JP3598025B2 - Reactive linseed oil composition and method for producing the same - Google Patents
Reactive linseed oil composition and method for producing the same Download PDFInfo
- Publication number
- JP3598025B2 JP3598025B2 JP22856299A JP22856299A JP3598025B2 JP 3598025 B2 JP3598025 B2 JP 3598025B2 JP 22856299 A JP22856299 A JP 22856299A JP 22856299 A JP22856299 A JP 22856299A JP 3598025 B2 JP3598025 B2 JP 3598025B2
- Authority
- JP
- Japan
- Prior art keywords
- linseed oil
- reactive
- fat composition
- oil
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 235000021388 linseed oil Nutrition 0.000 title claims description 93
- 239000000944 linseed oil Substances 0.000 title claims description 93
- 239000000203 mixture Substances 0.000 title claims description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000976 ink Substances 0.000 claims description 19
- 239000003973 paint Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 15
- 238000011282 treatment Methods 0.000 claims description 15
- 238000002835 absorbance Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000004332 deodorization Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 235000019197 fats Nutrition 0.000 description 40
- 239000003921 oil Substances 0.000 description 31
- 235000019198 oils Nutrition 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 21
- 238000001035 drying Methods 0.000 description 20
- 235000004426 flaxseed Nutrition 0.000 description 17
- 230000009257 reactivity Effects 0.000 description 16
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 235000004431 Linum usitatissimum Nutrition 0.000 description 14
- 240000006240 Linum usitatissimum Species 0.000 description 14
- 238000000354 decomposition reaction Methods 0.000 description 12
- 238000006317 isomerization reaction Methods 0.000 description 12
- 229920000180 alkyd Polymers 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 230000003685 thermal hair damage Effects 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- MJYQFWSXKFLTAY-OVEQLNGDSA-N (2r,3r)-2,3-bis[(4-hydroxy-3-methoxyphenyl)methyl]butane-1,4-diol;(2r,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O.C1=C(O)C(OC)=CC(C[C@@H](CO)[C@H](CO)CC=2C=C(OC)C(O)=CC=2)=C1 MJYQFWSXKFLTAY-OVEQLNGDSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 3
- 229960004488 linolenic acid Drugs 0.000 description 3
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001256 steam distillation Methods 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- JBYXPOFIGCOSSB-GOJKSUSPSA-N 9-cis,11-trans-octadecadienoic acid Chemical compound CCCCCC\C=C\C=C/CCCCCCCC(O)=O JBYXPOFIGCOSSB-GOJKSUSPSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229940108924 conjugated linoleic acid Drugs 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000008157 edible vegetable oil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000003904 phospholipids Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002383 tung oil Substances 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 229920000715 Mucilage Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229940106134 krill oil Drugs 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Landscapes
