JP3301681B2 - Water-based ink recording film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel recording film, and more particularly, to a water-based ink having good absorbability, not causing a decrease in water resistance or sticky surface for a long period of time, and a dot shape. The present invention relates to a water-based ink recording film having excellent performance such as being close to a perfect circle, and particularly used when writing or drawing with a water-based ink such as an ink jet printer, an ink jet plotter, or a pen plotter.

[0002]

2. Description of the Related Art In recent years, with the widespread use of computer technology, materials created by computers have been frequently printed out using a printer or the like. Printers used at this time include dot impact printers, laser printers, thermal printers, and inkjet printers.However, there is almost no mechanical noise at the time of printout, and the running cost associated with printout is low. Printers are often used. Normally, plain paper and coated paper are often used as the paper used when using this ink jet printer.However, an ink receiving layer made of a hydrophilic polymer substance is provided on the surface of a base film made of a plastic film. The provided recording film is also used.

[0003] As the ink receiving layer provided on the substrate film, there have hitherto been used those comprising polyvinyl alcohol and polyvinyl pyrrolidone (Japanese Patent Publication No. 6-427), and those comprising at least two layers on a support. Provided, a polyvinyl acetal resin layer on the outermost layer,
A water-soluble resin is used for the ink receiving layer below the layer (Japanese Patent Application Laid-Open No. H5-262028). A dye-adsorbing layer is provided on a substrate, and a swellable polymer compound such as polyvinyl An ink receiving layer containing polyvinyl alcohol, polyvinyl acetal, and polyvinyl pyrrolidone has been proposed, such as one provided with a mixture layer of alcohol and polyvinyl pyrrolidone (Japanese Patent Laid-Open No. 5-286228).

However, when an ink receiving layer is formed by a combination of polyvinyl alcohol or polyvinyl acetal and polyvinyl pyrrolidone, the water resistance of the ink absorbing layer is low, the stickiness of the surface of the ink receiving layer cannot be avoided, and the ink jet recording cannot be avoided. The conditions required as a recording film for use, that is, (1) that the diameter of the ink dot does not become larger than necessary, and (2) that the shape of the ink dot is close to a perfect circle and the periphery thereof is smooth In addition, the dot shape becomes polygonal (for example, a star pattern), which causes a problem that the resolution (sharpness, sharpness of image lines, etc.) of the obtained image is reduced.

[0005]

SUMMARY OF THE INVENTION The present invention overcomes the above-mentioned drawbacks of the conventional recording film using a water-soluble ink, has a good water-absorbing ink absorption property, and has a low water resistance over a long period of time. Water-based ink recording used when writing or drawing with water-based inks such as ink-jet printers, ink-jet plotters and pen plotters, in addition to causing no stickiness on the surface and having a dot shape close to a perfect circle and excellent image resolution. It was made for the purpose of providing a film.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to develop a recording film having the above-mentioned preferable properties, and as a result, a specific ink receiving layer and a dot are formed on at least one surface of a base film. It has been found that the object can be achieved by sequentially laminating the shape-controlling agent-containing layers, and the present invention has been completed based on this finding.

That is, according to the present invention, (A) (a) polyvinylpyrrolidone,
(B) polyvinyl alcohol or polyvinyl acetal or both, and (c) a particulate substance as a main component, and the content ratio of the component (a) to the component (b) is 2: 8 to 4: 6 by weight, And the content of the component (c) is 30 to 1 with respect to the total weight of the component (a) and the component (b).
A water-based ink recording film characterized by sequentially laminating an ink-receiving layer of 100% by weight and (B) a dot shape adjusting agent-containing layer made of a quaternary ammonium salt type acrylic resin. .

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The substrate film used in the recording film of the present invention is not particularly limited, and those conventionally used as a substrate for a recording film, for example, polyethylene terephthalate, polyethylene, polypropylene, polyamide, etc. Any of these can be selected and used, and among these, polyethylene terephthalate is particularly preferred. The thickness of the substrate film is usually 25 to 250 μm, preferably 50 to 10 μm.
The range is 0 μm.

In the recording film of the present invention, an ink receiving layer is provided as a layer (A) on one or both sides of the base film, and the adhesion between the ink receiving layer and the base film is improved. For this purpose, an undercoat layer may be provided between the base film and the ink receiving layer, if desired. As the undercoat layer, a saturated polyester resin, a urethane resin, or the like is usually used, but a urethane resin is particularly preferable because of good adhesion to the ink receiving layer.
The thickness of the undercoat layer is usually in the range of 0.5 to 1.5 μm.

