JP2002012649A - Epoxy resin composition, sheet molding compound and molded product - Google Patents
Epoxy resin composition, sheet molding compound and molded productInfo
- Publication number
- JP2002012649A JP2002012649A JP2000194603A JP2000194603A JP2002012649A JP 2002012649 A JP2002012649 A JP 2002012649A JP 2000194603 A JP2000194603 A JP 2000194603A JP 2000194603 A JP2000194603 A JP 2000194603A JP 2002012649 A JP2002012649 A JP 2002012649A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- weight
- molding compound
- sheet molding
- 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.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 76
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000003677 Sheet moulding compound Substances 0.000 title claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000000049 pigment Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000004088 foaming agent Substances 0.000 claims abstract description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 13
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 13
- 229920003986 novolac Polymers 0.000 claims abstract description 13
- 238000013329 compounding Methods 0.000 claims abstract description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 11
- 239000012779 reinforcing material Substances 0.000 claims description 11
- 239000004604 Blowing Agent Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 52
- 239000011342 resin composition Substances 0.000 description 5
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- -1 for example Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 101100407151 Arabidopsis thaliana PBL6 gene Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 101000777456 Mus musculus Disintegrin and metalloproteinase domain-containing protein 15 Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
(57)【要約】
【課題】 ホルマリンが発生しない成形品であって、剛
性に優れる成形品を得ることができるエポキシ樹脂組成
物を提供する。また、このエポキシ樹脂組成物を用いた
シートモールディングコンパウンドを提供する。また、
このシートモールディングコンパウンドを用いた成形品
を提供する。
【解決手段】 エポキシ樹脂、硬化剤、硬化触媒、発泡
剤及び顔料を含有していて、これらの合計量に対し液状
エポキシ樹脂を少なくとも４０重量％、硬化剤である酸
無水物及びフェノールノボラックを合計で３０〜４０重
量％含有すると共に、前記酸無水物と前記フェノールノ
ボラックの配合比が重量で８：２〜６：４であることを
特徴とするエポキシ樹脂組成物。(57) [Problem] To provide an epoxy resin composition capable of obtaining a molded article which does not generate formalin and has excellent rigidity. Also provided is a sheet molding compound using the epoxy resin composition. Also,
A molded article using the sheet molding compound is provided. SOLUTION: An epoxy resin, a curing agent, a curing catalyst, a foaming agent and a pigment are contained, and at least 40% by weight of a liquid epoxy resin based on the total amount thereof, and a total of an acid anhydride and a phenol novolak as a curing agent are added. An epoxy resin composition characterized by containing 30 to 40% by weight of the above, and the compounding ratio of the acid anhydride and the phenol novolak is 8: 2 to 6: 4 by weight.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、接着剤やシートモ
ールディングコンパウンド（ＳＭＣ）等を製造するのに
好適な液状のエポキシ樹脂組成物及びこれを用いたシー
トモールディングコンパウンド及びこのシートモールデ
ィングコンパウンドを用いた成形品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid epoxy resin composition suitable for producing an adhesive or a sheet molding compound (SMC), a sheet molding compound using the same, and a sheet molding compound using the same. Related to molded products.
【０００２】[0002]
【従来の技術】近年、化学物質が人体に与える影響や環
境問題が大きく取り上げられ、居住空間におけるホルマ
リンの存在によるシックハウス症候群等について関心が
寄せられている。従来、自動車の内装部材や、住宅関連
部材などの成形品を製造するのに、ホルマリン系重縮合
物を含有してなるフェノール樹脂組成物やメラミン樹脂
組成物を用いた接着剤やＳＭＣ等が使用されてきたが、
環境調和の観点からこれらの樹脂組成物の使用が見直さ
れている。そして、ホルマリン系重縮合物を含有してな
る樹脂組成物を使用した部材の低ホルマリン化のため
に、熱処理によるホルマリン除去や、各種ホルマリンキ
ャッチャー剤の添加などの対策が施されている。しか
し、熱処理やホルマリンキャッチャー剤の添加による低
ホルマリン化は一定のホルマリン低減効果をもたらす
が、不充分であり、さらなる改善が望まれている。2. Description of the Related Art In recent years, the influence of chemical substances on the human body and environmental problems have been widely taken up, and sick house syndrome caused by the presence of formalin in living spaces has attracted attention. Conventionally, phenolic resin compositions containing formalin-based polycondensates, adhesives using melamine resin compositions, SMC, etc. have been used to manufacture molded products such as automobile interior parts and housing related parts. Has been
Use of these resin compositions has been reviewed from the viewpoint of environmental harmony. In order to reduce the formalin of a member using a resin composition containing a formalin-based polycondensate, countermeasures such as removal of formalin by heat treatment and addition of various formalin catchers are taken. However, the reduction of formalin by heat treatment or addition of a formalin catcher agent has a certain formalin reduction effect, but is insufficient, and further improvement is desired.
【０００３】そこで、本発明者は先に、ホルマリンが発
生しない部材を得る手段として、硬化剤として酸無水物
を含有するエポキシ樹脂組成物を用いたシートモールデ
ィングコンパウンドを提案している（特開2000−6145公
報）。このような酸無水物を含有するエポキシ樹脂組成
物を用いたシートモールディングコンパウンドによる
と、ホルマリンが発生しない部材を得ることが可能とな
るが、剛性が不充分であり、その改善が求められてい
る。Therefore, the present inventor has previously proposed a sheet molding compound using an epoxy resin composition containing an acid anhydride as a curing agent as means for obtaining a member that does not generate formalin (Japanese Patent Laid-Open No. 2000-2000). -6145 publication). According to the sheet molding compound using the epoxy resin composition containing such an acid anhydride, it is possible to obtain a member that does not generate formalin, but the rigidity is insufficient, and improvement is required. .
