WO2012115067A1 - Frpの製造方法 - Google Patents
Frpの製造方法 Download PDFInfo
- Publication number
- WO2012115067A1 WO2012115067A1 PCT/JP2012/054033 JP2012054033W WO2012115067A1 WO 2012115067 A1 WO2012115067 A1 WO 2012115067A1 JP 2012054033 W JP2012054033 W JP 2012054033W WO 2012115067 A1 WO2012115067 A1 WO 2012115067A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- preform
- flow resistance
- resistance region
- high flow
- 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.)
- Ceased
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C39/10—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
- B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/22—Component parts, details or accessories; Auxiliary operations
- B29C39/24—Feeding the material into the mould
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0046—Details relating to the filling pattern or flow paths or flow characteristics of moulding material in the mould cavity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
- B29C70/546—Measures for feeding or distributing the matrix material in the reinforcing structure
- B29C70/548—Measures for feeding or distributing the matrix material in the reinforcing structure using distribution constructions, e.g. channels incorporated in or associated with the mould
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
Definitions
- the resin injection speed is relatively easy to control, and the position of the flow front and its progress are easily monitored.
- the flow front shape line does not advance in the desired shape or there are places where the flow front is difficult to reach, insufficient impregnated resin parts (resin starve parts or resin non-impregnated parts) are likely to occur, There is a possibility that a part with poor quality is generated.
- the high flow resistance region is formed at a position outside the product to be molded, it is preferable that the high flow resistance region be suppressed to a necessary minimum area in terms of material yield and the like.
- a high flow resistance region can be provided around the product, it can be said that it is a molding method that does not require trimming and trimming the end of the base material. Therefore, it is preferable in that the step of trimming the end portions is unnecessary and the product can be molded stably.
- the volume of the air trap region is preferably 0.1 times or more and 50 times or less as compared with the space volume within the product range. More preferably, it is 0.1 to 2 times the space volume after compression when the space volume is compressed by the resin injection pressure. When the space volume is evacuated, it may be reduced by that ratio. It is sufficient that at least air is trapped in this air trap region (that is, at a position unrelated to the molded product), but more preferably, trapped air is drawn from a suction port opened at an appropriate position in the air trap region. Aspirated and removed.
- a runner for injecting resin is provided around the preform, and the resin is injected from the periphery of the preform toward the center of the preform.
- the suction path is arranged in the center of the preform, and a high flow resistance region is formed in the preform itself around the suction path to increase the resin flow resistance and make it difficult for the resin to partially flow.
- the resin injected from the runner flows toward the suction path disposed in the center of the preform, and the flow front of the injected resin also advances toward the suction path. Eventually, when a part of the flow front reaches the high flow resistance region formed around the suction path, the flow resistance of the resin suddenly increases at the reaching part.
- the preform is pressed from both sides with an appropriate pressing force by the clamping of the mold so that it is slightly compressed, so that the inner surface of the mold and the surface of the preform are well adhered, and the resin injection Even when a small amount of air is contained in the injection resin from the road, it is possible to suppress the air or air-containing resin from running on the preform surface, contributing to the improvement of the surface quality of the molded product. It will be possible.
- the high flow resistance region 22 is formed by changing the thickness of the outer periphery of the preform 7 at the position outside the product with respect to the product outer shape 22 (upper die 4, lower die) as shown in FIG. It is formed by reducing according to 5).
- the high flow resistance region can also be formed by increasing the reinforcing fiber density in the outer peripheral portion of the preform in advance at a position outside the product with respect to the outer shape of the product to be molded.
- the plurality of resin injection ports 9 are each configured as a resin injection port that can be controlled to open and close independently, and the front end (flow front) of the resin flow injected from each resin injection port 9 is substantially At the same time, control means for controlling the opening timing of each resin injection port 9 can be provided so as to reach the high flow resistance region 22 at the same time.
- the resin spreading from the inside of the preform 7 toward the outer periphery of the preform 7 is at least over the entire range of the product region to be molded.
- the air that was sufficiently satisfactorily filled and impregnated in the reinforcing fiber base material of the preform 7 and the air existing in the preform 7 with the spread of the resin was further mixed in the resin. Even (bubbles) are sequentially pushed out toward the high flow resistance region 22 located outside the product range and further into the air trap region 23.
- FIG. 7 shows a planar arrangement.
- the suction port 109 is disposed at the center of the preform 107, and a portion corresponding to the periphery of the suction port 109 of the preform 107 itself is located from the periphery of the portion. It is formed in the high flow resistance region 121 that makes the resin flowing toward the portion difficult to flow in the portion.
