JPS63160875A - Sheet for aqueous ink recording - Google Patents

Abstract

PURPOSE:To achieve clear printing excellent in water resistance of a recorded matter and free of bleeding, by coating the face side of a base with a composition comprising as a main constituent a mixture of a cationic synthetic resin, a cellulose derivative and the like, followed by drying. CONSTITUTION:A sheet for aqueous ink recording is produced by coating the face side of a base sheet with a composition comprising as a main constituent a mixture of (A) a cationic synthetic resin, (B) a cellulose derivative, (C) a partially or completely saponified polyvinyl alcohol, a partially or completely saponified product of a copolymer resin of 20-100 wt.% of vinyl acetate with 80-0 wt.% of other polymeric monomer or a derivative thereof, and/or (D) a homopolymer or copolymer resin of N-vinyl pyrrolidone, followed by drying. The mixing ratio of the mixture is (A) 10-90 wt.%, (B) 1-30 wt.%, (C) 0-89 wt.% and (D) 0-89 wt.%, with the weight ratio of (A)/(B)/[(C)+(D)] being 90-10/1-30/9-89.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to recording sheets using water-based inks, and particularly to paper, plastic films, synthetic papers, metal sheets, etc. that can produce high-quality color images using an inkjet recording method. This invention relates to an inkjet recording sheet used as a base material.

The inkjet recording method is noiseless, does not require a fixing process, 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. It is being done. 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 field of color graphics, which use seven expressive colors (CR, magenta, cyan, red, green, purple, and black), and have recently become full-color printers that achieve high image quality similar to gravure printing or silver halide photography. Copy, place. High resolution color printers have been developed that produce Victorian copies.

[Prior art]

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

The basic properties required of an inkjet recording sheet are: 1. The dot shape should 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 sharpness and good clarity.

3. It has a fast ink absorption speed, excellent drying properties, and has a large amount of ink absorption, so when ink dots overlap, it has good multi-color recording performance, such as preventing the dots that adhere later from flowing out. 4. Inkjet The recorded material has good water resistance,
9. Ink recorded when wet with water should not bleed or run out.

5. Small dimensional change after recording, no curling, waving, or deformation.

Examples include.

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

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, unabsorbed ink will flow out), resulting in not only not being able to obtain a clear image, but also causing 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 tension according to the recording method, its conditions, and ink. The reality is that various physical properties of paper such as hardness, smoothness, and elongation in water are adjusted. On the other hand, in order to obtain high-fidelity color recording, which is a recent trend, it is not possible to control these paper properties alone. A coated paper-type inkjet recording paper with a coated layer and optimized binder, binder, etc. is being considered. However, the high 1dii3 is still satisfactory in terms of not only the recording performance but also the water resistance, weather resistance, and dimensional stability of the recording section! The reality is that there is no inkjet recording paper for this purpose. As a trend toward appropriate quantities, there is a demand for using not only paper but also water-resistant sheets and transparent sheets such as impregnated paper, plastic film, synthetic paper, and metal sheets as base sheets. For example, specifically, as the use of color displays in personal computers progresses, transparent films capable of inkjet recording are being manufactured for use in color hardcopy for OHP (overhead projectors). However, unlike paper base materials, plastic films such as polyester used in OHP films are hydrophobic and have no ability to absorb water-based inks, so they cannot be used. Other processed products such as impregnated paper,
The same applies to synthetic paper, metal sheets, etc.

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

Furthermore, when used as an inkjet ink solvent, water alone usually causes clogging of the ejection nozzle due to evaporation, and water is mixed with polyalkylene glycol or a humectant to prevent clogging due to drying. We are making various efforts. 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 mentioned above, the most important problem in this field is how to make the ink droplets produced by inkjet clearly adhere to recording sheets, especially transparent synthetic resin films such as polyester, and quickly absorb and dry them. .

