JP2002113959A - Image receiving film for printing and thermal transfer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin film which is a thermal transfer film, a melting thermal transfer film in particular, being excellent in the transferability, adhesion and water-resistant adhesion of ink in an environment of high temperature and high humidity and enabling attainment of a clear image in regard to a thermal transfer type print and which is excellent in the transition property, adhesion and water-resistant adhesion of ink in various printing methods. SOLUTION: The present image receiving film for printing and thermal transfer has a coating layer constituted of the constituent (A) and (B) and provided on the surface of a substrate constituted of the thermoplastic resin film. (A) a water-based dispersion of a resin which is prepared by dispersing in water an olefin copolymer (a) to which an unsaturated carboxylic acid or an anhydride thereof is bonded, with at least one kind selected out of a group comprising a nonionic surfactant, a nonionic water-soluble polymer, a cationic surfactant and a cationic water-soluble polymer used as a dispersant (b), wherein the weight ratio per solids of (a)/(b) is 100/1-100/30 and of which the average particle size is 5 ×m or less (B) an ethylene imine adduct of a polyimine-series polymer or a polyamine polyamide which is expressed by specific general formula (I).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer film for a thermal transfer printer, which is excellent in ink transferability, adhesion and water resistance under high-temperature and high-humidity environment, and which can obtain a clear image, particularly a fusion thermal transfer film. The present invention also relates to a thermoplastic resin film having excellent ink transferability, adhesion and water-resistant adhesion in various printing methods.

[0002]

2. Description of the Related Art As a thermal transfer recording method, there are a sublimation thermal transfer method, a fusion thermal transfer method, an electrophotographic method, an electrostatic recording method, and the like, which are widely used for recording images and information. These use thermal energy for transfer and fixing and adhesion of images.For example, a color material is transferred from the ink ribbon to the recording medium by pressing against the recording medium via the ink ribbon, or the toner is transferred to the recording medium at a high temperature. Or by heating with a roll or light. Among these, a description will be given of a fusion heat transfer system generally used for recording information such as a bar code. As shown in FIG. 1, a thermal transfer ink ribbon 1 composed of a heat-meltable ink 1a and a substrate 1b supporting the same is provided. The image receiving film 2 is sandwiched between a print head 3 provided with a thermal head or the like as a heat source and a drum 4, and the thermal head is controlled by an electric signal to control the heat in the thermal transfer ink ribbon 1. This is to directly transfer the melted ink 1a to the image receiving film 2 by heating the meltable ink 1a.

In the case of such a fusion heat transfer system, the support itself may be used as an image receiving film, but a layer of a polyester resin or epoxy resin having good adhesion to the hot-melt ink on the surface of the support. And a primer layer are often provided. Accordingly, the support of these image-receiving films is generally a pulp paper, a synthetic paper comprising a stretched film of a propylene-based resin containing an inorganic fine powder such as calcined clay or calcium carbonate, a polyethylene terephthalate stretched film, or a polyolefin. Coated synthetic paper etc. whose whiteness and dyeability have been enhanced by applying a pigment coating containing inorganic fine powder such as silica or calcium carbonate and a binder to these surfaces. Used. However, as a support of the image receiving film after transfer, from the viewpoint of strength, dimensional stability, etc., obtained by stretching an inorganic fine powder-containing polyolefin resin film,
It is said that synthetic paper having a large number of microvoids (micropores) therein is preferable (Japanese Patent Publication No. 46-40 / 1976).
794, JP-A-56-55433, JP-A-57-1
49363 and JP-A-57-181829.

[0004] By forming microvoids in the film, these synthetic papers provide good flexibility and heat insulation, resulting in improved cushioning with the print head and higher thermal energy efficiency. It became. However, in the image receiving film used in the above-mentioned melt heat transfer system, the support is the above-mentioned stretched film made of the above-mentioned inorganic fine powder-containing polyolefin-based resin, and further, as an image receiving layer, to impart various printability and antistatic performance. Coated with a water-soluble primer of a nitrogen-containing polymer (see JP-A-57-149363)
In a high-temperature and high-humidity environment, the transfer of the hot-melt ink is hindered because the primer layer has a hygroscopic property and contains a large amount of water, and the hot-melt ink is transferred to the image receiving film. However, as a result, there are problems such as line breaks in printing of bar codes and the like, and images becoming unclear.

[0005] In order to solve this problem, the inorganic fine powder contained in the support is mixed with 30 fine colloidal calcium carbonate having an average particle size of 0.02 to 0.5 µm and a specific surface area of 60,000 to 300,000 cm ² / g. The use of an image receiving film obtained by applying a water-soluble primer of a nitrogen-containing polymer compound to a microporous support formed of a stretched polyolefin-based resin film containing from 65 to 65% by weight, It has been reported that a clear image can be obtained even in a humid environment (see JP-A-8-80684). However, in the image receiving film used in the melt thermal transfer system, the support is a stretched film made of a polyolefin resin, and the image receiving layer using a water-soluble primer of a nitrogen-containing polymer compound as the image receiving layer has a high temperature and a long time. When placed in a high-humidity environment, the moisture absorption of the primer layer serving as the transfer surface (printing surface) of the hot-melt ink increased, and the evaporated water was retained on the surface of the primer layer serving as the ink transfer surface. It is considered to be in a state.

For this reason, it has been pointed out that a printed matter placed in a high-temperature, high-humidity environment for a long time may have a problem of poor ink adhesion such that the ink is easily peeled off when the printed surface is peeled off with a cellophane tape. ing. Regarding this problem, it has been reported that providing the coating layer described in Japanese Patent Application No. 11-344554 improves ink adhesion. However, the film provided with the coating layer has good transferability of the printing ink, but the printed matter immersed in water has a problem of poor ink adhesion such that the ink is easily peeled off when the printing surface is peeled off with a cellophane tape. It became clear to do.

[0007]

Accordingly, an object of the present invention is to solve these problems of the prior art and to provide a thermoplastic resin film having excellent printability. That is, the present invention is a thermal transfer film which is excellent in ink transferability, adhesion and water resistance under high temperature and high humidity environment in a thermal transfer type print, and provides a clear image, particularly a melt thermal transfer film, and various printing methods. The object of the present invention is to provide a thermoplastic resin film having excellent ink transferability, adhesion and water resistance.

