JPH10272740A - Fiber-reinforced resin plate and its manufacture - Google Patents
Fiber-reinforced resin plate and its manufactureInfo
- Publication number
- JPH10272740A JPH10272740A JP9434697A JP9434697A JPH10272740A JP H10272740 A JPH10272740 A JP H10272740A JP 9434697 A JP9434697 A JP 9434697A JP 9434697 A JP9434697 A JP 9434697A JP H10272740 A JPH10272740 A JP H10272740A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- liquid
- paper
- titanium paper
- carrier film
- 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.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 107
- 239000011347 resin Substances 0.000 title claims abstract description 107
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000010936 titanium Substances 0.000 claims abstract description 56
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 56
- 239000000835 fiber Substances 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 29
- 238000000465 moulding Methods 0.000 claims description 15
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004744 fabric Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000005728 strengthening Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 239000003365 glass fiber Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920006337 unsaturated polyester resin Polymers 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 229920006267 polyester film Polymers 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000013007 heat curing Methods 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-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
- 239000004698 Polyethylene Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、表面材として合
板、石膏板など他の板材と接着一体化することによっ
て、壁材、床材、天井材などの建築材料に使用すること
ができる、表面装飾性に優れた繊維強化樹脂板およびそ
の製造方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a surface material which can be used for building materials such as wall materials, floor materials, ceiling materials, etc. by bonding and integrating with other plate materials such as plywood and gypsum board as the surface material. The present invention relates to a fiber reinforced resin plate having excellent decorativeness and a method for producing the same.
【０００２】[0002]
【従来の技術】屋外で使用される表示板や浴室の壁に耐
久性を付与するために、繊維強化樹脂板が使用されてい
る。この繊維強化樹脂板の装飾性を高めるために、色、
図形または模様などが施されるが、色、図形または模様
などを与える方法としては、スクリーン印刷、塗装など
外面に後加工する方法の他に、繊維強化樹脂板の透明性
を利用して、予め色、図形または模様などが印刷された
紙状のものを繊維強化樹脂板用成形材料の内部に封入し
て成形する方法がある。この封入成形としては、例えば
ガラス繊維チョップドストランドマットに硬化剤を配合
した不飽和ポリエステル樹脂を含浸した後、硬化させ、
繊維強化樹脂板を製造する工程において、ガラス繊維チ
ョップドストランドマットと同様に、印刷紙に樹脂液を
含浸して封入し、硬化させる方法が挙げられる。この方
法では、繊維強化樹脂板の製造時に使用される印刷紙
は、未硬化樹脂液が浸透できるような材質からなる紙で
あることが必要である。2. Description of the Related Art A fiber reinforced resin plate is used to impart durability to a display panel or a bathroom wall used outdoors. In order to enhance the decorativeness of this fiber reinforced resin plate,
Although a figure or pattern is applied, as a method of giving a color, a figure or a pattern, in addition to a method of post-processing the outer surface such as screen printing, painting, etc., utilizing the transparency of the fiber reinforced resin plate, There is a method in which a paper-like material on which a color, a figure, a pattern, or the like is printed is sealed in a molding material for a fiber-reinforced resin plate and molded. As this encapsulation molding, for example, after impregnating an unsaturated polyester resin blended with a curing agent into a glass fiber chopped strand mat, it is cured,
In the process of manufacturing a fiber reinforced resin plate, a method of impregnating a printing paper with a resin liquid, enclosing the resin liquid, and curing the same as in the case of the glass fiber chopped strand mat is used. In this method, it is necessary that the printing paper used in the production of the fiber reinforced resin plate is a paper made of a material through which the uncured resin liquid can penetrate.
【０００３】しかしながら、一般に未硬化樹脂液が容易
に浸透するような紙は隠蔽性が劣り、出来上がった板の
色、図形または模様などの発色性や鮮明性に劣る欠点が
あった。一方、紙繊維の間に酸化チタン粉末を充填した
通称チタン紙のように隠蔽性や発色性に優れた紙を封入
した場合、紙の性質上、樹脂液の浸透が妨げられ、紙に
よって樹脂板が表裏に分離された状態になり、板として
の性能が極端に低下し、実用上、耐水性、耐候性などの
問題があった。特に、連続的に未硬化樹脂含浸と硬化を
高速で行いながら連続的に板を成形する「連続パネル成
形法」においては、その成形速度の高速性ゆえにチタン
紙の含浸性の悪さは致命的となり、所望の性能を持った
板を得ることができなかった。[0003] However, paper in which the uncured resin liquid easily penetrates is generally inferior in concealing properties and inferior in coloration and clarity of the color, figure or pattern of the finished board. On the other hand, if paper with excellent concealing properties and coloring properties is enclosed, such as titanium paper filled with titanium oxide powder between paper fibers, the permeation of the resin liquid is impeded due to the nature of the paper, and the paper causes Were separated on the front and back, and the performance as a plate was extremely reduced, and there were problems in practical use such as water resistance and weather resistance. In particular, in the `` continuous panel molding method, '' which continuously forms a board while continuously impregnating and curing the uncured resin at a high speed, the poor impregnation of titanium paper is fatal due to the high speed of the molding speed. However, a plate having the desired performance could not be obtained.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、前述の従来
技術が有する課題に鑑みてなされたものであり、色、図
形または模様などの発色性や鮮明性に優れ、耐水性およ
び耐候性に優れた繊維強化樹脂板および繊維強化樹脂板
の製造方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is excellent in coloring and sharpness of a color, a figure or a pattern, and has excellent water resistance and weather resistance. An object is to provide an excellent fiber-reinforced resin plate and a method for producing the fiber-reinforced resin plate.
