JP4344570B2 - Fused thermal transfer recording paper - Google Patents

Description

  The present invention relates to a melt thermal transfer recording sheet. More specifically, the transferability and adhesion of the ink are excellent in various printing methods, and particularly the transferability, adhesion, water resistance, and solvent resistance of the hot melt ink when using a melt thermal transfer recording apparatus. The present invention relates to a melt thermal transfer recording sheet.

  As the image recording method, there are a sublimation thermal transfer method, a melt thermal transfer method, an electrophotographic method, an electrostatic recording method, and the like, which are widely used for image and information recording. These use thermal energy for transfer and image fixing and adhesion. For example, the color material is transferred from the ink ribbon to the recording medium by pressing the ink medium via the ink ribbon, or the toner is transferred to the recording medium at a high temperature. It is heated and adhered by a roll or light.

  Among them, the heat transfer method generally used for recording information such as a barcode is a heat transfer ink ribbon composed of a heat-meltable ink and a substrate that supports the ink and a recording paper, a thermal head that is a heat source, etc. The heat-meltable ink in the thermal transfer ink ribbon is heated to transfer the dissolved ink directly to the recording paper by sandwiching it between the print head equipped with the drum and the drum and controlling the thermal head with an electrical signal To do.

  The recording paper used for such a melt heat transfer system often has a layer or primer layer made of a polyester resin or epoxy resin having good adhesion to the heat melt ink on the surface.

  These recording papers are generally synthetic paper (for example, see Patent Documents 1 to 15) made of a stretched film of a propylene-based resin containing inorganic fine powder such as calcined clay or calcium carbonate, a stretched polyethylene terephthalate film, or a polyolefin-based resin. Film. In addition, the surface of these films is coated with a pigment coating agent containing an inorganic fine powder such as silica or calcium carbonate and a binder as an image receiving layer, so that the whiteness, dyeability and printability are improved. (For example, Patent Documents 16 to 23).

  In addition, as a recording paper, a stretched film of a polyolefin resin containing inorganic fine powder, which is coated with a water-soluble primer of a nitrogen-containing polymer compound for imparting various printability and antistatic performance as an image receiving layer. It has been proposed (for example, Patent Document 24). However, when this recording paper is used, the water-based primer layer that absorbs moisture absorbs moisture in a high-temperature and high-humidity environment. There have been problems such as line breakage and image blurring.

  In order to remedy this problem, a recording was made by applying a water-soluble primer of a nitrogen-containing polymer compound to a molded microporous film made of a stretched polyolefin resin film containing finer inorganic fine powder. It has been reported that a clear image can be obtained even in a high temperature and high humidity environment by using paper (for example, Patent Documents 25 to 27). However, it has been found that printed matter printed on these recording materials has a problem of poor ink adhesion after being placed in a high temperature and high humidity environment for a long time.

  In order to further improve this problem, it has been reported that by providing a specific image-receiving layer, the adhesion of ink is improved even for a printed matter placed for a long time in a high temperature and high humidity environment. (For example, patent document 28).

However, when bar code printing is performed on the recording paper described in Patent Document 28 using a fusion thermal transfer recording apparatus and used for information management of a drum can or container containing an organic solvent, the content of the organic solvent is reduced. Due to leakage, the heat-meltable ink or the image receiving layer is dissolved by the organic solvent, and the printed information is peeled off, which causes a problem in information management. For this reason, the demand for improvement from the market was high.
Japanese Patent Laid-Open No. 62-290790 JP 63-152029 A Japanese Patent Laid-Open No. 62-193836 JP 63-222891 A Japanese Unexamined Patent Publication No. 01-49640 Japanese Patent Laid-Open No. 01-95097 JP 05-305780 A Japanese Patent Laid-Open No. 06-79979 JP 07-25174 A Japanese Patent Laid-Open No. 07-76186 Japanese Patent Application Laid-Open No. 07-179078 Japanese Patent Application Laid-Open No. 07-232397 Japanese Patent Laid-Open No. 08-20169 JP-A-11-334228 JP 2000-155941 A Japanese Patent Laid-Open No. 09-86057 JP 09-267571 A Japanese Patent Laid-Open No. 10-264543 JP 2000-190433 A JP 2000-218950 A JP 2000-247048 A JP 2001-18542 A JP 2001-225422 A JP-A-62-148292 JP-A-8-80684 JP-A-9-76647 JP-A-9-295466 JP 2001-219661 A

  Accordingly, the present invention has been made to solve the problem of providing a melt thermal transfer recording sheet that does not interfere with information management even when it is rubbed in a state exposed to an organic solvent and is excellent in various printability.

As a result of continuing investigations in view of such problems of the prior art, the inventors of the present invention are melt thermal transfer recording sheets made of a stretched resin film stretched in at least one direction, and are resin stretched according to JIS-B-0601-2001. The center line average roughness (Ra) of the surface of the film is 0.4 to 2.5 μm, and the outermost layer of the stretched resin film is 30 to 75% by weight of inorganic fine powder and / or organic filler, JIS-K Includes a total of 70 to 25% by weight of a thermoplastic resin having a Vicat softening point of 140 ° C. or less as measured in −7206-1999 and a polyolefin resin having a Vicat softening point of 140 ° C. or more as measured in JIS-K-7206-1999 , outermost layer, with respect to the polyolefin-based resin 100 parts by weight, more 900 wt than 75 parts by weight of thermoplastic resin of the resin stretched film Melt thermal transfer recording sheet of the present invention which comprises in the following amounts were found to overcome the problems.

  By incorporating an inorganic fine powder and / or an organic filler into a polyolefin resin and stretching in at least one direction, fine irregularities are produced on the surface, and fine voids (microvoids) are also produced inside. Further, by containing a thermoplastic resin having a Vicat softening point of 140 ° C. or lower, the thermal transfer ink melted by the heat and pressure of the thermal head enters the irregularities and voids when performing melt thermal transfer printing, and then the surface thermoplastic resin However, the thermal transfer ink is contained inside by plasticizing and deforming and covering the surface layer of these irregularities and voids, and as a result, the ink does not melt even after being rubbed in an exposed state to an organic solvent.

  These phenomena are the ratio of the area where the surface of the stretched resin film of the present invention was coated after heating the surface of the stretched resin film of the present invention at a temperature of 110 ° C. and a printing speed of 3 inches / second using a melt thermal transfer recording apparatus. It can be confirmed from the fact that is 35% or more.

  The polyolefin resin is preferably a propylene resin having a Vicat softening point exceeding 140 ° C.

  Further, these films preferably contain a filler dispersant, and preferably contain more than 0% by weight and 20% by weight or less of the dispersant.

  Moreover, in order to improve various printability on the film surface, it is preferable to provide a coating layer made of an ethyleneimine adduct of a polyimine copolymer represented by the following general formula (a) or polyamine polyamide.

