JP2021143264A - Gravure or flexographic ink and use of the same - Google Patents

Abstract

To provide gravure or flexographic ink using a biomass polyurethane resin which has good printability, laminate strength and printed matter density, and has a small content of a residual solvent in a multilayer printed matter and a laminate.SOLUTION: Gravure or flexographic ink contains a biomass polyurethane resin as a binder resin. The biomass polyurethane resin contains a polyester polyol-derived structural unit and a polyether polyol-derived structural unit that are condensates of a dibasic acid and diol, the dibasic acid contains at least one biomass dibasic acid selected from a succinic acid, a sebacic acid and a dimer acid, the diol contains branched diol and linear diol, and the polyether polyol contains biomass-derived 1,3-propane diol and/or 1,2-propane diol as a structural unit.SELECTED DRAWING: None

Description

The present invention relates to a solvent-type laminating gravure or flexographic ink, and a printed matter and a laminate thereof.

Gravure or flexo ink is widely used for pattern printing for the purpose of imparting beauty and functionality to the printed material, but in recent years, it has become more diverse in packaging, advanced packaging technology, and used as an organic solvent. Demands for printing inks are diversifying year by year, such as environmental measures from the legal and regulatory aspects represented.

Among the gravure or flexographic inks, the ink used for the laminated laminate often uses a polyurethane resin in order to maintain and improve the laminated strength. This is because by selecting isocyanate, polyol, or the like for the polyurethane resin, it is possible to freely design a coating film from a hard and tough coating film to a flexible and elastic coating film.
Furthermore, the use of biomass-derived raw materials that use plants as starting materials cancels out the amount of carbon dioxide emitted by combustion and the amount of carbon dioxide that is absorbed and fixed by the growth of plants, etc., so that carbon dioxide in the air It does not affect the increase or decrease (also called carbon neutral). Therefore, the use of biomass-derived raw materials for gravure for film packaging or polyurethane resin and other ink components used for flexographic ink is an urgent task to avoid an increase in carbon dioxide, which is a greenhouse gas. There is.

Even when a biomass polyurethane resin is used, it is possible to maintain the same performance (lamination strength, printability, etc.) as that of a conventional non-biomass polyurethane resin, and further improvement in performance is required in the future. Therefore, various studies have been conducted on biomass-derived polyester polyols, which are constituent raw materials of polyurethane resins (Patent Documents 1, 2 and 3). However, not all of the properties of the biomass polyurethane resin as an ink raw material have been clarified, and there is a possibility that unexpected problems may occur.

As a packaging bag using a laminated laminate, it is important to suppress deterioration of the contents such as taste and odor. The cause of deterioration of taste and odor is considered to be migration components from the printing layer, but it is also considered that residual components (residual solvent, etc.) contained in the printing layer or laminate formed from the printing ink also have an effect. It is expected that these residual components will remain even after printing ink on a plastic base material such as OPP film, PET film, NY film, and then processing it into a laminated laminate or packaging bag. NS. As described above, the residual solvent in the laminated laminate has not been studied so far. Although it is considered that the properties of the binder resin among the ink constituents affect the amount of residual solvent in the printed matter or laminate, no specific means for reducing the amount of residual solvent has been established.

Furthermore, titanium oxide pigments are mainly used in gravure or flexographic white inks, and the proportion of titanium oxide pigments in the ink composition is high in order to secure the printed matter density. For this reason, it is more difficult to increase the degree of biomass in the ink film and to secure the laminate strength and concentration. Further, the white ink may be printed several times in order to give a feeling of density and concealment, and in that case, there is a concern about the problem of the residual solvent.

Japanese Unexamined Patent Publication No. 2018-95831 JP-A-2018-062642 WO2018 / 199085 Pamphlet Japanese Unexamined Patent Publication No. 2019-203066 Japanese Unexamined Patent Publication No. 2019-218453

An object of the present invention is to provide a gravure or flexographic ink using a biomass polyurethane resin, which has good printability, laminate strength and printed matter density, and also has a small amount of residual solvent in a multilayer printed matter and a laminated laminate.

As a result of diligent studies in view of the above problems, the present inventors have found that the problems can be solved by using the gravure or flexographic ink described below, and have completed the present invention.

The present invention is a gravure or flexographic ink containing a biomass polyurethane resin as a binder resin.
The biomass polyurethane resin contains a constituent unit derived from a polyester polyol which is a condensate of a dibasic acid and a diol and a constituent unit derived from a polyether polyol.
The dibasic acid contains at least one biomass dibasic acid selected from succinic acid, sebacic acid and dimer acid, and the diol contains a branched diol and a linear diol.
The polyether polyol relates to a gravure or flexo ink having 1,3-propanediol and / or 1,2-propanediol derived from biomass as constituent units.

The present invention also relates to the above-mentioned gravure or flexo ink in which the dibasic acid contains 60% by mass or more of succinic acid and / or sebacic acid in 100% by mass of the dibasic acid.

The present invention also relates to the above-mentioned gravure or flexographic ink, wherein the diol contains a branched diol and a linear diol in a mass ratio of 10:90 to 90:10.

The present invention also relates to the above-mentioned gravure or flexographic ink, wherein the linear diol contains a linear diol having 3 to 8 carbon atoms.

Further, in the present invention, the binder resin further contains a vinyl chloride copolymer resin and / or a rosin resin, and the mass ratio of the polyurethane resin to the vinyl chloride copolymer resin and / or the rosin resin is 95: 5 to 30:70 with respect to the gravure or flexo ink.

The present invention also relates to the above-mentioned gravure or flexographic ink in which the biomass degree of the biomass polyurethane resin is 40 to 100% by mass.

The present invention also relates to the above-mentioned gravure or flexo ink, which further contains a titanium oxide pigment and has a biomass degree of 10% or more in a total of 100 mass of the titanium oxide pigment and the binder resin.

The present invention also relates to a printed matter having a printed layer made of the above-mentioned gravure or flexographic ink on the base material 1.

The present invention also relates to a laminate having at least a base material 1, a printing layer made of the above-mentioned gravure or flexographic ink, and a base material 2 in this order.

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a gravure or flexographic ink using a biomass polyurethane resin, which has good printability, laminate strength and printed matter density, and also has a small amount of residual solvent in a multilayer printed matter and a laminated laminate.

The embodiments of the present invention will be described in detail below with reference to examples, but the matters described below are examples or representative examples of the embodiments of the present invention, and the present invention includes these contents as long as the gist thereof is not exceeded. Not limited.

