JP6089453B2 - Curable lignin resin composition and method for producing the same - Google Patents
Curable lignin resin composition and method for producing the same Download PDFInfo
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- JP6089453B2 JP6089453B2 JP2012125860A JP2012125860A JP6089453B2 JP 6089453 B2 JP6089453 B2 JP 6089453B2 JP 2012125860 A JP2012125860 A JP 2012125860A JP 2012125860 A JP2012125860 A JP 2012125860A JP 6089453 B2 JP6089453 B2 JP 6089453B2
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- 229920005610 lignin Polymers 0.000 title claims description 74
- 239000011342 resin composition Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 150000001923 cyclic compounds Chemical class 0.000 claims description 32
- 239000007849 furan resin Substances 0.000 claims description 32
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 32
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 16
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 16
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical group O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 claims description 4
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 26
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- PXIKRTCSSLJURC-UHFFFAOYSA-N Dihydroeugenol Chemical group CCCC1=CC=C(O)C(OC)=C1 PXIKRTCSSLJURC-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000011121 hardwood Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- YHEWWEXPVKCVFY-UHFFFAOYSA-N 2,6-Dimethoxy-4-propylphenol Chemical group CCCC1=CC(OC)=C(O)C(OC)=C1 YHEWWEXPVKCVFY-UHFFFAOYSA-N 0.000 description 2
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 2
- 241000218631 Coniferophyta Species 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000000350 glycoloyl group Chemical group O=C([*])C([H])([H])O[H] 0.000 description 2
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 2
- 235000008216 herbs Nutrition 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- ZSSJQYMNCUJSBR-UHFFFAOYSA-N 4,5-dimethoxy-1,3-bis(methoxymethyl)imidazolidin-2-one Chemical compound COCN1C(OC)C(OC)N(COC)C1=O ZSSJQYMNCUJSBR-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical group CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000000075 primary alcohol group Chemical group 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、硬化性リグニン樹脂組成物およびその製造方法に関するものである。 The present invention relates to a curable lignin resin composition and a method for producing the same.
石油資源の枯渇が心配され、石油から植物由来の樹脂の開発が急がれている。植物由来の樹脂としてはバイオマスより抽出するリグニン樹脂が注目されている。抽出により得られるリグニンはノボラック系のフェノール樹脂の硬化剤として知られるヘキサメチレンテトラミンのような含窒素架橋型環式化合物添加剤を添加して加熱させることにより硬化させることができ、リグニン樹脂組成物を得ることができる。しかしながら、リグニンと含窒素架橋型環式化合物添加剤を添加したものは加熱硬化時の溶融粘度が高いため、ノボラック系のフェノール樹脂の硬化に比べ成形性が悪く、使用できないという問題があった。 There is concern about the depletion of petroleum resources, and there is an urgent need to develop plant-derived resins from petroleum. As plant-derived resins, lignin resins extracted from biomass have attracted attention. The lignin obtained by extraction can be cured by adding a nitrogen-containing cross-linked cyclic compound additive such as hexamethylenetetramine, which is known as a curing agent for novolak-based phenolic resins, and heating the lignin resin composition. Can be obtained. However, the addition of lignin and a nitrogen-containing cross-linked cyclic compound additive has a high melt viscosity at the time of heat curing, and therefore has a problem that it cannot be used because it has poor moldability compared to the curing of a novolac phenol resin.
本発明は上記の様な状況に鑑み、リグニン樹脂の成形性を向上させるべく鋭意検討し、リグニンとヘキサメチレンテトラミンのような含窒素架橋型環式化合物を添加したものにフラン樹脂を混合して加熱することにより、溶融粘度が低下し且つ、硬化終了までの時間を遅らせることができることを見出し、リグニン樹脂の成形性を向上させる方法を提供するものである。 In view of the situation as described above, the present invention has been intensively studied to improve the moldability of lignin resin, and a furan resin is mixed with a mixture containing a nitrogen-containing crosslinked cyclic compound such as lignin and hexamethylenetetramine. It is found that, by heating, the melt viscosity is lowered and the time until the completion of curing can be delayed, and a method for improving the moldability of the lignin resin is provided.
