JPH0641312A - Method for judging degree of curing of thermosetting resin - Google Patents
Method for judging degree of curing of thermosetting resinInfo
- Publication number
- JPH0641312A JPH0641312A JP19070691A JP19070691A JPH0641312A JP H0641312 A JPH0641312 A JP H0641312A JP 19070691 A JP19070691 A JP 19070691A JP 19070691 A JP19070691 A JP 19070691A JP H0641312 A JPH0641312 A JP H0641312A
- Authority
- JP
- Japan
- Prior art keywords
- curing
- degree
- thermosetting resin
- resin
- color tone
- 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
Landscapes
- Investigating Or Analysing Materials By Optical Means (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、複合材料用のマトリッ
クス樹脂、もしくは単独で成形材料として使用されてい
る熱硬化性樹脂の硬化度を簡便に判定することによっ
て、それを利用するＦＲＰ製造等の効率を高め、省エネ
ルギ化を図るものである。FIELD OF THE INVENTION The present invention relates to a matrix resin for a composite material, or FRP production using the matrix resin by simply judging the degree of curing of a thermosetting resin used alone as a molding material. The energy efficiency is improved by increasing the efficiency of.
【０００２】[0002]
【従来の技術】熱硬化性樹脂は樹脂系複合材料のマトリ
ックス樹脂、もしくは単独での成形材料として幅広く使
用されている。特に最近では、軽薄短小化の流れによ
り、その伸びは著しい。熱硬化性樹脂はその優れた機械
的特性、耐熱性、耐薬品性等によって、複合材料用マト
リックス樹脂の主要材料であるとともに、成形材料とし
ても古くから使用されている。2. Description of the Related Art Thermosetting resins are widely used as matrix resins for resin-based composite materials or as individual molding materials. Especially in recent years, the growth has been remarkable due to the trend of miniaturization. A thermosetting resin is a main material of a matrix resin for composite materials due to its excellent mechanical properties, heat resistance, chemical resistance and the like, and has been used as a molding material for a long time.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、熱硬化
性樹脂にも欠点があり、その一つとして硬化度が最終製
品の機械的性質に大きく影響することがあげられる。完
全に硬化度が高められれば不溶不融となり優れた特性を
発揮するが、配合不良もしくは不適切な硬化条件下で
は、硬化度を充分に高めることができず、本来の特性が
発揮できないため製造過程において硬化度を細心の注意
をもって監視する必要がある。また、熱硬化性樹脂は熱
可塑性樹脂のように成形不良となった樹脂を再使用する
ことができないため、硬化度の測定が非常に重要な生産
過程における要素となっている。熱硬化性樹脂の硬化度
の測定に関しては、従来からも種々の方法が考えられて
いる。例えば、針入度を利用する方法（特開昭５１−１
３１５８９）、ねじれ角を利用する方法（特開昭５３−
１１３５９１）、圧力を利用する方法（特開昭５４−９
７６６０）や電気物性を利用する方法（特開昭５８−１
３９０５７）、有機染料を利用する方法（特開昭５４−
１２４０９４）があげられる。しかしこれらの方法はい
ずれも製造工程に組み込むには工程変更を有するほど大
規模となったり、測定に長時間が必要であったり、製品
に傷をつけてしまったり、配合を変更するなどの難点を
有する。本発明は、従来配合を何ら変更することなく、
また製品に傷をつけることなく、簡便な装置で非常な短
時間で硬化度を測定する方法を提供するものである。However, thermosetting resins also have drawbacks, and one of them is that the degree of curing greatly affects the mechanical properties of the final product. When the degree of cure is completely increased, it becomes insoluble and infusible and exhibits excellent properties, but under poor compounding conditions or inadequate curing conditions, the degree of cure cannot be sufficiently increased, and the original properties cannot be exhibited, so the production The degree of cure needs to be monitored closely in the process. Further, since a thermosetting resin cannot reuse a resin that has been poorly molded like a thermoplastic resin, measuring the degree of curing is a very important factor in the production process. Conventionally, various methods have been considered for measuring the degree of curing of a thermosetting resin. For example, a method of utilizing penetration (Japanese Patent Application Laid-Open No. 51-1).
31589), a method using a twist angle (Japanese Patent Laid-Open No. 53-
113591), a method utilizing pressure (JP-A-54-9)
7660) and a method utilizing electric properties (Japanese Patent Laid-Open No. 58-1).
39057), a method utilizing an organic dye (JP-A-54-54).
124094). However, all of these methods have the drawbacks that they need to be changed in order to incorporate them into the manufacturing process, require a long time for measurement, damage the product, and change the formulation. Have. The present invention, without any modification of the conventional formulation,
It also provides a method for measuring the degree of curing in a very short time with a simple device without damaging the product.
