KR20150106882A - Transparent resin layer composition, receiving layer for inkjet inks which is produced using same, and display element - Google Patents

Abstract

Provided is a transparent resin layer composition for forming a receptive layer capable of sufficiently accommodating a jetted ink jet, and stabilizing the shape after drying, while controlling the droplet spreading diameter. A receptive layer for an ink-jet ink and a display element formed using the same are provided.
(1) A copolymer obtained by polymerizing a mixed monomer containing methyl methacrylate (i) and a (meth) acrylic acid alkyl ester (ii) having 2 to 8 carbon atoms in an alkyl group, by emulsion polymerization, (Meth) acrylic acid alkylester copolymer resin fine particle dispersion emulsion having a weight average molecular weight of 100,000 or more and less than 800,000 and a number average particle diameter of 10 nm or more and less than 500 nm; (3) a transparent resin layer composition containing an organic solvent, wherein the transparent resin layer is a inkjet ink receiving layer formed on a support substrate, or a transparent resin layer formed by using the transparent resin layer, And drawing the ink-jet ink on the ink-jet recording medium.

Description

TECHNICAL FIELD [0001] The present invention relates to a transparency resin layer composition, a receptive layer for an ink-jet ink using the same, and a display element,

The present invention relates to a transparent resin layer composition, a receptive layer for an inkjet ink using the same, and a display device, and more particularly to a transparent resin layer composition for forming an ink receptive layer at the time of drawing using inkjet ink, Device.

In recent years, in the ink-jet printing related industry, which has remarkable growth, the performance of the ink-jet printer has improved dramatically and the improvement of the ink has progressed remarkably, and it is now possible to obtain a high-definition and clear image such as silver- For this reason, the inkjet printer is not limited to use in the home, but is also being studied for use in the manufacture of large advertising signboards, electronic devices such as color filters for liquid crystal displays and printing of alignment films.

In addition, high image quality of the inkjet printed material is high due to improvement of the printing ink as well as high performance of the printer. More specifically, the use of pigment inks, which are known to be capable of forming printed images having high color reproducibility comparable to dye inks and having excellent durability as compared with conventional dye inks, have become mainstream in the field of printed matter in recent years. On the other hand, as a pigment ink for use in an electronic device, a solvent-based pigment ink in which particles of pigment ink are dispersed in an organic solvent is desirably used from the reliability requirement of a device, which is also referred to as a pigmented pigment ink. Such inks have attracted attention recently because they can be preferably used for forming printed images having a water resistance level that does not cause blurring of printed images due to moisture in the environment or the like on a printed substrate since the particles themselves of the ink are relatively hydrophobic.

However, most of the conventional inkjet recording media have an ink receiving layer developed for aqueous dye inks and are designed for the purpose of improving the water absorption of the aqueous medium in the ink and improving the fixability of the dye (see, for example, Patent See Document 1). Therefore, even if the ink-jet recording medium is printed using the solvent-based pigment ink, the ink receiving layer can not efficiently absorb the organic solvent, and as a result, a sharp image is obtained that prevents blur and discoloration none.

For example, in Patent Document 2, there has been proposed a method in which 50 to 100% by weight of methyl methacrylate and 50 to 100% by weight of a (meth) acrylic or vinyl (meth) acrylate other than methyl methacrylate Based monomer having a weight average molecular weight of 300,000 or more and 1,000,000 or less, and 0 to 50% by weight of a monomer as a main component.

However, in the ink receiving layer as described in Patent Document 2, for example, when inkjet printing is performed on a relatively large medium such as an outdoor advertisement, the organic solvent contained in the ink can not be sufficiently absorbed, There is a case where significant degradation of the property, blurring of the printed image, crack, and the like occur. Further, since the ink receiving layer described in Patent Document 2 is formed using an inkjet repairing agent in which the specific acrylic resin is dissolved in an organic solvent, a step of volatilizing a large amount of the organic solvent is required when the inkjet recording medium is manufactured . ≪ / RTI >

On the other hand, Patent Document 3 discloses an ink jet receiving layer for an oil-based pigment ink in which a vinyl polymer having a glass transition temperature of 10 to 70 DEG C and a weight average molecular weight of 800,000 or more is dispersed in an aqueous medium. However, when the oil-based ink-jet ink is dropped on the coating film obtained after drying the ink-jet repairing agent, there is a problem that the absorption rate is slow and the droplet diameter is expanded when the molecular weight is 800,000 or more. This is also the case when the glass transition temperature of the vinyl polymer is 70 DEG C or higher, and it is difficult to control the droplet spreading.

Japanese Patent Application Laid-Open No. 11-216945 Japanese Patent Application Laid-Open No. 2004-291561 Japanese Patent No. 4442718

The present invention relates to a water-soluble ink-jet ink, such as a solvent-based pigment ink, which is capable of sufficiently accommodating a jetted ink jet and capable of stabilizing the shape after drying while controlling the spreading diameter thereof And a transparent resin layer composition for forming a receptive layer. Another object of the present invention is to provide a display element obtained by drawing an ink-jet ink on a transparent resin layer formed of a transparent ink-receiving layer for an ink-jet ink and a transparent resin layer formed using the transparent resin layer composition.

As means for solving these problems, the present inventors have found that the glass transition temperature and the molecular weight of the resin constituting the emulsion particle in the transparent resin layer composition are important in suppressing the spreading diameter of the ink droplet and securing the stability of the shape after drying Further, it has been found that the problem of the prior art can be solved by coexistence of a predetermined surfactant and an organic solvent besides the particle size of the emulsion particle in the transparent resin layer composition, and the present invention has been accomplished.

That is, the present invention relates to (1) a polymer obtained by polymerizing a mixed monomer containing methyl methacrylate (i) and (meth) acrylic acid alkyl ester (ii) having 2 to 8 carbon atoms in the alkyl group, (Meth) acrylic acid alkyl ester copolymer resin fine particle dispersion emulsion having a glass transition temperature of 10 ° C or more and less than 70 ° C, a weight average molecular weight of 100,000 or more and less than 800,000, and a number average particle diameter of 10 nm or more and less than 500 nm , (2) a surfactant having fluidity at room temperature of 23 ° C, and (3) an organic solvent.

Further, the present invention is an ink-jet ink-receiving layer formed by forming a transparent resin layer formed using the above-mentioned transparent resin layer composition on a supporting substrate. Further, the present invention is a display element obtained by drawing an ink-jet ink on a transparent resin layer formed using the transparent resin layer composition.

In order to obtain the (meth) acrylic acid alkylester copolymer resin fine particle dispersion emulsion according to the present invention, it is preferable that (i) methyl methacrylate is used as an essential component and the glass transition temperature is in the range of 10 ° C or more and less than 70 ° C (Meth) acrylic acid alkyl ester having 2 to 8 carbon atoms, and at least a mixed monomer containing (i) and (ii) is polymerized by emulsion polymerization. The resin contained in the resulting (meth) acrylic acid alkylester copolymer resin fine particle dispersion emulsion has a weight average molecular weight of 100,000 or more and less than 800,000, and a number average particle diameter of 10 or more and less than 500 nm.

