JP2998294B2 - Print laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed laminate having excellent adhesion to hot stamp foils, printing inks, etc., and having improved scratch resistance, workability and gloss.

[0002]

2. Description of the Related Art For the purpose of protecting the surface of a printed body and finishing the appearance of the printed body, surface coating, printing lamination in which a plastic film is bonded, and the like are performed. In particular, in recent years, print laminations with a large surface protection effect and a beautifully finished print lamination have been greatly expanded. ing.

[0003] Conventionally, films used for print lamination are polypropylene films for general use and polyvinyl chloride films for high-end products and boxes. Since the polypropylene film is inferior in glossiness and poor in adhesiveness, a laminate using such a film was inferior in box making. About polyvinyl chloride film, there is a problem in terms of fish eye and thickness deflection, and when the print laminate is incinerated,
There is also a problem that chlorine gas is generated.

[0004] In order to improve the above drawbacks, the use of a polyester film as a base film has been studied. However, the polyester film has poor adhesion to printing inks and hot stamp foils, so that it is used only in very limited applications. Can only be used. Corona treatment, coating and the like have been applied to improve the adhesiveness, but they are still insufficient, and the surface is scratched or the gloss becomes poor.

[0005]

Means for Solving the Problems In view of the above-mentioned problems, the present inventors have conducted intensive studies and as a result, have found that a printed laminate having a specific structure has a problem in terms of adhesiveness, scratch resistance, workability and glossiness. And found that the present invention was completed. That is, the gist of the present invention is to provide a print in which a polyester film is laminated on a print layer side of a print, and a coating layer containing a water-soluble or water-dispersible resin and a lubricant is laminated on an exposed surface side of the film. Exists in laminate.

Hereinafter, the present invention will be described in detail. The polyester referred to in the present invention is an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid or an ester thereof and ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol. And polyesters produced by polycondensation with glycols such as

[0007] The polyester comprising the acid component and the glycol component can be produced by arbitrarily employing a commonly used method. For example, a transesterification reaction is performed between a lower alkyl ester of an aromatic dicarboxylic acid and glycol, or a direct esterification of an aromatic dicarboxylic acid and glycol to substantially form a bisglycol ester of an aromatic dicarboxylic acid. Alternatively, a method of forming a low polymer thereof and then performing polycondensation under reduced pressure at a temperature of 240 ° C. or more is employed. At this time, ordinary catalysts, stabilizers, various additives and the like can be arbitrarily used.

Typical examples of such polyesters include poly (ethylene terephthalate), poly (ethylene naphthalate) and poly (butylene terephthalate). This polyester may be a homopolymer, a polymer obtained by copolymerizing the third component, or a mixture of these polyesters.

Further, the polyester film may contain various stabilizers, ultraviolet absorbers, lubricants, pigments, antioxidants, plasticizers, antistatic agents and the like. Examples of the water-soluble or water-dispersible resin in the present invention include starch, cellulose derivatives such as methylcellulose and hydroxyethylcellulose, alginic acid, gum arabic, gelatin, sodium polyacrylate, polyacrylamide, polyvinyl alcohol, polyethylene oxide,
Polyvinylpyrrolidone, urethane resin, acrylic resin, polyamide resin, ether resin, epoxy resin,
Ester resins and the like can be mentioned. In the present invention, particularly preferred are urethane resins, acrylic resins,
It is a polyester resin.

The main components of the urethane resin are as follows:
An aqueous urethane resin comprising a polyisocyanate, a polyol, a chain extender, a crosslinking agent and the like can be used. In making the aqueous solution, it is a general method to use a polyisocyanate, a polyol and a chain extender in which a hydrophilic group is introduced. It is also a well-known method to react an unreacted isocyanate group of a polyurethane with a compound having a hydrophilic group.

As the acrylic resin, the main component is a reaction of an alkyl acrylate or an alkyl methacrylate with a carboxyl group or a salt thereof, an acid anhydride group, a sulfonic acid group or a salt thereof, an amide group, an amino group, a hydroxyl group, an epoxy group or the like. An aqueous acrylic resin obtained by copolymerizing a vinyl monomer having a hydrophilic functional group can be used.

