JPH04142933A - Receptive sheet for printing - Google Patents

Abstract

PURPOSE:To obtain a receptive sheet for printing which has excellent ink stickiness, printability, water-proofing and anti-solvent properties and superb thermal size stability, whiteness, softness and pliability in a coating layer by applying the coating layer consisting mainly of poly(metha) acrylic acid ester copolymer containing a reactive monomer, at least, on one side of polyester film. CONSTITUTION:This receptive sheet for printing consists of a coating layer based on poly(metha) acrylic acid ester copolymer containing a reactive monomer, applied at least, to one side of polyester film. The poly(metha) acrylic acid ester copolymer is a poly(metha) acrylic acid ester copolymer containing a reactive monomer. The reactive monomer is compound containing a functional group, for example, a carboxylic group (e.g. (metha)acrylic acid, etc.). When this sheet is printed, for example, with a bar code, white concealing pigment of inorganic or organic pigment which makes the coating layer appear white is added to the coating layer. Further it is recommended that a cross-linking binder be added to the coating layer to improve the stickiness, water-proofing and anti-chemical properties and heat resistance of the coating layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a receiving sheet for printing. Specifically, the present invention relates to a printing receiving sheet having a coating layer with excellent printability, ink adhesion, water resistance, and solvent resistance, as well as excellent whiteness and cushioning properties.

[Prior art] Paper supports have traditionally been the dominant material for printing receiving sheets, but in recent years, plastic films have been used, and among them, polyester films, which have excellent properties such as mechanical properties and transparency, have become popular. It is becoming popular. However, polyester film surfaces generally have high cohesiveness and poor adhesion, so when performing various printing treatments on the surface, in order to ensure strong ink adhesion, it is necessary to use materials with excellent ink affinity. Forming a coating layer with a high temperature is widely practiced. As such a printing receiving sheet, a printing receiving sheet in which a water-based polymer resin containing a white pigment is coated on the surface of a polyester film, for example,
-82085 publication etc. are known.

However, in such printing receiving sheets, the coating layer has poor water resistance and hot water resistance, so the coating layer may undergo deformation such as dissolution or swelling in a high temperature or high humidity atmosphere, or may be susceptible to hot water treatment. The adhesion strength of the equal coating layer is significantly reduced. Furthermore, when printing with an ink containing an organic solvent, the solvent resistance is poor, so in some cases, the coating around the print may partially dissolve, making the print unclear or the coating layer becoming cloudy.

Furthermore, it has been pointed out that polyester films conventionally used for this purpose have poor thermal dimensional stability, are inferior in softness, flexibility, and whiteness compared to paper, and have a high specific gravity. A support film for printing receiving sheets that satisfies all of these characteristics has not been obtained.

[Problems to be Solved by the Invention] Therefore, an object of the present invention is to eliminate the drawbacks of these conventional techniques, and to provide a coating layer with excellent ink adhesion, printability, water resistance, and solvent resistance, and with thermal dimensional stability. whiteness, softness,
It is an object of the present invention to provide a receiving sheet for printing which also has excellent flexibility.

[Means for Solving the Problems] The present invention provides at least one side of a polyester film,
The gist of the present invention is a receiving sheet for printing characterized in that it is coated with a coating layer mainly composed of a poly(meth)acrylate copolymer containing a reactive monomer.

The polyester used in the present invention refers to well-known polyesters, specifically, for example, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, bis-α,β(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, adipine Polyester obtained by polycondensing at least one difunctional carboxylic acid such as acid/sebacic acid and at least one glycol such as ethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, etc. can be mentioned. In addition, the polyester may be blended or copolymerized with other polymers within a range that does not impede the purpose of the present invention, and may contain antioxidants, heat stabilizers, lubricants, pigments, ultraviolet absorbers, etc. It may be

The intrinsic viscosity of polyester (measured in orthochlorophenol at 25°C) is 0. 4 to 2.0, preferably 0
．． A value in the range of 5 to 1.0 is usually used.

The present invention includes polyesters such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-α, β-bis(2-chlorophenoxy)ethane-
Particularly excellent effects are obtained when 4,4'-dicarboxylate is used.