Since the number of alkyl groups of the alkyl (meth) acrylate of (ii) may manifest tackiness of the coating film comprising the composition of the present invention, or the stability of the pixel shape formed on the coating film by inkjet ink may decrease, 2 to 8. In the case of 1 carbon atom, the meaning of the mixed monomer is lost in the methyl methacrylate of (i). On the other hand, when the number of carbon atoms is 8 or more, the transparency resin layer tends to be remarkably tacky, or a pixel crack may occur in drying performed after ink printing, resulting in deteriorated pixel shape.

(Meth) acrylic acid alkyl ester having 2 to 8 carbon atoms in the alkyl group of the above (ii) is one kind of monomers (monomers) constituting the (meth) acrylic acid alkyl ester copolymer, examples of which include (meth) Butyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec- 2-hydroxyethyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Further, the (meth) acrylic acid alkyl ester means an acrylic acid alkyl ester or a methacrylic acid alkyl ester.

The glass transition temperature of the resin in the (meth) acrylic acid alkyl ester copolymer microparticle dispersion emulsion is in the range of 10 ° C or more and less than 70 ° C. In the case of less than 10 캜, the pixels formed by the factors at the time of absorbing and drying the solvent in the ink are caused by the outflow of the resin and are connected to the adjacent pixels, so that the color inks are mixed with each other, There is a risk of cracking on the pixel. In addition, there is a tendency that the conveyability of the coated substrate is lowered due to the manifestation of the tackiness of the coated film. On the other hand, at 70 deg. C or higher, since the absorption of the solvent in the ink is poor, the solvent spreads wet and spreads, and a uniform pixel shape can not be obtained in a desired size. Further, since the penetration of the solvent into the coating film becomes uneven, There is a possibility that the flatness of the surrounding coating film remarkably lowers and consequently the transparency deteriorates.

The composition ratio of the (meth) acrylic acid methyl ester and (ii) the (meth) acrylic acid alkyl ester having 2 to 8 carbon atoms in the (meth) acrylic acid alkyl ester copolymer resin falling within the glass transition temperature range described in the preceding paragraph is, (i): (ii) = 1: 0.25 to 1: 2. Particularly, in the region where the weight ratio of methyl methacrylate of (i) is smaller than this range, there is a possibility that the above-described mixture of printed matter and cracks in printed pixels occur. In a region larger than this range, deterioration of the pixel shape, It is preferable to fall within the above range because there is a fear of deterioration.

In the copolymer resin, a monomer having a crosslinking group can be introduced within the range that does not affect the strength of the transparent resin layer and the above-described physical properties for the purpose of preventing pixel cracking of the ink-jet ink. Examples thereof include glycidyl group-containing polymerizable monomers such as glycidyl (meth) acrylate and allyl glycidyl ether, aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, -Dialkylaminoalkyl, amino group-containing polymerizable monomers such as vinyltrichlorosilane, vinyltrimethoxysilane, N -? - (N-vinylbenzylaminoethyl) -? - aminopropyltrimethoxysilane and hydrochloride thereof Silyl group-containing polymerizable monomers, aziridinyl group-containing polymerizable monomers such as 2-aziridinyl ethyl (meth) acrylate, (meth) acryloyl isocyanate, phenol of (meth) acryloyl isocyanate ethyl or methyl ethyl ketoxime An isocyanate group-containing polymerizable monomer such as an isocyanate group and / or a blocked isocyanate group-containing polymer such as an adduct, an oxazoline group-containing polymerizable monomer such as 2-isopropenyl-2-oxazoline or 2- (Meth) acrylate, allyl group-containing polymerizable monomers such as allyl (meth) acrylate, carbonyl group-containing vinyl monomers such as acrolein, ethylene glycol di (meth) acrylate, 1,6- (Meth) acrylic esters such as hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di Maleic acid, maleic anhydride, fumaric acid, crotonic acid, citraconic acid, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, Acid, and cinnamic acid. If the addition amount is in the range of 0.01 to 3% by weight based on the total amount of the essential monomer components (i) and (ii), the effect of the composition of the present invention is not affected.

The weight average molecular weight of the resin in the (meth) acrylic acid alkyl ester copolymer microparticle dispersion emulsion should be 100,000 or more and less than 800,000, and if it is less than 100,000, the absorption of the solvent in the ink is good, The blurring occurs in the pixels and the image quality of the printing material is lowered. On the other hand, in the case of 800,000 or more, since the absorption of the solvent is poor, the solvent becomes wet and spreads, which is not preferable because a desired shape and size can not be obtained.

The particle diameter of the above-mentioned (meth) acrylic acid alkylester copolymer resin fine particle dispersion emulsion should be in the range of 10 nm or more and less than 500 nm in terms of the number average particle diameter and less than 10 nm in the emulsion polymerization method employed in the present invention I can not get it. On the other hand, when the particle diameter is 500 nm or more, the ink absorptivity is not uniform, irregularities are generated on the dot end and a regular pixel shape can not be obtained. As the particle diameter increases, aggregation occurs, It is not preferable in terms of lack of stability. The number average particle diameter referred to herein is an average particle diameter obtained by analyzing the autocorrelation function obtained by the dynamic light scattering method by the Kyulmun method.

The above-mentioned emulsion polymerization method is not particularly limited, and is obtained by continuously supplying the monomer mixture, the polymerization initiator and, if necessary, a chain transfer agent, an emulsifier and the like to the aqueous medium under stirring at a predetermined temperature. When the concentration of the mixture of the monomer mixture and the emulsifier is in the range of 10 to 80% by weight based on the whole amount of the monomer mixture, the (meth) acrylic acid alkyl ester copolymer resin fine particle dispersion emulsion can be obtained stably. 50% by weight is more preferable because it is more stabilized.

Examples of the polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, organic peroxides such as benzoyl peroxide, cumene hydroperoxide and tert-butyl hydroperoxide, and hydrogen peroxide. Radical polymerization using only these peroxides, a redox polymerization initiator system in which the peroxide is combined with a reducing agent such as ascorbic acid, a metal salt of formaldehyde sulfoxylate, sodium thiosulfate, ferric chloride or the like, or a 4,4'-azo Azo type polymerization initiators such as bis (4-cyanovaleric acid) and 2,2'-azobis (2-amidinopropane) dibasic acid can be used, and these can be used alone or in combination.

Examples of the emulsifier include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like. From the applicability to the composition of the present invention, anionic surfactants and nonionic surfactants And they may be used singly or in combination of two or more kinds.

