TW202214620A - Two-component polymerizable liquid crystal composition - Google Patents

Abstract

Provided are a polymerizable liquid crystal composition whereby a liquid crystal cured film having excellent optical performance even after prolonged storage can be obtained, a method for storing the composition, a method for manufacturing the composition, and a method for manufacturing a liquid crystal cured film. A two-component polymerizable liquid crystal composition configured from an agent A that contains a solvent and a reactive additive having a polymerizable group and an active-hydrogen-reactive group in each molecule thereof, and an agent B that contains a solvent and a polymerizable liquid crystal compound, the value of Ra in formula (1) satisfying the expression Ra > 37.0 in the solvent overall in agent A. Formula (1): Ra=\{4*([delta]D(W)-[delta]D(S))2+([delta]P(W)-[delta]P(S))2+([delta]H(W)-[delta]H(S))2\}0.5. [In formula (1), [delta]D(W) represents the dispersion term in the Hansen solubility parameters for water, [delta]D(S) represents the dispersion term in the Hansen solubility parameters for the solvent overall based on a weighted average for the solvent, [delta]P(W) represents the polarity term in the Hansen solubility parameters for water, [delta]P(S) represents the polarity term in the Hansen solubility parameters for the solvent overall based on a weighted average for the solvent, [delta]H(W) represents the hydrogen bonding term in the Hansen solubility parameters for water, and [delta]H(S) represents the hydrogen bonding term in the Hansen solubility parameters for the solvent overall based on a weighted average for the solvent.].

Description

Two-component polymerizable liquid crystal composition

The present invention relates to a two-component type polymerizable liquid crystal composition, a storage method thereof, a method for producing the polymerizable liquid crystal composition, and a method for producing a liquid crystal cured film.

In recent years, with the thinning of image display devices, optical films such as polarizing plates and retardation plates using polarizing films are being developed. The liquid crystal hardening layer obtained by hardening it in an aligned state. In the manufacture of such an optical film, the polymerizable liquid crystal compound is usually a polymerizable liquid crystal composition obtained by dissolving the polymerizable liquid crystal compound in a solvent etc. In the form of coating on the substrate or alignment film. It is known that in the case of producing an optical film by applying the composition on a substrate or an alignment film, if the adhesiveness between the substrate or alignment film and the obtained optical film is higher, the processing will not work. Since peeling etc. arise, it is easy to obtain a high-quality optical film, and it is preferable, and the composition which has the characteristic of providing the optical film with high adhesiveness is proposed (patent document 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 6019591

[Problems to be Solved by Invention]

However, when this composition is stored for a long time and is formed into a liquid crystal cured film, there is a problem in that an alignment defect is generated and a favorable alignment cannot be obtained. Therefore, the objective of this invention is to provide the polymerizable liquid crystal composition which can obtain the liquid crystal cured film which has favorable optical performance after long-term storage, its storage method, the manufacturing method of this composition, and the manufacturing method of a liquid crystal cured film. [Technical means to solve problems]

[式中，δ _D(W)表示水之漢森溶解度參數之分散項，δ _D(S)表示基於溶劑之加權平均之溶劑整體之漢森溶解度參數之分散項，δ _P(W)表示水之漢森溶解度參數之極性項，δ _P(S)表示基於溶劑之加權平均之溶劑整體之漢森溶解度參數之極性項，δ _H(W)表示水之漢森溶解度參數之氫鍵項，δ _H(S)表示基於溶劑之加權平均之溶劑整體之漢森溶解度參數之氫鍵項] 所表示之Ra之值滿足Ra＞37.0。 [2]如[1]之二液型聚合性液晶組合物，其中上述B劑中之溶劑之由上述式(1)所表示之Ra之值滿足Ra≦37.0。 [3]如[1]或[2]之二液型聚合性液晶組合物，其中上述A劑中所包含之上述反應性添加劑之量相對於上述聚合性液晶化合物100質量份為0.5質量份以上且10質量份以下。 [4]如[1]至[3]中任一項之二液型聚合性液晶組合物之保管方法，其將上述A劑及B劑分開保管。 [5]如[4]之保管方法，其將上述A劑保管於塑膠製容器或金屬製容器中。 [6]如[4]或[5]之保管方法，其將上述A劑保管於乾燥惰性氣體氛圍下。 [7]一種聚合性液晶組合物之製造方法，其包括將構成如[1]至[3]中任一項之二液型聚合性液晶組合物之上述A劑與B劑進行混合之步驟。 [8]一種液晶硬化膜之製造方法，其包括： 於基材上形成配向膜之步驟； 將構成如[1]至[3]中任一項之二液型聚合性液晶組合物之上述A劑與B劑進行混合而獲得聚合性液晶組合物之步驟； 於上述配向膜上塗佈上述混合後之聚合性液晶組合物而獲得塗膜之步驟；及 使上述塗膜硬化之步驟。 [發明之效果] The present inventors have completed the present invention as a result of repeated detailed studies in order to solve the above-mentioned problems. That is, the present invention includes the following preferred aspects. [1] A two-component type polymerizable liquid crystal composition comprising agent A and agent B, agent A including a reactive additive having a polymerizable group and an active hydrogen reactive group in the molecule and a solvent, agent B including a polymerizable liquid crystal compound and solvent, and the solvent in the above-mentioned A agent is given by the following formula (1) [Equation 1]

[In the formula, δ _D(W) represents the dispersion term of the Hansen solubility parameter of water, δ _D(S) represents the dispersion term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent, and δ _P(W) represents the water The polar term of the Hansen solubility parameter, δ _P(S) represents the polar term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent, δ _H(W) represents the hydrogen bond term of the Hansen solubility parameter of water, δ _H(S) represents the hydrogen bond term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent] The value of Ra represented by Ra satisfies Ra>37.0. [2] The two-component polymerizable liquid crystal composition according to [1], wherein the value of Ra represented by the above formula (1) of the solvent in the above-mentioned B agent satisfies Ra≦37.0. [3] The two-component polymerizable liquid crystal composition according to [1] or [2], wherein the amount of the reactive additive contained in the agent A is 0.5 parts by mass or more relative to 100 parts by mass of the polymerizable liquid crystal compound and 10 parts by mass or less. [4] The storage method of the two-component polymerizable liquid crystal composition according to any one of [1] to [3], wherein the A agent and the B agent are separately stored. [5] The storage method according to [4], wherein the agent A is stored in a plastic container or a metal container. [6] The storage method according to [4] or [5], wherein the agent A is stored in a dry inert gas atmosphere. [7] A method for producing a polymerizable liquid crystal composition, comprising the step of mixing the above-mentioned agent A and agent B constituting the two-component type polymerizable liquid crystal composition according to any one of [1] to [3]. [8] A method for producing a liquid crystal cured film, comprising: forming an alignment film on a base material; The step of mixing the agent and the agent B to obtain a polymerizable liquid crystal composition; the step of coating the mixed polymerizable liquid crystal composition on the above-mentioned alignment film to obtain a coating film; and the step of curing the above-mentioned coating film. [Effect of invention]

ADVANTAGE OF THE INVENTION According to this invention, the polymeric liquid crystal composition which can obtain the liquid crystal cured film which has favorable optical performance after long-term storage, its storage method, the manufacturing method of this composition, and the manufacturing method of a liquid crystal cured film can be provided. Furthermore, the adhesiveness of the liquid crystal cured film obtained from the polymerizable liquid crystal composition of this invention is high, and it has an excellent external appearance.

Hereinafter, embodiments of the present invention will be described in detail. In addition, the scope of the present invention is not limited to the embodiment to be described here, and various modifications can be made without departing from the gist of the present invention.

[式中，δ _D(W)表示水之漢森溶解度參數之分散項，δ _D(S)表示基於溶劑之加權平均之溶劑整體之漢森溶解度參數之分散項，δ _P(W)表示水之漢森溶解度參數之極性項，δ _P(S)表示基於溶劑之加權平均之溶劑整體之漢森溶解度參數之極性項，δ _H(W)表示水之漢森溶解度參數之氫鍵項，δ _H(S)表示基於溶劑之加權平均之溶劑整體之漢森溶解度參數之氫鍵項] 所表示之Ra之值滿足Ra＞37.0。 The two-component polymerizable liquid crystal composition of the present invention contains agent A and agent B, agent A includes a reactive additive having a polymerizable group and an active hydrogen reactive group in the molecule and a solvent, agent B includes a polymerizable liquid crystal compound and a solvent, And the solvent in the above-mentioned A agent is given by the following formula (1) [Equation 2]

[In the formula, δ _D(W) represents the dispersion term of the Hansen solubility parameter of water, δ _D(S) represents the dispersion term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent, and δ _P(W) represents the water The polar term of the Hansen solubility parameter, δ _P(S) represents the polar term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent, δ _H(W) represents the hydrogen bond term of the Hansen solubility parameter of water, δ _H(S) represents the hydrogen bond term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent] The value of Ra represented by Ra satisfies Ra>37.0.

The two-component type polymerizable liquid crystal composition of the present invention contains a reactive additive, a polymerizable liquid crystal compound, and a solvent for dissolving them as essential components, and the reactive additive and the polymerizable liquid crystal compound are separately prepared in agents A and B, respectively. in the agent.

＜Agents＞ [Reactive Additives] A reactive additive generally means what is added to a polymerizable liquid crystal composition in order to improve the adhesiveness of a liquid crystal cured film. The so-called polymerizable group of the reactive additive contained in the A agent means a group that participates in the polymerization reaction. The polymerizable group may be, for example, a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, and specifically, a vinyl group, a (meth)acrylic group, a vinyloxy group, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloyloxy, oxiranyl, oxetanyl and the like.

The so-called active hydrogen reactive group contained in the reactive additive contained in agent A refers to the reactive group having active hydrogen such as carboxyl group (-COOH), hydroxyl group (-OH), amine group (-NH ₂ ), etc. group, representative examples are epoxy group, glycidyl group, oxazolyl group, carbodiimide group, aziridine group, imide group, isocyanato group, thioisocyanato group, maleic Diacid anhydride group, alkoxysilyl group, etc. In the reactive additive, preferably at least two active hydrogen reactive groups are present, and in this case, the plurality of active hydrogen reactive groups present may be the same or different.

