JP2000141885A - Coating agent for photopolymerization setting ink jet recorded image receiving layer, and recording sheet thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerization setting coating agent for forming a recorded image receiving layer into which ink or water printed by the ink jet recording method is permeated easily and a dye or a pigment can be fixed thereon firmly, and also to provide an ink jet recording sheet with the recorded image receiving layer. SOLUTION: In a coating agent for a photopolymerization setting ink jet recorded image receiving layer, a 0.5-99.5 pts.wt. acryloyl containing polymeric monomers of at least one kind selected out of cationic monomers containing amino and hydrophilic monomers is contained in both of 0.1-50 pts.wt. micromonomers polymerized with olefin and a 0.5-99.5 pts.wt. N vinyl acetoamide. A recorded image receiving layer is formed by setting a coating agent for a photopolymerization setting ink jet recorded image receiving layer on the surface of a recording base sheet of an ink jet recording sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerization-curable coating used as a recording image receiving layer for satisfactorily reproducing a clear, high-resolution image without bleeding or unevenness when printing by inkjet recording. And an ink-jet recording sheet having the recording image-receiving layer.

[0002]

2. Description of the Related Art Ink jet recording is printing by spraying fine particles of ink on paper. Since the density of the particles is expressed by the density of the particles, the ink particles are conspicuous in the lightly colored portions. Therefore, by improving the resolution to reduce the size of the ink particles, or in the case of color ink,
In addition to the four colors C, M, Y, and K (cyan, magenta, yellow, and black), inks of 6 to 7 colors can be used to reduce the graininess, or by overprinting ink with low density to achieve 2. Description of the Related Art A printer capable of clearly printing by expressing a tone has been developed.

On the other hand, when the recording medium is made of a material such as a plastic film that does not absorb ink, a recording image receiving layer is provided on the surface of the film to absorb the ink. Such an ink jet recording sheet has excellent ink absorbency, does not cause bleeding or unevenness, has excellent smoothness and glossiness, has water resistance to the sheet and the image, and has moisture attached thereto. It is also required that the image does not bleed or run off, that the sheet does not bend even if a large amount of ink is absorbed, and that the image has excellent color density and sharpness.

For example, Japanese Patent Application Laid-Open No. 60-168651 discloses a recording image receiving layer containing polyvinyl alcohol (PVA) and a polyacrylic acid-based water-soluble polymer in order to increase ink absorption. JP-A-62-168
No. 35 discloses a cationized PVA containing a water-proofing agent in order to improve the fixability of the dye. However, these recording image receiving layers have a problem that unevenness occurs due to slow drying of the ink and a low absorption speed of the ink and water in the solid portion of the color overlap. Further, as a recording sheet such as a color film for an overhead projector, a sheet obtained by diluting and coating a water-soluble polymer substance composed of PVA and its derivative with water is used. This polymer substance requires skill and time to dissolve, and 5%
If the concentration is not lower than the following, the coating cannot be performed because of high viscosity. Therefore, drying of water after coating took time and productivity was not good.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a recording image receiving layer in which ink or water printed by an ink jet recording system easily penetrates and dyes and pigments are firmly fixed. It is an object of the present invention to provide a photopolymerizable curable coating agent for constituting the above, and an ink jet recording sheet on which a recording image receiving layer is formed.

[0006]

The coating agent for a photopolymerizable curable ink jet recording image receiving layer of the present invention made to achieve the above object comprises 0.1 to 50 parts by weight of an olefin polymerized macromonomer. 0.5 to 99.5 parts by weight of N-vinylacetamide is 0.5 to 99.5 parts by weight of at least one acryloyl group-containing polymerizable monomer selected from a cationic monomer having an amino group and a hydrophilic monomer. Contains.

[0007] The coating agent is a resin having a polymerizable acryloyl group-containing polymerizable monomer, which is different from that described above, and is used as a resin.
-99.5 parts by weight. The number average molecular weight of this resin is 2,000 to 100,000. Further, 0.5 to 9 of a resin obtained by graft copolymerization of another acryloyl group-containing polymerizable monomer and a different macromonomer from the above.
It may contain 9.5 parts by weight. The number average molecular weight of the graft copolymerized resin is 2,000 to 100,000.