Examples of the anionic surfactant include higher fatty acid salts such as sodium oleate, alkyl aryl sulfonic acid salts such as sodium dodecylbenzenesulfonate, alkyl sulfuric acid ester salts such as sodium lauryl sulfate, poly Polyoxyethylene alkylaryl ether sulfuric acid ester salts such as oxyethylene alkyl ether sulfuric acid ester salts and polyoxyethylene nonylphenyl ether sulfuric acid sodium salt, monooctylsulfosuccinic acid sodium, dioctylsulfosuccinic acid sodium, polyoxyethylene laurylsulfosuccinic acid sodium and the like Sulfosuccinic acid ester salts and derivatives thereof, and the like. Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, Sorbitan higher fatty acid esters such as sorbitan monolaurate, sorbitan monolaurate, sorbitan monostearate and sorbitan trioleate; polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate; Polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate, glycerol higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride, and other polyoxyethylene-polyoxypropylene block Copolymers and the like can be mentioned .

As the surfactant other than those exemplified above, a reactive surfactant can be mentioned. Examples thereof include alkylsulfosuccinic acid alkenyl ether salt type, alkylsulfosuccinic acid alkenyl ester salt type, methylene bis polyoxyethylene alkylphenyl alkenyl ether sulfuric acid ester salt type, alkyl alkenyl succinic acid ester salt type, polyoxyalkylene (meth) acrylate sulfuric acid ester (Meth) acrylic acid sulfoalkyl ester salt type, phthalic acid dihydroxyalkyl (meth) acrylate sulfuric acid ester salt type, mono or di (glycerol-1-alkylphenyl 3-allyl-2-polyoxyalkylene ether) phosphate ester salt type surfactants, polyoxyalkylene alkyl phenyl ether (meth) acrylate type reactive surfactants and the like. The addition amount of the surfactant exemplified as the emulsifier is usually from 0.1 to 20% by weight based on the total amount of the above-described essential monomer components, but is preferably from 1 to 15% by weight in view of the stability of the composition of the present invention and the above- Do.

Next, the surfactant having the fluidity of (2) is added separately from the emulsifier, and indicates a liquid or slurry surfactant having fluidity at room temperature of 23 DEG C, and may be an anionic surfactant, a nonionic surfactant, A surfactant, a fluorine-based surfactant, or a mixture thereof. The addition of the surfactant not only improves the permeability of the printing ink and the prevention of ink bleeding, but also improves the stability of the composition, improves the leveling property at the time of application to the substrate, and improves the defoaming property. Is an essential component.

Examples of the anionic surfactant include higher fatty acid salts such as sodium oleate, alkylarylsulfonic acid salts such as sodium dodecylbenzenesulfonate, alkylsulfuric ester salts such as sodium laurylsulfate, polyoxyethylene lauryl ether sulfate such as sodium polyoxyethylene lauryl ether sulfate, Alkyl ether sulfuric acid ester salts, polyoxyethylene alkylaryl ether sulfuric acid ester salts such as sodium polyoxyethylene nonylphenyl ether sulfate, alkyl monosulfates such as sodium monooctylsulfosuccinate, sodium dioctylsulfosuccinate and sodium polyoxyethylene laurylsulfosuccinate Succinic acid ester salts and derivatives thereof, and the like. It is preferable that the above-mentioned middle alkyl chain has 4 to 18 carbon atoms and the polyoxyethylene chain has 4 to 22 oxyethylene as a repeating unit.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether Sorbitan monolaurate, sorbitan monostearate, and sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene Polyoxyethylene higher fatty acid esters such as monooleate and polyoxyethylene monostearate, glycerol higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride, and polyoxyethylene-polyoxypropylene block copolymer And the like. It is preferable that the above-mentioned middle alkyl chain has 2 to 22 carbon atoms, the polyoxyethylene chain has 2 to 22 oxyethylene as a repeating unit, and the polyoxypropylene chain has 1 to 20 oxypropylene as a repeating unit.

Examples of the silicone surfactant include dimethylsilicone, aminosilane, acrylsilane, vinylbenzylsilane, vinylbenzylaminosilane, glycidosilane, mercaptosilane, dimethylsilane, polydimethylsiloxane, polyalkoxysiloxane, hydrogene modified siloxane, vinyl modified siloxane Modified siloxane, alkyl modified siloxane, alkyl modified siloxane, alkyl modified siloxane, alkyl modified siloxane, alkyl modified siloxane, alkyl modified siloxane, alkyl modified siloxane, alkyl modified siloxane, alkyl modified siloxane, alkyl modified siloxane, modified siloxane, modified siloxane, modified siloxane, modified siloxane, methacryloxy modified siloxane, mercapto modified siloxane, Siloxane, and the like. Among them, the alkylene oxide-modified siloxane is listed as being highly applicable to the composition of the present invention, and the copolymer resin with the (meth) acrylic acid alkyl ester compound in which the skeleton is assembled is more preferable because of its high applicability.

Examples of the fluorine-based surfactant include known fluorine-containing surfactants such as tetrafluoroethylene, perfluoroalkylammonium salt, perfluoroalkylsulfonamide, sodium perfluoroalkylsulfonate, perfluoroalkylpotassium salt, perfluoroalkyl Perfluoroalkylsulfonic acid salts, perfluoroalkyl ethylene oxide adducts, perfluoroalkyltrimethylammonium salts, perfluoroalkylaminosulfonic acid salts, perfluoroalkyl phosphoric acid esters, perfluoroalkylalkyl compounds, perfluoroalkylsulfonic acid salts, Perfluoroalkyl alkyl betaine, perfluoroalkyl halide, and the like. Among them, perfluoroalkyl ethylene oxide adducts are listed as high applicability to the composition of the present invention, and the copolymer resin with the (meth) acrylic acid acryl ester compound in which the above skeleton is assembled has applicability And is more preferable.

The amount of the surfactant to be added is preferably such an amount as not to impair the printing properties, tackiness and the like of the coating film, and is preferably 0.1 to 10% by weight based on the total amount of the composition of the present invention. When the addition amount is 0.1% by weight or less, the stability of the composition is lost, and the effect such as leveling property is deteriorated. When the content is more than 10% by weight, the absorption ability of the ink is remarkably lowered to cause blurring or bunching, or the coating film strength tends to remarkably decrease. Therefore, the range of 0.1 to 5% Do.

Further, the organic solvent (3) is an essential component since the composition of the present invention is applied by a later application method, thereby giving an effect of preventing the formation of an antibacterial effect by drying the composition. In the case of no addition, accumulation of foreign matter on the coating equipment at the time of continuous coating may cause adhesion of foreign matter on the coating film, deterioration of the flatness of the coating film, and deterioration of the image quality of the ink print. The organic solvent preferably has compatibility with an aqueous medium and boiling point of 150 to 300 캜. The reason for this is that when the boiling point is 150 ° C or lower, the effect of preventing the film formation is not obtained. When the temperature is higher than 300 ° C, the dryability tends to deteriorate and the ink absorption ability tends to deteriorate.

