JP2011116571A - Method for producing laminated interlayer sheet for laminated glass, laminated interlayer sheet, and functional laminated glass and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a laminated interlayer sheet for laminated glass laminated with a functional hardened film without deteriorating functions as an interlayer for laminated glass. <P>SOLUTION: The method for producing such a laminated interlayer sheet for laminated glass includes: a first step of preparing a first laminated body comprising a support and a functional layer formed thereon by curing a liquid crystal composition; a second step of obtaining a second laminated body by bringing a surface (hereinafter called an "adhesion surface") of a first interlayer sheet, at least one surface of which has been embossed, into contact with the functional layer and laminating the first laminated body and the first interlayer sheet under conditions which do not lose the embossed state of a surface (hereinafter called a "non-adhesion surface") of the first interlayer sheet opposite to the adhesion surface; and a third step of sticking a second interlayer sheet to the second laminated body. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to a method for producing a laminated interlayer sheet useful for efficiently incorporating a functional layer into a laminated glass, which is a laminated interlayer sheet used for producing laminated glass.
The present invention also relates to a laminated interlayer sheet produced by the method, a functional laminated glass using the laminated interlayer sheet, and a method for producing the same.

  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 one of them is glass that is effective in shielding heat from window glass of houses and automobiles, that is, reducing the heat load caused by sunlight. And films are sought. In order to reduce the heat load caused by sunlight, it is necessary to prevent the transmission of sunlight in either the visible light region or the infrared region of the sunlight spectrum.

A multi-layer glass coated with a special metal film that cuts off heat radiation, called Low-E pair glass, is often used as eco-glass with high heat insulation and heat shielding properties. The special metal film can be manufactured by laminating a plurality of layers by, for example, a vacuum film forming method. Although these special metal film coatings produced by vacuum film formation have excellent reflection performance, the vacuum process has low productivity and high production cost. In addition, when a metal film is used, electromagnetic waves are simultaneously shielded. Therefore, when a mobile phone or the like is used, there are problems such as causing radio wave interference or being unable to use ETC when used in an automobile.
A heat ray reflective transparent substrate having a layer containing metal fine particles has been proposed. Although a film containing metal fine particles has excellent visible light transmission performance, there is a problem in that the reflectance with respect to light in the wavelength range of 700 to 1200 nm, which is greatly involved in heat shielding, is low, and the heat shielding performance cannot be increased.
A heat ray shielding sheet having a layer containing an infrared absorbing dye is also disclosed. When an infrared absorbing dye is used, the solar transmittance can be lowered, but there is a problem that the heat shielding performance is lowered due to an increase in film surface temperature due to the absorption of solar radiation and the re-release of the heat.

  On the other hand, laminated glass is used for window glass of automobiles and construction because of its safety and crime prevention. In recent years, the laminated glass has been required to have not only the above-mentioned performance but also various other functions, including, for example, an ultraviolet ray prevention function, a heat ray shielding function, a soundproofing function, etc. (patents) References 1-3).

  Usually, a laminated glass is manufactured through a crimping process by sandwiching an interlayer film for laminated glass between two pieces of glass. At this time, in the crimping process, air generated at the interface between the glass and the intermediate film is removed by vacuum deaeration and pressurization, but in order to facilitate the deaeration at that time, the intermediate film has a surface thereof. In order to produce a laminated glass stably, embossing the surface of the interlayer film will be indispensable.

  By the way, in order to insert the functional film (or film) in order to give the above function to the laminated glass, the film is directly bonded or transferred to the intermediate film to produce a laminated interlayer film. It will be used for the production of laminated glass. However, when laminating the functional film to the interlayer film, in many cases, thermocompression bonding is performed, so that the embossing applied to the surface of the interlayer film is crushed by the heat during lamination, and re-embossing after lamination is performed. There were problems such as the need for processing steps. Furthermore, since the functional layer has already been provided at the time of re-embossing, there is a problem that the functional layer is destroyed or the function is lowered by the embossing.

JP-A-2-293356 JP 2004-26547 A JP-A-6-926

The present invention has been made in view of the above-mentioned problems, and efficiently manufactures a laminated interlayer sheet for laminated glass laminated with a functional cured film without reducing the function as an interlayer film for laminated glass. It is an object to provide a method.
The present invention also provides a laminated interlayer sheet useful for efficiently incorporating a functional layer into the functional laminated glass produced by the method, and a functional laminated glass and functionality using the laminated interlayer sheet. It is an object to provide a method for producing a laminated glass.