（式中、Ｒ¹とＲ²はそれぞれ独立して水素原子、炭素数１〜１０の範囲の直鎖、分岐状もしくは脂環式構造を有するアルキル基、またはアリール基であり、Ｒ³は水素原子、または炭素数１〜２０の範囲のアルキル基、アリル基、脂環式構造を有するアルキル基、アリール基もしくはこれらの水酸化物であり、ｍは２〜６の範囲の整数であり、ｎは２０〜３０００の範囲の整数であり、ｍ×ｎ個のＲ¹ ならびにＲ² 、およびｎ個のＲ³は、それぞれ互いに同一であっても異なっていてもよい。）
さらに上記塗布層が水溶性のエポキシ系架橋剤、イソシアネート系架橋剤、ホルマリン系架橋剤、オキサゾリン系架橋剤、ポリアミンポリアミドのエピクロルヒドリン付加物の架橋剤、およびポリマー型帯電防止剤を含有することが好ましい。

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having a linear, branched or alicyclic structure having 1 to 10 carbon atoms, or an aryl group, and R ³ is hydrogen. An atom, 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, m is an integer in the range of 2 to 6, and n Is an integer in the range of 20 to 3000, and m × n R ¹ and R ² and n R ³ may be the same as or different from each other.
Further, the coating layer preferably contains a water-soluble epoxy crosslinking agent, an isocyanate crosslinking agent, a formalin crosslinking agent, an oxazoline crosslinking agent, a crosslinking agent of an epichlorohydrin addition product of polyamine polyamide, and a polymer type antistatic agent. .

  These melt heat transfer recording papers can be printed in various ways, and can be laminated with other resin films or materials other than resin films, or laminated with release paper via an adhesive to produce a base paper for labels It can also be used as

  Furthermore, the present invention also includes a recorded matter using the above-described melt thermal transfer recording paper, laminated body, or label base paper.

  The melt thermal transfer recording paper of the present invention is excellent not only in transferability, adhesion and water resistance of the hot melt ink, but also in solvent abrasion resistance. In particular, even if it is rubbed in a state exposed to an organic solvent, information management is not hindered and various printability is excellent. Because of such characteristics, the melt thermal transfer recording paper of the present invention can be used in a wide range of applications.

BEST MODE FOR CARRYING OUT THE INVENTION

  The melt thermal transfer recording paper of the present invention will be described in detail below. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[1] Melt Thermal Transfer Recording Paper (1) Layer Configuration The melt thermal transfer recording paper of the present invention may be a single layer or a multilayer, and may have a base layer and a surface layer, or a two-layer structure. Even a three-layer structure in which a surface layer exists on the front and back surfaces may be a multilayer structure in which another resin film layer exists between the base layer and the surface layer. In the three-layer structure, the number of stretching axes is 1 axis / 1 axis / 1 axis, 1 axis / 1 axis / 2 axis, 1 axis / 2 axis / 1 axis, 2 axis / 1 axis / 1 axis, 1 axis / Two axes / 2 axes, 2 axes / 2 axes / 1 axis, 2 axes / 2 axes / 2 axes, and the like can be mentioned. In the case of a layer structure having more than that, the number of stretching axes can be arbitrarily combined.

  The melt thermal transfer recording paper of the present invention may be laminated with other thermoplastic resin film, pulp paper, plain woven fabric (pongy) or non-woven fabric (spunbond), and if necessary, an adhesive layer, Release paper may be provided. In that case, the stretched resin film may be the outermost layer.

(2) Thermoplastic resin having a Vicat softening point of 140 ° C. or lower The thermoplastic resin having a Vicat softening point of 140 ° C. or lower measured according to JIS-K-7206-1999 used in the present invention preferably has a Vicat softening point of 50 It is -130 degreeC, More preferably, it is 60-125 degreeC. The stretched resin film constituting the melt thermal transfer recording paper of the present invention contains the thermoplastic resin in an amount of more than 75 parts by weight and not more than 900 parts by weight, preferably 100 parts by weight to 700 parts by weight, based on 100 parts by weight of the polyolefin resin. Contained, more preferably more than 100 parts by weight and 400 parts by weight or less.

  When the Vicat softening point exceeds 140 ° C., the plastic surface deformation of the film surface due to the heat of the thermal head is not sufficient when performing melt thermal transfer printing, and the ratio of the coated area of the stretched film surface becomes small. For this reason, the thermal transfer ink is easily dissolved after rubbing with a solvent, and the object of the present invention cannot be achieved.

  Further, when the content of these thermoplastic resins is less than 75 parts by weight with respect to 100 parts by weight of the polyolefin-based resin, the amount of the resin that is similarly plastically deformed is small, and the ratio of the surface coverage area of the film is small. After that, the thermal transfer ink is likely to melt. In addition, when the thermoplastic resin content exceeds 900 parts by weight with respect to 100 parts by weight of the polyolefin resin, a stretched film is formed because it sticks to a manufacturing device such as a roll or a tenter or the sheet breaks during stretching. Becomes difficult.

As a thermoplastic resin having a Vicat softening point of 140 ° C. or less, a random propylene copolymer containing ethylene or butene as a comonomer, a high density polyethylene having a density of 0.940 to 0.970 g / cm ³ , and a density of 0.8. 900~0.935g / cm ³ low-density polyethylene, linear low density polyethylene having a density of 0.880~0.940g / cm ^3, a polyethylene-based resins such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid Acrylic acids such as copolymers, ethylene / acrylic acid alkyl ester copolymers, ethylene / methacrylic acid alkyl ester copolymers, metal salts of ethylene / methacrylic acid copolymers (Zn, Al, Li, K, Na, etc.) Resin, ionomer, polybutene-1, polybutadiene, methacrylic resin, etc. can be used. Among these, high-density polyethylene, low-density polyethylene, random polypropylene copolymer, and acrylic resin are preferable from the viewpoint of chemical resistance and cost, and high-density polyethylene and low-density polyethylene are particularly preferable.

(3) Polyolefin-based resin As the polyolefin-based resin used in the present invention, it is preferable to use a propylene-based resin having a Vicat softening point exceeding 140 ° C. measured according to JIS-K-7206-1999. By using a propylene-based resin having a Vicat softening point exceeding 140 ° C., irregularities and voids are easily formed on the stretched film surface, the surface roughness becomes moderately large, and the thermal transfer ink is melted by heating the thermal head. There is an advantage that there are more parts to enter.

  As the propylene-based resin, an isotactic polymer and a syndiotactic polymer obtained by homopolymerizing propylene are preferable. In addition, the main component is polypropylene having various stereoregularities obtained by copolymerizing propylene with an α-olefin such as ethylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene. Copolymers can also be used. The copolymer may be a binary system or a multi-system of ternary system or higher. One of these polyolefin resins may be selected and used alone, or two or more may be selected and used in combination.

