JP2018104612A - Tackifier resin emulsion and aqueous adhesive compound - Google Patents
Tackifier resin emulsion and aqueous adhesive compound Download PDFInfo
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本発明は、粘着付与樹脂エマルジョン及び水系粘・接着剤組成物に関する。 The present invention relates to a tackifier resin emulsion and a water-based adhesive / adhesive composition.
ロジンとポリオールの反応物であるロジンエステルは、粘着付与樹脂としてホットメルト接着剤や溶剤型粘・接着剤、エマルジョン型粘・接着剤等において賞用されている（特許文献１〜３）。 Rosin ester, which is a reaction product of rosin and polyol, is used as a tackifier resin in hot melt adhesives, solvent-type adhesives / adhesives, emulsion-type adhesives / adhesives, etc. (Patent Documents 1 to 3).
それらの粘・接着剤は、高温条件で使用されることがあり、その場合、ロジンエステルとしては高軟化点のものが使用される。特にエマルジョン型としては、軟化点が１６５〜１８５℃で、重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）が１．０〜３．０である重合ロジンエステル樹脂を乳化して得られる粘着付与樹脂エマルジョン（特許文献４）や、ベースポリマーおよび粘着付与剤からなる粘着剤組成物において、粘着付与剤が部分強化不均化ロジンのペンタエリスリトールエステルであり、かつその軟化点が１１０から１４０℃である樹脂を被分散体としてなる樹脂エマルジョンであることを特徴とする軟質塩化ビニル用水性粘着剤組成物（特許文献５）が公知である。 These adhesives / adhesives may be used under high temperature conditions, and in that case, a rosin ester having a high softening point is used. In particular, as an emulsion type, tackification is obtained by emulsifying a polymerized rosin ester resin having a softening point of 165 to 185 ° C. and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 1.0 to 3.0. In a resin emulsion (Patent Document 4) and a pressure-sensitive adhesive composition comprising a base polymer and a tackifier, the tackifier is a pentaerythritol ester of partially strengthened disproportionated rosin, and its softening point is 110 to 140 ° C. An aqueous pressure-sensitive adhesive composition for soft vinyl chloride (Patent Document 5) is known which is a resin emulsion in which a certain resin is used as a dispersion.
しかしながら、前記エマルジョンは、樹脂の軟化点を高めることにより、耐熱保持力は向上するものの、分子量が増加するため、ベースポリマーとの相溶性が低下する問題があった。 However, the emulsion has a problem that compatibility with the base polymer is decreased because the heat resistance is improved by increasing the softening point of the resin, but the molecular weight is increased.
本発明の課題は、水系粘・接着剤の粘着付与樹脂エマルジョンとして使用した場合において、ベースポリマーとの相溶性が良好であり、かつ、耐熱保持力にも優れる、新規なロジンエステルタイプの粘着付与樹脂エマルジョンを提供することにある。 The object of the present invention is to provide a novel rosin ester type tackifier that, when used as a tackifier resin emulsion for aqueous adhesives / adhesives, has good compatibility with the base polymer and also has excellent heat resistance. It is to provide a resin emulsion.
本発明者は、上記課題を解決するため、ロジンエステルの軟化点を高めることに着目した。その手段としては、原料ロジンにα，β−不飽和ジカルボン酸を付加させた後にエステル化することが挙げられるが、本手法では、下記構造で示される多塩基樹脂酸を多く含んでおり、これが分岐点となって非常に高分子量化されている。そのため、粘・接着剤組成物のベースポリマーとは相溶し難いと考えられる。 In order to solve the above problems, the present inventor has focused on increasing the softening point of rosin ester. As the means, esterification is performed after adding α, β-unsaturated dicarboxylic acid to the raw material rosin. However, in this method, a lot of polybasic resin acid represented by the following structure is contained, It becomes a branch point and has a very high molecular weight. Therefore, it is considered that it is difficult to be compatible with the base polymer of the adhesive / adhesive composition.
そこで本発明では、α，β−不飽和カルボン酸を使用せずとも高分子量化を達成できる原料ロジンについて検討を重ねた結果、反応性に富む二塩基性樹脂酸を含むロジンを用いることによって、所期の効果を奏する粘着付与樹脂が得られることを見出した。すなわち、本発明は、以下の粘着付与樹脂エマルジョン及び水系粘・接着剤組成物に関する。 Therefore, in the present invention, as a result of repeated studies on a raw material rosin that can achieve high molecular weight without using an α, β-unsaturated carboxylic acid, by using a rosin containing a dibasic resin acid rich in reactivity, It has been found that a tackifier resin exhibiting the desired effect can be obtained. That is, the present invention relates to the following tackifying resin emulsion and aqueous adhesive / adhesive composition.
１．下記一般式で示される二塩基性ジテルペンカルボン酸を含むロジン類（ａ１）及びポリオール（ａ２）を反応成分とするロジンエステル（Ａ）を含む粘着付与樹脂エマルジョン。
２．（ａ１）成分が、更に重合ロジンを含む、前記項１の粘着付与樹脂エマルジョン。 2. (A1) The tackifier resin emulsion according to Item 1, wherein the component further contains a polymerized rosin.
３．前記反応成分が、α，β−不飽和カルボン酸類（ａ３）を含む、前記項１又は２の粘着付与樹脂エマルジョン。 3. Item 3. The tackifier resin emulsion according to Item 1 or 2, wherein the reaction component comprises an α, β-unsaturated carboxylic acid (a3).
４．前記項１〜３のいずれかの粘着付与樹脂エマルジョンを含む水系粘・接着剤組成物。 4). A water-based adhesive / adhesive composition comprising the tackifying resin emulsion according to any one of Items 1 to 3.
５．前記項１〜３のいずれかの粘着付与樹脂エマルジョン及びアクリル系共重合体エマルジョンを含む水系粘・接着剤組成物。 5. 4. A water-based adhesive / adhesive composition comprising the tackifying resin emulsion according to any one of Items 1 to 3 and an acrylic copolymer emulsion.
