JP2012126886A - Thermosetting furan resin composition and furan resin laminate using the same - Google Patents
Thermosetting furan resin composition and furan resin laminate using the same Download PDFInfo
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- JP2012126886A JP2012126886A JP2011221973A JP2011221973A JP2012126886A JP 2012126886 A JP2012126886 A JP 2012126886A JP 2011221973 A JP2011221973 A JP 2011221973A JP 2011221973 A JP2011221973 A JP 2011221973A JP 2012126886 A JP2012126886 A JP 2012126886A
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- 239000007849 furan resin Substances 0.000 title claims abstract description 114
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 51
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 93
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000003085 diluting agent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 10
- 239000012783 reinforcing fiber Substances 0.000 claims description 9
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 claims description 5
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 5
- 238000007336 electrophilic substitution reaction Methods 0.000 claims description 5
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 abstract description 12
- 238000005470 impregnation Methods 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000007859 condensation product Substances 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 7
- -1 aromatic alcohols Chemical class 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical compound CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 description 1
- QVYAWBLDJPTXHS-UHFFFAOYSA-N 5-hydroxyfuran-2-carbaldehyde Chemical compound OC1=CC=C(C=O)O1 QVYAWBLDJPTXHS-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- CBPYOHALYYGNOE-UHFFFAOYSA-M potassium;3,5-dinitrobenzoate Chemical compound [K+].[O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 CBPYOHALYYGNOE-UHFFFAOYSA-M 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229940117957 triethanolamine hydrochloride Drugs 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
本発明は、熱硬化性フラン樹脂組成物及びこれを用いたフラン樹脂積層体に関し、更に詳しくは、水分含有量が少ないにもかかわらず粘度が低く、積層体のマトリックス樹脂として使用した場合に含浸性が良好であり、しかも、硬化後の寸法収縮が小さい熱硬化性フラン樹脂組成物及びこれを用いたフラン樹脂積層体に関する。 The present invention relates to a thermosetting furan resin composition and a furan resin laminate using the same, and more specifically, it has a low viscosity despite its low water content and is impregnated when used as a matrix resin for a laminate. The present invention relates to a thermosetting furan resin composition having good properties and small dimensional shrinkage after curing, and a furan resin laminate using the same.
従来、フルフリルアルコールとホルムアルデヒドとの共縮合物からなる、いわゆるフラン樹脂を主成分とする熱硬化性フラン樹脂組成物は、その硬化物が耐熱性・耐溶剤性・耐薬品性に優れていることから、鋼管ライニング、メジセメント、ＦＲＰ等の積層体及び複合材のマトリックス樹脂として各種産業分野において使用されている。 Conventionally, a thermosetting furan resin composition composed mainly of a so-called furan resin composed of a co-condensation product of furfuryl alcohol and formaldehyde has excellent heat resistance, solvent resistance, and chemical resistance. Therefore, it is used in various industrial fields as a laminate resin of steel pipe lining, medge cement, FRP, etc. and a matrix resin for composite materials.
しかしながら、従来の熱硬化性フラン樹脂組成物は、フラン樹脂合成時の縮合反応に由来する水分を含有しているため、積層体のマトリックス樹脂として使用した際、水分放散による積層体の寸法収縮が大きな問題となった。 However, since the conventional thermosetting furan resin composition contains moisture derived from the condensation reaction at the time of synthesizing the furan resin, when used as a matrix resin of the laminate, the dimensional shrinkage of the laminate due to moisture dissipation is reduced. It became a big problem.
これを踏まえ、フラン樹脂の縮合水を合成終了後留去することで水分含有量を低下させる方法（特許文献１参照）が提案されている。 Based on this, a method for reducing the water content by distilling off the condensed water of the furan resin after the synthesis has been proposed (see Patent Document 1).
しかしながら、この方法では、水分の減少に伴いフラン樹脂の粘度が指数的に増加し、積層体のマトリックス樹脂として必要不可欠である含浸性を確保することが困難であった。 However, with this method, the viscosity of the furan resin increases exponentially with the decrease in moisture, and it has been difficult to ensure impregnation properties that are indispensable as a matrix resin for a laminate.
本発明の目的は、上記従来技術の問題点に鑑み、水分含有量が少ないにもかかわらず粘度が低く、積層体のマトリックス樹脂として使用した場合に含浸性が良好であり、しかも、硬化後の寸法収縮が小さい熱硬化性フラン樹脂組成物及びこれを用いたフラン樹脂積層体を提供することにある。 In view of the above-mentioned problems of the prior art, the object of the present invention is that the viscosity is low despite the low water content, the impregnation is good when used as a matrix resin of a laminate, and the The object is to provide a thermosetting furan resin composition with small dimensional shrinkage and a furan resin laminate using the same.
