TW201434928A - 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 receiving layer which can receive a spotted droplet of an inkjet ink sufficiently, and whereby it becomes possible to stabilize the shape of the dried droplet of the inkjet ink while controlling the spreading diameter of the droplet of the inkjet ink. Also provided are: a receiving layer for inkjet inks, which is formed using the transparent resin layer composition and a display element. A transparent resin layer composition comprising (1) an emulsion in which alkyl (meth)acrylate ester-type copolymer resin microparticles are dispersed, (2) a surfactant which has fluidability at room temperature that is 23 not C and (3) and an organic solvent, wherein the emulsion is produced by the emulsion polymerization of a monomer mixture comprising (i) methyl methacrylate and (ii) an alkyl (meth)acrylate ester having a C2-8 alkyl group, the glass transition temperature of a resin contained in the emulsion is 10 not C or higher and lower than 70 not C, and the 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 nm or more and less than 500 nm a receiving layer for inkjet inks, which comprises a support base and a transparent resin layer comprising the above-mentioned composition and formed on the support base and a display element which is produced by drawing with an inkjet ink on a transparent resin layer formed using the above-mentioned composition.

Description

Transparent resin layer composition, receiving layer and display member for inkjet ink using the same

The present invention relates to a composition of a transparent resin layer, a receiving layer for a inkjet ink using the same, and a display element, and more specifically relates to a composition for forming a transparent resin layer for forming an ink receiving layer when inkjet ink is used, and inkjet. A receiving layer for ink and a display element.

In recent years, in the industry of inkjet printing, which has grown significantly, the high performance of inkjet printers and the improvement of inks have progressed steadily, and even in the general household, it is becoming possible to easily take photos with silver salts. The same high precision, get a sharp image. Therefore, the inkjet printer is not only used in the home, but also is used for the manufacture of electronic devices such as the manufacture of large-sized advertisement billboards or the printing of color filters for liquid crystal displays or alignment films.

Moreover, the high image quality of the inkjet printed matter is accompanied by the improvement of the performance of the above-mentioned printer, and the improvement of the printing ink is also large. Specifically, it has a high color rendering property comparable to a dye ink, and compared with a conventional dye ink, the use of a known pigment ink which can form a printed image excellent in durability is in recent years in the field of printed matter. Become the mainstream. On the other hand, as an electron For the pigment ink for a device, since the reliability of the device is required, a solvent-based pigment ink in which particles of a pigment ink are dispersed in an organic solvent is preferably used, and this is also called an oil-based pigment ink. Such an ink is suitable for the formation of a printed image because the particles of the ink are relatively hydrophobic, and have a level of bleeding of a printed image caused by moisture or the like on the printed substrate. Water resistance has attracted attention in recent years.

However, most of the conventional ink jet recording media are ink-receiving layers which have been developed for aqueous dye inks, and are designed for the purpose of improving the absorbability of the aqueous medium in the ink or improving the fixability of the dye (for example, refer to the patent). Document 1). Therefore, even if the inkjet recording medium is used for printing using the solvent-based pigment ink, the ink receiving layer cannot efficiently absorb the organic solvent, and as a result, a clear image with high color development and preventing bleeding or discoloration cannot be obtained.

Therefore, in recent years, the acceptance layer corresponding to the solvent-based pigment ink has been examined. For example, Patent Document 2 discloses that (meth)acrylic acid or ethylene other than methyl methacrylate 50 to 100% by weight and methyl methacrylate. The monomer is composed of 0 to 50% by weight, and an acrylic resin having a weight average molecular weight of 300,000 or more and 1,000,000 or less is used as a main component to form an ink receiving layer.

However, in the ink receiving layer described in the above-mentioned Patent Document 2, for example, when inkjet printing is applied to a relatively large medium such as an outdoor advertisement, the organic solvent contained in the ink cannot be sufficiently absorbed, and the ink is caused. The drying property is remarkably lowered or the bleeding of the printed image, cracks, and the like occur. Moreover, the ink receiving layer described in Patent Document 2 is used as it is. The above-mentioned specific acrylic resin is formed by dissolving an inkjet receptor in an organic solvent, and in the production of an inkjet recording medium, a step of volatilizing a large amount of an organic solvent is required.

On the other hand, in the inkjet receiving layer for an oil-based pigment ink, Patent Document 3 discloses an oil-based pigment ink obtained by dispersing a vinyl polymer having a glass transition temperature of 10 to 70 ° C and a weight average molecular weight of 800,000 or more in an aqueous medium. An inkjet receptor is used. However, when the oil-based inkjet ink is dropped onto the coating film obtained by drying the ink-jet receiving agent, the molecular weight is 800,000 or more, the absorption rate is slow, and the droplet diameter is enlarged. This is also the case in the case where the glass transition temperature of the vinyl polymer is 70 ° C or more, and the droplet expansion cannot be controlled.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 11-216945

[Patent Document 2] Japanese Patent Publication No. 2004-291561

[Patent Document 3] Japanese Invention Patent No. 4442718

An object of the present invention is to provide an ink-jet ink which can fully absorb an ink-jet ink containing a bomb-like bomb in an oil-based inkjet ink such as a solvent-based pigment ink, and which is capable of controlling the droplet expansion diameter while drying it. A composition of a transparent resin layer for forming a receiving layer. Further, it is an object of the present invention to provide a spray formed using the composition of the transparent resin layer A display element obtained by drawing an inkjet ink on a receiving layer for ink ink and a transparent resin layer formed of a composition of a transparent resin layer.

As a means for solving this problem, the present inventors have found that the glass transition temperature and molecular weight of the resin constituting the emulsified particles in the composition of the transparent resin layer are stable in suppressing the expanded diameter of the ink droplets or the shape after the drying is ensured. In addition to the particle size of the emulsified particles in the composition of the transparent resin layer, the problem of the prior art can be solved by coexisting the specified surfactant or organic solvent, and the present invention has been completed.

That is, the present invention is a transparent resin layer composition comprising: (1) an alkyl (meth)acrylate containing 2 to 8 carbon atoms of methyl methacrylate (i) and an alkyl group. (ii) The mixed monomer is obtained by emulsion polymerization and polymerization, and the resin has a glass transition temperature of 10 ° C or more and less than 70 ° C, a weight average molecular weight of 100,000 or more to less than 800,000, and a number average particle diameter. a (meth)acrylic acid alkyl ester copolymer resin fine particle dispersion emulsion 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.

Moreover, in the present invention, the inkjet ink receiving layer formed on the supporting substrate is formed by using the transparent resin layer formed of the above transparent resin layer composition. Furthermore, the present invention is a display element obtained by drawing an inkjet ink on a transparent resin layer formed using the above transparent resin layer composition.

