JP5777463B2 - Film, infrared reflector, laminate and laminated glass - Google Patents

Description

  The present invention relates to a film, an infrared reflector, a laminate, and a laminated glass. More specifically, the present invention relates to a film using a cholesteric liquid crystal composition excellent in laminating applicability, an infrared reflector using the film, a laminate, and a laminated glass.

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. Laminated glass in which a thermal barrier film is inserted between two glass plates is used for automotive windshields and building glass windows. Thermal barrier films used for these applications are required to have low haze and good visibility.
In order to reduce the heat load due to 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 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, so that there is a problem that the use of a mobile phone or the like causes radio wave interference, and the ETC or GPS cannot be used when used in an automobile.

  As a heat shielding film, a selective wavelength reflection film having a configuration in which a liquid crystal film formed by fixing a cholesteric liquid crystal phase on an arbitrary support is provided. Such a liquid crystal film is also excellent in electromagnetic wave permeability, and can be prepared by, for example, applying and drying a coating liquid containing a polymerizable cholesteric liquid crystal compound, polymerizing, and fixing a cholesteric liquid crystal layer ( For example, see Patent Documents 1 and 2.)

  Among these documents, Patent Document 1 mentions that haze is lowered, and it is described that the haze value of a cholesteric liquid crystal film can be lowered by using a thiol compound when forming a cholesteric liquid crystal layer. Moreover, in the Example of the same document, BYK361 which is a surfactant is used as a haze reducing agent, and it is disclosed that a two-layer laminated liquid crystal film having a haze of 1.6% was obtained.

Special table 2009-514022 gazette Japanese Patent No. 3745221

When the present inventors examined the characteristics of the liquid crystalline mixture described in Patent Documents 1 and 2, it was found that the haze required for use in automotive windshields and building glass windows could not be reduced. In contrast, the present inventors have found that cholesteric haze can be reduced by adding a fluorine-based haze reducing agent, particularly a haze reducing agent having a perfluoroalkyl chain, to the curable liquid crystal composition.
However, when a haze reducing agent having a general perfluoroalkyl chain is added and a cholesteric liquid crystal film in which a plurality of cholesteric liquid crystal layers are laminated by coating is produced, a coating liquid for the second and subsequent curable liquid crystal compositions is obtained. We found that the problem of being repelled arises. In particular, such a problem is remarkable when high-speed coating of, for example, about 20 to 40 m / min is performed, and there is a problem that desired performance cannot be obtained when uneven coating occurs.

  The present invention aims to improve the above problems. That is, the problem to be solved by the present invention is to provide a film having low haze and excellent suitability for high-speed laminate coating.

  As a result of intensive studies by the present inventors for the purpose of solving the above-mentioned problems, by using a haze reducing agent having a perfluoroalkyl chain having a specific embossing ratio as a haze reducing agent used in Patent Document 1, The inventors have found that it is possible to produce a film having good suitability for high-speed lamination coating while improving haze.

The present invention, which is means for solving the above problems, is as follows.
[1] A first liquid crystal layer formed by fixing the first curable liquid crystal composition by curing it in a cholesteric liquid crystal phase;
Having at least one second liquid crystal layer laminated on the first liquid crystal layer and fixed by curing the curable liquid crystal composition in a cholesteric liquid crystal phase;
The first curable liquid crystal composition comprises polymerizable liquid crystal molecules and a first haze reducing agent having at least one perfluoroalkyl chain;
The film according to the first haze-reducing agent, wherein the embossing rate represented by the following formula (1) is 50% or less.
Formula (1)
Raising rate (%) = 100% × B / A
(In the formula (1), a lower layer curable liquid crystal composition containing polymerizable liquid crystal molecules and a haze reducing agent is fixed by curing in the state of a cholesteric liquid crystal phase to form a lower layer, and haze reduction is performed on the lower layer. When the upper layer is laminated by applying the upper layer curable liquid crystal composition having the same composition as the lower layer curable liquid crystal composition except for the agent, and fixing by curing in the state of the cholesteric liquid crystal phase, A is This represents the fluorine atom content relative to the total amount of carbon atoms and fluorine atoms present on the surface of the lower layer, that is, one-layer product. Represents the rate.)
[2] In the film according to [1], the first haze reducing agent is preferably non-polymerizable.
[3] In the film according to [1] or [2], the first haze-reducing agent preferably has at least two perfluoroalkyl chains.
[4] In the film according to any one of [1] to [3], it is preferable that the first haze reducing agent has two perfluoroalkyl chains.
[5] In the film according to any one of [1] to [4], the first haze-reducing agent is 0. 0 relative to the polymerizable molecule in the first curable liquid crystal composition. It is preferable that 1 mass% or more is contained.
[6] In the film according to any one of [1] to [5], the curable liquid crystal composition preferably includes a second haze-reducing agent.
[7] In the film according to [6], the second haze reducing agent is preferably non-polymerizable.
[8] The film according to [6] or [7] preferably has an embossing ratio represented by the formula (1) of the second haze reducing agent of more than 50%.
[9] In the film according to any one of [6] to [8], the second haze reducing agent preferably has a perfluoroalkyl chain.
[10] In the film according to any one of [6] to [9], it is preferable that the second haze-reducing agent has six perfluoroalkyl chains.
[11] In the film according to any one of [6] to [10], the second haze-reducing agent is 0.005 to the polymerizable molecule in the first curable liquid crystal composition. It is preferable that 0.10 mass% is contained.
[12] In the film according to any one of [1] to [11], the curable liquid crystal composition used for the second liquid crystal film preferably contains a haze reducing agent.
[13] The film according to any one of [1] to [12] preferably exhibits selective reflection characteristics in an infrared wavelength region.
[14] A step of forming a first liquid crystal layer for curing and fixing the first curable liquid crystal composition in a cholesteric liquid crystal phase; and a cholesteric liquid crystal composition on the first liquid crystal layer. A step of forming at least one second liquid crystal layer formed by being cured and fixed in a liquid crystal phase,
The first curable liquid crystal composition comprises polymerizable liquid crystal molecules and a first haze reducing agent having at least one perfluoroalkyl chain;
The embossing rate represented by the following formula (1) of the first haze reducing agent is 50% or less,
The method for producing a film, wherein the step of forming at least one second liquid crystal layer includes a step of applying the curable liquid crystal composition at 20 to 40 m / min.
Formula (1)
Raising rate (%) = 100% × B / A
(In the formula (1), a lower layer curable liquid crystal composition containing polymerizable liquid crystal molecules and a haze reducing agent is fixed by curing in the state of a cholesteric liquid crystal phase to form a lower layer, and haze reduction is performed on the lower layer. When the upper layer is laminated by applying the upper layer curable liquid crystal composition having the same composition as the lower layer curable liquid crystal composition except for the agent, and fixing by curing in the state of the cholesteric liquid crystal phase, A is This represents the fluorine atom content relative to the total amount of carbon atoms and fluorine atoms present on the surface of the lower layer, that is, one-layer product. Represents the rate.)
[15] In the method for producing a film according to [14], the amount of the first haze-reducing agent contained in the first curable liquid crystal composition is the polymerizable property contained in the curable liquid crystal composition. It is preferable that it is 0.10 mass% with respect to a liquid crystal molecule.
[16] A film produced by the method for producing a film according to [15].
[17] An infrared reflecting plate comprising the film according to any one of [1] to [13] and [16].
[18] The infrared reflecting plate according to [17] preferably includes a λ / 2 plate.
[19] The infrared reflector according to [17] or [18] preferably has an easy-adhesion layer as the outermost layer.
[20] It is formed by using the infrared reflecting plate according to any one of [17] to [19], and has at least the first liquid crystal film and the second liquid crystal film of the film. A laminate characterized by the following.
[21] A laminated glass comprising the laminate according to [20] and at least two glass plates, wherein the laminate is inserted into the two glasses.
[22] An automotive windshield including the laminated glass according to [21].
[23] Glass for building materials including the laminated glass according to [21].

  According to the present invention, it is possible to provide a film having a low haze and excellent suitability for high-speed laminate coating. Moreover, the manufacturing method of the film which can manufacture the film of this invention stably at high speed can be provided.

FIG. 1 is a schematic view showing a cross section of an example of the laminated glass of the present invention. FIG. 2 is a schematic view showing a cross section of another example of the laminated glass of the present invention. FIG. 3 is a schematic view showing a cross section of another example of the laminated glass of the present invention. FIG. 4 is a schematic view showing a cross section of an example of the film of the present invention.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. 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 film]
The film of the present invention includes a first liquid crystal layer formed by fixing the first curable liquid crystal composition by curing in the state of a cholesteric liquid crystal phase, and a curable liquid crystal layer laminated on the first liquid crystal layer. The composition has at least one second liquid crystal layer fixed by curing in a cholesteric liquid crystal phase, and the first curable liquid crystal composition comprises a polymerizable liquid crystal molecule and at least one perfluoroalkyl. And a first haze-reducing agent having a chain, wherein the first haze-reducing agent has an embossing ratio represented by the following formula (1) of 50% or less.
Formula (1)
Raising rate (%) = 100% × B / A
(In the formula (1), a lower layer curable liquid crystal composition containing polymerizable liquid crystal molecules and a haze reducing agent is fixed by curing in the state of a cholesteric liquid crystal phase to form a lower layer, and haze reduction is performed on the lower layer. When the upper layer is laminated by applying the upper layer curable liquid crystal composition having the same composition as the lower layer curable liquid crystal composition except for the agent, and fixing by curing in the state of the cholesteric liquid crystal phase, A is This represents the fluorine atom content relative to the total amount of carbon atoms and fluorine atoms present on the surface of the lower layer, that is, one-layer product. Represents the rate.)
With such a configuration, the film of the present invention has low haze and is excellent in high-speed laminate coating suitability. Hereafter, each structure of the film of this invention is demonstrated.

<First liquid crystal layer>
The film of the present invention includes a first liquid crystal layer formed by fixing the first curable liquid crystal composition by curing it in a cholesteric liquid crystal phase.
The first curable liquid crystal composition includes a polymerizable liquid crystal molecule and a first haze reducing agent having at least one perfluoroalkyl chain, and is represented by the formula (1) of the first haze reducing agent. The raised ratio is 50% or less.

(1) Haze reducing agent In this invention, a haze reducing agent means the material which can reduce the haze of the film obtained.
The haze reducing agent may be an alignment control agent. The fluorine-based alignment control agent can reduce the tilt angle of the molecules of the liquid crystal compound or substantially horizontally align it 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 less likely to occur, and thus transparency in the visible light region is increased. On the other hand, when the molecules of the liquid crystal compound are aligned at a large tilt angle, for example, in the case of a cholesteric liquid crystal phase, the spiral axis is deviated from the film surface normal, so that the reflectivity is reduced or a fingerprint pattern is generated. This is not preferable because it increases haze and shows diffractive properties.
Examples of the fluorine-containing (meth) acrylate-based polymer that can be used as the fluorine-based alignment control agent are described in JP-A 2007-272185, [0018] to [0043].
An example of a liquid crystal alignment accelerator having a discotic core usable as the fluorine-based alignment control agent and a long-chain fluorinated alkyl group at its end is described in JP-A No. 2002-129162.
Below, the haze reducing agent used for this invention is demonstrated.

