JPH08305064A - Transfer picture transfer material for electrophotography - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a transfer image transfer material for electrophotography, which has improved water resistance, reduced curl amount after standing, and stable release property of film layer. A transfer picture transfer material for electrophotography comprising a polymer resin film on a substrate, wherein the polymer resin film comprises three layers of an adhesive layer, a release layer and a transfer layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is an apparatus for forming an image by using a charged powder such as an electrophotographic apparatus and an electrostatic recording apparatus, and the obtained powder image is retransferred to another final transfer material. And a transferable transfer material for electrophotography.

[0002]

2. Description of the Related Art Conventionally, it is widely known to transfer an image three-dimensionally by using a technique called a transfer picture. For example, a base material such as paper is coated with a water-soluble glue typified by dextrin. , A required image is formed on this coating film by using acrylic ink by screen printing, etc., the paper with this image is dipped in water to dissolve the dextrin, and the acrylic ink image floating in water is made into a three-dimensional object such as pottery. A water pressure transfer method of transferring the water pressure by water pressure is widely known. An example of a direct application of the transfer paper used in this method to electrophotography is Templin manufactured by Muto Kogyo. This transfer material is made by forming a film of dextrin on rice paper as a transfer material,
This is applied to an electrophotographic device to form a toner image on the surface of the dextrin, and then this transfer material is passed through an organic solvent that can soften the resin in the toner, and transferred to the transfer medium that is the object of retransfer to the toner image. After applying this adhesive force, the transfer material is brought into close contact so that the toner image faces the retransfer medium, and then water is applied from the back surface of the paper to dissolve the dextrin film and transfer only the toner image. Is.

However, with a transfer material formed by forming a water-soluble coating film on such an opaque paper, not only is it difficult to align the position at the time of retransfer, but also the influence of moisture in the atmosphere causes the image to be formed before image formation. There is a problem that the surface of the transfer material is softened and the softened dextrin adheres to the photosensitive drum or the like in the electrophotographic apparatus. Further, as described above, since it is sensitive to moisture in the air, it expands and shrinks greatly with respect to the amount of moisture, causing unnecessary curling of the transfer material, which considerably deteriorates the sheet conveyance property in the apparatus.

To solve the above two problems, Japanese Patent Laid-Open No. 4-361
In 086, there is proposed a retransfer material using polyvinyl alcohol, which is a saponified product of vinyl acetate, instead of dextrin. The transfer material proposed here is a paper coated with a silicone resin and coated with Nichika Chemical's Casesol 0-5 mixed with a silicone defoaming agent. After forming a toner image on the coating film by an electrophotographic apparatus, the caser film is peeled off from the base material and superposed so that the toner image faces the retransfer medium.

By applying heat and pressure, the resin in the toner image is softened to obtain the adhesive force to the retransfer medium, and after cooling, 80% of ethyl alcohol is added from the rear surface of the caser film.
% Aqueous solution to reduce the adhesive force between the caser film and the toner image to complete the retransfer.

According to this method, since the thin film having the toner image is peeled off from the base material, it becomes a substantially transparent film, and the alignment is easy.

[0007]

However, in the above-mentioned conventional example, since the coating material used is a partial saponification product of vinyl acetate, it is sensitive to moisture in the air like temprin. However, there is a problem that remarkable curling occurs before image formation, and further, the coating film remains due to dissolution of the film when the coating film is peeled off. Further, it has been found that since silicone is used as the release film, the film peels off during the transfer of the transfer material in the electrophotographic apparatus.

An object of the present invention is to provide a transfer picture transfer material for electrophotography, which has improved water resistance, a reduced amount of curl on standing and a stable release property of the film layer.

[0009]

[Means for Solving the Problems] That is, the first aspect of the present invention is an electrophotographic transfer picture transfer material having a polymer resin film on a substrate, wherein the polymer resin film comprises an adhesive layer, a release layer and It is a transfer picture transfer material for electrophotography, which is composed of three transfer layers.

The second invention is the same as the first invention,
This is the case where the polymer resin film can be peeled off at the interface between the adhesive layer and the release layer.

A third aspect of the present invention is the same as the first aspect of the present invention.
The adhesive force between the adhesive layer and the release layer is 1.5 g / cm or more and 4 g / c
This is the case of m or less.

The fourth invention is the same as the first invention,
This is the case where the adhesive layer contains a resin selected from acrylic, polyester and nylon.

