JP6665198B2 - Solvent-based printing ink binder and solvent-based printing ink using the same - Google Patents

Description

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

Conventionally, printing inks using a polyurethane resin as a binder have excellent adhesion to polyester films and nylon films alone, but have sufficient adhesion to polyolefin films such as polyethylene and polypropylene films, which are general-purpose films. The printing ink using chlorinated polyolefin as a binder has good adhesion to polyolefin films, but has no sufficient adhesion to polyester films and nylon films. There is a problem of being restricted. It has been proposed to mix and use a polyurethane resin and a chlorinated polyolefin for the purpose of general use for various plastic films (for example, see Patent Document 1).

However, in recent years, efforts have been made to address environmental issues, and it has been strongly desired to suppress the generation of harmful substances in the disposal of used products, and chlorinated polyolefins contain chlorine. Therefore, there is a problem that harmful substances are generated at the time of incineration, which may pollute the environment.

In addition, solvents such as toluene, methyl ethyl ketone (MEK), and ethyl acetate have been mixed and used as solvents for printing inks for plastic films. However, due to the revision of the Industrial Safety and Health Law, the environmental concentration regulations for toluene have been strengthened, and the demand for solvent-based printing inks that do not contain toluene has increased. In recent years, there has been a demand for more environmentally compatible alcohol-based printing inks. Is increasing. A polyurethane resin containing polypropylene glycol has been proposed using only a solvent such as MEK and ethyl acetate without using toluene (for example, see Patent Document 2). Occasionally, plate clogging occurs, and inks using alcohol containing a large amount of water have problems such as deterioration of stability and deterioration of boiling resistance.

JP-A-10-251594 JP 2005-298618 A

The problem to be solved by the present invention is excellent in versatility that can be used for various plastic films, excellent in resolubility in a solvent, extremely low plate clogging during printing, and ink stability even when moisture is mixed. It is an object of the present invention to provide a solvent-based printing ink binder which is excellent in boil resistance and boil resistance.

The present inventors have conducted intensive studies to achieve the above object, and as a result, have reached the present invention. That is, the present invention relates to a solvent-based printing ink binder containing a polyurethane urea resin (U), wherein the polyurethane urea resin (U) comprises a compound (F) having two active hydrogens and ethylene oxide and 1,2- Polyether diol (A), diamine (B) and diisocyanate (C), which are adducts to which an alkylene oxide containing propylene oxide has been added, are essential constituent monomers, and an oxyethylene group for the polyurethane urea resin (U) is used. Is a solvent-based printing ink binder having a content of 2 to 24% by weight; a solvent-based printing ink containing the solvent-based printing ink binder, a pigment, and a solvent.

The binder for a solvent-based printing ink of the present invention is excellent in versatility that can be used for various plastic films, excellent in resolubility in a solvent, has very little plate clogging at the time of printing, and can be used even when water is mixed. Excellent stability and excellent boil resistance.

The binder for a solvent-based printing ink of the present invention comprises an alkylene oxide (hereinafter abbreviated as PO) and ethylene oxide (hereinafter abbreviated as EO) and 1,2-propylene oxide (hereinafter abbreviated as PO) in a compound (F) having two active hydrogens. , AO) and a polyurethane urea resin (U) containing polyether diol (A), diamine (B) and diisocyanate (C), which are adducts to which is added an essential constituent monomer.

Examples of the compound (F) having two active hydrogens of the polyether diol (A) include water; an aliphatic dihydric alcohol having 2 to 8 carbon atoms [linear diol (ethylene glycol, diethylene glycol, 1,3-propanediol) , 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.), diols having a branched alkyl chain (1,2-propanediol, neopentyl glycol, 3-methyl-1,5- Pentanediol, 2,2-diethyl-1,3-propanediol, 1,2-, 1,3- or 2,3-butanediol, etc.); an alicyclic group-containing dihydric alcohol having 6 to 10 carbon atoms. [1,4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, etc.]; an aromatic ring having 8 to 20 carbon atoms Dihydric alcohol [m- or p-xylylene glycol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene, bisphenols (such as bisphenol A, bisphenol S and bisphenol F), dihydroxynaphthalene], and carbon number 1 To 12 monoalkylamines [monomethylamine, monoethylamine, monobutylamine, etc.].

AO added to the compound (F) having two active hydrogens contains EO and PO.
AO added to the compound (F) having two active hydrogens includes, in addition to EO and PO, 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran And other AO such as 3-methyltetrahydrofuran, styrene oxide and α-olefin oxide. The content of these other AOs is preferably 30% by weight or less based on the total weight of EO and PO.
The weight ratio between EO and PO is preferably EO / PO = 10/90 to 90/10, more preferably 20/80 to 75/25, and more preferably 30/70 to 80/20.
There are random and block addition forms of EO and PO, and random is preferable from the viewpoint of boiling resistance.

The distinction between random and block can be determined by C-NMR measurement when the copolymer adduct is EO and PO. Among the integrated values (X) of all peaks (60.0 to 62.0, 68.0 to 68.8, 70.0 to 71.0 ppm) derived from EO, EO adjacent to the secondary carbon of PO Assuming that the ratio of the integrated value (Y) of the peak (68.0 to 68.8 ppm) derived from is (Z), it can be calculated by (Z) = (Y) / (X) × 100. It can be said that the larger the ratio, the higher the ratio of random copolymerization.
For example, when the molar ratio of the added EO / PO is 50/50 and the number average molecular weight of the copolymerized adduct is 4,000, the ratio (Z) of the integrated value of the peak derived from EO adjacent to the secondary carbon of PO is (Z) 20 to 50 for random copolymerization and 1 to 5 for block copolymerization. When the addition mole ratio of EO / PO is 80/20 and the number average molecular weight of the copolymerization adduct is 4,000, the ratio (Z) of the integral value of the peak derived from EO adjacent to the secondary carbon of PO is random. It is 7 to 15 for copolymerization and 0.5 to 3 for block copolymerization.

As the polyether diol (A), from the viewpoint of resolubility, an adduct obtained by adding only EO and PO to water, an adduct obtained by adding only EO and PO to 1,2-propanediol, or EO added to ethylene glycol And an adduct to which only PO is added.

The polyurethane urea resin (U) further comprises, as constituent monomers, a polyether diol (a1) other than the polyether diol (A), a polyester diol (a2), a polylactone diol (a3) and a polycarbonate diol (a4). It is preferable to contain at least one diol (a) selected from the group from the viewpoint of resolubility and adhesion. The number average molecular weight of the diol (a) is preferably 500 or more. Among the diols (a), polyether diol (a1) or polyester diol (a2) is more preferable from the viewpoint of resolubility and adhesion.
The diol (a) preferably has a branched alkyl group from the viewpoint of resolubility.

