JPS63193932A - Flat or corrugated resin plate reinforced with reinforcing fiber - Google Patents
Flat or corrugated resin plate reinforced with reinforcing fiberInfo
- Publication number
- JPS63193932A JPS63193932A JP2446187A JP2446187A JPS63193932A JP S63193932 A JPS63193932 A JP S63193932A JP 2446187 A JP2446187 A JP 2446187A JP 2446187 A JP2446187 A JP 2446187A JP S63193932 A JPS63193932 A JP S63193932A
- Authority
- JP
- Japan
- Prior art keywords
- syrup
- film
- flat
- weight
- polymerizable
- 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
- 239000012783 reinforcing fiber Substances 0.000 title claims abstract description 12
- 229920005989 resin Polymers 0.000 title claims description 5
- 239000011347 resin Substances 0.000 title claims description 5
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000006188 syrup Substances 0.000 claims abstract description 23
- 235000020357 syrup Nutrition 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 11
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 10
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000009835 boiling Methods 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000036760 body temperature Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010011878 Deafness Diseases 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 241000981595 Zoysia japonica Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 231100000895 deafness Toxicity 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 208000016354 hearing loss disease Diseases 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、耐水性・耐候性に優れた建築用材として使用
し得る、半透明の美麗に光を散乱する平・波板に関する
ものである。[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a translucent flat/corrugated plate that beautifully scatters light and can be used as a construction material with excellent water resistance and weather resistance. .
(従来の技術)
従来よシ、メチルメタクリレートに?リメチルス繊維や
ナイロン・テトロン等の有機繊維等の補強用繊維で強化
された樹脂(以下、FRPと略称することがある。)製
の平・波板は公知である。(Conventional technology) Methyl methacrylate instead of conventional technology? Flat and corrugated plates made of resin (hereinafter sometimes abbreviated as FRP) reinforced with reinforcing fibers such as remethylus fibers and organic fibers such as nylon and Tetron are well known.
(発明が解決しようとする問題点)
しかし、これら公知の技術で得られるFRP製の平・波
板は、生産性や、耐水性・耐熱性・耐候性・強度・耐久
性に問題があり、それぞれ使用場所が限定されていた。(Problems to be solved by the invention) However, FRP flat and corrugated plates obtained using these known techniques have problems in productivity, water resistance, heat resistance, weather resistance, strength, and durability. The places where they could be used were limited.
アクリル光子・波板では、その製造過程で硬化室温度を
不飽和ポリエステル樹脂板のように60℃から140℃
まで上げていくと、低沸点のメチルメタクリレートが硬
化発熱で発泡し製品に気泡が残ってしまうため、70℃
以下の硬化温度で連続成形されている。従りて硬化時間
が長くかかり、ラインスピードが50α/分以下で生産
性が悪くコストが高くついている。また、アクリル光子
・波板は、熱変形温度が100℃程度で低く熱変形し易
い欠点がちシ、熱が伝わシ易い環境での使用に制限があ
った。For acrylic photon/corrugated plates, the curing chamber temperature during the manufacturing process is changed from 60℃ to 140℃ like unsaturated polyester resin plates.
If the temperature is raised to 70℃, methyl methacrylate, which has a low boiling point, will foam due to the heat generated by curing, leaving bubbles in the product.
It is continuously molded at the following curing temperature. Therefore, the curing time is long, and the line speed is less than 50 α/min, resulting in poor productivity and high costs. Furthermore, acrylic photon/corrugated plates have a low thermal deformation temperature of about 100° C. and are prone to thermal deformation, which limits their use in environments where heat is easily transmitted.
塩化ビニル樹脂の平・波板は耐久性に問題があった。す
なわち、使用中途々に可塑剤が抜は出して行く為1〜2
年で柔軟性が失なわれ、耐衝撃性が極端に低下して割れ
易くなってしまう欠点があった。Flat and corrugated plates made of vinyl chloride resin had durability problems. In other words, the plasticizer is removed during use, so 1 to 2
It has the disadvantage that it loses its flexibility over time, and its impact resistance is extremely reduced, making it more likely to break.
