JP5828815B2 - Laminated interlayer film and method for producing the same, laminated glass and method for producing the same - Google Patents

Description

  The present invention relates to a laminated interlayer film and a manufacturing method thereof, and a laminated glass and a manufacturing method thereof. The present invention particularly relates to laminated glass used for building material windows, automotive windows, etc., preferably laminated glass in which a thermal barrier film and an interlayer film for laminated glass are sandwiched between two sheets of glass, a method for producing the same, The present invention relates to a laminated interlayer film used in a manufacturing method and a manufacturing method thereof.

  In recent years, there has been a great need for industrial products related to energy conservation due to increased interest in the environment and energy, and as one of them, it is effective in reducing the heat load of window glass of houses and automobiles, that is, the heat load due to sunlight. There is a demand for glass and functional films. In order to reduce the heat load caused by sunlight, it is necessary to prevent the transmission of sunlight in the infrared region of the sunlight spectrum.

  Among them, a laminated glass in which a functional film is inserted between two glass plates has been proposed from the viewpoint of improving heat shielding performance (see Patent Documents 1 and 2). The functional film is usually used as a laminated intermediate film including an intermediate film for enhancing adhesion with a glass plate. For example, Patent Document 1 discloses a configuration in which a plastic film including an infrared reflecting film is formed as a laminated intermediate film sandwiched between two laminated glass resin intermediate films, and the laminated intermediate film is sandwiched between two glass plates. ing. Moreover, when manufacturing the laminated glass of such a structure, the method of preventing a wrinkle from forming in the inserted plastic film is described from a viewpoint of suppressing the appearance defect and the heat insulation performance fall.

  Further, in Patent Document 1, a plastic film with an infrared reflecting film is cut into a shape that overlaps with a colored film having an opaque end, and then sandwiched between two intermediate films together with the colored film. A method for producing a laminated glass using a laminated interlayer film is described. According to the method described in Patent Document 1, since the wrinkles of the plastic film are prominent in the peripheral portion of the glass plate, an opaque colored film is provided in the peripheral portion of the laminated glass, so that the wrinkle is substantially formed in the central portion of the laminated glass. And cracks can be prevented from being visually recognized. However, Patent Document 1 discloses only an embodiment in which a plastic film in which a metal oxide film having a different refractive index or a polymer thin film infrared reflective film is laminated on a resin film as a support is sandwiched between intermediate films.

  In Patent Document 2, after a glass transfer material provided with a heat ray cut layer containing a metal oxide or metal on a film support is thermally bonded to an intermediate film, the film support is peeled off, and a laminated glass is obtained. A method of manufacturing is disclosed. However, Patent Document 2 does not disclose an example in which a liquid crystal film is used as a functional film having a heat ray cut layer and a heat shielding performance, and Patent Document 2 further uses a second intermediate film to cut the heat ray. The configuration in which the layers are sandwiched between the interlayer films has not been disclosed.

JP 2010-265160 A JP 2000-219543 A JP-A-3-237427

Under these circumstances, the present inventors manufactured laminated glass using an infrared reflective film using a brittle liquid crystal film as a functional film. When the support with a liquid crystal film was cut, It was found that the floating of the edge part was likely to occur, and the peeling part spread during the laminated glass, resulting in failure.
On the other hand, Patent Document 3 discloses a method in which a laminated film including a liquid crystal film and a support is cut by rotating a round blade-like cutter so that the film cut surface can be accurately formed in a desired molding angle such as a linear shape. Have been described. However, Patent Document 3 pays attention only to the shape of the cut surface of the film, and has not studied film cracking that occurs in the liquid crystal film itself. Further, no consideration was given to sandwiching a liquid crystal layer between two interlayer films for laminated glass. Thus, when the laminated film including the conventional liquid crystal film and the support is cut and the support with the liquid crystal film is sandwiched between the two intermediate films, the cut end of the liquid crystal film is peeled off (floating of the end). )) Has not been solved in the past and has not been studied.

  In view of the above, the problem to be solved by the present invention is to provide a method for producing a laminated intermediate film that includes a support with a liquid crystal film between two intermediate films, and the end face peeling of the liquid crystal film is suppressed. .

  As a result of intensive studies by the present inventors to solve the above problems, the liquid crystal film and the support of the support with a liquid crystal film were simultaneously cut, and the first intermediate film and the support with a liquid crystal film were supported before or after the cutting. Can be cut without applying stress to the edge of the film by laminating a body and laminating a second intermediate film on the support-side surface of the support with a liquid crystal film before or after the cutting. I came to find out what I could do. That is, even when the film is highly brittle, it has been found that peeling (lifting) of the end portion can be prevented at the time of cutting, and the above problem can be solved.

The present invention, which is a specific means for solving the above problems, is as follows.
[1] simultaneously cutting the support and the liquid crystal film with the liquid crystal film including the liquid crystal film formed on the support and the support;
Laminating a first intermediate film on the liquid crystal film side surface of the support with the liquid crystal film;
A method for producing a laminated intermediate film, comprising the step of laminating a second intermediate film on a support side surface of the support with a liquid crystal film.
[2] In the method for producing a laminated intermediate film according to [1], the step of laminating the first intermediate film on the surface of the support with a liquid crystal film on the liquid crystal film side includes: It is preferable to include a step of adhering the first intermediate film to the side surface.
[3] In the method for producing a laminated interlayer film according to [2], it is preferable that the step of bonding the liquid crystal film to the first interlayer film is thermal bonding.
[4] In the method for producing a laminated intermediate film according to any one of [1] to [3], the first intermediate film, the liquid crystal film, and the support are simultaneously cut after the thermal bonding step. It is preferable to do.
[5] The method for producing a laminated intermediate film according to [4] preferably includes a step of cutting using a laser in the step of simultaneously cutting the first intermediate film, the liquid crystal film, and the support. .
[6] The method for producing a laminated intermediate film according to [4], wherein the first intermediate film, the liquid crystal film, and the support are simultaneously cut, and the die blade is inserted from the support side and punched out. It is preferable to contain.
[7] The method for producing a laminated intermediate film according to any one of [1] to [3], wherein the liquid crystal film of the support with a liquid crystal film is provided after the step of simultaneously cutting the liquid crystal film and the support. It is preferable to thermally bond the first interlayer film and the first interlayer film.
[8] The method for producing a laminated intermediate film according to [7], wherein the liquid crystal film and the support are cut at the same time, and all ends of the support and all ends of the liquid crystal film are It is preferable to cut so as to be 1 mm or more inside from the end of the first intermediate film.
[9] The method for producing a laminated interlayer film according to [7] or [8] preferably includes a step of cutting the first interlayer film before the thermal bonding step.
[10] The method for producing a laminated interlayer film according to any one of [7] to [9] includes a step of cutting the liquid crystal film and the support at the same time using a laser. Features.
[11] The method for producing a laminated intermediate film according to any one of [7] to [10], wherein the mold blade is inserted from the support side in the step of simultaneously cutting the liquid crystal film and the support body. It includes a step of punching.
[12] In the method for producing a laminated interlayer film according to any one of [1] to [11], in the cutting step, it is preferable to cut using a laser under a condition satisfying the following formula (1).
Formula (1): 0.0002 <W / (T × V) <0.0008
(In formula (1), W represents the laser output (unit: W), T represents the thickness of the laminate to be cut (unit: μm), and V represents the laser scanning speed (mm / second).)
[13] The method for producing a laminated intermediate film according to any one of [1] to [12] preferably uses a laser having a wavelength in an infrared region in the cutting step.
[14] The method for producing a laminated interlayer film according to any one of [1] to [13] preferably uses a die blade having a blade edge angle of 20 ° to 40 ° in the cutting step.
[15] In the method for producing a laminated interlayer film according to [14], it is preferable that a corner shape of the die blade has a radius of 2 mm or more.
[16] In the method for producing a laminated interlayer film according to [14] or [15], the material of the mold blade is SK material, high speed steel or SUS440C, Rockwell hardness is HRA70 or more, and bending strength is 2. It is preferably 5 MPa or more.
[17] In the method for producing a laminated interlayer film according to any one of [14] to [16], it is preferable that a pressing rubber having a rubber hardness of 20 to 80 ° is provided in the vicinity of the blade portion of the mold blade. .
[18] In the method for producing a laminated intermediate film according to any one of [1] to [17], a liquid crystal film-forming coating solution is applied on the support to form the support with a liquid crystal film. It is preferable that the process to include is included.
[19] A laminated interlayer film produced by the method for producing a laminated interlayer film according to any one of [1] to [18].
[20] A method for producing a laminated glass, comprising a step of sandwiching the laminated interlayer film according to [19] between at least two glass plates.
[21] A laminated glass produced by the method for producing a laminated glass according to [20].

  According to the present invention, a method for producing a laminated intermediate film that includes a liquid crystal film between two intermediate films, the support for the liquid crystal film is removed, and generation of cracks in the liquid crystal film and film cracking are suppressed. Can be provided.

FIG. 1 is a schematic view showing a cross section of an example of an implementation process of the method for producing a laminated interlayer film of the present invention. FIG. 2 is a schematic view showing a cross section of an example of the laminated interlayer film of the present invention obtained in the embodiment of the method for producing a laminated interlayer film of the present invention. FIG. 3 is a schematic view showing a cross section of an example of the laminated glass of the present invention obtained in the embodiment of the method for producing the laminated glass of the present invention. FIG. 4 is a schematic view showing a cross section of another example of the process for carrying out the method for producing a laminated interlayer film of the present invention. FIG. 5 is a schematic view showing a cross section of another example of the laminated interlayer film of the present invention obtained in another embodiment of the method for producing a laminated interlayer film of the present invention. FIG. 6 is a schematic view showing a cross section of an example of a liquid crystal film used in the method for producing a laminated intermediate film of the present invention.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Method for producing laminated interlayer film]
The method for producing a laminated interlayer film of the present invention includes a step of simultaneously cutting a support, a liquid crystal film with a liquid crystal film including the liquid crystal film formed on the support, and the liquid crystal of the support with the liquid crystal film. The method includes a step of laminating a first intermediate film on a surface on the film side, and a step of laminating a second intermediate film on the surface on the support side of the support with a liquid crystal film.
With such a configuration, according to the method for producing a laminated interlayer film of the present invention, the laminated interlayer film can be cut while suppressing the stress applied to the interface between the support and the liquid crystal film, and the failure of the liquid crystal film is suppressed. Can provide. Further, if the cost is increased to increase the interface between the support and the liquid crystal film, it may be possible to provide an easy-adhesion layer, but according to the method for producing a laminated intermediate film of the present invention, there is no need to provide an easy-adhesion layer. Manufacturing cost can be reduced.
Hereinafter, preferred embodiments of the method for producing a laminated interlayer film of the present invention will be described. Needless to say, the present invention is not limited to these examples.