[0008]

According to the present invention, there is provided a printing and heat transfer method comprising providing a coating layer formed by coating and drying the following components (A) and (B) on the surface of a support. To provide an image receiving film for use. (A) An olefin copolymer (a) having an unsaturated carboxylic acid or an anhydride thereof bonded thereto is prepared from a nonionic surfactant, a nonionic water-soluble polymer, a cationic surfactant, or a cationic water-soluble polymer. An aqueous dispersion obtained by dispersing in water using at least one selected from the group consisting of a dispersant (b), wherein the weight ratio of (a) / (b) per solid is 100/1 to 100 / 30 and an average particle diameter of 5 μm or less.

(B) An ethyleneimine adduct of a polyimine polymer or a polyamine polyamide represented by the following general formula (I).

Embedded image (Linear or branched alkyl group wherein, R ¹ and R ² are each independently a hydrogen atom or a range of 1 to 10 carbon atoms, an alkyl group having an alicyclic structure, an aryl group, R ³ Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an allyl group, an alkyl group having an alicyclic structure, an aryl group or a hydroxide thereof, and m is 2 to 6
And n is an integer in the range of 20 to 3000, and these may be used alone or in combination of several kinds. )

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION [1] Coating Agent (1) Constituent Material (A) Component The coating layer formed by applying and drying the component (A) constituting the present invention is heated by printing. The ink component of the hot-melt ink and the resin component of the component (A) soften,
Further fusion is considered to bring about an effect by showing strong adhesion. In the above component (A), the olefin copolymer (a) to which an unsaturated carboxylic acid or an anhydride thereof is bonded refers to an ethylene- (meth) acrylic acid copolymer or an ethylene- (meth) acrylic acid copolymer. Alkali (earth) metal salt, ethylene- (meth) acrylate-maleic anhydride copolymer, (meth) acrylic acid-grafted polyethylene, maleic anhydride-grafted polyethylene, maleic anhydride-grafted ethylene-vinyl acetate copolymer, Maleic anhydride grafted (meth) acrylic acid ester-ethylene copolymer, maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-propylene copolymer, maleic anhydride grafted ethylene-propylene-butene copolymer, maleic anhydride grafted Ethylene-butene copolymer, maleic anhydride It refers to butene copolymer - raft propylene.

Among them, the melting point or softening point is 130
C. or lower ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate-maleic anhydride copolymer, maleic anhydride-grafted ethylene-vinyl acetate copolymer, maleic anhydride-grafted (meth) acrylic Acid ester-ethylene copolymer, maleic anhydride-grafted ethylene-propylene-butene copolymer, maleic anhydride-grafted ethylene-butene copolymer, and maleic anhydride-grafted propylene-butene copolymer from the viewpoint of ink acceptability Particularly preferred. The dispersant (b) for dispersing the olefin copolymer to which the unsaturated carboxylic acid or anhydride thereof is bonded in water includes a nonionic surfactant, a nonionic water-soluble polymer, a cationic surfactant, It is necessary to use at least one selected from the group consisting of soluble water-soluble polymers.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oxypropylene block polymer, polyethylene glycol fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Examples of the nonionic water-soluble polymer include completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and modified products thereof, and hydroxyethyl cellulose. Examples of the cationic surfactant include stearylamine hydrochloride, lauryltrimethylammonium chloride, trimethyloctadecylammonium chloride and the like.

Further, as the cationic water-soluble polymer,
Examples thereof include a polymer having a quaternary ammonium salt structure or a phosphonium salt structure, a nitrogen-containing (meth) acrylic polymer, and a nitrogen-containing (meth) acrylic polymer having a quaternary ammonium salt structure. Among these, from the viewpoint of adhesion to the thermoplastic resin film, a cationic water-soluble polymer such as a nitrogen-containing (meth) acrylic polymer or a nitrogen-containing (meth) acrylic polymer having a quaternary ammonium salt structure is used. Is particularly preferred. In order to disperse an olefin copolymer (a) to which an unsaturated carboxylic acid or an anhydride thereof is bound in water using a dispersant (b), it is necessary to use (a) /
(B) the weight ratio per solid content is 100/1 to 10
It must be 0/30. If the amount of the dispersant used is out of this range and the amount of the dispersant used is small, the olefin copolymer to which the unsaturated carboxylic acid or its anhydride is bonded cannot be dispersed in water. Conversely, when the amount of the dispersant used increases, the effect of improving poor ink adhesion in a high-temperature and high-humidity environment is adversely affected.

The average particle diameter of the resin particles in the component (A) in the present invention must be 5 μm or less. 5μ
If m is exceeded, not only the stability of the aqueous dispersion during standing will deteriorate, but also the adhesion of the thermoplastic resin film to the support will deteriorate. In order to disperse an olefin copolymer (a) to which an unsaturated carboxylic acid or an anhydride thereof is bound in water using a dispersant (b), for example, the olefin copolymer is dissolved in an aromatic hydrocarbon solvent. Is heated and dissolved, and the dispersant (b) is mixed and stirred, followed by phase inversion while adding water, and then an aromatic hydrocarbon-based solvent is distilled off to obtain an aqueous dispersion. As disclosed in JP-A-29447, the olefin-based copolymer is supplied to a hopper of a twin-screw extruder, and an aqueous solution of a dispersant (b) is added thereto while being melted by heating and melt-kneaded. Is added to obtain a dispersion. Among these, when the dispersant (b) is a cationic water-soluble polymer such as a nitrogen-containing (meth) acrylic polymer or a nitrogen-containing (meth) acrylic polymer having a quaternary ammonium salt structure, It is preferable to use a twin-screw extruder from the viewpoint of the average particle size of the resin particles in the obtained aqueous dispersion.

