JP2001225422A - Coated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin film base material having an ink absorbing layer which simultaneously satisfies melt heat transfer suitability and impact dot suitability and also has offset print suitability. SOLUTION: A thermoplastic resin film having a support (I) as a support (I) and a primer coating layer (II) provided on at least one side, and further comprising at least three kinds of inorganic pigments and a binder resin on the surface. Coated film provided with an ink absorbing layer (III).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated film for printing and printing which has excellent suitability for printer printing, such as fusion thermal transfer and impact dot printing, and also has suitability for offset printing.

[0002]

2. Description of the Related Art A fusing thermal transfer recording system using a thermal transfer ink sheet and a thermal head has been widely used in various printers because of its simple mechanism and easy maintenance, and high quality paper has been used as an ink image receiving sheet. As a support for these thermal transfer image receiving sheets, pulp papermaking, opaque synthetic paper made of a stretched film of a propylene-based resin containing an inorganic fine powder such as calcined clay or calcium carbonate, or a transparent polyethylene terephthalate stretched film, Or, a pigment coating composition containing a white inorganic fine powder and a resin binder is applied to the surface of a transparent polyolefin film, thereby increasing the whiteness and dyeing properties of a pigment coating type synthetic paper. I have. Furthermore, the thermal transfer image receiving sheet is used for labeling drums and containers,
When used as an aerial tag, a pressure-sensitive adhesive is applied to the opposite side (back side) of the support from the image-receiving layer, and is further covered with release paper, and is used when sticking a label or in a luggage of an aerial tag. The release paper is peeled off when sticking, and labels and aviation tags are used by sticking.

[0003] Conventionally, labels are printed in advance with a frame pattern, a ruled line, a product name, an own address and a company name, etc. on the surface of a plastic film or paper, and a lot number,
Record individual information such as date of manufacture and barcode. In recent years, a personal computer has appeared in this information recording, and a fusion heat transfer printer, a wire dot printer, and an ink jet printer are often used for information output. Therefore, it is necessary that a plastic film or paper as a recording medium be easy to print and be easily recorded by each printer. Generally, paper has good printability and is adaptable to various printers, but cannot be used for those requiring water resistance and strength. In that respect, plastic films are excellent, but printing is difficult and some printers cannot record. Among the printing methods, the offset printing method can easily and inexpensively make a plate making cost, and the image gradation is good and clear. Therefore, it is desirable to be able to print on a plastic film by offset printing. However, in offset printing using general ink, drying and curing of the ink are extremely slow, so printing on a plastic film is difficult. In addition, since the structure does not absorb ink, the ink is easily peeled off and the ink adhesion is poor. Although a coated film which has been subjected to a surface treatment suitable for an offset printing method for the purpose of improving such a defect exists, a coated film suitable for a thermal transfer and an impact dot printing method at the same time has not been obtained.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin film substrate having an ink absorbing layer which also has suitability for melt heat transfer, suitability for impact dots, and suitability for offset printing. That is.

[0005]

Means for Solving the Problems According to the present invention, as a result of intensive studies to solve the above problems, a thermoplastic resin film is used as a support (I) and a primer coating layer (II) is provided on at least one surface. The above-mentioned problem is effectively solved by a coated film characterized in that an ink absorbing layer (III) comprising at least three kinds of inorganic pigments and a binder resin is further provided on the surface of the thermoplastic resin film. This led to the completion of the present invention. The present invention relates to a method of preparing a thermoplastic film by combining three types of inorganic pigments having different powder characteristics with a binder resin and a dispersion medium and applying the mixture to the surface of a thermoplastic film. An object of the present invention is to provide a coated film having excellent adhesiveness, ink drying property, rub resistance and the like. The coated film comprises a porous resin film comprising a stretched thermoplastic resin film as a support (I).
A coated film for both printing and printing, wherein the surface of the support (I) is provided with an ink absorbing layer (III) via a primer coating layer (II) having the following composition. I will provide a.

That is, the present invention relates to a primer coating layer (I
I) is (a) the following monomers (i), (ii) and (i)
(ii) a quaternary nitrogen-containing acrylic resin, which is an amphoteric product obtained by quaternizing a tertiary nitrogen atom of a polymer obtained by copolymerizing with a cationizing agent: 100 parts by weight;

Embedded image Wherein R ¹ is H or CH ₃ , R ² is an alkyl group having 1 to 18 carbon atoms, R ³ and R ⁴ are each H
Alternatively, A is an alkyl group having 1 to 2 carbon atoms, and A is an alkylene group having 2 to 6 carbon atoms. ]

(B) Ethyleneimine adducts of polyethyleneimine, poly (ethyleneimine-urea) and polyamine polyamide, or alkyl-modified, alkenyl-modified, benzyl-modified or aliphatic cyclic hydrocarbon-modified thereof A polyimine compound selected from the group consisting of: 20 to 300 parts by weight, and (c) an epichlorohydrin adduct of polyamine polyamide: 20 to 300 parts by weight, are coated with an aqueous solution of a composition, and dried. It is obtained.

