JP2020069664A - Mold release sheet and its manufacturing method - Google Patents
Mold release sheet and its manufacturing method Download PDFInfo
- Publication number
- JP2020069664A JP2020069664A JP2018203367A JP2018203367A JP2020069664A JP 2020069664 A JP2020069664 A JP 2020069664A JP 2018203367 A JP2018203367 A JP 2018203367A JP 2018203367 A JP2018203367 A JP 2018203367A JP 2020069664 A JP2020069664 A JP 2020069664A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- release sheet
- methyl
- resin layer
- modified
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 229920005989 resin Polymers 0.000 claims abstract description 93
- 239000011347 resin Substances 0.000 claims abstract description 93
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical class CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229920000642 polymer Polymers 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 49
- -1 oxazoline compound Chemical class 0.000 claims abstract description 36
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims description 26
- 239000011344 liquid material Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 17
- 229920005992 thermoplastic resin Polymers 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 71
- 239000006185 dispersion Substances 0.000 description 25
- 239000003960 organic solvent Substances 0.000 description 15
- 239000000123 paper Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
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- 239000011521 glass Substances 0.000 description 8
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- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
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- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
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- 239000000428 dust Substances 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920000393 Nylon 6/6T Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 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
- 239000002216 antistatic agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
本発明は、離型シートに関するものである。 The present invention relates to a release sheet.
離型シートは工業的に広く用いられており、例えば、粘着テープ、接着シート、フレキシブルプリント配線板、多層プリント配線板、液晶ディスプレイ用部品である偏光板・位相差板、層間絶縁材料であるエポキシプリプレグ、ゴムシートなどのシート状構造体などの製造工程で用いられる。
離型シートの中でも、樹脂層にシリコーン系離型剤を用いた離型シートは、シリコーン系離型剤の中に含まれる低分子量のシリコーン化合物が、製品の表面に移行して残存する場合があり、プリント配線板等の高度な信頼性が要求されるような製品の製造工程において、製品へのシリコーンの汚染による悪影響を及ぼす場合があった。
そこで、樹脂層にシリコーン系離型剤を含有しない非シリコーン系離型シートの開発が行われており、非シリコーン系離型剤が、例えば特許文献１に開示されている。
Release sheets are widely used industrially, and examples thereof include adhesive tapes, adhesive sheets, flexible printed wiring boards, multilayer printed wiring boards, liquid crystal display components such as polarizing plates and retarders, and interlayer insulating materials such as epoxy. It is used in the manufacturing process of sheet-like structures such as prepregs and rubber sheets.
Among the release sheets, the release sheet using the silicone release agent in the resin layer may have a low molecular weight silicone compound contained in the silicone release agent transferred to the surface of the product and remain. In some cases, in the manufacturing process of a product such as a printed wiring board that requires high reliability, the product may be adversely affected by contamination of silicone.
Therefore, a non-silicone release sheet containing no silicone release agent in the resin layer has been developed, and a non-silicone release agent is disclosed in Patent Document 1, for example.
近年、プリント配線板用の絶縁材料には、エポキシ樹脂などの熱硬化性樹脂が用いられており、製造工程時間の短縮や接着性向上の観点から、従来よりも高温の熱硬化処理が行われている。特許文献１には、離型性、耐熱性に優れた離型剤が開示されているものの、前記離型剤は、プリント配線板製造工程時に晒されるほどの高温に対する耐熱性や、エポキシ樹脂などの熱硬化性樹脂に対する離型性は不十分な場合があった。
本発明はこれらの問題に鑑み、高温で熱処理がなされても、離型性、耐熱性、寸法安定性に優れる離型シートを提供しようとするものである。
In recent years, thermosetting resins such as epoxy resins have been used as insulating materials for printed wiring boards, and from the viewpoint of shortening the manufacturing process time and improving adhesiveness, thermosetting treatment at a higher temperature than before is performed. ing. Although Patent Document 1 discloses a mold release agent having excellent mold releasability and heat resistance, the mold release agent has heat resistance to a high temperature that is exposed during a manufacturing process of a printed wiring board, an epoxy resin, and the like. In some cases, the releasability from the thermosetting resin was insufficient.
In view of these problems, the present invention intends to provide a release sheet that is excellent in mold release property, heat resistance, and dimensional stability even when heat-treated at high temperature.
本発明者は、上記課題を解決するために鋭意検討した結果、離型シートを構成する樹脂層が、酸変性４−メチル−１−ペンテン系重合体と架橋剤とを含有することで、上記課題が解決することを見出し、本発明に到達した。
すなわち、本発明の要旨は下記の通りである。
MEANS TO SOLVE THE PROBLEM As a result of earnestly studying in order to solve the said subject, this inventor said that the resin layer which comprises a release sheet contains an acid-modified 4-methyl-1-pentene-based polymer and a crosslinking agent. The inventors have found that the problems can be solved and arrived at the present invention.
That is, the gist of the present invention is as follows.
（１）基材上に樹脂層を設けてなる離型シートであって、樹脂層が、酸変性４−メチル−１−ペンテン系重合体１００質量部と架橋剤０．１〜５０質量部とを含有することを特徴とする離型シート。
（２）架橋剤が、オキサゾリン化合物および／またはカルボジイミド化合物であることを特徴とする（１）記載の離型シート。
（３）基材が熱可塑性樹脂からなるフィルムであることを特徴とする（１）または（２）記載の離型シート。
（４）熱可塑性樹脂がポリエステル樹脂であることを特徴とする（３）記載の離型シート。
（５）上記（１）〜（４）のいずれかに記載の離型シートを製造するための方法であって、
基材に、酸変性４−メチル−１−ペンテン系重合体と架橋剤とを含有する樹脂層形成用液状物を塗布する工程と、乾燥して樹脂層を形成する工程とを有することを特徴とする離型シートの製造方法。
（６）上記（３）または（４）記載の離型シートを製造するための方法であって、
酸変性４−メチル−１−ペンテン系重合体と架橋剤とを含有する樹脂層形成用液状物が塗布された基材を乾燥、延伸する工程を含むことを特徴とする離型シートの製造方法。
(1) A release sheet having a resin layer provided on a substrate, wherein the resin layer comprises 100 parts by mass of an acid-modified 4-methyl-1-pentene polymer and 0.1 to 50 parts by mass of a crosslinking agent. A release sheet comprising:
(2) The release sheet according to (1), wherein the crosslinking agent is an oxazoline compound and / or a carbodiimide compound.
(3) The release sheet according to (1) or (2), wherein the base material is a film made of a thermoplastic resin.
(4) The release sheet according to (3), wherein the thermoplastic resin is a polyester resin.
(5) A method for producing the release sheet according to any one of (1) to (4) above, which comprises:
It has a step of applying a liquid material for forming a resin layer containing an acid-modified 4-methyl-1-pentene-based polymer and a cross-linking agent to a base material, and a step of forming a resin layer by drying. And a method for manufacturing a release sheet.
(6) A method for producing the release sheet according to (3) or (4) above, which comprises:
A method for producing a release sheet, comprising the steps of drying and stretching a substrate coated with a resin layer-forming liquid containing an acid-modified 4-methyl-1-pentene polymer and a crosslinking agent. ..
本発明の離型シートは、基材上に、酸変性４−メチル−１−ペンテン系重合体と架橋剤とを含有した樹脂層が形成されており、高温で熱処理された、例えば２００℃程度またはそれ以上の高温で硬化させた熱硬化性樹脂に対しても、良好な離型性および耐熱性を備えており、また、高温での寸法安定性に優れている。 The release sheet of the present invention has a resin layer containing an acid-modified 4-methyl-1-pentene-based polymer and a cross-linking agent formed on a substrate, and is heat-treated at a high temperature, for example, about 200 ° C. It also has good mold releasability and heat resistance even for a thermosetting resin cured at a higher temperature than that, or has excellent dimensional stability at high temperatures.
以下、本発明を詳細に説明する。
本発明の離型シートは、基材上に樹脂層が設けられたものであり、樹脂層は、酸変性４−メチル−１−ペンテン系重合体と架橋剤とを含有する。
Hereinafter, the present invention will be described in detail.
The release sheet of the present invention has a resin layer provided on a base material, and the resin layer contains an acid-modified 4-methyl-1-pentene polymer and a crosslinking agent.
酸変性４−メチル−１−ペンテン系重合体は、４−メチル−１−ペンテン系重合体が酸変性されたものであり、４−メチル−１−ペンテン系重合体としては、４−メチル−１−ペンテンの重合体、および、４−メチル−１−ペンテンとα−オレフィン（４−メチル−１−ペンテンを除く）との共重合体が挙げられる。 The acid-modified 4-methyl-1-pentene-based polymer is a 4-methyl-1-pentene-based polymer acid-modified, and as the 4-methyl-1-pentene-based polymer, 4-methyl-pentene-based polymer is used. Examples thereof include a polymer of 1-pentene and a copolymer of 4-methyl-1-pentene and α-olefin (excluding 4-methyl-1-pentene).
前記共重合体を構成するα−オレフィンとしては、炭素数が２〜２０のものを挙げることができ、例えば、エチレン、プロピレン、１−ブテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセンおよび１−エイコセンなどが挙げられ、好ましくは、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセンおよび１−エイコセンが挙げられる。これらα−オレフィンは、１種単独で、または２種以上を組み合わせて用いられる。
共重合体は、４−メチル−１−ペンテンと上記α−オレフィンとから、従来公知の方法により共重合させて製造することができる。共重合反応は、α−オレフィンが反応物の合計モル量に対して、通常１５モル％以下、好ましくは９モル％以下である条件で行われる。
Examples of the α-olefin constituting the copolymer include those having 2 to 20 carbon atoms, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, and 1-octene. -Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, and preferably 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eikosen is mentioned. These α-olefins may be used alone or in combination of two or more.