(1-1) First haze reducing agent The first curable liquid crystal composition includes a first haze reducing agent having at least one perfluoroalkyl chain, and the following formula (1) of the first haze reducing agent ( The embossing ratio represented by 1) is 50% or less.
Formula (1)
Raising rate (%) = 100% × B / A
(In the formula (1), a lower layer curable liquid crystal composition containing polymerizable liquid crystal molecules and a haze reducing agent is fixed by curing in the state of a cholesteric liquid crystal phase to form a lower layer, and haze reduction is performed on the lower layer. When the upper layer is laminated by applying the upper layer curable liquid crystal composition having the same composition as the lower layer curable liquid crystal composition except for the agent, and fixing by curing in the state of the cholesteric liquid crystal phase, A is This represents the fluorine atom content relative to the total amount of carbon atoms and fluorine atoms present on the surface of the lower layer, that is, one-layer product. Represents the rate.)

The measuring method for the fluorine atom content relative to the total amount of carbon atoms and fluorine atoms present on the surface of each layer used when measuring the raising ratio of the haze reducing agent is not limited.
In the present invention, fluorine atoms / carbon atoms (F / C) existing on the surface of each layer were measured by X-ray photoelectron spectroscopy, and the calculation was performed based on these values.

In the film of the present invention, the first haze reducing agent is preferably non-polymerizable.
In the film of the present invention, the first haze reducing agent preferably has at least two perfluoroalkyl chains, and the first haze reducing agent more preferably has two perfluoroalkyl chains.

  In the film of the present invention, the first haze-reducing agent is preferably contained in an amount of 0.03% by mass or more, more preferably 0.10% by mass or more based on the polymerizable molecule in the first curable liquid crystal composition. Is more preferable.

The first haze reducing agent is preferably represented by the following general formula (I).
The compound of the following formula (I) is characterized by having a divalent group at the center and a fluorinated alkyl group at the terminal. A compound having a fluorinated alkyl group at the terminal is effective as an alignment accelerator, but conventionally known alignment accelerators have a limited use concentration range and low solubility, limiting their use. It had been. Since the compound of the following formula (I) exhibits the same or better orientation performance in a wider concentration range and good solubility, a composition containing them has an advantage that it is easy to use in production. Moreover, since it can be hardened | cured by superposition | polymerization, it is useful for various uses, such as an optical member.

In the general formula (I), L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently a single bond, —O—, —S—, —CO—, —COO—, —OCO. -, -COS-, -SCO-, -NRCO-, -CONR- (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), more preferably -O-, -S-, -CO-. , -COO-, -OCO-, -COS-, -SCO-, more preferably -O-, -CO-, -COO-, -OCO-. The alkyl group that R can take may be linear or branched. As for carbon number, it is more preferable that it is 1-3, and a methyl group, an ethyl group, and n-propyl group can be illustrated.

  Sp represents a single bond or an alkylene group having 1 to 10 carbon atoms, more preferably a single bond or an alkylene group having 1 to 7 carbon atoms, still more preferably a single bond or an alkylene group having 1 to 4 carbon atoms, Non-adjacent methylene groups in the alkylene are substituted with —O—, —S—, —CO—, —COO—, —OCO—, —COS—, —SCO—, —NRCO—, —CONR—, —OH. It may be. The alkylene group may or may not be branched, but a linear alkylene group having no branch is preferred.

A ¹ and A ^{2 each} represent a divalent aromatic hydrocarbon group or a divalent heterocyclic group, and more preferably a divalent aromatic hydrocarbon. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, still more preferably 6 to 10 carbon atoms, and still more preferably a phenylene group. . In the case of a phenylene group, it is preferable to have a bond at the meta or para position, and it is particularly preferable to have a bond at the para position. The divalent heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring. A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is most preferable. As the hetero atom constituting the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocycle is preferably an aromatic heterocycle. The aromatic heterocycle is generally an unsaturated heterocycle. An unsaturated heterocyclic ring having the most double bond is more preferable. Examples of heterocyclic rings include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline Ring, pyrazolidine ring, triazole ring, triazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring included. The divalent aromatic hydrocarbon group or divalent heterocyclic group represented by A ¹ and A ² may have a substituent. Examples of such a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group, or an ester group. For the explanation and preferred ranges of these groups, the corresponding description of T below can be referred to. Examples of the substituent for the divalent aromatic hydrocarbon group or divalent heterocyclic group represented by A ¹ or A ² include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a bromine atom, a chlorine atom, and a cyano group. Examples include groups. A ¹ and A ² are preferably the same.

で表される二価の基または二価の芳香族複素環基を表す（Ｘは炭素数１〜８のアルキル基、アルコキシ基、ハロゲン原子、シアノ基またはエステル基を表し、Ｙａ、Ｙｂ、Ｙｃ、Ｙｄはおのおの独立して水素原子または炭素数１〜４のアルキル基を表す）であり、より好ましくは

であり、さらに好ましくは

である。Ｘがとりうるアルキル基の炭素数は１〜８であり、１〜５であることが好ましく、１〜３であることがより好ましい。アルキル基は、直鎖状、分枝状、環状のいずれであってもよく、直鎖状または分枝状であることが好ましい。好ましいアルキル基として、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などを例示することができる。Ｘがとりうるアルコキシ基のアルキル部分については、Ｘがとりうるアルキル基の説明と好ましい範囲を参照することができる。Ｘがとりうるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子を挙げることができ、塩素原子、臭素原子が好ましい。Ｘがとりうるエステル基としては、ＲＣＯＯ−で表される基を例示することができる。Ｒとしては炭素数１〜８のアルキル基を挙げることができる。Ｒがとりうるアルキル基の説明と好ましい範囲については、上記のＸがとりうるアルキル基の説明と好ましい範囲を参照することができる。エステルの具体例として、ＣＨ₃ＣＯＯ−、Ｃ₂Ｈ₅ＣＯＯ−を挙げることができる。Ｙａ、Ｙｂ、Ｙｃ、Ｙｄがとりうる炭素数１〜４のアルキル基は、直鎖状であっても分枝状であってもよい。例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などを例示することができる。二価の芳香族複素環基の説明と好ましい範囲については、下記のＡ¹とＡ²の芳香族複素環基に関する説明と記載を参照することができる。 T is

(X represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group, or an ester group, Ya, Yb, Yc. , Yd each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably

And more preferably

It is. Carbon number of the alkyl group which X can take is 1-8, it is preferable that it is 1-5, and it is more preferable that it is 1-3. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. Preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. For the alkyl part of the alkoxy group that X can take, the description and preferred range of the alkyl group that X can take can be referred to. Examples of the halogen atom that X can take include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferable. Examples of the ester group that X can take include a group represented by RCOO-. Examples of R include an alkyl group having 1 to 8 carbon atoms. For the description and preferred range of the alkyl group that R can take, the description and preferred range of the alkyl group that X can take can be referred to. Specific examples of the ester include CH ₃ COO— and C ₂ H ₅ COO—. The alkyl group having 1 to 4 carbon atoms that can be taken by Ya, Yb, Yc, and Yd may be linear or branched. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like can be exemplified. For the explanation and preferred range of the divalent aromatic heterocyclic group, the following explanation and description regarding the aromatic heterocyclic group of A ¹ and A ² can be referred to.

Hb represents a fluorinated alkyl group having 3 to 30 carbon atoms, more preferably a fluorinated alkyl group having 3 to 20 carbon atoms, and further preferably a fluorinated alkyl group having 3 to 10 carbon atoms. Here, the fluorinated alkyl group may or may not be substituted with hydrogen. The fluorinated alkyl group may be linear, branched or cyclic, but is preferably linear or branched, and more preferably linear. Preferred examples of the fluorinated alkyl group include those having a perfluoroalkyl group at the end. That is, it is preferably a group represented by the following general formula.
(C _p F _{2p + 1} ) − (C _q H _2q ) −
In the above formula, p is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. q is preferably from 0 to 20, more preferably from 0 to 10, and even more preferably from 0 to 5. p + q is 3-30.

k, l, m, n, and p represent an integer of 0 or more, and o is an integer of 1 to 4. Further, when k, l, m, n, o, and p are 2 or more, a plurality of structures in parentheses may be the same or different. For example, when k is 2, two L ¹ existing in the molecule may be the same or different from each other. K, l, m, n in the general formula (I) is preferably an integer of 0 to 6, more preferably an integer of 0 to 4, and any of 0 to 3 It is more preferably an integer, and even more preferably an integer of 0 to 2. As a preferable combination of k, l, m, and n in the general formula (I), a combination in which l = m = 1 and k = n = 0 and a combination in which l = m = 1 and k = n = 1 More preferable combinations include a combination in which l = m = 1 and k = n = 0. o is preferably 1 or 2. p is preferably an integer of 1 to 4, and more preferably 1 or 2.

  The compound represented by the general formula (I) may have a symmetrical molecular structure or may have no symmetry. In addition, the symmetry here means one corresponding to any of point symmetry, line symmetry, or rotational symmetry, and asymmetry means one not corresponding to any of point symmetry, line symmetry, or rotational symmetry. .

The compound represented by formula (I), above mentioned fluorinated alkyl group (Hb), the linking group _{^{(L 1) k -Sp- (L}} 2 -A 1) l -L 3 and -L ⁴ - ( A ² -L ⁵ ) _m -Sp- (L ⁶ ) _n , and T, which is a divalent group having an excluded volume effect. The two fluorinated alkyl groups (Hb) present in the molecule are preferably the same as each other, and the linking group (L ¹ ) _k -Sp- (L ² -A ¹ ) ₁ -L ³ present in the molecule and ^{-L 4 - (a 2 -L 5} ) m -Sp- (L 6) n also is preferably identical to each other. End of Hb- (L ¹⁾ _k -Sp- and -Sp- (L ⁶⁾ _n -Hb is preferably a group represented by any one of formulas below.
(C _p F _{2p + 1} ) − (C _q H _2q ) −
_{(C p F 2p + 1)} - (C q H 2q) -O- (C r H 2r) -
_{(C p F 2p + 1)} - (C q H 2q) -COO- (C r H 2r) -
_{(C p F 2p + 1)} - (C q H 2q) -OCO- (C r H 2r) -
In the above formula, p is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. q is preferably from 0 to 20, more preferably from 0 to 10, and even more preferably from 0 to 5. p + q is 3-30. r is preferably from 1 to 10, and more preferably from 1 to 4.
When l in the general formula (I) is 1 or more, terminal Hb- (L ¹ ) _k -Sp-L ² -and -L ⁵ -Sp- (L ⁶ ) _n -Hb are any of the following: A group represented by the general formula is preferred.
_{(C p F 2p + 1)} - (C q H 2q) -O
_{(C p F 2p + 1)} - (C q H 2q) -COO-
_{(C p F 2p + 1)} - (C q H 2q) -O- (C r H 2r) -O-
_{(C p F 2p + 1)} - (C q H 2q) -COO- (C r H 2r) -COO-
_{(C p F 2p + 1)} - (C q H 2q) -OCO- (C r H 2r) -COO-
The definitions of p, q and r in the above formula are the same as the definitions immediately above.
Specific examples of the compound represented by the general formula (I) are shown below. However, the compound represented by the general formula (I) that can be employed in the present invention should not be limitedly interpreted by the following specific examples.

