WO2017073332A1

WO2017073332A1 - Binder for solvent-based printing ink, and solvent-based printing ink including same

Info

Publication number: WO2017073332A1
Application number: PCT/JP2016/080272
Authority: WO
Inventors: 正考藤岡
Original assignee: 三洋化成工業株式会社
Priority date: 2015-10-30
Filing date: 2016-10-12
Publication date: 2017-05-04
Also published as: CN107949611A; JPWO2017073332A1; JP6665198B2

Abstract

Provided is a binder for solvent-based printing inks which are extensively usable on various plastic films, can be highly easily redissolved in solvents, and rarely cause printing plate clogging during printing, which have excellent ink stability even in case where water has come thereinto, and which have excellent boiling resistance. The binder for solvent-based printing inks according to the present invention comprises a polyurethane-urea resin (U), wherein the polyurethane-urea resin (U) is a resin obtained from, as essential constituent monomers, a polyether diol (A) that is an adduct obtained by causing alkylene oxides comprising ethylene oxide and 1,2-propylene oxide to add to a compound (F) having two active hydrogen atoms, a diamine (B), and a diisocyanate (C), the polyurethane-urea resin (U) having a content of oxyethylene groups of 2-24 wt%.

Description

Binder for solvent-based printing ink and solvent-based printing ink using the same

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

Conventionally, printing inks that use polyurethane resin as a binder have excellent adhesive strength for polyester films and nylon films alone, but sufficient adhesion to polyolefin films such as polyethylene films and polypropylene films, which are general purpose films. Printing ink with chlorinated polyolefin as a binder shows good adhesion to polyolefin film, but there is not enough adhesion to polyester film or nylon film. There is a problem of being restricted. For the purpose of general-purpose use in various plastic films, it has been proposed to use a mixture of polyurethane resin and chlorinated polyolefin (for example, see Patent Document 1).

However, in recent years, efforts to address environmental issues have become important, and it is strongly desired to suppress the generation of harmful substances in the disposal of used products. Chlorinated polyolefins contain chlorine. Therefore, there is a problem that harmful substances are generated during incineration and there is a risk of polluting 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, the revision of the Occupational Safety and Health Act has tightened the environmental concentration regulations for toluene, increasing the demand for solvent-based printing inks that do not contain toluene. In recent years, there has been a demand for alcohol-based printing inks that are more suitable for the environment. Is increasing. Polyurethane resins containing polypropylene glycol using only solvents such as MEK and ethyl acetate without using toluene have been proposed (see, for example, Patent Document 2), but printing with insufficient ink redissolvability Plate clogging sometimes occurs, and inks using alcohol that contains a lot of water have problems such as poor stability and poor boil resistance.

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

The problems to be solved by the present invention are excellent in versatility that can be used for various plastic films, excellent in re-solubility in solvents, very little clogging during printing, and ink stability even when moisture is mixed It is to provide a binder for solvent-based printing inks that is excellent in resistance and boil resistance.

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

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

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

Examples of the polyether diol (A) compound (F) having two active hydrogens include water; 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), 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 alcohols having 6 to 10 carbon atoms [1,4-bis (hydroxymethyl) cyclohexane and 2,2-bis (4-hydroxycyclohexyl) propane, etc.]; aromatic ring having 8 to 20 carbon atoms Divalent alcohol [m- or p-xylylene glycol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene, bisphenols (such as bisphenol A, bisphenol S and bisphenol F), dihydroxynaphthalene], and 1 carbon atom To 12 monoalkylamines [monomethylamine, monoethylamine, monobutylamine, etc.] and the like.

AO added to the compound (F) having two active hydrogens contains EO and PO.
AO added to compound (F) having two active hydrogens includes 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran in addition to EO and PO. Other AO such as 3-methyltetrahydrofuran, styrene oxide and α-olefin oxide may be contained. 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 of EO to 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.
EO and PO addition types include random and block, and random is preferable from the viewpoint of boil resistance.

The distinction between random and block can be judged by C-NMR measurement when the copolymerization adduct is EO and PO. Of the integral values (X) of all peaks derived from EO (60.0-62.0, 68.0-68.8, 70.0-71.0 ppm), EO adjacent to the secondary carbon of PO (Z) = (Y) / (X) × 100, where (Z) is the ratio of the integral value (Y) of peaks derived from (68.0 to 68.8 ppm). It can be said that the larger one has a higher proportion of random copolymerization.
For example, when the ratio of addition mole of EO / PO is 50/50 and the number average molecular weight of the copolymerization 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 The random copolymerization is 20 to 50, and the block copolymer is 1 to 5. When the EO / PO addition mole ratio 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 in which only EO and PO are added to water, an adduct in which only EO and PO are added to 1,2-propanediol, or EO to ethylene glycol. And adducts with only PO added.

