WO2017099146A1 - Résine pour encre d'impression, vernis pour encre d'impression, encre d'impression et procédé de production de résine pour encre d'impression - Google Patents

Résine pour encre d'impression, vernis pour encre d'impression, encre d'impression et procédé de production de résine pour encre d'impression Download PDF

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Publication number
WO2017099146A1
WO2017099146A1 PCT/JP2016/086438 JP2016086438W WO2017099146A1 WO 2017099146 A1 WO2017099146 A1 WO 2017099146A1 JP 2016086438 W JP2016086438 W JP 2016086438W WO 2017099146 A1 WO2017099146 A1 WO 2017099146A1
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Prior art keywords
tall oil
rosin
acid
parts
polymerized
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PCT/JP2016/086438
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English (en)
Japanese (ja)
Inventor
啓至郎 大川内
博之 久田
笹倉　敬司
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ハリマ化成株式会社
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Application filed by ハリマ化成株式会社 filed Critical ハリマ化成株式会社
Priority to JP2017555114A priority Critical patent/JP6773681B2/ja
Priority to CN201680072042.3A priority patent/CN108368243B/zh
Publication of WO2017099146A1 publication Critical patent/WO2017099146A1/fr

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    • 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
    • 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

Definitions

  • the present invention relates to a resin for printing ink, a varnish for printing ink, a printing ink and a method for producing a resin for printing ink.
  • the printing ink resin obtained by the present invention is particularly useful as an offset printing ink resin. Moreover, it can be used suitably also for newspaper ink, letterpress printing ink, and gravure printing ink.
  • offset printing ink is prepared by heating and mixing the rosin-modified phenolic resin, drying oil or semi-drying oil, solvent or fatty acid ester, and gelling agent as necessary, and uniforming the ink varnish. After the preparation, a pigment is further mixed, and a product is produced through a kneading process and a preparation process.
  • Specific printing inks include, for example, a resole resin having an average number of phenols of 6 to 10, a rosin and / or a condensation product of rosin and unsaturated carboxylic acid, and a reaction product of a polyhydric alcohol.
  • a printing ink containing a varnish containing a rosin-modified phenol resin having a weight average molecular weight of 40,000 to 200,000 has been proposed (Patent Document 1).
  • Patent Document 3 a varnish for printing ink obtained from rosins, fatty acids or fatty acid esters, resol type phenol resins, and polyhydric alcohols has been developed (for example, Patent Document 3).
  • JP 2002-322411 A JP 2000-159867 A JP 2005-154703 A
  • an object of the present invention is to provide a novel printing ink resin that is inexpensive while maintaining the characteristics of a rosin-modified phenolic resin used in conventional offset printing inks.
  • the rosin-modified resin of the present invention comprises: at least
  • the rosin-modified resin of the present invention which is a printing ink resin, will be described.
  • the “rosin-modified resin” in the present invention means at least (A) crude tall oil and / or distilled tall oil, or a mixture containing crude tall oil and / or distilled tall oil and rosin, and (B) a polyhydric alcohol. Is a rosin-modified resin obtained by reacting The “rosin-modified polyester resin” can be obtained by esterifying the component (A) using the component (B).
  • the rosin-modified resin in the present invention may be a rosin-modified resin obtained by adding (C) a resol type phenol resin and reacting in addition to the components (A) and (B).
  • the obtained rosin-modified resin is “rosin-modified phenol resin”.
  • (A) Component crude tall oil and / or distilled tall oil, or mixture of crude tall oil and / or distilled tall oil and rosin is modified with aldehyde and phenols
  • B component resole type phenolic resin To do. The resulting resin is introduced with a cross-linked structure, and printing inks made using this resin have preferred characteristic values.
  • rosin-modified polyester resin means (A) crude tall oil and / or distilled tall oil, or a mixture containing crude tall oil and / or distilled tall oil and rosin, and (B) polyhydric alcohol. It means a resin obtained by esterification.
