JP2008200880A - Release sheet and sticking member - Google Patents
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- JP2008200880A JP2008200880A JP2007036380A JP2007036380A JP2008200880A JP 2008200880 A JP2008200880 A JP 2008200880A JP 2007036380 A JP2007036380 A JP 2007036380A JP 2007036380 A JP2007036380 A JP 2007036380A JP 2008200880 A JP2008200880 A JP 2008200880A
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 125000000524 functional group Chemical group 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 50
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 239000012790 adhesive layer Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 52
- 239000000758 substrate Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- -1 polyethylene Polymers 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 239000000123 paper Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001723 curing Methods 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920006289 polycarbonate film Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- LWIGVRDDANOFTD-UHFFFAOYSA-N hydroxy(dimethyl)silane Chemical group C[SiH](C)O LWIGVRDDANOFTD-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical group C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本発明は、剥離シートおよび粘着体に関するものである。さらに詳しくは、特定の化学構造を有するシリコーン化合物を活性エネルギー線照射により硬化してなる剥離剤層を剥離シート基材上に有する剥離シートおよび前記と同じ剥離剤層と粘着剤層とが接するように貼合された構成を有する粘着体に関するものである。本発明の剥離シートおよび粘着体における剥離剤は硬化性に優れ、形成された剥離剤層は剥離シート基材への密着性および耐溶剤性に優れている。 The present invention relates to a release sheet and a pressure-sensitive adhesive body. More specifically, the release sheet having a release agent layer formed by curing a silicone compound having a specific chemical structure by irradiation with active energy rays on the release sheet substrate, and the same release agent layer and the adhesive layer as described above are in contact with each other. It is related with the adhesive body which has the structure bonded together. The release agent in the release sheet and the pressure-sensitive adhesive body of the present invention is excellent in curability, and the formed release agent layer is excellent in adhesion to the release sheet substrate and solvent resistance.
一般に、剥離シートは、紙、プラスチックフィルム、ポリエチレンラミネート紙などの剥離シート基材の少なくとも片面に、反応性化合物を含む剥離剤組成物を塗布し、硬化させて剥離剤層を設けたものであって、例えば粘着テープおよび粘着シート等の粘着体や樹脂シート製造時のキャリアーシート、それらの保護シート、セラミックグリーンシート成膜用工程フィルムなどとして用いられる。
上記粘着体には、例えば紙や高分子フィルム等からなる粘着シート基材、その表面に形成された粘着剤層、およびその粘着剤層と剥離剤層とが接するように貼合された剥離シートから構成されたものや、粘着シート基材の粘着剤層を設ける面とは反対の面に剥離剤層を設け、剥離剤層と粘着剤層とが接するように貼合されロール状に巻回された構成のものがある。
反応性化合物を含む剥離剤組成物を硬化させる方法としては、例えば、熱硬化性化合物を含む剥離剤組成物を加熱硬化させる方法、活性エネルギー線硬化性化合物を含む剥離剤組成物を活性エネルギー線の照射により硬化させる方法などが挙げられる。
熱硬化性化合物を含む剥離剤組成物を加熱硬化させる方法としては、ビニル基を官能基とするポリジメチルシロキサンと架橋剤（ポリメチルハイドロジェンシロキサン）からなる主剤を主成分とした付加反応型シリコーン樹脂組成物（特許文献１）、アルケニル基含有ポリオルガノシロキサン、ポリオルガノハイドロジェンシロキサン、白金系触媒からなる組成物（特許文献２）、ジメチルシロキサンユニットとメチル-ビニルシロキサンユニットの比率を一定の範囲にコントロールしたシリコーン樹脂を主成分として含む剥離剤組成物（特許文献３）が例示される。
活性エネルギー線硬化性化合物を含む剥離剤組成物を活性エネルギー線の照射により硬化させる方法としては、活性エネルギー線として電子線を照射して基材上に塗布された各種シリコーン化合物を硬化させて剥離剤層を形成させたものが報告されている (例えば、特許文献４)。
また、活性エネルギー線として紫外線を用いたものとしては、アクリル・トリアルコキシシリル官能基又はアクリル・トリアリルオキシシリル官能基を末端基として有する反応性ポリオルガノシロキサンを主成分とする組成物（特許文献５）、分子鎖末端にビニル基を有する分岐状のオルガノポリシロキサンとオルガノハイドロジェンポリシロキサンを主成分とする組成物（特許文献６）、２個のラジカル重合性基を有するオルガノポリシロキサン、３級アミン化合物、光開始剤からなる組成物（特許文献７）、フェニル基と分子末端のアルケニル基を含有するオルガノポリシロキサン、メルカプトアルキル基を含有するオルガノポリシロキサン及び光開始剤を主成分とする組成物（特許文献８）が例示される。
しかしながら、上記硬化性化合物を含む剥離剤組成物はいずれも重合性または架橋性官能基を有しているため、貯蔵安定性(ポットライフ)に問題がある。
また、電子線硬化型シリコーンを用いた場合、酸素による表面の反応阻害を解消するために、不活性ガスによるイナーティングが必須であるなどの問題点があった。
In general, a release sheet is one in which a release agent composition containing a reactive compound is applied to at least one surface of a release sheet substrate such as paper, plastic film, polyethylene laminated paper, etc., and cured to provide a release agent layer. For example, it is used as a pressure-sensitive adhesive such as a pressure-sensitive adhesive tape and a pressure-sensitive adhesive sheet, a carrier sheet when producing a resin sheet, a protective sheet thereof, a process film for forming a ceramic green sheet, or the like.
For example, a pressure-sensitive adhesive sheet substrate made of paper or a polymer film, a pressure-sensitive adhesive layer formed on the surface thereof, and a release sheet bonded so that the pressure-sensitive adhesive layer and the release agent layer are in contact with the pressure-sensitive adhesive body. A release agent layer is provided on the surface opposite to the surface on which the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet substrate is provided, and the release agent layer and the pressure-sensitive adhesive layer are bonded and wound into a roll. There is a thing of the structure.
Examples of a method for curing a release agent composition containing a reactive compound include a method of heat-curing a release agent composition containing a thermosetting compound, and a release agent composition containing an active energy ray-curable compound as an active energy ray. And a method of curing by irradiation.