The number of polymerizable groups and active hydrogen reactive groups possessed by the reactive additive is usually 1 to 20, and preferably 1 to 10, respectively.

In a preferred embodiment, the reactive additive preferably contains vinyl and/or (meth)acrylic groups as polymerizable groups, preferably contains epoxy groups, glycidyl groups, isocyanato groups and at least one group in the group consisting of an alkoxysilyl group as an active hydrogen reactive group, more preferably a reactive additive with an acrylic group and an isocyanate group or a reaction with an acrylic group and an alkoxysilyl group Sexual additives.

Specific examples of the reactive additives include compounds having (meth)acrylic acid groups and epoxy groups, such as methacryloyloxy glycidyl ether and acryloxy glycidyl ether; oxetane acrylic acid Compounds with (meth)acrylic group and oxetanyl group such as ester or oxetane methacrylate; compounds with (meth)acrylic group and lactone such as lactone acrylate or lactone methacrylate compounds with vinyl groups and oxazoline groups such as vinyloxazoline or isopropenyloxazoline; isocyanatomethyl acrylate, isocyanatomethyl methacrylate, 2-isocyanato acrylic acid Compounds with (meth)acrylic acid group and isocyanato group, such as acid ethyl ester and 2-isocyanatoethyl methacrylate; 3-acryloyloxypropyltrimethoxysilane, 3-methacrylic acid An oligomer of a compound having a (meth)acrylic group and an alkoxysilyl group, such as oxypropylmethyldimethoxysilane, etc. Moreover, the compound etc. which have a vinyl group, a vinyl group, and an acid anhydride, such as methacrylic anhydride, an acrylic anhydride, maleic anhydride, and vinyl maleic anhydride, are mentioned. Among them, preferred are methacryloyloxy glycidyl ether, acryloxy glycidyl ether, isocyanatomethyl acrylate, isocyanatomethyl methacrylate, vinyloxazoline, acrylic acid 2- Isocyanatoethyl ester, 2-isocyanatoethyl methacrylate, 3-acryloyloxypropyltrimethoxysilane and oligomers of the above, especially isocyanatomethyl acrylate, acrylic acid 2-Isocyanatoethyl ester, 3-propenyloxypropyltrimethoxysilane and oligomers above.

The reactive additive may be used as it is, or after being purified as necessary. Examples of commercially available products include Laromer (registered trademark) PR9000 (manufactured by BASF Corporation), Karenz AOI (registered trademark) (manufactured by Showa Denko Co., Ltd.), KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like .

The amount of the reactive additive contained in the agent A is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, more preferably 1.5 part by mass or more, more preferably 1.5 part by mass or more, with respect to 100 parts by mass of the polymerizable liquid crystal compound described below. It is more preferably 2 parts by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, and still more preferably 4 parts by mass or less. When the quantity of the said reactive additive is more than the said lower limit and below the upper limit, it becomes easy to improve adhesiveness, without impairing the orientation of the liquid crystal cured film manufactured from the two-component polymerizable liquid crystal composition of this invention. The reactive additives may be used alone or in combination of two or more. When using 2 or more types of reactive additives, the quantity of the said reactive additive shows the total amount.

[式中，δ _D(W)表示水之漢森溶解度參數之分散項，δ _D(S)表示基於溶劑之加權平均之溶劑整體之漢森溶解度參數之分散項，δ _P(W)表示水之漢森溶解度參數之極性項，δ _P(S)表示基於溶劑之加權平均之溶劑整體之漢森溶解度參數之極性項，δ _H(W)表示水之漢森溶解度參數之氫鍵項，δ _H(S)表示基於溶劑之加權平均之溶劑整體之漢森溶解度參數之氫鍵項] 基於溶劑之加權平均之溶劑整體之漢森溶解度參數之分散項可根據A劑中所包含之各溶劑之漢森溶解度參數之分散項及各溶劑之體積分率並根據以下式(1-1)而求出。 [數4]

[式(1-1)中，δ _D(S1)表示A劑中所包含之溶劑1之漢森溶解度參數之分散項，c _S1表示A劑中所包含之溶劑1之體積分率，δ _D(S2)表示A劑中所包含之溶劑2之漢森溶解度參數之分散項，c _S2表示A劑中所包含之溶劑2之體積分率] [Solvent] The value of Ra represented by the following formula (1) of the solvent contained in agent A satisfies Ra>37.0. [Number 3]

[In the formula, δ _D(W) represents the dispersion term of the Hansen solubility parameter of water, δ _D(S) represents the dispersion term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent, and δ _P(W) represents the water The polar term of the Hansen solubility parameter, δ _P(S) represents the polar term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent, δ _H(W) represents the hydrogen bond term of the Hansen solubility parameter of water, δ _H(S) represents the hydrogen bond term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent] The dispersion term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent can be determined according to the The dispersion term of the Hansen solubility parameter and the volume fraction of each solvent were obtained according to the following formula (1-1). [Number 4]

[In formula (1-1), δ _D(S1) represents the dispersion term of the Hansen solubility parameter of the solvent 1 contained in the A agent, c _S1 represents the volume fraction of the solvent 1 contained in the A agent, δ _{D (S2)} represents the dispersion term of the Hansen solubility parameter of the solvent 2 contained in the A agent, c _S2 represents the volume fraction of the solvent 2 contained in the A agent]

[式(1-2)中，δ _P(S1)表示A劑中所包含之溶劑1之漢森溶解度參數之極性項，c _S1表示A劑中所包含之溶劑1之體積分率，δ _P(S2)表示A劑中所包含之溶劑2之漢森溶解度參數之極性項，c _S2表示A劑中所包含之溶劑2之體積分率] [數6]

[式(1-3)中，δ _H(S1)表示A劑中所包含之溶劑1之漢森溶解度參數之氫鍵項，c _S1表示A劑中所包含之溶劑1之體積分率，δ _H(S2)表示A劑中所包含之溶劑2之漢森溶解度參數之氫鍵項，c _S2表示A劑中所包含之溶劑2之體積分率] 各溶劑之δ _D、δ _P及δ _H例如可使用書籍：「Hansen Solubility Parameters: A user's handbook, Second Edition(漢森溶解度參數：用戶手冊 第二版)」,Hansen, Charles(2007)或軟體：HSPiP等而算出。 Similarly, the polar term and hydrogen bond term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent can be obtained according to the following equations (1-2) and (1-3). [Number 5]

[In formula (1-2), δ _P(S1) represents the polar term of the Hansen solubility parameter of the solvent 1 contained in the A agent, c _S1 represents the volume fraction of the solvent 1 contained in the A agent, δ _{P (S2)} represents the polarity term of the Hansen solubility parameter of the solvent 2 contained in the A agent, c _S2 represents the volume fraction of the solvent 2 contained in the A agent] [Numeric 6]

[In formula (1-3), δ _H(S1) represents the hydrogen bond term of the Hansen solubility parameter of the solvent 1 contained in the A agent, c _S1 represents the volume fraction of the solvent 1 contained in the A agent, δ _H(S2) represents the hydrogen bond term of the Hansen solubility parameter of solvent 2 contained in agent A, c _S2 represents the volume fraction of solvent 2 contained in agent A] δ _D , δ _P and δ _H of each solvent For example, it can be calculated using books: "Hansen Solubility Parameters: A user's handbook, Second Edition", Hansen, Charles (2007) or software: HSPiP, etc.

When Ra represented by the said formula (1) of the solvent contained in A agent does not satisfy Ra>37.0, it becomes difficult to obtain the liquid crystal cured film which is excellent in orientation after long-term storage. The Ra represented by the said formula (1) of the solvent contained in A agent becomes like this. Preferably it is 37.3 or more, More preferably, it is 37.5 or more, More preferably, it is 38.0 or more, More preferably, it is 39.0 or more. When Ra represented by the said formula (1) of the solvent contained in A agent satisfies the said value, even after long-term storage, it becomes easy to obtain the liquid crystal cured film which is excellent in orientation. Moreover, the adhesiveness and external appearance of a liquid crystal cured film also become favorable after long-term storage. The Ra represented by the said formula (1) of the solvent contained in A agent is 45.0 or less normally.

Specific examples of the solvent contained in agent A include methanol, ethanol, butanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, Alcohol-based solvents such as hexanol and phenol; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate ; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and methyl isobutyl ketone; non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane ; alicyclic hydrocarbon solvents such as cyclohexane; non-chlorinated aromatic hydrocarbon solvents such as toluene, anisole, trimethylbenzene and xylene; nitrile solvents such as acetonitrile; tetrahydrofuran, diethylene and dimethoxyethane ether solvents such as alkane; dichloromethane, dichloroethane, chlorotoluene, chloroform, chlorobenzene and dichlorobenzene and other chlorinated solvents; dimethyl sulfoxide and other sulfite solvents; dimethylformamide, dimethyl Ethylacetamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone and other amide solvents; pyridine and other heterocyclic solvents, etc. Among the above, especially preferred are methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, methyl isobutyl ketone, pentane, hexane, heptane, cyclohexane, toluene, benzene Methyl ether, trimethylbenzene, xylene, dichloroethane, chlorotoluene, chloroform, chlorobenzene, dichlorobenzene and pyridine.

The solvent may be used alone or in combination of two or more. In the case of using two or more kinds in combination, it is not negated to include a solvent with Ra≦37.0, as long as Ra of the whole solvent satisfies Ra>37.0 as described above. However, it is preferable that each Ra of all the solvents contained in the A agent satisfies Ra>37.0.

The content of the solvent in the agent A is preferably 50% by mass or more, more preferably 55% by mass or more, more preferably 60% by mass or more, and more preferably 99% by mass relative to the total mass of the total components contained in the agent A. mass % or less, more preferably 98 mass % or less, still more preferably 97 mass % or less. If the content of the solvent in agent A is more than the above lower limit value and less than or equal to the above upper limit value, it is easy to uniformly dissolve relatively high-viscosity solid content such as reactive additives in the following method for producing a liquid crystal cured film. can form a uniform coating film, so it is easy to obtain a liquid crystal cured film with a good appearance.

