JP2019094411A - Gravure ink for laminate and printed matter and laminate of the same - Google Patents

Abstract

To provide a gravure ink for laminate which has good temporal stability of an ink even when using a biomass-derived component, has good characteristics even in various laminated laminate structure, and has good printability.SOLUTION: A gravure ink for laminate contains a polyurethane resin, a rosin resin and a vinyl chloride-vinyl acetate copolymer resin, and satisfies the following (1) and (2): (1) the rosin resin has an acid value of 100 mgKOH/g or less and a softening point of 60-150°C; and (2) the vinyl chloride-vinyl acetate copolymer resin has a hydroxyl value of 30-200 mgKOH/g.SELECTED DRAWING: None

Description

  The present invention relates to a gravure ink for lamination, a printed matter and a laminate thereof.

  When a film substrate such as an OPP film, a PET film, a NY film, a metallized film or the like is used for a packaging material, printing using a printing ink is usually applied for decoration or surface protection of the substrate. The printed substrate is then passed through a slitting process to a laminating process, and finally to a package for food packaging, cosmetic packaging and any other applications.

In many cases, a gravure printing method is employed for printing on the film substrate. The plate used for the gravure printing method is an intaglio plate in which the part such as letters and patterns is an intaglio, soak the ink in the plate to the extent that the ink enters this cell, and scrape the excess ink with the doctor blade while rotating the plate And transfer the gravure ink to the substrate and make it adhere. Since this printing method can express fine gradations, it is suitable for reproduction of rich gradations such as photographs, and is suitable for mass production because high-speed printing is possible.

The pattern printed with gravure ink may be used as the outermost surface of the packaging bag, or may be used as an intermediate layer when the substrate is attached. All are used separately for surface printing and the latter for laminating. This is because there is a method of use as a packaging material appropriate for each case.

In the gravure ink for lamination, after the ink is printed on the substrate, the substrate is further bonded with an adhesive on the printing layer. The methods are roughly classified into three types, an extrusion laminating method, a dry laminating method, and a non-solvent laminating method. In addition to the above-mentioned problems, what is concerned in the laminating step are appearance defects, insufficient laminating strength, resistance to boiling and retorting, etc., various improvements have been made to improve them (Patent Document 1, Patent Document 1) 2, Patent Document 3).

In recent years, the use of biomass-derived materials has attracted attention for environmental response. When a biomass-derived material or raw material is applied to the above-described gravure ink for lamination, it is generally difficult to improve the characteristics as compared with a gravure ink for lamination that does not use a biomass material. In recent years, a gravure ink using a polyurethane resin and a rosin resin in combination has been proposed (Patent Document 4 and Patent Document 5).

JP, 2010-270216, A JP 2005-298618 A JP, 2013-213109, A JP, 2015-160947, A JP, 2015-160949, A

In the present invention, even when a biomass-derived component is used, the temporal stability of the ink is good. It is an object of the present invention to provide a gravure ink for lamination, which is excellent in characteristics even in various laminate laminate configurations, and is further excellent in printability.

  As a result of intensive researches for the above-mentioned problems, the present inventor has found that the solution is achieved by using the gravure ink for lamination described below, and the present invention has been accomplished.

That is, the present invention is a gravure ink for lamination containing a polyurethane resin, a rosin resin and a vinyl chloride-vinyl acetate copolymer resin, and the gravure ink for lamination characterized by satisfying the following (1) and (2): About.
(1) The rosin resin has an acid value of 100 mg KOH / g or less and a softening point of 60 to 150 ° C.
(2) The vinyl chloride-vinyl acetate copolymer resin has a hydroxyl value of 30 to 200 mg KOH / g.

In the present invention, the mass ratio of the rosin resin to the vinyl chloride-vinyl acetate copolymer resin (rosin resin: vinyl chloride-vinyl acetate copolymer resin) is 20:80 to 90:10. The present invention relates to a gravure ink for lamination.

Further, the present invention is characterized in that the rosin resin is an ester condensation resin of a low molecular weight polyol having a number average of molecular weight of 2 to 4 and a number average molecular weight of less than 1,000 and rosin acid. The present invention relates to the gravure ink for laminating.

Further, the present invention relates to the gravure ink for laminating, characterized in that it further contains carnauba wax.

The present invention also relates to a printed material characterized by having a printing layer comprising the gravure ink for lamination on a substrate 1.

The present invention also relates to a laminate, which has a substrate 1, a printing layer comprising the gravure ink for laminating, an adhesive layer and a substrate 2 in this order.

According to the present invention, even when a biomass-derived component is used, the stability over time of the ink is good. It was possible to provide a gravure ink for lamination having good properties in various laminate laminate configurations and further having good printability.

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

The gravure ink for lamination of the present invention is hereinafter sometimes simply referred to as "gravure ink" or "ink", but is the same. Moreover, the layer on which the gravure ink for lamination is printed may be described as “printing layer”, “ink layer” or “ink film”, but is the same.

In the present invention, by using a polyurethane resin, a vinyl chloride-vinyl acetate copolymer resin and a rosin resin having certain requirements in combination as a binder resin, lamination strength and printability are improved. When the acid value and the softening point of the rosin resin are in the above-mentioned range, the base material adhesiveness and the pigment dispersibility become good and the printability is also improved.

