JP2013119601A - Transparent incombustible sheet and method for producing the same - Google Patents
Transparent incombustible sheet and method for producing the same Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims abstract description 100
- 229920005989 resin Polymers 0.000 claims abstract description 86
- 239000011347 resin Substances 0.000 claims abstract description 86
- 239000004744 fabric Substances 0.000 claims abstract description 74
- 239000004641 Diallyl-phthalate Substances 0.000 claims abstract description 41
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 32
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 31
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 27
- 125000003277 amino group Chemical group 0.000 claims abstract description 15
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 4
- 239000000779 smoke Substances 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 238000003825 pressing Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 21
- 239000011342 resin composition Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002759 woven fabric Substances 0.000 description 14
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 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
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical compound OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HRBYCVPFYWTROV-UHFFFAOYSA-M dimethyl-octadecyl-(3-triethoxysilylpropyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCC[Si](OCC)(OCC)OCC HRBYCVPFYWTROV-UHFFFAOYSA-M 0.000 description 1
- WSFMFXQNYPNYGG-UHFFFAOYSA-M dimethyl-octadecyl-(3-trimethoxysilylpropyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCC[Si](OC)(OC)OC WSFMFXQNYPNYGG-UHFFFAOYSA-M 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- BMYQRNYLBVFWRL-UHFFFAOYSA-N n-methyl-n-(3-trimethoxysilylpropyl)decan-1-amine;hydrochloride Chemical compound Cl.CCCCCCCCCCN(C)CCC[Si](OC)(OC)OC BMYQRNYLBVFWRL-UHFFFAOYSA-N 0.000 description 1
- 239000012934 organic peroxide initiator Substances 0.000 description 1
- 150000001451 organic peroxides Chemical group 0.000 description 1
- -1 phosphate ester Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229960001147 triclofos Drugs 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
【課題】透明性と不燃性にすぐれているのみならず、靱性乃至曲げ特性にすぐれていて、曲げや衝撃によって割れ難い透明不燃性シートとその製造方法を提供する。
【解決手段】分子中にアミノ基又は第４級アンモニウム構造を有するシランカップリング剤にて表面処理したガラス繊維織物をジアリルフタレート１０〜９０重量％と不飽和ポリエステル樹脂９０〜１０重量％からなる熱硬化性樹脂混合物の硬化物と一体化させてなる透明不燃性シートが提供される。このような透明不燃性シートは、分子中にアミノ基又は第４級アンモニウム構造を有するシランカップリング剤で表面処理したガラス繊維織物にジアリルフタレートプレポリマー１０〜９０重量％と不飽和ポリエステル樹脂９０〜１０重量％からなる熱硬化性樹脂混合物を含浸してプリプレグを得、これを加熱加圧して、上記ガラス繊維織物を上記硬化性樹脂混合物の硬化物と一体化することによって得ることができる。
【選択図】なしDisclosed is a transparent non-combustible sheet that is excellent not only in transparency and non-combustibility but also in toughness and bending properties and is difficult to break by bending and impact, and a method for producing the same.
A glass fiber fabric surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule is heated from 10 to 90% by weight of diallyl phthalate and 90 to 10% by weight of an unsaturated polyester resin. A transparent noncombustible sheet is provided which is integrated with a cured product of a curable resin mixture. Such a transparent noncombustible sheet is composed of a glass fiber fabric surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule, 10 to 90% by weight of a diallyl phthalate prepolymer and an unsaturated polyester resin 90 to 90%. It can be obtained by impregnating a thermosetting resin mixture comprising 10% by weight to obtain a prepreg, heating and pressing it, and integrating the glass fiber fabric with a cured product of the curable resin mixture.
[Selection figure] None
Description
本発明は、例えば、防煙垂壁として好適に用いることができる透明不燃性シートとその製造方法に関し、詳しくは、ガラス繊維織物を熱硬化性樹脂硬化物と一体化させてなり、透明性と不燃性にすぐれるのみならず、靱性乃至曲げ特性にすぐれる透明不燃性シートとその製造方法に関する。更に、本発明は、上記透明不燃性シートからなる防煙垂壁に関する。 The present invention relates to a transparent incombustible sheet that can be suitably used as, for example, a smoke-proof hanging wall and a method for producing the same, and more specifically, a glass fiber fabric is integrated with a thermosetting resin cured product, The present invention relates to a transparent non-combustible sheet that is excellent not only in incombustibility but also in toughness and bending properties, and a method for producing the same. Furthermore, this invention relates to the smoke-proof hanging wall which consists of the said transparent incombustible sheet.
商業ビル等の建築物には、火災時に煙や有毒ガスの流動拡散を妨げるために、天井に防煙垂壁を設置することが義務付けられている。従来、防煙垂壁には、良好な視野を確保することができると共に美観を損なわないように、通常、プラスチック板や板ガラスが用いられている。 Buildings such as commercial buildings are obliged to install smoke barriers on the ceiling to prevent the flow and diffusion of smoke and toxic gases in the event of a fire. Conventionally, a plastic plate or plate glass is usually used for the smoke-proof hanging wall so that a good visual field can be secured and the aesthetic appearance is not impaired.
プラスチック板は軽量であり、また、衝撃によっても損傷し難いものもあるが、不燃性については、十分ではない。そこで、プラスチック板に多量の無機物を配合して、不燃性を高めれば、透明性に劣ることとなる。 Plastic plates are lightweight and some are not easily damaged by impact, but they are not sufficient for nonflammability. Therefore, if a large amount of inorganic material is blended in the plastic plate to enhance nonflammability, the transparency will be inferior.
一方、板ガラスからなる防煙垂壁は、確かに透明性と不燃性にすぐれているが、重いという欠点があり、また、天井からの落下防止のための措置が施されているが、それでも、例えば、大きい地震が発生したときには、落下して、破損することが懸念される。 On the other hand, smoke-proof wall made of flat glass is certainly excellent in transparency and incombustibility, but has the disadvantage of being heavy, and measures are taken to prevent falling from the ceiling, For example, when a large earthquake occurs, there is a concern that it will fall and be damaged.
そこで、近年、ガラス繊維織物に樹脂硬化物層を設けてなるものが提案されているが（特許文献１及び２参照）、透明性において、尚、十分でない。 Therefore, in recent years, a glass fiber fabric provided with a cured resin layer has been proposed (see Patent Documents 1 and 2), but the transparency is still insufficient.
本発明は、従来の透明不燃性シートにおける上述した問題を解決するためになされたものであって、透明性と不燃性にすぐれているのみならず、靱性乃至曲げ特性にすぐれていて、曲げや衝撃によって割れ難い透明不燃性シートとその製造方法を提供することを目的とする。 The present invention has been made in order to solve the above-described problems in the conventional transparent non-combustible sheet, and is not only excellent in transparency and non-combustibility but also excellent in toughness or bending properties, An object of the present invention is to provide a transparent non-combustible sheet that is difficult to break by impact and a method for producing the same.