[Problem that the invention seeks to solve]

The present invention has the advantage of inkjet technology that it is possible to record multicolor full-color copies clearly and neatly, and it also has excellent ink absorption and drying properties, and the water resistance of inkjet recording is good, so it can record even when it gets wet with water. To provide a water-based ink recording sheet that does not cause ink to smudge or run out.

[Means to solve problems]

The present invention relates to cationic synthetic resins, cellulose derivatives, partially or fully saponified polyvinyl alcohol, partially or completely saponified copolymer resins of vinyl acetate and other polymerizable monomers, or derivatives thereof, and/or N
- A composition based on a monopolymer resin of vinylpyrrolidone or a mixture consisting of a copolymer resin with other polymerizable monomers is applied to the surface of a support sheet and dried to form a resin on the support. By providing a film layer, the absorbency of water-based ink is improved, and water-based ink recorded matter is provided with excellent water resistance and clear printing without bleeding.

The present inventors have previously developed cationic synthetic resins, partially or fully saponified polyvinyl alcohol, or partially or fully saponified copolymer resins of vinyl acetate and other polymerizable monomers,
or derivatives thereof, and/or a resin composition based on a mixture consisting of a homopolymer resin of N-vinylpyrrolidone, or a copolymer resin with other polymerizable monomers, is applied to the surface of the support sheet. Invention of a water-based ink recording sheet in which a resin coating layer is provided on a support by drying (Japanese Patent Application No. 6L-1
673) by Kawahara. This d-recording sheet has excellent ink drying properties, sharpness of recording, and water resistance of recording.
In recent years, as the development of hard disks has become extremely fast, there has been a demand for improved ink drying properties and shorter r/h.

In order to meet these demands, the present inventors have conducted extensive research and have arrived at the present invention. The recording sheet of the present invention has very good absorption and drying properties of ink droplets, does not cause the ink droplets to flutter, and does not penetrate deeply into the interior of the inkjet recording sheet. Excellent recordability. Furthermore, since the cationic synthetic resin in the resin composition penetrates the aqueous ink, the water resistance of the recording itself is also good, and no deformation of the recording sheet itself is observed after recording. Furthermore, since the cationic synthetic resin is a topolyte polymer, it has good antistatic properties and does not attract dust.

[Structure of the invention]

The present invention comprises (4) a cationic synthetic resin, and (B) a cellulose rust conductor, and 20 to 100% by weight of partially or completely saponified polyvinyl alcohol or vinyl acetate and 8O-Offit% of other polymerizable monomers. The main ingredient is a partially or fully saponified copolymer resin of or a derivative thereof, and/or a monopolymer resin of ON-vinylpyrrolidone, or a mixture consisting of a copolymer resin with other polymerizable monomers. The present invention provides an aqueous ink recording sheet in which the composition is coated on the surface of a support sheet and then dried to provide a resin film layer on the support.

(Cationic Synthetic Resin) The cationic synthetic resin of the present invention is a synthetic bone fat having a quaternary ammonium salt functional group, and includes, for example, the following (i) and (10).

(1) Polymer resin containing 10 to 100% by weight of a polymerizable monomer having a tertiary nitrogen atom with no nitrogen lone pair conjugated and 90 to 0% by weight of other polymerizable monomers Then, alkyl halides, haloacetic esters, Lewis acids, etc. are added to 0.1 to 1 of the tertiary nitrogen atom-containing polymerizable monomer of the polymer resin.
．． 0 f A resin in which the tertiary nitrogen atom of the polymer resin is quaternized by reacting with an electric current, or a polymerizable monomer having a tertiary nitrogen atom whose nitrogen lone pair is not conjugated. A resin obtained by quaternizing the polymer with an alkyl halide, haloacetyl ester, Lewis acid, etc., and then polymerizing it with other polymerizable monomers.

