JPH0230581A - Recording film - Google Patents

Abstract

PURPOSE:To enable recording to be easily performed by the use of water resistant and water-base ink by a method wherein a film having polyvinyl alcohol and a polymethacrylate polymer as main components is formed on at least one side face of a base material film, and each polymer is crosslinked to cellulose reactive resin. CONSTITUTION:Polyvinyl alcohol, at least one type of polymer selected among polyacrylic acid, polymethacrylic acid and copolymer thereof, and aqueous solution containing cellulose reactive resin are used as coating liquid, which is applied on one side or both sides of a base material film, and is dried by heating to produce the title film for recording. In that case, saponification degree of polyvinyl alcohol is 75 to 90%, and polymerization degree is 1000 or over. As polyacrylic acid, molecular weight is 60000 or over and as polymethacrylic acid, molecular is 40000 or over. As copolymer of those polymers, molecular weight 40000 or over, and a weight ratio of polyvinyl alcohol and poly(meth)acrylate polymer is 95/5 to 50/50. Thereby, a water resistant and water-base ink can be obtained from the test results.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a recording film used for writing and drawing using aqueous ink.

[Prior art and its problems]

It is known that a film in which a hydrophilic polymer film is formed on the surface of a support film is used as a recording film for inkjet printers, pen plotters, and the like. For example, according to Japanese Patent Application Laid-open No. 61193879,
It has been proposed that an ink-receiving film made of a mixture of water-soluble cellulose and polyvinylpyrrolidine is formed on at least one side of a transparent support.

However, when an ink-receiving film is formed using a water-soluble polymer in this way, although ink absorption is good at the beginning of ink drawing, the water-soluble polymer is dissolved by the water-based ink after a while. As a result, ink wads become uneven, making it impossible to draw. In addition, it has a disadvantage that it has poor water resistance and becomes sticky on its surface due to moisture in the air or sweat during handling.

〔the purpose〕

An object of the present invention is to provide a recording film that overcomes the above-mentioned drawbacks found in conventional recording films.

[Means for solving problems]

The present inventors have completed the present invention as a result of intensive research to achieve the above object.

That is, according to the present invention, at least one side of the support film is coated with polyvinyl alcohol and at least one poly(meth)acrylic acid selected from polyacrylic acid, polymethacrylic acid, and copolymers thereof. The polyvinyl alcohol and/or poly(meth)acrylic acid-based polymer is crosslinked by reaction with a cellulose-reactive resin. A recording film is provided.

As the support film used in the present invention, a transparent plastic film is preferably used.

Examples of such materials include polyester films, polyamide films, acetate-1-films, polyvinyl chloride films, polycarbonate films, and polyethylene films. The thickness of the support film is 12 to 250 μm, preferably 25 to 250 μm.
It is 188 μm. If the support film has poor adhesion to the coating, or if it is difficult to uniformly coat the surface, a chemically or physically pretreated film can be used.

The recording film of the present invention comprises polyvinyl alcohol,
An aqueous solution containing at least one polymer selected from polyacrylic acid, polymethacrylic acid, and copolymers thereof and a cellulose-reactive resin is used as a coating liquid, and this coating liquid is coated on one or both sides of the support film. It can be manufactured by applying it to the surface and drying it by heating. in this case,
Heat drying temperature is 100-150°C, preferably 120-150°C
The temperature is 140°C.

As polyvinyl alcohol, the degree of polymerization is too high,
Preferably, those in the range of 1000 to 3000 are used. This polyvinyl alcohol is obtained by saponifying polyvinyl acetate, and in this case, the preferred degree of saponification is 75 to 90%. When the degree of polymerization of polyvinyl alcohol is less than 1000, the ink drying properties (ink absorption properties) of the film become poor, and the water resistance also becomes poor. If the degree of saponification is too high, the ink drying properties of the film will be poor.

The polyacrylic acid used has a molecular weight of 60,000 or more, preferably 80,000 to 200 QOO. As polymethacrylic acid, one having a molecular weight of 40,000 or more, preferably 50,000 or more is used.

The polyacrylic acid/methacrylic acid copolymer used has a molecular weight of 40,000 or more, preferably 50,000 or more, and has an arbitrary copolymerization ratio. If the molecular weight is smaller than the above range, the ink drying properties of the film will be poor.

The crosslinking agent used for the polymer in the present invention is known as a so-called cellulose-reactive resin that exhibits crosslinking reactivity toward the hydrogen groups of cellulose. As such, for example, dimethylol ethylene urea, dimethylol alkyl triazone, methylated dimethylol uron, dimethylol glyoxal monourein, dimethylol propylene urea and derivatives thereof are used.

These crosslinking agents react under acidic conditions to form ether bonds or ester bonds, thereby crosslinking the polyvinyl alcohol or poly(meth)acrylic acid polymer.

This reaction is promoted by an acidic catalyst, but in the case of the present invention, it is preferable to use latent catalysts such as ammonium chloride and ammonium sulfate. This latent catalyst acts during heat drying of the film and promotes the crosslinking reaction.

The weight ratio of polyvinyl alcohol and poly(meth)acrylic acid polymer is 9515 to 50150. The ratio of cellulose-reactive resin used is the total amount of polyvinyl alcohol and poly(meth)acrylic acid polymer: 10
The ratio is 0.1 to 5.0 parts by weight, preferably 0.2 to 3.5 parts by weight. If the proportion of polyvinyl alcohol used is too high, the ink absorption by the polymer film formed on the film will deteriorate.
On the other hand, if the amount is too low, the water resistance will deteriorate and the film will have a sticky coating on the surface.
~ Luck will begin to appear. If the ratio of the cellulose-reactive resin used is too high, the ink absorbency of the film will be poor, and if it is too low, the water resistance will be poor and stickiness will occur on the surface of the film.

A filler can be included in the film to prevent blocking. Examples of such fillers include silica, colloidal silica, alumina, talc, and fine resin powder. The average particle size of the filler is 0.01 to 5 μm
, preferably 0.01 to 1 μm.

In addition, the usage ratio is polyvinyl alcohol and poly(
The amount is 1 to 10 parts by weight, preferably 3 to 7 parts by weight, based on 100 parts by weight of the total amount of the meth)acrylic acid polymer. The thickness of the film is 2 to 20 μm, preferably 3 to 10 μm.
It is m.

〔effect〕

Since the recording film of the present invention has the polymer film formed on its surface having the above-mentioned structure, it has good ink absorbency during use and can be easily recorded (written) with water-based ink. Moreover, it has excellent water resistance, so it does not cause stickiness on the surface.

The recording film of the present invention is suitable as recording paper for pen plotters and Infusiera 1 to printers. In addition, since the recording film of the present invention has good recording properties (writing properties), it can be used with overhead projectors (
It is suitable as a recording base paper used for OHP).

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Polyvinyl alcohol (polymerization degree 1500, saponification degree 90
%) 80 parts by weight and polyacrylic acid (molecular weight 100.0
00) Add 2 parts by weight of dimethylolglyoxal monourein and 6 parts by weight of ammonium chloride as a crosslinking agent to an aqueous solution of 20 parts by weight of a polymer component dissolved in water at a polymer concentration of 10%, and apply it on a polyester film. Then, it was dried at 1.30°C to form a polymer film with a thickness of 5 μm.

Comparative Example 1 A polymer film having a thickness of 5 μm was formed on a polyester film in the same manner as in Example 1 except that 100 parts by weight of polyvinyl alcohol was used as the polymer component.

Comparative Example 2 In the same manner as in Example 1 except that the crosslinking agent was removed,
A polymer film with a thickness of 5 μm was formed on a polyester film.

The performance of each of the recording films obtained as described above was evaluated as follows, and the results are shown in Table 1.

(1) Using black ink from an ink-drying fiber tip pen (manufactured by VHP), draw a straight line on the film to be inspected. The ink was rubbed with absorbent cotton at regular intervals, and the time required for the ink to dry was expressed as the time required for the ink to dry.

(2) Water Resistance The coated surface was rubbed 100 times with absorbent cotton containing water, and the presence or absence of peeling of the film was examined.

O: There is no peeling of the film.

O: The filled pattern is projected using 01 (P), and the pattern has no uneven shading or fading.

× - After performing the same evaluation as above, uneven shading or fading appears in the pattern.

Table 1 Example 2 In the same manner as in Example 1, except that the weight ratio of polyvinyl alcohol (PVA) and polyacrylic acid (FAA) was changed, a film with a thickness of 5IJJn was deposited on a polyester film.
A polymer film was formed. Table 2 shows the ink drying properties and water resistance of this film. In this case, the water resistance is expressed as a relative value with the film shown in Example 1 being 100.

Table 2 6 parts by weight of Ni was added and applied onto a polyester film, and dried at 130°C to form a polymer film with a thickness of 5 μm.

Comparative Example 3 In the same manner as in Example 2 except that the crosslinking agent was removed,
A polymer film with a thickness of 5 μm was formed on a polyester film.

The performance of each of the recording films obtained as described above was evaluated as follows, and the results are shown in Table 3.

Table-3 It means a state in which it becomes impossible to

Example 3

Claims (3)

[Claims] (1) At least one side of the support film contains polyvinyl alcohol and at least one poly(meth)acrylic acid-based polymer selected from polyacrylic acid, polymethacrylic acid, and copolymers thereof. 1. A recording film comprising a film formed thereon, wherein each of the polymers is crosslinked by reaction with a cellulose-reactive resin. (2) The film according to claim 1, wherein the weight ratio of polyvinyl alcohol/poly(meth)acrylic acid polymer is from 95/5 to 50/50. (3) The polyvinyl alcohol has a degree of polymerization of 1,000 or more and a degree of saponification of 75 to 90%, and the poly(meth)acrylic acid-based polymer is polyacrylic acid with a molecular weight of 60,000 or more and/or polymethacrylic acid with a molecular weight of 40,000 or more. and/or a copolymer of these polymers having a molecular weight of 40,000 or more.