Means for solving the above problems are as follows.
[1] A first step of preparing a first laminate having a support and a functional layer formed by curing a liquid crystal composition on the support,
The surface of the first intermediate film sheet (hereinafter referred to as “adhesive surface”) having at least one surface embossed is brought into contact with the functional layer, and the opposite side of the adhesive surface of the first intermediate film sheet The second step of obtaining the second laminate by laminating the first laminate and the first interlayer film sheet under the condition that the embossing of the surface (hereinafter referred to as “non-adhesive surface”) is not lost. And the 3rd process of bonding the 2nd interlayer film sheet to the 2nd layered product,
For producing a laminated interlayer sheet for laminated glass.
[2] Before carrying out the second step, the first interlayer film is preheated, and when the second step is carried out, the temperature of the adhesive surface with the functional layer of the first interlayer sheet The first intermediate film is laminated with the first laminated body under the condition that the temperature of the non-adhesive surface with the functional layer of the first intermediate film sheet is 30 ° C. or lower. 1].
[3] The second step is performed using a pair of laminate rolls, the temperature of the laminate roll supporting the first laminate is relatively high, and the laminate roll supporting the first intermediate film is relatively The method for producing a laminated interlayer sheet according to [1] or [2], characterized in that a temperature difference is provided between the adhesion surface and the non-adhesion surface of the first interlayer film with the functional layer. .
[4] In any one of [1] to [3], in the second step, the first intermediate film and the first laminate are laminated under a pressure condition of less than 2 kg / cm ² . A method for producing a laminated interlayer sheet.
[5] The method for producing a laminated interlayer sheet according to any one of [1] to [4], wherein the thickness of the first interlayer sheet is 0.3 mm or more.
[6] In the second step, the first laminate and the first intermediate film are laminated, and the support is peeled off from the functional layer. In the third step, the second intermediate film is The method for producing a laminated interlayer film sheet according to any one of [1] to [5], wherein the functional layer support is bonded to the peeled surface.
[7] The method for producing a laminated interlayer sheet according to [6], wherein the temperature of the support when peeling the support from the functional layer is 40 ° C. or higher.
[8] The [1] to [7], wherein the first and second intermediate film sheets are films made of a composition containing polyvinyl butyral or a composition containing an ethylene / vinyl acetate copolymer. A method for producing any of the laminated interlayer sheets.
[9] The method for producing a laminated interlayer sheet according to any one of [1] to [7], wherein the functional layer includes two or more layers in which a cholesteric liquid crystal phase is fixed.
[10] A laminated intermediate film sheet produced by the method of any one of [1] to [9], comprising two intermediates comprising a composition containing polyvinyl butyral or a composition containing an ethylene / vinyl acetate copolymer A laminated interlayer sheet comprising a film sheet and a functional layer including two or more layers in which a cholesteric liquid crystal phase is fixed therebetween.
[11] A functional laminated glass comprising the laminated interlayer sheet of [10] between a pair of transparent substrates.
[12] A method for producing a functional laminated glass, comprising disposing the laminated interlayer film sheet of [10] between a pair of transparent substrates and bonding the pair of transparent substrates via the sheets.

ADVANTAGE OF THE INVENTION According to this invention, the efficient manufacturing method of the laminated intermediate film sheet for laminated glasses laminated | stacked with the functional cured film can be provided, without reducing the function as an intermediate film for laminated glasses.
In addition, according to the present invention, a laminated interlayer sheet useful for efficiently incorporating a functional layer into the functional laminated glass produced by the method, and a functional laminated glass using the laminated interlayer sheet And the manufacturing method of functional laminated glass can be provided.

It is the schematic diagram used in order to demonstrate an example of the manufacturing method of this invention. It is a cross-sectional schematic diagram of an example of the lamination | stacking intermediate film sheet of this invention. It is a cross-sectional schematic diagram of an example of the functional laminated glass of this invention.

  Hereinafter, the present invention will be described in detail. 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.

1. The present invention relates to a method for producing a laminated interlayer film sheet.
A first step of preparing a first laminate having a support and a functional layer formed thereon by curing a liquid crystal composition;
The surface of the first intermediate film sheet (hereinafter referred to as “adhesive surface”) having at least one surface embossed is brought into contact with the functional layer, and the opposite side of the adhesive surface of the first intermediate film sheet The second step of obtaining the second laminate by laminating the first laminate and the first interlayer film sheet under the condition that the embossing of the surface (hereinafter referred to as “non-adhesive surface”) is not lost. And a third step of bonding the second intermediate film to the second laminate,
The present invention relates to a method for producing a laminated interlayer film sheet for laminated glass.
Hereinafter, each step will be described with reference to FIG.

(1) First Step First, in the first step, a first laminate 10 having a support 12 and a functional layer 14 formed thereon by curing a liquid crystal composition is prepared ( FIG. 1 (a)). The functional layer 14 included in the first laminate 10 is a layer that is incorporated in a laminated glass and imparts functionality such as an ultraviolet ray prevention function, a heat ray shielding function, and a soundproofing function to the laminated glass. Since the support 12 may be finally removed, the material and the like are not particularly limited. A highly versatile polymer film such as PET film would be used. Further, an easy-adhesion layer, an alignment layer, or the like may be disposed between the functional layer 14 and the support 12. Further, in FIG. 1, the functional layer 14 is expressed as a single layer, but the functional layer 14 may be composed of a plurality of layers. In particular, in order to provide a heat shielding function described later, a cholesteric liquid crystal is used. It is preferable to have two or more layers in which the phases are fixed.

