JP2008201908A - Coated substrate having coating film comprising hollow silicone particulate and fluorine resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent coated substrate exerting a low reflectance and a high film strength by providing a coated film comprising a hollow silicone particulate and a fluorine resin for forming the coating film, provided that the hollow silicone particulate has a high porosity and a low reflectance, shows a high productivity, is hardly breakable and has a narrow particle size distribution and a particle size of ≤1 μm, and the fluorine resin for forming the coating film has a low reflectance. <P>SOLUTION: The transparent substrate having a low reflectance and a high film strength is obtained by providing the coating film comprising the hollow silicone particulate and the fluorine resin for forming the coating film. Here, the hollow silicone particulate is obtained by removing an organic polymer particle and/or an organic solvent from a core-shell particle, provided that the core-shell particle is obtained by coating a particle comprising the organic polymer particle and/or the organic solvent with a particular silicone compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a coated substrate in which a film comprising hollow silicone fine particles obtained by removing core components of core-shell particles obtained by coating core particles made of organic polymer particles or the like with silicone and a fluorine-based resin for film formation is formed on the surface. It relates to materials.

  When a low refractive index layer (decreasing reflection layer) made of a material having a lower refractive index than the base material is formed on the outermost layer of the transparent base material with a film thickness (about 100 nm) that is 1/4 of the visible light wavelength, the surface reflectance is reduced. It is known. Films and glass antireflection transparent substrates applying this principle are widely used in the fields of electrical products, optical products, building materials and the like.

  As a method for forming the antireflection layer, a dry coating method in which magnesium fluoride or the like is deposited or sputtered and a wet coating method in which a solution of a low refractive index material is applied to a substrate are known. In recent years, wet coating methods that have few restrictions on applicable base materials and are superior in terms of continuous productivity and cost have attracted attention.

  As a low refractive index material for the wet coating method, firstly, a fluororesin is known (see Patent Documents 1 and 2). These exhibit relatively good antireflection performance, but leave the problem of low film strength.

  As a low refractive index material of the wet coating method, a material composed of porous or hollow silica and a film forming matrix is also known (see Patent Document 3).

  Hollow silica having a particle size of about 0.1 to 300 μm and a method for producing the same are already known (see Patent Documents 4 and 5). In the technique disclosed in Patent Document 4, first, an organic solvent is added to and mixed with an inorganic substance such as silicate to form an oil-in-water type (O / W type) emulsion, and an organic solvent containing a lipophilic surfactant therein. To make an oil-in-water oil-in-water (O / W / O type) emulsion, and finally transform the inorganic compound into a water-insoluble precipitate with an inorganic acid or an ammonium salt of the inorganic acid. It has gained. Thereafter, various methods for producing hollow silica particles have been disclosed (see Patent Documents 6 to 8). In Patent Document 6, silicates such as alkali metals and alkali-soluble inorganic compounds are made into colloidal particles with an alkaline aqueous solution having a pH of 10 or more, and after removing some of the elements other than silicon and oxygen in the particles, A method of coating with a hydrolyzable organosilicon compound or the like is disclosed. According to Patent Document 7, when tetraalkoxysilane solubilized in water is emulsified in an organic solvent with a surfactant, hydrolysis / condensation reaction occurs, and when the water content is high, micron-sized hollow silica particles can be synthesized. Is disclosed. Patent Document 8 discloses a process for obtaining hollow silica by precipitating active silica from an alkali metal silicate on a core of a material other than silica and removing the core.

However, with these technologies, there are problems such as a large number of pores in the silica layer and the thickness of the thin silica layer, which are easily broken during processing, or that a considerable part of the core particles remain in the cavity and the porosity does not increase. Many problems remain, such as the problem that only micron-sized products with a wide distribution can be produced, and the application is limited, or the problem is that productivity is poor because of a long reaction time and many processes.
JP-A-4-355401 JP-A-9-203801 JP 2001-233611 A JP-A 63-258642 JP-A-6-330606 JP 7-133105 A Japanese Patent Laid-Open No. 11-29318 Special Table 2000-500113

  The present invention has a high void ratio, a low refractive index, good productivity, is not easily broken, and has a narrow particle diameter distribution and a hollow silicone fine particle having a particle diameter of 1 μm or less, and a low refractive index fluorine-based film forming film. An object of the present invention is to provide a transparent coated substrate having a low reflectivity and a high film strength by a coating composed of a resin.

  In view of the above problems, the present inventors have made extensive studies, and as a result, organic polymer particles and / or organic polymer particles in core-shell particles obtained by coating organic polymer particles and / or particles made of an organic solvent with a specific silicone compound and / or Alternatively, it has been found that a transparent base material having a desired low reflectance and a high film strength can be obtained by a film comprising hollow silicone fine particles and a fluorine resin for film formation characterized by removing an organic solvent, The present invention has been completed.

