JPH11263066A - Ink jet recording sheet and application agent for formation of this sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To raise the absorptivity and coloring property of ink, and form a stable, high quality printing image by manufacturing the ink receptor layer of an ink jet recording sheet with hydrophilic polyurethane resin, hydrophilic polyurethane resin, hydrophilic polyurethane-polyurea resin, and the like. SOLUTION: At least on one surface of a base material sheet, there is furnished with an ink receptor layer for formation of an ink jet recording sheet. In this instance, a resin component constituting the ink receptor layer is made up of hydrophilic resin having a hydrolytic silyl group in molecule. Although hydrophilic resin is available having a hydrolytic silyl group, from the point of view of introduction of such a group, it is most suitable to be hydrophilic resin selected from hydrophilic polyurethane resin, hydrophilic polyurea resin, and hydrophilic polyurethane-polyurea resin. In addition, hydrophilic resin having a hydrolytic silyl and a tertiary amino group can be used instead of these resins.

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 (hereinafter simply referred to as "recording sheet"), and more particularly to a printed character, picture, pattern, etc. (hereinafter referred to as "printed image" for simplicity). Provides an ink-receiving layer that imparts water resistance and moisture resistance, is excellent in ink absorption and ink color development, gives stable high-quality printed images, and has excellent transportability and blocking resistance in a printer. The present invention relates to a recording sheet and a coating agent for producing the sheet.

[0002]

2. Description of the Related Art An ink jet recording system employs various operating principles, for example, an electrostatic suction system, a system for applying mechanical vibration or displacement to ink by using a piezoelectric element, and heating and bubbling ink to utilize the pressure. In this method, fine droplets of ink are made to fly and adhere to a recording sheet such as paper to record images and characters. High-speed printing is possible, low noise is generated, high-quality printing and As a recording system capable of performing color printing, it has rapidly spread to various uses.

[0003] In such a recording sheet used for ink-jet recording, the ink adhering to the recording sheet causes bleeding or flow, and absorbs the ink onto a support such as paper so that the print quality is not impaired. It is proposed to provide an ink receiving layer containing various pigments and resins as main components so that clear ink dots can be formed, or to use a recording sheet in which the paper itself contains a porous pigment. Have been.

For example, JP-A-57-82085 discloses a recording sheet having an ink receiving layer made of a water-soluble resin containing an inorganic pigment and an organic pigment.
No. 68682 discloses recording sheets each having an ink receiving layer comprising a polyvinyl alcohol copolymer containing finely divided silica and having a silanol group.

[0005] However, with the improvement of the performance of ink-jet recording apparatuses such as high-speed recording, high-definition or full-color recording, and expansion of applications, recording sheets are required to have the following advanced characteristics. It became so. (1) the ink absorption is fast and the ink absorption capacity is large; (2) the color development of the ink is high; (3) the surface strength of the ink receiving layer is high; and (4) the support has water resistance. (5) that the ink receiving layer has excellent image storability such as water resistance and ozone resistance after image printing; and (6) that the ink receiving layer has excellent image storability after image printing.
For example, the quality of the ink receiving layer does not change with time.

Conventionally, a porous pigment or a water-soluble resin having excellent ink absorbency has been used as a component of an ink receiving layer provided on a recording sheet in order to satisfy these requirements, or to improve the water resistance of the ink receiving layer. Use latex,
Further, the use and use of a synthetic paper or a plastic sheet having water resistance for the support itself have been studied and implemented.

However, when paper is used for the support or when only the aqueous resin is used as the ink receiving layer, the water resistance of the ink receiving layer is poor, and the printed portion of the ink is bleeding.
There is a disadvantage that the formed image is inferior in sharpness. On the other hand, in a recording sheet using a synthetic paper or a plastic film for the support, or using a latex for the resin forming the ink receiving layer, the adhesiveness between the ink receiving layer and the support and the absorption of the ink in the ink receiving layer. There is a problem in the properties and drying properties of the applied ink.

Generally, in order to improve the water resistance and moisture resistance of a printed image on a recording sheet, a method of providing a protective layer on the ink receiving layer or adding a mordant or the like to the ink receiving layer has been used. As a method of providing a protective layer, a method of coating a hydrophobic resin on the ink receiving layer after printing an image or a method of laminating a film can improve water resistance and moisture resistance, but in such a method, Since multiple steps are required, it is not preferable in terms of cost when forming an image.

The method of adding a mordant or the like to the ink receiving layer is such that the dye used in the color ink for ink jet is a direct dye or an acidic dye, and the dye molecule has an anionic carboxyl group or a sulfonic acid group. A cationic mordant or the like is added to the ink image-receiving layer in order to improve the water resistance and fixability of an image formed by these dyes, but the bond between the mordant and the dye is moisture. Since ionic bonds are easily dissociated in the presence of, there is a limit in water resistance and moisture resistance in an image formed in this way.

[0010]

DISCLOSURE OF THE INVENTION The present inventors have solved the problems of the conventional recording sheet as described above, and formed a printed image having excellent water resistance and moisture resistance, as well as ink absorption and ink absorption. As a result of various studies to develop a recording sheet that is excellent in color development, gives a stable high-quality printed image, and is excellent in transportability and blocking resistance in a printer, the recording sheet is made of a specific hydrophilic resin. It has been found that the above object can be achieved by forming an ink receiving layer, and the present invention has been completed.

[0011]

That is, according to a first aspect of the present invention, in a recording sheet having at least one ink-receiving layer provided on at least one surface of a base sheet, a resin component constituting the ink-receiving layer comprises: A recording sheet comprising a hydrophilic resin having a hydrolyzable silyl group in a molecule (hereinafter, referred to as a first resin).
A recording sheet using a hydrophilic resin having a hydrolyzable silyl group and a tertiary amino group in a molecule (hereinafter referred to as a second resin) instead of the first resin in the invention, and The invention provides a recording method using a hydrophilic resin having a hydrolyzable silyl group, a tertiary amino group and a polysiloxane segment in a molecule (hereinafter referred to as a third resin) instead of the first resin in the first invention. It is a sheet.

[0012]

Next, the present invention will be described in more detail with reference to preferred embodiments. The recording sheet of the first invention is characterized in that at least one ink receiving layer provided on at least one side of the base sheet is made of a first resin. In the recording sheet of the second invention, at least one ink receiving layer provided on at least one side of the base sheet is formed of the second sheet.
The resin is characterized by the following. The recording sheet of the third invention is characterized in that at least one ink receiving layer provided on at least one side of the base sheet is made of a third resin. The term “hydrophilic resin” in the present invention means a polymer having a hydrophilic group in its molecule, but insoluble in water or hot water, such as polyvinyl alcohol, polyvinyl pyrrolidone, and cellulose derivatives. It is distinguished from a water-soluble resin.

[First Invention] In the first invention of the present invention, the following formula (I) and / or (II) can be obtained by using the first resin as a resin component constituting the ink receiving layer. As shown in the above, the crosslinking of the resin with moisture improves the fixing property of the dye and the water resistance of the ink receiving layer, and the crosslinking also improves the surface strength, blocking resistance, printer transportability, etc. of the ink receiving layer. it is conceivable that.

[0014]

The crosslinking of the resin component of the ink receiving layer is caused by moisture. However, the supply of water for crosslinking is not particularly limited, and the method of adding moisture when forming the receiving layer, the resin constituting the receiving layer is hydrophilic. Therefore, either of a method utilizing the moisture in the air absorbed by the ink receiving layer and a method utilizing the moisture of the aqueous ink at the time of printing may be used. Crosslinking is performed by converting a hydrolyzable silyl group into a silanol group by moisture as described above, and this silanol group is condensed, so that a catalyst is added to the ink receiving layer in order to promote silanol condensation. It is preferable to keep it. As such a catalyst, a tin-based carboxylate, an acidic catalyst and a basic catalyst are generally preferred, and the use amount thereof is preferably in the range of 0.0001 to 10% by weight based on the hydrophilic resin.