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記の事情
に鑑みてなされたもので、その目的とする所は、シート
モールディングコンパウンドを製造するのに好適な液状
のエポキシ樹脂組成物であり、且つホルマリンが発生し
ない成形品であって、剛性に優れる成形品を得ることが
できるエポキシ樹脂組成物を提供することである。ま
た、このエポキシ樹脂組成物を用いていて、ホルマリン
が発生しない成形品であって、剛性に優れる成形品を得
ることができるシートモールディングコンパウンドを提
供することである。また、このシートモールディングコ
ンパウンドを用いて製造されるホルマリンが発生しない
成形品であって、剛性に優れる成形品を提供することで
ある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid epoxy resin composition suitable for producing a sheet molding compound, Another object of the present invention is to provide an epoxy resin composition which does not generate formalin and can obtain a molded article having excellent rigidity. Another object of the present invention is to provide a sheet molding compound using the epoxy resin composition, which is a molded product that does not generate formalin and can obtain a molded product having excellent rigidity. Another object of the present invention is to provide a molded article which is produced by using the sheet molding compound and which does not generate formalin and which has excellent rigidity.
【０００５】[0005]
【課題を解決するための手段】請求項１に係る発明のエ
ポキシ樹脂組成物は、エポキシ樹脂、硬化剤、硬化触
媒、発泡剤及び顔料を含有していて、これらの合計量に
対し液状エポキシ樹脂を少なくとも４０重量％、硬化剤
である酸無水物及びフェノールノボラックを合計で３０
〜４０重量％含有すると共に、前記酸無水物と前記フェ
ノールノボラックの配合比が重量で８：２〜６：４であ
ることを特徴とするエポキシ樹脂組成物である。The epoxy resin composition according to the first aspect of the present invention contains an epoxy resin, a curing agent, a curing catalyst, a foaming agent, and a pigment. At least 40% by weight, and a total of 30 parts by weight of a curing agent, acid anhydride and phenol novolak.
An epoxy resin composition containing the acid anhydride and the phenol novolak in a weight ratio of 8: 2 to 6: 4 by weight.
【０００６】請求項２に係る発明のエポキシ樹脂組成物
は、液状エポキシ樹脂としてビスフェノールＡ型エポキ
シ樹脂を用いることを特徴とする請求項１記載のエポキ
シ樹脂組成物である。[0006] The epoxy resin composition according to the second aspect of the present invention is the epoxy resin composition according to the first aspect, wherein a bisphenol A type epoxy resin is used as the liquid epoxy resin.
【０００７】請求項３に係る発明のエポキシ樹脂組成物
は、エポキシ樹脂、硬化剤、硬化触媒、発泡剤及び顔料
の合計量に対し、融点が１３７〜１４５℃のイミダゾー
ル系硬化触媒を３〜６重量％含有している請求項１又は
請求項２記載のエポキシ樹脂組成物である。The epoxy resin composition according to the third aspect of the present invention comprises an imidazole curing catalyst having a melting point of 137 to 145 ° C. based on the total amount of the epoxy resin, curing agent, curing catalyst, foaming agent and pigment. The epoxy resin composition according to claim 1, wherein the epoxy resin composition contains 1% by weight.
【０００８】請求項４に係る発明のエポキシ樹脂組成物
は、エポキシ樹脂、硬化剤、硬化触媒、発泡剤及び顔料
の合計量に対し、重炭酸塩である発泡剤を２〜６重量％
含有している請求項１乃至請求項３の何れかに記載のエ
ポキシ樹脂組成物である。The epoxy resin composition according to the fourth aspect of the present invention is characterized in that the bicarbonate blowing agent is contained in an amount of 2 to 6% by weight based on the total amount of the epoxy resin, the curing agent, the curing catalyst, the blowing agent and the pigment.
The epoxy resin composition according to any one of claims 1 to 3, which contains the epoxy resin composition.
【０００９】請求項５に係る発明のエポキシ樹脂組成物
は、エポキシ樹脂、硬化剤、硬化触媒、発泡剤及び顔料
の合計量に対し、顔料を１〜２重量％含有している請求
項１乃至請求項４の何れかに記載のエポキシ樹脂組成物
である。[0009] The epoxy resin composition of the invention according to claim 5 contains the pigment in an amount of 1 to 2% by weight based on the total amount of the epoxy resin, the curing agent, the curing catalyst, the blowing agent and the pigment. The epoxy resin composition according to claim 4.
【００１０】請求項６に係る発明のエポキシ樹脂組成物
は、エポキシ樹脂、硬化剤、硬化触媒、発泡剤及び顔料
の合計量１００重量部に対し、さらに無機粉末充填材を
５〜３５重量部の割合で配合している請求項１乃至請求
項５の何れかに記載のエポキシ樹脂組成物である。The epoxy resin composition of the invention according to claim 6 further comprises 5 to 35 parts by weight of an inorganic powder filler based on 100 parts by weight of the total amount of the epoxy resin, the curing agent, the curing catalyst, the blowing agent and the pigment. The epoxy resin composition according to any one of claims 1 to 5, which is blended in a ratio.
【００１１】請求項７に係る発明のシートモールディン
グコンパウンドは、請求項１乃至請求項６の何れかに記
載のエポキシ樹脂組成物を繊維質の補強材に含浸してな
るシートモールディングコンパウンドである。A sheet molding compound according to a seventh aspect of the present invention is a sheet molding compound obtained by impregnating a fibrous reinforcing material with the epoxy resin composition according to any one of the first to sixth aspects.
【００１２】請求項８に係る発明の成形品は、請求項７
記載のシートモールディングコンパウンドを成形してな
る成形品である。[0012] The molded article of the invention according to claim 8 provides the molded article according to claim 7.