- Fats And Perfumes (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
【発明の属する技術分野】
【０００１】
本発明は、原料アマニ油を高度精製処理することによって、軽度精製アマニ油と比較して、熱重合性、酸化重合性、共役異性化反応性などラジカル反応性を高めた反応性アマニ油脂組成物に関する。また、これをアクリル樹脂などの光反応性樹脂に添加して硬化した場合、軽度精製アマニ油を添加した樹脂と比較して、重合度の高い樹脂を提供する。また、これを塗料やインキの原料に用いた場合、従来のボイル油、スタンド油、異性化油と比較して、高付着性、耐溶剤性に優れた塗料またはインキを提供する。
【従来の技術】
【０００２】
アマニ油はヨウ素価が高く、代表的な乾性油として古くから工業用途（塗料、インキ、リノリウムなど）に用いられている植物油である。アマニは圧抽法により搾油し、得られたアマニ粗油は脱ガム工程、脱酸工程、脱色工程を経て精製される。リン脂質や粘質物が含まれていると２９０℃以上に加熱すると、もろもろしたブレークと呼ばれる不溶物が析出する。一般的にはブレークの析出が認められないノンブレーク（Ｎ／Ｂ）アマニ油が流通している。
アマニ油は、さらに反応性を高めるために古くから様々な加工が施されてきた。例えば、アマニ油に酸化促進剤（例えば、ナフテン酸金属塩）を加え、空気を吹き込みながら１００〜１５０℃に加熱し酸化を促進させて乾燥性を高めたボイル油、アマニ油を真空または不活性気流下で３００℃近くで加熱させて乾燥性を高めたスタンド油、アマニ油をアルカリ、ニッケル、金属酸化物、二酸化硫黄、アントラキノン、ベントナイト、ヨウ化メチル、シリカなどの触媒に用いて共役異性化させた異性化油などである。このように、分子を重合させて分子量を大きくする方法、分子内の二重結合の位置を変える方法以外にも、アマニ油の反応性を高めるために、エポキシ化、マレイン化などの様々な方法が行われてきた。
これらの方法により得られたアマニ油誘導体は、その製造の過程において、熱的ダメージを受けることにより、重合物や脂肪酸の二重結合の部分で切れた低分子量の熱分解物などを含有する。そのため、これらのアマニ油誘導体を用いて塗料やインキを作った場合、付着性、耐溶剤性などの点で問題が生じる。
【０００３】
植物油の精製度と反応性の関係については、キリ油や食用油で検討されている。キリ油を無溶剤あるいは非極性溶剤に希釈した状態で通常のレベルに比較して非常に大量の吸着剤、例えば活性白土、シリカゲル等に接触させたり、いわゆるカラム精製のような処理を施すことにより、光散乱物質や光吸収物質等の反応阻害物質を除去することで、本来キリ油が持っていないＵＶ硬化性機能を持つことができたものである（特開平１０−９５９４５号公報；特開平１０−６０３０５号公報）。
また、ラジカルを不活性化する成分を含有させることで反応性を低下させ、劣化しにくい安定性の高い食用油を得る報告がある（特開平９−１５７６８７号公報；特開昭６０−２０３８９号公報；特開昭５３−９１９１１号公報）。
【発明が解決しようとする課題】
【０００４】
本発明品は、従来のボイル油、スタンド油、異性化油等と比較して、熱的ダメージが少なく分解物含量が少ないので、これを原料とした塗料やインキ等の場合、金属やガラスに対する付着性が良好で、乾燥後分解物の溶出または揮発等の可能性が少なく、さらに色、臭いなども良好な塗料またはインキを提供する。
【課題を解決するための手段】
【０００５】
本発明者らは、上記課題を解決すべく鋭意検討を行った結果、原料アマニ油脂組成物を精製処理することにより、原料アマニ油脂組成物より著しく反応性を高め、従来からあるボイル油、スタンド油、異性化油等と比較して、熱的ダメージが少なく分解物含量が少ない反応性アマニ油脂組成物を得、これを原料とした塗料やインキ等の場合、塗膜の付着性が良好で、乾燥後分解物の溶出または揮発等の可能性も少ない、色、臭いの点で優れた反応性アマニ油脂組成物が得られることを見出し、本発明を完成させた。
すなわち、紫外吸光分析において、濃度が０．０１５ｇ／Ｌのときの２３７ｎｍの吸光度指数が０．６以下、かつ５ｇ／Ｌのときの３１７ｎｍにおける吸光度指数が０．２以下である反応性アマニ油脂組成物である。
反応性アマニ油脂組成物は、原料アマニ油脂組成物を精製処理することにより得られる。精製処理は、高度精製処理で、脱臭、吸着、イオン交換の処理の単独または２以上組合わせが可能である。即ち、脱臭は水蒸気吹き込み、窒素吹き込みなど、吸着、イオン交換は、白土、活性炭、シリカゲル、イオン交換樹脂などによる処理が挙げられる。さらに、該油脂組成物を含むことにより、熱または酸化重合反応性の高い塗料またはインキ用原料を得ることができる。本発明の高度精製処理とは、熱的ダメージを最小限に押さえた高度の精製処理をすることで、酸化重合性、熱重合性、共役異性化反応性などのラジカル反応性を高めた反応性アマニ油組成物を提供し、また、これをアクリル樹脂などの光反応性樹脂に添加して硬化した場合、軽度精製アマニ油を添加した樹脂と比較して、重合度の高い樹脂を提供し、また、これを塗料やインキの原料に用いた場合、金属、ガラスに対する付着性、耐溶剤性に優れた塗料やインキを提供するものである。
【実施の形態】
【０００６】
