JP5297359B2 - Method for producing adhesive laminate, adhesive laminate, functional laminated glass and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for stably manufacturing an adhesive laminate which is useful for incorporating a functional cured film without self-supporting property to the inside of laminated glass. <P>SOLUTION: The method for manufacturing the adhesive laminate includes: at least a first process for preparing a first laminate having a support body and a functional layer formed by curing liquid crystal composition thereon; a second process for obtaining a first adhesive film by casting molten resin composition on a surface of a support member to produce a film; and a third process for heat-bonding the functional layer and the first adhesive film by laminating the first adhesive film on a surface of the functional layer of the first laminate while heating the first adhesive film, and for obtaining a second laminate having at least the functional layer and the first adhesive film by separating the support body from the first laminate. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to an adhesive laminate useful for producing laminated glass and the like, and more particularly to a method for producing an adhesive laminate useful for efficiently incorporating a functional layer in laminated glass.
Moreover, this invention relates also to the adhesive laminated body manufactured by this method, the functional laminated glass using this adhesive laminated body, and its manufacturing method.

  In recent years, there has been a great need for industrial products related to energy conservation due to increasing interest in the environment and energy. One of these is glass that is effective in reducing the heat load from sunlight, that is, heat insulation from window glass in houses and automobiles. 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. Various methods for producing an interlayer film for laminated glass have also been studied (for example, Patent Document 4).
By the way, in order to give the laminated glass the above-mentioned functionality, it is necessary to incorporate a functional layer into the laminated glass. Conventionally, various methods have been proposed for incorporating a self-supporting functional film such as a heat ray reflective film into a laminated glass. However, although the cured film of the liquid crystalline composition is a film having no self-supporting property and excellent in functionality, it is difficult to incorporate such a cured film without self-supporting into a laminated glass by a conventional method. Yes, it is a negative effect of practical use.

JP-A-2-293356 JP 2004-26547 A JP-A-6-926 JP 2009-45874 A

The present invention has been made in view of the above problems, and provides a stable method for producing an adhesive laminate useful for incorporating a functional cured film having no self-supporting property into a laminated glass. Let it be an issue.
In addition, the present invention is an adhesive laminate 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 adhesive laminate. 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 molten resin composition is cast on the surface of the support member to form a film, the first step of obtaining the first adhesive film, and the surface of the functional layer of the first laminate, under heating, the first And the functional layer and the first adhesive film are thermally bonded to each other, and the support is peeled off from the first laminated body so that the functional layer and the first adhesive film are at least A third step of obtaining a second laminate having
The manufacturing method of the adhesive laminated body which contains at least.
[2] The method according to [1], wherein, in the third step, heat bonding is performed at a temperature of an adhesive surface between the first adhesive film and the functional layer of 50 to 130 ° C.
[3] The method according to [1] or [2], wherein in the third step, the first adhesive film and the functional layer are thermally bonded under a pressure condition of less than 2 kg / cm ² .
[4] The molten resin composition used in the second step is a molten resin composition containing polyvinyl butyral as a main component, and is extruded from a casting die at a temperature of 150 to 250 ° C. [1] to [1] 3] Any one of the methods.
[5] The surface of the functional layer and the first support member between the first support member that transports while supporting the first laminate and the second support member that transports while supporting the first adhesive film. The method according to any one of [1] to [4], wherein the adhesive film is continuously thermally bonded to the surface of the adhesive film.
[6] The second support member that supports the first adhesive film is a support member in which a molten resin composition is cast, and the second step and the third step are continuously performed. The method of [5].
[7] The method according to any one of [1] to [6], wherein, in the second step, the support member for pouring the molten resin composition is any one of a roll, a belt, and a release film.
[8] In the second step, the surface of the support member on which the molten resin composition is poured is embossed, and the embossing is transferred to the surface of the first adhesive film [1] Any method of [7].
[9] The method according to any one of [1] to [8], further comprising a fourth step of bonding a second adhesive film on the surface of the functional layer from which the support has been peeled.
[10] The molten resin composition used in the second step is a melt of a composition containing polyvinyl butyral or a composition containing an ethylene / vinyl acetate copolymer [1] to [9] Either way.
[11] The method according to any one of [1] to [10], wherein the functional layer includes two or more layers in which a cholesteric liquid crystal phase is fixed.
[12] An adhesive laminate produced by the method according to any one of [1] to [11], which is composed of a composition containing polyvinyl butyral or a composition containing an ethylene / vinyl acetate copolymer And an adhesive laminate comprising at least a functional layer including two or more layers in which a cholesteric liquid crystal phase is fixed.
[13] An adhesive laminate produced by the method of any one of [1] to [12], comprising two compositions comprising a composition containing polyvinyl butyral or a composition containing an ethylene / vinyl acetate copolymer An adhesive laminate comprising at least a functional layer including two or more layers each having a cholesteric liquid crystal phase fixed between the adhesive film and the two adhesive films.
[14] A functional laminated glass comprising the adhesive laminate of [13] between a pair of transparent substrates.
[15] A method for producing a functional laminated glass, comprising disposing the adhesive laminate according to [13] between a pair of transparent substrates and bonding the pair of transparent substrates via the laminate. .

ADVANTAGE OF THE INVENTION According to this invention, the stable manufacturing method of the adhesive laminated body useful for incorporating the functional cured film without self-supporting property in a laminated glass can be provided.
Moreover, according to this invention, the adhesive laminated body useful for incorporating a functional layer efficiently in the functional laminated glass manufactured by the said method, and the functional laminated glass using this adhesive laminated body 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 adhesive laminated body of this invention. It is a cross-sectional schematic diagram of an example of the functional laminated glass of this invention.

  The present invention will be described in detail below. 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 an adhesive laminate.
A first step of preparing a first laminate having a support and a functional layer formed thereon by curing a liquid crystal composition;
The molten resin composition is cast on the surface of the support member to form a film, the first step of obtaining the first adhesive film, and the surface of the functional layer of the first laminate under heating, the first And the functional layer and the first adhesive film are thermally bonded to each other, and the support is peeled off from the first laminated body so that the functional layer and the first adhesive film are at least A third step of obtaining a second laminate having
It is related with the manufacturing method of the adhesive laminated body containing at least.

One feature of the method of the present invention is that the first adhesive film formed by casting is directly thermally bonded to the functional layer of the first laminate. For example, while transporting the first adhesive film formed on a support member such as a casting roll as it is, continuously with the first laminate supported and transported by the support member such as another transport roll It can be heat bonded and the method of the present invention is suitable for continuous production. Furthermore, in film formation by casting, it is easy to control the molten resin temperature when extruding from a casting die, the shape, size or temperature of a supporting member such as a casting roll, and the casting speed. By controlling any one or more, it is also possible to easily control the bonding surface temperature during thermal bonding of the adhesive film. As a result, it can be manufactured with high stability.
In addition, a method of bonding at the same time as film formation (for example, a method of casting a molten resin composition on the surface of the functional layer or a method of extruding the molten resin composition to the nip portion between the roll and the functional layer) Due to the resin composition, there is a problem that the functional layer is chemically or physically damaged and its function is lost. If the temperature of the molten resin composition is lowered in order to avoid damage, the unevenness of the film thickness of the adhesive film becomes remarkable, and the usefulness in various applications is impaired. In the method of the present invention, since the adhesive film is once formed and then thermally bonded to the functional layer, the above problem does not occur, and it is possible to stably provide an adhesive laminate useful in various applications. it can.

Hereinafter, each step will be described with reference to FIG.
(1) 1st process First, in the 1st process, the 1st laminated body 10 which has the support body 12 and the functional layer 14 formed by hardening a liquid-crystal composition on it is prepared. 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 is 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.
In FIG. 1, the functional layer 14 is expressed as a single layer. However, 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 after being processed 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. If the thickness of the functional layer 14 is too thin, the functional layer 14 becomes fragile, and defects may occur when the present invention is continuously carried out while being conveyed. In this respect, the overall thickness of the functional layer 14 is preferably 5 μm or more, and more preferably 5 to 50 μm.
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, the molten resin composition is formed into a film by a casting method to obtain the first adhesive film 20. As shown in FIG. 1, the molten resin composition 20 ′ can be cast from the casting die 22 to the surface of the casting roll 24 to form a film. The molten resin composition contains a resin that becomes an adhesive film as a main component. For example, a composition containing polyvinyl butyral or a composition containing an ethylene / vinyl acetate copolymer.

  The temperature of the molten resin composition 20 ′ when extruded from the casting die 22 affects the variation in the film thickness of the obtained first adhesive film 20. In order to stably thermally bond with the first laminated body 10, it is preferable that the film thickness of the first adhesive film is uniform. The preferable temperature range of the molten resin composition at the time of extrusion will depend on the melting point of the resin contained as the main component in the composition. In the embodiment in which the molten resin composition 20 ′ includes polyvinyl butyral as a main component, the temperature of the resin composition 20 ′ during extrusion from the casting die 22 is preferably 150 to 250 ° C.