The hydrophilic resin which is the first resin constituting the ink receiving layer in the present invention is not particularly limited as long as it is a hydrophilic resin having a hydrolyzable silyl group at any position. From the viewpoint of introducing a group, at least one hydrophilic resin selected from a hydrophilic polyurethane resin, a hydrophilic polyurea resin, and a hydrophilic polyurethane-polyurea resin is preferable.

As a method for introducing a hydrolyzable silyl group into a hydrophilic resin, a silane coupling agent having a reactive group and a hydrolyzable group or a reaction product of the silane coupling agent and an organic polyisocyanate is used. And a method of reacting a hydrophilic resin with a reactive group in a molecular terminal and / or a molecular side chain of the hydrophilic resin. Examples of typical hydrolyzable groups in the hydrolyzable silyl group of the silane coupling agent are alkoxy groups such as methoxy group, ethoxy group and methoxyethoxy group, but other hydrolyzable groups can also be used. Of course.

Examples of the silane coupling agent having a reactive group and a hydrolyzable group used in the present invention include the following compounds. (1) A silane coupling agent having a free isocyanate group represented by the following general formula (1). (Wherein, R ₁ is a lower alkyl group, R ₂ is a lower alkyl group or a lower alkoxy group. X is a divalent organic group, and preferred are a C ₀ -C ₅₀ alkylene group, an aromatic or aliphatic group. And two groups out of R ₁ , R ₂ and X are —N—, —O—, —CO—, —COO—, —NHC
O -, - S -, - SO- or -SO ₂ - may be linked by a linking group such as. m = 0 to 2; n = 3-m;
m + n = 3)

Preferred specific examples of the silane coupling agent having a free isocyanate group are as follows.

(2) a reaction product of a silane coupling agent having a reactive group and an organic polyisocyanate,
The product has at least one free isocyanate group in the molecule. The silane coupling agent having a reactive group used at this time includes those represented by the following general formula (2). (Wherein, Y is _{-NH -, - NR 3 -,} - O-, or -S
And R ₁ , R ₂ , X, m and n are as defined above. R ₃ is a lower alkyl group. )

Preferred specific examples of the silane coupling agent having a reactive group are as follows.

[0022]

The silane coupling agents as described above are examples of preferred silane coupling agents used in the present invention, and the present invention is not limited to the use of these exemplified coupling agents. Therefore, not only the above-mentioned compounds but also other known silane coupling agents that are currently commercially available and easily available from the market can be used in the present invention.

An example of a method for introducing a hydrolyzable silyl group into a molecular terminal and / or a molecular side chain of a hydrophilic resin using the above silane coupling agent is illustrated as follows, for example. (1) Introduction to molecular terminals (Wherein R ₁ , R ₂ , X, Y, m and n are the same as above, and [P] is a hydrophilic polyurethane containing at least two urethane bonds and / or urea bonds per polymer molecule; Represents hydrophilic polyurea or hydrophilic polyurethane-polyurea.)

(2) Introduction into molecular side chains (Wherein, Z is, -O -, - S -, - NR 3 - or -NH
And R ₁ , R ₂ , R ₃ , [P], m and n are the same as above. The hydrolyzable silyl group can be introduced into the molecular terminal and / or the molecular side chain of the hydrophilic resin by a method other than the above, and the introduction method is not limited to the above examples. is there.

In the above reaction, the molecular terminals and / or
Or a hydrophilic resin in which a hydrolyzable silyl group is introduced into a molecular side chain, a particularly preferred hydrophilic polyurethane resin,
The hydrophilic polyurea resin and the hydrophilic polyurethane-polyurea resin can be obtained according to a conventionally known synthesis (polymerization) method of these resins, and the synthesis method and raw material components of these resins are not particularly limited. . [Second invention]

In the second invention of the present invention, the second resin is used. In the second resin, the tertiary amino group introduced into the resin molecule forms an ionic bond between the dye molecule and the resin. As a result, the fixing property of the dye and the water resistance of the formed image are reduced. It is thought to improve.

Considering that the bond between the dye and the tertiary amino group is an ionic bond, as in the conventional case where a mordant is used in the ink receiving layer, the water resistance of the formed image is the same as that of the prior art. Although the reason for the improvement is not clear, the resin used in the present invention is hydrophilic but water-insoluble,
There are also many hydrophobic moieties in the molecule, and after ionic bonds are formed between the tertiary amino groups in the resin and the dye, the hydrophobic moieties in the resin become It is believed that the water resistance of the formed image is improved as compared with the prior art because of the surroundings.

Also, unlike the prior art using the above mordant, in the present invention, the tertiary amino group in the resin molecule forms an ionic bond with the dye, while the hydrophobic portion in the resin molecule forms an ionic bond. It has an effect of surrounding the dye, which is considered to be the cause of improving the water resistance of the formed image.

In the present invention, a method for introducing a tertiary amino group into the resin in addition to the hydrolyzable silyl group includes one or more reactive groups such as an amino group and an epoxy group in the molecule. Having a group, a hydroxyl group, a mercapto group, a carboxyl group, an alkoxy group, an acid halide group, a carboxylester group, an acid anhydride group, a carbon-carbon unsaturated group,
And a compound having a tertiary amino group in the molecule,
Examples include a method of using as a part of a synthesis (polymerization) raw material of the second resin, and (b) a method of reacting with a reactive group in the first resin.

Preferred examples of such a tertiary amino group-containing compound having a reactive group include compounds represented by the following general formulas (3) to (5). (R ₃ in the formula is an alkyl group having 20 or less carbon atoms, an alicyclic group, an aromatic group which may have a substituent such as a halogen element or an alkyl group; R ₄ and R ₅ are lower alkylene Group or -O-, -CO-, -COO-, -NHCO-, -S
-, - SO -, - SO ₂ - a lower alkylene group having a linking group such as; X and Y may be the same or different, -
OH, represents _{-COOH, -NH 2, -NHR 3,} -SH , etc., or an epoxy group that can be induced in these groups, an alkoxy group, an acid halide group, an acid anhydride group or a carboxylic ester group, respectively. )

[0032] _{(R 3, R 4, R} 5, X and Y in the formula is the same as defined above, may form a cyclic structure with two R ₃ together, R ₆
Is _{- (CH 2) n - (} n is 0 to 20 integer) are the same as, or R ₄ or R _5, Z represents CH or N. )

[0033] (X and Y in the formula are the same as described above, and W represents a heterocycle containing nitrogen, a heterocycle containing nitrogen and oxygen, or a heterocycle containing nitrogen and sulfur.)

Specific examples of the compounds represented by formulas (3), (4) and (5) include the following.
N, N-dihydroxyethyl-methylamine, N, N-
Dihydroxyethyl-ethylamine, N, N-dihydroxyethyl-isopropylamine, N, N-dihydroxyethyl-n-butylamine, N, N-dihydroxyethyl-t-butylamine, methyliminobispropylamine, N, N-dihydroxyethyl Aniline, N, N
-Dihydroxyethyl-m-toluidine, N, N-dihydroxyethyl-p-toluidine, N, N-dihydroxyethyl-m-chloroaniline, N, N-dihydroxyethylbenzylamine, N, N-dimethyl-N'N ' −
Dihydroxyethyl-1,3-diaminopropane, N,
N-diethyl-N ′, N′-dihydroxyethyl-1,
3-diaminopropane, N-hydroxyethyl-piperazine, N, N′-dihydroxyethyl-piperazine, N
-Hydroxyethoxyethyl-piperazine, 1,4-bisaminopropyl-piperazine, N-aminopropyl-
Piperazine, dipicolinic acid, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,6-diamino-4-methylpyridine, 2,6
-Dihydroxypyridine, 2,6-pyridine-dimethanol, 2- (4-pyridyl) -4,6-dihydroxypyrimidine, 2,6-diaminotriazine, 2,5-diaminotriazole, 2,5-diaminooxazole and the like. is there.

