JP6720673B2 - Fine particle unevenly distributed composite and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fine particle unevenly distributed composite in which fine particles are unevenly distributed inside a polymer substrate and a method for producing the same.

The technique of making fine particles unevenly distributed on the surface of the substrate or inside thereof to form a composite is indispensable in the development of a functional film material exhibiting optical, biological, and thermal properties.

An example of a film in which fine particles are unevenly distributed on the surface of a base material is an antireflection film used in a liquid crystal display device. By unevenly distributing fine particles having a low refractive index on the surface, an antireflection function and scratch resistance are imparted. A film that has been proposed has been proposed (see Patent Documents 1 and 2).

For example, in Patent Document 1, the surface of silica fine particles is modified with fluorinated silane, and the silica fine particles are unevenly distributed in a coating liquid mixed with a resin by surface free energy, so that when the coating liquid is thinly formed, silica Disclosed is an antireflection laminate in which fine particles are unevenly distributed on the surface of a coating film and function as a coating layer having antireflection properties and scratch resistance.

Further, in Patent Document 2, after coating a composition containing fine particles on a cellulose substrate, the poor affinity of the fine particles with the substrate component eluted in the composition is used as a driving force to make the fine particles opposite to the substrate. There is disclosed an antireflection laminate which is moved to the surface side of to form a fine particle laminate.

On the other hand, examples of the film in which fine particles are dispersed inside the substrate include a heat insulating film or a heat shielding film. It is known that indoor temperature rises in buildings and windows of vehicles due to the effect of infrared rays contained in sunlight.In summer, when the sunshine is strong and the sunshine is long, air-conditioner consumption due to room temperature rise Although the increase in electric power has become a big problem, in recent years, a heat shield film has been proposed for suppressing a rise in room temperature while maintaining the brightness of sunlight.

For example, in Patent Document 3 and Patent Document 4, by using a heat shield film in which hollow silica particles, which are heat insulating particles, particles of composite tungsten oxide, which are heat ray shielding particles, and the like are dispersed inside a resin, the indoor temperature is kept outside. A method for suppressing fluctuations due to physical factors has been proposed.

JP 2001-316604 A JP 2012-42960 A JP2012-56138A JP, 2005-160390, A

As described in Patent Documents 1 to 4 described above, a film having a function has been proposed so far by unevenly distributing fine particles on the surface of the film or by dispersing fine particles inside the film. ing.

However, a film in which fine particles are unevenly distributed on the film surface and fine particles are dispersed inside the film by sandwiching a resin layer containing no fine particles has not been reported. No technique capable of forming by a film forming process has been reported.

In the existing method, in order to produce a film in which fine particles are unevenly distributed on the surface of the film, and a resin layer containing no fine particles is sandwiched between the fine particles, the fine particles are dispersed in the film. After the formation, it was necessary to carry out a multi-stage laminating process in which a resin layer was formed on the film and then fine particles were unevenly distributed on the film surface. Such a multi-stage laminating process has a problem in that it is disadvantageous in manufacturing a product such as a reduction in yield and an increase in product price due to restrictions on material cost, resin selection, and an increase in processing steps.

An object of the present invention is to provide a fine particle unevenly distributed composite in which fine particles are unevenly distributed on at least one surface, and fine particles are dispersed inside with a resin layer containing no fine particles interposed therebetween, and a method for producing the fine particle unevenly distributed composite. Is to provide.

A fine particle unevenly distributed composite comprising a cured film of a coating liquid containing silica fine particles and urethane acrylate, wherein one surface side of the fine particle unevenly distributed composite has a portion in which silica fine particles are unevenly distributed, and the other of the fine particle unevenly distributed composites There is a portion in which silica fine particles are dispersed on the surface side, a portion not containing silica fine particles is present between the portion in which the silica fine particles are unevenly distributed and the portion in which the silica fine particles are dispersed, and the portion in which the silica fine particles are unevenly distributed, and the silica fine particles A resin obtained by curing urethane acrylate is distributed in a portion containing no silica and a portion in which silica fine particles are dispersed, the average particle diameter of the silica fine particles is 100 nm or more and 500 nm or less, and the addition rate of the silica fine particles is silica. and wherein 50 weight below der Rukoto 30 wt% or more of total particulates and urethane acrylate.