The functional layer 14 can be formed by the following method, for example.
First, a liquid crystal composition containing a liquid crystal compound and optionally an additive such as an alignment control agent is prepared as a coating liquid, the coating liquid is applied to the surface of the support 12, and a solvent is removed from the coating film under heating if desired. Remove and dry the coating. The liquid crystal molecules are aligned by drying to obtain a predetermined alignment state, the alignment state is fixed by a curing reaction, and the functional layer 14 is formed. However, it is not limited to this method, and it can also be formed using a transfer method or the like. Further, a commercially available functional film can be used as it is or as desired to be used as the first laminate. Although there is no restriction | limiting in particular about the thickness of the functional layer 14, Generally, it is about 2-50 micrometers.
Examples of materials used for forming the functional layer 14 will be described in detail in the section of the laminated interlayer sheet of the present invention.

(2) Second Step In the second step, at least one is an embossed surface 20a (hereinafter sometimes referred to as “embossed surface 20a” or “non-adhesive surface 20a”) and an adhesive surface. A first intermediate film 20 having a surface 20b is prepared (FIG. 1B). The surface 20b is an adhesive surface to be bonded to the functional layer 14, and is shown as a non-embossed surface in FIG. 1, but may be embossed. Lamination is performed by bringing one surface 20b of the first intermediate film 20 into contact with the surface of the functional layer 14 of the first laminate 10 (FIG. 1C). As the intermediate film 20, a general intermediate film used for producing laminated glass can be used. For example, polyvinyl butyral resin (PVB) or ethylene / vinyl acetate copolymer (EVA) is used as a main raw material. The sheet | seat etc. which gave the embossing to the sheet | seat etc. which were produced from the composition to contain can be utilized. Moreover, you may use the sheet | seat marketed as an intermediate film sheet for laminated glasses (after embossing if necessary). When incorporated in the laminated glass, the embossed surface 20a of the first intermediate film 20 is adhered to the surface of a transparent substrate such as a glass plate, and the degassing is promoted by the unevenness of the embossed surface 20a, thereby stabilizing Can be bonded together.

  In the present invention, in the second step, the lamination is performed under the condition that the embossing of the embossed surface 20a of the first intermediate film 20 is not lost. In order to adhere the first interlayer film sheet 20 and the functional layer 14 so that peeling does not occur, a certain amount of heating and pressurization is required. On the other hand, when heating and / or pressurization is strengthened, the embossing of the surface 20a is lost, and after laminating with the functional layer 14, the surface of the first intermediate film 20 needs to be embossed again. Reduce. Furthermore, the functional layer 14 is a cured film made of a liquid crystal composition, and is thin and difficult to deform. Therefore, the functional layer 14 is fragile to external force. Therefore, the embossing after lamination causes defects such as cracks in the functional layer 14. There is a fear. In the present invention, since the lamination is performed under the condition that the embossing of the surface 20a is not lost, such a problem can be solved.

  In order not to lose the embossing of the surface 20a of the first intermediate film 20, it is necessary not to apply excessive heating to the embossed surface 20a but to apply heat sufficient for bonding to the adhesive surface 20b. In one aspect of the present invention, the first intermediate film 20 is preheated and the temperature of the adhesive surface 20b of the first intermediate film 20 with the functional layer 14 is 50 before performing the second step. The first intermediate film 20 is laminated with the first laminate 10 under the condition that the temperature of the non-adhesive surface 20a of the first intermediate film is 30 ° C. or lower. In order to stably perform bonding, the temperature of the bonding surface 20b is preferably 50 to 130 ° C, and more preferably 70 to 100 ° C. On the other hand, the temperature of the non-adhesive surface 20a is preferably 0 to 30 ° C, and more preferably 20 to 30 ° C, in order to ensure that the embossing is not lost and the adhesiveness is sufficiently secured. Moreover, it is preferable that it is 20-80 degreeC, and, as for the temperature difference of the adhesive surface 20b and the non-adhesion surface 20a at the time of lamination, it is more preferable that it is 30-60 degreeC. In order to make the temperature of the bonding surface 20b and the non-bonding surface 20a within the above range and to form the temperature difference without requiring a long time, the temperature of the first intermediate film 20 is set to 50 to 50 at the time of preheating. Heating at about 100 ° C. for about 5 to 60 seconds is preferable, and heating at 60 to 80 ° C. for the same time is more preferable. However, a desired temperature difference can be obtained by adjusting the roll temperature without preheating.