  • At least one of crude tall oil and distilled tall oil can be used. Moreover, you may use the mixture containing at least 1 type of crude tall oil and distilled tall oil, and a rosin as (A) component. Crude tall oil and distilled tall oil may be used alone or in combination.
  • the crude tall oil is recovered as a by-product in a kraft method in which chemicals such as sodium hydroxide are added to wood chips and decomposed under high temperature and high pressure to take out pulp fibers. It can be obtained by neutralizing a black liquor obtained by concentrating a liquid containing a mixture of lignin and resin components and chemicals that has hardened pulp fibers with an acid such as sulfuric acid. That is, tall rosin is obtained by rectifying crude tall oil. Distilled tall oil is recovered as a by-product when rectifying crude tall oil and separating tall rosin and tall fatty acids.
  • the type of wood that is the raw material for crude tall oil is not particularly limited, but is preferably pine-derived crude tall oil.
  • the type of pine is not particularly limited, and examples include horse ear pine, Tuda pine, and Eliotti pine.
  • the mixture can contain rosin.
  • rosin include tall rosin, gum 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 mixture of component (A) can contain rubber and petroleum resin as required. Regardless of the type, any publicly known materials can be used, and the softening point can be easily adjusted by using the resin, and a resin having a desired softening point can be obtained.
  • the rubber examples include natural rubber, isoprene rubber, butadiene rubber, natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, and ethylene propylene rubber. These rubbers may be used alone or in combination of two or more.
  • Examples of petroleum resins include aliphatic polymers, aromatic polymers, alicyclic polymers, and the like. These petroleum resins may be used alone or in combination of two or more.
  • the total content of crude tall oil and distilled tall oil in the mixture of component (A) is usually 50% by weight or less, and preferably 30% by weight or less. Since crude tall oil and distilled tall oil contain fatty acids (hereinafter, fatty acids contained in tall oil may be simply referred to as “fatty acids”), resins obtained from them as raw materials have low softening points. It tends to be. If the total content of crude tall oil and distilled tall oil increases, the softening point of the resulting resin may be below 120 ° C., so the total content of crude tall oil and distilled tall oil is usually 50% by weight. Or less, preferably 30% by weight or less. In addition, since crude tall oil and distilled tall oil contain impurities, if the total content of crude tall oil and distilled tall oil increases, the reaction becomes complicated and the physical properties of the resulting rosin-modified resin must be adjusted. May be difficult.
  • the crude tall oil and / or distilled tall oil in component (A) those obtained by polymerizing crude tall oil (polymerized crude tall oil) and those obtained by polymerizing distilled tall oil (polymerized distilled tall oil) are used. You may do it. Since the softening point of the resulting resin is improved by using a raw material obtained by polymerizing crude tall oil and / or distilled tall oil, the proportion of crude tall oil and distilled tall oil used as a raw material may be increased. it can. Polymerized crude tall oil and polymerized distilled tall oil are mainly obtained by polymerizing rosin and fatty acids contained in crude tall oil and distilled tall oil.
  • the total amount of polymerized crude tall oil and polymerized distilled tall oil is determined by the following formula: In general, it can be contained in an amount of 90% by weight or less, preferably 80% by weight or less, and more preferably 70% by weight or less, based on the total amount of the mixture. Even when polymerized crude tall oil or polymerized distilled tall oil is used, if these are excessively contained, the softening point may be lowered. Although there is no particular lower limit of the content of the polymerized crude tall oil and / or polymerized distilled tall oil, it is usually good up to 30% by weight based on the mixture to add unpolymerized crude tall oil or distilled tall oil.