【０００４】[0004]
【問題点を解決するための手段】本発明は上記課題を解
決するために、複合材料用のマトリックス樹脂、もしく
は単独で成形材料として使用されている熱硬化性樹脂の
硬化度を簡便に判定する熱硬化性樹脂の硬化度判定方法
において、熱硬化性樹脂の硬化時に、その配合によって
自然に発生する色調を測定することにより、判定するこ
とを特徴とする熱硬化性樹脂の硬化度判定方法を提供す
るものである。In order to solve the above problems, the present invention simply determines the degree of cure of a matrix resin for a composite material or a thermosetting resin used alone as a molding material. In the method for determining the degree of curing of a thermosetting resin, a method for determining the degree of curing of a thermosetting resin is characterized by determining the color tone that naturally occurs due to its composition when the thermosetting resin is cured. It is provided.
【０００５】[0005]
【作用】本発明は、従来の配合条件を変更することな
く、また簡単な装置で１〜２秒という非常に短時間で測
定を可能とし、しかも非破壊的な測定方法を提供するに
ある。非破壊的な測定方法であるので製品に傷をつける
ことがなく、したがって、製品の全数について測定する
ことができるとともに、工程に組み込むことも容易であ
る。また、色調の測定は簡便な装置で行うことができる
ため、コスト面でも有利となる。The present invention provides a non-destructive measuring method which enables measurement in a very short time of 1 to 2 seconds with a simple device without changing the conventional compounding conditions. Since it is a non-destructive measuring method, it does not damage the product, and therefore it is possible to measure the total number of products and it is easy to incorporate it into the process. Further, the color tone can be measured with a simple device, which is advantageous in terms of cost.
【０００６】[0006]
【実施例】従来から熱硬化性樹脂の硬化物の色調はラン
ダムなものであり、その構造的特徴たとえば硬化度とは
関係がないと考えられてきた。そのため、色調によって
硬化度を判定するには特定の有機染料を追加すること
（特開昭５４−１２４０９４）が必要と考えられた。し
かし、出願人はこの問題に取組み各種の実験を行った結
果、熱硬化性樹脂の硬化度は、その構造的特徴と密接な
関係があるとともに、複合材料であってもその色調と相
関関係が成り立つことを明らかとした。以下、実施例に
より説明する。炭素繊維ぺーパー（日本カーボン ＳＨ
−３５Ｚ）にビスフェノール形エポキシ樹脂（油化シェ
ル ＥＰ８２８）を含浸させ、風乾（２４時間）した
後、８枚を積層して、エポキシ樹脂の硬化度制御を行
い、各種硬化度をもつＣＦＲＰ板（厚さ約２ｍｍ×幅約
３５ｍｍ×長さ約１００ｍｍ）を製作した。製作したＣ
ＦＲＰ板の表面の色調を、国際照明学会による規格（Ｃ
ＩＥ１９７６）に準拠し、色彩色差計（ミノルタ（株）
ＣＲ−１００）を用いて測定した。また、架橋密度は同
一ＣＦＲＰ板から切り出した試料の動的弾性率を測定
し、その値からゴム理論により算出した。その結果を表
１に示す。EXAMPLES It has been conventionally considered that the color tone of a cured product of a thermosetting resin is random and has no relation to its structural characteristics such as the degree of curing. Therefore, it was considered necessary to add a specific organic dye (Japanese Patent Laid-Open No. 54-124094) in order to judge the degree of curing based on the color tone. However, as a result of various experiments carried out by the applicant on this problem, the degree of cure of the thermosetting resin is closely related to its structural characteristics, and even the composite material is correlated with its color tone. It was made clear that it holds. Hereinafter, description will be made with reference to examples. Carbon fiber paper (Nippon Carbon SH
-35Z) is impregnated with a bisphenol type epoxy resin (oiled shell EP828), air-dried (24 hours), and then eight sheets are laminated to control the degree of curing of the epoxy resin, and CFRP plates having various degrees of curing ( A thickness of about 2 mm × width of about 35 mm × length of about 100 mm) was manufactured. Manufactured C
The color tone of the surface of the FRP plate is specified by the International Lighting Institute (C
Color difference meter (Minolta Co., Ltd.)
It was measured using CR-100). Further, the crosslink density was calculated by measuring the dynamic elastic modulus of a sample cut out from the same CFRP plate and using the value based on the rubber theory. The results are shown in Table 1.
