JP5004465B2 - Molding method for thermosetting polyurethane molded product and mold release agent - Google Patents
Molding method for thermosetting polyurethane molded product and mold release agent Download PDFInfo
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- JP5004465B2 JP5004465B2 JP2005357420A JP2005357420A JP5004465B2 JP 5004465 B2 JP5004465 B2 JP 5004465B2 JP 2005357420 A JP2005357420 A JP 2005357420A JP 2005357420 A JP2005357420 A JP 2005357420A JP 5004465 B2 JP5004465 B2 JP 5004465B2
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- 229920001187 thermosetting polymer Polymers 0.000 title claims description 46
- 238000000465 moulding Methods 0.000 title claims description 44
- 239000004814 polyurethane Substances 0.000 title claims description 41
- 229920002635 polyurethane Polymers 0.000 title claims description 41
- 239000006082 mold release agent Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 32
- 239000003112 inhibitor Substances 0.000 claims description 27
- -1 isocyanate compound Chemical class 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 19
- 229920002545 silicone oil Polymers 0.000 claims description 19
- 229920002050 silicone resin Polymers 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 229910008051 Si-OH Inorganic materials 0.000 claims description 3
- 229910006358 Si—OH Inorganic materials 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 150000002483 hydrogen compounds Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Description
本発明は、熱硬化性ポリウレタン成型品の成型方法及び金型用離型剤に関する。 The present invention relates to a molding method of a thermosetting polyurethane molded product and a mold release agent.
従来のエラストマーの金型成型技術においては、その成型時において成型体を容易に金型から離型するために、原料と金型の接触面に離型剤処理を施すのが一般的である。
これには、離型剤成分を予め溶剤希釈し、スプレーやハケ塗り等で型の内面に塗布し、成型される場合が多い。
しかし、ポリイソシアネートとポリオールからなる液状の熱硬化性ウレタンの成型においては、そのものが接着剤としても用いられるように他部材への密着度が高く、この成型時の離型方法の選択は困難なものとなっている。
In the conventional elastomer mold molding technology, a mold release agent treatment is generally performed on the contact surface between the raw material and the mold in order to easily release the molded body from the mold at the time of molding.
In many cases, the release agent component is diluted with a solvent in advance and applied to the inner surface of the mold by spraying or brushing.
However, in the molding of a liquid thermosetting urethane composed of polyisocyanate and polyol, the adhesiveness to other members is high so that it can be used as an adhesive, and it is difficult to select a mold release method at the time of molding. It has become a thing.
このような金型用離型剤として、一般にはシリコーンオイル系が用いられることが多いが、これ単独では実用性が無いのが現状であり他の材料と組み合わせて用いられる。
例えば、特許文献１ではシリコーンオイル中にポリフルオロアルキル基含有アルコールが併用された離型剤組成物が提案されている。
また、特許文献２ではポリイソシアネート化合物と反応活性な官能基を有した成分が含まれた離型層を形成する離型方法が提案されている。
このような成分は長期間にわたった連続使用環境下において生産性を低減させる汚れの原因に成り得る事が本検討で明らかとなった。
For example, Patent Document 1 proposes a release agent composition in which a polyfluoroalkyl group-containing alcohol is used in combination with silicone oil.
Patent Document 2 proposes a mold release method for forming a mold release layer containing a component having a functional group reactive with a polyisocyanate compound.
It has been clarified in this study that such components can cause soiling that reduces productivity in a continuous use environment for a long period of time.
しかしながら、上記従来例のものにおいては、それぞれつぎのような問題を有している。
上記従来例の特許文献１のようなハロゲン化合物を使用する場合においては、環境上の規制が問題となる場合があり、さらにコストメリット上不利な面がある。また、上記従来例の特許文献２のような成分では、長期間に亙り連続して使用した際に汚れが生じ、生産性を低下させることとなる。
However, each of the above conventional examples has the following problems.
In the case of using the halogen compound as in Patent Document 1 of the above conventional example, environmental regulations may be a problem, and there is a disadvantage in terms of cost merit. In addition, in the component as described in Patent Document 2 of the above-mentioned conventional example, when it is continuously used over a long period of time, dirt is generated and productivity is lowered.