Having a part where the silica fine particles are unevenly distributed on one surface side, having a part where the silica fine particles are dispersed on the other surface side, silica fine particles are provided between the part where the silica fine particles are unevenly distributed and the part where the silica fine particles are dispersed. A method for producing a fine particle unevenly distributed composite having a part not containing, a coating solution adjusting step of preparing a fine particle-containing coating solution containing silica fine particles and urethane acrylate, and a coating step of applying the coating solution onto a support. A heat treatment step of heat-treating the coating liquid applied on the support to form a film, and an ionizing radiation irradiation step of forming a film by irradiating the film with ionizing radiation and curing the film to form a fine particle unevenly distributed complex supported on the support. And a peeling step of peeling the fine particle unevenly distributed composite from the support , the average particle diameter of the silica fine particles is 100 nm or more and 500 nm or less, and the addition rate of the silica fine particles is 30% by weight of the total amount of the silica fine particles and the urethane acrylate. characterized in der Rukoto 50 wt inclusive.

According to the present invention, a fine particle unevenly distributed composite in which fine particles are unevenly distributed on at least one surface, and fine particles are dispersed inside with a resin layer containing no fine particles interposed therebetween, and a method for producing this fine particle unevenly distributed composite are provided. Can be provided.

The figure which showed the structure of the cutting|disconnection part end surface of the particulate unevenly distributed composite which concerns on embodiment of this invention. The figure which showed the electron microscope cross-sectional image of the fine particle uneven distribution composite obtained in Example 1. The figure which showed the electron microscope cross-sectional image of the fine particle uneven distribution composite obtained in Examples 1-2 and Comparative Examples 1-7.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a diagram showing a configuration of an end surface of a cut portion of a particulate unevenly distributed composite according to an embodiment of the present invention. The fine particle unevenly distributed composite 1 is in the form of a film composed of fine particles 3 and a resin 5, and has a fine particle unevenly distributed layer 7 in which the fine particles 3 are unevenly distributed from at least one surface side, and a resin single layer 9 not containing the fine particles 3. The fine particle dispersion layer 11 in which the fine particles 3 are dispersed is provided in this order.

(Fine particles)
Next, the fine particles 3 according to the present invention will be described. As the fine particles 3, inorganic fine particles or organic fine particles are used. Examples of the inorganic fine particles include oxides such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, tin oxide, and antimony pentoxide, and complex oxides such as antimony-doped tin oxide and phosphorus-doped tin oxide. In addition to these, as the inorganic fine particles, calcium carbonate, talc, clay, kaolin, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate and the like can be used. Further, as the organic fine particles, polymethacrylic acid methyl acrylate resin powder, acrylic-styrene resin powder, polymethylmethacrylate resin powder, silicon resin powder, polystyrene powder, polycarbonate powder, melamine resin powder, polyolefin resin powder, etc. Can be used. Further, as the fine particles 3, a mixture of two or more kinds of the above-mentioned inorganic fine particles and/or organic fine particles may be used.

Here, the fine particle unevenly distributed composite 1 can exhibit functions of optical characteristics such as antireflection and structural coloring by the fine particles 3 unevenly distributed on the surface. For example, by using metal fine particles as the fine particles 3. Hard coat properties can be exhibited, and by forming irregularities on the surface of the unevenly distributed fine particle composite 1, it is possible to exhibit functions such as adhesiveness. In addition, the unevenly distributed fine particles composite 1 can have a plurality of functions such as a reduction in the linear expansion coefficient of the unevenly distributed fine particles composite 1 due to the fine particles 3 dispersed therein, and heat insulation or heat shielding by lowering the thermal conductivity. ..

The average particle diameter of the fine particles 3 is preferably 100 nm or more and 500 nm or less.

The average particle size of the fine particles 3 according to the present invention is measured from the cross section of the fine particle unevenly distributed composite 1. A transmission electron microscope (TEM) can be used for observing the cross section of the unevenly distributed fine particle composite 1. However, it is not particularly limited to this. When obtaining the average particle diameter of the fine particles 3 from the cross section of the unevenly distributed fine particle composite body 1, two or more arbitrary cross sections of the unevenly distributed fine particle composite body 1 are observed. Further, when observing the cross section of the unevenly distributed fine particle composite 1, it is preferable to set the magnification so that 20 or more, preferably 30 or more fine particles are observed. In each cross section, 10 or more fine particles 3 are arbitrarily selected and the particle diameter is measured, and the average value is taken as the average particle diameter of the fine particles 3.