本発明の粘着付与樹脂エマルジョンは、二塩基性ジテルペンカルボン酸を含むため、α，β−不飽和カルボン酸で変性しなくても軟化点を高めることができ、かつ、ベースポリマーと相溶し、かつ、水系粘・接着剤組成物とした際の耐熱保持力に優れる。 Since the tackifying resin emulsion of the present invention contains a dibasic diterpene carboxylic acid, the softening point can be increased without modification with an α, β-unsaturated carboxylic acid, and it is compatible with the base polymer. And it is excellent in the heat-resistant holding force at the time of setting it as a water-based viscosity and adhesive composition.
本発明の粘着付与樹脂エマルジョンは、下記構造式で示される二塩基性ジテルペンカルボン酸を含むロジン類（ａ１）（以下、（ａ１）成分ともいう。）、ポリオール（ａ２）を反応成分とするロジンエステル（Ａ）（以下、（Ａ）成分ともいう。）を含有する。 The tackifying resin emulsion of the present invention comprises a rosin containing a dibasic diterpenecarboxylic acid represented by the following structural formula (a1) (hereinafter also referred to as the component (a1)) and a polyol (a2) as a reaction component. Contains ester (A) (hereinafter also referred to as component (A)).
二塩基性ジテルペンカルボン酸は、その立体異性構造により、ジヒドロアガト酸、オリベリ酸、エペルエンジカルボン酸及びピニフォリン酸に分類できる。以下に、ジヒドロアガト酸の非限定的な構造を示す。 Dibasic diterpene carboxylic acids can be classified into dihydroagatoic acid, olivelic acid, eperene dicarboxylic acid and pinifolinic acid according to their stereoisomeric structure. The non-limiting structure of dihydroagatoic acid is shown below.
該二塩基性ジテルペンカルボン酸は、一級カルボキシル基が柔軟なアルキル鎖を介して脂環骨格に結合した特異な構造を有する。また、該一級カルボキシル基は反応性が高く、後述の（ａ２）と容易に反応し、高分子量ポリエステルを容易に形成する。該ポリエステルの非限定的な構造を以下に示す。 The dibasic diterpene carboxylic acid has a unique structure in which a primary carboxyl group is bonded to an alicyclic skeleton via a flexible alkyl chain. In addition, the primary carboxyl group is highly reactive, and easily reacts with (a2) described later to easily form a high molecular weight polyester. The non-limiting structure of the polyester is shown below.
（Ａ）成分は、そうした特徴的な分子骨格のポリエステルを含むため、α，β−不飽和カルボン酸で変性されていなくても従来の強化ロジンエステルと同等以上の作用効果を奏するのであろうと推察される。 Since the component (A) contains polyester having such a characteristic molecular skeleton, it is presumed that even if it is not modified with an α, β-unsaturated carboxylic acid, it will have the same or better effect than the conventional reinforced rosin ester. Is done.
（ａ１）成分における前記二塩基性ジテルペンカルボン酸の含有量は、特に限定されないが、該カルボン酸の含有量が少なすぎると（Ａ）成分の軟化点が低くなり、耐熱保持力が低下しやすくなる。また、該カルボン酸の含有量が多すぎると、（Ａ）成分の分子量が高くなり、ベースポリマーとの相溶性が悪化しやすい。本発明では、耐熱保持力及びベースポリマーとの相溶性の点より、二塩基性ジテルペンカルボン酸の含有量は通常２０重量％未満、好ましくは０．５〜１５重量％程度、より好ましくは０．５〜１０重量％程度であるのが良い。 The content of the dibasic diterpene carboxylic acid in the component (a1) is not particularly limited, but if the content of the carboxylic acid is too small, the softening point of the component (A) is lowered, and the heat resistance holding force is likely to decrease. Become. Moreover, when there is too much content of this carboxylic acid, the molecular weight of (A) component will become high and compatibility with a base polymer will deteriorate easily. In the present invention, the content of dibasic diterpene carboxylic acid is usually less than 20% by weight, preferably from about 0.5 to 15% by weight, more preferably from the standpoint of heat resistance and compatibility with the base polymer. It is good that it is about 5 to 10% by weight.
（ａ１）成分としては、例えば、以下の態様が挙げられる。 Examples of the component (a1) include the following embodiments.
（ア）：二塩基性ジテルペンカルボン酸をもともと含むロジン
（イ）：（ア）成分と、二塩基性ジテルペンカルボン酸を含まないロジンとを組み合わせてなるロジン
(A): Rosin originally containing dibasic diterpene carboxylic acid (A): Rosin formed by combining (A) component with rosin not containing dibasic diterpene carboxylic acid
（ア）成分としては、二塩基性ジテルペンカルボン酸を含むロジンであれば、産地及び松種は問わない。例えば、インドネシア産のロジンやベトナム産のロジンには二塩基性ジテルペンカルボン酸が比較的多く含まれている。特に、インドネシア産やベトナム産のメルクシ松（Pinus merkusii）由来のロジン（ガムロジン、トール油ロジン、ウッドロジン等）には、専らジヒドロアガト酸が含まれる。また、該ロジンの水素化物や不均化物、二量化物も使用できる。 (A) As a component, if it is a rosin containing dibasic diterpene carboxylic acid, a production center and a pine seed will not ask | require. For example, Indonesian rosin and Vietnamese rosin contain a relatively large amount of dibasic diterpene carboxylic acid. In particular, rosins derived from Pinus merkusii from Indonesia and Vietnam (such as gum rosin, tall oil rosin and wood rosin) contain exclusively dihydroagatoic acid. In addition, a hydride, disproportionation or dimerization product of the rosin can be used.
