Composite particles, varnishes, coatings, and adhesives

Abstract

To provide composite particles that enable the simple and efficient production of coatings with excellent refractive index and transparency. ru. [Solution] A composite particle comprising a compound having a dinaphthothiophene skeleton and a resin.

Description

Technical Field

[0001] The present invention relates to composite particles, varnishes, coating agents, and adhesives.

Background Art

[0002] A compound having a dinaphthothiophene skeleton (hereinafter referred to as "dinaphthothiophene derivative") is known to be usable as a high refractive index material, and is expected to be applied to applications such as optical films, coating films, optical lenses, and refractive index improvers that require high refractive index and high transparency. ) For example, Patent Document 1 aims to provide a novel refractive index improver using an organic compound, and a resin composition, polymerization or curable composition, and optical material containing the same. A refractive index improver containing a compound having a predetermined dinaphthothiophene skeleton, and a resin composition, polymerization or curable composition, and optical material containing the same are described.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] When a dinaphthothiophene derivative is used alone as a refractive index improver, the dinaphthothiophene derivative is dispersed or dissolved in a solvent, and then applied to a substrate whose refractive index is to be improved, etc., and the solvent is volatilized. However, in that case, there is a high possibility that the problem of reduced transparency occurs due to precipitation of crystals of the dinaphthothiophene derivative.

[0005] Furthermore, for the purpose of application in optical materials, the dinaphthothiophene derivative contains a predetermined functional group. Furthermore, curable compositions containing a reaction initiator that reacts with the functional group by heating or light irradiation are being investigated. However, it is possible to use this method for fabricating optical materials in a simpler and more efficient way. There is a need for dinaphthothiophene derivatives and compositions thereof.

[0006] Therefore, based on the above findings, the present invention provides a simple and effective coating film with excellent refractive index and transparency. The objective is to provide composite particles, varnishes, coatings, and adhesives that can be manufactured efficiently. do. [Means for solving the problem]

[0007] As a result of diligent research by the present inventors, the compounding of a dinaphthothiophene derivative with a resin is The composite particles obtained by this method can be used to easily and efficiently produce coatings with excellent refractive index and transparency. We discovered this and completed the present invention.

[0008] The present invention includes the following embodiments. [1] A composite particle comprising a compound having a dinaphthothiophene skeleton and a resin. [2] The average particle diameter of the composite particles is 1 μm or more. [1] The composite particles described above. [3] The compound includes a compound having a nanofiber-like dinaphthothiophene skeleton, The composite particles described in [1] or [2]. [4] The composite particle according to [3], wherein the thickness of the compound is 1 μm or less. [5] The aforementioned compound is a compound represented by the following formula (1), or a compound represented by the following formula (1). The composite particles according to any one of [1] to [4], which are polymers containing constituent units derived therefrom. [Chemical formula] (In the formula, R , , [Figure 2] , [Figure 1] ,

[0010] , , , , , , , , , , , , , , ,

[0009] , are each independently an organic group, a hydroxyl group, an amino group, a nitro group, a thiol group , a sulfo group, a halogen atom, or an optionally substituted silyl group, and R 2 are each independently an organic group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group, and m is each independently an integer of 0 to 2 and n is each independently an integer of 0 to 4.) [6] A varnish containing a compound having a dinaphthothiophene skeleton, a resin, and a solvent. [7] The varnish according to [6], wherein the compound contains a compound having a nanofibrous dinaphthothiophene skeleton. [8] The varnish according to [7], wherein the thickness of the compound is 1 μm or less. [9] A coating agent or an adhesive containing the composite particles according to any one of [1] to [5], or the varnish according to any one of [6] to [8]. [Advantages of the Invention]

[0009] According to the present invention, it is possible to provide composite particles, a varnish, a coating agent, and an adhesive capable of easily and efficiently producing a coating film excellent in refractive index and permeability. [Brief Description of the Drawings] <000^101>

[0010] [Figure 1] It is a conceptual diagram showing composite particles containing a dinaphthothiophene derivative and a resin. [Figure 2]This is a scanning electron microscope image showing the composite particles prepared in the example. [Figure 3] This is the powder X-ray diffraction measurement profile of the composite particles prepared in the example. [Figure 4] This is the investigative scanning calorimetry profile of the composite particles prepared in the example. [Figure 5] This is the scan calorimetry profile of the mixed powder before the composite particles were prepared in the example. [Figure 6] This is a scanning electron microscope image showing the composite particles prepared in the example. [Figure 7] This is the powder X-ray diffraction measurement profile of the composite particles prepared in the example. [Figure 8] This is the investigative scanning calorimetry profile of the composite particles prepared in the example. [Figure 9] This is the scan calorimetry profile of the mixed powder before the composite particles were prepared in the example. [Figure 10] This is a scanning electron microscope image showing the mixed powder prepared in the example. [Figure 11] This is a scanning electron microscope image showing the composite particles prepared in the example. [Figure 12] This shows the measurement profiles of the refractive index and extinction coefficient of coating films prepared using the varnishes of the examples. [Figure 13] This shows the measurement profiles of the refractive index and extinction coefficient of coating films prepared using the varnishes of the examples. [Modes for carrying out the invention]

[0011] The embodiments of the present invention (hereinafter referred to as "this embodiment") will be described in detail below. However, the present invention is not limited to these, and various modifications can be made without departing from the spirit of the invention. It is possible.

[0012] In this embodiment, "particles" does not refer to perfectly spherical particles, but to various known shapes. This shall include, but is not limited to, needle-shaped, rod-shaped, and Examples include elliptical shapes.