That is, this invention relates to the manufacturing method of the base material with a film which consists of following process (a)-process (c).
(A) Particles composed of organic polymer particles (A) and / or organic solvent (B) are _converted into SiO _4/2 units, RSiO _3/2 units (wherein R is an alkyl group having 1 to 4 carbon atoms, An aromatic group having 6 to 24 carbon atoms, a vinyl group, a γ- (meth) acryloxypropyl group, or an organic group having an SH group) and an R ₂ SiO _2/2 unit (wherein R is Or an organic group having 1 to 4 carbon atoms, an aromatic group having 6 to 24 carbon atoms, a vinyl group, a γ- (meth) acryloxypropyl group, or an SH group). Covered with a silicone compound (C) consisting of one unit or two or more units selected, wherein the proportion of R ₂ SiO _2/2 units is 20 mol% or less and the proportion of RSiO _3/2 units is 50 mol% or more. And (b) core-shell process for producing core-shell particles (D) A step of producing hollow silicone fine particles (E) having a volume average particle diameter of 0.001 to 1 μm by removing particles comprising organic polymer particles (A) and / or organic solvent (B) in the child (D) ( c) A step of forming a coating (G) containing hollow silicone-based fine particles (E) and a coating-forming fluororesin (F) alone or together with other coatings on the substrate surface.

  In a preferred embodiment, the weight ratio of the total amount of the organic polymer particles (A) and / or the organic solvent (B) to the silicone compound (C) is 2/98 to 95/5. It is related with the manufacturing method of the said base material with a film.

  In a preferred embodiment, the film-coated base is characterized in that the organic polymer particles (A) and / or the organic solvent (B) in the core-shell particles (D) are removed using an organic solvent. The present invention relates to a method for manufacturing a material.

Further, in the present invention, the outer peripheral portion has SiO _4/2 units and RSiO _3/2 units (wherein R is an alkyl group having 1 to 4 carbon atoms, an aromatic group having 6 to 24 carbon atoms, a vinyl group, γ -Represents at least one organic group having (meth) acryloxypropyl group or SH group) and R ₂ SiO _2/2 unit (wherein R is an alkyl group having 1 to 4 carbon atoms, 6 to 6 carbon atoms) 1 unit selected from the group consisting of 24 aromatic groups, vinyl group, γ- (meth) acryloxypropyl group, or an organic group having SH group), or R ₂ SiO Hollow silicone fine particles (E) having a volume average particle diameter of 0.001 to 1 μm comprising a silicone compound (C) having a ratio of _2/2 units of 20 mol% or less and a ratio of RSiO _3/2 units of 50 mol% or more. ) And a fluororesin (F) for film formation The G) alone or with other coating related film-coated substrate having on the substrate surface.

  In a preferred embodiment, the hollow silicone fine particles (E) are in the core-shell particles (D) in which the particles composed of the organic polymer particles (A) and / or the organic solvent (B) are coated with the silicone compound (C). It is related with the said coating-coated base material characterized by the hollow silicone type microparticles | fine-particles obtained by removing the particle | grains which consist of organic polymer particle (A) and / or organic solvent (B) from.

  The hollow silicone fine particles of the present invention have a high porosity, a low refractive index, good productivity, are not easily broken, and have a particle size of 1 μm or less with a narrow particle size distribution. By forming a coating comprising a fluororesin for forming a coating on the surface of the substrate, a transparent coated substrate with a very low reflectance and high film strength can be provided.

The present invention includes the following steps (a) to (c).
(A) 1 unit selected from the group consisting of SiO _4/2 units, RSiO _3/2 units and R ₂ SiO _2/2 units, wherein the particles comprising organic polymer particles (A) and / or organic solvent (B) Alternatively, it is coated with a silicone compound (C) consisting of 2 units or more, wherein the proportion of R ₂ SiO _2/2 units is 20 mol% or less and the proportion of RSiO _3/2 units is 50 mol% or more. Step (b) for producing D) Hollow silicone having a volume average particle size of 0.001 to 1 μm by removing particles comprising organic polymer particles (A) and / or organic solvent (B) in core-shell particles (D) (C) A step of forming a coating (G) containing hollow silicone fine particles (E) and a fluororesin (F) for forming a film on the surface of a substrate alone or together with other coatings Method for producing a coated substrate comprising Is to provide.

In the present invention, the outer peripheral portion is composed of one unit or two or more units selected from the group consisting of SiO _4/2 units, RSiO _3/2 units and R ₂ SiO _2/2 units, and R ₂ SiO _2/2 units. Formation of a film with hollow silicone fine particles (E) having a volume average particle diameter of 0.001 to 1 μm comprising a silicone compound (C) having a ratio of 20 mol% or less and an RSiO _3/2 unit ratio of 50 mol% or more The base material with a film which has the film (G) containing the fluororesin (F) for use on a base material surface alone or with another film is provided.

