JP2013144373A - Method of manufacturing resin molded article - Google Patents
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本発明は、樹脂成形品の製造方法に関する。 The present invention relates to a method for producing a resin molded product.
液状の熱硬化性樹脂及び液状の硬化剤を金型内に供給し、加熱により硬化させて樹脂成形品を形成するにあたり、熱硬化性樹脂に予め硬化剤を配合し、その配合物を金型内に供給することが行われている（例えば、特許文献１の段落0004参照）。このような方法において樹脂成形品を比較的短時間で形成したい場合には、分解温度の低い硬化剤を選択して熱硬化性樹脂に配合し、熱硬化性樹脂をより速く硬化させることが考えられる。しかしながら、分解温度の低い硬化剤を熱硬化性樹脂に予め配合しておくとポットライフが短くなり、特に夏場の暑い時期には金型内への供給前に硬化反応が進行してゲル化してしまうという問題がある。 When a liquid thermosetting resin and a liquid curing agent are supplied into a mold and cured by heating to form a resin molded product, a curing agent is blended in advance with the thermosetting resin, and the mixture is molded into the mold. (For example, refer to paragraph 0004 of Patent Document 1). In such a method, when it is desired to form a resin molded product in a relatively short time, it is considered to select a curing agent having a low decomposition temperature and mix it with the thermosetting resin to cure the thermosetting resin faster. It is done. However, if a curing agent having a low decomposition temperature is pre-mixed with the thermosetting resin, the pot life is shortened, and the gelation is caused by the hardening reaction progressing before being fed into the mold, especially in the hot summer season. There is a problem of end.
そこで、上記特許文献１では、硬化剤をマイクロカプセル化することによって、金型内への供給前に熱硬化性樹脂の硬化反応が進行することを抑制している。 Therefore, in Patent Document 1, the curing reaction of the thermosetting resin is suppressed from proceeding before being supplied into the mold by microencapsulating the curing agent.
上記したようなマイクロカプセル型硬化剤は、硬化剤、及びマイクロカプセルの壁材となる樹脂を有機溶媒に溶解する工程、その溶液を水中で乳化分散させる工程、有機溶媒を除去する工程等を順次経て製造される。このように複数の工程を経て製造されるため手間がかかり、また専用の設備が必要になることから、コスト高の問題がある。 The above-described microcapsule-type curing agent sequentially includes a step of dissolving the curing agent and the resin that becomes the wall material of the microcapsule in an organic solvent, a step of emulsifying and dispersing the solution in water, a step of removing the organic solvent, and the like. It is manufactured after. Since it is manufactured through a plurality of steps as described above, it takes time and a dedicated facility is required, resulting in a problem of high cost.
本発明は、以上のとおりの事情に鑑みてなされたものであり、樹脂成形品を比較的短時間で簡便に形成可能な樹脂成形品の製造方法を提供することを課題としている。 This invention is made | formed in view of the situation as mentioned above, and makes it the subject to provide the manufacturing method of the resin molded product which can form a resin molded product easily in a comparatively short time.
上記の課題を解決するために、本発明の樹脂成形品の製造方法は、液状の熱硬化性樹脂及び液状の硬化剤を金型内に供給し、加熱により硬化させて樹脂成形品を形成する樹脂成形品の製造方法において、前記熱硬化性樹脂及び前記硬化剤のうち少なくとも一方の成分を成分毎に、前記樹脂成形品の成形温度で溶融する樹脂フィルム状物で包んだ状態にして前記金型内に供給することを特徴とする。 In order to solve the above-mentioned problems, the method for producing a resin molded product according to the present invention supplies a liquid thermosetting resin and a liquid curing agent into a mold and cures them by heating to form a resin molded product. In the method for producing a resin molded product, the gold is prepared by wrapping at least one component of the thermosetting resin and the curing agent for each component with a resin film that melts at a molding temperature of the resin molded product. It is characterized by being supplied into a mold.
