WO1990007559A1 - Production of liquid rosin ester - Google Patents
Production of liquid rosin ester Download PDFInfo
- Publication number
- WO1990007559A1 WO1990007559A1 PCT/JP1986/000423 JP8600423W WO9007559A1 WO 1990007559 A1 WO1990007559 A1 WO 1990007559A1 JP 8600423 W JP8600423 W JP 8600423W WO 9007559 A1 WO9007559 A1 WO 9007559A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rosin ester
- liquid
- alcohol
- rosin
- reaction
- Prior art date
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000003784 tall oil Substances 0.000 title abstract description 26
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 23
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 23
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims abstract description 11
- 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 claims abstract description 10
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 235000009518 sodium iodide Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 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 abstract 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- 150000004694 iodide salts Chemical class 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000005886 esterification reaction Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- -1 acid Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- MXYATHGRPJZBNA-KRFUXDQASA-N isopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)CC2=CC1 MXYATHGRPJZBNA-KRFUXDQASA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical class OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- MXYATHGRPJZBNA-UHFFFAOYSA-N 4-epi-isopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)CC1=CC2 MXYATHGRPJZBNA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
Definitions
- the present invention relates to a method for producing a liquid rosin ester, and more particularly, to a method for producing a liquid rosin ester which is pale and excellent in stability.
- the rosin ester obtained by esterifying rosin with a monovalent or polyvalent alcohol and converting it into a resin is a liquid resin. It has been awarded as an additive, modifier and the like.
- liquid rosin esters are used as so-called liquid tackifiers as important constituents of adhesives due to their adhesive properties.
- the liquid tackifier in addition to the above-mentioned rosin ester, for example, liquid terpene resin, liquid petroleum resin, polybutene, liquid polyisoprene and the like are known.
- Process oils are used as plasticizers, but liquid rosin esters are other than the above liquid resins in terms of adhesive properties. Although it is superior to other products, such as process oils and process oils, it is not always satisfactory in terms of color tone and heating stability.
- the adhesive properties are excellent.
- a new liquid resin which is light-colored and excellent in stability, especially a liquid rosin ester.
- Japanese Unexamined Patent Publication No. 59-23072 discloses that an esterification reaction of distilled and purified rosin with alcohol in the presence of a specific organic sulfur compound gives a pale color and good stability.
- a technology for producing a liquid mouth gin ester is disclosed.
- two steps of a distillation step and an esterification step are indispensable, the production efficiency is low and the method is disadvantageous in terms of economy.
- the present inventors have aimed at developing a novel liquid rosin ester which can simultaneously satisfy various conditions such as color tone, heating stability, and production efficiency.
- the specific alkali metal iodide and anthraquinone are used in combination, It has been found that a technique for producing a liquid rosin ester that meets the requirements can be provided.
- the present invention has been completed based on this new finding.
- the present invention relates to a method for producing a compound comprising at least one alkali metal iodide selected from sodium iodide and potassium iodide, and an anthraquinone;
- the present invention relates to a method for producing a light-colored and stable liquid rosin ester, which is characterized in that a gin and an alcohol are heated and reacted.
- any of various conventionally known rosin substances can be used as the rosin.
- rosin Contains resin acids such as acid, parastrinic acid, neoabietic acid, pimaric acid, isopimaric acid, devidroabietic acid as a main component
- resin acids such as acid, parastrinic acid, neoabietic acid, pimaric acid, isopimaric acid, devidroabietic acid as a main component
- Examples include wood trousers, wood trousers, and trolley trousers.
- the alcohols may be any of monovalent alcohols and divalent alcohols in consideration of the deterioration point of the obtained rosin ester. Can be selected and used as appropriate. Specific examples are propyl alcohol, butyl alcohol, pentyl alcohol, and hexyl alcohol. Other alcohols having 3 to 7 carbon atoms, such as heptyl alcohol, and other monovalent alcohols such as octyl alcohol, 2—ethylhexyl alcohol, decyl alcohol, and lauric alcohol, and ethyl alcohol. Examples thereof include divalent alcohols such as length alcohols, diethyl alcohols, triethylene glycols, and polyethylene glycols.
- the esterification reaction of the present invention comprises the presence of at least one kind of alkali metal iodide selected from sodium iodide and potassium iodide and anthraquinone. It is important to do the following, and only then will the particular and remarkable effect peculiar to the present invention be achieved.
- the esterification reaction can be carried out in the same manner as the known seed esterification reaction, except that the above specific alkali metal iodide and anthraquinone are used.
- a rosin and an alcohol are usually charged in the presence of the above-mentioned specific alkali metal iodide and anthraquinone, and are charged under an inert gas stream, in the presence or absence of a solvent.
- This ripening reaction is carried out by heating the mixture to a temperature higher than that of the conventionally known seed esterification reaction. You can do the same thing as.