本発明者らは、上記課題を解決すべく鋭意研究した結果、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）と、反応性希釈剤（ａ２）とからなるフラン樹脂（Ａ）と、硬化触媒（Ｂ）とからなる熱硬化性フラン樹脂組成物により、さらにはこれを用いたフラン樹脂積層体により、上記課題を解決することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have found that a furan resin (A) comprising a cocondensate (a1) of furfuryl alcohol and formaldehyde and a reactive diluent (a2), and curing. It has been found that the above-mentioned problems can be solved by a thermosetting furan resin composition comprising the catalyst (B), and further by a furan resin laminate using the same, and the present invention has been completed.
すなわち、本発明の第１の発明によれば、フラン樹脂（Ａ）と硬化触媒（Ｂ）とからなる熱硬化性フラン樹脂組成物において、フラン樹脂（Ａ）は、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）と、反応性希釈剤（ａ２）とからなることを特徴とする熱硬化性フラン樹脂組成物が提供される。 That is, according to the first invention of the present invention, in the thermosetting furan resin composition comprising the furan resin (A) and the curing catalyst (B), the furan resin (A) comprises furfuryl alcohol and formaldehyde. There is provided a thermosetting furan resin composition comprising a cocondensate (a1) and a reactive diluent (a2).
また、本発明に第２の発明によれば、第１の発明において、反応性希釈剤（ａ２）は、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）に対し、求電子置換反応、求核置換反応及びＤｉｅｌｓ−Ａｌｄｅｒ反応よりなる群から選ばれる少なくとも１つの反応が可能な反応点を有することを特徴とする熱硬化性フラン樹脂組成物が提供される。 Further, according to the second invention of the present invention, in the first invention, the reactive diluent (a2) is an electrophilic substitution reaction, an electrolysis reaction to the cocondensate (a1) of furfuryl alcohol and formaldehyde. There is provided a thermosetting furan resin composition characterized by having a reactive site capable of at least one reaction selected from the group consisting of a nuclear substitution reaction and a Diels-Alder reaction.
また、本発明に第３の発明によれば、第１または２の発明において、反応性希釈剤（ａ２）は、フルフリルアルコール、フルフラール及びアニスアルコールよりなる群から選ばれる少なくとも１種であることを特徴とする熱硬化性フラン樹脂組成物が提供される。 According to the third invention of the present invention, in the first or second invention, the reactive diluent (a2) is at least one selected from the group consisting of furfuryl alcohol, furfural and anise alcohol. A thermosetting furan resin composition is provided.
また、本発明に第４の発明によれば、第１〜３の発明において、反応性希釈剤（ａ２）は、共縮合物（ａ１）１００重量部に対して、１０〜１００重量部含有されることを特徴とする熱硬化性フラン樹脂組成物が提供される。 According to the fourth invention of the present invention, in the first to third inventions, the reactive diluent (a2) is contained in an amount of 10 to 100 parts by weight with respect to 100 parts by weight of the cocondensate (a1). A thermosetting furan resin composition is provided.
また、本発明に第５の発明によれば、第１〜４のいずれかの発明において、フラン樹脂（Ａ）は、粘度が５０〜２０００ｍＰａ・ｓであることを特徴とする熱硬化性フラン樹脂組成物が提供される。 According to the fifth invention of the present invention, in any one of the first to fourth inventions, the furan resin (A) has a viscosity of 50 to 2000 mPa · s, and is a thermosetting furan resin. A composition is provided.
また、本発明に第６の発明によれば、第１〜５のいずれかの発明において、フラン樹脂（Ａ）は、水分含有量が３重量％以下であることを特徴とする熱硬化性フラン樹脂組成物が提供される。 According to the sixth invention of the present invention, in any one of the first to fifth inventions, the furan resin (A) has a moisture content of 3% by weight or less. A resin composition is provided.
また、本発明に第７の発明によれば、第１〜６のいずれかの発明の熱硬化性フラン樹脂組成物を、強化繊維からなる積層体に含浸・硬化させたことを特徴とするフラン樹脂積層体が提供される。 According to a seventh aspect of the present invention, there is provided a furan obtained by impregnating and curing a thermosetting furan resin composition according to any one of the first to sixth aspects into a laminate comprising reinforcing fibers. A resin laminate is provided.
本発明の熱硬化性フラン樹脂組成物によれば、高粘度のフルフリルアルコールとホルムアルデヒドとの共縮合物を、低粘度の反応性希釈剤で希釈することで、水分含有量が小さくともフラン樹脂の低粘度化を図る事ができ、低水分量と低粘度の両立を実現できるという効果がある。 According to the thermosetting furan resin composition of the present invention, the co-condensate of high-viscosity furfuryl alcohol and formaldehyde is diluted with a low-viscosity reactive diluent, so that the furan resin is low even if the water content is small. It is possible to reduce the viscosity of the resin, and there is an effect that it is possible to realize both a low moisture content and a low viscosity.
