JPH09208853A - Composition for forming ink-receiving layer and ink-receiving recording material prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for forming an ink-receiving layer suitable for an ink jet recording system for a variety of substrates by compounding a specific polymerizable cationic polyacryloyl compound with a specific acrylic copolymer. SOLUTION: This composition comprises the following components I and II. Component I is a polymerizable cvationic polyacryloyl compound represented by formula 1 and/or formula 2 which has two or more acryloyl groups and one or more cationic groups in the molecule. In the formulae 1 and 2 Z1 and Z2 are each an aliphatic residue of an aliphatic polyol; R1 -R7 are each an ethylene oxide chain; K is an atomic group selected among formulae (a)-(e) whose end is cationic; A is a residue of a (meth)acrylic ester; and X is an atomic group selected among formulae (a)-(e) and A. Component II is an acrylic polymer comprising the following monomers by weight: 20-60% acrylamide, 10-35% acrylic ester having an ethylene glycol side chain, and 15-40% alkyl acrylate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition used for forming an ink-receiving layer and an ink-receiving recording material using the composition, more specifically, a novel polymerizable cationic polyacryloyl compound. An ink-receiving layer-forming composition using the same, as an application thereof, a water-based printing ink, particularly an ink-receiving layer-forming composition used for a water-based inkjet ink suitably used in an inkjet recording system, and an ink receiving using the same. Recording material.

[0002]

2. Description of the Related Art In recent years, the ink jet recording system has made great progress in the digital recording system and has been widely used as an output device from a personal computer which is widely used in offices. These are the result of the development of a compact high-density multi-nozzle inkjet recording head, the development of precision driving technology for driving them, and the development of a recording medium having printability capable of achieving high image quality. In many of the ink jet printers that have become widespread in this way, water-based inks mainly containing water are used. Water-based inks are desirable ink-based inks not only in offices but also in industrial fields from the viewpoints of environmental protection and effects on the human body. However, regarding recording media suitable for such water-based inks, some recording media specially developed for these printers (for example, inkjet paper, OHP film, etc.) are currently available. It leaves basic functional challenges.

That is, the basic problems mentioned above include the following. (1) Regarding paper, the coloring material in the water-based ink may cause diffusion and bleeding even in the case of paper developed for inkjet, especially in a high humidity environment, and the waterfastness of the image is not sufficient. I can't say. (2) Regarding the OHP film, not only the water resistance of the film itself and the water resistance of the image are still extremely insufficient, but special attention needs to be paid to the use environment and the storage environment. The above problems are the results of the use of mainly water-soluble polymer compounds as the material for forming the recording medium for inkjet recording, because it is necessary to impart high-speed absorbability to aqueous ink. . That is, in common with both of the above problems, in the design of the recording medium for water-based ink, the improvement of water resistance as an image receiving paper is inevitably incompatible with the improvement of ink receptivity and ink absorption. This is because it has been considered to be a trade-off problem of satisfying mutually conflicting performance requirements.

On the other hand, in recent years, there is a trend to apply the above-mentioned ink jet printer having excellent performance as a digital printing apparatus for industrial use. In this case, the recording medium to be printed often does not have the absorbability of the water-based ink, and it is essential to form an ink absorbing layer having the ink absorbability on the recording medium in advance. . Here, for industrial use, for example,
Prepaid cards, compact discs, laser discs, nameplates, image displays, image formation on FRP plates, image formation on pottery, printing, skin coloring, stained glass making, painting reproduction, calligraphy reproduction, etc. .
A wide variety of recording media are used as the recording medium used at this time, and examples thereof include metal plates, plastics, rubbers, ceramics, cloth, leather, glass, and foods. Obviously, most of these substrates are not receptive to water-based inks by themselves.

However, in the conventional coating material used for the above-described coated paper or OHP film designed for ink jet recording, an ink receiving layer (hereinafter, simply referred to as an ink jet ink receiving layer) is formed. However, it is not possible to meet the practical demand as the print quality just by applying this. The main reasons are that these coating materials have good adhesion to various substrates, suitability for coating,
This is because the properties such as the durability of the coating film, the water resistance of the coating film, the water resistance of the image, and the scratch resistance are very insufficient. That is, as the performance required for the material for forming the ink-jet ink-receiving layer required for the industrial use as described above, it is considered that the following properties are required in addition to having a good color developing property. . The ink receiving layer can be formed on various substrates in a short time. Must have high adhesion to the substrate. Ink fixing time is short when printed. The coloring material components (dye, pigment) in the ink are strongly dyed. Be able to form clear, high-resolution images. Must be a resin layer with high robustness

On the other hand, the conventional ink-jet ink-receiving layer-forming material has an insufficient performance in the first place as described above, and is also used in the industry in which a base material having no water-based ink receptivity is used. For practical applications, diversion of these materials would be almost difficult. One of the features of the present invention is to solve the trade-off problem of how to satisfy the contradictory required performances as described above.

