JPH0686143B2 - Recording material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a recording material, particularly a recording material suitable for printing with an aqueous ink, and more specifically, it has excellent ink absorption, adhesion and color development, and is free from bleeding. The present invention relates to a recording material capable of forming not only a high-resolution image but also an image excellent in water resistance and light resistance.

(Problems to be Solved by the Related Art and the Present Invention) The recording method using an aqueous ink is widely used because of its high safety and good printability. However,
The image formed by the water-based ink is inherently poor in water resistance, and there is a problem that the image bleeds or melts by contact with water after the image is formed.

For example, in the ink jet recording method, which has recently received attention, water-based ink is mainly used in consideration of safety and printability. The ink jet recording method is a method in which small droplets of ink generated by various operating principles fly and adhere to a recording material such as paper to form an image, which produces less noise and enables high-speed printing and multicolor printing. As a recording method, it is rapidly spreading in various fields. As a recording material used in this ink jet recording method, ordinary paper has been generally used. However, with the improvement of the performance of the ink jet recording apparatus such as high speed printing or multicolor printing, more advanced characteristics are required for the recording material. That is, in order to obtain a high-resolution and high-quality image comparable to a color photograph, the following (1) to (6) (1) Ink absorption is fast.

(2) Even when the ink dots overlap, the ink that adheres later does not flow out to the previous dot.

(3) The color development of the ink is excellent, the density of the ink dots is high, and the areas around the dots are not blurred. The shape of the dot is close to a circle and there is no undulations on its periphery.

(4) The diameter of the ink dots should not become larger than necessary on the recording material.

(5) The ink color should not change depending on the recording material.

(6) The formed image has good water resistance and light resistance.

A recording material having improved characteristics such as is desired.

However, the reality is that no recording material satisfying all of these characteristics has been found.

Especially when using a water-based ink, it is important to make the formed image waterproof. As a method for making images water resistant, for example, JP-A-53-49113 and JP-A-56-84992 propose ink jet recording paper containing a polycation such as polyethyleneimine. However, although the water resistance can be improved to some extent by the method using polyethyleneimine, it has a defect that the image disappears when it is exposed to light such as sunlight for a long time due to poor light resistance. Therefore, in order to improve water resistance and light resistance, JP-A-59-198186 and JP-A-59-198188 propose methods using an organic acid salt of polyethyleneimine and a quaternized product of polyethyleneimine, respectively. ing. Furthermore, in JP-A-61-58788, a method using polyallylaminone hydrochloride is disclosed in JP-A-59-20696 and JP-A-60-10989.
In JP-A-4, a method of using a dimethyldiallylammonium chloride polymer and a method of using polyethyleneimine in combination with the polymer are proposed, but both methods have satisfactory water resistance to some extent, but still have poor light resistance. Sufficiently slow ink absorption speed, and many undulations around the ink dots, making it impossible to obtain high-resolution recording. There was a problem that the color of the ink was likely to change.

Therefore, the object of the present invention is to satisfy the above-mentioned various characteristics required for a recording method for printing using an aqueous ink, and particularly in the absorbability, adhesion, and color development of the ink during printing. It is an object of the present invention to provide a recording material which is excellent in water resistance and light resistance after forming an image.

(Means and Actions for Solving Problems) In view of such a current situation, the present inventors have earnestly studied to obtain a recording material that can satisfy all the above-mentioned characteristics required for a recording method for printing using an aqueous ink. As a result of repeating the above, it was found that this can be achieved by containing a polyamine compound having a specific structure in the base material, and the present invention has been completed. In the present invention, the use of an amine compound generally improves the ink adhesion, color developability and water resistance of the image after printing, but on the other hand reduces the ink absorptivity, the resolution of the image after printing, and the light resistance. On the other hand, it is based on a new finding that a polyamine having a specific structure enhances absorptivity and image resolution and also improves light resistance.

