Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
  • C09D11/104—Polyesters
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
  • C09D11/104—Polyesters
  • C09D11/105—Alkyd resins

Definitions

• the present invention relates to a rosin-modified polyester-based resin for offset printing ink that has high solubility in varnishing, gives a good gloss to printed matter, and has excellent drying properties and misting resistance during printing.
• Offset printing is suitable for multicolor printing, gradation expression, and clear printing, and is also suitable for mass printing. Therefore, it is frequently used for printing newspapers, flyers, catalogs, books, and the like.
• rosin-modified phenolic resins are mainly used as binder resins for offset printing. The reason is that the rosin-modified phenolic resin has the following characteristics (A) to (C).
• A) It has high pigment dispersibility and can impart good gloss.
• B It is easy to adjust the viscoelasticity of the ink.
• C It is easy to adjust the balance between the hardness and flexibility of the printed film.
• the rosin-modified phenolic resin is generally obtained by modifying a phenol formaldehyde initial condensate with rosin and, if necessary, esterifying with a polyhydric alcohol or the like.
• rosin-modified phenolic resins use formaldehyde as a raw material, and thus have problems in terms of environment and work hygiene. Furthermore, it has been reported that the alkylphenol component exhibits an environmental hormone action.
• a rosin-modified polyester-based binder resin for offset ink that does not use aldehydes and phenols as a raw material has been developed (Patent Document 1).
• the rosin-modified polyester resin is obtained, for example, by reacting rosin with a polyhydric alcohol, a polybasic acid, a fatty acid, or the like.
• rosin-modified polyester resins are easier to set than the rosin-modified phenolic resin, such as the balance of physical properties such as ink gloss, solubility in ink solvents and drying properties, and the balance between printed film hardness and flexibility. is not.
• offset printing gives the printed matter good gloss and film flexibility, and also requires compatibility with non-aromatic ink solvents (aliphatic hydrocarbon solvents) and fats and oils during varnishing. .
• non-aromatic ink solvents aliphatic hydrocarbon solvents
• the amount of fatty acid, particularly higher fatty acid, in the raw material may be increased, and this formulation is economically advantageous.
• the alkylphenol component achieves a balance of hardness and flexibility, hydrophilicity and lipophilicity.
• the amount of fatty acid used is increased, the hardness and drying properties of the ink are greatly impaired, and the misting resistance during printing is also reduced. This is presumably because long-chain alkyl groups derived from higher fatty acids contribute to lipophilicity and plasticity, but the ink resin lacks sites related to hardness and hydrophilicity.
• An object of the present invention is to provide a resin for offset printing ink, which has high solubility during varnishing, can give a good gloss to printed matter, and has excellent drying properties and misting resistance during printing, and To provide an offset printing ink using a resin for offset printing ink. Still another object of the present invention is to provide a method for easily producing such a resin for offset printing ink.
• Offset printing containing a resin obtained by reacting rosins, a resin raw material containing an ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof, a metal compound, a fatty acid or oil, and a polyhydric alcohol.
• a resin for ink containing 10 to 50% by mass of the fatty acid or fat with respect to the total amount of the resin raw material, and the metal compound with respect to the total amount of the resin raw material in terms of metal amount of the metal compound
• a resin for offset printing ink characterized by containing 0.5 to 5% by mass.
• the resin for offset printing ink according to (1) wherein the fatty acid contains a fatty acid having 12 or more carbon atoms as a main component.
• the fatty acid At least one selected from the group consisting of the rosins, the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, and an adduct consisting of the rosins and the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride.
• the crosslinked body includes a carboxyl group present in the fatty acid, At least one selected from the group consisting of the rosins, the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, and an adduct consisting of the rosins and the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride.
• the carboxyl group present in the seed The resin for offset printing ink according to (3), which is formed through metal ions derived from the metal compound.
• the resin for offset printing ink according to (1) wherein the fat is triglyceride of a fatty acid and glycerin, and at least one fatty acid has 12 or more carbon atoms.
• the cross-linked product is composed of the rosin, the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, and an adduct comprising the rosin and the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride.
• the ratio of the metal compound is 0.5 to 5% by mass in terms of the amount of metal in the metal compound.
