JP2009084421A - Tackifier, tackifier for medical plaster, self-adhesive or self-adhesive composition, and self-adhesive for medical plaster - Google Patents
Tackifier, tackifier for medical plaster, self-adhesive or self-adhesive composition, and self-adhesive for medical plaster Download PDFInfo
- Publication number
- JP2009084421A JP2009084421A JP2007255577A JP2007255577A JP2009084421A JP 2009084421 A JP2009084421 A JP 2009084421A JP 2007255577 A JP2007255577 A JP 2007255577A JP 2007255577 A JP2007255577 A JP 2007255577A JP 2009084421 A JP2009084421 A JP 2009084421A
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- Prior art keywords
- acid
- tackifier
- adhesive
- weight
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Materials For Medical Uses (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本発明は、粘着付与剤、医療用貼布剤用粘着付与剤、粘着剤または接着剤組成物および医療用貼付剤用粘着剤に関する。 The present invention relates to a tackifier, a tackifier for a medical patch, a pressure-sensitive adhesive or an adhesive composition, and a pressure-sensitive adhesive for a medical patch.
従来、ロジン類とアルコールの反応生成物、いわゆるロジンエステルは、粘・接着剤用の粘着付与樹脂、ゴム類や各種プラスチック、ポリマー類の改質剤、チューイングガム基材などの各種用途に使用されている。しかし、一般にロジンエステルは色調が悪く、黄色ないしは黄褐色に着色している。また加熱や日光照射による酸化に起因する色調の悪化に対する安定性（以下、安定性という）に欠けており、他にも臭気等の点で満足し得るものではなかった。 Conventionally, reaction products of rosins and alcohol, so-called rosin esters, have been used for various applications such as tackifier resins for adhesives and adhesives, rubbers and various plastics, polymer modifiers, chewing gum bases, etc. Yes. However, rosin esters generally have a poor color tone and are colored yellow or tan. Further, it lacks stability (hereinafter referred to as stability) against deterioration in color tone caused by oxidation due to heating or irradiation with sunlight, and is not satisfactory in terms of odor and the like.
ロジンエステルを合成する際に用いるロジン類として、安定性に優れた不均化ロジンや水素化ロジンを使用することで上記欠点をある程度解決したロジンエステルが市販されているが、これらの色調、安定性は満足し得るものではない。 As rosins used when synthesizing rosin esters, rosin esters that have solved the above disadvantages to some extent by using disproportionated rosin or hydrogenated rosin with excellent stability are commercially available. Sex is not satisfactory.
安定性に優れたロジンエステルの製造法として、蒸留精製した不均化ロジンとアルコールをエステル化する方法が提案されている。（特許文献１参照）しかし、この方法で得られるロジンエステルは従来のロジンエステルと比べると安定性が比較的良好であるが、満足し得るものではなく、さらに、エステル化工程における加熱時にロジンエステルが着色するといった問題がある。 As a method for producing a rosin ester having excellent stability, a method for esterifying a disproportionated rosin obtained by distillation purification and an alcohol has been proposed. However, the rosin ester obtained by this method has relatively good stability as compared with the conventional rosin ester, but is not satisfactory, and further, the rosin ester is heated during the esterification step. There is a problem of coloring.
また、安定性、かつ色調に優れたロジンエステルの製造方法として、蒸留精製した不均化ロジン化合物とアルコールを、不均化能力と淡色化能力を併せ持つ特定の有機硫黄化合物の存在下においてエステル化する方法も提案されている（特許文献２参照）。しかし、当該方法で得られるロジンエステルも安定性の点で未だ改善の余地があり、しかも加熱時に有機硫黄化合物に起因する硫黄臭がするといった問題もあった。 In addition, as a method for producing rosin esters with excellent stability and color, esterification of disproportionated rosin compounds and alcohols that have been purified by distillation in the presence of specific organosulfur compounds that have both disproportionation and lightening ability. There has also been proposed a method (see Patent Document 2). However, the rosin ester obtained by this method still has room for improvement in terms of stability, and there is also a problem that a sulfur odor due to the organic sulfur compound is produced during heating.
ところで、色調を改良することを目的として、ロジンまたは不均化ロジンを精製した後にエステル化、および水素化することにより無色ロジンエステルの誘導体の製造方法が提案されている（特許文献３参照）が、具体的なロジンの水素化率の記載なく、各種のべースポリマーへの適合性や、水素化率の最適範囲などについては全く記載されていない。 By the way, for the purpose of improving the color tone, a method for producing a colorless rosin ester derivative has been proposed by purifying rosin or disproportionated rosin, followed by esterification and hydrogenation (see Patent Document 3). No specific rosin hydrogenation rate is described, and no compatibility with various base polymers, optimal range of hydrogenation rate, etc. are described.
さらに、不均化ロジンを精製したのちにエステル化し、脱水素する淡色ロジンエステルの製造方法も提案されている（特許文献４参照）が、水素化を経ていないためか、その色調などは水素化工程を経たロジンエステルに比較して劣っていた。 Furthermore, although a method for producing a light-colored rosin ester that is esterified and then dehydrogenated after purification of the disproportionated rosin has been proposed (see Patent Document 4), the color tone or the like may be due to hydrogenation. It was inferior compared with the rosin ester which passed the process.
これらの特許文献には従来の既存技術（ロジンの水素化、精製、不均化などを組み合わせて無色、淡色なロジンおよびロジンエステルなどを製造する方法）においては、明確な技術開示がなされているものの、粘着付与樹脂として使用する場合の組成面からの検討は行なわれておらず、また、それらの利用、特に医療用貼布剤用粘着付与剤への応用についての検討はなされていなかった。 In these patent documents, a clear technical disclosure is made in the conventional existing technology (a method for producing colorless, light-colored rosin and rosin ester by combining hydrogenation, purification and disproportionation of rosin). However, no studies have been made on the composition when used as a tackifier resin, and their use, particularly application to a tackifier for medical patch, has not been studied.
本発明は、淡色で、臭気がなく、安定性に優れ、粘着剤等に用いられる各種ベースポリマーとの相溶性に優れる粘着付与剤、特に医療用貼付剤用粘着剤に適した粘着付与剤を提供することを目的とする。また、粘着特性等に優れた粘着剤または接着剤、特に医療用貼布剤として好適な粘着剤または接着剤を提供することを目的とする。 The present invention provides a tackifier that is light-colored, has no odor, excellent stability, and excellent compatibility with various base polymers used for pressure-sensitive adhesives, particularly a pressure-sensitive adhesive suitable for pressure-sensitive adhesives for medical patches. The purpose is to provide. Another object of the present invention is to provide a pressure-sensitive adhesive or adhesive excellent in pressure-sensitive adhesive properties, particularly a pressure-sensitive adhesive or adhesive suitable as a medical patch.
本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、精製ロジン類とアルコール類を反応させて得られるある特定の分光学的性質を有する反応生成物を用いることにより前記課題を解決することができることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors solved the above problems by using a reaction product having a specific spectroscopic property obtained by reacting purified rosins with alcohols. The present invention has been completed.
すなわち本発明は、精製ロジン類とアルコール類を反応させて得られる、ＵＶ吸光光度法の２７６ｎｍにおける吸光度Ａ（１％ １ｃｍ）が４．５以上１９．５未満であって、１Ｈ−ＮＭＲにおける５．４〜６．６ｐｐｍにピークを有さない反応生成物を含有することを特徴とする粘着付与剤；前記粘着付与剤を含有する医療用貼付剤用粘着付与剤；前記粘着付与剤を含有する粘着剤または接着剤組成物；前記医療用貼付剤用粘着付与剤を含有する医療用貼付剤用粘着剤に関する。 That is, in the present invention, the absorbance A (1% 1 cm) at 276 nm obtained by reacting purified rosins with alcohols is 4.5 or more and less than 19.5, and in 1 H-NMR A tackifier comprising a reaction product having no peak at 5.4 to 6.6 ppm; a tackifier for a medical patch containing the tackifier; and containing the tackifier The present invention relates to a pressure-sensitive adhesive or adhesive composition; a pressure-sensitive adhesive for medical patches containing the above-described tackifier for medical patches.
本発明の粘着付与剤は、淡色で臭気がなく良好な安定性を示すうえ、粘着剤等に用いられる各種ベースポリマーとの相溶性に優れる。そのため、特に医療用貼付剤用粘着付与剤として用いることができる。また、本発明の粘着付与剤を用いて得られる粘着剤または接着剤は良好な粘・接着特性を発揮することができるため、粘着テープまたは接着テープの製造に有用である。 The tackifier of the present invention is light in color, has no odor, exhibits good stability, and is excellent in compatibility with various base polymers used in pressure-sensitive adhesives. Therefore, it can be used as a tackifier for medical patches. Moreover, since the adhesive or adhesive obtained by using the tackifier of the present invention can exhibit good adhesive / adhesive properties, it is useful for the production of adhesive tapes or adhesive tapes.
本発明の粘着付与剤は、精製ロジン類とアルコール類を反応させることにより得られ、ＵＶ吸光光度法の２７６ｎｍにおける吸光度Ａ（１％ １ｃｍ）が４．５以上１９．５未満であって、１Ｈ−ＮＭＲにおける５．４〜６．６ｐｐｍにピークを有さない反応生成物を含有することを特徴とする。ＵＶ吸光光度法の２７６ｎｍにおける吸光度Ａ（１％ １ｃｍ）が４．５より小さくなると、粘着剤等に用いられるアクリルポリマー等との相溶性が劣るため好ましくない。また、ＵＶ吸光光度法の２７６ｎｍにおける吸光度Ａ（１％ １ｃｍ）が１９．５以上となると、安定性が劣るため、またブロックゴム系粘着剤に使用した場合は、粘着性能（保持力）の低下を招き好ましくない。また、１Ｈ−ＮＭＲにおける５．４〜６．６ｐｐｍの領域にピークを有するということは、不安定な二重結合（非芳香族）、すなわち酸化を受けやすいようなオレフィン性二重結合（４置換オレフィンを除く）を有することを意味し安定性が悪くなるため好ましくない。また、不安定な二重結合を有するロジンは、酸化を受け容易に感作性が高いといわれる酸化ロジンになるおそれがあることから、オレフィン性二重結合の存在をなくすことが好ましい。 Tackifiers of the present invention is obtained by reacting the purified rosin and alcohol, the absorbance A at 276nm in UV absorption spectroscopy (1% 1 cm) is less than 19.5 4.5 or more, 1 It contains a reaction product having no peak at 5.4 to 6.6 ppm in H-NMR. When the absorbance A (1% 1 cm) at 276 nm in the UV absorptiometry is less than 4.5, it is not preferable because the compatibility with an acrylic polymer or the like used for an adhesive or the like is poor. In addition, when the absorbance A (1% 1 cm) at 276 nm of UV absorption spectrophotometry is 19.5 or more, the stability is inferior, and when used as a block rubber adhesive, the adhesive performance (holding power) decreases. Is undesirable. In addition, having a peak in the region of 5.4 to 6.6 ppm in 1 H-NMR means that it is an unstable double bond (non-aromatic), that is, an olefinic double bond that is susceptible to oxidation (4 (Excluding substituted olefins). Moreover, since the rosin having an unstable double bond is likely to be oxidized rosin that is easily oxidized and is said to have high sensitization, it is preferable to eliminate the presence of an olefinic double bond.