When the (meth)acrylic acid alkyl ester copolymer resin fine particle dispersion emulsion of the present invention is obtained, (i) methyl methacrylate is used as an essential component, Introducing (ii) an alkyl (meth)acrylate having 2 to 8 carbon atoms in a manner that the glass transition temperature is 10 ° C or more and less than 70 ° C, and at least the mixture of (i) and (ii) is contained. The monomer is polymerized by emulsion polymerization. Further, the resin contained in the obtained (meth)acrylic acid alkyl ester-based copolymer resin fine particle-dispersed emulsion has a weight average molecular weight of 100,000 or more and less than 800,000, and the number average particle diameter is 10 or more and is not reached. 500nm.

The alkyl carbon number of the above (ii) alkyl (meth)acrylate is due to the fear that the coating film formed by the composition of the present invention exhibits adhesiveness or the shape of the pixel formed on the coating film by the inkjet ink. The property is reduced, so the number of carbon atoms is 2-8. When the carbon number is 1, the methyl methacrylate of (i) does not mean to be a mixed monomer. On the other hand, when the carbon number is 8 or more, the adhesiveness of the transparent resin layer is remarkably exhibited, and after the ink is printed and drawn, the crack of the pixel occurs due to drying, and the shape of the pixel is deteriorated.

The (meth)acrylic acid alkyl ester having 2 to 8 carbon atoms in the alkyl group of the above (ii) is one of a monomer (single amount) of the (meth)acrylic acid alkyl ester copolymer, and examples thereof may be mentioned. Ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, (methyl) 2-ethylhexyl acrylate, octyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate or the like. Further, the alkyl (meth)acrylate means an alkyl acrylate or an alkyl methacrylate.

The glass transition temperature of the resin in the above-mentioned (meth)acrylic acid alkyl ester copolymer resin fine particle dispersion emulsion is 10 ° C or more and less than 70 ° C Wai. If it is less than 10 ° C, the solvent in the ink is absorbed and the pixel formed by printing is connected to the adjacent pixel due to the outflow of the resin, and the colored inks are mixed or dissolved. Dry shrinkage and cracking on the printed pixels. Moreover, the adhesiveness of the coating film tends to decrease due to the adhesiveness of the coating film. On the other hand, if it is 70 ° C or more, the absorption of the solvent in the ink is deteriorated, and the solvent wets and spreads, the size of the object and the shape of the pixel are not obtained, and the penetration of the solvent in the coating film is not obtained. Evenly, the flatness of the coating film around the pixels is remarkably lowered, and as a result, the transparency is lowered.

(i) methyl methacrylate and (ii) (meth)acrylic acid having 2 to 8 carbon atoms in the (meth)acrylic acid alkyl ester copolymer resin in the glass transition temperature range described in the above paragraph The composition ratio of the ester may be in the range of (i): (ii) = 1:0.25 to 1:2 by weight ratio. In particular, if the weight ratio of methyl methacrylate (i) is in a range smaller than this range, the color mixture of the printed matter or the crack of the printed pixel may occur, and if it is more than this range In the range, there is a deterioration in the shape of the pixel and a decrease in transparency, so it is preferable to be within the range.

In the above-mentioned copolymer resin, for the purpose of preventing the crack of the inkjet ink by the strength of the transparent resin layer, a monomer having a crosslinking group can be introduced without affecting the physical properties. Examples thereof include a glycidyl group-containing polymerizable monomer such as glycidyl (meth)acrylate or allylepoxypropyl ether, and an aminoethyl (meth)acrylate or a (meth) group. An amine group-containing polymerizable monomer such as N-monoalkylaminoalkyl acrylate or N,N-dialkylaminoalkyl (meth)acrylate, vinyltrichloromethane or vinyltrimethoxydecane , an alkylene group-containing polymerizable monomer such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane and its hydrochloride, (meth)acrylic acid 2 - an aziridinyl group-containing polymerizable monomer such as aziridinyl ethyl ester, (meth) propylene decyl isocyanate, (meth) propylene decyl isocyanate phenol or methyl ethyl ketone a polymerizable monomer containing an isocyanato group and/or a blocked isocyanate group, 2-isopropenyl-2-, etc. Oxazoline, 2-vinyl-2- Oxazoline An allyl group-containing polymerizable monomer such as a polymerizable monomer having an oxazoline group, a polymerizable monomer containing a cyclopentyl group such as dicyclopentenyl (meth)acrylate, or an allyl (meth)acrylate a carbonyl group-containing vinyl monomer such as acrolein, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate , trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, diallyl phthalate, divinyl benzene, ( a hydroxymethyl group-containing acrylamide-based vinyl monomer such as methyl allyl acrylate or N-methylol acrylamide, oriconic acid, maleic acid, maleic anhydride, fumaric acid, or croton a carboxyl group-containing vinyl monomer such as acid, citraconic acid or cinnamic acid. The amount of addition is in the range of 0.01 to 3% by weight based on the total amount of the above-mentioned essential monomer components (i) and (ii), and the effect of the composition of the present invention is not affected.

The weight average molecular weight of the resin in the above-mentioned (meth)acrylic acid alkyl ester type copolymer resin fine particle dispersion emulsion must be 100,000 or more and less than 800,000, and the absorption of the solvent in the ink is good, but it is not good. Due to poor drying properties, bleeding occurs in the pixels, and the image quality of the printed matter is lowered. On the other hand, in the case of more than 800,000 people, the solvent is wetted and spread due to poor absorption of the solvent, and it is not suitable because the size and the neat shape of the object are not obtained.

The particle diameter of the above-mentioned (meth)acrylic acid alkyl ester-based copolymer resin fine particle-dispersed emulsion must be 10 nm or more and less than 500 nm in terms of the number average particle diameter, and even if it is less than 10 nm, it cannot be used in various monomer mixtures. The emulsion polymerization method employed in the present invention is obtained. On the other hand, in the case of 500 nm or more, the ink absorbability is uneven, unevenness occurs at the end portion, and a uniform pixel shape is not obtained, and the occurrence of aggregates is observed as the particle diameter becomes larger, and the present invention is lacking as the present invention. The stability of the composition of the transparent resin layer composition is not preferable. Further, the number average particle diameter referred to herein is a particle diameter obtained by analyzing the self-correlation function obtained by the dynamic light scattering method by a cumulative amount method.

The emulsion polymerization method described above is not particularly limited, and the monomer mixture, the polymerization initiator, the optional chain transfer agent or the emulsifier, etc., may be continuously supplied to the aqueous medium under stirring at a predetermined temperature. Got it. When the concentration of the mixture of the monomer mixture and the emulsifier is 10 to 80% by weight based on the total amount of the monomer mixture, the (meth)acrylic acid alkyl ester copolymer resin fine particle dispersion emulsion can be obtained stably, but in the present invention In the emulsion, it is preferably 20 to 50% by weight because it is more stable.

