JP2007131706A - Tackifier and hot melt adhesive composition - Google Patents
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本発明は、粘着付与剤及びホットメルト接着剤組成物に関する。より詳しくは、ベースポリマーに優れた粘着性を付与する粘着付与剤、及びこの粘着付与剤を添加することにより、良好な接着性が維持され、さらに優れた凝集力を発現することができるホットメルト接着剤組成物に関する。 The present invention relates to a tackifier and a hot melt adhesive composition. More specifically, a tackifier that imparts excellent tackiness to the base polymer, and a hot melt that can maintain good adhesiveness and exhibit excellent cohesion by adding this tackifier. The present invention relates to an adhesive composition.
ナプキン、紙おむつ等の衛生材料に塗布して加熱により接着効果を発揮する接着剤としてＳＩＳ、ＳＢＳ、ＳＥＢＳなどのスチレンブロックコポリマーをベースとし、これに粘着付与樹脂を添加してなるホットメルト接着剤がよく知られている。通常、この種のホットメルト接着剤の粘着付与樹脂には、清潔感を得るため各種水添樹脂およびスチレン系樹脂が配合されている。 Hot melt adhesives based on styrene block copolymers such as SIS, SBS, SEBS, etc., which are applied to sanitary materials such as napkins and paper diapers and exert an adhesive effect when heated, and to which tackifying resins are added well known. Usually, a tackifying resin of this type of hot melt adhesive is blended with various hydrogenated resins and styrene resins in order to obtain a clean feeling.
しかし、この用途に使用される水添樹脂はホットメルト接着剤に配合すると接着力を低下させるという問題点がある。近年、接着力に優れたスチレン系樹脂が使用される様になったが、更に高い耐熱クリープ性を持ったホットメルト接着剤が求められている。 However, the hydrogenated resin used for this purpose has a problem that when it is blended with a hot melt adhesive, the adhesive strength is lowered. In recent years, styrenic resins having excellent adhesive strength have been used, but there is a demand for hot melt adhesives having higher heat-resistant creep properties.
本発明の目的は、適正な分子量を有する特定のスチレン共重合系粘着付与剤を添加することで、優れた接着力及び耐熱クリープ性を発現することができるホットメルト接着剤組成物を提供することにある。 An object of the present invention is to provide a hot melt adhesive composition that can exhibit excellent adhesive force and heat-resistant creep property by adding a specific styrene copolymer tackifier having an appropriate molecular weight. It is in.
本発明者は、前記の課題を検討し、特定の共重合体を含む粘着付与剤をベースポリマーに添加することにより、目的が達成されることを見出し、本発明を完成するに至った。 The present inventor has studied the above-mentioned problems, found that the object can be achieved by adding a tackifier containing a specific copolymer to the base polymer, and completed the present invention.
すなわち、本発明は、下記の粘着付与剤及びホットメルト接着剤を提供するものである。
［１］下記の（ｉ）〜（ｉｉｉ）で規定される共重合体を含む粘着付与剤（Ｂ）。
（ｉ）α−メチルスチレンおよびイソプロペニルトルエンからなる群から選ばれる少なくとも１種のモノマーと、スチレンとの共重合体であり、
（ｉｉ）スチレンから導かれる構成単位の含有率が５０〜８０モル％であり、
（ｉｉｉ）軟化点（Ｔｍ）が７０〜１６０℃である共重合体
［２］前記共重合体が、軟化点（Ｔｍ（℃））と重量平均分子量（Ｍｗ）との関係が下記の式（１）を満足する共重合体である［１］に記載の粘着付与剤（Ｂ）。
Ｔｍ＜０．０２７×Ｍｗ＋４４．９６５ （１）
［３］共重合体の重量平均分子量（Ｍｗ）が１０００〜５０００である［１］に記載の粘着付与剤（Ｂ）。
［４］ベースポリマー（Ａ）１００重量部と［１］に記載の粘着付与剤（Ｂ）１０〜３００重量部からなるホットメルト接着剤組成物。
［５］ベースポリマー（Ａ）が、ビニル芳香族化合物と共役ジエン化合物からなる共重合体及び／又はその水添物である［４］に記載のホットメルト接着剤組成物。
That is, the present invention provides the following tackifier and hot melt adhesive.
[1] A tackifier (B) containing a copolymer defined by the following (i) to (iii).
(I) a copolymer of at least one monomer selected from the group consisting of α-methylstyrene and isopropenyltoluene and styrene;
(Ii) The content of the structural unit derived from styrene is 50 to 80 mol%,
(Iii) Copolymer having a softening point (Tm) of 70 to 160 ° C. [2] In the copolymer, the relationship between the softening point (Tm (° C.)) and the weight average molecular weight (Mw) is represented by the following formula ( The tackifier (B) according to [1], which is a copolymer satisfying 1).
Tm <0.027 × Mw + 44.965 (1)
[3] The tackifier (B) according to [1], wherein the copolymer has a weight average molecular weight (Mw) of 1000 to 5000.
[4] A hot melt adhesive composition comprising 100 parts by weight of the base polymer (A) and 10 to 300 parts by weight of the tackifier (B) according to [1].
[5] The hot melt adhesive composition according to [4], wherein the base polymer (A) is a copolymer comprising a vinyl aromatic compound and a conjugated diene compound and / or a hydrogenated product thereof.
本発明の粘着付与剤は、ベースポリマーに添加した場合、他のスチレン系単独又は各共重合体と比べ良好な接着性を維持したまま、同一軟化点で比較すると優れた耐熱クリープ性を発現させることができる。 When added to the base polymer, the tackifier of the present invention exhibits excellent heat-resistant creep resistance when compared at the same softening point while maintaining good adhesion compared to other styrene-based homopolymers or copolymers. be able to.
また、本発明のホットメルト接着剤組成物は、他のスチレン系単独又は各共重合体と比べ良好な接着性を維持したまま、同一軟化点で比較すると優れた耐熱クリープ性を発現する。 In addition, the hot melt adhesive composition of the present invention exhibits excellent heat-resistant creep resistance when compared at the same softening point while maintaining good adhesion as compared with other styrene-based homopolymers or copolymers.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の粘着付与剤（Ｂ）の成分である共重合体は、α−メチルスチレンおよびイソプロペニルトルエンからなる群から選ばれる少なくとも１種のモノマーと、スチレンとの共重合体である。 The copolymer that is a component of the tackifier (B) of the present invention is a copolymer of styrene and at least one monomer selected from the group consisting of α-methylstyrene and isopropenyltoluene.
前記共重合体中の、スチレンから導かれる構成単位の含有率は５０〜８０モル％の範囲であり、好ましくは５５から７０モル％である。スチレンから導かれる構成単位の含有率がこの範囲であれば、ホットメルト接着剤組成物は、接着強度を保ったまま耐熱クリープ性が向上する。 The content of the structural unit derived from styrene in the copolymer is in the range of 50 to 80 mol%, preferably 55 to 70 mol%. When the content of the structural unit derived from styrene is within this range, the hot melt adhesive composition has improved heat-resistant creep resistance while maintaining the adhesive strength.
また、前記共重合体の軟化点（Ｔｍ）（ＪＩＳ Ｋ ２２０７に規定された環球法により測定される軟化点）は７０〜１６０℃、好ましくは８０〜１５０℃である。軟化点がこの範囲であれば、ホットメルト接着剤組成物は、接着強度を保ったまま耐熱クリープ性が向上する。 The copolymer has a softening point (Tm) (softening point measured by the ring and ball method defined in JIS K 2207) of 70 to 160 ° C, preferably 80 to 150 ° C. When the softening point is within this range, the hot melt adhesive composition has improved heat-resistant creep resistance while maintaining adhesive strength.