<Process for forming a support with a liquid crystal film>
The support used in the method for producing a laminated interlayer film of the present invention and the support with a liquid crystal film including the liquid crystal film formed on the support are not particularly limited, and a known support with a liquid crystal film is commercially available. Alternatively, a liquid crystal film produced on a support may be used.
Among them, the method for producing a laminated interlayer film according to the present invention preferably includes a step of forming a liquid crystal film on a support, and a liquid crystal film-forming coating solution is applied onto the support to attach the liquid crystal film. More preferably, the method includes a step of forming a support. A support with a liquid crystal film in which such a coating-type liquid crystal film is provided on a support is more liquid crystal with a liquid crystal film than a liquid crystal film laminated on a support through an easily adhesive layer or an adhesive layer. In the process of cutting the support and the support at the same time, edge peeling (floating) is likely to occur. However, in the method for producing a laminated intermediate film of the present invention, the edge at the time of cutting can be sufficiently applied to such a coating type liquid crystal film. Peeling of the part can be suppressed.
In the method for producing a laminated interlayer film of the present invention, the liquid crystal film contains a liquid crystal compound. The liquid crystal compound is preferably a rod-like cholesteric liquid crystal. In the method for producing a laminated intermediate film of the present invention, the liquid crystal film is preferably a selective reflection film, and more preferably includes an infrared reflection film (hereinafter also referred to as an infrared reflection layer) as the selective reflection film. The liquid crystal film is preferably an infrared reflective layer. In addition, the said infrared reflective layer means the layer which has the capability to reflect infrared rays.
In the method for producing a laminated interlayer film of the present invention, the liquid crystal film is preferably a layer in which a polymerizable liquid crystal compound is fixed, and is a layer in which a cholesteric liquid crystal phase is fixed (hereinafter referred to as “cholesteric liquid crystal layer”). It is more preferable that it is a cholesteric liquid crystal layer and an infrared reflection layer.
In the following, a support with a liquid crystal film, which is a preferred embodiment of the present invention, including a liquid crystal film that is a cholesteric liquid crystal layer and is an infrared reflective layer will be mainly described. However, in the present invention, the liquid crystal film is not limited to a liquid crystal film of a preferred embodiment described later.

(Support)
In the step of forming the support with a liquid crystal film in the method for producing a laminated interlayer film of the present invention, using a support such as a transparent plastic resin film stably stabilizes the infrared light reflection layer that is the cholesteric liquid crystal layer. It is preferable from the viewpoint of film formation. However, the method for producing a laminated intermediate film of the present invention does not include a step of peeling the support described later, and the support remains in the obtained laminated intermediate film of the present invention. Therefore, it is preferable that the support is transparent and has little retardation so that the support is not visually recognized when it is formed into a laminated glass and does not exhibit unnecessary optical properties.

The support is self-supporting and supports the liquid crystal film. In particular, when a liquid crystal film is formed by laminating a plurality of infrared reflecting films, an infrared reflecting film is sequentially laminated on a lower infrared reflecting layer as a support including a lower infrared reflecting layer as a support. be able to.
Moreover, the said support body needs to be transparent. Among these, it is preferable that the said support body is a transparent plastic resin film. The haze of the support is preferably 3% or less, more preferably 1% or less.

The support used in the method for producing a laminated interlayer film of the present invention preferably has a rigidity that can withstand pressure bonding with an interlayer film such as a polyvinyl butyral resin film, and the Young's modulus is an interlayer film (for example, a polyvinyl butyral resin). About 100 times to 1000 times. The Young's modulus of the support is preferably 2.0 to 3.0 Pa, for example.
By adopting such a configuration, it is possible to suppress cracks and wrinkles including the peripheral portion of the laminated intermediate film, and more effectively suppress reflection unevenness of the laminated glass of the present invention obtained by being sandwiched between glass plates. can do.

  Examples of the polymer film having high transparency to visible light include polymer films for various optical films used as members of display devices such as liquid crystal display devices. Examples of the transparent plastic resin film include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate and polyethylene naphthalate (PEN); polycarbonate (PC) and polymethyl methacrylate; polyolefins such as polyethylene and polypropylene; polyimides and triacetyl cellulose. A film mainly composed of (TAC) is exemplified. Among these, a film mainly composed of polyethylene terephthalate and / or triacetyl cellulose is preferable.

  In this invention, it is preferable that the thickness of the said support body is 30 micrometers-100 micrometers, and it is more preferable that it is 50-80 micrometers. By setting it as such thickness, the said infrared light reflection layer can be manufactured stably and the film crack and wrinkle of the liquid crystal film of the lamination | stacking intermediate film of this invention can be suppressed. Moreover, the reflection nonuniformity of the laminated glass of this invention obtained using the lamination | stacking intermediate film of this invention can be suppressed more effectively. Further, if the thickness of the support is within the above range, in the step of thermally bonding the intermediate film and the liquid crystal film of the support with the liquid crystal film, which will be described later, the opposite side of the surface in contact with the liquid crystal film It is easy to suppress uneven crushing of the emboss formed on the surface.

(Liquid crystal film)
As described above, the liquid crystal film is preferably a layer formed by fixing a cholesteric liquid crystal phase.
In the present invention, the layer formed by fixing the cholesteric liquid crystal phase is preferably a laminate of four or more layers. That is, the liquid crystal film preferably has four or more layers formed by fixing the cholesteric liquid crystal phase. FIG. 6 shows an example of the laminated structure of the liquid crystal film, where 1 is the liquid crystal film, and 15a, 15b, 16a and 16b are the infrared reflecting layers.
The infrared reflection layers 15a, 15b, 16a and 16b are preferably layers formed by fixing a cholesteric liquid crystal phase, and light selective reflectivity for reflecting light of a specific wavelength based on the helical pitch of the cholesteric liquid crystal phase. It is preferable to show. In one embodiment of the present invention, adjacent infrared reflective layers 15a and 15b have opposite cholesteric liquid crystal phase spiral directions and the same reflection center wavelength λ ₁₅ . Similarly, adjacent the infrared reflective layer 16a and 16b, together with the spiral directions of the respective cholesteric liquid crystal phase are opposite to each other, the reflection center wavelength lambda ₁₆ is the same. In the present embodiment, since λ ₁₅ ≠ λ ₁₆ is satisfied, the left and right circularly polarized light having a predetermined wavelength λ ₁₅ is selectively reflected by the infrared reflecting layers 15a and 15b, and the wavelength is reflected by the infrared reflecting layers 16a and 16b. Left circularly polarized light and right circularly polarized light having a wavelength λ ₁₆ different from λ ₁₅ are selectively reflected, and as a whole, the reflection characteristics can be broadened.

In FIG. 6, the center wavelength λ ₁₅ of selective reflection by the infrared reflecting layers 15a and 15b is in the range of 1010 to 1070 nm, for example, and the center wavelength λ ₁₆ of selective reflection by the infrared reflecting layers 16a and 16b is, for example, 1190 to 1290 nm. It may be different, such as being in range. The infrared reflection efficiency can be improved by using two pairs of infrared reflection layers each having a selective reflection wavelength in the above range. The spectral distribution of the solar energy intensity shows a general tendency that the shorter the wavelength, the higher the energy, but the spectral distribution in the infrared light wavelength region includes a wavelength of 950 to 1130 nm and a wavelength of 1130 to 1350 nm. There are two energy intensity peaks. At least one pair of infrared reflective layers having a selective reflection center wavelength in the range of 1010 to 1070 nm (more preferably 1020 to 1060 nm) and a selective reflection center wavelength of 1190 to 1290 nm (more preferably 1200 to 1280 nm). By utilizing at least one pair of infrared reflecting layers in the range, light corresponding to the two peaks can be reflected more efficiently, and as a result, the heat shielding property can be further improved.

The helical pitch of the cholesteric liquid crystal phase exhibiting the reflection center wavelength is generally about 650 to 690 nm at the wavelength λ ₁₅ and about 760 to 840 nm at the wavelength λ ₁₆ . Moreover, the thickness of each infrared reflective layer is about 1 μm to 8 μm (preferably about 3 to 7 μm). However, it is not limited to these ranges. An infrared reflective layer having a desired spiral pitch can be formed by adjusting the type and concentration of materials (mainly polymerizable liquid crystal compound and chiral agent) used for forming the layer. Moreover, the thickness of a layer can be made into a desired range by adjusting the application quantity.

As described above, the adjacent infrared reflection layers 15a and 15b have the spiral directions of the respective cholesteric liquid crystal phases opposite to each other, and similarly, the adjacent infrared reflection layers 16a and 16b have the spiral directions of the respective cholesteric liquid crystal phases. It is preferable that they are opposite to each other. As described above, by arranging an infrared reflection layer made of a reverse cholesteric liquid crystal phase and having the same selective reflection center wavelength close to each other, both left circularly polarized light and right circularly polarized light having the same wavelength can be reflected. .
For example, the light that has passed through the infrared reflecting layer 16b (the light that is reflected by the right circularly polarized light having the wavelength λ ₁₆ and only the left circularly polarized light is transmitted) is selected so that the next light passes through 15a and 15b instead of 16b. when the center wavelength of the reflected is not lambda _16, left-handed circularly polarized light component of the wavelength lambda ₁₆ will be the size of the helical pitch passes through different cholesteric liquid crystal layer. In this case, the left circularly polarized light component having the wavelength λ ₁₆ is slightly affected by the optical rotatory power of the cholesteric liquid crystal phase in the other infrared reflecting layer, and the wavelength of the left circularly polarized light component is shifted. Occurs. Naturally, this phenomenon is not limited to the “left circularly polarized light component of wavelength λ ₁₆ ”, but is a change that occurs when circularly polarized light with a certain wavelength passes through cholesteric liquid crystal phases with different helical pitches. is there. As a result of various studies by the present inventor, although it is empirical data, one circularly polarized light component that has not been reflected by the cholesteric liquid crystal layer having a predetermined helical pitch is not reflected, but is another cholesteric liquid crystal having a different helical pitch. When passing through a layer, if the number of the layers passing through becomes 3 or more, the adverse effect on the circularly polarized light component that passes through becomes significant, and even after reaching the cholesteric liquid crystal layer that can reflect the circularly polarized light, It was found that the reflectance due to the layer is significantly reduced. In the present invention, the effects of the present invention can be obtained even if a pair of infrared reflecting layers having the same selective reflection center wavelengths and different spiral directions are not disposed adjacent to each other. Other infrared reflective layers (infrared reflective layers formed by fixing cholesteric liquid crystal phases having different helical pitches and having different central wavelengths of selective reflection) disposed between the infrared reflective layers are 2 or less. Is preferred. Of course, it is preferable that the set of infrared reflecting layers be adjacent to each other.

The aspect of the cholesteric liquid crystal layer is not limited to the above aspect. The structure which laminated | stacked the infrared reflective layer 5 layers or more on one surface of a board | substrate may be sufficient.
The thickness of each infrared reflecting layer constituting the liquid crystal film is preferably 1 to 10 μm, and more preferably 2 to 7 μm. The total thickness of the liquid crystal film is preferably 10 to 50 μm, and more preferably 20 to 40 μm.

  The liquid crystal film used in the laminated intermediate film of the present invention preferably uses a polymerizable liquid crystal compound for forming each infrared reflective layer. Among these, it is preferable to use a curable liquid crystal composition. A preferable example of the liquid crystal composition includes a rod-like liquid crystal compound, a horizontal alignment agent, an optically active compound (chiral agent), and a polymerization initiator. The infrared reflective layer is preferably formed by fixing a composition containing a polymerizable liquid crystal compound and further contains a horizontal alignment agent. The infrared reflection layer may contain two or more of the above-described components. For example, a polymerizable liquid crystal compound and a non-polymerizable liquid crystal compound can be used in combination. Also, a combination of a low-molecular liquid crystal compound and a high-molecular liquid crystal compound is possible. Furthermore, in order to improve the uniformity of alignment, applicability, and film strength, it may contain at least one selected from various additives such as a non-uniformity inhibitor, a repellency inhibitor, and a polymerizable monomer. In the liquid crystal composition, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, a coloring material, inorganic fine particles, metal fine particles, metal oxide fine particles, etc. Can be added within a range that does not degrade the mechanical performance.

Rod-shaped liquid crystal compound:
Examples of the rod-like liquid crystal compound that can be used in the present invention are rod-like nematic liquid crystal compounds. Examples of the rod-like nematic liquid crystal compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoates, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted Phenylpyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only low-molecular liquid crystal compounds but also high-molecular liquid crystal compounds can be used.

The rod-like liquid crystal compound that can be used in the present invention is preferably polymerizable.
The polymerizable rod-like liquid crystal compound can be obtained by introducing a polymerizable group into the rod-like liquid crystal compound. Examples of the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group. The polymerizable group can be introduced into the molecule of the rod-like liquid crystal compound by various methods. The number of polymerizable groups possessed by the polymerizable rod-like liquid crystal compound is preferably 1 to 6, and more preferably 1 to 3. Examples of the polymerizable rod-like liquid crystal compound are described in Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648 and 5,770,107, International Publication WO95 / 22586. No. 95/24455, No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No. 6-16616, and No. 7-110469. 11-80081 and JP-A 2001-328773, and the like. Two or more kinds of polymerizable rod-like liquid crystal compounds may be used in combination. When two or more kinds of polymerizable rod-like liquid crystal compounds are used in combination, the alignment temperature can be lowered.

Orientation control agent:
In the present invention, it is preferable to add a horizontal alignment agent to the liquid crystal composition as an alignment control agent that contributes to stable or rapid formation of a cholesteric liquid crystal phase. Examples of the horizontal alignment agent include fluorine-containing (meth) acrylate polymers and compounds represented by the following general formulas (X1) to (X3), and fluorine-based ones are more preferable. You may contain 2 or more types selected from these. These compounds can reduce the tilt angle of the molecules of the liquid crystal compound or can be substantially horizontally aligned at the air interface of the layer. In this specification, “horizontal alignment” means that the major axis of the liquid crystal molecule is parallel to the film surface, but it is not required to be strictly parallel. An orientation with an inclination angle of less than 20 degrees is meant. When the liquid crystal compound is horizontally aligned in the vicinity of the air interface, alignment defects are unlikely to occur, so that the transparency in the visible light region is increased and the reflectance in the infrared region is increased. On the other hand, when the molecules of the liquid crystal compound are aligned at a large tilt angle, the spiral axis of the cholesteric liquid crystal phase is shifted from the normal of the film surface, so that the reflectivity is reduced or a fingerprint pattern is generated, resulting in an increase in haze or diffraction. It is not preferable because it is shown.
Examples of the fluorine-containing (meth) acrylate-based polymer that can be used as an orientation control agent are described in JP-A No. 2007-272185, [0018] to [0043].

  Hereinafter, the compounds represented by the following general formulas (X1) to (X3) that can be used as a horizontal alignment agent will be described in order.

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and X ¹ , X ² and X ^{3 each} represent a single bond or a divalent linking group. The substituent represented by each of R ^{1 to} R ³ is preferably a substituted or unsubstituted alkyl group (more preferably an unsubstituted alkyl group or a fluorine-substituted alkyl group), an aryl group (particularly a fluorine-substituted alkyl). An aryl group having a group is preferred), a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group, and a halogen atom. The divalent linking groups represented by X ¹ , X ² and X ³ are each an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic residue, —CO—, —NRa— (Ra Is a divalent linking group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), —O—, —S—, —SO—, —SO ₂ — and combinations thereof. Is preferred. The divalent linking group is selected from the group consisting of an alkylene group, a phenylene group, —CO—, —NRa—, —O—, —S— and —SO ₂ —, or the group. It is more preferably a divalent linking group in which at least two groups are combined. The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The number of carbon atoms of the divalent aromatic group is preferably 6-10.

In the formula, R represents a substituent, and m represents an integer of 0 to 5. When m represents an integer greater than or equal to 2, several R may be same or different. Preferred substituents for R are the same as those listed as preferred ranges for the substituents represented by R ¹ , R ² , and R ³ . m preferably represents an integer of 1 to 3, particularly preferably 2 or 3.

In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent. The substituents represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each preferably a substituent represented by R ¹ , R ² and R ³ in the general formula (X1). It is the same as that mentioned as a thing.

Examples of the compounds represented by the formulas (X1) to (X3) that can be used as the alignment control agent include compounds described in JP-A-2005-99248.
In the present invention, as the alignment control agent, one type of the compounds represented by the general formulas (X1) to (X3) may be used alone, or two or more types may be used in combination.

In each infrared reflective layer constituting the liquid crystal film used in the laminated intermediate film of the present invention, the amount of the horizontal alignment agent added is preferably 0.01 to 10% by mass with respect to the polymerizable liquid crystal compound. More preferably, it is 0.01-5 mass%, and it is especially preferable that it is 0.01-1 mass%.
In particular, when a fluorine-based aqueous alignment agent is added, the content is preferably 0.01 to 0.09% by mass and more preferably 0.01 to 0.06% by mass with respect to the polymerizable liquid crystal compound. On the other hand, when adding a non-fluorine type | system | group aqueous orientation agent, 0.1-1 mass% is preferable with respect to a polymeric liquid crystal compound, and 0.2-0.6 mass% is more preferable.

In addition, each infrared reflective layer constituting the liquid crystal film used in the laminated intermediate film of the present invention preferably contains a fluorine atom from the viewpoint of suppressing the amount of the horizontal alignment agent added to the above range. More preferably a perfluoroalkyl group, and particularly preferably a perfluoroalkyl group having 3 to 10 carbon atoms.
When the horizontal alignment agent is non-fluorine-based, it is preferable that the addition amount is 0.1% by mass or more because the problem of alignment defects does not occur.

Optically active compound (chiral agent):
The liquid crystal composition preferably exhibits a cholesteric liquid crystal phase, and for that purpose, it preferably contains an optically active compound. However, when the rod-like liquid crystal compound is a molecule having an illegitimate carbon atom, a cholesteric liquid crystal phase may be stably formed without adding an optically active compound. The optically active compounds are known various kinds of chiral agents (for example, liquid crystal device handbook, Chapter 3-4-3, TN, chiral agent for STN, 199 pages, edited by Japan Society for the Promotion of Science, 42nd Committee, 1989. Description). The optically active compound generally contains an asymmetric carbon atom, but an axially asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom can also be used as a chiral agent. Examples of the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof. The optically active compound (chiral agent) may have a polymerizable group. When the optically active compound has a polymerizable group and the rod-like liquid crystal compound used in combination also has a polymerizable group, it is derived from the rod-like liquid crystal compound by a polymerization reaction of the polymerizable optically active compound and the polymerizable rod-like liquid crystal compound. A polymer having a repeating unit and a repeating unit derived from an optically active compound can be formed. In this embodiment, the polymerizable group possessed by the polymerizable optically active compound is preferably the same group as the polymerizable group possessed by the polymerizable rod-like liquid crystal compound. Accordingly, the polymerizable group of the optically active compound is also preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and an ethylenically unsaturated polymerizable group. Is particularly preferred.
The optically active compound may be a liquid crystal compound.

  The optically active compound in the liquid crystal composition is preferably 1 to 30 mol% with respect to the liquid crystal compound used in combination. A smaller amount of the optically active compound is preferred because it often does not affect liquid crystallinity. Therefore, the optically active compound used as the chiral agent is preferably a compound having a strong twisting power so that a twisted orientation with a desired helical pitch can be achieved even with a small amount. Examples of such a chiral agent exhibiting a strong twisting force include the chiral agents described in JP-A-2003-287623, and can be preferably used in the present invention.

Polymerization initiator:
Since the liquid crystal composition used for forming the infrared reflective layer is a polymerizable liquid crystal composition, it preferably contains a polymerization initiator. In the present invention, since the curing reaction is advanced by irradiation with ultraviolet rays, the polymerization initiator to be used is preferably a photopolymerization initiator capable of starting the polymerization reaction by irradiation with ultraviolet rays. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbons. Substituted aromatic acyloin compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (Described in U.S. Pat. No. 3,549,367), acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850), oxadiazole compounds (described in U.S. Pat. No. 4,221,970), etc. Is mentioned.

  The amount of the photopolymerization initiator used is preferably 0.1 to 20% by mass, more preferably 1 to 8% by mass, based on the liquid crystal composition (solid content in the case of a coating liquid).

Method for forming the liquid crystal film:
The support with a liquid crystal film in which a liquid crystal film is provided on the support can be produced by a known method, but is preferably formed by applying a predetermined composition on the support. More specifically, a curable liquid crystal composition capable of forming a cholesteric liquid crystal phase is applied to the surface of a support, an alignment layer, an infrared reflective layer, or the like, and the composition is converted into a cholesteric liquid crystal phase, followed by a curing reaction. It can be formed by curing (for example, polymerization reaction or crosslinking reaction).

An example of a manufacturing method is
(A) Applying a composition containing an alignment controller and a polymerizable (curable) liquid crystal compound to the surface of a support such as a transparent plastic resin film to form a cholesteric liquid crystal phase;
(B) irradiating the polymerizable liquid crystal composition (hereinafter also referred to as a curable liquid crystal composition) with ultraviolet rays to advance a curing reaction, fixing the cholesteric liquid crystal phase, and forming an infrared reflective layer;
Is a production method comprising at least
By repeating the steps (A) and (B) four times on one surface of the support, a liquid crystal film having the structure shown in FIG. 6 (the support is not shown in FIG. 6) can be produced. By further repeating, a liquid crystal film (infrared light reflection layer) having a further increased number of layers can be formed.

The undercoat layer is preferably formed on the surface of a support such as a transparent plastic resin film by coating. There is no limitation in particular about the coating method at this time, A well-known method can be used.
The alignment layer can be provided by means such as a rubbing treatment of an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound, or formation of a layer having a microgroove. Furthermore, an alignment layer in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known. The alignment layer is preferably formed on the surface of the polymer film by rubbing treatment. In the method for producing a laminated interlayer film of the present invention, it is preferable not to provide an alignment film because the support is not peeled off.

Step (A) In the step (A), first, the curable liquid crystal composition is applied to the surface of the support or the lower infrared reflection layer. The curable liquid crystal composition is preferably prepared as a coating solution in which a material is dissolved and / or dispersed in a solvent. The coating liquid can be applied by various methods such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method. Alternatively, a liquid crystal composition can be discharged from a nozzle using an ink jet apparatus to form a coating film.

