JP2020183489A - Binder for printing ink and printing ink using the same - Google Patents

Abstract

To provide a binder for printing ink which is composed of a biomass-derived polyurethane urea resin, and is excellent in blocking resistance, laminate suitability and boiling and retort resistance.SOLUTION: The binder for printing ink is provided that contains a polyurethane urea resin (U) containing, as essential constituent monomers, polyol (A) having a number average molecular weight of 500 or more, polyisocyanate (B) and a chain extender (C) having a number average molecular weight or a chemical formula weight of less than 500, the polyol (A) contains, as essential constituent monomers, polyester polyol (A11) containing biomass-derived 1,3-propane diol and/or biomass-derived 1,4-butane diol and biomass-derived sebacic acid, the chain extender (C) contains polyamine (C1), and a weight average molecular weight of the polyurethane urea resin (U) is 120,000 to 200,000.SELECTED DRAWING: None

Description

The present invention relates to a binder for printing ink and a printing ink.

Conventionally, as a solvent-based binder resin for printing inks, polyurethane resins have been widely used because they have excellent adhesion to polyester films, nylon films, and the like and printability. On the other hand, urethane resin-based inks have a problem that blocking is likely to occur when the film is wound after ink coating, and many polyurethane resins having improved blocking resistance have been developed (see, for example, Patent Document 1). Further, in the conventional urethane resin-based ink, when the dry laminating process is performed, it may be dissolved in ethyl acetate or the like which is an adhesive solvent, which causes a problem in laminating suitability.

Further, in recent years, interest in carbon neutrality has increased worldwide, and biomass conversion has been studied for printing inks, and development of printing inks using a binder resin derived from biomass is being promoted (for example, Patent Document 2). reference). However, a polyurethane resin having excellent blocking resistance and laminating suitability while maintaining the biomass concentration in a sufficient range and satisfying boil and retort resistance has not been obtained.

Japanese Unexamined Patent Publication No. 2011-122064 Japanese Unexamined Patent Publication No. 2018-012744

An object of the present invention is to provide a binder for printing ink, which contains a biomass-derived polyurethane urea resin and is excellent in blocking resistance, laminating suitability and boil / retort resistance.

The present inventor has arrived at the present invention as a result of diligent studies to achieve the above object. That is, the present invention is a polyurethane urea resin containing a polyol (A) having a number average molecular weight of 500 or more, a polyisocyanate (B), and a chain extender (C) having a number average molecular weight or a chemical formula less than 500 as essential constituent monomers. A binder for printing ink containing (U), wherein the polyol (A) contains 1,3-propanediol derived from biomass and / or 1,4-butanediol derived from biomass and sebacic acid derived from biomass. It contains a polyester polyol (A11) as an essential constituent monomer, the chain extender (C) contains a polyamine (C1), and the polyurethane urea resin (U) has a weight average molecular weight of 120,000 to 200. A printing ink binder of 000; a printing ink containing the printing ink binder, the pigment, and the solvent (S).

Since the binder for printing ink of the present invention contains a polyester polyol derived from biomass, it can greatly contribute to carbon neutrality for the purpose of measures against global warming and reduction of environmental load, and also has blocking resistance, laminating suitability and boil resistance. -Excellent retort property.

The binder for printing ink of the present invention contains a polyol (A) having a number average molecular weight (hereinafter abbreviated as “Mn”) of 500 or more, a polyisocyanate (B), and a chain extender (C) having a chemical formula of less than 500. It contains a polyurethane urea resin (U) as an essential constituent monomer.

Examples of the polyol (A) of the present invention include a condensed polyester polyol (A1), a polylactone polyol (A2), a polycarbonate polyol (A3), a polyether polyol (A4), and the like, and the polyol (A) is an essential component. A polyester polyol (A1) in which 1,3-propanediol derived from biomass and / or 1,4-butanediol derived from biomass and sebacic acid derived from biomass are essential constituent monomers of the condensed polyester polyol (A1). Contains A11).

The polyol (A) requires a polyester polyol (A11) containing 1,3-propanediol derived from biomass and / or 1,4-butanediol derived from biomass and sebacic acid derived from biomass as essential constituent monomers. By containing it as a component of, a binder for printing ink having a high biomass concentration and excellent blocking resistance, laminating suitability and boil / retort resistance can be obtained.

