WO2014112543A1

WO2014112543A1 - Transparent resin layer composition, receiving layer for inkjet inks which is produced using same, and display element

Info

Publication number: WO2014112543A1
Application number: PCT/JP2014/050634
Authority: WO
Inventors: 今野　高志; 和久浦野; 藤城　光一
Original assignee: 新日鉄住金化学株式会社
Priority date: 2013-01-17
Filing date: 2014-01-16
Publication date: 2014-07-24
Also published as: TW201434928A; JPWO2014112543A1; KR20150106882A; CN104918995A

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˚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 C_2-8 alkyl group, the glass transition temperature of a resin contained in the emulsion is 10˚C or higher and lower than 70˚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, ink-jet ink receiving layer and display element using the same

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

In recent years, in the industry related to ink-jet printing, where the growth is remarkable, the performance of ink-jet printers and the improvement of ink have advanced dramatically, making it possible to easily obtain high-definition and clear images similar to silver halide photographs even in ordinary households. It's getting on. For this reason, inkjet printers are not only used in homes, but are also being considered for use in the manufacture of electronic devices such as the manufacture of large advertising signs and the like, the printing of color filters for liquid crystal displays and alignment films.

Also, the improvement in image quality of inkjet prints is largely due to improvements in printing ink as well as higher performance of the printer. Specifically, the use of pigment inks, which are known to be capable of forming printed images having high colorability comparable to dye inks and superior in durability compared to conventional dye inks, has recently been in the field of printed matter. Then, it is becoming mainstream. On the other hand, as pigment inks used for electronic devices, solvent-based pigment inks in which pigment ink particles are dispersed in an organic solvent have come to be suitably used because of device reliability requirements. Also called pigment ink. Since the ink particles themselves are relatively hydrophobic, the ink can be suitably used for forming a printed image having a level of water resistance that does not cause bleeding of the printed image due to moisture in the environment on the printed substrate. Has attracted attention in recent years.

By the way, many of the conventional ink jet recording media have an ink receiving layer developed for aqueous dye inks, with the aim of improving the absorbability of aqueous media in ink and improving the fixability of dyes. It is designed (see, for example, Patent Document 1). Therefore, even if printing is performed on such an ink jet recording medium using the solvent-based pigment ink, the ink receiving layer cannot absorb the organic solvent efficiently, and as a result, high color development, bleeding and discoloration occur. Prevented clear images cannot be obtained.

In recent years, therefore, studies have been made on a receiving layer corresponding to a solvent-based pigment ink. For example, Patent Document 2 discloses that 50 to 100% by weight of methyl methacrylate and (meth) acrylic or vinylic monomers other than methylmethacrylate. A receiving agent is disclosed which forms an ink receiving layer composed mainly of an acrylic resin composed of 0 to 50% by weight of a monomer and having a weight average molecular weight of 300,000 to 1,000,000.

However, the ink receiving layer described in Patent Document 2 can sufficiently absorb the organic solvent contained in the ink when inkjet printing is performed on a relatively large medium such as an outdoor advertisement. Therefore, it may cause a significant decrease in the drying property of the ink and the occurrence of bleeding and cracks in the printed image. The ink receiving layer described in Patent Document 2 is formed by using an ink jet receiving agent in which the specific acrylic resin as described above is dissolved in an organic solvent. In some cases, a process for volatilizing a large amount of an organic solvent is required.

On the other hand, regarding the ink jet receiving layer for oil pigment inks, Patent Document 3 discloses that ink jet ink acceptance for oil pigment inks in which a vinyl polymer having a glass transition temperature of 10 to 70 ° C. and a weight average molecular weight of 800,000 or more is dispersed in an aqueous medium. Agents are disclosed. However, when oil-based ink-jet ink is dropped on a coating film obtained after drying the ink-jet receiving agent, there is a problem that when the molecular weight is 800,000 or more, the absorption speed is slow and the droplet diameter is widened. This is the same even when the glass transition temperature of the vinyl polymer is 70 ° C. or higher, and the droplet spreading has not been controlled.

JP-A-11-216945 Japanese Patent Laid-Open No. 2004-291561 Japanese Patent No. 4444218

In the receiving layer for drawing an oil-based ink-jet ink such as a solvent-based pigment ink, the present invention sufficiently receives the landed ink-jet ink and stabilizes the shape after drying while controlling the droplet spreading diameter. An object of the present invention is to provide a transparent resin layer composition for forming a receiving layer. In addition, the present invention is obtained by drawing an inkjet ink on a receiving layer for inkjet ink formed using this transparent resin layer composition and a transparent resin layer formed from the transparent resin layer composition. An object of the present invention is to provide a display element.

As means for solving such problems, the present inventors have determined that the glass transition temperature and the molecular weight of the resin constituting the Elsion particles in the transparent resin layer composition suppress the spread diameter of the ink droplets or the shape after drying. In addition to the particle size of Elsion particles in the transparent resin layer composition, it is possible to solve the problems of the prior art by coexisting a predetermined surfactant or organic solvent. The present invention was completed.

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

Further, the present invention is an ink-jet ink receiving layer in which a transparent resin layer formed using the transparent resin layer composition is formed on a support substrate. Furthermore, this invention is a display element obtained by drawing an inkjet ink on the transparent resin layer formed using the said transparent resin layer composition.

In obtaining the (meth) acrylic acid alkyl ester copolymer resin fine particle dispersed emulsion in the present invention, (i) using methyl methacrylate as an essential component so that the glass transition temperature is in the range of 10 ° C. or higher and lower than 70 ° C. (Ii) A (meth) acrylic acid alkyl ester having 2 to 8 carbon atoms is introduced and a mixed monomer containing at least (i) and (ii) is polymerized by emulsion polymerization. The resin contained in the obtained (meth) acrylic acid alkyl ester copolymer resin fine particle dispersed emulsion has a weight average molecular weight of 100,000 to less than 800,000 and a number average particle diameter of 10 to 500 nm. Less than.