本発明における反応性アマニ油脂組成物の反応性とは、主として、酸化重合性、熱重合性、共役異性化反応性など、ラジカル反応性が高いことを意味する。本発明の反応性アマニ油脂組成物は、高度精製処理により、原料アマニ油脂組成物より著しく反応性を高め、アクリル樹脂等の硬化阻害を低減する。また、従来からあるボイル油、スタンド油、異性化油等と比較して、熱的ダメージが少なく分解物含量が少ない反応性アマニ油脂組成物で、これを原料とした塗料やインキ等の塗膜の付着性が均一良好で、乾燥後分解物の溶出または揮発等の可能性も少なく、色、臭いの点で優れたものである。
一般に抗酸化物質と呼ばれている、リン脂質等のリン含有成分、トコフェロール等のフェノール性水酸基をもつ成分、葉緑素、カロチノイドやその関連物質、あるいはアミノ基を有する成分等には、酸素存在量の低減、光、熱、放射線のエネルギーの遮断、光増感剤の作用の抑制、金属の触媒作用とその防止、ラジカルの安定化およびラジカル連鎖反応の停止等の作用がある。したがって、原料アマニ油脂組成物中のこのような抗酸化物質を高度精製処理によって低減させることによって、原料アマニ油脂組成物（例えば、Ｎ／Ｂアマニ油）より著しく反応性を高めた反応性アマニ油脂組成物を得ることができる。
反応性アマニ油脂組成物は、主として反応性アマニ脂肪酸トリグリセライド、反応性アマニ脂肪酸で、反応性アマニ脂肪酸ジグリセライド、反応性アマニ脂肪酸モノグリセライドも部分的に含まれる。
本発明における原料アマニ油脂組成物とは、本発明の高度精製処理品に対し、軽度精製処理品または未処理品と位置づけられるもので、具体的には、ＪＡＳで規定するところのアマニ油、Ｎ／Ｂアマニ油、精製アマニ油で、これらの原料油も含まれ、さらに原料アマニ脂肪酸なども含まれる。これらはそれぞれ単独、もしくは２種以上を混合して使用することができる。
原料アマニ脂肪酸とは、原料アマニ油を１８９７年Ｔｗｉｔｃｈｅｌｌ Ｅ．が開発した硫酸を用いるトイッチェル分解法、高温アルカリ分解と酸分解および熱時分離を組み合わせた方法（特開昭４９−１２４１０３号公報）、１９３５年にＶｉｃｔｏｒ−Ｍｉｌｌｓが発表した連続高圧分解法、あるいは酵素を用いた酵素分解法（特願平１１−２２５３５号公報）などにより分解して得られる。
【０００７】
本発明における精製処理とは、脱臭、吸着、イオン交換による精製を指し、具体的には、脱臭は、通常の植物油に用いられる温度２００℃以上による水蒸気蒸留や、窒素などの不活性ガスを吹き込む一般蒸留、吸着、イオン交換は、活性白土、活性炭、活性アルミナ、シリカゲル、ゼオライト、イオン交換樹脂、キレート樹脂などを用いたものが挙げられ、これらはそれぞれ、単独もしくは２種以上の処理を組み合わせて行うことができる。
【０００８】
反応性アマニ油脂組成物は、原料アマニ油脂組成物を上記の精製処理を行うことにより得ることができ、また、原料アマニ脂肪酸から得られた反応性アマニ脂肪酸をエステル合成することにより得ることもできる。
反応性アマニ脂肪酸は、原料アマニ脂肪酸を膜分離、吸着等によって得ることができ、また、原料アマニ油脂組成物から得られた反応性アマニ油脂組成物を上記の分解方法により分解して得ることもできる。
【０００９】
本発明は、熱的ダメージが少なく、ラジカル反応に影響を及ぼすラジカル捕捉能を有する物質の残存量を低減した反応性アマニ油脂組成物を得るものである。具体的には下記の式に示す吸光度指数が一定値以下になることである。なお、油脂組成物の、ある濃度での波長ｘｎｍの吸光度指数αＸを次のように定義する。
αＸ＝ＡＸ／Ａ２１２
α２３７＝Ａ２３７／Ａ２１２≦０．６
α３１７＝Ａ３１７／Ａ２１２≦０．２
Ａ２１２：油脂組成物の濃度が０．０１５ｇ／Ｌのときの２１２ｎｍの吸光度
Ａ２３７：油脂組成物の濃度が０．０１５ｇ／Ｌのときの２３７ｎｍの吸光度
Ａ３１７：油脂組成物の濃度が５ｇ／Ｌのときの３１７ｎｍの吸光度
【００１０】
【実施例】
以下、実施例および比較例にて本発明を説明する。実施例中の％は重量％を示す。尚、本発明はここに挙げた実施例に限定されるものではない。
実施例、比較例中の吸光度指数、重合物含量、乾燥方法および乾燥時間、異性化反応率、付着性、耐溶剤性の評価は下記のごとく実施した。
［吸光度指数］
測定するアマニ油脂組成物の濃度が０．０１５ｇ／Ｌ、または、５ｇ／Ｌになるように、アマニ油脂組成物をシクロヘキサンに溶解し、液層の長さ１０ｍｍの石英硝子セルを用いて分光光度計により、２１２、２３７、３１７ｎｍの吸光度を測定した。そして、前述の式により吸光度指数を求めた。
［乾燥方法および乾燥時間］
ＪＩＳ Ｋ５４００ ６．５ 乾燥時間
常乾：塗料を試験片に塗布した後、２５℃に放置した場合で、粘着性を失い、塗膜を形成するまでの乾燥時間を表した。
焼き付け：塗料を試験片に塗布した後、１２０℃の恒温槽中に放置した場合で、粘着性を失い、塗膜を形成するまでの乾燥時間を表した。
なお、常乾、焼き付けとも、アマニ油脂組成物５０部に、増粘のための酸化チタン７０部、ドライヤーとしてナフテン酸コバルト（コバルト含量６％）を０．３５部加えたものを塗料とした。
［異性化反応率］
異性化反応前の非共役不飽和脂肪酸含量（リノール酸・リノレン酸）に対する、異性化反応後の共役不飽和脂肪酸含量（共役リノール酸・共役リノレン酸）（％）なお、異性化反応は以下の方法で行った。
原料アマニ油脂組成物１４０部に、ヨウ素の０．５％ヘキサン溶液を３２部、ｎ−ヘキサン２６０部を加えた混合物に対して、高圧水銀ランプ（ウシオ電機（株）製、型式：ＵＭ−１０２）を用い、水冷しながら７時間照射して異性化反応を行い、異性化油を得た。
［硬化阻害指数］
トリメチロールプロパントリアクリレート（新中村化学社製）８８部、ＩＲＧＣＵＲＥ１８４（チバガイギー社製）２部、アマニ油脂組成物１０部を混合し、塩化ビニルのチューブに入れて、高圧水銀ランプ（ウシオ電機（株）製、型式：ＵＭ−１０２）を用いて、１分間ＵＶ硬化する。この硬化物をヘキサンに３日間浸した後、８０℃で３時間乾燥し、（乾燥後の重量／仕込み重量）×１００（％）より、乾燥後樹脂分（％）を求めた。そして、硬化阻害指数を以下の式により定義した。
液体クロマトグラフィーにより定量した。
［付着性］
ＪＩＳ Ｋ５４００ ８．５．３ Ｘカットテープ法
試験片の上の塗膜を貫通して、素地面に達するＸ状の切傷をカッターナイフで付け、その上にセロハン粘着テープを張りつけて引き剥がし、素地との付着性を０（劣）〜１０（優）点で評価した。
［耐溶剤性］
試験片をトルエンに一定時間含浸させ、試験片重量の減少率（％）で評価した。
【００１１】
実施例１ 反応性アマニ油脂組成物の製造例
