JPS62146929A - Fiber-reinforced composite material - Google Patents
Fiber-reinforced composite materialInfo
- Publication number
- JPS62146929A JPS62146929A JP28567085A JP28567085A JPS62146929A JP S62146929 A JPS62146929 A JP S62146929A JP 28567085 A JP28567085 A JP 28567085A JP 28567085 A JP28567085 A JP 28567085A JP S62146929 A JPS62146929 A JP S62146929A
- Authority
- JP
- Japan
- Prior art keywords
- mixture
- fiber
- resin
- weight
- reinforced composite
- 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
- Reinforced Plastic Materials (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、加熱加圧条件下において高速成形が可能であ
って車輌用部材、建築材料、道路資材等において特に屋
外使用に好適な、新規な繊維強化複合材料に関するもの
である。[Detailed Description of the Invention] [Industrial Application Field] The present invention is a novel product which can be formed at high speed under heating and pressurizing conditions and is particularly suitable for outdoor use in vehicle parts, building materials, road materials, etc. The present invention relates to fiber-reinforced composite materials.
従来より、ta維強化複合材料はプラスチックの有する
易加工性、非腐食性に機械的強度を付加しうることから
、車輛用部材、建築材料、住設機器等に広く利用されて
いる。これらの繊維強化複合材料としては、不飽和ポリ
エステル樹脂やエポキシ樹脂が樹脂成分として広く用い
られているが、いずれも耐候性が不良なことから屋外使
用においては塗装が必須であり、塗装を必要としない繊
維強化複合材料の提供が希求されてきた。Conventionally, TA fiber-reinforced composite materials have been widely used in vehicle components, building materials, housing equipment, etc. because they can add mechanical strength to the easy processability and non-corrosion properties of plastics. Unsaturated polyester resins and epoxy resins are widely used as resin components for these fiber-reinforced composite materials, but both have poor weather resistance and must be painted when used outdoors. There has been a desire to provide fiber-reinforced composite materials that do not.
一方、繊維強化複合材料の成形法はハンドレーアツブ法
にはじまり、レジンインジェクション法、コールドプレ
ス法、プルトルージョン法、フィラメントワインディン
グ法、シートモールディング法(SMC法)、バルクモ
ールディング法(BMC法)等が各種提案されているが
、任意の形状の成形品を高速に生産するには、SMC法
、BMC法の加熱加圧成形法がすぐれており、これ等の
方法によって屋外使用可能な耐候性にすぐれた繊維強化
複合材料が特に望まれている。On the other hand, molding methods for fiber-reinforced composite materials include the Handley Atsushi method, resin injection method, cold press method, pultrusion method, filament winding method, sheet molding method (SMC method), bulk molding method (BMC method), etc. Although various proposals have been made, the SMC method and BMC method are excellent for rapidly producing molded products of arbitrary shapes, and these methods have excellent weather resistance that can be used outdoors. Fiber-reinforced composite materials that have a similar structure are particularly desirable.
これ等の要求を満たす為、古くから例えば特開昭49−
104937に示されているように、メタクリル酸エス
テルモノマー及びメタクリル樹脂からなるアクリル系複
合材料の提案がなされているが、従来開始された方法に
おいてはSMC法、BMC法等の加熱加圧成形に適した
成形前の粘度特性や成形時のフロー特性が得られず実用
化に到っていない。In order to meet these demands, for example, JP-A-49-
104937, an acrylic composite material consisting of a methacrylic acid ester monomer and a methacrylic resin has been proposed, but in conventional methods, it is not suitable for hot pressure molding such as SMC method and BMC method. The viscosity characteristics before molding and the flow characteristics during molding cannot be obtained, so it has not been put into practical use.
本発明は、耐候性にすぐれた繊維強化複合材料をSMC
法又はBMC法で成形するにあたり、その成形前の粘度
特性及び成形時のフロー特性を上記方法に適するように
改善しようとするものである。The present invention uses SMC fiber reinforced composite materials with excellent weather resistance.
The aim is to improve the viscosity characteristics before molding and the flow characteristics during molding to make them suitable for the above-mentioned method.