As a method for heat-curing a release agent composition containing a thermosetting compound, an addition reaction type silicone mainly composed of a main agent composed of polydimethylsiloxane having a vinyl group as a functional group and a crosslinking agent (polymethylhydrogensiloxane). Resin composition (Patent Document 1), composition comprising alkenyl group-containing polyorganosiloxane, polyorganohydrogensiloxane, platinum catalyst (Patent Document 2), ratio of dimethylsiloxane unit to methyl-vinylsiloxane unit within a certain range A release agent composition (Patent Document 3) containing a controlled silicone resin as a main component is exemplified.
As a method of curing a release agent composition containing an active energy ray-curable compound by irradiation with active energy rays, various silicone compounds applied on a substrate are cured by irradiating an electron beam as active energy rays and then peeled off. An agent layer is reported (for example, Patent Document 4).
In addition, as a composition using ultraviolet rays as active energy rays, a composition mainly composed of a reactive polyorganosiloxane having an acrylic / trialkoxysilyl functional group or an acrylic / triallyloxysilyl functional group as a terminal group (Patent Documents) 5) A composition mainly composed of a branched organopolysiloxane having a vinyl group at the molecular chain terminal and an organohydrogenpolysiloxane (Patent Document 6), an organopolysiloxane having two radical polymerizable groups, 3 A composition comprising a secondary amine compound, a photoinitiator (Patent Document 7), an organopolysiloxane containing a phenyl group and an alkenyl group at the molecular end, an organopolysiloxane containing a mercaptoalkyl group, and a photoinitiator. A composition (patent document 8) is illustrated.
However, since any release agent composition containing the curable compound has a polymerizable or crosslinkable functional group, there is a problem in storage stability (pot life).
Further, when electron beam curable silicone is used, there is a problem that inert gas inerting is indispensable in order to eliminate surface reaction inhibition by oxygen.
このような状況の下、本発明の課題は、従来から用いられてきた上記のような重合性または架橋性官能基を有する硬化型シリコーン化合物における上記のような問題を解決することにある。 Under such circumstances, an object of the present invention is to solve the above-described problems in curable silicone compounds having a polymerizable or crosslinkable functional group as described above.
本発明者らは、種々研究を重ねた結果、剥離剤として用いられるシリコーン化合物が（メタ）アクリロイル基のような重合性または架橋性官能基を含んでいなくても、一定量のアリール基を含んでいれば、活性エネルギー線により硬化させることができることを見出し、本発明を完成させた。 As a result of extensive research, the present inventors have found that a certain amount of aryl groups can be obtained even if the silicone compound used as a release agent does not contain a polymerizable or crosslinkable functional group such as a (meth) acryloyl group. If it is included, it was found that it can be cured by active energy rays, and the present invention was completed.
すなわち、本発明は、下記
（１）置換基を有していてもよいアリール基およびアルキル基を有し、重合性または架橋性官能基を含まないシリコーン化合物を活性エネルギー線により硬化してなる剥離剤層を剥離シート基材上に有する剥離シート、
（２）シリコーン化合物がオルガノポリシロキサンである上記（１）に記載の剥離シート、
（３）アリール基がフェニル基であり、アルキル基がメチル基である上記（１）または（２）に記載の剥離シート、
（４）アリール基とアルキル基の比率が個数基準で２/９８〜５０/５０である上記（１）〜（３）のいずれかに記載の剥離シート、
（５）活性エネルギー線が紫外線である上記（１）〜（４）のいずれかに記載の剥離シート、
（６）剥離剤層の厚みが０．０５〜２μｍである上記（１）〜（５）のいずれかに記載の剥離シート、
（７）前記シリコーン化合物が架橋剤、触媒または開始剤不存在下、活性エネルギー線により硬化されてなる上記（１）〜（６）のいずれかに記載の剥離シート、および
（８）上記（１）〜（７）のいずれかに記載の剥離剤層と粘着剤層とが接するように貼合された構成を有する粘着体を提供する。
That is, the present invention provides the following (1) peeling formed by curing a silicone compound having an aryl group and an alkyl group which may have a substituent and not containing a polymerizable or crosslinkable functional group with active energy rays. Release sheet having an agent layer on a release sheet substrate,
(2) The release sheet according to (1), wherein the silicone compound is an organopolysiloxane,
(3) The release sheet according to (1) or (2), wherein the aryl group is a phenyl group and the alkyl group is a methyl group,
(4) The release sheet according to any one of (1) to (3), wherein the ratio of the aryl group to the alkyl group is 2/98 to 50/50 on a number basis,
(5) The release sheet according to any one of (1) to (4), wherein the active energy ray is ultraviolet light,
(6) The release sheet according to any one of (1) to (5), wherein the release agent layer has a thickness of 0.05 to 2 μm,
(7) The release sheet according to any one of the above (1) to (6), wherein the silicone compound is cured by active energy rays in the absence of a crosslinking agent, a catalyst or an initiator, and (8) the above (1) The adhesive body which has the structure bonded so that the peeling agent layer and adhesive layer in any one of ()-(7) may contact | connect.
本発明によれば、粘着剤層に対する適度な剥離力、硬化性、密着性および耐溶剤性をバランスよく有する剥離剤層が形成され、同剥離剤層を剥離シート基材上に有する剥離シートおよび同剥離剤層と粘着剤層が同じ基材の両面にそれぞれ形成された粘着シート、ならびに、前記剥離シートと基材上に形成された粘着剤層とを貼合してなる粘着シートが得られる。 According to the present invention, a release sheet having an appropriate release force, curability, adhesion and solvent resistance with respect to the pressure-sensitive adhesive layer is formed in a balanced manner, and a release sheet having the release agent layer on the release sheet substrate and A pressure-sensitive adhesive sheet in which the release agent layer and the pressure-sensitive adhesive layer are respectively formed on both surfaces of the same substrate, and a pressure-sensitive adhesive sheet obtained by bonding the release sheet and the pressure-sensitive adhesive layer formed on the substrate are obtained. .
