JPH0818455B2 - Aqueous ink recording sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to a recording sheet using a water-based ink, and particularly to a paper, a plastic film, a synthetic paper, a metal sheet, etc., which can obtain a high-quality color image by an ink jet recording system. The present invention relates to an ink jet recording sheet as a base material.

The ink jet recording method has no noise, does not require development and fixing processes, can perform high-speed recording, and can easily perform multicolor color recording, and thus has rapidly spread to facsimiles, word processors, terminal printers, etc. in recent years. It's starting. In particular, the development of a color printer using an ink jet recording method for making a color hard copy from a color display is in progress. Inkjet color printers have recently achieved high image quality similar to gravure printing or silver halide photography, including in the field of color graphics using 7 expression colors (yellow, magenta, cyan, red, green, purple, black). High-resolution color printers have been developed to produce full color copies, so-called pictorial copies.

[Prior art]

Inkjet recording has the advantage that plain paper (PPC) can be used. However, in general, ordinary plain paper is not satisfactory as an ink jet recording paper suitable for multicolor recording.

The basic performance required of an ink jet recording sheet is that the dot shape is circular, there is no spread such as bleeding, and the area around the dot is sharp and has high resolution.

2 High dot color density and good sharpness.

3 The ink has a fast absorption speed and is excellent in drying property, the ink absorption amount is large, and when the dots of ink overlap, the multi-color color recordability such that the dots that adhere later do not flow out is good.

4 The dimensional change after recording is small and there is no curling, waviness, or deformation.

And the like.

Above all, it is a technical problem among those skilled in the art to satisfy both the absorptivity of ink, which controls the drying property of ink, and the contradictory property of spread (bleeding) of dots. That is, if the ink absorbency of the recording paper is fast, the spread of the dots is generally large and the dot shape is also distorted, resulting in deterioration of the resolution. In addition, the ink tends to penetrate deeply into the paper layer, which lowers the color density and its sharpness.

Further, in order to obtain high image quality by recent multi-color recording, it is required that the ink of each color adheres to the same location on or near the recording sheet in a short time, so that the ink absorbency and especially the ink absorption capacity are large. To be done. Otherwise, the unabsorbed ink will flow out (flow), and as a result, a clear image cannot be obtained or it may cause stains.

As the ink jet recording paper, plain paper such as high-quality paper can be basically used, but those skilled in the art of manufacturing recording paper can adjust the size, air permeability, and tightness according to the recording method and its conditions or the ink. Actually, the physical property values of paper such as smoothness and elongation in water are adapted. On the other hand, in order to obtain a high-quality color record, which is a recent trend, it is not possible to control the physical properties of these papers alone, and in order to obtain the recordability that satisfies the above basic requirements, the surface of the sheet is coated. Coated paper type ink jet recording paper in which layers are provided and pigments and binders are optimized has been studied.
However, in reality, there is no ink jet recording paper for high image quality which satisfies not only the recording performance but also the water resistance, weather resistance and dimensional stability of the recording portion.
As a recent trend, there is a demand for using not only paper but also impregnated paper, plastic film, synthetic paper, water resistant sheets such as metal sheets, and transparent sheets as the base sheet. For example, specifically, as the color display of personal computers progresses, color hard copy will be transcribed.
There is a demand for a transparent film capable of ink jet recording for use in (overhead projector). However, plastic films such as polyester used for OHP films cannot be used because they are hydrophobic and have no absorbability of water-based ink unlike paper substrates. The same applies to other paper products such as impregnated paper, synthetic paper, and metal sheets.

The development of ink jet recording sheets using such new materials as a base material is technically limited by the conventional approach based on the concept of manufacturing plain paper and coated paper.

Further, as the ink solvent for the ink jet, if water is usually used alone, the ejection nozzle will be clogged due to evaporation,
Various contrivances have been made by adding polyalkylene glycol and a wetting agent to water so as not to cause clogging due to drying. On the contrary, when recording is performed on a recording sheet such as a synthetic resin film, it causes the ink drying property to be further deteriorated.

As described above, the most important problem in this field is how to make the ink droplets of the ink jet stick to the recording sheet, in particular, the transparent synthetic resin film such as polyester, so that the ink droplets clearly stick to each other and quickly absorb and dry.

[Problems to be solved by the invention]

The present invention provides a water-based ink recording sheet that can clearly and firmly record a multicolor full-color copy, which is an advantage of an ink jet, and has excellent ink absorption and drying properties.