<Binder resin>
The binder resin preferably contains a polyurethane resin, a vinyl chloride-vinyl acetate copolymer resin, and a rosin resin in an amount of 60 to 100% by mass in the total mass of the binder resin. It is more preferable to contain by 80-100 mass%. The binder resin is a binder of ink and refers to a thermoplastic resin soluble in an organic solvent.

<Polyurethane resin>
The polyurethane resin preferably has a weight average molecular weight of 10,000 to 100,000, and a glass transition temperature of -60 ° C to 0 ° C. In the present invention, the glass transition temperature is measured by a differential scanning calorimeter (DSC), and represents the middle point of the temperature range in which the glass transition occurs. In the dynamic viscoelasticity measurement, the maximum value of Tan δ may be substituted.

The polyurethane resin preferably has an amine value and / or a hydroxyl value, and the amine value is preferably 1 to 20 mg KOH / g. Moreover, it is preferable that a hydroxyl value is 1-20 mgKOH / g.

The polyurethane resin may or may not have a urea bond, and two or more types may be used in combination.

The polyurethane resin preferably contains a structural unit derived from a polyether polyol, and the content thereof is preferably 0.5 to 30% by mass, and more preferably 1 to 25% in 100% by mass of the solid content of the polyurethane resin. It is mass%. In the present specification, the structural unit derived from polyether polyol shows a structure from the oxygen atom of the hydroxyl group at one end of the polyether polyol which is a raw material of the polyurethane resin to the oxygen atom of the hydroxyl group at the other end, It is a value calculated from the blending amount of polyether polyol.

The polyurethane resin preferably contains a structural unit derived from a polyester polyol, and the content thereof is preferably 30 to 75% by mass, more preferably 40 to 75% by mass in 100% by mass of the polyurethane resin solid content. It is more preferably 45 to 70% by mass. In the present specification, the structural unit derived from polyester polyol refers to the structure from the oxygen atom of the hydroxyl group at one end to the oxygen atom of the hydroxyl group at the other end of polyester polyol which is a raw material of polyurethane resin. Calculated from the compounding amount of

The polyurethane resin preferably contains both a structural unit derived from a polyester polyol and a structural unit derived from a polyether polyol, and the structural unit derived from the polyester polyol and the structural unit derived from the polyether polyol (polyester / polyether) are mass The ratio is preferably 50/50 to 99/1, preferably 60/40 to 90/10, and more preferably 70/90 to 90/10. Is more preferred.

There is no restriction | limiting in particular in a polyurethane resin, For example, it manufactures suitably by the well-known method described in Unexamined-Japanese-Patent No. 2013-213109, 2005-298618. For example, it can be obtained by further reacting a polyamine with a polyurethane resin comprising a polyol and a polyisocyanate, and a urethane prepolymer of a terminal isocyanate comprising a polyol and a polyisocyanate. When using a polyamine, a polyurethane resin is obtained which forms a urea bond by reaction with an isocyanate group. Polyurethane resins containing structural units derived from polyols are preferred.

Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone diol, polycarbonate polyol, polyolefin polyol, castor oil polyol, hydrogenated castor oil polyol, dimer diol, hydrogenated dimer diol and the like. Among them, a combination of polyether polyol and polyester polyol is preferred.

The polyether polyol is preferably, for example, polyethylene glycol, polytetramethylene glycol, polytrimethylene glycol, polypropylene glycol and the like, and two or more of them may be used in combination. The number average molecular weight is preferably 500 to 10,000. The number average molecular weight of the polyol described in the present specification is calculated from the valence number of the hydroxyl group of one molecule of the polyol and the hydroxyl value per 1 g of the solid content of the polyol (converted value of potassium hydroxide in hydroxyl number). And is obtained by (Equation 1).
(Formula 1) Number average molecular weight of polyol = 1000 × 56.1 × valence of hydroxyl group / hydroxyl value

As said polyester polyol, the condensate etc. which are obtained by the esterification reaction of a dibasic acid and diol are mentioned, for example.
Examples of 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 And 4-cyclohexyl dicarboxylic acid, dimer acid, hydrogenated dimer acid and the like. Among them, adipic acid and sebacic acid are preferable.
As the diol, 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-monoglycerin ether, 2-monoglycerin ether, dimer diol , Hydrogenated dimer diol etc. It is below.
The diol is preferably a diol having an alkyl group. The diol having an alkyl group means a diol having a structure in which at least one hydrogen atom of an alkylene group contained in the diol is substituted by an alkyl group, and 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.

Known polyisocyanates can be used as the above-mentioned polyisocyanate, and aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates and the like can be mentioned.
For example, as aromatic diisocyanate, 1,5-naphthyl diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, Examples include tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, m-tetramethyl xylylene diisocyanate, 1,4-phenylene diisocyanate, and tolylene diisocyanate.
Examples of aliphatic diisocyanates include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Moreover, as alicyclic diisocyanate, cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane And methylcyclohexane diisocyanate, norbornane diisocyanate, and dimeric isocyanate obtained by converting the carboxy group of a dimer acid into an isocyanate group.
Among them, aromatic diisocyanates and / or alicyclic diisocyanates are preferred.
Among the above exemplified compounds, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isocyanurate of hexamethylene diisocyanate, and the like are preferable.