本発明は、上記課題に鑑み、長期間に亙る繰り返し成型においても金型や成型品を汚すことを抑制することができ、磨きや清掃を行わなくても連続成型することが可能となる熱硬化性ポリウレタン成型品の成型方法及び金型用離型剤の提供を目的とする。 In view of the above problems, the present invention can suppress the mold and molded product from being soiled even in repeated molding over a long period of time, and can be continuously molded without polishing or cleaning. An object of the present invention is to provide a method for molding a flexible polyurethane molded product and a mold release agent.
本発明は、上記課題を解決するため、つぎのように構成した熱硬化性ポリウレタン成型品の成型方法及び金型用離型剤を提供するものである。
本発明は、イソシアネート化合物を含む熱硬化性ウレタン材料を、金型に注型して脱型することにより熱硬化性ポリウレタン成型品を成型する成型方法であって、
前記熱硬化性ウレタン材料が接触する前記金型との界面に、活性水素化合物を含有する離型剤と前記活性水素化合物と前記イソシアネート化合物の反応を阻害する阻害剤とを共存させて成型する工程を有することを特徴としている。
また、本発明の熱硬化性ポリウレタン成型品の成型方法は、前記離型剤と阻害剤とを共存させて成型する工程は、前記離型剤中に前記阻害剤を含む離型剤を前記金型に塗布して成型することを特徴としている。
また、本発明の熱硬化性ポリウレタン成型品の成型方法は、前記阻害剤が、ポリウレタン原料の安定剤であることを特徴としている。
また、本発明の熱硬化性ポリウレタン成型品の成型方法は、前記阻害剤が、塩基触媒の作用を阻害する酸であることを特徴としている。
また、本発明の熱硬化性ポリウレタン成型品の成型方法は、前記塩基触媒の作用を阻害する酸が、リン酸エステルであることを特徴としている。
また、本発明の熱硬化性ポリウレタン成型品の成型方法は、前記離型剤が、シリコーンオイルとシリコーンレジンの混合物を溶剤希釈したものからなることを特徴としている。
また、本発明の金型用離型剤は、金型に塗布する金型用離型剤であって、
前記金型用離型剤中に、活性水素化合物と、前記活性水素化合物とイソシアネート化合物の反応を阻害する阻害剤が含まれていることを特徴としている。
また、本発明の金型用離型剤は、前記阻害剤が、ポリウレタン原料の安定剤であることを特徴としている。
また、本発明の金型用離型剤は、前記阻害剤が、塩基触媒の作用を阻害する酸であることを特徴としている。
また、本発明の金型用離型剤は、前記塩基触媒の作用を阻害する酸が、リン酸エステルであることを特徴としている。
また、本発明の金型用離型剤は、前記金型用離型剤に含まれる活性水素化合物が、シリコーンオイルとシリコーンレジンの混合物に含まれるＳｉ−ＯＨ基であることを特徴としている。
In order to solve the above-described problems, the present invention provides a molding method for a thermosetting polyurethane molded product and a mold release agent configured as follows.
The present invention is a molding method for molding a thermosetting polyurethane molded article by casting a thermosetting urethane material containing an isocyanate compound into a mold and removing the mold.
A step of coexisting a mold release agent containing an active hydrogen compound and an inhibitor that inhibits the reaction of the active hydrogen compound and the isocyanate compound at the interface with the mold in contact with the thermosetting urethane material; It is characterized by having.
Further, in the molding method of the thermosetting polyurethane molded article of the present invention, the step of molding in the presence of the mold release agent and the inhibitor includes the step of molding the mold release agent containing the inhibitor in the mold release agent. It is characterized by being applied to a mold and molded .
Also, method of molding thermosetting polyurethane molded article of the present invention, the inhibitor is characterized by a stabilizer for polyurethane raw materials.
Moreover, the molding method of the thermosetting polyurethane molded article of the present invention is characterized in that the inhibitor is an acid that inhibits the action of a base catalyst.