Various methods may be used for forming the temperature difference between the bonding surface 20b and the non-bonding surface 20a during lamination. In an embodiment in which lamination is performed using a pair of laminate rolls, the temperature of the laminate roll that supports the first laminate 10 is relatively high (for example, heated), and the first interlayer sheet 20 is supported. A method of relatively lowering the temperature of the laminate roll (for example, non-heating or cooling) is effective. Each temperature of the pair of laminate rolls can be set so as to form the temperature difference. Moreover, there is no restriction | limiting in particular also about the conveyance speed by a laminate roll, Generally, it is about 0.1-5 m / min.
In addition, even in a mode in which no laminate roll is used, hot air is supplied from the back surface of the first laminate 10 (the surface on the side where the functional layer 14 of the support 12 is not formed), while the first intermediate The non-adhesive surface 20a of the membrane sheet 20 could supply cold air or room temperature air to form a temperature difference.

It is preferable to apply pressure during lamination. However, excessive pressurization causes the embossing of the non-adhesive surface 20a to be lost, which is not preferable. In this respect, the pressure condition is preferably less than 2 kg / cm ^2, more preferably from 0.5~1.8kg / cm ^2, in the range of 0.5~1.5kg / cm ² Is more preferable. The aspect using the laminate roll is also preferable in terms of easy adjustment of pressure.

  Here, if the thickness of the first intermediate film 20 is too thin, it becomes more difficult to form a temperature difference between the non-adhesive surface 20a and the adhesive surface 20b. In this respect, the thickness of the first intermediate film is preferably 0.3 mm or more, preferably about 0.3 to 1 mm, and more preferably about 0.3 to 0.5 mm. .

  In the present invention, the support 12 may be peeled from the first laminate 10 simultaneously with the lamination, immediately after or just before the lamination. That is, the second laminate 30 obtained after lamination may not have the support 12 (FIG. 1 (d)). In order to peel the support 12 stably without breakage or the like, the temperature of the support when peeling the support 12 from the functional layer 14 is preferably 40 ° C or higher, and is 40 to 60 ° C. Is more preferable.

(3) Third Step In the third step, the second interlayer sheet 40 is bonded to the second laminate 30 obtained by lamination. Similarly to the first interlayer film sheet 20, the second interlayer film sheet 40 may be a general interlayer film used for production of laminated glass. For example, a composition containing polyvinyl butyral, or A sheet prepared from a composition containing an ethylene / vinyl acetate copolymer can be used. Moreover, you may utilize a commercial item similarly to the 1st intermediate film sheet 20. FIG. Furthermore, when the second intermediate film is used for bonding to glass, it is preferable that the bonding surface with the glass is embossed, similarly to the first intermediate film.

  The 2nd intermediate film sheet 40 can be bonded to the surface from which the support body of the 2nd laminated body 30 was peeled, for example. In addition, the 2nd laminated body 30 may have the support body 12, and in that case, the 2nd intermediate film is formed in the back surface (surface by which the functional layer 14 is not arrange | positioned) of the support body 12. The sheet 40 may be bonded. There is no restriction | limiting in particular about the method of bonding, Various methods, such as thermal bonding, can be utilized. A laminate roll may be used. Moreover, the 2nd laminated body 30 and / or the 2nd intermediate film sheet 40 may be heated previously, and may be crimped | bonded and bonded after that.

In FIG. 2, the cross-sectional schematic diagram of an example of the lamination | stacking intermediate film sheet 50 manufactured by the method of this invention is shown.
A laminated interlayer sheet 50 in FIG. 2 includes a first interlayer sheet 20, a second interlayer sheet 40, and a functional layer 14 therebetween. The first and second interlayer film sheets 20 and 40 are sheets made of a composition containing polyvinyl butyral, and can be thermally bonded to a transparent substrate such as a glass substrate or a plastic substrate. The functional laminated glass which has the functional layer 14 inside can be easily manufactured by arrange | positioning the lamination | stacking intermediate film sheet 50 between a pair of transparent substrates, and heat-bonding. Moreover, since the adhesion surface with the glass plate etc. of the 1st intermediate film sheet 20 is embossed (in FIG. 2, about embossing is not shown), when thermally bonding with transparent substrates, such as a glass plate, The unevenness of the embossed surface facilitates degassing and enables stable thermal bonding.

