WO2021260977A1 - Primer composition, printed article, and laminate - Google Patents

Abstract

The present invention is a primer composition containing a block copolymer (A) comprising: a styrene-based polymer block (a); and at least one (b) among a butadiene-based polymer block, an isoprene-based polymer block, and hydrogenated product blocks thereof. The mass ratio (a)/(b) between the polymer block (a) and the polymer block (b) is 5/95 to 70/30. The present invention makes it possible to improve the adhesiveness and laminate strength of a laminate of extrusion lamination and, in particular, to achieve high adhesiveness and laminate strength without separation of a polypropylene extrusion resin layer even if a print layer is included for which general-purpose ink has been used.

Description

Primer compositions, printed matter and laminates

The present invention relates to a primer composition, a printed matter and a laminate used for a laminate formed by extrusion lamination.

Polyolefins (films) typified by polyethylene and polypropylene are widely used for food packaging materials and various industrial packaging materials. Laminates made by laminating multiple films are the mainstream for these packages, but as packaging materials using polyolefin, a laminating method using an adhesive and melting without using an adhesive are used. There is a laminating method that extrudes resin.

In the case of extruded lamination, the extruded resin is mostly polyethylene. Such a laminated body of polyethylene extruded lamination is produced, for example, by providing a printing layer (ink layer) on a biaxially stretched polypropylene film base material and melt-extruding polyethylene on the surface of the printing layer to laminate it. On the other hand, polypropylene may be used as the extruded resin instead of polyethylene.

However, many of the current liquid inks for general-purpose packages have the extruded resin suitable for the extruded lamination of polyethylene, but the liquid ink for packages whose extruded resin is suitable for the extruded lamination of polyproprene is chlorinated. There are only some types of ink such as propylene-based ink. Such chlorinated polypropylene-based inks have an environmental problem because toluene is used at the time of printing. Furthermore, since the resin contains a large amount of chlorine, there are concerns about the environment such as dioxin generation.
In recent years, due to the problem of marine plastic pollution, it has become necessary to promote the recycling of packages, and monomaterial packages composed of a single material are required as packages that are easier to recycle.

From this point of view, a laminate produced by melt-extruding polypropylene with a general-purpose ink that does not contain chlorinated polypropylene as a main component and laminating is desired.
Patent Document 1 describes melt-extruding a polypropylene resin onto an anchor coat layer containing an acid-modified polypropylene in order to enable extrusion lamination using the polypropylene resin. However, in the method of Patent Document 1, the anchor coat layer is directly provided on the polyolefin film (base material), and there is a concern that the adhesion may be deteriorated as in the case of using a base material having a printed layer. Is not supposed to be used. Therefore, it is desired to realize a laminate capable of realizing polyproprene extrusion lamination having sufficient adhesion even when having a print layer using a general-purpose ink.

Japanese Unexamined Patent Publication No. 2015-163688

An object of the present invention is to improve the adhesion and the laminating strength of the laminated body of the extruded lamination. In particular, even when a printed layer using a general-purpose ink is provided, the polypropylene extruded resin layer does not peel off. It is an object of the present invention to provide a primer composition, a printed matter and a laminate used for a laminate of extruded resins, which can realize high adhesion and laminade strength.

As a result of diligent research to solve the above-mentioned problems, the present inventors have obtained a styrene-based polymer block (a), a butadiene-based polymer block, an isoprene-based polymer block, or these in polypropylene resin melt extrusion. It is a primer composition containing a block copolymer (A) composed of at least one of the hydrogenated material blocks (b) of the above, and is a mass ratio (a) of the polymer block (a) and the polymer block (b). ) / (B) has been found to solve the above-mentioned problems by using a primer composition having 5/95 to 70/30 as a coating agent.

That is, the present invention is a block copolymer composed of a styrene-based polymer block (a) and at least one (b) of a butadiene-based polymer block, an isoprene-based polymer block, or a hydrogenated product block thereof (b). A primer composition containing A), wherein the mass ratio (a) / (b) of the polymer block (a) to the polymer block (b) is 5/95 to 70/30. Regarding the composition.

The present invention also relates to a primer composition in which the block copolymer (A) is a maleic anhydride-modified block copolymer and has an acid value of 1 to 30 [mgCH ₃ ONa / g].

Further, the present invention contains the auxiliary resin (B) and / or the blocking inhibitor (C), and when the auxiliary resin (B) is contained, the following (1) is satisfied and the blocking inhibitor (C) is contained. In this case, it is a primer composition satisfying the following (2).
(1) The Tg of the auxiliary resin (B) is 50 ° C. or higher, and the mass ratio (A) / (B) of the block copolymer (A) to the auxiliary resin (B) is 99/1 to 50/50. (2) The total amount of the primer composition contains 0.1 to 5.0% by mass of the blocking inhibitor (C). Further, the present invention is a primer in which the primer composition is in contact with the extruded resin, and the extruded resin is said to be contained. Relates to a primer composition containing at least polypropylene.

The present invention also relates to a primer composition in which the substrate on which the primer composition is printed contains at least polypropylene.

The present invention also relates to a primer composition in which the primer composition is printed on a printing ink layer.

The present invention also relates to a printed matter having a primer layer formed by printing a primer composition on a substrate.

The present invention also relates to a laminate laminate in which a printing ink layer, the primer layer, and an extruded resin layer are laminated at least in this order on a substrate.

Further, the present invention is a laminate in which a printing ink layer, the primer layer, an extruded resin layer, and a sealant layer are laminated at least in this order on a substrate, and the sealant layer contains at least polypropylene. Regarding the laminated body to be used.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to improve the adhesion and the laminating strength of the laminated body of polyproprene extruded lamination. Further, since a general-purpose resin other than chlorinated polypropylene can be used in the laminated body of polypropylene extruded lamination, the environmental load can be reduced.

<Primer composition>
The primer composition of the present invention has a block copolymer weight consisting of a styrene-based polymer block (a) and at least one of a butadiene-based polymer block, an isoprene-based polymer block, or a hydrogenated product block thereof (b). A primer composition containing the coalescence (A), wherein the weight ratio (a) / (b) of the polymer block (a) to the polymer block (b) is 5/95 to 70/30. be. By providing the primer layer formed by the primer composition of the present invention on the substrate, the adhesion to the melted extruded resin can be improved.

(Block Copolymer (A))
As the copolymer composed of at least one of the styrene-based polymer block (a), the butadiene-based polymer block, and the isoprene-based polymer block (b), triblock copolymers and tetrablock copolymers are preferable. , Preferably a linear structure. Specifically, a styrene-butadiene-styrene copolymer, a styrene-isoprene-styrene copolymer, a styrene-butadiene-isoprene-styrene copolymer or a styrene-butadiene-styrene-isoprene-styrene copolymer is preferable.
The butadiene structural unit constituting the butadiene polymer block may be composed of 1,4-bonded butadiene or 1,2-bonded butadiene, but may be composed of 1,4-bonded butadiene. It is preferable to have both a butadiene-based polymer block (b-1) and a 1,2-bonded butadiene-based polymer block (b-2). The ratio of the 1,4-bonded butadiene-based polymer block (b-1) and the 1,2-linked butadiene-based polymer block (b-2) in the block copolymer (A) is not particularly limited. For example, the weight ratio is preferably (b-1) :( b-2) = 90:10 to 30:70.