The dicarboxylic acid component of the polyester resin includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid, and oxybenzoic acid. Oxycarboxylic acids such as acids and their ester-forming derivatives can be used.
Examples of the glycol component of the polyester resin include aliphatic glycols such as ethylene glycol, 1,4-butanediol, diethylene glycol and triethylene glycol, alicyclic glycols such as 1,4-cyclohexanedimethanol, and p-xylene diol. Poly (oxyalkylene) glycols such as aromatic diols, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can be used.

As the polyester resin, not only the above-mentioned saturated linear polyester comprising an ester-forming component but also a compound having a trivalent or higher ester-forming component or a compound having a reactive unsaturated group can be used as a polyester component. You may do it. The polyester-based resin preferably has a functional group such as sulfonic acid, carboxylic acid, phosphoric acid or a salt thereof in order to improve solubility and dispersibility in water.

In the present invention, these resins may be used in an appropriate combination. As the lubricant in the present invention, an anionic surfactant, a cationic surfactant,
Amphoteric surfactants, nonionic surfactants, fluorosurfactants, organic carboxylic acids and derivatives thereof, higher aliphatic alcohols, paraffins, waxes, organopolysiloxanes and the like, particularly preferred are water-soluble or water-soluble It is a dispersible polyolefin.

Examples of such polyolefins include (i) waxes, resins, and rubbers made of homo- or copolymers of 1-olefin unsaturated hydrocarbons such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. Object, for example, polyethylene, polypropylene, poly-1-
Butene, poly-4-methyl-1-pentene, ethylene-
Propylene copolymer, ethylene-1-butene copolymer,
Propylene-1-butene copolymer (ii) Rubbery copolymer of two or more of the above 1-olefins with a conjugated or non-conjugated diene, for example, ethylene-propylene-butadiene copolymer, ethylene-propylene-dicyclopentadiene Copolymer, ethylene-propylene-
Ethylidene norbornene copolymer, ethylene-propylene-1,5-hexadiene copolymer or isobutene-isoprene copolymer (iii) Copolymer of 1-olefin and conjugated or non-conjugated diene, for example, ethylene-butadiene copolymer , Ethylene-butadiene copolymer, ethylene-ethylidene norbornel copolymer, (iv) 1-olefin, especially copolymer of ethylene and vinyl acetate and its fully or partially saponified product (v) 1-olefin alone or A graft polymer obtained by grafting the above-mentioned conjugated or non-conjugated diene or vinyl acetate onto a copolymer and a completely or partially saponified product thereof as a basic skeleton, and these are dissolved or dispersed in water. Can be used.

In order to dissolve or disperse the polyolefin in water and to stabilize the polyolefin so that coagulation does not occur, a conventionally known surfactant may be used in combination.
A method in which a hydrophilic polymer such as a water-soluble polyester coexists at the time of dispersion is also effective. Further, by introducing a vinyl compound having a hydrophilic group such as a carboxyl group, a sulfo group, an amino group, a polyether, an alkylolamide group, or a salt thereof into the skeleton of the polyolefin by copolymerization or grafting, the water is dissolved. What facilitated formation or dispersion in water can also be used.

The mixing ratio of the water-soluble or water-dispersible resin and the lubricant used in the present invention is usually 0.1 to 30 parts by weight of the lubricant per 100 parts by weight of the water-soluble or water-dispersible resin.
Parts by weight. By mixing the lubricant, the sliding of the coated surface is improved, and the scratch resistance of the coated surface is significantly improved. If the mixing ratio of the lubricant is too small, the above effect is not exhibited.If the mixing ratio is too large, the applied surface is sticky, the printing ink,
Adhesion with hot stamp foil etc. decreases.

The coating layer may contain a crosslinking agent, inorganic particles and organic particles for improving blocking and the like. If necessary, an antistatic agent, an antifoaming agent, An improving agent, a thickener, an antioxidant, an ultraviolet absorber, a dye and the like may be contained. The thickness of the coating layer of the film used in the present invention is usually 0.01 to 3 μm,
The range of μm is preferred. If the thickness is less than 0.01 μm, it is difficult to obtain a uniform coating layer. On the other hand, when the thickness is more than 3 μm, the slipperiness is reduced and the handling of the film becomes difficult.

