JP2002121515A - Laminated film and laminating method using this laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film capable of neatly cutting a protective layer along the peripheral edge of a print when the protective layer formed on a substrate is contact-bonded to the image surface of the print and then the above substrate is separated from the image. SOLUTION: In forming a laminated film obtained by laminating at least a surface layer and an adhesive layer on a substrate, the surface layer is formed by coating with a coating material obtained by mixing at least two types of emulsions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film for forming a protective layer on a print, and a laminating method using the laminated film. In particular, the present invention relates to a laminate film for forming a protective layer by peeling a substrate after thermocompression bonding a resin for a protective layer formed on a substrate to a print, and a laminating method using the same.

[0002]

2. Description of the Related Art A transparent resin layer applied on a heat-resistant substrate is thermocompression-bonded to an electrophotographic or ink-jet output print.
A method of peeling a heat-resistant substrate or obtaining a completed print without peeling has been widely used. For example, as disclosed in JP-A-6-91767, when the heat-resistant base material is peeled, the size of the heat-resistant base material coated with the protective layer resin in the printing dimension and the width direction is increased. There is a method in which the feeding direction is continuous, and only the protective layer portion adhered to the print is peeled off together with the print. As a means for applying such a protective layer, it is common to apply a coating material in which a polymer is dissolved in a solvent, or to apply a coating material in which resin particles are dispersed in a solvent as an emulsion, followed by drying.

On the other hand, as a technique for improving the functionality of the protective layer itself, Japanese Patent Application Laid-Open No. 2000-44901 discloses a technique for forming a stable ultraviolet absorbing layer by incorporating an ultraviolet absorbing molecular structure into a polymer constituting the protective layer resin. Have been. This publication states that the resin disclosed as an example is stable on a polycarbonate substrate, but the resin of the same formulation cannot withstand the elongation of the paper when absorbing moisture on a paper substrate and breaks. Things.

[0004]

In the prior art described above, the protective layer adhered to the print can be cut accurately at the edge of the print and the size of the print can be enlarged by moisture absorption. In some cases, two contradictory requirements that the protective layer is not cracked cannot be met.

According to the present invention, when a laminate film is laminated on a print and peeled off, the protective layer is cut accurately at the end of the print, and the protective layer does not crack even if the print absorbs moisture. It is an object to provide a film and a laminating method using the laminated film.

[0006]

The laminate film of the present invention is obtained by laminating at least a surface layer and an adhesive layer on a base material, and applying a paint obtained by mixing at least two or more types of emulsions. Is formed.

Further, the laminating method of the present invention comprises laminating at least a surface layer and an adhesive layer on a base material, and applying a coating material obtained by mixing at least two or more emulsions having different glass transition temperatures. Using a laminated film having a layer formed thereon, at a temperature equal to or higher than the glass transition temperature of the emulsion having a relatively high glass transition temperature, a step of pressing the laminate film and the print, and then the laminate film and the print. And a step of separating

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Prior to the description of the embodiments of the present invention,
A fixing mechanism for providing a thermocompression bonding / transfer process of a protective layer and a print according to the present invention will be described.

In FIG. 1, reference numeral 1 denotes an unwinding reel of a roll of the laminated film 2 of the present invention wound with the protective layer on the outside. The back tension is applied to the film 2 by a torque in the CCW direction in the drawing. I have. A heating roll 3 has a rotary encoder 4 on its center axis for detecting the rotation amount of the roll. Reference numeral 5 denotes a pressure roll for pressing the film 2 against a heating roll. The pressure is a linear pressure of 5 to 50 N / c.
m, especially about 15 to 35 N / cm.

Reference numeral 6 denotes a cooling fan for cooling the laminated film 2 and the print P, which have been pressed by the rolls 3 and 5, 7a and 7
Reference numeral b denotes a guide roll of the rear end peeling section, which is configured to be rotatable about a central axis. Reference numeral 7c denotes a movable peeling roll at the trailing end peeling portion, which is a print P which is pressure-bonded to the film 2 via a protective layer.
The printed matter P is peeled off from the film 2 by rapidly pressing the rear end of the printed matter P. Reference numeral 8 denotes a guide roll of a leading end peeling portion, and a printed material P obtained by pressing the roll 8 to the film 2 via a protective layer.
, The leading end of the print P is peeled off due to a difference in rigidity with the film 2. Reference numeral 10 denotes a take-up reel for the laminate film 2, which gives tension in the take-up direction. 11 is a guide for the print P, 12 is a photo interrupter constituting a first paper passage sensor, and 13 is a second photo interrupter.
Is a photo interrupter that constitutes the paper passage sensor of FIG.

When the print P is inserted into the guide 11 and the first paper passage sensor 12 generates a "presence" signal of the print P, the pressure roll 5 is pressed against the heating roll 3 and the heating roll 3 rotates to CW. Start. The linear velocity of the rotation is 5
It can be selected from the range of about mm / s to 40 mm / s, but is preferably in the range of 10 mm / s to 30 mm / s. The print P is adhered to the laminate film 2 by the rolls 3 and 5 via the protective layer.

The heating roll 3 when the first paper passage sensor 12 detects the change of the print P from "present" to "absent"
The rotary encoder 4 monitors the angular position of the heating roll 3 from the angular position to the rear end of the printed material at the rear end peeling section, and the rear end peeling is performed by the movable peeling roll 7c of the rear end peeling section. Thereby, the print P is peeled off from the laminate film 2 only at the rear end together with the protective layer. After that, after the second paper passage sensor 13 detects "absence" of the print P, the laminate film 2 has a length required for completing the discharge.
Is sent. This is also performed by the rotary encoder 4 monitoring the rotation of the heating roll 3 for a distance from the rear end of the print P after passing through the second sensor 13 until the paper ejection is completed. On this occasion,
Since the print P passes through the leading end peeling portion and is rapidly bent, the highly rigid print P and the protective layer adhered to the print P are peeled off from the laminate film as described in detail later.