[0008] The coating agent for the photopolymerizable curable ink jet recording image receiving layer of the present invention comprises 0.5 to 99.5 parts by weight of at least one acryloyl group-containing polymerizable monomer selected from a cationic monomer and a hydrophilic monomer. A graft copolymer of an olefin polymerized macromonomer and N-vinylacetamide;
It may contain 9.5 parts by weight. The number average molecular weight of the graft copolymerized resin is 2,000 to 100,000.

The macromonomer is preferably at least one selected from polymethyl methacrylate, polybutyl acrylate, polystyrene, a polymer of styrene and acrylonitrile, and polydimethylsiloxane. Specifically, in a macromonomer manufactured by Toagosei Co., Ltd., the segment components constituting the macromonomer are AA-6 which is methyl methacrylate, AB-6 which is butyl acrylate, AS-6 which is styrene, and styrene. AN- which is a polymer with acrylonitrile
6, AK-6 which is dimethylsiloxane.
A copolymer of a macromonomer and an unsaturated compound may be used, or the macromonomer may be used after being diluted with a solvent.
The macromonomer is selected according to the desired glass transition temperature Tg and physical properties of the recording image receiving layer.

The cationic monomer having an amino group is preferably at least one selected from N-vinyl lactams, acrylates and acrylamides having an aminoalkyl group. Specifically, the N-vinyllactams include N-vinylpyrrolidone. Acrylic esters having an aminoalkyl group are N, N-dimethylaminoethyl methacrylate (trade name Light Ester D manufactured by Kyoeisha Chemical Co., Ltd.)
M), and DE. Acrylamides having an aminoalkyl group include N, N-dimethylaminopropylmethacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminoethylacrylamide, and N, N-dimethylacrylamide. When a recording image receiving layer is formed using a coating agent containing these cationic monomers, and an aqueous and water-dispersed ink is printed by an inkjet recording method,
Since the anionic site of the ink is ionically bonded to the cationic site in the resin, the ink is firmly fixed. Therefore, while the image-receiving layer made of PVA resin diffuses ink in a high-humidity atmosphere and causes bleeding and unevenness, the recording image-receiving layer using this coating agent provides a clear image without ink bleeding and unevenness. Can be.

The hydrophilic monomer has an acrylate containing a hydroxyl group and an alkylene oxide adduct thereof, an acrylate of polyethylene glycol, an epoxy acrylate, a hydroxyl group, an amino group, a carboxyl group or a mercapto group. It is preferably at least one selected from acrylates or epoxy acrylates of alkylene oxide adducts of aliphatic or aromatic compounds, and acrylamide derivatives.

Specifically, the acrylate containing a hydroxyl group is an acrylate or methacrylate of a hydroxyalkyl group. Examples thereof include light esters HO, HOP and HOPE manufactured by Kyoeisha Chemical Co., Ltd.
HOB, Kyoeisha Chemical Co., Ltd., trade names light acrylate HOA, HOPA, and HOBA. Acrylic esters obtained by further adding alkylene oxides having 2 to 4 carbon atoms to light esters or light acrylates, such as Blemmer P (trade name, manufactured by NOF Corporation)
E, the same PP may be used. The acrylates of polyethylene glycol are specifically acrylates of methoxypolyethylene glycol (Kyoeisha Chemical Co., Ltd.)
Acrylate 130A), methacrylic acid ester of methoxypolyethylene glycol (130MA of light ester), diacrylate of polyethylene glycol (light acrylate EG-A,
2EG-A, 3EG-A, 4EG-A, 9EG
-A and 14EG-A). The acrylic acid epoxy esters are, specifically, acrylic acid epoxy esters of phenylglycidyl ether (Kyoeisha Chemical Co., Ltd.)
Epoxy ester M-600A), glycidyl ether acrylate epoxy ester (80MFA), ethylene glycol diglycidyl ether acrylate epoxy ester (Epolite 40E) and modified acrylic acid (epoxy ester) EpEs40EA, EpEs100EA, Ep
Es200EA and EpEs400EA) and glycerol polyglycidyl ether acrylate epoxy ester (epoxy ester EX-313A). Hydroxyl, amino, carboxyl or acrylic acid esters of alkylene oxide adducts of aromatic or aromatic compounds having a mercapto group acrylic acid esters or acrylic acid epoxy esters, specifically, Kyoeisha Chemical Co., Ltd.
Trade name light ester NP-8A, NP-10A
Is mentioned. Acrylamide derivatives include, for example, (meth) acrylamide, N-methylol (meth) acrylamide, diacetone acrylamide, N-methoxymethylacrylamide, N-ethoxyethylacrylamide, N- (n-butoxymethyl) acrylamide, te
rt-butylacrylamide.