【０００５】[0005]
【課題を解決するための手段】本発明者は、上記課題を
解決するために鋭意検討した結果、多数の孔を開けたチ
タン紙に「未硬化樹脂液が含浸された補強繊維」（以
下、含浸補強繊維と略す）を積層し、加圧成形すること
により、上記課題を解決することができることを見い出
し、その知見に基づいて本発明を完成するに至った。す
なわち、本発明は、多孔チタン紙の両面に硬化性樹脂硬
化層を有し、該硬化性樹脂硬化層の少なくとも一方が補
強繊維で強化されていることを特徴とする繊維強化樹脂
板を提供するものである。また、本発明は、多孔チタン
紙の片面または両面に、未硬化硬化性樹脂液が含浸され
た補強繊維の層を形成し、続いて加圧成形によりこの未
硬化硬化性樹脂液を硬化させ、硬化性樹脂硬化層を形成
することを特徴とする繊維強化樹脂板の製造方法を提供
するものである。Means for Solving the Problems As a result of diligent studies to solve the above-mentioned problems, the present inventor has found that titanium paper having a large number of holes is provided with a "reinforcing fiber impregnated with an uncured resin solution" It has been found that the above-mentioned problems can be solved by laminating (abbreviated as impregnated reinforcing fibers) and press-forming, and the present invention has been completed based on the findings. That is, the present invention provides a fiber-reinforced resin plate having a curable resin cured layer on both surfaces of a porous titanium paper, wherein at least one of the curable resin cured layers is reinforced with reinforcing fibers. Things. Further, the present invention, on one or both sides of the porous titanium paper, to form a layer of reinforcing fibers impregnated with the uncured curable resin liquid, and then cure this uncured curable resin liquid by pressure molding, An object of the present invention is to provide a method for producing a fiber reinforced resin plate, which comprises forming a cured resin layer.
【０００６】[0006]
【発明の実施の形態】本発明において使用される硬化性
樹脂としては、種々の熱硬化性樹脂や光硬化性樹脂を使
用することができ、たとえば不飽和ポリエステル樹脂、
ビニルエステル樹脂、フェノール樹脂、ユリア樹脂、メ
ラミン樹脂、アルキッド樹脂、エポキシ樹脂、シリコー
ン樹脂などの熱硬化性樹脂、メチルメタクリレートモノ
マーやそのオリゴマー、アクリレートモノマーやそのオ
リゴマーなどの光硬化性樹脂が適用でき、不飽和ポリエ
ステル樹脂、ビニルエステル樹脂、エポキシ樹脂が好ま
しく、特に不飽和ポリエステル樹脂が好ましい。また、
硬化性樹脂としては、未硬化時に繊維およびチタン紙に
含浸を良好ならしめるには低粘度である方がよいが、２
５℃における粘度が１００〜２０００ｍＰａ・ｓの範囲
が特に好ましい。また、未硬化硬化性樹脂には、他の成
分として、充填材、増粘剤、低収縮剤、架橋剤、硬化
剤、硬化促進剤、重合禁止剤、内部離型剤、滑剤、着色
剤、重合開始剤、紫外線吸収剤などの添加剤が加えられ
る。充填材としては、たとえば炭酸カルシウム、水酸化
アルミニウム、塩化パラフィン、三酸化アンチモン、ホ
ウ酸塩、マイカ、クレー、タルク、無水珪酸、アルミナ
などが挙げられる。低収縮剤としてはポリスチレン、ポ
リメタクリル酸メチル、ポリ酢酸メチル、ポリ酢酸ビニ
ル、ポリエチレン、ポリ塩化ビニル、またはこれらの共
重合体などの熱可塑性ポリマーなどが挙げられる。硬化
剤としては、メチルエチルケトンパーオキサイドを１〜
３重量％、硬化促進剤としては、ナフテン酸コバルト６
重量％溶液を０．０５〜０．５重量％配合したものが適
している。BEST MODE FOR CARRYING OUT THE INVENTION As the curable resin used in the present invention, various thermosetting resins and photo-curable resins can be used.
Thermosetting resins such as vinyl ester resins, phenolic resins, urea resins, melamine resins, alkyd resins, epoxy resins, silicone resins, and photocurable resins such as methyl methacrylate monomers and their oligomers, acrylate monomers and their oligomers can be applied, Unsaturated polyester resins, vinyl ester resins and epoxy resins are preferred, and unsaturated polyester resins are particularly preferred. Also,
As the curable resin, it is preferable that the viscosity is low to improve the impregnation of the fiber and the titanium paper when not cured.
