TW201707946A - Laminate film, optical member, and image display device - Google Patents

Abstract

The purpose of the present invention is to provide a laminate film that has a porous layer and is capable of achieving both high porosity and film strength. This laminate film has a porous layer laminated upon a resin film, said laminate film characterized by being manufactured according to a manufacturing method that includes a precursor forming step for forming, upon the resin film, a porous structure that is a precursor of the porous layer, and a cross-linking reaction step for triggering a cross-linking reaction within the precursor after the precursor forming step. Said laminate film is further characterized in that the precursor includes a substance that generates a basic substance due to light or heat, said basic substance is not generated at the precursor forming step but said basic substance is generated at the cross-linking reaction step as a result of light irradiation or heating, and the cross-linking reaction step has multiple stages.

Description

Method for producing laminated film, laminated film, optical member, image display device, method for manufacturing optical member, and method for manufacturing image display device Technical field

The present invention relates to a laminated film, a method for producing a laminated film, an optical member, an image display device, a method for producing an optical member, and a method for producing the image display device.

Background technique

When two substrates are arranged at regular intervals, the gap between the two substrates becomes an air layer. The air layer formed between the substrates as described above has, for example, a function as a low refractive layer of total reflection light. Therefore, for example, in the case of an optical film, a member such as a ruthenium, a polarizing film, or a polarizing plate is disposed at a constant distance, and an air layer serving as a low refractive index layer can be provided between the members. However, in order to form the air layer in this way, it is necessary to arrange the members at a certain distance, so that it is impossible to laminate the members in order, which makes the manufacturing laborious. In addition, if the optical member is combined by a separator (frame) or the like in order to maintain the air layer, the thickness of the whole becomes large, which is contrary to the requirement of thinness and weight reduction.

In order to solve such a problem, attempts have been made to develop a member that exhibits a film of low refractive index or the like in place of the air layer formed by the gap 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 radical polymerizable monomer and a catalyst and curing it by light irradiation (Patent Document 1). Further, for example, a method of improving the scratch resistance by performing alkali treatment after the formation of the cerium oxide aerogel film (void layer) has been proposed (Patent Document 2).

Prior technical literature Patent literature

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

Patent Document 2: Japanese Laid-Open Patent Publication No. 2009-258711

Summary of invention

However, when the film strength is increased by a catalyst or the like simultaneously with the formation of the void layer, there is a problem that the film strength is increased by the catalyst reaction, but the void ratio is lowered. Further, as described in Patent Document 2, as described above, it is revealed that the alkali treatment is performed after the formation of the void layer, and the film strength is improved. 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 applying an alkali solution, since the solvent resistance of the void layer is low or high water repellency due to the presence of voids, there is a problem that the effect of the alkali solution reaching the inside of the void layer is easily affected. On the other hand, in the method of contacting ammonia gas, there is a problem that the film strength improvement treatment takes too long, and thus the production efficiency is low.

Accordingly, an object of the present invention is to provide a laminated film having a void layer capable of having both a high void ratio and a film strength, a method for producing a laminated film, an optical member, a video display device, a method for producing an optical member, and a method for producing a video display device .

In order to achieve the above object, the laminated film of the present invention has a void layer laminated on the resin film, and is characterized in that it is produced by a production method comprising the step of forming a void on the resin film. a layer precursor, that is, a void structure; and a crosslinking reaction step, after the precursor formation step, a crosslinking reaction is generated inside the precursor; the precursor contains crosslinks which can be used to promote the crosslinking reaction a substance of a reaction accelerator; the foregoing substance generates the crosslinking reaction accelerator by light or heat; the crosslinking reaction accelerator is not produced in the precursor formation step, and the crosslinking reaction step is performed by light irradiation or heating The aforementioned crosslinking reaction accelerator is produced, and the crosslinking reaction step has a plurality of stages.

In the method for producing a laminated film according to the present invention, the laminated film has a void layer laminated on the resin film, and the manufacturing method is characterized by comprising the step of forming a precursor layer on the resin film, that is, a precursor a void structure; and a crosslinking reaction step of generating a crosslinking reaction inside the precursor after the precursor formation step; the precursor comprising a substance capable of generating a crosslinking reaction accelerator for promoting the crosslinking reaction: The foregoing substance generates the aforementioned crosslinking reaction accelerator by light or heat; The crosslinking reaction accelerator is not produced in the precursor formation step; in the crosslinking reaction step, the crosslinking reaction accelerator is generated by light irradiation or heating, and the crosslinking reaction step has a plurality of stages.

The optical member of the present invention comprises the above laminated film of the present invention.

The image display device of the present invention comprises the optical member of the present invention described above.

In the method of producing an optical member according to the present invention, the optical member comprises a laminated film, and the production method comprises the step of producing the laminated film by the method for producing a laminated film of the present invention.

In the method of manufacturing an image display device of the present invention, the image display device includes an optical member, and the manufacturing method includes the step of manufacturing the optical member by the method for producing an optical member of the present invention.

According to the present invention, it is possible to provide a laminated film which can have a void layer having a high void ratio and a film strength, a method for producing a laminated film, an optical member, an image display device, a method for producing an optical member, and a method for producing a video display device. The laminated film of the present invention can be used, for example, in the optical member and image display device of the present invention, but is not limited thereto and can be used for any purpose.

10‧‧‧Substrate

20‧‧‧Precursors (previously treated by cross-linking)

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

20”‧‧‧Sol particle liquid

21‧‧‧void layer

101,201‧‧‧Send rolls

102‧‧‧Application roller

105,241‧‧‧Winding roller

106‧‧‧ Roll

110,210‧‧‧Oven area

111,211‧‧‧Hot air heater (heating device)

120,220‧‧‧Chemical treatment area

121,221‧‧‧ lamps (light irradiation devices) or air heaters (heating devices)

130,230‧‧‧cross-linking reaction zone (aged zone)

131,231‧‧‧Hot air heater (heating device)

202‧‧‧Liquid Storage Department

203‧‧‧Scraper (scraping blade)

204‧‧‧ microgravure

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

Fig. 2 is a view schematically showing a part of the steps of a method for producing a laminated film of the present invention (hereinafter sometimes referred to as "the laminated film roll of the present invention"), and A diagram of an example of a device used therein.

Fig. 3 is a view schematically showing a part of the steps in the method for producing a laminated film roll of the present invention, and another example of the apparatus used therein.

Form for implementing the invention

Hereinafter, the present invention will be specifically described by way of examples. However, the invention is not limited or limited by the following description. The laminated film of the present invention may be a laminated film of the present invention (the laminated film roll of the present invention) as described above. The laminated film roll of the present invention may, for example, be cut out as a laminated film of the present invention. Hereinafter, in the case of "the laminated film of the present invention", the laminated film roll of the present invention is also included unless otherwise specified. Similarly, the "manufacturing method of the laminated film of the present invention" is hereinafter referred to as a method for producing a laminated film roll of the present invention unless otherwise specified.

In the method for producing a 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 alkaline substance is not produced in the aforementioned precursor formation step, and in the aforementioned crosslinking reaction step, the aforementioned acidic substance or alkaline substance is produced by light irradiation or heating.

In the method for producing a laminated film according to the present invention, for example, in at least one stage after the second stage of the crosslinking reaction step, a crosslinking reaction is generated inside the precursor by heating the precursor. Further, in the present invention, the crosslinking reaction step has a plurality of stages as described above, and specifically, may be two stages or three stages or more.

At least one after the second stage of the aforementioned crosslinking reaction step In the stage, for example, the strength of the aforementioned precursor can be further increased. Further, in at least one stage after the second stage of the crosslinking reaction step, for example, the adhesion peeling strength of the precursor to the resin film can be further increased.

In the method for producing a laminated film of the present invention, as described above, the precursor contains a substance which generates a basic substance by light or heat, and in the precursor forming step, the alkalinity is generated by light irradiation or heating. substance.

In the method for producing a laminated film of the present invention, the void layer may include, for example, a portion directly or indirectly chemically bonded by one or more constituent units forming a fine void structure. Further, for example, in the above-mentioned void layer, even if the constituent unit is in contact, there may be a portion which is not chemically bonded. Further, in the present invention, the "indirect bonding" of the constituent units means that the constituent units are bonded by a small amount of the binder component which is less than the constituent unit amount. The "direct bond" of the constituent unit means that the constituent unit is directly bonded without being bonded to the binder component or the like. The combination of the above constituent units may be, for example, a combination of a catalytic action. The combination of the aforementioned constituent units may include, for example, a hydrogen bond or a covalent bond. In the present invention, the constituent unit forming the void layer may be formed, for example, by a structure having at least one of a particle shape, a fiber shape, and a flat shape. The constituent elements of the particulate form and the flat shape may be formed of, for example, an inorganic material. Further, the constituent elements of the particulate constituent unit may include, for example, at least one element selected from the group consisting of Si, Mg, Al, Ti, Zn, and Zr. The structural body (constituting unit) which forms a particle shape may be a solid particle or a hollow particle, and specifically, a polyoxynium particle or a polysiloxane particle having a micropore, Examples of cerium oxide hollow nanoparticles or cerium oxide hollow nanospheres are exemplified. The fibrous constituent unit is, for example, a nanofiber having a diameter of a nanometer, and specific examples thereof include cellulose nanofibers and alumina nanofibers. The flat-shaped constituent unit is exemplified by a nano-clay, and specifically, a nano-sized benton (for example, Kunipia F "trade name") or the like can be exemplified. The fibrous constituent unit is not particularly limited, but may be, for example, selected from the group consisting of carbon nanofibers, cellulose nanofibers, alumina nanofibers, chitinite fibers, chitin nanofibers, and polymer naphthalenes. At least one fibrous substance of the group consisting of rice fibers, glass nanofibers, and cerium oxide nanofibers. Further, the above constituent unit may be, for example, fine pore particles. For example, the void layer is a porous body in which fine pore particles are chemically bonded, and in the step of forming the void layer, for example, the fine pore particles may be chemically bonded. Further, in the present invention, the shape of the "particles" (for example, the above-mentioned fine pore particles) is not particularly limited, and may be, for example, a spherical shape or another shape. Further, in the present invention, the fine pore particles may be, for example, sol gel beaded particles, nano particles (hollow nano cerium oxide, nanosphere particles), or nanofibers, as described above. In the method for producing a laminated film according to the present invention, the fine pore particles are, for example, fine pore particles of a ruthenium compound, and the porous system is a porous polysiloxane. The fine pore particles of the above ruthenium compound include, for example, a pulverized body of a gelatinous cerium oxide compound. Further, another aspect of the void layer includes a void layer formed of a fibrous material such as nanofibers, and the fibrous material is entangled to form a layer in the form of a void. The method for producing the void layer is not particularly limited, but may be the same as the void layer of the porous body chemically bonded to the fine pore particles, for example. Furthermore, as mentioned earlier, it also includes A void layer comprising hollow layer particles or nano-clay, a hollow layer formed using hollow nanospheres or magnesium fluoride. Further, the void layer may be a void layer formed of a single constituent material, or may be a void layer formed of a plurality of constituent materials. Further, the form of the void layer may be a single form as described above, or may be a void layer formed by most of the above aspects. Hereinafter, the void layer of the porous body chemically bonded to the fine pore particles will be mainly described.

