TWI831967B - Zinc carboxylate composition and zinc carboxylate solution containing the zinc carboxylate composition - Google Patents
Zinc carboxylate composition and zinc carboxylate solution containing the zinc carboxylate composition Download PDFInfo
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- TWI831967B TWI831967B TW109114542A TW109114542A TWI831967B TW I831967 B TWI831967 B TW I831967B TW 109114542 A TW109114542 A TW 109114542A TW 109114542 A TW109114542 A TW 109114542A TW I831967 B TWI831967 B TW I831967B
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- carboxylic acid
- zinc carboxylate
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- zinc
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- -1 Zinc carboxylate Chemical class 0.000 title claims abstract description 93
- 239000011701 zinc Substances 0.000 title claims abstract description 65
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 150000001721 carbon Chemical group 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 14
- 229920006395 saturated elastomer Polymers 0.000 abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 46
- 229910052751 metal Inorganic materials 0.000 description 34
- 239000002184 metal Substances 0.000 description 34
- 229910052783 alkali metal Inorganic materials 0.000 description 27
- 150000003839 salts Chemical class 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 150000003751 zinc Chemical class 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002096 quantum dot Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005649 metathesis reaction Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 4
- 235000020778 linoleic acid Nutrition 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UWHZIFQPPBDJPM-FPLPWBNLSA-M Vaccenic acid Natural products CCCCCC\C=C/CCCCCCCCCC([O-])=O UWHZIFQPPBDJPM-FPLPWBNLSA-M 0.000 description 2
- 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 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- DJCQJZKZUCHHAL-UHFFFAOYSA-N (Z)-9-Pentadecensaeure Natural products CCCCCC=CCCCCCCCC(O)=O DJCQJZKZUCHHAL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 235000021322 Vaccenic acid Nutrition 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UWHZIFQPPBDJPM-FPLPWBNLSA-N cis-vaccenic acid Chemical compound CCCCCC\C=C/CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-FPLPWBNLSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-AVQMFFATSA-N linoelaidic acid Chemical compound CCCCC\C=C\C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-AVQMFFATSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
本發明在使羧酸鋅溶解於溶劑、或者使羧酸鋅自身熔融而進行使用的用途中，提高羧酸鋅的黏度穩定性、耐熱性、及溶解穩定性。構成羧酸鋅組合物的羧酸含有0.5~6.0質量%的成分(A)、0.05~1.2質量%的成分(B)，及88.0~98.0質量%的成分(C)，成分(A)相對於成分(B)的質量比[(A)/(B)]為99/1~75/25。 The present invention improves the viscosity stability, heat resistance, and dissolution stability of zinc carboxylate in applications where zinc carboxylate is dissolved in a solvent or zinc carboxylate itself is melted and used. The carboxylic acid constituting the zinc carboxylate composition contains 0.5 to 6.0 mass % of component (A), 0.05 to 1.2 mass % of component (B), and 88.0 to 98.0 mass % of component (C). The component (A) is The mass ratio [(A)/(B)] of component (B) is 99/1~75/25.
(A)碳原子數為12~22的直鏈飽和羧酸。 (A) Straight-chain saturated carboxylic acid with 12 to 22 carbon atoms.
(B)具有1個不飽和鍵，且不飽和鍵為反式雙鍵的碳原子數為18的直鏈不飽和羧酸。 (B) A linear unsaturated carboxylic acid having 18 carbon atoms and having one unsaturated bond, and the unsaturated bond is a trans double bond.
(C)具有1個不飽和鍵，且不飽和鍵為順式雙鍵的碳原子數為18的直鏈不飽和羧酸。 (C) A linear unsaturated carboxylic acid having 18 carbon atoms and having one unsaturated bond, and the unsaturated bond is a cis double bond.
Description
本發明涉及一種能夠提高羧酸鋅的耐熱性(低色調)、黏度穩定性、溶解穩定性的羧酸金屬鹽。羧酸鋅能夠用於：用於防止金屬彼此的磨損的潤滑脂的增稠劑、潤滑油用添加劑、半導體的量子點的前驅體原料等、在製造製程中使羧酸鋅溶解於溶劑或油、或者使羧酸鋅自身熔融而進行使用的用途中。 The present invention relates to a carboxylic acid metal salt capable of improving the heat resistance (low tone), viscosity stability, and dissolution stability of zinc carboxylate. Zinc carboxylate can be used as a thickener for greases to prevent the wear of metals, additives for lubricating oils, precursor materials for quantum dots in semiconductors, etc. Zinc carboxylate can be dissolved in solvents or oils during the manufacturing process. , or in applications where zinc carboxylate itself is melted and used.
以往，廣泛知曉羧酸金屬鹽可用於：用於防止金屬彼此的磨損的潤滑脂的增稠劑、潤滑油用添加劑、半導體的量子點的前驅體原料等、在製造製程中使羧酸鋅溶解於溶劑或油、或者使羧酸鋅自身熔融而進行使用的用途中。 In the past, it has been widely known that metal carboxylate salts can be used as thickeners in greases to prevent wear between metals, as additives for lubricating oils, as precursor materials for quantum dots in semiconductors, etc., and to dissolve zinc carboxylates in the manufacturing process. In applications where zinc carboxylate itself is melted and used in solvents or oils.