The butadiene-based polymer block or isoprene-based polymer block constituting the block copolymer (A) is preferably a hydrogenated product block. By hydrogenation, the heat resistance of the block copolymer (A) can be improved, and the blocking resistance can be improved. For example, when hydrogenated to 1,4-bonded butadiene, the butadiene becomes a block of ethylene units, and when hydrogenated to 1,2-bonded butadiene, the butadiene becomes a block of butylene units. Butadiene-based polymer blocks and / or isoprene-based polymer blocks may be partially hydrogenated, but 1,4-bonded butadiene polymer blocks (b-) in the block copolymer (A). If both 1) and the 1,2-bonded butadiene-based polymer block (b-2) are present, hydrogenation should be selectively applied to the 1,2-linked butadiene-based polymer block (b-2). Is preferable. When selectively watering the block (b-2) composed of 1,2-bonded butadiene, the styrene-based polymer block (a) and the 1,4-bonded butadiene-based polymer block (b-) are used. 1), a block composed of butylene (a block hydrogenated with a 1,2-bonded butadiene polymer (b-2)), and a constituent unit (styrene-butadiene-) of a styrene polymer block (a). Butadiene-styrene) is preferably contained in the block copolymer (A).

It is also preferable to have a portion of the butadiene-based polymer block and / or the isoprene-based polymer block completely hydrogenated. In this case, a block composed of a styrene polymer block (a), a block composed of ethylene (a block hydrogenated with a 1,4-bonded butadiene polymer (b-1)), and a block composed of butylene (a block composed of butylene). A block hydrated with a 1,2-bonded butadiene polymer (b-2)) and a structural unit of the styrene polymer block (a) (styrene-ethylene-butylene-styrene, styrene-ethylene-propylene-styrene). ) Is preferably contained in the block copolymer (A).

The weight ratio (a) / (b) of the polymer block (a) to the polymer block (b) is 5/95 to 70/30, but in order to improve the blocking resistance, the polymer block (a) is used. The ratio of styrene in the above is preferably high, and the weight ratio (a) / (b) of the polymer block (a) to the polymer block (b) is preferably 10/90 or more, preferably 15/85 or more. More preferably, it is more preferably 25/75 or more, and even more preferably 30/70. On the other hand, if the proportion of styrene is too high, the laminating characteristics tend to deteriorate, so that the weight ratio (a) / (b) of the coalesced block (a) and the polymer block (b) is 65/35 or less. It is preferably 60/40 or less, more preferably 50/50, more preferably 40/60, and even more preferably 35/65.

The block copolymer (A) is preferably an acid-modified α-β-unsaturated carboxylic acid or an acid anhydride thereof by graft-polymerizing. As the α-β-unsaturated carboxylic acid or its acid anhydride, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, fumaric acid, maleic anhydride and the like are used, but maleic anhydride improves adhesion. It is preferable from the viewpoint of improving solubility and compatibility with other resins. The amount of α-β-unsaturated carboxylic acid or its acid anhydride added is not particularly limited, but the acid value is preferably 1 to 30 [mgCH ₃ ONa / g], and 5 to 20 [mgCH _3]. ONa / g] is more preferable.

The glass transition temperature of the block copolymer (A) (hereinafter sometimes referred to as "Tg") is preferably in the range of -60 ° C to 30 ° C, more preferably in the range of -40 to 10 ° C. In the present invention, the glass transition temperature is obtained by measurement with a differential scanning calorimeter.

(Auxiliary resin (B))
The primer composition of the present invention may contain an auxiliary resin (B) in addition to the block copolymer (A) described above. The auxiliary resin (B) preferably further contains a resin having a glass transition temperature higher than the glass transition temperature of the block copolymer (A) used in the primer composition of the present invention, for example, having a Tg of 50 ° C. or higher. It is preferable to use a resin having a temperature of 60 ° C. or higher, more preferably 70 ° C. or higher. By containing the resin (C) having a high glass transition temperature, the hardness of the coating film of the composition can be increased and the blocking resistance can be improved. Examples of the auxiliary resin (B) used in combination with the primer composition of the present invention as needed include a polyolefin resin, a polyurethane resin, an ethylene-vinyl acetate copolymer resin, a vinyl acetate resin, a polyamide resin, an acrylic resin, and a polyester. Examples thereof include resins, alkyd resins, polyvinyl chloride resins, rosin-based resins, rosin-modified maleic acid resins, ketone resins, cellulose resins, cyclized rubbers, rubber chlorides, polyvinyl butyral resins, and petroleum resins. These auxiliary resins (B) can be used alone or in combination of two or more.
The content of the auxiliary resin (B) is not particularly limited, but from the viewpoint of improving both the adhesion to the molten resin provided on the primer layer and the blocking resistance, the block copolymer (A) and the block copolymer (A) are used. The weight ratio (A) / (B) of the auxiliary resin (B) is preferably 99/1 to 50/50, preferably 98/2 to 55/45, and 97/3 to 50/50. It is preferably 95/5 to 60/40.

(Anti-blocking agent (C))
In addition, the primer composition of the present invention may contain an antiblocking agent (C). By containing the blocking inhibitor (C), the blocking resistance can be improved. Various waxes and fine particles can be used as the blocking inhibitor (C) to be used in combination with the primer composition of the present invention as needed. As the fine particles, commonly used anti-blocking agents such as inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles can be used.

Examples of the inorganic fine particles include silica, zirconia, barium sulfate, calcium carbonate, titanium oxide and the like. Examples of the organic fine particles include resin beads using urethane resin, acrylic resin, melamine resin and the like. Examples of the organic-inorganic composite fine particles include acrylic-silicon-based and silicone-based fine particles. Above all, it is preferable to use inorganic fine particles, and it is preferable to use silica. More specifically, it is preferable to use synthetic amorphous silica as the silica.

It is also preferable to use wax as the blocking inhibitor (C). Examples of the wax include waxes such as carnauba wax, polyolefin wax, paraffin wax, Fisher Tropsch wax, mitsuro, microcrystallin wax, polyethylene oxide-wax, and amido wax. These may be used alone or in combination. Above all, it is preferable to use polyolefin wax and / or amide wax.

Specific examples of the polyolefin wax include polyethylene wax and polypropylene wax, such as MPP-635VF (MicroPowerers, Inc.), MP-620VFXF (manufactured by MicroPowerers), and high wax 200P (Mitsui Chemicals, Inc.). ), High wax NP055 (manufactured by Mitsui Chemicals, Inc.) and the like.

Specific examples of the amide wax include fatty acid amide waxes, such as palmitic acid amide, stearic acid amide, ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, erucic acid amide, oleic acid amide, and stearyl erucic acid amide. And so on.

The blending amount of the blocking inhibitor (C) is not particularly limited, but it is preferable that the blocking inhibitor (C) is contained in an amount of 0.1 to 5.0% by mass in the total amount of the primer composition of the present invention. , 0.1 to 3.0% by mass, preferably 0.1 to 2.0% by mass, and preferably 0.1 to 1% by mass. If the total amount of the blocking inhibitor (C) is 0.1% by mass or more with respect to the total amount of the primer composition of the present invention, the blocking property tends to be maintained, and the total amount of the blocking inhibitor (C) is the total amount of the primer composition. On the other hand, if it is 5% by mass or less, the adhesion and the laminating strength tend to be maintained. The blending amount of the blocking inhibitor (C) is a mass ratio (total resin weight) to the total weight of the resin components (block copolymer (A) and auxiliary resin (B)) in the primer composition of the present invention. ) / (Total weight of the blocking inhibitor (C)) is preferably 99/1 to 80/20, and preferably 95/5 to 90/10.

(Other additives)
The anchor coating agent of the present invention obtained by the above method may contain other additives and the like, if necessary, in addition to the above-mentioned components.

Examples of the additive include antioxidants, lightfasteners, plasticizers, film-forming aids, leveling agents, foaming agents, thickeners, colorants, flame retardants, other aqueous resins, various fillers, and the like. It can be used within the range that does not impair the effect of.