[0013] In this embodiment, "crystalline" means obtained by X-ray diffraction (XRD) measurement. This means that the X-ray diffraction measurement spectrum has diffraction peaks. This is thought to mean that the molecules have a layered structure in which they are arranged in a specific way.

[0014] In this embodiment, "nanofiber-like" means that the fiber thickness is approximately 1.0 to 1000 This refers to something that is nanometer-sized.

[0015] 1. Composite particles The composite particles of this embodiment include dinaphthothiophene derivative particles and resin particles, and may be used as needed. Depending on the circumstances, other components may also be included. Here, the composite particles of this embodiment have a refractive index and The following factors are thought to contribute to the simple and efficient production of coatings with excellent permeability: Composite The dinaphthothiophene derivative contained in the particles is present whether as a compound alone or in a mixture with the resin. However, because it exhibits a very high refractive index, the composite particles contain a dinaphthothiophene derivative. This allows for the creation of coatings with excellent refractive index. Furthermore, the composite particles contain dinaphthothiophene. By including a resin in addition to the derivative, the shape and / or crystallinity of each component in the composite particles is altered. This makes it possible to create a coating film that is less prone to formation and has excellent permeability. Furthermore, composite particles Since it can be used as a powder or varnish to create a coating film, it allows for simple and efficient coating film production. It can be manufactured easily.

[0016] Figure 1 is a conceptual diagram showing a composite particle containing a dinaphthothiophene derivative and a resin. The composite particle 1 consists of multiple dinaphthothiophene derivative nanofibers 11 and multiple derivatum Contains 12 fat particles.

[0017] In this embodiment, "composite particles" refers to a mixture of a dinaphthothiophene derivative and a resin. Secondary particles formed by the physical association, aggregation, or bonding of two or more components. This refers to the composite particles in this embodiment, which contain two or more components. Because the uneven distribution of shape and / or crystallinity resulting from this is extremely unlikely, the shape and / or crystallinity This is clearly distinguishable from mixtures where segregation occurs (for example, the mixed powder described in the examples).

[0018] The average particle size of the composite particles is preferably 1 μm or larger, and more preferably 10 μm or larger. It is more preferably 50 μm or more, and even more preferably 100 μm or more. Yes. Also, there is no particular upper limit to the average particle size of the composite particles, but for example, 1000 μm. Yes. Because the average particle size of the composite particles is within this range, the powdered composite particles flow It offers excellent mobility and prevents dust generation during handling, making it easier and more efficient to use. Cut.

[0019] Furthermore, the content of dinaphthothiophene derivative particles relative to the resin content in the composite particles (B) The mass ratio (A / B) of quantity (A) is preferably 1.0 or more and 5.0 or less, and more preferably The above quality is 1.5 or more and 4.0 or less, and more preferably 2.0 or more and 3.0 or less. Because the ratio (A / B) is within this range, the dinaphthothiophene in the composite particles The derivative and the resin tend to become more uniformly intermingled.

[0020] In this embodiment, the average particle size of the composite particles is determined using a scanning electron microscope (SEM). Identify the compound particles. Specifically, the compound particles are photographed with a SEM, and the individual particles are identified from the multiple compound particles shown. Ten particles are selected, and the average length of these composite particles in the longitudinal direction is defined as the average particle diameter. Specific conditions for the SEM include, for example, those described in the examples.

[0021] The crystallinity of composite particles can be evaluated by powder X-ray diffraction (XRD). Specific conditions for XRD include, for example, those described in the examples.

[0022] 1.1. Dinaphthothiophene derivatives In this embodiment, the dinaphthothiophene derivative is more effective in achieving the effects of the present invention. From the viewpoint of ensuring reliable performance, it is preferable that it be crystalline (i.e., crystalline). Also, Gina The shape of the phthothiophene derivative when it is a particle is not particularly limited, but for example, Examples include needle-shaped, needle-shaped, rod-shaped, and spherical shapes.

[0023] The dinaphthothiophene derivative is preferably a nanofiber dinaphthothiophene derivative. It contains a body. By including such nanofiber-like dinaphthothiophene derivatives, The stability of the nanocrystals dispersed within the composite particles tends to increase.

[0024] When the dinaphthothiophene derivative is in the form of particles, its average particle size is preferably 10 μm. The following are more preferably 5 μm or less, and even more preferably 1.0 μm or less. The lower limit of the average particle size is not particularly limited, but for example, 20 nm, 50 nm, or 10 It can also be 0 nm.

[0025] When the dinaphthothiophene derivative includes a nanofiber-type dinaphthothiophene derivative The length of the nanofiber is not particularly limited.

[0026] Furthermore, the thickness of the above nanofibers is preferably 200 nm or less, and more preferably It is 150 nm or less, and more preferably 100 nm or less. The lower limit of its thickness is particularly The following are examples of the following, but are not limited to: 10nm, 30nm, or 50nm.

[0027] The aspect ratio (length / thickness) of the above nanofiber is preferably 10 or more. Preferably it is 50 or more, and even more preferably 100 or more. Upper limit of aspect ratio The number is not particularly limited, but for example, it may be 500, 1000, or 5000.

[0028] In this embodiment, the average particle size of the dinaphthothiophene derivative particles was determined using SEM. Specifically, the composite particles are photographed with a SEM, and the dinaphthothiophene inducer is identified. Ten conductive particles were randomly selected, and the longitudinal direction of these dinaphthothiophene derivative particles was measured. The average value of the length in each direction is defined as the average particle diameter. Specific SEM conditions include, for example, the example. The items listed can be cited.

