WO2014030652A1 - 重合ロジン化合物及びその製造方法 - Google Patents
重合ロジン化合物及びその製造方法 Download PDFInfo
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- WO2014030652A1 WO2014030652A1 PCT/JP2013/072209 JP2013072209W WO2014030652A1 WO 2014030652 A1 WO2014030652 A1 WO 2014030652A1 JP 2013072209 W JP2013072209 W JP 2013072209W WO 2014030652 A1 WO2014030652 A1 WO 2014030652A1
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- Prior art keywords
- rosin
- acid
- component
- group
- dimer
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/34—Chemically modified polycondensates by natural resins or resin acids, e.g. rosin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
-
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08746—Condensation polymers of aldehydes or ketones
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08746—Condensation polymers of aldehydes or ketones
- G03G9/08748—Phenoplasts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/54—Ortho- or ortho- and peri-condensed systems containing more than five condensed rings
Definitions
- the present invention relates to a polymerized rosin compound and a method for producing the same.
- the polymerized rosin compound of the present invention can be applied to applications where a polymerized rosin has been applied.
- the polymerized rosin compound of the present invention can be used as a dicarboxylic acid component in various polymers such as polyester resins. Polyester resins incorporating a polymerized rosin skeleton into the main skeleton can be used, for example, for toner resins, film resins, paint resins, and the like.
- Polymerized rosin is a resin obtained by polymerizing rosins such as gum rosin, wood rosin or tall oil rosin.
- Derivatives such as polymerized rosin and polymerized rosin ester compounds have properties such as pigment dispersibility, compatibility, viscosity and adhesion. It is used as a binder and additive in a wide range of fields such as printing inks, paints, adhesives / adhesives, and fluxes.
- Patent Document 1 a method using a polymer having a pendant sulfonic acid group as a catalyst
- Patent Document 2 a method using an aliphatic sulfonic acid as a catalyst
- Patent Document 2 a method using an aliphatic sulfonic acid as a catalyst
- Patent Document 2 Polymerization reaction of rosin acid in organic solvents such as toluene and xylene using acidic compounds such as formic acid, para-toluenesulfonic acid, methanesulfonic acid, hydrogen fluoride, zinc chloride, aluminum chloride, and titanium tetrachloride as catalysts.
- acidic compounds such as formic acid, para-toluenesulfonic acid, methanesulfonic acid, hydrogen fluoride, zinc chloride, aluminum chloride, and titanium tetrachloride
- Rosin that can be collected from rosin is a component derived from natural products, and contains resin acids such as abietic acid and pimaric acid.
- resin acids such as abietic acid and pimaric acid.
- abietic acid it is known to use abietic acid as a polymer material.
- a polymer obtained by polymerizing abietic acid with a polyhydric alcohol is known (see Patent Document 3).
- the polymer described in Patent Document 3 is not a high molecular weight linear polymer. This is because abietic acid is a monofunctional monocarboxylic acid, so that it is not incorporated into the main skeleton and is grafted to the terminal or main chain of the polymer and cannot be introduced into the polymer in a large amount. Therefore, this polymer is not fully utilized for improving the functions such as heat resistance, which is a characteristic of rosin.
- An object of the present invention is to provide a polymerized rosin compound having a high content of a rosin dimer component and a method for producing the same.
- Another object of the present invention is to provide a method for producing a polyester resin using a polymerized rosin compound having a high content of the rosin dimer component, and a polyester resin obtained by the production method.
- rosin was incorporated into the main skeleton of the polymer, and two or more reactions occurred in the molecular structure of rosin to obtain a linear polymer.
- the introduction of a functional group was considered.
- a commercially available polymerized rosin has a trimer or higher component in which three or more rosin acids are bonded, a rosin dimer component (hereinafter referred to as “dicarboxylic acid” having two rosin acids and two carboxyl groups).
- Acid rosin dimer and rosin dimer component (hereinafter referred to as“ mono ”) in which decarboxylation of dicarboxylic acid rosin dimer proceeds as a side reaction during the production of polymerized rosin and one carboxyl group is eliminated. It was found that a rosin dimer component from which two carboxyl groups were eliminated (hereinafter referred to as “dimer decomposition product”) was included. Furthermore, when unreacted rosin acid was distilled off under reduced pressure after the reaction, it was found that decarboxylation increased the components of monocarboxylic acid rosin dimer and rosin acid trimer.
- a rosin ester as a specific rosin compound as a starting material, two rosins are bonded and dimerized, and rosin diester having two functional groups (carboxyl group and / or carboxylic acid ester group) is used.
- a dimer component hereinafter referred to as “bifunctional group-containing rosin dimer”
- decarboxylation of the bifunctional group-containing rosin dimer proceeds as a side reaction during the production of the polymerized rosin compound.
- the present invention 1 has a rosin dimer component (A) content of 80% by weight or more, and the rosin dimer component (A) has the general formula (1): ROOC-X— Containing a bifunctional rosin dimer component (a1) represented by COOR (wherein X represents a rosin dimer residue, R represents hydrogen, an alkyl group having 1 to 5 carbon atoms or a benzyl group) It is a polymerized rosin compound whose amount is 80% by weight or more.
- the present invention 2 relates to the present invention 1, wherein in the rosin dimer component (A), the general formula (1 ′): R 1 OOC-X-COOR 1 (wherein X is a rosin dimer residue, R is a polymerized rosin compound in which the content of the dicarboxylic acid ester-containing rosin dimer (a10) represented by C 1-5 alkyl group or benzyl group is 80% by weight or more.
- Invention 3 is the invention 1 or 2, wherein the component (B) is a rosin trimer or higher, the general formula (2): ROOC- (wherein R is hydrogen, an alkyl group having 1 to 5 carbon atoms or benzyl) A monofunctional group-containing rosin dimer component (a2) having one functional group represented by formula (2) and the general formula (2): ROOC- (wherein R is hydrogen or an alkyl having 1 to 5 carbon atoms) A polymerized rosin compound having a total content of 20% by weight or less of the rosin dimer component (a3) having no functional group represented by a group or a benzyl group.
- the present invention 4 relates to the present invention 2 or 3, wherein the general formula (1 ′): R 1 OOC—X—COOR 1 (wherein X is a rosin dimer residue, R is an alkyl having 1 to 5 carbon atoms) Dicarboxylic acid ester-containing rosin dimer (a10) represented by the general formula (1 ′′): CH 3 OOC—X—COOCH 3 (wherein X represents the residue of the rosin dimer).
- a polymerized rosin compound containing a dimethyl ester group-containing rosin dimer represented by:
- the present invention 5 is represented by the general formula (3): X 1 -COOR 1 (wherein X 1 represents a rosin residue, R represents hydrogen, R 1 , an alkyl group having 1 to 5 carbon atoms or a benzyl group).
- X 1 represents a rosin residue
- R represents hydrogen
- R 1 an alkyl group having 1 to 5 carbon atoms or a benzyl group.
- the raw material containing a rosin ester is polymerized using a polymerization rosin production catalyst.
- Invention 6 is the invention 5, wherein the polymerized rosin production catalyst comprises sulfuric acid, formic acid, acetic acid, phosphoric acid, paratoluenesulfonic acid, methanesulfonic acid, a solid acid having a sulfonic acid group, and zinc chloride.
- This is a method for producing a polymerized rosin compound using at least one selected.
- the present invention 7 is the invention 5 or 6, wherein the purity of the rosin ester in the raw material is 80% by weight or more, and is at least one resin selected from abietic acid, neoabietic acid and a parastriic acid component in the rosin ester 6.
- the present invention 8 is a method for producing a polyester resin in which at least a dicarboxylic acid component and a dialcohol component are reacted, wherein the dicarboxylic acid component contains the polymerized rosin compound according to any one of claims 1 to 4. It is a manufacturing method.