Examples of the polymerizable monomer having a tertiary nitrogen atom with which the nitrogen lone pair is not conjugated include 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-dimethylamino Butyl (meth)acrylate, etc., or N,
N-dimethylaminoethyl (meth)acrylamide, N
, N-diethylaminepropyl (meth)acrylamide, etc. [R1 in the above formulas (1) and (2) is a hydrogen atom or a methyl group, R and R are each an alkyl group having 1 to 4 carbon atoms, nF
Indicates the number of il~4. ] (Meth)acrylic monomers represented by; dimethylaminomethylstyrene, diethylaminomethylstyrene,
General formulas such as dimethylaminomethylstyrene [wherein R1 and R2 each represent an alkyl group having 1 to 4 carbon atoms]; ] Styrenic monomers represented by general formulas such as vinylpyridine, methylvinylpyridine, etervinylpyridine [wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]. ] There is one kind or a mixture of two or more kinds of pyridine monomers represented by the following.

Other polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (
meth)acrylate, octyl(meth)acrylate,
Alkyl (meth)acrylates such as lacryl (meth)acrylate and stearyl (meth)acrylate, benzyl (meth)acrylate, ethoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate,
Hydroxypropyl (meth)acrylate, styrene,
Examples include vinyltoluene and vinyl acetate.

Examples of alkyl halides include methyl chloride, ethyl chloride, butyl chloride, benzyl chloride, 3-chloro-2
-Hydroxypropyltrimethylammonium chloride and the like can be used, and as the haloacetic acid ester, methyl monochloroacetate, ethyl monochloroacetate, etc. can be used. Examples of Lewis acids 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 4IN acid and acetic acid.

(11) Polymerizable monomer 1 having a covalently bonded halogen atom
O-Zoo heavy stitch 9 and other polymerizable monomers 90 to 0 weight! d
% of the tertiary amine to a polymer resin, and 0.1 to 1. O
A resin into which a quaternary ammonium base is introduced by reacting with f equivalent.

Examples of polymerizable monomers containing covalent halogen atoms include allyl halides such as allyl chloride, allyl bromide, and allyl iodide;
Vinylbenzyl halides such as chloromethylstyrene, bromomethylstyrene, iodomethylstyrene, 3-halo-2-hydroxyp such as 3-chloro-2- and do-tetraxyglobyl (meth)acrylate, vinyl (meth)acrylate, chloromethyl ( General formula % formula % (5) of meth)acrylate, ricIc1 ethyl (meth)acrylate, prosobutyl (meth)acrylate, etc. [In the formula, R is a hydrogen atom or a methyl group, X is chlorine, bromine, iodine, and n is Indicates a number from 1 to 4. ] and the like are ω-haloalkyl (meth)acrylates.

In addition, as other polymerizable monomers, the same ones as in (1) can be used, and as tertiary amines, trimethylamine,
Examples include triethylamine and triethanolamine.

In these resins (1) and (10), the lone electron pair of nitrogen for obtaining the polymer resin of the precursor is not conjugated.
The nitrogen atom-containing polymerizable monomer or the covalently bonded halogen atom-containing polymerizable monomer has a weight of 10 to 100, preferably 2
0 to 90% by weight, and the amount of other polymerizable monomers is 90 to 0% by weight, preferably I! Used at a rate of 10-2 Gm [[ff1-deaf.

In addition, the lone pair of nitrogen electrons is not conjugated to the 3rd aq
Alkyl halide, The acetic acid ester, Lewis acetate, or tertiary amine is used in an amount of 0.1 to 1.0 equivalent, preferably 0.2 to 1.0 equivalent.

The lone pair of nitrogen electrons in the precursor resin is unconjugated.
If the amount of the polymerizable monomer containing a nitrogen atom or a covalently bonded halogen atom 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.On the other hand, if the proportion of other polymerizable monomers is less than the above ratio, the water-based ink will bleed, making it impossible to obtain clear prints. can't get it. On the other hand, if it is too large, the coating film becomes hydrophobic and the absorption and drying properties of water-based ink deteriorate.

