KR100191063B1 - Recording film - Google Patents

Abstract

The present invention not only has good water absorption of the aqueous ink, but also does not reduce water resistance or surface stickiness over a long period of time, and has a dot shape that is true to a circle, and has an excellent image resolution, in particular, an ink jet printer. To provide a recording film suitably used when typing or painting with an aqueous ink such as an ink jet plotter or a pen plotter, and as a solution, on one or both sides of the base film, (A) (A) an ink-receiving layer composed mainly of polyvinylpyrrolidone, (B) polyvinyl alcohol and / or polyvinyl acetal, and (C) particulate material, and (B) a dot form made of a quaternary ammonium salt type acrylic resin It is characterized by adapting the adjustment agent-containing layer sequentially.

Description

Recording film

1 is an enlarged cross-sectional view of one example of the recording film of the present invention.

* Explanation of symbols for main parts of the drawings

1: base film 2: lower support layer

3: ink containing layer 4: dot shape adjusting agent containing layer

5: mat layer

The present invention is a novel sheet for the film, more specifically, the water-absorbing ink is good, and the water resistance and surface stickiness does not occur over a long period of time, the dot shape is true to the circle, etc. The present invention relates to a recording film that has excellent performance and is used when typing or painting by water-based ink such as an ink jet printer, an ink jet plotter, or a pen plotter.

In recent years, with the spread of computer-use technology, it has become common to print out data produced by a computer using a printer or the like. The printer used at this time may include a dot impact printer, a laser printer, a thermal printer, an ink jet printer, and the like. However, the ink jet printer has a low mechanical noise at the time of printout, and a low maintenance cost associated with printout. It is used a lot. As the recording paper used when the ink jet printer is used, plain paper or coated paper is usually used, but a recording film having an ink receiving layer made of a hydrophilic polymer material on the surface of a base film made of a plastic film is also used.

And as an ink receiving layer formed on this base film, what consists of polyvinyl alcohol and polyvinylpyrrolidone so far (Japanese Unexamined-Japanese-Patent No. 6-427), forms the receiving layer which consists of at least 2 layer on the base film, Using a polyacetal resin layer on the outermost layer and a water-soluble resin on the ink receiving layer below it (JP-A-5-262028), forming a dye adsorption layer on one side of the substrate, and swellable polymer on the opposite side Ink receiving layer containing polyvinyl alcohol or polyvinyl acetal and polyvinylpyrrolidone, such as a compound layer formed of a mixture layer of polyvinyl alcohol and polyvinylpyrrolidone (see Japanese Patent Application Laid-Open No. 5-286228). Is proposed.

However, when the ink receiving layer is formed by the combination of polyvinyl alcohol, polyvinal acetal, and polyvinylpyrrolidone, the water absorption of the ink absorbing layer is low and the stickiness of the surface of the ink receiving layer cannot be avoided. The conditions required for the recording film for jets, i.e., the diameter of the ink dot should not be made larger than necessary, and the condition that the shape of the ink dot is close to a true circle, and its surroundings are smooth, is not satisfied. A dot shape becomes a polygon, a star, etc., and the problem of causing the fall of the resolution (sharpness, sharpness of a line, etc.) of the image obtained arises.

The present invention overcomes the drawbacks of such a conventional recording film using an aqueous ink, has good absorbency of the modified ink, and prevents water resistance and surface stickiness from occurring over a long period of time. It is made for the purpose of providing a recording film used when typing or painting by water-based ink such as an ink jet printer, an ink jet plotter, a pen plotter, and the shape of which is close to a real circle and excellent in image resolution.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to develop the recording film which has the said preferable property, the present inventors laminated | stacked the specific ink receiving layer and the dot-form adjustment layer sequentially on one side or both sides of the base film, and the objective The present invention has been accomplished based on this finding.

That is, the present invention is based on (A) (a) polyvinylpyrrolidone, (b) polyvinyl alcohol and / or polyvinyl acetal, and (poly) particulate matter as main components on one or both surfaces of the base film. It is an object of the present invention to provide a recording film comprising an ink-receiving layer and a dot-shaped regulator-containing layer made of (B) a quaternary ammonium salt type acrylic resin.

There is no restriction | limiting in particular about the base film used in the recording film of this invention, The thing conventionally used as a base material in the recording film conventionally, for example, selects arbitrary from polyethylene terephthalate, polyethylene, polypropylene, and polyamide. Although it can be used, among these, polyethylene terephthalate is especially suitable. The thickness of this base film is 25-250 micrometers normally, Preferably it is the range of 50-100 micrometers.

