JPH1086507A - Ink jet recording sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink jet recording sheet excellent in ink absorbency dry-up performance, providing high image quality causing no fluctuation of density or line and excellent feeding performance causing no warp. SOLUTION: The ink jet recording sheet comprising an ink receiving layer on at least one side of a support wherein the ink receiving layer contains denatured polyvinyl alcohol having structural unit represented by a formula. In the formula, R is a hydrogen atom or an alkyl group, allyl group or an acyl group, m1 is an integer of 0-2, an j1, j2 and j3 are integers of 0-500 satisfying a relationship j1+j2+j321. A1 , A2 and A3 are substituted or not substituted direct chains of alkylane group of branch.

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 particularly to an ink jet recording sheet having high image quality and excellent transportability.

[0002]

2. Description of the Related Art An ink jet recording apparatus (hereinafter, also referred to as an ink jet printer) has low noise, can perform high-speed printing, and can easily perform multicolor recording by using a plurality of ink nozzles. Therefore, in recent years, the image information output device for computers has rapidly spread.

Some ink jet printers developed for full-color recording include transparent films and glossy resins as recording media capable of outputting high-quality images comparable to silver halide photographic color images. The use of coated paper and the content of images to be output are also expanding from characters and figures to color prints and design images that require image quality close to photographs.

[0004] By the way, in terms of safety and recording characteristics, aqueous inks mainly composed of water and a water-soluble organic solvent are mainly used as inks for ink-jet recording to prevent clogging of ink and to improve discharge characteristics. And so on. Further, as a recording sheet, a recording sheet in which a porous ink absorbing layer is provided on a support called ordinary paper or ink jet recording paper has been conventionally used.

[0005] However, these recording sheets have not been able to meet recent demands for high image quality due to large ink bleeding and low glossiness. Furthermore, when a conventional porous ink absorption layer is used for a transparent film or a glossy resin-coated paper, the porous ink absorption layer has a low light transmittance, and thus has a disadvantage that transparency and glossiness are lost. . When the ink absorbing layer is non-porous, light transmittance is improved, but due to poor aqueous ink receptivity, the ink remains on the sheet surface for a long time after image recording and printing, and the drying and fixing time is long. There was a problem of becoming.

In order to solve these problems, a water-soluble polymer such as gelatin, polyvinyl alcohol, polyethylene glycol and polyvinyl pyrrolidone is used as a material for forming an ink absorbing layer which suppresses bleeding and has excellent aqueous ink receptivity. Proposed. For example, in JP-A-62-263084, a receptor layer formed from an aqueous gelatin solution having a specific pH is obtained, and in JP-A-6-64306, a coated gelatin is once gelled and then dried by a cold dry method. In JP-A-60-234879, the receiving layer containing a polyvinyl alcohol having a saponification degree of 50 to 90 mol% and its crosslinking agent is disclosed in JP-A-60-234879, and in JP-A-62-214985, the average molecular weight is 5
Receiving layers containing at least × 10 ⁴ polyethylene oxide have been proposed.

However, as described in the above publication, a receiving layer using a specific water-soluble polymer has a certain degree of excellent ink absorbency, but it is a latest high resolution and high speed printing printer. In the case of printing, it has been confirmed that high density printing and uneven printing due to aggregation of ink occur due to insufficient ink absorptivity using only the technique disclosed in the above publication, and high-quality printing cannot be obtained.

[0008] Further, with the above technique alone, when printing is performed using a certain kind of ink or a certain kind of ink jet printer, the ink dries extremely slowly and cannot be used, or the ink absorption is poor and the image quality is poor. Was found to be extremely deteriorated.

Further, when a polymer such as gelatin or polyvinylpyrrolidone is used, the film expands and contracts due to a change in humidity, and curling occurs particularly at low humidity. It has been found that streaks and irregularities due to irregularities in transport are likely to occur.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a high image quality with excellent ink absorbency and no unevenness in density or streak, excellent drying property, no curl, and improved transportability. An object of the present invention is to provide a recording sheet for ink jet which has no problem.

[0011]

The object of the present invention is achieved by the following constitution.

(1) In an ink jet recording sheet having an ink receiving layer provided on at least one side of a support, the ink receiving layer may be made of a modified polyvinyl alcohol having a structural unit represented by the following general formula (V). A recording sheet for ink jet, characterized by containing.

[0013]

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[Wherein, R represents a hydrogen atom or an alkyl group, an aryl group, or an acyl group, m1 represents an integer of 0 to 2, and j1, j2, and j3 each represent an integer of 0 to 500. However, j1 + j2 + j3 ≧ 1. A ₁ , A ₂ , A
₃ represents a substituted or unsubstituted linear or branched alkylene group. (2) The inkjet recording sheet according to (1), wherein in the general formula (V), m1 is an integer of 1.

(3) The ink for inkjet according to (1) or (2), wherein the modified polyvinyl alcohol is a modified polyvinyl alcohol having 1 to 40 mol% of a structural unit represented by the general formula (V). Recording sheet.

(4) The ink jet recording sheet according to any one of (1) to (3), wherein the ink receiving layer contains gelatin.

(5) The ink jet recording sheet according to any one of (1) to (4), wherein the support is a film or a resin-coated paper in which both sides of a paper are coated with a resin. .

Hereinafter, the present invention will be described in detail.