A molded product obtained by molding the sheet molding compound described in the above.
【００１３】[0013]
【発明の実施の形態】以下に本発明の実施の形態を説明
する。Embodiments of the present invention will be described below.
【００１４】本発明のエポキシ樹脂組成物は、エポキシ
樹脂、硬化剤、硬化触媒、発泡剤及び顔料を含有してい
る。そして、エポキシ樹脂、硬化剤、硬化触媒、発泡剤
及び顔料の合計量に対し、液状エポキシ樹脂を少なくと
も４０重量％、硬化剤である酸無水物及びフェノールノ
ボラックを合計で３０〜４０重量％含有している。シー
トモールディングコンパウンドを製造するための樹脂組
成物はガラス繊維等の繊維質補強材を含浸するためには
液状であることが必要であり、この液状化を実現するた
めに、本発明では液状エポキシ樹脂を少なくとも４０重
量％含有するようにしている。なお、ここでいう液状と
は常温で流動性を有している状態を指している。この液
状エポキシ樹脂としては、各種のものを使用することが
可能であるが、入手の容易さからビスフェノールＡ型エ
ポキシ樹脂を用いることが好ましく、エポキシ当量とし
ては１８０〜１９０のものが好ましい。The epoxy resin composition of the present invention contains an epoxy resin, a curing agent, a curing catalyst, a foaming agent and a pigment. And, based on the total amount of the epoxy resin, the curing agent, the curing catalyst, the foaming agent and the pigment, the liquid epoxy resin contains at least 40% by weight, and the acid anhydride and phenol novolak as the curing agent in a total amount of 30 to 40% by weight. ing. A resin composition for producing a sheet molding compound needs to be in a liquid state in order to impregnate a fibrous reinforcing material such as glass fiber, and in order to realize this liquefaction, a liquid epoxy resin is used in the present invention. At least 40% by weight. Here, the liquid refers to a state having fluidity at normal temperature. Various liquid epoxy resins can be used, but it is preferable to use a bisphenol A type epoxy resin because of easy availability, and an epoxy equivalent of 180 to 190 is preferable.
【００１５】そして、本発明のエポキシ樹脂組成物で、
エポキシ樹脂、硬化剤、硬化触媒、発泡剤及び顔料の合
計量に対し、硬化剤である酸無水物及びフェノールノボ
ラックを合計で３０〜４０重量％含有しているのは、こ
の範囲内であることが、得られる成形品の剛性を優れた
ものとするのに有効だからである。また、本発明のエポ
キシ樹脂組成物では、酸無水物とフェノールノボラック
の配合比を重量で８：２〜６：４と特定している。フェ
ノールノボラックの配合比が２より少ないと、得られる
成形品の剛性が低下し、４を越えると、本発明のエポキ
シ樹脂組成物の粘度が高くなり、樹脂混合、塗布、含浸
作業等に支障をきたすからである。本発明で使用する酸
無水物としては、ヘキサヒドロ無水フタル酸（ＨＨＰ
Ａ）、テトラヒドロ無水フタル酸（ＴＨＰＡ）、メチル
ヘキサヒドロ無水フタル酸（Ｍｅ−ＨＨＰＡ）、メチル
テトラヒドロ無水フタル酸（Ｍｅ−ＴＨＰＡ）等を例示
できるが、液状のものであることが、シートモールディ
ングコンパウンドを製造する際の塗布、含浸作業を容易
にするので好ましい。本発明で使用するフェノールノボ
ラックは水洗等によってホルマリンを除去処理したもの
を用いる。フェノールノボラック中の遊離ホルマリンの
含有量は、０．５重量％以下であることが望ましい。Then, the epoxy resin composition of the present invention comprises:
It is within this range that the total content of the acid anhydride and phenol novolak as the curing agent is 30 to 40% by weight based on the total amount of the epoxy resin, the curing agent, the curing catalyst, the foaming agent and the pigment. However, this is effective for improving the rigidity of the obtained molded article. Further, in the epoxy resin composition of the present invention, the compounding ratio of the acid anhydride and the phenol novolak is specified to be 8: 2 to 6: 4 by weight. If the compounding ratio of phenol novolak is less than 2, the rigidity of the obtained molded article is reduced, and if it exceeds 4, the viscosity of the epoxy resin composition of the present invention becomes high, which hinders the resin mixing, coating, impregnation work and the like. Because it is cool. The acid anhydride used in the present invention is hexahydrophthalic anhydride (HHP).
A), tetrahydrophthalic anhydride (THPA), methylhexahydrophthalic anhydride (Me-HHPA), methyltetrahydrophthalic anhydride (Me-THPA) and the like can be exemplified. It is preferable because it facilitates the application and impregnation work in the production of. The phenol novolak used in the present invention is one obtained by removing formalin by washing with water or the like. The free formalin content in the phenol novolak is desirably 0.5% by weight or less.
【００１６】また、本発明のエポキシ樹脂組成物では、
エポキシ樹脂、硬化剤、硬化触媒、発泡剤及び顔料の合
計量に対し、融点が１３７〜１４５℃のイミダゾール系
硬化触媒を３〜６重量％含有していることが得られる成
形品の剛性を向上するためには好ましい。なお、６重量
％を越えて配合しても剛性を向上する効果は大きくなら
ないため、６重量％を越えて配合する利点はない。In the epoxy resin composition of the present invention,
Increasing the rigidity of a molded article obtained by containing 3 to 6% by weight of an imidazole-based curing catalyst having a melting point of 137 to 145 ° C based on the total amount of the epoxy resin, the curing agent, the curing catalyst, the blowing agent and the pigment Is preferred. It should be noted that the effect of improving the rigidity does not increase even when the content exceeds 6% by weight, so that there is no advantage in the content exceeding 6% by weight.
