JP2016094492A - Acrylic adhesive composition and adhesive tape - Google Patents
Acrylic adhesive composition and adhesive tape Download PDFInfo
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Abstract
Description
本発明は、アクリル系粘着剤組成物ならびに粘着テープに関する。 The present invention relates to an acrylic pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape.
アクリル系粘着剤組成物において、早期に架橋反応を完了させる目的で錫触媒が使用されている（特許文献１参照）。近年、環境の観点から錫を使用しない粘着テープが求められている。特許文献２には、２つの異なるアクリル系共重合体とイソシアネート化合物、ジルコニウム錯体、ならびに過剰のアセチルアセトンなどのキレート剤を含む粘着剤組成物が記載されている。この粘着剤組成物では、凝集力と応力緩和性の調整を容易にすることができ、養生期間が数日に短縮され、耐久性の向上、白ヌケの発生の抑制ができると記載されている。
アクリル系粘着剤においては、錫不使用で、十分なポットライフを有しながら養生の要らない粘着剤組成物が求められていた。
In the acrylic pressure-sensitive adhesive composition, a tin catalyst is used for the purpose of completing the crosslinking reaction at an early stage (see Patent Document 1). In recent years, there has been a demand for an adhesive tape that does not use tin from the viewpoint of the environment. Patent Document 2 describes a pressure-sensitive adhesive composition containing two different acrylic copolymers, an isocyanate compound, a zirconium complex, and an excess of a chelating agent such as acetylacetone. In this adhesive composition, it is described that it is possible to easily adjust the cohesive force and stress relaxation property, the curing period is shortened to several days, durability can be improved, and generation of white spots can be suppressed. .
In the acrylic pressure-sensitive adhesive, there has been a demand for a pressure-sensitive adhesive composition that does not require curing while not using tin and having a sufficient pot life.
従って、本発明の課題は、汎用性の高いアクリル系粘着剤組成物において、錫触媒を使用せずに、乾燥直後に被着体に直接貼り合せることができ、１工程で加工可能な粘着層ならびにそれを含む粘着テープを製造することにある。 Accordingly, an object of the present invention is to provide a highly versatile acrylic pressure-sensitive adhesive composition that can be directly bonded to an adherend immediately after drying without using a tin catalyst and can be processed in one step. And manufacturing an adhesive tape containing the same.
本発明者らは、上記課題に鑑み鋭意研究した結果、アクリル系共重合体とイソシアネート系硬化剤と特定量のジルコニウム錯体触媒と特定量の遅延剤とを含み、特定の乾燥条件で乾燥後に養生が不要となるアクリル系粘着剤組成物が、被着体に直接貼り合せることができ、１工程で加工可能であることを見出し、本発明を完成するに至った。 As a result of diligent research in view of the above problems, the inventors of the present invention include an acrylic copolymer, an isocyanate curing agent, a specific amount of a zirconium complex catalyst, and a specific amount of a retarder, and are cured after drying under specific drying conditions. The present inventors have found that an acrylic pressure-sensitive adhesive composition that eliminates the need can be directly bonded to an adherend and can be processed in one step, thereby completing the present invention.
すなわち、本発明のアクリル系粘着剤組成物（Ｉ）は、アクリル系共重合体（Ａ）と、イソシアネート系硬化剤（Ｂ）と、ジルコニウム錯体触媒（Ｃ）と、遅延剤（Ｄ）とを含んでいる。上記ジルコニウム錯体触媒（Ｃ）の含有量は、上記アクリル系共重合体（Ａ）１００質量部に対して、０．０２質量部以上であり、上記遅延剤（Ｄ）の含有量は、上記ジルコニウム錯体触媒（Ｃ）１質量部に対して、３０〜３５０質量部である。さらに、本発明のアクリル系粘着剤組成物は、４０℃〜１４０℃、０．５分〜５分の乾燥条件で乾燥後に養生が不要である。
本発明のアクリル系粘着剤組成物（Ｉ）は、好ましくは、上記乾燥条件で乾燥後の上記アクリル系粘着剤組成物（Ｉ）について測定したイソシアネートピークの面積が、１１０℃、２分の乾燥条件で乾燥後の基準アクリル系粘着剤組成物について測定したイソシアネートピークの面積を１００％とした場合に、５５％以下である。なお、イソシアネートピークと基準アクリル系粘着剤組成物は、以下のように定義される。
・イソシアネートピーク：ＦＴ−ＩＲチャートに表れる２２７５ｃｍ−１のイソシアネート基の逆対称伸縮ＩＲピーク
・基準アクリル系粘着剤組成物：上記アクリル系共重合体（Ａ）と上記イソシアネート系硬化剤（Ｂ）とを上記アクリル系粘着剤組成物（Ｉ）とほぼ同じ割合で含み、上記ジルコニウム錯体触媒（Ｃ）と上記遅延剤（Ｄ）とを含まないアクリル系粘着剤組成物
That is, the acrylic pressure-sensitive adhesive composition (I) of the present invention comprises an acrylic copolymer (A), an isocyanate curing agent (B), a zirconium complex catalyst (C), and a retarder (D). Contains. The content of the zirconium complex catalyst (C) is 0.02 parts by mass or more with respect to 100 parts by mass of the acrylic copolymer (A), and the content of the retarder (D) is the zirconium. It is 30-350 mass parts with respect to 1 mass part of complex catalysts (C). Furthermore, the acrylic pressure-sensitive adhesive composition of the present invention does not require curing after drying under the drying conditions of 40 ° C. to 140 ° C. and 0.5 minutes to 5 minutes.
The acrylic pressure-sensitive adhesive composition (I) of the present invention preferably has an isocyanate peak area measured with respect to the acrylic pressure-sensitive adhesive composition (I) after drying under the above-mentioned drying conditions, dried at 110 ° C. for 2 minutes. When the area of the isocyanate peak measured for the reference acrylic pressure-sensitive adhesive composition after drying under conditions is 100%, it is 55% or less. In addition, an isocyanate peak and a reference | standard acrylic adhesive composition are defined as follows.
・ Isocyanate peak: reverse symmetric stretching IR peak of 2275 cm −1 isocyanate group appearing on the FT-IR chart ・ Reference acrylic pressure-sensitive adhesive composition: acrylic copolymer (A) and isocyanate curing agent (B) In the same proportion as the acrylic pressure-sensitive adhesive composition (I), and does not include the zirconium complex catalyst (C) and the retarder (D).
また、本発明の粘着テープは、基材と、上記基材上に配置され、上記のアクリル系粘着剤組成物を上記乾燥条件で乾燥した粘着層とを含んでいる。 Moreover, the adhesive tape of this invention contains the base material and the adhesive layer which is arrange | positioned on the said base material and dried said acrylic adhesive composition on the said drying conditions.
本発明によれば、被着体に直接貼り合せることができ、１工程で加工可能なアクリル系粘着剤組成物ならびにそれを含む粘着テープを製造できる。本発明のアクリル系粘着剤組成物は、錫レスであるため、環境に優しく、また、アクリル系粘着剤であるため、汎用性が高い粘着テープをより低コストで製造できる。また、本発明の粘着テープによれば、環境に優しく、汎用性が高い粘着テープをより低コストで製造できる。また、各種保護フィルム等に使用される微粘着の粘着テープにおいては、セパレータレスとすることも可能である。さらには、強粘着の粘着テープにおいては、巻き取り後の経時凹凸の発生等の継時変化の少ない粘着層ならびにそれを含む粘着テープを製造できる。 According to the present invention, an acrylic pressure-sensitive adhesive composition that can be directly bonded to an adherend and can be processed in one step, and a pressure-sensitive adhesive tape including the same can be produced. Since the acrylic pressure-sensitive adhesive composition of the present invention is tin-free, it is environmentally friendly, and since it is an acrylic pressure-sensitive adhesive, a highly versatile pressure-sensitive adhesive tape can be produced at a lower cost. Further, according to the pressure-sensitive adhesive tape of the present invention, a pressure-sensitive adhesive tape that is environmentally friendly and highly versatile can be produced at a lower cost. Moreover, in the slightly adhesive adhesive tape used for various protective films etc., it is also possible to make it separatorless. Furthermore, in the strongly adhesive pressure-sensitive adhesive tape, it is possible to produce an adhesive layer with little change over time such as occurrence of unevenness with time after winding, and an adhesive tape including the same.
１．アクリル系粘着剤組成物（Ｉ）
本発明のアクリル系粘着剤組成物（Ｉ）は、アクリル系共重合体（Ａ）と、イソシアネート系硬化剤（Ｂ）と、ジルコニウム錯体触媒（Ｃ）と、遅延剤（Ｄ）とを含んでいる。
1. Acrylic adhesive composition (I)
The acrylic pressure-sensitive adhesive composition (I) of the present invention contains an acrylic copolymer (A), an isocyanate curing agent (B), a zirconium complex catalyst (C), and a retarder (D). Yes.
１−１ アクリル系共重合体（Ａ）
本発明のアクリル系粘着剤組成物（Ｉ）に含まれるアクリル系共重合体（Ａ）としては、特に限定されず、公知のアクリル系共重合体が使用できる。具体的には、例えば、（メタ）アクリル酸エステル単量体と反応性官能基を有する単量体とを共重合させた共重合体が挙げられる。アクリル系共重合体（Ａ）を合成する単量体成分中、（メタ）アクリル酸エステル単量体が５０質量％以上含まれることが好ましく、６０質量％以上含まれることがより好ましい。
1-1 Acrylic copolymer (A)
The acrylic copolymer (A) contained in the acrylic pressure-sensitive adhesive composition (I) of the present invention is not particularly limited, and known acrylic copolymers can be used. Specific examples include a copolymer obtained by copolymerizing a (meth) acrylic acid ester monomer and a monomer having a reactive functional group. In the monomer component for synthesizing the acrylic copolymer (A), the (meth) acrylic acid ester monomer is preferably contained in an amount of 50% by mass or more, and more preferably 60% by mass or more.
反応性官能基を有する単量体としては、例えば、カルボキシル基含有単量体、水酸基含有単量体、グリシジル基含有単量体、アミド基，Ｎ−置換アミド基含有単量体、三級アミノ基含有単量体等が挙げられ、これらの１種又は２種以上を用いることができる。なかでも水酸基含有単量体が好ましい。 Examples of the monomer having a reactive functional group include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, a glycidyl group-containing monomer, an amide group, an N-substituted amide group-containing monomer, and a tertiary amino acid. Examples thereof include group-containing monomers, and one or more of these can be used. Of these, a hydroxyl group-containing monomer is preferred.
アクリル系共重合体（Ａ）としては、例えば、ＳＫ−１４９６［綜研化学（株）製］、ダイカラック５２５０［大同化成工業（株）製］などの市販品を好適に使用できる。 As the acrylic copolymer (A), for example, commercially available products such as SK-1496 [manufactured by Soken Kagaku Co., Ltd.] and Daikarak 5250 [manufactured by Daido Kasei Kogyo Co., Ltd.] can be suitably used.
アクリル系粘着剤組成物におけるアクリル系共重合体（Ａ）の含有量は、５〜６０質量％が好ましく、５〜４０質量％がより好ましく、１０〜３５質量％がさらに好ましい。 The content of the acrylic copolymer (A) in the acrylic pressure-sensitive adhesive composition is preferably 5 to 60% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 35% by mass.
１−２ イソシアネート系硬化剤（Ｂ）
本発明のアクリル系粘着剤組成物に含まれるイソシアネート系硬化剤（Ｂ）としては、特に限定されないが、例えば、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、トリフェニルメタントリイソシアネート、トリレンジイソシアネート等の芳香族イソシアネート；ヘキサ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、上記芳香族イソシアネート化合物の水素添加物等の脂肪族又は脂環族イソシアネート；それらイソシアネートの２量体もしくは３量体又はそれらイソシアネートと、トリメチロールプロパンなどのポリオールの付加物などの各種イソシアネートに由来するイソシアネート化合物が挙げられる。これらは単独で、あるいは２種以上を組み合せて使用することができる。
1-2 Isocyanate-based curing agent (B)
The isocyanate-based curing agent (B) contained in the acrylic pressure-sensitive adhesive composition of the present invention is not particularly limited. For example, aromatic isocyanates such as xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, and tolylene diisocyanate Aliphatic or alicyclic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated products of the above aromatic isocyanate compounds; dimer or trimer of these isocyanates or addition of these isocyanates and polyols such as trimethylolpropane; And isocyanate compounds derived from various isocyanates such as products. These may be used alone or in combination of two or more.
イソシアネート化合物（Ｂ）としては、例えば「コロネートＬ」、「コロネートＨＸ」、「コロネートＨＬ−Ｓ」、「コロネート２２３４」［以上日本ポリウレタン工業（株）製］などの市販品を好適に使用できる。 As the isocyanate compound (B), for example, commercially available products such as “Coronate L”, “Coronate HX”, “Coronate HL-S”, “Coronate 2234” [manufactured by Nippon Polyurethane Industry Co., Ltd.] can be suitably used.
イソシアネート系硬化剤（Ｂ）の含有量としては、アクリル系共重合体（Ａ）１００質量部に対し、０．１〜２０質量部が好ましく、０．１〜１０質量部がより好ましく、０．１質量部以上５質量部未満がさらに好ましい。 As content of an isocyanate type hardening | curing agent (B), 0.1-20 mass parts is preferable with respect to 100 mass parts of acrylic copolymers (A), 0.1-10 mass parts is more preferable, and 0.1. The amount is more preferably 1 part by mass or more and less than 5 parts by mass.
１−３ ジルコニウム錯体触媒（Ｃ）
本発明のアクリル系粘着剤組成物（Ｉ）に含まれるジルコニウム錯体触媒（Ｃ）としては、特に限定されないが、例えば、ジルコニウムテトラアセチルアセトネート等のジルコニウムとアセチルアセトンとがキレート化したものが挙げられる。
1-3 Zirconium complex catalyst (C)
The zirconium complex catalyst (C) contained in the acrylic pressure-sensitive adhesive composition (I) of the present invention is not particularly limited, and examples thereof include those obtained by chelating zirconium such as zirconium tetraacetylacetonate with acetylacetone. .
ジルコニウム錯体触媒（Ｃ）としては、例えば、「オルガチックスＺＣ−１５０」、「オルガチックスＺＣ−５４０」、「オルガチックスＺＣ−５７０」、「オルガチックスＺＣ−５８０」、「オルガチックスＺＣ−７００」［マツモトファインケミカル（株）製］などの市販品を好適に使用することができる。 Examples of the zirconium complex catalyst (C) include “Orgatics ZC-150”, “Orgatics ZC-540”, “Orgatics ZC-570”, “Orgatics ZC-580”, and “Orgatics ZC-700”. Commercial products such as [Matsumoto Fine Chemical Co., Ltd.] can be preferably used.
ジルコニウム錯体触媒（Ｃ）の含有量は、上記アクリル系共重合体（Ａ）１００質量部に対して、０．０２質量部以上（例えば０．０２〜０．４０質量部）であり、好ましくは、０．１質量部超０．４０質量部以下、より好ましくは０．１２〜０．３５質量部、さらに好ましくは０．１４〜０．３５質量部である。ジルコニウム錯体触媒（Ｃ）の含有量をこのような範囲とすることにより、十分なポットライフを有しながら、４０℃〜１４０℃、０．５分〜５分の乾燥条件で乾燥後に養生が不要なアクリル系粘着剤組成物とすることができる。 The content of the zirconium complex catalyst (C) is 0.02 parts by mass or more (for example, 0.02 to 0.40 parts by mass) with respect to 100 parts by mass of the acrylic copolymer (A), preferably More than 0.1 part by mass and 0.40 part by mass or less, more preferably 0.12 to 0.35 part by mass, and still more preferably 0.14 to 0.35 part by mass. By setting the content of the zirconium complex catalyst (C) in such a range, curing is unnecessary after drying under drying conditions of 40 ° C. to 140 ° C. and 0.5 minutes to 5 minutes while having a sufficient pot life. Acrylic pressure-sensitive adhesive composition can be obtained.
１−４ 遅延剤（Ｄ）
本発明のアクリル系粘着剤組成物（Ｉ）に含まれる遅延剤（Ｄ）としては、例えばβ−ジケトン類やβ−ケトエステル類等を用いることができ、具体的にはアセチルアセトン、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸−ｎ−プロピル、アセト酢酸−ｉ−プロピル等が挙げられる。なかでも、アセチルアセトンが好ましい。
1-4 Retarder (D)
As the retarder (D) contained in the acrylic pressure-sensitive adhesive composition (I) of the present invention, for example, β-diketones and β-ketoesters can be used. Specifically, acetylacetone, methyl acetoacetate, Examples include ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, and the like. Of these, acetylacetone is preferred.
遅延剤（Ｄ）の含有量は、上記ジルコニウム錯体触媒（Ｃ）１質量部に対して、３０〜３５０質量部であり、好ましくは３０〜３００質量部であり、より好ましくは３０〜１００質量部であり、さらに好ましくは３０質量部以上５０質量部未満である。遅延剤（Ｄ）の含有量をこのような範囲とすることにより、十分なポットライフを有しながら、養生レスのアクリル系粘着剤組成物とすることができる。 The content of the retarder (D) is 30 to 350 parts by weight, preferably 30 to 300 parts by weight, more preferably 30 to 100 parts by weight with respect to 1 part by weight of the zirconium complex catalyst (C). More preferably, it is 30 parts by mass or more and less than 50 parts by mass. By setting the content of the retarder (D) in such a range, a curing-less acrylic pressure-sensitive adhesive composition can be obtained while having a sufficient pot life.
１−５ その他の成分
本発明のアクリル系粘着剤組成物（Ｉ）は、本発明の効果を損なわない範囲で、例えば、各種添加剤、溶剤、粘着付与剤、耐候性安定剤、可塑剤、軟化剤、染料、顔料、無機充填剤等のその他の成分を含んでいてもよい。
1-5 Other components The acrylic pressure-sensitive adhesive composition (I) of the present invention is, for example, various additives, solvents, tackifiers, weathering stabilizers, plasticizers, and the like within a range not impairing the effects of the present invention. Other components such as a softener, a dye, a pigment, and an inorganic filler may be included.
１−６ 養生不要性
本発明のアクリル系粘着剤組成物（Ｉ）は、４０℃〜１４０℃、０．５分〜５分の乾燥条件で乾燥後に養生が不要である。「養生が不要である」とは、アクリル系粘着剤組成物を上記乾燥条件での乾燥後、直接、被着体に貼り合せることができる状態であることである。粘着層を被着体に貼り合せることができる状態とは、例えば、微粘着のアクリル系粘着剤組成物の場合は、指で触れたときに糸を引かない状態であることとすることができる。また、粘着層の架橋状態が、後述の特定の「イソシアネートピーク面積率」を有することであるとすることができる。
1-6 Curing unnecessary The acrylic pressure-sensitive adhesive composition (I) of the present invention does not require curing after drying under drying conditions of 40 ° C. to 140 ° C. for 0.5 minutes to 5 minutes. “No curing is required” means that the acrylic pressure-sensitive adhesive composition can be directly bonded to an adherend after drying under the above-mentioned drying conditions. The state in which the adhesive layer can be bonded to the adherend can be, for example, a state in which a thread is not pulled when touched with a finger in the case of a slightly adhesive acrylic adhesive composition. . Moreover, it can be said that the crosslinked state of the adhesion layer has a specific “isocyanate peak area ratio” described later.
１−７ イソシアネートピーク面積率
本発明のアクリル系粘着剤組成物（Ｉ）は、好ましくは、４０℃〜１４０℃、０．５分〜５分の乾燥条件で乾燥後の上記アクリル系粘着剤組成物（Ｉ）について測定したイソシアネートピークの面積が、１１０℃、２分の乾燥条件で乾燥後の基準アクリル系粘着剤組成物について測定したイソシアネートピークの面積を１００％とした場合に、５５％以下である。なお、イソシアネートピークと基準アクリル系粘着剤組成物は、以下のように定義される。
・イソシアネートピーク：ＦＴ−ＩＲチャートに表れる２２７５ｃｍ−１のイソシアネート基の逆対称伸縮ＩＲピーク
・基準アクリル系粘着剤組成物：上記アクリル系共重合体（Ａ）と上記イソシアネート系硬化剤（Ｂ）とを上記アクリル系粘着剤組成物（Ｉ）とほぼ同じ割合で含み、上記ジルコニウム錯体触媒（Ｃ）と上記遅延剤（Ｄ）とを含まないアクリル系粘着剤組成物
1-7 Isocyanate Peak Area Ratio The acrylic pressure-sensitive adhesive composition (I) of the present invention is preferably the acrylic pressure-sensitive adhesive composition after drying under drying conditions of 40 to 140 ° C. and 0.5 to 5 minutes. The area of the isocyanate peak measured for the product (I) is 55% or less when the area of the isocyanate peak measured for the reference acrylic pressure-sensitive adhesive composition after drying at 110 ° C. for 2 minutes is 100%. It is. In addition, an isocyanate peak and a reference | standard acrylic adhesive composition are defined as follows.
・ Isocyanate peak: reverse symmetric stretching IR peak of 2275 cm −1 isocyanate group appearing on the FT-IR chart ・ Reference acrylic pressure-sensitive adhesive composition: acrylic copolymer (A) and isocyanate curing agent (B) In the same proportion as the acrylic pressure-sensitive adhesive composition (I), and does not include the zirconium complex catalyst (C) and the retarder (D).
また、以下において、１１０℃、２分の乾燥条件で乾燥後の基準アクリル系粘着剤組成物について測定したイソシアネートピークの面積を１００％とした場合の、４０℃〜１４０℃、０．５分〜５分の乾燥条件で乾燥後の上記アクリル系粘着剤組成物（Ｉ）について測定したイソシアネートピークの面積の割合を、イソシアネートピーク面積率と称する。イソシアネートピーク面積率が５５％以下である場合に、乾燥直後に、より好ましく被着体に直接貼り合せることができ、製品化しやすくなる。 Moreover, in the following, when the area of the isocyanate peak measured about the reference | standard acrylic adhesive composition after drying on drying conditions at 110 degreeC for 2 minutes is made into 100%, 40 degreeC-140 degreeC, 0.5 minute- The ratio of the area of the isocyanate peak measured for the acrylic pressure-sensitive adhesive composition (I) after drying under a drying condition of 5 minutes is referred to as an isocyanate peak area ratio. When the isocyanate peak area ratio is 55% or less, it can be directly bonded to the adherend more preferably immediately after drying, which facilitates commercialization.
基準アクリル系粘着剤組成物では、上記アクリル系共重合体（Ａ）と上記イソシアネート系硬化剤（Ｂ）とを上記アクリル系粘着剤組成物（Ｉ）とほぼ同じ割合で含むようにするために、上記遅延剤（Ｄ）の代わりに、上記の溶剤を加えてもよい。また、ほぼ同じ割合とは、全く同じ割合を１００％とした場合に、例えば９０〜１１０％の範囲での割合を含むものとすることができる。 In the reference acrylic pressure-sensitive adhesive composition, in order to contain the acrylic copolymer (A) and the isocyanate curing agent (B) in substantially the same proportion as the acrylic pressure-sensitive adhesive composition (I). Instead of the retarder (D), the above solvent may be added. Further, the substantially same ratio can include a ratio in the range of 90 to 110%, for example, when the completely same ratio is 100%.
基準アクリル系粘着剤組成物については１１０℃、２分の乾燥条件での乾燥後にイソシアネートピーク面積を測定し、評価対象組成物については、それぞれの所定の乾燥条件での乾燥後にイソシアネートピーク面積を測定して比較する。 For the reference acrylic pressure-sensitive adhesive composition, the isocyanate peak area is measured after drying under a drying condition of 110 ° C. for 2 minutes, and for the composition to be evaluated, the isocyanate peak area is measured after drying under each predetermined drying condition. And compare.
１−８ 乾燥条件
本発明のアクリル系粘着剤組成物（Ｉ）は、４０℃〜１４０℃、０．５分〜５分の乾燥条件での乾燥により、養生が不要となる。乾燥条件は、好ましくは４０℃〜１４０℃で０．５分〜２．５分であり、より好ましくは６０℃〜１２０℃で０．５分〜２．５分であり、例えば１１０℃２分とすることができる。また、４０℃〜１４０℃、好ましくは６０℃〜１２０℃の温度勾配を有する乾燥炉中を、０．５分〜５分、好ましくは０．５分〜２．５分で通過させることでもよい。乾燥時間が短すぎると養生不要とすることができず、長すぎるとコスト的に問題となる。乾燥は、大気中で行うことが好ましい。
1-8 Drying conditions Curing of the acrylic pressure-sensitive adhesive composition (I) of the present invention is not required by drying under drying conditions of 40 ° C. to 140 ° C. and 0.5 minutes to 5 minutes. The drying conditions are preferably 40 ° C to 140 ° C for 0.5 minutes to 2.5 minutes, more preferably 60 ° C to 120 ° C for 0.5 minutes to 2.5 minutes, for example, 110 ° C for 2 minutes. It can be. Further, it may be passed through a drying furnace having a temperature gradient of 40 ° C. to 140 ° C., preferably 60 ° C. to 120 ° C., for 0.5 minutes to 5 minutes, preferably 0.5 minutes to 2.5 minutes. . If the drying time is too short, curing cannot be made unnecessary, and if it is too long, there is a problem in cost. Drying is preferably performed in the air.
本発明のアクリル系粘着剤組成物では、上記乾燥条件での乾燥直後に実用可能な架橋状態となるため、被着体に直接貼り合せることができ、１工程で加工可能な保護フィルム等の粘着テープを製造できる。強粘着のアクリル系粘着剤組成物では、乾燥直後に粘着層をより固くすることができ、巻き取り後の経時凹凸の発生等の継時変化の少ない粘着層ならびにそれを含む粘着テープを製造できる。 In the acrylic pressure-sensitive adhesive composition of the present invention, since it becomes a practically crosslinked state immediately after drying under the above drying conditions, it can be directly bonded to an adherend and can be processed in one step. Tape can be manufactured. The strong adhesive acrylic pressure-sensitive adhesive composition can make the pressure-sensitive adhesive layer harder immediately after drying, and can produce a pressure-sensitive adhesive layer with little change over time, such as occurrence of unevenness after winding, and a pressure-sensitive adhesive tape containing the same. .
２．粘着テープ
本発明の粘着テープは、基材と、上記基材上に配置された粘着層とを含んでいる。基材としては、ＰＥＴならびに表面処理されたＰＥＴ等の公知のフィルムを使用できる。粘着層は、上記のアクリル系粘着剤組成物を上記基材上に公知の方法で塗工して形成できる。
2. Adhesive tape The adhesive tape of this invention contains the base material and the adhesive layer arrange | positioned on the said base material. As the substrate, known films such as PET and surface-treated PET can be used. The pressure-sensitive adhesive layer can be formed by coating the acrylic pressure-sensitive adhesive composition on the base material by a known method.
上記粘着層は、上記のアクリル系粘着剤組成物を４０℃〜１４０℃、０．５分〜５分の乾燥条件で乾燥した粘着層で構成されている。乾燥条件の好ましい態様は上記と同様である。上記粘着層の、イソシアネートピーク面積率は５５％未満である。 The said adhesion layer is comprised by the adhesion layer which dried said acrylic adhesive composition on 40 to 140 degreeC and the drying conditions for 0.5 minute-5 minutes. A preferred embodiment of the drying conditions is the same as described above. The adhesive layer has an isocyanate peak area ratio of less than 55%.
本発明の粘着テープは、微粘着である場合、セパレータレスの粘着テープとすることができ、被着体に直接貼り合せることができ、１工程で加工可能な保護フィルム等として使用できる。また、本発明の粘着テープは、強粘着の場合、従来よりも粘着層を固くできるため、巻き取り後の経時凹凸等の発生等の継時変化が抑制された粘着テープとすることができる。 When the adhesive tape of the present invention is slightly adhesive, it can be a separatorless adhesive tape, can be directly bonded to an adherend, and can be used as a protective film that can be processed in one step. Moreover, since the pressure-sensitive adhesive tape of the present invention can be made harder than the conventional adhesive layer in the case of strong adhesion, it can be made into a pressure-sensitive adhesive tape in which changes over time such as the occurrence of unevenness with time after winding are suppressed.
３．粘着テープの製造方法
本発明の粘着テープの製造方法は、（i）アクリル系粘着剤組成物の調合工程と（ii）粘着テープの作製工程とを含んでいる。
（i）アクリル系粘着剤組成物の調合工程では、アクリル系共重合体（Ａ）とイソシアネート系硬化剤（Ｂ）とジルコニウム錯体触媒（Ｃ）と遅延剤（Ｄ）などの原料を調合して、アクリル系粘着剤組成物（Ｉ）を製造する。
（ii）粘着テープの作製工程では、ＰＥＴなどの基材フィルムの上に、（i）アクリル系粘着剤組成物の調合工程で得られたアクリル系粘着剤組成物（Ｉ）を塗工し、４０℃〜１４０℃、０．５分〜５分の乾燥条件で乾燥させ、粘着層を形成する。
アクリル系粘着剤組成物（Ｉ）の塗工量は、乾燥後の厚さが、保護フィルム用途（微粘着）の場合は５〜２０μｍ、ＯＣＡ用途（強粘着）の場合は２０〜３５０μｍになるように調節するのが好ましい。
この基材上に粘着層が形成されたフィルムを、乾燥後直ちに、任意の被着体あるいはＰＥＴセパレータと貼り合せたのち、ゴムニップロール等で圧着して、粘着テープを製造する。乾燥条件の好ましい態様は上記と同様である。
3. 2. Manufacturing method of adhesive tape The manufacturing method of the adhesive tape of this invention includes the preparation process of (i) preparation of an acrylic adhesive composition, and (ii) preparation process of an adhesive tape.
(I) In the preparation step of the acrylic pressure-sensitive adhesive composition, raw materials such as an acrylic copolymer (A), an isocyanate-based curing agent (B), a zirconium complex catalyst (C), and a retarder (D) are prepared. An acrylic pressure-sensitive adhesive composition (I) is produced.
(Ii) In the production process of the pressure-sensitive adhesive tape, on the base film such as PET, (i) the acrylic pressure-sensitive adhesive composition (I) obtained in the step of preparing the acrylic pressure-sensitive adhesive composition is applied, It is dried under drying conditions of 40 ° C. to 140 ° C. for 0.5 minutes to 5 minutes to form an adhesive layer.
The coating amount of the acrylic pressure-sensitive adhesive composition (I) is 5 to 20 μm in the case of protective film use (slight adhesion) and 20 to 350 μm in the case of OCA use (strong adhesion). It is preferable to adjust as follows.
The film having the adhesive layer formed on the substrate is bonded to an arbitrary adherend or PET separator immediately after drying, and then pressure-bonded with a rubber nip roll or the like to produce an adhesive tape. A preferred embodiment of the drying conditions is the same as described above.
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらにより何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these.
（１）微粘着−剥離力測定用フィルムの実機試作
微粘着用の粘着剤組成物の実機での塗工性の確認、および、乾燥時間を制御することで架橋状態を制御できるかを確認する目的で以下の実験を行った。
(1) Prototype production of a film for measuring fine adhesion-peeling force Confirmation of coating property with an actual machine of an adhesive composition for fine adhesion and whether the crosslinking state can be controlled by controlling the drying time The following experiment was conducted for the purpose.
実施例Ａ−１
（１−１）粘着剤組成物の調合
以下の原料を調合し、粘着剤組成物を製造した。
・主剤 綜研化学製 ＳＫ−１４９６（アクリル系共重合体、不揮発分３７〜３９質量％） １００質量部
・硬化剤 綜研化学製 Ｄ−９０ （イソシアネート系硬化剤、有効成分８０〜９０質量％） ２質量部
・触媒 マツモトファインケミカル製 ＺＣ−７００（有効成分２０質量％） ０．３質量部
・遅延剤 アセチルアセトン ３質量部
・希釈溶剤 酢酸エチル ９０質量部
Example A-1
(1-1) Preparation of pressure-sensitive adhesive composition The following raw materials were prepared to produce a pressure-sensitive adhesive composition.
・ Main agent SK-1496 manufactured by Soken Chemical Co., Ltd. (acrylic copolymer, nonvolatile content: 37 to 39% by mass) 100 parts by mass ・ Curing agent manufactured by Soken Chemical Co., Ltd. D-90 (Isocyanate-based curing agent, active ingredient 80 to 90% by mass) 2 Mass parts / catalyst ZM-700 (active ingredient 20% by mass) manufactured by Matsumoto Fine Chemical 0.3 parts by mass retarder 3 parts by mass of acetylacetone / diluting solvent 90 parts by mass of ethyl acetate
（１−２）粘着テープの作製
ポリエチレンテレフタレート（ＰＥＴ）フィルムの上に、乾燥後の塗工量が１０μｍになるように、上記で得られた粘着剤組成物を塗工した。上記粘着剤組成物は、実機で十分塗工可能であった。また、次に５Ｚ、２０ｍからなる乾燥機に６０℃〜１２０℃の温度勾配を持たせ、この中を線速１０、１５、２５ｍ／ｍｉｎで通過させ、粘着剤組成物を乾燥させ、粘着層とした。ＰＥＴ上に粘着層が形成されたフィルムを未処理ＰＥＴと貼り合せたのち、ゴムニップロールで圧着して、評価用粘着テープを得た。この粘着テープについて、下記の評価方法で評価を行った。
(1-2) Preparation of pressure-sensitive adhesive tape The pressure-sensitive adhesive composition obtained above was coated on a polyethylene terephthalate (PET) film so that the coating amount after drying was 10 μm. The above-mentioned pressure-sensitive adhesive composition was sufficiently coatable with an actual machine. Further, a dryer composed of 5Z and 20m is provided with a temperature gradient of 60 ° C to 120 ° C, and this is passed through at a linear speed of 10, 15, and 25 m / min to dry the adhesive composition, and the adhesive layer It was. A film having an adhesive layer formed on PET was bonded to untreated PET, and then pressure-bonded with a rubber nip roll to obtain an evaluation adhesive tape. This adhesive tape was evaluated by the following evaluation method.
（１−３）剥離力の測定
ＪＩＳ Ｚ０２３７（２０００年版）に従って試験を行った。結果を表１に示す。
(1-3) Measurement of peeling force The test was conducted according to JIS Z0237 (2000 version). The results are shown in Table 1.
（１−４）イソシアネートピーク面積率の測定
ＦＴ−ＩＲ測定装置［（株）島津製作所製、赤外顕微鏡システム ＡＩＭ−８８００］を用いて、所定の乾燥条件で乾燥後の粘着剤組成物について、２２７５ｃｍ−１のイソシアネート基の逆対称伸縮ピーク（イソシアネートピーク）を測定した。また、触媒と遅延剤を含まず、上記主剤１００質量部と上記硬化剤２質量部と酢酸エチル９０質量部とを調合した基準アクリル系粘着剤組成物について、空気中１１０℃、２分の乾燥条件で乾燥した後、イソシアネートピークを測定した。イソシアネートピーク面積率は、何れの乾燥速度の粘着剤においても、５５％以下であった。
(1-4) Measurement of isocyanate peak area ratio About the pressure-sensitive adhesive composition after drying under predetermined drying conditions using an FT-IR measuring apparatus [manufactured by Shimadzu Corporation, infrared microscope system AIM-8800] The inverse symmetrical stretching peak (isocyanate peak) of the isocyanate group at 2275 cm −1 was measured. In addition, a reference acrylic pressure-sensitive adhesive composition containing 100 parts by mass of the main agent, 2 parts by mass of the curing agent, and 90 parts by mass of ethyl acetate without containing a catalyst and a retarder was dried at 110 ° C. in air for 2 minutes. After drying under conditions, the isocyanate peak was measured. The isocyanate peak area ratio was 55% or less in any pressure sensitive adhesive.
（１−５）架橋状態の評価
微粘着のアクリル塗料では、乾燥後の架橋状態が不十分な場合に、指で触れたときに糸を引く性質がある。この場合には、養生が必要である。そこで、糸を引くものを×、完全に糸を引かないものを○、僅かに糸を引くものを○△とした。結果を表１に示す。
(1-5) Evaluation of cross-linked state A slightly tacky acrylic paint has a property of pulling a thread when touched with a finger when the cross-linked state after drying is insufficient. In this case, curing is necessary. Therefore, the thread pulling was marked with ×, the thread that did not pull the thread completely was marked with ○, and the thread that pulled the thread slightly was marked with ○ △. The results are shown in Table 1.
実施例Ａ−２
ＰＥＴ上に粘着層が形成されたフィルムを、未処理ＰＥＴの代わりにシリコンアクリレートハードコート層を形成したＰＥＴと貼り合せた以外は実施例Ａ−１と同様にして、評価用粘着テープを得た。この粘着テープについて、実施例Ａ−１と同様に剥離力とイソシアネートピーク面積率と架橋状態の評価を行った。剥離力と架橋状態の評価結果を表１に示す。イソシアネートピーク面積率は、何れの乾燥速度の粘着剤においても、５５％以下であった。
Example A-2
An adhesive tape for evaluation was obtained in the same manner as in Example A-1, except that a film having an adhesive layer formed on PET was bonded to PET having a silicon acrylate hard coat layer instead of untreated PET. . About this adhesive tape, the peeling force, the isocyanate peak area ratio, and the crosslinked state were evaluated in the same manner as in Example A-1. Table 1 shows the evaluation results of the peel force and the crosslinked state. The isocyanate peak area ratio was 55% or less in any pressure sensitive adhesive.
実施例Ａ−３
ＰＥＴ上に粘着層が形成されたフィルムを、未処理ＰＥＴの代わりにフッ素含有シリコンアクリレートハードコート層を形成したＰＥＴと貼り合せた以外は実施例Ａ−１と同様にして、評価用粘着テープを得た。この粘着テープについて、実施例Ａ−１と同様に剥離力とイソシアネートピーク面積率と架橋状態の評価を行った。剥離力と架橋状態の評価結果を表１に示す。イソシアネートピーク面積率は、何れの乾燥速度の粘着剤においても、５５％以下であった。
Example A-3
An evaluation adhesive tape was prepared in the same manner as in Example A-1, except that a film having an adhesive layer formed on PET was bonded to PET having a fluorine-containing silicon acrylate hard coat layer instead of untreated PET. Obtained. About this adhesive tape, the peeling force, the isocyanate peak area ratio, and the crosslinked state were evaluated in the same manner as in Example A-1. Table 1 shows the evaluation results of the peel force and the crosslinked state. The isocyanate peak area ratio was 55% or less in any pressure sensitive adhesive.
表１に示すように、加工速度が１０ｍ／ｍｉｎ（乾燥時間２．０分）、１５ｍ／ｍｉｎ（乾燥時間１．３分）、２５ｍ／ｍｉｎ（乾燥時間０．８分）の何れの粘着剤組成物においても、イソシアネートピーク面積率が５５％以下であり、架橋状態も指で触れた場合に糸を引かず、養生不要であった。 As shown in Table 1, any pressure sensitive adhesive having a processing speed of 10 m / min (drying time 2.0 minutes), 15 m / min (drying time 1.3 minutes), or 25 m / min (drying time 0.8 minutes). Also in the composition, the isocyanate peak area ratio was 55% or less, and when the crosslinked state was touched with a finger, the yarn was not pulled and curing was unnecessary.
（２）微粘着−乾燥条件の最適化の卓上実験
養生不要とできる乾燥条件を特定する目的で下記の実験を行った。
(2) Slight adhesion-tabletop experiment for optimization of drying conditions The following experiment was conducted for the purpose of specifying drying conditions that can be cured.
実施例Ａ−４
（２−１）粘着剤組成物の調合
以下の原料を調合し、粘着剤組成物を製造した。
・主剤 綜研化学製 ＳＫ−１４９６（不揮発分３７〜３９質量％） １００質量部
・硬化剤 綜研化学製 Ｄ−９０ （有効成分８０〜９０質量％） ２質量部
・触媒 マツモトファインケミカル製 ＺＣ−７００（有効成分２０質量％）０．３質量部
・遅延剤 アセチルアセトン ２．５質量部
・希釈溶剤 酢酸エチル ９０質量部
Example A-4
(2-1) Preparation of pressure-sensitive adhesive composition The following raw materials were prepared to produce a pressure-sensitive adhesive composition.
・ Main agent SK-1496 made by Soken Chemical (non-volatile content: 37 to 39% by mass) 100 parts by mass ・ Curing agent D-90 made by Soken Chemical (active ingredient 80 to 90% by mass) ・ Catalyst ZC-700 made by Matsumoto Fine Chemical Active ingredient 20% by mass) 0.3 parts by mass / retarding agent acetylacetone 2.5 parts by mass / diluting solvent ethyl acetate 90 parts by mass
（２−２）粘着層の作製
ポリエチレンテレフタレート（ＰＥＴ）フィルムの上に、乾燥後の塗工量が１０μｍになるように粘着剤組成物を塗工した。次に１１０℃の乾燥機で、０．５〜３２分の種々の乾燥時間で粘着剤組成物を乾燥させ、それぞれ粘着層を得た。
(2-2) Preparation of pressure-sensitive adhesive layer A pressure-sensitive adhesive composition was coated on a polyethylene terephthalate (PET) film so that the coating amount after drying was 10 μm. Next, the pressure-sensitive adhesive composition was dried with a dryer at 110 ° C. for various drying times of 0.5 to 32 minutes to obtain pressure-sensitive adhesive layers, respectively.
（２−３）イソシアネートピーク面積率の測定
上記で得られた各粘着層について、実施例Ａ−１と同様に、イソシアネートピーク面積率を求めた。結果を図１に示す。
(2-3) Measurement of isocyanate peak area ratio About each adhesive layer obtained above, the isocyanate peak area ratio was calculated | required similarly to Example A-1. The results are shown in FIG.
図１に示すように、１１０℃、０．５分の乾燥条件においても、イソシアネートピークの面積率は５５％以下であった。１１０℃、５分の乾燥条件では、イソシアネートピークの面積率は１０％以下であった。 As shown in FIG. 1, the area ratio of the isocyanate peak was 55% or less even under the drying condition at 110 ° C. for 0.5 minutes. Under a drying condition of 110 ° C. for 5 minutes, the area ratio of the isocyanate peak was 10% or less.
（２−４）架橋状態の評価
上記で得られた各粘着層について、実施例Ａ−１と同様に、指で触れたときに糸を引くかどうかの架橋状態の評価を行った。この結果、全ての粘着層において完全に糸を引かず、養生が不要であった。
(2-4) Evaluation of crosslinked state About each adhesion layer obtained above, evaluation of the crosslinked state whether a thread | yarn was pulled when it touched with the finger | toe similarly to Example A-1 was performed. As a result, all the adhesive layers did not draw the yarn completely, and curing was unnecessary.
（３）微粘着−触媒量と遅延剤量の最適化の卓上実験
養生不要とできる触媒量の下限ならびに遅延剤倍率の上限を特定し、また、十分なポットライフを保持できる遅延剤倍率の下限を特定する目的で下記の実験を行った。
(3) Slight adhesion-Tabletop experiment for optimization of catalyst amount and retarder amount Specify lower limit of catalyst amount that can be cured and upper limit of retarder factor, and lower limit of retarder factor that can maintain sufficient pot life The following experiment was conducted for the purpose of identifying
実施例Ｂ−１
（３−１）粘着剤組成物の調合
以下の原料を調合し、粘着剤組成物を製造した。
・主剤 綜研化学製 ＳＫ−１４９６（不揮発分３７〜３９質量％） １００質量部
・硬化剤 綜研化学製 Ｄ−９０（有効成分８０〜９０質量％） ２質量部
・触媒 マツモトファインケミカル製 ＺＣ−７００（有効成分２０質量％）０．０５質量部
・遅延剤 アセチルアセトン ３質量部
・希釈溶剤 酢酸エチル ９０質量部
Example B-1
(3-1) Preparation of pressure-sensitive adhesive composition The following raw materials were prepared to produce a pressure-sensitive adhesive composition.
・ Main agent SK-1496 made by Soken Chemical (non-volatile content: 37 to 39% by mass) 100 parts by mass Curing agent D-90 made by Soken Chemical (active ingredient 80 to 90% by mass) 2 parts by catalyst ZC-700 made by Matsumoto Fine Chemical Active ingredient 20% by mass) 0.05 part by mass, retarder 3 parts by mass acetylacetone, diluting solvent ethyl acetate 90 parts by mass
（３−２）保護フィルムの作製
ポリエチレンテレフタレート（ＰＥＴ）フィルムの上に、乾燥後の塗工量が１０μｍになるように粘着剤組成物を塗工した。次に１１０℃の乾燥機で、２分乾燥させ、粘着剤組成物を乾燥させ、粘着層を得た。ＰＥＴ上に粘着層が形成されたフィルムを未処理ＰＥＴと貼り合せたのち、ゴムニップロールで圧着して、評価用粘着テープを得た。この粘着テープについて、下記の評価方法で評価を行った。
(3-2) Preparation of protective film The pressure-sensitive adhesive composition was coated on a polyethylene terephthalate (PET) film so that the coating amount after drying was 10 µm. Next, it was dried for 2 minutes with a dryer at 110 ° C., and the pressure-sensitive adhesive composition was dried to obtain a pressure-sensitive adhesive layer. A film having an adhesive layer formed on PET was bonded to untreated PET, and then pressure-bonded with a rubber nip roll to obtain an evaluation adhesive tape. This adhesive tape was evaluated by the following evaluation method.
（３−３）架橋状態の評価
実施例Ａ−１と同様に架橋状態の評価を行った。結果を表２に示す。
(3-3) Evaluation of crosslinked state The crosslinked state was evaluated in the same manner as in Example A-1. The results are shown in Table 2.
（３−４）イソシアネートピーク面積率の測定
上記で得られた各粘着層について、実施例Ａ−１と同様に、イソシアネートピーク面積率を求めた。イソシアネートピーク面積率は５５％以下であった。
(3-4) Measurement of isocyanate peak area ratio About each adhesion layer obtained above, the isocyanate peak area ratio was calculated | required similarly to Example A-1. The isocyanate peak area ratio was 55% or less.
実施例Ｂ−２〜Ｂ−４、ならびに比較例Ｂ−１〜Ｂ−５
触媒ならびに遅延剤の添加量を表２に示すように変更した以外は実施例Ｂ−１と同様にして、評価用フィルムを得た。このフィルムについて、実施例Ｂ−１と同様に評価を行った。結果を表２に示す。イソシアネートピーク面積率はいずれも５５％以下であった。
Examples B-2 to B-4 and Comparative Examples B-1 to B-5
A film for evaluation was obtained in the same manner as in Example B-1, except that the addition amounts of the catalyst and retarder were changed as shown in Table 2. This film was evaluated in the same manner as in Example B-1. The results are shown in Table 2. The isocyanate peak area ratios were all 55% or less.
表２に示すように、主剤１００質量部(アクリル樹脂３７〜３９質量部)に対し、０．０５質量部のＺＳ−７００（触媒量０．０１質量部）を添加した場合に、炉内で乾燥後に良好な架橋状態が得られた。また、遅延剤を、触媒に対して質量比で３００倍量添加しても、炉内で乾燥後に良好な架橋状態が得られた。そして、イソシアネートピーク面積率を５５％以下にできた。 As shown in Table 2, when 0.05 part by weight of ZS-700 (catalyst amount 0.01 part by weight) is added to 100 parts by weight of the main agent (acrylic resin 37 to 39 parts by weight), in the furnace A good cross-linked state was obtained after drying. Further, even when the retarder was added in a mass ratio of 300 times with respect to the catalyst, a good cross-linked state was obtained after drying in the furnace. And the isocyanate peak area ratio was able to be 55% or less.
実施例Ｃ−１〜Ｃ−４
触媒ならびに遅延剤の添加量を表３に示すように変更した以外は実施例Ｂ−１と同様にして、粘着剤組成物ならびに粘着層を得た。これらの粘着剤組成物について、以下の評価を行った。
Examples C-1 to C-4
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive layer were obtained in the same manner as in Example B-1, except that the addition amounts of the catalyst and the retarder were changed as shown in Table 3. The following evaluation was performed about these adhesive compositions.
（３−５）架橋状態の評価
実施例Ａ−１と同様に架橋状態の評価を行った。結果を表３に示す。
(3-5) Evaluation of crosslinked state The crosslinked state was evaluated in the same manner as in Example A-1. The results are shown in Table 3.
（３−６）イソシアネートピーク面積率の測定
上記で得られた各粘着層について、実施例Ａ−１と同様に、イソシアネートピーク面積率を求めた。イソシアネートピーク面積率は５５％以下であった。
(3-6) Measurement of isocyanate peak area ratio About each adhesion layer obtained above, the isocyanate peak area ratio was calculated | required similarly to Example A-1. The isocyanate peak area ratio was 55% or less.
（３−７）ポットライフの測定
実施例Ｃ−１〜Ｃ−４で製造した粘着剤組成物を、室温環境下（２５℃前後）に蓋をして保管し、１時間ごとに粘度測定を行った。４時間以上ゲル化しないものを使用可能とした。望ましくは６時間以上ゲル化しないものが良い。結果を表４に示す。
(3-7) Measurement of pot life The pressure-sensitive adhesive composition produced in Examples C-1 to C-4 was stored under a room temperature environment (around 25 ° C.), and the viscosity was measured every hour. went. Those that did not gel for more than 4 hours could be used. Desirably, it does not gel for 6 hours or more. The results are shown in Table 4.
表３に示すように、遅延剤を、触媒に対して質量比で４０倍量添加した場合に、炉内で乾燥後に良好な架橋状態が得られた。そして、イソシアネートピーク面積率を５５％以下にできた。また、表４に示すように、いずれの粘着剤組成物もポットライフは４時間以上であった。 As shown in Table 3, when the retarder was added in a mass ratio of 40 times with respect to the catalyst, a good cross-linked state was obtained after drying in the furnace. And the isocyanate peak area ratio was able to be 55% or less. Moreover, as shown in Table 4, the pot life of any pressure-sensitive adhesive composition was 4 hours or longer.
（４）強粘着−応用の可能性の確認とポットライフ延長の為の試作
強粘着塗料で養生不要とできるか、また、強粘着塗料で十分なポットライフが得られるか確認する目的で下記の実験を行った。
(4) Strong Adhesion-Prototype for Confirmation of Possibility of Application and Extension of Pot Life For the purpose of confirming whether curing is unnecessary with strong adhesive paint and whether sufficient pot life can be obtained with strong adhesive paint, the following The experiment was conducted.
実施例Ｄ−１
（４−１）粘着剤組成物（塗料）の調合
以下の原料を調合し、粘着剤組成物を製造した。
・主剤 大同化成工業製 ダイカラック５２５０（不揮発分３９〜４１質量％）１００質量部
・硬化剤 日本ポリウレタン工業製 コロネートＨＸ（不揮発分１００％） ０．２質量部
・触媒 マツモトファインケミカル製 ＺＣ−７００（有効成分２０質量％） ０．３質量部
・遅延剤 アセチルアセトン ３質量部
・希釈溶剤 酢酸エチル ３０質量部
なお、ここでは触媒の有効成分質量に対する遅延剤の質量を５０倍とした。
Example D-1
(4-1) Preparation of adhesive composition (paint) The following raw materials were prepared to produce an adhesive composition.
・ Daikaraka 5250 (non-volatile content 39-41 mass%) 100 parts by mass, main agent Daido Kasei Kogyo Co., Ltd. Coronate HX (non-volatile content 100%) 0.2% by mass made by Nippon Polyurethane Industry ・ Catalyst ZC-700 (effective) 0.3 parts by mass / retarding agent 3 parts by mass of acetylacetone / diluting solvent 30 parts by mass of ethyl acetate Here, the mass of the retarding agent with respect to the active ingredient mass of the catalyst was 50 times.
（４−２）粘着テープの作製
ポリエチレンテレフタレート（ＰＥＴ）フィルムの上に、乾燥後の塗工量が１０μｍになるように上記で得られた粘着剤組成物を塗工した。次に１１０℃の乾燥機で２分乾燥させ、ＰＥＴフィルム上に粘着層が形成された粘着テープを得た。
(4-2) Preparation of pressure-sensitive adhesive tape The pressure-sensitive adhesive composition obtained above was coated on a polyethylene terephthalate (PET) film so that the coating amount after drying was 10 μm. Next, it was dried with a dryer at 110 ° C. for 2 minutes to obtain an adhesive tape having an adhesive layer formed on a PET film.
（４−３）イソシアネートピーク面積率の測定
ＦＴ−ＩＲ測定装置［（株）島津製作所製、赤外顕微鏡システム ＡＩＭ−８８００］を用いて、乾燥後の粘着剤組成物（粘着層）について、２２７５ｃｍ−１のイソシアネート基の逆対称伸縮ピーク（イソシアネートピーク）を測定した。また、触媒と遅延剤を含まず、上記主剤１００質量部と上記硬化剤０．２質量部と酢酸エチル３３質量部とを調合した基準アクリル系粘着剤組成物について、空気中１１０℃、２分の乾燥条件で乾燥した後、イソシアネートピークを測定し、イソシアネートピーク面積率を求めた。結果を表５に示す。
(4-3) Measurement of isocyanate peak area ratio About the adhesive composition (adhesion layer) after drying using an FT-IR measurement device [manufactured by Shimadzu Corporation, infrared microscope system AIM-8800], 2275 cm The reverse symmetrical stretching peak (isocyanate peak) of the isocyanate group of -1 was measured. Moreover, about the reference | standard acrylic adhesive composition which did not contain a catalyst and a retarder and prepared the said main ingredient 100 mass part, the said hardening | curing agent 0.2 mass part, and ethyl acetate 33 mass part, 110 degreeC in air, 2 minutes Then, the isocyanate peak was measured to obtain the isocyanate peak area ratio. The results are shown in Table 5.
実施例Ｄ−２〜Ｄ−６、ならびに比較例Ｄ−１
触媒、遅延剤、ならびに酢酸エチルの添加量を表５に示すように変更した以外は実施例Ｄ−１と同様にして、評価用フィルムを得た。このフィルムについて、実施例Ｄ−１と同様に評価を行った。結果を表５に示す。
Examples D-2 to D-6 and Comparative Example D-1
A film for evaluation was obtained in the same manner as in Example D-1, except that the addition amounts of the catalyst, retarder, and ethyl acetate were changed as shown in Table 5. This film was evaluated in the same manner as in Example D-1. The results are shown in Table 5.
実施例Ｄ−８〜Ｄ−１０
触媒、遅延剤、ならびに酢酸エチルの添加量を表６に示すように変更した以外は実施例Ｄ−１と同様にして、評価用フィルムを得た。このフィルムについて、以下の方法でポットライフの評価を行った。結果を表６に示す。
Examples D-8 to D-10
A film for evaluation was obtained in the same manner as in Example D-1, except that the addition amounts of the catalyst, retarder, and ethyl acetate were changed as shown in Table 6. The pot life of this film was evaluated by the following method. The results are shown in Table 6.
（４−４）ポットライフの測定
調液後、室温環境下（２５℃前後）に蓋をして保管し、１時間ごとに粘度測定を行った。４時間後の粘度が２倍以下を使用可能とした。望ましくは６時間後でも２倍以下が良い。
(4-4) Measurement of pot life After preparation, the cap was stored in a room temperature environment (around 25 ° C.), and the viscosity was measured every hour. The viscosity after 4 hours could be used less than 2 times. Desirably, it should be twice or less even after 6 hours.
表５に示すように、強粘着塗料でも、イソシアネートピーク面積率は５５％以下であり、養生が不要であった。また、表６に示すように、強粘着塗料でも実用可能なポットライフが得られた。 As shown in Table 5, even in the strong adhesion paint, the isocyanate peak area ratio was 55% or less, and curing was unnecessary. Further, as shown in Table 6, a pot life that can be practically used even with a strong adhesive paint was obtained.
本発明のアクリル系粘着剤組成物によれば、錫レスで環境に優しく、汎用性が高い粘着テープをより低コストで製造できる。また、各種保護フィルム等に使用される微粘着の粘着テープにおいては、セパレータレスの微粘着の粘着テープを製造できる。さらには、強粘着の粘着テープにおいては、巻き取り後の経時凹凸の発生等の継時変化の少ない粘着層ならびにそれを含む粘着テープを製造できる。
According to the acrylic pressure-sensitive adhesive composition of the present invention, a pressure-sensitive adhesive tape that is tin-free and environmentally friendly and highly versatile can be produced at a lower cost. Moreover, in the slightly adhesive adhesive tape used for various protective films etc., a separatorless slightly adhesive tape can be manufactured. Furthermore, in the strongly adhesive pressure-sensitive adhesive tape, it is possible to produce an adhesive layer with little change over time such as occurrence of unevenness with time after winding, and an adhesive tape including the same.
Claims (3)
該ジルコニウム錯体触媒（Ｃ）の含有量が、該アクリル系共重合体（Ａ）１００質量部に対して、０．０２質量部以上であり、
該遅延剤（Ｄ）の含有量が、該ジルコニウム錯体触媒（Ｃ）１質量部に対して、３０〜３５０質量部であり、
４０℃〜１４０℃、０．５分〜５分の乾燥条件で乾燥後に養生が不要である
アクリル系粘着剤組成物。 An acrylic pressure-sensitive adhesive composition (I) comprising an acrylic copolymer (A), an isocyanate curing agent (B), a zirconium complex catalyst (C), and a retarder (D),
The content of the zirconium complex catalyst (C) is 0.02 parts by mass or more with respect to 100 parts by mass of the acrylic copolymer (A),
The content of the retarder (D) is 30 to 350 parts by mass with respect to 1 part by mass of the zirconium complex catalyst (C),
An acrylic pressure-sensitive adhesive composition that does not require curing after drying under drying conditions of 40 ° C to 140 ° C for 0.5 minutes to 5 minutes.
請求項１に記載のアクリル系粘着剤組成物。
・イソシアネートピーク：ＦＴ−ＩＲチャートに表れる２２７５ｃｍ−１のイソシアネート基の逆対称伸縮ＩＲピーク
・基準アクリル系粘着剤組成物：前記アクリル系共重合体（Ａ）と前記イソシアネート系硬化剤（Ｂ）とを前記アクリル系粘着剤組成物（Ｉ）とほぼ同じ割合で含み、前記ジルコニウム錯体触媒（Ｃ）と前記遅延剤（Ｄ）とを含まないアクリル系粘着剤組成物 The area of the isocyanate peak defined below measured for the acrylic pressure-sensitive adhesive composition (I) after drying under the drying conditions is 110 ° C., and the reference acrylic defined below after drying under the drying conditions for 2 minutes. When the area of the isocyanate peak measured for the pressure-sensitive adhesive composition is 100%, it is 55% or less.
The acrylic pressure-sensitive adhesive composition according to claim 1.
・ Isocyanate peak: reverse symmetric stretching IR peak of 2275 cm −1 isocyanate group appearing on the FT-IR chart ・ Reference acrylic pressure-sensitive adhesive composition: the acrylic copolymer (A) and the isocyanate curing agent (B) Acrylic pressure-sensitive adhesive composition containing the zirconium complex catalyst (C) and the retarder (D) in substantially the same proportion as the acrylic pressure-sensitive adhesive composition (I)
該基材上に配置され、請求項１又は２に記載のアクリル系粘着剤組成物を前記乾燥条件で乾燥した粘着層と
を含む、
粘着テープ。
A substrate;
An adhesive layer disposed on the substrate and dried with the acrylic pressure-sensitive adhesive composition according to claim 1 or 2 under the drying conditions;
Adhesive tape.
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|---|---|---|---|---|
| JP2001240830A (en) * | 2000-02-28 | 2001-09-04 | Saiden Chemical Industry Co Ltd | Adhesive composition and surface protective film |
| JP2005247909A (en) * | 2004-03-02 | 2005-09-15 | Saiden Chemical Industry Co Ltd | Pressure-sensitive adhesive composition and surface protective film |
| JP2011132269A (en) * | 2009-12-22 | 2011-07-07 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition and optical film |
| JP2013147631A (en) * | 2011-12-20 | 2013-08-01 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet |
| WO2015072795A1 (en) * | 2013-11-15 | 2015-05-21 | 주식회사 엘지화학 | Adhesive composition |
| JP2015105299A (en) * | 2013-11-29 | 2015-06-08 | 藤森工業株式会社 | Adhesive composition and surface protective film |
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| JP2001240830A (en) * | 2000-02-28 | 2001-09-04 | Saiden Chemical Industry Co Ltd | Adhesive composition and surface protective film |
| JP2005247909A (en) * | 2004-03-02 | 2005-09-15 | Saiden Chemical Industry Co Ltd | Pressure-sensitive adhesive composition and surface protective film |
| JP2011132269A (en) * | 2009-12-22 | 2011-07-07 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition and optical film |
| JP2013147631A (en) * | 2011-12-20 | 2013-08-01 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet |
| WO2015072795A1 (en) * | 2013-11-15 | 2015-05-21 | 주식회사 엘지화학 | Adhesive composition |
| JP2015105299A (en) * | 2013-11-29 | 2015-06-08 | 藤森工業株式会社 | Adhesive composition and surface protective film |
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