  The compound represented by the general formula (I) is synthesized by appropriately selecting and combining the synthesis methods described in JP-A No. 2002-129162, JP-A No. 2002-97170 and literatures cited in the gazette. can do. Moreover, it can synthesize | combine by combining another well-known synthesis method as needed.

(1-2) Second haze reducing agent In the film of the present invention, the curable liquid crystal composition preferably contains a second haze reducing agent.
The second haze reducing agent is not particularly limited as long as it does not contradict the gist of the present invention.

  In the film of the present invention, the second haze reducing agent is preferably non-polymerizable.

  In the film of the present invention, the embossing rate represented by the formula (1) of the second haze reducing agent is preferably more than 50%, more preferably more than 50% and 90% or less.

  In the film of the present invention, the second haze reducing agent preferably has a perfluoroalkyl chain, and the second haze reducing agent preferably has six perfluoroalkyl chains.

  In the film of the present invention, the second haze reducing agent is preferably contained in an amount of 0.003 to 0.10% by mass, and 0.005 to 0.05% by mass, based on the polymerizable molecule in the first curable liquid crystal composition. More preferably.

The second haze reducing agent is preferably represented by the following general formula (II). Also, it can be preferably used as a liquid crystal alignment accelerator. Therefore, the composition containing the compound represented by the following general formula (II) has an advantage of being easy to use in production. Moreover, since it can be hardened | cured by superposition | polymerization, it is useful for various uses, such as an optical member.

In the general formula (II), L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently a single bond, —O—, —S—, —CO—, —COO—, —OCO. -, -COS-, -SCO-, -NRCO-, -CONR- (in the general formula (I), R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -NRCO-,- CONR- has the effect of reducing solubility, and more preferably -O-, -S-, -CO-, -COO-, -OCO-, -COS-, because the haze value tends to increase during film formation. -SCO-, and -O-, -CO-, -COO-, and -OCO- are more preferable from the viewpoint of the stability of the compound. The alkyl group that R can take may be linear or branched. As for carbon number, it is more preferable that it is 1-3, and a methyl group, an ethyl group, and n-propyl group can be illustrated.

Sp ¹ , Sp ² , Sp ³ and Sp ⁴ each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, more preferably a single bond or an alkylene group having 1 to 7 carbon atoms, and more preferably It is a single bond or an alkylene group having 1 to 4 carbon atoms. However, the hydrogen atom of the alkylene group may be substituted with a fluorine atom. The alkylene group may or may not be branched, but a linear alkylene group having no branch is preferred. From the viewpoint of synthesis, it is preferable that Sp ¹ and Sp ⁴ are the same, and Sp ² and Sp ³ are the same.

A ¹ and A ² are trivalent or tetravalent aromatic hydrocarbons. The carbon number of the trivalent or tetravalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 14, still more preferably 6 to 10, and further preferably 6. More preferred. The trivalent or tetravalent aromatic hydrocarbon group represented by A ¹ or A ² may have a substituent. Examples of such a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group, or an ester group. For the explanation and preferred ranges of these groups, the corresponding description of T below can be referred to. Examples of the substituent for the trivalent or tetravalent aromatic hydrocarbon group represented by A ¹ or A ² include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a bromine atom, a chlorine atom, and a cyano group. be able to. A molecule having a large number of perfluoroalkyl moieties in the molecule can orient the liquid crystal with a small addition amount, leading to a decrease in haze. Therefore, A ¹ and A ² are tetravalent so as to have many perfluoroalkyl groups in the molecule. It is preferable that From the viewpoint of synthesis, A ¹ and A ² are preferably the same.

で表される二価の基または二価の芳香族複素環基を表す（Ｘは炭素数１〜８のアルキル基、アルコキシ基、ハロゲン原子、シアノ基またはエステル基を表し、Ｙａ、Ｙｂ、Ｙｃ、Ｙｄはおのおの独立して水素原子または炭素数１〜４のアルキル基を表す）であり、より好ましくは

であり、さらに好ましくは

であり、よりさらに好ましくは、

である。
Ｘがとりうるアルキル基の炭素数は１〜８であり、１〜５であることが好ましく、１〜３であることがより好ましい。アルキル基は、直鎖状、分枝状、環状のいずれであってもよく、直鎖状または分枝状であることが好ましい。好ましいアルキル基として、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などを例示することができ、その中でもメチル基が好ましい。Ｘがとりうるアルコキシ基のアルキル部分については、Ｘがとりうるアルキル基の説明と好ましい範囲を参照することができる。Ｘがとりうるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子を挙げることができ、塩素原子、臭素原子が好ましい。Ｘがとりうるエステル基としては、Ｒ’ＣＯＯ−で表される基を例示することができる。Ｒ’としては炭素数１〜８のアルキル基を挙げることができる。Ｒ’がとりうるアルキル基の説明と好ましい範囲については、上記のＸがとりうるアルキル基の説明と好ましい範囲を参照することができる。エステルの具体例として、ＣＨ₃ＣＯＯ−、Ｃ₂Ｈ₅ＣＯＯ−を挙げることができる。Ｙａ、Ｙｂ、Ｙｃ、Ｙｄがとりうる炭素数１〜４のアルキル基は、直鎖状であっても分枝状であってもよい。例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などを例示することができる。
前記二価の芳香族複素環基は、５員、６員または７員の複素環を有することが好ましい。５員環または６員環がさらに好ましく、６員環が最も好ましい。複素環を構成する複素原子としては、窒素原子、酸素原子および硫黄原子が好ましい。複素環は、芳香族性複素環であることが好ましい。芳香族性複素環は、一般に不飽和複素環である。最多二重結合を有する不飽和複素環がさらに好ましい。複素環の例には、フラン環、チオフェン環、ピロール環、ピロリン環、ピロリジン環、オキサゾール環、イソオキサゾール環、チアゾール環、イソチアゾール環、イミダゾール環、イミダゾリン環、イミダゾリジン環、ピラゾール環、ピラゾリン環、ピラゾリジン環、トリアゾール環、フラザン環、テトラゾール環、ピラン環、チイン環、ピリジン環、ピペリジン環、オキサジン環、モルホリン環、チアジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペラジン環およびトリアジン環が含まれる。二価の複素環基は置換基を有していてもよい。そのような置換基の例の説明と好ましい範囲については、上記のＡ¹とＡ²の３価または４価の芳香族炭化水素が取り得る置換基に関する説明と記載を参照することができる。 T is

(X represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group, or an ester group, Ya, Yb, Yc. , Yd each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably

And more preferably

And even more preferably

It is.
Carbon number of the alkyl group which X can take is 1-8, it is preferable that it is 1-5, and it is more preferable that it is 1-3. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. Examples of preferable alkyl groups include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and among them, a methyl group is preferable. For the alkyl part of the alkoxy group that X can take, the description and preferred range of the alkyl group that X can take can be referred to. Examples of the halogen atom that X can take include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferable. Examples of the ester group that X can take include a group represented by R′COO—. Examples of R ′ include an alkyl group having 1 to 8 carbon atoms. For the description and preferred range of the alkyl group that R ′ can take, the description and preferred range of the alkyl group that X can take can be referred to. Specific examples of the ester include CH ₃ COO— and C ₂ H ₅ COO—. The alkyl group having 1 to 4 carbon atoms that can be taken by Ya, Yb, Yc, and Yd may be linear or branched. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like can be exemplified.
The divalent aromatic heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring. A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is most preferable. As the hetero atom constituting the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocycle is preferably an aromatic heterocycle. The aromatic heterocycle is generally an unsaturated heterocycle. An unsaturated heterocyclic ring having the most double bond is more preferable. Examples of heterocyclic rings include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline Ring, pyrazolidine ring, triazole ring, triazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring included. The divalent heterocyclic group may have a substituent. For the explanation and preferred ranges of examples of such substituents, reference can be made to the explanations and descriptions regarding the substituents that can be taken by the trivalent or tetravalent aromatic hydrocarbons of A ¹ and A ² .

  Hb represents a perfluoroalkyl group having 2 to 30 carbon atoms, more preferably a perfluoroalkyl group having 3 to 20 carbon atoms, and still more preferably a perfluoroalkyl group having 3 to 10 carbon atoms. The perfluoroalkyl group may be linear, branched or cyclic, but is preferably linear or branched, and more preferably linear.

m and n are each independently 2 or 3, and a plurality of parenthesized structures may be the same or different from each other, but are preferably the same. M and n in the general formula (II) are determined by the valences of A ¹ and A ² described above, and a preferable range is also determined by a preferable range of the valences of A ¹ and A ² . It is not bound by any theory that a compound in which m and n are 2 or 3 has a remarkably good haze reduction performance even if the addition amount is small as compared with a conventionally known compound and n is 1. Is presumed to be due to the fluorine content in the compound.
o and p are each independently an integer of 0 or more, and when o and p are 2 or more, a plurality of Xs may be the same or different from each other. o is preferably 1 or 2. p is preferably an integer of 1 to 4, and more preferably 1 or 2.

  The compound represented by the general formula (II) may have a symmetrical molecular structure or may have no symmetry. In addition, the symmetry here means one corresponding to any of point symmetry, line symmetry, or rotational symmetry, and asymmetry means one not corresponding to any of point symmetry, line symmetry, or rotational symmetry. .