That is, the present invention is a recording material comprising a substrate containing a polyamine compound (A) to which a surface-active property is imparted by introducing a C _{6 to} C ₁₈ alkyl group at the molecular end, Amino group-containing polymerizable monomers (a) represented by formulas (I) to (V), salts of organic or inorganic acids of the monomers (a), and quaternized products of the monomers (a). The present invention relates to the above recording material, which has a structure in which an alkyl group is bonded to the molecular end of a (co) polymer derived by using at least one monomer selected from the following as an essential monomer component. .

(In the formulas (I) to (V), Y represents an amide bond, an ester bond, a methylene bond containing a substituent, or a combination mode of two or more kinds of these bonds,
R ₁ , R ₂ and R ₃ independently represent hydrogen or a C _{1 to} C ₁₂ alkyl group. However, X is an integer of 1 to 5. ) More specifically, by making the polyamine compound (A) have sufficient surface-active ability, not only the water resistance but also the water-based ink quickly lowers the surface tension of the ink and is easily absorbed by the recording material. The present invention relates to a recording material characterized by being improved so as to suppress scooping and bleeding.

The polyamine compound (A) used in the present invention is characterized by having a long-chain alkyl group at the molecular end, and various methods can be used to introduce a long-chain alkyl group at the molecular end. Advantageously, the methods and are described.

The amino group-containing polymerizable monomer (a) may be added to the other polymerizable monomer (b) if necessary by using a relatively small amount of a polymerization initiator in the presence of a long chain (6 to 18 carbon atoms) alkyl mercaptan. A method of polymerizing by using as a copolymerization component.

First, a reactive group-containing initiator and / or a reactive group-containing chain transfer agent having a reactive group such as a hydroxyl group, a carboxyl group, an amino group, or a halogen atom (including a latent group) is used to contain an amino group. If necessary, the polymerizable monomer (a) is polymerized by using another polymerizable monomer (b) as a copolymerization component to synthesize an oligomer having a reactive group at a molecular end, and then, at the molecular end, A compound having a group capable of reacting with the reactive group (for example, a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an epoxy group, an aziridine group, an oxazoline group) and an alkyl group having 6 to 18 carbon atoms (hereinafter referred to as an alkylating agent It is referred to as a).

Among these methods, the method (1) is particularly advantageous because the reaction step can be simplified because a low molecular weight polymer having an alkyl group directly introduced into the terminal can be obtained simultaneously with the polymerization.

Specific examples of the amino group-containing polymerizable monomer (a) represented by the general formulas (I) to (V) include (3or4) -dimethylaminomethylstyrene, (3or4) -diethylaminomethylstyrene, (3or4)- Styrene derivatives such as dimethylaminomethyl α-methylstyrene and (3or4) -diethylaminomethyl α-methylstyrene; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth)
(Meth) acrylic acid ester derivatives such as acrylate, dipropylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate; dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide And (meth) acrylamide derivatives such as diethylaminopropyl (meth) acrylamide; vinyl pyridine, diallylamine, diallylmethylamine, diallylethylamine, allylamine, allyldimethylamine, allyldiethylamine, and the like. Examples of the salt or quaternary compound of the monomer (a) include salts of these amino group-containing polymerizable monomers (a) with an organic acid or an inorganic acid, and alkyl halides having 1 to 12 carbon atoms, Quaternized by halogenated benzyl can be mentioned, it can be used in these one or more thereof.

In the present invention, the other polymerizable monomer (b) used in the copolymerization component of the amino group-containing polymerizable monomer (a), if necessary, is, for example, methyl (meth) acrylate or ethyl (meth) acrylate. , (Meth) butyl acrylate, (meth)
(Meth) such as 2-ethylhexyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate
Ester compounds of acrylic acid and an alkyl alcohol having 1 to 18 carbon atoms; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; (meth) acrylamide, Examples thereof include (meth) acrylamides such as N, N-dimethyl (meth) acrylamide; (meth) acrylonitrile; styrene and the like, and one or a mixture of two or more thereof can be used. However, the amount of the other polymerizable monomer (b) to be used should be such that the water solubility of the polyamine compound (A) does not hinder practical use. Further, the average molecular weight of the polyamine compound (A) is preferably in the range of 500 to 10,000 so that sufficient surface activity can be obtained. In addition, in order to obtain a quaternized polyamine compound (A) in which the amino group in the molecule is salted with an acid, a polyamine compound ((a) produced using the amino group-containing polymerizable monomer (a) is prepared. A) may be treated with an organic acid or an inorganic acid or a quaternizing agent. Instead of the amino group-containing monomer (a) during the polymerization, a salt or quaternary agent of the monomer (a) may be used. A method using a grade may be used.

As the base material used in the present invention, paper can be mentioned as a representative, but cloth, resin film, synthetic paper, resin molded body and the like can also be used.

The recording material of the present invention contains the polyamine compound (A) as a base material by, for example, a method of impregnating the base material with the polyamine compound (A) or a method of providing an ink receiving tank containing the polyamine compound (A) on the base material. It is obtained by including it in a material.

Various methods can be used for incorporating the polyamine compound (A) into the substrate. For example, a method of previously incorporating the polyamine compound (A) in the production of the substrate, or after the substrate is prepared. , The base material is a polyamine compound (A)
A method of immersing the substrate in a liquid containing, a method of applying a liquid containing the polyamine compound (A) to the substrate, and the like can be appropriately adopted. Further specific examples of typical embodiments are: (1) When paper is used as the substrate, a method in which the polyamine compound (A) is contained in the papermaking solution at the time of papermaking, (2) Examples thereof include a method of applying a coating liquid containing the polyamine compound (A).

The amount of the polyamine compound (A) used in this case is preferably in the range of 0.01 to 5% by weight with respect to the base material. If the amount used is less than 0.01% by weight, the water resistance decreases and if it exceeds 5% by weight. Light resistance is reduced.

When the recording material of the present invention is obtained by the method (1),
In addition to the polyamine compound, an antioxidant, an ultraviolet absorber, a water-soluble polymer, an aqueous dispersion of a synthetic resin, a thickener, a pH adjuster and the like can be freely added to the papermaking liquid according to the purpose.

Further, when the recording material of the present invention is obtained by the method (2), a component which has been conventionally used in, for example, a coating liquid used for paper coating may be added to the coating liquid. Examples of such components include finely divided silicic acid, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, satin white, aluminum silicate, lithopone and other inorganic pigments; starch,
Water-soluble polymers such as gelatin, casein, gum arabic, sodium alginate, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone and sodium polyacrylate; synthetic resin aqueous dispersions of synthetic rubber latex, acrylic emulsion, polyvinyl butyral, polyvinyl chloride, etc. Organic solvent soluble resin; further dispersant fluorescent dye, pH adjusting agent, defoaming agent, lubricant,
Various additives such as preservatives can be mentioned. The coating solution is generally applied on the substrate by a known method such as a roll coater method, a blade coater method or an air knife coater method in an amount of about 1 to 50 g / m ² (dry coating amount).

(Effect of the Invention) The recording material of the present invention thus obtained has C ₆ -C at the molecular end.
_{Since the} base material contains the polyamine compound (A) to which surface activity is imparted by introducing ₁₈ alkyl groups, the ink is absorbed quickly and the coloring property is excellent, and ink bleeding is suppressed. Therefore, a high-resolution recorded image is obtained, the recorded image exhibits excellent water resistance and also satisfies light resistance, and does not have a C _{6 to} C ₁₈ alkyl group at the end, which is a conventional technique. The problem that occurs when using a polyamine, that is, the water resistance of the recorded image is excellent, but the absorption of the ink is slow.

This is a solution to the problems that a high-resolution recorded image cannot be obtained because unevenness (bleeding) occurs in the peripheral area of the ink dot, and the light resistance is poor.

Although the mechanism of action of the recording material of the present invention exerting these excellent characteristics is not clear, the polyamine compound (A) has the surface active ability, so that the water resistance is improved and the ink absorption is fast. Not only that, but bleeding is suppressed, so the resolution is improved. As for the light resistance, an improvement is recognized because the amount of the amine component that reduces the light resistance can be reduced as compared with the conventional polyamine.

(Example) Hereinafter, although an example of the present invention is given and explained, it is not limited to these examples. In the examples, parts and% mean parts by weight and% by weight.

The structures of the polyamine compound (A) used in the examples and the evaluation methods for various physical properties are shown below.

(1) Structure of the polyamine compound (A) used in the production of the recording material of the present invention A C ₆ -C ₈ alkyl group is introduced at the molecular end used in the production of the recording material of the present invention to impart surface activity. The polyamine compounds (a) to (g) are shown below.

(2) Ink absorption speed Ink drop of water-based ink (magenta) for ink jet.
The time from the moment when 3 μ was attached to the surface to the time when all the ink droplets were absorbed by the recording material was measured.

(3) Ink dot shape Ink droplets of water-based ink (magenta) for ink jet.
The shape of the ink dots when 3 μ is absorbed by the recording material is shown.

○: The dots are close to a perfect circle and the circumference is smooth.

△: The dots are close to a perfect circle, and some mottled chestnut-like bleeding appears on the circumference.

×: The dots are blurred. The shape of the dots becomes a moth.

(4) Water resistance After printing with a water-based ink for ink jet (magenta), the color difference (Hunter ΔE) before and after immersion in running water for 3 minutes was measured using a colorimeter ND-1001DP (Nippon Denshoku Industries Co., Ltd.). It was measured. The smaller the color difference, the better the water resistance.

(5) Lightfastness As for lightfastness, the Shimadzu Fade Tester CF-20N type was irradiated at 60 ° C. for 10 hours, and the color difference from that of unirradiated light was obtained using a colorimeter. The smaller the color difference, the better the light resistance.

(6) Hue When the color is expressed by L, a, b values with a colorimeter The value of is called hue. The color of the ink was expressed numerically, and the influence of the recording material on the color of the ink was investigated by this.

Examples 1 to 7 General high-quality paper having a basis weight of 63 g / m ² and a Steckigt sizing degree of 30 seconds was added to a 0.5% aqueous solution of polyamine compounds (a) to (g) so that the dry coating amount was 0.2 to 0.4 g / m ² . No. 1 to N
A recording material of o.7 was obtained.

For these recording materials, the ink jet suitability, ink absorption speed, ink dot shape, water resistance, light resistance,
The hue was measured. The results are shown in Table 1.

Comparative Examples 1 to 5 The same procedure as in Example 1 except that a 2.0% aqueous solution of a polyamine compound not corresponding to the polyamine compound (A) in the present invention was used, and a dry coating amount of 0.2 to 0.4 g / m ² was applied. Recording materials No. 1'to No. 2'shown in the table were prepared.

Inkjet suitability test results are also shown in Table 1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masuji Izumibayashi 5-8 Nishimitabicho, Suita City, Osaka Prefecture Central Research Laboratory of Nippon Shokubai Kagaku Kogyo Co., Ltd. (56) Reference JP-A-61-146591 (JP, A) JP-A-60-49990 (JP, A) JP-A-60-11389 (JP, A) JP-A-58-177390 (JP, A)

Claims (1)

[Claims] 1. A recording material comprising a base material containing a polyamine compound (A) having a surface-active property by introducing a C ₆ -C ₁₈ alkyl group at the molecular end, and the polyamine compound (A). A) is an amino group-containing polymerizable monomer (a) represented by the following general formulas (I) to (V), an organic acid or inorganic acid salt of the monomer (a), and the monomer. (A)
The recording material having a structure in which an alkyl group is bonded to the molecular terminal of a (co) polymer derived by using at least one monomer selected from . (In the formulas (I) to (V), Y represents an amide bond, an ester bond, a methylene bond containing a substituent, or a combination mode of two or more kinds of these bonds,
R ₁ , R ₂ and R ₃ independently represent hydrogen or a C _{1 to} C ₁₂ alkyl group. However, X is an integer of 1 to 5. )