[Means for solving problems]

The present invention is a special cationic active energy ray curable resin, and partially or completely saponified polyvinyl alcohol,
Alternatively, a partial or complete saponification product of a copolymer resin of vinyl acetate and another polymerizable monomer, or a derivative thereof, and / or a homopolymer resin of N-vinylpyrrolidone, or another polymerizable monomer The resin composition containing the mixture of the copolymer resin as a main component is applied to the surface of the support sheet, and then the active energy ray is irradiated to cure the resin composition to form a resin film layer on the support. As a result, the adhesion of the water-based ink is improved, and clear printing without bleeding is provided.

That is, the ink jet recording property is excellent in that the resin film layer absorbs and dries ink droplets well, does not spread the ink droplets, and does not penetrate deeply into the interior, so that the ink droplets are obtained as a clear and sticky image. . Further, since the cationic synthetic resin in the resin composition is three-dimensionalized by irradiation with active energy rays, the water resistance is good, and the recording sheet itself is not deformed after recording. Further, since the cation-based synthetic resin is an electrolyte polymer, it has excellent antistatic properties and does not have dust.

[Structure of Invention]

The present invention includes (A) a cationic synthetic resin having a photopolymerizable double bond, and (B) partially or completely saponified polyvinyl alcohol, or 20 to 100% by weight of vinyl acetate and 80 to 50% of another polymerizable monomer. 0% by weight of partially or completely saponified copolymer resin or derivative thereof, and / or (C) N-vinylpyrrolidone homopolymer resin, or copolymer resin with other polymerizable monomer A water-based ink in which a resin composition containing a mixture as a main component is applied to the surface of a support sheet, and then dried and irradiated with an active energy ray to cure the resin composition to form a resin film layer on the support. A recording sheet is provided.

(Cationic Polymerizable Resin) The cationic synthetic resin having a photopolymerizable double bond of the component (A) of the present invention is a polymerizable resin having a polymerizable double bond and a functional group of a quaternary ammonium salt. There are, for example, the following (i) to (iii).

(I) A polymer resin containing 10 to 100% by weight of a polymerizable monomer having a tertiary nitrogen atom to which a lone pair of nitrogen is not conjugated, and 90 to 0% by weight of another polymerizable monomer. Further, a polymerizable monomer having a Lewis acid capable of donating a proton and an epoxy group is reacted with 0.1 to 1.0 g equivalent of the tertiary nitrogen atom-containing polymerizable monomer of the polymer resin, Resin third
Resin with quaternary nitrogen atom.

Examples of the polymerizable monomer having a tertiary nitrogen atom in which the lone electron pair of nitrogen is not conjugated include, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, or N General formula of N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, etc. Or [In the above formulas (1) and (2), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each an alkyl group having 1 to 4 carbon atoms, and n is 1
~ Indicates a number of 4. ] A (meth) acrylic monomer represented by the following; a general formula such as dimethylaminomethylstyrene, diethylaminomethylstyrene, dibutylaminomethylstyrene, etc. [In the formula, R ¹ and R ² each represent an alkyl group having 1 to 4 carbon atoms. ] A styrene-based monomer represented by the general formula: vinyl pyridine, methyl vinyl pyridine, ethyl vinyl pyridine, etc. [In formula, R shows a hydrogen atom or a C1-C4 alkyl group. ] One or a mixture of two or more of the pyridine-based monomers represented by

As the other polymerizable monomer, a cation-modified monomer such as methyl chloride, ethyl chloride or methyl monochloroacetate of the tertiary nitrogen atom-containing monomer of the above formulas (1) to (4) (these cationized monomers are It may be used in polymerization after quaternization or may be quaternized after polymerization.) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) Alkyl (meth) acrylates such as acrylate, octyl (meth) acrylate, ularyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, ethoxyacryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl ( (Meth) acrylate, styrene , Vinyl toluene, vinyl acetate, and the like.

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

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

(Ii) A polymer resin containing 10 to 100% by weight of a polymerizable monomer having a tertiary nitrogen atom to which a lone pair of nitrogen is not conjugated, and 90 to 0% by weight of another polymerizable monomer. Further, the polymerizable monomer having a covalently bonded halogen atom is reacted with 0.1 to 1.0 g equivalent of the polymerizable monomer containing a tertiary nitrogen atom of the polymer resin to give a tertiary nitrogen atom of the polymer resin. Resin that has been quaternized.