When a recording image-receiving layer is formed using a coating agent containing a hydroxyl group-containing acrylic acid ester or acrylic acid epoxy ester, acid ions of the ink are reduced when printing an aqueous or water-dispersible ink. Ink is firmly fixed because it undergoes ionic crosslinking with the hydroxyl groups in the resin. Therefore, no bleeding or unevenness occurs in the solid portion, and a high-resolution image with good color fixability can be obtained.

The coating agent has a property that the macromonomer undergoes graft copolymerization with N-vinylacetamide or an acryloyl group-containing polymerizable monomer by light irradiation, and is cured.

Preferably, a photopolymerization initiator is added to the coating agent. Photopolymerization initiators include, for example, benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin-n-butyl ether, benzoin-iso-butyl ether, benzophenone, diacetyl, acetophenone, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone Benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 1,4-iso-propylphenyl-2-hydroxy-2-methylpropan-1-one.

[0016] A thermal polymerization inhibitor may be added to the coating agent. The thermal polymerization inhibitor does not inhibit the photopolymerization reaction,
This is for improving the storage stability of the coating agent, and examples thereof include hydroquinone, hydroquinone monomethyl ether, catechol, p-tert-butylcatechol, and triphenylphosphite.

The ink jet recording sheet of the present invention comprises:
The coating agent for the photopolymerizable curable ink jet recording image receiving layer is cured by photopolymerization on the surface of the recording base sheet to form a recording image receiving layer. The base sheet is preferably made of a transparent plastic film.

When the coating agent is applied to a recording base sheet and irradiated with light, the macromonomer and its copolymerized resin in the coating agent are polymerized with N-vinylacetamide and an acryloyl group-containing polymerizable monomer, and are cured. An ink jet recording sheet having an image receiving layer is obtained. For photopolymerization, it is preferable to irradiate ultraviolet rays in a wavelength region of 150 to 500 nm. As an ultraviolet light source,
Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, and metal halide lamps can be used.

The recording image receiving layer contains a resin sharing a hydrophilic group derived from N-vinylacetamide or a polymerizable monomer and a hydrophobic group derived from a macromonomer. This resin is a hydrophilic resin that is soluble in both water and a lipophilic solvent, that is, an amphiphilic hydrophilic resin. Therefore, this recording image receiving layer has good absorption of water and organic solvent in the ink composition, and can quickly fix dyes and pigments. In general, when printing is performed by an ink jet recording method, a large amount of ink tends to be consumed at a high resolution. This recording image receiving layer does not have bleeding or blocking properties because it has good absorbability even when a large amount of ink and pigment ink are used.

This ink jet recording sheet does not adhere even when layered, and is excellent in water resistance. The ink jet recording sheet does not require drying when forming the recording image receiving layer because the coating agent does not contain water and a lipophilic solvent, and has high productivity.

[0021]

EXAMPLES A coating agent for a photopolymerizable curable ink jet recording image receiving layer and an ink jet recording sheet to which the present invention is applied are specifically manufactured as follows.

