JPS6294380A - Aqueous base ink recording sheet - Google Patents

Abstract

PURPOSE:To enable a clear multicolor full-color copy to be recorded and obtain excellent ink absorbing and drying properties, by coating the surface of a sheet form base with a resin composition comprising a mixture of a specified synthetic resin, a partially or completely saponified product of a specific copolymeric resin or a derivative thereof, and/or a specified copolymeric resin as a main constituent, followed by photo-crosslinking. CONSTITUTION:A resin composition comprising as a main constituent a mixture of (A) 90-10wt% of a cationic synthetic resin having photo-polymerizable double bonds, (B) 0-90wt% of a partially or completely saponified polyvinyl alcohol, a partially or completely saponified product of a copolymeric resin comprising 20-100wt% of vinyl acetate and 80-0wt% of other polymerizable monomer, or a derivative thereof, and/or (C) 0-90wt% of a homopolymeric resin of N-vinylpyrrolidone or a copolymeric resin thereof with other polymerizable monomer, the weight ratio of (A)/[(B)+(C)] being 90/10$10/90, is applied to the surface of a base sheet, and is hardened by irradiating with active energy rays to provide a coated resin layer.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to recording sheets using water-based inks (particularly paper, plastic films, synthetic papers, and metal sheets on which high-quality color images can be obtained by inkjet recording). This invention relates to an inkjet recording sheet using a sheet or the like as a base material.

The inkjet recording method is noiseless, does not require developing or fixing processes, can perform high-speed recording, and can easily perform multicolor recording, so it has rapidly become popular in facsimiles, word processors, terminal printers, etc. in recent years. In particular, the development of color printers using an inkjet recording method that creates color hard copies from color displays is progressing. Inkjet color printers are used in the color graphics field, which uses seven expressive colors (yellow, magenta, cyan, red, green, purple, and black), and have recently been used in high-resolution printing similar to gravure printing or silver halide photography. High-resolution color printers have been developed that produce full-color copies, so-called Victorian copies.

[Prior art]

Inkjet recording has the advantage of being able to use plain paper (PPC). However, the reality is that ordinary RTL plain paper is not satisfactory as an inkjet recording paper suitable for multicolor recording.

The basic performances required of an inkjet recording sheet are: 1. The dot shape must be circular, there should be no spread such as bleeding, the dot periphery should be sharp, and the resolution should be high.

2. High dot color density and good clarity.

3. The ink absorption speed is fast, the drying property is excellent, and the amount of ink absorbed is large. When the ink dots become wet, the dots attached later do not flow out, so that the multicolor recording properties are good.

4. Little dimensional change after recording 1+2, curls, waves, etc.
No deformation.

Examples include.

Above all, it is a technical challenge for those skilled in the art to balance the contradictory properties of ink absorption, which governs the drying properties of ink, and dot spreading (bleeding). That is,
If the ink absorbency of the recording paper is fast, generally the dots will spread out and the shape of the dots will become distorted, resulting in poor resolution. In addition, the ink tends to penetrate deeper into the paper layer, reducing color density and sharpness.

Furthermore, in order to obtain high image quality with recent multi-color recording, ink of each color adheres to the same location on the recording sheet or in the vicinity in a short time, so it is necessary to have high ink absorption capacity and especially high ink absorption capacity. be done. Otherwise, the unabsorbed ink will flow out), and as a result, not only will a clear image not be obtained, but it will also cause stains.

Plain paper such as high-quality paper can basically be used as inkjet recording paper, but those skilled in the art who manufacture recording paper can adjust the size, air permeability, and tightness according to the recording method, its conditions, or ink. The reality is that various physical properties of paper such as smoothness, elongation in water, etc. are adapted. On the other hand, in order to obtain high-quality color recording, which is a recent trend, it is not possible to control these paper properties alone.In order to obtain recording performance that satisfies the basic requirements mentioned above, it is necessary to coat the sheet surface. Coated paper-type inkjet recording paper with layers and optimized pigments, binders, etc. is being considered. However, the reality is that there is still no inkjet recording paper for high image quality that is satisfactory in terms of recording performance, water resistance, weather resistance, dimensional stability, etc. of the recording area. Recently, there has been a demand for the use of not only paper but also water-resistant sheets such as impregnated paper, plastic films, synthetic papers, metal sheets, transparent sheets, etc. as base material sheets.

For example, as the use of color displays in personal computers progresses, color hard copies are becoming increasingly popular.
There is a demand for a transparent film capable of inkjet recording for use in HP (overhead projectors). However, plastic films such as polyester used for OH)' films cannot be used because they are hydrophobic, unlike paper base materials, and have no ability to absorb water-based inks. The same applies to other paper products such as impregnated paper, synthetic paper, metal sheets, etc.