本発明によれば、分子中にアミノ基又は第４級アンモニウム構造を有するシランカップリング剤にて表面処理したガラス繊維織物をジアリルフタレート１０〜９０重量％と不飽和ポリエステル樹脂９０〜１０重量％からなる熱硬化性樹脂混合物の硬化物と一体化させてなることを特徴とする透明不燃性シートが提供される。 According to the present invention, glass fiber fabric surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule is prepared from 10 to 90% by weight of diallyl phthalate and 90 to 10% by weight of unsaturated polyester resin. A transparent noncombustible sheet is provided which is integrated with a cured product of the thermosetting resin mixture.
また、本発明によれば、分子中にアミノ基又は第４級アンモニウム構造を有するシランカップリング剤にて表面処理したガラス繊維織物にジアリルフタレートプレポリマー１０〜９０重量％と不飽和ポリエステル樹脂９０〜１０重量％からなる熱硬化性樹脂混合物を含浸してプリプレグを得、これを加熱加圧して、上記ガラス繊維織物を上記硬化性樹脂混合物の硬化物と一体化することを特徴とする透明不燃性シートの製造方法が提供される。 Further, according to the present invention, a glass fiber fabric surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule is added to 10 to 90% by weight of a diallyl phthalate prepolymer and an unsaturated polyester resin 90 to 90%. A transparent non-flammable, characterized in that a prepreg is impregnated with a thermosetting resin mixture comprising 10% by weight, and this is heated and pressurized to integrate the glass fiber fabric with a cured product of the curable resin mixture. A method for manufacturing a sheet is provided.
更に、本発明によれば、上述した透明不燃性シートからなる防煙垂壁が提供される。 Furthermore, according to this invention, the smoke-proof hanging wall which consists of a transparent noncombustible sheet | seat mentioned above is provided.
本発明による透明不燃性シートは、予め、シランカップリング剤にて表面処理したガラス繊維織物を所定の割合のジアリルフタレートと不飽和ポリエステル樹脂からなる熱硬化性樹脂混合物の硬化物と一体化してなるので、透明性と不燃性にすぐれているのみならず、靱性乃至曲げ特性にもすぐれていて、曲げや衝撃によっても割れ難いという特性を有する。従って、本発明による透明不燃性シートは、防煙垂壁として好適に用いることができる。 The transparent noncombustible sheet according to the present invention is formed by integrating a glass fiber woven surface-treated with a silane coupling agent in advance with a cured product of a thermosetting resin mixture comprising a predetermined proportion of diallyl phthalate and an unsaturated polyester resin. Therefore, it has not only excellent transparency and nonflammability, but also excellent toughness and bending characteristics, and it is difficult to break even by bending or impact. Therefore, the transparent noncombustible sheet according to the present invention can be suitably used as a smoke-proof hanging wall.
本発明による透明不燃性シートは、分子中にアミノ基又は第４級アンモニウム構造を有するシランカップリング剤にて表面処理したガラス繊維織物をジアリルフタレート１０〜９０重量％と不飽和ポリエステル樹脂９０〜１０重量％からなる熱硬化性樹脂混合物の硬化物と一体化させてなるものである。 The transparent noncombustible sheet according to the present invention comprises 10 to 90% by weight of diallyl phthalate and 90 to 10 unsaturated polyester resins of a glass fiber fabric surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule. It is formed by integrating with a cured product of a thermosetting resin mixture consisting of% by weight.
このような透明不燃性シートは、本発明に従って、分子中にアミノ基又は第４級アンモニウム構造を有するシランカップリング剤にて表面処理したガラス繊維織物にジアリルフタレートプレポリマー１０〜９０重量％と不飽和ポリエステル樹脂９０〜１０重量％からなる熱硬化性樹脂混合物を含浸してプリプレグを得、これを加熱加圧して、上記ガラス繊維織物を上記硬化性樹脂組成物の硬化物と一体化することによって得ることができる。 According to the present invention, such a transparent noncombustible sheet is 10% to 90% by weight of diallyl phthalate prepolymer on a glass fiber fabric surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule. By impregnating a thermosetting resin mixture consisting of 90 to 10% by weight of a saturated polyester resin to obtain a prepreg, heating and pressurizing it, and integrating the glass fiber fabric with a cured product of the curable resin composition Can be obtained.
先ず、本発明による透明不燃性シートの製造方法について説明する。 First, the manufacturing method of the transparent incombustible sheet by this invention is demonstrated.
本発明において、ガラス繊維織物を構成するガラス繊維は、汎用の無アルカリガラス繊維（Ｅガラス）、耐酸性の含アルカリガラス繊維（Ｃガラス）、高強度で高弾性率のガラス繊維（Ｓガラス、Ｔガラス等）、耐アルカリ性ガラス繊維（ＡＲガラス）等のいずれであってもよく、特に限定されるものではないが、なかでは、汎用性の高い無アルカリガラス繊維が好ましく用いられる。 In the present invention, the glass fiber constituting the glass fiber fabric is a general-purpose non-alkali glass fiber (E glass), acid-resistant alkali-containing glass fiber (C glass), high-strength and high-modulus glass fiber (S glass, T glass or the like) or alkali resistant glass fiber (AR glass) may be used, and is not particularly limited, but among them, alkali-free glass fiber having high versatility is preferably used.
本発明によれば、このようなガラス繊維は、そのフィラメント直径が１〜２０μｍの範囲にあることが好ましく、特に、３〜１２μｍの範囲にあることが好ましい。更に、本発明によれば、このようなガラス繊維からなるガラス繊維織物は、その織組織は、平織、朱子織、綾織、斜子織、畦織等のいずれでもよいが、これらのなかでは、平織、斜子織、畦織が好ましい。 According to the present invention, such a glass fiber preferably has a filament diameter in the range of 1 to 20 μm, particularly preferably in the range of 3 to 12 μm. Furthermore, according to the present invention, the glass fiber woven fabric composed of such glass fibers may be any of plain weave, satin weave, twill weave, oblique weave, silk weave, etc., among these, Plain weave, oblique weave and silk weave are preferred.
また、本発明によれば、ガラス繊維織物は、その坪量が４０〜２２０ｇ／ｍ2の範囲にあることが好ましい。また、ガラス繊維織物は、その厚みが０．０３〜０．２０ｍｍの範囲にあることが好ましい。 Moreover, according to this invention, it is preferable that the basic weight of a glass fiber fabric exists in the range of 40-220 g / m < 2 >. Moreover, it is preferable that the thickness of a glass fiber fabric exists in the range of 0.03-0.20 mm.
更に、本発明によれば、ガラス繊維織物が火炎に接しても、火炎がガラス繊維織物を通過し難いように、ガラス繊維織物中の隣接する経糸間の隙間が０．５ｍｍ以下であり、ガラス繊維織物中の隣接する緯糸間の隙間が０．５ｍｍ以下であることが好ましく、特に、いずれの隙間も０．２ｍｍ以下であることが好ましい。 Furthermore, according to the present invention, the gap between adjacent warps in the glass fiber fabric is 0.5 mm or less so that the flame does not easily pass through the glass fiber fabric even if the glass fiber fabric contacts the flame. It is preferable that a gap between adjacent wefts in the fiber fabric is 0.5 mm or less, and it is particularly preferable that any gap is 0.2 mm or less.