A fifth aspect of the present invention is the same as the first aspect of the present invention.
This is the case where the release layer contains polyvinyl alcohol.

A sixth aspect of the present invention is the same as the fifth aspect of the present invention.
This is a case where the release layer contains polyvinyl alcohol having a saponification degree of 90% or less and a silicone resin.

A seventh aspect of the present invention is the same as the fifth aspect of the present invention.
This is the case where the polyvinyl alcohol is obtained by saponifying polyvinyl acetate at 95% or more.

An eighth aspect of the present invention is the same as the first aspect of the present invention.
The transfer layer contains 95% or more polyvinyl acetate saponified polyvinyl alcohol and 90% or less vinyl acetate saponified polyvinyl alcohol, and the saponification degree of 95% or more of the polyvinyl alcohol content is 25% by weight or more as a solid component. This is the case of less than 75% by weight. The transfer layer is not a partially saponified vinyl acetate simple substance like the conventional casezole 0-5,
By using a partially saponified vinyl acetate and a vinyl acetate saponified at 95% or more together, the water resistance is improved and is stabilized against moisture in the air.

A ninth aspect of the present invention is the same as the first aspect of the present invention.
The surface resistivity of the transfer layer is 10 ⁸ to 10 ¹² Ω / □ under the environment of 20 ° C. and 65% RH.

[0018]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 shows a transfer picture transfer material 1 for electrophotography according to the present invention.
FIG. 3 is a schematic cross-sectional view showing the layer structure of FIG. 11 is the transfer material 1 coated
A medium or high-quality plain paper, or
Use talc, decals, etc. on one or both sides of these papers for
Paper coated with surface coating such as rubber
A heat resistant film such as ethylene terephthalate is used.
For paper, the basis weight is 30 g / m² Above is preferred, 45g
/ M² The above is more preferable. 30 g / m² Less than paper
Can be transported in an electrophotographic device even if the coating resin film is thickened.
Is difficult to secure. The basis weight is 200 g / m² Less than
Is preferred, 150 g / m² The following is more preferable. 20
0 g / m² If the temperature exceeds the limit, the rigidity of the base paper will be too high,
Deliverability tends to be poor. In addition, this base paper
In order to maintain good image transferability in storage,
An inorganic salt such as thorium is added in an amount of 0.2 to 4% by weight.
Leave for 24 hours in an environment with volume resistance of 20 ° C and 65% RH
In 10⁸ -10^TenIt is preferable that it is adjusted to Ω · cm
New Also, when using a film material for the base,
Biaxially stretched heat resistant PET film from the viewpoint of transportability
In the case of, the thickness is preferably 50 μm or more,
It is more preferably m or more and 150 μm or less. In addition, this file
As for Rum, cationic or non-iodinated on the B side of the drawing.
Coated with an antistatic layer consisting of a surface-active agent
Specific resistance is 10 ⁸ -10¹²Ω / □ (20 ° C, 65% R
It is preferably adjusted to H).

Reference numeral 12 is an adhesive layer, which is provided to prevent the release layer 13 and the transfer layer 14 to be applied later from peeling off easily in the electrophotographic apparatus. Examples of the material used include aqueous acrylic emulsion, water-soluble acrylic, water-soluble polyester, 6.6 nylon, polyacrylonitrile, and acrylic resin soluble in an organic solvent. When the paper is the base material, all of the above materials can be used. However, in the case of a resin film such as PET, the base material should be selected so as to obtain a sufficient adhesive force.
In the case of PET or the like, a water-soluble polyester is preferable, and a type in which the water resistance after drying the coating film is improved by adding ammonium chloride at the time of forming the coating film is preferable.

Next, 13 is a release layer, which is mainly composed of polyvinyl alcohol which is a saponification product of polyvinyl acetate, and whose saponification degree is 95% or more, preferably 98%.
The above is more preferable. When polyvinyl alcohol having a saponification degree of 90% or less is used, it is possible to use a release agent mixed with a small amount of a water-soluble silicone resin. However, it is difficult to use polyvinyl alcohol having a saponification degree of less than 70% in terms of water resistance.

The mutual selection of materials for the release layer 13 and the adhesive layer 12 is also influenced by the adhesive force, and the adhesive strength is at least 1.5 g at 90 ° peeling so that the peeling layer 13 and the adhesive layer 12 are not peeled off by the carrying force in the electrophotographic apparatus. / Cm or more is preferable, and the transfer layer 14 and the release layer 13 described later are preferably used.
It is preferably 4 g / cm or less so that the film does not break when the retransfer film layer consisting of is peeled from the substrate.