【００１７】また、本発明のエポキシ樹脂組成物では、
エポキシ樹脂、硬化剤、硬化触媒、発泡剤及び顔料の合
計量に対し、発泡剤を２〜６重量％含有していること
が、軽量で且つ剛性の優れた成形品を得るのに好まし
い。発泡剤は成形時に分解発泡してガスを発生するもの
であり、このガスにより成形品に多数の空隙（気泡）を
生じて成形品の軽量化を図ることができる。発泡剤とし
ては各種のものを使用することができるが、重炭酸塩
（例えばＮａＨＣＯ3）であると、発泡剤が熱分解して
発生するガス成分として、無臭で人体に無害な二酸化炭
素や水蒸気のみを発生することになるので好ましい。Further, in the epoxy resin composition of the present invention,
It is preferable to contain a foaming agent in an amount of 2 to 6% by weight based on the total amount of the epoxy resin, the curing agent, the curing catalyst, the foaming agent, and the pigment in order to obtain a lightweight and excellent rigid molded article. The foaming agent decomposes and foams at the time of molding to generate a gas, and this gas generates a large number of voids (bubbles) in the molded product, thereby reducing the weight of the molded product. As the blowing agent, various types can be used. If it is a bicarbonate (for example, NaHCO 3 ), odorless and harmless carbon dioxide or water vapor is generated as a gas component generated by thermal decomposition of the blowing agent. This is preferable because only this will occur.
【００１８】また、本発明のエポキシ樹脂組成物では、
エポキシ樹脂、硬化剤、硬化触媒、発泡剤及び顔料の合
計量に対し、顔料を１〜２重量％含有させることによ
り、着色した成形品を得ることができるようになる。顔
料としては、各種のものを使用でき、例えばカーボンブ
ラックを例示できる。Further, in the epoxy resin composition of the present invention,
By containing the pigment in an amount of 1 to 2% by weight based on the total amount of the epoxy resin, the curing agent, the curing catalyst, the foaming agent and the pigment, a colored molded article can be obtained. Various pigments can be used as the pigment, for example, carbon black.
【００１９】また、本発明のエポキシ樹脂組成物では、
エポキシ樹脂、硬化剤、硬化触媒、発泡剤及び顔料の合
計量１００重量部に対し、さらに無機粉末充填材を５〜
３５重量部の割合で配合して、寸法精度の向上等の性能
改善を行うことができる。しかし、無機粉末充填材の配
合が３５重量部を越えると、混合物の粘度が高くなり、
シートモールディングコンパウンドを製造する際の塗
布、含浸作業に支障をきたす傾向を生じるため、３５重
量部以下とすることが好ましい。使用する無機粉末充填
材としては、例えば、炭酸カルシウム、シリカ、水酸化
アルミニウム、タルク等を例示できる。Further, in the epoxy resin composition of the present invention,
The total amount of the epoxy resin, the curing agent, the curing catalyst, the foaming agent, and the pigment is 100 parts by weight, and the inorganic powder filler is further added to 5 parts by weight.
By blending at a ratio of 35 parts by weight, performance improvement such as improvement of dimensional accuracy can be performed. However, when the amount of the inorganic powder filler exceeds 35 parts by weight, the viscosity of the mixture increases,
The amount is preferably 35 parts by weight or less, since there is a tendency that the coating and impregnating operations at the time of manufacturing the sheet molding compound are hindered. Examples of the inorganic powder filler used include calcium carbonate, silica, aluminum hydroxide, and talc.
【００２０】本発明のシートモールディングコンパウン
ドは、上記で説明した本発明のエポキシ樹脂組成物を繊
維質の補強材に含浸してなるシートモールディングコン
パウンドである。エポキシ樹脂組成物と繊維質の補強材
の各目付量については、特に限定するものではないが、
エポキシ樹脂組成物の目付量とほぼ同じ目付量の繊維質
の補強材となるようにして、シートモールディングコン
パウンドとすることが、得られる成形品の剛性を向上す
るためには好ましい。使用する繊維質の補強材として
は、素材としてはガラス繊維、植物性繊維、有機樹脂繊
維等が挙げられ、これらの素材を、必要な長さにカット
した短繊維や、マット状に織りこんだもの等の形態にし
て使用することができる。本発明のシートモールディン
グコンパウンドは、例えば、まずポリプロピレンフィル
ム等のキャリアフィルム上に液状のエポキシ樹脂組成物
を所定の目付量（例えば１００〜８００ｇ／ｍ2）とな
るように塗布する。次いで、キャリアフィルム上のエポ
キシ樹脂組成物にガラス繊維等の繊維質の補強材を上側
から散布し、エポキシ樹脂組成物を繊維質の補強材に含
浸させる。この後、必要に応じてシートモールディング
コンパウンドを熟成させる。熟成条件は例えば４０〜１
００℃で５〜１００時間程度行い、エポキシ樹脂組成物
をＢステージ化（半硬化状態）にして、その後の成形工
程に適する状態にシートモールディングコンパウンドを
調整する。The sheet molding compound of the present invention is a sheet molding compound obtained by impregnating the above-described epoxy resin composition of the present invention into a fibrous reinforcing material. The weight per unit area of the epoxy resin composition and the fibrous reinforcing material is not particularly limited,
It is preferable to use a sheet molding compound so as to be a fibrous reinforcing material having a basis weight substantially equal to the basis weight of the epoxy resin composition in order to improve the rigidity of the obtained molded article. Examples of the fibrous reinforcing material to be used include glass fiber, vegetable fiber, organic resin fiber, and the like, and these materials are woven into a short fiber cut into a required length or a mat shape. It can be used in the form of an object or the like. In the sheet molding compound of the present invention, for example, a liquid epoxy resin composition is first applied on a carrier film such as a polypropylene film so as to have a predetermined basis weight (for example, 100 to 800 g / m 2 ). Next, a fibrous reinforcing material such as glass fiber is sprinkled from above onto the epoxy resin composition on the carrier film, and the epoxy resin composition is impregnated into the fibrous reinforcing material. Thereafter, the sheet molding compound is aged as required. The aging conditions are, for example, 40 to 1
This is performed at 00 ° C. for about 5 to 100 hours to bring the epoxy resin composition into the B-stage (semi-cured state), and adjust the sheet molding compound to a state suitable for the subsequent molding step.
