JP2014059486A - Pulverization toner for thermal transfer print sheet, thermal transfer print sheet, and method for producing the toner and the sheet - Google Patents

Abstract

A pulverized toner for a thermal transfer printed sheet, which can be bonded to an object to be printed by heat melting on a white background without using an adhesive, and which does not damage the pulverizer, and obtained using the pulverized toner To provide a thermal transfer printed sheet, a thermal transfer printed body manufactured using the thermal transfer printed sheet, and a manufacturing method thereof.
A pulverized toner for a thermal transfer print sheet is obtained by pulverizing a melt-kneaded product containing a polyester resin containing a unit obtained by condensing an aliphatic dicarboxylic acid and an aliphatic diol, and a white pigment having a new Mohs hardness of 5 or less. It is characterized by becoming. The thermal transfer print sheet has a releasable sheet having a releasable surface, a print image formed on the releasable sheet and thermally transferable to a transfer medium, and the pulverized toner is transferred and fixed onto the print image. And a white toner layer.
[Selection] Figure 3

Description

  The present invention relates to a pulverized toner for a thermal transfer print sheet, a thermal transfer print sheet obtained by using the pulverized toner, a thermal transfer print manufactured using the thermal transfer print sheet, and a manufacturing method thereof.

Conventionally, there is a method of creating a label with a back paste. This label is produced by printing a pattern on a label paper that is peelably pasted to the release sheet, and then cutting the label paper into an arbitrary shape with a blade. The method is generally done.
This type of label creation method does not interfere with this when creating a large number of labels, but when the number of labels to be created is small, the original printing plate and design are cut. As a result, the production cost of the cutting edge is high, resulting in a problem that the unit price of the label becomes high.

In addition, as a method of printing a design such as a desired image or logo mark on fabric products such as T-shirts, trainers, work clothes, wood, metal plates, etc., the design is directly applied to the object to be printed using an inkjet printer. Methods and apparatuses for printing have been proposed. (For example, see Patent Documents 1 and 2.)
In addition, an apparatus that directly prints on a cloth such as clothing using a thermal transfer printer (see Patent Document 3), and a method and apparatus that prints an image on a transfer paper and then thermally transfers the image onto a print medium using an iron or the like have been proposed. (For example, see Patent Documents 4 and 5.)

Japanese Patent Application Laid-Open No. 07-336466 Japanese Patent Laid-Open No. 08-207263 JP-A-11-157139 Japanese Patent Laid-Open No. 05-077575 Japanese Patent Application Laid-Open No. 09-087980 JP 2007-283745 A

  However, a direct printing method using an ink jet printer or a thermal transfer printer (Patent Documents 1, 2, and 3) is effective when a large number of the same shape or a large size is manufactured. When a large variety of products having a small size (such as clothing) and different shapes are prepared, the method of transporting the print object to the printer is different, which takes time and effort.

  In addition, the method of thermally transferring the image onto the print object after printing the image on the transfer paper (Patent Document 4) does not have the problem of the above-described method in that the shape of the print object is not selected, but the size of the transfer paper is fixed ( For example, there are many A4 size and A3 size), and a shape to be transferred to the printing object must be separately prepared.

  The method of Patent Document 5 is a method in which a shape is prepared using two transfer papers and thermally transferred to a printing object, and these problems are solved. However, there is a trouble that it is necessary to perform two thermal transfer operations using two transfer sheets. Actually, the temperature at the time of transfer, the pressing pressure, etc. are different for each manufactured sample, and the work requires a technique.

  In Patent Document 6, a toner layer is developed into a label shape on an adhesive layer to create a label shape only by development processing. However, not only is the release paper pre-coated with a pressure-sensitive adhesive on the surface, but also the process of applying a quality-changing process to remove the pressure-sensitive adhesive surface on the outer surface of the pressure-sensitive adhesive after the development process. Problem.

  On the other hand, a method of directly forming an image on a medium by using an electrophotographic method using toner has been proposed. In this case, when the medium is a colored material, a method of making the image stand out by using white toner to make the background of the image white is often used. The white toner usually contains a white pigment such as titanium oxide.

  However, since titanium oxide is a hard material, when a toner is prepared by a pulverization method, there is a drawback that the pulverizer is damaged due to its hardness. In particular, the toner used for adhesion between the media and the image is generally poor in pulverization, and freeze pulverization using liquid nitrogen is suitable for the pulverization. However, the freeze pulverizer has a measure for pulverizing hard materials due to its characteristics. Difficult to do, especially susceptible to damage.

  The present invention solves the above-described conventional problems, and can thermally melt and bond an image to a printing object on a white background without using an adhesive, and does not damage the pulverizer. It is an object of the present invention to provide a pulverized toner for a thermal transfer print sheet, a thermal transfer print sheet obtained by using the pulverized toner, a thermal transfer print body produced using the thermal transfer print sheet, and a method for producing them.

  In order to solve the above problems, a first aspect of the present invention is a melt kneading comprising a polyester resin containing a unit obtained by condensing an aliphatic dicarboxylic acid and an aliphatic diol, and a white pigment having a new Mohs hardness of 5 or less. There is provided a pulverized toner for a thermal transfer print sheet, which is obtained by pulverizing a product.

In the pulverized toner for a thermal transfer print sheet configured as described above, at least one selected from the group consisting of talc, kaolin, zinc sulfide, barium sulfate, calcium carbonate, and zinc oxide can be used as the white pigment. .
Further, the aliphatic dicarboxylic acid can be succinic acid, and the aliphatic diol can be 1,4-butanediol.