本発明においては、ジアリルフタレート樹脂の屈折率が１．５７であり、用いる熱硬化性樹脂混合物の硬化物が１．５４〜１．５７の範囲の屈折率を有するので、用いるガラス繊維織物も、１．５４〜１．５７の範囲の屈折率を有することが好ましい。 In the present invention, the refractive index of diallyl phthalate resin is 1.57, and the cured product of the thermosetting resin mixture used has a refractive index in the range of 1.54 to 1.57. It is preferable to have a refractive index in the range of 1.54 to 1.57.
本発明によれば、ガラス繊維織物は、これに熱硬化性樹脂混合物の硬化物を一体化して得られるいわば複合シートがすぐれた透明性を有するように、予め、シランカップリング剤にて表面処理されていることが必要であり、ここに、上記シランカップリング剤は、分子中にアミノ基又は第４級アンモニウム構造を有するものである。例えば、分子中にエポキシ基有するシランカップリング剤を用いるときは、透明性にすぐれる不燃性シートを得ることが困難である。また、ガラス繊維織物が上記シランカップリング剤で表面処理されていない場合には、得られた複合シートを折り曲げたとき、ガラス繊維織物と硬化樹脂の間で剥離や割れが生じ、部分的に白くなって、透明性が損なわれるので、取扱い性に問題がある。 According to the present invention, the glass fiber fabric is previously surface-treated with a silane coupling agent so that the composite sheet obtained by integrating the cured product of the thermosetting resin mixture with the so-called composite sheet has excellent transparency. Here, the silane coupling agent has an amino group or a quaternary ammonium structure in the molecule. For example, when a silane coupling agent having an epoxy group in the molecule is used, it is difficult to obtain a nonflammable sheet having excellent transparency. In addition, when the glass fiber fabric is not surface-treated with the silane coupling agent, peeling or cracking occurs between the glass fiber fabric and the cured resin when the obtained composite sheet is folded, and partially white. As a result, transparency is impaired, and there is a problem in handling.
分子中にアミノ基を有するシランカップリング剤として、例えば、３−アミノプロピルトリエトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン等を挙げることができるが、しかし、本発明において、分子中にアミノ基を有するシランカップリング剤は、これら例示に限定されるものではない。 Examples of the silane coupling agent having an amino group in the molecule include 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl) -3. -Aminopropyltrimethoxysilane and the like can be mentioned. However, in the present invention, the silane coupling agent having an amino group in the molecule is not limited to these examples.
また、分子中に第４級アンモニウム構造を有するシランカップリング剤として、例えば、トリメトキシシリルプロピルオクタデシルジメチルアンモニウムクロリド、トリメトキシシリルプロピルデシルメチルアンモニウムクロリド、トリエトキシシリルプロピルオクタデシルジメチルアンモニウムクロリド、１−トリメトキシシリルプロピル−１−メチルモルホリニウムヨージド（iodide）等を挙げることができるが、しかし、本発明において、分子中に第４級アンモニウム構造を有するシランカップリング剤は、上記例示に限定されるものではない。 Examples of the silane coupling agent having a quaternary ammonium structure in the molecule include trimethoxysilylpropyloctadecyldimethylammonium chloride, trimethoxysilylpropyldecylmethylammonium chloride, triethoxysilylpropyloctadecyldimethylammonium chloride, 1-trimethyl. Examples thereof include methoxysilylpropyl-1-methylmorpholinium iodide, but in the present invention, the silane coupling agent having a quaternary ammonium structure in the molecule is limited to the above examples. It is not something.
本発明によれば、必要に応じて、上記分子中にアミノ基を有するシランカップリング剤と上記第４級アンモニウム構造を有するシランカップリング剤を併用してもよい。 According to the present invention, if necessary, a silane coupling agent having an amino group in the molecule and a silane coupling agent having a quaternary ammonium structure may be used in combination.
本発明による透明不燃性シートは、このように予め、前記シランカップリング剤で表面処理したガラス繊維織物にジアリルフタレートプレポリマーと不飽和ポリエステル樹脂からなる硬化性樹脂混合物を含浸してプリプレグを得、これを、加熱加圧して、即ち、熱圧成形して、上記ガラス繊維織物を上記熱硬化性樹脂混合物の硬化物と一体化させることによって得ることができる。 The transparent non-combustible sheet according to the present invention is obtained by impregnating a curable resin mixture composed of a diallyl phthalate prepolymer and an unsaturated polyester resin into a glass fiber fabric surface-treated with the silane coupling agent in advance as described above, This can be obtained by heating and pressurizing, that is, hot pressing, and integrating the glass fiber fabric with the cured product of the thermosetting resin mixture.
本発明の方法において、プリプレグとは、上記ガラス繊維織物に上記熱硬化性樹脂混合物を付与して得られる成形用シート材をいう。 In the method of the present invention, the prepreg refers to a molding sheet material obtained by applying the thermosetting resin mixture to the glass fiber fabric.
かくして得られる透明不燃性シートにおいては、上記熱硬化性樹脂混合物の硬化物は、ガラス繊維織物の内部の空隙を充填していると共に、ガラス繊維織物の表裏の両表面を被覆して、上記熱硬化性樹脂混合物の硬化物と一体化している。 In the transparent noncombustible sheet thus obtained, the cured product of the thermosetting resin mixture fills the voids inside the glass fiber fabric and covers both the front and back surfaces of the glass fiber fabric. It is integrated with the cured product of the curable resin mixture.
ジアリルフタレートプレポリマーは、ジアリルフタレートモノマーに有機過酸化物やアゾ系重合開始剤を加え、塊状重合させて、線状ポリマーの生成の段階で重合を中止し、貧溶媒中で沈殿させ、濾過、乾燥して得られる白色の粉末である。このようなジアリルフタレートプレポリマーが硬化して得られる樹脂は、前述したように、屈折率が１．５７である。 The diallyl phthalate prepolymer is an organic peroxide or azo polymerization initiator added to the diallyl phthalate monomer, bulk polymerization is performed, the polymerization is stopped at the production stage of the linear polymer, precipitated in a poor solvent, filtered, It is a white powder obtained by drying. The resin obtained by curing such a diallyl phthalate prepolymer has a refractive index of 1.57 as described above.
不飽和ポリエステル樹脂は、典型的には、無水マレイン酸のような不飽和酸と無水フタル酸のような飽和多塩基酸を併用して、これらを２価アルコールと縮合させて得られる不飽和ポリエステルをスチレンモノマーのような重合性単量体や適宜の有機溶媒に溶解させた液状樹脂をいう。 The unsaturated polyester resin is typically an unsaturated polyester obtained by condensing an unsaturated acid such as maleic anhydride and a saturated polybasic acid such as phthalic anhydride and condensing them with a dihydric alcohol. Is a liquid resin in which a polymerizable monomer such as a styrene monomer is dissolved in an appropriate organic solvent.