この樹脂成形品の製造方法においては、前記樹脂フィルム状物を袋状の形態にして、前記熱硬化性樹脂及び前記硬化剤のうち少なくとも一方の成分を成分毎に包むことが好ましい。 In this method for producing a resin molded article, it is preferable that the resin film is formed into a bag shape and at least one component of the thermosetting resin and the curing agent is wrapped for each component.
本発明によれば、樹脂成形品を比較的短時間で簡便に形成することができる。 According to the present invention, a resin molded product can be easily formed in a relatively short time.
以下、本発明に係る樹脂成形品の製造方法の一実施形態について説明する。
本実施形態に係る樹脂成形品の製造方法においては、液状の熱硬化性樹脂及び液状の硬化剤を成形材料として金型内に供給し、加熱により硬化させて樹脂成形品を形成する。ここで、「液状」とは、流動性を有し、硬化反応が進行していない状態を意味し、固体状とは区別される。
Hereinafter, an embodiment of a method for producing a resin molded product according to the present invention will be described.
In the method for producing a resin molded product according to the present embodiment, a liquid thermosetting resin and a liquid curing agent are supplied as molding materials into a mold and cured by heating to form a resin molded product. Here, “liquid” means a state having fluidity and a curing reaction not progressing, and is distinguished from a solid state.
成形材料として使用することができる液状の熱硬化性樹脂としては、不飽和ポリエステル樹脂、エポキシ樹脂、ビニルエステル樹脂、アクリル樹脂等が挙げられる。これらは一種を単独で用いてもよく、二種以上を組み合わせて使用することもできる。 Examples of the liquid thermosetting resin that can be used as the molding material include unsaturated polyester resins, epoxy resins, vinyl ester resins, and acrylic resins. These may be used individually by 1 type, and can also be used in combination of 2 or more type.
不飽和ポリエステル樹脂は、無水マレイン酸等の不飽和二塩基酸及び無水フタル酸等の飽和二塩基酸と、エチレングリコール等の多価アルコールとを縮合反応させて合成され、分子内に不飽和結合とエステル結合を有するものである。 Unsaturated polyester resins are synthesized by condensation reaction of unsaturated dibasic acids such as maleic anhydride and saturated dibasic acids such as phthalic anhydride and polyhydric alcohols such as ethylene glycol, and unsaturated bonds in the molecule. And having an ester bond.
エポキシ樹脂は、一分子中に２個以上のエポキシ基を有する化合物であり、具体例として、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等が挙げられる。これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。 The epoxy resin is a compound having two or more epoxy groups in one molecule, and specific examples thereof include bisphenol A type epoxy resin, bisphenol AD type epoxy resin, and bisphenol F type epoxy resin. These may be used individually by 1 type, and may be used in combination of 2 or more types.
ビニルエステル樹脂は、分子末端に（メタ）アクリロイル基を有する化合物であり、例えば、分子内にエポキシ基を２個以上有するエポキシ化合物と、（メタ）アクリル酸と、必要に応じて多塩基酸とを付加反応させることにより得られる。 The vinyl ester resin is a compound having a (meth) acryloyl group at a molecular end, for example, an epoxy compound having two or more epoxy groups in the molecule, (meth) acrylic acid, and a polybasic acid as necessary. Is obtained by addition reaction.
アクリル樹脂は、（メタ）アクリル系重合体と、カルボキシル基を有するビニル単量体とで構成される（メタ）アクリルシラップ等が挙げられる。 Examples of the acrylic resin include (meth) acrylic syrup composed of a (meth) acrylic polymer and a vinyl monomer having a carboxyl group.