(solvent)
The primer composition of the present invention is preferably mixed with a solvent and has a liquid form. Examples of the solvent include aromatic organic solvents such as toluene and xylene, aliphatic organic solvents such as cyclohexane and methylcyclohexane, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl acetate and ethyl acetate. Ester solvents such as n-propyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, alcohol solvents such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol and 1-methoxy2-propanol, propylene glycol monomethyl ether , Glycol ether solvent such as ethylene glycol monopropyl ether, and these can be used alone or in a mixture of two or more kinds. In recent years, from the viewpoint of working environment, it is desirable not to use aromatic solvents such as toluene and xylene.

Above all, from the viewpoint of the solubility of the resin and the drying property of the primer, it is preferable to use a solvent selected from an aliphatic organic solvent, an ester solvent, and an aliphatic alcohol solvent, and more specifically, methylcyclohexane or n acetate. -It is preferable to use propyl. Only one of them may be used, but it is preferable to have both.
The blending amount of the solvent is not particularly limited, but it is preferable that the total amount of the primer composition of the present invention contains 85 to 95% by mass of the solvent.

(Primer composition)
The viscosity of the primer composition of the present invention is preferably in the range of 10 mPa · s or more and 1000 mPa · s or less from the viewpoint of workability at the time of manufacturing the primer composition and at the time of applying the primer. The viscosity is a viscosity measured at 25 ° C. with a B-type viscometer manufactured by Tokimec.

The viscosity of the primer composition is determined by appropriately selecting the type and amount of the block copolymer (A) and the raw material used with the block copolymer (A), such as the auxiliary resin (B) and the organic solvent. Can be adjusted.

In the primer composition of the present invention, the block copolymer (A), another resin (B) if necessary, an antiblocking agent (C), and other additives are dissolved and / or other in an organic solvent. It can be manufactured by dispersing. When the blocking inhibitor (C) is contained, the block copolymer (A) and, if necessary, another resin (B) are directly added to the composition dissolved and / or dispersed in an organic solvent to mix and disperse. Alternatively, after preparing a dispersion of the blocking inhibitor, it may be mixed with the composition containing the block copolymer (A). As a dispersion method, a known method, for example, a paint shaker, a ball mill, an attritor, a basket mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a spike mill, an agitator mill or the like is used as a dispersion device using a medium. It can be dispersed by an ultrasonic homogenizer, a high-pressure homogenizer, a nanomizer, a resolver, a disper, a high-speed impeller disperser, or the like without using a medium.

If the primer composition contains air bubbles or unexpectedly coarse particles, it is preferable to remove them by filtration or the like in order to reduce the adhesion to the extruded molten resin. As the filter, a conventionally known one can be used.
The primer composition of the present invention is, for example, a coating agent for forming a primer layer for improving adhesion with an extruded resin layer and improving laminating strength in a laminated film (laminated body) produced by melt-extruding polyolefin. Can be suitably used as.
<Laminated body>
Hereinafter, the laminate using the primer composition of the present invention will be described. The layer structure of the laminate of the present invention has a primer layer formed by the primer composition of the present invention and a polyolefin resin layer formed by melt extrusion on the primer layer, and other configurations are described. It is not limited, and can be appropriately designed according to the application and purpose. Hereinafter, as an example thereof, a laminate having a structure in which a base material layer / a printing ink layer / a primer layer / an extruded resin layer / a sealant layer are sequentially laminated will be described. In the present invention, a printed matter having a primer layer on the printed matter is also referred to as a printed matter.

(Base layer)
The base material layer is not particularly limited, but when the printing layer is provided on the base material layer, various base materials used as the printing base material can be mentioned. Examples of such a base material include polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate (hereinafter sometimes referred to as PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, and poly. Polyester resins such as butylene terephthalate and polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, biodegradable resins such as aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate), polypropylene. (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyolefin resin such as polyethylene (LLDPE: low density polyethylene film, HDPE: high density polyethylene film), polyimide resin, polyallylate resin or a mixture thereof. Examples thereof include a film made of a thermoplastic resin and a laminate thereof. Further, for applications that do not require transparency, paper, synthetic paper, non-woven fabric, and aluminum foil can also be used. Above all, a polyolefin film is preferable from the viewpoint of monomaterialization. The primer layer of the present invention can improve the adhesion between each layer, and can be used as a polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) or a polypropylene film (CPP: unstretched polypropylene film, OPP: two). A film using a polyolefin resin such as axially stretched polyethylene film) is preferable. In particular, since it has excellent adhesion to a polypropylene material, a polypropylene film can be preferably used.

These base films may be unstretched films or stretched films, and the manufacturing method thereof is not limited.

The printed surface of the base film is preferably corona discharge treated, and silica, alumina, or the like may be vapor-deposited. Further, the thickness of the base film is not particularly limited, but usually it may be in the range of 1 to 500 μm.

(Printing ink layer)
A printing ink layer, which is a decorative layer for characters, figures, symbols, etc., can be provided on the base material layer. The printing can be provided by printing various printing inks used for printing on a film.

Various inks can be used as the printing ink. The colorant used may be any of a color pigment, a white pigment and the like. Examples of the colorant include organic pigments, inorganic pigments and dyes used in general inks, paints, recording agents and the like. Organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, diketopyrrolopyrrole, isoindole, etc. Pigment of.

Examples of inorganic pigments include carbon black, red iron oxide, aluminum, and mica (mica). Further, a bright pigment (Metashine; Nippon Sheet Glass Co., Ltd.), which is made of glass flakes or lumpy flakes as a base material and coated with a metal or a metal oxide, can be used. It is preferable to use carbon black for black ink, aluminum for gold and silver ink, and mica (mica) for pearl ink from the viewpoint of cost and coloring power. Although aluminum is in the form of powder or paste, it is preferably used in the form of paste from the viewpoint of handleability and safety, and whether reefing or non-reefing is used is appropriately selected from the viewpoint of luminance and concentration.

Examples of the white pigment include titanium oxide, zinc sulfide, lead white, zinc flower, lithobon, antimony white, basic lead sulfate, basic lead silicate, barium sulfate, calcium carbonate, gypsum, silica, and the like. Be done. The average particle size of the pigment is preferably in the range of 10 to 200 nm, more preferably about 50 to 150 nm.

The amount of the coloring pigment added is preferably in the range of 1 to 20% by mass of the total amount of the ink in order to obtain sufficient image density and light resistance of the printed image.

Regarding the resin system used, polyolefin resin, polyurethane resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, Examples thereof include rosin-based resins, rosin-modified maleic acid resins, ketone resins, cyclized rubbers, rubber chlorides, butyral, and petroleum resins. Various resin systems are selected depending on the required properties. For example, a chlorinated polypropylene resin is used to obtain adhesion to an olefin, and a cellulose acetate resin is chain-stretched with polyisocyanate to obtain oil resistance. Is used. In addition, polyester-polyurethane resin, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, etc. are used, and when durability is required, a curing agent is further added to these resin-based inks at the time of printing. It may also improve the strength of the film. In the present invention, since the adhesion with the polyolefin molten resin can be enhanced by providing the primer layer on the printing ink layer, for example, the adhesion with the polypropylene extruded resin layer is poor, so that it can be used so far. Ink materials other than the chlorinated polypropylene resin-based ink that could not be used can be preferably used. When extruding and laminating a polypropylene molten resin, the adhesion was maintained by using a chlorinated polypropropylene-based ink in the past, but by providing the primer layer of the present invention, various ink materials can be used. Become. Therefore, the use of a toluene solvent, which has been a problem when using a chlorinated polypropylene-based ink, can be avoided, and the problem of dioxin generation due to a large amount of chlorine can be avoided. Therefore, it is possible to obtain a laminated body having a further reduced environmental load.