（ア）成分は、各種公知の方法で精製してもよく、例えば、蒸留、再結晶及び抽出等が挙げられる。蒸留条件は特に限定されず、通常、温度が２００〜３００℃程度、及び圧力が１３０〜１３００Ｐａ程度である。再結晶は、（ア）成分をベンゼンやトルエン、キシレン、クロロホルム、低級アルコール、アセトン、酢酸エチル等の良溶媒に溶解させた後、該良溶媒を留去して濃厚な溶液となし、該溶液に、ｎ−ヘキサンやｎ−ヘプタン、シクロヘキサン、イソオクタン等の貧溶媒を添加すれば良い。抽出は、（ア）成分をアルカリ水溶液となし、不溶性の不ケン化物を適当な溶媒を用いて抽出した後、水層を中和すればよい。 The component (a) may be purified by various known methods, and examples thereof include distillation, recrystallization and extraction. The distillation conditions are not particularly limited, and the temperature is usually about 200 to 300 ° C. and the pressure is about 130 to 1300 Pa. In recrystallization, the component (a) is dissolved in a good solvent such as benzene, toluene, xylene, chloroform, lower alcohol, acetone, ethyl acetate, and the good solvent is distilled off to form a concentrated solution. In addition, a poor solvent such as n-hexane, n-heptane, cyclohexane, or isooctane may be added. The extraction may be carried out by neutralizing the aqueous layer after forming the component (a) as an alkaline aqueous solution and extracting an insoluble unsaponifiable product using a suitable solvent.
（イ）成分をなす、二塩基性ジテルペンカルボン酸を含まないロジンとしては、特に限定されず、各種公知のものを使用することができる。例えば、ガムロジン、トール油ロジン、ウッドロジンなどの天然ロジンや、天然ロジンを精製して得られる精製ロジン、天然ロジンを水素化反応させて得られる水素化ロジン、天然ロジンを不均化反応させて得られる不均化ロジン、天然ロジンを二量化反応させて得られる重合ロジン等が挙げられる。 The rosin that does not contain the dibasic diterpene carboxylic acid that constitutes the component (a) is not particularly limited, and various known rosins can be used. For example, natural rosin such as gum rosin, tall oil rosin, wood rosin, purified rosin obtained by purifying natural rosin, hydrogenated rosin obtained by hydrogenating natural rosin, obtained by disproportionating natural rosin Examples thereof include disproportionated rosin and polymerized rosin obtained by dimerization reaction of natural rosin.
これらの（イ）成分の中でも、耐熱保持力に優れる点から重合ロジンを使用した方が好ましい。重合ロジンの使用量は特に限定されないが、オレフィン系樹脂に対する接着力、タックおよび低温での接着力に優れる点で、（ａ１）成分を１００重量％として、重合ロジンを１０〜９５重量％程度とするのが好ましい。 Among these components (a), it is preferable to use a polymerized rosin from the viewpoint of excellent heat resistance. The amount of the polymerized rosin used is not particularly limited, but the component (a1) is 100% by weight and the polymerized rosin is about 10 to 95% by weight in terms of excellent adhesion to olefinic resins, tack and low temperature adhesiveness. It is preferable to do this.
（ａ１）成分における二塩基性ジテルペンカルボン酸の含有量は、各種公知の手段で定量できる。例えば、ガスクロマトグラフィー（ＧＣ）を用い、二塩基性ジテルペンカルボン酸に由来するピーク面積を全樹脂酸のピーク面積で除することにより求め得る。 The content of the dibasic diterpene carboxylic acid in the component (a1) can be quantified by various known means. For example, it can be determined by dividing the peak area derived from dibasic diterpene carboxylic acid by the peak area of all resin acids using gas chromatography (GC).
（ａ１）成分の物性は特に限定されないが、軟化点が通常７０〜１６０℃程度であり、また、酸価が通常１３０〜２００ｍｇＫＯＨ／ｇ程度である。 Although the physical property of (a1) component is not specifically limited, A softening point is about 70-160 degreeC normally, and an acid value is about 130-200 mgKOH / g normally.
（ａ２）成分としては、各種公知のポリオールを使用できる。具体的には、例えば、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、ダイマージオール及び１，６−ヘキサンジオール等のジオールや、グリセリン、トリメチロールエタン及びトリメチロールプロパン等のトリオール、ペンタエリスリトール等のテトラオール、ジペンタエリスリトール等の５価以上のポリオール等が挙げられ、二種以上を併用できる。これらの中でも、（Ａ）成分とベースポリマーとの相溶性や、本発明に係る粘着剤・接着剤の性能を考慮すると、ジオール、トリオール及びテトラオールからなる群より選ばれる少なくとも一種が好ましい。 As the component (a2), various known polyols can be used. Specifically, for example, diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimer diol and 1,6-hexanediol, triols such as glycerin, trimethylolethane and trimethylolpropane, Examples thereof include tetraols such as pentaerythritol and pentavalent or higher polyols such as dipentaerythritol, and two or more kinds can be used in combination. Among these, considering the compatibility between the component (A) and the base polymer and the performance of the pressure-sensitive adhesive / adhesive according to the present invention, at least one selected from the group consisting of diol, triol, and tetraol is preferable.
（ａ２）成分の使用量は特に限定されないが、耐熱保持力を特に考慮すると、（ａ１）成分の酸価（ＪＩＳ Ｋ ００７０。以下、酸価というときは同様）と（ａ２）成分中水酸基価（ＪＩＳ Ｋ ００７０。以下、水酸価というときは同様）との比率（ＯＨ／ＣＯＯＨ）が通常０．５〜４程度となる範囲であるのがよい。 The amount of the component (a2) used is not particularly limited, but considering the heat resistance, the acid value of the component (a1) (JIS K 0070; hereinafter referred to as the acid value is the same) and the hydroxyl value of the component (a2) The ratio (OH / COOH) to (JIS K 0070, hereinafter referred to as the hydroxy value) is usually in the range of about 0.5 to 4.
（Ａ）成分の反応成分には、必要に応じて、各種公知のα，β−不飽和カルボン酸類（ａ３）（以下、（ａ３）成分ともいう。）を含めてよい。具体的には、例えば、アクリル酸及びメタクリル酸等のα，β−不飽和モノカルボン酸、並びにフマル酸及び（無水）マレイン酸等のα，β−不飽和ジカルボン酸等が挙げられ、二種以上を併用できる。 The reaction component of the component (A) may include various known α, β-unsaturated carboxylic acids (a3) (hereinafter also referred to as the component (a3)) as necessary. Specific examples include α, β-unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, and α, β-unsaturated dicarboxylic acids such as fumaric acid and (anhydrous) maleic acid. The above can be used together.