The viscosity at 5 ° C. is particularly preferably in the range of 100 to 2000 mPa · s. In addition, the uncured curable resin has, as other components, a filler, a thickener, a low-shrinking agent, a crosslinking agent, a curing agent, a curing accelerator, a polymerization inhibitor, an internal mold release agent, a lubricant, a coloring agent, Additives such as a polymerization initiator and an ultraviolet absorber are added. Examples of the filler include calcium carbonate, aluminum hydroxide, paraffin chloride, antimony trioxide, borate, mica, clay, talc, silicic anhydride, and alumina. Examples of the low shrinkage agent include thermoplastic polymers such as polystyrene, polymethyl methacrylate, polymethyl acetate, polyvinyl acetate, polyethylene, polyvinyl chloride, and copolymers thereof. As a curing agent, methyl ethyl ketone peroxide is 1 to
3% by weight, as a curing accelerator, cobalt naphthenate 6
A solution containing 0.05 to 0.5% by weight of a solution by weight is suitable.
【０００７】硬化性樹脂を強化する補強繊維としては、
種々の繊維を使用することができる。補強繊維の具体例
としては、たとえば、硝子繊維、炭素繊維、ボロン繊
維、炭化ケイ素繊維、ポリチタノカルボシラン繊維、ア
ルミナ繊維、チタン酸カルシウム繊維などの無機繊維、
アラミド繊維、ポリエチレン繊維、ポリエステル繊維、
ビニロン繊維などの有機繊維などが挙げられ、経済性と
光透過性から硝子繊維が好ましい。補強繊維は、短繊
維、長繊維または連続繊維のいずれであってもよい。ま
た、補強繊維は、熱硬化性樹脂中に分散させてもよい
し、あるいはシート状、マット状またはクロス状にして
使用してもよい。補強繊維の平均繊維径は、特に制限な
いが、通常１〜５０μｍであればよく、好ましくは５〜
３０μｍである。補強繊維は１種または２種以上を組み
合わせて使用できる。硬化性樹脂中の補強繊維の割合
は、硬化性樹脂１００重量部に対して通常５〜６０重量
部であり、好ましくは１０〜５０重量部、より好ましく
は１０〜４０重量部である。硬化された硬化性樹脂層の
厚みは、特に制限されないが、通常０．１〜１０ｍｍの
範囲であり、好ましくは０．２〜５ｍｍの範囲である。[0007] As a reinforcing fiber for reinforcing the curable resin,
Various fibers can be used. Specific examples of the reinforcing fiber include, for example, glass fiber, carbon fiber, boron fiber, silicon carbide fiber, polytitanocarbosilane fiber, alumina fiber, inorganic fiber such as calcium titanate fiber,
Aramid fiber, polyethylene fiber, polyester fiber,
Organic fibers such as vinylon fibers are exemplified, and glass fibers are preferable from the viewpoint of economy and light transmittance. The reinforcing fibers may be any of short fibers, long fibers or continuous fibers. The reinforcing fibers may be dispersed in a thermosetting resin, or may be used in the form of a sheet, mat, or cloth. The average fiber diameter of the reinforcing fibers is not particularly limited, but may be usually 1 to 50 μm, and preferably 5 to 50 μm.
30 μm. The reinforcing fibers can be used alone or in combination of two or more. The proportion of the reinforcing fibers in the curable resin is usually 5 to 60 parts by weight, preferably 10 to 50 parts by weight, more preferably 10 to 40 parts by weight, per 100 parts by weight of the curable resin. The thickness of the cured curable resin layer is not particularly limited, but is usually in the range of 0.1 to 10 mm, and preferably in the range of 0.2 to 5 mm.
【０００８】本発明において使用される多孔チタン紙
は、多数の孔が開けられているチタン紙である。孔は、
チタン紙を貫通している孔であり、熱硬化性樹脂がこの
孔を通ってチタン紙の反対表面に流動することができ
る。チタン紙は、紙繊維の間に酸化チタン粉末を充填し
たものであり、その紙としては、などの種々の紙を使用
することができる。また、酸化チタンの配合量は、特に
制限ないが、通常１０〜５０重量％であり、好ましくは
２０〜４０重量％である。The porous titanium paper used in the present invention is a titanium paper having a large number of holes. The hole is
Holes through the titanium paper through which thermosetting resin can flow to the opposite surface of the titanium paper. Titanium paper is one in which titanium oxide powder is filled between paper fibers, and various papers such as can be used as the paper. The amount of titanium oxide is not particularly limited, but is usually 10 to 50% by weight, and preferably 20 to 40% by weight.