The modified polyvinyl alcohol having a structural unit represented by the general formula (V) used in the present invention can be synthesized by a general method for synthesizing a modified polyvinyl alcohol.
For example, a method described in U.S. Pat. Nos. 1,971,662, 2,844,570, and 2,990,398, in which ethylene oxide is added to polyvinyl alcohol by an addition reaction, Kaisho 59-1655
No. 408, a method for saponifying a copolymer of vinyl acetate and a vinyl monomer having a polyoxyalkylene group, and a method for producing a polymer having a structural unit represented by the general formula (V) in the backbone of polyvinyl alcohol. Or a method of grafting a branch of polyvinyl acetate using a polymer having a structural unit represented by the general formula (V) as a trunk and saponifying it. OKS-9162, OK from Nippon Synthetic Chemical Industry Co., Ltd.
It is available as S-7158G.

The effect of the present invention can be obtained irrespective of the proportion of the structural unit represented by the general formula (V) contained in the modified polyvinyl alcohol used in the present invention. It is preferably 40 mol%, and most preferably 2 to 20 mol%. When the proportion of the structural unit is 1 mol% or less, the effect of ink absorption is reduced, and
When the content is 0 mol% or more, the effect of drying property is reduced.

Further, m1 in the formula of the general formula (V) contained in the modified polyvinyl alcohol used in the present invention is preferably an integer of 0 to 2 from the viewpoint of its productivity, and more preferably an integer of 1 from the viewpoint of ink absorption. preferable. Also, j1 + j2 + j
3 is preferably an integer of 1 to 500 in production, and more preferably 2 to 5
An integer of 0 is a range with high practicality.

The degree of saponification of the modified polyvinyl alcohol used in the present invention is from 50 to 100 from the viewpoint of water solubility.
Mol% is preferable, and 80 to 100 mol% is more preferable.

The degree of polymerization of the modified polyvinyl alcohol used in the present invention is preferably from 100 to 3000, and more preferably from 200 to 1500 in view of the viscosity of the aqueous solution.

If necessary, 30 units of monomer units other than the general formula (V), vinyl alcohol and vinyl ester may be used.
Such a unit may be contained in an amount of about mol% or less. Examples of such a unit include an α-olefin (ethylene, propylene, a long-chain α-olefin, etc.), an ethylenically unsaturated carboxylic acid-based monomer (acrylate, methacrylate, Acrylonitrile, methacrylonitrile, vinyl chloride, vinyl ether, etc.).

Specific examples of the modified polyvinyl alcohol used in the present invention are shown below, but the present invention is not limited to these.

[0026]

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[0027]

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[0028]

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In the present invention, the amount of the modified polyvinyl alcohol contained in the ink receiving layer is 1 to 50 g / m ^2.
Is preferable, and 2-15 g / m < ² > is more preferable. When the amount of the modified polyvinyl alcohol contained in the ink receiving layer is 1 g / m ² or less, the effect of the present invention becomes small,
If it is 0 g / m ² or more, problems occur in terms of equipment and cost.

In the present invention, the ink receiving layer may be a single layer or two or more layers, and the modified polyvinyl alcohol of the present invention may be contained in any part or all of the layers. From the viewpoint of, it is preferable to contain at least the uppermost layer.

In the present invention, gelatin or a water-soluble polymer can be used alone or in combination of two or more in combination with the modified polyvinyl alcohol of the present invention in the ink receiving layer in order to enhance the ink absorption. In order to obtain high ink absorption, drying properties and high image quality, it is preferable to use gelatin in combination.

As the gelatin to be used in the present invention, any gelatin can be used as long as it is made of animal collagen, but gelatin made of collagen made of pig skin, cow skin and cow bone is preferred. The type of gelatin is not particularly limited, but lime-treated gelatin, acid-treated gelatin, and derivative gelatin (for example, Japanese Patent Publication No. 38-48)
No. 54, No. 39-5514, No. 40-12237,
No. 42-26345, U.S. Pat. No. 2,525,753
Nos. 2,594,293 and 2,614,928
Nos. 2,763,639 and 3,118,766
Nos. 3,132,945 and 3,186,846
No. 3,312,553, British Patent 861,414
And the derivative gelatin described in JP-A Nos. 103,189, etc. can be used alone or in combination thereof.
Use of acid-treated gelatin is advantageous in terms of water resistance.

The acid-treated gelatin preferably used in the present invention is characterized in that its isoelectric point is in the range of 5.5 to 9.6. Unlike the lime-processed gelatin usually used in silver salt photography, such gelatin is obtained by subjecting collagen whose weight is reduced to pigskin or bovine bone, to an acid treatment such as hydrochloric acid in the production process thereof. Are described in The Macromolecular Chemistry of Gelatin (Academic Press) and the like. The isoelectric point of the gelatin of the present invention is measured by a pH meter, and is preferably 8.0 to 8.0.
9.5 range.

In the present invention, the coating amount of the gelatin contained in the ink receiving layer is 3 to 20 g as a solid content.
/ M ^2, more preferably an 5 to 15 g / m ^2. If the ink receiving layer is less than 3 g / m ² , the ink receiving property is poor, and the ink overflows from the receiving layer after printing. Further, when the amount is more than 20 g / m ² , the ink receptivity is improved, but stripe unevenness and transport failure occur.