  • Resin characteristics can be obtained. Therefore, it is effective to use a polymerized crude tall oil or distilled tall oil when the crude tall oil or distilled tall oil is introduced in an amount exceeding 30% by weight with respect to the mixture. That is, the total amount of the polymerized crude tall oil and the polymerized distilled tall oil is 30% by weight or more and 90% by weight or less based on the total amount of the polymerized crude tall oil and / or the mixture containing the polymerized crude tall oil and rosin. It is preferable that In addition, when using for printing ink, the preferable softening point of resin is 100 degreeC or more normally, Preferably it is 120 degreeC or more and 200 degrees C or less. This is because when the softening point is 120 ° C.
  • the dryness and offset property of the printed matter can be kept good.
  • the softening point of the resin is 200 ° C. or less.
  • the ratio of the polymerized crude tall oil and / or polymerized distilled tall oil to the mixture is 30% by weight or less, the polymerized crude tall oil or polymerized distilled tall oil is used. It is effective to do.
  • Polymerization of crude tall oil and distilled tall oil is usually carried out at 100 to 200 ° C., preferably 130 to 180 ° C. in an atmosphere of an inert gas such as nitrogen or argon.
  • the polymerization time is usually 1 to 24 hours, although it depends on the crude tall oil used.
  • the polymerization in the present specification is a change in which two or more monomer molecules are bonded to form a compound having an integral multiple of molecular weight, and includes a phenomenon of oligomerization such as dimerization and trimerization.
  • Catalysts include formic acid, acetic acid, phosphoric acid, sulfuric acid, phenolsulfonic acid, paratoluenesulfonic acid, methanesulfonic acid, sulfosuccinic acid, 5-sulfosalicylic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, and other carboxylated sulfones Pendants such as acids, arylsulfonic acids substituted with alkyl groups, solid acids having sulfonic acid groups, fluorosulfonic acids, trifluoromethanesulfonic acids, polystyrene sulfonic acids, polyvinyl sulfonic acids, or fluorinated polymers having sulfonic acid type functional groups Polymer hydrogen fluoride having sulfonic acid group, clay, zinc chloride, aluminum chloride, titanium te
  • a more preferable catalyst is an acid catalyst, more preferably a sulfonic acid derivative, still more preferably 4-sulfophthalic acid or trifluoromethanesulfonic acid.
  • the catalyst is preferably used in an amount of 0.01 to 5% by weight based on the crude tall oil or distilled tall oil.
  • the amount of the catalyst used is within the range of 0.01 wt% to 5 wt% with respect to the total of the crude tall oil and distilled tall oil. It is preferable to use it.
  • the catalyst may remain in the final product or may optionally be neutralized with an alkali such as potassium hydroxide or amine.
  • the polymerized crude tall oil and / or distilled tall oil and rosin is mixed with rosin at the predetermined ratio described above.
  • prepare a mixture When preparing the mixture, mixing at an appropriate viscosity is easier to mix, so mixing is performed under heated conditions of 100 to 300 ° C, preferably 150 to 250 ° C.
  • the polymerization may be carried out after mixing crude tall oil and / or distilled tall oil and rosin. If the polymerization is carried out after mixing crude tall oil and / or distilled tall oil and rosin, it is preferable in terms of the process.
  • rosins examples include tall rosin, gum rosin, and wood rosin.
  • rosin derivatives may be used, and specific examples include polymerized rosin, acrylated rosin, hydrogenated rosin, disproportionated rosin and the like. These rosins may be used alone or in combination of two or more.
  • the rosin that can be used as the component (A) may be simply referred to as “rosins”.
  • rubber and petroleum resin can be mixed into the mixture as necessary. By mixing rubber and petroleum resin, it is easy to adjust the softening point of the resulting resin, and a resin having a desired softening point is obtained.
  • the types of rubbers and petroleum resins that can be mixed are not particularly limited, and any publicly known and publicly available materials can be used. Specific examples of the rubber include natural rubber, isoprene rubber, butadiene rubber, natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, and ethylene propylene rubber. These rubbers may be used alone or in combination of two or more.
  • petroleum resins include aliphatic polymers, aromatic polymers, and alicyclic polymers. These petroleum resins may be used alone or in combination of two or more.