- an ordinary esterification catalyst can be used in consideration of the reaction time.
- a solvent that can be used in the above reaction for example, aromatic solvents such as benzene, toluene, and xylene can be preferably exemplified.
- the esterification catalyst include sulfuric acid.
- Acid catalysts such as acetic acid, paratoluenesulfonic acid, etc. hydroxides of alkaline earth metals such as calcium hydroxide, metal oxides such as magnesium oxide and calcium oxide, and carbonic acid Examples thereof include ordinary esterified catalysts such as calcium and magnesium sulfate.
- the charging ratio of the rosin to the alcohol is not particularly limited, and may be appropriately determined in consideration of the type of rosin, its acid value, the softening point of the obtained esterified product, and the like.
- the hydroxyl group in the alcohol to the hydroxyl group in the rosin to be determined is preferably in an equivalent ratio of about 0.6 to 1.4.
- the amount of the aluminum metal iodide used in the above method of the present invention is preferably about 0.01 to 3.0% by weight (hereinafter simply referred to as%) with respect to the rosin. It is recommended that the amount of anthraquinone used in combination with the alkali metal iodide be as follows: Against It is desirable to select from a range of about 0.01 to 3.096, preferably about 0.1 to 1.0%. If either one of the above two is less than the above range, it is difficult to sufficiently exert the light-color effect, and conversely, there is no particular advantage if both components are used beyond the above range. Rather, it is economically disadvantageous.
- the timing of adding the alkali metal iodide and the entraquinone may affect the color tone and the heating stability of the resulting liquid rosin ester. It is preferred to add it beforehand or at the beginning of the reaction.
- a target liquid rosin ester can be easily obtained.
- the liquid rosin ester thus obtained has excellent adhesive properties, and exhibits unexpected characteristics in terms of color tone, heat stability and the like, as compared with conventionally known liquid rosin esters. is there .
- alkali metal iodide has the activity as a disproportionation catalyst and easily causes side reactions such as ring opening reaction and demethylation. It is considered that the softening point of the obtained rosin ester tends to decrease, and that the intraquinone has a decolorizing effect.
- the liquid rosin ester obtained by the method of the present invention is It can be widely applied to known applications, especially because it has the above-mentioned various properties, that is, adhesive properties, light color, and good heat stability, so that hot-melt adhesives and hot-melts can be used. It can be suitably used as a liquid tackifier, which is a component of the root adhesive. In preparing the composition, it goes without saying that general additives such as antioxidants, light stabilizers, and oils can be used in combination, if necessary.
- a four-hole flask equipped with a stirrer, cooling pipe, water separator and nitrogen inlet pipe was equipped with a toluene oil [acid value: 174.5 (ASTMD 465-51) , Softening point: 68.0 ° C (according to the ring and ball method, the same applies hereinafter), color tone: 6 G (gardner color, the same applies hereinafter)] , JET LENDER COLOR 909, sodium iodide 0.99 and anthraquinone 1.89, and ripened to 230 G under a nitrogen stream. After the reaction at the same temperature for 5 hours, the temperature was further raised to 270, and the reaction was continued at the same temperature for 5 hours. Table 1 shows the yield and various constants of the liquid rosin ester thus obtained.
- Example II triethylene glycol was used in place of diethyl alcohol, and a similar reaction was carried out to obtain a liquid rosin ester.
- Table II shows the yield and various constants of the obtained rosin ester.
- Example 1 gum rosin [acid value: 169,5, liquefaction point: 78.0, color tone: 6G] was used instead of tall oil rosin. The reaction was performed to obtain a liquid rosin ester.
- Table 1 shows the yield and various constants of the obtained rosin ester.
- Example 1 n-year-old alcohol 260 was used in place of diethyl alcohol 909, and the reaction was carried out in the same manner to obtain a liquid rosin ester.
- Table 1 shows the yield of the obtained rosin ester and various constants. Comparative example ⁇
- Example 1 The reaction was carried out in the same manner as in Example 1 except that sodium iodide was not used, and a liquid rosin ester was obtained. Table 1 shows the constants and various constants.
- Example 1 the amount of sodium iodide used was reduced.
- the reaction was carried out in the same manner except that the amount was 1.2 g, and no antraquinone was used, to obtain a liquid rosin ester.
- Table 1 shows the yield and various constants of the obtained rosin ester.
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
This invention relates to a process for producing a pale-color, stable liquid rosin ester, characterized by reacting rosin with an alcohol by heating them in the presence of at least one alkali metal iodide selected from among iodides of sodium and potassium and anthraquinone.