[0029] Furthermore, the length and thickness of the nanofibers were determined by imaging the nanofibers with a SEM. From the multiple nanofibers that were captured, 10 were randomly selected, and these nanofibers The average length in the longitudinal direction and the average length in the transverse direction of the nanofiber are respectively This refers to the length and thickness of the crystal.

[0030] From the perspective of obtaining a high refractive index, the content of the dinaphthothiophene derivative is the total quality of the composite particles. Preferably, it is 50% by mass or more, and more preferably 70% by mass or more, relative to the amount. Furthermore, the content of the dinaphthothiophene derivative is preferably 90% by mass or less. When the thiophene derivative content is 90% by mass or less, composite particles become easier to produce. Furthermore, when used as a varnish as described later, the resulting coating contains dinaphthothiophene derivatives. Crystal precipitation becomes less likely, and greater permeability tends to be achieved. From this perspective, Zinaf The tothiophene derivative content is more preferably 80% by mass or less.

[0031] The higher the content of the dinaphthothiophene derivative in the composite particles, the more effective the composite particles will be. Because the refractive index of the product tends to increase, the amount of dinaphthothiophene derivative should be adjusted according to the application. By adjusting these parameters, the refractive index of the transparent coating can be adjusted.

[0032] Next, a compound having a dinaphthothiophene (DNT) skeleton, which is a dinaphthothiophene derivative. This section will provide a detailed explanation of the compound (hereinafter referred to as "DNT compound").

[0033] DNT compounds, whether alone or in mixtures with resins, exhibit very high refractive indices. It can be used as a high refractive index optical material to indicate a ratio. The DNT compound is given by the following formula: (1) The compound represented by this compound, or a polymer containing a structural unit derived from this compound. preferable. [ka]

[0034] In equation (1), R 1 These are, independently, an organic group, a hydroxyl group, an amino group, and a nitro group. R is a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. 2 These are, independently, an organic group, a hydroxyl group, an amino group, a nitro group, a thiol group, and a sulfo group. m is a halogen atom or an optionally substituted silyl group, and each is independently, The integers are between 0 and 2, and each of the integers n is independently between 0 and 4.

[0035] In equation (1), R 1 and R 2 Preferably, each is independently of 2,3-epoxy Propoxy group, 2-(meth)acryloyloxyethoxy group, (meth)acryloyloxy A methoxy group, an RaO- group (where Ra is an alkyl group that may contain oxygen or sulfur). ), and HO-Rb-O- group (Rb is an alkylene group which may contain oxygen or sulfur) The group consists of an organic group selected from the group comprising an aralkylene group, or a hydroxyl group. "(Meth)acryloyl" is a general term for methacryloyl and acryloyl.

[0036] The DNT compound is preferably a compound represented by the following formula (2), or derived from this compound. It is a polymer containing the constituent units. [ka]

[0037] The DN of a compound represented by formula (2) above or a polymer containing a structural unit derived from this compound The content relative to the total amount of compound T is preferably 30% by mass or more, more preferably, It is 50% by mass or more, more preferably 70% by mass or more, and even more preferably It is 90% by mass or more. The content of those compounds and polymers is within this range. This tends to improve the refractive index of the resulting coating film.

[0038] DNT compounds and their crystals can be synthesized according to known methods. For example, Japanese Patent Publication No. 2018-83774, Japanese Patent Publication No. 2014-196288, Japanese Patent Publication No. 2011-1 Japanese Patent Publication No. 78985, Japanese Patent Publication No. 2017-137244, and Japanese Patent Publication No. 2015-30727 Examples of methods used in the official gazette include:

[0039] 1.2. Resin As a resin, one type may be used alone or in combination of two or more types. As such, it can be selected appropriately according to the application and is not particularly limited, but for example, poly Imides, polyamides, various cellulose resins, poly(meth)acrylic acid esters, polystyrene Polyvinyl ether, polyolefin, and copolymers of monomers constituting these, Recarbonate, polyester, polysulfide, polyurethane, polyether, pheno Examples include oleic resin, urea resin, melamine resin, epoxy resin, and oxetane resin. .

[0040] Among these, polyimide resin is preferred. By using polyimide resin, permeability, It tends to have even better heat resistance and light resistance, and is easier to process as an optical material, etc.

[0041] In composite particles, the resin may be formed by the aggregation and bonding of multiple resin particles. Below, the resin particles mentioned above are referred to as "primary resin particles." The average particle size of the primary resin particles is preferably... The particle size is 10 μm or less, more preferably 5.0 μm or less, and even more preferably 1. It is 0 μm or less. The lower limit of the average particle size of the primary resin particles is not particularly limited, but for example, 2 It may be 0nm, 50nm, or 100nm.

[0042] In this embodiment, the average particle size of the primary resin particles is determined using SEM. This involves imaging primary resin particles with an SEM and randomly selecting one from among multiple primary resin particles that appear in the image. Select 0 and use the average of the longitudinal lengths of these primary resin particles as the average of the primary resin particles This refers to the particle size. Specific SEM conditions include those described in the examples. It is possible.

[0043] The resin content in the composite particles is preferably 10% by mass relative to the total mass of the composite particles. The amount is 40% by mass or less, more preferably 15% by mass or more and 35% by mass or less, and further Preferably, the resin content in the composite particles is 20% by mass or more and 30% by mass or less. Due to being within such a range, when used as a varnish as described later, dispersion stability and viscosity It tends to be superior in this respect.