The coating layer of the present invention refers to poly(
This layer is made of a composition whose main component is a meth)acrylic acid ester copolymer. In the present invention, the main component layer is 50% by weight or more, preferably 6% by weight of the coating layer.
This refers to the amount of 0% by weight or more, and other substances may be added as appropriate. The resin to be added is not particularly limited, but typical examples include various resins such as urethane resin, polyester resin, vinyl resin, and styrene resin.
iJ Noh. In the present invention, such a coating layer is provided on at least one side of the Plus Deck film, but if it is provided on both sides, the following description of the coating layer applies to at least one/i. It is something that

The poly(meth)acrylic ester copolymer referred to in the present invention is a poly(meth)acrylic ester copolymer containing a reactive monomer. Such reactive monomers include functional groups such as carboxyl groups (for example, (meth)acrylic acid, etc.), hydroxyl groups (such as 2-hydroxyethyl (meth)acrylate), and amide groups ((meth)acrylic acid amide, etc.). etc.), glycidyl groups ((meth)acnolate glycidyl group, etc.), amino groups ((meth)acrylic acid 2-diethylaminoedyl group, etc.), and the like.

T of the poly(meth)acrylic acid ester copolymer of the present invention
Regarding g (glass transition temperature), the following formula, [where WA+,
WA2,...WAη, WIl+, WB2
,...WB-1 indicates the weight fraction of poly(meth)acrylic acid esters (A) and (B), and to Tg,
To rg8..., TgAη.

Tg L, Tg 82..., Tg B72
is poly(meth)acrylic acid ester (8),
(Tg of []) is expressed in absolute temperature] The T value is 30 to 1oo'c, more preferably 4
The temperature is preferably 0 to 90°C. If it is lower than this range, the blocking property will be poor, while if it is higher than this range, the adhesion will be poor, which is not preferable.

In the present invention, when used as a receiving sheet for printing, if the sheet is transparent, it may be difficult to confirm the resolution and clarity of printing, the printing location, etc., for example, when printing a bar code. In this case, it is preferable that the coating layer contains a white hidden pigment.

The white hidden pigment in the present invention is an inorganic or organic pigment that makes the coating layer appear white.
For example, zinc carbonate, zinc oxide, zinc sulfide, talc, kaolin, heavy/light or synthetic calsilyl carbonate 11, titanium oxide, silica, lithium fluoride, calcium fluoride, barium sulfate, alumina, zirconia, calcium phosphate, natural Alternatively, synthetic swelling or non-swelling mica may be used. Examples of organic pigments include polystyrene, polymethylstyrene, polymethoxystyrene, polyvinyl oxide, polyethylene, polypropylene, polyvinylidene chloride, polymethacrylate-1, etc. Examples include polymethyl methacrylate-1., polychloroacryle-1., etc., and at least one selected from these may be used, but is not particularly limited. Further, the pigment may be in a hollow porous state or a non-hollow porous state.

Furthermore, the pigment may be subjected to a treatment such as adding a functional group such as a glycidyl group or a methylol group to the surface in order to improve its dispersibility in a resin.

Further, the amount of the white hidden pigment added is preferably 0.1 to 70% by weight, more preferably 5 to 50% by weight. Added amount is 0
．． If it is less than 1% by weight, the white hiding property will be insufficient, and 70
If the amount exceeds 2% by weight, the adhesion between the coating layer and the base material tends to decrease.

In the present invention, it is preferable that the coating layer contains a crosslinking agent in order to further improve the adhesion, water resistance, chemical resistance, heat resistance, etc. of the coating layer.

The crosslinking agent used in the present invention is not particularly limited as long as it is a crosslinking agent that undergoes a crosslinking reaction with the above-mentioned reactive monomer and ultimately forms a coating layer having a three-dimensional network structure. , amino resin, epoxy resin, melamine resin,
It is appropriately selected from isocyanates and the like. Furthermore, additives such as crosslinking accelerators may be added.

The crosslinking agent may be used alone, or in some cases, two or more types may be used in combination. The amount of the crosslinking agent to be added is appropriately selected depending on the type of crosslinking agent, but usually the solid content of the poly(meth)acrylic acid ester copolymer containing the reactive monomer is 1-00.
It is preferably 0°OJ- to 50 parts by weight based on parts by weight,
More preferably 0.1 to 30 parts by weight. Addition amount is 0.01
If it is less than 50 parts by weight, the crosslinking effect will be low, and if it exceeds 50 parts by weight, the adhesion of the coating layer will be reduced, and furthermore, the coating properties will be deteriorated, making it difficult to form a uniform layer. In addition, as a crosslinking accelerator,
Known substances such as salts, inorganic substances, organic substances, acid substances, and alkaline substances can be used. The amount of the crosslinking accelerator to be added is 0.001 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the solid content of the poly(meth)acrylate copolymer containing the reactive monomer. It is 5 parts by weight.

