JPH02113018A - Silicone-based releasable film, tacky member and separator thereof - Google Patents
Silicone-based releasable film, tacky member and separator thereofInfo
- Publication number
- JPH02113018A JPH02113018A JP26677288A JP26677288A JPH02113018A JP H02113018 A JPH02113018 A JP H02113018A JP 26677288 A JP26677288 A JP 26677288A JP 26677288 A JP26677288 A JP 26677288A JP H02113018 A JPH02113018 A JP H02113018A
- Authority
- JP
- Japan
- Prior art keywords
- silicone
- film
- group
- layer
- separator
- 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
Links
- 229920001296 polysiloxane Polymers 0.000 title claims description 36
- 239000000853 adhesive Substances 0.000 claims abstract description 20
- 230000001070 adhesive effect Effects 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229920006268 silicone film Polymers 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 125000000962 organic group Chemical group 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 polysiloxane Polymers 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002390 adhesive tape Substances 0.000 description 8
- 239000001856 Ethyl cellulose Substances 0.000 description 7
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 7
- 235000019325 ethyl cellulose Nutrition 0.000 description 7
- 229920001249 ethyl cellulose Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 229920002367 Polyisobutene Polymers 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FASUFOTUSHAIHG-UHFFFAOYSA-N 3-methoxyprop-1-ene Chemical compound COCC=C FASUFOTUSHAIHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000002655 kraft paper 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- OLKHRYQRCJLWLL-UHFFFAOYSA-N 2-cyclohex-3-en-1-yloxirane Chemical compound C1OC1C1CC=CCC1 OLKHRYQRCJLWLL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- 101100221077 Arabidopsis thaliana CML12 gene Proteins 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GLROGUSVUGSGPO-UHFFFAOYSA-N bis(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1C2OC2CC(C)C1OC(=O)CCCCC(=O)OC1CC2OC2CC1C GLROGUSVUGSGPO-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、シリコーン皮膜層に易膨潤性ないし易溶解性
の樹脂からなる層を付加した複層構造を有し、油性イン
キ印字性、剥離特性に優れるシリコーン系剥離性皮膜、
並びにその粘着部材及びセパレータに関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention has a multi-layer structure in which a layer of easily swellable or easily soluble resin is added to a silicone film layer, and has excellent oil-based ink printability and release characteristics. Excellent silicone release film,
and its adhesive member and separator.
発明の背景
粘着テープ等の粘着部材における支持基材の背面を剥離
剤で処理して、基材背面より粘着面を容易に剥がせるよ
う対処されているが、その処理皮膜にはセパレータの場
合と同様、宛名書き等の必要から印字可能なことが望ま
れる。BACKGROUND OF THE INVENTION In adhesive members such as adhesive tapes, the back side of the supporting base material is treated with a release agent so that the adhesive side can be easily peeled off from the back side of the base material. Similarly, it is desirable that it be printable for purposes such as writing addresses.
従来、印字可能なシリコーン系剥離性皮膜としては、特
殊なポリシロキサンに微粉末シリカやエチルセルロース
を混合したものが知られていた（特開昭５９−１２６４
７５号公報、同５９−１４７０４８号公報）。Conventionally, a printable silicone-based release film made by mixing special polysiloxane with finely powdered silica or ethyl cellulose was known (Japanese Patent Laid-Open No. 59-1264).
No. 75, No. 59-147048).
しかし、その混合のためかポリシロキサンの硬化が阻害
され、形成皮膜の剥離特性が大きく低下するという致命
的な問題点があった。However, there was a fatal problem in that the curing of the polysiloxane was inhibited, possibly due to the mixing, and the peeling properties of the formed film were greatly reduced.
一方、分子中にエポキシ基官能性成分を含有するポリオ
ルガノシロキサンをオニウム塩系硬化触媒を用いて紫外
線硬化させたシリコーン系剥離性皮膜が知られていた（
特開昭５６−３８３５０号公報、同６０−４７０６４号
公報）。これは、剥離剤の無溶剤塗工を可能ならしめて
環境衛生性、火災に対する安全性、省エネルギー性、剥
離性付与処理の効率性を付与したものである。しかし、
油性インキによる印字性を有しない。また、皮膜の硬化
が不充分となりやすく、実用的レベルまで硬化させるに
は多（の紫外線照射量を要し、その場合でも形成される
剥離性皮膜の剥離特性がバラツキやすい。On the other hand, a silicone-based release film was known in which a polyorganosiloxane containing an epoxy functional component in the molecule was cured by ultraviolet light using an onium salt-based curing catalyst (
JP-A-56-38350, JP-A-60-47064). This makes it possible to apply a release agent without a solvent, thereby providing environmental hygiene, fire safety, energy saving, and efficiency in the process for imparting release properties. but,
Cannot be printed with oil-based ink. Further, the film tends to be insufficiently cured, requiring a large amount of ultraviolet irradiation to cure it to a practical level, and even in that case, the peeling characteristics of the peelable film formed tend to vary.
そのため、これに貼着される粘着面が汚染されて接着力
が低下する難点があった。As a result, the adhesive surface to which it is attached becomes contaminated, resulting in a decrease in adhesive strength.
先行技術及び課題
本発明者らは先に、分子中にポリエーテル・ポリメチレ
ン基を導入したポリオルガノシロキサンを成分とする剥
離剤からなるシリコーン系剥離性皮膜を提案した（特願
昭６２−２３５０９４号）。これは皮膜の硬化性が良好
で剥離性能に優れ、油性インキによる印字性も有する。Prior Art and Problems The present inventors previously proposed a silicone-based release film consisting of a release agent containing polyorganosiloxane with polyether/polymethylene groups introduced into the molecule (Japanese Patent Application No. 62-235094). ). This film has good curing properties, excellent peeling performance, and printability with oil-based inks.