As the polymerizable monomer having a tertiary nitrogen atom to which the lone pair of nitrogen is not conjugated and the other polymerizable monomer, the same ones as in (i) 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). General formulas such as 3-halo-2-hydroxypropyl (meth) acrylate such as acrylate, chloromethyl (meth) acrylate, chloroethyl (meth) acrylate, bromobutyl (meth) acrylate [In the formula, R represents a hydrogen atom or a methyl group, X represents chlorine, bromine, iodine, and n represents a number of 1 to 4. ] The ω-haloalkyl (meth) acrylate represented by

(Iii) Polymerizable monomer 1 having a covalently bonded halogen atom
Third, a lone electron pair of nitrogen is not conjugated to a polymer resin of 0 to 100% by weight and 90 to 0% by weight of another polymerizable monomer.
A resin in which a quaternary ammonium salt group is introduced by reacting a polymerizable monomer having a quaternary nitrogen atom with 0.1 to 1.0 g equivalent of a covalently bonded halogen atom-containing polymerizable monomer of the polymer resin.

The covalently bonded halogen atom-containing polymerizable monomer, other polymerizable monomer, and the tertiary nitrogen atom-containing polymerizable monomer in which the lone electron pair of nitrogen is not conjugated are the same as (i) and (ii). Can be used.

In these (i), (ii) and (iii) resins,
The tertiary nitrogen atom-containing polymerizable monomer or the covalently bonded halogen atom-containing polymerizable monomer in which the lone electron pair of nitrogen is not conjugated to obtain the precursor polymer resin is 10 to 100% by weight, preferably 20 The amount of the other polymerizable monomer is 90 to 0% by weight, preferably 80 to 20% by weight.

Further, to the polymer resin having a tertiary nitrogen atom or a covalently bonded halogen atom to which the lone pair of nitrogen is not conjugated, a Lewis acid capable of donating a proton and an epoxy group-containing polymerizable monomer, a covalent bond The halogen atom-containing polymerizable monomer or the tertiary nitrogen atom-containing polymerizable monomer in which the lone electron pair of nitrogen is not conjugated is a tertiary nitrogen atom or a shared nitrogen atom in which the lone electron pair of nitrogen is not conjugated. 0.1-1.0 g equivalent of the polymerizable monomer having a bound halogen atom, preferably 0.2-
Used at a rate of 1.0 g equivalent.

If the amount of the polymerizable monomer containing a tertiary nitrogen atom or a covalently bonded halogen atom to which a lone electron pair of nitrogen is not conjugated in the precursor resin is too small, the water-based ink has insufficient absorption and drying properties. On the other hand, if the amount is too large, the water-based ink bleeds and clear printing cannot be obtained. When the proportion of the other polymerizable monomer is less than the above amount, the water resistance of the coating film of the crosslinked resin layer obtained by photocuring the polymerizable resin is insufficient and the water-based ink is bleeding and is clear. Can not get a good print. On the other hand, if the amount is too large, the coating film after photocuring becomes hydrophobic and the absorption and drying of the water-based ink deteriorates.

Next, a method for producing the cationic synthetic resin having the photopolymerizable double bond of the component (A) of the present invention will be described. A predetermined monomer, which is a component of the photosensitive resin of the present invention, and optionally another monomer copolymerizable therewith are prepared by a known solution polymerization method in a hydrophilic or water-miscible solvent, for example by The polymer is dissolved in a solvent, a polymerization initiator is added, the mixture is stirred and heated under a nitrogen stream to polymerize, and a polymer as a precursor is first prepared.

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 another solvent may be added to obtain the cationic polymer solution having a predetermined concentration.

Examples of the hydrophilic or water-miscible solvent used in the above polymerization include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, diacetone alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl carbitol. And alcohols, dioxane, tetrahydrofuran and other ethers, acetone, methyl ethyl ketone and other ketones, and cellosolve acetate and other esters. This hydrophilic solvent is added to the final resin solution in an amount of 5-50
It may be contained by weight% or may be entirely distilled out of the system later by water replacement.

Examples of the polymerization initiator include benzoyl peroxide, acetyl peroxide, lauroyl peroxide,
Organic peroxides such as decanoyl peroxide and tertiary butyl peroxide, azobisisobutyronitrile, azobisisodimethylvaleronitrile, triazobenzene, phenylazotriphenylmethane, 1,1'-azobiscumene, etc. Azo compounds may be used alone or in combination.
The polymer thus obtained has a molecular weight of 1,000 to 1,00.
0,000 It is preferably 5,000 to 100,000.