Further, conventionally, a proposal has been made to form an ink-jet ink-receiving layer by ultraviolet curing,
For example, Japanese Patent Laid-Open No. 62-221591 is known. However, an ink-jet ink-receiving layer using a conventional water-soluble acrylic ester-based photosensitive resin is suitable for the performance required for an ink-jet color printer which has been particularly popular in recent years, and the above-mentioned requirements. The performance, especially high ink absorption capacity and absorption speed, was not satisfied with the perfect dyeing property of the coloring material.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems, and particularly to provide a composition for forming an ink-jet ink-receiving layer which is suitably used in an ink jet recording system, and a composition for the same. It is to provide an ink-receptive recording material used. Further, the object of the present invention is to
An ink-receiving layer-forming composition capable of forming an ink-receiving layer having excellent water resistance even in recording using an aqueous ink and also having excellent ink-receiving property and ink-absorbing property, and an ink using the composition An object is to provide a receptive recording material. Another object of the present invention is to provide adhesion, coating suitability, coating durability, coating water resistance, image water resistance to various substrates that themselves do not have water-based ink receptivity. Another object of the present invention is to provide an ink-receiving layer-forming composition capable of forming an ink-receiving layer capable of satisfying scratch resistance and the like, and an ink-receiving recording material using the composition.

[0009]

The above object is achieved by the present invention described below. That is, the present invention uses 2 in one molecule.
A polymerizable cationic polyacryloyl compound (a) represented by the following general formula (Chemical formula 1) and / or (Chemical formula 2) having at least one acryloyl group and at least one cationic group, and A composition comprising a water-insoluble and hydrophilic acrylic polymer (b) containing the following components (1) to (3), which is polymerized after coating the composition on a substrate. A composition for forming an ink-receiving layer, which comprises forming a coating film comprising a solid layer and using the coating film as an ink-receiving layer, and an ink-receptive recording material using the composition.

[0010]

Embedded image [In the general formula (Formula 1) or (Formula 2), Z ₁ and Z ₂ represent an aliphatic residue of an aliphatic polyhydric alcohol. R _{1 to} R ₇ represent ethylene oxide chains. In addition, R in the general formula (Formula 1)
The total number of ethylene oxide chains of _{1 to} R ₄ is 9 to 50, and the total number of ethylene oxide chains of R _{5 to} R _{7 in} the general formula (Formula 2) is 9 to 50. K represents an atomic group selected from the following formulas (a) to (e) having a cationic terminal.

[0011]

Embedded image (In the above formulas (a) to (e), the counter ion of the cation group is a residue of an ordinary acid such as chloride ion, sulfate ion, acetate ion, and lactate ion.) ) Or (Chemical Formula 2) is a residue of a (meth) acrylic acid ester and represents an atomic group containing the following formula (f) or (g). _{CH 2 = CHCOO (f) CH} 2 = C (CH 3) COO- (g) Further, X is any one of functional groups selected from the above equation (a) ~ (g). (1) 20 to 60% by weight of acrylamide monomer (2) 10 to 35% by weight of acrylic acid ester monomer having an ethylene glycol chain in the side chain (3) 15 to 4% of acrylic acid alkyl ester monomer
0% by weight

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in detail with reference to preferred embodiments. One of the basic substances constituting the ink receiving layer forming composition of the present invention is a compound having two or more acryloyl groups and one or more cation groups in one molecule. The ink receiving layer containing these compounds becomes a substantially solid inkjet ink receiving layer in a short time by applying ultraviolet rays or an electron beam after coating on a substrate. That is, the present invention is characterized in that a novel cationically polymerizable material is used, and by using the cationic UV-curable material, it is required as a material for forming the ink jet ink-receiving layer described above. An ink-receptive layer having many performances satisfied is provided.

First, a polymerizable polymer represented by the following general formula (Formula 1) and / or (Formula 2) having two or more acryloyl groups and one or more cation groups in one molecule used in the present invention is used. As a method for synthesizing the cationic polyacryloyl compound (a), there are, for example, the following two synthetic routes. [Synthesis Route 1] Step (1): Add 9 mol to 50 mol of ethylene oxide to the polyol having 3 or more hydroxyl groups. Step (2): The product of step (1) is reacted with epichlorohydrin to make all the terminal hydroxyl groups epoxides. Step (3): A tertiary amine is bound to the product of step (2) to quaternize (cationize) a part of the terminal. Step (4): (meth) acrylic acid is reacted with the remaining epoxide of the reaction product of step (3) to acryloylate the terminal.

[Synthesis Route 2] Step (1): 9 mol to 50 mol of ethylene oxide is added to a polyol having 3 or more hydroxyl groups. Step (2): A cationizing agent (for example, a compound having an epoxy group and a cation group such as 2,3-epoxypropyltrimethylammonium chloride) is reacted with the terminal hydroxyl group of the product of the step (1) to partially cationize Turn into. Step (3): The remaining hydroxyl groups of the product of step (1) are reacted with (meth) acrylic acid chloride to acryloylate the ends.

Examples of the polyol having three or more hydroxyl groups include glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, 1,2,5-dipentanetriol, 1,
3,5-pentanetriol, 1,2,4-butanetriol, dipentaneerythritol, polyglycerin,
Examples include trishydroxyethyl isocyanurate. Although not specifically exemplified here, it is of course possible to derive compounds having similar properties from compounds having 4 or more hydroxyl groups such as monosaccharides and disaccharides.