例如，只要為潤滑脂用增稠劑，則在機械裝置進行運作時，部件彼此會發生滑動接觸或者旋轉接觸，從而使金屬表面發生磨損。出於防止因此產生的金屬表面的磨損的目的或出於控制磨損的目的，使用有羧酸鋅。 For example, if a thickener is used for grease, when the mechanical device is operating, parts will come into sliding or rotational contact with each other, causing wear on the metal surface. Zinc carboxylates are used for the purpose of preventing the resulting wear of metal surfaces or for controlling wear.
專利文獻1中，記載有由黏度指數為190以下、40℃下的動態黏度為200mm2/s以上的基礎油與硬脂酸鋅組成的潤滑脂組合物。 Patent Document 1 describes a grease composition composed of a base oil and zinc stearate having a viscosity index of 190 or less and a dynamic viscosity at 40°C of 200 mm 2 /s or more.
此外，作為用於得到量子點的鋅前驅體，使用有油酸鋅，可將其在高溫下熔解而用作反應原料。進一步，引用文獻2涉及用於得到量子點的鋅前驅體溶液的製備，並記載有使醋酸鋅與油酸在1-十八碳烯中於120℃反應1小時而得到油酸鋅溶液。 In addition, as a zinc precursor for obtaining quantum dots, zinc oleate is used, which can be melted at high temperature and used as a reaction raw material. Furthermore, Cited Document 2 relates to the preparation of a zinc precursor solution for obtaining quantum dots, and describes that zinc acetate and oleic acid are reacted in 1-octadecene at 120° C. for 1 hour to obtain a zinc oleate solution.
現有技術文獻 existing technical documents
專利文獻 patent documents
專利文獻1：日本特開2016-121296號公報 Patent Document 1: Japanese Patent Application Publication No. 2016-121296
專利文獻2：日本特開2011-194562號公報 Patent Document 2: Japanese Patent Application Publication No. 2011-194562
然而，專利文獻1記載的潤滑脂組合物雖然能夠降低滑動載荷，且能夠賦予高潤滑性，但對於更高的高黏度狀態的環境領域下羧酸金屬鹽在基礎油中的溶解穩定性方面，仍存在技術問題。此外，使其熔融而進行使用時，若保持熔融狀態，則色調因著色而發生變化、或者黏度變化因攪拌條件而變大，存在產生品質差異的風險。進一步，專利文獻2記載的油酸鋅溶液有時會發生分離，存在無法得到品質穩定的量子點的風險。 However, although the grease composition described in Patent Document 1 can reduce the sliding load and provide high lubricity, it has problems with the dissolution stability of the carboxylic acid metal salt in the base oil in the environmental field of a higher high viscosity state. There are still technical issues. In addition, when it is melted and used, if it remains in a molten state, the color tone may change due to coloring, or the viscosity change may increase depending on the stirring conditions, thereby risking quality differences. Furthermore, the zinc oleate solution described in Patent Document 2 may separate, and there is a risk that quantum dots with stable quality cannot be obtained.
本發明的技術問題在於，在使羧酸鋅溶解於溶劑或使羧酸鋅熔融而進行使用的用途中，提高羧酸鋅的耐熱性(低色調)、黏度穩定性及溶解穩定性。 The technical problem of the present invention is to improve the heat resistance (low color tone), viscosity stability and dissolution stability of zinc carboxylate in applications where zinc carboxylate is dissolved in a solvent or melted and used.
本申請的發明入為了解決上述技術問題而進行了深入研究，結果發現，當構成羧酸鋅組合物的羧酸具有特定組成時，在使其溶解於溶劑而進行使用的用途中，能夠提高羧酸金屬鹽的耐熱性、黏度穩定性，及溶解穩定性，從而完成了本發明。 The inventors of the present application conducted intensive studies to solve the above technical problems, and as a result found that when the carboxylic acid constituting the zinc carboxylate composition has a specific composition, the carboxylic acid can improve the carboxylic acid content in an application in which it is dissolved in a solvent and used. The invention was completed by considering the heat resistance, viscosity stability, and dissolution stability of the acid metal salt.
即，本發明為下述(1)及(2)。 That is, the present invention is the following (1) and (2).
(1)一種羧酸鋅組合物，其特徵在於，構成羧酸鋅組合物的羧酸含有0.5~6.0質量%的下述成分(A)、0.05~1.2質量%的下述成分(B)，及88.0~98.0質量%的下述成分(C)，且成分(A)相對於成分(B)的質量比[(A)/(B)]為99/1~75/25。 (1) A zinc carboxylate composition, characterized in that the carboxylic acid constituting the zinc carboxylate composition contains 0.5 to 6.0 mass % of the following component (A) and 0.05 to 1.2 mass % of the following component (B), and 88.0 to 98.0 mass % of the following component (C), and the mass ratio [(A)/(B)] of component (A) to component (B) is 99/1 to 75/25.
(A)碳原子數為12~22的直鏈飽和羧酸。 (A) Straight-chain saturated carboxylic acid with 12 to 22 carbon atoms.
(B)具有1個不飽和鍵，且所述不飽和鍵為反式雙鍵的碳原子數為18的直鏈不飽和羧酸。 (B) A linear unsaturated carboxylic acid having 18 carbon atoms and having one unsaturated bond, and the unsaturated bond is a trans double bond.
(C)具有1個不飽和鍵，且所述不飽和鍵為順式雙鍵的碳原子數為18的直鏈不飽和羧酸。 (C) A linear unsaturated carboxylic acid with 18 carbon atoms having one unsaturated bond, and the unsaturated bond is a cis double bond.