Known methods such as a gravure coating method, a reverse coating method, a rod coating method, and an air doctor coating method can be applied as a method for providing a coating layer on the polyester film. A method of sequentially or simultaneously biaxially stretching, a method of applying to a uniaxially stretched polyester film, and a method of further stretching in a direction perpendicular to the uniaxially stretched direction, or a method of applying to a biaxially stretched polyester film. is there. The coating layer may be applied to only one side of the polyester film, or may be applied to both sides. When coating is performed on only one surface, a layer other than the coating layer in the present invention may be formed on the opposite surface as necessary.
For example, when heat-bonding to a print, it is preferable to form a heat-fusible polymer layer.

Further, by subjecting the polyester film to a chemical treatment or a discharge treatment in advance, the adhesiveness between the polyester film and the coating layer is improved. The printed body referred to in the present invention is a printed body on a base material such as art paper, coated paper, woodfree paper, Japanese paper, synthetic paper, film, etc., and may be any of a single body and a laminate. The printing is not particularly limited, and may be any of gravure printing, offset printing, letterpress printing, intaglio printing, flexographic printing, and the like.

In the print laminate of the present invention, for example, an adhesive dissolved in an organic solvent is applied to the base film at the coating portion of the laminator, and after drying, the adhesive applied surface of the base film and the printed surface of the printed body are compared. Obtained by thermocompression bonding or extrusion lamination of a heat-fusible polymer such as ethylene vinyl acetate copolymer on a base film, and thermocompression bonding between the heat-fusible polymer layer surface of the base film and the printed surface of the printed body. be able to.

[0022]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. The evaluations in the examples are as follows.

(1) Adhesiveness Adhesiveness with hot stamp foil After transferring the hot stamp foil from Nakai Kogyo Co., Ltd. to the base film surface of the print laminate by the up-down method, affixing Nichiban Co., Ltd. cellophane tape to the hot stamp foil surface, Rapid peeling was performed in the 180 ° direction. The criteria for determining the adhesiveness were as follows. ：: Does not peel at all. Δ: A portion of less than 50% peels off. X: 50% or more of the parts are peeled off. B. Adhesiveness to printing ink Screen ink (FDSS21 391 indigo and reducer P ″ mixed at a ratio of 10: 1) manufactured by Toyo Ink Co., Ltd. was used on the base film surface of the print laminate using a 300-mesh silk screen. It was applied to a thickness of about 10 μm and cured with a UV lamp, and after curing, a cellophane tape manufactured by Nichiban Co., Ltd. was applied to the ink-applied surface.
Rapid peeling was performed in the ° direction. The criteria for determining the adhesiveness were as follows. ：: Does not peel at all. Δ: A portion of less than 50% peels off. X: 50% or more of the parts are peeled off.

(2) Scratch Resistance The substrate film side of the print laminate was rubbed several times with the back of a nail to determine the degree of scratching. The criteria were as follows. ：: scarcely scarred Δ: Scratched. X: Strong scratches.

(3) Gloss The gloss of the print laminate was determined as follows. ：: Uniform and excellent gloss without unevenness in gloss. X: The gloss is uneven and the gloss is poor.

Example 1 Polyethylene terephthalate having an intrinsic viscosity of 0.65 and containing added particles was melt-extruded at 280 to 300 ° C.
Extrusion while applying static electricity onto a cooling drum at 0 ° C.
Sheeted. Next, after stretching 3.5 times in the machine direction at 83 ° C., 95 parts of Primal HA-12 (trade name) manufactured by Nippon Acryl Chemical Co., Ltd., which is a polyacrylate aqueous dispersion, was coated on one surface of the machine-stretched film. Solid content weight, the same shall apply hereinafter), polyethylene water dispersion Toho Chemical Industry Co., Ltd.
Coating solution consisting of 5 parts of Hitec E4B (trade name) manufactured by Nissan Co., Ltd., is stretched 3.2 times in the horizontal direction at 110 ° C., and heat-treated at 220 ° C., and has a coating layer of 0.05 μm thickness, 12 μm Was obtained. An adhesive was applied to the opposite side of the coating layer of the obtained film, and laminated on the printed surface of the printed white paperboard (manila ball) via the adhesive to obtain a print laminate. The adhesive used was Seika Bond A160 / Seika Bond C4 manufactured by Dainichi Seika Kogyo Co., Ltd.
6H (mixing ratio 1/1) was used. The coating amount was 2 g / m ² as a solid content.