The alkyl group carbon number of the (meth) acrylic acid alkyl ester of (ii) above shows the tackiness of the coating film made of the composition of the present invention or the stability of the pixel shape formed on the coating film with inkjet ink. The number of carbon atoms is 2 to 8 because there is a risk that the property may be lowered. When the number of carbon atoms is 1, the meaning of the mixed monomer is lost in the case of (i) methyl methacrylate. On the other hand, when the number of carbon atoms is 8 or more, the tackiness of the transparent resin layer is remarkably exhibited, or pixel cracking may occur due to drying performed after ink printing and drawing, which is not preferable.

The (meth) acrylic acid alkyl ester having 2 to 8 carbon atoms in the alkyl group (ii) is a kind of monomer constituting the (meth) acrylic acid alkyl ester copolymer. Examples include ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, octyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4- (meth) acrylic acid 4- Hydroxybutyl etc. are mentioned. In addition, (meth) acrylic acid alkyl ester means acrylic acid alkyl ester or methacrylic acid alkyl ester.

The glass transition temperature of the resin in the (meth) acrylic acid alkyl ester copolymer resin fine particle dispersed emulsion is in the range of 10 ° C. or higher and lower than 70 ° C. When the temperature is lower than 10 ° C., the pixels formed by printing when absorbing and drying the solvent in the ink are connected to adjacent pixels due to the outflow of the resin, and the color inks are mixed. There is a risk of cracks occurring on the printed pixels due to dissolution and drying shrinkage. Moreover, there exists a tendency for the conveyance property of a coating substrate to fall by expression of the tackiness of a coating film. On the other hand, when the temperature is 70 ° C. or higher, the solvent in the ink is poorly absorbed, so that the solvent wets and spreads, and an orderly pixel shape with a desired size may not be obtained. Since the penetration into the inside becomes uneven, the flatness of the coating film around the pixel is remarkably lowered, and as a result, the transparency may be lowered.

(I) Methyl methacrylate and (ii) (meth) acrylic acid alkyl ester having 2 to 8 carbon atoms in (meth) acrylic acid alkyl ester copolymer resin within the glass transition temperature range described in the previous section The composition ratio is preferably (i) :( ii) = 1: 0.25 to 1: 2 by weight. In particular, in a region where the weight ratio of methyl methacrylate (i) is less than this range, there is a risk of color mixing of printed matter and cracks in the print pixel as described above. It is desirable to be within this range because there is a concern about deterioration of the property.

In the copolymer resin, a monomer having a crosslinking group can be introduced within a range that does not affect the above-mentioned physical properties for the purpose of preventing the strength of the transparent resin layer and inkjet ink pixel cracks. Examples thereof include glycidyl group-containing polymerizable monomers such as glycidyl (meth) acrylate and allyl glycidyl ether, aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, (meth) acrylic acid N Amino group-containing polymerizable monomers such as N, N-dialkylaminoalkyl, vinyltrichlorosilane, vinyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and its hydrochloride Silyl group-containing polymerizable monomers, aziridinyl group-containing polymerizable monomers such as 2-aziridinylethyl (meth) acrylate, (meth) acryloyl isocyanate, phenols of (meth) acryloyl isocyanate ethyl or methyl ethyl ketoxime adducts, etc. Isocyanate Group and / or blocked isocyanate group-containing polymerizable monomers, 2-isopropenyl-2-oxazoline, oxazoline group-containing polymerizable monomers such as 2-vinyl-2-oxazoline, and cyclohexane such as (meth) acrylate dicyclopentenyl. Pentanyl group-containing polymerizable monomers, 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-hexanediol di ( (Meth) acrylic acid ester, neopentyl glycol di (meth) acrylic acid ester, trimethylolpropane tri (meth) acrylic acid ester, polyethylene glycol di (meth) acrylic acid ester, polypropylene glycol di (meth) acrylic acid ester, diary Phthalic acid esters, divinylbenzene, allyl (meth) acrylic acid esters, etc., methylol group-containing vinyl monomers such as N-methylolacrylamide, itaconic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, citraconic acid, cinnamon There are carboxyl group-containing vinyl monomers such as acids. If the amount added 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 resin fine particle dispersed emulsion must be 100,000 or more and less than 800,000, and absorption of the solvent in the ink is less than 100,000. Although it is good, since the drying property is poor, bleeding occurs in the pixels and the image quality of the printed matter is deteriorated. On the other hand, when the amount is 800,000 or more, the solvent is poorly absorbed, so that the solvent wets and spreads, and an orderly shape with a desired size cannot be obtained.

The particle diameter of the (meth) acrylic acid alkyl ester copolymer resin fine particle dispersed emulsion must be 10 nm or more and less than 500 nm in terms of number average particle diameter, and those less than 10 nm can be used in various monomer mixtures in the present invention. It cannot be obtained in the emulsion polymerization method employed. On the other hand, those having a thickness of 500 nm or more are not uniform in ink absorbability, have irregularities at the end of the dots and cannot form an orderly pixel shape, and the occurrence of aggregates is observed as the particle size increases. The transparency of the transparent resin layer composition is not preferable because it lacks stability. The number average particle size referred to here is an average particle size obtained by analyzing the autocorrelation function obtained by the dynamic light scattering method by the cumulant method.

The above emulsion polymerization method is not particularly limited, and the above monomer mixture, polymerization initiator, and optionally chain transfer agent and emulsifier are continuously supplied to the aqueous medium at a predetermined temperature and with stirring. It is obtained by doing it. If the concentration of the monomer mixture and the emulsifier mixture is 10 to 80% by weight based on the total amount charged, a (meth) acrylic acid alkyl ester copolymer resin fine particle dispersed emulsion can be stably obtained. In the emulsion of the present invention, 20 to 50% by weight is preferable for further stabilization.

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, Hydrogen peroxide etc. can be mentioned, radical polymerization using only these peroxides, or reducing agents such as the above-mentioned peroxides and ascorbic acid, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, ferric chloride, etc. And a redox polymerization initiator system in combination with azo polymerization initiators such as 4,4′-azobis (4-cyanovaleric acid) and 2,2′-azobis (2-amidinopropane) dibasic acid. These can be used singly or in combination.