The compound represented by the general formula (II) includes the perfluoroalkyl group (Hb), the linking group-(-Sp ¹ -L ¹ -Sp ² -L ² ) _m -A ¹ -L ³ -and -L described above. ^{4 -A 2 - (L 5 -Sp} 3 -L 6 -Sp 4 -) n -, and is preferably a compound which is a combination of T is a divalent group having the excluded volume effect. The two perfluoroalkyl groups (Hb) present in the molecule are preferably the same as each other, and the linking group present in the molecule-(-Sp ¹ -L ¹ -Sp ² -L ² ) _m -A ¹ -L ³ - and ^{-L 4 -A 2 - (L 5} -Sp 3 -L 6 -Sp 4 -) n - also is preferably identical to each other. Hb-Sp ¹ -L ¹ -Sp ² end - and -Sp ³ -L ⁶ -Sp ⁴ -Hb is preferably a group represented by any one of formulas below.
(C _a F _{2a + 1} ) − (C _b H _2b ) −
(C _a F _{2a + 1} )-(C _b H _2b ) -O- (C _r H _2r )-
(C _a F _{2a + 1} ) — (C _b H _2b ) —COO— (C _r H _2r ) —
(C _a F _{2a + 1} )-(C _b H _2b ) -OCO- (C _r H _2r )-
In the above formula, a is preferably 2 to 30, more preferably 3 to 20, and still more preferably 3 to 10. b is preferably 0 to 20, more preferably 0 to 10, and further preferably 0 to 5. a + b is 3-30. r is preferably from 1 to 10, and more preferably from 1 to 4.
In addition, Hb-Sp ¹ -L ¹ -Sp ² -L ² -and -L ⁵ -Sp ³ -L ⁶ -Sp ⁴ -Hb at the end of the general formula (II) are represented by any one of the following general formulas. It is preferred that
(C _a F _{2a + 1} ) − (C _b H _2b ) —O
(C _a F _{2a + 1} )-(C _b H _2b ) —COO—
(C _a F _{2a + 1} )-(C _b H _2b ) —O— (C _r H _2r ) —O—
(C _a F _{2a + 1} )-(C _b H _2b ) —COO— (C _r H _2r ) —COO—
(C _a F _{2a + 1} )-(C _b H _2b ) —OCO— (C _r H _2r ) —COO—
The definitions of a, b and r in the above formula are the same as the definitions immediately above.
Specific examples of the compound represented by the general formula (II) are shown below. However, the compound represented by the general formula (II) that can be employed in the present invention should not be limitedly interpreted by the following specific examples.

  The compound represented by the general formula (II) is synthesized by appropriately selecting and combining the synthesis methods described in JP-A No. 2002-129162, JP-A No. 2002-97170, and literatures cited therein. can do. Moreover, it can synthesize | combine by combining another well-known synthesis method as needed.

(2) Polymerizable liquid crystal molecule The first curable liquid crystal composition contains a polymerizable liquid crystal molecule.
As the polymerizable liquid crystalline molecule, a discotic liquid crystalline molecule or a rod-like liquid crystalline molecule is preferably used.

Discotic liquid crystalline molecules are known in various literatures (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); edited by the Chemical Society of Japan, Quarterly Chemical Review, No. 22, B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985); J. Zhang et al., J. Liquid Crystal Chemistry, Chapter 5, Chapter 10 Section 2 (1994); Am.Chem.Soc., Vol.116, page 2655 (1994)). The polymerization of discotic liquid crystalline molecules is described in JP-A-8-27284. In order to fix the discotic liquid crystalline molecules by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystalline molecules. However, when the polymerizable group is directly connected to the disc-shaped core, it becomes difficult to maintain the orientation state in the polymerization reaction. Therefore, a linking group is introduced between the discotic core and the polymerizable group. Accordingly, the discotic liquid crystalline molecule having a polymerizable group is preferably a compound represented by the following formula.
D (-LQ) _d
In the above formula, D is a discotic core; L is a divalent linking group; Q is a polymerizable group; and d is an integer of 4 to 12. Specific examples of the disk-shaped core (D) of the above formula are shown below.
In the following specific examples, LQ (or QL) means a combination of a divalent linking group (L) and a polymerizable group (Q). Among the following specific examples, triphenylene (D4) is particularly preferable.

  For details and preferred ranges of the linking group L and the polymerizable group Q, reference can be made to [0161] to [0171] of JP-A No. 2002-129162.

  Examples of the rod-like liquid crystal molecules include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used.

  The birefringence of the rod-like liquid crystal molecules is preferably 0.001 to 0.7. For specific examples of the polymerizable group, [0169] of JP-A No. 2002-129162 can be referred to. The rod-like liquid crystal molecules preferably have a molecular structure that is substantially symmetric with respect to the minor axis direction. For that purpose, it is preferable to have a polymerizable group at both ends of the rod-like molecular structure.

A compound represented by the following general formula (Ia) is also preferable as the polymerizable liquid crystal molecule.
Formula (Ia)
Z ¹ -Y ¹ -A ¹ -Y ³ -M ¹ -Y ⁴ -A ² -Y ² -Z ²
(In general formula (Ia), Z ¹ and Z ² each independently represent a polymerizable group, and A ¹ and A ² are each independently a spacer having an atomic linkage chain length of 1 to 30 (provided that the spacer is an alkylene group, Or represents a linking group in which a plurality of alkylene groups are bonded via —O— or —CO—, M ¹ represents (—T ¹ —Y ⁸ ) _n —T ² —, and n represents a natural number. And when n is 2 or more, a plurality of (-T ¹ -Y ⁸ ) may be the same or different from each other, and T ¹ and T ² are each independently a saturated or unsaturated hydrocarbon ring, Or a saturated or unsaturated heterocyclic ring (wherein the hydrocarbon ring and the heterocyclic ring may have an alkyl group or an alkoxy group), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁸ represents a single bond independently, -O -, - CO -, - O-CO -, - CO-O- or O-CO-O-represents a.)

(Z ^1, Z ²⁾
In the general formula (Ia), Z ¹ and Z ² each independently represent a polymerizable group.
As the polymerizable groups Z ^{1 to} Z ² , in connection with the crosslinking components Y ^{1 to} Y ⁸ , for example

[Wherein Y is a definition of the crosslinking components Y ^{1 to} Y ⁸ , that is, chemical single bond, oxygen, sulfur, —O—CO—, —CO—O—, —O—CO—O—, —CO -NR -, - NR-CO - , - O-CO-NR -, - NR-CO-O- or -NR-CO-NR- the stands, and R is hydrogen or C ₁ -C ₄ - alkyl, That is, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and t-butyl, and Y ′ represents a chemical single bond (hereinafter, polymerizable group Z). ^{1 to} Z ² are associated with the crosslinking components Y ^{1 to} Y ⁸ as polymerizable units and as ZY and / or ZY ′)].

  Among these polymerizable units, cyanate can spontaneously trimerize to cyanurate. The maleimide group is particularly suitable for radical copolymerization with liquid crystalline compounds of the formulas Ia and / or Ib having styryl groups as polymerizable groups.

  Compounds of formulas Ia and / or Ib having an epoxide group, oxetane group, carboxyl group, sulfonic acid group, thiirane group, aziridine group, isocyanate group and isothiocyanate group will have complementary reactive units for polymerization. Requires another compound to have. Thus, for example, suitable isocyanates can be polymerized into urethanes with alcohols and urea derivatives with amines. The same applies to the corresponding thiiranes and aziridines.

Complementary reactive units can be included in liquid crystalline compounds composed of liquid crystalline compounds similar to Formula Ia. However, instead of the groups Z ¹ -Y ^1- , Z ² -Y ^2- , these compounds contain, for example, hydroxyl, mercapto or NHR groups, wherein the last R is hydrogen or, for example, C _1- Has the meaning of C ₄ -alkyl. Furthermore, complementary reactive units can also be included in auxiliary compounds that are brought into the liquid crystalline material mixture.

In the general formula (Ia), A ¹ and A ² are each independently a spacer having an atomic linkage chain length of 1 to 30 (provided that the spacer is an alkylene group or a plurality of alkylene groups are —O— or —CO—). Represents a linking group bonded via each other.
A ¹ and A ² are preferably each independently a spacer having an atom-linked chain length of 1 to 12. A ¹ and A ² are each independently preferably a spacer having 1 to 12 carbon atoms (provided that the spacer is an unsubstituted alkylene group), and a spacer having 2 to 8 carbon atoms (provided that the spacer is unsubstituted) Are particularly preferred.
The spacers A ¹ and A ² usually have 1 to 30, preferably 1 to 12, carbon atoms and consist mainly of linear aliphatic groups. Furthermore, the carbon chain is substituted with one or more methyl, fluorine, chlorine or bromine and / or oxygen in the ether function, sulfur in the thioether function or non-adjacent imino groups or C _1- C ₄ - can be interrupted by an alkylimino group. As C ₁ -C ₄ -alkyl group, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and t-butyl correspond to the latter.

  Typical spacers are for example

[Wherein p is an integer of 1 to 30, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, and m is an integer of 1 to 14, preferably Takes 1, 2 or 3].

In the general formula (Ia), M ¹ represents (-T ¹ -Y ⁸ ) _n -T ^2- .
n represents a natural number, and when n is 2 or more, a plurality of (-T ¹ -Y ⁸ ) may be the same as or different from each other.
N represented by M ¹ in the general formula (Ia) is preferably 1 to 5, more preferably 2 to 5, particularly preferably 2 to 4, and more preferably 3 or 4. Particularly preferred is 3 and even more particularly preferred.

The groups T ¹ and T ² are, to the extent possible, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -alkoxy, C ₁ -C ₂₀ -alkoxycarbonyl, C ₁ -C ₂₀ -monoalkylaminocarbonyl, C ₁ -C ₂₀ - alkylcarbonyl, C ₁ -C ₂₀ - alkylaminocarbonyloxy, C ₁ -C ₂₀ - alkylcarbonylamino, formyl, halogen, cyano, same from the group consisting of hydroxy or nitro up to three selected Or have different substitutions. However, the substituents T ¹ and / or T ² are advantageously substituted once.

In particular, as groups T ¹ and T ² ,

Is applicable.

Particularly preferably, the mesogenic groups M ¹ and M ² are each independently of the formula

Wherein each ring Z is, independently of one another, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -alkoxy, C ₁ -C ₂₀ -alkoxycarbonyl, C ₁ -C ₂₀ -monoalkylaminocarbonyl, C ₁ -C ₂₀ - alkylcarbonyl, C ₁ -C ₂₀ - or alkylcarbonylamino, formyl, halogen, cyano, from the group consisting of hydroxy or nitro up to three selected same - alkylcarbonyloxy, C ₁ -C ₂₀ Or it can have different substituents.

  Preferred substituents for the aromatic ring Z are fluorine, chlorine, bromine, cyano, formyl, hydroxy, short-chain aliphatic groups (preferably having 1 to 4 carbon atoms, for example methyl, ethyl, n-propyl , I-propyl, n-butyl, i-butyl, t-butyl) and alkoxy groups containing these alkyl groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkylcarbonylamino groups and monoalkylaminocarbonyl groups It is.

Particularly preferred M ¹ benzene rings Z preferably have the following substitution pattern:

Alternatively, instead of Cl, F, Br, an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms, more preferably CH ₃ ), an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms, more preferably OCH ₃ ). , CHO, COCH ₃ , OCOCH ₃ or CN in the same manner, the substituents can also be present in admixture. Further structure

Are also preferred, where s takes an integer from 2 to 20, advantageously 8, 9, 10, 11, 12, 13, 14 or 15.

More particularly preferred substituents for the benzene ring Z of M ¹ are:

The compound represented by the general formula (Ia) is a compound in which at least one of the hydrocarbon ring and the heterocyclic ring represented by T ¹ and T ² or the heterocyclic ring has an alkyl group or an alkoxy group It is preferable that
Among them, the compound represented by the general formula (Ia) includes a hydrocarbon ring represented by T ¹ and T ² and one of the heterocyclic rings or the heterocyclic ring having an alkyl group or an alkoxy group. It is preferable that one hydrocarbon ring is an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms, more preferably CH ₃ ) or an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms). A compound having OCH ₃ ) is more preferable, and a compound in which one hydrocarbon ring or the heterocyclic ring has an alkyl group is particularly preferable.
In the compound represented by the general formula (Ia), when n contained in M ¹ is 3, one hydrocarbon ring at the center of the hydrocarbon ring and the heterocyclic ring or the heterocyclic ring is an alkyl group or A compound having an alkoxy group is preferred, and a more preferred range is the same as above.

(Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁸ )
In the general formula (Ia), Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁸ are each independently a single bond, —O—, —CO—, —O—CO—, —CO—O— or — O-CO-O- is represented.
Advantageously, in the compound of formula (Ia), Y ¹ to Y ⁴ and optionally Y ⁸ are each independently oxygen, —O—CO—, —CO—O— or —O—CO—O. -Represents.

Advantageously, the liquid crystalline substance mixture and preferred embodiment forms thereof are those in which the polymerizable units Z ¹ -Y ^1- , Z ² -Y ² -are selected from the group consisting of methacryloyloxy, acryloyloxy and vinyloxy. Including the compound of (Ia).

  Specific examples of the compound represented by the general formula (Ia) are shown below. However, the compound represented by the general formula (Ia) that can be employed in the present invention should not be limitedly interpreted by the following specific examples.

(3) Polymerization initiator The first curable liquid crystal composition preferably contains a polymerization initiator. For example, in an embodiment in which a curing reaction is caused to proceed by ultraviolet irradiation to form a cured film, the polymerization initiator used is preferably a photopolymerization initiator that can initiate 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 substituted aromatics. Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,221,970), acylphosphine Oxide compounds (Japanese Patent Publication No. 63-40 No. 799, JP-B-5-29234, JP-A-10-95788, JP-A-10-29997) and the like.
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 composition (solid content in the case of a coating solution).

(4) Other components In addition to the haze reducing agent, the polymerizable liquid crystal molecule, and the polymerization initiator, the first curable liquid crystal composition may include a solvent, an optically active compound containing an asymmetric carbon atom as necessary ( Chiral agent) and other additives (eg, cellulose esters).

solvent:
As the solvent for the first curable liquid crystal composition, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone, cyclohexanone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

Optically active compound (chiral agent):
The first curable liquid crystal composition preferably exhibits a cholesteric liquid crystal phase, and for that purpose, 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 first curable 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.

<Second liquid crystal layer>
The film of the present invention has at least one second liquid crystal layer laminated on the first liquid crystal layer and fixed by curing the curable liquid crystal composition in a cholesteric liquid crystal phase.
The curable liquid crystal composition that can be used for the second liquid crystal layer is the same as the first curable liquid crystal composition used for the first liquid crystal layer, and the preferred range of both is also the same.
That is, the types and composition ratios of the polymerizable liquid crystal molecules and the haze reducing agent in the curable liquid crystal composition used for the second liquid crystal film are the first liquid crystal film used for the first liquid crystal film. It is preferable that they are the same as the kind and composition ratio of the polymerizable liquid crystal molecule and the haze reducing agent in the curable liquid crystal composition.

As described above, the film of the present invention has liquid crystal films (first liquid crystal film and second liquid crystal film) formed by fixing a cholesteric liquid crystal phase.
In the present invention, the liquid crystal film formed by fixing the cholesteric liquid crystal phase is preferably a laminate of four or more layers. That is, the liquid crystal film preferably has four or more liquid crystal films formed by fixing the cholesteric liquid crystal phase. FIG. 4 shows an example of the laminated structure of the film of the present invention, wherein 1 is the film of the present invention, 15b is the first liquid crystal film, 15a, 16a and 16b are the second liquid crystal film ( Each is also referred to as an infrared reflective layer).
Each of the infrared reflection layers 15a, 15b, 16a and 16b is preferably a liquid crystal film in which a cholesteric liquid crystal phase is fixed, and light that reflects light of a specific wavelength based on the helical pitch of the cholesteric liquid crystal phase. It preferably exhibits selective reflectivity. 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. 4, 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 1200 to 1280 nm). By utilizing at least one pair of infrared reflecting layers in the range, light corresponding to the two peaks can be reflected more efficiently, and as a result, the heat shielding property can be further improved.

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

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

The aspect of the cholesteric liquid crystal layer is not limited to the above aspect. 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.
The thickness of each infrared reflective layer constituting the liquid crystal film formed by fixing the cholesteric liquid crystal phase is preferably 1 to 10 μm, and more preferably 2 to 7 μm. The total thickness of the liquid crystal film is preferably 10 to 50 μm, and more preferably 20 to 40 μm.

(Support)
The film of the present invention preferably includes a support such as a transparent plastic resin film from the viewpoint of stably forming an infrared light reflection layer which is a liquid crystal film formed by fixing the cholesteric liquid crystal phase. However, in the laminated body of this invention mentioned later and the laminated glass of this invention, the structure which the said support body does not remain may be sufficient.
Among these, in the laminated body of the present invention described later and the laminated glass of the present invention, it is preferable that no support remains in the film of the present invention. That is, in the laminated body of the present invention described later and the laminated glass of the present invention, the liquid crystal film formed by fixing the cholesteric liquid crystal phase is in contact with the first intermediate film described later, and the cholesteric liquid crystal phase is fixed. It is preferable that the liquid crystal film is in contact with a second intermediate film described later. However, the laminate of the present invention to be described later and the laminated glass of the present invention include a support and other thermoplastic resin between the liquid crystal film in which the cholesteric liquid crystal phase is fixed and the second intermediate film. In this case, the effect of the present invention can be sufficiently obtained.

The support is not particularly limited as long as it is self-supporting and supports the infrared light reflection layer. In particular, when forming an infrared reflecting layer by laminating a plurality of infrared reflecting films, including the lower infrared reflecting layer as a support, the infrared reflecting film is sequentially laminated on the lower infrared reflecting layer as a support. I can go.
In the present invention, the support is preferably plastic from the viewpoint of production on a roll-to-roll basis.
The support may be transparent or not transparent. Among these, it is preferable that the said support body is a transparent plastic resin film. However, when including the process of peeling the support, it is not necessary to be transparent. The haze of the support 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 support 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 support used in the present invention is a pressure bonding with the first and second intermediate films such as a polyvinyl butyral resin film, and when the support remains in the resin film, the expansion and contraction of the polybilyl butyral resin during laminated glass The Young's modulus is preferably about 100 to 1000 times that of polyvinyl butyral resin. By setting it as such a structure, a film | membrane crack and a wrinkle including the peripheral part of the said resin film can be suppressed, and the reflective nonuniformity of the laminated glass obtained 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.

  The material forming the support is determined depending on whether it is an optically isotropic support or an optically anisotropic support. In the case of an optically isotropic support, glass or cellulose ester is generally used. In the case of an optically anisotropic support, a synthetic polymer (eg, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate, norbornene resin) is generally used. However, optical properties may be reduced by (1) using a retardation increasing agent, (2) reducing the acetylation degree of cellulose acetate, or (3) producing a film by the cooling dissolution method described in the specification of European Patent 0911656A2. An isotropic (high retardation) cellulose ester film can also be produced. The support made of a polymer film is preferably formed by a solvent cast method.

In order to obtain an optically anisotropic support, it is preferable to perform a stretching treatment on the polymer film. When an optical uniaxial support is produced, a normal uniaxial stretching process or biaxial stretching process may be performed. When producing an optical biaxial support, it is preferable to perform an unbalanced biaxial stretching process. In unbalanced biaxial stretching, a polymer film is stretched in a certain direction (for example, 3 to 100%, preferably 5 to 30%) in a certain direction, and further in a direction perpendicular thereto (for example, 6 to 200%, preferably 10 to 90%). The bi-directional stretching process may be performed simultaneously. It is preferable that the stretching direction (the direction in which the stretching ratio is high in unbalanced biaxial stretching) and the slow axis in the plane of the stretched film are substantially the same direction. The angle between the stretching direction and the slow axis is preferably less than 10 °, more preferably less than 5 °, and most preferably less than 3 °.
The optically anisotropic support can also be used as a λ / 2 plate with a desired phase difference. In this case, the phase difference is preferably 350 nm to 700 nm, and more preferably 400 to 650 nm.

  The thickness of the support is preferably 30 μm to 200 μm, and more preferably 100 to 200 μm. By setting it as such thickness, the said infrared light reflection layer can be manufactured stably, and also when the laminated body pinched | interposed into the said glass plate contains the said support body, Film cracks and wrinkles including the peripheral portion can be suppressed, and reflection unevenness of the resulting laminated glass can be more effectively suppressed.

  In order to improve the adhesion between the support and the layer (adhesive layer, alignment film or optically anisotropic layer) provided thereon, the support is subjected to surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet light (UV)). Treatment, flame treatment). An ultraviolet absorber may be added to the support. An adhesive layer (undercoat layer) may be provided on the support. The adhesive layer is described in JP-A-7-333433. The thickness of the adhesive layer is preferably 0.1 to 2 μm, and more preferably 0.2 to 1 μm.

(Other constituent layers of the film)
Moreover, the film 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. In some cases, an alignment layer that more precisely defines the alignment direction of the liquid crystal compound is used.

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

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

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

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

Alignment layer:
The film of the present invention may have an alignment layer between the liquid crystal film and the intermediate film. However, in the method for producing a laminate of the present invention, when the support is peeled off, it is peeled off at that time. You can also
Since the alignment layer needs to be adjacent to the infrared reflective layer when forming the infrared reflective layer of the cholesteric liquid crystal phase, it is necessary to provide the alignment layer between the infrared reflective layer of the cholesteric liquid crystal phase and the substrate or undercoat layer. preferable. However, the undercoat layer may have a function of an alignment layer. Moreover, you may have an orientation layer between the infrared reflective layers.

(Characteristics of film)
The thickness of the film varies depending on the number of laminated infrared reflection layers, but is preferably 5 to 100 μm, more preferably 10 to 50 μm, and particularly preferably 20 to 40 μm.

(Use of the film of the present invention)
One embodiment of the film of the present invention is a film in which the orientation of the cholesteric liquid crystal phase (for example, horizontal orientation, vertical orientation, hybrid orientation, etc.) is fixed and exhibits optical anisotropy. The film is used as an optical compensation film such as a reflection film or a liquid crystal display device.
One embodiment of the film of the present invention is a film in which a cholesteric liquid crystal phase is fixed, and shows a selective reflection characteristic with respect to light in a predetermined wavelength range. The film exhibiting selective reflection characteristics in the infrared wavelength region (wavelength 800 to 1300 nm) is used as a heat shielding member, for example, affixed on a window glass of a building or a vehicle, or incorporated in a laminated glass.
The film of the present invention can be used for various applications such as polarizing elements, selective reflection films, color filters, antireflection films, viewing angle compensation films, holography, alignment films, which are constituent elements of optical elements. .

[Film Production Method]
The method for producing a film of the present invention comprises a step of forming a first liquid crystal layer for curing and fixing a first curable liquid crystal composition in a cholesteric liquid crystal phase, and curing on the first liquid crystal layer. Forming at least one second liquid crystal layer obtained by curing and fixing the curable liquid crystal composition in a cholesteric liquid crystal phase, and the first curable liquid crystal composition is a polymerizable liquid crystal. A first haze-reducing agent having a molecule and at least one perfluoroalkyl chain, wherein the first haze-reducing agent has a relief ratio represented by the following formula (1) of 50% or less, and a second liquid crystal The step of forming at least one layer includes a step of applying the curable liquid crystal composition at 30 to 40 m / min.
Formula (1)
Raising rate (%) = 100% × B / A
(In the formula (1), a lower layer curable liquid crystal composition containing polymerizable liquid crystal molecules and a haze reducing agent is fixed by curing in the state of a cholesteric liquid crystal phase to form a lower layer, and haze reduction is performed on the lower layer. When the upper layer is laminated by applying the upper layer curable liquid crystal composition having the same composition as the lower layer curable liquid crystal composition except for the agent, and fixing by curing in the state of the cholesteric liquid crystal phase, A is This represents the fluorine atom content relative to the total amount of carbon atoms and fluorine atoms present on the surface of the lower layer, that is, one-layer product. Represents the rate.)

The method for producing a film of the present invention includes a step of applying the curable liquid crystal composition at 20 to 40 m / min in the step of forming the second liquid crystal layer.
On the other hand, the first liquid crystal layer can be formed by forming the first curable liquid crystal composition by a method such as coating. An optically anisotropic element can also be produced by applying each curable liquid phase composition on an alignment film to form a liquid crystal layer. In addition, it is preferable that the film of this invention shows optical anisotropy.

  In the method for producing a film of the present invention, the amount of the first haze reducing agent contained in the first curable liquid crystal composition is 0 with respect to the polymerizable liquid crystal molecules contained in the curable liquid crystal composition. .10 mass% is preferable from the viewpoint of reducing the contact angle of water of the first liquid crystal film.

The polymerizable liquid crystalline molecules are preferably fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction of a polymerizable group introduced into the liquid crystalline molecule. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. A photopolymerization reaction is preferred.
It is preferable to use ultraviolet rays for light irradiation for polymerization of liquid crystalline molecules. The irradiation energy is preferably ^{20mJ / cm 2 ~50J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. The thickness of the liquid crystal layer is preferably 0.1 to 50 μm, more preferably 1 to 30 μm, and most preferably 2 to 20 μm. The coating amount of haze reduction agent represented by the general formula of the liquid crystal layer (I) is preferably 0.1 to 500 mg / m ^2, more preferably from 0.5~450mg / m ² 0.75 to 400 mg / m ² is more preferable, and 1.0 to 350 mg / m ² is most preferable.

An example of a manufacturing method is
(A) Applying a composition containing an alignment controller and a polymerizable (curable) liquid crystal compound to the surface of a support such as a transparent plastic resin film to form a cholesteric liquid crystal phase;
(B) irradiating the curable liquid crystal composition with ultraviolet rays to advance a curing reaction, fixing a cholesteric liquid crystal phase, and forming an infrared reflective layer;
Is a production method comprising at least
A liquid crystal film formed by fixing the cholesteric liquid crystal phase having the structure shown in FIG. 4 by repeating the steps (A) and (B) four times on one surface of the support (the support is not shown in FIG. 4). ) Can be produced on a support, and a liquid crystal film (infrared light reflection layer) formed by fixing a cholesteric liquid crystal phase having a further increased number of layers can be formed by repeating the process.

The undercoat layer is preferably formed on the surface of a support such as a transparent plastic resin film by coating. There is no limitation in particular about the coating method at this time, A well-known method can be used.
The alignment layer can be provided by means such as a rubbing treatment of an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound, or formation of a layer having 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. The alignment film is preferably peeled off together with the support described later.

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

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

(B) Step Next, in the step (B), the coating film in the cholesteric liquid crystal phase is irradiated with ultraviolet rays to advance the curing reaction. For ultraviolet irradiation, a light source such as an ultraviolet lamp is used. In this step, by irradiating with ultraviolet rays, the curing reaction of the curable 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 crystalline mixture in the infrared reflecting layer is no longer required to exhibit liquid crystal properties. For example, the liquid crystalline mixture may have a high molecular weight due to a curing reaction and may no longer have liquid crystallinity.

  In addition, when using the laminated body of this invention mentioned later and the laminated glass of this invention mentioned later as an infrared light reflecting plate, the other important performance is the transmittance | permeability and haze of visible light. By adjusting the selection of materials and manufacturing conditions, etc., an infrared light reflecting plate exhibiting preferable visible light transmittance and haze can be provided according to applications. For example, in an aspect used for an application having a high visible light transmittance, an infrared light reflecting plate having a visible light transmittance of 90% or more and an infrared light reflectance satisfying the above reaction can be obtained. .

[Infrared reflector]
The infrared reflecting plate of the present invention includes the film of the present invention.
The infrared reflecting plate of the present invention preferably includes a λ / 2 plate. There is no restriction | limiting in particular as said (lambda) / 2 board, It can change suitably as needed and can use a preferable thing.

The half-wave plate is obtained, for example, by stretching a film made of a transparent resin.
The transparent resin is not particularly limited as long as it has a thickness of 0.1 mm and a total light transmittance of 80% or more. Examples thereof include resins, chain polyolefin resins, polymer resins having an alicyclic structure, acrylic resins, polyvinyl alcohol resins, and polyvinyl chloride resins. Among these, a polycarbonate resin or a polymer resin having an alicyclic structure is preferable. Specifically, the alicyclic structure-containing polymer resin includes (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, and (4) vinyl fat. Examples thereof include cyclic hydrocarbon polymers and hydrogenated products thereof.

  If necessary, the resin may include an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antistatic agent, a dispersant, a chlorine scavenger, a flame retardant, a crystallization nucleating agent, an antiblocking agent, an antiblocking agent. Add known additives such as clouding agents, mold release agents, pigments, organic or inorganic fillers, neutralizing agents, lubricants, decomposition agents, metal deactivators, antifouling agents, antibacterial agents and thermoplastic elastomers be able to.

  In addition, as a half-wave plate, a liquid crystal compound applied, oriented, and fixed on a transparent resin, an inorganic crystal such as crystal or sapphire, or a structural birefringence with fine irregularities provided on a resin or glass substrate A plate can also be used.

  Instead of the glass sandwiching the infrared reflective layer, a glass substitute resin formed body or a combination of a glass substitute resin formed body and glass can be used. Examples of glass substitute resins include polycarbonate resins, acrylic resins, and methacrylic resins. It is also possible to use a glass substitute resin coated with a hard coat layer. Examples of hard coat layers include acrylic hard coat materials, silicone hard coat materials, melamine hard coat materials, and inorganic fine particles such as silica, titania, alumina, and zirconia dispersed in these hard coat materials. Things can be raised.

[Laminate]
The laminate of the present invention is formed using the infrared reflecting plate of the present invention, and has a liquid crystal film formed by fixing at least the cholesteric liquid crystal phase of the infrared reflecting plate. The laminate of the present invention preferably includes an intermediate film in at least one outermost layer from the viewpoint of facilitating laminated glass formation.

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

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

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

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

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

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

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

<The process of thermally bonding the intermediate film and the liquid crystal film of the film of the present invention>
It is preferable that the method for producing the laminate includes a step of thermally bonding the intermediate film and the liquid crystal film of the support with a liquid crystal film after lamination in the order of the support / liquid crystal film / intermediate film. The manufacturing method of the laminated body of this invention can suppress generation | occurrence | production of position shift, when peeling a support body by performing the said heat bonding before the peeling process of the support body mentioned later.
There is no restriction | limiting in particular as the method of the said heat bonding, The thermocompression bonding which presses a heating body, the heat sealing | fusion by the heating by laser irradiation, etc. are employable. Among them, in the method for producing a laminate of the present invention, it is preferable that the step of thermally bonding the liquid crystal film to the intermediate film is thermocompression bonding.
Although there is no restriction | limiting in particular as the method of the said thermocompression bonding, For example, the method of pressing a 80-140 degreeC heating body is preferable. The heating body may be a flat surface, a curved surface, or a roller. For the thermocompression bonding, a plurality of heating rollers, a heatable flat pressing surface, or the like may be used, or a combination thereof may be used. The thermocompression bonding may be performed on one surface of the support / liquid crystal film / intermediate film laminate or only on one surface. In that case, one of the rollers used for thermocompression is heated. It may be a roller or a pressing surface that is not. Among these, the method for producing a laminate of the present invention preferably uses a heating roller in the thermocompression bonding step, and more preferably uses a combination of a heating roller and a non-heating roller.

It is preferable that the manufacturing method of the said laminated body includes the process of thermally bonding at least the starting position of the peeling process of the said support body at the said thermobonding process. Here, the starting position of the support peeling step is specifically preferably within 10 mm from the end of the support, more preferably within 5 mm, and within 1.5 mm. Is particularly preferred.
By laminating the laminated body in the order of the support / liquid crystal film / intermediate film with a spot at any position, it is possible to suppress misalignment at the time of peeling of the support, but in the present invention, By laminating a specific position of the end portion of the support, the support can be peeled off more easily.

(Details of the method of thermally bonding the liquid crystal film of the intermediate film and the support with the liquid crystal film)
The liquid crystal film of the intermediate film and the support with the liquid crystal film is preferably thermocompression bonded by a thermocompression roller.
The temperature at this time is usually room temperature. When the liquid crystal film 1 and the first intermediate film 3 are adjacent to each other, for example, the temperature of the thermocompression roller can be set to 60 to 120 ° C.

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

<Step of peeling the support from the liquid crystal film>
The method for producing a laminate preferably includes a step of peeling the support from the liquid crystal film after heat bonding.
In the method for manufacturing the laminated body, it is preferable that peeling of the support is started from at least one corner of the support. Moreover, when peeling the said support body continuously using a peeling roller, it is more preferable to start peeling from the whole 1 side of the said support body.

<Step of laminating the second intermediate film>
It is preferable that the manufacturing method of the said laminated body includes the process of laminating | stacking a 2nd intermediate film on the surface by which the said support body of the said liquid crystal film was peeled after the peeling process of the said support body. That is, it is preferable that the laminated body of this invention has a 2nd intermediate film further.
The liquid crystal film 1 and the second intermediate film 3 ′ may be adjacent to each other and may include other constituent layers therebetween, but the liquid crystal film 1 and the second intermediate film 3 ′ are adjacent to each other. It is preferable. In this case, the other constituent layer includes an adhesive layer. The adhesive layer is usually provided on the second intermediate film side.
These laminates are preferably thermocompression bonded by a thermocompression roller.
The temperature at this time is usually room temperature. The temperature of the thermocompression-bonding roller can be set to 60 to 120 ° C., for example, when the liquid crystal film 1 and the second intermediate film are adjacent to each other.