In FIG. 3, the cross-sectional schematic diagram of an example of the functional laminated glass 60 using the lamination | stacking intermediate film sheet 50 is shown.
The functional laminated glass shown in FIG. 3 is a laminated glass manufactured by thermally bonding a pair of transparent substrates 52 and 52 ′ via a laminated interlayer film sheet 50. The laminated glass 60 is provided with, for example, an ultraviolet ray prevention function, a heat ray shielding function, a soundproofing function, and the like by the functional layer 14 included therein. The transparent substrates 52 and 52 ′ may be not only glass plates but also plastic substrates such as acrylic resin, polyester resin, polyimide resin, and polyolefin resin. Further, it is not necessary that both of the substrates are made of the same material, and one may be a glass substrate and the other may be a plastic substrate. Further, the transparent substrates 52 and 52 ′ may be colored as long as at least light is not completely blocked. There is no restriction | limiting in particular about thickness, such as a glass plate, A preferable range changes according to a use. For example, in the use of windshields (window shields) for transportation vehicles, it is generally preferable to use a glass plate having a thickness of 2.0 to 2.3 mm. Moreover, the thickness of the light transmissive support such as a glass plate of a heat-shielding window material for buildings such as houses and buildings is generally about 40 to 300 μm. However, it is not limited to this range.

  The functional laminated glass shown in FIG. 3 can be used as a windshield of a transportation vehicle, a window glass of a house, a building, or the like depending on its function.

Below, the aspect of the heat ray shielding functional layer using a cholesteric liquid crystal phase is demonstrated in detail as a functional layer which can be utilized for this invention.
One embodiment of the present invention is an embodiment having, as a functional layer, at least one light reflecting layer exhibiting characteristics of reflecting light in a wavelength region of 700 nm or more. Since light in the wavelength region of 700 nm or more is light that is a main cause of temperature rise, the functional layer of this aspect has a function of shielding heat rays by reflecting light in the wavelength region. The light reflecting layer is a layer formed by fixing a cholesteric liquid crystal phase. For the formation of the light reflecting layer, it is preferable to use a curable liquid crystal composition. An example of the liquid crystal composition contains at least a rod-like liquid crystal compound, an optically active compound (chiral agent), and a polymerization initiator. Two or more of each component may be included. 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 alignment uniformity, coating suitability, and film strength, it contains at least one selected from various additives such as a horizontal alignment agent, a non-uniformity inhibitor, a repellency inhibitor, and a polymerizable monomer. May be. In addition, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, and the like can be further added to the liquid crystal composition as necessary so long as the optical performance is not deteriorated.

(1) Rod-like liquid crystal compound An example of the rod-like liquid crystal compound that can be used in the present invention is a rod-like nematic liquid crystal compound. 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 used in the present invention may be polymerizable or non-polymerizable. The rod-like liquid crystal compound having no polymerizable group is described in various documents (for example, Y. Goto et.al., Mol. Cryst. Liq. Cryst. 1995, Vol. 260, pp. 23-28). .
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.

(2) Optically active compound (chiral agent)
The liquid crystal composition 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 asymmetric carbon atom, the cholesteric liquid crystal phase may be stably formed without adding an optically active compound. The optically active compound is known in various known 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, 142nd Committee, 1989). ) Can be selected. 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.

(3) Polymerization initiator The liquid crystal composition used for forming the light reflecting layer is preferably a polymerizable liquid crystal composition, and for that purpose, it preferably contains a polymerization initiator. An example of the polymerizable liquid crystal composition is an ultraviolet curable liquid crystal composition containing a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation. 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-hydrocarbon substitution 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 (US Patent 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850), oxadiazole compounds (US Pat. No. 4,221,970), and the like It is done.

  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).

(4) Alignment control agent In this invention, it is preferable to add the alignment control agent which contributes to becoming a cholesteric liquid crystal phase stably or rapidly in the said liquid-crystal composition. Examples of the orientation control agent include fluorine-containing (meth) acrylate polymers and compounds represented by the following general formulas (X1) to (X3). 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 to the film surface, resulting in a decrease in reflectivity, a fingerprint pattern, an increase in haze and diffraction. It is not preferable because it shows.
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 following general formulas (X1) to (X3) that can be used as the alignment control 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 (XI). 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 in the present invention 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.

  The addition amount of the compound represented by any one of the general formulas (X1) to (X3) in the liquid crystal composition is preferably 0.01 to 10% by mass, and 0.01 to 5% by mass of the liquid crystal compound. % Is more preferable, and 0.02 to 1% by mass is particularly preferable.

The light reflecting layer is preferably produced by a coating method. An example of a manufacturing method is
(1a) Applying a curable liquid crystal composition to the surface of the support to form a cholesteric liquid crystal phase;
(1b) irradiating the curable liquid crystal composition with ultraviolet rays to advance a curing reaction, fixing a cholesteric liquid crystal phase, and forming a light reflection layer;
Is a production method comprising at least
By repeating the steps (1a) and (1b) twice or more on one surface of the support, a heat shield member having two or more light reflecting layers can be produced.

  In the step (1a), first, the curable liquid crystal composition is applied to the surface of the support or the lower light 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, the curable liquid crystal composition applied to the surface to form a coating film is brought into 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. Further, 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. It will be disadvantageous.