Examples of the emulsifier include anionic surfactants, nonionic surfactants, cationic surfactants, and zwitterionic surfactants, but from the applicability to the composition of the present invention. It is desirable to use an anionic surfactant and a nonionic surfactant, each of which can be used alone or in combination of two or more.

Examples of the anionic surfactant include higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfate esters such as sodium lauryl sulfate, and polyoxyethylene lauryl ether. Polyoxyethylene alkyl ether sulfates such as sodium sulfate, polyoxyethylene alkylaryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate, sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, polyoxyethylene lauryl sulfosuccinic acid Examples thereof include alkylsulfosuccinic acid ester salts such as sodium and derivatives thereof. Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and other polyoxyethylene alkyl ethers. Sorbitan higher fatty acid esters such as oxyethylene alkylphenyl ethers, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene mono Polyoxyethylene higher fatty acid esters such as laurate and polyoxyethylene monostearate, oleic acid monoglyceride, stearic acid monoglyceride Glycerine higher fatty acid esters and the like, other, polyoxyethylene - can be exemplified polyoxypropylene block copolymers and the like.

Moreover, reactive surfactants can be mentioned as surfactants other than those exemplified above. Examples include alkylsulfosuccinic acid alkenyl ether salt systems, alkylsulfosuccinic acid alkenyl ester salt systems, methylene bispolyoxyethylene alkylphenyl alkenyl ether sulfate salt systems, alkylalkenyl succinic acid ester salt systems, polyoxyalkylene (meth) acrylates. Sulfate ester, polyoxyalkylene alkyl ether aliphatic unsaturated dicarboxylic acid ester salt, (meth) acrylic acid sulfoalkyl ester salt, dihydroxyalkyl (meth) acrylate sulfate ester salt, mono or di (glycerol- 1-alkylphenyl-3-allyl-2-polyoxyalkylene ether) phosphate ester-based, polyoxyalkylene alkylphenyl ether (meth) acrylate-based reactive surfactant It can be exemplified. Further, the general addition amount of the surfactants exemplified as these emulsifiers is 0.1 to 20% by weight with respect to the total amount of the essential monomer components described above, but the stability of the composition of the present invention and the aforementioned Considering printability, 1 to 15% by weight is preferable.

Next, the surfactant having fluidity (2) is added separately from the above emulsifier, and indicates a liquid or slurry surfactant having fluidity at room temperature of 23 ° C. It is a mixture of one or more selected from anionic surfactants, nonionic surfactants, silicon surfactants, and fluorine surfactants. The surfactant not only improves the penetrability of the printing ink and prevents ink bleeding, but also improves the stability of the composition and the leveling property when applied to the substrate, and the antifoaming property. Since an effect such as improvement is obtained, it is an essential component for the composition of the present invention.

Examples of anionic surfactants include higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfate salts such as sodium lauryl sulfate, polyoxyethylene lauryl ether sodium sulfate Polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene alkylaryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate, sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate, etc. Examples thereof include alkylsulfosuccinic acid ester salts and derivatives thereof. Of the above, the alkyl chain preferably has 4 to 18 carbon atoms, and the polyoxyethylene chain preferably has 4 to 22 oxyethylene as a repeating unit.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene such as polyoxyethylene octylphenyl ether and polyoxyethylene nonielphenyl ether. Sorbitan higher fatty acid esters such as alkylphenyl ethers, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate , Polyoxyethylene higher fatty acid esters such as polyoxyethylene monostearate, oleic acid monoglyceride, stearic acid monoglyceride, etc. Glycerine higher fatty acid esters, other polyoxyethylene - polyoxypropylene block copolymers and the like. Of these, the alkyl chain preferably has 2 to 22 carbon atoms, the polyoxyethylene chain preferably has 2 to 22 oxyethylene repeating units, and the polyoxypropylene chain has 1 to 20 oxypropylene repeating units.

Examples of silicone surfactants include dimethyl silicon, amino silane, acrylic silane, vinyl benzyl silane, vinyl benzicyl amino silane, glycid silane, mercapto silane, dimethyl silane, polydimethyl siloxane, polyalkoxy siloxane, hydrogen modified siloxane, vinyl modified. Siloxane, Vitroxy modified siloxane, Amino modified siloxane, Carboxyl modified siloxane, Halogenated modified siloxane, Epoxy modified siloxane, Methacryloxy modified siloxane, Mercapto modified siloxane, Fluorine modified siloxane, Alkyl group modified siloxane, Phenyl modified siloxane, Alkylene oxide modified siloxane etc. It can be illustrated. Among them, alkylene oxide-modified siloxane is exemplified as one having high applicability to the composition of the present invention, and a copolymer resin with a (meth) acrylic acid alkyl ester compound in which the skeleton is further incorporated is applicable. Is higher and more preferable.

As examples of the fluorosurfactant, known ones can be used. For example, tetrafluoroethylene, perfluoroalkyl ammonium salt, perfluoroalkyl sulfonic acid amide, sodium perfluoroalkyl sulfonate, perfluoroalkyl potassium. Salt, perfluoroalkylcarboxylate, perfluoroalkylsulfonate, perfluoroalkylethylene oxide adduct, perfluoroalkyltrimethylammonium salt, perfluoroalkylaminosulfonate, perfluoroalkyl phosphate ester, perfluoroalkylalkyl compound And perfluoroalkylalkylbetaines, perfluoroalkyl halides, and the like. Among them, a perfluoroalkylethylene oxide adduct is mentioned as one having high applicability to the composition of the present invention, and a copolymer resin with a (meth) acrylic acid acrylic ester compound in which the skeleton is further incorporated. High applicability and more preferable.

The addition amount of the surfactant is preferably an addition amount that does not impair the printing properties, tackiness and the like on the coating film, and is 0.1 to 10% by weight based on the total amount of the composition of the present invention. Is preferred. When the addition amount is 0.1% by weight or less, the composition lacks stability or the effects such as leveling properties are reduced. In addition, when the content is 10% by weight or more, the ink absorption ability is remarkably lowered to cause bleeding and repelling, and the coating film strength tends to be remarkably lowered. 5% by weight is more preferred.