Examples of the organic solvent include alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, phenyl ether, ethylene glycol Monobenzyl ether, ethylene glycol monoethylhexyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, di Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether acetate, ethylene glycol diethyl ether acetate, ethylene glycol dibutyl ether (ethylene glycol monoethyl ether acetate), ethylene glycol monomethyl ether acetate Acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether acetate, diethylene glycol diethyl ether acetate, diethylene glycol dibutyl ether acetate, propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol Monoethyl ether acetate, tripropylene glycol monomethyl ether acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate, dimethyl phthalate, diethyl phthalate, , And ketones such as cyclohexanone.

The amount of the organic solvent to be added is preferably such an amount as not to impair the printing properties, tackiness and the like of the coating film, and is preferably 1 to 20% by weight based on the total amount of the composition of the present invention. When the addition amount is less than 1% by weight, the effect of preventing film formation is not obtained. On the other hand, when the amount exceeds 20% by weight, the absorption ability of the ink remarkably lowers to cause blurring and bunching, or the conveying property of the coated substrate tends to decrease due to remarkable decrease in the strength of the coating film or development of tackiness of the coating film.

The transparent resin layer of the present invention is a layer formed by applying the composition of the present invention to a support substrate such as glass, polyethylene terephthalate film, polycarbonate film, cycloolefin copolymer film, polyimide film, polyethylene naphthalate film and the like and drying A coating method such as a spray coat, a spin coat, a die coat, a gravure coat, a knife coat, a dip coat, a comma coat, a kiss coat, a curtain coat, an air knife coat, a blade coat, a reverse roll coat and a slit coat And the drying method may be any of an in-line coating method and an off-line coating method in which a hot-air dryer is disposed.

Further, the transparent resin layer of the present invention is excellent in transparency because the resin constituting the (meth) acrylic acid alkylester copolymer resin fine particle dispersion emulsion has a number average particle diameter of nano size. Preferably, when a resin layer having a thickness of 1 to 30 탆 is formed by using a transparent resin layer composition, the light transmittance at a wavelength of 400 nm is 80% or more. The transparent resin layer formed by using the transparent resin layer composition of the present invention can form, for example, a color filter, a transparent conductive film, an edible portion surface protective film and the like by drawing an inkjet ink thereon, Device, an EL display device, a touch panel, and the like.

As described above, the present invention is characterized in that, in the receptive layer for drawing the oil-based ink-jet ink, the ink-jet ink is sufficiently accommodated and the shape after drying is controlled while controlling the droplet spreading diameter, The device provides a clear image. These contribute to fixed coloring of color filters, insulating layers, touch panels, and the like of liquid crystal displays, electronic papers, display devices for digital signage, for example.

FIG. 1 is a plan view showing the spread of dots of one RB.
2 is a plan view showing a dot drawing sequence of nine pixels.
Fig. 3 is a plan view showing a good state of the pixels consisting of nine pixels. Fig.
Fig. 4 is a plan view showing a state in which nine pixels of the pixel are thermally isolated. Fig.
5 is a plan view showing a pixel made up of 9 meshes.
6 is a 3D image analysis chart showing that the pixels are formed in a good state.
Fig. 7 is a 3D image analysis diagram showing a state in which a pixel is connected by the outflow of resin. Fig.

EXAMPLES Next, examples and comparative examples of the present invention are shown, but the present invention is not limited to these examples. First, measurement and evaluation methods used in the present invention are shown below.

≪ Solid content concentration >

W1 (g)] after impregnation with a glass filter (weight: W0 (g)) and heating for 2 hours at 105 DEG C [W2 g) from the following equation.

Solid content concentration (% by weight) = 100 x (W2-W0) / (W1-W0)

<Glass transition temperature>

The resin emulsion obtained in the following Examples and Comparative Examples was spin-coated on a glass substrate, dried at 70 캜 for 30 minutes, and then measured using a coating film obtained by using a differential scanning calorimeter EXSTAR-6000 DSC manufactured by SII Nano Technology .

<Particle Diameter Measurement>

1 g of the resin emulsion obtained in the following Synthesis Example was taken and purified water was added to make 5 g. Then, OTSUKA ELECTRONICS Co., LTD. The measurement was made using the product FPAR-1000. Here, the autocorrelation function obtained by the dynamic light scattering method was analyzed by the cumulant method to determine the number average particle diameter.

<Molecular Weight>

50 mg of the resin emulsion obtained in the following examples and comparative examples was sampled, and 5 mL of tetrahydrofuran (THF) was added and dissolved. The gel permeation chromatography method (GPC method) using THF as an eluent was used as a standard polystyrene conversion value The weight average molecular weight (Mw) was determined. As a measuring apparatus, a high-performance liquid chromatograph HLC-8220 manufactured by TOSOH CORPORATION was used, and a column system connected in the order of TSKgel Super H4000, 3000, 2000 and 2000 was used for the column.

&Lt; Preparation of Transparent Resin Layer Composition >

In order to clarify the performance of the resin of the present invention, the following composition ratios were fixed and evaluated, but the constituents and the composition ratios thereof are not limited in the present invention.

61.3 g of the resin emulsion (Synthesis Example 1 (1)) obtained in the following Synthesis Example, (2) 0.5 g of EMULGEN 103 (flowable surfactant: polyoxyethylene lauryl ether) from Kao Corporation, (3) 10.0 g of SOLFINE EP (organic solvent: ethyl-3-ethoxypropionate) and (4) 28.2 g of pure water were weighed and stirred for 30 minutes or more.

Based on this operation, a composition as shown in the following table was prepared and used in Examples 11 to 13 and Comparative Examples 8 to 12. In the composition H, the component (3) was changed to tetraethylene glycol manufactured by Tokyo Chemical Industry Co., Ltd.

<Adhesion>

The transparent resin layer composition having the above composition was spin-coated on a glass substrate and dried at 70 DEG C for 3 minutes to obtain a coated substrate. Then, another glass substrate was adhered to the coated surface, and 1 kg of weight was placed thereon for 5 minutes , And the glass substrate was peeled off. At this time, if the peeling was found to be possible, the result was rated &quot; o &quot;

&Lt; Measurement of film thickness &

8.5 mL of the transparent resin layer composition having the above composition was spin-coated on a glass substrate at a revolution of 200 rpm and dried at 70 캜 for 3 minutes to prepare a coated substrate. The product was measured using ET-4000AK.

<Measurement of light transmittance>

A substrate having a transparent resin layer having a thickness of 10 占 퐉 obtained in the same manner as described above was measured with a U-4000 manufactured by Hitachi High-Tech Fielding Corporation with a wavelength of 400 nm as a substrate itself as a reference.