  The composition of the organic polymer particles (A) of the present invention is not limited. For example, a soft polymer represented by polybutyl acrylate, polybutadiene, butyl acrylate-butadiene copolymer, etc. may be used. Even hard polymers such as butyl acrylate-styrene copolymer, butyl acrylate-acrylonitrile copolymer, butyl acrylate-styrene-acrylonitrile copolymer, and styrene-acrylonitrile copolymer can be used without any problem. Among these, a soft polymer is preferable and polybutyl acrylate is more preferable from the viewpoint of removability in the subsequent coagulation step.

  The production method of the organic polymer particles (A) of the present invention is not particularly limited, and known methods such as an emulsion polymerization method, a microsuspension polymerization method, a miniemulsion polymerization method, and an aqueous dispersion polymerization method can be used. Among these, it is particularly preferable to produce the emulsion by an emulsion polymerization method from the viewpoint of easy control of the particle diameter and suitability for industrial production.

  A radical polymerization initiator may be used for the polymerization of the organic polymer particles (A). Specific examples of the radical polymerization initiator include organic peroxides such as cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, paramentane hydroperoxide, and persulfuric acid. Examples thereof include inorganic peroxides such as potassium and ammonium persulfate, and azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis-2,4-dimethylvaleronitrile. For example, ferrous sulfate-sodium formaldehydesulfoxylate-ethylenediaminetetraacetic acid 2Na salt, ferrous sulfate-glucose-sodium pyrophosphate, ferrous sulfate-sodium pyrophosphate-sodium phosphate When the redox system is used, the polymerization can be completed efficiently even at a low polymerization temperature.

  The organic polymer particle (A) of the present invention is preferably a non-crosslinked polymer in consideration of the removal of the organic polymer performed in a later stage with an organic solvent. A lower molecular weight is preferred. Specifically, the weight average molecular weight is preferably less than 30000, and more preferably less than 10,000. In order to reduce the weight average molecular weight of the organic polymer particles (A), for example, use a suitable combination of various means such as use of a chain transfer agent, setting to a high polymerization temperature, and use of a large amount of initiator. Can do. The lower limit of the weight average molecular weight of the organic polymer particles (A) is not particularly limited, but is about 2000 from the viewpoint of the difficulty of synthesis. In addition, a weight average molecular weight can be measured by the analysis (polystyrene conversion) by gel permeation chromatography (GPC), for example.

  In the present invention, a seed polymerization method can be used to narrow the particle size distribution of the organic polymer particles (A). From the viewpoint that the hollow silicone-based particles have a uniform refractive index, it is preferable that the particle size distribution of the organic polymer particles (A) is narrow. In addition, the volume average particle diameter of the organic polymer particles (A) and the core-shell particles (D) in a latex state can be obtained from a light scattering method or observation with an electron microscope. The volume average particle size and the particle size distribution can be measured, for example, by using MICROTRAC UPA manufactured by LEED & NORTHRU INSTRUMENTS.

  The organic solvent (B) in the present invention may be any one that does not dissolve in water and can form fine particles with an emulsifier, and specific examples include toluene, benzene, xylene, n-hexane and the like, but are not limited thereto. It is not something.

  In the present invention, particles composed of organic polymer particles (A) and / or organic solvent (B) can be used as a core in the production of core-shell particles (D). In the present invention, since the organic polymer (A) and / or the organic solvent (B) is finally removed, the organic solvent (B) is used in combination with the organic polymer particles (A) so that the removal is easy. However, each of them may be used alone. In the particles, when the organic polymer particles (A) and the organic solvent (B) are used in combination, the weight ratio of the organic polymer particles (A) / the organic solvent (B) is 100/0 to 1 / A range of 99 is preferred.

In the core-shell particles (D) of the present invention, the silicone compound (C) serving as the coating part is one unit selected from the group consisting of SiO _4/2 units, RSiO _3/2 units and R ₂ SiO _2/2 units, or 2 units. The ratio of R ₂ SiO _2/2 units is 20 mol% or less, and the ratio of RSiO _3/2 units is 50 mol% or more.

Examples of the raw material of the SiO _4/2 unit include one or more selected from the group consisting of silicon tetrachloride, tetraalkoxysilane, water glass, and metal silicate. Specific examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and condensates thereof.

R in the RSiO _3/2 unit is an organic group having an alkyl group having 1 to 4 carbon atoms, an aromatic group having 6 to 24 carbon atoms, a vinyl group, a γ- (meth) acryloxypropyl group, or an SH group. At least one is selected. Depending on the substrate, an organic group having a small amount of vinyl group, γ- (meth) acryloxypropyl group or SH group for R, and a large amount of alkyl group or aromatic group may be selected. Examples of raw materials for RSiO _3/2 units include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, phenyltrimethoxysilane, and phenyltriethoxy. Examples thereof include silane, phenyltripropoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and the like, and these can be used singly or in combination of two or more. .