[0044] 1.3. Other ingredients The composite particles in this embodiment may contain other components as needed. Other components are not particularly limited, but examples include inorganic particles, and such inorganic The particles preferably have a refractive index of 1.8 or higher, more preferably 2.0 or higher, and further Preferably, the ratio is 2.2 or higher. Furthermore, the average particle diameter of the inorganic particles is preferably 100 nm. The following, more preferably 50 nm or less, and even more preferably 30 nm or less. In particular, the average particle size of the inorganic particles is 100 nm or less, resulting in a more transparent and rigid composite. Particles and coatings tend to be easily obtained. Such inorganic particles are not particularly limited, however For example, oxide particles such as titanium dioxide, zirconia, cerium oxide, zinc oxide, and tin oxide One example is that the refractive index can be improved by including such inorganic particles in the composite particles. can.

[0045] The inorganic particle content in composite particles can be appropriately selected according to the application, in particular While not limited to these, for example, 10% or less by mass, or 5.0% or less by mass, relative to the total mass of the composite particles. or 3.0% by mass or less. The lower limit of the inorganic particle content is not particularly limited. However, it may be, for example, 0% by mass.

[0046] 1.4. Manufacturing method As one embodiment of the method for producing composite particles in this embodiment, dinaphthothiophene derivative One example of a manufacturing method is one that includes a grinding step in which the crystals and resin of the material are ground in a mill. In the manufacturing method, even if the crystals of the dinaphthothiophene derivative are crushed, amorphous formation occurs. Without doing so, composite particles can be formed while maintaining the crystalline structure. By maintaining this property, the optical properties of the raw material crystal can be preserved even when composite particles are formed. Generally, it is known that crushing crystals reduces their degree of crystallinity (for example, Bu lletin of the Faculty of Engineering,Hok Kaido University, No. 102 (1981), pp. 55-66, and (and Japanese Patent Publication No. 2012-111841), the crystal structure is maintained while the particles are formed into composite particles. That is astonishing.

[0047] Specific examples of dinaphthothiophene derivatives are as described above. The crystal shape of the naphthothiophene derivative is preferably rod-shaped or needle-shaped.

[0048] Examples of mills used in the grinding process include ball mills, bead mills, and jet mills. Examples include planetary ball mills and vibrating ball mills. It can be listed.

[0049] In the grinding process, either dry grinding or wet grinding may be employed. Dry grinding is, This method involves grinding in a gas such as air, in a vacuum, or in an inert gas. Wet grinding involves using water, etc. This is a method of grinding in a liquid. In this embodiment, the grinding process is preferably dry grinding. Furthermore, more preferably, a process in which high shear force and compressive force are applied during dry grinding (hereinafter referred to as "mechanical grinding"). This is called "chemical compounding treatment."

[0050] The grinding conditions are determined by the size of the crystals of the dinaphthothiophene derivative used as the raw material and the desired composite particles. The size, shape, etc., will be modified as appropriate.

[0051] (Dry grinding method using planetary ball mill) While not strictly limited, a planetary ball mill is used when employing a dry grinding method. It is preferable to do so. A planetary ball mill is a grinding container filled with balls as a grinding medium. By making it rotate on its axis and then revolve in the opposite direction to its rotation, a large centrifugal force is generated. It can provide crushing power.

[0052] In a dry grinding method using a planetary ball mill, the material of the inner wall of the container and the balls is not particularly limited. Although this is not done, in order to minimize the inclusion of impurities due to wear of the inner wall of the container and the ball, It is preferable that the material of the inner wall of the container and the ball be the same. For example, agate, alumina, zirconia, tungsten carbide, chromium steel, And silicon nitride are also mentioned. From the viewpoint of wear resistance, agate, alumina, or zirconium are used. Conia is preferred for the container's inner wall and balls.

[0053] In a dry grinding method using a planetary ball mill, the size of the balls is not particularly limited. The diameter of the ball is preferably 1 mm or more and 15 mm or less, more preferably 5 mm or more. It is 10 mm or less. By making the diameter of the ball 1 mm or more, the crushed sample and the ball Separation from the ball becomes even easier. By making the diameter of the ball 15 mm or less, crushing becomes easier. Efficiency can be improved.

[0054] In a dry grinding method using a planetary ball mill, dinaphthothiophene is used as a raw material. The filling rate of the body crystals and balls into the grinding container is preferably 10% by volume or more. The volume percentage is less than or equal to 10%, and more preferably between 20% and 70% by volume. The filling rate is 10 By making it more than a certain volume percentage, the space between the balls and between the balls and the inner wall of the container is maintained. This further reduces direct collisions and minimizes wear on the balls and crushing container. By setting the ratio to 80% by volume or less, the crushing efficiency can be improved.

[0055] In a dry grinding method using a planetary ball mill, the space between the balls and the balls To suppress the rise in temperature inside the container due to collision and abrasion with the inner wall of the container, during the grinding operation It is preferable to stop operation as needed and allow a cooling period. During the shutdown, the substance adheres to the inner wall of the container. It is preferable to separate the sample and crush any samples that are in a lumpy state.

[0056] (Wet grinding method using a bead mill) While not strictly limited, a bead mill is used when employing a wet grinding method. Preferably, the bead mill uses beads as a grinding medium and a slurry containing raw materials to grind. The material is placed in a container, and the centrifugal force generated by the high-speed rotation of the agitator creates a powerful grinding force. It can be obtained.

