surface adhesion, and good substrate adhesion to a sheet-like substrate. However, it cannot be said that there is sufficient adhesion to the rough surface, and there is a demerit that the type of acrylic is limited.
このように、有機溶剤系の粘・接着剤の代替品として様々な水系の粘着剤・接着剤が提案されているが、粗面とオレフィン系樹脂表面の両方に対して優れた接着力を満たしつつ、保持力、定荷重剥離性等の粘着特性、耐水白化性を有し、アクリル系重合体エマルジョンの種類が限定されない水系の粘・接着剤は、未だ開発されていない。 As described above, various water-based pressure-sensitive adhesives and adhesives have been proposed as substitutes for organic solvent-based adhesives and adhesives, but they have excellent adhesion to both rough surfaces and olefin-based resin surfaces. On the other hand, a water-based adhesive / adhesive having adhesive properties such as holding power, constant load peelability, water whitening resistance, and the type of the acrylic polymer emulsion is not limited yet.
本発明は、ウレタンフォームやポリプロピレンフォーム等の粗面を有する基材、特に発泡体基材及びオレフィン系樹脂の表面に対して優れた接着力を満たしつつ、保持力、定荷重剥離性等の粘着特性、耐水白化性を有し、アクリル系重合体エマルジョンの種類が限定されない水系粘・接着剤用の粘着付与剤、粘着付与樹脂エマルジョン、水系粘・接着剤組成物、及び、粗面への接着方法を提供することを目的とする。 The present invention provides adhesives such as holding force and constant load peelability while satisfying excellent adhesion to substrates having rough surfaces such as urethane foam and polypropylene foam, particularly foam substrates and olefinic resin surfaces. Tackifier for water-based viscose / adhesive, which has properties and water whitening resistance, and the type of acrylic polymer emulsion is not limited, tackifier resin emulsion, water-based viscose / adhesive composition, and adhesion to rough surface It aims to provide a method.
本発明者らは上記課題を解決すべく鋭意検討を重ねた結果、常温（１５〜２５℃）で液体の重合ロジンエステルを用いることにより、上記課題を解決することができることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a polymerized rosin ester that is liquid at room temperature (15 to 25 ° C.). Completed.
すなわち、本発明１は、１５〜２５℃において液体の重合ロジンエステルを含有する水系粘・接着剤用の粘着付与剤である。 That is, the present invention 1 is a tackifier for an aqueous adhesive / adhesive containing a polymerized rosin ester which is liquid at 15 to 25 ° C.
本発明２は、本発明１における重合ロジンエステルが、重合ロジン並びに１及び／又は２個の水酸基を有する水酸基含有化合物のエステル化反応により得られるものである水系粘・接着剤用の粘着付与剤である。 The present invention 2 is a tackifier for an aqueous adhesive / adhesive, wherein the polymerized rosin ester in the present invention 1 is obtained by an esterification reaction of a polymerized rosin and a hydroxyl group-containing compound having 1 and / or 2 hydroxyl groups. It is.
本発明３は、ＪＩＳ Ｋ ７１１７−２に準拠し、Ｂ型粘度計を用いて６０℃において測定した上記重合ロジンエステルの粘度が１〜２００Ｐａ・ｓの範囲である本発明１又は２記載の水系粘・接着剤用の粘着付与剤である。 Invention 3 is an aqueous system according to Invention 1 or 2, wherein the viscosity of the polymerized rosin ester measured at 60 ° C. using a B-type viscometer is in the range of 1 to 200 Pa · s in accordance with JIS K 7117-2. It is a tackifier for sticky / adhesives.
本発明４は、ＪＩＳ Ｋ ７１２１に規定した示差走査熱量測定（熱流束ＤＳＣ）による上記重合ロジンエステルのガラス転移温度が−６０〜０℃の範囲である本発明１〜３記載の水系粘・接着剤用の粘着付与剤である。 Invention 4 is a water-based adhesive / adhesion according to Inventions 1 to 3, wherein the glass transition temperature of the polymerized rosin ester is in the range of −60 to 0 ° C. by differential scanning calorimetry (heat flux DSC) defined in JIS K7121. It is a tackifier for agents.
本発明５は、上記水系粘・接着剤が難接着基材に用いられる本発明１〜４のいずれかに記載の水系粘・接着剤用の粘着付与剤である。 This invention 5 is the tackifier for water-based adhesives / adhesives in any one of this invention 1-4 in which the said aqueous adhesive agent is used for a difficult-to-adhere substrate.
本発明６は、本発明１〜５のいずれかに記載の水系粘・接着剤用の粘着付与剤を乳化して得られる粘着付与樹脂エマルジョンである。 This invention 6 is the tackifying resin emulsion obtained by emulsifying the tackifier for water-based adhesives and adhesives in any one of this invention 1-5.
本発明７は、ベースポリマーと本発明１〜５のいずれかに記載の粘着付与剤を含有する水系粘・接着剤組成物である。 This invention 7 is the water-based adhesive and adhesive composition containing the base polymer and the tackifier in any one of this invention 1-5.
本発明８は、本発明７記載のベースポリマーがアクリル系重合体エマルジョンである水系粘・接着剤組成物である。 The present invention 8 is an aqueous adhesive / adhesive composition in which the base polymer according to the present invention 7 is an acrylic polymer emulsion.
本発明９は、粘・接着剤層を介して接着する接着面の少なくとも一方が粗面を含む接着方法であって、粘・接着剤層が本発明７又は８の水系粘・接着剤組成物を含む粗面への接着方法である。 The present invention 9 is an adhesion method in which at least one of the adhesion surfaces to be bonded via the adhesive / adhesive layer includes a rough surface, and the adhesive / adhesive layer is the aqueous adhesive / adhesive composition of the present invention 7 or 8. Is a method of bonding to a rough surface including
本発明によれば、ウレタンフォームやポリプロピレンフォーム等の発泡体基材及びオレフィン系樹脂の表面に対して優れた接着力を有しつつ、保持力、定荷重剥離性等の粘着特性を満足しつつ耐水白化性を有する水系粘・接着剤用の粘着付与剤を提供することができる。また、アクリル系重合体エマルジョンの種類が限定されず、どのようなアクリル系重合体エマルジョンでも含有することができる水系粘・接着剤用の粘着付与剤を提供することができる。 According to the present invention, while having excellent adhesion to the surface of a foam base material such as urethane foam or polypropylene foam and an olefin resin, the adhesive properties such as holding power and constant load peelability are satisfied. It is possible to provide a tackifier for water-based adhesive / adhesive having water whitening resistance. Moreover, the kind of acrylic polymer emulsion is not limited, The tackifier for water-system adhesives / adhesives which can contain any acrylic polymer emulsion can be provided.
本発明の水系粘・接着剤用の粘着付与剤は、１５〜２５℃において液体の重合ロジンエステルを含有する水系粘・接着剤用の粘着付与剤である。上記重合ロジンエステルは、粘着付与剤（粘着付与樹脂）として、重合ロジンに水酸基含有化合物を加えてエステル化反応させて得られるものである。 The tackifier for aqueous tackiness / adhesives of the present invention is a tackifier for aqueous tackiness / adhesives containing a polymerized rosin ester that is liquid at 15 to 25 ° C. The polymerized rosin ester is obtained by adding a hydroxyl group-containing compound to a polymerized rosin and performing an esterification reaction as a tackifier (tackifier resin).
上記重合ロジンとは、二量化された樹脂酸を含むロジン誘導体（ロジン二量体ともいう）である。重合ロジンを製造する方法としては、公知の方法を採用することができる。具体的には、例えば、原料として、ガムロジン、トール油ロジン、ウッドロジン等の原料ロジン類の樹脂酸モノマーを硫酸、フッ化水素、塩化アルミニウム、四塩化チタン等の触媒を含むトルエン、キシレン等の溶媒中、温度４０〜１６０℃程度で、１〜５時間程度反応させる方法等が挙げられる。得られる反応生成物中に占めるロジン二量体の割合は反応温度、反応時間等により異なるが、上記反応生成物中における、樹脂酸ダイマーの含有率は６０重量％以上（ＧＰＣ測定による面積比より算出した値）とすることがオレフィンへの接着性、保持力、定荷重剥離性向上の点から好ましい。 The polymerized rosin is a rosin derivative containing a dimerized resin acid (also referred to as rosin dimer). As a method for producing the polymerized rosin, a known method can be employed. Specifically, for example, a raw material rosin resin acid monomer such as gum rosin, tall oil rosin, and wood rosin as a raw material, and a solvent such as toluene and xylene containing a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride, and titanium tetrachloride. Among them, a method of reacting at a temperature of about 40 to 160 ° C. for about 1 to 5 hours may be mentioned. The proportion of the rosin dimer in the reaction product obtained varies depending on the reaction temperature, reaction time, etc., but the content of the resin acid dimer in the reaction product is 60% by weight or more (from the area ratio by GPC measurement). (Calculated value) is preferable from the viewpoint of improving adhesion to olefin, holding power, and constant load peelability.
上記重合ロジンの具体例としてはトール油系重合ロジン（例えば、商品名「シルバタック１４０」、アリゾナケミカル社製）、ウッド系重合ロジン（例えば、商品名「ダイマレックス」、ハーキュレス社製）、ガム系重合ロジン（例えば、商品名「重合ロジンＢ−１４０」、新洲（武平）林化有限公司製）等が挙げられる。色調が良好となる点で、好ましくは、ガム系重合ロジンである。 Specific examples of the polymerized rosin include tall oil-based polymerized rosin (for example, trade name “Silvatac 140”, manufactured by Arizona Chemical), wood-based polymerized rosin (for example, product name “Dimalex”, manufactured by Hercules), gum Type polymerized rosin (for example, trade name “polymerized rosin B-140”, manufactured by Shinshu (Takehira) Hayashi Kasei Co., Ltd.). A gum-based polymerized rosin is preferable from the viewpoint of good color tone.