Further, ethylene oxide adducts and propylene oxide adducts of these tertiary amino compounds can also be used in the present invention. Examples of such an adduct include the following compounds.

[0036] (In the formula, m represents an integer of 1 to 60, and n represents an integer of 1 to 6.)

In the present invention, the second resin, particularly preferably a hydrophilic polyurethane resin, a hydrophilic polyurea resin and a hydrophilic polyurethane-polyurea resin, is obtained according to a conventionally known synthesis (polymerization) method of these resins. The synthesis method and raw material components other than those described above are not particularly limited. [Third invention]

In the third invention of the present invention, a third resin having a polysiloxane segment introduced into the second resin is used. In the third resin, since the polysiloxane segment introduced into the resin is inherently hydrophobic (water-repellent), it is difficult to use the resin having the segment for forming the ink receiving layer. Good results should not be expected for ink absorption.

However, the surface of the ink receiving layer made of the third resin containing the polysiloxane segment in a specific range is completely covered with the polysiloxane segment in a dry state, but the ink receiving layer is immersed in water or the like. In such a case, it is known that the polysiloxane segment is buried in the resin, that is, it has an environmental response (see Polymer Collection, Vol. 48 [No. 4], p. 227 (19)
1991)).

The third invention of the present invention utilizes this phenomenon. When the ink receiving layer is formed using the third resin containing the above polysiloxane segment, unexpectedly, the ink absorbing property is improved. And a recording sheet that imparts good water resistance to the formed image and has transportability in a printer. That is, by appropriately controlling the polysiloxane segment content in the resin to form an ink receiving layer, due to environmental response, when printing with aqueous ink, the surface of the ink receiving layer shows hydrophilicity, The polysiloxane segment of the resin acts so as to wrap the dye bonded to the resin by the ionic bond between the tertiary amino group and the dye introduced into the hydrophilic resin. By covering the surface of the subsequent ink receiving layer with the polysiloxane segment, a recording sheet excellent in surface lubricity, water resistance, transportability in a printer, blocking resistance, and the like can be obtained.

As the third resin used in the present invention, any resin having a polysiloxane segment in addition to the silyl group and the tertiary amino group in the molecule can be used. Hydrophilic polyurethane resin having a hydrophilic polyurea resin, hydrophilic polyurethane-
Examples include a polyurea resin, a hydrophilic polyamide resin, a hydrophilic polyester resin, a hydrophilic acrylic resin, and a hydrophilic epoxy resin. Among them, preferred hydrophilic resins are hydrophilic polyurethane resin, hydrophilic polyurea resin,
Hydrophilic polyurethane-polyurea resin and hydrophilic polyamide resin.

As a method for introducing a polysiloxane segment into the second resin, one or more reactive groups such as an amino group, an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, etc. A method of synthesizing (polymerizing) a hydrophilic resin by using a polysiloxane compound having the above as a part of the raw material component of the third resin. Preferred examples of the polysiloxane compound having such a reactive group include the following compounds.

(1) Amino-modified polysiloxane compound

[0044]

[0045]

[0046]

(2) Epoxy-modified polysiloxane compound

[0048]

[0049]

(3) Alcohol-modified polysiloxane compound

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

(4) Mercapto-modified polysiloxane compound

[0058]

(5) Carboxyl-modified polysiloxane compound

[0060]

[0061]

A hydrophilic polyurethane resin having a hydrolyzable silyl group at a molecular terminal and / or a molecular side chain obtained from the raw material component and having a tertiary amino group and a polysiloxane segment in the molecule, The hydrophilic polyurea resin and the hydrophilic polyurethane-polyurea resin can be obtained according to a conventionally known synthesis method of these resins,
The method for synthesizing these resins and the synthesis raw material components other than those described above are not particularly limited.

Preferable examples of the other synthetic raw materials other than the above-mentioned first to third resins will be described in more detail. The preferred hydrophilic compound used to obtain the above-mentioned hydrophilic resin has a terminal group of a hydroxyl group. , An amino group, a carboxyl group, etc., having a molecular weight of 100 to 80.
A range of 00 is preferred.

Examples of the compound having a hydroxyl group at the end and having hydrophilicity include polyethylene glycol, polyethylene glycol / polytetramethylene glycol copolymer polyol, polyethylene glycol / polypropylene glycol copolymer polyol, polyethylene glycol adipate, polyethylene glycol succinate, and polyethylene. Glycol / poly-ε-caprolactone copolymer polyol, polyethylene glycol / polyγ-valerolactone copolymer polyol, and the like.

Examples of those having an amino group at the terminal and having hydrophilicity include polyethylene oxide diamine, polyethylene oxide propylene oxide diamine, polyethylene oxide triamine, and polyethylene oxide propylene oxide triamine. In addition to the above compounds, an ethylene oxide adduct having a carboxyl group or a vinyl group can also be used. If necessary, other polyols, polyamines and polycarboxylic compounds having no hydrophilicity can be used together with the above-mentioned raw material components in order to impart other properties.

The first resin according to the first invention, the second resin according to the second invention, obtained from the above-mentioned materials,
The preferred weight average molecular weight of the third resin in the third invention is about 5,000 to 500,000, and the more preferred weight average molecular weight is 30,000 to 200,000. When these resins are synthesized by a polymerization reaction using the above-mentioned raw material components, any of those synthesized without a solvent and those synthesized in water or an organic solvent may be used. In the production process, a resin solution obtained by synthesizing the above resin in an organic solvent or water that can be used when forming the ink receiving layer is advantageous because it can be directly used for forming the ink receiving layer.

The hydrolyzable silyl group in the first resin may be contained in one or both of a side chain (pendant) and the main chain, and the content in the resin is a raw material. The compound having a hydrolyzable silyl group is preferably in the range of 1 to 40% by weight of the whole. Further, the number of hydrolyzable silyl groups is 0.001 to 10.0 equivalents / g, preferably 0.01 to 1.0 equivalents / g, that is, about 0.001 equivalent per 1,000 weight average molecular weight of the hydrophilic resin. The ratio is preferably 001 to 10, preferably 0.01 to 1.0.

When the content of the hydrolyzable silyl group is less than the above range, the formed ink receiving layer does not sufficiently exhibit the desired properties such as blocking resistance, water resistance, and moisture resistance, which are the objectives of the present invention. On the other hand, if it exceeds the above range, the hydrophilic portion in the hydrophilic resin is reduced, and the cross-linked structure of the resin increases the water resistance of the ink receiving layer, thereby deteriorating the water absorbing performance and the quality of the printed image. It is not preferable.

The content of the silyl group in the second resin is the same as that of the first resin, and the tertiary amino group is
It may be contained in one or both of the side chain (pendant) and the main chain, and the content in the resin is preferably in the range of 1 to 60% by weight of the tertiary amino compound as the raw material. . When the content of the tertiary amino compound is less than the above range, the intended purpose of the present invention, such as water resistance and moisture resistance of the ink receiving layer, becomes insufficient. The decrease in the ratio is not preferable because the water repellency of the ink receiving layer becomes strong, and the water absorbing performance with respect to the aqueous ink and the quality of the printed image formed deteriorate.

The number of tertiary amino groups is from 0.1 to 50 equivalents / g, preferably from 0.2 to 10.0 equivalents / g, that is,
About 1 to 5 per 1,000 weight average molecular weight of hydrophilic resin
It is preferable that the ratio is 0, preferably 2 to 10. When the number of tertiary amino groups is less than the above range, the fixing property of the dye and the water resistance of the formed image are insufficient,
On the other hand, if the number of tertiary amino groups exceeds the above range, the water repellency of the resin due to the decrease in the proportion of the hydrophilic portion in the resin becomes strong, and there is a problem in terms of ink absorption of the ink receiving layer formed. There is.