The polyurethane urea resin (U) is further composed of a polyether diol (a1) other than the polyether diol (A), a polyester diol (a2), a polylactone diol (a3) and a polycarbonate diol (a4) as a constituent monomer. It is preferable from a viewpoint of re-solubility and adhesiveness to contain the at least 1 sort (s) of diol (a) chosen from the group which consists of. 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 viewpoints of resolubility and adhesion.
In addition, 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 measurement conditions for Mn are as follows.
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation)”
Sample solution: 0.25 wt% tetrahydrofuran solution solution injection amount: 10 μL
Flow rate: 0.6 mL / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polyethylene glycol

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

Examples of the polyether diol (a1) include a diol (a5) having an Mn of less than 500 and an AO adduct having 2 to 12 carbon atoms to a monoalkylamine as shown below. 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- Examples include olefin oxide. One type of these AOs having 2 to 12 carbon atoms may be added to the monoalkylamine, or a plurality of types may be added to the monoalkylamine.
The polyether diol (a1) does not include the polyether diol (A).

Examples of the diol (a5) having a 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), 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.]; divalent alcohols 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- Silylene glycol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene, bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.) C2-C12 AO adducts, dihydroxynaphthalene AO adducts and bis ( 2-hydroxyethyl) terephthalate and the like];

Of the polyether diol (a1), those having a branched alkyl chain are preferred from the viewpoint of resolubility. That is, a raw material using a diol having a branched alkyl chain among diols having an Mn of less than 500, or PO, 1,2-, 2,3- or 1,3-butylene oxide and 3- Those using methyltetrahydrofuran or the like. Further preferred is an AO adduct obtained by adding the above-mentioned AO of an aliphatic dihydric alcohol having a branched alkyl chain, and particularly preferred is polyoxypropylene glycol.

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

As the polyester diol (a2), a diol (a5) having an Mn of less than 500 is condensed with a dicarboxylic acid or an ester-forming derivative thereof [an acid anhydride, a lower (1 to 4 carbon atoms) alkyl ester, an acid halide, etc.]. What is obtained is mentioned.

Dicarboxylic acids or ester-forming derivatives thereof 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), carbon number 8-12 aromatic dicarboxylic acids (such as terephthalic acid and isophthalic acid) and ester-forming derivatives thereof [acid anhydrides, lower alkyl esters (such as dimethyl ester and diethyl ester), acid halides (such as acid chloride)], etc. Is mentioned. Dicarboxylic acid may be used individually by 1 type, or may use 2 or more types together.

Specific examples of the polyester diol (a2) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentylene adipate diol, polyethylene propylene adipate diol, 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.

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

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

As the polylactone diol (a3), a lactone monomer (γ-butyrolactone, γ-valerolactone, ε-caprolactone and a mixture of two or more thereof) is opened by using a diol (a5) having an Mn of less than 500 as an initiator. Polymerized products and the like can be mentioned. Specific examples of the polylactone diol include polybutyrolactone diol, polyvalerolactone diol, and polycaprolactone diol.

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

The polycarbonate diol (a4) includes a diol (a5) having an Mn of less than 500, a low-molecular carbonate compound (for example, an alkylene carbonate having an alkyl group having 1 to 6 carbon atoms and an alkylene group having 2 to 6 carbon atoms) And a polycarbonate diol produced by condensation with a dealcoholization reaction with 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). And a diol obtained by condensing a diol with a dialkyl carbonate while causing a dealcoholization reaction).

The polyurethane urea resin (U) contained in the solvent-based printing ink binder of the present invention may contain one type of polycarbonate diol (a4) as a constituent monomer, and may contain a plurality of types 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 the diol (a5) having an Mn of less than 500 described above as a constituent monomer, in addition to the polyether diol (A).
When manufacturing a polyurethane urea resin (U), the urethane group density | concentration and urea group density | concentration in a polyurethane urea resin (U) can be adjusted by using diol (a5) whose Mn is less than 500. The content of the diol (a5) having an 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 or derivatives thereof (dibasic acid dihydrazide such as adipic acid dihydrazide). Diamine (B) may be contained alone or in combination of two or more.

Examples of the diamine having 2 to 12 carbon atoms include ethylene diamine, propylene diamine, hexamethylene diamine, isophorone diamine, toluene diamine and piperazine.
Of these, isophoronediamine is preferred from the viewpoint of resolubility.

Also, when the polyurethane urea resin (U) contains a diol (a5) having an Mn of less than 500, that is, when a diamine (B) and a 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 re-solubility and solvent resistance.

Examples of the diisocyanate (C) include aliphatic diisocyanates (C1) having 4 to 22 carbon atoms, alicyclic diisocyanates (C2) having 8 to 18 carbon atoms, aromatic diisocyanates (C3) having 8 to 26 carbon atoms, and 10 carbon atoms. To 18 araliphatic diisocyanates (C4) and the like.

Examples of the aliphatic diisocyanate (C1) 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 include isocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, and bis (2-isocyanatoethyl) carbonate.

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-isocyanato). Ethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

Examples of the aromatic diisocyanate (C3) having 8 to 26 carbon atoms 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 Natodiphenylmethane, 1,5-naphthylene diisocyanate and m- or p-isocyanatophenylsulfonyl isocyanate.

Examples of the C10-18 araliphatic diisocyanate (C4) include m- or p-xylylene diisocyanate and α, α, α ', α'-tetramethylxylylene diisocyanate.

Among these, the diisocyanate (C) is preferably an alicyclic diisocyanate (C2) having 8 to 18 carbon atoms from the viewpoint of adhesion, and more preferably from the viewpoint of re-solubility of the polyurethane urea resin (U). Is IPDI.
Diisocyanate (C) may be contained singly or in combination of two or more.