- the present invention 9 is the method for producing a polyester resin according to the present invention 8, wherein the polyester resin has a number average molecular weight of 3000 to 400,000 and a weight average molecular weight of 3000 to 400,000.
- the present invention 10 is the method for producing a polyester resin according to the present invention 8 or 9, wherein the polyester resin has a thermal decomposition temperature of 350 ° C. or higher.
- the present invention 11 is a polyester resin obtained by the production method of the present invention 8-9.
- a rosin compound can be obtained.
- the polymerized rosin compound of the present invention contains a large amount of the bifunctional group-containing rosin dimer component (a1). Therefore, a polyester resin obtained using the polymerized rosin compound of the present invention as a dicarboxylic acid component has a rosin dimer skeleton as the main polymer than a polyester resin obtained using a conventional polymerized rosin as a dicarboxylic acid component.
- a polyester resin having a high molecular weight (a large number average molecular weight and large weight average molecular weight) can be produced. According to such a method for producing a polyester resin of the present invention, a glass transition temperature and a thermal decomposition temperature are improved, and a high molecular weight polyester resin excellent in water resistance and heat resistance can be obtained.
- the polymerized rosin compound of the present invention has a rosin dimer component (A) content of 80% by weight or more, and the rosin dimer component (A) has the general formula (1): ROOC-X— Containing a bifunctional rosin dimer component (a1) represented by COOR (wherein X represents a rosin dimer residue, R represents hydrogen, an alkyl group having 1 to 5 carbon atoms or a benzyl group) The amount is 80% by weight or more.
- the rosin dimer residue means a portion obtained by removing two of the functional groups (ROOC-) from the rosin dimer.
- the rosin dimer component (A) is a compound having a structure in which rosin is a dimer.
- the rosin dimer component (A) in addition to the above-mentioned bifunctional group-containing rosin dimer component (a1), the general formula (2): ROOC- (wherein R is hydrogen or having 1 to 5 carbon atoms) Monofunctional group-containing rosin dimer component (a2) having one functional group represented by the following formula (2): ROOC- (wherein R is hydrogen or carbon number) And a rosin dimer component (a3) having no functional group represented by 1 to 5 alkyl groups or benzyl groups).
- the monofunctional group-containing rosin dimer component (a2) is obtained by removing (decarboxylating) one of the functional groups (ROOC-) from the bifunctional group-containing rosin dimer component (a1).
- the rosin dimer component (a3) having no functional group is a decomposition product in which two eliminations (decarboxylation) of the functional group (ROOC-) of the bifunctional group-containing rosin dimer component (a1) proceeded. is there.
- the polymerized rosin compound of the present invention contains 80% by weight of the rosin dimer component (A) containing the component (a1), the component (a2) and the component (a3) as a total amount, such as a polyester resin.
- the polymerized rosin compound of the present invention may contain, in addition to the rosin dimer component (A), a component (B) of rosin trimer or higher, an unreacted rosin ester, and rosin acid (resin acid). Good.
- the rosin trimer or higher component (B) include rosin acid (resin acid) trimer or higher component or rosin acid (resin acid) trimer or higher esterified product.
- the difunctional group-containing rosin dimer component (a1) is not particularly limited as long as the rosin is a dimer and has two functional groups (ROOC-) in the dimer.
- the bifunctional group-containing rosin dimer component (a1) has, for example, the following general formula (1A) and general formula (1B) (R is hydrogen, an alkyl group having 1 to 5 carbon atoms or a benzyl group). To express).
- the functional group (ROOC-) is a carboxyl group and / or a carboxylate group
- the two functional groups in the difunctional group-containing rosin dimer component (a1) are both carboxylate groups ( a10), one is a carboxyl group and the other is a carboxylic acid ester group (a11), and both are carboxyl groups (a12).
- the (a11) and (a12) in the bifunctional rosin dimer component (a1) are obtained by hydrolysis of the carboxylic acid ester group of (a10). Therefore, the bifunctional group-containing rosin dimer component (a1) can also be contained as a rosin dimer having a carboxyl group of (a11) and (a12) by appropriate hydrolysis.
- the difunctional group-containing rosin dimer component (a1) is preferably a dicarboxylic acid ester-containing rosin dimer (a10) in which both of the functional groups (ROOC-) are carboxylic acid ester groups.
- the dicarboxylic acid ester-containing rosin dimer (a10) has the general formula (1 ′): R 1 OOC-X-COOR 1 (wherein X is a rosin dimer residue, R is an alkyl having 1 to 5 carbon atoms) Group or a benzyl group).
- the content of the dicarboxylic acid ester-containing rosin dimer (a10) in the rosin dimer component (A) is preferably 80% by weight or more.
- the dicarboxylic acid ester-containing rosin dimer (a10) is preferably 80% by weight or more, more preferably 90% by weight or more, and further 95% by weight in the bifunctional group-containing rosin dimer component (a1). % Or more, more preferably 99% by weight or more.
- all the difunctional group-containing rosin dimer component (a1) can be a dicarboxylic acid ester-containing rosin dimer (a10).
- the content of the bifunctional group-containing rosin dimer component (a1) component in the rosin dimer component (A) is 80% by weight or more.
- the content of the bifunctional group-containing rosin dimer component (a1) is preferably 85% by weight or more, more preferably 90% by weight or more, and preferably 100% by weight.
- the polymerized rosin compound of the present invention is composed of the rosin trimer or higher component (B), the monofunctional group-containing rosin dimer component (a2), and the rosin dimer component (a3) not having the functional group.
- the total content is preferably 20% by weight or less.
- the total content is preferably 15% by weight or less, more preferably 10% by weight or less.
- the component (B) of the rosin trimer or higher is preferably 15% by weight or less, and more preferably 10% by weight or less to synthesize a linear polymer (polyester resin). This is preferable.
- the monofunctional group-containing rosin dimer component (a2) is preferably 15% by weight or less, and more preferably 5% by weight or less from the viewpoint of synthesizing a high molecular weight polyester resin.
- the rosin dimer component (a3) having no functional group is preferably 10% by weight or less, and more preferably 5% by weight or less from the viewpoint of reducing unreacted substances.
- the polymerized rosin compound of the present invention is represented by the general formula (3): X 1 -COOR 1 (wherein X 1 represents a rosin residue and R 1 represents an alkyl group having 1 to 5 carbon atoms or a benzyl group). It can be obtained by purifying a raw material containing a rosin ester after polymerization using a catalyst.
- the rosin residue means a portion obtained by removing the functional group (ROOC-) from rosin ester.
- ROOC- functional group
- Examples of rosin esters used as raw materials include natural rosin esters. Examples of the natural rosin include gum rosin, tall oil rosin, wood rosin and the like. These can be used after purification such as distillation to improve the color tone of the resulting polymerized rosin compound.
- the purity of the rosin ester in the raw material is preferably 80% by weight or more, and more preferably 90% by weight or more from the viewpoint of improving the color tone. Further, from the viewpoint of obtaining the polymerized rosin compound of the present invention, it is preferable to contain a large amount of rosin ester derived from a resin acid having a conjugated double bond such as abietic acid, neoabietic acid, and parastrinic acid. It is preferable that the total amount of rosin ester derived from at least one resin acid selected from abietic acid, neoabietic acid and parastrinic acid component in the rosin ester is 40% by weight or more, and more preferably 50% by weight or more. It is preferable from the viewpoint of improving the yield of the rosin dimer component (A) in the obtained polymerized rosin compound.
- rosin ester examples include rosin esters having 1 to 5 carbon atoms such as rosin methyl ester, rosin ethyl ester, rosin butyl ester, and rosin pentyl ester, and rosin benzyl ester.
