JP2003205678A - Ink jet recording element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porous ink jet recording element forming an image having good quality and resistant to water and abrasion at the time of printing using ink jet ink, easy to manufacture, having flexibility after printing and fusion bonding and resistant to cracking, and to provide a printing method using the porous ink jet recording element. <P>SOLUTION: The porous ink jet recording element is constituted by providing a meltable porous image receiving layer containing non-porous polymeric particles having a core/shell structure having a polymeric hydrophobic core coated with a polymeric hydrophobic shell on a support. The Tg of the polymeric hydrophobic core is higher than the Tg of the polymeric hydrophobic shell at least by 25°C. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a porous ink jet device.
Print recording elements and printing methods using the above elements.
You. [0002] 2. Description of the Related Art A typical ink jet recording system is described.
Or ink jet printing systems
Drops rise from the nozzle towards the recording element or medium.
Jet at high speed, producing an image on the media. Ink droplets
Or recording liquid) is generally a recording agent (eg, a dye or
Or pigments) and a large amount of solvent. Solvent (also
Is a carrier liquid), generally water and organic materials (eg,
Monohydric alcohols, polyhydric alcohols, or
Mixture). [0003] Ink-jet recording elements are generally small.
At least one ink-receiving layer or image-forming layer
Comprising a supporting body for supporting such an element.
Has an opaque support, intended for reflective viewing
Observation with transmitted light, having a transparent substrate
Includes those intended for [0004] An important characteristic of an ink jet recording element is:
That they need to dry quickly after printing
It is. For this purpose, liquid inks are effectively contained.
Almost instantaneous, as long as it has sufficient thickness and pore volume to
Porous recording elements that provide effective drying have been developed.
For example, a porous recording element may have a fine particle containing coating.
Apply to the support and in contact with a polished smooth surface
Dry, manufactured by cast coating
Can be. [0005] By printing on the ink jet recording element,
Inkjet prints are subject to environmental degradation.
It's easy. They include water and atmospheric gases (eg,
Zon) to deal with damage resulting from contact with
Vulnerable. Not generated as a result of post-imaging contact with water
Damage is the result of deglossing of the topcoat
Water spots that occur as undesired dyes
Dye smearing due to diffusion and image recording
It may even take the form of total dissolution of the layer. Ozone is ink
Bleaches the jet dye, causing loss of density. these
Inkjet printing is laminated to overcome defects
Often done. However, lamination is a separate
It is expensive because it requires rolls. Instead, two layers
Ink-jet recording elements having the same structure have been used
Was. These elements generally comprise a swellable ink-retaining layer.
Or on any of the porous ink retaining layers
Having a porous ink transfer topcoat of heat fusible particles
You. [0006] In addition, after an image is formed, ink jetting is performed.
A polymer solution or dispersion on the surface of the media
Can also provide print protection.
You. The aqueous coating solution fills once the water is removed
Be a polymer dispersion capable of forming
Many. [0007] EP-A-0 858 905
Is a method of converting a granular thermoplastic resin into a glass transition temperature (Tg).
Higher than the minimum film formation temperature (MF
Apply and dry at a higher temperature than FT)
For the preparation of a recording medium comprising a porous outermost layer
Related. The above elements can be used to achieve the desired result
Is that the drying temperature is very low between the Tg and the MFFT.
Question in that it must be precisely controlled
There is a title. If the drying temperature is lower than Tg,
A powder layer is formed. The drying temperature is higher than MFFT
If high, fully coalesced
A film is formed. [0008] [Patent Document 1] European Patent Application Publication No. 0 858 905 [0009] SUMMARY OF THE INVENTION The object of the present invention is to
Good quality when printed with jet ink
Providing images that are water and abrasion resistant,
It is to provide a porous ink jet recording element. Book
Another object of the invention is the ease of manufacture, printing and printing.
Flexible after splicing and provides resistance to cracking
By providing a porous inkjet recording element
is there. Yet another object of the present invention is to use the above-described elements.
The purpose is to provide a printing method to be used. [0010] SUMMARY OF THE INVENTION These and other objects are provided.
The purpose is to use a polymer hydrophobic shell covered with a polymer hydrophobic shell.
Non-porous polymer particles having a core / shell structure containing
A support carrying a fusible porous image receiving layer containing
An inkjet recording element comprising:
Tg of the hydrophobic core is smaller than Tg of the hydrophobic shell.
At least 25 ° C higher than the
This is achieved by the present invention. [0011] DETAILED DESCRIPTION OF THE INVENTION The use of the present invention provides
Good abrasion resistance and
Water resistant and flexible after printing and fusing.
Porous ink jet that provides resistance to cracking
A recording element is obtained. A preferred embodiment of the present invention is: A) Inkjet printer responding to digital data signal
The process of preparing a linter, B) The above-mentioned printer is provided with the above-mentioned ink jet recording element.