Example 2 The procedure of Example 1 was repeated except that the coating solution was changed as follows.
A print laminate was obtained in the same manner as in Example 1. Coating solution Polyacrylate aqueous dispersion 95 parts (Nippon Acrylic Chemical Co., Ltd. Primal HA-12) Sodium dodecylbenzenesulfonate 5 parts

Example 3 A print laminate was obtained in the same manner as in Example 1 except that the coating solution was changed as follows. Coating liquid Polyurethane aqueous dispersion 90 parts (Polychemicals Neoolez R960) Polyethylene aqueous dispersion 10 parts (Toho Chemical Industry Co., Ltd. Hitec E4B)

Example 4 A print laminate was obtained in the same manner as in Example 1 except that the coating solution was changed as follows. Coating liquid Polyester aqueous dispersion 95 parts (RZ-124 manufactured by Ryogo Chemical Industry Co., Ltd.) Polyethylene aqueous dispersion 5 parts (Hitec E-103N manufactured by Toho Chemical Industry Co., Ltd.)

Comparative Example 1 Example 1 was the same as Example 1 except that no coating layer was provided.
In the same manner as in the above, a print laminate was obtained.

Comparative Example 2 Example 1 was the same as Example 1 except that no coating layer was provided.
After a film having a thickness of 12 μm was obtained in the same manner as described above, one surface of the film was subjected to corona treatment, an adhesive was applied to the opposite surface of the corona treated surface, and the film faced the printed surface of the printed white paperboard (manila ball). They were laminated together to obtain a print laminate.

Comparative Example 3 The procedure of Example 1 was repeated except that the coating solution was changed as follows.
A print laminate was obtained in the same manner as in Example 1. Coating solution Polyacrylate aqueous dispersion 100 parts (Nippon Acrylic Chemical Co., Ltd. Primal HA-12)

Comparative Example 4 The procedure of Example 2 was repeated except that the coating solution was changed as follows.
A print laminate was obtained in the same manner as in Example 2. Coating liquid 100 parts of aqueous polyurethane dispersion (NEOLETZ R960 manufactured by Polyvinyl Chemical)

Comparative Example 5 An adhesive was applied to one side of a biaxially stretched polypropylene film (Trefane S645, manufactured by Toray Industries, Inc.) having a thickness of 20 μm, and the printed face of the printed white paperboard (manila ball) faced. They were laminated together to obtain a print laminate. The adhesive is Seika Bond E manufactured by Dainichi Seika Kogyo Co., Ltd.
270 and C30 (mixing ratio 1/1) were used. The coating amount was 2 g / m ² as a solid content. The results obtained above are shown in Table 1 below.

[0035]

[Table 1]

[0036]

The print laminate of the present invention has an adhesive property such as hot stamp foil and printing ink, a scratch resistance,
It has excellent gloss and its industrial value is high.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // B05D 7/24 301 B05D 7/24 301G (56) References JP-A-62-97890 (JP, A) JP-A-63 -46237 (JP, A) JP-A-59-215318 (JP, A) JP-A-63-265636 (JP, A) JP-A-2-269133 (JP, A) (58) Fields investigated (Int. . ^7, DB name) B32B 1/00 - 35/00 B05D 7/24

Claims (1)

(57) [Claims] 1. A print laminate in which a polyester film is laminated on a print layer side of a print, and a coating layer containing a water-soluble or water-dispersible resin and a lubricant is laminated on an exposed surface side of the film.