Agent A can be prepared by mixing the above-mentioned reactive additive, the above-mentioned solvent, and optionally the following optional components. Conditions such as the mixing method, temperature, and time are not particularly limited, and can be appropriately selected according to the type and amount of the components contained in the A agent.

The viscosity (25°C) of agent A is preferably 0.1-15 mPa·s, more preferably 0.1-10 mPa·s. When the viscosity of A agent is in the said range, it will be excellent in workability|operativity, and it will become easy to mix with B agent after that.

As described above, in the two-component polymerizable liquid crystal composition of the present invention, the reactive additives described above are separately prepared in agent A, and the following polymerizable liquid crystal compounds are prepared in agent B, respectively. Therefore, agent A does not substantially contain the following polymerizable liquid crystal compound. The term "substantially does not contain a polymerizable liquid crystal compound" means that the content of the polymerizable liquid crystal compound in the A agent is preferably less than 0.5 part by mass, more preferably less than 0.1 part by mass relative to 100 parts by mass of the reactive additive, More preferably, it is less than 0.05 mass part. Preferably, the content of the polymerizable liquid crystal compound in the A agent is 0 parts by mass.

＜Agent B＞ [Polymerizable liquid crystal compound] The agent B of the two-component polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound. The polymerizable liquid crystal compound is a compound that has a polymerizable group and exhibits a liquid crystal state, and as the polymerizable liquid crystal compound, for example, a polymerizable liquid crystal compound previously known in the field of retardation films can be used. The polymerizable group means a group that participates in the polymerization reaction of the polymerizable liquid crystal compound, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in a polymerization reaction by an active radical generated by the following photopolymerization initiator, an acid, or the like. As a polymerizable group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloxy group, methacryloyloxy group, ethylene oxide group may, for example, be mentioned. , oxetanyl, etc. Among them, acryloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloxy group is more preferable. The liquid crystallinity may be either a thermotropic liquid crystal or a liquid crystal.

In the present invention, the liquid crystallinity displayed by the polymerizable liquid crystal compound may be either a thermotropic liquid crystal or a liquid tropic liquid crystal, and is preferably a thermotropic liquid crystal from the viewpoint that the dense film thickness can be controlled. Moreover, as a phase order structure in a thermotropic liquid crystal, a nematic liquid crystal may be sufficient, and a smectic liquid crystal may be sufficient. As the polymerizable liquid crystal compound, only one type may be used, or two or more types may be used in combination.

The homopolymer of this polymerizable liquid crystal compound may exhibit positive wavelength dispersibility or reverse wavelength dispersibility. As a compound showing positive wavelength dispersibility, for example, Japanese Patent Laid-Open No. 2010-31223, Japanese Patent Laid-Open No. 2010-270108, Japanese Patent Laid-Open No. 2011-6360, and Japanese Patent Laid-Open No. 2011-207765 can be used. Compounds described in Gazette No.

In the case where the polymerizable liquid crystal compound is a compound that exhibits reverse dispersibility, from the viewpoint of exhibiting reverse wavelength dispersibility, it is preferable to be a liquid crystal having a mesogen structure in T-shaped or H-shaped, in order to obtain stronger dispersion. From a viewpoint, a T-shaped liquid crystal is more preferable, and the compound which has the characteristics of the following (1)-(4) as a structure of a T-shaped liquid crystal is preferable. (1) A compound capable of forming a nematic phase; (2) Having π electrons in the long axis direction (a) of the polymerizable liquid crystal compound. (3) It has π electrons in a direction intersecting with the long-axis direction (a) [intersection direction (b)]. (4) The sum of the π electrons existing in the long axis direction (a) is defined as N(πa) and the sum of the molecular weights existing in the long axis direction is N(Aa), and it is defined by the following formula (i) The π electron density in the long axis direction (a) of the polymerizable liquid crystal compound: D(πa)=N(πa)/N(Aa) (i) and the total of the π electrons present in the cross direction (b) is set is N(πb), the sum of the molecular weights present in the intersecting direction (b) is denoted as N(Ab), and the π electron density in the intersecting direction (b) of the polymerizable liquid crystal compound defined by the following formula (ii): D (πb)=N(πb)/N(Ab) (ii) in the relationship of 0≦[D(πa)/D(πb)]≦1 [that is, the π electron density in the cross direction (b) is larger than that in the long axis direction (a) π electron density]. Furthermore, the polymerizable liquid crystal compound satisfying all the features of (1) to (4) above can form a nematic phase by coating it on an alignment film and heating it to a phase transition temperature or higher. The nematic phase formed by the alignment of the polymerizable liquid crystal compound is usually aligned so that the long axis directions of the polymerizable liquid crystal compound are parallel to each other, and the long axis direction becomes the alignment direction of the nematic phase. As such a compound, the compound represented by following formula (A1) is mentioned specifically, for example. [hua 1]

In formula (A1), Ar represents a divalent group having an optionally substituted aromatic group. The aromatic group referred to here may have, for example, two or more Ar groups exemplified by the following (Ar-1) to (Ar-23). Preferably, the aromatic group contains at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. The aromatic group contained in the divalent group Ar may be one or two or more. When there are two or more aromatic groups contained in the divalent group Ar, the two or more aromatic groups can be bonded to each other by a single bond, -CO-O-, -O- and other divalent bonding groups. . G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, In the alkoxy group, cyano group or nitro group of 1 to 4, the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom. L ¹ and L ² , B ¹ and B ² are each independently a single bond or a divalent linking group. k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1≦k+l. Here, in the case of 2≦k+l, B ¹ and B ² , and G ¹ and G ² may be the same or different from each other, respectively. E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms, and here, more preferably an alkanediyl group having 4 to 12 carbon atoms. In addition, the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and the -CH ₂ - contained in the alkanediyl group may also be substituted with -O-, -S-, -COO-. The cases of -O-, -S-, and -COO- are not adjacent to each other. P ¹ and P ² each independently represent a polymerizable group or a hydrogen atom, and at least one of P ¹ and P ² is a polymerizable group.

G ¹ and G ² are each independently preferably a 1,4-phenylene group substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, optionally 1,4-cyclohexanediyl substituted with at least one substituent in the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenylene substituted with a methyl group , unsubstituted 1,4-phenylene or unsubstituted 1,4-trans-cyclohexanediyl, preferably unsubstituted 1,4-phenylene or unsubstituted 1 , 4-trans-cyclohexanediyl. Moreover, it is preferable that at least one of the plurality of G ¹ and G ² present is a divalent alicyclic hydrocarbon group, and it is more preferable that at least one of G ¹ and G ² bonded to L ¹ or L ² One is a divalent alicyclic hydrocarbon group.

L ¹ and L ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 COOR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, R ^a7 OC=OOR ^a8 -, -N=N-, -CR ^c =CR ^d - or -C≡C-. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and R ^d represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. L ¹ and L ² are each independently more preferably a single bond, -OR ^a2-1 -, -CH ₂ -, -CH ₂ CH ₂ -, ^{-COOR a4-1 - or OCOR a6-1 -} . Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent any one of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. L ¹ and L ² are each independently and more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ - or -OCO-.

B ¹ and B ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10 -, -R ^a11 COOR ^a12 -, -R ^a13 OCOR ^a14 - or R ^a15 OC=OOR ^a16 -. Here, R ^a9 to R ^a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. B ¹ and B ² are each independently more preferably a single bond, -OR ^a10-1 -, -CH ₂ -, -CH ₂ CH ₂ -, ^{-COOR a12-1} - or -OCOR ^a14-1 -. Here, R ^a10-1 , R ^a12-1 , and R ^a14-1 each independently represent any one of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. B ¹ and B ² are each independently and more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, -OCO- or -OCOCH ₂ CH ₂ -.

From the viewpoint of inverse wavelength dispersion performance, k and l are preferably in the range of 2≦k+l≦6, preferably k+l=4, more preferably k=2 and l=2. When k=2 and l=2, a symmetrical structure is obtained, which is preferable. E ¹ and E ² are preferably each independently an alkanediyl group having 1 to 17 carbon atoms, more preferably an alkanediyl group having 4 to 12 carbon atoms.

Examples of the polymerizable group represented by P ¹ or P ² include epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acrylyl group, methyl group Acryloyl, ethylene oxide, and oxetanyl groups, etc. Preferably at least one of P ¹ or P ² is acryl or methacryloyl, more preferably P ¹ and P ² are both acryl or methacryloyl, and more preferably acryl base.

Ar preferably has at least one selected from the group consisting of an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, and an electron withdrawing group. As this aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned, for example; Preferably, a benzene ring and a naphthalene ring are mentioned. As the aromatic heterocyclic ring, a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyridine ring, a pyrimidine ring, a triazole ring, a triazole ring, ring, pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, phenanthroline ring and the like. Among them, it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazolyl group. Moreover, when a nitrogen atom is contained in Ar, it is preferable that this nitrogen atom has a pi electron.

In formula (A1), the total number N _π of π electrons contained in Ar is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, particularly preferably 16 or more. Moreover, 32 or less are preferable, 30 or less are more preferable, 26 or less are still more preferable, and 24 or less are especially preferable.

As an aromatic group represented by Ar, the following group is mentioned, for example.

[hua 2]

In formulas (Ar-1) to (Ar-23), the symbol * represents a linking portion, and Z ⁰ , Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group , nitro, alkylsulfinyl with 1 to 12 carbon atoms, alkylsulfonyl with 1 to 12 carbons, carboxyl, fluoroalkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons , alkylthio with 1-12 carbons, N-alkylamine with 1-12 carbons, N,N-dialkylamine with 2-12 carbons, N-alkyl with 1-12 carbons Sulfasulfonyl group or N,N-dialkylaminesulfonyl group having 2 to 12 carbon atoms. Moreover, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

Q ¹ and Q ² each independently represent -CR ^{1' R} 2'-, -S-, -NH-, -NR 1'-, -CO- or -O-, and R ^{1 '} and R ^2' are each independently Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

J ¹ and J ² each independently represent a carbon atom or a nitrogen atom.

Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0-6.

Examples of the aromatic hydrocarbon group in Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, naphthyl, anthracenyl, phenanthrenyl, and biphenyl; preferably phenyl , naphthyl, more preferably phenyl. Examples of the aromatic heterocyclic group include a furyl group, a pyrrolyl group, a thienyl group, a pyridyl group, a thiazolyl group, a benzothiazolyl group, and the like, and a carbon number of 4 including at least one heteroatom such as a nitrogen atom, an oxygen atom, and a sulfur atom. Aromatic heterocyclic group of ~20; preferably furyl, thienyl, pyridyl, thiazolyl, benzothiazolyl.

Y ¹ , Y ² and Y ³ may each independently be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aggregated aromatic ring. The polycyclic aromatic heterocyclic group means a condensed polycyclic aromatic heterocyclic group or a group derived from a collection of aromatic rings.

Z ⁰ , Z ¹ and Z ² are preferably each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, and an alkoxy group having 1 to 12 carbon atoms, and Z ⁰ is more preferably Preferred are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group, and Z ¹ and Z ² are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, and a cyano group. Moreover, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

Q ¹ and Q ² are preferably -NH-, -S-, -NR ^1' -, -O-, and R ^1' is preferably a hydrogen atom. Among them, -S-, -O-, and -NH- are particularly preferred.

Among the formulae (Ar-1) to (Ar-23), the formula (Ar-6) and the formula (Ar-7) are preferred from the viewpoint of molecular stability.

In formulas (Ar-16) to (Ar-23), Y ¹ can form an aromatic heterocyclic group together with the nitrogen atom and Z ⁰ to which it is bonded. Examples of the aromatic heterocyclic group include those described above as the aromatic heterocyclic ring that Ar may have, and examples thereof include a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyridine ring, and a pyrimidine ring. ring, indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring, etc. The aromatic heterocyclic group may have a substituent. In addition, Y ¹ may be the above-mentioned optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom and Z ⁰ to which Y 1 is bonded. For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring, etc. are mentioned.

The amount of the polymerizable liquid crystal compound contained in the two-component polymerizable liquid crystal composition of the present invention is preferably 100 parts by mass, for example 70 parts by mass or more, preferably 80 parts by mass with respect to 100 parts by mass of the solid content in the agent B parts by mass or more, more preferably not less than 85 parts by mass, more preferably not less than 90 parts by mass, for example not more than 99.5 parts by mass, preferably not more than 99 parts by mass, more preferably not more than 98 parts by mass, further preferably not more than 95 parts by mass the following. It is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film that content of a polymerizable liquid crystal compound is more than the said lower limit and below the said upper limit. Here, the so-called solid content means the total amount of the components remaining by removing the solvent from the components in the B agent.

[solvent] It is preferable that the solvent contained in the B agent is such that the value of Ra represented by the above formula (1) satisfies Ra≦37.0. When the value of Ra represented by the above formula (1) of the solvent contained in the B agent satisfies Ra≦37.0, the polymerizable liquid crystal compound is easily dissolved. The lower limit value of Ra represented by the above formula (1) of the solvent contained in the agent B is usually 20.0. Such a solvent is not particularly limited, but is preferably a solvent that is inert to the polymerizable liquid crystal compound and can completely dissolve the compound. The solvent contained in the agent B may be used alone or in combination of two or more. When two or more types are mixed and used, the same solvent as the solvent used for A agent may be contained.

The content of the solvent in the B agent is preferably 50 mass % or more, more preferably 60 mass % or more, further preferably 70 mass % or more, preferably 95 mass %, relative to the total mass of the components contained in the B agent % or less, more preferably 90 mass % or less, still more preferably 88 mass % or less. If content of the solvent in B agent is more than the said lower limit and less than the said upper limit, it becomes easy to melt|dissolve the said polymerizable liquid crystal compound uniformly, and a uniform coating film can be formed in the manufacturing method of the following liquid crystal cured film, Therefore, it is easy to obtain a liquid crystal cured film with a good appearance.

Specific examples of such solvents include methanol, ethanol, butanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, cyclohexanol, and phenol. Alcohol solvents such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate and other ester solvents; acetone, methyl ether, etc. Ketone solvents such as methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and methyl isobutyl ketone; non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane; cyclohexane Alicyclic hydrocarbon solvents such as toluene, anisole, trimethylbenzene and xylene; non-chlorinated aromatic hydrocarbon solvents such as acetonitrile; nitrile solvents such as acetonitrile; ethers such as tetrahydrofuran, diethylene and dimethoxyethane Solvents; chlorinated solvents such as dichloromethane, dichloroethane, chlorotoluene, chloroform, chlorobenzene and dichlorobenzene; sulfite solvents such as dimethylsulfoxide; dimethylformamide, dimethylacetamide isoamide solvent; pyridine and other heterocyclic solvents, etc. These organic solvents may be used alone or in combination of two or more.

As described above, in the two-component polymerizable liquid crystal composition of the present invention, the above-mentioned reactive additives are separately prepared in the A component, and the above-mentioned polymerizable liquid crystal compound is separately prepared in the B component. Therefore, agent B does not substantially contain the above-mentioned reactive additive. The phrase "substantially does not contain reactive additives" means that the content of the reactive additives in the B agent is preferably less than 0.5 parts by mass, more preferably less than 0.1 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound, and further Preferably it is less than 0.05 mass part. Preferably, the content of the reactive additive in the B agent is 0 parts by mass.

Agent B can be prepared by mixing the above-mentioned polymerizable liquid crystal compound, the above-mentioned solvent, and optionally the following optional components. Conditions such as the mixing method, temperature, and time are not particularly limited, and can be appropriately selected according to the type and amount of the components contained in the B agent.

The viscosity (25°C) of agent B is preferably 0.1-15 mPa·s, more preferably 0.1-10 mPa·s. When the viscosity of the B agent is within the above-mentioned range, the handleability is excellent, and the mixing with the A agent thereafter becomes easy.

In addition to the above-mentioned components, the two-component polymerizable liquid crystal composition of the present invention may contain optional components such as a polymerization initiator, a sensitizer, a polymerization inhibitor, and a leveling agent.

[Polymerization initiator] The two-component polymerizable liquid crystal composition of the present invention may contain a polymerization initiator. A polymerization initiator is a compound which can start the polymerization reaction of a polymerizable liquid crystal compound, etc.. As the polymerization initiator, a photopolymerization initiator that generates active radicals by the action of light is preferred. A polymerization initiator may be contained in either or both of A agent or B agent which comprise the two-component type polymerizable liquid crystal composition of this invention.

系化合物、鹵代苯乙酮系化合物、二烷氧基苯乙酮系化合物、鹵代雙咪唑系化合物、鹵代三𠯤系化合物、三𠯤系化合物等。作為產生酸之光聚合起始劑，可使用錪鹽及鋶鹽等。就低溫下之反應效率優異之觀點而言，較佳為自裂解型光聚合起始劑，尤佳為苯乙酮系化合物、羥基苯乙酮系化合物、α-胺基苯乙酮系化合物、肟酯系化合物。 The polymerization initiator is preferably a photopolymerization initiator that generates active radicals by the action of light from the viewpoint of independent of the phase state of the thermotropic liquid crystal. As the photopolymerization initiator, a known photopolymerization initiator can be used as long as it is a compound that can start the polymerization reaction of the polymerizable liquid crystal compound. Specifically, a photopolymerization initiator capable of generating active radicals or an acid by the action of light can be exemplified, and among them, a photopolymerization initiator capable of generating a radical by the action of light is preferable. The photopolymerization initiators may be used alone or in combination of two or more. The photopolymerization initiator can fully utilize the energy emitted from the light source and is excellent in productivity. Therefore, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and among them, α-styrene is preferred. Ketone-based polymerization initiator and oxime-based photopolymerization initiator. As the photopolymerization initiator, known photopolymerization initiators can be used. For example, as the photopolymerization initiator generating active radicals, self-cleaving benzoin-based compounds, acetophenone-based compounds, and hydroxyacetophenone-based compounds can be used. Compounds, α-aminoacetophenone-based compounds, oxime ester-based compounds, acylphosphine oxide-based compounds, azo-based compounds, etc., dehydrogenated benzophenone-based compounds, alkylphenone-based compounds, and benzoin can be used Ether-based compounds, benzil ketal-based compounds, dibenzocycloheptanone-based compounds, anthraquinone-based compounds, ketone-based compounds, 9-oxosulfanyl-based compounds

system compounds, halogenated acetophenone-based compounds, dialkoxyacetophenone-based compounds, halogenated bisimidazole-based compounds, halogenated tris-based compounds, tris-based compounds, and the like. As an acid-generating photopolymerization initiator, an iodonium salt, a pernium salt, or the like can be used. From the viewpoint of being excellent in reaction efficiency at low temperatures, self-cleavage-type photopolymerization initiators are preferred, and acetophenone-based compounds, hydroxyacetophenone-based compounds, α-aminoacetophenone-based compounds, Oxime ester compounds.

As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

Examples of the acetophenone-based compound include dialkoxyacetophenone-based compounds such as diethoxyacetophenone; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1 -Hydroxystyrene such as ketones, oligomers of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one Ketone compounds; 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-2-benzyl-1-(4- α-aminoacetophenone-based compounds such as morpholinophenyl)butane-1-one and the like.

As the oxime ester compound, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzyl oxime)], ethanone, 1- Compounds such as [9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime) and the like.

Examples of the acylphosphine oxide-based compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzyl)phenyl oxide Phosphine etc.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzoate, 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl Thioether, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone, etc.

Examples of the alkylphenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2- -Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 ,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1 -Oligomers of ketone, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, etc.

Examples of the tris(2)-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris(2,4-bis()- Trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tristyryl, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl) )-1,3,5-tris𠯤, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-tris 𠯤, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tris𠯤, 2,4-bis(trichloromethyl) -6-[2-(4-Diethylamino-2-methylphenyl)vinyl]-1,3,5-tris(trichloromethyl)-6-[ 2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tris 𠯤, etc.

