FR2580232A1 - RECORDING MEDIUM - Google Patents

Abstract

THE INVENTION RELATES TO A RECORDING MEDIA INCLUDING A SUBSTRATE AND AN INK RECEPTION LAYER. THE INK RECEPTION COAT, APPLIED TO THE SUBSTRATE, CONTAINS, IN ASSOCIATION, A HYDROPHILIC RESIN AND A HYDROPHOBIC SUBSTANCE WHICH IS LIQUID OR WAXY AT NORMAL TEMPERATURE. THE SUBSTRATE AND THE INK RECEPTION LAYER MAY BE TRANSPARENT. THE INK RECEPTION LAYER MAY BE MAINLY CONSISTING OF A HYDROPHILIC RESIN AND MAY RECEIVE, ON ITS SURFACE, A HYDROPHOBIC SUBSTANCE WHICH IS LIQUID OR WAXY AT NORMAL TEMPERATURE. FIELD OF APPLICATION: MEDIA FOR RECORDING BY INK, ETC.

Description

258C232

  The invention relates to a recording medium

  to be used for recording made with an aqueous ink, and in particular a

  recording medium which is suitable for recording

  an image and the use of light transmitted through the recorded image, for example, for viewing an image projected on a screen, etc.,

  using an optical instrument such as a retroprojector

  the recording medium according to the invention

  also suitable for ink jet recording.

  Performing a recording using a recording liquid (ink) can be performed using writing instruments such as pen pens, water ink pens, pencils water-based signs, ceramic pencils,

  luminescent pencils, etc., and tracers use them

  health. In addition, the registration system that has recently attracted attention is the registration process

  by ink jets in which a recording is made

  killed by the production of small droplets of an ink, according to various principles of actuation, and

  by fixing them on a recording medium.

  An ink jet recording process performs recording by producing small ink droplets by means of various devices

  projection or discharge of ink (recording liquid

  such as an electronic attraction device

  static, a mechanical vibration device or a device displacing the ink by means of a piezoelectric element, a device using the pressure produced by foaming of the ink under the effect of heating, which makes it possible to project it and fix it in part or in full on a recording medium such as paper. This latter method now attracts attention as a less noisy recording method and capable of high speed printing.

and in multiple colors.

  For ink-jet recording, inks composed mainly of water have been used, in particular for reasons of safety and recording characteristics, and in most cases a polyhydric alcohol is added to prevent shutter

  nozzles and improve the stability of the discharge.

  As a recording medium for use in the ink jet recording process,

  recording media were used, including

  a porous ink-receiving layer applied to conventional paper or a substrate called ink-jet recording paper. However, as the characteristics of

  recording by ink jets, such as accelerating

  ration or the multiple coloring of the recording and its extension more and more wide, it is also asked the recording medium features

  more and more elevated and extended.

  In particular, the recording medium

  by ink jets, making it possible to obtain images

  High resolution and high quality must meet various basic requirements such as the following: (1) the receipt of ink on the recording medium should be as fast as possible; (2) even though ink dots may overlap, the ink last set must not overlap in the previously applied dot; (3) the ink droplets should not diffuse on the recording medium to form an ink dot of larger diameter than is necessary; (4) the shape of the ink dot must be

  approximately that of a real circle and its circumference

must be regular; -

  (5) the optical density of the ink dot should be high, without darkness around the point; etc. In addition, to obtain a high resolution recorded image quality, comparable to that

  of a color photograph, by the process of

  In addition, the following characteristics are required in addition to the characteristics indicated above: (6) ink dyes must have an excellent color-forming property;

  (7) since the liquid droplets

  which are the same number as the ink colors

  sometimes at the same point overlap with each other

  singing, the fixing characteristic of the ink must be excellent; (8) the surface must have luster;

  (9) the degree of whiteness must be high.

  Furthermore, although the recorded images obtained by the ink jet recording method have been used in the past exclusively for

  surface image observation, recording media,

  appropriate for uses other than the observa-

  Surface image are increasingly in demand with feature enhancements or a large expansion of the jet recording device.

ink.

  Uses of the recording medium

  other than for a surface image observation may

  include those in which recorded images

  stored on a screen, etc. thanks to

  an optical instrument such as a slide projector

  or an overhead projector, etc., and these images are observed, color resolution plates during the preparation of a positive plate for color printing, and color mosaic filters, etc., to be used for color display such as liquid crystal, etc. When the recording medium is intended to be used for the observation of a surface image, the scattered light of the recorded image is observed, whereas the light transmitted through the recorded images poses a problem in the

  recording medium for these uses.

  As a result, light transmission, and in particular an excellent linear transmission coefficient, are required in addition to the generally required characteristics of the carrier for

  to an ink jet recording.

  However, until the present invention, no recording medium was known yet.

  satisfying all the requirements.

  The recording medium known in the art, suitable for uses as mentioned above, comprises a transparent substrate and an ink-receiving layer applied to the substrate, and is particularly excellent with respect to the transmission of light

  and the absorption power of the ink, among the

  requested characteristics as mentioned above.

  Various materials have been used for forming the ink receiving layer in such a recording medium. Since ink, as mentioned above, is used as an ink, an aqueous ink, hydrophilic materials such as a polyamide, polyvinyl alcohol capable of imparting excellent ink absorption capacity.

  at the ink receiving layer, attracted attention.

  For example, Japanese Patent Application No. 80489/1981 discloses a non-porous recording medium having an ink absorbing layer comprised of a hydrophilic resin such as polyvinyl alcohol, polyvinylpyrrolidone, and the like. On the other hand, the recording medium comprising an ink-receiving layer formed of a hydrophilic material as mentioned above,

  although it can satisfy many of the

  requested and mentioned above, is subject to contamination by body fluids from the palm of the hand (fat of the skin or other types of constituents of sweat, or various dusts absorbed by sweat), for example

  fingerprints, when these record carriers

  are mounted on a recording device.

