TWI744241B - Laminated film, method of manufacturing laminated film, optical member, image display device, method of manufacturing optical member, and method of manufacturing image display device - Google Patents

Abstract

The object of the subject of the present invention is to provide a laminated film having a void layer that can have both high void ratio and film strength.

The solution of the present invention is a laminated film in which a void layer is laminated on a resin film, and is characterized in that it is manufactured by a manufacturing method including the following steps: a precursor formation step, which is formed on the aforementioned resin film The precursor of the void layer, that is, the void structure; and the cross-linking reaction step, after the precursor forming step, a cross-linking reaction is generated inside the precursor; the precursor includes a substance that generates an alkaline substance by light or heat; The basic substance is not generated in the precursor forming step; in the cross-linking reaction step, the basic substance is generated by light irradiation or heating, and the cross-linking reaction step has many stages.

Description

Laminated film, manufacturing method of laminated film, optical member, image display device, method of manufacturing optical member, and method of manufacturing image display device Technical field

The present invention relates to a laminated film, a method of manufacturing a laminated film, an optical member, an image display device, a method of manufacturing an optical member, and a method of manufacturing an image display device.

Background technique

If two substrates are arranged at a certain interval, the gap between the two substrates becomes an air layer. The air layer formed between the aforementioned substrates has a function of, for example, a low-refractive layer that totally reflects light. Therefore, for example, in the case of an optical film, by arranging members such as scallops, polarizing films, and polarizing plates at a certain distance, an air layer that becomes a low refractive index layer can be provided between the aforementioned members. However, in order to form the air layer in this way, each member must be arranged at a certain distance. Therefore, the members cannot be layered in sequence, which makes the manufacturing very labor-intensive. In addition, if combined optical members such as partitions (frames) are penetrated in order to maintain the air layer, the overall thickness becomes larger, which also runs counter to the requirements for thinness and weight reduction.

In order to solve this problem, some people try to develop members such as films showing low refraction to replace the air layer formed by the gaps between the members. For example, it has been proposed to modify the dispersion of inorganic compound particles on the surface An organic-inorganic composite film obtained by adding a radically polymerizable monomer and a catalyst and curing by light irradiation (Patent Document 1). In addition, for example, a method of improving scratch resistance by performing an alkali treatment after the formation of a silica aerogel film (void layer) has been proposed (Patent Document 2).

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2014-046518

Patent Document 2: Japanese Patent Application Publication No. 2009-258711

Summary of the invention

However, if the film strength is increased by a catalyst or the like at the same time as the formation of the void layer, there is a problem that the film strength is increased due to the progress of the catalyst reaction, but the porosity decreases. In addition, as described above, Patent Document 2 discloses that alkali treatment is performed after the formation of the void layer to improve the film strength. The aforementioned alkali treatment includes, for example, a method of applying an alkali solution or a method of contacting ammonia gas. However, in the method of coating the alkali solution, the void layer has low solvent resistance or due to the existence of voids and high water repellency, which easily affects the effect of the alkali solution reaching the interior of the void layer. On the other hand, in the method of contacting ammonia gas, there is a problem that the film strength enhancement treatment takes too long, and therefore the production efficiency is low.

Therefore, the object of the present invention is to provide a laminated film having a void layer with both high porosity and film strength, a method of manufacturing a laminated film, an optical member, an image display device, a method of manufacturing an optical member, and a method of manufacturing an image display device .

In order to achieve the foregoing object, the laminated film of the present invention has a void layer laminated on a resin film, and is characterized in that it is manufactured by a manufacturing method including the following steps: a precursor forming step is to form the voids on the resin film The layer precursor, that is, the void structure; and the cross-linking reaction step, after the precursor forming step, a cross-linking reaction is generated inside the precursor; the precursor includes cross-linking that can be generated to promote the cross-linking reaction The substance of the reaction promoter; the aforementioned substance generates the aforementioned cross-linking reaction promoter by light or heat; the aforementioned cross-linking reaction promoter is not produced in the aforementioned precursor forming step, and the aforementioned cross-linking reaction step is performed by light irradiation or heating The aforementioned cross-linking reaction accelerator is produced, and the aforementioned cross-linking reaction step has many stages.

The manufacturing method of the laminated film of the present invention, the laminated film is laminated with a void layer on the resin film, and the manufacturing method is characterized by comprising the following steps: a precursor forming step, which is to form the precursor of the void layer on the resin film The void structure; and the cross-linking reaction step, after the precursor forming step, a cross-linking reaction is generated inside the precursor; the precursor includes a substance that can generate a cross-linking reaction accelerator for promoting the cross-linking reaction: The aforementioned substance generates the aforementioned crosslinking reaction accelerator by light or heat; The aforementioned cross-linking reaction accelerator is not generated in the aforementioned precursor forming step; in the aforementioned cross-linking reaction step, the aforementioned cross-linking reaction accelerator is generated by light irradiation or heating, and the aforementioned cross-linking reaction step has many stages.

The optical member of the present invention includes the aforementioned laminated film of the present invention.

The image display device of the present invention includes the aforementioned optical member of the present invention.

The method of manufacturing an optical member of the present invention, the optical member including a laminate film, is characterized by including the step of manufacturing the foregoing laminate film by using the foregoing method of manufacturing the laminate film of the present invention.

The manufacturing method of the image display device of the present invention includes an optical member, and the manufacturing method is characterized by including the step of manufacturing the optical member using the manufacturing method of the optical member of the present invention.

According to the present invention, it is possible to provide a laminated film having a void layer with high porosity and film strength, a method of manufacturing a laminated film, an optical member, an image display device, a method of manufacturing an optical member, and a method of manufacturing an image display device. The laminated film of the present invention can be used for, for example, the optical member and image display device of the present invention, but it is not limited to this, and can also be used for any purpose.

10‧‧‧Substrate

20‧‧‧Precursor (precursor after cross-linking treatment)

20’‧‧‧Coating film (coating film after drying)

20"‧‧‧Sol particle liquid

21‧‧‧Void layer

101,201‧‧‧Send out roller

102‧‧‧Coating roller

105,241‧‧‧Reel roll

106‧‧‧roller

110,210‧‧‧Oven area

111,211‧‧‧Air heater (heating device)

120,220‧‧‧Chemical treatment area

121,221‧‧‧lamp (light irradiation device) or hot air device (heating device)

130,230‧‧‧Crosslinking reaction area (aging area)

131,231‧‧‧Air heater (heating device)

202‧‧‧Liquid Storage

203‧‧‧Scraper (scraper blade)

204‧‧‧Microgravure

1 is a cross-sectional view schematically showing an example of a method of forming a void layer 21 on a resin film 10 in the present invention.

2 is a schematic diagram showing a part of the manufacturing method of the laminated film of the present invention (hereinafter sometimes referred to as "the laminated film roll of the present invention") in the form of a roll, and A diagram of an example of the device used.

Fig. 3 is a diagram schematically showing a part of the steps in the method of manufacturing the laminated film roll of the present invention and another example of the device used therein.

The form used to implement the invention

Hereinafter, the present invention will be explained in more detail with examples. However, the present invention is not limited or restricted by the following description. As described above, the laminated film of the present invention may be the laminated film of the present invention in a roll (the laminated film roll of the present invention). The laminated film roll of the present invention can also be used as the laminated film of the present invention by cutting a part of it, for example. Hereinafter, when referred to as "the laminated film of the present invention", unless otherwise stated in advance, it also includes the laminated film roll of the present invention. Similarly, when referred to below as "the manufacturing method of the laminated film of the present invention", unless otherwise stated in advance, it also includes the manufacturing method of the laminated film roll of the present invention.

In the manufacturing method of the laminated film of the present invention, the crosslinking accelerator may contain, for example, an acidic substance or a basic substance. In this case, for example, the aforementioned acidic substance or basic substance is not generated in the aforementioned precursor forming step, and the aforementioned acidic substance or basic substance is generated by light irradiation or heating in the aforementioned crosslinking reaction step.

In the manufacturing method of the laminated film of the present invention, for example, in at least one stage after the second stage in the crosslinking reaction step, the precursor is heated to generate a crosslinking reaction in the precursor. In addition, in the present invention, the crosslinking reaction step has many stages as described above, and specifically, it may be two stages or three or more stages.

At least one after the second stage in the aforementioned cross-linking reaction step In the stage, for example, the strength of the aforementioned precursor can be further improved. In addition, in at least one stage after the second stage in the crosslinking reaction step, for example, the adhesion peel strength of the precursor to the resin film can be further improved.

In the manufacturing method of the laminated film of the present invention, as described above, the precursor includes a substance that generates an alkaline substance by light or heat, and in the precursor forming step, the alkaline substance is generated by light irradiation or heating. substance.

In the manufacturing method of the laminated film of the present invention, the aforementioned void layer may include, for example, a part chemically bonded directly or indirectly by one or more constituent units forming a fine void structure. In addition, for example, in the aforementioned void layer, even if the constituent units are in contact, there may be portions that are not chemically bonded. In addition, in the present invention, the "indirect bonding" of the structural unit means that the structural unit is bonded through a small amount of binder component less than the amount of the structural unit. The "direct bonding" of the building blocks refers to the direct bonding of the building blocks without the use of adhesive ingredients. The combination of the aforementioned structural units may be, for example, a combination through the action of a catalyst. The combination of the aforementioned structural units may include, for example, hydrogen bonding or covalent bonding. In the present invention, the structural unit forming the void layer may be formed of a structure having at least one of a particle shape, a fiber shape, and a plate shape, for example. The aforementioned particle-like and flat-plate-like constituent units can be formed of, for example, inorganic substances. In addition, the constituent element of the aforementioned particulate structural unit may include, for example, at least one element selected from the group consisting of Si, Mg, Al, Ti, Zn, and Zr. The particle-like structure (constituent unit) can be solid particles or hollow particles, specifically, polysiloxane particles or polysiloxane particles with micropores, Take hollow silicon dioxide nanoparticles or hollow silicon dioxide nanospheres as examples. The fibrous constituent unit is, for example, nanofibers with a diameter of nanometers. Specifically, cellulose nanofibers or alumina nanofibers can be cited as examples. For the flat-shaped structural unit, nano-clay can be cited as an example. Specifically, nano-size bentonite (for example, Kunipia F "trade name"), etc. can be cited as an example. The aforementioned fibrous constituent unit is not particularly limited, but for example, it may be selected from carbon nanofibers, cellulose nanofibers, alumina nanofibers, chitin nanofibers, chitin nanofibers, and polymer nanofibers. At least one fibrous substance in the group consisting of rice fiber, glass nanofiber and silica nanofiber. In addition, the aforementioned structural unit may be, for example, microporous particles. For example, the void layer is a porous body in which microporous particles are chemically bonded, and in the step of forming the void layer, for example, the microporous particles may be chemically bonded. In addition, in the present invention, the shape of the "particles" (for example, the aforementioned microporous particles, etc.) is not particularly limited. For example, it may be spherical or other shapes. In addition, in the present invention, the aforementioned microporous particles may be sol-gel beads, nanoparticles (hollow nanosilica, nanosphere particles), nanofibers, etc., as described above, for example. In the manufacturing method of the laminated film of the present invention, the aforementioned microporous particles are, for example, microporous particles of a silicon compound, and the aforementioned porous system polysiloxy porous body. The aforementioned microporous particles of the silicon compound include, for example, a crushed body of a gel-like silicon dioxide compound. In addition, another form of the aforementioned void layer includes a void layer formed of a fibrous substance such as nanofibers, and the aforementioned fibrous substance is entangled to form a layer in a form containing voids. The manufacturing method of such a void layer is not particularly limited, but for example, it may be the same as the void layer of the porous body in which the microporous particles are chemically bonded. Furthermore, as mentioned earlier, it also includes Contains a void layer using hollow nanoparticle or nano clay, and a void layer formed using hollow nanospheres or magnesium fluoride. In addition, the void layers may be void layers formed of a single constituent material, or void layers formed of a plurality of constituent materials. In addition, the shape of the void layer may be a single above-mentioned shape, or may be a void layer formed of a plurality of the above-mentioned shapes. Hereinafter, the void layer of the porous body in which the aforementioned microporous particles are chemically bonded is mainly explained.