&Lt; Contact angle measurement &

A substrate having a transparent resin layer having a thickness of 占 퐉 obtained in the same manner as above was placed on a horizontal holding die and 0.5 占 퐇 of ethylcarbitol acetate (organic solvent: ECA) droplets was dropped thereon. The contact angle was measured using an OCAH-200 high speed contact angle meter manufactured by EKO Instruments.

<Dot Diameter>

As shown in Fig. 1, using the inkjet apparatus equipped with a KONICA MINOLTA, INC. Product inkjet head KM512M (equipped with a nozzle for ejecting 14 pl, 512 holes), the above-mentioned transparent resin layer composition had a thickness of about 10 탆 The glass substrate coated with a slit coater so as to be drawn with one RB per 200 mu m pitch to observe the spreading region. And a dot area of 80 占 퐉 or less was a wet spreading area having a good wetting property.

&Lt; Pixel shape stability >

Next, as shown in Fig. 2, four dots are drawn by dropping the center-to-center distance so that the center-to-center distance is 50 占 퐉 in the X and Y directions as shown in Fig. 2, and the dots are repeatedly drawn so as to fill each dot, Pixel. Thereafter, after drying for 5 minutes at 60 ° C, a microscope at a magnification of 300x was observed. When the pixel shape was maintained as in the example of Fig. 3, . In the example of the evaluation of x in Fig. 4, a state of being insulated at the dots 5, 6, 7 to 9 shown in Fig. 2 is shown.

<Capacity>

Next, 8 meshes are further drawn adjacent to each other as shown in Fig. 5 with 1 mesh of the pixel shown in Fig. 2, thereby forming pixels of 9 meshes in total. At this time, when the grids were arranged in a regular manner by 3D image analysis using an optical interferometry surface roughness meter manufactured by Veeco, the evaluation was evaluated as O (Fig. 6), and the grid was connected by the outflow of resin caused by solvent dissolution If there is, the evaluation is evaluated as X (FIG. 7), and the interval therebetween is evaluated as?.

&Lt;

Among the evaluations described above, it was confirmed that the coating layer prepared by the composition of the present invention had a dot diameter of 80 mu m or less and a pixel shape stability of &amp; cir &amp; and a storage capacity of &amp; cir &amp; , And the acceptance performance were evaluated as &quot; DELTA &quot;

&Lt; Coatability >

The transparent resin layer composition comprising the above blend was continuously and repeatedly subjected to an operation of 280 占 퐉 mm on a 300 占 퐉 -thick glass substrate using a device in which a slit coater head with a width of 280 mm was arranged I did. When the number of glass substrates that can be coated with a target of 280 mm is continuously 20 or more, the result is indicated by?, When the number of continuous glass substrates is 10 or more and 20 or less, and when the number of continuous glass substrates is 10 or less,

(Synthesis Example 1)

175.3 g (1.75 mol) of methyl methacrylate, 175.3 g (1.75 mol) of ethyl acrylate, 16.0 g (0.07 mol) of ammonium persulfate as a polymerization initiator were added to the composition (weight ratio) shown in Example 1 of Table 2, 36.5 g (10% by weight based on the total weight of the monomer) of PD-104 (manufactured by Kao Corporation: ammonium polyoxyalkylenealkenyl ether sulfate) and 400 g of pure water were preliminarily emulsified in a beaker and homogenized with a homogenizer, Was added to a 1500 mL flask equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introducing tube and a thermometer, and the remaining 627 g of the preliminary emulsion was added to the dropping funnel. The temperature was raised to 70 to 80 캜 under a nitrogen atmosphere, The preliminary emulsion was continuously dropped from the dropping funnel over 3 hours, and after completion of the dropwise addition, stirring was continued for 5 hours to terminate the polymerization. After cooling at room temperature, the solid content concentration was measured, and pure water was added so that the solid content concentration became 40% to obtain Resin Emulsion 1. The resin contained in the obtained resin emulsion 1 had a Tg of 41 캜, a particle diameter of resin particles in the emulsion was 40 nm, and a weight average molecular weight Mw = 300000.

(Synthesis Example 2)

175.3 g (1.75 mol) of methyl methacrylate, 175.3 g (1.75 mol) of ethyl acrylate, 8.0 g (0.04 mol) of ammonium persulfate and LATEMUL PD-104 (manufactured by Kao Corporation) (10% by weight based on the total weight of the monomer) and 400 g of pure water were preliminarily emulsified in a beaker and homogenized with a homogenizer, and 160 g of the emulsion and 200 g of pure water were mixed with a stirrer, a reflux condenser, a dropping funnel, The remaining 630 g of the preliminary emulsion was further added to a dropping funnel in a 1500 mL flask, and the temperature was raised to 70 to 80 캜 under a nitrogen atmosphere and maintained for 30 minutes. Thereafter, the preliminary emulsion was continuously dropped from the dropping funnel over 3 hours, The polymerization was continued by stirring for 5 hours. After cooling at room temperature, the solid content concentration was measured, and pure water was added so that the solid content concentration became 40% to obtain Resin Emulsion 2. The Tg of the resin contained in the obtained Resin Emulsion 2 was 41 占 폚, the particle diameter of the resin particles in the emulsion was 38 nm, and the weight average molecular weight Mw was 580000.

(Synthesis Examples 3 and 4)

Resin emulsions 3 and 4 were obtained by polymerizing in the same manner as in Synthesis Example 1 except that methyl methacrylate and ethyl acrylate were blended so as to have compositions shown in Examples 3 and 4 in Table 2. The glass transition temperature, particle diameter, and weight average molecular weight were measured for each sample. The results are shown in Examples 3 and 4 of Table 2.

(Synthesis Examples 5 to 7)

Methyl methacrylate and ethyl acrylate were blended in the same manner as in Example 1 of Table 2. In Example 5, the emulsifier was blended from LATEMUL PD-104 to LATEMULPD-104 / LATEMUL PD-420 (manufactured by Kao Corporation: polyoxyalkylene LATEMUL PD-104 / LATEMUL PD-420 = 1: 4 in Example 6 and a mixture of LATEMUL PD-104 / LATEMUL PD-420 = 1: 450 = 1: 4, and polymerization was carried out in the same manner as described in Synthesis Example 1 except that the amounts were adjusted so as to be 10% by weight based on the total weight of the monomers. Thus, Resin Emulsions 5 to 7 were obtained. The glass transition temperature, particle diameter, and weight average molecular weight were measured for each sample. The results are shown in Examples 5 to 7 in Table 2.

(Synthesis Examples 8 to 10)

Methyl methacrylate and butyl acrylate or 2-ethylhexyl methacrylate were mixed so as to have compositions shown in Examples 8 to 10 in Table 2 and polymerized in the same manner as in Synthesis Example 1 to obtain Resin Emulsion 8 to 10 &Lt; / RTI &gt; The glass transition temperature, particle diameter, and weight average molecular weight were measured for each sample. The results are shown in Examples 8 to 10 in Table 2.