【０００７】[0007]
【表１】 [Table 1]
【０００８】架橋密度はすなわち硬化度を表わす値であ
る。架橋密度と感覚色度（Ｌ* ）、感覚色度（ｂ* ）な
らびに色差（△Ｅ* ab）を図示すると、図１〜３のよう
になりほぼ直線関係の相関がえられた。一部、架橋密度
の高い方でずれる試料もあるが、実用的には十分な直線
関係である。このことは、ＣＦＲＰ板の色調を測定する
ことにより、樹脂の硬化度を判定することができること
を証明している。また、感覚色度のＬ* 、ａ* 、ｂ* も
しくは、色差△Ｅ* abと架橋密度の関係は、樹脂の種類
や配合条件によって異なると考えられるが、最も相関関
係の強い因子、例えば本例では感覚色度Ｌ* 又はｂ* の
データを蓄積することにより、樹脂の硬化度を実用的に
判定することができる。The crosslink density is a value representing the degree of curing. The cross-linking density, the sensory chromaticity (L * ), the sensory chromaticity (b * ) and the color difference (ΔE * ab) are shown in FIG. There are some samples that deviate at the higher crosslink density, but the linear relationship is practically sufficient. This proves that the degree of cure of the resin can be determined by measuring the color tone of the CFRP plate. Further, the relationship between the sensory chromaticity L * , a * , b * or the color difference ΔE * ab and the crosslinking density is considered to vary depending on the type of resin and the compounding conditions. In the example, the degree of cure of the resin can be practically determined by accumulating the data of the sensory chromaticity L * or b * .
【０００９】炭素繊維朱子織布（日本カーボン（株）＃
３２４０）を用いて、実施例１と同じ方法によってＣＦ
ＲＰ板を製作し、その架橋密度と色調を測定した。その
結果を表２に示す。Carbon fiber satin woven fabric (Nippon Carbon Co., Ltd. #
3240) and CF in the same manner as in Example 1.
An RP plate was manufactured, and its crosslink density and color tone were measured. The results are shown in Table 2.
【００１０】[0010]
【表２】 [Table 2]
【００１１】架橋密度はすなわち硬化度を表わす値であ
る。架橋密度と感覚色度（Ｌ* ）、感覚色度（ｂ* ）な
らびに色差（△Ｅ* ab）を図示すると、図４〜６のよう
になりほぼ直線関係の相関がえられた。このことは、Ｃ
ＦＲＰ板の色調を測定することにより、樹脂の硬化度を
判定することができることを証明している。The crosslink density is a value representing the degree of curing. The cross-linking density, sensory chromaticity (L * ), sensory chromaticity (b * ), and color difference (ΔE * ab) are shown in FIGS. 4 to 6, and almost linear relationships are obtained. This means that
It has been proved that the degree of cure of the resin can be determined by measuring the color tone of the FRP plate.
【００１２】アラミド繊維平織布（東レ（株）Ｔ−１３
Ｄ）を用いて、実施例１と同じ方法によってＡＦＲＰ板
を製作し、その架橋密度と色調を測定した。その結果を
表３に示す。Aramid fiber plain woven cloth (Toray Co., Ltd. T-13)
Using D), an AFRP plate was manufactured by the same method as in Example 1, and its crosslink density and color tone were measured. The results are shown in Table 3.
【００１３】[0013]
【表３】 [Table 3]
【００１４】[0014]
【発明の効果】本発明によれば、簡便な装置で製品表面
の色調を測定することですぐに硬化度を推定することが
可能であるため、１〜２秒という非常に短い時間で測定
を完了できるとともに、対象物には光が極めて短い時間
照射されるのみで、機械的な力を全く負荷する必要がな
いため、製造作業工程にも容易に組み込むことができる
とともに、測定器は簡便で安価であるので、コスト面で
も有利であり、製品全数について測定を行うことで信頼
性のある樹脂硬化物の製造を行うことができる。本発明
によって、熱硬化性樹脂の成形時の最大の課題となって
いた硬化度の測定が容易となり、製品の均質性が向上す
ることで、信頼性のある製品が連続してえることが可能
となる。それによって、熱硬化性樹脂を用いたＦＲＰの
最大の特徴である優れた軽量性、機械的特性がますます
安定したものとなり、自動車、鉄道、航空機などの交通
分野、スポーツ用品の分野、漁業、工業などの産業分野
等の分野において、さらに広範囲な分野での使用が見込
まれる。According to the present invention, the degree of curing can be estimated immediately by measuring the color tone of the surface of a product with a simple device. Therefore, the measurement can be performed in a very short time of 1 to 2 seconds. It can be completed, and the object is only irradiated with light for an extremely short period of time, and no mechanical force has to be applied at all, so it can be easily incorporated into the manufacturing work process and the measuring device is simple. Since it is inexpensive, it is also advantageous in terms of cost, and it is possible to manufacture a reliable resin cured product by measuring all the products. According to the present invention, it becomes easy to measure the degree of curing, which has been the biggest problem during molding of thermosetting resin, and the homogeneity of the product is improved, so that a reliable product can be obtained continuously. Becomes As a result, the outstanding characteristics of FRP using thermosetting resin, which is excellent in lightness and mechanical properties, are becoming more and more stable, and the fields of transportation such as automobiles, railroads and airplanes, the field of sports equipment, the fishing industry, It is expected to be used in a wider range of fields such as industrial fields such as industry.