（ａ３）成分の使用量は特に限定されないが、本発明の粘着付与樹脂エマルジョンとベースポリマーとの相溶性等を考慮すると、通常、（ａ１）成分が１００重量部に対して１〜８重量部程度、好ましくは１〜５重量部である。 (A3) Although the usage-amount of a component is not specifically limited, When the compatibility etc. of the tackifying resin emulsion of this invention and a base polymer are considered, Usually, (a1) component is 1-8 weight part with respect to 100 weight part. Degree, preferably 1 to 5 parts by weight.
（Ａ）成分としては、例えば、以下の態様が挙げられる。 (A) As a component, the following aspects are mentioned, for example.
（Ａ１）：（ａ１）成分及び（ａ２）成分のエステル化物
（Ａ２）：（Ａ１）成分と（ａ３）成分のディールス・アルダー反応物
（Ａ３）：（ａ１）成分及び（ａ３）成分のディールス・アルダー反応物と、（ａ２）成分とのエステル化物
（Ａ４）：（ａ１）成分、（ａ２）成分及び（ａ３）成分の同時反応物
(A1): Esterified product of component (a1) and component (a2) (A2): Diels-Alder reaction product of components (A1) and (a3) (A3): Diels of components (a1) and (a3) Esterified product of Alder reaction product and component (a2) (A4): Simultaneous reaction product of component (a1), component (a2) and component (a3)
エステル化反応の条件は特に限定されず、例えば前記反応成分を、溶媒の存在下若しくは不存在下、及びエステル化触媒の存在下又は不存在下に、２５０〜２８０℃程度及び１〜８時間程度の条件で反応させればよい。該エステル化触媒としては、例えば、パラトルエンスルホン酸等の酸触媒や、水酸化カルシウム等のアルカリ金属の水酸化物、酸化カルシウム、酸化マグネシウム等の金属酸化物等が挙げられ、二種以上を併用できる。該エステル化反応は、常圧下、減圧下、加圧下及び窒素パージ下のいずれか又は組み合わせの雰囲気で行えばよい。 The conditions for the esterification reaction are not particularly limited. For example, the reaction component is about 250 to 280 ° C. and about 1 to 8 hours in the presence or absence of a solvent and in the presence or absence of an esterification catalyst. The reaction may be performed under the following conditions. Examples of the esterification catalyst include acid catalysts such as p-toluenesulfonic acid, alkali metal hydroxides such as calcium hydroxide, metal oxides such as calcium oxide and magnesium oxide, and the like. Can be used together. The esterification reaction may be performed in an atmosphere of any one or a combination under normal pressure, reduced pressure, increased pressure, and nitrogen purge.
（Ａ）成分の物性は特に限定されないが、（Ａ）成分とベースポリマーとの相溶性や、本発明に係る水系粘・接着剤組成物の耐熱保持力のバランスを考慮すると、重量平均分子量が通常８００〜４０００程度であり、また、軟化点が通常７０〜１８０℃程度であり、また、酸価が通常１〜１００ｍｇＫＯＨ／ｇ程度である。 Although the physical properties of the component (A) are not particularly limited, the weight average molecular weight is determined in consideration of the compatibility between the component (A) and the base polymer and the balance of the heat resistant holding power of the water-based adhesive / adhesive composition according to the present invention. It is usually about 800 to 4000, the softening point is usually about 70 to 180 ° C., and the acid value is usually about 1 to 100 mgKOH / g.
（Ａ）成分には、架橋剤、防滑剤、防腐剤、防錆剤、ｐＨ調整剤、消泡剤（シリコン系消泡剤等）、増粘剤、充填剤、酸化防止剤、耐水化剤、造膜助剤、顔料、染料等の添加剤を含めてもよい。 The component (A) includes a crosslinking agent, an anti-slip agent, an antiseptic, a rust inhibitor, a pH adjuster, an antifoaming agent (silicon-based antifoaming agent, etc.), a thickener, a filler, an antioxidant, and a water-proofing agent Additives such as film-forming aids, pigments and dyes may also be included.
本発明の粘着付与樹脂エマルジョンを得るには、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。これらは単独でも、二種以上を組み合わせてもよい。本発明では、特に高分子量乳化剤を用いることが粘着性能（特に保持力）を向上させる点で好ましい。 In order to obtain the tackifying resin emulsion of the present invention, 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 alone or in combination of two or more. In the present invention, it is particularly preferable to use a high molecular weight emulsifier from the viewpoint of improving the adhesive performance (particularly holding power).
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、等のスルホン酸系ビニルモノマー類；及びこれら各種有機酸のアルカリ金属塩、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、これらは単独又は２種以上を公知の方法で重合させたものが挙げられる。 Monomers used for the production of the high molecular weight emulsifier include, for example, (meth) acrylic acid ester monomers such as methyl (meth) acrylate and ethyl (meth) acrylate, and (meth) acrylic acid and crotonic acid. Monocarboxylic acid vinyl monomers; dicarboxylic acid vinyl monomers such as maleic acid and maleic anhydride; sulfonic acid vinyl monomers such as vinyl sulfonic acid and styrene sulfonic acid; and alkali metals of these various organic acids Salts, alkaline earth metal salts, ammonium salts, salts of organic bases; (meth) acrylamide monomers such as (meth) acrylamide and N-methylol (meth) acrylamide; nitrile monomers such as (meth) acrylonitrile Vinyl ester monomers such as vinyl acetate; (meth) acrylic acid 2- Hydroxy group-containing (meth) acrylic ester monomers such as droxyethyl, 2-hydroxypropyl (meth) acrylate; methyl vinyl ether, glycidyl (meth) acrylate, urethane acrylate, α-olefin having 6 to 22 carbon atoms, vinylpyrrolidone And other monomers such as those obtained by polymerizing a single monomer or two or more monomers by a known method.