(4) Inorganic fine powder The inorganic fine powder used in the present invention has an average particle size of usually 0.05 to 10 μm, preferably 0.1 to 7 μm, more preferably 0.3 μm to 5 μm, and particularly preferably 0.4 μm. One having a thickness of ˜2.5 μm, most preferably 0.5 μm to 1.5 μm can be used. When the average particle size is less than 0.05 μm, the inorganic fine powder does not uniformly disperse during the melt-kneading with the thermoplastic resin and the polyolefin resin having a Vicat softening point of 140 ° C. or less, or the inorganic fine powder is secondary agglomerated. In some cases, moisture foaming may occur due to the influence of adsorbed moisture. On the other hand, if the average particle size exceeds 10 μm, the strength of the film tends to be lowered, and the transfer concentration of the printing ink or the hot-melt ink tends to be lowered. Specifically, calcium carbonate, aluminosilicate, alumina, calcined clay, silica, diatomaceous earth, talc, titanium oxide, barium sulfate, etc. can be used as the inorganic fine powder. Among these, it is preferable to use calcium carbonate from the viewpoint of cost. Among calcium carbonates, those having a small average particle size and a small particle size distribution and having coarse particles removed (for example, “Caltex 7” manufactured by Maruo Calcium Co., Ltd.) have a transfer concentration of printing ink. It is preferable in terms of improvement.

  The particle size of the inorganic fine powder used in the present invention is 50% of the cumulative particle size measured by a particle measuring device, a laser diffraction particle measuring device “Microtrack” (trade name, manufactured by Nikkiso Co., Ltd.). % Particle size).

(5) Organic filler As the organic filler used in the present invention, those having an average particle diameter after dispersion of usually 0.05 to 10 μm, preferably 0.1 to 7 μm, more preferably 0.3 to 5 μm can be used.

  Specifically, the melting points of polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, cyclic olefin homopolymers and copolymers of cyclic olefin and ethylene, etc. are 160 ° C. to 300 ° C. or glass. Mention may be made of those having a transition temperature of 160 ° C. to 280 ° C.

  These inorganic fine powders and organic fillers can be used alone or in combination. These contents in the stretched resin film are 30 to 75% by weight, more preferably 40 to 65% by weight. If it is less than 30% by weight, unevenness and voids are hardly formed on the film surface, the surface roughness is small, there are few portions where the thermal transfer ink melted by heating of the thermal head enters, and the amount of ink that can be contained is small even if the surface is covered. The object of the present invention cannot be achieved. On the other hand, if it exceeds 75% by weight, the strength of the surface of the melt thermal transfer recording paper is lowered and the surface becomes brittle and easily damaged, and the object of the present invention cannot be achieved.

(6) Dispersant Examples of the dispersant that can be used in the present invention include acid-modified polyolefin and silanol-modified polyolefin. Among these, acid-modified polyolefin is preferable. Examples of the acid-modified polyolefin include a hydroxyl-free polyolefin containing a random copolymerization or graft copolymerization of maleic anhydride, or a carboxylic acid group-containing polyolefin obtained by a random copolymerization or graft copolymerization of an unsaturated carboxylic acid such as methacrylic acid or acrylic acid, Examples thereof include an epoxy group-containing polyolefin obtained by random copolymerization or graft copolymerization of glycidyl methacrylate. Specific examples include maleic anhydride modified polypropylene, maleic anhydride modified polyethylene, acrylic acid modified polypropylene, ethylene / methacrylic acid random copolymer, ethylene / glycidyl methacrylate random copolymer, ethylene / glycidyl methacrylate graft copolymer, glycidyl. Examples include methacrylate-modified polypropylene, among which maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene are preferable.

  By blending a dispersant, the dispersibility of the inorganic fine powder or the organic filler is improved, and in particular, the solvent scuff resistance of the melt thermal transfer ink is improved.

  Specific examples of maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene include Mitsubishi Chemical's Modic AP [P513V], AP [M513] (trade name), and Sanyo Chemical Co., Ltd. Yumex1001, 1010 (trade name) ), Yumex2000 (trade name), and Mitsui DuPont Polychemical Co., Ltd. HPR [VR101] (trade name).

  The acid modification rate of the acid-modified polyolefin is preferably 0.01 to 20%, more preferably 0.05 to 15%, and further preferably 0.1 to 10%.

  If the acid modification rate is less than 0.01%, the dispersion effect of the inorganic fine powder in the thermoplastic resin tends to be insufficient, and if it exceeds 20%, the heat resistance of the acid-modified polyolefin becomes too low. There is a tendency to be easily colored during molding.

  The content of the dispersant is preferably more than 0% by weight and 20% by weight or less, more preferably more than 0% by weight and 10% by weight or less, still more preferably 0.1 to 5% by weight, Particularly preferred is 0.15 to less than 2% by weight, and most preferred is 0.2 to 1.7% by weight.

  When the content of the dispersant exceeds 20% by weight, the occurrence of sag (such as thermally deteriorated resin composition) at the time of molding increases, and the stretchability tends to greatly decrease and the number of stretch breaks at the time of molding tends to increase. There is.

(7) Lubricant A lubricant is used for the purpose of improving the moldability of the stretched resin film of the present invention. It has the effect of increasing fluidity by reducing the intermolecular frictional force of the molten resin in the extruder or the frictional force between the inner wall of the extruder and the molten resin. The amount used is usually in the range of 0.01 to 4% by weight. Specifically, higher fatty acids such as oleic acid and stearic acid, and metal salts thereof, alcohols such as higher alcohols, polyhydric alcohols, polyglycols, polyglycerols, fatty acids and aliphatic alcohols, aromatic alcohols, polyglycols Etc., natural waxes, fatty acid amides and the like can be used.

(8) Other auxiliaries A stabilizer, a light stabilizer, etc. can be added to the stretched resin film constituting the melt thermal transfer recording paper of the present invention as required.

  When a stabilizer is added, it is usually added within a 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 within a range of 0.001 to 1% by weight. As the light stabilizer, specifically, a sterically hindered amine-based, benzotriazole-based, benzophenone-based light stabilizer, or the like can be used.

(9) Forming Method The forming method of the melt thermal transfer recording paper of the present invention is not particularly limited, and can be suitably selected from known methods and formed. For example, cast molding, calender molding, rolling molding, inflation molding, thermoplastic resin and organic solvent, which extrude molten resin into a sheet using a single layer or laminated T die or I die connected to a screw type extruder After the mixture with oil is cast or calendered, it can be molded using a method of removing the solvent or oil.

  The stretching method is performed by any of various methods that are usually used.

  As specific examples, longitudinal stretching using a difference in peripheral speed between rolls, 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 during stretching is within the temperature range of the Vicat softening point of the thermoplastic resin having a Vicat softening point of 140 ° C. or lower and below the melting point of the polyolefin resin (preferably 2-20 ° C. lower than the melting point). be able to. The stretching speed is preferably 20 to 350 m / min.