(2)一種羧酸鋅溶液，其特徵在於，其含有(1)的羧酸鋅組合物與溶劑，所述羧酸鋅組合物的含量為0.01~30質量%。 (2) A zinc carboxylate solution, characterized in that it contains the zinc carboxylate composition of (1) and a solvent, and the content of the zinc carboxylate composition is 0.01 to 30 mass%.
根據本發明，能夠在使塗料的乾燥劑、潤滑油用添加劑、量子點的前驅體原料等羧酸鋅溶解於溶劑而進行使用的用途中，提高本發明的羧酸鋅的耐熱性、黏度穩定性，及溶解穩定性。 According to the present invention, the heat resistance and viscosity stability of the zinc carboxylate of the present invention can be improved in applications where zinc carboxylate is dissolved in a solvent and used as a desiccant for paint, an additive for lubricating oil, and a precursor material for quantum dots. properties, and solubility stability.
(羧酸鋅組合物) (Zinc carboxylate composition)
對於作為羧酸鹼金屬鹽的原料的羧酸的組成，包含上述的成分(A)、成分(B)及成分(C)。 The composition of the carboxylic acid which is the raw material of the carboxylic acid alkali metal salt includes the above-mentioned component (A), component (B) and component (C).
此處，成分(A)為碳原子數為12~22的直鏈飽和羧酸。該直鏈飽和羧酸的碳原子數進一步優選為14以上，進一步優選為20以下。此外，成分(A)可以為一種，也可以為兩種以上。 Here, component (A) is a linear saturated carboxylic acid having 12 to 22 carbon atoms. The number of carbon atoms of the linear saturated carboxylic acid is more preferably 14 or more, and still more preferably 20 or less. In addition, the component (A) may be one type or two or more types.
成分(B)為具有1個不飽和鍵，且所述不飽和鍵為反式雙鍵的碳原子數為18的直鏈不飽和羧酸。該羧酸不具有三鍵、順式雙鍵。此外，成分(B)可以為一種，也可以為兩種以上。 Component (B) is a linear unsaturated carboxylic acid having 18 carbon atoms and having one unsaturated bond which is a trans double bond. This carboxylic acid does not have triple bonds or cis double bonds. In addition, the component (B) may be one type or two or more types.
作為成分(B)中的反式雙鍵的位置，沒有特別限定，能夠優選列舉出在9位具有雙鍵的反油酸、在11位具有雙鍵的異油酸，更優選反油酸。 The position of the trans double bond in component (B) is not particularly limited, but preferred examples include elaidic acid having a double bond at position 9 and vaccenic acid having a double bond at position 11, with elaidic acid being more preferred.
成分(C)為具有1個不飽和鍵，且不飽和鍵為順式雙鍵的碳原子數為18的直鏈不飽和羧酸。該羧酸不具有三鍵、反式雙鍵。此外，成分(C)可以為一種，也可以為兩種以上。 Component (C) is a linear unsaturated carboxylic acid having 18 carbon atoms and having one unsaturated bond, and the unsaturated bond is a cis double bond. This carboxylic acid does not have triple bonds or trans double bonds. In addition, the component (C) may be one type or two or more types.
作為成分(C)中的順式雙鍵的位置，沒有特別限定，能夠優選列舉出在9位具有雙鍵的油酸、在11位具有雙鍵的順式-異油酸，更優選油酸。 The position of the cis double bond in component (C) is not particularly limited, but preferred examples include oleic acid having a double bond at position 9 and cis-vaccenic acid having a double bond at position 11, with oleic acid being more preferred. .
將構成羧酸鋅組合物的羧酸的合計量設為100質量%時，將成分(A)的量設為0.5~6.0質量%。成分(A)的量小於0.5質量%時，所得到的 羧酸鋅組合物的觸變指數變大，溶解穩定性變低，因此設為0.5質量%以上，進一步優選為1.5質量%以上。另一方面，成分(A)的量大於6.0質量%時，在溶解時發生析出，穩定性變差，因此設為6.0質量%以下，進一步優選設為5.5質量%以下。 When the total amount of carboxylic acids constituting the zinc carboxylate composition is 100% by mass, the amount of component (A) is 0.5 to 6.0% by mass. When the amount of component (A) is less than 0.5% by mass, the resultant The thixotropic index of the zinc carboxylate composition becomes large and the dissolution stability becomes low, so the content is 0.5 mass% or more, and more preferably 1.5 mass% or more. On the other hand, if the amount of component (A) exceeds 6.0 mass %, precipitation occurs during dissolution and the stability becomes poor, so the amount is 6.0 mass % or less, and more preferably 5.5 mass % or less.
將構成羧酸鋅組合物的羧酸的合計量設為100質量%時，將成分(B)的量設為0.05~1.2質量%。由此，溶解穩定性得以提高。從這樣的角度出發，成分(B)的量進一步優選為0.10質量%以上，此外，進一步優選為1.0質量%以下。 When the total amount of carboxylic acids constituting the zinc carboxylate composition is 100% by mass, the amount of component (B) is 0.05 to 1.2% by mass. As a result, dissolution stability is improved. From this point of view, the amount of component (B) is more preferably 0.10 mass% or more, and further preferably 1.0 mass% or less.