Examples of the raw material of the R ₂ SiO _2/2 unit (R may be selected from the same group as R in the RSiO _3/2 unit) of the present invention include, for example, dimethyldimethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane. , Dimethyldiethoxysilane, diphenyldiethoxysilane, methylphenyldiethoxysilane, diethyldimethoxysilane, ethylphenyldimethoxysilane, diethyldiethoxysilane, ethylphenyldiethoxysilane, hexamethylcyclotrisiloxane (D3), octamethylcyclo In addition to cyclic compounds such as tetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), trimethyltriphenylcyclotrisiloxane, etc., linear or branched organs Siloxanes and, .gamma.-mercaptopropyl methyl dimethoxy silane, .gamma.-methacryloxypropyl methyl dimethoxy silane, vinyl methyl dimethoxy silane and the like.

In the present invention, a small amount of R ₂ SiO _2/2 unit can be mixed when the hollow silicone fine particles are desired to have flexibility. The ratio of R ₂ SiO _2/2 units in the silicone compound (C) in the core-shell particles (D) is 20 mol% or less. Furthermore, it is more preferable that it is 10 mol% or less. If the proportion of R ₂ SiO _2/2 units exceeds 20 mol%, the final hollow silicone fine particles may become too soft and a problem may arise in shape retention. The lower limit of the ratio of R ₂ SiO _2/2 units in the silicone compound (C) is 0 mol%.

In the present invention, the proportion of SiO _4/2 units in the silicone compound (C) is 0 to 50 mol% from the viewpoint of the balance between the shape retention and compatibility of the hollow silicone fine particles. It is preferably 0 to 25 mol%, and more preferably 0 to 10 mol%. When the proportion of SiO _4/2 units exceeds 50 mol%, the compatibility with the film-forming matrix is lowered, and the fine particles are aggregated in the film, so that the transparency of the coated substrate is greatly lowered.

Therefore, the ratio of RSiO _3/2 units in the silicone compound (C) of the present invention is 50 to 100 mol% from the viewpoint of the stability of the particle size distribution of the core-shell particles. It is preferably 75 to 100 mol%, more preferably 90 to 100 mol%.

  In the present invention, the weight ratio between the total amount of the organic polymer particles (A) and / or the organic solvent (B) and the silicone compound (C) is not necessarily limited, but is 2/98 to 95. / 5 is preferable, and 10/90 to 50/50 is more preferable. If the ratio is less than 2/98, the porosity of the final hollow silicone fine particles may be too low. On the other hand, if the ratio is greater than 95/5, the strength of the hollow silicone fine particles may be insufficient and may break during processing.

  The volume average particle diameter of the core-shell particles (D) of the present invention is preferably in the range of 0.001 to 1 μm, and more preferably in the range of 0.002 to 0.5 μm. Although it is possible to synthesize particles smaller than 0.001 μm or larger than 1 μm, it is difficult to synthesize stably.

  The particle size distribution of the core-shell particles (D) of the present invention is not particularly limited, but from the point that the hollow silicone-based particles have a uniform refractive index, the particle size distribution of the organic polymer particles (A) is Narrower is preferable.

In the present invention, for example, an organic polymer particle (A) and / or an organic solvent (B) and water at 5 to 120 ° C. containing an acid catalyst are used as an emulsifier, a SiO _4/2 unit raw material, RSiO _3/2 The core shell coated with the silicone compound (C) by adding the raw material of the unit and the emulsion obtained by emulsifying the mixture of the raw material of R ₂ SiO _2/2 unit and water with a line mixer or homogenizer all at once or continuously. Particles (D) can be obtained. The emulsified liquid may be added all at once or continuously. Although it takes a long time, it is preferable to employ continuous addition if importance is attached to the stability of the latex particles and the particle size distribution. If the acid catalyst is added before the addition of the emulsion and continuous addition is performed under conditions where hydrolysis and condensation proceed immediately, the core-shell particles grow large over time, and a narrow particle size distribution, as in normal seed polymerization. Can be obtained. When continuous addition is performed for a relatively short time of 30 minutes to 1 hour, both relatively good productivity and a narrow particle size distribution can be achieved.

  As the emulsifier that can be used in the present invention, an anionic emulsifier and a nonionic emulsifier can be suitably used. Specific examples of the anionic emulsifier include sodium alkylbenzene sulfonate, sodium lauryl sulfonate, potassium oleate and the like, and sodium dodecylbenzene sulfonate is particularly preferably used. Specific examples of nonionic emulsifiers include polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether.

