JP2023127634A - Ultraviolet-curable silicone release agent composition - Google Patents
Ultraviolet-curable silicone release agent composition Download PDFInfo
- Publication number
- JP2023127634A JP2023127634A JP2022031434A JP2022031434A JP2023127634A JP 2023127634 A JP2023127634 A JP 2023127634A JP 2022031434 A JP2022031434 A JP 2022031434A JP 2022031434 A JP2022031434 A JP 2022031434A JP 2023127634 A JP2023127634 A JP 2023127634A
- Authority
- JP
- Japan
- Prior art keywords
- release agent
- curable silicone
- agent composition
- silicone release
- viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- -1 iodonium iodonium salt compound Chemical class 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 20
- 239000010409 thin film Substances 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- 238000009501 film coating Methods 0.000 description 7
- 239000002985 plastic film Substances 0.000 description 7
- 229920006255 plastic film Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000003566 oxetanyl group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical group [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Epoxy Resins (AREA)
Abstract
Description
低粘度で、良好な薄膜塗工性と実用に耐え得る皮膜強度を両立した紫外線硬化型シリコーン剥離剤組成物に関する。 This invention relates to an ultraviolet curable silicone release agent composition that has low viscosity, has good thin film coating properties, and has film strength that can withstand practical use.
紫外線硬化性組成物は、紫外線を照射した時にラジカルを発生させる開始剤を添加し、そのラジカルを活性種として反応が進行していくタイプと、紫外線を照射した時にカチオン種を発生させる開始剤を添加し、そのカチオン種を活性種として反応が進行していくタイプに大別できる。前者は、（メタ）アクリル基、ビニル基等を有する化合物を重合させることができ、後者はエポキシ基、オキセタニル基、ビニルエーテル基を有する化合物を重合させることができる。
前者は、酸素阻害の影響を受け、表面が硬化せずに、表面タックが残りやすいこと、後者は酸素阻害の影響は受けず、表面が完全硬化し表面タックレスであることは広く知られている。
紫外線硬化型シリコーン組成物としては、この両方で反応が進行する組成物が市販されている。特許文献１は後者で、エポキシ基を含有するシリコーンを重合させている公報である。良好な薄膜塗工性を得るには改善の余地があった。
There are two types of ultraviolet curable compositions: one type contains an initiator that generates radicals when irradiated with ultraviolet rays, and the reaction proceeds using the radicals as active species, and the other type contains an initiator that generates cation species when irradiated with ultraviolet rays. It can be roughly divided into types in which the reaction proceeds with the cation species added as the active species. The former can polymerize compounds having (meth)acrylic groups, vinyl groups, etc., and the latter can polymerize compounds having epoxy groups, oxetanyl groups, vinyl ether groups.
It is widely known that the former is affected by oxygen inhibition and the surface does not harden and surface tack remains easily, whereas the latter is not affected by oxygen inhibition and the surface is completely hardened and surface tackless. .
As ultraviolet curable silicone compositions, compositions in which reactions proceed in both directions are commercially available. Patent Document 1 is the latter, and is a publication in which silicone containing an epoxy group is polymerized. There was room for improvement in obtaining good thin film coating properties.
特許文献２は、基材としてプラスチックフィルムを使用した場合においても、基材に対して優れた溶剤摩擦耐性を有し、任意の剥離性能に調整可能な剥離剤組成物に関する公報である。特許文献２も特許文献１同様、良好な薄膜塗工性を得るには改善の余地があった。
特許文献３は良好な剥離性を有する新規の剥離シートを提供することを目的とする公報であるが、皮膜強度には改善の余地があった。
Patent Document 2 is a publication regarding a release agent composition that has excellent solvent friction resistance against a base material even when a plastic film is used as the base material, and can be adjusted to any desired release performance. Similar to Patent Document 1, Patent Document 2 also has room for improvement in order to obtain good thin film coating properties.
Patent Document 3 is a publication aimed at providing a new release sheet having good peelability, but there is room for improvement in film strength.
