JPH03190951A - Composition comprising fluorosilicone polymer and fluoroacrylate polymer - Google Patents
Composition comprising fluorosilicone polymer and fluoroacrylate polymerInfo
- Publication number
- JPH03190951A JPH03190951A JP32733789A JP32733789A JPH03190951A JP H03190951 A JPH03190951 A JP H03190951A JP 32733789 A JP32733789 A JP 32733789A JP 32733789 A JP32733789 A JP 32733789A JP H03190951 A JPH03190951 A JP H03190951A
- Authority
- JP
- Japan
- Prior art keywords
- fluorosilicone
- polymer
- copolymer
- fluoroacrylate
- group
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000005395 methacrylic acid group Chemical group 0.000 claims abstract description 8
- 229920001519 homopolymer Polymers 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims 1
- 239000006082 mold release agent Substances 0.000 abstract description 9
- 239000005871 repellent Substances 0.000 abstract description 8
- 230000002940 repellent Effects 0.000 abstract description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- -1 lisLcla Chemical compound 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- FKTXDTWDCPTPHK-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)[C](F)C(F)(F)F FKTXDTWDCPTPHK-UHFFFAOYSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- PZGMUSDNQDCNAG-UHFFFAOYSA-N 2-Propenyl octanoate Chemical compound CCCCCCCC(=O)OCC=C PZGMUSDNQDCNAG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 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
- 229920005549 butyl rubber Polymers 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 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
- 150000002576 ketones Chemical class 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はフルオロシリコーン重合体とフルオロアクリレ
ート重合体からなる組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a composition comprising a fluorosilicone polymer and a fluoroacrylate polymer.
「従来の技術］
従来、撥水撥油剤や離型剤に例示されるような種々の用
途に、フルオロシリコーン重合体やフルオロアクリレー
ト重合体が各々単独で使用されることはあったが、これ
らを組み合わせて使用することは稀であった。“Prior Art” In the past, fluorosilicone polymers and fluoroacrylate polymers have been used individually for various purposes such as water and oil repellents and mold release agents. They were rarely used in combination.
特開昭６３−７５０８２号公報にはパーフルオロアルキ
ル基もしくはパーフルオロアルケニル基及びアクリル酸
基もしくはメタクリル酸基を有する重合性化合物にシリ
コーン油、シリコーン化合物を加え、エアゾル型組成物
として使用することが提案されている。しかし、このも
のは撥水撥油性に乏しいシリコーン化合物を使用してい
るために、撥水撥油剤として使用した場合、十分な性能
を発揮することができなかった。JP-A-63-75082 discloses that silicone oil and a silicone compound can be added to a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group and used as an aerosol type composition. Proposed. However, since this product uses a silicone compound with poor water and oil repellency, it was unable to exhibit sufficient performance when used as a water and oil repellent.
特開昭６４−３６６７４号公報にはフルオロシリコーン
重合体とフルオロアクリレート重合体を組み合わせて、
撥水撥油剤として使用することが提案されているが、こ
のものはフルオロシリコーン重合体中の弗素含有量が少
量なために、撥水撥油性能が不十分である。また、フル
オロシリコーン重合体どしては、直鎖のオイルにのみ限
定されており、離型剤として使用した場合、基材へのオ
イル分の移行が観察される欠点があった。JP-A No. 64-36674 discloses a combination of a fluorosilicone polymer and a fluoroacrylate polymer,
Although it has been proposed to be used as a water and oil repellent, this product has insufficient water and oil repellency because the fluorine content in the fluorosilicone polymer is small. Further, fluorosilicone polymers are limited to linear oils only, and when used as a mold release agent, there is a drawback that migration of oil components to the base material is observed.
［発明が解決しようとする課題］
本発明は、フルオロシリコーン重合体とフルオロアクリ
レート重合体を組み合わせて使用することにより、それ
ぞれが単独で使用されていた際の問題点を解決しようと
するものである。[Problems to be Solved by the Invention] The present invention attempts to solve the problems that would occur when each was used alone by using a fluorosilicone polymer and a fluoroacrylate polymer in combination. .