The development of inkjet recording sheets based on such new materials has been technically limited by approaches based on conventional manufacturing concepts for plain paper and coated paper.

Furthermore, since water alone as an inkjet ink solvent usually causes clogging of the ejection nozzle due to evaporation, various efforts have been made to mix polyalkylene glycol or a wetting agent with water to prevent clogging due to drying. On the other hand, when recording on a recording sheet such as a synthetic resin film, this causes further deterioration in the drying properties of the ink.

As described above, the most important problem in this field is how to make ink droplets formed by inkjet clearly and distinctly adhere to a recording sheet, particularly a transparent synthetic resin film such as polynisdel, and how to quickly absorb and dry the ink droplets.

[Problem that the invention seeks to solve]

The present invention provides an aqueous ink recording sheet that is capable of clearly and clearly recording multicolor full-color copies, which is an advantage of inkjet printing, and has excellent ink absorption and drying properties.

[Means to solve problems]

The present invention relates to special cationic active energy ray-curable resins, partially or fully saponified polyvinyl alcohol, partially or completely saponified copolymer resins of vinyl acetate and other polymerizable monomers, or A resin composition based on a mixture of these derivatives and/or a homopolymer resin of N-vinylpyrrolidone and a copolymer resin with other polymerizable monomers is applied to the surface of the support sheet. Then, the resin composition is cured by irradiation with active energy rays to form a resin film layer on the support, thereby improving the adhesion of the aqueous ink and providing clear printing without bleeding.

That is, the resin film layer absorbs and dries ink droplets well, does not spread the ink droplets, and does not penetrate deeply into the interior, resulting in excellent inkjet recording properties in which the ink droplets can be obtained as clear and sharp images. Further, since the cationic synthetic resin in the resin composition is made three-dimensional by irradiation with active energy rays, the water resistance is good and no deformation of the recording sheet itself is observed after recording. Furthermore, since the cationic synthetic resin is an electrolyte polymer, it has good antistatic properties and is characterized by the fact that it does not attract dust or the like.

[Structure of the invention]

The present invention relates to (A) a cationic synthetic resin having a photopolymerizable double bond, and (81 partially or completely saponified polyvinyl alcohol, and also vinyl acetate 20 to 10 to 100% by weight S
A partially or fully saponified copolymer resin or a derivative thereof, and/or Fi
(C) N-vinylpyrroli)” 7 monopolymer resin,
A resin composition whose main ingredient is a mixture of a copolymerized resin or a copolymerized resin with other polymerizable monomers is coated on the surface of the support sheet 17, and after drying, the resin composition is irradiated with an active energy beam. The present invention provides an aqueous ink recording sheet having a cured resin film layer on a support.

(Cationic Polymerizable Resin) The cationic synthetic resin having a photopolymerizable double bond as a captive component of the present invention is a polymerizable resin having a polymerizable double bond and a quaternary ammonium salt functional group. For example, the following (
1) - (Books may be mentioned.

(+) A polymer of 10 to 100 polymerizable monocapsules having a tertiary nitrogen atom in which the nitrogen lone pair is not conjugated, and 90 to 0 weight 1% of other polymerizable monomers. A polymerizable monomer having a Lewis acid and an epoxy group that can further donate protons to the resin is reacted with 0.1 to 1.0 g equivalent of the tertiary nitrogen atom-containing polymerizable monomer of the polymer resin. A resin in which the tertiary nitrogen atoms of the polymer resin are quaternized.

Examples of the polymerizable monomer having a tertiary nine atom with which the nitrogen lone pair is not conjugated include N,N-dimethylamineethyl (meth)acryle-1-1N, N-diethylaminoethyl (meth) ) acrylate, N,N-dibutylaminoethyl (meth)acrylate, N,N-dimethylaminepropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-
dimethylaminobutyl (meth)acrylate etc., or N
, N-dimethylamine ethyl (meth)acrylamide,
General formula of N,N-diethylaminepropyl (meth)acrylamide etc. [R1 in formulas (1) and (2) above: hydrogen atom or methyl group, R2 and R'' ii each alkyl group having 1 to 4 carbon atoms, n represents a number from 1 to 4.] (Meth)acrylic monomer represented by; dimethylaminomethylstyrene, diethylaminomethylstyrene,
General formulas such as dibutylaminomethylstyrene [wherein R1 and R8 each represent an alkyl group having 1 to 4 carbon atoms]; ] Styrenic monomers represented by general formulas such as vinylpyridine, methylvinylpyridine, and ethylvinylpyridine [wherein R represents a hydrogen atom or an argyl group having 1 to 4 carbon atoms]. ] There is one type of pyridine monomer represented by the following or a mixture of two or more types of Fi.