Next, the transfer layer 14 will be described. This layer receives a toner image by an electrophotographic apparatus, holds the toner image at least until it enters a retransfer step by heating, and at the time of retransfer, it is sufficient. It is required to have excellent toner peeling performance. Further, it is required to have sufficient water resistance as compared with the prior art. That is, it is necessary to ensure excellent solvent permeability at the time of retransfer and have excellent water resistance. Specifically, the transfer layer is formed by mixing polyvinyl alcohol obtained by saponifying polyvinyl acetate at 95% or more with polyvinyl alcohol obtained by saponifying polyvinyl acetate at 90% or less. The mixing ratio is such that the content of the highly saponified polyvinyl alcohol having a solid content ratio of 95% or more is preferably 10% by weight or more, and more preferably 25% by weight or more. Below 10% by weight, 90
The water-soluble property, which is a characteristic of polyvinyl alcohol having a low saponification degree of not more than%, appears strongly, and the surface layer may be melted out in a high temperature environment, possibly contaminating the members in the electrophotographic apparatus. Furthermore, the high saponification degree of polyvinyl alcohol is 7
When the content is 5% by weight or more, the alignment of the linear polymer forming the film itself has high regularity as in the case of the cellulose film, so that the film shrinkage may increase with a change in the amount of water in the air. That is, the high-saponification degree polyvinyl alcohol is more preferably 25% by weight or more and less than 75% by weight as a solid content ratio. Further, if necessary, a cationic or nonionic antistatic agent may be added to the transfer layer 14 to improve electrophotographic transferability. The amount of antistatic agent is 10 ⁸ to 10 ¹² Ω / □ as the target surface resistivity.
Adjust so that Further, an inorganic white pigment such as silica powder may be mixed in order to secure the paper transporting property.

Regarding the thickness of each layer, it is preferable that the adhesive layer 12 is a thin layer so that the film does not split and peel.
It is preferably not less than 10 μm and not more than 10 μm. If it is less than 2 μm, unevenness is likely to occur, and if it exceeds 10 μm, intralayer peeling is likely to occur.

The release layer 13 has a role of a primer layer of the transfer layer 14 and a role of achieving sufficient peeling at the interface between the transfer layer 14 and the adhesive layer 12, and the thickness thereof is 2 μm or more and 6 μm or less. preferable. If it exceeds 6 μm, the shrinkage of the layer due to moisture is strong and curling is likely to occur, and if it is less than 2 μm, unevenness is likely to occur.

The thickness of the transfer layer 14 is preferably 8 μm or more. If the thickness is smaller than this range, insufficient strength is likely to occur such as breakage of the film when peeled from the substrate. Also, 50μ
m or less is preferable. If it is thicker than this, the film after peeling becomes hard and the followability of the curved surface is likely to be lowered at the time of retransfer. A more preferable film thickness is 10 μm or more and 40 μm or less.

Next, the electrophotographic toner applicable to the copy transfer material of the present invention will be described in detail. Basically, for electrophotography, which contains dyes and pigments such as yellow, cyan and magenta in addition to carbon black in a binder resin mainly composed of a resin such as styrene-acrylic copolymer, styrene-butadiene copolymer, epoxy and polyester. Toner is available. Among them, in particular, the color toners described below can bring out the effect of the transfer picture transfer material of the present invention.

The toner powder for this color electrophotographic apparatus is
It is necessary to have good meltability and color mixing property when heat is applied, and a sharp melt toner having a low softening point and a short melting time is preferable.

By using a sharp melt toner, it is possible to widen the color reproduction range of the copy and obtain a good color copy faithful to the multicolor image of the original.

Such a sharp-melt toner may be a binder resin such as polyester resin or styrene-acrylic resin, a coloring agent (dye, sublimable dye),
A toner is manufactured by melt-kneading, pulverizing and classifying a charge control agent and the like. If necessary, an external addition step of adding various external additives to the toner may be added.

Considering the fixing property and the sharp melt property, the color toner preferably uses a polyester resin as a binder resin. The sharp melt polyester resin is a polymer compound having an ester bond in the main chain of a molecule synthesized from a diol compound and a dicarboxylic acid. In particular,

[0032]

Embedded image (In the formula, R is an ethylene or propylene group, x,
Each y is a positive integer of 1 or more, and the average value of x + y is 2 to 10. ), A bisphenol derivative represented by the formula (1) or a substituted product thereof is used as a diol component, and a carboxylic acid component composed of a carboxylic acid having a valence of 2 or more or an acid anhydride thereof or a lower alkyl ester thereof (eg fumaric acid
A polyester resin obtained by at least copolycondensing maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) is more preferable because it has sharp melting characteristics.

