JP4871671B2 - Laminated film for thermal lamination - Google Patents

Description

  The present invention is a laminated film for heat laminating, more specifically, excellent moldability, excellent productivity, excellent bondability with a substrate such as an inkjet printed material, and sufficient laminate strength, The present invention relates to a laminated film for thermally laminating a printed matter that is excellent in transparency and can be beautifully protected without impairing the clarity of a printed surface or the like.

  In recent years, a method of covering a printing surface of a magazine, an advertisement or the like with a thermoplastic resin film to give gloss and protecting the printing surface has been widely adopted.

  Such a thermoplastic resin that protects the printed surface is excellent in transparency, is not easily scratched, and needs to maintain excellent gloss over a long period of time. Bondability is important, and when a poorly bonded part occurs with the base material, a local transparent defective part called blur occurs, and the sharpness is impaired and the beauty of the printed surface is impaired. There's a problem.

In mass printing of magazines and advertisements, offset printing is usually performed, and offset printing paper is usually used as a printing medium. It is relatively easy to thermally laminate a resin film on offset printing paper subjected to offset printing.
However, recently, demand for printed materials in a variety of products and small lot items has been increasing rapidly because of on-demand correspondence. For this reason, the first correspondence is printing by an ink jet printer, and this is OA such as computers. Since images and designs created by devices can be printed immediately, the printers of this method are widely used not only for office and commercial purposes but also for general households due to the reduction in size and cost.

  In the ink jet printing method, basically, ink prepared by adjusting dyes / pigments, resins, additives, and the like with a mixed solvent of water and alcohol is ejected from a nozzle onto a printing paper and adhered to form a printed matter. Printing paper may contain silicone components and other additives to increase ink receptivity, or the adhering ink layer may contain additives to prevent it from flowing out due to moisture. is there. For this reason, there is a problem that even if a normal heat laminating film is laminated on these, the laminate strength is insufficient. In addition to the ink jet method, there is a similar problem when laminating a printed material with hot melt ink. For this reason, it is also practiced to carry out lamination after curing for a certain period of time after printing.

In order to solve such a problem, a sheet composed of a hot-melt adhesive or a microcapsule in which an adhesive is sealed between a protective layer and a printed material has been proposed as a protective sheet (for example, Patent Document 1). reference.). However, a good laminate strength cannot be obtained simply by using a hot-melt adhesive, and even an adhesive microcapsule cannot be used as an industrial laminated film.
Under such circumstances, the appearance of an improved laminated film suitable for the thermal laminating method that is frequently used for protective coating or beautifying the surface of a printed material printed with inkjet ink has been eagerly desired.
JP-A-9-66683

  In the state of the prior art, the present invention is excellent in moldability and productivity, excellent in bondability with a substrate such as an ink-jet print, expresses a sufficient laminate strength, and excellent in transparency. It is an object of the present invention to provide a laminated film for thermally laminating a printed material that can be beautifully protected without impairing the clarity of the printed surface or the like.

  As a result of intensive studies to solve the above problems, the present inventors laminated a specific ethylene-based resin layer and a specific anchor coat agent layer in this order on one side of a base material layer made of a thermoplastic resin. By doing so, it has excellent moldability, excellent productivity, excellent bondability with substrates such as inkjet prints, sufficient laminate strength, excellent transparency, and clearness of the printed surface, etc. The present inventors have found that a laminated film for thermally laminating a printed material that can be protected beautifully without loss is obtained, and the present invention has been completed.

That is, according to the first aspect of the present invention, the ethylene-based resin layer (B) and the anchor coat agent layer (C) are laminated in this order on one side of the base material layer (A) made of the thermoplastic resin. The ethylene-based resin layer (B) is (b1) an ethylene / α-olefin copolymer polymerized using a single site catalyst, (b2) ethylene / Vinyl acetate copolymer, (b3) ethylene / (meth) acrylic acid copolymer, or (b4) low density polyethylene, while anchor coat agent layer (C) is (c1) polyalkyleneimine There is provided a laminated film characterized in that it is a system anchor coating agent.