Next, the organic solvent (3) provides an effect of preventing skinning due to drying of the composition when the composition of the present invention is applied by a coating method described later. , An essential ingredient. When no additive is added, dry foreign matter accumulates on the coating equipment during continuous coating, resulting in 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. There is a fear. Further, the properties required for the organic solvent are preferably those having miscibility with an aqueous medium and a boiling point of 150 to 300 ° C. The reason for this is that the effect of preventing skinning cannot be obtained when the boiling point is 150 ° C. or lower, and when 300 ° C. or higher, the drying property deteriorates and the ink absorbability tends to decrease, or tackiness tends to be exhibited. .

Examples of the organic solvent include alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, phenyl ether, ethylene glycol Monobenzyl ether, ethylene glycol monoethyl hexyl 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 Ethers such as 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, tripropylene glycol monomethyl ether, ethylene 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 No ethyl 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 , Esters such as diethyl phthalate and butyl lactate, and ketones such as cyclohexanone.

The addition amount of the organic solvent is preferably such that it does not impair the printing properties and tackiness 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 skinning cannot be obtained. On the other hand, if it exceeds 20% by weight, the ink absorption ability is remarkably lowered to cause bleeding and repellency, or the coating film strength is significantly lowered and the transportability of the coated substrate is lowered due to the appearance of the tackiness of the coating film. There is a tendency.

The transparent resin layer of the present invention is obtained by coating the composition of the present invention on a supporting substrate such as glass, polyethylene terephthalate film, polycarbonate film, cycloolefin copolymer film, polyimide film, polyethylene naphthalate film, and drying. The coating method includes spray coating, spin coating, die coating, gravure coating, knife coating, dip coating, comma coating, kiss coating, curtain coating, air knife coating, blade coating, reverse roll coating, slit coating, etc. As a drying method, any of an in-line coating method and an offline coating method in which a hot air dryer is arranged can be applied.

The transparent resin layer of the present invention is excellent in transparency because the number average particle diameter of the resin constituting the (meth) acrylic acid alkyl ester copolymer resin fine particle dispersed emulsion is nano-sized. Preferably, when a resin layer having a thickness of 1 to 30 μm is formed using the transparent resin layer composition, the light transmittance at a wavelength of 400 nm is 80% or more. And the transparent resin layer formed using the transparent resin layer composition in this invention draws an inkjet ink on it, for example, a color filter, a transparent conductive film, a surface protection film with a decoration, etc. It is suitable for obtaining a display element such as a liquid crystal display device, an EL display device, a touch panel, or the like.

As described above, in the receiving layer for drawing the oil-based ink-jet ink, the ink-jet ink that has landed sufficiently is received, the shape after drying is stabilized while controlling the droplet spreading diameter, and the transparency is excellent. Therefore, the display element constituted thereby gives a clear image. These contribute to high-definition of color filters, insulating layers, touch panels, and the like of liquid crystal displays, electronic paper, and digital signage display elements.

Plane observation view showing the spread of dots at one dot Plan view showing the dot drawing order of 9-drop pixels Plane observation diagram showing a good state of a pixel consisting of 9 drops Plane observation diagram showing the state where the tear of the pixel consisting of 9 drops has occurred Plan view showing pixels consisting of 9 squares 3D image analysis diagram showing that pixels are formed in good condition 3D image analysis diagram showing a state in which pixels are connected by the outflow of resin

Next, examples and comparative examples of the present invention will be shown, but the present invention is not limited to these examples. First, the measurement / evaluation method used in the present invention is shown below.

<Concentration of solid content>
After impregnating 1 g of the resin emulsion or resin solution obtained in the following Examples and Comparative Examples into a glass filter [weight: W0 (g)] and weighing [W1 (g)], and heating at 105 ° C. for 2 hours From the weight [W2 (g)] of
Solid content concentration (% by weight) = 100 × (W2-W0) / (W1-W0)

<Glass transition temperature>
The resin emulsions obtained in the following examples and comparative examples were spin-coated on a glass substrate and dried at 70 ° C. for 30 minutes. Measurement was performed using a differential scanning calorimeter.

<Particle size measurement>
1 g of the resin emulsion obtained in the following synthesis example was collected and added with pure water to make 5 g, and then measured using an FPAR-1000 manufactured by Otsuka Electronics Co., Ltd. Here, the autocorrelation function obtained by the dynamic light scattering method was analyzed by the cumulant method to obtain the number average particle size.

<Molecular weight>
50 mg of the resin emulsions obtained in the following Examples and Comparative Examples were collected, and 5 mL of tetrahydrofuran (THF) was added and dissolved, followed by gel permeation chromatography method (GPC method) using THF as an eluent. The weight average molecular weight (Mw) was determined as a standard polystyrene equivalent value. A high-performance liquid chromatograph HLC-8220 manufactured by Tosoh Corporation was used as a measuring device, and a column system connected in the order of TSKgel SuperH4000, 3000, 2000, 2000 was used as a column, and measurement was performed using an RI detector.

<Preparation of transparent resin layer composition>
In order to clarify the performance of the resin of the present invention, evaluation was carried out with the following composition ratios fixed, but each component and its composition ratio are not limited in the present invention.
Resin emulsion obtained in the following synthesis example (Synthesis example 1: (1)) 61.3 g, (2) Emulgen 103 (fluid surfactant: polyoxyethylene lauryl ether) manufactured by Kao Corporation, (3 ) 10.0 g of Solfine EP (organic solvent: ethyl-3-ethoxypropionate) manufactured by Showa Denko KK and (4) 28.2 g of pure water were weighed, and stirred and mixed for 30 minutes or more.
Based on this operation, compositions as shown in the following table were prepared and used in Examples 11 to 13 and Comparative Examples 8 to 12. In composition H, component (3) was changed to tetraethylene glycol manufactured by Tokyo Chemical Industry.

