JPS63288746A - Marking film - Google Patents

Abstract

PURPOSE:To keep no color change of marks for a long time and to get rid of occurrence of crazings when exposed to a ultra violet ray, by laminating an unvulcanized rubber sheet where butyl rubber or halogenated butyl rubber is the main component on a printed face or a transparent or semi-transparent synthetic resin film where marks arc printed with an ink containing an unvulcanized rubber as the base material. CONSTITUTION:In a marking film 10, an unvulcanized rubber sheet 3 whose main component is butyl rubber or halogenated butyl rubber is laminated on a printed face of a transparent or semi-transparent synthetic resin film 2 where marks 1 and so on are printed with an ink containing unvulcanized rubber as the base material. As the above described synthetic resin film 2, a film having a softening temp. being higher than the vulcanization temp. of a rubber product on which marks are transferred, is preferable and a polyester film is usually used. Marks and so on transferred on the rubber product can sufficiently follow the large deformation of the rubber of the rubber product by using an unvulcanized rubber as the base material of the ink used for printing the marks 1 and so on the film 2. Flow deformation of the transferred marks and so on can be thereby surely prevented against the flow of the rubber generated at press-vulcanization of the rubber product.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a marking film, and in particular, to a marking film on the surface of a rubber product.
shall include marks, figures, characters, etc. ), a marking film that is suitably used when pasting a film with marks, etc. printed in advance on the surface of an unvulcanized rubber product and printing marks, etc. at the same time as vulcanization. .

[Prior Art] One method for marking the surface of rubber products is to apply an untreated coating to the surface of a transparent or semi-transparent synthetic resin film (hereinafter sometimes simply referred to as "synthetic resin film"). A film (hereinafter referred to as
Sometimes called "marking film." ) using
Conventionally, a method has been known in which this marking film is attached to the surface of an unvulcanized rubber product and the printing is transferred simultaneously with the vulcanization of the product.

[Problems to be solved by the invention] When a mark, etc. is applied using this method, if the rubber product is made of staining rubber, the part to which the mark, etc. is transferred may be exposed to ultraviolet rays such as sunlight. In this case, amine anti-aging agents and process oils contained in rubber products bleed onto the surface of the mark, and UV energy is added to the mark, causing discoloration of the mark, making it difficult to see, and damaging the image of the product. It has the disadvantage of significantly lowering the Also,
Furthermore, when exposed to ultraviolet light for a long period of time, there is also the problem that crazing (fine cracks) occurs on the mark surface.

In addition, when unvulcanized rubber is press-vulcanized in a mold to make a rubber product, the rubber flows during pressing, and the flow of this rubber causes the mark printed on the marking film to flow and deform, causing the mark to change. It also has the disadvantage of significantly deteriorating the appearance. As a method to prevent this flow deformation of the mark, the rubber sheet of the marking film is vulcanized in advance to provide sufficient resistance to the flow of rubber that occurs during press vulcanization of rubber products, and to prevent the deformation of the mark. There is a way to suppress this, but in this case, the adhesion between the rubber sheet of the marking film and the rubber of the product is between vulcanized rubber and unvulcanized rubber, so the problem is that the adhesive strength is significantly reduced. arise.

[Means for Solving the Problems] The present invention solves the above-mentioned conventional problems, and even when transferred to products using stain-prone rubber, marks etc. do not discolor for a long period of time, and are protected against ultraviolet rays for a long period of time. To provide a marking film for applying marks, etc. on the surface of rubber products, which does not cause crazing even when exposed to , unvulcanized rubber whose main component is butyl rubber or halogenated butyl rubber on the printed surface of a transparent or translucent synthetic resin film with marks, figures, characters, etc. printed with ink based on unvulcanized rubber. The gist of the present invention is a marking film characterized by being formed by laminating sheets.

Hereinafter, the present invention will be described in detail with reference to the drawings.

FIG. 1 is a cross-sectional view showing a marking film according to an embodiment of the present invention. As shown in the figure, the marking film 10 of the present invention has marks etc. 1 printed with an ink based on unvulcanized rubber. Furthermore, an unvulcanized rubber sheet 3 containing butyl rubber or halogenated butyl rubber as a main component is laminated on the printed surface of a transparent or translucent synthetic resin film 2.

The transparent or translucent synthetic resin film 2 is preferably a film having a softening point higher than the vulcanization temperature of the rubber product to which the mark is to be transferred, and usually a polyester film or the like is used.

By using unvulcanized rubber as the base material for the ink used to print marks etc. 1 on such film 2, the marks etc. transferred to the rubber product can sufficiently follow large deformations of the rubber of the rubber product. become able to.

In the present invention, natural rubber or synthetic rubber such as chlorosulfonated polyethylene rubber or halogenated butyl rubber can be used as the unvulcanized rubber material that is the base material of the ink, but in particular chlorosulfonated polyethylene rubber can be used. By using this, it is possible to more reliably prevent the transferred marks from being deformed due to the flow of rubber that occurs during press vulcanization of rubber products, and also to prevent the marks from being deformed due to long-term exposure to ultraviolet rays after being transferred. A product with excellent weather resistance can be obtained without any crazing occurring on the surface of the product.