- the high flow resistance region 121 is formed at a position outside the product with respect to the product to be molded, or at a position where the appearance designability is not required in the product to be molded. In this manner, the thickness of the preform 107 in the product region is partially reduced in the high flow resistance region 121 by the molding die 103 (the upper die 104 and the lower die 105).
- the high flow resistance region can be formed by increasing the reinforcing fiber density in the preform in the high flow resistance region in advance.
- the resin supplied into the runner 108 from each resin inlet 110 flows in the runner 108. Injected from the periphery of the preform 107 toward the preform 107 from the runner 108.
- the flow of the injected resin proceeds as shown in FIGS. 9A to 9D, for example.
- FIG. 9 (A) when the injection is started from the periphery of the preform 107 from the runner 108 toward the preform 107, the shape of the flow front 131 showing the tip of the injected resin flow is: It spreads from the preform outer periphery 122 toward the inside of the preform 107.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
I=(ε/(1-ε))√(αP/2)×∫〔dt/√(μ(t)t)〕
I:パーミアビリティ、ε:基材の抵抗、α:定数、P:基材内の真空圧、
μ(t):粘度、t:経過時間
ここで、パーミアビリティは樹脂が強化繊維基材に含浸する距離(厚み)に相当する。上記高流れ抵抗領域における樹脂の流れにくさをパーミアビリティで表すと、成形すべき製品の範囲内の部位におけるパーミアビリティに対し、高流れ抵抗領域のパーミアビリティが0.8倍以下であることが好ましく、さらに好ましくは0.5倍以下である。
2.5×10-6mm<t2/L
t<t’
t(mm):吸引口近傍のキャビティ厚、t’(mm):吸引口近傍外のキャビティ厚、L(mm):吸引口近傍から近傍外までの最小距離
このような設定により、成形型内のエアを効率よく極力減らすことができる。
図1は、本発明の第1の形態に係る方法の実施に用いるRTM成形装置の一例を示している。図1において、RTM成形装置1は、キャビティ2を形成する成形型3としての上型4と下型5を備えており、上型4は、プレス機構6によって型締め、型開けされるようになっている。キャビティ2内には、強化繊維基材の積層体からなり、例えば予め所定形状に賦形されたプリフォーム7が配置される。このプリフォーム7がキャビティ2内に配置された状態で、上型4が下型5に対し型締めされ、樹脂供給路8からFRPを構成するための樹脂が供給され、プリフォーム7の一面(上面)に対面して開口する複数の樹脂注入路としての樹脂注入口9からキャビティ2内に樹脂が注入されてプリフォーム7を構成している強化繊維基材に含浸される。樹脂注入口9は、例えばピン状の弁体10によって開閉され、キャビティ2の周囲はシール材12でシールされている。成形型3は、例えば熱媒流通路11に流通される熱媒によって加熱、冷却され、樹脂注入時には加熱されて樹脂の良好な含浸がはかられ、樹脂含浸後には、冷却(自然放冷も可能)されて注入、含浸された樹脂が硬化されて、所定のFRP成形品が作製される。
2 キャビティ
3 成形型
4 上型
5 下型
6 プレス機構
7 プリフォーム
8 樹脂供給路
9 樹脂注入口
10 弁体
11 熱媒流通路
12 シール材
21 製品外形
22 高流れ抵抗領域
23 エアトラップ領域
24 距離
25 吸引口
26 流路縮小部
27 樹脂検知センサ
28 弁体
31 フローフロント
32 トラップエア圧縮部
101 RTM成形装置
102 キャビティ
103 成形型
104 上型
105 下型
106 プレス機構
107 プリフォーム
108 ランナー
109 吸引口
110 樹脂注入口
111 弁体
112 シール材
113 熱媒流通路
121 高流れ抵抗領域
122 プリフォーム外周部
123 製品外形
124 樹脂検知センサ
131 フローフロント
132 未含浸領域
133 ボイド領域
134 製品外領域
Claims (15)
- 成形型のキャビティ内に強化繊維基材からなるプリフォームを配置し、前記成形型に、樹脂を注入する樹脂注入路と少なくともエアを吸引する吸引路を設け、前記キャビティ内において、前記樹脂注入路からの注入樹脂を前記吸引路に向かう方向に流動させてプリフォームの強化繊維基材に含浸させるFRPの製造方法において、前記プリフォーム自体に、前記プリフォーム内を流動する樹脂を部分的に流れにくくする高流れ抵抗領域を形成し、該高流れ抵抗領域を介して、前記吸引路に向かう方向に流れつつある樹脂のフローフロントを、成形すべき製品の形状に対し予め定めた許容領域内に納まるように制御することを特徴とするFRPの製造方法。