Description
明 Light
液状 ロ ジ ンエ ス テルの製造方法 Method for producing liquid rosin ester
技 術 分 野 Technical field
本発明 は 、 液状 ロ ジ ン エ ステルの製造方法 、 詳 し く は 淡色で且つ安定性 に優れた液状 ロ ジ ンエス テルの製造方 法 に 関する The present invention relates to a method for producing a liquid rosin ester, and more particularly, to a method for producing a liquid rosin ester which is pale and excellent in stability.
背 景 技 術 Background technology
ロ ジ ンを 1 価も し く は多価 アルコ ー ル と エ ス テル化反 応さ せ て得 ら れる ロ ジ ンエ ステルは 、 液状樹脂 と し て 、 従来よ り 粘接着剤 、 塗料等の添加剤 、 改質剤等 と し て 賞 用 さ れて いる 。 殊 に 液状 ロ ジ ンエステルは 、 そ の粘着特 性か ら 、 粘接着剤の重要構成成分 と し て 、 即 ち いわ ゆ る 液状粘着付与剤 と し て利用 さ れて いる 。 該液状粘着付与 剤 と し て は 、 上記 ロ ジ ン エ ス テル以外 に も 、 例え ば液状 テ ルペ ン系樹脂 、 液状石油樹脂 、 ポ リ ブテ ン 、 液状ポ リ イ ソプ レ ン等が知 ら れて お り 、 ま た 可塑剤 と し て はプ ロ セ ス オ イ ル等が用 い ら れて いる が 、 液状 ロ ジ ン エ ス テル は 、 粘着特性の点で上記他の液状樹脂やプ ロ セ ス オ イ ル 等 に 比べて優れて いる反面 、 色調 、 加熱安定性の点で必 ず し お満足で き るちので は な い 。 The rosin ester obtained by esterifying rosin with a monovalent or polyvalent alcohol and converting it into a resin is a liquid resin. It has been awarded as an additive, modifier and the like. In particular, liquid rosin esters are used as so-called liquid tackifiers as important constituents of adhesives due to their adhesive properties. As the liquid tackifier, in addition to the above-mentioned rosin ester, for example, liquid terpene resin, liquid petroleum resin, polybutene, liquid polyisoprene and the like are known. Process oils are used as plasticizers, but liquid rosin esters are other than the above liquid resins in terms of adhesive properties. Although it is superior to other products, such as process oils and process oils, it is not always satisfactory in terms of color tone and heating stability.
以上 の理由 か ら斯界 に おい て は 、 粘着特性 に 優れ 、 し
かも淡色で且つ安定性に優れた新 し い液状樹脂、 殊に液 状 ロ ジンエステルの開発が要望さ れて いる 。 For the above reasons, in the art, the adhesive properties are excellent. There is a demand for the development of a new liquid resin which is light-colored and excellent in stability, especially a liquid rosin ester.
ま た ロ ジ ンを不均化又は水素化 し た後、 エステル化す れば、 加熟安定性の改良された液状ロ ジ ンエステルを収 得できるこ とが知 ら れているが 、 かかる方法で は 、 反応 中 に ロ ジ ンの加熟劣化に よる着色が見 ら れ、 その防止は 困難であ り 、 ま た液状粘着付与剤 に要求さ れる加熱安定 性を尚満足できない 。 It is also known that if a rosin is disproportionated or hydrogenated and then esterified, a liquid rosin ester having improved ripening stability can be obtained. However, during the reaction, coloring due to ripening deterioration of the rosin is observed, it is difficult to prevent the coloring, and the heating stability required for the liquid tackifier cannot be satisfied.
更に特開昭 5 9 — 2 3 0 0 7 2 号公報に は 、 蒸留精製 ロ ジ ンを特定の有機硫黄化合物の存在下に アルコ ール と エステル化反応させ、 淡色で且つ安定性の良好な液状 口 ジンエステルを製造する技術が開示さ れて いる 。 し か し なが ら斯かる方法では 、 蒸留工程 とエステル化工程との 二工程が必須であるた め 、 生産効率が悪 く 、 経済性の面 でも不利である 。 Further, Japanese Unexamined Patent Publication No. 59-23072 discloses that an esterification reaction of distilled and purified rosin with alcohol in the presence of a specific organic sulfur compound gives a pale color and good stability. A technology for producing a liquid mouth gin ester is disclosed. However, in such a method, since two steps of a distillation step and an esterification step are indispensable, the production efficiency is low and the method is disadvantageous in terms of economy.