&Lt; Example 1 >

61.3 g of the (1) resin emulsion 1 obtained in Synthesis Example 1, (2) 0.5 g of EMULGEN 103 manufactured by Kao Corporation, (3) 10.0 g of SOLFINE EP manufactured by Showa Denko KK, and (4) 28.2 g of pure water, The mixture was stirred and mixed for 30 minutes or more and subjected to pressure filtration at 0.5 kg / cm ² with a 1.0 탆 filter to obtain a desired transparent resin layer composition. Next, this was applied to a glass substrate Corning EX-G (glass plate thickness: 0.75 mm) manufactured by Corning Incorporated, and dried by a slit coat so as to have a film thickness of about 10 탆 and thermally dried on a hot plate at 70 캜 for 5 minutes, A glass substrate having a layer was obtained. The film thickness of the transparent resin layer was 11 mu m, and the surface was not tacky. The transmittance at a wavelength of 400 nm was 92%.

Subsequently, the glass substrate having the transparent resin layer obtained above was placed on a horizontal holding die, and 0.5 占 퐇 of ECA droplets were dropped thereon. The contact angle after 1 second from landing was 45 占.

Then, KONICA MINOLTA, INC. Using the inkjet apparatus equipped with the product inkjet head KM512M (equipped with 14-pl dischargeable nozzles 512 holes), the ECA was drawn at one RB per 200 占 퐉 pitch as shown in Fig. 1 to observe the dot spread region. The dot diameter immediately after drawing was 67 탆.

Subsequently, as shown in Fig. 2, dots were drawn by dropping the center-to-center distance so that the center-to-center distance was 30 占 퐉 in the X and Y directions, and this dot was repetitively consecutively drawn to form nine overlapping pixels. Thereafter, after drying for 5 minutes at 60 캜, a microscope was observed, and the pixel shape was maintained as shown in Fig.

Next, as shown in Fig. 5, the pixels of Fig. 1 are set as one mesh, and eight meshes are further drawn adjacent to each other as shown in Fig. 5, thereby forming pixels of a total of 9 meshes. Since the landscape as shown in Fig. 6 was observed from the 3D image analysis using the optical interferometry surface roughness meter immediately thereafter, the evaluation was made to be ○, in which the grid was not connected by the outflow of resin but the grid was aligned in a regular manner.

From the above evaluation results, it was determined that the coated film produced by the composition shown in Example 1 had a high capability as a receptive layer because the dot diameter was 67 占 퐉 and the pixel shape stability was? And the accommodating performance was? .

Further, the composition shown in Example 1 was repeatedly subjected to an operation in which a 280 mm-wide slit-coater head was placed on a glass substrate with a size of 280 mm using a device without a head cleaning operation, , It was possible to apply more than 20 sheets continuously in 280 mm mm.

&Lt; Examples 2 to 10 &

The transparent resin layer compositions according to Examples 2 to 10 were obtained in the same manner as in Example 1 except that (1) the resin emulsions 2 to 10 obtained in Synthesis Examples 2 to 10 were respectively used. Using these materials, a glass substrate having each transparent resin layer was obtained in the same manner as in Example 1. Various evaluations were carried out in the same manner as in Example 1, and the evaluation results are shown in Table 2.

&Lt; Examples 11, 12 and 13 >

A transparent resin layer composition was obtained by applying Composition A in Example 11, Composition B in Example 12, and Composition C in Example 13 in the composition described in Table 1 above. Using these materials, a glass substrate having each transparent resin layer was obtained in the same manner as in Example 1. The evaluation was carried out in the same manner as in Example 1, and the evaluation results are shown in Table 2.

(Reference Synthesis Example 1)

176.2 g (1.76 mol) of methyl methacrylate, 447.8 g (1.76 mol) of lauryl methacrylate, 16.0 g (0.07 mol) of ammonium persulfate and 10 g of LATEMUL PD-104 (10% by weight based on the total weight of the monomer) and 700 g of pure water were preliminarily emulsified in a beaker and homogenized by a homogenizer. 280 g of the emulsion and 280 g of pure water were mixed in a stirrer, a reflux condenser, a dropping funnel, And the remaining 1123 g of the preliminary emulsion was added to the dropping funnel. The temperature was raised to 70 to 80 캜 under a nitrogen atmosphere, and the mixture was held for 30 minutes. Thereafter, the emulsion was continuously dropped from the dropping funnel over 3 hours, The polymerization was continued for 5 hours to terminate the polymerization. After cooling to room temperature, the solid content concentration was measured, and pure water was added so that the solid content concentration became 40% to obtain a resin emulsion. The resin contained in the resin emulsion thus obtained had a Tg of 20 DEG C, a particle diameter of the resin particles in the emulsion was 50 nm, and a weight average molecular weight Mw = 530000.

(Reference Synthesis Examples 2 to 7)

Methyl methacrylate and various monomers were mixed so as to have compositions shown in Comparative Examples 2 to 7 in Table 3 and polymerized in the same manner as described in Reference Synthesis Example 1 to obtain resin emulsions. The glass transition temperature, particle diameter, and weight average molecular weight were measured for each sample. The results are shown in Examples 2 to 7 in Table 3.

(Reference Synthetic Example 8)

175.3g (1.75mol) of methyl methacrylate, 175.3g (1.75mol) of ethyl acrylate, and 2,2'-azobis (2-methyl-butyronitrile) were added to a 1500ml four-necked flask equipped with a reflux condenser, AIBN) and 500 g of propylene glycol monomethyl ether acetate (PGMEA), and the mixture was polymerized by stirring at 80 to 85 캜 for 8 hours and 95 to 100 캜 for 5 hours under a nitrogen atmosphere. After cooling at room temperature, PGMEA was added to adjust the solid content to 40% to obtain a resin solution. The resin contained in this resin solution had a glass transition temperature of 41 占 폚 and a weight average molecular weight of 50,000.

(Reference Synthesis Examples 9 and 10)

Methyl methacrylate and ethyl acrylate were combined so that the composition shown in Comparative Examples 14 and 15 in Table 3 was used and the addition amount of AIBN was changed from 0.07 mol to 0.01 mol in Comparative Example 14 and 0.005 mol in Comparative Example 15 to obtain Reference Synthesis Example 8, to obtain respective resin solutions. The glass transition temperature and the weight average molecular weight were measured for each sample. The results are shown in Comparative Examples 14 and 15 in Table 3.

&Lt; Comparative Example 1 &

61.3 g of the resin emulsion (1) obtained in Synthesis Example 1, (2) 0.5 g of EMULGEN 103 manufactured by Kao Corporation, (3) 10.0 g of SOLFINE EP manufactured by Showa Denko KK, and (4) 28.2 g of pure water were weighed The mixture was stirred and mixed for 30 minutes or more, followed by pressure filtration at 0.5 kg / cm ² with a 1.0 μm filter to obtain a desired transparent resin layer composition. Next, this was applied to a glass substrate Corning EX-G (glass plate thickness: 0.75 mm) manufactured by Corning Corporation, dried, and then coated with a slit coat so as to have a film thickness of about 10 탆. To obtain a glass substrate having a transparent resin layer. The film thickness of the transparent resin layer was 13 mu m, and the surface was confirmed to be sticky. The transmittance at a wavelength of 400 nm was 85%.

Subsequently, the substrate was placed on a horizontal holding die, and 0.5 占 퐇 of ECA droplets were dropped therefrom. The contact angle after 1 second after landing was 43 占 폚.

Then, using an ink-jet apparatus equipped with KONICA MINOLTA, INC. Manufactured inkjet head KM512M (equipped with 14-pl dischargeable nozzles with 512 holes), as shown in Fig. 1, the ECA was drawn at one RB per 200 [mu] m pitch, The area was observed. The dot diameter immediately after drawing was 60 占 퐉.

Subsequently, as shown in Fig. 2, dots were drawn by dropping the center-to-center distance so that the center-to-center distance was 30 占 퐉 in the X and Y directions, and this dot was drawn repeatedly and successively to form nine overlapping pixels. Thereafter, after drying for 5 minutes at 60 占 폚, when the sample was observed under a microscope, the pixel was insulated as shown in Fig.

Subsequently, 8 meshes are further drawn so that the pixels of Fig. 1 are adjacent to each other as shown in Fig. 5 with one mesh, thereby forming pixels having a total of 9 meshes. From the 3D image analysis using the optical interferometric surface roughness meter immediately thereafter, the evaluation was evaluated as &quot; x &quot; because the gaps between the grids were connected by the outflow of the resin as shown in Fig.

From the above evaluation results, the dot diameter was 60 탆, but the coating film prepared from the composition shown in Comparative Example 1 was evaluated as poor in the capability of the receptive layer because of the pixel shape stability x and the acceptance performance x .

In addition, when the composition shown in Comparative Example 1 was repeatedly applied with a head cleaning apparatus in a 280 mm-wide slit-coater head on a glass substrate of 300 mm square at 280 mm, Was evaluated as &quot; x &quot; in that the number of substrates that could be continuously applied was 280 mm or less.

&Lt; Comparative Example 2 &

A transparent resin layer composition according to Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that the resin emulsion having the monomer composition described in Comparative Example 2 in Table 3 was used. Next, using this, a glass substrate having a transparent resin layer was obtained in the same manner as in Comparative Example 1. The evaluation was carried out in the same manner as in Comparative Example 1, and it was considered that the transparency was influenced by the fact that the transmittance was 75%.

In addition, although the dot diameter exceeded 82 탆 and 80 탆, since the shape of the nine overlapping pixels was maintained, the stability of the pixel shape was evaluated as ◯. However, even if the grid shown in Fig. 5 can be drawn, the evaluation is evaluated as? Since the pixel connection as shown in Fig. 7 is slightly observed.

From the above evaluation results, the coating film prepared from the composition shown in Comparative Example 2 was evaluated as &quot; poor &quot;

In addition, evaluation of coatability was carried out in addition to the above evaluation. As a result, evaluation was made on the point that the number of substrates that could be continuously applied at 280 탆 in the target was 20 or more.

&Lt; Comparative Example 3 &

A transparent resin layer composition according to Comparative Example 3 was obtained in the same manner as in Comparative Example 1 except that the resin emulsion having the monomer composition described in Comparative Example 3 in Table 3 was used. Next, using this, a glass substrate having a transparent resin layer was obtained in the same manner as in Comparative Example 1. When the same evaluation as in Comparative Example 1 was carried out, the dot diameter was reduced to 53 탆. However, in view of the heat insulation of the pixel as shown in Fig. 4 and the connection between the grid as shown in Fig. 7, , It was regarded as x.

From the above-described evaluation results, the coating film formed from the composition shown in Comparative Example 3 was evaluated as &quot; poor &quot;

In addition, evaluation of coatability was performed in addition to the above evaluation. As a result, the evaluation was X in that the number of substrates that could be continuously applied at 280 탆 was 10 or less.

&Lt; Comparative Example 4 &

A transparent resin layer composition according to Comparative Example 4 was obtained in the same manner as in Comparative Example 1 except that the resin emulsion having the monomer composition described in Comparative Example 4 in Table 3 was used. Next, using this, a glass substrate having a transparent resin layer was obtained in the same manner as in Comparative Example 1. When the same evaluation as in Comparative Example 1 was carried out, the dot diameter was extremely large, 110 탆, and the pixel shape stability and the acceptance performance evaluation were evaluated as &quot; x &quot; , And the coating film prepared from the composition shown in Comparative Example 4 was evaluated as &quot; poor &quot;

In addition, evaluation of coatability was carried out in addition to the above-mentioned evaluation. As a result, the evaluation was made in view of the fact that the number of substrates that could be continuously applied at 280 탆 in the target was 20 or more.

&Lt; Comparative Examples 5 and 6 >

A transparent resin layer composition according to Comparative Examples 5 and 6 was obtained in the same manner as in Comparative Example 1 except that the resin emulsion having the monomer composition described in Comparative Examples 5 and 6 in Table 3 was used. Next, using this, a glass substrate having a transparent resin layer was obtained in the same manner as in Comparative Example 1. Evaluation was conducted in the same manner as in Comparative Example 1, and it was considered that the transparency was influenced by the fact that the transmittance was 81% and 83%, respectively. The dot diameters were 57 탆 and 58 탆, respectively, which were equal to those of the examples. However, since the surface of the resin layer had a large particle diameter, a coarse and square grid could not be obtained.

From the above-described evaluation results, it was confirmed that the coated film formed from the compositions shown in Comparative Examples 5 and 6 had a capability of being a receptive layer, lower than that described in the Examples, and evaluated to be moderate.

In addition, evaluation of coatability was carried out in addition to the above evaluation. As a result, when the object was coated with 280 mm in length, protrusions derived from agglomerate appeared on the surface of the substrate, and the substrate with good flatness was not obtained.

&Lt; Comparative Example 7 &

A transparent resin layer composition according to Comparative Example 7 was obtained in the same manner as in Comparative Example 1 except that the resin emulsion having the monomer composition described in Comparative Example 7 in Table 3 was used. Next, using this, a glass substrate having a transparent resin layer was obtained in the same manner as in Comparative Example 1. The same evaluation as in Comparative Example 1 was carried out. As a result, the dot diameter was 62 占 퐉 and the pixel shape of nine overlapping pixels was maintained. However, since ECA absorbability was poor, wet liquid spreading The acceptance performance was evaluated as x.