不飽和ポリエステル樹脂の平・波板は、強度の耐久性に
優れているが、ガラス繊維の浮き出しがあシ美観に劣っ
たものである。そして、これを屋外で@露すると、2〜
3年でガラス繊維が露出して不透明の汚れた外観となる
欠点があり、これを防止するために、表面にダルコート
したシ四弗化ピニリガンフィルム等の耐水性・耐候性の
良いフィルムを貼シ付けたシしているが、いずれもコス
トアップになっている。Flat and corrugated sheets made of unsaturated polyester resin have excellent strength and durability, but the glass fibers are embossed and the appearance is poor. And when this is exposed outdoors, 2~
The disadvantage is that the glass fibers become exposed after 3 years, resulting in an opaque and dirty appearance. Although there are some improvements, the cost has increased in both cases.
本発明は、かかる現状の改良を行うのを目的とするもの
であって、耐水性・耐熱性・耐候性に優れ且つ強度の大
きい透明または半透明の美麗な外観を有する平・波板を
提供するものである。The present invention aims to improve the current state of the art, and provides a flat/corrugated plate having excellent water resistance, heat resistance, weather resistance, high strength, and a beautiful transparent or translucent appearance. It is something to do.
(問題点を解決するための手段および作用)本発明者ら
は、種々検討した結果、特定の単量体を特定の割合で混
合したものに熱可塑性ポリマーを特定量溶解して得られ
る重合性シラツブを用いることによシ、その目的が達成
できることを見い出して、本発明を完成させた。(Means and effects for solving the problem) As a result of various studies, the present inventors have discovered that a polymerizable polymer obtained by dissolving a specific amount of a thermoplastic polymer in a mixture of specific monomers in a specific ratio. The present invention was completed by discovering that the purpose could be achieved by using silica.
すなわち、本発明は、移動する第1フィルム上に重合性
シラップ(I)および補強用繊維を供給して該シラツブ
(I)含浸繊維層を形成し、該層上に第1フィルムと同
方向に移動する第2フィルムを置いて該層を第1フィル
ムと第2フィルムとで挾み、該層を形付するかあるいは
せずして該シラ7f(1)(記)
脂肪族多官能(メタ)アクリレート(ト)15〜55]
(7%、芳香族ビニル化合物(B)85〜45重i%お
よびこれらと共重合可能な沸点が120℃以上である他
の単量体C)0〜40重量%(ただし、囚、(B)およ
び(C)成分の合計は100重量%である。)からなる
単量体混液10 Q!量部に対して、熱可嵐性ポリマー
5〜40重量部、および硬化剤を混合して得られ、かつ
30℃で測定した粘度が1.0〜100ポイズの範囲に
ある重合性シラツブ(I)。That is, in the present invention, a polymerizable syrup (I) and reinforcing fibers are supplied onto a moving first film to form a fiber layer impregnated with the syrup (I), and a fiber layer impregnated with the syrup (I) is formed on the layer in the same direction as the first film. A moving second film is placed, the layer is sandwiched between the first film and the second film, and the layer is formed with or without shaping. ) Acrylate (g) 15-55]
(7%, aromatic vinyl compound (B) 85-45% by weight and other monomers C which can be copolymerized with these and have a boiling point of 120°C or higher) 0-40% by weight (However, ) and (C) component is 100% by weight.) Monomer mixture 10 Q! Polymerizable sillage (I ).
本発明に使用される脂肪族多官能(メタ)アクリレート
(5)とは、エチレングリコールジ(メタ)アクリレー
ト、プロピレングリコールジ(メタ)アクリレート、プ
チレングリコールジ(メタ)アクリレート、ネオペンチ
ルグリコールジ(メタ)アクリレート、グリセリントリ
(メタ)アクリレート、トリメチロールプロノIントリ
(メタ)アクリレート、シヘンタエリスリトールヘキサ
(メタ)アクリレートなどを含むものである。中でも、
硬化速度や耐熱性の点から例えばトリメチロールプロ・
せントリメタクリレートに代表される3官能の(メタ)
アクリレートが望ましい。2官能の(メタ)アクリレー
トでは、硬化速度が遅く、得られる平・波板の耐水性や
耐熱性が劣る傾向にある。The aliphatic polyfunctional (meth)acrylates (5) used in the present invention include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. These include meth)acrylate, glycerin tri(meth)acrylate, trimethylolprono-I tri(meth)acrylate, hexa(meth)acrylate, and the like. Among them,
In terms of curing speed and heat resistance, for example, trimethylol pro-
Trifunctional (meth) represented by centrimethacrylate
Acrylate is preferred. Difunctional (meth)acrylates have a slow curing speed, and the resulting flat/corrugated sheets tend to have poor water resistance and heat resistance.