上記重合ロジンに水酸基含有化合物を加えてエステル化反応させる製造方法としては、重合ロジン及び水酸基含有化合物を溶媒の存在下又は不存在下に、必要によりエステル化触媒を加え、２５０〜２８０℃程度で、１〜８時間程度加熱脱水反応させればよい。 As a production method in which a hydroxyl group-containing compound is added to the polymerized rosin and subjected to an esterification reaction, the polymerized rosin and the hydroxyl group-containing compound are added in the presence or absence of a solvent, and an esterification catalyst is added if necessary, at about 250 to 280 ° C. The heat dehydration reaction may be performed for about 1 to 8 hours.
上記水酸基含有化合物としては、重合ロジンエステルが１５〜２５℃において液体となるものであれば、特に限定されず、例えば、メタノール、エタノール、プロパノール、ステアリルアルコール、イソステアリルアルコール等の１価のアルコール類、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ネオペンチルグリコール、ダイマージオール、１，６−ヘキサンジオール等の２価のアルコール類、グリセリン、トリメチロールエタン、トリメチロールプロパン等の３価のアルコール類や、ひまし油が挙げられる。これらは一種を単独で用いても、複数を併用してもよい。また、ペンタエリスリトール、ジグリセリンなどの４価のアルコール類、ジペンタエリスリトールなどの６価アルコール等の多価アルコール類は、１〜３価のアルコール類と併用することが好ましい。また、重合ロジンエステルが液体であれば、モノエステル、ジエステル、トリエステル等構造は限定されない。１５〜２５℃において、重合ロジンエステルを液体にすることができ、発泡体基材及びオレフィン系樹脂の表面に対して優れた接着力を満たしつつ、保持力、定荷重剥離性等の粘着特性が優れたものとなるだけでなく、優れた耐水白化性を有する点から、好ましくは、１及び／２個の水酸基を含有することである。より好ましくは、１個の水酸基を含有する水酸基含有化合物である。全水酸基含有化合物中の１及び／２個の水酸基を含有する水酸基含有化合物の含有量は、発泡体基材及びオレフィン系樹脂の表面に対する接着力向上の点で、水酸基含有化合物を１００重量％としたときに、５０〜１００重量％であることが好ましい。 The hydroxyl group-containing compound is not particularly limited as long as the polymerized rosin ester becomes liquid at 15 to 25 ° C., for example, monovalent alcohols such as methanol, ethanol, propanol, stearyl alcohol, and isostearyl alcohol. , Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimer diol, 1,6-hexanediol and other divalent alcohols, glycerin, trimethylolethane, trimethylolpropane and other trivalent alcohols Or castor oil. These may be used alone or in combination. In addition, polyhydric alcohols such as tetrahydric alcohols such as pentaerythritol and diglycerin, and hexahydric alcohols such as dipentaerythritol are preferably used in combination with 1-3 trihydric alcohols. If the polymerized rosin ester is liquid, the structure such as monoester, diester, triester is not limited. At 15 to 25 ° C., the polymerized rosin ester can be made into a liquid and has adhesive properties such as holding power and constant load peelability while satisfying excellent adhesion to the surface of the foam substrate and the olefin resin. From the point of having excellent water whitening resistance as well as being excellent, it preferably contains 1 and / 2 hydroxyl groups. More preferably, it is a hydroxyl group-containing compound containing one hydroxyl group. The content of the hydroxyl group-containing compound containing 1 and / 2 hydroxyl groups in the total hydroxyl group-containing compound is 100% by weight of the hydroxyl group-containing compound in terms of improving the adhesion to the surface of the foam substrate and the olefin resin. When it is, it is preferable that it is 50 to 100 weight%.
上記エステル化反応における重合ロジンの酸価と水酸基含有化合物の水酸基価の比は、（酸価）：（水酸基価）＝１：０．５〜１程度が好ましい。粗面を有する基材、特に発泡体基材及びオレフィン系樹脂の表面に対して優れた接着力を満たしつつ、保持力、定荷重剥離性等の粘着特性についても優れ、バランスのとれたものとする点で、より好ましくは、（酸価）：（水酸基価）＝１：０．５〜０．７５である。 The ratio between the acid value of the polymerized rosin and the hydroxyl value of the hydroxyl group-containing compound in the esterification reaction is preferably about (acid value) :( hydroxyl value) = 1: 0.5-1. While satisfying excellent adhesion to substrates with rough surfaces, especially foam substrates and olefinic resins, it also has excellent adhesive properties such as holding power and constant load peelability, and is well-balanced. More preferably, (acid value) :( hydroxyl value) = 1: 0.5 to 0.75.
なお、重合ロジン生成反応とエステル化反応の順番は、上記に限定されず、エステル化反応の後に、重合反応を行ってもよい。 Note that the order of the polymerization rosin formation reaction and the esterification reaction is not limited to the above, and the polymerization reaction may be performed after the esterification reaction.
こうして得られた重合ロジンエステルは、１５〜２５℃において液体となるものである。 The polymerized rosin ester thus obtained becomes liquid at 15 to 25 ° C.
本発明の粘着付与剤は、水系粘・接着剤用である。この水系粘・接着剤は、環境保護の観点から水に溶解可能な水溶液系の粘着剤及び接着剤、又は、水中に安定に分散された水分散系の粘着剤及び接着剤の両者を意味するものとする。 The tackifier of the present invention is for an aqueous adhesive / adhesive. This water-based adhesive / adhesive means both aqueous solution pressure-sensitive adhesives and adhesives that are soluble in water from the viewpoint of environmental protection, or water-dispersed pressure-sensitive adhesives and adhesives that are stably dispersed in water. Shall.
本発明の重合ロジンエステルは、ＪＩＳ Ｋ ７１１７−２に準拠し、Ｂ型粘度計を用いて６０℃において測定したときの粘度が１〜２００Ｐａ・ｓの範囲であることが好ましい。この範囲とすることで、本発明の重合ロジンエステルを１５〜２５℃において液体に調整しやすくなる。重合ロジンエステルの６０℃における粘度が１Ｐａ・ｓ未満の場合には、粘・接着剤の接着力や保持力の向上効果が充分でなく、２００Ｐａ・ｓを超えると粘・接着剤の粗面に対する接着力が低下する傾向がある。上記観点から、重合ロジンエステルの６０℃における粘度は、より好ましくは、９０〜１９０Ｐａ・ｓの範囲である。更に好ましくは、１００〜１８０Ｐａ・ｓの範囲である。 The polymerized rosin ester of the present invention preferably has a viscosity of 1 to 200 Pa · s when measured at 60 ° C. using a B-type viscometer in accordance with JIS K 7117-2. By setting it as this range, it becomes easy to adjust the polymerized rosin ester of the present invention to a liquid at 15 to 25 ° C. When the viscosity at 60 ° C. of the polymerized rosin ester is less than 1 Pa · s, the effect of improving the adhesive strength and holding power of the adhesive / adhesive is not sufficient. There is a tendency for adhesive strength to decrease. From the above viewpoint, the viscosity of the polymerized rosin ester at 60 ° C. is more preferably in the range of 90 to 190 Pa · s. More preferably, it is the range of 100-180 Pa.s.
上記粘度を１〜２００Ｐａ・ｓの範囲の重合ロジンエステルを調製する方法としては、上記重合ロジンと上記水酸基含有化合物をエステル化する方法が挙げられる。 Examples of a method for preparing a polymerized rosin ester having a viscosity in the range of 1 to 200 Pa · s include a method of esterifying the polymerized rosin and the hydroxyl group-containing compound.
さらに、本発明に使用する重合ロジンエステルは、ＪＩＳ Ｋ ７１２１に規定した示差走査熱量測定（熱流束ＤＳＣ）によるガラス転移温度が−６０〜０℃の範囲であることが好ましい。この範囲とすることで、重合ロジンエステルを１５〜２５℃において液体に調整しやすくなる。また、ガラス転移温度が−６０〜０℃の範囲であることにより、粘・接着剤の粗面及びオレフィン系樹脂に対する接着力を維持しつつ、保持力や定荷重剥離性などの性能の両立が可能である。より好ましくは、−４０〜０℃の範囲である。更に好ましくは、−２０〜０℃の範囲である。 Further, the polymerized rosin ester used in the present invention preferably has a glass transition temperature in the range of −60 to 0 ° C. by differential scanning calorimetry (heat flux DSC) defined in JIS K7121. By setting it as this range, it becomes easy to adjust the polymerized rosin ester to a liquid at 15 to 25 ° C. In addition, when the glass transition temperature is in the range of −60 to 0 ° C., it is possible to achieve coexistence of performance such as holding power and constant load peelability while maintaining the adhesive force to the rough surface of the adhesive / adhesive and the olefin resin. Is possible. More preferably, it is the range of -40-0 degreeC. More preferably, it is the range of -20-0 degreeC.
上記ガラス転移温度が−６０〜０℃の重合ロジンエステルを調整する方法としては、上記ロジン樹脂と上記水酸基含有化合物をエステル化する方法が挙げられる。 Examples of the method for adjusting the polymerized rosin ester having a glass transition temperature of −60 to 0 ° C. include a method of esterifying the rosin resin and the hydroxyl group-containing compound.
こうして得られる重合ロジンエステルは、その種類により、酸価、水酸基価等は異なるものであるが、通常、酸価は、１〜１００ｍｇＫＯＨ／ｇ程度、水酸基価は、１〜１００ｍｇＫＯＨ／ｇ程度のものであり、特に粘・接着性が良好な点で、酸価は、１０〜９０ｍｇＫＯＨ／ｇ、水酸基価は１０〜７０ｍｇＫＯＨ／ｇ程度のものが好ましい。 The polymerized rosin ester thus obtained has different acid value, hydroxyl value, etc. depending on the type, but usually the acid value is about 1 to 100 mgKOH / g, and the hydroxyl value is about 1 to 100 mgKOH / g. The acid value is preferably about 10 to 90 mgKOH / g, and the hydroxyl value is preferably about 10 to 70 mgKOH / g in terms of particularly good viscosity and adhesiveness.