本発明におけるシリコーン化合物中に含まれない重合性または架橋性官能基とは具体的には、（メタ）アクリロイル基、アルケニル基、ビニルアミド基、ヒドロシリル基、アセチレン基、グリシジル（エポキシ）基、イソシアナート基等をいう。通常、官能基に分類されるヒドロキシル基、カルボキシル基、アミノ基、シアノ基、シラノール基、ジアゾ基、チオール基、ハロゲン基等はその基自身で架橋または重合しないのでシリコーン化合物中に含まれていても良い。 Specific examples of the polymerizable or crosslinkable functional group not included in the silicone compound in the present invention include (meth) acryloyl group, alkenyl group, vinylamide group, hydrosilyl group, acetylene group, glycidyl (epoxy) group, and isocyanate. Refers to the group. Usually, hydroxyl groups, carboxyl groups, amino groups, cyano groups, silanol groups, diazo groups, thiol groups, halogen groups, etc. classified as functional groups are not included in the silicone compound because they are not crosslinked or polymerized by themselves. Also good.
本発明における重合性または架橋性官能基を含まないシリコーン化合物中のアリール基としては、フェニル基、クロルフェニル基、ニトロフェニル基、ベンジル基、トリル基、キシリル基、ナフチル基、ビフェニリル基、アントリル基、フェナントリル基等が挙げられる。工業的に製造され、入手のし易さの観点でアリール基としてフェニル基を有するシリコーン化合物が好ましく用いられる。
アリール基が有していてもよい置換基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基のようなアルキル基、前記したような官能基に分類されることのあるヒドロキシル基等のその基自身で架橋または重合しない基である。
As the aryl group in the silicone compound not containing a polymerizable or crosslinkable functional group in the present invention, a phenyl group, a chlorophenyl group, a nitrophenyl group, a benzyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenylyl group, an anthryl group And a phenanthryl group. A silicone compound which is produced industrially and has a phenyl group as an aryl group is preferred from the viewpoint of availability.
Examples of the substituent that the aryl group may have include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and a hydroxyl group that may be classified into the functional groups described above. This group is a group that does not crosslink or polymerize itself.
本発明における重合性または架橋性官能基を含まないシリコーン化合物中のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基等が挙げられるが、工業的に製造され、入手のし易さの観点でアルキル基としてメチル基を有するシリコーン化合物が好ましく用いられる。 Examples of the alkyl group in the silicone compound that does not contain a polymerizable or crosslinkable functional group in the present invention include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. From the viewpoint of ease of use, a silicone compound having a methyl group as an alkyl group is preferably used.
シリコーン化合物は１分子中に２個以上のアリール基を有するものである。アリール基とアルキル基の比率は、個数基準で通常２/９８〜５０/５０、好ましくは５/９５〜４５/５５、より好ましくは１０/９０〜４０/６０程度である。１分子中のアリール基の数を２個以上とすることにより、剥離剤層が良好な皮膜強度を有するものとなり、比率を５０/５０以下とすることにより、粘着剤層に対する剥離力が過度に高くなるのを防止できる。 The silicone compound has two or more aryl groups in one molecule. The ratio of the aryl group to the alkyl group is usually 2/98 to 50/50, preferably 5/95 to 45/55, more preferably about 10/90 to 40/60 on the number basis. By setting the number of aryl groups in one molecule to 2 or more, the release agent layer has good film strength, and by setting the ratio to 50/50 or less, the release force on the pressure-sensitive adhesive layer is excessive. It can be prevented from becoming high.
本発明における重合性または架橋性官能基を含まないシリコーン化合物はより具体的には、オルガノポリシロキサンであり、下記式（I）のようなアリール基およびアルキル基を有するシロキサンユニットを基本骨格として有するオルガノポリシロキサンである。
Ｒ1 3ＳｉＯ（Ｒ2ＳｉＯ）nＳｉＲ1 3・・・（I）
ここで、Ｒは置換基を有していてもよいアリール基またはアルキル基、Ｒ1はＲまたは水酸基であり、ｎは正の整数を表す。なお、ＲまたはＲ1のうち２個以上は置換基を有していてもよいアリール基である。
市販のものとしては、東レ・ダウコーニング社製の品番ＢＹ２４−８４２、ＢＹ２４−８５０、ＢＹ１６−８４６、ＢＹ１６−８７３、ＳＨ７０９０、ＳＨ２００、ＳＨ２０３、ＳＨ２３０、ＳＨ７１０、ＳＦ８４１６、ＳＲ２３０６等が挙げられる。
More specifically, the silicone compound containing no polymerizable or crosslinkable functional group in the present invention is an organopolysiloxane, and has a siloxane unit having an aryl group and an alkyl group represented by the following formula (I) as a basic skeleton. Organopolysiloxane.
R 1 3 SiO (R 2 SiO) n SiR 1 3 (I)
Here, R is an aryl group or an alkyl group which may have a substituent, R 1 is R or a hydroxyl group, and n represents a positive integer. In addition, two or more of R or R 1 are aryl groups which may have a substituent.
Examples of commercially available products include Toray Dow Corning product numbers BY24-842, BY24-850, BY16-846, BY16-873, SH7090, SH200, SH203, SH230, SH710, SF8416, SR2306, and the like.
本発明において、剥離剤であるシリコーン化合物は通常、０．１〜１０質量％、好ましくは１〜３質量％程度になるように有機溶剤に溶解した溶液として後で述べる剥離シート基材または基材に塗布される。
用いられる有機溶剤としては、公知の溶剤の中から適宜選択して用いることができる。このような溶剤としては、例えばトルエン、キシレン、シクロヘキサンのような炭化水素系の溶剤；メタノール、エタノール、イソブタノール、ｎ−ブタノールのようなアルコール類；アセトン、メチルエチルケトンのようなケトン類；テトラヒドロフランのような環状エーテル類などが挙げられる。これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
シリコーン化合物の溶解性および乾燥性の観点からトルエン、メチルエチルケトンが好ましく用いられる。
In the present invention, the silicone compound as the release agent is usually 0.1 to 10% by mass, preferably a release sheet substrate or substrate described later as a solution dissolved in an organic solvent so as to be about 1 to 3% by mass. To be applied.