このような目的は、下記の本発明第（１）項〜第（９）項により達成される。
（１）リグニンと含窒素架橋型環式化合物とフラン樹脂を含有することを特徴とする硬化性リグニン樹脂組成物。
（２）前記含窒素架橋型環式化合物が、キヌクリジン、ピジンおよびヘキサメチレンテトラミンから選ばれる少なくとも１種である（１）に記載の硬化性リグニン樹脂組成物。
（３）前記含窒素架橋型環式化合物が、下記一般式（Ｉ）で表わされるものである（１）記載の硬化性リグニン樹脂組成物。
Ｚ−（ＣＨ２ＯＲ）ｍ （Ｉ）
［式（Ｉ）中のＺはメラミン残基、尿素残基、グリコルリル残基またはイミダゾリジノン残基のいずれか１種を表わす。ｍは２〜１４の整数を表わす。Ｒは独立して水素または炭素数１〜４のアルキル基を表わす。ただし、−ＣＨ２ＯＲはメラミン残基の１級アミノ基の窒素原子、尿素残基の１級アミノ残基の窒素原子、グリコリル残基の２級アミノ残基の窒素原子またはイミダゾリジノン残基の２級アミノ基の窒素原子のいずれかに直接結合する。］
（４）前記含窒素架橋型環式化合物が、一般式（１）である（１）に記載の硬化性リグニン樹脂組成物。
（５）前記含窒素架橋型環式化合物が一般式（２）および（３）から選ばれる少なくとも１種である（１）に記載の硬化性リグニン樹脂組成物。
（６）前記含窒素架橋型環式化合物が式（４）および（７）から選ばれる少なくとも１種である（１）に記載の硬化性リグニン樹脂組成物。
（７）リグニンと含窒素架橋型環式化合物とフラン樹脂を混合し、硬化させることを特徴とする（１）乃至（６）のいずれか１項に記載の硬化性リグニン樹脂組成物の製造方法。
（８）（１）乃至（６）のいずれか１項に記載の硬化性リグニン樹脂組成物を硬化することによって得られる、硬化物。
（９）（８）に記載の硬化物を有している積層板。
Such an object is achieved by the following items (1) to (9) of the present invention.
(1) A curable lignin resin composition comprising lignin, a nitrogen-containing crosslinked cyclic compound, and a furan resin.
(2) The curable lignin resin composition according to (1), wherein the nitrogen-containing bridged cyclic compound is at least one selected from quinuclidine, pyridine and hexamethylenetetramine.
(3) The curable lignin resin composition according to (1), wherein the nitrogen-containing crosslinked cyclic compound is represented by the following general formula (I).
Z- (CH 2 OR) m ( I)
[Z in Formula (I) represents any one of a melamine residue, a urea residue, a glycoluril residue, or an imidazolidinone residue. m represents an integer of 2 to 14. R independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms. However, —CH 2 OR is a nitrogen atom of a primary amino group of a melamine residue, a nitrogen atom of a primary amino residue of a urea residue, a nitrogen atom of a secondary amino residue of a glycolyl residue, or an imidazolidinone residue To the nitrogen atom of the secondary amino group. ]
(4) The curable lignin resin composition according to (1), wherein the nitrogen-containing crosslinked cyclic compound is General Formula (1).
(5) The curable lignin resin composition according to (1), wherein the nitrogen-containing crosslinked cyclic compound is at least one selected from general formulas (2) and (3).
(6) The curable lignin resin composition according to (1), wherein the nitrogen-containing crosslinked cyclic compound is at least one selected from formulas (4) and (7).
(7) The method for producing a curable lignin resin composition according to any one of (1) to (6), wherein lignin, a nitrogen-containing crosslinked cyclic compound, and a furan resin are mixed and cured. .
(8) A cured product obtained by curing the curable lignin resin composition according to any one of (1) to (6).
(9) A laminate having the cured product according to (8).
本発明は、リグニンにヘキサメチレンテトラミンのような含窒素架橋型環式化合物を添加して加熱硬化させる時にフラン樹脂を混合することで、溶融粘度が低下し且つ、硬化終了までの時間を遅らせることができ、リグニン樹脂の成形性を向上させることができる。 The present invention adds a furan resin when adding a nitrogen-containing crosslinked cyclic compound such as hexamethylenetetramine to lignin and curing it, thereby reducing the melt viscosity and delaying the time until the curing is completed. And moldability of the lignin resin can be improved.