The copolymer can be produced by copolymerizing 4-methyl-1-pentene and the above α-olefin by a conventionally known method. The copolymerization reaction is carried out under the condition that the amount of α-olefin is usually 15 mol% or less, preferably 9 mol% or less, based on the total molar amount of the reactants.
４−メチル−１−ペンテン系重合体は、共重合体である場合、４−メチル−１−ペンテンとα−オレフィンとのランダム共重合体であることが好ましい。４−メチル−１−ペンテン・α−オレフィンランダム共重合体は、４−メチル−１−ペンテン単位が８０〜９９．９質量％であることが好ましく、９０〜９８質量％であることがより好ましく、α−オレフィン単位が０．１〜２０質量％であることが好ましく、２〜１０質量％であることがより好ましい。 When the 4-methyl-1-pentene-based polymer is a copolymer, it is preferably a random copolymer of 4-methyl-1-pentene and α-olefin. The 4-methyl-1-pentene / α-olefin random copolymer has a 4-methyl-1-pentene unit content of preferably 80 to 99.9% by mass, more preferably 90 to 98% by mass. , Α-olefin units are preferably 0.1 to 20% by mass, and more preferably 2 to 10% by mass.
酸変性に用いることができる４−メチル−１−ペンテン系重合体の市販品としては、三井化学社製の「ＤＸ８４５」、「ＤＸ８２０」、「ＤＸ２３１」、「ＤＸ３１０」、「ＭＸ００４」、「ＭＸ００２」などが挙げられる。 Examples of commercially available 4-methyl-1-pentene-based polymers that can be used for acid modification include "DX845", "DX820", "DX231", "DX310", "MX004", and "MX002" manufactured by Mitsui Chemicals, Inc. And the like.
樹脂層を構成する酸変性４−メチル−１−ペンテン系重合体は、上記４−メチル−１−ペンテン系重合体が酸変性されたものである。
酸変性４−メチル−１−ペンテン系重合体における酸変性成分の含有量は、１〜１０質量％であることが好ましく、１〜７質量％であることがより好ましく、２〜５質量％であることがさらに好ましく、２〜３質量％であることが特に好ましい。酸変性４−メチル−１−ペンテン系重合体は、酸変性成分の量が１質量％未満であると、水性分散化することが困難になることがあり、また、得られる樹脂層は、基材との十分な密着性が得られないことがあり、被着体を汚染する可能性がある。一方、酸変性４−メチル−１−ペンテン系重合体における酸変性成分の量が１０質量％を超えると、得られる樹脂層は、離型性が低下することがある。
The acid-modified 4-methyl-1-pentene-based polymer constituting the resin layer is an acid-modified 4-methyl-1-pentene-based polymer.
The content of the acid-modified component in the acid-modified 4-methyl-1-pentene polymer is preferably 1 to 10% by mass, more preferably 1 to 7% by mass, and 2 to 5% by mass. It is more preferable to be present, and it is particularly preferable to be 2 to 3% by mass. When the amount of the acid-modified component of the acid-modified 4-methyl-1-pentene-based polymer is less than 1% by mass, it may be difficult to disperse it in an aqueous solution, and the obtained resin layer has a base group. There is a case where sufficient adhesion with the material cannot be obtained, which may contaminate the adherend. On the other hand, when the amount of the acid-modified component in the acid-modified 4-methyl-1-pentene-based polymer exceeds 10% by mass, the releasability of the obtained resin layer may decrease.
酸変性成分としては、不飽和カルボン酸成分が挙げられ、具体的には、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、フマル酸、クロトン酸等のほか、不飽和ジカルボン酸のハーフエステル、ハーフアミド等が挙げられる。中でも、酸変性４−メチル−１−ペンテン系重合体の分散安定性の面から、酸変性成分は、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸が好ましく、アクリル酸、メタクリル酸、無水マレイン酸がより好ましい。 Examples of the acid-modified component include unsaturated carboxylic acid components, and specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and the like. Examples thereof include saturated dicarboxylic acid half esters and half amides. Among them, from the viewpoint of dispersion stability of the acid-modified 4-methyl-1-pentene polymer, the acid-modified component is preferably acrylic acid, methacrylic acid, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, maleic anhydride. Acids are more preferred.
酸変性４−メチル−１−ペンテン系重合体は、メルトフローレートが、２６０℃、２１６０ｇ荷重において、１〜１０００ｇ／１０分であることが好ましく、１〜５００ｇ／１０分であることがより好ましく、２〜３００ｇ／１０分であることがさらに好ましく、２〜２００ｇ／１０分であることが特に好ましい。メルトフローレートが１ｇ／１０分未満の酸変性４−メチル−１−ペンテン系重合体は、製造が困難なうえ、水性分散化するのが困難となることがある。酸変性４−メチル−１−ペンテン系重合体のメルトフローレートが１０００ｇ／１０分を超えると、得られる樹脂層は、基材との密着性が低下して、被着体への移行が起こりやすくなることがある。 The acid-modified 4-methyl-1-pentene-based polymer has a melt flow rate of preferably 1 to 1000 g / 10 minutes, more preferably 1 to 500 g / 10 minutes at 260 ° C. and a load of 2160 g. , 2 to 300 g / 10 minutes are more preferable, and 2 to 200 g / 10 minutes are particularly preferable. An acid-modified 4-methyl-1-pentene polymer having a melt flow rate of less than 1 g / 10 minutes may be difficult to manufacture and may be difficult to disperse in an aqueous solution. When the melt flow rate of the acid-modified 4-methyl-1-pentene-based polymer exceeds 1000 g / 10 minutes, the adhesiveness of the obtained resin layer to the base material is lowered, and transfer to an adherend occurs. It may be easier.
本発明の離型シートを構成する樹脂層は、架橋剤を含有することが必要である。
架橋剤の含有量は、酸変性４−メチル−１−ペンテン系重合体１００質量部に対して、０．１〜５０質量部であることが必要であり、３〜３０質量部であることが好ましく、５〜１０質量部であることがより好ましい。架橋剤は、含有量が０．１質量部未満であると添加効果が乏しく、架橋剤の含有量が５０質量部を超えると、樹脂層は、離型性が低下する場合がある。
The resin layer constituting the release sheet of the present invention needs to contain a crosslinking agent.
The content of the cross-linking agent needs to be 0.1 to 50 parts by mass and is 3 to 30 parts by mass with respect to 100 parts by mass of the acid-modified 4-methyl-1-pentene-based polymer. It is more preferably 5 to 10 parts by mass. When the content of the cross-linking agent is less than 0.1 parts by mass, the effect of addition is poor, and when the content of the cross-linking agent exceeds 50 parts by mass, the releasability of the resin layer may decrease.
架橋剤としては、オキサゾリン化合物、カルボジイミド化合物、エポキシ化合物、メラミン化合物、イソシアネート化合物、尿素化合物、アジリジン化合物、ジルコニウム塩化合物、シランカップリング剤等が挙げられ、酸変性４−メチル−１−ペンテン系重合体に含まれる酸変性成分との反応性の点から、オキサゾリン化合物および／またはカルボジイミド化合物であることが好ましい。オキサゾリン化合物とカルボジイミド化合物とを併用する場合には、オキサゾリン化合物とカルボジイミド化合物の合計量が上記した架橋剤の含有量の範囲を満たしていればよい。 Examples of the cross-linking agent include oxazoline compounds, carbodiimide compounds, epoxy compounds, melamine compounds, isocyanate compounds, urea compounds, aziridine compounds, zirconium salt compounds, and silane coupling agents, and acid-modified 4-methyl-1-pentene-based compounds. The oxazoline compound and / or the carbodiimide compound are preferable from the viewpoint of reactivity with the acid-modified component contained in the combination. When the oxazoline compound and the carbodiimide compound are used in combination, the total amount of the oxazoline compound and the carbodiimide compound may satisfy the above range of the content of the crosslinking agent.
オキサゾリン化合物は、分子中にオキサゾリン基を２つ以上有しているものであればよく、特に限定されない。例えば、２，２′−ビス（２−オキサゾリン）、２，２′−エチレン−ビス（４，４′−ジメチル−２−オキサゾリン）、２，２′−ｐ−フェニレン−ビス（２−オキサゾリン）、ビス（２−オキサゾリニルシクロヘキサン）スルフィドなどのオキサゾリン基を有する化合物や、オキサゾリン基含有ポリマーなどが挙げられる。これらは、１種または２種以上を用いることができる。これらの中でも、取り扱いやすさから、オキサゾリン基含有ポリマーが好ましい。オキサゾリン基含有ポリマーは、２−ビニル−２−オキサゾリン、２−ビニル−４−メチル−２−オキサゾリン、２−イソプロペニル−２−オキサゾリン等の付加重合性オキサゾリン重合させることにより得られる。必要に応じて他の単量体が共重合されていてもよい。オキサゾリン基含有ポリマーの重合方法は、特に限定されず、公知の種々の重合方法を採用することができる。 The oxazoline compound is not particularly limited as long as it has two or more oxazoline groups in the molecule. For example, 2,2'-bis (2-oxazoline), 2,2'-ethylene-bis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis (2-oxazoline) , A compound having an oxazoline group such as bis (2-oxazolinylcyclohexane) sulfide, and an oxazoline group-containing polymer. These can use 1 type (s) or 2 or more types. Among these, the oxazoline group-containing polymer is preferable because it is easy to handle. The oxazoline group-containing polymer is obtained by addition-polymerizing oxazoline such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline and 2-isopropenyl-2-oxazoline. Other monomers may be copolymerized if necessary. The polymerization method of the oxazoline group-containing polymer is not particularly limited, and various known polymerization methods can be adopted.