Examples of the polymerization initiator include persulfate such as ammonium persulfate, potassium persulfate, and sodium persulfate, benzammonium peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide. Organic peroxides such as hydrogen peroxide, hydrogen peroxide, etc., can be radically polymerized using only such peroxides, or a metal salt of the above-mentioned peroxide with ascorbic acid, formaldehyde sulfoxylate, or thio a redox polymerization initiator of a reducing agent such as sodium sulfate or ferric chloride, and 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-indenyl) The azo polymerization initiator such as a propane) dibasic acid may be used singly or in a mixture of the above.

Examples of the emulsifier include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric ionic surfactant. However, from the viewpoint of applicability to the composition of the present invention, it is preferred to use Each of the anionic surfactant and the nonionic surfactant may be used singly or in combination of two or more.

Examples of the anionic surfactants include higher fatty acid salts such as sodium oleate, alkylarylsulfonates such as sodium dodecylbenzenesulfonate, and alkyl sulfates such as sodium lauryl sulfate. a polyoxyethylene alkyl ether sulfate salt such as a salt or a polyoxyethylene lauryl ether sulfate, or a polyoxyethylene alkyl aryl ether sulfate salt such as a polyoxyethylene nonylphenyl ether sulfate or the like. An alkyl sulfosuccinate salt such as sodium octylsulfosuccinate, sodium dioctylsulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate or the like. Further, examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene. Sorbitol anhydride such as polyoxyethylene alkylphenyl ether such as nonylphenyl ether, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate Polyoxyethylene sorbitan higher fatty acid esters such as higher fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, polyoxyethylene monostearate, etc. A glycerin higher fatty acid ester such as an ethylene higher fatty acid ester, an oleic acid monoglyceride or a stearic acid monoglyceride, or a polyoxyethylene-polyoxypropylene block copolymer.

Moreover, as a surfactant other than the above-mentioned illustration, a reactive surfactant is mentioned. As an example, an alkyl sulfosuccinate alkenyl ether salt system, an alkyl sulfosuccinate alkenyl ester salt system, a methylene bis oxyethylene alkyl phenyl alkenyl ether sulfate system, and an alkyl group can be illustrated. Alkenyl succinate salt, polyoxyalkylene (meth) acrylate sulfate salt, polyoxyalkylene alkyl ether aliphatic unsaturated dicarboxylate salt, sulfoalkyl (meth) acrylate Salt, dihydroxyalkyl (meth) acrylate sulfate salt, mono or di (glycerol-1-alkylphenyl-3-allyl-2-polyoxyalkylene ether) phosphate salt A polyoxyalkylene alkylphenyl ether (meth) acrylate reactive surfactant or the like. Further, the general addition amount of the surfactant exemplified as the emulsifier is 0.1 to 20% by weight based on the total amount of the above-mentioned essential monomer components, but considering the stability of the composition of the present invention and the printing described above The property is preferably from 1 to 15% by weight.

Next, the surfactant having fluidity in (2) is a liquid or slurry-like surfactant having fluidity at room temperature of 23 ° C in addition to the above-mentioned emulsifier. The anionic surfactant, the nonionic surfactant, the lanthanoid surfactant, and the fluorine-based surfactant are selected singly or in combination of the above. Due to the addition of the surfactant, not only the permeability of the printing ink is increased, the effect of preventing the bleeding of the ink, but also the stability of the composition is increased and the leveling property of the substrate is increased. It has an effect such as an increase in defoaming property, and is therefore an essential component of the composition of the present invention.

Examples of the anionic surfactants include higher fatty acid salts such as sodium oleate and alkylarylsulfonates such as sodium dodecylbenzenesulfonate. Alkyl sulfate salts such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates such as polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyls such as polyoxyethylene nonylphenyl ether sulfate Alkyl sulfosuccinates such as aryl aryl ether sulfates, sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof Things and so on. Among the above, the alkyl chain is 4 to 18 in terms of carbon number, and the polyoxyethylene chain is preferably 4 to 22 in terms of oxyethylene as a repeating unit.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene fluorenyl groups. A sorbitan higher fatty acid such as polyoxyethylene alkylphenyl ether such as phenyl ether, sorbitan monolaurate, sorbitan monostearate or sorbitan trioleate Polyoxyethylene sorbitan higher fatty acid esters such as esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, polyoxyethylene monostearate, etc. A glycerin higher fatty acid ester such as a fatty acid ester, an oleic acid monoglyceride or a stearic acid monoglyceride, or a polyoxyethylene-polyoxypropylene block copolymer. Among the above, the alkyl chain is 2 to 22 in terms of carbon number, the polyoxyethylene chain is 2 to 22 in oxyethylene as a repeating unit, and the polyoxypropylene oxypropylene is preferably 1 to 20 in repeating units.

As an example of the lanthanoid surfactant, dimethyl hydrazine, amino decane, propylene decyl decane, vinyl benzyl decane, vinyl benzyl amide decane, glycidyl decane, decyl decane, dimethyl decane can be illustrated. , polydimethyl siloxane, polyalkoxy siloxane, hydrogen modified siloxane, vinyl modified siloxane, hydroxy modified siloxane, amine modified siloxane, carboxyl modification Oxygen Alkane, halogenated modified alkane, epoxy modified alkane, methacryloxy modified alkane, mercapto modified alkane, fluorine modified alkane, alkyl modified Oxyalkane, phenyl modified alkane, alkylene oxide modified alkane, and the like. Among the above, as the composition having high applicability to the present invention, an alkylene oxide-modified oxirane and a copolymer of an alkyl (meth) acrylate-based compound incorporating the skeleton may be mentioned. The resin is highly suitable and better.

As an example of the fluorine-based surfactant, those skilled in the art can be used, and examples thereof include tetrafluoroethylene, perfluoroalkylammonium salt, perfluoroalkylsulfonium decylamine, perfluoroalkylsulfonate sodium, and perfluoroalkyl potassium. Salt, perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium salt, perfluoroalkyl amine sulfonate, Perfluoroalkyl phosphate, perfluoroalkylalkyl compound, perfluoroalkylalkylbetaine, perfluoroalkyl halide, and the like. Among the above, as a composition having high applicability to the present invention, a perfluoroalkyl ethylene oxide adduct is further mentioned, and further, a (meth)acrylic acid acrylonitrile group incorporating the skeleton is mentioned. The copolymer resin of the ester compound is highly suitable and more preferable.

The amount of the surfactant to be added is preferably such that it does not inhibit the printing property and the adhesiveness 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 amount added is 0.1% by weight or less, the stability of the composition is lacking, or the effect of leveling or the like is lowered. When the amount is 10% by weight or more, the absorption capacity of the ink is remarkably lowered to cause bleeding or repellency, or the film strength tends to be remarkably lowered, and the range in which the above effects are more effectively obtained is more preferably 0.1 to 5% by weight.