In the method for producing a laminated film according to the present invention, for example, the fine pore particles are fine pore particles of a ruthenium compound, and the porous system is a porous polysiloxane.

In the method for producing a laminated film of the present invention, for example, the fine pore particles of the cerium compound include a pulverized body of a gelled cerium oxide compound.

In the method for producing a laminated film according to the present invention, for example, the porous structure of the porous body has a continuous pore structure.

The method for producing a laminated film of the present invention further includes a step of preparing a liquid containing a liquid containing the fine pore particles, a coating step of applying the liquid containing the resin film, and drying the applied coating liquid. In the drying step, and in the crosslinking reaction step, the microporous particles are chemically bonded.

In the method for producing a laminated film of the present invention, for example, in the crosslinking reaction step, the fine pore particles are chemically bonded 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 above-mentioned catalyst, and the fine pore particles can be chemically bonded by the action of the crosslinking reaction accelerator.

In the method for producing a laminated film of the present invention, for example, in the crosslinking reaction step, the fine pore particles are chemically bonded by light irradiation.

In the method for producing a laminated film of the present invention, for example, in the crosslinking reaction step, the fine pore particles are chemically bonded by heating.

In the method for producing a laminated film according to the present invention, for example, the refractive index of the void layer is equal to or less than a value obtained by adding 0.1 to the refractive index of the precursor.

In the method for producing a laminated film of the present invention, for example, the void layer is formed to have a refractive index of 1.25 or less.

In the method for producing a laminated film of the present invention, for example, the void layer is formed to have a void ratio of 40% by volume or more.

In the method for producing a laminated film of the present invention, for example, the void layer is formed to have a thickness of 0.01 to 100 μm.

The method for producing a laminated film of the present invention is, for example, to form the above-mentioned void layer and to have a haze value of less than 5%.

In the method for producing a laminated film of the present invention, for example, the void layer is formed, and the adhesion peeling strength of the void layer to the resin film is 1 N/25 mm or more.

In the method for producing a laminated film of the present invention, for example, the resin film is a long resin film, and the precursor and the void layer are continuously formed on the resin film. Further, in the method for producing a laminated film of the present invention, for example, a laminated film of the laminated film roll (the laminated film roll of the present invention) prepared as described above may be cut out as a laminated film of the present invention.

The laminated film roll of the present invention is not particularly limited in its production method, but may be, for example, a laminate film roll of the present invention. Method of manufacturing a laminated film roll. Further, the laminated film roll of the present invention is not particularly limited, and may be, for example, a laminated film produced by the method for producing a laminated film of the present invention.

Hereinafter, the present invention will be more specifically described.

[1. Laminate film and its manufacturing method]

The method for producing a laminated film of the present invention comprises, as described above, a precursor forming step of forming a void layer before forming a void layer on the resin film, and a crosslinking structure, and a crosslinking reaction step after the precursor forming step A cross-linking reaction is generated inside the aforementioned precursor. Further, the laminated film of the present invention is a laminated film produced by the above-described method for producing a laminated film of the present invention as described above. The laminated film of the present invention may be, for example, a long laminated film roll (the laminated film roll of the present invention).

[1-1. Laminate film]

In the laminated film of the present invention, the resin film is not particularly limited, and examples of the resin include polyethylene terephthalate (PET), acrylic, cellulose acetate propionate (CAP), and cyclic olefin. A thermoplastic resin having excellent transparency such as polymer (COP), triacetate (TAC), polyethylene naphthalate (PEN), polyethylene (PE), or polypropylene (PP).

The void layer (hereinafter referred to as "the void layer of the present invention") in the laminated film roll or the laminated film of the present invention may be directly laminated on the resin film, or may be passed through another laminated layer.

The laminated film of the present invention may be, for example, a low refractive material which is characterized by including the void layer and the resin film, and the void layer is laminated on the resin film and has the above characteristics.

The void layer of the present invention, for example, the residual resistance of the BEMCOT (registered trademark) scratch resistance test showing the film strength is 60 to 100%. If it has such a film strength, it is also strong, for example, for physical impact during winding or use at the time of manufacture. The lower limit of the 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, 98% or less, and the range is, for example, 60 to 100%, 80 to 99%. 90 to 98%.

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

(Evaluation of scratch resistance)

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

(2) The above-mentioned void layer which was subjected to the scratch resistance test of the above (1) was visually evaluated for scratch resistance. The number of damages after the scratch resistance test was evaluated as ○ if it was 0 to 9, and was evaluated as △ if it was 10 to 29, and × when it was 30 or more.

In the void layer of the present invention, the film density is not particularly limited, and the lower limit thereof is, for example, 1 g/cm ³ or more, 10 g/cm ³ or more, 15 g/cm ³ or more, and the upper limit thereof is, for example, 50 g/cm ³ or less, 40 g/cm. ³ or less, 30 g/cm ³ or less, 2.1 g/cm ³ or less, and the range thereof 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 . Further, in the void layer of the present invention, 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 and 95% or less, depending on the film density, and the range is For example, 50 to 98%, 70 to 95%, and 85 to 95%.

The film density can be measured, for example, by the following method, and the porosity can be calculated as follows, for example, based on the film density.

(Evaluation of film density and porosity)

After forming a void layer (the void layer of the present invention) on the substrate (acrylic film), the total reflection region was measured using the X-ray diffraction apparatus (RINT-2000, manufactured by RIGAKU Co., Ltd.) on the void layer of the laminate. X-ray reflectivity. Then, after the fitting of the intensity (Intensity) and 2θ, the film density (g/cm ³ ) is calculated from the total reflection critical angle of the laminate (void layer, substrate), and then the porosity is calculated by the following formula ( P%).

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

The void layer of the present invention, for example, has a pore structure. The void size of the aforementioned pores means the long axis diameter of the major axis diameter and the minor axis diameter of the void (hole). The pore size is not particularly limited, but is, for example, 2 nm to 500 nm. The lower limit of the void size is, for example, 2 nm or more, 5 nm or more, 10 nm or more, 20 nm or more, and the upper limit is, for example, 500 nm or less, 200 nm or less, or 100 nm or less, and the range is, for example, 2 nm to 500 nm, 5 nm to 500 nm, 10 nm to 200 nm, and 20 nm. To 100nm. The void size can be determined by the use of the void structure to determine the desired void size, and therefore, for example, must be adjusted to the desired void size. The void size can be evaluated, for example, by the following method.

(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 placed in a capillary tube of a specific surface area measuring device (manufactured by MICROMERITICS: ASAP2020) Thereafter, the mixture was dried under reduced pressure at room temperature for 24 hours to degas the gas in the void structure. Next, nitrogen gas was adsorbed on the sample to draw an adsorption isotherm, and a pore distribution was obtained. Thereby, the void size can be evaluated.

The void layer of the present invention may have a pore structure (porous structure) as described above, for example, and may be a continuous foam structure of the above pore structure. The above-mentioned continuous foam structure means, for example, that the pore structure is three-dimensionally connected in the porous polysiloxane porous body, that is, the internal void of the pore structure is continuous. When the porous body has a continuous foam structure, the porosity of the whole body may be increased, but when a single foam particle such as hollow ceria is used, a continuous foam structure cannot be formed. On the other hand, in the void layer of the present invention, for example, when cerium oxide sol particles (a pulverized product of a gel-like cerium compound forming a sol) are used, the particles have a three-dimensional tree structure, and the coating film (including the gelatinous shape described above) In the coating film of the pulverized product of the cerium compound, since the dendritic particles are deposited and deposited, the vesicle structure can be easily formed. Further, more preferably, the void layer of the present invention is preferably formed into a monolithic structure in which the continuous structure of the foam has a large pore distribution. The monolithic structure refers to, for example, a structure in which fine voids having a nanometer size exist, and a hierarchical structure in which a continuous bubble structure of the same nanovoid set is formed. When the monolithic structure is formed, for example, the film strength is imparted by the fine voids, and the high porosity is provided by the coarse continuous voids, so that the film strength and the high porosity can be achieved. In order to form the monolithic structure, for example, it is preferred to first control the pore distribution of the resulting void structure in the gel (gelatinous ruthenium compound) at the stage before the pulverization into the cerium oxide sol particles. Further, for example, when the gel-like cerium compound is pulverized, the particle size distribution of the pulverized cerium oxide sol particles is controlled to a desired size, whereby the aforementioned monolith can be formed. structure.

In the void layer of the present invention, the haze showing transparency is not particularly limited, and the upper limit thereof is, for example, less than 5% or less than 3%. Further, 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%, 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 the haze was measured in a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.: HM-150). The haze value was calculated by the following formula.

Haze (%) = [Diffuse Transmittance (%) / Total Light Transmittance (%)] × 100 (%)

The refractive index is generally referred to as the ratio of the propagation velocity of the optical wavefront in the vacuum to the propagation velocity in 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, or 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 and 1.25 or less, and 1.06 or more and 1.20 or less. , 1.07 or more to 1.15 or less.