Further, according to the second aspect of the present invention, in a first aspect, the ethylene-based resin layer (B) is a ethylene · alpha-olefin copolymer polymerized with (b1) single site catalyst Thus, a laminated film having a melting point of 60 to 90 ° C. and a density of 0.870 to 0.910 g / cm 3 is provided.
Furthermore, according to the third aspect of the present invention, in a first aspect, the ethylene-based resin layer (B) is, (b2) an ethylene-vinyl acetate copolymer, its vinyl acetate content of 3 to 50 There is provided a laminated film having a weight% and MFR (230 ° C., 21.18 N load) of 1 to 30 g / 10 min.

According to the fourth invention of the present invention, in any one of the first to third inventions, the base material layer (A) is a stretched or unstretched film of polypropylene, polyethylene terephthalate, polyamide or polystyrene. A featured laminated film is provided.

  The laminated film of the present invention is excellent in adhesive strength after lamination, has high initial adhesive strength, can be laminated under the same temperature conditions as conventional laminating conditions, and has the excellent effect that no bleeding of printing or printing occurs. Have. Moreover, it is excellent in transparency and can protect a base material without inhibiting an aesthetic sense. Furthermore, since the laminated film has a layer structure excellent in moldability, it can be efficiently produced by extrusion lamination.

The present invention relates to a laminated film for thermally laminating a printed material in which an ethylene resin layer (B) and an anchor coating agent layer (C) are laminated in this order on one side of a base material layer (A) made of a thermoplastic resin. Wherein the ethylene-based resin layer (B) is polymerized using (b1) a single site catalyst, (b2) ethylene / vinyl acetate copolymer, (b3) ethylene / ( It is a laminated film selected from a (meth) acrylic acid copolymer or (b4) low density polyethylene, and the anchor coating agent layer (C) is a (c1) polyalkyleneimine anchor coating agent. Hereinafter, the resin, laminated film, printed material base, and the like constituting each layer will be described in detail.

1. Base material layer (A)
The base material layer (A) of the laminated film of the present invention is made of a thermoplastic resin. Any thermoplastic resin can be used, such as polyethylene terephthalate, polyethylene naphthalate, polystyrene, polypropylene, polycarbonate, polyvinyl alcohol, polyethylene, polyvinyl chloride, nylon such as nylon, polyimide, etc., but preferably polypropylene. (In particular, a stretched polypropylene film usually referred to as OPP), a stretched or unstretched film of polyethylene terephthalate, polyamide, polystyrene (especially a stretched polystyrene film commonly referred to as OPS), and usually 0.5 to 50 μm. A film of a certain thickness is used.

2. Ethylene resin layer (B)
The ethylene-based resin layer (B) of the laminated film of the present invention is an ethylene / α-olefin copolymer laminated on one side of the base material layer (A) and polymerized using the following (b1) single site catalyst, (B2) an ethylene / vinyl acetate copolymer, (b3) an ethylene / (meth) acrylic acid copolymer, or (b4) a low density polyethylene.

(B1) ethylene / α-olefin copolymer polymerized using a single site catalyst used as an ethylene-based resin layer (B) (b1) ethylene / α-olefin copolymer polymerized using a single site catalyst The coalescence preferably has a melting point of 60 to 90 ° C., and is a copolymer of ethylene and preferably an α-olefin having 3 to 12 carbon atoms. The α-olefin other than ethylene used as a comonomer of the ethylene / α-olefin copolymer is preferably an α-olefin having 3 to 12 carbon atoms, specifically, propylene, 1-butene, 1 Preferred examples include -pentene, 1-hexene, 1-octene and the like.

The content of α-olefin in the ethylene / α-olefin copolymer is preferably 5 to 40% by weight, more preferably 7 to 35% by weight. When the α-olefin content is low, the impact strength and low-temperature heat sealability of the film cannot be obtained, and when it is too high, the blocking resistance is impaired. The α-olefin content is measured by a ¹³ C-NMR method.
Ethylene / α-olefin copolymers based on single-site catalysts are known, and polymerization catalysts and polymerization methods therefor are also known, and can be obtained by the same methods.