また、4官能以上の(メタ)アクリレートでは、架橋密
度が高くなって、得られる平・波板の靭性が低下する傾
向にある。Furthermore, in the case of (meth)acrylates having four or more functionalities, the crosslinking density becomes high, and the toughness of the obtained flat/corrugated sheet tends to decrease.
芳香族ビニル化合物(B)には、例えばスチレン、α−
メチルスチレン、p−メチルスチレン、ジビニルベンゼ
ンなどがある。中でも経済性の点からスチレンが望まし
い。The aromatic vinyl compound (B) includes, for example, styrene, α-
Examples include methylstyrene, p-methylstyrene, and divinylbenzene. Among them, styrene is preferred from the economical point of view.
脂肪族多官能(メタ)アクリレ−)(A)と芳香族ビニ
ル化合物(B)の割合は、前者が15〜55重量%、よ
り好ましくは20〜40重量%、後者が85〜45重量
%、よシ好ましくは80〜60重jjk%の割合で使用
される。脂肪族多官能(メタ)アクリレート囚の使用量
が前記範囲よシ多いと、得られる平・波板の耐候性や耐
熱性は良くなるが、耐水性が低下し、また柔軟性がなく
なって割れ易くなる。一方、芳香族ビニル化合物(B)
の使用量が前記範囲よシ多くなると、耐水性や透明性は
良くなるが、耐候性、耐熱性が低下する。The ratio of aliphatic polyfunctional (meth)acrylate (A) and aromatic vinyl compound (B) is 15 to 55% by weight, more preferably 20 to 40% by weight, and 85 to 45% by weight, It is preferably used in a proportion of 80 to 60% by weight. If the amount of aliphatic polyfunctional (meth)acrylate used is greater than the above range, the weather resistance and heat resistance of the obtained flat/corrugated sheet will be improved, but the water resistance will decrease, and the flexibility will be lost and cracking will occur. It becomes easier. On the other hand, aromatic vinyl compound (B)
If the amount used is greater than the above range, water resistance and transparency will improve, but weather resistance and heat resistance will decrease.
本発明における単量体温液は、前記二種の単量体(A)
および(B)が必須の成分であるが、前記単量体囚およ
びΦ)と共重合可能な沸点が120℃以上である他の単
量体(C) t−単量体温液中40重tcs以下、よシ
好ましくは25重量%以下の割合で使用することができ
る。このような単量体(C)としては、例えばプロピル
(メタ)アクリレート、n−、ls。The monomer body temperature liquid in the present invention contains the two types of monomers (A)
and (B) is an essential component, but other monomers having a boiling point of 120°C or higher that can be copolymerized with the monomers and Φ) (C) t-monomer 40% tcs in body temperature liquid Hereinafter, it can be used preferably in a proportion of 25% by weight or less. Examples of such a monomer (C) include propyl (meth)acrylate, n-, and ls.
+、 tsrt−ブチル(メタ)アクリレート等がある
。+, tsrt-butyl (meth)acrylate, etc.
これらの単量体(A) 、 (B)および必要により(
C)からなる単量体混液だけでは、粘度が低すぎて平・
波板製造時の作業性が劣9ておシ、また硬化収縮が大き
すぎて製品に変形・反シ・クラックが発生し平・波板の
連続成形用の重合性シラツブとして使用できな°い。These monomers (A), (B) and if necessary (
A monomer mixture consisting of C) alone has a viscosity that is too low to be flat or flat.
The workability during the production of corrugated sheets is poor, and the curing shrinkage is too large, causing deformation, cracking, and cracks in the product, making it impossible to use it as a polymerizable silicone for continuous molding of flat and corrugated sheets. .
本発明者らは、該単量体混液100重量部に対度を30
℃で測定して1.0〜100ポイズ、よシ好ましくは3
.0〜30ポイズの範囲とすれば、平・波板の連続成形
用の重合性シクロ!として好ましいものが得られ、かつ
補強用繊維への含浸性にも優れていることを見い出した
。The present inventors added 30 parts by weight to 100 parts by weight of the monomer mixture.
1.0 to 100 poise, preferably 3
.. If it is in the range of 0 to 30 poise, it is a polymerizable cyclo for continuous molding of flat and corrugated sheets! It has been found that a preferable product can be obtained, and that the impregnating properties into reinforcing fibers are also excellent.
