JP3097266B2 - Print laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent adhesion to hot stamp foils, printing inks, etc., and has antistatic properties, scratch resistance,
The present invention relates to a print laminate having improved 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. On the other hand, a polyvinyl chloride film has problems in terms of fisheye and thickness deflection, and also has a problem in that chlorine gas is generated when the print laminate is incinerated.

[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. In addition, since the antistatic property is insufficient, dust such as paper powder easily adheres to the printed matter, which degrades the appearance of the printed material.

[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 print laminate having a specific structure has an adhesive property, an antistatic property, a scratch resistance, a workability and I found it to be excellent in terms of gloss,
The present invention has been completed. That is, the gist of the present invention is that a polyester film is laminated on a printing layer side of a printed body, and (a) an aqueous resin is provided on an exposed surface side of the film.
(B) an antistatic aqueous polymer having a sulfonic acid group or a sulfonic acid group in the molecule, and (c) a water-soluble or
Exists in a print laminate in which a coating layer containing a water-dispersible polyolefin is laminated.

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 grolyl, 1,4-cyclohexanediyl. Polyester produced by polycondensation with a glycol such as methanol.

[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. In addition, various stabilizers, ultraviolet absorbers, lubricants, pigments, antioxidants, plasticizers, and the like may be added to the polyester film.

The aqueous resin used in the present invention refers to a water-soluble or water-dispersible resin such as starch, cellulose derivatives such as methylcellulose and hydroxyethylcellulose, alginic acid, gum arabic, gelatin, sodium polyacrylate, polyacrylamide. , Polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, urethane resin, acrylic resin, polyamide resin, ether resin, epoxy resin, ester resin, and the like. In the present invention, particularly preferred are urethane resins, acrylic resins, and polyester resins. As urethane resin, the main components are
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.

The main components of the acrylic resin are alkyl acrylate or alkyl methacrylate, and the reaction of carboxyl groups or salts thereof, acid anhydride groups, sulfonic acid groups or salts thereof, amide groups, amino groups, hydroxyl groups, epoxy groups and the like. An aqueous acrylic resin obtained by copolymerizing a vinyl monomer having a hydrophilic functional group can be used. As the dicarboxylic acid component of the polyester resin,
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; oxycarboxylic acids such as oxybenzoic acid; and ester-forming derivatives thereof. Etc. can be used. As the glycol component of the polyester-based resin, ethylene glycol, 1,4-butanediol, diethylene glycol, aliphatic glycols such as triethylene glycol,
Alicyclic glycols such as 1,4-cyclohexanedimethanol, aromatic diols such as p-xylene diol,
Polyethylene glycol, polypropylene glycol,
Poly (oxyalkylene) glycols such as polytetramethylene glycol can be used.

As the polyester resin, not only the above-mentioned saturated linear polyester comprising the ester-forming component but also a compound having a trivalent or higher valent ester-forming component or a compound having a reactive unsaturated group may be used as the 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, the above aqueous resins may be used in combination as appropriate. The mixing ratio of the aqueous resin is 1 to the components constituting the coating layer.
The content is preferably in the range of 0 to 90 wt%, more preferably 2 to 90 wt%.
It is in the range of 0 to 80 wt%.

The antistatic aqueous polymer compound having a sulfonic acid group or a sulfonic acid group in the molecule according to the present invention does not decrease the adhesiveness to a printing ink, a hot stamp foil or the like, and prevents the coating layer from having an antistatic property. It has the function of imparting properties. The term "aqueous polymer compound" as used herein refers to a water-soluble or water-dispersible polymer compound. Such compounds preferably have a molecular weight of 500 or more, and more preferably have a molecular weight of 1000 or more. Generally, a low-molecular-weight compound such as sodium alkyl sulfonate is contained in the coating layer in order to impart antistatic properties, but depending on the amount of the compound, such an antistatic compound bleeds out to the surface of the coating layer. In addition, the adhesive property of the coating layer is reduced. In particular, when stored under high temperature and high humidity, the adhesive performance is significantly reduced.