- rosin methyl ester it is preferable because unreacted rosin ester is easily distilled off under reduced pressure after the reaction. Therefore, as the bifunctional group-containing rosin dimer component (a1), a polymerized rosin compound containing a dimethyl ester group-containing rosin dimer is preferable.
- the dimethyl ester group-containing rosin dimer is such that R in the above general formula (1A) and general formula (1B) is a methyl group, and the general formula (1 ′′): CH 3 OOC—X—COOCH 3 ( Wherein X represents a rosin ester dimer residue.
- the rosin ester can be obtained by esterifying natural rosin and / or purified product thereof with a monohydric alcohol.
- the esterification is not particularly limited, and a known method can be adopted.
- rosin acid (resin acid) contained in natural rosin is used as an acid chloride (rosin acid chloride) to react alcohol, or after reacting rosin acid and alcohol under pressure for a certain period of time, alcohol and water
- Examples include a method in which the mixed solution is removed, fresh alcohol is added, and the reaction is repeated.
- a method for deriving rosin acid chloride from rosin acid it is preferable to employ the thionyl chloride method.
- alcohols having 1 to 5 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, i-butanol, t-butyl alcohol, pentanol, and benzyl alcohol can be used.
- the above rosin ester polymerization method is carried out by heating the rosin ester.
- the polymerization reaction conditions are not particularly limited, and are determined by appropriately selecting from conventionally known conditions.
- a rosin ester may be polymerized using an organic solvent as necessary in the presence of a catalyst.
- a known catalyst used for the production of polymerized rosin can be used.
- Specific examples include solids having sulfuric acid, formic acid, acetic acid, phosphoric acid, paratoluenesulfonic acid, methanesulfonic acid, and sulfonic acid groups.
- Polymer having pendant sulfonic acid group such as acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or fluorine-based polymer having sulfonic acid type functional group, hydrogen fluoride, zinc chloride, aluminum chloride, titanium tetrachloride, boron trifluoride and Examples thereof include boron trifluoride derivatives such as boron trifluoride phenol complex, boron trifluoride dimethyl ether complex, and boron trifluoride diethyl ether complex. These may be used alone or in combination of two or more.
- the catalyst it is possible to use at least one selected from the group consisting of sulfuric acid, formic acid, phosphoric acid, paratoluenesulfonic acid, methanesulfonic acid, solid acid having a sulfonic acid group, and zinc chloride for the removal of the catalyst after the reaction. It is preferable in terms of ease.
- the amount of the catalyst used is preferably 0.1 to 90 parts by weight with respect to 100 parts by weight of the rosin ester. From the viewpoint of suppressing side reactions, the amount is preferably 1 to 20 parts by weight.
- the organic solvent is not particularly limited as long as it does not inhibit the polymerization reaction of rosin ester.
- aromatic hydrocarbons such as toluene and xylene: aliphatic hydrocarbons such as heptane and octane: ketone hydrocarbons such as methyl ethyl ketone and methyl isopropyl ketone: ester hydrocarbons such as ethyl acetate and butyl acetate: Halogenated hydrocarbons such as carbon tetrachloride, ethylene dichloride, trichloroethane, tetratrichloroethane: acetic acid, propionic acid, butyric acid, and anhydrides thereof, organic acids containing carboxyl groups such as formic acid, chloroacetic acid, lactic acid, etc.
- formic acid and acetic acid can be used individually by 1 type or in combination of 2 or more types as appropriate.
- formic acid and acetic acid When formic acid and acetic acid are used as organic solvents, formic acid and acetic acid also function as a catalyst, so that it is not necessary to use another catalyst.
- formic acid and acetic acid are used as an organic solvent together with a catalyst, the following organic solvent ratio is applied as the ratio of formic acid and acetic acid.
- aromatic hydrocarbons or aliphatic hydrocarbons are preferable among organic solvents, and xylene, heptane, and octane are particularly optimal.
- the amount of the organic solvent to be used is not particularly limited, but is usually in the range of 5 to 900 parts by weight, more preferably 10 to 500 parts by weight with respect to 100 parts by weight of the charged rosin ester in the reaction system. .
- the reaction conditions for the polymerization are not particularly limited, and examples thereof include a method of reacting at a temperature of about 0 to 200 ° C., preferably 40 to 200 ° C. for about 0.5 to 24 hours.
- a polymerized rosin compound can be obtained by removing the solvent, catalyst, unreacted rosin ester and decomposition product used from the polymerization reaction product, if necessary.
- the catalyst removal method for example, water washing, alkali neutralization, filtration, and the like can be employed.
- vacuum distillation can be employed as a method for removing unreacted rosin ester and decomposition products. The vacuum distillation is preferably carried out under conditions of a temperature of 200 to 290 ° C. and a degree of vacuum of 60 to 8000 Pa.
- the polymerized rosin compound of the present invention contains many bifunctional group-containing rosin dimer components (a1) and is therefore useful as a dicarboxylic acid component in the production of polyester resins.
- the polyester resin of the present invention (hereinafter referred to as “rosin polyester”) is obtained, for example, by reacting at least a dicarboxylic acid component and a dialcohol component.
- the polymerized rosin compound of the present invention is used as the dicarboxylic acid component.
- dicarboxylic acid component other dicarboxylic acid components other than the polymerized rosin compound may be used in combination.
- dicarboxylic acid component that can be used in combination include at least one selected from the group consisting of aromatic dicarboxylic acids and aliphatic dicarboxylic acids.
- aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid
- aliphatic dicarboxylic acids such as pimelic acid, suberic acid, azelaic acid, and sebacic acid.
- unsaturated dibasic acids such as maleic acid, fumaric acid, citraconic acid, itaconic acid and glutaconic acid; aromatic dibasic acids such as phthalic acid, isophthalic acid and terephthalic acid; dodecenyl succinic acid, dodecyl succinic acid, octenyl succinic acid, Examples thereof include succinic acid substituted with an alkyl group or alkenyl group having 1 to 20 carbon atoms such as octyl succinic acid; (meth) acrylic acid-added rosin and the like.
- the ratio of the polymerized rosin compound of the present invention in the dicarboxylic acid component is not particularly limited, but is preferably 5 to 95% by weight, more preferably 20 to 90% by weight from the viewpoint of improving the thermal decomposition temperature. preferable.
- an acid component other than the dicarboxylic acid component can be used.
- a monovalent carboxylic acid or a trivalent or higher carboxylic acid including the carboxylic acid anhydride and the lower ester
- a monovalent carboxylic acid or a trivalent or higher carboxylic acid including the carboxylic acid anhydride and the lower ester
- Examples of the monovalent carboxylic acid include fatty acids, monofunctional rosins, and t-butylbenzoic acid.
- the amount of monovalent carboxylic acid used is usually 10 mol% or less, preferably 5 mol% or less of all carboxylic acid components.
- trivalent or higher carboxylic acids examples include 1,2,4-butanetricarboxylic acid, trimellitic acid, naphthalenetricarboxylic acid, pyromellitic acid, maleated rosin, fumarated rosin, and acid anhydrides thereof. And lower esters.
- the amount of trivalent or higher carboxylic acids used is usually 10 mol% or less, preferably 5 mol% or less of the total carboxylic acid component.
- the dialcohol component is not particularly limited as long as it does not inhibit the polymerization reaction of rosin polyester.
- examples thereof include at least one selected from the group consisting of aliphatic diols. Specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,4-butenediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 2-ethyl-2-methylpropane-1,3-diol, 2-butyl-2- Ethylpropane-1,3-diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol,
- an alcohol component other than the alcohol component can be used.
- trivalent or higher alcohols can be used as necessary.