[0057] In a wet grinding method using a bead mill, the raw material, a dinaphthothiophene derivative, is divided The solvent used for dispersion (dispersion medium) is not particularly limited as long as it is a solvent in which the raw materials are sparingly soluble or insoluble. For example, water, or methanol, ethanol, isopropanol, glycerin, or p Examples include alcohols such as polypropylene glycol. From an environmental and cost perspective, water is used. It is preferable to use it.

[0058] In a wet grinding method using a bead mill, when water is used as the dispersion medium, the surfactant Agents may be added. The type of surfactant depends on its effect in suppressing particle aggregation during the grinding process. It is not particularly limited as long as it possesses the properties of a surfactant. For example, as a surfactant, a nonionic surfactant Examples include amphoteric surfactants, cationic surfactants, and anionic surfactants.

[0059] In a wet grinding method using a bead mill, the material of the inner wall of the container and the beads is not particularly limited. However, in order to minimize the incorporation of impurities due to wear of the inner wall of the container and the beads, the container It is preferable that the material of the inner wall and the beads be the same. For example, alumina, zirconia, tungsten carbide, glass, chrome steel, and Silicon nitride is one example. From the viewpoint of wear resistance, the inner wall of the container and the beads made of zirconia are suitable. preferable.

[0060] In a wet grinding method using a bead mill, the size of the beads is not particularly limited. The diameter of the spool is preferably 0.03 mm or more and 2 mm or less, more preferably 0.1 mm The diameter is 0.8 mm or less. By making the diameter of the beads 0.03 mm or more, crushing is possible. This makes it even easier to separate the sample from the beads. By making the diameter of the beads 2 mm or less... This means improving the efficiency of generating nanofiber-like crystals of dinaphthothiophene derivatives. It is possible.

[0061] In a wet grinding method using a bead mill, the solid content concentration in the slurry is preferably 0 The concentration is 0.5% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 10% by mass or less. By setting the concentration of the form to 0.5% by mass or more, the space between the beads and the beads and Further suppressing direct collisions with the inner wall of the container and reducing wear on the beads and grinding container Yes, it is possible. By keeping the solid content concentration below 30% by mass, the fluidity of the slurry can be better maintained. This allows for improved grinding efficiency.

[0062] In a wet grinding method using a bead mill, the filling rate of beads into the grinding container is preferably The volume is 50% to 95% or less, and more preferably 70% to 90% or less. Therefore, by setting the packing ratio to 50% by volume or more, the nano-sized dinaphthothiophene derivative can be achieved. The efficiency of fibrous crystal formation can be improved. The packing rate is 95% by volume or less. This further reduces wear on the beads and grinding container.

[0063] In a wet grinding method using a bead mill, the peripheral speed of the stirring mechanism is preferably 6.0 m / s. The speed is between s / and 15 m / s, and more preferably between 8.0 m / s and 12 m / s. By setting the peripheral speed to 6.0 m / s or higher, the efficiency of generating nanofiber-like crystals can be increased. It can be improved. By keeping the peripheral speed below 15 m / s, the beads and crushed This further reduces wear and tear on the container.

[0064] In a wet grinding method using a bead mill, the slurry temperature is controlled by the cooling water temperature and the circulation rate. This can be controlled by adjusting peripheral speed, etc. The slurry at the outlet of the grinding container The temperature is preferably between 10°C and 30°C, and more preferably between 15°C and 25°C. Therefore, by raising the slurry temperature to 10°C or higher, the amount of cooling water required can be further reduced. This makes temperature control easier. By keeping the slurry temperature below 30°C, This further reduces wear on the sieve and grinding container.

[0065] In a wet grinding method using a bead mill, the operating method is not particularly limited, for example, Examples include the Chi-type, Pass-type, and Circulating-type. From the viewpoint of temperature control and work efficiency, the Circulating-type is preferable. The driving method is preferable.

[0066] 2. Varnish The varnish in this embodiment contains the composite particles and solvent of this embodiment, or dinaphthoth It comprises an offen derivative, a resin, and a solvent, and may contain other components as needed. That's fine.

[0067] 2.1. Solvent The solvent in this embodiment is poor at dissolving the dinaphthothiophene derivative and dissolves the resin. Preferably, it is possible to select one or more solvents according to the application. It is possible.

[0068] Such solvents are not particularly limited, but examples include toluene, xylene, and other aromatic solvents. Group solvents; ether-based solvents such as tetrahydrofuran and diphenyl ether; dimethylform Amide solvents such as amides and dimethylacetamide; carbonized waters such as cyclohexane and decalin. Elementary solvents; ketotic solvents such as methyl ethyl ketone and cyclohexanone; ethyl acetate, acetic acid Ester solvents such as butyl; nitrile solvents such as acetonitrile and butyronitrile; disulfur Carbon dioxide, sulfur-based solvents such as dimethyl sulfoxide; chloroform, dichloroethane, trichloroethylene Examples of halogenated solvents include loroethane.

[0069] The solvent content in the above varnish is preferably 50% by mass relative to the total mass of the varnish. The above is 95% by mass or less, more preferably 65% ​​by mass or more and 85% by mass or less, and further Preferably, the solvent content in the varnish is 70% by mass or more and 80% by mass or less. By maintaining such a range, it becomes possible to create an even thinner and more uniform coating film.