  Since the fingerprints, including a

  such body fluid, usually contain constituents

  When the aqueous ink as mentioned above is applied to the part where these fingerprints are attached, the contact angle between the recording surface and the ink changes because of the presence of the skin, etc., in these fingerprints, so that

  the ink absorption power of the absorption layer

  ink is substantially modified. As a result, the point formed by the ink may deviate from a truly circular shape, or the smearing of the ink

  passes from where fingerprints are

  to the part without fingerprints, thus varying the recording density of the ink

  and disadvantageously disturbing the recorded image

  Tree. In particular, in the recording medium

  transparency for observing an image recorded

  by magnification using a transmitted light,

this problem is very important.

  In particular, when ink droplets are attached to a high density, if the smudging is important, undried ink droplets, fixed in close proximity to each other on a recording medium, can touch and

  the ink of several droplets in contact can become

  glomerate in a single droplet. The irreversible appearance

  of such an agglomeration of undried ink droplets (pearl formation) disturbs the printing

  and makes the recorded image irregular.

  In addition, in the case of a recording medium

  by using these hydrophilic materials to form an ink-receiving layer, the surface of this layer becomes tacky by absorbing

  humidity in highly humid conditions

  , so that there are problems due to the risk of fixing the dust on the surface of the support

  in addition to those resulting from the accession

  between recording media when

  stacked or adhesion between the record carrier

  the record and the output roll at run time

  recording on the medium mounted in the

  recording, so that disadvantages such as unstable or impossible

  recording medium, or the impossibility of obtaining

  to ensure proper operation of the recording equipment

is lying.

  The object of the invention is to solve these problems.

  and it proposes a recording medium which can satisfy all the criteria requested and described above, which is particularly excellent as regards the ink absorption capacity and the light transmission coefficient, and on

2580232-

  which are difficult to fix fingerprints

  containing fatty substances from the skin, the

  Furthermore, the recording port according to the invention has no irregularity of the image even when it is printed on the fingerprints.

  Another object of the invention is to

  be a recording medium that can be used for purposes of observation or use of light

  transmitted from an image recorded by means of an

  such as a slide projector, an overhead projector, a contact printer, etc., which is also suitable for ink jet recording. The objects indicated above and other objects of the invention are realized by the present

  invention as described below.

  According to the invention, there is provided a recording medium comprising a substrate and an ink-receiving layer applied to the substrate, said ink-receiving layer containing, in combination, a hydrophilic resin and a hydrophobic substance which is liquid or waxy at normal temperature. The invention also provides a recording medium comprising a transparent substrate and a transparent ink-receiving layer applied to the substrate, the ink-receiving layer containing, in combination, a hydrophilic resin and a hydrophobic substance which is liquid. or waxy

at normal temperature.

  The invention further provides a recording medium comprising a substrate and an ink-receiving layer consisting mainly of a hydrophilic resin, applied to the substrate, said ink-receiving layer comprising a substance

258023;

  hydrophobic which is liquid or waxy at the temperature

normal, applied on its surface.

  To describe in detail the present invention, it has been found that by introducing 0.1 to 40% by weight of a waxy hydrophobic substance, which is liquid or waxy at normal temperature, into the ink receiving layer of a recording medium while being prepared by forming an ink-receiving layer, comprising a hydrophilic material,

  on the substrate of the recording medium, the

  Fingerprint adhesion problems, as well as the problem of pearl formation, as mentioned above, can be solved without any of the various benefits resulting from the presence of a hydrophilic material contained in

  the ink receiving layer is affected.

  The recording medium according to the invention

  The invention generally comprises a substrate as a support material and a recording surface, namely an ink-receiving layer, applied to the surface of the substrate. For example, particularly advantageous embodiments may have the following constitution: (1) the embodiment in which both the substrate and the ink receiving layer

  are transparent to light, and recording support

  as a whole is transparent to the light; (2) the embodiment in which the surface of the ink receiving layer is smooth and lustrous; (3) the embodiment in which the ink-receiving layer is made up of two layers including a lower layer which is an ink-retaining layer and a top layer

  which is a permeation layer of the ink.

25802-32 '

  Moreover, in each of the forms of

  the ink receiving layer can assume the same

the function of a support.

  The invention will be described in more detail with reference to some of its preferred embodiments, as mentioned above, data

as typical examples.

  Advantageous examples of trans-

  parents for use in the embodiments (1) and (2) may comprise films or plates, for example resins of polyester, diacetate, triacetate, acrylic, polycarbonate, polyvinyl chloride, polyimide, polysulfone, cellophane "," celluloid ", etc., and glass plates. By using these transparent substrates and forming

  also other transparent layers, it is pos-

  to obtain a recording medium suitable for observing the transmitted light, having an excellent light transmission coefficient,

  in the embodiments (1) and (2).

  Opaque substrates advantageous to use

  in the embodiments (2) and (3) can

  take, for example, paper, cloth, wood, a metal plate, synthetic paper in general

  or else, the transparent substrates

  above which have been subjected to an opacifying treatment by known means. The recording medium for observing a surface image according to embodiments (2) and (3) can be formed

using these opaque substrates.

  Such a substrate may have a thickness

  advantageously between about 10 and 200 μm.

  The ink receiving layer according to the invention

  It is formed mainly of a hydrophilic material capable of receiving an aqueous ink, and advantageous examples of such a material include natural resins such as albumin, gelatin, casein,

  starch, cationic starch, gum arabic, alginic acid,

  sodium nate, etc .; and synthetic resins such as polyvinyl alcohol, polyamide, polyacryl-

  amide, quaternized polyvinylpyrrolidone, polyethylene

  imine, polyvinylpyridinium halide, melamine resin,

  polyurethane, cellulose derivatives such as carboxyl

  methylcellulose and hydroxyethylcellulose, polyalcohol

  vinyl, cation-modified polyvinyl alcohol, polyester, sodium polyacrylate, etc. At least one

  of these materials can be used as desired.