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

Examples of the reaction terminator (D) include 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 ( n-butylamine and di-n-butylamine), mono- or dialkanolamines having 2 to 6 carbon atoms (monoethanolamine, diethanolamine, propanolamine, etc.)] and the like. Of these, preferred are mono- or dialkanolamines having 2 to 6 carbon atoms. A reaction terminator (D) may be used individually by 1 type, or may use 2 or more types together.

The content of oxyethylene groups in the binder for solvent-based printing inks of the present invention is 2 to 24% by weight based on the weight of the polyurethaneurea resin (U). If the oxyethylene group content is less than 2% by weight, the ink stability deteriorates, and if it exceeds 24% by weight, the boil resistance becomes poor. The oxyethylene group content is preferably 3 to 22% by weight, more preferably 4 to 20% by weight, still more preferably 5 to 18% by weight, and still more preferably 10 to 16 parts by weight. .
In particular, when the oxyethylene group content 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 oxyethylene groups 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 integrated amount derived from oxyethylene groups near the chemical shift of 3.5 ppm and the integrated amount of hydrogen derived from other constituents.
The oxyethylene group in the binder for solvent-based printing inks of the present invention includes polyether diol (A), which is a constituent monomer of the polyurethane urea resin (U), polyether diol (a1), polyester diol (a2), At least one diol (a) selected from the group consisting of polylactone diol (a3) and polycarbonate diol (a4) is derived from diol (a5) having an Mn of less than 500, but is derived from other compounds. May be.

The polyurethane urea resin (U) has 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 stopper (D) is preferably 0.01 to 1.0% by weight, more preferably 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 0.8 to 2.0 mmol /% from the viewpoint of resolubility 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 the nitrogen atom content determined by a nitrogen analyzer [ANTEK7000 (manufactured by Antec)]. It can be quantified by ¹ H-NMR. ^{The 1} H-NMR measurement is carried out by the method described in “Structural study of polyurethane resin by NMR: Takeda Laboratory Report 34 (2), 224-323 (1975)”. That is, when ¹ H-NMR is measured and aliphatic is used, the ratio of the urea group derived from the urea group derived from the urea group near the chemical shift of 6 ppm to the urea group derived from the ratio of the integral amount of hydrogen derived from the urethane group near the chemical shift of 7 ppm. The weight ratio of urethane groups is measured, and the urethane group concentration and urea group concentration are calculated from the weight ratio and the nitrogen atom content. When aromatic isocyanate is used, the weight ratio of urea group and urethane group is calculated from the ratio of the integral amount of hydrogen derived from urea groups near the chemical shift of 8 ppm and the integral amount of hydrogen derived from urethane groups near the chemical shift of 9 ppm, The urethane group concentration and urea group concentration are calculated from the weight ratio and the nitrogen atom content.

The polyurethane urea resin (U) is at least selected from the group consisting of a tri- to tetra-functional polyhydric alcohol, a tri- to 4-functional polyisocyanate, and a dihydroxy carboxylic acid from the viewpoint of resolubility. One kind of compound (E) may be contained in a very small amount. The polyurethane urea resin (U) may not contain any of tri- to tetra-functional polyhydric alcohol, tri- to tetra-functional polyisocyanate, and dihydroxycarboxylic acid.
When the polyurethane urea resin (U) contains the compound (E), the content of the compound (E) is preferably 0.4% by weight or less based on the weight of the urethane resin (U). The content is more preferably not more than wt%, and further preferably 0.0001 to 0.1 wt%.
When the polyurethane urea resin (U) contains a tri- to tetra-functional polyhydric alcohol, the tri- to 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 the 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 once. Alternatively, a multistage process in which the reaction is performed stepwise [for example, after reacting polyether diol (A) with diisocyanate (C) to form an isocyanate group-terminated prepolymer, diamine (B) and, if necessary, reaction stopper (D) are added. Any of the above methods may be used. However, from the viewpoint of adhesiveness, after forming an isocyanate group-terminated prepolymer, a diamine having 2 to 12 carbon atoms is used as the diamine (B). Polyurea is used in such a way that the total value of the amino groups of the amine is excessive relative to the equivalent of the isocyanate groups it has. A method of introducing an amino group at an end of N'urea molecular chain.

In the production of the polyurethane urea resin (U), the equivalent ratio of the isocyanate group of the diisocyanate (C) and the active hydrogen-containing group of the polyether diol (A), the diamine (B) and the reaction terminator (D) used as necessary ( The isocyanate group: active hydrogen-containing group) is preferably 0.7: 1 to 0.99: 1, more preferably 0.8: 1 to 0.98: 1.

The reaction temperature of the polyether diol (A) and the diisocyanate (C) is preferably 20 to 140 ° C, more preferably 40 to 120 ° C. However, the reaction temperature when the diamine (B) is reacted is preferably 100 ° C. or lower, more preferably 0 to 80 ° C.

In the case of the above reaction, a catalyst used in the urethane reaction, if necessary, to promote the reaction [amine catalyst (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), tin-based catalyst (dibutyltin dilaurate, dioctyltin dilaurate and octylic acid) Tin, 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, and preferably 0.001 to 0.1% by weight, based on the total weight of the compounds constituting the constituent monomer of the polyurethane urea resin (U). More preferred.