Examples of the antistatic aqueous polymer compound having a sulfonic acid group or a sulfonic acid group in the molecule used in the present invention include the following. For example, vinyl sulfonic acid, sodium vinyl sulfonate, potassium vinyl sulfonate, lithium vinyl sulfonate, ammonium vinyl sulfonate, allyl sulfonate, sodium allyl sulfonate, potassium allyl sulfonate, lithium allyl sulfonate, ammonium allyl sulfonate, meta Copolymerizable with at least one kind of monomer such as sulfonic acid, sodium methallylsulfonate, potassium methallylsulfonate, lithium methallylsulfonate, ammonium methallylsulfonate, sulfopropyl acrylate or a salt thereof. Those obtained by copolymerizing at least one kind of monomer with a method such as a non-emulsifier emulsion polymerization method or a solution polymerization method are exemplified.

Examples of such copolymerizable monomers include acrylic acid or methacrylic acid and methyl, ethyl,
Propyl, butyl, amyl, hexyl, heptyl, octyl, esters composed of lower alcohols such as 2-ethylhexyl and hydroxyalkyl esters of acrylic acid or methacrylic acid, alkoxyalkyl esters, alkyl alkylene glycol esters, glycidyl esters and the like, styrene and Styrene derivatives such as monoalkylstyrene, dialkylstyrene, and trialkylstyrene are exemplified. Among the above compounds, particularly preferred in the present invention are those having at least one of vinyl sulfonic acid and vinyl sulfonic acid salt as a component of the copolymer.
It is contained in the range of 0 to 70 mol%, preferably 15 to 50 mol%. If the content is less than 10 mol%,
In many cases, the copolymer itself does not have sufficient antistatic ability, and if it exceeds 70 mol%, the polymerizability may be poor.

In the present invention, the compounding ratio of the antistatic aqueous polymer having a sulfonic acid group or the like in the molecule is as follows:
The content is preferably in the range of 10 to 90% by weight, more preferably 20 to 80% by weight, based on the components constituting the coating layer. If the compounding ratio is less than 10 wt%, the antistatic effect may not be sufficiently exhibited, and 90 wt%
When it exceeds, the gloss of the surface of the coating layer may be inferior. The above compound may be appropriately adjusted so that the surface resistivity of the coating layer surface is 10 ¹² Ω / port or less, preferably 10 ¹¹ Ω / port or less. When the surface resistivity exceeds 10 ¹² Ω / mouth, the antistatic effect is not sufficiently exhibited, and dust and dust and paper dust are liable to adhere at the time of processing, which may deteriorate the aesthetic appearance and lower the commercial value. In addition, the print laminates may adhere to each other due to electrification, resulting in poor workability.

In the present invention, the water-soluble or water-dispersible polio
Refins must be used as lubricants.

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 copolymers of two or more of the above 1-olefins with conjugated or non-conjugated dienes, 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 with conjugated or non-conjugated diene, for example, ethylene-butadiene Copolymer,
Ethylene-butadiene copolymer, ethylene-ethylidene norbornel copolymer

(Iv) 1-olefins, especially copolymers of ethylene and vinyl acetate, and their fully or partially saponified products (v) The above-mentioned conjugated or non-conjugated gens or vinyl acetates alone or copolymerized with 1-olefins And a completely or partially saponified product thereof as a basic skeleton, and those obtained by dissolving or dispersing these 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. In addition, by introducing a vinyl compound having a hydrophilic group such as a carboxylic acid group, a sulfo group, a polyether, an alkylolamide group or a salt thereof into the skeleton of the polyolefin by copolymerization or grafting, the compound is rendered water-soluble or What facilitated water dispersion can also be used.

The mixing ratio of the lubricant used in the present invention is as follows:
The content is preferably in the range of 0.1 to 30% by weight, more preferably 0.5 to 15% by weight, based on the components constituting the coating layer.
Range. By the addition of the lubricant, the sliding of the surface of the coating layer is improved, and the scratch resistance of the surface of the coating layer is also significantly improved. If the blending ratio of the lubricant is too small, the above effect is not sufficiently exerted. If the blending ratio is too large, the surface of the coating layer becomes sticky or the adhesiveness to printing ink, hot stamp foil or the like is reduced. Further, in the coating layer, for improvement of blocking and the like, a crosslinking agent, inorganic particles, organic particles may be contained, if necessary, an antifoaming agent, a coating improver, a thickener,
It may contain an antioxidant, an ultraviolet absorber, a dye, and the like.

