JP6498406B2 - Release agent composition - Google Patents
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- JP6498406B2 JP6498406B2 JP2014196434A JP2014196434A JP6498406B2 JP 6498406 B2 JP6498406 B2 JP 6498406B2 JP 2014196434 A JP2014196434 A JP 2014196434A JP 2014196434 A JP2014196434 A JP 2014196434A JP 6498406 B2 JP6498406 B2 JP 6498406B2
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- release agent
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- polysiloxane
- organic polysilazane
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- 239000000203 mixture Substances 0.000 title claims description 49
- 239000003795 chemical substances by application Substances 0.000 claims description 43
- 229920001296 polysiloxane Polymers 0.000 claims description 33
- -1 polysiloxane Polymers 0.000 claims description 32
- 229920001709 polysilazane Polymers 0.000 claims description 31
- 239000006082 mold release agent Substances 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 150000002430 hydrocarbons Chemical group 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000548 poly(silane) polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000010068 moulding (rubber) Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Moulds For Moulding Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、離型剤組成物に関し、特に外部金型離型剤に適した離型剤組成物に関する。 The present invention relates to a release agent composition, and more particularly to a release agent composition suitable for an external mold release agent.
従来、ゴム製品を成形する際に、金型からの剥離を容易にすることを目的として、離型剤が使用される。 Conventionally, when a rubber product is molded, a mold release agent is used for the purpose of facilitating peeling from the mold.
離型剤組成物として、一般的にシリコーン、ワックス、界面活性剤またはフッ素成分を主成分とする、もしくはこれらを混合した離型剤が使用される。しかしながら、従来の離型剤は、成形毎あるいは成形数回程度で離型性能の低下が生じる。そのため、成形毎あるいは数回成形毎に離型剤を塗布する必要があり、生産効率が悪いことが問題とされており、従来より離型剤を簡便に塗布することにより連続して成形を可能とする方法が検討されてきた。 As the release agent composition, a release agent containing silicone, wax, surfactant or fluorine component as a main component or a mixture thereof is generally used. However, with conventional mold release agents, the mold release performance deteriorates at every molding or several moldings. Therefore, it is necessary to apply a mold release agent every molding or several times molding, and it is considered that production efficiency is poor. Continuous molding is possible by simply applying a mold release agent. A method has been studied.
簡便に塗布することにより多脱型可能な離型性能を有する離型剤として、ポリオルガノシロキサンをベースとする硬化型シリコーンゴムを離型剤組成物中に含有し、離型膜を焼き付け硬化させる方法（特許文献１）や皮膜形成シリコーンを金型表面をシリコーンアクリル系プライマーで下地処理し、反応性シリコーンオイルを積層し、離型膜を焼き付け硬化させる方法（特許文献２）が提案されている。しかしながら、前者の方法では、金型表面との密着性が不足しており、その離型性能は十分ではない。また、後者は、複数の塗布工程が必要になるといった問題がある。特許文献３は、シロキサンとシランを含みシラザンを含んでいてもよいシリコンベースのコーティング組成物を開示し、実施例では、ポリシラザン＋ポリシロキサン＋ポリシランの組成物、ポリシロキサン＋ポリシランの組成物、ポリシラザン＋ポリシランの組成物が開示されているが、ポリシラザンとポリシロキサンから構成される組成物は開示されていない。 As a release agent having a release property that can be easily removed by simple application, the release agent composition contains a curable silicone rubber based on polyorganosiloxane, and the release film is baked and cured. A method (Patent Document 1) and a method (Patent Document 2) in which a surface of a mold is pretreated with a silicone acrylic primer, a reactive silicone oil is laminated, and a release film is baked and cured are proposed. . However, the former method has insufficient adhesion to the mold surface, and its release performance is not sufficient. Moreover, the latter has a problem that a plurality of coating steps are required. U.S. Patent No. 6,099,077 discloses a silicon-based coating composition that includes siloxane and silane and may contain silazane, and in the examples, polysilazane + polysiloxane + polysilane composition, polysiloxane + polysilane composition, polysilazane. + A composition of polysilane is disclosed, but a composition composed of polysilazane and polysiloxane is not disclosed.