Loading the, C) water, a humectant, and a water-soluble dye
For loading an inkjet ink composition comprising
About D) The ink jet in response to the digital data signal
Printing on the above overcoat layer using inkjet ink
And an inkjet printing method. Non-porous polymer used in the present invention
The particles consist of a polymer core covered with a water-insoluble polymer shell.
A. Core / shell grains used in the present invention
Can be used as core and shell for child
Polymers are, for example, acrylic resin, styrene resin
Fats or cellulose derivatives (eg, cellulose acetate
, Cellulose acetate butyrate, cellulose propionate, vinegar
Cellulose propionate and ethyl cellulose
), Polyvinyl resin (for example, polyvinyl chloride, chloride
Copolymer of vinyl and vinyl acetate, and polyvinyl
Butyral, polyvinyl acetal, ethylene-vinyl acetate
Nyl copolymer, ethylene-vinyl alcohol copolymer
-), And ethylene-allyl copolymer (for example,
Tylene-allyl alcohol copolymer, ethylene-ant
Luacetone copolymer, ethylene-allylbenzenecopo
Limmer, ethylene-allyl ether copolymer), ethyl
Ren acrylic copolymer and polyoxymethyle
Polycondensation polymers (eg, polyethylene terephthalate)
Sheet, polybutylene terephthalate, polyurethane,
And polyesters such as polycarbonate).
You. In a preferred embodiment of the present invention,
The child core and the polymer shell are made of a styrene monomer
Alternatively, it is produced from an acrylic monomer. like this
For the production of styrenic or acrylic polymers
In this case, any suitable ethylenically unsaturated monomer
Alternatively, a mixture of monomers may be used. For example,
Len-based compounds (eg, styrene, vinyltoluene, p-
Chlorostyrene, vinylbenzyl chloride, or vinylna
Phthalene) or acrylic compound (for example, acrylic
Methyl acrylate, ethyl acrylate, n-butyl acrylate,
N-octyl acrylate, 2-chloroethyl acrylate,
Phenyl acrylate, methyl α-chloroacrylate, meta
Methyl acrylate, ethyl methacrylate, butyl methacrylate
Chill), and mixtures thereof. Already
In one preferred embodiment, methyl methacrylate or
Or styrene is used. [0016] Core-shell grains used in the present invention
The pellets are generally prepared by a sequential emulsion polymerization technique.
First, the latex of the core polymer is polymerized and then
Wherein the emulsion of the second monomer is supplied sequentially
Thus, a core-shell structure is formed. Core-shell particles
For an example of the preparation of Emulsion Polymerization and
Emulsion Polymers ", P.A.Lovell and M.S.El-Aass
er, John Wiley & Sons, Ltd., 1977
Can be. In a preferred embodiment of the present invention,
The Tg of the hydrophobic core is between 50 ° C and 200 ° C. Another one
In a preferred embodiment of the above, T
g is between -60 ° C and 125 ° C. Yet another preference
In an embodiment, the particles having a core / shell structure have a particle size of 0.
It has an average particle size of from 05 μm to 10 μm. One more thing
In one preferred embodiment, having a core / shell structure
The particles have a mass ratio of core to shell of 1:10 to 1:
0.1. In yet another preferred embodiment,
Particles with a core / shell structure have a particle size distribution of less than 1.3
Has a polydispersity index of If desired, said non-porous polymer particles
To modify the particles to produce particularly desirable properties.
Suitable cross-linking monomers are used in the formation of the polymer core.
May be used. Typical crosslinking monomers are aromatic dimers
Vinyl compounds (eg, divinylbenzene, divinylna
Phthalene or their derivatives), diethylenecarbo
Esters and amides of acids such as dimethacrylic acid
Ethylene glycol, diethylene glycol diacrylate
), And other divinyl compounds (eg, divinyl
Sulfide compound or divinyl sulfone compound)
You. Divinylbenzene and ethylene dimethacrylate
Recall is particularly preferred. Any crosslinking monomer
May be used in an amount of at least 27 mol%
preferable. If desired, the lightfastness of the image can be modified.
To improve the UV-absorbing monomer,
Alternatively, it may be used in forming a polymer shell. Use
UV absorbing monomers that can be used include the following:
Is included. [0020] Embedded image[0021] [Table 1] Non-porous polymer used in the present invention
Particles are, for example, obtained by milling and classifying organic compounds.
Emulsion polymerization, suspension polymerization, and dispersion weight of organic monomers.
Spray drying of solutions containing organic compounds, if appropriate
Or dissolve the organic material in a water-immiscible solvent
This solution is dispersed as fine droplets in an aqueous solution,
The solvent is then removed by evaporation or other suitable technique.