本発明に用いるリグニンは、セルロース及びヘミセルロースと共に、植物体の骨格を形成する主要成分であり、自然界に最も豊富に存在する物質の一つである。このリグニンには、針葉樹、広葉樹及び草本を由来とする３種類のリグニンがある。これらのリグニンは、針葉樹、広葉樹及び草本を酸化分解することにより得ることができる。また、その構造は、それぞれの原料から生成する分解生成物によって区別され、針葉樹リグニンは、主にグアイアシルプロパン構造から、広葉樹リグニンは、主に前記グアイアシルプロパン構造及びシリンギルプロパン構造から、又、草本類リグニンは、主に前記グアイアシルプロパン構造、前記シリンギルプロパン構造、及び４−ヒドロキシフェニルプロパン構造から成る。 Lignin used in the present invention is one of the most abundant substances in nature, which is a main component that forms a plant skeleton together with cellulose and hemicellulose. This lignin includes three types of lignin derived from conifers, hardwoods and herbs. These lignins can be obtained by oxidative degradation of conifers, hardwoods and herbs. The structure is distinguished by the decomposition products generated from the respective raw materials. Softwood lignin is mainly derived from the guaiacylpropane structure, and hardwood lignin is mainly derived from the guaiacylpropane structure and the syringylpropane structure. The herbaceous lignin mainly comprises the guaiacylpropane structure, the syringylpropane structure, and the 4-hydroxyphenylpropane structure.
本発明に用いるリグニンの製造方法としては、一例として高温、高圧の有機溶媒を使用してリグニンを溶媒和させる有機溶媒法をあげることができる。 As an example of the method for producing lignin used in the present invention, an organic solvent method in which lignin is solvated using an organic solvent at high temperature and high pressure can be mentioned.
フラン樹脂とはフラン環をもつ高分子のことであり、大きくフェノール・フルフラール樹脂、フルフラール・アセトン樹脂、フルフリルアルコール樹脂の３種に大別される。本発明で使用するフラン樹脂は主にフルフリルアルコール樹脂のフラン樹脂を指している。 フルフリルアルコール樹脂のフラン樹脂は主にフルフリルアルコールの第一級アルコール基とフラン環の５位の水素との脱水縮合により得られる樹脂である。フルフリルアルコールが農産廃物を原料として得られるものであるためフルフリルアルコール樹脂のフラン樹 脂は植物由来の樹脂といえる。同じく植物由来の樹脂であるリグニンと混合しても植物由来の比率を維持することができるため好ましい。
フラン樹脂は、強酸を添加することにより常温で単独でも硬化させることができる等、成形性が良好な植物由来樹脂であり、ヘキサメチレンテトラミンのような含窒素架橋型環式化合物を添加して更に１３０〜１７０℃加熱でも硬化させることができる。
Furan resin is a polymer having a furan ring, and is roughly divided into three types: phenol / furfural resin, furfural / acetone resin, and furfuryl alcohol resin. The furan resin used in the present invention mainly refers to a furfuryl alcohol resin furan resin. Furan resin of furfuryl alcohol resin is a resin obtained mainly by dehydration condensation between the primary alcohol group of furfuryl alcohol and hydrogen at the 5-position of the furan ring. Since furfuryl alcohol is obtained from agricultural waste, the furfuryl alcohol resin furan resin is a plant-derived resin. Similarly, even when mixed with lignin, which is a plant-derived resin, the ratio derived from plants can be maintained, which is preferable.
Furan resin is a plant-derived resin with good moldability, such as being able to be cured alone at room temperature by adding a strong acid, and further adding a nitrogen-containing crosslinked cyclic compound such as hexamethylenetetramine. It can also be cured by heating at 130 to 170 ° C.
リグニンにヘキサメチレンテトラミンのような含窒素架橋型環式化合物を添加して更に１３０〜１７０℃加熱により硬化させることができるが、溶融粘度が高く、成形性が悪い。 A nitrogen-containing crosslinked cyclic compound such as hexamethylenetetramine can be added to lignin and further cured by heating at 130 to 170 ° C., but the melt viscosity is high and the moldability is poor.
本発明においては、リグニンに含窒素架橋型環式化合物を添加して更に１３０〜１７０℃加熱により硬化させる際、フラン樹脂を同時に加えることを特長としている。これにより、リグニン樹脂組成物全体が低粘度化して且つ、架橋点が増えるため、得られるリグニン樹脂組成物の成形性と特性が向上する。 The present invention is characterized in that when a nitrogen-containing crosslinked cyclic compound is added to lignin and further cured by heating at 130 to 170 ° C., a furan resin is added simultaneously. Thereby, since the viscosity of the whole lignin resin composition becomes low and a crosslinking point increases, the moldability and characteristic of the obtained lignin resin composition improve.