Examples of amines used for cationization in Synthesis Route 1 include ethanolamine, methylethanolamine, diethanolamine, methyldiethanolamine, dimethylethanolamine, ethylethanolamine, diethylethanolamine, diisopropylethanolamine, isopropylaminoethanol. ,
Butyl ethanolamine, dibutyl ethanolamine,
Alkylalkanolamines such as dimethylisopropanolamine and dimethylaminoethoxyethanol are preferably used. Further, for example, trimethylamine, butylamine, di-n-propylamine, sec-butylamine, n-heptylamine, dimethylethylamine, dimethylbutylamine, dimethylaminopropylamine,
Alkyl amines such as diethylaminopropylamine may also be used in the same reaction. However, when these unreacted components remain in the coating film, these alkyl amines
Due to their relatively high vapor pressure, they can be odorous and have the disadvantage that industrial measures must be taken to eliminate them.

Examples of the cationizing agent used in Synthesis Route 2 include the compounds shown below. 2,
3-epoxypropyltrimethylammonium chloride (Product example: WeiStex-E100, manufactured by Nagase Kasei)

Embedded image

3-Chloro-2-hydroxypropyltrimethylammonium chloride (Product example: Waitex N)
-50, manufactured by Nagase Chemical Industries)

[Chemical 6]

[0019]

Embedded image

Next, specific examples of the polymerizable cationic polyacryloyl compound (a) used in the present invention synthesized as described above are shown below. The following structural formula (a-
Two moles of acryloyl groups in one molecule obtained by adding 30 moles of ethylene oxide to pentaerythritol represented by 1), epoxidizing with epichlorohydrin, cationizing with trimethylamine, and then esterifying with acrylic acid. And a compound having two cationic groups.

Embedded image

After adding 50 mol of ethylene oxide to glycerin represented by the following structural formula (a-2) and cationizing a part of hydroxyl groups with 3-chloro-2-hydroxypropyltrimethylammonium chloride, acrylic acid is added. A compound having two acryloyl groups and one cation group in one molecule, which is obtained by acryloylation with chloride.

Embedded image

9 mol of ethylene oxide was added to trimethylolpropane represented by the following structural formula (a-3), epoxidized with epichlorohydrin, cationized with diethanolamine, and then esterified with acrylic acid. A compound having two acryloyl groups and two cation groups in one molecule obtained by cyclization.

Embedded image

However, the above chemical structures (a-1) to (a)
-3) is ideal, and there is a distribution in the addition reaction of ethylene oxide, and since there are three or more reaction sites in one molecule, the number of acryloyl groups and cationic groups introduced in the molecule is It cannot be denied that there is a distribution in. However, if the reaction is controlled by controlling the reaction conditions to obtain reproducibility and the storage stability is obtained by stabilizing the catalyst, it can be used practically without further special purification. Is.

Next, the following (1) is added to the copolymer which is another forming material of the composition for forming the ink receiving layer of the present invention.
The water-insoluble and hydrophilic acrylic polymer (b) containing the components (3) to (3) will be described. (1) 20 to 60% by weight of an acrylamide-based monomer, and (2) 1 of an acrylic acid ester monomer having an ethylene glycol chain as a side chain.
0 to 35% by weight, (3) 15 to 40% by weight of acrylic acid alkyl ester monomer,

Here, (1) acrylamide-based monomer means, for example, the following substances. For example,
N, N-dimethylaminoacrylamide, N, N-dimethylaminomethacrylamide, N, N-dimethylaminoethylacrylamide, N, N-dimethylaminoethylmethacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethyl Aminopropylmethacrylamide, N, N-dimethylamino2-hydroxypropylacrylamide, N, N-methylamino2-
Hydroxypropyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, butoxymethyl acrylamide, N-morpholino acrylamide and the like. In the present invention, the amount of these monomers in the copolymer is in the range of 20 to 60% by weight. When the amount of the monomer is less than 20% by weight, the water-based ink absorbency of the ink receiving layer becomes insufficient,
If it is more than 60% by weight, the resin has too much water solubility and water resistance cannot be obtained.

Next, examples of (2) acrylic acid ester monomers having an ethylene glycol chain in the side chain include the following substances. (2-1) acrylate ester having an ethylene glycol chain in the side chain represented by the following general formula _{CH 2 = C (R) -COO-} (CH 2 CH 2 O) n -H (2-1) [ wherein In (2-1), n represents an integer of 2 to 24, and R represents a hydrogen atom or a methyl group. ]

Specific examples of the general formula (2-1) include:
For example, the following are mentioned. _{· CH 2 = C (CH 3} ) -COO- (CH 2 CH 2 O) n -H n = 1.9 ( product example BLEMMER PE-90, manufactured by NOF _{Corporation) · CH 2 = C (CH} 3) - _{COO- (CH 2 CH 2 O)} n -H n = 4.4 ( product e.g. Blemmer PE-200, manufactured by NOF _{Corporation) · CH 2 = C (CH} 3) -COO- (CH 2 CH 2 O) n -Hn = 7.7 (Product example: Bremmer PE-350, manufactured by NOF CORPORATION)