  In addition, to increase the mechanical resistance

  and / or improve adhesion to the substrate of the ink-receiving layer, resins such as

  styrene-butadiene rubber latex, rubber latex

  neoprene-butadiene rubber, polyvinylformal, polymethacrylate

  methyl lattice, polyvinyl butyral, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate, phenolic resin, alkyd type resin, can also be

  be used in combination if necessary.

  The main particular feature of the present invention is that it has, in combination, from 0.1 to 40% by weight of a hydrophobic substance which is liquid or waxy at normal temperature, in the receiving layer of ink,

  formed mainly of the aforementioned hydrophilic resin.

  The hydrophobic substance to be used in the present invention is a substance having no affinity for an aqueous ink, particularly a

  organic substance, preferably of molecular weight

  medium, which is a non-volatile liquid at

  normal or waxy structure, having a relatively low melting point. Specific examples may

  include saturated or unsaturated fatty acids

2580-232

  1 to 4 or more carbon atoms, such as linoleic, linolenic, palmitic, lauric, myristic, caprylic, caproic, capric, erucic, oleic, stearic, etc .; esters of fatty acids such as glycerin trioleate, soybean oil, coconut oil, linseed oil, safflower oil, glycerin tristearate, etc .; animal and vegetable oils such as squalene, cholesterol, lanolin, bacon, wax

  of bee, cottonseed oil, tung oil, olive oil

  ve, soybean oil, linseed oil, safflower oil, rapeseed oil, castor oil, coconut oil, etc .; other natural substances such as mineral oils, etc .; synthetic organic substances such as paraffin, silicone oil, fluorine compound, dioctyl phthalate, dibutyl phthalate, oligomers

  acrylic; and derivatives of these substances.

  The above-mentioned fatty acids and the metal salts of these acids are particularly preferred.

  such as calciun, aluminum, zinc, barium, magnesium

  sium, lead, cadmium, etc., their amine salts such as those of ammonium, triethanolamine, etc., and other esters of said fatty acids with alcohols such as ethanol, ethylene glycol, glycerin, etc. . At least one of these bodies or, in the case of natural products, those containing at least one of the

  mentioned above, can be suitably used.

  The above hydrophobic substance is

  in an amount of 0.1 to 40% by weight, advantageously

  0.1 to 20% by weight, more preferably 0.1

  at 5% by weight, in the ink-receiving layer.

  If the content of hydrophobic substance is less than 0.1% by weight, there is no more effect than in the absence of addition. On the other hand, when the content exceeds 40% by weight, the fixing characteristic

  ink decreases undesirably.

  The recording medium having a constitution

  The composition as described above has excellent adaptability to recording made with an aqueous ink as described above.

  and, moreover, it solves the problems posed by the

  fingerprints or the formation of pearls, so that it can give a high-power image

  light transmission and / or glossy surface.

  Hereinafter will be described preferred embodiments for obtaining an effective effect

of the present invention.

  In the present invention, the ink-receiving layer is more preferably hydrophilic

and insoluble in water.

  In the present invention, the water-insoluble polymer for forming an ink-receiving layer is not a hydrophobic polymer in general, having no hydrophilic power,

  but a sufficiently hydrophilic polymer, although

  soluble in water-. Particular examples of such a hydrophilic and insoluble polymer in water are

given below.

  (1) Grafted, block copolymers

  having hydrophilic segments and hydrophilic segments

  phobes in the molecule: Such block, grafted polymers are

  insoluble in water as a whole, but hydro-

  philes. Hydrophilic segaents of these polymers are segments of a polymer of two or more vinyl monomers having hydrophilic groups such as a carboxylic group, a sulfonic acid group, a hydroxyl group, an ether group, an amide group, acid, methylol groups thereof, primary to tertiary amino groups, quaternary ammonium groups, etc., and examples of such monomers.

  hydrophilic agents include (meth) acrylic acid, anhy-

  maleic anhydride, vinyl sulfonic acid, sulfonated styrene, vinyl acetate, polyol mono (meth) acrylate or monomaleate such as ethylene glycol, etc., (meth) acid amide acrylic or its product

  formed with methylol, mono (meth) acrylate

  or di-alkylaminoethyl, its quaternized product, the

  vinylpyrrolidone, vinylpyridine, and others.

  Hydrophobic polymer segments are polymers of two or more monomers including olefins such as ethylene, propylene, butylene, etc .; aromatic vinyl compounds such as styrene, methylstyrene, vinylnaphthalene, etc .; halogenated olefins such as vinyl chloride, vinylidene chloride, vinylidene fluoride, etc .;

  various esters of alcohols such as (meth) acrylic acid

  that, crotonic acid or other unsaturated carboxylic acids, etc. Water-soluble polymers other than those

  mentioned above, for example hydro-

  natural or synthetic philes such as natural resins (eg albumin, gelatin, casein, starch, cationic starch, gum arabic, alginate

  sodium, etc.), polyvinyl alcohol, a poly-

  amide, polyacrylamide, polyvinylpyrrolidone,

  polyethyleneimine, a polyvinylpyridine halide

  dinium, a melamine type resin, a polyurethane, a polyester, sodium polyacrylate, etc. or natural or synthetic hydrophobic polymers obtained

  by modifying precedents to make them insolent

  in water can also be used as a hydrophilic polymer segment or as a polymer segment

hydrophobic, as desired.

  (2) Crosslinking product of a water-soluble polymer:

  This is obtained by cross-linking of various poly-

  water-soluble mothers as described above or

  below, to the extent that they become insoluble in water without loss of hydrophilicity, with a crosslinking agent or a suitable radiation. (3) Polymer Complex Comprising an Acidic Polymer and a Basic Polymer: Such a polymer complex comprises a basic polymer and an acidic polymer and is known per se as described, for example, in US Pat.

  Japanese N 37017/1976 and 42744/1980.