フラン樹脂はリグニン１００重量部対し、３〜５０重量部添加する事が好ましく、更に３重量部（５重量部）〜５０重量部（３０重量部）添加することが好ましい。５重量部より少なければ得られるリグニン樹脂組成物の成形性と特性が向上せずまた、３０重量部より多ければ強度低下等の特性が低下するためいずれも好ましくない。 The furan resin is preferably added in an amount of 3 to 50 parts by weight, more preferably 3 parts by weight (5 parts by weight) to 50 parts by weight (30 parts by weight) based on 100 parts by weight of lignin. If it is less than 5 parts by weight, the moldability and properties of the resulting lignin resin composition will not be improved, and if it is more than 30 parts by weight, properties such as strength reduction will be reduced.
本発明に使用される含窒素架橋型環式化合物は、例えばキヌクリジン、ピジン、ヘキサメチレンテトラミンまたは一般式（Ｉ）
Ｚ−（ＣＨ２ＯＲ）ｍ （Ｉ）
［式（Ｉ）中のＺはメラミン残基、尿素残基、グリコルリル残基またはイミダゾリジノン残基のいずれか１種を表わす。ｍは２〜１４の整数を表わす。Ｒは独立して水素または炭素数１〜４のアルキル基を表わす。ただし、−ＣＨ２ＯＲはメラミン残基の１級アミノ基の窒素原子、尿素残基の１級アミノ残基の窒素原子、グリコリル残基の２級アミノ残基の窒素原子またはイミダゾリジノン残基の２級アミノ基の窒素原子のいずれかに直接結合する。］から選ばれる少なくとも１種などが挙げられる。
The nitrogen-containing bridged cyclic compound used in the present invention is, for example, quinuclidine, pyridine, hexamethylenetetramine, or general formula (I).
Z- (CH 2 OR) m ( I)
[Z in Formula (I) represents any one of a melamine residue, a urea residue, a glycoluril residue, or an imidazolidinone residue. m represents an integer of 2 to 14. R independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms. However, —CH 2 OR is a nitrogen atom of a primary amino group of a melamine residue, a nitrogen atom of a primary amino residue of a urea residue, a nitrogen atom of a secondary amino residue of a glycolyl residue, or an imidazolidinone residue To the nitrogen atom of the secondary amino group. And at least one selected from the group consisting of
一般式（Ｉ）で表わされる化合物としては、リグニン樹脂を架橋させ硬度を発現するものであれば特に限定されるものではないが、例えば、ホルムアルデヒドとメラミンとを反応させて得られたメラミン樹脂およびそのメタノール処理樹脂、下記一般式（１）〜（７）で表わされる化合物などが挙げられる。
一般式（Ｉ）で表わされる化合物としては、具体的には、スミカノール５０７Ａ（田岡化学工業株式会社製）、２，４，６−トリス［ビス（メトキシメチル）アミノ］−１，３，５−トリアジン（東京化成工業株式会社製）、ニカラックＭＸ−２９０（株式会社三和ケミカル製）、ニカラックＭＸ−２８０（株式会社三和ケミカル製）、ニカラックＭＸ−２７０（株式会社三和ケミカル製）などが挙げられる。 Specific examples of the compound represented by the general formula (I) include Sumikanol 507A (manufactured by Taoka Chemical Co., Ltd.), 2,4,6-tris [bis (methoxymethyl) amino] -1,3,5- Triazine (manufactured by Tokyo Chemical Industry Co., Ltd.), Nikarac MX-290 (manufactured by Sanwa Chemical Co., Ltd.), Nikalac MX-280 (manufactured by Sanwa Chemical Co., Ltd.), Nikalac MX-270 (manufactured by Sanwa Chemical Co., Ltd.), etc. Can be mentioned.