[0070] The varnish of this embodiment is not particularly limited in terms of other components, but for example, inorganic nanoparticles It may contain children. Such inorganic particles preferably have a refractive index of 1.8 or higher. More preferably 2.0 or higher, and even more preferably 2.2 or higher. Also, the inorganic particles The average particle size of the child is preferably 100 nm or less, and more preferably 50 nm or less. More preferably, the particle size is 30 nm or less. In particular, the average particle size of the inorganic particles is 100 nm or less. As a result, it tends to be easier to obtain a more transparent and hard coating film. However, these are not particularly limited to, for example, titanium dioxide, zirconia, cerium oxide, and zinc oxide. Examples include oxide nanoparticles such as tin oxide. This tends to improve the refractive index of the coating film.

[0071] 2.2. Manufacturing method When preparing a varnish containing particles of the dinaphthothiophene derivative of this embodiment, dinaphthothiophene For a solvent that is difficult to dissolve tothiophene derivatives but can dissolve resin particles This can be produced by adding the composite particles of this embodiment.

[0072] Furthermore, varnish containing the dinaphthothiophene derivative of this embodiment but without its particles. When preparing it, use a solvent that can dissolve the dinaphthothiophene derivative and resin. In contrast, the dinaphthothiophene derivative, resin, and other components as needed are added and stirred, etc. It can be obtained by doing so.

[0073] To rapidly disperse composite particles or dinaphthothiophene derivatives in a solvent, as needed A known device may be used, and such a device is not particularly limited, but for example, Examples include ultrasonic cleaners.

[0074] By using the composite particles and varnish of this embodiment, a transparent coating film (especially a transparent and hard coating) can be obtained. It is possible to produce films and other transparent, rigid molded bodies. Furthermore, such composite particles and Varnish can also be used as an adhesive for bonding materials together.

[0075] More specifically, simply heating the composite particles of this embodiment in their solid state will create a dry surface on an object. A coating can be produced and used for bonding two or more materials. For example, glass After creating a thin, uniform powder layer consisting of the composite particles of this embodiment on the surface of the plate, an appropriate temperature is applied. By heating for a certain amount of time, a transparent and hard coating can be created on the surface of the glass plate. By heating a powder layer of composite particles sandwiched between two glass plates, the powder layer changes into a transparent material. This allows the two glass plates to be bonded together at the same time.

[0076] Furthermore, all or part of the components of the composite particles of this embodiment can also be dissolved in a solvent and used. It is possible. Specifically, the varnish of this embodiment can be used as a coating agent or adhesive. For example, the varnish of this embodiment can be applied to the surface of a glass plate to form a thin, uniform coating layer. After preparing the varnish, the organic solvent in the varnish is evaporated, creating a transparent coating on the surface of the glass plate. A film can be fabricated. Also, by sandwiching varnish between two glass plates, the organic solvent in the varnish can be used. By volatilizing it, two glass plates can be bonded together.

[0077] The refractive index of the resulting coating film depends on the content of the dinaphthothiophene derivative in the composite particles or varnish. Since it correlates with the amount, the content of dinaphthothiophene derivatives in composite particles or varnish By adjusting this, it is possible to control the refractive index of the resulting rigid coating. [Examples]

[0078] The present invention will be described in more detail below using examples and comparative examples. This is not limited in any way by the examples provided.

[0079] 1. Measurement conditions <Conditions for Nuclear Magnetic Resonance (NMR)> Using an NMR spectrometer manufactured by JEOL Ltd. (product name: JNM-ECA600), the solvent was... Dimethyl sulfoxide-d6 (DMSO-d6) is used as the standard substance, and residual H-sulfate of the measurement solvent is used. Measurements were taken using Gunal (2.49 ppm).

[0080] <Conditions for Scanning Electron Microscope (SEM)> Analytical instrument: Scanning electron microscope manufactured by JEOL Ltd. (Product name: JSM-6610LA) Acceleration voltage: 20kV Pretreatment, etc.: The sample was fixed onto carbon tape and gold deposition was performed.

[0081] <Conditions for powder X-ray diffraction (XRD) measurement> Measurement device: Powder X-ray diffractometer manufactured by Rigaku Corporation (product name: RINT) X-ray:Cu / 40kV / 30mA Counting time / scan speed: 2 deg / min Goniometer: Ultima+ Horizontal Goniometer Sampling width: 0.02 deg Scan axis: 2θ / θ Scanning range: 5-80 degrees Long side limiting slit: 10mm Entrance slit: 1° Light-receiving slit 1:1° Light-receiving slit 2: 0.3 mm Detector: Scintillation counter Scan mode: Continuous

[0082] <Conditions for Differential Scanning Calorimetry (DSC)> Measurement device: Differential scanning calorimeter manufactured by Seiko Instruments Inc. (Product name: DSC6200) Reference: Al (container only) Heating rate: 10℃ / min Gas: N2 Gas flow rate: 50 mL / min

[0083] <Conditions for Mechanochemical Compounding Treatment> Equipment used: Planetary ball mill (product name: premium-line P-7, Fritsch) (Made by Japan Co., Ltd.) Container used: Volume; 80 mL, Type: Zirconia Compounding process: 10g of mixed powder is placed in the above container together with 80g of zirconia with a diameter of 5mm. The crushing process was carried out at a rotation speed of 600 rpm for a total rotation time of 45 minutes. During this process, friction To suppress the rise in temperature inside the container, the rotation and grinding process is repeated for 5 minutes, with an interval of about 60 minutes between each cycle. This was repeated until the transition time reached 45 minutes.

[0084] 2. Preparation of dinaphthothiophene derivatives Based on the method described in Example 1 of Japanese Patent Publication No. 2011-178985, Dinaphthothio I synthesized Yen (DNT).