特許文献４は、透明性と吸湿性とを兼ね備える有機ＥＬ発光装置用の封止材を作製できる紫外線硬化性組成物、この紫外線硬化性組成物を用いる有機ＥＬ発光装置の製造方法、及び有機ＥＬ発光装置に関する公報である。剥離剤としての検討は行われていなかった。 Patent Document 4 discloses an ultraviolet curable composition that can produce a sealing material for an organic EL light emitting device that has both transparency and hygroscopicity, a method for manufacturing an organic EL light emitting device using this ultraviolet curable composition, and an organic EL light emitting device. This is a publication regarding a light emitting device. It has not been studied as a stripping agent.
低粘度で、良好な薄膜塗工性と実用に耐え得る皮膜強度を両立した紫外線硬化型シリコーン剥離剤組成物を得ることである。 The object of the present invention is to obtain an ultraviolet curable silicone release agent composition that has low viscosity, has good thin film coating properties, and has film strength that can withstand practical use.
２５℃における粘度が１０～１，０００ｍＰａ・ｓであり一分子中に少なくとも２個のカチオン重合性基を有するオルガノポリシロキサン（Ａ）を４０～９５質量部、一般式（１）で表される化合物（Ｂ）を５～６０質量部、光カチオン重合開始剤（Ｃ）を０．５～１０質量部含み、２５℃における粘度が１０～１００ｍＰａ・ｓである紫外線硬化型シリコーン剥離剤組成物である。 40 to 95 parts by mass of organopolysiloxane (A) having a viscosity of 10 to 1,000 mPa·s at 25°C and having at least two cationic polymerizable groups in one molecule, represented by general formula (1) An ultraviolet curable silicone release agent composition containing 5 to 60 parts by mass of the compound (B) and 0.5 to 10 parts by mass of the photocationic polymerization initiator (C) and having a viscosity of 10 to 100 mPa s at 25 ° C. be.
低粘度による良好な薄膜塗工性と実用に耐え得る皮膜強度を両立したカチオン硬化型シリコーン系離型剤組成物、およびこれを用いた剥離紙、セパレータフィルムを提供することができる。 It is possible to provide a cationically curable silicone mold release agent composition that has both good thin film coating properties due to low viscosity and film strength that can withstand practical use, and a release paper and a separator film using the same.
以下、本願の発明に係る、低粘度で、良好な薄膜塗工性と実用に耐え得る皮膜強度を両立した紫外線硬化型シリコーン剥離剤組成物を具体的に説明する。 Hereinafter, the ultraviolet curable silicone release agent composition according to the invention of the present application, which is low in viscosity and has both good thin film coating properties and film strength that can withstand practical use, will be specifically described.
＜２５℃における粘度が１０～１，０００ｍＰａ・ｓであり一分子中に少なくとも２個のカチオン重合性基を有するオルガノポリシロキサン（Ａ）＞
２５℃における粘度が１０～１，０００ｍＰａ・ｓであり一分子中に少なくとも２個のカチオン重合性基を有するオルガノポリシロキサン（Ａ）は、カチオン重合性基を有するシリコーン化合物である。カチオン重合性基としては、エポキシ基、オキセタニル基、ビニルエーテル基等を挙げることができる。より好適なカチオン重合性基は、エポキシ基である。エポキシ基としては、グリシジル基、または３，４－エポキシシクロヘキシル基などのエポキシシクロヘキシル基、３，４－エポキシ－４－メチルシクロヘキシル基などのエポキシメチルシクロヘキシル基等の脂環式エポキシ基等を挙げることができる。
<Organopolysiloxane (A) having a viscosity of 10 to 1,000 mPa·s at 25°C and having at least two cationic polymerizable groups in one molecule>
The organopolysiloxane (A) having a viscosity of 10 to 1,000 mPa·s at 25° C. and having at least two cationically polymerizable groups in one molecule is a silicone compound having a cationically polymerizable group. Examples of the cationically polymerizable group include an epoxy group, an oxetanyl group, and a vinyl ether group. A more preferred cationically polymerizable group is an epoxy group. Examples of the epoxy group include glycidyl groups, epoxycyclohexyl groups such as 3,4-epoxycyclohexyl groups, and alicyclic epoxy groups such as epoxymethylcyclohexyl groups such as 3,4-epoxy-4-methylcyclohexyl groups. Can be done.