A commercially available one can be used as a polymerization initiator. Examples of commercially available polymerization initiators include Irgacure (registered trademark) 907, 184, 651, 819, 250, and 369 (manufactured by Ciba Refinery Co., Ltd.); Seikuol (registered trademark) BZ, Z, and BEE (manufactured by Seiko Chemical Co., Ltd.); kayacure (registered trademark) BP100 and UVI-6992 (manufactured by The Dow Chemical Co., Ltd.); Adeka Optomer SP-152 and SP-170 (manufactured by ADEKA Co., Ltd.); TAZ-A and TAZ-PP (manufactured by Nihon Siber Hegner Co., Ltd.); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.) and the like. The polymerization initiator may be one kind, or two or more kinds of polymerization initiators may be mixed according to the light source of light.

The content of the polymerization initiator can be appropriately adjusted according to the type and amount of the polymerizable liquid crystal compound, and is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, relative to 100 parts by mass of the content of the polymerizable liquid crystal compound, More preferably, it is 1-15 mass parts. If the content of the polymerization initiator is within the above-mentioned range, the reaction of the polymerizable group proceeds sufficiently, and the alignment of the polymerizable liquid crystal compound is not easily disturbed.

等𠮿酮化合物(例如2,4-二乙基9-氧硫𠮿

、2-異丙基9-氧硫𠮿

等)；蒽及含烷氧基之蒽(例如二丁氧基蒽等)等蒽化合物；啡噻𠯤及紅螢烯等。 [Sensitizer] The two-component polymerizable liquid crystal composition of the present invention may contain a sensitizer. A sensitizer may be contained in either or both of A agent or B agent which comprise the two-component polymerizable liquid crystal composition of this invention. As a sensitizer, a photosensitizer is preferable. As the sensitizer, for example, ketone and 9-oxosulfan are exemplified.

isoketone compounds (such as 2,4-diethyl 9-oxothio)

, 2-isopropyl 9-oxothio

etc.); anthracene and alkoxy-containing anthracene (such as dibutoxyanthracene, etc.) and other anthracene compounds;

The content of the sensitizer is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound content. When the content of the sensitizer is within the above range, the polymerization reaction of the polymerizable liquid crystal compound is easily accelerated.

[polymerization inhibitor] The two-component polymerizable liquid crystal composition of the present invention may contain a polymerization inhibitor from the viewpoint of stably advancing the polymerization reaction. A polymerization inhibitor may be contained in either or both of A agent or B agent which comprise the two-component type polymerizable liquid crystal composition of this invention. The degree of progress of the polymerization reaction can be controlled by the polymerization inhibitor.

Examples of the above-mentioned polymerization inhibitor include hydroquinone, alkoxy-containing hydroquinone, alkoxy-containing catechol (for example, butylcatechol, etc.), pyrogallol, etc. , 2,2,6,6-tetramethyl-1-piperidinyloxy free radicals and other free radical scavengers; thiophenols; β-naphthylamines and β-naphthols, etc.

When the two-component polymerizable liquid crystal composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the content of the polymerizable liquid crystal compound parts, more preferably 0.5 to 8 parts by mass. When the content of the polymerization inhibitor is within the above-mentioned range, the polymerization can be easily performed without disturbing the alignment of the polymerizable liquid crystal.

[leveler] The two-component polymerizable liquid crystal composition of the present invention may contain a leveling agent. The so-called leveling agent has the function of adjusting the fluidity of the composition to make the film obtained by coating the composition flatter, for example, a surfactant can be exemplified. A leveling agent may be contained in either or both of A agent or B agent which comprise the two-component polymerizable liquid crystal composition of this invention.

As a leveling agent, an organic-modified polysiloxane oil-based, polyacrylate-based, and perfluoroalkyl-based leveling agent may, for example, be mentioned. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of the above are manufactured by Toray Dow Corning), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (the above are all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (the above are all contracted by Momentive Performance Materials Japan Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (all of which are manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) R-08, Megafac R-30, Megafac R-90, Megafac F-410, Megafac F-411, Megafac F-443, Megafac F-445, Megafac F-470, Megafac F-477, Megafac F-479, Megafac F-482, Megafac F-483 (all of the above are manufactured by DIC Co., Ltd.), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (all of the above are manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S- 381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, SA-100 (all of the above are manufactured by AGC Kiyomi Chemical Co., Ltd.), trade name E1830 , the E5844 (manufactured by Daikin Institute of Fine Chemicals Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (all trade names: manufactured by BM Chemie Corporation). Among them, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

When the two-component polymerizable liquid crystal composition of the present invention contains a leveling agent, it is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of the content of the polymerizable liquid crystal compound, More preferably, it is 0.05-3 mass parts. If the content of the leveling agent is within the above-mentioned range, it is easy to align the polymerizable liquid crystal horizontally, and since the liquid crystal cured film obtained tends to be smoother, it is preferable. Furthermore, 2 or more types of leveling agents may be contained.

<Storage method> In the case of storing the two-component polymerizable liquid crystal composition of the present invention, the A agent and the B agent are separately stored. The so-called separate storage, for example, can be exemplified: the state of keeping A and B in two independent containers; The state in one container of mixing, etc. In this invention, it is preferable that A agent and B agent are stored in two independent containers.

As a container for storing agent A, a plastic container, a metal container, and a glass container can be mentioned, and a plastic container or a metal container is preferable. It is preferable that the container in which the agent A is stored is a plastic container or a metal container, since the side reaction of the reactive additive in the agent A is less likely to occur. As the material of the plastic container, for example, polypropylene, polyethylene, normethylene-based polymer, polystyrene, polyamide, poly(4-methylpentene-1), acrylic resin, polyamide Vinyl alcohol, acrylonitrile-butadiene-styrene copolymer, polymethacrylate, polyacrylate, cellulose ester, polycarbonate, polyethylene terephthalate, polyethylene, polyether, poly Ether ketone, polyethylene naphthalate, polyphenylene sulfide, polyphenylene ether, cyclic polyolefin such as cyclic olefin polymer or cyclic olefin copolymer, polyolefin such as amorphous polyarylate, polyester, Teflon, etc.; but not limited to these. As a material of a metal container, steel, such as SUS, tinplate, aluminum, etc. are mentioned, for example, However, It is not limited to these. When the container for storing agent A is a plastic container, it is preferably a light-shielding plastic container (for example, a brown plastic container) in terms of being less susceptible to the influence of ultraviolet rays, etc., which may cause deterioration of the composition. ). Moreover, you may apply coating etc. to the outer surface of a container.

It does not specifically limit as a container for storing the B agent, As a material of a container, a plastic, metal, glass, etc. are mentioned, for example. The container for storing the B agent is preferably a container having light-shielding properties as described above.

The shape of the container in which the A agent and the B agent are stored is not particularly limited. For example, a hexahedral shape such as a bucket can and a polyethylene can, a cylindrical shape such as a steel can and a barrel can for a paint brush, etc. may be mentioned. In addition, the capacity of the A agent and the B agent is not particularly limited, and a desired amount can be stored in a container.

When storing agent A, it is preferable to store agent A in a dry inert gas atmosphere. In this specification, the so-called dry gas generally refers to a gas whose dew point is below -50°C, and the so-called inert gas refers to, for example, nitrogen, argon, helium and other gases with low reactivity. The storage under a dry inert gas atmosphere includes, for example, a state in which the gas phase portion in the storage container is filled with a dry inert gas and then sealed and stored; and a storage container itself is stored in a space filled with a dry inert gas. Like and so on. By storing in a dry inert gas atmosphere, the side reaction between the moisture in the surrounding atmosphere and the active hydrogen reactive group of the reactive additive in the A agent can be avoided, so it is easy to improve the two-component type polymerizable liquid crystal composition of the present invention. In addition, the adhesiveness of the obtained liquid crystal cured film is easy to make the optical performance after long-term storage favorable.

The environment at the time of storing the agent B is not particularly limited, but it is preferably stored in a dry inert gas atmosphere.

The filling amount of agent A and agent B relative to the capacity of the storage container is not particularly limited. The filling amount of agent A and agent B is usually 30% or more of the storage container capacity, preferably 50% or more, which is easy to handle during mixing. From a sexual point of view, it is usually below 90%.

The temperature at which agents A and B are stored is not particularly limited. If the temperature is too high, the polymerization reaction of the polymerizable liquid crystal compound may start. If the temperature is too low, the solid content in agents A and B may precipitate. Therefore, the storage temperature is usually 0 to 50°C, preferably 10 to 40°C, and more preferably 15 to 35°C.

It may become difficult to manufacture the liquid crystal cured film which has favorable optical performance when it preserve|saves about 3-6 months in the state which mixed A agent and B agent. The two-component polymerizable liquid crystal composition of the present invention is advantageous in that a liquid crystal cured film having good optical properties can be obtained even after long-term storage. The period of storage of A and B is not particularly limited, but is usually within 3 years.

The two-component polymerizable liquid crystal composition of the present invention can be stored separately from the reactive additive and the polymerizable liquid crystal compound as described above, so that a liquid crystal cured film with good optical properties can be obtained even after long-term storage. According to the research conducted by the inventors of the present invention, in the two-component type polymerizable liquid crystal composition, when the solvent contained in the reactive additive satisfies Ra>37.0, it is difficult to produce a liquid crystal cured film after long-term storage. The molecular alignment of the polymerizable liquid crystal compound whose optical properties are deteriorated is disordered, and a liquid crystal cured film having good optical properties is obtained, and the adhesiveness and appearance of the liquid crystal cured film are also excellent.

<Production method of polymerizable liquid crystal composition> In the present invention, the polymerizable liquid crystal composition can be obtained by mixing the A agent and the B agent constituting the two-component type polymerizable liquid crystal composition. In addition, in this specification, the so-called "two-component type polymerizable liquid crystal composition" refers to a composition in a state in which agent A and agent B constituting the two-component type polymerizable liquid crystal composition are stored separately. The composition in the state where the agent and the agent B are mixed is referred to as a "polymerizable liquid crystal composition".