  According to a second aspect of the present invention, there is provided a step of melt-kneading a polyester resin containing a unit obtained by condensing an aliphatic dicarboxylic acid and an aliphatic diol and a white pigment having a new Mohs hardness of 5 or less, and obtaining There is provided a method for producing a pulverized toner for a thermal transfer print sheet, comprising a step of pulverizing the melted and kneaded product.

  According to a third aspect of the present invention, a releasable sheet having a releasable surface, a print image formed on the releasable sheet and thermally transferable to a transfer medium, and the print image Provided is a thermal transfer print sheet comprising a white toner layer formed by transferring and fixing the pulverized toner according to any one of.

  According to a fourth aspect of the present invention, there is provided a releasable sheet supplying step for supplying a releasable sheet having a releasable surface, an image forming step for transferring an image to be thermally transferred onto a transfer medium to the releasable sheet, A white toner layer forming step of developing the pulverized toner according to the first aspect of the present invention and transferring it onto the image transferred to the peelable sheet; the image transferred to the peelable sheet; and the white toner layer And a fixing step of fixing the film to a film shape by heating and pressurizing. A method for producing a thermal transfer printed sheet is provided.

  According to a fifth aspect of the present invention, a thermal transfer print sheet according to the third aspect of the present invention is overlapped with the image forming surface facing a transfer medium using a heating press, and the thermal transfer print sheet There is provided a thermal transfer printing method characterized by heating and pressurizing from the back surface of an image forming surface, peeling off the peelable sheet after cooling, and thermally transferring a white toner layer and an image of the thermal transfer print sheet to a transfer medium.

  According to the present invention, a pulverized toner for a thermal transfer printed sheet that can be bonded by melting and bonding an image to a printing object on a white background without using an adhesive, and that does not damage the pulverizer, The obtained thermal transfer printed sheet, a thermal transfer printed body manufactured using the thermal transfer printed sheet, and a manufacturing method thereof are provided.

It is sectional drawing which shows the internal structure of the thermal transfer print sheet manufacturing apparatus which enforces the method of manufacturing the thermal transfer print sheet which concerns on one Embodiment of this invention. It is a circuit block diagram including the control apparatus of the apparatus for producing the thermal transfer printed sheet which concerns on one Embodiment of this invention. (A)-(c) is a figure which shows the manufacturing process of the thermal transfer print sheet which concerns on one Embodiment of this invention typically, (d), (e) transfers the label image of a thermal transfer print sheet to a to-be-transferred medium. It is a figure which shows the process and procedure to perform.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
A pulverized toner for a thermal transfer print sheet according to an embodiment of the present invention is a melt-kneaded product containing a polyester resin containing a unit obtained by condensing an aliphatic dicarboxylic acid and an aliphatic diol, and a white pigment having a new Mohs hardness of 5 or less. It is characterized by being pulverized.

  According to the knowledge of the present inventors, as a result of studying various materials as the resin constituting the pulverized toner for thermal transfer print sheets, polybutylene succinic acid, which is a copolymer of succinic acid and 1,4-butanediol, is mainly used. By using the polyester resin as a constituent component, the film characteristics of the formed film were improved, and a great improvement was observed that the softening point at the time of fixing to the transfer medium was practically satisfactory.

In addition, when a white toner having a new Mohs hardness of 5 or less, particularly 1 to 5, is blended with such a polyester resin, when a white toner for a thermal transfer print sheet is produced by a pulverization method, the pulverizer is damaged. An excellent effect is obtained in that it is not given.
When an image is directly formed on a medium by an electrophotographic method, when the medium is a colored material, a method of making the image stand out by using white toner to make the background of the image white is often used. In such a case, in order to efficiently produce a white thermal transfer print sheet, the toner contains a white pigment, but titanium oxide (rutile type) most commonly used as a white pigment has a new Mohs hardness of 8-8. Since it is a high and hard material, the toner has a drawback of damaging the pulverizer due to its hardness when the toner is prepared by the pulverization method. The toner used as the base material of the label is generally poorly pulverized, and freeze pulverization using liquid nitrogen is suitable for the pulverization. However, the freeze pulverizer is difficult to take measures against pulverizing hard materials due to its characteristics. Easy to take damage.

In this embodiment, since a low white pigment having a new Mohs hardness of 5 or less is used, when a white toner for a thermal transfer print sheet is produced by a pulverization method, the pulverizer is not damaged.
Examples of the white pigment having a new Mohs hardness of 5 or less include at least one selected from the group consisting of talc, kaolin, zinc sulfide, barium sulfate, calcium carbonate, and zinc oxide.

Talc refers to phyllosilicate, also called talc. Kaolin is a clay mainly composed of kaolin minerals such as kaolinite.
The content of the white pigment is preferably 5 to 60% by mass with respect to the pulverized toner. If it is 5% by mass, it is difficult to obtain a white appearance, and if it exceeds 60% by mass, the physical strength as a film tends to deteriorate.

  In the pulverized toner for a thermal transfer print sheet according to this embodiment, the polyester resin as the resin component is a single monomer unit obtained by condensing an aliphatic dicarboxylic acid and an aliphatic diol, as represented by the following formula (1). Can be included.