反応性の観点からは、脂環式エポキシ基を有するものが好適である。粘度は１０～１，０００ｍＰａ・ｓである方が好ましい。粘度が１０ｍＰａ・ｓを下回った場合、基材上でハジキを生じる可能性がある。１，０００ｍＰａ・ｓを上回った場合、組成物の粘度が高すぎて塗工性が低下する。直鎖構造を主とするカチオン重合性基を有するオイル状のシリコーン化合物が好適である。粘度範囲を満たせば、架橋構造を有していても構わない。オルガノポリシロキサン（Ａ）は、複数種を併用することもできる。 From the viewpoint of reactivity, those having an alicyclic epoxy group are preferred. The viscosity is preferably 10 to 1,000 mPa·s. If the viscosity is less than 10 mPa·s, repellency may occur on the base material. If it exceeds 1,000 mPa·s, the viscosity of the composition will be too high and the coating properties will deteriorate. An oily silicone compound having a cationic polymerizable group mainly having a linear structure is suitable. It may have a crosslinked structure as long as it satisfies the viscosity range. A plurality of organopolysiloxanes (A) can also be used in combination.
２５℃における粘度が１０～１，０００ｍＰａ・ｓであり一分子中に少なくとも２個のカチオン重合性基を有するオルガノポリシロキサン（Ａ）の添加量は、２５℃における粘度が１０～１，０００ｍＰａ・ｓであり一分子中に少なくとも２個のカチオン重合性基を有するオルガノポリシロキサン（Ａ）と一般式（１）で表される化合物（Ｂ）の合計１００質量部に対して、４０～９５質量部、より好適には５０～９３質量部である。 The added amount of organopolysiloxane (A) having a viscosity of 10 to 1,000 mPa·s at 25°C and having at least two cationically polymerizable groups in one molecule is such that the viscosity at 25°C is 10 to 1,000 mPa·s. s and having at least two cationically polymerizable groups in one molecule (A) and a compound (B) represented by the general formula (1) of 40 to 95 parts by mass based on a total of 100 parts by mass. parts, more preferably 50 to 93 parts by weight.
＜一般式（１）で表される化合物（Ｂ）＞
一般式（１）で表される化合物（Ｂ）のうち、Ｒ１はカチオン重合性基を含有する非置換もしくは置換の炭素原子数１～１０の１価炭化水素基であり、Ｒ２は独立にカチオン重合性基を含有しない非置換もしくは置換の炭素原子数１～１０の１価炭化水素基であり、ｎは０～３の整数である。
Ｒ１はカチオン重合時における反応性の観点からビニルエーテル基、オキセタニル基よりもエポキシ基が好適で、エポキシ基の中でも脂環式エポキシ基がより好適である。また、Ｒ２は、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、ｔｅｒｔ－ブチル基、ヘキシル基、オクチル基、２－エチルヘキシル基、シクロヘキシル基、フェニル基、トリル基などや水素原子の一部または全部をヒドロキシ基、アノ基、ハロゲン原子などで置換した基などが挙げられるが、メチル基あるいはフェニル基がより好適である。
一般式（１）で表される化合物（Ｂ）は、組成物を低粘度化し、かつ皮膜強度を向上させる成分である。一般式（１）で表される化合物（Ｂ）添加量は、２５℃における粘度が１０～１，０００ｍＰａ・ｓであり一分子中に少なくとも２個のカチオン重合性基を有するオルガノポリシロキサン（Ａ）と一般式（１）で表される化合物（Ｂ）の合計１００質量部に対して、５～６０質量部、より好適には７～５５質量部である。添加量が５質量部を下回ると組成物の十分低粘度化効果が得られず、硬化物も十分な皮膜強度とを得ることができない。６０質量部を上回ると、硬化物の剥離強度が低下し剥離剤としての性能が低下してしまう。
<Compound (B) represented by general formula (1)>
In the compound (B) represented by the general formula (1), R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms containing a cationically polymerizable group, and R 2 is an independent is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms that does not contain a cationically polymerizable group, and n is an integer of 0 to 3.
From the viewpoint of reactivity during cationic polymerization, R 1 is preferably an epoxy group rather than a vinyl ether group or an oxetanyl group, and among the epoxy groups, an alicyclic epoxy group is more preferable. Furthermore, R 2 is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a cyclohexyl group, a phenyl group, a tolyl group, etc. Examples include groups in which part or all of the hydrogen atoms are substituted with a hydroxy group, an ano group, a halogen atom, etc., and a methyl group or a phenyl group is more preferred.