  • the mixture as the component (A) Prior to reacting with the component (B), the mixture as the component (A) is described as at least one of ⁇ , ⁇ -unsaturated carboxylic acid and its anhydride (hereinafter simply referred to as “ ⁇ , ⁇ -unsaturated carboxylic acids”). May be modified). That is, component (A) and ⁇ , ⁇ -unsaturated carboxylic acid undergo an addition reaction (Alder ene reaction or Diels-Alder reaction), and ⁇ , ⁇ -unsaturated carboxylic acid, rosin and / or (in tall oil) Of adducts of fatty acids.
  • this adduct has at least two carboxyl groups in the molecule, it forms an ester bond with the polyhydric alcohol as the component (B) to increase the molecular weight.
  • a resin having a desired viscoelasticity can be obtained by increasing the molecular weight of the ⁇ , ⁇ -unsaturated carboxylic acid in advance.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acids include a chain ⁇ , ⁇ -unsaturated monocarboxylic acid having 3 to 5 carbon atoms or an anhydride thereof, and a chain ⁇ having 3 to 5 carbon atoms. , ⁇ -unsaturated dicarboxylic acid or its anhydride, aromatic ⁇ , ⁇ -unsaturated carboxylic acid 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.
  • a metal compound may be used as a crosslinking agent as necessary.
  • metal compounds such as hydroxides and oxides such as lithium, sodium, potassium, calcium, zinc, magnesium, aluminum, cobalt, copper, lead, and manganese may be used as the crosslinking agent.
  • metal ions derived from the metal compound crosslink carboxyl groups (—COOH) present in the resin raw material, and increase the molecular weight of the resulting resin. More specifically, at least two molecules selected from the group consisting of fatty acids, rosin, ⁇ , ⁇ -unsaturated carboxylic acids, and the above adducts in the mixture are exchanged via metal ions derived from metal compounds.
  • a crosslinked body having a crosslinked structure is formed.
  • unreacted rosins; unreacted fatty acids; ⁇ , ⁇ -unsaturated carboxylic acids; reaction products of rosins and ⁇ , ⁇ -unsaturated carboxylic acids; fatty acids and ⁇ The compound selected from the group consisting of reactants of ⁇ -unsaturated carboxylic acids preferably includes a crosslinked product formed by crosslinking via a metal ion derived from a metal compound.
  • Specific examples of the crosslinked body include crosslinked bodies as shown in the following (I) to (X).
  • (V) A crosslinked product formed by crosslinking an unreacted rosin and a reaction product of rosins and ⁇ , ⁇ -unsaturated carboxylic acids via metal ions.
  • VII A crosslinked product formed by crosslinking an unreacted rosin and an ⁇ , ⁇ -unsaturated carboxylic acid via a metal ion.
  • VIII A crosslinked product formed by crosslinking ⁇ , ⁇ -unsaturated carboxylic acids with a reaction product of rosin and ⁇ , ⁇ -unsaturated carboxylic acids via a metal ion.
  • (X) A crosslinked product formed by crosslinking a reaction product of rosins and ⁇ , ⁇ -unsaturated carboxylic acids with a reaction product of fatty acids and ⁇ , ⁇ -unsaturated carboxylic acids via metal ions.
  • the molecular weight of the resulting resin can be increased by cross-linking carboxyl groups present in the resin raw material via metal ions derived from the metal compound. As a result, the drying property and misting resistance of the ink are improved. Moreover, by containing a specific metal compound, when preparing an ink, affinity with a pigment can be improved and dispersibility can be improved.
  • the rosin-modified resin according to this embodiment can be obtained by esterifying the above-described component (A) with the polyhydric alcohol (polyol) that is the component (B).
  • polyol polyhydric alcohol
  • the carboxyl group present in the resin raw material include a rosin in the mixture, a carboxyl group derived from a fatty acid, a carboxyl group derived from an ⁇ , ⁇ -unsaturated carboxylic acid or an anhydride thereof.