上記重合の方法としては、溶液重合、懸濁重合、後述する高分子量乳化剤以外の反応性乳化剤、高分子量乳化剤以外の非反応性乳化剤などを用いた乳化重合などが挙げられる。 Examples of the polymerization method include solution polymerization, suspension polymerization, emulsion polymerization using a reactive emulsifier other than the high molecular weight emulsifier described below, and a non-reactive emulsifier other than the high molecular weight emulsifier.
このようにして得られた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性と、粘着付与樹脂エマルジョンの耐熱保持力を高める点で好ましい。 Although the weight average molecular weight of the high molecular weight emulsifier thus obtained is not particularly limited, it is usually preferably about 1000 to 500,000 from the viewpoint of improving the emulsifiability and the heat resistance retention of the tackifier resin emulsion.
上記高分子量乳化剤以外の反応性乳化剤としては、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。 Examples of reactive emulsifiers other than the high molecular weight emulsifier include surfactants having a hydrophilic group such as a sulfonic acid group and a carboxyl group, and a hydrophobic group such as an alkyl group and a phenyl group, and carbon-carbon in the molecule. It has a double bond.
上記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。 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. Examples include sulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate ester salt, and polyoxyethylene alkyl phenyl ether sulfate ester salt.
低分子量ノニオン性乳化剤としては、例えば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 low molecular weight nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitan fatty acid ester and the like.
なお、乳化剤の使用量は、（Ａ）成分が１００重量部に対して、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、耐水性に優れる点で好ましい。 In addition, the usage-amount of an emulsifier is about 1-10 weight part in conversion of solid content with respect to 100 weight part of (A) component, 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, it is preferable in terms of excellent water resistance.
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、（Ａ）成分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、可塑剤等の非揮発性物質を混合して加熱してもよいが、本発明の粘着付与樹脂を使用した粘着剤を乾燥させた後、粘着剤層に溶剤が残存する可能性があり、環境への影響・作業環境・ハンドリング性が良くなる点で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 component (A) 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 can be heated alone, dissolved in a solvent and then heated, or mixed with a non-volatile substance such as a plasticizer and heated. After drying the pressure-sensitive adhesive using the resin, there is a possibility that the solvent may remain in the pressure-sensitive adhesive layer, and only heating without using a solvent is preferable in terms of improving environmental impact, working environment, and handling properties. 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、（Ａ）成分を加熱溶融した後、撹拌しながら乳化剤・水を加え、まず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, after the component (A) is heated and melted, an emulsifier and water are added while stirring to form a W / O emulsion first, and then the O / W emulsion is formed by adding water or changing temperature. This is a method of phase inversion.
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３５〜６５重量％程度となるように適宜に調整して用いる。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が、０．７μｍ以下とすることが、貯蔵安定性の点から好ましい。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）である。 The solid content concentration of the tackifying resin emulsion thus obtained is not particularly limited, but is usually adjusted appropriately so as to be about 35 to 65% 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, but 0.7 μm or less is storage stable. From the viewpoint of sex. The tackifier 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 content concentration of 50%).
本発明の水系粘・接着剤組成物は、本発明の粘着付与樹脂エマルジョンとベースポリマーとを含有する。 The water-based adhesive / adhesive composition of the present invention contains the tackifying resin emulsion of the present invention and a base polymer.
上記ベースポリマーとして、アクリル系共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。これらの水系粘・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 copolymer emulsions, rubber latexes, and synthetic resin emulsions, and can be used in combination with each other. Further, if necessary, a crosslinking agent, an antifoaming agent, a thickener, Fillers, antioxidants, water resistance agents, film-forming aids, and the like can also be used. The solid content concentration of these aqueous 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.
上記アクリル系共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、（メタ）アクリル酸エステル等の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 said acrylic copolymer emulsion, what is generally used for various acrylic-based adhesives / adhesives can be used, a batch preparation polymerization method of monomers such as (meth) acrylic acid ester, a monomer sequential addition polymerization method, It can be easily produced by a known emulsion polymerization method such as an emulsion monomer sequential addition polymerization method or a seed polymerization method.
上記（メタ）アクリル酸エステルとしては、たとえば、（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粘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上記のアニオン系乳化剤、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 (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, ( (Meth) acrylic acid 2-hydroxyethyl etc. can be mentioned, These are used individually or in mixture of 2 or more types. Further, in order to impart storage stability to the resulting emulsion, a small amount of (meth) acrylic acid may be used in place 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 above-mentioned anionic emulsifier, partially saponified polyvinyl alcohol and the like can be used as the emulsifier used in the acrylic polymer emulsion, and the amount used is about 0.1 to 5 parts by weight with respect to 100 parts by weight of the polymer. Preferably it is 0.5-3 weight part.
上記アクリル系重合体エマルジョンと上記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１〜７０重量部程度（固形分換算）とするのがよい。より好ましくは、５〜２０重量部程度（固形分換算）である。 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 due to excessive use. As an appropriate range of use that does not cause a decrease in holding power, the tackifying resin emulsion is usually about 1 to 70 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). It is good. More preferably, it is about 5 to 20 parts by weight (in terms of solid content).
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、過剰使用による耐熱保持力の低下を引き起こさない適当な使用範囲として、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 latex and the tackifying resin emulsion is not particularly limited, but the effect of modification by the tackifying resin emulsion can be sufficiently expressed, and appropriate use that does not cause a decrease in heat-resistant holding force due to excessive use As a range, 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、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等があげられる。 As the synthetic resin emulsion, various known ones used in water-based adhesive / adhesive compositions can be used. For example, synthetic resin emulsions such as vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, urethane emulsion, etc. Can be given.
