JPH0311248B2 - - Google Patents
Info
- Publication number
- JPH0311248B2 JPH0311248B2 JP237484A JP237484A JPH0311248B2 JP H0311248 B2 JPH0311248 B2 JP H0311248B2 JP 237484 A JP237484 A JP 237484A JP 237484 A JP237484 A JP 237484A JP H0311248 B2 JPH0311248 B2 JP H0311248B2
- Authority
- JP
- Japan
- Prior art keywords
- mold release
- release agent
- same
- substituted monovalent
- general formula
- 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
Links
- 239000000203 mixture Substances 0.000 claims description 22
- 239000006082 mold release agent Substances 0.000 claims description 20
- 229920001296 polysiloxane Polymers 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 150000001282 organosilanes Chemical class 0.000 claims description 6
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 239000002075 main ingredient Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 11
- -1 3,3,3-trifluoropropyl group Chemical group 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000005055 methyl trichlorosilane Substances 0.000 description 4
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000005047 Allyltrichlorosilane Substances 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- PFMKUUJQLUQKHT-UHFFFAOYSA-N dichloro(ethyl)silicon Chemical compound CC[Si](Cl)Cl PFMKUUJQLUQKHT-UHFFFAOYSA-N 0.000 description 1
- GNVPGBIHGALKRR-UHFFFAOYSA-N dichloro-methyl-propylsilane Chemical compound CCC[Si](C)(Cl)Cl GNVPGBIHGALKRR-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005053 propyltrichlorosilane Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/54—Nitrogen-containing linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は離型剤組成物、特には一液タイプの室
温で基体表面上に離型性皮膜を形成させることの
できる非移行型の新規な離型剤組成物に関するも
のである。
プラスチツク、ゴムなどの成形に当つては、目
的としての成形品の型からの取出しを容易にする
ため、その型の内面に金属石けん溶液や各種シリ
コーンを主剤とする離型剤を塗布するという方法
は汎用化されており、この離型剤についてはシリ
コーンオイル、シリコーングリース、シリコーン
レジン、シリコーンゴムなどのシリコーン系組成
物がすぐれた離型性を示すということから多方面
に使用されている。
しかし、このシリコーンオイル、シリコーング
リース系のものは離型面と接触する成形品に離型
剤が移行し易いために処理サイクルが短かく、得
られた成形品の表面がハジキ現象を起すために塗
料やインクの塗装や印刷が難しくなるという欠点
があり、シリコーンレジン系のものにはそのよう
な欠点は改善されるもののその処理温度が高いた
めにこの処理対象が金属、陶磁器などのような耐
熱性のある基体に限定されるという不利がある。
また、シリコーンゴム系のものは処理温度の低い
ものもあるが、処理時間が長く、また基体との密
着性が劣るという欠点があつた。
本発明はこのような不利を解決したシリコーン
系離型剤組成物に関するもので、これは分子中に
The present invention relates to a mold release agent composition, and particularly to a novel one-component type mold release agent composition that is non-migratable and can form a mold release film on the surface of a substrate at room temperature. When molding plastics, rubber, etc., in order to make it easier to remove the desired molded product from the mold, a method is to apply a metal soap solution or a mold release agent based on various silicones to the inside of the mold. has been widely used, and silicone compositions such as silicone oil, silicone grease, silicone resin, and silicone rubber are used in a wide variety of applications because they exhibit excellent mold release properties. However, with silicone oil and silicone grease, the mold release agent easily transfers to the molded product that comes into contact with the mold release surface, so the processing cycle is short, and the surface of the resulting molded product may cause repellency. Silicone resins have the disadvantage of being difficult to paint or print with paints and inks, and although these disadvantages can be improved, their high processing temperatures make it difficult to process materials such as metals, ceramics, etc. It has the disadvantage of being limited to certain substrates.
Furthermore, although some silicone rubber-based products have low processing temperatures, they have the drawbacks of long processing times and poor adhesion to the substrate. The present invention relates to a silicone mold release agent composition that solves these disadvantages, and which contains silicone in the molecule.