しかし、梱包用の粘着テープの如く、粘着部材やセパレ
ータの多様な用途において、その印字性がさらに良好な
ことが望まれる場合がある。However, in various uses of adhesive members and separators, such as adhesive tapes for packaging, it is sometimes desired that the printing performance be even better.
課題を解決するための手段
本発明は、特殊な造膜性樹脂を用いて複層構造の皮膜と
することにより、前記のシリコーン系剥離性皮膜の剥離
特性を低下させることなく、その印字性の向上をはかっ
たものである。Means for Solving the Problems The present invention uses a special film-forming resin to form a film with a multilayer structure, thereby improving the printability of the silicone-based release film without deteriorating its release characteristics. This is an attempt to improve the results.
すなわち、本発明は、有機溶剤に易膨潤性ないし易溶解
性の造膜性樹脂からなるインキ親和層の上にシリコーン
皮膜層を有してなり、そのシリコーン皮膜層が一般式
（ただし、Ｒは炭素数１〜２０のアルキル基、シクロア
ルキル基、アリール基又はアラルキル基であり、Ｘはエ
ポキシ基官能性有機基であり、Ｙはポリエーテル・ポリ
メチレン基であり、ｍ／（ｅ＋ｍ ＋ ｒｌ ）が０．
０５〜９０％であり％ ｎ ／ （ｅ ＋ ｍ ＋ ｎ
）が０．５〜９０％である。）
で表されるポリオルガノシロキサンを、オニウム塩系硬
化触媒を用いて硬化処理してなるものであることを特徴
とするシリコーン系剥離性皮膜、並びに
前記のシリコーン系剥離性皮膜を片面に有する支持基材
の他面に粘着層を有することを特徴とする粘着部材、及
び
支持基材の片面又は両面に前記のシリコーン系剥離性皮
膜を有することを特徴とするセパレータを提供するもの
である。That is, the present invention has a silicone film layer on an ink affinity layer made of a film-forming resin that is easily swellable or easily soluble in an organic solvent, and the silicone film layer has a general formula (where R is It is an alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, X is an epoxy group-functional organic group, Y is a polyether polymethylene group, and m/(e+m + rl) is 0.
05-90% and % n / (e + m + n
) is 0.5 to 90%. ) A silicone-based release film characterized by being formed by curing a polyorganosiloxane represented by the following with an onium salt-based curing catalyst, and a support having the silicone-based release film on one side. The present invention provides an adhesive member characterized by having an adhesive layer on the other side of the base material, and a separator characterized by having the silicone-based release film described above on one or both sides of the support base material.
作用
上記した造膜性樹脂からなるインキ親和層を被処理体側
に介在させることにより、剥離性皮膜と被処理体との密
着性が向上する。また、油性インキが染込みやすくなっ
て印字性が向上する。Effect: By interposing the ink affinity layer made of the film-forming resin described above on the object to be treated, the adhesion between the peelable film and the object to be treated is improved. In addition, the oil-based ink penetrates easily, improving printing performance.
一方、上記の一般式で表されるポリオルガノシロキサン
は、分子中に含有するポリエーテル・ポリメチレン成分
に基づいてオニウム塩系硬化触媒との相溶性に優れ、良
好で安定な紫外線硬化性、ないし熱硬化性を示す。On the other hand, the polyorganosiloxane represented by the above general formula has excellent compatibility with onium salt curing catalysts based on the polyether/polymethylene components contained in the molecule, and has good and stable UV curability or heat curability. Shows curability.
前記の結果、印字性と剥離特性に使れるシリコーン系剥
離性皮膜が形成される。As a result of the foregoing, a silicone-based release coating is formed which can be used for printability and release properties.
発明の構成要素の例示
本発明のシリコーン系剥離性皮膜は、被処理体側に位置
するインキ親和層と、シリコーン皮膜層の複層構造体か
らなる。Examples of Constituent Elements of the Invention The silicone-based release film of the present invention consists of a multilayer structure including an ink affinity layer located on the side of the object to be treated and a silicone film layer.
インキ親和層の形成には、有機溶剤に易膨潤性ないし易
溶解性の造膜性樹脂が用いられる。２５℃ないし室温に
おいて有機溶剤、就中油性インキに使用のものに膨潤、
ないし溶解するものが好ましく用いられる。一般に用い
られる造膜性樹脂としては、エチルセルロース、ポリイ
ソブチレン、アクリル系樹脂、熱可塑性ポリウレタン、
熱可塑性ポリエステルなどがあげられる。エトキシ基の
平均含有量が単位グルコースあたり４６〜５０重量％の
エチルセルロース、重量平均分子量が１．５万〜２００
万のポリイソブチレン、アクリル樹脂、メタクリル樹脂
の如きアクリル系樹脂、あるいはポリエチレングリコー
ルジメタクリレート、ポリエステルジアクリレート、ポ
リウレタンジアクリレートの如き多官能性アクリレート
の重合体からなるアクリル系樹脂、線状ポリマからなる
熱可塑性ポリウレタン、溶解度パラメータが８．９〜１
１の線状ポリマからなる熱可塑性ポリエステルなどが易
膨潤性、ないし易溶解性の点より好ましく用いられる。For forming the ink affinity layer, a film-forming resin that is easily swellable or easily soluble in an organic solvent is used. Swells in organic solvents, especially those used in oil-based inks, at 25°C to room temperature.
or soluble ones are preferably used. Commonly used film-forming resins include ethyl cellulose, polyisobutylene, acrylic resin, thermoplastic polyurethane,
Examples include thermoplastic polyester. Ethyl cellulose with an average content of ethoxy groups of 46 to 50% by weight per unit glucose, weight average molecular weight of 15,000 to 200
Acrylic resins such as polyisobutylene, acrylic resins, and methacrylic resins, or acrylic resins made of polymers of polyfunctional acrylates such as polyethylene glycol dimethacrylate, polyester diacrylate, and polyurethane diacrylate; Plastic polyurethane, solubility parameter 8.9-1
A thermoplastic polyester made of a linear polymer of No. 1 is preferably used from the viewpoint of easy swelling and easy solubility.