N-vinylacetamide, acrylic acid esters, acrylamides, acrylic acid epoxy esters and olefin polymerized macromonomer are mixed and stirred. Add the photopolymerization initiator to this and stir,
A coating agent for a photopolymerizable curable ink jet recording image receiving layer is obtained. This coating agent is applied to a polyethylene terephthalate film as a recording base sheet with a wire bar coater and irradiated with ultraviolet rays. The coating agent is cured by photopolymerization, and an ink jet recording sheet having a recording image receiving layer formed thereon is obtained.

In addition, a polyvinyl acetal resin, an ethylene-vinyl acetate copolymer resin, or a polyvinyl alcohol resin may be added to the coating agent in consideration of resin characteristics. In order to improve coating suitability, an antifoaming agent, a leveling agent, a thixotropic agent, a filler, and a pigment may be added. Further, a binder, a filler, a dye fixing agent, and a conductive polymer may be added. A hydrophobic monomer may be used in order to adjust the glass transition temperature and to provide adhesion and water resistance. The hydrophobic monomer is, for example, a (meth) acrylate compound or an allyl compound having an aliphatic group, an aromatic group, or an alicyclic group.

Hereinafter, embodiments of the present invention will be described in detail.
Examples 1 to 5 show examples of synthesizing a coating agent for a photopolymerizable curable ink jet recording image receiving layer to which the present invention is applied. Comparative Examples 1 to 4 show synthesis examples of coating agents to which the present invention is not applied.

(Example 1) N-vinylacetamide 25
Parts by weight, macromonomer AB-6 (manufactured by Toagosei Co., Ltd.) 1
0 parts by weight, light acrylate 130A (Kyoeisha Chemical
25 parts by weight, light acrylate HOPA
(Kyoeisha Chemical Co., Ltd.) 10 parts by weight, N, N-dimethylacrylamide 10 parts by weight, epoxy ester EX-3
10 parts by weight of 13A (manufactured by Kyoeisha Chemical Co., Ltd.) and 10 parts by weight of epoxy ester M-600A (manufactured by Kyoeisha Chemical Co., Ltd.)
The weight part was put in a flask and stirred at room temperature for about 30 minutes to make it uniform. Next, as a photopolymerization initiator, 2-hydroxy-
2-Methyl-1-phenylpropan-1-one (Darocur 1173, trade name, manufactured by Ciba-Geigy Japan) 3
A part by weight was added and stirred to obtain a coating agent.

Example 2 200 g of isopropanol was added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube, and light ester DE (Kyoeisha Chemical Co., Ltd.) 60 weight Parts, N, N-dimethylacrylamide 30 parts by weight, light ester HO
(Kyoeisha Chemical Co., Ltd.) 10 parts by weight, as a polymerization initiator,
2 parts by weight of 2,2′-azobisisobutyronitrile was added and dissolved, and the temperature was raised to 80 ° C. Aged at 80 ° C for 5 hours,
A polymerization reaction was performed. Next, isopropanol was distilled off under reduced pressure to obtain a polymer resin having a number average molecular weight of 35,000 as measured by gel permeation chromatography (GCP).

As shown in Table 1, except that N, N-dimethylacrylamide in Example 1 was replaced with a polymer resin.
A coating agent was obtained in the same manner as in Example 1.

Example 3 200 g of isopropanol was added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube, and a macromonomer AA-6 (manufactured by Toa Gosei Co., Ltd.) 10 Parts by weight, 50 parts by weight of light ester DE, 30 parts by weight of N, N-dimethylaminopropylacrylamide, HOPA light ester
And 2 parts by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator were added and dissolved, and the temperature was raised to 80 ° C. After aging at 80 ° C. for 5 hours, a polymerization reaction was carried out.
Next, isopropanol was removed by distillation under reduced pressure, and GCP was removed.
A polymer resin having a number average molecular weight of 30,000 as measured was obtained.

As shown in Table 1, except that N, N-dimethylacrylamide in Example 1 was replaced with a polymer resin.
A coating agent was obtained in the same manner as in Example 1.

(Example 4) As shown in Table 1, Example 1
In the same manner as in Example 1 except that N, N-dimethylacrylamide and epoxy ester EX-313A were replaced with the polymer resin synthesized in Example 3 and light acrylate 9EG-A (manufactured by Kyoeisha Chemical Co., Ltd.). A coating agent was obtained.

Example 5 200 g of isopropanol was added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube, and 10 parts by weight of macromonomer AA-6, N-vinylacetamide 30
Parts by weight, light ester 130MA (Kyoeisha Chemical Co., Ltd.)
40 parts by weight, light ester HOP (Kyoeisha Chemical)
10 parts by weight, 10 parts by weight of light ester DE, and 2 parts by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator were added and dissolved, and the temperature was raised to 80 ° C. 8
After aging at 0 ° C. for 5 hours, a polymerization reaction was carried out. Next, 30 parts by weight of light ester HOPA, epoxy ester M-
After adding 20 parts by weight of 600A and stirring, isopropanol was distilled off under reduced pressure to obtain a polymer resin having a number average molecular weight of 35,000 as measured by GCP.

As shown in Table 1, 70 parts by weight of the polymer resin, 15 parts by weight of the epoxy ester EX-313A, 15 parts by weight of the light acrylate 9EG-A, and 3 parts by weight of Darocur 1173 as a photopolymerization initiator were stirred. And dissolved to obtain a coating agent.

Comparative Example 1 As shown in Table 1, Example 1
N-vinylacetamide of light acrylate 9EG
A coating agent was obtained in the same manner as in Example 1 except that -A was used.

Comparative Example 2 As shown in Table 1, Example 1
Of the macromonomer AB-6 by light acrylate TM
A coating agent was obtained in the same manner as in Example 1 except that PA (manufactured by Kyoeisha Chemical Co., Ltd.) was used.

Comparative Example 3 As shown in Table 1, Example 1
N, N-dimethylacrylamide is converted to light ester T
Except having replaced with MPA, it carried out similarly to Example 1, and obtained the coating agent.

Comparative Example 4 As shown in Table 1, Example 1
A coating agent was obtained in the same manner as in Example 1 except that the epoxy ester M-600A was replaced with light acrylate TMPA.

[0037]

[Table 1]

The coating agent for the recording image receiving layer prepared in Examples and Comparative Examples was applied to a polyethylene terephthalate film having a thickness of 75 μm with a bar coater to a thickness of 20 μm. This is placed on a belt conveyor and moved at a speed of 6 m / min, and is irradiated with ultraviolet light once by one ultraviolet light irradiator 80 w high-pressure mercury lamp installed at a height of 10 cm to be cured to obtain a film sheet for color printing of an overhead projector. Was.

Next, dye ink was printed on the above-mentioned film sheet by an ink jet printer (Calario 750C (1440 resolution) manufactured by Epson Corporation).
In addition, the pigment-dispersed ink is transferred to a thermal inkjet printer (manufactured by Hewlett-Packard Japan Co., Ltd.) HP
Desk Writer 694C).

The film sheet was evaluated by the following test methods, and the results are shown in Table 2. In the table, except for the tests indicated by numerical values, those with good test results were indicated by 、, and others were indicated by ×.

In the test for transparency, the presence or absence of fogging of the recording image receiving layer was observed. In the gloss test, the presence or absence of gloss is visually observed. The blocking test was performed by observing the degree of adhesion when another sheet was placed on the printing surface 15 seconds after printing and a load of 10 g / cm ² was applied for 1 hour. Was evaluated. In the test of adhesion, after the coating layer on the sheet was cut into a gobang pattern, a cellophane tape was applied, and when the cellophane tape was peeled off, the coating layer having 100/100 was evaluated as good. Hardness test is height 10c
After curing by irradiating ultraviolet rays once at a moving speed of 6 m / min with one 80 w high pressure mercury lamp set at m and curing the film, no tackiness was recognized in the recording image receiving layer portion by finger feeling. The water resistance test was carried out 24 hours after printing K, C, M and Y, and a wiping test was carried out by dropping a drop of water. The resin and ink remaining were evaluated as good. In the test for bleeding, when a solid portion of the print was observed, one having no bleeding was evaluated as good. Mura's test is K,
When C, M, Y, R, G and B were observed after ink application, those without unevenness were evaluated as good. In the test of the curl characteristics, the presence or absence of warpage is observed when a sheet is manufactured and dried. After printing on sheet, 4
When stored at 0 ° C. and a humidity of 60% for one week, the light resistance test was performed by observing whether or not the ink and the resin were discolored, and the moisture resistance test was performed by observing whether or not the ink moved on the image receiving layer. The haze indicates a value measured by Ultrascan XE manufactured by Hunter Lab Co., Ltd., and needs to be 5 or less.
The productivity was evaluated based on whether the handling property during coating and printing was good and the drying time was short.

[0042]

[Table 2]

As shown in Table 2, with the ink jet recording sheets using the coating agents of Examples 1 to 5 to which the present invention is applied, good results were obtained in all the test items, and the coating agents of Comparative Examples 1 to 4 It was superior to the sheet using.

[0044]

As described in detail above, the coating agent for the photopolymerizable curable ink jet recording image receiving layer of the present invention has good coatability and cures promptly upon irradiation with ultraviolet light, so that the recording image receiving layer can be easily formed. It is. Therefore, the productivity of the ink jet recording sheet is good. The ink jet recording sheet has good fixability of the ink and does not cause bleeding or unevenness of a solid portion, and thus can be used as a film sheet for color printing of an overhead projector. Furthermore, since it has good absorbency for water and organic solvents, it can be used as an ink-jet backprint sheet for fixing ink solvents.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // B05D 5/04 B05D 5/04 (C08F 290/04 226: 02)

Claims (6)

[Claims] 1. An olefin polymerized macromonomer in an amount of 0.1 to 50 parts by weight and an N-vinylacetamide in an amount of 0.5 to 99.5 parts by weight are selected from a cationic monomer having an amino group and a hydrophilic monomer. 0.5 of at least one acryloyl group-containing polymerizable monomer
A coating agent for a photopolymerization-curable inkjet recording image-receiving layer, which comprises from 9 to 99.5 parts by weight. 2. The photopolymerizable curable ink jet recording image receiving apparatus according to claim 1, wherein the polymerizable monomer containing an acryloyl group-containing polymer other than the above contains 0.5 to 99.5 parts by weight of a polymerized resin. Coating agent for layer. 3. The method according to claim 1, wherein the polymer comprises 0.5 to 99.5 parts by weight of a resin obtained by graft copolymerization of another acryloyl group-containing polymerizable monomer and another macromonomer. 2. The coating agent for a photopolymerizable curable ink jet recording image receiving layer according to 1 above. 4. An acryloyl group-containing polymerizable monomer selected from a cationic monomer and a hydrophilic monomer, wherein 0.5 to 99.5 parts by weight of the olefin polymerized macromonomer is mixed with N-vinylacetamide. A coating agent for a photopolymerization-curable ink jet recording image receiving layer, comprising 0.5 to 99.5 parts by weight of a graft-copolymerized resin. 5. The method according to claim 1, wherein the macromonomer is polymethyl methacrylate, polybutyl acrylate, polystyrene,
A polymer of styrene and acrylonitrile, and at least one selected from polydimethylsiloxane, wherein the cationic monomer is at least one selected from N-vinyllactams, acrylates having an aminoalkyl group, and acrylamides Wherein the hydrophilic monomer is a acrylate containing a hydroxyl group and an alkylene oxide adduct thereof, an acrylate of polyethylene glycol,
At least one selected from acrylic acid epoxy esters, acrylic acid esters or acrylic acid epoxy esters of alkylene oxide adducts of aliphatic or aromatic compounds having a hydroxyl group, amino group, carboxyl group or mercapto group, and acrylamide derivatives The coating agent for a photopolymerizable curable ink jet recording image receiving layer according to claim 1 or 4, wherein: 6. The method according to claim 1, wherein a surface of the recording base sheet is provided.
An ink-jet recording sheet, characterized in that a coating agent for a photopolymerizable curable ink jet recording image receiving layer selected from the group consisting of (1) to (5) is cured by photo polymerization to form a recording image receiving layer.