本発明は、上記問題点を解決するためになされたものであり、金型との密着性が良好で１回塗布で多脱型可能な焼き付け型離型剤を提供することを目的とする。 The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a baking mold release agent that has good adhesion to a mold and can be removed multiple times by one application.
即ち本発明は下記項１〜項６の離型剤組成物を提供するものである。
項１． 有機ポリシラザンとポリシロキサンを含有する離型剤組成物において、有機ポリシラザンとポリシロキサンの合計を１００重量部としたとき有機ポリシラザンの配合量が６０〜９０重量部であり、有機ポリシラザンとポリシロキサンが反応しないものである離型剤組成物（但し、シランは含まない）。
項２． 有機ポリシラザンが一般式（１）で表される繰返し単位を有する項１に記載の離型剤組成物。
That is, this invention provides the mold release agent composition of the following items 1-6.
Item 1. In the release agent composition containing organic polysilazane and polysiloxane, when the total amount of organic polysilazane and polysiloxane is 100 parts by weight, the amount of organic polysilazane is 60 to 90 parts by weight, and the organic polysilazane and polysiloxane are reacted. A release agent composition that does not (but does not contain silane) .
Item 2. Item 2. The release agent composition according to Item 1, wherein the organic polysilazane has a repeating unit represented by the general formula (1).
（式中、Ｒ１、Ｒ２は互いに同一または相異なって、水素原子または置換されていてもよい炭化水素基を示す(炭化水素基の隣接する２つの炭素原子間の結合は、エーテル結合（−Ｏ−）、エステル結合（−ＣＯＯ−または-Ｏ−ＣＯ−）、アミド結合（−ＮＨＣＯ−または-ＣＯＮＨ−）、スルホン酸エステル結合（−ＳＯ２−Ｏ−または−Ｏ−ＳＯ２−）で介在されていてもよい。)。少なくともＲ１、Ｒ２のいずれか一方は炭化水素基である。ｎは２以上の整数である。）
項３． ポリシロキサンが一般式（２）で表される項１または２に記載の離型剤組成物。
(In the formula, R 1 and R 2 are the same or different from each other and represent a hydrogen atom or an optionally substituted hydrocarbon group (the bond between two adjacent carbon atoms of the hydrocarbon group is an ether bond ( —O—), ester bond (—COO— or —O—CO—), amide bond (—NHCO— or —CONH—), sulfonate ester bond (—SO 2 —O— or —O—SO 2 —) And at least one of R 1 and R 2 is a hydrocarbon group, and n is an integer of 2 or more.)
Item 3. Item 3. The release agent composition according to Item 1 or 2, wherein the polysiloxane is represented by the general formula (2).
（Ｒ３は、互いに同一または相異なってフェニル基又はアルキル基を表す。ｍは１以上の整数である。）
項４． ポリシロキサンがジメチルポリシロキサンである項１〜３のいずれかに記載の離型剤組成物。
項５． ポリシロキサンの動粘度が２５℃において１０００ｃSt以上である項1〜４のいずれかに記載の離型剤組成物。
項６． 離型剤組成物１００重量部に対して、有機ポリシラザンとポリシロキサンの配合量が０．２５〜１０重量部である項１〜５に記載の離型剤組成物。
(R 3 is the same as or different from each other and represents a phenyl group or an alkyl group. M is an integer of 1 or more.)
Item 4. Item 4. The release agent composition according to any one of Items 1 to 3, wherein the polysiloxane is dimethylpolysiloxane.
Item 5. Item 5. The release agent composition according to any one of Items 1 to 4, wherein the kinematic viscosity of the polysiloxane is 1000 cSt or more at 25 ° C.
Item 6. Item 6. The release agent composition according to Items 1 to 5, wherein the compounding amount of the organic polysilazane and the polysiloxane is 0.25 to 10 parts by weight with respect to 100 parts by weight of the release agent composition.