In the manufacturing method of the laminated film of the present invention, for example, the aforementioned microporous particles are microporous particles of a silicon compound, and the aforementioned porous system polysiloxy porous body.

In the manufacturing method of the laminated film of the present invention, for example, the microporous particles of the aforementioned silicon compound include a crushed body of a gel-like silicon dioxide compound.

In the manufacturing method of the laminated film of the present invention, for example, the porous structure of the aforementioned porous body is a continuous cell structure with continuous pore structure.

The manufacturing method of the laminated film of the present invention further includes, for example, a step of preparing a liquid containing liquid containing the microporous particles; a step of applying the liquid containing liquid on the resin film; and drying the coated liquid In the drying step, and in the aforementioned crosslinking reaction step, the aforementioned microporous particles are chemically combined.

In the manufacturing method of the laminated film of the present invention, for example, in the aforementioned crosslinking reaction step, the aforementioned microporous particles are chemically combined by the action of a catalyst. For example, in the crosslinking reaction step, the crosslinking reaction accelerator generated by light irradiation or heating is the catalyst, and the microporous particles can be chemically combined by the action of the crosslinking reaction accelerator.

In the manufacturing method of the laminated film of the present invention, for example, in the crosslinking reaction step, the microporous particles are chemically combined by light irradiation.

In the manufacturing method of the laminated film of the present invention, for example, in the aforementioned crosslinking reaction step, the aforementioned microporous particles are chemically bonded by heating.

In the method of manufacturing the laminated film of the present invention, for example, the refractive index of the void layer is a value equal to or less than the refractive index of the precursor plus 0.1.

The manufacturing method of the laminated film of the present invention is, for example, by forming the aforementioned void layer so that the refractive index becomes 1.25 or less.

The manufacturing method of the laminated film of the present invention is, for example, to form the aforementioned void layer so that the void ratio becomes 40% by volume or more.

The manufacturing method of the laminated film of the present invention is, for example, to form the aforementioned void layer so as to have a thickness of 0.01 to 100 μm.

The manufacturing method of the laminated film of the present invention is, for example, to form the aforementioned void layer and make the haze value less than 5%.

The manufacturing method of the laminated film of the present invention is, for example, to form the void layer and make the adhesive peel strength of the void layer to the resin film to be 1N/25mm or more.

The manufacturing method of the laminated film of the present invention is, for example, that the resin film is a long resin film, and the precursor and the void layer are continuously formed on the resin film. In addition, the manufacturing method of the laminated film of the present invention can also cut out a part of the laminated film roll made as described above (the laminated film roll of the present invention) to form the laminated film of the present invention.

Although the manufacturing method of the laminated film roll of the present invention is not particularly limited, for example, it may be produced by the aforementioned laminated film roll of the present invention Method of manufacturing laminated film rolls. In addition, although the manufacturing method of the laminated film roll of this invention is not specifically limited, it may be a laminated film manufactured by the manufacturing method of the laminated film of this invention, for example.

Hereinafter, the present invention will be explained more specifically.

[1. Laminated film and its manufacturing method]

The manufacturing method of the laminated film of the present invention, as described above, includes: a precursor forming step, forming a void layer precursor, that is, a void structure, on the resin film; and a crosslinking reaction step, after the precursor forming step , A cross-linking reaction occurs inside the aforementioned precursor. In addition, the laminated film of the present invention is a laminated film produced by the aforementioned method of producing the laminated film of the present invention as described above. The laminated film of the present invention may be, for example, an elongated laminated film roll (the laminated film roll of the present invention).

[1-1. Laminated film]

In the laminated film of the present invention, the aforementioned resin film is not particularly limited. Examples of the aforementioned resin include: polyethylene terephthalate (PET), acrylic, cellulose acetate propionate (CAP), cycloolefin Thermoplastic resins with excellent transparency such as polymers (COP), triacetate (TAC), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), etc.

The laminated film roll of the present invention or the aforementioned void layer in the laminated film (hereinafter referred to as "the void layer of the present invention"), for example, may be directly laminated on the aforementioned resin film, or through other laminated layers.

The laminated film of the present invention may be, for example, a low-refractive material characterized by including the aforementioned void layer and the aforementioned resin film, the aforementioned void layer being laminated on the aforementioned resin film, and having the aforementioned characteristics.

The void layer of the present invention, such as BEMCOT (registered trademark) showing film strength, has a residual rate of 60 to 100% in the scratch resistance test. If it has such a film strength, for example, it is also very strong against physical impacts such as winding during manufacturing or use. The lower limit of the aforementioned scratch resistance is, for example, 60% or more, 80% or more, or 90% or more, and the upper limit is, for example, 100% or less, 99% or less, or 98% or less, and the range is, for example, 60 to 100%, 80 to 99%. , 90 to 98%.

The aforementioned scratch resistance can also be measured by the following method, for example.

(Evaluation of scratch resistance)

(1) The laminated film of the present invention is made into a circular sample with a diameter of 15 mm, and the gap layer is subjected to a BEMCOT (registered trademark) sliding test (scratch resistance test). The sliding condition is a load of 100g, reciprocating 10 times.

(2) Visually evaluate the scratch resistance of the aforementioned void layer after the scratch resistance test of (1) above. After the scratch resistance test, if the number of damages after the scratch resistance test is 0 to 9, it is evaluated as ○, if it is from 10 to 29, it is evaluated as △, and if it is 30 or more, it is evaluated as x.

In the void layer of the present invention, the film density is not particularly limited. The lower limit 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 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 . In addition, in the void layer of the present invention, based on the aforementioned film density, the lower limit of the porosity is, for example, 50% or more, 70% or more, or 85% or more, and the upper limit is, for example, 98% or less, 95% or less, and the range is For example, 50 to 98%, 70 to 95%, 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.

(Evaluation of film density and porosity)

After forming the void layer (the void layer of the present invention) on the substrate (acrylic film), the total reflection area of the foregoing void layer of the laminate was measured using an X-ray diffraction device (RINT-2000, manufactured by RIGAKU) The X-ray reflectivity. Next, after fitting intensity (Intensity) and 2θ, the film density (g/cm ³ ) is calculated from the critical angle of total reflection of the aforementioned laminate (void layer, base material), and then the porosity ( P%).

Porosity (P%)=45.48×film density (g/cm ³ )+100(%)

The void layer of the present invention, for example, has a hole structure. The gap size of the aforementioned hole refers to the aforementioned major axis diameter among the major axis diameter and minor axis diameter of the gap (hole). The pore size is not particularly limited, but is, for example, 2 nm to 500 nm. The lower limit of the aforementioned void size is, for example, 2nm or more, 5nm or more, 10nm or more, or 20nm or more, and the upper limit is, for example, 500nm or less, 200nm or less, or 100nm or less, and its range is, for example, 2nm to 500nm, 5nm to 500nm, 10nm to 200nm, 20nm To 100nm. The gap size can be determined according to the purpose of using the gap structure. Therefore, for example, it must be adjusted to the desired gap size according to the purpose. The void size can be evaluated by the following method, for example.

(Evaluation of void size)

In the present invention, the aforementioned void size can be legally quantified by the BET test. Specifically, 0.1 g of the sample (the void layer of the present invention) was put into the capillary tube of the specific surface area measuring device (manufactured by MICROMERITICS: ASAP2020) Then, dry under reduced pressure at room temperature for 24 hours to degas the gas in the void structure. Next, nitrogen is adsorbed on the aforementioned sample, thereby drawing an adsorption isotherm, and obtaining the pore distribution. From this, the void size can be evaluated.

The void layer of the present invention may have, for example, a pore structure (porous structure) as described above, or may be, for example, a continuous cell structure with continuous pore structure as described above. The aforementioned continuous cell structure means, for example, that the pore structure in the aforementioned polysilicate porous body is three-dimensionally connected, that is, the internal voids of the aforementioned pore structure are in a continuous state. When the porous body has a continuous-cell structure, although it may increase the porosity occupied in the whole, when using single-cell particles such as hollow silica, the continuous-cell structure cannot be formed. In contrast, when the void layer of the present invention uses silica sol particles (a crushed product of a gel-like silicon compound forming a sol), since the particles have a three-dimensional tree structure, the coating film (including the aforementioned gel-like In the coating film of the pulverized product of silicon compound, the aforementioned dendritic particles settle and accumulate, so that the continuous bubble structure can be easily formed. In addition, more preferably, the void layer of the present invention is suitable to form a monolithic structure with a continuous bubble structure with a large number of pores distributed. The aforementioned monolithic structure refers to, for example, a structure in which there are microscopic voids of nanometer size, and a hierarchical structure that forms a group of interconnected bubbles of the same nano-voids. When the monolithic structure is formed, for example, fine voids are used to impart strength to the film, and coarse continuous cell voids are used to impart high porosity, so that both membrane strength and high porosity can be achieved. In order to form these monolithic structures, for example, it is advisable to first control the pore distribution of the generated void structure in the gel (gel-like silicon compound) before crushing into the aforementioned silica sol particles. In addition, for example, when the aforementioned gel-like silicon compound is pulverized, the particle size distribution of the pulverized silica sol particles is controlled to a desired size, thereby forming the aforementioned monolith structure.

In the void layer of the present invention, the haze exhibiting transparency is not particularly limited, and the upper limit thereof is, for example, less than 5% or less than 3%. In addition, the lower limit thereof is, for example, 0.1% or more and 0.2% or more, and the range thereof is, for example, 0.1% or more and less than 5%, and 0.2% or more and less than 3%.

The aforementioned haze is measured, for example, by the following method.

(Evaluation of Haze)

The void layer (the void layer of the present invention) was cut into a size of 50 mm×50 mm, and set in a haze meter (manufactured by Murakami Color Technology Research Institute Co., Ltd.: HM-150) to measure the haze. The haze value is calculated by the following formula.

Haze (%)=[Diffuse transmittance (%)/Total light transmittance (%)]×100(%)

The aforementioned refractive index generally refers to the ratio of the propagation speed of the light wavefront in vacuum to the propagation speed in the medium as the refractive index of the medium. The upper limit of the refractive index of the void layer of the present invention is, for example, 1.25 or less, 1.20 or less, and 1.15 or less, and the lower limit is, for example, 1.05 or more, 1.06 or more, or 1.07 or more, and the range is, for example, 1.05 or more to 1.25 or less, 1.06 or more to 1.20 or less , 1.07 above to 1.15 below.