Component (B) Addition of a polyimine-based polymer or an ethyleneimine adduct of a polyamine polyamide, which is a component (B), to the component (A) constituting the present invention, the adhesiveness of the printing ink, particularly the ultraviolet curable ink. Adhesion can be improved. Examples of such a compound include polyethyleneimine, poly (ethyleneimine-urea) and an ethyleneimine adduct of polyamine polyamide, or an alkyl-modified, cycloalkyl-modified, aryl-modified, allyl-modified, aralkyl-modified product thereof. Alkyral modified product, benzyl modified product, cyclopentyl modified product, or aliphatic cyclic hydrocarbon modified product, or a hydroxide thereof, which can be used alone or in combination of several types.

Among them, it is preferable to use a polyimine polymer represented by the following general formula (I) from the viewpoint of improving the adhesion to the offset ink and the transferability.
Here, the degree of polymerization of polyethyleneimine is not limited, but is preferably 20 to 3,000.

Embedded image (Linear or branched alkyl group wherein, R ¹ and R ² are each independently a hydrogen atom or a range of 1 to 10 carbon atoms, an alkyl group having an alicyclic structure, an aryl group, R ³ Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an allyl group, an alkyl group having an alicyclic structure, an aryl group or a hydroxide thereof, and m is 2 to 6
And n is an integer in the range of 20 to 3000, and these may be used alone or in combination of several kinds. )

Component (C) Addition of a water-soluble epoxy, isocyanate, formalin or oxazoline resin as a cross-linking agent as component (C) to the above components (A) and (B) results in a poor compatibility with printing ink. The water resistance can be further improved. As the crosslinking agent, in particular, bisphenol A-epichlorohydrin resin,
Epichlorohydrin resin of polyamine polyamide, aliphatic epoxy resin, epoxy novolak resin, alicyclic epoxy resin, brominated epoxy resin is preferred, most preferably epichlorohydrin adduct of polyamine polyamide, or monofunctional to polyfunctional glycidyl ether,
Glycidyl esters.

Component (D) By adding a polymer-type antistatic agent as the component (D) to the components (A) and (B), it is possible to reduce troubles caused by adhesion of dust and printing and charging during printing. Can be done. As the polymer type antistatic agent, cationic type, anionic type, amphoteric type, nonionic type and the like can be used. Examples of the cationic type include those having an ammonium salt structure or a phosphonium salt structure. Examples of the anionic type include alkali metal salts such as sulfonic acid, phosphoric acid and carboxylic acid, for example, alkali metal salts such as acrylic acid, methacrylic acid and (anhydride) maleic acid (for example, lithium salt,
Sodium salt, potassium salt, etc.) in the molecular structure. The amphoteric type contains both the cationic and anionic structures in the same molecule, and includes, for example, a betaine type. Examples of the nonionic type include an ethylene oxide polymer having an alkylene oxide structure and a polymer having an ethylene oxide polymerization component in a molecular chain. In addition, a polymer type antistatic agent having boron in the molecular structure can also be mentioned as an example. Among these, a nitrogen-containing polymer type antistatic agent is preferable, and a tertiary nitrogen or quaternary nitrogen-containing acrylic polymer is more preferable. In addition, an antifoaming agent, other auxiliaries, and the like may be added to the coating composition of the present invention, if necessary, as long as printing and thermal transfer characteristics are not impaired.

(2) Quantitative Ratio The coating agent used in the present invention has the following ratio for components (B) to (D) based on 100 parts by weight of component (A). Component (B) 1 to 25 parts by weight, preferably 2 to 15 parts by weight Component (C) 0 to 25 parts by weight, preferably 2 to 15 parts by weight Component (D) 0 to 25 parts by weight, preferably 2 to 15 parts by weight Part (3) Form of coating agent Each component of the coating agent is water or methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone,
It is used after being dissolved in a solvent such as methyl ethyl ketone, ethyl acetate, toluene, xylene, etc., but it is usually used in the form of an aqueous solution. The solution concentration is usually 0.5 to 40% by weight, preferably about 1 to 20% by weight.

(4) Coating (a) Coating amount The coating amount of the coating agent on the support is 0.03 to 5 in terms of solid content.
g / m^Two, Preferably 0.05 to 0.5 g / m^TwoIn
You. 0.03 g / m^TwoIf less than the heat in high temperature and high humidity environment
Insufficient transfer, adhesion and water resistance of meltable ink
And 5 g / m ^TwoIn the super, not only the drying property is inferior, but also
5g / m^TwoAlready provide sufficient performance,
It is not practical just to be a step. (B) Coating device As a coating device, a roll coater or a blade coater is used.
ー, bar coater, air knife coater, size press
Scoater, gravure coater, die coater, lip
Use a coating device that uses a coater, spray coater, etc.
Can be used.

[2] Support The support used in the present invention is a thermoplastic resin film, and the support is made of pulp paper or plain woven fabric (Ponzi).
Alternatively, it may be a laminate with a nonwoven fabric (spun bond). The type of the thermoplastic resin film used is not particularly limited. For example, ethylene-based resins such as high-density polyethylene and medium-density polyethylene, propylene-based resins, polyolefin-based resins such as polymethyl-1-pentene and ethylene-cyclic olefin copolymer; nylon-6, nylon-
Polyamide resins such as 6, 6; thermoplastic resins such as polyethylene terephthalate and copolymers thereof, polybutylene terephthalate and copolymers thereof, and aliphatic polyesters; polycarbonate, atactic polystyrene, syndiotactic polystyrene, etc. can do. Especially, it is preferable to use a nonpolar polyolefin resin.

Further, among the polyolefin resins, it is preferable to use a propylene resin from the viewpoint of chemical resistance and cost. Examples of the propylene-based resin include an isotactic polymer and a syndiotactic polymer obtained by homopolymerizing propylene.
In addition, ethylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene and other α-olefins and propylene copolymerized, polypropylene having various stereoregularities as a main component. Copolymers can also be used. The copolymer may be a binary system, a ternary system or more, or a random copolymer or a block copolymer. The propylene homopolymer is preferably used by blending a resin having a lower melting point than that of the propylene homopolymer in an amount of 2 to 25% by weight. High-density or low-density polyethylene can be exemplified as such a resin having a low melting point.

