JP4757504B2 - Silicone composition for forming a peelable cured film - Google Patents
Silicone composition for forming a peelable cured film Download PDFInfo
- Publication number
- JP4757504B2 JP4757504B2 JP2005027853A JP2005027853A JP4757504B2 JP 4757504 B2 JP4757504 B2 JP 4757504B2 JP 2005027853 A JP2005027853 A JP 2005027853A JP 2005027853 A JP2005027853 A JP 2005027853A JP 4757504 B2 JP4757504 B2 JP 4757504B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- cured film
- forming
- bonded
- film
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 37
- 229920001296 polysiloxane Polymers 0.000 title claims description 25
- -1 polyethylene terephthalate Polymers 0.000 claims description 52
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000002985 plastic film Substances 0.000 description 13
- 229920006255 plastic film Polymers 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920006267 polyester film Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 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 3
- 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 3
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 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 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 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 3
- 125000000913 palmityl 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])C([H])([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 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004079 stearyl 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])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])[H] 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-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
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、剥離性硬化皮膜形成用シリコーン組成物に係り、特に、ポリエステルフィルムやポリプロピレンフィルム等のプラスチックフィルムからなる基材に対する密着性を高めた剥離性硬化皮膜形成用シリコーン組成物に関する。 The present invention relates to a silicone composition for forming a peelable cured film, and more particularly to a silicone composition for forming a peelable cured film having improved adhesion to a substrate made of a plastic film such as a polyester film or a polypropylene film.
従来より、紙、プラスチックフィルム、金属箔等の基材表面に剥離性の硬化皮膜を形成するため、アルケニル基含有ポリオルガノシロキサン、ポリオルガノハイドロジェンシロキサンおよび白金系触媒からなる、いわゆる付加反応型のポリオルガノシロキサン組成物（シリコーン組成物）が汎用されている。 Conventionally, in order to form a peelable cured film on the surface of a substrate such as paper, plastic film, metal foil, etc., a so-called addition reaction type comprising an alkenyl group-containing polyorganosiloxane, polyorganohydrogensiloxane and a platinum-based catalyst. Polyorganosiloxane compositions (silicone compositions) are widely used.
しかしながら、従来のこの種のシリコーン組成物は、紙基材には良好に密着するものの、ポリエチレンテレフタレートのようなポリエステルフィルムやポリプロピレンフィルム等のプラスチックフィルムに対する密着性に乏しく、その硬化皮膜表面を強く擦ると部分的に脱落して剥離性が低下するという難点があった。しかも、密着性は時間の経過とともに低下し、硬化皮膜の脱落が発生しやすくなる傾向にあった。 However, although this type of conventional silicone composition adheres well to a paper substrate, it has poor adhesion to a plastic film such as a polyester film such as polyethylene terephthalate or a polypropylene film, and strongly rubs the surface of the cured film. And partly dropped out, resulting in a difficulty in peeling. Moreover, the adhesion tends to decrease with time and the cured film tends to fall off.
そこで、これらのシリコーン組成物に、γ‐グリシドキシプロピルトリメトキシシランやビニルトリアセトキシシラン等のシランカップリング剤を配合したり、基材表面にプライマ処理を施すことにより、基材に対する密着性を高める方法が提案されている（例えば、特許文献１参照。）。しかしながら、シランカップリング剤を配合した組成物は、高温で加熱処理しなければ基材に対する密着性が向上しないため、耐熱性が紙等に比べて低く高温での処理が困難なプラスチックフィルム基材への適用には不向きである。また、基材表面にプライマ処理を施す方法は、適用時の工程が増えることによる不利がある。 Therefore, these silicone compositions are mixed with a silane coupling agent such as γ-glycidoxypropyltrimethoxysilane or vinyltriacetoxysilane, or by applying a primer treatment to the surface of the base material, thereby making it possible to adhere to the base material. Has been proposed (see, for example, Patent Document 1). However, a composition containing a silane coupling agent does not improve adhesion to a substrate unless it is heat-treated at a high temperature, so that the heat resistance is lower than that of paper or the like, and a plastic film substrate that is difficult to process at a high temperature. It is not suitable for application. In addition, the method of applying the primer treatment to the substrate surface has a disadvantage due to an increase in the number of steps during application.
また、有機アルミニウム化合物、メタクリロキシ基もしくはアクリロキシ基含有オルガノアルコキシシランおよびアルケニル基含有オルガノアシロキシシランを併用したシリコーン組成物も提案されているが、その改善効果は十分なものではなかった（例えば、特許文献２参照。）。
上述したように、従来の剥離性硬化皮膜形成用シリコーン組成物は、ポリエステルフィルムやポリプロピレンフィルム等のプラスチックフィルムからなる基材に対する密着性が乏しいという問題があり、これを改善するため、シランカップリング剤を配合する等、様々な方法が提案されている。しかしながら、基材表面にプライマ処理を施すことなく、プラスチックフィルムからなる基材上に強固に密着した剥離性硬化皮膜を形成可能なシリコーン組成物は未だ得られていない。 As described above, the conventional silicone composition for forming a peelable cured film has a problem of poor adhesion to a substrate made of a plastic film such as a polyester film or a polypropylene film. In order to improve this, silane coupling is required. Various methods such as blending agents have been proposed. However, a silicone composition that can form a peelable cured film that is firmly adhered to a substrate made of a plastic film without performing a primer treatment on the substrate surface has not yet been obtained.