  Next, it is preferable that the curable liquid crystal composition applied to the surface to become a coating film is in a cholesteric liquid crystal phase. In the aspect in which the curable liquid crystal composition is prepared as a coating solution containing a solvent, the coating film may be dried and the solvent may be removed to obtain a cholesteric liquid crystal phase. Moreover, in order to set it as the transition temperature to a cholesteric liquid crystal phase, you may heat the said coating film if desired. For example, the cholesteric liquid crystal phase can be stably formed by heating to the temperature of the isotropic phase and then cooling to the cholesteric liquid crystal phase transition temperature. The liquid crystal phase transition temperature of the curable liquid crystal composition is preferably in the range of 10 to 250 ° C., more preferably in the range of 10 to 150 ° C. from the viewpoint of production suitability and the like. When the temperature is lower than 10 ° C., a cooling step or the like may be required to lower the temperature to a temperature range exhibiting a liquid crystal phase. When the temperature exceeds 200 ° C., a high temperature is required to make the isotropic liquid state higher than the temperature range once exhibiting the liquid crystal phase, which is disadvantageous from waste of thermal energy, deformation of the substrate, and alteration.

(B) Step Next, in the step (B), the coating film in the cholesteric liquid crystal phase is irradiated with ultraviolet rays to advance the curing reaction. For ultraviolet irradiation, a light source such as an ultraviolet lamp is used. In this step, by irradiating with ultraviolet rays, the curing reaction of the liquid crystal composition proceeds, the cholesteric liquid crystal phase is fixed, and an infrared reflecting layer is formed.
No particular limitation is imposed on the amount of irradiation energy of ultraviolet rays, in ^{general, 100mJ / cm 2 ~800mJ / cm} 2 is preferably about. Moreover, there is no restriction | limiting in particular about the time which irradiates the said coating film with an ultraviolet-ray, However, It will be determined from the viewpoint of both sufficient intensity | strength and productivity of a cured film.

  In order to accelerate the curing reaction, ultraviolet irradiation may be performed under heating conditions. Moreover, it is preferable to maintain the temperature at the time of ultraviolet irradiation in the temperature range which exhibits a cholesteric liquid crystal phase so that a cholesteric liquid crystal phase may not be disturbed. Also, since the oxygen concentration in the atmosphere is related to the degree of polymerization, if the desired degree of polymerization is not reached in the air and the film strength is insufficient, the oxygen concentration in the atmosphere is reduced by a method such as nitrogen substitution. It is preferable. A preferable oxygen concentration is preferably 10% or less, more preferably 7% or less, and most preferably 3% or less. The reaction rate of the curing reaction (for example, polymerization reaction) that proceeds by irradiation with ultraviolet rays is 70% or more from the viewpoint of maintaining the mechanical strength of the layer and suppressing unreacted substances from flowing out of the layer. Preferably, it is 80% or more, more preferably 90% or more. In order to improve the reaction rate, a method of increasing the irradiation amount of ultraviolet rays to be irradiated and polymerization under a nitrogen atmosphere or heating conditions are effective. In addition, after polymerization, a method of further promoting the reaction by a thermal polymerization reaction by maintaining the polymer at a temperature higher than the polymerization temperature, or a method of irradiating ultraviolet rays again (however, irradiation is performed under conditions satisfying the conditions of the present invention). Can also be used. The reaction rate can be measured by comparing the absorption intensity of the infrared vibration spectrum of a reactive group (for example, a polymerizable group) before and after the reaction proceeds.

In the above process, the cholesteric liquid crystal phase is fixed and an infrared reflective layer is formed. Here, the state in which the liquid crystal phase is “fixed” is the most typical and preferred mode in which the orientation of the liquid crystal compound in the cholesteric liquid crystal phase is maintained. However, it is not limited to this, and specifically, it is usually 0 ° C. to 50 ° C., and under severer conditions, in the temperature range of −30 ° C. to 70 ° C., the layer has no fluidity, and is oriented by an external field or an external force. It shall mean a state in which the fixed orientation form can be kept stable without causing a change in form. In the present invention, the alignment state of the cholesteric liquid crystal phase is fixed by a curing reaction that proceeds by ultraviolet irradiation.
In the present invention, it is sufficient that the optical properties of the cholesteric liquid crystal phase are maintained in the layer, and the liquid crystal composition in the infrared reflecting layer is no longer required to exhibit liquid crystal properties. For example, the liquid crystal composition may have a high molecular weight due to a curing reaction and may no longer have liquid crystallinity.

  In addition, when using the laminated intermediate film obtained by the laminated intermediate film production method of the present invention or the laminated glass obtained by the laminated glass production method of the present invention described later as an infrared light reflector, other important performances are: Visible light transmittance and haze. By adjusting the selection of materials and manufacturing conditions, etc., an infrared light reflecting plate exhibiting preferable visible light transmittance and haze can be provided according to applications. For example, in an aspect used for an application having a high visible light transmittance, an infrared light reflecting plate having a visible light transmittance of 90% or more and an infrared light reflectance satisfying the above reaction can be obtained. .

(Other constituent layers of support with liquid crystal film)
Moreover, the said support body with a liquid-crystal film | membrane may have a non-light-reflective layer containing an organic material and / or an inorganic material other than the said structure. Examples of the non-light-reflective layer that can be used in the present invention include an easy-adhesion layer and an adhesive layer for facilitating close contact with the intermediate film.
In another example of the non-light-reflective layer that can be used in the present invention, an undercoat layer that may be provided when forming an infrared reflective layer of a cholesteric liquid crystal phase, and an infrared reflective layer are formed. In some cases, an alignment layer that more precisely defines the alignment direction of the liquid crystal compound is used.

Adhesive layer:
As described above, the support with a liquid crystal film may include an adhesive layer.
As the adhesive material, general adhesive materials such as acrylic, polyester, polyurethane, polyolefin, and polyvinyl alcohol can be used as long as they do not contradict the gist of the present invention. In the present invention, among these, it is preferable to use polyester or acrylic, and it is more preferable to use acrylic.
The pressure-sensitive adhesive material may be obtained commercially, and examples of the pressure-sensitive adhesive material preferably used in the present invention include PET-W manufactured by Sunlitz Co., Ltd. and PD-S1 manufactured by Panac Industry Co., Ltd. Can be mentioned.
The thickness of the pressure-sensitive adhesive layer can be set to 0.1 to 5.0 μm, for example.

Easy adhesion layer:
The easy adhesion layer has a function of improving the adhesion between the infrared reflection layer and the pressure-sensitive adhesive layer, for example. Examples of materials that can be used for forming the easy-adhesion layer include polyvinyl butyral (PVB) resin. The polyvinyl butyral resin is a kind of polyvinyl acetal produced by reacting polyvinyl alcohol (PVA) and butyraldehyde with an acid catalyst, and is a resin having a repeating unit having the following structure.

The easy-adhesion layer may be a layer made of an acrylic resin, a styrene / acrylic resin, a urethane resin, a polyester resin, or the like, so-called an undercoat layer. An easy adhesion layer made of these materials can also be formed by coating. Some commercially available polymer films are provided with an undercoat layer. Therefore, these commercially available products can be used as a substrate. Furthermore, you may add a ultraviolet absorber, an antistatic agent, a lubricant, an antiblocking agent, etc. to the said easily bonding layer.
In addition, as for the thickness of an easily bonding layer, 0.1-5.0 micrometers is preferable.

Undercoat layer:
The support with a liquid crystal film may have an undercoat layer on the infrared reflective layer side. In general, the infrared reflective layer is preferably provided on the support, but at this time, depending on the support, it may be preferable to provide the infrared reflective layer on the undercoat layer.
Examples of materials that can be used to form the undercoat layer include acrylate copolymer, polyvinylidene chloride, styrene butadiene rubber (SBR), aqueous polyester, and the like. Further, in an embodiment in which the surface of the undercoat layer is bonded to the intermediate film, it is preferable that the adhesiveness between the undercoat layer and the intermediate film is good. It is preferable. Moreover, since it is necessary to adjust adhesive force moderately as above-mentioned for undercoat, dialdehydes, such as glutaraldehyde and 2, 3- dihydroxy- 1, 4- dioxane, or hardening agents, such as a boric acid, are used. It is preferable to use the film appropriately. The addition amount of the hardener is preferably 0.2 to 3.0% by mass of the dry mass of the undercoat layer.
The thickness of the undercoat layer is preferably 0.05 to 0.5 μm.

Alignment layer:
The support with a liquid crystal film may have an alignment layer between the liquid crystal film and the intermediate film, but in the method for producing a laminated intermediate film of the present invention, the support layer is not peeled off. It is preferable not to provide it.
Since the alignment layer needs to be adjacent to the infrared reflective layer when forming the infrared reflective layer of the cholesteric liquid crystal phase, it is necessary to provide the alignment layer between the infrared reflective layer of the cholesteric liquid crystal phase and the substrate or undercoat layer. preferable. However, the undercoat layer may have a function of an alignment layer. Moreover, you may have an orientation layer between the infrared reflective layers.

(Characteristics of support with liquid crystal film)
In the method for producing a laminated intermediate film of the present invention, it is preferable that the support with a liquid crystal film has a size in which all end portions of the support with a liquid crystal film are shorter by 1 mm or more than the end portions of the intermediate film. The support with a liquid crystal film is more preferably a size in which all ends of the support with a liquid crystal film are 5 to 30 mm shorter than an end of the intermediate film, and a size that is 10 to 20 mm shorter. Is particularly preferred.

  In the method for producing a laminated glass of the present invention to be described later, the heat shrinkage ratio before and after the step of pressure-bonding the laminated interlayer film of the present invention sandwiched between the glass plates to be described later of the liquid crystal film is the heating at that time In the temperature range, it is preferably 0.1 to 5%, more preferably 0.1 to 3%, and particularly preferably 0.5 to 2%.

  The thickness of the support with a liquid crystal film varies depending on the number of layers of the infrared reflective layer, but is preferably 40 to 150 μm, more preferably 60 to 130 μm in the method for producing a laminated intermediate film of the present invention, It is especially preferable that it is 70-120 micrometers. In particular, when the support with a liquid crystal film is cut using a laser in the cutting step described later, the thickness of the support with a liquid crystal film satisfies the condition of the formula (1) described later that the thickness is 70 to 100 μm. It is preferable from the viewpoint of facilitating.

  In the method for producing a laminated interlayer film of the present invention, a brittle film can be used as the liquid crystal film. Examples of the brittle liquid crystal film include the infrared reflective layer of the cholesteric liquid crystal layer. As a criterion for the brittleness of the liquid crystal film that can be used in the method for producing a laminated interlayer film of the present invention, the Young's modulus of the liquid crystal film is preferably 0.5 to 10 GPa, and preferably 1 to 8 GPa. More preferably, it is 2-5 GPa. The liquid crystal film preferably has an elongation at break by a tensile test of 0.1 to 20%, more preferably 0.5 to 10%, and particularly preferably 1 to 5%.

<Process for Laminating Liquid Crystal Film of Support with Liquid Crystal Film and First Intermediate Film>
The manufacturing method of the lamination | stacking intermediate film of this invention includes the process of laminating | stacking the liquid crystal film of a support body with a liquid crystal film containing the support body and the liquid crystal film formed on this support body, and a 1st intermediate film.
First, an intermediate film that can be used in the method for producing a laminated intermediate film of the present invention will be described.

(Interlayer film)
The laminated intermediate film obtained by the method for producing a laminated intermediate film of the present invention includes a first intermediate film and a second intermediate film. In ordinary laminated glass, the first and second intermediate films on both sides of the liquid crystal film have the same film thickness, but the present invention is not limited to the method for producing a laminated interlayer film for laminated glass in such an embodiment. A laminated interlayer film can be manufactured in such a manner that the thicknesses of the first and second interlayer films are different. Further, the compositions of the first and second intermediate films may be the same or different.

It is preferable that the thermal contraction rate before and after the step of pressure-bonding the laminated intermediate film described later of the first and second intermediate films is 1 to 20% in the range of the heating temperature at that time. It is more preferably ˜15%, and particularly preferably 2 to 10%.
The thickness of the first and second intermediate films is preferably 100 to 1000 μm, more preferably 200 to 800 μm, and particularly preferably 300 to 500 μm. The first and second intermediate films may be thickened by overlapping a plurality of sheets.
The brittleness of the first and second interlayer films is preferably 100 to 800%, more preferably 100 to 600%, more preferably 200 to 500%. It is particularly preferred that

resin:
The first and second intermediate films are preferably resin intermediate films. The resin interlayer is preferably a polyvinyl acetal-based resin film. There is no restriction | limiting in particular as said polyvinyl acetal type-resin film, For example, what is described in Unexamined-Japanese-Patent No. 6-000926, Unexamined-Japanese-Patent No. 2007-008797 etc. can be used preferably. Among the polyvinyl acetal resin films, a polyvinyl butyral resin film is preferably used in the present invention. The polyvinyl butyral resin film is not particularly defined as long as it is a resin film mainly composed of polyvinyl butyral, and a widely known polyvinyl butyral resin film as an interlayer film for laminated glass can be employed. Among them, in the present invention, the intermediate film is preferably polyvinyl butyral or ethylene vinyl acetate. In addition, resin which is a main component means resin which occupies the ratio of 50 mass% or more of the said resin intermediate film.

Additive:
The first and second intermediate films may contain an additive within a range not departing from the gist of the present invention.
Examples of the additive include fine particles for heat ray shielding, fine particles for sound insulation, and a plasticizer. Examples of the heat ray shielding fine particles and the sound insulation fine particles include inorganic fine particles and metal fine particles. By dispersing and mixing such fine particles in an elastic body such as the first or second intermediate film, a heat shielding effect can be obtained. At the same time, with such a configuration, it is preferable to inhibit the propagation of sound waves and obtain a vibration damping effect. The structure of the fine particles is preferably spherical, but may not be true. The shape may be changed. The fine particles are desirably dispersed in the intermediate film (preferably PVB), and may be added in a suitable capsule or added together with a dispersant. The addition amount in this case is not particularly limited, but is preferably 0.1 to 10% by mass of the resin component.

  Examples of the inorganic fine particles include calcium carbonate, alumina, kaolin clay, calcium silicate, magnesium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, talc, feldspar powder, mica, barite, barium carbonate, titanium oxide, silica, glass bead. And the like. These may be used alone or in combination.

  Further, as the heat ray shielding fine particles, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), tin-doped zinc oxide, silicon-doped zinc oxide, Examples thereof include zinc antimonate, lanthanum hexaboride, cerium hexaboride, fine gold powder, fine silver powder, fine platinum powder, fine aluminum powder, iron, nickel, copper, stainless steel, tin, cobalt, and alloy powders containing these. Examples of the light shielding agent include carbon black and red iron oxide. As the pigment, a dark pigment formed by mixing four kinds of black pigment carbon black, red pigment (CI Pigment red), blue pigment (CI Pigment blue) and yellow pigment (CI Pigment yellow). Examples include reddish-brown mixed pigments.

  It does not specifically limit as said plasticizer, The well-known plasticizer generally used as a plasticizer for this kind of intermediate film can be used. For example, triethylene glycol-di-2-ethylbutyrate (3GH), triethylene glycol-di-2-ethylhexanoate (3GO), triethylene glycol-di-n-heptanoate (3G7), tetraethylene glycol- Di-2-ethylhexanoate (4GO), tetraethylene glycol-di-n-heptanoate (4G7), oligoethylene glycol-di-2-ethylhexanoate (NGO) and the like are preferably used. These plasticizers are generally used in a range of 25 to 70 parts by mass with respect to 100 parts by mass of a resin (preferably polyvinyl acetal resin) that is a main component of the resin interlayer.

(Method of thermal bonding)
In the method for producing a laminated intermediate film of the present invention, since the support is not peeled off, the liquid crystal film and the first intermediate film of the support with a liquid crystal film do not necessarily need to be thermally bonded (or thermocompression bonded). . However, in the method for producing a laminated intermediate film of the present invention, from the viewpoint of improving handling and misalignment, the liquid crystal film of the support with a liquid crystal film and the first intermediate film are liquid crystal of the support with a liquid crystal film described later. Heat bonding is preferably performed before or after the film cutting step.
There is no restriction | limiting in particular as the method of the said heat bonding, The thermocompression bonding which presses a heating body, the heat sealing | fusion by the heating by laser irradiation, etc. are employable. In addition, methods described in JP 2010-265140 A, JP 2000-219543 A, and the like can also be employed. Among them, in the method for producing a laminated interlayer film of the present invention, it is preferable that the step of thermally bonding the liquid crystal film to the interlayer film is thermocompression bonding.
Although there is no restriction | limiting in particular as the method of the said thermocompression bonding, For example, the method of pressing a 80-140 degreeC heating body is preferable. The heating body may be a flat surface, a curved surface, or a roller. For the thermocompression bonding, a plurality of heating rollers, a heatable flat pressing surface, or the like may be used, or a combination thereof may be used. The thermocompression bonding may be performed on one surface of the support / liquid crystal film / intermediate film laminate or only on one surface. In that case, one of the rollers used for thermocompression is heated. It may be a roller or a pressing surface that is not. Among these, the method for producing a laminated interlayer film of the present invention preferably uses a heating roller in the thermocompression bonding step, and more preferably uses a combination of a heating roller and a non-heating roller.

  Here, the support body with a liquid crystal film which is a laminate of the support body and the liquid crystal film may include another constituent layer between the support body and the liquid crystal film. The liquid crystal film and the first intermediate film may be adjacent to each other, or other constituent layers may be included between them. In this case, the other constituent layer includes an adhesive layer. For example, when the liquid crystal film and the first intermediate film are adjacent to each other, the temperature of the thermocompression roller can be set to 60 to 120 ° C.

  Usually, the surface of the intermediate film is roughened by embossing or the like so that air can easily escape during sticking. The bonded surface becomes smooth following the adherend surface, and the optical performance is improved. However, the other surface needs to be maintained in a rough state in order to be bonded to a glass plate or the like. That is, in the method for producing a laminated intermediate film of the present invention, at least one surface of the intermediate film is embossed, and the embossed surface of the intermediate film is in contact with the liquid crystal film of the support with a liquid crystal film It is preferable to laminate so that it may become a surface on the opposite side. Alternatively, the surface of the intermediate film that is not in contact with the liquid crystal film after thermocompression bonding may be actively embossed.

<Step of simultaneously cutting the liquid crystal film and the support of the support with a liquid crystal film>
The manufacturing method of the lamination | stacking intermediate film of this invention includes the process of cut | disconnecting simultaneously the liquid crystal film and support body of the said support body with a liquid crystal film.
Hereinafter, the timing of the cutting process and a preferable cutting method will be described.

(Timing with the step of laminating the liquid crystal film of the support with the liquid crystal film and the first intermediate film)
The step of laminating the liquid crystal film of the support with a liquid crystal film and the first intermediate film may be performed before the step of simultaneously cutting the liquid crystal film and the support of the support with a liquid crystal film described later, It may be done later. That is, the method for producing a laminated intermediate film of the present invention is described as follows: “After the step of laminating the liquid crystal film of the support with a liquid crystal film and the first intermediate film, the first intermediate film, the liquid crystal film, and the An embodiment in which the support is simultaneously cut (hereinafter also referred to as a first preferred embodiment of the present invention), and a liquid crystal film of the support with a liquid crystal film after the step of simultaneously cutting the liquid crystal film and the support. A mode of laminating the first intermediate film (hereinafter also referred to as a second preferred mode of the present invention).
Hereinafter, the configuration of the intermediate film, the first preferred embodiment of the present invention, and the second preferred embodiment of the present invention will be described. In addition, the manufacturing method of the lamination | stacking intermediate film of this invention has a more preferable 2nd preferable aspect of this invention.

(1) First Preferred Aspect A first preferred aspect of the present invention is the first intermediate film, after the step of laminating the liquid crystal film of the support with a liquid crystal film and the first intermediate film, The liquid crystal film and the support are cut simultaneously.
The cutting method at this time is not particularly limited as long as the liquid crystal film does not crack and is not contrary to the gist of the present invention. For example, at the time of processing, it may be cut using a blade, or may be cut by laser, water jet or heat.
Among these, it is preferable that the step of cutting the first intermediate film, the liquid crystal film and the support at the same time includes a step of cutting using a blade or a laser.

・ Cutter:
In the step of cutting the first intermediate film, the liquid crystal film, and the support at the same time, when cutting with a blade, a punching method used in conventional film processing can be suitably used. The cutter may be a rotary round blade or a mold blade. Among these, in the method for producing a laminated interlayer film of the present invention, a die blade is preferable as the blade.
In the method for producing a laminated interlayer film of the present invention, the cutting edge angle is not particularly limited in the cutting step, but using a mold blade having a cutting edge angle of 20 ° to 40 ° suppresses the occurrence of cracks in the liquid crystal film. From the viewpoint, it is preferably 25 to 35 °.
In the method for producing a laminated interlayer film of the present invention, the corner shape of the die blade is not particularly limited, but a radius of 2 mm or more is preferable from the viewpoint of suppressing separation of the liquid crystal film and the support, and is 1 to 10 mm. It is more preferable.
In the method for producing a laminated interlayer film according to the present invention, the material of the die blade is not particularly limited, but is preferably SK material, high speed steel or SUS440C from the viewpoint of both prevention of blade chipping and sharpness quality, and is an SK material. It is more preferable.
In the method for producing a laminated interlayer film according to the present invention, the Rockwell hardness of the mold blade is preferably HRA 70 or more from the viewpoint of blade durability, and more preferably 74 to 85.
In the method for producing a laminated interlayer film of the present invention, the bending strength of the die blade is preferably 2.5 MPa or more from the viewpoint of blade durability, and more preferably 3.0 to 4.5 MPa.
The method for producing a laminated interlayer film according to the present invention is such that a pressing rubber having a durometer type A (Shore A) hardness of 20 to 80 ° based on JIS K 6253 is provided near the blade portion of the mold blade. It is preferable from a viewpoint of suppressing peeling of the body, and the hardness of the pressing rubber is more preferably 20 to 60 °.

The mold blade is not particularly limited, and includes a method of using one or a plurality of so-called Thomson blades according to a desired shape, and a method of penetrating an object with two punches and a die. Can do. As the mold blade, a Thomson blade is preferable from the viewpoint of suppressing separation of the liquid crystal film and the support and preventing cracking of the liquid crystal film.
The method using the Thomson blade is not particularly limited as long as it is not contrary to the gist of the present invention, and a known Thomson blade can be used. The Thomson blade can also be obtained and used commercially. For example, those manufactured by Nagoya Blade Type Co., Ltd. and Nakayama Co., Ltd. can be preferably used.
It is preferable that the punch and die opening have a desired punching hole shape, and the punch and die have a predetermined clearance. The punch and the die are combined with high precision, and the gap between the punch diameter and the die opening portion (one side clearance) is usually preferably 1 μm to 4 μm. However, punching is possible even if this range is exceeded. Specifically, a method described in JP-A-2005-183501 is preferably used. In addition, a large number of punches and dies may be formed on each mold, and the pitch between punches, the pitch between die openings, and the diameters of punch holes and die openings are finished with high accuracy.

In the method for producing a laminated interlayer film of the present invention, it is preferable to cut the support with a liquid crystal film by inserting a mold blade from the support side of the support with the liquid crystal film. According to the study by the present inventors, when the mold blade is inserted from the liquid crystal film side, the end of the liquid crystal film of the support with a liquid crystal film sometimes floats from the support. In general, when the end of the liquid crystal film of the support with a liquid crystal film is lifted from the support, the support and the liquid crystal film are inserted into two glasses by being sandwiched between two intermediate films to form a laminated glass. The edge floating between the two tends to cause a failure caused by spreading the liquid crystal film in the plane after the laminated glass. On the other hand, in a preferred embodiment of the method for producing a laminated interlayer film of the present invention, by causing a mold blade to enter from the support side of the support with a liquid crystal film, the end face peeling (floating) of the liquid crystal film at the time of cutting occurs. It is possible to suppress the failure caused by the peeling of the liquid crystal film spreading in the plane after the laminated glass.
Regarding the direction in which the mold blade enters, there is a similar tendency even when the intermediate film is laminated or thermally bonded, and the first intermediate film, the liquid crystal film, and the support are simultaneously cut. In the first preferred embodiment, it is preferable to include a step of punching the mold blade from the first support side (that is, from the support side to the liquid crystal film).

·laser:
In the step of simultaneously cutting the first intermediate film, the liquid crystal film, and the support, a laser that is used in conventional film processing can be suitably used when cutting using a laser.
In the method for producing a laminated interlayer film of the present invention, in the cutting step, the end of the liquid crystal film of the support with a liquid crystal film may be cut using a laser under a condition satisfying the following formula (1). This is preferable from the viewpoint of suppressing floating.
Formula (1): 0.0002 <W / (T × V) <0.0008
(In formula (1), W represents the laser output (unit: W), T represents the thickness of the laminate to be cut (unit: μm), and V represents the laser scanning speed (mm / second).)
When W / (T × V) satisfies 0.0005 ≦ W / (T × V) ≦ 0.008, the end of the liquid crystal film of the support with the liquid crystal film is lifted from the support. It is more preferable from the viewpoint of suppression.
By setting the irradiation intensity below the lower limit of the above formula (1), it is possible to suppress the end of the liquid crystal film of the support with a liquid crystal film from being lifted from the support because the irradiation intensity is low. In general, when the end of the liquid crystal film of the support with a liquid crystal film is lifted from the support, the support and the liquid crystal film are inserted into two glasses by being sandwiched between two intermediate films to form a laminated glass. The floating of the end portion of the liquid crystal tends to spread from the end portion of the liquid crystal film and cause a failure.
Although there is no restriction | limiting in particular as a wavelength of the said laser, In the manufacturing method of the lamination | stacking intermediate film of this invention, it is preferable to use the laser whose wavelength is an infrared region.
The wavelength of the infrared laser may be any of near-infrared, mid-infrared, and far-infrared wavelengths. Among them, it is preferable to use one having a far-infrared wavelength. Examples of the near infrared laser include a YAG laser (wavelength 1064 nm). Examples of the far-infrared infrared laser include a carbon dioxide laser (wavelength: 10600 nm).
The laser irradiation direction is preferably on the support side. Specifically, in the step of simultaneously cutting the first intermediate film, the liquid crystal film, and the support in the first preferred embodiment of the present invention, a laser is directed from the support to the first intermediate film. Is preferable from the viewpoint of suppressing floating of the end portion between the support and the liquid crystal film.

(2) Second Preferred Aspect A second preferred aspect of the present invention is that, after the step of simultaneously cutting the liquid crystal film and the support, the liquid crystal film of the support with a liquid crystal film, the first intermediate film, Are stacked.
A second preferred embodiment of the present invention is a step of simultaneously cutting the liquid crystal film and the support, wherein all ends of the support and all ends of the liquid crystal film are ends of the first intermediate film. It is preferable to cut so as to be 1 mm or more inside from the portion.
A second preferred embodiment of the present invention includes a step of cutting the first intermediate film into a desired shape before the step of laminating the liquid crystal film of the support with a liquid crystal film and the first intermediate film. Preferably, the desired shape is such that all the end portions of the support and all the end portions of the liquid crystal film are 1 mm or more inward from the end portions of the first intermediate film as described above. Size is preferred.
As a method for simultaneously cutting the liquid crystal film and the support in the second preferred embodiment of the present invention, the first intermediate film, the liquid crystal film and the support in the first preferred embodiment of the present invention are simultaneously cut. The method described in the step to be performed and other known methods can be adopted, and there is no particular limitation.
Among them, the second preferred embodiment of the present invention preferably includes a step of cutting using a laser. The description and preferred range of the step of cutting using a laser in the second preferred embodiment of the present invention are the same as the description and preferred range of the first preferred embodiment of the present invention.
Moreover, in the 2nd preferable aspect of this invention, it is also preferable to include the process of penetrating a die blade from the said support body side and punching out. The description and preferred range of the step of cutting using the blade in the second preferred embodiment of the present invention are substantially the same as the description and preferred range of the first preferred embodiment of the present invention.

  In a second aspect of the present invention, the support / liquid crystal film / intermediate film is formed such that all ends of the support and all ends of the liquid crystal film are 1 mm or more inward from the end of the intermediate film. It is preferable to include the process of laminating in this order. After laminating in this way, positional deviation can be suppressed by performing a process of thermally bonding the liquid crystal film of the support with the liquid crystal film and the first intermediate film.

<Step of laminating the second intermediate film>
The manufacturing method of the lamination | stacking intermediate film of this invention includes the process of laminating | stacking a 2nd intermediate film on the surface at the side of the support body of the said support body with a liquid crystal film. That is, the laminated intermediate film of the present invention further has a second intermediate film. The step of laminating the second intermediate film on the support-side surface of the support with a liquid crystal film may be performed before or after the step of simultaneously cutting the liquid crystal film and the support, Preferably it is done.
The liquid crystal film and the second intermediate film may be adjacent to each other, or other constituent layers may be included between them. In this case, the other constituent layer includes an adhesive layer. The adhesive layer is usually provided on the second intermediate film side.

  The laminated intermediate film including the second intermediate film may be cut using a blade, or may be cut by laser, water jet, or heat during processing.

[Laminated interlayer film]
The laminated interlayer film of the present invention is manufactured by the method for producing a laminated interlayer film.
In the second embodiment, the laminated intermediate film of the present invention has a first intermediate film 3 adjacent to the surface on the liquid crystal film 1 side of the support with a liquid crystal film as shown in FIG. A second intermediate film 3 ′ is adjacent to the surface of the support with film 2 on the support 2 side, and all the end portions of the liquid crystal film are 1 mm or more than the end portions of the two intermediate films. The inside is preferred. However, the laminated intermediate film of the present invention is manufactured using the support 5 with a liquid crystal film as shown in FIG. 4 so that all the end portions of the liquid crystal film and the end portions of the two intermediate films are in the same position. However, a laminated intermediate film having a structure as shown in FIG. 5 may be used. Furthermore, in the laminated intermediate film of the present invention, it is preferable that the liquid crystal film is a rod-like cholesteric liquid crystal and a reflection film in the infrared region.
In the second aspect, the preferred range of the positional relationship between all the end portions of the liquid crystal film and the end portions of the intermediate film is the support / liquid crystal film / This is the same as the preferable range of the positional relationship among all the end portions of the support, all the end portions of the liquid crystal film, and the end portions of the intermediate film in the step of laminating the intermediate films in order.

[Production method of laminated glass]
The method for producing a laminated glass of the present invention includes a step of sandwiching the laminated interlayer film of the present invention obtained as described above between at least two glass plates. The glass plate is preferably two sheets of a first glass and a second glass. A preferred embodiment at this time will be described below.
The method for laminating the laminated intermediate film of the present invention including the liquid crystal film and the intermediate film with the first glass or the second glass is not particularly limited, and is inserted between two glass plates by a known method. Can be laminated.

  The laminated intermediate film sandwiched between the glass plates has a structure in which the glass plate / first intermediate film / liquid crystal film / support / second intermediate film / glass plate are laminated in this order.

FIG. 3 is a schematic view showing an example of a structure of a laminated glass including a laminated intermediate film 7 sandwiched between glass plates, which is obtained by the manufacturing method in the second aspect of the present invention. In FIG. 3, 1 is a liquid crystal film (preferably a resin film which is an infrared reflecting layer), 2 is a support, 3 is an intermediate film, 3 'is a second intermediate film, and 4 is a first glass plate. 4 'represents a second glass plate, respectively. As shown in FIG. 3, the laminated intermediate film 7 sandwiched between the glass plates is such that the end portions of the liquid crystal film are the end portions of the glass plates 4 and 4 ′, the first intermediate film 3 and the second intermediate film. Although it is preferable that it exists inside the edge part of intermediate film 3 ', it may be the same length or may protrude. The end portions of the glass plates 4 and 4 ′ and the end portions of the first intermediate film 3 and the second intermediate film 3 ′ may be at the same position, or one of them may protrude.
When the laminated intermediate film obtained by the method for producing a laminated intermediate film of the present invention has such a preferable configuration, in the step of pressure-bonding the laminated intermediate film sandwiched between the glass plates described later while heating, the liquid crystal film Generation of wrinkles and cracks can be suppressed.

  In the laminate sandwiched between the glass plates, the end of the liquid crystal film is preferably 1 to 50 mm inside on the average at one end of each side of the end of the glass plate. It is more preferably 30 mm inside, and particularly preferably 10 to 20 mm inside.

  In the laminate sandwiched between the glass plates, the liquid crystal film 1 and the first intermediate film 3, and the support 2 and the second intermediate film 3 ′ may be adjacent to each other, or may have other constituent layers. You may do it.

(Glass plate)
In the method for producing a laminated glass of the present invention, it is preferable that the glass plate is a curved glass even if the glass plate has no curvature. When the glass plate is a glass having no curvature, particularly when the size of the laminated glass is large, wrinkles and cracks are likely to occur in the peripheral portion of the laminated glass, and the method for producing a laminated glass of the present invention is preferably applied. be able to.
On the other hand, when the glass plate is a curved glass, wrinkles and cracks are more likely to occur in the liquid crystal film as compared with a glass having no curvature. The method for producing a laminated glass of the present invention can suppress wrinkles and cracks even when the glass plate is a curved surface (curved glass plate).
The two glass plates sandwiching the liquid crystal film may have different thicknesses or may be colored. In particular, when used for a windshield of an automobile for the purpose of heat insulation, a coloring component such as a metal is added to the glass so that the visible light transmittance in a laminated glass state does not fall below 70% defined in JIS-R3211. The heat shielding property can be effectively improved by using green glass in general. About the color density of green glass, it is preferable to adjust to the density | concentration suitable for the objective by adjusting the quantity of the metal component to add or adjusting thickness.

The curved glass plate is obtained by bending soda-lime glass heated to a temperature equal to or higher than the softening point by a float method, and the use of a three-dimensional curved glass plate is simple.
The three-dimensionally curved glass plate is a glass plate having a different radius of curvature depending on the location, such as a spherical surface, an elliptical spherical surface, or a front glass of an automobile.
The curvature radius of the curved glass plate is not particularly limited, but is preferably 0.9 m to 3 m. If the radius of curvature is smaller than 0.9 m, the resin film generally tends to be wrinkled in the laminating process. However, in the manufacturing method of the present invention, the resin film is wrinkled even if the radius of curvature is less than 0.9 m. Can be suppressed. Further, when the radius of curvature is large, the shape is close to a flat surface, and in general, the resin film is less likely to be wrinkled, but cracking may occur in the peripheral portion of the resin film. Therefore, in the manufacturing method of the present invention, the effect of the present invention appears even if the curvature radius of the curved glass is 3 m or more, but from the viewpoint of suppressing the generation of wrinkles in addition to the occurrence of cracks, It can be particularly preferably used when the radius of curvature is 3 m.
Further, the laminated glass obtained by the method for producing laminated glass of the present invention includes at least two glass plates, but the method for producing laminated glass of the present invention is used even when the curvature of each glass plate is different. Can do.

<Step of crimping while heating the laminate sandwiched between the glass plates>
The method for producing a laminated glass of the present invention preferably includes a step of pressure bonding while heating the laminated interlayer film of the present invention sandwiched between the glass plates.
The lamination interlayer film of the present invention sandwiched between the glass plates and the glass plate are bonded together by, for example, pre-pressing at a temperature of 80 to 120 ° C. for 30 to 60 minutes under reduced pressure using a vacuum bag or the like, and then autoclave. The laminated glass is laminated at a temperature of 120 to 150 ° C. under a pressure of 1.0 to 1.5 MPa, and a laminate is sandwiched between two glasses.
At this time, it is preferable that the time of thermocompression bonding at a temperature of 120 to 150 ° C. under a pressure of 1.0 to 1.5 MPa is 20 to 90 minutes.
After the thermocompression bonding, there is no particular limitation on the method of cooling, and the laminated glass body may be obtained by cooling while releasing the pressure as appropriate. In the present invention, it is preferable to lower the temperature while maintaining the pressure after completion of the thermocompression bonding from the viewpoint of further improving the wrinkles and cracks of the obtained laminated glass body. Here, when the temperature is lowered while maintaining the pressure, the pressure inside the apparatus at the time of thermocompression bonding (preferably 130 ° C.) is such that the pressure inside the apparatus at 40 ° C. becomes 75% to 100% at the time of thermocompression bonding. It means to cool down. The method of lowering the temperature while maintaining the pressure is not particularly limited as long as the pressure when the temperature is lowered to 40 ° C. is within the above range, but the pressure inside the pressure device naturally decreases as the temperature decreases. In addition, a mode in which the temperature is lowered without leaking pressure from the inside of the apparatus or a mode in which the temperature is lowered while further pressurizing from the outside so that the internal pressure of the apparatus does not decrease as the temperature decreases is preferable. In the case where the temperature is lowered while maintaining the pressure, it is preferable to cool to 120 ° C. to 150 ° C. and then cool to 40 ° C. over 1 to 5 hours.
In the present invention, it is preferable to include a step of releasing the pressure after the temperature is lowered while the pressure is maintained. Specifically, it is preferable to lower the temperature by releasing the pressure after the temperature in the autoclave becomes 40 ° C. or lower after the temperature is lowered while the pressure is maintained.
From the above, the method for producing a laminated glass body according to the present invention includes a step of sandwiching the laminated interlayer film of the present invention between at least two glass plates, and then 120 to 150 ° C. under a pressure of 1.0 to 1.5 MPa. It is preferable to include a step of thermocompression bonding at a temperature, a step of lowering the temperature while maintaining the pressure, and a step of releasing the pressure.

  The range for thermocompression bonding of the glass plate and the laminated interlayer film of the present invention may be a range over the entire area of the glass plate, but it may be only the peripheral portion of the glass plate, and the thermocompression bonding of the peripheral portion generates wrinkles. It can also be suppressed.

[Laminated glass]
The laminated glass of the present invention is obtained by the method for producing a laminated glass of the present invention.
The laminated glass of the present invention is characterized in that the floating of the end of the liquid crystal film is suppressed.
The laminated glass of the present invention can be preferably cut to any size, and even in that case, the laminated glass of the present invention, including the peripheral part, is restrained from floating at the end between the support and the liquid crystal film, Even if it is cut into an arbitrary size, it is difficult for the end of the liquid crystal film to spread over the entire surface of the laminated glass.

  Although the use of the laminated glass of this invention does not have a restriction | limiting in particular, It is preferable for window glass, such as a house and a motor vehicle.

  Hereinafter, the features of the present invention will be described more specifically with reference to examples and comparative examples (note that comparative examples are not known techniques). The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
<Formation of support with liquid crystal film>
(Preparation of coating solution for undercoat layer)
An undercoat layer coating solution (S1) having the composition shown below was prepared.
Composition of undercoat layer coating solution (S1):
Acrylic ester resin Jurimer ET-410
(Toagosei Co., Ltd., solid content concentration 30%) 50 parts by mass Methanol 50 parts by mass

(Preparation of coating solution for alignment layer)
An alignment layer coating solution (H1) having the composition shown below was prepared.
Composition of coating liquid for alignment layer (H1):
Modified polyvinyl alcohol PVA203 (manufactured by Kuraray) 10 parts by weight Glutaraldehyde 0.5 parts by weight Water 371 parts by weight Methanol 119 parts by weight

(Preparation of coating liquid containing polymerizable liquid crystal (polymerizable liquid crystal composition))
Coating solutions (R1) and (L1) containing polymerizable liquid crystals having the compositions shown in the following table were prepared.

Composition of coating liquid containing polymerizable liquid crystal (R1)

Horizontal alignment agent: (compound described in JP-A-2005-99248)

A coating liquid (L1) was prepared in the same manner except that the chiral agent LC-756 of the coating liquid (R1) containing a polymerizable liquid crystal was changed to the following chiral agent compound 2.
Chiral agent: Compound 2 (compound described in JP-A No. 2002-179668)

  A coating solution (R2) was prepared in the same manner except that the formulation amount of the chiral agent LC-756 in the coating solution (R1) containing a polymerizable liquid crystal was changed to 0.236 parts by mass.

  A coating liquid (L2) was prepared in the same manner except that the formulation amount of the chiral agent compound 2 in the coating liquid (L1) containing a polymerizable liquid crystal was changed to 0.148 parts by mass.

(Coating and film formation of support with liquid crystal film)
On the surface of a PET film (no undercoat layer, manufactured by FUJIFILM Corporation, thickness: 50 μm, size 320 mm × 400 mm), the undercoat layer coating solution (S1) is dried using a wire bar. Was applied to a thickness of 0.25 μm. Then, it heated at 150 degreeC for 10 minute (s), dried and solidified, and formed the undercoat.
Next, an alignment layer coating solution (H1) was applied on the formed undercoat layer using a wire bar so that the film thickness after drying was 1.0 μm. Then, it heated at 100 degreeC for 2 minute (s), dried and solidified, and formed the orientation layer. The alignment layer was subjected to rubbing treatment (rayon cloth, pressure: 0.1 kgf, rotation speed: 1000 rpm, conveyance speed: 10 m / min, frequency: 1 reciprocation).

Next, using the prepared coating liquids (R1), (R2), (L1) and (L2) containing a polymerizable liquid crystal, the cholesteric liquid crystal phase is fixed by the following procedure, and an infrared reflective layer (hereinafter, also referred to as a liquid crystal film). Say) manufactured.
(1) Each coating solution was applied on the PET film at room temperature using a wire bar so that the thickness of the dried film was 6 μm.
(2) After drying at room temperature for 30 seconds to remove the solvent, the mixture was heated in an atmosphere of 125 ° C. for 2 minutes, and then made a cholesteric liquid crystal phase at 95 ° C. Next, UV irradiation was performed at an output of 60% for 6 to 12 seconds with an electrodeless lamp “D bulb” (90 mW / cm) manufactured by Fusion UV Systems Co., Ltd., and the cholesteric liquid crystal phase was fixed. ) Was produced.
(3) After cooling to room temperature, the above steps (1) and (2) were repeated to prepare a support with a liquid crystal film, in which a liquid crystal film of a cholesteric liquid crystal phase that was laminated in four layers was formed on PET.
The coating liquid was applied in the order of (R1), (R2), (L1), and (L2).
About the liquid crystal film of the support body with a liquid crystal film obtained in this way, Young's modulus was measured by the following method and found to be 2.0 GPa.
-Measuring method of Young's modulus The tensile test of the liquid crystal film (width 20mm, measurement length 50mm) was done, and the Young's modulus was calculated from the two-point inclination of the linear region of the stress strain curve.
E = (σ2-σ1) / (ε2-ε1).
(In the above formula, E represents Young's modulus (Pa), σ represents stress (Pa), and ε represents strain (%).)
The elongation at break of the liquid crystal film of the support with a liquid crystal film was measured by the following method and found to be 3.0%.
-Measuring method of elongation at break A tensile test of a liquid crystal film (width 20 mm, measurement length 50 mm) was conducted to calculate the elongation at break. Breaking progress (%) = (length after test−length before test) / (length before test) × 100

(surface treatment)
The surface of the liquid crystal film of the obtained support with a liquid crystal film was washed according to the following procedure.
The laminate formed as described above was immersed in a container containing 2-butanone, and washed at 40 ° C. for 10 minutes.

<Manufacture of laminated interlayer film>
(1) Lamination of liquid crystal film and intermediate film of support with liquid crystal film, thermal bonding Support with liquid crystal film including liquid crystal film formed on PET (total thickness of support 50 μm, thickness of liquid crystal film 4 layers 24 μm) Using a laser generator (trade name laser cutting device, manufactured by Crime Products Co., Ltd.) from the support side, the value of W / (T × V) represented by the above formula (1) is as follows: A carbon dioxide laser was irradiated at a wavelength of 10.6 μm so that the values shown in Table 2 were obtained, and the periphery was cut off to a size of 290 mm × 290 mm so that the end face was in the vertical direction.
On the other hand, a PVB film having both surfaces embossed as an intermediate film was cut off to a size of 300 mm × 300 mm so that the end face was in the vertical direction. The liquid crystal film is an intermediate film on the liquid crystal film of the support with the liquid crystal film in a state in which all end portions (end surfaces forming four sides) of the liquid crystal film support are 5 mm inside the intermediate film. PVB was overlaid to obtain a laminate. The structure of the obtained laminate is shown in FIG. In FIG. 1, the length represented by (d) is 5 mm.
About the obtained laminated body, the position of 1 mm or less from the edge part of the support body 5 with a liquid-crystal film | membrane is detected as a thermocompression-bonding position, and the position of the support body 5 with a liquid-crystal film | membrane is 120 degreeC, 0.2 MPa, 0.2 m Under the condition of / min, a position of 1 mm or less from the end of the support 5 with a liquid crystal film is sandwiched between two laminating heating rollers arranged on the front side and the back side of the obtained laminate, and the liquid crystal film and the intermediate The film was bonded by thermocompression bonding. At this time, the laminating heating roller is set to 25 ° C. so that the embossing of the back surface of the intermediate film (the surface 3a on the side not in contact with the liquid crystal film) is crushed, and conversely, the liquid crystal film side surface of the intermediate film The heating roller for laminating on the support 2 (PET) side was set to 120 ° C. so as to sufficiently crush the emboss 3a and improve the adhesion between the intermediate film 3 and the liquid crystal film 1.