Next, a method for producing the cationic synthetic resin as component (2) of the present invention will be explained. Predetermined monomers that are components of the cationic resin of the present invention and optionally other monomers that can be copolymerized with these monomers are prepared by a common solution polymerization method in a hydrophilic or water-miscible solvent. A monomer is dissolved in a solvent, a polymerization initiator is added, 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 of the present invention. Alternatively, after first modifying a predetermined monomer that is a component of a cationic resin with a predetermined modifier,
The cationic polymer of the present invention can also be obtained by polymerizing with other monomers copolymerizable with these. 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, impropanol, n-butanol, secondary butanol, diacetone alcohol, methyl cellosolve, methyl cellosolve, and methyl cellosolve. , alcohols such as butylcarpitol, ethers such as dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, and esters such as cellosolve acetate. This hydrophilic solvent may be contained in the final resin solution or may be completely removed from the system by water displacement afterwards.

As a polymerization initiator, for example, benzoyl peroxide,
Acetyl peroxide, Lauro (A, peroxide, decanoyl peroxide, tertiary butyl.

Organic peroxides such as ruberoxide, azobisisobutyminitrile, 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°, preferably 5. QOQ~100.000.

To modify the unmodified polymer thus obtained, it is sufficient to simply mix and stir the unmodified polymer and a modifier, and the presence of the hydrophilic or water-miscible solvent and/or water is sufficient. You can also do it below.

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.
The reaction time can generally be 1 to 1G hours, but in order to increase the denaturation rate, it is preferable to take a reaction time of 3 hours or more.

(Cellulose derivative) The cellulose derivative of component [F]) of the present invention will be described. Examples of cellulose derivatives used in the present invention include t
*Lulose powder, lower alkyl celluloses such as methyl cellulose and ethyl cellulose, hydroxy lower alkyl celluloses such as benzyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, ethyl hydroxypropyl cellulose, methyl cellulose, ethyl natono Examples include alkyl ethers, benzyl ethers, carboxymethyl cellulose, Wi acid of cellulose, sulfuric acid, acetic acid, propionic acid, butyric acid and other higher fatty acid esters, among which lower alkyl celluloses such as methyl cellulose and ethyl cellulose, hydroxyethyl cellulose, hydroxy Hydroxy lower alkyl celluloses such as propyl cellulose are particularly preferred from the viewpoints of ink drying properties, sharpness of recording, uniformity of coating films, transparency of coating films, and ease of preparing coating liquids.

(Polyvinyl alcohol and/or polyvinylpyrrolidone) Partially or completely saponified polyvinyl alcohol of component C) of the present invention, or vinyl acetate 20 to 100% by weight and other polymerizable monomers such as ethylene 80 to 1% by weight The partially or completely saponified copolymer resin will be described below. The degree of saponification of the partially or fully saponified polyvinyl alcohol used in the present invention, or the partially or completely saponified copolymer resin of vinyl acetate and other polymerizable monomers is preferably 60 mol% or more, particularly 70% by mole or more. More preferably mol% or more. If the degree of saponification is less than 60 mol%, ink drying properties are insufficient and compatibility with cationic synthetic resins is poor, causing whitening when formed into a coating. The molecular film of partially or completely saponified polyvinyl alcohol, or a partially or fully saponified copolymer resin of vinyl acetate and other polymerizable monomers is preferably 5,000 to 150,000, particularly 10,000 to 100,000. More preferred. Various commercially available polyvinyl alcohols are available.

In particular, the homopolymer resin of N-vinylpyrrolidone or the copolymer resin with other polymerizable monomers, which is component 0) of the present invention, will be described. As the homopolymer resin of N-vinylpyrrolidone or the copolymer resin with other polymerizable monomers used in the present invention, a homopolymer of vinylvinylpyrrolidone, a copolymer of vinylvicrytone and vinyl acetate, etc. Polymers are preferable, and the molecular membrane is preferably 5,000 to 10,000 to 80,000, especially 10,000 to 80,000.
10,000 is more preferable. These polyvinylpyrrolidone resins can be used in various types such as paper and plate.