The compound (B) represented by the general formula (1) is a component that lowers the viscosity of the composition and improves the film strength. The amount of compound (B) represented by general formula (1) to be added is an organopolysiloxane (A ) and the compound (B) represented by the general formula (1), 5 to 60 parts by weight, more preferably 7 to 55 parts by weight, based on a total of 100 parts by weight. If the amount added is less than 5 parts by mass, the composition will not have a sufficiently low viscosity effect, and the cured product will not have sufficient film strength. If it exceeds 60 parts by mass, the peel strength of the cured product will decrease and the performance as a release agent will decrease.
一般式（１）で表される化合物（Ｂ）の中でも、より好適な材料としては、一般式（２）で表される化合物が挙げられる。尚Ｘ１、Ｘ２は、いずれも炭素数１～５であらわされるアルキレン基である。 Among the compounds (B) represented by general formula (1), more preferable materials include compounds represented by general formula (2). Note that X 1 and X 2 are both alkylene groups having 1 to 5 carbon atoms.
＜光カチオン重合開始剤（Ｃ）＞
光カチオン重合開始剤（Ｃ）は、組成物を硬化させるための光開始剤である。紫外線照射によりカチオン種を発生できるオニウム塩系光開始剤が好適である。組成物への相溶性、硬化性から、カチオンとしてジビス［４－アルキルフェニル］ヨードニウム構造を持ち、アニオンとしてＳｂＦ６－、ＰＦ６－、ＢＦ４－、Ｂ（Ｃ６Ｆ５）４－といった構造を持つものが好適である。光カチオン重合開始剤（Ｃ）の添加量としては、２５℃における粘度が１０～１，０００ｍＰａ・ｓであり一分子中に少なくとも２個のカチオン重合性基を有するオルガノポリシロキサン（Ａ）と一般式（１）で表される化合物（Ｂ）の合計１００質量部に対して、０．１～１０質量部、より好適には０．５～５質量部である。０．１質量部より少ないと硬化が不十分、１０質量部より多いと硬化皮膜の表面状態に悪影響が生じて、剥離特性が悪くなる。
<Photocationic polymerization initiator (C)>
The photocationic polymerization initiator (C) is a photoinitiator for curing the composition. Onium salt photoinitiators that can generate cationic species upon irradiation with ultraviolet light are preferred. From the viewpoint of compatibility with the composition and curability, the cation has a dibis[4-alkylphenyl]iodonium structure, and the anion has a structure such as SbF 6- , PF 6- , BF 4- , B(C 6 F 5 ) 4- . Preferably, those with The amount of the cationic photopolymerization initiator (C) to be added is based on organopolysiloxanes (A) having a viscosity of 10 to 1,000 mPa·s at 25°C and having at least two cationic polymerizable groups in one molecule, and general The amount is 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on a total of 100 parts by weight of the compound (B) represented by formula (1). If it is less than 0.1 part by mass, curing will be insufficient, and if it is more than 10 parts by mass, the surface condition of the cured film will be adversely affected and the peeling characteristics will deteriorate.
本願の紫外線硬化型シリコーン剥離剤組成物の２５℃における適正粘度は、１０～１００ｍＰａ・ｓであり、より好適には２０～９０ｍＰａ・ｓである。１００ｍＰａ・ｓを上回ると、良好な薄膜塗工性が得られず、１０ｍＰａ・ｓを下回ると、硬化性が低下する。 The appropriate viscosity at 25° C. of the ultraviolet curable silicone release agent composition of the present application is 10 to 100 mPa·s, more preferably 20 to 90 mPa·s. When it exceeds 100 mPa·s, good thin film coating properties cannot be obtained, and when it falls below 10 mPa·s, curability decreases.
本願の紫外線硬化型シリコーン剥離剤組成物は、プラスチックフィルム等に塗布され、紫外線を照射し硬化させて、セパレータフィルムとして用いられる場合がある。
基材と成るプラスチックフィルムの材質としては、汎用品ではポリエチレンテレフタレート（ＰＥＴ）等のポリエステル類、ポリエチレン、ポリプロピレン、ナイロン、用途によってはポリエチレンナフタレート、液晶ポリマー、ポリフェニレンサルファイド、ポリエーテルエーテルケトン、ポリイミド、ポリエーテルイミド等が用いられる場合もある。
これらプラスチックフィルムと、紫外線硬化型シリコーン剥離剤組成物の密着性を向上させるために、プライマー処理、コロナ処理、エッチング処理、プラズマ処理などがされたプラスチックフィルムなどのシート状基材を用いてもよい。
The ultraviolet curable silicone release agent composition of the present application may be applied to a plastic film or the like, cured by irradiation with ultraviolet rays, and used as a separator film.
