JP6455535B2 - Gravure ink for solvent-type lamination, printed matter, and laminate - Google Patents

Description

  The present invention relates to a gravure ink for solvent-type laminating, a printed material thereof and a laminate.

  When a film substrate such as an OPP film, a PET film, or a NY film is used as a packaging material, printing using a printing ink is usually performed for decoration or surface protection of the substrate. The substrate subjected to printing is then sent to the laminating process through a slitting process, and finally becomes a package for food packaging, cosmetic packaging, and all other uses.

In many cases, a gravure printing method is employed for printing on the film substrate and paper substrate. The plate used for the gravure printing method is an intaglio plate with characters and patterns. Soak the ink in the plate to the extent that ink enters this cell, and rotate the plate while scraping off excess ink with a doctor blade. Then, the gravure ink is transferred to the base material and allowed to become thick. Since this printing method can express fine shades, it is optimal for reproducing rich gradations such as photographs and is suitable for mass production because high-speed printing is possible.

Problems with printability of this gravure printing method include: (I) whitening of the ink film, (II) wear of the doctor blade due to ink deposition, and (III) the ink pan on the ink pan. Cause, etc. If these occur, printing itself becomes impossible, causing work delays. Even if it can be printed, it will cause poor transfer to the substrate, doctor streaks, and deterioration of ink handling properties, resulting in a significant reduction in productivity. The defective print is handled as a defective lot by the print converter, causing a production loss. These defects are remarkable in the current mainstream non-toluene solvent-based gravure ink, and are caused by the lower solvent solubility of the solvent compared to the previous toluene-based solvent gravure ink. These troubles are conspicuous in white ink with a high pigment content, and are often seen particularly in white ink using titanium oxide, which is an inorganic pigment.

Conventionally, various attempts have been made to improve printability. For example, in addition to the above printability, solvent-based gravure ink containing glycol ether or water has been proposed in order to improve plate, ie, printability. (Patent Document 1). In addition, a gravure ink (liquid ink) in which a vinyl chloride / vinyl acetate copolymer and styrene-maleic anhydride are blended to improve ink stability and two-component stability has been proposed (Patent Document 2). However, a method for ensuring printability at high temperature and high humidity has not yet been established, and there is a method for improving printability by changing the design of the binder resin used, but the principle has not yet been established. Further, if there is a defective part in the printed matter, the possibility of causing a defect also in the subsequent lamination increases.

In laminating use, after the ink is printed on the base material, the base material is further bonded thereon with an adhesive. The methods are roughly classified into three types: an extrusion laminating method, a dry laminating method, and a non-solvent laminating method. What is concerned about these laminating processes is poor appearance, insufficient laminating strength, and resistance to boil and retort, and various ideas have been made to improve them (Patent Document 3, Patent Document 4, Patent Document 5). ). However, there has never been a satisfactory printability and laminate property, and it has been extremely difficult to improve the printability due to the stability of the ink depending on the pigment type.

JP-A-9-328646 JP, 2014-005318, A JP 2010-270216 A JP 2005-298618 A JP 2013-213109 A

  In gravure printing under conditions of high temperature and high humidity, there is provided a gravure ink for solvent-type laminating which has no printing layer whitening, has less skinning and doctor wear due to ink deposition, and has good printability.

  As a result of intensive studies on the above problems, the present inventor has found that the problem can be solved by using the printing ink composition for laminating described below, and has reached the present invention.

The present invention is a gravure ink for solvent-type laminating containing a titanium oxide pigment (A), a binder resin (B), an organic solvent (C), and water (D), and the following (1) and ( It is related with the gravure ink for solvent-type lamination characterized by satisfying 2).
(1) Binder resin (B) In 100% by weight, polyurethane resin (b1) and vinyl chloride copolymer resin (b2) are included in a total of 70 to 100% by weight, and the weight ratio of the resin is (b1) : (B2) = 95: 5 to 40:60.
(2) In 100% by weight of the gravure ink, 0.1 to 10% by weight of the glycol ether organic solvent (c1) and 0.1 to 6% by weight of water (D) are contained as the organic solvent (C).

The present invention relates to the gravure ink for solvent-type laminating, wherein the titanium oxide pigment (A) is a rutile type titanium oxide surface-treated with at least silica and / or alumina.

The present invention relates to the gravure ink for solvent-type lamination, wherein the solubility parameter of the glycol ether organic solvent (c1) is 9.0 to 12.0.

The present invention relates to the gravure ink for solvent-type lamination, wherein the boiling point of the glycol ether organic solvent (c1) is 110 to 240 ° C.

The present invention relates to the gravure ink for solvent-type laminating, wherein the glycol ether organic solvent (c1) is ethylene glycol monoalkyl ether and / or propylene glycol monoalkyl ether.

The present invention relates to a printed matter having a printing layer formed on the substrate 1 from the solvent-type laminating gravure ink.

The present invention relates to a laminate having at least an adhesive layer and a substrate 2 in this order on the printed layer of the printed matter.

  By using the gravure ink for solvent-type laminating of the present invention, in gravure printing under conditions of high temperature and high humidity, there is no whitening of the printed layer, there is little skinning and doctor wear due to ink deposition, and the solvent type with good printability A gravure ink for laminating could be provided.

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. The content is not limited.

The present invention is a gravure ink for solvent-type laminating containing a titanium oxide pigment (A), a binder resin (B), an organic solvent (C), and water (D), and the following (1) and ( 2) is satisfied.
(1) Binder resin (B) In 100% by weight, polyurethane resin (b1) and vinyl chloride copolymer resin (b2) are included in a total of 70 to 100% by weight, and the weight ratio of the resin is (b1) : (B2) = 95: 5 to 40:60.
(2) In 100% by weight of the gravure ink, 0.1 to 10% by weight of glycol ether organic solvent (c1) and 0.1 to 6% by weight of water (D) are contained.

In printing under high-temperature and high-humidity conditions, the solubility of the dispersion of the titanium oxide pigment (A) in the ink (solid content in the ink) decreases, so that the solid component tends to precipitate. In the present invention, the polyurethane resin (b1) and the vinyl chloride copolymer resin (b2) are contained in a total of 70 to 100% by weight, and the weight ratio of the resins is (b1) :( b2) = 95: 5 When contained at 40:60, the dispersion stability of the titanium oxide pigment (A) with respect to the organic solvent is improved, so that there is an effect of suppressing precipitation. On the other hand, the gravure ink for solvent-type lamination of the present invention contains an organic solvent (C). As the organic solvent (C), an organic solvent that does not contain an aromatic organic solvent such as toluene and xylene is preferable because it is highly safe and improves the saturation of the halftone dot. Min) is lower than that of toluene. However, when the organic solvent (C) contains 0.1 to 10% by weight of the glycol ether organic solvent (c1) and 0.1 to 6% by weight of water, the dissolving power of the mixed solvent is greatly increased. In addition, the fluidity and lubricity are greatly improved.
These effects are as follows: 1) Glycol ether organic solvent (c1) greatly improves the solubility of the pigment dispersion. 2) Water aggregates with urethane bonds between polyurethane resins (b1) and hydrogen bonds derived from urea bonds. 3) The vinyl chloride copolymer resin (b2) promotes the pigment dispersion and stabilizes the pigment dispersion, which is presumed to be the synergistic effects of the above 1) to 3). In addition, this description is based on guess to the last, and does not limit invention.