Further, the organic solvent of the above (3) is coated by a method described later. In the method of applying the composition of the present invention, in order to impart an essential component capable of preventing the effect of skinning due to drying of the composition. When there is no addition, the dry foreign matter is accumulated in the coating apparatus at the time of continuous coating, and the adhesion of the foreign matter to the coating film, the deterioration of the flatness of the coating film, and the deterioration of the image quality of the ink printed matter occur. Further, the property required for the organic solvent is preferably such that it has a miscibility with an aqueous medium and has a boiling point of 150 to 300 °C. The reason for this is that the anti-skinning effect is not obtained when the boiling point is 150° C. or less, and the drying property is deteriorated at 300° C. or higher, the ink absorption ability is lowered, or the adhesive property tends to be exhibited.

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, and B. 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene Ethers such as alcohol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, etc. Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether acetate, ethylene glycol diethyl ether Acetate, ethylene glycol dibutyl ether 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 butyl 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, phthalic acid An ester such as diethyl ester or butyl lactate or a ketone such as cyclohexanone.

The amount of the organic solvent to be added is preferably such an amount that the amount of the coating film is not impaired by the printing property or the adhesiveness of the coating film, and is preferably from 1 to 20% by weight based on the total amount of the composition of the present invention. When the amount added is less than 1% by weight, an anti-skinning effect is obtained. Moreover, when it exceeds 20% by weight, the absorption capacity of the ink is remarkably lowered to cause bleeding or repulsion, or the conveyance property of the coated substrate is lowered due to a significant decrease in the strength of the coating film or the adhesion of the coating film. tendency.

The transparent resin layer of the present invention is a composition of the present invention, for glass, polyethylene terephthalate film, polycarbonate film, cycloolefin copolymer film, polyimine film, polynaphthalene dicarboxylic acid A supporting substrate such as an ethylene glycol film, a layer coated and dried, and as a coating method thereof, spray coating, spin coating, die coating, gravure coating, knife coating, dip coating, and ke can be used. Comma coating, kiss coating, curtain coating, air knife coating, blade coating, reverse roll coating, slit coating, etc., and as a drying method, equipped with a hot air dryer in the line Both the coating method and the off-line coating method are applicable.

Further, in the transparent resin layer of the present invention, the number average particle diameter of the resin constituting the (meth)acrylic acid alkyl ester copolymer resin fine particle dispersion emulsion is Nano size, excellent transparency. It is preferable to form a resin layer having a thickness of 1 to 30 μm using a composition of a transparent resin layer, and the light transmittance at a wavelength of 400 nm is 80% or more. Further, 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, or a decorative surface protective film by drawing an inkjet ink thereon. For example, it is suitable for obtaining display elements such as liquid crystal display devices, EL display devices, touch panels, and the like.

As described above, in the present invention, in the receiving layer of the oil-based inkjet ink, the inkjet ink accommodating the bombardment is sufficiently received, and the shape of the droplet is stabilized while controlling the droplet expansion diameter, and the transparency is excellent. The display element thus constructed is given a sharp image. These are, for example, contributing to the high-performance of color filters, insulating layers, touch panels, and the like for liquid crystal displays, electronic papers, display elements for digital signage, and the like.

Fig. 1 is a plan view showing an expansion of a dot of 1 dot.

Fig. 2 is a plan view showing a dot drawing sequence of pixels composed of 9 drops.

Fig. 3 is a plan view showing a state of goodness of a pixel composed of 9 drops.

Fig. 4 is a plan view showing a state in which a pixel composed of 9 drops is broken.

Fig. 5 is a plan view showing a pixel composed of 9 squares.

Fig. 6 is a 3D image analysis diagram showing a person who is formed in a good state between pixels.

Fig. 7 is a 3D image analysis diagram showing a state in which pixels are connected by the outflow of resin.

[Formation of the Invention] [Examples]

Next, the examples and comparative examples of the present invention are shown, but the present invention is not limited by the examples. First, the measurement used in the present invention is shown below. Evaluation method.

<solid content concentration>

The glass filter [Weight: W0 (g)] was impregnated with 1 g of the resin emulsion or the resin solution obtained in the following Examples and Comparative Examples, and weighed [W1 (g)], and the weight after heating at 105 ° C for 2 hours [W2 ( g)], obtained by the following formula.

Solid content concentration (% by weight) = 100 × (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, and dried at 70 ° C for 30 minutes, and then the obtained coating film was used, and an EXSTAR-6000 DSC differential scanning calorimeter manufactured by SII Nanotechnology Co., Ltd. was used. The measurement was carried out.

<particle size measurement>

1 g of the resin emulsion obtained in the following Synthesis Example was collected, and 5 g of pure water was added thereto, followed by measurement using FPAR-1000 manufactured by Otsuka Electronics Co., Ltd. Here, the self-correlation function obtained by the dynamic light scattering method was analyzed by a cumulative amount method to obtain a number average particle diameter.

<molecular weight>

50 mg of the resin emulsion obtained in the following Examples and Comparative Examples was collected, and 5 mL of tetrahydrofuran (THF) was added thereto, and after dissolution, the gel was used as a standard solution by gel permeation chromatography (GPC method) using THF as a solution. The weight average molecular weight (Mw) of the styrene-converted value. The measurement apparatus was a high-speed liquid chromatograph HLC-8220 manufactured by Tosoh Corporation, and a column system connected in the order of TSKgel Super H4000, 3000, 2000, and 2000 was used in the column, and measurement was performed using an RI detector.

<Preparation of a composition of a transparent resin layer>

In order to clarify the performance of the resin of the present invention, the following composition ratios are fixed and evaluated, but the respective constituents and their composition ratios are not limited by the present invention.

The resin emulsion obtained in the following synthesis example (synthesis example 1: (1)) 61.3 g, (2) Emulgen 103 (mobile surfactant: polyoxyethylene lauryl ether) 0.5 g, (3) Showa Solfine made by an electric company 10.0 g of EP (organic solvent: ethyl-3-ethoxypropionate) and 28.2 g of pure water (4) were stirred and mixed for 30 minutes or more.

Based on this operation, the compositions of the following tables were prepared and used in Examples 11 to 13 and Comparative Examples 8 to 12. Further, in the composition H, the component (3) was changed to tetraethylene glycol manufactured by Tokyo Chemical Industry Co., Ltd.

<adhesiveness>

The transparent resin layer composition obtained by the above-described formulation was spin-coated on a glass substrate, and dried at 70 ° C for 3 minutes to obtain a coated substrate. Then, another glass substrate was bonded to the coated surface, and 1 kg of the glass substrate was placed thereon. The scale hammer was placed for 5 minutes to peel the glass substrate. At this time, the tear-off person is regarded as ○, and the tear-off person is regarded as ×.

<Measurement of film thickness>

8.5 mL of the transparent resin layer composition obtained by the above-described formulation was spin-coated on a glass substrate at a number of revolutions of 200 rpm, and dried at 70 ° C for 3 minutes to prepare a coated substrate, and then a part was cut off, and a small sputum study was used. The company made ET-4000AK to measure the step difference that occurred.

<Light transmittance measurement>

The substrate with a transparent resin layer having a film thickness of 10 μm obtained in the same manner as above was measured using a U-4000 manufactured by Hitachi High-Technologies Co., Ltd., using a substrate having a wavelength of 400 nm as a reference.