本発明の繊維強化複合材料は、
(A)側鎖に一〇GO−X−C:OOH(式中、Xは芳
香族基又は脂環族基)を樹脂1000 g中0.05〜
1.0モル含有するメタクリル酸エステル共重合樹脂1
0〜4゜重量%、
(B)一分子中に2個以上のアクリロイル又はメタクリ
ロイル基を含有する多価ビニルオリゴマー5〜40重量
%、および
(C)ビニル単量体20〜85重量%
からなる配合物に強化繊維及び二価金属の酸化物又は水
酸化物を混合せしめた後、加熱加圧成形してなるもので
ある。The fiber-reinforced composite material of the present invention has (A) 10GO-X-C:OOH (in the formula, X is an aromatic group or alicyclic group) in the side chain of 0.05 to 0.05 to 1000 g of resin.
Methacrylic acid ester copolymer resin 1 containing 1.0 mol
0 to 4% by weight, (B) 5 to 40% by weight of a polyvalent vinyl oligomer containing two or more acryloyl or methacryloyl groups in one molecule, and (C) 20 to 85% by weight of vinyl monomer. It is formed by mixing reinforcing fibers and divalent metal oxides or hydroxides into a compound, and then heating and press-molding the mixture.
上記(A)の共重合樹脂は、特定の構造、すなわち、−
0CO−X−COOH(Xは芳香族基又は脂環族基)を
側鎖に有することを特徴としている。この構造は、例え
ばヒドロキシエチルメタクリレート、ヒドロキシエチル
アクリレート、ヒドロキシプロピルメタクリレート、ヒ
ドロキシプロピルアクリレート、ヒドロキシブチルメタ
クリレート、ヒドロキシブチルアクリレートの如きヒド
ロキシ含有ビニル単量体と、例えば無水フタル酸、テト
ラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メ
チルテトラヒドロ無水フタル酸、無水ナジック酸等の芳
香族又は脂環族酸無水物類との付加反応によって得られ
る単量体類を共重合するか或いは、上記ヒドロキシル基
含有ビニル単量体の共重合体に、上記の酸無水物類を付
加反応することによって得られる。上記の構造を有する
単量体成分は、アクリル酸エステル類、又はメタクリル
酸エステル類が好適であり、メタクリル酸メチル、メタ
クリル酸エチル、メタクリル酸イソプロピル、メタクリ
ル酸イソブチル、メタクリル酸シクロヘキシル等が特に
好適であり、他のメタクリル酸エステル類、アクリル酸
エステル類、スチレン、α−メチルスチレン、ビニルト
ルエン、パラメチルスチレン、クロロスチレン等の芳香
族単量体、酢酸ビニル、プロピオン酸ビニル等のビニル
エステル類、塩化ビニル、塩化ビニリデン等のハロゲン
化ビニル単量体、アクリロニトリル、メタクリロイル基
ル等の不飽和ニトリル類等を共重合成分として併用して
も良い。The above copolymer resin (A) has a specific structure, that is, -
It is characterized by having 0CO-X-COOH (X is an aromatic group or an alicyclic group) in a side chain. This structure can be used with hydroxy-containing vinyl monomers such as hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, hydroxybutyl acrylate, and hydroxy-containing vinyl monomers such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydroanhydride. By copolymerizing monomers obtained by addition reaction with aromatic or alicyclic acid anhydrides such as phthalic acid, methyltetrahydrophthalic anhydride, and nadic anhydride, or by copolymerizing the above-mentioned hydroxyl group-containing vinyl monomers. It can be obtained by addition reaction of the above-mentioned acid anhydrides to the copolymer. The monomer component having the above structure is preferably acrylic esters or methacrylic esters, with methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, etc. being particularly preferred. Yes, other methacrylic esters, acrylic esters, aromatic monomers such as styrene, α-methylstyrene, vinyltoluene, paramethylstyrene, chlorostyrene, vinyl esters such as vinyl acetate and vinyl propionate, Vinyl halide monomers such as vinyl chloride and vinylidene chloride, unsaturated nitriles such as acrylonitrile and methacryloyl groups, etc. may be used in combination as copolymerization components.