また、本発明のフラン樹脂積層体によれば、反応性希釈剤は、熱硬化性フラン樹脂組成物が硬化する際にフルフリルアルコールとホルムアルデヒドとの共縮合物と、反応・固化するため放散が起こりにくく、硬化後の寸法収縮の小さな積層体であるという効果がある。 Further, according to the furan resin laminate of the present invention, the reactive diluent is diffused because it reacts and solidifies with the cocondensate of furfuryl alcohol and formaldehyde when the thermosetting furan resin composition is cured. It is less likely to occur and has the effect of being a laminate with small dimensional shrinkage after curing.
本発明の熱硬化性フラン樹脂組成物及びこれを用いたフラン樹脂積層体を、以下に、具体的かつ詳細に説明する。 The thermosetting furan resin composition of the present invention and the furan resin laminate using the same will be described specifically and in detail below.
１．熱硬化性フラン樹脂組成物
本発明の熱硬化性フラン樹脂組成物は、フラン樹脂（Ａ）と硬化触媒（Ｂ）とからなる熱硬化性フラン樹脂組成物であって、フラン樹脂（Ａ）が、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）と、反応性希釈剤（ａ２）とからなることを特徴とする。
1. Thermosetting furan resin composition The thermosetting furan resin composition of the present invention is a thermosetting furan resin composition comprising a furan resin (A) and a curing catalyst (B), and the furan resin (A) is And a co-condensate (a1) of furfuryl alcohol and formaldehyde and a reactive diluent (a2).
（１）フラン樹脂（Ａ）
本発明において、フラン樹脂（Ａ）は、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）と、反応性希釈剤（ａ２）とからなることが必要である。
本発明においては、硬化時の硬化速度が早く、最終硬化度が高いため、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）が最適である。
(1) Furan resin (A)
In the present invention, the furan resin (A) needs to comprise a cocondensate (a1) of furfuryl alcohol and formaldehyde and a reactive diluent (a2).
In the present invention, the co-condensate (a1) of furfuryl alcohol and formaldehyde is optimal because the curing speed during curing is high and the final curing degree is high.
本発明において使用される反応性希釈剤（ａ２）は、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）と相溶性があり、熱硬化性フラン樹脂組成物が硬化する際に共縮合物（ａ１）等と反応・固化するものであれば特に限定されないが、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）に対し、求電子置換反応、求核置換反応及びＤｉｅｌｓ−Ａｌｄｅｒ反応よりなる群から選ばれる少なくとも１つの反応が可能な反応点を有するものが好ましい。 The reactive diluent (a2) used in the present invention is compatible with the co-condensate (a1) of furfuryl alcohol and formaldehyde, and the co-condensate ( Although it will not specifically limit if it reacts and solidifies with a1) etc., The group which consists of an electrophilic substitution reaction, a nucleophilic substitution reaction, and Diels-Alder reaction with respect to the cocondensate (a1) of furfuryl alcohol and formaldehyde. Those having a reaction point capable of at least one reaction selected from the following are preferred.
フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）に対し、求電子置換反応、求核置換反応及びＤｉｅｌｓ−Ａｌｄｅｒ反応よりなる群から選ばれる少なくとも１つの反応が可能な反応点を有する反応性希釈剤（ａ２）としては、求電子剤としてアセトン・メチルエチルケトン等のケトン類、求核剤としてベンンジルアルコール、アニスアルコール等の芳香族アルコール類、アクリル酸エステル、メタクリル酸エステル、マレイン酸エステル等の不飽和酸エステル類、フルフラール、フルフリルアルコール、５−ヒドロキシフルフラール等のフラン類があげられるが、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）と相溶性の点から、フルフリルアルコール、フルフラール及びアニスアルコールよりなる群から選ばれる少なくとも１種以上のものが好ましい。したがって、反応性希釈剤（ａ２）としては、上記したような求電子置換反応、求核置換反応及びＤｉｅｌｓ−Ａｌｄｅｒ反応よりなる群から選ばれる少なくとも１つの反応が可能な反応点を有する化合物の単独あるいは混合物が好ましく用いられる。 Reactive dilution having a reaction point capable of at least one reaction selected from the group consisting of an electrophilic substitution reaction, a nucleophilic substitution reaction, and a Diels-Alder reaction with respect to the co-condensate (a1) of furfuryl alcohol and formaldehyde Examples of the agent (a2) include ketones such as acetone and methyl ethyl ketone as electrophiles, aromatic alcohols such as benzyl alcohol and anise alcohol, acrylates, methacrylates, and maleates as nucleophiles. Furans such as unsaturated acid esters, furfural, furfuryl alcohol, and 5-hydroxyfurfural are listed. From the viewpoint of compatibility with the cocondensate (a1) of furfuryl alcohol and formaldehyde, furfuryl alcohol and furfural. And from the group consisting of anise alcohol At least one or more of the barrel preferred. Therefore, as the reactive diluent (a2), a compound having a reaction point capable of at least one reaction selected from the group consisting of the above-mentioned electrophilic substitution reaction, nucleophilic substitution reaction, and Diels-Alder reaction is used. Alternatively, a mixture is preferably used.