From the above-described evaluation results, the coating film prepared from the composition shown in Comparative Example 7 was evaluated as DELTA evaluation in which the ability of the receptive layer was lower than that described in the examples and judged with a certainty.

In addition, evaluation of coatability was carried out in addition to the above evaluation. As a result, evaluation was made on the point that the number of substrates that could be continuously applied at 280 탆 in the target was 20 or more.

&Lt; Comparative Examples 8 to 12 &

In the composition described in Table 1, the composition D was used in Comparative Example 8, the composition E was used in Comparative Example 9, the composition F was used in Comparative Example 10, the composition G was used in Comparative Example 11, and the composition H To obtain a transparent resin layer composition. Using these materials, a glass substrate having the respective transparent resin layers was obtained in the same manner as in Comparative Example 1. Then, the evaluation was carried out in the same manner as in Comparative Example 1, the evaluation results are shown in Table 2, and the reasons for evaluation are described below.

In Comparative Example 8, since the dot diameter was as large as 82 占 퐉 and the ECA was wetted and widened, as shown in Fig. 7, connection of grid sheath was observed.

In Comparative Example 9, the coating film was tacky, and the shape of the nine overlapping pixels was as shown in Fig. 4. Therefore, the pixel shape stability was evaluated as x, and the connection between the grids was seen as shown in Fig. The performance was evaluated as × evaluation.

In Comparative Example 10, the dot diameter was as large as 81 占 퐉, the surface of the coating film was not uniform, the dot was slightly clustered, the pixel of a certain size could not be drawn by the position of the mesh, 4, the pixel shape stability was evaluated as &quot; x &quot;, and the acceptance performance was rated as &quot; DELTA &quot; in that a slight connection was observed between the grid as shown in Fig. From the above results, the performance of the receptive layer was evaluated as &quot; x &quot;.

In Comparative Example 11, the coating film had stickiness, and the shape of the nine overlapping pixels was as shown in Fig. 4. The pixel shape stability was evaluated as x, and the acceptance performance was evaluated as x from the point where the pixels were connected as shown in Fig. From the above results, the performance of the receptive layer was evaluated as &quot; x &quot;.

In Comparative Example 12, the coating film was tacky, and the shape of the nine overlapping pixels was as shown in Fig. 4. The pixel shape stability was evaluated as x, and the acceptance performance was evaluated as x in that pixels were connected as shown in Fig. From the above results, the performance of the receptive layer was evaluated as &quot; x &quot;.

In addition to the above evaluations, the coating properties were evaluated in Comparative Examples 8 to 12, and in Comparative Examples 10 and 11, the number of substrates which could be continuously applied at a target of 280 mm was 10 to 20 In the evaluation, since Comparative Examples 8, 9, and 12 were less than 10 sheets, the evaluation was X.

&Lt; Comparative Example 13 &

61.3 g of the resin solution obtained in Synthetic Example 8, 0.5 g of EMULGEN 103 manufactured by Kao Corporation, 38.2 g of SOLFINE EP manufactured by Showa Denko KK were weighed and stirred for 30 minutes or more, ² to obtain a desired transparent resin composition. Next, this was applied to a Corning glass substrate Corning EX-G (glass plate thickness: 0.75 mm), which was then dried by a slit coat so as to have a film thickness of about 10 탆 and then baked at 1200 Pa for 20 seconds, 400 Pa for 30 seconds, Dried, and then thermally dried on a hot plate at 70 캜 for 5 minutes to obtain a glass substrate having a transparent resin layer. The film thickness of the transparent resin layer was 11 mu m, and the surface was not tacky. The transmittance at a wavelength of 400 nm was 88%.

Subsequently, the substrate was placed on a horizontal holding die, and 0.5 占 퐇 of ECA droplets were dropped thereon. The contact angle after 1 second from the landing was 32 占 폚.

Then, using an ink-jet apparatus equipped with KONICA MINOLTA, INC. Manufactured inkjet head KM512M (equipped with 14-pl dischargeable nozzles with 512 holes), as shown in Fig. 1, the ECA was drawn at one RB per 200 [mu] m pitch, The area was observed. The dot diameter immediately after drawing was 91 占 퐉.

Subsequently, as shown in Fig. 2, four dots are drawn by dropping the center-to-center distance so that the center-to-center distance is 50 占 퐉 in the X and Y directions as shown in Fig. 2, The pixel shape stability and the acceptance performance evaluation were evaluated as &quot; X &quot;, and the coating film made of the composition shown in Comparative Example 4 was evaluated as &quot; The evaluation was judged to be low.

In addition, evaluation of coatability was carried out in addition to the above-mentioned evaluation. As a result, the number of substrates that could be continuously applied at 280 占 퐉 in the target was 20 or more.

&Lt; Comparative Examples 14 and 15 >

Evaluation was carried out in the same manner as in Comparative Example 13 described above, but since no pixel was obtained in the same manner as in Comparative Example 13, evaluation of the pixel shape stability, the acceptance performance, and the receptive layer performance was made by X evaluation.

In addition, evaluation of coatability was carried out in addition to the above evaluation. As a result, evaluation was made on the point that the number of substrates that could be continuously applied at 280 탆 in the target was 20 or more.

The meanings of abbreviations in Tables 2 and 3 are as follows.

MMA: methyl methacrylate

EA: Ethyl acrylate

BA: butyl acrylate

EHMA: 2-ethylhexyl methacrylate

LMA: Lauryl methacrylate

St: Styrene

Tg: glass transition temperature

Mw: weight average molecular weight

Claims (5)

(1) A copolymer obtained by polymerizing a mixed monomer containing methyl methacrylate (i) and a (meth) acrylic acid alkyl ester (ii) having 2 to 8 carbon atoms in an alkyl group, by emulsion polymerization, (Meth) acrylic acid alkylester copolymer resin fine particle dispersion emulsion having a weight average molecular weight of 100,000 or more and less than 800,000 and a number average particle diameter of 10 nm or more and less than 500 nm; And (3) an organic solvent. The transparent resin layer composition according to claim 1, The method according to claim 1,
The composition ratio of the (meth) acrylic acid alkyl ester copolymer resin fine particle dispersion emulsion (i) of methyl methacrylate and (ii) the alkyl (meth) acrylate ester having 2 to 8 carbon atoms is (i) = 1: 0.25 - 1: 2. 3. The method according to claim 1 or 2,
Wherein the resin layer has a light transmittance of 80% or more at a wavelength of 400 nm when the resin layer is formed in a thickness of 1 to 30 占 퐉. An inkjet ink-receiving layer characterized in that a transparent resin layer formed by using the transparent resin layer composition according to any one of claims 1 to 3 is formed on a support substrate. A display element obtained by drawing an ink-jet ink on a transparent resin layer formed using the transparent resin layer composition according to any one of claims 1 to 3.

Images