共重合樹脂中の上記の特定の構造のカルボキシル基の含
有量は、樹脂1000g中0.05〜1.0モルであり
、この範囲において適正な成形前の粘度特性及び成形時
のフロー特性が得られる。上記構造のカルボキシル基は
二価金属の酸化物又は水酸化物とイオン的に結合し、樹
脂成分を効率よく増粘させて適正な成形前の粘度特性(
通常10〜150万ボイズ/25℃)を付与すると共に
、加熱時にはイオン結合が適度に解離して良好なフロー
特性を示すものと考えられ、従来提案されたアクリル酸
又はメタクリル酸の如き不飽和単量体の共重合樹脂にお
いては実現しえなかった性質を示す。The content of carboxyl groups with the above-mentioned specific structure in the copolymer resin is 0.05 to 1.0 mol per 1000 g of resin, and within this range, appropriate viscosity characteristics before molding and flow characteristics during molding can be obtained. It will be done. The carboxyl group in the above structure ionically bonds with the divalent metal oxide or hydroxide, efficiently thickens the resin component, and provides appropriate viscosity characteristics before molding (
It is believed that the ionic bonds are moderately dissociated during heating and exhibit good flow characteristics. It exhibits properties that could not be achieved with polymeric copolymer resins.
上記の特定のカルボキシル基の含有量が樹脂1000g
中0.0中子。以下では増粘が不十分で、成形前のハン
ドリングが困難であり、又1.0モル以上では、成形時
のフロー特性が低下したり、成形した複合材料の耐水性
が低下し不適当である。特に、 0.2〜0.7モルが
好適である。The above specific carboxyl group content is 1000g of resin
0.0 middle child. If it is less than 1.0 mol, the viscosity will be insufficiently thickened and handling before molding will be difficult, and if it is more than 1.0 mol, the flow characteristics during molding will deteriorate and the water resistance of the molded composite material will decrease, making it unsuitable. . In particular, 0.2 to 0.7 mol is suitable.
前記(B)の多価ビニルオリゴマーとしては、多価アル
コールとアクリル酸又はメタクリル酸のエステル化物が
用いられ、例えばエチレングリコール、ジエチレングリ
コール、ポリエチレングリコール、プロピレングリコー
ル、ジプロビレングリコール、ブタンジオール、ベンタ
ンジオール、ヘキサンジオール、水添ビスフェノールA
、トリメチロールエタン、トリメチロールプロパン、ペ
ンタエリスリトール、ジペントール、ソルビトール、ト
リスヒドロキシエチルイソシアヌレート等の多価アルコ
ール類の他に上記多価アルコールの多価グリシジルエー
テル類、脂環族ポリエポキシド類、芳香族カルボン酸ジ
グリシジルエステル類も又多価アルコール成分として有
用である。上記(B)の多価ビニルオリゴマーは、成形
物に耐熱性を付与し、又、成形時に金型からの脱型を容
易にする。As the polyvalent vinyl oligomer (B), an esterified product of polyhydric alcohol and acrylic acid or methacrylic acid is used, such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, diprobylene glycol, butanediol, bentanediol, Hexanediol, hydrogenated bisphenol A
In addition to polyhydric alcohols such as , trimethylolethane, trimethylolpropane, pentaerythritol, dipentol, sorbitol, and trishydroxyethyl isocyanurate, polyglycidyl ethers of the above polyhydric alcohols, alicyclic polyepoxides, and aromatic carboxyl Acid diglycidyl esters are also useful as polyhydric alcohol components. The polyvalent vinyl oligomer (B) above imparts heat resistance to the molded product and also facilitates demolding from the mold during molding.