本発明はこのような従来技術の課題に対処してなされたもので、ポリエステルフィルムやポリプロピレンフィルム等のプラスチックフィルムからなる基材に対して極めて良好な接着性を示し、適用にあたり基材表面にプライマ処理等を施す必要のない剥離性硬化皮膜形成用シリコーン組成物を提供することを目的とする。 The present invention has been made in response to such problems of the prior art, and exhibits extremely good adhesion to a substrate made of a plastic film such as a polyester film or a polypropylene film. It aims at providing the silicone composition for peelable cured film formation which does not need to give a process etc.
上記目的を達成するため、本願の請求項１に記載の発明の剥離性硬化皮膜形成用シリコーン組成物は、
ポリエチレンテレフタレートフィルムまたはポリプロピレンフィルムからなる基材表面に剥離性硬化皮膜を形成するために使用される剥離性硬化皮膜形成用シリコーン組成物であって、
（Ａ）１分子中に少なくとも２個のケイ素原子に直接結合したアルケニル基を有するポリオルガノシロキサン １００重量部、
（Ｂ）１分子中に少なくとも３個のケイ素原子に直接結合した水素原子を有し、２５℃における動粘度が１ｍｍ２／ｓ以上であるポリオルガノハイドロジェンシロキサン
０．１〜３０重量部、
（Ｃ）１分子中にケイ素原子に炭素原子を介して結合した、下記式（１）で示されるエポキシ基を有するシロキサン単位を１０モル％以上含有し、かつ、ケイ素原子に直接結合した水素原子を実質的に有さない、前記エポキシ基以外のケイ素原子に結合する有機基がメチル基である重合度が５以上のポリオルガノシロキサン ０．１〜３０重量部、
および
（Ｄ）白金系触媒 触媒量
を含有することを特徴とするものである。
A silicone composition for forming a peelable cured film used for forming a peelable cured film on a substrate surface comprising a polyethylene terephthalate film or a polypropylene film,
(A) 100 parts by weight of a polyorganosiloxane having an alkenyl group directly bonded to at least two silicon atoms in one molecule;
(B) A polyorganohydrogensiloxane having hydrogen atoms directly bonded to at least three silicon atoms in one molecule and a kinematic viscosity at 25 ° C. of 1 mm 2 / s or more
0.1 to 30 parts by weight,
(C) A hydrogen atom containing 10 mol% or more of a siloxane unit having an epoxy group represented by the following formula (1) bonded to a silicon atom via a carbon atom in one molecule and directly bonded to the silicon atom 0.1 to 30 parts by weight of a polyorganosiloxane having a polymerization degree of 5 or more, wherein the organic group bonded to the silicon atom other than the epoxy group is a methyl group ,
And (D) a platinum-based catalyst containing a catalyst amount.
本発明の剥離性硬化皮膜形成用シリコーン組成物によれば、プライマ処理等を施さずとも、ポリエステルフィルムやポリプロピレンフィルム等のプラスチックフィルムからなる基材上に極めて強固に接着した剥離性硬化皮膜を形成することができる。 According to the silicone composition for forming a peelable cured film of the present invention, it is possible to form a peelable cured film that adheres extremely firmly to a substrate made of a plastic film such as a polyester film or a polypropylene film without performing a primer treatment or the like. can do.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明で用いられる（Ａ）成分のポリオルガノシロキサンは、１分子中に少なくとも２個のケイ素原子に直接結合したアルケニル基を有するものである。 The polyorganosiloxane of component (A) used in the present invention has an alkenyl group directly bonded to at least two silicon atoms in one molecule.
アルケニル基としては、例えばビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基等が挙げられるが、合成の容易さや熱安定性等の点から、なかでもビニル基が好ましい。このアルケニル基の結合位置は、特に限定されるものではなく、分子鎖末端および分子鎖側鎖のいずれであってもよく、また、その両方であってもよい。 Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. Among these, a vinyl group is preferable from the viewpoint of ease of synthesis and thermal stability. The bonding position of the alkenyl group is not particularly limited, and may be either the molecular chain end or the molecular chain side chain, or both.