The ethylene / α-olefin copolymer (b1) based on a single site catalyst has the following properties (i) and (ii), and is preferably a copolymer having the properties (iii) and (iv).
(I) Melting point The melting point of the ethylene / α-olefin copolymer (b1) is particularly preferably 60 to 90 ° C, and more preferably 65 to 90 ° C. If the melting point is less than 60 ° C, the blocking suitability tends to be poor, and if it exceeds 125 ° C, the print laminate suitability tends to be poor.
Here, the melting point is a value measured by a differential thermal analysis method.
(Ii) Density The density of the ethylene / α-olefin copolymer (b1) is preferably 0.870 to 0.910 g / cm ³ , more preferably 0.890 to 0.905 g / cm ³ . If the density is less than 0.870 g / cm ³ , the film tends to be sticky, and if it exceeds 0.910 g / cm ³ , adhesion suitability such as adhesive strength tends to be deteriorated.
Here, a density is a value measured at 23 degreeC based on the case of the low density polyethylene of JIS-K6922-2: 1997 appendix.
(Iii) Melt flow rate (MFR)
The melt flow rate (190 ° C., 21.18 N load) of the ethylene / α-olefin copolymer (b1) is preferably 5 to 100 g / 10 minutes, more preferably 10 to 50 g / 10 minutes.
Here, MFR is a value measured based on JIS-K6921-2: 1997 appendix (190 degreeC, 21.18N load).
(Iv) Ratio of average molecular weight (Mz) to number average molecular weight (Mn) Z average molecular weight (Mz) and number average determined by gel permeation chromatography (GPC) of ethylene / α-olefin copolymer (b1) The ratio (Mz / Mn) to the molecular weight (Mn) is preferably 8.0 or less, particularly preferably 5.0 or less. When Mz / Mn exceeds 8.0, transparency tends to deteriorate.

  Further, the ethylene / α-olefin copolymer (b1) based on a single site catalyst can be appropriately selected from those commercially available as metallocene polyethylene. Examples of commercial products include “Kernel” and “Harmolex” manufactured by Nippon Polyethylene, and “Affinity” manufactured by DuPont Dow. The ethylene / α-olefin copolymer may be used singly or as a mixture of two or more thereof, and blending with other polyethylene, particularly high-pressure low-density polyethylene is also a preferred embodiment.

(B2) Ethylene / vinyl acetate copolymer (EVA)
The (b2) ethylene / vinyl acetate copolymer (EVA) used as the ethylene-based resin layer (B) may be produced by a tubular system or an autoclave system.
The vinyl acetate content of the ethylene / vinyl acetate copolymer is preferably about 3 to 50% by weight, more preferably about 5 to 30% by weight, and particularly preferably about 15 to 25% by weight. When the vinyl acetate content exceeds this, stickiness tends to occur, and when it falls below, adhesion tends to be poor.
MFR (230 degreeC, 21.18N load) becomes like this. Preferably it is 1-30 g / 10min, Furthermore, it is about 2-20 g / 10min. When the MFR exceeds this value, the stability of the molten resin film at the time of molding tends to deteriorate, and when it falls below, the adhesion tends to deteriorate.
Here, MFR is a value measured based on JIS-K6921-2: 1997 appendix (230 degreeC, 21.18N load).

(B3) Ethylene / (meth) acrylic acid copolymer (b3) Ethylene / (meth) acrylic acid copolymer used as the ethylene resin layer (B) is composed of ethylene and acrylic acid, methacrylic acid, It means a generically named copolymer having acrylic acid ester and / or methacrylic acid ester as a copolymerization component. As a copolymerization ratio with these ethylene, it is preferable that (meth) acrylic acid or a (meth) acrylic ester-based comonomer is 5% by weight to less than 50% by weight, and more preferably 10 to 40% by weight. Furthermore, it is 15 to 40% by weight.
When the comonomer ratio is less than 5% by weight, it is difficult to obtain a sufficient adhesive force, and when it exceeds 50% by weight, handling as a resin tends to be difficult.