【００２１】このようにして、得られる本発明のシート
モールディングコンパウンドを用いて成形加工を行い、
本発明の成形品を製造する。例えば、１枚のシートモー
ルディングコンパウンドあるいは複数枚のシートモール
ディングコンパウンドを重ねて、１対の成形型の間にセ
ットし、１５０〜２３０℃で３〜６０分間加熱して、エ
ポキシ樹脂組成物を硬化させ、成形品を得る。また、本
発明のシートモールディングコンパウンドは、ダンボー
ル等のハニカム構造体を芯材とし、その両面又は片面に
シートモールディングコンパウンドを配して製造される
成形品にも適用できる。本発明の成形品は、上述の本発
明のエポキシ樹脂組成物を用いて製造されるため、ホル
マリンが発生しない成形品であって、剛性に優れる成形
品となる。A molding process is performed using the thus obtained sheet molding compound of the present invention.
The molded article of the present invention is manufactured. For example, one sheet molding compound or a plurality of sheet molding compounds are stacked, set between a pair of molds, and heated at 150 to 230 ° C. for 3 to 60 minutes to cure the epoxy resin composition. , To obtain molded products. Further, the sheet molding compound of the present invention can be applied to a molded product manufactured by using a honeycomb structure such as a cardboard as a core material and arranging the sheet molding compound on both surfaces or one surface thereof. Since the molded article of the present invention is manufactured using the above-described epoxy resin composition of the present invention, the molded article does not generate formalin and has excellent rigidity.
【００２２】[0022]
【実施例】以下本発明を実施例により具体的に説明す
る。The present invention will be specifically described below with reference to examples.
【００２３】実施例１〜７、比較例１〜５ 表１及び表２に示す配合割合で各種の材料を下記の手順
で混合してエポキシ樹脂組成物を得、次いでシートモー
ルディングコンパウンドを作製し、さらに成形品を作製
した。表１及び表２に示す硬化剤Ａは酸無水物：メチル
テトラヒドロ無水フタル酸（Ｍｅ−ＴＨＰＡ）であり、
硬化剤Ｂは遊離ホルマリンの含有量が０．５重量％以下
のフェノールノボラックであり、硬化触媒の２ＰＨｚは
融点が１４０℃のイミダゾール系硬化触媒であり、発泡
剤(永和化成製ＳＣ８５５)の主成分はＮａＨＣＯ3であ
る。 （１）液状のエポキシ樹脂組成物の作製 エポキシ樹脂及び硬化剤を１００℃で６０分間ディスパ
ーにて混合して、混合液を得、この混合液を３０℃以下
まで冷却し、硬化触媒、発泡剤、顔料、離型剤、無機粉
末充填材を添加し、６０分間ディスパーにて混合して、
液状のエポキシ樹脂組成物を作製した。なお、レゾール
を用いた比較例５では、レゾール、発泡剤、顔料、離型
剤、無機粉末充填材を６０分間ディスパーにて混合し
て、液状のフェノール樹脂組成物を作製した。 （２）シートモールディングコンパウンドの作製 上記のエポキシ樹脂組成物をキャリアフィルム上に、目
付け量５００ｇ／ｍ2となるように塗布し、次いで、こ
のエポキシ樹脂組成物に同目付け量の繊維質補強材を散
布する。さらに、新たなキャリアフィルムで全面を覆
い、熟成処理を行ってシートモールディングコンパウン
ドを作製した。 （３）成形品の作製 上記のシートモールディングコンパウンドからキャリア
フィルムを剥がし、７ｍｍ厚みのダンボールハニカム構
造体の上面及び下面に積層する。この積層物を、２００
℃に昇温させた金型で５分間挟持して加熱成形して、エ
ポキシ樹脂組成物が硬化した板状の成形品を得た。 （４）樹脂組成物及び成形品の評価 ＳＭＣ塗布作業性：樹脂組成物をキャリアフィルム上に
塗布した際の広がり性と、その後の繊維質補強材への含
浸性を観察して評価する。Examples 1 to 7 and Comparative Examples 1 to 5 Various materials were mixed in the mixing ratios shown in Tables 1 and 2 by the following procedure to obtain an epoxy resin composition, and then a sheet molding compound was prepared. Further, molded articles were produced. The curing agent A shown in Tables 1 and 2 is an acid anhydride: methyltetrahydrophthalic anhydride (Me-THPA),
Curing agent B is a phenol novolak having a free formalin content of 0.5% by weight or less, and 2 PHz of the curing catalyst is an imidazole-based curing catalyst having a melting point of 140 ° C. Is NaHCO 3 . (1) Preparation of Liquid Epoxy Resin Composition An epoxy resin and a curing agent were mixed by a disper at 100 ° C. for 60 minutes to obtain a mixed solution, and the mixed solution was cooled to 30 ° C. or lower, and a curing catalyst, a foaming agent , A pigment, a release agent, and an inorganic powder filler are added and mixed with a disper for 60 minutes.