(2-2) Acrylic ester having an ethylene glycol chain of an alkyl ether at the side chain end CH ₂ = C (R) -COO- (CH ₂ CH ₂ O) _m- (CH ₂ ) _p -H ( 2-2) [In the formula (2-2), m represents an integer of 2 to 24, p represents an integer of 1 to 16, and R represents a hydrogen atom or a methyl group. ]

Specific examples of the general formula (2-2) include:
For example, the following monomers having an ethylene oxide chain as a side chain may be mentioned.・ Methoxytriethylene glycol acrylate (R =
H, m = 3, p = 1, trade name: NK ester AM-30
G, manufactured by Shin-Nakamura Chemical Co., Ltd.-Methoxypolyethylene glycol # 400 acrylate (R = H, m = about 10, p = 1, trade name: NK ester AM-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.)・ Methoxydiethylene glycol methacrylate (R
_{= CH 3, m = 2,} p = 1, trade name: NK ester M-
20G, manufactured by Shin-Nakamura Chemical Co., Ltd.)-Methoxytetraethylene glycol methacrylate (R = CH ₃ , m = 4, p = 1, trade name: NK ester M-40G, manufactured by Shin-Nakamura Chemical Co., Ltd.) Methoxy polyethylene glycol # 400 methacrylate (R = CH ₃ , m = about 10, p = 1, trade name: N
K ester M-90G, manufactured by Shin-Nakamura Chemical Industries Co.), methoxy polyethylene glycol # 1000 methacrylate (R = CH _3, m = about 24, p = 1, trade name: N
K ester M-230G, manufactured by Shin-Nakamura Chemical Co., Ltd.-Butoxydiethylene glycol acrylate (R =
H, m = 2, p = 4, trade name: NK ester AB-20
G, Shin-Nakamura Chemical Co., Ltd.) In the present invention, these monomers are used in the range of 10 to 35% by weight. It is important to use each monomer in the copolymer in this range in order to balance ink absorbency and water resistance. That is, if the amount of the above monomer is less than 10% by weight, the ink absorbency is poor, and if it is more than 35% by weight, the water resistance of the image is inferior, which is not preferable.

Next, (3) alkyl acrylate ester monomer means, for example, methyl (meth) acrylate,
Examples thereof include compounds having an alkyl group in the side chain, such as ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. In the present invention, these monomers are used in the range of 15-40% by weight. If it is less than 15% by weight, tack tends to occur as an ink absorbing layer and the water resistance of the non-printed portion is lowered, while if it is more than 40% by weight, the ink absorbing speed is lowered, which is not preferable.

Specific examples of the copolymer (b) used in the present invention which satisfies the above requirements (1) to (3) include the followings. N, N-dimethylaminoacrylamide / Blemmer PE-90 / methyl methacrylate = 50/35/15 N-morpholinoacrylamide / Blemmer PE-
200 / methyl methacrylate = 60/20/20 N-methyl roll acrylamide / NK ester M-
90 G / ethyl methacrylate = 20/40/40 N, N-dimethylamino 2-hydroxypropyl acrylamide / NK ester AM-30G / ethyl methacrylate = 50/35/15

The hydrophilic acrylic polymer which is the above-mentioned copolymer preferably has a weight average molecular weight of 50,000 to 350,000 and a glass transition temperature of 40 to 120 ° C. These materials do not dissolve in pure water. Examples of the solvent capable of dissolving these include polar solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, isopropyl alcohol, N-methylpyrrolidone, methyl ethyl ketone, acetone, tetrahydrofuran, acetonitrile and mixtures thereof.
Water can be used as a part of these mixed solvents.

Preferred examples of these mixed solvents include:
For example, the following may be mentioned. -Ethylene glycol monomethyl ether / isopropyl alcohol = 50 / 50-Ethylene glycol monoethyl ether / methyl ethyl ketone = 60 / 40-N-methylpyrrolidone / water = 70/30

It is preferable to add a polymerization initiator which can be activated by an active energy ray to the composition for forming the ink receiving layer in the present invention. By doing so, the composition of the present invention can be polymerized in a short time to form a solid layer easily by irradiating the composition with an ultraviolet ray which is an active energy ray using an ultraviolet light source or the like.

As the polymerization initiator used in this case,
For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 2,2
-Diethoxyacetophenone, 2,2-dimethoxy-2
-Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1
-[4- (Methylthio) phenyl] -2-morpholinopropane-1,4-phenoxydichloroacetophenone, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, pt-butyldichloro Acetophenones such as acetophenone, pt-butyltrichloroacetophenone and p-dimethylaminoacetophenone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether and benzyl dimethyl ketal; Benzophenone, benzophenone methyl ether, benzoylbenzoic acid, methyl benzoylbenzoate,
Hydroxybenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 3,3'-bis (N, N-dimethylamino) benzophenone, 4,4'-bis (N, N-diethylamino)
Benzophenone, 4 ', 4 "-diethylisophthalophen, 3,3', 4,4'-tetra (t-butyl-oxycarbonyl) benzophenone, 4-benzoyl-4'-
Benzophenones such as methyldiphenyl sulfide and acrylated benzophenone; thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,
4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2
Xanthones such as -chlorothioxanthone and 2,4-dichlorothioxanthone; diketones such as diacetyl and benzyl; 2-ethylanthraquinone, 2-tbutylanthraquinone, 2,3-diphenylanthraquinone, 1,
2-benzanthraquinone, octamethylanthraquinone, camphorquinone, dibenzosuberone, 9,10-
Quinones such as phenanthrenequinone; and the like.