【式】単位と[Formula] Unit and
【式】
（こゝにR1、R2、R3は水素原子または同種ある
いは異種の非置換または置換１価炭化水素基から
選択される基、ａ、ｂは１、２、３から選択され
る数）を少なくとも１個宛含有する有機けい素化
合物を主剤としてなることを特徴とするものであ
る。
すなわち、本発明者らは前記した不利を伴なわ
ないシリコーン系離型剤について種々検討した結
果、前記した[Formula] (where R 1 , R 2 , and R 3 are hydrogen atoms or groups selected from the same or different unsubstituted or substituted monovalent hydrocarbon groups, and a and b are selected from 1, 2, and 3. The main ingredient is an organosilicon compound containing at least one of the following. That is, as a result of various studies on silicone-based mold release agents that do not have the above disadvantages, the present inventors found that the above-mentioned
【式】単位と[Formula] Unit and
【式】単位をその分子中に少なくと
も１個宛有するオルガノシラザンシロキサンポリ
マーが室温または若干の加熱で基体との密着性に
すぐれた被膜を短時間で形成し、このようにして
得られた皮膜がすぐれた離型性を示すということ
を見出すと共に、これが接触する物質に移行する
ことも少なく、このように処理されたものは離型
サイクルが長くなるということを確認して本発明
を完成させた。
本発明の離型剤組成物を構成する主剤としての
オルガノシラザンシロキサンポリマーは例えば一
般式[Formula] An organosilazane siloxane polymer having at least one unit in its molecule forms a film with excellent adhesion to a substrate in a short time at room temperature or with slight heating, and the film thus obtained is The present invention was completed by discovering that it exhibits excellent mold releasability, and also confirming that it is less likely to be transferred to materials it comes in contact with, and that products treated in this way have a longer mold release cycle. . The organosilazane siloxane polymer as the main component constituting the mold release agent composition of the present invention has the general formula
【式】（こゝにR1は前記に同
じ、Ｘはハロゲン原子、０∠ｃ∠４、０∠ｄ∠
４、０∠ｃ＋ｄ∠４）で示されるオルガノポリシ
ロキサンの１種または２種以上と、一般式R2 e
SiX4-e（こゝにR2は前記に同じ、Ｘはハロゲン原
子、ｅは１、２、３から選択される数）で示され
るオルガノシランの１種または２種以上との混合
物をアンモニアまたは第１アミンと反応させるこ
とによつて得ることができる。
上記した一般式[Formula] (where R 1 is the same as above, X is a halogen atom, 0∠c∠4, 0∠d∠
4, one or more organopolysiloxanes represented by 0∠c+d∠4) and the general formula R 2 e