A liquid epoxy resin composition was prepared. In Comparative Example 5 using a resole, a resole, a foaming agent, a pigment, a release agent, and an inorganic powder filler were mixed by a disper for 60 minutes to prepare a liquid phenol resin composition. (2) Preparation of sheet molding compound The above epoxy resin composition was applied onto a carrier film so as to have a basis weight of 500 g / m 2, and then a fibrous reinforcing material having the same basis weight was applied to the epoxy resin composition. Spray. Further, the entire surface was covered with a new carrier film, and aging treatment was performed to produce a sheet molding compound. (3) Preparation of molded article The carrier film is peeled off from the above-mentioned sheet molding compound and laminated on the upper and lower surfaces of a cardboard honeycomb structure having a thickness of 7 mm. This laminate is
The resulting mixture was heated and molded in a mold heated to a temperature of 5 ° C. for 5 minutes to obtain a plate-like molded product in which the epoxy resin composition was cured. (4) Evaluation of resin composition and molded article SMC coating workability: The spreadability when the resin composition is coated on a carrier film and the subsequent impregnation into the fibrous reinforcing material are evaluated.
【００２４】成形品外観：目視にて、外観、発泡具合、
層剥離の有無を評価する。Molded product appearance: Visual appearance, foaming condition,
The presence or absence of delamination is evaluated.
【００２５】ホルマリン臭気：板状の成形品を２０ｍｍ
角に切断し試験片とし、この試験片を密閉した５Ｌの容
器中で、１２０℃で３０分間加熱処理し、室温まで冷却
する。この密閉容器中のガスについてホルマリン検知管
を用いてホルマリン臭気（ｐｐｍ）を測定する。Formalin odor: 20 mm
The test piece is cut into corners, and the test piece is heated in a sealed 5 L container at 120 ° C. for 30 minutes and cooled to room temperature. Formalin odor (ppm) is measured for the gas in the closed container using a formalin detector tube.
【００２６】剛性：板状の成形品を５０ｍｍ×２００ｍ
ｍに切断し、スパン距離６４ｍｍ、試験速度１ｍｍ／分
の条件にて曲げ強度（ＭＰａ）を測定し、剛性とした。Rigidity: 50 mm × 200 m plate-shaped molded product
m, and the bending strength (MPa) was measured under the conditions of a span distance of 64 mm and a test speed of 1 mm / min, and the result was defined as rigidity.
【００２７】以上の結果を表１、表２に示した。The above results are shown in Tables 1 and 2.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
【００３０】表１、表２から明らかなように、本発明の
実施例では、ホルマリンが発生しない成形品であって、
剛性に優れる成形品を得ることができている。As is clear from Tables 1 and 2, in the embodiment of the present invention, the molded article does not generate formalin,
A molded product having excellent rigidity can be obtained.
【００３１】[0031]
【発明の効果】請求項１〜請求項６に係る発明のエポキ
シ樹脂組成物は、シートモールディングコンパウンドを
製造するのに好適な液状のエポキシ樹脂組成物であり、
このエポキシ樹脂組成物によれば、ホルマリンが発生し
ない成形品であって、剛性に優れる成形品を得ることが
できる。The epoxy resin composition of the invention according to claims 1 to 6 is a liquid epoxy resin composition suitable for producing a sheet molding compound,
According to this epoxy resin composition, it is possible to obtain a molded article which does not generate formalin and has excellent rigidity.
【００３２】請求項７に係る発明のシートモールディン
グコンパウンドは、請求項１乃至請求項６の何れかに記
載のエポキシ樹脂組成物を用いているので、ホルマリン
が発生しない成形品であって、剛性に優れる成形品を得
ることができるシートモールディングコンパウンドとな
る。The sheet molding compound of the invention according to claim 7 uses the epoxy resin composition according to any one of claims 1 to 6, so that it is a molded product that does not generate formalin and has a high rigidity. It becomes a sheet molding compound from which an excellent molded product can be obtained.
【００３３】請求項８に係る発明の成形品は、請求項７
記載のシートモールディングコンパウンドを用いて製造
するので、ホルマリンが発生しない成形品であって、剛
性に優れる成形品となる。The molded article of the invention according to claim 8 is the same as the molded article according to claim 7
Since it is manufactured using the described sheet molding compound, it is a molded product that does not generate formalin and has excellent rigidity.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 63/00 Ｃ０８Ｌ 63/00 Ｚ Ｆターム(参考） 4F072 AA02 AB03 AB04 AB09 AB29 AD28 AD56 AE02 AF01 AF04 AG03 AH04 AH31 AJ04 AK02 AK14 AL02 AL17 4F074 BA03 CA23 CC03Y CC04Y CC10X DA35 DA58 4J002 CC04X CD05W DA037 DE148 DE206 DE238 DJ018 DJ048 FD018 FD097 FD326 4J036 AA01 AD08 DB21 DC41 FA02 FA03 FB08 JA11 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI theme coat ゛ (reference) C08L 63/00 C08L 63/00 Z F term (reference) 4F072 AA02 AB03 AB04 AB09 AB29 AD28 AD56 AE02 AF01 AF04 AG03 AH04 AH31 AJ04 AK02 AK14 AL02 AL17 4F074 BA03 CA23 CC03Y CC04Y CC10X DA35 DA58 4J002 CC04X CD05W DA037 DE148 DE206 DE238 DJ018 DJ048 FD018 FD097 FD326 4J036 AA01 AD08 DB21 DC41 FA02 FA03 FB08 JA11
Claims (8)
剤及び顔料を含有していて、これらの合計量に対し液状
エポキシ樹脂を少なくとも４０重量％、硬化剤である酸
無水物及びフェノールノボラックを合計で３０〜４０重
量％含有すると共に、前記酸無水物と前記フェノールノ
ボラックの配合比が重量で８：２〜６：４であることを
特徴とするエポキシ樹脂組成物。1. An epoxy resin, a curing agent, a curing catalyst, a foaming agent and a pigment, and at least 40% by weight of a liquid epoxy resin based on the total amount thereof, and an acid anhydride and a phenol novolak as curing agents. An epoxy resin composition containing 30 to 40% by weight in total, and the compounding ratio of the acid anhydride and the phenol novolak is 8: 2 to 6: 4 by weight.