The higher the biomass concentration of the polyester polyol (A11) containing 1,3-propanediol derived from biomass and / or 1,4-butanediol derived from biomass and sebacic acid derived from biomass as essential constituent monomers, the higher the biomass concentration. Since the biomass concentration of the polyurethane urea resin (U) is high, from the viewpoint of biomass concentration, a polyester polyol (A11) consisting of only 1,3-propanediol and / or 1,4-butanediol derived from biomass and sebacic acid derived from biomass. ) Is preferable, but since the crystallinity is high, the printing ink using the polyurethane urea resin (U) containing the same tends to deteriorate the adhesion and printability. Therefore, it is preferable to use a diol having a Mn of less than 500 described below and a dicarboxylic acid described below in combination for copolymerization. As the copolymerizable diol, 1,2-propanediol and neopentyl glycol are preferable from the viewpoint of adhesion, and as the dicarboxylic acid, succinic acid and adipic acid are preferable. (A11) may be used alone or in combination of two or more.

The polyol (A) includes, in addition to the polyester polyol (A11), a condensed polyester polyol (A12) other than the (A11), a polylactone polyol (A2), a polycarbonate polyol (A3), and a polyether polyol (A4). One or more types can be used in combination.

Examples of the condensed polyester polyol (A12) other than (A11) include a diol having a Mn of less than 500 and a dicarboxylic acid or an ester-forming derivative thereof [acid anhydride, lower (1 to 4 carbon atoms) alkyl ester, acid halide, etc.]. Examples thereof include those obtained by condensation with.

Examples of diols having Mn less than 500 include aliphatic dihydric alcohols having 2 to 8 carbon atoms [straight-chain diols (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol). And 1,6-hexanediol, etc.) and diols with branched alkyl chains (1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propane) Diol, 1,2-, 1,3- or 2,3-butanediol, etc.)]; Alicyclic group-containing dihydric alcohol with 6 to 10 carbon atoms [1,4-bis (hydroxymethyl) cyclohexane and 2, 2-Bis (4-hydroxycyclohexyl) propane, etc.]; Aromatic ring-containing dihydric alcohol having 8 to 20 carbon atoms [m- or p-xylylene glycol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene]; Bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.) with 2 to 12 carbon atoms of alkylene oxide (hereinafter abbreviated as "AO") adduct, dihydroxynaphthalene AO adduct, bis (2-hydroxyethyl) terephthalate, etc.] And so on. As for the diol having Mn less than 500, one type may be used alone or two or more types may be used in combination.

AOs having 2 to 12 carbon atoms include ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, and styrene. Examples thereof include oxides and α-olefin oxides. One type of AO may be used alone, or two or more types may be used in combination.

Examples of the dicarboxylic acid or its ester-forming derivative include aliphatic dicarboxylic acids having 2 to 15 carbon atoms [oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.] and carbon atoms. 8 to 12 aromatic dicarboxylic acids [terephthalic acid, isophthalic acid, etc.] and their ester-forming derivatives [acid anhydrides, lower alkyl esters (dimethyl ester, diethyl ester, etc.), acid halides (acid chloride, etc.), etc.], etc. Can be mentioned. One type of dicarboxylic acid may be used alone, or two or more types may be used in combination.

Specific examples of the condensed polyester polyol (A12) other than (A11) include polyethylene adipatediol, polybutylene adipatediol, polyhexamethylene adipatediol, polyhexamethyleneisophthalatediol, polyneopentyl adipatediol, and polyethylenepropylene adipate. Diore, Polyesterbutylene adipate diol, Polybutylene hexamethylene adipate diol, Poly (polyoxytetramethylene) adipate diol, Poly (3-methylpentylene adipate) diol, Polyethylene azelate diol, Polyethylene sebacate diol, Polybutylene azelate diol , Polybutylene sebacate diol, polyneopentyl terephthalate diol and the like.

Among the condensed polyester polyols (A12) other than (A11), polyester diols having a linear alkyl chain are preferable from the viewpoint of blocking resistance, polyethylene adipatediol and polybutylene adipatediol are particularly preferable, and polybutylene adipatediol is most preferable. Is a polybutylene adipatediol. From the viewpoint of resolubility, polyester diols having a branched alkyl chain are preferable, polyneopentyl adipate diols and poly (3-methylpentylene adipate) diols are particularly preferable, and poly (3-methylpentylene adipate) is most preferable. ) Diol. (A12) may be used alone or in combination of two or more.

As the polylactone polyol (A2), a lactone monomer (γ-butyrolactone, γ-valerolactone, ε-caprolactone, a mixture of two or more thereof, etc.) was ring-opened and polymerized using the diol having a Mn of less than 500 as an initiator. Things etc. can be mentioned. Specific examples of the polylactone polyol (A2) include polybutyrolactone diol, polyvalerolactone diol, polycaprolactone diol and the like. For (A2), one type may be used alone or two or more types may be used in combination.