In the present invention, unless otherwise stated in advance, the aforementioned refractive index is the refractive index measured at a wavelength of 550 nm. In addition, the method of measuring the refractive index is not particularly limited, and it can be measured by the following method, for example.

(Evaluation of refractive index)

After forming the void layer (the void layer of the present invention) on the acrylic film, it was cut into a size of 50mm×50mm and pasted on the surface of the glass plate (thickness: 3mm) through the adhesive layer. Paint the back of the aforementioned glass plate with a black marker The central part (about 20mm in diameter) was prepared as a non-reflective sample on the back of the aforementioned glass plate. The aforementioned sample was set in an ellipsometer (manufactured by J.A. Woollam Japan: VASE), the refractive index was measured under the conditions of a wavelength of 500 nm and an incident angle of 50 to 80 degrees, and the average value thereof was used as the refractive index.

When the void layer of the present invention is formed on the aforementioned resin film, for example, the adhesive peel strength showing the adhesion to the aforementioned resin film is not particularly limited. The lower limit is, for example, 1N/25mm or more, 2N/25mm or more, 3N/25mm or more, And its upper limit is, for example, 30N/25mm or less, 20N/25mm or less, 10N/25mm or less, and its range is, for example, 1 to 30N/25mm, 2 to 20N/25mm, 3 to 10N/25mm.

The measurement method of the aforementioned adhesive peel strength is not particularly limited, and it can be measured by the following method, for example.

(Evaluation of Adhesive Peel Strength)

The laminated film of the present invention was made into a rectangular sample of 50 mm×140 mm, and the sample was fixed on a stainless steel plate with a double-sided tape. The acrylic adhesive layer (thickness 20μm) was pasted on the PET film (T100: manufactured by MITSUBISHI PLASTIC FILM), and then the adhesive tape cut into 25mm×100mm was pasted on the gap layer of the laminated film of the present invention, and Laminate of the aforementioned PET film. Next, the aforementioned sample was clamped on an automatic drawing tensile tester (manufactured by Shimadzu Corporation: AG-Xplus) so that the distance between the chucks was 100 mm, and the tensile test was performed at a tensile speed of 0.3 m/min. Take the average test force of the 50mm peel test as the adhesive peel strength.

The thickness of the void layer of the present invention is not particularly limited, and the lower limit is For example, 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, or 0.3 μm or more, and the upper limit thereof is, for example, 1000 μm or less, 100 μm or less, 80 μm or less, 50 μm or less, or 10 μm or less, and the range thereof is, for example, 0.01 to 1000 μm.

The void layer of the present invention contains, for example, the pulverized product of the gel-like compound as described above, and the pulverized product is chemically bonded. In the void layer of the present invention, the form of the chemical bond (chemical bond) of the pulverized product is not particularly limited, and specific examples of the chemical bond include cross-linked bonds. In addition, the method of chemically bonding the aforementioned pulverized product will be described in detail in the manufacturing method of the present invention.

The gel form of the aforementioned gel-like compound is not particularly limited. "Gel" generally means that the solute has a structure that is assembled and solidified due to the loss of independent mobility due to interaction. In addition, in gels, generally wet gels contain a dispersion medium and the solute in the dispersion medium has the same structure, while dry gels remove the solvent and the solute has a mesh structure with voids. In the present invention, the aforementioned gel-like compound may be, for example, a wet gel or a dry gel.

The aforementioned gel-like compound can be exemplified by a gelled product obtained by gelling a monomer compound. Specifically, the aforementioned gel-like silicon compound can be an example of a gel product in which the aforementioned monomeric silicon compounds are bonded to each other, and a specific example can be a gel product in which the aforementioned silicon compounds are hydrogen-bonded or intermolecularly bonded to each other as example. The aforementioned combination can be exemplified by the combination of dehydration and condensation. The aforementioned gelation method will be described later in the manufacturing method of the present invention.

In the void layer of the present invention, the volume average particle size showing the particle size deviation of the pulverized product is not particularly limited. The lower limit is, for example, 0.10 μm or more, 0.20 μm or more, or 0.40 μm or more, and the upper limit is, for example, 2.00 μm or less. Below, 1.50 μm or less, 1.00 μm or less, and the range thereof is, for example, 0.10 μm to 2.00 μm, 0.20 μm to 1.50 μm, 0.40 μm to 1.00 μm. The aforementioned particle size distribution can be measured by a particle size distribution evaluation device such as a dynamic light scattering method and a laser diffraction method, and an electron microscope such as a scanning electron microscope (SEM) and a transmission electron microscope (TEM).

In addition, the particle size distribution showing the particle size deviation of the aforementioned pulverized product is not particularly limited. For example, particles with a particle size of 0.4 μm to 1 μm are 50 to 99.9% by weight, 80 to 99.8% by weight, 90 to 99.7% by weight, or a particle size of 1 μm to 2 μm. The particles are 0.1 to 50% by weight, 0.2 to 20% by weight, and 0.3 to 10% by weight. The aforementioned particle size distribution can be measured by a particle size distribution evaluation device or an electron microscope.

In the void layer of the present invention, the type of the aforementioned gel-like compound is not particularly limited. The aforementioned gel-like compound can be exemplified by a gel-like silicon compound. Hereinafter, the case of the gel-like compound-based gel-like silicon compound will be described as an example, but the present invention is not limited to this.

The aforementioned crosslinking bond is, for example, a siloxane bond. The siloxane bond can be exemplified by the T2 bond, T3 bond, and T4 bond shown below. When the void layer of the present invention has a siloxane bond, for example, it may have any kind of bonds, any two kinds of bonds, or all three kinds of bonds. Among the aforementioned siloxane bonds, the greater the ratio of T2 and T3, the higher the flexibility. Therefore, the original characteristics of the gel can be expected, but the film strength is weak. On the other hand, if the ratio of T4 in the siloxane bond is high, the film strength is easily developed, but the void size becomes smaller, and therefore the flexibility becomes lower. Therefore, for example, it is advisable to change the ratio of T2, T3, and T4 according to the application.

[化1]

When the void layer of the present invention has the aforementioned siloxane bond, the ratio of T2, T3, and T4 is expressed relative to, for example, when T2 is "1", T2: T3: T4 = 1: [1 to 100]: [0 to 50], 1: [1 to 80]: [1 to 40], 1: [5 to 60]: [1 to 30].

In addition, in the void layer of the present invention, for example, the silicon atoms contained therein are preferably siloxane bonds. A specific example is that the ratio of unbound silicon atoms (ie, residual silanol) among all silicon atoms contained in the aforementioned void layer is, for example, less than 50%, 30% or less, or 15% or less.

When the aforementioned gel-like compound is the aforementioned gel-like silicon compound, the aforementioned monomeric silicon compound is not particularly limited. The silicon compound of the aforementioned monomer can be exemplified by the compound represented by the following formula (1). When the aforementioned gelled silicon compound is a gelled product in which the silicon compounds of the monomers are hydrogen-bonded to each other or intermolecular force-bonded as described above, the monomers of formula (1) can, for example, be hydrogen-bonded through their respective hydroxyl groups. .

In the aforementioned formula (1), for example, X is 2, 3, or 4, and R ¹ is a linear or branched alkyl group. The carbon number of the aforementioned R ¹ is, for example, 1 to 6, 1 to 4, or 1 to 2. Examples of the aforementioned linear alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.; examples of the aforementioned branched alkyl group include isopropyl and isobutyl. The aforementioned X series is 3 or 4, for example.

A specific example of the silicon compound represented by the aforementioned formula (1) can be a compound represented by the following formula (1') of the X series 3 as an example. In the following formula (1′), R ^{1 is the} same as the aforementioned formula (1), and is, for example, a methyl group. When R ¹ is a methyl group, the aforementioned silicon compound is tri(hydroxy)methylsilane. In the case of the aforementioned X-based 3, the aforementioned silicon compound is, for example, a trifunctional silane having a trifunctional group.

In addition, the specific example of the silicon compound represented by the aforementioned formula (1) can be a compound of X series 4 as an example. In this case, the aforementioned silicon compound is, for example, a 4-functional silane having a 4-functional group.

The silicon compound of the aforementioned monomer may be, for example, a hydrolyzate of a silicon compound precursor. The aforementioned silicon compound precursor may be, for example, as long as the aforementioned silicon compound can be produced by hydrolysis, and specific examples include compounds represented by the following formula (2).

[化4]

In the aforementioned formula (2), for example, X is 2, 3, or 4, R ¹ and R ² are linear or branched alkyl groups, respectively, and R ¹ and R ² are the same or different. When X is 2, R ¹ To be the same or different from each other, R ² are the same or different from each other.

The aforementioned X and R ^{1 are} , for example, the same as ^{X and R 1} in the aforementioned formula (1). In addition, for the aforementioned R ² , for example, the example of R ¹ in formula (1) can be cited.

As a specific example of the silicon compound precursor represented by the aforementioned formula (2), a compound represented by the following formula (2') of the X series 3 can be cited as an example. In the following formula (2'), R ¹ and R ² are the same as the aforementioned formula (2), respectively. When R ¹ and R ² are methyl groups, the aforementioned silicon compound precursor is trimethoxy(methyl)silane (hereinafter also referred to as "MTMS").

The aforementioned monomeric silicon compound is preferably the aforementioned trifunctional silane from the viewpoint of having excellent low refractive index. In addition, the aforementioned monomeric silicon compound is preferably the aforementioned tetrafunctional silane from the viewpoint of having excellent strength (for example, scratch resistance). In addition, as the aforementioned gel-like silicon compound For example, only one kind of the aforementioned monomeric silicon compound of the raw material may be used, or two or more kinds may be used in combination. A specific example is the silicon compound of the aforementioned monomer. For example, it can include only the aforementioned trifunctional silane, can only contain the aforementioned tetrafunctional silane, can contain both the aforementioned trifunctional silane and the aforementioned tetrafunctional silane, and can further contain other silicon compounds. When two or more types of silicon compounds are used for the aforementioned monomeric silicon compounds, the ratio is not limited and can be set appropriately.

In the laminated film of the present invention, the void layer may include, for example, a catalyst for chemically bonding one or more constituent units forming the fine void structure. The content of the aforementioned catalyst is not particularly limited, but can be, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight relative to the weight of the aforementioned structural unit.

In addition, in the laminated film of the present invention, the void layer may further include, for example, a crosslinking auxiliary agent for indirectly bonding one or more constituent units forming the fine void structure. The content of the aforementioned crosslinking adjuvant is not particularly limited, but can be, for example, 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 10% by weight relative to the weight of the aforementioned structural unit.

The shape of the void layer of the present invention is not particularly limited, but it is usually in the shape of a film.

The void layer of the present invention is, for example, a roll. In addition, the void layer of the present invention further includes a resin film as described above, and the void layer can be formed on the elongated resin film. In this case, another long film may be laminated on the laminated film of the present invention, or another long resin film (for example, insulating Paper, release paper, surface protection film, etc.), The form of rolls.

The manufacturing method of the laminated film of this invention is not specifically limited, For example, it can manufacture by the manufacturing method of this invention shown below.

[1-2. Manufacturing method of laminated film]

The manufacturing method of the laminated film of the present invention, as described above, includes the following steps: a precursor forming step, forming a void layer precursor, that is, a void structure, on the resin film; and a crosslinking reaction step, in the foregoing precursor forming step Then, a cross-linking reaction occurs inside the aforementioned precursor.