  Basic polymers advantageous for

  formation of such a complex of polymers are indi-

below:

  homopolymers or copolymers

  ticks, block copolymers or copolymers

  grafted with other monomers in general N-vinyl-

  pyrrolidone, N-vinyl-3-methylpyrrolidone, N-vinyl

  methylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone,

  N-vinyl-3-benzylpyrrolidone, N-vinylpiperidone, N-

  vinyl-4-methylpiperidone, N-vinylcaprolactam, N-vinyl

  capryl-lactam, N-vinyl-3-morpholine, N-vinylthiopyr-

  rolidone, N-vinyl-2-pyridone and the like;

  homopolymers or copolymers

  ticks, block copolymers or copolymers

  grafted with other monomers in general N-vinyl-

  2-oxazolidone, N-vinyl-5-methyl-2-oxazolidone, N-vinyl

  ethyl-2-oxazolidone, N-vinyl-4-methyl-2-oxazolidone, N-

  vinyl-2-thio-oxazolidone, N-vinyl-2-mercaptobenzoate

thiazole and the like;

  homopolymers or copolymers

  ticks, block copolymers or copolymers

  grafted with other monomers in general N-vinyl-

  imidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methyl-

imidazole and the like;

  homopolymers or copolymers

  block copolymers or copolymers grafted with other monomers in general of 2- or 4-vinylpyridine; etc. Other copolymerizable monomers to be used in the above copolymers may include methacrylate, acrylate, acrylamide, acrylonitrile, vinyl ether, vinyl acetate, vinylimidazole,

  ethylene, styrene and other monomers in general.

* Particularly useful for the present invention

  are homopolymers and copolymers of N-

  vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam,

  N-vinylmorpholine, N-vinyl-2-oxazolidone, N-vinyl

  2-methyl-oxazolidone, etc. In the case of a copolymer,

  the monomer containing nitrogen, as indicated below

  above, must be incorporated in a quantity advantageously

50 mol% or more.

  Moreover, the acidic copolymer capable

  to form a complex with the basic polymer

  The "acid polymer" of the present invention also includes polymers having alcoholic hydroxyl groups, other than those having sulfonic acid groups, carboxylic acid groups, sulfuric acid ester groups, ester groups of the Phosphoric acid, phenolic hydroxyl groups, in their molecule) may include, for example, the following polymers: 1. polymers having carboxylic acid groups: carboxyl-terminated polyesters obtained by the reaction of polycarboxylic acids such as citric acid , tartaric acid, phthalic acid,

  with polyhydric alcohols such as ethylene glycol, 1,4-butanediol, diethylene glycol, etc. in the presence of a

  excessive amount of acids; acidic cellulose derivatives modified with various types of polycarboxylic acids (see Japanese Patent No. 5093/1960);

  homopolymers or copolymers

  block copolymers or graft copolymers formed with other monomers in general

  vinyl ester and vinyl ether monomers of polycarboxylic acids

  etc. (see Japanese Patent No. 8495/1960);

  homopolymers or copolymers

  block copolymers or graft copolymers formed with other monomers, in general, vinyl ester and vinyl ether monomers of acrylic acid, methacrylic acid, etc .;

  homopolymers or copolymers

  and block copolymers or graft copolymers formed with other monomers in general of vinyl ether and vinyl ester monomers of α, β-unsaturated vinyl monomers, such as maleic anhydride, itaconic acid, and the like. (see "Synthetic Polymer (III), edited by Murahashi, Inoue, Tani, pages 250-257 and 374-380, published by Asakura Shoten,

1971);

  2. polymers having sulfonic acid groups: cellulose derivatives such as acetate

  of 0-ethylcellulose-hydrogen sulphate-hydro phthalate

  gene, cellulose acetate-hydrogen sulphate-hydrogen phthalate, ethylcellulose hydrogen-O-sulphobenzoate,

  O-P-sulfobenzylcellulose acetate, acetate of 0-

  ethyl-O-P-sulfoethylcellulose, etc. (see Japanese patent

  5093/1960), polyvinyl alcohol polymers modified with sulfonic acid or copolymers

  of vinyl alcohol with sulfuric acid compounds

  that (for example 0-sulphobenzoic acid,

  sulfopropionic acid, sulphovaleric acid, sulpho

  benzaldehyde, sulfuric acid, qua, etc.);

  3. Polymers with a hydrofluoric group

  xyl: ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxyethylethylcellulose, hydroxyethylbenzylcellulose, etc .;

  other homopolymers, copolymers

  graft copolymers, block copolymers or copolymers formed with other monomers in general, with other

  monomers possessing sulphonic acids or groups

  phenol; various modified acidic polymers formed

  with other compounds containing carboxyl groups

  or sulfonic acid groups or phenol groups. Basic polymers and acidic polymers advantageously suitable for forming a complex as described above may be those having respective molecular weights of 500 or more, preferably 1000 or more, and they can form a substrate receiving layer. ink having high strength and excellent characteristics

  of ink reception, image finesse and resistance

water.

  The proportion of the two polymers to be used can be in the range from 20/1 to 1/10 with respect to the weight ratio of the basic polymer

to the polymer-acid.

  In the most advantageous embodiment

  of the present invention, using a hydrophilic and water-insoluble ink-receiving layer, as described above, even under conditions of high humidity or in the case where droplets

  of water settle on the surface, not only

  blemish does not appear, such as a mutual adherence between

  recording media or adhesion to the system.

  because the surface of the recording medium is made sticky or sticky, but also the surface of the recording medium.

  The registration is difficult to cover with

  coming from the skin, which makes it possible to obtain a recording medium having a much better resistance

fingerprints.

  In addition, in the preferred embodiment

  above the recording medium according to the

  to improve the fixing characteristic of the coloring material (eg dye) received by the recording medium and to prevent

  coloring matter to flow or migrate under the conditions

  previously indicated, the recording medium

  may also contain a cationic resin

as indicated below.