  The draw ratio is appropriately determined in consideration of the characteristics of the polyolefin resin used and the thermoplastic resin having a Vicat softening point of 140 ° C. or lower. In the case of stretching in one direction, it is 2 to 12 times, preferably 3 to 10 times, more preferably 4 to 8 times. In the case of biaxial stretching, the area magnification is 4 to 80 times, preferably 10 to 65 times, More preferably, it is 20 to 50 times.

(10) Thickness The thickness of the melt thermal transfer recording paper of the present invention is 0.5 μm to 1000 μm, preferably 1 μm to 500 μm.

  The thickness of the laminate obtained by laminating these by co-extrusion or extrusion laminating at the same time as molding, or by laminating with other resin films or materials other than resin films after molding, is preferably 20 μm to 3000 μm, more Preferably it is 30 micrometers-2000 micrometers.

[2] Coating Agent (1) Constituent Material (i) Component Printing ink when a coating layer made of an ethyleneimine adduct of polyimine polymer or polyamine polyamide as component (i) is provided on the melt thermal transfer recording paper of the present invention. In particular, the adhesiveness of the ultraviolet curable ink can be improved. Examples of such compounds include polyethyleneimine, poly (ethyleneimine-urea) and polyamine polyamide ethyleneimine adducts, or alkyl-modified products, cycloalkyl-modified products, aryl-modified products, allyl-modified products, aralkyl-modified products, Alchiral modified products, benzyl modified products, cyclopentyl modified products, aliphatic cyclic hydrocarbon modified products, or hydroxides thereof may be used alone or in combination of several kinds.

  Among these, it is preferable to use the polyimine-based polymer represented by the general formula (a) from the viewpoint of improving the adhesion to the offset ink and the transferability. Here, any degree of polymerization of polyethyleneimine is used, but it is preferably 20 to 3,000.

(Ii) Component Addition of an epoxy-based, isocyanate-based, formalin-based, or oxazoline-based water-soluble resin to the above-mentioned component (i) as a crosslinking agent that is the component (ii) further improves the water-resistant adhesion to the printing ink. be able to. As the crosslinking agent, bisphenol A-epichlorohydrin resin, polyamine polyamide epichlorohydrin resin, aliphatic epoxy resin, epoxy novolac resin, alicyclic epoxy resin, brominated epoxy resin are preferable, and most preferably, epiamine hydrin adduct of polyamine polyamide Or monofunctional to polyfunctional glycidyl ethers and glycidyl esters.

(Iii) Component By adding the polymer type antistatic agent as the component (iii) to the above components (i) and (ii), troubles due to dust adhesion and charging during printing and printing can be reduced. As the polymer type antistatic agent, a cation type, an anion type, an amphoteric type, a 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. Anionic types 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 (anhydrous) maleic acid (for example, lithium salt, sodium salt, potassium salt, etc. ) Having a structure in the molecular structure.

  The amphoteric type contains both the cation type and the anion type structures in the same molecule, and examples thereof include 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 be given as an example. Among these, nitrogen-containing polymer type antistatic agents are preferable, and tertiary nitrogen or quaternary nitrogen-containing acrylic polymers are more preferable. In addition, you may add to a coating agent of this invention in the range which does not impair printing and a thermal transfer characteristic as needed, such as an antifoamer and another adjuvant.

(2) Quantity ratio The coating agent used for this invention is the following ratio of (ii) and (iii) component with respect to 100 weight part of (i) component.
Component (ii) Usually 0 to 400 parts by weight, preferably 50 to 300 parts by weight (iii) Component Usually 0 to 800 parts by weight, preferably 25 to 500 parts by weight

(3) Form of coating agent Each component of the coating agent is used after being dissolved in water or a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, toluene, xylene, In particular, it is generally used in the form of an aqueous solution. The solution concentration is usually 0.5 to 40% by weight, preferably 1 to 20% by weight.

(4) Coating (a) Coating amount The coating amount of the coating agent on the melt thermal transfer recording paper is usually 0.01 to 3 g / m ² , preferably 0.01 to 1 g / m ² , more preferably 0 in terms of solid content. 0.02 to 0.3 g / m ² . If it is less than 0.01 g / m ² , sufficient antistatic performance cannot be obtained and there is a concern not only about feed troubles during printing, but also there is a tendency that adhesion of printing ink cannot be obtained. In the 3 g / m ² exceeds not only the drying property is inferior, is already sufficient performance in 3 g / m ² tend to be cost for the resulting.

(B) Coating device As the coating device, a coating device using a roll coater, blade coater, bar coater, air knife coater, size press coater, gravure coater, die coater, lip coater, spray coater or the like can be used. .

The melt thermal transfer recording paper of the present invention has a corona discharge treatment, a flame treatment, a plasma treatment, a glow discharge treatment, an ozone treatment and the like that are generally used for a film as a surface oxidation treatment before forming a coating layer on the surface. Are used alone or in combination. Of these, corona treatment and frame treatment are preferred, and in the case of corona treatment, the treatment amount is 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] Melting thermal transfer printing (1) Melting wax ink ribbon The melting wax ink ribbon is a polyester film (3 to 10 μm) having a heat-resistant resin coat (1 to 3 μm) applied to the surface on the side contacting the thermal head as a base film. Is used, and the opposite surface is coated with a hot melt ink that is solid at normal temperature and whose viscosity rapidly decreases when heated to a thickness of 3 to 8 μm by gravure or roll coating.

  The ink component of the wax ink ribbon is generally composed of various additives such as 10 to 20% by weight pigment, 60 to 80% by weight wax-based binder, and 10 to 20% by weight softener and dispersant. Yes.

  The wax-based binder exhibits a broad melting point and a characteristic that the viscosity rapidly decreases at a temperature equal to or higher than the melting point, and is capable of uniform ink transfer even if there is some temperature unevenness in the heating region. Specific examples include paraffin wax, ester wax and carnauba wax.

(2) Printing conditions The printing method for the melt thermal transfer recording paper of the present invention is not particularly limited, and can generally be performed using a melt thermal transfer recording apparatus. For specific printing conditions, Test Example 1 described later can be referred to.

  The melt thermal transfer recording paper of the present invention has an ANSI GRADE after solvent rubbing described in Test Example 2 to be described later, A to C, preferably B or more.

[4] Surface physical properties (1) Surface coverage area ratio after blank printing The surface coverage area ratio in the present specification is a value measured by the following procedure. In other words, using a fusion thermal transfer recording device, the surface of the thermal transfer recording paper is directly blank printed with the thermal head, and an arbitrary part of the film is cut out and pasted on the observation sample stage, and gold is deposited on the observation surface. Using a scanning microscope “S-2400” (trade name) manufactured by Co., Ltd., the surface was photographed at a magnification of 2000 times, and the portion of the surface covered by the heat of the thermal head was traced to the tracing film. The image that has been painted is subjected to image processing with an image analysis apparatus “Model Luzex IID” (trade name, manufactured by Nireco Corporation), and the surface coverage area ratio of the stretched resin film is measured.

