JPS58134784A - Recording material - Google Patents

Abstract

PURPOSE:To provide a recording material capable of speedily absorbing an ink and producing small-diameter ink dots in a high dot density, by a method wherein a coated layer consisting of a polymer comprising a hydrophilic structural part and a hydrophobic structural part is provided on a base. CONSTITUTION:A polymer which comprises 2-40wt%, preferably 25-40wt% of a hydrophilic structural part introduced by an alpha,beta-unsaturated monomer and a hydrophobic structural part introduced by styrene or the like and has a molecular weight of not less than 2,000 is dissolved or dispersed in a solvent to prepare a coating material. The coating material is applied onto the base 1 consisting of a liquid-absorptive porous material such as a paper in an amount of 1-10g/ m<2>, and is dried to produce the coated layer 2, thereby obtaining the desired recording material.

Description

[Detailed description of the invention] This book Ii@ is written in the character 中值等Oki IIk by Kiku 1Ik11E.
Concerning the layered recording material (hereinafter also referred to as paper) Conventionally, recording has been widely performed using recording liquid, ink, etc. ing. Also, recently, an inkjet recording system has appeared, and is used in ζζ.

Incidentally, Jin's inkjet recording method uses various ink ejection methods (for example, an electrostatic machine side method, a method using a piezoelectric element to apply mechanical vibration or displacement to the interlayer,
A method is known in which O is heated to loosen the water and O pressure is used.
), and records are made by attaching the O-S or the entire O-S to the O-deployed material such as the face. (It is necessary that the ink does not bleed onto the surface of the recording paper and a single character is not erased), and that the ink is dried as much as possible after recording so as not to accidentally contaminate the paper drawing. and,
It is desirable that the pigment in the ink is fixed on the paper and does not fade.

In addition, in the above inkjet recording method, 1) the recording liquid (ink) is obstructed from being absorbed into OIeIIk paper; 2) when performing color recording in %K, multicolor or 7, the ink・
Overlap of dots - Even if there is fi, do not let the ink that adheres later adhere to the front and laminate the dots. - The ink droplets will spread on the parent image for deployment, and the diameter of the interdots will be smaller than the diameter on the recording paper. ■The shape of the ink dot must be close to a perfect circle, and the area around it must be clean. (The ink dot must not make a loud sound or the area around the dot must be blurred.) ■The color of the recording paper must be white. (ink dots and O-con) 2 strokes are large, ■The ink color does not change depending on the type of recording paper, ■There is little scattering of ink drops around the ink dots, ■Dimension fluctuations of the recording paper (if there is a problem, Lt) It is necessary to satisfy the requirements of OIIm, such as having a small amount of SO (SO) before and after recording. However, conventionally, these are 01! *tllJj-5″
``tb''... It is generally understood that 11 paper per unit is largely due to its flexibility, but in terms of plain paper and processed paper, 111iIL, which meets the demands of Unegami 0111E, is widely accepted. The recording paper is still missing. For example,
The treated paper for inkjet recording, which is different from No. 4340, absorbs ink quickly, but the diameter of the ink dots is very steep, so it is easy to bleed, the periphery of the dots is easy to blur, and the paper after recording is It has the disadvantage that the size of the paper changes significantly. Therefore, the main object of the present invention is to satisfy the above-mentioned technical field that the prior art cannot solve and satisfy the following. In particular, in the present invention, a recording material (recording paper) with a performance that satisfies almost all of the MII* on the ridges in round writing using the Ryo-Autumn Interchanger based on the inkjet deployment method or the inkjet deployment method is used. is intended to provide.

Therefore, the recording material of the present invention which is intended to achieve such an objective requires that a coating layer be provided on the substrate using a coating material containing a polymer that eliminates both the wood-philic structure portion and the hydrophobic structure portion. This is a characteristic feature.

Hereinafter, the present invention will be explained in detail with reference to illustrated examples and examples.