Poly(meth)acrylic acid ester copolymers containing reactive monomers with a crosslinking agent added are crosslinked by heating, ultraviolet rays, electron beams, etc. after being applied to a substrate, but heating is usually the most common method. be.

The thickness of the polyester film constituting the printing receiving sheet of the present invention is not particularly limited, but is preferably in the range of 1 to 500 μm, more preferably in the range of 5 to 300 μm, and is excellent in practical handling as a base material. .

The laminated thickness of the coating layer constituting the printing receiving sheet of the present invention is not particularly limited, but is between 0°1 and 50 μm.
m is preferable, and one in the range of 0.5 to 20 μm is desirable from the viewpoints of uniform formation of the coating layer, adhesion, etc. Furthermore, the coating layer may contain known additives, such as antifoaming agents, coating properties improvers, thickeners, antistatic agents, antioxidants, and ultraviolet absorbers, as long as they do not impair the effects of the present invention. , a dye, a whitening agent, etc., or fine particles made of an inorganic or organic compound as a lubricant.

In the present invention, it is more preferable that the polyester film has a heat shrinkage rate of less than 2% at 150°C and a specific gravity of 0.95 or less.

In the present invention, the specific gravity of the polyester film is 0.9
5 or less, preferably 0.90 or less, more preferably 0
．． 80 or less. This is because if it is larger than 0.95, the film will not have a soft feel and flexibility.

Flexibility is necessary, for example, in order to be able to transfer images clearly even when the compression of a thermal recording head is reduced when used as a receiving paper for a video printer or the like. Of course, the feel of the product in your hand is also a significant factor.

For this reason, as will be described later, it is desirable that the cushioning ratio be 10% or more.

In the present invention, the polyester film has a heat shrinkage rate of less than 2%, preferably less than 1%, at 150°C in both the longitudinal and width directions. When the thermal shrinkage rate is 2% or more, the thermal dimensional stability of the film deteriorates, and the film becomes easily deformed during heat-applying processes such as thermal transfer, printing, and drying.

In particular, the heat shrinkage rate at 150°C is often important.

The incompatible polymer used in the present invention is poly-3-
Methylbutene-1, poly-4-methylpentene-1, polyvinyl-1-butane, 1.4-trans-poly2.3-
Dimethylbutadiene, polyvinylcyclohexane, polystyrene, polymethylstyrene, polydimethylstyrene, polyfluorostyrene, poly-2-methyl-4-fluorostyrene, polyvinyl 1-butyl ether, cellulose triacetate, cellulose tripropionate,
Examples include polymers having a melting point of 150° C. or higher selected from polyvinyl fluoride, polychlorotrifluoroethylene, polypropylene, and the like. In the case of the present invention, poly-4-methylpentene-1, cellulose triacetate, and modified products thereof are particularly preferred from the viewpoint of cost, thermal stability, dispersibility with polyester, and the like. Of course, the melting point of the incompatible polymer is 150°C or higher, preferably 200°C or higher, and more preferably 220°C or higher. Melting point is 150℃
If it is less than 200°C, the dispersion shape of the incompatible polymer in the polyester film will not be spherical, but will often take a layered, flat shape, and a polyester film with high cushioning properties will not be obtained, which is preferable. do not have.

Further, the melting point of the incompatible polymer is preferably 300°C or lower, preferably 280°C or lower, and more preferably 260°C or lower. This is because the incompatible polymer will not dissolve unless it is below the melt extrusion temperature of the polyester.

The amount of the incompatible polymer added is preferably 3 to 3.
0% by weight, more preferably 5 to 20% by weight. If the amount added is less than 3% by weight, not only will it be difficult to obtain a wood-based polyester film with a specific gravity of 0.95 or less, but also a white polyester film with a whiteness of 80% or more will not be obtained. It is difficult to obtain a polyester film having excellent cushioning properties with a high cushioning ratio of 1-0% or more. On the other hand, if the amount of the incompatible polymer added exceeds 30% by weight, not only the mechanical properties of the polyester film of the present invention will be inferior, but also the thermal dimensional stability will be poor, and the heat shrinkage rate at 150 ° C. Problems arise such as the increase in the amount of 5% or more.