Ｎ／Ｂアマニ油１００部を、２５０℃、１ｍｍＨｇで１時間、水蒸気蒸留して、反応性アマニ油脂組成物９９．５部を得た。吹き込み水蒸気量は約０．５部だった。
【００１２】
実施例２ 反応性アマニ油脂組成物の製造例
Ｎ／Ｂアマニ油１００部を、２５０℃、１ｍｍＨｇで３時間、窒素蒸留して、反応性アマニ油脂組成物９９．５部を得た。
【００１３】
実施例３ 反応性アマニ油脂組成物の製造例
Ｎ／Ｂアマニ油４０部を、シリカゲル（富士シリシア化学社製）１０００部を充填したカラムに添加し、ヘキサン−エーテル（９：１）溶媒を用いて展開したところ、反応性アマニ油脂組成物３９．８部を得た。
【００１４】
比較例１ 軽度精製アマニ油脂組成物の比較製造例
Ｎ／Ｂアマニ油１００部を、１５０℃、１ｍｍＨｇで１時間、水蒸気蒸留して、反応性アマニ油脂組成物９９．６部を得た。吹き込み水蒸気量は約０．５部だった。
【００１５】
比較例２ 軽度精製アマニ油脂組成物の比較製造例
軽度精製アマニ油として、アマニ原油（日清製油社製）を使用した。
【００１６】
比較例３ 軽度精製アマニ油脂組成物の比較製造例
軽度精製アマニ油として、Ｎ／Ｂアマニ油（日清製油社製）を使用した。
得られたアマニ油脂組成物について、乾燥時間、共役異性化反応率を測定した。
【００１７】
【表１】
実施例１〜３、比較例１〜３より、本発明の反応性アマニ油脂組成物は、軽度精製アマニ油脂組成物と比較して、酸化重合性（常乾）、熱重合性（焼き付け）、共役異性化反応性に優れていることが分かった。また、これをアクリル樹脂などの光反応性樹脂に添加して硬化した場合、軽度精製アマニ油を添加した樹脂と比較して、樹脂の硬化阻害を低減し、重合度の高い樹脂が得られることが分かった。
【００１９】
実施例４ 反応性アマニ油脂組成物変性アルキッド樹脂の製造例
無水フタル酸４３．６部とグリセリン２１．８部を１８０℃で５時間反応させて、これに、実施例１で脱臭により得られた反応性アマニ油脂組成物を４０．０部加え、２２０℃で１０時間反応して遊離水酸基をエステル化して、反応性アマニ油脂組成物変性アルキッド樹脂を１００部得た。
【００２０】
比較例４ 従来型反応性アマニ油脂組成物変性アルキッド樹脂の比較製造例
無水フタル酸４３．６部とグリセリン２１．８部を１８０℃で５時間反応させて、これに７号ボイル油（横瀬製油所社製）を４０．０部加え、２２０℃で１０時間反応して遊離水酸基をエステル化して、従来型反応性アマニ油脂組成物変性アルキッド樹脂を１００部得た。
【００２１】
比較例５ 従来型反応性アマニ油脂組成物変性アルキッド樹脂の比較製造例
無水フタル酸４３．６部とグリセリン２１．８部を１８０℃で５時間反応させて、これに８号ボイル油（日清製油社製）を４０．０部加え、以下比較例４と同様な方法により、従来型反応性アマニ油脂組成物変性アルキッド樹脂を１００部得た。
【００２２】
比較例６ 従来型反応性アマニ油脂組成物変性アルキッド樹脂の比較製造例
無水フタル酸４３．６部とグリセリン２１．８部を１８０℃で５時間反応させて、これにスタンド油（日清製油社製：スタンド油Ｌ−２）を４０．０部加え、以下比較例４と同様な方法により、従来型反応性アマニ油脂組成物変性アルキッド樹脂を１００部得た。
【００２３】
比較例７ 従来型反応性アマニ油脂組成物変性アルキッド樹脂の比較製造例
無水フタル酸４３．６部とグリセリン２１．８部を１８０℃で５時間反応させて、これに異性化油（日清製油社製：ＮＣ−１０１）を４０．０部加え、以下比較例４と同様な方法により、従来型反応性アマニ油脂組成物変性アルキッド樹脂を１００部得た。
得られたアルキッド樹脂塗料について、付着性、耐溶剤性を測定した。また、樹脂原料のアマニ油脂組成物中の重合物含量を測定した。
【００２４】
【表２】
実施例４、比較例４〜７より、熱的ダメージの少ない本発明の反応性アマニ油脂組成物を含む塗料用樹脂は、従来型反応性アマニ油脂組成物と比較して、付着性、耐溶剤性に優れていることが分かった。従来型反応性アマニ油脂組成物の製造過程で生じた低分子量の分解物が、これを含む樹脂の付着性及び耐溶剤性に影響していると考えられる。
【００２６】
【発明の効果】
本発明によれば、原料アマニ油を高度精製処理することによって、軽度精製アマニ油と比較して、熱重合性、酸化重合性、共役異性化反応性などラジカルを伴う反応の反応性を高めた反応性アマニ油脂組成物が得られる。また、従来のボイル油、スタンド油、異性化油等と比較して、熱的ダメージが少なく分解物含量が少ないので、これを原料とした塗料やインキ等の場合、金属やガラスに対する付着性が良好で、乾燥後分解物の溶出または揮発等の可能性が少なく、さらに色、臭いなども良好な塗料またはインキを提供することができる。TECHNICAL FIELD OF THE INVENTION
[0001]
The present invention relates to a reactive linseed oil and fat composition having a high degree of radical reactivity, such as thermal polymerization, oxidative polymerization, and conjugate isomerization reactivity, compared to lightly refined linseed oil by highly refining the raw linseed oil. About. When this is added to a photoreactive resin such as an acrylic resin and cured, a resin having a higher degree of polymerization is provided as compared with a resin to which lightly refined linseed oil is added. Further, when this is used as a raw material for paints and inks, the present invention provides paints or inks having high adhesion and solvent resistance as compared with conventional boil oils, stand oils, and isomerized oils.