Next, the ink receiving layer of the layer (A) comprises (a)
Polyvinylpyrrolidone, (b) polyvinyl alcohol or polyvinyl acetal, or both, and (c) a layer mainly composed of particulate matter. The polyvinylpyrrolidone of component (a) used in the ink receiving layer usually has a molecular weight of 40000 or more, preferably 6000
Those having a range of 00 to 2800000 are used. When the molecular weight is less than 40,000, the ink absorption rate and receptivity become insufficient, and as a result, the drying property of the ink decreases.

On the other hand, the polyvinyl alcohol used as the component (b) generally has a degree of polymerization of at least 1,000,
Preferably, those having a range of 1000 to 3000 are used. When the degree of polymerization is less than 1,000, the ink drying property (ink absorption property) and water resistance of the coating may be insufficient. The polyvinyl alcohol is preferably a partially saponified or completely saponified polyvinyl acetate having a saponification degree of 75 mol% or more, and particularly preferably a saponification degree of 75 to 9%.
0 mole% partially saponified is preferred. Saponification degree 75
If the amount is less than mol%, the ink absorption speed becomes low. The polyvinyl acetal is obtained by a reaction between polyvinyl alcohol and an aldehyde, and usually has a degree of acetalization of 2 to 20 mol%, preferably 5 to 15 mol%.
Is used. If the degree of acetalization is less than 2 mol%, sufficient water resistance cannot be obtained, and if it exceeds 20 mol%, although the water resistance is good, the ink drying property and the crosslinkability deteriorate.

In the present invention, the above-mentioned polyvinyl alcohol, polyvinyl acetal, or a mixture thereof may be used as the component (b), but these polyvinyl alcohols and polyvinyl acetal may be used. Is preferably cross-linked with a fibrous-reaction type cross-linking agent or urea in order to further improve the water resistance. The cellulose-reactive cross-linking agent is a cross-linking agent having reactivity to hydroxyl groups of cellulose, such as dimethylol ethylene urea, dimethylol propylene urea, dimethylol alkyl triazone, methylated Cyclic or heterocyclic urea derivatives such as dimethyloluron and dimethylolglyoxal monourein; These react with functional groups in polyvinyl alcohol or polyvinyl acetal in the presence of a catalyst such as ammonium chloride, ammonium nitrate, ammonium sulfate or the like to form a three-dimensional structure. The cellulose-reactive crosslinking agent or urea is usually used in an amount of 4 to 12 parts by weight per 100 parts by weight of polyvinyl alcohol or polyvinyl acetal.
It is used in a proportion of 5 parts by weight, preferably 5 to 10 parts by weight. If the amount is less than 4 parts by weight, the effect of improving water resistance is not sufficiently exhibited, and if it exceeds 12 parts by weight, the ink absorbency tends to decrease. The catalyst used in combination therewith is usually used in a proportion of 20 to 100% by weight based on the amount of the fibrin-reaction type crosslinking agent.

Further, the fine particles used as the component (c) include inorganic and organic materials. Examples of the inorganic fine particles include silica, zirconia, and the like.
Clay, kaolin, alumina, titania, zeolite,
Calcium carbonate, barium sulfate, magnesium hydroxide,
Examples include powders of calcium phosphate, glass and the like. Preferred among these are synthetic silica powder and calcium carbonate powder, which do not impair the dot shape and have excellent ink absorbency. Examples of the organic fine particles include powders of synthetic resins such as acrylic resins, urethane resins, vinyl chloride resins, benzoguanamine resins, and benzoguanamine / melamine / formaldehyde condensates. These fine particles may be used alone or in combination of two or more. In particular, it is preferable to use the synthetic silica powder and the calcium carbonate powder at a weight ratio of about 1: 1 because the ink drying property and the ink absorbing property are improved.

The fine particles of component (c) preferably have an average particle diameter of 0.5 to 15 μm, preferably 0.8 to 9 μm. This average particle diameter is 0.5 μm
If it is less than 15 μm, the ink drying property is inferior. If it exceeds 15 μm, the dot shape is difficult to become a perfect circle, and the image resolution tends to decrease.

The content ratio of the components (a), (b) and (c) is such that the weight ratio of the components (a) and (b) is in the range of 2: 8 to 4: 6. To be elected. If the amount of the component (a) is more than this range, the water resistance will be reduced, causing stickiness. If the amount of the component (b) is more than this range, the ink drying property (ink absorption) will be reduced. The component (c) is 30 to 100% by weight, preferably 40% by weight, based on the total weight of the components (a) and (b).
It must be in the range of ８０80% by weight. If the amount is less than 30% by weight, the ink drying property is poor, and if it exceeds 100% by weight, the water resistance of the coating film is reduced.