In the manufacturing method of the laminated film of the present invention, for example, as described above, the void layer is a porous body in which microporous particles are chemically bonded, and in the precursor forming step, the microporous particles are chemically bonded. The manufacturing method of the laminated film of the present invention, for example, as described above, further includes: a step of preparing a liquid containing liquid containing the aforementioned microporous particles; and a drying step of drying the containing liquid, and in the step of forming the precursor, The microporous particles in the dried body are chemically combined to form the porous body precursor. The containing liquid containing the aforementioned microporous particles (hereinafter, sometimes referred to as "microporous particle containing liquid" or simply "containing liquid") is not particularly limited, but may be, for example, a suspension containing the aforementioned microporous particles. In addition, the following mainly describes the case where the fine-pored particle-based gel-like compound is crushed, and the void layer is a porous body (preferably a polysilicate porous body) containing the crushed gel-like compound. However, when the aforementioned microporous particles of the present invention are other than the pulverized product of a gel-like compound, the same can be implemented.

According to the manufacturing method of the present invention, for example, an excellent display can be formed Low refractive index void layer. The reason is presumed as follows, for example, but the present invention is not limited to this presumption.

Since the pulverized product used in the manufacturing method of the present invention is obtained by pulverizing the gel-like silicon compound, the three-dimensional structure of the gel-like silicon compound before the pulverization is in a state of being dispersed into a three-dimensional basic structure. Furthermore, in the manufacturing method of the present invention, by coating the pulverized product of the gel-like silicon compound on the substrate, a porous structure precursor can be formed based on the three-dimensional basic structure. That is, according to the manufacturing method of the present invention, a new porous structure formed by the crushed product of the three-dimensional basic structure that is different from the three-dimensional structure of the gel-like silicon compound can be formed. Therefore, the aforementioned void layer produced finally, for example, can have a low refractive index with the same function as the air layer. In addition, in the manufacturing method of the present invention, since the pulverized product is further chemically combined, the new three-dimensional structure can be fixed. Therefore, the resulting void layer has a void structure, but can maintain sufficient strength and flexibility. In this way, the void layer produced by the manufacturing method of the present invention, for example, as a substitute for the aforementioned air layer, is useful in terms of the function of low refraction, and in terms of strength and flexibility. In addition, in the case of the aforementioned air layer, for example, it is necessary to form an air layer between the aforementioned members by inserting a partition or the like between the member and the member to provide a gap. However, the void layer produced by the manufacturing method of the present invention, for example, can exhibit low refraction with the same level of function as the aforementioned air layer by arranging it only at the target location. Therefore, as described above, it is easier and simpler than forming the air layer to provide, for example, the optical member with low refraction that has the same function as the air layer.

In addition, the present invention performs a precursor forming step of forming the void structure of the precursor of the void layer, and a crosslinking reaction step of generating a crosslinking reaction inside the precursor after the precursor forming step as another step. In addition, the aforementioned crosslinking reaction step is carried out in many stages. By carrying out the aforementioned cross-linking reaction step in multiple stages, for example, compared to carrying out the aforementioned cross-linking reaction step in one stage, the strength of the precursor can be further improved, so that the present invention with both high porosity and strength can be obtained Void layer. Although the mechanism is unknown, for example, it is estimated as follows. That is, as described above, if the film strength is increased by a catalyst or the like at the same time as the formation of the void layer, there is a problem that the film strength is increased due to the catalyst reaction, but the porosity is reduced. We speculate that this is because, for example, the number of crosslinks (chemical bonding) of the microporous particles increases due to the crosslinking reaction of the microporous particles of the catalyst, and therefore the bonding becomes stronger but the entire void layer condenses and the void ratio decreases. In contrast, by performing the aforementioned precursor formation step and the aforementioned crosslinking reaction step as another step, and performing the aforementioned crosslinking reaction step in many stages, we speculate that, for example, there is little change in the overall morphology of the aforementioned precursor. (For example, when there is almost no overall condensation), increase the number of crosslinks (chemical bonding). However, this is only an example of a presumable mechanism, and does not limit the present invention.

In the aforementioned precursor forming step, for example, although particles having a certain shape are laminated to form the aforementioned void layer precursor, the strength of the aforementioned precursor is very weak at this time. Then, for example, a light or thermally active catalyst is reacted to produce a crosslinking accelerator (for example, a strong base catalyst produced by a photobase generator, etc.) that can chemically bond the aforementioned microporous particles (the first step of the crosslinking reaction step) One stage). In order to respond more efficiently in a short time, by further After heat aging (the second stage of the cross-linking reaction step), we speculate that the aforementioned microporous particles further undergo chemical bonding (cross-linking reaction) and increase the strength. A specific example is that the aforementioned microporous particles are microporous particles of a silicon compound (for example, a crushed product of a gel-like silica compound), and in the case where the remaining silanol groups (OH groups) are present in the aforementioned precursors, I guess The aforementioned residual silanol groups are chemically combined by a cross-linking reaction. However, the description is also an example, not a limitation of the present invention.

As long as there is no special description for the method of manufacturing the laminated film of the present invention, the description of the void layer and the laminated film of the present invention can be cited.

In the manufacturing method of the laminated film of the present invention, the aforementioned gel compound and its pulverized product, the monomer compound and the precursor of the monomer compound can refer to the description of the void layer and the laminated film of the present invention.

Although the manufacturing method of the laminated film of this invention can be performed as follows, for example, it is not limited to this.

The manufacturing method of the laminated film of the present invention, for example, as described above, has a liquid-containing preparation step for preparing a liquid-containing liquid containing the aforementioned microporous particles. When the microporous particle is a pulverized product of a gel-like compound, the pulverized product is prepared, for example, by pulverizing the gel-like compound. By pulverizing the aforementioned gel-like compound, as described above, the three-dimensional structure of the aforementioned gel-like compound can be destroyed and dispersed into a three-dimensional basic structure.

Hereinafter, although the gelation of the monomer compound is used to produce the gel-like compound, and the gel-like compound is pulverized to prepare a pulverized product, the present invention is not limited to the following examples.

The gelation of the aforementioned monomer compound can be achieved, for example, by making the aforementioned The monomer compounds are hydrogen-bonded with each other or intermolecular force bonding.

The aforementioned monomer compound can be exemplified by the silicon compound represented by the aforementioned formula (1) described in the aforementioned void layer of the present invention.

Since the silicon compound of the aforementioned formula (1) has a hydroxyl group, the monomers of the aforementioned formula (1) can be bonded through hydrogen bonding of the respective hydroxyl groups or intermolecular forces, for example.

In addition, the silicon compound may be a hydrolyzate of the silicon compound precursor as described above, for example, it may be produced by hydrolyzing the silicon compound precursor represented by the above formula (2) in the void layer of the present invention.

The hydrolysis method of the aforementioned monomer compound precursor is not particularly limited, and it can be carried out by a chemical reaction in the presence of a catalyst, for example. Examples of the aforementioned catalyst include acids such as oxalic acid and acetic acid. The aforementioned hydrolysis reaction can be carried out, for example, by slowly mixing an aqueous solution of oxalic acid in a mixed liquid (such as a suspension) of the aforementioned silicon compound and dimethyl sulfide under room temperature environment, and then stirring immediately for about 30 minutes. . When the silicon compound precursor is hydrolyzed, for example, by completely hydrolyzing the alkoxy group of the silicon compound precursor, the subsequent gelation, maturation, heating and immobilization after the formation of the void structure can be further efficiently expressed.

The gelation of the aforementioned monomer compound can be carried out, for example, by a dehydration condensation reaction between the aforementioned monomers. The aforementioned dehydration condensation reaction, for example, is preferably carried out in the presence of a catalyst, and the aforementioned catalysts include, for example, acid catalysts such as hydrochloric acid, oxalic acid, and sulfuric acid, and alkaline catalysts such as ammonia, potassium hydroxide, sodium hydroxide, and ammonium hydroxide. Catalyst (alkaline catalyst) and other dehydration condensation catalysts. The aforementioned dehydration condensation catalyst is particularly preferably an alkali catalyst. In the aforementioned dehydration condensation reaction, the amount of the aforementioned catalyst added to the aforementioned monomer compound is not particularly limited, and relative to 1 mol of the aforementioned monomer compound, the catalyst can be, for example, 0.1 to 10 mol, 0.05 to 7 mol, 0.1 to 5 mol.

The gelation of the aforementioned monomer compound is preferably carried out in a solvent, for example. The ratio of the aforementioned monomer compound in the aforementioned solvent is not particularly limited. The aforementioned solvents can include, for example: dimethyl sulfide (DMSO), N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAc), dimethylformamide (DMF) , Γ-butyrolactone (GBL), acetonitrile (MeCN), ethylene glycol ether (EGEE), etc. The aforementioned solvent may be one type, or two or more types may be used in combination. Hereinafter, the solvent used for the aforementioned gelation is also referred to as "gelation solvent".

The conditions for the aforementioned gelation are not particularly limited. The treatment temperature of the aforementioned solvent containing the aforementioned monomer compound can be, for example, 20 to 30°C, 22 to 28°C, and 24 to 26°C, and the treatment time can be, for example, 1 to 60 minutes, 5 to 40 minutes, and 10 to 30 minutes. . When the aforementioned dehydration condensation reaction is carried out, the treatment conditions are not particularly limited, and these examples can be cited. By performing the aforementioned gelation, for example, the siloxane bond will grow to form primary silicon dioxide particles, and the reaction proceeds further, whereby the aforementioned primary particles are connected into a rosary shape to generate a three-dimensional structure gel.

The gel-like compound obtained by the gelation is preferably subjected to an aging treatment after the gelation reaction. By the aforementioned aging treatment, for example, by further growing the primary particles of the gel having the three-dimensional structure obtained by gelation, the size of the particles themselves can be increased, and as a result, the contact state of the mesh portion that the particles contact can be made Increase from point contact to surface contact. For the gel subjected to the above-mentioned aging treatment, for example, the strength of the gel itself is increased, and as a result, the strength of the three-dimensional basic structure after pulverization can be increased. Thereby, for example, in the drying step after coating the pulverized product, the pore size of the void structure formed by the accumulation of the three-dimensional basic structure can be prevented from shrinking due to the volatilization of the solvent during the drying process.

The aforementioned aging treatment is performed, for example, by keeping the aforementioned gel-like compound at a predetermined temperature for a predetermined time. The aforementioned predetermined temperature is not particularly limited, and its lower limit is, for example, 30°C or higher, 35°C or higher, or 40°C or higher, and its upper limit is, for example, 80°C or lower, 75°C or lower, or 70°C or lower, and its range is, for example, 30 to 80°C, 35 to 75°C, 40 to 70°C. The aforementioned predetermined time is not particularly limited. The lower limit is, for example, 5 hours or more, 10 hours or more, and 15 hours or more, and the upper limit is, for example, 50 hours or less, 40 hours or less, or 30 hours or less, and the range is, for example, 5 to 50 hours. 10 to 40 hours, 15 to 30 hours. In addition, the most appropriate conditions for maturation are, for example, the main purpose is to increase the size of the aforementioned silicon dioxide primary particles and to increase the contact area of the mesh portion. In addition, consideration should be given to the boiling point of the solvent used. For example, if the aging temperature is too high, the solvent will volatilize excessively, which may cause problems such as closing the pores of the three-dimensional void structure due to the concentration of the coating solution (gel solution). On the other hand, when the aging temperature is too low, not only the According to the effect of maturation, the temperature deviation of the mass production process will increase after a period of time, which may result in poor quality products.

The above-mentioned aging treatment can use, for example, the same solvent as the above-mentioned gelation treatment. Specifically, it is preferable to perform the reaction product after the above-mentioned gel treatment (that is, the above-mentioned solvent containing the aforementioned gel-like compound) as it is. The molar number of the residual silanol group contained in the gel (the gel-like compound, for example, the gel-like silicon compound) after the completion of the aging treatment after gelation is, for example, the added raw material (for example, the monomer compound) The ratio of residual silanol groups when the alkoxy molar number of the precursor) is 100, the lower limit is, for example, 1% or more, 3% or more, 5% or more, and the upper limit is, for example, 50% or less, 40% or less, 30% or less, and the range is, for example, 1 to 50%, 3 to 40%, 5 to 30%. In order to increase the hardness of the gel, for example, the lower the molar number of residual silanol groups, the better. If the molar number of the silanol group is too high, for example, the void structure may not be maintained until the precursor of the polysiloxane porous body is cross-linked. On the other hand, if the molar number of the silanol group is too low, for example, in the step of preparing the aforementioned microporous particle-containing liquid (such as a suspension) and/or the subsequent step, the pulverized product of the gel-like compound cannot be cross-linked, so It may not be able to impart sufficient film strength. In addition, the above is an example of the silanol group, but for example, when the silicon compound of the monomer is modified with various reactive functional groups, the same phenomenon can be applied to each functional group.

After the aforementioned monomer compound is gelled in the aforementioned solvent for gelation, the obtained gel-like compound is pulverized. The aforementioned pulverization system, for example, can pulverize the gel-like compound in the aforementioned gelation solvent as it is, or after replacing the aforementioned gelation solvent with another solvent, the aforementioned gel compound The gel-like compound in other solvents is crushed. In addition, for example, the catalyst and solvent used in the gelation reaction will remain after the maturation step, and the resulting liquid will gel after a period of time (use period), and when the drying efficiency during the drying step is reduced, it is advisable to use other Solvent substitution. Hereinafter, the aforementioned other solvents are also referred to as "solvents for pulverization".

The solvent for pulverization is not particularly limited, and, for example, an organic solvent can be used. Examples of the aforementioned organic solvent include solvents with a boiling point of 130°C or less, a boiling point of 100°C or less, and a boiling point of 85°C or less. Specific examples include, for example, isopropanol (IPA), ethanol, methanol, butanol, propylene glycol monomethyl ether (PGME), methyl siloxol, acetone, dimethylformamide (DMF), and the like. The aforementioned solvent for pulverization may be, for example, one type, or two or more types may be used in combination.

The combination of the solvent for gel and the solvent for pulverization is not particularly limited, and examples include a combination of DMSO and IPA, a combination of DMSO and ethanol, DMSO and methanol, and a combination of DMSO and butanol. In this way, by replacing the solvent for gel with the solvent for pulverization, for example, a more uniform coating film can be formed when the coating film is formed as described later.

The method for crushing the gel compound is not particularly limited. For example, it can be performed by an ultrasonic homogenizer, a high-speed rotating homogenizer, a crushing device that uses other cavitation phenomena, or a crushing device that causes liquid to collide diagonally under high pressure. Ball mills and other devices for media crushing, for example, physically destroy the void structure of the gel during crushing. In contrast, homogenizers, etc., the preferred cavity-forming crushing device of the present invention, for example, due to the medialess method, can use high speed The shear force peeling is contained in the bonding surface of the weakly bonded silica particles in the three-dimensional structure of the gel. With this, the three-dimensional structure of the sol produced, For example, a void structure with a certain range of particle size distribution can be maintained, and the void structure generated by accumulation during coating and drying can be reformed. The conditions for the aforementioned pulverization are not particularly limited. For example, it is preferable to impart a high-speed flow instantaneously to pulverize the gel without volatilizing the solvent. For example, it is preferable to pulverize into a pulverized product of the aforementioned particle size deviation (for example, volume average particle diameter or particle size distribution). Assuming that the amount of work such as grinding time and strength is insufficient, for example, not only coarse particles remain but dense pores cannot be formed, appearance defects are also increased, and high quality may not be obtained. On the other hand, when the workload is too large, for example, sol particles having a finer particle size distribution than a desired particle size distribution will be formed, and the size of the voids deposited after coating and drying will be fine, and the desired porosity may not be satisfied.

As described above, a liquid (e.g., a suspension) containing the aforementioned microporous particles (a crushed product of a gel-like compound) can be produced. In addition, after preparing the liquid containing the microporous particles, or during the production process, by adding a catalyst that chemically binds the microporous particles, a liquid containing the microporous particles and the catalyst can be prepared. The addition amount of the aforementioned catalyst is not particularly limited, but it is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight relative to the weight of the aforementioned microporous particles (grinded product of the gel-like compound). The aforementioned catalyst may be, for example, a catalyst (cross-linking reaction accelerator) that promotes cross-linking and bonding of the aforementioned microporous particles. The chemical reaction to chemically bond the aforementioned microporous particles preferably utilizes the dehydration condensation reaction of the residual silanol group contained in the silica sol molecule. By promoting the reaction of the hydroxyl group of the silanol group with the aforementioned catalyst, the void structure can be hardened in a short time and the film can be continuously formed. The aforementioned catalysts can be photoactive catalysts and thermally active catalysts as examples. If the aforementioned photoactive catalyst is used, for example, in the aforementioned precursor formation step, it can be used without heating The aforementioned microporous particles are chemically bonded (for example, cross-linked and bonded). In this way, for example, in the precursor forming step, since shrinkage of the precursor as a whole is not easy to occur, a higher porosity can be maintained. In addition, in addition to the aforementioned catalyst, a substance that generates a catalyst (catalyst generator) may be used, or the aforementioned catalyst may be replaced with this. For example, the aforementioned catalyst is a cross-linking reaction accelerator, and the aforementioned catalyst generator may be a substance that produces the aforementioned cross-linking reaction accelerator. For example, in addition to the aforementioned photoactive catalyst, a substance that generates a catalyst by light (photocatalyst generator) can be used in addition, or it can replace the aforementioned photoactive catalyst, and in addition to the aforementioned thermally active catalyst, another can be used. Substances that generate catalysts by heat (thermal catalyst generators), or replace the aforementioned thermally active catalysts. The aforementioned photoactive catalyst is not particularly limited, but photobase generators (substances that generate alkaline catalysts by light irradiation), photoacid generators (substances that generate acidic catalysts by light irradiation), etc. can be cited as examples. And the photobase generator is preferred. Examples of the aforementioned photobase generator include: 9-anthrylmethyl N, N-diethylcarbamate (trade name WPBG-018), (E)-1-[3- (2-hydroxyphenyl)-2-acrylic acid]piperidine ((E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine, trade name WPBG-027), 1-(anthraquinone-2 -Yl) ethyl imidazole carboxylate (1-(anthraquinon-2-yl)ethyl imidazolecarboxylate, trade name WPBG-140), 2-nitrobenzyl 4-methacryloyloxypyridine-1-carboxylic acid Ester (trade name WPBG-165), 1,2-diisopropyl-3-[bis(methylamino)methylene]guanidine 2-(3-benzylphenyl) propionate (trade name WPBG -266), 1,2-dicyclohexyl-4,4,5,5-tetraformin n-butyl triphenyl borate (trade name WPBG-300), and 2-(9-oxydibenzo Piperan-2-yl) propionic acid 1,5,7-triazide Heterobicyclo[4.4.0]dec-5-ene (Tokyo Chemical Industry Co., Ltd.), a compound containing 4-piperidine methanol (trade name HDPD-PB100: manufactured by HERAEUS), and the like. In addition, the trade names including "WPBG" are the trade names of Wako Pure Chemical Industries, Ltd. (stocks). Examples of the aforementioned photoacid generator include aromatic sulfonium salt (trade name SP-170: ADEKA company), triaryl sulfonium salt (trade name CPI101A: SAN-APRO company), aromatic sulfonium salt (trade name Irgacure 250: CHIBA JAPAN Company) etc. In addition, the catalyst that chemically binds the microporous particles is not limited to the photoactive catalyst and the photocatalyst generator, and may be, for example, a thermally active catalyst or a thermal catalyst generator such as urea. The catalyst for chemically bonding the aforementioned microporous particles includes, for example, alkaline catalysts such as potassium hydroxide, sodium hydroxide, and ammonium hydroxide, and acid catalysts such as hydrochloric acid, acetic acid, and oxalic acid. Among them, an alkali catalyst is preferred. The catalyst or catalyst generator that chemically binds the aforementioned microporous particles, for example, can be added to a sol particle liquid (e.g., suspension) containing the aforementioned pulverized product (microporous particles) before coating, or the aforementioned catalyst can be used. The medium or catalyst generator is mixed in the solvent to make a mixed liquid for use. The aforementioned mixed solution may be, for example, a coating solution obtained by directly adding to the aforementioned sol particle solution and dissolving, a solution obtained by dissolving the aforementioned catalyst or catalyst generator in a solvent, or the aforementioned catalyst or catalyst generator Dispersion liquid obtained by dispersing in a solvent. The aforementioned solvent is not particularly limited, and water, buffer solutions, etc. can be cited as examples.

In addition, for example, when the aforementioned microporous particle is a pulverized product of a gel-like silicon compound made of a silicon compound containing at least trifunctional saturated bond functional groups, it may be prepared in a liquid containing the aforementioned microporous particles. During the production process, further add to make the aforementioned microporous particles indirectly bond The crosslinking auxiliary agent. The cross-linking auxiliary agent enters between the particles, and the particles and the cross-linking auxiliary agent interact or bond with each other, and the particles that are slightly separated in distance can also be combined, so that the strength can be improved efficiently. The aforementioned crosslinking auxiliary agent is preferably a multi-crosslinked silane monomer. The aforementioned multi-crosslinked silane monomer, specifically, for example, may have 2 or more and 3 or less alkoxysilyl groups, and the chain length between the alkoxysilyl groups is 1 or more and 10 or less carbon atoms, and may contain other than carbon. Of the element. The aforementioned crosslinking auxiliary agent may include, for example: 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, bis(trimethoxysilyl)methane, bis(trimethoxysilyl)ethane, Ethoxysilyl) methane, 1,3-bis(triethoxysilyl)propane, 1,3-bis(trimethoxysilyl)propane, 1,4-bis(triethoxysilyl)butane, 1 ,4-bis(trimethoxysilyl)butane, 1,5-bis(triethoxysilyl)pentane, 1,5-bis(trimethoxysilyl)pentane, 1,6-bis(triethyl) Oxysilyl)hexane, 1,6-bis(trimethoxysilyl)hexane, bis(trimethoxysilyl)-n-butyl-n-propyl-ethane-1,2-diamine, tri-( 3-trimethoxysilylpropyl) isocyanate, tris-(3-triethoxysilylpropyl) isocyanate, etc. Among them, particularly preferred is 1,2-bis(trimethoxysilyl)ethane or 1,6-bis(trimethoxysilyl)hexane. The addition amount of the crosslinking auxiliary agent is not particularly limited, but for example, the weight of the microporous particles of the aforementioned silicon compound can be 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 10% by weight.