また、樹脂成分であるポリエステル樹脂は、下記式（２）により表されるような複数種のユニットの共重合体を含むものであってもよい。

Moreover, the polyester resin which is a resin component may contain the copolymer of the multiple types of unit as represented by following formula (2).

以上説明した熱転写プリントシート用粉砕トナーは、脂肪族ジカルボン酸と脂肪族ジオールを縮合させたユニットを含むポリエステル樹脂と、新モース硬度が５以下である白色顔料とを加熱しつつ溶融混練する工程、及び得られた溶融混練物を粉砕する工程により製造することができる。

The heat transfer printed sheet pulverized toner described above is a step of melt-kneading a polyester resin containing a unit obtained by condensing an aliphatic dicarboxylic acid and an aliphatic diol and a white pigment having a new Mohs hardness of 5 or less, And it can manufacture by the process of grind | pulverizing the obtained melt-kneaded material.

  The pulverization of the melt-kneaded product is preferably performed at a low temperature, particularly freeze pulverization. Freeze crushing means that even an elastic body such as rubber has a property (low temperature brittleness) that becomes extremely brittle against impact when cooled below the embrittlement point. In this method, pulverization is performed while suppressing heat generation and preventing thermal denaturation.

The pulverization temperature in this embodiment is preferably Tg or less of the sample, and -50 ° C. or less in the present study.
An example of a freeze pulverizer that performs freeze pulverization is Linlex Mill (manufactured by Hosokawa Micron Corporation).
A thermal transfer print sheet can be manufactured using the pulverized toner for a thermal transfer print sheet manufactured as described above. That is, a peelable sheet having a releasable surface is supplied, an image to be thermally transferred onto a transfer medium is transferred to the peelable sheet, the pulverized toner for the thermal transfer print sheet is developed, and transferred to the peelable sheet. A thermal transfer print sheet is formed by forming a white toner layer by transferring onto the peeled image, fixing the image transferred to the peelable sheet and the white toner layer by heating and pressurizing, and fixing to a film shape. Is manufactured.

FIG. 1 is a cross-sectional view showing the internal structure of an apparatus for producing such a thermal transfer printed sheet. As shown in FIG. 1, the thermal transfer print sheet manufacturing apparatus 1 includes an image forming unit 2, a re-conveying unit 3, and a paper feeding unit 4.
The image forming unit 2 has a configuration in which five image forming units 5 (5-1, 5-2, 5-3, 5-4, 5-5) are arranged in a multistage manner.

  Of the five image forming units 5, three image forming units 5-1, 5-2, and 5-3 on the upstream side in the sheet conveying direction (right side in the drawing) are magenta (M ), Cyan (C), and yellow (Y) color toners are formed.

  The fourth image forming unit 5-4 following the three image forming units 5-1, 5-2, 5-3 forms a black (K) monochrome image. These four color toner images are overlaid on a peelable sheet (hereinafter also referred to as paper), which will be described later, to form a full color image.

Of the five image forming units 5, the image forming unit 5-5 on the most downstream side in the paper conveyance direction (the left end in the figure) is a transfer substrate (T) made of a thermoplastic resin containing a white pigment, which will be described in detail later. ) To form a solid white toner layer.
Each of the image forming units 5-1 to 5-5 has the same configuration except for the color and type of the developer stored in the developing unit. Therefore, hereinafter, the configuration of the image forming unit 5-4 will be described as an example.

The image forming unit 5 is assembled to the photosensitive drum 6, the cleaner 7 disposed along the circumferential surface of the photosensitive drum 6, the charging roller 8, the developing unit 9, and the opening on the lower side surface of the developing unit 9. The developing roller 11 is provided.
An optical writing head 12 on the main unit side is disposed in the vicinity of the upper surface located between the charging roller 8 of the photosensitive drum 6 and the developing unit 9. Further, a transport belt 13 is disposed in the vicinity of the lower surface of the photosensitive drum 6. The transfer device 14 is pressed toward the lower surface of the photosensitive drum 6 with the conveying belt 13 interposed therebetween.

The conveyor belt 13 is made of a conductive sheet-like member made of resin containing conductive carbon or an ion conductive material, is stretched over the drive roller 15 and the driven roller 16 and is driven by the drive roller 15, and the arrow in the figure. Circulately moves in the counterclockwise direction indicated by a, b, and c.
The photosensitive drum 6 rotates in the clockwise direction in the figure. First, by applying charge from the charging roller 8, the peripheral surface of the photosensitive drum 6 is uniformly charged and initialized. Next, an electrostatic latent image is formed on the peripheral surface of the photosensitive drum 6 by optical writing from the optical writing head 12 based on the print information.

  The electrostatic latent image is converted into a toner image (development) by the toner stored in the developing unit 9 by the developing process by the developing roller 11. The toner image developed on the peripheral surface of the photosensitive drum 6 is rotated and conveyed to a transfer portion where the photosensitive drum 6 and the transfer device 14 face each other as the photosensitive drum 6 rotates.

  On the other hand, the sheet feed cassette 17 of the sheet feed unit 4 accommodates a large number of cut sheet-like peelable sheets 18. The peelable sheet 18 is unloaded from the sheet feeding cassette 17 by one rotation of the sheet feeding roller 19, and is fed to the standby roller pair 22 through the conveyance guide path 21. Alternatively, when a small number of thermal transfer print sheets are produced, the peelable sheet 18 is fed from the MPF tray 24 mounted on the opened mounting portion 23 to the standby roller pair 22 by the paper feed roller 25. .