The above polyamine refers to an amine compound having at least two amino groups. The polyamine to be a chain extender is not limited to the following, but a molecular weight of 500 or less is preferable, and diamines, polyfunctional amines and the like can be mentioned.
As the diamine, ethylenediamine, propylenediamine, hexamethylenediamine, pentamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, p-phenylenediamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxy Ethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyropirethylenediamine, di-2-hydroxypyropirethylenediamine, di-2-hydroxypropyl A diamine having a hydroxyl group such as ethylene diamine can also be used. These chain extenders can be used alone or in combination of two or more.
As a polyfunctional amine, a triamine etc. are preferable, for example. For example, diethylenetriamine, iminobispropylamine: (IBPA, 3,3'-diaminodipropylamine), triethylenetetramine, N- (3-aminopropyl) butane-1,4-diamine: (spermidine), 6,6 Preferred are iminodihexylamine, 3,7-diazanonane-1,9-diamine and N, N'-bis (3-aminopropyl) ethylenediamine.

The polyamine may contain a compound having a primary or secondary monovalent amino group. These compounds function as polymerization terminators for the purpose of terminating excessive reaction. Preferred examples of such a compound include dialkylamines such as di-n-butylamine and amino alcohols such as 2-ethanolamine.

<Vinyl chloride-vinyl acetate copolymer resin>
The vinyl chloride-vinyl acetate copolymer resin refers to a resin in which vinyl chloride and vinyl acetate are copolymerized. The hydroxyl value of the vinyl chloride-vinyl acetate copolymer resin is 30 to 200 mg KOH / g. A hydroxyl value will not be specifically limited if it is in the said range, It is excellent in the solvent property of resin. In addition, by combining with a polyurethane resin and a rosin resin, adhesion to a substrate, physical properties of a film, laminate strength and the like are excellent. More preferably, it is 50 to 150 mg KOH / g.

The weight average molecular weight of the vinyl chloride-vinyl acetate copolymer resin is preferably 5,000 to 100,000, and more preferably 20,000 to 70,000. The structure derived from vinyl acetate monomer in solid content 100% by mass of vinyl chloride-vinyl acetate copolymer resin is preferably 1 to 30% by mass, and the structure derived from vinyl chloride monomer is preferably 70 to 95% by mass . This is because adhesion to a substrate, film physical properties, laminate strength and the like become good by using a polyurethane resin and a rosin resin described later in combination. Moreover, it is preferable that vinyl chloride and vinyl acetate are 50 degreeC-90 degreeC in glass transition temperature.

<Rosin resin>
The rosin resin used in the present invention is one having a structural unit derived from a rosin acid (abietic acid, neoabietic acid, parastringic acid, pimaric acid, isopimaric acid, dehydroabietic acid, etc.) as a main component (50% by mass or more) Say The rosin acid or rosin resin may be hydrogenated. In addition, the acid value of this rosin resin is 100 mgKOH / g or less, and a softening point is 60-150 degreeC. By using the vinyl chloride-vinyl acetate copolymer resin and the polyurethane resin in combination, the physical properties of the laminate are improved, and the stability of the gravure ink for lamination is improved to improve the printability. Moreover, rosin resin is a biomass raw material derived from pine resin, and contributes to the biomass component improvement in solid content of ink.
Examples of the rosin resin include rosin-modified phenolic resin, rosin ester, rosin-modified maleic acid resin, polymerized rosin resin and the like, and it is preferable to be at least one rosin resin selected from these. As an acid value, 80 mgKOH / g or less is preferable, and it is more preferable that it is 50 mgKOH / g or less. Furthermore, as a softening point, it is preferable that it is 70-130 degreeC. It is because lamination strength improves.

The above-mentioned softening point means a measured value by a ring and ball method. For example, the measuring method as described in JIS K 2207 can be mentioned.

(Rosin ester)
The rosin resin is preferably a rosin ester which is an ester condensation resin of a low molecular weight polyol having a molecular weight of less than 1000 and a rosin acid. The low molecular weight polyol preferably has 2 to 4 hydroxyl groups (sometimes abbreviated as 2 to 4 functions). The low molecular weight polyol more preferably has a molecular weight of 50 to 500.
Examples of the low molecular weight polyol include bifunctional low molecular weight polyols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,10-decanediol, and trifunctional low molecular weight polyols such as glycerin and trimethylolpropane. Preferred are tetrafunctional low molecular weight polyols such as erythritol and pentaerythritol. Among them, trifunctional low molecular weight polyols are preferable.
The weight average molecular weight of the rosin ester is preferably 500 to 2,000. More preferably, it is 500-1500.

The mass ratio of the rosin resin to the vinyl chloride-vinyl acetate copolymer resin (rosin resin: vinyl chloride-vinyl acetate copolymer resin) is preferably 20:80 to 90:10. More preferably, 30:70 to 90:10.
The mass ratio of the polyurethane resin to the vinyl chloride-vinyl acetate copolymer resin (polyurethane resin: vinyl chloride-vinyl acetate copolymer resin) is preferably 95: 5 to 30:70. In addition, it is more preferable that it is 90: 10-40: 60.
The polyurethane resin, the vinyl chloride-vinyl acetate copolymer resin and the rosin resin are preferably contained in a total amount of 3 to 20% by mass, and preferably 5 to 15% by mass in 100% by mass of the gravure ink of the present invention.