The presence of the primer layer (II) on the recording paper makes it difficult for the ink absorbing layer to peel off from the support (I).
The ink absorbing layer (III) preferably contains 50 to 70% by weight of an inorganic pigment and 30 to 50% by weight of a resin binder. The mixing ratio of the inorganic pigment calcium carbonate to kaolin clay and amorphous silica is 2: 1: 2 to 2:
3: 2: oil absorption in the inorganic pigment (JIS-K-510)
1) is 40 ~ 100ml / 100g and 30 ~
50% by weight and specific surface area (BET method) of 280 to 45
A mixture of an inorganic pigment having a silica gel content of 15 to 20% by weight in a range of 0 m ² / g and having a pore volume (BET method) of 0.9 to 1.65 ml / g by an amorphous silica is used. An object of the present invention is to provide a thermoplastic resin film coated with a paint comprising a binder resin and a dispersion medium. In addition, if necessary, an average particle diameter of 5
An organic filler of 10 to 10 μm may be added in an amount of 0.5 to 1% by weight.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the coated film of the present invention having both the suitability for printers such as melt thermal transfer, impact dots and the like and the suitability for offset printing will be described in more detail. (I) Support: The support (I) on which the primer coating layer (II) is provided is made of a thermoplastic resin film such as a propylene-based resin, polyethylene terephthalate, polyimide, or polysulfone resin, or a stretched product thereof. so,
Preferably, it contains an inorganic fine powder and an organic filler, and has an opacity (JIS-P-8138) having fine voids inside the film by stretching of 65% or more, preferably 85% or more, and whiteness. (JIS-P-81
23) is at least 80%, preferably at least 90%.
The stretched porous resin film may be a laminated product of pulp papermaking, plain woven fabric (pongy) or nonwoven fabric (span pond). The porous resin film having fine voids inside the film has a porosity calculated by the following formula (1) of 10 to 60%, preferably 15 to 45%.

[0010]

(Equation 1) A porous resin film is one having a stretched film layer having many fine voids inside the film by stretching a thermoplastic resin film containing an inorganic fine powder or an organic fine powder. Can be

Inorganic fine powder or organic fine powder of 8 to
A biaxially stretched film of a microporous propylene-based resin containing 65% by weight (JP-B-56-55433, U.S. Pat. No. 4,483,965, and U.S. Pat. No. 4,377,616). For example, a biaxially stretched film of a thermoplastic resin film containing 5 to 40% by weight of a white inorganic fine powder is used as a base material layer (A). 0.3 pigment
Lamination of a uniaxially stretched thermoplastic resin film containing 10 to 60% by weight of a white inorganic fine powder selected from calcium carbonate, calcined clay, silica and zeolite as a front and back layer (B, B '). Film. Synthetic paper using a biaxially stretched thermoplastic resin film as a base material, and a uniaxially stretched thermoplastic resin film containing 8 to 65% by weight of inorganic fine powder as a paper-like layer (JP-B-46-4).
0794, JP-A-57-149363, JP-A-57-181829, etc.). As an example of a synthetic paper having a three-layer structure, 5 inorganic fine powders are used.
An inorganic fine powder is applied on both sides of a uniaxially oriented film obtained by unidirectionally stretching a propylene-based resin film containing -40% by weight at a temperature lower than the melting point of the resin.
It is obtained by laminating a molten film of a propylene-based resin containing 65% by weight, and then stretching this laminated film in a direction perpendicular to the above direction. There is a laminated structure in which the paper-like layer is uniaxially oriented and has many fine voids, and the base layer is biaxially oriented.

The type of the inorganic fine powder used for the white inorganic fine powder substrate layer (A) is not particularly limited, but heavy calcium carbonate, light calcium carbonate, clay having an average particle diameter of 0.1 to 10 μm, Silica, talc, titanium oxide, barium sulfate, zinc oxide, magnesium oxide, diatomaceous earth, silicon oxide and the like can be used. The combination of the white inorganic fine powders used for the front and back layers is as described above. In particular, the combination of titanium oxide and calcium carbonate or calcined clay is favorable in terms of economy and weather resistance. Organic Fine Powder The type of the organic fine powder used in the base material layer (A) is not particularly limited, but the average particle diameter after dispersion is 0.1 to 10 μm.
It is preferable to select a different kind of resin from the thermoplastic resin which is the main component of the above. For example, when the thermoplastic resin film is an olefin resin film, as the organic fine powder, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-
6, nylon-6,6, a homopolymer of cyclic olefin, a copolymer of cyclic olefin and ethylene, etc., having a melting point of 120 ° C to 300 ° C or a glass transition temperature of 120 ° C.
C. to 280C. When compounding and kneading these organic fine powders in an olefin resin, it is desirable to add a dispersant, an antioxidant, an ultraviolet stabilizer, a compatibilizer, and the like as necessary. In particular, since the compatibilizer determines the particle form of the organic fine powder, the selection of the amount and type of the compatibilizer is important.