本発明者 ら は 、 上記の如き現状に鑑み、 色調 、 加熱安 定性、 生産効率等の諸条件を同時に満足 し得る新規な液 状 ロ ジ ンエステルを 開発する こ と を目 的 と し て 、 特にェ ステル化反応時に添加すべき安定化剤 に着目 し て鋭意検 討を重ねた 。 その結果、 特定の アルカ リ 金属 ヨ ウ化物及 びアン 卜 ラ キ ノ ンを組合せて使用 す る場合に は 、 上記目
的に合致す る液状 ロ ジ ンエステルの製造技術が提供さ れ る こ と を見出 し た 。 本発明 は 、 こ の新 し い知見に 基づい て 完成さ れた ものである 。 In view of the current situation as described above, the present inventors have aimed at developing a novel liquid rosin ester which can simultaneously satisfy various conditions such as color tone, heating stability, and production efficiency. We focused on the stabilizers to be added during the esterification reaction and made extensive studies. As a result, when the specific alkali metal iodide and anthraquinone are used in combination, It has been found that a technique for producing a liquid rosin ester that meets the requirements can be provided. The present invention has been completed based on this new finding.
発 明 の 開 示 Disclosure of the invention
本発明 は、 ヨ ウ化ナ ト リ ウ ム及び ヨ ウ化カ リ ウムか ら 選ばれる少な く と も 1 種の アルカ リ 金属 ヨ ウ化物 と ア ン 卜 ラキ ノ ン と の存在下に 、 ロ ジ ン と アルコ ー ル類 と を加 熱反応さ せる こ と を特徴 と す る淡色で安定性良好な液状 ロ ジ ンエ ステルの製造方法に 係わ る 。 The present invention relates to a method for producing a compound comprising at least one alkali metal iodide selected from sodium iodide and potassium iodide, and an anthraquinone; The present invention relates to a method for producing a light-colored and stable liquid rosin ester, which is characterized in that a gin and an alcohol are heated and reacted.
本発明 に おいて 、 ロ ジ ン と し て は 、 従来よ り よ く 知 ら れて いる各種 ロ ジ ン物質をいずれも用 いる がでぎ る そ の例 と し て は 、 ァ ビ エ チン酸、 パ ラ ス 卜 リ ン酸、 ネ オ ァ ビ エ チン酸、 ピマ ール酸、 イ ソ ピマ ー ル酸、 デ ビ ド ロ ァ ビエ チ ン酸等の樹脂酸を主成分 と し て 含有す る ガ ム 口 ジ ン を始め と し て 、 ウッ ド ロ ジ ン 、 卜 ー ル油 ロ ジ ン等を 例示す る こ と がで きる 。 In the present invention, any of various conventionally known rosin substances can be used as the rosin. Contains resin acids such as acid, parastrinic acid, neoabietic acid, pimaric acid, isopimaric acid, devidroabietic acid as a main component Examples include wood trousers, wood trousers, and trolley trousers.
ま た本発明 に お いて 、 アルコ ー ル類 と し て は 、 得 ら れ る ロ ジ ン エ ス テルの软化点を考慮 し て 1 価 アルコ ー ル及 び 2 価アルコ ー ルの う ち か ら適宜選択使用 す る こ と がで き る 。 そ の具体例 と し て はプ ロ ピル アル コ ー ル、 ブチル アル コ ー ル 、 ペ ン チル アルコ ー ル 、 へキ シル アル コ ー ル
ヘプチルアルコ ール等の炭素数 3 〜 7 の アルコ ールの他 才 ク チルアルコ ール、 2 — ェチルへキシルアルコ ール、 デシルアルコ ール、 ラ ウ リ ルアルコ ール等の 1 価アルコ ール及びエチ レング リ コ ール、 ジエチ レ ング リ コ ール、 卜 リ エチ レング リ コ ール、 ポ リ エチ レ ング リ コ ール等の 2 価アルコ ールを例示できる。 ま た本発明で は、 上記 1 価アルコ ール及び 2価アルコ ールに加えて 、 更に例えば グ リ セ リ ン 、 卜 リ メ チロ ールプ ロ パン 、 ペ ン タ エ リ ス リ 卜 ール等の多価アルコ ールを併用 する こ ともできる 。 本発明のエステル化反応は、 ヨ ウ化ナ ト リ ウム及び ョ ゥ化カ リ ウムか ら選ばれる少な く と も 1 種の アルカ リ 金 属 ヨ ウ化物 と ア ン 卜 ラキ ノ ン と の存在下に行なう こ と が 重要であって 、 こ れに よ り始めて本発明に特有の格別顕 著な効果が奏さ れる 。 該エステル化反応は、 上記特定の アルカ リ 金属 ヨ ウ化物 と ア ン 卜 ラキノ ン と を用 いる こ と を除いて 、 公知の こ の種エステル化反応 と同様に し て実 施できる 。 即ち 、 通常上記特定の アルカ リ 金属 ヨ ウ化物 と ア ン 卜 ラ キ ノ ンと の存在下に 、 ロ ジン と アルコ ール類 と を仕込み、 不活性気流下、 溶媒の存在下又は不存在下 に加熱 し て脱水縮合させる こ と に よ り 行なわれ、 こ の加 熟反応条件は、 従来公知のこ の種エステル化反応のそれ