Hereinafter, the gravure ink for solvent-type laminating of the present invention may be referred to as “gravure ink” or “ink”.

<Titanium oxide pigment (A)>
In the present invention, as the titanium oxide pigment (A), any crystal structure of anatase type, rutile type or brookite type may be used. Among them, the use of rutile type titanium oxide is preferable because of good pigment dispersibility. In the industrial production of titanium oxide, rutile or ilmenite ore (FeTiO ₃ ) is used as a raw material. There are two main production methods, the chlorine method and the sulfuric acid method, and either method may be used.
Moreover, since the printability in gravure printing is improved, the titanium oxide pigment (A) is preferably subjected to a surface treatment. In particular, those which are surface-treated with at least one metal selected from Si, Al, Zn, Zr and oxides thereof are preferable.

Further, the oil absorption by the measurement method specified in JIS K5101 is preferably 14 to 35 ml / 100 g, and more preferably 17 to 32 ml / 100 g. Moreover, it is preferable that the average particle diameter (median particle diameter) measured with the transmission electron microscope is 0.2-0.3 micrometer. Further, the total content of the titanium oxide pigment (A) is preferably 10 to 60% by weight and more preferably 10 to 45% by weight in 100% by weight of the ink. A plurality of types of titanium oxide pigments may be used in combination.
In the gravure ink of the present invention, other inorganic pigments and organic pigments can be further used in addition to the titanium oxide pigment.

Moreover, it is preferable that solid content weight ratio (A) :( B) of a titanium oxide (A) and binder resin (B) is 15: 10-50: 10, and it is 20: 10-45: 10. Is more preferable.

The organic pigment is not limited to the following examples, but is soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, ansanthrone, dianthraquinonyl, anthrapyrimidine Perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, flavanthrone, diketopyrrolopyrrole, isoindoline, indanthrone, carbon black, etc. These pigments are mentioned. Also, for example, Carmine 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmine FB, Chromophthal Yellow, Chromophthal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance Long blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigment, and the like.

The hue of the organic pigment is preferably at least one selected from the group consisting of black pigments, indigo pigments, green pigments, red pigments, purple pigments, yellow pigments, orange pigments and brown pigments. Furthermore, at least one or more selected from the group consisting of black pigments, indigo pigments, red pigments, and yellow pigments are preferred. Specific examples of preferable organic pigments are shown by generic names of color indexes. C. I. Pigment red 57: 1, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 146, C.I. I. Pigment red 242, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 14, C.I. I. Pigment orange 38, C.I. I. Pigment orange 13, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 139, C.I. I. Pigment red 185, C.I. I. Pigment red 122, C.I. I. Pigment red 178, C.I. I. Pigment red 149, C.I. I. Pigment red 144, C.I. I. Pigment red 166, C.I. I. Pigment violet 23, C.I. I. Pigment violet 37, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 7, C.I. I. Pigment orange 34, C.I. I. Pigment orange 64, C.I. I. Pigment Black 7, and it is preferable to use one or more of them.

On the other hand, as inorganic pigments other than the titanium oxide pigment (A), zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, aluminum particles, mica (mica), bronze powder, chrome vermilion, yellow lead, Examples thereof include cadmium yellow, cadmium red, ultramarine blue, bitumen, bengara, yellow iron oxide, iron black, titanium oxide, and zinc oxide. Aluminum has a leafing type or a non-leafing type, but a non-leafing type is preferable.

<Binder resin (B)>
The binder resin (B) used in the present invention contains 70 to 100% by weight of the total amount of the polyurethane resin (b1) and the vinyl chloride copolymer resin (b2) in 100% by weight of the binder resin (B). The weight ratio is (b1) :( b2) = 95: 5 to 40:60.
Examples of other binder resins include acrylic resins, polyester resins, rosin resins, rosin modified maleic resins, polymerized rosin resins, styrene resins, styrene-maleic resins, maleic resins, polyamide resins, and cellulose resins. One or more of these can be used in combination.

<Polyurethane resin (b1)>
The structure of the polyurethane resin (b1) is not particularly limited, but a polyurethane resin (b1) containing 100 to 50% by weight of a polyether-derived structural unit is preferable. In this case, since the ether group derived from the glycol ether organic solvent (c1) described later, the ether group derived from the polyurethane resin (b1), and water are solvated by hydrogen bonds, the pigment dispersion stability is further improved. Examples of the polyether include polyether polyols and polyether polyamines, and polyether polyols are preferable. The structural unit derived from the polyether is 1% or more, the high solubility due to the interaction with the glycol ether organic solvent (c1) described later is good, the lamination strength and the ink film blocking resistance are 50% by weight or less. Is good. In addition, as content of the structural unit derived from a polyether, More preferably, it is 2 to 40 weight%, More preferably, it is 3 to 30 weight%.
In this specification, content of the structural unit derived from polyether shows weight% of polyether with respect to 100 weight% of solid content of a polyurethane resin (b1).

The weight average molecular weight is preferably 10,000 to 100,000, the glass transition temperature is preferably −60 ° C. to 40 ° C., and the storage elastic modulus at 40 ° C. is 1 to 100 MPa in dynamic viscoelasticity measurement. Are preferred. In the present invention, the glass transition temperature is measured by a differential scanning calorimeter (DSC) and represents the midpoint of the temperature range where the glass transition occurs.

The polyurethane resin (b1) preferably has an amine value or a hydroxyl value, and the amine value is preferably 1.0 to 20.0 mgKOH / g. Moreover, it is preferable that a hydroxyl value is 1.0-20.0 mgKOH / g.

The polyurethane resin (b1) preferably contains a structural unit derived from a polyester polyol, and the content thereof is preferably 5 to 80% by weight, more preferably 100% by weight of the solid content of the polyurethane resin (b1). 30 to 70% by weight.

The polyurethane resin (b1) is not particularly limited, and is appropriately produced by a known method. For example, a polyurethane resin composed of a polyol and a polyisocyanate, a polyurethane resin obtained by reacting a urethane prepolymer of a terminal isocyanate composed of a polyol and a polyisocyanate, and an amine chain extender are preferable.

Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone diol, polycarbonate polyol, polyolefin polyol, castor oil polyol, hydrogenated castor oil polyol, dimer diol, and hydrogenated dimer diol. Of these, polyether polyol and polyester polyol are preferable, and a polyurethane resin (b1) containing a polyether structure and a polyester structure made of these is more preferable.

Furthermore, a low molecular diol may be used in combination for the production of the polyurethane resin (b1). As such a low molecular diol, those having a molecular weight of 50 to 800 are preferable, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3 , 5-trimethylpentanediol, 2,4-diethyl-1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1 -Monoglycerol ether, 2-Monoglycerol ether Ether, dimer diol, hydrogenated dimer diol.

Examples of the polyether polyol include polymer or copolymer polyether polyols such as ethylene oxide, propylene oxide, and tetrahydrofuran. Among them, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol are preferable, and the number average molecular weight is preferably 500 to 10,000. The number average molecular weight is calculated from the hydroxyl value with the terminal being a hydroxyl group, and is obtained from (Equation 1).
(Formula 1) Number average molecular weight of polyol = 1000 × 56.1 × Hydroxyl number / Hydroxyl value

Examples of the polyester polyol include condensates obtained by esterification reaction of dibasic acid and diol. Dibasic acids include adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glutaric acid, 1 4-cyclohexyl dicarboxylic acid, dimer acid, hydrogenated dimer acid and the like. Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and 1,8-octanediol. 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl- 1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimer diol , Hydrogenated dimer diol, etc. It is below. Among these, a polyester polyol composed of a diol having a branched structure and a dibasic acid is preferable. The branched structure means a diol having an alkyl side chain in which at least one hydrogen atom of an alkylene group contained in the diol is substituted with an alkyl group, and includes propylene glycol, 1,3-butanediol, 2-methyl-1 , 3-propanediol, neopentyl glycol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,5-hexanediol, 2-methyl-1,4-pentanediol, 2,4- Diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, And 2,2,4-trimethyl-1,6-hexanediol and the like. These are particularly preferable for improving printability, printing effect, and laminate strength. These polyester polyols can be used alone or in admixture of two or more. The dibasic acid is particularly preferably sebacic acid or adipic acid. Also, a polyol having 3 or more hydroxyl groups and a polyvalent carboxylic acid having 3 or more carboxyl groups can be used in combination.

The number average molecular weight of the polyester polyol is preferably 500 to 10,000. The number average molecular weight is determined by the above (Formula 1). The acid value of the polyester polyol used in the present invention is preferably 1.0 mgKOH / g or less, and more preferably 0.5 mgKOH / g or less.

Examples of the polyisocyanate include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1 , 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, Cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate Nate, dimethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, bis Examples include -chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, dimerized isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group. These may be trimers to form an isocyanurate ring structure. These polyisocyanates can be used alone or in admixture of two or more. Of these, isocyanurate of tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate is preferable.

The amine chain extender is not limited to the following, but preferably has a molecular weight of 500 or less, and examples thereof include diamines and polyfunctional amines, such as ethylenediamine, propylenediamine, hexamethylenediamine, and pentamethylene. In addition to diamine chain extenders such as diamine, isophorone diamine, dicyclohexylmethane-4,4′-diamine, p-phenylenediamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di- 2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, di-2 Diamine chain extender having a hydroxyl group such as hydroxypropyl ethylenediamine can also be used. These chain extenders can be used alone or in admixture of two or more. If necessary, a polyfunctional amine chain extender having three or more functions can also be used. Specifically, diethylenetriamine, iminobispropylamine: (IBPA, 3,3′-diaminodipropylamine), triethylenetetramine N- (3-aminopropyl) butane-1,4-diamine: (spermidine), 6,6-iminodihexylamine, 3,7-diazanonan-1,9-diamine, N, N′-bis (3- Aminopropyl) ethylenediamine. Of these, isophoronediamine, hexamethylenediamine, and iminobispropylamine are preferable.

Moreover, a monovalent active hydrogen compound can also be used as a polymerization terminator for the purpose of terminating excess reaction. Such a compound is not particularly limited as long as it is a monoamine compound having a primary or secondary amino group, and examples thereof include dialkylamines such as di-n-butylamine and aminoalcohols such as 2-ethanolamine. . Furthermore, amino acids such as glycine and L-alanine can be used as a reaction terminator, particularly when it is desired to introduce a carboxyl group into the polyurethane resin. When using a polymerization terminator, the chain terminator and chain extender may be used together to carry out the chain extension reaction, and after the chain extension reaction has been performed to some extent with the chain extender, the end terminator is added alone. Thus, an end termination reaction may be performed. On the other hand, the molecular weight can be controlled without using a terminal terminator, but in this case, a method of adding a prepolymer to a solution containing a chain extender is preferable in terms of reaction control. The polymerization terminator is preferably an amino alcohol, and is preferably used in an amount of 0.01 to 2.0% by weight based on 100% by weight of the polyurethane resin (b1).

In the method of synthesizing the polyurethane resin (b1), it is preferable to react the polyol with polyisocyanate and then react with an amine chain extender and, if necessary, a polymerization terminator to form a polyurethane resin. For example, a polyol and a polyisocyanate are reacted with an inert solvent for an isocyanate group as necessary, and further, if necessary, reacted at a temperature of 50 ° C. to 150 ° C. using a urethanization catalyst (urethanization reaction). And a prepolymer method in which a polyurethane resin is obtained by reacting this prepolymer with an amine chain extender, or a polymer polyol, a polyisocyanate, an amine chain extender and ( And a polymerization stopper) can be produced by a known method such as a one-shot method in which a polyurethane resin (b1) is obtained by reacting in one step. The amine chain extender can also be used in a urethanization reaction with polyisocyanate together with a polymer polyol.

In producing the prepolymer, the amount of polyol and polyisocyanate is the ratio of the number of moles of isocyanate groups in the polyisocyanate to the number of moles of hydroxyl groups in the total of the polymer polyol. NCO / OH ratio = 1.1-3. It is preferable to be in the range of 0.0. More preferably, the NCO / OH ratio is 1.3 to 2.5.

In addition, it is preferable in terms of reaction control to use an organic solvent for the synthesis of the prepolymer. The organic solvent that can be used is preferably an organic solvent that is inactive with isocyanate groups, such as ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dioxane and tetrahydrofuran; ethyl acetate, butyl acetate, propyl acetate, and the like. And the like. These may be used alone or in combination as a mixed solvent.

Furthermore, a catalyst can also be used for the synthesis reaction of this prepolymer. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts are usually used in the range of 0.001 to 1 mol% with respect to the polyol compound.

