JP2012051220A - Laminate and method for producing laminate - Google Patents

Abstract

Provided are a laminate having excellent adhesion between an infrared reflective layer and a first polyvinyl butyral resin film, and a method for producing an infrared reflective film having high infrared reflective performance by suppressing wrinkles and breakage of the infrared reflective film. To do.
In a laminate having a transparent plastic resin film, an infrared reflection layer, and a first polyvinyl butyral resin film in this order, a horizontal alignment agent and a polymerizable liquid crystal compound are added to the infrared reflection layer, and the transparent plastic resin is added. The first polyvinyl butyral resin film is laminated inline on the infrared reflective layer side of the laminate including the film and the infrared reflective layer, and the laminate including the transparent plastic resin film and the infrared reflective layer and the first polyvinyl butyral resin film are provided. A method for producing a laminate comprising: pressing and pressing with a thermocompression roller, and the infrared reflective layer containing a horizontal alignment agent and a polymerizable liquid crystal compound.
[Selection figure] None

Description

  The present invention relates to a laminate including a transparent plastic resin film, an infrared reflective layer, and a polyvinyl butyral resin film, and a method for producing the same. TECHNICAL FIELD The present invention relates to a laminate for enhancing thermal insulation performance as a thermal insulation film or an interlayer film for laminated glass bodies, particularly to a building material window, an automobile window, and the like, 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 as one of them, it is effective in reducing the heat load of window glass of houses and automobiles, that is, the heat load due to sunlight. There is a need for glass and film. In order to reduce the heat load caused by sunlight, it is necessary to prevent the transmission of sunlight in the infrared region of the sunlight spectrum.

  A method using a cholesteric liquid crystal phase in an infrared light reflection film has been proposed. However, it was difficult to attach this to a target object because it was thin and fragile.

JP 2000-219543 A JP 2009-161406 A JP 2009-298661 A JP 2010-013311 A JP 2010-180089 A JP 59-223256 A Special table 2008-542065 gazette

In the case of using a cholesteric liquid crystal phase in an infrared reflecting film, a layer in which a cholesteric liquid crystal phase is fixed is formed on a transparent plastic resin film, and a polyvinyl butyral resin film is formed on one side or both sides. Lamination is being considered. However, problems such as wrinkles and breakage of the infrared reflecting film may occur with the bonding.
The present invention aims to solve such problems, and suppresses wrinkles and breakage of the infrared reflecting film, and manufactures an infrared reflecting film having high infrared reflecting performance and an infrared reflecting plate using the same. Provide a way to do it.

  In order to solve the above-mentioned problems, the present inventors diligently studied. As a result, the present inventors have found that the adhesiveness does not decrease when they are used.

Means for solving the above problems are as follows.
(1) A laminate comprising a transparent plastic resin film, an infrared reflective layer, and a first polyvinyl butyral resin film in this order, wherein the infrared reflective layer includes a horizontal alignment agent and a polymerizable liquid crystal compound.
(2) Furthermore, it has a 2nd polyvinyl butyral resin film, and has laminated | stacked in order of the 2nd polyvinyl butyral resin film, the transparent plastic resin film, the infrared reflective layer, and the 1st polyvinyl butyral resin film. The laminated body as described in 1).
(3) The laminate according to (1) or (2), wherein the infrared reflective layer is a layer formed by fixing a cholesteric liquid crystal phase.
(4) The laminate according to any one of (1) to (3), wherein the laminate is wound into a roll.
(5) The laminate according to any one of (1) to (4), wherein the horizontal alignment agent is a fluorine-based horizontal alignment agent.
(6) The laminate according to any one of (1) to (5), wherein an alignment layer is provided on the transparent plastic resin film, and an infrared reflective layer is provided on the surface of the alignment layer.
(7) The first polyvinyl butyral resin film is laminated inline on the infrared reflective layer side of the laminate comprising the transparent plastic resin film and the infrared reflective layer, and the laminate comprising the transparent plastic resin film and the infrared reflective layer and the first A method for producing a laminate, comprising: pressing and pressing the polyvinyl butyral resin film with a first thermocompression-bonding roller, and the infrared reflective layer including a horizontal alignment agent and a polymerizable liquid crystal compound.
(8) The method for producing a laminate according to (7), wherein the pressure bonding condition is 0.7 ≦ G / T <1:
However, T represents the total thickness before passing through the first thermocompression-bonding roller, and G represents the overall thickness after passing through the first thermocompression-bonding roller.
(9) The first polyvinyl butyral resin film is transported between the film feed roller and the first thermocompression-bonding roller with a transport tension of 50 to 200 g / cm (7) or ( The manufacturing method of the laminated body as described in 8).
(10) After pressure bonding of the first polyvinyl butyral resin film, after laminating the second polyvinyl butyral resin film inline on the side opposite to the first polyvinyl butyral resin film, the infrared reflective layer and the first polyvinyl butyral The laminate according to any one of (7) to (9), wherein the laminate including the resin film and the second polyvinyl butyral resin film are clamped by a pair of second thermocompression rollers. Body manufacturing method.
(11) The method for producing a laminate according to (10), wherein the pressure bonding condition is 0.7 ≦ G ′ / T ′ <1:
However, T ′ represents the entire thickness before passing through the second thermocompression roller, and G ′ represents the entire thickness after passing through the second thermocompression roller.
(12) After laminating a polyvinyl butyral resin film, the method includes a step of winding in a roll shape, and the winding tension is 75 to 250 g / cm, any one of (7) to (13) The manufacturing method of the laminated body as described in any one of.
(13) The method for producing a laminate according to (7) to (12), wherein the laminate is a laminate according to any one of (1) to (6).
(14) The laminate according to any one of (1) to (6);
A laminated glass body comprising a glass plate disposed on the first polyvinyl butyral resin film and / or the second polyvinyl butyral resin film of the laminate.
(15) A laminated body in which a pair of glass plates and a first polyvinyl butyral resin film, a transparent plastic resin film, an infrared reflective layer, and a second polyvinyl butyral resin film, which are disposed between the glass plates, are laminated in this order. A laminated glass body in which the laminate is a laminate according to any one of (2) to (6).