The ink used in the present invention is easily manufactured by uniformly dispersing rubber, vulcanizing agent, inorganic pigment, organic pigment, etc., which has been dissolved or swollen in advance with an appropriate amount of solvent on a Miki roll (ink roll). .

The unvulcanized rubber sheet 3 suppresses bleeding of contaminating antiaging substances in rubber products and suppresses discoloration of marks and the like. The rubber used for the unvulcanized rubber sheet 3 is generally preferably halogenated butyl rubber from the viewpoint of adhesion to rubber products. In particular, in order to improve this adhesiveness, the rubber component of the unvulcanized rubber sheet 3 is a blend of 0 to 30 parts by weight of natural rubber or other synthetic rubber to 100 to 70 parts by weight of butyl rubber or halogenated butyl rubber. It is preferable that the In addition, the unvulcanized rubber sheet 2 may contain carbon black, an inorganic filler, non-contaminating process oil, etc., as necessary, along with a vulcanizing agent. Note that adding a large amount of non-staining process oil may have an adverse effect on the discoloration resistance of marks, etc., so it is necessary to keep the blending amount to the minimum necessary. In addition, when chlorosulfonated polyethylene rubber is used as the ink base material, the transferability of marks etc. is affected by the vulcanization accelerator used in the unvulcanized rubber sheet 3, but sulfenamide-based By using the agent, a marking film with excellent transferability can be obtained. The unvulcanized rubber sheet 3 is made by applying an unvulcanized rubber compound to 0.2 to 3.0 with a calender roll or the like.
It is easily manufactured by rolling to about mm.

In order to manufacture such a marking film 10 of the present invention, for example, marks etc. 1 are printed on the surface of the synthetic resin film 2 using the ink by screen printing, gravure printing, etc., and this printed surface and the unprocessed surface are combined. Paste together with sulfur rubber sheet 3.

In order to print marks, etc. on rubber products using the marking film of the present invention produced in this way, the marking film is cut into a shape corresponding to the marks, etc. as necessary, and then unvulcanized. It is attached to the surface of the rubber product, the mark is transferred at the same time as the product is vulcanized, and then
Peel off the synthetic resin film. That is, for example, as shown in FIG. 2, a marking film 10 is bonded to the surface of an unvulcanized rubber product 4 with the unvulcanized rubber sheet 3 side in contact with the surface, and then the marking film 10 is pasted with the unvulcanized rubber sheet 3 side in contact with the surface of the unvulcanized rubber product 4. Press vulcanize for a certain period of time. After press vulcanization, vulcanized rubber product 4'
When the synthetic resin film 2 is removed, a vulcanized rubber product 4' as shown in FIG. 3 is obtained which has a vulcanization mark 1' integrated on its surface via a vulcanized rubber sheet 3'. By such a method, a rubber product on which marks etc. are clearly transferred can be obtained.

Note that when the synthetic resin film is peeled off, some of the ink may remain on the peeled-off lid film. When the transferability of marks and the like is poor as described above, the transferability can be significantly improved by using an ink containing a small amount of silane coupling agent as the ink for printing onto the synthetic resin film.

Adding a small amount of silane coupling agent to the ink also has the effect of improving the solvent resistance of vulcanized and transferred marks. The silane coupling agent is preferably added in an amount of 0.1 to 3% by weight based on the rubber component in the ink.

[Function] In the marking film of the present invention, marks and the like are printed on the surface of a transparent or translucent synthetic resin film with an ink based on unvulcanized rubber.

When marks printed with ink based on unvulcanized rubber are transferred to rubber products, they can sufficiently overcome the deformation of the rubber product during vulcanization and the flow of the rubber, preventing the marks from deforming. This enables highly accurate marking.

Further, the marking film of the present invention has an unvulcanized rubber sheet containing butyl rubber or halogenated butyl rubber as a main component laminated on the printed surface of the synthetic resin film printed in this manner. This unvulcanized rubber sheet, which mainly consists of butyl rubber or halogenated butyl rubber, suppresses the bleeding of contaminating anti-aging substances in the rubber product after transferring marks, etc. to rubber products, and prevents discoloration and crazing of marks, etc. It has the effect of

Therefore, according to the marking film of the present invention, it is possible to easily and efficiently mark rubber products with high precision. The transferred marks, etc. have a good appearance because they are not deformed in shape, etc., and have extremely good adhesion to the product. Moreover, marks, etc. do not discolor due to bleeding of contaminants in rubber products, and crazing is also prevented.
Its shape, color, etc. can be maintained beautifully.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

Examples 1 to 3, Comparative Example 1.2 With the formulation shown in Table 1 of the marking film, the rubber was dissolved in a solvent, and the vulcanizing agent, vulcanization accelerator, vulcanization aid, and pigment were added to it on three rolls. and a silane coupling agent were uniformly mixed to obtain blue ink and yellow ink. Using this ink, a blue-yellow two-color mark is printed by screen printing on a 100 μm thick polyester film, and after thoroughly drying the ink solvent, the printed surface has a thickness of 0 with the formulation shown in Table 2. A marking film with a length of 1 cm and a width of 5 cm was created by laminating .7 mm unvulcanized butyl rubber sheets and cutting them into the shape of the mark.