上述したような不飽和ポリエステル樹脂は、通常、１．５３〜１．５７の範囲の屈折率を有する。本発明によれば、不飽和ポリエステル樹脂を構成する成分にもよるが、前述したように、ジアリルフタレート樹脂の屈折率である１．５７に近い屈折率を有するものが好ましく用いられる。従って、通常、ジアリルフタレート樹脂と不飽和ポリエステル樹脂の共重合によって得られる硬化物は、１．５４〜１．５７の範囲の屈折率を有する。 The unsaturated polyester resin as described above usually has a refractive index in the range of 1.53 to 1.57. According to the present invention, although depending on the components constituting the unsaturated polyester resin, those having a refractive index close to 1.57 which is the refractive index of the diallyl phthalate resin are preferably used as described above. Therefore, usually, a cured product obtained by copolymerization of a diallyl phthalate resin and an unsaturated polyester resin has a refractive index in the range of 1.54 to 1.57.
ジアリルフタレートプレポリマーと不飽和ポリエステル樹脂からなる熱硬化性樹脂混合物は、通常、重合開始剤を含み、更に、必要に応じて、重合禁止剤、内部離型剤等を含む。上記重合開始剤としては、通常、ジクミルパーオキシド、ベンゾイルパーオキシド、ラウロイルパーオキシド、ｔ−ブチルパーベンゾエート、メチルエチルケトンパーオキシド等が用いられるが、これら例示に限定されるものではない。 The thermosetting resin mixture comprising a diallyl phthalate prepolymer and an unsaturated polyester resin usually contains a polymerization initiator, and further contains a polymerization inhibitor, an internal mold release agent and the like as necessary. As the polymerization initiator, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, methyl ethyl ketone peroxide, and the like are usually used, but are not limited to these examples.
更に、上記熱硬化性樹脂混合物は、必要に応じて、難燃剤、紫外線吸収剤、充填剤、帯電防止剤等の添加剤を含んでいてもよい。難燃剤としては、例えば、水酸化アルミニウム、水酸化マグネシウム、トリクロロエチルホスフェート、トリアリルホスフェート、ポリリン酸アンモニウム、リン酸エステル等を挙げることができる。紫外線吸収剤としては、例えば、ベンゾトリアゾール等を、また、充填剤としては、例えば、炭酸カルシウム、シリカ、タルク等を、帯電防止剤としては、例えば、界面活性剤を挙げることができる。 Furthermore, the said thermosetting resin mixture may contain additives, such as a flame retardant, a ultraviolet absorber, a filler, and an antistatic agent, as needed. Examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, trichloroethyl phosphate, triallyl phosphate, ammonium polyphosphate, and phosphate ester. Examples of the ultraviolet absorber include benzotriazole, examples of the filler include calcium carbonate, silica, and talc. Examples of the antistatic agent include a surfactant.
このような熱硬化性樹脂混合物は、ガラス繊維織物のガラス繊維間に十分に浸透し得る粘度を有するように、適宜の有機溶媒を用いて希釈して、適当な固形分濃度とした液状樹脂組成物とし、これをガラス繊維織物に含浸させ、例えば、スクイズロール等を用いて、樹脂量が所定量になるように調整した後、所定の揮発分を有するように、例えば、熱風乾燥機を用いて乾燥して、プリプレグを得る。上記有機溶媒は、上記乾燥において、樹脂中にボイドが生成しないように、低沸点溶媒と高沸点溶媒の組み合わせ、例えば、アセトンと酢酸プロピルの組み合わせが好ましく用いられる。 Such a thermosetting resin mixture is diluted with an appropriate organic solvent so as to have a viscosity that can sufficiently penetrate between glass fibers of a glass fiber fabric, and a liquid resin composition having an appropriate solid content concentration. For example, a hot air dryer is used so as to have a predetermined volatile content after adjusting the resin amount to be a predetermined amount using a squeeze roll or the like. And dry to obtain a prepreg. As the organic solvent, a combination of a low-boiling solvent and a high-boiling solvent, for example, a combination of acetone and propyl acetate is preferably used so that voids are not generated in the resin during the drying.
本発明によれば、得られる透明不燃性シートが透明性と不燃性にすぐれのみならず、曲げや衝撃に対して十分な抵抗を有するように、即ち、靱性を有して、割れ難いように、前記熱硬化性樹脂混合物は、ジアリルフタレートプレポリマーが１０〜９０重量％と不飽和ポリエステル樹脂が固形分にて９０〜１０重量％からなる。熱硬化性樹脂混合物において、ジアリルフタレートプレポリマーが１０重量％よりも少ないとき、即ち、不飽和ポリエステル樹脂が固形分にて９０重量％を越えるときは、得られるプリプレグを熱圧成形して得られる複合シートは透明性に劣る。一方、熱硬化性樹脂混合物において、ジアリルフタレートプレポリマーが９０重量％よりも多いとき、即ち、不飽和ポリエステル樹脂が１０重量％よりも少ないときは、得られるプリプレグを熱圧成形して得られるシートは曲げ特性乃至靱性に劣って、曲げや衝撃によって割れやすい。 According to the present invention, the obtained transparent non-combustible sheet is not only excellent in transparency and non-combustibility, but also has sufficient resistance to bending and impact, that is, has toughness and is difficult to break. The thermosetting resin mixture comprises 10 to 90% by weight of diallyl phthalate prepolymer and 90 to 10% by weight of unsaturated polyester resin in solid content. In the thermosetting resin mixture, when the diallyl phthalate prepolymer is less than 10% by weight, that is, when the unsaturated polyester resin exceeds 90% by weight in solid content, the resulting prepreg is obtained by hot pressing. The composite sheet is inferior in transparency. On the other hand, in the thermosetting resin mixture, when the diallyl phthalate prepolymer is more than 90% by weight, that is, when the unsaturated polyester resin is less than 10% by weight, a sheet obtained by hot pressing the resulting prepreg. Is inferior in bending properties or toughness and easily broken by bending or impact.
本発明によれば、前記熱硬化性樹脂混合物は、好ましくは、ジアリルフタレートプレポリマーが２０〜８０重量％と不飽和ポリエステル樹脂が固形分にて８０〜２０重量％からなる。 According to the present invention, the thermosetting resin mixture preferably comprises 20 to 80% by weight of diallyl phthalate prepolymer and 80 to 20% by weight of unsaturated polyester resin in solid content.
更に、本発明において、プリプレグにおける樹脂量、即ち、ジアリルフタレートプレポリマーと不飽和ポリエステル樹脂（固形分）の合計量は、得られるシートがすぐれた透明性を有するように、ガラス繊維織物１００重量部に対して６０重量部以上であり、すぐれた不燃性を有するように、ガラス繊維織物１ｍ2当たりに４００ｇ以下である。プリプレグにおける樹脂量は、得られる透明不燃性シートにおける樹脂量でもある。 Furthermore, in the present invention, the amount of resin in the prepreg, that is, the total amount of diallyl phthalate prepolymer and unsaturated polyester resin (solid content) is 100 parts by weight of glass fiber fabric so that the resulting sheet has excellent transparency. The amount is 400 g or less per 1 m 2 of the glass fiber fabric so as to have an excellent nonflammability. The amount of resin in the prepreg is also the amount of resin in the obtained transparent incombustible sheet.
プリプレグにおける樹脂量がガラス繊維織物１００重量部に対して６０重量部よりも少ないときは、得られるシートの透明性が低下するおそれがあり、一方、プリプレグにおける樹脂量がガラス繊維織物１ｍ2当たりに４００ｇよりも多いときは、得られるシートの不燃性が低下するおそれがある。 When the amount of resin in the prepreg is less than 60 parts by weight with respect to 100 parts by weight of the glass fiber woven fabric, the transparency of the resulting sheet may be lowered, while the amount of resin in the prepreg is about 1 m 2 of glass fiber woven fabric. When the amount is more than 400 g, the incombustibility of the obtained sheet may be lowered.
上記プリプレグにおける樹脂量の下限量、即ち、ガラス繊維織物１００重量部に対して６０重量部は、用いるガラス繊維織物の坪量が４０ｇ／ｍ2であるとき、樹脂量はガラス繊維織物１ｍ2当たりに２４ｇ／ｍ2であり、用いるガラス繊維織物の坪量が２２０ｇ／ｍ2であるとき、樹脂量はガラス繊維織物１ｍ2当たりに１３２ｇ／ｍ2である。 The lower limit of the amount of resin in the prepreg, that is, 60 parts by weight with respect to 100 parts by weight of the glass fiber fabric, when the basis weight of the glass fiber fabric used is 40 g / m 2 , the resin amount is 1 m 2 of glass fiber fabric. in a 24 g / m 2, when the basis weight of the glass fiber woven fabric used is 220 g / m 2, the resin amount is 132g / m 2 on glass fiber fabric 1 m 2 per.
また、上記プリプレグにおける樹脂量の上限量、即ち、ガラス繊維織物１ｍ2当たりに４００ｇは、用いるガラス繊維織物の坪量が４０ｇ／ｍ2であるとき、樹脂量はガラス繊維織物１００重量部に対して１０００重量部であり、用いるガラス繊維織物の坪量が２２０ｇ／ｍ2であるとき、樹脂量はガラス繊維織物１００重量部に対して１８２重量部である。 The upper limit of the amount of resin in the prepreg, that is, 400 g per 1 m 2 of glass fiber fabric, when the basis weight of the glass fiber fabric used is 40 g / m 2 , the resin amount is 100 parts by weight of the glass fiber fabric. When the basis weight of the glass fiber fabric used is 220 g / m 2 , the resin amount is 182 parts by weight with respect to 100 parts by weight of the glass fiber fabric.
従って、本発明によれば、プリプレグにおける樹脂量は、ガラス繊維織物１ｍ2当たりに２４〜４００ｇの範囲とガラス繊維織物１００重量部に対して６０〜１０００重量部の範囲の両方を満たす範囲の量であるということができる。 Therefore, according to the present invention, the amount of resin in the prepreg is an amount in a range satisfying both the range of 24 to 400 g per 1 m 2 of glass fiber fabric and the range of 60 to 1000 parts by weight with respect to 100 parts by weight of glass fiber fabric. It can be said that.
特に、本発明によれば、好ましくは、プリプレグにおける樹脂量は、固形分にて、ガラス繊維織物１００重量部に対して８０重量部以上で、ガラス繊維織物１ｍ2当たりに３６０ｇ以下である。 In particular, according to the present invention, preferably, the amount of resin in the prepreg is not less than 80 parts by weight with respect to 100 parts by weight of the glass fiber woven fabric and not more than 360 g per 1 m 2 of the glass fiber woven fabric.
本発明によれば、上述したように、上記熱硬化性樹脂混合物を含む液状組成物をガラス繊維織物に含浸させ、所定の樹脂量と揮発分を有するように調整して、プリプレグを得、これを熱圧成形することによって、目的とする透明不燃性シートを得ることができる。より詳細には、例えば、プリプレグをアルミニウム板の間に挟んで積層体とし、更に、この積層体をクッションの間に挟んだ後、一対の熱盤の間で温度１２０〜１５０℃、圧力１．０〜７．０ＭＰａで１０分乃至１時間加熱加圧し、上記ガラス繊維織物を上記硬化性樹脂混合物の硬化物と一体化することによって得ることができる。 According to the present invention, as described above, a glass fiber fabric is impregnated with a liquid composition containing the thermosetting resin mixture, and adjusted so as to have a predetermined resin amount and volatile matter, thereby obtaining a prepreg. The desired transparent noncombustible sheet can be obtained by hot pressing. More specifically, for example, a prepreg is sandwiched between aluminum plates to form a laminate, and further, the laminate is sandwiched between cushions, and then a temperature of 120 to 150 ° C. between a pair of hot plates and a pressure of 1.0 to It can be obtained by heating and pressing at 7.0 MPa for 10 minutes to 1 hour to integrate the glass fiber fabric with the cured product of the curable resin mixture.
かくして、本発明による透明不燃性シートは、分子中にアミノ基又は第４級アンモニウム構造を有するシランカップリング剤にて表面処理したガラス繊維織物をジアリルフタレート１０〜９０重量％と不飽和ポリエステル樹脂９０〜１０重量％からなる熱硬化性樹脂混合物の硬化物と一体化させてなり、好ましくは、シートにおける樹脂量は、ガラス繊維織物１００重量部に対して６０重量部以上で、ガラス繊維織物１ｍ2当たりに４００ｇ以下の範囲であり、透明性と不燃性にすぐれており、そのうえ、靱性や曲げ特性にもすぐれていて、衝撃を受けても割れ難い。 Thus, the transparent non-combustible sheet according to the present invention comprises 10% to 90% by weight of unsaturated polyester resin 90% by weight of diallyl phthalate in a glass fiber fabric surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule. It is integrated with a cured product of a thermosetting resin mixture composed of 10% by weight, and preferably, the amount of resin in the sheet is 60 parts by weight or more with respect to 100 parts by weight of the glass fiber woven fabric, and 1 m 2 of glass fiber woven fabric. It is in a range of 400 g or less per hit, is excellent in transparency and nonflammability, is excellent in toughness and bending characteristics, and is difficult to crack even when subjected to an impact.
以下に実施例を挙げて本発明を詳細に説明するが、本発明はそれら実施例によって何ら限定されるものではない。 EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
実施例１、２、比較例１及び２においては、ガラス繊維織物に対して樹脂量を比較的多くし、比較例１及び２においては、樹脂として、ジアリルフタレート又は不飽和ポリエステル樹脂のいずれか一方のみを用いた。また、用いたガラス繊維織物を構成するガラス繊維の屈折率は１．５６であり、不飽和ポリエステル樹脂の屈折率は１．５３であった。 In Examples 1 and 2 and Comparative Examples 1 and 2, the amount of resin is relatively large with respect to the glass fiber fabric, and in Comparative Examples 1 and 2, either one of diallyl phthalate or unsaturated polyester resin is used as the resin. Only was used. Moreover, the refractive index of the glass fiber which comprises the used glass fiber fabric was 1.56, and the refractive index of unsaturated polyester resin was 1.53.