Moreover, the molding method of the thermosetting polyurethane molded article of the present invention is characterized in that the acid that inhibits the action of the base catalyst is a phosphate ester.
Moreover, the molding method of the thermosetting polyurethane molded product of the present invention is characterized in that the mold release agent is obtained by diluting a mixture of silicone oil and silicone resin with a solvent .
Also, the mold for the release agent of the present invention is a mold release agent for the mold to be applied to the mold,
The mold release agent includes an active hydrogen compound and an inhibitor that inhibits the reaction between the active hydrogen compound and the isocyanate compound.
The mold release agent of the present invention is characterized in that the inhibitor is a stabilizer for a polyurethane raw material.
The mold release agent of the present invention is characterized in that the inhibitor is an acid that inhibits the action of a base catalyst.
In the mold release agent of the present invention, the acid that inhibits the action of the base catalyst is a phosphate ester.
The mold release agent of the present invention is characterized in that the active hydrogen compound contained in the mold release agent is a Si—OH group contained in a mixture of silicone oil and silicone resin .
本発明によれば、長期間に亙る繰り返し成型においても金型や成型品を汚すことを抑制することができ、磨きや清掃を行わなくても連続成型することが可能となる熱硬化性ポリウレタン成型品の成型方法及び金型用離型剤を実現することができる。 According to the present invention, it is possible to suppress molds and molded products from being soiled even in repeated molding over a long period of time, and thermosetting polyurethane molding that enables continuous molding without polishing or cleaning. An article molding method and a mold release agent can be realized.
本発明によれば、長期に亙って連続して安定した熱硬化性ポリウレタン成型品の成型方法を実現すること可能となるが、それは本発明者らの鋭意研究した結果による、つぎのような知見に基づくものである。
まず、本発明者らは、金型上に離型剤を塗布した熱硬化性ポリウレタンの成型方法において、その脱型の容易さ、離型力よりも、むしろ繰り返し使用における金型汚染や、そこから由来する成型品の曇りの発生を抑えることに主眼をおいて、検討を加えた。
また、含ハロゲン系の化合物を使う事なく、さらに環境上の規制も考慮して炭化水素系の溶剤に充分に溶解するものを選択した。
そこで、本発明者らはシリコーンオイル、シリコーンレジンをベースとし、これに可溶な炭化水素系溶剤アクトレル（エクソン化学（株）製）にて成型方法の確立を目的とした。
シリコーンオイル単独では金型への密着性が充分でなく、液状の熱硬化性ポリウレタン原料を注入した際に金型内に一緒に流れ出てしまい、充分な離型効果が得られない。そこでシリコーンレジンを混合させる事により金型密着性が向上し、安定した離型性を確保できる。
しかし、このように炭化水素系溶剤にシリコーンオイル、シリコーンレジンを混合させた離型剤では、離型剤塗布、熱硬化性ポリウレタン原料の投入、熱硬化、脱型の工程を繰り返していると、次第に金型上に白濁汚れの異物が蓄積する。
これが成型品へ移行してしまい、成型品の透明度が失われる汚れとなる結果となった。
According to the present invention, it becomes possible to realize a molding method of a thermosetting polyurethane molded article which is continuously and stable over a long period of time. This is based on the results of earnest research by the present inventors. Based on knowledge.
First, in the method of molding a thermosetting polyurethane in which a mold release agent is applied on a mold, the present inventors, rather than the ease of mold release and the mold release force, rather than mold contamination in repeated use, The study was conducted with a focus on suppressing the occurrence of cloudiness in the molded product derived from the above.
In addition, without using halogen-containing compounds, those that are sufficiently soluble in hydrocarbon solvents were selected in consideration of environmental regulations.
Therefore, the present inventors have aimed to establish a molding method using a hydrocarbon solvent actrel (made by Exxon Chemical Co., Ltd.) based on silicone oil and silicone resin and soluble in this.
Silicone oil alone does not have sufficient adhesion to the mold, and when the liquid thermosetting polyurethane raw material is injected, it flows out into the mold together, and a sufficient release effect cannot be obtained. Therefore, by mixing the silicone resin, the mold adhesion is improved, and a stable releasability can be secured.
However, in the release agent in which silicone oil and silicone resin are mixed in the hydrocarbon solvent in this way, when the release agent coating, the introduction of the thermosetting polyurethane raw material, the thermosetting, and the demolding process are repeated, Gradually foreign matter of cloudy dirt accumulates on the mold.
This shifted to a molded product, resulting in a stain that lost the transparency of the molded product.
このような現象が発生した場合、連続して生産するライン上では一度止めて、金型を取り出して磨き作業工程を入れて汚れを落とす必要性が出てくる。
これは生産性の大幅な低下を招いてしまうことなる。
熱硬化性ポリウレタンの生産上では、金型上に付着したポリウレタン樹脂はインライン化して容易に機械的に除去できる。しかし、金型に固着してしまう白濁汚れは容易に落ちず、装置を止める必要が生じ、連続生産においてはこれが最大の問題となる。
When such a phenomenon occurs, it becomes necessary to stop once on a continuous production line, take out a mold, and perform a polishing work process to remove dirt.
This leads to a significant decrease in productivity.
In the production of thermosetting polyurethane, the polyurethane resin adhering to the mold can be inlined and easily removed mechanically. However, the cloudy dirt that adheres to the mold is not easily removed, and it is necessary to stop the apparatus. This is the biggest problem in continuous production.
そのため、本発明者らはこの金型付着の発生原因を特定し、熱硬化性ポリウレタンの長期に亙っての安定した成型方法を確立すべく、鋭意検討を重ねた結果、熱硬化性ポリウレタン成型品の白濁汚れがつぎのような原因によることを突き止めた。
すなわち、生産性の低下を招く金型上の白濁固着汚れは、熱硬化性ポリウレタン原料中に含まれる反応性が高いイソシアネート化合物が、離型剤中の活性水素化合物の成分と反応してしまう。
これが度重なる連続注型生産工程において次第に金型汚れとして蓄積し、熱硬化性ポリウレタン成型品の白濁汚れの原因となることが見出された。
ここで挙げた例における離型剤中の活性水素化合物は、具体的にはシリコーンオイル、シリコーンレジン中に含まれるＳｉ−ＯＨ基を指すが、本発明はこれらに限られるものではない。
例えば、離型剤成分で熱硬化性エラストマー原料と反応し得る成分が離型剤中に微量でも含まれている場合、初期段階では離型性、金型・成型品の汚れ程度が良くても繰り返し使用によって微量成分が蓄積される。これにより、金型の白濁固着汚れ、及び成型品への曇りの移行を招き、生産性の低下を招く。
Therefore, the present inventors have identified the cause of the adhesion of the mold, and as a result of intensive studies to establish a stable molding method for a long period of thermosetting polyurethane, thermosetting polyurethane molding We found out that the cloudiness of the product was due to the following reasons.
That is, in the cloudy fixed stain on the mold that causes a decrease in productivity, the highly reactive isocyanate compound contained in the thermosetting polyurethane raw material reacts with the active hydrogen compound component in the release agent.
It has been found that this gradually accumulates as mold stains in the repeated continuous casting production process and causes white turbid stains of thermosetting polyurethane molded products.
The active hydrogen compound in the release agent in the examples given here specifically refers to Si—OH groups contained in silicone oil and silicone resin, but the present invention is not limited thereto.
For example, when the release agent component that can react with the thermosetting elastomer raw material is contained in a small amount in the release agent, the mold release property and the degree of contamination of the mold / molded product may be good at the initial stage. Trace components accumulate due to repeated use. Thereby, the cloudiness fixation dirt of a metal mold | die and the transfer of the cloudiness to a molded article are caused, and the fall of productivity is caused.