シリコーン皮膜層の形成には、下記の一般式で表される
ポリオルガノシロキサンが用いられる。A polyorganosiloxane represented by the following general formula is used to form the silicone film layer.
前記一般式中、Ｒは炭素数１〜２０のアルキル基、シク
ロアルキル基、アリール基又はアラルキル基である。剥
離性能の点よりはメチル基が好ましい。In the general formula, R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Methyl group is preferable from the viewpoint of peeling performance.
Ｘはエポキシ基官能性有機基である。゛その例としては
、γ−グリシジルオキシプロビル基：Ｃｓ Ｈａ −Ｏ
ＣＨ２Ｃ１−Ｉ ＣＨ２Ｎ２
β−（３，４−エポキシシクロヘキシル）エチルβ−（
４−メチル−３，４−エポキシシクロヘキなどがあげら
れる。X is an epoxy functional organic group.゛As an example, γ-glycidyloxyprobyl group: Cs Ha -O
CH2C1-I CH2N2 β-(3,4-epoxycyclohexyl)ethyl β-(
Examples include 4-methyl-3,4-epoxycyclohex.
Ｙはポリエーテル・ポリメチレン基である。この基は、
オニウム塩系硬化触媒と相溶性のよいポリエーテル・ポ
リメチレン基含有化合物であればよい。その例としては
、一般式。Y is a polyether polymethylene group. This group is
Any polyether/polymethylene group-containing compound that has good compatibility with the onium salt curing catalyst may be used. An example of this is the general formula.
−Ｒ１−０→Ｒ２０＋−ｑ−Ｒ３
で表されるものがあげられる。式中、Ｒ１はポリメチレ
ン基である。Ｒ２はエチレン基・ （−ＣＨ２ＣＨ２−
） 、プロピレン基： （−ＣＨ２ＣＨ（ＣＨ３））又
はブチレン基： （ＣＨ２ＣＨ（Ｃ２Ｈ５）−）である
。Ｒ３は水素原子又は炭素数が１〜２０のアルキル基で
ある。なお、本発明ではそのポリメチレン基（Ｒ１）が
トリメチレン基：［ＣＨ２Ｃ８２ＣＨ２］であるものが
入手容易さの点で好ましい。ポリエーテル部分の重合度
ｙはポリオルガノシロキサンにおけるポリエーテル・ポ
リメチレン基の含有割合にもよるが、一般には硬化触媒
との相溶性向上の点から２〜１００が適当であり、２〜
４０が好ましい。-R1-0→R20+-q-R3. In the formula, R1 is a polymethylene group. R2 is an ethylene group (-CH2CH2-
), propylene group: (-CH2CH(CH3)) or butylene group: (CH2CH(C2H5)-). R3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. In the present invention, it is preferable that the polymethylene group (R1) is a trimethylene group: [CH2C82CH2] from the viewpoint of easy availability. The degree of polymerization y of the polyether part depends on the content of polyether/polymethylene groups in the polyorganosiloxane, but in general, from the point of view of improving compatibility with the curing catalyst, a range of 2 to 100 is appropriate;
40 is preferred.
前記一般式中のｅ、ｍ、ｎは各構造単位の含有数を意味
する。本発明においてはｍ／ （ｅ ＋ｍ＋−ｎ）が０
．０５〜９０％で、ｎ／（ｆ！＋ｍ＋ｎ）が０．５〜９
０％のものが適当である。そのｍ／ （ｅ ＋ｍ＋ｎ）
が０．０５％未満であると得られる剥離剤が硬化性に乏
しくなり、９０％を超えると形成される剥離性皮膜が剥
離性能に乏しくなる。また、ｎ／（＋！＋ｍ＋ ｎ ）
が０．５％未満であるとオニウム塩系硬化触媒との相溶
性、得られる剥離剤の硬化性が乏しくなり、９０％を超
えると形成される剥離性皮膜が剥離性能に乏しくなる。e, m, and n in the general formula mean the number of each structural unit contained. In the present invention, m/(e +m+-n) is 0
．． 05-90%, n/(f!+m+n) is 0.5-9
0% is appropriate. That m/ (e +m+n)
If it is less than 0.05%, the resulting release agent will have poor curability, and if it exceeds 90%, the formed release film will have poor release performance. Also, n/(+!+m+ n )
If it is less than 0.5%, the compatibility with the onium salt curing catalyst and the curability of the resulting release agent will be poor, and if it exceeds 90%, the formed release film will have poor release performance.
剥離剤に無溶剤塗工性を付与する場合には、数平均分子
量が５００〜ｓｏｏ 、ｏｏｏ、就中１．０００〜５０
．０００のポリオルガノシロキサンが好ましく用いられ
る。When imparting solvent-free coating properties to the release agent, the number average molecular weight is 500 to soo, ooo, especially 1.000 to 50.
．． 000 polyorganosiloxane is preferably used.
上記した、分子中にエポキシ基官能性有機基とポリエー
テル・ポリメチレン基を含有するポリオルガノシロキサ
ンの調製は、例えば次の方法により行うことができる。The above-mentioned polyorganosiloxane containing an epoxy functional organic group and a polyether/polymethylene group in the molecule can be prepared, for example, by the following method.
すなわち、前記した各構造単位の含有割合となるように
所定数の未置換水素を有し、残りの水素は炭素数１〜２
０のアルキル基、シクロアルキル基、アリール基又はア
ラルキル基で置換されたポリシロキサンと、オレフィン
・グリシジルエーテルのようなエチレン性二重結合を有
する、あるいはケイ素に結合した水素と反応しつる官能
基を有するエポキシ基含有化合物の所定量と、オレフィ
ン・エチレングリコールのようなエチレン性二重結合を
有する、あるいはケイ素に結合した水素と反応しうる官
能基を有するポリエーテル系化合物の所定量とを反応さ
せて、前記ポリシロキサンにおける未置換水素を介して
エポキシ基含有化合物及びポリニー、２−ル系化合物を
ヒドロシリル化などにより導入する方法により得ること
ができる。That is, it has a predetermined number of unsubstituted hydrogens so as to have the content ratio of each structural unit described above, and the remaining hydrogens have 1 to 2 carbon atoms.