  • the polyhydric alcohol is an alcohol having a plurality of hydroxides in one molecule, and the kind thereof is not particularly limited in the present invention.
  • Specific examples of the polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, and 1,6-hexanediol as the dihydric alcohol.
  • Examples of the trihydric alcohol include glycerin, trimethylolpropane, trimethylolethane, triethylolethane, 3-methylpentane-1,3,5-triol, and 1,2,4-butanetriol.
  • Examples of the tetrahydric alcohol include pentaerythritol, diglycerin, sorbitan, and mannitan.
  • a trihydric or higher polyhydric alcohol from the viewpoint that the high molecular weight of the resin is easy and the viscoelasticity necessary for the ink is easily obtained.
  • a polyhydric alcohol may be used independently and may be used in combination of 2 or more types.
  • the (B) component polyhydric alcohol is preferably reacted with the (A) component at a ratio of preferably 0.5 to 2 equivalents with respect to 1 equivalent of the carboxyl group present in the resin raw material.
  • the esterification reaction between the component (A) and the component (B) is not particularly limited as long as the esterification reaction proceeds, but is usually performed in the range of 200 ° C to 350 ° C.
  • esterification catalyst In the esterification reaction, a known and publicly used esterification catalyst may be used as necessary.
  • the esterification catalyst include metal catalysts such as acid catalysts such as Bronsted acid and Lewis acid.
  • esterification may be carried out under a disproportionation catalyst.
  • the disproportionation catalyst include organic sulfur compounds, such as 4,4′-bis (phenol) sulfide, 4,4′-bis (phenol) sulfoxide, and 4,4′-bis (phenol) sulfone.
  • organic sulfur compounds it is preferable to use a compound in which a hydroxyl group bonded to a benzene ring is sterically hindered.
  • 4,4′-bis (6-tert-butylmetacresol) sulfide 4,4'-bis (phenol) sulfide, 2,2'-bis (p-cresol) sulfide, 2,2'-bis (pt-butylphenol) sulfide, 4,4'-bis (resorcinol) sulfide
  • a sulfide compound selected from 4,4'-bis ( ⁇ -naphthol) sulfide, t-amylphenol disulfide oligomers, and nonylphenol disulfide oligomers is preferred.
  • esterification reaction is completed after confirming the acid value, softening point, viscosity, solubility, etc. of the obtained resin and reaching the predetermined value.
  • the rosin-modified polyester resin obtained by the esterification reaction can be suitably used for components such as printing ink.
  • the rosin-modified ester polyester resin according to this embodiment preferably has a softening point of 120 ° C. or higher, more preferably about 130 to 200 ° C.
  • the acid value is preferably about 10 to 40 KOHmg / g.
  • the rosin-modified polyester resin according to this embodiment can be suitably used as a component of a resin for offset printing ink, and in addition to the rosin-modified polyester resin, shellac, gilsonite, Other ink resins such as alkyd resins and rosin-modified phenol resins may be contained.
  • Rosin modified phenolic resin means, as a raw material, (A) crude tall oil and / or distilled tall oil, or a mixture containing crude tall oil and / or distilled tall oil and rosin, and (B) polyhydric alcohol. (C) A resin obtained by reacting these using a resol type phenol resin.
  • component (A) The crude tall oil and / or distilled tall oil of component (A) according to this embodiment, or the mixture of crude tall oil and / or distilled tall oil and rosin is obtained from aldehyde, phenols, etc. It is modified with resole type phenolic resin. Therefore, the obtained resin has a preferable characteristic value with a crosslinked structure introduced therein.
  • the crude tall oil and / or distilled tall oil of component (A) contained in the rosin-modified phenolic resin, or a mixture of crude tall oil and / or distilled tall oil and rosin is the same type as the rosin-modified polyester. it can.