Further, the fine particles 3 may have a surface having an ionizing radiation curing group. As will be described later in detail, by using as the fine particles 3 those having an ionizing radiation curing group on the surface, a fine particle unevenly distributed composite 1 formed by applying a solution containing the resin 5 and the fine particles 3 onto a substrate and heat-treating the solution. When the resulting coating film is cured by ionizing radiation, it can also react with the surface of the fine particles 3 to improve the strength of the coating film.

(resin)
Next, the resin 5 according to the present invention will be described. As the resin 5, an ionizing radiation curable resin composition is used. Examples of the ionizing radiation curable resin composition include acrylic materials, which are synthesized from (meth)acrylate compounds such as acrylic acid or methacrylic acid ester of alcohol, diisocyanate and alcohol, and hydroxy ester of acrylic acid or methacrylic acid. Such urethane (meth)acrylate compounds can be used. In addition to these, as the ionizing radiation curable resin composition, a polyether resin having an acrylate functional group, a polyester resin, an epoxy resin, an alkyd resin, a spiro acetal resin, a polybutadiene resin, a polythiol polyene resin, or the like is used. be able to.

In addition, in this specification, "(meth)acrylate" indicates both "acrylate" and "methacrylate". For example, "urethane (meth)acrylate" indicates both "urethane acrylate" and "urethane methacrylate". Further, polyfunctional means having two or more functional groups active in the molecule by ionizing radiation.

Examples of the monofunctional (meth)acrylate compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl ( (Meth)acrylate, t-butyl (meth)acrylate, glycidyl (meth)acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth) ) Acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3- Methoxybutyl (meth)acrylate, ethylcarbitol (meth)acrylate, phosphoric acid (meth)acrylate, ethylene oxide modified phosphoric acid (meth)acrylate, phenoxy (meth)acrylate, ethylene oxide modified phenoxy (meth)acrylate, propylene oxide modified Phenoxy (meth)acrylate, nonylphenol (meth)acrylate, ethylene oxide modified nonylphenol (meth)acrylate, propylene oxide modified nonylphenol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol ( (Meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxy Propyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hexahydrohydrogen phthalate, 2-(meth)acryloyloxypropyl tetrahydrohydrogen phthalate, dimethylaminoethyl (meth)acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth ) Acrylate, hexafluoropropyl(meth)acrylate, octafluoropropyl(meth)acrylate, octafluoropropyl(meth)acrylate, 2 And adamantane derivative mono(meth)acrylates such as adamantyl acrylate having a monovalent mono(meth)acrylate derived from adamantane and adamantane diol.

Examples of the bifunctional (meth)acrylate compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth). Acrylate, ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di( (Meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, and other di(meth)acrylates. ) Acrylate and the like can be mentioned.

Examples of the trifunctional or higher functional (meth)acrylate compound include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and tris2-hydroxyethyl. 3 such as isocyanurate tri(meth)acrylate, tri(meth)acrylate such as glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate Functional (meth)acrylate compounds, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane penta(meth) ) Trifunctional or higher polyfunctional (meth)acrylate compounds such as acrylate, dipentaerythritol hexa(meth)acrylate, and ditrimethylolpropane hexa(meth)acrylate, and a part of these (meth)acrylates containing an alkyl group or ε-caprolactone. Examples thereof include polyfunctional (meth)acrylate compounds substituted with.

In addition to these, as the ionizing radiation curable resin composition, a polyether resin having an acrylate functional group, a polyester resin, an epoxy resin, an alkyd resin, a spiro acetal resin, a polybutadiene resin, a polythiol polyene resin, or the like is used. However, the material is not particularly limited.

In addition, polyfunctional urethane acrylate can be preferably used as the acrylic material. Urethane acrylate is obtained by reacting a polyhydric alcohol, a polyisocyanate and a hydroxyl group-containing acrylate. Specifically, UA-306H, UA-306T, UA-306I etc. (above, Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-6300B, UV-7600B, UV-7605B, UV-7640B, UV-7650B etc. (Above, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), U-4HA, U-6HA, UA-100H, U-6LPA, U-15HA, UA-32P, U-324A (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), Ebecryl-1290, Ebecryl-1290K, Ebecryl-5129 etc. (above, manufactured by Daicel Ornex), Negami Kogyo Co., UN-3220HA, UN-3220HB, UN-3220HC, UN-3220HS etc. (above, manufactured by Negami Kogyo Co., Ltd. ), but not limited to this.