The present invention is, for example, a gravure or flexographic ink for laminating containing a pigment, a binder resin containing a biomass polyurethane resin, and an organic solvent.
By containing the biomass polyurethane resin as a binder resin, it contributes to environmental protection.
The biomass polyurethane resin also contains a constituent unit derived from a polyester polyol, which is a condensation reaction product of a dibasic acid and a diol, and a constituent unit derived from a polyether polyol. The dibasic acid contains at least one kind of biomass dibasic acid selected from succinic acid, sebacic acid and dimer acid, and the diol is suitable as a binder resin by containing a branched diol and a linear diol. It is presumed that it has the effect of imparting hardness and flexibility and reducing the residual solvent in the multilayer printed matter.
Further, the polyether polyol has 1,3-propanediol and / or 1,2-propanediol derived from biomass as a constituent unit, thereby further improving the dispersibility and resolubility of the ink, and the multilayer printed matter and the laminate. It is presumed that it has the effect of reducing the residual solvent in the laminate.

In this specification, "gravure or flexographic ink" may be simply referred to as "ink" or "printing ink", but they are synonymous with each other. A layer formed from gravure or flexo ink is referred to as a "printing layer" or "ink film".

(Binder resin)
The binder resin refers to the binder resin in the laminating gravure or flexographic ink of the present invention, and is preferably a thermoplastic resin soluble in an organic solvent. As the binder resin, it is preferable to use a resin having a glass transition temperature of −80 ° C. or higher and lower than 20 ° C. and a resin having a glass transition temperature of 30 ° C. or higher and lower than 200 ° C. in combination. The former resin preferably contains a polyurethane resin, and the latter resin preferably contains at least one resin selected from a vinyl chloride copolymer resin, a rosin resin, and a cellulose resin. The glass transition temperature is still more preferably −60 ° C. to 0 ° C. for the former and 50 ° C. to 190 ° C. for the latter, respectively. In the present specification, the glass transition temperature is a measured value in the dynamic viscoelasticity measurement, and means a maximum value in Tan δ. The binder resin is preferably contained in an amount of 5 to 15% by mass, preferably 7 to 13% by mass, in the total mass of the ink.

Examples of the binder resin are not limited to the following, but are limited to polyurethane resin, cellulose resin, polyamide resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, rosin resin, and ethylene. -Vinyl acetate copolymer resin, vinyl acetate resin, acrylic resin, styrene resin, dammar resin, styrene-maleic acid copolymer resin, polyester resin, alkyd resin, terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, Examples thereof include rubber chloride, butyral, polyacetal resin, petroleum resin, and modified resins thereof. These resins can be used alone or in admixture of two or more.

The binder resin includes a polyurethane resin containing a biomass polyurethane resin. It is preferable that the total amount of the binder resin contains 30 to 95% by mass of the polyurethane resin. This is because the adhesiveness to the base material is good. As described above, the binder resin is at least one selected from the group consisting of a cellulose resin, a vinyl chloride copolymer resin (vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, etc.) and a rosin resin. It is preferable to contain the resin of. This is because the laminate strength is good.

Further, as described above, the binder resin preferably contains at least two kinds of resins. Above all, the combined use of the polyurethane resin and the vinyl chloride copolymer resin and / or the rosin resin is preferable. The content of the vinyl chloride copolymer resin and / or the rosin-based resin is preferably 1 to 6% by mass in the total mass of the ink. As the vinyl chloride copolymer resin, it is preferable to use a vinyl chloride-vinyl acetate copolymer resin and a vinyl chloride-acrylic copolymer resin. As the rosin-based resin, it is preferable to use a rosin ester or a rosin-modified maleic acid resin.
The mass ratio of the polyurethane resin containing the biomass polyurethane resin to the vinyl chloride copolymer resin and / or the rosin resin is preferably 95: 5 to 30:70, and is preferably 95: 5 to 50:50. It is more preferable, and it is more preferable to include it at 90: 10 to 65:35.
The total amount of the polyurethane resin containing the biomass polyurethane resin and the vinyl chloride copolymer resin and / or the rosin-based resin is preferably 60% by mass or more, and more preferably 70% by mass or more in the total mass of the binder resin. , 80% by mass or more is more preferable.

(Biomass polyurethane resin)
Biomass polyurethane resin refers to a polyurethane resin containing a raw material derived from biomass as a constituent component. The biomass polyurethane resin is preferably contained in an amount of 30% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more in the total mass of the polyurethane resin. The biomass polyurethane resin in the present invention functions as a binder resin. The mass average molecular weight of the biomass polyurethane resin is preferably 1000 to 100,000. More preferably, it is 30,000 to 80,000. When the mass average molecular weight is in the range of 1000 to 100,000, the laminate strength tends to improve. The glass transition temperature is preferably −60 ° C. to 0 ° C., and more preferably −50 ° C. to −30 ° C.

The (biomass) polyurethane resin in the present invention includes a polyurethane resin obtained by condensing a polyol and a polyisocyanate, a urethane prepolymer having an isocyanate group at the terminal which is a condensation reaction product of the polyol and the polyisocyanate, and a polyamine. A polyurethane resin obtained by a reaction with (referred to as chain extension) is preferable. It should be noted that any one of polyol, polyisocyanate and polyamine needs to contain a biomass-derived component.

The polyol used in the biomass polyurethane resin contains a polyester polyol and a polyether polyol, both of which preferably have a number average molecular weight of 400 to 10,000. The raw material polyol preferably contains a polyester polyol in an amount of 50% by mass or more, and more preferably 70% by mass or more. The mass ratio of the polyester polyol to the polyether polyol (the former: the latter) is preferably 50:50 to 99: 1, and more preferably 70:30 to 95: 5.
Further, polyols other than the above polyester polyols and polyether polyols may be used in combination. Examples thereof include polylactone polyols, polycarbonate polyols, polyolefin polyols, castor oil polyols, hydrogenated castor oil polyols, dimer diols, hydrogenated dimer diols and the like.

(Polyester polyol)
The polyester polyol is a polyester polyol obtained by condensing a dibasic acid and a diol, and a part or all of the dibasic acid is a biomass dibasic acid, and a part or all of the diol is a biomass diol.

The biomass dibasic acid includes at least one kind of biomass dibasic acid selected from succinic acid, sebacic acid and dimer acid among the dibasic acids listed above. It is still preferable that the biomass dibasic acid contains succinic acid and / or sebacic acid. The biomass dibasic acid is preferably contained in an amount of 60% by mass or more, more preferably 70% by mass or more, and more preferably 85% by mass or more in the total mass of the dibasic acid constituting the raw material of the polyester polyol. More preferably, it is particularly preferably composed of only biomass dibasic acid.
Biomass dibasic acids such as succinic acid, sebacic acid and dimer acid can be obtained as commercial products of Itoh Oil Chemicals, Inc., for example. The dibasic acid may contain a dibasic acid other than the biomass dibasic acid.