<Measurement of contact angle>

The substrate with the transparent resin layer having a film thickness of μm obtained in the same manner as above was placed on a stage maintained at a level, and 0.5 μl of ethyl carbitol acetate (organic solvent: ECA) droplets from the upper tribe was placed. For the contact angle after 1 second from the ground, the high-speed contact angle meter OCAH-200 system manufactured by Yinghong Seiki Co., Ltd. was used for measurement.

<dot path>

An inkjet apparatus equipped with an inkjet head KM512M manufactured by Konica-Minolta (with a nozzle 512 hole capable of discharging 14 pl) is used, and as shown in Fig. 1, the composition of the transparent resin layer is a film thickness of about 10 μm. The pattern was drawn on a glass substrate coated with a slit coater at a dot pitch of 200 μm, and the expanded region was observed. A point having a spot diameter of 80 μm or less is regarded as a good wetting extension region.

<Pixel shape stability>

Next, as shown in FIG. 2, the first point is drawn at a distance of 50 μm from each other in the X and Y directions, and four points are drawn, and the continuous drawing is repeated so as to fill between the points, thereby forming nine overlapping pixels. Then at 60 ° C After drying for 5 minutes, when the microscope was observed at a magnification of 300 times, the pixel shape was kept as ○ as in the case of FIG. 3, and × as the pixel shape was not observed as in the case of FIG. Further, in the example of the evaluation of Fig. 4, the state of partial breakage of 5, 6, and 7 to 9 shown in Fig. 2 is displayed.

<capacity performance>

Next, the pixel of Fig. 2 is regarded as a square, and in the manner shown in Fig. 5, the adjacent cells are further depicted as 8 squares, and a total of 9 squares of pixels are formed. At this time, by using the 3D image analysis of the optical interferometer surface roughness meter manufactured by Veeco Co., the squares were aligned and evaluated as ○ (Fig. 6), and the resin was discharged due to solvent dissolution. The case where the connection was made was evaluated as × (Fig. 7), and the relationship between them was regarded as Δ.

<Receiving layer performance>

In the above evaluation, the spot diameter is 80 μm or less, the pixel shape stability is ○, and the capacity is ○, and the coating film produced by the composition of the present invention has a high ability as a receiving layer, and is evaluated as ○. Among the three items of the spot diameter, the pixel shape stability, and the capacity acceptance performance, two were evaluated as Δ, and two or less were evaluated as low capacity ×.

<Coating property>

The transparent resin layer composition prepared by the above-described formulation was applied to a 300 mm-mm glass substrate at 280 mm using a device equipped with a sizing head of 280 mm width, and continuously weighted under a nozzleless cleaning operation. Repeat this operation. In this case, when the number of sheets of the glass substrate which can be coated with a target of 280 mm is 20 or more, it is regarded as ○, and when 10 or more sheets are continuous, it is regarded as Δ, and when it is 10 or less, it is regarded as ×. .

(Synthesis Example 1)

175.3 g (1.75 mol) of methyl methacrylate, 175.3 g (1.75 mol) of ethyl acrylate, and ammonium persulfate 16.0 as a polymerization initiator were used as the composition (weight ratio) shown in Example 1 of Table 2. g (0.07 mol), etc., ate emulsifier, Latemul PD-104 (manufactured by Kao Corporation: polyoxyalkylene alkenyl ether ammonium sulfate), 36.5 g (10% by weight based on the total weight of the monomers), and 400 g of pure water were added to the beaker. The emulsification was carried out by a homogenizer, and 160 g of the inside and 200 g of pure water were placed in a 1500 mL flask equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introduction 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 ° C in a nitrogen atmosphere, and after maintaining for 30 minutes, the preliminary emulsion was continuously dropped through a dropping funnel for 3 hours, and the mixture was stirred for 5 hours to complete the polymerization after the completion of the dropwise addition. After cooling to room temperature, the solid content concentration was measured, and pure water was added so that the solid content concentration became 40%, and the resin emulsion 1 was obtained. The Tg of the resin contained in the obtained resin emulsion 1 was 41 ° C, the particle diameter of the resin particles in the emulsion was 40 nm, and the weight average molecular weight Mw was 300,000.

(Synthesis Example 2)

Methyl propylene was obtained in the form of the composition shown in Example 2 of Table 2. 175.3 g (1.75 mol) of methyl ester, 175.3 g (1.75 mol) of ethyl acrylate, 8.0 g (0.04 mol) of ammonium persulfate, and 36.5.g of Latemul PD-104 (manufactured by Kao Corporation) (relative to the total weight of the monomers, 10% by weight) and 400 g of pure water were placed in a beaker, and pre-emulsified by a homogenizer, and 160 g of the inside and 200 g of pure water were placed in a 1500 mL flask equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introduction tube, and a thermometer. The remaining 630 g of the preliminary emulsion was placed in a dropping funnel, and the temperature was raised to 70 to 80 ° C in a nitrogen atmosphere for 30 minutes. Then, the preliminary emulsion was continuously dropped through the dropping funnel for 3 hours, and the stirring was continued for 5 hours after the completion of the dropping. And complete the aggregation. After cooling to room temperature, the solid content concentration was measured, and pure water was added so that the solid content concentration became 40%, and the resin emulsion 2 was obtained. The Tg of the resin contained in the obtained resin emulsion 1 was 41 ° C, the particle diameter of the resin particles in the emulsion was 38 nm, and the weight average molecular weight Mw was 580,000.

(Synthesis Examples 3 and 4)

The resin emulsions 3 and 4 were obtained in the same manner as in Synthesis Example 1 except that methyl methacrylate or ethyl acrylate was blended in the form of the compositions shown in Examples 3 and 4 of Table 2. For each, the glass transition temperature, the particle diameter, and the weight average molecular weight were measured. The results are shown in the columns of Examples 3 and 4 of Table 2.

(Synthesis Examples 5 to 7)

In the same manner as in Example 1 of Table 2, methyl methacrylate and ethyl acrylate were blended, and in Example 5, the emulsifier was changed from Latemul PD-104. Further, a mixture of Latemul PD-104/Latemul PD-420 (manufactured by Kao Corporation: polyoxyalkylene alkenyl ether) = 4:1 was changed to Latemul PD-104/Latemul PD-420=1:4 in Example 6. The mixture was changed to a mixture of Latemul PD-104/Latemul PD-450=1:4 in Example 7, and each was blended so as to be 10% by weight based on the total weight of the monomers, and the synthesis and synthesis examples were carried out. The method described in 1 was similarly polymerized to obtain resin emulsions 5 to 7. For each, the glass transition temperature, the particle diameter, and the weight average molecular weight were measured. The results are shown in the columns of Examples 5 to 7 in Table 2.