• (11) At least selected from the group consisting of rosins, ⁇ , ⁇ -unsaturated carboxylic acids or anhydrides thereof, and adducts comprising the rosins and the ⁇ , ⁇ -unsaturated carboxylic acids or anhydrides thereof Step A in which one kind forms a crosslinked body crosslinked through metal ions derived from a metal compound; The rosin, the ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof, the adduct, and at least one selected from the group consisting of the cross-linked product and a polyhydric alcohol are subjected to an esterification reaction, And B step for forming the ester; the ester obtained in the B step and the fat and oil are subjected to a transesterification reaction, and an alkyl group in the fat and oil is introduced into the ester.
• the ratio of the fatty acid is 10 to 50 mass with respect to the total amount of the resin raw materials including the rosin, the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, the metal compound, the oil and fat, and the polyhydric alcohol. %, And the ratio of the metal compound is 0.5 to 5% by mass in terms of the amount of metal in the metal compound.
• An offset printing ink comprising the offset printing ink resin according to any one of (1) to (9), a drying oil or semi-drying oil, a solvent, and a pigment.
• a resin for offset printing ink having high solubility during varnishing can be obtained.
• the ink for offset printing obtained using the said resin can give favorable gloss to printed matter, and is excellent in drying property and the misting resistance at the time of printing.
• the method for producing a resin for offset printing ink of the present invention such a resin for offset printing ink can be easily obtained.
• the resin for offset printing ink according to the present invention is a resin obtained by reacting a resin raw material containing rosins, ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, metal compound, fatty acid or oil and fat, and polyhydric alcohol. contains.
• resin raw materials including rosins, fatty acids or oils, ⁇ , ⁇ -unsaturated carboxylic acids or anhydrides thereof, polyhydric alcohols, and metal compounds, and if necessary, contain aromatic carboxylic acids.
• rosins used as the same include rosin and rosin derivatives.
• rosin refers to a residual resin after a volatile substance such as essential oil is distilled off from a resin oil obtained from a pine family plant.
• This resin is a mixture containing a resin acid mainly composed of abietic acid and its analog and a small amount of a neutral component.
• rosins examples include gum rosin, tall oil rosin, and wood rosin.
• rosin derivatives include polymerized rosin, acrylated rosin, hydrogenated rosin, and disproportionated rosin. These rosins may be used alone or in combination of two or more.
• the rosins are contained in a proportion of preferably 20 to 60% by mass, more preferably 30 to 50% by mass, based on the total amount of the resin raw material.
• ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride used as a resin raw material is used for increasing the molecular weight of a resin for offset printing ink. That is, ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride and rosin undergo an addition reaction (Alder's ene reaction or Diels-Alder reaction), and ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride and rosin The adduct is generated. Since this adduct has at least two carboxyl groups in the molecule, it forms an ester bond with a polyhydric alcohol described later to increase the molecular weight. Thus, the resin which has desired viscoelasticity is obtained by high molecular weight.
• Examples of the ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof include a chain ⁇ , ⁇ -unsaturated monocarboxylic acid or anhydride thereof having 3 to 5 carbon atoms and 3 to 5 carbon atoms.
• Examples thereof include linear ⁇ , ⁇ -unsaturated dicarboxylic acids or anhydrides thereof, aromatic ⁇ , ⁇ -unsaturated carboxylic acids and the like. Specific examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, crotonic acid, and cinnamic acid.
• These ⁇ , ⁇ -unsaturated carboxylic acids or anhydrides thereof may be used alone or in combination of two or more.
• the ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof is contained in an amount of preferably 1 to 15% by mass, more preferably 3 to 10% by mass, based on the total amount of the resin raw material.
• the ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof is contained in such a range, the molecular weight can be easily controlled, and a resin having a desired viscoelasticity necessary for the ink can be obtained more easily.
• the metal compound used as the resin raw material is used as a crosslinking agent for increasing the molecular weight by crosslinking the carboxyl group (—COOH) present in the compound contained in the resin raw material.
• a fatty acid described later when used as a resin raw material, it comprises a fatty acid and a rosin, an ⁇ , ⁇ -unsaturated carboxylic acid or an anhydride thereof, and a rosin and an ⁇ , ⁇ -unsaturated carboxylic acid or an anhydride thereof.
• a crosslinked body is formed in which at least one selected from the group consisting of adducts is crosslinked via metal ions derived from the metal compound.
• crosslinked bodies shown in the following (i) to (iv) are formed.
• a cross-linked body is formed in which at least one selected from the group consisting of the cross-linked metal ions derived from the metal compound is cross-linked.
• crosslinked bodies shown in the following (i ′) to (x ′) are formed.