  Examples of the acid catalyst that can be used in the present invention include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. Among these, aliphatic substituted benzenesulfonic acid is preferable and n-dodecylbenzenesulfonic acid is particularly preferable from the viewpoint of excellent emulsion stability of the organosiloxane.

  The heating for the reaction in producing the core-shell particles (D) is preferably 5 to 120 ° C, more preferably 20 to 80 ° C in that an appropriate polymerization rate can be obtained.

  In the present invention, examples of the method for removing the particles composed of the organic polymer particles (A) and / or the organic solvent (B) from the core-shell particles (D) include a method using an organic solvent and a combustion method. It is done. As the organic solvent used for removing the particles composed of the organic polymer particles (A) and / or the organic solvent (B) in the core-shell particles (D), the organic polymer particles (A) and / Or what melt | dissolves the particle | grains which consist of an organic solvent (B), and does not melt | dissolve the silicone type compound (C) used as a shell is preferable. Specific examples include acetone, toluene, benzene, xylene, n-hexane and the like.

  In the present invention, after removing the core, the hollow silicone fine particles (E) can be washed with an organic solvent. Specific examples of the organic solvent that can be used for washing include methanol and n-hexane.

  The volume average particle diameter of the hollow silicone fine particles (E) of the present invention obtained by removing particles comprising the organic polymer particles (A) and / or the organic solvent (B) is in the range of 0.001 to 1 μm. Is more preferable, and the range of 0.002 to 0.5 μm is more preferable. Particles smaller than 0.001 μm and particles larger than 1 μm tend to lower the transparency of the coated substrate.

  Since the hollow silicone fine particles (E) of the present invention have a larger porosity than conventional hollow silica, the reflectance can be lowered with a small amount of use. For this reason, the base material with a film which shows a low reflectance without the fall of film strength can be obtained.

  Examples of the fluororesin (F) for film formation of the present invention include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), a copolymer of ethylene and tetrafluoroethylene (ETFE), and a perfluoroethylene propene copolymer (FEP). ), Tetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD), etc., and modified compounds thereof. In order to lower the refractive index, it is preferable to lengthen the fluorine-substituted alkyl chain of the fluororesin. On the other hand, if the alkyl chain is too long, the film strength of the formed low refractive index layer is lowered. . From the viewpoint of refractive index, solvent dissolution during film formation, and availability, Mitsubishi Rayon's 17FM, Asahi Glass's CYTOP, DuPont's TEFLON-AF, and the like are suitable as the film-forming fluororesin.

  In addition to these, the coating (G) containing the hollow silicone fine particles (E) and the fluororesin (F) for film formation is used for paints such as acrylic resin, urethane resin, polyester resin, melamine resin, and silicone resin, if necessary. Hydrolyzable organosilicon compounds such as resins and alkoxysilanes may be added.

  In order to form a coating (G) containing hollow silicone fine particles (E) and a film-forming fluororesin (F) on a substrate, the hollow silicone fine particles (E) are dispersed in a solvent, and this dispersion is used. And a film-forming fluororesin (F) may be mixed, applied onto a substrate and dried. Solvents used for film formation include ketones, esters, phenols, aromatic hydrocarbons such as toluene, chlorofluorocarbons such as perfluoro (2-butyltetrahydrofuran), alcohols such as methanol, ethanol, propanol, and ethylene glycol. Can be used. As a method for coating on the substrate, a coating method, a spinner method, a dip method, a spray method, or the like can be usually used.

  The ratio between the hollow silicone fine particles and the film-forming fluororesin in the coating is preferably in the range of 99/1 to 1/99, more preferably in the range of 45/55 to 5/95. . When this ratio is greater than 99/1 and the amount of hollow silicone fine particles increases, the coating strength tends to decrease. When this ratio is less than 1/99 and the number of hollow silicone fine particles is decreased, the refractive index of the coating does not decrease, and the antireflection effect tends to decrease.

  The coating (G) may be formed alone on the substrate, or may be formed together with other coatings. Examples of the other coating include a protective film, a hard coat film, a planarizing film, a high refractive index film, an insulating film, a conductive resin film, a conductive metal fine particle film, a conductive metal oxide fine particle film, and a primer film. It is done.

  Examples of the substrate used in the present invention include plastics such as polyethylene terephthalate (PET), polycarbonate, and acrylic, and glass. The shape of the substrate is not particularly limited, and may be a film shape, a plate shape, or a lens shape.

  The present invention will be specifically described based on examples, but the present invention is not limited thereto. Measurements and tests in the following examples and comparative examples were performed as follows.

[Volume average particle diameter]
The volume average particle diameter of the organic polymer particles and the core-shell particles was measured in a latex state. The volume average particle size (μm) was measured by a light scattering method using MICROTRAC UPA manufactured by LEED & NORTHRUUP INSTRUMENTS as a measuring device.