【０００９】チタン紙に開ける孔の大きさおよび孔の間
隔は樹脂液の粘度との関係で決定されるが、孔の大きさ
は、通常直径０．０５〜０．６ｍｍの範囲が好ましく、
孔の間隔は通常１〜２０ｍｍが好ましい。特に好ましい
樹脂液粘度２００〜５００ｍＰａ・ｓの粘度範囲の場合
では、孔の大きさは直径０．１〜０．３ｍｍが好まし
く、孔の間隔は１〜８ｍｍが好ましい。上記の範囲より
孔の大きさが小さいと熱硬化性樹脂液はチタン紙の反対
表面に浸透しないことがある。逆に孔の大きさが上記の
範囲より大きいと浸透量が多過ぎて、キャリアフィルム
を使用して成形する場合、チタン紙表面と下側のキャリ
アフィルムの間で大きな樹脂の溜まりが発生してしま
い、チタン紙のしわ、破れにつながることがあり、また
外観上孔が目立ってしまい、装飾性の観点から好ましく
ない。孔は、チタン紙全面にわたって開けられているこ
とが望ましい。The size of the holes and the interval between the holes formed in the titanium paper are determined by the relationship with the viscosity of the resin liquid. The size of the holes is preferably in the range of usually 0.05 to 0.6 mm in diameter.
Usually, the interval between the holes is preferably 1 to 20 mm. In the case of a particularly preferable viscosity range of the resin liquid having a viscosity of 200 to 500 mPa · s, the diameter of the holes is preferably 0.1 to 0.3 mm, and the interval between the holes is preferably 1 to 8 mm. If the pore size is smaller than the above range, the thermosetting resin liquid may not penetrate the opposite surface of the titanium paper. Conversely, if the pore size is larger than the above range, the permeation amount is too large, and when molding using a carrier film, a large resin pool occurs between the titanium paper surface and the lower carrier film. This may lead to wrinkling and tearing of the titanium paper, and the appearance of the hole is conspicuous, which is not preferable from the viewpoint of decorativeness. The holes are desirably formed over the entire surface of the titanium paper.
【００１０】チタン紙に孔を開ける方法としては、たと
えば孔の径に相当する径を有する針を多数表面に備えた
押し圧板をチタン紙に押し付けて孔を開ける方法などが
挙げられる。テーパー状の針を用いれば、突き込み深さ
で孔の径を調節できる。多孔チタン紙の片面または両面
には、装飾性を向上させるために、色、図形または模様
などを施すことが好ましい。これらの色、図形または模
様などは、通常は印刷によって施される。チタン紙の厚
みは、特に制限ないが、目付に換算して通常４０〜２０
０ｇ／ｍ2の範囲であればよく、好ましくは４０〜１０
０ｇ／ｍ2の範囲である。As a method of perforating the titanium paper, for example, there is a method in which a pressing plate having a large number of needles having a diameter corresponding to the diameter of the hole is pressed against the titanium paper to form the holes. If a tapered needle is used, the diameter of the hole can be adjusted by the penetration depth. It is preferable to apply a color, a figure or a pattern to one or both sides of the porous titanium paper in order to improve decorativeness. These colors, figures or patterns are usually applied by printing. The thickness of the titanium paper is not particularly limited, but is usually 40 to 20 in terms of basis weight.
0 g / m 2 , preferably 40 to 10 g / m 2.
The range is 0 g / m 2 .
【００１１】本発明の繊維強化樹脂板の製造方法におい
ては、最初に多孔チタン紙の片面または両面に、含浸補
強繊維を積層する。多孔チタン紙と含浸補強繊維との積
層物は、キャリアフィルムで挟むことが好ましい。多孔
チタン紙の片面に含浸補強繊維の層を形成する場合、キ
ャリアフィルムを使用する方法としては、たとえばキャ
リアフィルムの上面に未硬化樹脂液を塗布し、次いでチ
タン紙を載せ、次いで未硬化樹脂液を塗布し、さらに補
強繊維をこの樹脂液に含ませ、続いて未硬化樹脂液表面
をキャリアフィルムで覆い、未硬化樹脂液を硬化させる
方法が挙げられる。なお、キャリアフィルムの上面にチ
タン紙を載せる際、チタン紙を載せる前に、キャリアフ
ィルムの上面には、未硬化樹脂液を塗布しなくても、チ
タン紙の孔を通って未硬化樹脂液が浸透するので、チタ
ン紙は上下両面を未硬化樹脂で被覆されることになり、
本発明の繊維強化樹脂板を製造することができるが、キ
ャリアフィルムの上面に予め熱硬化性樹脂液または補強
繊維含量の少ない含浸補強繊維を塗布していても差し支
えない。また、多孔チタン紙の両面に含浸補強繊維の層
を形成する場合、キャリアフィルムを使用する方法とし
ては、たとえばキャリアフィルムの上面に未硬化樹脂液
を塗布し、さらに補強繊維をこの樹脂液に含ませ、その
上にチタン紙を載せ、次いで未硬化樹脂液を塗布し、さ
らに補強繊維をこの樹脂液に含ませて、続いて未硬化樹
脂液表面をキャリアフィルムで覆い、未硬化樹脂液を硬
化させる方法が挙げられる。In the method for producing a fiber-reinforced resin plate of the present invention, first, impregnated reinforcing fibers are laminated on one or both sides of a porous titanium paper. The laminate of the porous titanium paper and the impregnated reinforcing fibers is preferably sandwiched between carrier films. When a layer of impregnated reinforcing fibers is formed on one side of the porous titanium paper, a method of using a carrier film is, for example, to apply an uncured resin liquid on the upper surface of the carrier film, then place the titanium paper, and then apply the uncured resin liquid. Is applied, the reinforcing fibers are contained in the resin liquid, the surface of the uncured resin liquid is subsequently covered with a carrier film, and the uncured resin liquid is cured. When the titanium paper is placed on the upper surface of the carrier film, the uncured resin liquid passes through the holes in the titanium paper without applying the uncured resin liquid on the upper surface of the carrier film before placing the titanium paper. Because it penetrates, the titanium paper will be coated on both upper and lower surfaces with uncured resin,
Although the fiber reinforced resin plate of the present invention can be manufactured, a thermosetting resin liquid or an impregnated reinforcing fiber having a low reinforcing fiber content may be previously applied to the upper surface of the carrier film. When the layers of the impregnated reinforcing fibers are formed on both surfaces of the porous titanium paper, a method of using a carrier film is, for example, to apply an uncured resin liquid on the upper surface of the carrier film and further include the reinforcing fibers in the resin liquid. Titanium paper is placed on top of it, then the uncured resin liquid is applied, reinforcing fibers are included in this resin liquid, and the surface of the uncured resin liquid is covered with a carrier film, and the uncured resin liquid is cured. There is a method to make it.