In the recording film of the present invention, an ink receiving layer is formed as one (A) layer on one side or both sides of the base film. However, in order to improve the adhesion between the ink receiving layer and the base film, the base film can be used as desired. And a lower support layer may be formed between the ink receiving layer and the ink receiving layer. As this lower support layer, saturated polyester resin, urethane resin, etc. are used normally, but urethane resin is especially preferable because adhesiveness with an ink receiving layer is favorable. The thickness of this lower support layer is the range of 0.5-1.5 micrometers normally.

Next, the ink receiving layer of the layer (A) is a layer containing (a) polyvinylpyrrolidone, (b) polyvinyl alcohol and / or polyvinyl acetal and (c) particulate matter as main components. As the polyvinylpyrrolidone of the (0) component used in the above, the molecular weight is usually in the range of 40000 or more, preferably in the range of 600000 to 2800000. When the molecular weight is less than 40000, the absorption rate and water solubility of the ink are insufficient. As a result, the dryness of the ink is lowered.

On the other hand, as polyvinyl alcohol used as (b) component, the thing of the range of polymerization degree 1000 or more preferably 1000-3000 is used normally. If the degree of polymerization is less than 1000, there is a fear that the ink dryness (ink absorbability) and the water resistance of the film become insufficient. In addition, as the polyvinyl alcohol, a partial or full soaped product of polyvinyl acetate having a saponification degree of 75 mol% or more is preferable, and a partial soap having a saponification degree of 75 to 90 mol% is particularly preferable. If the saponification degree is less than 75 mol%, the ink absorption speed becomes slow. Moreover, polyvinyl acetal is obtained by reaction of polyvinyl alcohol and an aldehyde, and acetalization degree is 2-20 mol%, The thing of 5-15 mol% is used normally. If the acetalization degree is less than 2 mol%, sufficient water resistance cannot be obtained. If the acetalization degree exceeds 20 mol%, the water resistance is good, but the ink drying property and the crosslinkability described later are lowered.

In the present invention, the polyvinyl alcohol may be used as the component (b), polyvinyl acetal may be used, or a mixture thereof may be used. These polyvinyl alcohols and polyvinyl acetal may further improve the water resistance. For this purpose, crosslinking with a fibrinated crosslinking agent or urea is preferable. Fibrin-reactive crosslinking agents are crosslinking agents reactive with hydroxyl groups of cellulose, such as dimethylol ethylene urea, dimethylol propylene urea, dimethylol alkyltriazone, methylated dimethyluron, dimethylolglyoxal monourea And urea derivatives in the form of a ring or heterocyclic ring such as phosphorus. These react with a functional group of polyvinyl alcohol or polyvinyl acetal in the presence of a catalyst such as ammonium chloride, ammonium nitride, ammonium sulfate or the like to form a three-dimensional structure. The fibrinated crosslinking agent or urea is usually used in an amount of 4 to 12 parts by weight, preferably 5 to 10 parts by weight based on 100 parts by weight of polyvinyl alcohol or polyvinyl acetal. If the amount is less than 4 parts by weight, the effect of improving water resistance is not sufficiently exhibited. If the amount exceeds 12 parts by weight, the ink absorbency tends to be lowered. Moreover, the catalyst used together with this is normally used in the ratio of 20-100 weight% with respect to a cellulose reactive crosslinking agent.

Moreover, as a particulate-form substance used as (C) component, there are an inorganic type and an organic type thing, As an inorganic particulate matter material, for example, silica, zirconia, clay, kaolin, alumina, titania, zeolite, calcium carbonate, barium sulfate, Powders, such as magnesium hydroxide, a calcium phosphate, and glass, are mentioned. Preferred of these are synthetic silica powders or calcium carbonate powders, which do not impair the dot shape and are excellent in the absorbency of aqueous ink. Examples of the organic particulate material include powders of synthetic resins such as acrylic resins, urethane resins, vinyl chloride resins, benzoguanamine resins, and benzoguanamine / melamine / formaldehyde condensates. These particulate matters may be used alone, or may be used in combination of two or more thereof. In particular, by using the synthetic silica powder and the calcium carbonate powder in a ratio of about 1: 1 by weight, ink drying property and ink absorbency are improved, which is preferable.

As for the particulate-form substance of the said (poly) component, it is suitable that the average particle diameter is 0.5-15 micrometers, Preferably it is the range of 0.8-9 micrometers. When the average particle diameter is less than 0.5 mu m, the ink drying property is inferior, and when the average particle diameter exceeds 15 mu m, the dot shape is less likely to become a true circle shape, and the image resolution tends to be lowered.

