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WO2016104763A1 - Film structuré à vides lié par action catalytique et procédé pour le fabriquer - Google Patents

Film structuré à vides lié par action catalytique et procédé pour le fabriquer Download PDF

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Publication number
WO2016104763A1
WO2016104763A1 PCT/JP2015/086363 JP2015086363W WO2016104763A1 WO 2016104763 A1 WO2016104763 A1 WO 2016104763A1 JP 2015086363 W JP2015086363 W JP 2015086363W WO 2016104763 A1 WO2016104763 A1 WO 2016104763A1
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Prior art keywords
void structure
structure film
silicon compound
film according
void
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Ceased
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PCT/JP2015/086363
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English (en)
Japanese (ja)
Inventor
大輔 服部
裕宗 春田
恒三 中村
一貴 宇和田
武本　博之
村上　奈穗
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Nitto Denko Corp
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Nitto Denko Corp
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Priority claimed from JP2015176205A external-priority patent/JP6599699B2/ja
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to CN201580071018.3A priority Critical patent/CN107108943B/zh
Priority to KR1020177018503A priority patent/KR102477732B1/ko
Priority to US15/539,946 priority patent/US11618807B2/en
Priority to EP15873331.1A priority patent/EP3246355B1/fr
Publication of WO2016104763A1 publication Critical patent/WO2016104763A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/24—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by surface fusion and bonding of particles to form voids, e.g. sintering
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum

Definitions

  • the present invention relates to a void structure film bonded through catalytic action and a method for producing the same.
  • porous structures there are many examples using various materials and manufacturing methods, and they are used in a wide range of products such as optical members such as low refractive index layers, heat insulating materials, sound absorbing materials, and regenerative medical base materials.
  • the porous structure has a definition expressed in a dispersed state, such as a closed cell structure in which single voids (holes) are dispersed and an open cell structure in which the closed cell structure is attached.
  • void size there are also definitions of void size and various porous structures.
  • the skeletal structure of the wet gel is frozen as it is without shrinkage.
  • a method for obtaining a dried gel body see, for example, Patent Document 1.
  • the dried gel body is divided into a xerogel obtained by gradually evaporating and removing the gel solvent under normal pressure, and an “air-like gel” having a low bulk density and a high porosity, that is, an airgel.
  • Non-patent Document 1 such as using a solvent having a boiling point higher than that of water and having a small surface tension, or mixing fine particle silica for the purpose of suppressing the occurrence of cracks during such high-temperature treatment.
  • an object of the present invention is, for example, to provide a void structure film that forms a porous structure with a high porosity while suppressing the occurrence of cracks and also has strength, and a method for producing the same.
  • the void structure film of the present invention is characterized in that one or a plurality of types of structural units forming a fine void structure are chemically bonded to each other through a catalytic action.
  • a porous void layer in which silicone microporous particles are chemically bonded directly or indirectly will be described.
  • the void structure film of the present invention which is a silicone porous body may be referred to as “silicone porous body of the present invention”.
  • the method for producing a porous silicone body of the present invention includes: Producing a liquid containing microporous particles of a silicon compound; Adding a catalyst for chemically bonding the fine pore particles of the silicon compound to the liquid; and, The method includes a bonding step of chemically bonding the fine pore particles to each other by a catalytic action.
  • the void structure film of the present invention and the silicone porous body of the present invention are not limited to this production method, and may be produced by any production method.
  • the silicone porous body of the present invention uses the microporous particles of the silicon compound, and the microporous particles of the silicon compound are chemically bonded to each other through a catalytic action, whereby the porous structure is formed. Is fixed. Thereby, it is possible to provide a void structure film that forms a porous structure having a high porosity while suppressing the occurrence of cracks (cracks) and also has strength.
  • FIG. 1 is a process cross-sectional view schematically showing an example of a method for forming a porous silicone body 20 on a substrate 10 in the present invention.
  • FIG. 2 is a diagram schematically showing a part of steps in the method for producing a void structure film of the present invention and an example of an apparatus used therefor.
  • Drawing 3 is a figure showing typically a part of process in a manufacturing method of a void structure film of the present invention, and another example of an apparatus used therefor.
  • FIG. 4 is a cross-sectional SEM image of the silicone porous body of the example.
  • FIG. 5 is a TEM image of microporous particles in the silicone porous body of the example.
  • FIG. 6 is a process cross-sectional view schematically showing another example of a method for forming a porous silicone body on a substrate in the present invention.
  • FIG. 7 is a diagram schematically showing a part of steps in the method for producing a void structure film of the present invention and still another example of an apparatus used therefor.
  • FIG. 8 is a diagram schematically showing a part of steps in the method for producing a void structure film of the present invention and still another example of an apparatus used therefor.
  • FIG. 9 is a process cross-sectional view schematically showing still another example of a method for forming a porous silicone body on a substrate in the present invention.
  • FIG. 7 is a diagram schematically showing a part of steps in the method for producing a void structure film of the present invention and still another example of an apparatus used therefor.
  • FIG. 8 is a diagram schematically showing a part of steps in the method for producing a void structure film of the present invention and still another example of an apparatus used therefor.
  • FIG. 10 is a diagram schematically showing a part of steps in the method for producing a void structure film of the present invention and still another example of an apparatus used therefor.
  • FIG. 11 is a diagram schematically showing a part of steps in the method for producing a void structure film of the present invention and still another example of an apparatus used therefor.
  • the silicone porous body of the present invention is, for example, an open cell structure in which the porous structure is a continuous pore structure.
  • the catalyst is a catalyst that promotes cross-linking between silicon compound sols.
  • the bond between the structural units may include a hydrogen bond or a covalent bond.
  • the structural unit forming the void structure film of the present invention may be composed of, for example, a structure having at least one of a particle shape, a fiber shape, and a plate shape.
  • the particulate and flat structural units may be made of an inorganic substance, for example.
  • the constituent element of the particulate structural unit may include at least one element selected from the group consisting of Si, Mg, Al, Ti, Zn, and Zr, for example.
  • the structure (structural unit) that forms the particles may be a real particle or a hollow particle, and specifically includes silicone particles, silicone particles having fine pores, silica hollow nanoparticles, silica hollow nanoballoons, and the like.
  • the fibrous structural unit is, for example, a nanofiber having a diameter of nanometer, and specifically includes cellulose nanofiber and alumina nanofiber.
  • Examples of the plate-like structural unit include nanoclay, specifically, nano-sized bentonite (for example, Kunipia F [trade name]) and the like.
  • the fibrous structural unit is not particularly limited, but for example, from the group consisting of carbon nanofiber, cellulose nanofiber, alumina nanofiber, chitin nanofiber, chitosan nanofiber, polymer nanofiber, glass nanofiber, and silica nanofiber. It may be at least one fibrous material selected.
  • one type or plural types of structural units forming the fine void structure are chemically bonded, for example, directly or indirectly via a catalytic action. Contains parts. In the void structure film of the present invention, it suffices that at least a part of the one type or a plurality of types of structural units is chemically bonded via a catalytic action.
  • the structural units are “indirectly bonded” means that the structural units are bonded to each other through a small amount of a binder component equal to or less than the structural unit amount.
  • the structural units are “directly bonded” means that the structural units are directly bonded without using a binder component or the like.
  • the void structure film of the present invention will be described mainly with reference to the silicone porous body of the present invention.
  • the void structure film of the present invention is not limited to the silicone porous body.
  • the void structure film of the present invention forms a porous structure having a high porosity while suppressing the occurrence of cracks, as described above, even if it is other than the silicone porous body, and has a high strength. There is an effect of combining.
  • the silicone porous body of the present invention includes fine pore particles of a silicon compound, and the fine pore particles of the silicon compound are chemically bonded to each other through a catalytic action.
  • the shape of the “particles” is not particularly limited, and may be, for example, spherical or non-spherical.
  • the silicone porous body of the present invention has a three-dimensional structure formed by chemically bonding (for example, crosslinking) the fine pore particles of the silicon compound through catalytic action.
  • the silicone porous body of the present invention has a structure having voids, but it is also possible to maintain sufficient strength and sufficient flexibility to suppress the occurrence of cracks. Therefore, the silicone porous body of the present invention can be used for various members, for example, as a porous film body.
  • the silicone porous body of the present invention can be used as, for example, an optical member such as a low refractive index layer, a heat insulating material, a sound absorbing material, a regenerative medical base material, a dew condensation preventing material, an ink image receiving material, and the like.
  • the silicone porous body of the present invention is particularly preferably xerogel, although it varies depending on, for example, the application and purpose. Conventionally, xerogel has excellent strength but low porosity, while airgel has high porosity but low strength. On the other hand, the silicone porous body of the present invention has high porosity and strength.
  • the porous silicone of the present invention can realize a high porosity even if it is a xerogel, for example, like an airgel.
  • the fine pore particles of the silicon compound are preferably a pulverized product of a gel silicon compound.
  • the pulverized product of the gel-like silicon compound forms a new three-dimensional structure different from that of the uncrushed gel-like silicon compound, and a chemical bond (for example, cross-linking) between the pulverized products.
  • the silicone porous body of the present invention can exhibit physical properties (for example, the above-mentioned sufficient strength, sufficient flexibility, etc.) different from those of the uncrushed gel-like silicon compound.
  • the fine pore particles of the silicon compound may be, for example, sol-gel bead-like particles, nanoparticles (hollow nanosilica / nanoballoon particles), nanofibers, or the like.
  • the porous silicon body of the present invention includes fine pore particles of the silicon compound (preferably a pulverized product of a gel-like silicon compound), and the fine pore particles of the silicon compound are chemically reacted with each other through a catalytic action. Is bound to.
  • the form of chemical bonding (chemical bonding) between the microporous particles of the silicon compound is not particularly limited, and specific examples of the chemical bonding include, for example, cross-linking. .
  • the method for chemically bonding the fine pore particles of the silicon compound will be described in detail in the production method of the present invention.
  • the cross-linking is, for example, a siloxane bond.
  • the chemical bond of the present invention is not limited to a siloxane structure.
  • the siloxane bond include T2 bond, T3 bond, and T4 bond shown below.
  • the silicone porous body of the present invention may have any one kind of bond, may have any two kinds of bonds, or may have all three kinds of bonds. May be.