The above-obtained prepolymer having an isocyanate group at the terminal is reacted with diamine, triamine or the like as an amine chain extender at 10 to 60 ° C., and a high molecular weight polyurethane resin containing an active hydrogen group at the terminal (b1 ) Is obtained.

The ratio of the total number of moles of amino groups of the amine chain extender to the number of moles of isocyanate groups in the prepolymer is 1.01 to 2.00, preferably 1.03 to 1.06. It is preferable to make it react.

<Vinyl chloride copolymer resin (b2)>
Examples of the vinyl chloride copolymer resin (b2) include vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, and the like, but not limited thereto, solubility in organic solvent (C). In particular, a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group and a vinyl chloride-acrylic copolymer resin having a hydroxyl group are particularly preferred. Compared with the case where the pigment dispersion is carried out only with the polyurethane resin (b1), the pigment dispersion having excellent dissolution stability and dispersion stability by further using the vinyl chloride copolymer resin (b2) having a hydroxyl group at the time of pigment dispersion. Can be obtained.

The weight ratio of the polyurethane resin (b1) and the vinyl chloride copolymer resin (b2) (b1) :( b2) in the solvent-type laminating gravure ink of the present invention is preferably 95: 5 to 40:60. Pigment dispersibility is improved. The weight ratio is more preferably 90:10 to 50:50. Within this range, pigment dispersion stability, printability, substrate adhesion, coating film properties and laminate strength are good.

<Vinyl chloride-vinyl acetate copolymer resin>
The vinyl chloride-vinyl acetate copolymer resin is a copolymer of vinyl chloride and vinyl acetate, and the molecular weight is preferably 5,000 to 100,000 in terms of weight average molecular weight, and 20,000 to 70,000. Is more preferable. The structure derived from the vinyl acetate monomer in the solid content of 100% by weight of the vinyl chloride-vinyl acetate copolymer resin is preferably 1 to 30% by weight, and the structure derived from the vinyl chloride monomer is preferably 70 to 95% by weight. . In this case, pigment dispersibility is improved, solubility in an organic solvent is improved, and adhesion to a substrate, film properties, laminate strength, and the like are improved.
A copolymer with a monomer containing a hydroxyl group is more preferred, and the hydroxyl value is preferably 20 to 200 mgKOH / g. The glass transition temperature is preferably 50 ° C to 90 ° C. Examples of the monomer containing a hydroxyl group include vinyl alcohol and hydroxyalkyl acrylate.

<Vinyl chloride-acrylic copolymer resin>
The vinyl chloride-acrylic copolymer resin is mainly composed of a copolymer of vinyl chloride monomer and acrylic monomer. It is preferable that the vinyl chloride-acrylic copolymer resin contains a hydroxyl group in the structure, and as a corresponding acrylic monomer, (meth) acrylic acid hydroxyalkyl ester is used in order to improve adhesion to a substrate and solubility in an organic solvent. It is preferable to include. The acrylic monomer may be incorporated into the main chain of the polyvinyl chloride in a block or randomly, or may be grafted to the side chain of the polyvinyl chloride. The vinyl chloride-acrylic copolymer resin having a hydroxyl group preferably has a weight average molecular weight of 10,000 to 100,000, and more preferably 30,000 to 70,000.

Moreover, it is preferable that the structure derived from the vinyl chloride monomer in the vinyl chloride-acrylic copolymer resin having a hydroxyl group is 70 to 95% by weight in 100% by weight of the solid content of the vinyl chloride-acrylic copolymer resin having a hydroxyl group. In this case, pigment dispersibility is improved, solubility in an organic solvent is improved, and adhesion to a substrate, film properties, laminate strength, and the like are improved. What copolymerized with the monomer containing a hydroxyl group is still more preferable, and it is preferable that it is 20-200 mgKOH / g as a hydroxyl value.

In the following description, (meth) acryl or (meth) acrylate means methacryl and acryl, methacrylate and acrylate, respectively.

Examples of the acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. (Meth) acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate And glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, caprolactone-modified (meth) acrylate And hydroxyethyl acrylamide. Among these, (meth) acrylic acid hydroxyalkyl esters are preferable, and the alkyl group preferably has 1 to 10 carbon atoms. Among them, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl acrylate are more preferable because they improve solubility in solvents. These can be used alone or in combination of two or more.

Moreover, (meth) acrylic-acid alkylester is mentioned as another acrylic monomer, As for carbon number of an alkyl group, 1-10 are preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, (meth) acrylic acid Examples include octadecyl. Furthermore, the alkyl group may further have a benzene ring structure. These can be used alone or in combination of two or more.

In addition, the acrylate ester may have a functional group other than a hydroxyl group, and examples of the functional group include a carboxyl group, an amide bond group, an amino group, and an alkylene oxide group.

Among the acrylic monomers, acrylic acid esters having a hydroxyl group-containing alkyl group are preferable, and those having 2 to 10 carbon atoms are particularly preferable.

In 100% by weight of the gravure ink for solvent-type lamination of the present invention, the total of the polyurethane resin (b1) and the vinyl chloride copolymer resin (b2) having a hydroxyl group is 3.0 to 25.0% by weight in terms of solid content. It is preferably contained at 4.0 to 18% by weight.

<Organic solvent (C)>
The gravure ink for lamination of the present invention contains an organic solvent (C) as a liquid medium. The organic solvent (C) is preferably a non-toluene organic solvent that does not contain an aromatic organic solvent such as toluene or xylene, a ketone organic solvent such as methyl ethyl ketone or methyl isobutyl ketone, ethyl acetate, n-propyl acetate, Known organic solvents such as isopropyl acetate, isobutyl acetate, ester organic solvents, alcohol organic solvents such as methanol, ethanol, 1-propanol (n-propanol), isopropanol, n-butanol, etc. can be used and mixed. May be. Among them, an organic solvent that does not contain a ketone organic solvent such as methyl ethyl ketone (hereinafter referred to as “MEK”) is more preferable. Furthermore, an organic solvent composed of an ester organic solvent and an alcohol organic solvent is most preferable.

In the case of an ester organic solvent and an alcohol organic solvent, the weight ratio of the ester organic solvent to the alcohol organic solvent is desirably 95: 5 to 40:60. More preferably, it is 90: 10-50: 50.

The alcohol-based organic solvent preferably contains 1-propanol, and particularly preferably contains 0.5 to 10.0% by weight of 1-propanol in 100% by weight of the gravure ink for solvent-type lamination.