[Prior art]
[0002]
Linseed oil is a vegetable oil which has a high iodine value and has been used as a typical drying oil for a long time in industrial applications (paints, inks, linoleum, etc.). The flaxseed is squeezed by a pressure extraction method, and the resulting flaxseed crude oil is purified through a degumming step, a deacidifying step, and a decolorizing step. When it is heated to 290 ° C. or higher when it contains a phospholipid or a mucilage, insolubles called friable breaks are precipitated. In general, non-break (N / B) linseed oil in which break precipitation is not recognized is distributed.
Linseed oil has been subjected to various processings since ancient times to further enhance the reactivity. For example, boiled oil and linseed oil, which are added with an oxidizing agent (eg, a metal salt of naphthenic acid) to linseed oil and heated to 100 to 150 ° C. while blowing air to promote oxidation to enhance drying properties, are vacuum- or inertized. Conjugated isomerization using stand oil and linseed oil heated to near 300 ° C in a stream to enhance drying properties as a catalyst for alkali, nickel, metal oxide, sulfur dioxide, anthraquinone, bentonite, methyl iodide, silica, etc. And isomerized oil. Thus, besides the method of polymerizing molecules to increase the molecular weight, the method of changing the position of the double bond in the molecule, various methods such as epoxidation and maleation to increase the reactivity of linseed oil Has been done.
The linseed oil derivative obtained by these methods is subjected to thermal damage in the course of its production, and contains a polymer or a low-molecular-weight pyrolyzate cut at a double bond portion of a fatty acid. Therefore, when a paint or ink is made using these linseed oil derivatives, problems arise in terms of adhesion, solvent resistance, and the like.
[0003]
The relationship between the degree of refining and the reactivity of vegetable oils has been studied for tung oil and edible oil. By contacting a very large amount of adsorbent, such as activated clay, silica gel, etc., compared to the usual level in a state in which krill oil is diluted in a non-solvent or non-polar solvent, or by performing a treatment such as column purification By removing a reaction-inhibiting substance such as a light-scattering substance or a light-absorbing substance, a UV-curable function which is not originally possessed by tung oil can be obtained (Japanese Patent Laid-Open No. 10-95945; No. 10-60305).
In addition, there is a report that a reactive oil is reduced by adding a component that inactivates a radical to obtain a highly stable edible oil which is hardly deteriorated (JP-A-9-157687; JP-A-60-20389). Gazette; JP-A-53-91911).
[Problems to be solved by the invention]
[0004]
Compared with conventional boil oil, stand oil, isomerized oil, etc., the product of the present invention is less thermally damaged and has a lower content of decomposed products. Provided is a paint or ink having good adhesion, little possibility of elution or volatilization of a decomposed product after drying, and good color and odor.
[Means for Solving the Problems]
[0005]
The present inventors have conducted intensive studies to solve the above problems, and as a result, by refining the raw linseed oil / fat composition, the reactivity was significantly enhanced compared to the raw linseed oil / fat composition. Oil, isomerized oil, etc., to obtain a reactive linseed oil / fat composition having a low thermal damage and a low decomposition product content, and in the case of a paint or ink using this as a raw material, the adhesion of the coating film is good. The present inventors have found that a reactive linseed oil / fat composition excellent in color and odor with little possibility of elution or volatilization of a decomposition product after drying is obtained, and completed the present invention.
That is, in ultraviolet absorption analysis, a reactive linseed oil composition having an absorbance index at 237 nm of 0.6 or less at a concentration of 0.015 g / L and an absorbance index at 317 nm of 0.2 or less at 5 g / L. Things.
The reactive linseed oil and fat composition is obtained by subjecting the raw linseed oil and fat composition to a purification treatment. The refining treatment is an advanced refining treatment, and a single or a combination of two or more of deodorization, adsorption, and ion exchange treatments is possible. That is, deodorization includes treatment with steam, nitrogen, and the like, and adsorption and ion exchange include treatment with clay, activated carbon, silica gel, ion exchange resin, and the like. Further, by containing the oil / fat composition, it is possible to obtain a coating or ink raw material having high thermal or oxidative polymerization reactivity. The advanced purification treatment of the present invention is a highly purified treatment that minimizes thermal damage, thereby increasing radical reactivity such as oxidative polymerization, thermal polymerization, and conjugate isomerization reactivity. Providing a linseed oil composition, and when this is added to a photoreactive resin such as an acrylic resin and cured, compared to a resin to which lightly refined linseed oil is added, to provide a resin having a high degree of polymerization, Further, when this is used as a raw material for paints and inks, the present invention provides paints and inks excellent in adhesion to metals and glass and solvent resistance.
Embodiment
[0006]
The reactivity of the reactive linseed oil composition in the present invention mainly means high radical reactivity such as oxidative polymerization, thermal polymerization, and conjugate isomerization reactivity. The reactive linseed oil and fat composition of the present invention, by a highly refined treatment, significantly enhances the reactivity compared to the raw linseed oil and fat composition, and reduces the inhibition of curing of acrylic resin and the like. In addition, compared to conventional boil oil, stand oil, isomerized oil, etc., it is a reactive linseed oil and fat composition with less thermal damage and less decomposition product content, and a coating such as paint or ink using this as a raw material Is excellent in terms of color and odor, with little possibility of elution or volatilization of decomposition products after drying.
Phosphorus-containing components such as phospholipids, components having a phenolic hydroxyl group such as tocopherol, chlorophyll, carotenoids and related substances, or components having an amino group, which are generally called antioxidants, have an oxygen abundance. There are functions of reducing, blocking the energy of light, heat, and radiation, suppressing the action of a photosensitizer, catalyzing and preventing the action of a metal, stabilizing a radical, and stopping a radical chain reaction. Therefore, by reducing such antioxidants in the raw linseed oil composition by a highly refined treatment, a reactive linseed oil having a significantly higher reactivity than the raw linseed oil composition (for example, N / B linseed oil) A composition can be obtained.