本発明は、前述の問題点を解決すべくなされたものであ
り、式（Ａ）で示されるフルオロシリコーンオイル及び
（Ｂ）で示されるフルオロシリコーン共重合体からなる
フルオロシリコーン重合体と
ｆ
［式中、Ｒ１は炭素数１〜２１のパーフルオロアルキル
基、ｍ、ｎはｎ／ｎ＋ｍ≧０．］を満足する整数］
（（：Ｒ３）ｎｓ１０４−ｎｚ２
（Ｒ’、）□（ＣＨａ） ＳｉＯ＋４−＋ｍ＋＋＋＋ｚ
□、又はＳｉＯ□の少なくとも２種からなる共重合体・
・・・・・・・・（Ｂ）
［式中、Ｒｌ、は炭素数１〜２１のパーフルオロアルキ
ル基、ｎ 、ｍ 、Ｑは１≦ｎ≦３，１≦ｍ＋Ｑ≦３を
満足する整数］
パーフルオロアルキル基及びアクリル酸基もしくはメタ
クリル酸基を有する重合性化合物の少な（とも１種のホ
モ重合体もしくは共重合体または前記重合性化合物の少
なくとも１種と共重合可能な重合性化合物との共重合体
からなるフルオロアクリレート重合体を含有することを
特徴とするフルオロシリコーン重合体とフルオロアクリ
レート重合体からなる組成物とパーフルオロアルキル基
及びアクリル酸基もしくはメタクリル酸基を有する重合
性化合物の少な（とも１種のホモ重合体もしくは共重合
体又は前記重合性化合物の少な（とも１種と共重合可能
な重合性化合物との共重合体からなるフルオロアクリレ
ート重合体と式（Ｂ）で示されるフルオロシリコーン共
重合体を含有することを特徴とするフルオロシリコーン
重合体とフルオロアクリレート重合体からなる組成物を
提供するものである。The present invention has been made to solve the above-mentioned problems, and includes a fluorosilicone polymer consisting of a fluorosilicone oil represented by formula (A) and a fluorosilicone copolymer represented by (B), and f [formula In the formula, R1 is a perfluoroalkyl group having 1 to 21 carbon atoms, and m and n are n/n+m≧0. ] ((:R3)ns104-nz2 (R',)□(CHa) SiO+4-+m++++z
□, or a copolymer consisting of at least two types of SiO□.
・・・・・・・・・(B) [In the formula, Rl is a perfluoroalkyl group having 1 to 21 carbon atoms, and n, m, and Q are integers satisfying 1≦n≦3, 1≦m+Q≦3 ] A small amount of a polymerizable compound having a perfluoroalkyl group and an acrylic acid group or a methacrylic acid group (both one type of homopolymer or copolymer or a polymerizable compound copolymerizable with at least one of the above polymerizable compounds) A composition comprising a fluorosilicone polymer and a fluoroacrylate polymer characterized by containing a fluoroacrylate polymer comprising a copolymer of A fluoroacrylate polymer consisting of a homopolymer or copolymer of one type of polymerizable compound or a copolymer of a polymerizable compound copolymerizable with one type of the polymerizable compound and a fluoroacrylate polymer represented by formula (B). A composition comprising a fluorosilicone polymer and a fluoroacrylate polymer is provided.
（ＣＨ３）ｎ５ｉ０４−＋＋ｚ。(CH3)n5i04-++z.
（Ｒ’ｒ）□（ＣＨ３） 、５ｉＯ（＋−１□１０／２
．又はＳｉＯ□の少なくとも２種からなる共重合体・・
・・・・・・・（Ｂ）
［式中、Ｒ１，は炭素数１〜２１のパーフルオロアルキ
ル基、ｎ 、ｍ 、Ｑは１≦ｎ≦３１≦ｍ＋Ｑ≦３を満
足する整数］
本発明で用いられるフルオロシリコーンオイルは、下記
式（Ａ）で示される直鎖状のポリオルガノシロキサンで
あり、これは
ＲＦＣ２Ｈ４（ＣＨ３）ＳｉＣ１２、（ＣＨ３）２５ｉ
Ｃ１２の共加水分解物を、分子量調整剤としての
（ＣＨａ）ｘｓｉＯ３ｉ（ＣＨ３）３存在下に、トリフ
ルオロメタンスルホン酸や硫酸のような酸性触媒や、水
酸化ナトリウム、水酸化カリウムのようなアルカリ触媒
により、縮合重合する方法、あるいは（ＣＨ３１−３ｉ
Ｏ３ｉ（Ｃ；Ｒ３１３存在下に［ＲｆＣ２）１４（ＣＨ
３）Ｓｊ、ＯＪつ、 ［（ＣＨ３）２５ｉＯ］ｙ、［式
中Ｘ＋ｙは３か６５の整数］をトリフルオロメタンスル
ボン酸のような酸性触媒により開環重合する方法等によ
り得ることができる。またｎ、ｍはｎ／ｎ＋ｍ≧０．１
であることが望ましく、ＲｆＣ２Ｈ，（ｆｌ：Ｒ３）Ｓ
ｉＯの含量がこれ以下では、弗素の好ましい効果は発現
しない。(R'r)□(CH3), 5iO(+-1□10/2
．． Or a copolymer consisting of at least two types of SiO□...