The standby roller pair 22 feeds onto the transport belt 13 at a timing at which the print start position of the peelable sheet 18 coincides with the front end of the toner image on the photosensitive drum 6 of the image forming unit 5-1 at the most upstream in the paper transport direction. .
The peelable sheet 18 is electrostatically adsorbed and conveyed on the upper surface of the circulating and conveying belt 13, and moves together with the conveying belt 13 directly below the photosensitive drum 6 from the upstream side to the downstream side in the paper conveying direction.

  Then, the peelable sheet 18 is transferred with the first color toner image at the transfer portion of the image forming unit 5-1, and transferred with the next color toner image at the transfer portion of the image forming unit 5-2. The third toner image is transferred by the transfer unit of the unit 5-3, and the black toner image is transferred by the transfer unit of the image forming unit 5-4. Further, the white toner layer on which the transfer base material (T) made of the thermoplastic resin containing the white pigment according to the present invention is printed is transferred at the transfer portion of the image forming unit 5-5.

  In the printing process in the full color printing mode in this example, the image forming units 5-1 to 5-4 are set to the printing state. On the other hand, the image forming unit 5-5 can be moved away from the contact position with the conveying belt 13 in accordance with the method for producing the thermal transfer print sheet.

  The thermal transfer printed sheet can be created by several different procedures, but there are roughly two types. That is, as a first method, the peelable sheet 18 on which the four color toner images are transferred as described above is continuously transferred with the white toner layer serving as a transfer substrate in the transfer portion of the image forming unit 55. Then, it is carried into the fixing unit 26. As a second method, the peelable sheet 18 onto which the four color toner images are transferred as described above is once carried into the fixing unit 26 and fixed, and then again through the re-conveying unit 3. In this method, after returning to the conveyance belt 13, a white toner layer serving as a transfer substrate is transferred onto the transfer unit of the image forming unit 5-5 and transferred to the fixing unit 26.

The fixing unit 26 includes a heat roller 26a, a pressure roller 26b, and a cleaner 26c.
In any case, the releasable sheet 18 is nipped and conveyed between the heat roller 26a and the pressure roller 26b, and the toner image is melted by heat and pressure and pressed onto the paper surface to fix the toner image and the white toner layer. The The cleaner 26c removes the toner remaining on the heat roller 26a.

  As described above, the peelable sheet 18 on which the full-color toner image and the transfer base material are fixed by the fixing unit 26 is rotated by the conveying roller 29 because the switching plate 27 is rotated downward as indicated by the broken line in the drawing. The sheet is conveyed upward, and is discharged to the paper discharge unit 32 by the paper discharge roller 31 with the image forming surface down. On the other hand, in the case of the peelable sheet 18 on which the four color toner images have been transferred and once carried into the fixing unit 26 as they are, the switching plate 27 is rotated downward, as indicated by the solid line in FIG. It is sent to the re-conveying unit 3 for printing.

Here, the re-conveyance unit 3 is provided with a plurality of conveyance rollers 33a to 33e. The re-conveyance unit 3 returns the paper to the conveyance guide path 21 so that it can be overprinted by temporarily stopping the conveyance of the paper and conveying by the plurality of conveyance rollers 33a to 33e.
In this example, the peelable sheet 18 on which the full-color toner image is fixed is sent to the re-conveying unit 3 as it is when the switching plate 27 is rotated upward as indicated by the solid line in the drawing.

In this case, the standby roller pair 22 has a timing at which the white toner layer printing position of the transfer base of the peelable sheet 18 coincides with the front end of the toner image on the photosensitive drum 6 of the image forming unit 5-5 at the most downstream side in the paper conveyance direction. Is fed onto the conveyor belt 13.
In the development and transfer of the white toner layer of the transfer substrate by the image forming unit 5-5, the conveyance belt 13 is separated downward from the image forming units 5-1 to 5-4. Then, the image forming unit 5-5 responsible for printing the white toner layer of the transfer base material is lowered from the upper retracted position, and the photosensitive drum 6 comes into contact with the transport belt 13.

  The subsequent printing of the white toner layer of the transfer substrate onto the peelable sheet 18 on which the image has been formed is almost the same as the image formation with the color toner described above. However, it is slightly different from the image formation with the color toner, that the print formation image by the white toner layer of the transfer base material is solid printing, and the solid image is printed in a predetermined shape on the other fixed toner image. That is.

The releasable sheet 18 on which the white toner layer of the transfer base material is solid-printed is again carried into the fixing unit 26 and the solid print image of the transfer base material is fixed on the paper surface.
Then, when the switching plate 27 operates to guide the peelable sheet 18 upward, the switching plate 27 is transported upward by the transport roller 29, and is discharged to the paper discharge unit 32 by the paper discharge roller 31 with the image forming surface down. The

Here, the control unit controls the drive of each unit of the thermal transfer print sheet creating apparatus 1 as described above, and controls the process of forming the color image and the white toner layer of the transfer base material on the peelable sheet 18 as described later. Will be described.
FIG. 2 is a circuit block diagram including the control device of the thermal transfer print sheet creating apparatus 1 described above. As shown in FIG. 2, the circuit block has a central processing unit (CPU) 35 as a center, and an interface controller (I / F_CONT) 36 and a printer controller (PR_CONT) 37 are connected to the CPU 35 via data buses. ing. A printer printing unit 38 is connected to the PR_CONT 37.