The reactive linseed oil and fat composition is mainly a reactive linseed fatty acid triglyceride and a reactive linseed fatty acid, and partially includes a reactive linseed fatty acid diglyceride and a reactive linseed fatty acid monoglyceride.
The raw linseed oil composition according to the present invention is one that is positioned as a lightly refined or untreated product with respect to the highly refined treated product of the present invention. Specifically, linseed oil, N / B linseed oil and refined linseed oil, including these raw material oils, and also raw linseed fatty acids. These can be used alone or in combination of two or more.
Raw linseed fatty acid means raw linseed oil in 1897 from Twitterell E.C. A method combining toychel decomposition using sulfuric acid, a method combining high-temperature alkali decomposition, acid decomposition and thermal separation (JP-A-49-124103), a continuous high-pressure decomposition method published by Victor-Mills in 1935, or It is obtained by decomposition by an enzyme decomposition method using an enzyme (Japanese Patent Application No. 11-22535).
[0007]
The refining treatment in the present invention refers to purification by deodorization, adsorption, and ion exchange. Specifically, deodorization involves steam distillation at a temperature of 200 ° C. or higher, which is used for ordinary vegetable oils, and blowing in an inert gas such as nitrogen. General distillation, adsorption and ion exchange include those using activated clay, activated carbon, activated alumina, silica gel, zeolite, ion exchange resin, chelate resin, etc., each of which may be used alone or in combination of two or more treatments. It can be carried out.
[0008]
The reactive linseed oil and fat composition can be obtained by performing the above-mentioned purification treatment on the raw linseed oil and fat composition, and can also be obtained by ester-forming a reactive linseed fatty acid obtained from the raw linseed fatty acid. .
The reactive linseed fatty acid can be obtained by subjecting the raw linseed fatty acid to membrane separation, adsorption, or the like, and can also be obtained by decomposing the reactive linseed oil or fat composition obtained from the raw linseed oil or fat composition by the decomposition method described above. it can.
[0009]
The present invention is to obtain a reactive linseed oil and fat composition with reduced thermal damage and a reduced residual amount of a substance having a radical scavenging ability that affects a radical reaction. Specifically, this means that the absorbance index shown in the following equation becomes a certain value or less. The absorbance index αX at a certain concentration of the oil / fat composition at a certain wavelength xnm is defined as follows.
αX = AX / A212
α237 = A237 / A212 ≦ 0.6
α317 = A317 / A212 ≦ 0.2
A212: Absorbance at 212 nm when the concentration of the fat or oil composition is 0.015 g / L A237: Absorbance at 237 nm when the concentration of the fat or oil composition is 0.015 g / L A317: When the concentration of the fat or oil composition is 5 g / L Absorbance at 317 nm
【Example】
Hereinafter, the present invention will be described with reference to Examples and Comparative Examples. % In Examples shows% by weight. Note that the present invention is not limited to the embodiments described here.
The evaluation of the absorbance index, the content of the polymer, the drying method and the drying time, the isomerization reaction rate, the adhesion and the solvent resistance in Examples and Comparative Examples were carried out as follows.
[Absorbance index]
The linseed oil / fat composition is dissolved in cyclohexane so that the concentration of the linseed oil / fat composition to be measured is 0.015 g / L or 5 g / L, and spectrophotometry is performed using a quartz glass cell having a liquid layer length of 10 mm. The absorbance at 212, 237 and 317 nm was measured with a meter. And the light absorbency index was calculated | required by the above-mentioned formula.
[Drying method and drying time]
JIS K5400 6.5 Drying time: Drying: When the paint was applied to a test piece and left at 25 ° C., the adhesiveness was lost and the drying time until a coating film was formed was represented.
Baking: When the paint was applied to the test piece and left in a constant temperature bath at 120 ° C., the drying time until the film lost its tackiness and formed a coating film was expressed.
In addition, the coating which added 70 parts of titanium oxides for thickening and 0.35 parts of cobalt naphthenate (cobalt content: 6%) as a dryer to 50 parts of the flaxseed oil and fat composition was added to both the normal drying and baking.
[Isomerization reaction rate]
Conjugated unsaturated fatty acid content (conjugated linoleic acid / conjugated linolenic acid) after isomerization reaction (conjugated linoleic acid / conjugated linolenic acid) to non-conjugated unsaturated fatty acid content (linoleic acid / linolenic acid) before isomerization reaction (%) Made by the way.
To a mixture obtained by adding 32 parts of a 0.5% hexane solution of iodine and 260 parts of n-hexane to 140 parts of the raw linseed oil / fat composition, a high-pressure mercury lamp (manufactured by Ushio Inc., Model: UM-102) ), Irradiation was performed for 7 hours while cooling with water to carry out an isomerization reaction to obtain an isomerized oil.
[Curing inhibition index]
A mixture of 88 parts of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), 2 parts of IRGCURE 184 (manufactured by Ciba Geigy), and 10 parts of linseed oil and fat composition, put the mixture in a tube of vinyl chloride, and put it in a high-pressure mercury lamp (USHIO INC. ), UV curing for 1 minute using model: UM-102). The cured product was immersed in hexane for 3 days, dried at 80 ° C. for 3 hours, and a resin content (%) after drying was calculated from (weight after drying / weight charged) × 100 (%). And the cure inhibition index was defined by the following formula.
It was quantified by liquid chromatography.