  For this cationic resin, it is possible to use

  in the present invention, any of the polymers known in the art and having cationic groups, but preferably polymers

  having quaternary ammonium groups, in particular

  bind a compound of the following formula (I) or derivatives

  polydiallylamine containing

  monomers represented by the following formulas:

  (II) - (IV): (I) CZ- (CH 2 -CH-O) n -H (CH 2) m

R1-N ± R3. Y-

R2

  in which R1, R2 and R3 represent a hydro-

  gene or alkyl, m is between 1 and 7, n is between 2 and 30 and Y is an acidic group; (II)

(C 1 H 2 -CH-CH-CH 2) -

I I 2

CH2 CH2

N + .... Y-

R R

l 2 (III) CH

- (CH2-CH CH) -

\ /

CH2 CH2

N + ..... Y-

/ \ RR RR (IV) CH2

- (CH CH-CH -S) -

CH2 CH2 O O

N ..... + y

R1 R2

  In formulas (II) to (IV), R1 and R2 are

  present -CH3, -CH2CH3, -CH2CH20H and Y is an acidic group. Examples of the compound represented by the

  formula (I) include a compound of the type "arpoly-

  607 "(produced by the firm Narco Chemical Co.), of the" Polyfix 601 "type (produced by the company Showa Kobunshi KK), etc. The compounds represented by the formulas (II) - (IV) are polydiallylamine derivatives and obtained by cyclization polymerization of diallylamine compounds, and may include compounds of the type "Percol 1697" (produced by the firm Allied Colloid Go.), of the type "Catflowe" (produced by the company Chalgon Corp.), of the type " PAS "(produced by Nitto Boseki KK)," Neofix RPD "(produced by the firm

Nikka Kagaku K.K.).

  The ink-receiving layer of the recording medium according to the invention is formed from the hydrophilic and water-insoluble polymer and the cationic resin, advantageously non-porous,

  and the amount of cationic resin added is

between 2 and 20% by weight.

  In addition, in the present invention and in any of the embodiments, to improve

  the ink absorption capacity of the receiver layer

  ink, it is possible to disperse fillers such as silica, clay, talc, diatomaceous earth, calcium carbonate, sulphate

  of calcium, barium sulphate, aluminum silicate,

  ntum, a synthetic zeolite, alumina, zinc oxide, lithopone, satin white, etc., in the ink-receiving layer, in the range that does not porous the receiving layer of ink, or in the range that does not affect the transparency of the shape

above embodiment (1).

  Regarding the training process

  of such an ink-receiving layer, it is possible to

  usefully a method in which a coating solution is prepared by dissolving or dispersing the preceding polymer complex or a mixture with another suitable polymer, and this solution is applied to the light-transmitting substrate by a known method such as that a roll coating,

  bar coating, spray coating

  air-bladed coating, etc., followed by rapid drying. It is also possible to form an ink-receiving layer on the substrate by the method in which the ink-receiving layer,

  only, is formed using the materials listed below.

  above, by a known method such as the dissolving process

  or the T-die process, so as to also have the support function, or by the method in which the sheet is laminated to the support, or the process

  wherein the above polymeric material is

  put in a coating of hot melt material.

  The ink-receiving layer thus formed may also be in the ink-holding range, which may also differ depending on the amount of ink used for recording, but it is not particularly limited, provided its thickness is 0.1 pm or more. In practice, a thickness of between 1 and 200 μm,

  advantageously between 3 and 100 Vm, and more advantageously

  between 5 and 30 Vm, can be used.

  Having described above the forms of reali-

  in which the hydrophobic substance is contained in the ink-receiving layer, an embodiment can now be described in which the hydrophobic substance can also be applied

  on the surface of the ink-receiving layer.

  It is possible to apply, in the same way as for the formation of the ink-receiving layer or the ink-permeation layer, as described

  above, a method for applying the hydrophilic substance

  phobe as described above on the

  ink reception (or on the permeation layer of

  cre), the hydrophobic substance above being applied

  alone or after having formed a coating liquid in

  solution, suspension or dispersion in a suitable liquid.

  The hydrophobic layer thus formed can be a layer

continuous or a discontinuous layer.

  The amount of hydrophobic substance

  This may generally be from about 0.5 to 500 mg / m 2, more preferably from 0.5 to 30 mg / m 2. If the applied amount is less than 0.5 mg / m 2, the objects of the present invention can not be realized, while an amount greater than 500 mg / m 2 undesirably lowers the ink-receiving power.

of the ink-receiving layer.

  Thus, in the Applied Quantity within the above range, the fingerprint problem can be solved without the operating characteristics such as the excellent ink reception capability of the ink receiving layer. obtained by the use of a hydrophilic polymer

are affected.

  Sufficient light transmission, such

  mentioned here for the above embodiment.

  dente (1), means that the linear transmission coefficient of the recording medium is advantageously

  at least 2%, and preferably at least 10%.

  If the linear transmission coefficient

  is 2% or more, the recorded image can be

  by projection, for example, by means of a retro-

  projector, on a screen. In addition, to allow

2580232U

  a fine observation of the details of the recorded image,

  the linear transmission coefficient must be

tentatively 10% or more.

  The linear transmission coefficient T (%) as mentioned here is a value which is determined by measuring the transmission coefficient

  spectrum of linear light arriving perpendicular

  sample stretch, transmitted through the sample

  passing through a slot on the receiving side

  at least 8 cm from the sample, on the line from the incident light beam, and received on a detector by means of, for example, an automatic recording spectrophotometer of the Hitachi model 323 type (product by Hitachi Co., Ltd.)

  determining in addition the Y value of the compounds

  tricomatic values and by calculating, according to the following formula: T = Y / Yo x 100 (1) where: T is the linear transmission coefficient Y is the Y value of the sample

Yo is the Y value of white.