Other polymerizable monomers include cationically modified monomers of the tertiary nitrogen atom-containing monomers of formulas (1) to (4) above with methyl chloride, ethyl chloride, methyl monochloroacetate, etc. (these cations (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate. , alkyl (meth)acrylates such as hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, ethoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate. Examples include acrylate, hydroxypropyl (meth)acrylate, styrene, vinyltoluene, vinyl acetate, and the like.

Examples of Lewis acids capable of donating protons include hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen iodide; mineral acids such as nitric acid, sulfuric acid, and phosphoric acid; and organic carboxylic acids such as formic acid and acetic acid.

Examples of the polymerizable monomer having an epoxy group include compounds having a vinyl group and an epoxy group, such as glycidyl (meth)acrylate, allyl glycidyl ether, styryl glycidyl ether, and glycidyl cinnamate.

(1) The lone pair of nitrogen electrons is conjugated 1. A polymer resin containing 10 to 100% by weight of a polymerizable monomer having no tertiary nitrogen atom and 90 to 90% by weight of another polymerizable monomer, and a polymerizable monomer having a covalently bonded halogen atom. mer of the tertiary nitrogen atom-containing polymerizable monomer of the polymer resin.
A resin in which the tertiary nitrogen atoms of the polymer resin are quaternized by reacting with 0 f equivalent.

As the polymerizable monomer having a tertiary nitrogen atom with which the nitrogen lone pair is not conjugated and other polymerizable monomers, the same ones as in (1) can be used, and the polymerizable monomer has a covalently bonded halogen atom. Examples of polymerizable monomers include allyl halides such as allyl chloride, allyl bromide, and allyl iodide, vinylbenzyl halides such as chloromethylstyrene, bromomethylstyrene, and iodomethylstyrene, and 3-chloro-2-hydroxypropyl (meth). 3-halo 2-hydroxypropyl (meth)acrylate such as acrylate, chloromethyl (
General formula % formula % (5) of meth)acrylate, chloroethyl (meth)acrylate, bromobutyl (meth)acrylate, etc. [In the formula, R is a water bulk atom or a methyl group, Show the number. W-haloalkyl (meth)acrylate represented by ] and the like can be mentioned.

(Polymerizable monomer 1 having 110 covalently bonded halogen atoms
A polymerizable monomer having a tertiary nitrogen atom with no nitrogen lone pair conjugated to a polymer resin with a weight ratio of 0 to 100 and another polymerizable monomer of 90 to 0. , the covalent bond of the polymer resin) and the rhodan atom-containing polymerizable monomer.
1~1.0? A resin into which a quaternary ammonium base is introduced by reacting with this prize.

Covalently bonded halogen atom-containing polymerizable monomers, other polymerizable monomers, and tertiary nitrogen atom-containing polymerizable basemers in which the nitrogen lone pair is not conjugated are the same as (+) and (11). can be used.

In these (1), (ii) and (1:1) resins, a tertiary nitrogen atom-containing polymerizable monomer or a covalent bond in which the nitrogen lone pair to obtain the precursor polymer resin is not conjugated. The halogen atom-containing polymerizable monomer is 10 to 100% by weight,
It is preferably 20 to 80 weight parts, and the other polymerizable monomers are used in a proportion of 90 to 0 weight parts, preferably 80 to 20 weight parts.

In addition, a polymerizable monocage containing a Lewis acid and an epoxy group that can donate protons to a polymer resin having a tertiary nitrogen atom or a covalently bonded halogen atom with which the nitrogen lone pair is not conjugated, and a covalent bond A halogen atom-containing polymerizable monomer or a tertiary nitrogen atom-containing polymerizable monomer in which a nitrogen lone pair is not conjugated is a tertiary nitrogen atom-containing polymerizable monomer in which a nitrogen lone pair is not conjugated. 0.1-1 of the polymerizable monomer having a bonded halogen atom. Of equivalent, preferably 0.2-1. It is used in a proportion of Ov equivalent.

If the amount of the tertiary nitrogen atom or covalently bonded halogen atom-containing polymerizable monomer in the III precursor resin to which the lone pair of nitrogen electrons is not conjugated is too small, the absorption and drying properties of the aqueous ink will be insufficient. . On the other hand, if the amount is too high, the water-based ink will bleed, making it impossible to obtain clear prints. In addition, if the proportion of other polymerizable monomers is lower than the above, the water resistance of the coating film of the crosslinked resin layer obtained by photocuring the polymerizable resin will be insufficient, and the water-based ink will bleed and become clear. On the other hand, if the amount is too high, the coating film after photocuring becomes hydrophobic, and the absorption and drying properties of water-based ink deteriorate.

Next, a method for producing the cationic synthetic resin having a photopolymerizable double bond, component (5) of the present invention, will be explained.