In the present invention, the component (A)
The component (b) and the component (c) are dissolved or dispersed in an aqueous medium at a predetermined ratio, respectively, to prepare a coating solution having a solid concentration of about 10 to 15% by weight. The ink receiving layer, which is the layer (A), is provided on the undercoating layer by applying and drying according to a conventional method. At this time, conventionally used various additives such as a surfactant, a lubricant, a stabilizer, and a coloring agent can be added to the coating liquid. The thickness of the ink receiving layer is usually in the range of 5 to 30 μm, preferably 10 to 20 μm.

In the present invention, it is necessary to provide a dot shape adjusting agent-containing layer as layer (B) on the ink receiving layer thus provided. Examples of the dot shape adjusting agent include a quaternary ammonium salt type acrylic resin, for example, a copolymer salt of an alkyl acrylate or an alkyl methacrylate with a dialkylamino acrylate or a dialkylaminoalkyl methacrylate. Such quaternary ammonium salt type acrylic resins are known. For example, a quaternary salt of a copolymer of butyl methacrylate and dimethylaminoethyl methacrylate having a molar ratio of 1: 1 is available as a commercial product.

In order to form the dot shape adjusting agent-containing layer of the layer (B), the dot shape adjusting agent is dissolved in a suitable solvent, for example, alcohol or a mixture of alcohol and water, and this solution is applied to the ink receiving layer. After applying on the top, it may be dried.

The coating amount of the dot shape adjusting agent (B) is suitably in the range of 3 to 10 g / m ² . When the coating amount of the dot shape adjusting agent of the layer (B) is less than 3 g / m ² , the image clarity (image resolution) is insufficient, and the coating amount of the dot shape adjusting agent of the layer (B) is insufficient. If it exceeds 10 g / m ² , the ink absorbency and the ink drying property tend to be reduced.
This (B) layer has the effect of forming the dot shape to a more perfect circle and further preventing the ink from bleeding.

In the present invention, when (A) the ink receiving layer and (B) the dot shape adjusting agent-containing layer are provided on one surface of the substrate film, the back surface of the substrate film [the ink receiving layer of the (A) layer and May be provided with a mat layer or an ink receiving layer, if desired. The mat layer is formed by a binder and a matting agent.Examples of the binder include a thermoplastic resin, a thermosetting resin, a photocurable resin, and the like.Specifically, acrylic, urethane, polyester, Examples of each resin include vinyl chloride resins. As the matting agent, for example, silica, zirconia, clay, kaolin, alumina, titania, zeolite, calcium carbonate, barium sulfate, magnesium hydroxide, calcium phosphate, inorganic powders such as glass, acrylic resin, urethane resin, Synthetic resin powders such as vinyl chloride resin, benzoguanamine resin, and benzoguanamine / melamine / formaldehyde condensate are exemplified.
The average particle diameter of the matting agent is in the range of 0.1 to 20 μm, preferably 2 to 10 μm. Further, when the ink receiving layer is also formed on the back surface of the base film, the same one as provided on the front surface of the base film may be provided, or the other, for example, does not contain a matting agent, Alternatively, a transparent ink receiving layer containing a very small amount may be provided.

The thickness of the mat layer is advantageously in the range of 1 to 10 μm, preferably 3 to 7 μm, from the viewpoint of preventing curling and good writing properties. Further, the mat layer may contain those conventionally used as additives, for example, a surfactant, a lubricant, a stabilizer, and a colorant.

FIG. 1 is a cross-sectional view showing the structure of an example of the recording film of the present invention.
The undercoat layer 2, the ink receiving layer 3, and the dot shape adjusting agent-containing layer 4 are sequentially laminated, and a mat layer 5 is provided on the back surface (the surface opposite to the ink receiving layer) of the base film 1. are doing.

[0023]

As described above, the recording film of the present invention is excellent in the absorption rate and receptivity of the aqueous ink, and the dot shape is closer to a perfect circle, so that the image formed on the ink receiving layer is clear (high image resolution). ) And has excellent water resistance, so that a clear and sharp image can be obtained without blurring or fattening of the image after the image is formed. Because it does not dissolve, it is excellent in handling without causing stickiness,
It has excellent performance such as improved work efficiency, and is particularly suitable as a water-soluble ink recording film used when writing or drawing with an aqueous ink such as an ink jet printer, an ink jet plotter, or a pen plotter.

[0024]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The physical properties of the recording film were evaluated according to the following methods. (1) Dot shape Visually observe the dot shape and dot outline with a stereo microscope,
Evaluation was made according to the following criteria. ：: circular and sharp outline △: turbulence observed

(2) Printability 10 images with a width of 0.176 mm at intervals of 0.220 mm are drawn out of 10 images processed by a computer using an inkjet plotter (Design Jet650C) manufactured by HEWLETT PACKARD, and the sharpness of the image and the ink Was evaluated according to the following criteria. ：: 9 or more lines can be identified (good) Δ: Only 7 to 8 lines can be identified (bad)

(3) Ink drying property An image was formed with an ink jet plotter (Design Jet650C) manufactured by HEWLETT PACKARD, and when the finger was dried within 30 seconds after drawing, it was evaluated as ○ 3.
When drying for more than 0 seconds and less than 60 seconds, Δ, 6
The case where it took more than 0 seconds was evaluated as x.

(4) Stickiness Under the conditions of a temperature of 25 ° C. and a humidity of 80%, the degree of stickiness was judged by touch with a finger according to the following criteria. ：: Not sticky. △: Slightly sticky. ×: Not sticky.

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 size of 3.5 μm, average 4 parts by weight of calcium carbonate powder having a particle size of 2.0 μm, 1.4 parts by weight of dimethylol glyoxal monourein as a cellulose reaction crosslinking agent, 0.3 parts by weight of ammonium chloride, 40 parts by weight of ethanol, and propylene glycol monomethyl ether 20 By weight, 108.3 parts by weight of water and 108.3 parts by weight of water were mixed to prepare a coating liquid for forming an ink receiving layer.

On one side of a polyethylene terephthalate film having a thickness of 50 μm, a urethane resin having a thickness of 1.0
After the undercoat layer having a thickness of μm was provided, the coating solution was applied onto the undercoat layer using a wire bar, and heated at 130 ° C. for 5 minutes to form an ink receiving layer having a thickness of about 15 μm.

Further, a quaternary ammonium salt type acrylic resin [Saftomer CP-2000, manufactured by Mitsubishi Yuka Co., Ltd.]
1.0 part by weight, 10.0 parts by weight of ethanol and 89.0 parts of water
A part of the dot shape adjusting agent-containing layer forming liquid is prepared, applied to the ink receiving layer, and dried to form a dot shape adjusting agent-containing layer containing 4 g / m ² of the dot shape adjusting agent. Formed.

Next, on the back surface of the ink receiving layer, 20 parts by weight of a binder (acrylic resin), 10 parts by weight of a matting agent (synthetic silica powder, average particle size of 3.5 μm) and water 7
0 parts by weight of a mat layer forming coating solution,
By heating at 2 ° C. for 2 minutes, a mat layer having a thickness of 5 μm was formed. Table 3 shows the physical properties of the water-soluble ink recording film thus obtained.

Examples 2 and 3 A water-soluble ink recording film was prepared in the same manner as in Example 1, except that the composition shown in Table 1 was used as the coating liquid for forming the ink receiving layer. It was manufactured and its physical properties were determined. Table 3 shows the results.

Example 4 In the same manner as in Example 1, a laminated film having an ink receiving layer and a dot shape adjusting agent-containing layer on one side of a polyethylene terephthalate film via an undercoat layer was produced.
Next, instead of providing the mat layer on the back surface of the ink receiving layer, 8 parts by weight of polyvinyl alcohol (polymerization degree 1700, saponification degree 88 mol%), 4 parts by weight of polyvinyl pyrrolidone (molecular weight 630,000), quaternary ammonium salt Type styrene copolymer (manufactured by Sanyo Chemical Industries, Chemistat 612)
0) 1.5 parts by weight, 0.25 parts by weight of dimethylol glyoxal monourein, which is a cellulose-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 were mixed. To prepare a layer forming coating solution,
The coating solution was applied on a subbing layer of a coating amount of urethane resin of 0.7 g / m ² using a wire bar, and heated at 130 ° C. for 5 minutes to form a coating layer having a thickness of 10 μm on one side. A water-soluble ink recording film was formed in the same manner as in Example 1 except that the film was provided. Table 3 shows the physical properties of the recording film thus obtained.

Example 5 In the same manner as in Example 1, a laminated film having an ink receiving layer and a dot shape adjusting agent-containing layer on one side of a polyethylene terephthalate film via an undercoat layer was produced.
Then, instead of providing a mat layer on the back surface of the ink receiving layer, 7 parts by weight of polyvinyl alcohol (polymerization degree 1700, saponification degree 88 mol%), 1 part by weight of polyvinylpyrrolidone (molecular weight 630,000), quaternary ammonium salt Type styrene copolymer (manufactured by Sanyo Chemical Industries, Chemistat 612)
0) 2 parts by weight, 0.2 part by weight of dimethylol glyoxal monourein, which is a cellulose-reactive crosslinking agent, 0.1 part by weight of ammonium chloride, 20 parts by weight of ethanol, and 69.
66 parts by weight and 0.04 parts by weight of synthetic silica (average particle size: 6 μm) were mixed to prepare a layer forming coating solution, and the coating solution was coated with a urethane resin with a wire bar at a coating amount of 0.7 g /
A water-soluble ink recording film was formed in the same manner as in Example 1 except that the composition was coated on the undercoat layer of m ² and heated at 130 ° C. for 5 minutes to provide a coating layer having a thickness of 10 μm on one side. . Table 3 shows the physical properties of the recording film thus obtained.

Comparative Example 1 A recording film was produced in exactly the same manner as in Example 1 except that the layer containing the dot shape adjusting agent in Example 1 was not provided. Table 3 shows the physical properties of this product.

Comparative Example 2 A recording film was produced in exactly the same manner as in Example 2, except that the dot shape adjusting agent-containing layer in Example 2 was not provided. Table 3 shows the physical properties of this product.

Comparative Example 3 A recording film was produced in exactly the same manner as in Example 1 except that the synthetic silica powder and calcium carbonate powder were not blended in the ink receiving layer of Example 1. Table 3 shows the physical properties of this product.

Comparative Example 4 A recording film was produced in exactly the same manner 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. Table 3 shows the physical properties of this product. The mixing ratios of the ink receiving layer forming coating liquids for Comparative Examples 1 to 4 are as shown in Table 2.

Comparative Examples 5 and 6 A water-soluble ink recording film was produced in the same manner as in Example 1 except that the composition of the ink receiving layer forming coating liquid in Example 1 was changed to the composition shown in Table 2. The physical properties were sought. Table 3 shows the results.

[0040]

[Table 1]

[0041]

[Table 2] (Note) 1) Polyvinylpyrrolidone: molecular weight 1280 000 2) Polyvinyl alcohol: Degree of polymerization 2000, saponification degree 88.0 mol% 3) Polyvinyl acetal: Acetalization degree 8.0 mol% 4) Synthetic silica powder: Average particle size 3. 5 μm 5) Calcium carbonate powder: average particle size 2.0 μm

[0042]

[Table 3]

From the results shown in Table 3, the recording film of the present invention (Examples 1 to 5) has a circular dot shape, a sharp outline, excellent image resolution, and good ink drying properties. It can be seen that there is no sticky surface.
Further, since the recording films of Examples 4 and 5 were provided with a transparent ink receiving layer on the back surface, it was possible to see what was recorded with the ink receiving layer on the front surface from the ink receiving layer on the back surface. This is an excellent effect that the images can be compared.

[Brief description of the drawings]

FIG. 1 is an enlarged sectional view of an example of a recording film of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base film 2 Undercoat layer 3 Ink receiving layer 4 Dot shape adjusting agent containing layer 5 Matt layer

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Yoshihiro Yasuhiko 4-11-2 Ginza, Chuo-ku, Tokyo Inside Somar Corporation (56) References JP-A-6-72015 (JP, A) JP-A Sho 63-115779 (JP, A) JP-A-58-177390 (JP, A) JP-A-2-30582 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/00

Claims (4)

(57) [Claims] Claims: At least one surface of a substrate film
(A) (a) polyvinylpyrrolidone, (b) polyvinyl alcohol or polyvinyl acetal or both, and (c) a particulate material as a main component, and the content ratio of the component (a) to the component (b) is 2 by weight. : 8 to 4: 6
And the content of the component (c) is the component (a) and the component (b)
An aqueous ink layer comprising: an ink-receiving layer in an amount of 30 to 100% by weight based on the total weight of the components; and (B) a dot shape adjusting agent-containing layer made of a quaternary ammonium salt type acrylic resin. Ink recording film. 2. The ink-receiving layer according to claim 1, wherein polyvinyl alcohol and / or polyvinyl acetal as the component (b) in the ink receiving layer is crosslinked by a reaction with a cellulose-reactive crosslinking agent or urea. Water-based ink recording film. 3. The resin according to claim 1, wherein the component (b) is a resin 100 to be crosslinked.
3. A water-based ink recording film according to claim 2, wherein the film is crosslinked by a reaction between 4 parts by weight of a cellulose-reactive crosslinking agent and 4 to 12 parts by weight of urea. 4. The aqueous ink recording film according to claim 1, wherein the fine particles of the component (C) in the ink receiving layer (A) have an average particle diameter of 0.5 to 15 μm.