  The CPU 35 is connected to a ROM (read only memory) 39, an EEPROM (electrically erasable programmable ROM) 41, an operation panel 42 of the main body operation unit, and a sensor unit 43 to which outputs from sensors arranged in the respective units are input. ing.

A system program is stored in the ROM 39, and the CPU 35 performs processing by controlling each unit in accordance with the system program.
That is, in each unit, first, the I / F_CONT 36 converts print data supplied from a host device such as a personal computer into bitmap data and develops it in the frame memory 44.

In the frame memory 44, storage areas are set for each of black (K), magenta (M), cyan (C), yellow (Y), and transfer base (T), and data of each color and transfer base corresponds. It is expanded to the area to be.
The data expanded in the frame memory 44 is output to the PR_CONT 37, and is output from the PR_CONT 37 to the printer printing unit 38.

  The printer printing unit 38 is an engine unit, and is controlled by the PR_CONT 37, such as a rotation driving system (not shown) including the photosensitive drum 6 shown in FIG. 1, the charging roller 8, the optical writing head 12, and the like. An image forming unit having a driving unit and a driving unit (not shown) that drives the vertical movement of the conveying belt 13 are provided.

Then, the printer control unit 38 supplies the image data of each color of black (K), magenta (M), cyan (C), and yellow (Y) to the corresponding optical writing head 12 shown in FIG.
Further, the printer control unit 38 forms the electrostatic latent image on the photosensitive drum 6 based on the image data by the optical writing head 12 and the color or color corresponding to the formed electrostatic latent image via the developing unit 45. Controls development of the transfer substrate with toner.

Further, the printer printing unit 38 performs various controls such as an applied voltage to a heat generating unit built in the heat roller 26a of the fixing unit 26 and adjustment of pressure applied to the pressure roller 26b that presses the heat roller 26a via the fixing unit 46. Controls the drive output to be performed.
Further, the printer printing unit 38 controls a driving output for performing vertical movement of the belt position control mechanism of the conveying belt 13 and rotational driving of the driving roller 15 that circulates and moves the conveying belt 13 via the belt driving unit 47.

  FIGS. 3A to 3C are diagrams schematically showing a manufacturing process of a thermal transfer print sheet performed by the thermal transfer print sheet manufacturing apparatus 1 having the above-described configuration. FIGS. It is a figure which shows the process and procedure which transfer the label image of a thermal transfer print sheet to a transfer medium.

  FIG. 3A shows the first step, which is placed and accommodated in the paper feed cassette 17 or MPF tray 24 and sent out to the conveyor belt 13 by the paper feed roller 19 or 25 with the releasable surface facing up. A transparent sheet 18 (shown by hatching in order to distinguish it from a transfer substrate in a later step) is shown.

  FIG. 3B shows the second step, in which a normal image of an image to be transferred and printed on a transfer medium is optically written by the image forming units 5-1, 5-2, 5-3, and 5-4. A state is shown in which writing is performed by the head 12, this is developed, and the developed normal image is transferred as a mirror image 48 to the releasable surface of the peelable sheet 18.

  FIG. 3C shows a third step. The peelable sheet 18 is covered so that the white thermoplastic resin layer 49 in which the white toner is developed into a film shape by the image forming unit 5-5 covers the mirror image 48. Then, the peelable sheet 18 onto which the white thermoplastic resin layer 49 has been transferred is transferred to the fixing unit 26, and is sandwiched between the heat roller 26a and the pressure roller 26b to be heated and heated. The state of the thermal transfer print sheet 50 to which the film-shaped white thermoplastic resin layer 49 is fixed by pressure is shown.

That is, the processes from the first step to the third step complete the creation of the thermal transfer print sheet 50 including the peelable sheet 18, the mirror image 48, and the white thermoplastic resin layer 49 of the film-shaped transfer base.
The mirror image 48 and the white thermoplastic resin layer 49 may be fixed by simultaneously fixing the mirror image 48 and the white thermoplastic resin layer 49 by heating and pressing after the mirror image 48 and the white thermoplastic resin layer 49 are transferred. However, after the mirror image 48 is transferred, the mirror image 48 is preliminarily fixed, and after the white thermoplastic resin layer 49 is transferred, the white thermoplastic resin layer 49 may be fixed by heating and pressing.

  Subsequently, FIG. 3D shows a fourth step. For example, the heat transfer print sheet 50 is transferred to a transfer medium 52 such as a T-shirt using, for example, a heat press machine 51 commercially available for industrial use. On the other hand, the mirror image forming surface (releasing surface) 50-1 is made to face and overlap.

  Then, the thermal transfer print sheet 50 can be peeled off from the back surface 50-2 of the mirror image forming surface 50-2 of the thermal transfer print sheet 50 by heating and pressurization so that the peelable sheet 18 can be peeled off after cooling. The layer 49 is adhered to the transfer medium 52 via the layer 49.

In the above example, the heating press machine 51 is used. However, since the heating press machine 51 is large and expensive as a machine, the thermal transfer print sheet 50 and the mirror image 48 are transferred to the medium to be transferred by manual ironing. You may make it adhere to 52.
Thereafter, when the thermal transfer printed sheet 50 is cooled to about room temperature and the peelable sheet 18 is peeled off manually, as shown in FIG. 3E, the transferred object which is a printing object such as a T-shirt. On the medium 52, transfer printing of the image label 53 from the mirror image 48 to the normal image 48a is completed.