  The laminate including the liquid crystal film and the intermediate film may be cut using a cutting tool, or may be cut by a laser, a water jet, or heat during processing.

[Laminated glass]
The laminated glass of the present invention has the laminate of the present invention obtained as described above and at least two glass plates, and the laminate is inserted into the two glasses. The glass plate is preferably two sheets of a first glass and a second glass.
Although the use of the laminated glass of this invention does not have a restriction | limiting in particular, It is preferable for window glass, such as a house and a motor vehicle.
A preferred embodiment at this time will be described below.
The laminated glass of the present invention can be preferably cut to an arbitrary size. In this case, the laminated glass of the present invention also suppresses cracking of the liquid crystal film including the peripheral portion. Wrinkles and cracks are difficult to spread over the entire laminated glass.

  The method of laminating the laminate of the present invention including the liquid crystal film and the intermediate film with the first glass or the second glass is not particularly limited, and is inserted between two glass plates by a known method. Can be stacked.

  The laminate sandwiched between the glass plates preferably has a configuration in which glass plates / intermediate films / films of the present invention / intermediate films / glass plates are laminated in this order.

1-3 is schematic which shows an example of the structure of the laminated glass containing the laminated body 7 clamped by the glass plate. 1 to 3, reference numeral 1 denotes a film of the present invention (a laminate of a first liquid crystal film and a second liquid crystal film formed by fixing a cholesteric liquid crystal phase), 3 denotes an intermediate film, and 3 ′ denotes a second film. , 4 represents a first glass plate, and 4 ′ represents a second glass plate. FIG. 2 shows that the laminated body 7 sandwiched between the glass plates is such that the end of the film 1 of the present invention is the end of the glass plates 4 and 4 ′, the first intermediate film 3 and the second intermediate film. It is an aspect which exists inside the edge part of 3 '. The end portions of the glass plates 4 and 4 ′ and the end portions of the first intermediate film 3 and the second intermediate film 3 ′ may be at the same position, or one of them may protrude.
In the laminate 7 sandwiched between the glass plates, as shown in FIG. 1, the end portions of the liquid crystal film formed by fixing the cholesteric liquid crystal phase are at the same positions as the end portions of the glass plate and the intermediate film. There may be. For example, when the laminate 7 sandwiched between the glass plates has a shape having four sides, the end portion of the liquid crystal film 1 formed by fixing the cholesteric liquid crystal phase as shown in FIG. It is the structure of the same position as the edge part of board 4 and 4 ', and the edge part of said 1st intermediate film 3 and 2nd intermediate film 3'.
On the other hand, as shown in FIG. 3, the end portion of the film 1 of the present invention is formed on all four sides of the end portions of the glass plates 4 and 4 ′ and the first intermediate film 3 and the second intermediate film 3 ′. The structure which protruded rather than the edge part may be sufficient.

  In the laminate sandwiched between the glass plates, the film 1 of the present invention and the first intermediate film 3, and the film 1 of the present invention and the second intermediate film 3 ′ may be adjacent to each other. You may have a structure layer. In the case where the liquid crystal film 1 formed by fixing the cholesteric liquid crystal phase includes an infrared reflecting layer described later, the manufacturing method of the laminate achieves further thinning of the laminate by adopting a step of peeling the support. can do.

  The laminate sandwiched between the glass plates is laminated in the order of glass plate / intermediate film / liquid crystal film formed by fixing cholesteric liquid crystal / λ / 2 film / liquid crystal film formed by fixing cholesteric liquid crystal / intermediate film / glass plate. A configuration may be used. At this time, it is desirable that the spiral direction of the liquid crystal film formed by fixing the cholesteric liquid crystal on both sides of the λ / 2 film is the same direction when the reflection center wavelength is the same.

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

The curved glass plate is obtained by bending soda-lime glass heated to a temperature equal to or higher than the softening point by a float method, and the use of a three-dimensional curved glass plate is simple.
The three-dimensionally curved glass plate is a glass plate having a different radius of curvature depending on the location, such as a spherical surface, an elliptical spherical surface, or a front glass of an automobile.
The curvature radius of the curved glass plate is not particularly limited, but is preferably 0.9 m to 3 m. If the radius of curvature is smaller than 0.9 m, the resin film is likely to be wrinkled in general, but the above manufacturing method suppresses the generation of wrinkles in the resin film even if the radius of curvature is less than 0.9 m. can do. Further, when the radius of curvature is large, the shape is close to a flat surface, and in general, the resin film is less likely to be wrinkled, but cracking may occur in the peripheral portion of the resin film. Therefore, in the above manufacturing method, the radius of curvature of the curved glass may be 3 m or more, but from the viewpoint of suppressing the generation of wrinkles in addition to the occurrence of cracks, the radius of curvature of the curved glass is 3 m. In particular, it can be preferably used.
Moreover, although the laminated glass obtained by the above-mentioned manufacturing method contains the said glass plate at least 2 sheets, even if it is a case where the curvature of each glass plate differs, the above-mentioned manufacturing method can be used.

<Step of crimping while heating the laminate sandwiched between the glass plates>
It is preferable that the manufacturing method of the above-mentioned laminated glass includes the process of crimping | bonding, heating the laminated body of this invention pinched | interposed into the said glass plate.
The lamination of the laminate of the present invention sandwiched between the glass plates and the glass plate is performed, for example, by pre-pressing at a temperature of 80 to 120 ° C. for 30 to 60 minutes under reduced pressure with a vacuum bag or the like, and then in an autoclave. And laminated at a temperature of 120 to 150 ° C. under a pressure of 1.0 to 1.5 MPa, and a laminated glass in which a laminate is sandwiched between two glasses can be obtained. Moreover, you may bond together using an adhesive material etc.
At this time, it is preferable that the time of thermocompression bonding at a temperature of 120 to 150 ° C. under a pressure of 1.0 to 1.5 MPa is 20 to 90 minutes.
After the thermocompression bonding, there is no particular limitation on the method of cooling, and the laminated glass body may be obtained by cooling while releasing the pressure as appropriate. In the present invention, it is preferable to lower the temperature while maintaining the pressure after completion of the thermocompression bonding from the viewpoint of further improving the wrinkles and cracks of the obtained laminated glass body. Here, when the temperature is lowered while maintaining the pressure, the pressure inside the apparatus at the time of thermocompression bonding (preferably 130 ° C.) is such that the pressure inside the apparatus at 40 ° C. becomes 75% to 100% at the time of thermocompression bonding. It means to cool down. The method of lowering the temperature while maintaining the pressure is not particularly limited as long as the pressure when the temperature is lowered to 40 ° C. is within the above range, but the pressure inside the pressure device naturally decreases as the temperature decreases. In addition, a mode in which the temperature is lowered without leaking pressure from the inside of the apparatus or a mode in which the temperature is lowered while further pressurizing from the outside so that the internal pressure of the apparatus does not decrease as the temperature decreases is preferable. In the case where the temperature is lowered while maintaining the pressure, it is preferable to cool to 120 ° C. to 150 ° C. and then cool to 40 ° C. over 1 to 5 hours.
In the present invention, it is preferable to include a step of releasing the pressure after the temperature is lowered while the pressure is maintained. Specifically, it is preferable to lower the temperature by releasing the pressure after the temperature in the autoclave becomes 40 ° C. or lower after the temperature is lowered while the pressure is maintained.
As mentioned above, the laminated glass of this invention is the thermocompression bonding at the temperature of 120-150 degreeC under the process of clamping the laminated body of this invention between at least 2 glass plates, and a 1.0-1.5 MPa pressurization after that. It is preferable to include a step of reducing the temperature while maintaining the pressure, and a step of releasing the pressure.

  The range in which the glass plate and the laminate of the present invention are thermocompression-bonded may be a range over the entire area of the glass plate, but it may be only the peripheral portion of the glass plate. It can also be suppressed.

  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.

[Examples 1-6 and Comparative Examples 1-9]
<Preparation of first curable liquid crystal composition (R1) for first liquid crystal film>
The following compound A, compound B, fluorine-based horizontal alignment agent, chiral agent, polymerization initiator, and solvent methyl ethyl ketone were mixed to prepare a coating solution having the following composition. The obtained coating liquid was made into the cholesteric liquid crystalline mixture (R1) of each Example and a comparative example.
・ 100 parts by mass of the following polymerizable liquid crystal molecule A ・ Haze reducing agent described in Table 1 below ・ Amount described in Table 1 below ・ 5.0 parts by mass of the following chiral agent (A) ・ Polymerization initiator IRGACURE 819 (Ciba Japan) 3 parts by mass / solvent (methyl ethyl ketone) The amount that the solute concentration is 25% by mass

<Manufacture of film>
(Preparation of curable liquid crystal composition for second liquid crystal film)
Further, the curing for the second liquid crystal film is similarly performed except that the chiral agent (A) of the coating liquid (R1) containing the polymerizable liquid crystal is changed to 3.0 parts by mass of LC-756 (manufactured by BASF). The coating liquid (L1) which is a crystalline liquid crystal composition was prepared.

  A coating solution (R2) was prepared in the same manner except that the amount of the chiral agent (A) in the coating solution (R1) containing the polymerizable liquid crystal was changed to 4.0 parts by mass.

  A coating liquid (L2) was prepared in the same manner except that the amount of the chiral agent LC-756 in the coating liquid (L1) containing a polymerizable liquid crystal was changed to 2.4 parts by mass.

(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

(Coating, drying and film formation)
On the surface of a PET film (no undercoat layer, manufactured by FUJIFILM Corporation, thickness: 50 μm, size 320 mm × 400 mm), the undercoat layer coating solution (S1) is dried using a wire bar. Was applied to a thickness of 0.25 μm. Then, it heated at 150 degreeC for 10 minute (s), dried and solidified, and formed the undercoat.
Next, the alignment layer coating liquid (H1) was applied onto the formed undercoat layer at a coating speed of 25 m / min 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 cholesteric liquid crystal phase that is the infrared reflective layer is fixed. A fixed liquid crystal film was produced.
(1) Each coating solution was coated on the PET film at a coating speed of 25 m / min 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 is 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. to fix the cholesteric liquid crystal phase and to fix the cholesteric liquid crystal phase. A liquid crystal film (infrared reflective layer) was prepared.
(3) After cooling to room temperature, the above steps (1) and (2) are repeated, and a film of each example and comparative example in which a liquid crystal film of a cholesteric liquid crystal phase laminated in four layers is formed on PET is produced. did.
The coating liquid was applied in the order of (R1), (R2), (L1), and (L2).

<Evaluation>
The raising ratio of the haze reducing agent used in each example and comparative example, the haze and water contact angles of the first liquid crystal film (R1) produced in each example and comparative example, and the first example in each example and comparative example. The suitability for high-speed lamination coating when the liquid crystal film (R2) 2 was applied was evaluated by the following method. The obtained evaluation results are shown in Table 1 below.