- trihydric or higher alcohols include glycerin, trimethylolpropane, 2-methylpropanetriol, pentaerythritol, dipentaerythritol, sorbitol, etc., and these compounds may be used alone or in appropriate combination. Used.
- the amount of the trihydric or higher alcohols is not particularly limited, but is usually 10 mol% or less, preferably 5 mol% or less of all alcoholic acid components.
- the production method of the rosin polyester of the present invention is not particularly limited, and various known esterification reactions and transesterification reactions can be appropriately selected.
- the above-mentioned all carboxylic acid components and all alcohol components are charged into a predetermined reaction vessel, and dehydration condensation proceeds at about 180 to 300 ° C. while blowing an inert gas in the presence or absence of an esterification catalyst. It can be carried out.
- the reaction method either a transesterification reaction or a direct esterification reaction can be applied.
- polycondensation can be promoted by a method of increasing the reaction temperature by pressurization, a pressure reduction method, or a method of flowing an inert gas under normal pressure.
- the charging ratio of the total carboxylic acid component and the total alcohol component is not particularly limited, but usually the OH / COOH (equivalent ratio) is about 1.2 to 0.8, preferably 0.9 to 1.1. What is necessary is just to determine each preparation amount.
- the reaction can be traced by measuring the acid value, viscosity or softening point.
- esterification catalysts such as at least 1 sort (s) of metal compound chosen from antimony, titanium, tin, zinc, aluminum, and manganese, are used, and reaction may be accelerated
- Examples thereof include zinc acetate, zinc oxide, stannous oxide, monobutyltin oxide, dibutyltin oxide, dibutyltin dilaurate, tetraalkylorthotitanate, zirconium alkoxide and the like.
- tetraalkyl orthotitanate tetraethyl orthotitanate and tetrabutyl orthotitanate are preferably used.
- zirconium alkoxide tetraethyl orthozirconate, tetraisopropyl orthozirconate and the like are preferably used.
- the addition amount of these esterification catalysts is preferably 0.01 parts by weight or more and 5 parts by weight or less, more preferably 0.1 parts by weight or more and 2 parts by weight or less with respect to 100 parts by weight of the total amount of all carboxylic acid components and all alcohol components. .
- a high molecular weight polyester resin having a number average molecular weight of 3000 to 400,000 and a weight average molecular weight of 3000 to 40000 can be obtained.
- the number average molecular weight is preferably 5000 to 300000, and more preferably 8000 to 200000.
- the weight average molecular weight is preferably from 5,000 to 300,000, more preferably from 8,000 to 200,000.
- the molecular weight distribution of the polyester resin preferably satisfies 1.0 to 3.0.
- a polyester resin having a thermal decomposition temperature of 350 ° C. or higher can be obtained.
- the thermal decomposition temperature is preferably 350 to 450 ° C, more preferably 350 to 420 ° C.
- rosin component (resin acid component) in the rosin ester in the present invention was analyzed by gas chromatographic analysis (GC).
- GC gas chromatographic analysis
- the GC was Agilent Technologies Agilent 6890, the column was Spellco BDS, and the rosin ester was dissolved in a 1: 1 mixed solution of toluene and methanol.
- the purity of the rosin ester is obtained by subtracting the neutral component ratio calculated from the sum of all peak area ratios detected at a retention time of 1.4 minutes to 6.0 minutes and the unreacted rosin ratio calculated from the acid value described later. Refers to the value.
- the total amount of the ester components of various abietic acid, neoabietic acid and parastrinic acid was calculated from the sum of the respective peak area ratios. For example, in rosin methyl ester, the peak detected at 8.4 minutes was calculated as the parastriic acid methyl ester component, 12.7 minutes as the abietic acid methyl ester component, and 14.3 minutes as the neo abietic acid methyl ester component peak. .
- the softening point of the polymerized rosin compound in the present invention was measured by the JIS method (JIS K 2425 ring and ball method).
- the acid value of the rosin methyl ester, polymerized rosin compound and rosin polyester in the present invention was measured by the JIS method (JIS K 0070).
- the hydroxyl value of the rosin polyester in the present invention was measured by the JIS method (JIS K 0070).
- GC-MS gas chromatography mass spectrometry
- the rosin dimer component (a3) having no functional group refers to all peaks of m / z; 520 detected at a retention time of 22 to 24 minutes.
- the various monofunctional group-containing rosin dimer components (a2) and the bifunctional group-containing rosin dimer (a1) show all peaks corresponding to their respective molecular weights (m / z). For example, when a compound of general formula (1) where R is a methyl group is produced, the monofunctional group-containing rosin dimer component (a2) in the resulting polymerized rosin compound is detected at a retention time of 24 minutes to 32 minutes.
- M / z refers to all peaks at 574
- the bifunctional rosin dimer (a1) refers to all peaks at m / z; 632 detected at a retention time of 33 to 44 minutes.
- the content ratio is set to 0. Further, the content ratio when the monofunctional group-containing rosin dimer component (a2) was detected was a numerical value obtained by a method for calculating the constituent ratio of various rosin components described later.
- composition ratio of various rosin components in the present invention was measured by gel permeation chromatography (GPC).
- GPC uses Tosoh Co., Ltd. HLC-8220, the column uses "Tskel column” made by Tosoh Co., Ltd., the solvent is measured by THF, the amount of liquid fed 1.0ml / min, each obtained Component peak area ratio of component (B) of rosin trimer or higher, rosin dimer component (A) (bifunctional group-containing rosin dimer component (a1), monofunctional group-containing rosin dimer component (a2) ), Rosin dimer component having no functional group (a3)), rosin acid and rosin ester component composition ratios are shown in Table 3.
- the method for measuring the number average molecular weight, weight average molecular weight, and molecular weight distribution of the rosin polyester in the present invention was measured by gel permeation chromatography (GPC).
- GPC uses HLC-8220 manufactured by Tosoh Corporation, and uses “Tskel column” manufactured by Tosoh Corporation. Sample concentration is 1.0%, solvent is THF, liquid feeding amount is 0.6 ml / min, The sample injection volume was 10 ⁇ l, the measurement temperature was 40 ° C., and the measurement was performed using an RI detector.
- the calibration curve is “TSK Standard Polystyrene” manufactured by Tosoh Corporation: “A-1000”, “A-5000”, “F-1”, “F-2”, “F-4”, “F-10”. ”,“ F-20 ”,“ F-40 ”,“ F-80 ”, and“ F-128 ”.
- the glass transition temperature Tg of the rosin polyester is shown in Table 5 when measured using a thermal analyzer DSC3100S manufactured by Bruker A.X. at a nitrogen flow rate of 200 ml / min and a heating rate of 10 ° C./min. .
- the thermal decomposition temperature of rosin polyester was measured at a nitrogen flow rate of 200 ml / min and a heating rate of 5 ° C./min using a TG-DTA2000S differential thermal thermogravimetric simultaneous measurement device manufactured by Bruker Ax. Table 5 shows the temperature at the time of the thermal decomposition.
- Prototype 1 purified rosin methyl ester (prototype 1) was obtained.
- the acid value was 0.5 mgKOH / g (unreacted rate 0.3%).
- the amount of neutral components in Prototype 1 was 1.1% (rosin ester purity 98.6%), and the total amount of abietic acid, neoabietic acid, and parastolic acid was 74.7%.
- xylene and methanol were distilled off under conditions of a liquid temperature of less than 200 ° C. and a reduced pressure of 1300 Pa, and further distilled under a condition of a liquid temperature of 240 ° C. and a reduced pressure of 1200 Pa.
- 75 g of purified rosin ethyl ester (prototype 2) was obtained.
- the acid value was 0.4 mgKOH / g (unreacted rate 0.2%).