For printing inks, if necessary, use combined resins, extender pigments, pigment dispersants, leveling agents, defoamers, waxes, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, dispersants, etc. It can also be included. As the dispersant, a surfactant such as anionic, nonionic, cationic or amphoteric can be used. For example, a comb-shaped structure polymer compound obtained by adding polyester to polyethyleneimine, an alkylamine derivative of an α-olefin maleic acid polymer, or the like can be mentioned. Specific examples thereof include the Sol Spurs series (ZENECA), the Azisper series (Ajinomoto), and the Homogenol series (Kao). Further, BYK series (Big Chemie), EFKA series (EFKA) and the like can also be used as appropriate. The dispersant is preferably contained in the ink in an amount of 0.05% by mass or more and 5% by mass or less from the viewpoint of laminating suitability with respect to the total mass of the ink from the viewpoint of storage stability of the ink, and more preferably 0. It is in the range of 1 to 2% by mass.

The ink used for the printing ink layer of the present invention is obtained by mixing the above-mentioned colorants, resins, additives and the like, and is used in various forms such as solvent-based, water-based, and solvent-free. The most popular is the solvent system, but it is also preferable to use a solvent-free system such as an aqueous solution or a UV curable system which emits very little organic solvent because of the emission due to evaporation of the organic solvent and the deterioration of the working environment.
Examples of the solvent include aromatic organic solvents such as toluene and xylene, aliphatic organic solvents such as cyclohexane and methylcyclohexane, ketone solvents such as acetone, methylethylketone and methylisobutylketone, ethyl acetate and n-acetate. Examples thereof include ester solvents such as propyl, butyl acetate and propylene glycol monomethyl ether acetate, alcohol solvents such as n-propanol, isopropanol and n-butanol, glycol ether solvents such as propylene glycol monomethyl ether and ethylene glycol monopropyl ether. These can be used alone or in admixture of two or more.

As described above, when an ink other than chlorinated polypropylene is used, the use of a toluene solvent can be avoided, so that the work environment load can be reduced.

The printing ink layer of the present invention can be formed by printing ink on a base film. Examples of the printing method include gravure printing, flexographic printing, flat plate printing, and inkjet printing. When the production quantity is prioritized, gravure printing and flexographic printing capable of high-speed printing are mainly used. On the contrary, in the case of printing a small amount, an inkjet method that does not require plate making is useful. The film thickness of the printing ink layer of the present invention thus formed is not limited, but is, for example, 10 μm or less, preferably 5 μm or less. The thickness of the printed ink layer, it is preferred in the case of color inks from about 0.4 ~ 0.9g / ^{m 2,} when the white ink is about 0.8 ~ 1.5g / ^{m 2.}

(Primer layer)
A primer layer for improving the adhesion with the extruded resin layer is provided on the printing ink layer. The primer layer of the present invention is formed by a primer composition. Since the composition of the primer composition is as described above, the description thereof is omitted here.

The primer layer is obtained by coating a primer composition on a printing ink layer. Specific examples of the coating method include roll coater, gravure coater, flexo coater, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, transfer coater, kiss coater, curtain coater, cast coater, and spray coater. , A die coater, an offset printing machine, a screen printing machine and the like can be appropriately adopted. The film thickness of the primer layer of the present invention thus formed is preferably 0.1 μm or more and 10 μm or less in order to maintain adhesion to the base material layer, the ink layer, and the extruded resin layer. The thickness of the primer layer is preferably 0.1 to 2.0 g / m ² , preferably 0.3 to 1.0 g / m ² . If the film thickness of the primer layer is too thin, the adhesion to the extruded resin layer becomes insufficient, and if the film thickness of the primer layer is too thick, the blocking resistance becomes insufficient.

(Extruded resin layer)
After forming the primer layer, the thermoplastic resin is extruded and laminated on the primer layer to form the extruded resin layer. A step may be provided in which a laminated film having a printed layer and a primer layer formed on a substrate is once wound into a roll, or an extruded resin layer may be provided as it is without being wound into a roll.

As the thermoplastic resin used for the extruded resin layer, a polyethylene-based resin or a polypropylene-based resin polyolefin-based resin is preferable. Since the primer layer of the present invention has excellent adhesiveness to a polypropylene-based resin, it is more preferable to use a polypropylene-based resin.

The polypropylene-based resin is, for example, a propylene homopolymer, a propylene / α-olefin random copolymer such as a propylene-ethylene copolymer, a propylene-butene-1 copolymer and a propylene-ethylene-butene-1 copolymer. Further, a metallocene-catalyzed polypropylene and the like can be mentioned. These may be used alone or in combination.

The polypropylene resin preferably has an MFR (230 ° C.) of 0.5 to 30.0 g / 10 minutes and a melting point of 110 to 165 ° C., and more preferably MFR (230 ° C.) of 2.0 to 15 ° C. It is at 0.0 g / 10 minutes and has a melting point of 115 to 162 ° C. When the MFR and the melting point are in this range, the processing stability, the processability at the time of coextrusion with other layers, and the film forming property of the film are improved.

Further, although it is preferable to use a polypropylene-based resin for the extruded resin layer, another resin may be used in combination with the polypropylene-based resin as a main component. Other resins that can be used together include linear polyethylene such as linear low density polyethylene (LLDPE) and low density polyethylene (LDPE), branched polyethylene, ethylene-vinyl acetate copolymer (EVA), and ethylene-methylmetha. Acrylic copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene -Eethylene-based copolymers such as acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA); further, ionomers of ethylene-acrylic acid copolymers, ionomers of ethylene-methacrylic acid copolymers and the like. Examples thereof include a copolymer of a monomer having a cyclic olefin structure such as a norbornene-based monomer and ethylene or the like, and the polymer may be used alone or in combination of two or more.

When a polypropylene-based resin is used as the base material, it is preferable to use polypropylene as a propylene homopolymer as the extruded resin layer.

The extruded resin layer of the present invention may be a single-layer extruded resin layer, or may be a multi-layered extruded resin layer laminated by a coextrusion laminating method. In the case of a multilayer, the configuration of each layer can be appropriately selected according to the application and performance required by the laminate, but since the laminate of the present invention has a primer layer having excellent adhesion to the polypropylene resin, the primer layer The layer in direct contact with the polypropylene-based resin can be used. Further, the extruded resin layer may be a woven fabric. The resin constituting the woven fabric may be any resin used for the above-mentioned extruded resin layer, and is preferably a polypropylene-based resin.
The film thickness of the extruded resin layer of the present invention thus formed is not limited, but is, for example, 50 μm or less, preferably 30 μm or less.

(Sealant layer)
In the laminate of the present invention, a sealant layer can be provided on the extruded resin layer. The material of the sealant layer is not particularly limited, and the same material as that used for the base material layer can be used, but when polypropylene is used for the extruded resin layer, polypropylene (CPP: unstretched polypropylene) can be used. Film, OPP: biaxially stretched polypropylene film) is preferably used. The sealant layer can be formed by adhering the film used for the sealant layer at the same time as flowing the molten resin layer at the time of forming the extruded resin layer.

The layer structure of the laminate of the present invention is not limited to the above-mentioned structure of the base material layer / printing ink layer / primer layer / extruded resin layer / sealant layer. For example, it may be a laminate of a base material layer / a primer layer / an extruded resin layer without providing a printing ink layer, or it may be a laminate without a sealant layer.
Further, the structure of the laminated body of the present invention may be, for example, a laminated body in which a base material layer or an extruded resin layer is further bonded to another base material. The other base material is not particularly limited, and can be appropriately selected depending on the use of the laminate and the required function. When another base material is further provided, examples of the laminating method include methods such as dry lamination, wet lamination, non-solvent lamination, and extrusion lamination.