Prepared by a polymer suspension technique consisting of leaving
With a polymer core that can be Bulk polymerization, emulsification weight
For the procedures of dispersion polymerization and suspension polymerization,
Well known to those skilled in the limer art, G.
 Odian's "Principles of Polymerization", 2nd Ed., W
iley (1981), and W.P.Sorenson and T.W.
ell's "Preparation Method of Polymer Chemistry", 2n
d Ed., Wiley (1968)
I have. As mentioned above, the high
The molecular particles are non-porous. Non-porous means no voids
Particles, either squid or not liquid permeable
Means These particles have a smooth or rough surface.
It may have any of the surfaces. The image receiving layer is made of, for example, p
H regulator, rheology regulator, surfactant, UV absorption
Agent, biocide, lubricant, water-dispersible latex, mordant, color
It may also contain additives such as sulfur and a fluorescent whitening agent. The image-receiving layer may be a conventional pre-metered or post-metered layer.
Metering coating methods (eg blade coating
, Air knife coating, rod coating, b
Coating, slot die coating, courtesy
Coating, slide coating, etc.)
Can be applied to one or both surfaces of the substrate
You. The choice of coating method depends on the economics of operation.
This is then the coating solids, coating
Determine formulation specifications such as viscosity and coating speed.
Will be determined. The image receiving layer has a thickness of 5 to 100 μm,
Preferably it can range from 10 to 50 µm. Must
The required coating thickness depends on whether the coating
The need to act as a reservoir to absorb the medium
It is determined accordingly. Use for imaging recording elements of the invention
Inkjet inks are known in the art.
Is knowledge. Generally used in inkjet printing
The ink composition comprises a solvent or carrier liquid, a dye or
Are pigments, wetting agents, organic solvents, detergents, thickeners, preservatives
A liquid composition comprising: Solvent or carrier
The liquid can be just water or a polyhydric alcohol
Water mixed with other water-miscible solvents such as
it can. Organic materials such as polyhydric alcohols are mainly used.
You may use ink that is a carrier or solvent liquid.
No. Particularly useful are mixed solutions of water and polyhydric alcohols.
Medium. Dyes used in such compositions
Are generally water-soluble direct or acid dyes.
You. Such liquid compositions are described, for example, in U.S. Pat.
81,946, 4,239,543, and 4,781,758
It has been extensively described in the prior art, such as in the specification. Recording element disclosed herein
Mentions that it is primarily useful for inkjet printers
However, they were used for pen plotter assembly
It can also be used as a recording medium. Pen plotter
A pen consisting of a bundle of capillaries in contact with the ink reservoir.
By writing directly on the surface of the recording medium using
Operate. In another embodiment of the present invention,
A recording layer is present between the support and the image receiving layer.
And preferably continuous and the fusible porous
Coextensive with the image receiving layer. Preferred embodiment of the present invention
In the above, the continuous and coextensive ink
Retention layer is porous and contains organic or inorganic particles
are doing. Examples of organic particles that may be used include core / shell
Cell Particles (eg, Kapus, filed June 30, 2000)
Niak et al. in U.S. Patent Application Serial No. 09/609/969.
As shown), and homogeneous particles (eg, 2000
Kapusniak et al., US Patent Application No. 09, filed June 30
/ 608/466).
It is. Examples of organic particles that may be used include acrylic trees
Fat, styrene resin, cellulose derivative, polyvinyl resin
Fats, ethylene-allyl copolymers, and polycondensation polymers
(Eg, polyester). In the present invention
Examples of inorganic particles that may be used include silica, alumina,
Titanium dioxide, clay, calcium carbonate, barium sulfate
Or zinc oxide. In a preferred embodiment of the present invention,
The quality ink holding layer contains 20% to 100% particles and 0% to 80%.
% Polymer binder, preferably 50% to 95% particles and
And 5% to 50% of a polymeric binder. the above
The polymer binder is a hydrophilic polymer (for example, polyvinyl chloride).
Nyl alcohol, polyvinylpyrrolidone, gelatin,
Lulose ether, polyoxazoline, polyvinyl ace
Toamide, partially hydrolyzed poly (vinyl acetate /
(Vinyl alcohol), polyacrylic acid, polyacrylic acid
Amide, polyalkylene oxide, sulfonated or
Polyester and polystyrene), case
In, zein, albumin, chitin, chitosan, dex
Tolan, pectin, collagen derivative, colodian (col
lodian), agar, arrowroot, gar, carrageenan, tiger
Gacant, xanthan, rhamsan, etc.
May be. Preferably, the hydrophilic polymer is a polyvinyl
Nyl alcohol, hydroxypropyl cellulose, hydr
Roxypropyl methylcellulose, polyalkylene oxide
Sid, polyvinylpyrrolidone, polyvinyl acetate or
Are their copolymers or gelatin. In a preferred embodiment of the present invention,
The holding layer has a thickness of 1 μm to 50 μm.