本発明の離型剤組成物によれば、金型との密着性が良好であるため簡便な塗布方法によりゴム製品を多数回脱型することができる。また、本発明の離型剤組成物は金型との密着性に優れる一方、洗浄剤で剥離することができるため、金型洗浄が容易である。 According to the release agent composition of the present invention, the rubber product can be demolded many times by a simple coating method because of good adhesion to the mold. Moreover, since the mold release agent composition of this invention is excellent in adhesiveness with a metal mold | die, since it can peel with a washing | cleaning agent, metal mold | die washing | cleaning is easy.
以下に、本発明の詳細を実施形態に基づいて更に詳しく説明する。 Below, the detail of this invention is demonstrated in more detail based on embodiment.
本発明の離型剤組成物に含有される有機ポリシラザンは、下記一般式（１）により表される繰返し単位を有する。 The organic polysilazane contained in the release agent composition of the present invention has a repeating unit represented by the following general formula (1).
（式中、Ｒ１、Ｒ２は互いに同一または相異なって、水素原子または置換されていてもよい炭化水素基を示す(炭化水素基の隣接する２つの炭素原子間の結合は、エーテル結合（−Ｏ−）、エステル結合（−ＣＯＯ−または-Ｏ−ＣＯ−）、アミド結合（−ＮＨＣＯ−または-ＣＯＮＨ−）、スルホン酸エステル結合（−ＳＯ２−Ｏ−または−Ｏ−ＳＯ２−）で介在されていてもよい。)。少なくともＲ１、Ｒ２のいずれか一方は炭化水素基である。ｎは２以上の整数である。）
有機ポリシラザンの粘度は通常５〜５０ｍPa・ｓであり、好ましくは１０〜３５ｍPa・ｓである。
(In the formula, R 1 and R 2 are the same or different from each other and represent a hydrogen atom or an optionally substituted hydrocarbon group (the bond between two adjacent carbon atoms of the hydrocarbon group is an ether bond ( —O—), ester bond (—COO— or —O—CO—), amide bond (—NHCO— or —CONH—), sulfonate ester bond (—SO 2 —O— or —O—SO 2 —) And at least one of R 1 and R 2 is a hydrocarbon group, and n is an integer of 2 or more.)
The viscosity of the organic polysilazane is usually 5 to 50 mPa · s, preferably 10 to 35 mPa · s.
Ｒ１、Ｒ２において、炭化水素基としてはアルキル基、アルケニル基、シクロアルキル基、アリール基を挙げることができる。具体的には、メチル基、エチル基、プロピル基、ブチル基等の炭素数１〜４の直鎖又は分岐を有するアルキル基、ビニル基、アリル基等の炭素数２〜４のアルケニル基、シクロへキシル基等の炭素数３〜８のシクロアルキル基、フェニル基等のアリール基を挙げることができる。 In R 1 and R 2 , examples of the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl group. Specifically, a C1-C4 linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, a C2-C4 alkenyl group such as a vinyl group or an allyl group, a cyclo Examples thereof include cycloalkyl groups having 3 to 8 carbon atoms such as a hexyl group and aryl groups such as a phenyl group.
Ｒ１、Ｒ２の置換基としては、ハロゲン原子やトリアルコキシシリル基（-Ｓｉ（ＯＲ）３）（Ｒはメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル又はｔｅｒｔ−ブチルである）、トリクロロシリル基（−ＳｉＣｌ３）等が挙げられる。好ましい置換された炭化水素基は、下記の基を挙げることができる。
―ＣＨ２ＣＨ２Ｓｉ（ＯＭｅ）３、―ＣＨ２ＣＨ２Ｓｉ（ＯＥｔ）３、
―ＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＥｔ）３、―ＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＭｅ）３。
The substituent for R 1 and R 2 is a halogen atom or a trialkoxysilyl group (—Si (OR) 3 ) (R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl. ), A trichlorosilyl group (—SiCl 3 ) and the like. Preferred examples of the substituted hydrocarbon group include the following groups.