  • the siloxane bonds the greater the ratio of T2 and T3, the more flexible and the expected properties of the gel can be expected, but the strength becomes weaker.
  • the T4 ratio in the siloxane bond is large, the strength is easily developed, but the void size becomes small and the flexibility becomes brittle. For this reason, for example, it is preferable to change the ratio of T2, T3, and T4 according to the application.
  • the silicon atoms contained are preferably bonded with siloxane bonds.
  • the proportion of unbonded silicon atoms (that is, residual silanol) in the total silicon atoms contained in the porous silicone material is, for example, less than 50%, 30% or less, or 15% or less.
  • the fine pore particles of the silicon compound are not particularly limited, but are preferably a pulverized product of a gel-like silicon compound as described above.
  • the gel form of the gel silicon compound is not particularly limited. “Gel” generally refers to a solidified state in which a solute has a structure in which it loses independent motility due to interaction and aggregates.
  • a wet gel includes a dispersion medium and a solute has a uniform structure in the dispersion medium.
  • a xerogel is a network structure in which the solvent is removed and the solute has voids.
  • wet gel is preferably used as the gel silicon compound.
  • the void structure film of the present invention (typically, the silicone porous body of the present invention, hereinafter the same) has, for example, a pore structure, and the pore size of the pore is determined by the diameter of the major axis of the void (pore) and the short axis. Among the diameters of the shafts, the diameter of the major axis is indicated. A preferable pore size is, for example, 5 nm to 10 cm.
  • the lower limit of the void size is, for example, 5 nm or more, 10 nm or more, 20 nm or more
  • the upper limit thereof is, for example, 10 cm or less, 1 mm or less, 1 ⁇ m or less, and the range thereof is, for example, 5 nm to 10 cm, 10 nm. 1 mm, 20 nm to 1 ⁇ m.
  • a preferable void size is determined depending on the use of the void structure, it is necessary to adjust the void size to a desired void size according to the purpose, for example.
  • gap structure film of this invention is as having shown in FIG. 4 (cross-sectional SEM image) in the below-mentioned Example, for example.
  • FIG. 4 is an example and does not limit the present invention.
  • the void size can be evaluated by, for example, the following method.
  • the form of the void structure film can be observed and analyzed using an SEM (scanning electron microscope).
  • SEM scanning electron microscope
  • a silanol porous body sample formed on a resin film is subjected to FIB processing (acceleration voltage: 30 kV) under cooling, and the obtained cross-sectional sample is FIB-SEM (manufactured by FEI: trade name Helios NanoLab600).
  • Acceleration voltage: 1 kV Acceleration voltage: 1 kV
  • a cross-sectional electron image can be obtained at an observation magnification of 100,000.
  • the void size can be quantified by a BET test method. Specifically, 0.1 g of a sample (the void structure film of the present invention) was put into a capillary of a specific surface area measuring apparatus (trade name: ASAP2020, manufactured by Micromeritic), and then dried under reduced pressure at room temperature for 24 hours. The gas in the void structure is degassed. The adsorption isotherm is drawn by adsorbing nitrogen gas to the sample, and the pore distribution is obtained. Thereby, the gap size can be evaluated.
  • a specific surface area measuring apparatus trade name: ASAP2020, manufactured by Micromeritic
  • the void structure film of the present invention has a scratch resistance of 60 to 100% by Bencott (registered trademark).
  • the scratch resistance means, for example, strength such as film strength. Since the present invention has such strength, for example, it is excellent in scratch resistance in various processes.
  • the present invention has, for example, scratch resistance in the production process when winding the product after forming the void structure film and handling the product film.
  • the void structure film of the present invention can increase the film strength while adjusting the film density, for example.
  • silanol of fine pore particles of a silicon compound preferably silica sol fine particles, more preferably silica sol fine particles obtained by pulverizing a gel-like silica compound
  • the group can be cross-linked to increase the bonding force between the microporous particles of the silicon compound.
  • the lower limit of the scratch resistance is, for example, 60% or more, 80% or more, 90% or more, and the upper limit thereof is, for example, 100% or less, 99% or less, 98% or less, and the range is For example, they are 60 to 100%, 80 to 99%, 90 to 98%.
  • the scratch resistance can be measured by, for example, the following method.
  • a void layer (a void structure film of the present invention) coated and formed on an acrylic film is sampled in a circular shape having a diameter of about 15 mm.
  • silicon is identified with fluorescent X-rays (manufactured by Shimadzu Corporation: ZSX Primus II), and the Si coating amount (Si 0 ) is measured.
  • the gap layer on the acrylic film is cut to 50 mm ⁇ 100 mm from the vicinity sampled, and fixed to a glass plate (thickness 3 mm), and then according to Bencott (registered trademark). Perform a sliding test.
  • the sliding condition is a weight of 100 g and 10 reciprocations.
  • the residual amount of Si (Si 1 ) after the scratch test is measured by sampling and fluorescent X measurement in the same manner as in (1) above from the gap layer after sliding.
  • the void structure film of the present invention has a folding endurance of 100 or more by the MIT test.
  • the folding resistance number indicates, for example, flexibility, and the flexibility means, for example, the ease of deformation of a substance. Since the present invention has such flexibility, for example, the occurrence of cracks as described above is suppressed, and for example, it is excellent in handleability during winding or use during production.
  • the lower limit of the folding endurance number is, for example, 100 times or more, 500 times or more, 1000 times or more, and the upper limit is not particularly limited, for example, 10,000 times or less, and the range is, for example, 100 10000 times, 500 times to 10000 times, 1000 times to 10000 times.
  • the folding endurance by the MIT test can be measured by the following method, for example.
  • the void layer (the void structure film of the present invention) is cut into a strip of 20 mm ⁇ 80 mm, and then attached to an MIT folding resistance tester (manufactured by Tester Sangyo Co., Ltd .: BE-202), and a load of 1.0 N is applied.
  • the chuck part that embeds the gap layer uses R 2.0 mm, performs the folding endurance up to 10,000 times, and sets the number of times when the gap layer is broken as the number of folding endurances.
  • the film density is not particularly limited, and the lower limit thereof is, for example, 1 g / cm 3 or more, 10 g / cm 3 or more, 15 g / cm 3 or more, and the upper limit thereof is, for example, 50 g. / Cm 3 or less, 40 g / cm 3 or less, 30 g / cm 3 or less, 2.1 g / cm 3 or less, and the range is, for example, 5 to 50 g / cm 3 , 10 to 40 g / cm 3 , 15 to 30 g / Cm 3 and 1 to 2.1 g / cm 3 .
  • the porosity based on the film density is not particularly limited, and the lower limit thereof is, for example, 40% or more, 50% or more, 70% or more, 85% or more,
  • the upper limit is, for example, 98% or less and 95% or less, and the range is, for example, 40 to 98%, 50 to 95%, 70 to 95%, or 85 to 95%.
  • the film density can be measured by the following method, for example, and the porosity can be calculated as follows based on the film density, for example.
  • the void structure film of the present invention may have, for example, a pore structure (porous structure) as described above, and may be, for example, an open cell structure in which the pore structure is continuous.
  • the open cell structure means, for example, that the pore structure is three-dimensionally connected in the void structure film, and can be said to be a state in which the internal voids of the pore structure are continuous.
  • the porous body has an open cell structure, it is possible to increase the porosity occupied in the void structure film.
  • a closed cell particle such as hollow silica is used, the open cell structure is formed. Can not.
  • the porous silicon body of the present invention has a three-dimensional tree in which the fine pore particles of the silicon compound (preferably silica sol fine particles, more preferably silica sol fine particles which are a pulverized product of a gel-like silicon compound forming a sol).
  • the dendritic particles settle and deposit in the coating film (sol coating film containing the silica sol fine particles) in the manufacturing process, so that an open cell structure is easily formed.
  • the void structure film of the present invention more preferably forms a monolith structure in which the open cell structure has a plurality of pore distributions.
  • the monolith structure refers to, for example, a structure in which nano-sized fine voids exist and a hierarchical structure that exists as an open cell structure in which the nano voids are aggregated.
  • a structure in which nano-sized fine voids exist and a hierarchical structure that exists as an open cell structure in which the nano voids are aggregated In the case of forming the monolith structure, for example, while providing strength with fine voids, high porosity can be imparted with coarse open-cell voids, and both strength and high porosity can be achieved.
  • the haze indicating transparency is not particularly limited, and the lower limit is, for example, 0.1% or more, 0.2% or more, 0.3% or more, and the upper limit is For example, it is 30% or less, 10% or less, 3% or less, and the range is, for example, 0.1 to 30%, 0.2 to 10%, or 0.3 to 3%.
  • the haze can be measured by, for example, the following method.
  • the void layer (the void structure film of the present invention) is cut into a size of 50 mm ⁇ 50 mm, and set in a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd .: HM-150) to measure haze.
  • the refractive index is generally the ratio of the transmission speed of the wavefront of light in a vacuum to the propagation speed in the medium is called the refractive index of the medium.
  • the refractive index of the void structure film of the present invention is not particularly limited, and the upper limit thereof is, for example, 1.25 or less, 1.20 or less, 1.15 or less, and the lower limit thereof is, for example, 1.05 or more,
  • the range is 1.06 or more and 1.07 or more, and the range is, for example, 1.05 or more and 1.25 or less, 1.06 or more and 1.20 or less, and 1.07 or more and 1.15 or less.
  • the refractive index means a refractive index measured at a wavelength of 550 nm unless otherwise specified.
  • the measuring method of a refractive index is not specifically limited, For example, it can measure with the following method.
  • a void layer (the void structure film of the present invention) on the acrylic film, it is cut into a size of 50 mm ⁇ 50 mm, and this is bonded to the surface of a glass plate (thickness: 3 mm) with an adhesive layer.
  • the back surface central part (diameter of about 20 mm) of the glass plate is painted with black magic to prepare a sample that does not reflect on the back surface of the glass plate.
  • the sample is set in an ellipsometer (manufactured by JA Woollam Japan: VASE), the refractive index is measured under the conditions of a wavelength of 500 nm and an incident angle of 50 to 80 degrees, and the average value is taken as the refractive index.