The material of the base plastic film is polyester such as polyethylene terephthalate (PET), polyethylene, polypropylene, nylon for general purpose products, polyethylene naphthalate, liquid crystal polymer, polyphenylene sulfide, polyether ether ketone, polyimide, etc. depending on the purpose. Polyetherimide or the like may also be used.
In order to improve the adhesion between these plastic films and the UV-curable silicone release agent composition, a sheet-like base material such as a plastic film that has been subjected to primer treatment, corona treatment, etching treatment, plasma treatment, etc. may be used. .
基材のプラスチックフィルムに対する紫外線硬化型シリコーン剥離剤組成物の塗布方法としては、ロール塗布、グラビア塗布、ワイヤードクター塗布、エアーナイフ塗布、ディッピング塗布などの公知の方法を用いることができる。塗布量としては ０．０１～１００ ｇ／ｍ２、より好適には０．０５～５０ｇ／ｍ２である。
紫外線硬化型シリコーン剥離剤組成物を塗布したプラスチックフィルムに、紫外線を照射すると、容易に硬化させることができる。紫外線の光源としては、高圧水銀ランプ、中圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、水銀アーク灯などを用いることができる。
As a method for applying the ultraviolet curable silicone release agent composition to the plastic film of the base material, known methods such as roll coating, gravure coating, wire doctor coating, air knife coating, and dipping coating can be used. The coating amount is 0.01 to 100 g/m 2 , more preferably 0.05 to 50 g/m 2 .
When a plastic film coated with an ultraviolet curable silicone release agent composition is irradiated with ultraviolet rays, it can be easily cured. As the ultraviolet light source, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a mercury arc lamp, etc. can be used.
次に、本願の紫外線硬化型シリコーン剥離剤組成物について、実施例及び比較例により詳細に説明する。 Next, the ultraviolet curable silicone release agent composition of the present application will be described in detail with reference to Examples and Comparative Examples.
＜粘度測定＞
実施例、比較例で用いるシリコーン材料、および実施例１～４、比較例１～５の紫外線硬化型シリコーン剥離剤組成物の２３℃における粘度を、Ｂ形粘度計(東機産業ＴＶＢ－２５Ｍ)にて測定した。
紫外線硬化型シリコーン剥離剤組成物の判定基準としては、粘度が１０～１００ｍＰａ・ｓの範囲であれば合格、それ以外は不合格とした。結果を表３、表４に示す。
<Viscosity measurement>
The viscosity at 23°C of the silicone materials used in Examples and Comparative Examples and the ultraviolet curable silicone release agent compositions of Examples 1 to 4 and Comparative Examples 1 to 5 was measured using a B-type viscometer (Toki Sangyo TVB-25M). Measured at
The criteria for determining the ultraviolet curable silicone release agent composition was that it passed if the viscosity was in the range of 10 to 100 mPa·s, and otherwise it was judged to be rejected. The results are shown in Tables 3 and 4.
＜セパレータフィルムの作製＞
紫外線硬化型シリコーン剥離剤組成物をＰＥＴフィルム（東レ社製、製品名：ルミラー７５Ｕ４８３）に 約０．５ｇ／ｍ２となるように塗布し、高圧水銀灯を用い８０ｍＪ／ｃｍ２の照射量の紫外線を照射し、セパレータフィルムを作製した。
<Preparation of separator film>
An ultraviolet curable silicone release agent composition was applied to a PET film (manufactured by Toray Industries, Inc., product name: Lumirror 75U483) at an amount of about 0.5 g/m 2 , and then exposed to ultraviolet light at a dose of 80 mJ/cm 2 using a high-pressure mercury lamp. was irradiated to produce a separator film.