これら含窒素架橋型環式化合物の添加量は、添加量はリグニン１００重量部に対し、５〜２５重量部が好ましく、更に１０〜２０重量部が好ましい。添加量が、前記下限値より少なければリグニン樹脂組成物の硬化が不十分となる場合があり、前記上限値より多くても硬化密度が変わらない傾向にあり、いずれも好ましくない。 The addition amount of these nitrogen-containing crosslinked cyclic compounds is preferably 5 to 25 parts by weight, more preferably 10 to 20 parts by weight, with respect to 100 parts by weight of lignin. If the addition amount is less than the lower limit, curing of the lignin resin composition may be insufficient, and if it is greater than the upper limit, the curing density tends not to change.
本発明にて使用される含窒素架橋型環式化合物はキヌクリジン、ピジンおよびヘキサメチレンテトラミンの中から選ばれる少なくとも１種であり、添加量はリグニン１００重量部に対し、５〜２５重量部が好ましい。５重量部より少なければリグニン樹脂組成物の硬化が不十分であり、２５重量部より多くても硬化密度は変わらず、いずれも好ましくない。 The nitrogen-containing bridged cyclic compound used in the present invention is at least one selected from quinuclidine, pyridine and hexamethylenetetramine, and the addition amount is preferably 5 to 25 parts by weight with respect to 100 parts by weight of lignin. . If it is less than 5 parts by weight, the lignin resin composition is not sufficiently cured, and if it is more than 25 parts by weight, the curing density does not change, and neither is preferable.
本発明に用いるリグニンの製造方法としては、一例として高温、高圧の有機溶媒を使用してリグニンを溶媒和させる有機溶媒法をあげることができるが、特にその製造方法を限定するものではなく、市販のリグニンを用いても良い。 As an example of the method for producing lignin used in the present invention, an organic solvent method in which lignin is solvated using an organic solvent at high temperature and high pressure can be mentioned, but the production method is not particularly limited, and is commercially available. The lignin may be used.
リグニン１００重量部に対し、含窒素架橋型環式化合物は５〜２５重量部、フラン樹脂は５〜３０重量部添加することが好ましい。フラン樹脂については５重量部未満では成形性向上が不十分であるため好ましくない、また５０重量部を超えるとフローが大きくなり過ぎ、例えば積層板を作成する場合においてはバリが大きくなり過ぎる等悪影響が出てくるためこれも好ましくない。 It is preferable to add 5 to 25 parts by weight of the nitrogen-containing crosslinked cyclic compound and 5 to 30 parts by weight of the furan resin with respect to 100 parts by weight of lignin. If the furan resin is less than 5 parts by weight, it is not preferable because the moldability is insufficiently improved, and if it exceeds 50 parts by weight, the flow becomes too large. For example, when making a laminate, the burr becomes too large. This is also undesirable because of
フラン樹脂とリグニンの混合を促進させるため、フラン樹脂の原料であるフルフラール、やフルフリルアルコールを追加しても良い。 In order to promote mixing of furan resin and lignin, furfural or furfuryl alcohol, which is a raw material of furan resin, may be added.
また、フラン樹脂のほかに、エポキシ樹脂をさらに加えることで成形性を向上させることが可能である。また、エポキシ樹脂以外の原料を用いても構わない。 In addition to the furan resin, it is possible to improve the moldability by further adding an epoxy resin. Moreover, you may use raw materials other than an epoxy resin.
以下、実施例及び比較例により本発明を具体的に説明するが、本発明はこれらの例によって何ら限定されるものではない。ここで、「％」、「部」、「倍」は、すべて「重量％」、「重量部」、「重量倍」である。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited at all by these examples. Here, “%”, “part”, and “fold” are all “% by weight”, “part by weight”, and “times by weight”.
＜実施例１＞
市販の有機溶媒法によるリグニン、「オルガノソルブ」（シグマ・アルドリッチ社製、品番３７１０１７）を使用した。
リグニン１００重量部に対してヘキサメチレンテトラミンを１０重量部、フルフリルアルコール樹脂のフラン樹脂（住友ベークライト社製ＦＲ−１６４７５）を５０重量部添加し、更にリグニンに対して固形分４０％となる様にメタノールとアセトンの混合溶剤を加え、ワニスを作成した。ワニスの一部をサンプリングし、混合溶剤を風乾により除去した後、溶融粘度の測定を行った。
坪量１４６ｇ／ｍ２のクラフト紙にワニスを塗布して風乾によりメタノールを除去して塗布紙を得た。塗布紙を５枚積層し、１５０℃、１００ｋｇ／ｃｍ２の製品圧力にて３０ｍｉｎ．プレスすることにより積層板を得た。この積層板について、外観と曲げ強度の測定を行った。
<Example 1>
A commercially available organic solvent method lignin, “organosolve” (manufactured by Sigma-Aldrich, product number 371017) was used.