ここでは、特に金型密着性を向上させるために添加しているシリコーンレジンの方が特に活性水素官能基が多く、汚れ発生の要因として大きい。
このようなことから、原材料と接触する界面である離型剤成分の存在する金型界面部分にこの反応を阻害する成分を共存させることにより、長期間に亙って連続して離型剤塗布、熱硬化性ポリウレタン原料の投入、熱硬化、脱型の工程を続けられる量産手法及び金型用離型剤を見出した。
この反応活性の高い原料中のイソシアネート化合物と離型剤中に含まれる活性水素化合物の反応を阻害するには、イソシアネートの反応を遅延させる化合物が適用される。
例えば、プレポリマー法で作られるポリウレタン原料の安定剤や、型内で反応を進行させる塩基触媒の作用を阻害する酸（例えば、リン酸エステル）などが挙げられる。
阻害剤は離型剤そのものに混合して混合物として用いても、二工程に別けて、金型の内面に離型剤と阻害剤とを個別に塗布し、これらを金型界面に共存させても構わない。
Here, especially the silicone resin added to improve the mold adhesion has a larger number of active hydrogen functional groups, which is a major cause of contamination.
For this reason, it is possible to apply a release agent continuously over a long period by coexisting a component that inhibits this reaction in the mold interface portion where the release agent component, which is an interface that contacts the raw material , exists. The present inventors have found a mass production method and a mold release agent capable of continuing the steps of charging thermosetting polyurethane raw material, thermosetting and demolding .
In order to inhibit the reaction between the isocyanate compound in the raw material having a high reaction activity and the active hydrogen compound contained in the release agent, a compound that delays the reaction of the isocyanate is applied.
Examples thereof include a stabilizer for a polyurethane raw material produced by a prepolymer method, and an acid (for example, a phosphate ester) that inhibits the action of a base catalyst that causes a reaction to proceed in a mold.
Even if the inhibitor is mixed with the mold release agent itself and used as a mixture , the mold release agent and the inhibitor are individually applied to the inner surface of the mold and separated from each other in two steps. It doesn't matter.
このような手法により、長期に亙って連続して安定した熱硬化性ポリウレタン成型品の成型方法を実現することが可能となる。
すなわち、ポリイソシアネートとポリオールからなる熱硬化性ポリウレタンの金型成型で離型剤塗布、原料投入、熱硬化、脱型を繰り返し行って量産される設備において、生産効率の向上を図ることが可能となる。
より具体的には、離型剤塗布、原料投入、熱硬化、脱型を繰り返した連続成型においても、長期間に亙って成型品の曇り等の発生を抑え、金型への汚れ付着を低減し、金型の磨き作業頻度を減収させることが可能となり、生産効率を向上させることができる。
By such a method, it is possible to realize a molding method of a thermosetting polyurethane molded product that is continuously stable over a long period of time.
In other words, it is possible to improve production efficiency in facilities that are mass-produced by repeatedly applying mold release agents, charging raw materials, thermosetting, and demolding by molding a thermosetting polyurethane made of polyisocyanate and polyol. Become.
More specifically, even in continuous molding where release agent application, raw material charging, thermosetting, and demolding are repeated, the occurrence of fogging of the molded product is suppressed over a long period of time, and dirt adheres to the mold. This makes it possible to reduce the frequency of mold polishing work and improve production efficiency.
以下、本発明のイソシアネート化合物を含む熱硬化性ウレタン材料を、金型に注型して脱型することにより熱硬化性ポリウレタン成型品を成型する成型方法を適用した実施例およびに比較例について説明する。
ただし、本発明はこれらの実施例および比較例によって、何ら限定されるものではない。
ここでは、１３０℃の金型上への離型剤塗布、熱硬化性ポリウレタン原料の投入、熱硬化、脱型を１ｓｈｏｔとした一つのサイクルとした。
そして、金型上の汚れとその汚れがポリウレタン成型品上に移行した白濁曇りが起こるまで、どの程度連続して成型ができるかを指標とした。
また、ここでは熱硬化性ポリウレタンを用いた精密部品として電子写真技術に用いられるクリーニングブレードの製造ラインを例として取り上げた。
Hereinafter, a thermosetting urethane material containing the isocyanate compound of the present invention is cast into a mold and demolded, and examples of applying a molding method for molding a thermosetting polyurethane molded product and comparative examples are described. To do.
However, the present invention is not limited to these examples and comparative examples.