將構成羧酸鋅組合物的羧酸的合計量設為100質量%時，將成分(C)的量設為88.0~98.0質量%。由此，色相變好，溶解穩定性得以提高。從這樣的角度出發，對於(C)，成分(C)的量進一步優選為89.0質量%以上，此外，進一步優選為95.0質量%以下。 When the total amount of carboxylic acids constituting the zinc carboxylate composition is 100% by mass, the amount of component (C) is 88.0 to 98.0% by mass. This improves the hue and improves dissolution stability. From such a viewpoint, regarding (C), the amount of component (C) is more preferably 89.0 mass% or more, and further preferably 95.0 mass% or less.
本發明中，將成分(A)相對於成分(B)的質量比[(A)/(B)]設為99/1~75/25。由此，溶解穩定性得以提高。從這樣的角度出發，質量比[(A)/(B)]進一步優選為98/2~80/20。 In the present invention, the mass ratio [(A)/(B)] of component (A) to component (B) is set to 99/1 to 75/25. As a result, dissolution stability is improved. From this point of view, the mass ratio [(A)/(B)] is further preferably 98/2 to 80/20.
構成本發明的羧酸鋅組合物的羧酸可以由成分(A)、(B)及(C)組成，或者，除了成分(A)、(B)及(C)，可以進一步含有其他成分(D)作為剩餘部分。即，其他成分(D)的含量為從100質量%中扣除成分(A)、(B)及(C)的合計量後的剩餘部分，優選為10質量%以下，進一步優選為5質量%以下，也可以為0.0質量%。 The carboxylic acid constituting the zinc carboxylate composition of the present invention may be composed of components (A), (B) and (C), or may further contain other components (A), (B) and (C) in addition to components (A), (B) and (C). D) as the remainder. That is, the content of other component (D) is the remainder after subtracting the total amount of components (A), (B), and (C) from 100 mass %, and is preferably 10 mass % or less, more preferably 5 mass % or less. , it can also be 0.0 mass%.
構成其他成分(D)的羧酸優選具有2個以上的雙鍵，進一步優選具有2或3個雙鍵。此外，構成其他成分(D)的羧酸的碳原子數優選為16~22，進一步優選為16~18，特別優選為18。 The carboxylic acid constituting the other component (D) preferably has two or more double bonds, and more preferably has 2 or 3 double bonds. In addition, the number of carbon atoms of the carboxylic acid constituting the other component (D) is preferably 16 to 22, more preferably 16 to 18, and particularly preferably 18.
對於成分(D)中的雙鍵，可以為順式，也可以為反式，作為雙鍵的位置，能夠優選列舉出在9位與12位具有順式雙鍵的亞油酸、在9位與12位具有反式雙鍵的反式亞油酸(linoelaidic acid)、在9位、12位、15位具有順式雙鍵的亞麻酸，更優選亞油酸與亞麻酸，進一步優選亞油酸。 The double bond in component (D) may be cis or trans. As the position of the double bond, linoleic acid having a cis double bond at the 9-position and 12-position, and linoleic acid having a cis double bond at the 9-position may be preferably used. trans-linoleic acid (linoelaidic acid) having a trans double bond at position 12, linolenic acid having cis double bonds at position 9, 12, and 15, more preferably linoleic acid and linolenic acid, and even more preferably linoleic acid acid.
(羧酸鋅組合物的製法) (Method for producing zinc carboxylate composition)
作為羧酸金屬鹽的主要製備方法，有直接法與複分解法。直接法為通過熔融羧酸與金屬氧化物或金屬氫氧化物的直接反應而得到羧酸金屬鹽的方法。另一方面，複分解法為通過羧酸鹼金屬鹽的水溶液與無機金屬鹽的反應而得到羧酸金屬鹽的方法。 As the main preparation methods of carboxylic acid metal salts, there are direct method and metathesis method. The direct method is a method of obtaining a carboxylic acid metal salt through a direct reaction between a molten carboxylic acid and a metal oxide or metal hydroxide. On the other hand, the metathesis method is a method of obtaining a carboxylic acid metal salt by reaction of an aqueous solution of a carboxylic acid alkali metal salt and an inorganic metal salt.
直接法具有製程簡略、設備規模小等設備上的優點，但另一方面，存在以下的技術問題。 The direct method has the advantages of simple manufacturing process and small equipment scale, but on the other hand, it has the following technical problems.
(a)缺乏反應的完結性，在羧酸金屬鹽中殘留大量未反應的羧酸、原料的金屬氧化物或金屬氫氧化物。(b)由於在高溫下進行反應，因此羧酸金屬鹽的色相差。 (a) The completion of the reaction is lacking, and a large amount of unreacted carboxylic acid, metal oxide or metal hydroxide of the raw material remains in the carboxylic acid metal salt. (b) Since the reaction proceeds at high temperature, the carboxylic acid metal salt has a color difference.
(c)由於缺乏反應性，以往使金屬氧化物或金屬氫氧化物相對於羧酸以等摩爾以上進行反應，因此所得到的羧酸金屬鹽中殘留鹼性羧酸金屬鹽(單鹽)，熔點變高，或者溶解性降低。 (c) Due to lack of reactivity, metal oxides or metal hydroxides have been conventionally reacted in equimolar or higher amounts with respect to carboxylic acids, so that a basic carboxylic acid metal salt (single salt) remains in the resulting carboxylic acid metal salt, The melting point becomes higher or the solubility decreases.
另一方面，複分解法與上述直接法完全相反，具有未反應的羧酸、原料的金屬化合物、不同種類的金屬等的含量少、色相好、為微粉末等的品質上的優點，但另一方面，也存在以下的技術問題。 On the other hand, the metathesis method is completely opposite to the above-mentioned direct method. It has the quality advantages of having a small content of unreacted carboxylic acid, metal compounds of raw materials, different types of metals, etc., good color, and fine powder. However, on the other hand, In this regard, there are also the following technical problems.
(a)需要巨大的製造設備。 (a) Huge manufacturing equipment is required.
(b)反應漿料在水中的分散性不穩定，作業性差。(c)難以降低製品的水分。 (b) The dispersion of the reaction slurry in water is unstable and the workability is poor. (c) It is difficult to reduce the moisture content of the product.
本發明的羧酸鋅組合物可以採用直接法或複分解法中的任意一種製法，從提高熔融狀態下的耐熱性、黏度穩定性、提高溶劑中的溶解穩定性的角度出發，進一步優選利用複分解法得到的羧酸鋅組合物。 The zinc carboxylate composition of the present invention can be produced by either the direct method or the metathesis method. From the perspective of improving the heat resistance and viscosity stability in the molten state and improving the dissolution stability in the solvent, the metathesis method is further preferably used. The obtained zinc carboxylate composition.
作為成為羧酸鹼金屬鹽的原料的一價堿化合物，可列舉出鹼金屬(鈉、鉀等)的氫氧化物，及氨、單乙醇胺、二乙醇胺、三乙醇胺等胺類等。從製成羧酸鹼金屬鹽時對水的溶解度高的點、耐著色性的角度出發，優選為鈉、鉀等鹼金屬的氫氧化物。一般以羧酸的熔點以上、且該羧酸不發生分解的程度的溫度、優選以40~85℃、更優選以50~80℃、進一步優選以60~75℃，使一價堿化合物與羧酸反應，從而得到羧酸鹼金屬鹽。 Examples of monovalent chlorine compounds used as raw materials for carboxylic acid alkali metal salts include hydroxides of alkali metals (sodium, potassium, etc.), and amines such as ammonia, monoethanolamine, diethanolamine, and triethanolamine. From the viewpoint of high solubility in water and coloring resistance when used as an alkali metal carboxylate salt, hydroxides of alkali metals such as sodium and potassium are preferred. Generally, the monovalent chlorine compound and the carboxyl compound are reacted at a temperature above the melting point of the carboxylic acid and at which the carboxylic acid does not decompose, preferably 40 to 85°C, more preferably 50 to 80°C, and still more preferably 60 to 75°C. The acid reacts to obtain an alkali metal carboxylate.
本發明的二價羧酸鋅為通過使上述得到的羧酸鹼金屬鹽、與二價鋅鹽在水溶液中進行反應而得到的羧酸金屬鹽顆粒。具體而言，上述二價鋅鹽為二價鋅金屬與無機酸或有機酸的鹽。作為二價無機鋅鹽，優選硫酸鋅、氯化鋅、硝酸鋅。其中，從工業上能夠容易獲得的點出發，特別優選硫酸鋅、氯化鋅。 The zinc divalent carboxylate of the present invention is a metal carboxylate particle obtained by reacting the alkali metal carboxylate obtained above with a divalent zinc salt in an aqueous solution. Specifically, the above-mentioned divalent zinc salt is a salt of divalent zinc metal and an inorganic acid or an organic acid. As the divalent inorganic zinc salt, zinc sulfate, zinc chloride, and zinc nitrate are preferred. Among these, zinc sulfate and zinc chloride are particularly preferred from the viewpoint of being easily available industrially.
具體而言，上述反應通過分別製備含二價鋅鹽的水溶液及含羧酸鹼金屬鹽的水溶液後，將它們混合而進行。例如通過向含羧酸鹼金屬 鹽的水溶液中添加含二價鋅鹽的水溶液、或者通過在另一個反應槽內添加兩者而進行。 Specifically, the above reaction is performed by separately preparing an aqueous solution containing a divalent zinc salt and an aqueous solution containing an alkali metal carboxylate salt, and then mixing them. For example, by adding a carboxylic acid-containing alkali metal The aqueous solution containing a divalent zinc salt is added to the aqueous salt solution, or both are added to another reaction tank.
在混合含羧酸鹼金屬鹽的水溶液與含二價鋅鹽的水溶液時，例如若向含羧酸鹼金屬鹽的水溶液中一次性添加含二價鋅鹽的水溶液，則所得到的羧酸金屬鹽顆粒的形狀會變得不均勻，存在粒度分布變廣的可能。此外，還存在析出的羧酸鋅發生凝聚的可能。因此，優選以適度的速度向含羧酸鹼金屬鹽的水溶液中逐漸滴加含二價鋅鹽的水溶液。 When mixing an aqueous solution containing an alkali metal carboxylate salt and an aqueous solution containing a divalent zinc salt, for example, if an aqueous solution containing a divalent zinc salt is added to the aqueous solution containing an alkali metal carboxylate salt at once, the resulting metal carboxylate The shape of the salt particles will become uneven, and there is a possibility that the particle size distribution will become wider. In addition, there is a possibility that the precipitated zinc carboxylate may aggregate. Therefore, it is preferable to gradually drop the aqueous solution containing the divalent zinc salt into the aqueous solution containing the alkali metal carboxylate at a moderate speed.
從羧酸金屬鹽的生產率的點，及含羧酸鹼金屬鹽的水溶液或所得到的羧酸金屬鹽漿料的操作性的點出發，製備羧酸金屬鹽時的羧酸鹼金屬鹽的濃度通常為1質量%~20質量%，優選為5質量%~15質量%。羧酸鹼金屬鹽的濃度小於1質量%時，羧酸金屬鹽的生產率可能會降低，在實際應用上不優選。羧酸鹼金屬鹽的濃度大於20質量%時，由於含羧酸鹼金屬鹽的水溶液或所得到的羧酸金屬鹽漿料的黏度會上升，因此有時難以進行均一的反應。 The concentration of the alkali metal carboxylate salt when preparing the metal carboxylate salt is determined from the viewpoint of the productivity of the metal carboxylate salt and the operability of the aqueous solution containing the alkali metal carboxylate salt or the resulting slurry of the metal carboxylate salt. It is usually 1 mass% to 20 mass%, preferably 5 mass% to 15 mass%. When the concentration of the alkali metal carboxylate salt is less than 1% by mass, the productivity of the metal carboxylate salt may decrease, which is not preferable in practical applications. When the concentration of the alkali metal carboxylate salt exceeds 20% by mass, the viscosity of the aqueous solution containing the alkali metal carboxylate salt or the resulting metal carboxylate salt slurry increases, making it sometimes difficult to perform a uniform reaction.
另外，從羧酸金屬鹽的生產率的點，及含羧酸鹼金屬鹽的水溶液或所得到的羧酸金屬鹽漿料的操作性的點出發，含二價鋅鹽的水溶液中的二價鋅鹽的濃度通常為10質量%~50質量%，優選為10質量%~40質量%。 In addition, from the viewpoint of the productivity of the carboxylic acid metal salt and the operability of the aqueous solution containing the carboxylic acid alkali metal salt or the obtained carboxylic acid metal salt slurry, the divalent zinc in the divalent zinc salt-containing aqueous solution The concentration of salt is usually 10 mass% to 50 mass%, preferably 10 mass% to 40 mass%.
考慮羧酸鹼金屬鹽的溶解度，羧酸鹼金屬鹽與二價鋅鹽的反應在所得到的羧酸金屬鹽的軟化點以下的溫度下進行，該溫度優選為40~85℃，更優選為50~80℃。該反應溫度小於40℃時，羧酸鹼金屬鹽與二價鋅鹽的反應率可能會降低。 Considering the solubility of the alkali metal carboxylate salt, the reaction between the alkali metal carboxylate salt and the divalent zinc salt is carried out at a temperature below the softening point of the obtained metal carboxylate salt. The temperature is preferably 40 to 85°C, and more preferably 50~80℃. When the reaction temperature is less than 40° C., the reaction rate between the alkali metal carboxylate salt and the divalent zinc salt may decrease.
出於在羧酸鹼金屬鹽與二價鋅鹽進行反應時使羧酸金屬鹽漿料穩定化、從而提高羧酸金屬鹽的生產率的目的，優選在羧酸金屬鹽漿料中存在聚亞烷基二醇類醚、特別是具有氧丙烯嵌段被氧乙烯嵌段夾持的結構(EO-PO-EO)的三嵌段醚。相對於羧酸鹼金屬鹽100質量份，羧酸金屬鹽漿料中的聚亞烷基二醇類醚的含量通常為0.01質量份~5質量份，優選為0.05質量份~2質量份。另外，可以使聚亞烷基二醇類醚在一價堿化合物與羧酸反應前存在於反應體系中，或者也可以在羧酸鹼金屬鹽與二價鋅鹽的反應前存在於反應體系中。 For the purpose of stabilizing the carboxylic acid metal salt slurry when the alkali metal carboxylic acid salt and the divalent zinc salt react, thereby improving the productivity of the carboxylic acid metal salt, it is preferable that polyalkylene is present in the carboxylic acid metal salt slurry. glycol ethers, especially triblock ethers having a structure (EO-PO-EO) in which an oxypropylene block is sandwiched by an oxyethylene block. The content of the polyalkylene glycol ether in the carboxylic acid metal salt slurry is usually 0.01 to 5 parts by mass, preferably 0.05 to 2 parts by mass relative to 100 parts by mass of the alkali metal carboxylate salt. In addition, the polyalkylene glycol ether may be present in the reaction system before the reaction between the monovalent chlorine compound and the carboxylic acid, or may be present in the reaction system before the reaction between the alkali metal carboxylic acid salt and the divalent zinc salt. .
通過上述方法，可得到羧酸金屬鹽漿料。直接、或者利用離心脫水機、壓濾機、真空旋轉過濾機等將溶劑分離，並根據需要進行洗滌，將副產生成的無機鹽去除後，利用櫃式乾燥機、旋轉乾燥機、氣流乾燥裝置、通氣式乾燥機、噴霧式乾燥機、流動層型乾燥裝置等，使該羧酸金屬鹽漿料乾燥。乾燥方法可以為連續式或間歇式、或者常壓或真空下中的任一種。進一步，根據需要將乾燥後的羧酸鋅粉碎。粉碎方法沒有特別限定，例如能夠利用銷棒粉碎機(pin mill)、氣流粉碎機(jet mill)、霧化器(atomizer)等。粉碎後的羧酸鋅顆粒被分級。即，使用施予振動而進行分篩的多段篩裝置等而進行分級，調節粒度分布。由此，能夠得到本發明的羧酸鋅的顆粒。 Through the above method, a carboxylic acid metal salt slurry can be obtained. Separate the solvent directly or by using a centrifugal dehydrator, filter press, vacuum rotary filter, etc., and wash it as needed. After removing the inorganic salts produced by the by-products, use a cabinet dryer, rotary dryer, or air flow drying device. , ventilation dryer, spray dryer, fluidized bed drying device, etc., to dry the carboxylic acid metal salt slurry. The drying method may be continuous or intermittent, or under normal pressure or vacuum. Furthermore, the dried zinc carboxylate is pulverized as necessary. The grinding method is not particularly limited, and for example, a pin mill, a jet mill, an atomizer, etc. can be used. The crushed zinc carboxylate particles are classified. That is, classification is performed using a multi-stage sieve device that applies vibration to perform sieving, and the particle size distribution is adjusted. Thus, the zinc carboxylate particles of the present invention can be obtained.
(羧酸鋅組合物的物性) (Physical properties of zinc carboxylate composition)
對於本發明的羧酸鋅組合物，從溶劑中的分散性、溶解穩定性的角度出發，黏度穩定性(利用B型黏度計測定的於100℃熔解後的試料 的1rpm時的黏度除以2.5rpm時的黏度而得到的值)為1.04~1.10，優選為1.04~1.09。 Regarding the zinc carboxylate composition of the present invention, from the viewpoint of dispersibility and dissolution stability in a solvent, the viscosity stability (sample after melting at 100°C measured using a B-type viscometer The value obtained by dividing the viscosity at 1 rpm by the viscosity at 2.5 rpm) is 1.04 to 1.10, preferably 1.04 to 1.09.
此外，從耐熱性(低色調)的角度出發，於100℃使其熔融時，色調以加德納(gardner)計優選為3以下，進一步優選為2以下。進一步，在100℃下保持1小時熔融狀態時，色調以加德納計優選為4以下，進一步優選為3以下。作為色調變化，保持1小時後的色調與剛熔融後的色調的差以加德納計優選為2以下，進一步優選為1以下。 In addition, from the viewpoint of heat resistance (low color tone), when melted at 100° C., the color tone is preferably 3 or less in Gardner (gardner), and more preferably 2 or less. Furthermore, when the molten state is maintained at 100° C. for 1 hour, the color tone is preferably 4 or less on a Gardner scale, and more preferably 3 or less. As a change in color tone, the difference between the color tone after holding for 1 hour and the color tone immediately after melting is preferably 2 or less in Gardner's terms, and more preferably 1 or less.
(羧酸鋅溶液) (zinc carboxylate solution)
用於使本發明的羧酸鋅組合物溶解的溶劑沒有特別限制，從羧酸鋅組合物的溶解性的角度出發，適宜列舉出具有170℃以上的沸點的非極性溶劑。作為非極性溶劑，具體而言，例如可列舉出正癸烷、正十二烷、正十六烷、正十八烷等脂肪族飽和烴；1-癸烯、1-十二碳烯、1-十六碳烯、1-十八碳烯等脂肪族不飽和烴；三辛基膦等。 The solvent used to dissolve the zinc carboxylate composition of the present invention is not particularly limited. From the viewpoint of the solubility of the zinc carboxylate composition, non-polar solvents having a boiling point of 170° C. or higher are suitably used. Specific examples of the nonpolar solvent include aliphatic saturated hydrocarbons such as n-decane, n-dodecane, n-hexadecane, and n-octadecane; 1-decene, 1-dodecene, 1 - Aliphatic unsaturated hydrocarbons such as hexadecene and 1-octadecene; trioctylphosphine, etc.
其中，優選脂肪族飽和烴，更優選碳原子數為12~18的脂肪族飽和烴。 Among them, aliphatic saturated hydrocarbons are preferred, and aliphatic saturated hydrocarbons having 12 to 18 carbon atoms are more preferred.
本發明的羧酸鋅溶液中，將溶劑與羧酸鋅組合物的合計量設為100質量%時，優選含有0.01~30質量%的羧酸鋅組合物。 The zinc carboxylate solution of the present invention preferably contains 0.01 to 30 mass% of the zinc carboxylate composition when the total amount of the solvent and the zinc carboxylate composition is 100 mass%.
實施例 Example
以下，舉出實施例及比較例對本發明進一步具體地進行說明。 Hereinafter, the present invention will be described in further detail with reference to Examples and Comparative Examples.
(實施例1：羧酸鋅組合物的製備) (Example 1: Preparation of zinc carboxylate composition)
向3L可分離燒瓶中加入250g具有表1的“No.1”的組成比的羧酸組合物及2500g水，並升溫至70℃。接著，加入77.2g 48質量%氫氧化鈉水溶液，在相同溫度(70℃)下攪拌1小時，得到羧酸鹼金屬鹽水溶液。然後，保持70℃，經1小時將151.2g 25質量%氯化鋅水溶液滴加至羧酸鹼金屬鹽水溶液中。滴加結束後，進一步於70℃攪拌1小時。向所得到的羧酸鋅水溶液漿料中加入1500g水，並冷卻至60℃以下。然後，利用吸濾機進行過濾，並用1000g的水進行2次水洗，對於所得到的濾餅，使用櫃式乾燥機於75℃乾燥72小時，進行粉碎及分級從而得到羧酸鋅組合物顆粒。 250g of the carboxylic acid composition having the composition ratio of "No. 1" in Table 1 and 2500g of water were added to a 3L separable flask, and the temperature was raised to 70°C. Next, 77.2 g of 48% by mass sodium hydroxide aqueous solution was added, and the mixture was stirred at the same temperature (70° C.) for 1 hour to obtain an alkali metal carboxylate aqueous solution. Then, while maintaining 70° C., 151.2 g of a 25% by mass zinc chloride aqueous solution was added dropwise to the alkali metal carboxylate aqueous solution over 1 hour. After completion of the dropwise addition, the mixture was further stirred at 70° C. for 1 hour. 1500g of water was added to the obtained zinc carboxylate aqueous solution slurry, and the mixture was cooled to below 60°C. Then, it was filtered with a suction filter and washed twice with 1000 g of water. The obtained filter cake was dried at 75° C. for 72 hours using a cabinet dryer, pulverized and classified to obtain zinc carboxylate composition particles.