At this time, the print is not adhered to the laminated film 2 from the position of the heating roll 3 to the leading end peeling portion, and can be reused. After rewinding this unused portion, the pressure roll 5 retreats to the non-pressure position again.

FIG. 2 is a sectional view of the laminated film of the present invention. The laminate film 2 has a protective layer on the substrate 2a. The protective layer has a configuration in which at least a surface layer 2b and an adhesive layer 2c are sequentially laminated from the substrate 2a side.

As the substrate 2a, any material may be used as long as the protective layer is easily peeled off from the substrate of the laminated film when the protective layer of the laminated film 2 is adhered to the ink receiving layer of the print P. Terephthalate, polyethylene terephthalate / isophthalate copolymer,
Polyester such as polybutylene terephthalate, polyolefin such as polypropylene, polyamide, polyimide resin, triacetyl cellulose, polyvinyl chloride, vinylidene chloride-vinyl chloride copolymer resin, acrylic resin, films and sheets made of materials such as polyether sulfone, etc. Can be used. The thickness of the base material 2a is not particularly limited, but economical efficiency and "wrinkles"
The range is from 5 μm to 50 μm, and more preferably from 10 μm to 40 μm, in consideration of the difficulty of the generation of slag.

The surface of the base material 2a on which the protective layer is to be formed may be subjected to a surface roughening treatment such as embossing or sandblasting, or a surface roughening treatment using a resin layer containing powder particles. If the surface roughening treatment is not performed, after laminating the laminate film to the print, and then peeling the base film, a glossy image having a protective layer can be obtained. Is obtained.

The surface layer of the protective layer is formed by applying an emulsion composed of an aqueous suspension in which two or more polymer substances are mixed. As the polymer substance constituting the emulsion used in the present invention, an acrylic resin, a styrene resin, a vinyl chloride resin, a vinyl acetate resin, or a copolymer resin thereof is used.

The two or more polymer substances to be mixed include:
Two or more polymer substances having different glass transition temperatures (Tg) or minimum film formation temperatures (MFT) are preferable. Tg is 80
An emulsion having a polymer substance having a temperature of not lower than 30 ° C. and a polymer substance having a Tg of not higher than 30 ° C. is more preferable.

As the acrylic resin, (meth) acrylic acid ester alone or a copolymer using the same can be used. Specific examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. n
-Hexyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, and the like. These (meth) acrylic esters can be used alone or in combination. Further, monomers copolymerizable with these (meth) acrylic acid esters can be additionally polymerized and used. Examples of such monomers include (meth) acrylic acid, crotonic acid, maleic acid, and fumaric acid. Unsaturated carboxylic acids such as acid and itaconic acid; hydroxylethyl (meth) acrylate, (meth)
Monomers having a hydroxyl group such as hydroxylpropyl acrylate and hydroxylbutyl (meth) acrylate; monomers having an alkoxy group such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; (meth) acrylic Monomers having a glycidyl group such as glycidyl acid and allyl glycidyl ether; monomers having a (meth) acrylonitrile nitrile group; styrene, (meth)
Monomers having an aromatic ring such as phenyl acrylate and benzyl (meth) acrylate; monomers having an amide group such as (meth) acrylamide; monomers having an N-alkoxy group and N-methoxymethyl (meth) ) Acrylamide, N-
Monomers having an N-alkoxyalkyl group such as methoxyethyl (meth) acrylamide; monomers having an N-alkylol group such as N-methylol (meth) acrylamide and N-butyrol (meth) acrylamide; vinyl chloride , Vinyl bromide, allyl chloride,
Monomers having a group to which a halogen atom is bonded, such as 2-chloroethyl (meth) acrylate, chloromethylstyrene, and vinyl fluoride; and olefin monomers such as ethylene, propylene, and butadiene. It is also possible to partially crosslink using the reactive groups of the above-mentioned materials.

The emulsion used in the present invention can be synthesized by generally well-known techniques, and of course, commercially available materials can be used. The Tg of the resin used in the emulsion can be adjusted by changing the ratio of the monomer component and its ratio.

As the emulsion composed of a polymer substance having a higher Tg or MFT, an emulsion using a methacrylic acid ester resin having a small expansion is particularly preferable.
As an emulsion composed of a polymer material having a lower Tg or MFT, a resin containing a large amount of an acrylate monomer having a low Tg is particularly preferable. An emulsion composed of a polymer substance having a higher Tg has a Tg of 80 ° C.
One type of emulsion composed of the above resins may be used, or a plurality of emulsions composed of resins having a Tg of 80 ° C. or more may be used by blending.

The emulsion composed of a polymer having a lower Tg or MFT may be one kind of emulsion composed of a resin having a Tg of 30 ° C. or less, and in any case, it may be a Tg.
May be used by blending a plurality of emulsions composed of resins having a temperature of 30 ° C. or lower.

In the surface protective layer of the present invention, a blend of the emulsion having a relatively high Tg (HTgE) and the emulsion having a relatively low Tg (LTgE) is used. Hereinafter, unless otherwise noted, “parts” and “%” mean “parts by mass” and “% by mass”, respectively.) When the solid content of HTgE is 10 parts to 90 parts, particularly 40 parts to 80 parts, preferable. LTgE solids content is 10 to 90 parts, especially 20 to 6 parts
0 parts is preferred.