A mixture with one or more organosilanes represented by SiX 4-e (where R 2 is the same as above, X is a halogen atom, and e is a number selected from 1, 2, and 3) is mixed with ammonia. Alternatively, it can be obtained by reacting with a primary amine. General formula above
【式】で示され
るオルガノポリシロキサンは、このR1が水素原
子またはメチル基、エチル基、プロピル基、ブチ
ル基などのアルキル基、ビニル基、アリル基など
のアルケニル基、フエニル基、α−メチルスチレ
ン基などのアリール基、シクロヘキシル基などの
シクロアルキル基、さらにこれらの基の炭素原子
に結合した水素原子の１部または全部をハロゲン
原子、シアノ基など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、シアノメ
チル基などで例示される同種あるいは異種の非置
換または置換１価炭化水素基から選択され、０∠
ｃ∠４、０∠ｄ∠４、０∠ｃ＋ｄ∠４とされるも
のであるが、このｃはこのオルガノポリシロキサ
ンから得られオルガノシラザンシロキサンポリマ
ーの離型性の面から1.8〜2.2とし、ｄについては
その硬化速度の点から1.5〜3.5とすることが好ま
しい。このようなオルガノポリシロキサンとして
は
（ｍは８以上の正数）が例示されるが、このよう
な塩素含有線状ポリロキサンは公知の方法、例え
ば環状オルガノポリシロキサンとジメチルジクロ
ロシラン、エチルジクロロシランなどのようなジ
クロロオルガノシランとを酸によつて平衡化反応
させることによつて容易に得ることができる。
また、前記した一般式R2 eSiX4-eで示されるオ
ルガノシランは、このR2が水素原子または上記
したR1と同一の同種あるいは異種の非置換また
は置換１価炭化水素から選択され、ｅが１、２、
３から選択される数とされるものであるが、これ
にはテトラクロロシラン、メチルトリクロロシラ
ン、ジメチルジクロロシラン、トリメチルクロロ
シラン、エチルトリクロロシラン、ジエチルジク
ロロシラン、プロピルトリクロロシラン、プロピ
ルメチルジクロロシラン、ビニルトリクロロシラ
ン、アリルトリクロロシラン、フエニルトリクロ
ロシラン、ジフエニルジクロロシラン、トリフル
オロプロピルトリクロロシランなどが例示され
る。
このオルガノポリシロキサンとオルガノシラン
との反応はこれらを適宜の有機溶剤に溶解させ、
これにアンモニアまたは第１アミンを接触反応さ
せればよく、この第１アミンとしてはNR3で示
されこのR3が前記したR1と同一の同種あるいは
異種の非置換または置換１価炭化水素から選択さ
れるメチルアミン、エチレンアミン、ブチルアミ
ンなどが例示されるが、これは合成の容易さから
アンモニアとすることがよい。また、この有機溶
剤としてはアンモニアガス、第１アミンに対して
不活性で生成するオルガノシラザンシロキサンポ
リマーをよく溶かすものがよく、ジクロロエタ
ン、トリクロロエタン、メチレンクロライド、テ
トラハイドロフラン、ベンゼン、トルエン、キシ
レンなどが例示される。なお、この反応は発熱反
応であるが、通常は０〜50℃で反応温度を制御し
ながら行えばよい。また、上記した末端塩素含有
オルガノポリシロキサンと塩素含有オルガノシラ
ンの配合比はこの反応で得られるオルガノシラザ
ンシロキサンポリマー中でのシロキサン単位が50
モル％を超えると硬化速度が遅くなるし、接着性
もわるくなり、またシロキサン単位が５％モル以
下では離型性がわるくなるので、このオルガノポ
リシロキサン成分が50〜５モル％の範囲となるよ
うにすることがよい。
このようにして得られたオルガノシラザンシロ
キサンポリマーは処理対象物の種類、用途に応じ
て濃縮あるいは溶剤などでさらに稀釈して離型剤
組成物とされるが、この濃度はオルガノシラザン
シロキサンポリマーが0.1〜10％となるようにジ
クロロエタン、トリクロロエタン、メチレンクロ
ライドなどの塩素系溶剤、トルエン、キシレンエ
ーテル、ヘキサンなどで適宜調整すればよい。こ
の離型剤組成物は刷毛塗り、ロール塗り、噴霧、
浸漬などの方法で処理すべき基体表面に塗布し、
室温または若干の加熱で溶剤を揮発させると室温
下でも10分以内に硬化して離型性皮膜を与える
が、この皮膜は接触する相手物質に移行すること
がなく、基体表面への密着性にもすぐれているの
で、繰り返しの離型に耐えるという有利性が与え
られる。
本発明の離型剤組成物はガラス、木材、ブラス
チツク、金属、コンクリートなどの表面を離型性