To modify the thus obtained unmodified polymer, for example, a Lewis acid and an epoxy group-containing polymerizable monomer which can donate a proton to a tertiary nitrogen atom to which a lone pair of nitrogen is not conjugated are used. In the case of modification by the body, the reaction is carried out by first reacting the Lewis acid to quaternize the tertiary nitrogen atom and then reacting with the epoxy group of the epoxy group-containing polymerizable monomer. Reaction with epoxy groups is 4
It is not necessary to add a new catalyst because the primary nitrogen atom portion acts as a catalyst, but a Lewis acid or Lewis base catalyst may be added additionally in some cases.

The temperature is 90 ° C to avoid polymerization of polymerizable monomers during quaternization.
The following is preferable. In order to avoid polymerization, a polymerization inhibitor such as hydroquinone or hydroquinone monoalkyl ether may be used depending on the case.

Similarly, when a covalently-bonded halogen atom-containing polymerizable monomer is modified as a modifier, or when a covalently-bonded halogen atom-containing precursor polymer is polymerized with a tertiary nitrogen atom-containing nitrogen lone electron pair not conjugated. The same reaction as described above can be carried out in the case of modifying with a polar monomer.

The above-mentioned modification reaction may be carried out only by mixing and stirring the unmodified polymer and the modifier, and it 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 varies depending on the boiling point of the solvent, but is 10 to 120 ° C., particularly preferably 30 to 90 ° C. at which polymerization of the modifier monomer is avoided, and the reaction time is usually 1
The reaction time can be up to 10 hours, but it is preferable to take a reaction time of 3 hours or more in order to increase the modification rate.

(Polyvinyl alcohol and / or polyvinyl pyrrolidone) (B) Partially or completely saponified polyvinyl alcohol of the present invention, or a copolymer resin of 20 to 100% by weight of vinyl acetate and another polymerizable monomer such as 80 to 0% by weight of ethylene. The partially or completely saponified product of, or a derivative thereof will be described.
The partially or completely saponified polyvinyl alcohol used in the present invention, or the saponification degree of the partially or completely saponified product of a copolymer resin of vinyl acetate and another polymerizable monomer is preferably 60 mol% or more, and particularly 70 mol% or more. Is more preferable. If the degree of saponification is less than 60 mol%, the ink drying property is insufficient and the compatibility with the cationic polymerizable resin is poor, causing whitening when formed into a coating film. Further, the molecular weight of the partially or completely saponified product of vinyl alcohol or a copolymer resin of vinyl acetate and another polymerizable monomer is preferably 5,000 to 150,000, particularly 10,000 to 100,000. Is more preferable. As such polyvinyl alcohol, various commercially available products can be used.
Partially or completely saponified polyvinyl alcohol, or partially or completely saponified derivative of a copolymer resin of vinyl acetate and another polymerizable monomer, for example, cinnamic acid ester derivative, styrylpyridinium salt derivative, cationized compound and the like. Can be mentioned.

Next, the homopolymerized resin of N-vinylpyrrolidone as the component (C) of the present invention or a copolymerized resin with other polymerizable monomer will be described. The N-vinylpyrrolidone homopolymer resin used in the present invention or a copolymer resin with another polymerizable monomer may be a vinylpyrrolidone homopolymer or a vinylpyrrolidone vinyl acetate copolymer. Is preferred,
The molecular weight is preferably 5,000 to 1,000,000, particularly 10,000 to 80
10,000 is more preferable. As such a polyvinylpyrrolidone-based resin, various commercially available products can be used.

(A) Cationic synthetic resin having a photopolymerizable double bond, and (B) component or completely saponified polyvinyl alcohol, or partially or completely saponified product of a copolymer resin of vinyl acetate and another polymerizable monomer. , Or their derivatives, and / or (C) the homopolymerization resin of N-vinylpyrrolidone, or the compounding ratio of the copolymerization resin with other polymerizable monomers,
(A) is 10 to 90% by weight, (B) is 0 to 90% by weight, (C)
Is 0 to 90% by weight, and (A) / [(B) +
(C)] is 90/10 to 10/90 weight ratio, more preferably 80/20
It is desirable that the ratio is from 20 to 80% by weight, and if the sum of the components (B) and (C) is less than 10% by weight, it is difficult to obtain a record in which the drying property and sharpness of the ink are further improved. B)
When the sum of the component and the component (C) is more than 90% by weight, the water resistance of the coating film is insufficient, the ink bleeds, and clear recording cannot be obtained.