) cationic synthetic resin, (11 cellulose derivative,
and partially or fully saponified copolymer resins of polyvinyl alcohol 1 or vinyl acetate with other polymerizable monomers, and/or homopolymer resins of ON-vinylpyrrolidone, or other polymerizable monomers. The blending ratio of the monomer and the copolymer resin is 1% to 90% by weight for ■, and 1 to 1% for (6).
30 weight, 0 is 0 to 89 weight 4%, ■ is 0 to 89 weight i%
and (A/e)/(10+0)) is 90~
lO/l~30/9~89 weight ratio, more preferably 80
A weight ratio of ~20/1 to 20/19 to 79 is desirable; if the component (1) is less than 11% per weight, dramatic ink drying properties cannot be expected; conversely, if it exceeds 30% by weight, the coating The viscosity of the solution becomes so high that it becomes difficult to handle it, and it is difficult to obtain a uniform coating, resulting in whitening of the coating.

Also, if the sum of the 0 component and the 0 component is less than 9 times @deaf, it will be difficult to obtain a record with improved ink drying properties and clarity, and the reverse K
If the sum of component (') and component 0 exceeds 89% by weight or 9%, 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 provides (4) a cationic synthetic resin and a Q
3) Cellulose derivatives and partially or fully saponified polyvinyl alcohol, or partially or fully saponified copolymer resins of vinyl acetate and other polymerizable monomers, and/or ΩN
- By using a homopolymer resin of vinylpyrrolidone or a copolymer resin with other polymerizable monomers, a better record can be obtained, and when only the solid component is used, the ink drying property is lower. However, there are some color bleeding and clumps.

If only component (b) is used, the coating film becomes white during coating, and the ink permeates into the coating film during coating, making it impossible to obtain clear and good recordings. In addition, if 0 component and/or 0 component only is used, the paint film may show cracks during coating, whitening of the paint film, lack of water resistance, ink smearing, and lumps may occur during printing. Records cannot be obtained.

(Optional ingredients) In addition to the above-mentioned fat composition, in order to improve the condition of the coating film, etc.
Nonionic surfactants such as higher alcohol ethoxylates, cationic surfactants, amphoteric surfactants, silicone i'H@, wetting agents, other electrolyte polymers, additives (e.g. fillers such as clay and carbonaceous) There is no problem in adding colloidal sols such as silica sol, alumina sol, etc.

(Recording sheet) The coating of the layer-forming resin composition is carried out on a base material such as polyethylene terephthalate film by air knife coating, plaid coating, barcode coating, gravure coating, curtain coating, roll coating, spray coating, etc. After drying the solvent, a recording layer is formed on the base sheet. Is the coating surface of the recording layer 1-2 ot/w? , preferably 2~
102/m" range.The base sheet is a plastic film, synthetic paper, size, air permeability, smoothness, etc., and a barrier coating layer is coated with resin or extruded with thermoplastic resin. Paper products coated with paper, resin-impregnated paper, metal sheets, etc. are conveniently used.

In order to increase the adhesion of the recording layer to these base sheets, an anchor coat is sometimes applied to the base material.

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-Y7' rotters using water-based ink felt pens. The reality is that when creating 0HP (overhead projector) sheets using a special KX-Y plotter, the color water-based pens currently used for drawing on plain paper are replaced with oil-based pens. However, if the recording sheet of the present invention is used, it is possible to make a drawing with a conventionally used water-based pen, thereby eliminating the complicated work of setting up a pen at once.

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 numbers in the examples are based on weight.

(A) Manufacturing side resin of cationic synthetic resin! In a flask, 80 parts (C) of N,N-dimethylaminoethyl methacrylate, 51 f equivalent), methyl methacrylate were added.
), 10 parts of cyclohexyl methacrylate), ioo parts of Impropatool and 0.5 parts of 2*2'-azobisinbutyronitrile were added, and the mixture was heated to 80 parts under a nitrogen atmosphere.
The polymerization reaction was carried out at ℃ for 6 hours.