......(B) [In the formula, R1 is a perfluoroalkyl group having 1 to 21 carbon atoms, and n, m, and Q are integers satisfying 1≦n≦31≦m+Q≦3] This invention The fluorosilicone oil used in
The C12 cohydrolyzate is treated with an acidic catalyst such as trifluoromethanesulfonic acid or sulfuric acid or an alkaline catalyst such as sodium hydroxide or potassium hydroxide in the presence of (CHa)xsiO3i(CH3)3 as a molecular weight regulator. method of condensation polymerization, or (CH31-3i
[RfC2)14(CH
3) Sj, OJ, [(CH3)25iO]y, [wherein X+y is an integer of 3 or 65] can be obtained by ring-opening polymerization using an acidic catalyst such as trifluoromethanesulfonic acid. Also, n and m are n/n+m≧0.1
It is desirable that RfC2H, (fl:R3)S
If the iO content is less than this, the favorable effects of fluorine will not be exhibited.
ｔ
［式中、Ｒｒは炭素数１〜２１のパーフルオロアルキル
基、ｍ、ｎ はｎ／ｎ＋ｍ≧０．１を満足する０以上
の整数］
式（Ｂ）で表わされる、フルオロシリコーン共重合体は
（Ｃ：Ｈ，）３ＳｊＣ１、（ＣＨ３）２５ｉＣ１□、
Ｃ）ｌｉｓＬｃｌａ等のメチルクロロシラン、（Ｒｌ
ｒ）３ｓｉｃｌ 。t [wherein Rr is a perfluoroalkyl group having 1 to 21 carbon atoms, m and n are integers of 0 or more satisfying n/n+m≧0.1] Fluorosilicone copolymer represented by formula (B) is (C:H,)3SjC1, (CH3)25iC1□,
C) Methylchlorosilane, such as lisLcla, (Rl
r) 3sicl.
（Ｒ’ｄ（ＣＨ３）ＳｉＣ１２，（Ｒ’ｄＳｉＣ１：＋
等のＲ１，基含有クロロシラン又はＳＩ（ＯＭｅ）４，
５ｉ（ＯＥｔ）４，５ｉＣ１４等のシリケート類の少な
くとも２種の共加水分解物を、水酸化ナトリウム等のア
ルカリ触媒により縮合することにより得ることができる
。フルオロシリコーンオイルとフルオロシリコーン共重
合体との混合割合は、前者対後者の重量比が、９５１５
〜６０／４０、好ましくは９０／１０〜７０／３０であ
る。(R'd(CH3)SiC12, (R'dSiC1:+
R1, group-containing chlorosilane or SI(OMe)4,
It can be obtained by condensing at least two co-hydrolysates of silicates such as 5i(OEt)4, 5iC14, etc. using an alkali catalyst such as sodium hydroxide. The mixing ratio of the fluorosilicone oil and the fluorosilicone copolymer is such that the weight ratio of the former to the latter is 9515.
-60/40, preferably 90/10 - 70/30.
（ＣＩ（３）ｎｓｉｏ４−ｎｚ２＋
（Ｒ’ ｆ） −（ＣＨ−） ｅ Ｓ １０ ＋ ４−
ｔ−１ｌｌｌ／２ ＋又はＳｉＯ□の少な（とも２種
からなる共重合体・・・・・・・・・（Ｂ）
［式中、Ｒ１，は炭素数１〜２１のパーフルオロアルキ
ル基、ｎ 、ｍ 、Ｑは １≦ｎ≦３，１≦ｍ＋Ｑ≦３
を満足する整数］
フルオロシリコーン共重合体中の各共重合モノマーの割
合は、各々 ０〜９０ ｗｔ％の広い範囲で変更可能で
ある。(CI(3)nsio4-nz2+ (R' f) -(CH-) e S 10 + 4-
t-1lll/2 + or low in SiO n, m, and Q are 1≦n≦3, 1≦m+Q≦3
[an integer satisfying]] The proportion of each copolymerizable monomer in the fluorosilicone copolymer can be varied within a wide range of 0 to 90 wt%.