Next, in the step (1b), 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 ultraviolet rays, the curing reaction of the liquid crystal composition proceeds, the cholesteric liquid crystal phase is fixed, and a light 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 once polymerized, a method in which the reaction is further promoted by a thermal polymerization reaction while being held at a temperature higher than the polymerization temperature, or a method in which ultraviolet rays are irradiated 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 step, the cholesteric liquid crystal phase is fixed and the light reflecting 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 layer no longer needs 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 the above, the embodiment of the heat ray shielding functional layer using a cholesteric liquid crystal phase as the functional layer has been described in detail, but the present invention is not limited to this embodiment. By changing the cholesteric pitch of the liquid crystal phase, it is possible to form layers that are reflective to light of different wavelength ranges, and by utilizing the orientation of liquid crystal phases other than the cholesteric liquid crystal phase, It is also possible to form a functional layer having characteristics other than the reflection characteristics. Furthermore, various functional laminated glasses can be provided by incorporating the functional layer thereof.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. 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. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

1. Preparation of substrate A PET film manufactured by Fuji Film Co., Ltd. was prepared as a support.

2. Formation of Reflective Layer Coating solutions (A) and (B) having the compositions shown in the following table were prepared.

3. Production of first laminate sheet (1) PET film (substrate 1) manufactured by Fuji Film Co., Ltd., using a prepared coating solution (A) so that the dry film thickness after drying is 6 μm using a wire bar. ) At room temperature.
(2) After drying at room temperature for 30 seconds to form a cholesteric liquid crystal phase, the mixture was heated in an atmosphere of 125 ° C. for 2 minutes, and then heated at 95 ° C. with a fusion D bulb (lamp 90 mW / cm) at an output of 60%. UV irradiation was performed for ˜12 seconds, the cholesteric liquid crystal phase was fixed, and a film (light reflecting layer) was produced.
(3) After cooling to room temperature, the coating liquid (A) was replaced with the coating liquid (B), and the above steps (1) and (2) were repeated.
Thus, the 1st laminated sheet which has two light reflection layers which fixed the cholesteric liquid crystal phase on PET film was produced. This 1st laminated sheet was a heat ray thermal insulation functional member which shows the maximum peak of light reflection in 1000 nm.
This produced first laminate sheet was used in each of the following examples and comparative examples.

4). Example 1
Using the laminator (manufactured by Taisei Laminator Co., Ltd.), the reflection of the first laminate sheet produced above and the polyvinyl butyral interlayer film for laminated glass (thickness 0.38 mm) whose surface was embossed was used. The surface of the layer and the surface of the polyvinyl butyral interlayer sheet were thermally bonded. At this time, the polyvinyl butyral interlayer sheet was preheated at 70 ° C. for 1 minute in advance, and then passed through a laminator. At the time of thermal bonding, the temperature of the laminating roll for supporting the first laminate sheet and the laminating roll for supporting the interlayer film is set such that the former is relatively high (specifically 60 ° C.) and the latter is relatively low ( Specifically, the temperatures of the adhesive surface and the non-adhesive surface with the functional layer of the intermediate film at the time of lamination were set to 60 ° C. and 30 ° C., respectively. Heat bonding was performed at a pressure of 1.5 kg / cm ² and a conveying speed of 0.1 m / min.
Immediately after thermal bonding, the support (PET film) is peeled off from the first laminate sheet at a support temperature of 55 ° C., and the other polyvinyl butyral interlayer sheet is peeled off from the reflective layer from the support. A laminated interlayer sheet having a configuration of polyvinyl butyral interlayer / reflective layer / polyvinyl butyral interlayer was prepared by bonding.

5). Example 2
The first laminate sheet prepared above and the polyvinyl butyral interlayer film for laminated glass (thickness 0.38 mm) whose surfaces were embossed were laminated in the same manner as in Example 1. However, the polyvinyl butyral interlayer sheet was passed through a laminator without preheating. At the time of thermal bonding, the temperature of the laminating roll that supports the first laminate sheet and the laminating roll that supports the intermediate film is set such that the former is relatively high (specifically, 80 ° C.) and the latter is relatively low ( Specifically, the temperatures of the adhesive surface and the non-adhesive surface with the functional layer of the intermediate film at the time of lamination were set to 60 ° C. and 30 ° C., respectively. Heat bonding was performed at a pressure of 1.5 kg / cm ² and a conveyance speed of 0.1 m / min.
Immediately after thermal bonding, the support (PET film) is peeled off from the first laminated sheet at a support temperature of 55 ° C., and another polyvinyl butyral interlayer sheet is attached to the release surface of the reflective layer from the support. By combining them, a laminated interlayer sheet having a configuration of polyvinyl butyral interlayer / reflective layer / polyvinyl butyral interlayer was produced.