<Other binder resin>
The binder resin described above may be used in combination with resins other than those described above as long as the effects of the present invention are not impaired. For example, polyolefin resin, chlorinated polyolefin resin, ethylene-vinyl acetate copolymer resin, polyester resin Acrylic resin, polyamide resin, cellulose resin, urethane-acrylic resin, styrene resin, styrene-acrylic resin, styrene-maleic resin, maleic anhydride resin, maleic resin, vinyl acetate resin, cycloolefin resin, alkyd resin Polyvinyl chloride resin, terpene resin, phenol modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, silicone resin and modified resins thereof are preferable. These resins may be used alone or in combination of two or more, and the content thereof is preferably 0 to 40% by mass, and 0 to 20% by mass with respect to 100% by mass of the solid content of the binder resin. % Is more preferable.

<Pigment>
In the present invention, any of inorganic pigments and organic pigments can be used as the pigment, and although not particularly limited, good substrate adhesion can be obtained by using an organic pigment. Examples of the organic pigment include, but not limited to, soluble azo type, insoluble azo type, azo type, phthalocyanine type, halogenated phthalocyanine type, anthraquinone type, ansanthrone type, dianthraquinonyl type, anthrapyrimidine type, Perylene, Perinone, Quinacridone, Thioindigo, Dioxazine, Isoindolinone, Quinophthalone, Azomethine Azo, Flavanthrone, Diketopyrrolopyrrole, Isoindoline, Indanthrone, Carbon Black, etc. And pigments. Also, for example, carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, chromophal yellow, chromophal red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indance Ron Blue, Pyrimidine Yellow, Thioindigo Bordeaux, Thioindigo Magenta, Perylene Red, Perinone Orange, Isoindolinone Yellow, Aniline Black, Diketopyrrolopyrrole Red, Daylight Fluorescent Pigment, and the like.

Hereinafter, as the organic pigment, at least one or more selected from the group consisting of a black pigment, an amber pigment, a green pigment, a red pigment, a violet pigment, a yellow pigment, an orange pigment and a brown pigment are preferable. In addition, C.I. I. Pigments can be used as appropriate.

On the other hand, examples of the inorganic pigment include white inorganic pigments such as titanium oxide and zinc oxide. Among the inorganic pigments, the use of titanium oxide is particularly preferred. Titanium oxide has a white color and is preferable in view of coloring power, hiding power, chemical resistance and weather resistance, and from the viewpoint of printing performance, the titanium oxide is preferably treated with silica and / or alumina.

Examples of inorganic pigments other than white include aluminum particles, mica (mica), bronze powder, chromium vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, bitumen, red iron oxide, iron black, zinc oxide, etc. Although aluminum is in the form of powder or paste, it is preferably used in the form of paste in terms of handleability and safety, and may be leafing type or non-leafing type.

Among the inorganic pigments, the extender pigment is preferably, but not limited to, barium sulfate, kaolin, clay, calcium carbonate, magnesium carbonate, silica and the like.

The pigment is preferably contained in an amount sufficient to secure the concentration and coloring power of the gravure ink, that is, 1 to 50% by mass, and 2 to 45% by mass in 100% by mass of the total mass of the gravure ink. It is more preferable to do. Moreover, these pigments can be used individually or in combination of 2 or more types.

The hues in the gravure ink of the present invention are, if necessary, ink compositions of other hues (as a basic color, a total of five colors of yellow, red, amber, black and white, white as a process gamut outer color, red (orange), grass (Green), three colors of purple, and further transparent yellow, peony, persimmon, tea, pearl) may be mixed and used.

<Organic solvent>
The gravure ink of the present invention contains an organic solvent as a liquid medium. The organic solvent to be used is preferably a mixed solvent, and is preferably an aromatic organic solvent such as toluene and xylene, a ketone organic solvent such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate Known organic solvents such as ester organic solvents, alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol and the like can be used. Among them, organic solvents (non-toluene based organic solvents) which do not contain aromatic organic solvents such as toluene and xylene are more preferable. More preferably, an organic solvent which does not contain an aromatic organic solvent and / or a ketone organic solvent such as methyl ethyl ketone (hereinafter referred to as "MEK") is more preferable. In particular, one containing an ester organic solvent and an alcohol organic solvent as main components is preferable.

<Additives>
The gravure ink composition of the present invention may appropriately contain known additives as additives, and in the production of the ink composition, known additives such as pigment derivatives, dispersants, wetting agents, and adhesion aids may be used as necessary. An agent, a leveling agent, an antifoaming agent, an antistatic agent, a trapping agent, an antiblocking agent, a wax component, an isocyanate-based curing agent, a silane coupling agent and the like can be used. In order to improve the blocking resistance, it is preferable to contain 0.01 to 3% by mass of carnauba wax as a wax component.

(Carnauba wax)
The carnauba wax is preferably derived from coconut oil. The carnauba wax preferably has a melting point of 60 to 110 ° C. Furthermore, it is preferable that it is 70-100 degreeC.

A dispersing agent can also be used to disperse the pigment stably. As the dispersing agent, surfactants such as anionic, nonionic, cationic and amphoteric surfactants can be used. The dispersant is preferably contained in the ink in an amount of 0.1 to 10.0% by mass with respect to 100% by mass of the total mass of the ink from the viewpoint of storage stability of the ink. Furthermore, it is more preferable to include in the range of 0.1-3.0 mass%.