Polysiloxane substituted with zero alkyl group, cycloalkyl group, aryl group, or aralkyl group and a functional group that has an ethylenic double bond such as olefin glycidyl ether or that reacts with silicon-bonded hydrogen. A predetermined amount of an epoxy group-containing compound is reacted with a predetermined amount of a polyether compound having an ethylenic double bond, such as olefin or ethylene glycol, or a functional group capable of reacting with silicon-bonded hydrogen. It can be obtained by a method in which an epoxy group-containing compound and a polynylene, 2-l compound are introduced through hydrosilylation or the like via unsubstituted hydrogen in the polysiloxane.
なお、本発明において、
の各構造単位の連なりはブロック状でもよいし、ランダ
ムでもよい。In addition, in this invention, the series of each structural unit may be block-like and may be random.
本発明においてポリオルガノシロキサンは、オニウム塩
系硬化触媒を用いて紫外線照射により、あるいは加熱に
より硬化処理される。用いるオニウム塩系硬化触媒につ
いては特に限定はなく、公知物のいずれも用いうる。そ
の例としては、式：％式％（
だし、Ａ「はアリール基、Ｒはアルキル基又はアリール
基、Ｚ−はＢＦ４− Ｐ Ｆｓ −ＡｓＦｅ″″５
ｂＦｅ″″ ５ｂＣ１ａ−Ｈ８Ｏ４″″
ＣｌＯ４−などの如き非塩基性かつ非求核性の陰イオン
である。）で表されるようなジアゾニウム塩、スルホニ
ウム塩、ヨードニウム塩などがあげられる。In the present invention, polyorganosiloxane is cured by ultraviolet irradiation or heating using an onium salt curing catalyst. There is no particular limitation on the onium salt curing catalyst used, and any known catalyst can be used. Examples include the formula: %Formula% (where A is an aryl group, R is an alkyl group or an aryl group, Z- is BF4-PFs-AsFe''''5
bFe″″ 5bC1a-H8O4″″
It is a non-basic and non-nucleophilic anion such as ClO4-. ), diazonium salts, sulfonium salts, iodonium salts, etc.
オニウム塩系硬化触媒の配合量は、ポリオルガノシロキ
サン１００重量部あたり０．１〜２０重量部が適当であ
り、０．５〜ｌＯ重量部が好ましい。その配合量が０．
１重量部未満では硬化性に乏しいし、２０重量部を超え
ると剥離性能が阻害される場合がある。The amount of the onium salt curing catalyst to be blended is suitably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of polyorganosiloxane. Its blending amount is 0.
If it is less than 1 part by weight, the curability is poor, and if it exceeds 20 parts by weight, the peeling performance may be impaired.
本発明においては、必要に応じ１個又は２個以上のエポ
キシ系官能基を有する単量体を配合してもよい。かかる
単量体はオニウム塩系硬化触媒の分散に有効で、硬化性
、印字性の向上にも有効である。一般に用いられる当該
単量体の例としては、エチレングリコールジグリシジル
エーテル、グリセリンジグリシジルエーテル、ビニルシ
クロヘキセンジオキサイド、リモネンジオキサイド、３
゜４−エポキシシクロヘキシルメチル〜３’、４’エポ
キシシクロへキシルカルボキシレート、ビス−（６−メ
チル−３，４−エポキシシクロヘキシル）アジペートな
どがあげられる。エポキシ系官能基を有する単量体の配
合量は、ポリオルガノシロキサン１００重量部あたり１
〜１万重量部が適当であり、１０−１．０００重量部が
好ましい。In the present invention, a monomer having one or more epoxy functional groups may be blended as required. Such monomers are effective in dispersing onium salt-based curing catalysts, and are also effective in improving curability and printability. Examples of commonly used monomers include ethylene glycol diglycidyl ether, glycerin diglycidyl ether, vinylcyclohexene dioxide, limonene dioxide,
Examples include 4-epoxycyclohexylmethyl to 3',4'epoxycyclohexylcarboxylate, and bis-(6-methyl-3,4-epoxycyclohexyl)adipate. The blending amount of the monomer having an epoxy functional group is 1 per 100 parts by weight of polyorganosiloxane.
~10,000 parts by weight is suitable, and 10-1,000 parts by weight is preferred.
なお、エポキシ系官能基を有する単量体を配合する場合
、オニウム塩系硬化触媒の使用量は、当該単量体とポリ
オルガノシロキサンの合計１００重量部あたり０．１〜
２０重量部とすることが適当である。In addition, when blending a monomer having an epoxy functional group, the amount of onium salt curing catalyst used is 0.1 to 100 parts by weight in total of the monomer and polyorganosiloxane.
A suitable amount is 20 parts by weight.
本発明のシリコーン系剥離性皮膜の形成は、例えば、水
又は有機溶剤に分散又は溶解させた造膜性樹脂を被処理
体に塗布し、乾燥させてインキ親和層を形成したのち、
その上にオニウム塩系硬化触媒等を配合したポリオルガ
ノシロキサンを塗布し、硬化処理してシリコーン皮膜層
を形成する方法、あるいは造膜性樹脂、ポリオルガノシ
ロキサン、オニウム塩系硬化触媒等を水又４は有機溶剤
に分散又は溶解させ、その液を被処理体に塗布し、乾燥
、硬化処理してインキ親和層とシリコーン皮膜層を形成
する方法などにより行うことができる。The silicone-based release film of the present invention can be formed by, for example, applying a film-forming resin dispersed or dissolved in water or an organic solvent to the object to be treated and drying it to form an ink-friendly layer.