<Tackiness>
A transparent resin layer composition having the composition shown above 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 The weight was placed and left for 5 minutes, and the glass substrate was peeled off. At this time, if it can be peeled off, it was marked as ◯, and if it could not be peeled off, it was marked as x.

<Film thickness measurement>
After producing a coated substrate obtained by spin-coating 8.5 mL of the transparent resin layer composition having the above composition on a glass substrate at a rotation speed of 200 rpm and drying at 70 ° C. for 3 minutes, The level difference that can be obtained by scraping the surface was measured using an ET-4000AK manufactured by Kosaka Laboratory.

<Light transmittance measurement>
A substrate with a transparent resin layer having a film thickness of 10 μm obtained by the same method as above was measured with U-4000 manufactured by Hitachi High-Tech Fielding Co., Ltd., using the substrate itself as a reference with a wavelength of 400 nm.

<Contact angle measurement>
Place a substrate with a transparent resin layer with a film thickness of μm obtained in the same manner as above on a table that is kept horizontal, drop 0.5 μl of ethyl carbitol acetate (organic solvent: ECA) droplets from the top, The contact angle 1 second after landing was measured using a high-speed contact angle meter OCAH-200 system manufactured by Eihiro Seiki Co., Ltd.

<Dot diameter>
Using an inkjet apparatus equipped with a Konica Minolta inkjet head KM512M (equipped with a nozzle that can eject 14 pl), the ECA has a thickness of about 10 μm as shown in FIG. On the glass substrate coated with the slit coater, the spread area was observed by drawing with one dot every 200 μm pitch. Those having a dot system of 80 μm or less were regarded as good wet spread areas.

<Pixel shape stability>
Subsequently, as shown in FIG. 2, four dots are drawn with the distance between the centers to be 50 μm in the X and Y directions with respect to the first dot, and repeated continuously so as to fill the space between the dots. Nine drops of overlapping pixels were formed by drawing. Thereafter, when the sample was dried at 60 ° C. for 5 minutes and observed with a microscope at a magnification of 300 times, if the pixel shape was maintained as in the example of FIG. 3, the pixel shape was maintained as in the example of FIG. Otherwise, it was marked as x. Note that the x evaluation example in FIG. 4 shows a state where the

dots

5, 6, and 7 to 9 shown in FIG. 2 are broken.

<Acceptance performance>
Next, assuming that the pixels in FIG. 2 are one square, and further adjacent eight squares are drawn as shown in FIG. 5, pixels in a total of nine squares are formed. At this time, when 3D image analysis using an optical interference type surface roughness meter manufactured by Veeco was used, the evaluation was ○ when the cells were neatly arranged (FIG. 6). In the case of connection, the evaluation is x (FIG. 7), and the interval between them is Δ.

<Receiving layer performance>
Among the above evaluations, a film having a dot diameter of 80 μm or less, a pixel shape stability of ○, and a receptive performance of ○ is evaluated as having a high ability as a coating layer made from the composition of the present invention. The dot system, the pixel shape stability, and the receptive performance satisfying two of the three items were evaluated as Δ.

<Coating property>
Using a device with a slit coater head having a width of 280 mm, the transparent resin layer composition having the composition shown above is continuously applied to a 300 mm glass substrate at 280 mm without a head cleaning operation. And repeated. Here, the target number of glass substrates coated at 280 □ mm is ○ when the number is 20 or more, Δ when the number is 10 or more and 20 or less continuously, and × when the number is 10 or less continuously. .

(Synthesis Example 1)
175.3 g (1.75 mol) of methyl methacrylate, 175.3 g (1.75 mol) of ethyl acrylate, and ammonium persulfate as a polymerization initiator so that the composition (weight ratio) shown in Example 1 of Table 2 is obtained. 0g (0.07 mol), Latemul PD-104 (manufactured by Kao Corporation: polyoxyalkylene alkenyl ether ammonium sulfate) as an emulsifier 36.5 g (10% by weight based on the total monomer weight), 400 g of pure water were charged into a beaker and preliminarily prepared with a homogenizer. Emulsify, 160 g of that and 200 g of pure water are charged into a 1500 mL flask equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube and thermometer, and the remaining 627 g of the pre-emulsified liquid is charged into the dropping funnel. After raising the temperature to 70 to 80 ° C. and holding for 30 minutes in an atmosphere, reserve from the dropping funnel Continuously added dropwise over of liquid 3 hours to terminate the polymerization and stirring continued After completion of the dropwise 5 hours. After cooling to room temperature, the solid content concentration was measured, and pure water was added so that the solid content concentration was 40% to obtain a resin emulsion 1. 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 = 300,000.

(Synthesis Example 2)
In order to achieve the composition shown in Example 2 of Table 2, methyl methacrylate 175.3 g (1.75 mol), ethyl acrylate 175.3 g (1.75 mol), ammonium persulfate 8.0 g (0.04 mol), latemul PD-104 (manufactured by Kao Corporation) 36.5. g (10% by weight with respect to the total weight of monomers), 400 g of pure water was charged into a beaker and pre-emulsified with a homogenizer, and 160 g and 200 g of pure water were agitated, reflux condenser, dropping funnel, nitrogen inlet tube and thermometer. The remaining 630 g of the preliminary emulsion was charged into a dropping funnel and heated to 70-80 ° C. under a nitrogen atmosphere and maintained for 30 minutes, and then the preliminary emulsion was added from the dropping funnel for 3 hours. The solution was continuously dropped over a period of 5 hours after the dropping was completed, and the polymerization was terminated by stirring. After cooling to room temperature, the solid content concentration was measured, and pure water was added so that the solid content concentration was 40% to obtain a resin emulsion 2. The Tg of the resin contained in the obtained resin emulsion 2 was 41 ° C., the particle size of the resin particles in the emulsion was 38 nm, and the weight average molecular weight Mw = 5800000.