The layer has a thickness of between 2 μm and 30 μm. Mechanical durability for ink jet recording elements
The binders discussed above for applying
A small amount of a cross-linking agent acting on the polymer may be added. this
Such additives improve the cohesive strength of the layer. For example,
Carbodiimide, polyfunctional aziridine, aldehyde,
Socyanate, epoxide, polyvalent metal cation, vinyl
Sulfone, pyridinium, pyridylium di
Cationic ether, methoxyalkyl melamine, tria
Gin, dioxane derivative, chromium alum, zirconium sulfate
A cross-linking agent such as a rubber may be used. Preferably, the frame
The crosslinking agent can be an aldehyde, acetal, or ketal (eg,
For example, 2,3-dihydroxy-1,4-dioxane). In the ink jet printing method, the ink
Droplets quickly penetrate into porous coating by capillary action
The image is absorbed by the finger immediately after coming out of the printer.
It is dry to the touch. Therefore, the porous coating
Ink can be quickly “dried” and has stain resistance.
The resulting image is The porous ink holding layer has an open air
Perforated polyolefin, open pore polyester, or open
It may also comprise a pore membrane. Open porosity membranes are known
Can be formed according to the phase inversion technique. Open pores
An example of a porous ink holding layer comprising a membrane is July 2000
U.S. Patent Application Serial No. 09/626/752, filed 27
09/626/883 (All Landry-Coltrain and others)
In the book. In the ink jet recording element of the present invention
The support used is opaque but translucent.
Or it may be transparent. For example, plain paper, tree
Fat-coated paper, polyester resin (eg, polyethylene
Terephthalate, polyethylene naphthalate,
Ester diacetate), polycarbonate resin, fluorine
Resin (eg, polytetrafluoroethylene)
Various plastics, metal foils, various glass materials, etc.
May be used. In a preferred embodiment, the support is
It is a resin-coated paper. Support used in the present invention
Has a thickness of 12 to 500 μm, preferably 75 to 300 μm.
Can be If desired, the support of the base layer
Base layer or solvent absorption to improve adhesion
Before applying the layer to the support, corona discharge the surface of the support
It may be subjected to processing. The image recording element can be another image recording product or
Places that come into contact with the drive mechanism or transfer mechanism of the image recording device
So that, for example, surfactants, lubricants, matting particles
Add additives such as so that they do not degrade important properties
It may be added each time. Further, the top layer of the present invention has a viscosity
It also contains other additives such as conditioning agents or mordants
Is also good. The above including the base layer and the uppermost layer
Layers are commonly used in the art.
By conventional coating means.
be able to. For the application method, wire-wound rod coating
, Slot coating, slide hopper coating
Coating, gravure coating, curtain coating
Which includes but is not limited to
Absent. Some of these methods involve applying both layers simultaneously.
Some of these methods can be used in manufacturing.
It is preferable from an economic viewpoint. Used to image the recording element of the present invention
Inkjet inks are known in the art.
Is knowledge. Generally used in inkjet printing
The ink composition comprises a solvent or carrier liquid, a dye or
Are pigments, wetting agents, organic solvents, detergents, thickeners, preservatives
A liquid composition comprising: Solvent or carrier
The liquid can be just water or a polyhydric alcohol
Water mixed with other water-miscible solvents such as
it can. Organic materials such as polyhydric alcohols are mainly used.
You may use ink that is a carrier or solvent liquid.
No. Particularly useful are mixed solutions of water and polyhydric alcohols.
Medium. Dyes used in such compositions
Are generally water-soluble direct or acid dyes.
You. Such liquid compositions are described, for example, in U.S. Pat.
81,946, 4,239,543, and 4,781,758
It has been extensively described in the prior art, such as in the specification. The following examples are provided to illustrate the invention.
I do. [0041] 【Example】Example 1 Preparation of polymer particles Synthesis of Control CP-1 Particles Latex was prepared by emulsion polymerization technique. First, 4
50 g of deionized water, 3.0 g of surfactant, Triton 770
(Trademark) (solid content 30% by mass), 1.0 g initiator, persulfuric acid
Potassium, and 19 g of monomer, methyl methacrylate
With a nitrogen inlet, mechanical stirrer, and condenser
Charged into a 2 L 3-neck flask. Keep the flask at 80 ° C
, And purged with nitrogen for 20 minutes. 280g removal
Ionic water, 7.8 g surfactant, Triton 770 ™,
0.8 g initiator, potassium persulfate (KPS), 139 g
Monomer, methyl methacrylate (MMA), and 4.2
g of sodium 2-sulfo-1,1-dimethylethyl acryl
By mixing amide (SSDMEAA) monomer
Thus, a monomer emulsion was prepared. This monomer
The emulsion mixture is added to the flask while stirring.