When laminating other base materials, the outermost layer of the laminate is laminated with the base material in order to improve the applicability of the adhesive or adhesive, or after printing on the outermost surface. In such cases, it is preferable to apply a surface treatment to the extruded resin layer in order to improve the adhesiveness with the adhesive, the pressure-sensitive adhesive, the printing ink, and the like. Examples of such surface treatments include corona treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, surface oxidation treatment such as ozone / ultraviolet treatment, and surface unevenness treatment such as sandblasting. Corona treatment is preferable.

The printed matter or laminate of the present invention can be used for various purposes such as flexible packaging materials used for foods, pharmaceuticals, cosmetics, sanitary products, industrial parts, miscellaneous goods, magazines, etc., packaging bags, containers, lid materials for containers, etc. ..

The present invention will be described in more detail by way of examples. Hereinafter, both "part" and "%" are based on the mass standard. Blanks in the table indicate that they have not been mixed.

<Example 1>
(Preparation of primer composition)
As the block copolymer (A), a maleic acid-modified styrene-ethylene-butylene-styrene block copolymer (mass ratio (a) / (b) of the styrene-based polymer block (a) and the butadiene-based polymer block (b)). The primer composition of Example 1 was prepared by dissolving 30/70 and an acid value of 19 [mgCH ₃ ONa / g]) (Clayton FG1901: manufactured by Clayton Co., Ltd.) in a solvent at the blending ratios shown in Table 1. .. As the solvent, methylcyclohexane and n-propyl acetate were used.

(Preparation of polyurethane urea resin solution P)
84.5 parts of neopentyl glycol adipatediol (hydroxyl value: 56.6 mgKOH / g) and 15.5 parts of polyethylene glycol (hydroxyl group) in a four-necked flask equipped with a stirrer, thermometer, recirculation cooler and nitrogen gas introduction tube. Value: 278 mgKOH / g) and 27.55 parts of isophorone diisocyanate were charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.84% by weight, which was then subjected to ethyl acetate. 68.7 parts were added to make a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 7.83 parts of isophorondiamine, 0.11 part of di-n-butylamine, 136.8 parts of ethyl acetate and 110.7 parts of isopropyl alcohol, and 5 at 45 ° C. The reaction was stirred for a time to obtain a polyurethane urea resin solution P. The obtained polyurethane urea resin solution P had a resin solid content concentration of 30.4% by mass, a Tg of 3 ° C., and a resin solid content of Mw of 54,000 (adjustment of vinyl chloride vinyl acetate copolymer resin solution K).
A 15% solution of vinyl chloride vinyl acetate copolymer resin having a hydroxyl group (resin monomer composition is vinyl chloride / vinyl acetate / vinyl alcohol = 92/3/5, hydroxyl value (mgKOH) = 64) is made up of ethyl acetate in 15% solution. This was designated as a vinyl chloride resin solution K.
(Adjustment of urethane / vinyl acetate ink)
30 parts of polyurethane resin solution P, 30 parts of vinyl chloride vinyl acetate copolymer resin solution K, 10 parts of phthalocyanine blue pigment (FASTGEN Blue LA5380 manufactured by DIC Corporation), and 30 parts of ethyl acetate are mixed with Dynomill (Willie E.).・ We kneaded the meat using (manufactured by Bacoffen) to create a urethane / vinyl acetate-based blue printing ink.

The viscosity of the obtained printing ink was adjusted to 16 seconds (25 ° C.) with Ethyl acetate / IPA = 70/30 with Zahn Cup # 3 (manufactured by Rigosha).

(Preparation of printed matter and laminate)
Next, the adjusted ink is printed on a biaxially stretched polypropylene film (hereinafter, OPP film, manufactured by Toyo Spinning Co., Ltd.) having a corona treatment on one side by a gravure calibrator equipped with a gravure plate having a plate depth of 30 μm. Then, by drying, a printing ink layer is formed on a substrate (OPP film), and subsequently, a primer composition is printed and dried to form a primer layer, which has a printed layer and a primer layer. An OPP film print was obtained.
Subsequently, the film is sequentially taken out from the OPP film printed matter to provide an extruded resin layer, and at the same time, a non-stretched polypropylene film (hereinafter referred to as CPP film) is attached to the extruded resin layer to form an OPP film / printing ink layer / primer layer. / The laminated body of Example 1 of the extruded resin layer / CPP film was prepared. The extruded resin layer uses a propylene homopolymer [density: 0.90 g / cm3, MFR: 7.5 g / 10 minutes], and the propylene homopolymer is extruded from a T die at an extrusion temperature of 250 ° C. by an extrusion method. It was formed by extruding the resin layer so that the thickness was 10 μm.

<Example 2>
In the primer composition of Example 1, the maleic acid-modified styrene-ethylene-butylene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) is used as the block copolymer (A). Examples except that the mass ratios (a) / (b) were 13/87 and the acid value was 11 [mgCH ₃ ONa / g]) (Clayton FG1924: manufactured by Clayton Co., Ltd.) in the blending ratios shown in Table 1. The primer composition, printed matter and laminate of Example 2 were prepared in the same manner as in 1.

<Example 3>
In the primer composition of Example 1, the mass ratio of the styrene-butadiene-butylene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) as the block copolymer (A) ( The primer composition and printed matter of Example 3 are the same as in Example 1 except that a) / (b) are 30/70) (Clayton G1652: manufactured by Clayton Co., Ltd.) in the blending ratios shown in Table 1. And a laminate was produced.

<Example 4>
In the primer composition of Example 1, the mass ratio of the styrene-ethylene-propylene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) as the block copolymer (A) ( The primer composition and printed matter of Example 4 are the same as in Example 1 except that a) / (b) are 20/80) (Clayton G1730: manufactured by Clayton Co., Ltd.) in the blending ratios shown in Table 1. And a laminate was produced.

<Example 5>
In the primer composition of Example 1, the maleic acid-modified styrene-ethylene-butylene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) is used as the block copolymer (A). Mass ratio (a) / (b) is 30/70, acid value is 10 [mgCH ₃ ONa / g]) (Tough Tech (registered trademark) M-1913: manufactured by Asahi Kasei Co., Ltd.) with the compounding ratio shown in Table 1. The primer composition, printed matter, and laminate of Example 5 were prepared in the same manner as in Example 1 except that they were mixed.

<Example 6>
In the primer composition of Example 1, the maleic acid-modified styrene-ethylene-butylene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) is used as the block copolymer (A). Mass ratio (a) / (b) is 20/80, acid value is 10 [mgCH ₃ ONa / g]) (Tough Tech (registered trademark) M-1943: manufactured by Asahi Kasei Co., Ltd.) with the compounding ratio shown in Table 1. The primer composition, printed matter, and laminate of Example 6 were prepared in the same manner as in Example 1 except that they were mixed.

<Example 7>
The primer composition of Example 7 and the laminate of Example 7 were prepared in the same manner as in Example 1 except that Example 1 was mixed at the blending ratios shown in Table 1.

<Example 8>
In the primer composition of Example 1, the mass ratio of the styrene-ethylene-butylene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) as the block copolymer (A) ( Examples were the same as in Example 1 except that a) / (b) were 30/70) (Tough Tech (registered trademark) H-1041: manufactured by Asahi Kasei Co., Ltd.) in the blending ratios shown in Table 1. The primer composition, printed matter and laminate of No. 8 were prepared.