Next, the specific gravity lowering agent used in the present invention is a compound that is added to polyester and has the effect of lowering the specific gravity, and only certain compounds have this effect. for example,
Polyalkylene glycols such as polyethylene glycol, di-polyethylene glycol, polytetramethylene glycol, and polypropylene glycol, ethylene oxide/propylene oxide copolymers, as well as sodium dodecylbenzenesulfonate, alkylsulfonate sodium salt, and glycerin monostearate. ,
Representative examples include tetrabutylphosphonium para-aminobenzenesulfone-1.

In the case of the present invention, polyethylene glycol is particularly preferred. By adding a specific gravity lowering agent, the specific gravity of the polyester film can be reduced by 0.1 g/cc or more. Furthermore, the addition of this specific gravity lowering agent not only improves the whiteness of the polyester film and smoothes the surface, but also improves the opening resistance and greatly improves the stretchability of the polyester. There is also.

The amount of the specific gravity lowering agent added in the present invention is preferably 0. It is 1 to 5% by weight, more preferably 0.5 to 3% by weight. If the amount added is less than 0.1% by weight, the specific gravity of the polyester film will not be lowered, the film will not be soft, and the specific gravity of the polyester film will be less than 0.95. On the other hand, if the amount added exceeds 5% by weight, not only will the effect of lowering the specific gravity not be recognized, but the whiteness of the film will decrease and the b value will become a large positive value.

Next, in the present invention, it is preferable that the incompatible polymer has a nearly spherical shape in the polyester film, that is, the shape factor is in the range of 1-4. Significant differences arise in the film properties obtained depending on the shape of the incompatible polymer in the polyester film, particularly in the correlation between the film's specific gravity and cushioning ratio, thermal dimensional stability, surface roughness, whiteness, etc. In other words, when the shape of the incompatible polymer is close to spherical, it is not only possible to lower the specific gravity compared to when it is dispersed in layers, but also to obtain a film with high whiteness, high cushioning rate, and good thermal dimensional stability. can. Dispersing the polymer in a nearly spherical shape means that the shape of the polymer depends on the viscosity of the incompatible polymer added to the polyester,
Compatibility parameters, melting point, and even the type of specific gravity lowering agent,
It strongly depends on the amount added. A shape close to a spherical shape refers to a case where the shape factor of the incompatible polymer dispersed in the film, that is, the ratio of the major axis to the minor axis is 1 to 4, preferably 1 to 2.

The cushioning ratio of the polyester film in the present invention is preferably 10% or more, more preferably 15% or more. If the cushioning ratio is less than 10%, for example, when used as a receiving paper for a video printer, it will not be possible to transfer a clear image when the pressure of the thermal recording head is lowered, and it will not be possible to transfer a clear image when touched with the hand. It feels worse.

The whiteness of the polyester film in the present invention is preferably 80% or more, more preferably 90% or more.

Further, the color tone value determined by a color difference meter is preferably 13 or less, more preferably 14 or less - 20 or more. The smaller the b value, the better the apparent whiteness of the film, giving it a high-quality image.

Although the color tone changes by adding the above-mentioned incompatible polymer, specific gravity lowering agent, etc., a fluorescent whitening agent may be added if necessary. As an optical brightener, the product name “UBITEC°”OT is used.
3. Examples include MD (manufactured by Ciba Geigy) and "0B-1" (manufactured by Eastman).

The optical density of the polyester film 1\ in the present invention is
Preferably 0. It is 7 or more and 1.6 or less, more preferably 0.8 or more and 1.6 or less. If the optical density is less than 0.7, the masking properties of the fill 11 will be insufficient and the back side will be transparent, which is not preferable. On the other hand, if the optical density exceeds 1.6, a large amount of microbubbles must be included, which is undesirable because the film strength becomes weak.

The polyester film of the present invention contains calcium carbonate,
Amorphous zeolite particles, anatase titanium dioxide,
Fine particles of calcium phosphate, silica, kaolin, talc, clay, etc. may be used in combination. The amount of these added is 0.005 to 25 parts by weight per 1.00 parts by weight of the polyester composition.
Preferably, it is expressed in parts by weight. In addition to such fine particles, fine particles precipitated by a reaction between a catalyst residue and a phosphorus compound in a polyester polycondensation reaction system can also be used. Examples of the precipitated fine particles include those made of calcium, lithium and phosphorus compounds, or those made of calcium, magnesium and phosphorus compounds. The content of these particles in the polyester is preferably 0.05 to 1.0 parts by weight per 100 parts by weight of the polyester.