  Thereby, the thermal transfer printed sheet 50 in which the image is formed on the opaque white label can be created. When this is transferred and printed on a dark-colored garment, a label having an image formed on a white background is transferred and printed, so that the appearance of the image is improved even if the transfer medium 52 is a dark-colored garment.

The thermal transfer print sheet manufacturing apparatus, the manufacturing method, and the thermal transfer print sheet according to one embodiment of the present invention have been described above. The pulverized toner that is the transfer substrate composition will be described below.
EXAMPLES Hereinafter, the Example and comparative example of this invention are shown and this invention is demonstrated concretely.
<Measurement method of each physical property value>
The measuring method of the physical property value used in each example is shown below.
<Measurement of softening point>
For measurement of the softening point, the apparatus is a flow tester (manufactured by Shimadzu Corporation, CFT-500D), the sample is 1 g, the heating rate is 6 ° C./min, the load is 20 kg, the nozzle is 1 mm in diameter, 1 mm in length, The softening point was 1/2 method (temperature at which half of the sample was discharged).
<Measurement of particle size>
To measure the toner particle size, the apparatus was FPIA-2100 (manufactured by Sysmex Corporation), and the sample was dispersed in a beaker with a small amount of sample, purified water, and a surfactant in an ultrasonic cleaner. As a measurement result, a volume average particle size (D50) was obtained.
<Synthesis of polybutylene succinic acid as resin component of pulverized toner>
As a synthesis example, 5 parts by mass of 88% lactic acid aqueous solution in which 0.4 part by mass of malic acid and 1 part by mass of germanium dioxide were dissolved was added to 100 parts by mass of succinic acid and 89 parts by mass of 1,4-butanediol. . After making the inside of a reaction system into nitrogen atmosphere, it was made to react at 220 degreeC for 1 hour, and it was pressure-reduced to 70 Pa over 1.5 hours then heating up at 230 degreeC. Polymerization was further allowed to proceed for 2 hours to obtain polybutylene succinic acid.
<Manufacture of white toner>
Example 1
81.5 parts by mass of polybutylene succinic acid obtained in Synthesis Example, 15 parts by mass of talc (SG-2000; manufactured by Nippon Talc Co., Ltd.), 1 mass of LR-147 (manufactured by Nippon Carlit Co., Ltd.) as a charge control agent And 2.5 parts by mass of Carnauba wax (manufactured by Kato Yoko Co., Ltd.) were mixed, and the mixture was kneaded with a biaxial extrusion kneader.

The obtained kneaded product was pulverized under liquid nitrogen by a low-temperature pulverizer (Linlex Mill; manufactured by Hosokawa Micron Corporation) to obtain a powder having a D50 (volume) of 37 μm.
Stirring with a Henschel mixer together with 0.2 parts by mass of two types of silica particles RY200 (manufactured by Nippon Aerosil Co., Ltd.) and 0.7 parts by mass of NY50 (manufactured by Nippon Aerosil Co., Ltd.), wherein 100 parts by mass of this powder were hydrophobized Thus, Toner 1 having silica particles added thereto was obtained. The toner 1 had a D50 (volume) of 33 μm and a softening point of 126 ° C.

Example 2
Toner 2 was obtained in the same procedure as in Example 1 except that 15 parts by mass of kaolin (ASP072; Hayashi Kasei Co., Ltd.) was used instead of 15 parts by mass of talc. The toner 1 had a D50 (volume) of 39 μm and a softening point of 126 ° C.
Example 3
Toner 3 was obtained in the same procedure as in Example 1 except that 15 parts by mass of zinc sulfide fine particles were used instead of 15 parts by mass of talc. The toner 1 had a D50 (volume) of 39 μm and a softening point of 126 ° C.

The zinc sulfide fine particles were produced by the following method. 100 parts by mass of zinc sulfide (Sachtolish L; manufactured by Zachtreben Co., Ltd.) was mixed with 800 parts by mass of ion-exchanged water and 500 parts by mass of 100 μm-diameter alumina beads, and stirred for 10 hours in a ball mill.
Next, after the alumina beads were removed from the mixed solution through a sieve having an opening of 50 μm, the precipitate was collected and dried to obtain zinc sulfide fine particles having a D50 (volume) of 0.4 μm.

Example 4
Toner 4 was obtained in the same manner as in Example 1, except that 15 parts by mass of barium sulfate (B-30; manufactured by Sakai Chemical Industry Co., Ltd.) was used instead of 15 parts by mass of talc. The toner 1 had a D50 (volume) of 39 μm and a softening point of 126 ° C.
Example 5
Toner 5 was obtained in the same procedure as in Example 1 except that 15 parts by mass of calcium carbonate (Imeris Mineral Co., Ltd.) having a D50 of 0.4 μm was used instead of 15 parts by mass of talc. The toner 1 had a D50 (volume) of 40 μm and a softening point of 126 ° C.

Example 6
Toner 6 was obtained in the same procedure as in Example 1 except that 15 parts by mass of zinc oxide (Hisui Tech Co., Ltd.) was used instead of 15 parts by mass of talc. The toner 6 had a D50 (volume) of 38 μm and a softening point of 126 ° C.
Comparative Example 1
Toner 7 was obtained in the same procedure as in Example 1 except that 15 parts by mass of zirconium oxide was used instead of 15 parts by mass of talc. The toner 7 had a D50 (volume) of 33 μm and a softening point of 126 ° C.