• (I ′) A crosslinked product in which adducts are crosslinked via metal ions.
• (Ii ′) A crosslinked product obtained by crosslinking an adduct and an unreacted rosin through a metal ion.
• (Iii ′) A crosslinked product obtained by crosslinking an adduct and an unreacted ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof via a metal ion.
• (Iv ′) A crosslinked product obtained by crosslinking an adduct and an aromatic carboxylic acid, which is an optional component described later, via a metal ion.
• V ′ A crosslinked product in which unreacted rosins are crosslinked via metal ions.
• Vi ′ A crosslinked product in which an unreacted rosin and an unreacted ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof are crosslinked via a metal ion.
• Vii ′ A crosslinked product in which an unreacted rosin and an aromatic carboxylic acid which is an optional component described later are crosslinked via a metal ion.
• Viii ′ A crosslinked product in which unreacted ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride is crosslinked through a metal ion.
• (Ix ′) A crosslinked product in which an unreacted ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof and an aromatic carboxylic acid, which is an optional component described later, are crosslinked via a metal ion.
• (X ′) A crosslinked product in which aromatic carboxylic acids, which are optional components described later, are crosslinked via metal ions.
• the molecular weight of the cross-linked product formed by cross-linking carboxyl groups present in the resin raw material via metal ions increases, and as a result, the drying property and misting resistance of the ink are improved.
• affinity with a pigment can be improved and dispersibility can be improved.
• the metal compound examples include hydroxides and oxides of divalent or higher metals such as calcium, zinc, magnesium, aluminum, cobalt, copper, lead, and manganese.
• calcium such as calcium hydroxide, calcium oxide, zinc hydroxide, zinc oxide, magnesium hydroxide, magnesium oxide is highly reactive with respect to carboxyl groups present in resin raw materials and has high affinity with pigments.
• Compounds, zinc compounds or magnesium compounds are preferred. These metal compounds may be used independently and may use 2 or more types together.
• the metal compound is contained in an amount of 0.5 to 5% by mass with respect to the total amount of the resin raw material in terms of the metal amount of the metal compound (the ratio of the mass corresponding to the metal portion; By containing the metal compound in such a ratio, a resin having an excellent balance between hydrophilicity and lipophilicity can be obtained.
• the content of the metal compound in terms of the amount of metal is less than 0.5% by mass, the molecular weight becomes small, and the misting resistance at the time of printing and the drying property of the ink are deteriorated.
• the content of the metal compound in terms of metal amount is preferably 1 to 3% by mass.
• the content of the metal compound is set to a ratio of about 2 to 15 parts by mass.
• the amount is preferably about 3 to 10 parts by mass.
• gravure printing metal salts of rosins are generally used as ink resins.
• gravure printing is a printing method that is completely different from offset printing. For this reason, even if a gravure printing ink resin is used as an offset printing ink resin, the solubility in an aliphatic hydrocarbon solvent is inferior, and furthermore, printing with water causes problems such as easy emulsification of the ink. .
• a metal compound may be used as an esterification catalyst in the production of a rosin-modified polyester resin. Since the metal catalyst used for esterification is reused many times in the reaction system, a very small amount is sufficient. On the contrary, if a large amount of metal is added before the addition of alcohol, an insoluble material of metal is deposited, and the performance as an ink resin is deteriorated. In contrast, in the present invention, a relatively large amount of metal compound is used. The reason is that a small part of the metal compound may act as an esterification catalyst, but the main purpose is to crosslink the carboxyl group present in the resin raw material via metal ions derived from the metal compound. It is. For example, when fatty acids are used, the amount of fatty acids used is relatively large, so that even though a large amount of metal is used, the metal compound dissolves quickly and forms a crosslinked structure via metal ions. be able to.
• the fatty acid used as a resin raw material is used to impart lipophilicity to the resin. That is, a crosslinked body as shown in the above (i) to (iv) is formed to impart lipophilicity. Since the lipophilicity of the fatty acid depends on the alkyl group portion of the fatty acid, a higher fatty acid having a large number of carbon atoms is preferred, and a fatty acid having 12 or more carbon atoms is the main component. Examples of the fatty acid include fatty acids derived from animal oils and fats described later, fatty acids derived from vegetable oils, and the like.
• the fatty acid having 12 or more carbon atoms may be either a saturated fatty acid or an unsaturated fatty acid.