Thermoplastic resin The thermoplastic resin used is, for example, an ethylene resin such as high-density polyethylene or medium-density polyethylene, or a polyolefin resin such as propylene resin, polymethyl-1-pentene, or ethylene-cycloolefin copolymer. resin,
Polyamide resin such as nylon-6, nylon-6,6, nylon-6, T, thermoplastic polyester resin such as polyethylene terephthalate, aliphatic polyester, thermoplastic such as polocarbonate, atactic polystyrene, syndiotactic polystyrene Resins. These may be used in combination of two or more.

[0014] Among these thermoplastic resins, it is preferable to use a non-polar polyolefin resin. Further, among the polyolefin resins, a propylene resin is preferable in terms of chemical resistance, cost, and the like. Such a propylene-based resin is a propylene homopolymer, a polypropylene having isotactic or syndiotactic and various degrees of stereoregularity, and propylene as a main component, and ethylene, butene-1, hexane-
Copolymers with α-olefins such as 1, heptane-1, 4-methylpentene-1 are used. This copolymer is
It may be a binary, ternary or quaternary system, and may be a random copolymer or a block copolymer. Further, it is preferable to blend 2 to 25% by weight of a resin having a lower melting point than that of the propylene homopolymer, for example, a high-density or low-density polyethylene.

[Formation of Resin Film] The method of forming the thermoplastic resin film is not particularly limited, and various known methods can be used. As a specific example, a single-layer or multi-layer film connected to a screw-type extruder can be used. Cast molding, calender molding, rolling molding, inflation molding, extrusion molding of a mixture of a thermoplastic resin and an organic solvent or oil using a T-die or I-die, or a solvent or oil after calender molding , Molding of a thermoplastic resin from a solution and removal of a solvent. In the case of stretching, various known methods can be used, and specific examples include longitudinal stretching using a peripheral speed difference between roll groups, and transverse stretching using a tenter oven.

[Stretching] Various known methods can be used for stretching. As a specific example, in the case of an amorphous resin, the temperature is equal to or higher than the glass transition temperature of the thermoplastic resin to be used, and in the case of a crystalline resin, It can be performed in a known temperature range suitable for each thermoplastic resin from the glass transition point temperature of the non-crystalline part to the melting point of the crystalline part or less, and the longitudinal stretching using the peripheral speed difference of the roll group, using a tenter oven Transverse stretching, rolling, and simultaneous biaxial stretching using a combination of a tenter oven and a linear motor. The stretching ratio is not particularly limited, and is appropriately selected depending on the purpose and the characteristics of the thermoplastic resin to be used. For example, when using a propylene homopolymer or a copolymer thereof as a thermoplastic resin,
In the case of stretching in one direction, it is about 1.2 to 12 times, preferably 2 to 10 times, and in the case of biaxial stretching, the area ratio is 1.
It is 5 to 60 times, preferably 10 to 50 times. When using other thermoplastic resins, when stretched in one direction is 1.2 to 10 times, preferably 2 to 5 times, in the case of biaxial stretching, 1.5 to 20 times in area magnification, Preferably 4
~ 12 times. Further, a heat treatment at a high temperature is performed as necessary.

The stretching temperature is a temperature 2 to 60 ° C. lower than the melting point of the thermoplastic resin used, and 152 to 164 when the resin is a propylene homopolymer (melting point: 155 to 167 ° C.).
110 ° C. for high-density polyethylene (melting point 121-134 ° C.), and 104-115 ° C. for polyethylene terephthalate (melting point 246-252 ° C.). The stretching speed is from 20 to 350 m / min.

[Layer Structure] The thermoplastic resin film may be composed of a single layer or may have a multilayer structure. For example, a single-layer support composed of a polyolefin-based resin film is a polyolefin-based resin 40 to
A resin film comprising a resin composition containing 99.5% by weight and 60 to 0.5% by weight of an inorganic fine powder is heated to a temperature lower than the melting point of the polyolefin resin (preferably 3 to 60).
(Low temperature by 1 ° C.) and can be prepared by stretching in a uniaxial or biaxial direction. In addition, the support having a multilayer structure has a temperature lower than the melting point of the polyolefin resin (preferably 3 to 60 ° C).
Stretching at a low temperature) and laminating a resin film comprising a resin composition containing 25 to 100% by weight of a polyolefin resin and 75 to 0% by weight of an inorganic fine powder on at least one surface of the stretched film. Can be prepared. The surface layer laminated on the stretched film may be an unstretched resin layer.