(Raising ratio of haze reducing agent)
In the production of the film of each example and comparative example, the same as the first curable liquid crystal composition, except that 0.03 parts by mass of a haze reducing agent was added to 100 parts by mass of the polymerizable liquid crystal molecule A. Thus, a lower layer coating solution was prepared.
Moreover, the upper layer curable liquid crystal composition having the same composition as the first curable liquid crystal composition was prepared except that the haze reducing agent was removed.
A lower liquid crystal layer was formed in the same manner except that the obtained lower layer coating solution was used instead of the first curable liquid crystal composition. On the lower liquid crystal layer, the upper layer curable liquid crystal composition was applied and fixed in the state of a cholesteric liquid crystal phase in the same manner as the lower layer, and the upper layer was laminated.
The fluorine atom content rate existing on the surface of the lower layer and the fluorine atom content rate existing on the surface of the upper layer were measured under the following conditions using X-ray photoelectron spectroscopy.
From the measured results, the fluorine atom content A with respect to the total amount of carbon atoms and fluorine atoms present on the surface of the first liquid crystal layer, and the fluorine atom content with respect to the total amount of carbon atoms and fluorine atoms present on the surface of the upper layer Using B, the relief ratio was determined according to the following formula (1).
Formula (1)
Raising rate (%) = 100% × B / A

(Water contact angle of the first liquid crystal film)
In the production of the film of each example and comparative example, the contact angle when 2 μL of water was dropped on the sample coated only with the coating solution (R1) was measured by a contact angle meter DM700 manufactured by Kyowa Interface Science Co., Ltd. The measured results were evaluated according to the following criteria.
◎ Less than 100 ° ○ More than 100 °, less than 115 ° × 115 ° or more

(Haze of film)
In the production of the film of each Example and Comparative Example, a sample coated only with the coating liquid (R1) was produced.
The haze of the film was measured using a haze meter NDH2000 manufactured by Nippon Denka Co., Ltd. The measured results were evaluated according to the following criteria.
○ Less than 0.4% × 0.4% or more

(Applicability for high-speed lamination coating)
In the production of the film of each example and comparative example, the high-speed lamination application suitability when the second liquid crystal film (R2) was applied was evaluated according to the following criteria.
○ Visually confirm that the upper layer liquid can be applied at a speed of 25 m / min or more.
× Visually confirm that it cannot be applied at a speed of 25m / min.

As shown in Table 1 above, from each Example , it was found that the film of the present invention has a low water contact angle of the first liquid crystal film and is excellent in haze and high-speed laminate coating suitability.
On the other hand, from Comparative Examples 1 to 9, when using a haze reducing agent whose relief ratio is outside the scope of the present invention , the obtained film has a high water contact angle of the first liquid crystal film, and has high-speed lamination coating suitability. I knew it was n’t there.

[Example 11]
<Manufacture of laminated glass>
(surface treatment)
The surface of the liquid crystal film of the film of each Example and Comparative Example obtained was washed according to the following procedure.
The laminate formed as described above was immersed in a container containing 2-butanone, and washed at 40 ° C. for 10 minutes.

<Manufacture of laminated body (laminated intermediate curtain)>
The periphery was cut off so that the end faces of the films of Examples and Comparative Examples including the liquid crystal film formed on the PET were in the vertical direction. On the other hand, the periphery of a PVB film having both surfaces embossed as an intermediate film was cut off so that the end face was in the vertical direction. A laminate was obtained by overlaying PVB as an intermediate film on the liquid crystal film of the film of each Example and Comparative Example. A position of 1 mm or less from the end of the support 5 with the liquid crystal film on the entire circumference (4 sides) is sandwiched between two laminating heating rollers arranged on the front side and the back side of the obtained laminate, and the liquid crystal film The interlayer film was bonded by thermocompression bonding. At this time, the laminating heating roller does not crush the embossing on the back surface of the intermediate film, the laminating roller on the intermediate film side is set to 25 ° C. The heating roller for laminating on the support 2 (PET) side was set to 120 ° C. so as to improve the adhesion of the liquid crystal film 1.
Thereafter, PVB as the second intermediate film was laminated.

<Laminated glass>
The resulting laminate was laminated to be a glass / intermediate film / liquid crystal film formed by fixing a cholesteric liquid crystal phase / second intermediate film / glass, and a laminate was produced that was sandwiched between glass plates. Here, the edge part of the said glass plate and the edge part of the said intermediate film were the same positions.
The glass plate having a thickness of 2 mm was used. The radius of curvature of the curved glass plate was between 0.9 m and 3.0 m.
The laminate sandwiched between the obtained glass plates was pre-pressed under vacuum at 95 ° C. for 30 minutes. After the pre-bonding, the laminate sandwiched between the glass plates was pressure-bonded while being heated in an autoclave under the conditions of 1.3 MPa and 120 ° C. to produce a laminated glass. In this way, each of the examples and comparative examples in which the laminated body in which the upper and lower sides of the infrared reflective layer (liquid crystal film 1) of the four layers of cholesteric liquid crystal phases are sandwiched between the two intermediate films 3 and 3 ′ is inserted is combined. Glass was obtained.

  In Example 1 and 2, when the performance of the produced laminated glass was evaluated, it confirmed that it worked as a favorable thermal insulation glass without a remarkable defect and a stripe.

[Example 12]
In the production of the films of Examples 1 and 2, only the coating liquids (R1) and (R2) were applied, and a glass / intermediate film / cholesteric liquid crystal was fixed at the time of laminated glass production / liquid crystal film / λ / 2 plate / Samples were produced in which only the second cholesteric liquid crystal was fixed to form a laminated body sandwiched between a glass plate and a liquid crystal film formed by fixing a second cholesteric liquid crystal / second intermediate film / glass.
When the performance of the produced laminated glass was evaluated, it was confirmed that it worked as a good heat-shielding glass free from significant defects and streaks.

1 Film of the present invention (a liquid crystal film in which a cholesteric liquid crystal phase is fixed, and may contain a support)
3 Intermediate film 3 ′ Second intermediate film 4, 4 ′ Glass plate 6 Laminated glass 15b First liquid crystal film (infrared reflective layer formed by fixing a cholesteric liquid crystal phase)
15a Second liquid crystal film (infrared reflective layer formed by fixing a cholesteric liquid crystal phase)
16a Second liquid crystal film (infrared reflective layer formed by fixing a cholesteric liquid crystal phase)
16b Second liquid crystal film (infrared reflective layer formed by fixing a cholesteric liquid crystal phase)

Claims (21)

Forming a first liquid crystal layer for curing and fixing the first curable liquid crystal composition in a cholesteric liquid crystal phase;
Forming a curable liquid crystal composition on the first liquid crystal layer in a cholesteric liquid crystal phase and fixing it to form at least one second liquid crystal layer,
The first curable liquid crystal composition comprises polymerizable liquid crystal molecules and a first haze reducing agent having at least one perfluoroalkyl chain;
The embossing rate represented by the following formula (1) of the first haze reducing agent is 50% or less,
The first haze reducing agent is contained in an amount of 0.03% by mass or more based on the polymerizable molecule in the first curable liquid crystal composition,
The step of forming at least one second liquid crystal layer includes a step of applying the curable liquid crystal composition at 20 to 40 m / min,
The first liquid crystal layer and the second liquid crystal layer are infrared reflection layers that selectively reflect left circularly polarized light or right circularly polarized light, and the circularly polarized light reflected by the first liquid crystal layer and the second liquid crystal layer The method for producing a film is characterized in that the direction of circularly polarized light reflected from the film is opposite.
Formula (1)
Raising rate (%) = 100% × B / A
(In the formula (1), the lower layer curable liquid crystal composition containing the polymerizable liquid crystal molecules and the haze reducing agent for measuring the embossing rate is fixed by curing in the state of the cholesteric liquid crystal phase to form the lower layer, A curable liquid crystal composition for the upper layer having the same composition as the lower layer curable liquid crystal composition is applied to the lower layer except that the haze reducing agent for measuring the embossing rate is removed, and cured in the state of a cholesteric liquid crystal phase. When the upper layer is laminated by fixing, A represents the fluorine atom content with respect to the total amount of carbon atoms and fluorine atoms present on the surface of the lower layer, that is, the one-layer product, and B represents the surface of the upper layer, that is, the two-layer product. (Represents the fluorine atom content relative to the total amount of carbon atoms and fluorine atoms present.) The amount of the first haze reducing agent contained in the first curable liquid crystal composition is 0.10% by mass or more based on the polymerizable liquid crystal molecules contained in the curable liquid crystal composition. The method for producing a film according to claim 1 . The method for producing a film according to claim 1 or 2 , wherein the first haze reducing agent is non-polymerizable. The method for producing a film according to any one of claims 1 to 3, wherein the first haze-reducing agent has at least two perfluoroalkyl chains. The method for producing a film according to any one of claims 1 to 4 , wherein the first haze reducing agent has two perfluoroalkyl chains. The said 1st haze reducing agent is contained 0.1 mass% or more with respect to the said polymeric molecule in a said 1st curable liquid crystal composition, The any one of Claims 1-5 characterized by the above-mentioned. A method for producing the film according to 1 . The first curable liquid crystal composition, film manufacturing method according to any one of claims 1 to 6, characterized in that it comprises a second haze lowering agent. The method for producing a film according to claim 7 , wherein the second haze reducing agent is non-polymerizable. Method of producing a film according to claim 7 or 8 relief rate represented by the formula of the second haze reducing agent (1) is equal to or greater than 50%. The method for producing a film according to any one of claims 7 to 9 , wherein the second haze-reducing agent has a perfluoroalkyl chain. The method for producing a film according to any one of claims 7 to 10 , wherein the second haze-reducing agent has six perfluoroalkyl chains. Any second haze lowering agent of claim 7 to 11, characterized in that contained 0.003-0.10 wt% relative to the polymerizable molecules of said first curable liquid crystal composition The method for producing a film according to claim 1. Wherein the curable liquid crystal composition used in the second liquid crystal film, a film manufacturing method according to any one of claims 1 to 12, characterized in that it comprises a haze reducing agent. Method of producing a film according to any one of claims 1 to 13, characterized in that show selective reflection characteristic infrared wavelength range. Production method of the infrared reflecting plate, which comprises a method of producing a film according to any one of claims 1-14. The method for manufacturing an infrared reflecting plate according to claim 15 , comprising a λ / 2 plate. The method for producing an infrared reflecting plate according to claim 15 or 16 , wherein the outermost layer has an easy adhesion layer. Forming an infrared reflector using the manufacturing method of the infrared reflecting plate according to any one of claims 15-17,
A method for producing a laminate, comprising a step of laminating an intermediate film on at least one of the first liquid crystal film and the second liquid crystal film of the film . And laminates prepared using the method for manufacturing a laminated body according to claim 18, a method for producing a laminated glass which have at least two glass plates,
Method for producing a laminated glass, which comprises inserting the laminate during said two glass. Method for manufacturing a windscreen vehicle including a method of manufacturing a laminated glass according to claim 19. Method of manufacturing a glass for a building material comprising a method for producing a laminated glass according to claim 19.

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