The formation of the emulsion layer is performed by applying a coating solution containing the emulsion by a roll coating method, a rod bar coating method, a spray coating method, an air knife coating method, a slot die coating method, etc., and drying. Can be. The thickness of the surface layer must be such that cracks due to stress can be prevented. On the other hand, if the thickness is too large, the performance of peeling along the periphery of the print is impaired. Therefore, the thickness of the surface layer is 1μ
m to 10 μm are preferred.

An adhesive layer is formed on the surface layer formed as described above. The adhesive layer is also obtained by applying and drying the emulsion paint, but it is required that the resin be sufficiently softened during thermocompression bonding and adapted to the printing surface. Examples of the resin used in the emulsion for the adhesive layer include an acrylic resin, a vinyl acetate resin, a vinyl chloride resin, an ethylene / vinyl acetate copolymer resin,
Examples thereof include a polyamide resin, a polyester resin, a polyurethane resin, and a polyolefin resin. Among them, an acrylic resin adhesive is particularly preferable from the viewpoint of conformity to the surface of a print and transparency of a coating film.

Acrylic monomers used in the acrylic resin adhesive include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate,
Alkyl ester monomers such as pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate and nonyl acrylate, and alkoxyalkyl acrylates such as 2-ethoxyethyl acrylate and 3-ethoxypropyl acrylate are used.

In adjusting the cohesive force of the adhesive layer, a methacrylate monomer, vinyl acetate, styrene, acrylonitrile, and (meth) acrylamide can be appropriately used as a copolymer component. As another means for adjusting the cohesion, a hydroxyl-containing monomer such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate, or a carboxyl-containing monomer such as (meth) acrylic acid is used. There is a method in which the active hydrogen is introduced and partially crosslinked with an isocyanate, a blocked isocyanate, an epoxy or the like using the active hydrogen.

In order to ensure a sharp cut of the protective layer at the end bonded to the print, an extreme increase in the molecular weight due to crosslinking is not preferred. Therefore, the crosslinkable monomer is at most 10% by mass of all monomers. % Is preferred. As another means for adjusting the cohesive force, there is a method in which crosslinking is performed using N-methylol acrylamide, N-methylol methacrylate, butoxymethyl acrylamide, or the like.

The emulsion used in the adhesive layer of the present invention can be synthesized by a generally well-known technique similarly to the case of the emulsion for the surface layer, and it is of course possible to use commercially available materials. . The Tg or MFT of the resin used in the emulsion is determined by the monomer component, but particularly in the case of an acrylic resin adhesive, it can be adjusted by changing the ratio of the monomer component and its ratio. The coating method is exactly the same as for the surface layer.

The thickness of the adhesive layer must have a thickness necessary to finally adhere sufficiently to the ink receiving layer of the recording medium and to adhere so that no air bubbles exist. For this reason, the thickness is suitably from 2 μm to 30 μm, and a particularly preferred range is from 4 μm to 20 μm. The lower limit is based on the above-mentioned reason, and the upper limit is due to a decrease in image sharpness due to an increase in the thickness of the entire protective layer and a cost reason. A release paper may be used for the adhesive layer, or a method of releasing the surface of the base material from the release paper may be used. The latter method is superior in terms of cost, and a fluorine-based resin or a silicon-based resin is used as a release agent.

Examples of the recording medium whose surface is modified by such a protective layer to provide excellent image quality include ink jet recording paper, thermal sublimation recording paper, electrophotographic recording paper, and photographs. It can be formed as follows.

Examples of the base material of the recording medium include plastic films such as polyethylene and polyethylene terephthalate (PET), and sheets made of paper materials such as high-quality paper, coated paper, and laminated paper. As the ink receiving layer applied to this surface, a water-soluble polymer emulsion such as polyvinyl alcohol, vinyl acetate, acryl, urethane and the like, a combination thereof, and a coating in which synthetic silica is further dispersed therein are applied. Can be used. As a coating method, a recording medium is obtained by using a roll coating method, a rod bar coating method, a spray coating method, a slot die coating method, etc., followed by drying after application.

As described above, according to the present invention, a protective layer free of cracks is realized, and a laminate film is hot-pressed and fixed on a print such as an inkjet print or a photograph, and then, the base material of the laminate film is peeled off. In this case, the surface layer and the adhesive layer of the laminate film can be sharply cut along the edge of the print (Problem 1).

Further, in the present invention, a laminated film on which a protective layer having high light resistance can be formed can be provided (Problem 2).

In order to achieve both the objects 1 and 2 of the present invention, an appropriate amount of an ultraviolet absorber may be contained in either the surface layer or the adhesive layer. As the ultraviolet absorber to be added, an ultraviolet absorber composed of compounds of the following systems can be used.

1) 2-hydroxyphenylbenzotriazole type 2) 2-hydroxybenzophenone type 3) 2,4-diphenyl-6- [2-hydroxyphenyl] -s-triazine type 4) salicylate type 5) cyanoacrylate type The benzene ring hydrogen of the basic skeleton is a halogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group,
It may be substituted by a substituent such as a hydroxyl group. The UV absorber used is UV-absorbing because low-molecular UV absorbers may deteriorate in performance due to volatilization or bleeding from the layer containing them, or cause the strength of the polymer film to deteriorate due to the inclusion of low-molecular materials. It is more desirable to use a polymer having a group for exhibiting the property.

In order to polymerize, it is necessary to introduce a reactive group into the benzene nucleus in the above-mentioned basic skeleton having ultraviolet absorbing properties. Typical examples thereof include a group represented by the following general formula (1).