本発明で用いられるフルオロアクリレート重合体は、パ
ーフルオロアルキル基及びアクリル酸基もしくはメタク
リル酸基を有する重合性化合物の少なくとも１種のホモ
重合体もしくは共重合体または前記重合性化合物の少な
（とも１種と共重合可能な重合性化合物との前者対後者
の重量比が９５１５〜５／９５、好ましくは８０／２０
〜２０／ ８０である共重合体からなる重合体であり、
パーフルオロアルキル基及びアクリル酸基もしくはメタ
クリル酸基を有する重合性化合物の例として
式
％式％（２）
（３）
（４）
（５）
（６）
［式中、Ｒ２，は炭素数１〜２１のパーフルオロアルキ
ル基またはパーフルオロアルケニル基、Ｒ１は水素また
は炭素数１〜１０のアルキル基、Ｒ２は炭素数１〜１０
のアルキレン基、Ｒ３は水素またはメチル基、Ａｒは置
換基を有することもあるアリーレン基、ｎは１〜１０の
整数を表わすコで示される化合物を挙げることができる
。The fluoroacrylate polymer used in the present invention is a homopolymer or copolymer of at least one polymerizable compound having a perfluoroalkyl group and an acrylic acid group or a methacrylic acid group, or a small amount (or a copolymer of at least one polymerizable compound) of the polymerizable compound having a perfluoroalkyl group and an acrylic acid group or a methacrylic acid group. The weight ratio of the former to the latter of the species and the copolymerizable polymerizable compound is 9515 to 5/95, preferably 80/20.
It is a polymer consisting of a copolymer with a ratio of % to 20/80, and an example of a polymerizable compound having a perfluoroalkyl group and an acrylic acid group or a methacrylic acid group is the formula % (2) (3) (4) ( 5) (6) [In the formula, R2 is a perfluoroalkyl group or perfluoroalkenyl group having 1 to 21 carbon atoms, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R2 is a C1 to 10 alkyl group.
Examples include compounds represented by an alkylene group, R3 is hydrogen or a methyl group, Ar is an arylene group which may have a substituent, and n is an integer from 1 to 10.
さらに具体的には、
ＣＦ３（ＣＦ２） ？ （ＣＨ２）ＯＣＯＣ：Ｈ＝ＣＨ
□。More specifically, CF3 (CF2)? (CH2)OCOC:H=CH
□.
ＣＦ３（ＣＦ２）７（ＣＨ２）ＯＣＯＣ（Ｃ１１３）＝
ＣＩＪ２（ＣＦ３）２ＣＦ（ＣＦ２）、（ＣＨ２）２０
ＣＯＣＲ＝ＣＨ２゜ＣＦ３（ＣＦｚ）７（ＣＨ２）２０
ｃＯｃ（Ｃｔ（ａ）＝Ｃ：Ｈ２゜ＣＦ−（ＣＦ２） ７
（ＣＨ２） ＪＣ：０ＣＣＩ（＝ＣＨ□。CF3(CF2)7(CH2)OCOC(C113)=
CIJ2(CF3)2CF(CF2), (CH2)20
COCR=CH2゜CF3(CFz)7(CH2)20
cOc(Ct(a)=C:H2゜CF-(CF2) 7
(CH2) JC:0CCI (=CH□.
ＣＦ３（ＣＦ２）？ （ＣＩ（２） ２０ＣＯＣｔ（２
ＣＬＣＦ３（ＣＦ２）７Ｓ０２−Ｎ（ＣＨ３）（ＣＨ２
）２０ＣＯＣＨ＝Ｃ）１２ 。CF3 (CF2)? (CI(2) 20COCt(2
CLCF3(CF2)7S02-N(CH3)(CH2
)20COCH=C)12.
ＣＦ、 （ＣＦ２）、ＳＯ□−Ｎ（Ｃ２Ｈｅ） （ＣＨ
２）２０ＣＯＧ（ＣＨ３）＝ＣＨ２（ＣＦｉ）ｚｃＦ（
Ｃｈ）ｒ、ＣＨ８ＣＨ（ＯＣＯＣＨ３）ＣＨ２０ＣＯＣ
（ＣＨ３）＝Ｃ：Ｈ２（ＣＦ３） ２ＣＦ ＣＧＦ２）
、ＣＨ２Ｃ）ｌ （ＯＨ） ＣＨ３０Ｃ：０ＣＨ＝Ｃ
Ｈ２゜Ｃ，Ｆ、、−０−Ｐｈ−ＣＩ−１２０−ＣＯＣ：
）Ｉ”ＣＨ２゜Ｃ，Ｆ、 、−０−Ｐｈ−ＣＨ，０−Ｃ
ＯＣ（ＣＨ，）＝ＣＨ２を例示することができる。CF, (CF2), SO□-N(C2He) (CH
2) 20COG(CH3)=CH2(CFi)zcF(
Ch)r, CH8CH(OCOCH3)CH20COC
(CH3)=C:H2(CF3) 2CF CGF2)
, CH2C)l (OH) CH30C:0CH=C
H2°C,F, -0-Ph-CI-120-COC:
)I”CH2゜C,F, ,-0-Ph-CH,0-C
An example is OC(CH,)=CH2.
他の共重合可能な重合性化合物には種々のものがあるが
例示すると、
（１）アクリル酸及びメタクリル酸ならびにこれらのメ
チル、エヂル、ブチル、イソブヂル。There are various other polymerizable compounds that can be copolymerized, but examples include: (1) Acrylic acid and methacrylic acid, and their methyl, edyl, butyl, and isobutyl.
ｔ−ブヂル、プロピル、２−エチルへキシルヘキシル、
デシル、ラウリル ステアリル イソボロニル、β−ヒ
ドロキシエヂル、グリシジルエステル、フェニル、ベン
ジル、４−シアノエチルエステル類、 ＲＯ（ＣＨ２Ｃ
Ｈ２０）、Ｈ（ここで、Ｒはアルキル類、ｐは１以上の
整数である）とのエステル、（２）酢酸、プロピオン酸
、カプリル酸、ラウリル酸、ステアリン酸等の脂肪酸の
ビニルエステル類、（３）スチレン、α−メチルスチレ
ン、ｐ−メチルスチレン等のスチレン化合物、（４）フ
ッ化ビニル、塩化ビニル、臭化ビニル、フッ化ビニリデ
ン、塩化ビニリデン等のハロゲン化ビニル、またはビニ
リデン化合物、（５）ヘプクン酸アリル、カプリル酸ア
リル等の脂肪酸のアリルエステル類、（６）ビニルメチ
ルケトン、ビニルエチルケトン等のビニルアルギルケト
ン類、（７）Ｎ−メチルアクリルアミドＮ−メチロール
メタクリルアミド等のアクリルアミド類、（８） ２，
３−ジクロロ−１，３−ブタジエ１
ン、イソプレン等のジエン類、及び（９）ジメタクル酸
エチレン等のアルキレングリコール類またはポリアルキ
レングリコールのアクリル酸またはメタクリル酸などを
例示することができる。t-butyl, propyl, 2-ethylhexylhexyl,
Decyl, lauryl stearyl isobornyl, β-hydroxyedyl, glycidyl ester, phenyl, benzyl, 4-cyanoethyl esters, RO(CH2C
(2) vinyl esters of fatty acids such as acetic acid, propionic acid, caprylic acid, lauric acid, and stearic acid; (3) Styrene compounds such as styrene, α-methylstyrene, p-methylstyrene, (4) Vinyl halides such as vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride, or vinylidene compounds, ( 5) Allyl esters of fatty acids such as allyl hebucnate and allyl caprylate; (6) vinyl argyl ketones such as vinyl methyl ketone and vinyl ethyl ketone; (7) acrylamide such as N-methylacrylamide and N-methylolmethacrylamide. Class, (8) 2,
Examples include dienes such as 3-dichloro-1,3-butadiene and isoprene, and (9) alkylene glycols such as ethylene dimethacrylate, or acrylic acid or methacrylic acid of polyalkylene glycol.
フルオロシリコーンオイル及びフルオロシリコーン共重
合体からなるフルオロシリコーン重合体とフルオロアク
リレート重合体との混合割合は、前者対後者の重量比が
、５／９５〜９５１５であり、好ましくは１０／９０〜
５０／ ５０である。The mixing ratio of the fluorosilicone polymer consisting of fluorosilicone oil and fluorosilicone copolymer and the fluoroacrylate polymer is such that the weight ratio of the former to the latter is 5/95 to 9515, preferably 10/90 to 10/90.