と 同様のあの と す る こ と ができる 。 ま た上記エステル化 反応の際に は反応時間 を考慮 し て 通常のエ ステル化触媒 を 用 いる こ ともできる 。 上記反応に用 い得る溶媒 と し て は 、 例え ばベ ンゼ ン 、 ト ルエ ン 、 キ シ レ ン等の芳香族系 溶媒を好適に例示でき 、 ま た エステル化触媒 と し て は 、 例えば硫酸、 酢酸、 パ ラ 卜 ルエ ンスルホ ン酸等の酸触媒 水酸化 カルシ ウ ム等の アルカ リ 土類金属の水酸化物 、 酸 化マ グネ シ ウム 、 酸化 カ ルシ ウ ム等の金属酸化物 、 炭酸 カ ルシ ウ ム 、 齚酸マグネ シ ウ ム等の通常のエ ステル化触 媒を例示できる 。 Further, in the present invention, the alcohols may be any of monovalent alcohols and divalent alcohols in consideration of the deterioration point of the obtained rosin ester. Can be selected and used as appropriate. Specific examples are propyl alcohol, butyl alcohol, pentyl alcohol, and hexyl alcohol. Other alcohols having 3 to 7 carbon atoms, such as heptyl alcohol, and other monovalent alcohols such as octyl alcohol, 2—ethylhexyl alcohol, decyl alcohol, and lauric alcohol, and ethyl alcohol. Examples thereof include divalent alcohols such as length alcohols, diethyl alcohols, triethylene glycols, and polyethylene glycols. Further, in the present invention, in addition to the above-mentioned monovalent alcohol and divalent alcohol, for example, glycerin, trimethylolpropane, pentaerythritol, etc. These polyvalent alcohols can be used in combination. The esterification reaction of the present invention comprises the presence of at least one kind of alkali metal iodide selected from sodium iodide and potassium iodide and anthraquinone. It is important to do the following, and only then will the particular and remarkable effect peculiar to the present invention be achieved. The esterification reaction can be carried out in the same manner as the known seed esterification reaction, except that the above specific alkali metal iodide and anthraquinone are used. That is, a rosin and an alcohol are usually charged in the presence of the above-mentioned specific alkali metal iodide and anthraquinone, and are charged under an inert gas stream, in the presence or absence of a solvent. This ripening reaction is carried out by heating the mixture to a temperature higher than that of the conventionally known seed esterification reaction. You can do the same thing as. In the above esterification reaction, an ordinary esterification catalyst can be used in consideration of the reaction time. As a solvent that can be used in the above reaction, for example, aromatic solvents such as benzene, toluene, and xylene can be preferably exemplified. Examples of the esterification catalyst include sulfuric acid. Acid catalysts such as acetic acid, paratoluenesulfonic acid, etc. hydroxides of alkaline earth metals such as calcium hydroxide, metal oxides such as magnesium oxide and calcium oxide, and carbonic acid Examples thereof include ordinary esterified catalysts such as calcium and magnesium sulfate.
上記反応に おい て ロ ジ ン と アルコ ール類 と の仕込み比 率は 、 特に制限さ れず 、 ロ ジ ン の種類、 そ の酸価、 得 ら れるエステル化物の軟化点等を考慮 し て適宜決定さ れる 通常、 ロ ジ ン中の 力 ルポキ シル基に 対ずる アル コ ー ル中 の水酸基が当量比で約 0 . 6 〜 1 . 4 の範囲 と するのが 好 ま し い 。 In the above reaction, the charging ratio of the rosin to the alcohol is not particularly limited, and may be appropriately determined in consideration of the type of rosin, its acid value, the softening point of the obtained esterified product, and the like. Usually, the hydroxyl group in the alcohol to the hydroxyl group in the rosin to be determined is preferably in an equivalent ratio of about 0.6 to 1.4.