The number average molecular weight (hereinafter, abbreviated as Mn) of the polyether diol (A) and the diol (a) can be measured by gel permeation chromatography.
The measuring conditions of Mn are as follows.
Apparatus: "Waters Alliance 2695" [manufactured by Waters]
Column: "Guardcolumn Super HL" (one), "TSKgel SuperH2000, TSKgel SuperH3000, and TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected one by one"
Sample solution: 0.25 wt% tetrahydrofuran solution solution injection volume: 10 μL
Flow rate: 0.6 mL / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference substance: Standard polyethylene glycol

Mn of the polyether diol (A) and the diol (a) is preferably from 500 to 10,000, and more preferably from 1,000 to 4,000, from the viewpoint of adhesiveness and solubility.

Examples of the polyether diol (a1) include a diol (a5) having the following Mn of less than 500 and an AO adduct having 2 to 12 carbon atoms to a monoalkylamine. Examples of AO having 2 to 12 carbon atoms include EO, PO, 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, styrene oxide and α- Olefin oxide and the like can be mentioned. One of these AOs having 2 to 12 carbon atoms may be added to a monoalkylamine, or a plurality of AOs may be added to a monoalkylamine.
The polyether diol (a1) does not include the polyether diol (A).

Examples of the diol (a5) having Mn of less than 500 include aliphatic dihydric alcohols having 2 to 8 carbon atoms [linear diols (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5 -Pentanediol and 1,6-hexanediol, etc.), diols having a branched alkyl chain (1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1, 3-propanediol, 1,2-, 1,3- or 2,3-butanediol, etc.); alicyclic group-containing dihydric alcohol having 6 to 10 carbon atoms [1,4-bis (hydroxymethyl) cyclohexane And 2,2-bis (4-hydroxycyclohexyl) propane and the like]; an aromatic ring-containing dihydric alcohol having 8 to 20 carbon atoms [m- or p- Silene glycol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene, AO adducts of bisphenols (such as bisphenol A, bisphenol S and bisphenol F) having 2 to 12 carbon atoms, AO adducts of dihydroxynaphthalene and bis ( 2-hydroxyethyl) terephthalate and the like];

Among the polyether diols (a1), those having a branched alkyl chain are preferred from the viewpoint of resolubility. That is, as a raw material, a diol having a branched alkyl chain among diols having Mn of less than 500 or PO, 1,2-, 2,3- or 1,3-butylene oxide and 3- And those using methyltetrahydrofuran or the like. More preferred is an AO adduct of the aliphatic dihydric alcohol having a branched alkyl chain to which the above-mentioned AO has been added, and particularly preferred is polyoxypropylene glycol.

The polyurethane urea resin (U) contained in the binder for a solvent-based printing ink of the present invention may contain one kind of polyether diol (a1) as a constituent monomer, and plural kinds of polyether diol (a1). May be included.

As the polyester diol (a2), a diol (a5) having an 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.] are condensed. And the like obtained.

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

Specific examples of the polyester diol (a2) include, for example, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, and polyethylene butylene 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 And polyneopentyl terephthalate diol.

Among the polyester diols (a2), polyester diols having a branched alkyl chain are preferred from the viewpoint of resolubility, and particularly preferred are polyneopenthylene adipate diol, polyethylene propylene adipate diol and poly (3-methylpentylene adipate). ) Diols, most preferably polyneopentylene adipate diol, poly (3-methylpentylene adipate) diol.

The polyurethane urea resin (U) contained in the binder for a solvent-based printing ink of the present invention may contain one kind of polyester diol (a2) as a constituent monomer, or contain plural kinds of polyester diol (a2). You may go out.

As the polylactone diol (a3), a lactone monomer (γ-butyrolactone, γ-valerolactone, ε-caprolactone, a mixture of two or more of these, etc.) is opened with a diol (a5) having an Mn of less than 500 as an initiator. Examples thereof include those obtained by polymerization. Specific examples of the polylactone diol include polybutyrolactone diol, polyvalerolactone diol, and polycaprolactone diol.

The polyurethane urea resin (U) contained in the binder for a solvent-based printing ink of the present invention may contain one kind of polylactone diol (a3) as a constituent monomer, and plural kinds of polylactone diol (a3) May be included.

As the polycarbonate diol (a4), a diol (a5) having an Mn of less than 500 and a low molecular carbonate compound (for example, a dialkyl carbonate having 1 to 6 carbon atoms of an alkyl group, an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms) And a diaryl carbonate having an aryl group having 6 to 9 carbon atoms).

Specific examples of the polycarbonate diol include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, and poly (tetramethylene / hexamethylene) carbonate diol (for example, 1,4-butanediol and 1,6-hexane). A diol obtained by condensing a diol with a dialkyl carbonate while performing a dealcoholation reaction).

The polyurethane urea resin (U) contained in the binder for a solvent-based printing ink of the present invention may contain one kind of polycarbonate diol (a4) as a constituent monomer, or contain plural kinds of polycarbonate diol (a4). You may go out.

In the solvent-based printing ink binder of the present invention, the total content of the diol (a) is preferably 0 to 90% by weight, more preferably 5 to 80% by weight, based on the weight of the polyurethane urea resin (U). It is.

The polyurethane urea resin (U) may contain, as a constituent monomer, the diol (a5) having an Mn of less than 500 described above, in addition to the polyether diol (A).
When producing the polyurethane urea resin (U), the urea group concentration and the urea group concentration in the polyurethane urea resin (U) can be adjusted by using the diol (a5) having Mn of less than 500. The content of the diol (a5) having Mn of less than 500 is preferably 0 to 3% by weight, more preferably 0.001 to 3% by weight, based on the weight of the polyurethane urea resin (U).

Examples of the diamine (B) include diamines having 2 to 12 carbon atoms, hydrazine and derivatives thereof (dibasic dihydrazide such as adipic dihydrazide). The diamine (B) may be contained alone or in combination of two or more.

Examples of the diamine having 2 to 12 carbon atoms include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, toluenediamine, and piperazine.
Among these, isophoronediamine is preferred from the viewpoint of resolubility.

When the polyurethane urea resin (U) contains a diol (a5) having an Mn of less than 500, that is, when the diamine (B) and the diol (a5) having an Mn of less than 500 are used in combination, the Mn is less than 500. As the diol (a5), 1,4-butanediol is preferable from the viewpoint of resolubility and solvent resistance.