成形材料として使用することができる液状の硬化剤としては、上記した不飽和ポリエステル樹脂、ビニルエステル樹脂、アクリル樹脂等については、過酸化ベンゾイルやメチルエチルケトンパーオキサイド等の有機過酸化物が挙げられる。エポキシ樹脂については、メチルヘキサヒドロフタル酸無水物、メチルテトラヒドロフタル酸無水物、無水メチルナジック酸無水物等の酸無水物、ｍ−キシリレンジアミン、ジアミノジフェニルメタンアダクト、変性芳香族アミンやそのアダクト等の芳香蔟アミン等が硬化剤として用いることができる。 Examples of the liquid curing agent that can be used as the molding material include organic peroxides such as benzoyl peroxide and methyl ethyl ketone peroxide for the unsaturated polyester resin, vinyl ester resin, and acrylic resin. For epoxy resins, acid anhydrides such as methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic acid anhydride, m-xylylenediamine, diaminodiphenylmethane adduct, modified aromatic amine and its adduct, etc. Aromatic amines can be used as curing agents.
本実施形態において何よりも特徴的なのは、成形材料を金型内に供給するにあたり、液状の熱硬化性樹脂及び液状の硬化剤のうち少なくとも一方の成分を成分毎に樹脂フィルム状物で包んだ状態にして金型内に供給することである。例えば、液状の熱硬化性樹脂及び液状の硬化剤のうち一方の成分を樹脂フィルム状物で包んだ状態にして金型内に供給し、他方の成分を樹脂フィルム状物で包まずに金型内に供給する。又は、液状の熱硬化性樹脂及び液状の硬化剤をそれぞれ個別に樹脂フィルム状物で包んだ状態にして金型内に供給する。つまり、液状の熱硬化性樹脂と液状の硬化剤とを樹脂フィルム状物を介して非接触状態にして金型内に供給する。 What is most characteristic in the present embodiment is that when supplying the molding material into the mold, at least one of the liquid thermosetting resin and the liquid curing agent is wrapped in a resin film for each component. And supplying it into the mold. For example, one component of a liquid thermosetting resin and a liquid curing agent is supplied in a mold in a state of being wrapped in a resin film, and the other component is not wrapped in a resin film. Supply in. Alternatively, the liquid thermosetting resin and the liquid curing agent are individually wrapped in a resin film and supplied into the mold. That is, a liquid thermosetting resin and a liquid curing agent are supplied into the mold in a non-contact state via a resin film.
樹脂フィルム状物は、フィルム状の熱可塑性樹脂で形成されており、樹脂成形品の成形温度で溶融する融点を有する。樹脂成形品の成形温度は、樹脂成形品の形成にあたり熱硬化性樹脂を硬化させる温度であり、使用する硬化剤の分解温度等によって適宜設定される。樹脂フィルム状物は、その溶融前は金型内において液状の熱硬化性樹脂と液状の硬化剤とを非接触状態とし、溶融後は液状の熱硬化性樹脂と液状の硬化剤とを接触させて熱硬化性樹脂を硬化反応可能な状態とする。このため、樹脂フィルム状物は液状の成分を封入できる程度の強度を有していればよく、例えば、厚み５μｍ以上の樹脂フィルム状物を採用することができる。厚みの上限値は溶融性等を考慮すると３００μｍ程度とすることができる。 The resin film is made of a film-like thermoplastic resin and has a melting point that melts at the molding temperature of the resin molded product. The molding temperature of the resin molded product is a temperature at which the thermosetting resin is cured in forming the resin molded product, and is appropriately set depending on the decomposition temperature of the curing agent to be used. Before melting, the resin film-like material is in a non-contact state between the liquid thermosetting resin and the liquid curing agent in the mold, and after melting, the liquid thermosetting resin and the liquid curing agent are brought into contact with each other. Thus, the thermosetting resin is brought into a state capable of curing reaction. For this reason, the resin film-like material should just have the intensity | strength which can enclose a liquid component, for example, the resin film-like material of thickness 5 micrometers or more is employable. The upper limit of the thickness can be set to about 300 μm in consideration of meltability and the like.
樹脂フィルム状物の大きさは液状の成分を封入できれば特に制限されるものではない。いずれか一方の液状の成分の全量を一枚の樹脂フィルム状物で包んでもよいし、小分けして複数枚の樹脂フィルム状物で包んでもよい。 The size of the resin film is not particularly limited as long as a liquid component can be enclosed. The entire amount of any one of the liquid components may be wrapped with a single resin film, or may be divided into a plurality of resin films.