<Manufacture of gravure ink>
The gravure ink of the present invention can be produced by dissolving and / or dispersing a pigment, a binder resin and the like in an organic solvent. Specifically, for example, a pigment dispersion obtained by mixing an organic pigment, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer resin, and the above-mentioned rosin resin and dispersing it in an organic solvent is produced. A gravure ink can be manufactured by mix | blending resin components, such as a polyurethane resin, and another resin, an additive, etc. as needed. In addition, the particle size distribution of the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the dispersing machine, the filling rate of the grinding media, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. As a dispersing machine, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill, etc. can be used.

The viscosity of the gravure ink for lamination manufactured by the above method corresponds to high-speed printing (50 to 300 m / min) by the gravure printing method, so that the viscosity at 25 ° C. with a B-type viscometer is a viscosity range of 40 to 500 cps Is preferred. More preferably, it is 50 to 400 cps. This viscosity range corresponds to a viscosity of about 9 seconds to 40 seconds in the Zahn cup # 4. The viscosity of the gravure ink can be adjusted by appropriately selecting the type and amount of the raw material used, for example, the amount of the organic pigment, binder resin, organic solvent and the like. 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 material>
The gravure ink of the present invention can be printed by a gravure printing method. For example, it is diluted with a dilution solvent to a viscosity and concentration suitable for gravure printing, and supplied alone or mixed to each printing unit. After printing using the gravure ink composition of this invention on the base material 1, a printing layer can be formed by removing a volatile component, and a printed matter can be obtained.

<Base 1>
Substrates that can be used for the printed matter of the present invention include, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate and polylactic acid, polystyrene, AS resins, polystyrene resins such as ABS resin, nylon, polyamide, polyvinyl chloride And film-like substrates made of polyvinylidene chloride, cellophane, paper, aluminum, etc., or composite materials thereof. In addition, it is possible to use a vapor deposition base material in which an inorganic compound such as silica, alumina, or aluminum is vapor-deposited on polyethylene terephthalate or nylon film, and a vapor deposition treated surface may be further coated with polyvinyl alcohol or the like.
It is preferable that the surface to be printed (surface in contact with the print layer) be subjected to easy adhesion treatment, and examples of easy adhesion treatment include corona discharge treatment, ultraviolet light / ozone treatment, plasma treatment, oxygen plasma treatment, Primer treatment etc. are mentioned. For example, in the corona discharge treatment, a hydroxyl group, a carboxyl group, a carbonyl group or the like is expressed on the substrate. Since hydrogen bonds can be used, the ink preferably contains a compound having a functional group such as a hydroxyl group or an amino group.

<Base material 2>
The base material 2 may be the same as or different from the base material 1, and furthermore, different types of base materials 2 may be stacked to form a laminate. Among them, an unstretched polyolefin substrate is preferable, and an unstretched polyethylene substrate and an unstretched polypropylene substrate are preferable.

<Laminate>
The laminate of the present invention is obtained by further laminating a film layer comprising the substrate 2 in order to the printed layer of the above-mentioned printed matter. The laminate is preferably a laminate including an adhesive layer, and is preferably a laminate having a substrate, a printing layer, an adhesive layer, and a film layer in this order. The film layer may be the same as or different from the substrate.
Examples of the adhesive layer include layers made of an anchor coating agent, a urethane-based laminating adhesive, a molten resin, and the like. Examples of anchor coating agents (AC agents) include imine-based AC agents, isocyanate-based AC agents, polybutadiene-based AC agents and titanium-based AC agents, and as urethane-based laminating adhesives, polyether urethane-based laminating adhesives and polyester-based laminating agents Adhesives and the like can be mentioned, and there are those containing an organic solvent and those containing no solvent. Moreover, as a molten resin, a molten polyethylene etc. are mentioned.
As a method for producing a laminate, for example, a conventional extrusion laminate (extrusion laminate) in which a molten polyethylene resin is laminated via various anchor coating agents such as imine type, isocyanate type, polybutadiene type, titanium type, etc. on a printing layer ), A method such as a dry laminating method or non-solvent laminating method in which an adhesive such as urethane is coated on the printing surface and a plastic film is laminated thereon, and a direct laminating method in which molten polypropylene is directly crimped and laminated on the printing surface. Etc., obtained by a known laminating process.

EXAMPLES Hereinafter, the present invention will be described in detail by way of examples, but the present 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 JIS K0070.
(Acid number)
It calculated | required according to JIS K0070.
(Amine value)
The amine value was determined according to the following method according to JIS K 0070 using 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.
The sample was precisely weighed from 0.5 to 2 g (sample solid content: Sg). To the 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 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). The amine value was determined by the following (Formula 2) using the titration amount (AmL) at the end point as a point where the color of the solution changed from green to yellow.
(Formula 2) Amine titer = (A × f × 0.2 × 56.108) / S [mg KOH / g]

(Softening point)
It measured according to the ring and ball method (JISK2207).