ールＡ型エポキシ樹脂を用いることを特徴とする請求項
１記載のエポキシ樹脂組成物。2. The epoxy resin composition according to claim 1, wherein a bisphenol A type epoxy resin is used as the liquid epoxy resin.
剤及び顔料の合計量に対し、融点が１３７〜１４５℃の
イミダゾール系硬化触媒を３〜６重量％含有している請
求項１又は請求項２記載のエポキシ樹脂組成物。3. An imidazole-based curing catalyst having a melting point of 137 to 145 ° C. based on the total amount of the epoxy resin, the curing agent, the curing catalyst, the foaming agent and the pigment is contained in an amount of 3 to 6% by weight. Item 3. The epoxy resin composition according to Item 2.
剤及び顔料の合計量に対し、重炭酸塩である発泡剤を２
〜６重量％含有している請求項１乃至請求項３の何れか
に記載のエポキシ樹脂組成物。4. A blowing agent which is a bicarbonate is added to the total amount of the epoxy resin, the curing agent, the curing catalyst, the blowing agent and the pigment.
The epoxy resin composition according to any one of claims 1 to 3, wherein the content of the epoxy resin composition is from 6 to 6% by weight.
剤及び顔料の合計量に対し、顔料を１〜２重量％含有し
ている請求項１乃至請求項４の何れかに記載のエポキシ
樹脂組成物。5. The epoxy resin according to claim 1, wherein the content of the pigment is 1 to 2% by weight based on the total amount of the epoxy resin, the curing agent, the curing catalyst, the foaming agent and the pigment. Composition.
剤及び顔料の合計量１００重量部に対し、さらに無機粉
末充填材を５〜３５重量部の割合で配合している請求項
１乃至請求項５の何れかに記載のエポキシ樹脂組成物。6. An inorganic powder filler is further added in a proportion of 5 to 35 parts by weight based on 100 parts by weight of the total amount of the epoxy resin, the curing agent, the curing catalyst, the foaming agent and the pigment. Item 6. The epoxy resin composition according to any one of items 5.
エポキシ樹脂組成物を繊維質の補強材に含浸してなるシ
ートモールディングコンパウンド。7. A sheet molding compound obtained by impregnating a fibrous reinforcing material with the epoxy resin composition according to any one of claims 1 to 6.
ンパウンドを成形してなる成形品。8. A molded product obtained by molding the sheet molding compound according to claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000194603A JP3633449B2 (en) | 2000-06-28 | 2000-06-28 | Epoxy resin composition, sheet molding compound and molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000194603A JP3633449B2 (en) | 2000-06-28 | 2000-06-28 | Epoxy resin composition, sheet molding compound and molded product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002012649A true JP2002012649A (en) | 2002-01-15 |
| JP3633449B2 JP3633449B2 (en) | 2005-03-30 |
Family
ID=18693401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000194603A Expired - Fee Related JP3633449B2 (en) | 2000-06-28 | 2000-06-28 | Epoxy resin composition, sheet molding compound and molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3633449B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004175892A (en) * | 2002-11-26 | 2004-06-24 | Matsushita Electric Works Ltd | Acrylic resin composition for smc, smc and molding |
| WO2013065516A1 (en) | 2011-10-31 | 2013-05-10 | 東レ株式会社 | Two-pack type epoxy resin composition for fiber-reinforced composite materials, and fiber-reinforced composite material |
| CN104226022A (en) * | 2013-06-06 | 2014-12-24 | 阿尔斯通技术有限公司 | Moisture separator configuration |
| EP3119836A1 (en) * | 2014-03-21 | 2017-01-25 | Henkel AG & Co. KGaA | Thermally expandable compositions |
| JPWO2018190329A1 (en) * | 2017-04-12 | 2019-04-25 | 三菱ケミカル株式会社 | Sheet molding compound and fiber reinforced composite material |
| WO2020050200A1 (en) * | 2018-09-05 | 2020-03-12 | 三菱ケミカル株式会社 | Sheet molding compound and fiber-reinforced composite material |
| WO2020071360A1 (en) * | 2018-10-05 | 2020-04-09 | 三菱ケミカル株式会社 | Sheet molding compound, fiber-reinforced composite material and method for producing fiber-reinforced composite material |
| EP3207092B1 (en) | 2014-10-16 | 2021-08-11 | Henkel AG & Co. KGaA | Thermally expandable compositions |
| JP2022061078A (en) * | 2020-10-06 | 2022-04-18 | 小島プレス工業株式会社 | A resin composition for a sheet molding compound, a sheet molding compound using the same, a molded product, and a method for producing the same. |
-
2000
- 2000-06-28 JP JP2000194603A patent/JP3633449B2/en not_active Expired - Fee Related
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004175892A (en) * | 2002-11-26 | 2004-06-24 | Matsushita Electric Works Ltd | Acrylic resin composition for smc, smc and molding |
| WO2013065516A1 (en) | 2011-10-31 | 2013-05-10 | 東レ株式会社 | Two-pack type epoxy resin composition for fiber-reinforced composite materials, and fiber-reinforced composite material |
| CN103917574A (en) * | 2011-10-31 | 2014-07-09 | 东丽株式会社 | Two-component epoxy resin composition for fiber-reinforced composite material, and fiber-reinforced composite material |
| US20140288214A1 (en) * | 2011-10-31 | 2014-09-25 | Toray Industries Inc. | Two-pack type epoxy resin composition for fiber-reinforced composite materials, and fiber-reinforced composite material |
| US9328237B2 (en) | 2011-10-31 | 2016-05-03 | Toray Industries, Inc. | Two-pack type epoxy resin composition for fiber-reinforced composite materials, and fiber-reinforced composite material |
| CN104226022A (en) * | 2013-06-06 | 2014-12-24 | 阿尔斯通技术有限公司 | Moisture separator configuration |