—CH 2 CH 2 Si (OMe) 3 , —CH 2 CH 2 Si (OEt) 3 ,
-CH 2 CH 2 CH 2 Si ( OEt) 3, -CH 2 CH 2 CH 2 Si (OMe) 3.
Ｒ１、Ｒ２で表される炭化水素基の隣接する２つの炭素原子間の結合は、エーテル結合（−Ｏ−）、エステル結合（−ＣＯＯ−または-Ｏ−ＣＯ−）、アミド結合（−ＮＨＣＯ−または-ＣＯＮＨ−）、スルホン酸エステル結合（−ＳＯ２−Ｏ−または−Ｏ−ＳＯ２−）等の結合で介在されていてもよい。具体的には、隣接する２つの炭素原子間の結合（−C−C−結合）は、−C−Ｏ−C-、−C−ＣＯＯ−C-、−C−Ｏ−ＣＯ−C-、−C−ＮＨＣＯ−C-、−C−ＣＯＮＨ−C-、−C−ＳＯ２−Ｏ−C-、−C−Ｏ−ＳＯ２−C−のいずれかであってもよい。 The bond between two adjacent carbon atoms of the hydrocarbon group represented by R 1 or R 2 is an ether bond (—O—), an ester bond (—COO— or —O—CO—), an amide bond (— NHCO- or -CONH-), sulfonic acid ester bond (-SO 2 -O- or -O-SO 2 -) may be interposed in the binding, such as. Specifically, a bond between two adjacent carbon atoms ( -C - C -bond) is -C- O- C- , -C- COO- C- , -C- O-CO- C- , - C -NHCO- C -, - C -CONH- C -, - C -SO 2 -O- C -, - C -O-SO 2 - C - may be either.
有機ポリシラザンは単一の繰返し単位から構成されていてもよく、複数の繰返し単位を有していてもよい。複数の繰返し単位を有する有機ポリシラザンとしては例えば下記式で表されるポリシラザンを挙げることができる。 The organic polysilazane may be composed of a single repeating unit or may have a plurality of repeating units. Examples of the organic polysilazane having a plurality of repeating units include polysilazane represented by the following formula.
(式中、ｐ、ｑは、１以上の整数である。)
有機ポリシラザンの側鎖の置換されていてもよい炭化水素基（さらにエーテル結合、エステル結合、アミド結合、スルホン酸エステル結合で炭素−炭素結合が介在されていてもよい）の割合は、Ｒ１、Ｒ２およびＳｉに結合したメチル基をあわせた全ての側鎖の中、通常４０〜１００％であり、好ましくは５０〜８０％である。この場合の全ての側鎖の中の水素原子の割合は、通常６０〜０％であり、好ましくは５０〜２０％である。
(In the formula, p and q are integers of 1 or more.)
The proportion of the hydrocarbon group which may be substituted on the side chain of the organic polysilazane (further, an ether bond, an ester bond, an amide bond or a sulfonic acid ester bond may have a carbon-carbon bond interposed) is R 1 , Among all side chains in which methyl groups bonded to R 2 and Si are combined, it is usually 40 to 100%, preferably 50 to 80%. In this case, the ratio of hydrogen atoms in all side chains is usually 60 to 0%, preferably 50 to 20%.
有機ポリシラザンの市販品としては、ＡＺエレクトロマテリアルズ社のＫｉＯＮ ＭＬ３３、ＫｉＯＮ ＨＴＡ１５００ slow cure、ＫｉＯＮ ＨＴＡ１５００ ｒapid cureを挙げることができる。 Examples of commercially available organic polysilazane include KiON ML33, KiON HTA 1500 slow cure, and KiON HTA 1500 rapid cure manufactured by AZ Electromaterials.
ポリシロキサンは側鎖が非反応性基から構成されるポリシロキサンであり、下記一般式（２）により表される。 Polysiloxane is a polysiloxane whose side chain is composed of non-reactive groups, and is represented by the following general formula (2).