The organic solvent used can be appropriately selected from known solvents. Examples of such solvents include hydrocarbon solvents such as toluene, xylene and cyclohexane; alcohols such as methanol, ethanol, isobutanol and n-butanol; ketones such as acetone and methyl ethyl ketone; and tetrahydrofuran. And cyclic ethers. These may be used individually by 1 type, and may be used in combination of 2 or more types.
Toluene and methyl ethyl ketone are preferably used from the viewpoints of solubility and drying properties of the silicone compound.
剥離シート基材または基材上に形成される剥離剤層の厚さは、特に限定されないが、０．０５〜２．０μｍであるのが好ましく、０．１〜１．５μｍであるのがより好ましい。剥離剤層の厚さをこのような範囲とするためのシリコーン化合物の塗布量としては０．０５〜５．０ｇ/ｍ2程度である。
剥離剤層の厚さを前記下限値以上とすることにより、剥離性能が不安定となるのを防止する。一方、剥離剤層の厚さを前記上限値以下とすることにより、剥離シートまたは粘着シートをロール状に巻き取ったときのシリコーン化合物塗工面が、剥離シート背面または粘着剤面とブロッキングし易くなり、シリコーン塗工面の剥離性能がブロッキングにより、低下するのを防止する。シリコーン化合物の有機溶剤溶液は剥離シート基材または基材の全面または剥離性の必要な箇所に部分的に塗布する。剥離シート基材または基材に塗布した後、７０〜２２０℃程度で、１．５〜１２０秒程度の加熱によって有機溶剤を蒸発させ、次いで、後で述べる紫外線のような活性エネルギー線を照射して硬化させて、本発明の剥離シートまたは粘着シートを得る。
The thickness of the release sheet substrate or the release agent layer formed on the substrate is not particularly limited, but is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.5 μm. preferable. The thickness of the release agent layer as the coating amount of the silicone compound for such a range is about 0.05 to 5.0 g / m 2.
By making the thickness of the release agent layer equal to or more than the lower limit value, the release performance is prevented from becoming unstable. On the other hand, by setting the thickness of the release agent layer to the upper limit or less, the silicone compound coated surface when the release sheet or the pressure-sensitive adhesive sheet is rolled up is easily blocked from the release sheet back surface or the pressure-sensitive adhesive surface. The peeling performance of the silicone coated surface is prevented from being lowered by blocking. The organic solvent solution of the silicone compound is partially applied to the release sheet substrate, the entire surface of the substrate, or a place where releasability is required. After application to the release sheet substrate or substrate, the organic solvent is evaporated by heating at about 70 to 220 ° C. for about 1.5 to 120 seconds, and then irradiated with active energy rays such as ultraviolet rays described later. And cured to obtain the release sheet or pressure-sensitive adhesive sheet of the present invention.
本発明の剥離シートは、下記のような剥離シート基材を用意し、この剥離シート基材上に剥離剤であるシリコーン化合物の有機溶剤溶液を塗工して剥離剤層を形成させることにより作製するが、剥離剤を剥離シート基材上に塗工する方法としては、例えば、グラビアコート法、バーコート法、スプレーコート法、スピンコート法、ナイフコート法、ロールコート法、ダイコート法等の既存の方法が使用できる。
剥離シート基材の材料としては、特に限定されず、従来から剥離シートにおいて基材として用いられているものの中から、任意のものを適宜選択して用いることができる。このような剥離シート基材は、例えば、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム等のポリエステルフィルム、ポリプロピレンフィルムやポリメチルペンテンフィルム等のポリオレフィンフィルム、ポリカーボネートフィルム等のプラスチックフィルム、アルミニウム、ステンレス等の金属箔、グラシン紙、クラフト紙、クレーコート紙、ポリエチレンラミネート上質紙、ポリエチレンラミネートクラフト紙などのラミネート紙、含浸紙、合成紙等の紙基材、これら紙基材にポリエチレンなどの熱可塑性樹脂をラミネートした紙等で構成されている。
剥離シート基材としてプラスチックフィルムを用いる場合には、プラスチックフィルムと剥離剤層との密着性を向上させるなどの目的で、所望により、プラスチックフィルムの剥離剤層が設けられる側の面に、酸化法や凹凸化法などの物理的又は化学的表面処理を施すことができる。酸化法としては、例えばコロナ放電処理、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線照射処理などが挙げられ、また、凹凸化法としては、例えばサンドブラスト法、溶剤処理法などが挙げられる。これらの表面処理法は、剥離シート基材の種類に応じて適宜選ばれるが、一般にはコロナ放電処理法が、効果及び操作性などの面から、好ましく用いられる。また、プライマー処理を施すこともできる。
The release sheet of the present invention is prepared by preparing a release sheet substrate as described below, and applying a release agent layer by applying an organic solvent solution of a silicone compound as a release agent on the release sheet substrate. However, as a method of coating the release agent on the release sheet substrate, for example, existing methods such as gravure coating method, bar coating method, spray coating method, spin coating method, knife coating method, roll coating method, die coating method, etc. Can be used.
The material for the release sheet substrate is not particularly limited, and any material can be appropriately selected from those conventionally used as a substrate in a release sheet. Such release sheet base materials are, for example, polyester films such as polyethylene terephthalate films and polybutylene terephthalate films, polyolefin films such as polypropylene films and polymethylpentene films, plastic films such as polycarbonate films, and metal foils such as aluminum and stainless steel. Glass paper, kraft paper, clay coated paper, polyethylene laminated fine paper, laminated paper such as polyethylene laminated kraft paper, paper substrates such as impregnated paper, synthetic paper, etc., and these paper substrates were laminated with thermoplastic resin such as polyethylene It consists of paper.
When a plastic film is used as the release sheet substrate, an oxidation method may be applied to the surface of the plastic film on which the release agent layer is provided, for the purpose of improving the adhesion between the plastic film and the release agent layer. Or a physical or chemical surface treatment such as an uneven method. Examples of the oxidation method include corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment. Examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected according to the type of the release sheet substrate, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability. Moreover, primer treatment can also be performed.