It's 50/50.
又、フルオロシリコーン共重合体とフルオロアクリレー
ト重合体との混合割合も、同様に、５／９５〜９５１５
、好ましくは１０／９０〜５（］／ ５０である。Similarly, the mixing ratio of the fluorosilicone copolymer and the fluoroacrylate polymer is 5/95 to 9515.
, preferably 10/90 to 5(]/50.
これら、重合体組成物の使用形態は特に限定されるもの
ではないが、適当な溶剤にこれらの成分を溶解させて使
用する方法、適当な乳化剤を使用してこれらを水に分散
させて乳化型組成物として使用する方法、さらに溶剤と
噴射剤を配合してエアゾル型組成物として使用する方法
］ ２
等を例示することができる。用途としてば、撥水撥油剤
、離型剤、剥離剤５等を挙げることかできる。There are no particular limitations on the form in which these polymer compositions are used, but they can be used by dissolving these components in a suitable solvent, or by dispersing them in water using a suitable emulsifier. A method of using it as a composition, and a method of using it as an aerosol type composition by blending a solvent and a propellant] 2 can be exemplified. Examples of uses include water and oil repellents, mold release agents, and release agents.
［実施例１
を發） ・十′ １へのｒ二 列
撥水性は、ＪＳＬ １００５のスプレー法による撥水性
ＮＯとして表わした。撥水性の評価基準を第１表に示す
。[Example 1] Water repellency was expressed as water repellency NO by JSL 1005 spray method. Table 1 shows the evaluation criteria for water repellency.
第１表
［フルオロシリコーン（ＦＬＳと略）重合体コフルオロ
シリコーンオイルとして下記式に示すオイル
Ｃ４Ｆ。Table 1 [Fluorosilicone (abbreviated as FLS)] Oil C4F shown in the following formula as cofluorosilicone oil.
［フルオロアクリレート（ＦＡ）重合体］フルオロアク
リレート重合体としての含弗素モノマー
ＣＦ３（ＣＦ２）ｎＣ８２ＣＨ２０ＣＯＣ：＝ＣＨ２［
ｎ＝８のもの、ｎ：１０のもの及びｎ＝１２のものの混
合物］ （以下モノマーａと略す）の重合体もしくは第
２表に示すモノマーとの共重合体を使用した。[Fluoroacrylate (FA) polymer] Fluorine-containing monomer CF3 (CF2)nC82CH20COC:=CH2[
A mixture of n=8, n:10 and n=12] (hereinafter abbreviated as monomer a) or a copolymer with the monomer shown in Table 2 was used.
４Ｆｓ
４Ｆ９
■
フルオロシリコーン共重合体としては
（Ｃ：Ｈ３）、＋ＳｉＯ＋７２６０部、Ｃ４Ｆ９Ｃ２Ｈ
ａＳｉＯ３ｙ□２００部、５ｉ０２８０部から成る９共
重合体
を使用した。4Fs 4F9 ■ Fluorosilicone copolymer (C:H3), +SiO+7260 parts, C4F9C2H
A 9 copolymer consisting of 200 parts of aSiO3y□ and 280 parts of 5i0 was used.
６
姐、ＭＵＬさ９」コ１俣
第３表に示すＦＬＡ、 ＦＡ重合体のトリクロロトリフ
ルオロエタンの５ｗｔ％溶液を調整し、はけで金型に塗
布した。次にブチル製のゴム１万個をこの金型を使用し
て成形化工した時の結果を示す。A 5 wt % solution of the FLA and FA polymers shown in Table 3 in trichlorotrifluoroethane was prepared and applied to the mold with a brush. Next, we will show the results when 10,000 pieces of butyl rubber were molded using this mold.
［発明の効果］
従来、撥水撥油剤や離型剤に例示されるような種々の用
途に、フルオロシリコーン重合体やフルオロアクリレー
ト重合体が使用されていた。[Effects of the Invention] Conventionally, fluorosilicone polymers and fluoroacrylate polymers have been used for various purposes such as water and oil repellents and mold release agents.