• saturated fatty acid include lauric acid (carbon number 12), myristic acid (carbon number 14), palmitic acid (carbon number 16), stearic acid (carbon number 18), and the like.
• unsaturated fatty acids include ⁇ -linolenic acid (carbon number 18), linoleic acid (carbon number 18), oleic acid (carbon number 18), and the like.
• saturated fatty acids such as stearic acid are preferable because they are excellent in various physical properties such as solubility in an ink solvent and drying properties.
• the fatty acid need not be a purified fatty acid and may be a mixed fatty acid.
• the mixed fatty acid include a mixture of two or more fatty acids, a fatty acid derived from animal fats and oils, a fatty acid derived from vegetable fats and oils, and the like.
• fatty acids derived from animal fats and oils mainly composed of fatty acids having 12 or more carbon atoms include beef tallow fatty acids, pork tallow fatty acids, fish oil fatty acids, and fatty acids obtained by hydrogenating (curing) them.
• examples of fatty acids derived from vegetable oils and fats mainly composed of fatty acids having 12 or more carbon atoms include tall oil fatty acids, soybean oil fatty acids, linseed oil fatty acids, tung oil fatty acids, coconut oil fatty acids, castor oil fatty acids and the like. Is mentioned.
• the fats and oils used as a resin raw material are used in order to provide lipophilicity to resin.
• solubility in a solvent or the like used in ink production is enhanced.
• Lipophilic properties include rosins, ⁇ , ⁇ -unsaturated carboxylic acids or anhydrides thereof, adducts described above, cross-linked products described above, aromatic carboxylic acids described below (used as necessary), and polyhydric alcohols described below. It is provided by introducing an alkyl group derived from fat (triglyceride) into the polyester resin by a transesterification reaction between the polyester resin obtained from the fat and fat.
• the fats and oils are not particularly limited, and examples thereof include animal fats and oils and vegetable fats and oils.
• these oils and fats those containing at least triglyceride composed of fatty acids in which at least one of the three fatty acids has 12 or more carbon atoms are preferable.
• animal fats include beef tallow, pork tallow, and fish oil.
• vegetable oils include soybean oil, linseed oil, tung oil, palm oil, castor oil, palm oil, and rapeseed oil.
• the regeneration treatment method includes removal of precipitates and decolorization by filtration or the like. These fats and oils may be used independently and may use 2 or more types together.
• Fatty acids or fats and oils are contained in a proportion of 10 to 50% by mass with respect to the total amount of resin raw materials. If the fatty acid or fat content is less than 10% by mass, the solubility in the solvent used in the production of the ink will be low, resulting in poor pigment dispersibility and poor gloss on the printed matter. . On the other hand, when the content of the fatty acid or fat exceeds 50% by mass, the resin becomes soft and the misting resistance during printing and the drying property of the ink deteriorate.
• the fatty acid or fat is preferably contained in a proportion of 20 to 40% by mass with respect to the total amount of the resin raw material.
• the fatty acid or fats and oils used as a resin raw material are used in distinction from the solvent used when manufacturing ink, such as resin varnishing.
• the fatty acid and the fat may be used alone, or the fatty acid and the fat may be used in combination.
• the fatty acid and fat are contained in a total amount of 10 to 50% by mass, preferably 20 to 40% by mass, based on the total amount of the resin raw materials.
• the polyhydric alcohol used as a resin raw material includes the above-mentioned adduct, unreacted rosin, unreacted ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof, the above-mentioned crosslinked product, fatty acid, and the following Reacts with an aromatic carboxylic acid to form an ester.
• the ink tends to be easily emulsified in printing with water.
• polyhydric alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, D- Examples include sorbitol.
• a trihydric or higher polyhydric alcohol is preferable in that the resin can have a high molecular weight and the viscoelasticity necessary for the ink can be easily obtained.
• a polyhydric alcohol may be used independently and may use 2 or more types together.
• the polyhydric alcohol is preferably contained in an amount of 0.5 to 2 equivalents, more preferably 0.9 to 1.3 equivalents, relative to 1 equivalent of the carboxyl group present in the resin raw material.
• a resin imparting desired viscoelasticity necessary for the ink is more easily obtained.
• the solubility in a solvent used in the production of the ink becomes better, and the ink is less likely to be emulsified even in printing with water.
• the carboxyl group present in the resin raw material includes a carboxyl group derived from rosins, a carboxyl group derived from an ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, a carboxyl group derived from a fatty acid, and an aromatic group described later. Examples thereof include a carboxyl group derived from a carboxylic acid.