＜剥離力＞
セパレータフィルムの作製にて作製したセパレータフィルムの紫外線硬化型シリコーン剥離剤組成物硬化物面に、粘着テープ（商品名ニットー３１Ｂテープ日東電工製）を貼り付け２ｋｇロールで一往復圧着した。粘着テープの剥離力は、室温２３℃、湿度５０％の条件において、粘着テープを１８０度の方向に０．３ｍ／ｍｉｎの速度で引き剥がして求めた。判定基準としては、１０～２００ｍＮ／２５ｍｍが合格である。結果を表３、表４に示す。
<Peeling force>
Adhesive tape (trade name: Nitto 31B Tape, manufactured by Nitto Denko) was applied to the cured surface of the ultraviolet curable silicone release agent composition of the separator film prepared in the preparation of the separator film, and pressed back and forth once with a 2 kg roll. The peeling force of the adhesive tape was determined by peeling off the adhesive tape in a direction of 180 degrees at a speed of 0.3 m/min at a room temperature of 23° C. and a humidity of 50%. As a criterion, 10 to 200 mN/25 mm is acceptable. The results are shown in Tables 3 and 4.
＜皮膜強度＞
セパレータフィルムの作製にて作製したセパレータフィルムの紫外線硬化型シリコーン剥離剤組成物硬化物面を、指で１０回擦り、曇り（スミア）および剥離剤層の脱落（ラブオフ）の有無を目視にて確認した。そして、以下の判断基準により、剥離剤層の皮膜強度を評価した。
判定基準としては、スミアおよびラブオフの両方とも確認されなかった場合は合格（：〇）、スミアおよびラブオフの少なくとも一方が確認された場合は不合格（：×）とした。結果を表３、表４に示す。
<Film strength>
Rub the cured surface of the ultraviolet curable silicone release agent composition of the separator film prepared in the separator film production process with your fingers 10 times, and visually check for cloudiness (smear) and peeling off of the release agent layer (rub-off). did. Then, the film strength of the release agent layer was evaluated according to the following criteria.
As for the judgment criteria, if neither smear or rub-off was observed, the test was passed (:○), and when at least one of smear and rub-off was confirmed, the test was judged as fail (:×). The results are shown in Tables 3 and 4.
＜実施例１の紫外線硬化型シリコーン剥離剤組成物の作製＞
ＥｐＭｅ２ＳｉＯ１／２単位、Ｍｅ２ＳｉＯ２／２単位からなり２５℃で４７ｍＰａ・ｓの粘度を示すオイル状のポリシロキサン（ａ－１）を９０ｇ、下記式（４）で示される化合物（ｂ－１）を１０ｇ、均一になるまで攪拌した。その混合液に光カチオン重合開始剤（Ｃ）として、炭酸プロピレンに５０質量％溶解させたビス－［４－ｎアルキル（Ｃ１０～Ｃ１３）フェニル］ヨードニウムテトラキスペンタフルオロフェニルホウ酸溶液２ｇを均一になるまで攪拌混合し、実施例１の紫外線硬化型シリコーン剥離剤組成物を得た。
尚、Ｅｐは下記式（３）の構造であり、Ｍｅはメチル基を表す。
・・・（３）
・・・（４）
<Preparation of ultraviolet curable silicone release agent composition of Example 1>
90 g of oily polysiloxane (a-1), which is composed of EpMe 2 SiO 1/2 units and Me 2 SiO 2/2 units and has a viscosity of 47 mPa·s at 25°C, and a compound represented by the following formula (4) ( 10g of b-1) was stirred until homogeneous. Add 2 g of bis-[4-n alkyl (C10-C13) phenyl]iodonium tetrakis pentafluorophenyl boric acid solution dissolved in propylene carbonate at 50% by mass as a photocationic polymerization initiator (C) to the mixed solution until it becomes uniform. The UV-curable silicone release agent composition of Example 1 was obtained.
In addition, Ep has the structure of the following formula (3), and Me represents a methyl group.
...(3)
...(4)
＜実施例２、３、比較例１、３の紫外線硬化型シリコーン剥離剤組成物の作製＞
実施例１における（ａ－１）、（ｂ－１）を表１、表２に示す添加量に変更したこと以外は実施例１と同様にして、実施例２、３、比較例１、２、３の紫外線硬化型シリコーン剥離剤組成物を作製した。
<Preparation of ultraviolet curable silicone release agent compositions of Examples 2 and 3 and Comparative Examples 1 and 3>
Examples 2 and 3 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 except that (a-1) and (b-1) in Example 1 were changed to the amounts shown in Tables 1 and 2. An ultraviolet curable silicone release agent composition of No. 3 was prepared.