  Therefore, the transmission coefficient

  linear voltage as mentioned herein is in relation to the linear light, and is different from the diffuse transmission coefficient (the transmission coefficient is determined by including light scattered by the use of a sphere

  integration at the back of a sample) or opacity

  quoted (determined from the ratio of values when white and black backgrounds are applied to the back side of a sample) in accordance with the process in

  which transmission of light is evaluated with-

a diffused light.

  Since the problem in an instrument using optical techniques is the

  behavior of the right light, it is particularly

  important to determine the transmission coefficient

  linear mission of a recording medium

  the transmission of light from the recording medium

  to be used in such an instrument.

  For example, in the case of observation

  an image projected by an overhead projector, to obtain

  to create a high contrast image between the part

  recorded and the unregistered part, fine and easy to see, it is requested that the unregistered

  of the projected image is clear, namely that the coeffi-

  linear transmission of the recording medium

  either a certain level or a higher level.

  In the test consisting in using a test pattern in an overhead projector, to obtain an image suitable for the purpose above, the linear transmission coefficient of the recording medium must be 2% or more, advantageously 10% or plps, for obtaining a sharper image, and more preferably 50 Z or

  more. Therefore, the recording medium

  to this end must have a coefficient of trans-

  linear mission of at least 2 X. The preferred embodiment (2) as mentioned above is also of the type of the preceding embodiment (1) and is characterized in that the surface of its receiving layer ink is smooth and has a specular surface gloss at 45 of at least 30 Z based on the

JIS Z8741 standard.

  The recording medium of this type is particularly excellent as regards the luster of the surface and is particularly useful as a recording medium for the observation of a surface.

  surface image in complete colors and an excellent

  slow finesse. This embodiment of the support

  according to the invention may be transparent

  rent or opaque and any of the trans-

  parent and opaque mentioned above can be used. In addition, the ink-receiving layer may be transparent or opaque. The materials and the process to be used for formation of the receiving layer

  may be identical to those described above.

  above for the embodiment (1), but the

  The above-mentioned methods can be used even if the ink-receiving layer can become opaque, provided that the surface of this layer can

stay smooth.

  In addition, if desired, in addition to the coating methods as described above,

  it is also possible to use the coating process

  by casting or buffing by means of

  of polishing or calendering rolls.

  Further, in the present invention, using a fine organic or inorganic powder, in a proportion of about 0.01 to about 1.0 g / m 2 of surface of the recording medium, particularly in the embodiment (2), the characteristic

  inside the printer, the characteris-

  anti-self-adherence feature during stacking, fingerprint resistance, etc. support

  obtained registration can be further improved.

  Such a powder may advantageously be a fine powder of particles having a size of 20 μm or less, comprising an inorganic powder such as silica, clay, talc, earth of

  diatoms, calcium carbonate, calcium sulphate

  cium, barium sulphate, aluminum silicate, synthetic zeolite, alumina, zinc oxide, lithopone, satin white, etc .; an organic powder such as salts of higher fatty acids (for example aluminum stearate, calcium stearate, etc.), anionic, cationic, nonionic and amphoteric surfactants which are solid at normal temperature ( for example dodecylbenzenesulfonate

  sodium lauryl sulphonate, lauryl sulphonate,

  potassium fonate, sodium stearyl sulphonate, nonylphenyl polyethylene glycol ether, with a relatively higher RHL (hydrophilelipophilic ratio)),

  plastic pigments such as benzo-type resin

  guanamine powder, acrylic resin powder, etc.

  These powders can be used in

from about 0.01 to 1.0 g / m 2.

  The recording medium according to the invention

  tion is not, of course, limited to the forms of

  described above as examples. In each of these embodiments, the ink-receiving layer may contain various known additives, including dispersing agents, fluorescent dyes, pH adjusting agents, defoamers, lubricants, preservatives. , surfactants, etc.

  The recording medium according to the invention

  It does not have to be colorless, but it can also be a colored recording medium.

  The recording medium according to the invention

  As described above, the ink reception capability and fixing feature are significantly improved and it can produce a recorded image of excellent fineness and can exhibit

a glossy surface.

  At the same time, in the

  According to the invention, because of the introduction of a suitable amount of a hydrophobic substance into the ink-receiving layer, the fingerprints attach little during the handling of the recording medium or, if they attach due to the appropriate degree of hydrophobicity of the surface of the ink-receiving layer, the circular shape of the ink dot is not disturbed by the fixed fingerprint, or any noticeable difference in density of the ink-receiving layer. ink does not appear because of this finger trace, which makes it possible to obtain an excellent recorded image. In particular, by forming the ink-receiving layer into a polymer which is hydrophilic and insoluble in water, one can improve even more

  - notably resistance to fingerprints.

  In addition, in the present invention, by controlling the amount of hydrophobic substance contained in the ink-receiving layer comprising a

  hydrophilic resin, it becomes possible to limit

  the blurring effect of the fixed ink droplets, as well as suppressing the stickiness of the surface, which significantly improves transportability and self-adherence resistance. At the same time, the problem posed by pearl formation, as mentioned earlier, can also be

solved by the present invention.

  Therefore, even when different colors of ink are fixed on the same point

  in a short time, so as to overlap

  mutually when recording in complete colors, ie the opposite of a monochromatic recording, no phenomenon such as pouring or

  a fine and sharp image, high resolution.

  In the present invention, it is also possible to obtain a recording medium having excellent water resistance as well as a glossy surface, unknown in prior art ink jet recording media. . In addition, the

  recording port according to the invention can be applied

  for uses other than a surface image observation as is the case in the prior art, for example to the projection observation of a recorded image, by means of an optical instrument such as a slide projector, overhead projector, etc., to a color resolution plate used during the preparation of a positive plate for color printing, or to a color mosalc filter, etc., to be used for display in color. color, for example by liquid crystals, etc. The present invention will be described more

  in detail with reference to the following examples in the-

  which parts are given by weight.