すなわち、本発明に用いられる重合性シラップ(I)は
、前記単量体混液1003iii部に対して、熱可塑性
/ リフ−5〜40重量部および硬化剤を混合して得ら
れ、かつ30℃で測定した粘度が1.0〜100−イズ
の範囲にあるものである。熱可塑性ポリマーの使用量が
5重量部未満の少量であると、硬化時の収縮が大きくな
シ製品に変形・反シ・クラックが発生しやすくなる。逆
に40重量部を維への含浸性が不十分となシ、また得ら
れる平・波板の耐熱性も低下する。That is, the polymerizable syrup (I) used in the present invention is obtained by mixing 1003 parts of the monomer mixture with 5 to 40 parts by weight of a thermoplastic/refrigerant and a curing agent, and is heated at 30°C. The measured viscosity is in the range of 1.0 to 100-Is. If the amount of the thermoplastic polymer used is small, less than 5 parts by weight, the product will easily undergo deformation, deformation, and cracks due to large shrinkage during curing. On the other hand, if 40 parts by weight is used, the impregnation into the fibers will be insufficient, and the heat resistance of the resulting flat or corrugated sheets will also be reduced.
本発明に用いることができる熱可塑性プリマーには、例
えばポリメチルメタクリレート等の(メタ)アクリレー
ト系プリマー、(メタ)アクリル−スチレン系共重合ポ
リマー、ポリスチレン、ポリ酢酸ビニル、スチレ/−酢
酸ビニル共重合体、ポリブタジェン、飽和ポリエステル
、ポリカプロラクタム、ポリ塩化ビニル、ポリエチレン
等がある。Thermoplastic primers that can be used in the present invention include (meth)acrylate primers such as polymethyl methacrylate, (meth)acrylic-styrene copolymers, polystyrene, polyvinyl acetate, and styrene/vinyl acetate copolymers. Polymers, polybutadiene, saturated polyester, polycaprolactam, polyvinyl chloride, polyethylene, etc.
中でも、得られる平・波板の透明性を高めて美麗な外観
とするために、使用する熱可塑性ポリマーの屈折率が単
量体混液の硬化物の屈折率と同じか±O,Oaの範囲に
あるものが好ましい。従って、使用する熱可塑性ポリマ
ーは、単量体温液の配合に近いものが望ましく、例えば
メチルメタクリレートとスチレンとのコポリマーに代表
される(メタ)アクリレートモノマーと芳香族ビニルモ
ノマーとの重合比率を種々に変えた共重合体が用いられ
る。Above all, in order to improve the transparency of the obtained flat/corrugated plate and give it a beautiful appearance, it is necessary to make sure that the refractive index of the thermoplastic polymer used is the same as the refractive index of the cured product of the monomer mixture or within the range of ±O, Oa. Preferably the one in Therefore, it is desirable for the thermoplastic polymer to be used to have a composition close to that of a monomer body temperature liquid. Different copolymers are used.
本発明に使用される硬化剤としては、例えばペンゾイル
ノ々−オキサイド、シクロヘキサノンtJ? −オキサ
イド、メチルエチルケトンパーオキサイド、ビス(A−
t−ブチルシクロヘキシル)ノ臂−オキシジカーボネー
ト、t−ブチルパーオキシオクトエート等があシ、単独
もしくは、促進剤として有機アミンや多価金属の塩類と
共に用いられる。硬化剤の添加量は単量体混液の重量を
基準にして、0.3〜3.0%に相当する量を加えるの
が普通である。Examples of the curing agent used in the present invention include penzoyl oxide, cyclohexanone tJ? -oxide, methyl ethyl ketone peroxide, bis(A-
Examples include t-butylcyclohexyl oxydicarbonate and t-butylperoxyoctoate, which are used alone or together with organic amines or polyvalent metal salts as accelerators. The amount of curing agent added is usually 0.3 to 3.0% based on the weight of the monomer mixture.
重合性シラップ(I)を調製するに際し、得られる平・
波板の耐熱性や耐燃性を高める目的で無機質充填材を混
合分散して使用することもできる。このような無機質充
填材としては、炭酸カルシウム、メルク、クレー、シリ
カ、アルミナ、石英、硅酸カルシウムや、各種金属酸化
物の水和物例えば水酸化アルミニウム、水酸化マグネシ
ウム等がある。When preparing polymerizable syrup (I), the obtained plain and
In order to improve the heat resistance and flame resistance of the corrugated sheet, an inorganic filler may be mixed and dispersed. Examples of such inorganic fillers include calcium carbonate, Merck, clay, silica, alumina, quartz, calcium silicate, and hydrates of various metal oxides such as aluminum hydroxide and magnesium hydroxide.