本発明において、シリコーン化合物を硬化させるために用いられる活性エネルギー線としては、紫外線、電子線、Ｘ線等があるが、紫外線を用いるのが好ましい。紫外線発生源として、従来公知のもの、例えば高圧水銀ランプ、メタルハライドランプ、ハイパワーメタルハライドランプ、無電極紫外線ランプなどを用いることができるが、紫外線発光効率、赤外線照射量などから、剥離シート基材に対する熱損傷が少なく、かつシリコーン化合物の硬化性が良いことなどから、無電極紫外線ランプが好ましい。
紫外線を照射する際の出力については、通常は３０Ｗ/ｃｍ〜６００Ｗ/ｃｍ、好ましくは５０Ｗ/ｃｍ〜３６０Ｗ/ｃｍである。紫外線の照射量は１〜１５０ｍＪ/ｃｍ2 の範囲が好ましく、特に２〜１００ｍＪ/ｃｍ2 の範囲が好ましい。また、紫外線を照射する際の温度については特に制限はなく、インラインにおいて紫外線照射処理を行うのであれば、加熱処理直後の加熱された状態や、室温状態などのいずれであってもよい。さらに、紫外線等の活性エネルギー線を照射する際の雰囲気中の酸素濃度については特に制限はなく、酸素による表面の反応阻害を解消するための、不活性ガスによるイナーティングは不要である。通常、大気中下での酸素濃度約２１％の条件で硬化を行うことができる。
このようにして、剥離シート基材上に、シリコーン化合物の硬化層が密着性良く形成され、熱収縮による皺などがなく、極めて高い平坦性を有すると共に、粘着剤層等からの剥離性に優れる剥離シートが生産性よく得られる。
In the present invention, examples of active energy rays used for curing the silicone compound include ultraviolet rays, electron beams, and X-rays, and it is preferable to use ultraviolet rays. Conventionally known sources such as high pressure mercury lamps, metal halide lamps, high power metal halide lamps, electrodeless ultraviolet lamps and the like can be used as the ultraviolet ray generation source. An electrodeless ultraviolet lamp is preferred because it has little thermal damage and good curability of the silicone compound.
About the output at the time of irradiating an ultraviolet-ray, it is 30W / cm-600W / cm normally, Preferably it is 50W / cm-360W / cm. The dose of ultraviolet rays is preferably in the range of 1~150mJ / cm 2, in particular in the range of 2~100mJ / cm 2 is preferred. Moreover, there is no restriction | limiting in particular about the temperature at the time of irradiating an ultraviolet-ray, As long as an ultraviolet irradiation process is performed in-line, any of the heated state immediately after heat processing, a room temperature state, etc. may be sufficient. Further, the oxygen concentration in the atmosphere when irradiating active energy rays such as ultraviolet rays is not particularly limited, and inert gas inerting is not required to eliminate surface reaction inhibition by oxygen. Usually, curing can be performed under conditions of an oxygen concentration of about 21% in the air.
In this way, a cured layer of the silicone compound is formed on the release sheet substrate with good adhesion, has no wrinkles due to heat shrinkage, has extremely high flatness, and is excellent in peelability from the pressure-sensitive adhesive layer and the like. A release sheet can be obtained with high productivity.
硬化性の化合物を電子線以外の活性エネルギー線で硬化させる際、通常、架橋剤、触媒または光重合開始剤が用いられるが、本発明においては、それらを用いなくても硬化して剥離層を形成させることができ、貯蔵安定性(ポットライフ)に優れていることから、液換え作業なしでの長時間塗工が可能であり、経済性および剥離物性の安定性という観点で好ましい。従来、付加反応タイプのシリコーン系化合物を硬化させる場合は、架橋剤としてはヒドロシリル基含有のもの、硬化触媒としては白金系触媒が用いられ、光硬化タイプのシリコーン系化合物を硬化させる場合は、光重合開始剤が用いられていたが、いずれも貯蔵安定性(ポットライフ)に問題があった。 When a curable compound is cured with an active energy beam other than an electron beam, a crosslinking agent, a catalyst or a photopolymerization initiator is usually used. Since it can be formed and is excellent in storage stability (pot life), it can be applied for a long time without a liquid changing operation, which is preferable from the viewpoint of economy and stability of peeled physical properties. Conventionally, when curing an addition reaction type silicone compound, a hydrosilyl group-containing one is used as a crosslinking agent, a platinum catalyst is used as a curing catalyst, and when curing a photocuring type silicone compound, A polymerization initiator was used, but all had a problem in storage stability (pot life).
本発明は剥離シートとともに粘着体も提供する。
本発明の粘着体は、剥離剤層と粘着剤層とが接するように貼合された構成を有する粘着体であれば特に限定されないが、例えば、後で述べる粘着シート基材の表面に後で述べる粘着剤層が形成され、その粘着剤層と剥離剤層とが接するように貼合された剥離シートを有する形態のものや、粘着シート基材の粘着剤層を設ける面とは反対の面に剥離剤層を設け、剥離剤層と粘着剤層とが接するように貼合されロール状に巻回された構成のものがある。
The present invention also provides a pressure-sensitive adhesive body together with a release sheet.
The pressure-sensitive adhesive body of the present invention is not particularly limited as long as it has a structure bonded so that the release agent layer and the pressure-sensitive adhesive layer are in contact with each other. The adhesive layer to be described is formed, and the surface having the release sheet bonded so that the adhesive layer and the release agent layer are in contact, or the surface opposite to the surface on which the adhesive layer of the adhesive sheet substrate is provided There is a structure in which a release agent layer is provided, and the release agent layer and the pressure-sensitive adhesive layer are bonded so as to be in contact with each other and wound in a roll shape.