Examples of the water-soluble polymer in the present invention include vinyl formals such as polyvinyl alcohols, polyvinyl pyrrolidones, polyvinyl pyridinium halides and various modified polyvinyl alcohols and derivatives thereof (JP-A-60-145879 and JP-A-60-220750).
Nos. 61-143177 and 61-235182
No. 61-235183, No. 61-237681
No. 61-26189), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, sodium polyacrylate, methacrylic acid copolymer salt, polysodium methacrylate, vinyl alcohol acrylate copolymer salt, etc. Acrylic group-containing polymers (JP-A-60-168651 and JP-A-62-99)
88, etc.), starch, oxidized starch, carboxyl starch, dialdehyde starch, cationized starch, dextrin, sodium alginate, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, etc. Polymer materials or derivatives thereof (JP-A-59-174382, JP-A-60-262885,
No. 61-143177, No. 61-181679, No. 61-193879, No. 61-287778), polyethylene glycol, polypropylene glycol, polyvinyl ether, polyglycerin, maleic acid alkyl vinyl ether copolymer, maleic acid -N-
Synthetic polymers such as vinyl pyrrole copolymer, styrene-maleic anhydride copolymer, and polyethyleneimine (JP-A-61-32787, JP-A-61-237680, and 61)
-277483).
Among these polymers, polyvinylpyrrolidones, polyvinyl alcohols, polyalkylene oxides, methacrylic acid / acrylic acid copolymers and salts thereof are preferred.

The polyalkylene oxides in the present invention include, for example, polyethylene oxides, polyethylene glycols, polypropylene glycols, and compounds represented by the following general formula [P].

Formula [P] R ₃ O— (A ₄ —O) _j4 — (A ₅ —O) _j5 — (A ₆ —O) _j6
-R ₄ Formula, A _4, A _5, A ₆ is substituted respectively, represent an unsubstituted straight chain or branched alkylene group, it is not that all are the same. R ₃ and R ₄ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or an acyl group.

Examples of each substituent include a hydroxy group, a carboxy group, a sulfonyl group, an alkoxy group, a carbamoyl group and a sulfamoyl group. Preferably used, R ₄ and R ₅ are hydrogen atoms,
A ₄ , A ₅ , and A ₆ are each unsubstituted. Most preferably, A ₄ , A ₅ and A ₆ are each —CH ₂ CH
₂ - or -CH (CH ₃₎ -CH ₂ - it is.

J4, j5 and j6 are each 0 or 0
Represents an integer of ~ 500. Where j4 + j5 + j6 ≧ 5
It is.

The preferred polyalkylene oxides in the present invention are polyethylene oxides, and those having an average molecular weight in the range of 10,000 to 500,000 are preferred, and polyethylene glycol (PEG) is particularly preferred. The average molecular weight is in the range of 50,000 to 300,000.

Here, the average molecular weight of the polyalkylene oxides in the present invention is a molecular weight calculated from a hydroxyl value.

In the present invention, a basic latex or a cationic water-soluble polymer can be contained in the ink receiving layer to impart water resistance.

The basic latex referred to in the present invention is a basic latex having a monomer unit to be copolymerized,
As the monomer unit, an ethylenic monomer, for example,
Acrylic acids, vinyl esters, olefins, styrenes, crotonic acids, itaconic acids, maleic acids,
One or more selected from fumaric acids, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers, and various unsaturated acids Although the combined monomer unit can be mentioned, a basic latex represented by the following general formula [X] is preferable.

Formula (X)-(A) _n1- (B) _n2- (C) _{n3- wherein} A represents a substituted or unsubstituted copolymerizable monomer unit having an amino group or an ammonium group. .

B represents an ethylenically unsaturated monomer unit having at least two ethylenically unsaturated groups.

C represents a copolymerizable ethylenically unsaturated monomer unit other than A and B.

N1 is 10 to 99 mol%;
Is 0 to 10 mol%, and n3 is 0 to 90 mol%.

The cationic water-soluble polymer referred to in the present invention refers to a polymer in which the main component of the polymer exhibits cationicity in an aqueous solution, and a typical example thereof is described in JP-A-61-6188.
No. 7, 61-63477, JP-A-5-104848
No. 5,124,329, and the like.
Polymers containing primary, secondary, tertiary amino groups and quaternary ammonium salts. Any water-soluble cationic polymer can be used, and the type thereof is not particularly limited. Examples of the cationic polymer preferably used in the present invention include the following.

A) polyallylamines b) dicyandiamide-based condensates c) polyethyleneimines d) cation-modified PVA e) cation-modified PVP f) epichlorohydrin derivative g) amino-substituted nylon i) represented by the following general formula [1] J) A polymer containing a structural unit derived from a monomer unit represented by the following general formula [2] k) A polymer containing a structural unit derived from a monomer unit represented by the following general formula [2] k) A monomer represented by the following general formula [3] Polymer containing structural units derived from units

[0050]

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In the formula, R ¹ represents a hydrogen atom or a substituted or unsubstituted lower alkyl group, and Q represents an oxygen atom or —NH—. R ² , R ³ and R ⁴ each represent a substituted or unsubstituted lower alkyl group, which may be the same or different.
X ^- represents a halogen ion, a sulfonate anion, an alkyl sulfonate anion, acetate anion or alkyl carboxylate anion. n represents 2 or 3.