10 parts by weight of hexamethylenetetramine and 50 parts by weight of furfuryl alcohol resin furan resin (FR-16475 manufactured by Sumitomo Bakelite Co., Ltd.) are added to 100 parts by weight of lignin, and the solid content is 40% with respect to lignin. A mixed solvent of methanol and acetone was added to varnish. A part of the varnish was sampled, the mixed solvent was removed by air drying, and then the melt viscosity was measured.
Varnish was applied to kraft paper having a basis weight of 146 g / m 2 and methanol was removed by air drying to obtain a coated paper. Five coated papers were stacked and 30 min. At 150 ° C. and a product pressure of 100 kg / cm 2 . A laminate was obtained by pressing. About this laminated board, the external appearance and the bending strength were measured.
＜実施例２＞
実施例１のフルフリルアルコールの添加量を５重量部に変更した以外は実施例１と同じ。
<Example 2>
The same as Example 1 except that the amount of furfuryl alcohol added in Example 1 was changed to 5 parts by weight.
＜実施例３＞
実施例１のフルフリルアルコールの添加量を２０重量部に変更した以外は実施例１と同じ。
<Example 3>
The same as Example 1 except that the amount of furfuryl alcohol added in Example 1 was changed to 20 parts by weight.
＜実施例４＞
実施例１のヘキサメチレンテトラミンの添加量を２０重量部へ変更した以外は実施例１と同じ。
<Example 4>
The same as Example 1 except that the amount of hexamethylenetetramine added in Example 1 was changed to 20 parts by weight.
＜実施例５＞
実施例１のヘキサメチレンテトラミンをスミカノール５０７Ａ（田岡化学工業株式会社製、式（２）の化合物に相当。）に変更した以外は実施例１と同じ。
<Example 5>
The same as Example 1 except that the hexamethylenetetramine in Example 1 was changed to Sumikanol 507A (Taoka Chemical Industries, Ltd., equivalent to the compound of formula (2)).
＜実施例６＞
実施例１のヘキサメチレンテトラミンを２，４，６−トリス［ビス（メトキシメチル）アミノ］−１，３，５−トリアジン（東京化成工業株式会社製。式（４）の化合物のＲがＣＨ３の化合物に相当。）に変更した以外は実施例１と同じ。
<Example 6>
Hexamethylenetetramine of Example 1 was converted to 2,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine (manufactured by Tokyo Chemical Industry Co., Ltd. R in the compound of formula (4) is CH 3. The same as in Example 1 except that the compound was changed to
＜実施例７＞
実施例１のヘキサメチレンテトラミンをニカラックＭＸ−２９０（株式会社三和ケミカル製。式（５）のＲがＣＨ３の化合物に相当。）に変更した以外は実施例１と同じ。
<Example 7>
The same as Example 1 except that the hexamethylenetetramine of Example 1 was changed to Nicalac MX-290 (manufactured by Sanwa Chemical Co., Ltd., R in formula (5) corresponds to a compound of CH 3 ).
＜実施例８＞
実施例１のヘキサメチレンテトラミンをニカラックＭＸ−２８０（株式会社三和ケミカル製。式（６）のＲがＣＨ３の化合物に相当。）に変更した以外は実施例１と同じ。
<Example 8>
The same as Example 1 except that the hexamethylenetetramine of Example 1 was changed to Nicalac MX-280 (manufactured by Sanwa Chemical Co., Ltd., R in formula (6) corresponds to a compound of CH 3 ).
＜実施例９＞
実施例１のヘキサメチレンテトラミンをニカラックＭＸ−２７０（株式会社三和ケミカル製。式（７）のＲがＣＨ３の化合物に相当。）に変更した以外は実施例１と同じ。
<Example 9>
The same as Example 1 except that the hexamethylenetetramine of Example 1 was changed to Nicalac MX-270 (manufactured by Sanwa Chemical Co., Ltd., R in formula (7) corresponds to a compound of CH 3 ).
＜比較例１＞
実施例１のフルフリルアルコールを添加しなかったこと以外は実施例１と同じ。
<Comparative Example 1>
Same as Example 1 except that the furfuryl alcohol of Example 1 was not added.