As described above, the present invention provides (A) a cationic synthetic resin having a photopolymerizable double bond, and (B) a partially or completely saponified polyvinyl alcohol, or a copolymer resin of vinyl acetate and another polymerizable monomer. Good recording can be obtained by using a partially or completely saponified product, or a derivative thereof, and / or a homopolymerized resin of (C) N-vinylpyrrolidone or a copolymerized resin with another polymerizable monomer. Is
When only the component (A) is used, the ink drying property is not good enough, and color bleeding and lumps occur. Further, when only the component (B) and / or the component (C) is used, the coating film may be repelled during coating, the coating film may be whitened, and the water resistance may be insufficient, resulting in ink bleeding or lumps during recording. You cannot get a good record.

(Optional component) In addition to the above resin composition, in order to improve the coating film state and the like, special monomers such as acrylates of higher alcohol ethoxylates and polyalkylene glycols, diacrylates, pentaerythritol triacrylate, and trimethylolpropane triacrylate, It is possible to add a wetting agent, another electrolyte polymer, an additive (for example, a filler such as clay or calcium carbonate, or a colloidal sol such as silica gel or alumina sol).

Further, when the resin is cured by ultraviolet rays, 0.5 to 5 parts by weight of the photoreaction initiator must be added to 100 parts by weight of the resin. Examples of the photoreaction initiator include benzophenones such as benzophenone, methyl o-benzoylbenzoate, and 4,4′-bisdimethylaminobenzophenone,
Benzoin alkyl ethers such as benzoin methyl and benzoin ethyl, acetophenone diethyl ketal,
Ketals such as benzyl dimethyl ketal, chlorothioxanthone, methylthioxanthone, thioxanthones such as isopropylthioxanthone, dibenzyl and the like can be used, and as the amine used in combination, triethanolamine, diethanolamine, ethanolamine, trialkylamine, dialkylamine, Alkylamine etc. can be used. The amount of amine used is 0.001 to 3 parts by weight per 100 parts by weight of the polymerizable resin.

(Recording sheet) Coating of the resin composition for forming the recording layer is carried out on a substrate such as polyethylene terephthalate film by an air knife coat, blade coat, bar coat, gravure coat, curtain coat, roll coat or spray coat method. Then, after the solvent is dried, the polymerizable resin is crosslinked by irradiating with ultraviolet rays or electron beams to form a recording layer on the substrate sheet. The coating amount of the recording layer is in the range of 1 to ²⁰ g / m ² , preferably ² to 10 g / m ² . As the base material sheet, plastic film, synthetic paper, paper with controlled size, air permeability, smoothness, etc., and paper processed product with a barrier coating layer provided by resin coating or extrusion coating of thermoplastic resin, resin impregnation Use paper, metal sheet, etc. In some cases, an anchor coat is applied to the base material sheet to improve the adhesiveness of the recording layer.

Examples of active energy rays used for curing the polymerizable resin include high energy ionizing radiation and ultraviolet rays.

As a high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as Kotsk Croft accelerator, Van De Graaf accelerator, linear accelerator, betatron, cyclotron is the most convenient and economical in industry. In addition, radiation such as γ-rays, X-rays, α-rays, β-rays, neutron rays and proton rays emitted from radioactive isotopes and nuclear reactors can be used.

Examples of the ultraviolet ray source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and sunlight.

When the high-energy ionizing radiation is used as the radiation, it is not necessary to use a photoreaction initiator, but when ultraviolet rays are used, the photoreaction initiation to start the polymerization by absorbing the ultraviolet rays to generate radicals. Use agents.

The water-based ink recording sheet of the present invention is also most suitable as a drawing film for making a block drawing with a water-based ink or a film for an XY plotter using a water-based ballpoint pen, a water-based ink felt pen, or the like. In particular, when making an OHP (Overhead Projector) sheet using an XY plotter, the fact is that the color water-based pens currently used for drawing plain paper are replaced with oil-based pens for drawing. However, if the recording sheet of the present invention is used, it is possible to perform continuous drawing with a water-based pen that has been conventionally used, and it is possible to eliminate complicated pen replacement work at once.