上記本発明方法 に用 いる アル 力 リ 金属 ヨ ウ化物 の使用 量 は 、 ロ ジ ン に対 し て 約 0 . 0 1 〜 3 . 0 重量% ( 以下 単 に % と い う 〉 、 好 ま し く は約 0 . Ί 〜 Ί . 0 % の範囲 か ら 選択す る の がよ い 。 ま た 、 該 アルカ リ 金属 ヨ ウ化物 と 併用 さ れる ア ン ト ラ キ ノ ン の使用 量 は 、 ロ ジ ン に対 し
て約 0 . 0 1 〜 3 . 0 96 、 好ま し く は約 0 . 1 〜 1 . 0 %の範囲か ら選択さ れるのが望ま しい。 上記 2 者の内い ずれか一方であ前記範囲 に満たない場合は、 淡色効果が 充分に は発揮さ れ難く なり 、 逆に両成分を上記範囲を越 えて用 いても特に利点はな く 、 む し ろ経済的に不利 とな る 。 尚、 アルカ リ 金属 ヨ ウ化物及びア ン 卜 ラ キノ ンの添 加時期 は、 得 ら れる液状 ロ ジンエステルの色調 、 加熱安 定性に影響を与える場合があ り 、 通常は、 エステル化前 に予め添加するか又は該反応の初期に添加するのが好ま しい 。 The amount of the aluminum metal iodide used in the above method of the present invention is preferably about 0.01 to 3.0% by weight (hereinafter simply referred to as%) with respect to the rosin. It is recommended that the amount of anthraquinone used in combination with the alkali metal iodide be as follows: Against It is desirable to select from a range of about 0.01 to 3.096, preferably about 0.1 to 1.0%. If either one of the above two is less than the above range, it is difficult to sufficiently exert the light-color effect, and conversely, there is no particular advantage if both components are used beyond the above range. Rather, it is economically disadvantageous. The timing of adding the alkali metal iodide and the entraquinone may affect the color tone and the heating stability of the resulting liquid rosin ester. It is preferred to add it beforehand or at the beginning of the reaction.
上記反応に よ り 、 目 的 とする液状 ロ ジ ンエステルを容 易 に収得する こ と ができる 。 かく し て得ら れる液状 ロ ジ ンエステルは、 優れた粘着特性を有 し 、 且つ色調 、 加熱 安定性等の点で従来公知の液状ロ ジ ンエステルと比較 し て 予期せぬ特徴を発揮するものである 。 その理由 は尚明 確で はないが 、 アルカ リ 金属 ヨ ウ化物が不均化触媒 と し て の活性を有する こ と 、 開環反応や脱メ チル化等の副反 応が生 じや す く 、 得ら れる ロ ジ ン エステルの軟化点が低 下する傾向がある こ と 、 ア ン 卜 ラキ ノ ンが脱色効果を有 する こ と等がその要因 と なっ ている と考え ら れる 。 By the above-mentioned reaction, a target liquid rosin ester can be easily obtained. The liquid rosin ester thus obtained has excellent adhesive properties, and exhibits unexpected characteristics in terms of color tone, heat stability and the like, as compared with conventionally known liquid rosin esters. is there . Although the reason is not clear, the fact that alkali metal iodide has the activity as a disproportionation catalyst and easily causes side reactions such as ring opening reaction and demethylation. It is considered that the softening point of the obtained rosin ester tends to decrease, and that the intraquinone has a decolorizing effect.
本発明方法 に よ り 得 ら れる液状 ロ ジンエステルは 、 従
来公知の用途 に 広 く 適用 する こ と がでさ 、 殊 に 上記各種 特性、 即ち粘着特性、 淡色、 良好な加熱安定性を有す る た め 、 ホッ ト メ ル 卜 粘着剤 、 ホッ 卜 メ ル 卜 接着剤の配合 成分であ る液状粘着付与剤 と し て好適 に使用 す る こ と が で き る 。 尚 、 之等組成物の調製 に際 し て は 、 必要に応 じ て 酸化防止剤 、 光安定剤 、 オ イ ル等の一般的な添加剤 を 併用 し得る こ と は言う ま でもない 。 The liquid rosin ester obtained by the method of the present invention is It can be widely applied to known applications, especially because it has the above-mentioned various properties, that is, adhesive properties, light color, and good heat stability, so that hot-melt adhesives and hot-melts can be used. It can be suitably used as a liquid tackifier, which is a component of the root adhesive. In preparing the composition, it goes without saying that general additives such as antioxidants, light stabilizers, and oils can be used in combination, if necessary.
発明を実施す る ための最良の形態 以下 、 本発明方法を更に 詳 し く 説明する た め実施例を 挙げるが 、 本発明 は之等 に 限定 さ れない こ と はも と よ り で ある 。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, but it should be understood that the present invention is not limited thereto.
実施例 1 Example 1
撹拌装置、 冷却管、 分水器及び窒素導入管を備えた 4 つ 口 フ ラ ス コ に 、 卜 ール油 ロ ジ ン [ 酸価 : 1 7 4 . 5 ( A S T M D 4 6 5 — 5 1 に よ る 、 以下同 じ ) 、 軟化 点 : 6 8 . 0 °C ( 環球法 に よ る 、 以下同 じ ) 、 色調 : 6 G ( ガ ー ドナ ー カ ラ ー 、 以下同 じ ) ] 6 0 09 、 ジェ チ レ ンダ リ コ ール 9 09 、 ヨ ウ化ナ ト リ ウ ム 0 . 99 及び ア ン 卜 ラキ ノ ン 1 . 89 を仕込み 、 窒素気流下に 2 3 0Gま で加熟 し 、 同温度で 5 時間反応さ せ た 後 、 更に 2 7 0で ま で昇温 し て 、 同温度で 5時間反応させ た 。
か く して得ら れた液状 ロ ジンエ ステルの収率及ぴ各種 恒数を第 1 表に示す 。 A four-hole flask equipped with a stirrer, cooling pipe, water separator and nitrogen inlet pipe was equipped with a toluene oil [acid value: 174.5 (ASTMD 465-51) , Softening point: 68.0 ° C (according to the ring and ball method, the same applies hereinafter), color tone: 6 G (gardner color, the same applies hereinafter)] , JET LENDER COLOR 909, sodium iodide 0.99 and anthraquinone 1.89, and ripened to 230 G under a nitrogen stream. After the reaction at the same temperature for 5 hours, the temperature was further raised to 270, and the reaction was continued at the same temperature for 5 hours. Table 1 shows the yield and various constants of the liquid rosin ester thus obtained.