(Synthesis Examples 3 and 4)

Resin emulsions

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

(Synthesis Examples 5 to 7)
In the same manner as in Example 1 in Table 2, methyl methacrylate and ethyl acrylate were blended. In Example 5, the emulsifiers were Latemul PD-104 to Latemul PD-104 / Latemuru PD-420 (manufactured by Kao Corporation: Polyoxy Alkylene alkenyl ether) = 4: 1, changed to a mixture of Latem PD-104 / latemul PD-420 = 1: 4 in Example 6, and changed to a mixture of Latem PD-104 / latem PD in Example 7. The mixture was changed to a mixture of −450 = 1: 4 and blended so as to be 10% by weight with respect to the total weight of the monomers. Otherwise, polymerization was performed in the same manner as described in Synthesis Example 1, and resin emulsions 5 to 7 was obtained. The glass transition temperature, particle diameter, and weight average molecular weight were measured for each. 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 blended so as to have the compositions shown in Examples 8 to 10 in Table 2, and polymerized in the same manner as described in Synthesis Example 1 to obtain resin emulsions 8 to 10 was obtained. The glass transition temperature, particle diameter, and weight average molecular weight were measured for each. The results are shown in Examples 8 to 10 in Table 2.

<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) pure 28.2 g of water was weighed, stirred and mixed for 30 minutes or more, and subjected to pressure filtration with a 1.0 μm filter at 0.5 kg / cm ² to obtain a desired transparent resin layer composition. Next, using this, a glass substrate Corning EX-G (glass plate thickness 0.75 mm) manufactured by Corning Co., Ltd. was applied by slit coating so that the film thickness after drying was about 10 μm, and was applied on a hot plate at 70 ° C. And dried 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 the surface was not tacky. Further, the transmittance at a wavelength of 400 nm was 92%.

Subsequently, the glass substrate with the transparent resin layer obtained as described above was placed on a table that was kept horizontal, 0.5 μl of ECA droplets were dropped from the top, and the contact angle after 1 second from the landing was measured. It was 45 °.

Subsequently, using an inkjet apparatus equipped with a Konica Minolta inkjet head KM512M (equipped with a nozzle that can eject 14 pl), as shown in FIG. 1, the ECA is drawn at one dot every 200 μm pitch. The spreading area was observed. The dot diameter immediately after drawing was 67 μm.

Subsequently, as shown in FIG. 2, the dots are drawn with the center-to-center distance being 30 μm apart in the X and Y directions with respect to the first dot, and this is repeated continuously to draw nine drops. Pixels were formed. Thereafter, when the sample was dried at 60 ° C. for 5 minutes and observed with a microscope, the pixel shape was maintained as shown in FIG.

Subsequently, the pixels of FIG. 1 were taken as one square, and as shown in FIG. 5, a further 9 squares were drawn so as to be adjacent to each other, thereby forming a total of 9 square pixels. Since the landscape as shown in FIG. 6 was observed from the 3D image analysis using the optical interference type surface roughness meter immediately after that, the grids were not connected by the outflow of the resin, and the grids were neatly arranged. ○.

From the above evaluation results, since the dot diameter was 67 μm, the pixel shape stability was ○, and the receiving performance was ○, the coating film made from the composition shown in Example 1 has a high ability as the receiving layer. It was set as ○ evaluation judged to be a thing.

Furthermore, the operation of coating the composition shown in Example 1 with a 280 mm wide slit coater head on a 300 □ mm glass substrate at 280 □ mm was repeated without a head cleaning operation. Since 20 or more sheets could be continuously coated at the target 280 □ mm, it was evaluated as “Good”.

<Examples 2 to 10>
Transparent resin layer compositions according to Examples 2 to 10 were obtained in the same manner as in Example 1 except that (1) resin emulsions 2 to 10 obtained in Synthesis Examples 2 to 10 were used, respectively. . Next, using these, each glass substrate with a transparent resin layer was obtained in the same manner as in Example 1. Various evaluations were performed in the same manner as in Example 1, and the evaluation results are shown in Table 2.

<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. Next, using these, each glass substrate with a transparent resin layer was obtained in the same manner as in Example 1. And evaluation was implemented similarly to Example 1, and the evaluation result was described 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, lathemul so as to have the composition shown in Comparative Example 1 of Table 3 PD-104 (manufactured by Kao Corporation) 64.0 g (10% by weight with respect to the total weight of monomers) and 700 g of pure water were placed in a beaker and pre-emulsified with a homogenizer. Into a 3000 mL flask equipped with a dropping funnel, a nitrogen introducing tube and a thermometer, the remaining 1123 g of the preliminary emulsion was charged into the dropping funnel, heated to 70-80 ° C. under a nitrogen atmosphere, and held for 30 minutes. The emulsion was continuously dropped from the dropping funnel over 3 hours, and stirred for 5 hours after the dropping was completed 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 was 40% to obtain a resin emulsion. 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 = 530000.

(Reference Synthesis Examples 2 to 7)
Methyl methacrylate and various monomers were blended so as to have the 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 each resin emulsion. The glass transition temperature, particle diameter, and weight average molecular weight were measured for each. The results are shown in Examples 2 to 7 in Table 3.

(Reference Synthesis Example 8)
In a 1500 ml four-necked flask equipped with a nitrogen introduction tube and a reflux tube, 175.3 g (1.75 mol) of methyl methacrylate, 175.3 g (1.75 mol) of ethyl acrylate, 2,2′-azobis (2-methyl-butyronitrile) ) (AIBN) 11.5 g (0.07 mol) and propylene glycol monomethyl ether acetate (PGMEA) 500 g were charged and polymerized by stirring at 80 to 85 ° C. for 8 hours and at 95 to 100 ° C. for 5 hours in a nitrogen atmosphere. It was. After cooling to 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 ° C. and a weight average molecular weight of 50,000.

(Reference Synthesis Examples 9 and 10)
Methyl methacrylate and ethyl acrylate were prepared so as to have the compositions shown in Comparative Examples 14 and 15 of Table 3, and the amount of AIBN added was 0.07 mol to 0.01 mol in Comparative Example 14, and 0.2 in Comparative Example 15. Polymerization was carried out in the same manner as described in Reference Synthesis Example 8 while changing to 005 mol to obtain each resin solution. The glass transition temperature and the weight average molecular weight were measured for each. The results are shown in Comparative Examples 14 and 15 in Table 3.