反応性希釈剤（ａ２）の添加量は、反応性希釈剤の種類、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）の粘度により異なるが、少なすぎると積層体成形時の含浸性が低下するおそれがあり、一方、多すぎると積層体成形時タレが発生するおそれがあることから、共縮合物（ａ１）１００重量部に対して、１０〜１００重量部であることが好ましく、２０〜９０重量部が更に好ましく、３０〜８０重量部が最も好ましい。 The addition amount of the reactive diluent (a2) varies depending on the type of the reactive diluent and the viscosity of the cocondensate (a1) of furfuryl alcohol and formaldehyde, but if it is too small, the impregnation property at the time of forming the laminate is lowered. On the other hand, if the amount is too large, sagging may occur at the time of forming the laminate, and therefore it is preferably 10 to 100 parts by weight with respect to 100 parts by weight of the cocondensate (a1). 90 parts by weight is more preferable, and 30 to 80 parts by weight is most preferable.
本発明における、フラン樹脂（Ａ）の製造方法としては、特に限定されないが、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）を製造する工程の後、反応性希釈剤（ａ２）を添加する工程を行うことにより製造する方法、または、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）を製造する工程の後、過剰に添加され、フラン樹脂（Ａ）中に残ることとなったフルフリルアルコールを、そのまま、反応性希釈剤（ａ２）として使用する製造方法等があげられる。 Although it does not specifically limit as a manufacturing method of furan resin (A) in this invention, A reactive diluent (a2) is added after the process which manufactures the cocondensate (a1) of furfuryl alcohol and formaldehyde. Furfuryl which was added excessively after the method of manufacturing by performing the process or the process of manufacturing the cocondensate (a1) of furfuryl alcohol and formaldehyde and remained in the furan resin (A) Examples thereof include a production method using alcohol as it is as the reactive diluent (a2).
本発明において、フラン樹脂（Ａ）の粘度は、積層体の成形方法等により決定される為、特に限定されないが、大きすぎると積層体成形時の含浸性が低下するおそれがあり、一方、小さすぎると積層体成形時タレが発生するおそれがあることから、５０〜２０００ｍＰａ・ｓが好ましく、１００〜１５００ｍＰａ・ｓが更に好ましく、２００〜１０００ｍＰａ・ｓが最も好ましい。 In the present invention, the viscosity of the furan resin (A) is not particularly limited because it is determined by the molding method of the laminate and the like. However, if it is too large, the impregnation property at the time of molding the laminate may be reduced, whereas it is small. If the amount is too large, sagging may occur at the time of forming the laminate, so 50 to 2000 mPa · s is preferable, 100 to 1500 mPa · s is more preferable, and 200 to 1000 mPa · s is most preferable.
本発明において、フラン樹脂（Ａ）の水分含有量は、積層体の寸法精度等により決定される為、特に限定されないが、小さい程硬化収縮が小さくなる事から、３重量％以下が好ましく、２重量％以下が更に好ましく、１重量％以下が最も好ましい。 In the present invention, the moisture content of the furan resin (A) is not particularly limited because it is determined by the dimensional accuracy and the like of the laminate. % By weight or less is more preferable, and 1% by weight or less is most preferable.
（２）硬化触媒（Ｂ）
本発明において、硬化触媒（Ｂ）としては、はフラン樹脂（Ａ）を硬化できるものであれば特に限定されず、塩酸、硫酸等の無機酸等の無機酸、キシレンスルホン酸、トルエンスルホン酸、フェノールスルホン酸等の有機酸の水溶液が使用できる。
(2) Curing catalyst (B)
In the present invention, the curing catalyst (B) is not particularly limited as long as it can cure the furan resin (A), and includes inorganic acids such as hydrochloric acid and inorganic acids such as sulfuric acid, xylenesulfonic acid, toluenesulfonic acid, An aqueous solution of an organic acid such as phenolsulfonic acid can be used.