There is a method in which polyorganosiloxane mixed with an onium salt curing catalyst, etc. is applied and cured to form a silicone film layer, or a film-forming resin, polyorganosiloxane, onium salt curing catalyst, etc. is applied with water or Step 4 can be carried out by dispersing or dissolving in an organic solvent, applying the solution to the object to be treated, drying and curing to form an ink affinity layer and a silicone film layer.
後者の、各成分を一括に混合した液を塗布する方法によ
っても、造膜性樹脂とポリオルガノシロキサンの相分離
により目的とする複層構造のシリコーン系剥離性皮膜を
形成することができる。塗布には、スクイズコータ等の
適宜な塗布機を用いてよい。シリコーン皮膜層を形成す
るための硬化処理は、高圧水銀ランプやメタルハライド
ランプなどの適宜な紫外線発生装置を用いての紫外線照
射方式、加熱方式、それらの併用方式などにより行うこ
とができる。従って、前記の一括混合液方法の場合には
、塗布層の乾燥を兼ねた加熱処理でシリコーン皮膜層を
形成することもできるし、乾燥後に紫外線を照射してシ
リコーン皮膜層を形成することもできる。なお加熱温度
は、被処理体の耐熱性等により適宜に決定してよい。一
般には、６０〜２００℃、就中１００〜１５０℃とされ
る。The latter method of applying a solution in which each component is mixed at once can also form a silicone-based release film with a multilayer structure through phase separation of the film-forming resin and polyorganosiloxane. For coating, an appropriate coating machine such as a squeeze coater may be used. The curing treatment for forming the silicone film layer can be performed by an ultraviolet irradiation method using an appropriate ultraviolet generator such as a high-pressure mercury lamp or a metal halide lamp, a heating method, or a combination thereof. Therefore, in the case of the batch liquid mixture method described above, the silicone film layer can be formed by heat treatment that also serves as drying of the coating layer, or the silicone film layer can be formed by irradiating ultraviolet rays after drying. . Note that the heating temperature may be appropriately determined depending on the heat resistance of the object to be processed. Generally, the temperature is 60 to 200°C, especially 100 to 150°C.
シリコーン系剥離性皮膜におけるインキ親和層の厚さは
、０．１〜５０μｓ、シリコーン皮膜層の厚さは０．１
〜２ｕ−が適当である。インキ親和層の厚さが０．１μ
■未満では油性インキによる印字性の向上効果に乏しい
。The thickness of the ink affinity layer in the silicone release film is 0.1 to 50 μs, and the thickness of the silicone film layer is 0.1 μs.
~2u- is appropriate. The thickness of the ink affinity layer is 0.1μ
If it is less than (2), the effect of improving printing performance by oil-based ink is poor.
本発明のシリコーン系剥離性皮膜は、例えばセパレータ
の形成や、粘着テープ等の粘着部材における背面処理な
ど、粘着面に接着され、その粘着面より容易に剥離でき
ること′が望まれる用途などに好ましく用いられる。The silicone-based release film of the present invention is preferably used in applications where it is desired to be adhered to an adhesive surface and easily peeled off from the adhesive surface, such as in the formation of separators and back treatment of adhesive members such as adhesive tapes. It will be done.
本発明の粘着部材は、かかるシリコーン系剥離性皮膜を
支持基材の片面に設け、他面に粘着層を付設したもので
ある。また、セパレータは、かかるシリコーン系剥離性
皮膜を支持基材の片面又は両面に設けたものである。用
いる支持基材ついては特に限定はない。一般には、紙、
プラスチックラミネート紙、布、プラスチックラミネー
ト布、プラスチックフィルム、金属箔、発泡体などが用
いられる。なお、粘着部材の形成は、予めシリコーン系
剥離性皮膜を設けた支持基材の他面に粘着剤を付設する
方法など、公知の方法で行ってよい。The adhesive member of the present invention has such a silicone-based releasable film provided on one side of a supporting base material, and an adhesive layer provided on the other side. Furthermore, the separator is one in which such a silicone-based releasable film is provided on one or both sides of a supporting base material. There are no particular limitations on the supporting base material to be used. Generally, paper,
Plastic laminated paper, cloth, plastic laminated cloth, plastic film, metal foil, foam, etc. are used. The adhesive member may be formed by a known method, such as applying an adhesive to the other side of a supporting base material on which a silicone-based releasable film has been previously provided.
発明の効果
本発明のシリコーン系剥離性皮膜は、被処理体側に位置
するインキ親和層とシリコーン皮膜層の複層構造からな
るで、被処理体との密着性に優れて脱落しに＜（、かつ
油性インキが染込みやすくて良好な印字性を有する。ま
た、シリコ−ン皮膜層は良好な硬化性に基づいて剥離特
性に優れている。Effects of the Invention The silicone-based release film of the present invention has a multilayer structure of an ink affinity layer and a silicone film layer located on the side of the object to be treated, and has excellent adhesion to the object to be treated and is resistant to falling off. In addition, the silicone film layer has good printability because it is easily penetrated by oil-based ink.Furthermore, the silicone film layer has excellent peeling properties based on good curability.
その結果、かかるシリコーン系剥離性皮膜を有する本発
明の粘着部材及びセパレータは、剥離性皮膜で粘着面が
汚染されに＜＜、接着力が良好に維持される。As a result, the adhesive member and separator of the present invention having such a silicone-based releasable film can maintain good adhesion strength without contaminating the adhesive surface with the releasable film.