上記合成樹脂系エマルジョンと上記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、過剰使用による耐熱保持力の低下を引き起こさない適当な使用割合として、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 synthetic resin emulsion and the tackifying resin emulsion is not particularly limited, but the effect of the modification of the tackifying resin emulsion can be sufficiently expressed, and it does not cause a decrease in heat-resistant holding force due to excessive use. As a proper use ratio, the tackifying resin emulsion is usually about 2 to 40 parts by weight (in terms of solid content) with respect to 100 parts by weight (in terms of solid content) of the synthetic resin emulsion.
以下、本発明を、実施例及び比較例を通じて詳細に説明するが、それらによって本発明の範囲が制限されないことはもとよりである。なお、各実施例及び比較例において、部又は％は重量基準である。 Hereinafter, the present invention will be described in detail through examples and comparative examples, but the scope of the present invention is not limited by them. In the examples and comparative examples, parts or% is based on weight.
＜ジヒドロアガト酸の含有量＞
原料ロジン中のジヒドロアガト酸の含有量は、以下のガスクロマトグラフ質量分析装置で測定した。測定には試料（ロジン類）０．００５ｇをオンカラムメチル化剤（フェニルトリメチルアンモニウムヒドロキサイド（ＰＴＨＡ）０．２モルメタノール溶液、ジーエルサイエンス（株））０．５ｇに溶解させ、１μｌをガスクロマトグラフ質量分析（ＧＣ／ＭＳ）に注入し、測定を行った。樹脂酸のメチルエステル体から、各含有量を決定した。使用装置はガスクロマトグラフ質量分析装置（製品名「Ａｇｉｌｅｎｔ６８９０」、「Ａｇｉｌｅｎｔ５９７３Ｎ」；Ａｇｉｌｅｎｔ ｔｅｃｈｎｏｌｏｇｉｅｓ製）及び市販カラム（製品名「Ａｄｖａｎｃｅ−ＤＳ」、信和化工（株）製）である。
<Content of dihydroagatoic acid>
The content of dihydroagatoic acid in the raw material rosin was measured with the following gas chromatograph mass spectrometer. For the measurement, 0.005 g of a sample (rosin) was dissolved in 0.5 g of an on-column methylating agent (phenyltrimethylammonium hydroxide (PTHA) 0.2 molar methanol solution, GL Sciences Inc.), and 1 μl was gas chromatograph mass. Injected into analysis (GC / MS) and measured. Each content was determined from the methyl ester form of the resin acid. The apparatus used is a gas chromatograph mass spectrometer (product names “Agilent 6890”, “Agilent 5973N”; manufactured by Agilent technologies) and a commercial column (product name “Advance-DS”, manufactured by Shinwa Kako Co., Ltd.).
＜重量平均分子量＞
ロジンエステルの重量平均分子量（Ｍｗ：ポリスチレン換算値）は以下の条件で求めた。
分析装置：ＨＬＣ−８２２０（東ソー（株）製）
カラム：ＴＳＫｇｅｌＳｕｐｅｒＨＭ−Ｌ×３本
溶離液：テトラヒドロフラン
注入試料濃度：５ｍｇ/ｍＬ
流量：０．６ｍＬ/ｍｉｎ
注入量：１００μＬ
カラム温度：４０℃
検出器：ＲＩ
<Weight average molecular weight>
The weight average molecular weight (Mw: polystyrene conversion value) of the rosin ester was determined under the following conditions.
Analyzer: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSKgelSuperHM-L × 3 eluent: Tetrahydrofuran Injection sample concentration: 5 mg / mL
Flow rate: 0.6mL / min
Injection volume: 100 μL
Column temperature: 40 ° C
Detector: RI
各例中、ロジンエステルの軟化点（Ｓｐ（℃））は、ＪＩＳ Ｋ ２５３１の環球法により測定した。 In each example, the softening point (Sp (° C.)) of the rosin ester was measured by the ring and ball method of JIS K2531.
＜体積平均粒子径＞
粘着付与樹脂エマルジョンの体積平均粒子径を、レーザー回折式粒度測定装置（（株）島津製作所製、商品名「ＳＡＬＤ−２０００」）を用い、屈折率１．７０−０．２０ｉ、吸光度０．０６の条件下で測定した。
<Volume average particle diameter>
The volume average particle size of the tackifying resin emulsion was measured using a laser diffraction particle size measuring device (manufactured by Shimadzu Corporation, trade name “SALD-2000”), refractive index 1.70-0.20i, absorbance 0.06. The measurement was performed under the following conditions.
１．ロジンエステル（Ａ）の製造1. Production of rosin ester (A)
製造例１
撹拌装置、冷却管、温度計及び窒素導入管を備えた反応容器に、インドネシア産のガムロジン（ジヒドロアガト酸１０重量％、酸価１９０ｍｇＫＯＨ／ｇ、軟化点８０℃。以下、ＩＤロジンともいう。）１００部を仕込み、２００℃で溶融させた。次いで、同温度の溶融物に、ペンタエリスリトール１５部を仕込み、窒素ガス気流下、２８０℃で１０時間エステル化反応を行った。その後、３時間減圧処理することにより、ロジンエステル（Ａ−１）を合成した。物性を表１に示す。（以下同様）
Production Example 1
Indonesian gum rosin (dihydroagatoic acid 10% by weight, acid value 190 mgKOH / g, softening point 80 ° C., hereinafter also referred to as ID rosin) in a reaction vessel equipped with a stirrer, a cooling tube, a thermometer and a nitrogen introduction tube. 100 parts were charged and melted at 200 ° C. Next, 15 parts of pentaerythritol was charged into the melt at the same temperature, and an esterification reaction was performed at 280 ° C. for 10 hours in a nitrogen gas stream. Then, rosin ester (A-1) was synthesize | combined by carrying out pressure reduction processing for 3 hours. The physical properties are shown in Table 1. (The same applies hereinafter)
製造例２
製造例１と同様の反応容器に、ＩＤロジン１００部を仕込み、２００℃で溶融させた。次いで、反応系にフマル酸１．４部を仕込み、２００℃で１時間反応させた。次いで、同温度の溶融物に、ペンタエリスリトール１４部を仕込み、窒素ガス気流下に２８０℃で１０時間、エステル化反応を行い、次いで３時間減圧処理することにより、ロジンエステル（Ａ−２）を合成した。
Production Example 2
In a reaction container similar to Production Example 1, 100 parts of ID rosin was charged and melted at 200 ° C. Next, 1.4 parts of fumaric acid was charged into the reaction system and reacted at 200 ° C. for 1 hour. Next, 14 parts of pentaerythritol was charged into the melt at the same temperature, subjected to esterification reaction at 280 ° C. for 10 hours under a nitrogen gas stream, and then subjected to reduced pressure treatment for 3 hours to obtain rosin ester (A-2). Synthesized.