Was added. The addition time of this monomer emulsion is 3 o'clock
Between. Polymerization is performed by adding this monomer emulsion.
Later, it continued for another hour. Cool latex to room temperature
And filtered. Final solids content is 18.77%, particle size
Was 149 nm. [0042]Synthesis of Control CP-2 Particles 44 kg of stainless steel reactor of about 76 L (20 gallon)
Demineralized water was added. Purge the system with nitrogen for 15-30 minutes
Was. The temperature was set at 15 ° C and the agitation was set at 150 rpm.
Was. Add the following to the reactor in the order listed.
Added. 104.6 g of medium dissolved in 500 mL of demineralized water
Potassium tabisulfite, 421.9 g itaconic acid, 2109.5 g
Of ethyl acrylate, 18.56 kg of vinylidene chloride, 1 kg
469 g of Dowfax ™ 2EP rinsed with demineralized water, and
104.6 g of sulfuric acid dissolved in 1.5 kg of demineralized water
Lium. The reactor port and vent were closed. This anti
The reactor pressure was adjusted to about 14 kPa (2 psi) with nitrogen. Initial temperature
The temperature was set at 40 ° C. and kept at this temperature for 16-20 hours. Next
The product was cooled to 20 ° C. and the vacuum was broken with nitrogen. Raw
The product was filtered through cheesecloth. [0043]Synthesis of Control CP-3 Particles Latex is prepared by the same emulsion polymerization technique as the above synthesis.
Prepared. First, 260g of deionized water, 3.0g of surfactant
, Triton 770 ™, 1.0 g initiator, persulfate
Lithium, and 10 g of monomer, methyl methacrylate
With a nitrogen inlet, mechanical stirrer, and condenser
Charged into a 2 L 3-neck flask. Keep the flask at 80 ° C
, And purged with nitrogen for 20 minutes. 100g
Ionic water, 7.8 g surfactant, Triton 770 ™,
0.8 g of initiator, potassium persulfate, 31 g of monomer,
Methyl methacrylate and 122 g of butyl methacrylate
By mixing the monomers, the monomer emulsion
Was prepared. The monomer emulsion mixture is stirred.
While stirring, it was added to the flask. This monomer
The addition time of the marjon was 3 hours. The polymerization is
After addition of the nomer emulsion, it was continued for another hour. La
The tex was cooled to room temperature and filtered. Final solids
Was 32.9% and the particle size was 122.0 nm. [0044]Synthesis of P-1 particles (the present invention) Core-shell latex used in the present invention,
It was prepared by a sequential emulsion polymerization technique. Generally, first,
A polymer latex is polymerized and then a second monomer
-Feed the emulsion sequentially. Core of the present invention
A typical synthetic procedure for a cell latex is described below.
The following components were used for preparing the P-1 particles of the present invention.
Was. [0045]   A: Deionized water (50g)       Triton 770 ™ (30% active) (0.4 g)   B: Potassium persulfate (0.12 g)   C: Methyl methacrylate (17.1 g)       Sodium 2-sulfo-1,1-dimethylethylacrylamide (0.9 g)       Potassium persulfate (0.1g)       Triton 770 ™ (30% active) (0.9 g)       Deionized water (35g)   D: Ethyl acrylate (3.6 g)       Vinylidene chloride (31.0 g)       Sodium 2-sulfo-1,1-dimethylethylacrylamide (1.44 g)       Potassium persulfate (0.21g)       Potassium metabisulfite (0.42g)       Triton 770 ™ (30% active) (5.80 g)       Deionized water (160g) 1. First, the nitrogen inlet, mechanical stirrer,
(A) in a 1-L three-necked flask equipped with
I filled it. This flask is immersed in a constant temperature bath at 80 ° C.
Purged for minutes. 2. (B) is added, then the monomer emulsion
(C) was added. This mixture is added to the monomer emulsion
During the feeding of the solvent, the mixture was stirred. Monomer emulsion
(C) was added for 2 hours. 3. 30 minutes after the addition of the first monomer emulsion
After a while, the latex was cooled to 40 ° C. 4. The second monomer emulsion (D) is prepared as described above.
Prepared. The total addition time was 2 hours. 5. The latex was heated at 40 ° C. for 1 hour. 6. 10% t-butyl hydroperoxide and 10%
Add 4 mL of lumaldehyde sulfite to obtain residual monomer.
