KR920001484B1 - Transfer paper and process for using the same - Google Patents

Abstract

A transfer paper for heat-resistant, non-absorbing surfaces is prepared by finely coating transfer film solution for releasing on transfer board. The transfer film solution is obtained by adding 0.05-2 parts non-ionic surfactant of HLB value 5-18 to 100 parts of solid portion of acrylic copolyaer resin solution. Especially the surfactant is polypropylene glycol having a molecular weight of 500-3000. The process for transfering patterns onto the porcelaim surface using the above transfer paper comprises (A) releasing printed transfer film from transfer paper, (B) attaching the released film to the porcelain surface by a fluid contg. more than 20 % C10-C50 hydrocarbon, and (C) burning it in a furance.

Description

Transfer paper used for heat-resistant non-absorbent surface such as ceramics and transfer method using the same

The present invention provides a variety of letters to give aesthetic appearance to the outer surface of heat-resistant non-absorbent surface, such as pottery, porcelain, enamel glazed, and stainless steel, The present invention relates to a transfer sheet used for transferring a picture or a pattern, and a method of using the same to make a transfer more efficiently.

In other words, the transfer film used for printing on the surface of ceramics (hereinafter, only "pottery" will be described as an example) can be easily removed from the transfer sheet in its original state without physical deformation. The present invention relates to a transfer paper using a hydrocarbon-based flowable material having a special property as an adhesive medium, which shortens the number of transfer work steps and eliminates defects in pattern printing and a transfer method using the same. It is well known that a transfer paper and a transfer method for transferring various kinds of paintings or patterns on the surface of ceramics are well known in the art, but due to the problems described below, it is a major factor that causes an increase in the defect rate of ceramics. Functioned. That is, a metal oxide component (ceramic pigment) and an oil-based resin solution (transfer printing) are prepared on a transfer sheet prepared by adding water-soluble resins such as starch grass, dextrin, gum arabic, and gelatin on a thin paper processed with pure pulp. Oil) is a printing ink prepared by mixing a predetermined letter, picture or pattern with a printing layer by screen or offset printing, and then drying the liquid protective film solution (transfer film solution) on the dried printing layer. Was applied over the entire surface and dried again to form a thin film-shaped tough transfer film that strongly adhered to the back side to produce a transfer paper for use in ceramics. Since the method must go through several steps as described below, there is a drawback of unnecessary labor and time wasting.

That is, look at the manufacturing process for this in detail,

1. Impregnation process: By impregnating the transfer paper prepared above into water, the transfer sheet rapidly absorbs the water so that the water-soluble resin applied on the surface of the paste dissolves with water so that the printing layer is transferred from the transfer sheet to the back side. An atmosphere in which the transferred film formed is peeled off is created.

2. Peeling process: Peel off the transfer film with the transfer sheet and printing layer from the transfer paper taken out of the water.

3. Attachment process: The peeled transfer film is attached to the surface of ceramics using water as an adhesive medium while removing moisture.

4. Drying process: Ceramics with a transfer film attached with water as a medium are left to dry for 24 hours in order to completely dry the moisture remaining on the oil surface.

5. Firing process: Put the dried ceramics into a kiln and fire them at a predetermined temperature (approximately 780 ~ 830 ℃) so that the pattern printing layer on the transfer film is deposited on the ceramics surface so that the desired decoration can be expressed.

According to the conventional transfer paper described above and the transfer method using the same, since water must be used from the beginning to the end during transfer, it is a main factor that causes a large number of defective products such as ceramics to be transferred due to moisture. Even during work, it can be seen that unnecessary labor and time are wasted a lot due to an increase in the number of unnecessary work processes due to moisture removal. In other words, if the transfer paper does not completely remove moisture from the transfer film or the porcelain surface to which the film is attached, the defect rate due to moisture causes a large loss of 5% of the total porcelain defect rate. Becomes If the main loss factors directly caused by such moisture are largely classified, they can be summarized as follows. Firstly, moisture is absorbed by the water-soluble resin interposed between the transfer sheet constituting the transfer paper and the transfer film. Second, the film and the porcelain are attached to the transfer film by using water as an adhesive medium on the porcelain surface. This is due to the moisture remaining between the oil surface (surface) and the moisture that penetrates into the film.