Examples of the diisocyanate (C) include an aliphatic diisocyanate (C1) having 4 to 22 carbon atoms, an alicyclic diisocyanate (C2) having 8 to 18 carbon atoms, an aromatic diisocyanate (C3) having 8 to 26 carbon atoms, and To 18 araliphatic diisocyanates (C4).

Examples of the aliphatic diisocyanate having 4 to 22 carbon atoms (C1) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanate. Isocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and the like can be mentioned.

Examples of the alicyclic diisocyanate (C2) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2-isocyanate). Ethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

Examples of the aromatic diisocyanate having 8 to 26 carbon atoms (C3) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4′- or 2,4 '-Diphenylmethane diisocyanate, polyaryl diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanate Examples include natodiphenylmethane, 1,5-naphthylene diisocyanate and m- or p-isocyanatophenylsulfonyl isocyanate.

Examples of the araliphatic diisocyanate (C4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

Of these, preferred as the diisocyanate (C) is an alicyclic diisocyanate (C2) having 8 to 18 carbon atoms from the viewpoint of adhesiveness, and further preferred from the viewpoint of resolubility of the polyurethane urea resin (U). Is IPDI.
The diisocyanate (C) may be contained alone or in combination of two or more.

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

As the reaction terminator (D), monoalcohols having 1 to 10 carbon atoms (such as methanol, propanol, butanol and 2-ethylhexanol) and monoamines having 2 to 8 carbon atoms [mono- or dialkylamines having 2 to 8 carbon atoms ( mono- or dialkanolamines having 2 to 6 carbon atoms (such as monoethanolamine, diethanolamine and propanolamine)]. Preferred among these are mono- or dialkanolamines having 2 to 6 carbon atoms. As the reaction terminator (D), one type may be used alone, or two or more types may be used in combination.

The content of oxyethylene groups in the binder for a solvent-based printing ink of the present invention is 2 to 24% by weight based on the weight of the polyurethane urea resin (U). When the content of the oxyethylene group is less than 2% by weight, the ink stability deteriorates, and when it exceeds 24% by weight, the boil resistance becomes poor. The content of the oxyethylene group is preferably 3 to 22% by weight, more preferably 4 to 20% by weight, further preferably 5 to 18% by weight, and still more preferably 10 to 16% by weight. .
In particular, when the content of the oxyethylene group is 5 to 18% by weight based on the weight of the polyurethane urea resin (U), both ink stability and boil resistance can be improved.
The content of the oxyethylene group in the polyurethane urea resin (U) can be quantified by ¹ H-NMR. ¹ H-NMR is measured, and the oxyethylene group content is calculated from the ratio of the integral amount derived from the oxyethylene group near the chemical shift of 3.5 ppm to the integral amount of hydrogen derived from other constituent components.
The oxyethylene group in the binder for the solvent-based printing ink of the present invention is a polyether diol (A) which is a constituent monomer of the polyurethane urea resin (U), a polyether diol (a1), a polyester diol (a2), At least one diol (a) selected from the group consisting of a polylactone diol (a3) and a polycarbonate diol (a4), which is derived from a diol (a5) having an Mn of less than 500, but derived from another compound. You may.

The polyurethane urea resin (U) contains polyether diol (A), diamine (B) and diisocyanate (C) as constituent monomers, and the ratio is preferably (A) :( B) :( C) = 100: 0.1 to 20: 5 to 40, more preferably 100: 1 to 10:15 to 25.
The content of the reaction terminator (D) is preferably from 0.01 to 1.0% by weight, more preferably from 0.1 to 0.6% by weight, based on the weight of the polyurethane resin (U).

The total value of the urethane group [-NHCOO-] concentration and the urea group [-NHCONH-] concentration in the polyurethane urea resin (U) is preferably from 0.8 to 2.0 mmol / from the viewpoint of re-dissolving property and adhesiveness. g, more preferably 0.9 to 1.9 mmol / g, and still more preferably 1.1 to 1.9 mmol / g.
The total value of the urethane group [-NHCOO-] concentration and the urea group [-NHCONH-] concentration in the polyurethane urea resin (U) is calculated based on the nitrogen atom content determined by a nitrogen analyzer [ANTEK7000 (manufactured by Antech)]. It can be quantified by ¹ H-NMR. ^{The 1} H-NMR measurement is performed by the method described in “Structural Study of Polyurethane Resin by NMR: Takeda Research Laboratory Report 34 (2), 224-323 (1975)”. That is, ¹ H-NMR was measured, and when an aliphatic was used, the ratio of the integral amount of hydrogen derived from the urea group near the chemical shift of 6 ppm to the integral amount of hydrogen derived from the urethane group near the chemical shift of 7 ppm showed that the urea group was used. The weight ratio of the urethane group is measured, and the urethane group concentration and the urea group concentration are calculated from the weight ratio and the nitrogen atom content. When an aromatic isocyanate is used, the weight ratio of the urea group and the urethane group is calculated from the ratio of the integral amount of hydrogen derived from the urea group near the chemical shift of 8 ppm and the integral amount of hydrogen derived from the urethane group near the chemical shift of 9 ppm. The urethane group concentration and the urea group concentration are calculated from the weight ratio and the nitrogen atom content.

From the viewpoint of resolubility, the polyurethane urea resin (U) has, as a constituent monomer thereof, at least one selected from the group consisting of a trifunctional tetrafunctional polyhydric alcohol, a trifunctional tetrafunctional polyisocyanate, and a dihydroxycarboxylic acid. One kind of compound (E) may be contained in a very small amount or less. Further, the polyurethane urea resin (U) may not contain any of a trifunctional to tetrafunctional polyhydric alcohol, a trifunctional to tetrafunctional polyisocyanate, and a dihydroxycarboxylic acid.
When the compound (E) is contained in the polyurethane urea resin (U), the content of the compound (E) is preferably 0.4% by weight or less with respect to the weight of the urethane resin (U). % By weight, and more preferably 0.0001 to 0.1% by weight.
When the polyurethane urea resin (U) contains a tri- or tetra-functional polyhydric alcohol, the tri- or tetra-functional polyhydric alcohol is preferably trimethylolpropane.
When the polyurethane urea resin (U) contains a dihydroxycarboxylic acid, the dihydroxycarboxylic acid is preferably dimethylolpropionic acid.

The method for producing the polyurethane urea resin (U) is not particularly limited, and is a one-shot method in which the polyether diol (A), the diamine (B), the diisocyanate (C) and, if necessary, the reaction terminator (D) are reacted at one time. Alternatively, a multi-step method of reacting stepwise [for example, after reacting polyetherdiol (A) and diisocyanate (C) to form an isocyanate group-terminated prepolymer, diamine (B) and, if necessary, reaction terminator (D) are added. And a method of producing a prepolymer by further reacting the same. However, from the viewpoint of adhesiveness, after forming an isocyanate group-terminated prepolymer, the prepolymer may be a diamine having 2 to 12 carbon atoms as diamine (B). Polyurethane is used so that the total value of amino groups of the amine is excessive with respect to the equivalent of isocyanate groups. A method of introducing an amino group at the end of N'urea molecular chain.