硬化時間の短縮とポットライフの両立を狙いとして、硬化触媒（Ｂ）として、熱反応型潜在性酸触媒を使用する事も好ましく、熱反応型潜在性酸触媒としては、フラン系樹脂に含有する成分と常温では反応しにくく硬化時の加熱ですばやく反応し酸を発生させるものであれば特に限定されないが、常温時の安定性と硬化時の加熱による反応速度の点から、無機アンモニウム塩、１級アミン塩、２級アミン塩・３級アミン塩の少なくともいずれかを含有することが好ましく、塩化アンモニウム、硫酸アンモニウム、硝酸アンモニウム、エチルアミン塩酸塩、ジエチルアミン塩酸塩、トリエチルアミン塩酸塩、トリエタノールアミン塩酸塩の少なくともいずれかを含有することが特に好ましい。 It is also preferable to use a thermal reaction type latent acid catalyst as the curing catalyst (B) for the purpose of shortening the curing time and pot life, and the thermal reaction type latent acid catalyst is contained in a furan resin. It is not particularly limited as long as it does not easily react with components at room temperature and can react quickly with heating during curing to generate an acid. From the viewpoint of stability at room temperature and reaction rate due to heating during curing, an inorganic ammonium salt, 1 It is preferable to contain at least one of a secondary amine salt, a secondary amine salt, and a tertiary amine salt, and at least ammonium chloride, ammonium sulfate, ammonium nitrate, ethylamine hydrochloride, diethylamine hydrochloride, triethylamine hydrochloride, triethanolamine hydrochloride It is particularly preferable to contain any of them.
硬化触媒（Ｂ）の添加量は、フラン樹脂（Ａ）および硬化触媒（Ｂ）の種類や希釈濃度、目的とする硬化温度・硬化時間により調整されるため特に限定されないが、フラン樹脂（Ａ）１００重量部に対し、１〜２０重量部が好ましく、２〜１０重量部とするのが特に好ましい。１重量部より少ないと、硬化不良の問題となるおそれがある。一方、２０重量部より多いと、ポットライフが短くなるおそれがある。 The addition amount of the curing catalyst (B) is not particularly limited because it is adjusted according to the type and dilution concentration of the furan resin (A) and the curing catalyst (B), and the target curing temperature / curing time, but the furan resin (A). 1 to 20 parts by weight is preferable with respect to 100 parts by weight, and 2 to 10 parts by weight is particularly preferable. When the amount is less than 1 part by weight, there is a possibility of causing a problem of curing failure. On the other hand, if it is more than 20 parts by weight, the pot life may be shortened.
（３）熱硬化性フラン樹脂組成物
本発明の熱硬化性フラン樹脂組成物は、フラン樹脂（Ａ）と硬化触媒（Ｂ）とからなることが必要である。
(3) Thermosetting furan resin composition The thermosetting furan resin composition of the present invention needs to be composed of a furan resin (A) and a curing catalyst (B).
２．フラン樹脂積層体
本発明のフラン樹脂積層体は、上記熱硬化性フラン樹脂組成物を、強化繊維からなる積層体に含浸・硬化させたことを特徴とする。
2. Furan resin laminate The furan resin laminate of the present invention is characterized in that the thermosetting furan resin composition is impregnated and cured in a laminate comprising reinforcing fibers.
本発明において、強化繊維は特に限定されないが、ガラス繊維、アラミド繊維、炭素繊維等が好ましく、得られるフラン樹脂積層体の強度と価格のバランスからガラス繊維が最も好ましい。また、強化繊維は繊維径が３〜２５μｍの範囲のものであることが好ましく、強度面及び価格面の観点から５〜２０μｍの繊維径のものがより好ましい。 In the present invention, the reinforcing fiber is not particularly limited, but glass fiber, aramid fiber, carbon fiber and the like are preferable, and glass fiber is most preferable from the balance of strength and price of the obtained furan resin laminate. The reinforcing fiber preferably has a fiber diameter in the range of 3 to 25 μm, and more preferably has a fiber diameter of 5 to 20 μm from the viewpoint of strength and price.
強化繊維に熱硬化性フラン樹脂組成物を含浸させる方法は特に限定されず、例えば、強化繊維に熱硬化性フラン樹脂組成物を含浸ロールにて含浸させる方法等が挙げられる。 A method of impregnating the reinforcing fiber with the thermosetting furan resin composition is not particularly limited, and examples thereof include a method of impregnating the reinforcing fiber with the thermosetting furan resin composition with an impregnation roll.