(Synthesis examples 8 to 10)

The methyl methacrylate, butyl acrylate or 2-ethylhexyl methacrylate was blended in such a manner as to have the compositions shown in Examples 8 to 10 of Table 2, and polymerization was carried out in the same manner as in the method of Synthesis Example 1. , obtained resin emulsion 8~10. For each, the glass transition temperature, the particle diameter, and the weight average molecular weight were measured. The results are shown in the columns of Examples 8 to 10 of Table 2.

<Example 1>

The (1) resin emulsion obtained by synthesizing Example 1 was 61.3 g, (2) Emulgen 103 0.5 g manufactured by Kao Corporation, (3) Solfine EP 10.0 g manufactured by Showa Denko Co., Ltd., and (4) pure water 28.2 g, and stirred. The mixture was mixed for 30 minutes or more, and subjected to pressure filtration at 0.5 kg/cm ² with a 1.0 μm filter to obtain a desired transparent resin layer composition. Then, it was applied to Corning's glass substrate Corning EX-G (glass plate thickness: 0.75 mm) by a slit coater so that the film thickness after drying was about 10 μm, and it was dried by heat on a hot plate at 70 ° C. After 5 minutes, a glass substrate with a transparent resin layer was obtained. The film thickness of the transparent resin layer was 11 μm and there was no adhesiveness on the surface. Further, the transmittance at a wavelength of 400 nm was 92%.

Next, the glass substrate with the transparent resin layer obtained above was placed on a stage maintained at a level, and 0.5 μl of ECA droplets from the upper tribe were measured, and the contact angle after one second from the ground was measured, and it was 45°.

Continuing, using an inkjet device equipped with Konica-Minolta inkjet head KM512M (with a nozzle 512 hole capable of discharging 14 pl), as shown in Fig. 1, ECA is drawn at a pitch of 1 per 200 μm, and the extended area of the observation point is observed. . The spot diameter immediately after the drawing was 67 μm.

Next, as shown in FIG. 2, for the first point, the distance between the centers in the X and Y directions is 30 μm, and the dots are drawn, and the continuous drawing is repeated to form nine overlapping pixels. Then, when it was dried at 60 ° C for 5 minutes and observed under a microscope, it was evaluated as ○ because the pixel shape was maintained as shown in FIG. 3 .

Continuing, the pixel of Fig. 1 is regarded as a square, and as shown in Fig. 5, the manner of such adjacency is further depicted as 8 squares, and a total of 9 squares of pixels are formed. Immediately after the 3D image analysis using the optical interference type surface roughness meter, the landscape as shown in Fig. 6 was observed, and the cells were not connected by the outflow of the resin, and the squares were aligned and evaluated as ○.

According to the above evaluation results, the spot diameter was 67 μm, the pixel shape stability was ○, and the acceptance performance was ○. Therefore, it was judged that the coating film system produced by the composition shown in Example 1 had high ability as a receiving layer, and evaluation was performed. It is ○.

Furthermore, using a device equipped with a sizing machine head having a width of 280 mm, The composition shown in Example 1 was applied to a 300 mm-mm glass substrate at 280 mm, and the operation was repeated continuously in the no-head cleaning operation. As a result, 20 or more sheets were continuously applied at a target of 280 mm. The evaluation is ○.

<Examples 2 to 10>

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

<Examples 11, 12, 13>

In the composition shown in Table 1 shown above, the composition A was used in the example 11, the composition B was used in the example 12, and the composition C was used in the example 13, to obtain a transparent resin layer composition. Then, using each of these, a glass substrate each having a transparent resin layer was obtained in the same manner as in Example 1. Then, evaluation was carried out in the same manner as in Example 1, and the evaluation results are shown in Table 2.

(Refer to Synthesis Example 1)

In a manner of the composition shown in Comparative Example 1 of Table 3, 176.2 g (1.76 mol) of methyl methacrylate, 447.8 g (1.76 mol) of lauryl methacrylate, and 16.0 g (0.07 mol) of ammonium persulfate, Latemul were used. PD- 104 (manufactured by Kao Corporation) 64.0 g (10% by weight based on the total weight of the monomer) and 700 g of pure water were placed in a beaker, preliminarily emulsified by a homogenizer, and 280 g of the solution and 280 g of pure water were placed in a mixer and refluxed. , a dropping funnel, a nitrogen introduction tube, and a thermometer in a 3000 mL flask, and the remaining 1123 g of the preliminary emulsion was placed in a dropping funnel, and the temperature was raised to 70 to 80 ° C in a nitrogen atmosphere, and held for 30 minutes, and then passed through a dropping funnel. The emulsion was continuously dropped for 3 hours, and the mixture was further stirred for 5 hours to complete 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%, and the resin emulsion was obtained. The Tg of the resin contained in the obtained resin emulsion was 20 ° C, the particle diameter of the resin particles in the emulsion was 50 nm, and the weight average molecular weight Mw was 530000.

(Refer to Synthesis Example 2~7)

Methyl methacrylate and various monomers were blended in such a manner as to have the compositions shown in Comparative Examples 2 to 7 of Table 3, and polymerization was carried out in the same manner as in the method described in Reference Synthesis Example 1, to obtain each resin emulsion. For each, the glass transition temperature, the particle diameter, and the weight average molecular weight were measured. The results are shown in the columns of Examples 2 to 7 in Table 3.

(Refer to Synthesis Example 8)

In a 1500 ml four-necked flask equipped with a nitrogen gas introduction tube and a reflux tube, 175.3 g (1.75 mol) of methyl methacrylate, 175.3 g (1.75 mol) of ethyl acrylate, and 2,2'-azobis (2-A) were added. Base-butyronitrile) (AIBN) 11.5g (0.07mol) and propylene glycol monomethyl ether acetate (PGMEA) 500 g, stirred under a nitrogen atmosphere at 80 to 85 ° C for 8 hours, and stirred at 95 to 100 ° C for 5 hours to cause polymerization. After cooling to room temperature, PGMEA was added to adjust the solid content to 40% to obtain a resin solution. The resin contained in the resin solution had a glass transition temperature of 41 ° C and a weight average molecular weight of 50,000.

(Refer to Synthesis Example 9, 10)

Methyl methacrylate and ethyl acrylate were blended in such a manner as to have the compositions shown in Comparative Examples 14 and 15 of Table 3. The amount of AIBN added was changed from 0.07 mol to 0.01 mol in Comparative Example 14, and 0.005 mol in Comparative Example 15. The polymerization was carried out in the same manner as in the method described in Reference Synthesis Example 8, and each resin solution was obtained. For each, the glass transition temperature and the weight average molecular weight were measured. The results are shown in the columns of Comparative Examples 14 and 15 of Table 3.