前記の(C)ビニル単量体としては、メタクリル酸メチ
ル、メタクリル酸エチル、メタクリル酸イソプロピル等
のメタクリル酸エステル類が好んで用いられ、スチレン
等の芳香族単量体も併用可能であるが、メタクリル酸エ
ステル類が単量体の50重量%以上であることが好まし
い。これ等(C)ビニル単量体は、樹脂成分を強化繊維
中に十分含浸せしめる反応性希釈剤としての役割を果す
。As the vinyl monomer (C), methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and isopropyl methacrylate are preferably used, and aromatic monomers such as styrene can also be used in combination. It is preferable that the methacrylic acid ester accounts for 50% by weight or more of the monomer. These vinyl monomers (C) serve as a reactive diluent that sufficiently impregnates the reinforcing fibers with the resin component.
前記(A)、 (B)及び(C)成分の配合割合は、(
A)が10〜40重量%、(B)が5〜40重量%、(
C)が20〜85重量%において良好な成形性、成形物
物性を示すが、(A)が15〜30重量%、(B)が1
0〜30重量%、(C)が40〜75重量%が最も好適
である。The blending ratio of the components (A), (B) and (C) is (
A) is 10-40% by weight, (B) is 5-40% by weight, (
C) exhibits good moldability and physical properties of molded products at 20 to 85% by weight, but when (A) is at 15 to 30% by weight and (B) is at 1
Most preferably, the amount of (C) is 0 to 30% by weight, and 40 to 75% by weight.
前記の樹脂形成成分(A)、 (B)及び(C)に、ガ
ラス繊維、カーボン繊維等に代表される強化用繊維、増
粘剤である二価金属の酸化物又は水酸化物、例えばマグ
ネシウム、カルシュラム、亜鉛、ストロンチウム等、並
びに公知のラジカル重合開始剤、又必要に応じ、例゛え
ば炭酸カルシウム、硫酸バリウム、タルク、シリカ、ア
ルミナ、砕砂、ガラス球等の充填剤、低収縮化助剤、着
色剤、離型剤等を混合し、通常、常温〜50℃の温度に
保持して液状の配合物を、25°Cにおける粘度を10
万〜150万ボイズに増粘せしめて切断、金型へのチャ
ージを行い易い形にして実用に供する。The resin-forming components (A), (B) and (C) include reinforcing fibers such as glass fibers and carbon fibers, and oxides or hydroxides of divalent metals as thickeners, such as magnesium. , calcilum, zinc, strontium, etc., and known radical polymerization initiators, and if necessary, fillers such as calcium carbonate, barium sulfate, talc, silica, alumina, crushed sand, glass spheres, etc., and low-shrinkage auxiliary agents. , a coloring agent, a mold release agent, etc. are mixed, and the mixture is usually maintained at a temperature of room temperature to 50°C to form a liquid formulation, with a viscosity of 10°C at 25°C.
The viscosity is increased to 1,000,000 to 1,500,000 voids, and the material is made into a form that is easy to cut and charge into a mold for practical use.
成形は通常120〜160℃に加熱された金型において
、20〜250 kg/cm’の圧力で2〜10分加圧
し、流動と硬化を同時に行わせて成形を行うことによっ
て本発明の繊維強化複合材料をうる。Molding is usually carried out in a mold heated to 120 to 160°C by applying pressure of 20 to 250 kg/cm' for 2 to 10 minutes to simultaneously flow and harden the fiber-reinforced material of the present invention. Obtain composite materials.
本発明は、特定の構成を有する共重合体樹脂を用いるこ
とにより、極めて良好な成形性を加熱加圧成形において
実現し、良好な外観、機械的物性及び極めて良好な耐候
性を有する繊維強化複合材料を得ることができた。By using a copolymer resin with a specific structure, the present invention achieves extremely good moldability in heat-pressure molding, and provides fiber-reinforced composites with good appearance, mechanical properties, and extremely good weather resistance. I was able to obtain the materials.
以下に実施例を示して本発明を具体的に説明する。 EXAMPLES The present invention will be specifically described below with reference to Examples.