The timing of mixing the A component and the B component of the two-component polymerizable liquid crystal composition of the present invention is as long as the reactive additive in the A component and the moisture of the solvent that can be contained in the B component do not react. , it is not limited, and can be appropriately determined according to the type and amount of the reactive additive and the solvent in the B agent, mixing conditions, and environment.

The method of mixing the A agent and the B agent is not particularly limited, and a known mixing method can be used. For example, a method of mixing using a mixing device having a stirring blade such as a planetary mixer and a kneading mixer, or a method of static mixing using a static mixer or the like can be mentioned.

The ambient temperature at the time of mixing A agent and B agent is not specifically limited, Preferably it is 0-50 degreeC, More preferably, it is 15-40 degreeC, More preferably, it is mixed at 20-35 degreeC. The humidity (relative humidity) is also not particularly limited, but is preferably 30 to 60% RH, more preferably 40 to 55% RH. In addition, mixing is usually carried out under normal pressure (atmospheric pressure).

The mixing time is also not particularly limited, and can be appropriately adjusted according to the types and amounts of the components contained in the two-component polymerizable liquid crystal composition. The mixing time is usually 0.5 to 12 hours, preferably 0.5 to 6 hours.

<The manufacturing method of liquid crystal cured film> The manufacturing method of the liquid crystal curing film of the present invention includes: the step of forming an alignment film on the substrate; The step of mixing agent A and agent B constituting the two-component polymerizable liquid crystal composition of the present invention to obtain a polymerizable liquid crystal composition; The step of coating the above-mentioned mixed polymerizable liquid crystal composition on the above-mentioned alignment film to obtain a coating film; and The step of hardening the above-mentioned coating film.

[Substrate] As a base material for forming a liquid crystal cured film, a glass base material and a plastic base material are mentioned. Plastic substrates are better than glass substrates in terms of being able to perform Roll-to-Roll (roll-to-roll) processing and having higher productivity. Examples of plastics constituting the plastic base material include polyolefins such as polyethylene, polypropylene, and normethylene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; acrylic acid esters; polyacrylates; cellulose esters such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polyethylene; polyether Polyether ketone; polyphenylene sulfide and polyphenylene ether and other plastics.

Examples of commercially available cellulose ester substrates include "Fujitac Film" (manufactured by Fujifilm Co., Ltd.); "KC8UX2M", "KC8UY", and "KC4UY" (all of which are manufactured by Konica Minolta Opto Co., Ltd.) Wait.

Examples of commercially available cyclic olefin-based resins include "Topas" (registered trademark) (manufactured by Ticona Corporation (sole proprietorship)), "ARTON" (registered trademark) (manufactured by JSR Co., Ltd.), "ZEONOR" (registered trademark), "ZEONEX" (registered trademark) (all of the above are manufactured by ZEON Co., Ltd.), and "APEL" (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.). Such a cyclic olefin-based resin can be formed into a film by a known method such as a solvent casting method or a melt extrusion method to form a substrate. A commercially available cyclic olefin-based resin substrate can also be used. Examples of commercially available cyclic olefin resin substrates include "S-SINA" (registered trademark), "SCA40" (registered trademark) (all of which are manufactured by Sekisui Chemical Industry Co., Ltd.), and "ZEONOR FILM" (registered trademark) (manufactured by Optronics Co., Ltd.) and "ARTON Film" (registered trademark) (manufactured by JSR Co., Ltd.).

The thickness of the base material is preferably thin in terms of the quality to the extent that it can be handled practically, but if it is too thin, the strength tends to decrease and the workability tends to deteriorate. The thickness of the substrate is usually 5-300 μm, preferably 20-200 μm.

[Alignment Film] In the present invention, the alignment film is a film composed of a polymer compound, and has an alignment regulation force that allows the polymerizable liquid crystal compound to align liquid crystals in a desired direction.

The alignment film facilitates the alignment of the liquid crystal of the polymerizable liquid crystal compound. The state of liquid crystal alignment, such as horizontal alignment, vertical alignment, hybrid alignment, and oblique alignment, varies according to the properties of the alignment film and the polymerizable liquid crystal compound, and the combination thereof can be arbitrarily selected. For example, if the alignment film exhibits horizontal alignment as the material for the alignment regulation force, the polymerizable liquid crystal compound can form horizontal alignment or mixed alignment, and if it is a material that exhibits vertical alignment, the polymerizable liquid crystal compound can form vertical alignment or oblique alignment . Expressions such as horizontal and vertical represent the long-axis direction of the aligned polymerizable liquid crystal when the surface of the cured liquid crystal film is used as a reference. The so-called horizontal alignment is alignment with the long axis of the aligned polymerizable liquid crystal in the direction parallel to the plane of the liquid crystal cured film. Here, "parallel" means an angle of 0°±20° with respect to the plane of the cured liquid crystal film. The so-called vertical alignment refers to the long axis of the aligned polymerizable liquid crystal in the direction perpendicular to the plane of the liquid crystal cured film. The verticality here means 90°±20° with respect to the liquid crystal cured film plane.

Regarding the alignment regulation force, when the alignment film is formed of an alignment polymer, it can be arbitrarily adjusted by the surface state or rubbing conditions, and when it is formed by a photoalignment polymer, it can be adjusted by polarized light irradiation conditions, etc. Make any adjustments. In addition, the liquid crystal alignment can also be controlled by selecting physical properties such as surface tension and liquid crystallinity of the polymerizable liquid crystal compound.

The alignment film is preferably one that is insoluble in a solvent used for forming a liquid crystal cured film on the alignment film and has heat resistance for solvent removal or heat treatment for liquid crystal alignment. As the alignment film, an alignment film composed of an alignment polymer, a photo-alignment film and a groove (groove) alignment film, a stretched film extending in the alignment direction, etc. can be mentioned, and a photo-alignment film is preferable.

The thickness of the alignment film is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 1000 nm, and more preferably in the range of 50 to 300 nm.

Examples of the alignment polymer include polyamide and gelatin having an amide bond in the molecule, polyamide having an amide bond in the molecule, and polyamide acid and polyvinyl alcohol which are hydrolyzates thereof. , Alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylate, etc. Among them, polyvinyl alcohol is preferred. These alignment polymers may be used alone or in combination of two or more.

An alignment film composed of an alignment polymer is usually obtained by applying a composition prepared by dissolving an alignment polymer in a solvent (hereinafter, also referred to as an "alignment polymer composition") on a base. material and the solvent is removed; or the alignment polymer composition is applied to the substrate, the solvent is removed and the rubbing is performed (rubbing method).

Examples of the solvent include: water; alcohol-based solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ethyl acetate, butyl acetate , ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl pentane Ketone-based solvents such as methyl ketone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile-based solvents such as acetonitrile; tetrahydrofuran and dimethoxy Ether solvents such as ethane; chlorine-substituted hydrocarbon solvents such as chloroform and chlorobenzene, etc. These solvents may be used alone or in combination of two or more.

The concentration of the alignment polymer in the alignment polymer composition may be a range in which the alignment polymer can be completely dissolved in the solvent, and is preferably 0.1 to 20 mass % in terms of solid content with respect to the solution, more preferably It is 0.1-10 mass %.

As the alignment polymer composition, a commercially available alignment film material can also be used as it is. As a commercially available alignment film material, Sunever (registered trademark) (manufactured by Nissan Chemical Industry Co., Ltd.), Optomer (registered trademark) (manufactured by JSR Co., Ltd.), and the like can be exemplified.

As a method of applying the alignment polymer composition to a substrate, spin coater, extrusion coater, gravure coater, die coater, bar coater, and applicator may be mentioned. A known method such as a coating method such as a flexographic coating method or a printing method such as a flexographic coating method. In the case of manufacturing the alignment film of the present invention by a continuous manufacturing method in the form of Roll-to-Roll, the coating method usually adopts a printing method such as a gravure coating method, a die coating method or a flexographic coating method.

The solvent contained in the alignment polymer composition is removed, thereby forming a dry coating film of the alignment polymer. As a solvent removal method, a natural drying method, a ventilation drying method, a heating drying method, a vacuum drying method, etc. are mentioned.

As a rubbing method, a film of the oriented polymer formed on the surface of the substrate by applying the oriented polymer composition to the substrate and annealing, and a rubbing roll wound with a rubbing cloth and rotating can be exemplified method of contact.

Photo-alignment films generally contain polymers and oligomers or monomers with photoreactive groups. When the polymerizable liquid crystal is continuously formed, from the viewpoint of solvent resistance, etc., a polymer having a molecular weight of 5000 or more is preferable, and from the viewpoint of affinity, the polymerizable liquid crystal is a (meth)acryloyl group. In this case, an acrylic polymer is preferred. The photo-alignment film is formed by coating a composition (hereinafter, also referred to as a "photo-alignment film-forming composition") comprising a polymer, oligomer or monomer having a photoreactive group and a solvent on a substrate, After drying and removing the solvent, it is obtained by irradiating polarized light (preferably polarized light UV). The photo-alignment film can arbitrarily control the direction of the alignment regulatory force by selecting the polarization direction of the irradiated polarized light, which is more preferable in this respect.

The so-called photoreactive group refers to a group that produces liquid crystal alignment ability by irradiating light. Specifically, photoreactions such as alignment-induced or isomerization reactions of molecules, dimerization reactions, photocrosslinking reactions, or photodecomposition reactions, which are generated by irradiating light, are the origins of the liquid crystal alignment ability. Among the photoreactive groups, those that cause a dimerization reaction or a photocrosslinking reaction are preferred in terms of excellent orientation. As the photoreactive group capable of producing the above reaction, it is preferably one having an unsaturated bond, especially a double bond, and more preferably one having a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond ( C=N bond), nitrogen-nitrogen double bond (N=N bond), and carbon-oxygen double bond (C=O bond) group consisting of at least one group.

As a photoreactive group which has a C=C bond, a vinyl group, a polyalkenyl group, a stilbene group, a styryl pyridine, a styryl pyridinium group, a chalcone group, a cinnamonyl group, etc. are mentioned, for example. As a photoreactive group which has a C=N bond, the group which has structures, such as an aromatic Schiff base and an aromatic hydrazone, is mentioned. Examples of the photoreactive group having an N=N bond include azophenyl, azonaphthyl, aromatic heterocyclic azo, bisazo, and formazan groups. Oxyazobenzene is used as a base. structur. As a photoreactive group which has a C=O bond, a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group, etc. are mentioned. These groups may also have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

As the solvent of the composition for forming a photo-alignment film, it is preferable to dissolve the polymer and monomer having a photoreactive group, and as the solvent, for example, the above-mentioned solvents for the alignment polymer composition can be exemplified. solvent, etc.