Next, one example of the method for producing a printing receiving sheet of the present invention will be described, but the method is not limited to this example.

First, the base sheet of the present invention is molded. 4-methylpentene-1 polymer as an incompatible polymer and polyalkylene gelcol as a specific gravity lowering agent were added to polyethylene terephthalate, thoroughly mixed and dried, and then 270
It can be fed to extruder A heated to ~300°C and molded into a sheet through a T-die. In addition, polyethylene terephthalate containing additives such as inorganic particles is fed to extruder B using a conventional method, and the polymer in layer B of the extruder becomes the surface layer using a T-die three-layer nozzle to form three layers B/A/B. It can also be laminated into a structure and formed into a sheet.

The sheet-like film obtained as described above was heated at a temperature of 1
It can be cooled and solidified in a cooling drum at 0 to 60°C to form an unstretched film. Next, this unstretched film was
Guided to a group of rolls heated to 120'C,
A -axis stretched film can be obtained by longitudinally stretching the film 5 times and cooling it with a group of rolls at 20 to 30°C. Subsequently, the longitudinally stretched film is introduced into a tenter while holding both ends with clips, and is laterally stretched in a direction perpendicular to the longitudinal direction in an atmosphere heated to 90 to 140'C to obtain a biaxially stretched film.

The stretching ratio is 2 to 5 times in both the length and width directions, and the area ratio (longitudinal stretch ratio x lateral stretch ratio) is preferably 6 to 20 times. If the area magnification is less than 6 times, the resulting film will have poor whiteness, while if it exceeds 20 times, it will tend to tear easily during stretching and the film formability will tend to be poor.

Next, poly(meth) containing a reactive monomer on at least one surface of the obtained biaxially oriented polyester film
A coating layer made of a composition containing an acrylic ester copolymer as a main component is provided. Methods for providing coating waste include: 1. A method in which the film support is biaxially stretched in advance during the film forming process, and then a solution adjusted to a predetermined amount is applied and dried; 2. A method in which the film support is rolled as a single film. Apply after removing
A method including a drying step, etc. can be preferably applied. The solution of the components to be applied is an organic solvent solution using an organic solvent, for example, an alcohol type, a carboxylic acid ester type, a ketone type, an aliphatic hydrocarbon type, an alicyclic or aromatic hydrocarbon type, or a mixture thereof. used in the form of

The coating method is not particularly limited, and extrusion lamination, melt coating, etc. may be used, but gravure coating, reverse coating, kitsu coating, die coating, etc. are used because they enable high-speed thin film coating.
Known methods such as the metaling barcode method can be applied.

In addition, by performing known surface treatments such as corona discharge treatment in the air or in various other atmospheres as necessary before coating, not only will the coating properties be improved, but the coating layer will also be made stronger. Can be formed on the surface of polyester film. Although the coating material concentration and coating film drying conditions are not particularly limited, it is desirable to carry out the drying within a range that does not adversely affect the properties of the coating layer or the base film.

The film laminated with the coating layer in this way has a thickness of 150 to 230 mm in a tenter in order to provide flatness and dimensional stability.
The sheet is heat-set at .degree. C., cooled uniformly and slowly, and then cooled to room temperature and rolled up to obtain the printing receiving sheet of the present invention.

[Method for measuring physical properties and evaluating effects] (1) Surface roughness: Cutoff 0.25n+n+ according to JIS B060]-1976.

The center line average roughness Ra (μm) and the maximum roughness Rt (μmη) are determined at a measurement length of 4 mm.

(2) Average spherical diameter of voids A cross section cut in the machine direction or perpendicular direction of the film during the film forming process was magnified by a scanning electron microscope of 1000x to 5000x.
Take a twice-enlarged photograph, apply an image analyzer to at least 100 voids in the specified thickness range, and find the distribution of diameters of circles corresponding to the area of the voids. The volume average diameter of this distribution is defined as the average spherical equivalent diameter of the void.

(3) Specific gravity carbon tetrachloride-〇-hebutane-based density gradient tube
Use the value in °C.