Next, a method for producing the fine particle laminated composite 1 of the present invention will be described.

The fine particle unevenly distributed composite of the present invention is prepared by using a coating liquid comprising a monomer which is a precursor of the resin 5, fine particles 3 which are unevenly distributed in the resin, and a solvent which may be optionally added. Multi-layer composites can be formed with a single application to the material.

[Coating liquid preparation process]
First, the fine particles 3, the ionizing radiation curable monomer, and the ionizing radiation polymerization initiator are mixed and, if necessary, dissolved or dispersed in a solvent to prepare a coating liquid.

In the present invention, the coating liquid may or may not have a solvent, but when a solvent is used, any solvent can be used as long as it dissolves the ionizing radiation-curable resin monomer. In order to improve the surface properties after forming the coating film, the one having a relatively high boiling point improves the leveling property (uniform coating property). Further, when the film thickness of the coating film is large, the solvent is likely to remain in the coating film, and therefore the boiling point is preferably as low as possible, and the solvent can be determined in consideration of the balance between the former and the latter.

The ionizing radiation polymerization initiator used in the coating liquid in the present invention is not particularly limited, but Irg184 (1-hydroxycyclohexyl phenyl ketone), which is particularly less colored when the transparent resin is cured, can be used. Further, a surface-curing polymerization initiator α-hydroxyketone such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy) -Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, an α-aminoketone 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 with a high molar extinction coefficient -One and an acylphosphine oxide that is an internal curing type polymerization initiator, for example, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and an α-aminoketone having an absorption region at the h-line, for example, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and the like may be used in combination.

In addition to those shown above, for example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like, surface-curing system, polymerization initiation having internal curing system characteristics Any agent can be appropriately selected and used.

The amount of the ionizing radiation polymerization initiator used is preferably 0.5 to 15% by weight, based on the total solid content of the ionizing radiation curable resin, and if it is more or less than this range, the film hardness tends to be low. is there. In particular, when the amount of the polymerization initiator used is too large, the coating film may be colored.

Further, n-butylamine, triethylamine, poly-n-butylphosphine, etc. may be mixed with the coating liquid as a photosensitizer.

In addition, a coating solution prepared by dissolving ionizing radiation curable resin monomer and polymerization initiator in a solvent is added with additives for antifouling property, imparting slipperiness, preventing defects and improving dispersibility of particles. You may. For example, as the additive, polyether-modified polymethylalkylsiloxane, polyether-modified polydimethylsiloxane, fluorine-modified polymer, acrylic copolymer, polyester-modified acryl-containing polydimethylsiloxane, silicon-modified polyacryl, or the like can be used. ..

The addition rate of the fine particles 3 is preferably 60% by weight or less, and more preferably 30% by weight to 50% by weight, based on the total amount of the ionizing radiation curable resin and the fine particles 3. When the addition rate of the fine particles 3 is more than 60% by weight, the resin ratio decreases and the strength of the film decreases, so that the film shape cannot be maintained. The addition rate of the fine particles 3 is the weight ratio of the fine particles 3 in the total weight of the ionizing radiation curable resin and the fine particles 3 (solid content).

[Coating process]
Next, the coating liquid prepared in the coating liquid preparation step is applied onto the base material. As a coating method, a known method can be adopted. Specifically, bar coating method, dip coating method, spin coating method, flow coating method, spray coating method, roll coating method, gravure roll coating method, air doctor coating method, blade coating method, wire doctor coating method, knife coating. Method, reverse coating method, transfer roll coating method, microgravure coating method, kiss coating method, cast coating method, slot orifice coating method, calender coating method, die coating method and the like can be used.

Further, as a coating method, (1) a single-wafer method of applying on a single-wafer-shaped base material, (2) a coating liquid is applied to the base material while unrolling a roll-shaped base material, and a fine particle laminated composite produced Any of the roll-to-roll coating methods for winding up may be used. In particular, the roll-to-roll method is preferable because the fine particle laminated composite can be continuously formed. For example, when a roll-to-roll method is adopted, the unwinding part, the coating unit, and the winding part are passed through the base material in this order, and the fine particle laminated composite is continuously run by running continuously. It can be manufactured.