Examples of the polycarbonate polyol (A3) include the diol having a Mn of less than 500, a low molecular weight carbonate compound (for example, a dialkyl carbonate having an alkyl group having 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms, and carbon. Examples thereof include a polycarbonate diol produced by condensing a diaryl carbonate having an aryl group of No. 6 to 9 while carrying out a dealcohol reaction. (A3) may be used alone or in combination of two or more.

Specific examples of the polycarbonate polyol (A3) include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol and poly (tetramethylene / hexamethylene) carbonate diol (for example, 1,4-butanediol and 1, A diol obtained by condensing 6-hexanediol with a dialkyl carbonate while dealcoholizing it) and the like.

Examples of the polyether polyol (A4) include an AO adduct having 2 to 12 carbon atoms to a diol having a Mn of less than 500. Examples of the AO used in (A4) include the same AO used for the diol having a Mn of less than 500, and the AO may be one type alone or two or more types may be block copolymerized or randomly copolymerized. Good.

Among the polyether polyols (A4), those having a branched alkyl chain are preferable from the viewpoint of resolubility, that is, those using a diol having a branched alkyl chain among diols having a Mn of less than 500 as a raw material, or AO. As the AO in the adduct, 1,2-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, 3-methyl tetrahydrofuran and the like are used, and more preferably, it has a branched alkyl. Aliphatic polyether diols of dihydric alcohols, particularly preferred are polyoxypropylene glycols. (A4) may be used alone or in combination of two or more.

Condensation other than (A11) with polyester polyol (A11) containing 1,3-propanediol derived from biomass and / or 1,4-butanediol derived from biomass and sebacic acid derived from biomass as essential constituent monomers. When the type polyester polyol (A12), the polylactone polyol (A2), the polycarbonate polyol (A3) and / or the polyether polyol (A4) are used in combination, the condensed polyester polyol other than (A11) with respect to the weight of the polyester polyol (A11). The ratio of the total weight of (A12), the polylactone polyol (A2), the polycarbonate polyol (A3) and the polyether polyol (A4) is preferably 50% by weight or less.

The Mn of the polyol (A) is preferably 500 to 4,000, more preferably 1,000 to 3,000, from the viewpoint of laminating suitability and boil / retort resistance.
Mn in the present invention is measured by gel permeation chromatography under the following conditions.
Equipment: "Waters Alliance 2695" [manufactured by Waters]
Column: "Guardcolum SuperH-L" (1), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected together"
Sample solution: 0.25 wt% tetrahydrofuran solution Injection volume: 10 μl
Flow rate: 0.6 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polyethylene glycol

The polyisocyanate (B) in the present invention includes an aliphatic diisocyanate (B1) having 4 to 22 carbon atoms, an alicyclic diisocyanate (B2) having 8 to 18 carbon atoms, and an aromatic diisocyanate (B3) having 8 to 26 carbon atoms. And aromatic aliphatic diisocyanate (B4) having 10 to 18 carbon atoms.

Examples of the aliphatic diisocyanate (B1) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanate. Examples thereof include isocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate and bis (2-isocyanatoethyl) carbonate.

Examples of the alicyclic diisocyanate (B2) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as “IPDI”), 4,4-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2-isosia). Natethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornandiisocyanate can be mentioned.

Examples of the aromatic diisocyanate (B3) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-or 2,4. '-Diphenylmethane diisocyanate, polyaryldiisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanate Included are natodiphenylmethane, 1,5-naphthylene diisocyanate and m- or p-isocyanatophenylsulfonyl isocyanate.

Examples of the aromatic aliphatic diisocyanate (B4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α', α'-tetramethylxylylene diisocyanate.

Of these, alicyclic diisocyanate (B2) having 8 to 18 carbon atoms is preferable from the viewpoint of adhesiveness, and further preferable from the viewpoint of laminating suitability and boil / retort resistance of the polyurethane urea resin (U). Is IPDI.
One type of polyisocyanate (B) may be used alone, or two or more types may be used in combination.

Examples of the chain extender (C) having Mn or a chemical formula of less than 500 in the present invention include polyamine (C1) as an essential component and polyol (C2) as an optional component. In (C), one type may be used alone or two or more types may be used in combination.

Examples of polyamines (C1) include diamines having 2 to 12 carbon atoms (ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, toluenediamine, piperazine, etc.), poly (n = 2 to 6) alkylene (2 to 6 carbon atoms). Poly (n = 3-7) amines (diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, etc.) and hydrazine or derivatives thereof (dibasic acid dihydrazide, for example) Adipic acid dihydrazide, etc.) and the like.