(B4) Low density polyethylene
The (b4) low density polyethylene used as the ethylene-based resin layer (B) usually has a density of 0.905 to 0.930 g / cm ³ , preferably 0.910 to 0.925 g / cm ³ , and MFR Is 190-50 ° C., 0.2-50 g / 10 min, preferably 3-20 g / 10 min, melting point 100-130 ° C., preferably 105-120 ° C. 20 is a copolymer with 50 mol% or less of α-olefin. Such low density polyethylene preferably includes, for example, a method of radical polymerization at high pressure and high temperature by adding oxygen to an ethylene monomer, or one produced by a low / medium pressure method using a Ziegler catalyst. Can be used.
Here, the density is a value measured at 23 ° C. according to the case of the low density polyethylene of JIS-K6922-2: 1997 appendix, and MFR is JIS-K6921-2: 1997 appendix (190 ° C., 21.21). 18N load), and the melting point is a value measured by differential thermal analysis.

  In addition, other additional arbitrary components can be mix | blended with the ethylene-type resin layer (B) of this invention in the range which does not impair the effect of this invention remarkably. Examples of such optional components include an antioxidant, a clarifying agent, a lubricant, an antiblocking agent, an antistatic agent, an antifogging agent, a neutralizing agent, a metal deactivator, a colorant, and a fluorescent brightening agent. it can.

3. Anchor coating agent layer of the laminated film of the anchor coating agent layer present invention (C) is laminated on the ethylene-based resin layer (B), which is (c1) a polyalkylene imine-based anchor coating agents described below.

(C1) Polyalkyleneimine anchor coating agent Examples of the (c1) polyalkyleneimine anchor coating agent used as the anchor coating agent include polyethyleneimine and polypropyleneimine, and polyethyleneimine is preferred.
Polyethyleneimine is produced by ring-opening polymerization of ethylene using carbon dioxide, hydrochloric acid, hydrobromic acid, p-toluenesulfonic acid, aluminum chloride, boron trifluoride or the like as a catalyst, or by polycondensation of ethylene chloride and ethylenediamine. A general formula — [CH ₂ CH ₂ N (CH ₂ CH ₂ NH ₂ ) CH ₂ CH ₂ NH] _n —
It is typically a viscous liquid that also has a partially crosslinked structure, is extremely hydrophilic, and has a primary or tertiary amino group in the molecule, so that it can adhere to inkjet printing surfaces. Excellent.
Any degree of polymerization of polyethyleneimine can be used, but it is preferably 20 to 300. Examples of commercially available products include EL-420 manufactured by Toyo Ink Manufacturing Co., Ltd., Epomin SP-200 and SP-012 manufactured by Nippon Shokubai Co., Ltd., Polymin SN manufactured by BASF, Lupazole-P, and AC-108 manufactured by Dainippon Ink & Chemicals, Inc. .

(C2) Polybutadiene anchor coating agent (c2) The polybutadiene anchor coating agent used as an anchor coating agent is a liquid polymer dispersed in water with polybutadiene modified with a hydroxyl group or a carboxyl group at the end of the polybutadiene chain, It can be diluted with water or alcohol. In particular, those derived from 1,2-polybutadiene can be used particularly preferably. Examples of commercially available products include EL451 manufactured by Toyo Ink Co., Ltd., Chitabond T-180 and T-200 manufactured by Nippon Soda Co., Ltd., and epomin manufactured by Toyo Morton.

(C3) Isocyanate-based anchor coating agent The (c3) isocyanate-based anchor coating agent used as the anchor coating agent may be of any type as long as it is an anchor coating agent containing an isocyanate compound. An isocyanate-effect urethane-based anchor coating agent that forms a urethane bond by a reaction between a polyol and an isocyanate is preferred.
As the isocyanate component, 4,4-diphenylmethane diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate and the like are used, and isophorone diisocyanate is particularly preferable. The polyol is preferably a polyester polyol, a polyether polyol or a mixture thereof, preferably having a weight average molecular weight of 5,000 to 50,000, more preferably 15,000 to 30,000.