-X-OOCC (-H or -CH ₃ ) = CH ₂ (1) A reactive monomer having a substituent introduced as shown by the formula (1) is polymerized alone, or Copolymers with other copolymerizable monomers as described in the surface layer resin in the specification can be used. In the formula (1), X represents an alkylene group or oxyalkylene group having 1 to 12 carbon atoms, or a divalent group such as —CH ₂ C (OH) CH ₂ —. With respect to the resin having such an ultraviolet absorbing group, JP-A-6-73368: On the other hand, JP-A-7-126536: JP-A-9-118720, JP-A-9-118720: IOLUB CORPORATION Japanese Patent Application Laid-Open No. 11-348199: Nippon Shokubai Co., Ltd. Japanese Patent Application Laid-Open No. 2000-44901: Otsuka Chemical Co., Ltd.

Another means for improving the light resistance of the protective layer is to add a light stabilizer. The method of addition is the same as in the case of the ultraviolet absorber. A typical material is a hindered amine-based material. High T as in the case of UV absorber
It is more desirable to use a resin emulsion in which at least one of the g resin, the low Tg resin, and the adhesive layer resin contains an appropriate amount of a monomer containing a photostable group. For example, a piperidine-based reactive light stabilizer as disclosed in the claims and examples of JP-A-11-348199 is homopolymerized, or a reactive ultraviolet absorber,
It can also be used as a copolymer resin emulsion with other copolymerizable monomers.

FIG. 3 is an enlarged cross-sectional view of a state where the leading end of the print P passes through the leading end peeling portion as viewed from the side. The direction of the base material 2a of the laminated film 2 is rapidly changed by the roll 8 having a small curvature at the exfoliation portion (FIG. 3A). At this time, the print P adhered to the adhesive layer 2c tends to separate from the substrate 2a due to its rigidity. At this time, the surface layer 2b constituting the protective layer cannot follow the deformation and breaks by shearing, and accordingly, the low Tg or low MFT adhesive layer 2c also breaks. Therefore, the resin forming the surface layer is required to have a property of brittlely breaking against deformation accompanied by a sudden shear force.

The separation of the rear end is performed by the same mechanism. The movable peeling roll 7c at the trailing end peeling section in FIG.
b, when the laminated film to which the printed matter is adhered is rapidly extruded, the rear end peeling section against the winding tension applied to the take-up reel 10 because the thermocompression bonding section exists upstream of the laminating film path. Will be moved in the direction of rewinding the entire laminated film on the downstream side. As a result, when the trailing edge of the printed material performs the trailing edge peeling operation after passing through the movable peeling roll 7c, the rigidity of the printed material and the sudden change in the pass direction at the trailing edge of the printed material protect according to the same mechanism as the leading edge peeling. The layer is destroyed, and as a result, the print is peeled off from the heat-resistant substrate 2a of the laminate film together with the protective layer.

FIG. 4 is a cross-sectional view of a state in which the printed material passes through the leading end peeling portion and both sides of the protective layer are cut, as viewed from the traveling direction of the printed material. After the leading edge separation, the print tends to advance in a direction different from the traveling direction of the laminate film due to its rigidity. This cuts both sides of the protective layer following the tip of the protective layer. In this case, the cutting mechanism cuts by pulling as shown in FIG. FIG. 4 shows a state immediately after the start of cutting both sides of the protective layer. As shown in the drawing, the print starts to separate from the base material 2a with the protective layer. At this time, since the entire protective layer has a tensile strength sufficiently smaller than the adhesive strength of the surface layer 2b to the substrate 2a, the print is cut in the vicinity of both sides. If the tensile strength is large with respect to the adhesion, the protective layer at a position distant from both sides of the print may be largely separated from the substrate 2a and then cut at a position distant from both sides of the print. As a result, extra fin-like protective layer resin may remain around the print. Therefore, it is preferable that the tensile strength of the entire resin layer forming the protective layer be smaller than the adhesion between the protective layer and the substrate.

Further, since the protective layer resin is adhered to the print by the pair of rolls, the adhesion may cause a tensile residual stress in some cases. Further, when the print is paper, it is stretched by moisture absorption, and stress is generated by pulling the protective layer on the surface. In such a case, cracks may occur on the surface of the protective layer due to these stresses. In order to prevent this, it is desirable to increase the breaking elongation in a minute section related to cracks while keeping the tensile strength of the surface layer 2b small.

FIG. 5 is a diagram showing a resin structure constituting the surface layer 2b of the protective layer. A layer is formed by mixing an emulsion of the first resin 20 having a high Tg or high MFT and the second resin 21 having a low Tg or low MFT and applying and drying the mixture on a substrate. Therefore, even after the first resin 20 and the second resin 21 have been formed, their areas are gently mixed. More precisely, the structure is such that an island of the first resin 20 for forming a film at a higher temperature is formed in the sea of the second resin 21 for forming a film at a lower temperature in the drying process. Because of its structure, the low molecular weight region simultaneously achieves ease of shearing, low tensile strength, and large breaking elongation in a minute section. Further, at this time, the temperature characteristics such as the strength and stickiness of the film surface are stable up to around Tg of the first resin 20 due to the contribution of the polymer region.

FIG. 6 shows the surface layer 2 on the substrate 2a.
b, a schematic diagram for measuring the adhesion strength of the adhesive layer 2c, in which the tension F generated on the tape when the protective layer adhered to the adhesive tape T is pulled at a constant speed V is measured. FIG. 7 is a graph plotting this against the ambient temperature at the time of measurement.
It is.

The surface layer 2b adhered to the substrate 2a is made of a resin having a Tg (Tg1) higher than the first predetermined temperature T1 and a Tg (Tg2) lower than the second predetermined temperature T2. The adhesive force is kept substantially constant between T2 and T1, and the adhesive force increases in a temperature region higher than T1 and a temperature region lower than T2. The reason for this is that, when Tg2 is exceeded, the adhesive strength of the resin having a low Tg is increased due to the increase in tackiness, and when T2 is exceeded, the adhesion is reduced due to loss of tackiness. By not getting big until you win.