Examples of the polyol (C2) include those similar to those exemplified as the diol having a Mn of less than 500, and 1,4-butanediol is preferable from the viewpoint of laminating suitability and boil / retort resistance.

As the chain extender (C), an alicyclic diamine is preferable from the viewpoint of laminating suitability and boil / retort resistance, and isophorone diamine is more preferable.

In obtaining the polyurethane urea resin (U), in addition to the essential components (A), (B) and (C), a reaction terminator (D) is used for the purpose of adjusting the molecular weight of the polyurethane urea resin. Can be done.

Examples of the reaction terminator (D) include monoalcohols having 1 to 10 carbon atoms (methanol, propanol, butanol, 2-ethylhexanol, etc.) and monoamines having 2 to 8 carbon atoms [mono or dialkylamines having 2 to 8 carbon atoms (mono or dialkylamines having 2 to 8 carbon atoms). n-Butylamine and di-n-butylamine, etc.), mono- or dialkanolamines having 2 to 6 carbon atoms (monoethanolamine, diethanolamine, propanolamine, etc.)] and the like. Of these, mono or dialkanolamines having 2 to 6 carbon atoms are preferable. The reaction terminator (D) may be used alone or in combination of two or more.

The amine value of the polyurethane urea resin (U) is preferably 0.1 to 20 mgKOH / g, more preferably 0.1 to 5 mgKOH / g, and particularly preferably 0.2 to 2 mgKOH / g. When the amine value is 0.1 mgKOH / g or more, the adhesion is good, and when it is 20 mgKOH / g or less, the viscosity and molecular weight are stable over time.

The weight ratio of the polyol (A), the polyisocyanate (B), and the chain extender (C) in the polyurethane urea resin (U) is preferably (A) :( B) :( C) = 100: 5 to 40: 0. It is 1 to 20, more preferably 100: 15 to 25: 1 to 10.

The method for producing the polyurethane urea resin (U) is not particularly limited, and is a one-shot method in which the polyol (A), the polyisocyanate (B), the chain extender (C) and, if necessary, the reaction terminator (D) are reacted at once. Alternatively, a multi-step method in which the reaction is carried out stepwise [for example, (A), (B) and, if necessary, (C) are reacted to form an isocyanate group-terminated prepolymer, and then (C) and, if necessary, (D) are further added. Any method may be used, such as a method for producing by reacting], but from the viewpoint of adhesion, the prepolymer uses a diamine having 2 to 12 carbon atoms as the chain extender (C) after forming the isocyanate group-terminated prepolymer. A method of introducing an amino group at the end of the polyurethane urea molecular chain is preferable by using such that the total value of the amino groups of the amine is excessive with respect to the equivalent amount of the isocyanate groups.

Equivalent ratio of the isocyanate group of the polyisocyanate (B) to the active hydrogen-containing group of the polyol (A), the chain extender (C) and the reaction terminator (D) used if necessary in the production of the polyurethane urea resin (U). The (isocyanate group: active hydrogen-containing group) is preferably 0.7: 1 to 0.99: 1, and more preferably 0.8: 1 to 0.98: 1.

The reaction between the polyol (A) and the polyisocyanate (B) is preferably carried out at a temperature of 20 to 140 ° C, more preferably 40 to 120 ° C. The reaction temperature of the isocyanate group-terminated prepolymer obtained by reacting the polyisocyanate (B) or the polyol (A) with the polyisocyanate and the chain extender (C) is preferably 100 ° C. or lower, more preferably 0. ~ 80 ° C.

In the above reaction, in order to accelerate the reaction, catalysts generally used in urethane reactions [amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), tin-based catalysts (dibutyltin dilaurate, dioctyltin dilaurate, etc.), dibutyltin dilaurate, etc. And tin octylate, etc.) and titanium-based catalysts (tetrabutyl titanate, etc.)] and the like may be used. The amount of the catalyst used is preferably 0.1% by weight or less based on the polyurethane urea resin.

Further, the reaction may be carried out in the solvent (S), or the solvent (S) may be added during or after the reaction.
Examples of the solvent (S) include ester solvents (ethyl acetate, butyl acetate and ethyl cellosolve acetate, etc.), ketone solvents (acetone, methyl isobutyl ketone, methyl isobutyl ketone, etc.), and ether solvents (dioxane, tetrahydrofuran, propylene glycol monomethyl, etc.). (Ester, etc.), aliphatic hydrocarbon solvents (n-hexane, n-heptane, cyclohexane, etc.) and alcohol solvents (ethanol, methanol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc.) and the like.