- 前記樹脂注入路を前記キャビティ内に配置されたプリフォームの一面に対面して開口する複数の樹脂注入口から形成し、前記高流れ抵抗領域を、前記プリフォームの内方から前記プリフォームの外周部に向かって前記プリフォーム内を流動する樹脂を部分的に流れにくくする高流れ抵抗領域として、成形すべき製品の外形に対し製品外の位置にて前記プリフォームの外周部に沿って延びるように形成する、請求項1に記載のFRPの製造方法。
- 前記プリフォームの高流れ抵抗領域の外側に、該高流れ抵抗領域に沿って延びるように、前記成形型により、少なくとも前記高流れ抵抗領域を通して排出されてきたエアを吸引するエアトラップ領域を形成する、請求項2に記載のFRPの製造方法。
- 前記エアトラップ領域に開口された吸引口の設置部またはその近傍に、前記成形型により、前記高流れ抵抗領域を通して樹脂が排出されてきた場合にその樹脂を流れにくくする流路縮小部を形成する、請求項3に記載のFRPの製造方法。
- 前記吸引口の設置部近傍で、前記高流れ抵抗領域を通して樹脂が排出されてきた場合にその樹脂を検知する、請求項4に記載のFRPの製造方法。
- 前記高流れ抵抗領域を、成形すべき製品の外形に対し製品外の位置にて前記プリフォームの外周部の厚みを前記成形型により縮小することにより形成する、請求項2~5のいずれかに記載のFRPの製造方法。
- 前記高流れ抵抗領域を、成形すべき製品の外形に対し製品外の位置にて前記プリフォームの外周部における強化繊維密度を予め高めておくことにより形成する、請求項2~5のいずれかに記載のFRPの製造方法。
- 前記複数の樹脂注入口をそれぞれ独立に開閉制御可能な樹脂注入口に構成し、各樹脂注入口から注入された樹脂のフローフロントが実質的に同時に前記高流れ抵抗領域に到達するように、各樹脂注入口の開タイミングを制御する、請求項2~7のいずれかに記載のFRPの製造方法。
- 前記樹脂注入路を前記プリフォームの周囲に設けられたランナーから形成するとともに、前記吸引路を前記プリフォームの中央部に配置し、前記高流れ抵抗領域を、前記吸引路の周囲に対応する部分に、該部分の周囲から該部分に向かって前記プリフォーム内を流動する樹脂を該部分では流れにくくする高流れ抵抗領域として形成する、請求項1に記載のFRPの製造方法。
- 前記高流れ抵抗領域を、成形すべき製品に対し製品外となる位置、または、成形すべき製品において外観の意匠性を求めない位置に形成する、請求項9に記載のFRPの製造方法。
- 前記吸引路の設置部近傍で、前記高流れ抵抗領域内に流入してきた樹脂を検知する、請求項9または10に記載のFRPの製造方法。
- 前記高流れ抵抗領域を、該高流れ抵抗領域における前記プリフォームの厚みを前記成形型により縮小することにより形成する、請求項9~11のいずれかに記載のFRPの製造方法。
- 前記高流れ抵抗領域を、該高流れ抵抗領域での前記プリフォームにおける強化繊維密度を予め高めておくことにより形成する、請求項9~11のいずれかに記載のFRPの製造方法。
- 前記プリフォームを複数枚の強化繊維基材の積層体から形成し、表層の強化繊維基材よりも内層の強化繊維基材の樹脂の流れ抵抗を低くする、請求項1~13のいずれかに記載のFRPの製造方法。
- 成形すべき製品の範囲内における前記プリフォームの前記キャビティ内への配置前厚みを、対応する前記キャビティの高さよりも大きくしておく、請求項1~14のいずれかに記載のFRPの製造方法。
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/001,358 US9604415B2 (en) | 2011-02-25 | 2012-02-21 | Method for producing FRP |
| EP12749717.0A EP2679372B1 (en) | 2011-02-25 | 2012-02-21 | Method for producing frp |
| KR1020137020242A KR101914803B1 (ko) | 2011-02-25 | 2012-02-21 | Frp의 제조 방법 |
| CN201280006053.3A CN103328178B (zh) | 2011-02-25 | 2012-02-21 | Frp的制造方法 |
| JP2012511079A JP5812438B2 (ja) | 2011-02-25 | 2012-02-21 | Frpの製造方法 |
| US15/230,978 US9950479B2 (en) | 2011-02-25 | 2016-08-08 | Method for producing FRP |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011040626 | 2011-02-25 | ||
| JP2011-039842 | 2011-02-25 | ||
| JP2011-040626 | 2011-02-25 | ||
| JP2011039842 | 2011-02-25 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US14/001,358 A-371-Of-International US9604415B2 (en) | 2011-02-25 | 2012-02-21 | Method for producing FRP |
| US15/230,978 Division US9950479B2 (en) | 2011-02-25 | 2016-08-08 | Method for producing FRP |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012115067A1 true WO2012115067A1 (ja) | 2012-08-30 |
