JP2015114588A - Resin composition for light-scattering layer, light-scattering layer, and organic electroluminescence device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To minimize influences of a scattering layer on layers to be formed thereon by improving flatness of the scattering layer itself, to prevent generation of dark spots or short circuits, and to extend a service life of an organic EL device.SOLUTION: A resin composition for a light-scattering layer is provided, which comprises light-scattering particles (E) having an average primary particle diameter of 200 to 800 nm, inorganic oxide fine particles (F) having a minor axial diameter of 5 to 60 nm in primary particles, and a polyester dispersant (D).

Description

  The present invention relates to a resin composition for a light scattering layer used to increase the luminous efficiency of an organic electroluminescence (hereinafter also referred to as EL) device, a light scattering layer formed from the resin composition for a light scattering layer, and the The present invention relates to an organic EL device having a light scattering layer.

An organic EL element is a self-luminous element utilizing the principle that a fluorescent substance or the like emits light by recombination energy between holes injected from an anode and electrons injected from a cathode when an electric field is applied. In recent years, organic EL elements have been actively researched and developed in applications such as lighting devices and display devices.
In this specification, the “organic EL device” refers to all devices using organic EL elements such as an organic EL lighting device and an organic EL display device.

  For example, the organic EL display device has advantages in terms of visibility and viewing angle as compared with conventional CRTs and LCDs, and has excellent features such as weight reduction, thinning, and flexibility. However, in general, the refractive index of the organic layer including the light emitting layer is 1.6 to 2.1, which is higher than that of air. Therefore, total reflection or interference easily occurs at the interface of the emitted light, the light extraction efficiency is less than 20%, and most of the light is lost.

  The basic structure of the organic EL device is a structure in which a translucent electrode, at least one organic layer including a light emitting layer, and a back electrode are sequentially stacked on a translucent substrate. In an active matrix organic EL device, for example, a TFT substrate in which a plurality of pixel electrodes forming the back electrode and TFTs (thin film transistors) as switching elements are formed in a matrix is stacked on the organic layer. .

Light emitted from the organic layer is reflected directly or by a back electrode formed of aluminum or the like, and is emitted from the translucent substrate. At that time, it is preferable that the generated light is efficiently extracted to the translucent substrate side. However, depending on the angle of incidence on the interface between adjacent layers having different refractive indexes, the light undergoes total reflection, and becomes guided light that is totally reflected in the plane direction inside the device. I can't. The ratio of the guided light is determined by the relative refractive index of the adjacent layer. In the case of a general organic EL device, the relationship of the refractive index n is, for example, air (n = 1.0) / translucent substrate (n = 1.5) / translucent electrode (n = 2.0) / Organic layer (n
= 1.7) / Back electrode. In this case, the proportion of light that is not emitted into the atmosphere (air) but is guided inside the device is about 81%, and only about 19% of the total light emission amount can be effectively used.

As a technique for improving the light extraction efficiency, it has been proposed to provide a light scattering layer at the translucent substrate / translucent electrode interface (see, for example, Patent Documents 1 to 3). Since relatively large light scattering particles are included, the unevenness degree (flatness) of the scattering layer surface often deteriorates.
In addition, the surface of the translucent electrode formed on the scattering layer also follows the surface and becomes uneven, which causes dark spots and short circuits. In order to solve such problems, improvements have been proposed by forming a flat layer on the scattering layer and devising the layer structure. (See Patent Document 4)
However, since a complicated process is required and the layer configuration is limited, demerits occur in the formation of the organic EL device.

JP 2004-296429 A JP 2005-190931 A JP 2009-110930 A JP 2012-069920 A

  In the present invention, by improving the flatness of the scattering layer itself, the influence on each layer formed on the scattering layer is minimized, the occurrence of dark spots and short circuits is eliminated, and the lifetime of the organic EL device is extended. For the purpose.

  As a result of intensive studies, the present inventors have determined that light scattering particles (E) having an average primary particle diameter of 200 to 800 nm and inorganic oxide fine particles (F) having a minor axis diameter of primary particles of 5 to 60 nm. And a resin composition for a light scattering layer containing a polyester dispersant (D), and having excellent optical properties (transparency, refractive index), brings about an excellent light extraction efficiency improvement effect and flatness. It discovered that the composition which can be provided was obtained and came to this invention.

  That is, the present invention relates to light scattering particles (E) having an average primary particle diameter of 200 to 800 nm, inorganic oxide fine particles (F) having a minor axis diameter of primary particles of 5 to 60 nm, and a polyester dispersant (D). The resin composition for light-scattering layers characterized by including these.

  The present invention also relates to the resin composition for a light scattering layer, wherein the inorganic oxide fine particles (F) contain titanium oxide.

  Further, the present invention provides the resin composition for a light scattering layer, wherein the polyester dispersant (D) has a weight average molecular weight of 2,000 to 25,000 and an acid value of 5 to 200 mgKOH / g. Related to things.

  Further, in the present invention, the polyester dispersant (D) is obtained by reacting the hydroxyl group of the polyol (a) with the acid anhydride group of the polycarboxylic acid anhydride (b), and the polyol part (A) and the polycarboxylic acid. A polyester dispersant having alternating portions (B), wherein a part or all of the polyol portion (A) is obtained by radical polymerization of an ethylenically unsaturated monomer (c) via an S atom. It has a vinyl polymer site | part (C), It is related with the said resin composition for light scattering layers characterized by the above-mentioned.

  In the present invention, the polyester dispersant (D) is obtained by radical polymerization of the ethylenically unsaturated monomer (c) in the presence of the compound (a1) having two hydroxyl groups and one thiol group in the molecule. An acid in a polycarboxylic acid anhydride (b) containing at least a hydroxyl group in a polyol (a) containing at least a vinyl polymer (a2) having two hydroxyl groups at one end and a tetracarboxylic dianhydride (b1) A polyester dispersant obtained by reacting an anhydride group, or a hydroxyl group in a polyol (a) containing at least a compound (a1) having two hydroxyl groups and one thiol group in the molecule, and tetracarboxylic dianhydride A vinyl polymer site (C) is formed in the presence of the polyester (d) obtained by reacting the acid anhydride group in the polycarboxylic acid compound (b) containing at least the product (b1). Ethylenic unsaturated monomers and (c) relating to the light scattering layer resin composition which is a polyester dispersant formed by radical polymerization.

The present invention also relates to the resin composition for a light scattering layer, wherein the tetracarboxylic dianhydride (b1) is represented by the following general formula (1) or general formula (2).
General formula (1):
[In General Formula (1), k is 1 or 2. ]
General formula (2):
[In General Formula (2), Q1 represents a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, General Formula (3):
Or a group represented by the general formula (4):
It is group represented by these. ]

  The present invention also relates to the resin composition for a light scattering layer, wherein the vinyl polymer moiety (C) has a weight average molecular weight of 1,000 to 20,000.

Moreover, this invention relates to the said resin composition for light scattering layers characterized by the ethylenically unsaturated monomer (c) containing the monomer represented by following General formula (5).
General formula (5):
[In General Formula (5), R ³² is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 carbon atom which may have a substituent. -20 alkenyl group, phenyl group which may have a substituent, or a compound represented by the following general formula (6), R ³¹ is a hydrogen atom or a methyl group. ]
General formula (6):
[In General Formula (6), R ³³ is a linear or branched alkylene group having 1 to 8 carbon atoms, and R ³⁴ is a linear chain having 1 to 20 carbon atoms which may have a substituent. Or a branched or cyclic alkyl group, an optionally substituted alkenyl group having 1 to 20 carbon atoms, or an optionally substituted phenylene group, and n is an integer of 1 to 30 It is. ]

  The present invention also relates to the resin composition for a light scattering layer, wherein the glass transition temperature of the vinyl polymer portion (C) is less than 50 ° C.

  Moreover, this invention relates to the said resin composition for light scattering layers characterized by including a photoinitiator (H) further.

  Moreover, this invention relates to the light-scattering layer formed using the said resin composition for light-scattering layers.

  According to another aspect of the present invention, on the light-transmitting substrate, the light scattering layer, the light-transmitting first electrode, the at least one organic layer including the light-emitting layer, and the light-reflecting second electrode; Relates to an organic electroluminescence device in which are sequentially stacked.

  The present invention also relates to the organic electroluminescence device which is a lighting device or a display device.

  According to the present invention, it can be used as a light scattering layer installed between a translucent electrode and a translucent substrate to improve the light extraction efficiency of the organic EL device, and can improve the light extraction efficiency, transmittance, and flatness. The resin composition for light-scattering layers excellent in property, the light-scattering layer formed using this, and the organic EL apparatus which comprises this light-scattering layer can be provided.

Schematic cross section of bottom emission EL element Schematic cross section of thin film printing device

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. Not specific to the content.

Hereinafter, the present invention will be described in detail.
In the present application, when expressed as “(meth) acrylate”, “(meth) acrylic acid”, or “(meth) acrylamide”, unless otherwise specified, “acrylate and / or methacrylate”, It shall represent “acrylic acid and / or methacrylic acid” or “acrylamide and / or methacrylamide”.

"Resin composition for light scattering layer"
The resin composition for a light scattering layer of the present invention includes light scattering particles (E) having an average primary particle diameter of 200 to 800 nm, and inorganic oxide fine particles (F) having a minor axis diameter of primary particles of 5 to 60 nm. And a polyester dispersant (D).

<Light scattering particles (E)>
The light scattering particles (E) in the resin composition for a light scattering layer of the present invention have an average primary particle diameter of 200 to 800 nm. When the average primary particle diameter of the light scattering particles (E) is less than 200 nm, a sufficient scattering effect does not appear and the refractive index of the binder composition is affected. On the other hand, if it is larger than 800 nm, even if the scattering intensity (haze value) is high, the scattering angle becomes narrow, so that effective scattering for total reflection cannot be obtained, the extraction efficiency is lowered, or the light extraction efficiency changes with wavelength. It becomes larger and the color tone tends to change. More preferably, it is 250 nm-500 nm.

(Light scattering particle (E) average primary particle size measurement)
In the present invention, the “average primary particle diameter” of the light scattering particles (E) is measured by a method of directly measuring the size of primary particles from an electron micrograph using a TEM (transmission electron microscope). Can do. Specifically, as the measuring method, the minor axis diameter and major axis diameter of the primary particles of each light scattering particle (E) are measured, and the average is taken as the average primary particle diameter of the primary particles.
In the case of resin particles, since a solvent is included at the time of synthesis, the particle diameter can be observed after drying with a vacuum dryer and removing the solvent. Aggregation may occur due to drying, and a plurality of particles may adhere as a lump. In this case, there is no problem if the particle diameter is measured by paying attention to each particle.

The light scattering particle (E) is not particularly limited as long as it has an effect of scattering and extracting light guided by total reflection in the organic EL device, and even if it is an organic particle, it is an inorganic particle. May be.
Examples of the organic particles include methacrylate ester copolymer beads, acrylic-styrene copolymer beads, melamine resin beads, polycarbonate beads, polystyrene beads, crosslinked polystyrene beads, polyvinyl chloride beads, and benzoguanamine-melamine formaldehyde condensate beads. Used. Examples of inorganic particles include silicon oxide (SiO ₂ ), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), Tin oxide (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ), and the like are used. These may be used alone or in combination of two or more.

In the case of organic particles, the light scattering particles (E) are aggregated by drying. Therefore, the light scattering particles (E) are preferably used as they are in the synthesis. However, when the dried organic particles or inorganic particles are dispersed, the aggregation is loosened. Therefore, a method using a dispersant or a surfactant and using a disperser is preferable.
As a dispersing agent used here, it is preferable to use a polyester dispersing agent (D), and, thereby, favorable flatness can be obtained.
Dispersers include paint conditioner (manufactured by Red Devil), ball mill, sand mill (such as “Dyno mill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eirich), coball mill, homomixer, Homogenizers (such as “Clairemix” manufactured by M Technique Co., Ltd.), wet jet mills (“Genus PY” manufactured by Genus, “Nanomizer” manufactured by Nanomizer), microbead mills (“Super Apeck Mill” manufactured by Kotobuki Industries Co., Ltd.) And “Ultra Apeck Mill”), an ultrasonic disperser, and the like.
When media are used in the disperser, glass beads, zirconia beads, alumina beads, magnetic beads, polystyrene beads, and the like are preferably used. Regarding dispersion, two or more types of dispersers or two or more types of media having different sizes may be used and may be implemented step by step.

(Measurement of dispersion particle diameter of light scattering particle (E) dispersion)
The average particle diameter of the light scattering particle (E) dispersion can be measured using, for example, “Nanotrack UPA” manufactured by Nikkiso Co., Ltd. Specifically, several drops of a light scattering particle dispersion whose solid content weight% concentration is adjusted to 20% are put into a cell filled with the same solvent as the dispersion, and the signal level is measured at the optimum value. can do.

  The particle size distribution of the light scattering particle (E) dispersion preferably has a variation coefficient of 30% or less. The “variation coefficient” is expressed as a percentage of a value obtained by dividing the standard deviation of the particle diameter by the average particle diameter, and is an index of the degree of variation with respect to the average particle diameter. If the coefficient of variation is greater than 30%, the change in the light extraction efficiency with the wavelength increases and the color tone tends to change, which may not be preferable. More preferably, the coefficient of variation is 20% or less.

  In the case of inorganic particles, the average particle size and particle size distribution of the light scattering particle (E) dispersion are adjusted to a suitable range by appropriately adjusting the dispersion conditions, for example, the disperser, the dispersion medium, the dispersion time, and the dispersant. Is possible. In the case of organic particles, it can be adjusted by the synthesis conditions such as the polymerization temperature and the polymerization composition, or the dispersion conditions such as the disperser, dispersion medium, dispersion time, and dispersant.

  1-30 weight% is preferable in the solid content of the resin composition for light-scattering layers, and, as for the usage-amount of light-scattering particle (E), 1-20 weight% is more preferable. If the amount is less than 1% by weight, a sufficient scattering effect may not be exhibited. If the amount exceeds 30% by weight, the particles tend to aggregate and the surface roughness of the light scattering layer may increase.

Examples of the refractive index of the light scattering particles (E) include methacrylic acid ester copolymer beads: 1.45 to 1.60, acrylic-styrene copolymer beads: 1.5 to 1.6, and melamine resin beads: 1 .65, SiO ₂ : 1.45, ZrO ₂ : 2.2, and TiO ₂ : 2.5.
Preferred are trifluoroethyl methacrylate copolymer beads: 1.46 and TiO ₂ : 2.5 that can increase the refractive index difference from the binder composition.
In the present specification, the “refractive index of light scattering particles” means the bulk refractive index of the material constituting the inorganic oxide fine particles. The refractive index of the bulk material can be measured using an Abbe refractometer or a V block refractometer.

<Inorganic oxide fine particles (F)>
The resin composition of this invention contains the inorganic oxide microparticles | fine-particles (F) whose short axis diameter of a primary particle is 5-60 nm. Thereby, a resin composition can be adjusted to arbitrary refractive indexes.

  If the minor axis diameter of the primary particles exceeds 60 nm, the transparency of the coated film is lowered and the surface roughness is deteriorated. When the minor axis diameter of the primary particles is less than 5 nm, it is not preferable from the viewpoint of availability, and it is difficult to obtain a stable dispersion because of high cohesion.

  The aspect ratio of the minor axis diameter to the major axis diameter of the inorganic oxide fine particles (F) is preferably 1 to 10, and more preferably 1 to 6. If the aspect ratio exceeds 10, the particle size distribution of the inorganic oxide dispersion becomes wide and the transmittance tends to decrease, which may be undesirable.

The inorganic oxide fine particles (F) used in the present invention desirably have a refractive index of 1.8 to 2.8 in the visible light region.
Especially, since the refractive index of inorganic oxide microparticles | fine-particles (F) is 1.8-2.5 normally, by adding inorganic oxide microparticles | fine-particles (F) to a resin composition as a dispersion, an acrylic resin is used. Compared with a refractive index of about 1.4 to 1.5, the refractive index of the entire light scattering layer can be improved.

  In this specification, the “refractive index of inorganic oxide fine particles (F)” means the bulk refractive index of the material constituting the inorganic oxide fine particles. The refractive index of the bulk material can be measured using an Abbe refractometer or a V block refractometer.

Specific examples of the inorganic oxide fine particles (F) include titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), cerium oxide (CeO ₂ ), hafnium oxide (HfO ₂ ), and niobium pentoxide (Nb ₂ O). ₅ ) at least selected from the group consisting of tantalum pentoxide (Ta ₂ O ₅ ), indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), indium tin oxide (ITO), and zinc oxide (ZnO) A particle composed of one kind of material can be mentioned.

Among these, titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), zinc oxide (ZnO), and tin oxide (SnO ₂ ) are preferable. Titanium oxide (TiO ₂ ) and zirconium oxide (ZrO ₂ ) are particularly preferable from the viewpoints of translucency, dispersibility, weather resistance, light resistance, and the like. Most preferred is titanium oxide (TiO ₂ ).

(Measurement of particle diameter of primary particles of inorganic oxide fine particles (F))
The minor axis diameter of the primary particles of the inorganic oxide fine particles (F) referred to in the present invention indicates individual particle diameters that do not take into account aggregation, and is obtained from an electron micrograph using a transmission (TEM) electron microscope. It can be measured by a method of directly measuring the particle size. Specifically, the short axis diameter of the primary particle of each inorganic oxide fine particle (F) was measured as a measuring method, and the average was set as the short axis diameter of the primary particle.
Similarly, the major axis diameter of the primary particles of the inorganic oxide fine particles (F) can also be measured. When the aspect ratio is in the range of 0.9 to 1.1 and the shape is almost spherical, the average of the minor axis diameter and major axis diameter of the primary particles of the individual inorganic oxide fine particles (F). The value was defined as the minor axis diameter of the primary particles.

<Inorganic oxide fine particle (F) dispersion>
As the inorganic oxide fine particles (F), the powder can be used as it is, and since the dispersion state can be maintained, a dispersion liquid previously dispersed in a solvent may be used. The dispersion method is preferably a method using a disperser using a dispersant that matches the surface state of the inorganic oxide fine particles (F) as in the case of the light scattering particles (E). Of these, the polyester dispersant (D) is most preferably used.

  The dispersion and resin composition containing the inorganic oxide fine particles (F) preferably have a light transmittance of 80% or more, more preferably 85% or more in a visible light wavelength region and an optical path length of 1 mm. This light transmittance varies depending on the content of the inorganic oxide fine particles (F) in the dispersion and the resin composition.

  The amount of the inorganic oxide fine particles (F) used in the resin composition for light scattering layer of the present invention is preferably 80% by weight or less, more preferably 60% by weight or less in the resin composition for light scattering layer. preferable. If it exceeds 80% by weight, the particles may aggregate and the coating film may become brittle.

  The inorganic oxide fine particles (F) are preferably surface-coated with an organic compound or an organometallic compound. Examples of the surface coating treatment method include a pretreatment method and an integral blend method. In the present invention, the pretreatment method is preferred. Pretreatment methods include wet methods and dry methods, and wet methods include water treatment methods and solvent treatment methods.

  Water treatment methods include a direct dissolution method, an emulsion method, and an amine adduct method. In the wet method, a surface treatment agent is dissolved or suspended in an organic solvent or water, inorganic oxide fine particles are added thereto, and such a solution is stirred and mixed for several minutes to 1 hour. In this method, the surface of the inorganic oxide fine particles is coated after the heat treatment and then dried through a process such as filtration. Note that a surface treatment agent may be added to a suspension in which inorganic oxide fine particles are dispersed in an organic solvent or water. As the surface treatment agent, a variety that dissolves in water in the direct dissolution method, a variety that can be emulsified in water in the emulsion method, and a variety that has a phosphate residue can be applied in the amine adduct method. In the amine adduct method, a small amount of a tertiary amine such as trialkylamine or trialkylolamine is added to adjust the adjustment solution to pH = 7 to 10, and cooling is performed in order to suppress an increase in the liquid temperature due to the neutralization exothermic reaction. It is preferable to perform the treatment while the other steps can be surface-coated by treating in the same manner as other wet methods. The surface treatment agent that can be used in the wet method is limited to those that can be dissolved or suspended in the organic solvent or water used.

  Examples of the dispersion solvent include water, alcohols such as methanol, ethanol, isopropanol, and n-butanol; polyhydric alcohols such as ethylene glycol and derivatives thereof; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and dimethyldimethylacetamide; dimethyl ether; Ethers such as THF; esters such as ethyl acetate and butyl acetate; nonpolar solvents such as toluene and xylene; acrylates such as 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate and 4-hydroxybutyl acrylate and others Organic solvents can be used. The amount of the dispersion solvent is usually 100 to 2000 parts by weight with respect to 100 parts by weight of the particles.

  The dry method is a method in which a surface treatment agent is directly added to inorganic oxide fine particles, and the surface is coated by stirring and mixing with a mixer. In general, it is preferable to perform preliminary drying in order to remove moisture on the surface of the inorganic oxide fine particles. For example, after pre-drying at a temperature of about 100 ° C. at a speed of several tens of rpm (number of revolutions per minute) using a mixer such as a Henschel mixer, the surface treatment agent is dissolved directly or in an organic solvent or water. Add the dispersed and mixed solution. In that case, it can mix more uniformly by spraying with dry air or nitrogen gas.

  The integral blend method is a method generally used in the field of paint, and a surface treatment agent is added to coat the surface when kneading with the inorganic oxide fine particle resin.

  As the surface treating agent that can be used for the surface coating treatment of the inorganic oxide fine particles (F) of the present invention, at least one of an organic compound and an organometallic compound is used. Specific examples of these compounds include various silicone oils such as methylhydrogenpolysiloxane, dimethylpolysiloxane, and methylphenylpolysiloxane, methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyl. Various alkyl silanes such as trimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride, trifluoromethylethyltrimethoxysilane, hepta Various fluoroalkylsilanes such as decafluorodecyltrimethoxysilane, especially vinyltrimethoxysilane, γ-aminopropyltrimethoxysilane Organometallic compounds of various metal coupling agents such as silane, titanium, aluminum, and alumina-zirconia, represented by silane coupling agents such as, fatty acids such as isostearic acid and stearic acid, and metal salts thereof Furthermore, any treatment agent for organic compounds such as surfactants can be used, and these can be used alone or in admixture of two or more. In particular, in the case where hardness, adhesion, and scratch resistance are expressed in a coating film obtained from a coating composition containing the same, the surface treatment preferably includes treatment with an inorganic compound including aluminum, silicon, and zirconium. Those that are coated are particularly preferred.