R ⁵ , R ⁶ and R ⁷ each represent a substituted or unsubstituted lower alkyl group, which may be the same or different. X ^- represents a halogen ion, a sulfonate anion, an alkyl sulfonate anion, acetate anion or alkyl carboxylate anion. n represents 2 or 3.

R ⁸ , R ⁹ and R ¹⁰ each represent a substituted or unsubstituted lower alkyl group, which may be the same or different. X ^- represents a halogen ion, a sulfonate anion, an alkyl sulfonate anion, acetate anion or alkyl carboxylate anion. n represents 2 or 3.

The lower alkyl group represented by R ^{1 to} R ¹⁰ is preferably a methyl group or an ethyl group.

The polyallylamines referred to in the present invention include a polyallylamine represented by the following general formula [4], a polydiallylamine represented by the following general formula [5-1] or [5-2], and a polyallylamine represented by the following general formula [6] -1] or the polydiallylamine derivative represented by [6-2], or a polymer thereof.

[0056]

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In the general formula [4], n is 5 to 1000
0 integer, X ₁ ^- represents the residue of an inorganic or organic acid.

[0058]

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Formulas [5-1], [5-2], [6-
In 1] and [6-2], R ₁ and R ₂ are each represents a hydrogen atom, a methyl group, an ethyl group or a hydroxyethyl group, X ₂ ^- represents an inorganic acid residue or organic acid residue, Y Represents a divalent linking group. Also, n / m = 9/1 to 2/8, l =
5 to 10,000.

Specific examples of the polydiallylamine derivative represented by the general formula [6-1] or [6-2] include a SODI represented by the general formula described in JP-A-60-83882.
_A copolymer containing _two groups in a repeating unit, a copolymer with acrylamide described on page 2 of JP-A-1-9776, and represented by the general formula [6-1] or [6-2] of the present invention. And copolymers with polydiallylamine.

Specific examples of the dicyandiamide condensate used in the present invention include dicyandiamide formalin condensate and polyalkylene polyamine dicyandiamide ammonium salt condensate. These are Sanfix 70 of Sanyo Chemical Co., Ltd., and Nicafloc of Nihon Carbide Co. D
-1000, Neofix F, Neofix RP-70Y of Nikka Chemical Co., Ltd., respectively.

The polyethyleneimines referred to in the present invention are:
It is a polymer obtained by polymerizing ethyleneimine or a derivative thereof, and particularly preferably a polyethyleneimine quaternary ammonium compound. Specifically, JP-A-60-727
No. 85 and No. 60-76386.

The cation-modified PVA referred to in the present invention is a copolymer of vinyl alcohol and a monomer unit having a cationic group, and is specifically described in JP-A-62-138280.
Nos. 3 and 4 of the publication can be used.

The cation-modified PVP referred to in the present invention is a copolymer of vinylpyrrolidone and a monomer unit having a cationic group. Specific examples of the monomer unit having a cationic group include quaternized vinylimidazole, quaternized dialkylaminoethyl methacrylate, and methacrylamidopropyltrialkylammonium salt.

Specific examples of the epichlorohydrin derivative used in the present invention include polyamide epichlorohydrin resin, a reaction product of epichlorohydrin with a tertiary amine described on page 2 of JP-A-61-252189, and And the compounds of the general formula (II) described on page 4 of JP-A-62-259882.

These can be synthesized by a known method. Commercially available products include Nalpoly-607 (Nalco Chemical) and Polyfix 601 (Showa Kogaku).

Specific examples of the amino-substituted nylon used in the present invention are described on page 2 of JP-A-59-33179, and as a commercially available product, AQ nylon (trade name:
Toray).

As the cationic polyaluminum hydroxide used in the present invention, those described in Item 2 of JP-A-60-257286 can be used.

Preferred compounds among the monomers represented by the general formula [1] include, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylamino Propyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) ) Acrylamide and N, N
A quaternary product of diethylaminopropyl (meth) acrylamide with methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide or ethyl iodide, or a sulfonate, alkyl sulfonate or acetate obtained by substituting the anion thereof; Alternatively, an alkyl carboxylate can be used.
Among these, particularly preferred compounds include, for example, trimethyl-2- (methacryloyloxy) ethylammonium chloride, triethyl-2- (methacryloyloxy) ethylammonium chloride, trimethyl-2-
(Acryloyloxy) ethylammonium chloride, triethyl-2- (acryloyloxy) ethylammonium chloride, trimethyl-3- (methacryloyloxy) propylammonium chloride, triethyl-3- (methacryloyloxy) propylammonium chloride, trimethyl-2- (methacryloyl) Amino) ethylammonium chloride, triethyl-2
-(Methacryloylamino) ethylammonium chloride, trimethyl-2- (acryloylamino) ethylammonium chloride, triethyl-2- (acryloylamino) ethylammonium chloride, trimethyl-3- (methacryloylamino) propylammonium chloride, triethyl-3- ( (Methacryloylamino) propylammonium chloride, trimethyl-3
-(Acryloylamino) propylammonium chloride, triethyl-3- (acryloylamino) propylammonium chloride, N, N-dimethyl-N-ethyl-2- (methacryloyloxy) ethylammonium chloride, N, N-diethyl-N-methyl -2-
(Methacryloyloxy) ethylammonium chloride, N, N-dimethyl-N-ethyl-3- (acryloylamino) propylammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium bromide, trimethyl-3- (acryloylamino)
Propyl ammonium bromide, trimethyl-2-
(Methacryloyloxy) ethylammonium sulfonate, trimethyl-3- (acryloylamino) propylammonium acetate and the like can be mentioned.

Preferred examples of the monomer represented by the general formula [2] include trimethyl-p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride, and triethyl-m-vinyl. Benzyl ammonium chloride, N, N-dimethyl-N
-Ethyl-p-vinylbenzylammonium chloride, N, N-diethyl-N-methyl-p-vinylbenzylammonium chloride, trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-
Vinylbenzylammonium sulfonate, trimethyl-m-vinylbenzylammonium sulfonate, trimethyl-p-vinylbenzylammonium acetate,
And trimethyl-m-vinylbenzylammonium acetate.

Preferred examples of the monomer represented by the general formula [3] include diallyldimethylammonium chloride, diallyldiethylammonium chloride, diallyldimethylammonium bromide, diallyldimethylammonium sulfolate, diallyldimethylammonium acetate and the like.

Further, acrylamide, methacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, N-methylolacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) are added to these monomer units. By copolymerizing a monomer selected from acrylate and N-vinylpyrrolidone in the range of 20 to 80 parts by weight, the ink absorption capacity and the ink absorption rate of the polymer having the quaternary ammonium base itself are increased, and the ink dot diameter is further increased. Extremely favorable properties can be imparted, such as adjusting the size to an appropriate size and eliminating printing unevenness in a solid portion.

Among these cationic polymers, particularly preferred are polyallylamines, dicyandiamide-based condensates, cation-modified PVP, epichlorohydrin derivatives, and cationic polyaluminum hydroxide.

In the present invention, a suitable crosslinking agent can act on the ink receiving layer for the purpose of improving water resistance. Specific examples of the crosslinking agent include formaldehyde, aldehyde compounds such as glutaraldehyde, diacetyl, ketone compounds such as chloropentanedione,
Bis (2-chloroethylurea), 2-hydroxy-4,
6-dichloro-1,3,5-triazine, U.S. Pat.
No. 288,775, compounds having a reactive halogen, divinyl sulfone, U.S. Pat.
No. 8, compounds having reactive olefins, N-methylol compounds described in U.S. Pat. No. 2,732,316, isocyanates described in U.S. Pat. No. 3,103,437, U.S. Pat. No. 3,017,280 No.2,98
Aziridine compounds as described in US Pat. No. 3,611, carbodiimide compounds as described in US Pat. No. 3,100,704, epoxy compounds as described in US Pat. No. 3,091,537, halogen carboxaldehydes as mucochloric acid, There are dioxane derivatives such as dihydroxydioxane, and these can be used alone or in combination of two or more. The amount of the crosslinking agent added is 0.01 g to 1 with respect to 100 g of the modified polyvinyl alcohol.
0 g is preferable, and 0.1 to 5 g is more preferable.

The method for forming the ink receiving layer of the present invention includes a size press method, a roll coater method, a blade coater method, an air knife coater method, a gate roll coater method, a rod bar coater method, a curtain method, a slide hopper method, and an extrusion method. A commonly used coating method such as a lubrication method is used.

In the present invention, in addition to a surfactant, a binder, and a hardener, an inorganic pigment, a coloring dye, a coloring pigment, a fixing agent for an ink dye, a UV absorber, an antioxidant, Various known additives such as a dispersant, an antifoaming agent, a leveling agent, a preservative, an optical brightener, a viscosity stabilizer, and a pH adjuster can also be added.

In the present invention, it is preferable to add a surfactant to the ink receiving layer within a range not to impair the ink absorbency, for the purpose of improving the image quality. The surfactant used may be any of anionic, cationic, nonionic and betaine types, and may be of low molecular weight, high molecular weight or different types. More preferred are fluorine-based surfactants.

As a conventional method of using a surfactant, it has been considered that when an anionic surfactant and a cationic surfactant are used in combination, aggregation in a solution state before coating occurs, which is not preferable. The system surfactant does not aggregate in the solution state, and when used in an ink jet recording sheet, exhibits excellent ink receptivity, has a small phenomenon that ink droplets diffuse with time, and uses larger droplets. It was found that an image having higher density and less unevenness could be obtained.

In the present invention, the anionic fluorine-containing surfactant or the cationic fluorine-containing surfactant is described, for example, in US Pat. Nos. 2,559,751 and 2,567,011.
No. 2,732,398, No. 2,764,602
No. 2,806,866, 2,809,998
Nos. 2,915,376 and 2,915,528
No. 2,918,501, 2,934,450
No. 2,937,098 and No. 2,957,031
No. 3,472,894, No.3,555,089
No., British Patent Nos. 1,143,927 and 1,130,8
No. 22, JP-B-45-37304, JP-A-47-96
No. 13, No. 49-134614, No. 50-11770
No. 5, No. 50-117727, No. 50-112243
Nos. 52-41182 and 51-12392, British Chemical Society (J. Chem. Soc.) 1950, 27
89, 1957, pages 2574 and 2640, Journal of the American Chemical Society (J. Amer. Chem. Soc.) 79, 2549 (1957), Oil Chemistry (J. Japan)
Oil Chemist Soc. ) Volume 12 653
Page, Journal of the Society of Organic Chemistry (J. Org. Chem.), Vol. 30, No. 3
It can be synthesized by the method described on page 524 (1965) and the like.

Certain of these fluorine surfactants are trade names Megafac F from Dainippon Ink and Chemicals, Inc., and Fluorad (trade name) from Minnesota Mining and Manufacturing Company. Fluorad) under the trade name of FC, Imperial Chemical Industry under the trade name of Monflor, E.I.Dupont Nemelas and Company under the trade name of Zonyls, and Farbeberke. Licovet V from Hoechst
Each is marketed under the trade name PF.

The total amount of the cationic fluorine-based surfactant and the anionic fluorine-based surfactant used is preferably from 0.1 to 1000 mg / m ² , more preferably from 0.5 to 3 mg / m ^2.
00 mg, more preferably 1.0 to 150 mg.
When used together, two or more of them may be used in combination. In addition, a nonionic fluorine-based surfactant, a betaine-type fluorine-based surfactant, or a hydrocarbon-based surfactant may be used in combination.

The molar ratio of the anionic fluorinated surfactant to the cationic fluorinated surfactant of the present invention is preferably 1:10 to 10: 1, and more preferably 3: 7 to 7: 3.
Is preferred.

The coating amount of the ink receiving layer of the present invention is 3
To 100 g / m ^2, more preferably from 5 to 50 g / m ^2.

Although the ink receiving layer is provided on at least one side of the support, it may be provided on both sides of the support for the purpose of preventing curling.

In the present invention, a matting agent can be used in the ink receiving layer to prevent sticking.

A matting agent is well known in the photographic art and can be defined as discontinuous solid particles of an inorganic or organic material dispersible in a hydrophilic organic colloid binder. Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.) and alkaline earth metal salts (eg, sulfates and carbonates, specifically, barium sulfate, carbonate Calcium, magnesium sulfate, calcium carbonate, etc., silver halide grains which do not form an image (silver chloride, silver bromide, etc., to which iodine atom may be added as a halogen component even a little), glass and the like.

Examples of the organic matting agent include starch, cellulose ester (for example, cellulose acetate propionate), cellulose ether (for example, ethyl cellulose), and synthetic resin. Examples of synthetic resins are water-insoluble or poorly soluble synthetic polymers such as alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate,
(Meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin (for example, ethylene), styrene, benzoguanamine / formaldehyde condensate alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturation A polymer having a combination of dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

Other epoxy resin, nylon, polycarbonate, phenol resin, polyvinyl carbazole,
Polyvinylidene chloride can also be used.

From the viewpoint of transportability, these preferably have a weight average particle diameter of 3 to 20 μm and a total weight (also referred to as an attached amount) in the ink receiving layer of 10 to 100 mg / m ² . From the viewpoint of the stability of the coating solution, it is preferable that particles having a size of 3 μm or less or particles having a size of 20 μm or more are previously excluded by classification.

These can be used in combination.

As the support used in the present invention, either a transparent support or an opaque support can be used according to the purpose of use.

As the transparent support, any of those conventionally known can be used. For example, films such as polyester resin, cellulose acetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride resin, polyimide resin, cellophane and celluloid can be used. is there. Among these, a polyester resin, particularly a polyethylene terephthalate film, is preferred from the viewpoint of the rigidity and transparency of the support.

As the opaque support, high-quality paper, medium-quality paper,
Uncoated paper such as super calendered paper, single-sided base paper, tracing paper, etc., coated paper such as art paper, coated paper, lightweight coated paper, lightly coated paper, cast coated paper, etc., plastic film, opaque with pigment Films, films such as foamed films, resin-coated papers, resin-impregnated papers, nonwoven fabrics, cloths and composites thereof can be used. Among these, resin-coated paper and various films are preferable from the viewpoint of glossiness and smoothness, and resin-coated paper, polyolefin resin-coated paper, and polyester-based film are more preferable from the feeling of touch and high quality.

The base paper constituting the preferably used resin-coated paper is not particularly limited, and generally used paper can be used. More preferably, for example, a smooth base paper used for a photographic support is used. preferable. As the pulp constituting the base paper, natural pulp, recycled pulp, synthetic pulp or the like may be used alone or in combination of two or more. The base paper is blended with additives generally used in papermaking, such as a sizing agent, a paper strength enhancer, a filler, an antistatic agent, a fluorescent whitening agent, and a dye.

Further, a surface sizing agent, a surface paper strengthening agent, a fluorescent whitening agent, an antistatic agent, a dye, an anchoring agent and the like may be applied to the surface.

The thickness of the base paper is not particularly limited. However, it is preferable that the base paper has good surface smoothness such as by applying a pressure by a calender or the like during or after paper making.

As the resin of the resin-coated paper, a polyolefin resin or a resin curable by an electron beam can be used.
Examples of the polyolefin resin are low-density polyethylene, high-density polyethylene, polypropylene, polybutene, a homopolymer of an olefin such as polypentene or a copolymer of two or more olefins such as an ethylene-propylene copolymer and a mixture thereof, Those having various densities and melt viscosity indices (melt index) can be used alone or in combination.

The resin of the resin-coated paper includes white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate and stearic acid. Aluminum, fatty acid metal salts such as magnesium stearate, antioxidants such as Irganox 1010 and Irganox 1076, blue pigments and dyes such as cobalt blue, ultramarine blue, cecilian blue, and phthalocyanine blue, cobalt violet, fast violet, and manganese purple It is preferable to add various additives such as magenta pigments and dyes, fluorescent brighteners and ultraviolet absorbers in an appropriate combination.

In the present invention, an aqueous ink is preferably used, and a recording liquid comprising the following colorant, liquid medium and other additives is used. Examples of the coloring agent include direct dyes, acid dyes, basic dyes, reactive dyes, and water-soluble dyes such as food colorants.

As the solvent for the aqueous ink, water and various water-soluble organic solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, sec-butyl alcohol, t-
alkyl alcohols having 1 to 4 carbon atoms such as tert-butyl alcohol and isobutyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones and ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; Polyalkylene glycols such as polyethylene glycol and polypropylene glycol; alkylene groups such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol and diethylene glycol having 2 to 2 6 alkylene glycols; glycerin, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, triethyl Glycol, lower alkyl ethers of polyhydric alcohols such as mono-methyl ether,
Pyrrolidinones such as 2H-pyrrolidinone, 1-methyl-
Examples thereof include pyrrolidones such as 2-pyrrolidone and 2-pyrrolidone. Among these many water-soluble organic solvents,
Preferred are polyhydric alcohols such as diethylene glycol, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, and pyrrolidones.

In the present invention, a mixed solvent of water and the above-mentioned organic solvent is preferably used as a solvent of the ink from the viewpoint of preventing clogging of the ink head nozzle. / 9 to 9/1, more preferably 4/6 to 9/1.

Other additives to the ink include, for example, a pH adjuster, a metal sequestering agent, a fungicide, a viscosity adjuster,
Examples include surface tension adjusters, wetting agents, surfactants, and rust inhibitors.

[0103]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 to 7 A resin composition comprising 70 parts of low-density polyethylene and 20 parts of high-density polyethylene was coated on a surface of a base paper having a basis weight of 140 g by 30 parts.
g / m ² , and a resin composition comprising 50 parts of low-density polyethylene and 50 parts of high-density polyethylene on the back surface at 30 g / m ^2.
A resin coating paper coated with m ^{2 was} coated with a coating solution (solid content 8%) having the following composition by a bar coating method so that the film weight after drying was 12 g / m ² , and then dried. Example 1
To 13 were prepared.

Example 1-100 parts of Exemplified Compound 1 Example 2-100 parts of Exemplified Compound 2 Example 3-100 parts of Exemplified Compound 9 Example 4-100 parts of Exemplified Compound 6 Example 5-100 parts of Exemplified Compound 7 Example 6-Exemplified Compound 8 100 parts Example 7-Exemplified Compound 10 100 parts Comparative Examples 1-4 A coating liquid was prepared from the following composition in the same manner as in Example 1,
A recording sheet for inkjet for comparison was obtained.

Comparative Example 1-Polyvinyl pyrrolidone (PVP K-90, manufactured by BASF) 100 parts Comparative Example 2-Polyvinyl alcohol (Gosenol GL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 100 parts Comparative Example 3-Polyethylene glycol (Meisei Chemical Co., Ltd.) 100 parts of alkox R-150) Comparative Example 4 Lime-treated gelatin (KV-3000 manufactured by Konica Gelatin Co.) 100 parts Next, the samples prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were applied to an inkjet printer. 1 (MJ-5000
C; manufactured by Seiko Epson Corporation) and a dedicated ink, an inkjet printer 2 (BJC-600J; manufactured by Canon) and a dedicated ink were evaluated by the following evaluation methods.

(Evaluation of Drying Property) A uniform image portion of K (black) was visually observed to determine its glossiness.

Evaluation criteria ◎: Excellent without any problems ；: Dry within 10 minutes after printing and no problem in practical use ；: Dried within 1 hour after printing but requires care in handling ×: Dried for 1 hour or more Not practical.

(Evaluation of density unevenness) A uniform image of red, blue and green was printed and the state of density unevenness was determined.

◎: No density unevenness of each color at all ○: Slight density unevenness occurs in one part of color but no particular problem △: Slight density unevenness occurs in all colors X: Density unevenness in all colors It cannot be determined as a uniform density part.

(Evaluation of Streak Unevenness) A black uniform image of the sample after printing was visually observed to determine the state of the streak unevenness.

◎: No streak unevenness, uniform image ○: Very slight streak unevenness confirmed, but no problem △: Streak unevenness observed at regular intervals ×: Streak unevenness observed in all images Can be

(Continuous transportability) 20 sheets of A4 size
The film was continuously conveyed under an environment of 20 ° C. and 20%, and the conveyability was determined.

A: Forty sheets could be conveyed without any problem. O: One or two sheets were misfeeded on the way, but they were conveyed without any problem when re-pointed by hand. Δ: One in ten sheets was misfeeded. ×: The paper is not conveyed unless it is manually reinserted. ××: The paper can be manually fed, but hit the head during printing, and image evaluation could not be performed.

The evaluation results are summarized in Table 1.

[0116]

[Table 1]

As is clear from Table 1, it was confirmed that the use of the compound of the present invention did not cause unevenness in density and unevenness and was excellent in drying property.

Examples 8 to 13 The same support as in Examples 1 to 7 was coated with a coating solution having the following composition (solid content: 8%) by a bar coating method so that the film weight after drying was 15 g / m ^2. , And dried to prepare inkjet recording sheet samples of Examples 8 to 13.

Example 8-50 parts of Exemplified Compound 1-50 parts of polyvinylpyrrolidone (PVP K-90 manufactured by BASF)-0.5 part of organic fine particle matting agent (MR-13G manufactured by Soken Chemical Co., Ltd.)-The following surfactant FA 0.05 part ・ The following surfactant FK 0.05 part Example 9 ・ 50 parts of Exemplified Compound 1 ・ 50 parts of polyvinyl alcohol (Gosenol GL-05 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) ・ Mat agent for organic fine particles (manufactured by Soken Chemical Co., Ltd.) MR-13G) 0.5 part ・ The following surfactant FA 0.05 part ・ The following surfactant FK 0.05 part Example 10 ・ Example compound 1 50 parts ・ Polyethylene glycol (Alcox R-150 manufactured by Meisei Chemical Co., Ltd.) 50 parts) Organic particle matting agent (MR-13G manufactured by Soken Chemical Co., Ltd.) 0.5 part * The following surfactant FA 0.05 part * The following surfactant FK 5 parts Example 11-Exemplified Compound 1 50 parts-Lime-treated gelatin (KV-3000 manufactured by Konica Gelatin Co.) 50 parts-Organic fine particle matting agent (MR-13G manufactured by Soken Chemical Co., Ltd.) 0.5 part-The following surfactant FA 0.05 part Surfactant FK 0.05 part Example 12 Example compound 9 60 parts Lime-processed gelatin (KV-3000 manufactured by Konica Gelatin Co.) 40 parts Organic fine particle matting agent (MR- manufactured by Soken Chemical Co., Ltd.) 13G) 0.5 part ・ The following surfactant FA 0.05 part ・ The following surfactant FK 0.05 part Example 13 ・ Exemplary compound 1 50 parts ・ Acid-treated gelatin (isoelectric point 9 manufactured by SBI) 50 parts 0.5 parts of organic fine particle matting agent (MR-13G manufactured by Soken Chemical Co., Ltd.) 0.05 parts of the following surfactant FA 0.05 parts of the following surfactant FK Comparative Examples 5 to 7 A coating solution was prepared in the same manner as in Example 1,
A recording sheet for inkjet for comparison was obtained.

Comparative Example 5-50 parts of polyvinylpyrrolidone (PVP K-90, manufactured by BASF)-50 parts of lime-treated gelatin (KV-3000, manufactured by Konica Gelatin)-Organic fine particle matting agent (MR-13G, manufactured by Soken Chemical Co., Ltd.) 0 .5 parts ・ The following surfactant FA 0.05 parts ・ The following surfactant FK 0.05 parts Comparative Example 6 ・ Polyvinyl alcohol (Gosenol GL-05 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 50 parts ・ Lime-treated gelatin (Konica gelatin) KV-3000) 50 parts-Organic fine particle matting agent (MR-13G manufactured by Soken Chemical Co., Ltd.) 0.5 parts-The following surfactant FA 0.05 parts-The following surfactant FK 0.05 parts Comparative Example 7 Polyethylene glycol (Alcox R-150 manufactured by Meisei Chemical Co., Ltd.) 50 parts ・ Lime treated gelatin (KV-3000 manufactured by Konica Gelatin) 0 parts organic particles matting agent (Soken Chemical Co., Ltd. MR-13G) 0.5 parts The following surfactant FA 0.05 parts The following surfactant FK 0.05 parts

[0121]

Embedded image

The samples prepared in Examples 8 to 13 and Comparative Examples 5 to 7 were evaluated in the same manner as in Examples 1 to 7. Table 2 summarizes the evaluation results.

[0123]

[Table 2]

As is clear from Table 2, it was confirmed that the effect of the present invention was further increased by using the modified polyvinyl alcohol of the present invention in combination with gelatin.

[0125]

By using a modified polyvinyl alcohol for the ink receiving layer, an ink jet recording sheet excellent in dryness without density unevenness or stripe unevenness was obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D21H 19/10 D21H 1/34 B

Claims (5)

[Claims] 1. An ink jet recording sheet having an ink receiving layer provided on at least one side of a support, wherein the ink receiving layer contains a modified polyvinyl alcohol having a structural unit represented by the following general formula (V). A recording sheet for ink jet, characterized in that: Embedded image [Wherein, R represents a hydrogen atom or an alkyl group, an aryl group, or an acyl group, m1 represents an integer of 0 to 2, j1, j
2, j3 each represents an integer of 0 to 500. Where j
1 + j2 + j3 ≧ 1. A ₁ , A ₂ and A ₃ each represent a substituted or unsubstituted linear or branched alkylene group. ] 2. The ink jet recording sheet according to claim 1, wherein m1 is an integer of 1 in the general formula (V). 3. The modified polyvinyl alcohol according to claim 1, wherein the modified polyvinyl alcohol has 1 to 40 mol% of a structural unit represented by the general formula (V).
Or the recording sheet for inkjet according to 2. 4. The ink jet recording sheet according to claim 1, wherein the ink receiving layer contains gelatin. 5. The ink-jet recording sheet according to claim 1, wherein the support is a film or a resin-coated paper in which both surfaces of a paper are coated with a resin.