[Weight average molecular weight of organic polymer]
The weight average molecular weight of the organic polymer was determined by conversion from a GPC measurement data using a calibration curve prepared with a polystyrene standard sample.

[Confirmation of core-shell particles]
Confirmation of the core-shell particles in the latex state was performed by dissolving and curing the latex in an epoxy resin, dyeing it with ruthenium, and observing it with a TEM. Those that could be confirmed to have a core-shell structure were judged as “good”, and those that could not be confirmed as “poor”.

[Confirmation of hollow silicone fine particles in coating]
The hollow silicone fine particles in the coating were confirmed by staining the coating with ruthenium and TEM observation.

[Confirmation of organic polymer removal from core-shell particles]
Addition of 5 times the amount of latex n-hexane to the core-shell particles after coagulation, mixing, stirring, standing and fractionating were performed, and the removal of the core was confirmed by determining the amount of polybutyl acrylate in the transparent supernatant. . The case where it was confirmed that the core was removed was judged as ◯, and the case where the core could not be confirmed as x.

[Measurement of reflectance]
Using a spectrophotometer (UV-spectrophotometer V-560 type, integrating sphere device ISV-469 type, manufactured by JASCO Corporation), the surface of the PET film opposite to the coated surface is roughened with sandpaper and painted with black paint. The reflectance was measured, and the minimum value in the visible light range was read.

[Measurement of total light transmittance]
The total light transmittance was measured using a haze meter (NDH-300A manufactured by Nippon Denshoku Industries Co., Ltd.).

[Measurement of adhesion]
Eleven parallel scratches were made on the surface of the coated substrate with a knife at intervals of 1 mm in length and width to make 100 squares, and cellophane tape was adhered thereto. Thereafter, the cellophane tape was peeled off, and the adhesion was determined based on the number of squares on which the film remained. A sample having a residual mesh of 95-100 was designated as A, a sample having a residual cell of 90-94 was designated as B, and a sample having a residual mesh of 0-89 was designated as C.

[Eraser resistance measurement]
A commercially available eraser (Crown) was used to evaluate the presence or absence of scratches on the surface of the coated substrate after 5 reciprocations at 1 kg weight.

(Example 1)
In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, thermometer, 400 parts by weight of water (total amount of water including various dilution water) and sodium dodecylbenzenesulfonate (SDBS) ) After 2 parts by weight (solid content) were taken and mixed, the temperature was raised to 50 ° C., and after the liquid temperature reached 50 ° C., nitrogen substitution was performed. Thereafter, a mixed solution of 10 parts by weight of butyl acrylate, 3 parts by weight of t-dodecyl mercaptan, and 0.01 parts by weight of paramentane hydroperoxide was added. After 30 minutes, add 0.002 parts by weight of ferrous sulfate (FeSO ₄ .7H ₂ O), 0.005 parts by weight of ethylenediaminetetraacetic acid 2Na salt, and 0.2 parts by weight of sodium formaldehydesulfoxylate. The polymerization was further continued for 1 hour. Thereafter, a mixed solution of 90 parts by weight of butyl acrylate, 27 parts by weight of t-dodecyl mercaptan, and 0.1 parts by weight of paramentane hydroperoxide was continuously added over 3 hours. Post-polymerization was performed for 2 hours to obtain an organic polymer latex (P-1). The latex had a volume average particle size of 0.1 μm and a weight average molecular weight of 6000.

  In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, thermometer, 500 parts by weight of water (total amount of water including various dilution waters), dodecylbenzenesulfonic acid (DBSA) 3 parts by weight and 25 parts by weight (solid content) of an organic polymer (P-1) were mixed. The pH at this time was 1.8. The temperature was raised to 80 ° C., and nitrogen substitution was performed. Thereafter, a total amount of 100 parts by weight of pure water, 0.5 parts by weight of SDBS (solid content), and 25 parts by weight of methyltrimethoxysilane (MTMS) was added at a constant rate over 30 minutes. After completion of the addition, stirring was continued for 5 hours, followed by cooling to 25 ° C. and allowing to stand for 20 hours to obtain latex-like core-shell particles. The confirmation results of the volume average particle diameter of the core-shell particles are shown in Table 1. Further, the core-shell structure was confirmed by TEM observation, and the results are shown in Table 1.