In order to separate the front and rear ends of the printed matter having the protective layer thermocompressed from the substrate 2a, the protective layer surface layer 2b and the substrate 2a are separated.
It is necessary that the adhesion between them is small. Therefore, the temperature suitable for front and rear end separation is preferably between T2 and T1.

The process of separating from thermocompression ensures stable operation in the normal room temperature fluctuation range, ie, between about 10 ° C. and 30 ° C. Furthermore, the mechanism operates stably from a state immediately after the power is turned on to a state after the inside of the casing of the mechanism thermally reaches parallel. Therefore, there is preferably a difference of at least 40 ° C. between T1 and T2.

To stabilize the thermocompression bonding process at a speed of, for example, 25 mm / s, the thermocompression bonding process temperature is 160
It is desirable that the temperature is not less than ° C. At this time, the temperature of the prints coming out of the thermocompression-bonded roll pair rapidly drops, but the separation process can be stabilized by separating the front and rear ends between 30 ° C and 80 ° C. Therefore, it is more preferable that T1 is 80 ° C. or more and T2 is 30 ° C. or less.

[0050]

EXAMPLES Example 1 [1] Preparation of Laminate Film (1) Surface Layer Coating Solution (Coating Solution S1) (a) Synthesis of High Tg Resin Emulsion A stirrer and reflux condenser were placed in a first glass reaction vessel. , A thermometer and a nitrogen gas inlet tube, then Aqualon RN-30 (available from Daiichi Kogyo Seiyaku Co., Ltd.) as a nonionic emulsifier
6 g, anionic emulsifier Aqualon HS-30 (Daiichi Kogyo Seiyaku Co., Ltd.) 6 g, methyl methacrylate 11
9.0 g, 22.3 g of ethyl acrylate, 7.4 g of methacrylic acid, and 156 g of water were added and stirred, and the total amount was 316.7 g.
Was prepared. Next, 36 g of this mixture was taken out, transferred to the same second reaction vessel, and emulsified at 73 ° C. for 40 minutes under nitrogen gas introduction. Next, 17 g of ammonium peroxodisulfate as a polymerization initiator was dissolved in 36 g of water and added to the emulsion. Thereafter, the remaining amount of the mixture was taken out of the first reaction vessel, and gradually dropped into the second reaction vessel over 100 minutes, and polymerization was carried out at 73 ° C. After dropping the remaining amount of the mixture, stirring was continued at 73 ° C. for 80 minutes to obtain a high Tg resin emulsion (Tg: 82 ° C.,
(Resin solid content: 47.0%). The average particle size of the dispersed particles was 80 nm.

(B) Synthesis of Low Tg Resin Emulsion Ethyl acrylate 74.4 g, methyl methacrylate 2
9.8 g, 2-hydroxyethyl methacrylate
2g and 7.4g of methacrylic acid, and the other conditions were the same as in the synthesis of the high Tg resin emulsion, and the low Tg resin emulsion (Tg: 27 ° C, resin solid content 47.0)
%). The average particle size of the dispersed particles is 87 n.
m.

(C) Preparation of Surface Layer Coating Solution The above-mentioned high Tg resin emulsion (Tg: 82 ° C.) was mixed with 60 parts by mass (solid content) of the above-mentioned low Tg resin emulsion (Tg).
g: 27 ° C.) 40 parts by mass (solid content) and water were added and mixed and stirred to prepare a coating liquid S1 having a total solid content of 40%.

(2) Adhesive Layer Coating Solution (Coating Solution A1) (a) Synthesis of Adhesive Resin Emulsion As a polymer material constituting the emulsion, 111.6 g of ethyl acrylate, 14.9 g of methyl methacrylate, 2-hydroxyethyl methacrylate 1
Synthesis of adhesive layer resin emulsion (Tg: 1 ° C, solid content: 47.0%) using 4.9 g and 7.4 g of methacrylic acid, and otherwise using exactly the same as the synthesis of the high Tg resin emulsion of the surface coating liquid. Was done. The average particle size of the dispersed particles was 100 nm.

(B) Preparation of Coating Solution for Adhesive Layer Water was added to the adhesive resin emulsion and stirred to prepare a coating solution A1 having a solid content of 40%.

(3) Preparation of Laminate Film A coating liquid S1 was applied to a 38 μm-thick PET film by a slot die coating method so as to have a dry film thickness of 5 μm. The coating liquid A1 was applied thereon and dried so as to have a dry film thickness of 8 μm to form a laminate film.

[2] Preparation of Ink-Jet Receiving Paper and Printed Material To 160 parts by mass of synthetic silica (trade name: Fine Seal X60) manufactured by Tokuyama Corporation, an emulsion (trade name manufactured by Takamatsu Yushi Co., Ltd.) was used as a binder. Name: NS-120X
K) 100 parts by mass were mixed and dispersed to prepare a coating liquid having a solid content of 18%, and the coating liquid was dried on a high-quality paper of 186 g / m ² with a slot die coater so that the coating film thickness after drying was 50 μm. I let it. The printer H-10 manufactured by Canon Inc. is applied to the A4 size inkjet image receiving paper thus produced.
0 was used to form an image.

[3] Lamination of Printed Object Using Apparatus of FIG. 1 and Characteristic Evaluation The laminated film produced as described above was laminated on the ink-jet printed object from the protective layer side, and the diameter was 80 mm.
mm from the base film side of the laminate film with a steel roll of 50 mm, and 50 mm in diameter from the receiving paper side
With a rubber roll. At this time, the nip weight is 12
0N, and the feed speed was 25 mm / sec. Thus, a print having the protective layer laminated thereon was prepared. The cutability of the cut protective layer was examined, and the resulting print was inspected for 6
2 hours at 0 ° C (condition 1), 1 at 30 ° C and 90% RH
The specimen was allowed to stand for a week (condition 2), and an acceleration test for cracking of the surface layer was performed. Table 1 shows the evaluation results.