- the amount of neutral components in Prototype 2 was 1.5% (rosin ester purity 98.3%), and the total amount of abietic acid, neoabietic acid, and parastolic acid was 72.6%.
- xylene and methanol were distilled off under conditions of a liquid temperature of less than 200 ° C. and a reduced pressure of 1300 Pa, and further distilled under a condition of a liquid temperature of 250 ° C. and a reduced pressure of 1200 Pa.
- 80 g of purified rosin ethyl ester (prototype 3) was obtained.
- the acid value was 0.6 mgKOH / g (unreacted rate 0.4%).
- the amount of neutral components in prototype 2 was 1.6% (rosin ester purity: 98.0%), and the total amount of abietic acid, neoabietic acid, and parastolic acid was 75.1%.
- Example 1 Synthesis of Polymerized Rosin Compound 1 (Compound of General Formula (1) where R is Hydrogen or Methyl Group))
- a reactor equipped with a cooling pipe, a thermometer, a stirrer, and a nitrogen introduction pipe was charged with 900 g of Prototype 1 (purified rosin methyl ester) manufactured by Arakawa Chemical Co., Ltd., 900 g of xylene, 45.0 g of zinc chloride as a catalyst, and 45 sulfuric acid. 0.0 g was charged, and a polymerization reaction was carried out at 145 ° C. for 6 hours under a nitrogen stream.
- Prototype 1 purified rosin methyl ester
- the xylene solution of the reaction product was washed by adding 7 g of concentrated hydrochloric acid and 500 g of warm water, and then washed twice with 500 g of warm water. After washing, the xylene solution is distilled off under conditions of a liquid temperature of less than 200 ° C. and a reduced pressure of 6000 Pa, and further, a purified rosin methyl ester decomposition product and an unreacted purified product under the conditions of a liquid temperature of 275 ° C. and a reduced pressure of 150 Pa. Rosin methyl ester was distilled off to obtain 405 g of polymerized rosin compound 1. The softening point was 110 ° C. and the acid value was 0.5 mgKOH / g.
- the rosin dimer component (A) and the rosin dimer component (a3) having no functional group were not detected in the rosin dimer component (A) by GC / MS measurement.
- the rosin dimer component (A) of the polymerized rosin compound 1 was 91.6% (the content of the bifunctional group-containing rosin dimer component (a1) in the rosin dimer component (A) was 100).
- % Most of the bifunctional group-containing rosin dimer component (a1) was a dimethyl ester group-containing rosin dimer), rosin acid and rosin ester monomers were 5.4%, rosin trimer or more
- the content of component (B) was 3.0%.
- Example 2 Synthesis of Polymerized Rosin Compound 2 (Compound of General Formula (1) where R is Hydrogen or Methyl Group)) The treatment was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 except that 45.0 g of zinc chloride and 45.0 g of 85% aqueous phosphoric acid solution were used as the catalyst. The results are shown in Table 3.
- Example 3 Synthesis of Polymerized Rosin Compound 3 (Compound of General Formula (1) where R is Hydrogen or Methyl Group))
- the reaction was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 except that 900 g of formic acid was used as a catalyst (also serving as a solvent).
- 900 g of heptane was charged, the formic acid layer was separated, 500 g of water was added to the heptane solution of the reaction product and washed, and then washed twice with 500 g of water.
- the washed heptane solution was treated in the same manner as in Example 1, and the results are shown in Table 3.
- Example 4 Synthesis of Polymerized Rosin Compound 4 (Compound of General Formula (1) where R is Hydrogen or Methyl Group)) The reaction was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 except that 45.0 g of paratoluenesulfonic acid was used as the catalyst. After completion of the reaction, the same treatment as in Example 3 was performed, and the results are shown in Table 3.
- Example 5 Synthesis of Polymerized Rosin Compound 5 (Compound of General Formula (1) where R is Hydrogen or Methyl Group)) The reaction was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 except that 36.0 g of methanesulfonic acid was used as the catalyst. After completion of the reaction, the same treatment as in Example 3 was performed, and the results are shown in Table 3.
- Example 6 Synthesis of Polymerized Rosin Compound 6 (Compound of General Formula (1) where R is Hydrogen or Methyl Group)) The reaction was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 except that 36.0 g of methanesulfonic acid and 47.4 g of acetic acid were used as the catalyst. After completion of the reaction, the same treatment as in Example 3 was performed, and the results are shown in Table 3.
- Example 7 Synthesis of Polymerized Rosin Compound 7 (Compound of General Formula (1) where R is Hydrogen or Methyl Group)) The reaction was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 except that 19.5 g of a solid acid catalyst Teika Cure (acid component was sulfonic acid group) manufactured by Teika Co., Ltd. was used as the catalyst. After completion of the reaction, 68.3 g of heptane was charged, the heptane solution of the reaction product and the solid acid catalyst were separated, and 16 g of water was added to the reaction product heptane solution and washed. The washed heptane solution was treated in the same manner as in Example 1, and the results are shown in Table 3.
- Teika Cure acid component was sulfonic acid group
- Example 8 Synthesis of Polymerized Rosin Compound 8 (Compound of General Formula (1) where R is Hydrogen or Methyl Group)) The reaction was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 except that 22.7 g of solid acid catalyst Amberlist (acid component was sulfonic acid group) manufactured by Organo Corporation was used as the catalyst. After completion of the reaction, the same treatment as in Example 7 was performed, and the results are shown in Table 3.
- Example 9 Synthesis of Polymerized Rosin Compound 9 (Compound of General Formula (1) where R is Hydrogen or Ethyl Group)) The reaction was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 except that 900 g of Prototype 2 (purified rosin ethyl ester) manufactured by Arakawa Chemical Industries, Ltd. and 36.0 g of methanesulfonic acid were used as the catalyst. did. After completion of the reaction, the same treatment as in Example 3 was performed, and the results are shown in Table 3.
- Example 10 Synthesis of polymerized rosin compound 10 (compound of general formula (1) wherein R is hydrogen or butyl group)) The reaction was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 except that 900 g of Prototype 3 (purified rosin butyl ester) manufactured by Arakawa Chemical Industries, Ltd. and 36.0 g of methanesulfonic acid were used as the catalyst. did. After completion of the reaction, the same treatment as in Example 3 was performed, and the results are shown in Table 3.
- Example 11 Synthesis of linear high molecular weight polymer (polyester resin: rosin polyester) using polymerized rosin compound) 316 g of the polymerized rosin compound 1 obtained in Example 1, 90 g of 1,4 butanediol, and 5 g of tetrabutyl titanate were charged into a 1 L separable corben equipped with a thermometer, a nitrogen introduction tube, a water separator and a stirrer. The temperature was raised to 235 ° C., the temperature was kept for 5 hours, and the transesterification reaction was performed while discharging methanol. 101 g of sebacic acid was charged, the temperature was raised from 195 ° C. to 245 ° C.
- polyester resin polymer resin
- the acid value of the reaction solution was 3.3 mgKOH / g.
- the reflux dehydration apparatus was replaced with a vacuum decompression apparatus, and a reduced pressure polycondensation reaction was performed under vacuum (400 Pa or less).
- the reaction was completed after 6.5 hours.
- the same reaction was carried out for the polymerized rosin compounds of Examples 2 to 10, and the results are shown in Table 4.
- Comparative Example 1 Synthesis of Polymerized Rosin 1 The treatment was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1, except that 900 g of unpurified rosin (Chinese gum rosin), 40 g of zinc chloride and 6.0 g of sulfuric acid were used as catalysts.