さらに、前記共重合体は、軟化点（Ｔｍ（℃））と重量平均分子量（Ｍｗ）との関係が下記の式（１）を満足する共重合体が好ましく、この関係式を満足すれば、ホットメルト接着剤組成物は接着強度を保ったまま、さらに耐熱クリープ性が向上する。
Ｔｍ＜０．０２７×Ｍｗ＋４４．９６５ （１）
Further, the copolymer is preferably a copolymer in which the relationship between the softening point (Tm (° C.)) and the weight average molecular weight (Mw) satisfies the following formula (1). The hot melt adhesive composition further improves the heat resistant creep property while maintaining the adhesive strength.
Tm <0.027 × Mw + 44.965 (1)
また、前記共重合体の重量平均分子量（Ｍｗ）は、好ましくは１０００〜５０００である。 Moreover, the weight average molecular weight (Mw) of the copolymer is preferably 1000 to 5000.
本発明で用いられる、α−メチルスチレンおよびイソプロペニルトルエンからなる群から選ばれる少なくとも１種のモノマーとスチレンとの共重合体は、触媒の存在下にモノマーを重合反応させることにより得ることができる。 The copolymer of styrene and at least one monomer selected from the group consisting of α-methylstyrene and isopropenyltoluene used in the present invention can be obtained by polymerizing the monomer in the presence of a catalyst. .
重合に用いられる触媒としては、一般にフリーデルクラフツ触媒として知られているものなどがあげられ、例えば塩化アルミニウム、臭化アルミニウム、ジクロルモノエチルアルミニウム、四塩化チタン、四塩化スズ、三フッ化ホウ素などの各種錯体等をあげることができる。触媒の使用量はモノマーの合計に対して０．０１〜５重量％、好ましくは０．０５〜３重量％である。 Examples of the catalyst used for polymerization include those generally known as Friedel-Crafts catalysts, such as aluminum chloride, aluminum bromide, dichloromonoethylaluminum, titanium tetrachloride, tin tetrachloride, boron trifluoride and the like. And the like. The amount of the catalyst used is 0.01 to 5% by weight, preferably 0.05 to 3% by weight, based on the total amount of monomers.
また重合反応の際に、反応熱の除去や反応混合物の高粘度化の抑制等のために、芳香族炭化水素、脂肪族炭化水素および脂環族炭化水素からなる群から選ばれる少なくとも１種の炭化水素溶媒中で重合反応を行うのが好ましい。好ましい炭化水素溶媒としては、トルエン、キシレン、エチルベンゼン、メシチレン、クメン、シメン等の芳香族炭化水素またはこれらの混合物；またはこれらとペンタン、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素および／またはシクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素との混合物などをあげることができる。これらの反応溶媒の使用量は、反応混合物中のモノマーの初期濃度が１０〜８０重量％となる量が好ましい。 Further, at the time of the polymerization reaction, at least one selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons for the purpose of removing reaction heat and suppressing the increase in viscosity of the reaction mixture. The polymerization reaction is preferably carried out in a hydrocarbon solvent. Preferred hydrocarbon solvents include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, cumene, and cymene, or mixtures thereof; or aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and / or cyclopentane. And mixtures with alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. The amount of these reaction solvents used is preferably such that the initial monomer concentration in the reaction mixture is 10 to 80% by weight.
重合温度は使用するモノマーや触媒の種類および量などにより適宜選択できるが、通常−３０〜＋５０℃である。重合時間は一般には０．５〜５時間程度であり、通常１〜２時間で重合はほとんど完結する。重合様式としては、回分式または連続式のいずれの方式を採用することもできる。また多段重合を行うこともできる。 The polymerization temperature can be appropriately selected depending on the monomer used, the type and amount of the catalyst, etc., but is usually -30 to + 50 ° C. The polymerization time is generally about 0.5 to 5 hours, and the polymerization is usually almost completed within 1 to 2 hours. As the polymerization mode, either a batch system or a continuous system can be adopted. Multistage polymerization can also be performed.
重合終了後は洗浄して触媒残さを除去するのが好ましい。洗浄液としては水酸化カリウム、水酸化ナトリウム等を溶解したアルカリ水溶液；メタノール等のアルコールなどを用いるのが好ましく、特にメタノールによる洗浄脱灰が好ましい。洗浄終了後は未反応モノマー、重合溶媒などを減圧留去して、本発明で用いる重合体または共重合体を得ることができる。 It is preferable to remove the catalyst residue by washing after completion of the polymerization. As the cleaning solution, it is preferable to use an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide or the like is dissolved; alcohol such as methanol or the like, and cleaning deashing with methanol is particularly preferable. After completion of the washing, unreacted monomers, polymerization solvent and the like are distilled off under reduced pressure to obtain a polymer or copolymer used in the present invention.
本発明のホットメルト接着剤組成物に使用されるベースポリマー（Ａ）は、ホットメルト接着剤に通常使用されるスチレンブロックポリマーを用いることができるが、特に制限されず、例えば、以下のものを例示することができる。 As the base polymer (A) used in the hot melt adhesive composition of the present invention, a styrene block polymer usually used in a hot melt adhesive can be used, but is not particularly limited. It can be illustrated.
ビニル芳香族化合物と共役ジエン化合物からなる共重合体、およびその水添物：具体的には、スチレン・ブタジエンランダム共重合体、スチレン・イソプレンランダム共重合体、ブタジエン・ポリスチレンブロック共重合体、ポリスチレン・ポリイソプレンブロック共重合体、ポリスチレン・ポリイソプレン・ポリスチレントリブロック共重合体（ＳＩＳ）、ポリスチレン・ポリブタジエン・ポリスチレントリブロック共重合体（ＳＢＳ）、ポリ（α−メチルスチレン）・ポリブタジエン・ポリ（α−メチルスチレン）トリブロック共重合体、およびこれらの水添物、例えば、ポリスチレン・ポリブタジエン・ポリスチレントリブロック共重合体（ＳＢＳ）の水添物（ＳＥＢＳ）、ポリスチレン・ポリイソプレン・ポリスチレントリブロック共重合体（ＳＩＳ）の水添物（ＳＥＰＳ）等を挙げることができる。 Copolymer composed of vinyl aromatic compound and conjugated diene compound, and hydrogenated product thereof: Specifically, styrene / butadiene random copolymer, styrene / isoprene random copolymer, butadiene / polystyrene block copolymer, polystyrene・ Polyisoprene block copolymer, polystyrene / polyisoprene / polystyrene triblock copolymer (SIS), polystyrene / polybutadiene / polystyrene triblock copolymer (SBS), poly (α-methylstyrene) / polybutadiene / poly (α -Methylstyrene) triblock copolymer, and hydrogenated products thereof such as polystyrene / polybutadiene / polystyrene triblock copolymer (SBS) hydrogenated (SEBS), polystyrene / polyisoprene / polystyrene triblock Examples thereof include a hydrogenated product (SEPS) of a polymer (SIS).
これらの重合体は、市販品として入手することができ、また水添品も市販されている。例えば、カリフレックスＴＲ−１１０１、ＴＲ−１１０７、ＴＲ−４１１３（シェル化学社製）、クレイトンＧ−６５００、Ｇ−６５２１、Ｇ−１６５０、Ｇ−１６５２、Ｇ−１６５７（シェル化学社製）、ソルブレン、水素化ソルブレン（フィリップス社製）等の商品名で上市されているものを例示することができる。 These polymers can be obtained as commercial products, and hydrogenated products are also commercially available. For example, Califlex TR-1101, TR-1107, TR-4113 (manufactured by Shell Chemical Co., Ltd.), Clayton G-6500, G-6521, G-1650, G-1652, G-1657 (manufactured by Shell Chemical Co., Ltd.), sorbulene And those marketed under trade names such as hydrogenated sorbulene (manufactured by Philips).
本発明の組成物において、これらのベースポリマー（Ａ）は１種単独でも２種類以上を組み合わせて使用してもよい。 In the composition of the present invention, these base polymers (A) may be used singly or in combination of two or more.
本発明のホットメルト接着剤組成物において、前記のベースポリマー（Ａ）と粘着付与剤（Ｂ）との配合割合は、ベースポリマー（Ａ）１００重量部に対して、（Ｂ）粘着付与剤１０〜３００重量部の割合であり、ベースポリマー（Ａ）、粘着付与剤（Ｂ）の働きがバランス良く発揮され、さらに、良好な接着性を維持したまま、優れた耐熱クリープ性を発現することができる点で、ベースポリマー（Ａ）１００重量部に対して、粘着付与剤（Ｂ）５０〜２５０重量部割合が好ましい。 In the hot melt adhesive composition of the present invention, the blending ratio of the base polymer (A) and the tackifier (B) is (B) tackifier 10 with respect to 100 parts by weight of the base polymer (A). It is a ratio of ˜300 parts by weight, and the functions of the base polymer (A) and the tackifier (B) are exerted in a well-balanced manner, and furthermore, excellent heat-resistant creep resistance can be expressed while maintaining good adhesiveness. In terms of the ability, the proportion of the tackifier (B) is preferably 50 to 250 parts by weight relative to 100 parts by weight of the base polymer (A).
本発明のホットメルト接着剤組成物は、前記ベースポリマー（Ａ）、粘着付与剤（Ｂ）以外に、必要に応じて、本発明の目的を損なわない範囲において、配合剤、例えば、各種ワックス、軟化剤、安定剤、充填剤、酸化防止剤等を配合することができる。 In addition to the base polymer (A) and the tackifier (B), the hot-melt adhesive composition of the present invention can be formulated in a range that does not impair the object of the present invention, if necessary, for example, various waxes, Softeners, stabilizers, fillers, antioxidants and the like can be blended.
本発明のホットメルト接着剤組成物の調製は、前記ベースポリマー（Ａ）、粘着付与剤（Ｂ）、ならびに必要に応じて、前記各種の成分を、所定の配合割合でブラベンダー等の混合機に供給し、加熱して溶融混合し、これを所望の形状、例えば、粒状、フレーク状、棒状等に成形することによって行うことができる。 The hot melt adhesive composition of the present invention is prepared by mixing the base polymer (A), the tackifier (B), and, if necessary, the various components in a blender such as Brabender at a predetermined blending ratio. , Heated and melt-mixed, and formed into a desired shape, for example, a granular shape, a flake shape, a rod shape, or the like.
本発明のホットメルト接着剤組成物は、これを加熱溶融して、不織布、クラフト紙、アルミ箔、ポリエステルフィルム等の被塗布体に、通常の方法によって塗布してホットメルト接着剤層を形成し、使用に供することができる。 The hot melt adhesive composition of the present invention is heated and melted and applied to a coated body such as a nonwoven fabric, kraft paper, aluminum foil, polyester film, etc. by an ordinary method to form a hot melt adhesive layer. Can be used for use.
以下、本発明の実施例および比較例を挙げ、本発明をより具体的に説明するが、本発明はこれらの実施例により何等制限されるものではない。 EXAMPLES Hereinafter, although the Example and comparative example of this invention are given and this invention is demonstrated more concretely, this invention is not restrict | limited at all by these Examples.
各実施例および比較例における測定方法は以下の通りである。 The measuring method in each example and comparative example is as follows.
分子量：テトラヒドロフランを溶媒としてＧＰＣ法により測定した。 Molecular weight: Measured by GPC method using tetrahydrofuran as a solvent.
軟化点（Ｔｍ）：ＪＩＳ Ｋ ２２０７に規定された環球法により測定した。 Softening point (Tm): Measured by the ring and ball method defined in JIS K 2207.
実施例１
＜粘着付与剤の合成＞
攪拌翼を備えた実容量１２７０ｍｌのオートクレーブに、スチレン、α−メチルスチレンおよび脱水精製したトルエンの混合物（容量比：モノマーの合計／トルエン＝１／１）と、脱水精製したトルエンで１０倍に希釈したボロントリフロライドフェノラート錯体（フェノール１．７倍当量）とを連続的に供給し、反応温度を５℃で重合反応させた。スチレンとα−メチルスチレンとのモル比は６０／４０の割合とし、モノマーおよびトルエンの混合物の供給量は１．０リットル／時間、希釈した触媒の供給量は９０ミリリットル／時間とした。引き続き、この反応混合物を２段目のオートクレーブに移送し、５℃で重合反応を続けさせた後、１段目と２段目のオートクレーブ中での合計滞留時間が２時間になった所で、連続的に反応混合物を排出し、滞留時間の３倍となった所で１リットルの反応混合物を採取し、重合反応を終了させた。重合終了後、採取した反応混合物に１規定のＮａＯＨ水溶液を添加し、触媒残さを脱灰した。更に、得られた反応混合物を多量の水で５回洗浄した後、エバポレーターで溶媒および未反応モノマーを減圧留去して、スチレン・α−メチルスチレン共重合体（１）を得た。得られたスチレン・α−メチルスチレン共重合体（１）は軟化点（Ｔｍ）＝１２４℃、数平均分子量（Ｍｎ）＝１６７０、重量平均分子量（Ｍｗ）＝３３６０、樹脂中のスチレン／αメチルスチレン比は５８／４２モル％であった。結果を表１に示す。
Example 1
<Synthesis of tackifier>
Dilute 10-fold with a mixture of styrene, α-methylstyrene and dehydrated and purified toluene (volume ratio: total monomer / toluene = 1/1) and dehydrated and purified toluene in a 1270 ml autoclave equipped with a stirring blade The boron trifluoride phenolate complex (phenol 1.7 times equivalent) was continuously fed, and the polymerization reaction was carried out at a reaction temperature of 5 ° C. The molar ratio of styrene to α-methylstyrene was 60/40, the supply amount of the monomer and toluene mixture was 1.0 liter / hour, and the supply amount of the diluted catalyst was 90 milliliter / hour. Subsequently, after the reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C., the total residence time in the first and second stage autoclaves was 2 hours. The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was three times the residence time, and the polymerization reaction was terminated. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and the unreacted monomer were distilled off under reduced pressure using an evaporator to obtain a styrene / α-methylstyrene copolymer (1). The obtained styrene / α-methylstyrene copolymer (1) has a softening point (Tm) = 124 ° C., a number average molecular weight (Mn) = 1670, a weight average molecular weight (Mw) = 3360, styrene / α methyl in the resin. The styrene ratio was 58/42 mol%. The results are shown in Table 1.
＜ホットメルト接着剤の合成＞
ベースポリマーとしてスチレン−ブタジエン−スチレン三元ブロック共重合体の水添物（シェル化学製、クレイトンＧ−１６５７）１００重量部に対して粘着付与樹脂としてスチレン・α−メチルスチレン共重合体（１）を２００重量部の割合で配合し、ラボプラストミルを使用して１８０℃で１５分混練しホットメルト接着剤組成物を製造した。
<Synthesis of hot melt adhesive>
Styrene / α-methylstyrene copolymer (1) as a tackifying resin with respect to 100 parts by weight of a hydrogenated product of styrene-butadiene-styrene ternary block copolymer (manufactured by Shell Chemical, Kraton G-1657) as a base polymer Was mixed at a ratio of 200 parts by weight, and kneaded at 180 ° C. for 15 minutes using a Laboplast mill to produce a hot melt adhesive composition.
＜ホットメルト接着剤の性能評価＞
得られたホットメルト接着剤組成物をアルミ箔（５０μｍ）に厚さ２５μｍに塗工し、次いで塗工面同士を張り合わせ、上部バー１２０℃，下部バー１２０℃、３ｋｇ／ｃｍ2 ，１０秒加熱の条件でヒートシールし、さらに２５ｍｍ幅に切断し、接着試料を作成した。この接着試料を、０℃〜８０℃の測定温度下でＴ型剥離試験に供し、接着強度を測定した（引張速度：３００ｍｍ／ｍｉｎ）。また、この接着試料に５００ｇの荷重をかけ、昇温速度２５℃／ｈｒの雰囲気下で荷重の落下温度を測定し、耐熱クリープ性を測定した。接着強度，耐熱クリープ性の測定結果を表２に示した。
<Performance evaluation of hot melt adhesive>
The obtained hot melt adhesive composition was applied to aluminum foil (50 μm) to a thickness of 25 μm, and then the coated surfaces were bonded together, and the upper bar was 120 ° C., the lower bar was 120 ° C., 3 kg / cm 2 , and heated for 10 seconds. It heat-sealed on conditions, and also cut | disconnected to 25 mm width, and created the adhesion | attachment sample. This adhesion sample was subjected to a T-type peel test at a measurement temperature of 0 ° C. to 80 ° C., and the adhesion strength was measured (tensile speed: 300 mm / min). Further, a load of 500 g was applied to this adhesive sample, and the drop temperature of the load was measured in an atmosphere with a temperature rising rate of 25 ° C./hr to measure heat-resistant creep resistance. Table 2 shows the measurement results of adhesive strength and heat-resistant creep resistance.
実施例２
＜粘着付与剤の合成＞
実施例１と同様な装置、方法で触媒の供給量を１０８ミリリットル／時間とすることでスチレン・α−メチルスチレン共重合体（２）を得た。得られたスチレン・α−メチルスチレン共重合体（２）は軟化点（Ｔｍ）＝１３６℃、数平均分子量（Ｍｎ）＝２３００、重量平均分子量（Ｍｗ）＝４７００、樹脂中のスチレン／αメチルスチレン比は５７／４３モル％であった。結果を表１に示す。
Example 2
<Synthesis of tackifier>
A styrene / α-methylstyrene copolymer (2) was obtained by setting the catalyst supply rate to 108 ml / hour using the same apparatus and method as in Example 1. The obtained styrene / α-methylstyrene copolymer (2) has a softening point (Tm) = 136 ° C., a number average molecular weight (Mn) = 2300, a weight average molecular weight (Mw) = 4700, and styrene / α methyl in the resin. The styrene ratio was 57/43 mol%. The results are shown in Table 1.
実施例３
＜粘着付与剤の合成＞
実施例１と同様な装置、方法でスチレンとα−メチルスチレンとのモル比を７０／３０とし、触媒の供給量を８１ミリリットル／時間とすることでスチレン・α−メチルスチレン共重合体（３）を得た。得られたスチレン・α−メチルスチレン共重合体（４）は軟化点（Ｔｍ）＝１２３℃、数平均分子量（Ｍｎ）＝１８４０、重量平均分子量（Ｍｗ）＝３７００、樹脂中のスチレン／αメチルスチレン比は６６／３４モル％であった。結果を表１に示す。
Example 3
<Synthesis of tackifier>
By using the same apparatus and method as in Example 1, the molar ratio of styrene and α-methylstyrene was 70/30, and the supply amount of the catalyst was 81 ml / hour, so that the styrene / α-methylstyrene copolymer (3 ) The obtained styrene / α-methylstyrene copolymer (4) has a softening point (Tm) = 123 ° C., a number average molecular weight (Mn) = 1840, a weight average molecular weight (Mw) = 3700, and styrene / α methyl in the resin. The styrene ratio was 66/34 mol%. The results are shown in Table 1.
実施例４
＜粘着付与剤の合成＞
（１）スチレン・イソプロペニルトルエン共重合体の調製
攪拌翼を備えた実容量１２７０ｍｌのオートクレーブに、スチレン、イソプロペニルトルエンおよび脱水精製したトルエンの混合物（容量比：モノマーの合計／トルエン＝１／１）と、脱水精製したトルエンで１０倍に希釈したボロントリフロライドフェノラート錯体（フェノール１．７倍当量）とを連続的に供給し、反応温度を５℃で重合反応させた。スチレンとイソプロペニルトルエンとのモル比は７０／３０の割合とし、モノマーおよびトルエンの混合物の供給量は１．０リットル／時間、希釈した触媒の供給量は８１ミリリットル／時間とした。引き続き、この反応混合物を２段目のオートクレーブに移送し、５℃で重合反応を続けさせた後、１段目と２段目のオートクレーブ中での合計滞留時間が２時間になった所で、連続的に反応混合物を排出し、滞留時間の３倍となった所で１リットルの反応混合物を採取し、重合反応を終了させた。重合終了後、採取した反応混合物に１規定のＮａＯＨ水溶液を添加し、触媒残さを脱灰した。更に、得られた反応混合物を多量の水で５回洗浄した後、エバポレーターで溶媒および未反応モノマーを減圧留去して、スチレン・イソプロペニルトルエン共重合体（４）を得た。得られたスチレン・イソプロペニルトルエン共重合体（４）は軟化点（Ｔｍ）＝１２２℃、数平均分子量（Ｍｎ）＝１７３０、重量平均分子量（Ｍｗ）＝３４５０、樹脂中のスチレン／イソプロペニルトルエン比は５６／４４モル％であった。結果を表１に示す。
Example 4
<Synthesis of tackifier>
(1) Preparation of Styrene / Isopropenyl Toluene Copolymer A mixture of styrene, isopropenyl toluene and dehydrated and purified toluene (volume ratio: total of monomers / toluene = 1/1) in an autoclave with a real capacity of 1270 ml equipped with a stirring blade. ) And boron trifluoride phenolate complex (phenol 1.7 times equivalent) diluted 10-fold with dehydrated and purified toluene, and polymerized at a reaction temperature of 5 ° C. The molar ratio of styrene to isopropenyltoluene was 70/30, the feed rate of the monomer and toluene mixture was 1.0 liter / hour, and the feed rate of diluted catalyst was 81 milliliter / hour. Subsequently, after the reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C., the total residence time in the first and second stage autoclaves was 2 hours. The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was three times the residence time, and the polymerization reaction was terminated. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and the unreacted monomer were distilled off under reduced pressure using an evaporator to obtain a styrene / isopropenyltoluene copolymer (4). The obtained styrene / isopropenyltoluene copolymer (4) has a softening point (Tm) = 122 ° C., a number average molecular weight (Mn) = 1730, a weight average molecular weight (Mw) = 3450, and styrene / isopropenyltoluene in the resin. The ratio was 56/44 mol%. The results are shown in Table 1.
実施例５
＜粘着付与剤の合成＞
重合温度を１５℃とし、触媒の供給量を１１２ミリリットル／時間とした以外は実施例１と同様な装置、方法でスチレン・α−メチルスチレン共重合体（５）を得た。得られたスチレン・α−メチルスチレン共重合体（５）は軟化点（Ｔｍ）＝９８℃、数平均分子量（Ｍｎ）＝１１６０、重量平均分子量（Ｍｗ）＝２２６０、樹脂中のスチレン／αメチルスチレン比は５９／４１モル％であった。結果を表１に示す。
Example 5
<Synthesis of tackifier>
A styrene / α-methylstyrene copolymer (5) was obtained by the same apparatus and method as in Example 1 except that the polymerization temperature was 15 ° C. and the amount of catalyst supplied was 112 ml / hour. The obtained styrene / α-methylstyrene copolymer (5) has a softening point (Tm) = 98 ° C., a number average molecular weight (Mn) = 1160, a weight average molecular weight (Mw) = 2260, and styrene / α methyl in the resin. The styrene ratio was 59/41 mol%. The results are shown in Table 1.
実施例２〜５の＜ホットメルト接着剤の合成＞
ベースポリマーとしてスチレン−ブタジエン−スチレン三元ブロック共重合体の水添物（シェル化学製、クレイトンＧ−１６５７）１００重量部に対して粘着付与樹脂としてスチレン・α−メチルスチレン共重合体（１）を２００重量部の割合で配合し、ラボプラストミルを使用して１８０℃で１５分混練しホットメルト接着剤組成物を製造した。
<Synthesis of hot melt adhesive> in Examples 2 to 5
Styrene / α-methylstyrene copolymer (1) as a tackifying resin with respect to 100 parts by weight of a hydrogenated product of styrene-butadiene-styrene ternary block copolymer (manufactured by Shell Chemical, Kraton G-1657) as a base polymer Was mixed at a ratio of 200 parts by weight, and kneaded at 180 ° C. for 15 minutes using a Laboplast mill to produce a hot melt adhesive composition.
実施例２〜５の＜ホットメルト接着剤の性能評価＞
実施例１と同様に、得られたホットメルト接着剤組成物をアルミ箔（５０μｍ）に厚さ２５μｍに塗工し、次いで塗工面同士を張り合わせ、上部バー１２０℃，下部バー１２０℃、３ｋｇ／ｃｍ2 ，１０秒加熱の条件でヒートシールし、さらに２５ｍｍ幅に切断し、接着試料を作成した。この接着試料を、０℃〜８０℃の測定温度下でＴ型剥離試験に供し、接着強度を測定した（引張速度：３００ｍｍ／ｍｉｎ）。また、この接着試料に５００ｇの荷重をかけ、昇温速度２５℃／ｈｒの雰囲気下で荷重の落下温度を測定し、耐熱クリープ性を測定した。接着強度，耐熱クリープ性の測定結果を表２に示した。
<Evaluation of Performance of Hot Melt Adhesive> in Examples 2 to 5
In the same manner as in Example 1, the obtained hot melt adhesive composition was applied to an aluminum foil (50 μm) to a thickness of 25 μm, and then the coated surfaces were bonded to each other, and an upper bar 120 ° C., a lower bar 120 ° C., 3 kg / It heat-sealed on the conditions of cm < 2 > and 10 second heating, and also cut | disconnected to 25 mm width, and produced the adhesion | attachment sample. This adhesion sample was subjected to a T-type peel test at a measurement temperature of 0 ° C. to 80 ° C., and the adhesion strength was measured (tensile speed: 300 mm / min). Further, a load of 500 g was applied to this adhesive sample, and the drop temperature of the load was measured in an atmosphere with a temperature rising rate of 25 ° C./hr to measure heat-resistant creep resistance. Table 2 shows the measurement results of adhesive strength and heat-resistant creep resistance.
比較例１
＜粘着付与剤の合成＞
（１）スチレン・α−メチルスチレン共重合体の調製
攪拌翼を備えた実容量１２７０ｍｌのオートクレーブに、スチレン、α−メチルスチレンおよび脱水精製したトルエンの混合物（容量比：モノマーの合計／トルエン＝１／１）と、脱水精製したトルエンで１０倍に希釈したボロントリフロライドフェノラート錯体（フェノール１．７倍当量）とを連続的に供給し、反応温度を５℃で重合反応させた。スチレンとα−メチルスチレンとのモル比は４０／６０の割合とし、モノマーおよびトルエンの混合物の供給量は１．０リットル／時間、希釈した触媒の供給量は９０ミリリットル／時間とした。引き続き、この反応混合物を２段目のオートクレーブに移送し、５℃で重合反応を続けさせた後、１段目と２段目のオートクレーブ中での合計滞留時間が２時間になった所で、連続的に反応混合物を排出し、滞留時間の３倍となった所で１リットルの反応混合物を採取し、重合反応を終了させた。重合終了後、採取した反応混合物に１規定のＮａＯＨ水溶液を添加し、触媒残さを脱灰した。更に、得られた反応混合物を多量の水で５回洗浄した後、エバポレーターで溶媒および未反応モノマーを減圧留去して、スチレン・α−メチルスチレン共重合体（６）を得た。得られたスチレン・α−メチルスチレン共重合体（６）は軟化点（Ｔｍ）＝１２５℃、数平均分子量（Ｍｎ）＝１５８０、重量平均分子量（Ｍｗ）＝２６８０、樹脂中のスチレン／αメチルスチレン比は３７／６３モル％であった。結果を表１に示す。
Comparative Example 1
<Synthesis of tackifier>
(1) Preparation of Styrene / α-Methylstyrene Copolymer A mixture of styrene, α-methylstyrene and dehydrated and purified toluene (volume ratio: total of monomers / toluene = 1) in an autoclave with a real capacity of 1270 ml equipped with a stirring blade. / 1) and boron trifluoride phenolate complex (phenol 1.7 times equivalent) diluted 10-fold with dehydrated and purified toluene were continuously fed, and a polymerization reaction was carried out at a reaction temperature of 5 ° C. The molar ratio of styrene to α-methylstyrene was 40/60, the supply amount of the monomer and toluene mixture was 1.0 liter / hour, and the supply amount of the diluted catalyst was 90 milliliter / hour. Subsequently, after the reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C., the total residence time in the first and second stage autoclaves was 2 hours. The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was three times the residence time, and the polymerization reaction was terminated. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and the unreacted monomer were distilled off under reduced pressure using an evaporator to obtain a styrene / α-methylstyrene copolymer (6). The obtained styrene / α-methylstyrene copolymer (6) has a softening point (Tm) = 125 ° C., a number average molecular weight (Mn) = 1580, a weight average molecular weight (Mw) = 2680, and styrene / α methyl in the resin. The styrene ratio was 37/63 mol%. The results are shown in Table 1.
比較例２
＜粘着付与剤の合成＞
（１）スチレン・α−メチルスチレン共重合体の調製
攪拌翼を備えた実容量１２７０ｍｌのオートクレーブに、スチレン、α−メチルスチレンおよび脱水精製したトルエンの混合物（容量比：モノマーの合計／トルエン＝１／１）と、脱水精製したトルエンで１０倍に希釈したボロントリフロライドフェノラート錯体（フェノール１．７倍当量）とを連続的に供給し、反応温度を５℃で重合反応させた。スチレンとα−メチルスチレンとのモル比は２０／８０の割合とし、モノマーおよびトルエンの混合物の供給量は１．０リットル／時間、希釈した触媒の供給量は９０ミリリットル／時間とした。引き続き、この反応混合物を２段目のオートクレーブに移送し、５℃で重合反応を続けさせた後、１段目と２段目のオートクレーブ中での合計滞留時間が２時間になった所で、連続的に反応混合物を排出し、滞留時間の３倍となった所で１リットルの反応混合物を採取し、重合反応を終了させた。重合終了後、採取した反応混合物に１規定のＮａＯＨ水溶液を添加し、触媒残さを脱灰した。更に、得られた反応混合物を多量の水で５回洗浄した後、エバポレーターで溶媒および未反応モノマーを減圧留去して、スチレン・α−メチルスチレン共重合体（７）を得た。得られたスチレン・α−メチルスチレン共重合体（７）は軟化点（Ｔｍ）＝１２０℃、数平均分子量（Ｍｎ）＝１１００、重量平均分子量（Ｍｗ）＝１９３０、樹脂中のスチレン／αメチルスチレン比は１９／８１モル％であった。結果を表１に示す。
Comparative Example 2
<Synthesis of tackifier>
(1) Preparation of Styrene / α-Methylstyrene Copolymer A mixture of styrene, α-methylstyrene and dehydrated and purified toluene (volume ratio: total of monomers / toluene = 1) in an autoclave with a real capacity of 1270 ml equipped with a stirring blade. / 1) and boron trifluoride phenolate complex (phenol 1.7 times equivalent) diluted 10-fold with dehydrated and purified toluene were continuously fed, and a polymerization reaction was carried out at a reaction temperature of 5 ° C. The molar ratio of styrene to α-methylstyrene was 20/80, the supply amount of the monomer and toluene mixture was 1.0 liter / hour, and the supply amount of the diluted catalyst was 90 milliliter / hour. Subsequently, after the reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C., the total residence time in the first and second stage autoclaves was 2 hours. The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was three times the residence time, and the polymerization reaction was terminated. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and the unreacted monomer were distilled off under reduced pressure using an evaporator to obtain a styrene / α-methylstyrene copolymer (7). The obtained styrene / α-methylstyrene copolymer (7) has a softening point (Tm) = 120 ° C., a number average molecular weight (Mn) = 1100, a weight average molecular weight (Mw) = 1930, and styrene / α methyl in the resin. The styrene ratio was 19/81 mol%. The results are shown in Table 1.
比較例３
＜粘着付与剤の合成＞
（１）スチレン・α−メチルスチレン共重合体の調製
攪拌翼を備えた実容量１２７０ｍｌのオートクレーブに、スチレン、α−メチルスチレンおよび脱水精製したトルエンの混合物（容量比：モノマーの合計／トルエン＝１／１）と、脱水精製したトルエンで１０倍に希釈したボロントリフロライドフェノラート錯体（フェノール１．７倍当量）とを連続的に供給し、反応温度を５℃で重合反応させた。スチレンとα−メチルスチレンとのモル比は８５／１５の割合とし、モノマーおよびトルエンの混合物の供給量は１．０リットル／時間、希釈した触媒の供給量は８１ミリリットル／時間とした。引き続き、この反応混合物を２段目のオートクレーブに移送し、５℃で重合反応を続けさせた後、１段目と２段目のオートクレーブ中での合計滞留時間が２時間になった所で、連続的に反応混合物を排出し、滞留時間の３倍となった所で１リットルの反応混合物を採取し、重合反応を終了させた。重合終了後、採取した反応混合物に１規定のＮａＯＨ水溶液を添加し、触媒残さを脱灰した。更に、得られた反応混合物を多量の水で５回洗浄した後、エバポレーターで溶媒および未反応モノマーを減圧留去して、スチレン・α−メチルスチレン共重合体（８）を得た。得られたスチレン・α−メチルスチレン共重合体（８）は軟化点（Ｔｍ）＝１２０℃、数平均分子量（Ｍｎ）＝１８４０、重量平均分子量（Ｍｗ）＝３８６０、樹脂中のスチレン／αメチルスチレン比は８２／１８モル％であった。結果を表１に示す。
Comparative Example 3
<Synthesis of tackifier>
(1) Preparation of Styrene / α-Methylstyrene Copolymer A mixture of styrene, α-methylstyrene and dehydrated and purified toluene (volume ratio: total of monomers / toluene = 1) in an autoclave with a real capacity of 1270 ml equipped with a stirring blade. / 1) and boron trifluoride phenolate complex (phenol 1.7 times equivalent) diluted 10-fold with dehydrated and purified toluene were continuously fed, and a polymerization reaction was carried out at a reaction temperature of 5 ° C. The molar ratio of styrene to α-methylstyrene was 85/15, the supply amount of the monomer and toluene mixture was 1.0 liter / hour, and the supply amount of the diluted catalyst was 81 milliliter / hour. Subsequently, after the reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C., the total residence time in the first and second stage autoclaves was 2 hours. The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was three times the residence time, and the polymerization reaction was terminated. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and the unreacted monomer were distilled off under reduced pressure using an evaporator to obtain a styrene / α-methylstyrene copolymer (8). The obtained styrene / α-methylstyrene copolymer (8) has a softening point (Tm) = 120 ° C., a number average molecular weight (Mn) = 1840, a weight average molecular weight (Mw) = 3860, and styrene / α methyl in the resin. The styrene ratio was 82/18 mol%. The results are shown in Table 1.
比較例４
＜粘着付与剤の合成＞
（１）イソプロペニルトルエン・α−メチルスチレン共重合体の調製
攪拌翼を備えた実容量１２７０ｍｌのオートクレーブに、イソプロペニルトルエン、α−メチルスチレンおよび脱水精製したトルエンの混合物（容量比：モノマーの合計／トルエン＝１／１）と、脱水精製したトルエンで１０倍に希釈したボロントリフロライドフェノラート錯体（フェノール１．７倍当量）とを連続的に供給し、反応温度を５℃で重合反応させた。イソプロペニルトルエンとα−メチルスチレンとのモル比は５０／５０の割合とし、モノマーおよびトルエンの混合物の供給量は１．０リットル／時間、希釈した触媒の供給量は９０ミリリットル／時間とした。引き続き、この反応混合物を２段目のオートクレーブに移送し、５℃で重合反応を続けさせた後、１段目と２段目のオートクレーブ中での合計滞留時間が２時間になった所で、連続的に反応混合物を排出し、滞留時間の３倍となった所で１リットルの反応混合物を採取し、重合反応を終了させた。重合終了後、採取した反応混合物に１規定のＮａＯＨ水溶液を添加し、触媒残さを脱灰した。更に、得られた反応混合物を多量の水で５回洗浄した後、エバポレーターで溶媒および未反応モノマーを減圧留去して、イソプロペニルトルエン・α−メチルスチレン共重合体（９）を得た。得られたイソプロペニルトルエン・α−メチルスチレン共重合体（９）は軟化点（Ｔｍ）＝１２２℃、数平均分子量（Ｍｎ）＝１２１０、重量平均分子量（Ｍｗ）＝２０６０、樹脂中のイソプロペニルトルエン／αメチルスチレン比は５１／４９モル％であった。結果を表１に示す。
Comparative Example 4
<Synthesis of tackifier>
(1) Preparation of isopropenyltoluene / α-methylstyrene copolymer A mixture of isopropenyltoluene, α-methylstyrene and dehydrated and purified toluene (volume ratio: total of monomers) in an autoclave with a real capacity of 1270 ml equipped with a stirring blade / Toluene = 1/1) and boron trifluoride phenolate complex (1.7 equivalents of phenol) diluted 10-fold with dehydrated and purified toluene, and polymerized at a reaction temperature of 5 ° C. I let you. The molar ratio of isopropenyltoluene and α-methylstyrene was 50/50, the feed rate of the monomer and toluene mixture was 1.0 liter / hour, and the feed rate of the diluted catalyst was 90 milliliter / hour. Subsequently, after the reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C., the total residence time in the first and second stage autoclaves was 2 hours. The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was three times the residence time, and the polymerization reaction was terminated. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and unreacted monomers were distilled off under reduced pressure using an evaporator to obtain an isopropenyltoluene / α-methylstyrene copolymer (9). The resulting isopropenyltoluene / α-methylstyrene copolymer (9) has a softening point (Tm) = 122 ° C., a number average molecular weight (Mn) = 1210, a weight average molecular weight (Mw) = 2060, and isopropenyl in the resin. The toluene / α-methylstyrene ratio was 51/49 mol%. The results are shown in Table 1.
比較例５
＜粘着付与剤の合成＞
（１）イソプロペニルトルエン単独重合体の調製
攪拌翼を備えた実容量１２７０ｍｌのオートクレーブに、イソプロペニルトルエンおよび脱水精製したトルエンの混合物（容量比：１／１）と、脱水精製したトルエンで１０倍に希釈したボロントリフロライドフェノラート錯体（フェノール１．７倍当量）とを連続的に供給し、反応温度を５℃で重合反応させた。イソプロペニルトルエンおよびトルエンの混合物の供給量は１．０リットル／時間、希釈した触媒の供給量は９０ミリリットル／時間とした。引き続き、この反応混合物を２段目のオートクレーブに移送し、５℃で重合反応を続けさせた後、１段目と２段目のオートクレーブ中での合計滞留時間が２時間になった所で、連続的に反応混合物を排出し、滞留時間の３倍となった所で１リットルの反応混合物を採取し、重合反応を終了させた。重合終了後、採取した反応混合物に１規定のＮａＯＨ水溶液を添加し、触媒残さを脱灰した。更に、得られた反応混合物を多量の水で５回洗浄した後、エバポレーターで溶媒および未反応モノマーを減圧留去して、イソプロペニルトルエン単独重合体（１０）を得た。得られたイソプロペニルトルエン単独重合体（１０）は軟化点（Ｔｍ）＝１２０℃、数平均分子量（Ｍｎ）＝１０６０、重量平均分子量（Ｍｗ）＝１６００であった。結果を表１に示す。
Comparative Example 5
<Synthesis of tackifier>
(1) Preparation of isopropenyltoluene homopolymer 10 times with a mixture of isopropenyltoluene and dehydrated and purified toluene (volume ratio: 1/1) and dehydrated and purified toluene in a 1270 ml autoclave equipped with a stirring blade A boron trifluoride phenolate complex (1.7-fold equivalent of phenol) diluted to 1 was continuously fed to cause a polymerization reaction at a reaction temperature of 5 ° C. The feed rate of the mixture of isopropenyltoluene and toluene was 1.0 liter / hour, and the feed rate of the diluted catalyst was 90 ml / hour. Subsequently, after the reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C., the total residence time in the first and second stage autoclaves was 2 hours. The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was three times the residence time, and the polymerization reaction was terminated. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and unreacted monomers were distilled off under reduced pressure using an evaporator to obtain an isopropenyltoluene homopolymer (10). The obtained isopropenyl toluene homopolymer (10) had a softening point (Tm) = 120 ° C., a number average molecular weight (Mn) = 1060, and a weight average molecular weight (Mw) = 1600. The results are shown in Table 1.
比較例６
＜粘着付与剤の合成＞
（１）α−メチルスチレン単独重合体の調製
攪拌翼を備えた実容量１２７０ｍｌのオートクレーブに、α−メチルスチレンおよび脱水精製したトルエンの混合物（容量比：１／１）と、脱水精製したトルエンで１０倍に希釈したボロントリフロライドフェノラート錯体（フェノール１．７倍当量）とを連続的に供給し、反応温度を５℃で重合反応させた。α−メチルスチレンおよびトルエンの混合物の供給量は１．０リットル／時間、希釈した触媒の供給量は９０ミリリットル／時間とした。引き続き、この反応混合物を２段目のオートクレーブに移送し、５℃で重合反応を続けさせた後、１段目と２段目のオートクレーブ中での合計滞留時間が２時間になった所で、連続的に反応混合物を排出し、滞留時間の３倍となった所で１リットルの反応混合物を採取し、重合反応を終了させた。重合終了後、採取した反応混合物に１規定のＮａＯＨ水溶液を添加し、触媒残さを脱灰した。更に、得られた反応混合物を多量の水で５回洗浄した後、エバポレーターで溶媒および未反応モノマーを減圧留去して、α−メチルスチレン単独重合体（１１）を得た。得られたα−メチルスチレン単独重合体（１１）は軟化点（Ｔｍ）＝１２０℃、数平均分子量（Ｍｎ）＝１３００、重量平均分子量（Ｍｗ）＝２３２０であった。結果を表１に示す。
Comparative Example 6
<Synthesis of tackifier>
(1) Preparation of α-methylstyrene homopolymer In a 1270 ml autoclave equipped with a stirring blade, a mixture of α-methylstyrene and dehydrated and purified toluene (volume ratio: 1/1) and dehydrated and purified toluene Boron trifluoride phenolate complex diluted 10-fold (1.7 equivalents of phenol) was continuously supplied, and a polymerization reaction was carried out at a reaction temperature of 5 ° C. The supply amount of the mixture of α-methylstyrene and toluene was 1.0 liter / hour, and the supply amount of the diluted catalyst was 90 milliliter / hour. Subsequently, after the reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C., the total residence time in the first and second stage autoclaves was 2 hours. The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was three times the residence time, and the polymerization reaction was terminated. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and the unreacted monomer were distilled off under reduced pressure using an evaporator to obtain an α-methylstyrene homopolymer (11). The obtained α-methylstyrene homopolymer (11) had a softening point (Tm) = 120 ° C., a number average molecular weight (Mn) = 1300, and a weight average molecular weight (Mw) = 2320. The results are shown in Table 1.
比較例７
＜粘着付与剤の合成＞
（１）スチレン・α−メチルスチレン共重合体の調製
攪拌翼を備えた実容量１２７０ｍｌのオートクレーブに、スチレン、α−メチルスチレンおよび脱水精製したトルエンの混合物（容量比：モノマーの合計／トルエン＝１／１）と、脱水精製したトルエンで１０倍に希釈したボロントリフロライドフェノラート錯体（フェノール１．７倍当量）とを連続的に供給し、反応温度を５℃で重合反応させた。スチレンとα−メチルスチレンとのモル比は４０／６０の割合とし、モノマーおよびトルエンの混合物の供給量は１．０リットル／時間、希釈した触媒の供給量は１１７ミリリットル／時間とした。引き続き、この反応混合物を２段目のオートクレーブに移送し、５℃で重合反応を続けさせた後、１段目と２段目のオートクレーブ中での合計滞留時間が２時間になった所で、連続的に反応混合物を排出し、滞留時間の３倍となった所で１リットルの反応混合物を採取し、重合反応を終了させた。重合終了後、採取した反応混合物に１規定のＮａＯＨ水溶液を添加し、触媒残さを脱灰した。更に、得られた反応混合物を多量の水で５回洗浄した後、エバポレーターで溶媒および未反応モノマーを減圧留去して、スチレン・α−メチルスチレン共重合体（１２）を得た。得られたスチレン・α−メチルスチレン共重合体（１２）は軟化点（Ｔｍ）＝９８℃、数平均分子量（Ｍｎ）＝９６０、重量平均分子量（Ｍｗ）＝１８１０、樹脂中のスチレン／αメチルスチレン比は３９／６１モル％であった。結果を表１に示す。
Comparative Example 7
<Synthesis of tackifier>
(1) Preparation of Styrene / α-Methylstyrene Copolymer A mixture of styrene, α-methylstyrene and dehydrated and purified toluene (volume ratio: total of monomers / toluene = 1) in an autoclave with a real capacity of 1270 ml equipped with a stirring blade. / 1) and boron trifluoride phenolate complex (phenol 1.7 times equivalent) diluted 10-fold with dehydrated and purified toluene were continuously fed, and a polymerization reaction was carried out at a reaction temperature of 5 ° C. The molar ratio of styrene to α-methylstyrene was 40/60, the supply amount of the monomer and toluene mixture was 1.0 liter / hour, and the supply amount of the diluted catalyst was 117 milliliter / hour. Subsequently, after the reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C., the total residence time in the first and second stage autoclaves was 2 hours. The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was three times the residence time, and the polymerization reaction was terminated. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and the unreacted monomer were distilled off under reduced pressure using an evaporator to obtain a styrene / α-methylstyrene copolymer (12). The obtained styrene / α-methylstyrene copolymer (12) has a softening point (Tm) = 98 ° C., a number average molecular weight (Mn) = 960, a weight average molecular weight (Mw) = 1810, and styrene / α-methyl in the resin. The styrene ratio was 39/61 mol%. The results are shown in Table 1.
比較例１〜７の＜ホットメルト接着剤の合成＞
実施例１と同様に、ベースポリマーとしてスチレン−ブタジエン−スチレン三元ブロック共重合体の水添物（シェル化学製、クレイトンＧ−１６５７）１００重量部に対して粘着付与樹脂としてスチレン・α−メチルスチレン共重合体（１）を２００重量部の割合で配合し、ラボプラストミルを使用して１８０℃で１５分混練しホットメルト接着剤組成物を製造した。
<Synthesis of hot melt adhesive> in Comparative Examples 1 to 7
In the same manner as in Example 1, styrene / α-methyl as a tackifying resin with respect to 100 parts by weight of a hydrogenated product of styrene-butadiene-styrene ternary block copolymer (manufactured by Shell Chemical, Kraton G-1657) as a base polymer. The styrene copolymer (1) was blended at a ratio of 200 parts by weight, and kneaded at 180 ° C. for 15 minutes using a Laboplast mill to produce a hot melt adhesive composition.
比較例１〜７の＜ホットメルト接着剤の性能評価＞
実施例１と同様に、得られたホットメルト接着剤組成物をアルミ箔（５０μｍ）に厚さ２５μｍに塗工し、次いで塗工面同士を張り合わせ、上部バー１２０℃，下部バー１２０℃、３ｋｇ／ｃｍ2 ，１０秒加熱の条件でヒートシールし、さらに２５ｍｍ幅に切断し、接着試料を作成した。この接着試料を、０℃〜８０℃の測定温度下でＴ型剥離試験に供し、接着強度を測定した（引張速度：３００ｍｍ／ｍｉｎ）。また、この接着試料に５００ｇの荷重をかけ、昇温速度２５℃／ｈｒの雰囲気下で荷重の落下温度を測定し、耐熱クリープ性を測定した。接着強度，耐熱クリープ性の測定結果を表２に示した。
<Performance evaluation of hot melt adhesives> in Comparative Examples 1 to 7
In the same manner as in Example 1, the obtained hot melt adhesive composition was applied to an aluminum foil (50 μm) to a thickness of 25 μm, and then the coated surfaces were bonded to each other, and an upper bar 120 ° C., a lower bar 120 ° C., 3 kg / It heat-sealed on the conditions of cm < 2 > and 10 second heating, and also cut | disconnected to 25 mm width, and produced the adhesion | attachment sample. This adhesion sample was subjected to a T-type peel test at a measurement temperature of 0 ° C. to 80 ° C., and the adhesion strength was measured (tensile speed: 300 mm / min). Further, a load of 500 g was applied to this adhesive sample, and the drop temperature of the load was measured in an atmosphere with a temperature rising rate of 25 ° C./hr to measure heat-resistant creep resistance. Table 2 shows the measurement results of adhesive strength and heat-resistant creep resistance.
本発明の粘着付与剤は、ベースポリマーに添加した場合、他のスチレン系単独又は各共重合体と比べ良好な接着性を維持したまま、優れた耐熱クリープ性を発現させることができるので、産業上有用である。
When added to the base polymer, the tackifier of the present invention can exhibit excellent heat-resistant creep resistance while maintaining good adhesiveness compared to other styrene-based homopolymers or copolymers. It is useful above.
Claims (5)
（ｉ）α−メチルスチレンおよびイソプロペニルトルエンからなる群から選ばれる少なくとも１種のモノマーと、スチレンとの共重合体であり、
（ｉｉ）スチレンから導かれる構成単位の含有率が５０〜８０モル％であり、
（ｉｉｉ）軟化点（Ｔｍ）が７０〜１６０℃である共重合体 The tackifier (B) containing the copolymer prescribed | regulated by following (i)-(iii).
(I) a copolymer of at least one monomer selected from the group consisting of α-methylstyrene and isopropenyltoluene and styrene;
(Ii) The content of the structural unit derived from styrene is 50 to 80 mol%,
(Iii) A copolymer having a softening point (Tm) of 70 to 160 ° C.
Ｔｍ＜０．０２７×Ｍｗ＋４４．９６５ （１） The tackifier (B) according to claim 1, wherein the copolymer is a copolymer in which a relationship between a softening point (Tm (° C)) and a weight average molecular weight (Mw) satisfies the following formula (1). ).
Tm <0.027 × Mw + 44.965 (1)
The hot melt adhesive composition according to claim 4, wherein the base polymer (A) is a copolymer comprising a vinyl aromatic compound and a conjugated diene compound and / or a hydrogenated product thereof.
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| JP2010235807A (en) * | 2009-03-31 | 2010-10-21 | Bridgestone Corp | Method for producing aromatic vinyl compound polymer, aromatic vinyl compound polymer produced by the production method, and rubber composition and tire prepared using the aromatic vinyl compound polymer |
| CN102959032A (en) * | 2010-06-29 | 2013-03-06 | 汉高公司 | Hot melt adhesive |
| WO2019203101A1 (en) * | 2018-04-18 | 2019-10-24 | 三井化学株式会社 | Tackifier and hot melt adhesive composition |
| KR102070586B1 (en) * | 2019-06-27 | 2020-01-29 | 주식회사 제이엠이엔씨 | complex sheet for waterproofing and waterproofing method using the same |
| JP2020117661A (en) * | 2019-01-28 | 2020-08-06 | 旭化学合成株式会社 | Hot-melt composition and sealing material |
| JP7368675B1 (en) * | 2023-02-01 | 2023-10-25 | 東洋インキＳｃホールディングス株式会社 | Alkaline removable hot melt adhesive and container |
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| WO2019203101A1 (en) * | 2018-04-18 | 2019-10-24 | 三井化学株式会社 | Tackifier and hot melt adhesive composition |
| CN111936591A (en) * | 2018-04-18 | 2020-11-13 | 三井化学株式会社 | Tackifier and hot-melt adhesive composition |
| JPWO2019203101A1 (en) * | 2018-04-18 | 2021-01-14 | 三井化学株式会社 | Adhesive and hot melt adhesive compositions |
| CN111936591B (en) * | 2018-04-18 | 2021-08-27 | 三井化学株式会社 | Tackifier and hot-melt adhesive composition |
| JP2020117661A (en) * | 2019-01-28 | 2020-08-06 | 旭化学合成株式会社 | Hot-melt composition and sealing material |
| JP7289502B2 (en) | 2019-01-28 | 2023-06-12 | 旭化学合成株式会社 | Hot melt composition and sealing material |
| KR102070586B1 (en) * | 2019-06-27 | 2020-01-29 | 주식회사 제이엠이엔씨 | complex sheet for waterproofing and waterproofing method using the same |
| JP7368675B1 (en) * | 2023-02-01 | 2023-10-25 | 東洋インキＳｃホールディングス株式会社 | Alkaline removable hot melt adhesive and container |
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