  Subsequently, 50 parts by weight of acetone was first added to 100 parts by weight of latex-like core-shell particles and stirred for 5 minutes, and then 150 parts by weight of acetone was added and stirred for 25 minutes. When allowed to stand for 3 hours, it separates into a solidified particle layer and a transparent supernatant layer. After removing the supernatant, the coagulated particle layer was isolated using filter paper. This was dispersed in 300 parts by weight of a mixed solvent of 70% by weight of methanol and 30% by weight of n-hexane. When this dispersion is allowed to stand for 3 hours, it is separated into a coagulated particle layer and a transparent supernatant layer. The coagulated particle layer was isolated using filter paper. Table 1 shows the results of confirming the removal of the organic polymer from the core-shell particles. The isolated filtered particles were dispersed in toluene to obtain a dispersion having a particle concentration of 1% by weight.

  This dispersion was mixed with a film-forming fluororesin previously dissolved in toluene at a concentration of 1% by weight, and the ratio of the hollow silicone-based particles to the fluororesin was adjusted as shown in Table 1. 17FM (manufactured by Mitsubishi Rayon) was used as the fluorine-based resin for film formation.

  This coating solution was applied to a PET film by a dip method, and then dried at 110 ° C. for 20 minutes to obtain a coated substrate with a coating thickness of 0.1 to 0.2 μm.

  The reflectance of this coated substrate was measured to determine the minimum reflectance in the visible light region. In addition, Table 1 also shows the evaluation results of the total light transmittance, resistance to erase rubber, and adhesion of the substrate.

(Examples 2-4, Comparative Examples 2-3)
In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, thermometer, 400 parts by weight of water (total amount of water including various dilution water) and sodium dodecylbenzenesulfonate (SDBS) ) After 12 parts by weight (solid content) was taken and mixed, the temperature was raised to 50 ° C., and after the liquid temperature reached 50 ° C., nitrogen substitution was performed. Thereafter, a mixed solution of 10 parts by weight of butyl acrylate, 3 parts by weight of t-dodecyl mercaptan, and 0.01 parts by weight of paramentane hydroperoxide was added. After 30 minutes, add 0.002 parts by weight of ferrous sulfate (FeSO ₄ .7H ₂ O), 0.005 parts by weight of ethylenediaminetetraacetic acid 2Na salt, and 0.2 parts by weight of sodium formaldehydesulfoxylate. The polymerization was further continued for 1 hour. Thereafter, a mixed solution of 90 parts by weight of butyl acrylate, 27 parts by weight of t-dodecyl mercaptan, and 0.1 parts by weight of paramentane hydroperoxide was continuously added over 3 hours. Post-polymerization was performed for 2 hours to obtain an organic polymer latex (P-2). The latex had a volume average particle size of 0.015 μm and a weight average molecular weight of 6000.

  In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, thermometer, 500 parts by weight of water (total amount of water including various dilution waters), dodecylbenzenesulfonic acid (DBSA) 3 parts by weight and 25 parts by weight (solid content) of an organic polymer (P-2) were mixed. The pH at this time was 1.8. The temperature was raised to 80 ° C., and nitrogen substitution was performed. Thereafter, a total amount of 100 parts by weight of pure water, 0.5 parts by weight of SDBS (solid content), and 75 parts by weight of methyltrimethoxysilane (MTMS) was added at a constant rate over 30 minutes. After completion of the addition, stirring was continued for 5 hours, followed by cooling to 25 ° C. and allowing to stand for 20 hours to obtain latex-like core-shell particles. The confirmation results of the volume average particle diameter of the core-shell particles are shown in Table 1. Further, the core-shell structure was confirmed by TEM observation, and the results are shown in Table 1.

  Subsequently, 50 parts by weight of acetone was first added to 100 parts by weight of latex-like core-shell particles and stirred for 5 minutes, and then 150 parts by weight of acetone was added and stirred for 25 minutes. When allowed to stand for 3 hours, it separates into a coagulated particle layer and a transparent supernatant layer. After removing the supernatant, the coagulated particle layer was isolated using filter paper. This was dispersed in 300 parts by weight of a mixed solvent of 70% by weight of methanol and 30% by weight of n-hexane. When this dispersion is allowed to stand for 3 hours, it is separated into a coagulated particle layer and a transparent supernatant layer. The coagulated particle layer was isolated using filter paper. Table 1 shows the results of confirming the removal of the organic polymer from the core-shell particles. The isolated filtered particles were dispersed in toluene to obtain a dispersion having a particle concentration of 1% by weight.

  This dispersion and a fluororesin for film formation (and acrylic resin) dissolved in the solvent shown in Table 1 at a concentration of 1% by weight were mixed, and hollow silicone-based particles and fluororesin (and acrylic resin) were mixed. ) Was adjusted as shown in Table 1. As the solvent, toluene or Flinate FC (manufactured by Sumitomo 3M, perfluoro (2-butyltetrahydrofuran)) was used. As the fluorine-based resin for film formation, 17FM (manufactured by Mitsubishi Rayon), TEFLON AF1600 (manufactured by DuPont), or CYTOP (manufactured by Asahi Glass) was used. As the acrylic resin, Hitaroid 1007 (manufactured by Hitachi Chemical) was used.