Particularly preferred supports are calcined clay,
8 to 65% by weight of inorganic fine powder such as calcium carbonate, diatomaceous earth, barium sulfate, silica, titanium oxide, talc, etc.
By uniaxially stretching the contained polyolefin resin film, a number of cracks centering on the inorganic fine powder are formed in the film to form a translucent or opaque film, and the content of the inorganic fine powder is further reduced on the surface. 0.5
A film obtained by laminating a resin composition of about 65% by weight and then stretching this laminated film in a direction perpendicular to the uniaxial stretching direction can be mentioned. The thickness of the support used in the present invention is usually in the range of 20 to 350 μm, preferably 35 to 300 μm.

(II) Primer coating layer: Support (I)
And good adhesion between the ink absorbing layer (III) and
The primer coating layer (II) for improving the paper feeding / discharging property of the coated film comprises (a) the following monomers (i) and (ii):
And a tertiary nitrogen-containing acrylic resin, which is an amphoteric compound obtained by copolymerizing (iii) with a tertiary nitrogen atom of a polymer obtained by copolymerizing the tertiary nitrogen atom with a cationizing agent: 100 parts by weight,

Embedded image Wherein R ¹ is H or CH ₃ , R ² is an alkyl group having 1 to 18 carbon atoms, R ³ and R ⁴ are each H
Alternatively, A is an alkyl group having 1 to 2 carbon atoms, and A is an alkylene group having 2 to 6 carbon atoms. ]

(B) Ethyleneimine adducts of polyethyleneimine, poly (ethyleneimine-urea) and polyaminepolyamide, or alkyl-, alkenyl-, benzyl- or aliphatic cyclic hydrocarbon-modified products thereof. The surface of the support (I) was treated with an aqueous solution of a composition prepared by mixing 20 to 300 parts by weight of a polyimine compound selected from the group consisting of: 20 to 300 parts by weight, and (c) an epichlorohydrin adduct of polyamine polyamide: 20 to 300 parts by weight. Alternatively, it is obtained by applying to the front and back surfaces and drying.

The quaternary nitrogen-containing acrylic resin as the component (a) is a primer component that contributes to antistatic properties, and the one described in JP-B-2-2910 is used. Examples of the monomer (ii) include ethyl acrylate, propyl acrylate, butyl acrylate, capryl acrylate, and stearyl methacrylate. As the hydrophobic vinyl monomer (iii), styrene,
Vinyl chloride or the like can be used.

The polyimine compound as the component (b) is a primer component for enhancing the adhesive force, and is, for example, a polyethyleneimine represented by the following general formula (1) and an ethyleneimine adduct of a polyamine polyamide, or Alkyl-modified, alkenyl-modified, benzyl-modified,
Alternatively, a polyimine compound selected from the group consisting of modified aliphatic cyclic hydrocarbons and poly (ethyleneimine-urea) can be mentioned (Japanese Patent Publication No. 2-2910, JP-A-1-141736).

[0024]

Embedded image [In the formula, R ^{5 to} R ⁸ are each independently H, having 1 carbon atom.
Represents an alkyl group or alkenyl group, an aliphatic cyclic hydrocarbon group or a benzyl group, m is 0 to 300,
n, p and q each represent a numerical value of 1 to 300. ]

The polyamine polyamide / epichlorohydrin adduct of the component (c) is also a primer for strengthening the adhesive force, such as a polyamide comprising a saturated dibasic carboxylic acid having 3 to 10 carbon atoms and a polyalkylene polyamine. It is a water-soluble, cationic thermosetting resin obtained by reacting with epichlorohydrin. The details of such a thermosetting resin are described in JP-B-35-3547. Specific examples of the above-mentioned saturated dibasic carboxylic acid having 3 to 10 carbon atoms include dicarboxylic acids having 4 to 8 carbon atoms, particularly adipic acid. Further, specific examples of the polyalkylene polyamine include polyethylene polyamines, particularly ethylene diamine, diethylene triamine, and triethylene tetramine, and among them, diethylene triamine.

In addition to these components, sodium carbonate, sulfuric acid
Sodium, sodium sulfite, sodium thiosulfate
, Barium hydroxide, sodium metasilicate, sodium pyrophosphate
(Na_FourP_TwoO₇・ 10H_TwoO), tripolyphosphate
(Na_FiveP_ThreeO_Ten・ 6H_TwoO), sodium phosphate monobasic
(NaH_TwoPO_Four・ 2H_TwoO), potassium alum (KAl (S
O _Four)_Two・ 12H_TwoO), ammonium alum (Al (N
H_Four) (SO_Four)_Two・ 12H_TwoO) and other inorganic compounds
Can be combined. These (a), (b) and (c)
The amount is usually 0.1 to 10% by weight of solid content,
Preferably, an aqueous solution (coating agent) having a concentration of 0.1 to 5% by weight
Used as Further, propylene as the support (I)
The amount applied to the resin film is generally 0.0
05-10g / m^Two, Preferably 0.02 to 5 g / m^Two
Range. As a method of applying the primer,
Normal blades, blades, air knives, size presses, etc.
A coating method can be adopted.