  The content of the surface treatment agent in the inorganic oxide fine particles (F) after the surface coating treatment is preferably 5 to 20% by weight. When the content of the surface treatment agent is less than 5% by weight, it may be difficult to obtain an effect for preventing aggregation of inorganic oxide fine particles. On the other hand, when the content of the surface treatment agent is more than 20% by weight, the high refractive index component contained in the inorganic oxide fine particles (F) after the surface coating treatment is relatively small, and the refractive index of the resin composition. May not be raised sufficiently.

  In general, these fine powder particles have a very strong cohesive force, and the primary particles are aggregated in clusters to form secondary aggregates. Therefore, it is not possible to obtain a dispersion by simply adding the agglomerated powder subjected to the surface coating treatment to the dispersion medium as it is and stirring and mixing. In order to form a dispersion of inorganic oxide fine particles (F), mechanical energy is added to these powders, the aggregation between the particles is broken, and the particles are finely pulverized to a position close to the original primary particle size. Visible light transparency can be achieved when a coating film is formed. In this case, as described later, it is preferable to add a dispersant for stabilizing the dispersion. In the present invention, the surface treatment agent does not include a dispersant used when mechanical energy is applied to loosen the aggregation.

As the mechanical pulverization / dispersion apparatus, known ones such as a bead mill, a jet mill, an attritor, and a sand mill can be used. The liquid is preferred because it is easily obtained in a short time. As specific examples of the bead mill, Ashizawa Finetech Co., Ltd. mini-zeta, Labstar, Star Mill LMZ, Star Mill ZRS, Kotobuki Industries Co., Ltd. Ultra Apex Mill, Imex Co., Ltd. Max Visco Mill, etc. can be used. The dispersion time varies depending on the bead diameter, the bead material used, the peripheral speed of the bead mill, etc., but generally the bead diameter is about 0.03 to 0.5 mm, and the use of ceramic beads such as alumina and zirconia is suitable. The grinding time in the bead mill is preferably about 20 minutes to 5 hours, more preferably about 30 minutes to 3 hours.
The dispersion medium can be used regardless of whether it is water or an organic solvent, but more preferably water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, diacetone alcohol, propylene glycol monomethyl ether Preferred are polar solvents such as ethers such as propylene glycol monoethyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and mixed solvents thereof.

  At the time of pulverization and dispersion, it is preferable to use a dispersant from the viewpoint of dispersion stability, and it is particularly preferable to add and disperse the polyester dispersant (D). It is because the coating film which was more excellent in flatness can be formed by disperse | distributing using a polyester dispersing agent (D).

  Other dispersants may be used simultaneously or independently, and known ones such as resin-type dispersants, silane coupling agents, titanate coupling agents, silicone dispersants such as modified silicone oils, and the like are used. It is possible. Dispersant used at the time of pulverization / dispersion has an organic functional group that is adsorbed and oriented on the surface of the inorganic powder and plays a role of protecting fine particles refined by pulverization. It is essential when preparing Examples of the organic functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, an imino group, and salts thereof, an amide group, and an acetylacetonate group. In particular, a carboxyl group, a phosphate group, and sodium salts and ammonium bases thereof are preferable.

  In the resin type dispersant, in addition to the polyester dispersant (D), a resin type dispersant having the functional group in the side chain may be used. Specific product names include Disperbyk 182, 2155, 2022 (by Big Chemie), Pois 520, 521, 532A, 2100 (by Kao Corporation), Disperbyk 102, 111, 180 (by Big Chemie), Aaron T- 40 (manufactured by Toagosei Co., Ltd.) can be used.

  These dispersants are preferably allowed to coexist when the powder and dispersion medium are mechanically pulverized and dispersed with a bead mill. When a dispersant is added after mechanically pulverizing and dispersing only with powder and a dispersion medium, aggregation may not be solved until the target average particle diameter of the dispersion liquid is reached.

  The solid content concentration of the inorganic oxide fine particles (F) in the dispersion is preferably 1 to 80% by weight, more preferably 2 to 65% by weight. If the amount is less than 1% by weight, the total solid content concentration of the resin composition is too small, and a coating film having an appropriate film thickness cannot be obtained. Inconvenience in handling is likely to occur. In addition, the usage-amount of the said dispersing agent is 0.5-30 weight part with a dispersing agent active ingredient with respect to 100 weight part of inorganic oxide microparticles | fine-particles (F) solid content, Preferably 1-20 weight part is preferable. If the amount is less than 0.5 part by weight, the effect of adding a dispersant hardly appears. If the amount is more than 30 parts by weight, the excessive dispersant causes a decrease in scratch resistance and weather resistance of the coating film, and the resin composition is sufficiently refracted. You may not get the rate.

  The inorganic oxide fine particles (F) of the present invention preferably contain titanium oxide. By using such particles, a coating film having excellent optical properties (transparency, refractive index) and light extraction efficiency can be formed.

  In the case of titanium oxide, there are three types of crystal forms: rutile, anatase, and brookite. In the present invention, the rutile type is preferred from the viewpoint of refractive index.

  The titanium oxide may be used by subjecting the titanium oxide before the surface treatment to the surface treatment by the above-described method, or the commercially available titanium oxide particles after the surface coating treatment having an average primary particle diameter of 5 nm to 60 nm may be used. good.

Below, the commercial item of the rutile type titanium oxide whose short axis diameter of the primary particle of this invention is 5-60 nm is illustrated.
“MT-500SA” manufactured by Teika Co., Ltd. (short axis diameter: 35 nm, Al (OH) ₃ surface treatment, etc.),
“MT-500T” (short axis diameter: 35 nm, Al (OH) ₃ surface treatment, etc.),
“SMT-500SAS” (short axis diameter: 35 nm, Al (OH) ₃ surface treatment, etc.),
“SMT-500SAM” (short axis diameter: 35 nm, Al (OH) ₃ surface treatment, etc.),
“SMT-100SAS” (short axis diameter: 15 nm, Al (OH) ₃ surface treatment, etc.),
“MTY-100SAS” (short axis diameter: 15 nm, Al (OH) ₃ surface treatment, etc.),
“MT-100SA” (short axis diameter: 15 nm, Al (OH) ₃ surface treatment, etc.),
“MT-100AQ” (short axis diameter: 15 nm, Al (OH) ₃ surface treatment, etc.),
“MT-100TV” (short axis diameter: 15 nm, Al (OH) ₃ surface treatment, etc.),
“MT-100Z” (short axis diameter: 15 nm, Al (OH) ₃ surface treatment, etc.),
“MT-150EX” (short axis diameter: 15 nm, Al (OH) ₃ surface treatment, etc.),
“MT-100WP” (short axis diameter: 15 nm, silica surface treatment, etc.),
“MT-05” (short axis diameter: 10 nm, Al (OH) ₃ surface treatment, etc.),
“MTY-02” (short axis diameter: 10 nm, Al (OH) ₃ surface treatment, etc.),
“MTY-110M3S” (short axis diameter: 10 nm, Al (OH) ₃ surface treatment, etc.),
“MT-01” (short axis diameter: 10 nm, Al (OH) ₃ surface treatment, etc.),
“MT-10EX” (short axis diameter: 10 nm, Al (OH) ₃ surface treatment, etc.),
“JMT-150IB” (short axis diameter: 15 nm, alkylsilane surface treatment, etc.),
“JMT-150AQ” (short axis diameter: 15 nm, alkylsilane surface treatment, etc.),
“JMT-150FI” (short axis diameter: 15 nm, alkylsilane surface treatment, etc.),
“JMT-150ANO” (short axis diameter: 15 nm, alkylsilane surface treatment, etc.),
“TTO-51A” manufactured by Ishihara Sangyo Co., Ltd. (short axis diameter: 10 nm, long axis diameter: 30 nm, Al (OH) ₃ surface treatment),
“TTO-51C” (short axis diameter: 10 nm, long axis diameter: 30 nm, Al (OH) ₃ surface treatment, etc.),
“TTO-55A” (short axis diameter: 30 nm, long axis diameter: 50 nm, Al (OH) ₃ surface treatment),
“TTO-55C” (short axis diameter: 30 nm, long axis diameter: 50 nm, Al (OH) ₃ surface treatment, etc.),
“TTO-S-2” (short axis diameter: 15 nm, long axis diameter: 75 nm, Al (OH) ₃ surface treatment, etc.),
“MPT-136” (short axis diameter: 15 nm, long axis diameter: 75 nm, Al (OH) ₃ surface treatment, etc.),
“TTO-V-3” (short axis diameter: 10 nm, long axis diameter: 60 nm, Al (OH) ₃ surface treatment, etc.),
“ST-455” manufactured by Titanium Industry Co., Ltd. (short axis diameter: 20 nm, long axis diameter: 120 nm, Al (OH) ₃ surface treatment, etc.),
“ST-455WS” (short axis diameter: 20 nm, long axis diameter: 120 nm, silica surface treatment),
“ST-485SA15” (short axis diameter: 8 nm, long axis diameter: 100 nm, Al (OH) ₃ surface treatment, etc.),
“Titanium dioxide P25” (short axis diameter: 21 nm) manufactured by Nippon Aerosil Co., Ltd.
“Titanium dioxide T805” (short axis diameter: 21 nm)
Among these, titanium oxide subjected to Al (OH) ₃ surface treatment is preferable.

  Further, other inorganic oxide fine particles may be used. Other inorganic oxide fine particles include the following.

  Commercially available products as silicon oxide fine particle dispersions include MA-ST-MS, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA-ST-ZL manufactured by Nissan Chemical Industries, Ltd. , IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like, and hollow silica CS60-IPA manufactured by Catalyst Chemical Industry Co., Ltd. can be exemplified. As powder silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Commercially available products as aluminum oxide fine particle dispersions include Alumina Sol-100, Alumina Sol-200, Alumina Sol-520 manufactured by Nissan Chemical Industries, Ltd., AS-150I and AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd. Can be mentioned.

  Commercially available products as zirconia oxide fine particle dispersions include ZR-40BL, ZR-30BS, ZR-30BF, ZR-30AL, ZR-30AH manufactured by Nissan Chemical Industries, Ltd., Sumitomo Osaka Cement Co., Ltd. There may be mentioned HXU-110JC. In addition, the oxide fine particle dispersion of zirconia can be obtained by the method described in Japanese Patent No. 469630.

  In addition, as a commercially available product of oxide fine particle dispersions such as zinc, nanotech manufactured by CI Kasei Co., Ltd. can be exemplified.

(Dispersion particle size of inorganic oxide fine particles (F))
The dispersed particle diameter of the inorganic oxide fine particle (F) dispersion can be measured using, for example, “Nanotrack UPA” manufactured by Nikkiso Co., Ltd. The light scattering particle dispersion liquid whose solid content weight% concentration is adjusted to 20% is dropped into a cell filled with the same solvent as the dispersion liquid, and the signal level can be measured at the optimum value.

  The dispersed particle diameter of the inorganic oxide fine particles (F) in the present invention is preferably 10 nm or more and 70 nm or less. When the average primary particle diameter exceeds 70 nm, the transparency of the coated film may be lowered, or the surface roughness may be deteriorated. When the dispersed particle size is less than 10 nm, it may not be preferable from the viewpoint of stability.

<Polyester dispersant (D)>
The resin composition of the present invention contains a polyester dispersant (D), and the polyester dispersant (D) can be used without limitation as long as it has an ester skeleton in the main chain and side chains. Preferably, the dispersant has an ester skeleton in the main chain.
More preferably, a polyester dispersing agent (D1), (D2) etc. are mentioned. By containing an ester skeleton in the main chain, it acts as an affinity group for light scattering particles or inorganic oxide fine particles.
Especially, it is preferable to use for disperse | distributing light-scattering particle | grains (E) or inorganic oxide microparticles | fine-particles (F), and by having an ester skeleton, to the surface of light-scattering particle | grains (E) or inorganic oxide microparticles | fine-particles (F). In addition to being excellent in dispersion stability and compatibility, it has excellent flatness and can prevent aggregation and protrusion in the coating film.

  The polyester dispersant (D) may be used for dispersing either the light scattering particles (E) or the inorganic oxide fine particles (F). However, the polyester dispersant (D) may be used for dispersing the inorganic oxide fine particles (F). It is preferable from the viewpoint of the stability of the composition and the flatness of the coating film. Moreover, it is most preferable from the surface of flatness to disperse | distribute with the polyester dispersing agent (D) in both light-scattering particle | grains (E) and inorganic oxide microparticles | fine-particles (F).

  In general, a dispersant has a structure of a part adsorbed on light scattering particles or inorganic oxide fine particles and a part having a high affinity for a light scattering particle or a solvent that is an inorganic oxide fine particle carrier or dispersion medium. The balance of the two parts determines the performance of the dispersant. That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the light scattering particles or the inorganic oxide fine particles and the affinity to the solvent as the dispersion medium are very important.

  The polyester dispersant (D) in the present invention is preferably a dispersant having an acidic group, and particularly preferably an acidic resin type dispersant having an aromatic carboxyl group. Of these, a dispersant obtained by reacting a polymer having a hydroxyl group at one end with an aromatic tricarboxylic acid anhydride and / or aromatic tetracarboxylic dianhydride is most preferable. Examples of such resin-type dispersants include Japanese Patent No. 40201050, Japanese Patent Application Laid-Open No. 2007-140487, International Publication No. 2008/007776, Japanese Patent Application Laid-Open No. 2010-163500, and Japanese Patent Application Laid-Open No. 2010-223888. And exhibits excellent effects such as compatibility between fluidity and dispersibility.

  From the viewpoint of adsorptivity to light scattering particles or inorganic oxide fine particles, tetracarboxylic dianhydrides having two or more aromatic rings are preferable because they are suitable skeletons and are excellent in dispersion stability.

[Polyester dispersant (D1)]
As a preferable resin-type dispersant described in JP-A No. 2007-140487, a polyester dispersant (D1) represented by the following formula can be given.
(HOOC-) _m1 -R ₅₄ -(-COO-[-R ₅₆ -COO-] _q -R ₅₅ ) _t
[Wherein R ₅₄ is a tetravalent tetracarboxylic acid compound residue, R ₅₅ is a monoalcohol residue, R ₅₆ is a lactone residue, m1 is 2 or 3, q is an integer of 1 to 50, and t is (4 -M1). ]

[Polyester dispersant (D2)]
The polyester dispersant (D) of the present invention includes a hydroxyl group of the polyol (a) and an acid of the polycarboxylic acid anhydride (b) from the viewpoint of better stability of the light scattering particles or the inorganic oxide fine particle dispersion. A polyester dispersant having a polyol site (A) and a polycarboxylic acid site (B) alternately formed by reacting an anhydride group, wherein a part or all of the polyol site (A) is introduced via an S atom. More preferably, it is a polyester dispersant (D2) having a vinyl polymer site (C) obtained by radical polymerization of an ethylenically unsaturated monomer (c).
At this time, the polycarboxylic acid part (B) of the main chain serves as a light scattering particle or inorganic fine particle adsorbing group, and the vinyl polymer part (C) of the side chain serves as a light scattering particle or inorganic oxide fine particle carrier affinity group. Act.
Such polyester dispersants are described in International Publication No. 2008/007776 pamphlet and the like.

  The polyester dispersant (D2) is prepared by radically polymerizing an ethylenically unsaturated monomer (c) in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule. A hydroxyl group in the polyol (a) containing at least the vinyl polymer (a2) having two hydroxyl groups, and an acid anhydride group in the polycarboxylic acid anhydride (b) containing at least the tetracarboxylic dianhydride (b1). , Obtained by reacting.

  Also, a polycarboxylic acid compound (b) containing at least a hydroxyl group in the polyol (a) containing at least a compound (a1) having two hydroxyl groups and one thiol group in the molecule and a tetracarboxylic dianhydride (b1). It can also be obtained by radical polymerization of the ethylenically unsaturated monomer (c) forming the vinyl polymer site (C) in the presence of the polyester (d) obtained by reacting with an acid anhydride group in .

Each component of the polyester dispersant (D2) will be described.
<< ethylenically unsaturated monomer (c) >>
Examples of the ethylenically unsaturated monomer (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) ) Acrylate, 2-methyl-2-adamantyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meta Acrylate, oxetane (meth) acrylate, etc., methoxypolypropylene glycol (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylates such as ethoxypolyethylene glycol (meth) acrylate, (meth) acrylamide, and N, N-dimethyl (meth) N-substituted (meth) acrylamides such as acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, N, N-dimethylaminoethyl (meth) Examples include acrylates, amino group-containing (meth) acrylates such as N, N-diethylaminoethyl (meth) acrylate, nitriles such as (meth) acrylonitrile, and mixtures thereof. .

  Also, styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate and vinyl propionate, and the like These mixtures may be used in combination.

  Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. As the carboxyl group-containing ethylenically unsaturated monomer, one or more kinds can be selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.

  The polyester dispersant (D2) has a vinyl polymer part (C) formed by radical polymerization of these ethylenically unsaturated monomers (c), and the glass transition temperature of the vinyl polymer part (C). (Hereinafter abbreviated as Tg) is preferably less than 50 ° C.

  However, these ethylenically unsaturated monomers (c) are not only those having a glass transition temperature of the homopolymer (hereinafter abbreviated as Tg) of less than 50 ° C. Forming a vinyl polymer portion (C) having a Tg of less than 50 ° C. in the polyester dispersion of the present invention by copolymerizing a monomer having a high Tg of the copolymer and a monomer having a low Tg of the homopolymer Can do.

  One molecule of the polyester dispersant (D2) of the present invention has many vinyl polymer sites (C) having a Tg of less than 50 ° C., and has an affinity for light scattering particles or inorganic oxide fine particle carriers and solvents. Functions as a site. When the vinyl polymer site (C) is 50 ° C. or higher, the development residue in the development process may be deteriorated when forming a film as a photosensitive composition. In general, a film forming process such as an insulating film for a touch panel requires a development process, and development resistance is required. Therefore, a decrease in cross-linking reaction efficiency caused by including a molecule having rigidity due to high Tg results in development resistance. Also affects. Therefore, the Tg of the vinyl polymer portion (C) is more preferably 30 ° C. or less. There is no particular lower limit on the Tg of the vinyl polymer site (C), but a material below -50 ° C generally has a long alkyl chain, and the dispersibility of light scattering particles or inorganic fine particles may deteriorate. is necessary.

The Tg of the vinyl polymer portion (C) referred to in the present invention is a value calculated by the following Fox formula from the Tg of each homopolymer of the ethylenically unsaturated monomer (c) to be copolymerized. Yes.

Formula of Fox 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn
W1 to Wn represent the weight fraction of the monomer used, and Tg1 to Tgn represent the glass transition temperature of the monomer homopolymer (unit is absolute temperature “K”).

  The Tg of the main monomer homopolymer is exemplified below.

n-butyl acrylate: -45 ° C (228K)
n-butyl methacrylate: 18 ° C. (291 K)
tert-butyl methacrylate: 107 ° C. (380 K)
Ethyl acrylate: -22 ° C (251K)
Cyclohexyl acrylate: 83 ° C (356K)
Benzyl methacrylate: 54 ° C (327K)
2-Methoxyethyl acrylate: -50 ° C (223K)
tert-butyl acrylate: 41 ° C. (314 K)
Acrylic acid: 105 ° C (378K)
Methacrylic acid: 228 ° C (501K)
2-Ethylhexyl methacrylate: -10 ° C (263K)
2-hydroxyethyl acrylate: -15 ° C (258K)
2-hydroxybutyl acrylate: −40 ° C. (233 K)
2-Ethylhexyl acrylate: -70 ° C (203K)
Methyl methacrylate: 105 ° C (378K)
Methacrylic acid: 228 ° C (501K)
Acrylic acid: 105 ° C (378K)
Isobornyl acrylate: 94 ° C (367K)
Isobornyl methacrylate: 180 ° C (453K)
Dicyclopentanyl acrylate: 120 ° C (393K)
Dicyclopentanyl methacrylate: 175 ° C (448K)
Adamantyl acrylate: 153 ° C (426K)
Adamantyl methacrylate: 250 ° C (523K)

For example, when the calculation is performed by the above method, the glass transition temperature of the vinyl polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer synthesized using 90 parts by weight of methyl methacrylate and 10 parts by weight of ethyl acrylate is 86. 8 ° C.

In particular, in order to make Tg less than 50 ° C., it is necessary to contain an ethylenically unsaturated monomer having a low homopolymer Tg in the copolymer composition. Among the ethylenically unsaturated monomers, the following are low in Tg, and are effective for lowering the Tg of the vinyl polymer portion of the polyester dispersant.
Therefore, among the ethylenically unsaturated monomers (c), n-butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2-ethylhexyl Acrylate and the like are preferable.

  In the present invention, among the ethylenically unsaturated monomers (c), a monomer represented by the following general formula (5) is preferable from the viewpoint of dispersibility of the inorganic oxide fine particles. It is preferable that the usage-amount of the monomer represented by following General formula (5) is contained 5weight% or more with respect to the whole monomer which comprises a vinyl polymer (a2). If it is 5% by weight or more, the affinity effect to the solvent is more excellent, and from the viewpoint of the balance between the dispersibility of the inorganic oxide fine particles and the development resistance, 10 to 40% by weight is more preferable, and 15 to 35% by weight is the most. preferable.

General formula (5):
[In General Formula (5), R ³² is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 carbon atom which may have a substituent. -20 alkenyl groups, a phenyl group which may have a substituent, or a compound represented by the following general formula (6), R ³¹ is a hydrogen atom or a methyl group. ]
General formula (6):
[In General Formula (6), R ³³ is a linear or branched alkylene group having 1 to 8 carbon atoms, and R ³⁴ is a linear chain having 1 to 20 carbon atoms which may have a substituent. A branched or cyclic alkyl group, an optionally substituted alkenyl group having 1 to 20 carbon atoms, or an optionally substituted phenylene group, and n is 1 to 30 It is an integer. ]

In the general formula (5), specific examples of R ³² include methyl group, ethyl group, n-butyl group, 2-ethylhexyl group, lauryl group (dodecyl group), palmityl group (hexadecyl group), stearyl group (octadecyl group). ), An isostearyl group, an undecenyl group, an oleyl group, a cyclohexyl group, a dicyclohexyl group, a dicyclohexyl group, a phenyl group, a nonylphenyl group, or a paracumylphenyl group, but is not limited thereto.

In the general formula (5), specific examples of R ³¹ include a hydrogen atom or a methyl group.

In the general formula (6), specific examples of R ³³ include ethylene group, ethylene group and propylene group, propylene group, ethylene group and tetramethylene group, tetramethylene group, hexamethylene group, and octamethylene group. However, it is not limited to these.