このような樹脂フィルム状物の具体例としては、エチレン−酢酸ビニル共重合体（ＥＶＡ）、低密度ポリエチレン（ＬＤＰＥ）、ポリ塩化ビニル（ＰＶＣ）、ポリ塩化ビニリデン（ＰＶＤＣ）、ポリビニルアルコール（ＰＶＡ）、ポリプロピレン（ＰＰ）、ポリメチルメタクリレート（ＰＭＭＡ）等が挙げられる。なかでもエチレン−酢酸ビニル共重合体は柔軟性を備え、また安価であることから好適であるが、これに限定されず、得られる樹脂成形品の耐熱性等の各種物性に影響の小さい材質を選択すればよい。 Specific examples of such a resin film include ethylene-vinyl acetate copolymer (EVA), low density polyethylene (LDPE), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA). , Polypropylene (PP), polymethyl methacrylate (PMMA) and the like. Among them, the ethylene-vinyl acetate copolymer is preferable because it has flexibility and is inexpensive, but is not limited to this, and a material that has little influence on various physical properties such as heat resistance of the obtained resin molded product is used. Just choose.
樹脂フィルム状物は、袋状の形態にして使用することが望ましい。袋状の形態の樹脂フィルム状物は、液状の成分を封入しやすく、また金型内への設置も容易であり、作業性をより向上させることができる。 The resin film is preferably used in the form of a bag. The bag-like resin film-like material can easily enclose liquid components and can be easily installed in a mold, thereby improving the workability.
成形材料を金型に供給する際の液状の熱硬化性樹脂及び液状の硬化剤の供給順序は特に問わない。例えば、液状の熱硬化性樹脂及び液状の硬化剤のうち一方の成分のみを樹脂フィルム状物で包む場合、樹脂フィルム状物で包んでいない他方の成分を金型内に供給する前もしくは供給した後に、樹脂フィルム状物で包んだ一方の成分を金型内に設置することができる。樹脂フィルム状物で包んだ一方の成分と、樹脂フィルム状物で包んでいない他方の成分とを同時に金型内に設置することもできる。作業性の点から、まず、樹脂フィルム状物で包んだ一方の成分を金型内に設置し、次いで、樹脂フィルム状物で包んでいない他方の成分を金型内に供給することが望ましい。特に使用量の少ない成分を樹脂フィルム状物で包んで金型内に設置し、樹脂フィルム状物が溶融してから他方の成分を供給すると、この供給力によって両方の成分が混合されるため、両方の成分の分散性が良好になり好ましい。なお、液状の熱硬化性樹脂及び液状の硬化剤をそれぞれ個別に樹脂フィルム状物で包んだ場合も金型内への供給順序は特に問わない。 The supply order of the liquid thermosetting resin and the liquid curing agent when supplying the molding material to the mold is not particularly limited. For example, when only one component of a liquid thermosetting resin and a liquid curing agent is wrapped in a resin film, the other component not wrapped in the resin film is supplied before or supplied to the mold. Later, one component wrapped with a resin film can be placed in the mold. One component wrapped with the resin film and the other component not wrapped with the resin film can be placed in the mold at the same time. From the viewpoint of workability, it is desirable to first place one component wrapped in a resin film in a mold and then supply the other component not wrapped in a resin film into the mold. In particular, when the component with a small amount of use is wrapped in a resin film and placed in a mold and the other component is supplied after the resin film has melted, both components are mixed by this supply force. The dispersibility of both components is good, which is preferable. Even when the liquid thermosetting resin and the liquid curing agent are individually wrapped in a resin film, the supply order in the mold is not particularly limited.