As the thermoplastic resin for the support, one of the above thermoplastic resins may be selected and used alone, or two or more may be selected and used in combination. The thermoplastic resin of the support includes inorganic fine powder and / or
Alternatively, an organic filler can be included. As the inorganic fine powder, the average particle size is usually 0.01 to 15 μm, preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.
μm can be used. When the average particle size is less than 0.01 μm, the inorganic fine powder is not uniformly dispersed at the time of melt-kneading with the thermoplastic resin, or the inorganic fine powder is secondary aggregated,
Moisture foaming may occur due to the influence of absorbed moisture. If the average particle size exceeds 15 μm, the strength of the film tends to decrease. Specifically, calcium carbonate, calcined clay, silica, diatomaceous earth, talc, titanium oxide, barium sulfate, alumina and the like can be used. Among them, calcium carbonate is preferred. The particle size of the inorganic fine powder used in the present invention can be measured using a particle measuring device, a laser diffraction particle measuring device “Microtrack” (manufactured by Nikkiso Co., Ltd.,
(Accumulated 50% particle size).

The organic filler has an average particle size after dispersion of usually 0.01 to 15 μm, preferably 0.01 to 8 μm.
m, more preferably 0.03 to 4 μm. It is preferable to select a different type of resin from the thermoplastic resin that is the main component. For example, when the thermoplastic resin film is a polyolefin-based resin film, as the organic filler, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, a cyclic olefin homopolymer or cyclic olefin Melting point of 1 such as copolymer with ethylene
20 ° C to 300 ° C or glass transition temperature of 120 ° C
280 ° C.

To the thermoplastic resin of the support, a stabilizer, a light stabilizer, a dispersant, a lubricant and the like can be added, if necessary, in addition to the inorganic fine powder and the organic filler. When a stabilizer is added, it is usually added in the range of 0.001 to 1% by weight. Specifically, sterically hindered phenol-based, phosphorus-based, amine-based stabilizers and the like can be used. When a light stabilizer is added, it is usually added in the range of 0.001 to 1% by weight. Specifically, sterically hindered amine-based, benzotriazole-based, benzophenone-based light stabilizers and the like can be used. The dispersant and the lubricant are used, for example, for the purpose of dispersing the inorganic fine powder. The amount used is usually in the range from 0.01 to 4% by weight. Specifically, silane coupling agents, higher fatty acids such as oleic acid and stearic acid, metal soaps, polyacrylic acid, polymethacrylic acid, and salts thereof can be used.

The method of forming the support made of a thermoplastic resin film is not particularly limited, and the support can be formed by appropriately selecting from known methods. For example, cast molding for extruding a molten resin into a sheet using a single-layer or laminated T-die or I-die connected to a screw type extruder, calender molding, rolling molding, inflation molding, thermoplastic resin and organic solvent or Casting or calendering a mixture with oil and then removing the solvent or oil can be used for molding. The thermoplastic resin film used for the support may be unstretched or stretched. Stretching is
It can be carried out by any of various commonly used methods.

As specific examples, longitudinal stretching utilizing the peripheral speed difference of the roll group, transverse stretching using a tenter oven, rolling, simultaneous biaxial stretching using a combination of a tenter oven and a linear motor, and the like can be used. The temperature at the time of stretching is not lower than the glass transition temperature of the thermoplastic resin to be used in the case of non-crystalline resin, and is not lower than the melting point of the crystal part in the case of crystalline resin. It can be performed within a known temperature range suitable for the resin. Specifically, the stretching temperature is preferably a temperature lower by 2 to 60 ° C. than the melting point of the thermoplastic resin used. When the resin is a propylene homopolymer (melting point: 155 to 167 ° C.), the stretching temperature is 152 ° C.
~ 164 ° C, high density polyethylene (melting point 121-134
° C), and 110 to 120 ° C for polyethylene terephthalate (melting point: 246 to 252 ° C).
Preferably, the temperature is set at 5 ° C. The stretching speed is 20 to
Preferably it is 350 m / min.

The stretching ratio is not particularly limited, and is appropriately determined in consideration of the characteristics of the thermoplastic resin used. For example, when a propylene homopolymer or a copolymer thereof is used as the thermoplastic resin, it is about 1.2 to 12 times, preferably 2 to 10 times when stretched in one direction, and 2 to 10 times when stretched biaxially. 1.5 to 60 times in area magnification, preferably 10
~ 50 times. When using other thermoplastic resins, when stretched in one direction is 1.2 to 10 times, preferably 2 to 5 times, and in the case of biaxial stretching, 1.5 to 20 times in area magnification, Preferably it is 4 to 12 times. If a thermoplastic resin containing an inorganic fine powder or an organic filler is stretched, a stretched porous resin film having fine pores therein can be obtained.

The porosity indicates a porosity represented by the following equation (1).

(Equation 1) Ρ ₀ in the equation (1) represents the true density of the stretched film,
Represents the density of the stretched film (JIS-P-8118). Unless the material before stretching contains a large amount of air, the true density is almost equal to the density before stretching.

The porosity is 5 to 60%, preferably 10 to 5
It is within the range of 9%. The physical properties of the stretched thermoplastic resin film are as follows: density is 0.65 to 1.20 g / cm ³ ,
Opacity (JIS-P-8138) is 50-100%,
Preferably 70 to 100%, whiteness (JIS-P-812)
3) is 80 to 100%, preferably 90 to 100%. If the opacity and whiteness are out of the above ranges, the film is printed with a barcode, and when used as a label, it is unfavorable because a barcode reading error may occur due to the influence of the background.

The thermoplastic resin film forming the support of the present invention may have a surface layer on the front and back surfaces of the base layer, whether it is a single layer or a two-layer structure of a base layer and a surface layer.
It may have a layered structure or a multilayered structure in which another resin film layer exists between the base layer and the surface layer, and may be stretched in at least one axial direction. When the multilayer structure is stretched, the number of stretching axes is 1 in a three-layer structure.
Axis / 1 axis / 1 axis, 1 axis / 1 axis / 2 axes, 1 axis / 2 axes / 1
Axis, 2 axes / 1 axis / 1 axis, 1 axis / 2 axes / 2 axes, 2 axes / 2 axes / 1 axis, 2 axes / 2 axes / 2 axes, and in the case of a layer structure of more layers The number of stretching axes is arbitrarily combined.