A predetermined monomer that is a component of the photosensitive resin of the present invention and, if necessary, other monomers copolymerizable with these monomers are prepared by a known solution polymerization method in a hydrophilic or water-miscible solvent, for example, the monomer is The polymer is dissolved in a solvent, a polymerization initiator is added thereto, and the mixture is stirred and heated under a nitrogen stream to polymerize, thereby producing a polymer as a precursor.

Next, this polymer is modified with a predetermined modifier to obtain the cationic polymer having a photopolymerizable double bond of the present invention. If necessary, water or other solvent can be added to obtain the cationic polymer solution at a predetermined concentration.

Examples of the hydrophilic or water-miscible solvent used during the polymerization include methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, diacetone alcohol, methyl cellosolve, ethyl cellosolve, butyl Examples include alcohols such as Rosolve and butylcarpitol, ethers such as dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, and esters such as cellosolve heptatate. This hydrophilic solvent is added to the final resin solution at a concentration of 5 to 50%.
It is also possible that the total amount of carbon dioxide is 1 or more, or that all of it can be distilled out of the thread by water displacement.

Examples of polymerization initiators include benzoyl peroxide,
Organic peroxides such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, tertiary butyl peroxide, azobisisobutyronitrile, azobisisodimethylvaleronitrile, triazobenzene, phenylazotriphenylmethane, 1 .Azo compounds such as 1'-azobiscumene are used alone or in combination. The molecular weight of the polymer thus obtained is 1,000 to 1
゜ o o o, o o o preferably 5,000 to 10
It is 0,000.

In order to modify the unmodified polymer thus obtained, for example, a Lewis acid and an epoxy group-containing polymerizable monomer capable of donating a proton to a tertiary nitrogen atom to which the nitrogen lone pair is not conjugated are used. In the case of modification by the reaction, the Lewis acid is first reacted to convert the tertiary nitrogen atom into 4R, and then,
This is carried out by reacting with the epoxy group of an epoxy group-containing polymerizable monomer. In the reaction with the epoxy group, since the quaternary nitrogen atom portion acts as a catalyst, it is not necessary to add a new catalyst, but a Lewis acid or Lewis base catalyst may be additionally added depending on the case.

During quaternization, the temperature is 90℃ to avoid polymerization of polymerizable monomers.
In order to avoid zero polymerization, which is preferably carried out below, a polymerization inhibitor such as hydroquinone, hydrogynone monoalkyl ether, etc. can be used if necessary.

Similarly, when a covalently bonded halogen atom-containing polymerizable polymer is modified as a modifying agent, or when a covalently bonded halogen atom-containing precursor polymer is modified with a tertiary nitrogen atom to which the nitrogen lone pair is not conjugated In the case of modification using the contained polymerizable monomer, the reaction can be carried out in the same manner as the above reaction.

The above-mentioned modification reaction can be carried out simply by mixing and stirring the unmodified polymer and the modifier, and can also be carried out in the presence of the hydrophilic or water-miscible solvent and/or water.

When a solvent is used, the reaction temperature is 10 to 120°C, although it varies depending on the boiling point of the solvent, particularly preferably 30 to 90°C to avoid polymerization of the modifier monomer, and the reaction time is usually 1 to 10°C. However, in order to increase the rate of modification, it is preferable to take a reaction time of 3 hours or more.

(Polyvinyl Alcohol and/or Polyvinylpyrrolidone) (6) Partially or fully saponified polyvinyl alcohol of the present invention, or a combination of 20 to 100 parts by weight of vinyl acetate and 80 to 0 parts by weight of other polymerizable monomers, such as ethylene. Partially or fully saponified polymer resins, or derivatives thereof will be described. Partially or fully saponified polyvinyl alcohol used in the present invention, or partially or fully saponified copolymer resins of vinyl acetate and other polymerizable monomers. The degree of saponification is preferably 60 molar or higher, particularly preferably 70 molar or higher.

If the degree of saponification is less than 60 molar ratio, ink drying properties are insufficient and compatibility with cationic polymerizable resins is poor, causing whitening when formed into a film. - Also, 5,000 to 5,000 molecule per molecule of partially or completely saponified polyvinyl alcohol, or partially or completely saponified copolymer resin of vinyl acetate and other polymerizable monomers.
150,000 is preferable, particularly 10,000 to 100,000 is more preferable.

Various commercially available polyvinyl alcohols are available. Derivatives of partially or completely saponified polyvinyl alcohol, or partially or fully saponified copolymer resins of vinyl acetate and other polymerizable monomers include, for example, cinnamate ester derivatives, styrylpyridinium salt derivatives, and cationized products. etc.

Next, the present invention's three-component homopolymer resin of N-vinylpyrrolidone or copolymer resin with other polymerizable monomers will be described. The homopolymer resin of N-vinylpyrrolidone used in the present invention As the copolymerized resin with other polymerizable monomers, monopolymers of vinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, etc. are preferable, and the molecular weight is preferably Fi 5,000 to 1,000,000. ,% [10,000~
800,000 is more preferable. Commercially available polyvinylpyrrolidone resins of various types are available.