[Adhesiveness]
JIS K5400 8.5.3 X-cut tape method An X-shaped cut that penetrates the coating film on the test piece and reaches the bare ground with a cutter knife, affixes cellophane adhesive tape on the cut, and peels off. Was evaluated from 0 (poor) to 10 (excellent).
[Solvent resistance]
The test piece was impregnated with toluene for a certain period of time, and evaluated by the weight reduction (%) of the test piece.
[0011]
Example 1 Production Example of Reactive Linseed Oil Composition 100 parts of N / B linseed oil were subjected to steam distillation at 250 ° C. and 1 mmHg for 1 hour to obtain 99.5 parts of a reactive linseed oil composition. The amount of steam blown was about 0.5 part.
[0012]
Example 2 Production Example of Reactive Linseed Oil Composition 100 parts of N / B linseed oil were subjected to nitrogen distillation at 250 ° C. and 1 mmHg for 3 hours to obtain 99.5 parts of a reactive linseed oil composition.
[0013]
Example 3 Production Example of Reactive Linseed Oil Composition 40 parts of N / B linseed oil was added to a column filled with 1000 parts of silica gel (manufactured by Fuji Silysia Chemical Ltd.), and a hexane-ether (9: 1) solvent was used. Then, 39.8 parts of a reactive linseed oil composition was obtained.
[0014]
Comparative Example 1 Comparative Production Example of Lightly Refined Linseed Oil Composition 100 parts of N / B linseed oil were subjected to steam distillation at 150 ° C. and 1 mmHg for 1 hour to obtain 99.6 parts of a reactive linseed oil composition. The amount of steam blown was about 0.5 part.
[0015]
Comparative Example 2 Comparative Production Example of Lightly Refined Linseed Oil Composition Flaxseed crude oil (manufactured by Nisshin Oil Co., Ltd.) was used as the lightly refined linseed oil.
[0016]
Comparative Example 3 Comparative Production Example of Lightly Refined Linseed Oil Composition N / B linseed oil (manufactured by Nisshin Oil Co., Ltd.) was used as the lightly refined linseed oil.
About the obtained linseed oil and fat composition, the drying time and the conjugate isomerization reaction rate were measured.
[0017]
[Table 1]
From Examples 1 to 3 and Comparative Examples 1 to 3, the reactive linseed oil / fat composition of the present invention is compared with the lightly purified linseed oil / fat composition by oxidative polymerization (normal drying), thermal polymerization (baking), It was found that the conjugate isomerization reactivity was excellent. In addition, when this is added to a photoreactive resin such as an acrylic resin and cured, compared to a resin to which lightly refined linseed oil is added, inhibition of curing of the resin is reduced, and a resin having a high degree of polymerization can be obtained. I understood.
[0019]
Example 4 Production Example of Reactive Linseed Oil / Fat Composition Modified Alkyd Resin 43.6 parts of phthalic anhydride and 21.8 parts of glycerin were reacted at 180 ° C. for 5 hours, and this was obtained by deodorization in Example 1. 40.0 parts of the reactive linseed oil / fat composition was added, and the mixture was reacted at 220 ° C. for 10 hours to esterify free hydroxyl groups, thereby obtaining 100 parts of a reactive linseed oil / fat composition-modified alkyd resin.
[0020]
Comparative Example 4 Comparative Production Example of Conventional Reactive Linseed Oil-Fat Composition Modified Alkyd Resin 43.6 parts of phthalic anhydride and 21.8 parts of glycerin were reacted at 180 ° C. for 5 hours. (Manufactured by Toshosha Co., Ltd.), and reacted at 220 ° C. for 10 hours to esterify free hydroxyl groups, thereby obtaining 100 parts of a conventional reactive linseed oil / fat composition-modified alkyd resin.
[0021]
Comparative Example 5 Comparative Production Example of Conventional Reactive Linseed Oil-Fat Composition Modified Alkyd Resin 43.6 parts of phthalic anhydride and 21.8 parts of glycerin were reacted at 180 ° C. for 5 hours. (Manufactured by Oil Refinery Co., Ltd.), and 100 parts of a conventional reactive linseed oil / fat composition-modified alkyd resin was obtained in the same manner as in Comparative Example 4 below.
[0022]
Comparative Example 6 Comparative Production Example of Conventional Reactive Linseed Oil-Fat Composition Modified Alkyd Resin 43.6 parts of phthalic anhydride and 21.8 parts of glycerin were reacted at 180 ° C. for 5 hours, and a stand oil (Nisshin Oil Co., Ltd.) was added thereto. 40.0 parts of stand oil L-2) was added, and 100 parts of a conventional reactive linseed oil / fat composition-modified alkyd resin was obtained in the same manner as in Comparative Example 4 below.
[0023]
Comparative Example 7 Comparative Production Example of Conventional Reactive Linseed Oil-Fat Composition Modified Alkyd Resin 43.6 parts of phthalic anhydride and 21.8 parts of glycerin were reacted at 180 ° C. for 5 hours, and an isomerized oil (Nisshin Oil) was added. And NC-101) (40.0 parts), and 100 parts of a conventional reactive linseed oil / fat composition-modified alkyd resin was obtained in the same manner as in Comparative Example 4 below.
The obtained alkyd resin coating was measured for adhesion and solvent resistance. Further, the polymer content in the linseed oil / fat composition as a resin raw material was measured.
[0024]
[Table 2]
From Example 4 and Comparative Examples 4 to 7, the coating resin containing the reactive linseed oil / fat composition of the present invention, which has less thermal damage, has higher adhesion and solvent resistance than the conventional reactive linseed oil / fat composition. It turned out that it was excellent. It is considered that a low molecular weight decomposed product generated during the production process of the conventional reactive linseed oil composition affects the adhesion and solvent resistance of the resin containing the same.