Example 2 [1] Preparation of Laminate Film (1) Surface Layer Coating Solution (Coating Solution S2) (a) Synthesis of High Tg Resin Emulsion Methyl methacrylate was used as a material of a polymer material constituting an emulsion. 133.9 g, 7.4 g of ethyl acrylate and 7.4 g of methacrylic acid were used, and the other conditions were exactly the same as the high Tg resin emulsion of Example 1 (Tg: 100 ° C., solid content: 47.
0%). The average particle size of the dispersed particles is 96
nm.

(B) Synthesis of Low Tg Resin Emulsion As a polymer material constituting the emulsion, 29.8 g of methyl methacrylate and 9 acrylate of ethyl acrylate were used.
Example 1 used 6.7 g, 7.4 g of methacrylic acid, and 14.9 g of 2-hydroxyethyl methacrylate.
Low Tg just like high Tg resin emulsion of
Resin emulsion (Tg: 11 ° C, solid content 47.0%)
Was synthesized. The average particle size of the dispersed particles is 105 nm.
Met.

(C) Preparation of Coating Solution for Surface Layer The above high Tg resin emulsion (Tg: 100 ° C.)
Parts by mass (solid content) and the low Tg resin emulsion (T
g: 11 ° C) 50 parts by mass (solid content) and water were added and mixed and stirred to prepare a coating liquid S2 having a total solid content of 40%.

(2) Adhesive Layer Coating Solution (Coating Solution A2) (a) Preparation of Adhesive Layer Resin Emulsion As a polymer material constituting the emulsion, 119.0 g of ethyl acrylate, 7.4 g of propyl acrylate, methyl Using 22.3 g of methacrylate,
Other than that, the adhesive layer resin emulsion (Tg: -1) was exactly the same as the synthesis of the high Tg resin emulsion of Example 1.
(1 ° C., solid content: 47.0%). The average particle size of the dispersed particles was 87 nm.

(B) Preparation of Adhesive Layer Coating Solution Water was added to the adhesive layer resin emulsion, followed by stirring to prepare an adhesive layer coating solution A2 having a solid content of 40%.

(3) Preparation of Laminated Film A coating liquid S2 was applied to a 38 μm-thick PET film by a slot die coating method so as to have a dry film thickness of 7 μm. The coating liquid A2 was dried thereon to a dry film thickness of 12 μm.
And dried to prepare a laminated film.

[2] Preparation of Inkjet Image-Receiving Paper and Printed Material After forming an inkjet image-receiving layer on 210 g of high-quality paper in exactly the same manner as in Example 1, a printed material was prepared.

[3] Lamination of Printed Material and Evaluation of Characteristics Laminating treatment and evaluation of characteristics were performed in the same manner as in Example 1 using the above-described ink-jet image-receiving paper and the above-described laminated film. Table 1 shows the evaluation results.

Comparative Example 1 After a solution polymerization of a high Tg resin and a low Tg resin having the same monomer composition as in Example 1, respectively, a coating solution having the same solid content ratio as in Example 1 was prepared. A surface layer having the same thickness was formed on the material. The same aqueous emulsion adhesive coating solution A1 as in Example 1 was applied thereon, and dried to form an adhesive layer having the same film thickness, thereby obtaining a laminate film.

A printed matter was formed on the same ink-jet image-receiving paper as in Example 1 in the same manner as in Example 1, and the printed material and the above-mentioned laminated film were subjected to laminating treatment and property evaluation in the same manner as in Example 1. went. Table 1 shows the evaluation results.
It was shown to.

Comparative Example 2 After a solution polymerization of a high Tg resin and a low Tg resin having the same monomer composition as in Example 2, respectively, a coating liquid having the same solid content ratio as in Example 2 was prepared. A surface layer having the same thickness was formed on the material. The same aqueous emulsion adhesive coating liquid A2 as in Example 2 was applied thereon, and dried to form an adhesive layer having the same film thickness, thereby obtaining a laminate film.

A printed matter was formed on the same ink-jet image-receiving paper as in Example 2 in the same manner as in Example 2, and the printed matter and the above-mentioned laminated film were subjected to laminating treatment and property evaluation in the same manner as in Example 1. went. Table 1 shows the evaluation results.
It was shown to.

[0070]

[Table 1]

Example 3 Coating liquid 1: high Tg emulsion manufactured by JSR Corporation
Acrylic emulsion T371 (Tg = 85 ° C.) 60 parts by mass (solid content), Nissin Chemical Co., Ltd. acrylic emulsion 2706 (Tg = 14) as a low Tg emulsion
C) and 40 parts by mass (solid content).
Adjusted to 8%. Coating liquid 2: Acrylic emulsion 2 manufactured by Nissin Chemical Co., Ltd.
706 (Tg = 14 ° C., solid content ratio 40%). Substrate: 38 μm-thick PET film First, a coating liquid 1 was applied and dried by a slot die coating method so as to have a dry film thickness of 5 μm.
Was applied and dried so as to have a dry film thickness of 8 μm to obtain a laminate film.

