JPH09110939A - Highly water-resistant polymer for recording material and recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording material which is excellent in ink absorption and water resistance, is usable not only for uses in which surface images are viewed but for uses in optical apparatuses in which light transmitted through recorded images are utilized, such as a slide projector, an OHP, and a tight- contact printer, and is suitable for ink-jet recording. SOLUTION: This polymer comprises a copolymer obtained from 20-60wt.% hydrophobic vinyl monomer having a solubility at 20 deg.C in 100g water of 10g or lower, 1-30wt.% cationic hydrophilic vinyl monomer, and 10-79wt.% nonionic hydrophilic monomer. The recording material comprises a nonporous substrate and a coating film of this polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material, and more particularly to an ink jet printer having a non-porous support on which a film capable of high density recording in an ink jet printer is formed. And a polymer for recording material having excellent water resistance and recording material.

[0002]

2. Description of the Related Art Inkjet printers have recently begun to be widely used due to their excellent features such as clarity of recording, quietness of sound, and easy colorization. Ink jet printers use ink that is difficult to dry to prevent clogging of jet nozzles.The components of this ink are those in which binders, dyes, additives, etc. are dissolved in water, polyhydric alcohol, polyhydric alcohol ether, pyrrolidone, etc. General. For this reason, when printing and recording with an inkjet printer, the recording sheet must have water absorbency, and normally paper specially designed to give the ability to sufficiently absorb ink is used.

On the other hand, recording is performed on various recording materials with the use of color ink jet printers and used as a base paper for an overhead projector (OHP).
The demand for use as interior and exterior goods is increasing. These recording materials are usually composed of plastic films, glass plates, metal plates, tiles, etc., but the above materials are non-porous and hydrophobic and do not absorb any aqueous ink for inkjet printers, Directly recorded ink does not dry easily, and when rubbed or overlapped with a finger, the recorded portion becomes dirty and is not practical.

That is, in order to obtain a high-resolution and high-quality recording image as a recording material used in an ink-jet recording method, it is necessary that the ink absorption speed is high and the diameter of the ink dots does not become larger than necessary. It is required that the required performance is satisfied.

Further, the recording material used in the ink jet recording system has a water resistance such that the recording material itself does not deteriorate due to sweat or moisture in the air during use, or does not deteriorate due to accidental immersion in water, and does not damage the printed portion. It is necessary to satisfy required performance such as high performance.

[0006] With respect to the improvement of ink absorbency, for example,
JP-A-60-145879, JP-A-61-01048
No. 3, JP-A-61-203788 and the like disclose recording materials of the type in which a water-soluble polymeric substance film layer is provided on a support such as a plastic film, sheet or glass plate. Poor water resistance, the film easily dissolves with sweat, etc., and the stickiness due to moisture in the air is large, making practical use difficult.

Regarding the improvement of water resistance, Japanese Patent Laid-Open No.
No. 1-012388, JP-A No. 61-237682, JP-B No. 3-029596 and the like, a two-layer structure in which an ink receiving layer is first provided on a support and an ink permeating layer having water resistance is provided on the surface of the ink receiving layer. Although a recording material having a structure is disclosed, there are problems in productivity and cost.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to satisfy the above-mentioned various requirements, and in particular, has excellent ink absorbency and water resistance. An object of the present invention is to provide a recording material having excellent water resistance, which is suitable for inkjet recording and can be used in optical equipment such as a slide, an OHP, and a contact printer.

[0009]

The inventors of the present invention have conducted various studies in order to solve the above problems and achieve the object, and as a result, a copolymer having a specific composition has excellent ink absorbability. Moreover, they have found that they are effective in providing a recording material having excellent water resistance, and have reached the present invention.

That is, according to the present invention, a) 20 to 60% by weight of a hydrophobic vinyl monomer having a solubility in 100 g of water at 20 ° C. of 10 g or less, and b) 1 to 30% by weight of a cationic hydrophilic vinyl monomer. And c) a polymer for recording material having excellent water resistance, comprising a copolymer of 10 to 80% by weight of a nonionic hydrophilic vinyl monomer, and a non-porous support and the support. A recording material having a coating layer formed on at least one surface of a body, wherein the coating layer is made of the above polymer, and having excellent water resistance.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer of the present invention has the above a),
It is composed of vinyl monomers b) and c). The specifics of these monomers are shown below.