6). Comparative Example 1
The first laminate sheet prepared above and the polyvinyl butyral interlayer film for laminated glass (thickness 0.38 mm) whose surfaces were embossed were laminated in the same manner as in Example 1. However, the polyvinyl butyral interlayer sheet was passed through a laminator without preheating. At the time of thermal bonding, the temperature of the laminating roll for supporting the first laminate sheet and the laminating roll for supporting the interlayer film is set such that the former is relatively high (specifically 60 ° C.) and the latter is relatively low ( Specifically, the temperature of the adhesive surface and non-adhesive surface with the functional layer of the interlayer film sheet during lamination was set to 40 ° C. and 30 ° C., respectively. Heat bonding was performed at a pressure of 1.5 kg / cm ² and a conveyance speed of 0.1 m / min.
Immediately after heat bonding, the support (PET film) was peeled from the first laminated sheet at a support temperature of 55 ° C., but the transfer of the reflective film to the polyvinyl butyral intermediate film was insufficient.

7). Comparative Example 2
The first laminate sheet prepared above and a polyvinyl butyral interlayer film for laminated glass (thickness 0.38 mm) having an embossed surface were laminated in the same manner as in Example 1. That is, the polyvinyl butyral interlayer film sheet was preliminarily heated at 70 ° C. for 1 minute and then passed through a laminator. At the time of thermal bonding, the temperature of the laminating roll for supporting the first laminate sheet and the laminating roll for supporting the interlayer film is set such that the former is relatively high (specifically 60 ° C.) and the latter is relatively low ( Specifically, the temperatures of the adhesive surface and the non-adhesive surface with the functional layer of the intermediate film at the time of lamination were set to 60 ° C. and 30 ° C., respectively. However, heat bonding was performed at a pressure of 3.0 kg / cm ² and a conveyance speed of 0.1 m / min.
Immediately after thermal bonding, the support (PET film) is peeled off from the first laminated sheet at a support temperature of 55 ° C., and another polyvinyl butyral interlayer sheet is attached to the release surface of the reflective layer from the support. By combining them, a laminated interlayer sheet having a configuration of polyvinyl butyral interlayer / reflective film / polyvinyl butyral interlayer was produced. When the surface of the obtained laminated intermediate film sheet was observed, the embossed surface was crushed because the applied pressure was high, that is, the uneven surface properties were lost.

8). Comparative Example 3
Lamination was carried out under the same conditions as in Example 1 to prepare a laminated interlayer sheet having a configuration of polyvinyl butyral interlayer / reflective film / polyvinyl butyral interlayer. However, an interlayer film having a thickness of 0.28 mm was used as the interlayer film. As a result, the embossing of the obtained laminated interlayer sheet surface was too thin because the polyvinyl butyral interlayer film used was not sufficiently cooled, and the surface was uneven, The property was lost.

(Comparative Example 4)
The first laminate sheet prepared above and the polyvinyl butyral interlayer film for laminated glass (thickness 0.38 mm) whose surfaces were embossed were laminated in the same manner as in Example 1. However, at the time of thermal bonding, the temperature of the laminating roll that supports the first laminate sheet and the laminating roll that supports the interlayer film sheet is relatively low (specifically, 25 ° C.), and the latter is relatively By setting it high (specifically, 80 ° C.), the temperatures of the adhesion surface and the non-adhesion surface with the functional layer of the interlayer film during lamination were set to 40 ° C. and 60 ° C., respectively. Other than that, the preheating temperature, the applied pressure, and the conveyance speed of 0.1 m / min are all the same as those in the first embodiment.
Immediately after thermal bonding, the support (PET film) is peeled off from the first laminated sheet at a support temperature of 55 ° C., and another polyvinyl butyral interlayer sheet is attached to the release surface of the reflective layer from the support. A laminated interlayer sheet having the configuration of polyvinyl butyral interlayer / reflective film / polyvinyl butyral interlayer was manufactured by combining them, but the transfer was incomplete and the surface temperature on the polyvinyl butyral interlayer sheet side was too high. Processing has been crushed.

  The conditions of the above Examples and Comparative Examples and the results are shown in the table below.

＊１：ポリビニルブチラール中間膜シートの熱接着時の接着面の温度（非接触式の温度計で測定）
＊２：ポリビニルブチラール中間膜シートの熱接着時の非接着面の温度（非接触式の温度計で測定）
＊３：熱接着時の圧力
＊４：PETフィルム剥離時の支持体の温度

* 1: Adhesive surface temperature during thermal bonding of polyvinyl butyral interlayer sheet (measured with a non-contact thermometer)
* 2: Temperature of the non-adhered surface of the polyvinyl butyral interlayer sheet during thermal bonding (measured with a non-contact thermometer)
* 3: Pressure during thermal bonding * 4: Temperature of support when peeling PET film

(Example 3)
Using the laminated interlayer sheets for laminated glass respectively obtained in Example 1, Comparative Example 2 and Comparative Example 3, laminated glass was produced in the following steps.
(Preliminary crimping)
Each laminated interlayer film sheet for laminated glass obtained above was sandwiched between two transparent glass plates having a thickness of 2 mm, placed in a rubber bag, and decompressed with a vacuum pump. Then, it heated up to 90 degreeC under pressure reduction, hold | maintained for 30 minutes, returned to normal temperature normal pressure, and completed the precompression bonding process.
(Final crimping)
The pre-crimped laminated glass was held in an autoclave under conditions of a pressure of 1.3 MPa and a temperature of 130 ° C. for 20 minutes, and then returned to room temperature and normal pressure to complete the main crimping step.

  As a result, in the laminated glass produced using the laminated interlayer sheet for laminated glass produced in Example 1, no bubbles remained in the glass, and the internal reflective film maintained good light reflection characteristics. On the other hand, the laminated glass produced by using the laminated interlayer sheets obtained in Comparative Example 2 and Comparative Example 3 each had bubbles left in the glass because the embossing of the interlayer sheet surface was crushed. I have.

  From the above results, according to the examples of the present invention, the laminated interlayer sheet was produced with good productivity while maintaining the embossing of the surface of the interlayer sheet in contact with the glass by appropriately adjusting the temperature during lamination. It was shown that it can be manufactured.

DESCRIPTION OF SYMBOLS 10 1st laminated body 12 Support body 14 Functional layer 20 1st intermediate film sheet 30 2nd laminated body 40 2nd intermediate film sheet 50 Laminated intermediate film sheets 52 and 52 'Transparent substrate 60 Functional laminated glass

Claims (12)

A first step of preparing a first laminate having a support and a functional layer formed thereon by curing a liquid crystal composition;
The surface of the first intermediate film sheet (hereinafter referred to as “adhesive surface”) having at least one surface embossed is brought into contact with the functional layer, and the opposite side of the adhesive surface of the first intermediate film sheet The second step of obtaining the second laminate by laminating the first laminate and the first interlayer film sheet under the condition that the embossing of the surface (hereinafter referred to as “non-adhesive surface”) is not lost. And the 3rd process of bonding the 2nd interlayer film sheet to the 2nd layered product,
For producing a laminated interlayer sheet for laminated glass. Before carrying out the second step, the first intermediate film is preheated, and when the second step is carried out, the temperature of the adhesive surface with the functional layer of the first intermediate film is 50 ° C. The first intermediate film is laminated with the first laminate under the condition that the temperature of the non-adhesive surface with the functional layer of the first intermediate film sheet is 30 ° C. or lower. The manufacturing method of the laminated intermediate film sheet of description. The second step is performed using a pair of laminate rolls, the temperature of the laminate roll supporting the first laminate is relatively high, and the laminate roll supporting the first intermediate film is relatively low. 3. The method for producing a laminated interlayer sheet according to claim 1, wherein a temperature difference is provided between an adhesion surface and a non-adhesion surface with the functional layer of the first interlayer film. In the second step, the laminated according to the first intermediate layer and the first laminate, in any one of claims 1 to 3, characterized in that laminating below pressurized condition 2 kg / cm ² A method for producing an interlayer film. The thickness of the said 1st intermediate film is 0.3 mm or more, The manufacturing method of the lamination | stacking intermediate film of any one of Claims 1-4 characterized by the above-mentioned. In the second step, the first laminate and the first interlayer sheet are laminated, and the support is peeled off from the functional layer. In the third step, the second interlayer sheet is removed from the functional layer. The method for producing a laminated interlayer sheet according to any one of claims 1 to 5, wherein the support is bonded to the peeled surface. The method for producing a laminated interlayer film according to claim 6, wherein the temperature of the support when peeling the support from the functional layer is 40 ° C. or higher. The first and second intermediate film sheets are films made of a composition containing polyvinyl butyral or a composition containing an ethylene / vinyl acetate copolymer, according to any one of claims 1 to 7. The manufacturing method of the laminated intermediate film sheet of description. The method for producing a laminated interlayer sheet according to any one of claims 1 to 7, wherein the functional layer includes two or more layers in which a cholesteric liquid crystal phase is fixed. Two interlayer films made of a composition containing polyvinyl butyral or a composition containing an ethylene / vinyl acetate copolymer, the laminated interlayer sheet produced by the method according to any one of claims 1 to 9 A laminated interlayer sheet comprising a sheet and a functional layer including two or more layers having a cholesteric liquid crystal phase fixed therebetween. The functional laminated glass which contains the lamination | stacking intermediate film sheet of Claim 10 between a pair of transparent substrates. The manufacturing method of functional laminated glass including arrange | positioning the lamination | stacking intermediate film sheet of Claim 10 between a pair of transparent substrates, and adhere | attaching a pair of said transparent substrate through this sheet | seat.

Images