The main reason for the first cause is that, as described in (i), in order to peel the transfer sheet and the transfer film constituting the transfer sheet, the transfer sheet must be impregnated in water, and the water-soluble resin coated on the transfer sheet is dissolved in water. This is because the transfer paper is separated from the ground by making it.

In this process, the water-soluble resin applied on the transfer sheet is naturally buried on the backside of the transfer film with the print layer in the state of water, so that when it is attached to the surface of porcelain, the transfer film adheres closely to the oil surface. The moisture contained in the water-soluble resin does not dry well even if the water is removed and dried during the normal drying time (the time when the water is completely dried in the state where the water-soluble resin is not attached to the back of the transfer film). It may remain without. When ceramics in such a state are put into a sintering furnace and fired, they remain on the back of the transfer film, or because the water is heated and evaporated as water vapor expands, causing the transfer film to swell and eventually penetrate the transfer film. The print layer (pigment layer) is deformed, and as a result, the traces of the defects of the ceramics are left on the surface of the ceramics. In addition, due to the water-soluble resin in addition to the moisture factor is the cause of defective porcelain during ceramic firing. The water-soluble resin carbonizes (after burning and turns into ash and carbonate gas), whether buried on the back of the film during firing of porcelain, so that the carbonized solid resin forms a gap between the porcelain surface and the print layer formed on the transfer film. The gaseous vaporized sesame in the pores, which is attached to the backside of the transfer film, escapes to the outside at the same time as the pigment on the print layer melts and is colored, thereby leaving a trace of bubbles on the porcelain surface. It causes the same cause as the same as the above-mentioned moisture factor.

In order to prevent such defects in advance, the water-soluble resin buried in the transfer film from the transfer sheet must be cleanly removed with water during the initial peeling process. However, it is almost impossible to completely remove the resin, as there are many restrictions. .

The second reason is that water is used as the adhesive medium in attaching the transfer film peeled from the transfer sheet to the ceramic surface during transfer using the transfer paper.

In this case, if the mixing ratio of the printing layer (pigment layer), which is transferred to the backside of the transfer film from the transfer sheet, that is, the pigment and the printing oil is not properly blended, water penetrates into the printing layer. Become self.

In other words, the printing pigment is prepared by mixing a metal oxide component, which is a ceramic pigment, and a printing oil. The dual printing oil is composed of approximately 40-50% of a resin solid and the remaining volatiles. Therefore, if the blending amount of oil in the printing pigment is lower than the set standard value, the resin solids in the printing oil cannot be filled in precisely into the porcelain pigment particle gap. In this case, after the volatile material is volatilized, porcelain pigment particles are not formed precisely because the amount of oil blended in the printing layer is lower than the reference value, resulting in void generation.

When the transfer film with the printing layer is used when transferring the porcelain, water is used as an adhesive medium when the porcelain is transferred to the porcelain, so that water penetrates into the pores formed in the printing layer.

Therefore, even if the drying process is left for a normal drying time (usually, when the water does not penetrate into the printing layer pores, it is time to dry the moisture), some of the water penetrated into the printing layer pores is not dried. Since residuals always occur without occurrence, a failure cause occurs in the firing operation as described in the first cause. That is, since the air bubbles in the process of evaporation of the moisture remaining in the printing layer voids attached to the back of the transfer film during the firing operation, there was a closed end that leaves the porcelain on the surface of the porcelain.

Moreover, conventionally, water is always used from the transfer film peeling process to the adhesion process on the porcelain surface, and thus the transfer process step is increased, which causes the economic burden due to unnecessary labor and time consumption. Furthermore, there existed a disadvantage that productivity improvement falls.

As a result of intensive research to solve the above problems, it has been found that the transfer film can be easily removed from the transfer sheet without impregnation of the transfer sheet for printing.

That is, according to the present invention, the transfer sheet is formed by applying a peeling transfer film solution obtained by adding a suitable release agent to an acrylic resin solution on a transfer sheet on which a printed layer is printed and formed into a transfer film. The transfer film for peeling was easily peeled off from the transfer board in the dry state as it was.

In addition, the present invention by using a hydrocarbon-based fluid material as an adhesive medium when the transfer paper obtained by using the transfer paper attached to the surface of the transfer porcelain porcelain, eliminating the defect of porcelain printing due to moisture and transfer process water Was shortened.

Next, the present invention will be described in detail. The manufacturing method of the transfer paper is as follows. Inorganic substances are not eluted, and on the thin processed paper processed as pure pulp different from ordinary paper, water-soluble resin such as starch grass, dextrin, gum arabic, gelatin, etc. In order to prevent the liquid from penetrating into the inside, or to prepare a transfer sheet, or in the present invention, the transfer sheet does not need to be impregnated with water, unlike conventional transfer sheet, unlike ordinary art paper with less shrinkage expansion, gum arabic, gelatin, polyvinyl Water-soluble resins, such as alcohol, are carefully applied and dried to prepare a transfer sheet prepared only so that the oil-based liquid does not penetrate inside. On the transfer site, print letters, pictures, patterns, etc. that fit your taste are printed on the screen or offset printing machine using printing ink made by mixing the ceramic color (metal oxide component) of the desired color and oily resin solution (printing oil). Dry to form a printed layer. A peeling transfer film solution is applied as a thickness of about 100 mu over the entire surface of the electronic layer printed layer on which the printed layer is printed. After application, the film is dried at a predetermined temperature and the peeling transfer film solution is transformed into a hard and tough film-like transfer film. In the original dry state, the transfer paper that can be easily peeled off is produced.

Here, the peeling transfer film solution, which is applied to the transfer sheet printing layer to form a thin film film, is made by adding 0.05 to 20 parts by weight of a release agent (per 100 parts by weight of the synthetic resin solids in the acrylic copolymer resin solution) to the acrylic copolymer resin solution. The release agent used above is suitable when using a nonionic surfactant in the range of 5-18 (Hydrophillic-Lipophilic Balance) HLB. Nonionic surfactants are polypropylene glycols having a molecular weight ranging from 500 to 3,000.

The present invention is in no way limited by the following examples.

Example 1

○ The company used the site of Sammi Industrial Company's products.

○ The transfer printing oil used MK-707N (Poongsan Chemical Co., Ltd.).

○ Pigment (metal oxide component) for ceramics: The oil compounding ratio was 1: 7.

○ Use The print screen used was 250Mesh (manufactured by ZBF Corporation).

1 degree printing was printed using white 191230 (made by Degussa), and it dried at room temperature for 1 hour.

○ Second-degree printing was printed overlaid on light blue 121231 (manufactured by Degussa) and dried at room temperature for 1 hour.

○ 3rd degree printing was overprinted on 2nd degree printing using black 141231 (made by Deguss), and it dried at room temperature for 2 hours.

A peeling film solution (Exp-1011) was applied onto the printed layer printed on the transfer sheet with a 45-mesh screen at a thickness of about 100μ and dried at room temperature for about 48 hours (2 days).

※ Composition ratio of peeling film solution (Exp-1011)

○ Cyclohexyl methacrylate (CHMA) 20

○ Normal Butyl Methacrylate (NBMA) 5

○ Isobutyl methacrylate (IBMA) 7

○ Butyl acrylate (BA) 4

2-ethyl hexyl methacrylate (2-EHMA) 9

○ Benzoyl Peroxide (BPO) 4

○ Polypropylene glycol (molecular weight: 500 ~ 3,000) 2

Dibutyl butyrate (DBP) 2

○ Benzene-based hydrocarbon (boiling point range 160-180 ° C) 55 / 104.4 (parts by weight)

※ Synthetic resin

① Put benzene-based hydrocarbon 55 (weight part) into four-necked flask and raise the temperature to 100 ℃ to maintain.

② Mix the mixture of CHMA 20 (part by weight) + NBMA 5 (part by weight) + IBMA 7 (part by weight) + BA 4 (part by weight) + 2 EHMA 9 (part by weight) + BPO 0.4 (part by weight) for about 2 hours. It keeps as a temperature of 100 degreeC, continuously dropping.

③ After the dropping, the temperature is maintained at 100 ° C. for 4 hours and then gradually cooled.