  • the total amount may be crude tall oil and / or distilled tall oil, but is preferably 50% by weight or less. Since crude tall oil and distilled tall oil contain fatty acids (hereinafter, fatty acids contained in tall oil may be simply referred to as “fatty acids”), resins obtained from them as raw materials have low softening points. It tends to be. If the total content of crude tall oil and distilled tall oil increases, the softening point of the resulting resin may be below 120 ° C., so the total content of crude tall oil and distilled tall oil is usually 50% by weight. It is as follows.
  • component (A) a polymerized crude tall oil and / or a polymerized distilled tall oil, or a polymerized crude toll Oils and / or mixtures of polymerized distilled tall oil and rosin may be used.
  • component (A) considering the raw material cost, it is preferable to use the total amount of the polymerized crude tall oil and / or polymerized distilled tall oil as the component (A).
  • a mixture containing the above-mentioned rosins may be used as the component (A).
  • the content of the polymerized crude tall oil and / or polymerized distilled tall oil and the polymerized crude tall oil and / or polymerized distilled tall oil in the rosin mixture is From the viewpoint of raw material costs, it is preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably no rosin (100% by weight).
  • the content of the polymerized crude tall oil and / or polymerized distilled tall oil is preferably 50% by weight or more and 90% by weight or less, more preferably 70% by weight. Above 90% by weight. Therefore, the content of the polymerized crude tall oil and / or polymerized distilled tall oil is preferably 50% by weight or more and 100% by weight or less from the viewpoint of achieving both the raw material costs and the properties of the obtained resin.
  • the B component polyhydric alcohol that can be used in the rosin-modified phenolic resin according to this embodiment can be the same as the rosin-modified polyester resin described above.
  • the amount of polyols used in the production of the rosin-modified phenol resin is not particularly limited, but it is usually sufficient to add from 0.3 equivalents to an excess amount with respect to 1 equivalent of carboxyl group, more preferably 0.5. To 1.5 equivalents, more preferably 0.7 to 1.2 equivalents.
  • phenols (P) and formaldehyde (F) are subjected to addition condensation in the presence of alkali catalysts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide, triethylamine.
  • alkali catalysts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide, triethylamine.
  • alkali catalysts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide, triethylamine.
  • alkali catalysts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide, triethylamine.
  • the phenols are preferably phenols having a C 1 to C 20 alkyl group, more preferably phenols having a C 1 to C 10 alkyl group. Specific examples thereof include carboxylic acid, cresols, amylphenol. Bisphenol-A, p-butylphenol, p-octylphenol, p-nonylphenol, p-dodecylphenol and the like.
  • the amount of the resol type phenol resin used relative to the component (A) is not particularly limited, but is usually 10 to 120% by weight, preferably 30 to 100% by weight.
  • the resol type phenol resin which is (C) component, and resole type
  • Method for producing rosin-modified phenolic resin examples include the following three methods (i) to (iii).
  • the above-mentioned crosslinking reaction for increasing the molecular weight can be carried out at an appropriate stage in the production methods (i) to (iii).
  • the acid value, softening point, viscosity, solubility, etc. of the obtained resin are confirmed, and the reaction is terminated as soon as a predetermined value is reached.
  • the obtained resin can be suitably used for components such as printing ink.
  • the rosin-modified ester polyester resin and rosin-modified phenol resin of the present invention preferably have a softening point of 120 ° C. or higher, more preferably about 130 to 200 ° C.
  • the acid value is preferably about 10 to 40 KOHmg / g.
  • the resin for offset printing ink according to the present embodiment includes, in addition to the rosin-modified polyester resin and / or rosin-modified phenol resin, shellac, gilsonite, alkyd resin, and rosin-modified phenol as long as the effects of the present invention are not impaired. You may contain other resin for inks, such as resin.
  • the rosin-modified polyester resin or rosin-modified phenol resin according to the present invention can be used as a resin for printing ink, particularly as a resin for ink for offset printing.