4). Laminated film The laminated film of the present invention is a laminated film in which an ethylene-based resin layer (B) and an anchor coating agent layer (C) are laminated in this order on one side of the base material layer (A) made of the thermoplastic resin. .
The thickness ratio of the laminated film is preferably in the range of base material layer (A): ethylene resin layer (B) = 10 to 150: 5 to 100 μm, preferably 10 to 50:10 to 50 μm.
The thickness of the anchor coating agent layer (C) is preferably from 0.005 to 3 g / ^{m 2} The coating amount, more preferably 0.01 to 0.5 g / ^{m 2.}

  Although there is no restriction | limiting in particular in the manufacturing method of the laminated | multilayer film of this invention, the ethylene-type resin layer (B) is extrusion-lamination-molded to the base material layer (A) which consists of a thermoplastic resin, and it anchors to an ethylene-type resin layer (B). It can manufacture especially suitably by combining the method of coating a coating layer (C).

There is no restriction | limiting in particular as an extrusion laminating method, A general extrusion laminating method can be used. Specifically, a base material layer made of a thermoplastic resin is fed out, and if necessary, an anchor coat agent for extrusion laminating is anchored inline by a technique such as a gravure coater, and then ethylene is extruded in an extruder. The resin is extruded while being melted by heat, and is nipped between a cooling roll and a rubber roll. There is no particular restriction on the heat melting temperature of the ethylene-based resin, but if it is too low, the adhesive strength between the layers may not be obtained, so it is preferable that it is somewhat high, specifically 180 ° C. or higher, preferably 200 ° C. or higher. More preferably, 220 ° C. is particularly preferable. Further, if the heat melting temperature is too high, thermal deterioration may occur and a laminated film having a good appearance shape may not be obtained. Therefore, it is preferable that the film is low to some extent, specifically 320 ° C. or lower, preferably 300 ° C. or lower. More preferably, it is preferably 280 ° C.
Moreover, ozone can also be irradiated between the base material layer and the layer of the ethylene-based resin as necessary. Then, strong adhesion can be obtained without increasing the melting temperature. Thereafter, the wetting tension is increased by corona discharge treatment or flame (flame) treatment on the ethylene resin layer.

  The conditions for molding the laminated film by extrusion lamination are not particularly limited as long as the characteristics specified in the present invention are obtained, but the molding temperature is 200 to 340 ° C., preferably 200 to 300 ° C., and the molding speed is 50 to 500 m / min. Preferably, 100 to 300 m / min is suitable.

  Examples of the coating method include a method of coating the anchor coating agent with a gravure coater, a transfer roll coater, an air knife coater, or a wire bar coater.

  Extrusion laminating machines, gravure coaters, cooling rolls, compressed rubber rolls, corona discharge treatment machines, transfer roll coaters, air knife coaters, wire bar coaters, etc. that can be used in these molding methods should be those that are commonly used. Can do.

5. Printed material base material The printed material base material to which the laminated film of the present invention is laminated and protected is not particularly limited as long as it is printed and printed, and is used for paper, fabrics, plastics, metals, and the like. The product can be affixed to magazines, book covers such as magazines, labels, posters, packaging boxes, and other devices to protect the surface. Especially, it is suitable as protection of the printing surface of sheets, such as printed paper and plastics.

  EXAMPLES Hereinafter, the present invention will be specifically described according to examples, but the present invention is not limited to these examples. In addition, the characteristic evaluation method of the print laminate product in an Example and resin used in the Example are as follows.

1. Characteristics of Print Laminate Products (1) Adhesive strength: Print laminate products are cut into test pieces with a width of 25 mm and a length of 100 mm, and 50 mm in the length direction is peeled off by hand, and then in a 180 degree direction with a Shimadzu tensile tester. The value of tensile strength peeled at a tensile speed of 300 mm / min was shown.

2. Substrate, resin, anchor coat agent, molding machine, printing paper (1) Substrate (A layer)
(I) PB260: Biaxially stretched polypropylene film (hereinafter referred to as OPP) manufactured by Futamura Chemical Co., Ltd.
(2) Ethylene resin (B layer)
(I) XM138: ethylene · α-olefin copolymer by single site catalyst manufactured by Nippon Polyethylene MFR = 40 g / 10 min, density = 0.895 g / cm ³ , melting point = 70 ° C.
(Ii) Novatec LV570: Ethylene / vinyl acetate copolymer (EVA) manufactured by Nippon Polyethylene Co., Ltd. MFR = 15 g / 10 min, vinyl acetate (VA) content = 20 wt%
(Iii) Everflex: Ethylene / ethyl acrylate copolymer (EEA) manufactured by Mitsui DuPont Polychemical Co., Ltd.
(3) Anchor coating agent (C layer)
(I) EL420: Polyethyleneimine anchor coating agent manufactured by Toyo Ink Manufacturing Co. (ii) EL451: Polybutadiene anchor coating agent manufactured by Toyo Ink Manufacturing Co. (iii) EL510: Isocyanate anchor coating agent manufactured by Toyo Ink Manufacturing ( 4) Extrusion laminate molding machine Sumiju Modern Machinery Co., Ltd. 1 type 1 layer single layer extrusion machine Extruder diameter φ90mm
(5) Printed paper Matte anchor coat paper (Ulite) manufactured by Tokyo Rismatic Co., Ltd., which has been subjected to inkjet printing on black ink and mixed color ink using CDT60V manufactured by Fuji Xerox Co., Ltd.

Example 1
An OPP film (thickness: 15 μm) was used as the base material layer (A layer), and a polyethyleneimine anchor coating agent (EL-420 manufactured by Toyo Ink Manufacturing Co., Ltd.) was applied to the surface. After drying, (B Layer), an ethylene / α-olefin copolymer (XM138 manufactured by Nippon Polyethylene Co., Ltd.) with a single site catalyst is laminated to a thickness of 15 μm with an extrusion laminating machine, and the B layer surface is subjected to in-line corona discharge treatment and then an ethylene-based resin. As a C layer on the surface (B layer) side, a polybutadiene-based anchor coating agent (EL451 manufactured by Toyo Ink Co., Ltd.) was coated with a gravure coater in an amount of 0.015 g / m ² to obtain a laminated film.
Next, two types of matte anchor coating papers of monochromatic black and mixed color black on which the C layer side of the obtained laminated film was inkjet-printed were applied to roll temperatures of 100 ° C., 110 ° C., 120 ° C., and a linear pressure of 55.6 kgf / A printed laminate product was obtained by thermocompression bonding with a crimping machine having a speed of 20 cm / min. Table 1 shows the results of adhesion strength immediately after bonding and 3 days after the obtained printed laminate product.

(Comparative Example 1)
In the same manner as in Example 1, an OPP film (thickness 15 μm) was used as the base material layer (A layer), and a polyethyleneimine anchor coating agent (EL-420 manufactured by Toyo Ink Manufacturing Co., Ltd.) was applied to the surface. After drying, After laminating an ethylene / α-olefin copolymer (XM138 manufactured by Nippon Polyethylene Co., Ltd.) with a single site catalyst on the coated surface to a thickness of 15 μm with a single-site catalyst as the (B layer), corona discharge treatment is applied to the B layer surface in-line. The laminated film which does not have C layer only given was obtained. Next, using the obtained laminated film, a print laminate product was obtained in the same manner as in Example 1. The evaluation results of the obtained print laminate product are shown in Table 1.

(Example 2)
A laminated film and a printed laminate product were obtained in the same manner as in Example 1 except that the layer C was coated with the polyethyleneimine anchor coat agent EL-420 instead of the polybutadiene anchor coat agent. The evaluation results are shown in Table 1.

(Example 3)
A laminated film and a printed laminate product were obtained in the same manner as in Example 1 except that the B layer was changed to LV570 of an ethylene vinyl acetate copolymer (EVA). The evaluation results of the obtained print laminate product are shown in Table 1.

(Comparative Example 2)
In Example 3, the same process was performed until the corona discharge treatment was performed on the EVA surface of the B layer in-line, and then a laminated film having no C layer was obtained. Next, using the obtained laminated film, a print laminate product was obtained in the same manner as in Example 1. The evaluation results of the obtained print laminate product are shown in Table 1.

Example 4
A laminated film and a printed laminate product were obtained in the same manner as in Example 1, except that EVA LV570 was used as the B layer component and a polyethyleneimine-based anchor coating agent was coated as the C layer component. The evaluation results are shown in Table 1.