(Weight average molecular weight)
The weight average molecular weight was determined by measuring molecular weight distribution using a GPC (gel permeation chromatography) apparatus (HLC-8220 manufactured by Tosoh Corporation), and determining polystyrene as a converted molecular weight using a standard substance. The measurement conditions are shown below.
Column: The following columns were connected in series and used.
Tosoh Corporation TSKgel SuperAW2500
Tosoh Corporation TSKgel SuperAW 3000
Tosoh Corporation TSKgel SuperAW 4000
Tosoh Corporation TSKgel guardcolumn SuperAWH
Detector: RI (differential refractometer)
Measurement conditions: Column temperature 40 ° C
Eluent: tetrahydrofuran flow rate: 1.0 mL / min

(Synthesis example 1) [polyurethane resin PU1]
Polypropylene glycol having a number average molecular weight of 2000, 80 parts of polyester polyol which is a condensation product of 3-methyl-1,5-pentanediol (hereinafter, "MPD") and adipic acid (hereinafter, "AA"), having a number average molecular weight of 2000 20 parts of (hereinafter "PPG"), 1.5 parts of 1,3-propanediol, 31 parts of isophorone diisocyanate (hereinafter "IPDI"), and 33.1 parts of ethyl acetate are reacted at 80 ° C for 5 hours under a nitrogen stream To obtain a solvent solution of terminal isocyanate urethane prepolymer.
Then 11 parts of isophorone diamine (hereinafter "IPDA"), 1.5 parts of iminobispropylamine (hereinafter "IBPA"), 0.8 parts of 2-ethanolamine (hereinafter "2EtAm"), ethyl acetate / isopropanol (hereinafter "IPA" The resulting terminal isocyanate prepolymer solution is gradually added at 40 ° C. to a mixture of 307.1 parts of a mixed solvent of 60/40, and then reacted at 80 ° C. for 1 hour, and the solid content is 30% A polyurethane resin solution PU1 having an amine value of 4.2 mg KOH / g, a hydroxyl value of 5.0 mg KOH / g and a weight average molecular weight of 50,000 was obtained.

(Synthesis Example 2) [Polyurethane Resin PU2]
70 parts of polyester polyol which is a condensation product of neopentyl glycol (hereinafter "NPG") and sebacic acid (hereinafter "SA") having a number average molecular weight of 2000, 30 parts of PPG having a number average molecular weight of 1000, 28.9 parts of IPDI, and ethyl acetate 32.2 parts were reacted at 80 ° C. for 5 hours under a nitrogen stream to obtain a solvent solution of a terminal isocyanate urethane prepolymer.
Next, the resulting terminal isocyanate prepolymer solution is gradually added at 40 ° C. to a mixture of 11.5 parts of IPDA, 2.0 parts of 2 EtAm, and 300 parts of a mixed solvent of ethyl acetate / IPA = 60/40, and then 80 The mixture was reacted at 0 C for 1 hour to obtain a polyurethane resin solution PU2 having a solid content of 30%, an amine value of 8.9 mg KOH / g, a hydroxyl value of 12.9 mg KOH / g, and a weight average molecular weight of 40000. Sebacic acid is derived from castor oil.

(Synthesis example 3) [polyurethane resin PU3]
50 parts of polyester polyol which is a condensation product of MPD and SA having a number average molecular weight of 2000, 50 parts of a castor oil polyol having a number average molecular weight of 2500 (URIC manufactured by Ito Oil Co., Ltd.), 28.9 parts of IPDI and 39.7 parts of ethyl acetate The mixture was reacted at 80 ° C. for 5 hours under air flow to obtain a solvent solution of a terminal isocyanate urethane prepolymer.
Next, the resulting terminal isocyanate prepolymer solution is gradually added to a mixture of 11 parts of IPDA, 0.5 parts of 2EtAm, and 357.9 parts of a mixed solvent of ethyl acetate / IPA = 60/40 at 40 ° C., and then 80 The mixture was reacted for 1 hour at .degree. C. to obtain a polyurethane resin solution PU3 having a solid content of 30%, an amine value of 5.0 mg KOH / g, a hydroxyl value of 2.7 mg KOH / g and a weight average molecular weight of 60000. The castor oil polyol is derived from castor oil.

Example 1 Preparation of Gravure Ink S1
30 parts of a polyurethane resin solution PU1 (solid content 30%), vinyl chloride-vinyl acetate copolymer resin (Solvain TA5R: manufactured by Nisshin Chemical Industry Co., Ltd. vinyl chloride: vinyl acetate: vinyl alcohol = 88: 1: 11 (hydroxyl value 140 mg KOH) 6 parts of solid content 30% in ethyl acetate solution), 9 parts of the following rosin resin 1 and C.I. I. Pigment Blue 15: 4 (manufactured by Toyo Cara Co., Ltd. Product Name: 10 parts of Lionol Blue FG 7330) and 45 parts of a solution of propyl acetate / IPA = 70/30 are mixed, and dispersed for 20 minutes with an Eiger mill to obtain a gravure ink S1. I got