製造例３
製造例１と同様の反応容器に、ＩＤロジン５０部と中国産のガムロジン（ジヒドロアガト酸０重量％、酸価１７０ｍｇＫＯＨ／ｇ、軟化点７５℃。以下、ＣＮロジンともいう。）５０部とを仕込み、２００℃で溶融させた。次いで、同温度の溶融物に、ペンタエリスリトール１５部を仕込み、窒素ガス気流下２８０℃で８時間、エステル化反応を行い、次いで３時間減圧処理することによりロジンエステル（Ａ−３）を合成した。
Production Example 3
In the same reaction vessel as in Production Example 1, 50 parts of ID rosin and 50 parts of Chinese gum rosin (dihydroagatoic acid 0% by weight, acid value 170 mgKOH / g, softening point 75 ° C., hereinafter also referred to as CN rosin). Charged and melted at 200 ° C. Next, 15 parts of pentaerythritol was charged into the melt at the same temperature, subjected to esterification at 280 ° C. for 8 hours under a nitrogen gas stream, and then subjected to reduced pressure treatment for 3 hours to synthesize rosin ester (A-3). .
製造例４
製造例１と同様の反応容器に、重合ロジン９５部とＩＤロジン５部とを仕込み、２００℃で溶融させた。次いで、同温度の溶融物に、ペンタエリスリトール１５部を仕込み、窒素ガス気流下に２８０℃で１０時間、エステル化反応を行い、次いで３時間減圧処理することにより、ロジンエステル（Ａ−４）を合成した。
Production Example 4
In the same reaction vessel as in Production Example 1, 95 parts of polymerized rosin and 5 parts of ID rosin were charged and melted at 200 ° C. Next, 15 parts of pentaerythritol was charged into the melt at the same temperature, subjected to esterification reaction at 280 ° C. for 10 hours under a nitrogen gas stream, and then subjected to reduced pressure treatment for 3 hours to obtain rosin ester (A-4). Synthesized.
比較製造例１
製造例１と同様の反応容器に、ＣＮロジン１００部を仕込み、窒素ガス気流下２００℃で溶融させた。次いで、同温度の溶融物に、ペンタエリスリトール１５部を仕込み、窒素ガス気流下で２８０℃で８時間、エステル化反応を行った。その後、２時間減圧処理することにより、ロジンエステル（Ａ−５）を合成した。
Comparative production example 1
In a reaction vessel similar to Production Example 1, 100 parts of CN rosin was charged and melted at 200 ° C. under a nitrogen gas stream. Next, 15 parts of pentaerythritol was charged into the melt at the same temperature, and an esterification reaction was performed at 280 ° C. for 8 hours under a nitrogen gas stream. Then, rosin ester (A-5) was synthesize | combined by carrying out pressure reduction processing for 2 hours.
比較製造例２
製造例１と同様の反応容器に、ＣＮロジン１００部を仕込み、窒素ガス気流下２００℃で溶融させた。次いで、反応系にフマル酸１０部を仕込み、２００℃で１時間反応させた。次いで、同温度の溶融物に、ペンタエリスリトール１２部を仕込み、窒素ガス気流下で２８０℃で１０時間、エステル化反応を行った。その後、４時間減圧処理することにより、ロジンエステル（Ａ−６）を合成した。
Comparative production example 2
In a reaction vessel similar to Production Example 1, 100 parts of CN rosin was charged and melted at 200 ° C. under a nitrogen gas stream. Next, 10 parts of fumaric acid was charged into the reaction system and reacted at 200 ° C. for 1 hour. Next, 12 parts of pentaerythritol was charged into the melt at the same temperature, and an esterification reaction was performed at 280 ° C. for 10 hours under a nitrogen gas stream. Then, rosin ester (A-6) was synthesize | combined by carrying out pressure reduction processing for 4 hours.
２．高分子量乳化剤の製造2. Production of high molecular weight emulsifier
合成例１
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、スチレン３０部、メタクリル酸メチル３０部、およびメタクリル酸４０部を仕込んだ。次いで、これに２，４−ジフェニル−４−メチル−１−ペンテン５部、過硫酸カリウム２部および水３００部を混合し重合を開始した。８５℃で２時間攪拌した後、過硫酸カリウム１部を添加し同温度で１時間保温した。さらに４８％水酸化カリウム２４部を添加後、常温まで冷却した。不揮発分２４．５％の高分子量乳化剤の分散液を得た。
Synthesis example 1
30 parts of styrene, 30 parts of methyl methacrylate, and 40 parts of methacrylic acid were charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. Next, 5 parts of 2,4-diphenyl-4-methyl-1-pentene, 2 parts of potassium persulfate and 300 parts of water were mixed with this to initiate polymerization. After stirring at 85 ° C. for 2 hours, 1 part of potassium persulfate was added and kept at the same temperature for 1 hour. Further, 24 parts of 48% potassium hydroxide was added, and then cooled to room temperature. A dispersion of a high molecular weight emulsifier having a nonvolatile content of 24.5% was obtained.