粘着シート基材としては、粘着剤層を支持する機能を有しており、例えば、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリメチルペンテンフィルム、ポリカーボネートフィルム等のプラスチックフィルム、アルミニウム、ステンレス等の金属箔、無塵紙、合成紙等の単体もしくは複合物等が用いられる。
粘着シート基材の厚さは、特に限定されないが、５〜３００μｍであるのが好ましく、１０〜２００μｍであるのがより好ましい。
粘着シート基材は、その表面（粘着剤層が形成される面と反対側の面）に印刷や印字が施されていてもよい。また、粘着剤層や剥離剤層との密着性を向上させる等の目的で、粘着シート基材は、前記剥離シート基材の説明において述べたコロナ放電処理等の表面処理が施されていてもよい。
The adhesive sheet substrate has a function of supporting the adhesive layer, for example, polyethylene terephthalate film, polybutylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, plastic film such as polycarbonate film, aluminum In addition, a simple substance such as a metal foil such as stainless steel, dust-free paper, or synthetic paper, or a composite material is used.
Although the thickness of an adhesive sheet base material is not specifically limited, It is preferable that it is 5-300 micrometers, and it is more preferable that it is 10-200 micrometers.
The pressure-sensitive adhesive sheet substrate may be printed or printed on the surface (the surface opposite to the surface on which the pressure-sensitive adhesive layer is formed). In addition, for the purpose of improving the adhesiveness with the pressure-sensitive adhesive layer or the release agent layer, the pressure-sensitive adhesive sheet substrate may be subjected to a surface treatment such as the corona discharge treatment described in the description of the release sheet substrate. Good.
粘着剤層は、粘着剤を主剤とした粘着剤組成物で構成されており、粘着剤としては、例えば、アクリル系粘着剤、ポリエステル系粘着剤、ウレタンアクリレート系粘着剤、シリコーン系粘着剤（付加反応型、過酸化物硬化型）、ポリイソブチレン系粘着剤、ゴム系粘着剤（天然ゴム系、スチレン/ブタジエンラテックス系、熱可塑性ゴム系、ブチルゴム系）等が挙げられる。中でも、粘着剤はアクリル系など、シリコーン系粘着剤とは異なる種類の材料を用いることが好ましい。剥離剤層を形成するシリコーン化合物と類似のシリコーン系粘着剤を用いると剥離力が強くなりすぎて剥がれにくくなることがある。 The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive composition mainly composed of a pressure-sensitive adhesive. Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, urethane acrylate-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives (additional). Reactive type, peroxide curable type), polyisobutylene type adhesive, rubber type adhesive (natural rubber type, styrene / butadiene latex type, thermoplastic rubber type, butyl rubber type) and the like. Among these, it is preferable to use a different type of material from the silicone-based pressure-sensitive adhesive, such as acrylic. If a silicone-based pressure-sensitive adhesive similar to the silicone compound that forms the release agent layer is used, the release force may be too strong and difficult to peel off.
粘着剤層の厚さは、特に限定されないが、５〜２００μｍであるのが好ましく、１０〜１００μｍであるのがより好ましく、この程度の厚さにするには粘着剤の塗布量は１０〜２００ｇ/ｍ2が好ましく、より好ましくは、３０〜８０ｇ/ｍ2である。 Although the thickness of an adhesive layer is not specifically limited, It is preferable that it is 5-200 micrometers, It is more preferable that it is 10-100 micrometers, The application amount of an adhesive is 10-200 g in order to make this thickness. / m 2 is preferable, and more preferably 30 to 80 g / m 2 .
粘着剤組成物を粘着シート基材に塗工する方法としては、例えば、グラビアコート法、バーコート法、スプレーコート法、スピンコート法、ナイフコート法、ロールコート法、ダイコート法等の既存の方法が使用できる。
この場合の粘着剤組成物の形態としては、溶剤型、エマルション型、ホットメルト型等が挙げられる。
Examples of methods for applying the pressure-sensitive adhesive composition to the pressure-sensitive adhesive sheet substrate include existing methods such as gravure coating, bar coating, spray coating, spin coating, knife coating, roll coating, and die coating. Can be used.
Examples of the form of the pressure-sensitive adhesive composition in this case include a solvent type, an emulsion type, and a hot melt type.
次に、本発明を実施例および比較例によりさらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。 EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these examples.
〔実施例1〕
重合性または架橋性官能基を含まないシリコーン化合物としてフェニル基含有ポリオルガノシロキサン(東レ・ダウコーニング社製、ＢＹ２４−８４２、フェニル基/メチル基の個数比率３３/６７、末端基：ジメチルシラノール基、固形分５０質量％のトルエン溶液)をトルエンでシリコーン化合物の濃度が１．０質量％になるように溶解して剥離剤の有機溶剤溶液とした。
この有機溶剤溶液をメイヤーバーを用いて乾燥後の膜厚が０．１μmとなるように剥離シート基材である厚み３８μmのＰＥＴフィルム(三菱ポリエステルフィルム社製、Ｔ１００)の片面に塗工し、１００℃で３０秒間乾燥させることにより剥離シート基材上に塗工層を形成させた。
次いで、フュージョンＨバルブ（２４０Ｗ/ｃｍ）を１灯(高圧水銀灯)具備するベルトコンベヤー式紫外線照射装置［フュージョンＵＶ社製、ＶＰ５−６］により、コンベヤー速度４０ｍ/分の条件(紫外線照射量：１００ｍＪ/ｃｍ2)にて、塗工層に紫外線照射を行い、硬化させて剥離剤層を有する本発明の剥離シートを得た。
Example 1
As a silicone compound containing no polymerizable or crosslinkable functional group, a phenyl group-containing polyorganosiloxane (manufactured by Toray Dow Corning, BY24-842, phenyl group / methyl group number ratio 33/67, terminal group: dimethylsilanol group, A toluene solution having a solid content of 50% by mass was dissolved in toluene so that the concentration of the silicone compound was 1.0% by mass to obtain an organic solvent solution of a release agent.
The organic solvent solution was applied to one side of a 38 μm thick PET film (Mitsubishi Polyester Film Co., Ltd., T100) as a release sheet substrate so that the film thickness after drying was 0.1 μm using a Mayer bar. A coating layer was formed on the release sheet substrate by drying at 100 ° C. for 30 seconds.
Next, a belt conveyor type ultraviolet irradiation device equipped with one fusion H bulb (240 W / cm) (high pressure mercury lamp) [manufactured by Fusion UV, VP5-6], the condition of the conveyor speed 40 m / min (UV irradiation amount: 100 mJ) / cm 2 ), the coating layer was irradiated with ultraviolet rays and cured to obtain a release sheet of the present invention having a release agent layer.