[0085] Furthermore, based on the methods described in Examples 2, 3 and 7 of Japanese Patent Publication No. 2011-178985 We synthesized a methacrylate monomer (DNTMA) having a dinaphthothiophene skeleton, and purified it. A 100% pure white powder was obtained. [ka]

[0086] The results of the NMR measurement of DNTMA are as follows: 1H NMR (DMSO-d6, 600MHz): δ(ppm) 1.94(3H,s ), 5.63(2H,s), 5.75(1H,s), 6.15(1H,s), 7.63- 7.67(4H,m), 8.10-8.11(1H,d), 8.16-8.19(3H, m), 8.23-8.24(1H,d), 8.69-8.73(2H,m)

[0087] 3. Fabrication of composite particles <Example 1: Composite Particle 1> A mixture of the following composition was prepared by placing the mixture into a mortar and grinding and mixing it for about 5 minutes. The powder was subjected to the above-described mechanochemical compounding treatment to obtain composite particles 1. [Mixing ratio (mass%)] DNTMA: 64.3% DNT: 7.1% Polyimide resin (product number: KPI-MX300F, manufactured by Kawamura Sangyo Co., Ltd.): 28.6%

[0088] <Example 2: Composite Particle 2> A mixture of the following composition was prepared by placing the mixture into a mortar and grinding and mixing it for about 5 minutes. The powder was subjected to the above-described mechanochemical compounding treatment to obtain composite particles 2. [Mixing ratio (mass%)] DNTMA: 64.3% DNT: 7.1% Ethylcellulose (product number 14076-01, Grade 1, manufactured by Kanto Chemical Co., Ltd.): 28.6%

[0089] <Comparative Example 1 and Example 3: Mixed Powder 1 and Composite Particles 3> Mixture 1 is obtained by placing a mixture of the following composition into a mortar and grinding and mixing for about 5 minutes. Obtained. A portion of the mixed powder 1 was subjected to the above mechanochemical compounding treatment to obtain composite particles 3. I obtained it. [Mixing ratio (mass%)] DNTMA: 50% Ethylcellulose (product number 14076-01, Grade 1, manufactured by Kanto Chemical Co., Ltd.): 50%

[0090] 4. Making the varnish <Example 4: Varnish 1> After placing 1 g of composite particles 1 prepared in Example 1 into a 9 mL glass vial, the solvent and Then, 3.5 mL of THF was added, and the cap of the glass vial was closed. After that, a tabletop ultrasonic cleaner was used. Using (W-170ST, manufactured by Honda Electronics Co., Ltd.), the solvent and composite particles in the glass vial were stirred. Stir for 10 minutes, then allow a 60-minute interval, and repeat this 6 times for a total of 60 minutes. A transparent varnish 1 was obtained by stirring.

[0091] <Example 5: Varnish 2> The only difference from Example 4 is that the composite particles were changed from composite particle 1 to composite particle 2, which was prepared in Example 2. Similarly, a transparent varnish 2 was obtained.

[0092] <Example 6: Varnish 3> The only difference from Example 4 is that the composite particles were changed from composite particle 1 to composite particle 3, which was prepared in Example 3. Similarly, a transparent varnish 3 was obtained.

[0093] 5. Rating <Composite particle 1> Scanning electron microscope image of composite particle 1 obtained by the above mechanochemical composite treatment, powder The terminal X-ray diffraction measurement profile and the introductory scanning calorimetry measurement profile are shown in Figures 2 and 3, respectively. , and as shown in Figure 4. In addition, the scanning calorimetry profile of the mixed powder before the production of composite particle 1 was obtained. The file is shown in Figure 5.

[0094] As seen in Figure 2, scanning electron microscope observations indicate that composite particle 1 is dinaphthothiophene. It was found that the derivative and the resin were uniformly intermingled.

[0095] From the powder X-ray diffraction measurement profile shown in Figure 3, the composite particle 1 and the mixed powder before composite formation are as follows: When comparing the X-ray diffraction measurement profiles of the end (not shown for mixed powder), composite particle 1 Although the intensity of each peak in the X-ray diffraction measurement profile decreased, the peak shape and each peak The positions of the particles are almost identical, and even when compound particles are formed, the dinaphth in compound particle 1 It was found that the thiophene derivative particles possess crystalline properties.

[0096] Furthermore, the endothermic peak of composite particle 1 can be seen from the results of the investigative scanning calorimetry profile shown in Figure 4. And the heat dissipation peak is on the lower temperature side compared to the investigative scanning calorimetry profile of the mixed powder shown in Figure 5. It has shifted to, and furthermore, the amount of heat at the heat absorption peak and heat release peak has also changed, and composite It was found that particle 1 has different thermophysical properties compared to the mixed powder before compounding.

[0097] <Composite particles 2> Scanning electron microscope image of composite particle 2 obtained by the above mechanochemical composite treatment, powder The terminal X-ray diffraction measurement profile and the introductory scanning calorimetry measurement profile are shown in Figures 6 and 7, respectively. , and as shown in Figure 8. In addition, the scanning calorimetry profile of the mixed powder before the preparation of composite particle 2 was obtained. The file is shown in Figure 9. As seen in Figure 6, the results of scanning electron microscopy indicate that composite particle 2 is dinaphthothiophene. It was found that the derivative and the resin were uniformly intermingled.