The mixing ratio of the components (a), (b) and (c) is such that the polyimine compound (b) is 20 to 30 parts by weight based on 100 parts by weight of the nitrogen-containing acrylic resin (a).
0 parts by weight, preferably 20 to 100 parts by weight, wherein the epichlorohydrin adduct of the polyamine polyamide of (c) is 20 parts by weight.
The range is from 300 to 300 parts by weight, preferably from 35 to 200 parts by weight. By maintaining these compositions, the antistatic property of the thermoplastic resin film is maintained, and the adhesion between the ink absorbing layer (III) and the support (I) is high through the primer coating layer (II). Become.

(III) Ink absorbing layer: As the binder resin in the present invention, an acrylate polymer,
It is characterized by using an acetoacetylated modified vinyl acetate copolymer. Styrene / acrylic acid alkyl ester copolymer, polyvinyl alcohol, ethylene / vinyl alcohol copolymer containing silanol group, polyvinylpyrrolidone, ethylene / vinyl acetate copolymer, methyl ethyl cellulose, sodium polyacrylate, starch, polyethylene polyamine, polyester , Polyacrylamide, vinylpyrrolidone / vinyl acetate copolymer, ester / ether-based urethane resin, ester-based urethane resin, etc. as a binder, and light calcium carbonate,
It contains kaolin clay, amorphous silica and the like, and may contain a plastic pigment such as a titanium oxide, a zinc oxide, a cross-linked polymethyl methacrylate acrylic resin filler, or a hollow polystyrene filler, if necessary. Further, an ink setting agent, an ultraviolet absorber, a surfactant and the like are blended as required. The binder resin is used in the range of 30 to 50% by weight, preferably 40 to 50% by weight, and the inorganic pigment is used in the range of 50 to 70% by weight, preferably 50 to 60% by weight.

It is preferable to use two kinds of inorganic pigments in combination with calcium carbonate and kaolin clay in order to improve ink receptivity. The oil absorption is preferably from 40 to 100 ml / 100 g according to JIS K-5101. , 40
30 to 50% by weight of 〜60 ml / 100 g
(60 to 72% by weight in the inorganic pigment) and the specific surface area (B
ET method) is in the range of 280 to 450 m ² / g, and the pore volume (BET method) is 0.9 ml / g to 1.65 ml / g.
g of amorphous silica produced by a gel method of 0.9 ml / g to 1.20 ml / g, preferably 15 to 20% by weight (28 to 40% by weight in the inorganic pigment). . That is, in the present invention, it is desirable to use calcium carbonate, kaolin clay and amorphous silica produced by the gel method in combination in order to obtain a strong and suitable surface for ink absorption and dense voids. If the oil absorption of calcium carbonate and kaolin clay in the ink absorbing layer is 40 ml / 100 g or less, ink receptivity will be poor, and if it exceeds 100 ml / 100 g, ink adhesion and friction resistance will be poor. The specific surface area (BET method) is in the range of 280 to 450 m ² / g, and the pore volume (BET method) is 0.9 ml / g to 1.65.
Amorphous silica produced by the ml / g gel method itself has a certain degree of ink absorption, and hastens ink drying and forms a strong ink absorbing layer to improve ink adhesion. When the pore volume is 0.9 ml / g or less, the voids formed by the secondary particles are reduced, and the ink absorbing ability is reduced. On the other hand, if the pore volume exceeds 1.65 ml / g, the primary particles are large and relatively loose secondary particles may be formed, so that the particle size becomes large and a dense and strong absorbent layer cannot be formed. In addition, ink adhesion and friction resistance are poor, and the transfer density is hard to increase.

Examples of the ink setting agent include a tertiary ammonium salt of polyethyleneimine, an acrylic copolymer containing a quaternary ammonium group as a copolymerization component, and an epichlorohydrin adduct of polyamine polyamide. The ink-absorbing layer is formed on the support by applying a coating composition containing the above components to the primer coating layer (II) formed on the surface of the support (I) in an amount of 0.5 to 50 g / m ² , preferably. Is 1-3
It is obtained by applying at a ratio in the range of 0 g / m ² (solid content) and drying. To form an ink absorbing layer on a support, a Meyer bar method, a gravure roll method,
What is necessary is just to apply by well-known coating methods, such as a reverse roll method, a blade method, a knife method, an air knife method, a slit die method, and a gate roll method, and to dry and solidify. If necessary, the surface of the dried coating layer is subjected to a super calender treatment to smooth the coating layer (ink absorbing layer).

Melt thermal transfer sheet: The above ink absorbing layer (I
II) As a molten heat transfer sheet (ink ribbon) used to form an image by transferring a transfer ink to the transfer ink,
Various things can be used. Specifically, a binder component, a coloring component, and the like as main components, as necessary,
It is obtained by laminating a composition comprising a softener, a plasticizer, a melting point regulator, a leveling agent, a dispersant and the like as additive components on a base material layer such as a polyester film.
As specific examples of the main component, known waxes such as paraffin wax, carnauba wax, and ester wax as binder components and various polymers having a low melting point are useful, and carbon black and various organics as coloring components are useful. Inorganic pigments or dyes are useful.

Melt transfer printer: As shown in FIG. 1, the melt transfer system employs a thermal transfer ink ribbon (1) comprising a heat fusible ink (5) and a substrate (4) supporting the ink.
And a coated film (2) are sandwiched between a platen roll (9) and a heat source (thermal head) (3), and heat is generated by a heat source (3) that can be controlled by an electric signal such as a thermal head. When the molten ink (5) is heated, the dissolved ink is directly transferred as the ink (5 ') transferred to the coated film (2).

[0033]

The present invention will be described in more detail with reference to the following examples. Production Example of Support: (Example 1) (1) Mixture of 72% by weight of propylene homopolymer having MFR of 0.8 g / 10 min, 15% by weight of high-density polyethylene, and 13% by weight of calcium carbonate powder having a particle size of 1.5 μm ( A) was melt-kneaded with an extruder, extruded from a die into a sheet, and cooled by a cooling device to obtain a non-stretched sheet. After heating this sheet to 145 ° C., it was stretched 5 times in the machine direction.

(2) A composition (B) for a surface layer obtained by mixing 45% by weight of calcium carbonate having an average particle size of 1.5 μm with 55% by weight of a propylene homopolymer having an MFR of 4.0 g / 10 minutes was set at 270 ° C. The sheet kneaded and extruded with an extruder is laminated on both sides of the 5-fold stretched sheet obtained in the step (1), and then cooled to a temperature of 60 ° C.
The film was heated to a temperature of ° C. and stretched 7.5 times in the transverse direction with a tenter to obtain a three-layer film. (3) The surface of the three-layer laminated film is subjected to a corona discharge treatment, and the thickness of each film of (B) / (A) / (B) is 15
A laminate having a three-layer structure of / 50/15 (80 μm in total) microns was obtained. The physical properties of the obtained film are as follows: porosity 32%,
Density 0.77 g / cm ³ , whiteness 95%, opacity 90
%Met.

(Example 2) (1) 80% by weight of propylene homopolymer having an MFR of 1.2 g / 10 minutes, 3.5% by weight of high-density polyethylene, 16% by weight of calcium carbonate having an average particle size of 1.5 μm, and titanium white 0 2.5% by weight of the composition (A) at 270 ° C.
The resin mixture melt-kneaded with an extruder set to
55 g of a polypropylene homopolymer of 4.0 g / 10 min, 44.5 wt% of calcium carbonate having an average particle size of 1.5 μm and anatase-type titanium oxide having an average particle size of 0.8 μm.
A resin mixture obtained by melt-kneading the composition (B) mixed with 5% by weight of the composition (B) by an extruder set at 270 ° C. is extruded by one main extruder and two sub-extruders, and they are combined to form a resin mixture. It was extruded with two T-die heads to obtain a three-layer sheet-like laminated film having a three-layer structure.

(2) Next, after cooling the three-layered laminated film to 60 ° C. with a cooling roller,
After heating to a temperature of 0 ° C., stretching in the longitudinal direction, stretching the film 7 times in the longitudinal direction by annealing, heating again to a temperature of 160 ° C., and stretching in the transverse direction using a tenter. Stretched 7 times, cooled to a temperature of 65 ° C., and subjected to corona discharge treatment.
A synthetic paper having a three-layer structure (B / A / B / = 20/80/20) was obtained. The physical properties of this film were as follows: porosity 30%, density 0.79 g / cm ³ , whiteness 95%, opacity 89%,
The gloss was 91%.

Production Example of Primer Coating Agent (Example 3) A coating agent having the following composition was used. (A) 0.5% by weight of a terpolymer containing the following units:

Embedded image

(B) 0.3% by weight of butylated modified polyethyleneimine (c) 0.5% by weight of epichlorohydrin adduct of water-soluble polyamine polyamide (“WS-570: trade name” manufactured by Nippon PMC Co., Ltd.) ) Water residue