Then cooled with water, 16.3 parts of methyl monochloroacetate (C),
15? (equivalent) and 126 parts of water were poured into the mixture, and after the dropwise addition, the mixture was stirred for 1 hour in a room-temperature cap, and further heated to 70°C and stirred for 6 hours to obtain resin 1. This methacrylic resin has a molecular weight of about 30,000 and contains the following unit Hs 1 Hs in its molecular chain.

Resin ■ As in the case of resin ■, N,N-dimethylaminoethyl methacrylate (50 parts (C), 32 equivalents) and droxyethyl methacrylate (10 g (C), 08 f equivalent)
, 40 parts of butyl methacrylate, 100 parts of ethanol and 0.5 part of 2,2'-azobisisobutyronitrile, and then 20.6 parts of ethyl chloride (C), 32 g equivalent), water Modification was carried out with 134 parts to obtain resin (■). Is this methacrylic resin the next unit? H3 fortune telling.

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

Resin ■ Tree + fft As in the case of I, 80% aqueous solution of methyl chloride modified product of N,N-dimethylaminoethyl methacrylate (Mitsubishi rayon product) 75 parts, methyl methacrylate L/-) 20 parts, butyl methacrylate 20 parts of ethanol, 100 parts of ethanol, and 0.5 part of 2,2'-azobisinbutyronitrile, and then 11 parts of water.
0 parts was added to obtain resin (2) having a molecular weight of approximately 25,000.

Resin ■ As in the case of resin I, 60 parts of 4-vinylpyridine (C
), 57f equivalent), human mixyethyl methacrylate L/ −
), 30 parts of butyl methacrylate, 100 parts of ethanol, and 0.5 parts of 2,2'-azobisisobutyronitrile, and then at 70°C for 3
-chloro-2-hydroxypropyltrimethylammonium chloride toyg (o, s7), and water 23
Resin W was obtained by carrying out a modification reaction using 5 parts for 6 hours. This resin has a molecular weight of about 26,000 and contains the following unit H in its molecular chain.

Resin V As in the case of Resin I, 50 parts of 3-chloro-2-hydroxypropyl methacrylate (C), 28 equivalents), 30 parts of methyl methacryle), 20 parts of cyclohexyl methacrylate), isopropanol 100 parts and 2.2'-
A polymerization reaction was carried out using 0.5 parts of azobisin butyronitrile, and then a modification reaction was carried out at 70°C for 6 hours using 25 parts (C) of N,N-dimethylaminoethanol per 28 f and 160 parts of water. Resin V was obtained. This methacrylic resin has a molecular weight of about 24,000 and contains the following unit Hs in its molecular chain.

Comparative Resin I As in the case of Resin I, 5 parts of N,N-dimethylaminoethyl methacrylate (C), 03F@Year), 95 parts of methyl methacrylate, 100 parts of Improper Tool, and 2.
A polymerization reaction was carried out using 0.5 part of 2'-azobisisobutyronitrile, followed by 3.9 parts (C) of monochloroethyl acetate (03f equivalent), 40 parts of water, and 5 parts of imbupanol.
A comparative resin (■) having a molecular weight of about 35,000 was obtained by modifying with 4 parts.

Comparative resin "Similar to the case of resin 1, 125 parts of an 80% aqueous solution of methyl chloride modified N,N-dimethylaminoethyl methacrylate (Mitsubishi Rayon ■ product), 100 parts of ethanol, 21
A polymerization reaction was carried out using O and S parts of 2'-azobisinbutyronitrile, 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 explained.

Examples 1-14, Comparative Examples 1-14, Reference Examples 1-2 and IK
10 parts by weight of the composition described in water/ingropanol (l/
1 weight ratio) 10% diluted solution dissolved in 90 parts by weight of solvent,
Anchor treatment agent (Anchor treatment agent Underlacquer RU manufactured by Toyo Ink Co., Ltd.)

Polyester film (10
0 micron thickness) or unanchored polyester film (100 micron thickness) or coat with a percoater and solids coating amount is 4 f/m
' was applied.

Then, it was dried to obtain a transparent recording film.