Specific examples of R ³⁴ in general formula (6) include the same substituents as R ³² in general formula (5), but are not limited thereto.

<< Polyol (a) >>
<< Compound having two hydroxyl groups and one thiol group in the molecule (a1) >>
Examples of the compound (a1) having two hydroxyl groups and one thiol group in the molecule used in the present invention include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3 -Mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1, 3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, etc. Can be mentioned.

<< Vinyl polymer (a2) >>
The vinyl polymer (a2) having two hydroxyl groups at one end used in the invention and having two hydroxyl groups and one thiol group in the molecule is the vinyl polymer (a2) at the vinyl polymer site (C). According to the molecular weight of the intended vinyl polymer (a2), it can be obtained by mixing one or more ethylenically unsaturated monomers (a1) and, optionally, a polymerization initiator and heating. .

  The compound (a1) having two hydroxyl groups and one thiol group is used in an amount of 0.5 to 30 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (c), and bulk polymerization or solution polymerization is performed. It is preferably carried out, more preferably 3 to 12 parts by weight, still more preferably 4 to 12 parts by weight, particularly preferably 5 to 9 parts by weight. If the amount is less than 0.5 part by weight, the molecular weight of the vinyl polymer part (C) is too high, and the absolute amount increases as an affinity part for the inorganic fine particle carrier and the solvent, and the dispersibility effect itself decreases. When the amount exceeds 30 parts by weight, the molecular weight of the vinyl polymer part (C) is too low, and the effect of steric repulsion is lost as an affinity part for the inorganic fine particle carrier and solvent, and the aggregation of inorganic fine particles It may be difficult to suppress this.

  The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. When the temperature is lower than 40 ° C., the polymerization does not proceed sufficiently, and when the temperature is higher than 150 ° C., the molecular weight is increased.

The weight average molecular weight of the vinyl polymer moiety (C) is preferably 1,000 to 20,000, more preferably 2000 to 12,000, still more preferably 2,000 to 10,000, and particularly preferably 3,000 to 3,000. 8,000. This site becomes an affinity site for the inorganic fine particle carrier and the solvent. When the weight average molecular weight of the vinyl polymer site (C) is less than 1,000, the steric repulsion effect is lost as an affinity site for the inorganic fine particle carrier and the solvent, and it is difficult to suppress the aggregation of the inorganic fine particles. There is. On the other hand, if it exceeds 20,000, the absolute amount increases as an affinity site for the inorganic fine particle carrier and the solvent, and the dispersibility effect itself may decrease. Further, the viscosity of the dispersion may increase.
The vinyl polymer (a2) can easily adjust the molecular weight to the above range, and also has good affinity for the solvent.

  In the polymerization, 0.001 to 5 parts by weight of a radical polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (c). As the radical polymerization initiator, azo compounds and organic peroxides can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These radical polymerization initiators can be used alone or in combination of two or more.

  In the case of solution polymerization, the polymerization solvents are ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like are used, but are not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more. After completion of the reaction, the solvent used in the polymerization reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

《Other polyols》
Examples of the polyol other than the compound (a1) contained in the polyol (a) and the polyol other than the vinyl polymer (a2) contained in the polyol (a) (hereinafter abbreviated as “other polyols”). A well-known thing can be used. Among them, there are those belonging to the following groups (1) to (7) as long as only typical ones are exemplified.
(1) ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, or Polyhydric alcohols such as hexanetriol; (2) polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol or Such as polyoxyethylene polyoxypropylene polyoxytetramethylene glycol, various polyether glycols;
(3) Various polyhydric alcohols described above and various (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether. Modified polyether polyols obtained by ring-opening polymerization with
(4) Polyester polyols obtained by co-condensation with one or more of the various polyhydric alcohols described above and polycarboxylic acids, wherein the polycarboxylic acids are succinic acid, adipic acid, sebacic acid, Azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1 , 2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid Polyols that can be used;
(5) A lactone system obtained by a polycondensation reaction between one or more of the various polyhydric alcohols described above and various lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. Polyester polyols, or
Lactone-modified polyester polyols obtained by polycondensation reaction of the various polyhydric alcohols, polycarboxylic acids, and various lactones;
(6) Various epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids (7) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated A castor oil derivative, a hydroxyl group-containing acrylic copolymer, a hydroxyl group-containing fluorine-containing compound, or a hydroxyl group-containing silicon resin can be used.

  The other polyols optionally added shown in (1) to (7) may be used alone or in combination of two or more, but the weight average molecular weight is compatible or dispersed. From the viewpoint of stability, it is preferably 40 to 10,000, more preferably 100 to 2,000, and still more preferably 100 to 1,000. When the weight average molecular weight is less than 40, there is no effect of improving the compatibility and dispersion stability, and when the weight average molecular weight is 10,000 or more, the compatibility is deteriorated.

  The number of hydroxyl groups in one molecule of other polyol is not particularly limited as long as the intended dispersant can be synthesized, but diol (a5) other than a compound having two hydroxyl groups and one thiol group in the molecule is preferable. In particular, by reacting with tetracarboxylic dianhydride (b1), carboxyl groups serving as inorganic oxide fine particle adsorption groups can be regularly arranged in the main chain, which is advantageous for inorganic oxide fine particle dispersion. When a polyol having more than two hydroxyl groups is used in a large amount, the main chain of the polyester is branched and becomes complicated and bulky, making it difficult to obtain a dispersion effect. It should be kept to a minimum from the viewpoint of design, for example, for adjusting the molecular weight of the polyester dispersant and adjusting the viscosity of the dispersion. The blending amount will be described later.

<< Polycarboxylic anhydride (b) >>
The polycarboxylic anhydride (b) used in the present invention preferably contains at least a tetracarboxylic dianhydride (b1). The two anhydride groups of the tetracarboxylic dianhydride (b1) react with the hydroxyl groups of the polyol (a) so that the carboxyl groups serving as the inorganic fine particle adsorbing groups are regularly arranged on the main chain of the polyester dispersant. This is advantageous for dispersing inorganic fine particles.

Examples of the tetracarboxylic dianhydride (b1) used in the present invention include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, , 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride Product, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3- Aliphatic tetra such as methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Rubonic dianhydride, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′- Benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7 -Naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3, 3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) Diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) Phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′- Diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) Fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,
Aromatic tetra such as 3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride Carboxylic dianhydrides are mentioned.

  The tetracarboxylic dianhydride used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Since the tetracarboxylic dianhydride forms a dispersant having two carboxyl groups in one unit of the polyester by reaction with the polyol, it is a constituent element of the polyester dispersant of the present invention from the viewpoint of adsorbing inorganic fine particles. As preferred.

  Furthermore, what is preferably used in the present invention is an aromatic tetracarboxylic dianhydride, more preferably a tetracarboxylic dianhydride having two or more aromatic rings, from the viewpoint of adsorptivity to inorganic fine particles. It is. Aromatic carboxylic acids have a higher ability to adsorb inorganic fine particles than aliphatic carboxylic acids, and carboxylic acids having two or more aromatic rings are skeletons suitable for adsorbing inorganic fine particles and have high heat resistance.

  Specific examples include aromatic tetracarboxylic dianhydrides represented by the following general formula (1) or general formula (2).

General formula (1):
[In General Formula (1), k is 1 or 2. ]
General formula (2):
[In General Formula (2), Q ₁ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, General Formula (3) :

Or a group represented by the general formula (4):

It is group represented by these. ]
Further, a compound having one carboxylic anhydride group in the molecule or a compound having three or more carboxylic acid anhydride groups is used in combination, that is, tetracarboxylic dianhydride (b) contained in the polycarboxylic anhydride (b) used in the present invention ( Polycarboxylic acid anhydrides other than b1) can also be used.

  The polycarboxylic acid anhydrides other than the tetracarboxylic dianhydride (b1) contained in the polycarboxylic acid anhydride (b) used in the present invention are dicarboxylic acid anhydride, tricarboxylic acid anhydride, 5 or more carboxylic acids. From the viewpoint of adsorptivity to fine inorganic oxide particles, a tricarboxylic acid in which two carboxyl groups are generated in one unit of a polyester dispersant by reaction with a polyol in the design of the polyester dispersant. Anhydride (b2) is preferred. Since tricarboxylic acid anhydride (b2) also reacts with only one hydroxyl group of the polyol, it should be minimized from the viewpoint of designing the molecular weight of the polyester dispersant. The blending amount will be described later.

  Examples of the tricarboxylic acid anhydride (b2) include an aliphatic tricarboxylic acid anhydride or an aromatic tricarboxylic acid anhydride. Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned. Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride Products), 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, 3,4,4'-biphenyl Sulfonic tricarboxylic acid anhydrides. What is preferably used in the present invention is an aromatic tricarboxylic acid anhydride among the above from the viewpoint of adsorptivity to fine inorganic oxide particles.

<< Synthesis of polyester dispersant (D) >>
<Synthesis of polyester>
First, the process of synthesizing the polyester of the polyester dispersant (D) of the present invention will be described by taking the reaction of diol (aa) and tetracarboxylic dianhydride (b1) as an example.

The tetracarboxylic dianhydride (b1) used in the present invention can react with a hydroxyl group to form an ester bond and leave a pendant carboxyl group on the resulting polyester main chain. When the molar amount of the diol (a5) having two hydroxyl groups is a, the molar amount of the tetracarboxylic dianhydride is b, i) a> b, ii) a = b, and iii) a <b The reaction of tetracarboxylic dianhydride (b) and polyol (a) is shown in the following general formulas (26), (27), and (28). If the acid anhydride group remaining in the product of the following general formula (26) is hydrolyzed, the product obtained by this reaction has 2 or 3 carboxyl groups in the X1 moiety in the structural formula. The plurality of carboxyl groups are effective as adsorption sites for the inorganic oxide fine particles.

General formula (26):
i) a> b

Formula (27):
ii) a = b

Formula (28):
iii) a <b

However, the case where only one carboxyl group is bonded to X ₁ is not preferable because high dispersibility, fluidity, and storage stability are not exhibited.

In the present invention, X ₁ is a reaction residue after the tetracarboxylic dianhydride has reacted with a hydroxyl group, and Y is a reaction residue after the polyol compound has reacted with an acid anhydride group. X ₁ is preferably a reaction residue after the tetracarboxylic dianhydride represented by the general formula (1) or the general formula (2) has reacted with the polyol compound.

<< Synthesis of polyester dispersant (D2) >>
A preferred polyester dispersant (D2) of the present invention is a vinyl polymer (S) atom in Y in the diol (aa) in the description of the synthesis of the polyesters represented by the general formulas (26) to (28). C) is introduced.

The introduction method includes the following two methods.
(1) Radical polymerization of an ethylenically unsaturated monomer (c) forming a vinyl polymer site (C) in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule. An acid in a polycarboxylic acid anhydride (b) containing at least a hydroxyl group in a polyol (a) containing at least a vinyl polymer (a2) having two hydroxyl groups at one end and a tetracarboxylic dianhydride (b1) React with an anhydride group.
(2) A polycarboxylic acid anhydride containing at least a hydroxyl group in a polyol (a) containing at least a compound (a1) having two hydroxyl groups and one thiol group in the molecule and a tetracarboxylic dianhydride (b1) The ethylenically unsaturated monomer (c) forming the vinyl polymer site (C) is radically polymerized in the presence of the polyester (d) obtained by reacting the acid anhydride group in (b).

  Here, four main synthesis patterns are shown by taking the method of introducing the vinyl polymer site (C) in (2) later as an example. In (1) and (2), if the raw material and the reaction conditions are the same depending on whether the introduction of the vinyl polymer site (C) is performed first or later, the same can be theoretically achieved. The molecular weight and the like may be slightly different depending on various conditions.

(2) Synthesis pattern 1)
The following general formula (29) is a polyester obtained by reacting the hydroxyl group of the compound (a1) having two hydroxyl groups and one thiol group at one end with the acid anhydride group of tetracarboxylic dianhydride (b1). It is the synthetic pattern 1 which radically polymerized the ethylenically unsaturated monomer (c) which forms a vinyl polymer site | part (C) in presence of (d1). Theoretically, the molar ratio of (a1) is a (integer), the molar ratio of (b1) is b (integer), and b = a-1, so that no acid anhydride group remains from the viewpoint of stability. This is the case where the terminal is a hydroxyl group. The molecular weight is adjusted by changing a.

Formula (29):
In actual synthesis, a is often excessive from the theoretical value so that no acid anhydride remains. When b> a and the acidic group is increased, the anhydride group is hydrolyzed with a necessary amount of water and used. The molar ratio of the hydroxyl group of the compound (a1) having two hydroxyl groups and one thiol group at one end to the acid anhydride group of the tetracarboxylic dianhydride (b1) is 2b / 2a = b / a = 0. .3 to 1.2 are preferred. If it is less than 0.3, the number of acid anhydride residues in one molecule is reduced, resulting in insufficient adsorption to the inorganic oxide fine particles. If it exceeds 1.2, an acid anhydride group remains and storage stability is maintained. In many cases, even when hydrolyzed, the acidic group becomes excessive and the compatibility with the inorganic oxide fine particle carrier and the solvent is deteriorated. From the viewpoint of inorganic oxide fine particle dispersibility and stability, b / a = 0.4 to 0.8 is more preferable.

(2) Synthesis pattern 2)
The following general formula (30) is a compound (a1) having two hydroxyl groups and one thiol group at one end and the hydroxyl groups of other diols (a5) and an acid anhydride group of tetracarboxylic dianhydride (b1). In the presence of the polyester (d2) obtained by the reaction, a synthetic pattern 2 obtained by radical polymerization of an ethylenically unsaturated monomer (c) that forms a vinyl polymer portion (C) having a glass transition temperature of less than 50 ° C. is there. From the viewpoint of stability, the molar amount of (a1) is a (integer), the molar amount of (a5) is α (integer), the molar amount of (b1) is b (integer), and b = a + α-1. This is a case where the terminal is a hydroxyl group so that no anhydride group remains. The molecular weight, solubility, and carboxyl group density are adjusted by changing the type of other diol (a5) and the ratio of a and α.

Formula (30):

  When actually synthesizing, (a + α) is often excessive from the theoretical value so that no acid anhydride remains. When b> (a + α) and the acidic group is increased, the anhydride group is hydrolyzed with a necessary amount of water. The molar ratio of the hydroxyl group of the compound (a1) or other diol (aa) having two hydroxyl groups and one thiol group at one end to the acid anhydride group of the tetracarboxylic dianhydride (b1) is 2b / 2 (a + α) = b / (a + α) = 0.3 to 1.2 is preferable. If it is less than 0.3, the number of acid anhydride residues in one molecule is reduced, resulting in insufficient adsorption to the inorganic oxide fine particles. If it exceeds 1.2, an acid anhydride group remains and storage stability is maintained. In many cases, even when hydrolyzed, the acidic group becomes excessive and the compatibility with the inorganic oxide fine particle carrier and the solvent is deteriorated. From the viewpoint of inorganic fine particle dispersibility and stability, b / a = 0.6 to 0.8 is more preferable.

  a = 0 does not correspond to the polyester dispersant (D2) because there is no vinyl polymer part (C). The other diol (a5) is used for adjusting the molecular weight, viscosity, or compatibility of the polyester dispersant. When another diol (a5) is used as in (Synthesis pattern 2), the molar ratio between the other diol (a5) and the compound (a1) having two hydroxyl groups and one thiol group at one end is α /A=0.1-2.0 is preferable. If it is less than 0.1, there is no effect of using the diol (a5), and if it exceeds 2.0, the density of the vinyl polymer portion (C) having a glass transition temperature of less than 50 ° C. is lowered, and the dispersibility is adversely affected. .

(2) Synthesis pattern 3)
The following general formula (31) is a hydroxyl group of a compound (a1) having two hydroxyl groups and one thiol group at one end, and acid anhydrides of tetracarboxylic dianhydride (b1) and tricarboxylic acid anhydride (b2). Synthetic pattern 4 obtained by radical polymerization of ethylenically unsaturated monomer (c) that forms vinyl polymer portion (C) having a glass transition temperature of 50 ° C. or higher in the presence of polyester (d3) obtained by reacting a group. It is. The molar amount of (a1) is a, the molar amount of (b1) is b, the molar amount of (b2) is β, b = a−1, β = 1, and the molecular weight of the main chain is adjusted by changing a. One end becomes a polycarboxylic acid moiety (B) by tricarboxylic acid (b2).

Formula (31):

When β = 2, both ends are polycarboxylic acid sites (B).

  In actual synthesis, a is often excessive from the theoretical value so that no acid anhydride remains. When (b + β)> a and the acidic groups are increased, the anhydride groups are hydrolyzed with a necessary amount of water. However, since the tricarboxylic acid anhydride (b2) is monofunctional, in theory, when a = b + 1 and β ≦ 2, the polyester terminal reaction is stopped by (b2), so that no acid anhydride group remains. The molar ratio of the hydroxyl group of the compound (a1) having two hydroxyl groups and one thiol group at one end to the acid anhydride groups of tetracarboxylic dianhydride (b1) and tricarboxylic acid (b2) is (b + β) /A=0.3 to 1.2 is preferable. If it is less than 0.3, the number of acid anhydride residues in one molecule is reduced, resulting in insufficient adsorption to the inorganic oxide fine particles. If it exceeds 1.2, an acid anhydride group remains and storage stability is maintained. In many cases, even when hydrolyzed, the acidic group becomes excessive and the compatibility with the inorganic oxide fine particle carrier and the solvent is deteriorated. From the viewpoints of inorganic oxide fine particle dispersibility and stability, (b + β) /a=0.6 to 0.8 is more preferable.

  The tricarboxylic acid anhydride (b2) is used for adjusting the molecular weight of the polyester dispersant and the absolute amount of the polycarboxylic acid site, such as making the terminal of the polyester dispersant a polycarboxylic acid site (B). However, when b = 0, the tetracarboxylic dianhydride (b1) is not used, which is outside the scope of the present invention. When tricarboxylic acid anhydride (b2) is used as in (Synthesis pattern 3), the molar ratio of tricarboxylic acid anhydride (b2) to tetracarboxylic acid dianhydride (b1) is β / b = 0.1. To 10 is preferred. If it is less than 0.1, there are few polyesters which have a polycarboxylic-acid part (B) in the terminal, and the effect of using a tricarboxylic acid anhydride (b2) together is not acquired. If it exceeds 10, the balance between the length of the polyester main chain, the number of polycarboxylic acid sites (B), and the number of vinyl polymer sites (C) is deteriorated, and the dispersion stability is often deteriorated. β / b = 0.5-3 is preferable.

(2) Synthesis pattern 4)
The following general formula (32) is a compound (a1) having two hydroxyl groups and one thiol group at one end and the hydroxyl groups of other diols (a5), tetracarboxylic dianhydride (b1) and tricarboxylic anhydride. An ethylenically unsaturated monomer (c) that forms a vinyl polymer moiety (C) having a glass transition temperature of less than 50 ° C. in the presence of the polyester (d4) obtained by reacting the acid anhydride group of (b2). Is a synthetic pattern 4 obtained by radical polymerization of The molar amount of (a1) is a (integer), the molar ratio of (a5) is α (integer), the molar ratio of (b1) is b, the molar ratio of (b2) is β, b = a + α-1, β = 1, a1> b1, and the molecular weight and properties of the main chain are adjusted by changing the ratio of a to α, and the tricarboxylic acid anhydride (b2) becomes the polycarboxylic acid moiety (B).

Formula (32):
When β = 2, both ends are polycarboxylic acid sites (B).

When actually synthesizing, (a + α) is often excessive from the theoretical value so that no acid anhydride remains. When (b + β)> (a + α) and an acidic group is increased, an anhydride group is hydrolyzed with a necessary amount of water and used. However, since the tricarboxylic acid anhydride (b2) is monofunctional, in theory, when (a + α) = b + 1 and β ≦ 2, since the polyester terminal reaction is stopped by (b2), no acid anhydride group remains. Compound (a1) having two hydroxyl groups and one thiol group at one end and other hydroxyl groups of diol (a5), and acid anhydride groups of tetracarboxylic dianhydride (b1) and tricarboxylic anhydride (b2) Is preferably (b + β) / (a + α) = 0.3 to 1.2. If it is less than 0.3, the number of acid anhydride residues in one molecule is reduced, resulting in insufficient adsorption to the inorganic oxide fine particles. If it exceeds 1.2, an acid anhydride group remains and storage stability is maintained. In many cases, even when hydrolyzed, the acidic group becomes excessive and the compatibility with the inorganic oxide fine particle carrier and the solvent is deteriorated. From the viewpoint of inorganic oxide fine particle dispersibility and stability, (b + β) / (a + α) = 0.6 to 0.8 is more preferable.
The other diol (a5) is used to adjust the molecular weight, viscosity, or compatibility of the polyester dispersant. When another diol (a5) is used as in (Synthesis pattern 2), the molar ratio between the other diol (a5) and the compound (a1) having two hydroxyl groups and one thiol group at one end is α /A=0.1-2.0 is preferable. If it is less than 0.1, there is no effect of using the diol (a5). There is a case.

  The tricarboxylic acid anhydride (b2) is used for adjusting the molecular weight of the polyester dispersant and the absolute amount of the polycarboxylic acid site, such as making the terminal of the polyester dispersant a polycarboxylic acid site (B). When the tricarboxylic acid anhydride (b2) is used as in (Synthesis pattern 4), the molar ratio of the tricarboxylic acid anhydride (b2) to the tetracarboxylic acid dianhydride (b1) is β / b = 0.1. To 10 is preferred. If it is less than 0.1, there are few polyesters which have a polycarboxylic-acid part (B) in the terminal, and the effect of using a tricarboxylic acid anhydride (b2) together is not acquired. If it exceeds 10, the balance between the length of the polyester main chain, the number of polycarboxylic acid sites (B), and the number of vinyl polymer sites (C) is deteriorated, and the dispersion stability is often deteriorated. β / b = 0.5-3 is preferable.

(Reaction catalyst)
As the catalyst used for the production of the polyester (d) and the polyester dispersant of the present invention, known catalysts can be used. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene and the like.

(Reaction solvent)
The polyester of the present invention and the polyester dispersant (D) can be produced using only the raw materials listed so far, but in order to avoid problems such as high viscosity and non-uniform reaction, a solvent is used. It is preferable to use it. There is no limitation in particular as a solvent used, A well-known thing can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile and the like can be mentioned. After completion of the reaction, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

(Reaction temperature)
The reaction temperature for polyester synthesis is 50 ° C to 180 ° C, preferably 80 ° C to 140 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the carboxyl group and the hydroxyl group may undergo an esterification reaction, resulting in a decrease in acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride disappears by infrared absorption. The reaction may be stopped when entering the range of 200 mg KOH / g.