<Example 9>
In the primer composition of Example 1, the mass ratio of the styrene-ethylene-butylene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) as the block copolymer (A) ( Examples were the same as in Example 1 except that a) / (b) were 67/33) (Tough Tech (registered trademark) H-1043: manufactured by Asahi Kasei Co., Ltd.) in the blending ratios shown in Table 1. 9 primer compositions, printed matter and laminates were prepared.

<Example 10>
In the primer composition of Example 1, the mass ratio of the styrene-ethylene-butylene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) as the block copolymer (A) ( Examples are the same as in Example 1 except that a) / (b) are 12/88) (Tough Tech (registered trademark) H-1221: manufactured by Asahi Kasei Co., Ltd.) in the blending ratios shown in Table 1. Ten primer compositions, printed matter and laminates were prepared.

<Example 11>
In the primer composition of Example 1, the mass ratio of the styrene-butadiene-butylene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) as the block copolymer (A) ( Examples were the same as in Example 1 except that a) / (b) were 20/80) (Tough Tech (registered trademark) P-1083: manufactured by Asahi Kasei Co., Ltd.) in the blending ratios shown in Table 1. Eleven primer compositions, printed matter and laminates were prepared.

<Example 12>
In the primer composition of Example 1, the mass ratio of the styrene-butadiene-butylene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) as the block copolymer (A) ( Examples were the same as in Example 1 except that a) / (b) were 30/70) (Tough Tech (registered trademark) P-1500: manufactured by Asahi Kasei Co., Ltd.) in the blending ratios shown in Table 2. Twelve primer compositions, printed matter and laminates were prepared.

<Example 13>
In the primer composition of Example 1, the mass ratio (a) of the styrene-butadiene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) as the block copolymer (A). / (B) is 30/70) (Asaprene (registered trademark) T-411: manufactured by Asahi Kasei Co., Ltd.) was mixed in the same manner as in Example 1 except that the compounding ratios shown in Table 2 were mixed. Primer compositions, printed matter and laminates were prepared.

<Example 14>
In the primer composition of Example 1, the mass ratio (a) of the styrene-butadiene-styrene block copolymer (styrene-based polymer block (a) and butadiene-based polymer block (b)) as the block copolymer (A). / (B) is 30/70) (Asaprene (registered trademark) T-432: manufactured by Asahi Kasei Co., Ltd.) was mixed in the same manner as in Example 1 except that the compounding ratios shown in Table 2 were mixed. Primer compositions, printed matter and laminates were prepared.

<Example 15>
In the primer composition of Example 1, the same procedure as in Example 1 was carried out except that amido wax (ethylene bisoleic acid amide) was further added as the blocking inhibitor (C) and mixed at the blending ratios shown in Table 2. The primer composition, printed matter and laminate of Example 15 were prepared.

<Example 16>
In the primer composition of Example 2, Fischer-Tropschwax (Sasolwax H1, solid acid value 0.1 mgKOH / g: manufactured by Sasol Performance Chemicals) was further added and mixed in the blending ratio shown in Table 2. In the same manner as in the above, the primer composition, printed matter and laminate of Example 16 were prepared.

<Example 17>
In the primer composition of Example 3, polyethylene wax (High Wax 200P: manufactured by Mitsui Chemicals, Inc.) was further added and mixed at the blending ratios shown in Table 2 in the same manner as in Example 3. 17 primer compositions, printed matter and laminates were prepared.

<Example 18>
In the composition of Example 4, polypropylene wax (High Wax NP055: manufactured by Mitsui Chemicals, Inc.) was further added and mixed at the blending ratios shown in Table 2, except that Polypropylene wax (High Wax NP055) was mixed in the same manner as in Example 4 in the same manner as in Example 18. Primer composition, printed matter and laminate were prepared.

<Example 19>
In the composition of Example 5, the same as in Example 5 except that a ketone resin having a Tg of 50 ° C. (TEGO VariPlus AP: manufactured by Evonik Industries) was further added as an auxiliary resin and mixed at the blending ratio shown in Table 2. The primer composition, printed matter, and laminate of Example 19 were prepared.

<Example 20>
In the composition of Example 6, the same as in Example 6 except that a ketone resin having a Tg of 90 ° C. (TEGO VariPlus SK: manufactured by Evonik Industries) was further added as an auxiliary resin and mixed at the blending ratio shown in Table 2. To prepare the primer composition, printed matter, and laminate of Example 20.

<Example 21>
In the composition of Example 7, an acrylic resin having a Tg of 85 ° C. (DEGALAN LP 67/11, solvent-based acrylic resin (solid content 100%): manufactured by Evonik Industries) is further added as an auxiliary resin and is shown in Table 2. The primer composition, printed matter, and laminate of Example 21 were prepared in the same manner as in Example 7 except that they were mixed in the blending ratio of.

<Example 22>
In the composition of Example 8, a vinyl chloride / vinyl acetate copolymer resin having a Tg of 76 ° C. (Solvine AL: manufactured by Nisshin Kagaku Kogyo Co., Ltd.) was further added as an auxiliary resin, and the blending ratios shown in Table 2 were added. The primer composition, printed matter, and laminate of Example 22 were prepared in the same manner as in Example 8 except that they were mixed in.

<Example 23>
In the composition of Example 9, a vinyl chloride / vinyl acetate copolymer resin having a Tg of 68 ° C. (Solvine C5R: manufactured by Nisshin Kagaku Kogyo Co., Ltd.) was further added as an auxiliary resin, and the blending ratios shown in Table 3 were added. The primer composition, printed matter, and laminate of Example 23 were prepared in the same manner as in Example 9 except that they were mixed in.

<Example 24>
In the composition of Example 10, as an auxiliary resin, the viscosity of industrial vitrified cotton L1 / 8 (nitrocellulose, solid content 30%, solution concentration 25.0% by JIS K-6703) having a Tg of 150 ° C. 1. 6 to 2.9% product (manufactured by Taihei Chemicals Limited) was further added and mixed at the blending ratios shown in Table 3 in the same manner as in Example 10, and the primer composition, printed matter and laminate of Example 24. The body was made.

<Example 25>
In the composition of Example 11, the polyurethane urea resin solution P (Tg of 3 ° C., resin solid content of about 30%) prepared in Example 1 was further added as an auxiliary resin, and the mixture was mixed at the blending ratio shown in Table 3. The primer composition, printed matter, and laminate of Example 25 were prepared in the same manner as in Example 11 except for the above.

<Example 26>
In the composition of Example 12, a ketone resin having a Tg of 50 ° C. (TEGO VariPlus AP: manufactured by Evonik Industries) was further added as an auxiliary resin, and amide wax (ethylenebisoleic acid amide) was further added as a wax, and the results are shown in Table 3. The primer composition, printed matter, and laminate of Example 26 were prepared in the same manner as in Example 12 except that they were mixed in the blending ratio of.

<Example 27>
In the composition of Example 1, a vinyl chloride / vinyl acetate copolymer resin having a Tg of 68 ° C. (Solvine C5R: manufactured by Nisshin Kagaku Kogyo Co., Ltd.) was used as an auxiliary resin, and a polyethylene wax (High Wax 200P:) was used as a wax. The primer composition, printed matter and laminate of Example 27 were prepared in the same manner as in Example 1 except that (manufactured by Mitsui Chemicals, Inc.) was further added and mixed at the blending ratios shown in Table 3.

<Example 28>
In the composition of Example 3, a ketone resin having a Tg of 90 ° C. (TEGO VariPlus SK: manufactured by Evonik Industries) was further added as an auxiliary resin, and Fischer-Tropsch wax (Sasolwax H1) was further added as a wax, and the blending ratios shown in Table 3 were added. The primer composition, printed matter, and laminate of Example 28 were prepared in the same manner as in Example 3 except that they were mixed in.

<Example 29>
In the composition of Example 5, an acrylic resin having a Tg of 85 ° C. (DEGALAN LP 67/11: manufactured by Evonik Industries) was used as an auxiliary resin, and a polypropylene wax (high wax NP055: manufactured by Mitsui Chemicals, Inc.) was used as a wax. Was further added and mixed at the blending ratios shown in Table 3, and the primer composition, printed matter, and laminate of Example 29 were prepared in the same manner as in Example 5.

<Example 30>
In the composition of Example 2, a vinyl chloride / vinyl acetate copolymer resin having a Tg of 68 ° C. (solvine C5R: manufactured by Nisshin Kagaku Kogyo Co., Ltd.) was used as an auxiliary resin, and amide wax (ethylenebisoleic acid amide) was used as a wax. ) Was added, and toluene was used instead of methylcyclohexane as a solvent to mix them in the blending ratios shown in Table 3. The primer composition, printed matter, and laminate of Example 30 were prepared in the same manner as in Example 2. Made.

<Example 31>
In the composition of Example 6, a ketone resin having a Tg of 50 ° C. (TEGO VariPlus AP: manufactured by Evonik Industries) was added as an auxiliary resin, and apolyethylene wax (High Wax 200P: manufactured by Mitsui Chemicals, Inc.) was added as a wax. Further, the primer composition of Example 31 was prepared in the same manner as in Example 6 except that toluene and ethyl acetate were used instead of methylcyclohexane and n-propyl acetate as solvents and mixed at the blending ratios shown in Table 3. Printed matter and laminate were produced.

<Comparative Example 1>
In Example 1, after obtaining an OPP film printed matter in which a printing ink layer is formed on a substrate (OPP film), an extruded resin layer is directly provided on the printing ink layer without providing a primer layer, and at the same time, the extruded resin is provided. A laminate of Comparative Example 1 of OPP film / printing ink layer / extruded resin layer / CPP film was produced in the same manner as in Example 1 except that a non-stretched polypropylene film (hereinafter referred to as CPP film) was attached to the layer.

<Comparative Example 2>
In Example 1, a polyurethane urea resin solution P was used as a primer composition, and a printed matter and a laminate of Comparative Example 2 were prepared in the same manner as in Example 1 except that they were mixed at the blending ratios shown in Table 3.

The primer composition and laminate prepared as described above were evaluated as follows.

[Laminate suitability]
The laminates of Examples 1 to 31 and Comparative Examples 1 and 2 were cut out to a width of 15 mm, and a peeling test of 90 degrees was performed at a tensile speed of 300 mm / min.

(Evaluation criteria)
⊚: Laminate strength is 1.5 N / 15 mm or more.
◯: Laminate strength is less than 1.5N / 15mm to 1.0N / 15mm or more.
Δ: Laminate strength is less than 1.0 N / 15 mm to 0.5 N / 15 mm or more.
X: The laminate strength is less than 0.5 N / 15 mm.

[Blocking resistance]
In the method for producing the laminates of Examples 1 to 31 and Comparative Examples 1 and 2, the OPP film printed matter (OPP film / printing ink layer / primer layer) on which the primer layer before the extruded resin layer was provided was used as the primer layer. OPP film printed matter is overlapped so that the OPP film comes into contact with each other, ^{a load of 10 kgf / cm 2} is applied, the ink is allowed to elapse in an environment of 40 ° C. for 12 hours, and after taking out, the state of ink transfer to the non-printed surface is visually evaluated. did. It should be noted that the values above Δ can be used without any problem in practical use.

(Evaluation criteria)
⊚: There is no peeling resistance and no blocking is seen.
〇: There is peeling resistance, but no blocking is seen.
Δ: There is peeling resistance, and some blocking is observed.
X: The peeling resistance is strong, and blocking is seen over the entire surface.

[Transparency / stability]
The appearance and transparency of the solutions of Examples 1 to 31 and Comparative Example 2 after preparation were visually evaluated, and the appearance and transparency of the solution after 24 hours at 25 ° C. were visually evaluated. It should be noted that the values above Δ can be used without any problem in practical use.
⊚: The solution is clear and clear, and no agglutination or separation is observed.
〇: The solution is slightly turbid, but no agglutination or separation is observed.
Δ: The solution is turbid, but no agglutination or separation is observed.
X: The solution is turbid, and agglutination or separation is observed.
The results are shown in the table below.

From the results of Tables 1 to 4, it was found that by providing the primer layer of the present invention, the adhesion to the polypropylene extruded resin layer was improved and excellent laminating suitability was obtained. Even if a primer layer is provided, the blocking resistance is maintained at the same level as when there is no primer layer.
<Example 32>
In Example 1, a linear medium-density polyethylene [density: 0.930 g / cm3, melting point 125 ° C., MFR: 5 g / 10 minutes (190 ° C., 21.18N)] was used for the extruded resin layer. The printed matter and the laminate of Example 32 were produced in the same manner as in Example 1.
<Examples 33 to 57, Comparative Example 3>
Similar to Example 32, Example 33 is the same as in Examples 2 to 31 and Comparative Example 1 except that linear medium density polyethylene was used for the extruded resin layer in Examples 2 to 31 and Comparative Example 1. -57 and the printed matter and the laminate of Comparative Example 3 were produced.

The above evaluation was performed on the laminate prepared as described above.

From the results in Tables 5 to 7, it was found that by providing the primer layer of the present invention, the adhesion with the polyethylene extruded resin layer was improved and excellent laminating suitability was obtained. From the results of Comparative Examples 1 to 3, it can be seen that when the primer layer is not provided, the laminating suitability is superior when polyethylene is used as the extruded resin layer rather than polypropylene. However, it was found that when the primer layer of the present invention was used, a more excellent effect of laminating suitability could be obtained when polypropylene was used for the extruded resin layer.

<Example 58>
In the laminate of Example 15, the printed matter and the laminate of Example 58 were produced in the same manner as in Example 15 except that the ink of the printing ink layer was replaced with the following “urethane / polyvinyl butyral-based” printing ink. ..

(Adjustment of urethane / polyvinyl butyral ink)
30 parts of polyurethane resin solution P, 5 parts of polyvinyl butyral resin (ESREC BL-1 manufactured by Sekisui Chemical Industry Co., Ltd.), 10 parts of phthalocyanine blue pigment (FASTGEN Blue LA5380 manufactured by DIC Corporation), 30 parts of ethyl acetate, IPA25 The mixture of parts was kneaded using a Dynomill (manufactured by Willy et Bacoffen) to prepare a urethane-polyvinyl butyral-based blue printing ink. The viscosity of the obtained printing ink was adjusted to 16 seconds (25 ° C.) with Ethyl acetate / IPA = 70/30 with Zahn Cup # 3 (manufactured by Rigo Co., Ltd.).

<Example 59>
In the laminate of Example 16, the printed matter and the laminate of Example 59 were produced in the same manner as in Example 16 except that the ink of the printing ink layer was replaced with the “urethane / polyvinyl butyral-based” printing ink.

<Example 60>
In the laminate of Example 17, the printed matter and the laminate of Example 60 were produced in the same manner as in Example 17 except that the ink of the printing ink layer was replaced with the following “vinyl acetate-based” printing ink.
(Adjustment of salt and vinyl acetate ink)
Using 60 parts of vinyl chloride vinyl acetate copolymer resin solution K, 10 parts of phthalocyanine blue pigment (FASTGEN Blue LA5380 manufactured by DIC Corporation), and 30 parts of ethyl acetate using Dynomill (manufactured by Willy et Bacoffen). The meat was kneaded to create a vinyl acetate-based blue printing ink. The viscosity of the obtained printing ink was adjusted to 16 seconds (25 ° C.) with ethyl acetate using Zahn Cup # 3 (manufactured by Rigo Co., Ltd.).