Ｒ３は、互いに同一または相異なってフェニル基、アルキル基等の非反応性基を表す。アルキル基は、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル又はｔｅｒｔ−ブチル、好ましくはメチルである。好ましいポリシロキサンはＲ３がすべてメチル基であるジメチルポリシロキサンである。ポリシロキサンの動粘度は２５℃において通常１０００ｃＳｔ以上であり、好ましくは１０００ｃＳｔ〜８００万ｃＳｔ、より好ましく１０００〜１００００ｃＳｔである。ｍは１以上の整数である。 R 3 is the same as or different from each other and represents a non-reactive group such as a phenyl group or an alkyl group. The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, preferably methyl. A preferred polysiloxane is dimethylpolysiloxane in which R 3 is all methyl groups. The kinematic viscosity of polysiloxane is usually 1000 cSt or more at 25 ° C., preferably 1000 cSt to 8 million cSt, more preferably 1000 to 10000 cSt. m is an integer of 1 or more.
本発明において、一般式（１）で示される有機ポリシラザンの配合量は、有機ポリシラザン、及びポリシロキサンの合計１００重量部に対して、６０〜９０重量部であり、好ましくは７０〜９０重量部である。６０重量部よりも少ない場合は、求める離型性能が得られなくなる。また、９０重量部よりも高い場合は、金型洗浄性が悪くなる。 In this invention, the compounding quantity of organic polysilazane shown by General formula (1) is 60-90 weight part with respect to a total of 100 weight part of organic polysilazane and polysiloxane, Preferably it is 70-90 weight part. is there. When the amount is less than 60 parts by weight, the desired release performance cannot be obtained. Moreover, when higher than 90 weight part, metal mold | die washability worsens.
ポリシロキサンの配合量は、有機ポリシラザン、及びポリシロキサンの合計１００重量部に対して、４０〜１０重量部であり、好ましくは３０〜１０重量部である。 The compounding quantity of polysiloxane is 40-10 weight part with respect to a total of 100 weight part of organic polysilazane and polysiloxane, Preferably it is 30-10 weight part.
有機ポリシラザンとポリシロキサン混合物の配合量は、離型剤組成物１００重量部に対して、通常０．２５〜１０重量部であり、好ましくは０．５〜５重量部である。０．２５重量部よりも低い場合は、求める離型性能が得られなくなる。また、１０重量部よりも高い場合は、金型洗浄性が悪く、また高価になり実用的でない。 The compounding amount of the organic polysilazane and polysiloxane mixture is usually 0.25 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the release agent composition. When the content is lower than 0.25 parts by weight, the desired release performance cannot be obtained. On the other hand, when the content is higher than 10 parts by weight, the mold cleaning property is poor and the cost becomes impractical.
有機ポリシラザンとポリシロキサンの割合、及び離型剤組成物に対する有機ポリシラザンとポリシロキサン混合物の割合を上記範囲とすることによって、離型剤組成物が得られる。 By setting the ratio of the organic polysilazane and the polysiloxane and the ratio of the organic polysilazane and the polysiloxane mixture to the release agent composition within the above ranges, a release agent composition can be obtained.
本発明の離型剤組成物の残部は溶剤である。溶媒は上記有機ポリシラザンとポリシロキサン混合物を溶解し、構造中にヒドロキシ基を含まないもの、例えばヘキサン、オクタン、ノナン、メチルシクロヘキサン、トルエン、キシレン、ジメチルエーテル、ＬＰＧ，ジエチルエーテル等が挙げられる。これらの有機溶剤は、一種単独で使用してもよいし、二種以上を混合して使用してもよい。 The balance of the release agent composition of the present invention is a solvent. The solvent dissolves the above organic polysilazane and polysiloxane mixture and does not contain a hydroxy group in the structure, such as hexane, octane, nonane, methylcyclohexane, toluene, xylene, dimethyl ether, LPG, diethyl ether and the like. These organic solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.
本発明による離型剤組成物は、当該分野において常用されているゴム成形法における用法に従って使用することができ、該離型剤組成物を金型に塗布する方法としては、スプレー塗布、刷毛塗り、ディッピング等が挙げられる。 The release agent composition according to the present invention can be used in accordance with the usage in rubber molding methods commonly used in the field, and as a method of applying the release agent composition to a mold, spray coating, brush coating, etc. , Dipping and the like.