To the recording sheets obtained in the above Examples and Comparative Examples, commercially available U'4 series inkjet recording paper (Reference Example 1) and the coated paper used in Example 14 (Reference Example 2) were added to improve the inkjet recording properties. was evaluated using the following method.

(1) Measurement of dot density and dot diameter: Sakura densitometer PDM-5 (manufactured by Konishiroku Photo Industry Co., Ltd.) was used.

(2) Observation of the diameter of the dots: The shape of the dots displayed under the actual microscope and the edge portions were evaluated by ○ (circular and sharp) x (irregular and with large smearing).

(3) Ink drying property: A test pattern was recorded using a Sharp Color Image Prots fi-10-0700, and 1 minute later, the ink was transferred onto a paper to evaluate the drying property based on the presence or absence of transfer. The evaluation was done on a five-point scale: 5 (no transfer at all), 4 (one copy), 3 (transfer), 2 (not much transfer), and 1 (severe transfer).

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

(5) Water resistance of recording ink: The recording film was immersed in water, and after 30 seconds, it was removed and the flow of the recording ink was observed and evaluated. ○: No change at all, Δ: Slight change, ×: Everything has flowed away.

The results are shown in Table-1.

A color image printer (Sharp Corporation!
Comparative Example 1-
Compared to No. 14, the water-based ink has excellent drying properties, the printed area shows good adhesion and does not fall off even when rubbed, and the printed image has high color density, clarity, and high resolution, making it suitable for color overhead projectors. It is ideal as a film for use. 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 14 had different colors and
High ae: One-plane image with high resolution was obtained, and the image quality was superior to that of general coated paper (Reference Example 2) and high-quality inkjet recording paper (Reference Example 1) used as base materials. It had color image quality.

X-Y7 on the recording sheet of Example 2.5.8 according to the present invention
'When I drew with water-based ink pens (black, red, yellow, blue) using Rotter PL2000 (manufactured by Fuzutsu Denki Seisakusho),
The drawing lines of each color of aqueous ink and the drying properties of the ink were good, and the film showed excellent drawing performance and was suitable as a film for an overhead projector.

(Left below) tl) Cellulose derivative: MC (methyl cellulose,
“Marboros 1 Matsumoto oil ■ trade name), EC (ethyl cellulose, Percules ■ product), HEC (hydroxyethyl cellulose, Percules ■ product), polyvinyl alcohol: All products from Nippon Gosei Chemical Industry - KPO8 (saponification degree 71-75 mol%) ), GM14 (86
-89 mol%), NH2O (98-100 mol%), K
LO5 (78-82 mol%), polyvinylpyrrolidone: All three-oiled verdatesier■
Product - 30 for Rubiscoll (40,000 molecules), K2O (630,000)
, K2O (41,60,000),

Claims (1)

[Scope of Claims] 1) (A) 10 to 90% by weight of a cationic synthetic resin, (B) 1 to 30% by weight of a cellulose derivative, and (C)
0-89% by weight of a partially or completely saponified copolymer resin of 20-100% by weight of partially or completely saponified polyvinyl alcohol or vinyl acetate and 80-0% by weight of other polymerizable monomers, and/or (D ) N-vinylpyrrolidone homopolymer resin or copolymer resin with other polymerizable monomers 0 to 89% by weight (however, the sum of components (C) and (D) is 9 to 89% by weight)
1. A water-based ink recording sheet, characterized in that a composition containing a mixture of the following as a main ingredient is applied onto the surface of a support sheet and dried to form a resin coating layer on the support. 2) The aqueous ink recording sheet according to claim 1, wherein the cellulose derivative in (B) is lower alkyl cellulose. 3) The aqueous ink recording sheet according to claim 1, wherein the cellulose derivative in (B) is particularly lower hydroxyalkyl cellulose. 4) The aqueous ink recording sheet according to claim 1, wherein the aqueous ink recording sheet is an ink jet recording sheet. 5) The aqueous ink recording sheet according to claim 1, wherein the aqueous ink recording sheet is an X-Y plotter recording sheet.