３．粘着付与樹脂エマルジョン（Ｂ）の製造3. Manufacture of tackifying resin emulsion (B)
実施例１
撹拌装置、温度計、還流冷却管、滴下ロートおよび窒素導入管を備えた反応容器に、ロジンエステル（Ａ−１）１００部とトルエン６０部を仕込み、１００℃に昇温して溶解させた。８０℃まで冷却し、水１２０部及びポリオキシエチレンラウリルエーテル硫酸アンモニウム（商品名「ハイテノールＬＡ−１６」：第一工業製薬（株）製）４部からなる水溶液を添加した。その後、７５℃で１時間かけて強攪拌し、予備乳化を行った。得られた予備乳化液を高圧乳化機（装置名「１５ＭＲ−８ＴＡ Ｈｏｍｏｇｅｎｉｚｅｒ」、マントンガウリン社製）を用いて、圧力３０ＭＰａで乳化した後、６５℃、１３０ｈＰａの条件で、固形分５０．０％となるまでトルエンと水を減圧除去して粘着付与樹脂エマルジョン（Ｂ−１）を得た。物性を表２に示す（以下同様）。
Example 1
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 100 parts of rosin ester (A-1) and 60 parts of toluene were charged and heated to 100 ° C. to be dissolved. The mixture was cooled to 80 ° C., and an aqueous solution consisting of 120 parts of water and 4 parts of polyoxyethylene lauryl ether ammonium sulfate (trade name “HITENOL LA-16” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added. Thereafter, the mixture was vigorously stirred at 75 ° C. for 1 hour to perform preliminary emulsification. The obtained pre-emulsified solution was emulsified at a pressure of 30 MPa using a high-pressure emulsifier (device name “15MR-8TA Homogenizer”, manufactured by Manton Gaurin Co., Ltd.). Toluene and water were removed under reduced pressure until a tackified resin emulsion (B-1) was obtained. The physical properties are shown in Table 2 (the same applies hereinafter).
実施例２〜５、比較例１〜２
ロジンエステル（Ａ）または乳化剤の種類を表２のように変えて、実施例１と同様に製造し、粘着付与樹脂エマルジョン（Ｂ−２）〜（Ｂ−７）を得た。
Examples 2-5, Comparative Examples 1-2
The kind of rosin ester (A) or emulsifier was changed as shown in Table 2, and the same procedure as in Example 1 was performed to obtain tackifying resin emulsions (B-2) to (B-7).
４．アクリル系共重合体エマルジョンの製造4). Production of acrylic copolymer emulsion
合成例２
撹拌装置、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ラウリルエーテル硫酸アンモニウム（商品名「ハイテノールＬＡ−１６」：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、重曹（ｐＨ調整剤）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％のアクリル系共重合体エマルジョンを得た。
Synthesis example 2
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 43.4 parts of water and polyoxyethylene lauryl ether ammonium sulfate (trade name “HITENOL LA-16” under a nitrogen gas stream : Daiichi Kogyo Seiyaku Co., Ltd.) 0.92 part of an aqueous solution was charged, and the temperature was raised to 70 ° C. Next, a mixture comprising 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 sodium bicarbonate (pH adjuster) 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 copolymer emulsion having a solid content of 47.8%.
５．水系粘・接着剤組成物の調製5. Preparation of water-based adhesive / adhesive composition
合成例２のアクリル共重合体エマルジョン（固形分換算：９０部）および粘着付与樹脂エマルジョン（Ｂ−１）（固形分換算：１０部）を配合し、水系粘・接着剤組成物を得た。粘着付与樹脂エマルジョン（Ｂ−２）〜（Ｂ−７）についても同様にして水系粘・接着剤組成物を得た。 The acrylic copolymer emulsion of Synthesis Example 2 (solid content conversion: 90 parts) and the tackifier resin emulsion (B-1) (solid content conversion: 10 parts) were blended to obtain an aqueous viscous / adhesive composition. A water-based adhesive / adhesive composition was obtained in the same manner for tackifying resin emulsions (B-2) to (B-7).
ポリエチレンフィルム（商品名「Ｓ−１００」、三菱化学ポリエステルフィルム（株）製）厚み：３８μｍ）に、前記水系粘・接着剤組成物を１００μｍアプリケーターを用いて直接塗工し、１０５℃の循風乾燥機で５分間乾燥させて試料テープを作成した。試料テープの厚みは３０μｍであった。 The water-based adhesive / adhesive composition was directly applied to a polyethylene film (trade name “S-100”, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) thickness: 38 μm) using a 100 μm applicator, and the air circulation at 105 ° C. A sample tape was prepared by drying for 5 minutes with a dryer. The thickness of the sample tape was 30 μm.
＜相溶性＞
分光光度計（商品名「Ｕ−３２１０形自記分光光度計」、（株）日立製作所製）を用いて、前記試料テープに波長が５００ｎｍの光を照射し、その透過率（％）を測定し、下記基準で相溶性を評価した。結果を表２に示す。
○：８５％以上
△：７０％以上８５％未満
×：７０％未満
<Compatibility>
Using a spectrophotometer (trade name “U-3210 self-recording spectrophotometer”, manufactured by Hitachi, Ltd.), the sample tape was irradiated with light having a wavelength of 500 nm, and the transmittance (%) was measured. The compatibility was evaluated according to the following criteria. The results are shown in Table 2.
○: 85% or more Δ: 70% or more and less than 85% ×: less than 70%
＜耐熱保持力＞
ＰＳＴＣ−１０７（粘着テープ工業会（Pressure Sensitive Tape Council）（米国）によるクリープ法）に従い、前記試料テープ（２５ｍｍ×２５ｍｍ）をステンレス板に貼り付け、６０℃で１．０ｋｇの荷重を試料テープに加え、試料テープが落下するまでの時間を測定し、下記基準で耐熱保持力を評価した。結果を表２に示す。
○：６時間以上
△：３時間以上６時間未満
×：３時間未満
<Heat resistant holding power>
In accordance with PSTC-107 (creep method by Pressure Sensitive Tape Council (USA)), the sample tape (25 mm × 25 mm) is attached to a stainless steel plate, and a load of 1.0 kg is applied to the sample tape at 60 ° C. In addition, the time until the sample tape dropped was measured, and the heat resistant holding force was evaluated according to the following criteria. The results are shown in Table 2.
○: 6 hours or more Δ: 3 hours or more and less than 6 hours ×: Less than 3 hours
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