  • the thickness of the void structure film of the present invention is not particularly limited, and the lower limit thereof is, for example, 1 nm or more, 10 nm or more, 50 nm or more, 100 nm or more, and the upper limit thereof is, for example, 1000 ⁇ m or less, 500 ⁇ m or less, 100 ⁇ m or less, The range is, for example, 1 nm to 1000 ⁇ m, 10 nm to 500 ⁇ m, 50 nm to 100 ⁇ m, 100 nm to 80 ⁇ m. In the case of a film body, it is adjusted depending on the application and required characteristics. For example, when emphasizing the transmittance, it is preferably 0.01 ⁇ m or more and 10 ⁇ m or less. For example, when emphasizing heat insulation, it is 100 ⁇ m. It is preferably 1 m or less.
  • Examples of the gelled silicon compound include gelled products obtained by gelling a monomeric silicon compound.
  • examples of the gel silicon compound include gelled products in which the monomer silicon compounds are bonded to each other, and specific examples include gelled products in which the monomer silicon compounds are bonded to each other through hydrogen bonding or intermolecular force bonding.
  • Examples of the bond include a bond by dehydration condensation. The gelation method will be described later in the production method of the present invention.
  • the silicon compound of the monomer is not particularly limited.
  • the silicon compound of the monomer include a compound represented by the following formula (1).
  • the gelled silicon compound is a gelled product in which monomeric silicon compounds are bonded to each other by hydrogen bonding or intermolecular force bonding as described above, the monomers of formula (1) are bonded to each other through, for example, each hydroxyl group. it can.
  • X is 2, 3 or 4
  • R 1 is a linear or branched alkyl group.
  • the carbon number of R 1 is, for example, 1-6, 1-4, 1-2.
  • Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • Examples of the branched alkyl group include an isopropyl group and an isobutyl group.
  • X is, for example, 3 or 4.
  • the silicon compound represented by the formula (1) include a compound represented by the following formula (1 ′) in which X is 3.
  • R 1 is the same as in the above formula (1), and is, for example, a methyl group.
  • the silicon compound is tris (hydroxy) methylsilane.
  • X is 3, the silicon compound is, for example, a trifunctional silane having three functional groups.
  • silicon compound represented by the formula (1) examples include a compound in which X is 4.
  • the silicon compound is, for example, a tetrafunctional silane having four functional groups.
  • the silicon compound of the monomer may be, for example, a hydrolyzate of a silicon compound precursor.
  • the silicon compound precursor is not particularly limited as long as it can generate the silicon compound by hydrolysis, and specific examples thereof include a compound represented by the following formula (2).
  • R 1 and R 2 are each a linear or branched alkyl group, R 1 and R 2 may be the same or different, R 1 s may be the same as or different from each other when X is 2. R 2 may be the same as or different from each other.
  • X and R 1 are, for example, the same as X and R 1 in the formula (1).
  • R 2 is, for example, can be exemplified for R 1 is incorporated in the formula (1).
  • the silicon compound precursor represented by the formula (2) include compounds represented by the following formula (2 ′) in which X is 3.
  • R 1 and R 2 are the same as those in the formula (2), respectively.
  • the silicon compound precursor is trimethoxy (methyl) silane (hereinafter also referred to as “MTMS”).
  • the silicon compound of the monomer is not particularly limited, and can be appropriately selected according to the use of the silicone porous body of the present invention, for example.
  • the silicon compound of the monomer is preferably the trifunctional silane from the viewpoint of excellent low refractive index properties when, for example, low refractive index properties are important, and also has strength (for example, scratch resistance).
  • the tetrafunctional silane is preferable from the viewpoint of excellent scratch resistance.
  • the bifunctional silane is preferable from the viewpoint of excellent flexibility.
  • the silicon compound of the said monomer used as the raw material of the said gel-like silicon compound only 1 type may be used and 2 or more types may be used together, for example.
  • the silicon compound of the monomer for example, only the trifunctional silane may be included, only the tetrafunctional silane may be included, or both the trifunctional silane and the tetrafunctional silane may be included.
  • other silicon compounds may be included.
  • the ratio is not particularly limited and can be set as appropriate.
  • the volume average particle diameter showing the particle size variation of the fine pore particles of the silicon compound is not particularly limited, and the lower limit is, for example, 0 0.05 ⁇ m or more, 0.10 ⁇ m or more, or 0.20 ⁇ m or more, and the upper limit thereof is, for example, 2.00 ⁇ m or less, 1.50 ⁇ m or less, 1.00 ⁇ m or less, and the range thereof is, for example, 0.05 ⁇ m to 2 0.000 ⁇ m, 0.10 ⁇ m to 1.50 ⁇ m, and 0.20 ⁇ m to 1.00 ⁇ m.
  • the particle size distribution is determined by, for example, a particle size distribution evaluation apparatus such as a light centrifugal sedimentation method, a dynamic light scattering method, or a laser diffraction method, and an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Although it can be measured, it is not necessarily limited to these methods.
  • the fine pore particles of the silicon compound may be regular or irregular.
  • the silicon compound microporous particles preferably have a single or a plurality of micropores per particle.
  • a preferable form of the fine pore particles of the silicon compound is, for example, as shown in FIG. 5 (TEM image) in the examples described later.
  • FIG. 5 is merely an example and does not limit the present invention.
  • the TEM image of the fine pore particles of the silicon compound can be observed, for example, by the following method.
  • the morphology of the microporous particles of the silicon compound can be observed and analyzed using a TEM (transmission electron microscope). Specifically, a dispersion of the fine pore particles of the silicon compound is diluted to an appropriate concentration, and further dispersed and dried on a carbon support to obtain a fine pore particle sample. Then, an electronic image of the sample can be obtained with a TEM (manufactured by Hitachi, Ltd., trade name H-7650, acceleration voltage: 100 kV) at an observation magnification of 100,000.
  • TEM transmission electron microscope
  • the particle size distribution showing the particle size variation of the fine pore particles of the silicon compound is not particularly limited.
  • particles having a particle size of 0.4 ⁇ m to 1 ⁇ m are 50 to 99.9 wt% and 80 to 99.8 wt%. %, 90 to 99.7% by weight, or 0.1 to 50% by weight, 0.2 to 20% by weight, and 0.3 to 10% by weight of particles having a particle size of 1 to 2 ⁇ m.
  • the particle size distribution can be measured by, for example, a particle size distribution evaluation apparatus or an electron microscope.
  • the void structure film of the present invention may contain, for example, a catalyst for chemically bonding one type or plural types of structural units forming the fine void structure.
  • the content of the catalyst is not particularly limited, but is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight with respect to the weight of the structural unit.
  • the void structure film of the present invention may further contain, for example, a crosslinking aid for indirectly bonding one type or plural types of structural units forming the fine void structure.
  • the content of the crosslinking aid is not particularly limited, and is, for example, 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 10% by weight with respect to the weight of the structural unit. .
  • the form of the void structure film of the present invention is not particularly limited, and may be, for example, a film shape.
  • the manufacturing method of the void structure film of the present invention is not particularly limited, for example, it can be manufactured by the manufacturing method of the present invention shown below.
  • the manufacturing method of the void structure film of the present invention will be described mainly focusing on the manufacturing method of the silicone porous body of the present invention.
  • the method for producing a porous silicon body of the present invention includes a step of preparing a liquid containing microporous particles of a silicon compound, a step of adding a catalyst that chemically bonds the microporous particles to the liquid,
  • the liquid containing the microporous particles of the silicon compound is not particularly limited, for example, it is a suspension containing the microporous particles of the silicon compound.
  • the fine pore particles of the silicon compound are preferably a pulverized product of a gel-like silica compound.
  • pulverized product a case where the fine pore particles of the silicon compound are mainly a pulverized product of a gel-like silica compound (hereinafter sometimes simply referred to as “pulverized product”) will be described.
  • the method for producing a porous silicon body of the present invention can be similarly performed by using fine particles other than the pulverized product of the gel-like silica compound as the fine pore particles of the silicon compound.
  • a method of producing a porous silicone material from a solution other than a solution containing fine pore particles may be employed.
  • a dry film forming method such as aerosol deposition (AD method) is used to laminate a pulverized product on a substrate.
  • a porous body may be obtained.
  • the production method of the present invention it is possible to form a porous porous structure having a high porosity while suppressing the occurrence of cracks and having sufficient strength.
  • the reason is estimated as follows, for example, but the present invention is not limited to this estimation.
  • the pulverized product used in the production method of the present invention is obtained by pulverizing the gel silicon compound, the three-dimensional structure of the gel silicon compound before pulverization is dispersed in a three-dimensional basic structure. It has become. And in the manufacturing method of this invention, the said three-dimensional basic structure is deposited using the sol containing the ground material of the said gel-like silicon compound, and the porous structure based on the said three-dimensional basic structure is formed. That is, according to the production method of the present invention, a new porous structure formed from the pulverized product of the three-dimensional basic structure, which is different from the three-dimensional structure of the gel silicon compound, is formed.
  • the new three-dimensional structure is fixed in order to chemically bond the pulverized products.
  • the said silicone porous body obtained by the manufacturing method of this invention is a structure which has a space
  • the silicone porous body can be formed as an additional member for various objects.
  • the silicone porous body obtained by the present invention has a wide range of materials such as optical members such as a low refractive index layer, heat insulating materials, sound absorbing materials, regenerative medical base materials, anti-condensation materials, ink image receiving materials, etc. It can be used for products in the field, and can also be used to produce laminated films with various functions.
  • the production method of the present invention can be referred to the explanation of the silicone porous body of the present invention unless otherwise specified.
  • the present invention can be used for the production of any gel depending on, for example, the use and purpose, but is particularly effective for the production of a xerogel. Further, as described above, according to the silicone porous body of the present invention, for example, even a xerogel can achieve a high porosity as in the case of an airgel.
  • the description of the porous silicone material of the present invention can be used for the gel silicon compound and the pulverized product thereof, the silicon compound of the monomer and the silicon compound precursor.
  • the production method of the present invention includes a step of producing a liquid containing the fine pore particles of the silicon compound (preferably, a sol containing a pulverized product of the gel silicon compound).
  • the pulverized product is obtained, for example, by pulverizing the gel silicon compound.
  • the three-dimensional structure of the gel-like silicon compound is destroyed and dispersed into the three-dimensional basic structure as described above.