When manufactured by a roll-to-roll method, the thickness of the base material is preferably about 25 μm or more and 200 μm or less, and more preferably about 40 μm or more and 80 μm or less. However, the thickness of the base material is not limited to the above range.

A roll-shaped metal body, polyethylene terephthalate (PET film), or the like can be used as the substrate. As the base material, it will be described later in detail without being deformed in the steps such as the heat treatment step and the ionizing radiation irradiation step that are performed after applying the coating liquid. There is no particular limitation as long as it can be peeled off.

[Heat treatment process]
Next, the solvent in the coating liquid is removed by heat treatment or drying of the coating liquid applied on the substrate. For the heat treatment, a known drying means can be adopted as appropriate. For example, heating, air blowing, hot air, or the like can be used as the drying means.

[Ionizing radiation irradiation process]
Further, in order to obtain a coating film having higher hardness, an ionizing radiation irradiation step is provided after the heat treatment step. The ionizing radiation irradiation step is a step of curing the coating film by irradiating the coating film with ionizing radiation. By irradiating with ionizing radiation and curing the coating film, the fine particle unevenly distributed composite 1 having excellent solvent resistance and surface hardness can be obtained.

Ultraviolet rays, electron beams, etc. can be adopted as the ionizing radiation. In the case of ultraviolet curing, a light source such as a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc or a xenon arc can be used. In the case of electron beam curing, electron beams emitted from various electron beam accelerators such as Cockloft Wald type, Van de Graaff type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. are used. can do. The electron beam preferably has an energy of about 50 KeV or more and 1000 KeV or less, and more preferably an electron beam of about 100 KeV or more and 300 KeV or less.

[Peeling process]
By separating the coating film cured in the ionizing radiation irradiation step from the substrate, the unevenly distributed fine particle composite body 1 can be obtained.

By passing through the above steps, the unevenly distributed fine particle composite body 1 can be manufactured by a single film forming process. Therefore, the present invention can provide a simple and low-cost manufacturing process.

The fine particle unevenly distributed composite 1 according to the present invention can be used for various purposes by selecting the types of the fine particles 3 constituting the fine particle unevenly distributed layer 7 and the fine particle dispersed layer 11. In particular, it is important to select the type of the fine particles 3 that are unevenly distributed on the surface of the fine particle unevenly distributed composite 1 and that are dispersed inside, depending on the application. For example, when titanium oxide, which is generally called an optical semiconductor, is used as the fine particles 3, the fine particle unevenly distributed composite 1 has a specific light absorption band, which is suitable as a material having excellent light transmission controllability. is there. Further, by appropriately selecting the base material, the inorganic fine particles are caused on the surface of various articles such as optical equipment, housing/construction equipment, home appliance equipment, furniture/automobile interior equipment, packaging equipment, etc. Optical, thermal, electronic, magnetic, biological functions, etc. can be imparted to the particulate unevenly distributed composite 1. Optical functions include anti-reflection properties, anti-glare properties, ultraviolet blocking properties, infrared blocking properties, and scratch resistance, and thermal functions include heat blocking properties and heat insulating properties, and electronic and magnetic properties. The biological functions include conductivity, electromagnetic wave shielding property, antistatic property, and the biological functions include antibacterial property and antifungal property. In addition, various articles in which the finely-balanced particle-distributed composite body 1 having these functions can be used include an antireflection film as an optical device, an antiglare film, an ultraviolet cut film, an infrared cut film, an antistatic film, a transparent conductive film, and an electromagnetic wave. Shield film, UV cut film for housing/construction equipment, infrared cut film, heat insulation film, antibacterial/antifungal outer wall material, antistatic body/parts for home appliance equipment, antibacterial/antifungal body/parts, furniture/automobile Examples thereof include an antireflection film, an antiglare film, an antistatic film, an antibacterial/antifungal film as interior equipment, and an ultraviolet cut film, an infrared cut film, an antibacterial/antifungal film, etc. as packaging equipment.

When the fine particles 3 have pores, a material suitable for the purpose may be introduced into the pores for the purpose of imparting an optical, electronic, magnetic or biological function. The material can be introduced into the fine particles before or after the fine particle unevenly distributed composite 1 is formed.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

First, a coating liquid containing a curable composition was prepared. The composition is shown below.