<Glycol ether organic solvent (c1)>
The gravure ink for solvent-type lamination of the present invention contains 0.1 to 10% by weight of a glycol glycol organic solvent (c1) as the organic solvent (C) in 100% by weight of the ink. Although not limited to that effect, the dissolution stability of the pigment dispersion in the ink is improved by containing the glycol ether organic solvent (c1) in the corresponding range and using it together with water. Moreover, the whitening phenomenon can be suppressed in printing at high temperature and high humidity. The whitening phenomenon occurs because when the solvent is dried and vaporized, it rapidly absorbs moisture in the environment and crystallizes or precipitates. By containing water and the glycol ether organic solvent (c1), the pigment dispersion It is inferred that whitening and the like are unlikely to occur because the solubility and stability of the resin improve. The content of the glycol ether organic solvent (c1) is preferably 0.5 to 7% by weight, more preferably 1.0 to 5% by weight.

Examples of the glycol ether organic solvent (c1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol. Dipropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, methoxyethoxyethanol, ethylene glycol monoallyl ether, etc. Ethylene glycol ether Kind;
Diethylene glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono 2-ethylhexyl ether ;
Triethylene glycol ethers such as triethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether;
Propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, butoxypropanol;
Dipropylene glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether;
And tripropylene glycol ethers such as tripropylene glycol monomethyl ether.

The glycol ether organic solvent (c1) may be esterified, and those obtained by acetate formation of the glycol monoether can be mainly used. Typical examples include ethylene glycol monomethyl ether acetate, ethylene glycol monoester. Examples include ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like. In addition, you may use the said glycol ether type organic solvent (c1) in mixture of 2 or more types.

The glycol ether organic solvent (c1) is preferably at least one compound selected from the group consisting of ethylene glycol ethers, diethylene glycol ethers, propylene glycol ethers and dipropylene glycol ethers.
The ethylene glycol ethers are preferably ethylene glycol monoalkyl ethers, and the propylene glycol ethers are preferably propylene glycol monoalkyl ethers. The alkyl ether group in the ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether preferably has 1 to 4 carbon atoms.
The ethylene glycol monoalkyl ether is more preferably ethylene glycol monopropyl ether or ethylene glycol mono (iso) propyl ether, and the propylene glycol monoalkyl ether is more preferably propylene glycol monomethyl ether.
Further, ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether may be used alone, but it is more preferable to use them together.

Glycol ether organic solvent (c1) is preferred because the solubility of the pigment dispersion is maximized when the solubility parameter is 9.0 to 12.0, more preferably 9.0 to 11.0.
In the present specification, the solubility parameter (hereinafter, sometimes referred to as SP value) represents a value (Hansen solubility parameter) obtained by the formula (2) expressed by the square root of the molecular cohesive energy, and PolymerHandBook Fourth Edition VII. It is described in the chapter.
Formula (2) δ ² = δ _d ² + δ _p ² + δ _h ²
(In the formula (2), δ _d represents the contribution due to the dispersion force, δ _p represents the contribution due to the polar interaction, and δ _h represents the contribution due to the hydrogen bond.)
The unit is (cal / cm ³ ) ^1/2 and refers to the value at 25 ° C. Also, the Hansen solubility parameter values for many solvents have been investigated, see, for example, Wesley L. et al. Also described in Archer, Industrial Solvents Handbook.

In general, the solubility parameter is R.I. F. It can also be calculated by the method described in Fedors, Polymer Engineering Science, 14, p147 (1974). According to Fedors solubility parameter calculation method, both the cohesive energy density and molar molecular volume depend on the type and number of substituents, and are expressed by the following formula (3).
Formula (3) δ = [ΣEcoh / ΣV] ^1/2
(Where ΣEcoh represents cohesive energy and ΣV represents molar molecular volume)
It is known that Fedors solubility parameters are in good agreement with Hansen solubility parameters.

Further, the glycol ether organic solvent (c1) preferably has a boiling point of 110 to 240 ° C. More preferably, it is 110-200 degreeC. Examples of the glycol ether organic solvent (c1) include, but are not limited to, the following.
Ethylene glycol monomethyl ether (SP value 11.6 (cal / cm ³ ) ^1/2 , boiling point 124.5 ° C.)
Diethylene glycol monomethyl ether (SP value 10.7 (cal / cm ³ ) ^1/2 , boiling point 194.0 ° C.)
Ethylene glycol mono-n-propyl ether (SP value 9.8 (cal / cm ³ ) ^1/2 , boiling point 151.0 ° C.)
Ethylene glycol monoisopropyl ether (SP value 9.2 (cal / cm ³ ) ^1/2 , boiling point 141.8 ° C.)
Ethylene glycol monobutyl ether (SP value 9.8 (cal / cm ³ ) ^1/2 , boiling point 171.2 ° C.)
Diethylene glycol monobutyl ether (SP value 9.5 (cal / cm ³ ) ^1/2 , boiling point 230.6 ° C.)
Propylene glycol monomethyl ether (SP value 10.4 (cal / cm ³ ) ^1/2 , boiling point 121.0 ° C.)
Dipropylene glycol monomethyl ether (SP value 9.6 (cal / cm ³ ) ^1/2 , boiling point 187.2 ° C.)
Propylene glycol mono-n-propyl ether (SP value 9.4 (cal / cm ³ ) ^1/2 , boiling point 149.8 ° C.)
In addition, in order to promote improvement in overprinting suitability (trapping property), it is preferable that the surface tension measured by the measurement method according to JIS K 2241 of the du Nouy method (ring method, ring method) is 22.0 to 30.0 mN / m. . Furthermore, a water-soluble thing is preferable.

<Water (D)>
The gravure ink for solvent-type lamination of the present invention contains 0.1 to 6% by weight of water in 100% by weight of the ink. By containing water, aggregation by the hydrogen bond of the urethane bond and urea bond which polyurethane resin (b1) has is prevented, and the thickening of gravure ink and solid content precipitation are suppressed. Further, as described above, the combined use with the glycol ether organic solvent (c1) improves the dissolving power, stability, fluidity and lubricity of the pigment dispersion. In particular, the effect of improving fluidity and lubricity is remarkable when the polyurethane resin (b1) and the vinyl chloride copolymer resin (b2) are provided.
By containing 0.1% by weight or more of water, the ink viscosity is stabilized and the fluidity is improved. Further, when the content is 6% by weight or less, whitening can be suppressed during printing at high temperature and high humidity. The content is preferably 0.5 to 4% by weight in 100% by weight. There is no restriction | limiting in particular about the method at the time of containing water. Water may be contained at the time of pigment dispersion, or after pigment dispersion is completed, water may be added and mixed with stirring.