Example 4 Coating liquid 3: High Tg emulsion manufactured by JSR Corporation
60 parts by mass (solid content) of an acrylic emulsion T371 (Tg = 85 ° C.) and BASF as a low Tg emulsion
UVA-3, an emulsion type polymer ultraviolet absorber manufactured by Co., Ltd.
40 parts by mass (solid content) of 83 MG (Tg = 27 ° C., a self-crosslinking emulsion containing 30% of a benzophenone ultraviolet absorbing monomer) were mixed and dispersed to adjust the solid content ratio to 32%. Coating liquid 2: Acrylic emulsion 2 manufactured by Nissin Chemical Co., Ltd.
706 (Tg = 14 ° C., solid content ratio 40%). Substrate: PET film having a thickness of 38 μm First, coating liquid 3 was applied by a slot die coating method so as to have a dry film thickness of 5 μm, and then dried.
Was applied and dried so as to have a dry film thickness of 8 μm to obtain a laminate film.

Example 5 Coating liquid 4: High Tg emulsion manufactured by JSR Corporation
A copolymer emulsion EUV-601 containing 60 parts by mass (solid content) of an acrylic emulsion T371 (Tg = 85 ° C.) and a monomer having an ultraviolet light stable group manufactured by Nippon Shokubai Co., Ltd.
(Tg = 10 ° C.) and 40 parts by mass (solid content) were mixed and dispersed to adjust the solid content ratio to 37%. Coating liquid 2: Acrylic emulsion 2 manufactured by Nissin Chemical Co., Ltd.
706 (Tg = 14 ° C., solid content ratio 40%). Substrate: 38 μm thick PET film First, coating liquid 4 was applied and dried by slot die coating method so as to have a dry film thickness of 5 μm.
Was applied and dried so as to have a dry film thickness of 8 μm to obtain a laminate film.

Example 6 Coating liquid 5: High Tg emulsion manufactured by JSR Corporation
Acrylic emulsion T371 (Tg = 80 ° C or higher) 3
0 parts by mass (solid content) and an emulsion UV absorber manufactured by Sharp Yushi Kogyo Co., Ltd. (an acrylic resin emulsion containing a monomer having a benzotriazole UV absorber, and a monomer having a UV absorber 50%) UL
30 mass parts (solid content) of S-1635MH (Tg = 85 ° C.) and a low Tg emulsion manufactured by Nissin Chemical Co., Ltd.
40 parts by mass (solid content) of an acrylic emulsion 2706 (Tg = 14 ° C.) were mixed and dispersed to adjust the solid content ratio to 36%. Coating liquid 2: Acrylic emulsion 2 manufactured by Nissin Chemical Co., Ltd.
706 (Tg = 14 ° C., solid content ratio 40%). Substrate: 38 μm-thick PET film First, coating liquid 5 was applied by a slot die coating method so as to have a dry film thickness of 5 μm, and then coated with coating liquid 2.
Was applied and dried so as to have a dry film thickness of 8 μm to obtain a laminate film.

Example 7 Coating liquid 6: High Tg emulsion manufactured by JSR Corporation
30 parts by mass (solid content) of an acrylic emulsion T371 (Tg = 85 ° C.) and ULS-635MH, an emulsion-based ultraviolet absorber manufactured by YAS Co., Ltd. (Tg = 80)
30 ° C., 30 parts by mass of an acrylic resin emulsion containing a monomer having a benzophenone-based ultraviolet absorbing group, containing 50% of a monomer having an ultraviolet absorbing group, and an acrylic emulsion 2706 (Tg = 14 ° C) 40
Parts by mass were mixed and dispersed to adjust the solid content ratio to 36%. Coating liquid 2: Acrylic emulsion 2 manufactured by Nissin Chemical Co., Ltd.
706 (Tg = 14 ° C., solid content ratio 40%). Substrate: PET film having a thickness of 38 μm First, coating liquid 6 was applied by a slot die coating method so as to have a dry film thickness of 5 μm, and then dried.
Was applied and dried so as to have a dry film thickness of 8 μm to obtain a laminate film.

Example 8 Coating liquid 1: High Tg emulsion manufactured by JSR Corporation
Acrylic emulsion T371 (Tg = 85 ° C) 60
Parts by mass (solid content) and an acrylic emulsion 2706 (Tg = 1) manufactured by Nissin Chemical Co., Ltd. as a low Tg emulsion.
(4 ° C.) and 40 parts (solid content).
%.

Coating liquid 7: 70 parts by mass (solid content) of acrylic emulsion 2706 (Tg = 14 ° C.) manufactured by Nissin Chemical Co., Ltd. and 30 parts by mass (solid content) of UVA-383MG manufactured by BASF Corporation The solid content ratio was adjusted to 37%. Substrate: 38 μm thick PET film First, coating liquid 1 was applied and dried by a slot die coating method so as to have a dry film thickness of 5 μm.
Was applied and dried so as to have a dry film thickness of 8 μm to obtain a laminate film.

Comparative Example 3 Coating liquid 8: Polymer UV absorber PU manufactured by Otsuka Chemical Co., Ltd.
VA 30M (Tg = 90 ° C., a 30% toluene solution of an acrylic resin containing a monomer having a benzotriazole-based UV-absorbing group, 30% of the monomer having a UV-absorbing group is dissolved in toluene) Then, the solid content ratio was adjusted to 25%.

Coating liquid 2: Acrylic emulsion 2706 manufactured by Nissin Chemical Co., Ltd. (Tg = 14 ° C., solid content ratio 40)
%). Substrate: 38 μm-thick PET film First, coating liquid 8 was applied and dried by a slot die coating method so as to have a dry film thickness of 5 μm.
Was applied and dried so as to have a dry film thickness of 8 μm to obtain a laminate film.