(Examples 2 to 16) [Preparation of Gravure Inks S2 to S16]
Gravure inks S2 to S19 were obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used.
In addition, the abbreviation in Table 1 represents the following.
・ Solvain AL: Nisshin Chemical Industry Co., Ltd. vinyl chloride-vinyl acetate copolymer resin Hydroxyl value 63 mg KOH / g Solid content 30% Ethyl acetate solution ・ Titanium oxide: manufactured by Tayca Silica / alumina-treated rutile titanium oxide JR 701
· Rosin resin 1: Rosin ester which is an ester condensate of rosin acid and glycerin 10 mg KOH / g, weight average molecular weight 500 to 1,500, softening point 87 ° C solid content 30% ethyl acetate solution · rosin resin 2: rosin acid and penta Rosin ester, which is an ester condensate of erythritol, acid value 25 mg KOH / g, weight average molecular weight 1000-2000, softening point 120 ° C. solid content 30% ethyl acetate solution, rosin resin 3: hydrogenated rosin acid and polyol having a molecular weight of less than 500 Ester condensation product Acid value 5 mg KOH / g, Softening point 70 ° C Solid content 30% Ethyl acetate solution · Rosin resin 4: Rosin modified maleic acid resin Acid value 50 mg KOH / g Softening point 145 ° C Solid content 30% Ethyl acetate solution Note Rosin resin 1 to 4 contain 50% by mass or more of a rosin (pine fat) -derived component.
Carnauba wax: manufactured by Toa Kasei Co., Ltd. Carnauba wax Melting point 70-90 ° C

(Comparative Examples 1 to 8) [Preparation of Gravure Inks SS1 to SS8]
Gravure inks SS1 to SS8 were obtained in the same manner as the methods described in Examples 1 to 19 above, except that the raw materials shown in Table 2 were used. In addition, the abbreviation in Table 2 shows the following.
・ Solvain C: Nisshin Chemical Industry Co., Ltd. vinyl chloride-vinyl acetate copolymer resin hydroxyl group value 0 mg KOH / g solid content 30% ethyl acetate solution ・ Harrier MSR-4: Harima Chemicals Co., Ltd. ・ rosin resin acid value 140 mg KOH / g solid Min 30% ethyl acetate solution

(Example 17)
<Gravure ink printing>
Gravure ink S1 obtained above is mixed solvent (Methyl ethyl ketone "MEK": N propyl acetate "NPAC": isopropanol "IPA" = 40: 40: 20), viscosity is 16 seconds (25 ° C, Zahn cup No) .3) diluted and printed with Helio 175 linear solid plate (plate type compressed, 100% solid pattern) at the printing speed of 100 m / min on the surface treated with corona discharge or alumina of the plastic base shown below The printed materials J1 and K1 were obtained, respectively. The printing conditions were a temperature of 25 ° C. and a humidity of 60%.
-Substrate used for printing of J1: Toyobo Co., Ltd. Biaxially oriented polypropylene (OPP) substrate P2161 Film thickness 20 μm
-Substrate used for printing of K1: Mitsui Chemicals Tosoh Co., Ltd. Alumina-deposited biaxially oriented polyester (alumina-deposited PET) substrate TL-PET HS

<Dry laminating process 1>
On the printed surface of the printed matter J1, a 20% solid content ethyl acetate solution with a urethane-based laminating adhesive (TM320L / hardening agent manufactured by Toyo Moreton Co., Ltd.) was used so that the adhesive layer after drying would be 2.0 g / m ² After coating and drying, a 40 μm thick aluminum-deposited polypropylene film (VMCPP) (ML-WS manufactured by Mitsui Chemicals East Cell Corp. 40 μm thick) was attached to the adhesive layer and dry lamination was performed to obtain a laminate. .
<Dry laminating process 2>
On the printed surface of the printed matter K1, a 20% solid content ethyl acetate solution with a urethane-based laminating adhesive (TM320L / hardening agent manufactured by Toyo Moreton Co., Ltd.) was used so that the adhesive layer after drying would be 2.0 g / m ² After coating and drying, a 40 μm thick unstretched polypropylene film (CPP) (TUXFCS manufactured by Mitsui Chemicals Toshiro Co., Ltd .; film thickness 40 μm) was adhered to the adhesive layer, and dry lamination was performed to obtain a laminate.

(Examples 18 to 32)
Printed materials J2 to J16 and K2 to K16 were obtained in the same manner as in Example 17 except that the inks described in Table 1 were used in the combination described in Table 3. Furthermore, the ink coating surface of each printed material obtained was laminated in the same manner as the above-mentioned dry lamination 1 and dry lamination 2 to obtain a laminate. The evaluation described below was performed after holding the laminate at 40 ° C. for 48 hours.

(Comparative Examples 9 to 16)
Printed materials JJ1 to JJ8 and KK1 to KK8 were obtained in the same manner as in Example 17 except that the inks described in Table 2 were used in the combination described in Table 4. Furthermore, the ink coating surface of each printed material obtained was laminated in the same manner as the above-mentioned dry lamination 1 and dry lamination 2 to obtain a laminate. The evaluation described below was performed after holding the laminate at 40 ° C. for 48 hours.

<Evaluation>
The following evaluation was performed using the gravure ink of the Example and the comparative example, printed matter, and a laminated body. The results are shown in Table 3 and Table 4.

<Temperature stability of ink>
The gravure ink S1 to S16 of the example and the gravure ink SS1 to SS8 of the comparative example were left at 40 ° C. for 7 days, and the viscosity measurement data according to the elapsed time was measured by using Zan cup # 4 manufactured by Rigosha Co., Ltd. The storage stability of the ink was evaluated from the difference in viscosity immediately after finishing and after an elapsed time. In each of the inks, the number of seconds (viscosity) measured with the Zahn cup # 4 before the aging test was in the range of 10 seconds to 30 seconds.
Judgment criteria
5. The change in viscosity over time is less than 1.2 times that after finishing. (Good)
4. The one whose viscosity change over time is 1.2 to 1.5 times immediately after the finish. (Practical use possible)
3. The change in viscosity over time is 1.5 to 2 times that after finishing. (Slightly poor)
2. The change in viscosity over time is at least twice that after finishing. (Defective)
1. What is causing separation, precipitation, separation. (Very bad)
In addition, evaluation with no problem in practical use is 5 or 4.

<Printability (plate cover)>
The plate fog evaluation was performed using the gravure inks S1 to S16 of the example and the gravure inks SS1 to SS8 of the comparative example. The dilution solvent is MEK: NPAC: IPA = 40: 40: 20, the viscosity is 16 seconds (25 ° C.) with Zahn cup # 3, and the area of the plate cover portion after 90 minutes of idle running of the plate in the printing machine It judged visually and evaluated.
Judgment criteria
5. Plate cover area is 0% or more and less than 5% (good)
4. Plate cover area is 5% or more and less than 10% (practical use possible)
3. Plate cover area is 10% or more and less than 15% (somewhat defective)
2. Plate cover area is 15% or more and less than 30% (defect)
1. Plate cover area is over 30% (very poor)
In addition, 5 and 4 are ranges which have no problem in practical use.

<Blocking resistance>
The blocking resistance of the printed matter J1 to J16 (example) and the printed matter JJ1 to JJ8 (comparative example) were evaluated under the following conditions.
(Sample and pressure)
Printed surface of OPP printed matter / OPP non-corona-treated surface 10 kg / cm ²
(Standing conditions) 40 ° C.-80% RH 48 hours (Evaluation method) The printed surface and the substrate were peeled off, and the degree of peeling of the ink film from the printed surface was visually judged.
Judgment criteria
5. There is no peeling of the ink film on the printed surface, and the peeling resistance is low (good)
4. Peeling area of ink film is 1% or more and less than 5%, and peeling resistance is small (practical)
3. Peeling area of ink film 5% or more and less than 20% (slightly poor)
2. Peeling area of ink film is 20% or more and less than 50% (defect)
1. 50% or more peeling of ink film (very poor)
In addition, 5 and 4 are ranges which have no problem in practical use.

<Laminated strength>
About the laminate using printed matter J1 to J16 (example) and printed matter JJ1 to JJ8 (comparative example) and the laminated body using K1 to K16 (example) and printed matter KK1 to KK8 (comparative example) After cutting at 15 mm and peeling on the ink surface and the substrate surface, the peel strength (laminate strength) was measured with an Intesco Co., Ltd. 201 universal tension tester.
Judgment criteria
(In the case of a laminate using printed matter J1 to J16 and printed matter JJ1 to JJ8)
5. Tensile strength is 1.0N / 15mm or more (good)
4. Tensile strength is 0.6N / 15mm or more, less than 1.0N / 15mm (practical)
3. Tensile strength is 0.4 N / 15 mm or more and less than 0.6 N / 15 mm (slightly poor)
2. Tensile strength is 0.2 N / 15 mm or more and less than 0.4 N / 15 mm (defect)
1. Tensile strength is less than 0.2 N / 15 mm (very poor)
In addition, 5 and 4 are ranges which have no problem in practical use.
Judgment criteria
(In the case of a laminate using printed matter K1 to K16 and printed matter KK1 to KK8)
5. Tensile strength is 1.5N / 15mm or more (good)
4. Tensile strength is 1.0N / 15mm or more and less than 1.5N / 15mm (practical)
3. Tensile strength is 0.8N / 15mm or more and less than 1.0N / 15mm (slightly poor)
2. Tensile strength is 0.4 N / 15 mm or more and less than 0.8 N / 15 mm (defect)
1. Tensile strength less than 0.4 N / 15 mm (very poor)
In addition, 5 and 4 are ranges which have no problem in practical use.

The present invention provides a gravure ink for lamination having good stability over time of ink even when using biomass-derived components, good characteristics even in various laminate laminate configurations, and good printability. We were able to.

In addition, it was further satisfied that blocking resistance is also good, and it was shown that it is useful as a gravure ink for environment-friendly lamination for forming a laminate, which is used for a packaging material.

Claims (6)

1. A gravure ink for lamination comprising a polyurethane resin, a rosin resin and a vinyl chloride-vinyl acetate copolymer resin, wherein the gravure ink for lamination is characterized by satisfying the following (1) and (2).
(1) The rosin resin has an acid value of 100 mg KOH / g or less and a softening point of 60 to 150 ° C.
(2) The vinyl chloride-vinyl acetate copolymer resin has a hydroxyl value of 30 to 200 mg KOH / g. The laminate according to claim 1, wherein the mass ratio of the rosin resin to the vinyl chloride-vinyl acetate copolymer resin (rosin resin: vinyl chloride-vinyl acetate copolymer resin) is 20:80 to 90:10. Gravure ink. The rosin resin is characterized in that it is an ester condensation resin of a low molecular weight polyol in which the number of hydroxyl groups per molecule is 2 to 4 and the number average molecular weight is less than 1000, and a rosin acid. The gravure ink for lamination as described in 2. The gravure ink for laminating according to any one of claims 1 to 3, further comprising carnauba wax. A printed material comprising a printing layer comprising the gravure gravure ink according to any one of claims 1 to 4 on a substrate 1. A laminate laminate comprising a substrate 1, a printing layer consisting of the gravure ink for lamination according to any one of claims 1 to 4, an adhesive layer and a substrate 2 in this order.