- the GC / MS measurement was performed by dissolving the polymerized rosin 1 in a 1: 1 mixed solution of toluene and methanol, then adding a few drops of a 10% hexane solution of trimethylsilyldiazomethane manufactured by Amax Co., Ltd. Analysis was performed after the application, and the results are shown in Table 3.
- Comparative Example 2 Analysis was performed after polymerizing rosin 2 (trade name: Silvaros PR140, manufactured by Arizona Chemical Co., Ltd.) was subjected to the same methyl esterification reaction as in Comparative Example 1, and the results are shown in Table 3.
- Comparative Example 3 Polymerization rosin 3 (trade name: Daimalex, Hercules Co., Ltd.) was subjected to the same methyl esterification reaction as in Comparative Example 1 and then analyzed. The results are shown in Table 3.
- Comparative Example 4 Polymerization rosin 4 (trade name: Aradim R-140, manufactured by Arakawa Chemical Industries, Ltd.) was subjected to the same methyl esterification reaction as in Comparative Example 1 and then analyzed, and the results are shown in Table 3.
- Comparative Example 8 Synthesis of Polymerized Rosin Compound 14
- a polymerized rosin having an acid value of 146.0 mg KOH / g and a softening point of 137 ° C. (trade name: Aradim R-140, manufactured by Arakawa Chemical Industries, Ltd.) 100 g, xylene 100 g, and methanol 83.3 g were charged. While stirring this, 46.4 g of thionyl chloride was added dropwise over 2 hours to subject the polymerized rosin to methyl esterification.
- the rosin dimer component (A) of the polymerized rosin compound 14 was 87.8% (the content of the bifunctional group-containing rosin dimer component (a1) in the rosin dimer component (A) was 51). 0.7%, content of monofunctional group-containing rosin dimer component (a2) is 48.1%, content ratio of rosin dimer component (a3) having no functional group is 0.2%), rosin acid The rosin ester monomer was 2.8%, and the content of the rosin trimer or higher component (B) was 9.4%.
- Examples 1 to 8 are dimethyl ester group-containing rosin dimers, and Example 9 is mostly a diethyl ester group-containing rosin dimer, Examples. No. 10 was mostly a dibutyl ester group-containing rosin dimer.
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Abstract
Description
これらエステル化触媒の添加量は全カルボン酸成分と全アルコール成分の総量100重量部に対して0.01重量部以上5重量部以下が好ましく、0.1重量部以上2重量部以下がより好ましい。
本発明におけるロジンエステル中のロジン成分(樹脂酸成分)の分析についてはガスクロマトグラフ分析(GC)によって分析した。GCはアジレントテクノロジー社製 Agilent6890を使用し、カラムはスペルコ社製BDSを使用し、ロジンエステルはトルエンおよびメタノールの1:1混合溶液に溶解させてから測定した。ロジンエステルの純度は、リテンションタイム1.4分~6.0分に検出されるすべてのピーク面積比の和から算出される中性成分比と後述する酸価から算出した未反応ロジン比率を差し引いた値を指す。また、各種アビエチン酸、ネオアビエチン酸及びパラストリン酸のエステル成分の総量は、各ピーク面積比の和から算出した。例えばロジンメチルエステルにおいては、8.4分に検出されるピークをパラストリン酸メチルエステル成分、12.7分をアビエチン酸メチルエステル成分、14.3分をネオアビエチン酸メチルエステル成分のピークとして算出した。
本発明における重合ロジン化合物はJIS法(JIS K 2425 環球法)により軟化点を測定した。
本発明におけるロジンメチルエステル、重合ロジン化合物及びロジンポリエステルはJIS法(JIS K 0070)により酸価を測定した。
本発明におけるロジンポリエステルはJIS法(JIS K 0070)により水酸基価を測定した。
本発明における重合ロジン化合物の一官能基含有ロジン二量体成分(a2)、及び官能基を有しないロジン二量体成分(a3)の確認については、ガスクロマトグラフ質量分析(GC-MS)によって分析した。GC-MSは、アジレントテクノロジー社製 Agilent6890(GC)及びAgilent5973N(MS)を使用し、カラムはアジレントテクノロジー社製DB-5を使用し、重合ロジン化合物はトルエン及びメタノールの1:1混合溶液に溶解させてから測定した。官能基を有しないロジン二量体成分(a3)は、リテンションタイム22分~24分に検出されるm/z;520のすべてのピークを指す。また、各種一官能基含有ロジン二量体成分(a2)及び二官能基含有ロジン二量体(a1)は、それぞれの分子量(m/z)に対応するすべてのピークを差す。例えば、一般式(1)でRがメチル基の化合物を製造する場合、得られる重合ロジン化合物中の一官能基含有ロジン二量体成分(a2)は、リテンションタイム24分~32分に検出されるm/z;574のすべてのピークを指し、二官能基含有ロジン二量体(a1)はリテンションタイム33分~44分に検出されるm/z;632のすべてのピークを指す。表1には一官能基含有ロジン二量体成分(a2)、官能基を有しないロジン二量体成分(a3)が検出されなければ含有比率を0とした。また、一官能基含有ロジン二量体成分(a2)が検出された時の含有比率は後述する各種ロジン成分の構成比率の算出方法で得られた数値を示した。
本発明における各種ロジン成分の構成比率は、ゲルパーミエーションクロマトグラフィー(GPC)によって測定した。GPCは、東ソー(株)製HLC-8220を使用し、カラムとしては東ソー(株)製「Tskgelカラム」を用い、溶媒をTHF、送液量1.0ml/minで測定し、得られた各成分のピーク面積比をロジン三量体以上の成分(B)、ロジン二量体成分(A)(二官能基含有ロジン二量体成分(a1)、一官能基含有ロジン二量体成分(a2)、官能基を有しないロジン二量体成分(a3))、ロジン酸及びロジンエステル成分の構成比率として表3に示した。