Comparative Example 4 Coating solution 9: PVC vinegar bi-emulsion 6 manufactured by Nissin Chemical Co., Ltd.
02 (MFT = 130 ° C., solid content ratio 48%). Coating liquid 2: Acrylic emulsion 2 manufactured by Nissin Chemical Co., Ltd.
706 (Tg = 14 ° C., solid content ratio 40%). Substrate: PET film having a thickness of 38 μm First, a coating liquid 9 was applied and dried by a slot die coating method so as to have a dry film thickness of 5 μm.
Was applied and dried so as to have a dry film thickness of 8 μm to obtain a laminate film.

On the same ink-jet image-receiving paper as in Example 1,
A plurality of prints were prepared in the same manner as in Example 1. Then, these prints and Examples 3 to 8 and Comparative Examples 3 and 4
Laminating treatment and property evaluation were performed in the same manner as in Example 1 using the laminated film of Example 1.

As a result, in Examples 3 to 8, the protective layer was cut cleanly around the print, and the protective layer did not protrude from the edge of the print. Further, no cracks occurred on the surface of the protective layer even after being left in the environment. In the examples, a resin component blended with a UV absorber is an Atlas fade meter 1
After exposure for 00 hours, a sufficient ultraviolet ray cut function with a concentration reduction of less than 30% was exhibited.

In Comparative Example 3, the protective layer was cut cleanly at both ends in the direction of travel of the print, but the protective layer was not cut at the front and rear ends in the direction of travel of the print. Furthermore,
Cracks occurred on the surface of the protective layer after leaving the environment under the conditions 1 and 2.

In Comparative Example 4, the protective layer was cut cleanly at the front and rear ends in the traveling direction of the print, but the protective layers were not cut cleanly at both ends in the traveling direction, and both sides of the print were removed. In this case, a large protective layer overhang occurred. No cracks were observed in the protective layer after leaving the environment under the conditions 1 and 2.

[0085]

According to the present invention, after the protective layer formed on the substrate is transferred to the surface of the print by thermocompression bonding, the print with the protective layer is peeled off from the substrate. It is cut neatly along the peripheral edge of the object. Further, even if the print having the protective layer formed thereon is left in a high-temperature and high-humidity environment, the protective layer does not crack. Further, by incorporating an ultraviolet absorber into this protective layer, sufficient light resistance can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing an example of a laminating apparatus using a laminated film of the present invention.

FIG. 2 is a cross-sectional view showing an example of the laminate film of the present invention.

FIG. 3 is a partial view of a leading end peeling portion showing a mechanism for cutting a protective layer of the laminate film of the present invention.

FIG. 4 is a partial view showing a mechanism for cutting a protective layer of the laminate film of the present invention.

FIG. 5 is a partially enlarged view showing a surface layer of the laminate film of the present invention.

FIG. 6 is a partial view showing a method for measuring the adhesion strength between the protective layer of the laminate film of the present invention and a laminate film substrate.

FIG. 7 is a graph showing the ambient temperature of the adhesion strength between the protective layer of the laminate film of the present invention and the laminate film substrate.

[Explanation of symbols]

 1: Roll unwinding reel 2: Laminated film 2a: Heat-resistant substrate 2b: Surface layer 2c: Adhesive layer 3: Heating roll 4: Rotary encoder 5: Pressure roll 6: Cooling fans 7a, 7b: Rear end peeling mechanism 7c: movable peeling roll at the trailing end peeling section 8: guide at the leading end peeling section 10: take-up reel 11: guide for printed matter P 12: photo interrupter 13: photo interrupter P: printed matter V: tension of protective layer Speed F: tension when the protective layer is pulled

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 201/00 C09D 201/00 (72) Inventor Kenji Suzuki 3-30-2 Shimomaruko, Ota-ku, Tokyo, Japan Inside Non-corporation (72) Inventor Yoshinari Yasui 148-1, Kadawabashi, Ebina-shi, Kanagawa Prefecture In-house lab (72) Inventor Hiroshi Ochiai 148-1 Kadzawabashi, Ebina-shi, Kanagawa In-house lab F-term (reference) 4F100 AK01C AK25B AK25C AK25K AK42A AL05C AR00B AT00A BA03 BA07 BA10A BA10B CA07C GB71 GB90 JA05C JL00 JL01 JL11B JM01C YY00C 4J004 AA07 AA09 AA10 AA14 AA15 A0201 CC02 CA01 CD02 NA17

Claims (9)

[Claims] 1. A laminate film comprising at least a surface layer and an adhesive layer laminated on a base material, wherein the surface layer is formed by applying a paint obtained by mixing at least two or more types of emulsions. . 2. The laminate film according to claim 1, wherein the two or more types of emulsions are two or more types of emulsions having different glass transition temperatures. 3. The laminate film according to claim 1, wherein the paint contains two or more emulsions having glass transition temperatures different by 40 ° C. or more. 4. The laminated film according to claim 3, wherein the two or more types of emulsions are composed of an emulsion having a glass transition temperature of 80 ° C. or higher and an emulsion having a glass transition temperature of 30 ° C. or lower. 5. The laminate film according to claim 2, wherein the solid content of the emulsion having a relatively high glass transition temperature is 10 to 90% by mass based on the solid content of the whole emulsion. 6. The laminate film according to claim 1, wherein the surface layer has an ultraviolet absorbing property. 7. The laminate film according to claim 1, wherein the adhesive layer has an ultraviolet absorbing property. 8. A step of using the laminate film according to claim 2 to pressure-bond the laminate film and the print at a temperature equal to or higher than the glass transition temperature of an emulsion having a relatively high glass transition temperature, and thereafter, A step of separating a laminate film and the printed matter. 9. An emulsion glass having a relatively high glass transition temperature, wherein the temperature at which the laminate film and the print are separated is equal to or higher than the glass transition temperature of an emulsion having a relatively low glass transition temperature. 9. The method according to claim 8, wherein the temperature is lower than the transition temperature.