〔実施例２〕
剥離剤の有機溶剤溶液に光重合開始剤である1−ヒドロキシ−シクロヘキシル−フェニル−ケトン(チバガイギー社製、商品名：イルガキュア１８４)を０．０５質量部添加した以外は実施例1と同様にして本発明の剥離シートを得た。
[Example 2]
Example 1 was repeated except that 0.05 part by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Geigy Co.), which is a photopolymerization initiator, was added to the organic solvent solution of the release agent. A release sheet of the present invention was obtained.
〔比較例1〕
ＢＹ２４−８４２の替わりに、重合性または架橋性官能基もフェニル基も含有していないポリジメチルオルガノシロキサン(東レ・ダウコーニング社製：ＢＹ２４−８５０、固形分３０質量％、末端基：トリメチルシラン基)を用いた以外は実施例1と同様にして比較用の剥離シートを得た。
(Comparative Example 1)
Instead of BY24-842, polydimethylorganosiloxane containing no polymerizable or crosslinkable functional group or phenyl group (manufactured by Toray Dow Corning: BY24-850, solid content 30% by mass, terminal group: trimethylsilane group A comparative release sheet was obtained in the same manner as in Example 1 except that (2) was used.
〔比較例２〕
ＢＹ２４−８４２の替わりにＢＹ２４−８５０を用い、剥離剤の有機溶剤溶液に光重合開始剤である1−ヒドロキシ−シクロヘキシル−フェニル−ケトン(チバガイギー社製、商品名：イルガキュア１８４)を０．０５質量部添加した以外は実施例1と同様にして比較用の剥離シートを得た。
[Comparative Example 2]
Instead of BY24-842, BY24-850 was used, and 0.05 mass of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Geigy Co.) as a photopolymerization initiator was used in the organic solvent solution of the release agent. A comparative release sheet was obtained in the same manner as in Example 1 except that a part thereof was added.
〔比較例３〕
塗工層に紫外線照射を行わなかった以外は実施例1と同様にして比較用の剥離シートを得た。
[Comparative Example 3]
A comparative release sheet was obtained in the same manner as in Example 1 except that the coating layer was not irradiated with ultraviolet rays.
〔比較例４〕
塗工層に紫外線照射を行わなかった以外は実施例２と同様にして比較用の剥離シートを得た。
[Comparative Example 4]
A comparative release sheet was obtained in the same manner as in Example 2 except that the coating layer was not irradiated with ultraviolet rays.
〔応用例および比較応用例〕
上記実施例および比較例で作製された剥離シートまたは比較用の剥離シート上に形成された剥離剤層面上にアクリル系粘着剤(東洋インキ製：ＢＰＳ−５１２７)を塗工(塗工量：２４ｇ/ｍ2)し、粘着シート基材であるＰＥＴフィルム(東レ製：ルミラーＥ２０＃５０、厚さ５０μｍ)と上記粘着剤の塗工面を貼合させ、１９．６Ｎの荷重をかけたローラーで1往復させて本発明の粘着体および比較用の粘着体を作製した。温度２３℃・湿度５０％ＲＨの条件下に1日放置後、各々の剥離力を測定し、結果を表１に示した。
[Application examples and comparative application examples]
An acrylic pressure-sensitive adhesive (manufactured by Toyo Ink: BPS-5127) is coated on the release agent layer surface formed on the release sheet prepared in the above Examples and Comparative Examples or the release sheet for comparison (coating amount: 24 g). / m 2 ), and a PET film (Toray: Lumirror E20 # 50, thickness 50 μm) as an adhesive sheet base material and a coated surface of the above-mentioned adhesive are bonded to each other with a roller applied with a load of 19.6 N. The pressure-sensitive adhesive body of the present invention and a comparative pressure-sensitive adhesive body were produced by reciprocating. After leaving for 1 day under the conditions of a temperature of 23 ° C. and a humidity of 50% RH, each peel force was measured, and the results are shown in Table 1.
＜評価項目と測定方法＞
１．剥離力
測定は、万能引っ張り試験機(オリエンテック製：ＴＥＮＳＩＬＯＮ ＵＴＭ−４−１００)を用いて、温度２３℃・５０％ＲＨの条件下で本発明の粘着体または比較用の粘着体の粘着シート基材側を１８０°方向に３００ｍｍ/分の速度で剥離させることにより行った。
<Evaluation items and measurement method>
1. Peeling force is measured using a universal tensile tester (Orientec: TENSILON UTM-4-100) under the conditions of a temperature of 23 ° C. and 50% RH, the pressure-sensitive adhesive sheet of the present invention or the pressure-sensitive adhesive for comparison. It was performed by peeling the substrate side in the 180 ° direction at a speed of 300 mm / min.
２．硬化性
本発明の剥離シートまたは比較用の剥離シートの剥離剤の層を指で１０回擦り、曇り(スミヤー)発生の有無を目視により確認し判定した。
評価基準は以下の通りである。
○：スミアーなし(硬化性良好)
×：スミアーあり(硬化性不良)
2. Curability The release agent layer of the release sheet of the present invention or the release sheet for comparison was rubbed 10 times with a finger, and the presence or absence of cloudiness (smear) was visually confirmed and judged.
The evaluation criteria are as follows.
○: No smear (good curability)
×: Smear is present (hardness is poor)
３．密着性
本発明の剥離シートまたは比較用の剥離シートの剥離剤の層を指で１０回擦り、市販の粘着シート(日東電工製３１Ｂテープ)の粘着剤の層を貼り合わせ、剥離した際の処理面の剥離性の変化を確認し、塗膜剥がれ(ラブオフ)発生有無により密着性の判定を行なった。評価基準は以下の通りである。
○：ラブオフなし。剥離力変化がほとんど見られないもの(密着性良好)
×：ラブオフあり。重剥離化が生じたもの(密着性不良)
なお、剥離力が１０００ｍＮ/２０ｍｍを超えると重剥離化しており、実質的に使用不可である。
3. Adhesiveness The release layer of the release sheet of the present invention or the release sheet for comparison is rubbed 10 times with a finger, and the adhesive layer of a commercially available adhesive sheet (31B tape manufactured by Nitto Denko) is bonded and peeled off. The change in the peelability of the surface was confirmed, and the adhesion was judged by the presence or absence of occurrence of coating film peeling (love off). The evaluation criteria are as follows.