実施例
の ゛
表1の実験番号1〜6(6は比較例)に示す単量体混合
物にアゾビスイソブチロニトリル10重量部を溶解し、
各々1000重量部のトルエンを入れた反応器に4時間
にわたって上記単量体混合物を連続的に添加し、その間
反応物の温度を90〜95°Cに維持し、添加終了後ア
ゾビスイソブチロニトリル10重量部を更に追加して同
温度で3時間加熱攪拌した。しかる後に反応液をエバポ
レーターに移し、減圧加熱してトルエンを蒸発除去して
固型の樹脂を得た。得られた樹脂のカルボキシル基量な
苛性カリ滴定法によって測定し併せて表1に記載した。In the example, 10 parts by weight of azobisisobutyronitrile was dissolved in the monomer mixture shown in experiment numbers 1 to 6 (6 is a comparative example) in Table 1,
The above monomer mixture was added continuously over a period of 4 hours to a reactor containing 1000 parts by weight of toluene each, during which the temperature of the reactants was maintained at 90-95°C, and after the addition was completed, azobisisobutyro 10 parts by weight of nitrile was further added and the mixture was heated and stirred at the same temperature for 3 hours. Thereafter, the reaction solution was transferred to an evaporator and heated under reduced pressure to evaporate toluene to obtain a solid resin. The carboxyl group content of the resulting resin was measured by caustic potassium titration and is also listed in Table 1.
表1
注1)樹脂番号(1)〜(6)で各々用いたカルボキシ
ル基含有単量体は〕ケ表のとおりである。Table 1 Note 1) The carboxyl group-containing monomers used in resin numbers (1) to (6) are as shown in Table 1.
シートモールデ ングコンパウンドの ゛実験番号1〜
6の各々の樹脂を用い、表2に示す多価ビニルオリゴマ
ー、ビニル単量体、重合開始剤、増粘剤、充填剤、低収
縮化剤、離型剤を混合溶解し、ポリエチレンフィルム上
に塗布し、25.4mmにカットされたガラスm維を連
続的に上部から均一に散布し、もう一枚のポリエチレン
フィルムでカバーして巻きとった後、24時間40℃に
放置してシートモールディングコンパウンドを製造した
。表2にはガラス繊維添加前の混合液の24時間40°
C放置後の粘度(40℃にて測定)及び燃焼法によって
求めた各実験番号のシートモールディングコンパウンド
のガラス繊維含有量を併せて記載する。Sheet molding compound experiment number 1~
Using each of the resins listed in Table 6, polyvalent vinyl oligomers, vinyl monomers, polymerization initiators, thickeners, fillers, low shrinkage agents, and mold release agents shown in Table 2 were mixed and dissolved, and the mixture was applied onto a polyethylene film. Glass m fibers cut to 25.4 mm were continuously and evenly sprinkled from the top, covered with another polyethylene film, rolled up, and left at 40°C for 24 hours to form a sheet molding compound. was manufactured. Table 2 shows the temperature of the mixed liquid at 40° for 24 hours before adding glass fiber.
The viscosity after standing (measured at 40° C.) and the glass fiber content of the sheet molding compound of each experimental number determined by the combustion method are also listed.
/ び / 雪
上記の各シートモールディングコンパウンドを、上型(
145℃)、下型(140℃)の金型間にチャージし、
100 kg/am’の圧力で5分間、加圧、加熱成形
して厚さ約4mmの成形品を得た。/ Bi / Snow Each of the above sheet molding compounds was added to the upper mold (
145℃) and the lower mold (140℃),
Pressure and heat molding was performed at a pressure of 100 kg/am' for 5 minutes to obtain a molded product with a thickness of about 4 mm.
尚、実験番号7は比較例として不飽和ポリエステル系の
市販シートモールディングコンパウンドを上記と同様な
条件で成形品を得た。表3には外観、光沢、曲げ強度、
曲げ弾性率、耐候性(サンシャインウェザオフ−ター5
00時間照射後の光沢保持率)を測定し記載した。In Experiment No. 7, as a comparative example, a molded product was obtained using a commercially available sheet molding compound based on unsaturated polyester under the same conditions as above. Table 3 shows appearance, gloss, bending strength,
Flexural modulus, weather resistance (Sunshine Weather Off-Ter 5)
The gloss retention rate after irradiation for 00 hours was measured and described.
