KR890003579B1 - Method for preparing mat film for drawing - Google Patents

Abstract

An aq. polyester resin is used as a binding agent of mat layer, where a matting material such as CaCO3, SiO2, Al2O3 and TiO2 pretreated with a titanateous coupling agent is added or a small quantity of coupling agent is added to the mixed solution of an aq. polyester and the matting material for preventing running of ink on mat film at both parts of start and end of draft line and for the preventing adhesion of films owing to tacky property of aq. polymer. The quantity of titanteous coupling agent in application soln. for mat layer is 0.01-5 wt.% on the basis of matting material.

Description

Manufacturing method of mat film for drawing

The present invention adds a mat agent pretreated with a titanate-based coupling agent when a water-based polyester resin is used as a binder of the mat layer, or a predetermined amount of a coupling agent in a mixed solution of an aqueous polyester and a mat agent. When drawing the line segment by adding, it eliminates the phenomenon of ink clumping at the beginning and end of the line segment (especially when thick line segment) and at the same time stacking and processing multiple layers of matt film processed in high temperature and high humidity environment. The present invention relates to the preparation of a writing mat film for removing the adhesion between the films due to the sticking phenomenon frequently occurring in the aqueous polymer.

Conventional methods for imparting handwriting on a synthetic resin film support include a method of matting a surface by sandblust mold pressure, a method of corroding the surface with an organic solvent, CaCO ₃ , SiO ₂ , It is known to apply a certain thickness of a mixed solution of inorganic and organic fine particles (hereinafter referred to as matting agent) such as TiO ₂ and polymethyltaacrylate to matt the surface thereof. I) 44-25238, Japanese Patent Application No. 44-29385, US Patent No. 3,142,582, US Patent No. 3,607,473, US Patent No. 3,078,178 and British Patent 817184.

Among these methods, the corrosion method for organic solvents is insufficient in the degree of matting, so it has a drawback of using organic solvents harmful to the human body. In the case of matting by physical methods such as spraying, the writing ability for pencils is sufficient. However, there is a problem that the ink is smeared or smeared when hand rubbed after writing because the writing ability of water-based ink such as a fountain pen and an aqueous ink for drawing is very bad.

On the other hand, when the binder containing the mat agent is applied on the film support to make it mat, the physical properties of the processed mat film largely depend on the property of the binder to be used.

In other words, as disclosed in British Patent No. 1047697, when the hydrophobic polymer (vinylidene chloride copolymer) is used as the binder of the mat layer, the adhesion between the mat layer and the hydrophobic film support is very good, There is a lack of handwriting. Therefore, as a way to improve the handwriting properties of aqueous ink, Japanese Unexamined Patent Application No. 53-89169 proposes to matte the surface by using a hydrophilic resin (eg, polyvinyl alcohol, gelatin, etc.) as a binder.

In this case, the matte film has good writing ability to pencil and water-based ink, so there is no problem from the viewpoint of writing ability, but the adhesion to the film support is relatively weaker than that of using a hydrophobic binder. When rubbed, the matte layer and the base film layer not only have the drawbacks of each other but also have the drawback of causing adhesion between films by absorbing the surrounding moisture when left in the overlapping state in a high temperature and humid atmosphere.

Japanese Patent Application No. 61-2556 proposes the production of a mat film having improved erase and writing properties and adhesion between the mat layer and the base film by using an aqueous polyester as a binder of the mat layer on the polyester film. In this case, a good compatibility between the polyester base film and the water-based polyester, and excellent adhesion between the mat layer and the base film was able to obtain a mat film excellent in writing and erasability to the desired water-based ink. In this case, however, the dispersibility of the matting agent is poor, and the surface of the coated matte layer is not uniform. When drawing the line segment, the ink may not only bleed at the beginning and end of the segment, but also at a high temperature. In the case of using a plurality of sheets overlapping each other in a humid atmosphere, it is difficult to peel off one by one due to adhesion between the mat films due to moisture absorption of the polymer.

In the present invention, a method for solving such a drawback is carefully examined, and when the water-soluble polyester resin is used as the binder of the mat layer, the mat agent is added with a titanate-based coupling agent, or the aqueous polyester resin and the mat agent are mixed and dispersed. It has been found that the above drawbacks can be solved by adding a predetermined amount of titanate-based coupling agent. In other words, due to the coupling effect of the coupling agent, the dispersion of the aqueous polyester is improved, and the mat agent is uniformly dispersed on the surface of the mat layer. In addition, the adhesive strength between the mat agent and the binder could be improved by adding about 30-40% of the mat agent more than when the untreated mat agent was added, thereby preventing the adhesive phenomenon due to the adhesive phenomenon.

As the titanate coupling agent which can be used in the present invention, any of the product names KRTTS, KR9S, KR38S, KR41B, KR46B, KR55, KR138S, KR238S may be used, but KR38S, KR55, KR138S-amine addition salts are preferable. In this case, the amount of the coupling agent may be 0.01wt% -5wt% based on the weight of the mat agent, but is preferably in the range of 1wt% -3wt%.