(1) Composite pattern)
In the presence of polyesters (d1) to (d4) having a thiol group and a polycarboxylic anhydride residue (carboxyl group) obtained by the method 2) represented by the synthesis patterns 1 to 4, the thiol groups are linked. As a transfer agent, the vinyl polymer moiety (C) can be introduced into the polyester (d) by radical polymerization of the ethylenically unsaturated monomer (c) that forms the vinyl polymer moiety (C). In accordance with the molecular weight of the intended dispersant, the dispersant is obtained by mixing the ethylenically unsaturated monomer (c) with a polymerization initiator and heating. Bulk polymerization or solution polymerization is performed using 3 to 100 parts by weight of an ethylenically unsaturated monomer per 1 part by weight of the compound (a1) unit having two hydroxyl groups and one thiol group in the molecule. preferable. More preferably, it is 8-25 weight part, More preferably, it is 10-20 weight part. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C.

  In addition, the detailed polymerization method is as described above.

  In the method 1), for example, as shown in the general formula (33), -SH of the compound (a1) having two hydroxyl groups and one thiol group in the synthesis patterns 1 to 4 is converted to -S- [vinyl polymer part. (C)] is replaced from the beginning, and the polyester dispersant of the present invention is produced through the same polyester synthesis route, without the radical polymerization step in the presence of the polyesters (d1) to (d4).

Formula (33):

(Molecular weight)
The weight average molecular weight of the obtained polyester dispersant is preferably 2,000 to 25,000, more preferably 4,000 to 20,000, still more preferably 6,000 to 15,000, and particularly preferably 7,000. ~ 12,000. If the weight average molecular weight is less than 2000, the stability of the inorganic fine particle dispersion may be lowered, and if it exceeds 25,000, the interaction between the resins may be strengthened and the inorganic fine particle dispersion may be thickened. .

(Acid value)
Further, the acid value of the obtained polyester dispersant is preferably 5 to 200 mgKOH / g. More preferably, it is 10-150 mgKOH / g, More preferably, it is 15-100 mgKOH / g, Most preferably, it is 20-80 mgKOH / g. If the acid value is less than 5 mgKOH / g, the ability to adsorb inorganic fine particles may be reduced, and there may be a problem in dispersibility. There is a case.

  As described above, the polyol moiety (A) and the polycarboxylic acid moiety (B) are bonded to the main chain of the polyester obtained by reacting the hydroxyl group of the polyol (a) with the acid anhydride group of the polycarboxylic anhydride (b). ) In the polyester dispersant alternately having a vinyl polymer moiety (C) obtained by radical polymerization of an ethylenically unsaturated monomer (c) via an S atom on part or all of the polyol moiety (A). A polyester dispersant (D) is obtained.

  As shown in the general formula (34), the polyester dispersant of the present invention has a plurality of polycarboxylic acid sites (B) serving as an inorganic fine particle adsorbing portion in the main chain, and a solvent and an inorganic oxide fine particle carrier as side chains. Since it has a plurality of vinyl polymer sites (C) having high properties, it is suitable for dispersing the inorganic oxide fine particle dispersion, and the heat resistance of the inorganic fine particle dispersion carrier affinity portion is high. In addition, since the surfaces of light scattering particles and inorganic oxide fine particles are regularly coated, it is possible to prevent the particles from projecting to the surface during the formation of the coating film, thereby improving the flatness.

General formula (34)
SHAPE \ * MERGEFORMAT
The vinyl polymer portion (C) formed by radical polymerization of the ethylenically unsaturated monomer referred to in the present invention does not include a portion derived from tetracarboxylic dianhydride (b1) or tricarboxylic anhydride (b2). A plurality of vinyl polymer sites (C) are usually contained in one molecule constituting the polyester dispersant of the present invention.

  One molecule of the polyester dispersant (D) of the present invention has many vinyl polymer sites (C) and functions as an affinity site for the inorganic oxide fine particle carrier and the solvent. There is no practical lower limit or upper limit for the Tg of the vinyl polymer part (C), but a temperature lower than 50 ° C. is particularly preferable because the flatness is further improved.

When used for dispersing the light scattering particles (E) or the inorganic oxide fine particles (F), the blending amount of the polyester dispersant (D) is 100 parts by weight of the light scattering particles (E) or the inorganic oxide fine particles (F). The amount is preferably 1 to 200 parts by weight, more preferably 2 to 175 parts by weight, and most preferably 5 to 150 parts by weight. If it is 1 part by weight or more, the effect of dispersion stability can be confirmed. If it is 200 parts by weight or less, there is sufficient room for the polyester dispersant (D) to be a carrier, and there are practical problems such as flatness. It does not occur.
Moreover, in 100 weight% of resin compositions for light-scattering layers, Preferably it is 1-50 weight%, More preferably, it is 1-40 weight%, Most preferably, it is 2-30 weight%. Within this range, the flatness effect can be further improved.

<Resin (G)>
The resin composition for light scattering layers of the present invention contains a resin (G). By including resin (G), it can be made excellent in film formability, hardness, and adhesion to a substrate when used as a coating film.
Further, as described later, when the resin contains an acidic group, it is preferable because the resin composition for the light scattering layer can be provided with developability and can be patterned with an alkali developer, and further, inorganic oxide fine particles. When (F) is surface coated with aluminum hydroxide, it has a high affinity with the inorganic oxide fine particles (F), and a coating film excellent in transmittance and flatness can be obtained. This is preferable because it is possible.

  The resin (G) is preferably a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The resin (G) includes a thermoplastic resin, a thermosetting resin, a photosensitive resin, and the like, and these can be used alone or in combination of two or more.

  The content of the resin (G) is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, from the viewpoint of film formability.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of thermosetting resins include epoxy resins, benzoguanamine resins, melamine resins, rosin modified maleic resins, rosin modified fumaric resins, rosin modified maleic resins, rosin modified phenol resins, urea resins, amino resins, phenol resins, Saturated polyester resins, drying oils, synthetic drying oils and the like can be mentioned, but are not necessarily limited thereto. They can also be used in combination as a thermal crosslinking agent for the thermoplastic resin.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used. However, it is not necessarily limited to these.

When used in the form of an alkali development type photosensitive composition, an acid group is added after polymerization, such as a resin copolymerized with an acidic group-containing ethylenically unsaturated monomer, or a resin (g1) described later. It is preferable to use a resin obtained by polymerizing a polymerizable ethylenically unsaturated monomer as an ethylenically unsaturated monomer component. In order to further improve the photosensitivity, a photosensitive resin having an ethylenically unsaturated double bond can be used.
Examples of the acrylic alkali-soluble resin copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group.

  When copolymerizing using an acidic substituent-containing ethylenically unsaturated monomer, for example, (meth) acrylic acid, itaconic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meth) Ethylenically unsaturated monomers (unsaturated monobasic acids) having a carboxyl group, such as monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituents of acrylic acid, and phenols such as N-hydroxyphenylmaleimide An ethylenically unsaturated monomer having an ionic hydroxyl group, polybasic acid anhydrides such as tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like can be used.

The double bond equivalent of the resin (G) is preferably 350 g / mol or more and 1300 g / mol or less, and most preferably 350 g / mol or more and 1000 g / mol or less.
If the double bond equivalent of the resin (G) is larger than 1300 g / mol, the developing speed is slow, and even if patterning can be performed, a coating film with a large amount of residue may be formed. If the double bond equivalent is less than 350 g / mol, there are too many cross-linking components and the stability may be poor, or the coating film may become brittle.

  The average molecular weight Mw of the resin (G) is preferably 5000 or more and 20000 or less, and most preferably 5000 or more and 15000 or less. When the average molecular weight Mw of the resin (G) is larger than 20000, the developing speed may be slow and a residue may remain on the coating film, and when it is less than 5000, the chemical resistance may be deteriorated.

  Among these, as the resin (G) of the present invention, since a resin composition for a light scattering layer having excellent flatness, less dark spot generation, and excellent developability can be obtained, the resin (g1) described later. Or a resin (g2).

[Resin (g1)]
Resin (g1) includes an ethylenically unsaturated monomer (G1) having an epoxy group, and the following ethylenically unsaturated monomers (G2-1), (G2-2), (G2-2) other than (G1) 3) and a side chain epoxy group of the copolymer obtained by copolymerizing with one or more other ethylenically unsaturated monomers (G2) selected from the group consisting of (G2-4) , A resin in which an ethylenically unsaturated double bond and a carboxyl group are introduced by reacting a carboxyl group of an unsaturated monobasic acid (G3), and further reacting the generated hydroxyl group with a polybasic acid anhydride (G4). It is.

<< Ethylenically unsaturated monomer having epoxy group (G1) >>
Examples of the ethylenically unsaturated monomer (G1) having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4 epoxybutyl (meth). An acrylate and 3,4 epoxy cyclohexyl (meth) acrylate are mentioned, These may be used independently or may use 2 or more types together. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

<< Other ethylenically unsaturated monomers (G2) >>
Examples of the other ethylenically unsaturated monomer (G2) include the following (G2-1), (G2-2), (G2-3), and (G2-4), and an ethylenic group having an epoxy group Other than the unsaturated monomer (G1).

  Hereinafter, the ethylenically unsaturated monomers (G2-1), (G2-2), (G2-3), and (G2-4) will be described in order. In the present specification, the content% by weight of each monomer is the weight% of the precursor that brings each structural unit to the resin (g1).

<< ethylenically unsaturated monomer (G2-1) >>
The ethylenically unsaturated monomer (G2-1) has a cyclic structure with an aromatic ring group represented by the general formula (11) and the general formula (12), and contributes to improvement in hardness. From the viewpoint of developability, the ethylenically unsaturated monomer (G2-1) is preferably 2 to 80% by weight based on the weight of all the structural units of the resin (g1). If it is less than 2% by weight, the developability may deteriorate. On the other hand, if it exceeds 80% by weight, the dissolution rate in an alkaline developer becomes slow, and the development time may be long and the productivity may deteriorate.

General formula (11):

Formula (12):
[In General Formulas (11) and (12), R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

  Examples of the ethylenically unsaturated monomer (G2-1) include styrene, α-methylstyrene, divinylbenzene, indene, acetylnaphthene, benzyl acrylate, benzyl methacrylate, bisphenol A diglycidyl ether di (meth) acrylate, and methylolated melamine. Monomers (oligomers) such as (meth) acrylic acid esters, or ethylenically unsaturated monomers represented by the general formula (13). These are particularly preferable because a benzene ring can be introduced into the side chain of the resin (g1). By introducing a benzene ring into the side chain of the resin (g1), the side chain benzene ring is effective in improving developability. Furthermore, benzyl acrylate and / or benzyl methacrylate are most preferred from the viewpoint of development residue.

General formula (13):
(In General Formula (13), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon that may have a benzene ring. (It is an alkyl group of the number 1-20, and n is an integer of 1-15.)

Examples of the ethylenically unsaturated monomer represented by the general formula (13) include:
New Frontier CEA [EO-modified cresol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : methyl group, n = 1 or 2], NP-2 [n-nonylphenoxy polyethylene] Glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n = 2], N-177E [n-nonylphenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene Group, R ₈ : n-nonyl group, n = 16 to 17], or PHE [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
Daicel, IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], or Ebecryl 110 [ethoxylated phenyl acrylate (EO 2 mol), R _6: a hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n = 2],
Aronix M-101A manufactured by Toagosei Co., Ltd. [phenol EO modified (n≈2) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], M-102 [phenol EO modified ( n≈4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈4], M-110 [paracumylphenol EO modified (n≈1) acrylate, R ₆ : hydrogen atom , R _7: an ethylene group, R _8: Parakumiru, n ≒ 1], M-111 [n- nonylphenol EO-modified (n ≒ 1) acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: n- Nonyl group, n≈1], M-113 [n-nonylphenol EO-modified (n≈4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈4], or M-117 [n-nonyl Phenol PO modified (n≈2.5) acrylate, R ₆ : hydrogen atom, R ₇ : propylene group, R ₈ : n-nonyl group, n≈2.5],
Kyoeisha light acrylate PO-A [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], P-200A [phenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n ≒ 2], NP-4EA [nonylphenol EO adduct acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: n-nonyl group, n ≒ 4 ], Or NP-8EA [[nonylphenol EO adduct acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈8], or light ester PO [phenoxyethyl methacrylate, R ₆ : Methyl group, R ₇ : propylene group, R ₈ : hydrogen atom, n = 1],
Manufactured by NOF Corporation Blemmer ANE-300 [nonylphenoxy polyethylene glycol acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: - nonyl group, n ≒ 5], ANP-300 [nonylphenoxy polypropylene glycol acrylate, R _6: a hydrogen atom, R _7: a propylene group, R _8: n-nonyl group, n ≒ 5], 43ANEP-500 [nonylphenoxy - polyethylene glycol - polypropylene glycol - acrylate, R _6: a hydrogen atom, R _7: an ethylene group And propylene group, R ₈ : -nonyl group, n≈5 + 5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n -Nonyl group, n≈9 + 3], 75AN EP-600 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n-nonyl group, n≈5 + 2], AAE-50 [phenoxypolyethylene glycol Acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], AAE-300 [phenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen Atom, n≈5.5], PAE-50 [phenoxypolyethylene glycol methacrylate, R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], PAE-100 [phenoxypolyethylene glycol methacrylate, R _6: a methyl group, R _7: an ethylene group, R _8: a hydrogen atom, n = ], Or 43PAPE-600B [phenoxy - polyethylene glycol - polypropylene glycol - methacrylate, R _6: a methyl group, R _7: an ethylene group and a propylene group, R _8: a hydrogen atom, n ≒ 6 + 6],
Shin-Nakamura Chemical Co., Ltd. NK ESTER AMP-10G [phenoxy ethyleneglycol acrylate (EO1mol), R _6: a hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n = 1], AMP-20G [phenoxy ethyleneglycol acrylate (EO 2 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], AMP-60G [phenoxyethylene glycol acrylate (EO ₆ mol), R ₆ : hydrogen atom, R ₇ : ethylene group , R ₈ : hydrogen atom, n≈6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1 mol), R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
Biscoat # 192 manufactured by Osaka Organic Chemical Co., Ltd. [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], or
Nippon Kayaku SR-339A [2-phenoxy ethyleneglycol acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n = 1], or SR-504 (ethoxylated nonylphenol acrylate, R ₆ : Hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group] and the like, but not limited thereto, two or more kinds may be used in combination.

In the ethylenically unsaturated monomer represented by the general formula (13), the alkyl group of R ₈ has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group includes not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When the carbon number of the alkyl group of R ₈ is 1 to 10, the adhesion to the substrate is enhanced, but when the carbon number exceeds 10, the long alkyl group tends to prevent the adhesion with the substrate. This tendency becomes more prominent as the carbon chain length of the alkyl group of R ₈ becomes longer. When the carbon number exceeds 20, the adhesion with the substrate is extremely lowered. Examples of the alkyl group having a benzene ring represented by R ₈ include a benzyl group and a 2-phenyl (iso) propyl group. Developability is improved by adding one side chain benzene ring.

  In the ethylenically unsaturated monomer represented by the general formula (13), n is preferably an integer of 1 to 15. When n exceeds 15, the hydrophilicity increases and the effect of solvation decreases, and the viscosity of the resin (g1) increases, and the viscosity of the photosensitive composition using this increases, which affects the fluidity. May give. From the viewpoint of solvation, n is particularly preferably 1 to 4.

<< ethylenically unsaturated monomer (G2-2) >>
The ethylenically unsaturated monomer (G2-2) has a cyclic structure with an aliphatic ring group represented by the chemical formula (14) and the chemical formula (15), imparts hardness to the coating film, and alkali development. Functions as a hydrophobic site for the liquid. Based on the weight of all the structural units of the resin (g1), the ethylenically unsaturated monomer (G2-1) is 2 to 40% by weight with respect to the whole resin from the viewpoint of developability and imparting hardness. Is preferred. If it is less than 2% by weight, developability and hardness are insufficient, and a problem that a high-quality coating film for a touch panel cannot be obtained may occur. Further, since the hydrophobicity at the time of development is insufficient, there is a problem of pattern peeling or chipping in the pixel portion. If it exceeds 40% by weight, the dissolution rate in an alkali developer may be slow, and the development time may be long, resulting in poor coating productivity.

Chemical formula (14):

Chemical formula (15):

Examples of the ethylenically unsaturated monomer (G2-2) include an ethylenically unsaturated monomer represented by the general formula (16), an ethylenically unsaturated monomer represented by the general formula (17), and the like.
Formula (16):

Formula (17):
[In General Formula (16) and General Formula (17), R ₉ is a hydrogen atom or a methyl group, R ₁₀ is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 1 to 15. It is. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (16) include:
FANCLIL FA-513A [dicyclopentanyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], or FA-513M [dicyclopentanyl methacrylate, R ₉ : methyl, R ₁₀ manufactured by Hitachi Chemical Co., Ltd. : None, m = 0] and the like, but not limited thereto, two or more kinds can be used in combination.

Examples of the ethylenically unsaturated monomer represented by the general formula (17) include:
FANCLIL FA-511A [dicyclopentenyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], FA-512A [dicyclopentenyloxyethyl acrylate, R ₉ : hydrogen atom, R ₁₀ : Ethylene group, m = 1], FA-512M [dicyclopentenyloxyethyl methacrylate, R ₉ : methyl group, R ₁₀ : ethylene group, m = 1], or FA-512MT [dicyclopentenyloxyethyl methacrylate, R _9: methyl group, R _10: an ethylene group, m = 1] and the like but can be exemplified, without limitation, can be used in combination of two or more kinds.

<< ethylenically unsaturated monomer (G2-3) >>
The ethylenically unsaturated monomer (G2-3) is an ethylenically unsaturated monomer represented by the following general formula (40).
General formula (40):
[In General Formula (40), R ₂₁ and R ₂₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. ]

In the general formula (40), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ₂₁ and R ₂₂ is not particularly limited, and examples thereof include methyl, ethyl, linear or branched alkyl groups such as n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butyl An alicyclic group such as cyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; an alkyl group substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a hydrocarbon group which is difficult to be removed by heat are preferable from the viewpoint of heat resistance. R ₂₁ and R ₂₂ may be the same type of hydrocarbon group or different hydrocarbon groups.

  Specific examples of the ethylenically unsaturated monomer (G2-3) include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene). )] Bis-2-propenoate, di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis- 2-propenoate, di (n-butyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, Di (t-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis- 2-propenoate, di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di ( 2-ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1 -Ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis (Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate Di (t-butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2- Propenoate, di (tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di And adamantyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like. . Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred, and may be one kind or two or more kinds. Good.

  The ratio of the ethylenically unsaturated monomer (G2-3) in the monomer component in obtaining the resin (g1) is not particularly limited, but is 2 to 60% by weight, preferably 5 in the total monomer components. It is good that it is -55 weight%, More preferably, it is 5-50 weight%. If the amount of the ethylenically unsaturated monomer (G2-3) is too large, it may become difficult to obtain a low molecular weight during the copolymerization or may be easily gelled, while the amount is small. If it is too high, the coating film performance such as transparency and heat resistance may be insufficient.

<< ethylenically unsaturated monomer (G2-4) >>
The ethylenically unsaturated monomer (G2-4) is an ethylenically unsaturated monomer other than the ethylenically unsaturated monomer (G2-1), (G2-2), (G2-3). There is no particular limitation as long as it is copolymerizable with the ethylenically unsaturated monomer (G2-1), (G2-2), (G2-3). Among these, an ethylenically unsaturated monomer having a hydroxyl group, an ethylenically unsaturated monomer having a hydroxyl group, and a side chain cyclic ether-containing monomer are preferable.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

The side chain type cyclic ether-containing monomer is, for example, an unsaturated compound containing at least one skeleton selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a lactone skeleton.
Examples of the tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth) acrylic acid tetrahydrofuran-3-yl ester, and the like;
Examples of the furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, and 1-furan. 2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-ene -3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2-furyl) -6-methyl-1-hepten-3-one, and the like;
Examples of the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and tetrahydropyran 2-methacrylate. 2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like;
Examples of the pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone and 4- (1,5-dioxa-6-oxo-7-octenyl) -6. -Methyl-2-pyrone and the like;
Examples of the lactone skeleton include 2-propenoic acid 2-methyl-tetrahydro-2-oxo-3-furanyl ester, 2-propenoic acid 2-methyl-7-oxo-6-oxabicyclo [3.2.1] oct-2- Yl ester, 2-propenoic acid 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-7-yl ester, 2-propenoic acid 2-methyl-tetrahydro-2-oxo- 2H-pyran-3-yl ester, 2-propenoic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenoic acid hexahydro-2-oxo-2,6-methanofuro [3,2-b]- 6-yl ester, 2-propenoic acid 2-methyl-2- (tetrahydro-5-oxo-3-furanyl) ethyl ester, 2-propenoic acid 2-methyl ester Ru-decahydro-8-oxo-5,9-methano-2H-furo [3,4-g] -1-benzopyran-2-yl ester, 2-propenoic acid 2-methyl-2-[(hexahydro-2- Oxo-3,5-methano-2H-cyclopenta [b] furan-6-yl) oxy] ethyl ester, 2-propenoic acid 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl) oxy] propyl And 2-propenoic acid 2-methyl-2-oxy-1-oxaspiro [4.5] dec-8-yl ester.
Among these, tetrahydrofurfuryl (meth) acrylate is preferable from the viewpoint of coloring and availability. These side chain type cyclic ether-containing monomers may be used alone or in combination of two or more.

  The ratio of the side-chain cyclic ether-containing monomer in the monomer component when obtaining the resin (g1) is not particularly limited, but is 10 to 80 weights based on the weight of all the structural units of the resin (g1). %, Preferably 20 to 70% by weight, more preferably 30 to 60% by weight. If the amount of the side chain type cyclic ether-containing monomer is too large, the hydrophilicity becomes too strong and the surface is whitened during alkali development, the pattern is missing, or the adhesion to the substrate is likely to be lowered. On the other hand, if the amount is too small, performance such as heat resistance may be insufficient.

  Examples of other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid esters such as hydroxyethyl; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadiene, isoprene and the like Butadiene or substituted butadiene compounds; ethylene, propylene, vinyl chloride Le, ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate; and the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.

  The method for the polymerization reaction of the monomer component is not particularly limited, and various conventionally known polymerization methods can be employed, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used. Depending on the molecular weight of the target polymer, the polymerization temperature is preferably 40 to 150 ° C. and the polymerization concentration is 5 to 50%, and more preferably, the polymerization temperature is 60 to 130 ° C. and the polymerization concentration is 10 to 40%. It is good to do.