• the resin raw material may further contain an aromatic carboxylic acid as necessary.
• an aromatic carboxylic acid it is possible to adjust the solubility in a solvent used in the production of the ink, and to adjust the molecular weight of the resin.
• aromatic monocarboxylic acids are used to adjust solubility in solvents used in ink production
• aromatic dicarboxylic acids and aromatic polyvalent carboxylic acids are used to adjust the molecular weight of resins. .
• aromatic carboxylic acid examples include benzoic acid, salicylic acid, naphthoic acid, phthalic acid, phthalic anhydride, trimellitic acid, trimellitic anhydride, and these substituted products in which at least one alkyl group is introduced on the aromatic ring. Can be mentioned. These aromatic carboxylic acids may be used alone or in combination of two or more.
• the aromatic carboxylic acid is contained in a proportion of preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 4 to 10% by mass with respect to the total amount of the resin raw material when used as necessary.
• the method for producing the resin for offset printing ink according to the present invention is not particularly limited.
• the resin for offset printing ink according to the present invention is obtained, for example, by the following first step and second step when using a fatty acid.
• First step From the group consisting of fatty acids and rosins, ⁇ , ⁇ -unsaturated carboxylic acids or anhydrides thereof, and adducts comprising the rosins and the ⁇ , ⁇ -unsaturated carboxylic acids or anhydrides thereof.
• Second step Estimating at least one selected from the group consisting of the rosins, the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, the adduct, the cross-linked product, and a fatty acid, and a polyhydric alcohol.
• the reaction temperature in the first step and the second step is preferably 100 to 290 ° C., more preferably 200 to 270 ° C., although it varies depending on the composition of the raw material.
• the reaction time is preferably 2 to 20 hours, more preferably 3 to 10 hours. For example, when the raw materials are added sequentially, the reaction time is from the start of the addition of the raw materials until the final product is obtained. Is the total time.
• an ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof and an rosin having an unsaturated bond undergo an addition reaction (Alder ene reaction or Diels-Alder reaction), and ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride and rosin adduct is formed.
• the first step after completion of the addition reaction or in parallel with the addition reaction, from the adduct, the unreacted rosin, and the unreacted ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof. At least one selected from the group consisting of a fatty acid and a fatty acid forms a crosslinked product via a metal ion derived from the metal compound.
• the fatty acid, the above adduct, the above crosslinked body, the unreacted rosin, and the unreacted ⁇ , ⁇ The polyhydric alcohol reacts with at least one selected from the group consisting of unsaturated carboxylic acids or anhydrides to form esters. Since the adduct has two or more carboxyl groups in the molecule, it reacts with a polyhydric alcohol to form an ester, and a high molecular weight resin (rosin-modified polyester resin) is obtained.
• a crosslinked body what has a carboxyl group in a molecule
• numerator reacts with a polyhydric alcohol, and is esterified.
• the resin for offset printing ink according to the present invention can be obtained, for example, by the following steps A to C.
• Step A at least selected from the group consisting of rosins, ⁇ , ⁇ -unsaturated carboxylic acids or anhydrides thereof, and adducts comprising the rosins and the ⁇ , ⁇ -unsaturated carboxylic acids or anhydrides thereof
• Step B consisting of the rosin, the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, an adduct comprising the rosin and the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, and the crosslinked product
• Step C A step of subjecting the ester and fat obtained in Step B to a transesterification reaction and introducing an alkyl group in the fat into the ester.
• the reaction temperature and reaction time in Steps A to C are the same as those in the case of using a fatty acid.
• ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride and rosins having an unsaturated bond undergo an addition reaction (Alder ene reaction or Diels-Alder reaction), and ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride and rosins are formed.
• step A after completion of the addition reaction or in parallel with the addition reaction, the adduct, the unreacted rosin, and the unreacted ⁇ , ⁇ -unsaturated carboxylic acid or anhydride thereof are included. At least one selected from the group forms a crosslinked product via a metal ion derived from a metal compound.
• Step B after completion of the crosslinking reaction in Step A or in parallel with the crosslinking reaction, the adduct, the crosslinked body, the unreacted rosin, and the unreacted ⁇ , ⁇ -unsaturated carboxylic acid or At least one selected from the group consisting of the anhydrides reacts with the polyhydric alcohol to form an ester.
• the adduct Since the adduct has two or more carboxyl groups in the molecule, it reacts with a polyhydric alcohol to form an ester, and a high molecular weight resin (rosin-modified polyester resin) is obtained. As described above, the cross-linked product having a carboxyl group in the molecule is esterified by reacting with a polyhydric alcohol.
• Step C after completion of the esterification reaction in Step B or in parallel with the esterification reaction, an alkyl group in the fat is introduced into the rosin-modified polyester resin by a transesterification reaction between the produced ester and the fat. .
• the C step at least a part of the ester formed in the B step undergoes transesterification reaction with fats and oils, and alkyl groups derived from the fats and oils (for example, alkyl groups having 12 or more carbon atoms) are introduced.
• a rosin-modified polyester resin is obtained.
• the resin for offset printing ink according to the present invention includes, in addition to the above-mentioned rosin-modified polyester resin, other ink resins such as shellac, gilsonite, alkyd resin, and rosin-modified phenolic resin as long as the effects of the present invention are not impaired. It may contain.
• the resin for offset printing ink according to the present invention is generally a drying oil or a semi-drying oil (for example, linseed oil, tung oil, soybean oil, soybean white squeezed oil, etc.) and a solvent (for example, aliphatic Mixed with hydrocarbon solvent).
• a drying oil or a semi-drying oil for example, linseed oil, tung oil, soybean oil, soybean white squeezed oil, etc.
• a solvent for example, aliphatic Mixed with hydrocarbon solvent
• various gelling agents may be added in consideration of viscoelasticity as long as the effects of the present invention are not impaired.
• the gelling agent is not particularly limited, and examples thereof include aluminum compounds such as aluminum alcoholate and aluminum soap; metal soaps such as manganese, cobalt and zirconium; alkanolamine and the like.
• a gelling agent may be used independently and may use 2 or more types together.
• the resin for offset printing ink according to the present invention does not use aldehydes and phenols, synthesis of resole is unnecessary. Furthermore, since the crosslinked body is formed using the metal compound, the resin for offset printing ink according to the present invention can be varnished in a relatively short time as compared with the rosin-modified phenol resin.
• An offset printing ink is prepared by dispersing a pigment of a desired color (black pigment, blue pigment, red pigment, etc.) in the obtained varnish.
• the offset printing ink obtained by using the resin for offset printing ink according to the present invention is excellent in drying property and misting resistance during printing, and can be replaced with a conventional rosin-modified phenol resin. Furthermore, when this offset printing ink is used, a printed matter having a good gloss and a flexible coating film can be obtained.
• Example 1 When the total resin raw material is 100% by mass, the reaction vessel is charged so that the ratio of gum rosin is 38% by mass and soybean oil fatty acid is 36.8% by mass as the rosin. The solution was heated up to dissolve. After dissolution, maleic anhydride as an ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride is added at a rate of 7.6% by mass, and zinc oxide as a metal compound at a rate of 2.8% by mass, followed by reaction for 1 hour. I let you. Next, pentaerythritol as a polyhydric alcohol was added at a ratio of 14.8% by mass, and the temperature was raised to 270 ° C.
• the obtained resin contains the metal compound at a ratio of about 6.3 parts by mass in terms of metal with respect to 100 parts by mass of the fatty acid.
• polyhydric alcohol penentaerythritol
• penentaerythritol is contained so that it may become 1.1 equivalent with respect to 1 equivalent of carboxyl groups which exist in a resin raw material.
• the obtained resin for offset printing ink is 50% by mass, soy white squeezed oil is 15% by mass, and AF7 (manufactured by Shin Nippon Petrochemical Co., Ltd., aroma-free solvent) is 35% by mass.
• AF7 manufactured by Shin Nippon Petrochemical Co., Ltd., aroma-free solvent
• the obtained varnish was mixed in a proportion of 70% by mass and the indigo pigment in a proportion of 19% by mass, and the indigo pigment was obtained using a three roll mill (manufactured by Inoue Seisakusho, S-4 3/4 ⁇ 11). Dispersed in varnish.
• varnish was added at 4 mass% and AF7 was added at a ratio of 7 mass% to obtain an offset printing ink.
• Examples 2 to 8 and Comparative Examples 1 to 5 Resin for offset printing ink was obtained in the same procedure as in Example 1 except that the components shown in Table 1 were used in the proportions shown in Table 1.
• the polyhydric alcohol is contained in an amount of 1.0 to 1.3 equivalents relative to 1 equivalent of the carboxyl group present in the resin raw material.
• Example 2 a varnish was obtained in the same procedure as in Example 1 except that the obtained offset printing ink resin was used.
• the resin obtained in Comparative Example 1 was too low in solubility in AF7, the resin of Comparative Example 1 was clouded and a varnish could not be obtained.
• offset printing inks were obtained in the same manner as in Example 1, except that the varnish, AF7 and indigo pigment were used in the proportions shown in Table 2.
• the varnish content in Table 2 describes the total amount, and 70% by mass was used for dispersing the indigo pigment, and the rest was used for adjusting the tack.
• a varnish was prepared in the same procedure as in Example 1 except that a conventional rosin-modified phenolic resin (Harima Kasei Co., Ltd., Hariphenol P-600) was used as the offset printing ink resin. Offset printing inks were obtained using varnish, AF and indigo pigments in proportions.
• Haliphenol P-600 is a resin obtained by reacting rosin pentaerythritol ester with phenol formaldehyde precondensate.
• the offset printing inks of Examples 1 to 8 were prepared by using a conventional offset printing ink using rosin-modified phenolic resin (reference example), (1) gloss value, (2) drying property, (3 It can be seen that both the) resistance to misting and the (4) maximum emulsification amount are equivalent or equivalent.
• the offset printing ink of Comparative Example 2 contained too little fatty acid in the resin, the solubility in the solvent was lowered and the gloss was deteriorated.
• the offset printing ink of Comparative Example 3 had good glossiness due to the high fatty acid content, but had poor drying and misting resistance.
• the offset printing ink of Comparative Example 4 had poor drying properties and misting resistance because the metal compound content was too small relative to the fatty acid content.
• the offset printing ink of Comparative Example 5 had a large maximum emulsification amount because the metal compound content was too much relative to the fatty acid content.
• Example 9 When the total resin raw material is 100% by mass, 41.0% by mass of gum rosin and 38.0% by mass of soybean oil are charged into a reaction vessel and heated to 200 ° C. while blowing nitrogen gas, These were dissolved. After dissolution, maleic anhydride was added at 7.6% by mass and zinc oxide at 2.8% by mass and reacted for 2 hours. Next, pentaerythritol as a polyhydric alcohol was added at a ratio of 10.6% by mass, and the temperature was raised to 270 ° C. and reacted for about 7 hours to obtain a resin for offset printing ink. In the obtained resin, the metal compound is contained at a ratio of about 6.1 parts by mass in terms of metal with respect to 100 parts by mass of the fats and oils. Moreover, polyhydric alcohol (pentaerythritol) is contained so that it may become 1.1 equivalent with respect to 1 equivalent of carboxyl groups which exist in a resin raw material.
• Example 10 to 16 and Comparative Examples 6 to 10 Resins for offset printing inks were obtained in the same procedure as in Example 9, except that the components shown in Table 3 were used in the proportions shown in Table 3.
• Comparative Example 6 is the same as Comparative Example 1 described above.
• the polyhydric alcohol is contained in an amount of 1.0 to 1.2 equivalents relative to 1 equivalent of the carboxyl group present in the resin raw material.
• a varnish was obtained in the same procedure as in Example 9, except that the obtained offset printing ink resin was used.
• the resin of Comparative Example 6 was too low in solubility in AF7, so that the resin of Comparative Example 6 was clouded and a varnish could not be obtained.
• varnishes were obtained in the same manner as in Example 9, except that varnish, AF and indigo pigment were used in the proportions shown in Table 4.
• the varnish content in Table 4 describes the total amount, and 70% by mass was used for dispersing the indigo pigment, and the rest was used for adjusting the tack.
• the offset printing inks of Examples 9 to 16 are the offset printing ink using a conventional rosin-modified phenol resin (reference example), (1) gloss value, (2) drying property, (3 It can be seen that both the) resistance to misting and the (4) maximum emulsification amount are equivalent or equivalent.
• the offset printing ink of Comparative Example 7 contained too little oil and fat in the resin, the solubility in the solvent was lowered and the glossiness was deteriorated.
• the offset printing ink of Comparative Example 8 had good glossiness due to a high content of fats and oils, but had poor drying and misting resistance.
• the offset printing ink of Comparative Example 9 had poor dryability and misting resistance because the metal compound content was too small relative to the fat content.
• the offset printing ink of Comparative Example 10 had a large maximum emulsification amount because the metal compound content was too much relative to the fat content.

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