また、ケイ素原子に結合するアルケニル基以外の有機基としては、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基等の鎖状アルキル基；シクロヘキシル基等のシクロアルキル基；フェニル基、ナフチル基、トリル基等のアリール基；β‐フェニルエチル基、β‐フェニルプロピル基等のアラルキル基、または、これらの基の炭素原子に結合した水素原子の一部もしくは全部を、ハロゲン原子、シアノ基、水酸基等で置換した、クロロメチル基、３，３，３‐トリフルオロプロピル基、シアノプロピル基、フェノール基、ヒンダードフェノール基等の、同種または異種の置換または非置換の１価の炭化水素基等が挙げられる。これらの基のなかでも、合成が容易で、硬化後に良好な物理的性質を保つ上で必要な重合度を与え、かつ、硬化前においては低い粘度を与えることから、メチル基が好ましい。 Examples of organic groups other than alkenyl groups bonded to silicon atoms include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, Chain alkyl groups such as octadecyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group, naphthyl group and tolyl group; aralkyl groups such as β-phenylethyl group, β-phenylpropyl group, etc. A chloromethyl group, a 3,3,3-trifluoropropyl group, a cyanopropyl group, a phenol group, wherein a part or all of the hydrogen atoms bonded to the carbon atoms of the group are substituted with a halogen atom, a cyano group, a hydroxyl group, etc. Examples include the same or different substituted or unsubstituted monovalent hydrocarbon groups such as hindered phenol groups. . Among these groups, a methyl group is preferred because it is easy to synthesize, gives a degree of polymerization necessary for maintaining good physical properties after curing, and gives a low viscosity before curing.
このポリオルガノシロキサンの分子構造は、直鎖状もしくは分枝鎖状のいずれであってもよく、直鎖状のものと分枝鎖状のものを混合して使用することもできる。また、このポリオルガノシロキサンとしては、液状のものから生ゴム状のものまで使用可能であるが、粘度があまり低いと基材への浸透が多くなり過ぎて剥離特性が低下するおそれがあることから、２５℃における粘度が２０ｍＰａ・ｓ以上のものが好ましい。 The molecular structure of this polyorganosiloxane may be either linear or branched, and a mixture of linear and branched ones can also be used. In addition, as this polyorganosiloxane, it can be used from liquid to raw rubber, but if the viscosity is too low, there is a possibility that the penetration property will be too much and the peeling property may be lowered. Those having a viscosity at 25 ° C. of 20 mPa · s or more are preferred.
本成分の具体例としては、両末端ジメチルビニルシロキシ基封鎖ポリジメチルシロキサン、両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルビニルシロキサン・ジメチルシロキサン共重合体、両末端水酸基封鎖メチルビニルシロキサン・ジメチルシロキサン共重合体等が挙げられる。 Specific examples of this component include polydimethylsiloxane blocked with dimethylvinylsiloxy at both ends, dimethylsiloxane / methylvinylsiloxane copolymer blocked with dimethylvinylsiloxy at both ends, and trimethylsiloxy-blocked methylvinylsiloxane / dimethylsiloxane copolymer at both ends. Examples thereof include a copolymer, a hydroxyl group-blocked methyl vinyl siloxane / dimethyl siloxane copolymer and the like.
本発明で用いられる（Ｂ）成分のポリオルガノハイドロジェンシロキサンは、１分子中に少なくとも３個のケイ素原子に直接結合した水素原子を有し、かつ、２５℃における動粘度が１ｍｍ２／ｓ以上であるものである。本成分は（Ａ）成分のポリオルガノシロキサンの架橋成分として作用する。 The polyorganohydrogensiloxane of component (B) used in the present invention has hydrogen atoms directly bonded to at least three silicon atoms in one molecule, and has a kinematic viscosity at 25 ° C. of 1 mm 2 / s or more. It is what is. This component acts as a crosslinking component of the polyorganosiloxane (A).
ケイ素原子に結合する水素原子以外の基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基等の鎖状アルキル基；シクロヘキシル基等のシクロアルキル基；フェニル基、ナフチル基、トリル基、キシリル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基；または、これらの基の炭素原子に結合した水素原子の一部もしくは全部を、ハロゲン原子、シアノ基、水酸基等で置換した、３‐クロロプロピル基、３，３，３‐トリフルオロプロピル基、シアノプロピル基、フェノール基、ヒンダードフェノール基等の、同種または異種の置換または非置換の１価の炭化水素基、その他少量の水酸基、メトキシ基、エトキシ基等のアルコキシ基等が例示されるが、なかでも、メチル基が合成が容易であるという点から好ましい。 Examples of a group other than a hydrogen atom bonded to a silicon atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group. A chain alkyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group, a naphthyl group, a tolyl group, and a xylyl group; an aralkyl group such as a benzyl group and a phenethyl group; or bonded to a carbon atom of these groups 3-chloropropyl group, 3,3,3-trifluoropropyl group, cyanopropyl group, phenol group, hindered phenol group, etc., in which part or all of the hydrogen atoms are substituted with halogen atoms, cyano groups, hydroxyl groups, etc. The same or different substituted or unsubstituted monovalent hydrocarbon group, a small amount of hydroxyl group, methoxy group, Although an alkoxy group such as butoxy group can be exemplified. Among them, preferred from the viewpoint of a methyl group is easy to synthesize.