<Unsaturated monobasic acid (G3)>
As unsaturated monobasic acid (G3), (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substitution And monocarboxylic acids such as isomers, and these may be used alone or in combination of two or more.

<Polybasic acid anhydride (G4)>
Examples of the polybasic acid anhydride (G4) include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having a radical polymerizable double bond is used as the polybasic acid anhydride, the radical polymerizable double bond can be further increased.

<< Resin (g2) >>
Resin (g2) includes an ethylenically unsaturated monomer having a carboxyl group such as an unsaturated monobasic acid (G3), the ethylenically unsaturated monomer (G2-1), (G2-2), ( G2-3) and a side chain carboxyl of the copolymer obtained by copolymerizing with one or more other ethylenically unsaturated monomers (G2) selected from the group consisting of (G2-4) It is a resin in which an ethylenically unsaturated double bond and a carboxyl group are introduced by adding an ethylenically unsaturated monomer (G1) having an epoxy group to a part of the group.

  The content of the resin (g2) is preferably 5 to 70% by weight and more preferably 10 to 60% by weight in the resin composition for a light scattering layer from the viewpoint of film formability.

<An ethylenically unsaturated monomer having a carboxyl group>
Examples of the ethylenically unsaturated monomer having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meth) acrylic described in unsaturated monobasic acid (G3). Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituents of acids, and itaconic acid, maleic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, terephthalic acid, N-hydroxyphenylmaleimide, etc. Examples include ethylenically unsaturated monomers having a phenolic hydroxyl group. These may be used alone or in combination of two or more.

<Thermal reactive compound>
The resin composition for a light scattering layer of the present invention can further contain a heat-reactive compound in order to further impart coating film durability. The thermoreactive compound is non-reactive at room temperature, but exhibits a crosslinking reaction, a polymerization reaction, a polycondensation reaction, or a polyaddition reactivity at a temperature of 100 ° C. or higher (preferably 150 ° C. or higher), for example. A compound. Although the molecular weight of a thermoreactive compound is not specifically limited, Preferably it is 50-2000, More preferably, it is 100-1000.

  Examples of thermally reactive compounds include melamine compounds, benzoguanamine compounds, carbodiimide compounds, epoxy compounds, oxetane compounds, phenolic compounds, benzoxazine compounds, blocked carboxylic acid compounds, blocked isocyanate compounds, acrylate monomers, and silane couplings. One or more compounds selected from the group consisting of agents can be used. Particularly preferred is a thermoreactive compound containing at least a melamine compound or a benzoguanamine compound.

  Examples of the melamine compound or benzoguanamine compound include those having an imino group, a methylol group, or an alkoxymethyl group. Among these, a melamine compound or a benzoguanamine compound containing an alkoxyalkyl group is preferable. When the melamine compound or benzoguanamine compound containing an alkoxyalkyl group is used, the storage stability of the resin composition for a light scattering layer of the present invention is remarkably improved.

  Examples of the melamine compound or benzoguanamine compound containing an alkoxyalkyl group include hexamethoxymethylol melamine, hexabutoxymethylol melamine, tetramethoxymethylol benzoguanamine, tetrabutoxymethylol benzoguanamine and the like, but are not necessarily limited thereto. .

  Specific examples of commercially available melamine compounds include the following. However, it is not necessarily limited to these.

  Nikarak MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX750, MX-708, MX- manufactured by Sanwa Chemical Co., Ltd. 706, MX-042, MX-035, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410, MX-302, Cymel 300, 301, 303 manufactured by Nihon Cytex Industry 350, 370, 325, 327, 703, 712, 01, 285, 232, 235, 236, 238, 211, 254, 204, 202, 207, My Coat 506, 508, 212, 715, and the like.

  Among them, an alkoxyalkyl group-containing melamine compound is preferable. Nikalac MW-30M, MW-30, MW-22, MS-21, MX-45, MX-500, MX-520, MX manufactured by Sanwa Chemical Co., Ltd. -43, MX-302, Cymel 300, 301, 303, 350, 285, 232, 235, 236, 238, My Coat 506, 508 manufactured by Nippon Cytex Industries.

  Specific examples of commercially available benzoguanamine compounds include, for example, Nikalac BX-4000, SB-401, BX-37, SB-355, SB-303, SB301, BL-60, SB-255, SB manufactured by Sanwa Chemical Co., Ltd. -203, SB-201, Cymel 1123 manufactured by Nippon Cytex Industries, Ltd., My Coat 105, 106, 1128, and the like.

  Among these, Sanka Chemical's Nikalac BX-4000 and SB-401 and Nippon Cytex Industries' Cymel 1123, which are alkoxyalkyl group-containing benzoguanamine compounds, are preferable.

Epoxy compounds include bisphenol A-based epoxy compounds / or resins, hydrogenated bisphenol A-based epoxy compounds / or resins, bisphenol F-based epoxy compounds / or resins, hydrogenated bisphenol F-based epoxy compounds / or resins, and novolak-type epoxy compounds / Or resin, cycloaliphatic epoxy compound / or resin, heterocyclic epoxy compound / or resin, glycidyl ether compound / or resin, glycidyl ester compound / or resin, glycidylamine compound / or resin, epoxidized oil Epoxy compounds / resins such as: Brominated derivatives of the epoxy compounds / resins, tris (glycidylphenyl) methane, triglycidyl isocyanurate and the like.
These epoxy compounds / or resins can be used singly or in combination of two or more at any ratio as required.

  Examples of commercially available epoxy compounds include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (the above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (above are trade names; manufactured by Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (trade names; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade names; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (Trade name; manufactured by Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 ( The above is the product name; Japan Epoxy Gin Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (above are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021P, EHPE-3150 (above trade names: Daicel Chemical) Manufactured by Kogyo Co., Ltd.), Denacol EX-810, EX-830, EX-851, EX-611, EX-512, EX-421, EX-411, EX-321, EX-313, EX-201, EX- 111 (the above is a trade name; manufactured by Nagase ChemteX Corporation) and the like, but is not limited thereto.

  Among these, Celoxide 2021P, EHPE-3150, EX-611, EX-411, EX-321, or EX-313 are preferable, and EX-611, EX-411, EX-321, EX-313.

  As the phenol compound, for example, both a novolac type phenol compound obtained by reacting phenols and aldehydes under an acidic catalyst and a resol type phenol compound obtained by reacting under a basic catalyst can be used. Examples of phenols include orthocresol, paracresol, paraphenylphenol, paranonylphenol, 2,3-xylenol, phenol, metacresol, 3,5-xylenol, resorcinol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol. B, bisphenol E, bisphenol H, bisphenol S and the like. Examples of aldehydes include formaldehyde and acetaldehyde. Phenols and aldehydes may be used singly or in combination of two or more.

  Examples of the isocyanate compound of the blocked isocyanate compound include hexamethylenediisocyanate, isophorone diisocyanate, toluidine isocyanate, diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, bis (4-isocyanatocyclohexyl) methane, tetra Diisocyanates such as methylxylylene diisocyanate, isocyanurates of these diisocyanates, trimethylolpropane adduct type, biuret type, prepolymer having an isocyanate residue (low polymer obtained from diisocyanate and polyol), uretdione having an isocyanate residue, etc. However, the present invention is not necessarily limited to this.

  Examples of the blocking agent for the blocked isocyanate compound include phenol (dissociation temperature of 180 ° C. or higher), ε-caprolactam (dissociation temperature of 160 to 180 ° C.), oxime (dissociation temperature of 130 to 160 ° C.), or active methylene (100 to 120 ° C.). ° C) and the like, but is not necessarily limited thereto. Moreover, it is used individually by 1 type or in combination of 2 or more types.

<Polyfunctional monomer (J)>
The resin composition for a light scattering layer of the present invention preferably contains a polyfunctional monomer (J). The polyfunctional monomer (J) includes a monomer or oligomer that is cured by ultraviolet rays or heat to generate a transparent resin. Among the polyfunctional monomers (J), a polyfunctional monomer having an acidic group or a polyfunctional monomer (J1) having 7 or more ethylenic double unsaturated bonds in one molecule is preferable because of excellent developability.

  Examples of the polyfunctional monomer (J) include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide modified trimethylolpropane Examples thereof include various acrylic esters and methacrylic esters such as tri (meth) acrylate and propylene oxide-modified trimethylolpropane tri (meth) acrylate.

  Commercially available products include M-350 (trimethylolpropane ethylene oxide modified triacrylate), M-450 (pentaerythritol tri and tetraacrylate), M-402 (dipentaerythritol penta and hexaacrylate) (manufactured by Toa Gosei Co., Ltd.), Examples include Kayrad DPCA30 (caprolactone-modified dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku Co., Ltd.).

  Further, it preferably contains a polyfunctional monomer having an acidic group, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid And esterified products of monohydroxyalkyl (meth) acrylates. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like monohydroxy oligoacrylates or monohydroxy oligomethacrylates And monoesterified products containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. be able to.

Moreover, the compound represented by the following general formula (18) can also be used preferably.
General formula (18):
_{(H 2 C = C (R} 51) COO) h -X- (OCOCH (R 9) CH 2 S (R 50) COOH) i
[In General Formula (18), R ₅₁ is a hydrogen atom or a methyl group, R ₅₀ is a hydrocarbon group having 1 to 12 carbon atoms, X is an (h + i) -valent organic group having 3 to 60 carbon atoms, h is 2 to 2 An integer of 18, i represents an integer of 1 to 3. ]

Here, the compound represented by the general formula (18) can be easily obtained by the following method, for example.
(1) A method of adding a mercapto compound to an obtained compound after esterifying the compound giving an organic group represented by X with acrylic acid to acrylate, and (2) a compound giving an organic group represented by X Is modified with a polyisocyanate compound, and then the resulting compound is acrylated with an acrylate compound having a hydroxyl group, and then a mercapto compound is added to the obtained compound. (3) An organic group represented by X is given. A method in which a compound is esterified with acrylic acid to be acrylated, then modified with a polyisocyanate compound, and a mercapto compound is added to the obtained compound.

  Examples of the compound giving an organic group represented by X include pentaerythritol, pentaerythritol modified caprolactone, pentaerythritol modified polyisocyanate, dipentaerythritol, dipentaerythritol caprolactone modified, dipentaerythritol polyisocyanate Denatured products can be mentioned.

  Examples of the mercapto compound include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.

[Multifunctional monomer (J1) having 7 or more ethylenic double unsaturated bonds in one molecule]
Among these polyfunctional monomers, the inclusion of a polyfunctional monomer (J1) having 7 or more ethylenically unsaturated bonds in one molecule is preferable because the developability is further improved.

The polyfunctional monomer (J1) having 7 or more ethylenically unsaturated bonds is preferably, for example, a polyfunctional monomer represented by the following general formula (19).
Especially, since it becomes what is excellent in developability, it is preferable that it is a polyfunctional monomer which has 7-16 ethylenically unsaturated bonds, and the case where it is 7-12 more is more preferable.

General formula (19):
[In the general formula (19), n is an integer of 0 to 4, and R ₂ is an ether group, an alkylene group, a tolylene group, an arylene group, a carbonyl group, a sulfonyl group, an ester group, and the general formula (20). R ₃ is a hydrogen atom or a methyl group, R ₄ is a group consisting of a hydroxyl group, a carboxyl group, and a (meth) acryloyloxy group. It is one selected from. ]

Formula (20):
[In the general formula (20), R ₅ represents an aliphatic, alicyclic or aromatic structure. ]

Among the compounds represented by the general formula (19), R ₂ is preferably an ether group or a divalent group having a structure represented by the general formula (20) in terms of surface hardness and adhesion.

Examples of R ₂ having an ether group include a compound obtained by reacting dipentaerythritol penta (meth) acrylate and polyfunctional isocyanate, and reacting dipentaerythritol penta (meth) acrylate with tetrabasic acid dianhydride. And a compound obtained by reacting dipentaerythritol penta (meth) acrylate with a polyfunctional epoxy compound.

Specific examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.
Specific examples of tetrabasic acid dianhydrides include pyromellitic anhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride. , Cyclopentanetetracarboxylic dianhydride, oxydiphthalic anhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydro trimellitate monoacetate), benzophenone tetracarboxylic dianhydride, methylcyclohexylene tetracarboxylic acid A dianhydride etc. can be mentioned.
Specific examples of the polyfunctional epoxy compound include tris (glycidylphenyl) methane, triglycidyl isocyanurate, bis (3,4-epoxycyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl). Examples thereof include adipate, methylene bis (3,4-epoxycyclohexane), bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and novolak type epoxy resin.

Among the polyfunctional monomers in which R ₂ is an ether group in the general formula (19), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol Deca (meth) acrylate, pentapentaerythritol undeca (meth) acrylate, or pentapentaerythritol dodeca (meth) acrylate is preferred.
Among these, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, or pentapentaerythritol dodeca (meth) acrylate is most preferable. It may be included.

  As such a polyfunctional monomer (J1), for example, biscoat # 802 (a mixture of tripentaerythritol octaacrylate, tetrapentaerythritol decaacrylate, and pentapentaerythritol dodecaacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) is used. Can be mentioned.

When R ₅ is a divalent group having a structure represented by the general formula (20), it is more preferable in terms of surface hardness if n = 1 and R ₄ is a (meth) acryloyl group.

  Examples of such a polyfunctional monomer (J1) include TO-2323, TO-2324, TO-2325, TO-2326, TO-2327, and TO-2328 (manufactured by Toa Gosei Co., Ltd.). it can.

  The content of the polyfunctional monomer (J1) is preferably 5 to 20% by weight in a total of 100% by weight of the solid content of the resin composition. In this case, if the polyfunctional monomer (J1) is less than 5% by weight, the effect of increasing the surface hardness and imparting solvent resistance cannot be obtained. The amount added is reduced and a high refractive index cannot be obtained. More preferably, it is 5 to 15% by weight.

<Photopolymerization initiator (H)>
The resin composition of the present invention is prepared by adding a photopolymerization initiator (H) to form a cured film by curing the composition by ultraviolet irradiation or to form a coating film by a photolithography method. It is preferable to do.

As photopolymerization initiator (H), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpho Acetophenone photopolymerization initiators such as linopropan-1-one, 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl- Such as 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) Oxime ester photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin photopolymerization initiators such as benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, Benzophenone photopolymerization initiators such as hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4- Thioxanthone photopolymerization initiators such as diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-to Azine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, A triazine photopolymerization initiator such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, a borate photopolymerization initiator, a carbazole photopolymerization initiator, or Imidazole-based photopolymerization initiator, or the like are used.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  Of these, acetophenone-based photopolymerization initiators and oxime ester-based photopolymerization initiators are preferable because yellowing is less during the heating step and the transmittance is increased. Specific examples of the acetophenone photopolymerization initiator include Irgacure 907 (manufactured by BASF), Irgacure 379 (manufactured by BASF), and Irgacure 379EG (manufactured by BASF).

Among them, the oxime ester-based photopolymerization initiator has high sensitivity and can be added in a small amount, so that the amount of inorganic oxide fine particles added can be increased and the refractive index can be increased accordingly. Particularly preferred. These may be used alone or in combination.
Among the oxime ester photoinitiators, 1,2-octanedione-1- [4- (phenylthio) phenyl-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) is less yellowed during the heating process and has a high transmittance as a coating film, particularly around a wavelength of 400 nm. Since the photosensitive composition with high transmittance | permeability of can be provided, it is more preferable. These may be used alone or in combination. Specifically, Irgacure OXE01 (manufactured by BASF), Irgacure OXE02 (manufactured by BASF) and the like.

  The photopolymerization initiator (H) is preferably used in an amount of 0.5 to 10% by weight in a total of 100% by weight of the solid content of the photosensitive resin composition, and 0.5 to 5% by weight from the viewpoint of transmittance. More preferably, it is used in an amount of%.

The resin composition of the present invention further includes α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4 as a sensitizer. , 4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone and the like can be used in combination.
The sensitizer can be used in an amount of 0.1 to 150 parts by weight relative to 100 parts by weight of the photopolymerization initiator (H).

<Antioxidant>
The resin composition for a light scattering layer of the present invention can contain an antioxidant. The antioxidant can suppress a decrease in transmittance due to yellowing or the like due to the heating process. Therefore, by including an antioxidant, yellowing during the heating step can be prevented, and a coating film having a high transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Among these antioxidants, phenol-based antioxidants, phosphorus-based antioxidants and sulfur-based antioxidants are preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Among phenol-based compounds, hindered phenol-based antioxidants having high steric hindrance are particularly preferable.

[Phenolic antioxidant]
For example, 2,6-di-t-butyl-4-ethylphenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 , 5-triazine, 2,2-thio-diethylenebis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, N, N'-hexamethylenebis (3,5-di- t-
Butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanate Nurate, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methoxyphenol, triethylene glycol-bis {3- ( 3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, pentaerythris Lityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, octadecyl-3- (3,5 Di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenyl) benzene, and the like. You may use individually or 2 or more types.

Among them, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t- A hindered phenolic antioxidant selected from the group consisting of butyl-4-hydroxybenzylphosphonate-diethyl ester and tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate is: It is preferable from the viewpoint of photocurability.
Specific examples of the hindered phenol antioxidant include Yoshinox BHT (= 2,6-di-t-butyl-4-methylphenol), Tominox TT (= tetrakis- [methylene-3- (3,5 ′). -Di-t-butyl-4'-hydroxyphenyl) propionate] methane), Yoshinox SR, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Tominox SS, Tominox 917, GSY-314 (or more, Manufactured by API Corporation), IRGANOX245, IRGANOX259, IRGANOX565, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX107 , IRGANOX 1425WL, IRGANOX 1222, IRGANOX 1330 (above, manufactured by BASF Japan Ltd.), ADK STAB AO-70, ADK STAB AO-50, ADK STAB AO-330, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-80 (Asahi Denka) (Manufactured by Kogyo Co., Ltd.), Sumizer BM, Sumizer GM, Sumizer GP, Sumizer GS, Sumizer GA-80, Sumizer BP-101, Sumizer BP-76, and Sumizer BP-101 (manufactured by Sumitomo Chemical Co., Ltd.).

[Amine antioxidant]
Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Specific examples of the hindered amine-based antioxidant include Sanol LS-770, Sanol LS-765, Sanol LS-622LD, Kimasorp 944 (Sankyo Co., Ltd.), CYASORB UV-3346 (San Chemical Co., Ltd.), Knock rack 224, knock rack CD, Uvasil 299-299LM (above, Ouchi Shinsei Chemical Industry Co., Ltd.), MARK LA-63, MARKLA-68 (above, Asahi Denka Kogyo Co., Ltd.), TINUVIN 144, TINUVIN 312 (above, BASF・ Made by Japan).

[Phosphorus antioxidant]
Although what is marketed can be used as phosphorus antioxidant, Tris [2,4-di- (tert) -butylphenyl] phosphinetris [2-[[2,4,8,10-tetrakis ( 1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11- Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl) oxy] ethyl] amine, ethylbisphosphite (2,4-ditert-butyl-6-) Methylphenyl), and at least one compound selected from the group consisting of these is preferable, and one or more of these can be used.
Specific examples of phosphorus-based antioxidants include IRGAFOS168, IRGAFOS12, IRGAFOS38, IRGAFOSEPQ, (manufactured by BASF Japan Ltd.), Sumizer Z-16 (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB PEP-4C, ADK STAB PEP-8F, ADK STAB PEP-8, ADK STAB PEP-45, ADK STAB PEP-11C, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB P, ADK STAB C, ADK STAB QL, ADK STAB 135A, ADK STAB 1178, ADK STAB 1500, ADK STAB 1500, ADK STAB 3010, ADK STAB 522A, ADK STAB TPP (above, manufactured by Asahi Denka Kogyo Co., Ltd.), GSY-202 (above, AP Aiko Ltd. poration), SANKOHCA (Sanko Co., Ltd.), JPH1200, JP302, JPM313, JP304, JP308, JPP100, JP333E, JP318E, JP312 (manufactured by API Corporation) and the like.

[Sulfur antioxidants]
A sulfur-based antioxidant is an antioxidant containing sulfur in the molecule. As such a sulfur-containing antioxidant, commercially available ones can be used, but dioctadecyl 3,3′-thiodipropanoate, dimyristyl-3,3′-thiodipropionate, dipalmityl-3,3′- Thiodipropionate, distearyl-3,3′-thiodipropionate, 4,4′-thiobis-3-methyl-6-tert-butylphenol, thiodiethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], and is preferably at least one compound selected from the group consisting of these, and one or more of these may be used.
Specific examples of sulfur-based antioxidants include IRGANOXPS800FD, IRGANOXPS802FD (above, manufactured by BASF Japan Ltd.), Adekastab AO-503, Adekastab AO-412S (above, made by Asahi Denka Kogyo Co., Ltd.), Sumizer ZPL-R, Sumizer TPM, Sumilizer , Sumitizer TP-D, Sumizer TL, Sumizer MB (manufactured by Sumitomo Chemical Co., Ltd.), DLTP “Yoshitomi”, DSTP “Yoshitomi”, DMTP “Yoshitomi”, and DTTP “Yoshitomi” (manufactured by API Corporation).

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzotriazole antioxidant include Tomisorp 600 (manufactured by Yoshitomi Fine Chemical), TINUVIN 326, TINUVIN 327, TINUVIN P, TINUVIN 328 (above, manufactured by BASF Japan Ltd.), VIOSORB583, VIOSORB590 (manufactured by Kyodo Yakuhin). .

  As the benzophenone-based antioxidant, oligomer type and polymer type compounds having a benzophenone structure can be used.

  Examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4 -Octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4 -Methoxy-5 sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone, LA-51 (manufactured by Asahi Denka Kogyo Co., Ltd.) and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Specific examples of the benzophenone antioxidant include Tomisorp 800 (manufactured by API Corporation) and LA-51 (manufactured by Asahi Denka Kogyo Co., Ltd.).

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Specific examples of the triazine antioxidant include CYASORB UV-1164 (manufactured by Sun Chemical Co., Ltd.).

  Specifically, a compound such as IRGASTABFS042 (above, manufactured by BASF Japan Ltd.) can be used as the hydroxylamine-based antioxidant.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  The content of the antioxidant is preferably 0.1 wt% or more and less than 4 wt% in the total solid content of the resin composition of 100 wt%. When the amount is less than 0.1% by weight, it is difficult to obtain the yellowing prevention effect due to insufficient antioxidant, and when the amount is more than 4% by weight, the radicals generated during UV exposure are captured. May be insufficiently cured.

<Organic solvent>
The resin composition of the present invention can contain an organic solvent. The organic solvent may be added when preparing the resin composition, or may be used when preparing a dispersion of light scattering particles (B) or inorganic oxide fine particles (F).
Examples of the organic solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2- Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butane Diol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-di Chlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl Lucol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert -Butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene Glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropylene Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, cyclopentanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl Ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol , Methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, ethanol, n-propanol, iso-propanol, n-butanol, 2- Examples include butanol, n-octanol, and n-hexanol.
These organic solvents can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  Among these organic solvents, propylene glycol monomethyl ether acetate is preferable from the viewpoints of solubility and drying properties. By including propylene glycol monomethyl ether acetate, a coating film having excellent transparency after drying can be obtained.

  Further, in consideration of the drying property of the solvent, it is preferable to include a high boiling point solvent of 160 ° C. or higher in die coating or printing method, for example, 3-methoxy-3-methyl-1-butanol (bp 174 ° C.), 1, 3 -Butanediol (bp 203 ° C.), 3-methyl-1,3-butanediol (bp 203 ° C.), 2-methyl-1,3-propanediol (bp 213 ° C.), diisobutyl ketone (bp 168.1 ° C.), ethylene glycol mono Butyl ether (bp 171.2 ° C.), ethylene glycol monohexyl ether (bp 208.1 ° C.), ethylene glycol monobutyl ether acetate (bp 191.5 ° C.), ethylene glycol dibutyl ether (bp 203.3 ° C.), diethylene glycol monomethyl ether (bp 194.0) ℃), Jie Ren glycol monoethyl ether (bp 202.0 ° C.), diethylene glycol diethyl ether (bp 188.4 ° C.), diethylene glycol monoisopropyl ether (bp 207.3 ° C.), propylene glycol monobutyl ether (bp 170.2 ° C.), propylene glycol diacetate (bp 190 0.0 ° C.), dipropylene glycol monomethyl ether (bp 187.2 ° C.), dipropylene glycol monoethyl ether (bp 197.8 ° C.), dipropylene glycol monopropyl ether (bp 212.0 ° C.), dipropylene glycol dimethyl ether (bp 175 ° C.) ), Tripropylene glycol monomethyl ether (bp 206.3 ° C.), ethyl 3-ethoxypropionate (bp 169.7 ° C.), 3-methoxy Tyl acetate (bp 172.5 ° C.), 3-methoxy-3-methylbutyl acetate (bp 188 ° C.), γ-butyrolactone (bp 204 ° C.), N, N-dimethylacetamide (bp 166.1 ° C.), N-methylpyrrolidone (bp 202 ° C), p-chlorotoluene (bp162.0 ° C), o-diethylbenzene (bp183.4 ° C), m-diethylbenzene (bp181.1 ° C), p-diethylbenzene (bp183.8 ° C), o-dichlorobenzene (bp180) 0.5 ° C), m-dichlorobenzene (bp 173.0 ° C), n-butylbenzene (bp183.3 ° C), sec-butylbenzene (bp178.3 ° C), tert-butylbenzene (bp169.1 ° C), cyclo Hexanol (bp 161.1 ° C.), cyclohexyl acetate (b 173 ° C.), and methyl cyclohexanol (bp174 ℃) and the like. The high boiling point solvent at 160 ° C. or higher is preferably 5 to 50% by weight based on the total amount of the solvent.

  The organic solvent can be used in an amount of 100 to 5000 parts by weight based on 100 parts by weight of the total solid content of the resin composition of the present invention.

<Other ingredients>
In the resin composition of the present invention, an adhesion promoting additive, a monofunctional monomer, a surfactant, a storage stabilizer, a leveling agent, a light stabilizer and the like can be used as necessary.
<Adhesion promoting additive>
The resin composition for a light scattering layer of the present invention is preferable because the adhesion to a glass substrate, ITO or the like is improved by further including an adhesion promoting additive.
Adhesion promoting additives include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3- Minopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxy Examples include silane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane. .

  Among these, inclusion of a silane-based additive is preferable because adhesion to a glass substrate, ITO, and the like is improved, and 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Silicone “KBM-503”) is more preferable. Xylpropyltrimethoxysilane (Shin-Etsu Silicone “KBM-403”) and 3-mercaptopropyltrimethoxysilane (Shin-Etsu Silicone “KBM-803”) are particularly preferred.

<Silane compound (K)>
In the resin composition of this invention, it is preferable that a silane compound (K) is further included as an adhesion promotion additive. As the silane coupling agent (K), known ones can be used without particular limitation. Specifically, there are silane coupling agents having a vinyl group, an epoxy group, an amino group, a ureido group, a mercapto group, an isocyanate group, or the like. Can be mentioned.
Among these, a silane compound represented by the following general formula (21) having a urethane skeleton or an amide skeleton is preferable in order to improve the adhesion between the light transmissive substrate or the light transmissive electrode and the light scattering layer.

For example, isocyanate group-containing silane compounds such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropyltripropoxysilane are used as solvents, resins, and single quantities in the resin composition for light scattering layers. It may react with the body and moisture to become cloudy or gel. In addition, the cured coating film may not exhibit stable adhesion.
On the other hand, since the silane compound (K) represented by the general formula (21) does not have a highly reactive site such as an isocyanate group, it is thermally and chemically stable and has a resin composition for a light scattering layer. Among them, it is excellent in stability over time, and can stably exhibit good adhesion.

Formula (21):

[In General Formula (21), R ¹ is an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number. An aralkyl group having 7 to 30 carbon atoms or an alkaryl group having 7 to 30 carbon atoms is represented. X represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 1 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms.
R ² , R ³ and R ⁴ are independently of each other an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Represents an aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms, a siloxane group having a substituent, a halogen atom, a hydroxy group, or a hydrogen atom. ]

  The weight average molecular weight (Mw) of the silane compound (K) used in the present invention is preferably 200 or more and less than 5000. When the weight average molecular weight (Mw) of the silane compound (K) is less than 200, sufficient adhesion may not be obtained. When the weight average molecular weight is 5000 or more, the etchant resistance deteriorates, which may not be preferable.

  It is preferable that the usage-amount of the silane compound (K) used with the resin composition for light-scattering layers of this invention is 3 to 50 mass% in the resin composition for light-scattering layers, and 10 to 40 masses. % Is more preferable. If it is less than 3% by mass, sufficient adhesion cannot be obtained, and if it exceeds 50% by mass, the transmittance may decrease.

  The silane compound (K) is preferably used in an amount of 0.1 to 10% by weight in a total of 100% by weight of the solid content of the resin composition. If the amount is less than 0.1% by weight from the viewpoint of adhesion, the adhesion improving effect is difficult to obtain because the amount of adhesion promoting additive is small, and if it exceeds 10% by weight, the resin or polyfunctional monomer in the resin composition, Since photopolymerization initiators and the like are relatively reduced, characteristics such as adhesion and surface hardness tend to deteriorate.

Examples of the silane compound represented by the general formula (21) include (3-carbamateethyl) propyltriethoxysilane, (3-carbamateethyl) propyltrimethoxysilane, (3-carbamateethyl) propyltripropoxysilane, (3 -Carbamatepropyl) propyltriethoxysilane, (3-carbamatepropyl) propyltrimethoxysilane, (3-carbamatepropyl) propyltripropoxysilane, (3-carbamatebutyl) propyltriethoxysilane, (3-carbamatebutyl) propyl Trimethoxysilane, (3-carbamatebutyl) propyltripropoxysilane, (3-carbamatebutyl) butyltripropoxysilane, (3-carbamatebutyl) propylmethyldiethoxysilane, (3- Rubamate pentyl) propyltriethoxysilane, (3-carbamate hexyl) propyltriethoxysilane, 3-carbamate octyl) pentyl riboxysilane, (3-carbamateethyl) propylsilyltrichloride, (3-carbamateethyl) propyltrimethylsilane , 3-carbamateethyl) propyldimethylsilane, 3-carbamateethyl) propyltributylsilane, 3-carbamateethyl) ethyl-p-xylenetriethoxysilane, and 3-carbamateethyl) -p-phenylenetriethoxysilane. .
The silane compound represented by the general formula (21) may be added to the resin composition for a light scattering layer in the form of a silanol compound that is a hydrolyzate or in the form of a polyorganosiloxane compound that is a condensate.

[Storage stabilizer]
Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 5% by weight in a total of 100% by weight of the resin composition.

[Leveling agent]
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the resin composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-330 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in a total of 100% by weight of the resin composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Method for producing resin composition for light scattering layer>
The resin composition for light scattering layers of the present invention comprises a light scattering particle (E), an inorganic oxide fine particle (F), a polyester dispersant (D), and a photopolymerization initiator (H) and a resin (G ), Organic solvents, additives, polyfunctional monomers (J), silane compounds (K), adhesion promoting additives, colorants, chain transfer agents, plasticizers, surface conditioners, UV inhibitors, light stabilizers, oxidation It can be produced by mixing and stirring other components such as an inhibitor, an antistatic agent, an antiblocking agent, an antifoaming agent, a viscosity modifier, a wax, a surfactant, and a leveling agent. The production method is not particularly limited as long as it is a method used to uniformly mix particles and the above materials, and any conventionally known method that is usually used may be used.

The polyester dispersant (D) may be added as a simple substance to the resin composition for a light scattering layer.
Further, it is used for dispersion of inorganic oxide fine particles (F) (inorganic oxide fine particle (F) dispersion) or light scattering particles (E) (light scattering particle (E) dispersion), thereby It may be added to the scattering layer resin composition. Furthermore, you may disperse | distribute inorganic oxide microparticles | fine-particles (F), light-scattering particle | grains (E), etc. simultaneously using a polyester dispersing agent (D).

  From the viewpoint of dispersion stability and flatness, it is preferable to disperse the inorganic oxide fine particles (F) using the polyester dispersant (D) to obtain an inorganic oxide fine particle (F) dispersion. Particularly preferably, the inorganic oxide fine particles (F) and the light scattering particles (E) are dispersed using the polyester dispersant (D), and the inorganic oxide fine particle (F) dispersion and the light scattering particles (E) are dispersed. In this case, the dispersion is mixed to obtain a resin composition for a light scattering layer.

  The resin composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust and foreign matter.

"Light scattering layer"
The light scattering layer of the present invention is formed using the above-described resin composition for a light scattering layer of the present invention.
The light scattering layer of the present invention is, for example, coated with a resin composition for a light scattering layer on a light-transmitting substrate such as glass and dried, and the obtained coating film is heated or irradiated with ultraviolet rays or electron beams. It is obtained by applying and curing. As a coating method, a known method can be used. For example, a method using a rod or a wire bar; and microgravure coating, gravure coating, die coating, curtain coating, lip coating, slot coating, spin coating, etc. Various coating methods can be used.
When patterning the light scattering layer on the translucent substrate using the resin composition for the light scattering layer,
1) A method of directly patterning on a translucent substrate by a printing method;
2) A method of patterning by a photolithography method can be used.

1) The printing method can be performed by a normal printing method such as flexographic printing, gravure printing, gravure offset printing, offset printing, reverse offset printing, screen printing, letterpress printing, and ink jet printing.
2) In the photolithography method, it is used in the form of a photosensitive resin composition. In that case,
2-1) The resin composition for light scattering layer of the present invention was directly applied to a translucent substrate and dried, or 2-2) dissolved in a solvent on a film substrate (hereinafter referred to as a separate film). After the resin composition is applied, the photosensitive dry film obtained by drying the solvent is bonded to the light-transmitting substrate, and then adhered to the light-transmitting substrate and air bubbles are removed by lamination or vacuum lamination. After forming a light-scattering layer by performing, pattern formation is performed by a solution development or an alkali development process. In development, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is used as an alkali developer, and an organic alkali such as tetramethylammonium hydroxide (TMAH), dimethylbenzylamine, triethanolamine or the like can also be used. . Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase UV exposure sensitivity, a film that prevents polymerization inhibition by oxygen by coating and drying a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin after coating and drying the photosensitive resin composition. After forming, UV exposure can also be performed.

  Although the thickness of a light-scattering layer is not specifically limited, Usually, it is preferable that it is 0.5-20 micrometers. Moreover, the resin composition of this invention can be used as a light-scattering layer use. In particular, it is preferably used as a light scattering layer application of an organic EL device, but is not particularly limited to this application.

  In addition, when the light scattering layer of the present invention is applied to an organic EL device, if the wavelength dependency of the refractive index of the light scattering layer is large, there may be a problem that the brightness is changed in each color pixel and the white balance is lost. The light scattering layer preferably has a small difference in refractive index at each wavelength. Specifically, when the refractive indexes at wavelengths 473 nm, 594 nm, and 633 nm measured by a prism coupler are n (473), n (594), and n (633), respectively, n (473) / n (594), The value of n (633) / n (594) is preferably 0.2 to 2.0, more preferably 0.5 to 1.5, and still more preferably 0.95 to 1.05.

"Organic EL device"
The organic EL device of the present invention includes an organic EL element having a light scattering layer formed from a resin composition for a light scattering layer. The structure of the organic EL element is not particularly limited. As an example of the basic structure, a translucent substrate, at least one organic layer (organic EL layer) including a light emitting layer, a back electrode, and a TFT substrate are provided on the translucent substrate. One example is a bottom emission structure in which layers are sequentially stacked and light is extracted from the anode side. As another example, at least one organic layer (organic EL layer) including a back electrode, a light emitting layer, a translucent electrode, and a sealing layer are sequentially stacked on a TFT substrate, and light is extracted from the cathode side. The structure of top emission can be mentioned. These methods and techniques are described in Shinji Kido, “All about organic EL”, published by Nihon Jitsugyo Shuppansha (published in 2003).

  As an organic electroluminescence device, a light-scattering layer according to claim 11, a first electrode having translucency, at least one organic layer including a light-emitting layer, and light reflectivity are provided on a translucent substrate. It is preferable that the second electrode is sequentially stacked.

A structure of an organic EL device according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view of a bottom emission structure which is one example of the present embodiment. The organic EL device 1 of the present embodiment includes at least one including a light scattering layer 12, a light-transmitting first electrode (anode, light-transmitting electrode) 13, and a light-emitting layer on a light-transmitting substrate 11. Two organic layers (organic EL layers) 14 and a second electrode (cathode, back electrode) 15 having light reflectivity are sequentially laminated.
The light scattering layer 12 is a layer formed using the above-described resin composition for a light scattering layer of the present invention.

The organic EL device can be used for an organic EL lighting device or an organic EL display device.
In an active matrix organic EL display device, a plurality of light emitting layers that emit different colors are arrayed in a matrix. Further, a TFT substrate on which a pixel electrode composed of a second electrode (cathode, back electrode) 15 and a TFT (thin film transistor) as a switching element thereof is formed for each dot is provided.

As a site where the light scattering layer of the present invention is provided, for example, the following cases can be considered.
In the case of the bottom emission structure, for example, the following cases can be considered.
(1) Translucent substrate / light scattering layer / translucent electrode / organic EL layer / back electrode (2) Light scattering layer / translucent substrate / translucent electrode / organic EL layer / back electrode (3) Light Scattering layer / translucent substrate / light scattering layer / translucent electrode / organic EL layer / back electrode

In the case of the top emission structure, for example, the following cases can be considered.
(4) Substrate / Back electrode / Organic EL layer / Translucent or semi-transparent electrode / Light scattering layer / Protective substrate (5) Substrate / Back electrode / Organic EL layer / Translucent or semi-transparent electrode / Sealing layer / light scattering layer /
Protective substrate (6) Substrate / Back electrode / Organic EL layer / Translucent or semi-transparent electrode / Sealing layer / Protective substrate /
Light scattering layer (7) Substrate / Back electrode / Organic EL layer / Translucent or semi-transparent electrode / Light scattering layer / Protective substrate / Light scattering layer At this time, between the translucent substrate and the translucent electrode What contains the organic EL element provided with the light-scattering layer is more preferable from a viewpoint of light extraction efficiency.

As a manufacturing method of a bottom emission structure, after providing a light-scattering layer on a translucent substrate as mentioned above, a translucent electrode is formed on a light-scattering layer. As a material for the translucent electrode, a metal, an alloy, an inorganic oxide, an electrically conductive compound, or a mixture thereof can be used, and a material having a work function of 4 eV or more is preferable.
Specific examples include conductive inorganic oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO);
Metals such as gold, silver, chromium and nickel;
Other inorganic conductive materials such as copper iodide and copper sulfide;
Organic conductive materials such as polyaniline, polythiophene, PEDOT / PSS, and polypyrrole;
And mixtures or laminates thereof.
A conductive inorganic oxide is preferable, and ITO is particularly preferable in terms of productivity, high conductivity, translucency, and the like.

Further, in order to control the injection property of electrons or holes into the organic EL layer while maintaining the translucency, it is possible to laminate a metal and ITO to form a translucent electrode. Here, the thickness of the ultrathin metal is preferably 0.1 nm to 20 nm from the viewpoint of maintaining translucency. Further, the metals referred to herein include alkali metals (for example, Li, Na, and K) and fluorides thereof;
Alkaline earth metals (such as Mg and Ca) and their fluorides;
Gold, silver, lead, aluminum, sodium-potassium alloys, and mixed metals containing them;
Lithium-aluminum alloys and mixed metals containing them;
LiF / Al alloys and mixed metals containing them;
Magnesium-silver alloys and mixed metals containing them;
And rare earth metals such as indium and ytterbium.
Of these, materials having a work function of 4 eV or less are preferable, and aluminum, lithium-aluminum alloys and mixed metals thereof, magnesium-silver alloys and mixed metals thereof, and the like are more preferable.

The film thickness of the translucent electrode can be appropriately selected depending on the material, but is usually preferably about 50 nm to 300 nm.
As a method for forming the translucent electrode, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (such as a sol-gel method), and a method of applying a dissolved material or a dispersion material are used. The formed translucent electrode is etched to form a pattern as desired. Furthermore, the driving voltage of the apparatus can be lowered and the light emission efficiency can be increased by washing and other processing. For example, in the case of ITO, UV-ozone treatment is effective.

Next, after providing a translucent electrode on the surface of the light scattering layer as described above, an organic EL layer is formed on the surface of the translucent electrode.
The organic EL layer includes a light emitting layer, and may include a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, or the like. Each of these layers may have other functions.

  The material of the hole injection layer and the hole transport layer has either a function of injecting holes from the anode, a function of transporting holes, or a function of blocking electrons injected from the cathode. I just need it. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, anilines Examples thereof include copolymers, thiophene oligomers, and conductive polymer oligomers such as polythiophene.

The material of the light emitting layer can inject holes from the anode, hole injection layer, or hole transport layer when an electric field is applied, and can inject electrons from the cathode, electron injection layer, or electron transport layer. Any layer can be used as long as it can form a layer having a function, a function of transferring injected charges, and a function of emitting light by providing a recombination field of holes and electrons. For example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazines Derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, and 8-quinolinol derivative metal complexes or rare earths Various metal complexes represented by complexes;
And polymer compounds such as polythiophene, polyphenylene, and polyphenylene vinylene.

  Specific examples of the light-emitting material that becomes the light-emitting layer are listed below, but are not limited to the following specific examples.

  Blue light emission is obtained by using, for example, perylene, 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP), a 9,10-diphenylanthracene derivative, or the like as a guest material. In addition, styrylarylene derivatives such as 4,4′-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi), 9,10-di-2-naphthylanthracene (abbreviation: DNA), and 9,10-bis It can also be obtained from an anthracene derivative such as (2-naphthyl) -2-tert-butylanthracene (abbreviation: t-BuDNA). A polymer such as poly (9,9-dioctylfluorene) may also be used.

Green light is emitted from coumarin dyes such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (abbreviation: FIrpic), and bis (2-phenylpyridinato) acetyl. It can be obtained by using acetonatoiridium (abbreviation: Ir (ppy) (acac)) or the like as a guest material. Further, metals such as tris (8-hydroxyquinoline) aluminum (abbreviation: Alq ₃ ), BAlq, Zn (BTZ), and bis (2-methyl-8-quinolinolato) chlorogallium (abbreviation: Ga (mq) ₂ Cl) It can also be obtained from the complex. A polymer such as poly (p-phenylene vinylene) may also be used.

Light emission from orange to red is caused by rubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6-methyl-4H-pyran (abbreviation: DCM1), 4- (dicyanomethylene) -2- Methyl-6- (9-julolidyl) ethynyl-4H-pyran (abbreviation: DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -4H-pyran (abbreviation: BisDCM) Bis [2- (2-thienyl) pyridinato] acetylacetonatoiridium (abbreviation: Ir (thp) ₂ (acac)), and bis (2-phenylquinolinato) acetylacetonatoiridium (abbreviation: Ir (pq) ( acac)) and the like as a guest material. It can also be obtained from a metal complex such as bis (8-quinolinolato) zinc (abbreviation: Znq ₂ ) or bis [2-cinnamoyl-8-quinolinolato] zinc (abbreviation: Znsq ₂ ). A polymer such as poly (2,5-dialkoxy-1,4-phenylenevinylene) may be used.

  White light emission defines the energy level of each layer of the organic EL laminated structure and emits light using tunnel injection (European Patent No. 0390551). A light emitting element is described (Japanese Patent Laid-Open No. 3-230584), a light emitting layer having a two-layer structure is described (Japanese Patent Laid-Open No. 2-220390 and Japanese Patent Laid-Open No. Hei 2-216790), and a light emitting layer Are made of materials having different emission wavelengths (JP-A-4-51491), a blue light emitter (fluorescent peak 380 to 480 nm) and a green light emitter (480 to 580 nm). Laminated and further containing a red phosphor (Japanese Patent Laid-Open No. 6-207170), blue light emitting layer contains blue fluorescent dye, green light emitting layer is red fluorescent It includes an area containing iodine, etc. construction of what (JP-A-7-142169) and the like further containing a green phosphor.

The material for the electron injection layer and the electron transport layer only needs to have a function of injecting electrons from the cathode, a function of transporting electrons, or a function of blocking holes injected from the anode. Specific examples include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine. Derivatives, metal complexes of heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, silole derivatives, phthalocyanine derivatives, and 8-quinolinol derivatives;
Examples thereof include various metal complexes represented by metal complexes having metal phthalocyanine, benzoxazole, and benzothiazole as a ligand.

The thicknesses of the hole injection layer, the hole transport layer, the light emitting layer, the electron injection layer, and the electron transport layer are not particularly limited, but are preferably 10 nm to 500 nm. Each layer may have a single layer structure, or a multilayer structure having the same composition or different compositions.
The formation method of these layers is not particularly limited, but resistance heating evaporation method, electron beam evaporation method, sputtering method, molecular lamination method, coating method (spin coating method, casting method, dip coating method, etc.), A method such as the LB (Langmuir Blodgett) method is used. The resistance heating vapor deposition method and the coating method are preferable.