本発明の水系粘・接着剤用の粘着付与剤は、水系粘・接着剤が難接着基材に用いられるものであることが好ましい。難接着基材としては、発泡体基材、オレフィン系樹脂、ＰＥＴ（ポリエチレンフタレート樹脂）、ナイロン等が挙げられる。本発明の水系粘・接着剤用の粘着付与剤は、難接着基材に対して優れた接着力を示す。 As for the tackifier for water-based adhesives / adhesives of this invention, it is preferable that water-based adhesives / adhesives are used for a difficult-to-adhere substrate. Examples of the hardly adhesive substrate include a foam substrate, an olefin resin, PET (polyethylene phthalate resin), and nylon. The tackifier for water-based adhesives / adhesives of the present invention exhibits excellent adhesion to difficult-to-adhere substrates.
上記発泡体基材としては、ポリオレフィンフォーム、ポリウレタンフォーム、塩化ビニルフォーム等の孔を有する基材であり、表面が凹凸を有する粗面である。 The foam substrate is a substrate having pores such as polyolefin foam, polyurethane foam, vinyl chloride foam, etc., and the surface is a rough surface having irregularities.
上記ポリウレタンフォームとしては、例えば軟質ポリエーテル系、軟質ポリエステル系、硬質ポリエーテル系、硬質ポリエステル系が挙げられる。これらの中でも軟質ポリエーテル系、軟質ポリエステル系が好ましく、軟質ポリエーテル系が特に好ましい。 Examples of the polyurethane foam include soft polyether, soft polyester, hard polyether, and hard polyester. Among these, a soft polyether type and a soft polyester type are preferable, and a soft polyether type is particularly preferable.
上記軟質ポリエーテル系ウレタンフォームは、ポリイソシアネートとポリオールに発泡剤、発泡助剤、触媒、着色剤等を混合し、樹脂化しながら発泡させて得られる。空孔が連続気泡となっており、荷重に対して復元性があるものを指す。 The flexible polyether-based urethane foam is obtained by mixing a polyisocyanate and a polyol with a foaming agent, a foaming aid, a catalyst, a colorant, and the like, and foaming the resin while forming a resin. The pores are open-celled and have a resilience to the load.
上記軟質ポリエステル系ウレタンフォームは、ポリイソシアネートとポリエステルジオールに発泡剤、発泡助剤、触媒、着色剤等を混合し、樹脂化しながら発泡させて得られる。空孔が連続気泡となっており、荷重に対して復元性があるものを指す。 The flexible polyester urethane foam is obtained by mixing a polyisocyanate and a polyester diol with a foaming agent, a foaming aid, a catalyst, a colorant, and the like, and foaming while forming a resin. The pores are open-celled and have a resilience to the load.
上記硬質ポリエーテル系ウレタンフォームは、ポリイソシアネートとポリオールに発泡剤、発泡助剤、触媒、着色剤等を混合し、樹脂化しながら発泡させて得られる。空孔が単独気泡となっており、荷重に対して復元性がないものを指す。 The rigid polyether-based urethane foam is obtained by mixing a polyisocyanate and a polyol with a foaming agent, a foaming aid, a catalyst, a colorant, and the like, and foaming while forming a resin. A void is a single bubble, which has no resilience to a load.
上記硬質ポリエステル系ウレタンフォームは、ポリイソシアネートとポリエステルジオールに発泡剤、発泡助剤、触媒、着色剤等を混合し、樹脂化しながら発泡させて得られる。空孔が単独気泡となっており、荷重に対して復元性がないものを指す。 The rigid polyester-based urethane foam is obtained by mixing a polyisocyanate and a polyester diol with a foaming agent, a foaming aid, a catalyst, a colorant, and the like, and foaming while forming a resin. A void is a single bubble, which has no resilience to a load.
上記オレフィン系樹脂としては、例えばポリエチレン、ポリプロピレン、ポリ−１−ブテン、ポリイソブチレン、プロピレンとエチレン及び／又は、１−ブテンとのあらゆる比率でのランダム共重合体又はブロック共重合体、エチレンとプロピレンとのあらゆる比率においてジエン成分が５０重量％以下である重合体（例えば、エチレン−プロピレン−ジエン三元共重合体、ポリメチルペンテン、シクロペンタジエンとエチレン及び／又はプロピレンとの共重合体などの環状ポリオレフィン、エチレン又はプロピレンと５０重量％以下のビニル化合物などとのランダム共重合体、ブロック共重合体）等が挙げられる。これらの中でも、ポリプロピレン、ポリエチレン、ポリイソブチレンが好ましく、ポリプロピレンが特に好ましい。 Examples of the olefin resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymer or block copolymer in any ratio of propylene and ethylene and / or 1-butene, ethylene and propylene. And a polymer having a diene component of 50% by weight or less in any ratio (for example, a cyclic copolymer such as ethylene-propylene-diene terpolymer, polymethylpentene, a copolymer of cyclopentadiene and ethylene and / or propylene). And a random copolymer or block copolymer of polyolefin, ethylene or propylene and 50% by weight or less of a vinyl compound. Among these, polypropylene, polyethylene, and polyisobutylene are preferable, and polypropylene is particularly preferable.
本発明はまた、水系粘・接着剤用の粘着付与剤を乳化して得られる粘着付与樹脂エマルジョンである。本発明の粘着付与樹脂エマルジョンは、上記重合ロジンエステルを乳化することにより得られる。 The present invention is also a tackifying resin emulsion obtained by emulsifying a tackifier for aqueous tackiness / adhesive. The tackifying resin emulsion of the present invention can be obtained by emulsifying the polymerized rosin ester.
上記重合ロジンエステルを乳化する際には、通常乳化剤を用いる。使用する乳化剤としては、特に限定されず公知の乳化剤を用いることができる。具体的には、モノマーを重合させて得られる高分子量乳化剤、低分子量アニオン性乳化剤、低分子量ノニオン性乳化剤などが挙げられる。これらは一種を単独で用いても、数種を併用してもよい。本発明では、特に高分子量乳化剤を用いることが接着性能（特に保持力）、及び機械的安定性を向上させることができるため好ましい。 When emulsifying the polymerized rosin ester, an emulsifier is usually used. It does not specifically limit as an emulsifier to use, A well-known emulsifier can be used. Specific examples include a high molecular weight emulsifier obtained by polymerizing monomers, a low molecular weight anionic emulsifier, and a low molecular weight nonionic emulsifier. These may be used individually by 1 type, or may use several types together. In the present invention, it is particularly preferable to use a high molecular weight emulsifier because adhesion performance (particularly holding power) and mechanical stability can be improved.
上記高分子量乳化剤の製造に用いられるモノマーとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸イソボルニル、ポリオキシアルキレン（メタ）アクリル酸エステル、等の（メタ）アクリル酸エステル系モノマー類；（メタ）アクリル酸、クロトン酸等のモノカルボン酸系ビニルモノマー類；マレイン酸、無水マレイン酸、フマル酸、イタコン酸、ムコン酸等のジカルボン酸系ビニルモノマー類；ビニルスルホン酸、スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸等の有機スルホン酸系ビニルモノマー類；２−（メタ）アクリロイルオキシエチルアシッドホスフェート、ジフェニル−２（メタ）アクリロイルオキシホスフェート等のリン酸エステル系ビニルモノマー等のリン酸系ビニルモノマー類；及びこれら各種有機酸のナトリウム塩、カリウム塩等のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、有機塩基類の塩；（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド等の（メタ）アクリルアミド系モノマー類；（メタ）アクリロニトリル等のニトリル系モノマー類；酢酸ビニル等のビニルエステル系モノマー類；（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシブチル等のヒドロキシ基含有（メタ）アクリル酸エステル系モノマー類；メチルビニルエーテル、グリシジル（メタ）アクリレート、ウレタンアクリレート、炭素数６〜２２のα−オレフィン、ビニルピロリドン等のその他のモノマー類などが挙げられ、これらの１種又は２種以上を公知の方法で重合させたものが挙げられる。 Examples of the monomer used for producing the high molecular weight emulsifier include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid. n-butyl, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, polyoxyalkylene (meth) acrylate (Meth) acrylic acid ester monomers such as (meth) acrylic acid, crotonic acid and other monocarboxylic acid vinyl monomers; maleic acid, maleic anhydride, fumaric acid, itaconic acid, muconic acid and other dicarboxylic acids Vinyl monomers; vinyl sulfonic acid, styrene sulfonic acid, 2 Organic sulfonic acid vinyl monomers such as acrylamido-2-methylpropanesulfonic acid; Phosphoric acid such as 2- (meth) acryloyloxyethyl acid phosphate and phosphate ester vinyl monomers such as diphenyl-2 (meth) acryloyloxyphosphate -Based vinyl monomers; and alkali metal salts such as sodium salts and potassium salts of these various organic acids, alkaline earth metal salts, ammonium salts, salts of organic bases; (meth) acrylamide, N-methylol (meth) acrylamide, etc. (Meth) acrylamide monomers; nitrile monomers such as (meth) acrylonitrile; vinyl ester monomers such as vinyl acetate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylic Hydroxy group-containing (meth) acrylic acid ester monomers such as 2-hydroxybutyl; other monomers such as methyl vinyl ether, glycidyl (meth) acrylate, urethane acrylate, α-olefin having 6 to 22 carbon atoms, vinylpyrrolidone, etc. And those obtained by polymerizing one or more of these by a known method.
上記高分子乳化剤の製造における重合の方法としては、乳化重合、溶液重合、懸濁重合等が挙げられる。 Examples of the polymerization method in the production of the polymer emulsifier include emulsion polymerization, solution polymerization, suspension polymerization and the like.