(實施例2) (Example 2)
除了將使用的羧酸組合物變更為表1所示的No.2以外，以與實施例1相同的條件進行製備。 It was prepared under the same conditions as Example 1 except that the carboxylic acid composition used was changed to No. 2 shown in Table 1.
(比較例1) (Comparative example 1)
除了將使用的羧酸的組成比變更為表1所示的No.3以外，以與實施例1相同的條件進行製備。 Preparation was performed under the same conditions as in Example 1, except that the composition ratio of the carboxylic acid used was changed to No. 3 shown in Table 1.
(比較例2) (Comparative example 2)
除了將使用的羧酸的組成比變更為表1所示的No.4以外，以與實施例1相同的條件進行製備。 Preparation was performed under the same conditions as in Example 1, except that the composition ratio of the carboxylic acid used was changed to No. 4 shown in Table 1.
然後，對於實施例1、2及比較例1、2、3的羧酸鋅組合物顆粒，分別以下述方式對100℃下的黏度(1rpm及2.5rpm)、黏度穩定性、耐熱性進行測定，並將測定結果示於表2。 Then, for the zinc carboxylate composition particles of Examples 1, 2 and Comparative Examples 1, 2, and 3, the viscosity (1 rpm and 2.5 rpm), viscosity stability, and heat resistance at 100°C were measured in the following manner, respectively. The measurement results are shown in Table 2.
(100℃下的黏度) (Viscosity at 100°C)
利用B型黏度計對100℃下熔解的試料的黏度(1rpm及2.5rpm)進行測定。 The viscosity (1 rpm and 2.5 rpm) of the sample melted at 100°C was measured using a B-type viscometer.
(黏度穩定性) (viscosity stability)
1rpm時的黏度除以2.5rpm時的黏度而得到的值 The value obtained by dividing the viscosity at 1 rpm by the viscosity at 2.5 rpm
(耐熱性) (heat resistance)
利用加德納色度，對使試料於100℃剛完全熔融之後的色調及於100℃保持熔融狀態1小時後的試料的色調進行測定。所有試料的剛熔融之後的加德納均為2。將保持1小時後的色調示於表2。此外，求出剛熔融之後的色調與保持1小時後的色調的差，並示於表2的括弧內。另外，按照JIS K-0071-2進行測定。 The Gardner color scale was used to measure the color tone immediately after the sample was completely melted at 100° C. and the color tone of the sample after maintaining the molten state at 100° C. for 1 hour. The Gardner values immediately after melting were 2 for all samples. Table 2 shows the color tone after maintaining for 1 hour. In addition, the difference between the color tone immediately after melting and the color tone after holding for 1 hour was determined and shown in parentheses in Table 2. In addition, the measurement was performed in accordance with JIS K-0071-2.
[羧酸鋅溶液的製備與評價] [Preparation and evaluation of zinc carboxylate solution]
向2升SUS制圓底燒瓶中投入800.0g 1-十八碳烯與200.0g表2的各例的羧酸鋅組合物，並在氮氣鼓泡下，於300℃混合5小時，得到溶液。混合後，溶液的溫度冷卻至室溫，得到樣品。 800.0 g of 1-octadecene and 200.0 g of the zinc carboxylate composition of each example in Table 2 were put into a 2-liter SUS round-bottomed flask, and mixed at 300° C. for 5 hours under nitrogen bubbling to obtain a solution. After mixing, the temperature of the solution was cooled to room temperature to obtain a sample.
對於得到的樣品，通過目視確認溶解穩定性。將其結果示於表3。 The dissolution stability of the obtained sample was visually confirmed. The results are shown in Table 3.
如表1~3所示，構成羧酸鋅組合物的羧酸滿足本發明的組成比時，羧酸鋅熔融物的黏度穩定性及耐熱性良好，且羧酸鋅溶液的溶解穩定性高。 As shown in Tables 1 to 3, when the carboxylic acid constituting the zinc carboxylate composition satisfies the composition ratio of the present invention, the zinc carboxylate melt has good viscosity stability and heat resistance, and the zinc carboxylate solution has high dissolution stability.
比較例1中，成分(A)、(B)的比率及(A)/(B)在本發明的範圍外，黏度穩定性低，觀察到了羧酸鋅的分離。 In Comparative Example 1, the ratio of components (A) and (B) and (A)/(B) were outside the range of the present invention, the viscosity stability was low, and separation of zinc carboxylate was observed.
比較例2中，成分(B)的比率及(A)/(B)在本發明的範圍外，黏度穩定性低，1小時後的色調變化較大，觀察到了溶液渾濁。 In Comparative Example 2, the ratio of component (B) and (A)/(B) were outside the range of the present invention, the viscosity stability was low, the color tone changed significantly after 1 hour, and the solution was turbid.
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