オキサゾリン基含有ポリマーの市販品としては、日本触媒社製のエポクロスシリーズが挙げられる。より具体的には、水溶性タイプの「ＷＳ−５００」、「ＷＳ−７００」や、エマルションタイプの「Ｋ−１０１０Ｅ」、「Ｋ−１０２０Ｅ」、「Ｋ−１０３０Ｅ」、「Ｋ−２０１０Ｅ」、「Ｋ−２０２０Ｅ」、「Ｋ−２０３０Ｅ」などが挙げられる。 Examples of commercially available oxazoline group-containing polymers include Epocros series manufactured by Nippon Shokubai Co., Ltd. More specifically, water-soluble type "WS-500", "WS-700", emulsion type "K-1010E", "K-1020E", "K-1030E", "K-2010E", "K-2020E", "K-2030E" etc. are mentioned.
カルボジイミド化合物は、分子中に少なくとも２つ以上のカルボジイミド基を有しているものであればよく、特に限定されない。例えば、ｐ−フェニレン−ビス（２，６−キシリルカルボジイミド）、テトラメチレン−ビス（ｔ−ブチルカルボジイミド）、シクロヘキサン−１，４−ビス（メチレン−ｔ−ブチルカルボジイミド）などのカルボジイミド基を有する化合物や、カルボジイミド基を有する重合体であるポリカルボジイミドが挙げられる。これらの１種または２種以上を用いることができる。これらの中でも、取り扱いやすさから、ポリカルボジイミドが好ましい。ポリカルボジイミドの製法は、特に限定されない。ポリカルボジイミドは、例えば、イソシアネート化合物の脱二酸化炭素を伴う縮合反応により製造することができる。イソシアネート化合物も限定されず、脂肪族イソシアネート、脂環族イソシアネート、芳香族イソシアネートのいずれであってもよい。イソシアネート化合物は、必要に応じて多官能液状ゴムやポリアルキレンジオールなどが共重合されていてもよい。 The carbodiimide compound is not particularly limited as long as it has at least two carbodiimide groups in the molecule. Compounds having a carbodiimide group such as p-phenylene-bis (2,6-xylylcarbodiimide), tetramethylene-bis (t-butylcarbodiimide), cyclohexane-1,4-bis (methylene-t-butylcarbodiimide) And polycarbodiimide, which is a polymer having a carbodiimide group. These 1 type (s) or 2 or more types can be used. Among these, polycarbodiimide is preferable because it is easy to handle. The production method of polycarbodiimide is not particularly limited. Polycarbodiimide can be produced, for example, by a condensation reaction involving decarbonization of an isocyanate compound. The isocyanate compound is also not limited, and may be any of aliphatic isocyanate, alicyclic isocyanate, and aromatic isocyanate. The isocyanate compound may be copolymerized with a polyfunctional liquid rubber, polyalkylene diol, or the like, if necessary.
ポリカルボジイミドの市販品としては、日清紡社製のカルボジライトシリーズが挙げられる。より具体的には、水溶性タイプの「ＳＶ−０２」、「Ｖ−０２」、「Ｖ−０２−Ｌ２」、「Ｖ−０４」；エマルションタイプの「Ｅ−０１」、「Ｅ−０２」；有機溶液タイプの「Ｖ−０１」、「Ｖ−０３」、「Ｖ−０７」、「Ｖ−０９」；無溶剤タイプの「Ｖ−０５」が挙げられる。 Examples of commercially available products of polycarbodiimide include carbodilite series manufactured by Nisshinbo. More specifically, water-soluble type "SV-02", "V-02", "V-02-L2", "V-04"; emulsion type "E-01", "E-02". An organic solution type "V-01", "V-03", "V-07", "V09"; a solventless type "V-05".
エポキシ化合物は、１分子中に２個以上のエポキシ基を有するものであれば特に制限はなく、例えば、ビスフェノールＡグリシジルエーテル型、ビスフェノールＦグリシジルエーテル型、ビスフェノールＳ型グリシジルエーテル型、ビスフェノールＡＤグリシジルエーテル型、ビフェニルグリシジルエーテル型、フェノールノボラック型、クレゾールノボラック型、脂環式、複素環式、グリシジルエステル型、グリシジルアミン型、ソルビトールグリシジルエーテル型、グリセロールグリシジルエーテル型等のものが挙げられる。
エポキシ化合物の市販品としては、ＡＤＥＫＡ社製の「ＥＭ−０５１Ｒ」、三菱化学社製の「ＪＥＲ−８２８」、「ＪＥＲ−１００１」、「ＪＥＲ−１００４」、「ＪＥＲ−１００７」、「ＪＥＲ−１００９」、ナガセケムテックス社製の「ＥＸ−６１２」、「ＥＸ−６１４」、「ＥＸ−６１４Ｂ」、「ＥＸ−３１３」、「ＥＸ−３１４」、「ＥＸ−８１０」、「ＥＸ−８１１」、「ＥＸ−８５０」、「ＥＸ−８５１」、「ＥＸ−８２１」などが挙げられる。
The epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule, and examples thereof include bisphenol A glycidyl ether type, bisphenol F glycidyl ether type, bisphenol S glycidyl ether type, and bisphenol AD glycidyl ether. Type, biphenyl glycidyl ether type, phenol novolac type, cresol novolac type, alicyclic type, heterocyclic type, glycidyl ester type, glycidyl amine type, sorbitol glycidyl ether type, glycerol glycidyl ether type and the like.
Commercially available products of epoxy compounds include "EM-051R" manufactured by ADEKA, "JER-828", "JER-1001", "JER-1004", "JER-1007" and "JER-" manufactured by Mitsubishi Chemical Corporation. 1009 "," EX-612 "," EX-614 "," EX-614B "," EX-313 "," EX-314 "," EX-810 "," EX-811 "manufactured by Nagase Chemtex. , "EX-850", "EX-851", "EX-821" and the like.
樹脂層は、上記酸変性４−メチル−１−ペンテン系重合体と架橋剤とを含有するが、本発明の目的を損なわない範囲で、必要に応じて各種添加剤を含有してもよい。添加剤としては、例えば、シランカップリング剤、耐候安定剤、スリップ剤、核剤、顔料、染料などが挙げられる。 The resin layer contains the above acid-modified 4-methyl-1-pentene-based polymer and a crosslinking agent, but may contain various additives as necessary within the range not impairing the object of the present invention. Examples of the additives include silane coupling agents, weathering stabilizers, slip agents, nucleating agents, pigments, dyes and the like.
樹脂層の厚みは、０．０１〜５μｍであることが好ましく、０．１〜２μｍであることがより好ましく、０．２〜１μｍであることがさらに好ましく、０．３〜０．７μｍであることが特に好ましい。樹脂層は、厚みが０．０１μｍ未満であると、十分な離型性が得られず、５μｍを超えると、離型性が低下することがある。また、後述する帯電防止処理がなされた基材上に設けられた樹脂層においては、厚みが５μｍを超えると、十分な帯電防止性が得られず、剥離工程において帯電し、表面に大気中の塵や埃が付着することにより、剥離された製品において、欠陥および粘着力の低下の原因となる可能性がある。 The thickness of the resin layer is preferably 0.01 to 5 μm, more preferably 0.1 to 2 μm, further preferably 0.2 to 1 μm, and 0.3 to 0.7 μm. Is particularly preferable. If the thickness of the resin layer is less than 0.01 μm, sufficient releasability cannot be obtained, and if it exceeds 5 μm, the releasability may deteriorate. Further, in the resin layer provided on the base material subjected to the antistatic treatment described later, when the thickness exceeds 5 μm, sufficient antistatic property cannot be obtained, and the surface is exposed to the atmosphere in the atmosphere due to being charged in the peeling step. The adhesion of dust or dirt may cause defects and a decrease in adhesive strength in the peeled product.
離型シートを構成する基材としては、樹脂材料、紙、合成紙、布、金属材料、ガラス材料等で形成されたものが挙げられる。
基材の厚みは、特に限定されるものではないが、通常は１〜１０００μｍであればよく、１〜５００μｍが好ましく、１〜１００μｍがより好ましく、１〜５０μｍが特に好ましい。
Examples of the base material forming the release sheet include those formed of resin material, paper, synthetic paper, cloth, metal material, glass material and the like.
Although the thickness of the substrate is not particularly limited, it is usually 1 to 1000 μm, preferably 1 to 500 μm, more preferably 1 to 100 μm, and particularly preferably 1 to 50 μm.
基材に用いることができる樹脂材料としては、例えば熱可塑性樹脂として、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリ乳酸（ＰＬＡ）などのポリエステル樹脂；ポリプロピレン等のポリオレフィン樹脂；ポリスチレン樹脂；６−ナイロン、ポリ−ｍ−キシリレンアジバミド（ＭＸＤ６ナイロン）等のポリアミド樹脂；半芳香族ポリアミド樹脂；ポリカーボネート樹脂；ポリアクリルニトリル樹脂；ポリイミド樹脂；これらの樹脂の複層体（例えば、ナイロン６／ＭＸＤ／ナイロン６、ナイロン６／エチレン−ビニルアルコール共重合体／ナイロン６）や混合体等が挙げられる。
基材は熱可塑性樹脂からなるフィルムであることが好ましく、中でも、機械的特性、熱的寸法安定性に優れるポリエステル樹脂フィルムが好ましく、安価で入手が容易という点からポリエチレンテレフタレートフィルムであることが好ましい。
樹脂材料は、寸法安定性の観点から延伸されているものであることが好ましい。
Examples of the resin material that can be used as the base material include thermoplastic resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polylactic acid (PLA), and other polyester resins; polypropylene and other polyolefin resins; polystyrene resins; Polyamide resins such as 6-nylon and poly-m-xylylene adipamide (MXD6 nylon); semi-aromatic polyamide resins; polycarbonate resins; polyacrylonitrile resins; polyimide resins; multilayers of these resins (for example, nylon 6 / MXD / nylon 6, nylon 6 / ethylene-vinyl alcohol copolymer / nylon 6), a mixture and the like.
The substrate is preferably a film made of a thermoplastic resin, and among them, a polyester resin film having excellent mechanical properties and thermal dimensional stability is preferable, and a polyethylene terephthalate film is preferable from the viewpoint of being inexpensive and easily available. ..
The resin material is preferably stretched from the viewpoint of dimensional stability.
樹脂材料は、公知の添加剤や安定剤、例えば、帯電防止剤、可塑剤、滑剤、酸化防止剤などを含んでいてもよい。また、樹脂材料は、その他の材料と積層する場合の密着性を向上させるために、表面に前処理としてコロナ処理、プラズマ処理、オゾン処理、薬品処理、溶剤処理等を施したものでもよい。また、樹脂材料は、シリカ、アルミナ等が蒸着されていてもよく、バリア層や易接着層、帯電防止層、紫外線吸収層、接着層などの他の層が積層されていてもよく、さらに、紙、合成紙、布、他の樹脂材料、金属材料等を、樹脂層を設ける側とは反対側に積層してもよい。
樹脂材料は、非常に帯電しやすく、種々の障害を生じる場合があるため、樹脂材料からなる基材は、帯電防止処理されていることが好ましい。基材が帯電防止処理されていると、離型シートは、工程フィルムとして使用する場合には、剥離工程において発生する摩擦帯電や剥離帯電により帯びた静電気が大気中のゴミや塵、埃等を吸着することにより生じる製品の欠陥を防止できる。また、粘着剤の保護材料として使用した場合には、剥離帯電により発生した静電気により粘着面に塵や埃が付着して粘着力が低下することを防止できる。
帯電防止処理された樹脂材料を得る方法としては、樹脂材料中に帯電防止剤を練りこむ方法、樹脂材料に帯電防止層を積層する方法がある。帯電防止層を積層する方法が、より低コストで帯電防止処理することができる。
上記帯電防止処理は、樹脂材料に限定されるものではなく、後述する紙や合成紙、布やガラス材料などにも施されてもよい。
The resin material may contain known additives and stabilizers such as antistatic agents, plasticizers, lubricants, and antioxidants. Further, the resin material may have a surface subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment or the like as a pretreatment in order to improve adhesion when laminated with other materials. In addition, the resin material may be vapor-deposited with silica, alumina or the like, and may be laminated with other layers such as a barrier layer, an easily adhesive layer, an antistatic layer, an ultraviolet absorbing layer and an adhesive layer. Paper, synthetic paper, cloth, other resin material, metal material, etc. may be laminated on the side opposite to the side on which the resin layer is provided.
Since the resin material is very easily charged and may cause various troubles, the base material made of the resin material is preferably subjected to antistatic treatment. When the base material is subjected to antistatic treatment, the release sheet, when used as a process film, removes dust, dirt, dust, etc. in the atmosphere from static electricity caused by frictional charging and peeling charging generated in the peeling process. Product defects caused by adsorption can be prevented. Further, when it is used as a protective material for an adhesive, it is possible to prevent the adhesion force from being reduced due to dust or dirt adhering to the adhesive surface due to static electricity generated by peeling electrification.
As a method for obtaining an antistatic-treated resin material, there are a method of kneading an antistatic agent into a resin material and a method of laminating an antistatic layer on the resin material. The method of laminating the antistatic layer enables the antistatic treatment at a lower cost.
The antistatic treatment is not limited to the resin material, and may be applied to paper, synthetic paper, cloth, glass material, etc. described later.
基材として用いることができる紙としては、和紙、クラフト紙、ライナー紙、アート紙、コート紙、カートン紙、グラシン紙、セミグラシン紙等を挙げることができる。
基材として用いることができる合成紙は、その構造は特に限定されず、単独構造であっても多層構造であってもよい。多層構造としては、例えば基材層と表面層の２層構造、基材層の表裏面に表面層が存在する３層構造、基材層と表面層の間に他の樹脂フィルム層が存在する多層構造を例示することができる。各層は、無機や有機のフィラーを含有していてもよいし、含有していなくてもよい。微細なボイドを多数有する微多孔性合成紙も使用することができる。
基材として用いることができる布としては、上述した合成樹脂からなる繊維や、木綿、絹、麻などの天然繊維からなる、不織布、織布、編布などが挙げられる。
基材として用いることができる金属材料としては、アルミ箔や銅箔などの金属箔や、アルミ板や銅板などの金属板などが挙げられる。
基材として用いることができるガラス材料としては、ガラス板やガラス繊維からなる布などが挙げられる。
Examples of the paper that can be used as the substrate include Japanese paper, kraft paper, liner paper, art paper, coated paper, carton paper, glassine paper, semi-glassine paper, and the like.
The structure of the synthetic paper that can be used as the substrate is not particularly limited, and may be a single structure or a multi-layer structure. Examples of the multilayer structure include a two-layer structure of a base material layer and a surface layer, a three-layer structure in which the front surface and the back surface of the base material layer exist, and another resin film layer exists between the base material layer and the surface layer. A multilayer structure can be illustrated. Each layer may or may not contain an inorganic or organic filler. Microporous synthetic paper with many fine voids can also be used.
Examples of the cloth that can be used as the base material include a non-woven fabric, a woven fabric, and a knitted fabric made of the above-mentioned synthetic resin fibers and natural fibers such as cotton, silk, and hemp.
Examples of the metal material that can be used as the base material include metal foils such as aluminum foil and copper foil, and metal plates such as aluminum plate and copper plate.
Examples of the glass material that can be used as the base material include a glass plate and a cloth made of glass fiber.
本発明の離型シートは、酸変性４−メチル−１−ペンテン系重合体と架橋剤とを含有し、水性媒体などに分散または溶解された液状物を、基材上に塗布したのち乾燥して樹脂層を形成する方法によって、工業的に簡便に製造することができる。 The release sheet of the present invention contains an acid-modified 4-methyl-1-pentene-based polymer and a cross-linking agent, and a liquid material dispersed or dissolved in an aqueous medium or the like is applied onto a substrate and then dried. By the method of forming the resin layer by using the above method, the resin layer can be easily manufactured industrially.
酸変性４−メチル−１−ペンテン系重合体と架橋剤とを含有する樹脂層形成用液状物を調製する方法は、各成分が液状媒体中に均一に混合される方法であれば、特に限定されない。例えば、酸変性４−メチル−１−ペンテン系重合体の分散液または溶液に、架橋剤の分散液または溶液を添加して混合する方法が挙げられる。また、樹脂層が他の成分を含有する場合においても、任意の段階で他の成分を添加して液状物を調製することができる。 The method for preparing a resin layer-forming liquid containing an acid-modified 4-methyl-1-pentene-based polymer and a crosslinking agent is not particularly limited as long as each component is uniformly mixed in the liquid medium. Not done. For example, a method may be mentioned in which a dispersion liquid or solution of a cross-linking agent is added to and mixed with a dispersion liquid or solution of an acid-modified 4-methyl-1-pentene-based polymer. Further, even when the resin layer contains other components, other components can be added at any stage to prepare a liquid material.
樹脂層形成用液状物を構成する溶媒は、基材上に液状物の塗布が可能なものであれば、特に限定されず、水、有機溶剤、あるいは水と両親媒性有機溶剤とを含む水性媒体などが挙げられる。なかでも、環境上、水または水性媒体であることが好ましい。 The solvent constituting the liquid material for forming the resin layer is not particularly limited as long as the liquid material can be applied to the substrate, and water, an organic solvent, or an aqueous solution containing water and an amphipathic organic solvent. Examples include media. Of these, water or an aqueous medium is preferable in view of the environment.
有機溶剤としては、ジエチルケトン（３−ペンタノン）、メチルプロピルケトン（２−ペンタノン）、メチルイソブチルケトン（４−メチル−２−ペンタノン）、２−ヘキサノン、５−メチル−２−ヘキサノン、２−へプタノン、３−へプタノン、４−へプタノン、シクロペンタノン、シクロヘキサノン等のケトン類；トルエン、キシレン、ベンゼン、ソルベッソ１００、ソルベッソ１５０等の芳香族炭化水素類；ブタン、ペンタン、ヘキサン、シクロヘキサン、ヘプタン、オクタン、ノナン等の脂肪族炭化水素類；塩化メチレン、クロロホルム、四塩化炭素、１，２−ジクロロエタン、１，１，２，２−テトラクロロエタン、クロロベンゼン、ｏ−ジクロロベンゼン、ｍ−ジクロロベンゼン、ｐ−ジクロロベンゼン等の含ハロゲン類；酢酸エチル、酢酸イソプロピル、酢酸−ｎ−ブチル、酢酸イソブチル、酢酸−ｓｅｃ−ブチル、酢酸−３−メトキシブチル、プロピオン酸メチル、プロピオン酸エチル、炭酸ジエチル、γ−ブチロラクトン、イソホロン等のエステル類；後述の両親媒性有機溶剤などが挙げられる。 As the organic solvent, diethyl ketone (3-pentanone), methyl propyl ketone (2-pentanone), methyl isobutyl ketone (4-methyl-2-pentanone), 2-hexanone, 5-methyl-2-hexanone, 2-to Ketones such as butanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone; aromatic hydrocarbons such as toluene, xylene, benzene, Solvesso 100, Solvesso 150; butane, pentane, hexane, cyclohexane, heptane , Aliphatic hydrocarbons such as octane and nonane; methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, Halogen-containing compounds such as p-dichlorobenzene; acetic acid Esters such as chill, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, γ-butyrolactone and isophorone; Examples thereof include amphipathic organic solvents.