本発明の粘着付与剤の製造に用いられる精製ロジン類とは、ロジン類を後述する方法によって精製したものである。当該精製ロジン類を用いない場合には、色調、臭気、安定性等諸性能を満足した本発明の粘着付与剤は得られない。 The purified rosins used in the production of the tackifier of the present invention are those obtained by purifying rosins by the method described later. When the purified rosin is not used, the tackifier of the present invention that satisfies various performances such as color tone, odor, and stability cannot be obtained.
ロジン類としては、ガムロジン、ウッドロジン、トール油ロジンおよびこれらの、水素化物、不均化物などが挙げられる。一般に、ロジン類には、アビエチン酸、パラストリン酸、ネオアビエチン酸、ピマール酸、イソピマール酸、デヒドロアビエチン酸、テトラヒドロアビエチン酸、ジヒドロアビエチン酸等の樹脂酸が含まれている。 Examples of rosins include gum rosin, wood rosin, tall oil rosin, and hydrides and disproportionates thereof. In general, rosins include resin acids such as abietic acid, parastrinic acid, neoabietic acid, pimaric acid, isopimaric acid, dehydroabietic acid, tetrahydroabietic acid, and dihydroabietic acid.
精製ロジン類は、未精製のロジン類から樹脂酸の過酸化物から生起したと考えられる高分子量物や、未精製のロジン類に含まれていた不ケン化物を除去することにより得られる。精製方法は特に限定されず、公知の各種精製方法を適宜選択できる。具体的には蒸留、再結晶、抽出等の操作が挙げられる。工業的には蒸留による精製が好ましい。蒸留は、通常、２００〜３００℃程度、１００〜１５００Ｐａ程度の範囲から蒸留時間を考慮して適宜選択される。再結晶は、例えば、未精製ロジンを良溶媒に溶解し、ついで溶媒を留去して濃厚な溶液となし、この溶液に貧溶媒を添加することにより行なう。良溶媒としてはベンゼン、トルエン、キシレンなどの芳香族炭化水素溶媒、クロロホルムなどの塩素化炭化水素溶媒、低級アルコール、アセトンなどのケトン類、酢酸エチルなどの酢酸エステル類等が挙げられ、貧溶媒としてはｎ−ヘキサン、ｎ−ヘプタン、シクロヘキサン、イソオクタン等が挙げられる。抽出の場合は、アルカリ水を用いて未精製のロジンをアルカリ水溶液となし、これに含まれる不溶性の不ケン化物を有機溶媒を用いて抽出したのち、水層を中和することで精製ロジンを得ることができる。精製ロジン類中に含まれるアビエチン酸の含有量は０．１重量％以下、テトラヒドロアビエチン酸、デヒドロアビエチン酸およびジヒドロアビエチン酸の含有量の合計は９０重量％以上とすることが、安定性が良好となるため好ましく、９８重量％以上とすることが特に好ましい。また、精製ロジン類中に含まれるデヒドロアビエチン酸の含有量は、４０〜８０重量％とすることが好ましい。デヒドロアビエチン酸量を４０重量％以上とすることにより、芳香族を有する成分が増加するために各種ポリマーとの相溶性が良好となる。一方、８０重量％以下とすることにより、本発明の粘着付与剤の結晶性を抑制でき、その取り扱い性が良好となるため好ましい。なお、デヒドロアビエチン酸の含有量は５５〜７０重量％とすることが特に好ましい。なお、精製ロジン類の組成を、前記組成にするためには、例えば、蒸留したロジン類に不均化、水素化等の各操作を単独でまたは組み合わせておこなってもよいが、テトラヒドロアビエチン酸、ジヒドロアビエチン酸、デヒドロアビエチン酸等を調製し、これらを混合してもよい。なお、テトラヒドロアビエチン酸は、例えば、Ｊ. Ｏｒｇ. Ｃｈｅｍ. ３１, ４１２８(１９６６) 、Ｊ. Ｏｒｇ. Ｃｈｅｍ. ３４, １５５０(１９６９)に記載の方法で、ジヒドロアビエチン酸は、例えば、特開昭５１−１４９２５６に記載の方法で、デヒドロアビエチン酸は、例えば、ＵＳＰ３，７３７，４５３、Ｊ. Ｏｒｇ. Ｃｈｅｍ. ３１, ４２４６−４２４８ (１９６６)に記載の方法で得ることができる。 Purified rosins can be obtained by removing high molecular weight substances thought to have arisen from resin acid peroxides from unpurified rosins and unsaponified products contained in unpurified rosins. The purification method is not particularly limited, and various known purification methods can be appropriately selected. Specifically, operations such as distillation, recrystallization, extraction and the like can be mentioned. Industrially, purification by distillation is preferred. The distillation is appropriately selected from the range of about 200 to 300 ° C. and about 100 to 1500 Pa in consideration of the distillation time. The recrystallization is performed, for example, by dissolving unpurified rosin in a good solvent, then distilling off the solvent to form a concentrated solution, and adding a poor solvent to this solution. Examples of good solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene, chlorinated hydrocarbon solvents such as chloroform, ketones such as lower alcohol and acetone, and acetates such as ethyl acetate. N-hexane, n-heptane, cyclohexane, isooctane and the like. In the case of extraction, unpurified rosin is made into an alkaline aqueous solution using alkaline water, and insoluble unsaponifiable matter contained therein is extracted using an organic solvent, and then the aqueous layer is neutralized to obtain purified rosin. Obtainable. Stability is good when the content of abietic acid contained in the purified rosins is 0.1% by weight or less, and the total content of tetrahydroabietic acid, dehydroabietic acid and dihydroabietic acid is 90% by weight or more. Therefore, the content is preferably 98% by weight or more. The content of dehydroabietic acid contained in the purified rosins is preferably 40 to 80% by weight. By setting the amount of dehydroabietic acid to 40% by weight or more, the amount of aromatic components increases, so that compatibility with various polymers is improved. On the other hand, the content of 80% by weight or less is preferable because the crystallinity of the tackifier of the present invention can be suppressed, and the handleability is improved. The content of dehydroabietic acid is particularly preferably 55 to 70% by weight. In order to make the composition of the purified rosins into the above-mentioned composition, for example, each operation such as disproportionation and hydrogenation may be carried out alone or in combination with distilled rosins, but tetrahydroabietic acid, Dihydroabietic acid, dehydroabietic acid and the like may be prepared and mixed. Tetrahydroabietic acid is a method described in, for example, J. Org. Chem. 31, 4128 (1966), J. Org. Chem. 34, 1550 (1969). In the method described in 51-149256, dehydroabietic acid can be obtained by the method described in, for example, USP 3,737,453, J. Org. Chem. 31, 4246-4248 (1966).
本発明の粘着付与剤の製造に用いられるアルコール類の具体例としては、ｎ−オクチルアルコール、２−エチルヘキシルアルコール、デシルアルコール、ラウリルアルコール等の１価アルコール；エチレングリコール、ジ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等の２価アルコール；グリセリン、トリメチロールエタン、トリメチロールプロパン、シクロヘキサンジメタノール等の３価アルコール；ペンタエリスリトール、ジグリセリン等の４価アルコールなどが挙げられ、これらのうちいずれか一種を単独でまたは二種以上を混合して用いることができる。 Specific examples of alcohols used in the production of the tackifier of the present invention include monohydric alcohols such as n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, and lauryl alcohol; ethylene glycol, diethylene glycol, propylene glycol, and neopentyl. Dihydric alcohols such as glycol; trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and cyclohexanedimethanol; and tetrahydric alcohols such as pentaerythritol and diglycerin, and any one of these. Or 2 or more types can be mixed and used.
これらの中では、３価のアルコール、２価のアルコールを用いることが、得られる精製ロジン類とアルコール類の反応生成物の軟化点を所望の温度とすることができるため好ましい。なお、精製ロジン類およびアルコール類の使用量は特に限定されないが、通常、精製ロジン中のカルボン酸基とアルコール中の水酸基のモル比（ＯＨ／ＣＯＯＨ）を０．５〜２程度とすることが好ましい。 Among these, it is preferable to use a trivalent alcohol or a divalent alcohol since the softening point of the reaction product of the obtained purified rosins and alcohols can be set to a desired temperature. In addition, although the usage-amount of refined rosins and alcohol is not specifically limited, Usually, molar ratio (OH / COOH) of the carboxylic acid group in refined rosin and the hydroxyl group in alcohol shall be about 0.5-2. preferable.
精製ロジン類とアルコール類の反応は、公知のエステル化方法で行うことができる。具体的には、１５０〜３００℃程度の高温条件において、生成する水を系外に除去しながら行われる。また、エステル化反応中に空気が混入すると生成するエステル化物が着色するおそれがあるため、反応は窒素やヘリウム、アルゴン等の不活性ガス下で行うことが好ましい。なお、反応に際しては、必ずしもエステル化触媒を必要としないが、反応時間の短縮のために酢酸、パラトルエンスルホン酸等の酸触媒、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を使用することもできる。 The reaction between the purified rosin and the alcohol can be performed by a known esterification method. Specifically, it is performed while removing generated water out of the system under high temperature conditions of about 150 to 300 ° C. In addition, if air is mixed during the esterification reaction, the produced esterified product may be colored. Therefore, the reaction is preferably performed under an inert gas such as nitrogen, helium, or argon. In the reaction, an esterification catalyst is not necessarily required, but in order to shorten the reaction time, an acid catalyst such as acetic acid and paratoluenesulfonic acid, an alkali metal hydroxide such as calcium hydroxide, calcium oxide, and oxidation. Metal oxides such as magnesium can also be used.