The softening point of the sharp melt polyester resin is preferably 60 to 120 ° C. FIG. 2 shows the softening point characteristics of the toner containing the sharp melt polyester resin as a binder resin.

A flow tester CFT-500 type (manufactured by Shimadzu Corporation) was used, and the diameter of the die (nozzle) was 0.5 mm.
A thickness of 1.0 mm, an extrusion load of 50 kg, an initial set temperature of 80 ° C., a preheating time of 300 seconds, and a constant temperature increase at a rate of 5 ° C./min. Hereinafter, the softened S-shaped curve) is obtained. As the sample toner, fine powder finely weighed from 1 to 3 g is used, and the cross-sectional area of the plunger is 10 cm ² . The softened S-shaped curve is as shown in FIG. As the temperature rises at a constant rate, the toner is gradually heated and begins to flow (plunger descending A → B). When the temperature is further raised, the toner in a molten state largely flows out (B → C → D), and the plunger lowering is stopped and completed (D → E).

The height H of the S-shaped curve indicates the total outflow amount, and H /
The temperature T ₀ corresponding to point C of 2 indicates the softening point of the toner.

Such a sharp melt type toner or resin means that the temperature at which the melt viscosity is 10 ⁵ is T ₁ ,
When the temperature when 5 × 10 ⁴ cp is shown is T ₂ , T ₁ = 90 to 150 ° C. | ΔT | = | T ₁ −T ₂ | = 5 to
A resin that satisfies the condition of 30 ° C.

The sharp-melting toner or resin having these temperature-melt viscosity characteristics is characterized by extremely sharply decreasing the viscosity when heated. Such a decrease in viscosity causes a proper mixing of the uppermost toner layer and the lowermost toner layer, and further sharply increases the transparency of the toner layer itself, thereby causing good color-reducing mixing.

Next, specific examples of the present invention will be described. In the specific examples, parts indicate parts by weight.

[Example 1] A transfer material was obtained according to the following formulation by using, as a base paper, a single coated paper obtained by subjecting one side of a medium-weight paper having a basis weight of 64 g / m ² to a mixture of starch and talc. .

(Adhesive Layer) A coating liquid consisting of acrylic base resin (plus size LO-170, manufactured by Kyowa Chemical Co., Ltd.) 100 parts and toluene 100 parts was formed into a coating film thickness of 7 μm by a lip coater.

(Release Layer) Polyvinyl alcohol having a high degree of saponification (saponification degree 99%, Kuraray Poval PVA110, made by Kuraray) 10 parts Water A coating solution of 90 parts was formed on the adhesive layer with a comma coater to a coating thickness of 3 μm. did.

(Transfer Layer) Low Saponification Degree Polyvinyl Alcohol (Saponification Degree 88%, Casesol 05, Nika Kagaku) 50 parts High Saponification Degree Polyvinyl Alcohol (Kuraray Poval PVA110) 50 parts Water 5 parts Antistatic agent (solid content) 30%, cation AB, manufactured by NOF CORPORATION) 2.5 parts was prepared, and a coating film was formed on the release layer so as to have a thickness of 16 μm.

The peeling force of the obtained transfer material from the substrate of the transfer layer and the release layer was 2.5 g / cm. The surface resistance of the transfer material was 10 ¹¹ Ω / □.

When the above-mentioned transfer material was passed through a CLC700 manufactured by Canon, good transferability was obtained without peeling of the coating film from the substrate. Further, good primary fixing was obtained without peeling of the toner image.

A film in which a release layer having a toner image and a transfer layer are integrated is peeled off from the obtained transfer material, and the film is adhered to a prepared coated cardboard so that the toner image directly faces it and adjusted to 110 ° C. After heating and pressurizing with a household iron, a 90% ethyl alcohol aqueous solution was applied from the back side of the film. The polyvinyl alcohol film did not dissolve, and the solvent was allowed to penetrate to the interface with the toner to separate the toner and the film. I was able to.

Also, this film was treated at 30 ° C. and 80% RH.
It shows good water resistance without any change even if left in the environment, and has little shrinkage even in the environment of 20 ° C and 10% RH, and balances the curl due to the shrinkage of the base paper,
The curl was almost flat to convex.

Example 2 (Transfer Layer) A transfer material was prepared in the same manner as in Example 1 except that the low saponification degree polyvinyl alcohol (caseol 05) in the transfer layer was changed to 30 parts.

There was no problem in image formation of the obtained transfer material. However, when left in an environment of 20 ° C. and 10% RH, curling occurred, and the curl was concave with the image side of about 6 mm. When this transfer material was passed through CLC700, it was barely possible to be adsorbed to the transfer drum.

[Example 3] (Release layer) Polyvinyl alcohol with low saponification degree (Casesol 05, solid content 50%) 50 parts Silicone resin (solid content 20%) 5 parts Water 50 parts to form a release layer. A transfer material was produced in the same manner as in Example 1 except that the transfer material was formed. When an image was formed using the obtained transfer material, all good results were obtained as in Example 1.

Comparative Example 1 (Transfer Layer) Low saponification degree polyvinyl alcohol (Casesol 05) 100 parts Water 5 parts Antistatic agent 2 parts Transfer was performed in the same manner as in Example 1 except that the transfer layer was formed. A material was produced.

The obtained transfer material was unusable due to stickiness of the coating film in a high temperature environment.

Comparative Example 2 (Transfer Layer) A transfer material was produced in the same manner as in Example 1 except that the low saponification degree polyvinyl alcohol (caseol 05) was not used in the transfer layer.

The obtained transfer material had a curl of 20 mm or more in a low humidity environment and could not be passed at all. Further, the toner image after fixing was easily peeled off, and good transfer could not be performed.

Comparative Example 3 A transfer material was prepared in the same manner as in Example 1 except that the adhesive layer was made of silicone resin.

When the obtained transfer material was passed through CLC700, film peeling easily occurred and the paper could not be passed at all.

[0056]

As described above, in the transfer picture transfer material for electrophotography having the polymer resin film on the substrate of the present invention,
According to the electrophotographic transfer picture transfer material in which the polymer resin film is composed of three layers of an adhesive layer, a release layer and a transfer layer, 1) the water resistance is improved.

2) Decrease the amount of curl left to stand.

3) Stabilize the releasability of the film layer. It has become possible to provide a more stable transfer picture transfer material for electrophotography.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a transfer picture transfer material of the present invention.

FIG. 2 is a melting characteristic diagram of a toner preferably used in the present invention.

[Explanation of symbols]

 11 Base Material 12 Adhesive Layer 13 Release Layer 14 Transfer Layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kaoru Yamamoto 1-6-24 Sachimachi, Sabae City, Fukui Prefecture

Claims (9)

[Claims] 1. An electrophotographic transfer picture transfer material having a polymer resin film on a substrate, wherein the polymer resin film comprises three layers of an adhesive layer, a release layer and a transfer layer. Transfer picture transfer material for photographs. 2. The transfer picture transfer material for electrophotography according to claim 1, wherein the polymer resin film is peelable at the interface between the adhesive layer and the release layer. 3. The adhesive force between the adhesive layer and the release layer is 1.5 g / c.
The transfer picture transfer material for electrophotography according to claim 1, wherein the transfer picture transfer material is from m to 4 g / cm. 4. The transfer picture transfer material for electrophotography according to claim 1, wherein the adhesive layer contains a resin selected from acrylic, polyester and nylon. 5. The transfer picture transfer material for electrophotography according to claim 1, wherein the release layer contains polyvinyl alcohol. 6. The release layer comprises a polyvinyl alcohol having a saponification degree of 90% or less and a silicone resin.
Transfer picture transfer material for the described electrophotography. 7. The transfer picture transfer material for electrophotography according to claim 5, wherein the polyvinyl alcohol is obtained by saponifying polyvinyl acetate in an amount of 95% or more. 8. The transfer layer contains polyvinyl alcohol saponified with 95% or more of polyvinyl acetate and polyvinyl alcohol saponified with 90% or less of vinyl acetate, and has a saponification degree of 9
The transfer picture transfer material for electrophotography according to claim 1, wherein the content of polyvinyl alcohol of 5% or more is 25% by weight or more and less than 75% by weight as a solid content. 9. The surface resistivity of the transfer layer is 20.degree.
10 under% RH environment ⁸ -10¹²It is Ω / □.
Transfer picture transfer material for electrophotography.