【００１２】本発明の繊維強化樹脂板の製造方法におい
ては、多孔チタン紙と含浸補強繊維との積層物を封入成
形、連続パネル成形、プレス成形などの加圧成形により
硬化させ、多孔チタン紙の両面を熱硬化性樹脂硬化層で
被覆させる。この硬化層の少なくとも一方が含浸補強繊
維により形成された層である。この封入成形とは、多孔
チタン紙を熱硬化性樹脂硬化層の中に封じる成形方法を
いう。また、連続パネル成形とは、連続的に樹脂含浸と
硬化を高速で行いながら連続的に板を成形する方法をい
う。なお、上記方法においては、硬化させる前に、前記
積層物は押圧して未硬化樹脂液をチタン紙の孔に浸透さ
せることが好ましい。この押圧の圧力は、特に制限ない
が、通常０．０５〜１．０ｋｇ／ｃｍ2が好ましい。硬
化は、通常は加熱炉に前記積層物を入れて行う。加熱炉
の温度は、硬化性樹脂の種類により異なるが、通常は８
０〜１６０℃である。なお、加熱炉の中で硬化させる際
には、前記積層物を押圧することが好ましい。この押圧
の圧力は、特に制限ないが、通常０．０１〜０．１ｋｇ
／ｃｍ2が好ましい。本発明は、連続パネル成形法にお
いて特に有効である。連続パネル成形法における高速硬
化は、通常１０〜３０分で行われる。また、連続パネル
成形法では、通常３〜１０ｍ／分の速度で繊維強化樹脂
板を成形することができる。In the method for producing a fiber-reinforced resin plate of the present invention, a laminate of porous titanium paper and impregnated reinforcing fibers is cured by pressure molding such as encapsulation molding, continuous panel molding, press molding, and the like. Both sides are covered with a thermosetting resin cured layer. At least one of the cured layers is a layer formed of the impregnated reinforcing fibers. This encapsulation molding refers to a molding method in which the porous titanium paper is sealed in a thermosetting resin cured layer. Further, the continuous panel molding refers to a method of continuously forming a plate while continuously performing resin impregnation and curing at a high speed. In the above method, it is preferable that, before curing, the laminate is pressed to allow the uncured resin liquid to permeate the holes of the titanium paper. The pressure for this pressing is not particularly limited, but is usually preferably 0.05 to 1.0 kg / cm 2 . Curing is usually performed by placing the laminate in a heating furnace. The temperature of the heating furnace varies depending on the type of the curable resin.
0-160 ° C. In addition, when hardening in a heating furnace, it is preferable to press the laminate. The pressure of this pressing is not particularly limited, but is usually 0.01 to 0.1 kg.
/ Cm 2 is preferred. The present invention is particularly effective in a continuous panel forming method. The high-speed curing in the continuous panel molding method is usually performed in 10 to 30 minutes. In the continuous panel molding method, the fiber reinforced resin plate can be usually molded at a speed of 3 to 10 m / min.