実施例
参考例
撹拌羽根、温度計、滴下ロートを備えたガラス製三ツロ
フラスコに、４−ビニルシクロヘキセンモノオキサイド
３７．８部（重量部、以下同様）と、ポリエヂレングリ
コールアリルメチルエーテル（数平均分子ｆｆ１４５０
） １３７．１部をテトラヒドロフラン５００部に溶解
させた溶液を加え、乾燥窒素気流下で３０分間撹拌後、
これにヒドロシリル化用白金触媒（白金−ビニルシロキ
サン錯塩）２．０部を添加して更に１０分間撹拌後、系
を４０℃に加温した。Examples Reference Examples In a glass three-way flask equipped with a stirring blade, a thermometer, and a dropping funnel, 37.8 parts of 4-vinylcyclohexene monooxide (parts by weight, the same applies hereinafter) and polyethylene glycol allyl methyl ether (number average molecule ff1450
) A solution of 137.1 parts dissolved in 500 parts of tetrahydrofuran was added, and after stirring for 30 minutes under a stream of dry nitrogen,
To this was added 2.0 parts of a platinum catalyst for hydrosilylation (platinum-vinylsiloxane complex salt), and after further stirring for 10 minutes, the system was heated to 40°C.
あった。there were.
（ただし、ｐ ／ ｑ ＝１８／１０であり、はランダ
ムに配列している。）
次に、上記の分子構造を有する数平均分子量が２０００
のポリシメヂル・メチルハイドロジエンシロキサン共重
合体１００部を、撹拌下にある前記の４０℃に加温した
系に約１時間かけて徐々に滴下し、その後、系を４５℃
に保持して２４時間反応させた。(However, p / q = 18/10, and are arranged randomly.) Next, if the number average molecular weight is 2000 and has the above molecular structure,
100 parts of the polycymetyl-methylhydrodiene siloxane copolymer was gradually added dropwise over about 1 hour to the stirred system heated to 40°C, and then the system was heated to 45°C.
The reaction mixture was maintained at a temperature of 100.degree. C. and reacted for 24 hours.
得られた反応液を減圧乾燥機に入れてテトラヒドロフラ
ンを乾燥させたのち、その乾燥物をｎ −ヘプタン中で
繰り返し精製して未反応物を除去し、再度減圧乾燥機に
てｎ−ヘプタンを乾燥除去した。The obtained reaction solution was placed in a vacuum dryer to dry the tetrahydrofuran, and then the dried product was repeatedly purified in n-heptane to remove unreacted materials, and the n-heptane was dried again in a vacuum dryer. Removed.
得られた生成物は、赤外吸収スペクトル、ＮＭＲスペク
トル分析の結果、下記の分子構造を有するものであった
。また、その数平均分子量は４７００でＹａは−Ｃ３Ｈ
ａ ０（ＣＨ２ＣＨ２０ｈ′；ＴＣＨ３であり、ｐ／
ｒ／５＝１８１５１５である。また、実施例１
トルエン／エタノール： ８０／２０ （重量比）の混
合溶剤に５重量％の濃度で溶解させた場合の粘度（２５
℃〉が１０ ｃＰｓのエチルセルロース（エトキシ基の
平均含有量４８．０〜４９．５重量％／単位グルコース
）にメタノールを加えて１０Ｍ量％溶液を調製し、これ
をワイヤーバーＲＯＤ嵐３にて厚さ１２０ｎのポリエチ
レンラミネートクラフト紙のラミネート面に塗工し、１
００℃の熱風恒温機中に５分間入れて乾燥させた。As a result of infrared absorption spectrum and NMR spectrum analysis, the obtained product had the following molecular structure. In addition, its number average molecular weight is 4700 and Ya is -C3H
a 0(CH2CH20h'; TCH3, p/
r/5=181515. In addition, the viscosity (25
methanol was added to ethyl cellulose (average content of ethoxy groups: 48.0 to 49.5 wt%/unit glucose) with a temperature of 10 cPs to prepare a 10M mass % solution, which was then thickened using a wire bar ROD Arashi 3. Coating on the laminated surface of polyethylene laminated kraft paper with a thickness of 120 nm,
It was placed in a hot air constant temperature machine at 00°C for 5 minutes to dry it.
ついで、その上に参考例で得たポリオルガノシロキサン
１００部に紫外線反応型スルホニウム塩系硬化触媒を５
部添加してなる混合物をスクイズコータにて塗工し、高
圧水銀ランプを設置した紫外線照射装置にて塗工面に紫
外線を１ジュール／−照射して硬化処理し、本発明のシ
リコーン系剥離性皮膜を有するセパレータを得た。なお
、前記の混合物の塗工量は、Ｉｇ／−とした。Next, 5 parts of an ultraviolet-reactive sulfonium salt-based curing catalyst was added to 100 parts of the polyorganosiloxane obtained in the reference example.
The silicone-based release coating of the present invention is obtained by coating the mixture with a squeeze coater and curing the coated surface by irradiating 1 joule/- of ultraviolet light with an ultraviolet irradiation device equipped with a high-pressure mercury lamp. A separator having the following properties was obtained. In addition, the coating amount of the said mixture was made into Ig/-.
実施例２
エチルセルロース溶液に代えて、ポリイソブチレン（重
量平均分子量約１００万）にトルエンを加えてなる５重
量％溶液を用いたほかは実施例１に準じて本発明のシリ
コーン系剥離性皮膜を有するセパレータを得た。ただし
、塗工にはワイヤーバーＲＯＤ歯６を用いた。Example 2 A silicone-based release film of the present invention was prepared in accordance with Example 1, except that a 5% by weight solution of polyisobutylene (weight average molecular weight approximately 1 million) and toluene was used instead of the ethyl cellulose solution. I got a separator. However, wire bar ROD teeth 6 were used for coating.
実施例３
エチルセルロース溶液に代えて、線状ポリマからなる熱
可塑性ポリウレタン（重量平均分子量約４万）の１０重
量％エマルジョンを用いたほかは実施例１に準じて本発
明のシリコーン系剥離性皮膜を有するセパレータを得た
。Example 3 A silicone release film of the present invention was prepared in the same manner as in Example 1, except that a 10% emulsion of thermoplastic polyurethane (weight average molecular weight approximately 40,000) consisting of a linear polymer was used in place of the ethyl cellulose solution. A separator having the following properties was obtained.