The silyl group in the third resin and the third
The primary amino group is the same as described above, and the polysiloxane segment may be any one of a side chain (pendant) and a main chain,
Or both may be contained, and the content of the segment in the resin is 0.1 to 10% by weight of the whole, especially 0.5 to 10% by weight.
A range of 10% by weight is preferred. When the content of the polysiloxane segment is less than 0.1% by weight, the surface properties of the recording sheet such as water resistance, running property, transportability, blocking property, etc., which are the objects of the present invention, become insufficient, and on the other hand, 10%.
If the content is more than 10% by weight, the water repellency of the polysiloxane segment is increased, and the water absorption performance of the formed ink receiving layer for aqueous ink and the printed image formed on the ink receiving layer are undesirably deteriorated.

As the base sheet of the recording sheet of the present invention, paper, plastic film, sheet glass and the like are used, but are not particularly limited. As paper,
For example, high quality paper, medium quality paper, coated paper, cast coated paper and the like can be mentioned. Also, as a plastic film,
Examples of the sheet include polyester, cellulose triacetate, polycarbonate, polyvinyl chloride, polypropylene, polyamide, polystyrene, polyethylene, and polymethyl methacrylate having a thickness of 50 to 250 μm. In addition, these base sheets may have, as necessary, a primer layer for improving the adhesion of the ink receiving layer to the base sheet, and an anti-curl layer on the back surface on the ink receiving layer side and a lubricity for improving the coefficient of friction. Layers can also be provided.

As the resin component constituting the ink receiving layer, the above-mentioned hydrophilic resin can be used alone.
In order to adjust the hydrophilicity and / or water absorption of the ink receiving layer depending on the ink composition used for ink jet recording, or to apply these to the ink receiving layer, the hydrophilic resin is combined with another water-soluble resin. Can also be used. As the water-soluble resin used here, for example, polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, CMC, cellulose derivative,
Examples include polyvinylpyrrolidone, starch, cationic starch, gelatin, casein, and acrylic acid polymers.

Further, in order to further impart water resistance and durability to the ink receiving layer and the printed image formed thereon, a hydrophobic resin can be used in combination with the hydrophilic resin. As the hydrophobic resin used here, for example, polyester resin, polyvinyl chloride resin, polystyrene resin, polymethyl methacrylate resin, polycarbonate resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, acrylonitrile-styrene copolymer resin , Polyvinyl butyral resin, polyamide resin, epoxy resin, urea resin, melamine resin and the like.

Further, an inorganic or organic pigment or a resin particle is added to the ink receiving layer for the purpose of improving the ink absorbing property, the dye fixing property, the coloring property of the dye, the blocking property and the water resistance of the ink receiving layer. You can also. Examples of such pigments and resin particles include, for example, kaolin, delamikaolin, aluminum hydroxide, silica, diatomaceous earth, calcium carbonate, talc, titanium oxide, calcium sulfate, barium sulfate, zinc oxide, alumina, calcium silicate, magnesium silicate, Mineral pigments and porous pigments such as colloidal silica, zeolite, bentonite, sericite and lithopone; fine particles and porous fine particles such as plastic pigments such as polystyrene resin, urea resin, acrylic resin, melamine resin, benzoguanamine resin and polyurethane resin;
Depending on the quality design of the recording sheet, one or more kinds can be appropriately selected from known pigments and resin particles such as hollow particles made of these materials.

Further, if necessary, the ink receiving layer may contain
In addition to such resins and pigments, thickeners, release agents, penetrants,
Wetting agents, thermal gelling agents, sizing agents, defoamers, defoamers, foaming agents, coloring agents, optical brighteners, ultraviolet absorbers, antioxidants,
One or more auxiliaries such as a quencher, a preservative, an antistatic agent, a cross-linking agent, a dispersant, a lubricant, a plasticizer, a pH adjuster, a fluidity improver, a solidification accelerator, and a water resistance agent. It is also possible to mix.

Next, the formation of the ink receiving layer will be described. First, a hydrophilic resin having a hydrolyzable silyl group in the molecule, a hydrophilic resin having a hydrolyzable silyl group and a tertiary amino group, or a hydrolyzable silyl group, a tertiary amino group and a polysiloxane segment And a hydrophilic resin alone or, if necessary, together with another resin, dissolved or dispersed in various organic solvents or water, and further added and mixed as necessary with the above pigment or resin particles and various auxiliaries to form a coating solution. Is prepared. Examples of the solvent used for preparing the coating solution include water (in this case, the coating solution is a dispersion or an emulsion), methanol, ethanol, propanol, acetone, methyl ethyl ketone, toluene, xylene, ethyl acetate, ethyl butyrate, and dioxane. , Pyrrolidone, dimethylformamide,
Examples include formamide, dimethyl sulfoxide, and the like, and mixtures thereof. The concentration of the hydrophilic resin in the coating solution is usually about 5 to 50% by weight, preferably about 10 to 30% by weight. The viscosity of the coating solution is about 1 to 500 dPa · s, preferably about 10 to 200 d in consideration of suitability for coating.
Pa · s. The total amount of one or more of the above various pigments is usually from 0 to 5 per 100 parts by weight of the hydrophilic resin.
Parts by weight, preferably about 0.5 to 20 parts by weight.

Examples of the method of applying the coating solution to the base sheet include gravure coating, direct or reverse roll coating, wire bar coating, air knife coating, curtain coating, blade coating, rod coating, die coating, and the like. The recording sheet of the present invention can be obtained by coating and drying at least one surface of the base sheet so as to have a predetermined dry thickness. After applying the above coating liquid, machine calendar, super calendar,
The surface may be finished using a calender such as a soft calender.

[0079] The coating amount of the coating solution, typically, 0.5 to 50 g / m ² by dry weight, and preferably from 3 to 30 g / m ² approximately. If the coating amount is less than 0.5 g / m ² , the ink absorbing layer formed will have insufficient ink absorbency, and
If it exceeds 0 g / m ² , the effects of the present invention become saturated, which is not only uneconomical, but also causes the recording sheet to be easily broken, cracked or curled.

[0080]

EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples. In the following examples, parts and percentages are by weight unless otherwise specified. In the following, the first invention, the second invention, and the third invention will be specifically described with reference examples, examples, and comparative examples, respectively. [First invention] Reference Example 1 (Example of producing molecular side chain type hydrolyzable silyl group-polyurethane resin) Polyethylene glycol (molecular weight 2,04
0) 150 parts, 1,3-butylene glycol 15 parts
Dissolve in a mixed solvent of 125 parts of toluene and 100 parts of methyl ethyl ketone, and add 58 parts of diphenylmethane diisocyanate at 70 ° C. with good stirring. After the addition was completed, 100 parts of methyl ethyl ketone was further added,
For 6 hours. No hydroxyl group absorption was observed in the infrared absorption spectrum of the obtained resin, and the pyridine method (J
No hydroxyl group was confirmed by quantification according to ISK-0070 2.5). Next, a silane coupling agent having an isocyanate group [(C ₂ H ₅ O) ₃
8 parts of Si (CH ₂ ) ₃ NCO] was added and reacted at 80 ° C. for 8 hours. After confirming that the isocyanate group had disappeared, the solid content concentration was adjusted to 35%, and the first resin A solution was obtained. This resin solution had a viscosity of 380 dPa · s (25 ° C.).