中でも、より高度の難燃化が達成できる水酸化アルミニ
ウムが好ましい。Among these, aluminum hydroxide is preferred since it can achieve a higher degree of flame retardancy.
さらに、重合性シラップ(I)には、種々の添加剤や改
質剤を混合・使用できる。たとえば樹脂と補強用繊維特
にガラス繊維との界面接着を良くするためのシランまた
はチタネート系カップリング剤、フィルムとの離型性を
良くするための内部離型剤、着色剤が用いられ、また耐
候性を良くし製品を紫外線から保護する目的で紫外線吸
収剤が用いられる。Furthermore, various additives and modifiers can be mixed and used in the polymerizable syrup (I). For example, silane or titanate coupling agents are used to improve interfacial adhesion between resin and reinforcing fibers, especially glass fibers, internal mold release agents and colorants are used to improve mold release properties from the film, and weather resistant Ultraviolet absorbers are used to improve properties and protect products from ultraviolet rays.
補強用繊維としては、ガラス繊維が最も一般的に用いら
れるが、カーボン繊維や、ポリアミド・ナイロン・ポリ
エステル等の有機繊維も使用できる。Glass fibers are most commonly used as reinforcing fibers, but carbon fibers and organic fibers such as polyamide, nylon, and polyester can also be used.
本発明のFRP製の平・波板は、前記した重合性シラツ
ブ(I)および補強用繊維を用いて、従来公知の平・波
板連続成形機によシ製造される。具体的には、移動する
第1フィルム上に、例えば重合性シラップ(I)を塗布
ロールやナイフコーターを介して供給し、また補強用繊
維も散布等によシ第1フィルム上に供給する。次いで、
第1フィルム上に形成された重合性シラップ(I)含浸
繊維層に第1フィルムと同方向に移動する第2フィルム
を置いて、該層を両フィルム間で挾み、核層を必要によ
シ波聾等の形付しながら、重合性シラツブ(I)を連続
的に硬化する。硬化は、一般に重合性シラップ(I)含
浸繊維層を硬化室に導くことによシ行われる。The FRP flat/corrugated plate of the present invention is produced using the above-mentioned polymerizable silica (I) and reinforcing fibers using a conventionally known continuous flat/corrugated plate forming machine. Specifically, for example, polymerizable syrup (I) is supplied onto the moving first film via a coating roll or a knife coater, and reinforcing fibers are also supplied onto the first film by scattering or the like. Then,
A second film moving in the same direction as the first film is placed on the polymerizable syrup (I)-impregnated fiber layer formed on the first film, and the layer is sandwiched between the two films to remove the core layer as necessary. The polymerizable sillage (I) is continuously cured while being shaped into a shape such as a shiba deafness. Curing is generally carried out by introducing the fiber layer impregnated with polymerizable syrup (I) into a curing chamber.
硬化室は、例えば入口から出口まで雰囲気温度が段階的
に変化するよう分割され、入口部から中央部まで60℃
から120℃に徐々に上昇するよう設定されておシ、出
口付近では冷却部が設けられている。The curing chamber is divided, for example, so that the atmospheric temperature changes stepwise from the entrance to the exit, and the temperature is 60°C from the entrance to the center.
The temperature is set to gradually rise from 120°C to 120°C, and a cooling section is provided near the exit.
本発明の平・波板は、このようにして従来の不飽和ポリ
エステル樹脂で製造されていた平・波板と同じ2〜3m
/分のラインスピードで生産性良く製造することができ
る。また、透明または半透明の美麗な外観を有する平・
波板が、本発明によシ容易に提供される。The flat and corrugated sheets of the present invention have a length of 2 to 3 m, which is the same as the flat and corrugated sheets manufactured using conventional unsaturated polyester resin.
It can be manufactured with good productivity at a line speed of /min. In addition, flat and translucent surfaces with a beautiful transparent or translucent appearance
Corrugated sheets are readily provided in accordance with the present invention.