  According to the present invention, a laminated body in which a polyvinyl butyral resin film and an infrared reflective layer using a liquid crystal compound provided on a transparent plastic resin film are laminated, which is excellent in infrared reflective performance, at the time of transportation and laminated glass Thus, it has become possible to provide a laminate that suppresses the occurrence of wrinkles and breakage of the infrared reflecting film when formed into a body.

It is the schematic which shows an example of embodiment of the laminated body of this invention. It is the schematic which shows another example of embodiment of the laminated body of this invention. It is the schematic which shows an example of the more detailed structure of the structure of FIG. It is the schematic which shows an example of embodiment of the manufacturing method of the laminated body of this invention. It is the schematic which shows the state at the time of a film being conveyed by the 1st thermocompression-bonding roller of FIG. It is the schematic which shows an example of embodiment of the manufacturing method of the laminated body of this invention. It is the schematic which shows the state at the time of a film being conveyed by the 2nd thermocompression-bonding roller of FIG. It is the schematic of embodiment containing an ear cutting process. It is an image figure of the process of the ear cut in FIG.

  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.

The laminate of the present invention has a transparent plastic resin film, an infrared reflective layer, and a first polyvinyl butyral resin film in that order, and the infrared reflective layer includes a horizontal alignment agent and a polymerizable liquid crystal compound. To do.
Hereafter, the laminated body of this invention is demonstrated according to a figure. Needless to say, the present invention is not limited to these examples.
FIG. 1 is a schematic view showing an example of the structure of the laminate of the present invention, wherein 1 is an infrared reflecting layer, 2 is a transparent plastic resin film, and 3 is a first polyvinyl butyral resin film. The infrared reflection layer in the present invention is a layer formed by fixing a polymerizable liquid crystal compound, and is not particularly defined as long as it includes a horizontal alignment agent and has a capability of reflecting infrared rays. A layer having a fixed phase (hereinafter sometimes referred to as “cholesteric liquid crystal layer”) is preferable.
The transparent plastic resin film and the infrared reflection layer may be adjacent to each other, but usually include an alignment layer, and more preferably, the transparent plastic resin film, the undercoat layer, the alignment layer, and the infrared reflection layer are adjacent to each other in this order. It is the composition which includes.
The infrared reflective layer 1 and the first polyvinyl butyral resin film may be adjacent to each other or may have other functional layers such as an adhesive layer.

  FIG. 2 is a schematic view showing another example of the structure of the laminate of the present invention, and further has a second polyvinyl butyral resin 3 ′ on the transparent plastic resin film side. In FIG. 2, the first polyvinyl butyral resin film 3, the infrared reflection layer 1, the transparent plastic resin film 2, and the second polyvinyl butyral resin film are provided in a 3 ′ order. The transparent plastic resin film and the second polyvinyl butyral resin 3 ′ may be adjacent to each other or may have other constituent layers. Examples of other constituent layers include an easily adhesive layer and a pressure-sensitive adhesive layer.

(Transparent plastic resin film)
The transparent plastic resin film is not particularly limited as long as it is self-supporting and supports the infrared light reflection layer. The haze of the transparent plastic resin film is preferably 3% or less, more preferably 1% or less. It may be a special retardation plate such as a λ / 2 plate manufactured by managing the production process so as to satisfy predetermined optical characteristics, and there is a large variation in in-plane retardation. Specifically, when expressed in terms of variations in the in-plane retardation Re (1000) at a wavelength of 1000 nm, the variations in Re (1000) are 20 nm or more and 100 nm or more, and the polymer cannot be used as a predetermined retardation plate. A film etc. may be sufficient. The in-plane retardation of the resin base material is not particularly limited, and for example, a retardation plate having an in-plane retardation Re (1000) of a wavelength of 1000 nm of 800 to 13000 nm can be used.
The transparent plastic resin film used in the present invention preferably has a rigidity capable of withstanding the expansion and contraction of the polybilyl butyral resin during pressure bonding or laminated glass with the polyvinyl butyral resin film, and the Young's modulus is 100 times that of the polyvinyl butyral resin. About 1000 times is preferable. By setting it as such a structure, reflection nonuniformity can be suppressed more effectively.