Of these, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, n-propyl alcohol and isopropyl alcohol are preferable from the viewpoint of resolubility of the polyurethane urea resin (U), and more preferably. Are ethyl acetate, methyl ethyl ketone and isopropyl alcohol.
As the solvent (S), one type may be used alone or two or more types may be used in combination.

The weight average molecular weight (hereinafter abbreviated as "Mw") of the polyurethane urea resin (U) in the present invention needs to be 120,000 to 200,000. When Mw is lower than 120,000, blocking resistance, laminating suitability, and boil / retort resistance are deteriorated when one liquid is used. If Mw is higher than 200,000, the ink viscosity becomes too high, and printability and workability deteriorate.

The Mw of the polyurethane urea resin (U) in the present invention is measured by gel permeation chromatography under the following conditions.
Equipment: "HLC-8220GPC" [manufactured by Tosoh Corporation]
Columns: "Guardcolumn α" (1), "TSKgel α-M" (1) [both manufactured by Tosoh Corporation]
Sample solution: 0.125% by weight dimethylformamide solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene

The biomass concentration of the polyurethane urea resin (U) in the present invention is preferably 20 to 85% by weight, more preferably 40 to 85% by weight. Within this range, a polyurethane urea resin (U) having a high degree of contribution to carbon neutrality and excellent blocking resistance, laminating suitability, and boil / retort resistance can be obtained.
The biomass concentration in the present invention means the ratio (percentage) of the weight of the constituent monomer derived from biomass used to the weight of the polyurethane urea resin (U).

The printing ink of the present invention contains the binder for printing ink of the present invention, a pigment, and the solvent (S) as essential components. The pigment is not particularly limited, and preferably inorganic pigments and organic pigments used in printing inks can be used.
Examples of the solvent (S) include ester solvents (ethyl acetate and ethyl cellosolve acetate, etc.), ketone solvents (acetone, methyl ethyl ketone), ether solvents (dioxane, tetrahydrofuran, propylene glycol monomethyl ether, etc.) and alcohol solvents (ethanol, ethanol, Methanol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc.) and the like.
As the solvent (S), ethyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, n-propyl alcohol and isopropyl alcohol are preferable from the viewpoint of resolubility of the polyurethane urea resin (U), and ethyl acetate is more preferable. , Methyl ethyl ketone and isopropyl alcohol.

Further, if necessary, other resins generally preferably used for printing inks and additives such as pigment dispersants can be blended. As for the other resins and additives, one type may be used alone or two or more types may be used in combination.

Examples of other resins include polyamide resins, nitrocelluloses, acrylic resins, vinyl acetate resins, styrene maleic acid copolymer resins, epoxy resins and rosin resins. The amount of these other resins added is preferably 30% by weight or less, more preferably 20% by weight or less in the printing ink.

The method for producing the printing ink is not particularly limited, and the printing ink can be produced using a known method or the like, for example, a general-purpose ink producing apparatus such as a three-roll, ball mill, and sand grinder mill.

An example of the compounding formulation of the printing ink of the present invention is as follows.
Binder (amount of resin solid content) of the present invention: 5 to 40% by weight (preferably 10 to 30% by weight)
Pigment: 5-40% by weight (preferably 10-30% by weight)
Other resins: 0-30% by weight (preferably 0-20% by weight)
Solvent: 30-80% by weight (preferably 40-70% by weight)

The printing ink using the printing ink binder of the present invention may be used as a one-component printing ink, but may also be used as a two-component printing ink in combination with, for example, a polyisocyanate-based curing agent. As the polyisocyanate-based curing agent in this case, for example, an adduct from 1 mol of trimesterolpropane and 3 mol of 1,6-hexamethylene disiocyanate, tolylene diisocyanate or IPDI; 1,6-hexamethylene diisoy Isocyanurate group-containing trimer synthesized by cyclic trimerization of cyanate or IPDI isocyanate groups; partial burette reactants derived from 1 mol of water and 3 mol of 1,6-hexamethylene diisoicyanate and theirs. A mixture of two or more is suitable. When used as a two-component printing ink, the amount of the polyisocyanate-based curing agent used is preferably 0.5 to 10% by weight based on the weight of the binder for printing ink of the present invention.

Examples of the printing method using the printing ink of the present invention include printing methods such as special gravure printing, inkjet printing, offset printing, and heat-sensitive transfer printing used for printing conventional plastic films.