【００１３】次に、本発明の繊維強化樹脂板の製造方法
の好適な例を図１に基づいて説明する。図１において、
原反ロール４から離型フィルムを兼ねたキャリアフィル
ム３が送り出され、そのキャリアフィルム３の上に、原
反ロール２から送り出された多孔チタン紙１がロール５
の位置で載せられる。キャリアフィルム３は、加熱硬化
時の熱に耐え、かつ連続的に引っ張るための荷重にも耐
えるものが望ましく、２０〜１００μｍ厚さのポリエス
テルフィルムが適している。また、キャリアフィルム３
は繊維強化樹脂板表面に凹凸の模様を形成させ、表面の
装飾性を向上させる目的で、いわゆるエンボス加工され
たものを用いることができる。次に、多孔チタン紙１の
上面に未硬化樹脂液供給口７から硬化剤などを配合した
液状の未硬化樹脂液６を流下拡散させる。次に、未硬化
樹脂液量を均等化するためにドクターバー８を通し、広
がった未硬化樹脂液層の上に、連続繊維（たとえばガラ
スロービング）９をカッター１０で２５〜５０ｍｍに切
断した短繊維１１を散布し、多孔チタン紙１の上面に含
浸補強繊維の層１２を形成する。この含浸補強繊維の層
１２の上面に、原反ロール１４から送り出されたキャリ
アフィルム１３を載せ、続いて一対の厚さコントロール
ローラ１５を通した後、加熱硬化炉１６へと導く。加熱
硬化炉１６で未硬化樹脂液を硬化後、一対の送り出しロ
ーラ１７を通過させた後、キャリアフィルム３、１３を
剥離すると、所望のチタン紙入り繊維強化樹脂板２０を
得ることができる。なお、多孔チタン紙を挿入する位置
は、最外層、ガラス繊維を含む層の内側のどちらにでも
可能であり、ガラスサーフェイスマットその他の表面材
を外側に配置してもよい。Next, a preferred example of the method for producing a fiber reinforced resin plate of the present invention will be described with reference to FIG. In FIG.
A carrier film 3 also serving as a release film is sent out from the raw roll 4, and the porous titanium paper 1 sent from the raw roll 2 is rolled on the carrier film 3.
It is placed at the position. The carrier film 3 desirably withstands heat during heat curing and also withstands a load for continuous pulling, and a polyester film having a thickness of 20 to 100 μm is suitable. In addition, carrier film 3
For the purpose of forming an uneven pattern on the surface of the fiber reinforced resin plate and improving the decorativeness of the surface, what is called embossed can be used. Next, a liquid uncured resin liquid 6 containing a curing agent or the like is diffused downward from the uncured resin liquid supply port 7 on the upper surface of the porous titanium paper 1. Next, in order to equalize the amount of the uncured resin liquid, a continuous fiber (for example, glass roving) 9 was cut into 25 to 50 mm by a cutter 10 on the spread uncured resin liquid layer through a doctor bar 8. The fibers 11 are scattered to form a layer 12 of impregnated reinforcing fibers on the upper surface of the perforated titanium paper 1. The carrier film 13 sent out from the material roll 14 is placed on the upper surface of the layer 12 of the impregnated reinforcing fibers, and subsequently passed through a pair of thickness control rollers 15, and then guided to the heat curing furnace 16. After curing the uncured resin liquid in the heat-curing furnace 16 and passing it through a pair of delivery rollers 17, the carrier films 3 and 13 are peeled off to obtain a desired fiber-reinforced resin plate 20 containing titanium paper. The position where the porous titanium paper is inserted can be in either the outermost layer or the inner side of the layer containing glass fibers, and a glass surface mat or other surface material may be arranged on the outer side.
【００１４】[0014]
【実施例】次に、本発明を実施例に基づいて詳細に説明
する。これらの実施例は、本発明を何ら制限するもので
はない。Next, the present invention will be described in detail with reference to examples. These examples do not limit the invention in any way.
【００１５】［実施例１］最下層に、キャリアフィルム
として３５μｍ厚さの連続ポリエステルフィルム１００
０ｍｍ幅を敷き、その上に直径０．２ｍｍの孔を幅方向
２ｍｍ間隔、長さ方向３ｍｍ間隔の千鳥配列に開けた幅
７００ｍｍの、表面に模様が印刷された連続多孔チタン
紙（目付：６０ｇ／ｍ2、酸化チタン含量：２３重量
％、紙質：加工紙）を置いた。さらに、この多孔チタン
紙の上にメチルエチルケトンパーオキサイドを１．２重
量％、６重量％ナフテン酸コバルト溶液を０．０５重量
％配合した透明なオルソフタル酸系不飽和ポリエステル
樹脂液（粘度：３００ｍＰａ・ｓ）を全板厚１．２ｍｍ
になる量だけ流下させ、その上に、直径１３μｍのガラ
ス繊維からなるガラス繊維ロービングをカッターにて５
０ｍｍに切断し全面に散布する。そして、最後に、キャ
リアフィルムとして３５μｍ厚さ幅１０００ｍｍの連続
ポリエステルフィルムで上から覆い、厚さコントロール
用ローラーを通して硬化炉に送った。硬化炉の温度は、
１１０℃であり、硬化炉に入っている時間は１５分であ
った。硬化炉を出た後、上下両面のキャリアフィルムを
剥離して、ガラス繊維含有率２２重量％、厚さ１．２ｍ
ｍのチタン紙入り繊維強化樹脂板を６ｍ／分の速度で得
ることができた。この繊維強化樹脂板はチタン紙模様側
が透明樹脂硬化層で、裏側がガラス繊維強化樹脂硬化層
で覆われており、チタン紙の模様は、鮮明性に優れ、ま
た耐水性および耐候性に優れたものであった。図２に、
得られた繊維強化樹脂板の断面図を示した。Example 1 A continuous polyester film 100 having a thickness of 35 μm was formed as a carrier film on the lowermost layer.