The reaction may be performed in an organic solvent, or an organic solvent may be added during or after the reaction. Examples of organic solvents 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). Ether), aliphatic hydrocarbon solvents (n-hexane, n-heptane, cyclohexane, etc.) and alcohol solvents (ethanol, methanol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc.).

Of these, from the viewpoint of re-solubility of the polyurethane urea resin (U), ethyl acetate, butyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, n-propyl alcohol and isopropyl alcohol are more preferable. Are ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and isopropyl alcohol.
An organic solvent may be used individually by 1 type, or may use 2 or more types together.

The weight average molecular weight (hereinafter abbreviated as Mw) of the polyurethane urea resin (U) in the present invention is preferably 50,000 to 200,000 from the viewpoint of the resin physical properties, re-solubility 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.
Equipment: “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 injection amount: 100 μL
Flow rate: 1 mL / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene

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

The solvent-based printing ink of the present invention contains the binder for a solvent-based printing ink of the present invention, a pigment and a solvent as essential components. There is no restriction | limiting in particular as a pigment, The inorganic pigment, organic pigment, etc. which are used for normal solvent type printing ink can be used.
As the solvent, the organic solvent used in the above reaction can be used. From the viewpoint of re-solubility of the polyurethane urea resin (U), ethyl acetate, butyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, n- Propyl alcohol and isopropyl alcohol are more preferable, and ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and isopropyl alcohol are more preferable. Particularly preferred is a mixed solvent containing alcohol, such as a mixed solvent of ethyl acetate and isopropyl alcohol, a mixed solvent of methyl ethyl ketone and isopropyl alcohol, and the like.

If necessary, other resins usually used in solvent-based printing inks and additives such as pigment dispersants can be blended. Other resins and additives may be used alone or in combination of two or more.

Examples of other resins include polyamide resin, nitrocellulose, acrylic resin, vinyl acetate resin, styrene maleic acid copolymer resin, epoxy resin, and rosin resin. The addition amount of these other resins is preferably 30% by weight or less, more preferably 20% by weight or less in the solvent-based printing ink. Moreover, it is preferable that it is 0.5 weight% or more.

The method for producing the solvent-based printing ink of the present invention is not particularly limited, and the solvent-based printing ink can be produced using a known method or the like, for example, an ordinary ink production apparatus such as a three-roll, ball mill, or 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 (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 comprising the binder for the solvent-based printing ink of the present invention may be used as a one-component printing ink. For example, it is used as a two-component printing ink in combination with a polyisocyanate-based curing agent. You can also. The polyisocyanate curing agent in this case is, for example, an adduct formed from 1 mol of trimethylolpropane and 3 mol of 1,6-hexamethylene diisocyanate, tolylene diisocyanate, or IPDI; 1,6-hexamethylene diisocyanate Isocyanurate group-containing trimers synthesized by cyclic trimerization of isocyanate groups of cyanate or IPDI; partial burette reactants derived from 1 mole of water and 3 moles of 1,6-hexamethylene diisocyanate and their Two or more mixtures are preferred. When used as a two-component printing ink, the amount of polyisocyanate 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 a plastic film.

The binder for solvent-based printing inks of the present invention has excellent adhesiveness to various plastic films such as polyester, nylon and polyolefin, and can be used universally as a binder for solvent-based printing inks for various plastic films.
The solvent-based 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 films obtained by performing aluminum deposition on these films. It can use suitably for printing of various plastic films, such as.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In the following, “part” means part by weight.

Production Example 1
After charging 17.9 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 was 2380.3 parts of EO and 540.8 parts of PO under stirring. It was continuously added while being controlled to 100 to 110 ° C. Purification by adding 60.0 parts of water and 60.0 parts of an alkaline adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) to the crude polyether polyol containing the catalyst, followed by adsorption treatment, filtration and drying. Further, 0.9 parts of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan Ltd.) was added and dissolved by stirring to dissolve poly 3000 parts of ether diol (A-1) were obtained. The polyether diol (A-1) was an EO / PO random adduct of 1,2-propanediol, and had an EO / PO weight ratio of 80/20 and Mn = 4000.

Production Example 2
A reactor equipped with a stirrer and a temperature controller was charged with 50.6 parts of 1,2-propanediol and 1.0 part of potassium hydroxide, and then the reaction temperature was adjusted to 1651.2 parts of EO and 1297.2 parts of PO under stirring. It was continuously added while being controlled to 100 to 110 ° C. Purification by adding 60.0 parts of water and 60.0 parts of an alkaline adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) to the crude polyether polyol containing the catalyst, followed by adsorption treatment, filtration and drying. Further, 0.9 parts of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan Ltd.) was added and dissolved by stirring to dissolve poly 3000 parts of ether diol (A-2) were obtained. The polyether diol (A-2) was an EO / PO random adduct of 1,2-propanediol, and the EO / PO weight ratio was 55/45 and Mn = 4900.

Production Example 3
A reactor equipped with a stirrer and a temperature controller was charged with 87.8 parts of 1,2-propanediol and 1.0 part of potassium hydroxide, and then the reaction temperature was adjusted to 898.7 parts of EO and 2.51.5 parts of PO under stirring. It was continuously added while being controlled to 100 to 110 ° C. Purification by adding 60.0 parts of water and 60.0 parts of an alkaline adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) to the crude polyether polyol containing the catalyst, followed by adsorption treatment, filtration and drying. Further, 0.9 parts of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan Ltd.) was added and dissolved by stirring to dissolve poly 3000 parts of ether diol (A-3) were obtained. The polyether diol (A-3) was an EO / PO random adduct of 1,2-propanediol, and the weight ratio of EO / PO was 30/70 and Mn = 2000.