The diols that are not biomass in the above are diethylene glycol, 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-. Methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl-1,5-pentanediol, 1,12-octadecandiol, etc. can be mentioned, and the biomass diol is ethylene glycol. , Triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, dimerdiol, hydrogenated dimerdiol, and the like. Biomass diols and non-biomass diols may be used in combination, and there are no particular restrictions.

In polyester polyols, the diols include both branched diols and linear diols. As a result, the lamination strength in the laminate becomes better. Here, the linear diol is a compound having two hydroxyl groups, and refers to alkylene glycol, dialkylene glycol, trialkylene glycol and other diols.
Further, the branched diol refers to a diol in which at least one hydrogen atom of the hydrocarbon group of the alkylene glycol is substituted with a hydrogen atom other than the hydrogen atom. Each of the branched diol and the linear diol may optionally contain a diol derived from biomass. Since the linear diol imparts crystallinity and the branched diol imparts flexibility, the polyurethane resin as the binder resin has a tough ink film and high lamination strength can be obtained due to the balance.

Examples of the branched diol include 2-butyl-2-ethyl-1,3-propanediol (hereinafter, also referred to as BEPG), 2-methyl-1,3-propanediol (hereinafter, also referred to as MPO), and the like. 3-Methyl-1,5-pentanediol (also referred to as MPD), neopentyl glycol (also referred to as NPG), 1,2-propylene glycol (hereinafter also referred to as PG), 2,4-diethyl-1, 5-Pentanediol, 1,3-butanediol, dipropylene glycol and the like are preferably mentioned. Among them, at least one branched diol selected from MPO, MPD, BEPG, NPG, PG, 2,4-diethyl-1,5-pentanediol is preferable, and NPG and / or BEPG is more preferable. , BEPG is particularly preferred. Among them, the number of carbon atoms of the branched diol may be 3 or more, preferably 4 to 12, and even more preferably 4 to 10.

The linear diol is preferably alkylene glycol, and such compounds include ethylene glycol (also referred to as EG), diethylene glycol, 1,3-propanediol (also referred to as 1,3PD), and 1,4. -Butandiol (also referred to as 1,4-BD), 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,4-butanediol, 1, Examples thereof include 4-butylenediol, diethylene glycol and triethylene glycol.
Among them, the linear diol preferably has 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms. 1,3PD, 1,4-BD, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and the like are preferable.

The branched diol unit and the linear diol unit may be present in one kind of polyester polyol, or the polyester polyol containing only the branched diol unit and the polyester polyol containing only the linear diol unit. May be used as a raw material for a mixture and used as a biomass polyurethane resin. Approximately the same effect can be obtained.
Further, in 100% by mass of the above diol, the branched diol and the linear diol are preferably contained in a mass ratio (branched diol: linear diol) from 10:90 to 90:10, and 30: It is more preferably contained at 70 to 80:20, and even more preferably at 40:60 to 70:30. This is because these compositions have the effect of improving the resolubility, the lamination strength, and the residual solvent of the multilayer printed matter or the laminate.

(Other polyester polyols)
The polyester polyol may contain a polyester polyol that does not contain a biomass dibasic acid unit such as succinic acid, sebacic acid and dimer acid as an auxiliary, and is a polyester polyol obtained by condensing a dibasic acid and a diol. The dibasic acids include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, oxalic acid, malonic acid, glutaric acid, pimeric acid, speric acid, azelaic acid, trimellitic acid, pyromellitic acid, Etc., and succinic acid, sebacic acid and dimer acid which are not derived from biomass are not excluded.

The biomass polyurethane resin in the present invention preferably has the following biomass content of 40 to 100% by mass, more preferably 55 to 100% by mass. Further, the biomass degree in the non-volatile content of the gravure or flexo ink having the binder containing the biomass polyurethane resin in the present invention, that is, the biomass degree of the printing layer is preferably 5% by mass or more, and preferably 7% by mass or more. It is preferably 10% by mass or more, and more preferably 10% by mass or more.

The biomass degree refers to the ratio of plant-derived and other biomass-derived components contained in the compound. That is, the biomass degree is a value represented by the following formula (4).

Equation (4) Biomass degree = 100 × total mass of biomass-derived components in the compound / total mass of the compound

However, if the compound is a reaction product of a biomass-derived raw material and a non-biomass-derived raw material, it is calculated by converting it into a raw material before the reaction. For example, in the case of a polyester resin (polyester polyol) which is a reaction product of dibasic acid and diol.

Biomass degree = 100 x (biomass dibasic acid + biomass-derived diol) / (all dibasic acids + all diols)

Is. "All dibasic acids" refers to the sum of biomass-derived dibasic acids and non-biomass-derived dibasic acids, and refers to the sum of "all diols" and biomass-derived diols and non-biomass-derived diols.

(Polyether polyol)
The above-mentioned polyether polyol has 1,3-propanediol derived from biomass and / or 1,2-propanediol as a constituent unit. For example, a polyether polyol formed only from 1,3-propanediol becomes polytrimethylene glycol, and a polyether polyol formed only from 1,3-propanediol becomes polypropylene glycol. A form in which these 1,3-propanediol and 1,2-propanediol are copolymerized polyether polyols is also preferable. The biomass-derived 1,3-propanediol and / or the constituent unit derived from 1,2-propanediol is preferably contained in an amount of 50% by mass or more, preferably 70% by mass or more, in 100% by mass of the polyether polyol. It is still preferable.
The former: the latter is preferably 50:50 to 99: 1, more preferably 70:30 to 98: 2, and further preferably 80:20 to 95: 5. preferable. It is considered to contribute to the residual solvent in the laminated laminate, the resolubility of the ink, the pigment dispersibility (concentration), and the laminate strength.

(Other polyether polyols)
The above-mentioned polyether polyol may contain a polyether polyol having no biomass-derived 1,3-propanediol and / or 1,2-propanediol as a constituent unit, and examples of such a polyether polyol include polyethylene glycol. Examples thereof include polytetramethylene glycol and copolymers thereof. It does not exclude polytrimethylene glycol and polypropylene glycol that are not derived from biomass.
Further, for example, diethylene glycol, 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 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, A polyether polyol formed by ether bonding diols such as 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, and 2-monoglycerin ether may be used.

In the biomass polyurethane resin, the polyester polyol and the polyether polyol are used in combination in the polyol constituting the polyurethane resin, and the biomass dibasic acid in the dibasic acid constituting the biomass polyester polyol is 60% by mass or more, and When the branched diol and the linear diol are used in combination in a predetermined ratio, the characteristics of the biomass polyurethane resin work integrally as a cohesive structure, and the residual solvent in the laminated laminate, the resolubility of the ink, and the pigment dispersibility (concentration). ), It is considered to contribute to the lamination strength. The more preferable range is the same as the above range.

As the polyisocyanate, diisocyanate is preferable, and as the compound, various known diisocyanates of aromatic, aliphatic or alicyclic group can be used. For example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylenedi isocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexanediisocyanate, m- Typical examples include tetramethylxylylene diisocyanate and dimerized isocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group. These can be used alone or in combination of two or more. Of these, isophorone diisocyanate, tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate are preferable, and isophorone diisocyanate is more preferable from the viewpoint of solubility.

The polyamine is preferably an organic diamine, and examples of such diamines include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, and dicyclohexylmethane-4,4'-diamine. In addition, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyro Amines having a hydroxyl group in the molecule, such as pyruethylenediamine and di-2-hydroxypyrropyrethylenediamine, can also be used. These organic diamines can be used alone or in combination of two or more, but isophorone diamine is preferable. In addition, diethylenetriamine, iminobispropylamine: (IBPA, 3,3'-diaminodipropylamine), N- (3-aminopropyl) butane-1,4-diamine: (spermidine), 6,6-iminodihexylamine. , 3,7-Diazanonan-1,9-diamine, N, N'-bis (3-aminopropyl) ethylenediamine and other polyfunctional amines having 3 or more amino groups can be used in combination with the above organic diamine.

In the present invention, the polyurethane resin preferably has an amine value. The amine value of the polyurethane urea resin is preferably 0.5 to 15 mgKOH / g, and more preferably 1 to 13 mgKOH / g. Within this range, the lamination strength with respect to the base material tends to improve.

In the chain extension reaction using a polyamine, a monoamine may be used as a reaction terminator. Examples of the reaction terminator include dialkylamines such as dibutylamine, diethylamine, and dipropylamine, as well as monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, and the like. Amines having a hydroxyl group such as the above can also be used.

(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 is 20,000 to 70,000. Is more preferable. The structure derived from the vinyl acetate monomer in 100% by mass of the solid content of the vinyl chloride-vinyl acetate copolymer resin is preferably 1 to 30% by mass, and the structure derived from the vinyl chloride monomer is preferably 70 to 95% by mass. .. In this case, the solubility in an organic solvent is improved, and the adhesion to the substrate, the physical characteristics of the film, the lamination strength and the like are improved.
Further, in order to improve the solubility in an organic solvent, those containing a hydroxyl group derived from vinyl alcohol by saponification reaction or copolymerization are more preferable, and the hydroxyl value is preferably 20 to 200 mgKOH / g. The glass transition temperature is preferably 50 ° C to 90 ° C.

(Vinyl chloride-acrylic copolymer resin)
The vinyl chloride-acrylic copolymer resin contains a copolymer resin of a vinyl chloride monomer and an acrylic monomer as a main component, and as the acrylic monomer, the adhesiveness to the base material and the solubility in the organic solvent are improved (meth). ) It is preferable to contain an acrylic acid hydroxyalkyl ester. The acrylic monomer may be blocked or randomly incorporated into the main chain of polyvinyl chloride, or may be graft-polymerized on the side chain of polyvinyl chloride. The vinyl chloride-acrylic copolymer resin preferably has a weight average molecular weight of 10,000 to 100,000, and more preferably 30,000 to 70,000. The hydroxyl value is preferably 20 to 200 mgKOH / g, and the glass transition temperature is preferably 50 ° C to 90 ° C.

The structure derived from the vinyl chloride monomer in the vinyl chloride-acrylic copolymer resin is preferably 70 to 95% by mass based on 100% by mass of the vinyl chloride-acrylic copolymer resin solid content. In this case, the solubility in an organic solvent is improved, and the adhesion to the substrate, the physical characteristics of the film, the lamination strength and the like are improved.

In the following description, (meth) acrylic or (meth) acrylate means methacrylic and acrylic, methacrylate and acrylate, respectively.

The acrylic monomer preferably contains one having a hydroxyl group, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). (Meta) such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate. ) Acrylic acid hydroxyalkyl ester, glycol mono (meth) acrylate such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, caprolactone modified (meth) Examples thereof include acrylate and hydroxyethyl acrylamide. Among these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl acrylate are more preferable because they improve the solubility in a solvent. These can be used alone or in combination of two or more. An acrylic monomer other than the above may be contained at any time.

(Rosin resin)
The rosin-based resin used in the present invention refers to a resin having a structural unit derived from loginic acid (abietic acid, neoavietic acid, palastolic acid, pimaric acid, isopimalic acid, dehydroabietic acid, etc.). The rosin acid or rosin resin may be hydrogenated. The acid value of the rosin-based resin is 100 mgKOH / g or less, and the softening point is 60 to 150 ° C. The rosin-based resin is a biomass raw material derived from pine fat, and contributes to the improvement of the biomass content in the ink solid content and the improvement of the lamination strength and the like. Preferable examples of the type of rosin-based resin include rosin-modified phenolic resin, rosin ester, rosin-modified maleic acid resin, and polymerized rosin-based resin. Of these, the combined use of polyurethane resin, rosin ester, and rosin-modified maleic acid resin is preferable.

(Rosin ester)
The rosin-based 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 small molecule polyol preferably has 2 to 4 hydroxyl groups. Further, the small molecule polyol 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. , A tetrafunctional low molecular weight polyol such as erythritol and pentaerythritol are suitable. Of these, trifunctional small molecule polyols are preferred. The weight average molecular weight of the rosin ester is preferably 500 to 2000. More preferably, it is 500 to 1500.

(Rosin-modified maleic acid resin)
The rosin-modified maleic acid resin is a resin having a structure derived from rosin and a structure derived from maleic acid and / or maleic anhydride, and can contain a component derived from a polyhydric alcohol, if necessary. As the rosin, gum rosin, tall oil rosin, wood rosin, polymerized rosin and the like can be used, and as the polyhydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, glycerin and trimethylol can be used. Examples thereof include ethane, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol, pentaerythritol, sorbitol, and tertiary alkanolamine. In addition, other fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic acid, methacrylic acid, saturated acids and fatty acids, long-chain alkyl compounds having polar groups, surfactants and the like may be contained.

(Organic solvent)
The ink of the present invention preferably contains an organic solvent as a liquid medium. The organic solvent used is preferably used as a mixed solvent, such as aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate. , Ester-based organic solvents, alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and other known organic solvents can be used. Of these, an organic solvent (non-toluene-based organic solvent) that does not contain an aromatic organic solvent such as toluene or xylene is more preferable. More preferably, it is an organic solvent that does not contain an aromatic organic solvent and / or a ketone-based organic solvent such as methyl ethyl ketone (hereinafter referred to as "MEK"), and the ester-based organic solvent is the main component (all organic solvent) in the organic solvent. It is preferably contained as (50% by mass or more). In particular, those containing an ester-based organic solvent and an alcohol-based organic solvent are preferable.

(Pigment)
The gravure or flexo ink in the present invention preferably contains a pigment as a colorant, and preferably an inorganic pigment or an organic pigment. C.I. described in the color index. I. Pigments can be used as appropriate.

(Inorganic pigment)
Examples of the inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, aluminum particles, mica (mica), bronze powder, chromium vermilion, yellow lead, cadmium yellow, and cadmium red. Ultramarine blue, dark blue, red iron oxide, yellow iron oxide, iron black, titanium oxide, zinc oxide and the like can be mentioned. Aluminum has a leafing type and a non-leafing type, but the non-leafing type is preferable.

(Titanium oxide)
In the present invention, titanium oxide may have a crystal structure of any of anatase type, rutile type and brookite type. Of these, rutile-type titanium oxide is preferably used because it has good pigment dispersibility. In the industrial production of titanium oxide, rutile ore or ilmenite ore (FeTIO ₃ ) is used as a raw material. There are two main manufacturing methods, the chlorine method and the sulfuric acid method, and any manufacturing method may be used.
Further, titanium oxide is preferably surface-treated in order to improve printability in gravure printing. In particular, those surface-treated with at least one metal selected from Si, Al, Zn, Zr and their oxides are preferable. It is still preferable that the surface is treated with silica and / or alumina. The term "surface treated" means that the surface of titanium oxide is coated with the compound to be treated.

Further, the oil absorption amount according to the measurement method specified in JIS K5101 is preferably 14 to 35 ml / 100 g, and more preferably 17 to 32 ml / 100 g. Further, the average particle size (median particle size) measured by a transmission electron microscope is preferably 0.2 to 0.3 μm. The total content of titanium oxide is preferably 10 to 60% by weight, more preferably 10 to 45% by weight, based on 100% by weight of the ink. Further, a plurality of types of titanium oxide may be used in combination. In the present invention, the mass ratio of titanium oxide to the binder resin (titanium oxide / binder resin) is preferably 2.8 to 5, and more preferably 3.2 to 4.5. Further, in addition to the titanium oxide pigment, other inorganic pigments and organic pigments can be further used in combination.

(Organic pigment)
The organic pigments are not limited to the following examples, but are soluble azo type, insoluble azo type, azo type, phthalocyanine type, halogenated phthalocyanine type, anthraquinone type, anthraquinone type, dianslaquinonyl type, and anthrapyrimidine type. , Perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethinazo, flavanthron, diketopyrrolopyrrole, isoindoline, indanslon, carbon black, etc. Pigments can be mentioned.
Speaking of product names, for example, Carmin 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmin FB, Chromophtal Yellow, Chromophtal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Kinacridone Magenta, Kinacridone. Examples thereof include red, indanceron blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigment.

The pigment is preferably contained in an amount sufficient to secure the density and coloring power of the ink, that is, in a ratio of 1 to 50% by mass with respect to the total mass of the printing ink. It is still more preferable that it is contained in an amount of 3 to 25% by mass.

(Other additives)
The ink of the present invention is a leveling agent, a defoaming agent, a wax, a silane coupling agent, a plasticizer, a light stabilizer, silica particles, an infrared absorber, an ultraviolet absorber, a fragrance, a flame retardant, and a curing agent, if necessary. Additives such as agents can also be included.

(Ink manufacturing method)
In the gravure or flexo ink in the present invention, for example, a binder resin containing titanium oxide and a biomass polyurethane resin, an organic solvent, and the like are mixed in advance with a stirring mixer, and the mixture is further mixed in a pigment dispersion step using a disperser such as a bead mill. The ink of the present invention can be produced by additionally mixing a binder resin, various additives, an organic solvent, etc. with the obtained dispersion.
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. The particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the pulverized media of the disperser, the filling rate of the pulverized media, the dispersion treatment time, the discharge rate of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. Further, in the present invention, it can also be applied to a medium or the like containing no pigment.

The viscosity of the gravure or flexo ink is in the range of 10 mPa · s or more at 25 ° C. from the viewpoint of preventing the pigment from settling and appropriately dispersing, and 1000 mPa · s or less from the viewpoint of workability efficiency during ink production and printing. Is preferable. It is still more preferable that it is 20 to 500 mPa · s. For the above viscosity, a viscosity value measured at 25 ° C. with a B-type viscometer manufactured by Tokimec Co., Ltd. can be adopted.

(Printing of gravure or flexo ink)
The ink in the present invention can also be used in a gravure printing method and a flexographic printing method. In gravure printing, it is diluted with a diluting solvent to a viscosity and concentration suitable for printing and supplied to each printing unit alone or in combination.

(Gravure printing)
When the gravure or flexo ink in the present invention is gravure-printed, it is printed using a gravure plate. In the present invention, the gravure plate is a metal cylindrical one, and recesses are created in each color by engraving, corrosion, or laser. There are no restrictions on the use of engraving and laser, and it can be set arbitrarily according to the pattern. As the number of lines, those of 100 lines to 300 lines / inch are appropriately used, and the larger the number of lines, the higher the definition of printing.
(Printer)
As the printing machine, a printing machine provided with the above gravure plate can be preferably used. Normally, a printing unit is installed for each color, and a doctor blade that scrapes ink at the same time as the gravure plate rotates is placed in each unit, and the base material passes through each printing unit and is intaglio printed and then film-wound. It will be a gift. It is possible to use a finisher roll for the gravure version as the case may be. In addition, each unit is provided with a drying oven, and the printed base material is dried through the oven. The drying temperature is usually about 40 to 60 ° C.

(Flexographic printing)
Examples of the plate used for flexographic printing in the present invention include a photosensitive resin plate that utilizes ultraviolet curing by a UV light source or an elastomer material plate that uses a direct laser engraving method. Regardless of the method of forming the image portion of the flexographic plate, a plate having a screening line number of 75 lpi or more is used. Any sleeve or cushion tape can be used to attach the plate.
(Printer)
Flexographic printing machines include CI type multicolor flexographic printing machines, unit type multicolor flexographic printing machines, etc., and the ink supply method can be a chamber method or a two-roll method, and an appropriate printing machine can be used. can.

(Base material 1)
The gravure or flexographic ink of the present invention is printed on the base material 1 to obtain a printed matter.
Examples of the base material 1 to which the gravure or flexo ink of the present invention can be applied include polyethylene, polypropylene and other polyolefin base materials, polycarbonate base materials, polyester base materials (polyethylene terephthalate, polylactic acid, etc.), polystyrene base materials, AS resins or ABS resins. Polystyrene-based base material, polyamide base material, polyvinyl chloride base material, various base materials of polyvinylidene chloride, cellophane base material, paper base material, aluminum foil base material, etc., or a film made of a composite material thereof, or There is a sheet-like one. Of these, polyester base materials and polyamide base materials having a high glass transition temperature are preferably used.

The surface of the base material 1 may be coated with a metal oxide or the like by vapor deposition and / or a coating treatment such as polyvinyl alcohol. For example, GL manufactured by Toppan Printing Co., Ltd., in which aluminum oxide is vapor-deposited on the surface of the base material. -AE, IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd., and the like can be mentioned. Further, if necessary, those treated with additives such as antistatic agents and ultraviolet protective agents, and those treated with corona treatment or low temperature plasma treatment on the surface of the base material can also be used.

(Laminated body)
The laminate of the present invention can be obtained by further providing an adhesive layer on the printing layer on the base material 1 formed by gravure or flexographic ink, and laminating (laminating) the laminated body with the base material 2. As a typical example of the laminating process, extrusion laminating, dry laminating, non-sol laminating method and the like are preferably mentioned. Extrusion laminating is a method in which an anchor coating agent is applied onto a printed layer of printed matter, a molten polyethylene resin, a molten polypropylene resin, or the like is extruded therein, and at the same time, the molten polyethylene resin and the molten polypropylene resin are bonded to each other and laminated. The dry laminating method and the non-sol laminating method are methods in which an adhesive is applied onto a printed layer of a printed matter, dried, and thermocompression bonded to a sealant for laminating. The difference between the dry laminating method and the non-sol laminating method is whether or not an organic solvent or other volatile medium is contained.

(Adhesive layer)
The adhesive layer refers to a composition capable of adhering the above ink and a base material, and is a layer formed of molten polyethylene resin, molten polypropylene resin, urethane adhesive, a layer formed of acrylic adhesive, and an anchor coat. Layers and the like can be mentioned. For example, it is obtained by applying a urethane adhesive and drying it. As the urethane adhesive, a two-component adhesive composed of a mixture of a polyol and an isocyanate curing agent is preferable, and examples of the polyol include polyester-based adhesives and polyether-based adhesives. Specific examples thereof include TM-250HV / CAT-RT86L-60, TM-550 / CAT-RT37, TM-314 / CAT-14B manufactured by Toyo Morton Co., Ltd.

(Base material 2)
The base material 2 may be the same as the base material 1, and may be the same or different. It is preferably a thermoplastic base material (sometimes referred to as a sealant), and a non-stretched polyethylene base material, a non-stretched polypropylene base material, a non-stretched polyester base material, or the like is preferable.

The gravure or flexo ink of the present invention is preferably an embodiment for laminating. "For laminating" means a usage pattern in which the base material 1, the printing layer formed from the ink of the present invention, and the base material 2 are laminated in this order, and the base material 1, the printing layer, and the adhesive layer are used. A form in which the base material 2 and the base material 2 are provided in this order is more preferable.

Hereinafter, the present invention will be described in detail with reference to examples, but the following embodiments are only examples of the present invention, and the present invention is not limited to these examples. Unless otherwise specified, parts and% in the present invention represent parts by mass and% by mass.

<Measuring method of amine value>
The amine value was determined according to the following method according to JIS K0070 with the same amount of potassium hydroxide as the equivalent of hydrochloric acid required to neutralize the amino group contained in 1 g of the resin.
The sample was precisely weighed in an amount of 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 to the obtained solution as an indicator, and the obtained solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). With the point where the color of the solution changed from green to yellow as the end point, the amine titer was determined by the following (Equation 1) using the titration amount (AmL) at this time.
(Formula 1) Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g]

<Measurement method of number average molecular weight (Mn) and mass average molecular weight (Mw)>
The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by using GPC (gel permeation chromatography) "Shodex GPC System-21" manufactured by Showa Denko KK. GPC is a liquid chromatography in which a substance dissolved in a solvent is separated and quantified by the difference in its molecular size. The solvent is tetrohydrofuran, and the molecular weight is determined in terms of polystyrene.

<Measurement method of hydroxyl value>
It was obtained according to the method described in JIS K0070.

<Measurement method of acid value>
It was obtained according to the method described in JIS K0070.

[Synthesis Example 1-1] (Synthesis of Polyester Polyol A1)
25 parts of 2-butyl-2-ethyl-1,3-propanediol (hereinafter abbreviated as BEPG), 1,3-propanediol in a round-bottom flask equipped with a stirrer, a thermometer, a water divider and a nitrogen gas introduction tube. 22 parts (hereinafter abbreviated as 1,3-PD), 53 parts of succinic acid, and 0.002 part of tetrabutyl titanate were charged, and esterification was carried out for 8 hours under a nitrogen stream at 230 ° C. while removing water generated by condensation. .. After confirming that the acid value of the polyester was 15 or less, the degree of vacuum was gradually increased by a vacuum pump to complete the reaction. As a result, polyester polio (A1) having a number average molecular weight of 2000, a hydroxyl value of 56.1 mgKOH / g, an acid value of 0.3 mgKOH / g, and a biomass degree of 74.9% was obtained.

[Synthesis Example 1-2-1-19] (Synthesis of Polyester Polyols A2 to A19)
Polyester polyols A2 to A19 were obtained in the same manner as in Synthesis Example 1-1 except that the raw materials and the charging ratios shown in Table 1 were used. The abbreviations described in the table represent the following.
MPO: 2-Methyl-1,3-propanediol (derived from petroleum)
MPD: 3-Methyl-1,5-pentanediol (derived from petroleum)
NPG: Neopentyl glycol (plant-derived biomass 40%)
NPG: Neopentyl glycol (100% plant-derived biomass)
PG: 1,2-Propylene glycol (100% plant-derived biomass)
EG: Ethylene glycol (derived from petroleum)
1,3-PD: 1,3-Propanediol (100% plant-derived biomass)
1,4-BD: 1,4-butanediol (100% plant-derived biomass)
In the above, the biomass degree of NPG is derived from the catalog value of Perstoop.
-The dibasic acids in the table have the following biomass degrees.
Adipic acid: (derived from petroleum)
Succinic acid: (100% biomass-derived biomass)
Sebacic acid: (100% biomass-derived biomass)
Dimer acid: (100% biomass-derived biomass)

[Comparative Synthesis Examples 1-1 to 1-3] (Synthesis of Polyester Polyols B1 to B3)
Polyester polyols B1 to B3 were obtained in the same manner as in Synthesis Example 1-1 except that the raw materials and the charging ratios shown in Table 1 were used.

[Synthesis Example 2-1] (Synthesis of Polyurethane Resin P1)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, 20.0 parts of polyester polyol A1 and poly (1,3-propanediol) (hereinafter, also abbreviated as PPD) 4 .2 parts, isophorone diisocyanate (hereinafter abbreviated as IPDI) 4 parts, ethyl acetate (hereinafter abbreviated as EA) 10 parts, and tin 2-ethylhexanoate 0.003 parts were charged and reacted at 120 ° C. for 6 hours under a nitrogen stream. , 14 parts of propyl acetate (hereinafter abbreviated as NPA) was added and cooled to obtain a solution of terminal isocyanate prepolymer. Next, 1.7 parts of isocyanate diamine (hereinafter, also abbreviated as IPDA), 0.2 part of dibutylamine (hereinafter, also abbreviated as DBA), 18 parts of EA, and 28 parts of isopropyl alcohol (hereinafter, also abbreviated as IPA) were mixed, and the obtained terminal was obtained. A solution of the isocyanate prepolymer was gradually added at room temperature and then reacted at 50 ° C. for 1 hour to obtain a polyurethane resin P1 having a solid content of 30%, a mass average molecular weight of 72000, an amine value of 4 mgKOH / g, and a biomass degree of 63.9% by mass. A solution was obtained.

[Synthesis Example 2-2-2-26] (Synthesis of Polyurethane Resins P2-P26)
Polyurethane resins P2 to P26 were obtained in the same manner as in Synthesis Example 2-1 except that the raw materials and the charging ratios shown in Table 2 were used. The degree of biomass etc. is shown in the same table.
The abbreviations described in the table represent the following.
PEG: Polyethylene glycol (poly (1,2-ethanediol)) [number average molecular weight 2,000, plant-derived, biomass degree 100%]
PPG: Polypropylene glycol (poly (1,2-propanediol)) [number average molecular weight 2,000, plant-derived, biomass degree 100%]
PPD: Polytrimethylene glycol (poly (1,3-propanediol)) [number average molecular weight 2,000, plant-derived, biomass degree 100%]

[Comparative Synthesis Examples 2-1 to 2-5] (Synthesis of Polyurethane Resins PP1 to PP5)
Polyurethane resins PP1 to PP5 were obtained in the same manner as in Synthesis Example 2-1 except that the raw materials and the charging ratios shown in Table 2 were used. The degree of biomass etc. is shown in the same table.

[Example 1] (Manufacturing of ink S1)
35 parts of titanium oxide pigment (JR806 silica and alumina surface-treated rutile type titanium oxide oil absorption amount 21 g / 100 g), 31 parts of polyurethane resin P1 solution, vinyl chloride-acrylic copolymer resin solution (VINNNOL manufactured by Wacker Chemie) E15 / 40A Vinyl chloride component: Acrylic component = 84:16 Solid content 24% solution) 4 parts, mixed solvent (EA / IPA = 75/25 (mass ratio), biomass degree 0%) 13 parts are mixed by stirring and mixed with a sand mill. After the dispersion, 17 parts of the mixed solvent (EA / isopropyl alcohol = 75/25 (mass ratio)) was stirred and mixed to obtain ink S1. (Table 3-1 shows the total of each component.)

[Examples 2-41] (Manufacturing of inks S2-S41)
Inks S2 to S41 were obtained in the same manner as in Example 1 except that the raw materials and the charging ratios shown in Tables 3-1 and 3-2 were used. The description in the table shows the following.
Vinyl chloride-vinyl acetate copolymer resin: Solveine TA5R solid content 24% solution manufactured by Nissin Chemical Industry Co., Ltd., biomass degree 0%
Rosin ester: Harima Chemicals Co., Ltd. Haritac FK125 Solid content 24% solution Softening point 125 ° C, biomass degree 100%
Rosin-modified maleic acid resin: Marquid No5 solid content 24% solution manufactured by Arakawa Chemical Industry Co., Ltd. Softening point 145 ° C, biomass degree 98%
Copper phthalocyanine (indigo): Phthalocyanine manufactured by Toyo Color Co., Ltd. LIONOL BLUE FG-7358-G

[Comparative Examples 1 to 10] (Manufacturing of inks SS1 to SS10)
Inks SS1 to SS10 were obtained in the same manner as in Example 1 except that the raw materials and the charging ratios shown in Table 4 were used.

[Preparation of printed matter using ink S1]
The viscosity of ink S1 is diluted with an EA / IPA mixed solvent (mass ratio 75/25) to a viscosity of Zahn Cup # 3 (manufactured by Rigo Co., Ltd.) for 15 seconds (at 25 ° C.), and a plate depth of 30 μm is provided. A single-sided corona-treated polypropylene (OPP) film (Pyrene P2161 manufactured by Toyobo Co., Ltd.) was printed on the corona-treated surface with a gravure calibrator and dried at 40 to 50 ° C. to obtain a printed matter using ink S1.
Only in the following evaluation of the residual solvent in the printed matter, the printing process was repeated three times on the OPP to perform multi-layer printing, and a multi-layer printed matter was obtained and used for the evaluation.

[Preparation of printed matter using inks S2 to S41 and inks SS1 to SS10]
Printed matter (OPP, PET) using inks S2 to S41 and inks SS1 to SS10 were obtained in the same manner as in the example of printed matter using ink S1 except that inks S2 to S41 and inks SS1 to SS10 were used. ..

[evaluation]
Using the inks S1 to S41 (Example), SS1 to SS10 (Comparative Example) obtained in the above Examples and Comparative Examples, and their printed matter, the printed matter residual solvent and the laminate residual solvent, by the method described below. Lamination strength, printed matter density, and resolubility were evaluated.

[Printed matter residual solvent (multilayer printed matter, OPP)]
The printed matter of the inks S1 to S41 (Example) and SS1 to SS10 (Comparative Example) obtained in the above Examples and Comparative Examples was cut into a size of 10 cm in width and 10 cm in length, 200 sheets were placed in an eggplant flask, sealed, and then heated. bottom. (Temperature: 80 ° C., 60 minutes) After that, 0.4 ml of air in the flask was extracted and analyzed by gas chromatography (GC) to confirm the amount of solvent components.
(Evaluation criteria)
5: The total amount of residual solvent was less than ^{0.5 mg / cm 2.} (Yu)
4: The total amount of residual solvent was 0.5 mg / cm ² or more and less than 1 mg / cm ^2. (good)
3: The total amount of residual solvent was 1 mg / cm ² or more and less than 2 mg / cm ^2. (Yes)
2: The total amount of residual solvent was 2 mg / cm ² or more and less than 3 mg / cm ^2. (No)
1: The total amount of residual solvent was 3 mg / cm ² or more. (Inferior)
The practical level is 3 to 5.

[Residual solvent of laminate]
Immin-based anchor coating agent (EL420 manufactured by Toyo Morton Co., Ltd.) on the printed matter of the OPP film printed matter of the inks S1 to S41 (Example) and SS1 to SS10 (Comparative Example) obtained in the above Examples and Comparative Examples. Is coated with a methanol solution having a solid content of 1% by mass, and molten polyethylene (LC600A manufactured by Japan Polyethylene Corporation) is extruded at 320 ° C. and laminated at 18 μm using an extrusion laminating machine (manufactured by Musashinokikai) at a line speed of 100 m / min. At the same time, CPP (FCMN film thickness 20 μm manufactured by Futamura Chemical Co., Ltd.) was laminated in the same manner to obtain a laminated laminate.
After the laminating process, the laminated laminate was cut into a size of 10 cm in width and 10 cm in length, 200 sheets were placed in an eggplant flask, sealed, and then heated. (Temperature: 80 ° C., 60 minutes) After that, 0.4 ml of air in the flask was extracted and analyzed by gas chromatography (GC) to confirm the amount of solvent components.
(Evaluation criteria)
5: The total amount of residual solvent was less than ^{0.5 mg / cm 2.} (Yu)
4: The total amount of residual solvent was 0.5 mg / cm ² or more and less than 1 mg / cm ^2. (good)
3: The total amount of residual solvent was 1 mg / cm ² or more and less than 2 mg / cm ^2. (Yes)
2: The total amount of residual solvent was 2 mg / cm ² or more and less than 3 mg / cm ^2. (No)
1: The total amount of residual solvent was 3 mg / cm ² or more. (Inferior)
The practical level is 3 to 5.

[Laminate strength]
The laminated laminates of the inks S1 to S41 (Example) and SS1 to SS10 (Comparative Example) obtained in the above Examples and Comparative Examples were cut into a length of 150 mm and a width of 15 mm, opened at the ink / OPP film interface, and pulled. The lamination strength in the 90 ° direction was measured using a testing machine.
(Evaluation criteria)
5: 1.5N / 15mm or more (excellent)
4: 1.0N / 15mm or more, less than 1.5N / 15mm (good)
3: 0.8N / 15mm or more, less than 1.0N / 15mm (possible)
2: 0.5N / 15mm or more, less than 0.8N / 15mm (impossible)
1: 0.5N / less than 15mm (inferior)
The practical level is 3 to 5.

[Printed matter density (white)]
Multi-layer printed matter of inks S1 to S36 (Example) and SS1 to SS5 (Comparative Example) obtained in the above Examples and Comparative Examples was used as an excact manufactured by X-Rite, with a light source D50, a viewing angle of 2 °, and CIE1976 (L *). a * b *) Measured in the color space.
(Evaluation criteria)
5: L * 78.0 or higher (excellent)
4: L * 76.0 or more and less than 78.0 (good)
3: L * 74.0 or more and less than 76.0 (possible)
2: L * 72.0 or more and less than 74.0 (impossible)
1: L * Less than 72.0 (inferior)
The practical level is 3 to 5.
[Printed matter density (indigo)]
Multi-layer printed matter of inks S37 to S41 (Example) and SS6 to SS10 (Comparative Example) obtained in the above Examples and Comparative Examples was used as an excact manufactured by X-Rite, with a light source D50, a viewing angle of 2 °, and CIE1976 (L *). a * b *) Measured in the color space.
(Evaluation criteria)
5: CYAN concentration 1.80 or more (excellent)
4: CYAN concentration 1.70 or more and less than 1.80 (good)
3: CYAN concentration 1.60 or more and less than 1.70 (possible)
2: CYAN concentration 1.50 or more and less than 1.60 (impossible)
1: CYAN concentration less than 1.50 (inferior)
The practical level is 3 to 5.

[Resolubility]
10 ml of EA / IPA mixed solvent (mass ratio 75/25) was poured on the multilayer printed matter of the inks S1 to S41 (Example) and SS1 to SS10 (Comparative Example) obtained in the above Examples and Comparative Examples to dissolve the ink. The degree was visually evaluated.
5: All the ink film melts, leaving no trace of melting (excellent)
4: 75% of the ink film melts, leaving a slight melt mark (good)
3: 50% of the ink film melts, leaving a trace of melting (possible)
2: 25% of the ink film melts, leaving a trace of melting (impossible)
1: 5% of the ink film melts, leaving a trace of melting (inferior)
The practical level is 3 to 5.
The better the resolubility, the better the printability.

From the above results, the subject of the present application could be achieved by using the gravure or flexographic ink of the present invention. Further, when a biomass polyurethane resin using both a polyester polyol and a polyether polyol was used, excellent results were obtained for the residual solvent of the multilayer printed matter and the laminated laminate. Further, when a biomass polyurethane resin using a polyester polyol containing a branched diol and a linear diol was used as the polyurethane resin, excellent results were obtained in terms of laminate strength and resolubility. In the comparative example, any of the residual solvent, the laminate strength, the printed matter concentration, and the resolubility deteriorated, and the characteristics were inferior.

Claims (9)

A gravure or flexographic ink containing a biomass polyurethane resin as a binder resin.
The biomass polyurethane resin contains a constituent unit derived from a polyester polyol which is a condensate of a dibasic acid and a diol and a constituent unit derived from a polyether polyol.
The dibasic acid contains at least one biomass dibasic acid selected from succinic acid, sebacic acid and dimer acid, and the diol contains a branched diol and a linear diol.
The polyether polyol is a gravure or flexo ink having 1,3-propanediol and / or 1,2-propanediol derived from biomass as a constituent unit. The gravure or flexo ink according to claim 1, wherein the dibasic acid contains 60% by mass or more of succinic acid and / or sebacic acid in 100% by mass of the dibasic acid. The gravure or flexo ink according to claim 1 or 2, wherein the diol contains a branched diol and a linear diol in a mass ratio of 10:90 to 90:10. The gravure or flexo ink according to any one of claims 1 to 3, wherein the linear diol contains a linear diol having 3 to 8 carbon atoms. The binder resin further contains a vinyl chloride copolymer resin and / or a rosin-based resin, and the mass ratio of the polyurethane resin and the vinyl chloride copolymer resin and / or the rosin-based resin is 95: 5 to 30:70. The gravure or flexo ink according to any one of claims 1 to 4. The gravure or flexographic ink according to any one of claims 1 to 5, wherein the biomass of the polyurethane polyurethane resin has a biomass content of 40 to 100% by mass. The gravure or flexo ink according to any one of claims 1 to 6, further comprising a titanium oxide pigment and having a biomass degree of 10% or more in a total of 100 mass of the titanium oxide pigment and the binder resin. A printed matter having a printed layer made of the gravure or flexographic ink according to any one of claims 1 to 7 on the base material 1. A laminate having at least a base material 1, a printing layer made of the gravure or flexographic ink according to any one of claims 1 to 7, and a base material 2 in this order.