(4) A cationic synthetic resin having a photopolymerizable double bond and (13) a partially or completely saponified polyvinyl alcohol, or a partially or fully saponified copolymer resin of vinyl acetate and other polymerizable monomers. , casing or their derivatives, and/or (QN-vinylpyrrolidone homopolymer resin or copolymer resin with other polymerizable monomers) The blending ratio is (
5) is 10-90% by weight, ■ is 0-90% by weight, 0 is 0
~90% by weight, and (4)/[providing)+(C)] is in a weight ratio of 90710 to 10/90, preferably 80/90% by weight.
It is desirable that the weight ratio be 20 to 20,780. If the sum of component (a) and component (0) is less than 10%, it will be difficult to obtain a record with improved ink drying properties and clarity;
If the sum of the components and (Q component) exceeds 90%, the water resistance of the coating film will be insufficient and the ink will bleed, making it impossible to obtain clear records.

As mentioned above, the present invention relates to (2) a cationic synthetic resin having a photopolymerizable double bond, and (2) a copolymer resin of partially or completely saponified polyvinyl alcohol or vinyl acetate and other polymerizable monomers. Good records can be obtained by using partially or fully saponified products, or their derivatives, and/or monopolymer resins of ON-vinylpyrrolidone, or copolymer resins with other polymerizable monomers. When only component (A) is used, the ink drying properties are excellent.
Color bleeding and clumps may occur. In addition, if only the (mouth) component and/or the zero component are used, the coating film may show repellency during coating, the coating film may become white, water resistance may be insufficient, and ink may smear or clumps may occur during recording. You can't get a good record.

(Optional components) In addition to the above resin composition, in order to improve the state of the coating film, etc.
Special monomers such as higher alcohol ethoxylates, polyalkylene glycol acrylates, diacrylates, pentaerythritol triacrylate, trimethylolpropane triacrylate, wetting agents, other electrolyte polymers, additives (e.g. fillers such as clay, carbonaceous, etc.) , silica gel, colloidal sol such as alumina sol), etc. may be added.

In addition, when curing the resin with ultraviolet rays, 0.5 to 5] per 100 parts by weight of the resin! [An additional photoreaction initiator must be added.] Examples of photoreaction initiators include benzophenone, methyl 0-benzoylbenzoate, 4.4
benzophenones such as '-bisdimethylaminobenzophenone, benzoin alkyl ethers such as benzoinmethyl and hentzuinethyl, ketals such as acetophenone diethyl ketal and benzyl dimethyl ketal, thioxanthone such as chlorothioxanthone, methylthioxanthone, isopropylthioxanthone, Dibenzyls and the like can be used, and triethanolamine, jetanolamine, ethanolamine, trialkylamine, dialkylamine, alkylamine, etc. can be used as the amino acid used in combination. The amount of amine used is 0.001 to 3 parts by weight per 100 parts by weight of the polymerizable resin.

(Recording sheet) The resin composition for forming the recording layer is coated by air knife coating,
Crosslinking of polymerizable resin is performed on a base material such as polyethylene terephthalate film by blade coating, barcode coating, gravure coating, curtain coating, roll coating, spray coating, etc., and after solvent drying, irradiation with ultraviolet rays, electron beams, etc. At least a recording layer is formed on the base sheet. The coating amount of the recording layer is 1 to 20 t/
n? , preferably in the range of 2 to 10 t/d. The base sheet 26 includes plastic film, synthetic paper, size,
Used are paper whose air permeability, smoothness, etc. have been carefully adjusted, processed paper with a barrier coating layer coated with resin or extrusion coating of thermoplastic resin, resin-impregnated paper, metal sheets, and the like. In order to improve the adhesion of the Fi recording layer to these base material sheets, an anchor coat may be applied to the base material in some cases.

Active energy rays used to cure the polymerizable resin include high-energy ionizing radiation and ultraviolet rays.

As sources of high-energy ionizing radiation, for example, electron beams accelerated by accelerators such as Kotscroft accelerators, Pandegraaf accelerators, Linear accelerators, betatrons, and cyclotrons are the most convenient and economically used sources in industry. However, other radiation such as radioisotopes and r-rays, X-rays, α-rays, β-rays, neutron beams, and proton beams emitted from nuclear reactors can also be used.

Examples of ultraviolet sources include ultraviolet fluorescent lamps, low-pressure mercury lamps,
There are high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, and sunlight.

When using the high-energy ionizing radiation as the radiation, there is no particular need to use a photoreaction initiator, but when using ultraviolet rays, the photoreaction initiator absorbs ultraviolet rays, generates radicals, and initiates polymerization. using an agent.

The water-based ink recording sheet of the present invention can be used as a drafting film for creating block plates for drawing with water-based ink, a water-based ballpoint pen, etc.
It is also ideal as a film for X-Y plotters using water-based ink felt pens. In particular, when creating OHP (overhead projector) sheets using an X-Y plotter, the current situation is that the color water-based pens used to draw on plain paper are replaced with oil-based pens. However, if the recording sheet of the present invention is used, it is possible to draw the same with a conventionally used water-based pen, and the complicated work of replacing pens can be eliminated at once.

〔effect〕

The aqueous ink recording sheet of the present invention includes (A) a cationic synthetic resin having a photopolymerizable double bond on the surface of a sheet-like base material, and 03) partially or completely saponified polyvinyl alcohol, or vinyl acetate and other polymers. Partially or completely saponified copolymer resins with monomers, derivatives thereof, and/
or (2) A resin composition whose main ingredient is a homopolymer resin of N-vinylpyrrolidone or a mixture of a copolymer resin with other polymerizable monomers is coated and photo-crosslinked. Even if an electrolyte polymer having a cationic group is simply coated on a sheet and a water-based ink is placed on the sheet, the ink will diffuse due to surface tension and smearing will occur, making it difficult to obtain a clear image. By using a type of electrolyte polymer in combination with a polyvinyl alcohol-based resin and/or a polyvinylpyrrolidone-based resin and irradiating it with active energy rays, it is possible to impart appropriate hydrophobicity (monohydrophobicity) to the electrolyte polymer. The ink droplet is clearly absorbed into the surface layer of the photocrosslinked resin on the sheet, maintaining the shape of the ink droplet without spreading and maintaining an appropriate contact angle without smudging.

The resin composition according to the present invention is further characterized in that it has good adhesion even without an anchor coating to a polyester film, which is generally considered to have poor adhesion without an anchor coating.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Note that parts and sections in the examples are based on weight.

Production example of resin ■ In a flask, 80 parts of N,N-dimethylaminoethyl methacrylate (0.51 f equivalent), 10 parts of methyl methacrylate, 10 parts of cyclohexyl methacrylate, 100 parts of isopropanol and 2,2'-azobisisobutylene were added. 0.5 part of lonitrile was charged, and a polymerization reaction was carried out at 80° C. for 6 hours under a nitrogen atmosphere.

Then, cool with water and add 15.5 parts (0.15 g equivalent) of 36% hydrochloric acid.
and 126 parts of water were added dropwise, and after the addition, the mixture was stirred at room humidity for 1 hour, the temperature was further raised to 70°C, and 21.7 parts of glycidyl methacrylate (1 liter per 0.15 g) and 0.022 parts of hydroquinone monomethyl were added dropwise. 1. Stir for 6 hours at the same temperature. Resin ■ was obtained. This methacrylic resin has the following unit C)]3 in its molecular chain and has a molecular weight of about 30,000.

Resin [Similar to the case of resin ①, 50 parts (0.32 g equivalent) of N,N-dimethylaminoethyl methacrylate, 80 parts aqueous solution of methyl chloride modified N,N-dimethylaminoethyl methacrylate (Mitsubishi Rayon product) 12.5 parts, butyl methacrylate 40 parts, ethanol 100 parts and 2,
A polymerization reaction was carried out using 0.5 parts of 2'-azobisisobutyronitrile, and then 19.4 parts of 36-thihydrochloric acid (0,1
9r equivalent), 134 parts of water, 27.2 parts of glycidyl methacrylate (0.19V equivalent), and 0.027 part of hydroquinone monomethyl to obtain resin (2). This methacrylic resin has the following unit ('')]3 Hjell.

It has a molecular weight of about 27,000 including in its molecular chain.

Resin ■ As in the case of resin ■, 20 parts (0.13 van) of N,N-dimethylamine ethyl methacrylate, N,N-
50 parts of an 80% aqueous solution of methyl chloride modified dimethylaminoethyl methacrylate (Mitsubishi Rayon product), 20 parts of methyl methacrylate, 20 parts of butyl methacrylate,
A polymerization reaction was carried out using 100 parts of ethanol and 0.5 part of 2.2-axis azobisisobutyronitrile, and then 3
Modified with 12.9 parts of 6-dihydrochloric acid (0.13f equivalent), 110 parts of water, 18.1 parts of glycidyl methacrylate (0.13° equivalent), and 0.018 parts of hydroquinone monomethyl, with a molecular weight of about 2.5 Ten thousand resin ■ was obtained.