しかし、例えば、撥水撥油剤としてフルオロアクリレー
ト重合体を使用した場合、撥水・撥油性には優れている
が、この重合体は硬い化合物であるため、これを用いて
繊維織物の処理を行なった場合、風合いが堅くなる、あ
るいは伸びが悪いために処理ムラがおこり易い等の問題
が指摘されていた。一方、フルオロシリコーン重合体を
単独で繊維処理剤として使用した場合、フルオロシリコ
ーン重合体は柔らかい化合物であるため、繊維織物の風
合いを損なうことはないが、撥油性・耐久性に乏しい、
等の問題があった。However, for example, when a fluoroacrylate polymer is used as a water and oil repellent, although it has excellent water and oil repellency, this polymer is a hard compound, so it cannot be used to treat textile fabrics. It has been pointed out that problems such as a hard texture or poor spreadability tend to result in uneven processing. On the other hand, when a fluorosilicone polymer is used alone as a fiber treatment agent, since the fluorosilicone polymer is a soft compound, it does not impair the texture of the textile fabric, but it has poor oil repellency and durability.
There were other problems.
また、離型剤としてフルオロアクリレート重合体を使用
した場合、離型性（Ｊ優れるものの、離型剤の離型物へ
の移行が観察される。一方、 ９
フルオロシリコーン重合体を離型剤として使用した場合
、離型剤の離型物への移行は防止されるものの、離型性
に乏しいという欠点が指摘されていた。In addition, when a fluoroacrylate polymer is used as a mold release agent, although the mold release property (J is excellent), migration of the mold release agent to the mold release product is observed.On the other hand, when a fluorosilicone polymer is used as a mold release agent, When used, although migration of the mold release agent to the mold release material is prevented, it has been pointed out that it has a drawback of poor mold release properties.
本発明では、これらの欠点を解決し、優れた性能を発揮
する。The present invention solves these drawbacks and exhibits excellent performance.
０0
Claims (2)
び（Ｂ）で示されるフルオロシリコーン共重合体からな
るフルオロシリコーン重合体と▲数式、化学式、表等が
あります▼・・・・・・・・・（Ａ） ［式中、Ｒ＿ｆは炭素数１〜２１のパーフルオロアルキ
ル基、ｍ、ｎはｎ／ｎ＋ｍ≧０．１を満足する整数］ （ＣＨ＿３）＿ｎＳｉＯ＿４＿−＿ｎ＿／＿２、（Ｒ＾
１＿ｆ）＿ｍ（ＣＨ＿３）＿ｌＳｉＯ＿（＿４＿−＿（
＿ｍ＿＋＿１＿）＿）＿／＿２、又はＳｉＯ＿２の少な
くとも２種からなる共重合体・・・・・・・・・（Ｂ） ［式中、Ｒ＾１＿ｆは炭素数１〜２１のパーフルオロア
ルキル基、ｎ、ｍ、ｌは１≦ｎ≦３、１≦ｍ＋ｌ≦３を
満足する整数］ パーフルオロアルキル基及びアクリル酸基もしくはメタ
クリル酸基を有する重合性化合物の少なくとも１種のホ
モ重合体もしくは共重合体または前記重合性化合物の少
なくとも１種と共重合可能な重合性化合物との共重合体
からなるフルオロアクリレート重合体を含有することを
特徴とするフルオロシリコーン重合体とフルオロアクリ
レート重合体からなる組成物。(1) Fluorosilicone polymer consisting of fluorosilicone oil represented by formula (A) and fluorosilicone copolymer represented by (B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・・(A) [In the formula, R_f is a perfluoroalkyl group having 1 to 21 carbon atoms, m and n are integers satisfying n/n+m≧0.1] (CH_3)_nSiO_4_-_n_/_2, (R^
1_f)_m(CH_3)_lSiO_(_4_-_(
_m_+_1_)_)_/_2, or a copolymer consisting of at least two types of SiO_2 (B) [wherein R^1_f is a perfluoroalkyl group having 1 to 21 carbon atoms, n, m, l are integers satisfying 1≦n≦3, 1≦m+l≦3] At least one homopolymer or copolymer of a polymerizable compound having a perfluoroalkyl group and an acrylic acid group or a methacrylic acid group A composition consisting of a fluorosilicone polymer and a fluoroacrylate polymer, characterized in that it contains a fluoroacrylate polymer consisting of a copolymer of a polymerizable compound that can be combined or copolymerized with at least one of the above polymerizable compounds. .