強化繊維に含浸させた熱硬化性フラン樹脂組成物の硬化方法は特に限定されず、例えば、強化繊維に含浸させた熱硬化性フラン樹脂組成物を入れた容器を熱風にて硬化する方法、金型内に熱硬化性フラン樹脂組成物を注ぎ入れ、熱風であるいは熱板に挟み込んで加熱硬化する方法等が挙げられる。
上記本発明の熱硬化性フラン樹脂組成物を加熱硬化する際の温度は、特に限定されないが、一般的に、例えば７０〜１３０℃が好ましい。
The method for curing the thermosetting furan resin composition impregnated in the reinforcing fibers is not particularly limited. For example, a method of curing a container containing the thermosetting furan resin composition impregnated in the reinforcing fibers with hot air, gold Examples thereof include a method of pouring a thermosetting furan resin composition into a mold and heat-curing it with hot air or sandwiching it between hot plates.
Although the temperature at the time of heat-hardening the thermosetting furan resin composition of the said invention is not specifically limited, Generally 70-130 degreeC is preferable, for example.
本発明のフラン樹脂積層体は、上記のような本発明の熱硬化性フラン樹脂組成物を使用することにより、低水分量と低粘度の両立が実現されていることから、強化樹脂に簡易に含浸させることができるものである。 Since the furan resin laminate of the present invention achieves both low moisture content and low viscosity by using the thermosetting furan resin composition of the present invention as described above, it can be easily used as a reinforced resin. It can be impregnated.
また、本発明のフラン樹脂積層体によれば、反応性希釈剤が、熱硬化性フラン樹脂組成物が硬化する際にフルフリルアルコールとホルムアルデヒドとの共縮合物と、反応・固化するため放散が起こりにくく、硬化後の寸法収縮の小さな積層体を簡便に与える事ができる。したがって、本発明により、品質が良好なフラン樹脂積層体を低コストにて製造することができるものであり、例えばＦＲＰなどの用途に特に好適に用いることができるものである。 Further, according to the furan resin laminate of the present invention, the reactive diluent is diffused because it reacts and solidifies with the cocondensate of furfuryl alcohol and formaldehyde when the thermosetting furan resin composition is cured. It is difficult to occur, and a laminate with small dimensional shrinkage after curing can be easily provided. Therefore, according to the present invention, a furan resin laminate having good quality can be produced at a low cost, and can be particularly suitably used for applications such as FRP.
以下、実施例を用いて本発明をさらに詳しく説明するが、本発明はこれらの例によりなんら限定されるものではない。
本発明における各物性値の測定方法を以下に示す。
EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited at all by these examples.
The measuring method of each physical property value in the present invention is shown below.
１．測定法
（１）粘度（単位：％）
ＪＩＳ Ｋ７１１７−１『ブルックフィールド形回転粘度計による見かけ粘度の測定方法』におけるＢ型粘度計法に準拠してフラン樹脂の粘度を測定した。
1. Measurement method (1) Viscosity (unit:%)
The viscosity of the furan resin was measured according to the B-type viscometer method in JIS K7117-1 “Method for measuring apparent viscosity with Brookfield rotary viscometer”.
（２）水分含有量
ＪＩＳ Ｋ０１１３−８『カールフィッシャー滴定方法』における定量滴定方法に準拠してフラン樹脂の水分含有量を測定した。
(2) Water content The water content of the furan resin was measured according to the quantitative titration method in JIS K0113-8 “Karl Fischer titration method”.
（３）含浸性
フラン樹脂積層体の成形時の基材に対する熱硬化性フラン樹脂組成物の含浸度合いを目視にて観察した。
(3) Impregnation The degree of impregnation of the thermosetting furan resin composition with respect to the substrate during molding of the furan resin laminate was visually observed.
（４）寸法保持率
成形したフラン樹脂積層体を１００ｍｍ×１００ｍｍにカット後寸法測定し、２５℃の恒温室で１０日間養生した後、以下の式を元に比較、寸法保持率を求めた。
寸法保持率（％）＝１０日後の寸法（ｍｍ）／カット後寸法（ｍｍ）×１００
(4) Dimension retention The dimension of the molded furan resin laminate was measured after cutting into 100 mm × 100 mm, cured for 10 days in a thermostatic chamber at 25 ° C., and then compared with the following formula to determine the dimension retention.
Dimension retention (%) = dimension after 10 days (mm) / post-cut dimension (mm) × 100
２．実施例および比較例
（フラン樹脂（Ａ）の調整）
＜実施例１＞
フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１：表１中単に共縮合物と記す、以下同様。粘度２７００ｍＰａ・ｓ、水分含有量７．４重量％）１００重量部に対し、フルフリルアルコール（表１において、「ＦＡ」で示す。）５０重量％を添加した後、ホモディスパーを用い、１０００ｒｐｍで５分間攪拌し、フラン樹脂（Ａ）を得た。
2. Examples and comparative examples (adjustment of furan resin (A))
<Example 1>
Co-condensate of furfuryl alcohol and formaldehyde (a1: simply referred to as co-condensate in Table 1, the same shall apply hereinafter; viscosity 2700 mPa · s, water content 7.4% by weight) to 100 parts by weight of furfuryl alcohol ( In Table 1, indicated by “FA”) After adding 50% by weight, the mixture was stirred with a homodisper at 1000 rpm for 5 minutes to obtain a furan resin (A).