  • resins for offset printing ink are generally used as drying oil or semi-drying oil (for example, linseed oil, tung oil, soybean oil, soybean white squeezed oil, etc.) and solvents (for example, aliphatic hydrocarbon solvents, etc.) ).
  • 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 be used in combination of 2 or more types.
  • antioxidants may be added as long as the effects of the present invention are not impaired.
  • the antioxidant is not particularly limited, and examples thereof include hydroquinone, tertiary butyl hydroquinone, dibutylhydroxytoluene, eugenol, pyrogallol, catechol, and guaralacol.
  • An antioxidant may be used independently and may be used in combination of 2 or more types.
  • An offset printing ink is prepared by dispersing a pigment of a desired color (black pigment, indigo pigment, red pigment, yellow pigment, etc.) in the varnish obtained from the resin for offset printing ink according to the present embodiment.
  • the obtained printing ink is suitable for offset inks such as sheet-fed ink and off-wheel ink, and can also be used for newspaper ink, letterpress ink and gravure ink.
  • the rosin-modified polyester resin or rosin-modified phenol resin of the present invention is used as a binder for offset printing inks, etc.
  • printing properties such as emulsification characteristics, gloss, drying properties, misting, etc. of printing inks containing these resins
  • it is equal to or higher than that of conventionally known rosin-modified phenolic resins. Accordingly, the present invention can provide printing inks that meet recent market demands.
  • rosin-modified polyester resin 5 650 parts of crude tall oil and 350 parts of tall rosin were charged into a flask equipped with a stirrer, a water separator, a condenser tube and a thermometer, and the temperature was raised to 160 ° C. in a nitrogen atmosphere. Next, 15 parts of 4-sulfophthalic acid (50% aqueous solution) was added, held at the same temperature for 4 hours, and 7.5 parts of oleylamine was added.
  • soybean oil white squeezed oil and AF6 were added so that the ratio of soybean oil white squeezed oil in the varnish was not less than 30%, and a rheometer (manufactured by Thermo Haake, HAAKE Rheo Stress 600), 25 ° C., 1.0 Hz.
  • An ink varnish having a viscosity adjusted to about 100 Pa ⁇ s was obtained.
  • Linseed oil (Nisshin Oillio Group Co., Ltd.) and rosin-modified polyester resin were blended in a ratio of 2: 1 by weight, and normal hexane (Showa Chemical Co., Ltd.) was added to the mixture after heating and dissolving. The ratio of the amount of hexane required to do was measured.
  • the resin constants in Tables 1 to 4 are the evaluation results of the resins of Examples 1 to 18 and Comparative Examples 1 to 4, and the ink evaluation results in Tables 1 to 4 are the results of Examples 1 to 18 and the comparisons.
  • 4 is an evaluation result of inks containing each resin of Examples 1 to 4.
  • the printing ink containing the resin for printing inks of the present invention using crude tall oil and / or distilled tall oil has higher drying and misting resistance than the case of using tall oil fatty acid. It was found that the printed matter can be given a good gloss while keeping the color.
  • the printing ink containing the resin for printing ink of the present invention using the polymerized crude tall oil and / or the polymerized distilled tall oil maintains further drying and misting resistance than the case of using tall oil fatty acid.
  • the printing ink resin of the present invention can improve the performance of a plurality of inks in a trade-off relationship.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne une nouvelle résine pour des encres d'impression qui conserve les propriétés de résines phénoliques modifiées par de la colophane pour une utilisation dans des encres d'impression offset classiques et qui est peu coûteuse. La résine est une résine modifiée par de la colophane, obtenue par réaction d'au moins : (A) soit du tall-oil brut et/ou distillé, soit un mélange comprenant du tall-oil brut et/ou distillé et une colophane ; et (B) un alcool polyhydrique.
PCT/JP2016/086438 2015-12-09 2016-12-07 Résine pour encre d'impression, vernis pour encre d'impression, encre d'impression et procédé de production de résine pour encre d'impression WO2017099146A1 (fr)

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