このようにして得られた精製ロジン類とアルコール類の反応生成物の軟化点（環球法）は、５０〜１２０℃程度とすることが好ましい。５０℃以上とすることで、粘着付与剤の取り扱いが容易になるため好ましい。また、１２０℃以上とするにはロジン類を、例えば、フマル酸、マレイン酸、アクリル酸などの不飽和酸で変性等する必要があるが、これらの酸を用いて変性をすると分子量分布が広くなり、粘着剤等にする際に用いるベース樹脂との相溶性が悪化する場合がある。また、得られる精製ロジン類とアルコール類との反応物は、アルコールの精製ロジン類によるトリエステル体の含有量を７０〜８５重量％程度とすることが好ましい。トリエステル体の量が７０重量％以上とすることで、反応生成物の軟化点を高く維持することができる。また、８５重量％を超えるまでエステル化反応を進行させるには長時間必要となるため、工業的に好ましくない。また、精製ロジン類とアルコールの反応生成物の色調は、通常、１５０ハーゼン（ＪＩＳ Ｋ ００７１−１）以下の無色透明である。 The softening point (ring and ball method) of the reaction product of the purified rosins and alcohols thus obtained is preferably about 50 to 120 ° C. It is preferable to set the temperature to 50 ° C. or higher because the tackifier can be easily handled. Further, in order to increase the temperature to 120 ° C. or higher, it is necessary to modify rosins with unsaturated acids such as fumaric acid, maleic acid, and acrylic acid. If these acids are used for modification, the molecular weight distribution is wide. In other words, the compatibility with the base resin used when making an adhesive or the like may deteriorate. Moreover, it is preferable that content of the triester body by the refinement | purification rosins of alcohol is about 70 to 85 weight% in the reaction material of purified rosins and alcohols obtained. When the amount of the triester is 70% by weight or more, the softening point of the reaction product can be kept high. Further, since it takes a long time to advance the esterification reaction until it exceeds 85% by weight, it is not industrially preferable. The color tone of the reaction product of purified rosins and alcohol is usually colorless and transparent of 150 Hazen (JIS K 0071-1) or less.
本発明の粘着剤または接着剤は、前述の粘着付与剤を用いて得ることができる。粘着剤または接着剤としては、例えば、アクリル系感圧接着剤組成物、スチレン−共役ジエン系ブロック共重合体粘着剤組成物、エチレン系ホットメルト接着剤などが挙げられる。 The pressure-sensitive adhesive or adhesive of the present invention can be obtained using the aforementioned tackifier. Examples of the pressure-sensitive adhesive or adhesive include acrylic pressure-sensitive adhesive compositions, styrene-conjugated diene block copolymer pressure-sensitive adhesive compositions, and ethylene-based hot melt adhesives.
アクリル系感圧接着剤は、ベースポリマーであるアクリル系重合体に粘着付与剤を配合することによって得られる。 The acrylic pressure-sensitive adhesive is obtained by blending a tackifier with an acrylic polymer that is a base polymer.
アクリル系重合体は、特に制限はなく、アクリル系感圧接着剤として使用されている各種公知の単独重合体もしくは共重合体をそのまま使用することができる。アクリル系重合体に使用される単量体としては、各種（メタ）アクリル酸エステル（なお、（メタ）アクリル酸エステルとはアクリル酸エステルおよび／またはメタクリル酸エステルをいい、以下（メタ）とは同様の意味である）を使用できる。かかる（メタ）アクリル酸エステルの具体例としては、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−エチルヘキシル等を例示でき、これらを単独もしくは組合せて使用できる。また、得られるアクリル系重合体に極性を付与するために前記（メタ）アクリル酸エステルの一部に代えて（メタ）アクリル酸を少量使用することもできる。さらに、架橋性単量体として（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、Ｎ−メチロール（メタ）アクリルアミド等も併用しうる。更に所望により、（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他の共重合可能な単量体、たとえば酢酸ビニル、スチレン等を併用しうる。 The acrylic polymer is not particularly limited, and various known homopolymers or copolymers that are used as acrylic pressure-sensitive adhesives can be used as they are. As a monomer used for the acrylic polymer, various (meth) acrylic acid esters (in addition, (meth) acrylic acid ester refers to acrylic acid ester and / or methacrylic acid ester, and hereinafter referred to as (meth) Which has the same meaning). Specific examples of such (meth) acrylic acid esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Can be used alone or in combination. Further, in order to impart polarity to the resulting acrylic polymer, a small amount of (meth) acrylic acid can be used instead of a part of the (meth) acrylic acid ester. Furthermore, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide and the like may be used in combination as the crosslinkable monomer. Furthermore, if desired, other copolymerizable monomers such as vinyl acetate and styrene may be used in combination as long as the adhesive properties of the (meth) acrylic acid ester polymer are not impaired.
これら（メタ）アクリル酸エステルを主成分とするアクリル系重合体のガラス転移温度は特に制限はされないが通常は−９０〜０℃程度、好ましくは−８０〜−１０℃の範囲とするのがよい。ガラス転移温度が０℃よりもあまりにも高い場合にはタックが低下し、−９０℃よりもあまりにも低い場合には接着力が低下する傾向がある。また、分子量は特に限定されないが、通常、重量平均分子量が２０万〜１００万程度であり、３０万〜９０万程度であることが好ましい。分子量をこの範囲とすることにより、粘・接着性能が良好となる。 The glass transition temperature of the acrylic polymer containing these (meth) acrylic acid esters as a main component is not particularly limited, but is usually in the range of about −90 to 0 ° C., preferably in the range of −80 to −10 ° C. . If the glass transition temperature is too high than 0 ° C., the tack tends to decrease, and if it is too low, the adhesive strength tends to decrease. Moreover, although molecular weight is not specifically limited, Usually, a weight average molecular weight is about 200,000-1 million, and it is preferable that it is about 300,000-900,000. By setting the molecular weight within this range, the viscosity / adhesion performance is improved.
なお、該アクリル系重合体の製造方法は、各種公知の方法を採用すればよく、例えば、バルク重合法、溶液重合法、懸濁重合法等のラジカル重合法を適宜選択できる。ラジカル重合開始剤としては、アゾ系、過酸化物系の各種公知のものを使用でき、反応温度は通常５０〜８５℃程度、反応時間は１〜８時間程度とされる。また、アクリル系重合体の溶媒としては一般に酢酸エチル、トルエン等の極性溶剤が用いられ、溶液濃度は通常４０〜６０重量％程度とされる。 In addition, what is necessary is just to employ | adopt various well-known methods for the manufacturing method of this acrylic polymer, For example, radical polymerization methods, such as a bulk polymerization method, a solution polymerization method, and a suspension polymerization method, can be selected suitably. As the radical polymerization initiator, various known azo and peroxide compounds can be used, and the reaction temperature is usually about 50 to 85 ° C. and the reaction time is about 1 to 8 hours. Further, a polar solvent such as ethyl acetate or toluene is generally used as the solvent for the acrylic polymer, and the solution concentration is usually about 40 to 60% by weight.
本発明のアクリル系感圧接着剤組成物の組成比は、アクリル系重合体１００重量部に対して、前記粘着付与樹脂１〜４０重量部程度、好ましくは５〜３０重量部を配合して使用する。粘着付与樹脂の添加量が１重量部に満たない場合には十分な粘着特性を付与することが困難となり、４０重量部を超える場合には相溶性の低下のみならず接着剤組成物が固くなり接着力及びタックも低下するため好ましくない。 The composition ratio of the acrylic pressure-sensitive adhesive composition of the present invention is about 1 to 40 parts by weight, preferably 5 to 30 parts by weight of the tackifier resin, based on 100 parts by weight of the acrylic polymer. To do. When the amount of tackifying resin added is less than 1 part by weight, it becomes difficult to impart sufficient tackiness properties, and when it exceeds 40 parts by weight, the adhesive composition becomes hard as well as a decrease in compatibility. Adhesive strength and tack are also reduced, which is not preferable.
なお、本発明のアクリル系感圧接着剤組成物は、前記アクリル系重合体および粘着付与樹脂に、ポリイソシアネート化合物、ポリアミン化合物、メラミン樹脂、尿素樹脂、エポキシ樹脂等の架橋剤を加えることにより、凝集力、耐熱性を更に向上させることもできる。これら架橋剤のなかでも、特にポリイソシアネート化合物を使用するのが好ましく、その具体例としては、１，６−ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、トリレンジイソシアネート、４，４−ジフェニルメタンジイソシアネート等の各種公知のものがあげられる。さらに本発明のアクリル系感圧接着剤組成物は必要に応じて充填剤、酸化防止剤、紫外線吸収剤等を適宜使用しうる。また、本発明のアクリル系感圧接着剤組成物は、本発明の目的を逸脱しない範囲で各種公知の粘着付与樹脂を併用することもできる。 The acrylic pressure-sensitive adhesive composition of the present invention is obtained by adding a crosslinking agent such as a polyisocyanate compound, a polyamine compound, a melamine resin, a urea resin, or an epoxy resin to the acrylic polymer and the tackifier resin. The cohesive force and heat resistance can be further improved. Among these crosslinking agents, it is particularly preferable to use a polyisocyanate compound. Specific examples thereof include 1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, 4,4. -Various well-known things, such as diphenylmethane diisocyanate, are mention | raise | lifted. Furthermore, the acrylic pressure-sensitive adhesive composition of the present invention can appropriately use a filler, an antioxidant, an ultraviolet absorber and the like as necessary. In addition, the acrylic pressure-sensitive adhesive composition of the present invention can be used in combination with various known tackifying resins without departing from the object of the present invention.
本発明のスチレン−共役ジエン系ブロック共重合体粘着剤組成物は、前記粘着付与剤、スチレン−共役ジエン系ブロック共重合体およびオイルを配合したものである。 The styrene-conjugated diene block copolymer pressure-sensitive adhesive composition of the present invention is a mixture of the tackifier, styrene-conjugated diene block copolymer and oil.
スチレン−共役ジエン系ブロック共重合体とは、スチレン、メチルスチレン等のスチレン類と、ブタジエン、イソプレン等の共役ジエン類を、使用目的に応じて適宜に選択して共重合したブロック共重合体である。通常、スチレン類／共役ジエン類の重量比は、１０／９０〜５０／５０である。このようなブロック共重合体の好ましい具体例としては、たとえばスチレン類（Ｓ）／ブダジエン（Ｂ）の重量比が、１０／９０〜５０／５０の範囲にあるＳＢＳ型ブロック共重合体、スチレン類（Ｓ）／イソプレン（Ｉ）の重量比が、１０／９０〜３０／７０の範囲にあるＳＩＳ型ブロック共重合体等があげられる。また、本発明のスチレン−共役ジエン系ブロック共重合体には、前記ブロック共重合体の共役ジエン成分を水素化したものも含まれる。水素化したものの具体例としては、いわゆるＳＥＢＳ型ブロック共重合体、ＳＥＰＳ型ブロック共重合体などがあげられる。 The styrene-conjugated diene block copolymer is a block copolymer obtained by copolymerizing styrenes such as styrene and methylstyrene and conjugated dienes such as butadiene and isoprene as appropriate according to the purpose of use. is there. Usually, the weight ratio of styrenes / conjugated dienes is 10/90 to 50/50. Preferable specific examples of such a block copolymer include, for example, SBS type block copolymers and styrenes having a weight ratio of styrenes (S) / budadiene (B) in the range of 10/90 to 50/50. Examples thereof include SIS type block copolymers having a weight ratio of (S) / isoprene (I) in the range of 10/90 to 30/70. The styrene-conjugated diene block copolymer of the present invention includes those obtained by hydrogenating the conjugated diene component of the block copolymer. Specific examples of the hydrogenated material include so-called SEBS type block copolymers and SEPS type block copolymers.
また、オイルとしては、ナフテン系オイル、パラフィン系オイルや、芳香族系オイル等の可塑化オイルがあげられる。凝集力の低下が少ない点からすれば、ナフテン系オイル、パラフィン系オイルが好ましい。具体的には、ナフテン系プロセス油、パラフィン系プロセス油、液状ポリブテン等があげられる。 Examples of the oil include naphthenic oil, paraffinic oil, and plasticized oil such as aromatic oil. Naphthenic oils and paraffinic oils are preferable from the viewpoint of little reduction in cohesive strength. Specific examples include naphthenic process oil, paraffinic process oil, and liquid polybutene.
各成分の使用量としては、粘着付与剤１５〜２１０重量部、スチレン−共役ジエン系ブロック共重合体４〜２００重量部およびオイル４〜２００重量部を含有してなるものである。 The amount of each component used includes 15 to 210 parts by weight of a tackifier, 4 to 200 parts by weight of a styrene-conjugated diene block copolymer, and 4 to 200 parts by weight of oil.
スチレン−共役ジエン系ブロック共重合体が４重量部未満の場合には、保持力が不十分であり、２００重量部を超える場合には得られる粘着剤組成物の溶融粘度が高くなりいずれも好ましくない。また、オイルが４重量部未満の場合には、粘着剤組成物の溶融粘度が高くなり、２００重量部を超える場合には保持力が不十分になる場合がある。 When the styrene-conjugated diene block copolymer is less than 4 parts by weight, the holding power is insufficient, and when it exceeds 200 parts by weight, the resulting adhesive composition has a high melt viscosity, which is preferable. Absent. Moreover, when oil is less than 4 weight part, the melt viscosity of an adhesive composition will become high, and when it exceeds 200 weight part, holding power may become inadequate.
なお、本発明のスチレン−共役ジエン系ブロック共重合体粘着剤組成物には、さらに、必要に応じて、充填剤、酸化防止剤等の添加剤を加えることができる。 In addition, additives, such as a filler and antioxidant, can be further added to the styrene-conjugated diene block copolymer pressure-sensitive adhesive composition of the present invention as necessary.
このようにして得られた粘着剤または接着剤組成物を、各種プラスチックフィルム、紙テープ等の基材上に塗布後、乾燥させることにより、粘着テープを得ることができる。 A pressure-sensitive adhesive tape can be obtained by applying the pressure-sensitive adhesive or adhesive composition thus obtained onto a substrate such as various plastic films and paper tape and then drying it.
本発明のエチレン系ホットメルト接着剤組成物は、エチレン系共重合物に前記粘着付与剤を配合することによって得られる。 The ethylene-based hot melt adhesive composition of the present invention can be obtained by blending the tackifier in an ethylene copolymer.
エチレン系共重合物とは、エチレンと、エチレンと共重合可能な単量体との共重合物であり、従来、ホットメルト接着剤に使用されていたものを使用できる。エチレンと共重合可能な単量体とは、たとえば酢酸ビニル等があげられる。酢酸ビニル含有量は通常２０〜４５重量％程度である。なお、分子量は、メルトインデックス（１９０℃、荷重２１６０ｇ、１０分間）が１０〜４００ｇ／１０分程度のものが好ましい。 The ethylene-based copolymer is a copolymer of ethylene and a monomer copolymerizable with ethylene, and those conventionally used for hot melt adhesives can be used. Examples of the monomer copolymerizable with ethylene include vinyl acetate. The vinyl acetate content is usually about 20 to 45% by weight. The molecular weight is preferably such that the melt index (190 ° C., load 2160 g, 10 minutes) is about 10 to 400 g / 10 minutes.
ワックスとしては、ホットメルト接着剤において用いられるものを使用でき、具体的にはパラフィンワックス、マイクロクリスタリンワックスなどの石油系ワックス、フィシャー・トロプシュワックス、低分子量ポリエチレンワックスなどの合成ワックスがあげられる。 As the wax, those used in hot melt adhesives can be used, and specific examples include petroleum waxes such as paraffin wax and microcrystalline wax, synthetic waxes such as Fischer-Tropsch wax and low molecular weight polyethylene wax.
本発明のエチレン系ホットメルト接着剤は、エチレン系共重合物１００重量部、前記本発明の粘着付与剤５０〜１５０重量部およびワックス１０〜１００重量部を含有してなるものである。 The ethylene hot melt adhesive of the present invention comprises 100 parts by weight of an ethylene copolymer, 50 to 150 parts by weight of the tackifier of the present invention, and 10 to 100 parts by weight of wax.
粘着付与剤が５０重量部未満の場合には十分な接着力を得られず、また１５０重量部を超える場合は十分な保持力が得られない場合がある。また、ワックスが１０重量部未満の場合には、得られる接着剤組成物の溶融粘度が高くなりすぎ、また１００重量部を超える場合には、十分な保持力が得られないため好ましくない。なお、本発明のエチレン系ホットメルト接着剤には、さらに、必要に応じて、充填剤、酸化防止剤等の添加剤を加えることができる。 When the tackifier is less than 50 parts by weight, a sufficient adhesive force cannot be obtained, and when it exceeds 150 parts by weight, a sufficient holding force may not be obtained. Moreover, when the wax is less than 10 parts by weight, the melt viscosity of the resulting adhesive composition becomes too high, and when it exceeds 100 parts by weight, a sufficient holding power cannot be obtained, which is not preferable. In addition, additives, such as a filler and antioxidant, can be further added to the ethylene-based hot melt adhesive of the present invention as necessary.
本発明の粘着付与剤は、医療用用途に使用される各種のベースポリマー、例えば、ゴム、アクリルポリマーに好適に相溶し、また色調も１５０H（ハーゼン）以下で無色〜淡色と優れ、酸化反応性を有するオレフィン性二重結合を実質的に有さない、すなわち安定性と皮膚感作性に優れた粘着付与剤であり、該粘着付与剤は経皮吸収型製剤の各種用途に利用できる。 The tackifier of the present invention is suitably compatible with various base polymers used for medical applications, such as rubber and acrylic polymers, and has a color tone of 150H (Hazen) or less, excellent in colorless to light color, and oxidation reaction. It is a tackifier substantially free of olefinic double bonds having properties, that is, excellent in stability and skin sensitization, and the tackifier can be used for various uses of a transdermal preparation.
例えば、鎮痛消炎を目的とする貼布剤やプラスターに代表される局所性製剤、毛細血管中に薬物を吸収させ、作用部位に送達させる全身性製剤などがあげられる。具体的には、全身性製剤としては、心臓病用剤、ホルモン補充用剤、喘息用剤、禁煙補助用剤、癌性疼痛用剤、非がん性疼痛製剤などがあげられる。また、局所製剤としては、貼付用局所麻酔剤、経皮鎮痛消炎剤、鎮痛・抗炎症剤、気管支拡張剤などがあげられる。 Examples include topical preparations typified by patches and plasters for the purpose of analgesic and anti-inflammation, and systemic preparations that absorb drugs into capillaries and deliver them to the site of action. Specifically, examples of systemic preparations include heart disease agents, hormone replacement agents, asthma agents, smoking cessation aid agents, cancer pain agents, non-cancer pain agents and the like. Examples of topical preparations include local anesthetics for application, transdermal analgesic / anti-inflammatory agents, analgesic / anti-inflammatory agents, bronchodilators, and the like.
以下、実施例及び比較例をあげて本発明方法を更に詳しく説明するが、本発明がこれらに限定されないことはもとよりである。なお、実施例中％は重量％を示す。なお、精製ロジンの樹脂酸組成の同定と定量は下記の方法による。 Hereinafter, the method of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. In the examples,% indicates% by weight. The resin acid composition of purified rosin is identified and quantified by the following method.
実施例、比較例内に示す樹脂酸の組成と定量は、ガスクロマトグラフィーで実施した。樹脂酸０．１ｇをｎ−ヘキサノール２．０ｇに溶解する。この溶液０．１ｇと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））０．４ｇを均一混合し、１μｌをガスクロマトグラフィーに打ち込み組成分析と定量をおこなった。
ガスクロマトグラフィー：ＧＣ−１４Ａ （株）島津製作所
カラム：Ａｄｖａｎｃｅ−ＤＳ 信和化工（株）
The composition and quantification of the resin acid shown in the examples and comparative examples were carried out by gas chromatography. 0.1 g of resin acid is dissolved in 2.0 g of n-hexanol. 0.1 g of this solution and 0.4 g of an on-column methylating agent (phenyltrimethylammonium hydroxide (PTHA) 0.2 molar methanol solution, GL Science Co., Ltd.) were mixed uniformly, and 1 μl was put into gas chromatography to analyze the composition. Quantification was performed.
Gas chromatography: GC-14A Shimadzu Corporation Column: Advance-DS Shinwa Kako Co., Ltd.
製造例１（デヒドロアビエチン酸の製造）
不均化ロジン（酸価１６７、軟化点７７℃、荒川化学工業（株）製）をアルゴン気流中でメルト後、１ｍｍＨｇの減圧下で加熱し、１９５〜２００℃／０．３５ｍｍＨｇの留分を得た。この精製不均化ロジンは酸価１８０、軟化点９３℃であった。この精製不均化ロジン２００ｇをエタノール４８０ｇに加熱溶解し、これにモノエタノールアミン４０ｇを加えて1時間還流下で反応させた後、水５００ｇを加えた。得られたデヒドロアビエチン酸モノエタノールアミン塩をイソオクタン２００ｍｌで２回抽出し、不けん化物およびジヒドロアビエチン酸塩を除いた。一晩放置の後結晶をろ過し、さらにエタノール２５０ｇで３回再結晶をおこない、十分デヒドロアビエチン酸の純度をあげてから塩酸でアミン塩を分解しろ過した。この結晶をエーテルに溶解し十分に水洗したのちに完固、再度エタノール中で再結晶した。得られたデヒドロアビエチン酸の酸価は１８６、融点１７８℃、ガスクロマトグラフィー純度は９６％であった。
Production Example 1 (Production of dehydroabietic acid)
Disproportionated rosin (acid number 167, softening point 77 ° C, manufactured by Arakawa Chemical Industries, Ltd.) was melted in an argon stream and heated under a reduced pressure of 1 mmHg, and a fraction of 195 to 200 ° C / 0.35 mmHg was obtained. Obtained. This purified disproportionated rosin had an acid value of 180 and a softening point of 93 ° C. 200 g of this purified disproportionated rosin was dissolved in 480 g of ethanol by heating, 40 g of monoethanolamine was added thereto, and the mixture was reacted under reflux for 1 hour, and then 500 g of water was added. The obtained dehydroabietic acid monoethanolamine salt was extracted twice with 200 ml of isooctane to remove unsaponifiable matter and dihydroabietic acid salt. After standing overnight, the crystals were filtered, and recrystallized three times with 250 g of ethanol. After sufficiently increasing the purity of dehydroabietic acid, the amine salt was decomposed with hydrochloric acid and filtered. The crystals were dissolved in ether, washed thoroughly with water, completely solidified, and recrystallized again in ethanol. The obtained dehydroabietic acid had an acid value of 186, a melting point of 178 ° C., and a gas chromatography purity of 96%.
製造例２（テトラヒドロアビエチン酸の製造）
市販のアビエチン酸３００ｇ（関東化学 融点１７２〜１７５℃）およびシクロヘキサン５００ｇ、触媒としてニッケルけいそう土触媒Ｎ−１１３（日揮化学（株））１５ｇをオートクレーブに仕込み、水素置換後１０ＭＰａまで昇圧し２５０℃で５時間反応させた。反応終了後冷却し水素をブローした後に、ろ過により触媒を除去した。得られたクルードなテトラヒドロアビエチン酸を濃縮し、アセトン中で２回再結晶をおこない減圧下で乾燥した。得られたテトラヒドロアビエチン酸の酸価は１９４、融点１７０℃、ガスクロマトグラフィー純度は９７％であった。
Production Example 2 (Production of tetrahydroabietic acid)
300 g of commercially available abietic acid (Kanto Chemical Melting Point: 172 to 175 ° C.) and 500 g of cyclohexane and 15 g of nickel diatomaceous earth catalyst N-113 (JGC Chemical Co., Ltd.) as a catalyst were charged into an autoclave. For 5 hours. After completion of the reaction, the mixture was cooled and hydrogen was blown, and then the catalyst was removed by filtration. The obtained crude tetrahydroabietic acid was concentrated, recrystallized twice in acetone and dried under reduced pressure. The resulting tetrahydroabietic acid had an acid value of 194, a melting point of 170 ° C., and a gas chromatography purity of 97%.
製造例３（ジヒドロアビエチン酸の製造）
オートクレーブに未精製中国産ガムロジン１００ｇとミネラルターペン１００ｇ、水素化触媒としてラネーニッケル触媒５ｇを仕込み、水素置換後１０ＭＰａまで昇圧し１１０℃で５時間反応させた。触媒は窒素雰囲気下でろ過し、半水添ロジンのミネラルターペン溶液を得た。この溶液１００ｇにパラトルエンスルホン酸０．２ｇを加え、反応温度１５０℃で２時間異性化させたのち、引き続き減圧蒸留にてミネラルターペン、パラトルエンスルホン酸を留去し、粗結晶化した。この粗結晶をアセトン中で４回再結晶をおこなうことにより、目的のジヒドロアビエチン酸を得た。得られたテトラヒドロアビエチン酸の酸価は１９４、融点１８２℃、ガスクロマトグラフィー純度は９８％であった。
Production Example 3 (Production of dihydroabietic acid)
An autoclave was charged with 100 g of unpurified Chinese gum rosin, 100 g of mineral turpentine, and 5 g of Raney nickel catalyst as a hydrogenation catalyst. After hydrogen substitution, the pressure was increased to 10 MPa and the reaction was carried out at 110 ° C. for 5 hours. The catalyst was filtered under a nitrogen atmosphere to obtain a mineral terpene solution of semi-hydrogenated rosin. After adding 0.2 g of paratoluenesulfonic acid to 100 g of this solution and isomerizing at a reaction temperature of 150 ° C. for 2 hours, mineral terpene and paratoluenesulfonic acid were distilled off by distillation under reduced pressure, followed by rough crystallization. The crude crystal was recrystallized four times in acetone to obtain the target dihydroabietic acid. The resulting tetrahydroabietic acid had an acid value of 194, a melting point of 182 ° C., and a gas chromatography purity of 98%.
製造例４（溶剤型アクリル系重合体の製造）
撹拌装置、冷却管、２基の滴下ロートおよび窒素導入管を備えた反応装置に酢酸エチル５０部、トルエン３０部を仕込んだ後、窒素気流下に系内温度が約７５℃となるまで昇温した。次いで、あらかじめアクリル酸ブチル４８．５部、アクリル酸２−エチルヘキシル４８．５部、アクリル酸３部を混合して仕込んだ滴下ロートと、アゾビスイソブチロニトリル０．１部および酢酸エチル１０部を仕込んだ滴下ロートから約３時間を要して系内に滴下し、更に５時間同温度に保って重合反応を完結させた。酢酸エチルを追加して固形分を約５０％に調整し、アクリル系重合体を含有する組成物を得た。
Production Example 4 (Production of solvent-type acrylic polymer)
After charging 50 parts of ethyl acetate and 30 parts of toluene into a reaction apparatus equipped with a stirrer, a cooling pipe, two dropping funnels and a nitrogen introduction pipe, the temperature was raised to about 75 ° C. in the nitrogen stream. did. Next, a dropping funnel previously prepared by mixing 48.5 parts of butyl acrylate, 48.5 parts of 2-ethylhexyl acrylate, and 3 parts of acrylic acid, 0.1 part of azobisisobutyronitrile and 10 parts of ethyl acetate It took about 3 hours from the dropping funnel charged with No. 1 and dropped into the system, and the temperature was maintained at the same temperature for 5 hours to complete the polymerization reaction. Ethyl acetate was added to adjust the solid content to about 50% to obtain a composition containing an acrylic polymer.
実施例１
製造例１で得たデヒドロアビエチン酸４０ｇ、製造例２で得たテトラヒドロアビエチン酸３０ｇ、製造例３で得たジヒドロアビエチン酸３０ｇを４つ口フラスコにとり、アルゴンシール下で１８０℃に昇温し溶融攪拌下２００℃でグリセリン１２ｇを加えた。その後、２８０℃で１２時間反応させた。エステル化により発生した水は分縮器を介して、系外に排出し、エステル化を進行させ、軟化点９３℃、酸価４、色調１００Ｈ（ハーゼン）のロジンエステル樹脂を１０３ｇ得た。
Example 1
40 g of dehydroabietic acid obtained in Production Example 1, 30 g of tetrahydroabietic acid obtained in Production Example 2, and 30 g of dihydroabietic acid obtained in Production Example 3 are placed in a four-necked flask and heated to 180 ° C. under an argon seal and melted. 12 g of glycerin was added at 200 ° C. with stirring. Then, it was made to react at 280 degreeC for 12 hours. Water generated by esterification was discharged out of the system through a partial condenser, and the esterification proceeded to obtain 103 g of rosin ester resin having a softening point of 93 ° C., an acid value of 4 and a color tone of 100H (Hazen).
実施例２
実施例１において、デヒドロアビエチン酸、テトラヒドロアビエチン酸、ジヒドロアビエチン酸の使用量を、デヒドロアビエチン酸４５ｇ、テトラヒドロアビエチン酸３０ｇ、ジヒドロアビエチン酸２５ｇに変えた他は、実施例１と同様にして粘着付与剤を１０２ｇ得た。結果を表１に示す。
Example 2
In Example 1, except that the amount of dehydroabietic acid, tetrahydroabietic acid, and dihydroabietic acid used was changed to 45 g of dehydroabietic acid, 30 g of tetrahydroabietic acid, and 25 g of dihydroabietic acid. 102 g of agent was obtained. The results are shown in Table 1.
実施例３
実施例１において、デヒドロアビエチン酸、テトラヒドロアビエチン酸、ジヒドロアビエチン酸の使用量を、デヒドロアビエチン酸５７ｇ、テトラヒドロアビエチン酸２５ｇ、ジヒドロアビエチン酸１８ｇに変えた他は、実施例１と同様にして粘着付与剤を１０１ｇ得た。結果を表１に示す。
Example 3
In Example 1, tackifying was performed in the same manner as in Example 1 except that the amounts of dehydroabietic acid, tetrahydroabietic acid, and dihydroabietic acid used were changed to 57 g of dehydroabietic acid, 25 g of tetrahydroabietic acid, and 18 g of dihydroabietic acid. 101 g of agent was obtained. The results are shown in Table 1.
実施例４
実施例１において、デヒドロアビエチン酸、テトラヒドロアビエチン酸、ジヒドロアビエチン酸の使用量を、デヒドロアビエチン酸６１ｇ、テトラヒドロアビエチン酸２０ｇ、ジヒドロアビエチン酸１９ｇに変えた他は、実施例１と同様にして粘着付与剤を１０２ｇ得た。結果を表１に示す。
Example 4
In Example 1, except that the amount of dehydroabietic acid, tetrahydroabietic acid, and dihydroabietic acid used was changed to 61 g of dehydroabietic acid, 20 g of tetrahydroabietic acid, and 19 g of dihydroabietic acid. 102 g of agent was obtained. The results are shown in Table 1.
実施例５
実施例１において、デヒドロアビエチン酸、テトラヒドロアビエチン酸、ジヒドロアビエチン酸の使用量を、デヒドロアビエチン酸６９ｇ、テトラヒドロアビエチン酸１１ｇ、ジヒドロアビエチン酸２０ｇに変えた他は、実施例１と同様にして粘着付与剤を１０３ｇ得た。結果を表１に示す。
Example 5
In Example 1, tackifying was performed in the same manner as in Example 1 except that the amount of dehydroabietic acid, tetrahydroabietic acid, and dihydroabietic acid was changed to 69 g of dehydroabietic acid, 11 g of tetrahydroabietic acid, and 20 g of dihydroabietic acid. 103 g of the agent was obtained. The results are shown in Table 1.
実施例６
実施例１において、デヒドロアビエチン酸、テトラヒドロアビエチン酸、ジヒドロアビエチン酸の使用量を、デヒドロアビエチン酸７５ｇ、テトラヒドロアビエチン酸１３ｇ、ジヒドロアビエチン酸１２ｇに変えた他は、実施例１と同様にして粘着付与剤を１０３ｇ得た。
Example 6
In Example 1, tackifying was performed in the same manner as in Example 1 except that the amounts of dehydroabietic acid, tetrahydroabietic acid, and dihydroabietic acid were changed to 75 g of dehydroabietic acid, 13 g of tetrahydroabietic acid, and 12 g of dihydroabietic acid. 103 g of the agent was obtained.
実施例７
実施例１において、デヒドロアビエチン酸、テトラヒドロアビエチン酸、ジヒドロアビエチン酸の使用量を、デヒドロアビエチン酸７９ｇ、テトラヒドロアビエチン酸１１ｇ、ジヒドロアビエチン酸１０ｇに変えた他は、実施例１と同様にして粘着付与剤を１０２ｇ得た。結果を表１に示す。
Example 7
In Example 1, tackifying was performed in the same manner as in Example 1 except that the amount of dehydroabietic acid, tetrahydroabietic acid, and dihydroabietic acid was changed to 79 g of dehydroabietic acid, 11 g of tetrahydroabietic acid, and 10 g of dihydroabietic acid. 102 g of agent was obtained. The results are shown in Table 1.
実施例８
市販の中国水添ロジン（軟化点７３℃、色調６Ｇ、酸価１６３、広西梧州日成林産化工有限公司）と不均化ロジン（酸価１６７、軟化点７７℃、荒川化学工業（株）製）を１：１で混合して、窒素シール下に３ｍｍＨｇの減圧下で蒸留し、酸価１７２、軟化点７９．５℃、色調ガードナー１２０Ｈの精製混合ロジン酸を得た。この混合ロジン酸１００ｇとグリセリン１２ｇを実施例１と同様の方法でエステル化し、軟化点９３℃、酸価５、色調１４０Ｈ（ハーゼン）の粘着付与剤１０２ｇ得た。樹脂酸組成は、得られた粘着付与剤（ロジンエステル）を定法に従って加水分解（ｎ−ヘキサノール中、ＫＯＨを加えて、２時間還流反応させた後に、塩酸で中性とし、得られた樹脂酸を分析に用いる。）した後に、ガスクロマトグラフィーで決定した。
Example 8
Commercially available Chinese hydrogenated rosin (softening point 73 ° C, color tone 6G, acid value 163, Guangxi Yinzhou Nislin Industrial Chemical Co., Ltd.) and disproportionated rosin (acid value 167, softening point 77 ° C, manufactured by Arakawa Chemical Industries, Ltd.) ) And distilled under a reduced pressure of 3 mmHg under a nitrogen seal to obtain a purified mixed rosin acid having an acid value of 172, a softening point of 79.5 ° C., and a color tone Gardner 120H. 100 g of this mixed rosin acid and 12 g of glycerin were esterified in the same manner as in Example 1 to obtain 102 g of a tackifier having a softening point of 93 ° C., an acid value of 5, and a color tone of 140H (Hazen). The resin acid composition was obtained by subjecting the obtained tackifier (rosin ester) to hydrolysis according to a standard method (adding KOH in n-hexanol, refluxing for 2 hours, neutralizing with hydrochloric acid, and the resulting resin acid. Was used for analysis) and then determined by gas chromatography.
比較例１
実施例１において、デヒドロアビエチン酸、テトラヒドロアビエチン酸、ジヒドロアビエチン酸の使用量を、デヒドロアビエチン酸３５ｇ、テトラヒドロアビエチン酸６０ｇ、ジヒドロアビエチン酸５ｇに変えた他は、実施例１と同様にして粘着付与剤を１０２ｇ得た。
Comparative Example 1
In Example 1, tackifying was performed in the same manner as in Example 1 except that the amount of dehydroabietic acid, tetrahydroabietic acid, and dihydroabietic acid used was changed to 35 g of dehydroabietic acid, 60 g of tetrahydroabietic acid, and 5 g of dihydroabietic acid. 102 g of agent was obtained.
比較例２
実施例１において、デヒドロアビエチン酸、テトラヒドロアビエチン酸、ジヒドロアビエチン酸の使用量を、デヒドロアビエチン酸３９ｇ、テトラヒドロアビエチン酸５８ｇ、ジヒドロアビエチン酸３ｇに変えた他は、実施例１と同様にして粘着付与剤を１００ｇ得た。
Comparative Example 2
In Example 1, except that the amount of dehydroabietic acid, tetrahydroabietic acid, and dihydroabietic acid used was changed to 39 g of dehydroabietic acid, 58 g of tetrahydroabietic acid, and 3 g of dihydroabietic acid. 100 g of the agent was obtained.
比較例３
実施例１において、デヒドロアビエチン酸、テトラヒドロアビエチン酸、ジヒドロアビエチン酸の使用量を、デヒドロアビエチン酸８１ｇ、テトラヒドロアビエチン酸５ｇ、ジヒドロアビエチン酸１４ｇに変えた他は、実施例１と同様にして粘着付与剤を１０２ｇ得た。
Comparative Example 3
In Example 1, tackifying was performed in the same manner as in Example 1, except that the amount of dehydroabietic acid, tetrahydroabietic acid, and dihydroabietic acid used was changed to 81 g of dehydroabietic acid, 5 g of tetrahydroabietic acid, and 14 g of dihydroabietic acid. 102 g of agent was obtained.
比較例４
実施例１において、デヒドロアビエチン酸、テトラヒドロアビエチン酸、ジヒドロアビエチン酸の使用量を、デヒドロアビエチン酸８５ｇ、ジヒドロアビエチン酸１５ｇに変えた他は、実施例１と同様にして粘着付与剤を１０２ｇ得た。
Comparative Example 4
In Example 1, 102 g of a tackifier was obtained in the same manner as in Example 1 except that the amount of dehydroabietic acid, tetrahydroabietic acid and dihydroabietic acid used was changed to 85 g of dehydroabietic acid and 15 g of dihydroabietic acid. .
比較例５
不均化ロジン（酸価１６７、軟化点７７℃、荒川化学工業（株）製）を窒素シール下に３ｍｍＨｇの減圧下で蒸留し、酸価１７４、軟化点８２℃、色調ガードナー２５０Ｈの精製不均化ロジンを得た。精製不均化ロジンとグリセリンを実施例１と同様の方法でエステル化し、軟化点１００℃、酸価６、色調２５０Ｈのロジンエステル樹脂を１０３ｇ得た。このロジンエステル樹脂１００ｇ、触媒として５％Ｐｄ−カーボン触媒（エヌ・イーケムキャット（株） ５０％含水品）０．２ｇをフラスコに仕込み、アルゴン置換後常圧を保ちながら、２８０℃で２時間反応させた。反応後溶融ろ過により触媒を除去し粘着付与剤９８ｇを得た。樹脂酸組成は、得られた粘着付与剤（ロジンエステルを定法に従って加水分解（ｎ−ヘキサノール中ＫＯＨを加えて、２時間還流反応させた後に、塩酸で中性とし、得られた樹脂酸を分析に提供する。）した後に、ガスクロマトグラフィーで決定した。
Comparative Example 5
Disproportionated rosin (acid number 167, softening point 77 ° C., Arakawa Chemical Industries, Ltd.) was distilled under a reduced pressure of 3 mmHg under a nitrogen seal to give an acid number 174, softening point 82 ° C., tone Gardner 250H. An averaged rosin was obtained. Purified disproportionated rosin and glycerin were esterified in the same manner as in Example 1 to obtain 103 g of a rosin ester resin having a softening point of 100 ° C., an acid value of 6, and a color tone of 250H. 100 g of this rosin ester resin and 0.2 g of a 5% Pd-carbon catalyst (a product containing 50% water from N.E. Chemcat Co., Ltd.) as a catalyst were placed in a flask and reacted at 280 ° C. for 2 hours while maintaining atmospheric pressure after substitution with argon. I let you. After the reaction, the catalyst was removed by melt filtration to obtain 98 g of a tackifier. The resin acid composition was obtained by subjecting the obtained tackifier (rosin ester to hydrolysis according to a standard method (adding KOH in n-hexanol, refluxing for 2 hours, neutralizing with hydrochloric acid, and analyzing the obtained resin acid). And then determined by gas chromatography.
比較例６
不均化ロジン（酸価１６７、軟化点７７℃、荒川化学工業（株）製）を窒素シール下に３ｍｍＨｇの減圧下で蒸留し、酸価１７４、軟化点８２℃、色調ガードナー２５０Ｈの精製不均化ロジンを得た。精製不均化ロジンとグリセリンを実施例１と同様の方法でエステル化し、軟化点１００℃、酸価６、色調２５０Ｈのロジンエステル樹脂を１０３ｇ得た。このロジンエステル樹脂１００ｇをシクロヘキサン１００ｇに溶解し、触媒として５％Ｐｄ−カーボン触媒（エヌ・イーケムキャット（株） ５０％含水品）３．０ｇをオートクレーブに仕込み、水素置換後１５ＭＰａまで昇圧し２９０℃で４時間反応させた。反応終了後冷却し水素をブローした後に、ろ過により触媒を除去した。シクロヘキサンは減圧蒸留により留去して粘着付与剤９７ｇを得た。樹脂酸組成は、得られた粘着付与剤（ロジンエステル）を定法に従って加水分解（ｎ−ヘキサノール中ＫＯＨを加えて、２時間還流反応させた後に、塩酸で中性とし、得られた樹脂酸を分析に提供する。）した後に、ガスクロマトグラフィーで決定した。
Comparative Example 6
Disproportionated rosin (acid number 167, softening point 77 ° C., Arakawa Chemical Industries, Ltd.) was distilled under a reduced pressure of 3 mmHg under a nitrogen seal to give an acid number 174, softening point 82 ° C., tone Gardner 250H. An averaged rosin was obtained. Purified disproportionated rosin and glycerin were esterified in the same manner as in Example 1 to obtain 103 g of a rosin ester resin having a softening point of 100 ° C., an acid value of 6, and a color tone of 250H. 100 g of this rosin ester resin was dissolved in 100 g of cyclohexane, 3.0 g of 5% Pd-carbon catalyst (50% hydrous product of N.E. Chemcat Co., Ltd.) was charged into the autoclave as a catalyst, and after hydrogen substitution, the pressure was increased to 15 MPa and 290 ° C. For 4 hours. After completion of the reaction, the mixture was cooled and hydrogen was blown, and then the catalyst was removed by filtration. Cyclohexane was distilled off under reduced pressure to obtain 97 g of a tackifier. The resin acid composition is obtained by hydrolyzing the obtained tackifier (rosin ester) according to a standard method (adding KOH in n-hexanol and refluxing for 2 hours, then neutralizing with hydrochloric acid, Provided to analysis) and then determined by gas chromatography.
比較例７
不均化ロジン（酸価１６７、軟化点７７℃、荒川化学工業（株）製）を窒素シール下に３ｍｍＨｇの減圧下で蒸留し、酸価１７４、軟化点８２℃、色調ガードナー２５０Ｈの精製不均化ロジンを得た。精製不均化ロジンとグリセリンを実施例１と同様の方法でエステル化し、軟化点１００℃、酸価６、色調２５０Ｈの粘着付与剤を１０３ｇ得た。樹脂酸組成は、得られた粘着付与剤（ロジンエステル）を定法に従って加水分解（ｎ−ヘキサノール中ＫＯＨを加えて、２時間還流反応させた後に、塩酸で中性とし、得られた樹脂酸を分析に提供する。）した後に、ガスクロマトグラフィーで決定した。
Comparative Example 7
Disproportionated rosin (acid number 167, softening point 77 ° C., Arakawa Chemical Industries, Ltd.) was distilled under a reduced pressure of 3 mmHg under a nitrogen seal to give an acid number 174, softening point 82 ° C., tone Gardner 250H. An averaged rosin was obtained. Purified disproportionated rosin and glycerin were esterified in the same manner as in Example 1 to obtain 103 g of a tackifier having a softening point of 100 ° C., an acid value of 6, and a color tone of 250H. The resin acid composition is obtained by hydrolyzing the obtained tackifier (rosin ester) according to a standard method (adding KOH in n-hexanol and refluxing for 2 hours, then neutralizing with hydrochloric acid, Provided to analysis) and then determined by gas chromatography.
（２７６ｎｍにおける吸光度Ａ（１％ １ｃｍ）の算出）
得られた粘着付与剤５０．０ｍｇを２５ｍｌメスフラスコに精秤し、シクロヘキサン：エタノール＝１：１混合溶媒で溶解した後、２５ｍｌの秤線まで定容する。ピペットにて１ｍｌを量りとり２０ｍｌメスフラスコへ移し、２０ｍｌの秤線まで定容し２０倍希釈液とする。ＵＶ分光光度計（ＨＩＴＡＣＨＩ ｕ−３２１０ spectrophotometer）にて、セル厚１ｃｍの石英セルを用いることにより吸光度を測定する。２７６ｎｍにある極大ピークの吸光度を読み取る。得られた吸光度を１００倍することにより、吸光度Ａ（１％ １ｃｍ）を得る。結果を表１に示す。
なお、吸光度Ａ（１％ １ｃｍ）の１％は、基質（粘着付与樹脂）濃度を表し、１ｗ／ｖ％＝１基質重量／溶媒体積％のことを言う。１ｃｍは測定セルの光路長が１ｃｍであることを表す。
(Calculation of absorbance A (1% 1 cm) at 276 nm)
50.0 mg of the resulting tackifier is precisely weighed into a 25 ml volumetric flask, dissolved in a mixed solvent of cyclohexane: ethanol = 1: 1, and then the volume is adjusted to a 25 ml weighing line. Pipette 1 ml and transfer to a 20 ml volumetric flask. Keep the volume up to 20 ml and make 20-fold diluted solution. Absorbance is measured using a quartz cell having a cell thickness of 1 cm with a UV spectrophotometer (HITACHI u-3210 spectrophotometer). Read the absorbance of the maximum peak at 276 nm. Absorbance A (1% 1 cm) is obtained by multiplying the obtained absorbance by 100. The results are shown in Table 1.
In addition, 1% of the absorbance A (1% 1 cm) represents a substrate (tackifying resin) concentration, which means 1 w / v% = 1 substrate weight / solvent volume%. 1 cm represents that the optical path length of the measurement cell is 1 cm.
（ＮＭＲピークの観測）
重クロロホルム溶媒に得られた粘着付与剤を溶解し（５％溶液）、１Ｈ−ＮＭＲを測定した（Ｖａｒｉａｎ ＧＥＭＩＮＩ−３００ ３００ＭＨｚ）。０〜１０ｐｐｍ領域におけるプロトン積分値、５．４〜６．６ｐｐｍ領域における積分値を算出し、その比を指標としてオレフィン性二重結合の存在量を下記式より数値化（％）した。結果を表１に示す。
(NMR peak observation)
The obtained tackifier was dissolved in deuterated chloroform solvent (5% solution), and 1 H-NMR was measured (Varian GEMINI-300 300 MHz). The proton integral value in the 0 to 10 ppm region was calculated, and the integral value in the 5.4 to 6.6 ppm region was calculated, and the abundance of the olefinic double bond was quantified (%) from the following formula using the ratio as an index. The results are shown in Table 1.
（耐熱性）
得られた粘着付与剤１０gを試験管に採取し、200℃循風乾燥器に入れ、２時間後の色調を測定した。（ガードナーカラー表示）結果を表１に示す。
(Heat-resistant)
10 g of the obtained tackifier was collected in a test tube, put in a 200 ° C. circulating air dryer, and the color tone after 2 hours was measured. (Gardner color display) Table 1 shows the results.
（耐候性）
６０〜１００メッシュに粉砕した樹脂２．０ｇを採取し、４００Ｗ紫外線ランプを４０ｃｍの距離から１５時間照射した時の照射前後の色調（５０％トルエン溶液）を測定した。結果を表１に示す。
(Weatherability)
2.0 g of resin pulverized to 60 to 100 mesh was collected, and the color tone (50% toluene solution) before and after irradiation when a 400 W ultraviolet lamp was irradiated for 15 hours from a distance of 40 cm was measured. The results are shown in Table 1.
（アクリルポリマー相溶性）
製造例４で得たアクリル重合体組成物（５０％酢酸エチル溶液）４．２ｇと、粘着付与樹脂の５０％トルエン溶液１．８ｇを混合する。この混合液をガラス板上に塗布し、風乾ののち１０５℃循風乾燥機中で５分間乾燥後、取り出し室温まで冷却する。相溶性を目視評価した。結果を表１に示す。
○ 透明 △うすく白濁 ×白濁
(Acrylic polymer compatibility)
4.2 g of the acrylic polymer composition (50% ethyl acetate solution) obtained in Production Example 4 and 1.8 g of a 50% toluene solution of a tackifier resin are mixed. This mixed solution is coated on a glass plate, air-dried, dried in a circulating dryer at 105 ° C. for 5 minutes, taken out, and cooled to room temperature. The compatibility was visually evaluated. The results are shown in Table 1.
○ Transparent △ Lightly cloudy × Cloudy
（ＳＩＳ系ゴム相溶性）
ポリスチレン−ポリイソプレン−ポリスチレン系ブロックゴム（クインタック３４２１、日本ゼオン）の２５％トルエン溶液４．０ｇと、粘着付与樹脂の５０％トルエン溶液２．０ｇを混合する。この混合液をガラス板上に塗布し、風乾ののち１０５℃循風乾燥機中で５分間乾燥後、取り出し室温まで冷却する。相溶性を目視評価した。結果を表１に示す。
○ 透明 △うすく白濁 ×白濁
(SIS rubber compatibility)
4.0 g of 25% toluene solution of polystyrene-polyisoprene-polystyrene block rubber (Quintac 3421, Nippon Zeon) and 2.0 g of 50% toluene solution of tackifying resin are mixed. This mixed solution is coated on a glass plate, air-dried, dried in a circulating dryer at 105 ° C. for 5 minutes, taken out, and cooled to room temperature. The compatibility was visually evaluated. The results are shown in Table 1.
○ Transparent △ Lightly cloudy × Cloudy
（溶剤型アクリル系粘着剤組成物の調製）
製造例４で得られた溶剤型アクリル系重合体ワニス１００部に、実施例１〜８、比較例１〜７で得られた、樹脂の５０％トルエンワニスを２０部後添加した後、架橋剤としてポリイソシアネート系化合物（日本ポリウレタン（株）製、商品名「コロネートＬ」）１．６部を添加し、溶剤型アクリル系粘接着剤組成物を得た。得られた溶剤型アクリル系粘接着剤組成物を厚さ３８μｍのポリエステルフィルムにサイコロ型アプリケーターにて乾燥膜厚が３０μｍ程度となるように塗布（塗工幅２５ｍｍ）し、次いで該粘接着剤組成物ワニス中の溶剤を風乾の後１０５℃循風乾燥機中で５分間乾燥して試料テープを作成し、後述の性能評価方法にて各種試験を行った。
(Preparation of solvent-type acrylic pressure-sensitive adhesive composition)
After adding 20 parts of the resin 50% toluene varnish obtained in Examples 1 to 8 and Comparative Examples 1 to 7 to 100 parts of the solvent-based acrylic polymer varnish obtained in Production Example 4, the crosslinking agent was added. As a polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate L”), 1.6 parts were added to obtain a solvent-type acrylic adhesive composition. The obtained solvent-type acrylic adhesive composition was applied to a polyester film having a thickness of 38 μm with a dice-type applicator so that the dry film thickness was about 30 μm (coating width 25 mm), and then the adhesive was bonded. The solvent in the agent composition varnish was air-dried and then dried in a circulating air dryer at 105 ° C. for 5 minutes to prepare a sample tape, and various tests were conducted by the performance evaluation method described later.
（接着力）
ＪＩＳ Ｚ ０２３７法に従い、上記試料テープを、２ｋｇのゴムローラーを用いて、被着体であるポリエチレン板基材に接着面積２５ｍｍ×１２５ｍｍで圧着後、２０℃で２４時間放置した。その後テンシロン引張り試験機で２０℃にて剥離速度３００ｍｍ／分で１８０°剥離試験を行い幅２５ｍｍあたりの接着力（Ｎ／２５ｍｍ）を測定した。結果を表２に示す。
(Adhesive strength)
According to JIS Z 0237 method, the above-mentioned sample tape was pressure-bonded to a polyethylene plate substrate as an adherend with an adhesion area of 25 mm × 125 mm using a 2 kg rubber roller, and then allowed to stand at 20 ° C. for 24 hours. Thereafter, a 180 ° peel test was conducted at 20 ° C. and a peel rate of 300 mm / min with a Tensilon tensile tester, and the adhesive force per 25 mm width (N / 25 mm) was measured. The results are shown in Table 2.
（タック）
ＰＳＴＣ−６法に従い、３０度の角度を有する斜面から、Ｎｏ．１４の鋼球を転がし、水平面に置いた粘着面（試料テープ）上で鋼球が転がる距離（ｃｍ）を測定した。距離（ｃｍ）が短いほどタックに優れる。測定雰囲気温度は、２０℃である。結果を表２に示す。
(tack)
According to the PSTC-6 method, from a slope having an angle of 30 degrees, No. 14 steel balls were rolled, and the distance (cm) of rolling of the steel balls on an adhesive surface (sample tape) placed on a horizontal surface was measured. The shorter the distance (cm), the better the tack. The measurement ambient temperature is 20 ° C. The results are shown in Table 2.
（保持力）
ＰＳＴＣ−７法に従い、試料テープとステンレス鋼板を２ｋｇのゴムローラーを用いて、接着面積２５ｍｍ×２５ｍｍで圧着した後、２０℃で２４時間放置した。その後クリープテスターで４０℃、１ｋｇ、１時間の条件で荷重をかけたときの試料テープ（ポリエステルフィルム）とステンレス鋼板とのズレ（ｍｍ）を測定した。ズレ（ｍｍ）が短いほど保持力に優れる。結果を表２に示す。
(Holding power)
According to the PSTC-7 method, the sample tape and the stainless steel plate were pressure-bonded at a bonding area of 25 mm × 25 mm using a 2 kg rubber roller, and then allowed to stand at 20 ° C. for 24 hours. Thereafter, the deviation (mm) between the sample tape (polyester film) and the stainless steel plate when a load was applied with a creep tester under the conditions of 40 ° C., 1 kg, and 1 hour was measured. The shorter the deviation (mm), the better the holding power. The results are shown in Table 2.
（ＳＩＳ系ブロックゴム粘着剤組成物の調製）
ＳＩＳ型ブロック共重合体（商品名「クインタック３４２１」、日本ゼオン（株）製）５０ｇ、およびパラフィン系オイル（商品名「ＤＩプロセスＰＷ９０」、出光興産（株）製）１５ｇ、実施例１〜８、比較例１〜７で得られた樹脂５０ｇを、１１５ｇのトルエンに溶解し、粘着剤組成物の５０％ワニスを調製した。得られた粘着剤組成物ワニスを厚さ３８μｍのポリエステルフィルムにサイコロ型アプリケーターにて乾燥膜厚が３０μｍ程度となるように塗布（塗工幅２５ｍｍ）し、次いで該粘接着剤組成物ワニス中の溶剤を風乾の後１０５℃循風乾燥機中で５分間乾燥して試料テープを作成し、後述の性能評価方法にて各種試験を行った。
(Preparation of SIS block rubber adhesive composition)
50 g of SIS type block copolymer (trade name “Quintac 3421”, manufactured by Nippon Zeon Co., Ltd.), and 15 g of paraffinic oil (trade name “DI Process PW90”, manufactured by Idemitsu Kosan Co., Ltd.), Examples 1 to 8. 50 g of the resin obtained in Comparative Examples 1 to 7 was dissolved in 115 g of toluene to prepare a 50% varnish of an adhesive composition. The obtained pressure-sensitive adhesive composition varnish was applied to a polyester film having a thickness of 38 μm with a dice applicator so that the dry film thickness was about 30 μm (coating width 25 mm), and then in the pressure-sensitive adhesive composition varnish. The solvent was air-dried and then dried in a circulating drier at 105 ° C. for 5 minutes to prepare a sample tape, and various tests were performed by the performance evaluation method described later.
（接着力）
ＪＩＳ Ｚ ０２３７法に従い、上記試料テープを、２ｋｇのゴムローラーを用いて、被着体であるポリエチレン板基材に接着面積２５ｍｍ×１２５ｍｍで圧着後、２０℃で２４時間放置した。その後テンシロン引張り試験機で２０℃にて剥離速度３００ｍｍ／分で１８０°剥離試験を行い幅２５ｍｍあたりの接着力（Ｎ／２５ｍｍ）を測定した。結果を表３に示す。
(Adhesive strength)
According to JIS Z 0237 method, the above-mentioned sample tape was pressure-bonded to a polyethylene plate substrate as an adherend with an adhesion area of 25 mm × 125 mm using a 2 kg rubber roller, and then allowed to stand at 20 ° C. for 24 hours. Thereafter, a 180 ° peel test was conducted at 20 ° C. and a peel rate of 300 mm / min with a Tensilon tensile tester, and the adhesive force per 25 mm width (N / 25 mm) was measured. The results are shown in Table 3.
（タック）
ＰＳＴＣ−６法に従い、３０度の角度を有する斜面から、Ｎｏ．１４の鋼球を転がし、水平面に置いた粘着面（試料テープ）上で鋼球が転がる距離（ｃｍ）を測定した。距離（ｃｍ）が短いほどタックに優れる。測定雰囲気温度は、２０℃である。結果を表３に示す。
(tack)
According to the PSTC-6 method, from a slope having an angle of 30 degrees, No. 14 steel balls were rolled, and the distance (cm) of rolling of the steel balls on an adhesive surface (sample tape) placed on a horizontal surface was measured. The shorter the distance (cm), the better the tack. The measurement ambient temperature is 20 ° C. The results are shown in Table 3.
（保持力）
ＰＳＴＣ−７法に従い、試料テープとステンレス鋼板を２ｋｇのゴムローラーを用いて、接着面積２５ｍｍ×２５ｍｍで圧着した後、２０℃で２４時間放置した。その後クリープテスターで４０℃、１ｋｇ、３時間の条件で荷重をかけたときの試料テープ（ポリエステルフィルム）とステンレス鋼板とのズレ（ｍｍ）を測定した。ズレ（ｍｍ）が短いほど保持力に優れる。結果を表３に示す。
(Holding power)
According to the PSTC-7 method, the sample tape and the stainless steel plate were pressure-bonded at a bonding area of 25 mm × 25 mm using a 2 kg rubber roller, and then allowed to stand at 20 ° C. for 24 hours. Thereafter, the deviation (mm) between the sample tape (polyester film) and the stainless steel plate when a load was applied under the conditions of 40 ° C., 1 kg, and 3 hours with a creep tester was measured. The shorter the deviation (mm), the better the holding power. The results are shown in Table 3.
表中、ＤＥＡはデヒドロアビエチン酸、ＴＨＡはテトラヒドロアビエチン酸、ＤＨＡはジヒドロアビエチン酸を表す。 In the table, DEA represents dehydroabietic acid, THA represents tetrahydroabietic acid, and DHA represents dihydroabietic acid.
Claims (12)
A medical patch obtained using the pressure-sensitive adhesive or adhesive composition according to claim 10.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
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| JP2007255577A JP4534258B2 (en) | 2007-09-28 | 2007-09-28 | Tackifier, tackifier for medical patch, adhesive or adhesive composition, and adhesive for medical patch |
| TW97135744A TWI469769B (en) | 2007-09-28 | 2008-09-18 | Tackifier, tackifier for medical cataplasm, tacky or adhesive composition, tacky agent for medical cataplasm, tacky or adhesive tape and medical cataplasm |
| KR1020080091388A KR101520356B1 (en) | 2007-09-28 | 2008-09-18 | Tackifier, tackifier for medical cataplasm, tacky or adhesive composition, tacky agent for medical cataplasm, tacky or adhesive tape and medical cataplasm |
| CN 200810167108 CN101397479B (en) | 2007-09-28 | 2008-09-27 | Adhesion-imparting agent, adhesive or adhesive composite, bonding or adhesive belt and medical paster |
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| JP2007255577A JP4534258B2 (en) | 2007-09-28 | 2007-09-28 | Tackifier, tackifier for medical patch, adhesive or adhesive composition, and adhesive for medical patch |
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| JP4534258B2 JP4534258B2 (en) | 2010-09-01 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013111883A1 (en) * | 2012-01-28 | 2013-08-01 | 荒川化学工業株式会社 | Adhesiveness-imparting agent, adhesiveness-imparting agent for medical or industrial applications, adhesive/cohesive agent for medical or industrial applications, adhesive/cohesive sheet for medial or industrial applications, and adhesive tape for medial or industrial applications |
| WO2015048415A3 (en) * | 2013-09-27 | 2015-07-16 | Arizona Chemical Company, Llc | Rosin esters and compositions thereof |
| WO2015048421A3 (en) * | 2013-09-27 | 2015-07-16 | Arizona Chemical Company, Llc | Rosin esters and compositions thereof |
| JP2016535113A (en) * | 2013-09-27 | 2016-11-10 | アリゾナ・ケミカル・カンパニー・エルエルシー | Composition comprising ethylene polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009209178A (en) * | 2008-02-29 | 2009-09-17 | Arakawa Chem Ind Co Ltd | Tackifier, tackifier for medical cataplasm, self-adhesive or adhesive composition, self-adhesive for medical cataplasm, self-adhesive or adhesive tape and medical cataplasm |
| CN101612141B (en) * | 2009-07-29 | 2012-10-03 | 考司美德制药株式会社 | Buprenorphine patch |
| CN106496500A (en) * | 2016-10-19 | 2017-03-15 | 佛山市顺德区巴德富实业有限公司 | A kind of high tack hot melt polyurethane adhesive and preparation method thereof |
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| US5120781A (en) * | 1991-05-07 | 1992-06-09 | Union Camp Corporation | Acid-modified polyhydric alcohol rosin ester tackifiers and hot melt adhesive compositions containing those tackifiers |
| KR101195286B1 (en) * | 2005-03-30 | 2012-10-26 | 아라까와 가가꾸 고교 가부시끼가이샤 | Adhesion-Imparting Agent And Adhesion-Imparting Resin Emulsion |
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| JPH01161078A (en) * | 1987-12-18 | 1989-06-23 | Toagosei Chem Ind Co Ltd | Preparation of emulsified self-adhesive |
| JPH05279631A (en) * | 1992-03-30 | 1993-10-26 | Arakawa Chem Ind Co Ltd | Production of rosin ester |
| JPH0959570A (en) * | 1995-08-22 | 1997-03-04 | Arakawa Chem Ind Co Ltd | Rosin derivative and its production |
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| WO2013111883A1 (en) * | 2012-01-28 | 2013-08-01 | 荒川化学工業株式会社 | Adhesiveness-imparting agent, adhesiveness-imparting agent for medical or industrial applications, adhesive/cohesive agent for medical or industrial applications, adhesive/cohesive sheet for medial or industrial applications, and adhesive tape for medial or industrial applications |
| JPWO2013111883A1 (en) * | 2012-01-28 | 2015-05-11 | 荒川化学工業株式会社 | Tackifier, medical or industrial tackifier, medical or industrial adhesive / adhesive, medical or industrial adhesive / adhesive sheet, and medical or industrial adhesive tape |
| US9758703B2 (en) | 2012-01-28 | 2017-09-12 | Arakawa Chemical Industries, Ltd. | Tackifier, tackifier for medical or industrial use, adhesive and/or pressure-sensitive adhesive for medical or industrial use, adhesive sheet and/or pressure-sensitive adhesive sheet for medical or industrial use, and pressure-sensitive adhesive tape for medical or industrial use |
| JP2016535113A (en) * | 2013-09-27 | 2016-11-10 | アリゾナ・ケミカル・カンパニー・エルエルシー | Composition comprising ethylene polymer |
| KR20160061381A (en) * | 2013-09-27 | 2016-05-31 | 아리조나 케미칼 캄파니, 엘엘씨 | Rosin esters and compositions thereof |
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| CN101397479B (en) | 2013-07-03 |
| JP4534258B2 (en) | 2010-09-01 |
| CN101397479A (en) | 2009-04-01 |
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