＜実施例２＞
フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１：粘度２７００ｍＰａ・ｓ、水分含有量７．４重量％）１００重量部に対し、フルフラール（表１において、「ＦＬ」で示す。）４０重量％を添加した後、ホモディスパーを用い、１０００ｒｐｍで５分間攪拌し、フラン樹脂（Ａ）を得た。
<Example 2>
40% by weight of furfural (shown as “FL” in Table 1) is added to 100 parts by weight of a co-condensate of furfuryl alcohol and formaldehyde (a1: viscosity 2700 mPa · s, water content 7.4% by weight). After the addition, a furan resin (A) was obtained by stirring at 1000 rpm for 5 minutes using a homodisper.
＜実施例３＞
フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１：粘度２７００ｍＰａ・ｓ、水分含有量７．４重量％）１００重量部に対し、アニスアルコール（表１において、「ＡＡ」で示す。）６５重量％を添加した後、ホモディスパーを用い、１０００ｒｐｍで５分間攪拌し、フラン樹脂（Ａ）を得た。
<Example 3>
65% by weight of anise alcohol (indicated by “AA” in Table 1) with respect to 100 parts by weight of a co-condensate of furfuryl alcohol and formaldehyde (a1: viscosity 2700 mPa · s, water content 7.4% by weight). Then, using a homodisper, the mixture was stirred at 1000 rpm for 5 minutes to obtain furan resin (A).
＜実施例４＞
フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１：粘度１４０００ｍＰａ・ｓ、水分含有量１．３重量％）１００重量部に対し、フルフリルアルコール（表１において、「ＦＡ」で示す。）７０重量％を添加した後、ホモディスパーを用い、１０００ｒｐｍで５分間攪拌し、フラン樹脂（Ａ）を得た。
<Example 4>
70 weight parts of furfuryl alcohol (shown as “FA” in Table 1) with respect to 100 parts by weight of co-condensate of furfuryl alcohol and formaldehyde (a1: viscosity 14000 mPa · s, water content 1.3 weight%). % Was added and then stirred at 1000 rpm for 5 minutes using a homodisper to obtain furan resin (A).
＜比較例１＞
フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１：粘度２７００ｍＰａ・ｓ、水分含有量７．４重量％）をホモディスパーを用い、１０００ｒｐｍで５分間攪拌し、フラン樹脂（Ａ）を得た。
<Comparative Example 1>
A furanyl alcohol and formaldehyde cocondensate (a1: viscosity 2700 mPa · s, water content 7.4 wt%) was stirred with a homodisper at 1000 rpm for 5 minutes to obtain a furan resin (A).
＜比較例２＞
フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１：粘度１４０００ｍＰａ・ｓ、水分含有量１．３重量％）をホモディスパーを用い、１０００ｒｐｍで５分間攪拌し、フラン樹脂（Ａ）を得た。
<Comparative example 2>
A furanyl alcohol and formaldehyde cocondensate (a1: viscosity 14000 mPa · s, water content 1.3 wt%) was stirred with a homodisper at 1000 rpm for 5 minutes to obtain a furan resin (A).
（熱硬化性フラン樹脂組成物の調整）
実施例１〜４及び比較例１〜２で得られたフラン樹脂（Ａ）１００重量部に、硬化触媒（Ｂ）として、パラトルエンスルホン酸５０％水溶液２．５重量部を添加し、ホモディスパーを用いて１０００ｒｐｍ５分間攪拌することで熱硬化性フラン樹脂組成物を得た。
(Adjustment of thermosetting furan resin composition)
To 100 parts by weight of the furan resin (A) obtained in Examples 1 to 4 and Comparative Examples 1 to 2, 2.5 parts by weight of a 50% aqueous solution of paratoluenesulfonic acid was added as a curing catalyst (B), A thermosetting furan resin composition was obtained by stirring at 1000 rpm for 5 minutes.