本発明におけるロジンポリエステルの数平均分子量、重量平均分子量、分子量分布の測定方法は、ゲルパーミエーションクロマトグラフィー(GPC)によって測定した。GPCは、東ソー(株)製HLC-8220を使用し、カラムとしては東ソー(株)製「Tskgelカラム」を用い、試料濃度1.0%、溶媒をTHF、送液量0.6ml/min、サンプル注入量10μl、測定温度40℃、RI検出器を用いて測定した。また、検量線は東ソー(株)製「TSK標準ポリスチレン」:「A-1000」、「A-5000」、「F-1」、「F-2」、「F-4」、「F-10」、「F-20」、「F-40」、「F-80」、「F-128」の10サンプルから作成した。
ロジンポリエステルのガラス転移温度Tgは、ブルカー・エイエックス社製熱分析装置DSC3100Sを使用し、窒素流量200ml/分、昇温速度10℃/分で測定した時のガラス転移温度を表5に記載した。
ロジンポリエステルの熱分解温度は、ブルカー・エイエックス社製 示差熱熱重量同時測定装置TG-DTA2000Sを使用し、窒素流量200ml/分、昇温速度5℃/分で測定し、10%重量が減少したときの温度を熱分解温度として表5に記載した。
温度計、攪拌機、窒素導入管及び減圧装置を備えた反応装置に、酸価170.0mgKOH/g、の未精製ロジン(中国ガムロジン)100g、キシレン100g、メタノール83.3gを仕込んだ。これを攪拌しながら塩化チオニル46.4gを2時間かけて滴下して、未精製ロジンにメチルエステル化を施した。滴下終了後5時間還流温度で加熱攪拌後、液温200℃未満、減圧度1300Paの条件下でキシレン及びメタノールを留去した後、更に液温230℃、減圧度1200Paの条件下で蒸留し、精製ロジンメチルエステル(試作品1)を70g得た。酸価は0.5mgKOH/g(未反応率0.3%)であった。GC測定により試作品1中の中性成分量は1.1%(ロジンエステル純度98.6%)、アビエチン酸、ネオアビエチン酸、パラストリン酸の総量は74.7%であった。
温度計、攪拌機、窒素導入管及び減圧装置を備えた反応装置に、酸価170.0mgKOH/g、の未精製ロジン(中国ガムロジン)100g、キシレン100g、エタノール120.0gを仕込んだ。これを攪拌しながら塩化チオニル46.4gを2時間かけて滴下して、未精製ロジンにエチルエステル化を施した。滴下終了後5時間還流温度で加熱攪拌後、液温200℃未満、減圧度1300Paの条件下でキシレン及びメタノールを留去した後、更に液温240℃、減圧度1200Paの条件下で蒸留し、精製ロジンエチルエステル(試作品2)を75g得た。酸価は0.4mgKOH/g(未反応率0.2%)であった。GC測定により試作品2中の中性成分量は1.5%(ロジンエステル純度98.3%)、アビエチン酸、ネオアビエチン酸、パラストリン酸の総量は72.6%であった。
温度計、攪拌機、窒素導入管及び減圧装置を備えた反応装置に、酸価170.0mgKOH/g、の未精製ロジン(中国ガムロジン)100g、キシレン100g、ブタノール193.0gを仕込んだ。これを攪拌しながら塩化チオニル46.4gを2時間かけて滴下して、未精製ロジンにブチルエステル化を施した。滴下終了後5時間還流温度で加熱攪拌後、液温200℃未満、減圧度1300Paの条件下でキシレン及びメタノールを留去した後、更に液温250℃、減圧度1200Paの条件下で蒸留し、精製ロジンエチルエステル(試作品3)を80g得た。酸価は0.6mgKOH/g(未反応率0.4%)であった。GC測定により試作品2中の中性成分量は1.6%(ロジンエステル純度98.0%)、アビエチン酸、ネオアビエチン酸、パラストリン酸の総量は75.1%であった。
冷却管、温度計、攪拌機、窒素導入管を備えた反応装置に、荒川化学工業(株)製試作品1(精製ロジンメチルエステル)を900g、キシレン900g、触媒として塩化亜鉛45.0g及び硫酸45.0gを仕込み、窒素気流下145℃で6時間、重合反応を行なった。反応生成物のキシレン溶液を濃塩酸7g及び温水500gを加えて洗浄した後、更に各500gの温水にて2回洗浄した。洗浄後のキシレン溶液は液温200℃未満、減圧度6000Paの条件下でキシレンを留去した後、更に液温275℃、減圧度150Paの条件下で精製ロジンメチルエステルの分解物及び未反応精製ロジンメチルエステルを留去して、重合ロジン化合物1を405g得た。この軟化点は110℃、酸価は0.5mgKOH/gであった。GC/MS測定により、ロジン二量体成分(A)中に一官能基含有ロジン二量体成分(a2)及び官能基を有しないロジン二量体成分(a3)は検出されなかった。GPC測定により、重合ロジン化合物1のロジン二量体成分(A)は91.6%(ロジン二量体成分(A)中の二官能基含有ロジン二量体成分(a1)の含有率は100%,二官能基含有ロジン二量体成分(a1)の殆どはジメチルエステル基含有ロジン二量体であった)、ロジン酸及びロジンエステルの単量体は5.4%、ロジン三量体以上の成分(B)の含有量は3.0%であった。
触媒として塩化亜鉛45.0g及びリン酸85%水溶液45.0gを使用した以外は実施例1と同様に表1に示すとおりの反応条件で処理を実施した。またその結果を表3に記載した。
触媒(溶媒を兼ねる)としてギ酸900gを使用した以外は実施例1と同様に表1に示すとおりの反応条件で反応を実施した。反応終了後にヘプタン900gを仕込み、ギ酸層を分液し、反応生成物のヘプタン溶液に水500gを加えて洗浄した後、更に各500gの水にて2回洗浄した。洗浄後のヘプタン溶液は、実施例1と同様に処理を実施し、結果を表3に記載した。
触媒としてパラトルエンスルホン酸45.0gを使用した以外は実施例1と同様に表1に示すとおりの反応条件で反応を実施した。反応終了後は実施例3と同様の処理を実施し、結果を表3に記載した。
触媒としてメタンスルホン酸36.0gを使用した以外は実施例1と同様に表1に示すとおりの反応条件で反応を実施した。反応終了後は実施例3と同様の処理を実施し、結果を表3に記載した。
触媒としてメタンスルホン酸36.0g及び酢酸47.4gを使用した以外は実施例1と同様に表1に示すとおりの反応条件で反応を実施した。反応終了後は実施例3と同様の処理を実施し、結果を表3に記載した。
触媒としてテイカ株式会社製固体酸触媒テイカキュア(酸成分がスルホン酸基)19.5gを使用した以外は実施例1と同様に表1に示すとおりの反応条件で反応を実施した。反応終了後にヘプタン68.3gを仕込み、反応生成物のヘプタン溶液と固体酸触媒を分離し、反応生成物のヘプタン溶液に水16gを加えて洗浄した。洗浄後のヘプタン溶液は実施例1と同様に処理を実施し、結果を表3に記載した。
触媒としてオルガノ株式会社製固体酸触媒アンバーリスト(酸成分がスルホン酸基)22.7gを使用した以外は実施例1と同様に表1に示すとおりの反応条件で反応を実施した。反応終了後は実施例7と同様の処理を実施し、結果を表3に記載した。
荒川化学工業(株)製試作品2(精製ロジンエチルエステル)を900g、触媒としてメタンスルホン酸36.0gを使用した以外は実施例1と同様に表1に示すとおりの反応条件で反応を実施した。反応終了後は実施例3と同様の処理を実施し、結果を表3に記載した。
荒川化学工業(株)製試作品3(精製ロジンブチルエステル)を900g、触媒としてメタンスルホン酸36.0gを使用した以外は実施例1と同様に表1に示すとおりの反応条件で反応を実施した。反応終了後は実施例3と同様の処理を実施し、結果を表3に記載した。
実施例1で得られた重合ロジン化合物1を316g、1,4ブタンジオール90g、テトラブチルチタネート5gを温度計、窒素導入管、分水器及び攪拌装置のついた1Lのセパラブルコルベンに仕込み、235℃まで昇温し、5時間保温しメタノールを排出させながらエステル交換反応を行った。セバシン酸101gを仕込み、195℃から3.5時間かけ245℃まで昇温し、その後、2.5時間保温し、エステル化を完結させて高分子量体(ポリエステル樹脂)を得た。反応液の酸価は3.3mgKOH/gであった。次に還流脱水装置を真空減圧装置に替え、真空下(400Pa以下)で減圧重縮合反応を行った。反応は6.5時間行った時点で終了した。得られたポリエステル樹脂のメインピークは数平均分子量(Mn)10000、重量平均分子量(Mw)22000、Mw/Mn=2.2、酸価0.6mgKOH/g、水酸基価5.5mgKOH/gであった。また、実施例2~10の重合ロジン化合物についても同様の反応を実施し、その結果を表4に記載した。