Production Example 4
After charging 144.3 parts of 1,4-butanediol and 1.0 part of potassium hydroxide into a reaction vessel equipped with a stirrer and a temperature controller, the reaction temperature was 1202.5 parts of EO and 1582.1 parts of PO under stirring. It was continuously added while being controlled to 100 to 110 ° C. Purification by adding 60.0 parts of water and 60.0 parts of an alkaline adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) to the crude polyether polyol containing the catalyst, followed by adsorption treatment, filtration and drying. Further, 0.9 parts of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan Ltd.) was added and dissolved by stirring to dissolve poly 3000 parts of ether diol (A-4) were obtained. The polyether diol (A-4) was an EO / PO random adduct of 1,4-butanediol, with an EO / PO weight ratio of 50/50 and Mn = 2000.

Production Example 5
After charging 931.3 parts “New Pole BP-3P” (manufactured by Sanyo Kasei Kogyo Co., Ltd.), which is a PO adduct of bisphenol A, and 1.0 part of potassium hydroxide in a reaction vessel equipped with a stirrer and a temperature controller, Under stirring, EO1110.3 parts and PO1460.8 parts were continuously added while controlling the reaction temperature to be 100 to 110 ° C. Purification by adding 60.0 parts of water and 60.0 parts of an alkaline adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) to the crude polyether polyol containing the catalyst, followed by adsorption treatment, filtration and drying. Further, 0.9 parts of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan Ltd.) was added and dissolved by stirring to dissolve poly 3000 parts of ether diol (A-5) were obtained. Polyether diol (A-5) was an EO / PO random adduct of bisphenol A, and the weight ratio of EO / PO was 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 control device, 540.8 parts of PO are added so that the reaction temperature becomes 100 to 110 ° C. It was continuously fed while being controlled. Next, 2380.3 parts of EO was continuously added under stirring while controlling the reaction temperature to be 120 to 130 ° C. Purification by adding 60.0 parts of water and 60.0 parts of an alkaline adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) to the crude polyether polyol containing the catalyst, followed by adsorption treatment, filtration and drying. Further, 0.9 parts of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan Ltd.) was added and dissolved by stirring to dissolve poly 3000 parts of ether diol (A′-1) were obtained. Polyetherdiol (A′-1) was an EO / PO block adduct of 1,2-propanediol, and had an EO / PO weight ratio 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 control device, PO1297.2 parts are added so that the reaction temperature becomes 100 to 110 ° C. It was continuously fed while being controlled. Next, 1651.2 parts of EO was continuously added under stirring while controlling the reaction temperature to be 120 to 130 ° C. Purification by adding 60.0 parts of water and 60.0 parts of an alkaline adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) to the crude polyether polyol containing the catalyst, followed by adsorption treatment, filtration and drying. Further, 0.9 parts of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan Ltd.) was added and dissolved by stirring to dissolve poly 3000 parts of ether diol (A′-2) were obtained. The polyether diol (A′-2) was an EO / PO block adduct of 1,2-propanediol, and had an EO / PO weight ratio 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 into a reaction vessel equipped with a stirrer and a temperature control device, PO2012.5 parts are added so that the reaction temperature becomes 100 to 110 ° C. It was continuously fed while being controlled. Next, 898.7 parts of EO was continuously added under stirring while controlling the reaction temperature to be 120 to 130 ° C. Purification by adding 60.0 parts of water and 60.0 parts of an alkaline adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) to the crude polyether polyol containing the catalyst, followed by adsorption treatment, filtration and drying. Further, 0.9 parts of 6-methylheptyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1135” manufactured by BASF Japan Ltd.) was added and dissolved by stirring to dissolve poly 3000 parts of ether diol (A′-3) were obtained. The polyether diol (A′-3) was an EO / PO block adduct of 1,2-propanediol, and the weight ratio of EO / PO was 30/70 and Mn = 2000.

Example 1
In a reactor equipped with a stirrer, 50 parts of the above polyether diol (A-1), 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 part, and IPDI (C-1) 37.49 parts were allowed to react at 110 ° C. for 10 hours in a nitrogen atmosphere, and the NCO content was 2. A 42% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 390 parts of ethyl acetate was added to make a uniform solution. Next, add 195 parts of isopropyl alcohol and stir until uniform, then add 11.59 parts of isophoronediamine (B-1) and 0.52 part of monoethanolamine (D-1) and react at 40 ° C. for 1 hour. Thus, a solution of polyurethane urea resin (U-1) which is a binder for solvent-based printing ink of the present invention was obtained. The polyurethane urea resin (U-1) had an Mw of 83,000.

Example 2
In a reactor equipped with a stirrer, 6 parts of the above polyether diol (A-1), 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 allowed to react at 110 ° C. for 10 hours in a nitrogen atmosphere to give an NCO content of 3. A 36% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 380 parts of ethyl acetate was added to make a uniform solution. Next, after adding 191 parts of isopropyl alcohol and stirring until homogeneous, 15.50 parts of isophoronediamine (B-1) and 0.70 part of monoethanolamine (D-1) are added and reacted at 40 ° C. for 1 hour. Thus, a solution of polyurethane urea resin (U-2) which is a binder for solvent-based printing ink of the present invention was obtained. The polyurethane urea resin (U-2) had an Mw of 85,000.

Example 3
In a reactor equipped with a stirrer, 76 parts of the above polyether diol (A-1), 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 allowed to react at 110 ° C. for 10 hours in a nitrogen atmosphere to give 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 obtain a uniform solution. Next, 196 parts of isopropyl alcohol was added and stirred until uniform, and then 11.24 parts of isophoronediamine (B-1) and 0.81 part of monoethanolamine (D-1) were added and reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-3) which is a binder for solvent-based printing ink of the present invention was obtained. The polyurethane urea resin (U-3) had an Mw of 85,000.

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

Example 5
In a reactor equipped with a stirrer, 60 parts of the above polyether diol (A-2), polyneopentylene adipate diol [“Sanester 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. The NCO content was 0.37% by weight. A urethane prepolymer was obtained. After cooling to 40 ° C., 354 parts of ethyl acetate was added to make a uniform solution. Next, 177 parts of isopropyl alcohol was added and stirred until uniform, and then 2.14 parts of isophoronediamine (B-1) and 0.08 part of monoethanolamine (D-1) were added and reacted at 40 ° C. for 1 hour. Thus, a solution of polyurethane urea resin (U-5) which is a binder for solvent-based printing ink of the present invention was obtained. The Mw of the polyurethane urea resin (U-5) was 90,000.

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

Example 7
In a reactor equipped with a stirrer, 60 parts of the above polyether diol (A-1), polyneopentylene adipate diol [“Sanester 5620” manufactured by Sanyo Chemical Industries, Ltd .: Mn = 2000] (a2-2) 140 parts, 1,4-butanediol (a5) 1.18 parts, and tolylene diisocyanate (a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate 80 (% By weight, 2,6-tolylene diisocyanate 20% by weight) (C-2) 36.25 parts and reacted at 110 ° C. for 10 hours in a nitrogen atmosphere to obtain a urethane prepolymer having an NCO content of 3.82% by weight. It was. After cooling to 40 ° C., 398 parts of ethyl acetate was added to make a uniform solution. Next, add 199 parts of isopropyl alcohol and stir until homogeneous, then add 17.90 parts of isophoronediamine (B-1) and 0.80 part of monoethanolamine (D-1) and react at 40 ° C. for 1 hour. Thus, a solution of polyurethane urea resin (U-7) which is a binder for solvent-based printing ink of the present invention was obtained. The polyurethane urea resin (U-7) had an Mw of 79,000.

Example 8
In a reactor equipped with a stirrer, 32 parts of the above polyether diol (A-4), 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 allowed to react at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an NCO content of 2. 63% by weight of urethane prepolymer was obtained. After cooling to 40 ° C., 395 parts of ethyl acetate was added to make a uniform solution. Next, add 198 parts of isopropyl alcohol and stir until homogeneous, then add 12.78 parts of isophoronediamine (B-1) and 0.57 parts of monoethanolamine (D-1) and react at 40 ° C. for 1 hour. Thus, a solution of polyurethane urea resin (U-8) which is a binder for solvent-based printing ink of the present invention was obtained. The polyurethane urea resin (U-8) had an Mw of 89,000.

Example 9
In a reactor equipped with a stirrer, 155 parts of the above polyether diol (A-5), polyneopentylene adipate diol [“San Ester 5620” manufactured by Sanyo Chemical Industries, Ltd .: Mn = 2000] (a2-2) 45 parts, 0.74 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. The NCO content was 2.63% by weight. A urethane prepolymer was obtained. After cooling to 40 ° C., 395 parts of ethyl acetate was added to make a uniform solution. Next, add 198 parts of isopropyl alcohol and stir until homogeneous, then add 12.78 parts of isophoronediamine (B-1) and 0.57 parts of monoethanolamine (D-1) and react at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-9) which is a binder for solvent-based printing inks of the present invention was obtained. The polyurethane urea resin (U-9) had an Mw of 86,000.

Example 10
In a reactor equipped with a stirrer, 50 parts of the above polyether diol (A′-1), poly (3-methylpentylene adipate) diol [“Kuraray Polyol P-2010” manufactured by Kuraray Co., Ltd .: Mn = 2000] 150 parts of (a2-1), 0.95 part of 1,4-butanediol (a5), and 37.49 parts of IPDI (C-1) were charged and reacted at 110 ° C. for 10 hours in a nitrogen atmosphere to give an NCO content of 2 A 42% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 390 parts of ethyl acetate was added to make a uniform solution. Next, add 195 parts of isopropyl alcohol and stir until uniform, then add 11.59 parts of isophoronediamine (B-1) and 0.52 part of monoethanolamine (D-1) and react at 40 ° C. for 1 hour. As a result, a solution of polyurethane urea resin (U-10), which is a binder for solvent-based printing inks, was obtained. The polyurethane urea resin (U-10) had an Mw of 81,000.

Example 11
In a reactor equipped with a stirrer, 60 parts of the polyether diol (A′-2), polyneopentylene adipate diol [“San Ester 5620” manufactured by Sanyo Chemical Industries, Ltd .: Mn = 2000] (a2-2) ) 140 parts, 1,4-butanediol (a5) 1.24 parts, and IPDI (C-1) 24.47 parts, reacted under nitrogen atmosphere at 110 ° C. for 10 hours, NCO content 0.37% by weight The urethane prepolymer was obtained. After cooling to 40 ° C., 354 parts of ethyl acetate was added to make a uniform solution. Next, 177 parts of isopropyl alcohol was added and stirred until uniform, and then 2.14 parts of isophoronediamine (B-1) and 0.08 part of monoethanolamine (D-1) were added and reacted at 40 ° C. for 1 hour. Thus, a solution of polyurethane urea resin (U-11), which is a binder for solvent-based printing inks, was obtained. The polyurethane urea resin (U-11) had a Mw of 92,000.

Example 12
In a reactor equipped with a stirrer, 200 parts of the polyether diol (A′-3) and 44.81 parts of IPDI (C-1) were charged and reacted at 110 ° C. for 10 hours in a nitrogen atmosphere. A 43% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 406 parts of ethyl acetate was added to obtain a uniform solution. Next, 204 parts of isopropyl alcohol was added and stirred until homogeneous, and then 16.06 parts of isophoronediamine (B-1) and 1.15 parts of monoethanolamine (D-1) were added and reacted at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U-12) which is a binder for solvent-based printing inks of the present invention was obtained. The polyurethane urea resin (U-12) had a Mw of 79,000.

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

Example 14
In a reactor equipped with a stirrer, 50 parts of the above polyether diol (A-1), poly (3-methylpentylene adipate) diol [“Kuraray Polyol P-2010” manufactured by Kuraray Co., Ltd .: Mn = 2000] ( a2-1) 150 parts, dimethylolpropionic acid (DMPA) 0.23 parts, and IPDI (C-1) 34.16 parts were allowed to react at 110 ° C. for 10 hours in a nitrogen atmosphere, and the NCO content was 2.24 wt. % Urethane prepolymer was obtained. After cooling to 40 ° C., 381 parts of ethyl acetate was added to obtain a uniform solution. Next, after adding 191 parts of isopropyl alcohol and stirring until homogeneous, 10.59 parts of isophoronediamine (B-1) and 0.48 part of monoethanolamine (D-1) are added and reacted at 40 ° C. for 1 hour. Thus, a solution of polyurethane urea resin (U-14) which is a binder for solvent-based printing ink of the present invention was obtained. The polyurethane urea resin (U-14) had an Mw of 88,000.

Comparative Example 1
In a reactor equipped with a stirrer, polyoxyethylene glycol [“PEG-2000” manufactured by Sanyo Chemical Industries, Ltd .: Mn = 2000] (a1-2) 60 parts, 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 Was 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 was added to obtain a uniform solution. Next, add 198 parts of isopropyl alcohol and stir until homogeneous, then add 12.44 parts of isophoronediamine (B-1) and 0.56 parts of monoethanolamine (D-1) and react at 40 ° C. for 1 hour. As a result, a solution of polyurethane urea resin (U′-1), which is a binder for solvent-based printing inks, was obtained. The polyurethane urea resin (U′-1) had an Mw of 88,000.

Comparative Example 2
In a reactor equipped with a stirrer, 4 parts of the above polyether diol (A-1), 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 allowed to react at 110 ° C. for 10 hours under a nitrogen atmosphere, and an NCO content of 2. A 58% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 395 parts of ethyl acetate was added to make a uniform solution. Next, add 198 parts of isopropyl alcohol and stir until homogeneous, then add 12.45 parts of isophoronediamine (B-1) and 0.56 parts of monoethanolamine (D-1) and react at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U′-2), which is a binder for a solvent-based printing ink, was obtained. The polyurethane urea resin (U′-2) had an Mw of 79,000.

Comparative Example 3
In a reactor equipped with a stirrer, 86 parts of the polyether diol (A-1), 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 allowed to react at 110 ° C. for 10 hours in a nitrogen atmosphere to give an NCO content of 2. A 58% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 399 parts of ethyl acetate was added to obtain a uniform solution. Next, after adding 200 parts of isopropyl alcohol and stirring until homogeneous, add 12.57 parts of isophoronediamine (B-1) and 0.56 parts of monoethanolamine (D-1) and react at 40 ° C. for 1 hour. Thus, a solution of a polyurethane urea resin (U′-3) which is a binder for a solvent-based printing ink was obtained. The polyurethane urea resin (U′-3) had an Mw of 77,000.

Comparative Example 4
In a reactor equipped with a stirrer, polyoxypropylene glycol [Sanix PP-2000, Sanyo Chemical Industries, Ltd .: Mn = 2000] (a1-1) 60 parts, poly (3-methylpentylene adipate) 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 was added to obtain a uniform solution. Next, add 198 parts of isopropyl alcohol and stir until homogeneous, then add 12.44 parts of isophoronediamine (B-1) and 0.56 parts of monoethanolamine (D-1) and react at 40 ° C. for 1 hour. As a result, a solution of polyurethane urea resin (U′-4), which is a binder for solvent-based printing inks, was obtained. The polyurethane urea resin (U′-4) had an Mw of 82,000.

Examples 15 to 28 and Comparative Examples 5 to 8
Using the polyurethane urea resin solutions 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 formulation.

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

The results of the following performance test using the obtained solvent-based printing ink are 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). It shows in Table 1 with the total value.

[Production of test pieces]
Surface-treated polypropylene film (OPP) [“Pyrene P-2161” manufactured by Toyobo Co., Ltd. (thickness 30 μm)], surface-treated polyester film (PET) [“Espet E-5102” manufactured by Toyobo Co., Ltd. (thickness 12 μm)] And a surface-treated nylon film [“Harden N-1130” manufactured by Toyobo Co., Ltd. (thickness: 15 μm)], a solvent-based printing ink was applied by a bar coater to a thickness of 2 to 3 μm in solid content, and 1 at 60 ° C. Test pieces were prepared by drying for a minute.
[Adhesion test method]
A cellophane tape (made by Nichiban, 12 mm width) is applied to the coated surface of each test piece, and the ink is peeled off by observing the state of the coated surface when one end of this cellophane tape is rapidly peeled in a direction perpendicular to the coated surface. The area% that was not evaluated was evaluated.

[Boil resistance test method]
A dry laminate adhesive [main agent: polybond AY-651A, curing agent: polybond AY-651C (manufactured by Sanyo Kasei Kogyo Co., Ltd.)] is applied to the coated surface of the test piece using the above-mentioned surface-treated nylon film, and a laminator is used. It was used together with LLDPE (Mitsui Chemicals Tosero Co., Ltd.) and aged at 40 ° C. for 48 hours. Then, the bag is made by heat sealing with the LLDPE surface as the inside, the mixture of vinegar / salad oil / meat sauce = 1/1/1 (weight ratio) is enclosed as the contents, and the appearance after being boiled at 98 ° C. for 1 hour Was observed and evaluated according to the following criteria.
<Evaluation criteria>
A: No change in appearance.
○: Laminating float occurs in a very small part.
(Triangle | delta): The laminate float partially generate | occur | produces.
X: The laminate peels on the entire surface.

[Resolubility 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 with a depth of 35 μm, using a gravure printing test machine (TS-1 type printing machine; manufactured by Higashiya Iron Works Co., Ltd.) Table 1 shows the residual ink volume (% by volume) in the cell after the excess ink adhering to the gravure plate was washed off with a mixed solvent of isopropyl alcohol and ethyl acetate (weight ratio 3: 7).

[Test method of ink stability]
After adding 5% by weight of water to the prepared ink and stirring, the ink was allowed to stand at 25 ° C. for 1 week, and the viscosity immediately after preparation of the ink to which water was added (v0) and the viscosity after standing at 25 ° C. for 1 week (v1) ) With Zahn Cup # 4 (25 ° C.). Ink stability was expressed in terms of increased viscosity (seconds) calculated as (v1)-(v0) and is listed in Table 1.
In Table 1, “sedimentation” means that the pigment was partially agglomerated and sinked to the bottom of the container, and the viscosity could not be measured.

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

Claims

A solvent-based printing ink binder containing a polyurethane urea resin (U),
The polyurethane urea resin (U) is a polyether diol (A), a diamine, which is an adduct obtained by adding an alkylene oxide containing ethylene oxide and 1,2-propylene oxide to a compound (F) having two active hydrogens. (B) and diisocyanate (C) as essential constituent monomers,
A binder for solvent-based printing inks, wherein the content of oxyethylene groups in the polyurethane urea resin (U) is 2 to 24% by weight.
The polyurethane urea resin (U) is at least one compound (E) selected from the group consisting of tri- to tetra-functional polyhydric alcohols, tri- to 4-functional polyisocyanates, and dihydroxy carboxylic acids as constituent monomers. Containing
The binder for solvent-based printing ink according to claim 1, wherein the content of the compound (E) with respect to the polyurethane urea resin (U) is less than 0.1% by weight.
The solvent-based printing ink binder according to claim 1, wherein the content of the oxyethylene group in the polyurethane urea resin (U) is 5 to 18% by weight.
4. The compound according to claim 1, wherein the alkylene oxide comprises only ethylene oxide and 1,2-propylene oxide, and the compound (F) having two active hydrogens is water, ethylene glycol or 1,2-propanediol. The binder for solvent-based printing inks according to claim 1.
The polyether diol (A) is a random adduct obtained by randomly adding the ethylene oxide and the 1,2-propylene oxide to the compound (F) having two active hydrogens. The binder for solvent-based printing inks of any one of Claims 1.
The polyurethane urea resin (U) further includes, as a constituent monomer, a polyether diol (a1) other than the polyether diol (A), a polyester diol (a2), a polylactone diol (a3), and a polycarbonate diol (a4). The binder for solvent-based printing ink according to any one of claims 1 to 5, comprising at least one diol (a) selected from the group consisting of:
The at least one diol (a) selected from the group consisting of polyether diol (a1), polyester diol (a2), polylactone diol (a3) and polycarbonate diol (a4) has a branched alkyl group. The binder for solvent-type printing ink of description.
The solvent-based printing ink according to any one of claims 1 to 7, wherein a 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. Binder.
A solvent-based printing ink comprising the binder for a solvent-based printing ink according to any one of claims 1 to 8, a pigment, and a solvent.
The solvent-based printing ink according to claim 9, wherein the solvent contains an alcohol.