The binder for printing ink of the present invention has excellent adhesiveness to various plastic films such as polyester, nylon and polyolefin, and can be widely used as a binder for printing ink for various plastic films.
Further, the printing ink of the present invention includes polyester film, nylon film, surface-treated or untreated polypropylene film, polyethylene film, polyvinyl acetal film, acetate film, polyvinyl chloride film, and film in which aluminum is vapor-deposited on these films. It can be suitably used for printing various plastic films.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the following, "part" indicates a weight part.

Manufacturing example 1
In a four-necked flask equipped with a recirculator, thermometer, nitrogen introduction tube, and stirrer, 152 parts of biomass-derived 1,3-propanediol, 100 parts of biomass-derived 1,4-butanediol, and 100 parts of neopentyl glycol. , 432 parts of biomass-derived sebacic acid and 216 parts of adipic acid were charged, and esterification was carried out until the acid value became 1 or less while passing water through nitrogen gas under normal pressure at 190 to 210 ° C. to carry out polyester polyol. (A11-1) was obtained. The hydroxyl value of (A11-1) was 56.0, the acid value was 0.3, and Mn was 2,000.

Manufacturing example 2
The raw materials of Production Example 1 were added to 266 parts of biomass-derived 1,3-propanediol, 45 parts of biomass-derived 1,4-butanediol, 45 parts of neopentyl glycol, 215 parts of biomass-derived sebacic acid, and 429 parts of adipic acid. A polyester polyol (A11-2) was obtained in the same manner as in Production Example 1. The hydroxyl value of (A11-2) was 56.0, the acid value was 0.4, and Mn was 2,000.

Manufacturing example 3
The raw materials of Production Example 1 were changed to 289 parts of 1,3-propanediol derived from biomass and 711 parts of sebacic acid derived from biomass, and a polyester polyol (A11-3) was obtained by the same method as in Production Example 1. The hydroxyl value of (A11-3) was 37.4, the acid value was 0.3, and Mn was 3,000.

Manufacturing example 4
The raw material of Production Example 1 was changed to 154 parts of 1,3-propanediol derived from biomass, 154 parts of 1,4-butanediol derived from biomass, and 692 parts of sebacic acid derived from biomass, and the same method as in Production Example 1 A polyester polyol (A11-4) was obtained. The hydroxyl value of (A11-4) was 37.4, the acid value was 0.3, and Mn was 3,000.

Table 1 summarizes the raw materials, Mn, and biomass concentrations of the polyester polyols (A11-1) to (A11-4) produced in Production Examples 1 to 4.

Example 1
228 parts of the polyester polyol (A11-1) synthesized in Production Example 1, 3.64 parts of biomass-derived 1,4-butanediol and 54.87 parts of IPDI were charged into a reaction device equipped with a stirring device under a nitrogen atmosphere. The reaction was carried out at 110 ° C. for 6 hours to obtain a urethane prepolymer having an NCO content of 2.72% by weight. After cooling to 40 ° C., 466 parts of ethyl acetate was added to prepare a uniform solution. Next, 234 parts of isopropanol was added and stirred until uniform, then 9.85 parts of isophoronediamine, 1.56 parts of diethylenetriamine and 1.98 parts of monoethanolamine were added and reacted at 40 ° C. for 1 hour to print the present invention. A solution of a polyurethane urea resin (U-1) having a biomass concentration of 53% by weight, which is a binder for ink, was obtained. The viscosity of the solution of (U-1) at 20 ° C. was 1,000 mPa · s, and the Mw of (U-1) was 125,000.

Example 2
A urethane urea resin (U) produced in the same manner as in Example 1 except that the polyester polyol (A11-2) synthesized in Production Example 2 was used instead of the polyester polyol (A11-1) and had a biomass concentration of 41% by weight. The solution of -2) was obtained. The viscosity of the solution of (U-2) at 20 ° C. was 1,200 mPa · s, and the Mw of (U-2) was 131,000.

Example 3
256 parts of the polyester polyol (A11-3) and 34.06 parts of IPDI synthesized in Production Example 3 were charged into a reaction device equipped with a stirrer, and reacted at 110 ° C. for 8 hours in a nitrogen atmosphere to have an NCO content of 1.98 weight. % Urethane prepolymer was obtained. After cooling to 40 ° C., 466 parts of ethyl acetate was added to prepare a uniform solution. Next, 234 parts of isopropanol was added and stirred until uniform, then 7.95 parts of isophoronediamine, 1.07 parts of diethylenetriamine and 1.27 parts of monoethanolamine were added and reacted at 40 ° C. for 1 hour to print the present invention. A solution of a polyurethane urea resin (U-3) having a biomass concentration of 85% by weight, which is a binder for ink, was obtained. The viscosity of the solution of (U-3) at 20 ° C. was 1,200 mPa · s, and the Mw of (U-3) was 136,000.