(2) Lamination of PVB as second intermediate film Thereafter, PVB as a second intermediate film was further laminated on the surface of the PET support.
This was used as the laminated interlayer film of Example 1. FIG. 2 shows the structure of the laminated intermediate film 7 obtained by laminating the obtained intermediate film, liquid crystal film, and second intermediate film.

<Manufacture of laminated glass>
The laminated resin film and the laminated intermediate film 7 including the intermediate film were laminated so as to be glass / intermediate film / liquid crystal film / second intermediate film / glass to produce a laminated body sandwiched between glass plates. . Here, the edge part of the said glass plate and the edge part of the said intermediate film were the same positions. The structure of the obtained laminated glass is shown in FIG. In the drawing, the glass plate is simplified so as not to have a curvature.
Further, the glass plate having a size of 300 mm × 300 mm and a thickness of 2 mm was used. The radius of curvature of the curved glass plate was between 0.9 m and 3.0 m.
The laminate sandwiched between the obtained glass plates was pre-pressed under vacuum at 95 ° C. for 30 minutes. After the pre-bonding, the laminate sandwiched between the glass plates was pressure-bonded while being heated in an autoclave under the conditions of 1.3 MPa and 120 ° C. to produce a laminated glass. In this way, the laminated glass of Example 1 in which the laminated intermediate film 7 in which the upper and lower sides of the four layers of the cholesteric liquid crystal phase infrared reflective layer (liquid crystal film 1) are sandwiched between the two intermediate films 3 and 3 ′ is inserted. 6 was obtained.

[Examples 2 and 3]
In Example 1, when the support with a liquid crystal film was cut, the same method as in Example 1 was used, except that the following mold blade was used to cut the support from the support blade side. The laminated interlayer film and laminated glass of Examples 2 and 3 were produced.
(Mold blade)
・ Cutting method: Thomson blade;
・ Cutting edge angle: Angle described in Table 3 below (unit: °);
-Blade corner radius: 4 mm;
・ Blade material: SK material;
-Rockwell hardness of blade HRA: 80;
-Folding force of the blade: 3.5 MPa;
・ Hardness of blade pressing rubber: 30 °;

[Example 4]
In Example 2, when the support with a liquid crystal film was cut, the laminated intermediate film of Example 4 and the film of Example 4 were obtained in the same manner as in Example 2 except that the mold blade was inserted and cut from the liquid crystal film side. Laminated glass was produced.

[Example 5]
In Example 1, the support with a liquid crystal film including the liquid crystal film formed on PET and the PVB film on which both surfaces are embossed are overlapped and thermally bonded without adjusting the size, Later, the laminated interlayer film and laminated glass of Example 5 were produced in the same manner as in Example 1 except that the first interlayer film, the liquid crystal film, and the support were cut at the same time.

[Example 6]
In Example 2, the support with a liquid crystal film including the liquid crystal film formed on PET and the PVB film on which both surfaces are embossed are superposed and thermally bonded without adjusting the size, Thereafter, a laminated interlayer film and a laminated glass of Example 6 were produced in the same manner as in Example 2, except that the first interlayer film, the liquid crystal film, and the support were cut at the same time.

[Example 7]
In Example 3, the support with a liquid crystal film including the liquid crystal film formed on PET and the PVB film on which both surfaces are embossed are superposed and thermally bonded without adjusting the size, Later, the laminated intermediate film and laminated glass of Example 7 were produced in the same manner as in Example 3, except that the first intermediate film, the liquid crystal film, and the support were cut simultaneously.

[Example 8]
In Example 4, the support with a liquid crystal film including the liquid crystal film formed on PET and the PVB film on which both surfaces are embossed are overlapped and thermally bonded without adjusting the size, Thereafter, a laminated interlayer film and a laminated glass of Example 8 were produced in the same manner as in Example 4 except that the first interlayer film, the liquid crystal film, and the support were cut at the same time.

[Evaluation]
The laminated interlayer films having the configurations of the above examples and comparative examples were evaluated by the following methods. The results are shown in Table 2 and Table 3 below.

(End face peeling)
The length at which the end face of the liquid crystal film is peeled off from the support on the surface side of the liquid crystal film on which the support is laminated when the support with the liquid crystal film is cut. Was measured from the edge of the liquid crystal film and evaluated according to the following criteria.
○: No peeling.
(Triangle | delta): The liquid crystal film edge part peeled with the width | variety of 0.2 mm or less from the edge part of a liquid crystal film.
X: The edge part of the liquid crystal film was peeled from the edge part of the liquid crystal film with a width longer than 0.2 mm.

  From the above Tables 2 and 3, the laminates of Example 1, Example 2, Example 5 and Example 6 obtained by the method for producing a laminated interlayer film of the present invention were used for cutting the support with a liquid crystal film. It was found that the end face peeling was suppressed.

[Example 11]
In Examples 1 to 8, when the laminated glass was manufactured, after completion of the thermocompression bonding, it was allowed to cool for about 3 hours while maintaining the pressure, and the pressure was released when the temperature in the autoclave became 40 ° C. or lower. . At this time, the pressure before opening was 0.9 MPa.
About the produced laminated glass, when the wrinkle of the intermediate film and the crack of the liquid crystal film were evaluated, it was found that both were further improved from Examples 1 to 8.

DESCRIPTION OF SYMBOLS 1 Liquid crystal film 2 Support body 3 Intermediate film 3a Liquid crystal film side surface 3b of an intermediate film Surface 3 'of the intermediate film which is not in contact with the liquid crystal film Second intermediate film 4, 4' Glass plate 5 Support 6 with liquid crystal film Glass 7 Laminated intermediate film 15a Infrared reflective layer 15b formed by fixing cholesteric liquid crystal phase Infrared reflective layer 16a formed by fixing cholesteric liquid crystal phase Infrared reflective layer 16b formed by fixing cholesteric liquid crystal phase Fixed cholesteric liquid crystal phase Infrared reflective layer

Claims (19)

A step of simultaneously cutting the liquid crystal film and the support of the support having a liquid crystal film including the support and the liquid crystal film formed on the support; and
Laminating a first intermediate film on the liquid crystal film side surface of the support with the liquid crystal film;
Including a step of laminating a second intermediate film on the support-side surface of the support with a liquid crystal film,
The step of laminating the first intermediate film on the liquid crystal film side surface of the support with liquid crystal film includes the step of thermally bonding the first intermediate film to the liquid crystal film side surface of the support with liquid crystal film,
After the thermal bonding step, simultaneously cutting the first intermediate film, the liquid crystal film and the support,
A method for producing a laminated interlayer film, comprising only one support between the first interlayer film and the second interlayer film.   The method for producing a laminated intermediate film according to claim 1, wherein the liquid crystal film has a pair of infrared reflection layers having the same center wavelength for selective reflection and having different spiral directions. The first intermediate layer, the liquid crystal layer and the step of cutting the support at the same time, manufacturing method of a multilayer intermediate film according to claim 1 or 2, characterized in that it comprises a step of cutting with a laser. 3. The laminated intermediate according to claim 1, wherein the step of simultaneously cutting the first intermediate film, the liquid crystal film, and the support includes a step of punching out a die blade from the support. A method for producing a membrane. A step of simultaneously cutting the liquid crystal film and the support of the support having a liquid crystal film including the support and the liquid crystal film formed on the support; and
Laminating a first intermediate film on the liquid crystal film side surface of the support with the liquid crystal film;
Including a step of laminating a second intermediate film on the support-side surface of the support with a liquid crystal film,
The step of laminating the first intermediate film on the liquid crystal film side surface of the support with liquid crystal film includes the step of thermally bonding the first intermediate film to the liquid crystal film side surface of the support with liquid crystal film,
After the step of simultaneously cutting the liquid crystal film and the support , performing a step of thermally bonding the liquid crystal film of the support with the liquid crystal film and the first intermediate film ,
Manufacturing method of the first intermediate layer and the second intermediate layer wherein the support you comprising only one product layer intermediate layer between. In the step of simultaneously cutting the liquid crystal film and the support, all the end portions of the support and all the end portions of the liquid crystal film are 1 mm or more inward from the end portions of the first intermediate film. It cut | disconnects, The manufacturing method of the lamination | stacking intermediate film of Claim 5 characterized by the above-mentioned.   The method for producing a laminated intermediate film according to claim 5 or 6, wherein the liquid crystal film has a pair of infrared reflecting layers having the same center wavelength of selective reflection and different spiral directions. In previous SL liquid crystal film and the step of cutting the support at the same time, the so that all the ends of all of the end portion and the liquid crystal layer of the support facing inward 1mm or more from the end of the first intermediate layer The method for producing a laminated interlayer film according to any one of claims 5 to 7 , wherein the laminated interlayer film is cut into pieces. The method for producing a laminated interlayer film according to any one of claims 5 to 8 , further comprising a step of cutting the first interlayer film before the thermal bonding step. The method for producing a laminated intermediate film according to any one of claims 5 to 9 , wherein the step of cutting the liquid crystal film and the support at the same time includes a step of cutting using a laser. The laminated intermediate film according to any one of claims 5 to 9 , wherein the step of cutting the liquid crystal film and the support at the same time includes a step of punching out a die blade from the support side. Production method. The method for producing a laminated interlayer film according to any one of claims 1 to 11 , wherein in the cutting step, cutting is performed using a laser under a condition satisfying the following formula (1).
Formula (1): 0.0002 <W / (T × V) <0.0008
(In formula (1), W represents the laser output (unit: W), T represents the thickness of the laminate to be cut (unit: μm), and V represents the laser scanning speed (mm / second).) The method for producing a laminated interlayer film according to any one of claims 1 to 12 , wherein a laser having a wavelength in an infrared region is used in the cutting step. The method for producing a laminated interlayer film according to any one of claims 1 to 13 , wherein a die blade having a cutting edge angle of 20 ° to 40 ° is used in the cutting step. 15. The method for producing a laminated interlayer film according to claim 14 , wherein the corner shape of the mold blade has a radius of 2 mm or more. The laminated intermediate film according to claim 14 or 15 , wherein the material of the mold blade is SK material, high speed steel or SUS440C, the Rockwell hardness is HRA70 or more, and the bending strength is 2.5 MPa or more. Production method. The method for producing a laminated interlayer film according to any one of claims 14 to 17 , wherein a pressing rubber having a rubber hardness of 20 to 80 ° is provided in the vicinity of the mold blade. The laminated intermediate film according to any one of claims 1 to 17 , further comprising a step of applying a liquid crystal film-forming coating solution on the support to form the support with a liquid crystal film. Production method. A method for producing a laminated glass, comprising a step of sandwiching the laminated intermediate film produced by the method for producing a laminated intermediate film according to any one of claims 1 to 18 between at least two glass plates. .

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