〔effect〕

The aqueous ink recording sheet of the present invention comprises (A) a cationic synthetic resin having a photopolymerizable double bond on the surface of a sheet-like substrate, and (B) partially or completely saponified polyvinyl alcohol, or vinyl acetate and other Copolymerization with polymerizable monomer Partially or completely saponified resin, or derivative thereof, and / or (C) N-vinylpyrrolidone homopolymer resin, or copolymerization with other polymerizable monomer A resin composition containing a mixture of resins as a main component is applied and photocrosslinked. Even when an electrolytic polymer having a cationic group is simply applied onto a sheet, when an aqueous ink is placed on the sheet, the ink is diffused due to surface tension to cause bleeding and a clear image is not formed. Type electrolyte polymer, and by further using polyvinyl alcohol-based resin and / or polyvinylpyrrolidone-based resin in combination and irradiating with active energy rays, it is possible to impart appropriate hydrophobicity (water resistance) to the electrolyte polymer, The ink is absorbed clearly without bleeding while maintaining the shape of the ink droplet on the surface layer of the photocrosslinking resin, which is the surface layer on the sheet, while maintaining a suitable contact angle without diffusion.

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

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these examples. The parts and% in the examples are based on weight.

(A) Production Example of Cationic Synthetic Resin Having Photopolymerizable Double Bond Resin I In a flask, 80 parts of N, N-dimethylaminoethylmethacrylate (0.51 g equivalent), 10 parts of methylmethacrylate,
Cyclohexyl methacrylate 10 parts, isopropanol
100 parts and 0.5 parts of 2,2'-azobisisobutyronitrile were charged, and a polymerization reaction was carried out at 80 ° C for 6 hours in a nitrogen atmosphere.

Then water-cool and 36% hydrochloric acid 15.5 parts (0.15 g equivalent) and water 126
Part, and after stirring, stir at room temperature for 1 hour, then 70 ℃
21.7 parts of glycidyl methacrylate (0.15 g
Equivalent) and 0.022 parts of hydroquinone monomethyl are added dropwise,
Resin I was obtained by stirring at the same temperature for 6 hours. This methacrylic resin is And having a molecular weight of about 30,000.

Resin II As in the case of Resin I, 50 parts (0.32 g equivalent) of N, N-dimethylaminoethylmethacrylate, an 80% aqueous solution of methyl chloride modified N, N-dimethylaminoethylmethacrylate (Mitsubishi Rayon Co., Ltd. product ) 12.5 parts, 40 parts of butyl methacrylate, 100 parts of ethanol and 0.5 part of 2,2'-azobisisobutyronitrile were used to carry out the polymerization reaction, followed by 3
Resin II was obtained by modification with 6% hydrochloric acid 19.4 parts (0.19 g equivalent), water 134 parts, glycidyl methacrylate 27.2 parts (0.19 g equivalent) and hydroquinone monomethyl 0.027 part. This methacrylic resin is It has a molecular weight of about 27,000 including in the molecular chain.

Resin III As in the case of Resin I, 20 parts (0.13 g equivalent) of N, N-dimethylaminoethylmethacrylate, an 80% aqueous solution of methyl chloride-modified N, N-dimethylaminoethylmethacrylate (Mitsubishi Rayon Co., Ltd. product ) 50 parts, methyl methacrylate 20 parts, butyl methacrylate 20 parts, ethanol 100
And 0.5 parts of 2,2'-azobisisobutyronitrile were used to carry out a polymerization reaction, and then 12.9 parts of 36% hydrochloric acid (0.13 g
Equivalent), 110 parts of water, 18.1 parts of glycidyl methacrylate (0.13 g equivalent) and 0.018 part of hydroquinone monomethyl were modified to obtain Resin III having a molecular weight of about 25,000.

Resin IV As in Resin I, 60 parts of 4-vinylpyridine (0.
57 g equivalent), 80% aqueous solution of N, N-dimethylaminoethyl methacrylate modified with methyl chloride (Mitsubishi Rayon Co., Ltd.)
Product) 12.5 parts, butyl methacrylate 30 parts, ethanol 10
A polymerization reaction was carried out using 0 part and 0.5 part of 2,2'-azobisisobutyronitrile, and then 3-chloro-2-
A modification reaction was performed for 6 hours using 81.6 parts (0.46 g equivalent) of hydroxypropyl methacrylate, 0.082 parts of hydroquinone monomethyl, and 235 parts of water to obtain a resin IV. This resin is It has a molecular weight of about 26,000 including in the molecular chain.

Resin V As in Resin I, 50 parts of 3-chloro-2-hydroxypropyl methacrylate (0.28 g equivalent), 30 parts of methyl methacrylate, 20 parts of cyclohexyl methacrylate.
Parts, 100 parts of isopropanol and 0.5 parts of 2,2′-azobisisobutyronitrile were used to carry out the polymerization reaction, then 7 parts
A resin V was obtained by carrying out a modification reaction at 0 ° C. for 6 hours using 40.1 parts (0.28 g equivalent) of N, N-dimethylaminoethyl acrylate, 0.040 part of hydroquinone monomethyl, and 160 parts of water. This methacrylic resin is It has a molecular weight of about 24,000 including in the molecular chain.