When the thermoplastic resin film is a single-layer polyolefin resin film and contains an inorganic fine powder and / or an organic filler, the polyolefin resin is usually 40 to 99.5% by weight, the inorganic fine powder and / or
Or 60 to 0.5% by weight of an organic filler, preferably 50 to 97% by weight of a polyolefin resin, 50 to 3% by weight of an inorganic fine powder and / or an inorganic filler.
Consists of When the thermoplastic resin film has a multilayer structure and the base layer and the surface layer contain an inorganic fine powder and / or an organic filler, the base layer usually contains 40 to 99.5% by weight of a polyolefin-based resin, And / or an organic filler of 60 to 0.5% by weight, a surface layer of 25 to 100% by weight of a polyolefin resin, and an inorganic fine powder and / or 75 to 0% by weight of an organic filler, preferably a base layer of a polyolefin resin. 50 ~
97% by weight, 50 to 3% by weight of inorganic fine powder and / or organic filler, and the surface layer is composed of 30 to 97% by weight of polyolefin resin and 70 to 3% by weight of inorganic fine powder.

The inorganic fine powder and / or the organic filler contained in the base layer having a single-layer structure or a multi-layer structure may contain
If the amount is more than 10% by weight, the stretched resin film is liable to break at the time of transverse stretching performed after longitudinal stretching. If the amount of the inorganic fine powder and / or the organic filler contained in the surface layer exceeds 75% by weight, the surface strength of the surface layer after the transverse stretching is low, and the surface layer is easily broken by a mechanical impact or the like during use. Not preferred. The thickness of the support used in the present invention is usually 20 to 35.
It is in the range of 0 μm, preferably in the range of 35 to 300 μm.

Before forming a coating layer on the surface of the support of the present invention, a corona discharge treatment, a flame treatment, a plasma treatment, a glow discharge treatment, an ozone treatment generally used for a film as a surface oxidation treatment. Are used alone or in combination. Of these, corona processing and frame processing are preferable, and in the case of corona processing,
600 to 12,000 J / m ² (10 to 200 W / min /
m ² ), preferably 1,200 to 9,000 J / m
^{2 (20~180W} · min / m ^2), when the frame processing, 8,000~200,000J / m ^2, preferably 20,000~100,000J / m ² is used.

[3] Applications The image receiving film for printing and thermal transfer of the present invention can be used for recording in various thermal transfer systems such as a sublimation thermal transfer system, a melt thermal transfer system, an electrophotographic system, and an electrostatic recording system. Among them, the effect of the present invention, that is, high temperature and
From the viewpoint of obtaining a remarkable effect of improving the adhesion of the transferred print and the image portion even when placed in a high humidity environment,
Use in a fusion heat transfer system is preferred. Examples of the type of ink ribbon to be used include a wax type, a resin type, and a mixed type of both, and any of them can be applied. Further, various types of printing are also possible, including offset printing, gravure printing, and flexographic printing, as well as letterpress printing.

[0036]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples and the like. (1) Production Example of Component (A) (1) Synthesis Example of Cationic Water-Soluble Methacrylic Resin as Dispersant (b) N, N-dimethylaminoethyl methacrylate 62.9
Parts, 71 parts of butyl methacrylate, 25.4 parts of lauryl methacrylate, and 200 parts of isopropyl alcohol were charged into a four-necked flask equipped with a stirrer, a dry distillation cooler, a thermometer, and a dropping funnel.
0.9 parts of azobisisobutyronitrile was added as a polymerization initiator, and a polymerization reaction was carried out at 80 ° C. for 4 hours. Next, after neutralizing with 24 parts of acetic acid, water was added while distilling off isopropyl alcohol to finally obtain an aqueous solution (b) of a viscous dispersant having a solid content of 35%.

(2) Method for producing the component (A) A co-meshing twin-screw extruder "PCM45φ" (trade name)
Ethylene-methacrylic acid copolymer (methacrylic acid content 10% by weight, MFR 35 g / 10
(A) was continuously supplied at a rate of 100 parts / hour. The dispersant (b) was continuously supplied at a rate of 22.9 parts / hour (8 parts / hour as a solid content as a dispersant) from a first injection port of the extruder. The heating temperature (cylinder temperature) was 130 ° C. while continuously supplying water at a rate of 70 parts / hour from the second inlet of the extruder.
To obtain a milky white resin aqueous dispersion. After the aqueous resin dispersion was filtered through a 250-mesh stainless steel wire mesh, water was added so that the solid content became 45%. The average particle size of the aqueous resin dispersion was 0.74 μm as measured by a laser type particle size distribution analyzer: SALD-2000 manufactured by Shimadzu Corporation.

Preparation Example of Component (B): (B-1) Glycidol-Modified Polyimine-Based Polymer In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas inlet, polyethyleneimine “Epomin
P-1000 (degree of polymerization: 1600) (manufactured by Nippon Shokubai Co., Ltd., trade name), 100 parts of a 25% by weight aqueous solution, 10 parts of glycidol and 10 parts of propylene glycol monomethyl ether were added thereto, and the mixture was stirred under a nitrogen stream. 1 at the temperature of ℃
A denaturation reaction was performed for 6 hours to obtain a glycidol-modified polyethyleneimine aqueous solution. After drying, the product was subjected to infrared spectroscopy, ¹ H-nuclear magnetic resonance spectroscopy ( ¹ H-NMR), and ¹³ C-nuclear magnetic resonance spectroscopy ( ¹³ C-NMR).
It was confirmed that the epoxy group of glycidol was added to the nitrogen of the polyethyleneimine, and that the product was obtained by reacting 23% of the nitrogen of the polyethyleneimine with glycidol.