Family
ID=46720844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2012/054033 Ceased WO2012115067A1 (ja) | 2011-02-25 | 2012-02-21 | Frpの製造方法 |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US9604415B2 (ja) |
| EP (1) | EP2679372B1 (ja) |
| JP (1) | JP5812438B2 (ja) |
| KR (1) | KR101914803B1 (ja) |
| CN (1) | CN103328178B (ja) |
| WO (1) | WO2012115067A1 (ja) |
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| WO2013125641A1 (ja) * | 2012-02-22 | 2013-08-29 | 東レ株式会社 | Rtm方法 |
| WO2014115668A1 (ja) * | 2013-01-24 | 2014-07-31 | 東レ株式会社 | 中空成形品の成形方法および繊維強化プラスチックの製造方法 |
| JP2016112889A (ja) * | 2014-12-15 | 2016-06-23 | ベンテラー・エスゲーエル・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンディトゲゼルシャフト | 中間繊維層による樹脂トランスファ成形方法 |
| CN106313581A (zh) * | 2015-07-10 | 2017-01-11 | 北京化工大学 | 一种基于料流前峰监测的快速树脂浸润成型工艺 |
| WO2018225271A1 (ja) * | 2017-06-09 | 2018-12-13 | 日産自動車株式会社 | 複合材料の成形方法 |
| JP2020503191A (ja) * | 2016-12-27 | 2020-01-30 | コンチネンタル ストラクチュラル プラスティックス, インコーポレイテッド | 速いサイクルタイムでの連続チャネル樹脂トランスファー成形法 |
| JP2021112885A (ja) * | 2020-01-21 | 2021-08-05 | トヨタ自動車株式会社 | 繊維強化樹脂成形品の製造方法および製造装置 |
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| CN106313581B (zh) * | 2015-07-10 | 2019-10-29 | 北京化工大学 | 一种基于料流前峰监测的快速树脂浸润成型工艺 |
| CN106313581A (zh) * | 2015-07-10 | 2017-01-11 | 北京化工大学 | 一种基于料流前峰监测的快速树脂浸润成型工艺 |
| JP2020503191A (ja) * | 2016-12-27 | 2020-01-30 | コンチネンタル ストラクチュラル プラスティックス, インコーポレイテッド | 速いサイクルタイムでの連続チャネル樹脂トランスファー成形法 |
| JP7058015B2 (ja) | 2016-12-27 | 2022-04-21 | テイジン オートモーティブ テクノロジーズ, インコーポレイテッド | 速いサイクルタイムでの連続チャネル樹脂トランスファー成形法 |
| WO2018225271A1 (ja) * | 2017-06-09 | 2018-12-13 | 日産自動車株式会社 | 複合材料の成形方法 |
| JPWO2018225271A1 (ja) * | 2017-06-09 | 2019-12-26 | 日産自動車株式会社 | 複合材料の成形方法 |
| US11046028B2 (en) | 2017-06-09 | 2021-06-29 | Nissan Motor Co., Ltd. | Method for molding composite material |
| JP2021112885A (ja) * | 2020-01-21 | 2021-08-05 | トヨタ自動車株式会社 | 繊維強化樹脂成形品の製造方法および製造装置 |
| JP7230833B2 (ja) | 2020-01-21 | 2023-03-01 | トヨタ自動車株式会社 | 繊維強化樹脂成形品の製造方法および製造装置 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2679372A4 (en) | 2017-08-30 |
| CN103328178B (zh) | 2015-08-05 |
| US9604415B2 (en) | 2017-03-28 |
| US9950479B2 (en) | 2018-04-24 |
| EP2679372A1 (en) | 2014-01-01 |
| KR20140006856A (ko) | 2014-01-16 |
| US20160339648A1 (en) | 2016-11-24 |
| EP2679372B1 (en) | 2019-08-07 |
| JP5812438B2 (ja) | 2015-11-11 |
| JPWO2012115067A1 (ja) | 2014-07-07 |
| CN103328178A (zh) | 2013-09-25 |
| KR101914803B1 (ko) | 2018-11-02 |
| US20130328236A1 (en) | 2013-12-12 |
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