JPH02301480A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a material to be recorded especially excellent in ink absorbability, color forming properties and adhesiveness and suitable for ink jet recording by forming a film containing an ionomer type aqueous urethane resin, a polyvinyl acetal resin, an acrylic resin and org. and/or inorg. fine particles on a non-porous support. CONSTITUTION:A material to be recorded is prepared by forming a film containing an ionomer type aqueous urethane resin, a polyvinyl acetal resin, an acrylic resin and org. and/or inorg. fine particles on a non-porous support. The ionomer type aqueous urethane resin to be used has a structure having a carboxyl group as an ion group and the proper MW thereof is 1000-10000. The polyvinyl acetal resin is prepared by reacting aldehyde with polyvinyl alcohol and acetifying the obtained reaction product. The pref. addition amount of the polyvinyl acetal resin is 0.1-40% by wt. based on the total dry film. As org. fine particles, a urea/formaldehyde resin is especially pref. from the aspect of ink absorbability.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a recording material, and more specifically, a film formed on a flat surface of a non-porous support to enable high-density recording with an inkjet printer. The present invention relates to recording materials for inkjet printers.

[Conventional technology]

Inkjet printers have become popular in recent years due to their excellent features such as clear recording, quietness, and easy color printing. Inkjet printers use ink that does not dry easily to prevent clogging of jet nozzles, and the components of this ink are generally binders, dyes, additives, etc. dissolved in water, polyhydric alcohol, polyhydric alcohol ether, pyrrolidone, etc. It is true.

For this reason, when printing and recording is performed using an inkjet printer, the recording sheet must have water absorption properties, and paper specially designed to provide sufficient ink absorption performance is usually used.

On the other hand, with the advent of color inkjet printers, various types of recording materials are being used for recording, such as being used as base paper for overhead projectors (OHP), interior decoration, etc.
There is an increasing demand for its use as an Efsteria product.

These recording materials are usually made of plastic films, glass plates, metal plates, ties, etc., but these plastic films, glass plates, metal plates, tiles, etc. are non-porous and hydrophobic and cannot be used with water-based inks for inkjet printers. Since it does not absorb at all, ink recorded directly on it does not dry easily, and if it is rubbed with fingers or overlapped, the recorded area becomes dirty, making it impractical. - In other words, in order to obtain high resolution and high quality recorded images, the recording material used in the inkjet recording method must: 1) absorb ink as quickly as possible; 2) absorb the ink as quickly as possible, and 2) prevent ink from overlapping. K. The ink deposited later does not flow into the ink dot deposited before. 3) The diameter of the ink dot does not become larger than necessary. The shape of the ink dot is close to a perfect circle, and the surrounding area is smooth. , S) The density of the ink dot is high and the area around the dot is not blurred, 6) The ink has excellent color development. )OH
Sheets for P etc. are required to meet performance requirements such as the adsorption layer being transparent and (1) having excellent water resistance.

In order to meet these demands, K on plastic film
Many methods have been proposed for coating polymers with constant W.

For example, JP-A-7-1409/, JP-A-69-/
i2g'1 No. 1, Japanese Unexamined Patent Publication No. 1983-. 7.2/79 issue, JP-A-60-/3.2.7g! r issue, JP-A-Sho t, o-1tis
tr'ys, JP-A-60-2-0, ? &θ No., JP-A-67-/93. No. 79, JP-A-62-Kol.79
The number is mentioned.

However, recent rapid advances in printer technology have led to markedly higher density and higher speed recording, and with this, even more advanced ink drying properties, color development properties, and coating film and support properties have been developed for recording materials. Although adhesion with -
Nothing that meets these requirements has yet been found.

[Problems to be solved by the invention] In view of these problems, the present invention fully satisfies the above-mentioned required properties, has particularly excellent ink absorbency, color development, and adhesiveness, and is suitable for surface image observation. To provide a recording material suitable for inkjet recording, which can form a transparent recording layer and can be used in optical equipment such as slides, OHPs, and contact printers that utilize transmitted light of recorded images. There is a particular thing.

[Means to solve the problem]

The gist of the present invention is a recording material formed by forming a film containing an ionomer type water-based urethane resin, a polyvinyl acetal resin, an acrylic resin, and organic and/or inorganic fine particles on a non-porous support.

The ionomer type aqueous urethane resin used in the present invention has a structure having a carboxyl group as an ionic group, and examples thereof include those produced by the following method.

That is, polyester-based urethane is produced by esterifying dicarboxylic acids and diols in the presence of an acid or alkali catalyst, and then reacting the OH groups remaining at the end of the molecule with aromatic isocyanate or aliphatic isocyanate. A resin or polyether and a compound represented by the following formula CH,OH R-C-COOH CH,0H (R is an alkyl group having 1 to 3 carbon atoms), especially dimethylolpropionic acid and an aromatic compound. Examples include polyether-based urethane resins produced by reacting incyanate or aliphatic incyanate.

Specifically, the dicarboxylic acids mentioned above include maleic acid,
Examples include aliphatic dicarboxylic acids such as adipic acid, and diols include ethylene glycol, /A-hexanediol, and diols having a carboxyl group in the molecule such as dimethylolpropionic acid. Also,
Examples of polyethers include polyethylene glycol and polypropylene glycol.