(発明の効果)
時間以上漬浸しても、光沢を失わず、白化による透明性
の低下もなく、表面クラックも生じない耐水性に優れた
ものであり、透明ま九は半透明の美麗な外観を長期間保
持できるものである。また、本発明の平・波板は、熱変
型温度が高く、耐候性にも優れている。(Effects of the invention) It has excellent water resistance that does not lose its luster, does not reduce its transparency due to whitening, and does not cause surface cracks even when immersed for more than an hour, and has a beautiful semi-transparent appearance. can be maintained for a long period of time. Further, the flat/corrugated plate of the present invention has a high thermal deformation temperature and is excellent in weather resistance.
(実施例)
以下実施例について更に詳細に説明するが、これらが本
発明の全てを代表するものではない。なお、例中の部は
特にことわらない限り重量部を表わす。(Examples) Examples will be described in more detail below, but these do not represent the entirety of the present invention. In addition, parts in the examples represent parts by weight unless otherwise specified.
実施例1
トリメチロールプロパントリメタクリレート30部およ
びスチレン70部からなる単量体混液に、熱可塑性ポリ
マーとしてメチルメタクリレート−スチレン共重合体(
商品名MASφ10.ダイセル化学工業■fi)20部
、シランカップリング剤[KBM−503、信越化学■
製〕0.5部、紫外線吸収剤〔チヌピン3201チバガ
イギー社製〕0,1部、硬化剤のt−ブチルパーオキシ
オクトエート〔ツク加えて混合・溶解して重合性シラッ
プ(I)を得た。Example 1 A methyl methacrylate-styrene copolymer (as a thermoplastic polymer) was added to a monomer mixture consisting of 30 parts of trimethylolpropane trimethacrylate and 70 parts of styrene.
Product name MASφ10. Daicel Chemical Co., Ltd. fi) 20 parts, silane coupling agent [KBM-503, Shin-Etsu Chemical Co., Ltd.
[Manufactured by Ciba Geigy] 0.5 part, ultraviolet absorber [Tinupin 3201 manufactured by Ciba Geigy] 0.1 part, curing agent t-butyl peroxyoctoate [Tsuku] was added, mixed and dissolved to obtain polymerizable syrup (I). .
得られた重合性シラップ(I)の粘度は30℃で20ポ
イズでありた。The viscosity of the obtained polymerizable syrup (I) was 20 poise at 30°C.
得られ次重合性シラップ(I)を平・波板連続生産機(
ラインスピード2.5 m 7分)の移動する第1フィ
ルム(ポリエステル製)上にナイフコーターを介して供
給し、一方ガラス繊維をガラス含有量22重i%の割合
で第1フィルム上に散布した。The obtained next polymerizable syrup (I) is transferred to a continuous flat/corrugated plate production machine (
It was fed through a knife coater onto a moving first film (made of polyester) at a line speed of 2.5 m (7 min), while glass fibers were sprinkled onto the first film at a glass content of 22% by weight. .
重合性シラツブ(I)のガラス繊維への含浸および硬化
を第1フィルム上に置かれた第2フィルムと第1フィル
ムとの間で連続的に行って、板厚0.8 mの波板を製
造した。Impregnation of polymerizable silica (I) into glass fibers and curing were performed continuously between the second film placed on the first film and the first film to form a corrugated sheet with a thickness of 0.8 m. Manufactured.
得られた波板は、完全に硬化しており、透明〜乳白色半
透明の美麗なもので、第1表に示すごとく、高強度で耐
水性、耐候性に優れたものであった。The obtained corrugated sheet was completely cured and beautiful, transparent to milky white and translucent, and as shown in Table 1, had high strength and excellent water resistance and weather resistance.
実施例ま た。Examples Ta.
得られた重合性シラップ(I)■儒■儒lとガラス繊維
を用いて、実施例1と同様にして、波板を製造した。A corrugated sheet was produced in the same manner as in Example 1 using the obtained polymerizable syrup (I) and glass fiber.
得られた波板は、透明の美麗なもので第1表に示すとお
り高強度で耐水性・耐候性に優れたものでありた。The obtained corrugated sheet was beautiful and transparent, and as shown in Table 1, had high strength and excellent water resistance and weather resistance.