<Other resins>
The gravure ink for solvent-type laminating in the present invention may contain other polymer materials, and is not limited to the following, but is chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, alkyd Resin, polyvinyl chloride resin, rosin resin, rosin modified maleic resin, terpene resin, phenol modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, and modified resins thereof. it can. These resins can be used alone or in admixture of two or more, and the content thereof is preferably 1 to 20% by weight in 100% by weight of the resin solid content in the gravure ink for solvent-type lamination.

<Additives>
The gravure ink for solvent-type laminating of the present invention can appropriately include known additives as additives, and known additives such as pigment derivatives, extender pigments, dispersants, wets as necessary in the production of ink compositions. Agents, adhesion aids, silica particles, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, wax components, isocyanate curing agents, silane coupling agents, and the like can be used. In addition, since the blocking resistance of a printing layer improves, a fatty acid amide wax and / or a hydrocarbon-type wax are preferable as a wax component.

In order to disperse the pigment stably, the dispersant may be used in combination. As the dispersant, anionic, nonionic, cationic, amphoteric surfactants can be used. From the viewpoint of storage stability of the ink, the dispersant is preferably contained in the ink at 0.1 to 10.0% by weight with respect to 100% by weight of the total ink. Furthermore, it is more preferable that it is contained in the range of 0.1 to 3.0% by weight.

<Manufacture of ink composition>
The gravure ink for solvent-type lamination of the present invention is obtained by dissolving and / or dispersing a titanium oxide pigment (A), a polyurethane resin (b1), and a vinyl chloride copolymer resin (b2) having a hydroxyl group in an organic solvent (C). Can be manufactured. Specifically, for example, an organic pigment, a polyurethane resin (b1), a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group, and, if necessary, the dispersant is mixed and dispersed in an organic solvent (C). A dispersion is produced, and the obtained pigment dispersion is further mixed with a polyurethane resin (b1), a glycol ether solvent (c1), water, or other resin or additive as necessary, to obtain a solvent type. A gravure ink for laminating can be produced. The particle size distribution of the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion processing time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. As the disperser, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.

In the case where bubbles or unexpectedly large particles are included in the ink, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter. A conventionally well-known filter can be used.

<Viscosity>
The viscosity of the gravure ink for solvent-type laminating produced by the above method corresponds to high-speed printing (50 to 300 m / min) in the gravure printing method, so that the viscosity at 25 ° C. with a B-type viscometer is 40 to 700 cps. A viscosity range is preferred. More preferably, it is 50-500 cps. This viscosity range corresponds to a viscosity at Zahn cup # 4 of about 9 to 40 seconds. In addition, the viscosity of the gravure ink for solvent-type lamination is the kind and amount of raw materials used, for example, organic titanium oxide pigment (A), polyurethane resin (b1), vinyl chloride copolymer resin (b2) having a hydroxyl group, organic solvent. It can be adjusted by appropriately selecting an amount such as (C). The viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the organic pigment in the ink.

<Printed matter>
The solvent-type laminating gravure ink of the present invention can be printed by a gravure printing method. For example, it is diluted with a diluent solvent to a viscosity and concentration suitable for gravure printing, and is supplied to each printing unit alone or mixed. After printing on the substrate 1 using the gravure ink for solvent-type laminating of the present invention, a printed layer can be formed by removing a volatile component to obtain a printed matter.

<Substrate 1>
Examples of the substrate 1 that can be used in the printed matter of the present invention include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate, and polylactic acid, polystyrene resins such as polystyrene, AS resin, and ABS resin, nylon, polyamide, and polychlorinated. Examples include film bases made of vinyl, polyvinylidene chloride, cellophane, paper, aluminum, etc., or composite materials of these materials, and vapor-deposited bases that deposit inorganic compounds such as silica, alumina, and aluminum on polyethylene terephthalate and nylon films. A material can also be used. Further, a polyvinyl alcohol or the like may be coated on the vapor-deposited surface of an inorganic compound or the like, and a surface treatment such as a corona treatment may be further performed.

<Substrate 2>
Examples of the substrate 2 include those similar to the substrate 1, and the substrate 1 and the substrate 2 may be the same or different. Although not limited to the following, the base material 2 is preferably aluminum, nylon, unstretched polyolefin, or the like.

<Laminate>
The laminate of the present invention is obtained by sequentially bonding an adhesive layer and a film layer to the printed layer of the printed matter. For example, the usual extrusion laminating (extrusion laminating) method in which a molten polyethylene resin is laminated on the printing layer through various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium, and urethane on the printing surface It is obtained by a known laminating process such as a dry laminating method in which a plastic film is applied and a non-solvent laminating method, or a direct laminating method in which a molten polypropylene is directly pressed and laminated on the printing surface. It is done.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. In the present invention, parts and% represent parts by weight and% by weight unless otherwise noted.

(Hydroxyl value)
It calculated | required according to JISK0070.
(Acid value)
It calculated | required according to JISK0070.
(Amine number)
The amine value was determined according to the following method according to JISK0070 in terms of mg of potassium hydroxide in the same amount as the equivalent of hydrochloric acid required to neutralize the amino group contained in 1 g of resin.
0.5-2 g of the sample was precisely weighed (sample solid content: Sg). To a precisely weighed sample, 50 mL of a mixed solution of methanol / methyl ethyl ketone = 60/40 (mass ratio) was added and dissolved. Bromophenol blue was added as an indicator to the obtained solution, and the obtained solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). The point at which the color of the solution changed from green to yellow was taken as the end point, and the amine titer was determined by the following (formula 2) using the titration amount (AmL) at this time.
(Formula 2) Amine number = (A × f × 0.2 × 56.108) / S [mgKOH / g]

(Weight average molecular weight)
The weight average molecular weight was determined as a converted molecular weight using polystyrene as a standard substance by measuring a molecular weight distribution using a GPC (gel permeation chromatography) apparatus (HLC-8220 manufactured by Tosoh Corporation). The measurement conditions are shown below.
Column: The following columns were used in series.
TSKgel SuperAW2500 manufactured by Tosoh Corporation
TSKgel SuperAW3000 manufactured by Tosoh Corporation
TSKgel SuperAW4000 made by Tosoh Corporation
TSKgel guardcolumn SuperAWH manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Measurement conditions: Column temperature 40 ° C
Eluent: Dimethylformamide Flow rate: 1.0 mL / min

(Synthesis example 1) [Polyurethane resin PU1]
170 parts of a polyester polyol (hereinafter “NPG / AA”) obtained from adipic acid having a number average molecular weight of 2000 and neopentyl glycol, 30 parts of polyethylene glycol (hereinafter “PEG”) having a number average molecular weight of 1000, and isophorone diisocyanate (hereinafter “IPDI”). 58.8 parts and 64.7 parts of ethyl acetate were reacted at 80 ° C. for 4 hours under a nitrogen stream to obtain a solvent for a terminal isocyanate prepolymer. Next, 25.8 parts of isophorone diamine (hereinafter “IPDA”), 2.0 parts of iminobispropylamine (hereinafter “IBPA”), 1.5 parts of 2-ethanolamine (hereinafter “2EtAm”), ethyl acetate / isopropanol (hereinafter referred to as “below”) “IPA”) = To 707.4 parts of a mixed solvent of 70/30, the obtained terminal isocyanate prepolymer solution was gradually added at 40 ° C. and then reacted at 80 ° C. for 1 hour to obtain a solid. A polyurethane resin solution PU1 having an amine value of 30%, an amine value of 11.1 mgKOH / g, a hydroxyl value of 4.8 mgKOH / g, and a weight average molecular weight of 40000 was obtained.