  • the gelation of the silicon compound can be performed, for example, by hydrogen bonding or intermolecular force bonding of the monomer silicon compounds.
  • Examples of the silicon compound of the monomer include the silicon compound represented by the formula (1) described in the porous silicone body of the present invention.
  • the monomers of the formula (1) can be hydrogen bonded or intermolecularly bonded via, for example, each hydroxyl group.
  • the silicon compound may be a hydrolyzate of the silicon compound precursor.
  • the silicon compound precursor represented by the formula (2) described in the silicone porous body of the invention may be used. It may be produced by hydrolysis.
  • the method for hydrolysis of the silicon compound precursor is not particularly limited, and can be performed, for example, by a chemical reaction in the presence of a catalyst.
  • the catalyst include acids such as oxalic acid and acetic acid.
  • an aqueous solution of oxalic acid is slowly dropped and mixed in a mixed solution (for example, suspension) of the silicon compound and dimethyl sulfoxide in a room temperature environment, and then stirred for about 30 minutes. Can be done.
  • a mixed solution for example, suspension
  • hydrolyzing the silicon compound precursor for example, by completely hydrolyzing the alkoxy group of the silicon compound precursor, further heating and immobilization after gelation / aging / void structure formation, It can be expressed efficiently.
  • the gelation of the silicon compound of the monomer can be performed, for example, by a dehydration condensation reaction between the monomers.
  • the dehydration condensation reaction is preferably performed, for example, in the presence of a catalyst.
  • the catalyst include acid catalysts such as hydrochloric acid, oxalic acid, and sulfuric acid, and ammonia, potassium hydroxide, sodium hydroxide, ammonium hydroxide, and the like.
  • a dehydration condensation catalyst such as a base catalyst.
  • the dehydration condensation catalyst is particularly preferably a base catalyst.
  • the amount of the catalyst added to the silicon compound of the monomer is not particularly limited, and the catalyst is, for example, 0.1 to 10 mol, 0.05 mol per 1 mol of the silicon compound of the monomer. -7 mol, 0.1-5 mol.
  • the gelation of the monomer silicon compound is preferably performed, for example, in a solvent.
  • the ratio of the silicon compound in the solvent is not particularly limited.
  • the solvent include dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc), dimethylformamide (DMF), ⁇ -butyllactone (GBL), acetonitrile (MeCN), ethylene Examples thereof include glycol ethyl ether (EGEE).
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • DMAc N, N-dimethylacetamide
  • DMF dimethylformamide
  • GBL ⁇ -butyllactone
  • MeCN acetonitrile
  • EGEE glycol ethyl ether
  • one type of solvent may be used, or two or more types may be used in combination.
  • the solvent used for the gelation is also referred to as “gelling solvent”.
  • the gelation conditions are not particularly limited.
  • the treatment temperature for the solvent containing the silicon compound is, for example, 20-30 ° C., 22-28 ° C., 24-26 ° C., and the treatment time is, for example, 1-60 minutes, 5-40 minutes, 10-30. Minutes.
  • the process conditions in particular are not restrict
  • the gel-like silicon compound obtained by the gelation is preferably subjected to an aging treatment after the gelation reaction.
  • the aging treatment for example, by further growing primary particles of a gel having a three-dimensional structure obtained by gelation, it is possible to increase the size of the particles themselves.
  • the contact state of the contacting neck portion can be increased from point contact to surface contact.
  • the gel subjected to the aging treatment as described above for example, increases the strength of the gel itself, and as a result, can improve the strength of the three-dimensional basic structure after pulverization.
  • the pore size of the void structure in which the three-dimensional basic structure is deposited can be prevented from shrinking due to solvent volatilization during the drying process.
  • the aging treatment can be performed, for example, by incubating the gel silicon compound at a predetermined temperature for a predetermined time.
  • the predetermined temperature is not particularly limited, and the lower limit thereof is, for example, 30 ° C or higher, 35 ° C or higher, 40 ° C or higher, and the upper limit thereof is, for example, 80 ° C or lower, 75 ° C or lower, 70 ° C or lower.
  • the range is, for example, 30 to 80 ° C., 35 to 75 ° C., 40 to 70 ° C.
  • the predetermined time is not particularly limited, and the lower limit thereof is, for example, 5 hours or more, 10 hours or more, 15 hours or more, and the upper limit thereof is, for example, 50 hours or less, 40 hours or less, 30 hours or less.
  • the range is, for example, 5 to 50 hours, 10 to 40 hours, 15 to 30 hours.
  • the optimum conditions for aging are mainly the conditions under which, for example, the increase in the silica primary particle size and the increase in the contact area of the neck portion can be obtained.
  • the same solvent as the gelation treatment can be used.
  • the aging treatment can be performed as it is on the reaction product after the gel treatment (that is, the solvent containing the gelled silicon).
  • the number of moles of residual silanol groups contained in the gel (the gel-like silicon compound) that has been subjected to the aging treatment after gelation is, for example, the number of moles of alkoxy groups in the added raw material (for example, the silicon compound precursor).
  • the upper limit is, for example, 50% or less, 40% or less, 30% or less
  • the lower limit is, for example, 1% or more, 3% or more, 5% or more
  • the range is, for example, 1 to 50%, 3 to 40%, and 5 to 30%.
  • the lower the number of moles of residual silanol groups For the purpose of increasing the hardness of the gel, for example, the lower the number of moles of residual silanol groups, the better. If the number of moles of silanol groups is too high, for example, there is a possibility that the void structure cannot be maintained before the precursor of the porous silicone material is crosslinked. On the other hand, if the number of moles of silanol groups is too low, for example, in the bonding step, the precursor of the silicone porous body cannot be crosslinked, and sufficient strength may not be imparted.
  • a silanol group for example, when a silicon compound as a monomer is modified with various reactive functional groups, the same phenomenon can be applied to each functional group.
  • the obtained gelled silicon compound is pulverized.
  • the gel-like silicon compound in the gelation solvent may be pulverized as it is, or after the gelation solvent is replaced with another solvent, the other solvent is used. You may grind
  • the other solvent is also referred to as a “grinding solvent”.
  • the solvent for grinding is not particularly limited, and for example, an organic solvent can be used.
  • the organic solvent include solvents having a boiling point of 130 ° C. or lower, a boiling point of 100 ° C. or lower, and a boiling point of 85 ° C. or lower. Specific examples include isopropyl alcohol (IPA), ethanol, methanol, butanol, propylene glycol monomethyl ether (PGME), methyl cellosolve, acetone, dimethylformamide (DMF) and the like.
  • the pulverizing solvent may be, for example, one type or a combination of two or more types.
  • the combination of the gelling solvent and the grinding solvent is not particularly limited, and examples thereof include a combination of DMSO and IPA, DMSO and ethanol, DMSO and methanol, and a combination of DMSO and butanol.
  • a more uniform coating film can be formed, for example, in coating film formation described below.
  • the method for crushing the gel silicon compound is not particularly limited, but it is preferable to use a high-pressure medialess crusher.
  • a high-pressure medialess crusher For example, an ultrasonic homogenizer, a high-speed rotation homogenizer, a high-pressure extrusion pulverization apparatus, a wet medialess pulverization apparatus using a cavitation phenomenon, or a pulverization apparatus that obliquely collides liquids with each other can be used.
  • a device for performing media grinding such as a ball mill physically destroys the void structure of the gel at the time of grinding
  • a cavitation type grinding device preferable for the present invention such as a homogenizer performs physical destruction of a medium by a medialess method.
  • the relatively weakly bonded silica sol particle bonding surface already contained in the gel three-dimensional structure is peeled off by high pressure and high speed shearing force.
  • the obtained sol three-dimensional structure can maintain a void structure having a particle size distribution in a certain range in the submicron region, for example, and can re-form the void structure by deposition during coating and drying.
  • the conditions for the pulverization are not particularly limited.
  • the gel can be pulverized without volatilizing the solvent by instantaneously applying a high-speed flow.
  • a pulverized product having a particle size variation as described above for example, a volume average particle size or a particle size distribution. If the amount of work such as pulverization time and strength is insufficient, for example, coarse particles may remain and not only fine pores cannot be formed, but also appearance defects may increase and high quality may not be obtained. . On the other hand, when the work amount is excessive, for example, the sol particles become finer than the desired particle size distribution, and the void size deposited after coating and drying becomes fine, which may not satisfy the desired porosity. .
  • a liquid for example, a suspension
  • a catalyst containing the fine pore particles and the catalyst is produced by adding a catalyst that chemically bonds the fine pore particles to each other. can do.
  • the amount of the catalyst to be added is not particularly limited, but is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0 with respect to the weight of the fine pore particles (crushed product of the gel-like silicon compound). 1 to 5% by weight.
  • the fine pore particles can be chemically bonded in a bonding step described later.
  • the catalyst may be, for example, a catalyst that promotes cross-linking between the microporous particles.
  • a chemical reaction for chemically bonding the fine pore particles it is preferable to use a dehydration condensation reaction of residual silanol groups contained in silica sol molecules. By promoting the reaction between the hydroxyl groups of the silanol group with the catalyst, it is possible to form a continuous film that cures the void structure in a short time.
  • the catalyst include a photoactive catalyst and a thermally active catalyst. According to the photoactive catalyst, for example, the fine pore particles can be chemically bonded (for example, crosslinked) without being heated. According to this, for example, since shrinkage due to heating hardly occurs, a higher porosity can be maintained.
  • a substance that generates a catalyst may be used.
  • the catalyst may be a crosslinking reaction accelerator
  • the catalyst generator may be a substance that generates the crosslinking reaction accelerator.
  • a substance that generates a catalyst by light photocatalyst generator
  • a substance that generates water thermal catalyst generator
  • the acid and the photocatalyst generator are not particularly limited.
  • a photobase generator (a catalyst that generates a basic catalyst by light irradiation), a photoacid generator (a substance that generates an acidic catalyst by light irradiation), etc.
  • a photobase agent is preferable.
  • the photobase generator include 9-anthrylmethyl N, N-diethylcarbamate (trade name WPBG-018), (E) -1- [3- (2- Hydroxyphenyl) -2-propenoyl] piperidine ((E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, trade name WPBG-027), 1- (anthraquinone-2-yl) ethyl imidazolecarboxy Rate (1- (anthraquinon-2-yl) ethyl imidazolecarboxylate, trade name WPBG-140), 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate (trade name WPBG-165
  • the trade names including “WPBG” are trade names of Wako Pure Chemical Industries, Ltd.
  • Examples of the photoacid generator include aromatic sulfonium salts (trade name SP-170: ADEKA), triarylsulfonium salts (trade name CPI101A: San Apro), and aromatic iodonium salts (trade name Irgacure 250: Ciba Japan).
  • the catalyst for chemically bonding the fine pore particles is not limited to the photoactive catalyst, and may be a thermally active catalyst such as urea.
  • the catalyst that chemically bonds the fine pore particles examples include a base catalyst such as potassium hydroxide, sodium hydroxide, and ammonium hydroxide, and an acid catalyst such as hydrochloric acid, acetic acid, and oxalic acid. Of these, base catalysts are preferred.
  • the catalyst for chemically bonding the fine pore particles is used, for example, by adding to the sol particle liquid (for example, suspension) containing the pulverized product (fine pore particles) immediately before coating, or the catalyst. Can be used as a mixed solution mixed with a solvent.
  • the mixed liquid may be, for example, a coating liquid that is directly added and dissolved in the sol particle liquid, a solution in which the catalyst is dissolved in a solvent, or a dispersion liquid in which the catalyst is dispersed in a solvent.
  • the solvent is not particularly limited, and examples thereof include various organic solvents, water, and a buffer solution.
  • the liquid that can form a void structure other than the fine pore particles may contain a catalyst that generates radicals by heating or light irradiation other than the acid or base, and is optimal depending on the structural unit of the void structure film.
  • a catalyst can be selected.
  • the fine pore particles of the silicon compound are a pulverized product of a gel silicon compound obtained from a silicon compound containing at least a trifunctional or lower saturated bond functional group
  • the fine pore particles of the silicon compound are included.
  • a cross-linking aid for indirectly bonding the fine pore particles of the silicon compound may be added after the liquid is produced or during the production process.
  • the cross-linking aid enters between the particles, and the particles and the cross-linking aid interact or bond with each other, so that it is possible to bond particles that are slightly apart from each other and efficiently increase the strength. It becomes possible.
  • the crosslinking aid a polycrosslinked silane monomer is preferable.
  • the multi-crosslinked silane monomer has, for example, an alkoxysilyl group having 2 or more and 3 or less, the chain length between alkoxysilyl groups may be 1 to 10 carbon atoms, and an element other than carbon May also be included.
  • crosslinking aid examples include bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (triethoxysilyl) propane, bis (Trimethoxysilyl) propane, bis (triethoxysilyl) butane, bis (trimethoxysilyl) butane, bis (triethoxysilyl) pentane, bis (trimethoxysilyl) pentane, bis (triethoxysilyl) hexane, bis (tri Methoxysilyl) hexane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) -N-butyl-N-propyl-ethane-1
  • the silicone porous body can be formed, for example, by forming a coating film using a liquid containing microporous particles of the silicon compound (preferably, a sol containing a pulverized product of the gel-like silicon compound).
  • the coating of the fine pore particles of the silicon compound can use, for example, various coating methods described later, but is not limited thereto.
  • membrane can be formed by coating the solvent containing the said ground material directly on the said base material.
  • bonding process mentioned later, can also be called the precursor film
  • a new three-dimensional structure is constructed by the sedimentation and deposition of the pulverized material in which the three-dimensional structure is destroyed.
  • the solvent (hereinafter also referred to as “coating solvent”) is not particularly limited, and for example, an organic solvent can be used.
  • the organic solvent include solvents having a boiling point of 130 ° C. or lower. Specific examples include, for example, IPA, ethanol, methanol, butanol and the like, and the same solvents as the grinding solvent can be used.
  • the present invention includes a step of pulverizing the gel-like silicon compound, in the coating film forming step, for example, the pulverizing solvent containing the pulverized product of the gel-like silicon compound may be used as it is. Good.
  • sol particle liquid fine pore particles of the sol-like silicon compound dispersed in the solvent
  • the sol particle liquid of the present invention can continuously form a void layer having a strength of a certain level or more by performing chemical crosslinking by a bonding process after coating and drying on a substrate, for example. is there.
  • the “sol” in the present invention refers to a state in which the silica sol particles having a nano three-dimensional structure retaining a part of the void structure are dispersed in a solvent and exhibit fluidity by pulverizing the three-dimensional structure of the gel. Say.
  • the concentration of the fine pore particles of the silicon compound in the solvent is not particularly limited, and is, for example, 0.3 to 80% (v / v), 0.5 to 40% (v / v), 1.0 to 10 % (V / v).
  • concentration of the pulverized product is too high, for example, the fluidity of the sol particle liquid is remarkably lowered, and there is a possibility that aggregates and coating streaks during coating are generated.
  • the concentration of the fine pore particles of the silicon compound is too low, for example, not only does it take a considerable time to dry the solvent of the sol particle liquid, but also the residual solvent immediately after the drying becomes high. The rate may fall.
  • the physical properties of the sol particle liquid are not particularly limited.
  • the shear viscosity of the sol particle liquid is, for example, a viscosity of 100 cPa ⁇ s or less, a viscosity of 10 cPa ⁇ s or less, and a viscosity of 1 cPa ⁇ s or less at a shear rate of 10001 / s. If the shear viscosity is too high, for example, coating streaks may occur, and problems such as a decrease in the transfer rate of gravure coating may be observed. On the other hand, when the shear viscosity is too low, for example, the wet coating thickness at the time of coating cannot be increased, and a desired thickness may not be obtained after drying.
  • the amount of the fine pore particles of the silicon compound applied to the substrate is not particularly limited, and can be appropriately set according to, for example, the desired thickness of the silicone porous body.
  • the amount of the pulverized material applied to the substrate is, for example, 0.01 to 60000 g per 1 m 2 of the substrate. 0.1 to 5000 g and 1 to 50 g.
  • the preferable coating amount of the sol particle liquid is, for example, related to the concentration of the liquid, the coating method, etc., and thus it is difficult to define it uniquely. Is preferred.
  • the coating film may be subjected to a drying treatment.
  • the drying treatment temperature of the present invention is characterized in that it can be treated from a relatively low temperature, and is suitable for short-time continuous production.
  • the drying treatment for example, not only the solvent (the solvent contained in the sol particle liquid) in the coating film is removed, but also the sol particles are settled and deposited to form a void structure during the drying treatment.
  • the purpose is that.
  • the drying treatment temperature is, for example, 50 to 200 ° C., 60 to 150 ° C., 70 to 130 ° C.
  • the drying treatment time is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, 0 .3-3 minutes.
  • the drying process temperature and time are preferably lower and shorter in relation to, for example, continuous productivity and high porosity. If the conditions are too strict, for example, when the substrate is a resin film, the substrate is extended in a drying furnace by being close to the glass transition temperature of the substrate, and formed immediately after coating. Defects such as cracks may occur in the void structure. On the other hand, if the conditions are too loose, for example, since the residual solvent is included at the time of leaving the drying furnace, there is a possibility that defects in appearance such as scratches will occur when rubbing with the roll in the next process. is there.
  • the drying treatment may be, for example, natural drying, heat drying, or vacuum drying.
  • the drying method is not particularly limited, and for example, a general heating means can be used.
  • the heating means include a hot air fan, a heating roll, and a far infrared heater.
  • heat drying when it is premised on industrial continuous production, it is preferable to use heat drying.
  • a solvent having a low surface tension is preferable for the purpose of suppressing the generation of shrinkage stress accompanying the solvent volatilization during drying and the cracking phenomenon of the void layer (the silicone porous body).
  • the solvent examples include, but are not limited to, lower alcohols typified by isopropyl alcohol (IPA), hexane, perfluorohexane, and the like.
  • IPA isopropyl alcohol
  • the drying treatment temperature and time can be changed depending on the thickness of the target silanol porous material and the solvent type.
  • the base material is not particularly limited, and a porous body that does not use a base material or a porous body formed on the base material can be made according to the configuration of the target silanol porous body.
  • thermoplastic resin base materials glass base materials, inorganic substrates typified by silicon, plastics molded from thermosetting resins, elements such as semiconductors, carbon fiber systems typified by carbon nanotubes Although materials etc. can be used preferably, it is not limited to these.
  • Examples of the form of the substrate include a film and a plate.
  • thermoplastic resin examples include polyethylene terephthalate (PET), acrylic, cellulose acetate propionate (CAP), cycloolefin polymer (COP), triacetate (TAC), polyethylene naphthalate (PEN), polyethylene (PE), and polypropylene.
  • PET polyethylene terephthalate
  • CAP cellulose acetate propionate
  • COP cycloolefin polymer
  • TAC triacetate
  • PEN polyethylene naphthalate
  • PE polyethylene
  • polypropylene examples include highly transparent base materials such as (PP).
  • the bonding step is a step of chemically bonding the microporous particles of the silicon compound contained in the coating film, and it is preferable to perform either wet processing or dry processing. it can.
  • the bonding step for example, the three-dimensional structure of the microporous particles of the silicon compound in the precursor of the porous body is fixed.
  • fixing by conventional sintering for example, high temperature treatment at 200 ° C. or higher induces dehydration condensation of silanol groups and formation of siloxane bonds.
  • various additives that catalyze the above dehydration condensation reaction for example, when the base material is a resin film, the base material is not damaged and is around 100 ° C.
  • the wet processing can be carried out at a relatively low hot air drying temperature and a short processing time of less than a few minutes. Further, after the drying step, ultraviolet irradiation may be performed, and a binding reaction may be performed by a short dry treatment by a photocatalytic reaction, and a void structure can be continuously formed and immobilized. Since wet processing causes a crosslinking reaction while forming the coating film, there is an advantage that it can be processed only by a hot air drying process, while a cross-linking reaction occurs in parallel while forming a void structure. There is a disadvantage that the formation of is inhibited. In addition, the same phenomenon can be assumed when a bonding reaction is caused by immersing the catalyst solution after forming the void structure once.
  • the dry process has an advantage that the formation of the high void structure is hardly hindered due to the two-stage reaction that causes the crosslinking reaction after the high void structure of the silanol precursor is formed. It is preferable to properly use wet processing and dry processing according to the purpose.
  • the method of chemically bonding is not particularly limited, and can be appropriately determined according to, for example, the type of the gel silicon compound.
  • the chemical bonding can be performed, for example, by chemical cross-linking between the microporous particles of the silicon compound, and in addition, for example, inorganic particles such as titanium oxide can be bonded to the silicon.
  • the inorganic particles and the fine pore particles of the silicon compound may be chemically crosslinked.
  • a biocatalyst such as an enzyme
  • a site other than the catalytic active site and the pulverized product may be chemically crosslinked.
  • the present invention can be applied to, for example, not only a void layer (silicone porous body) formed by the sol particles but also an organic-inorganic hybrid void layer, a host guest void layer, and the like, but is not limited thereto.
  • the bonding step can be performed, for example, by a chemical reaction in the presence of a catalyst according to the kind of fine pore particles of the silicon compound.
  • a chemical reaction in the present invention it is preferable to utilize a dehydration condensation reaction of residual silanol groups contained in silica sol molecules. By promoting the reaction between the hydroxyl groups of the silanol group with the catalyst, it is possible to form a continuous film that cures the void structure in a short time.
  • silicon monomer materials in which other reactive functional groups are organically modified can be used as a silica gel raw material, and the functional groups that react in the bonding step are not limited to silanol groups.
  • the catalyst examples include base catalysts such as potassium hydroxide, sodium hydroxide and ammonium hydroxide, and acid catalysts such as hydrochloric acid, acetic acid and oxalic acid, but are not limited thereto.
  • the catalyst for the dehydration condensation reaction is particularly preferably a base catalyst.
  • a photoacid generator catalyst, a photobase generator catalyst, a photoacid generator, a photobase generator, or the like that exhibits catalytic activity when irradiated with light (for example, ultraviolet rays) can also be preferably used.
  • the photoacid generator catalyst, photobase generator catalyst, photoacid generator, and photobase generator are not particularly limited, and are, for example, as described above.
  • the catalyst is preferably added to the sol particle liquid containing the pulverized material immediately before coating, or used as a mixed liquid in which the catalyst is mixed with a solvent.
  • the mixed liquid may be, for example, a coating liquid that is directly added and dissolved in the sol particle liquid, a solution in which the catalyst is dissolved in a solvent, or a dispersion liquid in which the catalyst is dispersed in a solvent.
  • the solvent is not particularly limited, and examples thereof include various organic solvents, water, and a buffer solution.
  • the chemical reaction in the presence of the catalyst is, for example, light irradiation or heating to the coating film containing the catalyst previously added to the sol particle liquid, or spraying the catalyst on the coating film.
  • the catalyst is a photoactive catalyst
  • the porous body can be formed by chemically bonding the microporous particles by light irradiation.
  • grains can be chemically combined by heating and the said porous body can be formed.
  • Light irradiation amount in the irradiation (energy) is not particularly limited, @ in 360nm terms, for example, 200 ⁇ 800mJ / cm 2, 250 ⁇ 600mJ / cm 2 or 300 ⁇ 400mJ / cm 2,. From the viewpoint of preventing the irradiation amount from being insufficient and the decomposition due to light absorption of the catalyst generator from proceeding and preventing the effect from becoming insufficient, an integrated light amount of 200 mJ / cm 2 or more is good. Further, from the viewpoint of preventing the base material under the void layer from being damaged and generating thermal wrinkles, an integrated light amount of 800 mJ / cm 2 or less is good.
  • the conditions for the heat treatment are not particularly limited, and the heating temperature is, for example, 50 to 250 ° C., 60 to 150 ° C., 70 to 130 ° C., and the heating time is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes and 0.3 to 3 minutes.
  • the solvent used for example, a solvent having a low surface tension is preferable for the purpose of suppressing the generation of shrinkage stress accompanying the solvent volatilization during drying and the cracking phenomenon of the void layer. Examples thereof include, but are not limited to, lower alcohols typified by isopropyl alcohol (IPA), hexane, perfluorohexane, and the like.
  • the void structure film of the present invention can be produced, but the production method of the present invention is not limited to this.
  • the obtained void structure film of the present invention may be subjected to a strength improving step (hereinafter, also referred to as “aging step”) in which the strength is improved by, for example, heat aging.
  • a strength improving step in which the strength is improved by, for example, heat aging.
  • the adhesive peel strength to the resin film can be improved by the strength improving step (aging step).
  • the temperature in the aging step is, for example, 40 to 80 ° C., 50 to 70 ° C., 55 to 65 ° C.
  • the reaction time is, for example, 5 to 30 hours, 7 to 25 hours, or 10 to 20 hours.
  • the adhesive peel strength can be improved while suppressing the shrinkage of the void structure film, and both high porosity and strength can be achieved.
  • the catalyst contained in the void structure film of the present invention causes chemical bonding (for example, cross-linking reaction) between the fine pore particles. It is considered that the strength is improved by proceeding further.
  • the microporous particles are microporous particles of a silicon compound (for example, a pulverized product of a gel-like silica compound), and the residual silanol groups (OH groups) are present in the silicone porous body, the residual It is considered that silanol groups are chemically bonded by a crosslinking reaction.
  • the catalyst contained in the void structure film of the present invention is not particularly limited.
  • the catalyst used in the bonding step may be used, or the photobase generating catalyst used in the bonding step may be generated by light irradiation.
  • the photoacid generating catalyst used in the binding step may be an acidic substance generated by light irradiation or the like.
  • this description is illustrative and does not limit the present invention.
  • an adhesive layer may be further formed on the void structure film of the present invention (adhesive layer forming step).
  • the adhesive layer may be formed by applying (coating) a pressure-sensitive adhesive or an adhesive onto the silicone porous body of the present invention.
  • the adhesive layer side such as an adhesive tape in which the adhesive layer is laminated on a base material is bonded onto the silicone porous body of the present invention, whereby the above-mentioned silicone porous body of the present invention is An adhesive layer may be formed.
  • the base material such as the adhesive tape may be left as it is or may be peeled off from the adhesive layer.
  • adheresive and “adhesive layer” refer to, for example, an agent or layer premised on re-peeling of the adherend.
  • adheresive and “adhesive layer” refer to, for example, an agent or a layer that does not assume re-peeling of the adherend.
  • pressure-sensitive adhesive and “adhesive” are not necessarily clearly distinguished, and “pressure-sensitive adhesive layer” and “adhesive layer” are not necessarily clearly distinguished.
  • the adhesive or adhesive which forms the said adhesive layer is not specifically limited, For example, a general adhesive or adhesive etc. can be used.
  • the pressure-sensitive adhesive or adhesive examples include acrylic-based, vinyl alcohol-based, silicone-based, polyester-based, polyurethane-based, and polyether-based adhesives, rubber-based adhesives, and the like.
  • the adhesive agent comprised from the water-soluble crosslinking agent of vinyl alcohol polymers, such as glutaraldehyde, melamine, and oxalic acid, etc. are mentioned. These pressure-sensitive adhesives and adhesives may be used alone or in combination (for example, mixing, lamination, etc.).
  • the thickness of the adhesive layer is not particularly limited, and is, for example, 0.1 to 100 ⁇ m, 5 to 50 ⁇ m, 10 to 30 ⁇ m, or 12 to 25 ⁇ m.
  • the void structure film of the present invention may be reacted with the adhesive layer to form an intermediate layer disposed between the void structure film of the present invention and the adhesive layer (intermediate layer). Forming step).
  • the intermediate layer makes it difficult for the void structure film of the present invention and the adhesive layer to peel off, for example.
  • the reason (mechanism) is unknown, but is presumed to be due to, for example, the throwing property (throwing effect) of the intermediate layer.
  • the anchoring property an anchoring effect
  • the reaction between the silicone porous body of the present invention and the adhesive layer is not particularly limited, but may be a reaction by catalytic action, for example.
  • the catalyst may be, for example, a catalyst contained in the porous silicone body of the present invention.
  • the catalyst used in the coupling step may be used
  • the photobase generation catalyst used in the coupling step is a basic substance generated by light irradiation
  • the photoacid generation catalyst used in the coupling step is light.
  • An acidic substance generated by irradiation may be used.
  • the reaction between the void structure film of the present invention and the adhesive layer may be, for example, a reaction in which a new chemical bond is generated (for example, a crosslinking reaction).
  • the reaction temperature is, for example, 40 to 80 ° C., 50 to 70 ° C., 55 to 65 ° C.
  • the reaction time is, for example, 5 to 30 hours, 7 to 25 hours, or 10 to 20 hours.
  • middle layer formation process may serve as the said intensity
  • the void structure film of the present invention thus obtained may be laminated with another film (layer), for example, to form a laminated structure including the porous structure.
  • each component in the laminated structure, may be laminated via, for example, a pressure-sensitive adhesive or an adhesive.
  • the lamination may be performed by continuous processing using a long film (so-called Roll to Roll, etc.). May be laminated with batch processing.
  • the void structure film of the present invention can be produced by the continuous treatment process even in cases other than the silicone porous body.
  • FIG. 2 after forming the said silicone porous body, although the process which bonds and winds up a protective film is shown, when laminating
  • the illustrated film forming method is merely an example, and the present invention is not limited thereto.
  • FIG. 1 is a cross-sectional view schematically showing an example of steps in the method for forming the silicone porous body on the substrate.
  • the method for forming the silicone porous body includes a coating step (1) of applying a sol particle liquid 20 ′′ of fine pore particles of a silicon compound on a substrate 10, and a sol particle liquid 20 ′′.
  • a chemical treatment step for example, a crosslinking treatment step
  • the porous silicone body 20 can be formed on the substrate 10 as shown.
  • the method for forming a porous silicone body may or may not include steps other than the steps (1) to (3) as appropriate.
  • the coating method of the sol particle liquid 20 '' is not particularly limited, and a general coating method can be adopted.
  • the coating method include a slot die method, a reverse gravure coating method, a micro gravure method (micro gravure coating method), a dip method (dip coating method), a spin coating method, a brush coating method, a roll coating method, and flexographic printing.
  • the extrusion coating method, the curtain coating method, the roll coating method, the micro gravure coating method and the like are preferable from the viewpoints of productivity, coating film smoothness, and the like.