○: No love-off. There is almost no change in peel force (good adhesion)
X: There is a love-off. Heavy peeling occurred (adhesion failure)
In addition, when peeling force exceeds 1000 mN / 20mm, it will be heavy peeling and it cannot use substantially.
４．耐溶剤性
トルエンを含浸させたウェスを用いて本発明の剥離シートまたは比較用の剥離シートの剥離剤層を１０回擦った後、市販の粘着シート(日東電工製３１Ｂテープ)を貼り合わせ、前記剥離力を測定し、剥離した際の処理面の剥離性の変化を確認し、次のように評価した。評価基準は以下の通りである。
○：剥離力に変化が殆ど見られないもの(皮膜がトルエンに不溶)
×：重剥離化が生じたもの(皮膜がトルエンに可溶)
なお、剥離力が１０００ｍＮ/２０ｍｍを超えると重剥離化しており、実質的に使用不可である。
4). Solvent resistance After rubbing the release agent layer of the release sheet of the present invention or the release sheet for comparison with a waste impregnated with toluene 10 times, a commercially available adhesive sheet (31B tape manufactured by Nitto Denko) was bonded together, The peel force was measured, the change in peelability of the treated surface when peeled was confirmed, and evaluated as follows. The evaluation criteria are as follows.
○: The peel force hardly changes (the film is insoluble in toluene)
X: Heavy peeling occurred (film is soluble in toluene)
In addition, when peeling force exceeds 1000 mN / 20mm, it will be heavy peeling and it cannot use substantially.
表１から明らかなように、実施例で得られた本発明の剥離シートは比較用の剥離シートと比べて硬化性、密着性および耐溶剤性の点で優れていることがわかる。また、光重合開始剤を用いない場合は、剥離力の点でも優れていることが明らかである。実施例で得られた本発明の剥離シートの中でも、光重合開始剤を用いた場合は、硬化性等の性能は良いが、剥離力がやや大であまり好ましくないことが明らかである。 As is clear from Table 1, it can be seen that the release sheets of the present invention obtained in the examples are superior in terms of curability, adhesion, and solvent resistance as compared with comparative release sheets. In addition, when no photopolymerization initiator is used, it is clear that the peel strength is also excellent. Among the release sheets of the present invention obtained in Examples, it is clear that when a photopolymerization initiator is used, the performance such as curability is good, but the release force is somewhat large and not so preferable.
本発明の剥離シートは粘着ラベルや樹脂シート製造時のキャリアーシート、それらの保護シート、セラミックグリーンシート成膜用工程フィルムなどとして用いられる。本発明の粘着体は粘着ラベルや医療用貼付材、各種粘着テープ等に好ましく用いられる。 The release sheet of the present invention is used as a pressure-sensitive adhesive label, a carrier sheet for producing a resin sheet, a protective sheet thereof, a process film for forming a ceramic green sheet, or the like. The pressure-sensitive adhesive body of the present invention is preferably used for pressure-sensitive adhesive labels, medical patch materials, various pressure-sensitive adhesive tapes, and the like.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007036380A JP4914241B2 (en) | 2007-02-16 | 2007-02-16 | Release sheet and adhesive |
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|---|---|---|---|
| JP2007036380A JP4914241B2 (en) | 2007-02-16 | 2007-02-16 | Release sheet and adhesive |
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| JP2008200880A true JP2008200880A (en) | 2008-09-04 |
| JP4914241B2 JP4914241B2 (en) | 2012-04-11 |
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| JP (1) | JP4914241B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013145864A1 (en) * | 2012-03-28 | 2013-10-03 | リンテック株式会社 | Peeling film for step for producing ceramic green sheet |
| WO2015068859A1 (en) * | 2013-11-11 | 2015-05-14 | Dow Corning Toray Co., Ltd. | Curable organopolysiloxane composition and release film for use with dielectric ceramic layer-forming material using same |
| JP2015208940A (en) * | 2014-04-28 | 2015-11-24 | 三菱樹脂株式会社 | Release polyester film |
| JP2020111993A (en) * | 2019-01-15 | 2020-07-27 | 株式会社川島織物セルコン | Tile material |
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| JPH1135895A (en) * | 1997-07-18 | 1999-02-09 | Toagosei Co Ltd | Sheet for release |
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| JP2004351612A (en) * | 2003-05-26 | 2004-12-16 | Lintec Corp | Release sheet and pressure-sensitive adhesive element |
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| JPS61207471A (en) * | 1985-03-11 | 1986-09-13 | Toray Silicone Co Ltd | Strippable film-forming organopolysiloxane composition |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013145864A1 (en) * | 2012-03-28 | 2013-10-03 | リンテック株式会社 | Peeling film for step for producing ceramic green sheet |
| JP5492352B2 (en) * | 2012-03-28 | 2014-05-14 | リンテック株式会社 | Release film for ceramic green sheet manufacturing process |
| CN104220221A (en) * | 2012-03-28 | 2014-12-17 | 琳得科株式会社 | Peeling film for step for producing ceramic green sheet |
| WO2015068859A1 (en) * | 2013-11-11 | 2015-05-14 | Dow Corning Toray Co., Ltd. | Curable organopolysiloxane composition and release film for use with dielectric ceramic layer-forming material using same |
| JP2017503903A (en) * | 2013-11-11 | 2017-02-02 | 東レ・ダウコーニング株式会社 | Curable organopolysiloxane composition and release film for dielectric ceramic layer molding material using the same |
| JP2015208940A (en) * | 2014-04-28 | 2015-11-24 | 三菱樹脂株式会社 | Release polyester film |
| JP2020111993A (en) * | 2019-01-15 | 2020-07-27 | 株式会社川島織物セルコン | Tile material |
| JP7248372B2 (en) | 2019-01-15 | 2023-03-29 | 株式会社川島織物セルコン | tile material |
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| JP4914241B2 (en) | 2012-04-11 |
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