＜比較例２＞
実施例１のフルフリルアルコールの添加量を４重量部に変更した以外は実施例１と同じ。
<Comparative example 2>
The same as Example 1 except that the amount of furfuryl alcohol added in Example 1 was changed to 4 parts by weight.
（試験方法）
１．溶融粘度
Reologica Instruments A.B.社製RheoPolym@を用いてφ２０ｍｍのパラプレート、ギャップ０．５ｍｍ、１５０℃、１Ｈｚにおける初期溶融粘度を測定した。
２．曲げ強度
各サンプルの積層板に対し、ＪＩＳ Ｋ６９１１に準拠して曲げ強度の測定を行った。
以上の実施例及び比較例で行われた結果を表１に示す。
(Test method)
1. Melt viscosity
Using RheoPolym @ manufactured by Reologica Instruments AB, the initial melt viscosity was measured at 20 mm paraplate, gap 0.5 mm, 150 ° C., 1 Hz.
2. Bending strength The bending strength of each sample laminate was measured according to JIS K6911.
Table 1 shows the results obtained in the above examples and comparative examples.
結果から明らかなように、実施例１、２のフラン樹脂を５〜３０重量部添加したものは初期溶融粘度が低く、曲げ強度も高くなり、成形性を特性が向上する。比較例１と２はフラン樹脂の添加量が少ない場合であり、いずれも初期溶融粘度が高く、曲げ強度も低いという問題がある。 As is clear from the results, those obtained by adding 5 to 30 parts by weight of the furan resins of Examples 1 and 2 have low initial melt viscosity, high bending strength, and improved moldability characteristics. Comparative Examples 1 and 2 are cases in which the amount of furan resin added is small, and both have the problem of high initial melt viscosity and low bending strength.
表２の結果から明らかなように、実施例３は実施例１と比較してフラン樹脂の添加量を２０重量部へ低減した水準、実施例４は実施例１と比較して含窒素架橋型環式化合物の添加量を２０重量部へ増量した水準、実施例５〜９は実施例１の含窒素架橋型環式化合物を他の含窒素架橋型環式化合物に置換した水準であるが、いずれの水準も初期溶融粘度が低く、曲げ強度も高く、成形性と特性が向上する。 As is apparent from the results in Table 2, Example 3 is a level in which the amount of furan resin added is reduced to 20 parts by weight compared to Example 1, and Example 4 is a nitrogen-containing crosslinked type compared to Example 1. The level in which the addition amount of the cyclic compound was increased to 20 parts by weight, and Examples 5 to 9 were levels obtained by substituting the nitrogen-containing bridged cyclic compound of Example 1 with other nitrogen-containing bridged cyclic compounds. At any level, the initial melt viscosity is low, the bending strength is high, and the moldability and properties are improved.
本発明により得られるリグニン樹脂組成物は成形性と特性が良好であり、フェノール樹脂代替の熱硬化性樹脂として利用することができる。 The lignin resin composition obtained by the present invention has good moldability and properties, and can be used as a thermosetting resin instead of a phenol resin.
Claims (8)
前記リグニン１００重量部に対し前記フラン樹脂の添加量が５〜５０重量部であり、
前記リグニン１００重量部に対し前記含窒素架橋型環式化合物の添加量が５〜２５重量部であることを特徴とする硬化性リグニン樹脂組成物。 Containing at least one selected from quinuclidine, pyridine and hexamethylenetetramine as a lignin and a nitrogen-containing bridged cyclic compound, and a furan resin,
The addition amount of the furan resin is 5 to 50 parts by weight with respect to 100 parts by weight of the lignin,
The curable lignin resin composition, wherein an addition amount of the nitrogen-containing crosslinked cyclic compound is 5 to 25 parts by weight with respect to 100 parts by weight of the lignin.