(B-2) Butyl-modified polyimine-based polymer In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas inlet, polyethyleneimine “Epomin
100 parts of a 25% by weight aqueous solution of P-1000 (degree of polymerization: 1600, manufactured by Nippon Shokubai Co., Ltd.), 10 parts of n-butyl chloride, and 10 parts of propylene glycol monomethyl ether are stirred under a nitrogen stream. Then, a denaturation reaction was performed at a temperature of 80 ° C. for 20 hours to obtain a 20% by weight aqueous solution of butyl-modified polyethyleneimine. Component (C) Polyamine polyamide epichlorohydrin adduct “W
S-570 (solid content 12.5% by weight) "(Japan PMC
(Trade name, manufactured by Co., Ltd.).

Production Example of Component (D): A four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for purging nitrogen, and a stirrer was charged with 35 parts of dimethylaminoethyl methacrylate, 20 parts of ethyl methacrylate, and cyclohexyl. 20 parts of methacrylate, 25 parts of stearyl methacrylate, 150 parts of ethyl alcohol and 1 part of azobisisobutyronitrile were added, and a polymerization reaction was carried out at a temperature of 80 ° C. for 6 hours under a nitrogen stream. Then, 3-chloro-2
After adding 70 parts by weight of a 60% by weight ethyl alcohol solution of hydroxypropylammonium chloride, and further reacting at a temperature of 80 ° C. for 15 hours, ethyl alcohol was distilled off while adding water dropwise to obtain a fourth solid having a final solid content of 30%. A quaternary ammonium salt type copolymer was obtained.

This copolymer is an alkyl acrylate polymer containing a group represented by the following general formula in the molecular chain.

Embedded image

Production Example 1 of Support: (1) 81% by weight of a propylene homopolymer (melting point: 164 ° C.) having a melt flow rate (MFR) of 0.8 g / 10 min.
3 parts by weight of high-density polyethylene and 1.5 μm in average particle size
After kneading the composition (A) obtained by mixing 16% by weight of heavy calcium carbonate with an extruder set at 270 ° C,
The sheet was extruded into a sheet and further cooled by a cooling device to obtain a non-stretched sheet. Next, the sheet was heated again to a temperature of 150 ° C., and then stretched 5 times in the machine direction to obtain a 5 times stretched resin film.

(2) 55% by weight of a propylene homopolymer (melting point: 164 ° C.) having an MFR of 4 g / 10 min and an average particle diameter of 1.
The composition (B) mixed with 5 μm of heavy calcium carbonate (45% by weight) was kneaded by another extruder at an extruder set at a temperature of 270 ° C., and extruded into a sheet.
This was laminated on both sides of the 5-fold longitudinally stretched film obtained in the above step (1) to obtain a laminated film having a three-layer structure. Next, after cooling the three-layer laminated film to a temperature of 60 ° C., it is again heated to a temperature of 155 ° C., stretched 7.5 times in the transverse direction using a tenter, and annealed at a temperature of 165 ° C. After processing and cooling to a temperature of 60 ° C,
The thickness of the three-layer structure (uniaxial stretching / biaxial stretching / uniaxial stretching) is 80 μm (B / A / B = 15 μm / 50) by slitting the ear.
μm / 15 μm), a density (ρ) of 0.79 g / cm ³ , a porosity of 29%, an opacity of 90%, and a whiteness of 95%.

(3) Using a corona discharge treatment device “HF400F” (trade name, manufactured by Kasuga Electric Co., Ltd.), a 0.8 m long aluminum electrode was applied to the surface of the film.
A silicone-coated roll was used as a treater roll, and a corona discharge treatment was performed at a line treatment speed of 15 m / min and an applied energy density of 4,200 J / m ² , with a gap between the electrode and the roll of 5 mm.

Production Example 2 of Support: (1) MFR 0.8 g / 10 min propylene homopolymer
(Melting point: 164 ° C.) 81 parts by weight of high density polyethylene 3
1 part by weight and heavy calcium carbonate 1 having an average particle size of 1.5 μm
The composition (A) containing 6% by weight was set at 270 ° C.
A resin composition melt-kneaded with an extruder, and MFR 4 g / 10
55% by weight of propylene homopolymer (melting point: 164 ° C)
And 45 weights of heavy calcium carbonate having an average particle size of 1.5 μm
Extruder set at 270 ° C. for the composition (B) in which
The resin composition melt-kneaded in one main extruder and two
Extrude with a sub-extruder, and join them together to form one
Extruded from the T-die head of
The laminated film with a three-layer structure in the form of a sheet is cooled by a cooling device to 60
After cooling to 150 ° C, reheat to a temperature of 150 ° C.
And stretched 5 times in the machine direction, and annealed at 155 ° C.
80 μm (B / A / B = 20 μm / 40 μm
/ 20 μm), density (ρ) 1.00 g / cm ^Three, Porosity
15%, opacity 89%, whiteness 93% laminated stretch resin
A film was obtained. (2) A corona discharge treatment device “HF
400F "(made by Kasuga Electric Co., Ltd., trade name)
0.8m long aluminum electrode, Tretaro
A silicone coated roll is used for the
Is 5 mm, the line processing speed is 15 m / min,
Applied energy density 4,200 J / m^TwoCorona discharge at
Processing was performed.

Production Example 3 of Support: (1) 81 parts by weight of a propylene homopolymer (melting point: 164 ° C.) having an MFR of 0.8 g / 10 min.
1 part by weight and heavy calcium carbonate 1 having an average particle size of 1.5 μm
A resin composition obtained by melt-kneading the composition (A) containing 6% by weight with an extruder set at 270 ° C .;
55% by weight of propylene homopolymer (melting point: 164 ° C)
And a resin composition obtained by melting and kneading a composition (B) obtained by mixing 45% by weight of heavy calcium carbonate having an average particle size of 1.5 μm with an extruder set at 270 ° C., one main extruder and two And extruded with a single extruder, and extruded with one T-die head to obtain a three-layer laminated film.