実施例 2 Example 2
実施例 Ί において 、 ジエチ レ ング リ コ ー ルに代えて 卜 リ エチ レ ング リ コ ールを使用 し 、 同様に し て反応を行な い 、 液状 ロ ジンェステルを得た 。 In Example II, triethylene glycol was used in place of diethyl alcohol, and a similar reaction was carried out to obtain a liquid rosin ester.
得 ら れた ロ ジ ンエステルの収率及び各種恒数を第 Ί 表 に示す 。 Table II shows the yield and various constants of the obtained rosin ester.
実施例 3 Example 3
実施例 1 において 、 ト ール油 ロ ジン に代えて ガム ロ ジ ン [ 酸価 : 1 6 9 , 5、 钦化点 : 7 8 . 0 、 色調 : 6 G ] を使用 し 、 同様に して反応を行ない 、 液状 ロ ジ ンェ ステルを得た。 In Example 1, gum rosin [acid value: 169,5, liquefaction point: 78.0, color tone: 6G] was used instead of tall oil rosin. The reaction was performed to obtain a liquid rosin ester.
得 ら れた ロ ジンエステルの収率及び各種恒数を第 1 表 に示す。 Table 1 shows the yield and various constants of the obtained rosin ester.
実施例 4 Example 4
実施例 1 において 、 ジエチ レ ング リ コ ール 9 09 に代 えて n — 才 ク チルアルコ ー ル 2 6 09 を使用 し 、 同様に し て 反応を行ない 、 液状 ロ ジ ンエ ステルを得た 。 In Example 1, n-year-old alcohol 260 was used in place of diethyl alcohol 909, and the reaction was carried out in the same manner to obtain a liquid rosin ester.
得ら れた ロ ジ ンエ ステルの収率及び各種恒数を第 1 表 に示す 。
比較例 Ί Table 1 shows the yield of the obtained rosin ester and various constants. Comparative example Ί
実施例 1 に おいて 、 ヨ ウ化ナ ト リ ウムを使用 し な い以 外は同様に し て反応を行ない 、 液状 ロ ジ ン.エ ス テルを得 得 ら れた ロ ジ ンエステルの収率及び各種恒数を第 1 表 に示す 。 The reaction was carried out in the same manner as in Example 1 except that sodium iodide was not used, and a liquid rosin ester was obtained. Table 1 shows the constants and various constants.
比較例 2 Comparative Example 2
実施例 1 におい て 、 ヨ ウ化ナ 卜 リ ウ ムの使用 量を In Example 1, the amount of sodium iodide used was reduced.
1 . 2 g と し 、 且つ ア ン 卜 ラ キ ノ ンを使用 し ない以外は 同様 に し て反応を行ない 、 液状 ロ ジ ンエステルを得 た 。 The reaction was carried out in the same manner except that the amount was 1.2 g, and no antraquinone was used, to obtain a liquid rosin ester.
得 ら れた ロ ジ ンエ ステルの収率及び各種恒数を第 1 表 に 示す 。 Table 1 shows the yield and various constants of the obtained rosin ester.