  • the coating amount of the sol particle liquid 20 ′′ is not particularly limited, and can be appropriately set so that, for example, the thickness of the porous structure (silicone porous body) 20 is appropriate.
  • the thickness of the porous structure (silicone porous body) 20 is not particularly limited, and is as described above, for example.
  • the sol particle liquid 20 " is dried (that is, the dispersion medium contained in the sol particle liquid 20" is removed) to form a coating film (precursor layer) 20 '.
  • the conditions for the drying treatment are not particularly limited and are as described above.
  • the coating film 20 ′ containing the catalyst for example, a photoactive catalyst or a thermally active catalyst such as KOH
  • the catalyst for example, a photoactive catalyst or a thermally active catalyst such as KOH
  • the pulverized product in the film (precursor) 20 ′ is chemically bonded (for example, crosslinked) to form the porous silicone body 20.
  • the light irradiation or heating conditions in the chemical treatment step (3) are not particularly limited and are as described above.
  • FIG. 2 schematically shows an example of a coating apparatus using the slot die method and a method for forming the porous silicone material using the same.
  • FIG. 2 is a cross-sectional view, hatching is omitted for easy viewing.
  • each step in the method using this apparatus is performed while the substrate 10 is conveyed in one direction by a roller.
  • the conveyance speed is not particularly limited, and is, for example, 1 to 100 m / min, 3 to 50 m / min, or 5 to 30 m / min.
  • a coating process (1) for coating the base material 10 with the sol particle liquid 20 ′′ is performed on the coating roll 102 while the base material 10 is fed out and conveyed from the feed roller 101, and then the oven zone.
  • the process proceeds to the drying step (2).
  • a preliminary drying process is performed after a coating process (1) and prior to a drying process (2).
  • the preliminary drying step can be performed at room temperature without heating.
  • the heating means 111 is used.
  • the heating means 111 as described above, a hot air fan, a heating roll, a far infrared heater, or the like can be used as appropriate.
  • the drying step (2) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed.
  • the chemical treatment step (3) is performed in the chemical treatment zone 120.
  • the chemical treatment step (3) for example, when the dried coating film 20 ′ includes a photoactive catalyst, light irradiation is performed by lamps (light irradiation means) 121 disposed above and below the base material 10.
  • lamps (light irradiation means) 121 disposed above and below the base material 10.
  • a hot air fan 121 disposed above and below the substrate 10 using a hot air fan (heating means) instead of the lamp (light irradiation device) 121.
  • the pulverized material in the coating film 20 ′ is chemically bonded to each other, and the porous silicone body 20 is cured and strengthened.
  • an ultraviolet irradiator can also be preferably used in place of the hot air fan.
  • the laminated body in which the porous silicone body 20 is formed on the substrate 10 is wound up by the winding roll 105.
  • the porous silicone body 20 of the laminate is covered and protected with a protective sheet fed from the roll 106.
  • the protective sheet instead of the protective sheet, another layer formed of a long film may be laminated on the porous structure 20.
  • FIG. 3 schematically shows an example of a micro gravure method (micro gravure coating method) coating apparatus and a method for forming the porous structure using the same.
  • the hatch is abbreviate
  • each step in the method using this apparatus is performed while the substrate 10 is conveyed in one direction by a roller, as in FIG.
  • the conveyance speed is not particularly limited, and is, for example, 1 to 100 m / min, 3 to 50 m / min, or 5 to 30 m / min.
  • a coating step (1) for coating the base material 10 with the sol particle liquid 20 ′′ is performed while the base material 10 is fed out and conveyed from the feed roller 201.
  • the sol particle liquid 20 ′′ is applied by using a liquid reservoir 202, a doctor (doctor knife) 203, and a micro gravure 204 as shown in the figure.
  • the sol particle liquid 20 ′′ stored in the liquid reservoir 202 is attached to the surface of the microgravure 204, and further, the substrate 10 is controlled by the microgravure 204 while being controlled to a predetermined thickness by the doctor 203. Apply to the surface.
  • the microgravure 204 is merely an example, and the present invention is not limited to this, and any other coating means may be used.
  • a drying step (2) is performed. Specifically, as shown in the figure, the base material 10 coated with the sol particle liquid 20 ′′ is transported into the oven zone 210, heated by the heating means 211 in the oven zone 210, and dried.
  • the heating means 211 may be the same as that shown in FIG. Further, for example, by dividing the oven zone 210 into a plurality of sections, the drying step (2) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed.
  • the chemical treatment step (3) is performed in the chemical treatment zone 220.
  • the chemical treatment step (3) for example, when the dried coating film 20 ′ includes a photoactive catalyst, light irradiation is performed by lamps (light irradiation means) 221 disposed above and below the substrate 10.
  • lamps (light irradiation means) 221 disposed above and below the substrate 10.
  • a hot air fan (heating means) is used instead of the lamp (light irradiation device) 221 and is arranged below the base material 10 ( The substrate 10 is heated by the heating means 221.
  • the pulverized material in the coating film 20 ′ is chemically bonded to each other, and the porous silicone body 20 is formed.
  • the laminated body in which the silicone porous body 20 is formed on the substrate 10 is wound up by the winding roll 251. Thereafter, for example, another layer may be laminated on the laminate. Further, before the laminate is taken up by the take-up roll 251, for example, another layer may be laminated on the laminate.
  • FIGS. 6 to 8 show another example of the continuous treatment process in the method for forming a porous silicone body of the present invention.
  • this method is performed except that a chemical treatment step (for example, a crosslinking treatment step) (3) for forming the silicone porous body 20 is followed by a strength improving step (aging step) (4).
  • a chemical treatment step for example, a crosslinking treatment step (3) for forming the silicone porous body 20
  • a strength improving step (aging step) (4) Is the same as the method shown in FIGS.
  • the strength improving step (aging step) (4) the strength of the silicone porous body 20 is improved to obtain a silicone porous body 21 with improved strength.
  • the strength improving step (aging step) (4) is not particularly limited, and is as described above, for example.
  • FIG. 7 is a schematic view showing another example of the coating device of the slot die method and the method of forming the silicone porous body using the slot die method.
  • this coating apparatus has a strength improving zone (aging zone) 130 for performing a strength improving step (aging step) (4) immediately after the chemical processing zone 120 for performing the chemical processing step (3).
  • the strength improvement step (aging step) (4) is performed in the strength improvement zone (aging zone) 130 to improve the adhesive peel strength of the silicone porous body 20 to the resin film 10.
  • the porous silicone body 21 with improved adhesive peel strength is formed.
  • the strength improving step (aging step) (4) may be performed, for example, by heating the porous silicone body 20 as described above using the hot air fans (heating means) 131 disposed above and below the base material 10. .
  • heating temperature, time, etc. are not specifically limited, For example, it is as above-mentioned.
  • the laminated film in which the porous silicon body 21 is formed on the substrate 10 is wound up by the winding roll 105.
  • FIG. 8 is a schematic diagram showing another example of the coating apparatus of the micro gravure method (micro gravure coating method) and the method for forming the porous structure using the coating apparatus.
  • this coating apparatus has a strength improving zone (aging zone) 230 for performing a strength improving step (aging step) (4) immediately after the chemical processing zone 220 for performing chemical processing step (3).
  • the strength improvement step (aging step) (4) is performed in the strength improvement zone (aging zone) 230 to improve the adhesive peel strength of the porous silicone body 20 to the resin film 10.
  • the porous silicone body 21 with improved adhesive peel strength is formed.
  • the strength improving step (aging step) (4) may be performed, for example, by heating the porous silicone body 20 as described above using the hot air blowers (heating means) 231 disposed above and below the base material 10. . Although heating temperature, time, etc. are not specifically limited, For example, it is as above-mentioned. Thereafter, similarly to FIG. 3, the laminated film in which the silicone porous body 21 is formed on the substrate 10 is wound up by the winding roll 251.
  • FIGS. 9 to 11 show another example of the continuous treatment process in the method for forming a silicone porous body of the present invention.
  • this method applies the adhesive layer 30 on the silicone porous body 20 after the chemical treatment step (for example, the crosslinking treatment step) (3) for forming the silicone porous body 20.
  • An adhesive layer coating step adheresive layer forming step
  • an intermediate layer forming step (5) in which the porous silicone body 20 is reacted with the adhesive layer 30 to form the intermediate layer 22.
  • FIGS. 9 to 11 is the same as the method shown in FIGS. In FIG.
  • the intermediate layer forming step (5) also serves as a step for improving the strength of the porous silicone body 20 (strength improving step).
  • the silicone porous body 20 The porous silicon body 21 is improved in strength.
  • this invention is not limited to this,
  • the silicone porous body 20 does not need to change after an intermediate
  • the adhesive layer coating step (adhesive layer forming step) (4) and the intermediate layer forming step (5) are not particularly limited, and are as described above, for example.
  • FIG. 10 is a schematic view showing still another example of the coating apparatus of the slot die method and the method of forming the silicone porous body using the same.
  • this coating apparatus has an adhesive layer coating zone 130a for performing the adhesive layer coating step (4) immediately after the chemical processing zone 120 for performing the chemical processing step (3).
  • an intermediate layer forming zone (aging zone) 130 disposed immediately after the adhesive layer coating zone 130a is obtained by a hot air blower (heating means) 131 disposed above and below the base material 10, and the strength shown in FIG.
  • the same heat treatment as in the improvement zone (aging zone) 130 can be performed. That is, in the apparatus of FIG.
  • the pressure-sensitive adhesive or adhesive is applied on the porous silicone body 20 by the pressure-sensitive adhesive layer coating means 131a in the pressure-sensitive adhesive layer coating zone 130a.
  • An adhesive layer coating process (adhesive layer forming process) (4) for applying (coating) and forming the adhesive layer 30 is performed. Further, as described above, instead of application (coating) of the pressure-sensitive adhesive or adhesive, bonding (sticking) such as a pressure-sensitive adhesive tape having the adhesive layer 30 may be used. Further, an intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming zone (aging zone) 130 to react the silicone porous body 20 and the adhesive layer 30 to form the intermediate layer 22.
  • the silicone porous body 20 becomes the silicone porous body 21 with improved strength.
  • the heating temperature, time, etc. by the hot air fan (heating means) 131 are not specifically limited, For example, it is as above-mentioned.
  • FIG. 11 is a schematic view showing still another example of a micro gravure method (micro gravure coating method) coating apparatus and a method for forming the porous structure using the same.
  • this coating apparatus has an adhesive layer coating zone 230a for performing the adhesive layer coating step (4) immediately after the chemical processing zone 220 for performing the chemical processing step (3).
  • the intermediate layer forming zone (aging zone) 230 disposed immediately after the adhesive layer coating zone 230a is obtained from the strength shown in FIG.
  • the same heat treatment as that of the improvement zone (aging zone) 230 can be performed. That is, in the apparatus of FIG.
  • the pressure-sensitive adhesive or adhesive is applied on the silicone porous body 20 by the pressure-sensitive adhesive layer coating means 231a in the pressure-sensitive adhesive layer coating zone 230a.
  • An adhesive layer coating process (adhesive layer forming process) (4) for applying (coating) and forming the adhesive layer 30 is performed. Further, as described above, instead of application (coating) of the pressure-sensitive adhesive or adhesive, bonding (sticking) such as a pressure-sensitive adhesive tape having the adhesive layer 30 may be used.
  • an intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming zone (aging zone) 230, and the silicone porous body 20 and the adhesive layer 30 are reacted to form the intermediate layer 22. Further, as described above, in this step, the silicone porous body 20 becomes the silicone porous body 21 with improved strength.
  • the heating temperature, time, and the like by the hot air fan (heating means) 231 are not particularly limited, and are as described above, for example.
  • the void structure film of the present invention has the same function as an air layer. Therefore, it can be used for an object having the air layer instead of the air layer.
  • the present invention is characterized by including the void structure film of the present invention, and other configurations are not limited at all.
  • Examples of the present invention include an optical member such as a heat insulating material, a sound absorbing material, a dew condensation preventing material, a low refractive index layer, and the like characterized by including the void structure film.
  • these members of the present invention are transparent, they can be used, for example, by disposing them at a place where an air layer is required.
  • the form in particular of these members is not restrict
  • gap structure film is mentioned, for example.
  • the base material is, for example, a scaffold material.
  • the void structure film of the present invention has a porous structure that exhibits the same function as the air layer.
  • the void structure film of the present invention is useful as a scaffold for regenerative medicine because the void of the void structure film is suitable for holding cells, nutrient sources, air, and the like.
  • examples of the member including the void structure film of the present invention include a total reflection member, an ink image receiving material, a single layer AR (decrease reflection), a single layer moth eye, a dielectric constant material, and the like. .
  • Example 1 the void structure film (silicone porous body) of the present invention was produced as follows.
  • a homogenizer (trade name UH-50, manufactured by SMT Co., Ltd.) was used, and 1.18 g of gel and 1.14 g of IPA were weighed into a 5 cc screw bottle, and then for 2 minutes under conditions of 50 W and 20 kHz. It was performed by crushing.
  • the gelled silicon compound in the mixed solution was pulverized by the pulverization treatment, whereby the mixed solution became a sol particle solution of the pulverized product.
  • the volume average particle size indicating the particle size variation of the pulverized product contained in the mixed solution was confirmed with a dynamic light scattering nanotrack particle size analyzer (manufactured by Nikkiso Co., Ltd., UPA-EX150 type), 0.50 to It was 0.70.
  • a 0.3 wt% KOH aqueous solution was prepared, and 0.02 g of catalyst KOH was added to 0.5 g of the sol particle solution to prepare a coating solution.
  • the bar coating method is used to convert the coating liquid into polyethylene terephthalate (PET). It apply
  • PET polyethylene terephthalate
  • Example 1 A porous body was formed by the same method as in Example 1 except that the catalyst KOH was not added to the coating solution.
  • the obtained porous silicon body of Example 1 having a thickness of 1 ⁇ m has a porous structure with a high porosity, but it can be confirmed that it has sufficient strength and flexibility. It was. For this reason, it turned out that the silicone porous body of this invention is very useful as a silanol porous body which can make film
  • Example 2 the void structure film (silicone porous body) of the present invention was produced as follows.
  • Example 2 First, in the same manner as in Example 1, the “(1) Gelation of silicon compound” and “(2) Aging treatment” were performed. Next, instead of the 0.3 wt% KOH aqueous solution, an IPA (isopropyl alcohol) solution of 1.5 wt% photobase generating catalyst (Wako Pure Chemical Industries, Ltd .: trade name WPBG266) is used as the sol particle liquid. Except having added, it carried out similarly to Example 1 and performed the said (3) grinding
  • IPA isopropyl alcohol
  • Example 3 Except that heat aging was not performed after UV irradiation, the same operation as in Example 2 was performed to form the porous structure of this example.
  • Example 4 The same as in Example 2 except that after adding the IPA solution of the photobase generation catalyst, 0.018 g of 5 wt% bis (trimethoxy) silane was added to 0.75 g of the sol solution to prepare a coating solution. Thus, the porous structure of this example was formed.
  • Example 5 The porous structure of this example was formed by performing the same operation as in Example 2 except that the amount of the IPA solution of the photobase generation catalyst was 0.054 g with respect to 0.75 g of the sol solution. .
  • Example 6 In the same manner as in Example 2, after UV irradiation of the porous body after drying, before the heat aging, the pressure-sensitive adhesive side of the PET film coated with a pressure-sensitive adhesive (adhesive layer) on one side was changed to the porous surface. After affixing to the body at room temperature, it was heat-aged at 60 ° C. for 22 hours. Except this, the same operation as in Example 2 was performed to form the porous structure of this example.
  • Example 7 Except that heat aging was not performed after the PET film was pasted, the same operation as in Example 6 was performed to form the porous structure of this example.
  • Example 8 The same as in Example 6 except that after adding the IPA solution of the photobase generating catalyst, 0.018 g of 5% by weight of bis (trimethoxy) silane was added to 0.75 g of the sol solution to adjust the coating solution. Thus, the porous structure of this example was formed.
  • Example 9 The porous structure of this example was formed by performing the same operation as in Example 6 except that the amount of the IPA solution of the photobase generation catalyst was 0.054 g with respect to 0.75 g of the sol solution. .
  • Example 10 A porous structure of this example was formed by performing the same operation as in Example 6 except that MgF 2 and TEOS (tetraethoxysilane) were mixed in place of MTMS to form a porous structure.
  • MgF 2 and TEOS tetraethoxysilane
  • Tables 2 and 3 below show the results of measuring the refractive index and haze of the porous structures of Examples 2 to 10 by the methods described above.
  • each of the obtained porous silicon bodies of Examples 2 to 10 having a thickness of 1 ⁇ m has an extremely low refractive index of 1.14 to 1.18 and a haze value of 0.1. It had excellent optical properties of showing an extremely low value of 4. Note that such a very low refractive index means that the porosity is high. In addition, as shown in Tables 2 and 3, it was also confirmed that the porosity was high. Further, it was also confirmed that the porous silicone materials of Examples 2 to 10 had sufficient strength and flexibility as in Example 1. In Examples 2 to 10, since the change was not confirmed even after visual observation after the coating solution was stored for one week, the silicone porous body was excellent in storage stability of the coating solution and had a stable quality. It was also confirmed that can be manufactured efficiently.
  • the void structure film of the present invention one type or a plurality of types of structural units that form a fine void structure are chemically bonded through catalytic action.
  • the porous silicon body includes a pulverized product of the gel-like silicon compound to form a porous structure having voids, and the pulverized product is chemically bonded to each other by the porous structure.
  • the structure is fixed.
  • the void structure film of the present invention has a void structure, but can maintain sufficient strength and flexibility.
  • the void structure film of the present invention is useful in that it can provide a void structure that requires film strength and flexibility.
  • a member using a void it can be used for products in a wide range of fields such as an optical member such as a low refractive index layer, a heat insulating material, a sound absorbing material, and an ink image receiving material.
  • an optical member such as a low refractive index layer, a heat insulating material, a sound absorbing material, and an ink image receiving material.

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Abstract

La présente invention concerne, par exemple, un film structuré à vides dans lequel une structure poreuse dotée d'une porosité élevée est formée tout en prévenant la fissuration, et qui a une résistance élevée. Le film structuré à vides selon la présente invention se caractérise en ce qu'un ou plusieurs types de motifs structuraux pour former une structure à microvides sont chimiquement liés ensemble par une action catalytique. Le film structuré à vides selon la présente invention présente une résistance à l'excoriation de 60 à 100 % selon une mesure employant, par exemple, BEMCOT (marque déposée) et un nombre de résistance au pliage dans un test MIT de 100 ou plus. Le film structuré à vides peut être fabriqué par formation d'un précurseur d'un corps de silicone poreux en utilisant, par exemple, un sol contenant des morceaux broyés d'un composé de silicium de type gel, puis liaison chimique des morceaux broyés contenus dans le précurseur du corps de silicone poreux. Il est préférable que les morceaux broyés soient chimiquement liés ensemble, par exemple, par réticulation chimique.
PCT/JP2015/086363 2014-12-26 2015-12-25 Film structuré à vides lié par action catalytique et procédé pour le fabriquer Ceased WO2016104763A1 (fr)

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CN201580071018.3A CN107108943B (zh) 2014-12-26 2015-12-25 介由催化作用键合而成的空隙结构膜及其制造方法
KR1020177018503A KR102477732B1 (ko) 2014-12-26 2015-12-25 촉매 작용을 통하여 결합한 공극 구조 필름 및 그 제조 방법
US15/539,946 US11618807B2 (en) 2014-12-26 2015-12-25 Film with void spaces bonded through catalysis and method of producing the same
EP15873331.1A EP3246355B1 (fr) 2014-12-26 2015-12-25 Film structuré ayant des lacunes lié par action catalytique et procédé pour le fabriquer

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JP2014-266782 2014-12-26
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JP2015152966 2015-07-31
JP2015-176205 2015-09-07
JP2015176205A JP6599699B2 (ja) 2014-12-26 2015-09-07 触媒作用を介して結合した空隙構造フィルムおよびその製造方法

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JP2000119433A (ja) * 1998-10-20 2000-04-25 Matsushita Electric Ind Co Ltd 有機多孔体
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