  The surface coverage area ratio of the melt thermal transfer recording paper of the present invention after empty printing with the melt thermal transfer recording apparatus is preferably 35% or more, more preferably 40% or more, and further preferably 50% to 100%.

  A thermoplastic resin with a Vicat softening point of 140 ° C. or lower undergoes plasticization deformation of the film surface due to the heat of the thermal head during fusion thermal transfer printing, and is exposed to an organic solvent for fusing with the hot melt ink Even after rubbing, the ink melts less.

  However, even when the surface coating area ratio satisfies 35% or more, if the inorganic fine powder and / or the organic filler is less than 30% by weight, the unevenness and voids on the film surface before thermal transfer are not sufficient, so that the hot-melt ink is used. Insufficient penetration of the irregularities and voids of the organic solvent, and the scratching property of the organic solvent is not good.

(2) Centerline average roughness (Ra)
The centerline average roughness (Ra) in this specification is based on JIS-B-0601-2001, and is a three-dimensional roughness measuring machine SE-3AK (trade name) manufactured by Kosaka Laboratory and an analyzer Model SPA-11. It is measured by (trade name).

The center line average roughness of the melt thermal transfer recording sheet of the present invention (Ra) is Ri 0.4~2.5μm der, it is good Mashiku is 0.45～2.0Myuemu, 0.5 to 0.8 It is particularly preferred that

When the average roughness of the center line is less than 0.4 μm, fine irregularities are not formed on the film surface, there are few portions where the thermal transfer ink melted by the heating of the thermal head enters, and the amount of ink contained is small and the object of the present invention is achieved. The resulting stomach. In addition, the scratch property may be inferior when rubbed with a sharp object. Further, when the centerline average roughness exceeds 2.5 [mu] m, poor metastatic printing inks or melt thermal transfer ink, printing was chipped, not be obtained print density of interest.

[5] Lamination The lamination method of the present invention is not particularly limited, and various known methods can be used. Specific examples include a multilayer die method using a feed block and a multi-manifold, and an extrusion lamination method using a plurality of dies. A combination of multilayer dies and extrusion lamination may also be used. In addition, any known laminating method such as dry lamination using an adhesive, wet lamination, or application of a hot melt adhesive can be used.

[6] Adhesive The adhesive is typically a rubber adhesive, an acrylic adhesive, or a silicone adhesive. Specific examples of the rubber adhesive include polyisobutylene rubber, butyl rubber and a mixture thereof, Or the thing which mix | blended tackifiers, such as an abietic acid rosin ester, a terpene * phenol copolymer, a terpene * indene copolymer, with these rubber-type adhesives is mentioned. As specific examples of the acrylic pressure-sensitive adhesive, the glass transition point of 2-ethylhexyl acrylate / n-butyl acrylate copolymer, 2-ethylhexyl acrylate / ethyl acrylate / methyl methacrylate copolymer, or the like is −20 ° C. or lower. Things.

  As a form of these pressure-sensitive adhesives, a solvent type, an emulsion type, a hot melt type, and the like are used, and they are generally laminated by applying a solvent type or an emulsion type.

  Such coating is performed by a roll coater, a blade coater, a bar coater, an air knife coater, a gravure coater, a reverse coater, a die coater, a lip coater, a spray coater, a comma coater, etc. Then, an adhesive layer is formed.

  For the formation of the pressure-sensitive adhesive layer, it is common to apply a pressure-sensitive adhesive to the release paper, which will be described later, and if necessary, dry and then laminate the melt thermal transfer recording paper on the one formed with the pressure-sensitive adhesive layer. Depending on the case, it may be formed by directly applying an adhesive to the melt thermal transfer recording paper.

The coating amount of the pressure-sensitive adhesive is not particularly limited, but is usually in the range of ^{3 to} 60 g / m ² , preferably 10 to 40 g / m ² in terms of solid content. Moreover, it is preferable that the delamination strength of this adhesive layer is 200-3000 g / 20mm.

  When the adhesive force between the melt thermal transfer recording paper and the adhesive is small, it is preferable to apply an anchor coating agent to the back surface of the melt thermal transfer recording paper before applying the adhesive.

  As the anchor coating agent, polyurethane, polyisocyanate / polyether polyol, polyisocyanate / polyester polyol / polyethyleneimine, alkyl titanate, etc. can be used, and these are generally organic solvents such as methanol, ethyl acetate, toluene, hexane, Used by dissolving in water.

The coating amount of the anchor coating agent, 0.01-5 g / m ² by solid content after coating and drying, is preferably in the range of 0.02~2g / m ^2.

[7] Release paper Further, if necessary, release paper can be provided outside the pressure-sensitive adhesive layer.
The release paper provided on the melt heat transfer recording paper via the pressure-sensitive adhesive layer is generally subjected to silicon treatment on the surface in contact with the pressure-sensitive adhesive layer in order to improve the peelability from the pressure-sensitive adhesive layer.
Release paper can be used for general papers, and high-quality paper and kraft paper can be used as is, or they can be treated with silicon on glassine paper, coated paper, plastic film, etc. that are calendered, resin-coated, or film-laminated. Can be used.
By providing release paper with the above-mentioned pressure-sensitive adhesive on the melt thermal transfer recording paper or laminate of the present invention, it can be used as a base paper for labels.

[8] Printing The melt thermal transfer recording paper of the present invention can be used for recording by 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 use in the melt thermal transfer system is preferable from the viewpoint of remarkably obtaining the effect of the present invention, that is, the effect of improving the solvent scratch resistance of the transferred print and image portion.
Examples of the type of ink ribbon to be used include a wax type, a resin type, and a mixed type of both, and it is particularly preferable to use a wax type ink ribbon.

  Furthermore, various printing is also possible, and offset printing, gravure printing, flexographic printing as well as letterpress printing can be mentioned.

  A recorded matter can be obtained by performing printing / printing on the melt thermal transfer recording paper or laminate or label base paper of the present invention by various methods as described above.

  The features of the present invention will be described more specifically with reference to production examples, examples, comparative examples and test examples. The production example describes the production of the stretched resin film and the components (i) to (iii), the example describes the production of the melt thermal transfer recording paper that satisfies the conditions of the present invention, and the comparative example does not satisfy the conditions of the present invention. The melt thermal transfer recording paper is described, and the test example describes the test and evaluation of each melt thermal transfer recording paper. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

(Production Example 1) Production of stretched resin film (1) Propylene homopolymer “Novatech PP EA-8” (trade name, melting point 164 ° C., manufactured by Nippon Polychem Co., Ltd.) 85% by weight with an average particle size of 3.0 μm A composition (C) in which 15% by weight of heavy calcium carbonate “Softon 1800” (trade name, manufactured by Bihoku Flour Industry Co., Ltd.) was mixed by an extruder set at 270 ° C., and then in sheet form And then cooled by a cooling device to obtain an unstretched sheet. Next, the sheet was heated again to a temperature of 150 ° C., and then stretched 5 times in the longitudinal direction to obtain a longitudinally stretched resin film.

  (2) High density polyethylene “Novatech HD, HJ360” (trade name) manufactured by Nippon Polychem Co., Ltd., having a Vicat softening point of 122 ° C., 23% by weight, and a propylene homopolymer “Novatech PP MA-3” having a Vicat softening point of 145 ° C. (Nippon Polychem Co., Ltd., trade name, melting point 165 ° C.) 16.2% by weight, heavy calcium carbonate “Caltex 7” (trade name, Maruo Calcium Co., Ltd., trade name) 60% by weight with an average particle size of 1.1 μm A composition (A) in which 0.2% by weight of aluminum stearate and 0.6% by weight of oleic acid were mixed as a lubricant was prepared. Separately, a heavy calcium carbonate “Softon 1800” having an average particle size of 3.0 μm was added to 55% by weight of a propylene homopolymer “Novatech PP MA-3” (trade name, melting point 165 ° C., manufactured by Nippon Polychem Co., Ltd.). A composition (B) in which 45% by weight (trade name, manufactured by Bihoku Flour Industry Co., Ltd.) was mixed was prepared. These compositions (A) and (B) were melt-kneaded in separate extruders set at 270 ° C., laminated inside the die, and then co-extruded from a single die. It laminated | stacked so that the (A) layer might become a surface layer on the front side of the 5 times longitudinally stretched film obtained at the process.

  (3) Further, a heavy calcium carbonate “Softon 1800” having an average particle size of 3.0 μm and 55% by weight of a propylene homopolymer “Novatech PP MA-3” (trade name, melting point 165 ° C., manufactured by Nippon Polychem Co., Ltd.) (Bikoku Flour Industry Co., Ltd., trade name) A composition (D) mixed with 45% by weight was melted and kneaded in another extruder set at a temperature of 270 ° C., and then extruded into a sheet. Was laminated on the back surface of the 5-fold longitudinally stretched film obtained in the step (1) to obtain a laminated sheet having a four-layer structure. Next, the laminated sheet having the four-layer structure was cooled to a temperature of 60 ° C., then heated again to a temperature of 155 ° C., stretched 8.5 times in the transverse direction using a tenter, and annealed at a temperature of 165 ° C. After the treatment and cooling to a temperature of 60 ° C., the ears are slit and the thickness of the four-layer structure (uniaxial stretching / uniaxial stretching / biaxial stretching / uniaxial stretching) is 80 μm (A / B / C / D = 5 μm / 10 μm / 50 μm / 15 μm) stretched resin film was obtained.

(4) Corona discharge treatment was performed on both surfaces of the film using a corona discharge treatment apparatus “HF400F” (trade name, manufactured by Kasuga Electric Co., Ltd.). In the corona discharge treatment, an aluminum electrode having a length of 0.8 m was used, a silicone film roll was used as the treater roll, the gap between the electrode and the roll was 5 mm, the line treatment speed was 15 m / min, and the applied energy density was 4 , 200 J / m ² .

(Production Example 2) Production of stretched resin film (1) High-density polyethylene “Novatech HD, HJ360” (trade name, manufactured by Nippon Polychem Co., Ltd.) having a Vicat softening point of 122 ° C., propylene having a Vicat softening point of 145 ° C. Homopolymer “Novatech PP MA-3” (trade name, melting point 165 ° C., manufactured by Nippon Polychem Co., Ltd.) 16.2 wt%, heavy calcium carbonate “Caltex 7” (Maruo Calcium Co., Ltd., trade name) 60% by weight, composition (A) in which aluminum stearate 0.2% by weight and oleic acid 0.6% by weight are mixed as a lubricant, and propylene homopolymer "NOVATEC PP EA-8" (Nippon Polychem Co., Ltd., trade name, melting point 165 ° C.) 85% by weight, heavy calcium carbonate “Softon 1800” with an average particle size of 3.0 μm Co., Ltd., trade name: 15% by weight of the composition (B) and propylene homopolymer “Novatec PP MA-3” (manufactured by Nippon Polychem Co., Ltd., trade name, melting point 165 ° C.) 55% by weight A composition (C) was prepared by mixing 45% by weight of heavy calcium carbonate “Softon 1800” (trade name, manufactured by Bihoku Flour Industry Co., Ltd.) having an average particle size of 3.0 μm. These compositions (A), (B) and (C) are melt-kneaded in separate extruders set at 270 ° C., laminated inside the die, coextruded into a sheet, and further cooled by a cooling device. A three-layer unstretched laminated sheet was obtained. Next, after reheating to a temperature of 150 ° C., the film was stretched 7 times in the longitudinal direction and annealed at 155 ° C. to obtain a stretched resin film having a thickness of 80 μm (A / B / C = 5 μm / 70 μm / 5 μm). .

(2) The surface of the film was subjected to corona discharge treatment using a corona discharge treatment apparatus “HF400F” (trade name, manufactured by Kasuga Electric Co., Ltd.). In the corona discharge treatment, an aluminum electrode having a length of 0.8 m was used, a silicone film roll was used as the treater roll, the gap between the electrode and the roll was 5 mm, the line treatment speed was 15 m / min, and the applied energy density was 4 , 200 J / m ² .

(Production Example 3) Production of stretched resin film (1) High-density polyethylene “Novatech HD, HJ360” (trade name, manufactured by Nippon Polychem Co., Ltd.) having a Vicat softening point of 122 ° C., propylene having a Vicat softening point of 145 ° C. Homopolymer “Novatech PP MA-3” (manufactured by Nippon Polychem Co., Ltd., trade name, melting point 165 ° C.) 24.2% by weight, heavy calcium carbonate “Cartex 7” (Maruo Calcium Co., Ltd., trade name) 40% by weight, a composition (A) in which aluminum stearate 0.2% by weight and oleic acid 0.6% by weight are mixed as a lubricant, and a propylene homopolymer "Novatec PP EA-8" (Nippon Polychem Co., Ltd., trade name, melting point 165 ° C.) 85% by weight, heavy calcium carbonate “Softon 1800” with an average particle size of 3.0 μm Co., Ltd., trade name: 15% by weight of the composition (B) mixed with Nippon Polychem Co., Ltd., propylene homopolymer “NOVATEC PP MA-3” (trade name, melting point: 165 ° C.) 55% by weight A composition (C) was prepared by mixing 45% by weight of heavy calcium carbonate “Softon 1800” (trade name, manufactured by Bihoku Flour Industry Co., Ltd.) having an average particle size of 3.0 μm. These compositions (A), (B) and (C) are melt-kneaded in separate extruders set at 270 ° C., laminated inside the die, coextruded into a sheet, and further cooled by a cooling device. A three-layer unstretched laminated sheet was obtained.

  (2) Next, this three-layer laminated sheet was cooled to 60 ° C. by a cooling device, then reheated to a temperature of 150 ° C., then stretched 5 times in the longitudinal direction, and further a temperature of 155 ° C. And then stretched 6 times in the transverse direction using a tenter, annealed at a temperature of 165 ° C., cooled to a temperature of 60 ° C., slitted at the ear, and 80 μm thick (A / B / A laminated resin stretched film of C = 5 μm / 70 μm / 5 μm was obtained.

(3) The surface of the film was subjected to corona discharge treatment using a corona discharge treatment apparatus “HF400F” (trade name, manufactured by Kasuga Electric Co., Ltd.). In the corona discharge treatment, an aluminum electrode having a length of 0.8 m was used, a silicone film roll was used as the treater roll, the gap between the electrode and the roll was 5 mm, the line treatment speed was 15 m / min, and the applied energy density was 4 , 200 J / m ² .

(Production Example 4) Production of coating agent (i) component 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)” (Japan) 100 parts of a 25% by weight aqueous solution of a catalyst (trade name), 10 parts of n-butyl chloride and 10 parts of propylene glycol monomethyl ether are added and stirred under a nitrogen stream, and the modification reaction is carried out at a temperature of 80 ° C. for 20 hours. And a 20% by weight butyl-modified polyethyleneimine aqueous solution was obtained.

(Manufacture example 5) Preparation of coating agent (ii) component Epichlorohydrin adduct "WS-570 (solid content 12.5 weight%)" of polyamine polyamide (Nippon PMC Co., Ltd., brand name) coating agent (ii) Prepared as an ingredient.

(Production Example 6) Production of coating agent (iii) component 35 parts of dimethylaminoethyl methacrylate and 20 parts of ethyl methacrylate are attached to a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution, and a stirrer. Then, 20 parts of cyclohexyl methacrylate, 25 parts of stearyl methacrylate, 150 parts of ethyl alcohol and 1 part of azobisisobutyronitrile were added, and a polymerization reaction was performed at a temperature of 80 ° C. for 6 hours in a nitrogen stream.

  Next, 70 parts of a 60% by weight ethyl alcohol solution of 3-chloro-2-hydroxypropylammonium chloride was added and further reacted at a temperature of 80 ° C. for 15 hours, and then the ethyl alcohol was distilled off while adding water dropwise. A quaternary ammonium salt copolymer having a solid content of 30% was obtained.

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

Example 1
The laminated resin stretched film obtained in Production Example 1 was used as a melt thermal transfer recording paper. In addition, composition of resin etc. in following Table 1 represents the composition of A layer (outermost layer). The same applies to other examples and comparative examples described later.

(Examples 2 to 5)
A melt thermal transfer recording paper was obtained in the same manner as in Example 1 except that the blending amount of the propylene homopolymer of layer A, high density polyethylene or inorganic fine powder in Example 1 was changed as shown in Table 1.

(Example 6)
The same procedure as in Example 1 was conducted, except that the inorganic fine powder of layer A in Example 1 was changed to heavy calcium carbonate “Softon 1800” (trade name) with an average particle size of 3.0 μm manufactured by Bihoku Flour Industry Co., Ltd. A melt thermal transfer recording sheet was obtained.

(Example 7)
In the same manner as in Example 1, except that the high density polyethylene of layer A in Example 1 is changed to low density polyethylene “Novatech LD, LC604” (trade name, manufactured by Nippon Polychem Co., Ltd.) having a Vicat softening point of 84 ° C. A melt thermal transfer recording sheet was obtained.

(Example 8)
The high density polyethylene of layer A in Example 1 was changed to ethylene-methyl acrylate “Lex Pearl RB5120” (trade name, manufactured by Nippon Polyolefin Co., Ltd.) having a Vicat softening point of 60 ° C. A melt thermal transfer recording sheet was obtained.

Example 9
The laminated resin stretched film obtained in Production Example 2 was used as a melt thermal transfer recording paper.

(Example 10)
The laminated resin stretched film obtained in Production Example 3 was used as a melt thermal transfer recording paper.

Example 11
On both surfaces of the laminated resin stretched film obtained in Production Example 1, 100 parts by weight of the coating agent (i) component obtained in Production Example 4, 150 parts by weight of the coating agent (ii) component obtained in Production Example 5, and in Production Example 6 The obtained coating agent consisting of 150 parts by weight of the coating agent (iii) component is applied and dried using a roll coater so that the thickness of the coating film becomes 0.06 g / m ^2, and the film-like melt thermal transfer recording paper Got.

Example 12
In Example 1, in layer A, the blend of propylene homopolymer and high-density polyethylene was changed to the amounts shown in Table 1, and maleic acid-modified polypropylene having a maleic acid modification rate of 5% as a dispersant (Sanyo Chemical Co., Ltd.) Manufactured and trade name: “Yumex1001”) was added in the same manner as in Example 1 except that 0.5% by weight was added to obtain a melt thermal transfer recording sheet.

(Examples 13 to 17)
In Example 12, a melt thermal transfer recording paper was obtained in the same manner as in Example 12 except that the blending amounts of the propylene homopolymer of layer A, high-density polyethylene, inorganic fine powder, and dispersant were changed as shown in Table 1. .

(Comparative Example 1)
A stretched resin film described in Example 1 of JP-A-8-80684 was prepared. In addition, evaluation of the test example described below was performed about the surface layer (uniaxial stretching) of this film.

(Comparative Example 2)
A stretched resin film described in Example 1 of JP-A No. 2001-219661 was prepared. In addition, evaluation of the test example described below was performed about the surface layer (uniaxial stretching) of this film.

(Comparative Examples 3 to 7)
A melt thermal transfer recording paper was obtained in the same manner as in Example 1 except that the blending amounts of the propylene homopolymer, high-density polyethylene, and inorganic fine powder in layer A of Example 1 were changed as shown in Table 2.

(Comparative Example 8)
In the same manner as in Example 5, except that the polypropylene homopolymer of layer A in Example 5 is changed to “Cisso Polypro F8090” (trade name, melting point: 148 ° C., manufactured by Chisso Corporation) having a Vicat softening point of 131 ° C. A film was obtained and evaluated. The results are shown in Table 2.

  Tables 1 and 2 show the results of measuring the surface coverage area ratio and the centerline average roughness (Ra) after empty printing according to the measurement method described above for each of the thermal transfer recording sheets manufactured in Examples and Comparative Examples. Further, the following tests were conducted.

(Test Example 1) Evaluation of melt heat transfer suitability Printing on each melt heat transfer recording paper produced in Examples and Comparative Examples was performed to evaluate melt heat transfer suitability. For printing, a bar code printer “Zebra140 Xi II” (trade name, manufactured by Zebra Corporation) and a melt-type wax ink ribbon “FTR” (trade name, manufactured by Fuji Copian Corporation) were used. Conditions were set so that the temperature of the thermal head was 110 ° C. (measured by attaching a thermocouple to the thermal head).

  The molten wax ink ribbon was transferred to the recording paper at a temperature of 110 ° C. and a printing speed of 3 inches / second. Bar code (CODE39) printed by melt heat transfer is read with a bar code verifier “LASERCHEK II” (trade name, manufactured by Fuji Electric Refrigerator Co., Ltd.) under the conditions of a temperature of 23 ° C. and a relative humidity of 50%. The reading rate was evaluated by ANSI (American National Standards Institute) GRADE. ANSI GRADE appears in 6 stages of A to D, F and No Decode, and A indicates the best printing state. The results are as shown in Tables 1 and 2.

A: Extremely good (barcode is not faint at all, and commercially available barcode
(A level that can be read accurately with a single barcode reading using a reader)
B: Good (Basically, it is possible to read a single barcode, but
(A level that may require reading the barcode again)
C: Possible (Slight fading is seen in the barcode, and multiple times of reading the barcode.
Is necessary but practical level)
D, F: Impossible (bar code breaks, reading more bar codes than C level)
The number of times of taking is necessary and is not practical)
No Decord: Impossible (level not recognized as CODE39 barcode)

(Test Example 2) Evaluation of solvent abrasion resistance The printed matter obtained in Example 1 was evaluated by a method based on JIS-L-0849-1996. Specifically, using a friction tester “FR-II” (trade name, manufactured by Suga Test Instruments Co., Ltd.) for dyeing fastness test, ethanol is appropriately supplied so that the white cotton cloth for friction is always kept wet. However, it was rubbed 50 times with a load of 200 g. Solvent rub resistance was measured by measuring ANSI GRADE with a bar code verifier. Those having ANSI GRADE of A to C or higher were judged to be practical levels. The results are as shown in Tables 1 and 2.

(Test Example 3) Evaluation of printability For evaluation, the printing machine “RI-III type printability tester” (trade name, manufactured by Meisei Co., Ltd.) and printing ink “Best Cure 161 (black)” ) T & K TOKA, trade name) was used.

Each melt thermal transfer recording sheet was stored for 3 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and then the ink was applied to the application surface of the melt thermal transfer recording sheet with a thickness of 1.5 g / m ² using the printer. It was printed as it was. The Macbeth density of the printed surface was measured with a light reflection density “Macbeth densitometer” (trade name, manufactured by Colmorgen, Inc. (USA)). C or higher was determined as an acceptable level according to the following criteria. The results are as shown in Tables 1 and 2.
A: Macbeth concentration of 1.8 or higher, transition density is extremely good B: Macbeth concentration of 1.6 or higher and lower than 1.8, transfer density is good C: Macbeth concentration of 1.4 or higher and lower than 1.6, transition level is slightly thin Practical level D: Macbeth concentration of less than 1.4, transfer concentration is low, which may be a problem depending on the design

(Test Example 4) Evaluation of Meani In the molding of the resin films used in Examples 1 to 17 and Comparative Examples 1 to 8, the occurrence state of the meani at the tip of the die 1 hour after the start of molding was judged visually.
A: Excellent (There is almost no scum on the tip of the die, and there is no problem in molding.
Level)
B: Good (Mayani is seen at the tip of the die, but there is no problem in molding)
C: Yes (Mayan is observed at the tip of the die, and it is removed from the resin film.
Although it drops, it is possible to form by regular cleaning of the die tip)
D: Not possible (Mayan on the tip of the die is very large, and it is not on the resin film.
Is a level that often falls off and cannot withstand molding)

Claims (13)

A melt thermal transfer recording sheet comprising a stretched resin film stretched in at least one direction, and the centerline average roughness (Ra) of the surface of the stretched resin film according to JIS-B-0601-2001 is 0.4 to 2.5 μm. , and the outermost layer of the stretched resin film, an inorganic fine powder and / or organic filler 30-75 wt%, a thermoplastic resin Vicat softening point as measured by JIS-K-7206-1999 is 140 ° C. or less 70 to 25% by weight in total of polyolefin resins having a Vicat softening point measured in accordance with JIS-K-7206-1999 exceeding 140 ° C., and the outermost layer of the stretched resin film is based on 100 parts by weight of the polyolefin resin. A melt thermal transfer recording sheet comprising the thermoplastic resin in an amount of more than 75 parts by weight and not more than 900 parts by weight. 2. The melt thermal transfer recording sheet according to claim 1, wherein the polyolefin resin is a propylene resin having a Vicat softening point exceeding 140 ° C. Melt thermal transfer recording sheet according to claim 1 or 2, characterized in that it contains a dispersing agent. 4. The melt thermal transfer recording sheet according to claim 3 , wherein the dispersant is contained in an amount exceeding 0% by weight and not more than 20% by weight. The draw ratio is 2 to 12 times in the case of stretched resin film is stretched in one direction, more of claims 1-4 in which the area stretching ratio when biaxially stretching is characterized in that it is a 4 to 80-fold melt thermal transfer recording sheet according to one paragraph or. (I) below the melting thermal transfer recording sheet according to any one of claims 1 to 5, characterized in that a coating layer containing a component.
(I) An ethyleneimine adduct of a polyimine polymer or polyamine polyamide represented by the following general formula (a).

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having a linear, branched or alicyclic structure having 1 to 10 carbon atoms, or an aryl group, and R ³ is hydrogen. An atom, 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, m is an integer in the range of 2 to 6, and n Is an integer in the range of 20 to 3000, and m × n R ¹ and R ² and n R ³ may be the same as or different from each other. The molten thermal transfer recording sheet according to claim 6 , wherein the coating layer contains the following component (ii).
(Ii) Water-soluble epoxy-based, isocyanate-based crosslinking agent, formalin-based crosslinking agent, oxazoline-based crosslinking agent, and crosslinking agent for epichlorohydrin adduct of polyamine polyamide. The molten thermal transfer recording sheet according to claim 6 or 7 , wherein the coating layer contains the following component (iii).
(Iii) Polymer type antistatic agent. Melt thermal transfer recording sheet according to any one of claims 1 to 8, characterized in that subjected to at least printed on one side of the surface of the stretched resin film. A laminate having a structure in which the melt thermal transfer recording sheet according to any one of claims 1 to 9 is provided in an outermost layer and laminated with another resin film. A laminate having a structure in which the melt thermal transfer recording paper according to any one of claims 1 to 9 is laminated on a material other than a resin film. A base paper for label, wherein the melt thermal transfer recording paper according to any one of claims 1 to 9 or the laminate according to claim 10 or 11 is laminated on a release paper via an adhesive. A recorded matter using the melt thermal transfer recording sheet according to any one of claims 1 to 9 , the laminate according to claim 10 or 11 , or the label base paper according to claim 12 .