実施例４
ポリイソブチレン溶液に代えて、熱可塑性ポリエステル
（数平均分子量１．５万〜２万、軟化点１６３℃、溶解
度パラメータ１０．１ ＞に、トルエン／メチルエチル
ケトン： ８０／２０ （重量比）からなる混合溶剤を
加えてなる５重量％溶液を用いたほかは実施例２に準じ
て本発明のシリコーン系剥離性皮膜を有するセパレータ
を得た。Example 4 Instead of polyisobutylene solution, thermoplastic polyester (number average molecular weight 15,000 to 20,000, softening point 163°C, solubility parameter 10.1), toluene/methyl ethyl ketone: 80/20 (weight ratio) A separator having a silicone-based release film of the present invention was obtained in accordance with Example 2, except that a 5% by weight solution containing a mixed solvent was used.
実施例５
ポリイソブチレン溶液に代えて、アクリル系樹脂（アク
リル酸ブチル／メタクリル酸メチル／アクリル酸２−ヒ
ドロキシエチル： １０／８５／ ５ （重量比）、重
量平均分子量約５０万）にトルエン／メタノール： ９
０／１０ （重量比）からなる混合溶剤を加えてなる５
Ｍ量％溶液を用いたほかは実施例２に準じて本発明のシ
リコーン系剥離性皮膜を有するセパレータを得た。Example 5 Instead of polyisobutylene solution, toluene/methanol was added to acrylic resin (butyl acrylate/methyl methacrylate/2-hydroxyethyl acrylate: 10/85/5 (weight ratio), weight average molecular weight approximately 500,000). : 9
5 by adding a mixed solvent consisting of 0/10 (weight ratio)
A separator having a silicone-based peelable film of the present invention was obtained in accordance with Example 2, except that a %M solution was used.
実施例６
実施例４で用いた熱可塑性ポリエステル／参考例で得た
ポリオルガノシロキサン／熱反応型スルホニウム塩系硬
化触媒、 ３０／６６／４ （重量比）にトルエン／メ
チルエチルケトン： ８０／２０ （重量比）からなる
混合溶剤を加えて１０重量％溶液を調製し、これをワイ
ヤーバーＲＯＤＮｎ６にて、厚さ１２０μｍのポリエチ
レンラミネートクラフト紙のラミネート面に塗工量が１
ｇ／ｄとなるように塗工し、１００℃の熱風恒温機中に
ｌＯ分間入れて乾燥と共に硬化処理し、本発明のシリコ
ーン系剥離性皮膜を有するセパレータを得た。Example 6 Thermoplastic polyester used in Example 4/polyorganosiloxane obtained in reference example/thermal-reactive sulfonium salt curing catalyst, 30/66/4 (weight ratio) toluene/methyl ethyl ketone: 80/20 (weight ratio) A 10% by weight solution was prepared by adding a mixed solvent consisting of
g/d and placed in a hot air constant temperature machine at 100° C. for 10 minutes to dry and cure, thereby obtaining a separator having a silicone-based release film of the present invention.
比較例１
エチルセルロース溶液からなるインキ親和層を設けない
で、シリコーン皮膜層を直接ポリエチレンラミネートク
ラフト紙のラミネート面に設けたほかは実施例１に準じ
てシリコーン系剥離性皮膜を有するセパレータを得た。Comparative Example 1 A separator having a silicone-based release film was obtained in accordance with Example 1, except that the ink affinity layer made of ethyl cellulose solution was not provided, and the silicone film layer was directly provided on the laminate surface of polyethylene-laminated kraft paper.
比較例２
ポリエチレングリコールアリルメチルエーテルを使用し
ないで参考例に準じて調製した、エポキシ基官能性有機
基は有するが、ポリエーテル・ポリメチレン基は有しな
いポリオルガノシロキサンを用いたほかは実施例１に準
じてシリコーン系剥離性皮膜を有するセパレータを得た
。Comparative Example 2 Same as Example 1 except that a polyorganosiloxane having an epoxy functional organic group but not having a polyether or polymethylene group was used, which was prepared according to the reference example without using polyethylene glycol allyl methyl ether. A separator having a silicone-based releasable film was obtained in the same manner.
評価試験
実施例、比較例で得たセパレータにつき下記の特性を調
べた。The following properties of the separators obtained in the evaluation test examples and comparative examples were investigated.
［硬化性］
セパレータにおける剥離性皮膜にベトッキがない場合を
０、少々ある場合を△、ベトッキが大きい場合を×とし
て評価した。[Curability] Evaluation was given as 0 when there was no stickiness in the peelable film of the separator, Δ when there was some stickiness, and × when there was large stickiness.
［印字性］
市販の油性インキペンでセパレータにおける剥離性皮膜
の表面に文字を書き、ハジキの全（ない場合を◎、殆ど
ない場合を○、少々ある場合を△、著しい場合をＸとし
て評価した。[Printability] Characters were written on the surface of the releasable film on the separator using a commercially available oil-based ink pen, and the degree of repellency was evaluated as ◎ if there was no repellency, ○ if it was almost absent, △ if it was present, and X if it was significant.
［剥離力］
２０℃以下、６５％Ｒ，Ｉｌ下でセパレータの剥離性皮
膜面の上に幅２５ｎｗａの市販粘着テープ（日東電工社
製、クラフトテープＮｏ７１２）を重さ２ ｋｇのゴム
ローラを一往復させて圧着したのち、その粘着テープの
上に５０ ｇ ／ ｃｎｉの荷重をかけた状態で２０℃
下に４８時間放置する。その後、荷重を解いて２０℃、
６５％ｆｔ、）Ｉ下に２時間放置し、得られたものにつ
いてショツパーにより粘着テープを３００ ｗＲ／分の
速度で引き剥がしく１８０度ビール）、その剥離に要す
る力を求めた（４サンプルの平均値）。[Peeling force] A commercially available adhesive tape with a width of 25 nwa (manufactured by Nitto Denko Corporation, craft tape No. 712) was rolled back and forth with a rubber roller weighing 2 kg on the peelable film surface of the separator at 20° C. or lower and under 65% R and Il. After crimping, the adhesive tape was heated at 20°C with a load of 50 g/cni applied.