Monomer a) is 100 g of water at 20 ° C.
A hydrophobic monomer having a solubility in water of 10 g or less, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic Butyl acid, (meth)
Hexyl acrylate, octyl (meth) acrylate,
(Meth) acrylic acid esters such as lauryl (meth) acrylate, glucidyl (meth) acrylate, allyl (meth) acrylate, and allyloxyethyl (meth) acrylate; N-butoxymethylacrylamide, N-benzyloxymethylacrylamide , Amide-based monomers such as Nt-butylacrylamide; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-chlorostyrene; polyolefin-based compounds such as butadiene, isoprene and chloroprene; (meth) Vinyl cyanide compounds such as acrylonitrile; methyl isopropenyl ketone, vinyl acetate, vinyl propionate, vinyl vivalate and the like. Of these, methyl methacrylate is particularly preferable.

The monomer b) is a monomer of a cationic hydrophilic vinyl, and has a primary to tertiary amino group or a salt thereof or a quaternary ammonium salt and an ethylenically unsaturated divinyl group in the molecule. It is represented by a compound having a heavy bond, and examples thereof include propylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth). ) Acrylate, diethylaminopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyldimethylamine, dimethylaminomethyl (meth) acrylamide, diethylaminomethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethyl Monomers containing primary to tertiary amino groups such as minopropyl (meth) acrylamide, salts of these inorganic or organic acids such as hydrochloric acid, sulfuric acid, acetic acid or lactic acid, or methyl chloride, dimethyl sulfate, Examples thereof include monomers containing a quaternary ammonium salt obtained by reaction with a quaternizing agent such as diethyl sulfate or epichlorohydrin.

The monomer c) is a nonionic hydrophilic monomer, for example, N-methylol acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth). Acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-ethylacrylamide, N-methoxymethyl (meth) acrylamide,
N-substituted or N-unsubstituted (meth) acrylamides such as N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide; N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl Acetamide, N-vinyl imidazoline,
N-vinyl amides such as N-vinyl pyrrolidone and N-vinyl-ε-caprolactam; methoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol # 230 (meth) acrylate, methoxy polyethylene glycol # 400 (meth) acrylate, methoxy polyethylene glycol # 1000 (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol # 230 (meth) acrylate, phenoxy polyethylene glycol # 400 (meth) acrylate, phenoxy polyethylene glycol # 1000 (meth)
Examples thereof include monomers having an ethylene glycol unit structure such as acrylate. Among these, in particular, since it is possible to easily crosslink a film made of a copolymer coated on a support described below, ink absorbency and water resistance,
It is desirable to contain N-methylol acrylamide as an essential component.

The vinyl monomers a), b) and c) may be used alone or in each vinyl monomer.
It can be used in combination of more than one species.

The polymer of the present invention can be obtained by copolymerizing the above vinyl monomers a), b) and c). The proportions of these three components at the time of copolymerization can be changed depending on the performance desired for the recording material of the present invention, but in view of ink absorbency and water resistance, a) 20.
-60% by weight, b) 1-30% by weight, c) 10-80% by weight.

When the proportion of the vinyl monomer a) is less than 20% by weight, the film made of the copolymer is dissolved or swelled, and sufficient water resistance cannot be obtained. On the other hand, when it exceeds 60% by weight, the water resistance is improved but the ink absorbency is lowered. Therefore, the proportion of vinyl monomer a) is 20
-60% by weight, preferably 30-50% by weight.

When the proportion of the vinyl monomer b) is less than 1% by weight, the ink absorbency is lowered, and the fixability of the dye contained in the ink is also lowered. On the other hand, if it exceeds 30% by weight, the film made of the copolymer is dissolved or swelled, and sufficient water resistance cannot be obtained. Therefore,
The proportion of vinyl monomer b) is 1 to 30% by weight, preferably 5 to 20% by weight.

When the proportion of the vinyl monomer c) is less than 10% by weight, the ink absorbency is lowered. On the other hand, if it exceeds 80% by weight, the film made of the copolymer is dissolved or swelled, and sufficient water resistance cannot be obtained. Therefore,
The proportion of vinyl monomer c) is 10-80% by weight, preferably 30-65% by weight.

The copolymerization for obtaining the polymer of the present invention can be carried out by a known radical polymerization method such as a solution polymerization method, an emulsion polymerization method or a suspension polymerization method. Considering ease of handling after polymerization, solution polymerization is preferred.

Water and an organic solvent can be used as the solvent used in the solution polymerization, and as the organic solvent,
Examples thereof include alcohols, ethylene glycol, and mono- or dialkyl ethers thereof. The total amount of the vinyl monomer at the start of the polymerization is preferably from 10 to 80% by weight based on the total amount of the polymerization solution.

As the polymerization initiator, a redox type or azo type radical polymerization initiator can be used. Redox initiators, for example, oxidizing agents such as ammonium persulfate, potassium persulfate, aqueous hydrogen peroxide, cumene hydroperoxide, and thioglycolic acid, L-ascorbic acid, dimethylaminopropionitrile, sodium bisulfite, Examples thereof include a combination with a reducing agent such as β-mercaptoethanol and a divalent iron salt. As the azo-based initiator, azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile), 4, 4'-azobis (4-cyanopentanoic acid) and the like can be mentioned. Also,
A redox type polymerization initiator and an azo type polymerization initiator may be used in combination.

As the polymerization temperature, the initial temperature is 10 to 40.
The polymerization can be carried out in an adiabatic system at about ° C, or under a constant temperature condition of about 30 to 100 ° C while controlling the temperature from outside the system. The polymerization time varies depending on the type and concentration of the vinyl monomer, the polymerization temperature and the like, but is about 10 minutes to 20 hours.

Examples of the non-porous support in the recording material of the present invention include polyester, polyacrylonitrile, polyvinyl chloride, polycarbonate, polyamide,
Polyimide, diacetate, triacetate, cellophane, non-porous film made of semi-synthetic resin material such as celluloid, sheet or plate, glass plate,
Examples include a metal plate and a tile. The thickness of the non-porous support is not particularly limited and can be appropriately selected depending on the application.

The recording material of the present invention can be obtained by forming a film of the polymer on at least one surface of these non-porous supports.

The film is formed by, for example, a gravure coating method,
It can be carried out by coating the support with a polymer solution by a known method such as a reverse coating method, a kiss coating method, a die coating method, a bar coating method and then drying.

In the recording material of the present invention, when a polymer containing N-methylol acrylamide as an essential component of the vinyl monomer c) is used, a crosslinking reaction occurs during the drying step and a coating layer having a crosslinked structure is formed. Can be easily formed, and the water resistance can be further improved.
The amount of N-methylolacrylamide varies depending on the drying conditions such as heating temperature and heating time, but it may be 1% by weight or more based on all vinyl monomers.

In order to accelerate the crosslinking reaction with N-methylolacrylamide, a catalyst may be added to the copolymer solution and then coated on the support to form a film layer.
Examples of the catalyst for the cross-linking reaction with N-methylol acrylamide include inorganic or organic acids such as hydrochloric acid, sulfuric acid and p-toluenesulfonic acid, or salts such as ammonium chloride.

In the present invention, various fillers such as silica, clay, talc, diatomaceous earth, zeolite, calcium carbonate, calcium sulfate, barium sulfate, are added to the recording material in order to enhance the recording characteristics of the recording material. Fillers such as aluminum silicate, alumina, zinc oxide, and sathion white can be dispersed.

Further, within a range not impairing the characteristics of the present invention,
Known additives, for example, an antifoaming agent, a coating improver, a thickener, an antistatic agent, an antioxidant, an ultraviolet absorber, and a dye may be contained.

In addition, various water-soluble polymers such as starch, pectin, casein, dextrin, water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, etc. may be contained within the range not impairing the characteristics of the present invention. Good.

[0032]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified,
"%" And "parts" are based on weight. The methods for measuring various physical properties in the examples are shown below.

(1) Inkjet recording method Color bubble jet printer BJ manufactured by Canon Inc.
Monochromatic and multicolor inkjet recording was performed by ejecting four inkjet inks of cyan, magenta, yellow and black at C-400J, and the recording characteristics were evaluated.

(2) Ink Absorption Rate After ink jet recording, the print on the surface of the recording material was rubbed with a finger at regular intervals, and the time until the printed portion remained unchanged was measured. The shorter the time, the faster the ink absorption rate. …: Good (within 30 seconds) △: slightly poor (1-2 minutes) ×: no ink absorption

(3) Water resistance The appearance when water was applied to the printed portion on the surface of the recording material after ink jet recording was observed. …: Good (no change)…: slightly inferior (printed part is blurred or missing color when rubbed with a finger) ×: poor (dissolution, swelling)

(4) Print quality Cyan, magenta, yellow and black single color, red,
The color development of characters printed in multiple colors of green and blue and the bleeding of each dot were visually observed or observed with a loupe, and evaluated. …: Good (clear, uniform dots) や: slightly poor ×: poor (dot flow, repelling, bleeding, etc.)

Example 1 40 parts of methyl methacrylate and 10 parts of methacryloyloxyethyl trimethyl ammonium chloride were placed in a reaction vessel.
Part, N-methylol acrylamide 50 parts, 2,2'-
Mixed solvent 29 of 2 parts of azobis (2,4-dimethylvaleronitrile) and isopropanol / water = 3/2 (weight ratio)
8 parts were charged and stirred to prepare a reaction solution. Then
After purging the reaction vessel with nitrogen, the reaction vessel was heated at 65 ° C. for 4 hours to carry out polymerization to obtain a solution of a copolymer of 25% by weight. After adding p-toluenesulfonic acid to this solution in an amount of 0.15% by weight with respect to the copolymer, it was applied to a polyester film having a thickness of 100 μm so that the coating amount after drying would be 20 g / m ^2, and 120 The sheet of the recording material of the present invention was obtained by drying at 5 ° C. for 5 minutes. The ink absorption rate, water resistance, and print quality of this recording material sheet are also shown in Table 1.

Examples 2 to 5 and Comparative Examples 1 to 6 The same procedure as in Example 1 was carried out except that the components shown in Table 1 were charged in a reaction vessel to obtain a recording material sheet. The ink absorption rate, water resistance, and print quality of this recording material sheet are also shown in Table 1.

[0039]

[Table 1]

[0040]

The recording material of the present invention can perform high density recording by an ink jet printer and has both good water resistance and ink absorbability which cannot be obtained at the same time in conventional ones. An excellent recording material can be provided.

[Procedure amendment]

[Submission date] October 18, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

That is, according to the present invention, a) 20 to 60% by weight of a hydrophobic vinyl monomer having a solubility in 100 g of water at 20 ° C. of 10 g or less, and b) 1 to 30% by weight of a cationic hydrophilic vinyl monomer. And c) a polymer for recording material having excellent water resistance, which comprises a copolymer of nonionic hydrophilic vinyl monomer 10 to 79 % by weight, and a non-porous support and the support. A recording material having a coating layer formed on at least one surface of a body, wherein the coating layer is made of the above polymer, and having excellent water resistance.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

The polymer of the present invention can be obtained by copolymerizing the above vinyl monomers a), b) and c). The proportions of these three components at the time of copolymerization can be changed depending on the performance desired for the recording material of the present invention, but in view of ink absorbency and water resistance, a) 20.
60 wt%, b) 1 to 30 wt%, c) in the range of 10 to 79 wt%.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

When the proportion of the vinyl monomer c) is less than 10% by weight, the ink absorbency is lowered. On the other hand, if it exceeds 79 % by weight, the film made of the copolymer is dissolved or swelled, and sufficient water resistance cannot be obtained. Therefore,
The proportion of vinyl monomer c) is 10 to 79 % by weight, preferably 30 to 65% by weight.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location C08J 7/04 C08J 7/04 H (72) Inventor Takayuki Iseki 1-5 Marunouchi, Chiyoda-ku, Tokyo No. 1 Nitto Chemical Industry Co., Ltd.

Claims (4)

[Claims] 1. A) 20 to 60% by weight of a hydrophobic vinyl monomer having a solubility in 100 g of water at 20 ° C. of 10 g or less, and b) 1 to 30% by weight of a cationic hydrophilic vinyl monomer.
And c) a polymer for recording material having excellent water resistance, which comprises a copolymer of 10 to 80% by weight of a nonionic hydrophilic vinyl monomer. 2. The polymer according to claim 1, wherein the hydrophobic vinyl monomer a) having a solubility in 100 g of water at 20 ° C. of 10 g or less is methyl methacrylate. 3. The nonionic hydrophilic vinyl monomer c)
The polymer for recording material having excellent water resistance according to claim 1, which contains N-methylolacrylamide as an essential component. 4. A recording material comprising a non-porous support and a coating layer formed on at least one surface of the support, wherein the coating layer comprises the polymer according to claim 1. A recording material with excellent water resistance.