Finally, a back electrode is formed on the surface of the organic EL layer. The back electrode which is a negative electrode supplies electrons to an electron injection layer, an electron transport layer, a light emitting layer, or the like, and is selected in consideration of adhesion to an adjacent layer, ionization potential, stability, and the like. The back electrode preferably has light reflectivity. As a material for the back electrode, metals, alloys, conductive inorganic oxides, other conductive compounds, and mixtures thereof can be used. Specific examples include alkali metals (such as Li, Na, and K) and fluorides thereof;
Alkaline earth metals (such as Mg and Ca) and their fluorides;
Gold, silver, lead, aluminum, sodium-potassium alloys, and mixed metals containing them;
Lithium-aluminum alloys and mixed metals containing them;
LiF / Al alloys and mixed metals containing them;
Magnesium-silver alloys and mixed metals containing them;
And rare earth metals such as indium and ytterbium. A material having a work function of 4 eV or less is preferable, and aluminum, a lithium-aluminum alloy and a mixed metal thereof, a magnesium-silver alloy and a mixed metal thereof, and the like are more preferable. Further, in order to control the injection property of electrons or holes into the organic layer while maintaining the light reflectivity, the back electrode material and ITO can be laminated to form the back electrode.

  Although the film thickness of a back electrode can be suitably selected with material, 100 nm-1 micrometer are preferable normally. For the production of the back electrode, methods such as electron beam vapor deposition, sputtering, resistance heating vapor deposition, and coating are used. A metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. It is possible to deposit a plurality of metals at the same time to form an alloy electrode, or a previously prepared alloy may be deposited.

  As a manufacturing method of the top emission structure, there is a method in which a back electrode, an organic EL layer, a translucent electrode, and a light scattering layer are sequentially laminated on a substrate such as a TFT. The back electrode, organic EL layer, translucent electrode, light scattering layer material, lamination method, and the like described here may be the same as those described in the bottom emission manufacturing method.

  In addition, in order to improve the stability of the organic EL element against temperature, humidity, atmosphere, etc., a protective layer may be provided on the element surface or between layers, or the whole element may be covered or sealed with a resin or the like. . In particular, when covering or sealing the entire device, a molten glass, a photocurable resin that is cured by light, or the like is preferably used.

  The current applied to the organic EL element having the light scattering layer of the present invention is usually a direct current, but a pulse current or an alternating current may be used. The current value and the voltage value are not particularly limited as long as the element is within a range not destroying the element. However, considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electrical energy as possible.

  The driving method of the organic EL element having the light scattering layer of the present invention can be driven not only by the passive matrix method but also by the active matrix method. These methods and techniques are described in Shinji Kido, “All about organic EL”, published by Nihon Jitsugyo Shuppansha (published in 2003).

  The light emitted from the organic EL layer by applying a voltage between the translucent electrode and the back electrode of the organic EL device formed as described above is transmitted from the translucent electrode through the light scattering layer. Further, the light is transmitted through the translucent substrate and taken out. When the light emitted from the organic EL layer passes through the light scattering layer, the light is scattered and the directivity is changed, so that the totally reflected light is prevented from being guided.

  The organic EL device having the light scattering layer of the present invention can be applied in various forms. For example, the organic EL device comprising the light scattering layer of the present invention can be used as a full color display device. The main methods of the full color method include a three-color painting method, a color conversion method, and a color filter method. In the three-color coating method, an evaporation method using a shadow mask, an ink jet method, and a printing method can be used. In addition, Special Table 2002-53482, S.I. T. T. et al. Lee, et al. Proceedings of SID'02, p. 784 (2002) can also be used. The laser thermal transfer method (also referred to as Laser Induced Thermal Imaging, LITI method) can also be used. In the color conversion method, a light emitting layer that emits color light is used to convert green and red, which have wavelengths longer than colors, through a color conversion (CCM) layer in which fluorescent dyes are dispersed. The color filter method is a method of extracting light of three primary colors through a color filter for liquid crystal using a white light emitting organic EL light emitting element. In addition to these three primary colors, a part of white light is extracted and used for light emission. As a result, the luminous efficiency of the entire device can be increased.

  Furthermore, the organic EL element having the light scattering layer of the present invention may adopt a microcavity structure. This is because the organic EL element has a structure in which the light emitting layer is sandwiched between the anode and the cathode, and the emitted light causes multiple interference between the anode and the cathode, but the reflectance and transmission of the anode and the cathode. This is a technology that actively uses the multiple interference effect and controls the emission wavelength extracted from the device by appropriately selecting the optical characteristics such as the rate and the film thickness of the organic layer sandwiched between them. . Thereby, it is also possible to improve the emission chromaticity. For the mechanism of this multiple interference effect, see J.A. Yamada et al., AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002).

  The organic EL element having the light scattering layer of the present invention may adopt a multi-photon emission element structure. Multi-photon emission is an element structure in which a plurality of light emitting units including at least one light emitting layer are stacked so as to be connected in series via a charge generation layer (see, for example, Japanese Patent No. 3933593). According to such an element structure, light emission from a plurality of light emitting layers can be obtained simultaneously with the same amount of current as that of one unit element, so that current efficiency and external quantum efficiency equivalent to the number of light emitting units can be obtained. .

  As described above, the organic EL device having the light scattering layer of the present invention is used as a flat panel display such as a wall-mounted television or various flat light emitters, and further as a light source such as a copying machine or a printer, a liquid crystal display or an instrument. Application to a light source such as a light source, a display board, a marker lamp, etc. can be considered.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. Unless otherwise specified, “parts” represents “parts by weight” and “%” represents% by weight.

  First, the weight average molecular weight (Mw) of the vinyl polymer part (C) / resin (G) of the polyester dispersant / polyester dispersant, the double bond equivalent of the resin (G), the acid of the polyester dispersant / resin (G) Value, average primary particle diameter of light scattering particles, minor axis diameter of primary particles of inorganic oxide fine particles, and dispersion particle diameter of light scattering particle dispersion / inorganic oxide fine particle dispersion, and polyester dispersant vinyl The method for calculating the glass transition temperature of the polymerization site (C) will be described.

(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) was measured using gel permeation chromatography GPC-101 manufactured by Showa Denko K.K. Using THF (tetrahydrofuran) as a solvent, the molecular weight in terms of polystyrene was determined.

(Double bond equivalent)
Double bond equivalent is a measure of the amount of double bonds contained in a molecule. If the compounds have the same molecular weight, the amount of double bonds introduced increases as the double bond equivalent value decreases. . The double bond equivalent was calculated by the following formula.
[Double bond equivalent] = [molecular weight of monomer component having double bond] / [weight ratio of monomer component having double bond to all monomers in molecule]

(Acid value)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of a polyester dispersant solution or a resin solution and stirred to dissolve uniformly. An automatic titrator ("COM-") is used with a 0.1 mol / L KOH aqueous solution as a titrant. And the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Average primary particle size of light scattering particles)
The average primary particle size of the light scattering particles is measured directly from the electron micrograph using a transmission (TEM) electron microscope, and the minor axis diameter and major axis diameter of 100 light scattering particles are measured. The average value was measured as the primary particle diameter.
In the case of resin particles, since a solvent is included during synthesis, the particles were dried for 1 hour in a vacuum dryer at 100 ° C., and the particle size was observed after removing the solvent. In some cases, agglomeration occurs due to drying and a plurality of particles are adhered as a lump. In this case, a method of measuring the diameter by paying attention to each particle was used.

(Small axis diameter of primary particles of inorganic oxide fine particles)
Using a transmission (TEM) electron microscope, the size of primary particles is directly measured from an electron micrograph, the minor axis diameter of 100 inorganic oxide fine particles is measured, and the average value is the minor axis of the primary particles. The diameter.

(Dispersed particle size of light scattering particle dispersion and inorganic oxide fine particle dispersion)
Measurement was performed using “Nanotrack UPA” manufactured by Nikkiso Co., Ltd. A few drops of the light scattering particle dispersion liquid whose solid content weight% concentration was adjusted to 20% were poured into a cell filled with the same solvent as the dispersion liquid, and the signal level was measured at the optimum value.

(Calculation method of glass transition temperature of vinyl polymerization site (C))
The glass transition temperature of the vinyl polymerization site (C) is calculated from the following Fox formula from the glass transition temperature (catalog value) and weight fraction of each homopolymer of the ethylenically unsaturated monomer (c) used in the radical polymerization. Calculated with

Formula of Fox 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn
(W1 to Wn represent the weight fraction of the monomer used, and Tg1 to Tgn represent the glass transition temperature of the monomer homopolymer (unit is absolute temperature “K”).)

  Subsequently, the polyester dispersant (D), the resin (G) solution, the light scattering particle dispersion, the inorganic oxide fine particle dispersion, and the method for producing the silane compound will be described.

<Method for producing polyester dispersant (D)>
(Polyester dispersant (D-1))
(First step)
In a four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, 559 parts of dimethyl terephthalate, 420 parts of propylene glycol, 21.2 parts of glycerin, 0.2 part of zinc acetate, tetrabutyl ortho 0.025 parts of titanate was charged, and a transesterification reaction was performed at 160 to 220 ° C. with stirring under a nitrogen stream. When 95% (175 g) or more of the theoretical amount of methanol was distilled, the inside of the flask was gradually depressurized and reacted at 1 to 3 torr and 240 ° C. for 3 hours to obtain a polyester having a hydroxyl group at the terminal.
(Second step)
Next, the flask was depressurized with nitrogen and gradually cooled to 200 ° C. When the temperature reached 200 ° C., 65 parts of succinic anhydride was added and reacted for 1 hour to complete the reaction.
It melt | dissolved in cyclohexanone, the non volatile matter was adjusted to 50 weight%, and the cyclohexane solution of the polyester dispersing agent (D-1) of the weight average molecular weight 12,000 and acid value 40mgKOH / g was obtained.

(Polyester dispersant (D-2))
(First step)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. It was confirmed that 98% had reacted by solid content measurement, and the first step was completed. The weight average molecular weight of this reaction product was 2000.
(Second step)
To the reaction product, 36.6 parts of pyromellitic dianhydride was added and reacted at 100 ° C. for 5 hours. The acid value was measured to confirm that 97% or more of the acid anhydride had been half-esterified, and the second step was completed.
A solution with a non-volatile content of 50% was prepared by adjusting the solid content with cyclohexanone to obtain a cyclohexanone solution of a polyester dispersant (D-2) having a weight average molecular weight of 4000 and an acid value of 50 mgKOH / g.

(Polyester dispersant (D-3))
(First step)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 200 parts of n-butyl acrylate (n-BA) and 800 parts of methyl methacrylate (MMA) were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., 44 parts of 1,3-dimercapto-2-propanol was added and reacted for 12 hours. It was confirmed that 95% had reacted by solid content measurement.
(Second step)
Next, 500 parts of the solution obtained in the first step, 7.4 parts of pyromellitic anhydride (PMA), and 1,8-diazabicyclo- [5.4.0] -7-undecene (DBU) as a catalyst 1.4 parts were charged and reacted at 120 ° C. for 7 minutes. The reaction was continued until 98% or more of the acid anhydride was half-esterified as measured by the acid value.
The reaction solution was cooled and the solid content was adjusted with cyclohexanone to prepare a solution having a nonvolatile content of 50%. The weight average molecular weight was 20000, the acid value was 18 mgKOH / g, and the glass transition temperature of the vinyl polymerization site (C) was 61 ° C. A cyclohexanone solution of the polyester dispersant (D-3) was obtained.

(Polyester dispersant (D-4))
(First step)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 5 parts of n-butyl acrylate, 20 parts of tert-butyl methacrylate, 50 parts of 2-methoxyethyl acrylate, and 15 parts of methyl methacrylate. Replaced. A solution obtained by heating the inside of the reaction vessel to 80 ° C. and dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 45.7 parts of cyclohexanone in 6 parts of 3-mercapto-1,2-propanediol. And reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4000.
(Second step)
Next, 141.8 parts of the solution obtained in the first step, 9.7 parts of pyromellitic dianhydride, 70 parts of cyclohexanone, and 1,8-diazabicyclo- [5.4.0] -7- as a catalyst. 0.2 parts of undecene was added and reacted at 120 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value.
After completion of the reaction, the non-volatile content was adjusted to 50% by weight, cyclohexanone as a polyester dispersant (D-4) having a weight average molecular weight of 8100, an acid value of 50 mgKOH / g, and a glass transition temperature of vinyl polymerization site (C) of 22.5 ° C. A solution was obtained.

(Polyester dispersants (D-5) to (D-21))
The polyester dispersants (D-5) to (D-21) were synthesized in the same manner as the polyester dispersant (D-4) except that the raw materials and preparation amounts (parts by weight) described in Tables 4 to 5 were used. Of cyclohexanone was obtained.

The abbreviations in Table 4 and Table 5 are as follows.
n-BA: n-butyl acrylate EA: ethyl acrylate CHA: cyclohexyl acrylate BzMA: benzyl methacrylate t-BMA: tert-butyl methacrylate 2-MTA: 2-methoxyethyl acrylate MMA: methyl methacrylate MAA: methacrylic acid AIBN: 2, 2 '-Azobisisobutyronitrile PMA: pyromellitic dianhydride (Daicel Chemical Industries, Ltd.)
BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation)
BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.)
TMA: Trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.)
DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene (manufactured by Sun Apro Co., Ltd.)

<Method for Producing Resin (G) Solution>
(Resin solution (G-1))
Place 100 parts of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) into a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and inject nitrogen gas into the vessel While heating to 120 ° C., a mixture of 50.0 parts benzyl methacrylate, 15.8 parts methacrylic acid, 20.0 parts methyl methacrylate and 2.5 parts azobisisobutyronitrile from the dropping tube at the same temperature. The polymerization reaction was performed dropwise over 2.5 hours to obtain a resin solution having a weight average molecular weight of about 15,000. A resin solution (G-1) was prepared by adding propylene glycol monomethyl ether acetate such that the nonvolatile content was 40% by weight.

(Resin solution (G-2))
(First step)
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 100 ° C. while injecting nitrogen gas into the vessel. Mix 20.0 parts of benzyl methacrylate, 18.0 parts of methacrylic acid, 20.0 parts of methyl methacrylate, 40 parts of propylene glycol monomethyl ether acetate, and 3.5 parts of azobisisobutyronitrile from the dropping tube at a temperature. The solution was added dropwise over a period of time and further stirred at 100 ° C. for 5 hours to conduct a polymerization reaction.
(Second step)
Next, the inside of the flask was purged with air, and 1.0 part of trisdimethylaminomethylphenol and 2 parts of hydroquinone were dissolved in 21.6 parts of glycidyl methacrylate and charged into 30 parts of propylene glycol monomethyl ether acetate. The reaction was continued for 6 hours, and when the solid content acid value was 60 mg KOH / g, the reaction was terminated to obtain a resin solution having a weight average molecular weight of about 10,000. Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40% by weight to prepare a resin solution (G-2).

(Resin solution (G-3))
(Process 1)
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. M110 (paracumylphenol ethylene oxide modified acrylate) 17.2 parts, methyl methacrylate 25.0 parts, benzyl methacrylate 7.2 parts, glycidyl methacrylate 18.2 parts, and the precursor compound at this stage from the dropping tube at temperature As a required catalyst, a mixture of 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction.
(Process 2)
Next, the inside of the flask was purged with air, and 11.0 parts of methacrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.1 part of hydroquinone were added as a catalyst required for the combination of the precursors at this stage. Reaction was performed for 5 hours, and the resin solution whose weight average molecular weight is about 19000 was obtained. The introduced methacrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, so that no carboxyl group is generated in the resin structure.
(Process 3)
Further, 21.4 parts of phthalic anhydride and 0.5 part of triethylamine were added as a catalyst required for combining the precursors at this stage, and the mixture was reacted at 120 ° C. for 4 hours. In the added phthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other generates a carboxyl group terminal.
After completion of the reaction, propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40% by weight to obtain a resin solution (G-3).

(Resin solution (G-4))
A synthetic reaction is performed in the same manner as in the resin solution (G-3) except that the mixing ratio of the respective raw materials of the resin solution (G-3) is changed to the composition shown in Table 6 and the mixing amount (parts by weight). A resin solution (G-4) having a content of 40% by weight was prepared.

Each abbreviation in Table 6 is as follows.
PGMEA: propylene glycol monomethyl ether acetate M110: paracumylphenol ethylene oxide modified acrylate BzMA: benzyl methacrylate GMA: glycidyl methacrylate MMA: methyl methacrylate MAA: methacrylic acid DCPMA: dicyclopentanyl methacrylate St: styrene AA: acrylic acid AIBN: 2, 2'-azobisisobutyronitrile

<Method for producing light scattering particle dispersion>
(Light scattering particle dispersion (E-1))
Add 157.9 parts of methyl isobutyl ketone and 7.1 parts of a polyester dispersant (D-1) as a dispersion medium to 15 parts of titanium oxide particles “Ipehara CR-97 manufactured by Ishihara Sangyo Co., Ltd.” having an average primary particle size of 250 nm. It was. Using zirconia beads (1.25 mm) as a medium, dispersion treatment was performed with a dynomill for 1 hour to prepare a light scattering particle dispersion (E-1) (titanium oxide particle dispersion).
Table 7 shows the composition of the light scattering particle dispersion (E-1), the disperser, the average primary particle diameter of the particles, and the dispersed particle diameter in the dispersion.

(Light scattering particle dispersion (E-2), (E-3), (E-5), (E-6))
The light-scattering particle dispersion is the same as the production of the light-scattering particle dispersion (E-1) except that the mixing composition shown in Table 7 (prepared composition and mixing amount (parts by weight)) and the disperser are changed. Liquids (E-2), (E-3), (E-5), and (E-6) were prepared.

(Light scattering particle dispersion (E-4))
Under a nitrogen atmosphere, in a mixed solvent of 58 parts of methanol and 32 parts of water, 4.5 parts of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 5 parts of trifluoroethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), and allyl methacrylate (Japanese 0.5 parts of Kojun Pure Chemical Co., Ltd.) was polymerized at 60 ° C. for 8 hours using 0.025 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (W-50 Pure Chemical Co., V-50). . Then, 123 parts of PGMEA was added, methanol and water were removed by stripping, and a light scattering particle dispersion (E-4) (acrylic resin particle PGMEA dispersion) was produced.

Each abbreviation in Table 7 is as follows.
Titanium oxide 1: Taipei CR-97 manufactured by Ishihara Sangyo Co., Ltd.
Silica 1: Sea catalyst KE-E150 manufactured by Nippon Shokubai Co., Ltd.
Silica 2: Nippon Shokubai Co., Ltd. Sea Hoster KE-S30
Melamine: Nippon Shokubai Co., Ltd. poster S6
BYK-2155: “DISPERBYK-2155” manufactured by BYK Chemie; block copolymer having basic groups

<Method for producing inorganic oxide fine particle dispersion>
(Inorganic oxide fine particle dispersion (F-1))
15 parts of alumina particles having a minor axis diameter of 15 nm of primary particles (Alumina Sol-200, manufactured by Nissan Chemical Industries, Ltd.), 75 parts of propylene glycol monomethyl ether acetate as a dispersion medium, and polyester dispersant (D-1) as a dispersant 10 parts were added. A two-stage dispersion treatment was performed on the obtained liquid. As pre-dispersion, zirconia beads (average diameter: 1.25 mm) were used as media and dispersed for 1 hour with a paint shaker. As this dispersion, zirconia beads (average diameter: 0.1 mm) were used as media, and the dispersion was carried out for 7 hours with a disperser UAM-015 manufactured by Kotobuki Industries Co., Ltd. As described above, an inorganic oxide fine particle dispersion (F-1) (alumina particle dispersion) was produced.

(Inorganic oxide fine particle dispersions (F-2) to (F-25))
The inorganic oxide fine particle dispersion (F) was prepared in the same manner as the inorganic oxide fine particle dispersion (F-1) except that the composition, blending amount (parts by weight) and disperser described in Tables 8 to 12 were changed. -2) to (F-25) were produced.

The abbreviations in Tables 8 to 12 are as follows.
Alumina: manufactured by Nissan Chemical Industries, Alumina Sol-200, particle size 15 nm
Zirconia: ZR-30BF manufactured by Nissan Chemical Industries, Ltd., particle size 20 nm
Titanium oxide 1: MTY-700BS (manufactured by Teika Co., Ltd.) Silicone-treated product, particle size 80 nm
Titanium oxide 2: MT-05 (Taika Co., Ltd.) particle size 10 nm
BYK-2155: “DISPERBYK-2155” manufactured by BYK Chemie; block copolymer having basic groups

<Method for producing silane compound>
(Silane compound (K-1))
A flask equipped with a cooling pipe was prepared as a reaction vessel, and 100 parts of 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 parts of ethanol (manufactured by Kishida Chemical Co., Ltd.) were mixed well. Things were prepared and purged with nitrogen. Then, it heated with the oil bath, stirring, and raised the temperature of the reaction tank to 60 degreeC. After the temperature of the reaction vessel was stabilized at 60 ° C., the mixture was further stirred for 6 hours. After confirming the completion of the reaction by FT-IR spectrum, the temperature of the reaction vessel was lowered to room temperature and taken out into a nitrogen-substituted container to obtain a silane compound (K-1). The weight average molecular weight (Mw) was about 280.

[Example 1]
(Resin composition for light scattering layer R1)
The following materials were added, stirred and mixed so as to be uniform, and filtered through a filter having a mesh diameter of 5 μm to prepare a resin composition R1 for a light scattering layer.

・ Light scattering particle dispersion (E-1) 13.33 parts ・ Inorganic oxide fine particle dispersion (F-1) 60.0 parts ・ Leveling material 0.02 parts BYK330 (solid content 100%)
-PGMEA 22.65 parts-Cyclohexanone 4.0 parts

[Examples 2 to 42, Comparative Examples 1 to 6]
(Resin composition for light scattering layer R2 to R48)
Except having set it as the mixing | blending composition shown to Tables 13-15, it carried out similarly to resin composition R1 for light scattering layers of Example 1, and obtained resin composition R2-R48 for light scattering layers.