実施例３〜６、比較例３及び４においては、ガラス繊維織物に対する樹脂量を一定とし、実施例３〜６においては、硬化性樹脂として、ジアリルフタレートと不飽和ポリエステル樹脂の割合を変化させた。比較例３においては、予め、シランカップリング剤で表面処理しなかったガラス繊維織物を用い、比較例４においては、予め、ガラス繊維織物を分子中にエポキシ基を有するシランカップリング剤にて表面処理したものを用いた。 In Examples 3 to 6 and Comparative Examples 3 and 4, the amount of resin with respect to the glass fiber fabric was constant, and in Examples 3 to 6, the ratio of diallyl phthalate and unsaturated polyester resin was changed as the curable resin. . In Comparative Example 3, a glass fiber fabric that was not surface-treated with a silane coupling agent in advance was used, and in Comparative Example 4, the glass fiber fabric was previously surfaced with a silane coupling agent having an epoxy group in the molecule. What was processed was used.
また、以下実施例と比較例において、得られたシ−トの透明性と不燃性と反発圧縮力は以下のようにして評価乃至測定した。 Further, in the following examples and comparative examples, the transparency, nonflammability and rebound compression force of the obtained sheets were evaluated or measured as follows.
（透明性）
得られたシ−トを通して、２ｍ離れた紙上の６０ポイントの「新」なる文字が明瞭に識別できたときを「良好」とし、明瞭に識別できないときを「不良」とした。
(transparency)
When the 60-point “new” character on the paper 2 m away could be clearly identified through the obtained sheet, it was judged as “good”, and when it could not be clearly identified as “bad”.
（不燃性）
ＩＳＯ ５６６０−１に規定するコーンカロリーメーター法に準拠した発熱試験によって評価した。即ち、輻射電気ヒーターによって試料シートの表面に輻射熱５０ＫＷ／ｍ2を照射する発熱性試験において、（１）加熱開始後２０分間の総発熱量が８ＭＪ／ｍ2以下であると共に、（２）加熱開始後２０分間、最高発熱速度が１０秒以上継続して２００ＫＷ／ｍ2を超えず、更に、（３）上記発熱性試験の後も、ガラス繊維織物における経糸間の間隔と緯糸間の間隔がいずれも０．５ｍｍ以下であるという条件をすべて満たすときを「合格」とし、上記（１）〜（３）の条件の少なくとも１つを満たさないときを「不合格」とした。尚、不燃性の欄の括弧内の数値は、上記発熱性試験における加熱開始後２０分間の総発熱量を示す。
(Non Flammable)
It evaluated by the heat_generation | fever test based on the corn calorimeter method prescribed | regulated to ISO 5660-1. That is, in the exothermic test in which the surface of the sample sheet is irradiated with radiant heat 50 KW / m 2 by a radiant electric heater, (1) the total calorific value for 20 minutes after the start of heating is 8 MJ / m 2 or less, and (2) heating For 20 minutes after the start, the maximum heat generation rate continues for 10 seconds or more and does not exceed 200 KW / m 2 , and (3) even after the heat generation test, the distance between the warp and the distance between the wefts in the glass fiber fabric When all satisfy | fill all the conditions that it is 0.5 mm or less, it was set as "pass", and when not satisfying at least one of the conditions of said (1)-(3) was set as "fail". The numerical value in parentheses in the nonflammability column indicates the total calorific value for 20 minutes after the start of heating in the exothermic test.
（反発圧縮力）
得られたシートを幅２５ｍｍ、長さ５０ｍｍの短冊状に裁断し、これを長手方向に巻いて環状体を作製し、この環状体の周面を水平面に接触させて立てて、周面の最上部を５ｍｍ押し下げたときの環状体の反発力を反発圧縮力として測定した。測定には万能引張り試験機（ミネベア（株）製ＴＣＭ−１０ＫＮＢ）を用いた。
(Repulsive compression force)
The obtained sheet is cut into a strip shape having a width of 25 mm and a length of 50 mm, and this is wound in the longitudinal direction to produce an annular body. The circumferential surface of the annular body is brought into contact with a horizontal plane, and the outermost surface of the circumferential surface is formed. The repulsive force of the annular body when the upper part was pushed down by 5 mm was measured as the repulsive compression force. A universal tensile testing machine (TCM-10KNB manufactured by Minebea Co., Ltd.) was used for the measurement.
（全光線透透過率）
ＪＩＳ Ｋ−７１０５によった。
(Total light transmittance)
According to JIS K-7105.
実施例１
樹脂成分としてのジアリルフタレートプレポリマー粉末（ダイソー（株）製商品名ダイソーダップ、以下、同じ。）８０重量部と液状不飽和ポリエステル樹脂（固形分）（ディーエイチ・マテリアル（株）製商品名サンドーマ、以下、同じ。）２０重量部に過酸化ベンゾイル（固形分７５重量％）３．５重量部、離型剤（中京油脂（株）製リン酸アルキルエステル、セパール３２５、以下、同じ。）０．５重量部、アセトン６５重量部及び酢酸プロピル１０重量部を均一に混合して液状樹脂組成物を調製した。
Example 1
80 parts by weight of diallyl phthalate prepolymer powder as a resin component (Daiso Co., Ltd., trade name Daiso Dup, hereinafter the same) and liquid unsaturated polyester resin (solid content) (trade name SANDOMA, manufactured by DH Material Co., Ltd.) The same applies hereinafter.) 20 parts by weight, 3.5 parts by weight of benzoyl peroxide (solid content 75% by weight), release agent (Chukyo Yushi Co., Ltd. phosphoric acid alkyl ester, Separ 325, the same applies hereinafter) 0 A liquid resin composition was prepared by uniformly mixing 0.5 parts by weight, 65 parts by weight of acetone and 10 parts by weight of propyl acetate.
予め、第４級アンモニウム塩構造を有するカチオン性シランカップリング剤で表面処理した坪量４７ｇ／ｍ2の平織りのガラス繊維織物に上記液状樹脂組成物を含浸させ、所定の樹脂量となるようにスクイズロールを用いて調整した後、熱風式乾燥機を用いて所定の揮発分を有するように乾燥して、樹脂量３６０ｇ／ｍ2（ガラス繊維織物１００重量部に対して７６６重量部）を有するジアリルフタレートプリプレグを得た。 A glass fiber woven fabric having a basis weight of 47 g / m 2 and surface-treated with a cationic silane coupling agent having a quaternary ammonium salt structure is impregnated with the liquid resin composition in advance so that a predetermined resin amount is obtained. After adjusting using a squeeze roll, it is dried so as to have a predetermined volatile content using a hot air dryer, and has a resin amount of 360 g / m 2 (766 parts by weight relative to 100 parts by weight of glass fiber fabric). Diallyl phthalate prepreg was obtained.
このプリプレグをアルミニウム板の間に挟んで積層体とし、更に、この積層体をクッションの間に挟んだ後、一対の熱盤の間で温度１３０℃、圧力６．０ＭＰａ、時間２０分の条件で加熱加圧して、本発明による透明不燃性シートを得た。この透明不燃性シートは、透明性「良好」、不燃性「合格」（６．５ＭＪ／ｍ2）であった。 The prepreg is sandwiched between aluminum plates to form a laminate. Further, the laminate is sandwiched between cushions, and heated between a pair of heating plates at a temperature of 130 ° C., a pressure of 6.0 MPa, and a time of 20 minutes. To obtain a transparent incombustible sheet according to the present invention. This transparent incombustible sheet had transparency “good” and incombustibility “passed” (6.5 MJ / m 2 ).