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

(evaluation of refractive index)

After forming a void layer (the void layer of the present invention) on the acrylic film, it was cut into a size of 50 mm × 50 mm, and adhered to the surface of the glass plate (thickness: 3 mm) by an adhesive layer. Paint the back of the glass plate with a black marker The central portion (about 20 mm in diameter) modulates a sample that is not reflected on the back surface of the aforementioned glass plate. The sample was placed in an ellipsometer (manufactured by J.A. Woollam Japan Co., Ltd.: VASE), and 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 resin film, for example, the adhesive peeling strength showing adhesion to the resin film is not particularly limited, and the lower limit is, for example, 1 N/25 mm or more, 2 N/25 mm or more, and 3 N/25 mm or more. The upper limit thereof is, for example, 30 N/25 mm or less, 20 N/25 mm or less, 10 N/25 mm or less, and the range thereof is, for example, 1 to 30 N/25 mm, 2 to 20 N/25 mm, and 3 to 10 N/25 mm.

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

(Evaluation of adhesive peel strength)

The laminated film of the present invention was formed into a rectangular sample of 50 mm × 140 mm, and the sample was fixed to a stainless steel plate by a double-sided tape. Adhesive adhesive layer (thickness: 20 μm) was adhered to a PET film (T100: manufactured by MITSUBISHI PLASTIC FILM Co., Ltd.), and then an adhesive tape sheet cut into 25 mm × 100 mm was adhered to the void layer of the laminated film of the present invention. The laminate of the aforementioned PET film. Then, the sample was placed on an automatic drawing tensile tester (AG-Xplus, manufactured by Shimadzu Corporation) 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. The average test force of the 50 mm peel test was performed as the adhesive peel strength.

The thickness of the void layer of the present invention is not particularly limited, and the lower limit thereof is For example, 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, and 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 is, for example, 0.01 to 1000 μm.

The void layer of the present invention contains, for example, a pulverized product of a gel-like compound as described above, and the pulverized material is chemically bonded. In the void layer of the present invention, the form of chemical bonding (chemical bond) of the pulverized material is not particularly limited, and specific examples of the chemical bond may be, for example, a cross-linking bond. Further, a method of chemically bonding the aforementioned pulverized material is described in detail in the production method of the present invention.

The gel form of the aforementioned gelatinous compound is not particularly limited. "Gel" generally means a state in which a solute has a structure that is aggregated due to loss of independent mobility of the interaction and solidifies. Further, in the gel, generally, the wet gel contains a dispersion medium and the solute has the same structure in the dispersion medium, while the dry gel removes the solvent and the solute has a mesh structure having voids. In the present invention, the gelatinous compound may be, for example, a wet gel or a dry gel.

The gelled compound may be exemplified by a gelled compound in which a monomer compound is gelated. Specifically, the gel-like ruthenium compound is exemplified by a gelled product in which the ruthenium compounds of the above monomers are bonded to each other, and specific examples thereof include a gelled product in which the ruthenium compound is hydrogen-bonded or intermolecularly bonded to each other. example. The above combination may be exemplified by a combination of dehydration condensation. The aforementioned method of gelation is described later in the production method of the present invention.

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

Further, the particle size distribution showing the particle size deviation of the foregoing pulverized material is not particularly limited, for example, a particle diameter of 0.4 μm to 1 μm is 50 to 99.9% by weight, 80 to 99.8% by weight, 90 to 99.7% by weight, or a particle diameter of 1 μm to 2 μm. The particles are from 0.1 to 50% by weight, from 0.2 to 20% by weight, and from 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 kind of the gelled compound is not particularly limited. The gelled compound may be exemplified by a gelatinous quinone compound. Hereinafter, the case of a gelatinous compound-based gelatinous quinone compound will be described as an example, but the present invention is not limited thereto.

The aforementioned crosslinking bond is, for example, a decane bond. The oxime bond can be exemplified by the T2 bond, the T3 bond, and the T4 bond shown below. When the void layer of the present invention has a decane bond, for example, it may have any kind of bond, may have any two types, or may have all three kinds of bonds. Among the above-mentioned oxane bonds, the higher the ratio of T2 and T3, the higher the flexibility, so that the original properties of the gel can be expected, but the film strength is weak. On the other hand, when the ratio of T4 in the above-mentioned decane bond is large, the film strength is easily exhibited, but the void size is small, and thus the flexibility is lowered. Therefore, for example, it is preferable to change the ratio of T2, T3, and T4 depending on the use.

[Chemical 1]

When the void layer of the present invention has the above-described decane bond, the ratio of T2, T3, and T4 is, for example, when T2 is relatively "1", and T2: T3: T4 = 1: [1 to 100]: [0 to 50], 1: [1 to 80]: [1 to 40], 1: [5 to 60]: [1 to 30].

Further, the void layer of the present invention, for example, a ruthenium atom preferably contained, is subjected to a decane bond. Specifically, in the total ruthenium atom contained in the void layer, the ratio of unbound ruthenium atoms (that is, residual stanol) is, for example, less than 50%, 30% or less, and 15% or less.

When the gelled compound is the gelatinous quinone compound, the quinone compound of the above monomer is not particularly limited. The oxime compound of the above monomer is exemplified by a compound represented by the following formula (1). When the ruthenium compound of the gelled ruthenium compound-based monomer is hydrogen-bonded or intermolecularly bonded to each other as described above, the monomers of the formula (1) may, for example, be permeable to each of the hydroxy groups. .

In the above 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 above R ¹ is, for example, 1 to 6, 1 to 4, and 1 to 2. The linear alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group; and the above branched alkyl group may, for example, be an isopropyl group or an isobutyl group. The aforementioned X system is, for example, 3 or 4.

Specific examples of the ruthenium compound represented by the above formula (1) are exemplified by the compound represented by the following formula (1'). In the following formula (1'), R ^{1 is the} same as the above formula (1), and is, for example, a methyl group. When R ¹ is a methyl group, the above hydrazine compound is tris(hydroxy)methylnonane. In the case of the above X system 3, the oxime compound is, for example, a trifunctional decane having a trifunctional group.

Further, specific examples of the ruthenium compound represented by the above formula (1) are exemplified by the compound of the X system 4. In this case, the aforementioned hydrazine compound is, for example, a 4-functional decane having a 4-functional group.

The oxime compound of the above monomer may be, for example, a hydrolyzate of a ruthenium compound precursor. The ruthenium compound precursor may be, for example, a ruthenium compound which can be produced by hydrolysis. Specific examples thereof include a compound represented by the following formula (2).

[Chemical 4]

In the above formula (2), for example, X system 2, 3 or 4, R ¹ and R ² are each a linear or branched alkyl group, and R ¹ and R ² are the same or different, and in the case of X system 2, R ¹ R ² are the same or different from each other to be the same or different from each other.

The above X and R ^{1 are} , for example, the same as X and R ¹ in the above formula (1). Further, as the aforementioned R ² , for example, an example of R ¹ in the formula (1) can be used.

Specific examples of the ruthenium compound precursor represented by the above formula (2) include a compound represented by the following formula (2') of the X system 3 as an example. In the following formula (2'), R ¹ and R ² are each the same as the above formula (2). When R ¹ and R ² are a methyl group, the ruthenium compound precursor is trimethoxy(methyl)decane (hereinafter also referred to as "MTMS").

The above-mentioned monomeric ruthenium compound is preferably a trifunctional decane, for example, from the viewpoint of having excellent low refractive index. Further, the above-mentioned monomeric ruthenium compound is preferably the above-mentioned 4-functional decane from the viewpoint of excellent strength (for example, scratch resistance). In addition, as the aforementioned gelatinous bismuth compound The ruthenium compound of the above-mentioned monomer of the raw material may be used singly or in combination of two or more kinds. Specific examples of the above-mentioned monomeric ruthenium compound may include only the above-mentioned trifunctional decane, and may include only the above-mentioned tetrafunctional decane, and may include both the above-mentioned trifunctional decane and the above-mentioned tetrafunctional decane, and may further contain other ruthenium compounds. When two or more kinds of ruthenium compounds are used as the ruthenium compound of the above monomers, the ratio is not limited and can be appropriately set.

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 may be, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight based on the weight of the aforementioned constituent unit.

Further, 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 crosslinking auxiliary agent is not particularly limited, but may be, for example, 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 10% by weight based on the weight of the aforementioned constituent unit.

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

The void layer of the present invention is, for example, a wound body. Further, the void layer of the present invention further includes, for example, a resin film as described above, and the void layer can be formed on the long resin film. In this case, another long film may be laminated on the laminated film of the present invention, or another long resin film may be laminated on the laminated film of the present invention comprising the resin film and the void layer (for example, insulating After paper, release paper, surface protection film, etc.) The form of the roll is rolled into a roll.

The method for producing the laminated film of the present invention is not particularly limited, and can be produced, for example, by the production method of the present invention shown below.

[1-2. Method of Manufacturing Laminate Film]

The method for producing a laminated film of the present invention comprises the steps of: a precursor forming step of forming a void layer before the formation of a void layer on the resin film, that is, a void structure; and a crosslinking reaction step in the precursor forming step Thereafter, a crosslinking reaction is generated inside the aforementioned precursor.

In the method for producing a laminated film of the present invention, for example, as described above, the void layer is a porous body in which fine pore particles are chemically bonded, and in the precursor formation step, the fine pore particles are chemically bonded. The method for producing a laminated film of the present invention further includes, as described above, a step of preparing a liquid containing a liquid containing the fine pore particles, and a drying step of drying the liquid containing the liquid, and in the step of forming the precursor, The microporous particles in the dried body are chemically bonded to form the porous body precursor. The liquid containing the fine pore particles (hereinafter referred to as "microporous particle-containing liquid" or simply "containing liquid") is not particularly limited, and may be, for example, a suspension containing the fine pore particles. In the following, the pulverized material of the fine pore particle-based gel-like compound is mainly described, and the void layer is a porous body (preferably a porous oxyporous body) containing a pulverized product of a gel-like compound. However, when the fine pore particles of the present invention are other than the pulverized material of the gelled compound, the same can be carried out in the same manner.

According to the manufacturing method of the present invention, for example, excellent display can be formed a low refractive index void layer. The reason for this is estimated, for example, as follows, but the present invention is not limited to this estimation.

