JPS63260477A - Recording material - Google Patents

Abstract

PURPOSE:To accelerate an ink absorption, to enhance coloring property and to suppress the bleeding of ink by introducing specific alkyl group at the end of a molecule to contain polyamine compound imparted with surface active performance in a base material. CONSTITUTION:In order to introduce a long chain alkyl group to the end of a molecule, amino group-containing polymerizable monomer and, as required, other polymerizable monomer are used for a copolymer component to be polymerized by using relatively small amount of polymerization initiator in the presence of alkylmercaptan having long chain (6-18 carbons). Examples of the amino group-containing monomer include (3 or 4)-dimethylaminomethylstyrene as styrene derivatives, its salt, or quaternary compound. The other monomer used for the copolymerization component includes, for example, (meth)acrylic acid, such as methyl(meth) acrylate, ester compounds, such as 1-18C alkyl alcohol. The mean molecular weight of the polyamide compound is ranged in 500-10000 so as to obtain sufficient surface active performance. For example, when a paper is used as the base material, 0.01-5wt.% of polyamide compound is contained in the base material in the paper making solution in case of manufacturing paper.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a recording material, particularly a recording material suitable for printing with water-based ink, and more specifically to a recording material that has excellent ink absorption, adhesion, and coloring properties, and is free from bleeding. The present invention relates to a recording material capable of forming an image with excellent water resistance and light resistance, which can be polished by simply obtaining a high-resolution image.

(Prior Art and Problems to be Solved by the Present Invention) Recording methods using water-based inks are widely used because they are highly safe and have good printability.

However, images formed with water-based inks inherently have poor water resistance, and there are problems in that the images smear or dissolve when they come into contact with the water that formed the images.

For example, water-based inks are mainly used in inkjet recording methods, which have recently been attracting attention, in consideration of safety and printability. The inkjet recording method uses various operating principles to generate small ink droplets that fly and adhere to a recording material such as paper to form an image.It generates little noise and is capable of high-speed printing and multicolor printing. This recording method is rapidly becoming popular in various fields. As the recording material used in this inkjet recording method, conventional paper has generally been used. However, as the performance of inkjet recording apparatuses improves, such as faster printing and multicolor printing, recording materials are increasingly required to have even more sophisticated properties. That is, in order to obtain high-resolution, high-quality images comparable to color photographs, the following (1) to (6) (11) Ink absorption must be fast.

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

(3) The ink has excellent color development, and the ink dots have a high density and do not blur around the dots. The shape of the dot should be close to a circle and there should be no undulations around it.

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

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

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

There is a desire for a recording material with improved properties such as:

However, the reality is that there is no recording material that satisfies all of these characteristics.

Particularly when using water-based ink, it is important to make the formed image water resistant. As a method for making an image waterproof, for example, Japanese Patent Application Laid-open No. 53-49113 and Japanese Patent Application Laid-open No. 56-8499 are known.
No. 2 proposes an inkjet recording paper containing a polycation such as polyethyleneimine. However, although the water resistance can be improved to some extent by the method using polyethyleneimine, the light resistance is poor and the image disappears when exposed to sunlight or other light for a long time. Therefore, in order to improve water resistance and light resistance, Japanese Patent Application Laid-open No. 59-198186,
JP-198188 proposes a method using an organic acid salt of polyethyleneimine and a quaternized product of polyethyleneimine. Furthermore, JP-A No. 61-58788
The method using polyallylamine hydrochloride is described in JP-A-59-20696 and JP-A-60-109894.
The publication proposes a method using a dimethyldiallylammonium chloride polymer and a method using polyethyleneimine in combination with the polymer, but although both methods are satisfactory in water resistance to some extent, light resistance is still insufficient. , The ink absorption speed is slow, and there are many undulations around the ink dots, making it impossible to obtain high-resolution recording. There were problems such as the ink color changing easily.

Therefore, an object of the present invention is to satisfy the above-mentioned characteristics required for a recording method that prints using water-based ink, and in particular, to have excellent ink absorption, adhesion, and coloring properties during printing. The object of the present invention is to provide a recording material which also has excellent water resistance and light resistance after forming an image.

(Means and effects for solving the problems) In view of the current situation, the present inventors have conducted extensive research in order to obtain a recording material that can satisfy all of the above characteristics required for a recording method that prints using water-based ink. As a result of repeated research, they discovered that this can be achieved by incorporating a polyamine compound with a specific structure into the base material, and completed the present invention. In general, the use of amine compounds improves ink adhesion, color development, and water resistance of printed images, but on the other hand, it reduces ink absorption, resolution, and light resistance of printed images. However, this is based on new findings that polyamines with a specific structure increase absorption, image resolution, and light resistance.

That is, the present invention relates to a recording material in which a base material contains a polyamine compound (2) imparted with surfactant ability by introducing an alkyl group of K Cs to CI8 at the molecular terminal. By providing the polyamine compound with sufficient surfactant ability, it not only provides water resistance but also quickly lowers the surface tension of the ink when it adheres to the recording material, making it easier to absorb into the recording material and preventing bleeding. This relates to a recording material that has been improved to suppress .