Example 4
In a reaction device equipped with a stirrer, 133 parts of the polyester polyol (A11-4) synthesized in Production Example 4 and a poly (3-methylpentylene adipate) diol [Kuraray polyol P-4010 manufactured by Kuraray Co., Ltd .: Mn. = 4000] 133 parts and 27.51 parts of IPDI were charged and reacted at 110 ° C. for 10 hours in a nitrogen atmosphere to obtain a urethane prepolymer having an NCO content of 1.33% by weight. After cooling to 40 ° C., 466 parts of ethyl acetate was added to prepare a uniform solution. Next, 234 parts of isopropanol was added and stirred until uniform, then 4.82 parts of isophoronediamine, 0.97 parts of diethylenetriamine and 1.04 parts of monoethanolamine were added, and the mixture was reacted at 40 ° C. for 1 hour to print the present invention. A solution of a polyurethane urea resin (U-4) having a biomass concentration of 44% by weight, which is a binder for ink, was obtained. The viscosity of the solution of (U-4) at 20 ° C. was 1,500 mPa · s, and the Mw of (U-4) was 196,000.

Comparative Example 1
226 parts of the polyester polyol (A11-1) synthesized in Production Example 1, 3.61 parts of 1,4-butanediol derived from biomass and 54.40 parts of IPDI were charged into a reaction device equipped with a stirrer, and the atmosphere was nitrogen. The reaction was carried out at 110 ° C. for 6 hours to obtain a urethane prepolymer having an NCO content of 2.72% by weight. After cooling to 40 ° C., 466 parts of ethyl acetate was added to prepare a uniform solution. Next, 234 parts of isopropanol was added and stirred until uniform, then 14.59 parts of isophoronediamine and 1.31 parts of monoethanolamine were added and reacted at 40 ° C. for 1 hour to bring the biomass concentration of the printing ink binder to 53. A solution of a weight% polyurethane urea resin (U'-1) was obtained. The viscosity of the solution of (U'-1) at 20 ° C. was 950 mPa · s, and the Mw of (U'-1) was 69,000.

Comparative Example 2
254 parts of the polyester polyol (A11-3) and 33.84 parts of IPDI synthesized in Production Example 3 were charged into a reaction device equipped with a stirrer and reacted at 110 ° C. for 8 hours in a nitrogen atmosphere to have an NCO content of 1.98 weight. % Urethane prepolymer was obtained. After cooling to 40 ° C., 466 parts of ethyl acetate was added to prepare a uniform solution. Next, 234 parts of isopropanol was added and stirred until uniform, then 11.71 parts of isophoronediamine and 0.42 parts of monoethanolamine were added and reacted at 40 ° C. for 1 hour to bring the biomass concentration of the printing ink binder to 85. A solution of a weight% polyurethane urea resin (U'-2) was obtained. The viscosity of the solution of (U'-2) at 20 ° C. was 1,000 mPa · s, and the Mw of (U'-2) was 86,000.

Comparative Example 3
In a reactor equipped with a stirrer, 128 parts of poly (3-methylpentylene adipate) diol [“Kuraray polyol P-4010” manufactured by Kuraray Co., Ltd .: Mn = 4000], poly (3-methylpentylene adipate) diol [Kuraray Polyol P-2010 manufactured by Kuraray Co., Ltd .: Mn = 2000] 128 parts and 34.12 parts of IPDI were charged and reacted at 110 ° C. for 10 hours in a nitrogen atmosphere to make a urethane prepolymer having an NCO content of 1.67% by weight. A polymer was obtained. After cooling to 40 ° C., 466 parts of ethyl acetate was added to prepare a uniform solution. Next, 234 parts of isopropanol is added and stirred until uniform, then 7.83 parts of isophoronediamine, 0.63 parts of diethylenetriamine and 0.84 parts of monoethanolamine are added and reacted at 40 ° C. for 1 hour to make a binder for printing ink. A solution of polyurethane urea resin (U'-3) was obtained. The viscosity of the solution of (U'-3) at 20 ° C. was 1,400 mPa · s, and the Mw of (U'-3) was 100,500.

Examples 5-8 and Comparative Examples 4-6
Using the solutions of the polyurethane urea resins obtained in Examples 1 to 4 and Comparative Examples 1 to 3, printing inks were prepared according to the following formulations.

[Making white ink]
Paint conditioner (Red Devil) with a mixture of 35 parts of polyurethane urea resin solution, 35 parts of titanium oxide ("Titanics JR809" manufactured by Teika Co., Ltd.), 10 parts of isopropyl alcohol, 20 parts of ethyl acetate and 100 parts of glass beads. The glass beads were removed by filtration to obtain white ink.

The results of the following performance tests using the obtained printing ink are shown in Table 2 together with the raw materials used for the polyurethane urea resin (U) and Mw.

[Test method for blocking resistance]
Surface-treated polyester film (PET) ["Espet E-5102" (thickness 12 μm) manufactured by Toyobo Co., Ltd.] is coated with printing ink with a bar coater so that the solid content has a thickness of 2 to 3 μm, and the temperature is 40 ° C. After drying for 1 minute, the untreated surface of the polyester film was placed on the coated surface so as to be in close contact with each other, a pressure of ² kg / cm ² was applied with a blocking tester, and the film was left at a temperature of 50 ° C. for 24 hours. After that, the film was cooled to room temperature, the state of the coated surface when the stacked films were peeled off was observed, and the evaluation was made by the area% where the ink was not peeled off.

[Test method for ethyl acetate resistance]
Surface-treated polyester film (PET) [“Espet E-5102” (thickness 12 μm) manufactured by Toyo Spinning Co., Ltd.] is coated with printing ink with a bar coater so that the solid content has a thickness of 2 to 3 μm, and the temperature is 40 ° C. After drying for 1 minute, the ink surface was rubbed once with absorbent cotton soaked with ethyl acetate, and the area% of the area where the ink was not dissolved was evaluated.

[Boil resistance test method]
Surface-treated polyester film (PET) ["Espet E-5102" (thickness 12 μm) manufactured by Toyo Spinning Co., Ltd.] is coated with printing ink with a bar coater so that the solid content has a thickness of 2 to 3 μm, and the temperature is 40 ° C. After drying for 1 minute with, a dry laminating adhesive [main agent: Polybond AY-651A, curing agent: Polybond AY-651C (manufactured by Sanyo Kasei Kogyo)] is applied to the coated surface, and LLDPE (Mitsui Kagaku) is used with a laminator. It was laminated with (manufactured by Tohcello) and aged at 40 ° C for 48 hours. After that, the bag is made by heat sealing with the LLDPE side as the inside, and a mixture of vinegar: salad oil: meat sauce = 1: 1: 1 (weight ratio) is sealed as the contents, and the appearance after boiling at 98 ° C. for 1 hour. Was visually observed, and the portion where the laminated film was not peeled off or floated was evaluated by area%.

The binder for printing ink of the present invention contains a biomass-derived polyurethane urea resin and is excellent in blocking resistance, laminating suitability and boil / retort resistance. Therefore, various plastic films (polyester film, nylon film, polypropylene film and cellophane film) Etc.), which is particularly suitable as a binder for special gravure ink. Further, the binder of the present invention is useful not only for the above-mentioned applications but also as a binder for flexographic printing inks, a binder for paints, an adhesive, and a coating agent for paper and the like.

Claims (7)

Containing a polyurethane urea resin (U) containing a polyol (A) having a number average molecular weight of 500 or more, a polyisocyanate (B), and a chain extender (C) having a number average molecular weight or a chemical formula less than 500 as an essential constituent monomer. The polyol (A) is a binder for printing ink, and is an essential constituent unit amount of 1,3-propanediol derived from biomass and / or 1,4-butanediol derived from biomass and sebacic acid derived from biomass. Printing in which the polyester polyol (A11) as a body is contained, the chain extender (C) contains a polyamine (C1), and the polyurethane urea resin (U) has a weight average molecular weight of 120,000 to 200,000. Binder for ink. The binder for printing ink according to claim 1, wherein the polyurethane urea resin (U) has a biomass concentration of 20 to 85% by weight. The binder for printing ink according to claim 1 or 2, wherein the polyol (A) has a number average molecular weight of 500 to 4,000. The binder for printing ink according to any one of claims 1 to 3, wherein the polyisocyanate (B) is an alicyclic diisocyanate (B2) having 8 to 18 carbon atoms. The binder for printing ink according to any one of claims 1 to 4, wherein the polyamine (C1) is an alicyclic diamine. The binder for printing ink according to any one of claims 1 to 5, wherein the polyurethane urea resin (U) further comprises a reaction terminator (D) as a constituent monomer. A printing ink containing the binder for printing ink, the pigment, and the solvent (S) according to any one of claims 1 to 6.