[0098] From the powder X-ray diffraction measurement profile shown in Figure 7, composite particle 2 and the mixed powder before composite formation are shown. When comparing the X-ray diffraction measurement profiles of the end (not shown for mixed powder), composite particle 2 Although the intensity of each peak in the X-ray diffraction measurement profile decreased, the peak shape and each peak The positions of the particles are almost identical, and even when composite particles are formed, the dinaphth in composite particle 2 It was found that the thiophene derivative particles possess crystalline properties.

[0099] Furthermore, the endothermic peak of composite particle 2 can be seen from the results of the investigative scanning calorimetry profile shown in Figure 8. And the heat dissipation peak is on the lower temperature side compared to the investigative scanning calorimetry profile of the mixed powder shown in Figure 9. It has shifted to, and furthermore, the amount of heat at the heat absorption peak and heat release peak has also changed, complex It was found that the particles possessed different thermophysical properties compared to the mixed powder before compounding.

[0100] <Composite particles 3 and mixed powder 1> Scanning electron microscope images of the prepared mixed powder 1 and composite particles 3 are shown in Figures 10 and 11, respectively. As shown in Figure 10, the mixed powder 1 contains particles of dinaphthothiophene derivative and resin particles. While they exist separately without intertwining, the composite particle 3 shown in Figure 11 is dinaphthiooff It was found that the compound particles consisted of uniformly interwoven resin derivatives.

[0101] <Varnish 1> The procedure was carried out using a film applicator (slide glass size, manufactured by Allgood). After applying varnish 1 from Example 4 to the surface of the glass slide, it was left to stand under atmospheric conditions for one day. A transparent and hard coating was obtained on the surface of the glass slide. The obtained coating was subjected to high-speed spectroscopy. Using a liposometer M-2000V-Te (manufactured by JAWoollam Co.) The refractive index and extinction coefficient were measured.

[0102] A profile of the refractive index n and extinction coefficient k of a coating film obtained using varnish 1, with wavelength as the horizontal axis. The profile is shown in Figure 12. As an example of the profile shown in Figure 12, the refractive index at a wavelength of 589.5 nm is shown. The refractive index was 1.68. As shown in Figure 12, by using varnish 1, the refractive index and transparency It was found that a coating with excellent transient properties could be obtained.

[0103] <Varnish 2> Similarly, using varnish 2 of Example 5, the same procedure as with varnish 1 above was performed on the slide glass surface. After obtaining a transparent and hard coating on the surface, the obtained coating was subjected to a high-speed spectroscopic ellipsometer M-20. Using 00V-Te (manufactured by JAWoollam Co.), the refractive index of the above coating film and The extinction coefficient was measured.

[0104] A profile of the refractive index n and extinction coefficient k of a coating film obtained using varnish 2, with wavelength as the horizontal axis. The profile is shown in Figure 13. As an example of the profile shown in Figure 13, the refractive index at a wavelength of 589.5 nm is shown. The refractive index was 1.65. As shown in Figure 13, by using varnish 2, the refractive index and transparency were improved. It was found that a rigid coating with excellent permeability could be obtained.

[0105] <Varnish 3> Similarly, using varnish 3 of Example 6, the same procedure as with varnish 1 above was performed on the slide glass surface. After obtaining a transparent and hard coating on the surface, the obtained coating was subjected to a high-speed spectroscopic ellipsometer M-20. The refractive index of the above coating was measured using 00V-Te (manufactured by JAWoollam Co.). It was decided.

[0106] The coating obtained using varnish 3 had a refractive index of 1.59 at a wavelength of 589.5 nm. [Industrial applicability]

[0107] The composite particles and varnish of the present invention are used to produce transparent, hard coatings and other transparent, hard molded articles. It can be used for this purpose. Furthermore, the composite particles and varnish of the present invention can also be used for bonding between materials. It is possible to produce them. Therefore, the composite particles and varnishes of the present invention can be produced for their respective applications. It has potential for commercial use. [Explanation of symbols]

[0108] 1...Composite particles, 11...Dinaphthothiophene derivative nanofibers, 12...Resin particles .

Claims

1. A composite particle comprising a compound having a dinaphthothiophene skeleton and a resin.

2. The average particle diameter of the composite particles is 1 μm or more. The composite particle according to claim 1.

3. The aforementioned compound includes a compound having a nanofiber-like dinaphthothiophene skeleton. A composite particle as described in item 1 or 2.

4. The composite particle according to claim 3, wherein the thickness of the compound is 1 μm or less.

5. The aforementioned compound is a compound represented by the following formula (1), or a compound represented by the following formula (1). A composite particle according to any one of claims 1 to 4, which is a polymer containing the derived structural units. 【Chemistry 1】 (In the formula, R 1 These are, independently, an organic group, a hydroxyl group, an amino group, a nitro group, and a thiol group. R is a sulfo group, a halogen atom, or an optionally substituted silyl group. 2 Each These independently include organic groups, hydroxyl groups, amino groups, nitro groups, thiol groups, sulfo groups, and halogen groups. A silyl group, or a substituted silyl group, where m is an integer from 0 to 2, independently. (And n is an integer between 0 and 4, independently of each other.)

6. A varnish comprising a compound having a dinaphthothiophene skeleton, a resin, and a solvent.

7. The aforementioned compound includes a compound having a nanofiber-like dinaphthothiophene skeleton. The varnish described in item 6.

8. The varnish according to claim 7, wherein the thickness of the compound is 1 μm or less.

9. A composite particle as described in any one of claims 1 to 5, or as described in any one of claims 6 to 8. Coating agents or adhesives, including varnishes.

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