Leave it under for 48 hours. After that, the load was released and the temperature was 20°C.
65% ft, )I for 2 hours, and then the adhesive tape was peeled off using a Schopper at a speed of 300 wR/min (180°), and the force required for peeling was determined (for 4 samples). Average value).
［残留接着率］（粘着剤面の非汚染性〉上記剥離力を測
定した後の粘着テープを２０℃、６５％Ｒ０１１下でス
テンレス板（ＳＵＳ２７ＣＰ）の耐水研摩紙（２８０番
）で充分に研摩し、これを洗浄した面に重さ２ｋｇのゴ
ムローラを一往復させて圧着したのち、３０分間放置し
たものについて上記と同様にして剥離に要する力を求め
た。そして、得られた測定値の、前記と同様にして剥離
性皮膜面に接触させたことがない粘着テープについて求
めた測定値に対する残留接着力の割合を残留接着率とし
て算出した（４サンプルの平均値）。[Residual adhesion rate] (Non-staining property of adhesive surface) After measuring the above peeling force, thoroughly polish the adhesive tape with water-resistant abrasive paper (No. 280) on a stainless steel plate (SUS27CP) at 20°C and 65% R011. Then, a rubber roller weighing 2 kg was moved back and forth once on the cleaned surface to press it, and after leaving it for 30 minutes, the force required for peeling was determined in the same manner as above. The residual adhesion rate was calculated as the ratio of the residual adhesive force to the measured value obtained for the adhesive tape that had never been brought into contact with the peelable film surface in the same manner as above (average value of 4 samples).
結果を表に示した。The results are shown in the table.
表から明らかなように、本発明のシリコーン系剥離性皮
膜は硬化性、油性インキ印字性、粘着面の非汚染性に優
れている。As is clear from the table, the silicone release film of the present invention has excellent curability, oil-based ink printability, and non-staining property on the adhesive surface.
特許出願人 日東電工株式会社Patent applicant: Nitto Denko Corporation
Claims (1)
らなるインキ親和層の上にシリコーン皮膜層を有してな
り、そのシリコーン皮膜層が一般式 ▲数式、化学式、表等があります▼ （ただし、Ｒは炭素数１〜２０のアルキル基、シクロア
ルキル基、アリール基又はアラルキル基であり、Ｘはエ
ポキシ基官能性有機基であり、Ｙはポリエーテル・ポリ
メチレン基であり、ｍ／（ｌ＋ｍ＋ｎ）が０．０５〜９
０％であり、ｎ／（ｌ＋ｍ＋ｎ）が０．５〜９０％であ
る。）で表されるポリオルガノシロキサンを、オニウム
塩系硬化触媒を用いて硬化処理してなるものであること
を特徴とするシリコーン系剥離性皮膜。 ２、請求項１に記載のシリコーン系剥離性皮膜を片面に
有する支持基材の他面に粘着層を有することを特徴とす
る粘着部材。 ３、支持基材の片面又は両面に請求項１に記載のシリコ
ーン系剥離性皮膜を有することを特徴とするセパレータ
。[Claims] 1. A silicone film layer is provided on an ink affinity layer made of a film-forming resin that is easily swellable or easily soluble in organic solvents, and the silicone film layer has a general formula ▲ mathematical formula, There are chemical formulas, tables, etc.▼ (However, R is an alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, X is an epoxy functional organic group, and Y is a polyether/polymethylene group. is a group, and m/(l+m+n) is 0.05 to 9
0%, and n/(l+m+n) is 0.5 to 90%. 1. A silicone-based release film, characterized in that it is formed by curing a polyorganosiloxane represented by () using an onium salt-based curing catalyst. 2. An adhesive member comprising a support substrate having the silicone-based releasable film according to claim 1 on one side and an adhesive layer on the other side. 3. A separator comprising a silicone release film according to claim 1 on one or both sides of a supporting base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63266772A JP2554924B2 (en) | 1988-10-21 | 1988-10-21 | Silicone releasable coating, its adhesive member and separator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63266772A JP2554924B2 (en) | 1988-10-21 | 1988-10-21 | Silicone releasable coating, its adhesive member and separator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02113018A true JPH02113018A (en) | 1990-04-25 |
| JP2554924B2 JP2554924B2 (en) | 1996-11-20 |
Family
ID=17435484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63266772A Expired - Lifetime JP2554924B2 (en) | 1988-10-21 | 1988-10-21 | Silicone releasable coating, its adhesive member and separator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2554924B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0525443A (en) * | 1991-07-17 | 1993-02-02 | Nitto Denko Corp | Curable silicone release agent and its separator |
| JP2008078643A (en) * | 2006-09-08 | 2008-04-03 | Asml Netherlands Bv | Lithographic apparatus having mechanism providing gas bearing, and method of manufacturing device |
| JPWO2006043434A1 (en) * | 2004-10-18 | 2008-05-22 | 株式会社ニコン | Bearing apparatus, stage apparatus, and exposure apparatus |
-
1988
- 1988-10-21 JP JP63266772A patent/JP2554924B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0525443A (en) * | 1991-07-17 | 1993-02-02 | Nitto Denko Corp | Curable silicone release agent and its separator |
| JPWO2006043434A1 (en) * | 2004-10-18 | 2008-05-22 | 株式会社ニコン | Bearing apparatus, stage apparatus, and exposure apparatus |
| JP2008078643A (en) * | 2006-09-08 | 2008-04-03 | Asml Netherlands Bv | Lithographic apparatus having mechanism providing gas bearing, and method of manufacturing device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2554924B2 (en) | 1996-11-20 |
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