The thickness of the coating layer of the film used in the present invention is usually from 0.01 to 3 μm, preferably from 0.02 to 1 μm. If the thickness is less than 0.01 μm, it tends to be difficult to obtain a uniform coating layer. On the other hand, when the thickness is more than 3 μm, the slipperiness may be reduced and the handling of the film may be difficult. As a method of providing a coating layer on a polyester film, a known method such as a gravure coating method, a reverse coating method, a rod coating method, an air doctor coating method can be applied, and the coating liquid of the present invention is applied to a polyester unstretched film. The following or simultaneous biaxial stretching methods, a method of applying to a uniaxially stretched polyester film and further stretching in a direction perpendicular to the uniaxially stretching direction, or a method of applying to a biaxially stretched polyester film are available.

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 print laminate of the present invention essentially requires the above-mentioned coating layer to be formed on the exposed surface side of the polyester film. Can be provided. For example, the same coating layer as the above-mentioned coating layer can be provided, or an adhesive layer or a heat-fusible polymer layer can be provided. Further, these can be used in combination.

Incidentally, in order to enhance the adhesiveness between the polyester film and the adhesive or the heat-fusible polymer, the polyester film may be subjected to a chemical treatment or a discharge treatment in advance. 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 polyester film at the coating portion of the laminator and dried, and then the adhesive applied surface of the polyester film and the printed surface of the printed material are thermocompressed. Or by laminating a heat-sealing polymer such as an ethylene-vinyl acetate copolymer on a polyester film and thermocompression-bonding the heat-sealing polymer layer surface of the polyester film and the printing surface of the printed body.

[0026]

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. In the description, “parts” means “parts by weight (solid content)”. The evaluations in the examples are as follows. (1) Adhesiveness A. 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. Further, the above-mentioned sample with the hot stamp was placed at 40 ° C. for 8 hours.
After being stored at 0% RH for 48 hours, the above-mentioned adhesiveness was evaluated in the same manner.

B. Adhesiveness with printing ink Screen ink of Toyo Ink Co., Ltd. (a mixture of FDSS21 391 indigo and reducer P ″ at a ratio of 10: 1) is applied to the base film surface of the print laminate body with 300.
It was applied to a thickness of about 10 μm using a mesh silk screen and cured with a UV lamp. After curing, apply a cellophane tape manufactured by Nichiban Co., Ltd.
Rapid peeling was performed in the 0 ° 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. Further, the above-described sample on which the ink was printed was subjected to 40 ° C., 80% R
After storing for 48 hours in H, the above-mentioned adhesiveness was evaluated in the same manner.

(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.

(4) Antistatic Property The surface resistivity of the printed laminate body on the substrate film side was determined by measuring the inner electrode of Yokogawa-Hewlett-Packard Company 50 m.
160 which is a concentric electrode having a diameter of 70 mm and an outer diameter of 70 mm.
08A (trade name) and 4329A, the company's high resistance meter
Under the atmosphere of 23 ° C and 50% RH using (trade name)
A voltage of 100 V was applied for measurement.

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., a coating solution having the following composition is applied to one surface of the machine-stretched film, and then stretched 3.2 times in the transverse direction at 110 ° C. and 220 ° C. Heat treatment was performed to obtain a 12 μm thick film having a 0.1 μm thick coating layer. 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 C46H (mixing ratio 1/1) manufactured by Dainichi Seika Kogyo Co., Ltd. The coating amount was 2 g / m ² as a solid content.