表3Table 3
Claims (1)
芳香族基又は脂環族基)を樹脂1000g中0.05〜
1.0モル含有するメタクリル酸エステル共重合樹脂1
0〜40重量%、 (B)一分子中に2個以上のアクリロイル又はメタクロ
イル基を含有する多価ビニルオリゴ マー5〜40重量%、および (C)ビニル単量体20〜85重量% からなる配合物に強化繊維及び二価金属の酸化物又は水
酸化物を混合し増粘せしめた後加熱加圧成形してなる繊
維強化複合材料。[Claims] 1. (A) -OCO-X-COOH (in the formula, X is an aromatic group or alicyclic group) in the side chain in 0.05 to 0.05 to 1000 g of resin
Methacrylic acid ester copolymer resin 1 containing 1.0 mol
0 to 40% by weight, (B) 5 to 40% by weight of a polyvalent vinyl oligomer containing two or more acryloyl or methacryloyl groups in one molecule, and (C) 20 to 85% by weight of vinyl monomer. A fiber-reinforced composite material made by mixing reinforcing fibers and divalent metal oxides or hydroxides, thickening the mixture, and then heating and press-molding the mixture.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60285670A JPH0618906B2 (en) | 1985-12-20 | 1985-12-20 | Fiber reinforced composite material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60285670A JPH0618906B2 (en) | 1985-12-20 | 1985-12-20 | Fiber reinforced composite material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62146929A true JPS62146929A (en) | 1987-06-30 |
JPH0618906B2 JPH0618906B2 (en) | 1994-03-16 |
Family
ID=17694531
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60285670A Expired - Lifetime JPH0618906B2 (en) | 1985-12-20 | 1985-12-20 | Fiber reinforced composite material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0618906B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01287145A (en) * | 1988-05-13 | 1989-11-17 | Showa Denko Kk | Laminated board for electric circuit |
WO2018056458A1 (en) * | 2016-09-26 | 2018-03-29 | 日本合成化学工業株式会社 | Multilayer film for fiber bonding and/or fiber sheet surface protection, and thermosetting composition for fiber bonding and/or fiber sheet surface protection |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3466259A (en) * | 1966-12-15 | 1969-09-09 | Dow Chemical Co | Thickened thermosetting vinyl ester resins |
JPS55112221A (en) * | 1979-02-22 | 1980-08-29 | Shell Int Research | Vinylester resin composition |
JPS5731912A (en) * | 1980-08-01 | 1982-02-20 | Dainippon Ink & Chem Inc | Production of acrylic smc or bmc |
-
1985
- 1985-12-20 JP JP60285670A patent/JPH0618906B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3466259A (en) * | 1966-12-15 | 1969-09-09 | Dow Chemical Co | Thickened thermosetting vinyl ester resins |
JPS55112221A (en) * | 1979-02-22 | 1980-08-29 | Shell Int Research | Vinylester resin composition |
JPS5731912A (en) * | 1980-08-01 | 1982-02-20 | Dainippon Ink & Chem Inc | Production of acrylic smc or bmc |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01287145A (en) * | 1988-05-13 | 1989-11-17 | Showa Denko Kk | Laminated board for electric circuit |
JPH0583098B2 (en) * | 1988-05-13 | 1993-11-24 | Showa Denko Kk | |
WO2018056458A1 (en) * | 2016-09-26 | 2018-03-29 | 日本合成化学工業株式会社 | Multilayer film for fiber bonding and/or fiber sheet surface protection, and thermosetting composition for fiber bonding and/or fiber sheet surface protection |
EP3517558A4 (en) * | 2016-09-26 | 2019-10-02 | Mitsubishi Chemical Corporation | Multilayer film for fiber bonding and/or fiber sheet surface protection, and thermosetting composition for fiber bonding and/or fiber sheet surface protection |
US11198281B2 (en) | 2016-09-26 | 2021-12-14 | Mitsubishi Chemical Corporation | Laminated film for fiber adhesion and/or fiber sheet surface protection and thermosetting composition for fiber adhesion and/or fiber sheet surface protection |
Also Published As
Publication number | Publication date |
---|---|
JPH0618906B2 (en) | 1994-03-16 |
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Legal Events
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EXPY | Cancellation because of completion of term |