<Comparative Example 1>
61.3 g of the resin emulsion obtained in Reference 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, (4) Pure 28.2 g of water was weighed, stirred and mixed for 30 minutes or more, and subjected to pressure filtration with a 1.0 μm filter at 0.5 kg / cm ² to obtain a desired transparent resin layer composition. Next, using this, it was applied to a glass substrate Corning EX-G (glass thickness 0.75 mm) manufactured by Corning by slit coating so that the film thickness after drying was about 10 μm, and then applied to a hot plate at 70 ° C. And dried for 5 minutes to obtain a glass substrate with a transparent resin layer. The film thickness of the transparent resin layer was 13 μm, and tackiness was confirmed on the surface. Further, the transmittance at a wavelength of 400 nm was 85%.

Subsequently, the substrate was placed on a table that was kept horizontal as described above, 0.5 μl of ECA droplet was dropped from the top, and the contact angle one second after landing was measured to be 43 °.

Subsequently, using an inkjet apparatus equipped with a Konica Minolta inkjet head KM512M (equipped with a nozzle that can eject 14 pl), as shown in FIG. 1, the ECA is drawn at one dot every 200 μm pitch. The spreading area was observed. The dot diameter immediately after drawing was 60 μm.

Subsequently, as shown in FIG. 2, the dots are drawn with the center-to-center distance being 30 μm apart in the X and Y directions with respect to the first dot, and this is repeated continuously to draw nine drops. Pixels were formed. Thereafter, when the sample was dried at 60 ° C. for 5 minutes and observed with a microscope, the pixel was torn as shown in FIG.

Subsequently, the pixels of FIG. 1 were taken as one square, and as shown in FIG. 5, eight more squares were drawn so as to be adjacent to form a total of nine square pixels. From the 3D image analysis using the optical interference type surface roughness meter immediately after that, as shown in FIG. 7, the grids were connected by the outflow of the resin.

From the above evaluation results, the dot diameter was 60 μm, but the pixel shape stability was x and the receptive performance was x. Therefore, the coating film made from the composition shown in Comparative Example 1 has the ability as a receptive layer. X was evaluated as low.

Furthermore, when the composition shown in Comparative Example 1 was applied to a 300 □ mm glass substrate at 280 □ mm using an apparatus provided with a 280 mm wide slit coater head, the operation was repeated without a head cleaning operation. Since the number of substrates that could be continuously coated at a target of 280 mm was 10 or less, it was evaluated as x.

<Comparative Example 2>
A transparent resin layer composition according to Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that a resin emulsion having a 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. And when evaluation similar to the comparative example 1 was implemented, since the transmittance | permeability was 75%, it is estimated that it influences transparency.

In addition, although the dot diameters exceeded 82 μm and 80 μm, the shape of the pixel that overlapped 9 drops was maintained, so the pixel shape stability was evaluated as “good”. However, even though the cells shown in FIG. 5 could be drawn, the pixel connection as shown in FIG.
From the above evaluation results, the coating film made from the composition shown in Comparative Example 2 was evaluated as x evaluation that was judged to have a low ability as a receiving layer.

Furthermore, in addition to the above evaluations, coating property evaluation was performed. As a result, the number of substrates that could be continuously coated at a target of 280 □ mm was 20 or more, so it was rated as “Good”.

<Comparative Example 3>
A transparent resin layer composition according to Comparative Example 3 was obtained in the same manner as Comparative Example 1 except that the resin emulsion having 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, when the same evaluation as in Comparative Example 1 was performed, the dot diameter was as small as 53 μm. However, the pixel breaks as shown in FIG. 4 and the connections between the squares as shown in FIG. 7 were observed. The pixel shape stability and the acceptance performance evaluation were evaluated as x.
From the above evaluation results, the coating film made from the composition shown in Comparative Example 3 was evaluated as x evaluation that was judged to have low ability as a receiving layer.

Furthermore, in addition to the above evaluation, coating property evaluation was performed, and the number of substrates that could be continuously coated at a target of 280 □ mm was 10 or less.

<Comparative example 4>
A transparent resin layer composition according to Comparative Example 4 was obtained in the same manner as 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 with 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 performed, the dot diameter was as large as 110 μm, and the pixels and grids as shown in FIGS. 2 and 5 could not be drawn. The evaluation was x, and the coating film made from the composition shown in Comparative Example 4 was evaluated as x, which was judged to have a low ability as a receiving layer.

Further, in addition to the above evaluation, coating property evaluation was performed. As a result, the number of substrates that could be continuously coated at a target of 280 □ mm was 20 or more.

<Comparative Examples 5 and 6>
Transparent resin layer compositions according to Comparative Examples 5 and 6 were obtained in the same manner as Comparative Example 1 except that the resin emulsions having the monomer compositions described in Comparative Examples 5 and 6 in Table 3 were used. Next, using this, a glass substrate with a transparent resin layer was obtained in the same manner as in Comparative Example 1. And when the same evaluation as Comparative Example 1 was performed, the transmittances were 81% and 83%, respectively, and it is assumed that the transparency was affected. Further, the dot diameters were 57 μm and 58 μm, respectively, which were the same as those in the examples. However, the resin layer surface was coarse due to the large particle diameter, and no regular grid was obtained.
Based on the above evaluation results, the coating films made from the compositions shown in Comparative Examples 5 and 6 were evaluated as Δ evaluations that were judged to be moderate and lower in capacity as receiving layers than those described in the Examples.

Furthermore, in addition to the above evaluation, when coating property evaluation was performed, when coating was performed at the target 280 mm, a large number of projections derived from aggregates were observed on the substrate surface, and a substrate with good flatness was obtained. Since it was not possible, it was set as x evaluation.