The content of the photo-reactive group-containing polymer or monomer relative to the photo-alignment film-forming composition can be appropriately adjusted according to the type of the photo-reactive group-containing polymer or monomer or the thickness of the photo-alignment film to be produced , preferably at least 0.2 mass %, particularly preferably in the range of 0.3 to 10 mass %. In addition, a polymer material or a photosensitizer such as polyvinyl alcohol or polyimide may be included within the range in which the properties of the photoalignment film are not significantly impaired.

As a method of apply|coating the composition for photo-alignment film formation to a diffusion prevention layer, the method similar to the method of apply|coating an alignment polymer composition to a diffusion prevention layer can be mentioned. As a method of removing the solvent from the applied photoalignment film-forming composition, for example, the same method as the method of removing the solvent from the alignment polymer composition can be exemplified.

When irradiating with polarized light, a form of direct irradiation with polarized light after removing the solvent from the composition for forming a photoalignment film coated on a substrate, or a form of irradiating with polarized light from the substrate and allowing the polarized light to penetrate may be used. Moreover, it is especially preferable that this polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably a wavelength region in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength in the range of 250 to 400 nm is particularly preferred. Examples of the light source for the polarized light irradiation include: xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF, ArF, etc.; more preferably high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halide lamps object lamp. These lamps are preferred due to the greater luminous intensity of ultraviolet light with a wavelength of 313 nm. Polarized light can be irradiated by irradiating the light from the above-mentioned light source through an appropriate polarizing element. As the polarizing element, a polarizing filter, a polarizing element such as Grant-Thompson, Grant-Taylor, or the like, or a wire grid-type polarizing element can be used.

Furthermore, if it is covered during rubbing or polarized light irradiation, a plurality of regions (patterns) with different directions of liquid crystal alignment can also be formed.

The groove (groove) alignment film is a film with a concave-convex pattern or a plurality of grooves (grooves) on the surface of the film. When liquid crystal molecules are placed in a film having a plurality of linear grooves arranged at equal intervals, the liquid crystal molecules are aligned along the direction of the grooves.

As a method for obtaining a trench alignment film, there may be mentioned a method of forming a concave-convex pattern by developing and rinsing the surface of the photosensitive polyimide film after exposing the surface of the photosensitive polyimide film through an exposure mask having a slit in the shape of a pattern; A method of forming a UV curable resin layer before hardening on a plate-shaped disc having grooves on the surface, and transferring the resin layer to a base material and then curing; A method of forming unevenness on a film of UV curable resin before curing on the material, and then curing it. Specifically, the method described in Japanese Patent Laid-Open No. 6-34976 and Japanese Patent Laid-Open No. 2011-242743, etc. can be mentioned.

In order to obtain alignment with less misalignment, the width of the convex portion of the trench alignment film is preferably 0.05 to 5 μm, the width of the concave portion is preferably 0.1 to 5 μm, and the depth of the level difference between the concavities and convexes is preferably 2 μm or less. It is preferably 0.01 to 1 μm or less.

[Liquid crystal cured film] <Coating of polymerizable liquid crystal composition> A liquid crystal cured film can be formed by apply|coating the polymerizable liquid crystal composition after the said mixing on the said base material or an alignment film. As a method of coating the polymerizable liquid crystal composition on a substrate, extrusion coating method, direct gravure coating method, reverse gravure coating method, CAP coating method, slit coating method, Microgravure method, die nozzle coating method, inkjet method, etc. Moreover, the method etc. which apply|coat using a coating machine, such as a dip coater, a bar coater, and a spin coater, can also be mentioned. Among them, in the case of continuous coating in the form of Roll to Roll (roll-to-roll), the coating methods based on microgravure method, inkjet method, slit coating method and die coating method are preferred. When it is applied to a single substrate such as glass, a spin coating method with high uniformity is preferred. In the case of roll to roll coating, the composition for forming a photo-alignment film or the like may be coated on a substrate to form an alignment film, and the polymerizable liquid crystal composition may be continuously coated on the obtained alignment film.

<Drying of the polymerizable liquid crystal composition> As a drying method for removing the solvent contained in the polymerizable liquid crystal composition, for example, natural drying, ventilation drying, heat drying, drying under reduced pressure, and a method of combining these can be exemplified. Among them, natural drying or heating drying is preferable. The drying temperature is preferably in the range of 0 to 200°C, more preferably in the range of 20 to 150°C, and still more preferably in the range of 50 to 130°C. The drying time is preferably from 10 seconds to 20 minutes, more preferably from 30 seconds to 10 minutes. The composition for forming a photo-alignment film and the alignment polymer composition can also be dried in the same manner.

<Polymerization of polymerizable liquid crystal compounds> As a method for polymerizing the polymerizable liquid crystal compound, photopolymerization is preferable. The photopolymerization is carried out by irradiating an active energy ray to a laminate formed by applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound on a substrate or an alignment film. The active energy ray to be irradiated corresponds to the type of the polymerizable liquid crystal compound (especially the type of photopolymerizable functional group contained in the polymerizable liquid crystal compound) contained in the dry film, and the case where a photopolymerization initiator is included. The type of the photopolymerization initiator and the amount thereof are appropriately selected. Specifically, one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-ray, α-ray, β-ray, and γ-ray can be exemplified. Among them, in terms of easily controlling the progress of the polymerization reaction and being able to use it as a photopolymerization device widely used in the field, ultraviolet light is preferred, and it is preferred that photopolymerization can be carried out by ultraviolet light. The type of polymerizable liquid crystal compound is selected.

As a light source of the above-mentioned active energy rays, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, an emission wavelength LED (light-emitting diode, light-emitting diode) light sources, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, etc.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW/cm ² . The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activation of the photopolymerization initiator. The light irradiation time is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and still more preferably 0.1 second to 1 minute. When irradiated once or several times with such an ultraviolet irradiation intensity, the cumulative light intensity is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , more preferably 100 to 1,000 mJ/cm ² . When the cumulative light amount is below this range, the curing of the polymerizable liquid crystal compound becomes insufficient, and good transferability may not be obtained. Conversely, when the accumulated light amount is more than this range, the optical film including the optically anisotropic layer may be colored. [Example]

Hereinafter, the present invention will be described in more detail by way of examples. In addition, unless otherwise indicated, "%" and "part" in an example mean mass % and mass part, respectively. In addition, δD _(W) of water was 15.5, δP _(W) was 16.0, and δH _(W) was 42.3.

<Example 1> [Preparation of a composition for forming a photo-alignment film] The following components described in Japanese Patent Laid-Open No. 2013-033249 were mixed, and the obtained mixture was stirred at 80° C. for 1 hour to obtain A composition for forming a photo-alignment film.

將所製備之A劑(1)放入至SUS製罐中，並利用乾燥氮氣對氣相部進行置換後密封。 [Preparation of Agent A] Agent A (1) was obtained by mixing the following components and stirring at 25° C. for 1 hour. In addition, δD _(S) of cyclopentanone was 17.9, δP _(S) was 11.9, and δH _(S) was 5.2.

The prepared agent A (1) was put into a SUS tank, and the gas phase portion was replaced with dry nitrogen, and then sealed.

將所製備之B劑(1)放入至SUS製罐中，並利用乾燥氮氣對氣相部進行置換後密封。 [Preparation of Agent B] Agent B (1) was obtained by mixing the following components and stirring at 80° C. for 1 hour. The δD _(S) of N-methylpyrrolidone (NMP) was 18.0, the δP _(S) was 12.3, and the δH _(S) was 7.2.

The prepared B agent (1) was put into a SUS tank, and the gas phase portion was replaced with dry nitrogen, and then sealed.

<Production method of liquid crystal cured film> (1) Formation of photo-alignment film A cycloolefin polymer (COP) film (Zeonor Film (registered trademark) "ZF-14" manufactured by ZEON Co., Ltd., film thickness 23 μm) was used. As a base material, after corona treatment was performed on the film surface, the above-mentioned composition for forming a photo-alignment film was applied and dried at 80° C. to obtain a dry coating film. A photo-alignment film is formed by irradiating polarized light UV on the dried coating film, and a photo-alignment film-attached film is obtained. The polarized UV treatment was performed using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ/cm ² . In this way, a film with a photo-alignment film is obtained.

(2) Formation of liquid crystal cured film After preparing A agent (1) and B agent (1), and storing at 25° C. for 3 months or after storing for 6 months, A agent (1) and B agent (1) were prepared. The polymerizable liquid crystal composition (1) was obtained by mixing and stirring at 25°C for 1 hour. Immediately after obtaining the above-mentioned polymerizable liquid crystal composition (1), the above-mentioned polymerizable liquid crystal composition (1) was coated on the above-obtained photo-alignment film-attached film by a bar coating method, and then dried at 120° C. The solvent was sufficiently removed by heating and drying in an oven for 1 minute. Next, the layer formed of the polymerizable liquid crystal composition (1) was irradiated with ultraviolet rays with an exposure amount of 1000 mJ/cm ² (365 nm reference) using a high-pressure mercury lamp (Uniicure VB-15201BY-A; manufactured by Ushio Electric Co., Ltd.). This forms a liquid crystal cured film (1).

<Evaluation of Orientation> The obtained liquid crystal cured film was observed at a magnification of 400 times using a polarizing microscope (BX51, manufactured by Olympus Co., Ltd.). Those with good orientation were rated as ◯, those with slight misalignment were rated as Δ, and those with insufficient orientation such as poor alignment on the surface were rated as ×.

<Evaluation of Adhesion> Sellotape (manufactured by Nichiban) with a width of 25 mm was attached to the front surface and the back surface of the obtained liquid crystal cured film (1), respectively, and the 90° peeling test was performed on the front surface and the back surface, respectively. The case where peeling did not occur was evaluated as 0, the case where peeling occurred only in a part of the test site was evaluated as Δ, and the case where peeling occurred in the entire test site was evaluated as ×.