(4) Heat shrinkage rate The film has a width of 1.5 mm in the longitudinal direction or width direction. Omm length 30
After cutting it to 0 mm, marking it at 200 mm intervals and fixing it to a support plate under constant tension (5 g), measure the original length a (mm) of the marking intervals. Next, a load was applied using a 3 g clip and the sample was processed for 30 minutes while rotating in a hot air oven at 150° C., and the marking interval b (mm) was measured in the same manner as the original length measurement.

The heat shrinkage rate is determined using the following formula, and the average value of the five trees is used.

Heat shrinkage rate (%) = (a-b)/a (5) Layer the optical density films to a thickness of approximately 1.50 μm and measure the transmission density using an optical densitometer (TR927, manufactured by Macbeth). do. The thickness and optical density of the film are plotted, and the optical density corresponding to a thickness of 150 μm is determined.

(6) According to whiteness JT 5-L-IQI5, U manufactured by Shimadzu Corporation
When the reflectance at a wavelength of 450 hm and 550 nm using V-260 is defined as B% and G%, respectively, the whiteness (
%)=4B-3G.

(7) The surface color of the color tone film is measured with a color difference meter Σ80 manufactured by Nippon Heavy Industries, Ltd., and judged based on the obtained ■7 value, a value, and b value.

(8) Stretchability When the film was formed continuously for 24 hours, a film with no tearing was evaluated as "good", and a film with two or more tears was evaluated as "broken".

(9) Cushion rate (%) Mitoyo Seisakusho ■ Dial gauge No. 2] Use standard probe 900030 for 09-10, and dial gauge stand No. Thickness d of each film when loads of 50 g and 500 g are applied to the dial gauge holding part using 7001DGS-M 50. ,,d,0(calculated from l using the following formula.

(10) Shape factor In the same way as when determining the average diameter of voids, the shape of the incompatible polymer in the cross section of the film is measured using an image analyzer and expressed as the ratio of 100 average major diameters to minor diameters.

(11) Adhesion of the coating layer The adhesion between the coating layer and the base film can be determined by making a cross cut (100 pieces/cn?) on the coating layer and using cellophane tape (CT-24, Nichiban) at 45 degrees to the cross cut surface. (manufactured by ■), apply a load of approximately 5 kg using a hand roller, press it back and forth 10 times, and apply cellophane tape by hand for 18 cm.
The coating layer was forcibly peeled off in the 0° direction, and the degree of peeling of the coating layer was observed. The judgment criteria are as follows.

◎: Very good (no peeling) ○: Good (peeling area less than 5%) △: Slightly poor (peeling area 5% or more and less than 20%) ×: Poor (peeling area 20% or more) (12) Solvent-resistant coating After immersing the layered polyester film in tetrachlorethylene for 30 minutes, make cross cuts (100 pieces/cnf) in the coating layer, and observe and evaluate the degree of peeling of the coating layer in the same manner as in (11) above. .

(13) After immersing the polyester film on which the water-resistant coating layer was formed in warm water at 50°C for 30 minutes, the coating layer was cross-cut (1
00 pieces/C♂), and the degree of peeling of the coating layer was observed and evaluated in the same manner as in (11) above. In addition, if an abnormality (whitening, etc.) is observed on the surface condition with the naked eye, it is judged as poor even if the cellophage evaluation is good.

(14) Printability A character pattern is printed using a high-speed barcode printer "Toshi 8400 System (manufactured by Toshi Engineering Corporation)", and the print quality is visually observed with a magnifying glass and judged as follows.

◎: Very good printability ○: Good printability △: Slightly poor printability ×: Poor printability [Action of the invention] The present invention provides poly(meth) containing a reactive monomer on a polyester film. Because the coating layer was formed using a phase tester whose main component was an acrylic ester copolymer, we were able to obtain the following excellent effects without deteriorating the properties of the base film. .

[Effects of the Invention] The printing receiving sheet of the present invention has the following excellent effects.

(1) Excellent suitability for printing with various inks such as ultraviolet curable inks, electron beam curable inks, oil-based inks, thermal transfer ink ribbons, and electrophotographic toners.

(2) Since it has excellent solvent resistance, even when printing using organic solvent-based ink, the printing interface is not disturbed and clear printing can be achieved.