  The support member for casting the molten resin composition 20 'is not limited to the shape of the casting roll. In addition, it can also be cast on the surface of a belt having at least a surface made of metal and a release film. It is preferable that the support member has a transport function because film formation in the second step and lamination in the third step can be performed continuously. The form of a casting roll is particularly preferable. Moreover, the surface of these support members may be embossed, and the embossing may be transferred to the surface of the first adhesive film 20 to be formed. For example, when the adhesive laminate produced by the method of the present invention is used for laminating laminated glass, it is necessary to deaerate at the time of laminating. It can deaerate easily by bonding the embossed surface of the adhesive film to the glass surface side.

(3) Third Step In the third step, the first adhesive film 20 is laminated on the surface of the functional layer 14 of the first laminate 10 under heating, and the functional layer 14 and the first layer While thermally bonding the adhesive film 20, the support 12 is peeled from the first stacked body 10 to obtain a second stacked body 30 having at least the functional layer 14 and the first adhesive film 20. That is, in this step, the functional layer 14 is transferred onto the first adhesive film 20. As shown in FIG. 1, this step is preferably performed continuously while being conveyed by the support member. Specifically, while the first laminated body 10 is continuously transported by the first transport roll 16 and the first adhesive film 20 is transported by the second transport roll 24, respectively, at the nip portion, It is preferable that the surface of the functional layer 14 of the first laminate 10 and the surface of the first adhesive film 20 are thermally bonded. In particular, as shown in FIG. 1, when the second transport roll 24 also serves as a support member for casting the molten resin composition 20 ′, the second step and the third step can be performed continuously. It is preferable because it is possible.

Since the functional layer 14 is a cured film of a liquid crystal composition, it has a characteristic that it does not easily deform even under heating. On the other hand, the first adhesive film 20 has a characteristic that it is easily deformed under heating. When these are thermally bonded while being conveyed, there is a problem that the functional layer 14 cannot follow the deformation of the first adhesive film 20 and breaks. In order not to cause troubles such as breakage, it is preferable to control the surface temperature of the first adhesive film 20 during thermal bonding and / or the pressure applied during thermal bonding. Specifically, in order to carry out stable thermal bonding, the temperature of the adhesive surface of the first adhesive film 20 with the functional layer 14 is set to 50 to 130 ° C. (more preferably 70 to 110 ° C., more preferably 70 to 100 ° C.) and / or less than ² kg / cm ² (more preferably 0.5 to 1.8 kg / cm ² , still more preferably 0.5 to 1.5 kg / cm ² ). Thermal bonding is preferably performed under pressure. When the temperature at the time of thermal bonding of the first adhesive film 20 and / or the pressure at the time of thermal bonding exceeds the above range, the functional layer is applied to the deformation of the first adhesive film 20 when thermally bonded while being conveyed. 14 may not follow and may break; on the other hand, if it is less than the above range, adhesion may be insufficient. The surface temperature of the first adhesive film 20 at the time of thermal bonding can be adjusted to the above preferable range depending on the time from casting to thermal bonding and the temperature of the transport roll 24, and the pressure at the time of thermal bonding is the transport roll. By controlling the pressure applied to the nip portions 16 and 24, it is possible to adjust to the preferable range.

  Although there is no restriction | limiting in particular about the conveyance speed by the conveyance rolls 16 and 24, if the conveyance tension loaded on each of the 1st laminated body 10 and the 1st adhesive film 20 is high, the 1st adhesive film 20 will be If the deformation is too large, the functional layer 14 may not follow and may break. From this viewpoint, it is preferable that the transport tension applied to each of the first laminate 10 and the first adhesive film 20 during transport is about 20 to 200 N / m.

  In the third step, the functional layer 14 and the first adhesive film 20 are thermally bonded, and the support 12 is peeled from the functional layer 14. 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.

Furthermore, you may implement the process of bonding a 2nd adhesive film to the 2nd laminated body 30. FIG. Similarly to the second adhesive film, the second adhesive film may be a film made of a composition containing polyvinyl butyral or a composition containing an ethylene / vinyl acetate copolymer. A commercially available sheet can also be used as an interlayer film for laminated glass.
For example, the second adhesive film can be bonded to the surface of the second laminate 30 from which the support has been peeled off. 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. Alternatively, the second laminate 30 and / or the second adhesive film may be heated in advance, and then bonded by pressure bonding. Furthermore, pasting with the 2nd adhesive film and the 2nd laminated body 30 can also be performed continuously from a 3rd process using a conveyance roll.

  In addition, although the example which performs the 2nd and 3rd process continuously was shown above, you may perform each process discontinuously separately. Moreover, you may perform a 2nd process in the state which left the supporting member stationary.

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.
The adhesive laminate 50 in FIG. 2 includes a first adhesive film 20, a second adhesive film 40, and a functional layer 14 therebetween. The first and second adhesive films 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 adhesive laminated body 50 between a pair of transparent substrates, and heat-bonding. In addition, when the film is formed by casting on the embossed support surface, the adhesive surface of the first adhesive film 20 with the glass plate or the like is embossed (in FIG. The processing is not shown), and when heat-bonding to a transparent substrate such as a glass plate, the unevenness of the embossed surface facilitates degassing and stable heat bonding can be performed.

In FIG. 3, the cross-sectional schematic diagram of an example of the functional laminated glass 60 using the adhesive laminated body 50 is shown.
The functional laminated glass shown in FIG. 3 is a laminated glass manufactured by heat-bonding a pair of transparent substrates 52 and 52 ′ via the adhesive laminate 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. Further, a low molecular liquid crystal compound and a high molecular liquid crystal compound can be used in combination. 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. No. 4,683,327, US Pat. No. 5,622,648, US Pat. No. 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 No. 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, and also from waste of heat energy, deformation of the light transmissive support, alteration, and the like. 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 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 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 is 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). Examples 1-5
A PVB melt was cast from the casting die at a temperature shown in the following table on a support member shown in the following table, thereby forming a first adhesive film. In the following table, the release film used as the support member is a polyethylene film. In addition, about any support member, this film | membrane was conveyed, forming into a film on a support member.
Separately, the first laminate sheet produced above was conveyed (example of film formation on a casting roll or a metal belt) while being conveyed by a conveyance roll, or left standing (film formation on a release film). Example) The functional layer was thermally bonded to the first adhesive film under the conditions shown in the following table without first bonding, and the PET film was peeled off.

Adhesive laminates were obtained by the above methods, respectively, and the adhesiveness, cracking of the functional layer, reflection characteristics of the functional layer, and thickness unevenness of the first adhesive film were evaluated according to the following criteria. The results are shown in the table below.
-Adhesiveness ○: The functional layer and PVB do not peel ×: The functional layer and PVB peel off • The functional layer cracks ○: The functional layer does not wrinkle on the PVB sheet and does not crack △: The functional layer Wrinkles occur on the PVB sheet ×: The functional layer breaks on the PVB sheet • Reflective properties of the functional layer ○: There is no change in the reflective properties of the functional layer before and after creating the laminate ×: The reflective properties of the functional layer The reflectance decreases after the laminate is created. ・ Thickness unevenness of the first adhesive film ○: The thickness unevenness of the adhesive film cannot be visually recognized. Δ: The thickness unevenness of the adhesive film cannot be visually recognized. Unevenness of adhesion occurs ×: Unevenness of thickness of adhesive film can be visually recognized, and unevenness of adhesion occurs when glass is laminated.

5. Comparative Examples 1-4
In Comparative Examples 1 and 2, a PVB melt was cast directly from the fluent die at the temperature shown in the following table onto the functional layer surface of the first laminate sheet produced above to form a PVB film. At the same time, it adhered to the functional layer.
In Comparative Examples 3 and 4, the nip portion between the transport roll and the casting roll of the first laminate sheet prepared above, and the PVB melt between the functional layer and the casting roll is shown in the table below. The film was extruded from a fluted die at the indicated temperature, and a PVB film was formed and simultaneously adhered to the functional layer.
Comparative examples were also evaluated in the same manner as described above. The results are shown in the table below.

＊１ 熱接着時の圧力
＊２ 流延ダイから押し出される際のＰＶＢ溶融物の温度
＊３ ＰＶＢ膜を機能層と熱接着する際の熱接着面の温度（非接触式の温度計で測定した温度）

* 1 Pressure during thermal bonding * 2 Temperature of PVB melt when extruded from casting die * 3 Temperature of thermal bonding surface when PVB film is thermally bonded to functional layer (measured with non-contact thermometer temperature)

From the above results, in Examples 1 to 5, a laminate of the functional layer and the PVB film can be manufactured without losing the light reflection performance of the functional layer and maintaining the film thickness of the PVB film uniformly. It was. In Examples 4 and 5, the pressure at the time of thermal bonding and the bonding surface temperature of the PVB film were out of the preferred ranges, so the functional layer could not follow the deformation of the PVB film, and some wrinkles were generated.
On the other hand, in Comparative Examples 1 to 4, since the PVB melt is brought into contact with the functional layer before film formation, in the examples where the temperature of the melt is high (Comparative Examples 2 and 4), the functional layer is damaged. In the examples (Comparative Examples 1 and 3) in which the light reflection performance is lost and the temperature of the PVB melt is lowered to such a level that the functional layer is not damaged, the thickness unevenness of the PVB film becomes significant, and the intermediate for laminated glass It was not a satisfactory level for use as a membrane sheet or the like.

  A commercially available interlayer film is bonded to the back surface (the surface from which the support is peeled off) of the functional layer of the adhesive laminate obtained in Example 1, and a laminated interlayer film is prepared. A laminated glass having a functional layer inside was prepared by bonding a glass plate. This laminated glass exhibited light reflection performance by the functional layer.

DESCRIPTION OF SYMBOLS 10 1st laminated body 12 Support body 14 Functional layer 16 Conveyance roll 20 1st adhesive film 20 'Molten resin composition 22 Casting die 24 Casting roll and conveyance roll 30 2nd laminated body 40 2nd adhesion | attachment Layer 50 laminated interlayer sheet 52, 52 'transparent substrate 60 functional laminated glass

Claims (13)

A first step of preparing a first laminate having a support and a functional layer formed thereon by curing a liquid crystal composition;
The molten resin composition is cast on the surface of the support member to form a film, the first step of obtaining the first adhesive film, and the surface of the functional layer of the first laminate, under heating, the first And the functional layer and the first adhesive film are thermally bonded to each other, and the support is peeled off from the first laminated body so that the functional layer and the first adhesive film are at least A third step of obtaining a second laminate having
The manufacturing method of the adhesive laminated body which contains at least. The method according to claim 1, wherein, in the third step, heat bonding is performed at a temperature of an adhesive surface between the first adhesive film and the functional layer of 50 to 130 ° C. 5. 3. The method according to claim 1, wherein in the third step, the first adhesive film and the functional layer are thermally bonded under a pressure condition of less than 2 kg / cm ² . The molten resin composition used in the second step is a molten resin composition containing polyvinyl butyral as a main component, and is extruded from a casting die at a temperature of 150 to 250 ° C. 2. The method according to item 1. The surface of the functional layer and the first adhesive property between the first support member that transports while supporting the first laminate and the second support member that transports while supporting the first adhesive film. Continuously heat-bonding to the membrane surface ,
The first support member is a rotating roll;
The method according to any one of claims 1 to 4, wherein the second support member and wherein the rotary roll or belt der Rukoto. The second support member for supporting the first adhesive film is a support member cast from a molten resin composition, and the second step and the third step are continuously performed. Item 6. The method according to Item 5. The method according to any one of claims 1 to 6, wherein, in the second step, the support member for pouring the molten resin composition is any one of a roll, a belt, and a release film. In the second step, the surface of the support member that sheds the molten resin composition is embossed, and the embossing is transferred to the surface of the first adhesive film. The method according to any one of the above. The method according to any one of claims 1 to 8, further comprising a fourth step of bonding a second adhesive film on the surface of the functional layer from which the support has been peeled off. The molten resin composition used in the second step is a melt of a composition containing polyvinyl butyral or a composition containing an ethylene / vinyl acetate copolymer. The method described in 1. The method according to claim 1, wherein the functional layer includes two or more layers in which a cholesteric liquid crystal phase is fixed. A contact adhesive laminate, viewed contains between a pair of transparent substrates,
The said adhesive laminated body is the adhesive laminated body manufactured by the method of any one of Claims 1-11, Comprising: The composition containing polyvinyl butyral or the composition containing an ethylene-vinyl acetate copolymer A functional laminated glass having at least a functional layer comprising two or more layers each having an adhesive film made of the above and a layer in which a cholesteric liquid crystal phase is fixed . Between a pair of transparent substrates, by placing the contact adhesive laminate, viewed contains that bonding the pair of transparent substrates via the laminated body,
The said adhesive laminated body is the adhesive laminated body manufactured by the method of any one of Claims 1-11, Comprising: The composition containing polyvinyl butyral or the composition containing an ethylene-vinyl acetate copolymer And a method for producing a functional laminated glass having at least a functional layer including two or more layers each having an adhesive film made of cholesteric liquid crystal phase and an adhesive film .

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