(2) Next, the three-layer laminated film was cooled to 60 ° C. by a cooling device and then cooled to 150 ° C.
After reheating to a temperature of 5 ° C, the film is stretched 5 times in the longitudinal direction, further heated to a temperature of 155 ° C, stretched 7.5 times in the transverse direction using a tenter, and annealed at a temperature of 165 ° C. After processing, cooled to a temperature of 60 ° C., the ear part was slit and the wall thickness was 80 μm (B / A / B = 10 μm / 60 μm).
m / 10 μm), a density (ρ) of 0.70 g / cm ³ , a porosity of 41%, an opacity of 92%, and a whiteness of 96%. (3) A corona discharge treatment device “HF
400F "(trade name, manufactured by Kasuga Electric Co., Ltd.), a 0.8 m-long aluminum electrode, a silicone film roll as a treater roll, and a gap of 5 mm between the electrode and the roll. Processing speed 15m / min,
Corona discharge treatment was performed at an applied energy density of 4,200 J / m ² .

(Example 1) On the surface of the support of the laminated stretched resin film obtained in Production Example 1 of the support, component (A) 100
A coating agent consisting of 4 parts by weight of the component (B-2) and 4 parts by weight of the component (B-2) was applied to both sides using a roll coater and dried to obtain a film having a thickness of 0.06 g / m ² . [Evaluation] The suitability for melt heat transfer, the suitability for printing, and the antistatic property were evaluated as follows. (1) Suitability for fusion heat transfer For printing, use a barcode printer "B-30-S5"
(Tec Corporation, trade name) and a melt-type resinous ink ribbon "B110C" (Ricoh Corporation, trade name) were used. In the evaluation of Japanese Patent Application No. 11-344554, the ink transferability was evaluated by visually observing the state of the printed image, and the ink adhesion and water resistance were evaluated by visually inspecting the peeling state of the ink by peeling the printed screen with a cellophane tape. However, in this specification, a more practical bar code verifier “LASERCHEK II”
(Trade name, manufactured by Fuji Electric Refrigeration Machine Co., Ltd.).

[Evaluation of Ink Transfer Property] A bar code was printed (CODE39) on the coated surface of the film using the above-mentioned printer and ink ribbon at a temperature of 35 ° C. and a relative humidity of 85%. The performance was evaluated according to the following evaluation criteria by measuring ANSI GRADE with a bar code verifier. A, B: good (clear image is obtained) C: acceptable (slight blurring is observed in the bar code, but practical level is maintained) D to F: impossible (bar code is cut off) N / G : Not possible (level that cannot be recognized as a CODE39 barcode)

[Evaluation of Ink Adhesion] A bar code is printed (CODE39) on the coated surface of the film using the above-described printer and ink ribbon at a temperature of 23 ° C. and a relative humidity of 50%. After conditioning the printed matter for 2 hours or more at a temperature of 35 ° C. and a relative humidity of 85%, a cellophane tape was stuck to the printing screen, and after sufficient adhesion, the cellophane tape was slowly peeled off to verify the barcode. The following evaluation criteria were evaluated by measuring ANSI GEAD with a machine. A, B: good (clear image is obtained) C: acceptable (slight blurring is observed in the bar code, but practical level is maintained) D to F: impossible (bar code is cut off) N / G : Not possible (level that cannot be recognized as a CODE39 barcode)

[Evaluation of Water Resistance Adhesion]
With the above-mentioned printer and ink ribbon, printing a bar code (CO) at a temperature of 23 ° C. and a relative humidity of 50%.
DE39). The print was soaked in water at 40 ° C. for 24 hours and then taken out. The surface was wiped off with a rag and a cellophane tape was stuck on the printing screen 10 minutes later. An ANSIGEAD was measured with a bar code verifier and evaluated according to the following evaluation criteria. A, B: good (clear image is obtained) C: acceptable (slight blurring is observed in the bar code, but practical level is maintained) DF: acceptable (bar code is cut off, but practical level N / G: Not possible (level that cannot be recognized as a CODE39 barcode)

(2) Printing suitability "RI-III type printing suitability tester"
(Manufactured by Akira Seisakusho Co., Ltd., trade name) and a printing ink "Best Cure 161 (Sumi)" (trade name, manufactured by T & K TOKA Corporation) were used. [Ink transferability] The film was heated at a temperature of 23 ° C and a relative humidity of 5
After storing for 3 days in an atmosphere of 0%, the above ink was printed on the coated surface of the film so as to have a thickness of 1.5 g / m ² , and the printed surface was subjected to light reflection density “Macbeth densitometer”. The Macbeth concentration was measured using (Cormorgen Co., Ltd. (USA), trade name). Those with a Macbeth density of 1.4 or more are accepted.

[Ink Adhesion] The film was stored for 3 days in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%, and then 1.5 g / in of the ink was applied to the coated surface of the film using the printing machine.
Print to a thickness of m ^2, after irradiation with the place of 10cm was passed once 10 m / min under the Eye Graphics Co., Ltd. halide lamp (80W / cm) 1 lamp, adhesion strength The adhesion strength was measured using a measuring machine “Internal Bond Tester” (trade name, manufactured by Kumagai Riki Kogyo Co., Ltd.). Those having an adhesion strength of 1.4 kg · cm or more are accepted. The principle of measuring the adhesion strength is as follows. An aluminum angle is attached to the upper surface of a sample having cellophane tape attached to the printing surface, and the lower surface is also set in a predetermined holder.
The hammer is swung down from an angle of degrees, and an impact is applied to the aluminum angle to measure the peeling energy at that time.

[Evaluation of Water Resistance Adhesion] After storing the film in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 3 days, 1.5 g / in of the above ink was applied to the coated surface of the film by the above printing machine.
Print to a thickness of m ^2, after irradiation with the place of 10cm was passed once 10 m / min under the Eye Graphics Co., Ltd. halide lamp (80W / cm) 1 lamp, the printed matter Was immersed in water at 23 ° C. for 24 hours and then taken out. The surface moisture was wiped off with a rag, and 10 minutes later, the adhesion strength was measured with the adhesion strength measuring instrument. Those having an adhesion strength of 1.2 kg · cm or more are accepted. (3) Antistatic Property After conditioning the film under an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 2 hours or more, the coated surface of the film was insulated with “DSM-8103” (manufactured by Toa Denpa Kogyo Co., Ltd.). , Trade name). Surface specific resistance value is 1E + 12Ω / □
The following are judged to have good paper supply / discharge properties during printing and printing.