Next, a resin film (hereinafter sometimes referred to as a "substrate") is coated with a liquid (for example, a suspension) containing the aforementioned microporous particles (coating step). For the aforementioned coating, for example, various coating methods described later can be used, and it is not limited thereto. By directly applying a liquid containing the microporous particles (for example, a pulverized product of a gel-like silica compound) on the resin film, a coating film containing the microporous particles and the catalyst can be formed. The aforementioned coating The film can also be called a coating layer, for example. By forming the coating film, for example, by sedimentation and accumulation of the crushed product whose three-dimensional structure has been destroyed, a new three-dimensional structure can be constructed. In addition, for example, the liquid containing the aforementioned microporous particles may not contain a catalyst that chemically binds the aforementioned microporous particles. For example, as described later, a catalyst that chemically bonds the microporous particles may be sprayed on the coating film, or the precursor forming step may be performed while spraying. However, the liquid containing the microporous particles may also include a catalyst that chemically binds the microporous particles, and the catalyst contained in the coating film chemically binds the microporous particles to form the porous Body precursors.

The aforementioned solvent (hereinafter, also referred to as "coating solvent") is not particularly limited, and, for example, an organic solvent can be used. The aforementioned organic solvent may include a solvent with a boiling point of 150°C or less. Specific examples include IPA, ethanol, methanol, n-butanol, 2-butanol, isobutanol, pentanol, etc., and the same solvent as the aforementioned pulverization solvent can be used. When the present invention includes the step of pulverizing the gel-like compound, in the step of forming the coating film, for example, the solvent for pulverization containing the pulverized product of the gel-like compound can be used as it is.

In the coating step, for example, it is preferable to coat the ground material in the form of a sol dispersed in the solvent (hereinafter also referred to as "sol particle liquid") on the substrate. The sol particle liquid of the present invention, for example, is coated on a substrate and dried, and then subjected to the aforementioned chemical cross-linking, so that a void layer having a film strength above a certain level can be continuously formed into a film. In addition, the "sol" in the present invention refers to the so-called pulverization of the three-dimensional structure of the gel to maintain a part of the void structure of the nano-structured silica sol particles dispersed in a solvent And show the state of liquidity.

The concentration of the pulverized product in the solvent is not particularly limited, and may be, for example, 0.3 to 50% (v/v), 0.5 to 30% (v/v), 1.0 to 10% (v/v). If the concentration of the aforementioned pulverized product is too high, for example, the fluidity of the aforementioned sol particle solution is significantly reduced, which may cause agglomerates during coating and coating wrinkles. On the other hand, if the concentration of the pulverized product is too low, for example, not only the time equivalent to drying the solvent of the sol particle solution, but also the residual solvent after drying will increase, so the porosity may decrease.

The physical properties of the aforementioned sol are not particularly limited. The shear viscosity of the aforementioned sol can be, for example, a viscosity of 100cPa at a shear rate of 10001/s. Below s, viscosity 10cPa. Below s, viscosity 1cPa. s or less. If the shear viscosity is too high, for example, coating wrinkles may occur, so the transfer rate of the gravure coating may decrease. On the contrary, when the shear viscosity is too low, for example, the wet coating (coating) thickness during coating cannot be increased, and therefore, the desired thickness may not be obtained after drying.

The amount of the pulverized product applied to the substrate is not particularly limited. For example, it can be appropriately set according to the desired thickness of the porous polysilicate. When forming the aforementioned porous polysilicate body with a thickness of 0.1 to 1000 μm, a specific example of the amount of the pulverized product applied to the aforementioned substrate is per 1 m ² of the aforementioned substrate area, such as 0.01 to 60000 μg, 0.1 to 5000 μg, 1 to 50μg. The preferable coating amount of the aforementioned sol particle liquid is related to, for example, the concentration of the liquid or the coating method, so it is difficult to define it unambiguously. However, in consideration of productivity, it is preferable to coat as thinly as possible. If the coating amount (coating amount) is too large, for example, the possibility of being dried in a drying oven before the solvent volatilizes is high. Therefore, by sedimentation and accumulation of the pulverized nanoparticles in the solvent, and drying the solvent before forming the void structure, the formation of voids can be prevented and the porosity can be greatly reduced. On the other hand, if the coating amount is too thin, the risk of uneven surface coating due to unevenness of the substrate and uneven hydrophilicity and hydrophobicity may increase.

In addition, the manufacturing method of the present invention, for example, as described above, has a precursor forming step of forming a void structure of the precursor of the void layer on the resin film. The precursor formation step is not particularly limited, but for example, the precursor (void structure) can be formed by a drying step of drying the coating film formed by coating the microporous particle-containing liquid. By the drying process in the drying step, for example, not only the solvent (the solvent contained in the sol particle liquid) in the coating film can be removed, but the sol particles can also be settled and accumulated during the drying process to form a void structure. The temperature of the drying treatment is, for example, 50 to 250° C., 60 to 150° C., and 70 to 130° C., and the time of the drying treatment is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, and 0.3 to 3 minutes. Drying treatment temperature and time, for example, in terms of continuous productivity or showing high porosity, the lower the temperature and the shorter the time, the better. If the conditions are too strict, such as a base resin film, since the base material is close to the glass transition temperature of the base material, the base material stretches in the drying oven, and after coating, defects such as cracks may occur in the formed void structure. On the other hand, when the conditions are too loose, for example, since it contains residual solvent when leaving the drying furnace, it may cause appearance problems such as scratches when rubbing with the roller in the next step.

The aforementioned drying treatment may be, for example, natural drying, heat drying, or reduced pressure drying. The aforementioned drying method is not particularly limited, for example If you can use a general heating device. Examples of the aforementioned heating device include hot air heaters, heating rollers, and far-infrared heaters. Among them, when the industrial continuous production is the premise, it is advisable to use heating and drying. In addition, in order to suppress the shrinkage stress caused by the volatilization of the solvent during drying, and therefore the cracking of the void layer (the aforementioned polysiloxy porous body), the solvent used should preferably be a solvent with a low surface tension. The aforementioned solvents can be exemplified by lower alcohols represented by isopropanol (IPA), hexane, perfluorohexane, etc., but are not limited thereto. In addition, a small amount of perfluorinated surfactants or silicon-based surfactants may be added to the IPA, etc., to reduce the surface tension.

In addition, the manufacturing method of the laminated film of the present invention, as described above, includes a cross-linking reaction step in which a cross-linking reaction is generated inside the precursor after the precursor forming step, and in the cross-linking reaction step, The aforementioned cross-linking reaction accelerator is generated by light irradiation or heating, and the aforementioned cross-linking reaction step has many stages. In the first stage of the cross-linking reaction step, for example, the cross-linking reaction promoter (for example, an acidic substance or a basic substance) is used to chemically bond the microporous particles. By this, for example, the three-dimensional structure of the crushed product in the coating film (precursor) can be fixed. When the conventional sintering is performed for immobilization, for example, by performing a high-temperature treatment above 200°C, the dehydration condensation of silanol groups and the formation of siloxane bonds are induced. In the present invention, by reacting various additives that catalyze the dehydration and condensation reaction, for example, the aforementioned substrate (resin film) can not be damaged, and the drying temperature is relatively low at about 100°C and the processing time is less than a few minutes. Inside, the void structure is continuously formed and immobilized.

The aforementioned chemical bonding method is not particularly limited, for example, it can be It is appropriately determined according to the type of the aforementioned gel-like silicon compound. Specific examples of the aforementioned chemical bonding can be carried out by, for example, chemical cross-linking of the aforementioned pulverized product. In addition, it is also conceivable that, for example, when inorganic particles such as titanium oxide are added to the aforementioned pulverized product, the aforementioned inorganic The particles and the aforementioned pulverized product are chemically cross-linked and bonded. In addition, sometimes when a living catalyst such as an enzyme is supported, a site different from the active site of the catalyst and the aforementioned crushed product are chemically cross-linked and bonded. Therefore, in the present invention, for example, not only the void layer (polysiloxan porous body) formed by the aforementioned sol particles, but also the application of developing an organic-inorganic hybrid void layer, a host-guest void layer, etc., can be considered, but it is not limited to this.

The chemical reaction in the presence of the aforementioned catalyst (cross-linking reaction accelerator) can be carried out (occurred) at any stage of the manufacturing method of the present invention, and is not particularly limited, but for example, it can be carried out in the aforementioned multi-stage cross-linking reaction step At least one stage. For example, in the manufacturing method of the laminated film of the present invention, as described above, the drying step may also serve as the precursor forming step. In addition, for example, after the drying step, the cross-linking reaction step may be performed in multiple stages, and in at least one of the stages, the microporous particles may be chemically combined by the action of the catalyst. For example, as described above, the catalyst (crosslinking reaction accelerator) is a photoactive catalyst, and in the crosslinking reaction step, the microporous particles can be chemically combined by light irradiation. In addition, the catalyst-based thermally active catalyst can chemically bond the microporous particles by heating in the crosslinking reaction step.

The chemical reaction can be carried out, for example, by light irradiating the coating film containing the catalyst generator (substance that generates the crosslinking reaction promoter) added to the sol particle liquid (e.g., suspension) in advance Or heating, or spraying the aforementioned catalyst generator (substance that produces a cross-linking reaction accelerator) on the aforementioned coating film, followed by light irradiation or heating, or spraying the aforementioned catalyst generator (substance that produces a cross-linking reaction accelerator) on one side Light irradiation or heating is performed on one side. The cumulative light amount of the aforementioned light irradiation is not particularly limited, but it can be, for example, 200 to 800 mJ/cm ² , 250 to 600 mJ/cm ² , or 300 to 400 mJ/cm ² in @360nm conversion. From the viewpoint of preventing insufficient irradiation without light absorption and decomposition of the catalyst generating agent and insufficient effect, a ^{cumulative light amount of 200 mJ/cm 2} or more is preferable. In addition, from the viewpoint of preventing damage to the substrate under the void layer and generating thermal wrinkles, a ^{cumulative light quantity of 800 mJ/cm 2} or less is preferable. The conditions of the aforementioned heating treatment are not particularly limited. The aforementioned heating temperature can be, for example, 50 to 250°C, 60 to 150°C, or 70 to 130°C, and the aforementioned heating time can be, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, or 0.3 to 3 minutes. . Alternatively, the step of drying the coated sol particle liquid (e.g., suspension) as described above can also be used as a step of carrying out a chemical reaction in the presence of the aforementioned catalyst. That is, in the step of drying the applied sol particle liquid (e.g., suspension), the pulverized product (microporous particles) can be chemically combined by a chemical reaction in the presence of the catalyst. In this case, by further heating the coating film after the drying step, the pulverized product (microporous particles) can be further strongly bonded. In addition, it is estimated that a chemical reaction in the presence of the catalyst may also occur in the step of preparing the microporous particle-containing liquid (for example, a suspension) and the step of applying the microporous particle-containing liquid. However, this presumption does not impose any limitation on the present invention. In addition, in order to suppress the shrinkage stress caused by the volatilization of the solvent during drying, and thus the phenomenon of cracking of the void layer (the aforementioned polysiloxy porous body), the solvent used is preferably a solvent with low surface tension. Examples of lower alcohols represented by isopropanol (IPA), hexane, perfluorohexane, etc., are not limited thereto.

In the present invention, since the aforementioned cross-linking reaction step has many stages, for example, compared to the case where the aforementioned cross-linking reaction step is one stage, the strength of the aforementioned void layer can be further improved. Hereinafter, the steps after the second step of the aforementioned crosslinking reaction step are sometimes referred to as "aging step". In the aforementioned aging step, for example, by heating the aforementioned precursor, the cross-linking reaction can be further promoted in the aforementioned precursor. Although the phenomenon and mechanism generated in the aforementioned crosslinking reaction step are unknown, for example, it can be as described above. For example, in the aforementioned aging step, for example, by setting the heating temperature to a low temperature, the shrinkage of the precursor is suppressed while the cross-linking reaction occurs, thereby increasing the strength, so that both high porosity and strength can be achieved at the same time. The temperature in the aforementioned aging step is, for example, 40 to 70°C, 45 to 65°C, and 50 to 60°C. The time for performing the aforementioned aging step is, for example, 10 to 30 hours, 13 to 25 hours, or 15 to 20 hours.

As described above, the manufacturing method of the laminated film of the present invention can be carried out. The laminated film made by the manufacturing method of the present invention has excellent strength, for example, can be made into a roll-shaped porous body, and has the advantages of good manufacturing efficiency and easy handling.

The thus-obtained laminated film (void layer) of the present invention can be further laminated with other films (layers) to form a laminated structure including the aforementioned porous structure, for example. In this case, in the aforementioned laminated structure, each constituent element can be laminated through, for example, an adhesive or an adhesive.

For example, from the viewpoint of efficiency, the layering of the aforementioned constituent elements can be achieved by continuous processing using a long film (so-called roll-to-roll (Roll-to-roll)). to Roll) etc.). It is also possible to laminate the batch processing when the base material is a molded product, a component, or the like.

Hereinafter, regarding the continuous processing steps, the method of forming the aforementioned void layer of the present invention on the substrate (resin film) will be exemplified using FIGS. 1 to 3. Although Figure 2 shows the steps of forming the aforementioned porous polysilicate into a film, sticking a protective film and winding it up, when laminating on another functional film, the above method can be used, or another functional film can be coated. After drying, the above-mentioned porous polysilicate body after the above-mentioned film formation is pasted before winding. In addition, the film forming method shown in the figure is just an example, and it is not limited to this.

In addition, the aforementioned substrate may be the aforementioned resin film in the description of the void layer of the present invention. In this case, by forming the aforementioned void layer on the aforementioned substrate, the void layer of the present invention can be obtained. In addition, after the void layer is formed on the substrate, the void layer can be laminated on the resin film in the description of the void layer of the present invention, whereby the void layer of the present invention can also be obtained.

The cross-sectional view of FIG. 1 schematically shows an example of the steps in the method of forming the void layer on the substrate (resin film). In FIG. 1, the formation method of the aforementioned void layer includes: coating step (1), which is to coat the sol particle liquid 20" of the crushed product of the aforementioned gel-like compound on a substrate (resin film) 10 to form a coating film; The drying step (2) is to dry the sol particle liquid 20" to form a dried coating film (precursor of the void layer) 20'; the crosslinking step (3) is to crosslink the coating film 20' to form a crosslinking The precursor (void layer) 20 after the linking treatment; and the step of increasing the strength (aging step) (4), which improves the adhesion and peeling strength of the precursor 20 to the substrate 10 after the crosslinking treatment to form the void layer (strength Improved void layer) 21. In this way, as shown in the figure, a void layer 21 can be formed on the substrate 10. In this manufacturing method, the aforementioned drying step (2) corresponds to the aforementioned "precursor forming step" in the manufacturing method of the laminated film of the present invention. In addition, in the aforementioned cross-linking step (3) and the aforementioned strength improvement step (aging step) (4), a cross-linking reaction occurs inside the aforementioned precursor. That is, the two-step step of the aforementioned crosslinking step (3) and the aforementioned strength increasing step (aging step) (4) corresponds to the aforementioned "crosslinking reaction step" in the manufacturing method of the laminated film of the present invention. In addition, the formation method of the aforementioned void layer may or may not include steps other than the aforementioned (1) to (4) as appropriate.

In the aforementioned coating step (1), the coating method of the sol particle liquid 20" is not particularly limited, and general coating methods can be used. The aforementioned coating methods may include, for example, slot die method, reverse gravure coating method, and microgravure method (microgravure method). Coating method), dipping method (dip coating method), spin coating method, brush coating method, roll coating method, flexographic printing method, wire rod coating method, spray coating method, extrusion coating method, curtain coating method, reverse coating method Among them, from the viewpoints of productivity, smoothness of the coating film, etc., extrusion coating, curtain coating, roll coating, microgravure coating, etc. are preferred. Coating of the aforementioned sol particle liquid 20" The amount is not particularly limited, and for example, it can be appropriately set so that the thickness of the void layer 20 is appropriate. The thickness of the void layer 21 is not particularly limited. For example, it can be as described above.

In the aforementioned drying step (2), the sol particle liquid 20" is dried (i.e., the dispersion medium contained in the sol particle liquid 20" is removed) to form a dried coating film 20'. The conditions of the drying treatment are not particularly limited, and can be as described above.

In addition, in the aforementioned chemical treatment step (3), the catalyst containing the aforementioned catalyst generator (catalyst generation (crosslinking reaction accelerator)) added before coating Substances, for example, a photocatalyst generator or a thermal catalyst generator) coated film 20', irradiated with light or heated to chemically combine (for example, crosslink) the aforementioned pulverized product in the coated film 20' to form a cross-linking treatment Before the drive 20. The light irradiation or heating conditions in the aforementioned chemical treatment step (3) are not particularly limited, and can be as described above.

In addition, the aforementioned strength improvement step (aging step) (4) is performed by, for example, the precursor 20 after the heating and crosslinking treatment, and the void layer 21 is formed. The heating conditions of the aforementioned strength improvement step (aging step) (4) are not particularly limited, and can be as described above.

Next, FIG. 2 schematically shows an example of the coating device of the slot die method and the formation method of the aforementioned void layer using the coating device. In addition, although FIG. 2 is a cross-sectional view, hatching is omitted in order to make it easier to see.

As shown in the figure, each step in the method of using the device is carried out while conveying the substrate 10 in one direction by the roller. The conveying speed is not particularly limited, and may be, for example, 1 to 100 m/min, 3 to 50 m/min, and 5 to 30 m/min.

First, while the substrate 10 is sent out and transported by the sending roller 101, the coating step (1) of coating the sol particle liquid 20" on the substrate 10 is performed in the coating roller 102, and then transferred to the oven area 110 Drying step (2). In the coating device of Figure 2, after the coating step (1) and before the drying step (2), a preliminary drying step is performed. The preliminary drying step can be performed at room temperature without heating. In the drying step (2), the heating device 111 is used. The heating device 111, as described above, can appropriately use a hot air heater, a heating roller, a far-infrared heater, etc. In addition, for example, the drying step (2) can be divided into a plurality of Steps, and the later the drying step, the higher the drying temperature.

After the drying step (2), the chemical treatment step (3) is performed in the chemical treatment area 120. In the chemical treatment step (3), for example, when the dried coating film (precursor) 20' contains a photocatalyst generator, light is irradiated by a lamp (light irradiation device) 121 arranged above and below the substrate 10. Or, for example, when the dried coating film 20' contains a thermal catalyst generator, a hot air device (heating device) is used instead of the lamp (light irradiation device) 121, and the substrate is heated by the hot air device 121 disposed above and below the substrate 10. 10. Through this cross-linking treatment, the aforementioned pulverized product in the coating film 20' is chemically bonded, and the coating film 20' is hardened and strengthened to become the precursor 20 after the cross-linking treatment (hereinafter, sometimes only referred to as "precursor" ). In addition, in this example, although the chemical treatment step (3) is performed after the drying step (2), as described above, the aforementioned crushed product can be chemically bonded at any stage of the manufacturing method of the present invention, and there is no particular limitation. . For example, as mentioned above, the drying step (2) can double as the chemical treatment step (3). In addition, when the aforementioned chemical bond occurs in the drying step (2), the chemical treatment step (3) may be further performed to further strengthen the chemical bond of the crushed product. In addition, in the step before the drying step (2) (for example, the preliminary drying step, the coating step (1), the step of preparing a coating liquid (such as a suspension), etc.), the aforementioned pulverized product may be chemically bonded.

After the chemical treatment step (3), the strength improvement step (aging step) (4) is performed in the cross-linking reaction zone (aging zone) 130 to increase the strength of the precursor 20 of the void layer (for example, the adhesion and peeling of the resin film 10) Strength) is increased to form the void layer 21. The step of increasing the strength (aging step) (4), for example, a hot air heater (heating device) 131 disposed above and below the substrate 10 can be used, by such as The precursor 20 is heated as described above. The heating temperature, time, etc. are not particularly limited, but for example, they may be as described above.

Next, after the strength improvement step (aging step) (4), the laminate in which the void layer 21 is formed on the substrate 10 is wound up by the winding roller 105. In addition, in FIG. 2, the protective sheet sent by the roller 106 covers and protects the void layer 21 of the aforementioned laminate. Here, instead of the aforementioned protective sheet, another laminated layer formed of a long thin film may be formed on the void layer 21.

Fig. 3 schematically shows an example of a coating device using a micro-gravure method (micro-gravure coating method) and the aforementioned void layer forming method using the coating device. In addition, although FIG. 3 is a cross-sectional view, hatching is omitted in order to make it easier to see.

As shown in the figure, each step in the method of using this apparatus is performed while conveying the base material 10 in one direction by the roller in the same manner as in FIG. 2. The conveying speed is not particularly limited, and may be, for example, 1 to 100 m/min, 3 to 50 m/min, and 5 to 30 m/min.

First, while the substrate 10 is sent out and transported by the sending roller 201, the coating step (1) of coating the sol particle liquid 20" on the substrate 10 is carried out. The coating system of the sol particle liquid 20" is as shown in the figure. The liquid part 202, the doctor blade (squeegee blade) 203, and the micro intaglio 204 are performed. Specifically, the sol particle liquid 20" stored in the liquid reservoir 202 is adhered to the surface of the micro intaglio plate 204, and then, while being controlled to a predetermined thickness by a doctor blade 203, the micro intaglio plate 204 is used to coat the surface of the substrate 10. In addition, the micro-gravure plate 204 is an example and is not limited to this, and any other coating device can be used.

Next, the drying step (2) is performed. Specifically, as shown in the figure, In the oven area 210, the substrate 10 coated with the sol particle liquid 20" is transported, and the sol particle liquid 20" is heated by the heating device 211 in the oven area 210. The heating device 211 may be the same as that of FIG. 2, for example. In addition, the drying step (2) can be divided into a plurality of steps by dividing the oven area 210 into a plurality of blocks, and the later drying step has a higher drying temperature. After the drying step (2), in the chemical treatment area 220, the chemical treatment step (3) is performed. In the chemical treatment step (3), for example, when the dried coating film 20' contains a photocatalyst generating agent, light is irradiated with a lamp (light irradiation device) 221 arranged above and below the substrate 10. Or, for example, when the dried coating film (precursor) 20' contains a thermal catalyst generator, a hot air device (heating device) is used instead of the lamp (light irradiation device) 221, and a hot air device ( The heating device) 221 heats the substrate 10. Through this cross-linking treatment, the aforementioned pulverized products in the coating film 20' are chemically combined to form a precursor 20 for the void layer.

After the chemical treatment step (3), the strength improvement step (aging step) (4) is performed in the crosslinking reaction zone (aging zone) 230 to increase the adhesive peel strength of the void layer precursor 20 to the resin film 10 to form孔层21。 Hole layer 21. The step of increasing the strength (aging step) (4), for example, can be performed by using a hot air heater (heating device) 231 arranged above and below the substrate 10 by heating the precursor 20 as described above. The heating temperature, time, etc. are not particularly limited, but for example, they may be as described above.

Next, after the strength improvement step (aging step) (4), the laminated film having the void layer 21 formed on the substrate 10 is wound up by the winding roller 241. Then, for example, another layer may be laminated on the aforementioned laminated film. In addition, it is also possible to apply the laminated film on the laminated film before winding the laminated film by the take-up roller 241, for example, For example, build up other layers.

[2. Optical components]

The optical member of the present invention is characterized by including the laminated film of the present invention as described above. The optical member of the present invention is characterized by including the laminated film of the present invention, and other structures are not limited in any way. The optical member of the present invention may further include other layers in addition to the aforementioned laminated film of the present invention.

In addition, the optical member of the present invention includes the aforementioned laminated film of the present invention as a low reflection layer. The optical member of the present invention may further include other layers in addition to the aforementioned laminated film of the present invention. The optical member of the present invention has a roll shape, for example.

Example

Next, embodiments of the present invention will be described. However, the present invention is not limited to the following examples.

(Example 1)

In this example, the laminated film (laminated film roll) of the present invention was produced as follows.

(1) Gelation of silicon compounds

Dissolve 0.95 g of MTMS of the silicon compound precursor in 2.2 g of DMSO. In the aforementioned mixed solution, 0.5 g of 0.01 mol/L oxalic acid aqueous solution was added, and stirred at room temperature for 30 minutes, thereby hydrolyzing MTMS to generate tris (hydroxy) methyl silane.

After adding 0.38g of 28% ammonia water and 0.2g of pure water to 5.5g of DMSO, the aforementioned mixing after hydrolysis treatment is further added And stir at room temperature for 15 minutes to gelate the tris(hydroxy)methylsilane to obtain a gel-like silicon compound.

(2) Aging treatment

The above-mentioned gelatinized mixed liquid was kept at 40°C for 20 hours as it is, and the aging treatment was carried out.

(3) Crushing treatment and addition of photoalkali production catalyst

Next, use a spatula to pulverize the gel-like silicon compound after the aging treatment into granules with a size of several mm to several cm. Add 40 g of IPA to it, and after lightly stirring, let it stand at room temperature for 6 hours, and decanted the solvent and catalyst in the gel. Repeat the same decantation process 3 times to end the solvent replacement. Next, the gel-like silicon compound in the mixed solution is subjected to high-pressure, media-free pulverization. This crushing treatment is carried out using a homogenizer (trade name UH-50, manufactured by SMT Company), weighing 1.18g of gel and 1.14g of IPA in a 5cc screw bottle, and then performing it for 2 minutes under the conditions of 50W and 20kHz. Shattered.

Through the pulverization treatment, the gel-like silicon compound in the mixed solution is pulverized, so that the mixed solution becomes a sol particle liquid of the pulverized product. A dynamic light scattering nano-trajectory particle size analyzer (manufactured by Nikkiso Co., Ltd., model UPA-EX150) was used to confirm the volume average particle size showing the particle size deviation of the pulverized product contained in the mixed liquid, and the result was 0.50 to 0.70. In addition, an IPA (isopropanol) solution of 1.5% by weight of a photobase generator (Wako Pure Chemical Industries, Ltd. (stock): trade name WPBG266, a substance used as a photocatalyst (crosslinking reaction accelerator)) was prepared, To 0.75 g of the aforementioned sol particle liquid, 0.031 g was added to prepare a coating liquid. In addition, the above steps (1) to (3) are equivalent to the production of the above-mentioned fine The "contained liquid preparation step" of the liquid containing the pore particles.

(4) Formation of coating film and formation of polysiloxy porous body roll

Next, by the rod coating method, the aforementioned coating liquid is applied (coated) on the surface of a polyethylene terephthalate (PET) substrate (resin film, 100 m long) to form a coating film (coating step) . The coating system is to coat 6 μL of the sol particle liquid ^{per 1 mm 2 of the surface of the substrate.} Treated at a temperature of 100°C for 1 minute and dried the aforementioned coating film to form a polysilicate porous body film with a thickness of 1 μm (drying step). UV irradiation (precursor formation step) is performed on the aforementioned porous film after drying. The aforementioned UV irradiation was carried out at 350mJ/cm ² (@360nm). In addition, the aforementioned precursor was heated and aged at 60° C. for 20 hr to prepare a low refractive index film (void layer) having film strength.

(Comparative example)

The same operation as in Example 1 was carried out except that the post-treatment after the formation of the porous silica film was performed only by UV treatment (without heat aging), a laminated film with a low refractive index film (void layer) laminated on the resin film was obtained. roll.

(Example 2)

In addition to the step of "(3) Crushing treatment and addition of photobase generating catalyst" in Example 1, after adding the photobase generating catalyst solution, 0.018g of 5 wt% was further added to 0.75g of the aforementioned sol solution. Except that the bis(trimethoxysilyl)ethane was used to prepare the coating solution, the same operation as in Example 1 was performed to prepare a laminated film roll in which a low refractive index film (void layer) was laminated on a resin film.

(Example 3)

Except in the step of "(3) Crushing treatment and addition of photoalkali production catalyst" in Example 1, the addition of photoalkali production catalyst to 0.75g of the aforementioned sol liquid Except that the amount was 0.054 g, the same operation as in Example 1 was performed to prepare a laminated film roll in which a low refractive index film (void layer) was laminated on a resin film.

(Example 4)

Except that the bis(trimethoxysilyl)ethane of Example 2 was changed to 5 wt% 1,6-bis(trimethoxysilyl)hexane (trade name KBM3066: manufactured by Shin-Etsu Chemical Co., Ltd.), The same operation as in Example 2 was performed to prepare a laminated film roll in which a low refractive index film (void layer) was laminated on a resin film.

These results are shown in Table 1 below. In addition, the refractive index, adhesive peel strength, haze, and scratch resistance were measured by the aforementioned methods. The scratch resistance is evaluated by ○, △ or ×. In addition, the storage stability is the result of leaving the coating liquid at room temperature for 1 week, and visually confirming whether the coating liquid has changed.

As shown in the foregoing Table 1, Examples 1 to 4 in which the strength increasing step (aging step) (ie, the cross-linking reaction step has many stages) are compared to those without the strength increasing step (aging step) (ie, the cross-linking step). The reaction step is a comparative example of step 1), and the adhesive peel strength and scratch resistance are improved. In addition, there is almost no difference in refractive index between Examples 1 to 4 and Comparative Example, maintaining an extremely low refractive index of 1.14 to 1.17. That is, it is confirmed that the laminated film of the example can have both high voids Rate and film strength. In addition, the haze values of the laminated films of Examples 1 to 4 also maintained an extremely low value of 0.4, which is the same as that of the Comparative Example, so it was confirmed that the same degree of transparency as the Comparative Example was maintained. Furthermore, Examples 1 to 4 also have excellent storage stability of the coating solution, and therefore it was confirmed that a laminated film of stable quality can be produced efficiently.

Industrial availability

As described above, according to the present invention, it is possible to provide a method for manufacturing a laminated film, a laminated film, an optical member, and an image display device that can have both high porosity and film strength. Since the laminated film of the present invention exhibits the aforementioned characteristics, for example, it can easily achieve a low refractive index that can be used as a substitute for an air layer. Therefore, it is not necessary to arrange a large number of components with a certain distance to provide an air layer in order to obtain a low refractive index, and a low refractive index can be imparted by arranging the laminated film of the present invention at a desired position. Therefore, the laminated film of the present invention is useful for optical components that require a low refractive index. The laminated film of the present invention, for example, can be used for the optical member and image display device of the present invention, but it is not limited to this, and can be used for any purpose.

10‧‧‧Substrate

20‧‧‧Precursor (precursor after cross-linking treatment)

20’‧‧‧Coating film (coating film after drying)

20"‧‧‧Sol particle liquid

21‧‧‧Void layer

Claims (15)

A laminated film in which a gap layer is laminated on a resin film, and the laminated film is characterized in that it is manufactured by a manufacturing method including the following steps: a precursor forming step, which is driven before forming the gap layer on the resin film And the cross-linking reaction step is to generate a cross-linking reaction inside the precursor after the precursor forming step; the precursor contains a pulverized product of a gel-like silicon compound and can be produced to promote the aforementioned The cross-linking reaction accelerator is the substance of the cross-linking reaction; the aforementioned cross-linking reaction is the cross-linking reaction of the pulverized products with each other; the aforementioned substance generates the aforementioned cross-linking reaction accelerator by light or heat; the aforementioned precursor formation step does not produce the aforementioned Cross-linking reaction accelerator; in the aforementioned cross-linking reaction step, the aforementioned cross-linking reaction accelerator is generated by light irradiation or heating, and the aforementioned cross-linking reaction step has many stages. The laminated film of claim 1, wherein the cross-linking reaction promoter contains an acidic substance or a basic substance; the aforementioned acidic substance or basic substance is not produced in the aforementioned precursor forming step; and the aforementioned cross-linking reaction step is performed by light Irradiation or heating produces the aforementioned acidic substance or alkaline substance. The laminated film of claim 1 or 2, wherein in at least one stage after the second stage in the cross-linking reaction step, the cross-linking reaction is generated inside the precursor by heating the precursor. The laminated film of claim 1 or 2, wherein in at least one stage after the second stage in the aforementioned crosslinking reaction step, the strength of the aforementioned precursor is further improved. The laminated film of claim 1 or 2, wherein in at least one stage after the second stage in the crosslinking reaction step, the adhesive peel strength of the precursor to the resin film is further improved. The laminated film of claim 1 or 2, wherein the refractive index of the void layer is less than the value of the refractive index of the precursor plus 0.1. Such as the laminated film of claim 1 or 2, which forms the aforementioned void layer and has a refractive index of 1.25 or less. Such as the laminated film of claim 1 or 2, which forms the aforementioned void layer and has a void ratio of 40% by volume or more. Such as the laminated film of claim 1 or 2, which forms the aforementioned void layer and has a thickness of 0.01 to 100 μm. Such as the laminated film of claim 1 or 2, which forms the aforementioned void layer and makes the haze value less than 5%. The laminated film of claim 1 or 2, wherein the void layer includes a portion where the pulverized products forming a fine void structure are directly or indirectly chemically bonded to each other, and the laminated film is cross-linked to indirectly bond the pulverized products to each other Auxiliary agent, and formed with the aforementioned pulverized material that has been indirectly bonded to each other The aforementioned void layer of the combined part. The laminated film of claim 11, wherein the content of the crosslinking auxiliary agent in the void layer is 0.01 to 20% by weight relative to the weight of the pulverized product. The laminated film of claim 1 or 2, wherein the resin film is a long resin film, and the precursor layer and the void layer are continuously formed on the long resin film. An optical member comprising the laminated film according to any one of claims 1 to 13. An image display device characterized by including an optical member as claimed in claim 14.

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