上記各例で得 ら れた 液状 ロ ジ ンエステルにつ いて 酸価 粘度 ( 2 5 、 セ ン チボ イ ズ ) 、 色調及び加熟安定性を 調べた 。 尚 、 加熱安定性は 、 以下の方法 に よ り 試験 し た 〈 加熱安定性試験 〉 With respect to the liquid rosin ester obtained in each of the above examples, the acid value viscosity (25, centivoise), color tone and ripening stability were examined. The heating stability was tested by the following method <Heating stability test>
液状 ロ ジ ンエ ステル試料の各々 5 9 づっ を 、 内径 1 4 m m , 長さ 1 5 cmの試験管に入れ、 2 0 0 ^ の循風 乾燥器中 に放置 し 、 2 時間後及び 6 時間後の各内容物 の色調をガ ー ド ナ ー 比色計で測定 し た 。 測定 さ れた 初 期の色調 と加熱後の色調 と の変化が小さ い程 、 加熟安
定性は良好である 得ら れた結果を下記第 1 表に示す 第 Ί 表 試 料 収 率 酸 価 色 謂 加熱安 性(G)Place each of the 59 liquid rosin ester samples in a test tube with an inner diameter of 14 mm and a length of 15 cm, leave them in a circulating air dryer of 200 ^ ^, and after 2 hours and 6 hours The color tone of each of the contents was measured with a gardener colorimeter. The smaller the change between the measured initial color tone and the color tone after heating, the lower The qualities are good. The obtained results are shown in Table 1 below. Table II Sample yield Acid value Color So-called heating stability (G)
No . ft No. Ft
(G ) 2時間後 6時間後 実施例 1 94 27 56万 1+ 5 7 en (G) 2 hours later 6 hours later Example 1 94 27 560,000 1 + 57 en
実施例 2 93 37 42万 Ί + 5 7 Example 2 93 37 420 thousand Ί + 5 7
実施例 3 94 28 65万 2 5 + 7 + Example 3 94 28 65 million 25 + 7 +
実施例 4 89 15 3万 2 5 + 7 Example 4 89 15 30 25 + 7
比較例 1 93 20 100万 5 9 + 14 Comparative Example 1 93 20 1 million 5 9 + 14
比較例 2 93 26 55万 5 9 13
Comparative Example 2 93 26 550,000 5 9 13
Claims
請 求 の 範 囲 The scope of the claims
① ヨ ウ化ナ 卜 リ ウ ム及ぴ ヨ ウ化 カ リ ウ ム か ら選ばれる 少な く とも 1 種の アルカ リ 金属 ヨ ウ化物 と ア ン 卜 ラキ ノ ン と の存在下に 、 ロ ジ ン と アル コ ー ル類 と を加熱反 応さ せる こ と を特徴 と する淡色で安定性良好な液状 口 ジ ンエス テルの製造方法。 (1) At least one alkali metal iodide selected from sodium iodide and potassium iodide and an anthraquinone, A method for producing a light-colored and stable liquid mouth ester, characterized by reacting an alcohol with alcohol.
② ロ ジ ン に対 し て アルカ リ 金属 ヨ ウ化物 を約 0. 0 1 〜 3 . 0重量%及びア ン 卜 ラ キ ノ ン を約 0. 0 Ί 〜 3. 0重量%使用 する請求の範囲第 1 項に記載の方法
(2) Claims to use about 0.01 to 3.0% by weight of alkali metal iodide and about 0.03 to 3.0% by weight of anthraquinone to rosin. Method described in section 1
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP1986/000423 WO1990007559A1 (en) | 1986-08-18 | 1986-08-18 | Production of liquid rosin ester |
US07/184,448 US4822526A (en) | 1986-08-18 | 1986-08-18 | Process for preparing liquid rosin ester with anthraquinone and alkali metal iodide |
JP5015787A JPH06230170A (en) | 1986-08-18 | 1993-02-03 | Fast breeder reactor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP1986/000423 WO1990007559A1 (en) | 1986-08-18 | 1986-08-18 | Production of liquid rosin ester |
JP5015787A JPH06230170A (en) | 1986-08-18 | 1993-02-03 | Fast breeder reactor |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1990007559A1 true WO1990007559A1 (en) | 1990-07-12 |
Family
ID=26351994
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1986/000423 WO1990007559A1 (en) | 1986-08-18 | 1986-08-18 | Production of liquid rosin ester |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPH06230170A (en) |
WO (1) | WO1990007559A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2015137403A1 (en) * | 2014-03-12 | 2017-04-06 | 荒川化学工業株式会社 | Adhesive composition and acrylic adhesive composition |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101436497B1 (en) * | 2012-12-11 | 2014-09-01 | 한국원자력연구원 | Passive decay heat removal system for liquid metal cooled reactors with enhanced natural circulation cooling capability using a helical type sodium-to-sodium heat exchanger |
WO2019083695A2 (en) * | 2017-10-02 | 2019-05-02 | Westinghouse Electric Company Llc | Pool type liquid metal fast spectrum reactor using a printed circuit heat exchanger connection to the power conversion system |
-
1986
- 1986-08-18 WO PCT/JP1986/000423 patent/WO1990007559A1/en unknown
-
1993
- 1993-02-03 JP JP5015787A patent/JPH06230170A/en active Pending
Non-Patent Citations (1)
Title |
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No relevant documents disclosed. * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2015137403A1 (en) * | 2014-03-12 | 2017-04-06 | 荒川化学工業株式会社 | Adhesive composition and acrylic adhesive composition |
Also Published As
Publication number | Publication date |
---|---|
JPH06230170A (en) | 1994-08-19 |
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