上記乳化重合は、乳化剤として反応性乳化剤（Ａ）、非反応性乳化剤（Ｂ）などを用いて行うことができる。反応性乳化剤（Ａ）としては、例えば、スルホン酸基、カルボキシル基などの親水基と、アルキル基、フェニル基などの疎水基を有する界面活性剤であって、分子中に炭素−炭素二重結合を有するものをいう。炭素−炭素二重結合としては、たとえば、（メタ）アリル基、１−プロペニル基、２−メチル−１−プロペニル基、ビニル基、イソプロペニル基、（メタ）アクリロイル基等の官能基が挙げられる。反応性乳化剤（Ａ）の具体例としては、たとえば、上記官能基を分子中に少なくとも１つ有するポリオキシエチレンアルキルエーテル、上記官能基を分子中に少なくとも１つ有するポリオキシエチレンフェニルエーテル、及びそれらのスルホコハク酸エステル塩や硫酸エステル塩があげられ、さらに、上記官能基を分子中に少なくとも１つ有するポリオキシエチレンアルキルフェニルエーテル、及びそのスルホコハク酸エステル塩、その硫酸エステル塩、そのリン酸エステル塩、その脂肪族もしくは芳香族カルボン酸塩が挙げられるほか、酸性リン酸（メタ）アクリル酸エステル系乳化剤、ロジングリシジルエステルアクリレートの酸無水物変性物（特開平４−２５６４２９号公報参照）、特開昭６３−２３７２５号公報、特開昭６３−２４０９３１号公報、特開昭６２−１０４８０２号公報に記載の乳化剤等の各種のものが挙げられる。また、反応性乳化剤（Ａ）中のポリオキシエチレンを、ポリオキシプロピレン又はポリオキシエチレンとポリオキシプロピレンをブロック共重合又はランダム共重合したものに代えたものも挙げられる。なお、これらの市販品としては、例えば、「ＫＡＹＡＭＥＲ ＰＭ−１」、「ＫＡＹＡＭＥＲ ＰＭ−２」、「ＫＡＹＡＭＥＲ ＰＭ−２１」（以上、日本化薬（株）製）、「ＳＥ−１０Ｎ」、「ＮＥ−１０」、「ＮＥ−２０」、「ＮＥ−３０」、「アデカリアソープＳＲ−１０」、「アデカリアソープＳＲ−２０」、「アデカリアソープＥＲ−２０」（以上、（株）ＡＤＥＫＡ製）、「ニューフロンティアＡ２２９Ｅ」、「ニューフロンティアＮ１１７Ｅ」、「ニューフロンティアＮ２５０Ｚ」、「アクアロンＲＮ−１０」、「アクアロンＲＮ−２０」、「アクアロンＲＮ−５０」、「アクアロンＨＳ−１０」、「アクアロンＫＨ−０５」、「アクアロンＫＨ−１０」（以上、第一工業製薬（株）製）、「エレミノールＪＳ−２」（三洋化成工業（株）製）、「ラテムルＫ−１８０」（花王（株）製）等がその代表例として挙げられる。反応性乳化剤（Ａ）は、重合性、得られる高分子乳化剤を用いて重合ロジンエステルを乳化する際の乳化性の点からポリオキシエチレンアルキルエーテル系のものが好ましく、（メタ）アリル基を分子中に少なくとも１つ有するポリオキシエチレンアルキルエーテルの硫酸エステル塩を用いることが特に好ましい。これらの市販品としては、「アデカリアソープＳＲ−１０」、「アデカリアソープＳＲ−２０」（商品名、（株）ＡＤＥＫＡ製）、「アクアロンＫＨ−０５」、「アクアロンＫＨ−１０」（第一工業製薬（株）製）が好ましい。 The emulsion polymerization can be performed using a reactive emulsifier (A), a non-reactive emulsifier (B), or the like as an emulsifier. The reactive emulsifier (A) is, for example, a surfactant having a hydrophilic group such as a sulfonic acid group or a carboxyl group and a hydrophobic group such as an alkyl group or a phenyl group, and a carbon-carbon double bond in the molecule. The thing which has. Examples of the carbon-carbon double bond include functional groups such as a (meth) allyl group, 1-propenyl group, 2-methyl-1-propenyl group, vinyl group, isopropenyl group, and (meth) acryloyl group. . Specific examples of the reactive emulsifier (A) include, for example, polyoxyethylene alkyl ether having at least one functional group in the molecule, polyoxyethylene phenyl ether having at least one functional group in the molecule, and And a polyoxyethylene alkylphenyl ether having at least one of the above functional groups in the molecule, and a sulfosuccinic acid ester salt, a sulfuric acid ester salt thereof, and a phosphoric acid ester salt thereof. In addition to the aliphatic or aromatic carboxylate, acidic phosphoric acid (meth) acrylate ester emulsifier, acid anhydride modified product of rosin glycidyl ester acrylate (see JP-A-4-256429), JP Japanese Unexamined Patent Publication No. 63-23725, Japanese Unexamined Patent Publication No. 63-24 931 JP include the various emulsifiers such as described in JP-A-62-104802. Moreover, what replaced the polyoxyethylene in the reactive emulsifier (A) with the block copolymerization or random copolymerization of polyoxypropylene or polyoxyethylene and polyoxypropylene is also mentioned. In addition, as these commercial items, for example, “KAYAMER PM-1”, “KAYAMER PM-2”, “KAYAMER PM-21” (manufactured by Nippon Kayaku Co., Ltd.), “SE-10N”, “ "NE-10", "NE-20", "NE-30", "Adekalia Soap SR-10", "Adekalia Soap SR-20", "Adekalia Soap ER-20" (above, ADEKA Corporation) Manufactured), "New Frontier A229E", "New Frontier N117E", "New Frontier N250Z", "Aquaron RN-10", "Aquaron RN-20", "Aquaron RN-50", "Aquaron HS-10", " "Aqualon KH-05", "Aquaron KH-10" (Daiichi Kogyo Seiyaku Co., Ltd.), "Eleminol JS-2" (Sanyo Kasei) Co. business Ltd.), "Latemul K-180" (manufactured by Kao Corp.) and the like as a typical example. The reactive emulsifier (A) is preferably a polyoxyethylene alkyl ether type in terms of polymerizability and emulsifiability when emulsifying a polymerized rosin ester using the resulting polymer emulsifier. It is particularly preferred to use a polyoxyethylene alkyl ether sulfate ester salt having at least one of them. As these commercial products, “ADEKA rear soap SR-10”, “ADEKA rear soap SR-20” (trade name, manufactured by ADEKA Corporation), “AQUARON KH-05”, “AQUARON KH-10” (No. Ichi Kogyo Seiyaku Co., Ltd.) is preferable.
上記非反応性乳化剤（Ｂ）には、低分子量アニオン性乳化剤、低分子量ノニオン性乳化剤が挙げられる。低分子量アニオン性乳化剤としては、例えばジアルキルスルホコハク酸エステル塩、アルカンスルホン酸塩、α−オレフィンスルホン酸塩、ポリオキシエチレンアルキルエーテルスルホコハク酸エステル塩、ポリオキシエチレンスチリルフェニルエーテルスルホコハク酸エステル塩、ナフタレンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩等が挙げられる。低分子量ノニオン性乳化剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル等が挙げられる。 Examples of the non-reactive emulsifier (B) include a low molecular weight anionic emulsifier and a low molecular weight nonionic emulsifier. Examples of the low molecular weight anionic emulsifier include dialkyl sulfosuccinate, alkane sulfonate, α-olefin sulfonate, polyoxyethylene alkyl ether sulfosuccinate, polyoxyethylene styryl phenyl ether sulfosuccinate, naphthalene sulfone. Acid formalin condensate, polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene alkyl phenyl ether sulfate ester salt and the like can be mentioned. Examples of the low molecular weight nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitan fatty acid ester and the like.
上記高分子乳化剤の製造における乳化重合に際しては、上記乳化剤を１種を単独で又は２種以上を適宜選択して使用することができる。これらの中では、アニオン系乳化剤、ノニオン系乳化剤を用いることが、粘・接着剤組成物に用いられるベースポリマーとの相溶性・混合安定性の点から好ましい。 In the emulsion polymerization in the production of the polymer emulsifier, one type of the emulsifier may be used alone, or two or more types may be appropriately selected and used. Among these, anionic emulsifiers and nonionic emulsifiers are preferably used from the viewpoints of compatibility with the base polymer used in the adhesive / adhesive composition and mixing stability.
このようにして得られた重合ロジンエステル乳化用の高分子量乳化剤の重量平均分子量は特に限定されないが、通常１０００〜５０００００程度とすることが乳化能と得られる粘着付与樹脂エマルジョンの性能において好ましい。また、（メタ）アクリルアミド系モノマーを５０モル％以上用いて得られる（メタ）アクリルアミド系ポリマーを用いることが、粘着剤の塗工性能や接着剤の初期接着性の点で好ましい。また、全乳化剤成分中の少なくとも１０重量％以上、好ましくは８０重量％以上を高分子量乳化剤とすることにより、保持力、定荷重剥離性、曲面接着性を向上させることができるため好ましい。 Although the weight average molecular weight of the high molecular weight emulsifier for emulsification of the polymerized rosin ester thus obtained is not particularly limited, it is usually preferably about 1000 to 500,000 in terms of emulsifying ability and the performance of the resulting tackifier resin emulsion. In addition, it is preferable to use a (meth) acrylamide polymer obtained by using 50 mol% or more of a (meth) acrylamide monomer in terms of the coating performance of the pressure-sensitive adhesive and the initial adhesiveness of the adhesive. Further, it is preferable to use at least 10% by weight or more, preferably 80% by weight or more of the total emulsifier component as a high molecular weight emulsifier, since the holding power, constant load peelability and curved surface adhesion can be improved.
なお、乳化剤の使用量は、通常、重合ロジンエステル１００重量部に対し、固形分換算で１〜１０重量部程度、好ましくは２〜８重量部である。乳化剤の使用量を１重量部以上とすることにより、確実な乳化を行うことができ、また、１０重量部以下とすることにより、高い耐水性、粘着性能を確保することができる点で好ましい。 In addition, the usage-amount of an emulsifier is about 1-10 weight part normally in conversion of solid content with respect to 100 weight part of superposition | polymerization rosin esters, Preferably it is 2-8 weight part. When the amount of the emulsifier used is 1 part by weight or more, reliable emulsification can be performed, and when it is 10 parts by weight or less, high water resistance and adhesive performance can be ensured.
上記乳化方法としては、特に限定されず、高圧乳化法、転相乳化法等の公知の乳化法を採用することができる。 The emulsification method is not particularly limited, and a known emulsification method such as a high pressure emulsification method or a phase inversion emulsification method can be employed.
上記高圧乳化法は、粘着付与剤を液体状態とした上で、乳化剤と水を予備混合して、高圧乳化機を用いて微細乳化した後、必要に応じて溶剤を除去する方法である。粘着付与剤を液体状態とする方法は、加熱のみでも、溶剤に溶解してから加熱しても、可塑剤等の不非揮発性物質を混合して加熱してもよいが、溶剤を使用しない加熱のみが好ましい。なお、溶剤としては、トルエン、キシレン、メチルシクロヘキサン、酢酸エチル等の粘着付与剤成分を溶解できる有機溶剤が挙げられる。 The high-pressure emulsification method is a method in which the tackifier is in a liquid state, the emulsifier and water are premixed, finely emulsified using a high-pressure emulsifier, and then the solvent is removed as necessary. The method of bringing the tackifier into a liquid state may be heated alone, dissolved in a solvent and then heated, or mixed with a non-volatile substance such as a plasticizer and heated, but the solvent is not used. Only heating is preferred. In addition, as a solvent, the organic solvent which can melt | dissolve tackifier components, such as toluene, xylene, methylcyclohexane, and ethyl acetate, is mentioned.
上記転相乳化法は、粘着付与樹脂（粘着付与剤）を加熱溶融した後、攪拌しながら乳化剤・水を加えてＷ／Ｏエマルジョンを形成させ、次いで、水の添加や温度変化等によりＯ／Ｗエマルジョンに転相させる方法である。 In the above phase inversion emulsification method, a tackifier resin (tackifier) is heated and melted, and then an emulsifier and water are added with stirring to form a W / O emulsion. This is a method of phase inversion to W emulsion.
このようにして得られた粘着付与樹脂エマルジョンの固形分濃度は特に限定されないが、通常２０〜７０重量％程度となるように適宜調整して用いる。また、得られたエマルジョンの体積平均粒子径は、通常０．１〜２μｍ程度であり、大部分は１μｍ以下の粒子として均一に分散している。体積平均粒子径０．７μｍ以下とすることが、エマルジョンの貯蔵安定性を良好にできるため好ましい。また、粘着付与樹脂エマルジョンは白色ないし乳白色の外観を呈し、ｐＨは２〜１０程度で、粘度は通常１０〜１０００ｍＰａ・ｓ程度（２５℃、固形分濃度５０％において）ある。 The solid content concentration of the tackifier resin emulsion thus obtained is not particularly limited, but is usually adjusted appropriately so as to be about 20 to 70% by weight. Moreover, the volume average particle diameter of the obtained emulsion is usually about 0.1 to 2 μm, and most of them are uniformly dispersed as particles of 1 μm or less. A volume average particle size of 0.7 μm or less is preferable because the storage stability of the emulsion can be improved. The tackifying resin emulsion has a white to milky white appearance, has a pH of about 2 to 10, and a viscosity of usually about 10 to 1000 mPa · s (at 25 ° C. and a solid concentration of 50%).
本発明はまた、ベースポリマーと上記水系粘・接着剤用の粘着付与剤を含有する粘・接着剤組成物でもある。本発明の水系粘・接着剤組成物は水系粘・接着剤として使用することができる。 The present invention is also a sticky / adhesive composition containing a base polymer and a tackifier for the water-based sticky / adhesive. The aqueous sticky / adhesive composition of the present invention can be used as an aqueous sticky / adhesive.
上記ベースポリマーとして、アクリル系重合体エマルジョン、ゴム系ラテックス及び合成樹脂系エマルジョン等が挙げられ、またそれぞれを併用することもでき、さらに必要に応じて架橋剤、消泡剤、増粘剤、充填剤、酸化防止剤、耐水化剤、造膜助剤等を使用することもできる。また、公知の粘着付与剤を使用しても良い。これら水系粘・接着剤組成物の固形分濃度は通常４０〜７０重量％程度であり、好ましくは５５〜７０重量％である。ベースポリマーは、少なくとも１種以上用いればよいが、アクリル系重合体エマルジョンを用いることが好ましい。 Examples of the base polymer include acrylic polymer emulsions, rubber latexes and synthetic resin emulsions, and can be used in combination with each other. Further, a crosslinking agent, an antifoaming agent, a thickening agent, and a filler are added as necessary. Agents, antioxidants, water resistance agents, film-forming aids, and the like can also be used. Moreover, you may use a well-known tackifier. The solid content concentration of these water-based adhesive / adhesive compositions is usually about 40 to 70% by weight, preferably 55 to 70% by weight. Although at least one base polymer may be used, it is preferable to use an acrylic polymer emulsion.
上記粘着付与剤とベースポリマーの混合方法としては、特に限定されず、粘着付与剤をエマルジョン化した後に、ベースポリマーと混合してもよいし、粘着付与剤をベースポリマーに添加した後、高せん断回転ミキサーを使用して混合してもよい。 The method of mixing the tackifier and the base polymer is not particularly limited, and after emulsifying the tackifier, it may be mixed with the base polymer, or after adding the tackifier to the base polymer, high shear. You may mix using a rotary mixer.
アクリル系重合体エマルジョンとしては、一般に各種のアクリル系粘・接着剤に用いられているものを使用でき、モノマーの一括仕込み重合法、モノマー逐次添加重合法、乳化モノマー逐次添加重合法、シード重合法等の公知の乳化重合法により容易に製造することができる。 As the acrylic polymer emulsion, those generally used for various acrylic adhesives and adhesives can be used. Monomer batch polymerization method, monomer sequential addition polymerization method, emulsion monomer sequential addition polymerization method, seed polymerization method It can be easily produced by a known emulsion polymerization method such as
上記モノマーとしては、（メタ）アクリル酸エステルが挙げられる。具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２−ヒドロキシエチル等をあげることができ、これらを単独で又は二種以上を混合して用いる。また、得られるエマルジョンに貯蔵安定性を付与するため上記（メタ）アクリル酸エステルに代えて（メタ）アクリル酸を少量使用してもよい。さらに所望により（メタ）アクリル酸エステル重合体の接着特性を損なわない程度において、たとえば、酢酸ビニル、スチレン等の共重合可能なモノマーを併用できる。なお、アクリル系重合体エマルジョンに用いられる乳化剤にはアニオン系乳化剤、部分ケン化ポリビニルアルコール等を使用でき、その使用量は重合体１００重量部に対して０．１〜５重量部程度、好ましくは０．５〜３重量部である。 Examples of the monomer include (meth) acrylic acid esters. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and 2-hydroxy (meth) acrylate. Ethyl and the like can be mentioned, and these are used alone or in admixture of two or more. Further, in order to impart storage stability to the resulting emulsion, a small amount of (meth) acrylic acid may be used instead of the (meth) acrylic acid ester. Furthermore, if desired, a copolymerizable monomer such as vinyl acetate or styrene can be used in combination as long as the adhesive properties of the (meth) acrylic acid ester polymer are not impaired. The emulsifier used in the acrylic polymer emulsion may be an anionic emulsifier, partially saponified polyvinyl alcohol, etc., and the amount used is about 0.1 to 5 parts by weight, preferably 100 parts by weight of the polymer. 0.5 to 3 parts by weight.
アクリル系重合体エマルジョンと粘着付与樹脂エマルジョンの使用割合は、特に限定されないが、粘着付与樹脂エマルジョンによる発泡体基材及びオレフィン系樹脂への接着効果が充分に発現でき、かつ、過剰使用による保持力の低下を引き起こさない適当な使用範囲としては、アクリル系重合体エマルジョン１００重量部（固形分換算）に対して、粘着付与樹脂エマルジョンを通常１〜５０重量部程度（固形分換算）とするのがよい。 The use ratio of the acrylic polymer emulsion and the tackifier resin emulsion is not particularly limited, but the adhesive effect of the tackifier resin emulsion on the foam base material and the olefin resin can be sufficiently expressed, and the retention force due to excessive use As an appropriate range of use that does not cause a decrease in the viscosity, the tackifying resin emulsion is usually about 1 to 50 parts by weight (in terms of solid content) with respect to 100 parts by weight of the acrylic polymer emulsion (in terms of solid content). Good.
また、ゴム系ラテックスとしては、水系粘・接着剤組成物に用いられる各種公知のものを使用できる。例えば天然ゴムラテックス、スチレン−ブタジエン共重合体ラテックス、クロロプレンラテックス等が挙げられる。 Moreover, as rubber latex, various well-known things used for an aqueous | water-based adhesive / adhesive composition can be used. Examples thereof include natural rubber latex, styrene-butadiene copolymer latex, chloroprene latex and the like.
上記ゴム系ラテックスと粘着付与樹脂エマルジョンの使用割合は、特に限定されないが、粘着付与樹脂エマルジョンによる改質の効果が充分に発現でき、かつ、過剰使用による保持力、定荷重剥離性、曲面接着性の低下を引き起こさない適当な使用範囲としては、ゴム系ラテックス１００重量部（固形分換算）に対して、粘着付与樹脂エマルジョンを通常１０〜１５０重量部程度（固形分換算）とするのがよい。 The use ratio of the rubber-based latex and the tackifying resin emulsion is not particularly limited. However, the effect of the modification by the tackifying resin emulsion can be sufficiently exhibited, and the holding power, the constant load peelability, and the curved surface adhesiveness due to excessive use can be expressed. As an appropriate range of use that does not cause a decrease in the viscosity, the tackifying resin emulsion is usually about 10 to 150 parts by weight (in terms of solid content) with respect to 100 parts by weight of rubber latex (in terms of solid content).
上記合成樹脂系エマルジョンとしては、水系接着剤組成物に用いられる各種公知のものを使用でき、例えば酢酸ビニル系エマルジョン、エチレン−酢酸ビニル共重合体エマルジョン、ウレタン系エマルジョン等の合成樹脂エマルジョンがあげられる。 As the synthetic resin emulsion, various known ones used in aqueous adhesive compositions can be used, and examples thereof include synthetic resin emulsions such as vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, and urethane emulsion. .
上記合成樹脂系エマルジョンと粘着付与樹脂エマルジョンの使用割合は、特に限定されないが、粘着付与樹脂エマルジョンの改質の効果が充分に発現でき、かつ、過剰使用による保持力、定荷重剥離性、曲面接着性の低下を引き起こさない適当な使用割合としては、合成樹脂系エマルジョン１００重量部（固形分換算）に対して、粘着付与樹脂エマルジョンを通常２〜４０重量部程度（固形分換算）とするのがよい。 The use ratio of the above-mentioned synthetic resin emulsion and tackifying resin emulsion is not particularly limited, but the effect of modifying the tackifying resin emulsion can be fully expressed, and retention force, constant load peelability, curved surface adhesion due to excessive use Appropriate use ratio that does not cause deterioration of the property is that the tackifying resin emulsion is usually about 2 to 40 parts by weight (in terms of solids) with respect to 100 parts by weight of the synthetic resin emulsion (in terms of solids). Good.
本発明は更に、粘・接着剤層を介して接着する接着面の少なくとも一方が粗面を含む接着方法であって、粘・接着剤層が本発明７又は８記載の水系粘・接着剤組成物を含む粗面への接着方法でもある。この接着方法により、粘着剤層がウレタンフォームやポリプロピレンフォーム等の発泡体基材及びオレフィン系樹脂の表面に対して優れた接着力を示す。従来は粗面の空孔内に粘着剤を浸透させるために粘着剤を厚塗りする必要があったが、この方法によれば薄塗りでも良好な接着力が得られるため、厚塗りの必要がなく、歩留りが向上しコストダウンが可能となる。また、従来は接着力を向上させるため直接粗面に粘着剤を塗布する必要があったが、この方法によれば粘着剤を両面テープとし粗面に転写すればよく、作業効率が向上する。 The present invention further relates to an adhesion method in which at least one of the adhesion surfaces to be bonded via the adhesive / adhesive layer includes a rough surface, and the adhesive / adhesive layer is an aqueous adhesive / adhesive composition according to the present invention 7 or 8. It is also a method for bonding to a rough surface including an object. By this adhesion method, the pressure-sensitive adhesive layer exhibits excellent adhesion to the surface of the foam substrate such as urethane foam or polypropylene foam and the olefin resin. Conventionally, it was necessary to apply a thick adhesive to allow the adhesive to penetrate into the pores of the rough surface. However, this method can provide a good adhesive force even with a thin coating, so a thick coating is necessary. Therefore, the yield is improved and the cost can be reduced. Conventionally, it has been necessary to directly apply a pressure-sensitive adhesive to the rough surface in order to improve the adhesive force. However, according to this method, the pressure-sensitive adhesive may be transferred to the rough surface as a double-sided tape, and the working efficiency is improved.
以下に本発明を実施例により更に具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。また実施例中、「％」及び「部」は特に断りのない限り「重量％」、「重量部」を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “%” and “part” mean “% by weight” and “part by weight” unless otherwise specified.
製造例１ ［ベースポリマーエマルジョンの製造］
攪拌装置、温度計、還流冷却管、滴下ロート及び窒素導入管を備えた反応容器に、窒素ガス気流下、水４３．４部及びポリオキシエチレンアルキルエーテル硫酸エステルナトリウム塩（アニオン性乳化剤：商品名「ハイテノール０７３」，第一工業製薬（株）製）０．９２部からなる水溶液を仕込み、７０℃に昇温した。次いで、アクリル酸ブチル９０部、アクリル酸２−エチルヘキシル７部及びアクリル酸３部からなる混合物と、過硫酸カリウム（重合開始剤）０．２４部、ｐＨ調整剤（重曹）０．１１部及び水８．８３部からなる開始剤水溶液の１／１０量を反応容器に添加し、窒素ガス気流下にて７０℃、３０分間予備重合反応を行った。次いで、上記混合物と上記開始剤水溶液の残りの９／１０量を２時間にわたり反応容器に添加して乳化重合を行い、その後７０℃で１時間保持して重合反応を完結させた。こうして得られたアクリル系重合体エマルジョンを室温まで冷却した後１００メッシュ金網を用いてろ過し、固形分４７．８％のアクリル系重合体エマルジョンを得た。
Production Example 1 [Production of base polymer emulsion]
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, 43.4 parts of water and polyoxyethylene alkyl ether sulfate sodium salt (anionic emulsifier: trade name) under nitrogen gas flow An aqueous solution consisting of 0.92 part of “Hitenol 073” (Daiichi Kogyo Seiyaku Co., Ltd.) was charged, and the temperature was raised to 70 ° C. Next, a mixture of 90 parts of butyl acrylate, 7 parts of 2-ethylhexyl acrylate and 3 parts of acrylic acid, 0.24 parts of potassium persulfate (polymerization initiator), 0.11 part of pH adjuster (bicarbonate) and water 1/10 amount of the initiator aqueous solution consisting of 8.83 parts was added to the reaction vessel, and a prepolymerization reaction was performed at 70 ° C. for 30 minutes under a nitrogen gas stream. Next, the remaining 9/10 amount of the mixture and the initiator aqueous solution was added to the reaction vessel over 2 hours to carry out emulsion polymerization, and then held at 70 ° C. for 1 hour to complete the polymerization reaction. The acrylic polymer emulsion thus obtained was cooled to room temperature and then filtered using a 100 mesh wire net to obtain an acrylic polymer emulsion having a solid content of 47.8%.
製造例２［重合ロジンエステル１（粘着付与剤）の製造］
攪拌装置、コンデンサー、温度計及び窒素導入管を備えた反応容器に、重合ロジン１００部（樹脂酸ダイマー６５％、酸価１４０、軟化点１４０℃）、ステアリルアルコール２７．０部（酸価：水酸基価＝１：０．４）を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１２時間反応させ、エステル化を完了させた。その後、減圧下に水分等を除去し、１５〜２５℃において液体の重合ロジンエステル１を得た。得られた重合ロジンエステル１の特性（粘度、ガラス転移点、酸価、水酸基価）を下記方法により測定した。その結果を表１に示す。
Production Example 2 [Production of Polymerized Rosin Ester 1 (Tackifier)]
In a reaction vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen introduction tube, 100 parts of polymerized rosin (resin acid dimer 65%, acid value 140, softening point 140 ° C.), stearyl alcohol 27.0 parts (acid value: hydroxyl group) (Valence = 1: 0.4), the mixture was reacted at 250 ° C for 2 hours under a nitrogen gas stream, and further heated to 280 ° C and reacted at the same temperature for 12 hours to complete esterification. Thereafter, moisture and the like were removed under reduced pressure to obtain a liquid polymerized rosin ester 1 at 15 to 25 ° C. The properties (viscosity, glass transition point, acid value, hydroxyl value) of the obtained polymerized rosin ester 1 were measured by the following methods. The results are shown in Table 1.
（粘度）
ＪＩＳ Ｋ ７１１７−２に準拠し、Ｂ型粘度計を用いて６０℃において測定した。
(viscosity)
Based on JIS K7117-2, it measured at 60 degreeC using the B-type viscosity meter.
（ガラス転移点）
ＪＩＳ Ｋ ７１２１に規定した示差走査熱量測定（熱流束ＤＳＣ）により測定した。
ＤＳＣ測定機器：理学電気（株）製 ＤＳＣ８２３０Ｂ
(Glass transition point)
It measured by the differential scanning calorimetry (heat flux DSC) prescribed | regulated to JISK7121.
DSC measuring device: DSC8230B manufactured by Rigaku Denki Co., Ltd.
（酸価）
ＪＩＳ Ｋ ０７００に準ずる電位差滴定法で測定した。
(Acid value)
It measured by the potentiometric titration method according to JISK0700.
（水酸基価）
ＪＩＳ Ｋ ０７００に準ずる電位差滴定法で測定した。
(Hydroxyl value)
It measured by the potentiometric titration method according to JISK0700.
製造例３［重合ロジンエステル２の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、ステアリルアルコール３３．７部（酸価：水酸基価＝１：０．５）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル２の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 3 [Production of Polymerized Rosin Ester 2]
In the same manner as in Production Example 2, except that 100 parts of polymerized rosin (same as Production Example 2) and 33.7 parts of stearyl alcohol (acid value: hydroxyl value = 1: 0.5) were charged. Production was carried out. The properties of the obtained polymerized rosin ester 2 were measured by the same method as in Production Example 2. The results are shown in Table 1.
製造例４［重合ロジンエステル３の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、ステアリルアルコール５２．４部（酸価：水酸基価＝１：０．７５）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル３の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 4 [Production of Polymerized Rosin Ester 3]
In the same manner as in Production Example 2, except that 100 parts of polymerized rosin (same as Production Example 2) and 52.4 parts of stearyl alcohol (acid value: hydroxyl value = 1: 0.75) were charged. Production was carried out. The characteristics of the obtained polymerized rosin ester 3 were measured by the same method as in Production Example 2. The results are shown in Table 1.
製造例５［重合ロジンエステル４の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、ステアリルアルコール６７．５部（酸価：水酸基価＝１：１）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル４の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 5 [Production of Polymerized Rosin Ester 4]
The same production procedure as in Production Example 2 was conducted except that 100 parts of polymerized rosin (same as Production Example 2) and 67.5 parts of stearyl alcohol (acid value: hydroxyl value = 1: 1) were charged. Carried out. The properties of the obtained polymerized rosin ester 4 were measured in the same manner as in Production Example 2. The results are shown in Table 1.
製造例６［重合ロジンエステル５の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、ステアリルアルコール８１．０部（酸価：水酸基価＝１：１．２）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル５の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 6 [Production of Polymerized Rosin Ester 5]
In the same manner as in Production Example 2, except that 100 parts of polymerized rosin (same as Production Example 2) and 81.0 parts of stearyl alcohol (acid value: hydroxyl value = 1: 1.2) were charged. Production was carried out. The properties of the obtained polymerized rosin ester 5 were measured in the same manner as in Production Example 2. The results are shown in Table 1.
製造例７［重合ロジンエステル６の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、トリエチレングリコール１８．７部（酸価：水酸基価＝１：１）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル６の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 7 [Production of Polymerized Rosin Ester 6]
Produced in the same manner except that 100 parts of polymerized rosin (same as in Production Example 2) and 18.7 parts of triethylene glycol (acid value: hydroxyl value = 1: 1) were charged in the same reaction vessel as in Production Example 2. Carried out. The properties of the obtained polymerized rosin ester 6 were measured by the same method as in Production Example 2. The results are shown in Table 1.
製造例８［重合ロジンエステル７の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、ダイマージオール（クローダ製ＰＲＩＰＯＬ２０３３：ダイマー酸を完全水添して得られる炭素数３６個の脂肪族ジオール））３４．１部（酸価：水酸基価＝１：０．５）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル７の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 8 [Production of Polymerized Rosin Ester 7]
In the same reaction vessel as in Production Example 2, 100 parts of polymerized rosin (same as in Production Example 2), dimer diol (Cropa PRIPOL 2033: aliphatic diol having 36 carbon atoms obtained by complete hydrogenation of dimer acid) ) 34.1 parts (acid value: hydroxyl value = 1: 0.5) were prepared in the same manner. The properties of the obtained polymerized rosin ester 7 were measured by the same method as in Production Example 2. The results are shown in Table 1.
製造例９［重合ロジンエステル８の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、１，６−ヘキサンジオール７．４部（酸価：水酸基価＝１：０．５）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル８の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 9 [Production of Polymerized Rosin Ester 8]
In a reaction vessel similar to Production Example 2, 100 parts of polymerized rosin (same as Production Example 2) and 7.4 parts of 1,6-hexanediol (acid value: hydroxyl value = 1: 0.5) were charged. Others were manufactured in the same manner. The properties of the obtained polymerized rosin ester 8 were measured by the same method as in Production Example 2. The results are shown in Table 1.
製造例１０［重合ロジンエステル９の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、ひまし油（伊藤製油株式会社製：精製ひまし油）４３．８部（酸価：水酸基価＝１：０．５）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル９の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 10 [Production of Polymerized Rosin Ester 9]
In a reaction vessel similar to Production Example 2, 100 parts of polymerized rosin (same as Production Example 2) and 43.8 parts of castor oil (Ito Oil Co., Ltd .: refined castor oil) (acid value: hydroxyl value = 1: 0. Manufacture was carried out in the same manner except that 5) was charged. The properties of the obtained polymerized rosin ester 9 were measured by the same method as in Production Example 2. The results are shown in Table 1.
製造例１１［重合ロジンエステル１０の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、ステアリルアルコール１６．９部、グリセリン１．９部（酸価：水酸基価＝１：０．５）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル１０の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 11 [Production of Polymerized Rosin Ester 10]
In a reaction vessel similar to Production Example 2, 100 parts of polymerized rosin (same as Production Example 2), 16.9 parts of stearyl alcohol, 1.9 parts of glycerin (acid value: hydroxyl value = 1: 0.5) Manufacturing was carried out in the same manner except for charging. The properties of the obtained polymerized rosin ester 10 were measured in the same manner as in Production Example 2. The results are shown in Table 1.
製造例１２［重合ロジンエステル１１の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、ステアリルアルコール１６．９部、ペンタエリスリトール２．１部（酸価：水酸基価＝１：０．５）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル１１の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 12 [Production of Polymerized Rosin Ester 11]
In a reaction container similar to Production Example 2, 100 parts of polymerized rosin (same as Production Example 2), 16.9 parts of stearyl alcohol, 2.1 parts of pentaerythritol (acid value: hydroxyl value = 1: 0.5) Manufacturing was carried out in the same manner except that was charged. The properties of the obtained polymerized rosin ester 11 were measured by the same method as in Production Example 2. The results are shown in Table 1.
製造例１３［重合ロジンエステル１２の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、ダイマージオール１７．１部、グリセリン１．９部（酸価：水酸基価＝１：０．５）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル１２の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 13 [Production of Polymerized Rosin Ester 12]
In a reaction vessel similar to Production Example 2, 100 parts of polymerized rosin (same as Production Example 2), 17.1 parts of dimer diol, 1.9 parts of glycerin (acid value: hydroxyl value = 1: 0.5) Manufacturing was carried out in the same manner except for charging. The properties of the obtained polymerized rosin ester 12 were measured by the same method as in Production Example 2. The results are shown in Table 1.
製造例１４［重合ロジンエステル１３の製造］
製造例２と同様の反応容器に、重合ロジン（製造例２と同一のもの）１００部、ダイマージオール１７．１部、ペンタエリスリトール２．１部（酸価：水酸基価＝１：０．５）を仕込んだ他は同様に製造を実施した。得られた重合ロジンエステル１３の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 14 [Production of Polymerized Rosin Ester 13]
In the same reaction vessel as in Production Example 2, 100 parts of polymerized rosin (same as Production Example 2), 17.1 parts of dimer diol, 2.1 parts of pentaerythritol (acid value: hydroxyl value = 1: 0.5) Manufacturing was carried out in the same manner except that was charged. The properties of the obtained polymerized rosin ester 13 were measured in the same manner as in Production Example 2. The results are shown in Table 1.
製造例１５［ロジンエステル１の製造］
製造例２と同様の反応容器に、不均化ロジン（酸価１６０、軟化点７５℃）１００部、ジエチレングリコール３０．３部（酸価：水酸基価＝１：２）を仕込んだ他は同様に製造を実施した。得られたロジンエステル１の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 15 [Production of rosin ester 1]
The same reaction vessel as in Production Example 2 except that 100 parts of disproportionated rosin (acid value 160, softening point 75 ° C.) and 30.3 parts of diethylene glycol (acid value: hydroxyl value = 1: 2) were used. Production was carried out. The properties of the obtained rosin ester 1 were measured by the same method as in Production Example 2. The results are shown in Table 1.
製造例１６［ロジンエステル２の製造］
製造例２と同様の反応容器に、ガムロジン（酸価１７０、軟化点７０℃）１００部、ジエチレングリコール３２．２部（酸価：水酸基価＝１：２）を仕込んだ他は同様に製造を実施した。得られたロジンエステル２の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 16 [Production of rosin ester 2]
Production was carried out in the same manner except that 100 parts of gum rosin (acid value 170, softening point 70 ° C.) and 32.2 parts of diethylene glycol (acid value: hydroxyl value = 1: 2) were charged in the same reaction vessel as in Production Example 2. did. The properties of the obtained rosin ester 2 were measured by the same method as in Production Example 2. The results are shown in Table 1.
製造例１７［ロジンエステル３の製造］
製造例２と同様の反応容器に、水添ロジン（酸価１７０、軟化点６５℃）１００部、トリエチレングリコール３２．２部（酸価：水酸基価＝１：２）を仕込んだ他は同様に製造を実施した。得られたロジンエステル３の特性を製造例２と同様の方法で測定した。その結果を表１に示す。
Production Example 17 [Production of rosin ester 3]
The same as in Production Example 2, except that 100 parts of hydrogenated rosin (acid value 170, softening point 65 ° C.) and 32.2 parts of triethylene glycol (acid value: hydroxyl value = 1: 2) were charged. Manufacturing was carried out. The properties of the obtained rosin ester 3 were measured by the same method as in Production Example 2. The results are shown in Table 1.
表１における市販樹脂として以下に示すものを使用した。
スーパーエステルＬ：ロジンエステル４（荒川化学工業株式会社製）
ＰＲＩＰＯＬ２０３３：ダイマージオール（クローダジャパン株式会社製）
ＰＲＩＰＯＬ１０１７：ダイマー酸（クローダジャパン株式会社製）
Ｐｏｌｙ ｉｐ：水酸基末端液状Ｃ５系重合体（出光興産株式会社製）
Ｐｏｌｙ Ｂｄ：水酸基末端ポリブタジエン（出光興産株式会社製）
ペンセルＤ−１６０：固形重合ロジンエステル（荒川化学工業株式会社製）
The following commercially available resins in Table 1 were used.
Superester L: Rosin ester 4 (Arakawa Chemical Industries, Ltd.)
PRIPOL 2033: Dimer diol (manufactured by Croda Japan Co., Ltd.)
PRIPOL 1017: Dimer acid (manufactured by Croda Japan Co., Ltd.)
Poly ip: hydroxyl-terminated liquid C5 polymer (made by Idemitsu Kosan Co., Ltd.)
Poly Bd: hydroxyl-terminated polybutadiene (made by Idemitsu Kosan Co., Ltd.)
Pencel D-160: Solid polymerized rosin ester (Arakawa Chemical Industries, Ltd.)
製造例１８［粘着付与樹脂エマルジョンの製造］
市販の重合ロジン−ペンタエリスリトールエステル（商品名「ペンセルＤ−１６０」、荒川化学工業（株）製、軟化点１６０℃）を１００部、８０℃にてトルエン６０部に溶解させた後、アニオン性乳化剤（ドデシルベンゼンスルホン酸ナトリウム）を固形分換算で３部、水を１６０部加え、８０℃にて１時間程度撹拌し、予備乳化した。次いで、得られた予備乳化物を高圧乳化機（マントンガウリン社製）により３０ＭＰａの圧力下で高圧乳化した。次いで、得られた乳化物を２００部、減圧蒸留装置に仕込み、７０℃、２．９３×１０−２ＭＰａの条件下に６時間減圧蒸留を行い、不揮発分が５０重量％の粘着付与樹脂のエマルジョンを得た。
Production Example 18 [Production of Tackifying Resin Emulsion]
After dissolving commercially available polymerized rosin-pentaerythritol ester (trade name “Pencel D-160”, manufactured by Arakawa Chemical Industries, Ltd., softening point 160 ° C.) in 60 parts of toluene at 80 ° C., anionic 3 parts of an emulsifier (sodium dodecylbenzenesulfonate) and 160 parts of water were added, and the mixture was stirred at 80 ° C. for about 1 hour, and pre-emulsified. Subsequently, the obtained preliminary emulsion was high-pressure emulsified with a high-pressure emulsifier (mantongaurin) under a pressure of 30 MPa. Next, 200 parts of the obtained emulsion was charged into a vacuum distillation apparatus and subjected to vacuum distillation at 70 ° C. and 2.93 × 10 −2 MPa for 6 hours. An emulsion was obtained.
（実施例１）
（水系粘着剤組成物１の調製）
製造例２で得られた重合ロジンエステル１を４０部と製造例１で得られたアクリル系重合体のエマルジョン６０部（固形分換算）を、ホモディスパー（特殊機化工業社製）を用いて４０００ｒｐｍにて１分間混合し、増粘剤プライマルＡＳＥ−６０（ロームアンドハース社製）０．５部を添加し、アンモニア水を適量加え、増粘させて水系粘着剤組成物を得た。得られた水系粘着剤組成物について、以下の評価方法により、接着力、保持力、定荷重剥離性、及び、耐水白化性を評価した。結果を表２に示す。
Example 1
(Preparation of aqueous adhesive composition 1)
40 parts of the polymerized rosin ester 1 obtained in Production Example 2 and 60 parts of the acrylic polymer emulsion obtained in Production Example 1 (in terms of solid content) were used with a homodisper (manufactured by Koki Kogyo Co., Ltd.). It mixed for 1 minute at 4000 rpm, 0.5 part of thickener primal ASE-60 (made by Rohm and Haas) was added, an appropriate amount of ammonia water was added, and it was made to thicken, and the water-based adhesive composition was obtained. About the obtained water-based pressure-sensitive adhesive composition, adhesive strength, holding power, constant load peelability, and water whitening resistance were evaluated by the following evaluation methods. The results are shown in Table 2.
（実施例２〜１３、比較例１〜３）
（水系粘着剤組成物２〜１６の調製）
製造例１で得られたベースポリマーエマルジョンと樹脂成分の配合比は、実施例１と同様にして、樹脂成分を表２に示すように変更して、実施例２〜１３と比較例１〜３の水系粘・接着剤組成物を調整した。得られた水系粘着剤組成物について、接着力、保持力、定荷重剥離性及び耐水白化性を評価した。結果を表２に示す。
(Examples 2 to 13, Comparative Examples 1 to 3)
(Preparation of aqueous adhesive compositions 2 to 16)
The compounding ratio of the base polymer emulsion obtained in Production Example 1 and the resin component was changed as shown in Table 2 in the same manner as in Example 1, and Examples 2 to 13 and Comparative Examples 1 to 3 were changed. A water-based adhesive / adhesive composition was prepared. About the obtained water-based adhesive composition, adhesive force, holding power, constant load peelability, and water whitening resistance were evaluated. The results are shown in Table 2.
（比較例４〜８）
（水系粘着剤組成物１７〜２１の調製）
比較例４〜８として、粘・接着剤組成物の樹脂成分に表１に示す市販樹脂を用いた。製造例１で得られたベースポリマーエマルジョンと樹脂成分の配合比は、実施例１と同様にして、得られた水系粘着剤組成物について、これらの接着力、保持力、定荷重剥離性、及び、耐水白化性を評価した結果を表２に示す。
(Comparative Examples 4 to 8)
(Preparation of aqueous adhesive compositions 17 to 21)
As Comparative Examples 4 to 8, commercially available resins shown in Table 1 were used as the resin component of the adhesive / adhesive composition. The blending ratio of the base polymer emulsion obtained in Production Example 1 and the resin component is the same as in Example 1, and for the obtained water-based pressure-sensitive adhesive composition, these adhesive strength, holding power, constant load peelability, and The results of evaluating the water whitening resistance are shown in Table 2.
（比較例９）
（水系粘着剤組成物２２の調製）
製造例１８で得られた粘着付与樹脂エマルジョン４０部（固形分換算）と製造例１で得られたアクリル系重合体のエマルジョン６０部（固形分換算）を混合し、増粘剤プライマルＡＳＥ−６０（ロームアンドハース社製）０．５部を添加し、アンモニア水を適量加え、増粘させて水系粘着剤組成物を得た。得られた水系粘着剤組成物について、以下の評価方法により、接着力、保持力、定荷重剥離性、及び、耐水白化性を評価した。結果を表２に示す。
(Comparative Example 9)
(Preparation of aqueous adhesive composition 22)
40 parts of the tackifier resin emulsion obtained in Production Example 18 (in terms of solid content) and 60 parts of the acrylic polymer emulsion obtained in Production Example 1 (in terms of solid content) are mixed, and the thickener Primal ASE-60 is mixed. 0.5 part (made by Rohm and Haas) was added, an appropriate amount of aqueous ammonia was added, and the mixture was thickened to obtain an aqueous pressure-sensitive adhesive composition. About the obtained water-based pressure-sensitive adhesive composition, adhesive strength, holding power, constant load peelability, and water whitening resistance were evaluated by the following evaluation methods. The results are shown in Table 2.
（粘着評価用の試料フィルムの製造）
上記方法で得られた各水系粘着剤組成物を、サイコロ型アプリケーター（大佑機材（株）製）を用いて厚さ３８μｍのポリエステルフィルム（商品名「Ｓ−１００」、三菱化学ポリエステルフィルム（株）製）に乾燥膜厚が１６０μｍ程度となるように塗工した。次いで、フィルムを１０５℃循風乾燥機中にて５分間乾燥させ、粘着剤組成物中の水分を除去することで試料フィルムを調製した。
(Manufacture of sample film for adhesion evaluation)
Each water-based pressure-sensitive adhesive composition obtained by the above-described method was obtained by using a dice-type applicator (manufactured by Otsugi Equipment Co., Ltd.) and a 38 μm-thick polyester film (trade name “S-100”, Mitsubishi Chemical Polyester Film Co., Ltd.) The product was coated so that the dry film thickness was about 160 μm. Next, the film was dried for 5 minutes in an air circulation dryer at 105 ° C., and water in the pressure-sensitive adhesive composition was removed to prepare a sample film.
（接着力）
上記試料フィルムから幅２５ｍｍ×長さ１５０ｍｍに切り取ったものを試料テープとし、これを軟質エーテル系ウレタンフォーム、ＰＥフォーム又はポリプロピレン（ＰＰ）板に重ね、重量２ｋｇのロールを１往復して貼り付けた。２３℃にて剥離速度３００ｍｍ／分で１８０°剥離を行い、その時の幅２５ｍｍあたりの接着力（ｇ／２５ｍｍ）を測定した。
(Adhesive strength)
A sample tape obtained by cutting the sample film to a width of 25 mm and a length of 150 mm was used as a sample tape, and this was overlaid on a soft ether-based urethane foam, PE foam or polypropylene (PP) plate, and a roll having a weight of 2 kg was pasted once. . 180 ° peeling was performed at 23 ° C. at a peeling speed of 300 mm / min, and the adhesive force (g / 25 mm) per 25 mm width was measured.
（保持力）
上記試料フィルムから幅２５ｍｍ×長さ２５ｍｍに切り取ったものを試料テープとし、これをステンレス板に重ね合わせ、重量２ｋｇのローラーで１往復させて貼り合わせた。４０℃で１．２ｋｇ荷重し、落下した時間（秒）を測定した。落下するまでの時間が長い方が、保持力が強いといえる。
(Holding power)
A sample tape cut from the sample film to a width of 25 mm and a length of 25 mm was used as a sample tape, which was superposed on a stainless steel plate and pasted together by a reciprocating roller with a weight of 2 kg. A load of 1.2 kg was applied at 40 ° C., and the time (second) of dropping was measured. The longer the time it takes to drop, the stronger the holding power.
（定荷重剥離）
上記試料フィルムから幅２５ｍｍ×長さ１００ｍｍに切り取ったものを試料テープとし、これをＰＥ板に重ね合わせ、重量２ｋｇのローラーで１往復させて貼り合わせた。試料テープ末端に２００ｇの荷重をかけ、９０度剥離となるように固定し、２３℃で１時間あたりの剥離距離（ｍｍ）を測定した。１時間以内に落下したものはその時間（分）を測定した。
(Constant load peeling)
A sample tape cut from the sample film to a width of 25 mm and a length of 100 mm was used as a sample tape, which was superposed on a PE plate, and pasted together by a reciprocating roller with a weight of 2 kg. A 200 g load was applied to the end of the sample tape, and the sample tape was fixed so as to be peeled at 90 °, and the peel distance (mm) per hour was measured at 23 ° C. Those that fell within 1 hour were measured for time (minutes).
（耐水白化性）
上記試料フィルムを適当な大きさに切り、２３℃の水に７２時間浸漬した後、粘着剤皮膜の白化程度を以下の基準で目視評価した。
３：変化無し（透明）
２：僅かに白濁
１：強く白濁
(Water whitening resistance)
The sample film was cut to an appropriate size and immersed in water at 23 ° C. for 72 hours, and then the degree of whitening of the adhesive film was visually evaluated according to the following criteria.
3: No change (transparent)
2: Slightly cloudy 1: Strongly cloudy
Claims (9)
該粘・接着剤層が請求項７又は８記載の水系粘・接着剤組成物を含む粗面への接着方法。
An adhesion method in which at least one of the adhesion surfaces to be bonded via the adhesive / adhesive layer includes a rough surface,
A method for adhering to a rough surface, wherein the adhesive / adhesive layer comprises the aqueous adhesive / adhesive composition according to claim 7 or 8.
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| KR102524275B1 (en) * | 2015-09-11 | 2023-04-21 | 아라까와 가가꾸 고교 가부시끼가이샤 | Plasticizer and tacky or adhesive composition for optical applications |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |