JPH01287114A - Photo-setting type adhesive composition - Google Patents
Photo-setting type adhesive compositionInfo
- Publication number
- JPH01287114A JPH01287114A JP11477288A JP11477288A JPH01287114A JP H01287114 A JPH01287114 A JP H01287114A JP 11477288 A JP11477288 A JP 11477288A JP 11477288 A JP11477288 A JP 11477288A JP H01287114 A JPH01287114 A JP H01287114A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic copolymer
- weight
- acrylic
- meth
- adhesive
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 230000001070 adhesive effect Effects 0.000 title description 33
- 239000000853 adhesive Substances 0.000 title description 25
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 230000002165 photosensitisation Effects 0.000 claims abstract description 10
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 8
- 239000000470 constituent Substances 0.000 claims abstract description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 30
- 125000000524 functional group Chemical group 0.000 claims description 11
- 238000000016 photochemical curing Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012965 benzophenone Substances 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 12
- 239000002390 adhesive tape Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- MUEGIVAMQURJQO-UHFFFAOYSA-N 2-(aziridin-1-yl)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1CC1 MUEGIVAMQURJQO-UHFFFAOYSA-N 0.000 description 3
- -1 2-ethylhexyl Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は光硬化型感圧接着剤組成物に関し、詳しくは、
光照射によって接着特性ｔこ優れた感圧接着剤層を形成
し得る光硬化型感圧接着剤組成物に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photocurable pressure-sensitive adhesive composition, and specifically,
The present invention relates to a photocurable pressure-sensitive adhesive composition that can form a pressure-sensitive adhesive layer with excellent adhesive properties upon irradiation with light.
アクリル系感圧接着剤は、粘着テープ、粘着ラベル等の
粘着層の形成に用いられており、該粘着層の形成のため
に、従来より一般に用いられているアクリル系感圧接着
剤は、所望の接着特性を得るために、比較的高分子量の
アクリル系重合体をベースポリマーとして構成されてお
り、該ベースポリマーをエマルジョン型にしたり、ある
いは、有機溶媒に溶解させた溶液の形態で紙、布、プラ
スチックフィルム等の基材に塗布されている。Acrylic pressure-sensitive adhesives are used to form adhesive layers in adhesive tapes, adhesive labels, etc. Acrylic pressure-sensitive adhesives that have been commonly used in the past are used to form adhesive layers in adhesive tapes, adhesive labels, etc. In order to obtain adhesive properties, it is composed of a relatively high molecular weight acrylic polymer as a base polymer, and the base polymer is made into an emulsion type or dissolved in an organic solvent and applied to paper, cloth. , applied to base materials such as plastic films.
しかしながら、上記のエマルジョン型及び有機溶媒型の
アクリル系感圧接着剤とも、塗布後その分散媒もしくは
有機溶媒を除去するために、大量の熱エネルギーを必要
とし、生産性が著しく制限されるという問題点がある。However, both the emulsion-type and organic solvent-type acrylic pressure-sensitive adhesives mentioned above require a large amount of thermal energy to remove the dispersion medium or organic solvent after application, which significantly limits productivity. There is a point.
また、特に、有機溶媒型の感圧接着剤は有機溶媒を使用
していることから、該溶媒の除去にともなって大気汚染
等、種々の公害問題が発生するという欠点がある。Further, in particular, since organic solvent-type pressure sensitive adhesives use an organic solvent, there is a drawback that various pollution problems such as air pollution occur when the solvent is removed.
この点、放射線の照射ζこよって架橋硬化する感圧接着
剤は、必ずしも有機溶媒を使用する必要がないので、上
記従来の感圧接着剤におけるがごとき問題点の発生かな
いため、近年その検討が盛んに行われており、特に紫外
線の照射によって硬化する光硬化型アクリル系感圧接着
剤は、短時間の光照射で粘着層を形成することかでき、
生産性の点て優れている他、安全性、経済性等にも優れ
るという利点があり、注目されている。In this regard, pressure-sensitive adhesives that are cross-linked and cured by radiation irradiation do not necessarily require the use of organic solvents, so they do not have the same problems as the conventional pressure-sensitive adhesives mentioned above, so they have been studied in recent years. Photo-curing acrylic pressure-sensitive adhesives, which are widely used and cured by ultraviolet irradiation, can form an adhesive layer with short-term light irradiation.
It is attracting attention because it has advantages such as excellent productivity, safety, and economical efficiency.
しかしながら、・従来の光硬化型アクリル系感圧接着剤
には、以下のような問題点もあり・、その改善が望まれ
ている。However, conventional photocurable acrylic pressure-sensitive adhesives have the following problems, and improvements are desired.
すなわち、従来の光硬化型アクリル系感圧接着剤は、例
えば、特開昭５７−１４．１４７１号公報に開示されて
いるように、（メタ）アクリロイル基を持つ低分子量の
アクリル系共重合体をヘースボリマーとし、これにヘン
ジイン、ヘンシフエノン、アセトフェノン等の光増感剤
を配合して成るのが一般的であるが、この感圧接着剤は
光照射した時に発生するラジカルが多いため反応速度が
極めて早く、共重合体間で過剰の架橋結合が形成され易
く、その結果、得られた感圧接着剤層は凝集力が強くな
り過ぎて粘着性の乏しいものしか得られないという問題
点がある。一方、過剰の架橋結合の形成をを抑制するた
めに共重合体也こ付加されている（メタ）アクリロイル
基の密度を低くすると、凝集力が乏しく、かつ、被接接
着体への汚染の著しいものしか得られないという問題点
がある。That is, conventional photocurable acrylic pressure-sensitive adhesives are made of low molecular weight acrylic copolymers having (meth)acryloyl groups, as disclosed in JP-A-57-14.1471, for example. Generally, it is made by blending a hesyl polymer with a photosensitizer such as hengeine, hensifhenone, acetophenone, etc. However, this pressure-sensitive adhesive has a very high reaction rate because it generates many radicals when irradiated with light. There is a problem in that excessive cross-linking bonds are easily formed between the copolymers quickly, and as a result, the resulting pressure-sensitive adhesive layer has too strong a cohesive force and only has poor adhesiveness. On the other hand, if the density of the (meth)acryloyl groups added to the copolymer is lowered in order to suppress the formation of excessive crosslinks, the cohesive force will be poor and the contamination of the objects to be adhered will be significant. The problem is that you can only get things.
そこで本発明者等は、上記のような問題点のない光硬化
型アクリル系感圧接着剤を得るべく鋭意検討した結果、
（ａ） （メタ）アクリロイル基を有する重量平均分子
量（以下、ｒ Ｍ Ｗ Ｊと称する）が３００００〜５
００００のアクリル系共重合体（以下、「アクリル共重
合体（ａ）」と称する）８０〜９０重量％、及び、
（ｂ） 構成成分中、光増感作用を有する官能基含有
単量体５〜３０重量％を含有してなるＭＷが５０００〜
５００００のアクリル系共重合体（以下、「アクリル共
重合体（ｂ）」と称する）２０〜１０重量％、
とから成る感圧接着剤を提供することによって、粘着性
と凝集力のバランスが取れた接着特性に優れた光硬化型
アクリル系感圧接着剤となり得ることを見出し、本発明
を完成したものである。Therefore, the present inventors conducted intensive studies to obtain a photocurable acrylic pressure-sensitive adhesive free from the above-mentioned problems. (referred to as W J) is 30,000 to 5
0000 acrylic copolymer (hereinafter referred to as "acrylic copolymer (a)") 80 to 90% by weight, and (b) among the constituent components, a functional group-containing monomer 5 having a photosensitizing effect. MW containing ~30% by weight is ~5000~
50,000 acrylic copolymer (hereinafter referred to as "acrylic copolymer (b)") by 20 to 10% by weight, the tackiness and cohesive force are balanced. The present invention was completed based on the discovery that the present invention can be used as a photocurable acrylic pressure-sensitive adhesive with excellent adhesive properties.
本発明でいうアクリル共重合体（ａ）とは、その主鎖を
アクリル系ないしはメタアクリル系単量体く以下、「（
メタ）アクリル系単量体」と称する）からなるポリマー
で構成し、更に、この主鎖に（メタ）アクリロイル基を
付加させて成るものである。The acrylic copolymer (a) as used in the present invention refers to the term "(
It is composed of a polymer consisting of a meth)acrylic monomer (referred to as ``meth)acrylic monomer'' and further has a (meth)acryloyl group added to the main chain.
上記アクリル共重合体（ａ）において、主鎖を構成する
（メタ）アクリル系単量体の具体例としては、メチル（
メタ）アクリレート、エチル（メタ）アクリレート、ｎ
−または１ｓｏ−プロピル（メタ）アクリレート、ｎ−
または１ｓｏ−ブチル（メタ）アクリレート、２−エチ
ルヘキシル（メタ）アクリレート、（メタ）アクリル酸
、ヒドロキシエチル（メタ）アクリレート等の単量体の
１種もしくは２種以上の混合物であるが、得られるポリ
マー主鎖に（メタ）アクリロイル基を付加させる必要が
あるので、該付加反応の際に反応点を形成することので
きる（メタ）アクリル酸、または、ヒドロキシエチル（
メタ）アクリレート等のような官能基を有する（メタ）
アクリレート系単量体を存在させることが必要である。In the above acrylic copolymer (a), specific examples of the (meth)acrylic monomer constituting the main chain include methyl (
meth)acrylate, ethyl(meth)acrylate, n
- or 1so-propyl (meth)acrylate, n-
or a mixture of one or more monomers such as 1so-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid, and hydroxyethyl (meth)acrylate; the resulting polymer Since it is necessary to add a (meth)acryloyl group to the main chain, (meth)acrylic acid or hydroxyethyl (
(meth) with functional groups such as acrylate, etc.
It is necessary to have an acrylate monomer present.
また、これら（メタ）アクリル系単量体には、改質成分
としてスチレン、酢酸ビニル等の単量体を、最終的に得
られる感圧接着剤の接着特性を損なわない範囲で混合し
て用いても良い。In addition, these (meth)acrylic monomers are mixed with monomers such as styrene and vinyl acetate as modifying components to the extent that they do not impair the adhesive properties of the final pressure-sensitive adhesive. It's okay.
アクリル共重合体（ａ）は、公知の方法で製造すること
ができ、例えば、上記（メタ）アクリル系単量体にアゾ
ビスイソブチロニトリル、２，２′−アゾヒス（２，４
−ジメチルバレロニトリル）等の重合触媒の慣用量を加
え、温度７０〜１２０℃で６〜１２時間の重合条件で、
塊状重合または有機溶媒の存在下に溶液重合することに
よって得られる。The acrylic copolymer (a) can be produced by a known method, for example, by adding azobisisobutyronitrile, 2,2'-azohis(2,4
- dimethylvaleronitrile) and polymerization conditions for 6 to 12 hours at a temperature of 70 to 120 °C.
It can be obtained by bulk polymerization or solution polymerization in the presence of an organic solvent.
また、得られた共重合体に（メタ）アクリロイル基を例
加ざぜるには、例えは、該共重合体に含まれる（メタ）
アクリル酸のカルホキシル基に対して、グリシジル（メ
タ）アクリレートを、トリエチルアンモニウムクロライ
ド、トす］、チルアミン等の触媒と、ハイトロギノン、
ハイトロギノンモノメチルエーテル等の熱重合禁止剤の
存在下、温度８０〜１５０°Ｃて１〜２４時間の反応条
件で例加させる方法、あるいは、アジリジニルエチルア
クリレートを熱重合禁止剤の存在下、温度３０〜６０
’Ｃて３〜２４時間の反応条件で例加させる方法等でお
こなうことができる。In addition, in order to add a (meth)acryloyl group to the obtained copolymer, for example, the (meth)acryloyl group contained in the copolymer must be
For the carboxyl group of acrylic acid, glycidyl (meth)acrylate is combined with a catalyst such as triethylammonium chloride, thylamine, hytrogynone,
A method in which aziridinylethyl acrylate is added in the presence of a thermal polymerization inhibitor such as hytrogynone monomethyl ether at a temperature of 80 to 150°C for 1 to 24 hours, or aziridinylethyl acrylate is added in the presence of a thermal polymerization inhibitor. , temperature 30-60
This can be carried out, for example, by a method in which the reaction mixture is added under the reaction conditions of 3 to 24 hours.
なお、上記共重合体（ａ）力月容）ｔｋ重合法によって
得られた場合には、適宜の方法で脱溶剤するのが好まし
い。In addition, when the above-mentioned copolymer (a) is obtained by the tk polymerization method, it is preferable to remove the solvent by an appropriate method.
本発明に用いられる上記共重合体（ａ）の分子量は、Ｍ
ｗて３００００〜５ｏｏｏｏの範囲テアリ、Ｍｗが３０
０００より小さい場合、得られる感圧接着剤は凝集力に
乏しくなり、被接着体への汚染（糊残り）が生しるよう
になる。また、Ｍｗが５００００を超える場合は、得ら
れる接着剤の粘度が高くなり、種々の基材への塗工作業
が困難となるので好ましくない。The molecular weight of the copolymer (a) used in the present invention is M
The range is 30,000 to 5oooo, Mw is 30
If it is less than 000, the resulting pressure-sensitive adhesive will have poor cohesive force, resulting in contamination (adhesive residue) on the adherend. Moreover, when Mw exceeds 50,000, the viscosity of the resulting adhesive becomes high, making it difficult to apply it to various base materials, which is not preferable.
本発明でいうアクリル共重合体（１〕）とは、例えば、
特開昭６０−９９１８３号公報に開示されているような
光架橋型感圧接着剤組成物、すなわち、主鎖をアクリル
系またはメタアクリル系単量体で構成し、さらにこの主
鎖に光増感作用をもつ官能基含有単量体を共重合させて
成るものであり、その主鎖を構成する単量体の具体例と
しては、上記アクリル共重合体（ａ）において例示した
（メタ）アクリル系単量体をそのまま用いることができ
、また、改質成分としてのスチレン、酢酸ビニル等も同
様に用いることができる。The acrylic copolymer (1) in the present invention is, for example,
A photocrosslinkable pressure sensitive adhesive composition as disclosed in JP-A No. 60-99183, that is, the main chain is composed of an acrylic or methacrylic monomer, and the main chain is further photointensified. It is made by copolymerizing a functional group-containing monomer with a sensitizing effect, and specific examples of monomers constituting the main chain include (meth)acrylic as exemplified in the above acrylic copolymer (a). The system monomers can be used as they are, and styrene, vinyl acetate, etc. as modifying components can also be used in the same way.
また、該アクリル共重合体（ｂ）の必須構成成分である
光増感作用をもつ官能基含有単量体としては、例えば、
米国特許第３００４０７３号または同第３５７５９２５
号明細書等に開示されているような単量体を用いること
ができ、その様な単量体としては、例えば、ベンゾフェ
ノン、ベンゾイン、アンスラキノン等にカルボキシル基
や水酸基を導入し、これにグリシジル（メタ）アクリレ
ートを反応させて合成したもの、２−アクリロイルオキ
シＪ＼ンソフェノン、アクリロイル−２−（ｐ−クロル
ｌベンゾイル）フェニルカルボモイルエタン、１−（ｐ
−Ｊ＼ンソフエノギシ）−２−ヒドロキシ−４−ペンテ
ン、ポリクロロフェニルグリシジルエーテルと（メタ）
アクリル酸の反応生成物、３−（ペンタクロロフェノキ
シ）−２−ヒドロキシプロピルメタクリレ−１・等が挙
げられる。In addition, examples of the functional group-containing monomer having a photosensitizing effect, which is an essential component of the acrylic copolymer (b), include:
U.S. Patent No. 3004073 or U.S. Patent No. 3575925
Examples of such monomers include benzophenone, benzoin, anthraquinone, etc., into which a carboxyl group or hydroxyl group is introduced, and glycidyl Synthesized by reacting (meth)acrylates, 2-acryloyloxyJ＼sophenone, acryloyl-2-(p-chlorobenzoyl)phenylcarbomoylethane, 1-(p-chlorobenzoyl)phenylcarbomoylethane,
-2-hydroxy-4-pentene, polychlorophenyl glycidyl ether and (meth)
Examples include reaction products of acrylic acid, 3-(pentachlorophenoxy)-2-hydroxypropyl methacrylate-1.
上記光増゛感作用を持つ官能基含有単量体の構成比率は
、アクリル共重合体（ｂ）中、５〜３０重量％の範囲で
あり、特に７〜２５重竜％の範囲であるのか好ましい。The composition ratio of the functional group-containing monomer having a photosensitizing effect is in the range of 5 to 30% by weight, particularly in the range of 7 to 25% by weight, in the acrylic copolymer (b). preferable.
該単量体の構成比率が５重量％より少ないと、アクリル
共重合体（ａ）と組み合わせて光照射した場合、充分な
照射時間をとらないと未硬化を生しる恐れがあり、また
、充分照射した場合でも得られる感圧接着剤は凝集力に
乏しく、かつ、被接着体への糊残りのひどいものとなる
恐れがある。また、該単量体の構成比率が３０重量％を
超える場合は、光照射した時に部分的な過剰の架橋結合
が形成され易く、その結果、凝集力が強くなり過きて粘
着性に乏しくなる可能性がある。If the composition ratio of the monomer is less than 5% by weight, when irradiated with light in combination with the acrylic copolymer (a), there is a risk of uncuring unless sufficient irradiation time is taken; Even when sufficiently irradiated, the resulting pressure-sensitive adhesive has poor cohesive strength and may leave a significant amount of adhesive residue on objects to be adhered. In addition, if the composition ratio of the monomer exceeds 30% by weight, excessive cross-linking is likely to be partially formed when irradiated with light, and as a result, the cohesive force becomes too strong and the adhesiveness becomes poor. there is a possibility.
アクリル共重合体（ｂ）は、上記アクリル共重合体（ａ
）を得たのと同じ方法で、Ｍｗが５０００〜５００００
となるように重合せしめることによって共重合体とする
ことができる。該共重合体（ｂ）のＭｗが５０００より
小さいと得られる感圧接着剤は凝集力に乏しく、かつ、
被接着体への糊残りが生じるようになり、Ｍｗが５００
００より大きくなると、最終的に得られる接着剤組成物
の粘度が上昇し、基材への塗工作業が著しく困難となる
。The acrylic copolymer (b) is the acrylic copolymer (a)
), Mw is 5000 to 50000.
A copolymer can be obtained by polymerizing the following. When the Mw of the copolymer (b) is less than 5000, the resulting pressure-sensitive adhesive has poor cohesive force, and
Glue began to remain on the adhered object, and Mw reached 500.
When it is larger than 00, the viscosity of the adhesive composition finally obtained increases, making it extremely difficult to apply it to the substrate.
本発明の光硬化型感圧接着剤組成物は、上記アクリル共
重合体（ａ）８０〜９０重量％、及び、上記アクリル共
重合体（ｂ）２０〜１０重量％の比率で混合して成るも
のであり、該混合比率において共重合体（ａ）が８０重
量％より少ない場合も、また、９０重量％より多い場合
の何れにおいても、得られる感圧接着剤は粘着力、凝集
力、糊残り等、バランスの取れた接着特性が得られなく
なる恐れがある。The photocurable pressure-sensitive adhesive composition of the present invention is formed by mixing the above acrylic copolymer (a) in a ratio of 80 to 90% by weight and the above acrylic copolymer (b) in a ratio of 20 to 10% by weight. Whether the copolymer (a) is less than 80% by weight or more than 90% by weight in the mixing ratio, the resulting pressure-sensitive adhesive has poor adhesive strength, cohesive strength, and adhesive strength. Otherwise, there is a risk that balanced adhesion properties may not be obtained.
特に、本発明の感圧接着剤組成物においては、共重合体
（ｂ）中の光増感作用を持つ官能基含有７１量体が、ア
クリル共重合体（ａ）及びアクリル共重合体（ｂ）の合
計量に対して、０．２〜１，５重量％の範囲の含有率と
なるように、上記アクリル共重合体（ａ）とアクリル共
重合体（ｂ）とを、上記混合比率の範囲内で適宜に組み
合わせることによって、粘着力、凝集力、糊残り等の点
てバランスの取れた優れた接着特性が得られるので好ま
しく、特に０．５〜１．５重量％の範囲の含有率となる
ようにするのが好ましい。In particular, in the pressure-sensitive adhesive composition of the present invention, the functional group-containing 71-mer having a photosensitizing effect in the copolymer (b) is combined with the acrylic copolymer (a) and the acrylic copolymer (b). ) The above-mentioned acrylic copolymer (a) and acrylic copolymer (b) were mixed at the above-mentioned mixing ratio so that the content was in the range of 0.2 to 1.5% by weight based on the total amount of By appropriately combining within the range, excellent adhesive properties with a good balance in terms of adhesive force, cohesive force, adhesive residue, etc. can be obtained, so it is preferable, and the content is particularly preferably in the range of 0.5 to 1.5% by weight. It is preferable to make it so that
本発明の接着剤組成物の光硬１ヒ後の重合体のカラス転
移温度は、−２０〜−７０℃の範囲であるのが好ましい
。The glass transition temperature of the polymer of the adhesive composition of the present invention after photocuring is preferably in the range of -20 to -70°C.
また、本発明の接着剤組成物を硬化せしめるには、１８
０〜４００ｎｍの波長範囲の紫外線を用いるのが好まし
く、この様な紫外線の発生源としては、高圧水銀ランプ
、メタルハライドランプ等を好ましく用いることができ
る。Further, in order to cure the adhesive composition of the present invention, 18
It is preferable to use ultraviolet light in the wavelength range of 0 to 400 nm, and as a source of such ultraviolet light, a high-pressure mercury lamp, a metal halide lamp, etc. can be preferably used.
本発明は、上記アクリル共重合体（ａ）と上記アクリル
共重合体（ｂ）の所定量を組合せて、初めて優れた接着
特性が得られるものである。その理由は、光増感作用を
もつ官能基含有単量体を共重合せしめた低分子量のアク
リル重合体（ｂ）を光開始剤として用いることにより、
紫外線照射後の粘着層を形成する高分子鎖の架橋間分子
量が、通常の光開始剤、例えば、ベンゾフェノン、アセ
トフェノン、ベンゾインエチルエーテル等を使って形成
させた高分子鎖の架橋間分子量よりも大きく、また、紫
外線照射による架橋反応が安定し、架橋むらが少ないた
め、優れた接着特性が得られるものと推察される。なお
、上記アクリル共重合体（ａ）と上記アクリル共重合体
（ｂ）を絹み合わせた場合、その中に含まれる光開始剤
成分が少量で問題となる場合は、通常の光開始剤、例え
ば、ヘンジイン、ベンゾフェノン、ペンツインイソブチ
ルエーテル等を併用しても差し支えない。In the present invention, excellent adhesive properties can only be obtained by combining predetermined amounts of the acrylic copolymer (a) and the acrylic copolymer (b). The reason is that by using a low molecular weight acrylic polymer (b) copolymerized with a functional group-containing monomer that has a photosensitizing effect as a photoinitiator,
The inter-crosslink molecular weight of the polymer chains forming the adhesive layer after UV irradiation is larger than the inter-cross link molecular weight of polymer chains formed using a normal photoinitiator, such as benzophenone, acetophenone, benzoin ethyl ether, etc. Moreover, it is presumed that excellent adhesive properties can be obtained because the crosslinking reaction caused by ultraviolet irradiation is stable and crosslinking unevenness is small. In addition, when the above-mentioned acrylic copolymer (a) and the above-mentioned acrylic copolymer (b) are combined, if a small amount of the photoinitiator component contained therein causes a problem, a normal photoinitiator, For example, hengeine, benzophenone, pentwinisobutyl ether, etc. may be used in combination.
次に、本発明を実施例によってさらに詳細に説明するが
、本発明はこれら実施例の記載によって制限されるもの
ではない。なお、以下の実施例において、各成分の配合
量は重量部で示した。Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by the description of these Examples. In addition, in the following examples, the amount of each component is shown in parts by weight.
ム １−１ニアクリル 重Ａ ａ のパ告４ツロフラ
スコに酢酸ブチル３０部を加え、窒素気流中攪拌しなか
ら９５℃にする。そこへ、２−エチルへキシルアクリレ
ート９３部、アクリル酸７部、酢酸ブチル５０部、α、
α゛−アソヒスイソブチロニトリル３部から成る混合物
を３時間かけて滴下し、更に９５°Ｃて５時間反応を続
けることにより共重合体’４３ ｔ（ｙ、を得た（共重
合体のＭ ｗ ＝３９０００）。Add 30 parts of butyl acetate to a four-pack flask containing Niacryl Heavy A a and heat to 95° C. while stirring in a nitrogen stream. There, 93 parts of 2-ethylhexyl acrylate, 7 parts of acrylic acid, 50 parts of butyl acetate, α,
A mixture consisting of 3 parts of α゛-isohisisobutyronitrile was added dropwise over 3 hours, and the reaction was further continued at 95°C for 5 hours to obtain copolymer '43t(y). M w =39000).
さらに、この共重合体溶液に、アジリジニルエチルアク
リレ−１−２，７部、及び、ハイドロギノンモノメチル
エーテル ０．０５部からなる混合物を約１０分間をか
けて滴下し、５０°Ｃの温度で６時間反応を続け、側鎖
にメタクリロイル基を有するＭｗか４００００のアクリ
ル共重合体（ａ）を得た。Furthermore, a mixture consisting of 1-2.7 parts of aziridinylethyl acrylate and 0.05 parts of hydroginone monomethyl ether was added dropwise to this copolymer solution over about 10 minutes, and the mixture was heated to 50°C. The reaction was continued for 6 hours at a temperature of , to obtain an acrylic copolymer (a) having Mw of 40,000 and having a methacryloyl group in the side chain.
Δ゛ｌ−２： アクリル 重Δ″ｌ〕 のり゛告４ツ
ロフラスコに酢酸ブチル３０部を加え、窒素気流中攪拌
しながら９５℃にする。そこへ、下記表−１に示すそれ
ぞれの組成の単量体混合物１００部、酢酸ブチル５０部
、及び、α、α゛−アゾビスイソブチロニトリル２部か
ら成る混合物を３時間かけて滴下し、さらに９５で５時
間反応を続けることによって、Ｍｗ及び光増感作用を有
する官能基単量体含有率の各々異なるアクリル共重合体
（ｂ−１）〜（ｂ−７）溶液を得た。なお、得られた各
々の共重合体（ｂ）のＭｗを表−１に併せて示した。Δ゛l-2: Acrylic weight Δ″l] Glue 30 parts of butyl acetate was added to a 4-ton flask and heated to 95°C while stirring in a nitrogen stream.To this, each unit of composition shown in Table 1 below was added. A mixture consisting of 100 parts of the polymer mixture, 50 parts of butyl acetate, and 2 parts of α,α゛-azobisisobutyronitrile was added dropwise over 3 hours, and the reaction was continued at 95°C for 5 hours to obtain Mw and Solutions of acrylic copolymers (b-1) to (b-7) having different contents of functional group monomers having a photosensitizing effect were obtained. Mw is also shown in Table-1.
（以下余白）
＝１５一
実施例−１〜８
上記合成例−１で得たアクリル共重合体（ａ）、及び、
合成例−２で得たアクリル共重合体（ｂ）を、下記表−
２に示した組成で均一に混合して光硬化型感圧接着剤組
成物を調整した。(The following is a blank space) = 15 Examples-1 to 8 Acrylic copolymer (a) obtained in the above Synthesis Example-1, and
The acrylic copolymer (b) obtained in Synthesis Example-2 is shown in the table below.
A photocurable pressure-sensitive adhesive composition was prepared by uniformly mixing the composition shown in 2.
以上で得られた接着剤組成物を、厚さ２５μｍのポリエ
ステルフィルム上ここ、硬化後の厚さが約２５μｍとな
るように塗布し、次いで高圧水銀ランプ（８０ｗ／ ｃ
ｍ）２灯で１５ｃｍの照射距離にて、１２秒または１
８秒間光照射した後、１］２５ｍｍのテープ状乙こカッ
トして粘着テープを作成した。得られた粘着テープにつ
いて、その粘着特性を下記の評価方法で評価し、評価結
果を併せて表−２に示した。The adhesive composition obtained above was applied onto a polyester film with a thickness of 25 μm so that the thickness after curing would be approximately 25 μm, and then a high-pressure mercury lamp (80 w/c
m) 2 lights at 15cm irradiation distance for 12 seconds or 1
After irradiating with light for 8 seconds, 1] a 25 mm tape-like strip was cut to prepare an adhesive tape. The adhesive properties of the obtained adhesive tape were evaluated by the following evaluation method, and the evaluation results are also shown in Table 2.
止」１ブＬ詰
（１）粘着力（１８０°ビール）： ＪＩＳ Ｚ
０２３７に規定された試験方法に準拠し、粘着テープを
ステンレス板に貼着、３０分後に１８０°方向に剥離し
、その際の剥離強度を粘着力とする。1 bottle (1) Adhesive strength (180° beer): JIS Z
In accordance with the test method specified in 0237, an adhesive tape is attached to a stainless steel plate and peeled off in a 180° direction after 30 minutes, and the peel strength at that time is defined as adhesive strength.
（２）保持力（クリープ）：ＪＩＳ Ｚ ０２３７
に規定された試験方法に準拠し、粘着テープをステンレ
ス板に貼着、３０分後、粘着テープの一端に１ ｋｇの
荷重をかけ、４０℃で粘着テープがステンレス板から脱
落するまでの時間を測定する。(2) Holding force (creep): JIS Z 0237
Adhering the adhesive tape to a stainless steel plate in accordance with the test method specified in Measure.
（３）被接着体への糊残り： 上記（１）の粘着力測定
後のステンレス板表面を観察し、ステンレス板に粘着剤
か残っているか否か（糊残り状態）を゛評価する。(3) Adhesive residue on object to be adhered: Observe the surface of the stainless steel plate after measuring the adhesive force in (1) above, and evaluate whether or not there is any adhesive left on the stainless steel plate (glue residue state).
（以下余白）
比較例−１〜３
上記合成例で製造したアクリル共重合体（ａ）、及び、
アクリル共重合体（ｂ−５）〜（ｂ−７）を用い、下記
表−３に示した組成で均一に混合して光硬化型感圧接着
剤組成物を調整した。(Left below) Comparative Examples-1 to 3 Acrylic copolymer (a) produced in the above synthesis example, and
Using acrylic copolymers (b-5) to (b-7), a photocurable pressure-sensitive adhesive composition was prepared by uniformly mixing the compositions shown in Table 3 below.
以上で得られた接着剤組成物を、上記実施例と同様にし
て粘着テープを作成し、次いて評価した。An adhesive tape was prepared from the adhesive composition obtained above in the same manner as in the above example, and then evaluated.
評価結果を併せて表−３に示した。The evaluation results are also shown in Table-3.
（以下余白）
表−３
表の補足説明
（＊１）Ｐｈｏｔ、 Ｉｎ、濃度 ；接着剤組成物中の
光増感作用を有する官能基単量体の含有率
（重量％）
（＊２）ＵＶ照射時間 ；接着剤組成物を硬化させる際
の紫外線の照射時間（秒）
（１：３）１８０６ピール；テープの粘着力（ｇ／２５
ｍｍ）（ｔ４）クリープ ；テープがステンレス板
から脱落するまでの時間（分）、
○印は２４時間の試験後におい
ても脱落は勿論ずれの発生の全
くないもの
（＊５）糊残り ；○印は糊残りか全くないもの
〔発明の効果〕
本発明の光硬化型感圧接着剤組成物は、上記特定組成の
アクリル共重合体（ａ）と（ｂ）を、特定の比率で組み
合わせることからなっているので、粘着力、凝集力に優
れ、糊残りといった問題点の発生もなく、バランスのと
れた極めて優れた特性の感圧接着剤ということかできる
。(Margins below) Table 3 Supplementary explanation of the table (*1) Phot, In, concentration; content of functional group monomer with photosensitizing effect in adhesive composition (wt%) (*2) UV Irradiation time; UV irradiation time (seconds) when curing the adhesive composition (1:3) 1806 peel; Tape adhesive strength (g/25
mm) (t4) Creep; Time (minutes) until the tape falls off the stainless steel plate. ○ mark means that there is no slipping or falling off even after 24 hours of testing (*5) Adhesive residue; ○ mark [Effects of the Invention] The photocurable pressure-sensitive adhesive composition of the present invention is produced by combining acrylic copolymers (a) and (b) having the above-mentioned specific composition in a specific ratio. Therefore, it can be said that it is a pressure-sensitive adhesive with excellent adhesion and cohesive strength, and no problems such as adhesive residue, and has extremely well-balanced characteristics.
特許出願人 藤倉化成株式会社Patent applicant: Fujikura Kasei Co., Ltd.
Claims (2)
分子量が３００００〜５００００の アクリル系共重合体８０〜９０重量％、 及び、 （ｂ）構成成分中、光増感作用を有する官 能基単量体５〜３０重量％を含有してな る重量平均分子量が５０００〜５０００ ０のアクリル系共重合体２０〜１０重量 ％、 から成る光硬化型感圧接着剤組成物。(1) (a) 80 to 90% by weight of an acrylic copolymer having a (meth)acryloyl group and a weight average molecular weight of 30,000 to 50,000, and (b) a functional group having a photosensitizing effect among the constituent components; A photocurable pressure-sensitive adhesive composition comprising 20 to 10% by weight of an acrylic copolymer having a weight average molecular weight of 5,000 to 5,0000.
ａ）のアクリル系共重合体及び前記（ｂ）のアクリル系
共重合体の合計量中０．２〜１．５重量％の濃度で含有
して成るものである請求項１に記載の光硬化型感圧接着
剤組成物。(2) The functional group monomer having a photosensitizing effect is selected from the above (
The photocuring according to claim 1, which contains the acrylic copolymer (a) and the acrylic copolymer (b) at a concentration of 0.2 to 1.5% by weight based on the total amount. Type pressure sensitive adhesive composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11477288A JPH01287114A (en) | 1988-05-13 | 1988-05-13 | Photo-setting type adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11477288A JPH01287114A (en) | 1988-05-13 | 1988-05-13 | Photo-setting type adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01287114A true JPH01287114A (en) | 1989-11-17 |
Family
ID=14646305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11477288A Pending JPH01287114A (en) | 1988-05-13 | 1988-05-13 | Photo-setting type adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01287114A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008208299A (en) * | 2007-02-28 | 2008-09-11 | Konica Minolta Holdings Inc | Composition, liquid and gel-forming method |
-
1988
- 1988-05-13 JP JP11477288A patent/JPH01287114A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008208299A (en) * | 2007-02-28 | 2008-09-11 | Konica Minolta Holdings Inc | Composition, liquid and gel-forming method |
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