はメタクリル酸基を有する重合性化合物の少なくとも１
種のホモ重合体もしくは共重合体又は前記重合性化合物
の少なくとも１種と共重合可能な重合性化合物との共重
合体からなるフルオロアクリレート重合体と式 （Ｂ）で示されるフルオロシリコーン共重合体を含有す
ることを特徴とするフルオロシリ コーン重合体とフルオロアクリレート重合体からなる組
成物。 （ＣＨ＿３）＿ｎＳｉＯ＿４＿−＿ｎ＿／＿２、（Ｒ＾
１＿ｆ）＿ｍ（ＣＨ＿３）＿ｌＳｉＯ＿（＿４＿−＿（
＿ｍ＿＋＿ｌ＿）＿）＿／＿２、又はＳｉＯ＿２の少な
くとも２種からなる共重合体・・・・・・・・・（Ｂ） ［式中、Ｒ＾１＿ｆは炭素数１〜２１のパーフルオロア
ルキル基、ｎ、ｍ、ｌは１≦ｎ≦３、１≦ｍ＋ｌ≦３を
満足する整数］(2) At least one polymerizable compound having a perfluoroalkyl group and an acrylic acid group or a methacrylic acid group
A fluoroacrylate polymer consisting of a homopolymer or copolymer of species, or a copolymer of a polymerizable compound copolymerizable with at least one of the above polymerizable compounds, and a fluorosilicone copolymer represented by formula (B). A composition comprising a fluorosilicone polymer and a fluoroacrylate polymer. (CH_3)_nSiO_4_−_n_/_2, (R^
1_f)_m(CH_3)_lSiO_(_4_-_(
_m_+_l_)_)_/_2, or a copolymer consisting of at least two types of SiO_2 (B) [wherein R^1_f is a perfluoroalkyl group having 1 to 21 carbon atoms, n, m, l are integers satisfying 1≦n≦3, 1≦m+l≦3]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32733789A JPH03190951A (en) | 1989-12-19 | 1989-12-19 | Composition comprising fluorosilicone polymer and fluoroacrylate polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32733789A JPH03190951A (en) | 1989-12-19 | 1989-12-19 | Composition comprising fluorosilicone polymer and fluoroacrylate polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03190951A true JPH03190951A (en) | 1991-08-20 |
Family
ID=18198011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32733789A Pending JPH03190951A (en) | 1989-12-19 | 1989-12-19 | Composition comprising fluorosilicone polymer and fluoroacrylate polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03190951A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5698320A (en) * | 1994-08-08 | 1997-12-16 | Fujitsu Limited | Image forming device |
| US7087694B2 (en) | 2000-11-15 | 2006-08-08 | E. I. Du Pont De Nemours And Company | Fluorinated copolymers for hydrophobic and oleophobic treatment of building materials |
| US8003746B2 (en) | 2005-05-09 | 2011-08-23 | Dow Corning Corporation | Amino-mercapto functional organopolysiloxanes |
| WO2014046209A1 (en) * | 2012-09-24 | 2014-03-27 | 旭硝子株式会社 | Ink-repellent composition, negative photosensitive resin composition, hardened film, partition wall, and optical element |
-
1989
- 1989-12-19 JP JP32733789A patent/JPH03190951A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5698320A (en) * | 1994-08-08 | 1997-12-16 | Fujitsu Limited | Image forming device |
| US7087694B2 (en) | 2000-11-15 | 2006-08-08 | E. I. Du Pont De Nemours And Company | Fluorinated copolymers for hydrophobic and oleophobic treatment of building materials |
| US8003746B2 (en) | 2005-05-09 | 2011-08-23 | Dow Corning Corporation | Amino-mercapto functional organopolysiloxanes |
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| KR20150060689A (en) * | 2012-09-24 | 2015-06-03 | 아사히 가라스 가부시키가이샤 | Ink-repellent composition, negative photosensitive resin composition, hardened film, partition wall, and optical element |
| CN104684994A (en) * | 2012-09-24 | 2015-06-03 | 旭硝子株式会社 | Ink-repellent composition, negative photosensitive resin composition, hardened film, partition wall, and optical element |
| JPWO2014046209A1 (en) * | 2012-09-24 | 2016-08-18 | 旭硝子株式会社 | Ink-repellent composition, negative photosensitive resin composition, cured film, partition, and optical element |
| TWI649621B (en) * | 2012-09-24 | 2019-02-01 | 日商Ａｇｃ股份有限公司 | Ink-repellent composition, negative photosensitive resin composition, cured film, partition, optical component |
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