Further, in the composition for forming an ink receiving layer of the present invention, CGI-1700, CGI-149 (bisacylphosphine oxide, which is a polymerization initiator which is photosensitive to visible light and suitable for a white pigment system, is used. Blended products based on Ciba-Geigy (Japan) are also useful in dispersion systems. However, when the electron beam curing method is used, these polymerization initiators are not always necessary.

As described above, the constituent materials that are essentially used in the composition for forming the ink receiving layer of the present invention are:
(A) Polymerizable cationic polyacryloyl compound (abbreviated as Polymerizable Cationic Oligomer = PCO)
And (b) a water-insoluble and hydrophilic acrylic polymer (abbreviated as Hydrophobic Nonaqueous Polymer = HNP)
However, in the present invention, the composition ratio is PCO:
HNP = 50: 50 to 80:20 is preferable. When the ultraviolet curing method is used, the above PCO
It is preferable to add the above-mentioned polymerization initiator in the range of 3 to 10 parts by weight with respect to 100 parts by weight of the total of HNP component and HNP component.

The composition for forming an ink-jet ink-receiving layer of the present invention, in addition to the cationic compounds as exemplified in the above (a-1) to (a-3), has no conventional cationic group. Acrylic photopolymerizable compounds known from the above can be used in combination. Conventionally known photopolymerizable compound, unlike the above, does not have a dye group because it does not have a cationic group, adjustment of the hydrophilic balance of the solid layer itself when formed as an ink receiving layer, It may be used for the purpose of improving the adhesion to the base material, adjusting the physical properties of the solid layer (such as hardness and flexibility). For example, when the ink receiving layer is formed only of the polymerizable monomer having a cationic group, the receiving layer may have too high hydrophilicity, so that the substrate may be curled. Addition of an acrylic photopolymerizable monomer having no cationic group effectively acts to control in such a case.

Examples of substances used together for such purposes include polyhydric alcohols, glycols, polyethylene glycols, polyester polyols, polyether polyols and urethane-modified polyethers, which are widely used as photopolymerizable oligomers. Alternatively, (meth) acrylic acid esters such as polyester, (meth) acrylic acid esters such as epoxy resin, etc. may be mentioned.

Specific examples of these materials include, for example,
Ethylene glycol di (meth) acrylate, propanediol di (meth) acrylate, butanediol di (meth) acrylate, pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Hydroxypivalic acid neopentyl glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetrafuran glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Examples thereof include (meth) acrylate and pentaerythritol tetra (meth) acrylate.

Examples of the (meth) acrylic acid esters of polyester or polyurethane include, for example, trade names Aronix M-1100 and Aronix M-120.
0, Aronix M-6100, Aronix M-62
00, Aronix M-6250, Aronix M-6
300, Aronix M-6400, Aronix M-
7100, Aronix M-8030, Aronix M
-8100, (all manufactured by Toagosei Kagaku Kogyo Co., Ltd.), Kayarad DPCA-120, Kayarad DPCA-
20, Kayarad DPCA-30, Kayarad DP
CA-60, Kayarad R-526, Kayarad R
-629, Kayarad R-644, (above, Nippon Kayaku Co., Ltd. product) are mentioned.

Examples of substances derived from epoxy resins include 1,6-hexanediol diglycidyl ether di (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate,
Glycerin triglycidyl ether tri (meth) acrylate, isocyanuric acid triglycidyl ether tri (meth) acrylate, (meth) acrylic acid ester of novolac type epoxy resin, (meth) acrylic acid ester of bisphenol type epoxy resin, etc. in one molecule Examples thereof include (meth) acrylic acid esters of compounds having two or more epoxy groups, and trade names include denacol acrylate DM-201, DM-811, DM-85.
1, DM-832, DA-911, DA-920, DA
-931, DA-314, DA-701, DA-72
1, DA-722, (above, manufactured by Nagase Kasei) and the like. In addition to these polyfunctional monomers, it is also possible to use monofunctional monomers having a tertiary amine and a quaternary ammonium in order to adjust the viscosity to a low level.

The composition for forming the ink receiving layer of the present invention comprises
It is also possible to adjust the absorption amount and absorption speed of the ink when the ink receiving layer is formed by incorporating a water-soluble polymer within the range of compatibility. Examples of such water-soluble polymers include polyvinyl alcohol, polyvinyl alcohol and polyvinyl acetate copolymer, polyvinyl formal, polyvinyl butyral, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl starch, polyethyloxazoline, poly. Commercially available water-soluble or water-swellable polymers such as ethylene oxide, polyethylene glycol, polypropylene oxide, polyethylene oxide / propylene oxide block copolymers are mentioned. Particularly preferably, polyvinyl alcohol, polyacrylamide, poly N-vinylpyrrolidone,
Polyethylene oxide, polyoxyethylene oxide /
Examples include propylene oxide block copolymers.