にするという用途に使用とされるが、これはまた
連続使用によつて離型性の低下したシリコーン処
理をした各種基体の再処理にも有用とされるの
で、特にゴム、プラスチツクなどの成形品の離
型、剥離紙の製造、鋳物工場などに広く利用する
ことができる。
つぎに本発明の実施例をあげるが、例中におけ
る部、％は重量部、重量％を示したものであり、
例中の離型性はつぎの判定基準による結果を示し
たものである。
（離型性判定基準）
○……離型性良好
△……離型はするがやゝ重い力が必要
×……離型せず、樹脂が破壊する
くり返し回数……皮膜形成離型剤上での連続成形
回数
実施例 １
メチルトリクロロシラン88.8％とジメチルシロ
キサン単位を33個有する末端塩素含有ジメチルポ
リシロキサン11.2％の混合物40ｇｒと、塩化メチ
レン400mlとを反応容器に仕込み、５℃冷却し、
これに冷却を続けながら20℃でアンモニヤガスを
吹込み４時間反応させたのち、30分間加熱還流さ
せて液中に溶解していた過剰のアンモニアを除去
し、冷却後副生した塩化アンモニウムを過した
ところ、
と〔CH3Si（NH）1.5〕80とを主骨格とするメチルシ
ラザンジメチルポリシロキサンポリマーが得られ
た。
つぎに、この液状生成物を不揮発分が１％とな
るように塩化メチレンで稀釈して離型剤組成物を
作り、これを基体上に塗布して２時間放置したと
ころ、この基体上にシリコーン皮膜が形成された
ので、これを試料として下記の３種の樹脂成形品
についての離型性をしらべたところ、後記する第
１表に示したとおりの結果が得られた。
樹脂成形品
(1) ウレタン樹脂
ポリプロピレングリコールトリオール（分子量
3000） 20部
ポリプロピレングリコールポリオール・アクト
コート52−460（武田薬工社製商品名） 80部
フレオン−11（米国ジユポン社製商品名） 10部
ポリイソシアネート・ミリオネートMR（日本
ポリウレタン社製商品名） 96.5部
テトラメチルヘキサジアミン 1.0部
を均一に混合した後、これを50℃に加熱した上
記の離型剤処理をした型に注型して発泡フオー
ム化させ、室温で１時間硬化させて脱型した。
(2) エポキシ樹脂
エポキシ樹脂・エピコート828（シエル化学社
製商品名）100部にトリエチレンテトラミン12
部を均一に混合したのち、これを上記の離型剤
処理したアルミ皿中に注型し、これを室温で２
時間、さらに115℃に30分間加熱して硬化させ
てから、脱型した。
(3) アイオノマー樹脂
アイオノマー樹脂（米国デユポン社製商品
名）を前記離型剤で処理したみがき鋼板上にの
せ、150℃で30分間加熱して溶融させ、その離
型性をテストした。
実施例 ２
メチルトリクロロシラン57.4％、ジメチルジク
ロロシラン33％およびジメチルシロキサン単位を
300個有する末端塩素含有ジメチルポリシロキサ
ン9.6％とからなる混合物40ｇｒに塩化メチレン
400mlを添加し、実施例１と同様に処理したとこ
ろ、無色透明な液状物が得られたが、このものは
分析の結果、
と｛〔CH3Si（NH）1.5〕6〔（CH3）2Si（NH）〕｝80を
主
骨格とするメチルシラザンメチルシロキサンポリ
マーであることが確認された。
つぎにこの生成物を実施例１と同様に塩化メチ
レンで稀釈して離型剤組成物を作り、これについ
て実施例１と同様の離型性テストを行なつたとこ
ろ、後記する第１表に示したとおりの結果が得ら
れた。
比較例
メチルトリクロロシラン40ｇと塩化メチレン
400mlとから実施例１と同じ方法でシラザン化合
物を作つたところ、CH3Si（NH）1.5を主骨格とす
る無色透明な生成物が得られ、これを塩化メチレ
ンで１％に稀釈して得た離型剤組成物の離型性を
実施例１と同じ方法でしらべたところ、つぎの第
１表に示したとおりの結果が得られた。In the organopolysiloxane represented by the formula, R 1 is a hydrogen atom or an alkyl group such as methyl, ethyl, propyl, butyl, alkenyl such as vinyl or allyl, phenyl, α-methyl Aryl groups such as styrene groups, cycloalkyl groups such as cyclohexyl groups, and chloromethyl groups in which part or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc.