(3) Since it has excellent water resistance, the coating layer has excellent adhesion even under high temperature or high humidity atmospheres, and does not cause swelling of the coating layer.

(4) Characteristics do not deteriorate even when hot water treatment or solvent treatment is performed in post-processing.

Further, since the shape of the incompatible polymer dispersed in polyester is close to a spherical shape, the following effects can be obtained.

(5) Despite having a low specific gravity of 0.95, a film with excellent thermal dimensional stability, high cushioning properties and high whiteness can be obtained.

(6) If necessary, a film with excellent thermal dimensional stability can be obtained even if the specific gravity is as small as 0.6 to 0.7.

■ High whiteness and low color tone values are obtained, giving a high-class image.

Therefore, the printing receiving sheet of the present invention can be applied to a wide range of applications where printing is required, such as packaging, optical applications, graphic applications, electrical disconnection applications, and the like. Among them,
It is particularly suitable for barcode printing that requires high printing resolution and ink adhesion, and for cleaning, where barcode management is applied, and for process and quality control in product manufacturing.
It is useful as a label for price display, transportation, etc.

[Examples] The present invention will be explained using Examples, but the Examples of the present invention are not limited thereto.

Example 1 Homopolymer chips of polyethylene terephthalate produced by a conventional method (intrinsic viscosity: 0.62, melting point:: 25
9°C) at 180°C for 2 hours under reduced pressure (3 mm mm 1 liter)
did. The chips were fed to an extruder equipped with a screw with a compression ratio of 3.8 at 280°C, and melt-extruded from a T-shaped nozzle.
Using the electrostatic loading method, the film was wound around a cooling drum with a surface temperature of 20° C., and cooled and solidified to obtain an unstretched film. The obtained film was stretched at 90°C in the longitudinal direction by a roll stretching method.
After stretching 3 times, the film was stretched 3.times.6 times in the width direction by a tenter stretching method, and then heat treated at 210.degree. C. for 10 seconds while relaxing 2% in the transverse direction to obtain a biaxially oriented film with a thickness of 50 .mu.m.

The obtained two axially oriented polyethylene terephthalates 1-
After corona discharge treatment was applied to the film surface, a poly(meth)acrylate copolymer "coat" containing a reactive monomer was added to the diluent using toluene/methyl ethyl ketone (mixing ratio 1:1). ■ Made
A test phase with a concentration of 40% by weight (Tg = 72°C) was applied by gravure coating, and the coated layer was dried at 120°C for 4 minutes to obtain a printing receiving sheet with a coating layer of 2.0 μm. . The properties of this printing receiving sheet are as shown in Table 1, and the coating layer had excellent adhesion, water resistance, solvent resistance, and printability.

Example 2 Using the same base film as in Example 1, using toluene/methyl ethyl ketone (mixing ratio 1:1) as a solvent, a poly(meth)acrylate copolymer "Cotax" containing a reactive monomer was prepared. ”(Made by Toshi■ Tg=72°
C) and a white hidden pigment with an average particle size of 0. Titanium oxide having a thickness of 3 μm was uniformly dispersed at a weight ratio of 70:30 to prepare a test phase having a concentration of 15% by weight. This phase test was applied in the same manner as in Example 1 to obtain a printing receiving sheet having a coating layer of 3.0 μm. The properties of this printing receiving sheet are shown in Table 1. As seen in Table 1, it can be seen that the coating layer has excellent adhesion, water resistance, solvent resistance, and printability.

Example 3 The same profiteering film as in Example 2 was used, and a paint with the same composition as in Example 2 was used as a cross-linking agent to solidify the Isoshane-1/based curing agent "Coronet 1-" ETT (manufactured by 11 Polyurethane Industries). minutes], 5 parts by weight per part by weight of O0 were added and uniformly dispersed to prepare a phase test with a concentration of 15% on heavy paper. This phase inspection was applied using the same method as in Example 2, and the coating layer was 3.0 μm.
A receiving sheet for printing was obtained. The properties of this printing receiving sheet were excellent as shown in Table 1.

Comparative Example 1 - The same basic film as in Example 2 was used, and water-based polyester copolymer resin "Polyester W-9501" was used as a phase test.
(manufactured by B Honsei Kagaku Kogyo ■) and an average particle size of 0. /Iμm
An aqueous solution with a concentration of 10% by weight, in which titanium oxide was uniformly dispersed with a heavy electrolyte solid content ratio of 70:30, was applied using the barcode method, and the coating was dried at 1-10°C for 3 minutes to form a coating layer. 1
．． A printing receiving sheet of 0 μm was obtained. The properties of this printing receiving sheet are shown in Table 1, including the water resistance of the coating layer,
The solvent resistance was poor.