  This coating solution was applied to a PET film by a dip method, and then dried at 110 ° C. for 20 minutes to obtain a coated substrate with a coating thickness of 0.1 to 0.2 μm.

The reflectance of this coated substrate was measured to determine the minimum reflectance in the visible light region. In addition, Table 1 also shows the evaluation results of the total light transmittance, resistance to erase rubber, and adhesion of the substrate.
(Comparative Example 1)
Table 1 shows the evaluation results of the PET film not coated at all.

有機高分子粒子からなる粒子を、ＲＳｉＯ_4/2単位、ＲＳｉＯ_3/2単位およびＲ₂ＳｉＯ_2/2単位からなるシリコーン系化合物で被覆したコアシェル粒子中の有機高分子を除去した体積平均粒子径０．００１〜１μｍの中空シリコーン系微粒子と被膜形成用フッ素系樹脂を含む被膜を持つ実施例１〜４のＰＥＴフィルムは、比較例１〜３のＰＥＴフィルムよりも低い反射率を示した。また、実施例１〜４のＰＥＴフィルムは、比較例２のＰＥＴフィルムよりも高い密着性、膜強度を示した。

Volume average particle diameter obtained by removing organic polymer from core-shell particles in which organic polymer particles are coated with a silicone compound comprising RSiO _4/2 units, RSiO _3/2 units and R ₂ SiO _2/2 units. The PET films of Examples 1 to 4 having a coating containing 0.001 to 1 μm hollow silicone fine particles and a fluororesin for forming a film showed a lower reflectance than the PET films of Comparative Examples 1 to 3. In addition, the PET films of Examples 1 to 4 showed higher adhesion and film strength than the PET film of Comparative Example 2.

Claims (5)

The manufacturing method of the base material with a film which consists of following process (a)-process (c).
(A) Particles composed of organic polymer particles (A) and / or organic solvent (B) are _converted into SiO _4/2 units, RSiO _3/2 units (wherein R is an alkyl group having 1 to 4 carbon atoms, An aromatic group having 6 to 24 carbon atoms, a vinyl group, a γ- (meth) acryloxypropyl group, or an organic group having an SH group) and an R ₂ SiO _2/2 unit (wherein R is Or an organic group having 1 to 4 carbon atoms, an aromatic group having 6 to 24 carbon atoms, a vinyl group, a γ- (meth) acryloxypropyl group, or an SH group). Covered with a silicone compound (C) consisting of one unit or two or more units selected, wherein the proportion of R ₂ SiO _2/2 units is 20 mol% or less and the proportion of RSiO _3/2 units is 50 mol% or more. And (b) core-shell process for producing core-shell particles (D) A step of producing hollow silicone fine particles (E) having a volume average particle diameter of 0.001 to 1 μm by removing particles comprising organic polymer particles (A) and / or organic solvent (B) in the child (D) ( c) A step of forming the coating (G) containing the hollow silicone fine particles (E) and the fluororesin (F) for forming a film, alone or together with other coatings on the surface of the substrate.   The weight ratio of the total amount of the organic polymer particles (A) and / or the organic solvent (B) to the silicone compound (C) is 2/98 to 95/5. The manufacturing method of the base material with a film of 1 description.   3. The coated film according to claim 1, wherein particles comprising the organic polymer particles (A) and / or the organic solvent (B) in the core-shell particles (D) are removed using an organic solvent. A method for producing a substrate. The outer periphery is SiO _4/2 unit, RSiO _3/2 unit (wherein R is an alkyl group having 1 to 4 carbon atoms, an aromatic group having 6 to 24 carbon atoms, a vinyl group, γ- (meth) acryloxy). And an R ₂ SiO _2/2 unit (wherein R is an alkyl group having 1 to 4 carbon atoms, an aromatic group having 6 to 24 carbon atoms), and an R ₂ SiO _2/2 unit (which represents at least one organic group having a propyl group or SH group) 1 unit or 2 units or more selected from the group consisting of vinyl group, γ- (meth) acryloxypropyl group or SH group), and a ratio of R ₂ SiO _2/2 units Of hollow silicone fine particles (E) having a volume average particle diameter of 0.001 to 1 μm and a fluorine for film formation, comprising a silicone compound (C) having a ratio of 20 mol% or less and an RSiO _3/2 unit ratio of 50 mol% or more. A coating (G) containing a resin (F) alone or Film-coated substrate having on a substrate surface with the coating.   The hollow silicone fine particles (E) are composed of organic polymer particles (A) and / or organic solvent (B) coated with the silicone compound (C) and the core-shell particles (D). 5. The coated substrate according to claim 4, wherein the substrate is a hollow silicone fine particle obtained by removing particles comprising (A) and / or an organic solvent (B).