<Example 61>
In the laminate of Example 18, the printed matter and the laminate of Example 61 were produced in the same manner as in Example 18 except that the ink of the printing ink layer was replaced with the “vinyl acetate-based” printing ink.

<Example 62>
In the laminate of Example 19, the printed matter and the laminate of Example 62 were produced in the same manner as in Example 19 except that the ink of the printing ink layer was replaced with the “urethane / polyvinyl butyral-based” printing ink.

<Example 63>
In the laminate of Example 20, the printed matter and the laminate of Example 63 were produced in the same manner as in Example 20 except that the ink of the printing ink layer was replaced with the “urethane / polyvinyl butyral-based” printing ink.

<Example 64>
In the laminate of Example 21, the printed matter and the laminate of Example 64 were produced in the same manner as in Example 21 except that the ink of the printing ink layer was replaced with the “vinyl acetate-based” printing ink.

<Example 65>
In the laminate of Example 22, the printed matter and the laminate of Example 65 were produced in the same manner as in Example 22 except that the ink of the printing ink layer was replaced with the “vinyl acetate-based” printing ink.

<Example 66>
In the laminate of Example 23, the printed matter and the laminate of Example 66 were produced in the same manner as in Example 23 except that the ink of the printing ink layer was replaced with the “urethane / polyvinyl butyral-based” printing ink.

<Example 67>
In the laminate of Example 24, the printed matter and the laminate of Example 67 were produced in the same manner as in Example 24 except that the ink of the printing ink layer was replaced with the “urethane / polyvinyl butyral-based” printing ink.

<Example 68>
In the laminate of Example 25, the printed matter and the laminate of Example 68 were produced in the same manner as in Example 25 except that the ink of the printing ink layer was replaced with the “vinyl acetate-based” printing ink.

<Example 69>
In the laminate of Example 26, the printed matter and the laminate of Example 69 were produced in the same manner as in Example 26 except that the ink of the printing ink layer was replaced with the “vinyl acetate-based” printing ink.

<Example 70>
In the laminate of Example 27, the printed matter and the laminate of Example 70 were produced in the same manner as in Example 27 except that the ink of the printing ink layer was replaced with the “urethane / polyvinyl butyral-based” printing ink.

<Example 71>
In the laminate of Example 28, the printed matter and the laminate of Example 71 were produced in the same manner as in Example 28 except that the ink of the printing ink layer was replaced with the “urethane / polyvinyl butyral-based” printing ink.

<Example 72>
In the laminate of Example 29, the printed matter and the laminate of Example 72 were produced in the same manner as in Example 29 except that the ink of the printing ink layer was replaced with the “vinyl acetate-based” printing ink.

The above-mentioned laminating suitability and blocking resistance were evaluated for the laminated body prepared as described above.

From the results of Examples 58 to 72, it was found that excellent laminating suitability can be obtained regardless of the type of ink in the printing ink layer.

From the results of Examples 58 to 72, it was found that excellent laminating suitability can be obtained regardless of the type of ink in the printing ink layer.

<Example 73>
In the primer composition of Example 15, silica (manufactured by Fuji Silysia Chemical Ltd., Cylysia (registered trademark) 430) was used as the blocking inhibitor (C) and mixed with Example 15 in the blending ratios shown in Table 10. In the same manner, the printed matter and the laminate of Example 73 were produced.

<Example 74>
In the primer composition of Example 29, a ketone resin having a Tg of 90 ° C. (TEGO VariPlus SK: manufactured by Evonik Industries) was used as an auxiliary resin, and silica (manufactured by Fuji Silysia Chemical Ltd., registered) was used as the blocking inhibitor (C). The printed matter and the laminate of Example 74 were prepared in the same manner as in Example 29 except that they were mixed in the blending ratios shown in Table 10 using Trademark) 430).

<Example 75>
In Example 42, silica (manufactured by Fuji Silysia Chemical Ltd., Cylysia (registered trademark) 430) was used as the blocking inhibitor (C) and mixed in the blending ratios shown in Table 10 in the same manner as in Example 46. The printed matter and the laminate of Example 75 were prepared.

<Example 76>
In Example 55, silica (manufactured by Fuji Silysia Chemical Ltd., Cylysia (registered trademark) 430) was used as the blocking inhibitor (C) and mixed in the blending ratios shown in Table 10 in the same manner as in Example 60. The printed matter and the laminate of Example 76 were produced.

<Example 77>
In Example 72, a vinyl chloride / vinyl acetate copolymer resin (Solvine C5R: manufactured by Nissin Chemical Industry Co., Ltd.) having a Tg of 68 ° C. was used as the auxiliary resin, and silica (Fuji Silysia Chemical Ltd.) was used as the blocking inhibitor (C). A printed matter and a laminate of Example 77 were prepared in the same manner as in Example 72 except that they were mixed in the blending ratios shown in Table 10 using Silysia Chemical Ltd. (registered trademark) 430).

From the results of Examples 73 to 77, it was found that excellent laminating suitability can be obtained regardless of the type of the blocking inhibitor (C).

Claims (10)

1. A primer containing a block copolymer (A) consisting of a styrene-based polymer block (a) and at least one of a butadiene-based polymer block, an isoprene-based polymer block, or a hydrogenated product block thereof (b). A primer composition, which is a composition, wherein the mass ratio (a) / (b) of the polymer block (a) to the polymer block (b) is 5/95 to 70/30.
2. The primer composition according to claim 1, wherein the block copolymer (A) is a maleic anhydride-modified block copolymer and has an acid value of 1 to 30 [mgCH _{3 ONa / g].} thing.
3. When the primer composition contains the auxiliary resin (B) and / or the blocking inhibitor (C) and contains the auxiliary resin (B), the following (1) is satisfied and the blocking inhibitor (C) is contained. The primer composition according to claim 1 or 2, wherein the primer composition is characterized by satisfying the following (2).
   (1) The Tg of the auxiliary resin (B) is 50 ° C. or higher, and the mass ratio (A) / (B) of the block copolymer (A) to the auxiliary resin (B) is 99/1 to 50/50. (2) The total amount of the primer composition contains 0.1 to 5.0% by mass of the blocking inhibitor (C).
4. The primer composition according to claim 3, wherein the blocking inhibitor (C) contains at least one of a polyolefin wax, an amide wax, and silica.
5. The primer composition according to any one of claims 1 to 4, wherein the primer composition is a primer in contact with an extruded resin, and the extruded resin contains at least polypropylene.
6. The primer composition according to any one of claims 1 to 5, wherein the substrate on which the primer composition is printed contains at least polypropylene.
7. The primer composition according to any one of claims 1 to 6, wherein the primer composition is printed on a printing ink layer.
8. A printed matter having a primer layer formed by the primer composition according to any one of claims 1 to 7 on a substrate.
9. It is a laminate in which a printing ink layer, a primer layer, and an extruded resin layer are laminated at least in this order on a substrate, and the primer layer is formed by the primer according to any one of claims 1 to 7. Laminated body.
10. A laminate in which a printing ink layer, a primer layer, an extruded resin layer, and a sealant layer are laminated at least in this order on a substrate, and the primer layer is formed by the primer according to any one of claims 1 to 7. A laminate characterized in that the sealant layer contains at least polypropylene.