また、本発明による離型剤組成物は、原液、及びメチルシクロヘキサン、シクロヘキサン等の炭化水素系溶剤での希釈、あるいはLPG、DME等の噴射剤を混合したエアゾールでの使用も可能である。 Further, the release agent composition according to the present invention can be used in an undiluted solution and diluted with a hydrocarbon solvent such as methylcyclohexane or cyclohexane, or in an aerosol mixed with a propellant such as LPG or DME.
金型に付着させる離型剤の不揮発成分量は、１ｍ２当り０．１〜１００ｇ、好ましくは１〜３０ｇである。上記の量を金型に塗布することによって離型持続性能が十分に得られる。 The amount of the non-volatile component of the release agent attached to the mold is 0.1 to 100 g, preferably 1 to 30 g, per 1 m 2 . By applying the above amount to the mold, sufficient release performance can be obtained.
通常は、約１５０〜２００℃に設定した金型に上記の離型剤組成物を塗布し、該離型剤組成物中の揮発性成分を蒸発させることによって、該内壁表面上に皮膜を形成させる。この場合、金型に付着させる離型剤組成物中の不揮発成分の付着量は、１ｍ２当り０．１〜１００ｇ、好ましくは１〜３０ｇである。上記の量を金型に塗布することによって離型持続性能が十分に得られる。 Usually, a coating film is formed on the inner wall surface by applying the release agent composition to a mold set at about 150 to 200 ° C. and evaporating the volatile components in the release agent composition. Let In this case, the adhesion amount of the non-volatile component in the release agent composition to be adhered to the mold is 0.1 to 100 g, preferably 1 to 30 g, per 1 m 2 . By applying the above amount to the mold, sufficient release performance can be obtained.
上述のようにして内壁に離型剤皮膜が形成された金型内へ、ゴム材料を設置し、該樹脂組成物を加圧条件下で、加硫させ、成形品を離型させることによって、ゴム成形品が製造される。この場合、該成形品の離型性は実用上十分なものである。 By placing the rubber material in the mold having the release agent film formed on the inner wall as described above, vulcanizing the resin composition under pressure, and releasing the molded product, Rubber molded products are produced. In this case, the mold release property of the molded product is practically sufficient.
なお、対象となるゴム材料としては、当該分野において従来から使用されているものに対して使用でき、特に限定的ではないが、次のゴム種が挙げられる：天然ゴム、アクリルゴム、ニトリルゴム、イソプレンゴム、エチレンプロピレンゴム、クロロプレンゴム、シリコーンゴム、スチレンブタジエンゴム、ブタジエンゴム、ブチルゴム、フッ素ゴム。 In addition, as a target rubber material, although it can be used with respect to what is conventionally used in the said field | area, it is not specifically limited, The following rubber types are mentioned: Natural rubber, acrylic rubber, nitrile rubber, Isoprene rubber, ethylene propylene rubber, chloroprene rubber, silicone rubber, styrene butadiene rubber, butadiene rubber, butyl rubber, fluorine rubber.
以下に、本発明を実施例によって説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
評価に使用した原料を表1に記載した。 The raw materials used for the evaluation are shown in Table 1.
A１〜A２：有機ポリシラザン成分、B１〜B５:ポリシロキサン成分、及び炭化水素系溶剤を混合攪拌し、離型剤組成物を作製した。表２に各離型剤組成物の配合を示す。なお、A成分、B成分を除いた残部はメチルシクロヘキサンである。 A1-A2: Organic polysilazane component, B1-B5: Polysiloxane component, and hydrocarbon solvent were mixed and stirred to prepare a release agent composition. Table 2 shows the composition of each release agent composition. The balance excluding the A component and the B component is methylcyclohexane.