＜実施例４、比較例２の紫外線硬化型シリコーン剥離剤組成物の作製＞
実施例１における（ａ－１）成分をＭｅ３ＳｉＯ１／２単位、ＥｐＭｅＳｉＯ２／２単位、Ｍｅ２ＳｉＯ２／２単位からなり２５℃で１００ｍＰａ・ｓの粘度を示すオイル状のポリシロキサン（ａ－２）に変更し、表１に記載した添加量としたこと以外は同様にして実施例４、比較例２の紫外線硬化型シリコーン剥離剤組成物を作製した。
<Preparation of UV-curable silicone release agent compositions of Example 4 and Comparative Example 2>
Component (a-1) in Example 1 was replaced with an oil-like polysiloxane consisting of Me 3 SiO 1/2 units, EpMeSiO 2/2 units, and Me 2 SiO 2/2 units and exhibiting a viscosity of 100 mPa·s at 25°C. Ultraviolet curable silicone release agent compositions of Example 4 and Comparative Example 2 were prepared in the same manner except that a-2) was changed and the amount added was as shown in Table 1.
＜比較例４の紫外線硬化型シリコーン剥離剤組成物の作製＞
実施例1における（ｂ－１）成分を、ケイ素原子を含有しないエポキシ化合物である下記式（５）の成分（ｂ－２）に変更し、表1に記載した添加量としたこと以外は同様にして比較例４の紫外線硬化型シリコーン剥離剤組成物を作製した。尚、比較例４の組成物は相溶せずに２層に分離したので、粘度測定、剥離力、皮膜強度の評価は行っていない。
・・・（５）
<Preparation of ultraviolet curable silicone release agent composition of Comparative Example 4>
Same as Example 1 except that component (b-1) in Example 1 was changed to component (b-2) of the following formula (5), which is an epoxy compound containing no silicon atom, and the amount added was as shown in Table 1. An ultraviolet curable silicone release agent composition of Comparative Example 4 was prepared. In addition, since the composition of Comparative Example 4 was separated into two layers without being compatible with each other, viscosity measurement, peeling force, and film strength were not evaluated.
...(5)
＜比較例５の紫外線硬化型シリコーン剥離剤組成物の作製＞
実施例1における（ｂ－１）成分を、ケイ素原子を含有しないエポキシ化合物である式（６）の成分（ｂ－３）に変更し、表1に記載した添加量としたこと以外は同様にして比較例５の紫外線硬化型シリコーン剥離剤組成物を作製した。
・・・（６）
<Preparation of ultraviolet curable silicone release agent composition of Comparative Example 5>
The same procedure was followed except that component (b-1) in Example 1 was changed to component (b-3) of formula (6), which is an epoxy compound containing no silicon atom, and the amount added was set as shown in Table 1. An ultraviolet curable silicone release agent composition of Comparative Example 5 was prepared.
...(6)
Claims (5)
下記一般式（１）で表される化合物（Ｂ）を５～６０質量部、
・・・（１）
（Ｒ１はカチオン重合性基を含有する非置換もしくは置換の炭素原子数１～１０の１価炭化水素基であり、
Ｒ２は独立にカチオン重合性基を含有しない非置換もしくは置換の炭素原子数１～１０の１価炭化水素基であり、ｎは０～３の整数である。）
光カチオン重合開始剤（Ｃ）を０．５～１０質量部含み、
２５℃における粘度が１０～１００ｍＰａ・ｓである紫外線硬化型シリコーン剥離剤組成物。 40 to 95 parts by mass of organopolysiloxane (A) having a viscosity at 25 ° C. of 10 to 1,000 mPa s and having at least two cationic polymerizable groups in one molecule,
5 to 60 parts by mass of the compound (B) represented by the following general formula (1),
...(1)
(R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms containing a cationic polymerizable group,
R 2 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms that does not contain a cationic polymerizable group, and n is an integer of 0 to 3. )
Contains 0.5 to 10 parts by mass of a photocationic polymerization initiator (C),
An ultraviolet curable silicone release agent composition having a viscosity of 10 to 100 mPa·s at 25°C.