About the content ratio of the said (A) component, (B) component, and (C) component, (A) component and (B) component are weight ratio 1: 9-6: 4, Preferably 2: 8-4: 6 It is preferable to exist in the range of. When the amount of (a) component is more than this range, water resistance falls and it becomes a cause of stickiness, and when the amount of (b) component is more than this range, ink drying property (ink absorbency) tends to fall. Moreover, it is preferable that (a) component exists in the range of 30-100 weight%, Preferably it is 40-80 weight% with respect to the total weight of (a) component and (b) component. If this amount is less than 30% by weight, the ink drying property is inferior, and if it exceeds 100% by weight, the water resistance of the coating film tends to be lowered.

In the present invention, the above-mentioned (A) component, (B) component and (C) component are dissolved or dispersed in an aqueous medium at a predetermined ratio, respectively, to prepare a coating liquid having a solid content concentration of about 10 to 15% by weight. The ink receiving layer which is (A) layer is formed by apply | coating and drying according to a conventional method on the film or the lower support layer formed as desired. At this time, various additives conventionally used, such as surfactant, a lubricant, a stabilizer, a coloring agent, etc. can be added to this coating liquid. The thickness of this ink receiving layer is 5-30 micrometers normally, Preferably it is the range of 10-20 micrometers.

In the present invention, it is necessary to form a dot-form adjusting agent-containing layer as the (B) layer on the receiving layer thus formed. As this dot shape regulator, a quaternary ammonium salt type acrylic resin is mentioned preferably, for example. As a specific example of this quaternary ammonium salt type acrylic resin, the copolymer salt etc. of alkyl acrylate, alkyl methacrylate, and dialkylamino acrylate and dialkylamino alkyl methacrylate are mentioned. Such quaternary ammonium salt type acrylic resins are well known. For example, quaternary salts of a copolymer having a molar ratio of 1: 1 of butyl methacrylate and dimethylaminoethyl methacrylate are available as commercially available products.

To form the dot-form adjusting agent-containing layer of layer (B), the dot-shaped adjusting agent may be dissolved in a suitable solvent, for example, alcohol or a mixture of alcohol and water, and the solution may be applied onto the ink receiving layer and then dried. At this time, the dot shape adjusting agent may be formed on the ink receiving layer, or may be partially dissolved or impregnated in the ink receiving layer.

The range of 3-10 g / m <2> is suitable for the coating amount of the said dot shape regulator of (B). If the coating amount of the dot-shaped regulator of this layer (B) is less than 3 g / m 2, the sharpness (image resolution) of the image is insufficient, and if the coating amount of the dot-shaped regulator of (B) layer exceeds 10 g / m 2, the ink absorbency and ink gun The composition tends to be lowered. This (B) layer has a function of further forming a dot shape into a real circle and preventing the spread of ink.

In the present invention, when the (A) ink receiving layer and (B) the dot-shaped regulator-containing layer are formed on only one side of the base film, the mat on the other side of the base film, that is, the side opposite to the side (back side), as desired. A layer or the ink receiving layer similar to the above can be formed. The mat layer is formed of a binder and a matting agent, and examples of the binder include thermoplastic resins, thermosetting resins, and photocurable resins. Specific examples of the resin include acrylic resins, urethane resins, polyester resins, and vinyl chloride resins. Can be mentioned. As the matting agent, for example, silica, zirconia, clay, kaolin, alumina, titania, zeolite, calcium carbonate, barium sulfate, magnesium hydroxide, calcium phosphate, inorganic powder such as glass, acrylic resin, urethane resin, vinyl chloride Synthetic resin powders such as resin, benzoguanamine resin, and benzoguanamine / melamine / formaldehyde condensate. The average particle diameter of this matting agent is 0.1-20 micrometers, Preferably the range of 2-10 micrometers is preferable.

In addition, when forming an ink receiving layer on the back surface of a base film, you may form the same thing as what was formed in the surface of a base film, and it is a thing of another composition, for example, it does not contain a matting agent, or it contains a very small amount, and is transparent You may form the ink receiving layer with this.

The thickness of the mat layer is 1 to 10 µm, and preferably 3 to 7 µm, in terms of obtaining curl prevention property or good writing property. Moreover, this mat layer can contain what is conventionally used as an additive, for example, surfactant, a lubricant, a stabilizer, a coloring agent.

1 is a cross-sectional view showing a configuration in one example of the recording film of the present invention, wherein the lower support layer 2, the ink receiving layer 3, and the dot-shaped adjusting agent-containing layer 4 are formed on the surface of the base film 1; This has a structure which is laminated | stacked sequentially and the mat layer 5 was formed in the back surface of the base film 1 (opposite to an ink receiving layer).

The recording film of the present invention is excellent in the absorption rate and water solubility of the aqueous ink, and since the dot shape is closer to a true circle, the image formed on the ink receiving layer is clear (high resolution), and also excellent in water resistance. After the formation, the bleeding of the image does not become thick, and a sharp and sharp image can be obtained, and the ink receiving layer is not dissolved by moisture or hand sweat in the air, so that no stickiness is generated. It is easy to handle and has excellent performances such as improved work efficiency, and is particularly suitable as a recording film used when typing or painting by water-based ink such as ink get printers, ink jet plotters, and pen plotters.

Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.

In addition, the physical property of the recording film was evaluated in accordance with the method shown next.

(1) dot shape

Dot shape and dot outline were visually observed by a stereomicroscope, and evaluated according to the following criteria.

(Circle): Circular shape and sharp outline.

(Triangle | delta): It is circular, although there is some disorder

X: Not circular but polygonal.

(2) printability

10 lines of 0.716 mm wide, which were subjected to computer image processing by the Hewlett-Packard Inkjet Polo (Design Jet 650C), are shown in parallel at intervals of 0.220 mm, and the sharpness of the image and the degree of bleeding of the ink are shown below. Evaluation was made according to the standard.

○: 9 or more lines can be identified (good)

△: 7 to 8 can be identified (slightly defective)

×: only 6 or less can be identified (bad)

(3) ink drying

When an image is formed by an ink jet plotter (Design Jet 650C) manufactured by Hewlett-Packard Co., and dried by finger contact within 30 seconds after drawing the image, △, when drying for less than 60 seconds longer than 30 seconds, △, it takes longer than 60 seconds The case was made into x.

(4) stickiness

The degree of stickiness by finger contact was determined on the conditions of the temperature of 25 degreeC, and 80% of humidity on the following references | standards.

○: Stickiness cannot be confirmed.

△ can feel sticky to some extent but is not clear

×: Obvious stickiness can be confirmed

Example 1

6 parts by weight of polyvinylpyrrolidone (molecular weight 1280000), 14 parts by weight of polyvinyl alcohol (polymerization degree 2000, saponification degree 88.0 mol%), 6 parts by weight of synthetic silica powder having an average particle diameter of 3.5 μm, carbonic acid having an average particle diameter of 2.0 μm Forming an ink receiving layer by mixing 4 parts by weight of calcium powder, 1.4 parts by weight of dimethylolglyoxal monourene as a fibrinated crosslinking agent, 0.3 parts by weight of ammonium chloride, 40 parts by weight of ethanol, 20 parts by weight of propylene glycol monomethyl ether and 108.3 parts by water A solvent coating solution was prepared.

On one side of a 50-micron-thick polyethylene terephthalate film, a lower support layer having a thickness of 1.0 μm made of urethane resin was formed, and then the coating solution was applied onto the lower support layer using a wire bar coater, and then, at 130 ° C., 5 It heated for minutes, and formed the ink receiving layer of about 15 micrometers in thickness.

A quaternary ammonium salt type acrylic resin (manufactured by Mitsubishi Yuka Co., Ltd., Saftomer CP-2000) of 1.0 part by weight, 10.0 parts by weight of ethanol and 89.0 parts by weight of water was prepared, and this ink was prepared. It applied on the receiving layer, dried, and formed the dot shape adjuster containing layer whose usage-amount of a dot shape adjuster is 4 g / m <2>.

Subsequently, on the base film surface opposite to the coating layer, 20 parts by weight of a binder (acrylic copolymer), 10 parts by weight of a matting agent (synthetic silica powder, an average particle diameter of 3.5 μm), and 70 parts by weight of water were used for filling the mat. The coating solution was applied and heated at 30 ° C. for 2 minutes to form a mat layer having a thickness of 5 μm. The physical properties of the recording film thus obtained are shown in Table 3.

EXAMPLES 2-5

In Example 1, the recording film was produced like Example 1 except having used the composition shown in Table 1 as a coating liquid for ink receiving layer formation, and the physical property was calculated | required. The results are shown in Table 3.