Reference Example 2 (Production example of molecular-terminal hydrolyzable silyl group-polyurea resin) In a reactor, 38 parts of hydrogenated MDI were dissolved in 100 parts of dimethylformamide, and the mixture was stirred while maintaining the internal temperature at 20 ° C. While polyethylene oxide diamine dissolved in 50 parts of dimethylformamide ("Jeffamine ED":
Trade name; manufactured by Texaco Chemical Company; molecular weight: 2,000) 1
50 parts were gradually added dropwise, and after the completion of the addition, the mixture was reacted at 50 ° C. for 3 hours to obtain an isocyanate-terminated polyurea resin. The internal temperature was again raised to 20 ° C., and 2.8 parts of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone were gradually added dropwise. After the completion of the addition, the mixture was reacted at the same temperature for 1 hour. Next, 14 parts of γ-aminopropyltriethoxysilane dissolved in 100 parts of methyl ethyl ketone were gradually added dropwise, and reacted at 30 ° C. for 1 hour. After confirming that the isocyanate group had disappeared, the solid fraction was removed. Adjust the concentration to 35% and use another primary
To obtain a resin solution. This resin solution is 230dPa · s
(25 ° C.).

REFERENCE EXAMPLE 3 (Production example of molecular-terminal / side-chain type hydrolyzable silyl group-polyurethane-polyurea resin) (1) Production of isocyanate-terminated silane coupling agent Addition of hexamethylene diisocyanate and water in a reaction vessel 270 parts of a product (“Duranate 24A-100”: trade name; manufactured by Asahi Kasei Corporation, NCO% = 23.5) is stirred well at 25 ° C., and 111 parts of γ-aminopropyltriethoxysilane is gradually added dropwise thereto. To give a colorless transparent viscous liquid product (I). The product obtained has 10.5% of free isocyanate groups (theoretical value (the amount of stoichiometrically introduced groups when the reaction proceeds 100%): 11.2%). It seems that the compound has the following structure.

(2) Production of molecular terminal / side chain type hydrolyzable silyl group-polyurethane-polyurea resin In a reaction vessel, 8 parts of the above viscous liquid product (I) and 46 parts of toluene diisocyanate were added to 150 parts of dimethyl Polyethylene glycol (molecular weight 2,040) 15 dissolved in formamide and dissolved in 100 parts of methyl ethyl ketone
0 parts were added, and 6 parts of 1,3-butylene glycol were further added and reacted at 80 ° C. for 5 hours to obtain an isocyanate-terminated polyurethane resin.

While maintaining the internal temperature at 20 ° C., 7 parts of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone were gradually added dropwise, and after completion of the addition, the mixture was reacted at the same temperature for 1 hour. Further dissolved in 100 parts of methyl ethyl ketone
Part of γ-aminopropyltriethoxysilane was gradually added dropwise, and the mixture was reacted at 30 ° C. for 1 hour. After confirming that the isocyanate group had disappeared, the solid component concentration was adjusted to 35%. A solution of the first resin was obtained. This solution is 3
It had a viscosity of 30 dPa · s (25 ° C.).

Reference Example 4 (Production Example of Polyurethane Resin Used in Comparative Example 1) A polyurethane resin solution was obtained by the same material and formulation as in Reference Example 1 except that a silane coupling agent having an isocyanate group was not used. The solution had a solids content of 35% and
It had a viscosity of 0 dPa · s (25 ° C.).

Reference Example 5 (Production Example of Polyurea Resin Used in Comparative Example 2) A polyurea resin solution was obtained by the same material and formulation as in Reference Example 2 except that γ-aminopropyltriethoxysilane was not used. This solution has a solid content of 35% and 260 dPa ·
s (25 ° C.).

Reference Example 6 (Production Example of Polyurethane-Polyurea Resin Used in Comparative Example 3) Reference Example 3 except that an isocyanate-terminated silane coupling agent and γ-aminopropyltriethoxysilane were not used.
A polyurethane-polyurea resin solution was obtained according to the same materials and formulation as described above. This solution has a solid content of 35% and 220 dP
It had a viscosity of a · s (25 ° C.).

The weight-average molecular weights of the resins obtained in Reference Examples 1 to 6 and the equivalents of the hydrolyzable silyl groups were as shown in Table 1 below. Table 1

Examples 1 to 3 In each of the examples, 40 parts of the resin obtained in the corresponding reference example among reference examples 1 to 3 and tin octylate 0.005
Part, fine-particle synthetic amorphous silica (BET specific surface area 300m
² / g, 100 parts of Mizusawa Chemical Industry Co., Ltd.) and 0.2 parts of a dispersant (sodium polypyrophosphate) were dispersed and mixed with a mixed solvent of methyl ethyl ketone / toluene to adjust the solid content to 15%. Three types of coating liquids of the invention were obtained. This coating solution is applied to high-quality paper having a basis weight of 35 g / m ^{2 by} an air knife coater so that the solid content is 10 g / m ² , dried, and subjected to a super calender finish at a linear pressure of 200 kg / cm to form an ink. Forming a receiving layer, Examples 1-3
Of the present invention were obtained.

Comparative Examples 1 to 3 In each Comparative Example, 40 parts of the resin obtained in the corresponding Reference Example among Reference Examples 4 to 6, and fine-particle synthetic amorphous silica (B
(ET specific surface area 300 m ² / g, manufactured by Mizusawa Chemical Industry) 100
And 0.2 part of a dispersant (sodium polypyrophosphate) were dispersed and mixed with a mixed solvent of methyl ethyl ketone / toluene to adjust the solid content to 15% to obtain three types of coating liquids for forming an ink receiving layer. This coating solution was applied to a high quality paper having a basis weight of 35 g / m ^{2 by} an air knife coater to obtain a solid coating amount of 10 g / m 2.
² and was applied and dried so that a linear pressure 200 Kg / cm
To form an ink receiving layer, thereby obtaining three types of recording sheets of Comparative Examples 1 to 3.

Using the six types of recording sheets obtained as described above, an ink jet printer for printing and recording with an ink containing a water-soluble dye was used to print and record using four colors of yellow, magenta, cyan and black. The following items were evaluated. Table 2 shows the evaluation results.

[Ink Absorption] The number of seconds until the printed ink dries is measured. The ink absorbency is indicated by the following index. ：: 5 seconds or less. Δ: 6 to 10 seconds. X: 11 seconds or more.

[Color Visibility] After printing a color image with the above printer, the color vividness of the obtained color image is visually observed, and the color vividness is indicated by the following index. ：: Good. Δ: Normal. ×: Bad.

[Bleeding Resistance] The degree of bleeding and flowing out of the ink at the overlapping printing boundary portion between magenta and cyan was visually observed, and the bleeding resistance was indicated by the following index. ：: Good. Δ: Normal. ×: Bad.

[Water Resistance of Receptor Layer] Water is applied to the ink-receiving layer, and the state of peeling of the receptor layer when the water is wiped off at a constant finger pressure is visually observed. . ：: No change. Δ: The surface state changes. ×: Peeled.

[Water Resistance of Printed Image] After printing with a printer, the recording sheet is immersed in water for 10 minutes, and then, after drying at room temperature, bleeding of the recorded image and changes in color development are visually observed. Is indicated by the following index. ：: No change. Δ: Discoloration is partially observed. X: Discoloration.

Each of the resin solutions obtained in Reference Examples 1 to 6 was dried on a 100 μm PET film to a thickness of 20 μm.
It was applied to a thickness of μm to prepare a transparent sheet. Perform print recording with an inkjet printer in the same manner as above,
Each item was evaluated by the following method.

[Blocking property] An untreated PET film was superimposed on the resin-coated surface of each transparent sheet.
Untreated P after applying a load of 9MPa and left at 40 ° C for 1 day
The ET film was removed, and the blocking property of the transparent film was visually observed. ：: No blocking property. Δ: Slight blocking property. X: There is blocking property.

[Printer transportability] The printer transportability of each transparent sheet during printing and recording with an ink jet printer was observed, and is indicated by the following index. ：: Good transportability. Δ: Slight noise is generated. ×: Poor transportability. [Water resistance of printed image] After printing each transparent sheet with a printer, the recording sheet was immersed in water for 24 hours, and then dried at room temperature, and visually observed for bleeding of the recorded image and change in color development. Indicated by ：: No change. Δ: Discoloration is observed. X: The dye is completely dissolved and the image disappears.

Table 2 As described above, according to the first aspect of the present invention, a high-quality print image is provided, and further, the ink receiving layer and the print image are excellent in water resistance and moisture resistance, and transportability and blocking resistance in a printer. An ink jet recording sheet having excellent properties is provided.

[Second Invention] Reference Example 1 (Production Example of Polyurethane Resin Containing Hydrolytic Silyl Group-Tertiary Amino Group Containing Molecular Side Chain Type) Polyethylene glycol (molecular weight 2,04
0) 150 parts, 1,3-butylene glycol 7 parts, N-
15 parts of methyldiethanolamine are dissolved in a mixed solvent of 135 parts of toluene and 100 parts of methyl ethyl ketone, and 69 parts of diphenylmethane diisocyanate is added while stirring well at 70 ° C. After the addition is completed, 100 parts of methyl ethyl ketone is further added, and the mixture is reacted at 80 ° C. for 6 hours. No hydroxyl group absorption was observed in the infrared absorption spectrum of the obtained resin, and the pyridine method (JISK-0070)
No hydroxyl group was confirmed by the quantification according to 2.5). Next, 8 parts of a silane coupling agent having an isocyanate group [(C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NCO] was added and reacted at 80 ° C. for 8 hours to confirm that the isocyanate group had disappeared. After that, the concentration of the solid component was adjusted to 35% to obtain a second resin solution. This solution is 330dPa
s (25 ° C.).

Reference Example 2 (Production example of polyurea resin containing molecular-terminal hydrolyzable silyl group-tertiary amino group) In a reaction vessel, 71 parts of hydrogenated MDI were dissolved in 200 parts of dimethylformamide, and the internal temperature was reduced. While maintaining the temperature at 20 ° C. and stirring thoroughly, polyethylene oxide diamine dissolved in 50 parts of dimethylformamide (“Jeffamine ED”: trade name; manufactured by Texaco Chemical Company; molecular weight 2,0)
00) 150 parts were gradually added dropwise, and after the completion of the addition, 1 part was added at 50 ° C.
After the reaction for 10 hours, 10 parts of methyliminobispropylamine dissolved in 50 parts of methyl ethyl ketone were gradually added dropwise. After the completion of the addition, the mixture was reacted at 50 ° C. for 3 hours to obtain an isocyanate-terminated polyurea resin.

The internal temperature was again raised to 20 ° C., and 5.7 parts of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone were gradually added dropwise. After completion of the dropwise addition, the mixture was reacted at the same temperature for 1 hour. 28 dissolved in 100 parts of methyl ethyl ketone
Part of γ-aminopropyltriethoxysilane was gradually added dropwise and reacted at 30 ° C. for 1 hour. After confirming that the isocyanate group had disappeared, the solid component concentration was adjusted to 35% and another A second resin solution was obtained. This solution is 270
It had a viscosity of dPa · s (25 ° C.).

Reference Example 3 (Production Example of Polyurethane-Polyurethane Resin Containing Hydrolyzable Silyl Group Terminated by Molecular Terminal / Side Chain-Tertiary Amino Group) (1) Production of Silane Coupling Agent Having Isocyanate Termination Hexamethylene in Reaction Vessel 270 parts of an adduct of diisocyanate and water (“Duranate 24A-100”: trade name; manufactured by Asahi Kasei Corporation, NCO% = 23.5) are stirred well at 25 ° C., and γ-aminopropyltriethoxysilane 111 is added thereto. The reaction was carried out by gradually dropping a portion, to obtain a colorless, transparent and viscous liquid product (I). The resulting product had 10.5% free isocyanate groups (theoretical (100%
(The amount of the group in the reactant which is stoichiometrically formed when reacted): 11.2%), and theoretically has the following structure.

[0105]

(2) Production of molecular-terminal / side-chain type hydrolyzable silyl group-tertiary amino group-containing polyurethane-polyurea resin In a reaction vessel, 8 parts of the above viscous liquid product (I) and 50 parts of toluene diisocyanate Of polyethylene glycol (molecular weight 2,040) 15 dissolved in 200 parts of dimethylformamide and 100 parts of methyl ethyl ketone.
0 parts, 4 parts of 1,3-butylene glycol and 9 parts of N, N-dimethyl-N ', N'-dihydroxyethyl-1,3-diaminopropane are added, and the mixture is reacted at 60 ° C. for 6 hours. Thus, an isocyanate-terminated polyurethane-polyurea resin was obtained.

At an internal temperature of 20 ° C., 8 parts of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone were gradually added dropwise, and after completion of the addition, the mixture was reacted at the same temperature for 1 hour. 21 parts of γ dissolved in 100 parts of methyl ethyl ketone
-Aminopropyltriethoxysilane was gradually added dropwise, and the mixture was reacted at 30 ° C. for 1 hour. After confirming that the isocyanate group had disappeared, the solid component concentration was adjusted to 35%, and further another second component was added. A resin solution was obtained. This solution is 300d
It had a viscosity of Pa · s (25 ° C.).

Reference Example 4 (Production Example of Polyurethane Resin Used in Comparative Example 1) Reference Example 1 except that N-methyldiethanolamine and a silane coupling agent having an isocyanate group were not used.
A polyurethane resin solution was obtained using the same materials and formulation as described above.
This solution has a solid content of 35% and a viscosity of 350 dPa · s (25%).
C).

Reference Example 5 (Production Example of Polyurea Resin Used in Comparative Example 2) A polyurea resin solution was prepared by the same material and formulation as in Reference Example 2 except that methyliminobispropylamine and γ-aminopropyltriethoxysilane were not used. Obtained. This solution had a viscosity of 380 dPa · s (25 ° C.) at a solid content of 35%.

Reference Example 6 (Production Example of Polyurethane-Polyurea Resin Used in Comparative Example 3) Reference Example 3 except that no isocyanate-terminated silane coupling agent and γ-aminopropyltriethoxysilane were used.
A polyurethane-polyurea resin solution was obtained according to the same materials and formulation as described above. This solution has a solid content of 35% and 220 dPa
s (25 ° C.).

The weight average molecular weights, equivalents of hydrolyzable silyl groups and equivalents of tertiary amino groups of the resins obtained in Reference Examples 1 to 6 were as shown in Table 3 below. Table 3

Examples 1 to 3 In each of the examples, 40 parts of the resin obtained in the corresponding reference example among reference examples 1 to 3 and tin octylate 0.005
Part, fine-particle synthetic amorphous silica (BET specific surface area 300m
² / g, 100 parts by Mizusawa Chemical Industries, Ltd.) and 0.2 part of a dispersant (sodium polypyrophosphate) were dispersed and mixed with a mixed solvent of methyl ethyl ketone / toluene to adjust the solid content to 15%, and applied to form an ink receiving layer. A liquid was obtained. This coating solution was applied to high-quality paper having a basis weight of 35 g / m ^{2 using} an air knife coater so that the solid content was 10 g / m ² , followed by drying.
Super calendering was performed at a linear pressure of 200 kg / cm to form an ink receiving layer, and three types of recording sheets of the present invention of Examples 1 to 3 were obtained.

Comparative Examples 1 to 3 In each Comparative Example, 40 parts of the resin obtained in the corresponding Reference Example among Reference Examples 4 to 6, and fine-particle synthetic amorphous silica (B
(ET specific surface area 300 m ² / g, manufactured by Mizusawa Chemical Industry) 100
And 0.2 part of a dispersant (polysodium polypyrophosphate) were dispersed and mixed with a mixed solvent of methyl ethyl ketone / toluene, and the solid content was adjusted to 15% to obtain a coating liquid for forming an ink receiving layer. This coating solution was applied to high-quality paper having a basis weight of 35 g / m ^{2 with} an air knife coater so that the solid content was 10 g / m ² , and dried, and subjected to super calendering at a linear pressure of 200 kg / cm. An ink receiving layer was formed, and three types of recording sheets of Comparative Examples 1 to 3 were obtained.

The six types of recording sheets obtained as described above were evaluated by the same method as in the first invention. Table 4 shows the evaluation results. Table 4 As described above, according to the second aspect of the present invention, a high quality print image is provided, and further, the ink receiving layer and the print image are excellent in water resistance and moisture resistance, and transportability and blocking resistance in a printer. An ink jet recording sheet having excellent properties is provided.

[Third Invention] Reference Example 1 (Production Example of Silicone Polyurethane Resin Containing Hydrolytic Silyl Group-Tertiary Amino Group in Molecular Side Chain)

In a reaction vessel, 5 parts of polydimethylsiloxane polyol (molecular weight 3,200) having the above structure and 145 polyethylene glycol (molecular weight 2,040) having the above structure were used.
Parts, 7 parts of 1,3-butylene glycol and 12 parts of N-methyldiethanolamine were dissolved in a mixed solvent of 135 parts of toluene and 100 parts of methyl ethyl ketone.
While stirring well, 61 parts of diphenylmethane diisocyanate is added. After the addition is completed, 100 parts of methyl ethyl ketone is further added and the mixture is reacted at 80 ° C. for 6 hours. No hydroxyl group was observed in the infrared absorption spectrum of the obtained resin, and no hydroxyl group was confirmed by quantification by the pyridine method (JIS K-0070 2.5). Next, a silane coupling agent having an isocyanate group (C ₂ H ₅
O) ₃ Si (CH ₂ ) ₃ NCO 7 parts was added and reacted at 80 ° C. for 8 hours. After confirming that the isocyanate group had disappeared, the solid content concentration was adjusted to 35% and the third resin was adjusted. A solution was obtained. This solution had a viscosity of 390 dPa · s (25 ° C.).

Reference Example 2 (Production Example of Silicone Polyurea Resin Containing Molecularly Hydrolyzable Silyl Group / Tertiary Amino Group) In a reaction vessel, 71 parts of hydrogenated MDI are dissolved in 200 parts of dimethylformamide, and polyethylene oxide diamine (“Jeffamine ED”) dissolved in 100 parts of dimethylformamide while maintaining the internal temperature at 20 ° C. and stirring well. Trade name; manufactured by Texaco Chemical Co .; molecular weight 2,0
00) and 5 parts of polydimethylsiloxanediamine (molecular weight: 3,880) having the above structure were gradually added dropwise. After the completion of the dropwise addition, the mixture was reacted at 50 ° C. for 1 hour.
10 parts of methyliminobispropylamine dissolved in 0 parts of methyl ethyl ketone were gradually added dropwise.
The reaction was performed at a temperature of 3 ° C. for 3 hours to obtain an isocyanate-terminated polyurea resin.

The internal temperature was again raised to 20 ° C., and 5.7 parts of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone were gradually added dropwise. After completion of the dropwise addition, the mixture was reacted at the same temperature for 1 hour. 28 dissolved in 100 parts of methyl ethyl ketone
Part of γ-aminopropyltriethoxysilane was gradually added dropwise and reacted at 30 ° C. for 1 hour. After confirming that the isocyanate group had disappeared, the solid component concentration was adjusted to 35% and another A third resin solution was obtained. This solution is 250
It had a viscosity of dPa · s (25 ° C.).

Reference Example 3 (Molecule terminal / side chain type hydrolyzable silyl group-tertiary amino group-containing silicone polyurethane-
Production Example of Polyurea Resin) (1) Production of Isocyanate-Terminated Silane Coupling Agent Adduct of hexamethylene diisocyanate and water in a reaction vessel (“Duranate 24A-100”: trade name; manufactured by Asahi Kasei Corporation, NCO% = 23.5) ) While well stirring 270 parts at 25 ° C, 111 parts of γ-aminopropyltriethoxysilane was gradually added dropwise and reacted to obtain a colorless, transparent and viscous liquid product (I). The resulting product had 10.5% free isocyanate groups (theoretical (100%
Amount of the group introduced stoichiometrically when reacted): 1
1.2%), which is theoretically considered to be the following structure.

[0120]

(2) Production of molecular-terminal / side-chain type hydrolyzable silyl group-tertiary amino group-containing silicone polyurethane-polyurea resin In a reaction vessel, 8 parts of the above viscous liquid product (I) and 50 parts of toluene diisocyanate were dissolved in 200 parts of dimethylformamide, and polyethylene glycol (molecular weight: 2,040) 14 dissolved in 100 parts of methyl ethyl ketone 14
5 parts and 5 parts of ethylene oxide-added polydimethylsiloxane (molecular weight 4,500) having the above structure, and 4 parts
Parts of 1,3-butylene glycol and 9 parts of N, N-dimethyl-N ′, N′-dihydroxyethyl-1,3-diaminopropane, and reacted at 60 ° C. for 6 hours to obtain an isocyanate-terminated polyurethane-polyurea resin. I got

At an internal temperature of 20 ° C., 8 parts of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone were gradually added dropwise. After the completion of the addition, the mixture was reacted at the same temperature for 1 hour.
Further, 20 parts of γ-aminopropyltriethoxysilane dissolved in 100 parts of methyl ethyl ketone were gradually added dropwise, and the mixture was reacted at 30 ° C. for 1 hour to confirm that the isocyanate groups had disappeared. % To obtain another third resin solution. This solution is 320d
It had a viscosity of Pa · s (25 ° C.).

Reference Example 4 (Production Example of Polyurethane Resin Used in Comparative Example 1) The same material and formulation as in Reference Example 1 except that polydimethylsiloxane polyol, N-methyldiethanolamine and a silane coupling agent having an isocyanate group were not used. Thus, a hydrophilic polyurethane resin solution was obtained. This solution had a solids content of 35% and 340 dPa.s. s (25 ° C.).

Reference Example 5 (Production Example of Polyurea Resin Used in Comparative Example 2) The same material as in Reference Example 2 was used except that polydimethylsiloxanediamine, methyliminobispropylamine and γ-aminopropyltriethoxysilane were not used. According to the prescription, a hydrophilic polyurea resin solution was obtained. This solution contains 35 solid components.
%, And had a viscosity of 300 dPa · s (25 ° C.).

Reference Example 6 (Production example of polyurethane-polyurea resin used in Comparative Example 3) The same material as in Reference Example 3 except that polydimethylsiloxane, isocyanate-terminated silane coupling agent and γ-aminopropyltriethoxysilane were not used. Thus, a hydrophilic polyurethane-polyurea resin solution was obtained according to the following formula. This solution had a solid content of 35% and a viscosity of 220 dPa · s (25 ° C.).

The weight-average molecular weights, equivalents of hydrolyzable silyl groups, equivalents of tertiary amino groups, and siloxane segment contents (% by weight) of the resins obtained in Reference Examples 1 to 6 obtained above are shown in Table 5 below. It was as follows. Table 5

Examples 1 to 3 In each example, 40 parts of the resin obtained in the corresponding reference example among reference examples 1 to 3 and tin octylate 0.005
Part, fine-particle synthetic amorphous silica (BET specific surface area 300m
² / g, 100 parts by Mizusawa Chemical Industries, Ltd.) and 0.2 part of a dispersant (sodium polypyrophosphate) were dispersed and mixed with a mixed solvent of methyl ethyl ketone / toluene to adjust the solid content to 15%, and applied to form an ink receiving layer. A liquid was obtained. This coating solution was applied to high-quality paper having a basis weight of 35 g / m ^{2 using} an air knife coater so that the solid content was 10 g / m ² , and dried.
Super calendering was performed at a linear pressure of 200 kg / cm to form an ink receiving layer, and three types of recording sheets of the present invention of Examples 1 to 3 were obtained.

Comparative Examples 1 to 3 In each Comparative Example, 40 parts of the resin obtained in the corresponding Reference Example among Reference Examples 4 to 6, and fine-particle synthetic amorphous silica (B
(ET specific surface area 300 m ² / g, manufactured by Mizusawa Chemical Industry) 100
And 0.2 part of a dispersing agent (sodium polypyrophosphate) were dispersed and mixed with a methyl ethyl ketone / toluene mixed solvent to adjust the solid content to 15% to obtain a coating liquid for forming an ink receiving layer. This coating solution is applied to high-quality paper having a basis weight of 35 g / m ^{2 using} an air knife coater so that the solid content is 10 g / m ² , dried, and subjected to super calendering at a linear pressure of 200 Kg / cm to form an ink. The receiving layer was formed, and three types of recording sheets of Comparative Examples 1 to 3 were obtained. The six types of recording sheets obtained as described above were evaluated by the same method as in the first invention. Table 6 shows the evaluation results.

Table 6 As described above, according to the third aspect of the present invention, a high-quality print image is provided, and further, the ink receiving layer and the print image are excellent in water resistance and moisture resistance, and transportability and blocking resistance in a printer. An ink jet recording sheet having excellent properties is provided.

[0130]

As described above, the ink receiving layer of the ink jet recording sheet is formed of any one of the first to third resins, particularly preferably a hydrophilic polyurethane resin, a hydrophilic polyurea resin and a hydrophilic polyurethane. -By forming a polyurea resin or a hydrophilic polyamide resin as a constituent component, the ink absorbability and coloring properties are excellent, and a stable high-quality printed image is provided. Further, the ink receiving layer and the printed image have excellent water resistance. And a recording sheet having excellent transportability and blocking resistance in a printer.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Kenichi Takahashi 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Katsutoshi Torii 1-7 Nihonbashi Bakurocho, Chuo-ku, Tokyo No. 6 Inside Dainichi Seika Kogyo Co., Ltd. (72) Takeshi Kawaguchi 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Katsuyuki Fukui Nihonbashi Bakurocho, Chuo-ku, Tokyo No. 7-6 Inside Dainichi Seika Industry Co., Ltd.

Claims (25)

[Claims] 1. An ink jet recording sheet having at least one ink receiving layer provided on at least one surface of a base sheet, wherein a resin component constituting the ink receiving layer comprises:
An ink-jet recording sheet comprising a hydrophilic resin having a hydrolyzable silyl group in a molecule. 2. The method according to claim 1, wherein the hydrophilic resin is at least one selected from the group consisting of a hydrophilic polyurethane resin, a hydrophilic polyurea resin, and a hydrophilic polyurethane-polyurea resin.
The inkjet recording sheet according to claim 1, which is a seed. 3. The hydrophilic resin constituting the ink receiving layer,
The ink-jet recording sheet according to claim 1, which is crosslinked by moisture. 4. The ink-jet recording sheet according to claim 1, wherein the hydrophilic resin is a resin formed using a compound having a reactive group and a hydrolyzable group silyl group as a part of a raw material. 5. The hydrophilic resin having a weight average molecular weight of 5,000.
The inkjet recording sheet according to claim 1, wherein the number is from 0 to 500,000. 6. The hydrophilic resin having a weight average molecular weight of 10.0 or less.
The inkjet recording sheet according to claim 1, wherein the number is from 00 to 200,000. 7. The ink-jet recording sheet according to claim 1, wherein the hydrolyzable silyl group in the hydrophilic resin is present at a ratio of 0.001 to 10.0 equivalents / g. 8. The ink jet recording sheet according to claim 1, wherein the hydrolyzable silyl group in the hydrophilic resin is present at a ratio of 0.01 to 1.0 equivalent / g. 9. An ink jet recording sheet having at least one ink receiving layer provided on at least one side of a base sheet, wherein a resin component constituting the ink receiving layer comprises:
An inkjet recording sheet comprising a hydrophilic resin having a hydrolyzable silyl group and a tertiary amino group in a molecule. 10. The ink jet recording sheet according to claim 9, wherein the hydrophilic resin is at least one selected from a hydrophilic polyurethane resin, a hydrophilic polyurea resin, and a hydrophilic polyurethane-polyurea resin. 11. The ink jet recording sheet according to claim 9, wherein the hydrophilic resin constituting the ink receiving layer is crosslinked by moisture. 12. The ink jet recording sheet according to claim 9, wherein the hydrophilic resin is a resin formed by using a compound having a hydrolyzable silyl group and a compound having a tertiary amino group as a part of the raw material. 13. The hydrophilic resin having a weight average molecular weight of 5,0.
The inkjet recording sheet according to claim 9, wherein the number is from 00 to 500,000. 14. The hydrophilic resin having a weight average molecular weight of 10,
The inkjet recording sheet according to claim 9, wherein the number is from 000 to 200,000. 15. The hydrolyzable silyl group in the hydrophilic resin is present at a ratio of 0.001 to 10.0 equivalents / g, and the tertiary amino group is present at a ratio of 0.1 to 50 equivalents / g. The ink jet recording sheet according to claim 9 which is present. 16. The hydrolyzable silyl group in the hydrophilic resin is present at a rate of 0.01 to 1.0 equivalent / g, and the tertiary amino group is present at a rate of 0.2 to 10.0 equivalent / g. The ink jet recording sheet according to claim 1, which is present in a proportion. 17. In an ink jet recording sheet having at least one ink receiving layer provided on at least one surface of a base sheet, a resin component constituting the ink receiving layer contains a hydrolyzable silyl group, tertiary tertiary molecule in the molecule. An ink jet recording sheet comprising a hydrophilic resin having an amino group and a polysiloxane segment. 18. The ink-jet recording sheet according to claim 17, wherein the hydrophilic resin is at least one selected from a hydrophilic polyurethane resin, a hydrophilic polyurea resin, and a hydrophilic polyurethane-polyurea resin. 19. The ink jet recording sheet according to claim 17, wherein the hydrophilic resin constituting the ink receiving layer is crosslinked by moisture. 20. The hydrophilic resin having a weight average molecular weight of 5,0
The inkjet recording sheet according to claim 17, wherein the number is from 00 to 500,000. 21. The weight average molecular weight of the hydrophilic resin is 10,
The recording sheet for inkjet according to claim 17, wherein the number is from 000 to 200,000. 22. The hydrolyzable silyl group in the hydrophilic resin is present at a ratio of 0.001 to 10.0 equivalents / g, and the tertiary amino group is present at a ratio of 0.1 to 50 equivalents / g. Exists,
18. The ink jet recording sheet according to claim 17, wherein the polysiloxane segment is present at a ratio of 0.1 to 10% by weight. 23. The hydrolyzable silyl group in the hydrophilic resin is present at a ratio of 0.01 to 1.0 equivalent / g and the tertiary amino group is present at a ratio of 0.2 to 10.0 equivalent / g. Exist in proportions,
18. The ink jet recording sheet according to claim 17, wherein the polysiloxane segment is present at a ratio of 0.5 to 10.0% by weight. 24. The ink-jet recording sheet according to claim 1, 9 or 17, wherein the base sheet is plastic, glass, cloth, leather, wood, metal or paper. 25. A hydrophilic resin having a hydrolyzable silyl group in the molecule, a hydrophilic resin having a hydrolyzable silyl group and a tertiary amino group in the molecule, or a hydrolyzable silyl group in the molecule. A coating agent for producing an inkjet recording sheet, comprising a hydrophilic resin having a tertiary amino group and a polysiloxane segment.