＜Appearance evaluation＞ The obtained liquid crystal cured film (1) was visually confirmed, and the presence or absence of foreign matter was confirmed. Those with no foreign matter visually recognized were evaluated as 0, those with a slight foreign matter recognized as Δ, and those with a large amount of foreign matter recognized as ×.

<Examples 2 and 3> Except having made the storage container of A agent as described in the table, it carried out similarly to Example 1, and obtained polymerizable liquid crystal composition (2), (3) and liquid crystal cured film (2), (3). The orientation, adhesiveness, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

<Example 4> A polymerizable liquid crystal composition (4) and a liquid crystal cured film (4) were obtained in the same manner as in Example 1, except that the gas phase part of the container storing the agent A was air. The orientation, adhesiveness, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

<Example 5> Except having used the following compound as a reactive additive, it carried out similarly to Example 1, and obtained the polymerizable liquid crystal composition (5) and the liquid crystal cured film (5). The orientation, adhesiveness, and appearance of the obtained liquid crystal cured film (5) were evaluated in the same manner as in Example 1. Reactive additive: Karenz AOI (manufactured by Showa Denko Co., Ltd.) 5.0 parts

<Example 6> Except having used the following compound as a reactive additive, it carried out similarly to Example 1, and obtained the polymerizable liquid crystal composition (6) and the liquid crystal cured film (6). The orientation, adhesiveness, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1. Reactive additive: KBM-5103 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 2.0 copies

<Example 7> A polymerizable liquid crystal composition ( 7) and liquid crystal cured film (7). In addition, δD _(S) of chloroform was 17.8, δP _(S) was 3.1, δH _(S) was 5.7, and Ra was 39.1. The orientation, adhesiveness, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

<Example 8> A polymerizable liquid crystal composition was obtained in the same manner as in Example 1, except that the solvent of agent A was 70 parts by mass of anisole and the solvent of agent (B) was 644 parts by mass of NMP The object (8) and the liquid crystal cured film (8). In addition, δD _(S) of anisole was 17.8, δP _(S) was 4.4, δH _(S) was 6.9, and Ra was 37.5. The orientation, adhesiveness, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

<Example 9> A polymerizable liquid crystal composition (9) was obtained in the same manner as in Example 1, except that the polymerizable liquid crystal compound was LC242 (manufactured by BASF JAPAN Co., Ltd.) and the solvent of the agent B was 644 parts by mass of NMP. And liquid crystal cured film (9). The orientation, adhesiveness, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

<Example 10> The polymerizable liquid crystal compound was LC242 (manufactured by BASF JAPAN Co., Ltd.), and the solvent of agent B was set to the ratio of 370 parts by mass of cyclopentanone and 274 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). A polymerizable liquid crystal composition (10) and a liquid crystal cured film (10) were obtained in the same manner as in Example 1, except that the solvent was mixed. Furthermore, δD _(S) of PGMEA was 15.6, δP _(S) was 5.6, δH _(S) was 9.8, and the Ra of the whole solvent in agent B was 35.9. The orientation, adhesiveness, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

<Comparative Example 1> After preparing the agent (A) and agent (B) in the same manner as in Example 1, the two liquids were stirred at 25° C. for 1 hour in a SUS tank for mixing. After mixing the two liquids, they were sealed under dry nitrogen, and stored at 25° C. for 3 months or 6 months before coating. , Adhesion, and appearance were evaluated.

<Comparative Example 2> Agent (B) was prepared in the same manner as in Comparative Example 1 except that the reactive additive was not used, sealed under dry nitrogen, and applied after being stored at 25°C for 3 months or 6 months. 1 The orientation, adhesiveness, and appearance of the obtained liquid crystal cured film were evaluated in the same manner.

<Comparative Examples 3 and 4> Except having changed the reactive additives as described in the table, after preparing the agent (A) and agent (B) in the same manner as in Comparative Example 1, the two liquids were stirred at 25° C. in a SUS tank for 1 hours for mixing. After mixing the two liquids, they were sealed under dry nitrogen, and stored at 25° C. for 3 months or 6 months before coating. , Adhesion, and appearance were evaluated.

<Comparative Example 5> After preparing the agent (A) and the agent (B) in the same manner as in Example 10, the two liquids were stirred at 25° C. for 1 hour in a SUS tank for mixing. After mixing the two liquids, they were sealed under dry nitrogen, and stored at 25° C. for 3 months or 6 months before coating. , Adhesion, and appearance were evaluated.

[Table 1] Agent A Agent B Storage method Coating results after storage for 3 months Coating results after storage for 6 months reactive additives solvent Ra polymerizable liquid crystal solvent Ra Mixing sequence of two liquids storage container Agent A gas phase Orientation tightness Exterior Orientation tightness Exterior Example 1 PR9000 5 parts by mass cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Keep separate and mix before use SUS tank dry nitrogen 〇 〇 〇 〇 〇 〇 Example 2 PR9000 5 parts by mass cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Keep separate and mix before use brown plastic bottle dry nitrogen 〇 〇 〇 〇 〇 〇 Example 3 PR9000 5 parts by mass cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Keep separate and mix before use brown glass bottle dry nitrogen 〇 △ 〇 〇 × 〇 Example 4 PR9000 5 parts by mass cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Keep separate and mix before use SUS tank Air 〇 〇 〇 △ △ △ Example 5 Karenz AOI 5 parts by mass cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Keep separate and mix before use SUS tank dry nitrogen 〇 〇 〇 〇 〇 〇 Example 6 KBM-5103 2 parts by mass cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Keep separate and mix before use SUS tank dry nitrogen 〇 〇 〇 〇 〇 〇 Example 7 PR9000 5 parts by mass Chloroform 39.1 (C-1) 75 parts by mass (C-2) 25 parts by mass NMP 35.7 Keep separate and mix before use SUS tank dry nitrogen 〇 〇 〇 〇 〇 〇 Example 8 PR9000 5 parts by mass anisole 37.5 (C-1) 75 parts by mass (C-2) 25 parts by mass NMP 35.7 Keep separate and mix before use SUS tank dry nitrogen 〇 △ 〇 〇 × 〇 Example 9 PR9000 5 parts by mass cyclopentanone 37.6 LC242 100 parts by mass NMP 35.7 Keep separate and mix before use SUS tank dry nitrogen 〇 〇 〇 〇 〇 〇 Example 10 PR9000 5 parts by mass cyclopentanone 37.6 LC242 100 parts by mass Cyclopentanone/PGMEA 35.9 Keep separate and mix before use SUS tank dry nitrogen 〇 〇 〇 〇 〇 〇 Comparative Example 1 PR9000 5 parts by mass cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Storage after mixing SUS tank dry nitrogen × × × × × × Comparative Example 2 none - - (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 - SUS tank dry nitrogen 〇 ×× 〇 〇 ×× 〇 Comparative Example 3 Karenz AOI 5 parts by mass cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Storage after mixing SUS tank dry nitrogen × × × × × × Comparative Example 4 KBM-5103 2 parts by mass cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Storage after mixing SUS tank dry nitrogen × × × × × × Comparative Example 5 PR9000 5 parts by mass cyclopentanone 37.6 LC242 100 parts by mass Cyclopentanone/PGMEA 35.9 Storage after mixing SUS tank dry nitrogen △ × △ △ × △

It is known that according to the compositions of Examples 1 to 10, even if they are mixed and coated after being stored for 3 months or after storage for 6 months after preparation, they can obtain good optical properties, high adhesion, and excellent optical properties. Appearance of liquid crystal curing film. On the other hand, the comparative examples 1 and 3-5 stored after mixing two liquids obtained the liquid crystal cured film with poor orientation and appearance, and the comparative example 2 which does not contain a reactive additive obtained the liquid crystal cured film with poor adhesiveness.

Claims (8)

A two-liquid type polymerizable liquid crystal composition, which contains agent A and agent B, agent A includes a reactive additive having a polymerizable group and an active hydrogen reactive group in the molecule and a solvent, agent B includes a polymerizable liquid crystal compound and a solvent, And the value of Ra represented by the following formula (1) of the solvent in the above-mentioned A agent satisfies Ra>37.0, [Equation 1]

[In the formula, δ _D(W) represents the dispersion term of the Hansen solubility parameter of water, δ _D(S) represents the dispersion term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent, and δ _P(W) represents the water The polar term of the Hansen solubility parameter, δ _P(S) represents the polar term of the Hansen solubility parameter of the whole solvent based on the weighted average of the solvent, δ _H(W) represents the hydrogen bond term of the Hansen solubility parameter of water, δ _H(S) represents the hydrogen bond term of the Hansen solubility parameter of the solvent population based on the weighted average of the solvent]. The two-component polymerizable liquid crystal composition according to claim 1, wherein the value of Ra represented by the above formula (1) of the solvent in the above-mentioned B agent satisfies Ra≦37.0. The two-component polymerizable liquid crystal composition according to claim 1 or 2, wherein the amount of the reactive additive contained in the agent A is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound . A storage method of the two-component polymerizable liquid crystal composition according to any one of claims 1 to 3, wherein the A agent and the B agent are separately stored. According to the storage method of claim 4, the above-mentioned agent A is stored in a plastic container or a metal container. According to the storage method of claim 4 or 5, the above-mentioned agent A is stored under a dry inert gas atmosphere. A method for producing a polymerizable liquid crystal composition, comprising the step of mixing the above-mentioned agent A and agent B constituting the two-component type polymerizable liquid crystal composition according to any one of claims 1 to 3. A manufacturing method of a liquid crystal hardening film, comprising: the step of forming an alignment film on the substrate; The step of mixing the above-mentioned agent A and agent B constituting the two-component polymerizable liquid crystal composition according to any one of claims 1 to 3 to obtain a polymerizable liquid crystal composition; The step of coating the above-mentioned mixed polymerizable liquid crystal composition on the above-mentioned alignment film to obtain a coating film; and The step of hardening the above-mentioned coating film.