本発明において、水性媒体とは、水と両親媒性有機溶剤とを含み、水の含有量が２質量％以上である溶媒を意味する。両親媒性有機溶剤とは、２０℃における有機溶剤に対する水の溶解性が５質量％以上である有機溶剤をいう〔２０℃における有機溶剤に対する水の溶解性については、例えば「溶剤ハンドブック」（講談社サイエンティフィク、１９９０年第１０版）等の文献に記載されている〕。具体的には、メタノール、エタノール、ｎ−プロパノール、イソプロパノール等のアルコール類；テトラヒドロフラン、１，４−ジオキサン等のエーテル類；アセトン、メチルエチルケトン等のケトン類；酢酸メチル、酢酸−ｎ−プロピル、酢酸イソプロピル、プロピオン酸メチル、プロピオン酸エチル、炭酸ジメチル等のエステル類；そのほか、アンモニアを含む、ジエチルアミン、トリエチルアミン、ジエタノールアミン、トリエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ，Ｎ−ジエチルエタノールアミン、Ｎ−ジエタノールアミン等の有機アミン化合物；２−ピロリドン、Ｎ−メチル−２−ピロリドンなどのラクタム類等を挙げることができる。 In the present invention, the aqueous medium means a solvent containing water and an amphipathic organic solvent and having a water content of 2% by mass or more. The amphiphilic organic solvent refers to an organic solvent having a water solubility of 5% by mass or more in an organic solvent at 20 ° C. [For solubility of water in an organic solvent at 20 ° C., see, for example, “Solvent Handbook” (Kodansha Scientific, 1990, 10th Edition), etc.]. Specifically, alcohols such as methanol, ethanol, n-propanol and isopropanol; ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as acetone and methyl ethyl ketone; methyl acetate, acetic acid n-propyl and isopropyl acetate. , Esters such as methyl propionate, ethyl propionate, dimethyl carbonate; and others, including ammonia, diethylamine, triethylamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N- Organic amine compounds such as diethanolamine; lactams such as 2-pyrrolidone and N-methyl-2-pyrrolidone.
酸変性４−メチル−１−ペンテン系重合体を上記のような水性媒体に分散化する方法は、特に限定されず、例えば、国際公開ＷＯ０２／０５５５９８号に記載された方法が挙げられる。 The method of dispersing the acid-modified 4-methyl-1-pentene polymer in the above aqueous medium is not particularly limited, and examples thereof include the method described in WO02 / 055598.
水性媒体中の酸変性４−メチル−１−ペンテン系重合体の分散粒子径は、他の成分との混合時の安定性および混合後の保存安定性の点から、数平均粒子径が１μｍ以下であることが好ましく、０．８μｍ以下であることがより好ましい。このような粒子径は、ＷＯ０２／０５５５９８号に記載の製法により達成可能である。 The dispersed particle size of the acid-modified 4-methyl-1-pentene polymer in the aqueous medium has a number average particle size of 1 μm or less from the viewpoint of stability at the time of mixing with other components and storage stability after mixing. Is preferable, and 0.8 μm or less is more preferable. Such a particle size can be achieved by the production method described in WO02 / 055598.
樹脂層形成用液状物における固形分濃度は、積層条件、目的とする厚さや性能等により適宜選択でき、特に限定されないが、液状物の粘性を適度に保ち、かつ良好な樹脂層を形成させるためには、１〜６０質量％であることが好ましく、５〜３０質量％であることがより好ましい。 The solid content concentration in the liquid material for forming the resin layer can be appropriately selected depending on the lamination conditions, the target thickness and performance, and is not particularly limited, but to maintain the viscosity of the liquid material moderately and to form a good resin layer. In addition, 1 to 60 mass% is preferable, and 5 to 30 mass% is more preferable.
樹脂層形成用液状物を基材に塗布する方法としては、公知の方法、例えばグラビアロールコーティング、リバースロールコーティング、ワイヤーバーコーティング、リップコーティング、エアナイフコーティング、カーテンフローコーティング、スプレーコーティング、浸漬コーティング、はけ塗り法等を挙げることができる。これらの方法により液状物を基材の表面に均一に塗布し、必要に応じて室温付近でセッティングした後、乾燥処理または乾燥のための加熱処理に供することにより、均一な樹脂層を基材に密着させて形成することができる。
基材上に樹脂層を形成した後、酸変性４−メチル−１−ペンテン系重合体と架橋剤との反応を促進させるために、一定の温度にコントロールされた環境下でエージング処理をおこなってもよい。エージング温度は、基材へのダメージを軽減する観点からは、比較的低いことが好ましく、反応を十分かつ速やかに進行させるという観点からは、高温で処理することが好ましい。エージングは２０〜１００℃でおこなうことが望ましく、３０〜７０℃でおこなうことがより好ましく、４０〜６０℃でおこなうことがさらに好ましい。
The method for applying the resin layer-forming liquid material to the substrate is a known method, for example, gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, A brush coating method and the like can be mentioned. By uniformly applying the liquid material to the surface of the substrate by these methods, and setting the temperature near room temperature as necessary, by subjecting it to a drying treatment or a heating treatment for drying, a uniform resin layer is formed on the substrate. It can be formed in close contact.
After forming the resin layer on the base material, in order to promote the reaction between the acid-modified 4-methyl-1-pentene-based polymer and the cross-linking agent, aging treatment is performed in an environment controlled at a constant temperature. Good. The aging temperature is preferably relatively low from the viewpoint of reducing damage to the base material, and is preferably high temperature from the viewpoint of allowing the reaction to proceed sufficiently and quickly. Aging is preferably performed at 20 to 100 ° C, more preferably at 30 to 70 ° C, and further preferably at 40 to 60 ° C.
ポリエステル樹脂フィルムなどの熱可塑性樹脂フィルムからなる樹脂材料を基材とし、これに樹脂層形成用液状物を塗布する場合、二軸延伸されたフィルムに、樹脂層形成用液状物を塗布後、乾燥、熱処理してもよく（オフラインコート）、また、配向が完了する以前の未延伸フィルムあるいは一軸延伸の終了したフィルムに、樹脂層形成用液状物を塗布し、乾燥後、加熱して延伸するか、あるいは加熱して乾燥と同時に延伸して、熱可塑性樹脂の配向を完了させてもよい（インラインコート）。
後者の未延伸フィルムあるいは一軸延伸終了後のフィルムに液状物を塗布後、乾燥、延伸配向する方法は、熱可塑性樹脂フィルムの製膜と同時に樹脂層を積層することができるため、コストの点から好ましい。また延伸工程において樹脂層に高温の熱がかかることにより、酸変性４−メチル−１−ペンテン系重合体と架橋剤との反応を効率的に進められるという点からも好ましい。また、液状物として水性分散体を使用することが、製造工程内に防爆設備が不要であるなどの点からより好ましい。
When a resin material composed of a thermoplastic resin film such as a polyester resin film is used as a base material and a liquid material for forming a resin layer is applied thereto, the biaxially stretched film is applied with the liquid material for forming a resin layer and then dried. It may be heat-treated (off-line coating), or the unstretched film before orientation is completed or the film after uniaxial stretching is applied with the liquid material for forming the resin layer, dried and then heated and stretched. Alternatively, the thermoplastic resin may be stretched simultaneously with heating and drying to complete the orientation of the thermoplastic resin (in-line coating).
After applying a liquid material to the latter unstretched film or the film after uniaxial stretching, the method of drying and stretching orientation is a method in which the resin layer can be laminated at the same time as the thermoplastic resin film is formed. preferable. Further, it is also preferable from the viewpoint that the reaction between the acid-modified 4-methyl-1-pentene polymer and the crosslinking agent can be efficiently promoted by applying high temperature heat to the resin layer in the stretching step. In addition, it is more preferable to use an aqueous dispersion as the liquid substance, since explosion-proof equipment is not required in the manufacturing process.
以下に実施例によって本発明を具体的に説明する。ただし、本発明はこれらによって限定されるものではない。 The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.
（１）酸変性４−メチル−１−ペンテン系重合体の酸変性成分含有量
酸変性４−メチル−１−ペンテン系重合体における酸変性成分の含有量は、酸価をＪＩＳ Ｋ５４０７に準じて測定し、その値から不飽和カルボン酸の含有量（グラフト率）を次式から求めた。
酸変性成分含有量（質量％）＝（グラフトした不飽和カルボン酸の質量）/（酸変性４−メチル−１−ペンテン系重合体の質量）×１００
(1) Content of Acid-Modifying Component of Acid-Modified 4-Methyl-1-Pentene Polymer The content of the acid-modifying component in the acid-modified 4-methyl-1-pentene polymer has an acid value according to JIS K5407. The content was measured, and the content (graft ratio) of the unsaturated carboxylic acid was calculated from the following formula from the measured value.
Content of acid-modifying component (mass%) = (mass of grafted unsaturated carboxylic acid) / (mass of acid-modified 4-methyl-1-pentene-based polymer) × 100
（２）酸変性４−メチル−１−ペンテン系重合体のメルトフローレート
ＪＩＳ Ｋ６７３０記載（２６０℃、２１６０ｇ荷重）の方法で測定した。
(2) Melt flow rate of acid-modified 4-methyl-1-pentene polymer Measured by the method described in JIS K6730 (260 ° C., 2160 g load).