一般式（１）で表される化合物（Ｂ）が、下記一般式（２）で表される化合物である請求項１に記載の紫外線硬化型シリコーン剥離剤組成物。
・・・（２）
（Ｘ１、Ｘ２はいずれも炭素数１～５であらわされるアルキレン基である。） The cationic polymerizable group of the organopolysiloxane (A) having a viscosity at 25° C. of 10 to 1,000 mPa·s and at least two cationically polymerizable groups in one molecule is an epoxy group,
The ultraviolet curable silicone release agent composition according to claim 1, wherein the compound (B) represented by the general formula (1) is a compound represented by the following general formula (2).
...(2)
(X 1 and X 2 are both alkylene groups having 1 to 5 carbon atoms.)
一般式（２）で表される化合物のＸ１、Ｘ２がエチレン基であり、
光カチオン重合開始剤（Ｃ）が、ビス－［４－アルキルフェニル］ヨードニウムヨードニウム塩化合物である請求項２に記載の紫外線硬化型シリコーン剥離剤組成物。 The cationic polymerizable group of the organopolysiloxane (A) having a viscosity at 25° C. of 10 to 1,000 mPa·s and at least two cationically polymerizable groups in one molecule is an alicyclic epoxy group,
X 1 and X 2 of the compound represented by general formula (2) are ethylene groups,
The ultraviolet curable silicone release agent composition according to claim 2, wherein the photocationic polymerization initiator (C) is a bis-[4-alkylphenyl]iodonium iodonium salt compound.
A separator produced using the ultraviolet curable silicone release agent composition according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022031434A JP2023127634A (en) | 2022-03-02 | 2022-03-02 | Ultraviolet-curable silicone release agent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022031434A JP2023127634A (en) | 2022-03-02 | 2022-03-02 | Ultraviolet-curable silicone release agent composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2023127634A true JP2023127634A (en) | 2023-09-14 |
Family
ID=87972795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022031434A Pending JP2023127634A (en) | 2022-03-02 | 2022-03-02 | Ultraviolet-curable silicone release agent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2023127634A (en) |
-
2022
- 2022-03-02 JP JP2022031434A patent/JP2023127634A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0608273B1 (en) | Uv-curable silicone release compositions | |
| TWI421307B (en) | Ultraviolet-curable silicone composition | |
| JP4022292B2 (en) | Premium release photocurable silicone composition | |
| TWI431068B (en) | Low viscosity ultraviolet hardening type silicone oxygen composition for release paper | |
| WO1993020163A1 (en) | Silicone release compositions | |
| JP5494417B2 (en) | Radiation curable silicone composition | |
| US5364888A (en) | UV light-curable epoxy-functional organopolysiloxane/polyether composition release | |
| AU672213B2 (en) | Rapidly curable vinyl ether release coatings | |
| JP7202253B2 (en) | Radiation-curable organopolysiloxane composition and release sheet | |
| JP3661743B2 (en) | Method for producing epoxy group-containing organopolysiloxane and ultraviolet curable composition | |
| JP2023127634A (en) | Ultraviolet-curable silicone release agent composition | |
| JP2006291121A (en) | Mold releasing agent and method for coating the same | |
| JP3735857B2 (en) | Release substrate | |
| JP2000044688A (en) | Acrylic functional organopolysiloxane and radioactive ray-curable composition | |
| JP5201358B2 (en) | Cationic polymerizable UV curable silicone composition and release substrate | |
| JP2001348482A (en) | Radiation-curable silicone-containing releasable composition and release film | |
| JP7107303B2 (en) | Releaseable radiation-curable silicone composition and release sheet | |
| JP3177410B2 (en) | Radiation-curable organopolysiloxane composition | |
| JPH07331175A (en) | Ultraviolet-curing coating composition | |
| JPH0774326B2 (en) | UV curable silicone release agent | |
| JP2788933B2 (en) | UV-curable silicone release agent, adhesive member and separator | |
| JP2005120311A (en) | Hardenable separating agent and separator using it | |
| JP2892290B2 (en) | UV curable protective coating composition | |
| JPH0319266B2 (en) | ||
| JPH07316517A (en) | Electron ray curing release agent composition |