Was removed and held for 30 minutes. 7. The mixture was cooled to room temperature and filtered. [0047]Glass transition temperature measurement The glass transition temperature (Tg) of the dried polymer material is 20 ° C /
Differential Scanning Calorimetry (DSC) using heating rate in minutes
Was measured by In the present specification, Tg is
Is defined as the inflection point of the transition. [0048]Particle size measurement Brookhaven Instruments Corporation 90 plus Partic
Particle size was determined by le Sizer. Report volume average diameter
Announce. The polymer particles used in the above examples
Properties are shown in Table I below. [0050] [Table 2] [0051]Control element C-1 (fusible overcoat
No preparation) Two layers of porous glossy ink jet on polyethylene coated paper
A cut medium was prepared. The bottom layer has a mass ratio of 87: 9: 4
Fumed alumina (Cab-O-Sperse PG003 (trademark), Ca
bot Corp.), polyvinyl alcohol (GH-23, Nippon)
 Gohsei), and 2,3-dihydroxy-1,4-dioxane
(Clariant Corp.) with a thickness of 38 μm
Was. The top layer is a fume door with a mass ratio of 69: 6: 5: 20
Lumina (Cab-O-Sperse PG003 ™, Cabot Corp.
 ), Polyvinyl alcohol (GH-23, Nippon Gohsei)
 ), Surfactants (Zonyl FSN ™, DuPont Cor
p.), and mordant material MM, the thickness is 2 μm
And MM is 87% by weight of N-vinylbenzyl chloride-N,
N, N-trimethylammonium and 13% by mass divinylbenzene
Cross-linked, prepared from benzene, having an average particle size of 80 nm
Hydrogel polymer particles. [0052]Preparation of Control Element C-2 The control element C-1 includes the polymer particles CP-1.
Aqueous dispersion is further applied, and is applied at 25 ° C. for 3 minutes.
Dry and then dry at 40 ° C using forced air circulation.
And dried for 3 minutes. Small amount of coating solution
Nonionic surfactant (Olin 10G ™) (for the above layer)
0.1% to 4% of the total dry laydown)
Used to control the surface tension during application. [0053]Preparation of Control Element C-3 This element excludes the use of polymer particles CP-2.
And prepared in the same manner as C-2. [0054]Preparation of Control Element C-4 This element excludes the use of polymer particles CP-3.
And prepared in the same manner as C-2. [0055]Preparation of Control Element C-5 This element is composed of 50/50 mass ratio polymer particles CP-1 and
And C-2, except that a mixture of C-2 and CP-2 was used.
Prepared in the same manner. [0056]Preparation of Element 1 of the Invention This element excludes the use of polymer particles P-1.
And prepared in the same manner as C-2. [0057]Ink absorption Inkjet samples at Hewlett-Packard Deskjet 950 ° C
After loading it into the printer,
A pre-assembled digital image was printed. Printed
Immediately after being discharged from the printer,
Was rubbed with a finger in the area where the ink was applied. Immediately
Dry means that the print is dry to the touch and
The image may be dirty or damaged by rubbing.
Defined as not. When the above particles are dried after application
Ink to form a continuous film
Drops will form on the surface and will not penetrate the layers,
Image has low optical density and easily smudges by rubbing
Will. [0058]Fusion At least one of the printed samples is at a temperature of 157 degrees.
Heated at a rate of 2.5 cm / sec.
Fused between the pressure rollers. [0059]Testing for water and stain resistance 1 g dye on 1000 g of a mixture of acetic acid and water (5 parts: 95 parts)
By dissolving the ingredients, the Ponceau red dye solution
Prepared. Try a Ponceau red dye solution approximately 1 cm in diameter.
Placed on the surface of the preparation for 5 minutes. Next, Sturdi-Wipes paper
The liquid was wiped off using a towel. Visual view of test area
And recorded. No trace of dye contamination on image
That indicates that a water-resistant overcoat layer is present,
The red stain on the image indicates that the water-resistant overcoat layer is not present.
To indicate that [0060]A trial of the flexibility of the fusion overcoat
Trial With the overcoat layer on the outside, the fused sample is 0.65 cm in diameter
Wrapped around the rod. Next, in the bent area
Test the sample using the Ponceau red dye solution described above.
did. The red dye line shows that the overcoat is brittle and bent
Indicates that cracks have occurred when spilled, and there is no contamination
This indicates that the overcoat was flexible. Elements 1-2 to 1-6 correspond to control element C-
7.6g / m by applying particles on 1^TwoThe dry laydown
Prepared. Inkjet of the present invention
The performance of the media has no fusible core-shell particles
Inkjet media or single composition (non-core-shell)
The following table, compared to inkjet media with particles
Summarized in II. [0062] [Table 3]The above results indicate that the over
The coated layer is better before fusion than the control element
Good cohesion and binding, fast ink absorption, after printing
Is flexible and provides print protection
You. [0064]Example 2 Synthesis of P-2 to P-4 particles (the present invention) These particles have various pores as shown in Table III below.