比較例1
市販の建材用FRP波板(不飽和ポリエステル樹脂製)
の性能を測定した結果、第1表の通シであり、長所と欠
点があシ、総合的に優れたものではなかりた。Comparative Example 1 Commercially available FRP corrugated sheet for building materials (made of unsaturated polyester resin)
As a result of measuring the performance, the results were as shown in Table 1, which had both advantages and disadvantages, and was not excellent overall.
Claims (1)
および補強用繊維を供給して該シラップ( I )含浸繊
維層を形成し、該層上に第1フィルムと同方向に移動す
る第2フィルムを置いて該層を第1フィルムと第2フィ
ルムとで挾み、該層を形付するかあるいはせずして該シ
ラップ( I )を連続的に硬化させて得られる補強用繊
維で強化された樹脂製の平・波板。 (記) 脂肪族多官能(メタ)アクリレート(A)15〜55重
量%、芳香族ビニル化合物(B)85〜45重量%およ
びこれらと共重合可能な沸点が120℃以上である他の
単量体(C)0〜40重量%(ただし、(A)、(B)
および(C)成分の合計は100重量%である。)から
なる単量体混液100重量部に対して、熱可塑性ポリマ
ー5〜40重量部、および硬化剤を混合して得られ、か
つ30℃で測定した粘度が1.0〜100ポイズの範囲
にある重合性シラップ( I )。 2、脂肪族多官能(メタ)アクリレート(A)がトリメ
チロールプロパントリメタクリレートであり、芳香族ビ
ニル化合物(B)がスチレンである特許請求の範囲第1
項記載の平・波板。 3、熱可塑性ポリマーの屈折率が、単量体混液の硬化物
の屈折率±0.03の範囲である特許請求の範囲第1項
記載の平・波板。[Claims] 1. Polymerizable syrup (I) on the moving first film
and supplying reinforcing fibers to form the syrup (I)-impregnated fiber layer, and placing a second film moving in the same direction as the first film on the layer to separate the layer from the first film and the second film. A flat or corrugated resin sheet reinforced with reinforcing fibers obtained by sandwiching the syrup (I) with or without shaping the layers and curing the syrup (I) continuously. (Note) 15 to 55% by weight of aliphatic polyfunctional (meth)acrylate (A), 85 to 45% by weight of aromatic vinyl compound (B), and other monomers that can be copolymerized with these and have a boiling point of 120°C or higher. body (C) 0 to 40% by weight (however, (A), (B)
The total amount of component (C) is 100% by weight. ) is obtained by mixing 5 to 40 parts by weight of a thermoplastic polymer and a curing agent to 100 parts by weight of a monomer mixture consisting of Some polymerizable syrups (I). 2. Claim 1, wherein the aliphatic polyfunctional (meth)acrylate (A) is trimethylolpropane trimethacrylate and the aromatic vinyl compound (B) is styrene.
Flat/corrugated plates listed in section. 3. The flat/corrugated plate according to claim 1, wherein the thermoplastic polymer has a refractive index within a range of ±0.03 of the refractive index of the cured monomer mixture.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2446187A JPH075753B2 (en) | 1987-02-06 | 1987-02-06 | Resin flat / corrugated plate reinforced with reinforcing fibers |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2446187A JPH075753B2 (en) | 1987-02-06 | 1987-02-06 | Resin flat / corrugated plate reinforced with reinforcing fibers |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63193932A true JPS63193932A (en) | 1988-08-11 |
JPH075753B2 JPH075753B2 (en) | 1995-01-25 |
Family
ID=12138806
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2446187A Expired - Lifetime JPH075753B2 (en) | 1987-02-06 | 1987-02-06 | Resin flat / corrugated plate reinforced with reinforcing fibers |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH075753B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02232284A (en) * | 1989-03-06 | 1990-09-14 | Denki Kagaku Kogyo Kk | Adhesive composition and laminate |
CN108047673A (en) * | 2017-12-15 | 2018-05-18 | 常熟市金亿复合材料有限公司 | A kind of fiberglass corrosion-resistant clad plate |
-
1987
- 1987-02-06 JP JP2446187A patent/JPH075753B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02232284A (en) * | 1989-03-06 | 1990-09-14 | Denki Kagaku Kogyo Kk | Adhesive composition and laminate |
CN108047673A (en) * | 2017-12-15 | 2018-05-18 | 常熟市金亿复合材料有限公司 | A kind of fiberglass corrosion-resistant clad plate |
Also Published As
Publication number | Publication date |
---|---|
JPH075753B2 (en) | 1995-01-25 |
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