Table 1 Example 4 Polyethylene terephthalate (intrinsic viscosity [η] -〇,
65), 888% by weight, poly-4-methylpentene 1 (Mitsui Petrochemical ■TPX-d820), 10% by weight, molecular weight 4.
A raw material mixed with 2% by weight of polyethylene glycol of 0.000 was fed to an extruder, melted at 285°C in a conventional manner, and introduced into the center layer of a 3-layer T-die alloy.

On the other hand, 10% by weight of calcium carbonate (average particle size 0.8 μm) in 90% by weight of polyethylene terephthalate,
A raw material to which 0.01% by weight of the optical brightener "0B-1" was added was supplied to extruder B, melted at 285°C by a conventional method, and laminated on both surfaces of a T-die 3-layer composite die. The molten sheet was cooled and solidified by an electrostatic charging method on a cooling drum whose surface temperature was maintained at 25°C.Then, the cast sheet was heated in the longitudinal direction using a group of rolls heated to 98°C.3.
It was stretched 5 times and cooled to 25°C. Further, the stretched film was introduced into a tenter, stretched 3.2 times in the width direction in an atmosphere heated to 125°C, and heat-set at 225°C to obtain a film with a thickness of 100 μm. The thickness of the film was 5 μm for the surface layer and 90 μm for the center layer.

After subjecting the biaxially stretched film surface -L to corona discharge treatment, a printing receiving sheet was obtained in the same manner as in Example 3.

The properties of the obtained printing receiving sheet are shown in Table 2, and it can be seen that it is a low specific gravity film with excellent thermal stability, high cushioning properties and whiteness. Furthermore, the coating layer was excellent in terms of adhesion, solvent resistance, water resistance, and printability, all of which were very good (◎).

Table 1 Examples 5 to 6 All examples except for using polypropylene (Noblen, manufactured by Mitsui Toatsu Co., Ltd., [1) in place of the incompatible polymer poly-4-methylpentene-1 used in Example 4. Example 5 was a case in which the same procedure as above was performed, and Example 6 was a case in which heat treatment was not performed in Example 5.

The properties of the obtained film are shown in Table 3.

Examples 7 to 10 Specific gravity lowering agent polyethylene glycol used in Example 4 (
A receiving sheet for printing was obtained in the same manner as in Example 4 except that the amount of PEG) added was changed.

The properties of the obtained film are shown in Table 4. It can be seen that a film with a low specific gravity and excellent thermal dimensional stability can be obtained depending on the amount of the specific gravity lowering agent polyethylene glycol added.

Claims (9)

[Claims] (1) A receiving sheet for printing, characterized in that a coating layer mainly composed of a poly(meth)acrylate copolymer containing a reactive monomer is coated on at least one side of a polyester film. (2) The receiving sheet for printing according to claim (1), wherein the coating layer contains a white hidden pigment. (3) The printing receiving sheet according to claim (1) or (2), wherein the coating layer contains a crosslinking agent. (4) Claims (1) to (3) wherein the polyester film has a heat shrinkage rate of less than 2% at 150°C and a specific gravity of 0.95 or less.
) Printable receiving sheet as described in any of the above. (5) Claims (1)-(
4) The printing receiving sheet according to any one of 4). (6) A claim characterized in that the incompatible polymer is a polymer with a melting point of 200°C or higher selected from methylbutene polymer, methylpentene polymer, styrene polymer, fluorine polymer, cellulose acetate, and cellulose propionate polymer. The printing receiving sheet described in item (5). (7) Claim (1) characterized in that the color tone b value of the polyester film determined by a color difference meter is -3 or less.
The receiving sheet for printing according to any one of (6) to (6). (8) Claim (1) characterized in that the polyester film is obtained by adding a specific gravity lowering agent to polyester.
The printing receiving sheet according to any one of (7) to (7). (9) A claim in which the specific gravity lowering agent is selected from polyalkylene glycol, ethylene oxide/propylene oxide copolymer, alkylbenzene sulfonate, alkyl sulfonate, and modified products thereof ( 8) Printable receiving sheet as described above.