Production Example of Ink Absorbing Layer Coating Agent (Example 4) A coating agent having the following solid component ratio was used. The coating agent is dispersed in water, and the solid component concentration is adjusted to 30 with water.
% By weight. The following pigments and resin binders were used. Light calcium carbonate: Oil absorption: 44 ml / 100 g (manufactured by Shiraishi Industry Co., Ltd .: Brilliant S-15) 20 parts by weight Kaolin clay: Oil absorption: 50 ml / 100 g (manufactured by Engelhardt: UW-90) 10 Parts by weight Gel method silica: Pore volume: 0.9 ml / g (Grace Japan: WSSG-1U) 19 parts by weight Organic fine powder: Toshin Chemical Co., Ltd. Crosslinked PMMA 1 part by weight Binder: acrylic ester Resin emulsion (“Movinyl 735” manufactured by Clariant Polymer Co., Ltd.) 45 parts by weight Polyvinyl alcohol: 5 parts by weight Gosefimer Z-100 manufactured by Nippon Synthetic Chemical Company

Example 1 On the front and back surfaces of the film of Example 1,
Each of the primer coating layers of Example 3 was 0.2 g / m2 in solid amount.
^It was applied so as to be ² and dried at 65 ° C. On one surface of the dried primer layer, an ink absorbing layer coating composition having the composition shown in Example 4 was applied in an amount such that the solid content became 5.0 g / m ^2, and dried at 110 ° C. to form an ink absorbing layer. A coated film having a structure of / primer coating layer / synthetic paper / primer coating layer was obtained.

(1) Coating adhesion strength: Kumagaya Riki Kogyo Co., Ltd.
The surface strength of the coated surface was measured with an internal bond tester. Table 1 shows the results. <1> Suitability for fusion heat transfer printer On the coated surface of the coated film, a printing device “Barcode Printer B-30-S5” manufactured by TEC Co., Ltd. and a hot melt ink ribbon “WAX B110” manufactured by Ricoh Co., Ltd.
A "or" Resin type B110C "(trade name), 35
Bar code printing was performed in a constant temperature room at 85 ° C. and 85% RH. Table 1 shows the results.

(Evaluation) (1) Print evaluation: The appearance of the print was visually evaluated as follows. ：: A clear image can be obtained in a bar code, a solid, and a character portion. Δ: Although blurring and the like are observed in the character portion, the practical level is maintained. X: Line break occurs in bar code printing and the like. .

(2) Ink Adhesion: Nichiban Co., Ltd. adhesive tape trade name "Cellotape LP-2"
Paste 4 ”and press lightly with a gauze in the shape of a bead.
After repeated rubbing, the tape was peeled off by 180 degrees to evaluate the adhesive strength. Table 1 shows the results. The adhesion of the ink was evaluated as follows. A: No ink is peeled off. ：: The ink is slightly peeled off, but there is no practical problem. Δ: Partially missing. (Less than 25%) ×: The peeled portion was 25% or more. (Unreadable)

<2> Suitability of Dot Printer An impact dot printing printer “PC-PR” manufactured by NEC Corporation was applied to the coated surface of the coated film.
101/63 ”and NEC Corporation ribbon“ PC201 ”
G-01 ". Table 1 shows the results. (1) The printing characteristics were visually evaluated as follows. ◎: High printing density, clear printing without bleeding, print stains, etc. ：: Clear printing is possible without occurrence of ink bleeding, printing stains, etc. Δ: There is slight ink bleeding and printing stain. X: There are many ink bleeds and printing stains. (2) After one minute, the image printed in (1) was rubbed with tissue paper, and the drying property (fixing property) of the ink was visually evaluated as follows. ◎: No set-off on tissue paper, no soiling,
Clear print remains. ：: Offset slightly to tissue paper, but clear printing remains. Δ: Slight soiling occurs. ×: Smearing occurs, making it difficult to read.

<3> Suitability for Offset Printing The offset printing machine used was a printing machine RI tester manufactured by Akira Seisakusho Co., Ltd., and the printing ink used was oil-based ink “Best SP / Black” (trade name) manufactured by T & K TOKA CORPORATION. The color was changed (amount of 1.5 g / m ² ). Table 1 shows the results. (1) Ink adhesion: After the color-changed product was allowed to stand for one day, the ink adhesion strength of the printed surface was measured using an internal bond tester of Kumagaya Riki Kogyo Co., Ltd. Table 1 shows the results. (2) Ink drying property Immediately after the color change, Toyo Seiki's ink drying tester (Choyokai ceremony)
And the evaluation surface was visually evaluated as follows. Table 1 shows the results. ：: Ink transfer was small, and no ink transfer occurred in 1 to 2 hours. ：: Ink transfer is small and no ink transfer occurs in 3 to 4 hours. Δ: Ink transfer did not occur in 3 to 4 hours. X: Ink transfer is large and no ink transfer occurs after 4 hours or more.

<4> Evaluation of friction resistance Friction tester "FR-2" (trade name) manufactured by Suga Test Instruments Co., Ltd.
Apply a white cotton cloth moistened with water to the sliding surface of the friction element.
Place the frictional sliding surface on the printing surface of the sheet that has undergone color change during offset printing aptitude on the table, and further 200 g.
And then rubbed 500 times, and then the stain on the printed surface and the stain on the white cotton cloth were visually evaluated as follows. Table 1 shows the results. ：: There is almost no change on both the printed surface and the white cotton cloth. ：: Only the white cotton cloth is stained. Δ: The printing surface is slightly stained, and the white cotton cloth is slightly stained. ×: Both the printing surface and the white cotton cloth are stained.

Comparative Example 1 A coated film was manufactured and evaluated in the same manner as in Example 1, except that an ink absorbing layer was directly provided on the film without providing a primer coating layer. Table 1 shows the results. (Examples 2 to 4, Comparative Examples 2 to 7) Except that the film was changed as shown in Table 1, both the coating amount of the primer coating agent and the coating amount of the ink absorbing layer were the same as in Example 1 except for the ink absorption. A coated film was produced and evaluated in the same manner except that the composition of the layer was changed to the composition shown in Table 1 (shown below). The pigment used in Comparative Example 5 was light calcium carbonate (manufactured by Okutama Kogyo Co., Ltd., TM-123CS), oil absorption: 120 ml /
100 g. The pigment used in Comparative Example 6 was precipitated silica (P-527, manufactured by Mizusawa Chemical), pore volume:
0.13 ml / g. The resin binder used in Comparative Example 7 was an ester-based urethane resin emulsion (Superflex 410, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Table 1 shows the results.

[Table 1]

[0048]

According to the present invention, the suitability for a fusion heat transfer printer is good, the suitability for a dot printer, and also the suitability for offset printing, and various printing methods (letterpress, gravure, flexo, screen, electrophotography).
It was possible to provide a coated film that can handle the problems. Printed and printed paper is excellent in water resistance, and thus is useful as a label for drums and containers.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a fusion heat transfer system.

[Description of Signs] 1 Thermal transfer ink ribbon 2 Coated film 3 Heat source such as thermal head 4 Substrate 5 Thermal fusible ink 5 'Transferred ink 6 Ink absorption layer 7 Primer layer 8 Support 9 Platen roll

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B41M 5/26 BF

Claims (9)

[Claims] 1. A thermoplastic resin film having a thermoplastic resin film as a support (I) and a primer coating layer (II) provided on at least one surface, and further having at least three kinds of inorganic pigments and a binder resin on the surface thereof. A coated film provided with an ink absorbing layer (III) comprising: 2. The ink absorbing layer (III) contains 50 to 70% by weight of an inorganic pigment and 30 to 50% by weight of a binder resin.
The coated film according to claim 1, wherein the compounding ratio of calcium carbonate, which is an inorganic pigment, and kaolin clay and amorphous silica produced by a gel method is 2: 1: 2 to 2: 3: 2. . 3. The oil absorption (JIS-K-5101) of the inorganic pigments calcium carbonate and kaolin clay is 40 to 40.
30 to 50% by weight of 100 ml / 100 g,
The amorphous silica in the inorganic pigment has a specific surface area (BET).
(Method) is in the range of 280 to 450 m ² / g and the pore volume (BET method) is in the range of 0.9 to 1.65 ml / g. %. 4. The coated film according to claim 1, wherein the binder resin is an acrylate resin. 5. The coated ink according to claim 1, wherein the ink-absorbing layer is formed on the support (I) at least on one side at a rate of 0.5 to 50 g / m ^2. the film. 6. The coated film according to claim 1, wherein the thermoplastic resin film as the support (I) comprises a porous resin film. 7. The opacity of the porous resin film is 65 to 65.
The whiteness is 100 to 100% and the whiteness is 80 to 100%.
7. The coated film according to any one of 6. 8. The coated film according to claim 1, wherein the porous resin film is stretched. 9. The primer coating layer (II) comprises: (a) the following monomers (i), (ii) and (iii):
Acrylic resin containing quaternary nitrogen, which is an amphoteric compound obtained by copolymerizing a tertiary nitrogen atom of a polymer obtained by copolymerizing the tertiary nitrogen atom with a cationizing agent: 100 parts by weight: Wherein R ¹ is H or CH ₃ , R ² is an alkyl group having 1 to 18 carbon atoms, R ³ and R ⁴ are each H
Alternatively, A is an alkyl group having 1 to 2 carbon atoms, and A is an alkylene group having 2 to 6 carbon atoms. (B) an ethyleneimine adduct of polyethyleneimine, poly (ethyleneimine-urea) and polyamine polyamide, or an alkyl-modified, alkenyl-modified, benzyl-modified or aliphatic cyclic hydrocarbon-modified product thereof; Polyimine compounds selected from the group: 20
An aqueous solution of a composition blended in a ratio of 20 to 300 parts by weight: (c) an epichlorohydrin adduct of a polyamine polyamide: (c) 20 to 300 parts by weight, which is obtained by applying and drying.
9. The coated film according to any one of items 1 to 8.