<Comparative Example 7>
A transparent resin layer composition according to Comparative Example 7 was obtained in the same manner as 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 with a transparent resin layer was obtained in the same manner as in Comparative Example 1. Then, when the same evaluation as in Comparative Example 1 was performed, the dot diameter was 62 μm and the pixel shape of nine overlapping pixels was maintained. Since the eyes could not be drawn, the acceptance performance was set to x.
From the above evaluation results, the coating film made from the composition shown in Comparative Example 7 was evaluated as Δ evaluation that was judged to be moderate as the receiving layer having a lower ability than those described in the Examples.

<Comparative Examples 8-12>
In the composition described in Table 1 above, composition D in comparative example 8, composition E in comparative example 9, composition F in comparative example 10, composition G in comparative example 11, and composition 12 in comparative example 12 Composition H was applied to obtain a transparent resin layer composition. Next, using these, each glass substrate with a transparent resin layer was obtained in the same manner as in Comparative Example 1. And evaluation is implemented similarly to the comparative example 1, the evaluation result is described in Table 2, and the evaluation reason is described below.

In Comparative Example 8, since the dot diameter was as large as 82 μm and the ECA wetted and spread, the connection between the cells was seen as shown in FIG.

In Comparative Example 9, the coating film has tackiness, and the shape of the pixel that overlaps 9 drops is as shown in FIG. 4, so that the pixel shape stability is indicated as x, and further, the connection between the squares is visible as shown in FIG. Therefore, the receiving performance was evaluated as x, and the receiving layer performance was evaluated as x.

In Comparative Example 10, the dot diameter is as large as 81 μm, the coating film surface is not uniform, and some repellency is observed on the dots, a pixel of a certain size cannot be drawn depending on the position of the square, and 9 drops overlap Since the shape of the pixel was as shown in FIG. 4, the pixel shape stability was evaluated as x, and since a slight connection was observed between the cells as shown in FIG. From the above results, the receiving layer performance was evaluated as x evaluation.

In Comparative Example 11, the coating film has tackiness, and the shape of the pixel that overlaps 9 drops is as shown in FIG. 4, so that the pixel shape stability is x, and further, the pixels are connected as shown in FIG. The acceptability was marked with x. From the above results, the receiving layer performance was evaluated as x evaluation.

In Comparative Example 12, the coating film has tackiness, and the shape of the pixel that overlaps 9 drops is as shown in FIG. 4, so that the pixel shape stability is x, and further, the pixels are connected as shown in FIG. The acceptability was marked with x. From the above results, the receiving layer performance was evaluated as x evaluation.

Further, in addition to the above evaluation, when the coating properties were evaluated in Comparative Examples 8 to 12, in Comparative Examples 10 and 11, the target number of substrates that could be continuously coated at 280 mm was 10 to 20 Since it was a sheet, since Comparative Example 8, 9, and 12 were 10 sheets or less, it was set as x evaluation in △ evaluation.

<Comparative Example 13>
61.3 g of the resin solution obtained in Reference Synthesis Example 8, 0.5 g of Emulgen 103 manufactured by Kao Co., Ltd., and 38.2 g of Solfine EP manufactured by Showa Denko Co., Ltd. were weighed, and stirred and mixed for 30 minutes or more. Was filtered under pressure at 0.5 kg / cm ² to obtain a desired transparent resin composition. Next, using this, a glass substrate Corning EX-G (glass plate thickness 0.75 mm) manufactured by Corning Co., Ltd. was coated with a slit coat so that the film thickness after drying was about 10 μm, and 20 ° C. at 1200 Pa at room temperature. The film was vacuum-dried at 400 Pa for 30 seconds and then heat-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 the surface was not tacky. Further, the transmittance at a wavelength of 400 nm was 88%.

Subsequently, the substrate was placed on a table that was kept horizontal as described above, 0.5 μl of ECA droplet was dropped from the top, and the contact angle one second after landing was measured to be 32 °.

Subsequently, using an inkjet apparatus equipped with a Konica Minolta inkjet head KM512M (equipped with a nozzle that can eject 14 pl), as shown in FIG. 1, the ECA is drawn at one dot every 200 um pitch. The spreading area was observed. The dot diameter immediately after drawing was 91 μm.

Subsequently, as shown in FIG. 2, four dots are drawn with the distance between the centers to be 50 μm in the X and Y directions with respect to the first dot, and repeated continuously so as to fill the space between the dots. Although we tried to form a pixel with 9 drops by drawing, the pixels and grids as shown in FIGS. 2 and 5 could not be drawn. The coating film made from the composition shown in No. 4 was evaluated as x evaluated as having a low ability as a receiving layer.

<Comparative Examples 14 and 15>
Evaluation was performed in the same manner as in Comparative Example 13 described above. However, since pixels were not obtained in the same manner as in Comparative Example 13, pixel shape stability, receptive performance, and receptive layer performance were evaluated as x.

The meanings of the 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

(1) A resin obtained by polymerizing a mixed monomer containing methyl methacrylate (i) and (meth) acrylic acid alkyl ester (ii) having 2 to 8 carbon atoms in an alkyl group by emulsion polymerization, (Meth) acrylic acid alkyl ester copolymer 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 size of 10 nm or more and less than 500 nm. A transparent resin layer composition comprising a polymer resin fine particle-dispersed emulsion, (2) a surfactant having fluidity at room temperature of 23 ° C., and (3) an organic solvent.
The composition ratio of (i) methyl methacrylate and (ii) (meth) acrylic acid alkyl ester having 2 to 8 carbon atoms in the (meth) acrylic acid alkyl ester copolymer resin fine particle dispersed emulsion is as follows: 2. The transparent resin layer composition according to claim 1, wherein (i) :( ii) = 1: 0.25 to 1: 2.
3. The transparent resin layer composition according to claim 1, wherein when the resin layer is formed in a thickness range of 1 to 30 μm, the light transmittance at a wavelength of 400 nm is 80% or more.
An inkjet ink receiving layer, wherein a transparent resin layer formed 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 inkjet ink on a transparent resin layer formed using the transparent resin layer composition according to any one of claims 1 to 3.