Composition of coating solution Polyester aqueous dispersion A (56 mol% of terephthalic acid, 40 mol% of isophthalic acid, 4 mol% of 5-sodium sulfoisophthalic acid, 70 mol% of ethylene glycol, 13 mol% of diethylene glycol, 1,4- Butanediol 17
Aqueous dispersion of polyester consisting of mol%) 50 parts; SV
45 parts of an aqueous dispersion composed of S-MMA-MA-HEMA copolymer (SVS content: 25 mol%); 5 parts of a polyethylene aqueous dispersion (Hitec E4B manufactured by Toho Chemical Industry Co., Ltd.)

In the above composition, abbreviations are as follows. SVS: Sodium vinyl sulfonate MMA: Methyl methacrylate MA: Methyl acrylate HEMA: Hydroxymethyl methacrylate

Example 2 Example 1 was repeated except that the coating solution was changed as described below.
A print laminate was obtained in the same manner as in Example 1. Coating solution composition 70 parts of aqueous polyester dispersion A; SVS-MMA-MA
-HEMA copolymer aqueous dispersion (SVS content 2
5 parts by mole; 25 parts; polyethylene water dispersion (Hitec E4B manufactured by Toho Chemical Industry Co., Ltd.) 5 parts

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 composition 70 parts of aqueous polyester dispersion A; SVS-MMA-MA
-HEMA copolymer aqueous dispersion (SVS content 1
5 parts by mole; 25 parts; polyethylene water dispersion (Hitec E4B manufactured by Toho Chemical Industry Co., Ltd.) 5 parts

Example 4 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 Working Example 1. Coating liquid composition Polyester aqueous dispersion B (terephthalic acid 92 mol%, 5
50 parts of an aqueous dispersion of a polyester comprising 8 mol% of sodium sulfoisophthalic acid, 75 mol% of ethylene glycol, and 25 mol% of diethylene glycol); SVS-MM
A-MA-HEMA copolymer aqueous dispersion (SVS
45 parts; Polyethylene aqueous dispersion (Hi-Tech E-103N manufactured by Toho Chemical Industry Co., Ltd.) 5 parts

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 obtaining a film having a thickness of 12 μm in the same manner as described above, one surface of the film is subjected to corona treatment, an adhesive is applied to the opposite surface of the corona treated surface, and the printed surface of the printed white paperboard (manila ball) is opposed to the printed surface. 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. Composition of coating liquid 95 parts of aqueous polyester dispersion A; 5 parts of aqueous polyethylene dispersion (Hitec E4B manufactured by Toho Chemical Industry Co., Ltd.)

Comparative Example 4 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 composition 95 parts of polyester aqueous dispersion A; 5 parts of sodium dodecylbenzenesulfonate Comparative Example 5 Except that the coating solution in Example 1 was changed as follows.
A print laminate was obtained in the same manner as in Example 1. Composition of coating liquid 95 parts of an aqueous dispersion composed of SVS-MMA-MA-HEMA copolymer (SVS content: 25 mol%); polyethylene aqueous dispersion (Hitec E4B manufactured by Toho Chemical Industry Co., Ltd.) 5
Department

Comparative Example 6 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 liquid composition Aqueous dispersion of polyester A 50 parts; SVS-M
Aqueous dispersion (SV) composed of MA-MA-HEMA copolymer
Comparative Example 7 An adhesive was applied to one surface of a biaxially stretched polypropylene film (Trefane S645 manufactured by Toray Industries, Inc.) having a thickness of 20 μm, and printed on a white paperboard (manila ball) ) Was laminated so as to face the printing surface to obtain a print laminate. In addition. 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.

[0041]

[Table 1]

[0042]

The print laminate of the present invention is excellent in adhesiveness, antistatic property, scratch resistance and glossiness of hot stamp foil and printing ink, etc., and has high industrial value.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-638 (JP, A) JP-A-61-205137 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 C08J 7/04

Claims (1)

(57) [Claims] 1. A polyester film is laminated on a printed layer side of a printed body, and (a)
A print laminate comprising an aqueous resin, (b) a coating layer containing an antistatic aqueous polymer compound having a sulfonic acid group or a sulfonic acid group in a molecule, and (c) a water-soluble or water-dispersible polyolefin. .