First, the configuration of the present invention will be outlined using the schematic diagram shown in Figure 1.

In the figure, 14 is a substrate, and o2, which is made of a porous material such as paper, cloth, or a sticky film (sheet), is a covering layer that receives ink. This coating layer 2 is basically composed of a film-forming resin paint, but the paint contains a polymer having both a hydrophilic structural part and a hydrophobic structural part as a main component. Ru. Such polymers are mainly polymers of heptamers (monomers) having addition-polymerizable vinyl groups, and wood-loving structural moieties such as carboxylic acid groups, sulfonic acid groups, and sulfuric acid ester groups are Quantified amounts of acrylic, methacrylic, crotonic, and itaconic acids.

α, β-unsaturated heptanomers such as itaconic acid monoester, maleic acid 1ff, leic acid monoester, hexamaric acid, hexamaric acid monoester, vinyl sulfonic acid, sulfoethyl methacrylate, sulfopropyl methacrylate, and sulfonated vinylnaphthalene tmn introduced into the polymer structure.

On the other hand, the seven units that introduce hydrophobic structural moieties include styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, 4-units, and Uα, β-ethylenically unsaturated carbon, ll! Most preferred are C1-C5aO aliphatic alcohol esters.

In addition to the above monomer unit, for example, acrylonitrile, vinylidene chloride, and α,β-ethylenically unmalted carboxylic acid esters other than ridges.

Vinyl acetate, vinyl chloride, acrylamide, methacrylamide, Hitomi 4-diethyl methacrylate, hydroxyglobil methacrylate, glycidyl methacrylate,
N-methylol acrylamide, N-butyl dimethylacrylamide, etc. can be used.

Incidentally, in the present invention, it is necessary to form a salt of the polymer in order to solubilize the polymer in the paint solvent or to disperse it in a colloidal form. The partner that forms the salt with the above 1 coalescence is Na, which is an alkali metal,
Besides, things.

Di-related compounds include aliphatic compounds such as tri (methyl thymine), mono, di, or tri (ethyl thymine).

Nanano, Ji's relative is Tory (Ethanol Rua Kenn).

Seven no, Jiwei is Tory (Prono (Noramine)).

Alcohols such as methylethanolamine, dimethylethanol7, and morpholine.

N-Methylmorpholine, etc.O And in the above polymer, it is a hydrophilic structural moiety! The ratio of one unit is particularly important.

In other words, carboxyl groups, sulfonic acid groups, sulfate ester groups, etc. O! 1 unit oll that becomes the aqueous structure part
When the weight ratio exceeds approximately 40% by weight, the so-called sizing effect on the substrate 1 is reduced, and the amount of the recording liquid (ink) attached to the coating layer 2 becomes too large. On the other hand, when the weight ratio of the core is less than 2% by weight, the bonding force between the coating layer 2 and the substrate 1 decreases, resulting in easy peeling. The ratio of the wooden structural parts is more preferably about 25 to 25% by weight.
Appears to be 40-.

In addition, if the molecular weight of this polymer is too low, it will lead to deterioration in performance, so it is generally desirable to use a 031 polymer with a molecular weight of about 2000 or more. can be manufactured. For example, a polymer with a desired molecular weight is produced by mixing the essential components in a predetermined ratio and using a method such as the melt-casing heavy metal method, emulsion polymerization method, or II turbidity polymerization method (using a polymerization regulator if necessary). threaten In addition, polymers containing acid anhydrides, esters, nitrile groups, hydroxyl groups, etc. are first prepared, and these groups are then subsequently polymerized by hydrolysis, saponification, sulfuric acid esterification, or sulfonation. A method of generating carboxyl groups or the like during coalescence can also be adopted.

In addition, the timing of adding amine salt may be any time, for example, a method of polymerizing using ann salt of the above-mentioned carboxylic acid, a method of adding an amine etc. after polymerization or after the above-mentioned hydrolysis reaction, etc. , any method can be adopted.

In the present invention, a paint for a model is prepared by dissolving or dispersing these polymers alone or in combination in a paint solvent. At this time, if the polymer has poor IIII-forming ability, other binding trees rtrt may be used in combination.

Such resins include ice-melting or organic solvent-soluble o
*rrito can be used. For example, water-soluble resins include polyvinyl alcohol, starch, casein, gum arabic, -1&J=gelatin, polyacrylamide, carboxymethyl luulose, polyacrylic iron powder, sodium alginate, etc., and organic solvent-soluble resins include: These include polyvinyl butyl, polyvinyl chloride, polyvinyl acetate, polyacrylonitrile, polymethyl methacrylate, polyvinyl methacrylate, menon 11F, polyamide wti, phenolic resin, polyurethane resin, alkyd resin, and the like.

Further, as a solvent for mHing the paint, water alone or a mixture of water and a water-illuminative organic solvent may be used. Examples of water-soluble organic solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, etc. Al: ff-le, 1lB
6-propyl alcohol, n-butyl alcohol, 5e
e-butyl alcohol, t@rt-butyl alcohol,
1so-1 thyl alcohol-□ alcohol.

Alcohols such as furfuryl alcohol and tetrahydro-7-79 alcohol; ketone or keto alcohols such as acetone, methyl ethyl ketone, and sialic alcohol; ethers such as buto-2-hydrofuran and dioxane;
Esters such as ethylene carbonate and propylene carbonate; N,N'-dimethylformamide, N.

Examples of such solvents include nitrogen-containing solvents such as dimethylhydraudide, N-methyl-2-pyrrolidone, and jetanolamine. Generally, the above-mentioned paint is applied by Ig/Wr to 10g/Wt by a roll coating method, a rotor coating method, a spray coating method, or, practically, from 2g/Wr to sg/Wt. After such a coating layer is provided, the coating layer is dried in a shielded manner as much as possible.

When the ink adheres to the coating layer 2 explained above,
A pigment (for example, a dye) in the ink chemically or physically bonds with the polymer constituting the coating layer 2,
It is selectively adsorbed and captured.

Here, more detailed examples will be explained, and this percentage will also be explained.
Illustrating the effect of light.

In addition, prior to the Examples, examples of synthesis of a monomer, which is a main component according to the present invention, and examples of commercially available polymers are illustrated below. (・
...The number of copies in the synthetic example is the number of parts by weight. ) Lip synthesis example 1. 5 liters of water in a four-necked third-generation paraple flask with a stirrer
0 parts of Inglobil alcohol, 301'1 parts of dodecylbenzenesulfonic acid, 0.5 parts of IJ cum, ammonium persulfate, and ssta were combined and heated to 60°C. Separately, a mixed solution of 5 liters of styrene, 5 liters of acrylic [98] and 5@ of butyl acrylate was placed in a separating funnel and gradually added dropwise over 60 minutes. After dropping, raise the temperature to 80°C and further 2
Polymerization is carried out by stirring for 9 hours.

The molecular weight of the dead polymer obtained was approximately 50,000.

Example λ 8 methyl methacrylate in a flask similar to Example 1.
1 part, 5 parts of styrene, 154 g of itaconic acid, 1 part of penzoyl peroxide, 1 part of lacrylic mercabutane, 2 parts of diacetone alcohol SO, and 20 parts of ethylene glycol were polymerized for 6 hours while passing nitrogen gas. The molecular weight of the dead polymer obtained was approximately 30,000.

In the same manner as in Example 2, a polymer was obtained from the following raw materials. E diisobutylene-maleic acid copolymer product name: Demol EP [Kao Atlas ■] C9 polyacrylic iron soda product name: Nopcosanto R [San Nopco ■] -, polyacrylic ammonium product name: Nogcosanto RF M C San Nopco ■] ・, Polysodium methacrylate Trade name: Brimer k850 [Roam cloudy base ■] f, SufV7-MaVic acid 811 combination (monoester ammonium salt) Product name: SMA resin 440H [Al;ke (Cal ■]) g , PEG Product name: Macrogol 1500 (ゝ, Ba, [NOF ■] h, PEG-PPG Pro, 2, Polymer@Product name: Uniloop 400P-50B [NOF ■] Example 1 First, the following five types Each of the compositions was thoroughly stirred and mixed to create a slurry.
) on one side of the paper so that the dry isomorphic content is approximately 4 g/xlK, and dried the flakes according to the usual method to prepare the paper sample I.
- V oath creation and circle.

Regarding sample No. 9 obtained in this way,
Kurashita table of nine results after comparing and examining the characteristics of
Stop and show your friends. In addition, in Table-1 below, dot density o*
ji! Mine, Sakura Microdensitometer PDM-5
(Konishi Roku Photo Industry Co., Ltd.), medium 30μ, size 30
In the slit, the X-axis direction O@l1lk, l[ji10
x/see, f'r-t O's attack! IWm/se
The appropriate ratio of sample O delivery to the e-chart was adjusted using Zoo@, and the following results were obtained.

The dot diameter is determined by keeping the diameter of the printed dot constant using a solid inkjet mirror, and fixing time is determined by placing a rubber roller a certain distance away from the inkjet head, and varying the paper feeding speed so that the ink dots are fixed. It is possible to change the time until contact with the Zeng rubber roller (by means of a device), and to maintain a constant time from when ink dots are generated until ink is no longer adhered to the roller.

In addition, the ink ejection opening 1 liter (orifice diameter) of the inkjet recording device used here was Gos 69, and the ink used had the following composition of 40. gaps (adjusted with Tokyo Needle's E Shugo viscosity needle) Surface tension 5L4dyn@/aIK (Kyowa Kagaku Yo-suspension type l
11 (Note 1): Same place K11th, ink: Number of ink dots (Note 2) = W valence base ratio O - Very good 0・-Ryoge =- in pot Example 2 The polymer obtained in Synthesis Example 3 (100 parts by weight), water (110 parts by weight) and ethanol (50 parts by weight) were thoroughly stirred and mixed to create a slurry. did. This slurry has a basis weight of 65 tons.
/srl base paper surface to give a dry solid content of 4 g/rn', and then dried to produce a recording paper.

When inkjet recording was performed on this recording paper in the same manner as in Example 1, the results were the same as in the case of Sample V of Example 1.

Example 3.4 For the same sample as Sample I obtained in Example 1.

When inkjet recording was carried out in the same manner as in Example 1 using the inks shown in Table 2, the results were as shown in Table 2 below. The numerical values indicate parts by weight, and all other numerical values and symbols are as in Example IK.

Table-2 Example 5 Based on the same sample as the sample seal of Example 1), cyan.

When full-color recording was performed using each ink of magenta, yellow, and black, the fixing time, dot density, and dot diameter were the same as in Example 1, and each color was extremely clear. We were able to reproduce full-color photographs with excellent color reproduction.

Example 6 When each recording paper obtained in Example 4s1 was printed with a commercially available perpetual chain, in each case - there were no smudges, the ink O was absorbed quickly, and the calligraphy was very clean, with over 90 results. As mentioned above, in the present invention, the ink is attached to the ink.
Even if recording liquid of a different color is repeatedly deposited on the same spot within a short period of time, there is no phenomenon of the recording liquid flowing out or seeping out, and the color development of the ink is improved. The goal is to provide a recording material that is particularly suitable for multicolor inkjet recording, and which can suppress the spread of ink dots to a degree that does not impair the clarity of an image.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of the structure of the present invention, in which 1 is a base and 2 is a coating layer. le

Claims (1)

[Claims] A material in which a coating layer is applied to a substrate using a paint containing a multilayer body having both a hydrophilic structural part and a hydrophobic structural part.