成形材料には、本発明の目的が損なわれない範囲で必要に応じて、硬化促進剤、充填剤、カップリング剤、顔料、難燃剤等の添加剤を任意成分として適宜配合することができる。このような任意成分は、金型内に供給する前に、液状の熱硬化性樹脂及び液状の硬化剤のうちいずれか一方の成分に配合しておくことができる。 In the molding material, additives such as a curing accelerator, a filler, a coupling agent, a pigment, a flame retardant, and the like can be appropriately blended as optional components as needed within the range not impairing the object of the present invention. Such an arbitrary component can be blended with either one of the liquid thermosetting resin and the liquid curing agent before being supplied into the mold.
成形材料を金型内に供給した後、成形温度まで加熱された金型の熱によって樹脂フィルム状物が溶融する。この樹脂フィルム状物の溶融によって内包物が放出して液状の熱硬化性樹脂と液状の硬化剤とが金型内で接触、混合し、硬化反応が開始して所望の樹脂成形品を得る。 After the molding material is supplied into the mold, the resin film is melted by the heat of the mold heated to the molding temperature. The inclusion is released by melting of the resin film, the liquid thermosetting resin and the liquid curing agent are contacted and mixed in the mold, and the curing reaction starts to obtain a desired resin molded product.
このように本実施形態に係る方法は、液状の熱硬化性樹脂及び液状の硬化剤のうち少なくとも一方の成分を成分毎に樹脂フィルム状物で包んだ状態にして金型内に供給するため、成形材料を金型内に供給するにあたり、熱硬化性樹脂に予め硬化剤を配合する必要はない。つまり、成形材料を金型内に供給するまで、液状の熱硬化性樹脂と液状の硬化剤とを混合状態とすることなく、それぞれ個別に金型内に供給することができる。これによって、金型内への供給前に熱硬化性樹脂の硬化反応が進行することを抑制でき、熱硬化性樹脂のゲル化を抑えることができる。 As described above, the method according to the present embodiment supplies at least one of the liquid thermosetting resin and the liquid curing agent in a state of being wrapped in a resin film for each component, and is supplied into the mold. In supplying the molding material into the mold, it is not necessary to add a curing agent to the thermosetting resin in advance. That is, the liquid thermosetting resin and the liquid curing agent can be individually supplied into the mold without mixing them until the molding material is supplied into the mold. Thereby, it can suppress that the hardening reaction of a thermosetting resin advances before supply in a metal mold | die, and can suppress gelatinization of a thermosetting resin.
また、本実施形態に係る方法は液状の熱硬化性樹脂及び液状の硬化剤のうち少なくとも一方の成分を成分毎に樹脂フィルム状物で包むという簡便な方法であるので、従来公知のマイクロカプセル化の手法と比べて低コストである。 Further, since the method according to this embodiment is a simple method of wrapping at least one component of a liquid thermosetting resin and a liquid curing agent with a resin film for each component, a conventionally known microencapsulation method is used. Compared to this method, the cost is low.
さらにまた、本方法によれば、熱硬化性樹脂の速硬化に用いる分解温度の低い硬化剤を使用することができる。分解温度の低い硬化剤は、熱硬化性樹脂に予め配合すると熱硬化性樹脂がゲル化しやすくなるなど取扱いが難しいことからこれまで十分に利用されていなかったが、本方法ではゲル化を抑えることができるため取り扱いが簡単となり使用可能な硬化剤の範囲が広がる。例えば、硬化剤である日本油脂（株）製のパーオクタＯ（１０時間半減期温度６５℃）やパーブチルＰＶ（１０時間半減期温度５５℃）は、日本油脂（株）製のパーヘキサＨＣ（１０時間半減期温度８７℃）と比べて分解温度が低く熱硬化性樹脂に予め配合すると熱硬化性樹脂がゲル化しやすくなるため、その取扱いにはパーヘキサＨＣよりも制約があった。本実施形態に係る方法では、パーオクタＯやパーブチルＰＶ等の分解温度の低い硬化剤でも簡単に取り扱うことができる。 Furthermore, according to this method, a curing agent having a low decomposition temperature used for rapid curing of the thermosetting resin can be used. Curing agents with a low decomposition temperature have not been fully used so far because they are difficult to handle, such as when the thermosetting resin is pre-gelled in the thermosetting resin, it is difficult to handle. Can be handled easily and the range of usable curing agents is expanded. For example, Perocta O (10-hour half-life temperature 65 ° C.) and Perbutyl PV (10-hour half-life temperature 55 ° C.) manufactured by NOF Corporation, which are curing agents, are perhexa HC (10 hours) manufactured by NOF Corporation. Compared with Perhexa HC, the decomposition temperature is lower than that of Perhexa HC because the decomposition temperature is low compared to the half-life temperature (87 ° C.) and the thermosetting resin is likely to gel when pre-blended with the thermosetting resin. In the method according to the present embodiment, a curing agent having a low decomposition temperature such as perocta O or perbutyl PV can be easily handled.