未精製ロジン(中国産ガムロジン)900g、触媒として塩化亜鉛40g及び硫酸6.0gを使用した以外は、実施例1と同様に表1に示すとおりの反応条件で処理を実施した。またGC/MS測定は、重合ロジン1をトルエン及びメタノールの1:1混合溶液に溶解させた後、アヅマックス株式会社製トリメチルシリルジアゾメタン10%ヘキサン溶液を数滴加え、重合ロジン1にメチルエステル化反応を施してから分析を行い、その結果を表3に記載した。
重合ロジン2(商品名:シルバロスPR140、アリゾナケミカル(株)製)に比較例1と同様のメチルエステル化反応を施してから分析を実施し、その結果を表3に記載した。
重合ロジン3(商品名:ダイマレックス、ハーキュレス(株)製)に比較例1と同様のメチルエステル化反応を施してから分析を実施し、その結果を表3に記載した。
重合ロジン4(商品名:アラダイムR-140、荒川化学工業(株)製)に比較例1と同様のメチルエステル化反応を施してから分析を実施し、その結果を表3に記載した。
温度計、攪拌機、窒素導入管を備えた反応装置に、実施例1で得られた重合ロジン化合物1を10g、及び荒川化学工業(株)製試作品1(精製ロジンメチルエステル)を90g仕込み、150℃まで昇温し、攪拌しながら1時間保温して重合ロジン化合物11を100g得た。GPC測定により、重合ロジン化合物11のロジン二量体成分(A)は9.2%(二官能基含有ロジン二量体成分(a1)の含有率は100%)、ロジン酸及びロジンエステルの単量体は90.5%、ロジン三量体以上の成分(B)の含有量は0.3%であった。
比較例5と同様に表2に示すとおりの配合処方で混合した結果を表3に記載した。
比較例5と同様に表2に示すとおりの配合処方で混合した結果を表3に記載した。
温度計、攪拌機、窒素導入管及び減圧装置を備えた反応装置に、酸価146.0mgKOH/g、軟化点137℃の重合ロジン(商品名:アラダイムR-140、荒川化学工業(株)製)100g、キシレン100g、メタノール83.3gを仕込んだ。これを攪拌しながら塩化チオニル46.4gを2時間かけて滴下して、重合ロジンにメチルエステル化を施した。滴下終了後5時間還流温度で加熱攪拌後、液温200℃未満、減圧度1300Paの条件下でキシレン及びメタノールを留去した後、更に液温275℃、減圧度150Paの条件下でロジンメチルエステルの分解物及びロジンメチルエステルを留去して、重合ロジン化合物14を55g得た。この軟化点は109℃、酸価は1.8mgKOH/gであった。GC/MS測定により、ロジン二量体成分(A)中に一官能基含有ロジン二量体成分(a2)及び官能基を有しないロジン二量体成分(a3)が検出された。GPC測定により、重合ロジン化合物14のロジン二量体成分(A)は87.8%(ロジン二量体成分(A)中の二官能基含有ロジン二量体成分(a1)の含有率は51.7%、一官能基含有ロジン二量体成分(a2)の含有率は48.1%、官能基を有しないロジン二量体成分(a3)の含有比率は0.2%)、ロジン酸及びロジンエステルの単量体は2.8%、ロジン三量体以上の成分(B)の含有量は9.4%であった。
比較例1~8の重合ロジン化合物又は重合ロジンのエステル化物を実施例11と同様の反応を実施し、その結果を表4に記載した。
Claims (11)
- ロジン二量体成分(A)の含有量が80重量%以上であり、かつ、前記ロジン二量体成分(A)中の、一般式(1):ROOC-X-COOR(式中、Xはロジン二量体残基、Rは水素、又は炭素数1~5のアルキル基もしくはベンジル基を表す)で表わされる二官能基含有ロジン二量体成分(a1)の含有量が80重量%以上であることを特徴とする重合ロジン化合物。
- 前記ロジン二量体成分(A)中の、一般式(1´):R1OOC-X-COOR1(式中、Xはロジン二量体残基、Rは炭素数1~5のアルキル基又はベンジル基を表す)で表わされるジカルボン酸エステル含有ロジン二量体(a10)の含有量が80重量%以上であることを特徴とする請求項1記載の重合ロジン化合物。
- ロジン三量体以上の成分(B)、一般式(2):ROOC-(式中、Rは水素、又は炭素数1~5のアルキル基もしくはベンジル基を表す)で表わされる官能基を一つ有する一官能基含有ロジン二量体成分(a2)及び一般式(2):ROOC-(式中、Rは水素、又は炭素数1~5のアルキル基もしくはベンジル基を表す)で表わされる官能基を有しないロジン二量体成分(a3)を合わせた含有量が20重量%以下であることを特徴とする請求項1又は2に記載の重合ロジン化合物。
- 前記一般式(1´):R1OOC-X-COOR1(式中、Xはロジン二量体残基、Rは炭素数1~5のアルキル基又はベンジル基を表す)で表わされるジカルボン酸エステル含有ロジン二量体(a10)が、一般式(1´´):CH3OOC-X-COOCH3(式中、Xはロジン二量体残基を表す)で表わされるジメチルエステル基含有ロジン二量体を含有することを特徴とする請求項2又は3記載の重合ロジン化合物。
- 一般式(3):X1-COOR1(式中、X1はロジン残基、R1は炭素数1~5のアルキル基又はベンジル基を表す)で表わされるロジンエステルを含む原料を、重合ロジン製造用触媒を用いて重合することを特徴とする請求項1~4のいずれかに記載の重合ロジン化合物の製造方法。
- 前記重合ロジン製造用触媒として硫酸、ギ酸、酢酸、リン酸、パラトルエンスルホン酸、メタンスルホン酸、スルホン酸基を有する固体酸、及び塩化亜鉛からなる群より選ばれる少なくとも1種を用いることを特徴とする請求項5記載の重合ロジン化合物の製造方法。
- 前記原料中の前記ロジンエステルの純度が80重量%以上であり、かつ前記ロジンエステル中のアビエチン酸、ネオアビエチン酸及びパラストリン酸成分から選ばれる少なくとも1つの樹脂酸に由来するロジンエステルの総量が40重量%以上であることを特徴とする請求項6又は7記載の重合ロジン化合物の製造方法。
- 少なくともジカルボン酸成分とジアルコール成分を反応させるポリエステル樹脂の製造方法であって、前記ジカルボン酸成分が、請求項1~4のいずれかに記載の重合ロジン化合物を含有することを特徴とするポリエステル樹脂の製造方法。
- 前記ポリエステル樹脂の数平均分子量が3000~400000であり、重量平均分子量が3000~400000であることを特徴とする請求項8記載のポリエステル樹脂の製造方法。
- 前記ポリエステル樹脂の熱分解温度が350℃以上であることを特徴とする請求項8又は9記載のポリエステル樹脂の製造方法。
- 請求項8~10のいずれかに記載の製造方法により得られたポリエステル樹脂。
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WO2018203497A1 (ja) | 2017-05-01 | 2018-11-08 | 荒川化学工業株式会社 | ジアミン化合物、ジアミン化合物の製造方法およびポリイミド |
WO2020003780A1 (ja) * | 2018-06-27 | 2020-01-02 | Dic株式会社 | ウレタン樹脂組成物、表面処理剤、及び、物品 |
JPWO2020003780A1 (ja) * | 2018-06-27 | 2021-08-02 | Dic株式会社 | ウレタン樹脂組成物、表面処理剤、及び、物品 |
JP7294338B2 (ja) | 2018-06-27 | 2023-06-20 | Dic株式会社 | ウレタン樹脂組成物、表面処理剤、及び、物品 |
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JP6124151B2 (ja) | 2017-05-10 |
EP2889285A1 (en) | 2015-07-01 |
EP2889285B1 (en) | 2019-02-20 |
TW201410790A (zh) | 2014-03-16 |
TWI554573B (zh) | 2016-10-21 |
US20150232604A1 (en) | 2015-08-20 |
CN104583175B (zh) | 2017-12-19 |
CN104583175A (zh) | 2015-04-29 |
US20170152341A9 (en) | 2017-06-01 |
EP2889285A4 (en) | 2015-08-19 |
JPWO2014030652A1 (ja) | 2016-07-28 |
US10392465B2 (en) | 2019-08-27 |
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