(Examples 2 and 3) Table 1 shows the amount of coating on the support.
A film was obtained and evaluated in the same manner as in Example 1, except for the following changes. Table 1 shows the results. (Examples 4 and 5) Table 1 shows the support of the laminated stretched resin film.
A film was obtained and evaluated in the same manner as in Example 2, except for the following changes. Table 1 shows the results. (Comparative Example 1) A primer layer (B) used in Example 3 of JP-A-8-80684 was applied to both surfaces of a laminated stretched resin film described in Production Example 1 of a support using a roll coater. After drying, the thickness of the coating is 0.06 g /
The film was obtained so as to obtain m ² and evaluated. Table 2 shows the results.

Comparative Examples 2 and 3 Films were obtained and evaluated in the same manner as in Example 1 except that the components of the coating agent and the amount of coating were changed as shown in Table 2. Table 2 shows the results. (Comparative Examples 4 and 5) Table 1 shows the support of the laminated stretched resin film.
A film was obtained and evaluated in the same manner as in Comparative Example 3 except for the following changes. Table 1 shows the results. (Comparative Example 6) A film was obtained and evaluated in the same manner as in Comparative Example 3 except that the coating composition was changed as shown in Table 2. Table 2 shows the results.

Examples 6 to 11 Films were obtained and evaluated in the same manner as in Example 2 except that the coating composition was changed as shown in Table 1. Table 1 shows the results. (Comparative Example 7) A film was obtained and evaluated in the same manner as in Comparative Example 2 except that the coating composition was changed as shown in Table 2. Table 2 shows the results.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

According to the present invention, there is provided a thermal transfer film, particularly a melt thermal transfer film, which is excellent in ink transferability, adhesion and water resistance in a high-temperature and high-humidity environment in a thermal transfer printing, and which can obtain a clear image. In addition, it was possible to provide a thermoplastic resin film excellent in ink transferability, adhesion and water resistance in various printing methods.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a printing apparatus of a fusion heat transfer system.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 thermal transfer ink ribbon 1a heat fusible ink 1b base material 1c dissolved and transferred ink 2 image receiving film 3 print head 4 drum

Continuing on the front page (72) Inventor Kotobuki Tani, 23 Kazu-gun, Kashima-gun, Kashima-gun, Kashima-gun, Oka Oil Chemicals Co., Ltd. Co., Ltd. (72) Inventor Mitsuo Tsuruoka 1-13, Sumida, Hirakata-shi, Osaka Central Rika Kogyo Co., Ltd. F-term (reference) 2H111 AA05 AA26 AA33 CA03 CA12 CA25 CA31 CA44

Claims (10)

[Claims] 1. An image receiving film for printing and thermal transfer, wherein a coating layer comprising the following components (A) and (B) is provided on the surface of a support comprising a thermoplastic resin film. (A) An olefin copolymer (a) having an unsaturated carboxylic acid or an anhydride thereof bonded thereto is prepared from a nonionic surfactant, a nonionic water-soluble polymer, a cationic surfactant, or a cationic water-soluble polymer. An aqueous dispersion obtained by dispersing in water using at least one selected from the group consisting of a dispersant (b), wherein the weight ratio of (a) / (b) per solid is 100/1 to 100 / 30 and an average particle diameter of 5 μm or less. (B) An ethyleneimine adduct of a polyimine-based polymer or polyamine polyamide represented by the following general formula (I). Embedded image (Linear or branched alkyl group wherein, R ¹ and R ² are each independently a hydrogen atom or a range of 1 to 10 carbon atoms, an alkyl group having an alicyclic structure, an aryl group, R ³ Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an allyl group, an alkyl group having an alicyclic structure, an aryl group or a hydroxide thereof, and m is 2 to 6
And n is an integer in the range of 20 to 3000, and these may be used alone or in combination of several kinds. ) 2. The coating layer according to claim 1, wherein the coating layer contains a cross-linking agent of component (C), a water-soluble epoxy-based, isocyanate-based, formalin-based, oxazoline-based, or polyamine polyamide-epichlorohydrin adduct. The image receiving film for printing and thermal transfer according to claim 1. 3. The image receiving film for printing and thermal transfer according to claim 1, wherein the coating layer is a coating layer containing a polymer type antistatic agent as the component (D). 4. The image receiving film for printing and thermal transfer according to claim 1, wherein the support made of a thermoplastic resin film contains an inorganic fine powder and / or an organic filler. 5. The image receiving film for printing and thermal transfer according to claim 1, wherein the support made of a thermoplastic resin film is stretched. 6. An inorganic fine powder having a particle size of 0.1 to 15 μm
The image receiving film for printing and thermal transfer according to claim 4 or 5, which is calcium carbonate. 7. Each of the components of the coating layer on the surface of the support made of a thermoplastic resin film is provided with a coating layer made of the following components (A) and (B).
7. The image receiving film for printing and thermal transfer according to any one of claims 1 to 6. (A) Component 100 parts by weight (B) Component 1 to 25 parts by weight 8. A coating layer comprising the following components (A) to (C), wherein each component of the coating layer on the surface of the support made of a thermoplastic resin film is provided.
7. The image receiving film for printing and thermal transfer according to any one of claims 1 to 6. (A) 100 parts by weight of component (B) 1 to 25 parts by weight of component (C) 1 to 25 parts by weight of component 9. A coating layer comprising the following components (A), (B) and (D), wherein each component of the coating layer on the surface of the support made of a thermoplastic resin film is provided. 7. The image receiving film for printing and thermal transfer according to any one of 3 to 6. (A) 100 parts by weight of component (B) 1 to 25 parts by weight of component (D) 1 to 25 parts by weight of component 10. The method according to claim 3, wherein each component of the coating layer on the surface of the support made of a thermoplastic resin film is provided with a coating layer consisting of the following components (A) to (D). The image receiving film for printing and thermal transfer according to any one of the above. (A) 100 parts by weight of component (B) 1 to 25 parts by weight of component (C) 1 to 25 parts by weight of component (D) 1 to 25 parts by weight of component