The pulverized material used in the production method of the present invention is obtained by pulverizing the gelatinous ruthenium compound, and the three-dimensional structure of the gelatinous ruthenium compound before the pulverization is dispersed in a three-dimensional basic structure. Further, in the production method of the present invention, the porous structure precursor can be formed in accordance with the three-dimensional basic structure by applying the pulverized product of the gelatinous ruthenium compound onto the substrate. That is, according to the production method of the present invention, a new porous structure formed of the pulverized material of the three-dimensional basic structure different from the three-dimensional structure of the gel-like bismuth compound can be formed. Therefore, the aforementioned void layer finally obtained, for example, may have a low refractive index which is equivalent to the function of the air layer. Further, in the production method of the present invention, the new three-dimensional structure can be fixed by further chemically bonding the pulverized material. Therefore, the void layer finally obtained has a structure of voids, but maintains sufficient strength and flexibility. As described above, the void layer obtained by the production method of the present invention is useful as a substitute for the air layer in terms of low refractive power and strength and flexibility. Further, in the case of the above air layer, for example, it is necessary to form a gap by inserting a separator or the like between the member and the member, and an air layer is formed between the members. However, the void layer obtained by the production method of the present invention can exhibit low refractive properties similar to those of the air layer, for example, by being disposed only at a target portion. Therefore, as described above, the low refractive index of, for example, the optical member can be imparted with the same degree of function as the air layer more easily and simply than the formation of the air layer.

Further, the present invention performs a precursor formation step of forming a void structure of the precursor layer before the void layer, and a crosslinking reaction step of generating a crosslinking reaction inside the precursor after the precursor formation step as another step. Further, the aforementioned crosslinking reaction step is carried out in a plurality of stages. By performing the above-described crosslinking reaction step in a plurality of stages, for example, the strength of the precursor can be further improved by performing the crosslinking reaction step in one stage, so that the present invention having both high void ratio and strength can be obtained. Void layer. Although the institution is unknown, for example, it is presumed as follows. In other words, as described above, when the film strength is increased by a catalyst or the like simultaneously with the formation of the void layer, there is a problem that the film strength is increased by the catalyst reaction, but the void ratio is lowered. This is because, for example, the cross-linking reaction of the fine pore particles of the catalyst increases the number of cross-linking (chemical bonding) of the fine pore particles, so that the bonding becomes strong, but the entire void layer is condensed to lower the void ratio. On the other hand, by performing the above-described precursor formation step and the crosslinking reaction step as another step, and performing the crosslinking reaction step in a plurality of stages, it is estimated that, for example, the morphology of the entire precursor can be hardly changed. The cross-linking (chemical bonding) number is increased in the case of (for example, almost no overall condensation is produced). However, this is only one example of a speculative mechanism, and is not intended to limit the invention.

In the precursor formation step, for example, although the particles having a certain shape are laminated and the void layer precursor is formed, the strength of the precursor at this time is extremely weak. Then, for example, by a reaction with light or a thermal active catalyst, a crosslinking accelerator capable of chemically bonding the aforementioned fine pore particles (for example, a strong base catalyst produced by a photobase generator) is produced (the first step of the crosslinking reaction step) One stage). To react more efficiently in a short period of time, by further The heat aging (second stage of the crosslinking reaction step) is carried out, and it is presumed that the fine pore particles further undergo chemical bonding (crosslinking reaction) and increase the strength. In the specific example, the fine pore particles are fine pore particles of a ruthenium compound (for example, a pulverized body of a gelled cerium oxide compound), and in the case where a residual stanol group (OH group) exists in the precursor, it is presumed that The aforementioned residual stanol groups are chemically bonded by a crosslinking reaction. However, the description is intended to be illustrative, not limiting.

The method for producing the laminated film of the present invention can be applied to the description of the void layer and the laminated film of the present invention unless otherwise specified.

In the method for producing a laminated film of the present invention, the gel-like compound and the pulverized product thereof, the monomer compound, and the monomer compound precursor may be referred to the description of the void layer and the laminated film of the present invention.

The method for producing the laminated film of the present invention can be carried out, for example, as follows, but is not limited thereto.

The method for producing a laminated film of the present invention has, for example, a production liquid preparation step of preparing a liquid containing the fine pore particles as described above. When the fine pore particles are a pulverized product of a gel-like compound, the pulverized material is obtained by, for example, pulverizing the gel-like compound. By pulverizing the gel-like compound, as described above, the three-dimensional structure of the gelled compound can be destroyed and dispersed into a three-dimensional basic structure.

Hereinafter, the gelatinous compound is produced by gelation of the above-mentioned monomer compound, and the pulverized product is prepared by pulverizing the gelled compound, but the present invention is not limited to the following examples.

Gelation of the aforementioned monomer compound, for example, by The monomer compounds are bonded to each other by hydrogen bonding or intermolecular force bonding.

The above-mentioned monomer compound is exemplified by the hydrazine compound represented by the above formula (1) described in the above-mentioned void layer of the present invention.

Since the oxime compound of the above formula (1) has a hydroxyl group, the monomers of the above formula (1) can be bonded, for example, via respective hydroxy hydrogen bonding or intermolecular force.

Further, the ruthenium compound may be a hydrolyzate of the ruthenium compound precursor as described above, and may be produced, for example, by hydrolysis of the ruthenium compound precursor represented by the above formula (2) described in the void layer of the present invention.

The hydrolysis method of the aforementioned monomer compound precursor is not particularly limited and, for example, can be carried out by a chemical reaction in the presence of a catalyst. The catalyst may be exemplified by an acid such as oxalic acid or acetic acid. The hydrolysis reaction can be carried out, for example, by slowly dropping an aqueous solution of oxalic acid in a mixture (for example, a suspension) of the above-mentioned hydrazine compound and dimethyl hydrazine at room temperature, followed by stirring immediately for about 30 minutes. . When the precursor of the ruthenium compound is hydrolyzed, for example, by completely hydrolyzing the alkoxy group of the precursor of the ruthenium compound, it is possible to more efficiently express the subsequent gelation, aging, and heating and immobilization after formation of the void structure.

The gelation of the above monomer compound can be carried out, for example, by a dehydration condensation reaction between the above monomers. The dehydration condensation reaction is preferably carried out, for example, in the presence of a catalyst, and the catalyst may, for example, be an acid catalyst such as hydrochloric acid, oxalic acid or sulfuric acid, or an alkali contact such as ammonia, potassium hydroxide, sodium hydroxide or ammonium hydroxide. A dehydration condensation catalyst such as a medium (basic catalyst). The above dehydration condensation catalyst is particularly preferred as a base catalyst. In the above dehydration condensation reaction, the amount of the monomer compound added to the above-mentioned catalyst is not particularly limited, and the catalyst may be, for example, 0.1 to 10 mol, 0.05 to 7 mol, per 1 mol of the monomer compound. 0.1 to 5 moles.

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

The conditions of the aforementioned gelation are not particularly limited. The treatment temperature for the aforementioned solvent containing the aforementioned monomer compound may be, for example, 20 to 30 ° C, 22 to 28 ° C, 24 to 26 ° C, and the treatment time may be, for example, 1 to 60 minutes, 5 to 40 minutes, 10 to 30 minutes. . When the dehydration condensation reaction is carried out, the treatment conditions are not particularly limited, and such examples can be used. By performing the gelation, for example, a siloxane chain is grown to form ceria primary particles, and the reaction is further carried out, whereby the primary particles are connected in a bead shape to form a three-dimensional gel.

The gelatinous compound obtained by the gelation described above is preferably subjected to a ripening treatment after the gelation reaction. By the above-described ripening 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 in contact with the particles can be made. Increase from point contact to face contact. The gel which has been subjected to the ripening treatment as described above, for example, the strength of the gel itself is increased, and as a result, the strength of the three-dimensional basic structure after the pulverization can be improved. Thereby, for example, it is possible to suppress shrinkage of the pore structure of the void structure in which the three-dimensional basic structure is deposited in the drying step after the application of the pulverized material, with the solvent volatilization in the drying process.

The aforementioned ripening treatment is carried out, for example, by holding the gelled compound at a predetermined temperature for a predetermined time. The predetermined temperature is not particularly limited, and the lower limit is, for example, 30° C. or higher, 35° C. or higher, or 40° C. or higher, and the upper limit thereof is, for example, 80° C. or lower, 75° C. or lower, or 70° C. or lower, and the range is, for example, 30 to 80° C., 35 to 75 ° C, 40 to 70 ° C. The predetermined period of time is not particularly limited, and the lower limit is, for example, 5 hours or longer, 10 hours or longer, or 15 hours or longer, and the upper limit thereof is, for example, 50 hours or shorter, 40 hours or shorter, 30 hours or shorter, and the range is, for example, 5 to 50 hours. 10 to 40 hours, 15 to 30 hours. Further, the most suitable conditions for the ripening are, for example, the main purpose of increasing the size of the primary particle of the ceria and increasing the contact area of the mesh portion. Further, it is preferable to consider the boiling point of the solvent to be used. For example, if the temperature of the ripening is too high, the solvent is excessively volatilized, and there is a possibility that the pores of the three-dimensional void structure are closed by concentration of the concentration of the coating liquid (gel liquid). On the other hand, for example, when the ripening temperature is too low, not only cannot be sufficiently obtained before The effect of the ripening process, the temperature deviation of the mass production process after a period of time also increases, and it is possible to produce a product of poor quality.

For the above-mentioned ripening treatment, for example, the same solvent as the gelation treatment described above can be used. Specifically, the reaction product after the gel treatment (that is, the solvent containing the gelled compound) is preferably carried out as it is. The molar amount of the remaining stanol group contained in the gel (the gelled compound, for example, the gelatinous quinone compound) after completion of the gelation treatment, for example, the added raw material (for example, the aforementioned monomer compound) The ratio of the residual stanol group in the case where the alkoxy group number of the precursor is 100 is, for example, 1% or more, 3% or more, or 5% or more, and the upper limit thereof is, for example, 50% or less and 40% or less. It is 30% or less, and its range is, for example, 1 to 50%, 3 to 40%, and 5 to 30%. In order to increase the hardness of the gel, for example, the lower the number of moles of the residual stanol group, the better. If the number of moles of the stanol group is too high, for example, it is possible to maintain the void structure until the precursor of the polysiloxane porous body is crosslinked. On the other hand, if the number of moles of the stanol group is too low, for example, the step of preparing the fine pore particle-containing liquid (for example, a suspension) and/or the subsequent step, the pulverized product of the gelled compound cannot be crosslinked, It may not be possible to impart sufficient film strength. Further, in the case of the above-described stanol group, for example, when a ruthenium compound of a monomer is modified with various reactive functional groups, the same phenomenon can be applied to each functional group.

After the monomer compound is gelated in the solvent for gelation, the obtained gelatinous compound is pulverized. In the above-mentioned pulverization system, for example, the gelled compound in the solvent for gelation may be pulverized as it is, or another solvent may be substituted for the solvent for gelation, and the above-mentioned pulverization agent may be used. The gelatinous compound in the solvent is subjected to pulverization treatment. In addition, for example, the catalyst used in the gelation reaction and the solvent used may remain after the ripening step, and when the liquid is gelled after a period of time (lifespan) and the drying efficiency is lowered during the drying step, other Solvent substitution. Hereinafter, the other solvent is also referred to as "solvent solvent".

The solvent for pulverization is not particularly limited, and for example, an organic solvent can be used. The organic solvent may be exemplified by a solvent having 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 thereof include isopropyl alcohol (IPA), ethanol, methanol, butanol, propylene glycol monomethyl ether (PGME), methyl sarxin, acetone, dimethylformamide (DMF), and the like. The solvent for pulverization may be used alone or in combination of two or more.

The combination of the solvent for gel and the solvent for pulverization is not particularly limited, and examples thereof include a combination of DMSO and IPA, a combination of DMSO and ethanol, DMSO and methanol, DMSO and butanol, and the like. By substituting the solvent for the gel by the solvent for pulverization, for example, when a coating film is formed later, a more uniform coating film can be formed.

The pulverization method of the gelled compound is not particularly limited, and can be carried out, for example, by an ultrasonic homogenizer, a high-speed rotary homogenizer, a pulverization apparatus using another hollowing phenomenon, or a pulverizing apparatus which causes liquid oblique collision under high pressure. A device for pulverizing a medium such as a ball mill, for example, physically rupturing the void structure of the gel during pulverization, and a preferred clogging device of the present invention, such as a homogenizer, can be driven by a high speed, for example, by a medium-free method. The shear stripping has been incorporated into the weakly bonded cerium oxide particle interface of the three-dimensional structure of the gel. Thereby, the three-dimensional structure of the sol is obtained, For example, a void structure having a certain range of particle size distribution can be maintained, and a void structure resulting from deposition during coating and drying can be formed. The conditions of the pulverization are not particularly limited. For example, it is preferred to pulverize the gel without volatilizing the solvent by instantaneously imparting a high-speed flow. For example, it is preferred to pulverize into a pulverized material having a particle size deviation (for example, a volume average particle diameter or a particle size distribution) as described above. When the amount of work such as pulverization time and strength is insufficient, for example, not only coarse particles but also dense pores cannot be formed, and appearance defects are also increased, and high quality may not be obtained. On the other hand, when the amount of work is too large, for example, the sol particles are finer than the desired particle size distribution, and the void size deposited after application and drying becomes fine, and the desired porosity may not be satisfied.

As described above, a liquid (for example, a suspension) containing the above-mentioned fine pore particles (pulverized product of a gel-like compound) can be produced. Further, after the liquid containing the fine pore particles is produced, or a catalyst for chemically bonding the fine pore particles is added during the production, a liquid containing the fine pore particles and the catalyst can be produced. The amount of the catalyst to be added is not particularly limited, but is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight based on the weight of the fine pore particles (pulverized product of the gelled compound). The catalyst may be, for example, a catalyst (crosslinking reaction accelerator) that promotes cross-linking of the fine pore particles. The chemical reaction for chemically bonding the aforementioned fine pore particles is preferably carried out by a dehydration condensation reaction of a residual stanol group contained in the cerium oxide sol molecule. By promoting the reaction of the hydroxyl group of the stanol group with the above-mentioned catalyst, the void structure can be hardened and continuously formed into a film in a short time. The catalyst may be exemplified by a photoactive catalyst and a thermally active catalyst. If the aforementioned photoactive catalyst is used, for example, in the aforementioned precursor formation step, without heating The aforementioned microporous particles are chemically bonded (for example, crosslinked). Thereby, for example, in the precursor formation step, since the shrinkage of the entire precursor is less likely to occur, a higher void ratio can be maintained. Further, in addition to the above-mentioned catalyst, a substance (catalyst generating agent) which generates a catalyst may be additionally used or substituted for the above-mentioned catalyst. For example, the catalyst may be a crosslinking reaction accelerator, and the catalyst generator may be a substance that generates the crosslinking reaction accelerator. For example, in addition to the photoactive catalyst described above, a substance that generates a catalyst by light (photocatalyst generating agent) may be additionally used, or the photoactive catalyst may be replaced by the above, and in addition to the aforementioned thermally active catalyst, an additional borrowing may be used. The substance (thermal catalyst generating agent) which generates a catalyst by heat, or replaces the aforementioned thermally active catalyst. The photoactive catalyst is not particularly limited, and examples thereof include a photobase generator (a substance which generates an alkaline catalyst by light irradiation), a photoacid generator (a substance which generates an acid catalyst by light irradiation), and the like. It is preferred to use a photobase generator. The photobase generator may, for example, be 9-anthrylmethyl N (N-diethylcarbamate, trade name WPBG-018) or (E)-1-[3- (2-hydroxyphenyl)-2-acrylic acid] piperidine ((E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine, trade name WPBG-027), 1-(蒽醌-2 -Ethyl imidazolium carboxylate (1-(anthraquinon-2-yl)ethyl imidazolecarboxylate, trade name WPBG-140), 2-nitrobenzyl 4-methylpropenylpyridylpyridin-1-carboxylic acid Ester (trade name: WPBG-165), 1,2-diisopropyl-3-[bis(methylamino)methylene]indole 2-(3-benzimidylphenyl)propionate (trade name WPBG) -266), 1,2-dicyclohexyl-4,4,5,5-tetramethyldi-n-butyltriphenyl borate (trade name: WPBG-300), and 2-(9-oxydibenzo-benzoate Piperidin-2-yl)propionic acid 1,5,7-trinitrogen Heterobicyclo[4.4.0]non-5-ene (Tokyo Chemical Industry Co., Ltd.), a compound containing 4-piperidylmethanol (trade name: HDPD-PB100: manufactured by HERAEUS Co., Ltd.), and the like. In addition, the trade names including "WPBG" are the trade names of Wako Pure Chemical Industries Co., Ltd. The photoacid generator may, for example, be an aromatic onium salt (trade name: SP-170: ADEKA), a triarylsulfonium salt (trade name: CPI101A: SAN-APRO), or an aromatic onium salt (trade name: Irgacure 250: CHIBA JAPAN) Company) and so on. Further, the catalyst for chemically bonding the fine pore particles is not limited to the photoactive catalyst and the photocatalyst generating agent, and may be, for example, a thermal active catalyst or a thermal catalyst generating agent such as urea. The catalyst for chemically bonding the fine pore particles may, for example, be an alkali catalyst such as potassium hydroxide, sodium hydroxide or ammonium hydroxide, or an acid catalyst such as hydrochloric acid, acetic acid or oxalic acid. Among them, an alkali catalyst is preferred. The catalyst or catalyst generating agent which chemically bonds the microporous particles may be used, for example, in a sol particle liquid (for example, a suspension) containing the pulverized material (microporous particles) before application, or the foregoing contact may be used. The medium or the catalyst generating agent is mixed in a solvent to prepare a mixed solution. The mixed liquid may be, for example, a coating liquid obtained by directly adding the solution in the sol particle liquid, a solution obtained by dissolving the catalyst or a catalyst generating agent in a solvent, or the catalyst or catalyst generating agent. A dispersion obtained by dispersing in a solvent. The solvent is not particularly limited, and examples thereof include water, a buffer solution and the like.

Further, for example, when the fine pore particles are a pulverized product of a gel-like cerium compound obtained from a cerium compound containing at least a trifunctional or lower saturated functional group, after the liquid containing the fine pore particles is prepared, In the production process, further adding to indirectly combine the aforementioned microporous particles Crosslinking adjuvant. The crosslinking auxiliary agent enters between the particles, and by mutually interacting or bonding the particles and the crosslinking auxiliary agent, the particles which are slightly separated in distance can be bonded, so that the strength can be efficiently improved. The aforementioned crosslinking assistant is preferably a multi-crosslinked decane monomer. Specifically, the multi-crosslinked decane monomer may have an alkoxy fluorenyl group of 2 or more and 3 or less, and a chain length between the alkoxy fluorenyl groups may be 1 or more and 10 or less, and may contain carbon. The element. The crosslinking auxiliary agent may, for example, be 1,2-bis(trimethoxyindenyl)ethane, 1,2-bis(triethoxyindenyl)ethane, bis(trimethoxyindenyl)methane or bis (three) Ethoxylated methane, 1,3-bis(triethoxyindenyl)propane, 1,3-bis(trimethoxyindolyl)propane, 1,4-bis(triethoxyindenyl)butane, 1 , 4-bis(trimethoxyindenyl)butane, 1,5-bis(triethoxyindenyl)pentane, 1,5-bis(trimethoxyindolyl)pentane, 1,6-bis (triethyl) Oxyfluorenyl)hexane, 1,6-bis(trimethoxyindolyl)hexane, bis(trimethoxyindolyl)-n-butyl-n-propyl-ethane-1,2-diamine, tri-( 3-trimethoxysulfonylpropyl)isocyanate, tris-(3-triethoxyphosphoniumpropyl)isocyanate, and the like. Among them, particularly preferred is 1,2-bis(trimethoxyindolyl)ethane or 1,6-bis(trimethoxyindenyl)hexane. The amount of the crosslinking auxiliary agent to be added is not particularly limited, but may be, for example, 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 10% by weight based on the weight of the fine pore particles of the above-mentioned cerium compound.