Next, a method for producing various recording materials using the composition for forming an ink receiving layer of the present invention will be described. A recording material produced using the composition for forming an ink receiving layer of the present invention is OH in an inkjet recording system.
It is preferably used for a sheet for P (OHP film).
This is because the recording material has transparency and is excellent in ink absorbability and dyeability of the water-based ink. A film of the type used in graphic arts is preferably used as the support film for such an overhead projector. As such a thing, for example,
Polyethylene terephthalate, cellulose acetate,
Examples thereof include films made of polycarbonate, polyvinyl chloride, polystyrene, aliphatic polyester and the like.

The composition for forming an ink receiving layer of the present invention is used for the purpose of imparting ink absorbability and dyeability to the above-mentioned non-ink absorbable substrate. That is, it is used for forming an ink receiving layer on a substrate before printing using an inkjet printer. For that purpose, the composition is applied and cured on a substrate to form an ink receiving layer. As a coating method therefor, spinner, roll coater, spray coater, screen printing, etc. Either can be applied. After applying by such a method, evaporate and dry the solvent,
The ink receiving layer is formed by polymerizing by UV irradiation or electron beam irradiation to solidify.

As described above, the base material to which the composition for forming an ink receiving layer of the present invention can be applied is not only paper or plastic film, but also metal plate, plastic molded product, rubber, ceramics, cloth, leather. It is used for imparting ink receptivity to various non-ink-absorbing substrates such as glass, food and the like. Examples of the coating method therefor include a roll coater, screen printing, gravure printing, offset printing, spin coater, spray coater, dip coater and bar coater. In addition, a film may be formed on a release paper or the like using the composition for forming an ink receiving layer of the present invention to form another transfer paper, and the transfer paper may be used to transfer to the above substrate. Is also possible. Further, the ink-receiving layer-forming composition of the present invention is diluted with a solvent to have a viscosity of about 5 centipoise or less to form an ink-jet recording ink, which is applied onto a substrate by an ink-jet recording method to form an ink-receiving layer. It is also possible in principle to do so.

When the composition for forming an ink-receiving layer of the present invention is used in the production of an ink-jet paper, the porosity conventionally used in order to impart faster absorbency (speed, absorption amount) or whiteness. A fine particle material having a high viscosity and a white pigment may be dispersed and blended. Examples of such a particle material include inorganic compounds such as silica, magnesium carbonate, alumina, talc, clay, and titanium oxide, and acrylic, styrene, silicone, vinyl, fluorine, urea resin, and other porous materials. Organic fine particles.

[0048]

The present invention will be described more specifically with reference to the following examples. In the examples, "parts" and "%" are based on weight unless otherwise specified. Example 1 -Hydrochloride salt of PCO compound of the structural formula (a-1) (as solid content) 80 parts-From N, N-dimethylaminoacrylamide / Blemmer PE-90 / methyl methacrylate = 50/35/15 Ethylene glycol monomethyl ether / isopropyl alcohol (50/50) 25% solution of HNP compound (20 parts as solid content) 80 parts-Irgacure 2959 (photopolymerization initiator, manufactured by Ciba-Geigy Ltd.) 3.0 parts Consists of the above components The composition was applied to an untreated polyethylene terephthalate film having a thickness of 85 μm with a wire bar coater and dried at 70 ° C. for 3 minutes to form a layer having a dry thickness of about 20 μm. This film was irradiated with ultraviolet rays of 450 mJ / cm ² (amount of light near 365 nm) in total from a high pressure mercury lamp to polymerize and solidify to form an ink receiving layer.

Next, each of the obtained films was dipped for 60 seconds in each of the following dye aqueous solutions for ink jet (concentration of 8% by weight). The dye used in the aqueous dye solution for inkjet is C.I. I. Food Blac
k 2, C.I. I. Direct Blue 199,
C. I. Direct Yellow 86, black dyes of the following structural formulas (A) and (B), and structural formula (C)
It is a magenta dye.

Black dye (A)

Embedded image

Black dye (B)

Embedded image

Magenta dye (C)

Embedded image

Next, when the film immersed in the aqueous dye solution was washed with water and then dried, the film became transparent and had a deeply colored state. Further, the dyed film obtained did not elute the dye by further washing with water and showed a good dyeing state. Further, even when immersed in water, swelling and peeling of the coating film did not occur, and the film itself showed good water resistance.

Example 2 Lactate salt of PCO compound of structural formula (a-2) (as solid content) 50 parts N-morpholinoacrylamide / Blenmer PE-200 / methyl methacrylate = 60/20/20 Ethylene glycol monomethyl ether / methyl ethyl ketone (60/40) 25% solution of HNP compound (50 parts as solid content) 200 parts-CGI-1700 (photopolymerization initiator, manufactured by Ciba-Geigy Japan) 4.0 parts From the above components The composition was applied to an untreated polyethylene terephthalate film having a thickness of 85 μm with a wire bar coater and dried at 85 ° C. for 10 minutes to form a layer having a dry thickness of about 18 μm. 400 mJ / cm ² (light intensity near 365 nm) accumulated on this film from a high-pressure mercury lamp
Was irradiated with ultraviolet rays to polymerize and solidify to form an ink receiving layer on the polyethylene terephthalate film.

Example 3 Hydrochloride of PCO compound of structural formula (a-3) (as solid content) 75 parts N-methyl roll acrylamide / NK ester M-90G / ethyl methacrylate = 20/40/40 Ethylene glycol monomethyl ether / isopropyl alcohol (50/50) 25% solution of HNP compound consisting of (25 parts as solid content) 100 parts-Irgacure 184 (photopolymerization initiator, manufactured by Ciba-Gigi Japan) 3.5 parts From the above components The composition was applied to an untreated polyethylene terephthalate film having a thickness of 85 μm with a wire bar coater and dried at 85 ° C. for 10 minutes to form a layer having a dry thickness of about 18 μm. 350 mJ / cm ² (light intensity near 365 nm) accumulated on this film from a high-pressure mercury lamp
Was irradiated with ultraviolet rays to polymerize and solidify to form an ink receiving layer on the polyethylene terephthalate film.

Example 4 Hydrochloride of PCO compound of the above structural formula (a-1) (as solid content) 75 parts N, N-dimethylamino-2-hydroxypropylacrylamide / NK ester AM-30G / methacrylic acid Ethylene glycol monomethyl ether / methyl isobutyl ketone (50/50) 25% solution (25 parts as solid content) of HNP compound of ethyl = 50/35/15 100 parts-Irgacure 184 (photopolymerization initiator, manufactured by Ciba-Geigy, Japan) ) 3.5 parts A composition comprising the above components is applied to an untreated polyethylene terephthalate film having a thickness of 85 μm with a wire bar coater and dried at 100 ° C. for 10 minutes to form a layer having a dry thickness of about 15 μm. did. A transparent polyethylene terephthalate film having an ink receiving layer according to the present invention was produced by irradiating the film with ultraviolet rays of 350 mJ / cm ² (amount of light near 365 nm) in total from a high pressure mercury lamp to polymerize and solidify.

Example 5 : Hydrochloride of PCO compound of the above structural formula (a-1) (as solid content) 75 parts N, N-dimethylamino 2-hydroxypropyl acrylamide / NK ester AM-30G / methacrylic acid Ethylene glycol monomethyl ether / methyl isobutyl ketone (50/50) 25% solution of HNP compound consisting of ethyl = 50/35/15 (25 parts as solid content) 100 parts Titanium oxide pigment (CR-50, manufactured by Ishihara Sangyo) 10 parts-CGI-1700 (photopolymerization initiator, manufactured by Ciba-Geigy Japan) 3.5 parts A composition comprising the above components was subjected to a dispersion treatment at 8,000 rpm for 20 minutes using an ultra homogenizer to obtain a white ink receiving material. A layer forming composition was prepared. The composition thus obtained was applied to an untreated polyethylene terephthalate film having a thickness of 85 μm by a wire bar coater and dried at 100 ° C. for 10 minutes to give a dry thickness of about 17 μm.
m resin layer. This film was irradiated with ultraviolet rays of 600 mJ / cm ² (amount of light near 365 nm) in total from a high pressure mercury lamp to polymerize and solidify to form a white ink receiving layer on the polyethylene terephthalate film.

Comparative Example 1 In Example 1, except that the following components were used:
An ink receiving layer was formed on the polyethylene terephthalate film in the same manner as in Example 2. -Acrylic acid ester of glycerin polyglycidyl ether DA-314 (as a solid component) 25 parts-Ethylene of HNP compound consisting of N, N-dimethylaminoacrylamide / Blemmer PE-90 / methyl methacrylate = 50/35/15 Glycol Monomethyl ether / isopropyl alcohol (50/50) 25% solution (20 parts as solid content) 100 parts-Irgacure 2959 (photopolymerization initiator, manufactured by Nippon Ciba-Geigy) 2.0 parts

Comparative Example 2 In Example 2, except that the following components were used:
An ink receiving layer was formed on the polyethylene terephthalate film in the same manner as in Example 2. Lactic acid salt of PCO compound of the structural formula (a-2) (as solid content) 50 parts of water-soluble acrylic resin polymerized using 20% of 2-hydroxyethyl methacrylate, 65% of acrylamide and 15% of methyl methacrylate 20% aqueous solution 125 parts-CGI-1700 (photopolymerization initiator, manufactured by Nippon Ciba-Gigi) 4.0 parts

[0060]

[Evaluation] Color inkjet printing was carried out using the polyethylene terephthalate film having the ink receiving layer formed in each of Examples 1 to 6 and Comparative Example 1 or 2 obtained above, and ink absorption and water resistance were evaluated. An evaluation was made.

[Color Inkjet Printing] Using the polyethylene terephthalate film having the ink receiving layer formed in each of the examples produced as described above, printing was performed by a color inkjet printer to obtain ink absorption and water resistance. An evaluation was made. As the color inkjet printer, BJC-400J manufactured by Canon Inc. was used. The printing was performed by using seven color water-based inks of black, yellow, cyan, magenta, red, blue, and green to draw a solid pattern of 2 cm × 2 cm for each. When the solid pattern is formed, the amount of the ejected ink per unit area is changed variously to obtain 5 for 0.1 to 1 color.
Printing was performed with each step of ink amount.

[Ink Absorption] As a result of the above color ink jet printing, in any of the ink receiving layers prepared in Examples 1 to 5, uniform ink absorption up to solid printing for one color, which is the maximum ink ejection amount. And a clear color chart with clear boundaries between different colors was produced without the ink overflowing. On the other hand, Comparative Example 1
Also, the film having the ink receiving layer of Comparative Example 2 was inferior in the image quality because the formed image was not clear because the ink absorbability on the film surface was inferior.

[Water resistance] After completion of the above color ink jet printing, the film of each Example was immersed in tap water for 60 seconds to examine the water resistance of the image and the ink receiving layer. As a result, in each of the films of Examples 1 to 5, extremely good water resistance was exhibited without dissolving the coating film in the non-printed portion due to water immersion or elution of the dye in the printed portion. . On the other hand, the films having the ink receiving layer of Comparative Example 1 and Comparative Example 2 were inferior in ink absorbency and had insufficient water resistance.

Example 6 The same composition for forming an ink receiving layer as that used in Example 1 was prepared by using a polypropylene as a base material and having a dry thickness on the surface of a sheet having an adhesive layer and a separator film attached to the back surface. The layers were laminated so as to have a thickness of 25 μm to form an ink receiving layer. A photographic image was printed by ejecting yellow, magenta, cyan, and black color inks from this sheet from a color inkjet printer. After printing,
The sheet was attached to a plastic plate to create a display plate similar to that on which a color image was printed. This display plate was stored in an environment of 35 ° C. and 85% RH for 2 weeks, but blurring of the image due to bleeding of the dye did not occur at all.

[0065]

As described above, according to the present invention,
Excellent water resistance, even in recording using water-based ink
Provided is an ink receiving layer capable of satisfying both ink receiving and absorbing properties. Further, according to the present invention, adhesion, coating suitability, coating durability, coating water resistance, image water resistance and scratch resistance to a base material which itself does not have the receptivity of an aqueous ink, etc. An ink receiving layer that satisfies the above requirements is provided. Particularly, according to the present invention, there is provided an ink receiving layer capable of exhibiting the above excellent performance when recording by a color inkjet recording system.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D21H 27/00 D21H 1/34 J 5/00 Z C09D 4/06 PDW 133/06 (72) Invention Kenichi Moriya 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Masato Katayama 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Shinichi Tochihara Tokyo 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Tadayoshi Inamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (4)

[Claims] 1. A polymerizable cationic polyacryloyl compound represented by the following general formula (Chemical formula 1) and / or (Chemical formula 2) having two or more acryloyl groups and one or more cation groups in one molecule. A composition comprising (a) and a water-insoluble and hydrophilic acrylic polymer (b) containing the following components (1) to (3) in a copolymer. A composition for forming an ink-receptive layer, characterized in that the composition is coated on a substrate and then polymerized to form a coating film comprising a solid layer, and the coating film is used as an ink-receptive layer. Embedded image [In the general formula (Formula 1) or (Formula 2), Z ₁ and Z ₂ represent an aliphatic residue of an aliphatic polyhydric alcohol. R _{1 to} R ₇ represent ethylene oxide chains. In addition, R in the general formula (Formula 1)
The total number of ethylene oxide chains of _{1 to} R ₄ is 9 to 50, and the total number of ethylene oxide chains of R _{5 to} R _{7 in} the general formula (Formula 2) is 9 to 50. K represents an atomic group selected from the following formulas (a) to (e) having a cationic terminal. Embedded image (In the above formulas (a) to (e), the counter ion of the cation group is a residue of an ordinary acid such as chloride ion, sulfate ion, acetate ion, and lactate ion.) ) Or (Chemical Formula 2) is a residue of a (meth) acrylic acid ester and represents an atomic group containing the following formula (f) or (g). _{CH 2 = CHCOO (f) CH} 2 = C (CH 3) COO- (g) Further, X is any one of functional groups selected from the above equation (a) ~ (g). (1) 20 to 60% by weight of acrylamide monomer (2) 10 to 35% by weight of acrylic acid ester monomer having an ethylene glycol chain in the side chain (3) 15 to 4% of acrylic acid alkyl ester monomer
0% by weight 2. The composition for forming an ink receiving layer according to claim 1, which further contains a photopolymerization initiator. 3. A white pigment is further contained.
Alternatively, the composition for forming an ink receiving layer according to claim 2. 4. A coating film is formed by applying the composition for forming an ink receiving layer according to any one of claims 1 to 3 onto a substrate to form a coating film, and the coating film is polymerized with an active energy ray. 5 to
An ink-receptive recording material comprising a solid layer of 50 μm formed as an ink-receptive layer for inkjet recording.