Example 1

  88 parts of a 10% polyvinylpyrrolidone solution (of the "PVPK-90" type, produced by GAF) in dimethylformamide (hereinafter referred to as DMF) was mixed with 12 parts of a

  10% solution of a phenolic resin of the novola-

  that ("Resitop PSK-2320", produced by the firm Gunei Kagaku) in DMF. The mixture gelled to form a polymer complex, but heating the complex to 90 C with stirring solubilized it

  to give a solution. It has been added to this solu-

  0.7 parts of oleic acid and the solution was

  used as a coating solution.

  As a substrate transmitting light,

  a polyvinyl terephthalate film was used

  100 μm thick ethylene (produced by Toray), and this film was coated with a coating solution having the indicated composition

  below to form a film of 8 μm thick

  after drying, by the method using an application

  bar and the film was dried at 140 ° C.

  for 3 minutes to obtain a recording

  transmitting the light according to the invention.

  The recording medium according to the invention

  thus obtained was colorless and transparent.

Example 2

  A recording medium according to the invention was obtained in the same manner as in Example 1, except that a paper was used as a substrate.

  coated commercially available.

  Examples 3 and 4 and Comparative Example 1 Using the compositions indicated below, coating solutions were prepared

* and we obtained recording media, transparent

  according to the invention and by way of comparison, by forming an ink-absorbing layer on the same film of polyethylene terephthalate as used in Example 1 and the

  same way as in Example 1.

Example 3

  Polyvinylpyrrolidone ("PVPK-90", produced by the firm GAF) (10% solution in DMF) 84 parts Styrene / acrylic acid copolymer ("Oxylac SH2100", produced by the firm Nippon Shokubai Kagaku) (10% solution in DMF) ) 16 parts Aluminum stearate 0.5 part

Example 4

  Comb-shaped polymer (25% methylcellosolve solution) 60 parts Methylvinyl ether copolymer / maleic anhydride mono-n-butyl ester ("GANTREZ ES-425", produced by GAF) (10% solution) of ethanol in water) 40 parts Cottonseed 0.4 part

  * The comb-shaped polymer has been pre-

  parried by graft polymerization of 20 parts

  of an MMA macromer on 80 parts of a skeletal polymer

  derived from 64 parts of 2-hydroxy-methacrylate

  ethyl and 16 parts of dimethylacrylamide.

  Comparative Example 1 Polyvinyl Alcohol ("PVA-217", produced by Kuraray) 5 parts Polyvinylpyrrolidone ("PVPK-90", produced by GAF) 5 parts Water 90 parts

Example 5

  Using a polyethylene terephthalate film 100 μm thick (produced by the

  firm ICI) as a transparent substrate, a liquid of

  The coating, having the composition shown below, was coated by the blade coating process, with a thickener, after drying, of 20 μm, and dried at 80 ° C for 20 minutes to form a receiving layer. ink. Then a solution of 0.1% toluene in a silicone oil ("SH100-1000", produced by the firm Toray Silicone) was applied to the ink-receiving layer at a rate of 8 mg of silicone oil fixed by m2, followed by drying, to obtain a recording medium

  transmitting light, according to the invention.

  Composition of the coating liquid: Polyvinylpyrrolidone ("K-30", produced by the firm GAF) 5 parts Polyvinyl alcohol ("PVA-224", produced by the firm Kuraray) 5 parts Water 90 parts

  The recording medium according to the invention

  thus obtained was colorless and transparent.

Example 6

  Using a 100 μm thick polyethylene terephthalate film (produced by Toray), a coating liquid A having the composition indicated below was applied by the coating method to the bar. a thickness, after drying, of 6 μm, the application being followed by drying at 80 ° C. for 10 minutes, in order to form an ink-receiving layer. Next, a coating liquid B, having the composition shown below, was applied to the ink-receiving layer to form a film having, in the dried state, a thickness of 0.1 μm. followed by drying at 60 ° C for 5 minutes to form a microporous layer

  ink permeation and, in addition, an endocrine

  C, as indicated below, was applied at a rate of 0.1 to 0.2 g / m 2, in the dry state, so that

  obtain a recording medium according to the invention

at

tion, transmitting light.

  Composition of coating liquid A: Polyvinyl alcohol ("PVA-420", produced by Kuraray) 5 parts Polyacrylate (Gogum HW-7, produced by the company Showa Kobunshi) 20 parts Water 75 parts Composition of liquid B coating: Hydrophilic polyurethane ("Tricoat G", produced by Taiho Kogyo) 10 parts Yellow discolouring agent ("CHELEX-90", produced by Sakai Kagaku) 1 part Acetone 89 parts Composition of coating liquid C : Anhydrous silicon dioxide ("Aerosil-972", from the firm Nippon Aerosil ") 1.5 parts Oleic acid 0.2 part Methyl ethyl ketone 98 parts

Example 7

  The same film was used as a substrate

  polyethylene terephthalate as in Example 6, and a coating liquid, having the composition shown below, was applied to this film by the bar coating process, to form a film of a thickness, after drying, of Bu, the coating being followed by drying at 140 ° C. for 3 minutes in order to form an ink-receiving layer. Polyvinylpyrrolidone ("PVPK-90", produced by GAF) (10% solution in DMF) 88 parts Phenolic resin of the novolak type ("Resitop PSK-2320", produced by the firm Gunei Kagaku) (10% solution in DMF) Then a solution of 0.1% silicone oil in toluene was applied at a rate of 0.1 g silicone oil per m2, followed by

  drying to obtain a recording medium

transmitting light.

  Comparative Examples 2 and 3 Comparative recording media were prepared in the same manner as in Examples 5 and 6 except that the fixation was omitted.

hydrophobic substances.

  On the recording medium of the examples and comparative examples above, ink jet recording was carried out using the four types of ink indicated below, by means of a device.

  recording machine with a recording head

  by ink jets of the demand type, which ejects ink by means of a piezoelectric vibrator (diameter of the discharge orifice:

  60 Vm; control voltage of the piezoelectric vibrator

that: 70 V; frequency: 2 kHz).

  Yellow ink (composition) Yellow direct IC 86 2 parts Diethylene glycol 20 parts Polyethylene glycol N 200 10 parts Water 70 parts Red ink (composition) Red acid IC 35 2 parts Diethylene glycol 20 parts Polyethylene glycol N 200 10 parts Water 70 parts Blue ink (composition) Blue direct IC 86 2 parts Diethylene glycol 20 parts Polyethylene glycol N 200 10 parts Water 70 parts Black ink (composition) Food black IC 2 2 parts Diethylene glycol 20 parts Polyethylene glycol N 200 10 parts Water 70 parts The results of the media evaluation

  recording examples and comparative examples

  are given in the following table.

  The respective evaluation points of the table were measured according to the methods described below. (1) The fixing time of the ink was determined by leaving the recording medium under ambient conditions of 20 C and 65% relative humidity (RH) after recording, and measuring the time ink to dry -and not to stick to the finger when the recorded image is touched

finger.

  (2) The dot density was measured for a black spot, using a "Sakura PDM-5" type microdensitometer (produced by Konishiroku Photo Industry K.K.) by the application of the standard

  JIS K7505 for printed micropoints.

  (3) The linear transmission coefficient

  was determined by measuring the transmission coefficient

  spectral range by means of a recording spectrophotometer

  Hitachi model 323 (produced by Hitachi Co., Ltd) is a fully automatic machine, maintaining the distance from the sample to the opening on the light-receiving side to about 9 cm.

  performing a calculation according to the preceding formula (1).

  (4) The gloss measurement was based on the gloss of a specular surface at 45, measured on the surface of the recording medium according to the

JIS Z-8741 standard.

  (5) Resistance to fingerprints [I].

  The resistance to fingerprints was noted as 0 for the absence of a difference in recording density between the part stained with fatty substances coming from the skin and the part not stained, and it

  was noted X for the presence of a difference, when

  a finger is pressed against the surface of the support

recording.

  (6) Resistance to fingerprints 12].

  When viewing an image projected by means of an overhead projector, the projected image, on which it is confirmed the presence of finger spot during the maneuver of the film, is denoted X, and otherwise an O. ) The irregularity of the image was measured

  by printing with the printer

  previously indicated ink jet mantle to fix ink droplets at 7 dots per mm, and this irregularity was noted X when irregular pearl formation appeared on the printed surface, rendering the printing irregular, and she was otherwise rated an O.

BOARD

Example

Comparative example

1 2 3 4 5 6 7 1 2 3

  1. Fixing characteristics of the ink 3min 3min 3min 3min 3min 2min Smin lmin lmin 30s 2. Dense points 1.1 1.1 1.1 1.1 1.0 1 1.1 1.0 1.11, 1 1.0 1.0 3. Linear Transmission Coefficient 79% - 79% 79% 81% 78% 79% 80% 81% 78%

4. Luster of the sur-

face - 80% - - - - - - -

  5. Resistance to fingerprints [1] O O O O O O O O O O 6. Resistance to fingerprints [2] O - O O X X X X 7. Irregularity of the image O O O X C) X X X X o r <N4

Claims (17)

  1. Recording medium, characterized   in that it comprises a substrate and a receiver layer   an ink layer applied to the substrate, said ink receiving layer comprising a hydrophilic resin and a hydrophobic substance which is liquid or waxy at normal temperature.   2. Recording media according to the   1, characterized in that the surface of the   ink-receiving layer has a specular luster   to 45, on the basis of JIS-Z-8741, to % or more.   Recording medium, characterized in that it comprises a transparent substrate and a   transparent ink-receiving layer applied to the substrate   said ink-receiving layer comprising a hydrophilic resin and a hydrophobic substance which   is liquid or waxy at normal temperature.   4. Recording medium according to one   claims 1 and 3, characterized in that the   hydrophobic substance content of the receiving layer   of ink is 0.1 to 40% by weight.   5. Recording medium according to one   claims 1 and 3, characterized in that the   hydrophobic substance content of the receiving layer   of ink is from 0.1 to 20% by weight.   6. Recording medium according to one   claims 1 and 3, characterized in that the   hydrophobic substance content of the receiving layer of ink is 0.1 to 5% by weight.   7. Recording medium according to one   claims 1 and 3, characterized in that the   hydrophobic substance is a fatty acid and / or a salt   of fatty acid and / or a fatty acid ester.   8. Recording medium according to one   claims 1 and 3, characterized in that the   Ink-receiving layer is insoluble in water.   9. Recording medium according to one   claims 1 and 3, characterized in that the   ink receiving layer comprises a complex of a   basic polymer and an acidic polymer.   10. Recording medium according to the claim   3, characterized in that it has a coeffi-   linear transmission of at least 10%.   11. Recording medium, characterized   in that it comprises a substrate and a receiver layer   ink composition comprising a hydrophilic resin applied   on the substrate, a hydrophobic substance, which is   or waxy at normal temperature, being applied   on the surface of said ink-receiving layer.   12. Recording medium according to the   11, characterized in that the quantity of subsi-   The hydrophobic strength applied is 0.5 to 500 mg / m 2.   13. Recording media according to the   11, characterized in that the hydrophilic substance   phobe is a fatty acid and / or a fatty acid salt and / or a fatty acid ester.   14. Recording media according to the   11, characterized in that the receiver layer   ink is insoluble in water.   15. Recording media according to the   11, characterized in that the receiver layer   ink composition comprises a complex of a basic polymer and an acidic polymer.   16. Recording medium according to the   11, characterized in that it has a coefficient   linear transmission factor of 10% or more.   17. Recording media according to the   11, characterized in that the surface of the   ink-receiving layer has a specular luster   to 45, based on JIS-Z-8741, 30% or more.