Next, a liquid (for example, a suspension) containing the fine pore particles is applied to a resin film (hereinafter sometimes referred to as "substrate") (coating step). For the coating, for example, various coating methods described below can be used, and are not limited thereto. A coating liquid containing the fine pore particles and the catalyst can be formed by directly applying a solution containing the fine pore particles (for example, a pulverized product of a gel-like cerium oxide compound) onto the resin film. The aforementioned coating The film, for example, may also be referred to as a coating layer. By forming the coating film described above, for example, by depositing and depositing the pulverized material in which the three-dimensional structure has been broken, a new three-dimensional structure can be constructed. Further, for example, the liquid containing the fine pore particles may not contain a catalyst for chemically bonding the fine pore particles. For example, as described later, the precursor film forming step may be carried out by spraying a catalyst which chemically bonds the fine pore particles to the coating film or while spraying. However, the liquid containing the fine pore particles may include a catalyst for chemically bonding the fine pore particles, and the microporous particles may be chemically bonded to form the porous body by the action of the catalyst contained in the coating film. Body precursors.

The solvent (hereinafter also referred to as "solvent for coating") is not particularly limited, and for example, an organic solvent can be used. The organic solvent may be a solvent having a boiling point of 150 ° C or lower. Specific examples thereof include IPA, ethanol, methanol, n-butanol, 2-butanol, isobutanol, and pentanol, and the same as the above-mentioned solvent for pulverization can be used. In the step of forming the coating film, the pulverization solvent containing the pulverized material of the gelled compound can be used as it is, in the step of forming the coating film.

In the coating step, for example, the pulverized pulverized material (hereinafter also referred to as "sol particle liquid") dispersed in the solvent is preferably applied onto the substrate. The sol particle liquid of the present invention can be continuously formed into a film by, for example, being applied to a substrate and dried to carry out the above-described chemical crosslinking, whereby a void layer having a film strength of a certain degree or more can be continuously formed. Further, the "sol" in the present invention is a cerium oxide sol particle in which a three-dimensional structure of a nanostructure which maintains a part of a void structure is dispersed in a solvent by pulverizing a three-dimensional structure of a gel. It shows the state of fluidity.

The concentration of the aforementioned pulverized material in the aforementioned solvent is not particularly limited and may be, for example, 0.3 to 50% (v/v), 0.5 to 30% (v/v), and 1.0 to 10% (v/v). When the concentration of the pulverized material is too high, for example, the fluidity of the sol particle solution is remarkably lowered, and aggregates and wrinkles at the time of coating may occur. On the other hand, when the concentration of the pulverized material is too low, for example, not only the time required to dry the solvent of the sol particle solution but also the residual solvent after drying is increased, and thus the porosity may be lowered.

The physical properties of the aforementioned sol are not particularly limited. The shear viscosity of the aforementioned sol, for example, at a shear rate of 10001/s, may be, for example, a viscosity of 100 cPa. s below, viscosity 10cPa. s below, viscosity 1cPa. s below. If the shear viscosity is too high, for example, wrinkles are applied, there is a possibility that the transfer rate of the gravure coating is lowered. Conversely, when the shear viscosity is too low, for example, the wet coating (coating) thickness at the time of coating cannot be increased, and thus the desired thickness may not be obtained after drying.

The amount of the pulverized material to be applied to the substrate is not particularly limited. For example, it can be appropriately set depending on the thickness of the porous polysiloxane porous body or the like. In the case of forming the porous polysiloxane porous body having a thickness of 0.1 to 1000 μm, a specific example of the amount of the pulverized material applied to the substrate is, for example, 0.01 to 60000 μg, 0.1 to 5000 μg, 1 to 1 per ² m ² of the substrate area. 50 μg. The preferred coating amount of the sol particle liquid is, for example, related to the liquid concentration or the coating method, and thus it is difficult to define it in a straightforward manner. However, in consideration of productivity, it is preferable to apply it as thin as possible. If the amount of coating (coating amount) is too large, for example, the possibility of drying in a drying oven before the solvent is volatilized is high. Therefore, by depositing and depositing the nanopulverized particles in a solvent and drying the solvent before forming the void structure, void formation can be prevented and the porosity can be greatly reduced. On the other hand, if the coating amount is too small, the risk of uneven surface coating due to unevenness of the base material and uneven hydrophobicity may become high.

Further, the production method of the present invention has, for example, a precursor formation step of forming a void structure of the void layer precursor on the resin film as described above. The precursor formation step is not particularly limited. For example, the precursor (void structure) can be formed by a drying step of drying the coating film prepared by applying the fine pore particle-containing liquid. By the drying treatment in the drying step, for example, not only the solvent (the solvent contained in the sol particle liquid) in the coating film but also the sol particles may be deposited and deposited in a drying process to form a void structure. The temperature of the aforementioned drying treatment is, for example, 50 to 250 ° C, 60 to 150 ° C, 70 to 130 ° C, and the aforementioned drying treatment time is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, and 0.3 to 3 minutes. The drying treatment temperature and time, for example, in terms of continuous productivity or exhibiting a high porosity, the lower the temperature and the shorter the time, the better. When the conditions are too strict, for example, when the base resin film is used, the substrate is stretched in a drying furnace due to the glass transition temperature of the substrate, 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 the residual solvent is contained when leaving the drying furnace, when it is rubbed with the roller in the next step, there is a problem in appearance which causes scratching or the like.

The drying treatment may be, for example, natural drying, and may be heat drying or drying under reduced pressure. The aforementioned drying method is not particularly limited, and examples are If a general heating device can be used. The heating device may, for example, be a hot air heater, a heating roller, a far infrared heater or the like. Among them, when industrially continuous production is premised, heating and drying should be used. Further, in order to suppress the occurrence of shrinkage stress due to volatilization of the solvent during drying, and thus the occurrence of cracking of the void layer (the porous polysiloxane porous body), the solvent to be used is preferably a solvent having a low surface tension. The solvent may be exemplified by a lower alcohol represented by isopropyl alcohol (IPA), hexane, perfluorohexane or the like, but is not limited thereto. Further, a small amount of a perfluoro-based surfactant or a quinone-based surfactant may be added to the above IPA or the like to lower the surface tension.

Further, the method for producing a laminated film of the present invention comprises, as described above, a crosslinking reaction step of generating a crosslinking reaction inside the precursor after the precursor forming step, and in the crosslinking reaction step, The crosslinking reaction accelerator is produced by light irradiation or heating, and the crosslinking reaction step has a plurality of stages. In the first stage of the crosslinking reaction step, the fine pore particles are chemically bonded, for example, by the crosslinking reaction accelerator (for example, an acidic substance or a basic substance). Thereby, for example, the three-dimensional structure of the pulverized material in the coating film (precursor) can be fixed. When the conventional sintering is carried out, for example, by performing a high temperature treatment at 200 ° C or higher, dehydration condensation of a decyl alcohol group and formation of a decane bond are induced. In the present invention, by reacting various additives catalyzing the above-described dehydration condensation reaction, for example, the above substrate (resin film) may be not damaged, and a relatively low drying temperature of about 100 ° C and a short processing time of less than several minutes Inside, the void structure is continuously formed and fixed.

The method of chemical bonding described above is not particularly limited, for example, It is appropriately determined depending on the type of the gelatinous quinone compound. Specific examples of the chemical bonding can be carried out, for example, by chemical crosslinking bonding of the pulverized material, and it is also conceivable, for example, when inorganic particles such as titanium oxide are added to the pulverized material. The particles and the aforementioned pulverized material are chemically crosslinked. Further, in the case of carrying a living catalyst such as an enzyme, a portion different from the catalytic activity point and the pulverized material may be chemically crosslinked and bonded. Therefore, the present invention can be applied not only to the void layer (polyphosphorus porous body) formed of the sol particles but also to the application of the organic-inorganic hybrid void layer, the host-guest void layer, and the like, but is not limited thereto.

The chemical reaction in the presence of the aforementioned catalyst (crosslinking reaction accelerator) can be carried out (produced) at any stage in the production method of the present invention, and is not particularly limited, but can be, for example, in the crosslinking reaction step of most of the foregoing stages. At least one stage is carried out. For example, in the method for producing a laminated film of the present invention, as described above, the drying step may also serve as the precursor forming step. Further, for example, after the drying step described above, the crosslinking reaction step of the plurality of stages may be carried out, and in at least one stage, the microporous particles may be chemically bonded 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 fine pore particles can be chemically bonded by light irradiation. Further, in the catalyst-based thermally active catalyst, the fine pore particles may be chemically bonded by heating in the crosslinking reaction step.

The chemical reaction can be carried out, for example, by irradiating the coating film containing the catalyst generator (a substance which generates a crosslinking reaction accelerator) added to the sol particle liquid (for example, a suspension) beforehand. Or heating or spraying the above-mentioned catalyst generating agent (a substance which generates a crosslinking reaction accelerator) on the coating film, followed by light irradiation or heating, or spraying the above-mentioned catalyst generating agent (a substance which generates a crosslinking reaction accelerator) Light irradiation or heating is performed on one side. The cumulative amount of light of the aforementioned light irradiation is not particularly limited, but may be, for example, 200 to 800 mJ/cm ² , 250 to 600 mJ/cm ² , or 300 to 400 mJ/cm ² in terms of @360 nm. It is preferable that the cumulative amount of light is 200 mJ/cm ² or more from the viewpoint that the amount of irradiation is insufficient and the light absorption and decomposition of the catalyst generating agent are not performed so that the effect is insufficient. Further, from the viewpoint of preventing damage to the substrate under the void layer and causing thermal wrinkles, the cumulative amount of light of 800 mJ/cm ² or less is preferable. The conditions of the aforementioned heat treatment are not particularly limited, and the aforementioned heating temperature may be, for example, 50 to 250 ° C, 60 to 150 ° C, 70 to 130 ° C, and the aforementioned heating time may be, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, and 0.3 to 3 minutes. . Alternatively, the step of drying the coated sol particle liquid (for example, a suspension) as described above may also serve as a step of performing a chemical reaction in the presence of the above catalyst. That is, in the step of drying the applied sol particle liquid (for example, a suspension), the pulverized material (microporous particles) can be chemically bonded by a chemical reaction in the presence of the catalyst. In this case, the pulverized material (microporous particles) can be further strongly bonded by further heating the coating film after the drying step. In addition, it is presumed that a chemical reaction in the presence of the catalyst is also carried out in the step of producing the fine pore particle-containing liquid (for example, a suspension) and the step of applying the fine pore particle-containing liquid. However, this speculation does not impose any limitation on the present invention. Further, in order to suppress the occurrence of shrinkage stress due to volatilization of the solvent during drying, and thus the phenomenon that the void layer (the porous polysiloxane porous body) is broken, the solvent to be used is preferably a solvent having a low surface tension. A lower alcohol represented by isopropyl alcohol (IPA), hexane, perfluorohexane or the like can be exemplified, but is not limited thereto.

In the present invention, since the crosslinking reaction step has a plurality of stages, for example, in the case where the crosslinking reaction step is one stage, the strength of the void layer can be further increased. Hereinafter, the step after the second stage of the crosslinking reaction step may be referred to as an "aging step". In the aging step, for example, the crosslinking reaction can be further promoted inside the precursor by heating the precursor. Although the phenomenon and mechanism generated in the aforementioned crosslinking reaction step are not known, for example, as described above. For example, in the aging step, for example, by causing the heating temperature to be low, the crosslinking reaction is suppressed while suppressing the shrinkage of the precursor, whereby the strength is increased, so that a high void ratio and strength can be simultaneously achieved. 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 carrying out the aforementioned aging step is, for example, 10 to 30 hours, 13 to 25 hours, and 15 to 20 hours.

As described above, the method for producing the laminated film of the present invention can be carried out. The laminated film produced by the production method of the present invention has an excellent strength, for example, a porous body which can be formed into a roll, and has an advantage of being excellent in production efficiency and easy to handle.

The laminated film (void layer) of the present invention obtained in this manner can be further laminated with another film (layer) to form a laminated structure including the porous structure. In this case, in the above-mentioned laminated structure, each constituent element can be laminated, for example, by an adhesive or an adhesive.

The laminate of the above constituent elements can be continuously processed by using a long film, for example, from the viewpoint of efficiency (so-called roll-to-roll (Roll) To Roll), etc., may be laminated, and may be laminated when the substrate is a molded article, an element, or the like.

Hereinafter, with respect to the continuous treatment step, a method of forming the aforementioned void layer of the present invention on a substrate (resin film) will be exemplified using FIGS. 1 to 3. Although FIG. 2 shows the step of adhering the protective film to the film after the porous polysiloxane body is formed into a film, when the film is laminated on another functional film, the above method may be used, or another functional film may be coated. After drying, the porous polysiloxane porous body after the film formation described above was adhered before the winding. In addition, the film formation method shown in the figure is only an example, and is not limited to this.

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

Fig. 1 is a cross-sectional view schematically showing an example of a procedure in a method of forming the aforementioned void layer on the aforementioned substrate (resin film). In FIG. 1, the method for forming a void layer includes a coating step (1) of applying a sol particle liquid 20" of a pulverized product of the gelled compound onto 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 (void layer precursor) 20'; and the crosslinking step (3) is to cross-link the coating film 20' to form a cross After the combined treatment, the precursor (void layer) 20; and the strength increasing step (aging step) (4), the adhesion peeling strength of the precursor 20 to the substrate 10 after the crosslinking treatment is increased to form a void layer (strength) Improved void layer) 21. Thus, as shown, a void layer 21 can be formed on the substrate 10. In the production method, the drying step (2) corresponds to the "precursor forming step" in the method for producing a laminated film of the present invention. Further, in the crosslinking step (3) and the strength increasing step (aging step) (4), a crosslinking reaction is generated inside the precursor. That is, the two-stage step of the crosslinking step (3) and the strength increasing step (aging step) (4) corresponds to the aforementioned "cross-linking reaction step" in the method for producing a laminated film of the present invention. Further, the method of forming the void layer may be appropriately included or may not include the steps other than the above (1) to (4).

In the coating step (1), the coating method of the sol particle liquid 20" is not particularly limited, and a general coating method can be employed. The coating method may be, for example, a slit die method, a reverse gravure coating method, or a micro gravure method (micro gravure). Coating method), dipping method (dip coating method), spin coating method, brush coating method, roll coating method, flexographic printing method, wire coating method, spray coating method, extrusion coating method, curtain coating method, reverse coating method Among them, from the viewpoints of productivity, smoothness of a coating film, etc., extrusion coating, curtain coating, roll coating, microgravure coating, etc. are preferred. Coating of the 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, and for example, it can be as described above.

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

Further, in the chemical treatment step (3), the above-mentioned catalyst generating agent (the catalyst (crosslinking reaction accelerator)) which is added before the coating is contained The coating film 20' of the substance, for example, a photocatalyst generating agent or a thermal catalyst generating agent, is subjected to light irradiation or heating to chemically bond (for example, crosslink) the pulverized material in the coating film 20' to form a cross-linking treatment. Previously driven 20. The light irradiation or heating conditions of the aforementioned chemical treatment step (3) are not particularly limited and may be as described above.

Further, the strength raising step (aging step) (4) is performed by, for example, heating the cross-linking treatment precursor 20 or the like to form the void layer 21. The heating conditions of the aforementioned strength increasing step (aging step) (4) are not particularly limited and may be as described above.

Next, Fig. 2 schematically shows an example of a coating apparatus for a slit die method and a method of forming the void layer using the coating device. In addition, although FIG. 2 is a cross-sectional view, hatching is omitted for easy clarification.

As shown, each step in the method of using the apparatus is carried out while the substrate 10 is being conveyed in one direction by a roll. 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, the application step (1) of applying the sol particle liquid 20" to the substrate 10 is performed on the substrate roller 10 while the substrate 10 is being fed and conveyed by the delivery roller 101, and then transferred to the oven region 110. Drying step (2). In the coating apparatus of Fig. 2, after the coating step (1), before the drying step (2), a preliminary drying step is carried out. The preliminary drying step can be carried out at room temperature without heating. In the drying step (2), the heating device 111 is used. As described above, the heat device, the heating roller, the far-infrared heater, etc. can be suitably used. Further, for example, the drying step (2) can be divided into a plurality. The step, and the later drying step, the higher the drying temperature.

After the drying step (2), the chemical treatment step (3) is carried out in the chemical treatment zone 120. In the chemical treatment step (3), for example, when the coating film (precursor) 20' after drying contains a photocatalyst generating agent, light is irradiated by a lamp (light irradiation device) 121 disposed above and below the substrate 10. Alternatively, for example, when the coated film 20' after drying contains a thermal catalyst generating agent, a heat exchanger (heating device) is used instead of the lamp (light irradiation device) 121, and the substrate is heated by the air heater 121 disposed above the substrate 10. 10. By the crosslinking treatment, the pulverized material in the coating film 20' is chemically bonded, and the coating film 20' is hardened and strengthened to become the precursor 20 after the crosslinking treatment (hereinafter, sometimes referred to as "precursor"). ). Further, in this example, although the chemical treatment step (3) is carried out after the drying step (2), as described above, the pulverized material may be chemically bonded at any stage of the production method of the present invention without particular limitation. . For example, as described above, the drying step (2) can double as the chemical treatment step (3). Further, when the chemical bonding described above occurs in the drying step (2), the chemical treatment step (3) may be further carried out to further strengthen the chemical bonding of the pulverized material. Further, the pulverized material may be chemically bonded in a step before the drying step (2) (for example, a preliminary drying step, a coating step (1), a step of preparing a coating liquid (for example, a suspension), and the like.

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

Next, after the strength increasing step (aging step) (4), the layered body in which the void layer 21 is formed on the substrate 10 is taken up by the take-up roll 105. Further, in Fig. 2, the protective sheet fed by the roller 106 covers and protects the void layer 21 of the laminated body. Here, other laminated layers formed of a long film may be formed on the void layer 21 instead of the protective sheet.

Fig. 3 is a view schematically showing an example of a coating apparatus using a micro-gravure method (microgravure coating method) and a method of forming the above-described void layer using the coating apparatus. In addition, although FIG. 3 is a cross-sectional view, hatching is omitted for easy clarification.

As shown in the figure, each step in the method using the apparatus is carried out while the substrate 10 is being conveyed in one direction by a roll as in the case of 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, the coating step (1) of applying the sol particle liquid 20" onto the substrate 10 while the substrate 10 is being fed and conveyed by the delivery roller 201. The coating system of the sol particle liquid 20" is used as shown in the figure. The liquid portion 202, the doctor blade (blade) 203, and the micro gravure 204 are performed. Specifically, the sol particle liquid 20" stored in the liquid storage portion 202 is adhered to the surface of the micro gravure 204, and then controlled to a predetermined thickness by the doctor blade 203, and is applied to the surface of the substrate 10 by the micro gravure 204. Further, the micro gravure 204 is exemplified, and is not limited thereto, and any other coating device may be used.

Next, the drying step (2) is carried out. Specifically, as shown in the figure, In the oven region 210, the substrate 10 coated with the sol particle liquid 20" is transferred, and heated by the heating device 211 in the oven region 210 to dry the sol particle liquid 20". The heating device 211 can be the same as in Fig. 2, for example. Further, the drying step (2) can be divided into a plurality of steps by dividing the oven region 210 into a plurality of blocks, and the drying temperature is higher as the drying step is followed. After the drying step (2), the chemical treatment step (3) is carried out in the chemical treatment zone 220. In the chemical treatment step (3), for example, when the coating film 20' after drying contains a photocatalyst generating agent, light is irradiated by a lamp (light irradiation device) 221 disposed above and below the substrate 10. Alternatively, for example, when the coated film (precursor) 20' after drying contains a thermal catalyst generating agent, a heater (heating device) 221 is used instead of the lamp (light irradiation device) 221, and a hot air device disposed above the substrate 10 is used ( The heating device 221 heats the substrate 10. By the crosslinking treatment, the pulverized material in the coating film 20' is chemically bonded to form the void layer precursor 20.

After the chemical treatment step (3), a strength increasing step (aging step) (4) is performed in the crosslinking reaction region (aging region) 230 to form an adhesion peeling strength of the resin layer 10 of the void layer precursor 20 to be formed. The void layer 21. The strength increasing step (aging step) (4) can be performed, for example, by using a hot air heater (heating means) 231 disposed above and below the substrate 10, by heating the precursor 20 as described above. The heating temperature, time, and the like are not particularly limited, but may be, for example, as described above.

Next, after the strength increasing step (aging step) (4), the laminated film in which the void layer 21 is formed on the substrate 10 is taken up by the take-up roll 241. Then, other layers may be laminated on the laminated film as described above. Further, the laminated film may be applied to the laminated film before the winding film 241 is taken up by the take-up roll 241. For example, layering 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 comprising the laminated film of the present invention, and the other structure is not limited at all. The optical member of the present invention may further comprise other layers in addition to the laminated film of the present invention.

Further, the optical member of the present invention comprises the above-described laminated film of the present invention as a low reflection layer. The optical member of the present invention may further comprise other layers in addition to the laminated film of the present invention. The optical member of the present invention has, for example, a roll shape.

Example

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

(Example 1)

In the present embodiment, the laminated film (layered film roll) of the present invention is produced as follows.

(1) Gelation of bismuth compounds

The MTMS of 0.95 g of the ruthenium compound precursor was dissolved in 2.2 g of DMSO. To the mixed liquid, 0.5 g of a 0.01 mol/L aqueous oxalic acid solution was added, and the mixture was stirred at room temperature for 30 minutes to thereby hydrolyze MTMS to form tris(hydroxy)methylnonane.

After adding 0.38 g of 28% aqueous ammonia and 0.2 g of pure water to 5.5 g of DMSO, the above-mentioned mixing after the hydrolysis treatment is further added. The solution was stirred at room temperature for 15 minutes to carry out gelation of tris(hydroxy)methylnonane to prepare a gelatinous quinone compound.

(2) ripening treatment

The mixed solution subjected to the gelation treatment was kept at 40 ° C for 20 hours as it was, and the ripening treatment was carried out.

(3) pulverization treatment and addition of photobase generator

Next, the gelatinous ruthenium compound after the above-mentioned ripening treatment is pulverized into pellets having a size of several mm to several cm using a spatula. 40 g of IPA was added thereto, and after gently stirring, it was allowed to stand at room temperature for 6 hours, and the solvent and catalyst in the gel were decanted. The same decantation treatment was repeated 3 times to terminate the solvent substitution. Next, the gelatinous ruthenium compound in the mixed liquid was subjected to high-pressure medium-free pulverization. This pulverization treatment was carried out by using a homogenizer (trade name: UH-50, manufactured by SMT Co., Ltd.) in a 5 cc screw bottle, weighing 1.18 g of gel and 1.14 g of IPA, and then performing 2 minutes at 50 W and 20 kHz. Smash.

The gelled ruthenium compound in the mixed liquid is pulverized by the pulverization treatment, and the mixed liquid is a sol particle liquid of the pulverized material. The volume average particle diameter of the particle size deviation of the pulverized material contained in the mixed liquid was confirmed by a dynamic light scattering type nano trajectory particle size analyzer (Model UPA-EX150, manufactured by Nikkiso Co., Ltd.), and the result was 0.50 to 0.70. Further, an IPA (isopropyl alcohol) solution of 1.5% by weight of a photobase generator (Wako Pure Chemical Industries, Ltd.: trade name: WPBG266, a substance which generates a catalyst (crosslinking reaction accelerator) by light) is prepared. To 0.75 g of the above sol particle liquid, 0.031 g was added to prepare a coating liquid. Further, the steps (1) to (3) above are equivalent to the production of the above-described fine film in the method for producing a laminated film of the present invention. "Containing liquid preparation step" of the liquid containing the pore particles.

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

Then, the coating liquid was applied (coated) on the surface of a polyethylene terephthalate (PET) substrate (resin film, 100 m long) by a bar coating method to form a coating film (coating step). . In the coating system, 6 μL of the sol particle liquid was applied to the surface of the substrate of 1 mm ² . The coating film was dried at a temperature of 100 ° C for 1 minute and dried to form a polysiloxane porous body film having a thickness of 1 μm (drying step). UV irradiation (precursor forming step) is performed on the aforementioned porous body film after drying. The above UV irradiation was carried out at 350 mJ/cm ² (@360 nm). Further, the precursor was subjected to heat aging at 60 ° C for 20 hr to obtain a low refractive index film (void layer) having a film strength.

(Comparative example)

A laminate film having a low refractive index film (void layer) laminated on the resin film was obtained in the same manner as in Example 1 except that the cerium oxide porous film formation treatment was performed only by UV treatment (heat aging was not performed). volume.

(Example 2)

In addition to the above-mentioned "(3) pulverization treatment and addition of photobase generating catalyst" in the first embodiment, after adding a photobase generating catalyst solution, further adding 0.78 g of 5% by weight to 0.75 g of the above sol solution The bis(trimethoxyindenyl)ethane was prepared in the same manner as in Example 1 except that the coating liquid was prepared, and a laminated film roll in which a low refractive index film (void layer) was laminated on the resin film was obtained.

(Example 3)

In addition to the above-mentioned "(3) pulverization treatment and addition of a photobase generating catalyst" in the first embodiment, the photobase generating catalyst adds 0.75 g of the aforementioned sol liquid. A laminate film roll in which a low refractive index film (void layer) was laminated on a resin film was obtained in the same manner as in Example 1 except that the amount was 0.054 g.

(Example 4)

In addition to changing the bis(trimethoxyindenyl)ethane of Example 2 to 5% by weight of 1,6-bis(trimethoxyindolyl)hexane (trade name: KBM3066: manufactured by Shin-Etsu Chemical Co., Ltd.) In the same manner as in Example 2, a laminated film roll in which a low refractive index film (void layer) was laminated on a resin film was obtained.

These results are shown in Table 1 below. Further, the refractive index, adhesive peel strength, haze, and scratch resistance were measured by the aforementioned methods. The scratch resistance was evaluated by ○, Δ or ×. Further, the storage stability was carried out by allowing the coating liquid to stand at room temperature for one week, and visually confirming whether or not the coating liquid was changed.

As shown in Table 1 above, Examples 1 to 4 in which the strength increasing step (aging step) (i.e., the crosslinking reaction step has a plurality of stages) were performed, compared to the case where the strength increasing step (aging step) was not performed (ie, crosslinking) In the comparative example in which the reaction step was in the first stage, the adhesive peel strength and the scratch resistance were improved. Further, the refractive indices of Examples 1 to 4 and the comparative examples hardly differed, and the extremely low refractive index of 1.14 to 1.17 was maintained. That is, it was confirmed that the laminated film of the embodiment can have both high voids Rate and film strength. Further, the haze values of the laminated films of Examples 1 to 4 were also kept at extremely low values of 0.4 as in the comparative example, and therefore it was confirmed that the transparency was maintained to the same extent as in the comparative example. Further, in Examples 1 to 4, since the storage stability of the coating liquid was excellent, it was confirmed that a laminated film of stable quality can be efficiently produced.

Industrial availability

As described above, according to the present invention, it is possible to provide a method for producing a laminated film which can have both a high void ratio and a film strength, a laminated film, an optical member, and an image display device. In the laminated film of the present invention, since the characteristics as described above are exhibited, for example, a low refractive index which can be used as a substitute for the air layer can be easily realized. Therefore, it is not necessary to provide an air layer by arranging a plurality of members at a certain distance 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 portion. Therefore, the laminated film of the present invention is useful for an optical member requiring a low refractive index. The laminated film of the present invention can be used, for example, in the optical member and the image display device of the present invention, but is not limited thereto and can be used in any application.

10‧‧‧Substrate

20‧‧‧Precursors (previously treated by cross-linking)

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

20”‧‧‧Sol particle liquid

21‧‧‧void layer

Claims (15)

A laminated film in which a void layer is laminated on a resin film, and the laminated film is characterized in that it is produced by a manufacturing method comprising the steps of: forming a precursor layer on the resin film before forming the gap layer And a cross-linking reaction step, after the precursor formation step, a cross-linking reaction is generated inside the precursor; the precursor contains a cross-linking reaction accelerator capable of generating the cross-linking reaction The substance; the foregoing substance generates the crosslinking reaction accelerator by light or heat; the crosslinking reaction accelerator is not produced in the precursor formation step; and the crosslinking reaction step produces the aforementioned crosslinking by light irradiation or heating The reaction accelerator is combined, and the crosslinking reaction step has a plurality of stages. The laminated film according to claim 1, wherein the crosslinking reaction accelerator comprises an acidic substance or a basic substance; the acidic substance or the alkaline substance is not produced in the precursor formation step; and the crosslinking step is by light Irradiation or heating produces the aforementioned acidic or alkaline substance. The laminate film of claim 1 or 2, wherein the crosslinking reaction step In at least one stage after the second stage, a crosslinking reaction is generated inside the precursor by heating the precursor. The laminated film according to any one of claims 1 to 3, wherein the strength of the precursor is further increased in at least one stage after the second stage of the crosslinking reaction step. The laminated film according to any one of claims 1 to 4, wherein at least one stage after the second stage of the crosslinking reaction step further increases the adhesion peeling strength of the precursor to the resin film. The laminated film according to any one of claims 1 to 5, wherein the refractive index of the void layer is equal to or less than a value obtained by adding 0.1 to a refractive index of the precursor. The laminated film according to any one of claims 1 to 6, which forms the void layer and has a refractive index of 1.25 or less. The laminated film according to any one of claims 1 to 7, which forms the void layer and has a porosity of 40% by volume or more. The laminated film according to any one of claims 1 to 8, which forms the aforementioned void layer and has a thickness of 0.01 to 100 μm. The laminated film according to any one of claims 1 to 9, which forms the aforementioned void layer and has a haze value of less than 5%. The laminated film according to any one of claims 1 to 10, wherein the void layer comprises a portion directly or indirectly chemically bonded by one or more constituent units forming a fine void structure, and the laminated film is used to make the foregoing composition The unit indirectly bonds the crosslinking auxiliary agent to form the aforementioned void layer including the portion in which the aforementioned constituent unit has been indirectly bonded. The laminate film according to claim 11, wherein the content of the crosslinking auxiliary agent in the void layer is 0.01 to 20% by weight based on the weight of the constituent unit. The laminated film according to any one of claims 1 to 12, 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 comprising an optical member as claimed in claim 14.