このように本実施形態に係る方法は、簡便な方法で分解温度の低い硬化剤を使用して熱硬化性樹脂をより速く硬化させることができるため、樹脂成形品を比較的短時間で簡便に形成することができる。 As described above, the method according to this embodiment can cure the thermosetting resin more quickly by using a curing agent having a low decomposition temperature by a simple method. Can be formed.
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| JP2012004958A Expired - Fee Related JP5821017B2 (en) | 2012-01-13 | 2012-01-13 | Manufacturing method of resin molded products |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59109339A (en) * | 1982-12-13 | 1984-06-25 | Kuraray Co Ltd | Preparation of rubber compound |
| JPS6265724A (en) * | 1985-09-17 | 1987-03-25 | Chiyoda Tech & Ind Co Ltd | Method for kneading in bag |
| JPH03292378A (en) * | 1990-04-10 | 1991-12-24 | Nitto Denko Corp | Microcapsule, adhesive composition using same, and curing method therefor |
| JPH07304968A (en) * | 1994-03-15 | 1995-11-21 | Toray Ind Inc | Microencapsulated curing agent, production thereof, thermosetting resin composition, prepreg, and fiber-reinforced composite material |
| JP2007177151A (en) * | 2005-12-28 | 2007-07-12 | Mitsui Chemicals Inc | Package of propylene-based polymer and method for producing propylene-based polymer composition |
| JP2007296692A (en) * | 2006-04-28 | 2007-11-15 | Canon Chemicals Inc | Manufacturing method for conductive roller |
| JP2008056891A (en) * | 2006-08-04 | 2008-03-13 | Yokohama Rubber Co Ltd:The | Microcapsule type curing agent and curable resin composition containing the same |
-
2012
- 2012-01-13 JP JP2012004958A patent/JP5821017B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59109339A (en) * | 1982-12-13 | 1984-06-25 | Kuraray Co Ltd | Preparation of rubber compound |
| JPS6265724A (en) * | 1985-09-17 | 1987-03-25 | Chiyoda Tech & Ind Co Ltd | Method for kneading in bag |
| JPH03292378A (en) * | 1990-04-10 | 1991-12-24 | Nitto Denko Corp | Microcapsule, adhesive composition using same, and curing method therefor |
| JPH07304968A (en) * | 1994-03-15 | 1995-11-21 | Toray Ind Inc | Microencapsulated curing agent, production thereof, thermosetting resin composition, prepreg, and fiber-reinforced composite material |
| JP2007177151A (en) * | 2005-12-28 | 2007-07-12 | Mitsui Chemicals Inc | Package of propylene-based polymer and method for producing propylene-based polymer composition |
| JP2007296692A (en) * | 2006-04-28 | 2007-11-15 | Canon Chemicals Inc | Manufacturing method for conductive roller |
| JP2008056891A (en) * | 2006-08-04 | 2008-03-13 | Yokohama Rubber Co Ltd:The | Microcapsule type curing agent and curable resin composition containing the same |
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| JP5821017B2 (en) | 2015-11-24 |
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