[Example 1]
Particles: Silica fine particle dispersion A (40 wt%, methyl ethyl ketone (MEK) dispersion, Nissan Chemical Industries, Ltd., average particle diameter 100 nm) 63.4 parts by weight Binder matrix (ionizing radiation curable material): UA-32P (80 wt. %, containing methyl ethyl ketone (MEK), manufactured by Shin Nakamura Chemical Co., Ltd. 22.3 parts by weight, UV-7000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 7.6 parts by weight Photoinitiator: Irgacure 184 (manufactured by BASF Co., Ltd.) 1 .3 parts by weight/solvent: MEK 5.4 parts by weight It was prepared so that the solid content ratio of the particles would be 50 parts by weight.

Next, the prepared coating liquid was applied on the base material. The base material was polyethylene terephthalate (PET) (Lumirror T60, thickness 75 μm, manufactured by Toray Industries, Inc.). Moreover, the coating liquid was applied onto the base material using a wire bar coater. The coating amount of the coating liquid was adjusted so that the dry film thickness was 45 μm.

Next, the coating liquid applied to the base material was dried by heat treatment to form a coating film on the base material. The heat treatment condition was 100° C. for 3 minutes.

Next, the coating film formed on the substrate was irradiated with ionizing radiation to cure the coating film. At this time, ultraviolet rays were applied as ionizing radiation. Further, the irradiation of ultraviolet rays was carried out at an exposure dose of 400 mJ/cm ² using a conveyor type ultraviolet curing device.

After that, the cured coating film was peeled off from the substrate to obtain a fine particle unevenly distributed composite of Example 1.

[Example 2]
A fine particle ubiquitous composite was produced in the same manner as in Example 1 except that the mixing ratio of the coating liquid was changed to the following.
Particles: Silica fine particle dispersion A (40 wt%, methyl ethyl ketone (MEK) dispersion, Nissan Chemical Industries, Ltd., average particle diameter 100 nm) 42.8 parts by weight Binder matrix (ionizing radiation curable material): UA-32P (80 wt. %, containing methyl ethyl ketone (MEK), manufactured by Shin-Nakamura Chemical Co., Ltd. 35.1 parts by weight, UV-7000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 12 parts by weight Photoinitiator: Irgacure 184 (manufactured by BASF Co., Ltd.) 2 parts by weight Solvent: MEK 8.1 parts by weight It was prepared so that the solid content ratio of the particles would be 30 parts by weight.

[Comparative Example 1]
A fine particle ubiquitous composite was produced in the same manner as in Example 1 except that the mixing ratio of the curable composition was changed to the following.
Particles: 14.4 parts by weight of silica fine particle dispersion A (40 wt%, methyl ethyl ketone (MEK) dispersion, manufactured by Nissan Chemical Industries, average particle diameter 100 nm).
Binder matrix (ionizing radiation curable material): UA-32P (80 wt%, containing methyl ethyl ketone (MEK), Shin-Nakamura Chemical) 45.4 parts by weight, UV-7000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 15.5 parts by weight
Photopolymerization initiator: Irgacure 184 (manufactured by BASF) 2.6 parts by weight Solvent: MEK 22.1 parts by weight It was prepared so that the solid content ratio of the particles would be 10 parts by weight.

[Comparative example 2]
A fine particle ubiquitous composite was produced in the same manner as in Example 1 except that the mixing ratio of the coating liquid was changed to the following.
Particles: 69.9 parts by weight of silica fine particle dispersion A (30 wt%, methyl ethyl ketone (MEK) dispersion, Nissan Chemical Industries, Ltd., average particle diameter 50 nm).
Binder matrix (ionizing radiation curable material): UA-32P (80 wt%, containing methyl ethyl ketone (MEK), manufactured by Shin-Nakamura Chemical Co., Ltd.) 18.4 parts by weight, UV-7000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 6. 3 parts by weight Photoinitiator: Irgacure 184 (manufactured by BASF) 1 part by weight Solvent: MEK 4.4 parts by weight It was prepared so that the solid content ratio of the particles would be 50 parts by weight.