A continuous porous titanium paper having a width of 700 mm and a pattern printed on the surface having a width of 700 mm in which holes having a diameter of 0.2 mm are formed in a zigzag arrangement at intervals of 2 mm in the width direction and intervals of 3 mm in the length direction, and a pattern is printed on the surface (weight: 60 g) / M 2 , titanium oxide content: 23% by weight, paper quality: processed paper). Further, a transparent orthophthalic unsaturated polyester resin liquid (viscosity: 300 mPa · s) containing 1.2% by weight of methyl ethyl ketone peroxide and 0.05% by weight of a 6% by weight cobalt naphthenate solution on this porous titanium paper. ) Is 1.2mm
And a glass fiber roving made of glass fiber having a diameter of 13 μm is further cut with a cutter.
Cut to 0 mm and spread over the entire surface. And finally, it was covered from above with a continuous polyester film having a thickness of 35 μm and a width of 1000 mm as a carrier film, and sent to a curing furnace through a thickness control roller. The curing oven temperature is
110 ° C. and the time in the curing oven was 15 minutes. After leaving the curing furnace, the carrier film on both the upper and lower surfaces was peeled off, and the glass fiber content was 22% by weight and the thickness was 1.2m.
m was obtained at a speed of 6 m / min. This fiber reinforced resin plate is covered with a transparent resin cured layer on the titanium paper pattern side and a glass fiber reinforced resin cured layer on the back side, and the pattern of titanium paper is excellent in clarity, and also excellent in water resistance and weather resistance Was something. In FIG.
A cross-sectional view of the obtained fiber-reinforced resin plate was shown.
【００１６】［実施例２］最下層に、キャリアフィルム
として３５μｍ厚さで凹凸にエンボス加工された連続ポ
リエステルフィルム１０００ｍｍ幅を敷き、実施例１と
同様に配合された不飽和ポリエステル樹脂液を４００ｇ
／ｍ2流下拡散させ、その上に直径１３μｍのガラス繊
維を束ねたガラスロービングを５０ｍｍに切断しながら
２００ｇ／ｍ2散布し、そのガラス繊維強化不飽和ポリ
エステル樹脂層の上に直径０．２ｍｍの孔を幅方向２ｍ
ｍ間隔、長さ方向３ｍｍ間隔の千鳥配列に開けた幅７０
０ｍｍの、表面に模様が印刷された連続多孔チタン紙
（目付：６０ｇ／ｍ2、酸化チタン含量：２３重量％、
紙質：加工紙）を置いた。さらに、この多孔チタン紙の
上に実施例１同様に配合されたポリエステル樹脂を４０
０ｇ／ｍ2流下拡散させ、その上に、直径１３μｍのガ
ラス繊維からなるガラス繊維ロービングをカッターにて
５０ｍｍに切断し全面に散布する。そして、最後に、キ
ャリアフィルムとして３５μｍ厚さ幅１０００ｍｍの連
続ポリエステルフィルムで上から覆い、厚さコントロー
ル用ローラーを通して硬化炉に送った。硬化炉の温度
は、１１０℃であり、硬化炉に入っている時間は１５分
であった。硬化炉を出た後、上下両面のキャリアフィル
ムを剥離して、チタン紙側にエンボス模様をつけ、表面
をガラス繊維強化樹脂硬化層で覆い、チタン紙裏面をさ
らにガラス繊維強化樹脂硬化層で覆ったチタン紙入り繊
維強化樹脂板を４ｍ／分の速度で得ることができた。こ
の繊維強化樹脂板は、チタン紙の模様の鮮明性が優れ、
また耐水性および耐候性に優れたものであった。図３
に、得られた繊維強化樹脂板の断面図を示した。[Example 2] A continuous polyester film having a thickness of 35 µm and embossed into a concavo-convex pattern having a width of 1000 mm was laid on the lowermost layer as a carrier film, and 400 g of an unsaturated polyester resin liquid compounded in the same manner as in Example 1 was used.
/ M 2 falling to diffuse, the upper 200 g / m 2 by spraying with cut glass rovings obtained by bundling glass fibers with a diameter of 13μm to 50mm, the diameter 0.2mm over the glass fiber reinforced unsaturated polyester resin layer Hole 2m in width direction
Width 70 opened in a staggered pattern at m intervals and 3 mm intervals in the length direction
0 mm continuous porous titanium paper having a pattern printed on its surface (basis weight: 60 g / m 2 , titanium oxide content: 23% by weight,
Paper quality: processed paper). Further, a polyester resin compounded in the same manner as in Example 1 on this porous titanium paper was added with 40 wt.
Diffusion is performed under 0 g / m 2, and a glass fiber roving made of glass fiber having a diameter of 13 μm is cut into 50 mm with a cutter and sprayed on the entire surface. And finally, it was covered from above with a continuous polyester film having a thickness of 35 μm and a width of 1000 mm as a carrier film, and sent to a curing furnace through a thickness control roller. The temperature of the curing oven was 110 ° C., and the time in the curing oven was 15 minutes. After exiting the curing oven, the carrier film on both the upper and lower surfaces is peeled off, embossed on the titanium paper side, the surface is covered with a cured glass fiber reinforced resin layer, and the back of the titanium paper is further covered with a cured glass fiber reinforced resin layer. Thus, a fiber-reinforced resin plate containing titanium paper was obtained at a speed of 4 m / min. This fiber reinforced resin plate has excellent clearness of the pattern of titanium paper,
Further, it was excellent in water resistance and weather resistance. FIG.