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

  In this invention, it is preferable that the thickness of a transparent plastic resin film is 30 micrometers-200 micrometers, and it is more preferable that it is 100-200 micrometers. By setting it as such a thickness, reflection nonuniformity can be suppressed more effectively.

(Polyvinyl butyral resin film)
The first and second polyvinyl butyral resin films used in the present invention are not particularly defined as long as they are resin films mainly composed of polyvinyl butyral, and widely known polyvinyl butyral resin films can be employed. In addition, the resin film which has polyvinyl butyral resin as a main component means that 99.9 weight% or more of the resin component which comprises this film is polyvinyl butyral resin.
The thicknesses of the first and second polyvinyl butyral resin films are each preferably 200 to 1000 μm, and more preferably 300 to 800 μm.
The polyvinyl butyral resin film may contain other additives within the range not departing from the gist of the present invention, for example, may contain metal fine particles. The addition amount in this case is 1 to 10% by mass of the resin component.

(Cholesteric liquid crystal layer)
In the laminate of the present invention, the layer formed by fixing the cholesteric liquid crystal phase is preferably a laminate of four or more layers. FIG. 3 shows an example of the laminated structure of the cholesteric liquid crystal layer of FIG. 1, and 15a, 15b, 16a and 16b are infrared reflection layers, respectively, and the infrared reflection layer 1 is formed as a whole. ing. Reference numeral 26 denotes an alignment film.
Since the infrared reflective layers 15a, 15b, 16a and 16b are layers formed by fixing a cholesteric liquid crystal phase, the infrared reflective layers 15a, 15b, 16a and 16b exhibit light selective reflectivity for reflecting light of a specific wavelength based on the helical pitch of the cholesteric liquid crystal phase. . In one embodiment of the present invention, adjacent infrared reflective layers 15a and 15b have opposite cholesteric liquid crystal phase spiral directions and the same reflection center wavelength λ ₁₅ . Similarly, adjacent the infrared reflective layer 16a and 16b, together with the spiral directions of the respective cholesteric liquid crystal phase are opposite to each other, the reflection center wavelength lambda ₁₆ is the same. In the present embodiment, since λ ₁₅ ≠ λ ₁₆ is satisfied, the left and right circularly polarized light having a predetermined wavelength λ ₁₅ is selectively reflected by the infrared reflecting layers 15a and 15b, and the wavelength is reflected by the infrared reflecting layers 16a and 16b. Left circularly polarized light and right circularly polarized light having a wavelength λ ₁₆ different from λ ₁₅ are selectively reflected, and as a whole, the reflection characteristics can be broadened.

In FIG. 3, the center wavelength λ ₁₅ of selective reflection by the infrared reflecting layers 15a and 15b is in the range of 1010 to 1070 nm, for example, and the center wavelength λ ₁₆ of selective reflection by the infrared reflecting layers 16a and 16b is 1190 to 1290 nm, for example. It may be different, such as being in range. The infrared reflection efficiency can be improved by using two pairs of infrared reflection layers each having a selective reflection wavelength in the above range. The spectral distribution of the solar energy intensity shows a general tendency that the shorter the wavelength, the higher the energy, but the spectral distribution in the infrared light wavelength region includes a wavelength of 950 to 1130 nm and a wavelength of 1130 to 1350 nm. There are two energy intensity peaks. At least one pair of infrared reflective layers having a selective reflection center wavelength in the range of 1010 to 1070 nm (more preferably 1020 to 1060 nm), and a selective reflection center wavelength of 1190 to 1290 nm (more preferably, wave 1200 to 1280 nm). By utilizing at least one pair of infrared reflecting layers in the range, light corresponding to the two peaks can be reflected more efficiently, and as a result, the heat shielding property can be further improved.

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

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

  Each infrared reflective layer can be formed by various methods. An example is a method of forming by coating, which will be described later. More specifically, a curable liquid crystal composition capable of forming a cholesteric liquid crystal phase is applied to the surface of a transparent plastic resin film, an alignment layer, an infrared reflection layer, or the like. And after making the said composition into a cholesteric liquid crystal phase, it can harden | cure by making a hardening reaction (for example, polymerization reaction, a crosslinking reaction, etc.) advance, and can form.

The aspect of the cholesteric liquid crystal layer is not limited to the above aspect. 5 or more layers of infrared reflecting layers may be laminated on one surface of the substrate, and one or more pairs (5 layers or more in total) of infrared reflecting layers are laminated on both surfaces of the substrate. It may be the configuration. Moreover, the aspect which has 2 or more sets of infrared reflective layers which show the same reflection center wavelength may be sufficient.
Each thickness constituting the infrared reflective layer is preferably 1 to 10 μm, and more preferably 2 to 7 μm. The total thickness of the infrared reflective layer is preferably 10 to 50 μm, and more preferably 20 to 40 μm.

Moreover, the laminated body of this invention may have the non-light-reflective layer containing an organic material and / or an inorganic material other than the said structure. An example of the non-light-reflective layer that can be used in the present invention includes an easy-adhesion layer and an adhesive layer for facilitating close contact with other members (for example, a glass plate).
In another example of the non-light-reflective layer that can be used in the present invention, an undercoat layer that may be provided when forming an infrared reflective layer of a cholesteric liquid crystal phase, and an infrared reflective layer are formed. And an alignment layer that more precisely defines the alignment direction of the liquid crystal compound. The laminate of the present invention preferably includes an alignment layer. Further, it may have an undercoat layer. Further, the alignment layer 18 may be disposed between the respective infrared reflective layers (not shown).