| EP3119836A1 (en) * | 2014-03-21 | 2017-01-25 | Henkel AG & Co. KGaA | Thermally expandable compositions |
| US11578181B2 (en) | 2014-10-16 | 2023-02-14 | Henkel Ag & Co. Kgaa | Thermally expandable compositions |
| EP3207092B1 (en) | 2014-10-16 | 2021-08-11 | Henkel AG & Co. KGaA | Thermally expandable compositions |
| JP2020122162A (en) * | 2017-04-12 | 2020-08-13 | 三菱ケミカル株式会社 | Sheet molding compound and fiber-reinforced composite material |
| JP2022179548A (en) * | 2017-04-12 | 2022-12-02 | 三菱ケミカル株式会社 | Sheet molding compounds and fiber reinforced composites |
| JPWO2018190329A1 (en) * | 2017-04-12 | 2019-04-25 | 三菱ケミカル株式会社 | Sheet molding compound and fiber reinforced composite material |
| JP7552668B2 (en) | 2017-04-12 | 2024-09-18 | 三菱ケミカル株式会社 | Manufacturing method of sheet molding compound |
| US12275838B2 (en) | 2017-04-12 | 2025-04-15 | Mitsubishi Chemical Corporation | Sheet molding compound and fiber-reinforced composite material |
| JPWO2020050200A1 (en) * | 2018-09-05 | 2020-09-10 | 三菱ケミカル株式会社 | Sheet molding compound, and fiber reinforced composite material |
| CN112654666A (en) * | 2018-09-05 | 2021-04-13 | 三菱化学株式会社 | Sheet molding compound and fiber-reinforced composite material |
| WO2020050200A1 (en) * | 2018-09-05 | 2020-03-12 | 三菱ケミカル株式会社 | Sheet molding compound and fiber-reinforced composite material |
| JP7036122B2 (en) | 2018-09-05 | 2022-03-15 | 三菱ケミカル株式会社 | Manufacturing method of sheet molding compound |
| US12257745B2 (en) | 2018-09-05 | 2025-03-25 | Mitsubishi Chemical Corporation | Sheet molding compound and fiber-reinforced composite |
| WO2020071360A1 (en) * | 2018-10-05 | 2020-04-09 | 三菱ケミカル株式会社 | Sheet molding compound, fiber-reinforced composite material and method for producing fiber-reinforced composite material |
| JPWO2020071360A1 (en) * | 2018-10-05 | 2021-02-15 | 三菱ケミカル株式会社 | Manufacturing method of sheet molding compound, fiber reinforced composite material, fiber reinforced composite material |
| JP2022061078A (en) * | 2020-10-06 | 2022-04-18 | 小島プレス工業株式会社 | A resin composition for a sheet molding compound, a sheet molding compound using the same, a molded product, and a method for producing the same. |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3633449B2 (en) | 2005-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4242406A (en) | Fiber reinforced composite structural laminate composed of two layers tied to one another by embedded fibers bridging both layers | |
| JPH07258441A (en) | Fibrous preform containing cyclic polyester oligomer and its production | |
| JP2002012649A (en) | Epoxy resin composition, sheet molding compound and molded product | |
| JP2011512441A (en) | Thermosetting composition comprising silicone polyether, its manufacture and use | |
| EP0166275A2 (en) | Resin composition for molding material | |
| CN102325835B (en) | Improved polymer preparation | |
| KR20180001487A (en) | Epoxy resin composition and prepreg by using the same for fiber reinforcement plastics | |
| EP0149652B1 (en) | Method of preparing moulding compositions | |
| US4546674A (en) | Method for providing a tool for forming an article | |
| KR101333877B1 (en) | Phenolic resin foam | |
| EP1100674B1 (en) | Resin transfer moulding | |
| JPS5883032A (en) | Epoxy resin prepreg | |
| RU2655805C1 (en) | Epoxy binder, prepreg based thereon and article made therefrom | |
| JP2016175970A (en) | Prepreg and laminate sheet using the same | |
| JPH04234451A (en) | Thixotropic composition | |
| WO2018003690A1 (en) | Epoxy resin composition, prepreg, and fiber-reinforced composite material | |
| JPH01105735A (en) | Manufacture of fiber reinforced phenol resin molded object | |
| KR20070029061A (en) | Phenolic Resin Foam | |
| RU2815497C1 (en) | Chemically resistant tabletop coating | |
| US4355145A (en) | Furan resins of improved fire resistance | |
| JP2003041084A (en) | Diallyl phthalate resin composition, sheet molding compound and molded article | |
| KR20210025383A (en) | Light-weight prepreg and method for producing the same | |
| JP2568799B2 (en) | Method for producing fiber-reinforced phenolic resin molded product | |
| JP2011001442A (en) | Epoxy resin composition, fiber-reinforced composite material, and manufacturing method for fiber-reinforced composite material | |
| JPH0381383A (en) | Film adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20041008 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20041207 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20041220 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080107 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090107 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090107 Year of fee payment: 4 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090107 Year of fee payment: 4 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100107 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100107 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110107 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120107 Year of fee payment: 7 |
|
| LAPS | Cancellation because of no payment of annual fees |