（３）水性分散体の有機溶剤含有率
島津製作所社製、ガスクロマトグラフＧＣ−８Ａ［ＦＩＤ検出器使用、キャリアーガス：窒素、カラム充填物質（ジーエルサイエンス社製）：ＰＥＧ−ＨＴ（５％）−Ｕｎｉｐｏｒｔ ＨＰ（６０／８０メッシュ）、カラムサイズ：直径３ｍｍ×３ｍ、試料投入温度（インジェクション温度）：１５０℃、カラム温度：６０℃、内部標準物質：ｎ-ブタノール］を用い、水性分散体または水性分散体を水で希釈したものを直接装置内に投入して、有機溶剤の含有率を求めた。検出限界は０．０１質量％であった。
(3) Organic solvent content rate of aqueous dispersion, Shimadzu Corp. gas chromatograph GC-8A [using FID detector, carrier gas: nitrogen, column packing material (GL Science): PEG-HT (5%)- Uniport HP (60/80 mesh), column size: diameter 3 mm x 3 m, sample injection temperature (injection temperature): 150 ° C, column temperature: 60 ° C, internal standard substance: n-butanol], and an aqueous dispersion or aqueous solution The dispersion diluted with water was put directly into the apparatus to determine the content of the organic solvent. The detection limit was 0.01% by mass.
（４）水性分散体の固形分濃度
液状物を適量秤量し、これを１５０℃で残存物（固形分）の質量が恒量に達するまで加熱することで、固形分濃度を求めた。
(4) Solid Content Concentration of Aqueous Dispersion An appropriate amount of a liquid material was weighed and heated at 150 ° C. until the mass of the residual material (solid content) reached a constant amount, whereby the solid content concentration was determined.
（５）樹脂粒子の数平均粒子径
日機装社製、マイクロトラック粒度分布計ＵＰＡ１５０（ＭＯＤＥＬ Ｎｏ．９３４０、動的光散乱法）を用い、数平均粒子径を求めた。粒子径算出に用いた樹脂の屈折率は１．５７とした。
(5) Number average particle diameter of resin particles The number average particle diameter was determined by using Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340, dynamic light scattering method) manufactured by Nikkiso Co., Ltd. The refractive index of the resin used for the particle size calculation was 1.57.
（６）樹脂層の厚み
離型シートの全体の厚さを接触式膜厚計により測定し、その測定値から基材の厚さを減じて求めた。
(6) Thickness of Resin Layer The total thickness of the release sheet was measured by a contact-type film thickness meter, and the thickness of the substrate was subtracted from the measured value.
（７）基材と樹脂層との密着性
離型シートの樹脂層の表面に、粘着テープ（ニチバン社製ＴＦ−１２）を貼り付けた後、この粘着テープを勢いよく剥離した。そして、離型シートの表面状態を目視で観察し、以下の基準で密着性を評価した。
○：樹脂層が剥がれない
×：樹脂層の一部または全部が剥がれる
(7) Adhesion between base material and resin layer After sticking an adhesive tape (TF-12 manufactured by Nichiban Co., Ltd.) on the surface of the resin layer of the release sheet, the adhesive tape was peeled off vigorously. Then, the surface state of the release sheet was visually observed, and the adhesion was evaluated according to the following criteria.
◯: The resin layer is not peeled off ×: Part or all of the resin layer is peeled off
（８）離型性
３官能エポキシ樹脂(プリンテック社製 ＶＧ３１０１)およびメチルナジック酸を、質量比で７５／２５となるように、トルエン中で混合して、固形分濃度３０質量％の溶液を調製した。
この溶液を、離型シートの樹脂層表面に、乾燥後の厚みが５０μｍとなるように塗布し、１００℃で３分間乾燥させて、半硬化状態のエポキシ樹脂層が積層された離型シートを作製した。
次いで、離型シート上の半硬化状態のエポキシ樹脂層の上に、銅箔（古河電気工業社製Ｆ２−ＷＳ、厚み１８μｍ）を積層し、１．０７ｋＰａ（８Ｔｏｒｒ）の真空プレス機中で、３０℃から１９０℃まで１０℃／分で昇温し、６０分間保持した後、２３０℃まで１０℃／分で昇温し、２３０℃で２時間保持した後、室温まで冷却を行うことで、離型シート／エポキシ樹脂層／銅箔からなる構成の積層体を得た。なお、上記加熱処理は、１５ｋｇ／ｃｍ２の圧力をかけながら行った。
得られた積層体の、エポキシ樹脂層と離型シートとの間の剥離強度を、２５℃の恒温室で引張試験機（インテスコ社製、精密万能材料試験機、２０２０型）にて測定し、離型性を評価した。剥離角度は１８０度、剥離速度は３００ｍｍ／分とした。
離型シートは、通常の使用において、剥離強度が小さい方が好ましく、具体的には、製造工程における作業性の観点から３０ｇ／ｃｍ以下であることが好ましく、２０ｇ／ｃｍ以下であることがより好ましく、１０ｇ／ｃｍ以下であることがさらに好ましい。
(8) Releasability A trifunctional epoxy resin (VG3101 manufactured by Printec Co., Ltd.) and methyl nadic acid were mixed in toluene so that the mass ratio was 75/25, and a solution having a solid content concentration of 30 mass% was prepared. Prepared.
This solution is applied to the resin layer surface of the release sheet so that the thickness after drying is 50 μm, and dried at 100 ° C. for 3 minutes to obtain a release sheet having a semi-cured epoxy resin layer laminated thereon. It was made.
Then, a copper foil (F2-WS manufactured by Furukawa Electric Co., Ltd., thickness 18 μm) was laminated on the epoxy resin layer in a semi-cured state on the release sheet, and in a vacuum press of 1.07 kPa (8 Torr), By raising the temperature from 30 ° C. to 190 ° C. at 10 ° C./min, holding it for 60 minutes, raising it to 230 ° C. at 10 ° C./min, holding it at 230 ° C. for 2 hours, and then cooling it to room temperature, A laminate having a structure of release sheet / epoxy resin layer / copper foil was obtained. The heat treatment was performed while applying a pressure of 15 kg / cm 2 .
The peel strength between the epoxy resin layer and the release sheet of the obtained laminate was measured by a tensile tester (manufactured by Intesco, precision universal material tester, 2020 type) in a constant temperature chamber of 25 ° C., The releasability was evaluated. The peeling angle was 180 degrees, and the peeling speed was 300 mm / min.
In the normal use, the release sheet preferably has a low peel strength, and specifically, it is preferably 30 g / cm or less, more preferably 20 g / cm or less from the viewpoint of workability in the manufacturing process. It is more preferably 10 g / cm or less.
（９）寸法安定性
離型シートから２０ｃｍ×２０ｃｍの正方形の試験片を切り出した。
１７０℃に設定したオーブンの中に試験片を５分間静置させ、その後オーブンから取出し、常温冷却させた後に、試験片の面積を測定し、下記式から面積の減少率を算出した。
以下の基準で寸法安定性を評価した。
○：減少率が３．０％以下
△：減少率が３．０％を超え、５．０％以下であるか、熱しわが確認される
×：減少率が５．０％を超える
減少率（％）＝〔４００（ｃｍ２）−熱処理後の試験片の面積（ｃｍ２）〕／〔４００（ｃｍ２）〕×１００
(9) Dimensional stability A 20 cm × 20 cm square test piece was cut out from the release sheet.
The test piece was allowed to stand in an oven set at 170 ° C. for 5 minutes, then taken out from the oven and cooled at room temperature, the area of the test piece was measured, and the area reduction rate was calculated from the following formula.
The dimensional stability was evaluated according to the following criteria.
◯: Reduction rate is 3.0% or less Δ: Reduction rate is more than 3.0% and 5.0% or less, or heat wrinkles are confirmed ×: Reduction rate is more than 5.0% Reduction rate ( %) = [400 (cm 2 ) −area of test piece after heat treatment (cm 2 )] / [400 (cm 2 )] × 100
離型シートの原料として、下記のものを使用した。
〔酸変性４−メチル−１−ペンテン系重合体Ｐ−１〕
４−メチル−１−ペンテン系重合体（三井化学社製 ＴＰＸ ＤＸ８２０）２８０ｇを４つ口フラスコ中、窒素雰囲気下でキシレン４７０ｇに加熱溶解させた後、系内温度を１４０℃に保って攪拌下、不飽和カルボン酸として無水マレイン酸４０．０ｇとラジカル発生剤としてパークミルＤ（日本油脂社製）５．０ｇをそれぞれ２時間かけて加え、その後６時間反応させた。反応終了後、得られた反応生成物を多量のアセトン中に投入し、樹脂を析出させた。
この析出させた樹脂を、アセトンで繰り返し洗浄することで未反応の無水マレイン酸を除去した後、減圧乾燥機中で減圧乾燥して、酸変性４−メチル−１−ペンテン系重合体Ｐ−１を得た。その酸変性成分の含有量は３質量％、メルトフローレートは３５ｇ／１０分であった。
The following materials were used as the materials for the release sheet.
[Acid-modified 4-methyl-1-pentene polymer P-1]
After 280 g of 4-methyl-1-pentene polymer (TPX DX820 manufactured by Mitsui Chemicals, Inc.) was dissolved in 470 g of xylene under heating in a four-necked flask under nitrogen atmosphere, the system temperature was maintained at 140 ° C. under stirring. Then, 40.0 g of maleic anhydride as an unsaturated carboxylic acid and 5.0 g of Percumyl D (manufactured by NOF CORPORATION) as a radical generator were added over 2 hours, respectively, and then reacted for 6 hours. After the reaction was completed, the obtained reaction product was put into a large amount of acetone to precipitate a resin.
The precipitated resin is repeatedly washed with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer to obtain an acid-modified 4-methyl-1-pentene polymer P-1. Got The content of the acid-modified component was 3% by mass, and the melt flow rate was 35 g / 10 minutes.
〔酸変性４−メチル−１−ペンテン系重合体Ｐ−２〕
無水マレイン酸を４５．０ｇ、ラジカル発生剤のパークミルＤを１０．０ｇ使用した以外は、重合体Ｐ−１と同様にして、酸変性成分の含有量が５質量％、メルトフローレートが５０ｇ／１０分である酸変性４−メチル−１−ペンテン系重合体Ｐ−２を得た。
[Acid-modified 4-methyl-1-pentene polymer P-2]
As in Polymer P-1, except that 45.0 g of maleic anhydride and 10.0 g of the radical generator Perkmill D were used, the content of the acid-modified component was 5% by mass, and the melt flow rate was 50 g / An acid-modified 4-methyl-1-pentene-based polymer P-2 having 10 minutes was obtained.
〔酸変性４−メチル−１−ペンテン系重合体Ｐ−３〕
無水マレイン酸を２５．０ｇ、ラジカル発生剤のパークミルＤを２．８ｇ使用した以外は、重合体Ｐ−１と同様にして、酸変性成分の含有量が１．５質量％、メルトフローレートが１５ｇ／１０分である酸変性４−メチル−１−ペンテン系重合体Ｐ−３を得た。
[Acid-modified 4-methyl-1-pentene polymer P-3]
The content of the acid-modifying component was 1.5% by mass and the melt flow rate was the same as that of the polymer P-1, except that 25.0 g of maleic anhydride and 2.8 g of the radical generator Perkmill D were used. An acid-modified 4-methyl-1-pentene polymer P-3 having an amount of 15 g / 10 minutes was obtained.
〔酸変性ポリオレフィン樹脂Ｐ−４〕
無水マレイン酸変性ポリエチレン樹脂（アルケマ社製 ボンダイン ＬＸ−４１１０、酸変性成分の含有量２質量％、メルトフローレート５ｇ／１０分（１９０℃））を使用した。
[Acid-modified polyolefin resin P-4]
A maleic anhydride-modified polyethylene resin (Bondayne LX-4110 manufactured by Arkema, content of the acid-modified component of 2% by mass, melt flow rate of 5 g / 10 minutes (190 ° C.)) was used.
〔酸変性４−メチル−１−ペンテン系重合体Ｐ−１の水性分散体Ｅ−１〕
ヒーター付きの密閉できる耐圧１リットル容ガラス容器を備えた撹拌機を用い、６０．０ｇの酸変性４−メチル−１−ペンテン系重合体Ｐ−１、１８０ｇのテトラヒドロフラン（ＴＨＦ）、３０．０ｇのトリエチルアミン（ＴＥＡ）および３３０ｇの蒸留水をガラス容器内に仕込んだ。そして、撹拌翼の回転速度を３００ｒｐｍとし、系内温度を１３０℃に保って、３０分間撹拌した。その後、攪拌しながら室温付近（約３０℃）まで冷却し、５０ｇの蒸留水を追加した後、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧ろ過（空気圧０．２ＭＰａ）した。得られた水性分散体を１Ｌナスフラスコに入れ、８０℃に加熱した湯浴につけながらエバポレーターを用いて減圧し、ＴＨＦ、水の混合媒体約２５０ｇを留去し、乳白色の均一な水性分散体Ｅ−１を得た。
得られた水性分散体Ｅ−１は、固形分濃度が１５．０質量％、有機溶剤の含有率が０.５質量％であり、重合体Ｐ−１の数平均粒子径は０．０７μｍであった。
[Aqueous dispersion of acid-modified 4-methyl-1-pentene-based polymer P-1 E-1]
Using a stirrer equipped with a heater capable of sealing a pressure-resistant 1 liter glass container, 60.0 g of acid-modified 4-methyl-1-pentene polymer P-1, 180 g of tetrahydrofuran (THF), 30.0 g of Triethylamine (TEA) and 330 g of distilled water were charged into a glass container. Then, the rotation speed of the stirring blade was set to 300 rpm, the internal temperature of the system was maintained at 130 ° C., and stirring was performed for 30 minutes. Then, while stirring, cool to around room temperature (about 30 ° C), add 50 g of distilled water, and then press-filter with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) (air pressure 0.2 MPa). did. The obtained aqueous dispersion was placed in a 1 L eggplant flask, depressurized using an evaporator while being immersed in a hot water bath heated to 80 ° C., and about 250 g of a mixed medium of THF and water was distilled off to obtain a milky white uniform aqueous dispersion E. -1 was obtained.
The obtained aqueous dispersion E-1 had a solid content concentration of 15.0 mass% and an organic solvent content of 0.5 mass%, and the polymer P-1 had a number average particle diameter of 0.07 μm. there were.
〔酸変性４−メチル−１−ペンテン系重合体Ｐ−２の水性分散体Ｅ−２〕
酸変性４−メチル−１−ペンテン系重合体の種類をＰ−２に変更した以外は重合体Ｐ−１の水性分散体Ｅ−１と同様の操作を行って、乳白色の均一な水性分散体Ｅ−２を得た。
得られた水性分散体Ｅ−２は、固形分濃度が１５．１質量％、有機溶剤の含有率が０.４質量％であり、重合体Ｐ−２の数平均粒子径は０．０５μｍであった。
[Aqueous Dispersion E-2 of Acid-Modified 4-Methyl-1-Pentene Polymer P-2]
A milky white uniform aqueous dispersion was prepared in the same manner as the aqueous dispersion E-1 of the polymer P-1 except that the type of the acid-modified 4-methyl-1-pentene polymer was changed to P-2. E-2 was obtained.
The obtained aqueous dispersion E-2 had a solid content concentration of 15.1% by mass, an organic solvent content of 0.4% by mass, and the polymer P-2 had a number average particle size of 0.05 μm. there were.
〔酸変性４−メチル−１−ペンテン系重合体Ｐ−３の水性分散体Ｅ−３〕
酸変性４−メチル−１−ペンテン系重合体の種類をＰ−３に変更した以外は重合体Ｐ−１の水性分散体Ｅ−１と同様の操作を行って、乳白色の均一な水性分散体Ｅ−３を得た。
得られた水性分散体Ｅ−３は、固形分濃度が１５．０質量％、有機溶剤の含有率が０.６質量％であり、重合体Ｐ−３の数平均粒子径は０．１０μｍであった。
[Aqueous dispersion of acid-modified 4-methyl-1-pentene-based polymer P-3 E-3]
A milky white uniform aqueous dispersion was prepared by the same procedure as the aqueous dispersion E-1 of the polymer P-1, except that the type of the acid-modified 4-methyl-1-pentene polymer was changed to P-3. E-3 was obtained.
The obtained aqueous dispersion E-3 had a solid content concentration of 15.0 mass% and an organic solvent content of 0.6 mass%, and the polymer P-3 had a number average particle diameter of 0.10 μm. there were.
〔酸変性ポリオレフィン樹脂Ｐ−４の水性分散体Ｎ−１〕
ヒーター付きの密閉できる耐圧１リットル容ガラス容器を備えた撹拌機を用い、６０．０ｇの酸変性ポリオレフィン樹脂Ｐ−４、９０．０ｇのイソプロパノール、３．０ｇのＴＥＡおよび１４７．０ｇの蒸留水をガラス容器内に仕込んだ。そして、撹拌翼の回転速度を３００ｒｐｍとし、系内温度を１４０〜１４５℃に保って、３０分間撹拌した。その後、水浴につけて、回転速度３００ｒｐｍのまま撹拌しつつ室温（約２５℃）まで冷却した。さらに、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧ろ過（空気圧０．２ＭＰａ）した。これによって、乳白色の均一な水性分散体Ｎ−１を得た。
得られた水性分散体Ｎ−１は、固形分濃度が２０．０質量％、有機溶剤の含有率が３０．０質量％であり、樹脂Ｐ−４の数平均粒子径は０．１０μｍであった。
[Aqueous dispersion of acid-modified polyolefin resin P-4 N-1]
Using a stirrer equipped with a heater capable of sealing a pressure-resistant 1 liter glass container, 60.0 g of acid-modified polyolefin resin P-4, 90.0 g of isopropanol, 3.0 g of TEA and 147.0 g of distilled water were added. It was placed in a glass container. Then, the rotation speed of the stirring blade was set to 300 rpm, the temperature inside the system was maintained at 140 to 145 ° C., and stirring was performed for 30 minutes. Then, it was immersed in a water bath and cooled to room temperature (about 25 ° C.) with stirring at a rotation speed of 300 rpm. Furthermore, pressure filtration (air pressure 0.2 MPa) was performed with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave). Thereby, a milky white uniform aqueous dispersion N-1 was obtained.
The obtained aqueous dispersion N-1 had a solid content concentration of 20.0% by mass, an organic solvent content of 30.0% by mass, and a resin P-4 having a number average particle diameter of 0.10 μm. It was
〔架橋剤〕
・オキサゾリン化合物の水性溶液（日本触媒社製、エポクロス ＷＳ−７００、固形分濃度４０質量％）
・カルボジイミド基含有高分子分散体（日清紡ケミカル社製、カルボジライトシリーズＥ−０１、固形分濃度４０質量％）
・エポキシ基含有高分子水溶液（ＡＤＥＫＡ社製、アデカレジンＥＭ−０５１Ｒ、固形分濃度４９．８質量％）
[Crosslinking agent]
-Aqueous solution of oxazoline compound (Nippon Shokubai Co., Ltd., Epocros WS-700, solid content concentration 40 mass%)
-Carbodiimide group-containing polymer dispersion (Nisshinbo Chemical Co., Ltd., Carbodilite series E-01, solid content concentration 40% by mass)
Epoxy group-containing polymer aqueous solution (ADEKA Corporation, Adeka Resin EM-051R, solid content concentration 49.8% by mass)
〔基材〕
・二軸延伸ポリエステル樹脂フィルム（ユニチカ社製、エンブレット Ｓ−５０、厚み５０μｍ）
〔Base material〕
Biaxially stretched polyester resin film (Unitika, Emblet S-50, thickness 50 μm)
実施例１
酸変性４−メチル−１−ペンテン系重合体Ｐ−１の水性分散体Ｅ−１と、オキサゾリン化合物の水性溶液とを、それぞれの固形分の質量比が１００／０．１となるように混合し、室温で５分間攪拌して、樹脂層形成用液状物を得た。
この液状物をポリエステル樹脂フィルムに、マイヤーバーを用いて塗布した後、１２０℃で１５秒間乾燥することで、フィルム上に０．１μｍの樹脂層が形成された離型シートを得た。
Example 1
An aqueous dispersion E-1 of the acid-modified 4-methyl-1-pentene polymer P-1 and an aqueous solution of an oxazoline compound are mixed so that the mass ratio of each solid content is 100 / 0.1. Then, the mixture was stirred at room temperature for 5 minutes to obtain a liquid material for forming a resin layer.
This liquid material was applied to a polyester resin film using a Meyer bar and then dried at 120 ° C. for 15 seconds to obtain a release sheet having a resin layer of 0.1 μm formed on the film.
実施例２〜９、比較例１〜３
酸変性４−メチル−１−ペンテン系重合体の水性分散体と架橋剤の種類、それらの固形分の質量比が表１記載のものになるように樹脂層形成用液状物を調製した以外は実施例１と同様の操作を行って、離型シートを得た。
Examples 2-9, Comparative Examples 1-3
Except that the liquid material for forming the resin layer was prepared so that the aqueous dispersion of the acid-modified 4-methyl-1-pentene polymer and the kind of the cross-linking agent and the mass ratio of their solid contents were as shown in Table 1. The same operation as in Example 1 was performed to obtain a release sheet.
実施例１０
ポリエチレンテレフタレート樹脂（日本エステル社製、固有粘度０．６）を、Ｔダイを備えた押出機（７５ｍｍ径、Ｌ／Ｄが４５の緩圧縮タイプ単軸スクリュー）を用いて、シリンダー温度２６０℃、Ｔダイ温度２８０℃でシート状に押出し、表面温度２５℃に調節された冷却ロール状に密着させて急冷し、厚み５００μｍの未延伸フィルムとした。
続いて、未延伸フィルムを９０℃で縦方向に３．４倍延伸した後、グラビアコート機を用いて、実施例２で調製した樹脂層形成用液状物を、乾燥、延伸後の塗布量が０．１ｇ／ｍ２になるように塗布し、次に温度９０℃で２秒間予熱した後、２４０℃で横方向に３．５倍の倍率で延伸し、離型シートを得た。得られた離型シートにおける樹脂層の厚みは、０．１μｍであった。
Example 10
Using a polyethylene terephthalate resin (Nippon Ester Co., Ltd., intrinsic viscosity 0.6), an extruder equipped with a T die (75 mm diameter, L / D 45 slow compression type single screw), a cylinder temperature of 260 ° C., It was extruded into a sheet at a T-die temperature of 280 ° C., brought into close contact with a cooling roll having a surface temperature adjusted to 25 ° C., and rapidly cooled to obtain an unstretched film having a thickness of 500 μm.
Then, after stretching the unstretched film at 90 ° C. in the longitudinal direction by 3.4 times, the resin layer-forming liquid material prepared in Example 2 was dried and stretched with a gravure coater to obtain a coating amount after stretching. It was applied so as to have a concentration of 0.1 g / m 2 , then preheated at a temperature of 90 ° C. for 2 seconds, and then stretched at 240 ° C. in the transverse direction at a magnification of 3.5 times to obtain a release sheet. The thickness of the resin layer in the obtained release sheet was 0.1 μm.
実施例１１、１２
樹脂層形成用液状物を実施例８、９で調製したものに変更した以外は、実施例１０と同様の操作を行って、離型シートを得た。
Examples 11 and 12
A release sheet was obtained by performing the same operations as in Example 10 except that the liquid material for forming a resin layer was changed to those prepared in Examples 8 and 9.
比較例４、５
ポリプロピレンフィルム（ＯＰＰフィルム、東レ社製、トレファン ２５００Ｈ 厚み５０μｍ）、ポリメチルペンテンフィルム（ＰＭＰフィルム、三井化学東セロ社製、オピュラン Ｘ−８８Ｂ 厚み５０μｍ）を、それぞれ樹脂層を形成することなく、離型シートとして評価した。
Comparative Examples 4 and 5
Polypropylene film (OPP film, Toray, Trefan 2500H thickness 50 μm), polymethylpentene film (PMP film, Mitsui Chemicals Tohcello, Opulan X-88B thickness 50 μm) were separated without forming a resin layer. It was evaluated as a mold sheet.
得られた離型シートについて、樹脂層の構成、形成方法、特性を表１に示す。 Table 1 shows the constitution of the resin layer, the forming method, and the properties of the obtained release sheet.
表１に示すように、実施例において得られた離型シートは、基材上に酸変性４−メチル−１−ペンテン系重合体と架橋剤を含有する樹脂層が設けられたものであり、離型シート上で２３０℃の高温条件において硬化させたエポキシ樹脂に対して、良好な離型性を示した。また、高温で熱処理されても寸法安定性に優れるものであった。
なかでも、樹脂層形成用液状物を塗布後に基材とともに延伸した（インラインコート）離型シート（実施例１０〜１２）は、より離型性に優れていた。
一方、樹脂層が架橋剤を含有しない離型シート（比較例１）は、基材と樹脂層の間の密着性が劣っていた。
樹脂層における架橋剤の含有量が本発明で規定する範囲を超える離型シート（比較例２）や、樹脂層を構成する樹脂が、本発明で規定する酸変性４−メチル−１−ペンテン系重合体以外の樹脂である離型シート（比較例３）は、離型性が劣る結果となった。
ポリオレフィン樹脂単体からなる離型シート（比較例４、５）は、離型性や寸法安定性が劣っていた。
As shown in Table 1, the release sheets obtained in the examples are those in which a resin layer containing an acid-modified 4-methyl-1-pentene polymer and a cross-linking agent was provided on a substrate, Good releasability was exhibited for the epoxy resin cured on the release sheet at a high temperature of 230 ° C. Further, it was excellent in dimensional stability even when heat-treated at a high temperature.
Among them, the release sheets (Examples 10 to 12) in which the liquid material for forming the resin layer was applied and then stretched together with the substrate (in-line coating) were more excellent in releasability.
On the other hand, the release sheet in which the resin layer did not contain a crosslinking agent (Comparative Example 1) had poor adhesion between the base material and the resin layer.
The release sheet in which the content of the crosslinking agent in the resin layer exceeds the range specified in the present invention (Comparative Example 2), and the resin constituting the resin layer is an acid-modified 4-methyl-1-pentene-based resin specified in the present invention. The release sheet (Comparative Example 3), which is a resin other than the polymer, resulted in poor releasability.
The release sheets made of the polyolefin resin alone (Comparative Examples 4 and 5) were inferior in releasability and dimensional stability.
Claims (6)
基材に、酸変性４−メチル−１−ペンテン系重合体と架橋剤とを含有する樹脂層形成用液状物を塗布する工程と、乾燥して樹脂層を形成する工程とを有することを特徴とする離型シートの製造方法。 A method for producing the release sheet according to any one of claims 1 to 4, comprising:
It has a step of applying a liquid material for forming a resin layer containing an acid-modified 4-methyl-1-pentene-based polymer and a cross-linking agent to a base material, and a step of forming a resin layer by drying. And a method for manufacturing a release sheet.
酸変性４−メチル−１−ペンテン系重合体と架橋剤とを含有する樹脂層形成用液状物が塗布された基材を乾燥、延伸する工程を含むことを特徴とする離型シートの製造方法。
A method for producing the release sheet according to claim 3 or 4, comprising:
A method for producing a release sheet, comprising the steps of drying and stretching a substrate coated with a resin layer-forming liquid containing an acid-modified 4-methyl-1-pentene polymer and a crosslinking agent. ..
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10101868A (en) * | 1996-09-30 | 1998-04-21 | Mitsui Petrochem Ind Ltd | 4-methyl-1-pentene-based resin composition excellent in adhesive strength to substrate and laminate having the same resin composition layer |
| JP2004082717A (en) * | 2002-06-28 | 2004-03-18 | Mitsui Chemicals Inc | Multi-layer film of 4-methyl-1-pentene type polymer |
| JP2016104539A (en) * | 2014-12-01 | 2016-06-09 | ユニチカ株式会社 | Mold releasing biaxial oriented polyester film |
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2018
- 2018-10-30 JP JP2018203367A patent/JP7208617B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10101868A (en) * | 1996-09-30 | 1998-04-21 | Mitsui Petrochem Ind Ltd | 4-methyl-1-pentene-based resin composition excellent in adhesive strength to substrate and laminate having the same resin composition layer |
| JP2004082717A (en) * | 2002-06-28 | 2004-03-18 | Mitsui Chemicals Inc | Multi-layer film of 4-methyl-1-pentene type polymer |
| JP2016104539A (en) * | 2014-12-01 | 2016-06-09 | ユニチカ株式会社 | Mold releasing biaxial oriented polyester film |
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