In producing the polyurethane urea resin (U), the equivalent ratio of the isocyanate group of the diisocyanate (C) to the active hydrogen-containing group of the polyether diol (A), the diamine (B) and the reaction terminator (D) used as required ( (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 temperature of the polyether diol (A) and the diisocyanate (C) is preferably from 20 to 140C, more preferably from 40 to 120C. However, the reaction temperature when reacting the diamine (B) is preferably 100 ° C or lower, more preferably 0 to 80 ° C.

In the reaction, catalysts used in the urethane reaction [amine catalysts (such as triethylamine, N-ethylmorpholine and triethylenediamine) and tin-based catalysts (dibutyltin dilaurate, dioctyltin dilaurate and octylic acid) may be used to promote the reaction. Tin) and a titanium-based catalyst (such as tetrabutyl titanate). The amount of the catalyst to be used is preferably 0.1% by weight or less, and more preferably 0.001 to 0.1% by weight, based on the total weight of the compounds to be constituent monomers of the polyurethane urea resin (U). More preferred.

The reaction may be performed in an organic solvent, or the organic solvent may be added during or after the reaction. Examples of the organic solvent include ester solvents (such as ethyl acetate, butyl acetate and ethyl cellosolve acetate), ketone solvents (such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl isobutyl ketone), and ether solvents (dioxane, tetrahydrofuran and propylene glycol monomethyl). Ethers), aliphatic hydrocarbon solvents (such as n-hexane, n-heptane and cyclohexane), and alcohol solvents (such as ethanol, methanol, n-propyl alcohol, isopropyl alcohol and n-butanol).

Among these, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, n-propyl alcohol, and isopropyl alcohol are more preferable from the viewpoint of resolubility of the polyurethane urea resin (U). Are ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and isopropyl alcohol.
One organic solvent may be used alone, or two or more organic solvents may be used in combination.

The weight average molecular weight (hereinafter, abbreviated as Mw) of the polyurethane urea resin (U) in the present invention is preferably from 50,000 to 200, from the viewpoint of the resin physical properties, resolubility and solvent resistance of the polyurethane urea resin (U). 000, more preferably 100,000 to 150,000.

Mw in the present invention can be measured by gel permeation chromatography.
Apparatus: "HLC-8220GPC" [manufactured by Tosoh Corporation]
Column: "Guardcolumn α" (1), "TSKgel α-M" (1) [both manufactured by Tosoh Corporation]
Sample solution: 0.125 wt% dimethylformamide solution solution injection volume: 100 μL
Flow rate: 1 mL / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference substance: Standard polystyrene

The binder for a solvent-based printing ink of the present invention comprising the polyurethane urea resin (U) may be used as a solution (varnish) in which the polyurethane urea resin (U) is dissolved in the above-mentioned organic solvent from the viewpoint of handling properties and the like. preferable. The resin concentration of the polyurethane urea resin (U) in the organic solvent is preferably from 10 to 60% by weight, more preferably from 20 to 50% by weight, from the viewpoint of handling properties and the like. Further, the viscosity at 20 ° C. of the organic solvent solution of the polyurethane urea resin (U) is preferably 50 to 100,000 mPa · s, and more preferably 100 to 10,000 mPa · s from the same viewpoint.

The solvent-based printing ink of the present invention contains the binder, pigment and solvent for the solvent-based printing ink of the present invention as essential components. The pigment is not particularly limited, and inorganic pigments and organic pigments used in ordinary solvent-based printing inks can be used.
As the solvent, an organic solvent used in the above reaction can be used. From the viewpoint of resolubility of the polyurethane urea resin (U), preferred are ethyl acetate, butyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, n- Propyl alcohol and isopropyl alcohol are more preferred, and ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and isopropyl alcohol are more preferred. Particularly preferred is a mixed solvent containing alcohol, for example, a mixed solvent of ethyl acetate and isopropyl alcohol, a mixed solvent of methyl ethyl ketone and isopropyl alcohol, and the like.

If necessary, additives such as other resins and pigment dispersants commonly used in solvent-based printing inks can also be blended. As the other resins and additives, one kind may be used alone, or two or more kinds may be used in combination.

Examples of other resins include polyamide resins, nitrocellulose, acrylic resins, vinyl acetate resins, styrene / maleic acid copolymer resins, epoxy resins, and rosin resins. The amount of these other resins to be added is preferably 30% by weight or less, more preferably 20% by weight or less, in the solvent-based printing ink. Further, the content is preferably 0.5% by weight or more.

The method for producing the solvent-based printing ink of the present invention is not particularly limited, and a solvent-based printing ink can be produced by a known method such as a conventional ink production apparatus such as a three-roll, ball mill and sand grinder mill.

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

The solvent-based printing ink using the binder for a solvent-based printing ink of the present invention may be used as a one-part printing ink, but is used as a two-part printing ink in combination with, for example, a polyisocyanate-based curing agent. You can also. Examples of the polyisocyanate-based curing agent in this case include an adduct from 1 mol of trimethylolpropane and 3 mol of 1,6-hexamethylene diisoisocyanate, tolylene diisocyanate or IPDI; Isocyanurate group-containing trimers synthesized by cyclotrimerization of isocyanate groups of cyanate or IPDI; partial buret reactants derived from 1 mol of water and 3 mol of 1,6-hexamethylene diisoisocyanate; Mixtures of two or more are preferred. When used as a two-part 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 solvent-based printing ink binder of the present invention.

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

The solvent-based printing ink binder of the present invention has excellent adhesiveness to various plastic films such as polyester, nylon, and polyolefin, and can be generally used as a solvent-based printing ink binder for various plastic films.
The solvent-based printing ink of the present invention is a polyester film, a nylon film, a surface-treated or untreated polypropylene film, a polyethylene film, a polyvinyl acetal film, an acetate film, a polyvinyl chloride film, and a film obtained by subjecting these films to aluminum evaporation. For printing various plastic films.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In the following, “parts” indicates parts by weight.

Production Example 1
After charging 57.9 parts of 1,2-propanediol and 1.0 part of potassium hydroxide in a reaction vessel equipped with a stirrer and a temperature controller, the reaction temperature is adjusted to 2380.3 parts of EO and 540.8 parts of PO under stirring. It was charged continuously while controlling to 100 to 110 ° C. 60.0 parts of water and 60.0 parts of an alkali adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) are added to the obtained crude polyether polyol containing a catalyst, and the mixture is subjected to an adsorption treatment, filtration and drying, followed by purification. Further, 0.9 part of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan) was added, and the mixture was dissolved by stirring. 3000 parts of ether diol (A-1) was obtained. The polyether diol (A-1) was an EO / PO random adduct of 1,2-propanediol, with a weight ratio of EO / PO of 80/20 and Mn = 4000.

Production Example 2
After charging 50.6 parts of 1,2-propanediol and 1.0 part of potassium hydroxide in a reaction vessel equipped with a stirrer and a temperature controller, the reaction temperature is changed to 1651.2 parts of EO and 1297.2 parts of PO under stirring. It was charged continuously while controlling to 100 to 110 ° C. 60.0 parts of water and 60.0 parts of an alkali adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) are added to the obtained crude polyether polyol containing a catalyst, and the mixture is purified by adsorption treatment, filtration and drying. Further, 0.9 part of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan) is added, and the mixture is dissolved by stirring. 3000 parts of ether diol (A-2) was obtained. The polyether diol (A-2) was a random EO / PO adduct of 1,2-propanediol with a weight ratio of EO / PO of 55/45 and Mn = 4900.

Production Example 3
After charging 87.8 parts of 1,2-propanediol and 1.0 part of potassium hydroxide in a reaction vessel equipped with a stirrer and a temperature controller, the reaction temperature is changed to 898.7 parts of EO and 2012.5 parts of PO under stirring. It was charged continuously while controlling to 100 to 110 ° C. 60.0 parts of water and 60.0 parts of an alkali adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) are added to the obtained crude polyether polyol containing a catalyst, and the mixture is subjected to an adsorption treatment, filtration and drying, followed by purification. Further, 0.9 part of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan) was added, and the mixture was dissolved by stirring. 3000 parts of ether diol (A-3) was obtained. The polyether diol (A-3) was an EO / PO random adduct of 1,2-propanediol, with a weight ratio of EO / PO of 30/70 and Mn = 2000.

Production Example 4
After charging 214.3 parts of 1,4-butanediol and 1.0 part of potassium hydroxide in a reaction vessel equipped with a stirrer and a temperature controller, the reaction temperature is changed to 1202.5 parts of EO and 1582.1 parts of PO under stirring. It was charged continuously while controlling to 100 to 110 ° C. 60.0 parts of water and 60.0 parts of an alkali adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) are added to the obtained crude polyether polyol containing a catalyst, and the mixture is subjected to an adsorption treatment, filtration and drying, followed by purification. Further, 0.9 part of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan) was added, and the mixture was dissolved by stirring. 3000 parts of ether diol (A-4) was obtained. The polyether diol (A-4) was an EO / PO random adduct of 1,4-butanediol, with a weight ratio of EO / PO of 50/50 and Mn = 2000.

Production Example 5
A reaction vessel equipped with a stirrer and a temperature controller was charged with 931.3 parts of "New Pole BP-3P" (manufactured by Sanyo Chemical Industries, Ltd.), which is a PO adduct of bisphenol A, and 1.0 part of potassium hydroxide. While stirring, 1110.3 parts of EO and 1460.8 parts of PO were continuously charged while controlling the reaction temperature to be 100 to 110 ° C. 60.0 parts of water and 60.0 parts of an alkali adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) are added to the obtained crude polyether polyol containing a catalyst, and the mixture is subjected to an adsorption treatment, filtration and drying, followed by purification. Further, 0.9 part of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan) was added, and the mixture was dissolved by stirring. 3000 parts of ether diol (A-5) was obtained. The polyether diol (A-5) was a random EO / PO adduct of bisphenol A, with a weight ratio of EO / PO of 50/50 and Mn = 2000.

Production Example 6
After charging 57.9 parts of 1,2-propanediol and 1.0 part of potassium hydroxide in a reaction vessel equipped with a stirrer and a temperature controller, 540.8 parts of PO is added so that the reaction temperature becomes 100 to 110 ° C. It was thrown in continuously while controlling. Next, 2380.3 parts of EO was continuously charged with stirring while controlling the reaction temperature to be 120 to 130 ° C. 60.0 parts of water and 60.0 parts of an alkali adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) are added to the obtained crude polyether polyol containing a catalyst, and the mixture is subjected to an adsorption treatment, filtration and drying, followed by purification. Further, 0.9 part of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan) was added, and the mixture was dissolved by stirring. 3000 parts of ether diol (A'-1) was obtained. The polyether diol (A'-1) was an EO / PO block adduct of 1,2-propanediol, with a weight ratio of EO / PO of 80/20 and Mn = 4000.

Production Example 7
After charging 50.6 parts of 1,2-propanediol and 1.0 part of potassium hydroxide in a reaction vessel equipped with a stirrer and a temperature controller, PO1297.2 parts are added so that the reaction temperature becomes 100 to 110 ° C. It was thrown in continuously while controlling. Next, 1651.2 parts of EO were continuously charged under stirring while controlling the reaction temperature to be 120 to 130 ° C. 60.0 parts of water and 60.0 parts of an alkali adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) are added to the obtained crude polyether polyol containing a catalyst, and the mixture is subjected to an adsorption treatment, filtration and drying, followed by purification. Further, 0.9 part of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan) was added, and the mixture was dissolved by stirring. 3000 parts of ether diol (A'-2) was obtained. The polyether diol (A'-2) was an EO / PO block adduct of 1,2-propanediol, with a weight ratio of EO / PO of 55/45 and Mn = 4900.

Production Example 8
After charging 87.8 parts of 1,2-propanediol and 1.0 part of potassium hydroxide in a reaction vessel equipped with a stirrer and a temperature controller, PO2012.5 parts is added so that the reaction temperature becomes 100 to 110 ° C. It was thrown in continuously while controlling. Next, 898.7 parts of EO were continuously charged with stirring while controlling the reaction temperature to be 120 to 130 ° C. 60.0 parts of water and 60.0 parts of an alkali adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) are added to the obtained crude polyether polyol containing a catalyst, and the mixture is subjected to an adsorption treatment, filtration and drying, followed by purification. Further, 0.9 part of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan) was added, and the mixture was dissolved by stirring. 3000 parts of ether diol (A'-3) was obtained. The polyether diol (A'-3) was an EO / PO block adduct of 1,2-propanediol and had a weight ratio of EO / PO of 30/70 and Mn = 2000.

Example 1
In a reactor equipped with a stirrer, 50 parts of the above polyether diol (A-1) and poly (3-methylpentylene adipate) diol [“Kuraray polyol P-2010” manufactured by Kuraray Co., Ltd .: Mn = 2000] ( a2-1) 150 parts, 1,5-butanediol (a5) 0.95 parts, and IPDI (C-1) 37.49 parts were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 2. A 42% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 390 parts of ethyl acetate were added to make a uniform solution. Next, 195 parts of isopropyl alcohol is added and the mixture is stirred until uniform, 11.59 parts of isophoronediamine (B-1) and 0.52 parts of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-1) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-1) was 83,000.

Example 2
In a reactor equipped with a stirrer, 6 parts of the above polyether diol (A-1) and poly (3-methylpentylene adipate) diol [“Kuraray polyol P-2010” manufactured by Kuraray Co., Ltd .: Mn = 2000] ( a2-1) 181 parts, 1,4-butanediol (a5) 0.11 part, and IPDI (C-1) 41.79 parts were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 3. A 36% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 380 parts of ethyl acetate were added to make a uniform solution. Next, 191 parts of isopropyl alcohol is added and the mixture is stirred until uniform, 15.50 parts of isophoronediamine (B-1) and 0.70 parts of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-2) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-2) was 85,000.

Example 3
In a reactor equipped with a stirrer, 76 parts of the above polyether diol (A-1) and poly (3-methylpentylene adipate) diol [“Kuraray polyol P-2010” manufactured by Kuraray Co., Ltd .: Mn = 2000] ( a2-1) 124 parts, 1,4-butanediol (a5) 1.56 parts, and IPDI (C-1) 37.60 parts were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 2. A 42% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 391 parts of ethyl acetate was added to make a uniform solution. Next, 196 parts of isopropyl alcohol was added and stirred until uniform, 11.24 parts of isophoronediamine (B-1) and 0.81 part of monoethanolamine (D-1) were added, and the mixture was reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-3) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-3) was 85,000.

Example 4
In a reactor equipped with a stirrer, 60 parts of the above polyether diol (A-1) and polyoxypropylene glycol [Sannicks PP-2000 manufactured by Sanyo Chemical Industries, Ltd .: Mn = 2000] (a1-1). 140 parts, 1.92 parts of 1,4-butanediol (a5), and 59.48 parts of IPDI (C-1) were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 5.12% by weight. A urethane prepolymer was obtained. After cooling to 40 ° C., 448 parts of ethyl acetate was added to obtain a uniform solution. Next, 225 parts of isopropyl alcohol is added, and the mixture is stirred until uniform, 25.34 parts of isophoronediamine (B-1) and 1.82 parts of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-4) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-4) was 74,000.

Example 5
In a reactor equipped with a stirrer, 60 parts of the above polyether diol (A-2) and polyneopenthylene adipate diol [“San Ester 5620” manufactured by Sanyo Chemical Industries, Ltd .: Mn = 2000] (a2-2) 140 parts, 1.24 parts of 1,4-butanediol (a5) and 24.47 parts of IPDI (C-1) were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 0.37% by weight. A urethane prepolymer was obtained. After cooling to 40 ° C., 354 parts of ethyl acetate were added to make a uniform solution. Next, 177 parts of isopropyl alcohol is added, and the mixture is stirred until it becomes uniform. Then, 2.14 parts of isophoronediamine (B-1) and 0.08 part of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-5) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-5) was 90,000.

Example 6
A reactor equipped with a stirrer was charged with 200 parts of the above polyether diol (A-3) and 44.81 parts of IPDI (C-1), and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 3. 43% by weight of a urethane prepolymer was obtained. After cooling to 40 ° C., 406 parts of ethyl acetate were added to obtain a uniform solution. Next, 204 parts of isopropyl alcohol is added and the mixture is stirred until uniform, 16.06 parts of isophoronediamine (B-1) and 1.15 parts of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-6) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-6) was 78,000.

Example 7
In a reactor equipped with a stirrer, 60 parts of the above polyether diol (A-1) and polyneopenthylene adipate diol [“Sanester 5620” manufactured by Sanyo Chemical Industries, Ltd .: Mn = 2000] (a2-2) 140 parts, 1.18 parts of 1,4-butanediol (a5), and tolylene diisocyanate (a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate 80 36% by weight of 2,6-tolylene diisocyanate) (C-2) and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain a urethane prepolymer having an NCO content of 3.82% by weight. Was. After cooling to 40 ° C., 398 parts of ethyl acetate were added to make a uniform solution. Next, 199 parts of isopropyl alcohol is added and stirred until uniform, 17.90 parts of isophoronediamine (B-1) and 0.80 parts of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-7) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-7) was 79,000.

Example 8
In a reactor equipped with a stirrer, 32 parts of the above polyether diol (A-4) and poly (3-methylpentylene adipate) diol [“Kuraray polyol P-2010” manufactured by Kuraray Co., Ltd .: Mn = 2000] ( a2-1) 168 parts, 1,4-butanediol (a5) 0.79 part, and IPDI (C-1) 41.46 parts were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 2. A 63% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 395 parts of ethyl acetate were added to make a uniform solution. Next, 198 parts of isopropyl alcohol is added, and the mixture is stirred until it becomes uniform. Then, 12.78 parts of isophoronediamine (B-1) and 0.57 part of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-8) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-8) was 89,000.

Example 9
In a reactor equipped with a stirrer, 155 parts of the above polyether diol (A-5) and polyneopenthylene adipate diol [“San Ester 5620” manufactured by Sanyo Chemical Industries, Ltd .: Mn = 2000] (a2-2) 45 parts, 0.79 part of 1,4-butanediol (a5) and 41.46 parts of IPDI (C-1) were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 2.63% by weight. A urethane prepolymer was obtained. After cooling to 40 ° C., 395 parts of ethyl acetate were added to make a uniform solution. Next, 198 parts of isopropyl alcohol is added, and the mixture is stirred until it becomes uniform. Then, 12.78 parts of isophoronediamine (B-1) and 0.57 part of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-9) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-9) was 86,000.

Example 10
In a reactor equipped with a stirrer, 50 parts of the above polyether diol (A'-1) and poly (3-methylpentylene adipate) diol [“Kuraray polyol P-2010” manufactured by Kuraray Co., Ltd .: Mn = 2000] (A2-1) 150 parts, 1,4-butanediol (a5) 0.95 parts, and IPDI (C-1) 37.49 parts were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content 2 A .42% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 390 parts of ethyl acetate were added to make a uniform solution. Next, 195 parts of isopropyl alcohol is added and the mixture is stirred until uniform, 11.59 parts of isophoronediamine (B-1) and 0.52 parts of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-10) as a comparative solvent-based printing ink binder was obtained. Mw of the polyurethane urea resin (U-10) was 81,000.

Example 11
In a reactor equipped with a stirrer, 60 parts of the above polyether diol (A'-2), polyneopenthylene adipate diol [“San Ester 5620” manufactured by Sanyo Chemical Industries, Ltd .: Mn = 2000] (a2-2) ) 140 parts, 1,24 parts of 1,4-butanediol (a5) and 24.47 parts of IPDI (C-1) were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere, and the NCO content was 0.37% by weight. Was obtained. After cooling to 40 ° C., 354 parts of ethyl acetate were added to make a uniform solution. Next, 177 parts of isopropyl alcohol is added, and the mixture is stirred until it becomes uniform. Then, 2.14 parts of isophoronediamine (B-1) and 0.08 part of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-11) as a comparative solvent-based printing ink binder was obtained. Mw of the polyurethane urea resin (U-11) was 92,000.

Example 12
A reactor equipped with a stirrer was charged with 200 parts of the above polyether diol (A'-3) and 44.81 parts of IPDI (C-1), and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 3. 0.43% by weight of a urethane prepolymer was obtained. After cooling to 40 ° C., 406 parts of ethyl acetate were added to obtain a uniform solution. Next, 204 parts of isopropyl alcohol is added and the mixture is stirred until uniform, 16.06 parts of isophoronediamine (B-1) and 1.15 parts of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-12) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-12) was 79,000.

Example 13
In a reactor equipped with a stirrer, 50 parts of the above polyether diol (A-1) and poly (3-methylpentylene adipate) diol [“Kuraray polyol P-2010” manufactured by Kuraray Co., Ltd .: Mn = 2000] ( a2-1) 150 parts, trimethylolpropane 0.23 part, and IPDI (C-1) 34.48 parts were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain a urethane preform having an NCO content of 2.26% by weight. A polymer was obtained. After cooling to 40 ° C., 382 parts of ethyl acetate were added to make a uniform solution. Next, 191 parts of isopropyl alcohol is added, and the mixture is stirred until it becomes uniform. Then, 10.69 parts of isophoronediamine (B-1) and 0.48 part of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-13) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-13) was 113,000.

Example 14
In a reactor equipped with a stirrer, 50 parts of the above polyether diol (A-1) and poly (3-methylpentylene adipate) diol [“Kuraray polyol P-2010” manufactured by Kuraray Co., Ltd .: Mn = 2000] ( a2-1) 150 parts, 0.23 part of dimethylolpropionic acid (DMPA), and 34.16 parts of IPDI (C-1) were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere, and the NCO content was 2.24% by weight. % Of the urethane prepolymer was obtained. After cooling to 40 ° C., 381 parts of ethyl acetate were added to make a uniform solution. Next, 191 parts of isopropyl alcohol is added, and the mixture is stirred until it becomes uniform. Then, 10.59 parts of isophoronediamine (B-1) and 0.48 part of monoethanolamine (D-1) are added, and the mixture is reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-14) as a solvent-based printing ink binder of the present invention was obtained. Mw of the polyurethane urea resin (U-14) was 88,000.

Comparative Example 1
In a reactor equipped with a stirrer, 60 parts of polyoxyethylene glycol [“PEG-2000” manufactured by Sanyo Chemical Industries, Ltd .: Mn = 2000] (a1-2), poly (3-methylpentylene adipate) diol [ "Kuraray polyol P-2010" manufactured by Kuraray Co., Ltd .: Mn = 2000] (a2-1) 140 parts, 1,4-butanediol (a5) 0.52 parts, and IPDI (C-1) 40.32 parts And reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain a urethane prepolymer having an NCO content of 2.58% by weight. After cooling to 40 ° C., 394 parts of ethyl acetate were added to make a uniform solution. Next, 198 parts of isopropyl alcohol was added, and the mixture was stirred until it became uniform. Then, 12.44 parts of isophorone diamine (B-1) and 0.56 part of monoethanolamine (D-1) were added, and the mixture was reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U′-1) as a comparative solvent-based printing ink binder was obtained. Mw of the polyurethane urea resin (U′-1) was 88,000.

Comparative Example 2
In a reactor equipped with a stirrer, 4 parts of the above polyether diol (A-1) and poly (3-methylpentylene adipate) diol [“Kuraray polyol P-2010” manufactured by Kuraray Co., Ltd .: Mn = 2000] ( a2-1) 196 parts, 1,4-butanediol (a5) 0.61 part, and IPDI (C-1) 40.34 parts were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 2. A 58% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 395 parts of ethyl acetate were added to make a uniform solution. Next, 198 parts of isopropyl alcohol was added, and the mixture was stirred until it became uniform. Then, 12.45 parts of isophoronediamine (B-1) and 0.56 part of monoethanolamine (D-1) were added, and the mixture was reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U′-2) as a comparative solvent-based printing ink binder was obtained. Mw of the polyurethane urea resin (U′-2) was 79,000.

Comparative Example 3
In a reactor equipped with a stirrer, 86 parts of the above polyether diol (A-1) and poly (3-methylpentylene adipate) diol [“Kuraray polyol P-2010” manufactured by Kuraray Co., Ltd .: Mn = 2000] ( a2-1) 114 parts, 1,4-butanediol (a5) 2.52 parts, and IPDI (C-1) 40.73 parts were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 2. A 58% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 399 parts of ethyl acetate were added to make a uniform solution. Next, 200 parts of isopropyl alcohol was added, and the mixture was stirred until it became uniform. Then, 12.57 parts of isophoronediamine (B-1) and 0.56 part of monoethanolamine (D-1) were added, and the mixture was reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U′-3) as a comparative solvent-based printing ink binder was obtained. Mw of the polyurethane urea resin (U′-3) was 77,000.

Comparative Example 4
In a reactor equipped with a stirrer, 60 parts of polyoxypropylene glycol [“Sannicks PP-2000” manufactured by Sanyo Chemical Industries, Ltd .: Mn = 2000] (a1-1), poly (3-methylpentylene adipate) are used. Diol [Kuraray Co., Ltd. "Kuraray polyol P-2010": Mn = 2000] (a2-1) 140 parts, 1,4-butanediol (a5) 0.52 parts, and IPDI (C-1) 40. 32 parts were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain a urethane prepolymer having an NCO content of 2.58% by weight. After cooling to 40 ° C., 394 parts of ethyl acetate were added to make a uniform solution. Next, 198 parts of isopropyl alcohol was added, and the mixture was stirred until it became uniform. Then, 12.44 parts of isophorone diamine (B-1) and 0.56 part of monoethanolamine (D-1) were added, and the mixture was reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U′-4) as a comparative solvent-based printing ink binder was obtained. Mw of the polyurethane urea resin (U′-4) was 82,000.

Examples 15 to 28 and Comparative Examples 5 to 8
Using the solutions of the polyurethane urea resins obtained in Examples 1 to 14 and Comparative Examples 1 to 4, solvent-based printing inks of Examples 15 to 28 and Comparative Examples 5 to 8 were prepared according to the following formulations.

[Preparation of blue ink]
A mixture of 100 parts of a polyurethane urea resin solution, 30 parts of a pigment (β-type phthalocyanine blue), 30 parts of isopropyl alcohol, 70 parts of ethyl acetate and 150 parts of glass beads was applied for 1 hour with a paint conditioner (manufactured by Red Devil Co.). After kneading, the glass beads were removed by filtration to obtain a blue ink.

Using the obtained solvent-based printing ink, the following performance tests were performed to determine the results of the oxyethylene group content in the polyurethane urea resin (U), the urethane group concentration and the urea group concentration in the polyurethane urea resin (U). Are shown in Table 1 together with the total value of

[Production of test piece]
Surface-treated polypropylene film (OPP) [Toyobo Co., Ltd. “Pyrene P-2161” (thickness 30 μm)], surface-treated polyester film (PET) [Toyobo Co., Ltd. “Espet E-5102” (thickness 12 μm)] A solvent-based printing ink is applied to a surface-treated nylon film [Toyobo Co., Ltd. “Harden N-1130” (thickness: 15 μm)] with a bar coater so as to have a solid content of 2 to 3 μm. After drying for a minute, a test piece was prepared.
[Adhesion test method]
Adhere cellophane tape (Nichiban, 12 mm width) to the coating surface of each test piece, and observe the condition of the coating surface when one end of this cellophane tape is rapidly peeled off at right angles to the coating surface, and the ink is peeled off. The evaluation was made based on the area% that was not used.

[Test method for boil resistance]
An adhesive for dry lamination [base agent: Polybond AY-651A, curing agent: Polybond AY-651C (manufactured by Sanyo Chemical Industries)] is applied to the coated surface of the test piece using the surface-treated nylon film, and a laminator is used. The resultant was bonded to LLDPE (manufactured by Mitsui Chemicals Tosello Co.) and aged at 40 ° C. for 48 hours. Thereafter, a bag is formed by heat sealing with the LLDPE surface inside, a mixture of vinegar / salad oil / meat sauce = 1/1/1 (weight ratio) is enclosed as the contents, and boiled at 98 ° C. for 1 hour. Was observed and evaluated according to the following criteria.
<Evaluation criteria>
A: No change in appearance.
：: Lamination of the laminate occurred in only a part.
Δ: Laminate partially floated.
×: The laminate is peeled over the entire surface.

[Resolution test method]
After printing 100 m of solvent-based printing ink on an OPP film at a speed of 30 m / min using a gravure plate having a depth of 35 μm with a plate jam gravure printing test machine (TS-1 type printing machine; manufactured by Higashiya Ironworks Co., Ltd.) Table 1 shows the remaining amount (volume%) of the ink in the cell after the excess ink adhering to the gravure plate was lightly washed off with a mixed solvent of isopropyl alcohol and ethyl acetate (weight ratio 3: 7).

[Test method for ink stability]
After adding 5% by weight of water to the prepared ink and stirring, the mixture was allowed to stand at 25 ° C. for 1 week, and the viscosity immediately after preparation of the ink (v0) and the viscosity after standing at 25 ° C. for 1 week (v1) were added. ) Is measured with Zahn Cup # 4 (25 ° C.). Ink stability is expressed in terms of increased viscosity (seconds) calculated from (v1)-(v0) and is shown in Table 1.
In addition, in Table 1, "sedimentation" means that the pigment was partially aggregated and settled at the bottom of the container, and the viscosity could not be measured.

Since the binder of the present invention is excellent in adhesiveness, resolubility in a solvent, ink stability, and boil resistance, a binder for a special gravure ink for various plastic films (polyester film, nylon film, polypropylene film, cellophane film, etc.). It is particularly suitable as Further, the binder of the present invention is useful not only for the above-mentioned applications but also as a binder for flexographic solvent-based printing inks, a binder for paints, a coating agent for adhesives, paper and the like.

Claims (7)

A solvent-based printing ink binder containing a polyurethane urea resin (U),
The polyurethane urea resin (U) is a polyether diol (A) which is a random addition product of a compound (F) having two active hydrogens and an alkylene oxide consisting of only ethylene oxide and 1,2-propylene oxide added at random. A diol (a) other than the polyether diol (A), a diamine (B), a diisocyanate (C) and a reaction terminator (D) alone as constituent monomers;
The compound (F) having two active hydrogens is water, ethylene glycol or 1,2-propanediol,
The diol (a) other than the polyether diol (A) includes a polyether diol (a1) other than the polyether diol (A), a polyester diol (a2), a polylactone diol (a3), a polycarbonate diol (a4) and At least one selected from the group consisting of diols (a5) having a number average molecular weight of less than 500;
A solvent-based printing ink binder having an oxyethylene group content of 2 to 24% by weight based on the polyurethane urea resin (U). A solvent-based printing ink binder containing a polyurethane urea resin (U),
The polyurethane urea resin (U) is a polyether diol (A) which is a random addition product of a compound (F) having two active hydrogens and an alkylene oxide consisting of only ethylene oxide and 1,2-propylene oxide added at random. , Diamine (B), diisocyanate (C) and reaction terminator (D) only as constituent monomers,
The compound (F) having two active hydrogens is water, ethylene glycol or 1,2-propanediol,
A solvent-based printing ink binder having an oxyethylene group content of 2 to 24% by weight based on the polyurethane urea resin (U). The solvent-based printing ink binder according to claim 1, wherein the content of the oxyethylene group based on the polyurethane urea resin (U) is 5 to 18% by weight. The solvent-based printing ink binder according to claim 1 or 3 , wherein the polyether diol (a1), the polyester diol (a2), the polylactone diol (a3), and the polycarbonate diol (a4) have a branched alkyl group. The solvent-based printing ink according to any one of claims 1 to 4 , wherein the total value of the urethane group concentration and the urea group concentration in the polyurethane urea resin (U) is 0.8 to 2.0 mmol / g. For binders. A solvent-based printing ink comprising the binder for a solvent-based printing ink according to any one of claims 1 to 5 , a pigment, and a solvent. The solvent-based printing ink according to claim 6 , wherein the solvent contains an alcohol.