実施例２
ガラス繊維織物として、坪量２０９ｇ／ｍ2の平織りのガラス繊維織物を用いて、樹脂量３６０ｇ／ｍ2（ガラス繊維織物１００重量部に対して１７２重量部）を有するジアリルフタレートプリプレグを得た以外は、実施例１と同様にして、本発明による透明不燃性シートを得た。この透明不燃性シートは、透明性「合格」、不燃性「合格」（６．３ＭＪ／ｍ2）であった。
Example 2
As the glass fiber woven fabric, except that using a glass fiber fabric of plain weave having a basis weight of 209 g / m 2, to obtain a diallyl phthalate prepreg having a resin content 360g / m 2 (172 parts by weight per 100 parts by weight glass fiber fabric) In the same manner as in Example 1, a transparent noncombustible sheet according to the present invention was obtained. This transparent noncombustible sheet had transparency “pass” and nonflammability “pass” (6.3 MJ / m 2 ).
比較例１
樹脂成分として液状不飽和ポリエステル樹脂（固形分）１００重量部を用いた以外は、実施例１と同様にして、液状樹脂組成物を調製した。
Comparative Example 1
A liquid resin composition was prepared in the same manner as in Example 1 except that 100 parts by weight of a liquid unsaturated polyester resin (solid content) was used as the resin component.
実施例１と同じシランカップリング剤で表面処理した坪量４７ｇ／ｍ2の平織りのガラス繊維織物に上記液状樹脂組成物を含浸させ、所定の樹脂量となるようにスクイズロールを用いて調整した後、熱風式乾燥機を用いて所定の揮発分を有するように乾燥して、樹脂量１９０ｇ／ｍ2（ガラス繊維織物１００重量部に対して４００重量部）を有するジアリルフタレートプリプレグを得た。 A plain weave glass fiber fabric having a basis weight of 47 g / m 2 surface-treated with the same silane coupling agent as in Example 1 was impregnated with the liquid resin composition, and adjusted using a squeeze roll so as to obtain a predetermined resin amount. Then, it dried so that it might have predetermined | prescribed volatile content using a hot air type dryer, and obtained the diallyl phthalate prepreg which has a resin amount of 190 g / m < 2 > (400 weight part with respect to 100 weight part of glass fiber fabrics).
このプリプレグを用いて、実施例１と同様にして、比較例１としての透明不燃性シートを得た。この透明不燃性シートは、透明性「不良」、不燃性「合格」（３．６ＭＪ／ｍ2）であった。 Using this prepreg, a transparent incombustible sheet as Comparative Example 1 was obtained in the same manner as Example 1. This transparent incombustible sheet had transparency “bad” and incombustibility “passed” (3.6 MJ / m 2 ).
比較例２
樹脂成分としてジアリルフタレートプレポリマー粉末１００重量部を用いた以外は、実施例１と同様にして、液状樹脂組成物を調製した。
Comparative Example 2
A liquid resin composition was prepared in the same manner as in Example 1 except that 100 parts by weight of diallyl phthalate prepolymer powder was used as the resin component.
予め、実施例１と同じシランカップリング剤で表面処理した坪量４７ｇ／ｍ2の平織りのガラス繊維織物に上記液状樹脂組成物を含浸させ、所定の樹脂量となるようにスクイズロールを用いて調整した後、熱風式乾燥機を用いて所定の揮発分を有するように乾燥して、樹脂量１９０ｇ／ｍ2（ガラス繊維織物１００重量部に対して４００重量部）を有するジアリルフタレートプリプレグを得た。 A glass fiber woven fabric having a basis weight of 47 g / m 2 surface-treated with the same silane coupling agent as in Example 1 was impregnated with the liquid resin composition in advance, and a squeeze roll was used so as to obtain a predetermined resin amount. After the adjustment, drying is performed using a hot air dryer so as to have a predetermined volatile content, thereby obtaining a diallyl phthalate prepreg having a resin amount of 190 g / m 2 (400 parts by weight with respect to 100 parts by weight of glass fiber fabric). It was.
このプリプレグを用いて、実施例１と同じ条件下に加熱加圧して、比較例２としての透明不燃性シートを得た。この透明不燃性シートは、透明性「良好」、不燃性「合格」（３．７ＭＪ／ｍ2）であった。但し、この透明不燃性シートは、環状体の反発圧縮力の測定時に割れた。 Using this prepreg, it was heated and pressurized under the same conditions as in Example 1 to obtain a transparent incombustible sheet as Comparative Example 2. This transparent incombustible sheet had transparency “good” and incombustibility “passed” (3.7 MJ / m 2 ). However, this transparent incombustible sheet cracked when measuring the rebound compression force of the annular body.
実施例３
予め、実施例１と同じ第４級アンモニウム塩構造を有するカチオン性シランカップリング剤で表面処理した坪量１００ｇ／ｍ2の平織りのガラス繊維織物に実施例１と同じ液状樹脂組成物を含浸させ、所定の樹脂量となるようにスクイズロールを用いて調整した後、熱風式乾燥機を用いて所定の揮発分を有するように乾燥して、ガラス繊維織物１００重量部に対して樹脂量１１０重量部のジアリルフタレートプリプレグを得た。
Example 3
A glass fiber woven fabric having a basis weight of 100 g / m 2 and surface-treated with a cationic silane coupling agent having the same quaternary ammonium salt structure as in Example 1 is impregnated with the same liquid resin composition as in Example 1 in advance. After adjusting with a squeeze roll so as to have a predetermined resin amount, it is dried to have a predetermined volatile content using a hot air dryer, and the resin amount is 110 weights with respect to 100 parts by weight of the glass fiber fabric. Part of diallyl phthalate prepreg was obtained.
このプリプレグを実施例１と同じ条件下に加熱加圧して、本発明による透明不燃性シートを得た。この透明不燃性シートは、透明性「良好」、反発圧縮力２．５Ｎ、全光線透過率９２．４％であった。 This prepreg was heated and pressurized under the same conditions as in Example 1 to obtain a transparent noncombustible sheet according to the present invention. This transparent noncombustible sheet had transparency “good”, rebound compression force 2.5 N, and total light transmittance 92.4%.
実施例４
予め、アミノ基を有するシランカップリング剤で表面処理した坪量１００ｇ／ｍ2の平織りのガラス繊維織物に実施例１と同じ液状樹脂組成物を含浸させ、所定の樹脂量となるようにスクイズロールを用いて調整した後、熱風式乾燥機を用いて所定の揮発分を有するように乾燥して、ガラス繊維織物１００重量部に対して樹脂量１１０重量部のジアリルフタレートプリプレグを得た。
Example 4
A glass fiber fabric having a plain weave having a basis weight of 100 g / m 2 and surface-treated with a silane coupling agent having an amino group is impregnated with the same liquid resin composition as in Example 1, and a squeeze roll is used so that a predetermined resin amount is obtained. Then, it was dried so as to have a predetermined volatile content using a hot air drier, to obtain a diallyl phthalate prepreg having a resin amount of 110 parts by weight with respect to 100 parts by weight of the glass fiber fabric.