Table 1 *1 Hypalon 20 (manufactured by Dupont) *2 Mercaptopropyltrimethoxysilane Table 2 *I N-cyclohexyl-2-benzothiazyl sulfenamide *2 Tetramethylenethiuram disulfide Transfer to rubber products As shown in Figure 2, the above marking film 10 was pasted onto the surface of a separately prepared unvulcanized tire tread rubber 4 with a thickness of 6 mm, and the marking film 10 was placed in a mold 5 with a thickness of 5 mm.
Press vulcanization was performed at a temperature of 0° C. for 10 minutes.

After vulcanization, the polyester film 2 on the mark was peeled off to obtain a vulcanized rubber product 4' with the mark 1' transferred thereon as shown in FIG.

When the polyester film 2 was peeled off after the above-mentioned partial vulcanization, if a part of the ink remained on the polyester film 2, the clarity of the mark decreased, so the transferability was evaluated. In addition, the flow deformability of the mark was evaluated by observing the shape of the mark transferred to the tire tread rubber.

Furthermore, the obtained vulcanized rubber with the mark transferred was subjected to a weather resistance test for 20 to 400 hours using a sunshine carbon weather meter, and the performance was evaluated by observing changes in the color tone of the mark and the occurrence of crazing on the mark surface. did.

The results are shown in Table 3.

As is clear from Table 3, when the marking film of the present invention using a rubber sheet containing bromobutyl rubber as the main component was used as the unvulcanized rubber sheet to be attached to the printing surface, after the transfer, There is no change in the color tone of the mark, and the mark can be kept beautiful for a long time. on the other hand,
When natural rubber or styrene-butadiene rubber was used as the unvulcanized rubber sheet, discoloration occurred after only 20 hours of ultraviolet irradiation.

Examples 4 to 7 A mark was printed on a polyester film by screen printing using a white ink having a composition shown in Table 4 of the marking film, and the unvulcanized ink of No. and A composition of the above Table 2 was printed on the printed surface. Paste a butyl rubber sheet and cut it into the shape of the mark, 1cm long.
, a marking film with a width of 5 cm was obtained.

This marking film was pasted onto the surface of a separately prepared unvulcanized tire tread rubber with a thickness of 5.5 mm.
Press vulcanization was performed at 160° C. for 10 minutes in a 5 mm thick mold. After vulcanization, peel off the polyester film,
Transferability was evaluated based on whether ink remained on the polyester film.

In addition, when the surface of the mark transferred to the vulcanized rubber was rubbed with absorbent cotton soaked in toluene, the solvent resistance of the mark was evaluated by whether or not the mark would dissolve. The results are shown in Table 5.

From Table 4 and Table 5, it is clear that the marking film of the present invention has extremely good transferability, and the transferred marks have excellent solvent resistance. In particular, when the ink contains a silane coupling agent, extremely excellent solvent resistance can be obtained.

[Effects of the Invention] As detailed above, the marking film of the present invention has marks printed with an ink based on unvulcanized rubber.
It is made by laminating an unvulcanized rubber sheet whose main component is butyl rubber or halogenated butyl rubber on the printing surface of a transparent or translucent synthetic resin film, and ■ it is possible to transfer marks, etc. at the same time as vulcanization. Therefore, the adhesion of the mark to the product is extremely strong.

■During vulcanization, it can sufficiently overcome the deformation and flow of the rubber on the product side, and the marks are transferred well without deformation, resulting in high marking accuracy.

■ Since the bleeding of contaminating antiaging substances in rubber products is prevented, discoloration and crazing of marks etc. due to ultraviolet rays are prevented, and the shape and color of marks etc. can be maintained beautifully for a long period of time.

It has the following effects. Therefore, the marking film of the present invention has good transferability, excellent weather resistance, and durability.
Moreover, beautiful marks etc. can be applied to rubber products.

[Brief explanation of the drawing]

Fig. 1 is a cross-sectional view showing an embodiment of the marking film of the present invention, Fig. 2 is a cross-sectional view illustrating a method of transferring the marking film to a rubber product using the marking film of the present invention, and Fig. 3 is a cross-sectional view showing the marking film obtained by transfer. FIG. 1... Mark etc., 2... Synthetic resin film, 3... Unvulcanized rubber sheet, 10... Marking film.

Claims (3)

[Claims] (1) On the printed surface of a transparent or semi-transparent synthetic resin film with marks, figures, characters, etc. printed using ink based on unvulcanized rubber, an uncured rubber whose main component is butyl rubber or halogenated butyl rubber. A marking film characterized by being made by laminating sulfur rubber sheets. (2) The marking film according to claim 1, wherein the unvulcanized rubber serving as the base material of the ink is chlorosulfonated polyethylene rubber. (3) The marking film according to claim 1 or 2, wherein the ink contains a silane coupling agent.