ゴム原料は、エチレンプロピレンゴム３８重量部、充填剤としてカーボン３８重量部、軟化剤として鉱油１８重量部、架橋助剤２重量部、加硫剤４重量部を周知の練りロールで混練りし、未加硫のゴム生地を得たものを使用した。 The rubber raw material is obtained by kneading 38 parts by weight of ethylene propylene rubber, 38 parts by weight of carbon as a filler, 18 parts by weight of mineral oil as a softening agent, 2 parts by weight of a crosslinking aid, and 4 parts by weight of a vulcanizing agent with a known kneading roll, What obtained the unvulcanized rubber cloth was used.
離型性評価
（１）試験用金型（鉄製、成型品サイズ：直径２０ｍｍ×高さ２０ｍｍの円柱）に離型剤をスプレーガンで均一に約３ｇ(溶剤を含む全量)塗布した。
（２）ゴム原料約8ｇを試験用金型に設置し、加熱・加圧条件下で硬化させた。
（３）試験用金型から成型品を剥離したときの荷重をプッシュプルスケールで測定した。
（４）上記（２）、（３）の工程を繰り返し、該成形工程を２０回行った。尚、要した荷重が２５Ｎ未満である場合を○、２５Ｎ以上を×で表した。
Evaluation of releasability (1) About 3 g (total amount including solvent) of a release agent was uniformly applied to a test mold (made of iron, molded product size: 20 mm diameter × 20 mm height cylinder) with a spray gun.
(2) About 8 g of rubber raw material was placed in a test mold and cured under heating and pressure conditions.
(3) The load when the molded product was peeled from the test mold was measured with a push-pull scale.
(4) The steps (2) and (3) were repeated, and the molding step was performed 20 times. In addition, the case where the required load was less than 25N was represented by ◯, and the case where 25N or more was represented by x.
金型洗浄性評価
（１）鉄製テストピース（JIS G 3141）に離型剤を８ｇ塗布し、１７０℃、８時間焼き付けた。（２）離型剤塗布後のテストピースを３０ｗｔ％水酸化カリウム水溶液に、室温、１２時間浸漬した。（３）テストピースを水で洗浄しＦＴ−ＩＲによりテストピース表面の離型剤成分の有無を確認した。
Evaluation of mold cleanability (1) 8 g of a release agent was applied to an iron test piece (JIS G 3141) and baked at 170 ° C. for 8 hours. (2) The test piece after application of the release agent was immersed in a 30 wt% aqueous potassium hydroxide solution at room temperature for 12 hours. (3) The test piece was washed with water, and the presence or absence of a release agent component on the test piece surface was confirmed by FT-IR.
（ケイ素−炭素結合：1250cm‐1、窒素−水素結合1150cm‐1、ケイ素−酸素結合：、ケイ素−窒素結合：700〜800cm‐1）
試験結果は表２に示すとおりである。
(Silicon-carbon bond: 1250 cm -1 , Nitrogen-hydrogen bond 1150 cm -1 , Silicon-oxygen bond :, Silicon-nitrogen bond: 700-800 cm -1 )
The test results are as shown in Table 2.
表２に示されたように、有機ポリシラザンとポリシロキサンを特定の比率で配合した本発明の離型剤組成物は、金型洗浄性および離型性に優れることが示された。一方、ポリシロキサンを含有しないか含有量が少ない場合は、離型性には優れるが金型洗浄性に劣り、有機シラザンを含有しない場合は、離型性および金型洗浄性の両方において劣ることが分かった。 As shown in Table 2, it was shown that the release agent composition of the present invention in which organic polysilazane and polysiloxane were blended at a specific ratio was excellent in mold cleaning properties and mold release properties. On the other hand, when the polysiloxane is not contained or the content is low, the mold releasability is excellent but the mold detergency is inferior. When the organic silazane is not contained, both the mold releasability and the mold detergency are inferior. I understood.
本発明の離型剤組成物は、特にゴム製品を成形する際の離形剤組成物として有用であり、塗布方法が簡便でゴム製品を多数回脱型することができる焼き付け型離型剤として使用することができる。 The mold release agent composition of the present invention is particularly useful as a mold release agent composition for molding rubber products, and is a baking type mold release agent that can be easily demolded many times with a simple application method. Can be used.
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