The polyamine compound used in the present invention includes, for example, amine group-containing polymerizable monomers (a) represented by the following general formulas (1) to (V), organic acids or inorganic acids of the monomers (a), CP derived using at least one monomer selected from salts of and quaternized products of the monomer (a) as an essential monomer component; It has a bonded structure.

(1) (n) (1[[)
R1 (IV) (V) (above (
In the formulas 1) to (V), Y represents a bonding mode that is an amide bond, an ester bond, a methylene bond containing a substituent, or a combination of two or more of these bonds;
, R, independently represent hydrogen or a C1-C11 alkyl group. However, X is an integer from 1 to 5. ) The polyamine compound used in the present invention is characterized by having a long-chain alkyl group at the end of the molecule, and various methods can be used to introduce the long-chain alkyl group at the end of the molecule. It is advantageous to use the methods of (1) and (2).

■ In the presence of a long-chain (6 to 18 carbon atoms) alkyl mercaptan, a relatively small amount of polymerization initiator is used to convert the amino group-containing polymerizable monomer (a) into other polymerizable monomers (b). )
A method of polymerization using as a copolymerization component.

■ First, a reactive group-containing initiator and/or a reactive group-containing chain transfer agent having reactive groups such as a hydroxyl group, a carboxyl group, an amino group, a halogen atom, etc. The containing polymerizable monomer (a) is polymerized using the other polymerizable monomer (b) as a copolymerization component to synthesize an oligomer having a reactive group at the molecular end, and then the oligomer having a reactive group at the molecular end is synthesized. Compounds (hereinafter referred to as (referred to as alkylating agent).

Among these methods, method (1) is particularly advantageous because it can yield a low molecular weight polymer having an alkyl group directly introduced at the end at the same time as the polymerization, thereby simplifying the reaction steps.

Specific examples of the amino group-containing polymerizable monomer (a) represented by general formulas (1) to (V) include (3or4)-dimethylaminomethylstyrene, (3or4)-diethylaminomethylstyrene, (3or4)- Styrene derivatives such as dimethylaminomethyl α-methylstyrene, (3or4)-diethylaminomethyl α-methylstyrene; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dipropylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylic acid ester derivatives such as (meth)acrylate; dimethylaminoethyl (meth)acrylamide,
(Meth)acrylamide derivatives such as diethylamine ethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide; vinylpyridine, diallylamine, diallylmethylamine, diallylethylamine, allylamine, allyldimethylamine, etc. The salts and quaternized products of the amino group-containing polymerizable monomer (a) include salts of these amine group-containing polymerizable monomers (a) with organic acids or inorganic acids, and carbon atoms of 1 -12 quaternized products of alkyl halides and benzyl halides can also be mentioned, and one or two of these
It can be used in mixtures of m or more.

In the present invention, other polymerizable monomers (b) used as a copolymerization component of the diamino group-containing polymerizable monomer (a) include, for example, methyl (meth)acrylate, (meth)acrylic acid, etc. Ethyl, butyl (meth)acrylate, (meth)
(Meth) such as 2-ethylhexyl acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate
Ester compounds of acrylic acid and alkyl alcohol having 1 to 18 carbon atoms; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc.
(meth)acrylamides, such as meth)acrylamide, N,N-dimethyl(meth)acrylamide;
Examples include meth)acrylonitrile; styrene, and one type or a mixture of two or more of these can be used. However, the amount of the other polymerizable monomer (b) to be used should be within a range that does not practically impede the water solubility of the polyamine compound. In addition, the average molecular weight of the polyamine compound is 500 to 1 to obtain sufficient surfactant ability.
A range of 0000 is preferable. In addition, to obtain a quaternized polyamine compound (A) in which the amine group in the molecule is salted with an acid, a polyamine compound produced using the amino group-containing polymerizable monomer (a) may be used. (A) may be treated with an organic acid or an inorganic acid or a quaternizing agent, and in place of the amino group-containing monomer (a) during polymerization, a salt of the core monomer (a) or a quaternizing agent may be used. A method using a chemical compound may also be used.

The base material used in the present invention is typically paper, but cloth, resin film, synthetic paper, resin moldings, etc. can also be used.

The recording material of the present invention is obtained by, for example, containing the polyamide/cypolyamine compound (A) in the base material.

Various methods can be used to make the base material contain the polyamine compound (A), for example, a method in which the polyamine compound (A) is added in advance when manufacturing the base material, and a method in which the polyamine compound (A) is added to the base material in advance. , a method of immersing the base material in a solution containing the polyamine compound (A);
A method of applying a liquid material containing A) can be adopted as appropriate. As a specific example of a more typical embodiment, (
11 When paper is used as the base material, a method in which the polyamine compound (A) is contained in the papermaking liquid during paper manufacturing; (2) A coating liquid containing the polyamine compound (4) is applied to paper. Examples of methods include the method of

The amount of polyamine compound used is 0 to the base material.
．． It is preferable that the amount is in the range of 0.01 to 5% by weight, and if the amount used is less than 0.01% by weight, water resistance will decrease, and if the amount is less than 0.01% by weight,
If it exceeds this, the light resistance will decrease.

When obtaining the recording material of the present invention by the method (1) above,
In addition to the polyamine compound, antioxidants, ultraviolet absorbers, water-soluble polymers, synthetic resin aqueous dispersions, thickeners, pH adjusters, and the like may be blended into the papermaking solution depending on the purpose.

In addition, when obtaining the recording material of the present invention by the method (2) above, components conventionally used, for example, in coating solutions used for paper coating, may be added to the coating solution. Such components include, for example, inorganic pigments such as finely divided silicic acid, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, satin white, aluminum silicate, and IJ)bon; ; Water-soluble polymers such as starch, gelatin, casein, gum arabic, sodium alginate, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, and sodium polyacrylate; Synthetic resin aqueous dispersions such as synthetic rubber latex and acrylic emulsion; Polyvinyl butyral , organic solvent soluble resins such as polyvinyl chloride;
Further examples include various additives such as a dispersant, a fluorescent dye, a pH adjuster, an antifoaming agent, a lubricant, and a preservative. The coating solution is prepared by a known method such as a roll coater method, a blade coater method, or an air knife coater method.
Coat an amount of about 1/m (dry coating amount) onto the substrate.

(Effect of the invention) The recording material of the invention thus obtained has C6 to C6 at the molecular end.
Since the base material contains a polyamine compound which has been given surfactant ability by introducing an alkyl group of eta, ink absorption is fast and color development is excellent, and ink bleeding is suppressed. Therefore, a high-resolution recorded image can be obtained, and the recorded image exhibits excellent water resistance and satisfies light resistance. Problems that arise when using the product, i.e.
Although the recorded image has excellent water resistance, it solves all problems such as slow ink absorption, high-resolution recorded image cannot be obtained due to unevenness (bleeding) around the ink dots, and poor light resistance. It is resolved.

The mechanism by which the recording material of the present invention exhibits such excellent properties is not clear, but the surface-active properties of the polyamine compound improve water resistance and reduce ink absorption. Not only that, but blurring is suppressed, which increases resolution. Improvements in light resistance are also observed compared to conventional polyamines, since the amount of amine components that reduce light resistance can be reduced.

(Example) The present invention will be described below with reference to Examples, but it is not limited to these examples. In addition, parts and parts shown in the examples mean parts by weight and parts by weight.

The structure of the polyamine compound used in the examples and methods for evaluating various physical properties are shown below.

(11 Structure of the polyamine compound storage used in the production of the recording material of the present invention Molecular terminal K used in the production of the recording material of the present invention Cs-C1
Polyamine compounds (a) to (g) to which surface-active ability has been imparted by introducing an alkyl group are shown below.

C gourd O (Average molecular weight 1000) C feather O (Average molecular weight 8200) (Average molecule t 2300) (Average molecular weight 1β00゜ m:n-5:2) (Average molecular weight 3000) Fraud CH.

(Average molecule i 5000) CH.

δI-m (average molecule t 1500 mm: nm 5: 2) (21 Ink absorption speed Ink droplet of water-based inkjet ink (magenta) 0
．． The time from the moment the 3 μm ink droplet was attached to the surface until the entire amount of the ink droplet was absorbed by the recording material was measured.

(3) Ink dot shape Ink droplet of water-based inkjet ink (magenta) 0
．． The shape of an ink dot when 3 μl was absorbed into a recording material is shown.

○...The dot is close to a perfect circle and the circumference is smooth.

Δ・・・・・・ The dot is close to a perfect circle, and there is some burr-like blurring around the circumference.

×・・・・・・Dots are blurred. The shape of the dot becomes chestnut-like.

(4) After printing with water-resistant inkjet water-based ink (magenta), the color difference (Hunter ΔE) before and after immersion in running water for 3 minutes was measured using a colorimeter ND-1001DP (manufactured by Nippon Denshoku Kogyo ■). . The smaller the color difference, the better the water resistance.

(5) Light resistance: Shimadzu Fade Tester CF-2ON model 60℃
The sample was irradiated for 10 hours, and the color difference from that of the non-irradiated sample was determined using a colorimeter. The smaller the color difference, the better the light resistance.

(6) Hue measurement When a color is measured using a color difference meter and expressed as a and b values, the value of θ-tan''-'- is called hue.The color of ink is expressed numerically. Finally, we investigated the influence of the recording material on the color of the ink.

Examples 1 to 7 Basis weight 6311/7FLI, S, Tekicht size degree 3
A dry coating amount of 0.2 to 0.41 /
Recording materials of rot 1 to rot 7 were obtained by immersion treatment so that the recording materials had a temperature of

Regarding these recording materials, inkjet suitability includes 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 Example 1 except that a 2.0% aqueous solution of a polyamine compound that does not fall under the category of polyamine compound in the present invention was used.
In the same manner as above, recording materials 41' to 2' shown in Table 1 with dry coating amounts of 0.2 to 0.4 fi/ze were prepared.

The test results for inkjet suitability are also shown in Table 1.

Claims (1)

[Claims] 1. A recording material in which a base material contains a polyamine compound (A) imparted with surfactant ability by introducing an alkyl group of C_6 to C_1_8 to the molecular terminal.