[Comparative Example 3]
A fine particle ubiquitous composite was produced in the same manner as in Example 1 except that the mixing ratio of the coating liquid was changed to the following.
Particles: 50.2 parts by weight of silica fine particle dispersion A (30 wt%, methyl ethyl ketone (MEK) dispersion, Nissan Chemical Industries, Ltd., average particle diameter 50 nm).
Binder matrix (ionizing radiation curable material): UA-32P (80 wt%, containing methyl ethyl ketone (MEK), manufactured by Shin-Nakamura Chemical Co., Ltd.) 30.9 parts by weight, UV-7000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 10. 6 parts by weight Photopolymerization initiator: Irgacure 184 (manufactured by BASF) 1.8 parts by weight Solvent: MEK 6.5 parts by weight It was prepared so that the solid content ratio of the particles was 30 parts by weight.

[Comparative Example 4]
A fine particle ubiquitous composite was produced in the same manner as in Example 1 except that the mixing ratio of the coating liquid was changed to the following.
Particles: 19.1 parts by weight of silica fine particle dispersion A (30 wt%, methyl ethyl ketone (MEK) dispersion, Nissan Chemical Industries, Ltd., average particle diameter 50 nm).
Binder matrix (ionizing radiation curable material): UA-32P (80 wt%, containing methyl ethyl ketone (MEK), manufactured by Shin-Nakamura Chemical Co., Ltd.) 45.4 parts by weight, UV-7000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 15. 5 parts by weight Photopolymerization initiator: Irgacure 184 (manufactured by BASF) 2.6 parts by weight Solvent: MEK 17.4 parts by weight It was prepared so that the solid content ratio of the particles would be 10 parts by weight.

[Comparative Example 5]
A fine particle ubiquitous composite was produced in the same manner as in Example 1 except that the mixing ratio of the coating liquid was changed to the following.
Particles: Silica fine particle dispersion A (40 wt%, methyl ethyl ketone (MEK) dispersion, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 15 nm) 62.2 parts by weight.
Binder matrix (ionizing radiation curable material): UA-32P (80 wt%, containing methyl ethyl ketone (MEK), manufactured by Shin-Nakamura Chemical Co., Ltd.) 21.9 parts by weight, UV-7000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 7. 5 parts by weight Photoinitiator: Irgacure 184 (manufactured by BASF) 1.2 parts by weight Solvent: MEK 7.2 parts by weight It was prepared so that the solid content ratio of the particles would be 50 parts by weight.

[Comparative Example 6]
A fine particle ubiquitous composite was produced in the same manner as in Example 1 except that the mixing ratio of the coating liquid was changed to the following.
Particles: 42.8 parts by weight of silica fine particle dispersion A (40 wt%, methyl ethyl ketone (MEK) dispersion, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 15 nm).
Binder matrix (ionizing radiation curable material): UA-32P (80 wt%, containing methyl ethyl ketone (MEK), manufactured by Shin-Nakamura Chemical Co., Ltd.) 35.1 parts by weight, UV-7000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 12 parts by weight Parts-Photopolymerization initiator: Irgacure 184 (manufactured by BASF) 2 parts by weight-Solvent: MEK 8.1 parts by weight It was prepared so that the solid content ratio of the particles was 30 parts by weight.

[Comparative Example 7]
A fine particle ubiquitous composite was produced in the same manner as in Example 1 except that the mixing ratio of the coating liquid was changed to the following.
Particles: Silica fine particle dispersion A (40 wt%, methyl ethyl ketone (MEK) dispersion, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 15 nm) 14.4 parts by weight.
Binder matrix (ionizing radiation curable material): UA-32P (80 wt%, containing methyl ethyl ketone (MEK), manufactured by Shin-Nakamura Chemical Co., Ltd.) 45.4 parts by weight, UV-7000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 15. 5 parts by weight-Photopolymerization initiator: Irgacure 184 (manufactured by BASF) 2.6 parts by weight-Solvent: MEK 22.1 parts by weight It was prepared so that the solid content ratio of the particles would be 10 parts by weight.

[Comparative Example 8]
A fine particle ubiquitous composite was produced in the same manner as in Example 1 except that the mixing ratio of the coating liquid was changed to the following.
Particles: 75.5 parts by weight of silica fine particle dispersion A (40 wt%, methyl ethyl ketone (MEK) dispersion, Nissan Chemical Industries, Ltd., average particle diameter 100 nm).
Binder matrix (ionizing radiation curable material): UA-32P (80 wt%, containing methyl ethyl ketone (MEK), manufactured by Shin-Nakamura Chemical Co., Ltd.) 16.9 parts by weight, UV-7000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 6. 1 part by weight/photopolymerization initiator: Irgacure 184 (manufactured by BASF) 1 part by weight/solvent: MEK 0.5 part by weight It was prepared so that the solid content ratio of the particles would be 60 parts by weight.