(Example 5)
A laminated film and a printed laminate product were obtained in the same manner as in Example 1 except that an anchor coat agent coated with an EEA as a B layer component and a polyethyleneimine anchor coat agent as a C layer component was coated. The evaluation results are shown in Table 1.

(Comparative Example 3)
In Example 5, the same process was performed until the corona discharge treatment was performed on the EEA surface of the B layer in-line, and then a laminated film having no C layer was obtained. Next, using the obtained laminated film, a print laminate product was obtained in the same manner as in Example 1. The evaluation results of the obtained print laminate product are shown in Table 1.

(Example 6) As a reference example C layer, a laminated film and a printed laminate product were obtained in the same manner as in Example 1, except that the isocyanate anchor coating agent EL-510 was coated instead of the polybutadiene anchor coating agent. . The evaluation results are shown in Table 1.

As is clear from Table 1, in the lamination to the ink jet paper using monochromatic black, the print laminate product using the laminated film obtained in Example 1 does not have the C layer shown in Comparative Example 1. Compared to the laminated product, it was confirmed that the adhesive strength with the ink-printed mat anchor coat agent paper was sufficiently high, and the quality was excellent in practicality.
Further, in Example 2, by using a polyethyleneimine-based anchor coating agent as the C layer component, the adhesive strength of the laminated product obtained in Example 1 with the ink-printed mat anchor coating agent paper is even higher. It was confirmed that it had excellent strength.
The printed laminate product obtained in Example 3 has higher adhesive strength with the ink-printed mat anchor coat paper than the laminated product without the C layer shown in Comparative Example 2, and has excellent quality. I was able to confirm.
In Example 4, as in Example 3, compared with the laminated product not having (C layer) shown in Comparative Example 2, the adhesive strength with the mat anchor coat agent paper printed by ink jet printing is high, and excellent quality is achieved. It was confirmed that it had.
In Example 5, it was confirmed that the adhesive strength with the ink-printed mat anchor coat agent paper was high and excellent quality compared with the laminated product without (C layer) shown in Comparative Example 3. did it.
In Example 6, it was confirmed that the adhesive strength with the ink-printed mat anchor coat agent paper was high and excellent quality compared with the laminated product without (C layer) shown in Comparative Example 1. did it.
Furthermore, the laminate for ink-jet paper using mixed-color black ink is slightly inferior to the adhesive strength for the ink-jet paper using monochromatic black ink, but it can be confirmed that it has sufficiently high adhesive strength and excellent quality. It was.

  The laminated film of the present invention is excellent in adhesive strength after lamination, has high initial adhesive strength, can be laminated under the same temperature conditions as conventional laminating conditions, and has the excellent effect that no bleeding of printing or printing occurs. Therefore, it can be suitably used as an industrial laminated film for lamination.

Claims (4)

This is a laminated film for thermally laminating a printed material in which an ethylene resin layer (B) and an anchor coating agent layer (C) are laminated in this order on one side of a base material layer (A) made of a thermoplastic resin. And
The ethylene resin layer (B) consists of (b1) an ethylene / α-olefin copolymer polymerized using a single site catalyst, (b2) an ethylene / vinyl acetate copolymer, (b3) ethylene / (meth) acrylic. Selected from an acid copolymer or (b4) low density polyethylene,
On the other hand, an anchor coating agent layer (C) laminate film, which is a (c1) polyalkyleneimine-based anchor coating agents. The ethylene-based resin layer (B) is (b1) an ethylene / α-olefin copolymer polymerized using a single site catalyst, the melting point is 60 to 90 ° C., and the density is 0.870 to 0.910 g. The laminated film according to claim 1 , which is / cm ³ . The ethylene-based resin layer (B) is (b2) an ethylene / vinyl acetate copolymer having a vinyl acetate content of 3 to 50% by weight and an MFR (230 ° C., 21.18 N load) of 1 to 30 g / 10. The laminated film according to claim 1 , wherein the laminated film is a minute. The base film (A) is a stretched or unstretched film of polypropylene, polyethylene terephthalate, polyamide, or polystyrene. The laminated film according to any one of claims 1 to 3 .