3,3,3-trifluoropropyl group, cyanomethyl group, etc., selected from the same or different unsubstituted or substituted monovalent hydrocarbon groups, 0∠
c∠4, 0∠d∠4, 0∠c+d∠4, but this c is set to 1.8 to 2.2 from the viewpoint of mold release properties of the organosilazane siloxane polymer obtained from this organopolysiloxane, and d From the viewpoint of curing speed, it is preferable to set it to 1.5 to 3.5. As such organopolysiloxane, (m is a positive number of 8 or more). Such chlorine-containing linear polyloxane can be prepared by a known method, for example, by combining a cyclic organopolysiloxane with a dichloroorganosilane such as dimethyldichlorosilane or ethyldichlorosilane. It can be easily obtained by equilibration reaction with acid. Further, in the organosilane represented by the general formula R 2 e SiX 4-e , R 2 is selected from a hydrogen atom or the same or different unsubstituted or substituted monovalent hydrocarbon as R 1 described above, e is 1, 2,
3, including tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, ethyltrichlorosilane, diethyldichlorosilane, propyltrichlorosilane, propylmethyldichlorosilane, and vinyltrichlorosilane. Examples include chlorosilane, allyltrichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and trifluoropropyltrichlorosilane. The reaction between organopolysiloxane and organosilane involves dissolving them in an appropriate organic solvent.
This may be subjected to a catalytic reaction with ammonia or a primary amine, and this primary amine is represented by NR 3 , where R 3 is the same or different type of unsubstituted or substituted monovalent hydrocarbon as R 1 described above. Examples include methylamine, ethyleneamine, butylamine, etc., but ammonia is preferably used for ease of synthesis. The organic solvent is preferably one that dissolves well the organosilazane siloxane polymer that is inert to ammonia gas and primary amines, such as dichloroethane, trichloroethane, methylene chloride, tetrahydrofuran, benzene, toluene, and xylene. Illustrated. Although this reaction is an exothermic reaction, it may be carried out while controlling the reaction temperature, usually at 0 to 50°C. In addition, the blending ratio of the above-mentioned terminal chlorine-containing organopolysiloxane and chlorine-containing organosilane is such that the siloxane units in the organosilazane siloxane polymer obtained by this reaction are 50
If the siloxane unit exceeds 5% by mole, the curing speed will be slow and the adhesion will deteriorate, and if the siloxane unit is less than 5% by mole, the mold releasability will deteriorate, so the organopolysiloxane component should be in the range of 50 to 5% by mole. It is better to do so. The organosilazane siloxane polymer obtained in this way is concentrated or further diluted with a solvent depending on the type of object to be treated and the purpose of use, to make a mold release agent composition, but this concentration is 0.1 It may be adjusted as appropriate with a chlorinated solvent such as dichloroethane, trichloroethane, methylene chloride, toluene, xylene ether, hexane, etc. so that the concentration is ~10%. This mold release agent composition can be applied by brushing, rolling, spraying,
Apply it to the surface of the substrate to be treated by dipping or other methods,
When the solvent is evaporated at room temperature or with slight heating, it hardens within 10 minutes even at room temperature and provides a releasable film, but this film does not transfer to the other material it comes into contact with, and it does not adhere well to the substrate surface. This gives it the advantage of being resistant to repeated demolding. The mold release agent composition of the present invention is used to make the surfaces of glass, wood, plastic, metal, concrete, etc. It is said to be useful for reprocessing various silicone-treated substrates, so it can be widely used in mold release of molded products such as rubber and plastic, production of release paper, and foundries. Next, examples of the present invention will be given, in which parts and % indicate parts by weight and % by weight.
The mold releasability in the examples shows the results based on the following criteria. (Mold releasability criteria) ○...Good mold releasability△...Mold releases but requires heavy force ×...Number of times the resin is destroyed without being released...Film-forming mold release agent Example 1: 40g of a mixture of 88.8% methyltrichlorosilane and 11.2% dimethylpolysiloxane containing terminal chlorine having 33 dimethylsiloxane units and 400ml of methylene chloride were placed in a reaction vessel, cooled to 5°C,
Ammonia gas was blown into the solution at 20°C while continuing to cool it, and the mixture was reacted for 4 hours, then heated under reflux for 30 minutes to remove excess ammonia dissolved in the solution, and after cooling, the by-produced ammonium chloride was removed by filtration. Then, A methylsilazanedimethylpolysiloxane polymer having a main skeleton of and [CH 3 Si(NH) 1.5 ] 80 was obtained. Next, this liquid product was diluted with methylene chloride so that the non-volatile content was 1% to prepare a mold release agent composition, which was applied onto a substrate and left for 2 hours. Since a film was formed, this was used as a sample to examine the mold releasability of the following three types of resin molded products, and the results were obtained as shown in Table 1 below. Resin molded products (1) Urethane resin polypropylene glycol triol (molecular weight
3000) 20 parts polypropylene glycol polyol Actocoat 52-460 (trade name manufactured by Takeda Pharmaceutical Co., Ltd.) 80 parts Freon-11 (trade name manufactured by DuPont, USA) 10 parts polyisocyanate millionate MR (trade name manufactured by Nippon Polyurethane Co., Ltd.) After uniformly mixing 96.5 parts of 1.0 part of tetramethylhexadiamine, this was poured into a mold treated with the above mold release agent and heated to 50°C to form a foamed foam, which was then cured at room temperature for 1 hour and demolded. did. (2) Epoxy resin 100 parts of epoxy resin Epicoat 828 (product name manufactured by Ciel Chemical Co., Ltd.) and 12 parts of triethylenetetramine
After mixing the parts uniformly, the mixture was poured into an aluminum plate treated with the above mold release agent, and the mixture was heated at room temperature for 2 hours.
After curing by heating to 115° C. for 30 minutes, the mold was demolded. (3) Ionomer resin Ionomer resin (trade name, manufactured by DuPont, USA) was placed on a polished steel plate treated with the above mold release agent, heated at 150° C. for 30 minutes to melt it, and its mold releasability was tested. Example 2 57.4% methyltrichlorosilane, 33% dimethyldichlorosilane and dimethylsiloxane units
Add methylene chloride to 40g of a mixture of 9.6% dimethylpolysiloxane containing 300 chlorine terminals.
When 400ml was added and treated in the same manner as in Example 1, a colorless and transparent liquid was obtained, but as a result of analysis, It was confirmed that it is a methylsilazane methylsiloxane polymer having {[CH 3 Si(NH) 1.5 ] 6 [(CH 3 ) 2 Si(NH)]} 80 as its main skeleton. Next, this product was diluted with methylene chloride in the same manner as in Example 1 to prepare a mold release agent composition, and a mold release property test was conducted on this in the same manner as in Example 1. The results shown were obtained. Comparative example: 40g of methyltrichlorosilane and methylene chloride
A silazane compound was prepared from 400 ml in the same manner as in Example 1, and a colorless and transparent product having a main skeleton of CH 3 Si (NH) 1.5 was obtained, which was diluted to 1% with methylene chloride. When the mold release properties of the mold release agent compositions were examined in the same manner as in Example 1, the results shown in Table 1 below were obtained.
Claims (1)
いは異種の非置換または置換１価炭化水素から選
択される基、ａ、ｂは１、２、３から選択される
数）を少なくとも１個宛含有する有機けい素化合
物を主剤としてなることを特徴とする離型剤組成
物。 ２ 有機けい素化合物が一般式 （こゝにR1は水素原子または同種あるいは異種
の非置換または置換１価炭化水素基から選択され
る基、Ｘはハロゲン原子、０∠ｃ∠４、０∠ｄ∠
４、０∠ｃ＋ｄ∠４）で示されるオルガノポリシ
ロキサンの１種または２種以上と、一般式R2 e
SiX4-e（こゝにR2は水素原子または同種あるいは
異種の非置換または置換１価炭化水素基から選択
される基、Ｘはハロゲン原子、ｅは１、２、３か
ら選択される数）で示されるオルガノシランの１
種または２種以上との混合物をアンモニアまたは
第１アミンと反応させて得られるものである特許
請求の範囲第１項記載の離型剤組成物。 ３ 有機けい素化合物が一般式 （こゝにR1は水素原子または同種あるいは異種
の非置換または置換１価炭化水素基から選択され
る基、ｍは８以上の正数）で示されるオルガノポ
リシロキサンの１種または２種以上と、一般式
R2 eSiX4-e（こゝにR2は水素原子または同種あるい
は異種の非置換または置換１価炭化水素基から選
択される基、Ｘはハロゲン原子、ｅは１、２、３
から選択される数）で示されるオルガノシランの
１種または２種以上との混合物をアンモニアまた
は第１アミンと反応させて得られるものである特
許請求の範囲第１項記載の離型剤組成物。[Claims] 1 [Formula] unit and [Formula] unit (where R 1 , R 2 , and R 3 are selected from hydrogen atoms or the same or different unsubstituted or substituted monovalent hydrocarbons) in the molecule. 1. A mold release agent composition comprising, as a main ingredient, an organosilicon compound containing at least one group (a and b are numbers selected from 1, 2, and 3). 2 Organosilicon compounds have the general formula (Here, R 1 is a hydrogen atom or a group selected from the same or different unsubstituted or substituted monovalent hydrocarbon groups, X is a halogen atom, 0∠c∠4, 0∠d∠
4, one or more organopolysiloxanes represented by 0∠c+d∠4) and the general formula R 2 e
SiX 4-e (where R 2 is a hydrogen atom or a group selected from the same or different unsubstituted or substituted monovalent hydrocarbon groups, X is a halogen atom, and e is a number selected from 1, 2, and 3) ) 1 of the organosilanes shown in
The mold release agent composition according to claim 1, which is obtained by reacting a species or a mixture of two or more species with ammonia or a primary amine. 3 Organosilicon compounds have the general formula (Here, R 1 is a hydrogen atom or a group selected from the same or different unsubstituted or substituted monovalent hydrocarbon groups, and m is a positive number of 8 or more.) One or more organopolysiloxanes and the general formula
R 2 e SiX 4-e (R 2 is a hydrogen atom or a group selected from the same or different unsubstituted or substituted monovalent hydrocarbon groups, X is a halogen atom, and e is 1, 2, 3
The mold release agent composition according to claim 1, which is obtained by reacting a mixture of one or more organosilanes represented by the following formula with ammonia or a primary amine: .
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP237484A JPS60145815A (en) | 1984-01-10 | 1984-01-10 | mold release agent composition |
| US06/834,906 US4678688A (en) | 1983-12-28 | 1986-02-28 | Method for forming a surface film of cured organosilicon polymer on a substrate surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP237484A JPS60145815A (en) | 1984-01-10 | 1984-01-10 | mold release agent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60145815A JPS60145815A (en) | 1985-08-01 |
| JPH0311248B2 true JPH0311248B2 (en) | 1991-02-15 |
Family
ID=11527470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP237484A Granted JPS60145815A (en) | 1983-12-28 | 1984-01-10 | mold release agent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60145815A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0699561B2 (en) * | 1990-03-23 | 1994-12-07 | 信越化学工業株式会社 | Method for producing silicone block polymer |
| JPH0641309A (en) * | 1992-07-21 | 1994-02-15 | Toray Dow Corning Silicone Co Ltd | Production of diorganosiloxane diorganosilazane copolymer |
| JP3876961B2 (en) * | 2000-06-29 | 2007-02-07 | 信越化学工業株式会社 | Surface treatment agent and water / oil repellent article |
| US6534184B2 (en) * | 2001-02-26 | 2003-03-18 | Kion Corporation | Polysilazane/polysiloxane block copolymers |
| JP6498406B2 (en) * | 2014-09-26 | 2019-04-10 | 株式会社ネオス | Release agent composition |
| EP3368591B1 (en) * | 2015-10-30 | 2019-07-31 | AZ Electronic Materials Luxembourg S.à.r.l. | Method for producing silazane-siloxane copolymers and the use of such copolymers |
| MY190543A (en) * | 2016-02-15 | 2022-04-27 | Merck Patent Gmbh | Silazane-siloxane random copolymers, their production and use |
| TWI730145B (en) * | 2016-07-18 | 2021-06-11 | 德商馬克專利公司 | Formulation for led encapsulation material |
| JP7371592B2 (en) * | 2019-09-27 | 2023-10-31 | 信越化学工業株式会社 | Polysiloxasan compound having an alkoxysilyl group, method for producing the same, and composition and cured product containing the same |
-
1984
- 1984-01-10 JP JP237484A patent/JPS60145815A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60145815A (en) | 1985-08-01 |
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