  In the infrared light reflection layer in the present invention, a polymerizable liquid crystal compound and a horizontal alignment agent are used for forming each infrared reflection layer. Among these, it is preferable to use a curable liquid crystal composition. An example of the liquid crystal composition contains a rod-like liquid crystal compound, a horizontal alignment agent, 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 the uniformity of alignment, applicability, and film strength, it may contain at least one selected from various additives such as a non-uniformity inhibitor, a repellency inhibitor, and a polymerizable monomer. Further, in the liquid crystal composition, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, a colorant, metal oxide fine particles, and the like are added in a range that does not deteriorate the optical performance, if necessary. Can be added.

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

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

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

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

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

In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent. The substituents represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each preferably a substituent represented by R ¹ , R ² and R ³ in the general formula (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.

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

In the infrared reflective layer of the present invention, the horizontal alignment agent preferably contains a fluorine atom, more preferably a perfluoroalkyl group, from the viewpoint of suppressing the amount of the horizontal alignment agent added to the above range, It is particularly preferable that a perfluoroalkyl group of several 3 to 10 is included.
When the horizontal alignment agent is non-fluorine-based, it is preferable that the addition amount is 0.1% by mass or more because the problem of alignment defects does not occur.

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

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

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

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

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

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

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

Undercoat layer The laminate of the present invention may have an undercoat layer between the infrared reflective layer of the cholesteric liquid crystal phase and the transparent plastic resin film. If the adhesion between the infrared reflective layer of the cholesteric liquid crystal phase and the transparent plastic resin film is weak, a peeling failure may occur in the process of stacking the infrared reflective layer of the cholesteric liquid crystal phase, or the glass plate as an infrared light reflective plate. It causes a decrease in strength (impact resistance) when bonded. Therefore, a layer capable of improving the adhesion between the cholesteric liquid crystal layer and the transparent plastic resin film can be used as the undercoat layer. At the interface between the transparent plastic resin film and the undercoat layer, or between the undercoat layer and the infrared reflective layer of the cholesteric liquid crystal phase, an adhesive strength that does not peel off is required. Examples of materials that can be used to form the undercoat layer include acrylate copolymer, polyvinylidene chloride, styrene butadiene rubber (SBR), aqueous polyester, and the like. Further, in an embodiment in which the surface of the undercoat layer is bonded to the intermediate film, it is preferable that the adhesion between the undercoat layer and the intermediate film is good. From this viewpoint, the undercoat layer also contains a polyvinyl butyral resin together with the material. It is preferable. Moreover, since it is necessary to adjust adhesive force moderately as above-mentioned for undercoat, dialdehydes, such as glutaraldehyde and 2, 3- dihydroxy- 1, 4- dioxane, or hardening agents, such as a boric acid, are used. It is preferable to use the film appropriately. The addition amount of the hardener is preferably 0.2 to 3.0% by mass of the dry mass of the undercoat layer.
The thickness of the undercoat layer is preferably 0.05 to 0.5 μm.

The laminate of the present invention may have an alignment layer between the infrared reflective layer of the cholesteric liquid crystal phase and the transparent plastic resin film. The alignment layer has a function of more precisely defining the alignment direction of the liquid crystal compound in the cholesteric liquid crystal layer.
Since the alignment layer needs to be adjacent to the infrared reflective layer of the cholesteric liquid crystal phase, the alignment layer is preferably provided between the infrared reflective layer of the cholesteric liquid crystal phase and the substrate or the undercoat layer. However, the undercoat layer may have a function of an alignment layer. Moreover, you may have an orientation layer between the infrared reflective layers.

  The alignment layer preferably has a certain degree of adhesion to any of the adjacent infrared reflection layer, undercoat layer, and transparent plastic resin film. However, it is necessary to have such strength that peeling does not occur at any interface of the infrared reflective layer / alignment layer / undercoat layer / transparent plastic resin film of the cholesteric liquid crystal phase.

As a material used for the alignment layer, a polymer of an organic compound is preferable, and a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent is often used. Of course, polymers having both functions are also used. Examples of the polymer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylolacrylamide), styrene. / Vinyl toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, carboxymethyl cellulose, Examples thereof include polymers such as gelatin, polyethylene, polypropylene and polycarbonate, and compounds such as silane coupling agents. Examples of preferred polymers are water-soluble polymers such as poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvir alcohol and modified polyvinyl alcohol, and gelatin, polyvir alcohol and modified polyvinyl alcohol are preferred. Mention may be made in particular of polyvir alcohol and modified polyvinyl alcohol. Further, in the embodiment in which the surface of the alignment layer is bonded to the intermediate film, it is preferable that the adhesion between the alignment layer and the intermediate film is good. From this viewpoint, the alignment layer also contains the polyvinyl butyral resin together with the material. It is preferable.
The thickness of the alignment layer is preferably 0.1 to 2.0 μm.

  In processing, the laminate of the present invention may be cut using a blade, or may be cut by laser, water jet or heat.

[Laminated glass body]
The laminated glass body of the present invention is characterized by having a glass plate disposed on the first and / or second polyvinyl butyral resin film of the laminate of the present invention. Bonding with a glass plate is performed, for example, under a reduced pressure in a vacuum bag or the like, preliminarily pressure-bonded at a temperature of 80 to 120 ° C. for 30 to 60 minutes, and then in an autoclave under a pressure of 1.0 to 1.5 MPa. Bonding at a temperature of ˜150 ° C. can provide a laminated glass body in which a laminate is sandwiched between two glasses. Moreover, you may bond together using an adhesive material etc.

[Manufacturing method of laminate]
The method for producing a laminate of the present invention includes a step of laminating a first polyvinyl butyral resin film on the infrared reflective layer side of a laminate including a transparent plastic resin film and an infrared reflective layer, and the infrared reflective layer is a horizontal alignment agent. And a polymerizable liquid crystal compound. Hereinafter, the production method of the present invention will be described.

  FIG. 4 shows an example of a production method in the case where a laminate having the transparent plastic resin film, the infrared reflection layer, and the first polyvinyl butyral resin film as essential components as shown in FIG. 1 is produced in-line. In FIG. 4, reference numerals 11a and 11b denote first thermocompression rollers, respectively, which perform thermocompression bonding as a pair, and 21 is a laminate of a transparent plastic resin film and an infrared reflection layer. 1 is a polyvinyl butyral resin film feed roller, and 24 is a take-up roller for a laminate of the first polyvinyl butyral resin film and the infrared reflecting layer.

(1) in FIG.
In the present embodiment, a laminated body of the transparent plastic resin film 2 and the infrared reflection layer 1 is sent out from the feed roller 21. However, the laminate of the transparent plastic resin film 2 and the infrared reflective layer 1 may include other constituent layers between the transparent plastic resin film and the infrared reflective layer. Usually, an alignment layer and the like are included.
On the other hand, the first polyvinyl butyral resin film is fed from another feed roller 22 and laminated on the laminated body of the transparent plastic resin film 2 and the infrared reflective layer 1 on the infrared reflective layer side. The infrared reflective layer 1 and the first polyvinyl butyral resin film may be adjacent to each other, or other constituent layers may be included between them. In this case, the other constituent layer includes an adhesive layer.
These films are thermocompression-bonded by thermocompression-bonding rollers 11a and 11b.
The transport tension between the feed roller and the thermocompression roller of the first polyvinyl butyral resin film is preferably 50 to 200 g / cm, more preferably 100 to 200 g / cm. The temperature at this time is usually room temperature. For example, when the infrared reflective layer and the first polyvinyl butyral resin film are adjacent to each other, the temperature of the thermocompression roller can be set to 60 to 120 ° C.
FIG. 5 is a schematic view showing a state when the film is conveyed through the first thermocompression roller, and the thickness of the transparent plastic resin film 2 and the first polyvinyl butyral film 3 is reduced by thermocompression. Yes. Specifically, the pressure bonding condition is preferably 0.7 ≦ G / T <1, and more preferably 0.8 ≦ G / T <0.9. Here, T represents the total thickness before passing through the first thermocompression roller, and G represents the overall thickness after passing through the first thermocompression roller. By thermocompression bonding so as to have this configuration, the liquid crystal compound of the infrared reflective layer is not damaged, the first polyvinyl butyral resin film is not wrinkled, and the infrared reflective layer and the first polyvinyl butyral resin film The adhesion between them can be improved.
Usually, the surface of the polyvinyl butyral resin film is roughened by embossing or the like so that air can easily escape during sticking. The bonded surface becomes smooth following the adherend surface, and the optical performance is improved. However, the other surface needs to be maintained in a rough state in order to be bonded to a glass plate or the like. Therefore, it is preferable to make the surface of the roller in contact with the polyvinyl butyral resin film of the thermocompression-bonding roller rough and keep the rough surface of the P polyvinyl butyral resin film or to actively emboss.

(2) in FIG.
After the thermocompression bonding, the laminate of the first polyvinyl butyral resin film and the infrared reflective layer is wound up by the winding roller 24. At this time, it may be wound up so that any of them is on the inside, but it is preferable that the infrared reflection layer is on the inside. By setting it as such a structure, it exists in the tendency for an infrared reflective layer to receive a damage more easily.
The conveyance tension between the thermocompression-bonding roller and the take-up roller is preferably 50 to 200 g / cm, and more preferably 100 to 200 g / cm. The temperature at this time is usually room temperature.

Pressure bonding of the second polyvinyl butyral resin film In the present invention, as shown in FIG. 2, you may have a 2nd polyvinyl butyral resin film. The manufacturing method of such a laminated body is demonstrated according to FIG. FIG. 6 is a schematic diagram illustrating a method in which, after the first polyvinyl butyral resin film is provided in FIG. 2, the second polyvinyl butyral resin film is pressure-bonded to the opposite side of the first polyvinyl butyral resin film. In the figure, reference numerals 13a and 13b denote second press rollers, and 22 'denotes a second polyvinyl butyral resin film feed roller.
That is, in FIG. 4, after the first polyvinyl butyral resin film is laminated, the second polyvinyl butyral resin film is laminated. The second polyvinyl butyral resin film is provided on the side where the transparent plastic resin film is provided.
The transparent plastic resin film and the second polyvinyl butyral resin film may be adjacent to each other, or other constituent layers may be included between them. In this case, the other constituent layer includes an adhesive layer. These films are thermocompression bonded by thermocompression rollers 13a and 13b.
The conveyance tension ((3) in FIG. 6) between the thermocompression roller and the take-up roller is preferably 75 to 250 g / cm, and more preferably 100 to 200 g / cm. The temperature at this time is usually room temperature. When the transparent plastic resin film and the second polyvinyl butyral resin film are adjacent to each other, for example, the temperature of the thermocompression roller can be set to 60 to 120 ° C.
FIG. 7 is a schematic view showing a state when the film is conveyed on the second thermocompression-bonding roller, and the transparent plastic resin film and the first and second polyvinyl butyral films 3 and 3 ′ are obtained by thermocompression bonding. The thickness is decreasing. Specifically, the pressure bonding condition is preferably 0.7 ≦ G ′ / T ′ <1, and more preferably 0.7 ≦ G ′ / T ′ <0.9. Here, T ′ represents the total thickness before passing through the second thermocompression roller, and G ′ represents the overall thickness after passing through the second thermocompression roller. By thermocompression bonding so as to be in this configuration, the liquid crystal compound of the infrared reflective layer is not broken, wrinkles are not generated in the second polyvinyl butyral resin film, and between the infrared reflective layer and the second polyvinyl butyral resin film Adhesiveness can be improved.

Ear-cutting The method for producing a laminate of the present invention may further include an ear-cutting process. FIG. 8 shows a case in which an ear cutting step is included in FIG. 4, 31 and 31 ′ indicate receiving blades, and 32 and 32 ′ respectively indicate round blades. Usually, a round blade is rotated and pressed against the side of the rotating receiving blade, and the laminate is transported between them, and the receiving blade and the round blade are paired to cut the laminate, and then perform ear cutting. Yes. Slitting is performed with a so-called govel type cutting blade. In this embodiment, a pair of receiving blades and round blades are used to perform ear cutting, but it is needless to say that ear cutting may be performed using other blades. Moreover, in this embodiment, the ear cut is performed at two places, but the ear cut may be performed at one place. Preferably, only the positions 31 'and 32' are sufficient. Further, in the case of FIG.
As shown in FIG. 9, the edge cutting usually cuts off the end of the film in the width direction in the film being conveyed. In general, the thermal contraction rate differs between the infrared reflective layer and the polyvinyl butyral resin film. Therefore, even if an infrared reflective layer and a polyvinyl butyral resin film having the same width are laminated, the width after thermocompression may be different. Therefore, the width of the film can be made uniform by performing the edge cutting. Moreover, since the infrared reflective layer is formed by coating as described above, the thickness of the end portion is likely to be thinner than the central portion. From this point of view, by cutting off the edges, a high-quality laminate having a desired thickness over the entire surface can be manufactured.

Formation of Infrared Reflective Layer A laminate in which an infrared reflective layer is provided on the transparent plastic resin film of the present invention can be produced by a known method, but is prepared by applying a predetermined composition on the transparent plastic resin film. Preferably it is done. An example of a manufacturing method is
(1) Applying a composition containing a horizontal aligning agent and a polymerizable (curable) liquid crystal compound to the surface of the transparent plastic resin film to form a cholesteric liquid crystal phase;
(2) irradiating the polymerizable liquid crystal composition (hereinafter also referred to as a curable liquid crystal composition) with ultraviolet rays to advance a curing reaction, fixing a cholesteric liquid crystal phase, and forming an infrared reflective layer;
(3) forming an adhesive layer on the outermost layer of the infrared reflective layer;
Is a production method comprising at least
By repeating the steps (1) and (2) twice on one surface of the substrate, an infrared light reflection layer having the same configuration as that shown in FIG. 1 can be produced. Further, by repeating the steps (1) and (2) four times on one surface of the substrate, an infrared light reflection film having the same configuration as that shown in FIG. 2 can be produced.

<Formation of undercoat layer and alignment layer>
The undercoat layer is preferably formed on the surface of the transparent plastic resin film by coating. There is no limitation in particular about the coating method at this time, A well-known method can be used.
The alignment layer can be provided by means such as a rubbing treatment of an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound, or formation of a layer having microgrooves. Furthermore, an alignment layer in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known. The alignment layer is preferably formed on the surface of the polymer film by rubbing treatment.

<(1) Process>
In the step (1), first, the curable liquid crystal composition is applied to the surface of the transparent plastic resin film or the lower infrared reflection layer. The curable liquid crystal composition is preferably prepared as a coating solution in which a material is dissolved and / or dispersed in a solvent. The coating liquid can be applied by various methods such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method. Alternatively, a liquid crystal composition can be discharged from a nozzle using an ink jet apparatus to form a coating film.

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

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

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

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

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

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

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

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

Composition of coating liquid containing polymerizable liquid crystal

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

Horizontal alignment agent:

Chiral agent: Compound 2 (compound described in JP-A No. 2002-179668)

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

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

(Coating and film formation)
On the surface of a PET film (no undercoat layer, manufactured by FUJIFILM Corporation, thickness: 188 μm, resin 1), the undercoat layer coating solution (S1) is dried using a wire bar to a film thickness of 0. It apply | coated so that it might become 25 micrometers. Then, it heated at 150 degreeC for 10 minute (s), dried and solidified, and formed the undercoat.
Next, an alignment layer coating solution (H1) was applied on the formed undercoat layer using a wire bar so that the film thickness after drying was 1.0 μm. Then, it heated at 100 degreeC for 2 minute (s), dried and solidified, and formed the orientation layer. The alignment layer was subjected to rubbing treatment (rayon cloth, pressure: 0.1 kgf, rotation speed: 1000 rpm, conveyance speed: 10 m / min, frequency: 1 reciprocation).

Next, using the prepared coating liquids (R1), (R2), (L1), and (L2) containing the polymerizable liquid crystal, the cholesteric liquid crystal phase is fixed by the following procedure, and the infrared reflective layer (hereinafter referred to as the CL layer). Say) manufactured.
(1) Each coating solution was applied on the PET film at room temperature using a wire bar so that the thickness of the dried film was 6 μm.
(2) After drying at room temperature for 30 seconds to remove the solvent, the mixture was heated in an atmosphere of 125 ° C. for 2 minutes, and then made a cholesteric liquid crystal phase at 95 ° C. Next, UV irradiation was performed at an output of 60% for 6 to 12 seconds with an electrodeless lamp “D bulb” (90 mW / cm) manufactured by Fusion UV Systems Co., Ltd., and the cholesteric liquid crystal phase was fixed, and the film (infrared reflective layer) Was made.
(3) After cooling to room temperature, the above steps (1) and (2) were repeated to prepare an infrared reflective layer of a cholesteric liquid crystal phase in which four layers were laminated.
The coating liquid was applied in the order of (R1), (R2), (L1), and (L2).

(Lamination with polyvinyl butyral)
As shown in FIG. 4, the PET with the infrared reflection layer prepared above is overlaid with the polyvinyl butyral (thickness: 0.38 mm) on the infrared reflection layer, and the dry reflection laminator (manufactured by Taisei Laminator) is placed under the infrared reflection layer. A laminated film was made so as to be on the side. The conveyance tension at this time was 75 g / cm. The upper roller temperature was room temperature, the lower roller temperature was 120 ° C., the lamination pressure was 0.2 MPa, and the lamination speed was 0.2 m / min. The total thickness (T) before passing through the surface pressure and the thermocompression-bonding roller / the overall thickness (G) after passing through the thermocompression-bonding roller was 0.78.

(Production of laminated glass body)
The laminated film and new polyvinyl butyral (PVB) are stacked between two glass plates of 300mm x 300mm size so that they become glass plate / PVB / liquid crystal film / PET / PVB / glass plate, and are stacked on a vacuum rubber bag. Put a sample. The pressure inside the rubber bag was reduced (about 55 torr), and the rubber bag was placed in a heating oven and heated to 95 ° C. over 30 minutes. Thereafter, preliminary pressure bonding was performed at 95 ° C. for 40 minutes. After standing to cool, the laminated glass body sample was placed in an autoclave and heat-pressed under conditions of 130 ° C. and 1.2 MPa for 60 minutes to produce a laminated glass body with a heat ray reflective film.

(Adhesive strength)
In Example 1, the horizontal alignment agent was changed to the horizontal alignment agent shown in Table 2, and the addition amount was set to the following ratio in the infrared reflection layer. . Furthermore, the laminated glass body was produced on the conditions shown above using each laminated body. In order to evaluate the adhesive strength of the produced laminated glass body, a glass peeling test by dropping a steel ball was performed in accordance with an impact resistance test described in JIS R 3212. In the laminated glass body after the falling ball, the total weight of the glass pieces peeled from the glass plate on the side opposite to the falling surface was measured, and the adhesive strength was determined according to the following evaluation criteria.
A: Release glass amount is less than 6.0 g. O: Release glass amount is 6.0 g or more and less than 9.0 g. Δ: Release glass amount is 9.0 g or more and less than 12 g. X: Release glass amount is 12 g or more.

(Heat insulation performance)
About the laminated glass body of each Example and a comparative example, the transmission and reflection spectrum of a 300-2500 nm wavelength range was measured using JASCO Corporation spectrophotometer "V-670", and also the reflectance of the infrared region Was measured in the range of 2000 to 450 cm ⁻¹ using an infrared spectrophotometer “Varian 3000 FT-IR”, and a solar shading coefficient was obtained from the measured values of both (the smaller the value of the solar shading coefficient, the more the heat shielding High performance).
○: The shielding coefficient is less than 0.75.
(Triangle | delta): The shielding coefficient is 0.75 or more and less than 0.85.
X: A shielding coefficient of 0.85 or more.

(Comprehensive evaluation)
Considering the adhesive strength (anti-scattering property, impact resistance) and the heat shielding performance, it was comprehensively judged from the viewpoint of practicality. Any adhesive strength or heat shielding performance that was less than the practical performance (those with an evaluation of x) were judged to be not practical as a comprehensive evaluation, and were evaluated as x.

All examples were found to have impact resistance (anti-scattering resistance). In particular, it was found that even when a fluorine-based horizontal alignment agent was added, the adhesive strength was maintained and impact resistance could be achieved.
On the other hand, in Comparative Example 1, it was found that the heat shielding performance was remarkably inferior although it was excellent in impact resistance.

  In the above examples, the thickness of PET as a support was changed and others were performed in the same manner. As a result, it was found that reflection unevenness tends to be remarkably suppressed when the thickness of PET is 30 to 200 μm. .

DESCRIPTION OF SYMBOLS 1 Infrared reflective layer 2 Transparent plastic resin film 3 1st polyvinyl butyral resin film 3 '2nd polyvinyl butyral resin film 11a, 11b 1st thermocompression-bonding roller 13a, 13b 2nd thermocompression-bonding roller 15a Fixing a cholesteric liquid crystal phase Infrared reflective layer 15b Infrared reflective layer 16a formed by fixing a cholesteric liquid crystal phase Infrared reflective layer 16b formed by fixing a cholesteric liquid crystal phase Infrared reflective layer 18 formed by fixing a cholesteric liquid crystal phase 18 Orientation layer 21 Transparent plastic resin film And an infrared reflecting layer laminate feeding roller 22, 22 'Polyvinyl butyral resin film feeding roller 24 Polyvinyl butyral resin film and infrared reflecting layer take-up roller 31, 31' receiving blade 32, 32 'round blade T , Product before passing through T 'thermocompression roller Body overall thickness G, G 'thermocompression bonding roller passes laminate total thickness after

Claims (15)

  A laminate comprising a transparent plastic resin film, an infrared reflective layer, and a first polyvinyl butyral resin film in this order, wherein the infrared reflective layer includes a horizontal alignment agent and a polymerizable liquid crystal compound.   Furthermore, it has a 2nd polyvinyl butyral resin film, and has laminated | stacked in order of the 2nd polyvinyl butyral resin film, the transparent plastic resin film, the infrared reflective layer, and the 1st polyvinyl butyral resin film. The laminated body of description.   The laminate according to claim 1 or 2, wherein the infrared reflective layer is a layer formed by fixing a cholesteric liquid crystal phase.   The laminate according to any one of claims 1 to 3, wherein the laminate is wound into a roll.   The laminate according to any one of claims 1 to 4, wherein the horizontal alignment agent is a fluorine-based horizontal alignment agent.   The laminate according to any one of claims 1 to 5, wherein an alignment layer is provided on the transparent plastic resin film, and an infrared reflective layer is provided on the surface of the alignment layer.   The first polyvinyl butyral resin film is laminated inline on the infrared reflective layer side of the laminate comprising the transparent plastic resin film and the infrared reflective layer, and the laminate comprising the transparent plastic resin film and the infrared reflective layer and the first polyvinyl butyral A method for producing a laminate, comprising: pressing and pressing a resin film with a first thermocompression-bonding roller, and the infrared reflective layer including a horizontal alignment agent and a polymerizable liquid crystal compound. The method for producing a laminate according to claim 7, wherein the pressure-bonding condition is 0.7 ≦ G / T <1.
However, T represents the total thickness before passing through the first thermocompression-bonding roller, and G represents the overall thickness after passing through the first thermocompression-bonding roller.   The first polyvinyl butyral resin film is conveyed at a conveyance tension of 50 to 200 g / cm between the film feeding roller and the first thermocompression-bonding roller. A manufacturing method of a layered product.   After pressure bonding of the first polyvinyl butyral resin film, the second polyvinyl butyral resin film is laminated inline on the side opposite to the first polyvinyl butyral resin film, and then the infrared reflective layer and the first polyvinyl butyral resin film are The method for producing a laminate according to any one of claims 7 to 9, wherein the laminate and the second polyvinyl butyral resin film are sandwiched and pressed by a pair of second thermocompression rollers. The method for producing a laminate according to claim 10, wherein the pressure bonding condition is 0.7 ≦ G ′ / T ′ <1.
However, T ′ represents the entire thickness before passing through the second thermocompression roller, and G ′ represents the entire thickness after passing through the second thermocompression roller.   The laminate according to any one of claims 7 to 13, wherein the laminate comprises a step of winding the polyvinyl butyral resin film into a roll shape, and the winding tension is 50 to 200 g / cm. Manufacturing method.   The manufacturing method of the laminated body of Claims 7-12 whose said laminated body is a laminated body as described in any one of Claims 1-6. The laminate according to any one of claims 1 to 6,
A laminated glass body comprising a glass plate disposed on the first polyvinyl butyral resin film and / or the second polyvinyl butyral resin film of the laminate.   A laminate having a pair of glass plates and a first polyvinyl butyral resin film, a transparent plastic resin film, an infrared reflective layer, and a second polyvinyl butyral resin film, which are sandwiched between the glass plates, in that order. The said laminated body is a laminated glass body which is a laminated body as described in any one of Claims 2-6.

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