If the amount of the coupling agent is 0.01wt% or less, the desired adhesive strength between the mat agent and the binder cannot be obtained. If the coupling agent is 5wt% or more, the hydrophobic end groups of the coupling agent are formed on the surface without the improvement of the mat layer without the improvement of the physical properties. Rather it tends to reduce handwriting for aqueous ink.

Aqueous polyesters that may be used in the present invention include trade names FPY-6762, MPS-7762, WD-3652, WJL-6342, WMS-5113, WD SIZE, WNT, WMS, DFB, etc., manufactured by Estman Chemicals, USA. , WMS is preferred.

As the mat but may any of the inorganic fine particles such as _{CaCO3, SiO 2, Al 2 O} 3, TiO 2 also. The particle diameter (Ra) of the mat agent is about 1um-10um is good and the mat agent content is 1-7 parts by weight, in particular 4-5 parts by weight of the mat agent relative to the binder weight 1. As the coating method of the mat layer, a coating method generally known to those skilled in the art, for example, a gravure method, a reverse method, a wire-bar coating method and the like can be given.

EXAMPLE

The following examples and comparative examples are intended to more specifically illustrate the invention and are not intended to limit the scope in any way.

Example 1

On the polyester film of thickness 50um, the following composition liquid is generally applied by the application | coating method and dried for 3 minutes at 130 degreeC after application | coating so that it may become thickness 5m after drying, and a mat film is manufactured. At this time, the mat was added as the pre-treatment after the SiO ₂ of the titanate-based coupling agent of 4 weight% with respect to SiO ₂ by the wet method.

Water-based polyester resin WMT… … … … … … … … … … 5 wt%

Pretreated SiO ₂ (Ra = 3.2um). … … … … … … … … … 15 wt%

H ₂ O... … … … … … … … … … 80 wt%

Example 2

Instead of using pretreatment SiO ₂ as a mat agent under the conditions of Example 1, a titanate coupling agent was added directly to the mixed dispersion of the aqueous polyester resin and the untreated SiO ₂ by 3 wt% of the weight of SiO ₂ to form a mat film. Prepared.

Comparative Example 1

A mat film was prepared using the following composition solution in the same manner as in Example 1 except that the pretreated SiO _{2 used} was 1.5 wt% instead of 15 wt%.

Aqueous polyester… … … … … … … … … … 5 wt%

Pretreated SiO ₂ (Ra = 3.2um). … … … … … … … … … 1.5 wt%

H ₂ O... … … … … … … … … … 93.5 wt%

Comparative Example 2

All conditions were the matte film was prepared using a mat agent, untreated SiO ₂ equal to the first embodiment.

Comparative Example 3

The same conditions as in Example 1 except that the following liquid was applied to prepare a mat film.

Gelatin… … … … … … … … … … 6 g

SiO ₂ (Ra = 3.2 um)... … … … … … … … … … 0.6g

Phenolic… … … … … … … … … … 0.3 g

H ₂ O... … … … … … … … … … 150 g

[Comparative Example 4]

A commercially available sand mat film (manufactured by Nippon East) was prepared for comparison.

[Comparative Example 5]

All other conditions were the same as in Example 2, and only 7 wt% of the titanate coupling agent was added to the weight of SiO ₂ to prepare a mat film.

Comparative Example 6

A mat film was prepared in Example 2 with the titanate coupling agent added in an amount of 0.09% by weight or less based on the weight of SiO ₂ .

The mat film samples prepared in the above Examples and Comparisons were compared and tested in the following criteria, and the physical properties thereof are summarized in Table 1 below.

1) Adhesion resistance test: based on JIS K-6842

2) Adhesion strength: Cellophane adhesion angle test

3) Handwriting test: Visual inspection after drafting using DMP-50 series DIGITAL PLOTTER manufactured by Houston Instrument

TABLE 1

As can be seen from Table 1, it is apparent that the samples of Examples 1 and 2 according to the present invention exhibit excellent writing, adhesive strength and adhesion resistance compared to the samples of the comparative example.

That is, the dispersibility of the mat agent to the water-based polyester can be improved by pre-treating or adding a meat preparation agent with a titanate-based coupling agent or by adding a predetermined amount, so that the surface of the formed mat layer is uniformly matted. When drawing a line segment during manufacturing (especially for automatic drawing), it becomes possible to draw a line of uniform thickness without the phenomenon of ink agglomeration at the beginning.

In addition, it is possible to add about 30-40% more than the amount of the untreated mat agent by improving the adhesive force between the mat agent and the binder, thereby preventing adhesion between the mat film due to the adhesion phenomenon generated during high temperature and high humidity.

Claims (2)

A method of producing a draft mat film, wherein the mat agent is pretreated with a titanate coupling agent when a water-based polyester is used as the binder of the mat layer on the polyester film. The manufacturing method of Claim 1 which mixes 0.01-5 weight% titanate type coupling agent with respect to the weight of a mat at the time of composition of a mat layer coating liquid, and the dispersion of an aqueous polyester and a mat, and forms a mat layer.