Each abbreviation in Tables 13-15 is as follows.
M402: Aronix M402 manufactured by Toagosei Co., Ltd.
DPCA30: KAYARAD DPCA-30 manufactured by Nippon Kayaku Co., Ltd.
(Caprolactone-modified dipentaerythritol hexaacrylate)
Irg907: BASF Irgacure 907
OXE-01: Irgacure OXE01 manufactured by BASF,
BYK330: BYK330 manufactured by Big Chemie (solid content 100%)
KBM-403: Shin-Etsu Silicone (3-glycidoxypropyltrimethoxysilane)
EHPE-3150: EHPE-3150 manufactured by Daicel Chemical Industries, Ltd.
IRGANOX 1010: IRGANOX 1010 manufactured by BASF
D Poster MX050W: Nippon Shokubai Co., Ltd. Der Poster MX050W Polymethyl methacrylate particles, particle size 75 nm

<Evaluation of resin composition for light scattering layer>
The obtained resin composition for light scattering layers was evaluated by the following apparatus or method.

(Visible light transmittance of light scattering layer)
The finished film thickness after heating the resin composition for light scattering layer to a glass substrate of 100 mm × 100 mm and 0.7 mm thickness (Corning glass “Eagle 2000”) at 230 ° C. for 20 minutes using a spin coater is 2. It apply | coated so that it might be set to 0 micrometer. Next, the obtained coated substrate was held on a hot plate heated to 110 ° C. for 2 minutes, and then subjected to ultraviolet exposure at an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² using an ultrahigh pressure mercury lamp. . The coated substrate was heated at 230 ° C. for 20 minutes and allowed to cool, and then the transmittance at a wavelength of 400 nm of the obtained coating film was determined using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Evaluation was made based on the following criteria.

Transmittance 85% or higher: Excellent (◎)
Transmittance 80% or more and less than 85%:
Transmittance less than 80%: Impossible (x)

(Flatness)
Using a three-dimensional structural analysis microscope (manufactured by ZYGO System Canon Marketing Japan Co., Ltd.), the coating film of the resin composition-coated substrate for the light scattering layer obtained by the same method as that prepared for transmittance measurement The surface roughness (Ra) of was measured. The surface roughness (Ra) indicates an arithmetic average roughness defined in JIS B0601 and JIS B0031.
Evaluation was made based on the following criteria.

Surface roughness less than 100 mm: Excellent (◎),
Surface roughness of 100 mm or more and less than 150 mm: good (◯),
Surface roughness of 150 mm or more and less than 200 mm: possible (△),
Surface roughness 200 mm or more: Impossible (×)

(Evaluation of bottom emission structure EL element (light extraction efficiency))
Using the ITO ceramic target (In ₂ O ₃ : SnO ₂ = 90: 10 (weight ratio)) on the resin composition-coated substrate for the light scattering layer obtained by the same method as that prepared for the measurement of transmittance, An ITO film having a thickness of 150 nm was formed by a DC sputtering method to obtain a translucent electrode (anode).
The ITO film was etched using a photoresist to form a pattern so that the light emission area was 5 mm × 5 mm. After ultrasonic cleaning, ozone cleaning was performed using a low-pressure ultraviolet lamp. Next, organic EL layers were sequentially formed on the ITO surface by vacuum deposition as follows.
First, CuPc was formed to a thickness of 15 nm as a hole injection layer. Next, α-NPD was formed to a thickness of 50 nm as a hole transport layer. Next, the red light emitting layer shown in Table 16 was formed to a thickness of 40 nm, and the electron injection layer shown in Table 5 was formed to a thickness of 30 nm.
Thereafter, Mg and Ag were co-evaporated to form MgAg with a thickness of 100 nm, and from the viewpoint of preventing MgAg oxidation, 50 nm of Ag was further formed thereon to form a back electrode (cathode).
After taking out from the vacuum deposition apparatus, an ultraviolet curable epoxy resin was dropped onto the cathode electrode side, and a slide glass was placed thereon, the epoxy resin was cured using a high-pressure ultraviolet lamp, and the device was sealed.
In the same manner as described above, a light emitting layer and an electron injection layer shown in Table 16 were used to produce blue, green, and white light emitting elements, respectively.
Separately, an EL element was obtained by the same method as above except that a glass substrate on which a light scattering layer was not formed was used as a base material for evaluation.

About each light emitting element obtained using the light-emitting body of Table 16, a forward current of 10 mA / cm ^{2 was} applied at room temperature, and the appearance of light emission (dark spots, unevenness) was observed. Further, the front luminance was measured with a spectral radiance meter “CS-2000” manufactured by Konica Minolta Sensing Co., Ltd., and the white light emitting element was obtained based on the front luminance of the EL element produced on the substrate on which the light scattering layer was not formed. The improvement rate of the front luminance was calculated. The emission spectrum was measured using MCPD-9800 manufactured by Otsuka Electronics Co., Ltd. Evaluation was made based on the following criteria.

(Light extraction efficiency)
Front brightness improvement rate 1.5 times or more: Excellent (◎),
Front brightness improvement rate 1.2 times or more and less than 1.5 times: Good (○)
Front luminance improvement rate 1.05 times or more to less than 1.2 times: Possible (△),
Front brightness improvement rate less than 1.05 times: Impossible (×)

  As shown in Tables 17 and 18, a resin composition for a scattering film containing a light scattering particle (E) and inorganic oxide fine particles (F) having a specific particle size and a polyester dispersant (D) is used. As a result, both light extraction efficiency and flatness can be achieved.

In particular, when a dispersant having a specific molecular weight and an acid value and having a specific structure was used as the polyester dispersant (D), better results were obtained in terms of flatness.
In Examples 25 and 31 to 42, it was possible to achieve both flatness and light extraction efficiency at a higher level. In Example 25, the flatness was the best.

  In Examples 32-38, a resin composition excellent in all of transmittance, light extraction efficiency, and flatness could be obtained by using in combination with a photosensitive resin, a highly sensitive initiator and monomer.

<Evaluation of organic EL device with top emission structure and coating type structure (light extraction efficiency)>
(Top emission structure A)
An aluminum film is formed by vacuum deposition on a glass substrate that is ultrasonically cleaned with isopropyl alcohol and then dried with dry nitrogen gas under a condition of a thickness of 100 nm, and then an ITO ceramic target (In ₂ O ₃ : SnO _2). = 90% by weight: 10% by weight), an ITO film having a thickness of 20 nm is formed by DC sputtering, and patterned to have a light emitting area of 5 mm × 5 mm. An electrode (anode) was formed.
Next, without taking out from the vacuum, organic EL layers were sequentially formed on the ITO surface by vacuum deposition as follows. First, α-NPD was formed to a thickness of 40 nm as a hole injection / hole transport layer. Next, H1 and Ir-1 shown in Table 19 were adjusted to a deposition rate of 100: 6 and formed to a thickness of 30 nm. Next, BAlq was formed to a thickness of 10 nm as a hole blocking layer. Further, Alq3 was formed to a thickness of 20 nm as an electron transport layer. Next, magnesium is formed to a thickness of 2 nm by a vacuum deposition method, and further, a thickness of 100 nm is formed from an ITO ceramic target (In ₂ O ₃ : SnO ₂ = 90 wt%: 10 wt%) by a DC sputtering method. An ITO film was formed to form a translucent electrode (cathode) made of a laminate of aluminum and ITO. Finally, the glass substrate and the resin composition-coated substrates for light scattering layers of Examples 1-42 and Comparative Examples 1-6 prepared for measuring transmittance were used as sealing substrates, and epoxy-based as a sealing material around them. A photo-curing adhesive was applied, brought into close contact with the scattering film side of the substrate, and irradiated with UV light from the glass substrate side to be cured and sealed.
When the light extraction efficiency was evaluated, the results were similar to those obtained in Examples 1-42 and Comparative Examples 1-6.

(Top emission structure B)
On a glass substrate that has been ultrasonically cleaned with isopropyl alcohol and then dried with dry nitrogen gas, aluminum is deposited by vacuum deposition under a thickness of 100 nm, and then lithium fluoride is deposited by vacuum deposition. Then, a lithium fluoride film having a thickness of 0.5 nm was formed and patterned so as to have a light emission area of 5 mm × 5 mm to form a back electrode (cathode) made of a laminate of aluminum and lithium fluoride. Subsequently, without taking out from a vacuum, the organic EL layer was sequentially formed on the lithium fluoride surface by a vacuum deposition method as follows. First, Alq3 was formed to a thickness of 20 nm as an electron transport layer. Next, BAlq was formed to a thickness of 10 nm as a hole blocking layer. Next, H1 and Ir-1 shown in Table 19 were adjusted to a deposition rate of 100: 6 and formed to a thickness of 30 nm. Next, α-NPD was formed to a thickness of 40 nm as a hole injection / hole transport layer. Next, an ITO film having a thickness of 150 nm is formed by a DC sputtering method from an ITO ceramic target (In ₂ O ₃ : SnO ₂ = 90 wt%: 10 wt%), and an ITO transparent electrode (anode) is formed. did. Finally, the glass substrate and the resin composition-coated substrates for light scattering layers of Examples 1-42 and Comparative Examples 1-6 prepared for measuring transmittance were used as sealing substrates, and epoxy-based as a sealing material around them. A photo-curing adhesive was applied, brought into close contact with the scattering film side of the substrate, and irradiated with UV light from the glass substrate side to be cured and sealed.
When the light extraction efficiency was evaluated, the results were similar to those obtained in Examples 1-42 and Comparative Examples 1-6.

(Coating structure)
An ITO ceramic target (In ₂ O ₃ : SnO ₂ ) was formed on the resin composition-coated substrates for light scattering layers of Examples 1-42 and Comparative Examples 1-6 obtained in the same manner as those prepared for the measurement of transmittance. = 90% by mass: 10% by weight), an ITO film having a thickness of 150 nm was formed by a DC sputtering method to obtain a translucent electrode (anode). Separately from this, an ITO film was formed directly on the glass substrate in the same manner as described above without forming a light scattering layer, thereby obtaining a translucent electrode (anode). Thereafter, the ITO film was etched using a photoresist with respect to both the translucent electrodes to form a pattern so that the light emitting area was 5 mm × 5 mm. After ultrasonic cleaning, ozone cleaning was performed using a low-pressure ultraviolet lamp. PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, BAYTRON P VP CH8000 manufactured by Bayer) manufactured by a spin coat method on the cleaned glass plate with an ITO electrode A hole injection layer having a thickness of 40 nm was obtained. Next, PVK (Poly (9-vinylcarbazole), manufactured by Sigma-Aldrich Co.) was 60%, Ir-2 listed in Table 20 was 3%, and ETM-1 was 37% by weight. Then, it was dissolved in toluene so that a light emitting layer having a thickness of 70 nm was obtained by a spin coating method. Furthermore, after depositing 20 nm of Ca thereon, 200 nm of Al was deposited to form an electrode to obtain an organic EL device. Finally, an ultraviolet curable epoxy resin was dropped on the cathode electrode side, and a glass slide was placed thereon, the epoxy resin was cured using a high pressure ultraviolet lamp, and the device was sealed.
When the light extraction efficiency was evaluated, the results were similar to those obtained in Examples 1-42 and Comparative Examples 1-6.

<Evaluation as photosensitive dry film>
Uniform coating of the resin composition for light scattering layer used in Examples 1-42 and Comparative Examples 1-6 on a 12 μPET film (S-12 manufactured by Toray DuPont Co., Ltd.) so that the dry film thickness is 2 μm. The film was dried at 100 ° C. for 5 minutes, then cooled to room temperature, and a biaxially stretched polypropylene film (OPP film) was laminated on the light scattering layer resin composition side to obtain a photosensitive dry film. The OPP film was peeled off from the photosensitive dry film, and vacuum laminated to a glass substrate (Corning Glass Eagle 2000). The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds.
Next, ultraviolet exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² . Further, the obtained substrate was heated at 230 ° C. for 20 minutes and allowed to cool to obtain a light scattering layer. For the obtained light scattering layer, the element was created and evaluated in the same manner as described above, and the evaluation of the bottom emission type EL element (light extraction efficiency), flatness, developability, and transmittance of the light scattering layer were evaluated. The results were the same as those obtained in Examples 1-42 and Comparative Examples 1-6.

<Evaluation of resin composition for light scattering layer by various printing processes>
(A) Reverse offset printing (reverse offset printability)
Using the thin film printing apparatus shown in FIG. 2, the anilox roll was appropriately applied on the glass substrate so that the dry scattering film thickness of the resin compositions for Examples 1 to 42 and Comparative Examples 1 to 6 was 2 μm. While exchanging, a straight line having a line width of 100 μm was continuously printed, and a linear shape was observed.
All of the 30 or more continuous prints were able to print a linear pattern continuously.

(Flatness, transmittance, refractive index)

Using the thin film printing apparatus shown in FIG. 2, on the glass substrate, the finished film thickness after heating the light scattering layer resin compositions of Examples 1-42 and Comparative Examples 1-6 at 230 ° C. for 20 minutes is 2 μm. As described above, printing was performed while appropriately replacing the anilox roll, and a 100 mm × 100 mm square light scattering layer was formed on the glass substrate. Next, it was kept on a hot plate heated to 110 ° C. for 2 minutes. Thereafter, using an ultrahigh pressure mercury lamp, ultraviolet exposure was performed with an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² . The coated substrate was heated at 230 ° C. for 20 minutes to obtain a light scattering layer. About the obtained light-scattering layer, preparation and evaluation of the bottom emission type organic EL element were performed similarly to the above.

When the evaluation (light extraction efficiency), flatness, developability, and transmittance of the bottom emission type EL element of the light scattering layer were evaluated, the results were the same as those obtained in Examples 1-42 and Comparative Examples 1-6. Met.

(B) Flexographic printing (flexographic printability)
The second unit of the CI 6-color flexo printing machine (Windmoeller & Hoelscher KG's “SOLOFLEX” (CI 6-color press)) is equipped with a flexographic plate (DSF version) with a 100 micron line and space pattern, and 165-line anilox Using the roll (cell capacity 26.5 cm 2 / m 3), the resin compositions for light scattering layers of Examples 1 to 42 and Comparative Examples 1 to 6 were sequentially printed on a glass substrate so that the dry coating thickness was 2 μm. Whether or not the resin composition for the light scattering layer was continuously transferred from the anilox roll to the plate was visually determined.
All metastasis was good.

(Flatness, transmittance, refractive index)
A 165-line anilox roll with a 100 mm x 100 mm square pattern mounted on the second unit of a CI 6-color flexographic printing machine ("SOLOFLEX" (CI 6-color press manufactured by Windmoeller & Hoelscher KG)) Light scattering of Examples 1 to 42 and Comparative Examples 1 to 6 so that the finished film thickness after heating at 230 ° C. for 20 minutes on a glass substrate using (cell capacity 26.5 cm ² / m ³ ) is 2.0 μm. The layered resin compositions were sequentially printed, and then held for 2 minutes on a hot plate heated to 110 ° C. Thereafter, using an ultrahigh pressure mercury lamp, the illuminance was 20 mW / cm ² and the exposure amount was 50 mJ / cm ² . The coated substrate was heated at 230 ° C. for 20 minutes to obtain a light-scattering layer. Creation and evaluation mission-type organic EL element was carried out.
When the evaluation (light extraction efficiency), flatness, developability, and transmittance of the bottom emission type EL element of the light scattering layer were evaluated, the results were the same as those obtained in Examples 1-42 and Comparative Examples 1-6. Met

(C) Gravure printing (gravure printability)
The resin composition for light scattering layers of Examples 1 to 42 and Comparative Examples 1 to 6 was prepared using a corrosive plate having a plate depth of 30 microns using a gravure proofing machine, and the dry coating thickness was 2 μm on the glass substrate. Thus, continuous printing of a straight line having a line width of 100 μm was performed, and the linear shape was observed. In all cases, 30 or more continuous prints were able to print a linear pattern continuously.

(Flatness, transmittance, refractive index)
Finished films after heating the resin compositions for light scattering layers of Examples 1 to 42 and Comparative Examples 1 to 6 on a glass substrate at 230 ° C. for 20 minutes using a gravure proof machine using a corrosive plate having a plate depth of 30 microns. Printing was sequentially performed so that the thickness was 2.0 μm. Next, it was kept on a hot plate heated to 110 ° C. for 2 minutes. Thereafter, using an ultrahigh pressure mercury lamp, ultraviolet exposure was performed with an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² . The coated substrate was heated at 230 ° C. for 20 minutes to obtain a light scattering layer. About the obtained light-scattering layer, preparation and evaluation of the bottom emission type organic EL element were performed similarly to the above.
When the evaluation (light extraction efficiency), flatness, developability, and transmittance of the bottom emission type EL element of the light scattering layer were evaluated, the results were the same as those obtained in Examples 1-42 and Comparative Examples 1-6. Met

(D) Inkjet (IJ) printing (IJ printability)
The inks obtained in Examples 1 to 42 and Comparative Examples 1 to 6 were ejected onto a PET substrate with an ink jet printer having a piezo head capable of changing the frequency of 4 to 10 KHz, and the printing state was visually observed. The discharge stability was evaluated based on the standard.
In all cases, continuous printing and intermittent printing were accurately performed at predetermined positions.

(Flatness, transmittance, refractive index)
100 mm × 100 mm square pattern of the resin composition for light scattering layer obtained in Examples 1-42 and Comparative Examples 1-6 on a glass substrate with an inkjet printer having a piezo head capable of changing frequency of 4-10 KHz. Were sequentially printed so that the finished film thickness after heating at 230 ° C. for 20 minutes was 2.0 μm. Next, it was kept on a hot plate heated to 110 ° C. for 2 minutes. Thereafter, using an ultrahigh pressure mercury lamp, ultraviolet exposure was performed with an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² . The coated substrate was heated at 230 ° C. for 20 minutes to obtain a light scattering layer. About the obtained light-scattering layer, preparation and evaluation of the bottom emission type organic EL element were performed similarly to the above.
When the evaluation (light extraction efficiency), flatness, developability, and transmittance of the bottom emission type EL element of the light scattering layer were evaluated, the results were the same as those obtained in Examples 1-42 and Comparative Examples 1-6. Met

From the above results, the light scattering layer formed with the resin composition for light scattering layer of the present invention can be formed by various printing methods such as reverse offset printing, flexographic printing, gravure printing, ink jet printing, and the like with a spin coater. Similar results were obtained as in the case of processing and development.

  A light-scattering layer formed using a photosensitive resin composition for a light-scattering layer on a light-transmitting substrate; a light-transmitting first electrode; and at least one organic layer including a light-emitting layer; It was confirmed that the organic electroluminescence device in which the second electrode having light reflectivity was sequentially laminated had excellent performance as a lighting device or a display device.

DESCRIPTION OF SYMBOLS 1 Organic electroluminescent apparatus 11 Translucent board | substrate 12 Light-scattering layer 13 Translucent electrode 14 At least 1 organic layer (organic EL layer) containing a light emitting layer
15 Back electrode 21 Dispenser 22 Doctor 23 Anilox roll 24 Plate cylinder 25 Top plate 26 Silicone rubber blanket cylinder 27 Substrate 28 Printing table 29 Resin composition for light scattering layer

Claims (13)

  Containing light scattering particles (E) having an average primary particle diameter of 200 to 800 nm, inorganic oxide fine particles (F) having a minor axis diameter of primary particles of 5 to 60 nm, and a polyester dispersant (D). A resin composition for a light scattering layer.   The resin composition for a light scattering layer according to claim 1, wherein the inorganic oxide fine particles (F) contain titanium oxide.   The resin for light scattering layers according to claim 1 or 2, wherein the polyester dispersant (D) has a weight average molecular weight of 2,000 to 25,000 and an acid value of 5 to 200 mgKOH / g. Composition.   A polyol part (A) and a polycarboxylic acid part (B) formed by reacting the hydroxyl group of the polyol (a) with the acid anhydride group of the polycarboxylic acid anhydride (b), the polyester dispersant (D) A vinyl polymer part (A) in which a part or all of the polyol part (A) is radically polymerized with an ethylenically unsaturated monomer (c) via an S atom. The resin composition for a light scattering layer according to any one of claims 1 to 3, wherein C) is contained.   The polyester dispersant (D) is radically polymerized with one end of the ethylenically unsaturated monomer (c) in the presence of the compound (a1) having two hydroxyl groups and one thiol group in the molecule. A hydroxyl group in the polyol (a) containing at least the vinyl polymer (a2) having two hydroxyl groups, and an acid anhydride group in the polycarboxylic acid anhydride (b) containing at least the tetracarboxylic dianhydride (b1). A hydroxyl group in the polyol (a) containing at least a compound (a1) containing a compound (a1) having two hydroxyl groups and one thiol group in the molecule, and a tetracarboxylic dianhydride (b1). An ethylenically unsaturated compound forming a vinyl polymer site (C) in the presence of polyester (d) obtained by reacting at least with an acid anhydride group in polycarboxylic acid compound (b). Monomer (c) the claims 1-4 light scattering layer resin composition according to any one of which is a polyester dispersant formed by radical polymerization. The resin composition for a light scattering layer according to claim 5, wherein the tetracarboxylic dianhydride (b1) is represented by the following general formula (1) or general formula (2).
General formula (1):
[In General Formula (1), k is 1 or 2. ]
General formula (2):
[In General Formula (2), Q ₁ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, General Formula (3) :
Or a group represented by the general formula (4):
It is group represented by these. ]   The resin composition for a light scattering layer according to any one of claims 4 to 6, wherein the vinyl polymer part (C) has a weight average molecular weight of 1,000 to 20,000. The resin composition for a light scattering layer according to any one of claims 4 to 7, wherein the ethylenically unsaturated monomer (c) contains a monomer represented by the following general formula (5).
General formula (5):
[In General Formula (5), R ³² is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 carbon atom which may have a substituent. -20 alkenyl group, phenyl group which may have a substituent, or a compound represented by the following general formula (6), R ³¹ is a hydrogen atom or a methyl group. ]
General formula (6):
[In General Formula (6), R ³³ is a linear or branched alkylene group having 1 to 8 carbon atoms, and R ³⁴ is a linear chain having 1 to 20 carbon atoms which may have a substituent. Or a branched or cyclic alkyl group, an optionally substituted alkenyl group having 1 to 20 carbon atoms, or an optionally substituted phenylene group, and n is an integer of 1 to 30 It is. ]   9. The resin composition for a light scattering layer according to claim 4, wherein the glass transition temperature of the vinyl polymer portion (C) is less than 50 ° C. 9.   Furthermore, the photoinitiator (H) is included, The resin composition for light scattering layers of any one of Claims 1-9 characterized by the above-mentioned.   The light-scattering layer formed using the resin composition for light-scattering layers of any one of Claims 1-10.   A light-scattering layer according to claim 11, a first electrode having a light-transmitting property, at least one organic layer including a light-emitting layer, and a second electrode having a light-reflecting property are provided on a light-transmitting substrate. Organic electroluminescence device stacked sequentially.   The organic electroluminescence device according to claim 12, which is a lighting device or a display device.