Example 6

In Example 1, 8 parts by weight of polyvinyl alcohol (polymerization degree 1700, saponification degree 88 mol%), 4 parts by weight of polyvinylpyrrolidone (molecular weight 630,000), polystyrene, instead of forming a mat layer on the back side of the ink receiving layer 1.5 parts by weight of sulfonic acid salt (manufactured by Sanyo Chemical Co., Ltd., Chemistat 6120), 0.25 parts by weight of dimethylolglyoxal monourene, a fibrin-reactive crosslinking agent, 0.2 parts by weight of ammonium chloride, 30 parts by weight of ethanol and 106.1 parts by weight of water Then, the coating liquid for filling was apply | coated using a wire bar spreader, it heated at 130 degreeC for 5 minutes, and formed the recording film similarly to Example 1 except having formed another ink receiving layer of thickness 10micrometer. The physical properties of the recording film thus obtained are shown in Table 3.

Example 7

In Example 1, 7 weight part of polyvinyl alcohol (polymerization degree 1700, saponification degree 88 mol%), 1 weight part of polyvinylpyrrolidone (molecular weight 630,000), polystyrene instead of forming a mat layer on the back side of an ink receiving layer 2 parts by weight of sulfonic acid salt (manufactured by Sanyo Chemical Co., Ltd., Chemistat 6120), 0.2 parts by weight of dimethylolglyoxal monourene, a fibrin-reactive crosslinking agent, 0.1 parts by weight of ammonium chloride, 20 parts by weight of ethanol, 69.66 parts by weight of water, 0.04 parts by weight of synthetic silica (average particle diameter: 6 mu m) was mixed to prepare a coating solution for filling, and the coating solution was prepared on a bottom support layer of 0.7 g / m 2 made of urethane resin and coated with urethane resin. After applying the coating liquid on the lower support layer of the amount 0.7g / ㎡ using a wire bar coater, it was heated at 130 ° C. for 5 minutes and formed in the same manner as in Example 1 except that an ink receiving layer having a thickness of 10 μm was formed. Forming film It was. The physical properties of the recording film thus obtained are shown in Table 3.

Comparative Example 1

A recording film was produced in exactly the same manner as in Example 1 except that the dot-form adjusting agent-containing layer in Example 1 was not formed. This physical property is shown in Table 3.

Comparative Example 2

A recording film was produced in exactly the same manner as in Example 2 except that the dot-form adjusting agent-containing layer in Example 2 was not formed. This physical property is shown in Table 3.

Comparative Example 3

A recording film was produced in exactly the same way as in Example 1 except that the synthetic silica powder and the calcium carbonate powder were not blended in the ink receiving layer of Example 1. Its physical property is shown in Table 3.

[Comparative Example 4]

A recording film was produced in exactly the same way as in Example 2 except that the synthetic silica powder and the calcium carbonate powder were not blended in the ink receiving layer of Example 2. This physical property is shown in Table 3.

The mixing | blending ratio of the coating liquid for ink aqueous layer formation with respect to the comparative examples 1-4 mentioned above is as showing in Table 2.

In the results of Table 3, the recording film of the present invention (Examples 1 to 7) had a circular dot shape, sharpened outlines, excellent image resolution, good ink drying, and excellent surface quality. It can be seen that there is no stickiness. In addition, the recording films of Examples 6 and 7 are excellent in being able to prepare images on both sides because the recording film of the ink receiving layer having transparency is formed on the back side so that the recording of the ink receiving layer on the surface can be seen from the ink receiving layer on the back side. Effect.

Claims (5)

On one side or both sides of the base film, (A) (a) polyvinylpyrrolidone, (b) polyvinyl alcohol and / or polyvinyl acetal, and (c) an ink-receiving layer containing as a main component, (B) A film for recording, characterized in that a layer of dot-form adjusting agent made of a quaternary ammonium salt type acrylic resin is sequentially layered. The (A) ink-receiving layer according to claim 1, wherein the content ratio between the (A) component and the (NA component) is 1: 9 to 6: 4 by weight, and the content of the (C) component is (A) It is 30-100 weight% with respect to the total weight of a component and (b) component, The recording film characterized by the above-mentioned. The polyvinyl alcohol and / or polyvinyl acetal of the component (b) in the ink receiving layer (A) is crosslinked by a reaction with a fibrinated crosslinking agent or urea. Film for recording. (B) The recording film, characterized in that the component is crosslinked by the reaction of 100 parts by weight of polyvinyl alcohol and / or polyvinyl acetal with 4 to 12 parts by weight of a fibrinated crosslinking agent or urea. The film for recording according to claim 1 or 2, wherein the particulate material of the (multi) component in the (A) ink-receiving layer has an average particle diameter of 0.5 to 15 µm.