[Evaluation method]
The uneven distribution of fine particles was observed with an electron microscope. The observation method will be described below. After sandwiching the unevenly distributed fine particle composites of Examples 1 and 2 and Comparative Examples 1 to 8 with pellets of an ultraviolet curable resin and immobilizing them, the cross section of the pellets was excavated with a glass cutter and a diamond cutter using a microtome and flattened. The cross section was formed. Conductivity was imparted by forming a Pt (platinum) thin film on the cross section of the molded fine particle unevenly distributed composite by sputtering, and the cross section was observed with an electron microscope.

An electron beam microscope cross-sectional observation image of the fine particle unevenly distributed composite obtained in Example 1 is shown in FIG. From FIG. 2, the fine particle unevenly distributed composite obtained in Example 1 has a fine particle unevenly distributed layer in which fine particles are unevenly distributed on the surface, and the fine particle dispersed layer in which fine particles are dispersed is a resin-only layer containing no fine particles. It can be seen that it has a three-layer structure internally formed on the opposite side of the surface with the uneven distribution layer of fine particles.

FIG. 3 shows an electron microscopic cross-sectional observation image of the fine particle unevenly distributed composites obtained in Examples 1 and 2 and Comparative Examples 1 to 7. In the silica fine particles having an average particle diameter of 100 nm, the uneven distribution structure of the fine particles was observed at the addition rates of 30% by weight and 50% by weight, while at 10% by weight, the dispersion of the fine particles was sparse and the uneven distribution was clear. The structure could not be confirmed.

Further, in the silica fine particles having an average particle diameter of 15 nm, although silica particles unevenly distributed on the film surface were observed, no single resin layer was observed and a clear uneven distribution structure could not be confirmed.

On the other hand, in the sample to which 60% by weight of silica fine particles described in Comparative Example 8 was added, when the film was peeled from the base material, it was very fragile and the film was damaged, so that a self-supporting film could not be obtained.

INDUSTRIAL APPLICATION This invention can be utilized for the functional film material which expresses an optical, biological, and thermal characteristic.

DESCRIPTION OF SYMBOLS 1 Fine particle unevenly distributed complex 3 Fine particles 5 Resin 7 Fine particle unevenly distributed layer 9 Resin single layer 11 Fine particle dispersed layer

Claims (2)

A fine particle unevenly distributed composite comprising a cured film of a coating liquid containing silica fine particles and urethane acrylate ,
The fine particle unevenly distributed composite has a portion where the silica fine particles are unevenly distributed on one surface side, and the fine particle unevenly distributed composite has a portion where the silica fine particles are dispersed, and the silica fine particles are unevenly distributed. Between the portion and the portion in which the silica fine particles are dispersed, having a portion not containing the silica fine particles,
A resin formed by curing the urethane acrylate is distributed in a portion in which the silica fine particles are unevenly distributed, a portion not containing the silica fine particles, and a portion in which the silica fine particles are dispersed,
The average particle size of the silica fine particles is 100 nm or more and 500 nm or less,
The addition rate of the fine silica particles, wherein the silica fine particles and 50 wt less der Rukoto 30 wt% or more of the total of the urethane acrylate, fine uneven distribution complex. There is a portion where the silica fine particles are unevenly distributed on one surface side, and a portion where the silica fine particles are dispersed on the other surface side, and between the unevenly distributed portion and the silica fine particle dispersed portion. A method for producing a fine particle unevenly distributed composite having a portion not containing the silica fine particles ,
A coating liquid adjusting step of preparing a fine particle-containing coating liquid containing silica fine particles and urethane acrylate ,
A coating step of coating the coating liquid on a support,
A heat treatment step of forming a film by heat treating the coating liquid applied on the support;
Irradiating the film with ionizing radiation to cure it, and an ionizing radiation irradiating step of forming a fine particle unevenly distributed composite supported by the support,
And a peeling step of peeling the fine particle unevenly distributed composite from a support ,
The average particle size of the silica fine particles is 100 nm or more and 500 nm or less,
The addition rate of the silica fine particles, and the silica fine particles and wherein 50 weight below der Rukoto 30 wt% or more of the total of the urethane acrylate, a manufacturing method of the fine uneven distribution complex.