【図１】樹脂の硬化度と感覚色度（Ｌ* ）の関係を表わ
す図。（ＣＦペーパー／ＥＰ）FIG. 1 is a diagram showing a relationship between a resin curing degree and a sensory chromaticity (L * ). (CF paper / EP)
【図２】樹脂の硬化度と感覚色度（ｂ* ）の関係を表わ
す図。（ＣＦペーパー／ＥＰ）FIG. 2 is a diagram showing a relationship between a resin curing degree and a sensory chromaticity (b * ). (CF paper / EP)
【図３】樹脂の硬化度と感覚色度（△Ｅ* ab）の関係を
表わす図。（ＣＦペーパー／ＥＰ）FIG. 3 is a diagram showing a relationship between a resin curing degree and a sensory chromaticity (ΔE * ab). (CF paper / EP)
【図４】樹脂の硬化度と感覚色度（Ｌ* ）の関係を表わ
す図。（ＣＦクロス／ＥＰ）FIG. 4 is a diagram showing a relationship between a resin curing degree and a sensory chromaticity (L * ). (CF cross / EP)
【図５】樹脂の硬化度と感覚色度（ｂ* ）の関係を表わ
す図。（ＣＦクロス／ＥＰ）FIG. 5 is a diagram showing the relationship between the degree of cure of resin and the sensory chromaticity (b * ). (CF cross / EP)
【図６】樹脂の硬化度と感覚色度（△Ｅ* ab）の関係を
表わす図。（ＣＦクロス／ＥＰ）FIG. 6 is a diagram showing the relationship between the degree of cure of resin and the sensational chromaticity (ΔE * ab). (CF cross / EP)
Claims (1)
は単独で成形材料として使用されている熱硬化性樹脂の
硬化度を簡便に判定する熱硬化性樹脂の硬化度判定方法
において、熱硬化性樹脂の硬化時に、その配合によって
自然に発生する色調を測定することにより、判定するこ
とを特徴とする熱硬化性樹脂の硬化度判定方法。1. A method for determining the degree of cure of a thermosetting resin, which comprises simply determining the degree of cure of a matrix resin for a composite material or a thermosetting resin used alone as a molding material. A method for determining the degree of cure of a thermosetting resin, which comprises making a determination by measuring a color tone that naturally occurs due to its composition during curing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03190706A JP3083877B2 (en) | 1991-07-04 | 1991-07-04 | Method for determining the degree of cure of thermosetting resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03190706A JP3083877B2 (en) | 1991-07-04 | 1991-07-04 | Method for determining the degree of cure of thermosetting resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0641312A true JPH0641312A (en) | 1994-02-15 |
| JP3083877B2 JP3083877B2 (en) | 2000-09-04 |
Family
ID=16262486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03190706A Expired - Fee Related JP3083877B2 (en) | 1991-07-04 | 1991-07-04 | Method for determining the degree of cure of thermosetting resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3083877B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008046113A (en) * | 2006-07-21 | 2008-02-28 | Sekisui Chem Co Ltd | Inspection method of inspecting curing state of fiber reinforced plastic material lining buried pipe |
| JP2014512539A (en) * | 2011-04-19 | 2014-05-22 | オウェンス コーニング インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー | Online determination method for the curing state of glass fiber products |
| JP2014517917A (en) * | 2011-04-19 | 2014-07-24 | オウェンス コーニング インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー | Apparatus and method for monitoring curing, and process control of glass fiber molding operation |
-
1991
- 1991-07-04 JP JP03190706A patent/JP3083877B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008046113A (en) * | 2006-07-21 | 2008-02-28 | Sekisui Chem Co Ltd | Inspection method of inspecting curing state of fiber reinforced plastic material lining buried pipe |
| JP2014512539A (en) * | 2011-04-19 | 2014-05-22 | オウェンス コーニング インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー | Online determination method for the curing state of glass fiber products |
| JP2014517917A (en) * | 2011-04-19 | 2014-07-24 | オウェンス コーニング インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー | Apparatus and method for monitoring curing, and process control of glass fiber molding operation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3083877B2 (en) | 2000-09-04 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |