JP2024041313A - Gravure printing ink composition, laminate and laminated laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop one-liquid printing ink composition that can form a printed film excellent in adhesion with stability, on any of substrates of various surface structures used by applying print on a surface, has the film excellent in blocking property, further makes a laminated body have the printed film exhibiting practically sufficient laminate strength, can be used also in printing for laminate use, and can readily apply to print gravure printing.

SOLUTION: A printing ink composition comprises: a 5-membered cyclic carbonate compound formed by reacting an epoxy compound and carbon dioxide: a polyhydroxy polyurethane (A) which is a reaction product with an amine compound; a vinyl chloride-vinyl acetate copolymer (B) having a hydroxyl group; and an organic solvent (C), in which a mass ratio of nonvolatile components of polyhydroxy polyurethane (A) and vinyl chloride-vinyl acetate copolymer (B) is (A):(B)=95:5 to 20:80 and a laminate using the same.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a gravure printing ink composition, a laminate, and a laminate. Specifically, although a polyurethane resin is used as a binder, a gravure printing ink composition is laminated as a printed film on a base material of various plastic films, for example, without using a curing agent to form a laminate. In addition, the printed film exhibits sufficient adhesion to various substrates, and has excellent anti-blocking properties with set-off suppressed, and furthermore, when made into a laminate. The present invention relates to a technique for providing a highly practical gravure printing ink composition that exhibits sufficient lamination strength.

With recent advances in packaging technology, base materials to which printing is performed by gravure printing and the like have come to have a wide variety of configurations, such as transparent vapor-deposited films. As transparent vapor-deposited films, for example, films made by vapor-depositing inorganic substances such as silica and alumina on transparent films made of PET, nylon (NY), or biaxially oriented polypropylene (OPP) are known, and are also commercially available. ing. By forming a vapor-deposited film, a transparent film made of the above-mentioned materials can be provided with various functionalities such as gas barrier properties and water vapor barrier properties, so the demand for such films is increasing year by year. The vapor-deposited film can be given various functionalities depending on the type and amount of the vapor deposited material, and the coated product, so the transparent vapor-deposited film products manufactured and sold by different companies have different surface properties.

Differences in surface properties particularly have an effect when printing is performed on a transparent vapor-deposited film using gravure printing or the like. According to studies conducted by the present inventors, transparent vapor-deposited films are more prone to problems such as problems such as impaired adhesion of printing ink films and blocking problems that cause set-off, compared to general films. In order to deal with these problems, methods for applying printing ink compositions to transparent vapor-deposited films include the use of a so-called two-liquid specification, in which an ink and a curing agent are used together, and the method proposed in Patent Document 1. In addition, a three-component specification using ink, a hardening agent, and a silane coupling agent is being used. In addition, with recent advances in packaging technology, plastic films printed with gravure printing etc. are often used under harsh conditions, and in such cases, the printed film formed on the base material may be damaged. Higher adhesion is required. For this reason, for example, when printing on OPP, PET, or NY-made films, which are common for laminating, by gravure printing, etc., if the printing ink film formed on the base material lacks physical properties, the ink may harden. Agents may be added to improve physical properties.

Patent No. 4186089

In view of the above-mentioned circumstances, the present inventors have developed a printing method that can suppress the problems of blocking, which inhibits the adhesion of the printing ink film and causes set-off, when printing on a transparent vapor-deposited film using gravure printing or the like. We recognized that there is an urgent need to develop an ink composition suitable for the formation of printed matter such as gravure printing on plastic films for lamination. In particular, we are aiming to form a printed film with high physical properties using a 1-liquid specification, rather than creating a printed film with high physical properties using a complicated 2-liquid or 3-liquid specification, which is done with conventional printing inks. It would be extremely useful if it were possible to provide a printing ink composition that enables this.

Therefore, an object of the present invention is to provide stable adhesion to any plastic film base material having a variety of surface configurations, the surface of which is subjected to gravure printing or the like. It can form a printed film with excellent properties, the printed film also has excellent blocking properties, and the laminate laminate with the printed film exhibits practically sufficient laminating strength, so it can also be used for printing for laminating purposes. Moreover, the object of the present invention is to develop a one-liquid printing ink composition that is easy to apply to printing such as gravure printing.

The above objects are achieved by the invention described below. That is, the present invention provides the following gravure printing ink composition.
[1] A 5-membered cyclic carbonate compound formed by reacting an epoxy compound and carbon dioxide, a polyhydroxypolyurethane (A) having a hydroxyl group which is a reaction product with an amine compound, and a vinyl chloride-vinyl acetate copolymer having a hydroxyl group A gravure printing ink composition comprising a combination (B) and an organic solvent (C),
The polyhydroxypolyurethane (A) and the vinyl chloride-vinyl acetate copolymer (B) have a mass ratio of nonvolatile components of (A):(B)=95:5 to 20:80. A gravure printing ink composition.

Preferred forms of the gravure printing ink composition of the present invention include the following.
[2] The gravure printing ink composition according to [1] above, wherein the vinyl chloride-vinyl acetate copolymer (B) has a hydroxyl value in the solid content of 60 to 180 mgKOH/g.
[3] The gravure printing ink composition according to [1] or [2] above, wherein the polyhydroxy polyurethane (A) has a hydroxyl value in the solid content of 25 to 300 mgKOH/g.
[4] The gravure printing ink composition according to [3] above, wherein the polyhydroxy polyurethane (A) has a hydroxyl value in the solid content of 25 to 100 mgKOH/g, and a portion of the hydroxyl groups are silylated. thing.
[5] The gravure printing ink composition according to any one of [1] to [4] above, further comprising a colorant (D).

The present invention provides the following laminate as another embodiment.
[6] A laminate in which a gravure printing ink composition is laminated on a substrate, the gravure printing ink composition being the gravure printing ink composition according to any one of [1] to [5] above. A laminate characterized by:

The present invention provides the following laminate laminate as another embodiment.
[7] A laminate laminate in which a base material 1, a printing layer made of a gravure printing ink composition formed by printing on the base material 1, an adhesive layer, and a base material 2 are laminated in this order. , a laminate, wherein the gravure printing ink composition is the gravure printing ink composition according to any one of [1] to [5] above.

According to the present invention, it is possible to stably adhere to any of the plastic film base materials having various surface configurations and which are used with gravure printing etc. on the surface and have excellent adhesion to the base material. It is possible to form a printed film, and the printed film has excellent blocking properties, and furthermore, it can be used for printing for laminating purposes, where the laminate laminate having the printed film exhibits practically sufficient laminating strength. Furthermore, it is possible to provide a one-liquid printing ink composition that is easy to apply to printing such as gravure printing.

Hereinafter, the present invention will be explained by citing preferred embodiments. In order to solve the above-mentioned problems with the prior art, the present inventors have developed and proposed a greenhouse gas binder for gravure printing ink compositions (see Japanese Patent No. 5087063, etc.). We conducted extensive research with the belief that if we could utilize polyhydroxypolyurethane resin (hereinafter sometimes abbreviated as HPU), which consumes CO ₂ as a material, it would be possible to provide environmentally friendly technology, which has been an issue in recent years. . The applicant of the present application has already proposed and put into practical use a method for manufacturing polyhydroxypolyurethane resin that can be industrially mass-produced. The method is a simple one that first prepares a 5-membered cyclic compound using an epoxy compound and carbon dioxide as raw materials, and then reacts the 5-membered cyclic compound with a diamine. The resulting polyhydroxypolyurethane resin has a structural feature that immobilizes the raw material carbon dioxide in its structure, and has a structure that is completely different from conventional general urethane resins. In particular, unlike conventional general urethane resins, it is an epoch-making material that makes it possible to use carbon dioxide, a greenhouse gas, as a resin raw material.

The present inventors applied a polyhydroxypolyurethane resin having the above-mentioned advantages as a binder for oil-based ink for gravure printing, which is often used for printing on plastic films such as transparent vapor-deposited films that are widely used for packaging materials. We considered the possibility of this. During the study process, it was discovered that when turning into ink, HPU cannot be handled in the same way as general urethane resins because of its unique structure with hydroxyl groups in its main chain. There was an issue. In the specification of the present invention, conventional polyurethane resins synthesized using polyisocyanate compounds are referred to as "general urethane resins."

Specifically, HPU has poor compatibility with other resins and does not mix with resins used in conventional printing inks, so it cannot be said to be suitable as a material for preparing printing inks. For example, we confirmed that it does not mix with many resins used in conventional printing inks, such as common urethane resins, cellulose ester resins (CAB), chlorinated polypropylene (chlorinated PP), and acrylic resins.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies focusing on the presence of hydroxyl groups in the structure, which are not present in conventional general urethane resins, as an advantage of using HPU as a material for printing ink. Ta. In addition, we conducted intensive studies to solve the following problems with transparent vapor-deposited films, which are problems with conventional printing inks mentioned above, by using HPU as a material for printing ink. As mentioned above, transparent vapor-deposited films are more prone to problems than general films, such as problems such as poor adhesion of printing ink films and blocking problems that cause set-off. Currently, the methods of applying printing ink to transparent vapor-deposited films to address these problems include using a two-component system that uses both an ink and a hardening agent, or using an ink, a hardening agent, and a silane coupling agent. A three-liquid specification is being implemented. In addition, when printing with gravure printing on OPP (biaxially oriented polypropylene), PET, NY-made films, etc., which are commonly used for lamination, if the printing ink film formed on the base material lacks physical properties. In order to improve the physical properties, hardening agents are added to improve the physical properties. In response to the current situation, the present inventors recognized that it would be extremely useful if a one-component printing ink could solve the above problems, and as a result of intensive studies, the present invention was developed. It is.

<Gravure printing ink composition>
The present inventors investigated the possibility of using HPU when turning it into ink. First, in the case of a printing ink that uses 100% HPU as a binder, it was found that it could be applied to printing on a transparent vapor-deposited film as a base material. It was confirmed that the printed film had poor adhesion to the substrate and blocking properties. In this way, since printing inks that used 100% HPU were not suitable for transparent vapor-deposited films, it was found that it was necessary to create printing inks that used HPU and other resins together as a binder. Ta. As mentioned above, HPU has poor compatibility with resins that are generally used as binders for printing inks. On the other hand, the present inventors have conducted intensive studies on resin materials that are compatible with HPU and can solve the above-mentioned problems when used as a printing ink. It has been found that it is effective to use it in combination with a vinyl copolymer. Furthermore, when the mass ratio of non-volatile content (solid content) of HPU and vinyl chloride-vinyl acetate copolymer is (A) for HPU and (B) for vinyl chloride-vinyl acetate copolymer, It has been found that a gravure printing ink composition that can solve the problems aimed at by the present invention can be obtained by having a configuration in which (A):(B)=95:5 to 20:80. Hereinafter, vinyl chloride-vinyl acetate copolymer will also be referred to as "salt vinyl acetate resin".

As mentioned above, the printed film of printing ink using 100% HPU has poor adhesion to the substrate and blocking resistance. On the other hand, when HPU (A) is 10%: salt vinyl acetate resin (B) is 90%, the HPU is too small and the adhesion to the base material is poor. According to studies by the present inventors, it was found that the problems of the present invention can be solved by setting the HPU (A): salt vinyl acetate resin (B) = 95:5 to 20:80. More preferably, the composition is such that HPU (A): salt vinyl acetate resin (B) = 90:10 to 30:70. Particularly preferably, HPU (A) is in the range of 80 to 60%, and salt vinyl acetate resin (B) is used in the range of 20 to 40% in combination to achieve a more stable and noticeable effect. Obtainable.

The gravure printing ink composition of the present invention, which contains HPU (A) and salt-vinyl acetate resin (B) in a specific ratio, can be used in particular with various types of transparent vapor-deposited materials such as PET and NY (nylon), as described below. It was confirmed that the printed film (printed layer) formed on the film showed good adhesion and also had excellent blocking resistance. Of course, the formed printed film (printed layer) exhibits good adhesion to various general substrates such as PET, NY, PT (ordinary cellophane), and OPP, and also has excellent blocking resistance. Excellent in sex. On the other hand, a general urethane resin, a general urethane resin having a hydroxyl group, and a structure in which HPU (A): salt vinyl acetate resin (B) = 95:5 to 20:80 as defined in the present invention are used. When HPU (A) and salt-vinyl acetate resin (B) are used together in a combination that does not satisfy the above conditions, the printed film formed will have poor adhesion to the substrate in all cases, and in most cases This results in poor blocking resistance. Details will be explained with reference to specific examples and comparative examples. Each component constituting the gravure printing ink composition of the present invention will be explained below.

[Vinyl chloride-vinyl acetate copolymer]
First, the salt vinyl acetate resin (B) constituting the gravure printing ink composition of the present invention will be explained. The salt vinyl acetate resin (B) used in combination with HPU (A) is required to contain hydroxyl groups in addition to being used together with HPU (A) in the above-mentioned specific ratio. Among these, for example, it is preferable that the hydroxyl value in the solid content of the vinyl salt vinyl acetate resin is in the range of 60 to 180 mgKOH/g. More preferably, it is in the range of 80 to 170 mgKOH/g. More preferably, it is in the range of 100 to 160 mgKOH/g. According to studies by the present inventors, if the hydroxyl value of the salt-vinyl acetate resin is too low, the physical properties of the printed film when used as a printing ink tend to deteriorate. Moreover, if the hydroxyl value is too low, the compatibility with HPU will also deteriorate, which is not preferable.

As mentioned above, the salt-vinyl acetate resin used in combination with HPU, which constitutes the gravure printing ink composition of the present invention, must have a hydroxyl group. It is preferable that there be one, but there are no particular limitations other than that. Salt-vinyl acetate resin is known as a modified resin that takes advantage of the toughness and chemical resistance of vinyl chloride and the adhesiveness and plasticity of vinyl acetate, and is commercially available and used as a binder or coating agent. Examples of commercially available products that can be used as the hydroxyl group-containing vinyl chloride-vinyl acetate copolymer (B) constituting the present invention include the following. Solvine TA5R, Solvine TAO, Solvine A, Solvine AL, Solvine AP, and Solvine ALLP (all trade names) manufactured by Nissin Chemical Industry Co., Ltd. Vinnol E15/45M and Vinnol H15/45M manufactured by Wacker Chmie AG (All of the above are trade names), Kanevinyl T5HX (trade name) manufactured by Kaneka Corporation, and other commercially available products can be used as appropriate.

(Vinyl chloride-vinyl acetate copolymer resin varnish)
When producing the gravure printing ink composition of the present invention, a solid vinyl salt vinyl acetate resin may be used as it is. Not limited to this, for example, a solid vinyl chloride acetate resin may be dissolved in an organic solvent and used as a vinyl chloride-vinyl acetate copolymer resin varnish in a solution state (hereinafter referred to as vinyl chloride acetate resin varnish). is also a preferred embodiment. The organic solvent for dissolving the salt-vinyl acetate resin is not particularly limited, but ethyl acetate and the like are suitable, for example.

[Polyhydroxypolyurethane]
The polyhydroxypolyurethane (A) used in combination with the salt vinyl acetate resin (B) having a hydroxyl group, which constitutes the gravure printing ink composition of the present invention, is not particularly limited. For example, those described in the above-mentioned Japanese Patent No. 5087063 can be used as appropriate. Preferably, the HPU has a hydroxyl value in the solid content of 25 to 300 mgKOH/g. Further, those having a hydroxyl value of 25 to 300 mgKOH/g and having some of the hydroxyl groups silylated can also be preferably applied. The hydroxyl value of the HPU constituting the present invention is preferably 30 to 100 mgKOH/g, more preferably 35 to 80 mgKOH/g, and particularly preferably 45 to 70 mgKOH/g. What is important in the present invention is that, as mentioned earlier, the mass ratio of HPU and salt-vinyl acetate resin in terms of non-volatile content (solid content) is such that HPU is (A) and salt-vinyl acetate resin is (B). In this case, the configuration is such that (A):(B)=95:5 to 20:80.

The weight average molecular weight of the HPU constituting the present invention is preferably 10,000 to 100,000, more preferably 20,000 to 80,000. Furthermore, it is more preferably 30,000 to 60,000. In this specification, the weight average molecular weight of HPU is a value measured by gel permeation chromatography (GPC) in terms of polystyrene.

(Polyhydroxy polyurethane varnish)
As a specific embodiment of producing the gravure printing ink composition of the present invention, for example, the HPU resin solution, which is a mixture of HPU and a reaction solvent obtained during the synthesis of the above-mentioned polyhydroxypolyurethane (A), is directly used. May be used as HPU varnish. Furthermore, the HPU varnish may be diluted with any solvent and adjusted to any solid content ratio and used as the HPU varnish. For example, the following organic solvents are used as these solvents.

[Organic solvent]
When preparing the gravure printing ink composition of the present invention, a salt vinyl acetate resin varnish or HPU varnish containing an organic solvent can be used. Also used for dilution for adjustment. The organic solvent constituting the gravure printing ink composition of the present invention is preferably one that dissolves the HPU constituting the present invention, and any known organic solvent can be used as appropriate. From the viewpoint of working environment safety such as odor and safety, the organic solvent used in the present invention preferably does not contain toluene or does not contain toluene and MEK. In the present invention, for example, ester solvents/alcohol solvents are preferably used.

(ester solvent)
Examples of the ester solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate. Particularly suitable ester organic solvents for the gravure printing ink composition of the present invention include ethyl acetate and n-propyl acetate.

(alcohol solvent)
Examples of alcoholic solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tertiary butyl alcohol, and glycol monoalkyl ethers such as propylene glycol monomethyl ether. Particularly suitable alcoholic organic solvents for the gravure printing ink composition of the present invention include isopropyl alcohol and propylene glycol monomethyl ether.

[Colorant]
An embodiment of the gravure printing ink composition of the present invention further includes a colorant (D). The colorant (D) used in this case is not particularly limited, and conventionally known inorganic pigments and organic pigments can be used. Examples of inorganic pigments include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, red iron oxide, aluminum, and mica. These pigments can be used alone or in combination of two or more. In addition, these inorganic pigments are contained in an amount sufficient to ensure the concentration and coloring power of the ink, that is, in a proportion of about 10% by mass to 80% by mass based on the solid content of the gravure printing ink composition of the present invention. It is preferable that the

Examples of organic pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, and anthrapyrimidines. pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. These pigments can be used alone or in combination of two or more. Further, the content of the organic pigment based on the solid content of the gravure printing ink composition of the present invention is preferably 10% by mass to 80% by mass.

More specifically, the coloring agent used in the present invention can be exemplified by the following color index names, and any of them can be used.
C. I. Pigment Yellow 13, 14, 17, 83, 180;
C. I. Pigment Orange 13, 16;
C. I. Pigment Red 48:1, 48:2, 48:3, 49:1, 53:1, 57:1, 101, 122, 146, 185;
C. I. Pigment Violet 23, 24;
C. I. Pigment Blue 15:1, 15:3, 15:4, 17:1;
C. I. Pigment Green 7;
C. I. Pigment Black 7;
C. I. Pigment White 4, 6, 18 and the like.

[Additive]
In addition to the components listed above, the gravure printing ink composition of the present invention may further contain various additives as listed below, if necessary. Additives include pigment derivatives, dispersants, chelating agents, waxes, fatty acid amides, plasticizers, wetting agents, leveling agents, antifoaming agents, antistatic agents, viscosity modifiers, trapping agents, antiblocking agents, crosslinking agents, and Examples include silane coupling agents.

<Method for producing gravure printing ink composition>
The gravure printing ink composition of the present invention can be produced by a conventionally known method. For example, it can be manufactured by blending HPU (A), salt-vinyl acetate resin (B), and, if necessary, coloring agents, additives, etc., and dissolving or dispersing the mixture in an organic solvent. The physical properties such as viscosity of the gravure printing ink composition of the present invention can be adjusted by appropriately controlling the size and filling rate of the media used in the dispersion machine, the dispersion treatment time, etc. As the dispersing machine, it is preferable to use a bead mill. Examples of device names for bead mills include Mighty Mill, Dyno Mill, and Sand Mill. Other dispersers include, for example, a ball mill, a disperser stirrer, and the like.

[Laminated body]
In the first embodiment of the laminate of the present invention, a gravure printing ink composition is laminated on a base material, and the gravure printing ink composition is the gravure printing ink composition of the present invention described above. It is characterized by Further, in the present invention, as the laminate of the second embodiment, a printed layer consisting of the gravure printing ink composition of the present invention formed by printing on a base material, an adhesive layer on the printed layer, A laminate is provided in which base materials are laminated in this order on the adhesive layer. In addition, in the description of the laminate, the base material on which the printing layer is formed with the gravure printing ink composition of the present invention will be referred to as "base material 1", and the base material facing the adhesive layer will be referred to as "base material 2". It is called. The base material in the first embodiment is called "base material 1" because it is similar to "base material 1."

(Base material 1)
As the base material 1, for example, polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); low density polyethylene (LDPE), linear low density polyethylene (LLDPE), Polyolefin films such as high-density polyethylene (HDPE) and polypropylene (PP); cellulose films such as cellophane; polystyrene (PS) films; ethylene-vinyl acetate copolymer resin films; ethylene-vinyl alcohol copolymer resin films; nylon (NY ) films such as polyamide films; polycarbonate films; polyimide films; polyvinyl chloride films; and other plastic films and paper. Both stretched and unstretched plastic films can be used, such as biaxially stretched PP films and unstretched PP films. Further, a base material provided with a metal vapor deposited layer such as aluminum vapor deposited or a base material provided with a transparent vapor deposited layer such as alumina and silica can also be used. Furthermore, the surface of the base material is subjected to various surface treatments such as corona discharge treatment, plasma treatment, flame treatment, solvent treatment, and coating treatment, as well as various decorations such as printing using colored ink. Good too.

(Base material 2)
The base material 2 may be, for example, a polyolefin film such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), or polypropylene (PP); or a plastic film such as these. Examples include plastic films such as film sealants made of composite materials.

(glue)
The adhesive layer constituting the laminate of the present invention can be formed by applying an adhesive and then drying it. As the adhesive to be used, a two-component adhesive made of a mixture of a polyol and an isocyanate curing agent, which is generally used in the known dry lamination method described below, is suitable. Examples of the polyol include polyester polyols and polyether polyols. Specific examples include Seikabond E-263/C-75N and A-159/C89 (F) (all trade names) manufactured by Dainichiseika Chemical Industry Co., Ltd. Alternatively, a two-component adhesive consisting of a mixture of a polyol and an isocyanate curing agent, which is an adhesive called an anchor coating agent used in the known melt extrusion lamination method described below, can be suitably used. Specific examples of such products include Seikadyne 2710A/Seikadyne 2710C (trade name) manufactured by Dainichiseika Chemical Industry Co., Ltd.

(Method for manufacturing laminate)
The laminate of the present invention can be produced by a conventionally known method, except that the gravure printing ink composition of the present invention is used to form the printing layer. Specifically, a dry lamination method in which another plastic film (base material 2) is laminated via an adhesive layer on a printed layer provided on the plastic film of base material 1 as exemplified above, or Depending on the method, a known laminating method such as an extrusion laminating method in which a molten resin is laminated as a base material 2 via an anchor coating agent layer made of an adhesive can be used. In this case, the thickness of the base material 1 and the base material 2 is preferably 1 to 300 μm, for example. Furthermore, it is preferably 5 to 200 μm, particularly preferably 10 to 100 μm.

Examples of the method for producing a laminate according to a preferred embodiment of the present invention include the following. First, if a corona discharge treated film is used as the substrate 1, the gravure printing ink composition of the present invention (gravure Ink) is printed to form a printing layer. Then, an adhesive layer is formed on the formed printing layer, and the base material 1 and the base material 2, which is a plastic film made of the material mentioned above, are bonded together via the formed adhesive layer ( It can be easily obtained by laminating.

As mentioned above, the lamination process can be performed by using a known method such as a dry lamination method or a melt extrusion lamination method. The dry lamination method is a method in which an adhesive is applied onto the printed layer of a printed matter or a sealant, dried, and then the printed material and the sealant are pressed together and laminated. The melt extrusion lamination method is a method of obtaining a laminate by the following procedure. In this method, first, an adhesive called an anchor coating agent is applied onto the printing layer (printing surface) on the base material 1 to form an anchor coating agent layer, and then the resin is melted and extruded. A resin is laminated on the anchor coating agent layer. Alternatively, a method of laminating the base material 2, which is a plastic film made of the material mentioned above, on a layer formed by melt-extruding resin using the melt-extrusion lamination method (so-called melt-extrusion sandwich lamination method or A laminate is obtained by a melt extrusion tandem lamination method.

Hereinafter, the present invention will be specifically explained based on Examples, but the present invention is not limited to these Examples. Note that "parts" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

[Production Example 1] (Preparation of carbonate compound I)
Neopentyl glycol diglycidyl ether (trade name: "Denacol EX-211", manufactured by Nagase ChemteX) with an epoxy equivalent of 138 g/eq was placed in a reaction vessel equipped with a stirrer, a thermometer, a gas inlet tube, and a reflux condenser. 100 parts of N-methyl-2-pyrrolidone (NMP), and 20 parts of sodium iodide (manufactured by Wako Pure Chemical Industries, Ltd.) were added and uniformly dissolved. The reaction was carried out at 100° C. for 10 hours while stirring and introducing carbon dioxide gas (CO ₂ gas) at a rate of 0.5 L/min.

After the reaction was completed, 400 parts of ethyl acetate and 800 parts of water were added and stirred for 1 hour. Thereafter, the ethyl acetate phase was collected, and the solvent was removed using an evaporator to obtain a viscous liquid compound. An IR analysis of the powder obtained using an infrared spectrophotometer (trade name: "FT-720", manufactured by Horiba, Ltd., hereinafter referred to as FT-IR) revealed that there was a concentration of about 910 cm ^-1 in the raw material. It was found that the absorption peak derived from the epoxy group disappeared, and a new absorption peak derived from the carbonate group (carbonyl group) appeared around 1800 cm ^-1 . The obtained compound (reactant) was confirmed to be a compound represented by the following formula (Compound I) having a carbonate group with a cyclic structure formed by a reaction between an epoxy group and carbon dioxide. The calculated carbon dioxide content of Compound I obtained above is 24.1%.

[Synthesis example 1]
(Polyhydroxypolyurethane A: Synthesis of hydroxyl value 41.8 mgKOH/g)
In a reaction vessel equipped with a stirring device, a reflux device with an opening for opening to the atmosphere, and a nitrogen inlet tube, 100 parts of the cyclic carbonate-containing compound I obtained in Production Example 1 and hexamethylene diamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were placed. , similar materials were used in other examples), 94.6 parts of Priamine 1074 (trade name, manufactured by Croda Japan Co., Ltd.), and 65 parts of ethyl acetate as a reaction solvent were added, and the mixture was heated to about 80°C. The reaction was carried out for 5 hours under reflux conditions. The preamine 1074 used above is a 36-carbon dimer diamine having a 6-carbon ring structure (dimer structure ratio: 95% or more, amine value: 210 mgKOH/g).

When the resin solution after the reaction was analyzed by FT-IR, the absorption derived from the carbonyl group of the cyclic carbonate that had been observed near 1800 cm ^-1 completely disappeared, and a new urethane bond was observed near 1760 cm ^-1 . Absorption derived from the carbonyl group was confirmed. This is a prepolymer of _NH2 -terminated polyhydroxypolyurethane (HPU).

Next, without cooling the reaction solution obtained above, 30.5 parts of hexamethyldisilazane (product name: SZ-31, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 30 minutes. After 30 minutes of dropping, FT-IR was measured, and it was confirmed that the peak around 933 cm ⁻¹ derived from N—Si had disappeared, and the reaction was completed. After the reaction, 315.4 parts of ethyl acetate was added as a diluent to the solution, and the mixture was cooled to room temperature. Next, while stirring the cooled solution, 18.0 parts of isophorone diisocyanate (manufactured by Evonik Japan, the same product was used in other examples) was slowly added dropwise. After the dropwise addition, FT-IR was measured, and it was confirmed that the peak around 2260 cm ⁻¹ derived from the isocyanate group had disappeared, and the reaction was completed.

The resulting solution is pale yellow and transparent, and is a polyhydroxypolyurethane resin solution with a resin content (solid content) of 35%. The molecular weight of the obtained polyhydroxypolyurethane was measured by GPC using DMF (N,N-dimethylformamide) as a mobile phase under the conditions described below. As a result, the weight average molecular weight was 49,000. The GPC measurement was carried out using GPC-8820 (trade name, manufactured by Tosoh Corporation) as a measuring device and the following four columns. Specifically, four columns Super AW2500, AW3000, AW4000, and AW5000 (trade names, all manufactured by Tosoh Corporation) were used. Further, the hydroxyl value measured according to JIS-K 1557-1 was 41.8 mgKOH/g in terms of solid content. Note that GPC measurements in other examples were also performed using the same apparatus and under the same conditions as above.

[Synthesis example 2]
(Polyhydroxypolyurethane B: Synthesis of hydroxyl value 53mgKOH/g)
In a reaction vessel equipped with a stirring device, a reflux device with an opening to the atmosphere, and a nitrogen introduction tube, 100 parts of the cyclic carbonate-containing compound I obtained in Production Example 1 described above and 18.8 parts of hexamethylene diamine were placed. 87.3 parts of preamine 1074 and 59.9 parts of ethyl acetate as a reaction solvent were added, and the reaction was carried out for 5 hours under reflux conditions at about 80°C. When the resin solution after the reaction was analyzed by FT-IR, the absorption derived from the carbonyl group of the cyclic carbonate that had been observed near 1800 cm ^-1 completely disappeared, and a new urethane bond was observed near 1760 cm ^-1 . Absorption derived from the carbonyl group was confirmed. This is a prepolymer of _NH2 -terminated polyhydroxypolyurethane (HPU).

Next, without cooling the reaction solution, 26.1 parts of hexamethyldisilazane (product name: SZ-31, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 30 minutes. After 30 minutes of dropping, FT-IR was measured and it was confirmed that the peak around 933 cm ⁻¹ derived from N—Si had disappeared, and the reaction was terminated. After the reaction, 385.1 parts of ethyl acetate was added as a diluting solvent to the solution, and the mixture was cooled to room temperature. Next, while stirring the cooled solution, 12.0 parts of isophorone diisocyanate was slowly added dropwise. After the dropwise addition, FT-IR was measured and it was confirmed that the peak around 2260 cm ⁻¹ derived from the isocyanate group had disappeared, and the reaction was completed.

The resulting solution is pale yellow and transparent, and is a polyhydroxypolyurethane resin solution with a resin content of 35%. The molecular weight of the obtained polyhydroxypolyurethane was measured by GPC in the same manner as in Synthesis Example 1 using DMF as a mobile phase. As a result, the weight average molecular weight was 44,000. Further, the hydroxyl value measured according to JIS-K 1557-1 was 53 mgKOH/g in terms of solid content.

[Synthesis Example 3] (Polyhydroxypolyurethane C: Synthesis of hydroxyl value 64mgKOH/g)
In a reaction vessel equipped with a stirring device, a reflux device with an opening for opening to the atmosphere, and a nitrogen introduction tube, 100 parts of the cyclic carbonate-containing compound I obtained in Production Example 1, 18.8 parts of hexamethylene diamine, 87.3 parts of Priamine 1074 and 58.9 parts of ethyl acetate as a reaction solvent were added, and the reaction was carried out for 5 hours under reflux conditions at about 80°C. When the resin solution after the reaction was analyzed by FT-IR, the absorption derived from the carbonyl group of the cyclic carbonate that had been observed near 1800 cm ^-1 completely disappeared, and a new urethane bond was observed near 1760 cm ^-1 . Absorption derived from carbonyl groups was confirmed. This is a prepolymer of _NH2 -terminated polyhydroxypolyurethane.

Next, 21.8 parts of hexamethyldisilazane (product name: SZ-31) was added dropwise over 30 minutes without cooling the reaction solution. After 30 minutes of dropping, FT-IR was measured, and it was confirmed that the peak around 933 cm ⁻¹ derived from N—Si had disappeared, and the reaction was completed. After the reaction, 378.9 parts of ethyl acetate was added as a diluent to the solution, and the solution was cooled to room temperature. Next, while stirring the cooled solution, 12.0 parts of isophorone diisocyanate was slowly added dropwise. After dropping, FT-IR was measured and it was confirmed that the peak around 2260 cm ⁻¹ derived from isocyanate groups had disappeared, and the reaction was completed.

The resulting solution is pale yellow and transparent, and is a polyhydroxypolyurethane resin solution with a resin content of 35%. The molecular weight of the obtained polyhydroxypolyurethane was measured by GPC in the same manner as in Synthesis Example 1 using DMF as a mobile phase. As a result, the weight average molecular weight was 43,000. Further, the hydroxyl value measured according to JIS-K 1557-1 was 64 mgKOH/g in terms of solid content.

[Synthesis example 4]
(Polyhydroxypolyurethane D: Synthesis of hydroxyl value 82mgKOH/g)
In a reaction vessel equipped with a stirring device, a reflux device with an opening to the atmosphere, and a nitrogen inlet tube, 100 parts of the cyclic carbonate-containing compound I obtained in Production Example 1 described above and 18.8 parts of hexamethylene diamine were added. 87.3 parts of preamine 1074 and 58.0 parts of ethyl acetate as a reaction solvent were added, and the reaction was carried out for 5 hours under reflux conditions at about 80°C. When the resin solution after the reaction was analyzed by FT-IR, the absorption derived from the carbonyl group of the cyclic carbonate that had been observed near 1800 cm ^-1 completely disappeared, and a new urethane bond was observed near 1760 cm ^-1 . Absorption derived from carbonyl groups was confirmed. This is a prepolymer of _NH2 -terminated polyhydroxypolyurethane (HPU).

Next, 17.4 parts of hexamethyldisilazane (product name: SZ-31) was dropped over 30 minutes without cooling the reaction solution. After 30 minutes from the dropwise addition, FT-IR was measured, and it was confirmed that the peak at around 933 cm ⁻¹ derived from N-Si had disappeared, and the reaction was terminated. 372.6 parts of ethyl acetate was added as a diluting solvent to the solution after the reaction was completed, and the solution was cooled to room temperature. Next, 12.0 parts of isophorone diisocyanate was slowly dropped while stirring the cooled solution. After the dropwise addition, FT-IR was measured, and it was confirmed that the peak at around 2260 cm ⁻¹ derived from the isocyanate group had disappeared, and the reaction was terminated.

The resulting solution was pale yellow and transparent, and was a polyhydroxypolyurethane resin solution with a resin content of 35%. The molecular weight of the obtained polyhydroxypolyurethane was measured by GPC in the same manner as in Synthesis Example 1 using DMF as a mobile phase. As a result, the weight average molecular weight was 42,000. Further, the hydroxyl value measured according to JIS-K 1557-1 was 82 mgKOH/g in terms of solid content.

[Comparative synthesis example 1]
(Synthesis of polyurethane a)
Polyurethane a used in the comparative example was synthesized as follows. First, a polyester polyol used as a raw material for the synthesis of polyurethane a was prepared as follows. As raw materials for preparing polyester polyol, adipic acid/succinic acid=60/40 (mole ratio) was used as the dicarboxylic acid component, and 1,2-propanediol was used as the diol component. Next, these dicarboxylic acid components and diol components were used in appropriate amounts to achieve the desired molecular weight and polymerized to obtain a polyester polyol having a hydroxyl value of 37.3 mgKOH/g and a number average molecular weight of 3000. .

Next, 500 parts of the polyester polyol prepared above and 66.4 parts of isophorone diisocyanate similar to that used in Synthesis Example 1 were placed in a reaction vessel, and the mixture was reacted at 100°C for 5 hours under a nitrogen stream to form a polyester polyol containing NCO groups. A urethane prepolymer with a yield of 1.87% was obtained. The obtained urethane prepolymer was dissolved in 188.8 parts of ethyl acetate as a diluting solvent to obtain a urethane prepolymer solution with a nonvolatile content of 75%.

Next, a mixture (amine solution) of 22.2 parts of isophoronediamine, 0.850 parts of diethanolamine, 980.4 parts of ethyl acetate, and 206.3 parts of isopropyl alcohol was blended, and while stirring, the urethane obtained earlier was added. The prepolymer solution was added dropwise and reacted at 40°C for 1 hour. As a result, a polyurethane a resin solution having a nonvolatile content (solid content) of 30% and a hydroxyl value of 1.5 mgKOH/g was obtained.

[Comparative synthesis example 2]
(Synthesis of polyurethane b)
Polyurethane b used in the comparative example was synthesized in the following manner. First, a polyester polyol having a hydroxyl value of 37.3 mgKOH/g and a number average molecular weight of 3,000 was obtained in the same manner as in the synthesis of polyurethane a. Next, using the polyester polyol prepared above in a reaction vessel, a urethane prepolymer having an NCO group content of 1.87% was obtained in the same manner as in the synthesis of polyurethane a. The obtained urethane prepolymer was dissolved in 188.8 parts of ethyl acetate as a diluting solvent to obtain a urethane prepolymer solution with a nonvolatile content of 75%.

Next, a mixture (diamine solution) of 23.2 parts of isophoronediamine, 0.168 parts of monoethanolamine, 980.9 parts of ethyl acetate, and 206.5 parts of isopropyl alcohol was blended, and while stirring, the mixture obtained previously was mixed. The urethane prepolymer solution was added dropwise to the mixture, and the mixture was reacted at 40° C. for 1 hour. As a result, a polyurethane b resin solution having a nonvolatile content (solid content) of 30% and a hydroxyl value of 5.8 mgKOH/g was obtained.

[About polyurethane resin used in Examples or Comparative Examples]
Table 1 summarizes the properties of polyhydroxypolyurethanes (HPU) A to D prepared in Synthesis Examples 1 to 4 above and used as component A in Examples described later, and polyurethanes used in Comparative Examples described later. Ta. In Table 1, polyhydroxypolyurethane A is expressed as HPU-A, polyhydroxypolyurethane B as HPU-B, polyhydroxypolyurethane C as HPU-C, and polyhydroxypolyurethane D as HPU-D. Regarding the polyurethanes used in the comparative examples, the one obtained in Comparative Synthesis Example 1 was designated as PU-a, and the one obtained in Comparative Synthesis Example 2 was designated as PU-b.

[About vinyl chloride-vinyl acetate copolymer used in Examples or Comparative Examples]
Table 2 shows the properties of vinyl chloride-vinyl acetate copolymers A to C with different hydroxyl values, which were used as component B in the examples, and vinyl chloride-vinyl acetate copolymers D, which were used in the comparative examples. Ta. "Salt vinyl acetate resin D" has a hydroxyl value of 0 mgKOH/g and does not fall under the B component defined in the present invention.

[Preparation of salt-vinyl acetate resin varnish]
20 parts of salt vinyl acetate resin A shown in Table 2 was placed in a container, 80 parts of ethyl acetate was added, and the mixture was stirred at room temperature for 2 hours. After visually confirming that the salt-vinyl acetate resin in a solid state was completely dissolved, a salt-vinyl acetate resin varnish A having a solid content of 20 parts was obtained. Salt-vinyl acetate resin varnishes B, C, and D were also produced in the same manner as in the method used to obtain salt-vinyl acetate resin varnish A described above.

[Preparation of gravure printing ink composition]
In the examples, polyhydroxypolyurethane having the properties shown in Table 1 was used as the A component, and vinyl chloride-vinyl acetate copolymer having the hydroxyl value shown in Table 2 was used as the B component. The gravure printing ink composition of the example of the present invention was prepared by using a mixed solvent of ethyl acetate, isopropyl alcohol (IPA) and propylene glycol monomethyl ether (PM) as the organic solvent C. Created. In addition, when preparing the gravure printing ink composition, carbon black (abbreviated as CB in the table), titanium oxide (abbreviated as Ti oxide in the table), or phthalocyanine blue (in Table 3) may be used as a coloring agent, if necessary. (abbreviated as PB) was used. The preparation of the gravure printing ink composition of the example can be easily carried out by adding a colorant and other additives as necessary to the above A component and B component, and mixing with the organic solvent of the C component. I can do it. In the following Examples and Comparative Examples, a mixture of each component in the proportions listed in Tables 3 to 5 was kneaded in a bead mill (equipment name: Mighty Mill, manufactured by Inoue Seisakusho Co., Ltd.) to produce a gravure printing ink composition. (hereinafter also simply referred to as printing ink) was prepared.

[Examples 1 to 6]
Table 3 shows the formulations of the printing inks of Examples 1 to 6. In Examples 1 to 6, as shown in Table 3, HPU-C prepared in Synthesis Example 3 with a hydroxyl value of 64 mgKOH/g was used as the A component, and vinyl acetate with a hydroxyl value of 154 mgKOH/g was used as the B component. By using resin varnish A and changing the blending amounts of component A and component B, the mass ratio (A):(B) of non-volatile components in component A and component B was 95:5 to 20:80. A printing ink was prepared by the method described above. During the preparation, a mixed solvent of ethyl acetate, isopropyl alcohol (IPA) and propylene glycol monomethyl ether (PM) was used as organic solvent C. Furthermore, colored printing inks were prepared using phthalocyanine blue in Example 1, titanium oxide in Example 2, and carbon black in Examples 4 to 6 as colorants. In Example 3, a colorless printing ink was prepared without using a colorant.

[Examples 7 to 12]
Table 4 shows the formulations of the printing inks of Examples 7 to 12. In Examples 7 to 12, as shown in Table 4, the type of polyhydroxypolyurethane resin of the A component and the salt vinegar of the B component to be used together were changed without changing the mass ratio of nonvolatile components in the A component and the B component. Printing inks were prepared using different types of vinyl resin varnish. As shown in Table 4, in Examples 7 to 12, a mixed solvent in which ethyl acetate, isopropyl alcohol (IPA), and propylene glycol monomethyl ether (PM) were mixed at the same mixing ratio was used as the organic solvent C. , a printing ink was prepared using carbon black as a colorant. The printing ink of Example 12 is an example in which 3 parts of isophorone diisocyanate (IPDI) adduct with a solid content of 30% was added as a curing agent.

[Comparative Examples 1 to 5]
Table 5 shows the formulations of the printing inks of Comparative Examples 1 to 5. As shown in Table 5, in the printing inks of Comparative Examples 1 and 2, conventional polyurethane resin was used without using polyhydroxypolyurethane. The printing ink of Comparative Example 3 does not use the salt vinyl acetate resin varnish of component B. In addition, the printing ink of Comparative Example 4 has a small amount of polyhydroxypolyurethane, which is the A component defined in the present invention, and the mass ratio of nonvolatile content in the salt-vinyl acetate resin varnish, which is the A component and B component, is as defined in the present invention. This is a printing ink with a composition outside the range specified. In the printing ink of Comparative Example 5, a salt-vinyl acetate resin varnish D having no hydroxyl value, which does not fall under the B component specified in the present invention, was used.

[Evaluation of printing ink]
Printed matter was obtained by the method described below using each of the printing inks of Examples 1 to 12 and Comparative Examples 1 to 5 prepared as described above, and a printed film was formed using the evaluation method and evaluation criteria described below. And the laminate was evaluated for "adhesion to the base material", "blocking resistance" and "laminate strength". In order to confirm that the printing inks of the examples of the present invention show good effects on various substrates that are commonly used as substrates for printing, evaluations were conducted on various transparent substrates listed in Table 6. Various base materials were used: vapor-deposited PET film, various types of transparent vapor-deposited NY, untreated PET, PET, PT (ordinary cellophane), NY (nylon), and OPP (biaxially oriented polypropylene). Table 6 shows the product name, manufacturer, and characteristics of each base material used in the evaluation test with reference to the catalog.

The meaning of "protective layer" in Table 6 is that "presence" indicates that a protective layer that protects the deposited material is a film applied to the vapor deposition surface, and "absence" indicates a film that does not have a protective layer. shows. In addition, "treated PET" numbered 14 in Table 6 is a commercially available product whose film surface has been subjected to corona discharge treatment, which is a commonly performed process to increase the wetting index and make it easier for ink to print on the film. It means that. On the other hand, the number 13 in Table 6, "untreated PET", is a commercially available product that has not been subjected to corona discharge treatment. The evaluation results are summarized in Table 7 for the printing inks of Examples and in Table 8 for the printing inks of Comparative Examples. The evaluation was performed for each of the base materials numbered 1 to 17 listed in Table 6 above.

[Adhesion to base material 1]
Using the same solvent and mixed solvent in the same ratio as used in preparing the inks of the Examples and Comparative Examples described above, 20 parts of the mixed solvent was added to 100 parts of each ink having the composition listed in Tables 3 to 5. This was diluted to prepare an ink for evaluation. Using the obtained inks for each evaluation, using a flatbed printing machine using a Helio 175 line plate, using plastic films of different brands numbered 1 to 17 shown in Table 6 as the base material 1, the base material 1 Each of the obtained prints was used to evaluate the "adhesion to the base material 1" as described below. That is, after affixing cellophane tape (manufactured by Nichiban Co., Ltd.) to the printed surface (printed film surface) of the obtained printed matter, the tape was quickly peeled off, and the state of the printed surface after being peeled off was visually observed. Then, the "adhesion to the base material 1" was evaluated on the following five scales. Regarding the adhesion of the printing ink to the substrate 1, a rating of 4 or higher is within the practical range. Table 7-1 summarizes the evaluation results of the adhesion to the substrate 1 for printed matter using the printing ink of the example. Furthermore, Table 8-1 summarizes the evaluation results for printed matter using the printing ink of the comparative example.

(Evaluation criteria)
5: The printed film was not peeled off from the base film at all.
4: Less than 20% of the area ratio of the printed film has peeled off from the base film.
3: The area ratio of the printed film is 20% or more and less than 50% peeled off from the base film.
2: The area ratio of the printed film is 50% or more and less than 80% peeled off from the base film.
1: 80% or more of the area ratio of the printed film has peeled off from the base film.

[Blocking resistance]
Using the same solvent and mixed solvent in the same ratio as used in preparing the inks of the Examples and Comparative Examples described above, 20 parts of the mixed solvent was added to 100 parts of each ink having the composition listed in Tables 3 to 5. This was diluted to prepare an ink for evaluation. Using the obtained inks for each evaluation, prints were created by printing on each base material 1 listed in Table 7 using a flatbed printing machine using a Helio 175 line plate, and using the obtained prints, the following In this way, the "blocking resistance" was evaluated.

The printed matter obtained above was cut out into a size of 4 cm x 4 cm, and the ink-coated side was overlapped with the untreated side of the same plastic film used for printing cut into the same size. A load of cm ² was applied and the sample was left in an atmosphere at 40° C. for 24 hours. After standing, the printed surface (printed film surface) and the overlapping plastic film are peeled off by hand, and the degree of peeling of the ink film (printed film) is measured by the peeling resistance felt by the hand and the peeled area ratio by visual observation. evaluated. That is, a high peel resistance indicates that the printed film will set off on the overlaid film, so it is required that there be no peel resistance. Specifically, the blocking resistance was evaluated on the following five scales. As for blocking resistance, a rating of 4 or higher is within the practical range. Table 7-2 summarizes the evaluation results of blocking resistance of printed materials using the printing inks of Examples. Furthermore, Table 8-2 summarizes the evaluation results of printed matter using the printing ink of the comparative example.

(Evaluation criteria)
5: No peeling of the printed film was observed, and no peeling resistance was felt at all.
4: No peeling of the printed film was observed, but some peeling resistance was felt.
3: Some peeling of the printed film was observed, and some peeling resistance was felt.
2: Peeling of the printed film was observed, and obvious peeling resistance was felt.
1: Most of the printed film peeled off, and strong peeling resistance was felt.

[Suitability for lamination]
[Preparation of laminate laminate for evaluation by dry lamination method]
Using the same solvent and mixed solvent in the same ratio as used in preparing the inks of the Examples and Comparative Examples described above, 20 parts of the mixed solvent was added to 100 parts of each ink having the composition listed in Tables 3 to 5. This was diluted to prepare an ink for evaluation. As the base material 1, a corona discharge-treated PET film number 14 shown in Table 6 (trade name "Ester E5102", manufactured by Toyobo Co., Ltd., thickness 12 μm) was prepared. Using a Helio 175 line gravure plate, each ink for evaluation was applied to the treated side of the base material 1 by a gravure printing method to form a printing layer to obtain printed matter. This printed matter is a laminate in which the gravure printing ink composition of the present invention is laminated on a base material 1.

Gravure printing was applied to the printed matter obtained above with a dry laminating adhesive (trade name: "Seikabond E263/C-75N", manufactured by Dainichiseika Kagyo Co., Ltd.) at a dry coating amount of 3 g/ ^m2 . The film was coated and dried by the method, and then thermocompression bonded using LLDPE (trade name "TUX-HC", manufactured by Mitsui Chemicals Tohcello Co., Ltd., thickness 60 μm) as the base material 2. Thereafter, aging was performed at 40° C. for 48 hours to obtain a laminate. Furthermore, for base materials 1 other than number 14 shown in Table 6, laminates were obtained in the same manner as above except that each base material 1 was used.

[Measurement of laminate strength]
A rectangular sample with a width of 15 mm and a length of 100 mm was taken from the laminate obtained as described above, and a T-shaped peel test sample was prepared as a sample for measuring adhesive strength. For each T-type peel test sample, a T-type peel test was conducted using a tensile tester (trade name "Tensilon RTG-1225", manufactured by A&D Co., Ltd.) at a tensile speed of 300 mm/min. The adhesive strength (T-peel strength) between base material 1 and base material 2 in the sample was measured. In this case, it is required to have high peel strength and be difficult to peel off. Although the laminate strength depends on the application, a rating of 3 or higher is within the practical range. Table 7-3 summarizes the evaluation results of lamination strength for printed matter using the printing inks of Examples. Furthermore, Table 8-3 summarizes the evaluation results for printed matter using the printing ink of the comparative example.

(Evaluation criteria)
5: Peel strength is 2.0 N or more 4: Peel strength is 1.5 N or more and less than 2.0 N 3: Peel strength is 1.0 N or more and less than 1.5 N 2: Peel strength is 0.5 N or more and less than 1.0 N 1: Peel strength is less than 0.5N

Evaluation results for each printed matter printed using the printing inks of the examples shown in Tables 7-1 to 7-3 and the printing inks of the comparative examples shown in Tables 8-1 to 8-3. From the evaluation results for each printed material, the following was confirmed. According to the printing ink of the example, the printed matter showed good results in terms of adhesion to the substrate, blocking resistance, and lamination strength on any of the various commercially available substrates. It was confirmed that the printed matter was excellent in versatility with respect to the base material and that it was possible to form printed matter of stable quality. On the other hand, when printing with the printing ink of the comparative example, the evaluation obtained differs depending on the substrate used for printing, and the evaluation also differs depending on the evaluation item, regardless of which printing ink is used. It was not possible to obtain stable effects. In particular, as shown in Table 8-1, when the printing ink of the comparative example was used, there was a problem in the adhesion of the formed printed film to the substrate on most of the different types of substrates 1 printed. This was confirmed. On the other hand, when the printing ink of the example of the present invention was used, it was confirmed that it showed sufficient adhesion to various base materials provided by various companies to which it was applied. A remarkable effect was obtained.

Claims (7)

A polyhydroxypolyurethane (A) having a hydroxyl group, which is a reaction product of a five-membered cyclic carbonate compound formed by reacting an epoxy compound and carbon dioxide with an amine compound, and a vinyl chloride-vinyl acetate copolymer (B) having a hydroxyl group. ) and an organic solvent (C), the gravure printing ink composition comprises:
The polyhydroxypolyurethane (A) and the vinyl chloride-vinyl acetate copolymer (B) have a mass ratio of nonvolatile components of (A):(B)=95:5 to 20:80. A gravure printing ink composition. The gravure printing ink composition according to claim 1, wherein the vinyl chloride-vinyl acetate copolymer (B) has a hydroxyl value in the solid content of 60 to 180 mgKOH/g. The gravure printing ink composition according to claim 1 or 2, wherein the polyhydroxy polyurethane (A) has a hydroxyl value in the solid content of 25 to 300 mgKOH/g. The gravure printing ink composition according to claim 3, wherein the solid content of the polyhydroxy polyurethane (A) has a hydroxyl value of 25 to 100 mgKOH/g, and a portion of the hydroxyl groups are silylated. The gravure printing ink composition according to claim 1 or 2, further comprising a colorant (D). A laminate comprising a gravure printing ink composition laminated on a base material, wherein the gravure printing ink composition is the gravure printing ink composition according to claim 1 or 2. A laminate laminate in which a base material 1, a printing layer made of a gravure printing ink composition formed by printing on the base material 1, an adhesive layer, and a base material 2 are laminated in this order, and the gravure A laminate laminate, wherein the printing ink composition is the gravure printing ink composition according to claim 1 or 2.