[0026]
【The invention's effect】
According to the present invention, the raw linseed oil is highly refined to increase the reactivity of reactions involving radicals such as thermopolymerization, oxidative polymerization, and conjugate isomerization, as compared with lightly refined linseed oil. A reactive linseed oil composition is obtained. In addition, compared to conventional boil oil, stand oil, isomerized oil, etc., the thermal damage is small and the content of decomposition products is small. It is possible to provide a paint or ink which is good, has a low possibility of dissolving or volatilizing a decomposed product after drying, and has good color and odor.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22856299A JP3598025B2 (en) | 1999-08-12 | 1999-08-12 | Reactive linseed oil composition and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22856299A JP3598025B2 (en) | 1999-08-12 | 1999-08-12 | Reactive linseed oil composition and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001049289A JP2001049289A (en) | 2001-02-20 |
| JP3598025B2 true JP3598025B2 (en) | 2004-12-08 |
Family
ID=16878324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22856299A Expired - Fee Related JP3598025B2 (en) | 1999-08-12 | 1999-08-12 | Reactive linseed oil composition and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3598025B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10302299A1 (en) * | 2003-01-22 | 2004-07-29 | Cognis Deutschland Gmbh & Co. Kg | Deodorization of oils comprises treatment with a polymeric adsorbent in addition to distillation with steam or a carrier gas |
| JP4524547B2 (en) * | 2003-07-16 | 2010-08-18 | 株式会社カネカ | Oil and fat composition manufacturing method and oil and fat composition using the same |
| KR101053272B1 (en) * | 2004-12-21 | 2011-08-01 | 에스케이종합화학 주식회사 | Solvent composition for newspaper ink and its manufacturing method |
| RU2008100219A (en) | 2005-06-21 | 2009-07-27 | Дзе Кока-Кола Компани (US) | METHOD FOR REMOVING IMPURITIES FROM ESSENTIAL OILS |
| CN102482614A (en) * | 2009-07-21 | 2012-05-30 | 雀巢产品技术援助有限公司 | Process for the preparation of deodorized edible oils or fats containing low levels of bound MCPD and purified by carboxymethylcellulose and/or resins |
| CN109337759A (en) * | 2018-11-28 | 2019-02-15 | 宁夏君星坊食品科技有限公司 | A method of removing linseed oil bitter taste |
| JP7628362B2 (en) * | 2020-03-26 | 2025-02-10 | 日清オイリオグループ株式会社 | Method for producing fatty acids |
| CN115651539B (en) * | 2022-10-28 | 2023-06-02 | 金华市美林涂料有限公司 | High-solid low-viscosity wood wax oil and preparation method thereof |
| CN115975505B (en) * | 2022-12-01 | 2023-08-25 | 金华市美林涂料有限公司 | Ultraviolet light resistant wood wax oil and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07188692A (en) * | 1993-12-27 | 1995-07-25 | Ikeda Shiyokuken Kk | Method for removing peroxide from composition containing highly unsaturated fatty acids |
| JP3444728B2 (en) * | 1996-08-23 | 2003-09-08 | 日清オイリオ株式会社 | Curable ester base and curable composition containing the same |
-
1999
- 1999-08-12 JP JP22856299A patent/JP3598025B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001049289A (en) | 2001-02-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3598025B2 (en) | Reactive linseed oil composition and method for producing the same | |
| Bilal et al. | Photocatalytic degradation, toxicological assessment and degradation pathway of CI Reactive Blue 19 dye | |
| JP5131953B2 (en) | Composite membrane | |
| DE1081234B (en) | Process for polymerizing conjugated diolefins, especially isoprene | |
| WO2012066860A1 (en) | Method for producing regenerated clay, regenerated clay, and method for producing purified fats and oils | |
| CA2423698A1 (en) | Process for treating oils containing antioxidant compounds | |
| CA1142881A (en) | Separation process for acrylic polymers or cololymers soluble in water, with a high molecular weight and a low residual monomer(s) content | |
| KR20100119343A (en) | Method for preparing deodored and decolored fucoidan | |
| RU2152405C1 (en) | Method of clarifying substantially noncrystalline hydrocarbon resins | |
| JPH06296865A (en) | Method of regenerating used acid activated smectite clay and carbonizing the same optionally | |
| RU2708629C1 (en) | Desulfurization method of heavy oil product using microwave radiation | |
| CN101416931A (en) | Plant whitening agent and preparation method thereof | |
| CN111344061A (en) | an oxidant activator | |
| CN111804281A (en) | A kind of nano-adsorbent for vegetable oil decolorization, its pre-radiation synthesis method and application | |
| DE1093091B (en) | Process for the production of a copolymer from isoprene and styrene or butadiene | |
| JPH02145623A (en) | Deodorizing hydrogenated polyisobutylene for cosmetic | |
| JPS5811477B2 (en) | How to bleach wool wax | |
| US1871082A (en) | Bleaching artificial fatty acids | |
| CN100366701C (en) | Refining method of ultraviolet absorber, ultraviolet absorber and cosmetic raw material | |
| US2128984A (en) | Treatment of still residue | |
| JP2694184B2 (en) | Beeswax refining method | |
| US1180025A (en) | Process of making a thickened-oil product. | |
| JPS6393349A (en) | Adsorbent | |
| KR102882731B1 (en) | Carbon quantum dots loaded dressing material for antiaging and wound-healing applications and Method of preparing the same | |
| JPS6393348A (en) | Adsorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040318 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040427 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20040519 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040624 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20040701 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040831 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040910 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100917 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130917 Year of fee payment: 9 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |