JP2017178976A - Binder for printing ink and printing ink using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binder for printing ink excellent in adhesiveness, blocking resistance, boil resistance and remelting property just after ink coating on various films.SOLUTION: There is provided a binder for printing ink which is a polyurethane urea resin (U) having polymer diol (A), diisocyanate (B), a chain extender (C) and amine (D) containing an alkoxysilyl group in a molecular structure as constitution units and having number average molecular weight of the polyurethane urea resin (U) of 2,000 to 4,950 and total value of urethane group concentration and urea group concentration of 0.9 to 1.5 mmol/g. The concentration of the alkoxysilyl group in the polyurethane urea resin (U) is preferably 0.001 to 0.5 mmol/g.SELECTED DRAWING: None

Description

  The present invention relates to a printing ink binder and 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. A polyurethane resin containing polypropylene glycol using only a solvent such as MEK and ethyl acetate without using toluene has been proposed (for example, see Patent Document 2), but immediately after ink application to various films. It was difficult to achieve both adhesion, blocking resistance, and boil resistance.

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

  The subject of this invention is providing the binder for printing inks which is excellent in the adhesiveness immediately after ink application to various films, blocking resistance, boil resistance, and re-dissolution property.

  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 has a polymer diol (A), a diisocyanate (B), a chain extender (C), an alkoxysilyl group, and one or two primary amino groups and / or secondary amino groups. And a polyurethane urea resin (U) having an amine (D) that is not a chain extender (C) as an essential constituent monomer, and the polyurethane urea resin (U) has a number average molecular weight of 2,000 to 4,950. A binder for printing ink in which the total value of the urethane group concentration and the urea group concentration of the polyurethane urea resin (U) based on the weight of the polyurethane urea resin (U) is 0.9 to 1.5 mmol / g; A printing ink containing a binder for ink.

  The binder for printing inks of the present invention is excellent in adhesion, blocking resistance, boil resistance, and re-dissolvability immediately after ink application to various films.

  The binder for printing ink of the present invention has a polymer diol (A), a diisocyanate (B), a chain extender (C), an alkoxysilyl group, and one primary amino group and / or secondary amino group or Polyurethane urea resin (U) having two (2) amines (D) that are not chain extenders (C) as essential constituent monomers.

The number average molecular weight (hereinafter abbreviated as Mn) of the polymer 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: Mn of standard polyethylene glycol polymer diol (A) is preferably 500 to 10,000, more preferably 1,000 to 5,000.

Examples of the polymer diol (A) include polyether diol (a1), polyester diol (a2), polylactone diol (a3), and polycarbonate diol (a4). Specific examples include the following compounds.
As the polyether diol (a1), 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) And 1,6-hexanediol and the like, and diols having a branched alkyl chain (1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propane) Diol, 1,2-, 1,3- or 2,3-butanediol, etc.], etc.]; alicyclic group-containing dihydric 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-xy Lenglycol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene, bisphenols (such as bisphenol A, bisphenol S and bisphenol F) dihydroxynaphthalene, and monoalkylamines having 1 to 12 carbon atoms (monomethylamine, monoethylamine and C2-C12 alkylene oxide (hereinafter abbreviated as AO) adducts to monobutylamine and the like, and as C2-C12 AO, ethylene oxide (EO), 1,2-propylene oxide ( PO), 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, styrene oxide and α-olefin oxide. Moreover, AO may be used individually by 1 type, or 2 or more types may be block-copolymerized and random-copolymerized.

Mn of the polyether diol (a1) is preferably 500 to 10,000, more preferably 1,000 to 5,000, from the viewpoints of adhesiveness and solubility.

Among the polyether diols (a1), those having a branched alkyl chain are preferable from the viewpoint of resolubility, that is, those using a diol having a branched alkyl chain among diols having an Mn of less than 500 as a raw material, and AO. Those using PO, 1,2-, 2,3- or 1,3-butylene oxide, 3-methyltetrahydrofuran and the like as AO in the adduct, and more preferably a dihydric alcohol having a branched alkyl chain. Aliphatic polyether diols, particularly preferred are polyoxypropylene glycols.

  The polyester diol (a2) is obtained by condensation of a diol 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.]. Etc.

  Diols 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 and the like, and diols having a branched alkyl chain (1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propane) Diol, 1,2-, 1,3- or 2,3-butanediol, etc.]]; alicyclic group-containing dihydric 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-xylylene] AO adduct having 2 to 12 carbon atoms such as glycol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene, bisphenol (such as bisphenol A, bisphenol S and bisphenol F), an AO adduct of dihydroxynaphthalene and bis (2 -Hydroxyethyl) terephthalate, etc.];

  As AO having 2 to 12 carbon atoms, EO, PO, 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, styrene oxide, and α- Olefin oxide etc.]. AO may be used individually by 1 type, or may use 2 or more types together.

Examples of the dicarboxylic acid or its ester-forming derivative include aliphatic dicarboxylic acids having 2 to 15 carbon atoms [oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.] 8-12 aromatic dicarboxylic acids [terephthalic acid, isophthalic acid, etc.] and ester-forming derivatives thereof [acid anhydrides, lower alkyl esters (dimethyl ester, diethyl ester, etc.), acid halides (acid chloride, etc.)], 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, polyneopentyl 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 Examples include polyneopentyl terephthalate diol.

  Of the polyester diols (a2), polyester diols having a linear alkyl chain are preferable from the viewpoint of blocking resistance, polyethylene adipate diol and polybutylene adipate diol are particularly preferable, and polyethylene adipate diol is most preferable. From the viewpoint of resolubility, preferred are polyester diols having branched alkyl chains, particularly preferred are polyneopentyl adipate diol and poly (3-methylpentylene adipate) diol, and most preferred is poly (3-methylpentylene adipate). ) Diol. (A2) may be used alone or in combination of two or more.

As the polylactone diol (a3), a lactone monomer (γ-butyrolactone, γ-valerolactone, ε-caprolactone and a mixture of two or more thereof) was subjected to ring-opening polymerization using the diol having an Mn of less than 500 as an initiator. And the like. Specific examples of the polylactone diol include polybutyrolactone diol, polyvalerolactone diol, and polycaprolactone diol.

The polycarbonate diol (a4) includes a diol having a 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, an alkylene group having 2 to 6 carbon atoms, and carbon). And polycarbonate diol produced by condensing a diaryl carbonate having an aryl group of several 6 to 9 with a dealcoholization reaction.

  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).

  Polymer diol (A) may be used individually by 1 type, or may use 2 or more types together. The weight ratio of the polymer diol (A) is preferably 2 to 90%, more preferably 5 to 80%, based on the weight of the polyurethane urea resin (U).

As a constituent monomer of the polyurethane urea resin (U), in addition to the polymer diol (A), the above-described diol having an Mn of less than 500 is used to adjust the urethane group concentration and urea group concentration in the polyurethane urea resin (U). It can be used for adjustment purposes.

  As organic diisocyanate (B), what is conventionally used for manufacture of polyurethane can be used, C4-C22 aliphatic diisocyanate (B1), C8-C18 alicyclic diisocyanate (B2), carbon Examples thereof include an aromatic diisocyanate (B3) having 8 to 26 and an araliphatic diisocyanate (B4) having 10 to 18 carbon atoms.

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

  Examples of the alicyclic diisocyanate (B2) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2-isocyanato). 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 (B3) 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 araliphatic diisocyanate (B4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

Among these, alicyclic diisocyanate (B2) having 8 to 18 carbon atoms is preferable from the viewpoint of adhesiveness, and IPDI is preferable from the viewpoint of re-solubility of the polyurethane urea resin (U).
An organic diisocyanate (B) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the chain extender (C) include diamines having 2 to 12 carbon atoms, poly (n = 2 to 6) alkylene (2 to 6 carbon atoms) poly (n = 3 to 7) amines (diethylenetriamine, dipropylenetriamine, dihexane). Xylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and the like), hydrazine or a derivative thereof (dibasic acid dihydrazide such as adipic acid dihydrazide) and the like. (C) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the diamine having 2 to 12 carbon atoms include ethylene diamine, propylene diamine, hexamethylene diamine, isophorone diamine, toluene diamine, and piperazine.

Moreover, you may use together chain extender (C) and the said diol whose Mn is less than 500. Among diols having an Mn of less than 500, 1,4-butanediol is preferred as a chain extender from the viewpoint of resolubility and solvent resistance.
Preferred as the chain extender (C) is isophoronediamine from the viewpoint of resolubility.

  The amine (D) having an alkoxysilyl group and having one or two primary amino groups and / or secondary amino groups and not a chain extender (C) is a monoamine having an alkoxysilyl group. Examples thereof include a compound (D1) and a diamine compound (D2) having an alkoxysilyl group. Examples of the monoamine compound (D1) having an alkoxysilyl group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.

  Examples of the diamine compound (D2) having an alkoxysilyl group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane. .

The concentration of the alkoxysilyl group in the polyurethane urea resin (U) is preferably 0.001 to 0.5 mmol / g, more preferably 0.02 to 0.25 mmol / g, from the viewpoint of boil resistance and solubility. The printing ink binder according to claim 1.

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

  Examples of the reaction terminator (E) 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 (E) may be used individually by 1 type, or may use 2 or more types together.

  The total value (x) of the urethane group [—NHCOO—] concentration and the urea group [—NHCONH—] concentration in the polyurethane urea resin (U) based on the weight of the polyurethane urea resin (U) is 0.9 to 1.5 mmol. / G, more preferably 1.0 to 1.5 mmol / g, particularly preferably 1.2 to 1.4 mmol / g. When the total value (x) is less than 0.9 mmol / g, blocking resistance and boil resistance deteriorate, and when it exceeds 1.5 mmol / g, adhesion and re-dissolvability deteriorate.

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 an aliphatic group is used, the urea group is calculated from the ratio of the integral amount of hydrogen derived from a urea group near a chemical shift of 6 ppm and the integral amount of hydrogen derived from a urethane group near a chemical shift of 7 ppm. The weight ratio of the urethane groups is measured, and the urethane group concentration and the 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) has a polymer diol (A), a diisocyanate (B), a chain extender (C), an alkoxysilyl group, and one or two primary amino groups and / or secondary amino groups. The amine (D) which is individual and is not the chain extender (C) is an essential constituent monomer, but the ratio is preferably (A) :( B) :( C) :( D) in weight ratio. = 100: 5 to 40: 0.1 to 20: 0.1 to 10, more preferably 100: 15 to 25: 1 to 10: 1 to 7.

The method for producing the polyurethane urea resin (U) is not particularly limited, and has a polymer diol (A), a diisocyanate (B), a chain extender (C), an alkoxysilyl group, and a primary amino group and / or 2 A one-shot method in which an amine (D) having one or two primary amino groups and not a chain extender (C) and, if necessary, a reaction terminator (E) are reacted at once, or a stepwise reaction [For example, (A) and (B) are reacted to form an isocyanate group-terminated prepolymer, and then (C) and (D) and, if necessary, (E) are further reacted to produce, etc.] However, from the viewpoint of adhesion, after forming the isocyanate group-terminated prepolymer, the equivalent of the isocyanate group in which the prepolymer has a diamine having 2 to 12 carbon atoms as the chain extender (C). A preferred method of introducing an amino group at the end of the polyurethane urea molecular chains by using as the sum of the amino groups of the amine is excessive for.

  In the production of the polyurethane urea resin (U), the activity of the isocyanate group of the organic diisocyanate (B), the diol component (A), the chain extender (C), the amine (D), and the reaction terminator (E) used as necessary. The equivalent ratio of the hydrogen-containing groups (isocyanate group: active hydrogen-containing group) is usually 0.7: 1 to 0.99: 1, preferably 0.8: 1 to 0.98: 1.

  The reaction of the diol component and the organic diisocyanate component (C) is usually performed at a temperature of 20 to 140 ° C, preferably 40 to 120 ° C. However, when making an amine react, it is 100 degrees C or less normally, Preferably it is 0-80 degreeC.

  In the reaction, in order to promote the reaction, if necessary, a catalyst used in a usual urethane reaction [amine catalyst (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), tin-based catalyst (dibutyltin dilaurate, dioctyltin dilaurate and Tin octylate, etc.) and titanium catalysts (tetrabutyl titanate, etc.)] and the like may be used. The amount of the catalyst used is usually 0.1% by weight or less based on the polyurethane urea resin.

  Moreover, the said reaction may be performed in a solvent (F) and you may add a solvent (F) in the middle of reaction or after reaction. As the solvent (F), ester solvents (such as ethyl acetate, butyl acetate and ethyl cellosolve acetate), ketone solvents (such as acetone, methyl isobutyl ketone and methyl isobutyl ketone), ether solvents (dioxane, tetrahydrofuran and propylene glycol monomethyl) Ethers), aliphatic hydrocarbon solvents (n-hexane, n-heptane, cyclohexane, etc.) and alcohol solvents (ethanol, methanol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc.).

Among 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.
A solvent (F) may be used individually by 1 type, or may use 2 or more types together.

  The number average molecular weight (hereinafter abbreviated as Mn) of the polyurethane urea resin (U) in the present invention is 2,000 to 4,950, preferably 3,000 to 4,900, more preferably 3,500. ~ 4,800. When the Mn of (U) is less than 2,000, blocking resistance and boil resistance deteriorate, and when the Mn of (U) exceeds 4,950, adhesion and re-solubility deteriorate.

Mn of the polyurethane urea resin (U) 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% by weight dimethylformamide solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene

  The printing ink binder of the present invention comprising the polyurethane urea resin (U) of the present invention can be used as a solution (varnish) in which the polyurethane urea resin (U) is dissolved in the solvent (G) from the viewpoint of handling properties and the like. preferable. The resin concentration of the solvent (G) solution of (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 solvent (G) solution of (U) is preferably 50 to 100,000 mPa · s, more preferably 100 to 10,000 mPa · s from the same viewpoint.

The printing ink of the present invention contains the printing ink binder, the pigment, and the solvent (G) of the present invention as essential components. There is no restriction | limiting in particular as a pigment, The inorganic pigment, organic pigment, etc. which are used for normal printing ink can be used.
The solvent (G) may be the same as or different from the solvent (F) used for the reaction. The solvent (G) is preferably ethyl acetate, butyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, n-propyl alcohol or isopropyl alcohol from the viewpoint of re-solubility of the polyurethane urea resin (U). More preferred are ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and isopropyl alcohol.

  If necessary, other resins usually used in 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 amount of these other resins added is usually 30% by weight or less, preferably 20% by weight or less in the printing ink.

  The production method of the printing ink is not particularly limited, and the printing ink can be produced using a known method such as a normal ink production apparatus such as a three-roll, ball mill, and sand grinder mill.

An example of the formulation of the printing ink of the present invention is as follows.
Binder 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)

  Although the printing ink using the binder for printing inks of the present invention may be used as a one-component printing ink, it can also be used as a two-component printing ink in combination with, for example, a polyisocyanate curing agent. Examples of the polyisocyanate curing agent in this case include an adduct formed from 1 mol of trimethylolpropane and 3 mol of 1,6-hexamethylene diisocyanate, tolylene diisocyanate or IPDI; Isocyanurate group-containing trimers synthesized by cyclotrimerization 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 usually 0.5 to 10% by weight based on the weight of the printing ink binder of the present invention.

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

The binder for printing ink of the present invention has excellent adhesiveness to various plastic films such as polyester, nylon, and polyolefin, and can be used universally as a binder for printing ink for various plastic films.
The printing ink of the present invention includes polyester film, nylon film, surface-treated or non-treated polypropylene film, polyethylene film, polyvinyl acetal film, acetate film, polyvinyl chloride film, and films obtained by performing aluminum deposition on these films. It can be suitably used for printing various plastic films.

  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.

Example 1
In a reactor equipped with a stirrer, 70 parts of polyoxypropylene glycol [Sanix PP-4000 manufactured by Sanyo Chemical Industries, Ltd .: Mn = 4000], polyethylene adipate diol [San Esther manufactured by Sanyo Chemical Industries, Ltd. 2620 ": Mn = 2000], 130 parts of 1,4-butanediol 0.21 part, and 33.15 parts of IPDI were charged and reacted at 110 ° C. for 10 hours in a nitrogen atmosphere to obtain urethane prepolymer having an NCO content of 2.35% by weight. A polymer was obtained. After cooling to 40 ° C., 386 parts of ethyl acetate was added to obtain a uniform solution. Next, 194 parts of isopropanol was added and stirred until uniform, then 5.76 parts of isophoronediamine, 4.98 parts of 3-aminopropyltriethoxysilane and 4.74 parts of diethanolamine were added and reacted at 40 ° C. for 1 hour. A solution of polyurethane urea resin (U-1) which is a binder for printing ink of the present invention was obtained. The Mn of (U-1) was 3,700.

Example 2
In a reactor equipped with a stirrer, 70 parts of polyoxypropylene glycol [Sanix PP-4000 manufactured by Sanyo Chemical Industries, Ltd .: Mn = 4000], polyethylene adipate diol [San Esther manufactured by Sanyo Chemical Industries, Ltd. 2620 ": Mn = 2000], 130 parts of 1,4-butanediol 0.21 part, and 32.38 parts of TDI were charged and reacted at 80 ° C. for 3 hours in a nitrogen atmosphere to obtain a urethane prepolymer having an NCO content of 3.69% by weight. A polymer was obtained. After cooling to 40 ° C., 400 parts of ethyl acetate was added to obtain a uniform solution. Next, 200 parts of isopropanol was added and stirred until uniform, then 8.55 parts of isophoronediamine, 8.55 parts of 3-aminopropyltriethoxysilane and 11.62 parts of diethanolamine were added and reacted at 40 ° C. for 1 hour. A solution of polyurethane urea resin (U-2) which is a binder for printing ink of the present invention was obtained. The Mn of (U-2) was 2,040.

Example 3
In a reactor equipped with a stirrer, polyoxypropylene glycol [Sanyo Chemical Industry Co., Ltd. “Sanix PP-4000”: Mn = 4000] 100 parts, polyethylene adipate diol [Sanyo Chemical Industry Co., Ltd. “San Ester” 2620 ": Mn = 2000], 100 parts of 1,4-butanediol 0.18 parts, and 27.49 parts of IPDI were charged and reacted at 110 ° C. for 10 hours in a nitrogen atmosphere to obtain urethane prepolymer having an NCO content of 1.75% by weight. A polymer was obtained. After cooling to 40 ° C., 376 parts of ethyl acetate was added to make a uniform solution. Next, after adding 189 parts of isopropanol and stirring until uniform, 2.41 parts of isophoronediamine, 10.89 parts of 3-aminopropyltrimethoxysilane and 1.06 parts of diethanolamine are added and reacted at 40 ° C. for 1 hour. A solution of polyurethane urea resin (U-3) which is a binder for printing ink of the present invention was obtained. Mn of (U-3) was 4,600.

Example 4
In a reaction apparatus equipped with a stirrer, polyoxypropylene glycol [Sanyo Chemical Industries, Ltd. “Sanix PP-2000”: Mn = 2000] 40 parts, poly (3-methylpentylene adipate) diol [Kuraray Co., Ltd. ) “Kuraray polyol P-2010”: 160 parts of Mn = 2000], 0.79 part of 1,4-butanediol, and 45.07 parts of IPDI were allowed to react at 110 ° C. for 10 hours in a nitrogen atmosphere, and an NCO content of 3 15% by weight of urethane prepolymer was obtained. After cooling to 40 ° C., 418 parts of ethyl acetate was added to obtain a uniform solution. Next, after adding 209 parts of isopropanol and stirring until uniform, 8.06 parts of isophoronediamine, 12.12 parts of 3-aminopropyltrimethoxysilane, and 2.84 parts of diethanolamine are added and reacted at 40 ° C. for 1 hour. A solution of polyurethane urea resin (U-4) which is a binder for printing ink of the present invention was obtained. The Mn of (U-4) was 4,250.

Example 5
In a reactor equipped with a stirrer, 40 parts of polyoxypropylene glycol [Sanix PP-4000 manufactured by Sanyo Chemical Industries, Ltd .: Mn = 4000], poly (3-methylpentylene adipate) diol [Kuraray Co., Ltd. ) “Kuraray polyol P-2010”: 160 parts of Mn = 2000], 0.13 part of 1,4-butanediol, and 38.86 parts of IPDI were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere. Obtained 88 wt% urethane prepolymer. After cooling to 40 ° C., 397 parts of ethyl acetate was added to obtain a uniform solution. Next, after adding 199 parts of isopropanol and stirring until uniform, 3.58 parts of isophoronediamine, 4.68 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and 8.84 parts of diethanolamine were added. The solution was reacted at 40 ° C. for 1 hour to obtain a solution of polyurethane urea resin (U-5) which is a binder for printing ink of the present invention. The Mn of (U-5) was 4,950.

Comparative Example 1
In a reaction apparatus equipped with a stirrer, polyoxypropylene glycol [Sanyo Chemical Industries, Ltd. “Sanix PP-2000”: Mn = 2000] 40 parts, poly (3-methylpentylene adipate) diol [Kuraray Co., Ltd. ) “Kuraray polyol P-2010”: 160 parts of Mn = 2000], 0.79 part of 1,4-butanediol, and 45.07 parts of IPDI were allowed to react at 110 ° C. for 10 hours in a nitrogen atmosphere, and an NCO content of 3 15% by weight of urethane prepolymer was obtained. After cooling to 40 ° C., 410 parts of ethyl acetate was added to obtain a uniform solution. Next, 205 parts of isopropanol was added and stirred until uniform, and then 8.19 parts of isophoronediamine and 10.11 parts of diethanolamine were added and reacted at 40 ° C. for 1 hour to be a polyurethane urea resin which is a binder for printing inks of the present invention. A solution of (U′-1) was obtained. The Mn of (U′-1) was 4,180.

Comparative Example 2
In a reactor equipped with a stirrer, 40 parts of polyoxypropylene glycol [Sanix PP-4000 manufactured by Sanyo Chemical Industries, Ltd .: Mn = 4000], poly (3-methylpentylene adipate) diol [Kuraray Co., Ltd. ) “Kuraray polyol P-2010”: 160 parts of Mn = 2000], 0.99 parts of 1,4-butanediol, and 40.65 parts of IPDI were allowed to react at 110 ° C. for 10 hours in a nitrogen atmosphere. 80 wt% urethane prepolymer was obtained. After cooling to 40 ° C., 402 parts of ethyl acetate was added to obtain a uniform solution. Next, 201 parts of isopropanol was added and stirred until uniform, then 9.56 parts of isophoronediamine, 4.15 parts of 3-aminopropyltrimethoxysilane and 3.47 parts of diethanolamine were added and reacted at 40 ° C. for 1 hour. A solution of polyurethane urea resin (U′-2) which is a binder for printing ink of the present invention was obtained. The Mn of (U′-2) was 5,150.

Comparative Example 3
In a reactor equipped with a stirrer, 40 parts of polyoxypropylene glycol [Sanix PP-4000 manufactured by Sanyo Chemical Industries, Ltd .: Mn = 4000], poly (3-methylpentylene adipate) diol [Kuraray Co., Ltd. ) “Kuraray Polyol P-2010”: Mn = 2000], 160 parts of 1,4-butanediol 0.33 parts, and 46.00 parts of IPDI were charged and reacted at 110 ° C. for 10 hours in a nitrogen atmosphere to give an NCO content of 3 Obtained 81 wt% urethane prepolymer. After cooling to 40 ° C., 424 parts of ethyl acetate was added to obtain a uniform solution. Next, 212 parts of isopropanol was added and stirred until uniform, and then 1.79 parts of isophoronediamine, 5.36 parts of 3-aminopropyltriethoxysilane and 19.59 parts of diethanolamine were added and reacted at 40 ° C. for 1 hour. A solution of polyurethane urea resin (U′-3), which is a binder for printing ink of the present invention, was obtained. The Mn of (U′-3) was 1,850.

Comparative Example 4
In a reaction apparatus equipped with a stirrer, 70 parts of polyoxypropylene glycol [Sanix Chemical Industries, Ltd. “Sanniks PP-2000”: Mn = 2000], polyethylene adipate diol [Sanyo Chemical Industries, Ltd. 2620 ": Mn = 2000], 130 parts of 1,4-butanediol 1.29 parts and 50.15 parts of IPDI were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain urethane prepolymer having an NCO content of 3.74% by weight. A polymer was obtained. After cooling to 40 ° C., 428 parts of ethyl acetate was added to obtain a uniform solution. Next, 214 parts of isopropanol was added and stirred until uniform, and then 11.35 parts of isophoronediamine, 5.68 parts of 3-aminopropyltriethoxysilane and 7.31 parts of diethanolamine were added and reacted at 40 ° C. for 1 hour. A solution of a polyurethane urea resin (U′-4) which is a binder for printing ink of the present invention was obtained. The Mn of (U′-4) was 4,300.

Comparative Example 5
In a reactor equipped with a stirrer, 100 parts of polyoxypropylene glycol [Sanix PP-4000 manufactured by Sanyo Chemical Industries, Ltd .: Mn = 4000], poly (3-methylpentylene adipate) diol [Kuraray Co., Ltd. ) "Kuraray polyol P-2010": Mn = 2000], 100 parts of 1,4-butanediol 0.14 parts, and 20.61 parts of IPDI were charged and reacted at 110 ° C. for 10 hours in a nitrogen atmosphere. A 58% by weight urethane prepolymer was obtained. After cooling to 40 ° C., 354 parts of ethyl acetate was added to make a uniform solution. Next, after adding 178 parts of isopropanol and stirring until uniform, 0.53 parts of isophoronediamine and 6.81 parts of 3-aminopropyltriethoxysilane are added and reacted at 40 ° C. for 1 hour for use in the printing ink of the present invention. A solution of a polyurethane urea resin (U′-5) as a binder was obtained. The Mn of (U′-5) was 8,500.

Examples 6 to 10 and Comparative Examples 6 to 10
Using the polyurethane urea resin solutions obtained in Examples 1 to 5 and Comparative Examples 1 to 5, printing inks of Examples 6 to 10 and Comparative Examples 6 to 10 were prepared according to the following formulation.

[Preparation of white ink]
A mixture of 35 parts of a solution of polyurethane urea resin, 35 parts of titanium oxide (“Titanics JR809” manufactured by Teika Co., Ltd.), 10 parts of isopropyl alcohol, 20 parts of ethyl acetate, and 100 parts of glass beads is used as a paint conditioner (Red Devil Corporation). For 3 hours, and the glass beads were removed by filtration to obtain a white ink.

  The results of performing the following performance test using the obtained printing ink are the results of the number average molecular weight of the polyurethane urea resin (U), the total value of the urethane group concentration and the urea group concentration in the polyurethane urea resin (U), polyurethane Table 1 shows the concentration of alkoxysilyl groups in the urea resin (U).

[Adhesion test method]
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” (thickness: 15 μm) manufactured by Toyobo Co., Ltd.] with a bar coater so as to have a thickness of 2 to 3 μm in solid content, and at 40 ° C. After drying for 1 minute, a cellophane tape (made by Nichiban, 12 mm width) is applied to the coated surface, and the ink surface is observed by observing the coated surface state when one end of this cellophane tape is rapidly peeled in a direction perpendicular to the coated surface. Evaluation was based on the area% not peeled off.

[Testing method for blocking resistance]
A surface-treated polyester film (PET) [“SPET E-5102” manufactured by Toyobo Co., Ltd. (thickness: 12 μm)] was coated with a printing ink so as to have a solid content of 2 to 3 μm with a bar coater. And then dried so that the untreated surface of the polyester film is in close contact with the coated surface, applied with a pressure of ² kg / cm ^{2 with} a blocking tester, and left at a temperature of 50 ° C. for 24 hours. Then, it was cooled to room temperature, and the state of the coated surface when the stacked films were peeled off was observed, and the evaluation was made by area% where the ink was not peeled off.

[Boil resistance test method]
On the coated surface of the nylon film, an adhesive for dry lamination [main agent: polybond AY-651A, curing agent: polybond AY-651C (manufactured by Sanyo Chemical Industries)] is applied, and LLDPE (Mitsui Chemicals East Cello) is used with a laminator. 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.
○: Lami floating occurs in a small part.
(Triangle | delta): Lami floating generate | occur | produced partially.
X: The laminate peels on the entire surface.

[Resolubility test method]
Using a gravure printing test machine (TS-1 type printing machine; manufactured by Higashitani Iron Works), using a gravure plate with a depth of 35 μm, printing 100 m of printing ink on an OPP film at a speed of 30 m / min. Table 1 shows the residual ink volume (% by volume) in the cells after the excess ink adhered was washed off with a mixed solvent of isopropyl alcohol and ethyl acetate (weight ratio 3: 7).

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

Claims (6)

Polymer diol (A), diisocyanate (B), chain extender (C), alkoxysilyl group and one or two primary amino groups and / or secondary amino groups, and chain extender A polyurethane urea resin (U) having an amine (D) which is not (C) as an essential constituent monomer, wherein the polyurethane urea resin (U) has a number average molecular weight of 2,000 to 4,950, and is a polyurethane urea. A binder for printing ink in which the total value of the urethane group concentration and the urea group concentration of the polyurethane urea resin (U) based on the weight of the resin (U) is 0.9 to 1.5 mmol / g. The binder for printing ink according to claim 1, wherein the concentration of the alkoxysilyl group in the polyurethane urea resin (U) based on the weight of the polyurethane urea resin (U) is 0.001 to 0.5 mmol / g. The polymer diol (A) contains at least one diol (a) selected from the group consisting of polyether diol (a1), polyester diol (a2), polylactone diol (a3) and polycarbonate diol (a4). Item 3. A printing ink binder according to Item 1 or 2. The binder for printing inks according to any one of claims 1 to 3, wherein the polymer diol (A) has a branched alkyl group. Printing ink containing the binder for printing inks of any one of Claims 1-4, a pigment, and a solvent (G). The printing ink according to claim 5, wherein the solvent (G) contains an alcohol.