このポリオルガノハイドロジェンシロキサンの分子構造は、特に限定されるものではなく、直鎖状、一部分岐を有する直鎖状、分岐鎖状、環状、樹枝状等が例示され、これらの併用も可能である。また、粘度は、２５℃における動粘度が１ｍｍ２／ｓ未満であると、揮発性が大きく、硬化皮膜の形成に悪影響を及ぼすことから、２５℃における粘度が１ｍｍ２／ｓ以上であることが必要であるが、２５℃における粘度が５ｍｍ２／ｓ以上であるとより好ましい。 The molecular structure of this polyorganohydrogensiloxane is not particularly limited, and examples thereof include straight-chain, partially-branched straight-chain, branched-chain, cyclic, and dendritic shapes, and these can be used in combination. is there. In addition, the viscosity at 25 ° C. is less than 1 mm 2 / s, and the viscosity at 25 ° C. is 1 mm 2 / s or more because the volatility is large and adversely affects the formation of a cured film. Although it is necessary, the viscosity at 25 ° C. is more preferably 5 mm 2 / s or more.
本成分の具体例としては、両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端トリメチルシロキシ基封鎖ポリメチルハイドロジェンシロキサン、環状ポリメチルハイドロジェンシロキサン、環状ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体等が挙げられる。 Specific examples of this component include a trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, a dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, a trimethylsiloxy group-capped terminus. Examples thereof include polymethylhydrogensiloxane, cyclic polymethylhydrogensiloxane, and cyclic dimethylsiloxane / methylhydrogensiloxane copolymer.
この（Ｂ）成分のポリオルガノハイドロジェンシロキサンの配合量は、１分子中のケイ素原子に結合した水素原子の数によって異なるが、一般的には（Ａ）成分のポリオルガノシロキサン１００重量部に対し、０．１〜３０重量部の範囲である。０．１重量部未満では、硬化が不十分となり、また、３０重量部を超えると、硬化皮膜の剥離性および強度が低下する。 The blending amount of the polyorganohydrogensiloxane of the component (B) varies depending on the number of hydrogen atoms bonded to silicon atoms in one molecule, but is generally based on 100 parts by weight of the polyorganosiloxane of the component (A). In the range of 0.1 to 30 parts by weight. If it is less than 0.1 part by weight, curing becomes insufficient, and if it exceeds 30 parts by weight, the peelability and strength of the cured film are lowered.
本発明で用いられる（Ｃ）成分は、１分子中に少なくとも２個のケイ素原子に炭素原子を介して結合したエポキシ基を有し、かつ、ケイ素原子に直接結合した水素原子を実質的に有さないポリオルガノシロキサンである。本成分は、主として本発明の組成物の基材に対する密着性を向上させる作用を有する。特にポリエステルフィルムやポリプロピレンフィルム等のプラスチックフィルムからなる基材に対する密着性を向上させる。１分子中のケイ素原子に炭素原子を介して結合するエポキシ基数が１個では、かかる効果を得ることはできない。また、分子中にケイ素原子に直接結合した水素原子が存在すると、良好な剥離力が得られない。この（Ｃ）成分のポリオルガノシロキサンは、直鎖状、分岐状のいずれであってもよく、また、それらの混合物であってもよい。 The component (C) used in the present invention has an epoxy group bonded to at least two silicon atoms via a carbon atom in one molecule and substantially has a hydrogen atom bonded directly to the silicon atom. Not polyorganosiloxane. This component has the effect | action which mainly improves the adhesiveness with respect to the base material of the composition of this invention. In particular, adhesion to a substrate made of a plastic film such as a polyester film or a polypropylene film is improved. Such an effect cannot be obtained if the number of epoxy groups bonded to the silicon atom in one molecule via a carbon atom is one. In addition, when a hydrogen atom directly bonded to a silicon atom exists in the molecule, a good peeling force cannot be obtained. The polyorganosiloxane of component (C) may be linear or branched, or a mixture thereof.
ケイ素原子に結合するエポキシ基を有する１価の有機基としては、例えば下記の（１）〜（３）の構造式で示されるものが例示される。
また、ケイ素原子に結合するエポキシ基を有する１価の有機基以外の有機基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基等の鎖状アルキル基；シクロヘキシル基等のシクロアルキル基；フェニル基、ナフチル基、トリル基、キシリル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基；または、これらの基の炭素原子に結合した水素原子の一部もしくは全部を、ハロゲン原子、シアノ基、水酸基等で置換した、クロロメチル基、３，３，３‐トリフルオロプロピル基、シアノプロピル基、フェノール基、ヒンダードフェノール基等の、同種または異種の置換または非置換の１価の炭化水素基等が挙げられる。これらの基のなかでも、合成が容易であることから、メチル基が好ましい。 Examples of the organic group other than the monovalent organic group having an epoxy group bonded to a silicon atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, Chain alkyl groups such as tetradecyl group, hexadecyl group and octadecyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group, naphthyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group; or A chloromethyl group, a 3,3,3-trifluoropropyl group, a cyanopropyl group, in which a part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, a hydroxyl group, etc. Examples include the same or different substituted or unsubstituted monovalent hydrocarbon groups such as phenol groups and hindered phenol groups. It is. Among these groups, a methyl group is preferable because synthesis is easy.
この（Ｃ）成分のポリオルガノシロキサンは、ケイ素原子に炭素原子を介して結合したエポキシ基を有するシロキサン単位を５モル％以上含有するポリオルガノシロキサンであることが好ましく、ケイ素原子に炭素原子を介して結合したエポキシ基を有するシロキサン単位を１０モル％以上含有するポリオルガノシロキサンであるとより好ましい。 The polyorganosiloxane of component (C) is preferably a polyorganosiloxane containing 5 mol% or more of a siloxane unit having an epoxy group bonded to a silicon atom via a carbon atom, and the silicon atom via a carbon atom. More preferred is a polyorganosiloxane containing 10 mol% or more of siloxane units having epoxy groups bonded together.
また、（Ｃ）成分のポリオルガノシロキサンは、重合度が５以上のポリオルガノシロキサンであることが好ましい。 In addition, the polyorganosiloxane of component (C) is preferably a polyorganosiloxane having a degree of polymerization of 5 or more.
この（Ｃ）成分のポリオルガノシロキサンの配合量は、（Ａ）成分のポリオルガノシロキサン１００重量部に対し、０．１〜３０重量部の範囲であり、好ましくは０．５〜２０重量部の範囲である。０．１重量部未満では、密着性を向上させることができず、また、３０重量部を超えると、剥離特性に影響を与えたり、硬化皮膜の強度を低下させたりする。 The blending amount of the polyorganosiloxane of the component (C) is in the range of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane of the component (A). It is a range. If the amount is less than 0.1 parts by weight, the adhesion cannot be improved. If the amount exceeds 30 parts by weight, the peeling characteristics are affected, and the strength of the cured film is reduced.
本発明で用いられる（Ｄ）成分の白金系触媒は、（Ａ）成分中のアルケニル基と、（Ｂ）成分中のヒドロシリル基との間の付加反応を促進する触媒である。このような白金系触媒の具体例としては、白金、白金とオレフィン、アルケニルシロキサン、ケトン等との錯体、塩化白金酸、塩化白金酸のアルコール溶液、炭素粉末、アルミナ粉末、シリカ粉末等の担体上に吸着させた微粒子白金、白金黒、パラジウム、ロジウム触媒等が例示される。 The platinum-based catalyst of component (D) used in the present invention is a catalyst that promotes the addition reaction between the alkenyl group in component (A) and the hydrosilyl group in component (B). Specific examples of such platinum-based catalysts include platinum, complexes of platinum and olefins, alkenylsiloxanes, ketones, and the like, chloroplatinic acid, alcohol solutions of chloroplatinic acid, carbon powder, alumina powder, silica powder, and other supports. Examples thereof include fine-particle platinum, platinum black, palladium, rhodium catalyst and the like adsorbed on the catalyst.
この（Ｄ）成分の白金系触媒の配合量は、（Ａ）成分のポリオルガノシロキサンに対し、白金原子の量として、１０〜１０００ｐｐｍの範囲となる量である。１０ｐｐｍ未満では、添加による効果が得られず、１０００ｐｐｍを超えても、特に効果は変わらず、非経済的となる。 The blending amount of the platinum catalyst of component (D) is an amount that is in the range of 10 to 1000 ppm as the amount of platinum atoms with respect to the polyorganosiloxane of component (A). If it is less than 10 ppm, the effect by addition is not acquired, and even if it exceeds 1000 ppm, an effect will not change in particular and it will become uneconomical.
本発明のシリコーン組成物には、以上の成分の他に、組成物の硬化時間や使用可能時間を調節する目的で、この種の組成物に一般に使用されている反応遅延剤を、本発明の効果を阻害しない範囲で配合することができる。反応遅延剤としては、アセチレンアルコール、アセチレンアルコールのシリル化物、マレイン酸エステル、ビニル基またはアリル基を有するシロキサン化合物等が例示される。 In addition to the above components, the silicone composition of the present invention contains a reaction retarder generally used in this type of composition for the purpose of adjusting the curing time and usable time of the composition. It can mix | blend in the range which does not inhibit an effect. Examples of the reaction retarder include acetylene alcohol, silylated products of acetylene alcohol, maleic acid esters, siloxane compounds having a vinyl group or an allyl group.
また、その他、必要に応じて、有機溶剤、剥離調整剤、顔料、染料等を、本発明の効果を阻害しない範囲で配合することができる。有機溶剤としては、ベンゼン、トルエン、キシレンのような芳香族炭化水素；ヘプタン、ヘキサン、ペンタンのような脂肪族炭化水素；トリクロロエチレン、パークロロエチレンのようなハロゲン化炭化水素；酢酸エチル、メチルエチルケトン、イソプロパノール等が例示される。 In addition, if necessary, an organic solvent, a release modifier, a pigment, a dye, and the like can be blended within a range that does not impair the effects of the present invention. Organic solvents include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as heptane, hexane and pentane; halogenated hydrocarbons such as trichloroethylene and perchloroethylene; ethyl acetate, methyl ethyl ketone and isopropanol Etc. are exemplified.
本発明のシリコーン組成物は、上記（Ａ）〜（Ｄ）成分および任意成分を均一に混合することにより得られる。使用する際には、（Ｄ）成分を除く各成分を予め均一に混合した後、（Ｄ）成分を添加するか、もしくは（Ｂ）成分を除く各成分を均一に混合した後、（Ｂ）成分を添加することが好ましい。 The silicone composition of the present invention can be obtained by uniformly mixing the above components (A) to (D) and optional components. When using, after mixing each component except (D) component uniformly in advance, (D) component is added, or after mixing each component except (B) component uniformly, (B) It is preferred to add the components.
本発明の組成物の硬化皮膜を形成させるには、本発明の組成物を基材表面に塗布し、５０〜２００℃程度の温度で加熱すればよい。本発明の組成物は、従来のものに比べ、特にポリエステルフィルムやポリプロピレンフィルム等のプラスチックフィルムからなる基材に対する密着性が向上しているため、かかるプラスチックフィルム基材用のコーティング材、剥離性硬化皮膜形成材として好適に用いられる。 In order to form a cured film of the composition of the present invention, the composition of the present invention may be applied to the substrate surface and heated at a temperature of about 50 to 200 ° C. Since the composition of the present invention has improved adhesion to a substrate made of a plastic film such as a polyester film or a polypropylene film, compared to the conventional one, the coating material for such a plastic film substrate, peelable curing It is suitably used as a film forming material.
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではない。なお、以下の記載において、特に明記しない限り、「部」は「重量部」、「％」は「重量％」を意味し、粘度は２５℃における測定値である。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all. In the following description, unless otherwise specified, “part” means “part by weight”, “%” means “% by weight”, and the viscosity is a measured value at 25 ° C.
また、硬化皮膜の「密着性」の評価は次のようにして行った。
［密着性］
剥離性硬化皮膜形成用シリコーン組成物を、プラスチックフィルム（ポリエチレンテレフタレートフィルムおよびポリプロピレンフィルム）基材上に約０．８ｇ／ｍ２塗工し、１２０℃に設定した熱風循環式オーブン中で３０秒間熱処理して硬化皮膜を形成させた。次いで、これを４０℃、９０％ＲＨの条件にて２４時間セパレーターエージングした後、その硬化皮膜面を指で擦り、塗膜の脱落を目視により判定した。
The evaluation of the “adhesion” of the cured film was performed as follows.
[Adhesion]
The silicone composition for forming a peelable cured film was applied on a plastic film (polyethylene terephthalate film and polypropylene film) substrate at about 0.8 g / m 2 and heat-treated in a hot air circulation oven set at 120 ° C. for 30 seconds. Thus, a cured film was formed. Subsequently, this was subjected to separator aging under the conditions of 40 ° C. and 90% RH for 24 hours, and then the cured film surface was rubbed with a finger to determine whether the coating film had fallen off.
実施例１
分子鎖両末端がジメチルビニルシリル基で封鎖されたジメチルシロキサン・メチルビニルシロキサン共重合体（トルエンで濃度３０％に希釈したときの粘度１５Ｐａ・ｓ、ビニル基を有するシロキサン単位含有量２．０モル％；ポリジメチルシロキサンと表記）１００部、分子鎖両末端がトリメチルシロキシ基で封鎖された直鎖状ポリメチルハイドロジェンシロキサン（動粘度２５ｍｍ２／ｓ、ケイ素原子結合水素原子含有量１．６％；ポリメチルハイドロジェンシロキサンと表記）３．２部、密着性向上剤として、(ＣＨ３)３ＳｉＯ１／２単位８モル％、(ＣＨ３)２ＳｉＯ単位５６モル％および(ＣＨ３)ＸＳｉＯ単位（式中、Ｘは前記構造式（１）で示される基）３６モル％からなる鎖状シロキサン化合物（密着性向上剤Ｃ−１と表記）４部、反応遅延剤として、アセチレンアルコール０．３部と、トルエン／メチルエチルケトン（＝８０／２０）混合溶媒９００部を均一に混合した後、白金系触媒として、上記ポリジメチルシロキサンに対して白金量として１００ｐｐｍとなる量を添加し、均一に混合して剥離性硬化皮膜形成用シリコーン組成物を調製した。
Example 1
Dimethylsiloxane / methylvinylsiloxane copolymer in which both ends of the molecular chain are blocked with dimethylvinylsilyl groups (viscosity of 15 Pa · s when diluted with toluene to a concentration of 30%, content of siloxane units having vinyl groups is 2.0 mol) %; Expressed as polydimethylsiloxane) 100 parts, linear polymethylhydrogensiloxane blocked at both molecular chain ends with a trimethylsiloxy group (kinematic viscosity 25 mm 2 / s, silicon atom-bonded hydrogen atom content 1.6% ; Expressed as polymethylhydrogensiloxane) 3.2 parts, as adhesion improver, (CH 3 ) 3 SiO 1/2 unit 8 mol%, (CH 3 ) 2 SiO unit 56 mol% and (CH 3 ) XSiO A linear siloxane compound comprising 36 mol% (wherein X is a group represented by the structural formula (1)) Note) 4 parts, as a reaction retarder, 0.3 parts of acetylene alcohol and 900 parts of toluene / methyl ethyl ketone (= 80/20) mixed solvent were uniformly mixed, and as a platinum catalyst, An amount of 100 ppm as platinum was added and mixed uniformly to prepare a peelable cured film-forming silicone composition.
参考例
密着性向上剤として、下記式（４）で示されるシロキサン化合物（密着性向上剤Ｃ−２と表記）を用いた以外は、実施例１と同様にして剥離性硬化皮膜形成用シリコーン組成物を調製した。
比較例１
密着性向上剤を未配合とした以外は、実施例１と同様にして剥離性硬化皮膜形成用シリコーン組成物を調製した。
Comparative Example 1
A peelable cured film-forming silicone composition was prepared in the same manner as in Example 1 except that the adhesion improver was not blended.
比較例２
密着性向上剤を、γ‐グリシドキシプロピルトリメトキシシラン（密着性向上剤Ｃ−３と表記）に代えた以外は、実施例１と同様にして剥離性硬化皮膜形成用シリコーン組成物を調製した。
Comparative Example 2
A silicone composition for forming a peelable cured film was prepared in the same manner as in Example 1 except that the adhesion improver was replaced with γ-glycidoxypropyltrimethoxysilane (denoted as adhesion improver C-3). did.
比較例３
密着性向上剤を、ビニルトリエトキシシラン（密着性向上剤Ｃ−４と表記）に代えた以外は、実施例１と同様にして剥離性硬化皮膜形成用シリコーン組成物を調製した。
Comparative Example 3
A peelable cured film-forming silicone composition was prepared in the same manner as in Example 1 except that the adhesion improver was replaced with vinyltriethoxysilane (denoted as adhesion improver C-4).
比較例４
密着性向上剤を、下記式（５）で示されるメタクリロキシプロピルトリメトキシランとポリメチルハイドロジェンシロキサンの反応物（密着性向上剤Ｃ−５と表記）に代えた以外は、実施例１と同様にして剥離性硬化皮膜形成用シリコーン組成物を調製した。
Example 1 except that the adhesion improver was replaced with a reaction product of methacryloxypropyltrimethoxylane and polymethylhydrogensiloxane represented by the following formula (5) (denoted as adhesion improver C-5). Similarly, a silicone composition for forming a peelable cured film was prepared.
上記実施例、参考例および各比較例で得られた剥離性硬化皮膜形成用シリコーン組成物について、「密着性」を評価した。結果を表１に併せ示す。
表１から明らかなように、実施例の剥離性硬化皮膜形成用シリコーン組成物は、プラスチックフィルム基材に対する密着性において良好な特性を有していた。 As is clear from Table 1, the peelable cured film-forming silicone compositions of the examples had good characteristics in adhesion to the plastic film substrate.
Claims (1)
（Ａ）１分子中に少なくとも２個のケイ素原子に直接結合したアルケニル基を有するポリオルガノシロキサン １００重量部、
（Ｂ）１分子中に少なくとも３個のケイ素原子に直接結合した水素原子を有し、２５℃における動粘度が１ｍｍ２／ｓ以上であるポリオルガノハイドロジェンシロキサン
０．１〜３０重量部、
（Ｃ）１分子中にケイ素原子に炭素原子を介して結合した、下記式（１）で示されるエポキシ基を有するシロキサン単位を１０モル％以上含有し、かつ、ケイ素原子に直接結合した水素原子を実質的に有さない、前記エポキシ基以外のケイ素原子に結合する有機基がメチル基である重合度が５以上のポリオルガノシロキサン ０．１〜３０重量部、
および
（Ｄ）白金系触媒 触媒量
を含有することを特徴とする剥離性硬化皮膜形成用シリコーン組成物。
(A) 100 parts by weight of a polyorganosiloxane having an alkenyl group directly bonded to at least two silicon atoms in one molecule;
(B) A polyorganohydrogensiloxane having hydrogen atoms directly bonded to at least three silicon atoms in one molecule and a kinematic viscosity at 25 ° C. of 1 mm 2 / s or more
0.1 to 30 parts by weight,
(C) A hydrogen atom containing 10 mol% or more of a siloxane unit having an epoxy group represented by the following formula (1) bonded to a silicon atom via a carbon atom in one molecule and directly bonded to the silicon atom 0.1 to 30 parts by weight of a polyorganosiloxane having a polymerization degree of 5 or more, wherein the organic group bonded to the silicon atom other than the epoxy group is a methyl group ,
And (D) a platinum-based catalyst containing a catalyst amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005027853A JP4757504B2 (en) | 2005-02-03 | 2005-02-03 | Silicone composition for forming a peelable cured film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005027853A JP4757504B2 (en) | 2005-02-03 | 2005-02-03 | Silicone composition for forming a peelable cured film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011026206A Division JP2011132532A (en) | 2011-02-09 | 2011-02-09 | Silicone composition for forming releasable cured film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006213816A JP2006213816A (en) | 2006-08-17 |
| JP4757504B2 true JP4757504B2 (en) | 2011-08-24 |
Family
ID=36977306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005027853A Expired - Fee Related JP4757504B2 (en) | 2005-02-03 | 2005-02-03 | Silicone composition for forming a peelable cured film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4757504B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI519604B (en) * | 2012-07-27 | 2016-02-01 | Ｌｇ化學股份有限公司 | Curable composition |
| JP2016107531A (en) * | 2014-12-08 | 2016-06-20 | 三菱樹脂株式会社 | Release polyester film |
| TW202200674A (en) * | 2020-06-12 | 2022-01-01 | 日商信越化學工業股份有限公司 | Addition-reaction-curable organo-polysiloxane composition, release paper, and release film |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62240363A (en) * | 1986-04-10 | 1987-10-21 | Shin Etsu Chem Co Ltd | Silicone composition for release film |
| TW198054B (en) * | 1992-02-10 | 1993-01-11 | Gen Electric | |
| US5292787A (en) * | 1992-07-30 | 1994-03-08 | General Electric Company | Epoxysilicone controlled release composition |
| JP3022101B2 (en) * | 1993-10-19 | 2000-03-15 | 信越化学工業株式会社 | Release organopolysiloxane composition and release paper |
| JPH0912892A (en) * | 1995-07-04 | 1997-01-14 | Toray Dow Corning Silicone Co Ltd | Silicone rubber composition for in situ molding gasket |
| JPH10245540A (en) * | 1997-03-04 | 1998-09-14 | Toshiba Silicone Co Ltd | Peeling strength modifier, its production and ultraviolet-curing release agent containing the same |
| JP3700908B2 (en) * | 1998-09-25 | 2005-09-28 | 東レ・ダウコーニング株式会社 | Silicone adhesive sheet |
-
2005
- 2005-02-03 JP JP2005027853A patent/JP4757504B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006213816A (en) | 2006-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI622625B (en) | Organosiloxane compositions and coatings, manufactured articles, methods and uses | |
| JP5567296B2 (en) | Peeling regulator, peeling regulator composition, peelable cured film-forming organopolysiloxane composition, and sheet-like substrate having a peelable cured film | |
| TWI567137B (en) | A polyethylene oxide composition for a stripping sheet and a release sheet, and a release sheet | |
| EP0400614B1 (en) | Organopolysiloxane composition for the formation of a peelable cured coating | |
| JPH0791471B2 (en) | Organopolysiloxane composition for peelable film formation | |
| JP5569471B2 (en) | Silicone composition for release paper or release film | |
| JP2011132532A (en) | Silicone composition for forming releasable cured film | |
| JP2020512465A (en) | Heat dissipation gel type silicone rubber composition | |
| EP1221468A1 (en) | Essentially solventless silicone composition for forming cured release coatings | |
| JP5138205B2 (en) | Silicone composition for solvent-free release paper | |
| EP2860232A1 (en) | Emulsion-based high release additive for release sheet, emulsion composition for release sheet, and mold release sheet | |
| JP3813467B2 (en) | Curable silicone release agent composition | |
| JP3607441B2 (en) | Peelable cured film-forming organopolysiloxane composition | |
| JP3368161B2 (en) | Removable cured film-forming organopolysiloxane composition | |
| JPH05171047A (en) | Organopolysiloxane composition for formation of releasable cured film | |
| JP3012309B2 (en) | Curable organopolysiloxane composition | |
| EP3106494A1 (en) | Curable resin composition | |
| JP4757504B2 (en) | Silicone composition for forming a peelable cured film | |
| JP3891260B2 (en) | Curable silicone release agent composition and release paper | |
| JP5077560B2 (en) | Silicone composition for solvent-free release paper | |
| JPH09125004A (en) | Silicone composition for forming peelable and curable coating layer | |
| JP4190336B2 (en) | Curable silicone release agent composition | |
| JP2005314510A (en) | Curable silicone releasing agent composition | |
| JP2007284685A (en) | Silicone releasing agent composition and release coated paper | |
| JPH08217980A (en) | Release agent composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070510 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090805 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090811 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20091013 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20091016 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091111 |
|
| A072 | Dismissal of procedure [no reply to invitation to correct request for examination] |
Free format text: JAPANESE INTERMEDIATE CODE: A072 Effective date: 20100302 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20101109 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110209 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20110218 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110531 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110601 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4757504 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140610 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |