JPH08187933A - Ink jet recording sheet - Google Patents

Abstract

PURPOSE: To provide an ink jet recording sheet imparting high image absorbability and sharpness and forming an image excellent in light fastness and water resistance. CONSTITUTION: An ink receiving layer is provided on a support composed of a nonwoven fabric and the components thereof mainly consist of ultrafine particles of specific inorganic pigment and an ultraviolet absorbable cationized polymer and the fragile air permeability prescribed by JIS L1096 of the ink jet recording sheet after the ink receiving layer is applied is 100cc/cm<2> /sec or less. Pref., a structural unit having ultraviolet absorbing capacity is a 2- hydroxybenzophenone residue or a 2-hydroxybenzotriazole residue.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording sheet, and more specifically, it has a high image density, excellent ink absorbability, excellent water resistance and light resistance of an image, and has a unique texture. The present invention relates to an inkjet recording sheet.

[0002]

2. Description of the Related Art The ink jet recording system is a system for ejecting minute droplets of ink by various operating principles and adhering them to a recording sheet such as paper to record images, characters, etc., but at high speed and low noise. It is characterized by easy multicoloring, high flexibility in recording patterns, and no need for development-fixing, and is rapidly spreading in various applications as a recording device for various figures and color images including Chinese characters. Furthermore,
An image formed by the multicolor inkjet system can obtain a print comparable to that of the multicolor printing by the plate making system or the printing by the color photographic system. Also,
For applications requiring a small number of copies, it is being widely applied to the field of full-color image recording because it is cheaper than the photographic technique.

As an ink jet recording sheet used in this ink jet recording system, efforts have been made from the viewpoint of equipment and ink composition so as to use high quality paper or coated paper which is usually used for printing and writing. However, as the performance of inkjet recording devices has improved and the applications have expanded, such as higher-speed, higher-definition or full-color devices, it is expected that recording sheets will also have the following more advanced characteristics. Became. (1) The recording dot density and the image density are high. (2) Image color and sharpness are good. (3) The print dot shape is good. (4) Good ink absorption. (5) The recorded image has good image storability such as water resistance, light resistance, and ozone resistance.

On the other hand, in the fields of design, event, advertisement, etc., color image recording using a durable and water-resistant support and featuring the texture of the support itself has become popular, but it is used outdoors. For large-screen color image recording such as a hanging curtain, the inkjet recording method is simple and widely used. In the case of such color image recording, it is essential to impart water resistance and light resistance on the assumption that a durable support is used and is used outdoors.

In response to such demands, some proposals have been made in the past. For example, in order to improve water resistance, a method of impregnating a surface with a polycationic polyelectrolyte (JP-A-56-84992) and a water-resistant method of forming a dye and a chelate in a water-soluble ink (JP-A-56-84992). 55-1
No. 50396) is disclosed. Furthermore, in order to improve water resistance, light resistance, and ozone resistance at the same time,
Incorporation of a basic oligomer (JP-A-60-11)
No. 389), a polyvinylamine copolymer is used in a coating layer in or on a substrate (JP-A-64-808).
No. 5) is disclosed.

However, the ink jet recording sheet using a conventional non-woven fabric as a support has not yet been satisfied with the above required characteristics.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink jet recording sheet having high image density, excellent ink absorption, excellent water resistance and light resistance of an image, and a unique texture.

[0008]

DISCLOSURE OF THE INVENTION As a result of earnest studies in view of the above, the present inventor has found that an ink jet having a high image density, excellent ink absorptivity, and a unique texture having excellent water resistance and light resistance of an image. Invented the recording sheet.

That is, the ink jet recording sheet of the present invention is an ink jet recording sheet obtained by coating an ink receiving layer on a support, wherein the support is made of a non-woven fabric,
The ink receiving layer component is mainly composed of an ultrafine inorganic pigment having a primary particle size of 100 nm or less and a polymerizable vinyl compound having a quaternary ammonium salt group bonded thereto and a polymerizable vinyl compound having a structural unit having an ultraviolet absorbing ability bonded thereto. The recording sheet is characterized in that it is composed of a UV-absorbing cationized polymer and has a Frazier air permeability of 100 cc / cm ² / sec or less defined by JIS L1096 of the recording sheet.

Further, in the ink jet recording sheet of the present invention, the non-woven fabric is preferably a wet non-woven fabric.

More preferably, the structural unit having an ultraviolet absorbing ability is a 2-hydroxybenzophenone residue or a 2-hydroxybenzotriazole residue.

The ink jet recording sheet of the present invention will be described in detail below. In the ink jet recording sheet of the present invention, the ink receiving layer components are mainly composed of a specific ultrafine particle inorganic pigment and an ultraviolet absorbing cationized polymer on a support made of a non-woven fabric, and the Frazier air permeability defined by JIS L1096 is 100 cc. When it is / cm ² / sec or less, it has a texture unique to the nonwoven fabric, and a good recorded image can be obtained.

An ink jet recording sheet obtained by coating an ink receiving layer on one side of a non-woven fabric has almost the same surface as the non-woven fabric if the Frazier air permeability defined by the present invention is within 100 cc / cm ² / sec. Since the ink receiving layer is formed as a uniform coating layer, good recording characteristics can be maintained. However, the Frazier air permeability of the recording sheet is 100 cc / cm ²
If it exceeds / sec, a large number of voids are formed on the surface of the coating layer of the ink receiving layer, which is not preferable because the recorded image is uneven.

In the ink jet recording sheet of the present invention, when the ink receiving layer is provided on the surface of the nonwoven fabric which is the support, the nonwoven fabric itself has a Frazier air permeability of 350 cc / cm ² / s.
It is preferably ec or less. This is not preferable because when the ink receiving layer is applied to the nonwoven fabric, if it exceeds 350 cc / cm ² / sec, it becomes difficult to apply. However, even with a nonwoven fabric having high Frazier air permeability, the recording sheet within the scope of the present invention can be obtained by applying the ink-receiving layer using a pretreated product. Even with a non-treated non-woven fabric, the recording sheet within the scope of the present invention can be obtained by controlling the coating amount of the ink receiving layer.

As the pretreatment of the non-woven fabric, for example, before applying the ink receiving layer, an undercoat layer is provided on the surface of the non-woven fabric by using a pigment or the like, or the Frazier air permeability is lowered by a means such as a thermal calender. Thus, the coating of the ink receiving layer can be facilitated.

The nonwoven fabric used in the present invention is roughly classified into
There is a wet non-woven fabric, a dry non-woven fabric such as a stitch bond system, a spun bond system, a melt blow system, a thermal bond system, a jet bond system, or a spun lace non-woven fabric using a wet non-woven fabric or a dry non-woven fabric.

Generally, the wetness of nonwoven fabrics is smaller than that of dry nonwoven fabrics, and the Frazier air permeability is preferable when used as a support of the ink jet recording sheet of the present invention.

The fibers of the non-woven fabric used in the present invention may be any fibers as long as they can form the non-woven fabric. For example, polyester-based fibers such as homopolymers and copolymers such as polyethylene terephthalate, polybutylene terephthalate, or modified polymers of these polymers, polyolefin-based such as homopolymers and copolymers such as polypropylene, polyethylene, polystyrene, or modified polymers thereof. Fiber, acrylic fiber, polyacrylonitrile fiber such as modacrylic fiber, nylon 6, nylon 6
6 such as nylon fiber, polyvinyl alcohol fiber, urethane fiber, acrylic fiber, and other organic synthetic fiber; regenerated cellulose fiber such as rayon, or fiber obtained by spinning a solution of collagen, alginic acid, chitin, etc. Recycled fibers such as; semi-synthetic fibers such as acetate fibers; cellulosic fibers such as hemp, cotton and pulp; natural fibers such as protein fibers such as wool and silk; metal fibers, glass fibers, carbon Various fibers such as inorganic fibers such as fibers can be used, and these can be used alone or in combination. Further, these fibers can be used as a binder by combining a polyolefin-based heat-adhesive fiber or a polyester-based heat-adhesive fiber.

The fibers used in the above-mentioned non-woven fabric can be used by appropriately changing the fineness and the fiber length according to the manufacturing method of the non-woven fabric, and are not limited.

In the ink jet recording sheet of the present invention, the coating amount of the ink receiving layer can be appropriately changed according to the Frazier air permeability of the nonwoven fabric as the support. When the Frazier air permeability of the support is less than 150 cc / cm ² / sec, the coating amount of the ink receiving layer is about 1 to 10 g / m ² . The support has a Frazier air permeability of 150 to 3
When it is in the range of 50 cc / cm ² / sec, the coating amount of the ink receiving layer is about 10 to ²⁰ g / m ² .

In the ink jet recording sheet of the present invention, the UV absorbing cationic polymer in the ink receiving layer component is --SO ₃ Na group, which is a dye component in the ink,
Since it reacts with SO ₃ H groups, —NH ₂ groups and the like to form a water-insoluble salt, it has a function of ink fixing property and can exhibit an effect as water resistance. Further, it has a function of absorbing ultraviolet rays and can exert an effect as light resistance of an image.

In the ultraviolet-absorbing cationized polymer of the present invention, structural units having an ultraviolet-absorbing ability, that is, 2-hydroxybenzophenone residue, 2-hydroxybenzotriazole residue and the like are bonded to the main chain of the polymerizable vinyl compound monomer. And a polymerizable vinyl compound having a quaternary ammonium salt group bonded thereto.

The copolymerization ratio (p / q) in the copolymer of the polymerizable vinyl compound (p) having a structural unit having ultraviolet absorption ability and the polymerizable vinyl compound (q) having a quaternary ammonium salt group is , Can be set appropriately. The water-soluble or self-dispersible UV-absorbing cationized polymer can be obtained by changing the ratio of p and q. For example, when the ratio of the polymerizable vinyl compound to which a quaternary ammonium salt group is bound is reduced, the water-soluble type is shifted to the self-dispersible type.

As the structural unit having an ultraviolet absorbing ability,
A 2-hydroxybenzophenone derivative, a 2-hydroxybenzotriazole derivative, a salicylic acid derivative, a cyanoacrylate derivative, and the like, preferably a 2-hydroxybenzophenone derivative and a 2-hydroxybenzotriazole derivative can be mentioned. For example, they are exemplified as follows. be able to.

1) 2-Hydroxybenzophenone derivative 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfo Benzophenone, 2,
4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, bis (2
-Methoxy-4-hydroxy-5-benzoylphenyl) methane, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone, 2-hydroxy-4- (2-acryloyloxy) ethoxybenzophenone, 2 -Hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone, 2-hydroxy-4- (2-methyl-2)
-Acryloyloxy) ethoxybenzophenone and the like.

2) 2-hydroxybenzotriazole derivative 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-
Butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-amylphenyl) benzotriazole, 2- {2'-hydroxy-3'-(3 ", 4",
5 ", 6" -tetrahydrophthalimidomethyl) -5 '
-Methylphenyl} benzotriazole, 2,2-methylenebis {4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol}, 2- {2'- Hydroxy-5 '-(methacryloyloxy) phenyl} benzotriazole, 2-
{2'-hydroxy-5 '-(acryloyloxy) phenyl} benzotriazole, 2- {2'-hydroxy-3'-t-butyl-5'-(methacryloyloxy)
Phenyl} benzotriazole, 2- {2'-hydroxy-3'-methyl-5 '-(acryloyloxy) phenyl} benzotriazole, 2- {2'-hydroxy-
5 '-(methacryloyloxypropyl) phenyl}-
5-chlorobenzotritriazole, 2- {2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl} benzotriazole, 2- {2'-hydroxy-
5 '-(acryloyloxyethyl) phenyl} benzotriazole, 2- {2'-hydroxy-3'-t-butyl-5'-(methacryloyloxyethyl) phenyl} benzotriazole, 2- {2'-hydroxy-
3'-methyl-5 '-(acryloyloxyethyl) phenyl} benzotriazole, 2- {2'-hydroxy-5'-(methacryloyloxypropyl) phenyl}
-5-chlorobenzotriazole, 2- {2'-hydroxy-5 '-(acroyloxybutyl) phenyl}-
5-methylbenzotriazole, {2-hydroxy-3
-T-butyl-5- (acryloyloxyethoxycarbonylethyl) phenyl} benzotriazole and the like.

3) Salicylic Acid Derivatives Phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate and the like.

4) Cyanoacrylate derivative 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate and the like.

The polymerizable vinyl compound having a quaternary ammonium salt group is a polymerizable vinyl compound having a copolymerizable polymerizable vinyl compound having a tertiary amino group in the molecule as a monomer and a structural unit having an ultraviolet absorbing ability. After being copolymerized with a compound, the amino group is quaternized with an alkylating agent, or the tertiary amino group of the monomer is converted into a quaternary ammonium salt with an alkylating agent in advance, and then this is copolymerized. By doing so, it can be introduced into the ultraviolet absorbing cationized polymer.

Examples of the copolymerizable polymerizable vinyl compound having a tertiary amino group in the molecule include, for example, N, N-dimethylaminopropyl acrylate, N, N-diethylaminoethyl acrylate and N, N-dimethylaminoethyl methacrylate. , N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-dimethylaminobutyl methacrylate, N, N-dimethylaminoethyl acrylate, N,
N-dimethylaminopropyl acrylamide, N, N-
Examples thereof include dimethylaminoethylacrylamide, acryloylmorpholine, N-2-hydroxy-3-acryloyloxypropyl-N, N-dimethylamine, N-3-methacryloyloxy-2-hydroxypropyl-N, N-diethylamine and the like.

Examples of the alkylating agent for converting the amino group of the polymerizable vinyl compound having a tertiary amino group into a quaternary ammonium salt include halogenated alkyls such as benzyl chloride and methyl chloride; sulfuric acid such as dimethylsulfate and diethylsulfate. Examples thereof include esters, and the betaine-type quaternary ammonium group can be obtained by reacting with monochloroacetic acid, β-propiolactone and the like.

Examples of the polymerizable vinyl compound containing a quaternary ammonium salt group include glycidyl trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride.
Chloro-2-hydroxypropyltriethanolammonium chloride, glycidyldimethylbenzylammonium chloride, glycidyldimethylbutylammonium chloride, N-2-hydroxy-3-acryloyloxypropyl-N, N, N-trimethylammonium chloride, N-methacryloylaminoethyl -N,
N, N-dimethylbenzyl ammonium chloride, N
-Methacryloxy-N, N, N-triethylammonium ethyl sulfuric acid and the like can be mentioned.

In the ink jet recording sheet of the present invention, when an ink receiving layer is provided by using a support having a high Frazier air permeability, a support having an undercoat layer made of an inorganic or organic pigment on the surface of the support in advance. Alternatively, the use of a support having a heat-calendering treatment to reduce the voids on the support surface can reduce the coating amount of the ink receiving layer, which is an effective means.

The ink jet recording sheet according to the present invention comprises a support surface coated with a specific ultrafine particle inorganic pigment and an ink receiving layer component mainly composed of a UV-absorbing cationized polymer. High image density can be obtained due to the high ink absorbency.

In the ink jet recording sheet of the present invention, it is preferable to further use a binder as an ink receiving layer component, and the amount of the binder used is 5 to 30 parts by weight with respect to 100 parts by weight of the ultrafine particle inorganic pigment.
More preferably, it is 10 to 25 parts by weight. Here, if the amount of the binder in the coating liquid for the ink receiving layer is less than 5 parts by weight, the adhesiveness to the support will be poor, and if it is more than 30 parts by weight, the binder will impair the ink absorbency, which is not preferable. .

In the ink jet recording sheet of the present invention, the ink receiving layer coating liquid containing the above components preferably has a coating liquid concentration of 4 to 25% by weight. However, the coating liquid concentration may be appropriately changed depending on the method of coating on the support.

As a method for coating or impregnating the ink receiving layer on the support, various blade coaters, roll coaters, air knife coaters, bar coaters, rod coaters,
Gate roll coater, curtain coater, short dwell coater, gravure coater, flexo gravure coater,
Various devices such as a size press can be used on-machine or off-machine. However, in the present invention,
Particularly, an air knife coater, a rod coater and a gate roll coater are preferable.

The ultrafine particle inorganic pigment used in the present invention is
The primary particle size of the ultrafine inorganic pigment is 100 nm or less, preferably 50 nm or less. As these ultrafine particle inorganic pigments, those which are dispersed in water in a colloidal state while maintaining the primary particle size are used.

Examples of ultrafine particle inorganic pigments include the following. For example, silica (colloidal silica), alumina or alumina hydrate (alumina sol,
Colloidal alumina, cationic aluminum oxide or its hydrate, pseudo-boehmite, etc.), surface-treated cationic colloidal silica, aluminum silicate, magnesium silicate, magnesium carbonate and the like, more preferably primary particles are porous. However, even if it is non-porous, it aggregates at the time of preparing the coating liquid, and further aggregates at the time of coating drying,
It is preferable that a porous coating layer surface is formed on the surface of the support.

Further, as the inorganic pigment that can be used in combination with the ultrafine particle inorganic pigment, any conventionally known inorganic pigment can be used. For example, light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth,
Examples thereof include calcium silicate, synthetic amorphous silica, aluminum hydroxide, lithopone, zeolite, hydrohaloysite, magnesium hydroxide and the like.

Among these inorganic pigments, porous inorganic pigments are preferable, and examples thereof include porous synthetic amorphous silica, porous magnesium carbonate, porous alumina, etc., and particularly porous synthetic amorphous having a large pore volume. Silica is preferred. Further, organic pigments such as styrene-based plastic pigments, acrylic-based plastic pigments, polyethylene, microcapsules, urea resins and melamine resins can be used together with the above ultrafine inorganic pigments.

The binder used as a component of the ink receiving layer is, for example, polyvinyl alcohol, vinyl acetate, oxidized starch, etherified starch, cellulose derivative such as carboxymethyl cellulose, hydroxyethyl cellulose, casein, gelatin, soybean protein, silyl modified polyvinyl. Alcohol, etc .; Conjugated diene copolymer latex such as maleic anhydride resin, styrene-butadiene copolymer, methylmethacrylate-butadiene copolymer; polymer or copolymer of acrylic acid ester and methacrylic acid ester, acrylic acid and Acrylic polymer latex such as methacrylic acid polymer or copolymer; vinyl polymer latex such as ethylene-vinyl acetate copolymer; or functional group-containing unit such as carboxyl group of these various polymers Functional groups by modified polymer latex; melamine resin, aqueous binders such as thermosetting synthetic resin such as urea resin; polymethyl methacrylate,
Examples of the binder include synthetic resin binders such as polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, and alkyd resin, and at least one kind can be used.

Further, a cationic resin added for the purpose of fixing a conventionally known dye can be used together.

Further, as other additives, pigment dispersants, thickeners, fluidity improvers, defoamers, foam suppressors, release agents,
Foaming agents, penetrants, coloring dyes, coloring pigments, optical brighteners, ultraviolet absorbers, antioxidants, preservatives, anti-bacterial agents, water resistance agents, wet paper strength enhancers, dry paper strength enhancers, etc. It can also be blended.

The ink jet recording ink referred to in the present invention is a water-based ink comprising the following colorant, liquid medium and other additives.

Examples of the colorant include water-soluble dyes such as direct dyes, acid dyes, basic dyes, reactive dyes and food dyes.

As the solvent for the aqueous ink, water and various water-soluble organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, C1-C4 alkyl alcohols such as isobutyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyethylene glycol, polypropylene glycol Polyalkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol , Hexylene glycol,
Alkylene glycols having 2 to 6 alkylene groups such as diethylene glycol; lower alkyl ethers of polyhydric alcohols such as glycerin, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol and monomethyl ether. . Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether are preferable. Other additives include, for example, a pH adjusting agent, a sequestering agent, an antifungal agent, a viscosity adjusting agent, a surface tension adjusting agent, a wetting agent, a surfactant, and a rust preventive agent.

The ink jet recording sheet according to the present invention is not limited to use as an ink jet recording sheet, but may be used as any recording sheet using a liquid ink during recording. For example, for thermal transfer recording, an ink sheet that is formed by coating a non-woven fabric that is a support with a heat-fusible ink that contains a heat-fusible substance, dyes and pigments as the main component is heated from the back side to melt and transfer the ink. Image-receiving sheet, inkjet recording sheet that heat-melts heat-meltable ink to form fine droplets for flight recording, inkjet recording sheet using ink in which oil-soluble dye is dissolved in solvent, photopolymerizable monomer and colorless or colored dye An image receiving sheet corresponding to a light and pressure sensitive donor sheet using microcapsules containing a pigment can be used.

The common point of these recording sheets is that the ink is in a liquid state at the time of recording. The liquid ink penetrates or spreads in the depth direction or the horizontal direction of the ink receiving layer of the recording sheet before being cured, solidified, or fixed. The various recording sheets described above require absorptivity according to their respective systems, and the inkjet recording sheet of the present invention can be used as the various recording sheets described above without any limitation.

Further, the ink jet recording sheet according to the present invention can be used as a recording sheet for heating and fixing toner of the electrophotographic recording system which is widely used in copying machines and printers.

[0051]

In the ink jet recording sheet of the present invention, the ink jet layer after the ink receiving layer is coated on the support made of a non-woven fabric, the ink receiving layer component is mainly composed of a specific ultrafine particle inorganic pigment and an ultraviolet absorbing cationic polymer When the recording sheet has a Frazier air permeability defined by JIS L1096 of 100 cc / cm ² / sec or less, an inkjet recording sheet having excellent recording characteristics and light resistance and having a unique texture can be obtained.

The reason therefor is that the ultraviolet absorbing cationized polymer as an essential component of the gloss development layer is a dye component in the ink: --SO ₃ Na group, --SO ₃ H group, --NH ₂
It is considered that since it reacts with a group or the like to form a salt insoluble in water, it has a function of ink fixing property and can improve water resistance. Further, the UV-absorbing cationized polymer is fixed in the ink receiving layer without being affected by external conditions by bonding a structural unit having UV-absorbing ability to a polymerizable vinyl compound having a quaternary ammonium salt group. Therefore, it is presumed that the dye in the ink can contribute to the light resistance.

[0053]

EXAMPLES The present invention will be described in detail below with reference to examples. The present invention is not limited to this. All parts and% in the following are by weight.

Preparation examples of the ultraviolet absorbing cationized polymer are shown below in advance. Preparation Example 1 UV absorber polymer was prepared in the same manner as in Preparation Example 1 using 30 g of 2- [2′-hydroxy-5 ′-(methacryloyloxy) phenyl] benzotriazole, 70 g of N, N-diethylaminoethyl acrylate and 100 g of ethyl cellosolve. An aqueous solution was synthesized. Subsequently, 30 g of monochloroacetic acid was added dropwise over 30 minutes, and the reaction was performed for 2 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an ultraviolet absorbing cationized polymer aqueous solution (solid content 20% by weight) of Preparation Example 1.

Preparation Example 2 2-hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone 30 g, N-2-hydroxy-3
-Preparation Example 1 using 70 g of acryloyloxypropyl-N, N-dimethylamine and 100 g of ethyl cellosolve
An ultraviolet absorbent polymer aqueous solution was synthesized in the same manner as in.
Subsequently, 30 g of methyl chloride was added dropwise over 30 minutes, and the reaction was performed in a nitrogen atmosphere for 2 hours. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an ultraviolet absorbing cationic polymer aqueous solution (solid content 20% by weight) of Preparation Example 2.

Preparation Example 3 2- [2'-hydroxy-5 '-(methacryloyloxy) phenyl] -5-chlorobenzotriazole 30
g, N, N-diethylaminoethyl acrylate 70
g and 100 g of ethyl cellosolve, an ultraviolet absorbent polymer aqueous solution was synthesized in the same manner as in Preparation Example 1. Subsequently, 30 g of benzyl chloride was added dropwise over 30 minutes, and the reaction was performed in a nitrogen atmosphere for 2 hours. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an ultraviolet absorbing cationized polymer aqueous solution (solid content 20% by weight) of Preparation Example 3.

Preparation Example 4 2-hydroxy-4-methacryloyloxybenzophenone (30 g), N, N-dimethylaminopropyl acrylamide (70 g) and ethyl cellosolve (100 g) were added to a separa equipped with a Dimroth, a dropping funnel, a thermometer, a nitrogen introducing tube, and a stirrer. The mixture was charged into a bull flask and the temperature was raised to 80 ° C. while introducing nitrogen from a nitrogen introducing pipe. After that, 0.1 g of azobisisobutyronitrile dissolved in a small amount of ethyl cellosolve was divided into 4 portions and added dropwise over 30 minutes. After completion of the dropping, reaction was carried out for 2 hours in a nitrogen atmosphere to synthesize an ultraviolet absorbent polymer aqueous solution. Subsequently, 30 g of diethyl sulfuric acid
Was added dropwise over 30 minutes, and the reaction was performed for 2 hours under a nitrogen atmosphere. After the reaction is complete, cool to room temperature, dilute with water,
An ultraviolet absorbing cationic polymer aqueous solution (solid content 20% by weight) of Preparation Example 4 was obtained.

Example 1 [Preparation of Nonwoven Fabric] An aqueous slurry consisting of 95 parts of glass fiber having a fiber diameter of 1 μm and 5 parts of hot water-soluble polyvinyl alcohol fiber (2 denier, fiber length 3 mm) was prepared, and the wet papermaking method was used. A non-woven fabric having a basis weight of 60 g / m ² was produced. The Frazier air permeability of the produced non-woven fabric was 350 cc / cm ² / sec.

[Coating of ink receiving layer] As a component of the ink receiving layer, cationic colloidal silica (Snowtex-AK (3), manufactured by Nissan Chemical Co., Ltd., primary particle diameter 10 to 20 n)
m) 100 parts, polyvinyl alcohol (P
VA117, manufactured by Kuraray Co., Ltd.), 30 parts, and an aqueous dispersion having a solid content concentration of 20% and containing 15 parts of the ultraviolet-absorbing cationized polymer of Preparation Example 1 as a main component and dried solid content of 20.0 g / using an air knife coater. An inkjet recording sheet was prepared by coating and drying so as to have m ^2, and finishing by machine calendering. The produced inkjet recording sheet had a Frazier air permeability of 95 cc / cm ² / sec.

Comparative Example 1 InkJet recording in the same manner as in Example 4 except that the nonwoven fabric prepared in Example 1 was used to apply the components of the ink receiving layer so that the dry solid content would be 15.0 g / m ^2. A sheet was prepared. At this time, the Frazier air permeability of the inkjet recording sheet was 175 cc / cm ² / sec.

Example 2 [Preparation of Nonwoven Fabric] NBKP4 with Freeness of 480 mlcsf
0 parts, polyester fiber (fiber diameter 2 denier, fiber length 5
mm) 60 parts of an aqueous slurry was prepared, and a non-woven fabric having a basis weight of 50 g / m ² was prepared by using a wet papermaking method. The non-woven fabric thus produced had a Frazier air permeability of 100 cc / cm ² / sec.

[Coating of ink receiving layer] As a component of the ink receiving layer, colloidal silica (Snowtex-YL,
Nissan Chemical Co., Ltd., primary particle size 50-80 nm) 100 parts, polyvinyl alcohol (PVA117, Kuraray Co., Ltd.) 30 parts as an adhesive, solid content concentration 10 which is the main component of UV absorbing cationic polymer of Preparation Example 2 10 % Aqueous dispersion using an air knife coater to dry solid content 10.0
An inkjet recording sheet was prepared by coating and drying so as to be g / m ² and finishing by machine calendering. The ink jet recording sheet produced had a Frazier air permeability of 25.
It was cc / cm ² / sec.

Example 3 Using the components of the ink receiving layer of Example 2 to give a dry solid content of 5.
An inkjet recording sheet was produced in the same manner as in Example 2 except that the coating was performed so that the coating amount was 0 g / m ² . The inkjet recording sheet produced had a Frazier air permeability of 50 cc / c.
It was m ² / sec.

Comparative Example 2 Instead of the colloidal silica used in Example 2, another colloidal silica having a large primary particle size (Snowtex P) was used.
ST-3, Nissan Chemical, primary particle size 300 ± 30 nm)
An ink jet recording sheet was produced in the same manner as in Example 2 except that 100 parts of was used. The inkjet recording sheet produced had a Frazier air permeability of 100 cc / cm ² / sec.
Met.

Comparative Example 3 The Frazier air permeability of Example 2 was 100 cc / cm ² / s.
The ec non-woven fabric was used as it was as an inkjet recording sheet.

Example 4 [Preparation of Nonwoven Fabric] A 40% aqueous dispersion of 80 parts of calcined kaolin and 20 parts of styrene butadiene latex was added to the nonwoven fabric prepared in Example 4 so that the dry solid content was 15 g / m ^2. Was coated with an air knife coater, dried, and calendered to prepare an undercoated nonwoven fabric. The produced Frazier air permeability was 140 cc / cm ² / sec.

[Coating of Ink Receiving Layer] The ultraviolet absorbing cationized polymer of Example 2 was replaced with that of Preparation Example 3, and the ink receiving layer component was an aqueous dispersion having a solid content concentration of 10%.
An ink jet recording sheet was produced in the same manner as in Example 2 except that coating was performed using an air knife coater so that the dry solid content was 5 g / m ² . The Frazier air permeability of the manufactured inkjet recording sheet was 98 cc / cm ² / sec.

Comparative Example 4 The undercoated non-woven fabric prepared in Example 4 was used, the UV absorbing cationic polymer in the ink receiving layer component of Example 4 was not used, and the dry solid content was 3 g / m ² . An inkjet recording sheet was produced in the same manner as in Example 4 except that the coating was performed as described above. The Frazier air permeability of the inkjet recording sheet at this time was 130 cc / cm ² / sec.

Example 5 [Production of Nonwoven Fabric] 60 parts of polyester fiber (fiber diameter 1.4 denier, fiber length 51 mm), polypropylene fiber (fiber diameter 2 to 3 denier, fiber length 38 to 51 mm) 20
Part and 10 parts of polyester-based heat-bonded composite fiber (fiber diameter 2 denier, fiber length 51 mm) were uniformly mixed to prepare a nonwoven fabric having a basis weight of 60 g / m ² by the card method. The Frazier air permeability of the produced nonwoven fabric was 120 cc / cm ² / sec. Further, the produced non-woven fabric was calendered using a thermal calender to obtain the support of Example 5. The Frazier air permeability at this time was 30 cc / cm ² / sec.

[Coating of ink receiving layer] As an ink receiving layer component, 100 parts of alumina hydrate (Cataloid AS-3, manufactured by Catalysts & Chemicals Industries Co., Ltd., primary particle size: about 10 nm), polyvinyl alcohol (PVA 117, PVA 117, (Kuraray Co., Ltd.) 30 parts, and an aqueous dispersion having a solid content concentration of 10% and containing 20 parts of the UV-absorbing cationized polymer of Preparation Example 4 as a main component so as to have a dry solid content of 3 g / m ² using an air knife coater. An ink jet recording sheet was prepared by applying the composition to a sheet, drying, and machine calendering. The inkjet recording sheet produced had a Frazier air permeability of 25 cc / cm ² / sec.
Met.

Comparative Example 5 Instead of the alumina hydrate used in Example 5, 333 parts of a 30% aqueous dispersion of powder silica (Nipsil E220A, manufactured by Nippon Silica Industry Co., Ltd., average particle size 1.0 μm) was used. An inkjet recording sheet was produced in the same manner as in Example 5 except for the above. The ink jet recording sheet produced had a Frazier air permeability of 30 cc / cm ² / sec.

The ink jet recording sheets prepared in Examples 1 to 5 and Comparative Examples 1 to 5 above were evaluated according to the following methods, and the results are shown in Table 1 below.

[Ink Absorbency] Ink absorbency and image sharpness are determined by the boundaries between solid color solid print portions, for example, red print (magenta + yellow) and green print (cyan + yellow).
The degree of ink bleeding at the boundary portion of was visually determined. When the red printed portion and the green printed portion did not overlap and were separated, the characteristics were good, and when the overlapping was large and a black line was formed, the characteristics were bad. If the ink absorption is poor,
Since it significantly impairs the image quality (image sharpness), it does not make any sense even if other characteristics such as image density are good. In addition, as an evaluation criterion, A indicates a good characteristic, B indicates a good practically acceptable range, C indicates a practical problem, and D indicates a poor characteristic.

[Image Density] The image density is a reflection densitometer (Macbeth RD91
8: manufactured by Macbeth). The higher the value, the higher the image density and the better, but normally, 1.20 or more is good.

[Light resistance of image] Regarding the light resistance of the image, an ink jet printer (MJ-700V2C,
Solid printing of magenta ink was performed by using EPSON. The inkjet recording sheet after recording was used with a xenon arc fade meter, Atlas Ci-35f, black panel temperature 63 ° C., relative humidity 65% RH.
The color difference of the magenta ink color before and after the light irradiation for 30 hours under the above environment was measured. The color difference can be defined by the following mathematical formula 1 based on the result of measuring the color of each inkjet recording sheet before and after light irradiation according to L ^* a ^* b ^* (a colorimetric method according to CIE). The larger the color difference, the more the color deterioration occurs. The measurement was performed using a standard light C, CR100 manufactured by Minolta. If the color difference is less than 1.0, it is almost impossible to visually recognize the color difference.

[0076]

## EQU1 ## ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2 where ΔE is the color difference, ΔL ^* and Δa ^* and Δb ^* Is the difference between L ^* and a ^* and b ^* before and after light irradiation.

[Water resistance] With respect to water resistance, a recording sheet solidly printed with each of black ink, cyan, magenta, and yellow ink is dipped in running water for 10 minutes to obtain a residual ratio (residual ratio = optical density after treatment / original image). Was measured. If the residual ratio of the optical density is 90% or more, it is good, and even 85% is a level with no practical problem.

[0078]

[Table 1]

From the results shown in Table 1 above, the ink jet recording sheet of the present invention uses the ultrafine inorganic pigment having a particle size of 100 nm or less and the ultraviolet absorbing cationic polymer, and has a Frazier air permeability of the recording sheet. Since it was within the range of the invention, the image density was high, the ink absorbency and the sharpness were both good, and the light resistance and water resistance of the image were also good.

On the other hand, in the ink jet recording sheets of Example 1 and Comparative Example 1, there was a difference in the Frazier air permeability of the recording sheets, and Comparative Example 1 was inferior in image sharpness.
The inkjet recording sheets of Comparative Example 2 and Comparative Example 5 used large amounts of the ultrafine particle inorganic pigments, and lacked image clarity. In addition, the ink jet recording sheet of Comparative Example 3 does not have any properties when the ink receiving layer is not applied. The inkjet recording sheet of Comparative Example 4 did not use the ultraviolet absorbing cationized polymer of the present invention, but was inferior in light resistance and water resistance of the image.

[0081]

The ink jet recording sheet of the present invention is
Ink jet recording sheet after the ink receiving layer is coated on a non-woven support mainly composed of specific ultrafine particle inorganic pigment and UV absorbing cationized polymer is fragile aerated according to JIS L1096. When the degree is 100 cc / cm ² / sec or less, it is possible to obtain an inkjet recording sheet having excellent recording characteristics and light resistance and a unique texture.

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[Procedure amendment]

[Submission date] March 3, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction content]

Preparation examples of the ultraviolet absorbing cationized polymer are shown below in advance. Preparation Example 1 2- [2'-hydroxy-5 '-(methacryloyloxy) phenyl] benzotriazole (30 g), N, N-diethylaminoethyl acrylate (70 g), ethyl cellosolve (100 g) were added to a Dimroth, a dropping funnel, a thermometer, and nitrogen.
Put into a separable flask equipped with an element introduction tube and a stirrer
Then, while introducing nitrogen from the nitrogen introduction pipe, raise the temperature to 80 ° C.
Warmed. Then, dissolve in a small amount of ethyl cellosolve.
Divide 0.1g of zobisisobutyronitrile into 4 parts, 30 minutes
Dropped between. After dropping, react for 2 hours under nitrogen atmosphere
Then, an ultraviolet absorbent polymer aqueous solution was synthesized. Subsequently, 30 g of monochloroacetic acid was added dropwise over 30 minutes, and the reaction was performed for 2 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an ultraviolet absorbing cationized polymer aqueous solution (solid content 20% by weight) of Preparation Example 1.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

[0057] Preparation Example 4 2-hydroxy-4-methacryloyloxy benzophenone 30 g, N, N-dimethylaminopropyl acrylamide 70 g, ethyl cellosolve 100g used, the preparation
A UV absorber polymer aqueous solution was synthesized in the same manner as in Example 1 . Subsequently, 30 g of diethyl sulfuric acid was added dropwise over 30 minutes, and the reaction was performed for 2 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an ultraviolet absorbing cationic polymer aqueous solution (solid content 20% by weight) of Preparation Example 4.

Claims (3)

[Claims] 1. An ink jet recording sheet comprising an ink-receiving layer coated on a support, wherein the support is made of a non-woven fabric, and the ink-receiving layer component is mainly 100 nm.
Ultraviolet absorbing cationization consisting of a copolymer of an ultrafine inorganic pigment having the following primary particle diameter and a polymerizable vinyl compound having a quaternary ammonium salt group bonded thereto and a polymerizable vinyl compound having a structural unit having an ultraviolet absorbing ability bonded An ink jet recording sheet comprising a polymer and having a Frazier air permeability of 100 cc / cm ² / sec or less defined by JIS L1096 of the recording sheet. 2. The ink jet recording sheet according to claim 1, wherein the non-woven fabric is a wet non-woven fabric. 3. A structural unit having an ultraviolet absorbing ability is 2-
A hydroxybenzophenone residue or a 2-hydroxybenzotriazole residue.
Or the inkjet recording sheet according to 2.