In addition, as zirconium oxide, what pulverized UEP made from a 1st rare element chemical industry Co., Ltd. to the particle size of 0.3 micrometer with the bead mill was used.
Comparative Example 2
Toner 8 was obtained by the same procedure as in Example 1 except that 15 parts by mass of titanium oxide (CR-60; manufactured by Ishihara Sangyo Co., Ltd.) was used instead of 15 parts by mass of talc. This toner 8 had a D50 (volume) of 33 μm and a softening point of 126 ° C.

  In the production of the toners 1 to 8 in Examples 1 to 6 and Comparative Examples 1 and 2 above, the results of examining the damage of the low-temperature pulverizer used are shown below together with the Mohs hardness, new Mohs hardness and refractive index of the white pigment. Shown in the table.

上記表１に示すように、新モース硬度が５以下である白色顔料を用いてトナー１〜６を得た実施例１〜６では、いずれも粉砕機のダメージは認められなかった。これに対し、新モース硬度が１１である酸化ジルコニウムを用いた比較例１、及び新モース硬度が８〜８．５である酸化チタンを用いた比較例２では、いずれも粉砕機のダメージが認められ、その使用は困難であった。
＜シャツへのプリント＞
カシオ計算機（株）製Ｎ５３００プリンタにより、ＰＥＴ製透明セパレーター上にカラーの反転画像を現像した後、トナー１をカラー画像を覆うように現像して、熱定着させ、熱転写プリントシートを作成した。この熱転写プリントシートにおける定着後のトナー１の厚みは５０μｍであった。その後、黒色無地のＴシャツの印字箇所に熱転写プリントシートをトナー面が接するように合わせ、セパレーターの裏面から暖めたアイロンを押し当てた。Ｔシャツが室温程度まで十分に冷えた後、透明セパレーターを剥がしたところ、Ｔシャツ上に画像を転写することができた。得られたＴシャツを洗濯機にて洗濯して、その後の状態を確認した。

As shown in Table 1 above, in Examples 1 to 6 where toners 1 to 6 were obtained using a white pigment having a new Mohs hardness of 5 or less, no damage to the pulverizer was observed. In contrast, in Comparative Example 1 using zirconium oxide having a new Mohs hardness of 11 and Comparative Example 2 using titanium oxide having a new Mohs hardness of 8 to 8.5, damage to the grinder was recognized. And its use was difficult.
<Print on shirt>
A color reversal image was developed on a PET transparent separator using an N5300 printer manufactured by Casio Computer Co., Ltd., and then the toner 1 was developed to cover the color image and thermally fixed to prepare a thermal transfer print sheet. The thickness of toner 1 after fixing on this thermal transfer print sheet was 50 μm. Thereafter, the thermal transfer printed sheet was aligned with the printed portion of the black plain T-shirt so that the toner surface was in contact, and a heated iron was pressed from the back surface of the separator. After the T-shirt was sufficiently cooled to about room temperature, the transparent separator was peeled off, and an image could be transferred onto the T-shirt. The obtained T-shirt was washed in a washing machine, and the subsequent state was confirmed.

As a result, the image quality of the T-shirt image was good.
A thermal transfer print sheet was prepared in the same manner except that the toners 2 to 8 were used instead of the toner 1, and when the image was transferred onto the T-shirt, the image quality of the T-shirt was good.
The above-described example is a transfer printing method that is particularly effective for fabric products such as T-shirts and trainers. However, the object of transfer printing can also be applied to metals, wood, resin, paper, ceramics, and the like.

  In addition, 1,4-butanediol is used in the synthesis of polybutylene succinic acid that is a resin component of the white toner, but in addition to 1,4-butanediol, ethylene glycol, 1,3-propanediol, 1, Directly such as 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc. Chain end diols may be used.

  Further, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,5-hexanediol, 1,2-propanediol, 1,2-butanediol, 1, Branched diols such as 3-butanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol are also considered effective. It is also possible to use a plurality of these.

  It is also possible to copolymerize a dicarboxylic acid different from succinic acid. The following can be considered as the dicarboxylic acid. That is, oxalic acid, malonic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.

In particular, for T-shirt prints, the softer the film to be thermally transferred, the better the washing resistance. Therefore, it is considered effective to soften polybutylene succinic acid by copolymerization of adipic acid.
Although several embodiments of the present invention have been described, the present invention is included in the invention described in the claims and the equivalents thereof.