P-1 in Example 1, except that a limmer composition was used
Prepared the same as [0065] [Table 4] [0066]Control element C-6 (fusible overcoat
No preparation) This element is the control element, except that the top layer is omitted.
Prepared similarly to C-1. [0067]Control element C-7 (fusible overcoat
No preparation) Two layers of porous glossy ink jet on polyethylene coated paper
A cut medium was prepared. The bottom layer has a dry mass ratio of 50/50
AQ29 (available from Eastman Chemical Co.) and Bor
Apply ax, 3.8g / m^TwoAchieve a total dry laydown of
Was prepared. The pH of the coating solution
Adjusted to 7.0 before cloth. The top layer is polyvinyl alcohol
, Organic porous particles described below, and Olin 10G
Apply from the solution mixture, each 29.8g / m^Two, 4.5g /
m^Two, And 0.11g / m^TwoAchieved dry laydown. [0068]Preparation of organic porous particles The following components were added to a beaker. As a monomer
 200 g of ethylene glycol dimethacrylate, porogen
(porogen) as 188 g of toluene and 12 g of hexade
Can and 3.0 g of 2,2'-azobis (2,4-dimethylba
(Relonitrile) (Vazo ™ 52, manufactured by DuPont Corp.).
These components were stirred until the solids dissolved. To this solution was added 12 g of dodecylamine in 1200 g of water.
A mixture of sodium rubenzenesulfonate was added.
Next, this mixture is used with a ship propeller type stirrer.
And stirred for 5 minutes to form a coarse emulsion. This
At about 28 MPa (4000 psi)
Passed once through a Gaulin ™ homogenizer. Got
Disperse monomer droplets in a 2 liter three-necked round bottom flask
Put in. Place the flask in a constant temperature bath at 50 ° C.
Stir the powder under positive pressure for 16 hours to overlap the monomer droplets.
These were combined to obtain organic porous particles. Fill the product with coarse
Filtered through a filter to remove coagulum. Next, 0.3g
MAZU ™ defoamer (BASF Corp.) added to the dispersion
And remove toluene and some water under reduced pressure at 50 ° C.
The solvent was distilled off to a solid content of 18.3%. The above organic porous particles
Particle size analyzer, measured by Horiba LA-920 ™
However, it was found that the median diameter was 0.38 μm.
Was. [0070]Control element C-8 (fusible overcoat
No preparation) This element consists of barium sulfate particles, polyvinyl alcohol
2,3-dihydroxy-1,4-dioxane (Clariant Cor
p.) and a solution mixture of Olin 10G (Olin)
53.8g / m each applied on ren-coated paper^Two, 8.0
g / m^Two, 0.4g / m^Two, And 0.11g / m^TwoThe final dry lay
Prepared by achieving down. The above sulfuric acid burr
Particles (identified as Sachtosperse HU-N)
Obtained from SachtlebenChemie Corporation,
Average particle size less than 0.1μm and> 25m^Two/ g specific surface area
Is pure precipitated barium sulfate. In this element
The polyvinyl alcohol used was Nippon Gohsei Chem
GH-17 available from ical. [0071]Control element C-9 (fusible overcoat
No preparation) 185g / m^TwoPlain paper support having a basis weight of (Eastman Kodak
Co.) was used. [0072]Control element C-10 (fusible overcoat)
Preparation) A two-layer coating on plain paper was prepared as follows. Dry
254 g of dry mass precipitated calcium carbonate Albagloss-s (trademark)
(Specialty Minerals Inc.) (70% solution), dried
22 g silica gel Gasil® 23F (Crosfield
Ltd.), 2.6 g dry weight polyvinyl alcohol Airvol
(Trademark) 125 (Air Products) (10% solution), dry weight
21 g of styrene-butadiene latex CP692NA (trade name)
(Dow Chemical Co.) (50% solution), and 0.8 g
Alcogum ™ L-229 (Alco Chemical Co.)
The coating solution for the base layer.
A liquid was prepared. Adjust the concentration of this coating solution with water.
By addition, it was adjusted to 35% by mass. This coat
The coating solution at 25 ° C by bead coating.