FIG. 2 shows a cross-sectional view of the obtained fiber-reinforced resin plate.
【００１７】[0017]
【発明の効果】本発明によるチタン紙入り繊維強化樹脂
板は、チタン紙に印刷された色、図形や模様がそのま
ま、板の図形や模様として装飾性のある繊維強化樹脂板
を得ることができる。しかも、チタン紙の両表面は空気
泡、ドライスポットのない熱硬化性樹脂硬化物、もしく
は繊維で強化された熱硬化性樹脂硬化物で均一に覆われ
ているため、耐水性、耐候性と強度に優れた繊維強化樹
脂板を得ることができる。According to the fiber reinforced resin plate containing titanium paper according to the present invention, a fiber reinforced resin plate having decorativeness as a figure or pattern of the plate can be obtained without changing the color, figure or pattern printed on the titanium paper. . In addition, since both surfaces of the titanium paper are uniformly covered with thermosetting resin without air bubbles and dry spots, or with thermosetting resin reinforced with fiber, water resistance, weather resistance and strength A fiber-reinforced resin plate excellent in quality can be obtained.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明の繊維強化樹脂板の製造方法の好適な例
の概略図である。FIG. 1 is a schematic view of a preferred example of a method for producing a fiber-reinforced resin plate of the present invention.
【図２】本発明の繊維強化樹脂板の一例を示す断面図で
ある。FIG. 2 is a cross-sectional view showing one example of the fiber-reinforced resin plate of the present invention.
【図３】本発明の繊維強化樹脂板の一例を示す断面図で
ある。FIG. 3 is a cross-sectional view showing one example of the fiber-reinforced resin plate of the present invention.
１ 多孔チタン紙 ２ 原反ロール ３ キャリアフィルム ４ 原反ロール ５ ロール ６ 未硬化樹脂液 ７ 未硬化樹脂液供給口 ８ ドクターバー ９ 連続繊維 １０ カッター １１ 短繊維 １２ 含浸補強繊維の層 １３ キャリアフィルム １４ 原反ロール １５ 厚さコントロールローラ １６ 加熱硬化炉 １７ 送り出しローラ １８ 巻き取りローラ １９ 巻き取りローラ ２０ 繊維強化樹脂板 ２１ 繊維強化硬化性樹脂硬化層 ２２ 硬化性樹脂硬化層 ２３ エンボス面 DESCRIPTION OF SYMBOLS 1 Porous titanium paper 2 Raw roll 3 Carrier film 4 Raw roll 5 Roll 6 Uncured resin liquid 7 Uncured resin liquid supply port 8 Doctor bar 9 Continuous fiber 10 Cutter 11 Short fiber 12 Layer of impregnated reinforcing fiber 13 Carrier film 14 Material roll 15 Thickness control roller 16 Heat-curing furnace 17 Delivery roller 18 Take-up roller 19 Take-up roller 20 Fiber reinforced resin plate 21 Fiber reinforced hardened resin cured layer 22 Curable resin cured layer 23 Embossed surface
Claims (2)
有し、該硬化性樹脂硬化層の少なくとも一方が補強繊維
で強化されていることを特徴とする繊維強化樹脂板。1. A fiber reinforced resin plate having a hardened resin cured layer on both sides of a porous titanium paper, wherein at least one of the hardened resin cured layers is reinforced with reinforcing fibers.
硬化性樹脂液が含浸された補強繊維の層を形成し、続い
て加圧成形によりこの未硬化硬化性樹脂液を硬化させ、
硬化性樹脂硬化層を形成することを特徴とする繊維強化
樹脂板の製造方法。2. A layer of a reinforcing fiber impregnated with an uncured curable resin liquid is formed on one or both surfaces of the porous titanium paper, and then the uncured curable resin liquid is cured by pressure molding.
A method for producing a fiber-reinforced resin plate, comprising forming a cured resin layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9434697A JPH10272740A (en) | 1997-03-31 | 1997-03-31 | Fiber-reinforced resin plate and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9434697A JPH10272740A (en) | 1997-03-31 | 1997-03-31 | Fiber-reinforced resin plate and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10272740A true JPH10272740A (en) | 1998-10-13 |
| JPH10272740A5 JPH10272740A5 (en) | 2004-10-14 |
Family
ID=14107731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9434697A Pending JPH10272740A (en) | 1997-03-31 | 1997-03-31 | Fiber-reinforced resin plate and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10272740A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118789899A (en) * | 2024-06-24 | 2024-10-18 | 中国兵器科学研究院宁波分院 | A super hybrid fiber reinforced metal laminate and preparation method thereof |
-
1997
- 1997-03-31 JP JP9434697A patent/JPH10272740A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118789899A (en) * | 2024-06-24 | 2024-10-18 | 中国兵器科学研究院宁波分院 | A super hybrid fiber reinforced metal laminate and preparation method thereof |
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