（フラン樹脂積層体の成形）
上記、熱硬化性フラン樹脂組成物（８４００ｇ／ｍ２）をガラス繊維ステッチ（繊維径１３μｍ、１５００ｇ／ｍ２、縦横比１：１）の両面に不織布（３ｍｍ、６００ｇ／ｍ２）を重ね合わせた基材に含浸ロールにて均一に含浸した後、内寸２４０ｍｍ×２４０ｍｍ×７ｍｍの金型内に静置し、９０℃で１２時間硬化し、フラン樹脂積層体を得た。
(Formation of furan resin laminate)
The above-mentioned thermosetting furan resin composition (8400 g / m 2 ) is laminated with a nonwoven fabric (3 mm, 600 g / m 2 ) on both sides of a glass fiber stitch (fiber diameter 13 μm, 1500 g / m 2 , aspect ratio 1: 1). The base material was uniformly impregnated with an impregnation roll, and then placed in a mold having an inner size of 240 mm × 240 mm × 7 mm and cured at 90 ° C. for 12 hours to obtain a furan resin laminate.
上記実施例及び比較例により得られたフラン樹脂及びフラン樹脂積層体について、各評価を行った。評価結果を表１に示した。 Each evaluation was performed about the furan resin and furan resin laminated body which were obtained by the said Example and comparative example. The evaluation results are shown in Table 1.
３．評価
表１から明らかなように、実施例１〜４と比較例１、２とを対比すると、本発明の特定事項である「フラン樹脂（Ａ）は、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）と、反応性希釈剤（ａ２）とからなる」との要件を満たさない比較例１、２で得られたものは、粘度が高く含浸不良であり、しかも、寸法保持性が不良であったのに対して、本願発明の実施例１〜３においては、低粘度かつ水分含有量が小さな熱硬化性フラン樹脂組成物となっており、これにより含浸性の確保と低寸法収縮との両者を同時に実現する熱硬化性フラン樹脂組成物及びフラン樹脂積層体が得られることが明らかになった。
3. Evaluation As is apparent from Table 1, when Examples 1 to 4 and Comparative Examples 1 and 2 are compared, “furan resin (A) is a co-condensate of furfuryl alcohol and formaldehyde, which is a specific matter of the present invention. Those obtained in Comparative Examples 1 and 2 that do not satisfy the requirement of (a1) and the reactive diluent (a2) have high viscosity and poor impregnation, and also have poor dimensional retention. On the other hand, in Examples 1 to 3 of the present invention, it is a thermosetting furan resin composition having a low viscosity and a small water content, thereby ensuring impregnation and low dimensional shrinkage. It became clear that the thermosetting furan resin composition and furan resin laminated body which implement | achieve both simultaneously are obtained.
本発明の熱硬化性フラン樹脂組成物は、硬化後の寸法収縮が小さいフラン樹脂積層体を与える熱硬化性フラン樹脂組成物であり、ＦＲＰ等積層体のマトリックス樹脂として効果的な熱硬化性樹脂組成物が、少工程で簡便に得られるため、産業上大いに有用である。
The thermosetting furan resin composition of the present invention is a thermosetting furan resin composition that gives a furan resin laminate with small dimensional shrinkage after curing, and is an effective thermosetting resin as a matrix resin for laminates such as FRP. Since the composition can be easily obtained in a small number of steps, it is very useful industrially.
Claims (7)
フラン樹脂（Ａ）は、フルフリルアルコールとホルムアルデヒドとの共縮合物（ａ１）と、反応性希釈剤（ａ２）とからなることを特徴とする熱硬化性フラン樹脂組成物。 In the thermosetting furan resin composition comprising the furan resin (A) and the curing catalyst (B),
The furan resin (A) comprises a co-condensate (a1) of furfuryl alcohol and formaldehyde and a reactive diluent (a2).
A furan resin laminate obtained by impregnating and curing the thermosetting furan resin composition according to any one of claims 1 to 6 in a laminate comprising reinforcing fibers.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013199615A (en) * | 2012-03-26 | 2013-10-03 | Sekisui Chem Co Ltd | Thermosetting property furan resin composition and furan resin laminate using the same |
| CN111217658A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for preparing ethylbenzene and styrene from biomass platform compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4884192A (en) * | 1972-01-31 | 1973-11-08 | ||
| JP3219769B2 (en) * | 1993-02-02 | 2001-10-15 | ペルストルプ・ケミテック・アクチボラグ | Resin binder composition |
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- 2011-10-06 JP JP2011221973A patent/JP2012126886A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4884192A (en) * | 1972-01-31 | 1973-11-08 | ||
| JP3219769B2 (en) * | 1993-02-02 | 2001-10-15 | ペルストルプ・ケミテック・アクチボラグ | Resin binder composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013199615A (en) * | 2012-03-26 | 2013-10-03 | Sekisui Chem Co Ltd | Thermosetting property furan resin composition and furan resin laminate using the same |
| CN111217658A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for preparing ethylbenzene and styrene from biomass platform compound |
| CN111217658B (en) * | 2018-11-27 | 2021-05-25 | 中国科学院大连化学物理研究所 | Method for preparing ethylbenzene and styrene from biomass platform compound |
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