<Comparative Example 1>

The amount of (1) resin emulsion obtained in Synthesis Example 1 was 61.3 g, (2) Emulgen 103 0.5 g manufactured by Kao Corporation, (3) Solfine EP 10.0 g manufactured by Showa Denko Co., Ltd., and (2) pure water 28.2 g, and stirred. The mixture was mixed for 30 minutes or more, and subjected to pressure filtration at 0.5 kg/cm ² with a 1.0 μm filter to obtain a desired transparent resin layer composition. Then, it was applied to Corning's glass substrate Corning EX-G (glass plate thickness: 0.75 mm) by a slit coater so as to have a film thickness of about 10 μm after drying, and then heat was applied to a hot plate at 70 ° C. After drying for 5 minutes, a glass substrate with a transparent resin layer was obtained. The film thickness of the transparent resin layer was 13 μm, and it was confirmed that the surface was adhesive. Further, the transmittance at a wavelength of 400 nm was 85%.

Next, the above substrate was placed on a stage maintained at a level, and 0.5 μl of ECA droplets were measured from the upper tribe, and the contact angle after one second from the ground was measured, and the result was 43°.

Continuing, using an inkjet device equipped with Konica-Minolta inkjet head KM512M (with a nozzle 512 hole capable of discharging 14 pl), as shown in Fig. 1, ECA is drawn at a pitch of 1 per 200 μm, and the extended area of the observation point is observed. . The spot diameter immediately after the drawing was 60 μm.

Next, as shown in FIG. 2, for the first point, the distance between the centers in the X and Y directions is 30 μm, and the dots are drawn, and the continuous drawing is repeated to form nine overlapping pixels. Then, when it was observed by a microscope after drying at 60 ° C for 5 minutes, it was evaluated as × because the pixel of Fig. 4 was broken.

Continuing, the pixel of Fig. 1 is regarded as a square, and as shown in Fig. 5, the eight squares are further drawn to form a total of nine squares. According to the 3D image analysis using the optical interference type surface roughness meter immediately thereafter, as shown in Fig. 7, the squares were connected by the outflow of the resin, and evaluated as ×.

According to the evaluation result described above, the spot diameter is 60 μm, but the pixel shape stability is ×, and the receiving capacity is ×, so that the ability of the coating film produced by the composition shown in Comparative Example 1 as the receiving layer is low, and evaluation is performed. For ×.

Further, the composition shown in Comparative Example 1 was applied to a 300 mm-mm glass substrate at 280 mm using a device equipped with a slit coater having a width of 280 mm, and was continuously repeated under a nozzleless cleaning operation. Operation, the result is that the number of substrates that can be continuously coated at a target of 280 mm is 10 Below the film, the evaluation is ×.

<Comparative Example 2>

A transparent resin layer composition of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that the resin emulsion prepared from the monomer composition described in Comparative Example 2 of Table 3 was used. Next, using this, a glass substrate with a transparent resin layer was obtained in the same manner as in Comparative Example 1. Then, the same evaluation as in Comparative Example 1 was carried out, and as a result, it was estimated that the transmittance was 75%.

Further, the spot diameter is more than 80 μm of 82 μm, but the shape stability of the pixel is ○ by maintaining the shape of nine overlapping pixels. However, even if the squares shown in Fig. 5 can be depicted, a number of pixel connections as shown in Fig. 7 were observed, and it was evaluated as Δ.

From the above evaluation results, it was judged that the coating film produced by the composition shown in Comparative Example 2 had a low ability as a receiving layer, and was evaluated as ×.

In addition, the evaluation of the other coating properties was carried out in addition to the above evaluation. As a result, the number of the substrates which can be continuously applied at a target of 280 mm was 20 or more, and was evaluated as ○.

<Comparative Example 3>

A transparent resin layer composition of Comparative Example 3 was obtained in the same manner as in Comparative Example 1 except that the resin emulsion prepared from the monomer composition described in Comparative Example 3 of Table 3 was used. Next, using this, a glass substrate with a transparent resin layer was obtained in the same manner as in Comparative Example 1. Then, implementation and comparison example 1 In the same evaluation, the spot diameter was as small as 53 μm, but since the pixel breakage as shown in Fig. 4 and the connection between the squares in Fig. 7 were observed, the shape stability and the acceptability of the pixel were evaluated as ×.

From the above evaluation results, it was judged that the coating film produced by the composition shown in Comparative Example 3 had a low ability as a receiving layer, and was evaluated as ×.

In addition, in addition to the above evaluation, other coating property evaluations were carried out, and as a result, the number of the substrates which can be continuously applied at a target of 280 mm was 10 or less, and was evaluated as ×.

<Comparative Example 4>

A transparent resin layer composition of Comparative Example 4 was obtained in the same manner as in Comparative Example 1 except that the resin emulsion of the monomer composition described in Comparative Example 4 of Table 3 was used. Next, using this, a glass substrate with a transparent resin layer was obtained in the same manner as in Comparative Example 1. Then, the same evaluation as in Comparative Example 1 was carried out, and as a result, the spot diameter was extremely large at 110 μm, and since the pixels and squares in FIGS. 2 and 5 could not be drawn, the pixel shape stability and the acceptance performance were evaluated as ×, and it was judged by The coating film produced by the composition shown in Comparative Example 4 had a low ability as a receiving layer, and was evaluated as ×.

In addition, in addition to the above evaluation, other coating property evaluations were carried out, and as a result, the number of the substrates which can be continuously applied at a target of 280 mm was 20 or more, and it was evaluated as ○.

<Comparative Examples 5 and 6>

Except that the monomer compositions described in Comparative Examples 5 and 6 of Table 3 were used. The transparent resin layer compositions of Comparative Examples 5 and 6 were obtained in the same manner as in Comparative Example 1 except that the resin emulsion was formed. Next, using this, a glass substrate with a transparent resin layer was obtained in the same manner as in Comparative Example 1. Then, the same evaluation as in Comparative Example 1 was carried out, and as a result, the transmittance was 81% and 83%, respectively, and it was estimated that the transparency was affected. Further, the spot diameters were 57 μm and 58 μm, respectively, which were the same as in the examples. However, the surface of the resin layer was coarse due to the large particle size, and a square was not obtained. Therefore, it was evaluated as Δ.

From the above evaluation results, it was judged that the ability of the coating film produced by the compositions shown in Comparative Examples 5 and 6 as the receiving layer was lower than that described in the examples, and it was judged to be moderate, and Δ was evaluated.

In addition, in addition to the above evaluation, other applicability evaluations were carried out, and as a result, when a target was applied at 280 mm, many projections derived from aggregates were observed on the surface of the substrate, and a substrate having good flatness was not obtained. , the evaluation is ×.

<Comparative Example 7>

A transparent resin layer composition of Comparative Example 7 was obtained in the same manner as in Comparative Example 1 except that the resin emulsion prepared from the monomer composition described in Comparative Example 7 of Table 3 was used. Next, using this, a glass substrate with a transparent resin layer was obtained in the same manner as in Comparative Example 1. Then, the same evaluation as in Comparative Example 1 was carried out, and as a result, the spot diameter was 62 μm, and the pixel shape of the overlapping pixels of 9 drops was maintained. However, the wettability spread due to the poor absorbability of ECA, and the capacity was not able to be drawn. ×.

Based on the above evaluation results, the composition shown in Comparative Example 7 was judged. The ability of the produced coating film as a receiving layer was lower than that described in the examples, and it was judged to be moderate, and Δ was evaluated.

In addition, the evaluation of the other coating properties was carried out in addition to the above evaluation. As a result, the number of the substrates which can be continuously applied at a target of 280 mm was 20 or more, and was evaluated as ○.

<Comparative Examples 8 to 12>

In the composition shown in Table 1 shown above, 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, and the composition G was used in Comparative Example 11, for comparison. In the example 12, the composition H was used to obtain a transparent resin layer composition. Then, using the same as in Comparative Example 1, a glass substrate each having a transparent resin layer was obtained. Then, the evaluation was carried out in the same manner as in Comparative Example 1, and the evaluation results are shown in Table 2, and the evaluation results are described below.

In Comparative Example 8, the spot diameter was as large as 82 μm, and as the ECA wetting spread, the connection between the squares as shown in Fig. 7 was observed, the acceptance performance was ×, and the capacity of the receiving layer was evaluated.

In Comparative Example 9, the coating film was adhesive, and since the shape of the 9-drop overlapping pixels was as shown in Fig. 4, the shape stability of the pixel was evaluated as ×, and since the squares were seen as shown in Fig. 7, The connection, the capacity performance is ×, and the capacity of the receiving layer is evaluated.

In Comparative Example 10, the spot diameter was as large as 81 μm, and the surface of the coating film was uneven, and some repulsion was observed in the dots, and it was impossible to draw a pixel of a certain size due to the position of the square, and the shape of 9 overlapping pixels Become like Figure 4 The shape stability of the pixel shape is ×, and since a number of joints are seen between the squares as shown in Fig. 7, the capacity is Δ. According to the above results, the acceptance layer performance was evaluated as ×.

In Comparative Example 11, the coating film was adhesive, and since the shape of the 9-drop overlapping pixels was as shown in Fig. 4, the pixel shape stability was ×, and since the pixel connection was as shown in Fig. 7, the capacity was ×. According to the above results, the acceptance layer performance was evaluated as ×.

In Comparative Example 12, the coating film had adhesiveness, and since the shape of the 9-drop overlapping pixels was as shown in Fig. 4, the pixel shape stability was ×, and since the pixel connection was as shown in Fig. 7, the capacity was ×. According to the above results, the acceptance layer performance was evaluated as ×.

Further, in addition to the above evaluation, the coating properties were evaluated in Comparative Examples 8 to 12. As a result, in Comparative Examples 10 and 11, the number of substrates which can be continuously applied at a target of 280 mm was 10 to 20 sheets, and evaluated. In the case of Δ, in Comparative Examples 8, 9, and 12, it was evaluated as ×.

<Comparative Example 13>

61.3 g of the resin solution obtained in Synthesis Example 8, 0.5 g of Emulgen 103 manufactured by Kao Corporation, and 38.2 g of Solfine EP manufactured by Showa Denko Co., Ltd. were weighed and stirred. The mixture was mixed for 30 minutes or more, and subjected to pressure filtration at 0.5 kg/cm ² using a 0.5 μm filter to obtain a desired transparent resin composition. Then, it was applied to Corning's glass substrate Corning EX-G (glass plate thickness: 0.75 mm) by a slit coater so as to have a film thickness of about 10 μm after drying, and it was 1200 Pa for 20 seconds at a normal temperature and 400 Pa at a normal temperature. The vacuum was dried for 30 seconds, and then thermally dried on a hot plate at 70 ° C for 5 minutes to obtain a glass substrate with a transparent resin layer. The film thickness of the transparent resin layer was 11 μm and there was no adhesiveness on the surface. Further, the transmittance at a wavelength of 400 nm was 88%.

Next, the above substrate was placed on a stage maintained at a level, and 0.5 μl of ECA droplets were measured from the upper tribe, and the contact angle after one second from the ground was measured, and as a result, it was 32°.

Continuing, using an inkjet device equipped with Konica-Minolta inkjet head KM512M (with a nozzle 512 hole capable of discharging 14 pl), as shown in Fig. 1, ECA is drawn at a pitch of 1 per 200 μm, and the extended area of the observation point is observed. . The spot diameter immediately after the drawing was 91 μm.

Next, as shown in FIG. 2, in the X and Y directions, four points are drawn at a distance of 50 μm from each other in the X and Y directions, and the continuous drawing is repeated so as to fill each point, and an attempt is made to form nine overlapping pixels. Since the pixels and squares in Fig. 2 and Fig. 5 could not be drawn, the shape stability and the acceptance performance of the pixel were evaluated as ×, and the ability of the coating film produced by the composition shown in Comparative Example 4 as the receiving layer was judged to be low. , the evaluation is ×.

In addition, in addition to the above evaluation, other coating property evaluations were carried out, and as a result, the number of the substrates which can be continuously applied at a target of 280 mm was 20 or more, and it was evaluated as ○.

<Comparative Examples 14, 15>

Although the evaluation was carried out in the same manner as in Comparative Example 13 described above, the pixel was not obtained in the same manner as in Comparative Example 13, and the shape stability and the acceptability of the pixel were affected. The capacity performance of the layer is evaluated.

In addition, in addition to the above evaluation, other coating property evaluations were carried out, and as a result, the number of the substrates which can be continuously applied at a target of 280 mm was 20 or more, and it was evaluated as ○.

Furthermore, the abbreviations in Tables 2 and 3 mean the following.

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)

A transparent resin layer composition comprising: (1) a mixture of (meth)acrylic acid alkyl ester (ii) having methyl methacrylate (i) and an alkyl group having 2 to 8 carbon atoms; The monomer is obtained by emulsion polymerization and polymerization, and the resin has a glass transition temperature of 10 ° C or more and less than 70 ° C, a weight average molecular weight of 100,000 or more to less than 800,000, and a number average particle diameter of 10 nm or more. A 500 nm (meth)acrylic acid alkyl ester copolymer resin fine particle dispersion emulsion, (2) a surfactant having fluidity at room temperature of 23 ° C, and (3) an organic solvent. The transparent resin layer composition of claim 1, wherein the (meth)acrylic acid alkyl ester copolymer resin fine particle dispersion emulsion (i) methyl methacrylate and (ii) have 2 to 8 carbon atoms (A) The composition ratio of the alkyl acrylate is in the range of (i): (ii) = 1:0.25 to 1:2 by weight ratio. The transparent resin layer composition according to claim 1 or 2, wherein when the resin layer is formed in a thickness of from 1 to 30 μm, the light transmittance at a wavelength of 400 nm is 80% or more. An inkjet ink receiving layer formed by forming a transparent resin layer formed of the transparent resin layer composition according to any one of claims 1 to 3 on a support substrate. A display element obtained by drawing an inkjet ink on a transparent resin layer formed using the transparent resin layer composition according to any one of claims 1 to 3.