Here, it was set as one cycle which made 1shot the application | coating of the mold release agent on a 130 degreeC metal mold | die, injection | throwing in of the thermosetting polyurethane raw material, thermosetting, and mold release.
Then, the index was the degree of continuous molding until the dirt on the mold and the cloudiness clouding in which the dirt was transferred onto the polyurethane molded product.
Further, here, a production line of a cleaning blade used in electrophotographic technology as a precision part using thermosetting polyurethane is taken as an example.
熱硬化製ポリウレタンの原料としては、アジペート系ウレタンエラストマー１００質量部（Ｍｎ２０００ ＮＣＯ６．２５質量％ ）のプレポリマーに対し硬化剤をつぎのように選択した。
すなわち、１，４−ブタンジオール３．７質量部、トリメチロールプロパン１．９質量部にＴＥＤＡ１０００ｐｐｍを選択した。
そして、これらを二成分混合注型機を用いて混合した原料を用いた。
金型はＮＡＫ５５（大同特殊鋼（株）製）、この上にハードクロムメッキを施したもので実施した。
As a raw material for thermosetting polyurethane, a curing agent was selected as follows with respect to a prepolymer of 100 parts by mass of adipate-based urethane elastomer (Mn2000 NCO 6.25% by mass).
That is, TEDA 1000 ppm was selected for 3.7 parts by mass of 1,4-butanediol and 1.9 parts by mass of trimethylolpropane.
And the raw material which mixed these using the 2 component mixing casting machine was used.
The mold was NAK55 (Daido Special Steel Co., Ltd.), which was plated with hard chrome.
また、離型剤としてはシリコーンオイルＡ（ネオス（株）製）シリコーンレジンＡ（ネオス（株）製）、希釈溶剤としてアクトレル（エクソン化学（株）製）、ウレタン化反応の阻害剤として、２−Ｅｔｈｙｌｈｅｘｙｌ Ａｃｉｄ Ｐｈｏｓｐｈａｔｅを用いた。
その際、シリコーンオイルとシリコーンレジンを所定の質量比で混合し、これをアクトレルで２０倍に希釈して離型剤とした。
さらに、金型界面にイソシアネート反応阻害剤を共存させるため、２−Ｅｔｈｙｌｈｅｘｙｌ Ａｃｉｄ Ｐｈｏｓｐｈａｔｅを離型剤中に所定量加えた実施例１〜３と、所定量加え又は加えていない比較例１〜２とを比較した。
添加量はシリコーンオイルとシリコーンレジンの合計量の質量比で記載した。
評価は、金型上の汚れが発生するまで離型剤塗布−原料の金型投入−熱硬化−脱型のサイクルが何回まで持ちこたえ得るかを、離型剤としての弊害を考慮して総合的に判断した。
In addition, silicone oil A (manufactured by Neos Co., Ltd.), silicone resin A (manufactured by Neos Co., Ltd.) as a mold release agent, actrel (manufactured by Exxon Chemical Co., Ltd.) as a diluting solvent, 2 as an inhibitor of urethanization reaction -Ethylhexyl Acid Phosphate was used.
At that time, the silicone oil and the silicone resin were mixed at a predetermined mass ratio, and this was diluted 20 times with Actrel to obtain a release agent.
Furthermore, in order to allow an isocyanate reaction inhibitor to coexist on the mold interface, Examples 1-3 in which a predetermined amount of 2-Ethylhexyl Acid Phosphate was added to the mold release agent, and Comparative Examples 1-2 in which a predetermined amount was not added or added, Compared.
The addition amount was described as a mass ratio of the total amount of silicone oil and silicone resin.
The evaluation is based on how many times the cycle of application of mold release agent-raw material mold injection-thermosetting-mold release can last until dirt on the mold occurs, taking into account the adverse effects as a mold release agent. Judgment.