(Synthesis Examples 2 and 3) [Polyurethane resins PU2 and PU3]
Polyurethane resin solutions PU2 and PU3 were obtained in the same manner as in Synthesis Example 1 except that the raw materials shown in Table 1 were used. In Table 1, MPD / AA, PPG and TDI are respectively
MPD / AA: Polyester polyol, which is a condensate of 3-methyl-1,5-pentanediol and adipic acid PPG: Polypropylene glycol TDI: Tolylene diisocyanate (methyl-1,3-phenylene diisocyanate)
Represents.

(Synthesis Example 4) [Vinyl chloride-acrylic copolymer resin PVAc1]
In an autoclave, 1.0 part of potassium peroxodisulfate (K ₂ S ₂ O ₈ ) was dissolved in 500 parts of water and deaerated. After raising the temperature to 60 ° C., 425 parts of a mixture comprising 357 parts of vinyl chloride, 63 parts of 2-hydroxypropyl acrylate, and 5.0 parts of sodium di-2-ethylhexyl sulfosuccinate (product name: Aerosol OT) was placed in the autoclave. In addition, the reaction was performed at 60 ° C. and 6.5 atm. The reaction was continued until the autoclave reached 2.5 atm. Sodium chloride was added to the obtained emulsion for precipitation, and after filtration, washing and drying were performed to obtain a vinyl chloride-acrylic copolymer resin having a hydroxyl group. Further, ethyl acetate was added to obtain a 30% solid solution (PVAc1). The content of 2-hydroxypropyl acrylate in the obtained resin was 14.0%, the weight average molecular weight was 50000, and the glass transition temperature was 70 ° C.

Example 1 [Preparation of Gravure Ink S1 for Solvent Type Lamination]
30 parts of polyurethane resin solution PU1 (solid content 30%), vinyl chloride-vinyl acetate copolymer resin (manufactured by Nissin Chemical Industry Co., Ltd. Solvein TAO vinyl chloride: vinyl acetate: vinyl alcohol = 91: 2: 7 (solid content 30% Ethyl acetate solution)) 5.0 parts, titanium oxide (Taylor JR-806 rutile crystal structure surface treatment with silica and alumina, average particle size 0.27 μm oil absorption 21 (ml / 100 g)), 30 parts, n- 29 parts of a solution of propyl acetate / IPA = 70/30 was mixed and dispersed with an Eiger mill for 20 minutes. Then, while stirring with a disper, 3.0 parts of ethylene glycol monomethyl ether and 3.0 parts of water were mixed to obtain gravure ink S1 for solvent-type lamination.

(Examples 2 to 22) [Creation of gravure inks S2 to S22 for solvent-type lamination]
Except for using the glycol ether solvents shown in Table 2 and the raw materials shown in Table 3, gravure inks S2 to S22 for solvent-type lamination were obtained in the same manner as in Example 1.
In this specification, the ink of Example 22 and printed matter using the same are reference examples.
In Table 3, CR-57, CR-85 and JA-3 represent the following, respectively.
CR-57: manufactured by Ishihara Sangyo Co., Ltd. Titanium oxide Rutile crystal structure Surface treatment with alumina, zirconia and organic matter Average particle size 0.25 μm Oil absorption 17 (ml / 100 g)
CR-85: manufactured by Ishihara Sangyo Co., Ltd. Titanium oxide rutile crystal structure Silica and alumina surface treatment Average particle size 0.25 μm Oil absorption 30 (ml / 100 g)
JA-3: manufactured by Teica, titanium oxide anatase type crystal structure surface untreated, average particle size 0.18 μm, oil absorption 23 (ml / 100 g)

The boiling point in Table 2 of the glycol ether solvent is a catalog value, and the SP value is the Hansen solubility parameter value described in Polymer HandBook (Fourth Edition).

(Comparative Examples 1 to 9) [Creation of gravure inks T1 to T9 for solvent-type lamination]
Except having used the raw material shown in Table 4, the gravure inks T1-T9 for solvent-type lamination were obtained by the method similar to the said Examples 1-22.

(Example 23)
<Printing of gravure ink for solvent lamination>
The viscosity of the gravure ink S1 for solvent-type laminating obtained above was adjusted to 16 seconds (25 by mixing solvent (methyl ethyl ketone “MEK”: n-propyl acetate “NPAC”: isopropanol “IPA” = 40: 40: 20). C., Zahn Cup No. 3), and diluted with a Helio 175 line gradation plate (plate-type compressed, 100% to 3% gradation pattern) with a corona discharge treatment polyester (PET) film of 12 μm thickness (Toyobo) A printed product G1 was obtained by printing at a printing speed of 150 m / min on a corona discharge treated surface of E-5100). The printing conditions were printing at a printing distance of 4000 m under a high temperature and high humidity of 32 ° C. and a humidity of 80%.

The obtained printed matter G1 is further printed with a polyether urethane laminate adhesive (TM320 / CAT13B manufactured by Toyo Morton Co., Ltd.) as an ethyl acetate solution having a solid content of 25% by weight and a 10% by weight to 1.5 g / m ^2. The surface was coated and dried, and further laminated with aluminum-deposited unstretched polypropylene (VMCP 2203, film thickness 25 μm, manufactured by Toray Film Processing Co., Ltd.) to perform dry lamination.

(Examples 24-44)
For the solvent-type laminating gravure inks S2 to S22, printed materials G2 to G22 were obtained in the same manner as in Example 23. Further, each of the printed materials was dry laminated by the same method as described above. Evaluation was performed after the laminate was held at 50 ° C. for 48 hours.

(Comparative Examples 10-18)
About the gravure inks T1 to T9 for solvent-type lamination, printed materials H1 to H9 were obtained in the same manner as in Examples 23 to 44. Further, each of the printed materials was dry laminated by the same method as described above. Evaluation was performed after the laminate was held at 50 ° C. for 48 hours.

The following evaluation was performed on the obtained gravure ink for solvent-type lamination and printed matter, and the results are shown in Table 5-1 (Examples) and Table 5-2 (Comparative Examples).

<Ink stability>
The solvent-type laminating gravure inks S1 to S22 (Examples) and T1 to T9 (Comparative Examples) were stored at 40 ° C. for 14 days. Thereafter, the viscosity was measured to evaluate the change in viscosity before storage. The viscosity was measured at 25 ° C. with Zahn Cup No. Performed with 4 outflow seconds.
5: Viscosity change is less than 3 seconds 4 ... Viscosity difference is 3 seconds or more and less than 6 seconds 3 ... Viscosity difference is 6 seconds or more and less than 10 seconds 2 Is 10 seconds or more and less than 15 seconds 1... Viscosity difference is 15 seconds or more.

<Whitening>
The obtained printed materials G1 to G22 (Examples) and H1 to H9 (Comparative Examples) were stored in an oven at 40 ° C. and a humidity of 90% for 7 days, and the state of the printed surface was observed.
5 ··· No change 4 ··· Whitened portion on the printed surface is less than 5% 3 ··· Whitened portion on the printed surface is 5% or more and less than 20% 2 · · · On the printed surface The whitened portion is 20% or more and less than 50% 1... Front whitening. 5, 4 and 4 are ranges where there is no practical problem.

<Skinning>
Solvent type gravure inks S1 to S22 (Examples) and T1 to T9 (Comparative Examples) for mixed solvents (methyl ethyl ketone “MEK”: n-propyl acetate “NPAC”: isopropanol “IPA” = 40: 40: 20) , Diluted to 500 gram so that the viscosity is 16 seconds (25 ° C., Zaan Cup No. 3), opened in a 1 L glass container and stored in an oven at 40 ° C. for 30 minutes to evaluate the state of skinning did.
5 ... Skinning is not seen on the ink surface 4 ... Skinning is seen on less than 5% of the ink surface 3 ... Skinning is seen on 5% or more but less than 20% of the ink surface 2 ... The skin is seen on 20% or more and less than 50% of the ink surface 1 ... The whole skin is covered 5 and 4 are in a range where there is no practical problem.

<Doctor blade wearability>
Solvent type gravure inks S1 to S22 (Examples) and T1 to T9 (Comparative Examples) for mixed solvents (methyl ethyl ketone “MEK”: n-propyl acetate “NPAC”: isopropanol “IPA” = 40: 40: 20) The sample was diluted so that the viscosity was 16 seconds (25 ° C., Zaan Cup No. 3), and was idled for 180 minutes at a printing speed of 200 m / min and a doctor pressure of 3.0 kgf / cm ² without printing the plate. . Then, using the KEYENCE microscope VH, the blade length of the doctor blade was measured, and the difference from the blade length of the unused doctor blade was defined as the doctor blade wear amount (μm). A doctor blade having a cutting edge thickness of 65 μm (trade name “New Doctor High Blade” (manufactured by Fuji Shoko Co., Ltd.)) was used.
6 ··· Wear amount is less than 30 µm 5 · · · Wear amount is 30 µm to less than 50 µm 4 · · · Wear amount is 50 µm to less than 80 µm 3 · · · Wear amount 80 μm or more and less than 120 μm 2... Wear amount is 120 μm or more and less than 150 μm 1... Wear amount is 150 μm or more. .

<Plate castability>
Plate fogging evaluation was carried out for gravure inks S1 to S22 (Examples) and T1 to T9 (Comparative Examples) for solvent-type laminating. The evaluation was performed based on the colored area on the plate after 60 minutes of idling.
5. The plate cover area is 0% to less than 5%. 4. The plate cover area is 5% to less than 10%. 3. The plate cover area is 10% to 30. 2. The plate covering area is 30% or more and less than 50% 1. The plate covering area is 50% or more. In addition, 5 and 4 are ranges in which there is no practical problem. .

<Lamination strength>
For the obtained printed laminates G1 to G22 (Examples) and H1 to H9 (Comparative Examples), the printed part was cut at a width of 15 mm and peeled off at the ink surface and the substrate surface. ) Was measured with an Intesco 201 universal tensile tester. The practical level is 0.7 N / 15 mm or more.
5 ... Laminate strength is 1.0N / 15mm or more 4 ... Laminate strength is 0.7N / 15mm or more and less than 1.0N / 15mm 3 ... Laminate strength is 0.5N / 15mm or more and less than 0.7N / 15mm 2 ... Laminate strength is 0.3N / 15mm or more and less than 0.5N / 15mm 1 ... Laminate strength is less than 0.3N / 15mm is there.
In addition, 5 and 4 are ranges in which there is no practical problem.

From the evaluation results, the gravure ink for solvent-type laminating of the present invention is a solvent type that has no whitening of the printing layer, less skin peeling and doctor wear due to ink deposition, and good printability in gravure printing under conditions of high temperature and high humidity. It turned out to be a gravure ink for laminating.

Claims (7)

A gravure ink for solvent-type laminating containing a titanium oxide pigment (A), a binder resin (B), an organic solvent (C), and water (D), which satisfies the following (1) to (3) A gravure ink for solvent-type laminating.
(1) Binder resin (B) In 100% by weight, polyurethane resin (b1) and vinyl chloride copolymer resin (b2) are included in a total of 70 to 100% by weight, and the weight ratio of the resin is (b1) : (B2) = 95: 5 to 40:60.
(2) In 100% by weight of the gravure ink, 0.1 to 10% by weight of the glycol ether organic solvent (c1) and 0.1 to 6% by weight of water (D) are contained as the organic solvent (C).
(3) The titanium oxide pigment (A) is a rutile type titanium oxide surface-treated with at least silica and / or alumina, and has an average particle size of 0.2 to 0.3 μm and an oil absorption of 17 to 35 ml / 100 g. is there. 2. The gravure ink for solvent-type laminating according to claim 1, wherein the polyurethane resin (b1) contains a polyether structure and a polyester structure. The solvent parameter lamination gravure ink according to claim 1 or 2, wherein the solubility parameter of the glycol ether organic solvent (c1) is 9.0 to 12.0. The gravure ink for solvent-based laminating according to any one of claims 1 to 3, wherein the boiling point of the glycol ether organic solvent (c1) is 110 to 240 ° C. The gravure ink for solvent-type laminating according to any one of claims 1 to 4, wherein the glycol ether organic solvent (c1) is ethylene glycol monoalkyl ether and / or propylene glycol monoalkyl ether. The printed matter which has the printing layer formed from the gravure ink for solvent-type laminating in any one of Claims 1-5 on the base material 1. The laminated body which has an adhesive bond layer and the base material 2 in order on the printing layer of the printed matter of Claim 6.