このプリプレグを実施例１と同じ条件下に加熱加圧して、本発明による透明不燃性シートを得た。この透明不燃性シートは、透明性「良好」、反発圧縮力２．３Ｎ、全光線透過率９１．５％であった。 This prepreg was heated and pressurized under the same conditions as in Example 1 to obtain a transparent noncombustible sheet according to the present invention. This transparent noncombustible sheet had transparency “good”, repulsive compression force 2.3 N, and total light transmittance 91.5%.
実施例５
樹脂成分として、ジアリルフタレートプレポリマー粉末２０重量部と液状不飽和ポリエステル樹脂（固形分）８０重量部を用いた以外は、実施例１と同様にして、液状樹脂組成物を調製した。
Example 5
A liquid resin composition was prepared in the same manner as in Example 1 except that 20 parts by weight of diallyl phthalate prepolymer powder and 80 parts by weight of liquid unsaturated polyester resin (solid content) were used as the resin component.
予め、実施例１と同じアミノ基を有するシランカップリング剤で表面処理した坪量１００ｇ／ｍ2の平織りのガラス繊維織物に上記液状樹脂組成物を含浸させ、所定の樹脂量となるようにスクイズロールを用いて調整した後、熱風式乾燥機を用いて所定の揮発分を有するように乾燥して、ガラス繊維織物１００重量部に対して樹脂量１１０重量部のジアリルフタレートプリプレグを得た。 A plain glass fiber fabric having a basis weight of 100 g / m 2 and surface-treated with the same silane coupling agent having the same amino group as in Example 1 is impregnated with the above liquid resin composition, and squeezed so as to obtain a predetermined resin amount. After adjusting using a roll, it was dried using a hot air drier so as to have a predetermined volatile content, thereby obtaining a diallyl phthalate prepreg having a resin amount of 110 parts by weight with respect to 100 parts by weight of the glass fiber fabric.
このプリプレグを実施例１と同じ条件下に加熱加圧して、本発明による透明不燃性シートを得た。この透明不燃性シートは、透明性「良好」、反発圧縮力０．９８Ｎ、全光線透過率９０．４％であった。 This prepreg was heated and pressurized under the same conditions as in Example 1 to obtain a transparent noncombustible sheet according to the present invention. This transparent noncombustible sheet had transparency “good”, rebound compression force 0.98 N, and total light transmittance 90.4%.
実施例６
樹脂成分として、ジアリルフタレートプレポリマー粉末５０重量部と液状不飽和ポリエステル樹脂（固形分）５０重量部を用いた以外は、実施例１と同様にして、液状樹脂組成物を調製した。
Example 6
A liquid resin composition was prepared in the same manner as in Example 1 except that 50 parts by weight of diallyl phthalate prepolymer powder and 50 parts by weight of liquid unsaturated polyester resin (solid content) were used as the resin component.
予め、実施例１と同じ第４級アンモニウム塩構造を有するカチオン性シランカップリング剤で表面処理した坪量１００ｇ／ｍ2の平織りのガラス繊維織物に上記液状樹脂組成物を含浸させ、所定の樹脂量となるようにスクイズロールを用いて調整した後、熱風式乾燥機を用いて所定の揮発分を有するように乾燥して、ガラス繊維織物１００重量部に対して樹脂量１１０重量部のジアリルフタレートプリプレグを得た。 A glass fiber woven fabric having a basis weight of 100 g / m 2 and surface-treated with a cationic silane coupling agent having the same quaternary ammonium salt structure as in Example 1 is impregnated with the above liquid resin composition in advance. After adjusting using a squeeze roll so that the amount of the resin becomes 110% by weight, the resin is 110 parts by weight of diallyl phthalate with 100 parts by weight of the glass fiber fabric. A prepreg was obtained.
このプリプレグを実施例１と同じ条件下に加熱加圧して、本発明による透明不燃性シートを得た。この透明不燃性シートは、透明性「良好」、反発圧縮力１．５Ｎ、全光線透過率９１．６％であった。 This prepreg was heated and pressurized under the same conditions as in Example 1 to obtain a transparent noncombustible sheet according to the present invention. This transparent noncombustible sheet had transparency “good”, rebound compression force 1.5 N, and total light transmittance 91.6%.
比較例３
予め、シランカップリング剤で表面処理することなく、坪量１００ｇ／ｍ2の平織りのガラス繊維織物に実施例１と同じ液状樹脂組成物を含浸させ、所定の樹脂量となるようにスクイズロールを用いて調整した後、熱風式乾燥機を用いて所定の揮発分を有するように乾燥して、ガラス繊維織物１００重量部に対して樹脂量１１０重量部のジアリルフタレートプリプレグを得た。
Comparative Example 3
Before the surface treatment with a silane coupling agent, a plain weave glass fiber fabric having a basis weight of 100 g / m 2 is impregnated with the same liquid resin composition as in Example 1, and a squeeze roll is provided so as to obtain a predetermined resin amount. After adjusting using, it dried so that it might have a predetermined | prescribed volatile content using a hot air dryer, and obtained the diallyl phthalate prepreg of 110 weight part of resin with respect to 100 weight part of glass fiber fabrics.
このプリプレグを実施例１と同じ条件下に加熱加圧して、比較例３としてのシートを得た。このシートは透明性において「不良」であった。 This prepreg was heated and pressurized under the same conditions as in Example 1 to obtain a sheet as Comparative Example 3. This sheet was “poor” in transparency.
比較例４
予め、エポキシ基を有するシランカップリング剤で表面処理した坪量１００ｇ／ｍ2の平織りのガラス繊維織物に実施例１と同じ液状樹脂組成物を含浸させ、所定の樹脂量となるようにスクイズロールを用いて調整した後、熱風式乾燥機を用いて所定の揮発分を有するように乾燥して、ガラス繊維織物１００重量部に対して樹脂量１１０重量部のジアリルフタレートプリプレグを得た。
Comparative Example 4
A glass fiber woven fabric having a basis weight of 100 g / m 2 , which has been surface-treated with an epoxy group-containing silane coupling agent, is impregnated with the same liquid resin composition as in Example 1, and a squeeze roll so as to obtain a predetermined resin amount. Then, it was dried so as to have a predetermined volatile content using a hot air drier, to obtain a diallyl phthalate prepreg having a resin amount of 110 parts by weight with respect to 100 parts by weight of the glass fiber fabric.
このプリプレグを実施例１と同じ条件下に加熱加圧して、比較例４によるシートを得た。この不燃性シートは透明性において「不良」であった。
This prepreg was heated and pressurized under the same conditions as in Example 1 to obtain a sheet according to Comparative Example 4. This incombustible sheet was “poor” in transparency.
Claims (9)
A smoke barrier wall comprising the transparent incombustible sheet according to claim 1.
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| JP2016097622A (en) * | 2014-11-25 | 2016-05-30 | 株式会社トッパン・コスモ | Non-combustible decorative sheet and method for producing the same |
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