Comparative Resin I As with Resin I, 5 parts N, N-dimethylaminoethylmethacrylate (0.03 g equivalent), 95 parts methylmethacrylate, 100 parts isopropanol and 0.5 parts 2,2-azobisisobutyronitrile were used. To carry out a polymerization reaction, and then 3.2 parts of 36% hydrochloric acid (0.03 g equivalent), 40 parts of water, 54 parts of isopropanol and 4.5 parts of glycidyl methacrylate (0.03 g
Equivalent), and modified with 0.005 parts of hydroquinone monomethyl to obtain comparative resin I having a molecular weight of about 35,000.

Comparative resin II As in the case of resin I, 62.5 parts of an 80% aqueous solution of N, N-dimethylaminoethyl methacrylate modified with methyl chloride (Mitsubishi Rayon Co., Ltd.), methyl methacrylate 50
Part, ethanol 100 parts, and 2,2'-azobisisobutyronitrile 0.5 part were used to carry out a polymerization reaction, and then water 73 parts was added to obtain a comparative resin II having a molecular weight of about 20,000.

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

Examples 1-9, 12-13, Comparative Examples 1-3, 5-7, 9-1
0, 12 per 100 parts of the cationic synthetic resin having a photopolymerizable double bond shown in Table 1, water / isopropanol (1 of a composition containing 3 parts of a photoinitiator VICURE55 (trade name) manufactured by Stouffer) 10% diluted solution was used as an anchor treatment agent (anchor treatment agent under-rakka RU manufactured by Toyo Ink Co., Ltd.
(Product name), 0.5 g / m ² ) applied polyester film (100 μm thick) or anchor-free polyester film (100 μm thick) using a bar coater to give a solid coating amount of 4 g / It was applied so as to be m ² .

Then, after drying, it was ultraviolet-cured at a conveyor speed of 10 m / min using an ultraviolet irradiation device (manufactured by Nippon Batteries; lamp intensity 80 W / cm) to obtain a transparent recording film.

Examples 10 to 11 A 10% diluted solution of water / isopropanol (1/1 by weight) of the resin shown in Table 1 was pre-anchor-treated on a polyester film using a bar coater to give a solid content of 4 g.
After coating and drying so as to be / m ² , an electron beam irradiation device (manufactured by Electro Curtain Energy Science Co.) was used to irradiate an electron beam irradiation amount of 1.0 Mrad with an acceleration voltage of 150 KV and a current of 2.0 mA, and a transparent film for recording. Got

Example 14 Cationic synthetic resin having photopolymerizable double bond in Table 1
A 100% water / isopropanol (1/1 weight ratio) 10% dilution of a composition containing 3 parts of the photoinitiator VICURE55 per 100 parts was applied to coated paper (SK coat, Sanyo Kokusaku Pulp) to obtain a dry solid content of 5.0 g. A bar coater was applied so that the amount would be / m ^2, and after drying, ultraviolet rays were applied (conveyor speed 10 m / min) to prepare recording paper.

Comparative Examples 4, 8, 11, 13 Water / isopropanol (1/1 weight ratio) 10 of the resins in Table 1
The diluted solution (%) was applied to an anchor-treated polyester film (thickness of 100 μm) so that the solid content was 4 g / m ² , and dried to obtain a transparent recording film.

In addition to the above Examples 1 to 14 and Comparative Examples 1 to 13, a commercially available high quality ink jet recording paper (Reference Example 1) and the coated paper used in Example 14 (Reference Example 2) were added to give the following ink jet recording properties. It was evaluated by the method.

(1). Measurement of dot concentration and dot diameter: Sakura Densitometer PDM-5 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) was used.

(2). Observation of dot diameter: The shape of the dot and the edge of the dot observed with an actual microscope were evaluated by ○ (circular and sharp) × (large irregularity and bleeding).

(3). Ink Dryness: A test pattern was recorded using Sharp Color Image Protter IO-0700, and after 1 minute, the test pattern was transferred to paper and the dryness was evaluated by the presence or absence of transfer.
The evaluation was performed in 5 grades from 5 (no transfer at all) to 1 (terrible transfer).

(4). Surface specific resistance value: Measured with an insulation resistance meter TR-8601 manufactured by Takeda Riken Co., Ltd. under the conditions of 20 ° C. and 60% relative humidity.

(5). Water resistance: A certain amount of water droplets was dropped on the coating film with a dropper, and the degree of damage of the coating film when immediately wiped off was evaluated.
◯: No damage, Δ: Slight, X: all wiped off.

 The results are shown in Table 1.

The color image printer (IO, manufactured by Sharp Corporation) was applied to the transparent sheet for ink jet recording of Examples 1 to 12 according to the present invention.
-0700), it was superior to Comparative Examples 1 to 13 in that the water-based ink was dried, and the printed part showed good adhesion with no scratching and the printed image had a color density of It was high, clear, and had a high resolution, making it an optimal film for color overhead projectors. On the other hand, when the polyester film as the base material was printed, the ink did not dry at all, repellency appeared, and the ink fell off with the touch of a finger.

The printed matter of the ink jet recording paper of Example 13 had a high color density and a clear image with high resolution, and was a general coated paper used as a substrate (Reference Example 2) and a high-quality ink jet recording paper (Reference Example). The color image quality was far superior to that of 1).

The recording sheets of Examples 2, 5 and 8 according to the present invention have X-Y
When drawing with a water-based ink pen (black, red, yellow, blue) using Plotter PL2000 (made by Yokogawa Denki Seisakusho), the drawing lines of the water-based ink of each color and the drying property of the ink are good, and excellent drawing properties are shown. It was most suitable as a film for overhead projector.

Claims (7)

[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.
A partially or completely saponified copolymer resin of 80 to 0% by weight of another polymerizable monomer, or 0 to 90% by weight of a derivative thereof,
And / or (C) a homopolymerized resin of N-vinylpyrrolidone or a copolymerized resin with another polymerizable monomer in an amount of 0 to 90% by weight, and (A) / [(B) + (C)]. Is 90/10 to 10 /
A resin composition whose main component is a mixture having a weight ratio of 90 was applied to the surface of a support sheet, and then the active energy ray was irradiated to cure the resin composition to form a resin coating layer on the support. Water-based ink recording sheet. 2. A cationic synthetic resin having a photopolymerizable double bond as the component (A) is a polymerizable resin having a polymerizable double bond and a functional group of a quaternary ammonium salt. The water-based ink recording sheet according to claim 1. 3. A cationic synthetic resin (A) having a photopolymerizable double bond, wherein the lone electron pair of nitrogen is not conjugated.
Polymerization of 10-100% by weight of a polymerizable monomer having a primary nitrogen atom and 90-0% by weight of another polymerizable monomer having a Lewis acid and an epoxy group capable of further donating a proton to a resin. A resin obtained by reacting a monomer with 0.1 to 1.0 g equivalent of a polymerizable monomer containing a tertiary nitrogen atom of the polymer resin to quaternize the tertiary nitrogen atom of the polymer resin. The water-based ink recording sheet according to claim 2, wherein 4. A cationic synthetic resin having (A) a photopolymerizable double bond, wherein the lone electron pair of nitrogen is not conjugated.
A polymerizable monomer having a covalently bonded halogen atom is further added to a polymer resin containing 10 to 100% by weight of a polymerizable monomer having a primary nitrogen atom and 90 to 0% by weight of another polymerizable monomer, Patents characterized by being a resin in which the tertiary nitrogen atom of the polymer resin is quaternized by reacting with 0.1 to 1.0 g equivalent of a polymerizable monomer containing a tertiary nitrogen atom of the polymer resin. Claim 2
Item 2. A water-based ink recording sheet according to item. 5. A cationic synthetic resin having (A) a photopolymerizable double bond, 10 to 100% by weight of a polymerizable monomer having a covalently bonded halogen atom, and 90 to 0 of another polymerizable monomer. weight%
And a polymerizable resin having a tertiary nitrogen atom to which a lone electron pair of nitrogen is not conjugated, is added to the polymer resin with 0.1 to 1.0 of the covalently bonded halogen atom-containing polymerizable monomer of the polymer resin.
The aqueous ink recording sheet according to claim 2, which is a resin having a quaternary ammonium salt group introduced therein by reacting with a g equivalent. 6. The aqueous ink recording sheet according to claim 1, wherein the aqueous ink recording sheet is an ink / jet recording sheet. 7. The water-based ink recording sheet according to claim 1, wherein the water-based ink recording sheet is an XY plotter recording sheet.