実施例１〜３及び比較例１〜２において、シリコーンオイルとシリコーンレジンを以下の質量部混合して上記手法で調整し、また上記阻害剤を以下の量添加し、それぞれについて評価試験を行った。結果を表１に示す。
［実施例１］シリコーンオイル７０質量部、シリコーンレジン３０質量部、阻害剤５ｐｐｍ
［実施例２］シリコーンオイル７０質量部、シリコーンレジン３０質量部、阻害剤１００ｐｐｍ
［実施例３］シリコーンオイル７０質量部、シリコーンレジン３０質量部、阻害剤５００ｐｐｍ
（比較例１）シリコーンオイル７０質量部、シリコーンレジン３０質量部、阻害剤０ｐｐｍ
（比較例２）シリコーンオイル９５質量部、シリコーンレジン５質量部、阻害剤０ｐｐｍ
In Examples 1 to 3 and Comparative Examples 1 and 2, silicone oil and silicone resin were mixed in the following mass parts and adjusted by the above method, and the following amount of the inhibitor was added, and an evaluation test was performed for each. . The results are shown in Table 1.
[Example 1] 70 parts by mass of silicone oil, 30 parts by mass of silicone resin, 5 ppm of inhibitor
[Example 2] 70 parts by mass of silicone oil, 30 parts by mass of silicone resin, 100 ppm of inhibitor
[Example 3] 70 parts by mass of silicone oil, 30 parts by mass of silicone resin, 500 ppm of inhibitor
(Comparative Example 1) 70 parts by mass of silicone oil, 30 parts by mass of silicone resin, 0 ppm of inhibitor
(Comparative Example 2) 95 parts by mass of silicone oil, 5 parts by mass of silicone resin, 0 ppm of inhibitor
上記表１より、上記阻害剤が５ｐｐｍ以上５００ｐｐｍ以下、添加された実施例１〜３において、比較例１〜２より好ましい結果が得られると言える。
他にＳｈｏｔ数を延ばすためには、活性水素基の含有量を減らす手段もある。
これは比較例２のように、活性水素基がオイルよりも多いレジンを減らした例であるが、大きな効果は得られず、むしろ離型性が悪くなり成型品がちぎれる等の不具合が発生した。
したがって、活性水素基そのものの量を減らすより、阻害剤を添加する方に効果があると言える。
本実施例によれば、長期間に亙る繰り返し成型においても金型や成型品を汚すことを抑制することができ、連続して安定した熱硬化性ポリウレタン成型品の成型方法を実現することが可能となる。
From Table 1 above, it can be said that in Examples 1 to 3 in which the inhibitor was added in an amount of 5 ppm to 500 ppm , more preferable results than Comparative Examples 1 and 2 were obtained.
In addition, in order to increase the Shot number, there is a means for reducing the content of active hydrogen groups.
This is an example in which the resin having more active hydrogen groups than oil was reduced as in Comparative Example 2, but a great effect was not obtained, but rather problems such as poor releasability and tearing of the molded product occurred. .
Therefore, it can be said that it is more effective in adding an inhibitor than reducing the amount of active hydrogen groups.
According to the present embodiment, it is possible to suppress the mold and the molded product from being soiled even during repeated molding over a long period of time, and it is possible to realize a molding method of a thermosetting polyurethane molded product that is continuously stable. It becomes.
Claims (11)
前記熱硬化性ウレタン材料が接触する前記金型との界面に、活性水素化合物を含有する離型剤と前記活性水素化合物と前記イソシアネート化合物の反応を阻害する阻害剤とを共存させて成型する工程を有することを特徴とする熱硬化性ポリウレタン成型品の成型方法。 A molding method for molding a thermosetting polyurethane molded article by casting a thermosetting urethane material containing an isocyanate compound into a mold and removing the mold.
A step of coexisting a mold release agent containing an active hydrogen compound and an inhibitor that inhibits the reaction of the active hydrogen compound and the isocyanate compound at the interface with the mold in contact with the thermosetting urethane material; A method for molding a thermosetting polyurethane molded product, comprising:
前記金型用離型剤中に、活性水素化合物と、前記活性水素化合物とイソシアネート化合物の反応を阻害する阻害剤が含まれていることを特徴とする金型用離型剤。 A mold release agent applied to the mold,
The mold release agent, wherein the mold release agent contains an active hydrogen compound and an inhibitor that inhibits the reaction between the active hydrogen compound and the isocyanate compound.
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