④ Add polypropylene glycol 2 (part by weight) and DBP 2 (part by weight) and mix

Viscosity of Composition: W (Gardner Vis)

Solid: 45%)

<Characteristic>

The transfer paper thus obtained was able to easily peel off the peeling transfer film from the transfer sheet even in the natural dry state not impregnated in water.

The comparison result between the present product and the conventional product is as follows.

[Comparative Example]

Next, the method of transferring the pattern to the heat-resistant non-absorbing surface using the transfer paper obtained in the above example is as follows.

First step (peeling transfer film peeling step): The transfer film is peeled from the transfer paper obtained in the above example in a dry state.

Second Step (Adhesion Step): A thin film of hydrocarbon-based fluid is applied on the surface of porcelain with an adhesive medium to adhere the film that has already been peeled off in the above step.

※ The fluid used here contains 20% or more of hydrocarbons in the range of ₁₀ to ₅₀ carbon atoms (except for solutions containing 40% or more of water), 80% sulfuric acid and 2% liquid paraffin. 18% of the multi-wax was mixed with each other and then quenched by heating and stirring at a predetermined temperature until transparent.

In order to attach the transfer film to the porcelain surface, an adhesive medium (formerly used water) is required. The adhesive medium must satisfy the following conditions. In other words, the adhesive medium has a function of softening the transfer film to give softness and easy adhesion. The transfer film must not be infringed, damaged or deformed beyond restoration. In addition, even if it remains in the transfer film, it should not act as a defect requirement in the firing operation, there should be no harmful effects to the human body, and the flash point should be at least 50 ° C. In the present invention, a hydrocarbon-based fluid material is used as an adhesive material satisfying such a condition. Even if the hydrocarbon-based fluid material is present between the surface of ceramics and the transfer film, the plastic material does not cause plastic defects upon firing. It removes defects during firing. In other words, the hydrocarbon-based fluid material softens the transfer film slightly at room temperature, and as it heats up, the transfer film rapidly softens or dissolves and, unlike water, permeates the transfer film without any resistance and evaporates.

In addition, the flowable material is not carbonized at all, unlike the water-soluble resin buried on the back of the transfer film due to the use of conventional water, which is carbonized upon firing. This is because the residue content such as inorganic substances is negligible.

For this reason, the flowable material is introduced into the adhesive medium in the attachment process of the present invention.

Third process (firing process): Ceramics, which have completed the peeling transfer film attachment work on the surface of the ceramics, are heated at a temperature of about 780 to 830 ° C. in a conventional firing furnace, so that the patterns on the printed layer attached to the back of the transfer film It is to make the surface of the ceramic color.

<Characteristic>

According to the present invention, in the method of transferring using a conventional transfer paper, the process of impregnating the transfer film with water, which is peeled off from the earth, the process of adhering to the surface of the porcelain while removing moisture, and the process of drying water can be reduced. Productivity can be improved. In particular, because the water is not used in the leading edge, as in the conventional case, there is an effect that the ceramic printing defect due to moisture is not leading edge.

Claims (3)

A peeling transfer film solution obtained by adding 0.05 to 2 parts by weight of a nonionic surfactant in the range of 5 to 18 (per 100 parts by weight of a synthetic resin in an acrylic copolymer resin solution) to the acrylic copolymer solution as a release agent. Transfer paper used for heat-resistant non-absorbent surfaces such as ceramics, which are closely coated on the transfer ground. The non-ionic surfactant according to claim 1, wherein the non-ionic surfactant is polypropylene glycol having a molecular weight in the range of 500 to 3000. 1st process of peeling the transfer film printed in the dry state from the transcription | transfer paper which apply | coated the transfer film solution for peeling which mixed polypropylene glycol to the acrylic copolymer resin solution over the transfer sheet printing layer whole surface, and peeled The second step of attaching the transfer film on the surface of ceramics using an adhesive medium containing a fluid substance containing 20% or more of hydrocarbons having a carbon number of C ₁₀ -C ₅₀ (except for a solution containing more than 40% of water); A method of transferring a pattern to a heat-resistant non-absorbent surface such as ceramics, which is a third process of putting ceramics having a transfer film attached thereto in a firing furnace and firing.