185g / m^TwoPlain paper support having a basis weight of
 Kodak Co.) at 45 ° C with forced air
And dried. The thickness of this base layer is 25 μm or 2
7g / m^TwoMet. Alumina Dispal ™ having a dry weight of 15.0 g
14N4-80 (Condea Vista Co.) (20% by mass solution), dried
2.4 g fumed alumina Cab-O-Sperse ™
PG003 (Cabot Corp.) (40 mass% solution), dry mass
0.6 g of polyvinyl alcohol Gohsenol ™ GH-17
(Nippon Gohsei Co. Ltd.) (10% by mass solution), dry quality
1.2 g of (vinylbenzyl) trimethylammonium chloride
Co of nickel and divinylbenzene (molar ratio = 87:13)
Rimer (20% by mass solution), dry weight 1.2g, styrene
, (Vinylbenzyl) dimethylbenzylamine, and
Of divinylbenzene (molar ratio = 49.5: 49.5: 1.0)
-Polymer (20% by mass solution), 0.9 g dry mass
Particles 1 (40% by weight solution), 0.1 g of Silwet ™
L-7602 (Witco Corp), 0.2 g Silwet ™ FS300
(Witco Corp), as well as a mixture of water and a total of 153
g, the coating solution for the top layer
A liquid was prepared. For the preparation of encapsulated particles 1,
Sadasivan et al., United States Patent, filed August 31, 2001.
No. 09 / 944,547, disclosed in Example 1.
You. Apply the above coating solution at 25 ° C
By coating on the base layer described above.
The recording element is then brought to 45 ° C. by forced air.
And dried at 38 ° C. for 8 minutes.
I let you. The thickness of this image receiving layer is 8 μm or 8.6 g / m^Two
Met. [0074]Preparation of Control Elements C-11 to C-16 Control elements C-1 and C-6 to C-10, as in Example 1
Comprising polymer particles CP-3 used in
The dispersion is further applied and dried at 25 ° C. for 3 minutes,
Then for another 3 minutes at 40 ° C. using forced air circulation
7.6g / m^TwoAchieved dry laydown. Ko
Small amount of nonionic surfactant in the coating solution
(Olin 10G ™) (for total dry laydown of the above layers)
Using 0.1% to 4%)
The surface tension was controlled. [0075]Preparation of Elements 2-7 of the Invention These elements are based on the use of core-shell particles P-2.
And prepared the same as C-11 to C-16 except for [0076]Preparation of Elements 8-13 of the Invention These elements are based on the use of core-shell particles P-3.
And prepared the same as C-11 to C-16 except for [0077]Preparation of Elements 14-19 of the Invention These elements are based on the use of core-shell particles P-4.
And prepared the same as C-11 to C-16 except for [0078]Ink absorption and fusing Print on these elements, as in Example 1,
Fused. The following results were obtained. [0079] [Table 5] The above results show that the overco
Better coating before fusing compared to control elements
Agglutination and binding, fast ink absorption, after printing
Is flexible and shows that it has given print protection
You. Other preferred embodiments of the present invention are described in the claims.
In relation, it is described next. [1] A high polymer covered with a hydrophobic shell
Non-porous having core / shell structure including molecular hydrophobic core
Fusible porous image receiving layer containing porous polymer particles
Inkjet recording element comprising a support
Thus, the Tg of the polymer hydrophobic core is
Inkjet at least 25 ° C higher than the Tg of the gel
Recording element. [2] The polymer hydrophobic core has a Tg of 50
The element according to [1], wherein the temperature is from 200C to 200C. [3] The Tg of the polymer hydrophobic shell is
The element according to [1], wherein the temperature is −60 ° C. to 125 ° C. [4] between the support and the image receiving layer
The element according to [1], wherein an ink holding layer is present therebetween. [5] The ink holding layer has a thickness of 1 μm to 50 μm.
m, and the image receiving layer has a thickness of 2 μm to 30 μm.
The element according to [4], having only [6] The image receiving layer has a thickness of 5 μm to 100 μm.
The element of [1], having a thickness of m. [7] The support is a resin-coated paper
The element of [1]. [8] The ink holding layer is continuous,
Note that [4] is coextensive and porous.
The listed element. [9] The ink holding layer is 20% to 100%
No particles and 0% to 80% polymeric binder
The element of [8]. [10] A) In response to a digital data signal
The process of preparing an inkjet printer that answers B) The printer according to [1],
Loading the recording element, C) water, a humectant, and a water-soluble dye
For loading an inkjet ink composition comprising
About D) the ink jet in response to the digital data signal;
Printing on the overcoat layer using inkjet ink
And an inkjet printing method.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Shao Lu One             United States of America, New York 14623,             Rochester, East Squire             Live 112 (72) Inventor Wendy S.S. Kurzemian             United States, New York 14468,             Hilton, Walker Lake Ontari             O Lord 710 F-term (reference) 2C056 EA13 FC06                 2H086 BA15 BA31 BA34 BA41

Claims (1)

Claims: 1. A fusible porous image receiving layer comprising a non-porous polymer particle having a core / shell structure comprising a polymer hydrophobic core covered with a polymer hydrophobic shell. An ink jet recording element comprising a supported support, wherein the Tg of the polymer hydrophobic core is at least 25 ° C. higher than the glass transition temperature (Tg) of the polymer hydrophobic shell.