前記リグニン１００重量部に対し前記フラン樹脂の添加量が５〜５０重量部であり、
前記リグニン１００重量部に対し前記含窒素架橋型環式化合物の添加量が５〜２５重量部であることを特徴とする硬化性リグニン樹脂組成物。
Ｚ−（ＣＨ２ＯＲ）ｍ （Ｉ）
［式（Ｉ）中のＺはメラミン残基、グリコルリル残基またはイミダゾリジノン残基のいずれか１種を表わす。ｍは２〜１４の整数を表わす。Ｒは独立して水素または炭素数１〜４のアルキル基を表わす。ただし、−ＣＨ２ＯＲはメラミン残基の１級アミノ基の窒素原子、グリコリル残基の２級アミノ残基の窒素原子またはイミダゾリジノン残基の２級アミノ基の窒素原子のいずれかに直接結合する。］ A lignin and a nitrogen-containing crosslinked cyclic compound represented by the following general formula (I), and a furan resin,
The addition amount of the furan resin is 5 to 50 parts by weight with respect to 100 parts by weight of the lignin,
The curable lignin resin composition, wherein an addition amount of the nitrogen-containing crosslinked cyclic compound is 5 to 25 parts by weight with respect to 100 parts by weight of the lignin.
Z- (CH 2 OR) m ( I)
[Z in the formula (I) represents any one of melamine residues, grayed Rikoruriru residues or imidazolidinone residues. m represents an integer of 2 to 14. R independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms. However, the nitrogen atom of the primary amino groups of the -CH 2 OR melamine residues, to a nitrogen atom at the secondary amino group nitrogen atom or imidazolidinone residues of 2 amino acid residues of the grayed Rikoriru residues Join directly. ]
前記リグニン１００重量部に対し前記フラン樹脂の添加量が５〜５０重量部であり、
前記リグニン１００重量部に対し前記含窒素架橋型環式化合物の添加量が５〜２５重量部であることを特徴とする硬化性リグニン樹脂組成物。
［式（１）中、Ｘは−ＣＨ２ＯＲまたは水素原子であり、Ｒは独立して水素または炭素数１〜４のアルキル基である。また、ｎは１〜３の整数を表す。］ A lignin and a nitrogen-containing crosslinked cyclic compound represented by the following general formula (1), and a furan resin,
The addition amount of the furan resin is 5 to 50 parts by weight with respect to 100 parts by weight of the lignin,
The curable lignin resin composition, wherein an addition amount of the nitrogen-containing crosslinked cyclic compound is 5 to 25 parts by weight with respect to 100 parts by weight of the lignin.
[In the formula (1), X is -CH 2 OR or a hydrogen atom, R is independently hydrogen or an alkyl group having 1 to 4 carbon atoms. N represents an integer of 1 to 3. ]
前記リグニン１００重量部に対し前記フラン樹脂の添加量が５〜５０重量部であり、
前記リグニン１００重量部に対し前記含窒素架橋型環式化合物の添加量が５〜２５重量部であることを特徴とする硬化性リグニン樹脂組成物。
［式（２）中、ｎは１〜３の整数を表す。］
［式（３）中、ｎは１〜３の整数を表す。］ Containing at least one selected from the following general formulas (2) and (3) as a lignin and a nitrogen-containing bridged cyclic compound, and a furan resin,
The addition amount of the furan resin is 5 to 50 parts by weight with respect to 100 parts by weight of the lignin,
The curable lignin resin composition, wherein an addition amount of the nitrogen-containing crosslinked cyclic compound is 5 to 25 parts by weight with respect to 100 parts by weight of the lignin.
[In formula (2), n represents the integer of 1-3. ]
[In Formula (3), n represents the integer of 1-3. ]
前記リグニン１００重量部に対し前記フラン樹脂の添加量が５〜５０重量部であり、
前記リグニン１００重量部に対し前記含窒素架橋型環式化合物の添加量が５〜２５重量部であることを特徴とする硬化性リグニン樹脂組成物。
［式（４）中、Ｒは独立して水素または炭素数１〜４のアルキル基である。］
［式（６）中、Ｒは独立して水素または炭素数１〜４のアルキル基である。］
［式（７）中、Ｒは独立して水素または炭素数１〜４のアルキル基である。］ Containing at least one selected from the formulas (4) , (6) and (7) as a lignin and a nitrogen-containing crosslinked cyclic compound, and a furan resin,
The addition amount of the furan resin is 5 to 50 parts by weight with respect to 100 parts by weight of the lignin,
The curable lignin resin composition, wherein an addition amount of the nitrogen-containing crosslinked cyclic compound is 5 to 25 parts by weight with respect to 100 parts by weight of the lignin.
[In Formula (4), R is independently hydrogen or a C1-C4 alkyl group. ]
[In formula (6), R is independently hydrogen or a C1-C4 alkyl group. ]
[In formula (7), R is independently hydrogen or a C1-C4 alkyl group. ]
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