Examples of the aromatic isocyanate include diphenylmethane diisocyanate, xylene diisocyanate, 2II-
and co, 6-dolylene diisocyanate etc. are praised,
Examples of aliphatic incyanates include hexamethylene diisocyanate and inphorone diisocyanate.

Further, the appropriate molecular weight of such an ionomer type aqueous urethane resin is /000-/0.000.

The ionomer type aqueous urethane resin as mentioned above can be produced by a known method, for example, as described in Japanese Patent Application Laid-Open No. 1983-1921. /-3
It can be produced by the method described in No. A3/'1, JP-A-1.2-2701,13, JP-A-62-274114, and the like.

In addition, these are, for example, H from Dainippon Ink & Chemicals ■.
5uperfl from ydran or Daiichi Kogyo Seiyaku■
There are products sold under the trade name of "ex", and products easily available on the market may be used.

The amount added is preferably 10 to 60% based on the total weight of the dry film. In addition, as the acrylic resin used in the present invention, monomers of (meth)acrylic acid salts such as methacrylic acid, ammonium (meth)acrylate, and amine salts of (meth)acrylic acid are used by ordinary polymerization methods. In addition to homopolymerization or copolymerization, these monomers can be used with alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and hydroxyethyl acrylate. Monomers such as styrene,
Maleic acid, methylol acrylamide, etc. are appropriately copolymerized using normal polymerization methods, and the molecular weight is! ;,
000-200.000 and is soluble in water or uniformly dispersed in water.

In particular, those that are uniformly dispersed in water are preferred. Further, this acrylic resin is used in the form of an aqueous solution or an aqueous emulsion.

Addition 1 is preferably 7 to 20% based on the total weight of the dry film.

The above-mentioned acrylic resins are sold, for example, under the trade names of Voncoat by Dainippon Ink and Chemicals, or JSR Acrylic Emulsion by Japan Synthetic Rubber, and those readily available on the market may be used. .

Further, polyvinyl acetal resin is produced by reacting polyvinyl alcohol with an aldehyde to acetalize it. Saponification and acetalization may be performed simultaneously using polyvinyl acetate as a starting material. Conventionally known methods are employed for acetalization, such as dissolution method, precipitation method, and homogeneous method.

The polyvinyl alcohol used as a raw material for this resin is not particularly limited, and usually has a polymerization degree of 300.
~/1.100. Preferably, those having a molecular weight of 200 to ttsoo are used, and a high degree of polymerization is preferable because the ink fixability and water resistance become good. In addition, the degree of saponification of polyvinyl alcohol is not particularly limited, and usually, go,
It is preferable that the degree of saponification is set to θ˜99.5 mol % and the degree of saponification is low because the fixing properties of the ink will be good.

As an aldehyde that condenses with polyvinyl alcohol,
For example, aliphatic aldehydes such as formaldehyde, acetaldehyde, butyraldehyde, hexylaldehyde, octylaldehyde, and decylaldehyde, benzaldehyde, comethylbenzaldehyde, 3-methylbenzaldehyde, dermethylbenzaldehyde, other alkyl-substituted benzaldehydes, chlorbenzaldehyde, and other norogens. Aromatic aldehydes such as substituted benzaldehydes, phenylacetaldehyde, β-phenylpropionaldehyde, and other phenyl-substituted alkyl aldehydes, and aromatic aldehydes with substituents such as hydroxy groups, alkoxy groups, amino groups, and cyan groups on the aromatic ring. Examples include aldehydes. Further, aldehydes having a condensed aromatic ring such as nathaldehyde, anthra, and cenaldehyde may also be used.

Aromatic aldehydes are particularly preferably used because they provide resins with good ink fixability, water resistance, and transparency.

The degree of acetalization of the polyvinyl acetal used in the present invention is generally in the range of 2 to 0 mol%, preferably 3 to 30 mol%, and more preferably 5 to 20 mol%. If the degree of acetalization is too low, the ink will have good fixing properties, but the water resistance will be poor; if the degree of acetalization is too high, the water resistance will be good, but the ink will have poor fixing properties. .

The amount of such polyvinyl acetal resin added is preferably o,/-#0% based on the total weight of the dry film. The above-mentioned polyvinyl acetal resin is sold under the trade name of S-LEC by Tanemizu Kagaku Kogyo ■, and those readily available on the market may be used.

Examples of the organic fine particles include fine particles of polystyrene, polyethylene, polyethylene urea, urea formaldehyde resin, etc., and urea formaldehyde resin is particularly preferred from the viewpoint of ink absorbability.

These organic fine particles include those having a particle size of 0.1 to 708 m, preferably 0.3 to 708 m.

Examples of inorganic fine particles include colloidal silica, fine particles of dioxide/titanium oxide, etc. When forming a transparent recording material, colloidal silica fine particles are used, and when forming an opaque recording material, titanium dioxide fine particles are used. Particularly preferred. Further, the colloidal silica fine particles have a particle size of 10 to 1100n, preferably 20 to 1,000n! ; Titanium dioxide fine particles having a particle size in the range of 0.1 to 708 m, preferably 0.3 to 70 m are used. It is desirable that these fine particles be used in an amount of 70 to 70 wt% based on the total weight of the film.

In addition, the polycarboxylate type surfactant and the fluorine-based nonionic type surfactant are each added in an amount of 0.2 to 1/2% of the total weight of the film.
It is also desirable to use J wt %~ゝO As the non-porous support used in the present invention, a film,
A flat plate such as a sheet or plate is used, for example, a film or plate made of plastic such as polyester, diacetate, triacetate, acrylic polymer, cellonone, celluloid, polyvinyl chloride, polycarbonate, polyimide, polyamide, or glass. board, tile,
A metal plate or the like can be used. The thickness of the support used is not particularly limited, and any thickness can be used depending on the purpose.

The coating solvent used to form a film on the support mainly includes water, and may further contain lower alcohols such as isopropyl alcohol, and lower alkyl ketones such as methyl ethyl ketone.

The dry thickness of the film formed on the support as an ink absorbing layer is preferably -700 .mu.m, particularly about 30 .mu.m. If the film is too thin, the ink will dry slowly, making it impractical, while if it is too thick, the price per sheet will increase and coating will become difficult, both of which are undesirable.

When you are busy forming a film on the support, you can apply the coating solution directly as it is, but if the adhesion between the support and the formed film is insufficient, apply the coating solution to the support before forming the film. Preferably, a primer is applied on the body.

As a method for forming a film on the support, conventional coating methods such as gravure coating, barcode coating, reverse roll coating, and knife coating can be used.

In the present invention, the coating may be formed only on one side of the support, or may be formed on both sides.

〔Example〕

Hereinafter, the recording material of the present invention will be explained in more detail using Examples, but the following Examples are not intended to limit the present invention in any way.

Example 1 A 200 μm thick polyvinyl chloride film was used as the support, and H3/dran 1- was used as the ink absorption layer.
1w-J/0 (product name: manufactured by Nippon Ink Chemical Industry ■) 1 parts by weight (resin solid content 30%), S-LEC W-, 10/ (product name: Tanezu Kagaku ■) 5 parts by weight (resin Solid content 23%), Voncoat V (Product name Futari Nippon Ink Chemical Industry ■g) J,! ; parts by weight (resin solid content 30%), Demol EP (polycarboxylate type surfactant, trade name: manufactured by Kao ■) 0.7 parts by weight, Fluora
d Composition consisting of 0.7 parts by weight of FC-/70C (7-based nonionic surfactant, trade name: manufactured by 3M) and 72 parts by weight of urea formaldehyde resin (particle size 0.7 to 3 μm) The dry film thickness is 70μ by bar coater method.
Coat it on the film so that it becomes g0℃, 70
The recording material of the present invention was obtained by drying under the conditions of 10 minutes.

Inkjet recording was performed on the obtained recording material using an inkjet printer IQ-730 (manufactured by Sharp ■) that discharges ink using a piezo vibrator to obtain a recorded image.

The recorded images obtained as described above were tested for the following λ items to evaluate the recording suitability of the recording material.

(1) After quick-drying inkjet recording, leave the recorded matter at room temperature for 60 minutes.
The ink did not stick to the finger even if it melted on the recorded area after a few seconds, and the ink was sufficiently dry.

(2) Image quality The resulting image was a high-resolution image with no ink spreading or bleeding.

Example: A polyethylene terephthalate film with a thickness of ioum was used as the support, and Hydra was used as the ink absorbing layer.
n AP-,,70 (product name: Futari Nippon Ink Kagaku Kogyo ■) 5 parts by weight (resin solid content 30%), S-LEC KX
-/(Product name: Sekisui Chemical Co., Ltd.) IIs parts by weight (resin solids g%), Voncoat 39 g j (Product name: Futari Nippon Ink Chemical Co., Ltd.) Parts by weight (resin solids 3)
0%) and 46 parts by weight of colloidal silica (particle size 10~/
A composition consisting of 0 nm) was applied onto the film by a bar coater method so that the dry film thickness was µm.

After drying, a recorded image was formed and evaluated in the same manner as in Example 1. As a result, good results were obtained regarding items (1) and (2) above.

In addition, as a result of projecting the recorded image onto a screen using 0) (P and visually observing it, it was determined that the non-recorded area was bright, the OD (optical density) of the recorded image was high, and the projected image was clear and easy to see with high contrast. was gotten.

〔Effect of the invention〕

The recording material of the present invention is a recording material for performing high-density recording on a support by an inkjet printer, and is excellent in quick-drying ink after recording, printing quality, etc.

In addition, the recording material of the present invention can be used not only for surface observation of recorded images, but also for use in optical equipment such as slides, OHPs, and contact printers that utilize the transmitted light of recorded images. It also has particularly excellent translucency and is useful.

Claims (1)

[Claims] (1) A recording material characterized by forming a film containing an ionomer-type water-based urethane resin, a polyvinyl acetal resin, an acrylic resin, and organic and/or inorganic fine particles on a non-porous support.