Hereinafter, the invention described in the scope of claims of the present application will be appended.
[Appendix 1]
A pulverized toner for a thermal transfer print sheet comprising: a polyester resin containing a unit obtained by condensing an aliphatic dicarboxylic acid and an aliphatic diol; and a melt-kneaded product containing a white pigment having a new Mohs hardness of 5 or less. .
[Appendix 2]
The pulverized toner for thermal transfer printed sheets according to appendix 1, wherein the white pigment is at least one selected from the group consisting of talc, kaolin, zinc sulfide, barium sulfate, calcium carbonate, and zinc oxide.
[Appendix 3]
The pulverized toner for thermal transfer printed sheets according to appendix 1, wherein the aliphatic dicarboxylic acid is succinic acid and the aliphatic diol is 1,4-butanediol.
[Appendix 4]
A step of melt-kneading a polyester resin containing a unit obtained by condensing an aliphatic dicarboxylic acid and an aliphatic diol and a white pigment having a new Mohs hardness of 5 or less, and a step of pulverizing the obtained melt-kneaded product A method for producing a pulverized toner for a thermal transfer print sheet.
[Appendix 5]
A releasable sheet having a releasable surface;
A print image formed on the peelable sheet and thermally transferable to a transfer medium;
A thermal transfer print sheet comprising a white toner layer formed by transferring and fixing the pulverized toner according to any one of appendices 1 to 3 on the print image.
[Appendix 6]
A releasable sheet supplying step for supplying a releasable sheet having a releasable surface;
An image forming step of transferring an image to be transferred to a transfer medium to the peelable sheet;
A white toner layer forming step of developing the pulverized toner according to any one of appendices 1 to 3 and transferring the developed toner onto an image transferred to the release sheet;
A method for producing a thermal transfer print sheet, comprising: a fixing step of fixing the image and the white toner layer transferred to the peelable sheet by heating and pressurization to fix them in a film shape.
[Appendix 7]
Using a heating press, the thermal transfer print sheet according to appendix 5 is overlapped with the image forming surface facing the transfer medium, heated and pressurized from the back side of the image forming surface of the thermal transfer print sheet, and after cooling A thermal transfer printing method, wherein the release sheet is peeled off, and the white toner layer and the image of the thermal transfer print sheet are thermally transferred to a transfer medium.

  The present invention provides a pulverized toner for a thermal transfer print sheet that can be bonded by melting and bonding an image to a printing object on a white background without using an adhesive, and that does not damage the pulverizer. The thermal transfer printed sheet, the thermal transfer printed body manufactured using the thermal transfer printed sheet, and the manufacturing method thereof can be used.

DESCRIPTION OF SYMBOLS 1 ... Thermal transfer print sheet preparation apparatus 2 ... Image formation part 3 ... Re-conveyance unit 4 ... Paper feed part 5 (5-1, 5-2, 5-3, 5-4, 5-5) ... Image formation unit 6 ... Photosensitive drum 7... Cleaner 8, 8 a, 8 b... Charging roller 9. Developing unit 11. Developing roller 12... Optical writing head 13 ... Conveying belt 14 ... Transfer device 14 ′ Transfer roller 15. ... Paper cassette 18 ... Releasable sheet (paper)
DESCRIPTION OF SYMBOLS 19 ... Paper feed roller 21 ... Conveyance guide path 22 ... Waiting roller pair 23 ... Mounting part 24 ... MPF (Multi Paper Feeder) tray 25 ... Paper feed roller 26 ... Fixing unit 26a ... Heat roller 26b ... Pressure roller 26c ... Cleaner 27 ... Switching plate 28 ... fulcrum 29 ... conveying roller 31 ... discharge roller 32 ... discharging unit 33a to 33e ... conveying roller 35 ... CPU
36 ... Interface controller (I / F_CONT)
37 ... Printer controller (PR_CONT)
38 ... Printer printing section 39 ... ROM
41 ... EEPROM
DESCRIPTION OF SYMBOLS 42 ... Operation panel 43 ... Sensor part 44 ... Frame memory 45 ... Belt drive part 46 ... Fixing part 47 ... Belt drive part 48 ... Mirror image 48a Normal image 49 ... Film-shaped toner image of a transfer base material 50 ... Thermal transfer print sheet 50 ... Mirror image forming surface 50-2: Back surface of mirror image forming surface 51 ... Heating press machine 52 ... Medium to be transferred 53 ... Label image 53a ... Transfer image

Claims (7)

  A pulverized toner for a thermal transfer print sheet comprising: a polyester resin containing a unit obtained by condensing an aliphatic dicarboxylic acid and an aliphatic diol; and a melt-kneaded product containing a white pigment having a new Mohs hardness of 5 or less. .   2. The pulverized toner for a thermal transfer print sheet according to claim 1, wherein the white pigment is at least one selected from the group consisting of talc, kaolin, zinc sulfide, barium sulfate, calcium carbonate, and zinc oxide.   The pulverized toner for a thermal transfer printed sheet according to claim 1, wherein the aliphatic dicarboxylic acid is succinic acid, and the aliphatic diol is 1,4-butanediol. A step of melt-kneading a polyester resin containing a unit obtained by condensing an aliphatic dicarboxylic acid and an aliphatic diol and a white pigment having a new Mohs hardness of 5 or less, and a step of pulverizing the obtained melt-kneaded product A method for producing a pulverized toner for a thermal transfer print sheet. A releasable sheet having a releasable surface;
A print image formed on the peelable sheet and thermally transferable to a transfer medium;
A thermal transfer print sheet comprising a white toner layer formed by transferring and fixing the pulverized toner according to claim 1 on the print image. A releasable sheet supplying step for supplying a releasable sheet having a releasable surface;
An image forming step of transferring an image to be transferred to a transfer medium to the peelable sheet;
A white toner layer forming step of developing the pulverized toner according to any one of claims 1 to 3 and transferring the developed toner onto an image transferred to the peelable sheet;
A method for producing a thermal transfer print sheet, comprising: a fixing step of fixing the image and the white toner layer transferred to the peelable sheet by heating and pressurization to fix them in a film shape.   Using a heating press, the thermal transfer print sheet according to claim 5 is superposed with the image forming surface facing the transfer medium, heated and pressurized from the back side of the image forming surface of the thermal transfer print sheet, and cooled. A thermal transfer printing method, wherein the release sheet is peeled off later, and the white toner layer and the image of the thermal transfer print sheet are thermally transferred to a transfer medium.

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