Resin ■ As in the case of 4m fat T, 60 parts of 4-vinylpyridine (
0.57? equivalent), 80% aqueous solution of methyl chloride modified product of N,N-dimethylamine ethyl methacrylate (Mitsubishi Rayon product) 12.5%, butyl methacrylate 30%
The polymerization reaction was carried out using 100 parts of ethanol and 0.5 parts of 2.2'-azobisisobutyronitrile, and then 81.6 parts of 3-chloro-2-hydroxypropyl methacrylate (0.5 parts) was added at 70°C. , 46r per ik), 0.082 parts of hydroquinone monomethyl, and 235 parts of water.
A time denaturation reaction was performed to obtain resin 1v. This resin contains the following unit H3 in its molecular chain and has a molecular weight of approximately 26,000 〇 Resin V As in the case of Resin I, 50 parts of 3-chloro-2-hydroxypropyl methacrylate (0.28 f A polymerization reaction was carried out using 30 parts of methyl methacrylate, 20 parts of cyclohexyl methacrylate, 100 parts of isopropanol and 0.5 part of 2,2'-azobisisobutyronitrile, and then N,N- Resin V was obtained by carrying out a modification reaction for 6 hours using 40.1 parts (0.28 fit) of dimethylamine ethyl acrylate, 0.040 parts of hydroquinone monomethyl, and 160 parts of water. , this methacrylic resin is the next unit OH.

It has a molecular weight of about 24,000 including in its molecular chain.

Comparative resin ■ As in the case of resin I, 5 parts of N,N-dimethylamine ethyl methacrylate (0.03 f equivalent), 95 parts of methyl methacrylate, 100 parts of impropanol, and 2.2 parts of
- A polymerization reaction is carried out using 0.5 parts of azobisisobutyronitrile, followed by 3.2 parts of 36% hydrochloric acid (0.03 f equivalent), 40 parts of water, 54 parts of impropanol and 4.5 parts of glycidyl methacrylate. (0.03 f equivalent -It) and modified with 0.005 part of hydrogynone monomethyl to obtain comparative resin (2) having a molecular weight of about 35,000.

Comparative Resin ■ As in the case of Resin I, an 80% aqueous solution of a methyl chloride modified product of N,N-dimethylaminoethyl methacrylate (362.5 parts of Mitsubishi Rayon ■ product, 5 parts of methyl methacrylate)
A polymerization reaction was carried out using 0 parts of ethanol, 100 parts of ethanol, and 0.5 parts of 2.2'-azobisisobutyronitrile, and then 73 parts of water was added to obtain comparative resin (2) having a molecular weight of about 20,000.

Next, examples and comparative examples using the above-mentioned resin will be described.

Water/isopropanol (1 part 1 weight ratio)/n? of the cationic composition having a photopolymerizable double bond listed in Table 1? ) coated polyester film (100 microns thick) or unanchored polyester film (100 microns thick)
Is the solid content coating lid 411/n using a bar coater on micron thickness? It was applied so that it became Vc.

After drying, the film was cured with ultraviolet light using an ultraviolet irradiation device (manufactured by Nippon Battery; lamp strength: 80 W/cm) at a conveyor speed of 10 m+/min to obtain a transparent recording film.

Apply a water/improper tool (1 part 1 weight ratio) diluted solution of the resin listed in Table 1 to a polyester film that has been anchored in advance using a bar coater so that the solid content is 4 f/d. After drying, the film was irradiated with an electron beam at an acceleration voltage of 150 KV and a current of 2.0 mA at an electron beam dose of 1.0 Mrad using an electron beam irradiation device (manufactured by Electro Curtain Energy Sciences) to obtain a transparent film for recording.

Example 14 Cationic synthetic resin 1 having photopolymerizable double bonds shown in Table 1
A composition containing 3 parts of the photoreaction initiator VICURE55 per 00 parts was coated with a bar coater so that the composition was water/Impropano 5, Ot/-, dried, and then irradiated with ultraviolet light (conveyor speed 10 m/min) to prepare recording paper. It was created.

Comparative Example 4.8.11, 13 Water/isopropanol (1/IJi amount ratio) of the resin in Table 1
The lo% diluted solution was added to polyester with anchor treatment.
Film (100 micron thickness) K solid content coating amount is 42
/- and dried to obtain a transparent film for recording.

In addition to the above Examples 1 to 14 and Comparative Examples 1 to 13, commercially available high-quality inkjet recording paper (Reference Example 1) and Example 1
Inkjet recording performance was evaluated by the following method by adding the coated paper used in Example 4 (Reference Example 2). (1) Measurement of dot density and dot diameter: Sakura densitometer PDM-5 (Konishi Roku Photo Industry Co., Ltd.) The company exhibition) was used.

(2) Observation of dot diameter: Evaluation was made based on the shape of the dots observed with a stereomicroscope and the edge portion O (circular and sharp) x (irregular and with large smearing).

(3) Ink drying property: A test pattern was recorded using Sharp Color Image Blotter-IO-0700.
After a few minutes, it was transferred onto paper and the drying properties were evaluated based on the presence or absence of transfer. Evaluation was made on a five-point scale from 5 (no transfer at all) to 1 (severe transfer).

(4) 3 Surface specific resistance value: Measured using an insulation resistance meter TR-8601 manufactured by Takeda Riken under conditions of 20° C. and 60° relative humidity.

(5) A certain amount of water droplets were dropped onto the paint film using a water-resistant varnish void, and the degree of damage to the paint film was evaluated when the water was immediately wiped off.

0: No damage at all [2, △: Slightly damaged, ×: Completely wiped off.

The results are shown in Table-1.

A color image printer (Sharp Co., Ltd. I
Comparative Examples 1 to 7 were printed using
Excellent drying properties of water-based ink compared to No. 13, printing part Fi41
! It exhibited good adhesion and did not come off at all even when the film was exposed to sunlight, and the printed images had high color density, clarity, and resolution, making it ideal as a film for color overhead projectors. On the other hand, when printing on a polyester film as a base material, the ink did not dry at all, repelled, and fell off when touched with the finger.

The prints on the inkjet recording paper of Example 13 had high color density, were clear, and had high resolution. The color image quality was far superior to that of Example 1).

When drawing was performed on the recording sheet of Example 2.5.8 according to the present invention using an X-Y plotter PL2000 (manufactured by Yokogawa Electric Corporation) with water-based ink Ben C (black, red, yellow φ blue), it was found that the water-based inks of each color were The drawing properties and ink drying properties were good, and the film exhibited excellent drawing performance, making it ideal as a film for overhead projectors.

(Margin below)

Claims (1)

[Scope of Claims] 1) (A) 90 to 10% by weight of a cationic synthetic resin having a photopolymerizable double bond, and (B) 20 to 100% by weight of partially or completely saponified polyvinyl alcohol or vinyl acetate, and others. A partially or completely saponified copolymer resin with 80 to 0% by weight of a polymerizable monomer, or 0 to 90% by weight of a derivative thereof, and/or a homopolymer resin of (C) N-vinylpyrrolidone or others. Copolymerized resin with polymerizable monomer of 0 to 90
% by weight, and (A)/[(B)+(C)] is 9
A resin composition based on a mixture having a weight ratio of 0/10 to 10/90 is applied to the surface of a support sheet, and then irradiated with active energy rays to cure the resin composition and coated on the support. Water-based ink recording sheet with a resin coating layer. 2) A patent claim characterized in that the cationic synthetic resin having a photopolymerizable double bond of component (A) is a polymerizable resin having a polymerizable double bond and a quaternary ammonium salt functional group. The water-based ink recording sheet according to item 1. 3) (A) The cationic synthetic resin having a photopolymerizable double bond contains 10 to 100% by weight of a polymerizable monomer having a tertiary nitrogen atom with no nitrogen lone pair conjugated, and others. A polymerizable monomer having a Lewis acid and an epoxy group capable of donating protons to the polymer resin with 90 to 0% by weight of a polymerizable monomer,
0.0 of the tertiary nitrogen atom-containing polymerizable monomer of the polymer resin.
3. The aqueous ink recording sheet according to claim 2, which is a resin obtained by quaternizing the tertiary nitrogen atoms of the polymer resin by reacting with 1 to 1.0 g equivalent. 4), (A) The cationic synthetic resin having a photopolymerizable double bond contains 10 to 100% by weight of a polymerizable monomer having a tertiary nitrogen atom to which the nitrogen lone pair is not conjugated, and others. A polymerizable monomer having a covalently bonded halogen atom is further added to the polymer resin with 90 to 0% by weight of a polymerizable monomer containing 0.0% by weight of a tertiary nitrogen atom-containing polymerizable monomer of the polymer resin. 3. The aqueous ink recording sheet according to claim 2, which is a resin obtained by quaternizing the tertiary nitrogen atoms of the polymer resin by reacting with 1 to 1.0 g equivalent. 5) (A) The cationic synthetic resin having a photopolymerizable double bond is a polymerizable monomer 1 having a covalently bonded halogen atom.
0 to 100% by weight and 90 to 0% by weight of other polymerizable monomers
Further, a polymerizable monomer having a tertiary nitrogen atom to which a nitrogen lone pair is not conjugated is added to the polymer resin, and 0.1 of the covalently bonded halogen atom-containing polymerizable monomer of the polymer resin is added. ~
Claim 2, characterized in that the resin is a resin into which a quaternary ammonium base is introduced by reacting with 1.0 g equivalent.
Water-based ink recording sheet as described in Section 1. 6) Claim 1, wherein the aqueous ink recording sheet is an ink jet recording sheet.
Water-based ink recording sheet as described in Section 1. 7) Claim 1, wherein the aqueous ink recording sheet is an X-Y plotter recording sheet.
Water-based ink recording sheet as described in Section 1.