Composition for retardation material, and retardation material

Abstract

The objective of the present invention is to provide a retardation material that exhibits high retardation even when the heat treatment temperature is low, is free from turbidity, and has high transparency and excellent reliability. In particular, the objective of the present invention is to enable the reduction of energy consumption from the viewpoint of ESG and SDGs. In addition, the objective of the present invention is to provide a composition for a retardation material for producing the retardation material.　The composition for a retardation material contains a polymer having, in a side chain thereof, a structure represented by formula (1). (In formula (1), the meanings of the symbols are as defined in the description.) (The meanings of the symbols in formulae (1A) and (1B) are as defined in the present specification.)

Description

Composition for phase difference material and phase difference material

[0001] The present invention relates to a composition for phase difference materials used to manufacture phase difference materials used in phase difference films and the like, and to a phase difference material obtained from the phase difference material composition.

[0002] In response to the demands for improved display quality and weight reduction in flat panel displays such as liquid crystal displays and organic EL displays, polymer materials with controlled internal molecular orientation structures are being used as optical compensation components for these displays, such as polarizing films (polarizers) and phase difference films (phase difference plates). These polymer materials play a role in changing the polarization state of light and are given birefringence (hereinafter, polymer materials will also be referred to as "phase difference materials").

[0003] Currently, development is underway on phase difference materials that utilize the optical anisotropy of polymerizable liquid crystal compounds. The polymerizable liquid crystal compounds used here have polymerizable groups and liquid crystal structural parts (structural parts having spacer structures and mesogenic structures), and acrylic groups are widely used as polymerizable groups.

[0004] Polymerizable liquid crystal compounds exhibit optical anisotropy when brought into contact with an orientation-treated substrate, utilizing both their orientation-regulating force and the self-organizing properties of liquid crystals. Prior art includes methods such as supporting a specific polymerizable liquid crystal compound having an acrylic group between supports on which an orientation-treated polymer film (hereinafter also referred to as "orientation film") is formed, and irradiating with radiation (see, for example, Patent Document 1), or using a composition comprising two types of polymerizable liquid crystal compounds having acrylic groups, chiral liquid crystals, and a photopolymerization initiator (see, for example, Patent Document 2).

[0005] Furthermore, phase difference films using polymerizable liquid crystal compounds or their polymers without using alignment films (see, for example, Patent Documents 3 and 4), and phase difference films using polymers having photocrosslinking sites (see, for example, Patent Documents 5 and 6) have also been reported.

[0006] JP-A-62-70407, JP-A-9-208957, Special Publication No. 2002-517605, WO2008 / 031243, JP-A 2008-164925, JP-A 11-189665

[0007] In recent years, from the perspective of ESG and SDGs, there has been a demand for reducing energy consumption, specifically lowering the temperature of the heat treatment in the manufacturing process of phase difference materials. Furthermore, when using plastic substrates with low heat resistance as the base material for phase difference materials, firing at high temperatures is not possible. Therefore, there is a need to be able to obtain a high phase difference even at low heat treatment temperatures.

[0008] When the crystallinity of the composition used to produce the phase difference material is high, the crystallization of the polymer in the composition is promoted by the heat treatment and ultraviolet irradiation that are part of the manufacturing process of the phase difference material, making it easier for localized defects to occur. As a result, the phase difference material becomes cloudy (hereinafter also referred to as "haze"), which degrades the optical properties of the display element, i.e., the display quality.

[0009] Furthermore, in recent years, liquid crystal and organic light-emitting diode (OLED) display elements have been used in applications such as smartphones and car navigation systems. Therefore, these display elements are required to withstand harsh environments where they are exposed to high temperatures for extended periods. Consequently, the phase difference materials used in these elements need to be more reliable than before.

[0010] Therefore, the present invention aims to provide a phase difference material that exhibits a high phase difference even at low heat treatment temperatures, is free from turbidity, highly transparent, and highly reliable. In particular, it aims to enable a reduction in energy consumption from the perspective of ESG and SDGs. Furthermore, it aims to provide a composition for producing the phase difference material.

[0011] As a result of diligent research to achieve the above objective, the inventors have completed the present invention, which has the following gist.

[0012] That is, it is a phase difference material composition containing a polymer having a side chain with a structure shown in the following formula [1] (hereinafter also referred to as the "specific structure") (hereinafter also referred to as the "specific polymer").

[0013]

[0014] (X １ is, -CH ２-, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-, -NHCO- or -N(CH ３ )CO-. X ２ represents a hydrogen atom, a hydroxy group, -(CH ２ ) ａ -COOH (a represents an integer of 0 to 4), a cyano group, a structure represented by the following formula [1A] or the following formula [1B]. X Ａ and X Ｂ each independently represent an alkyl group having 1 to 3 carbon atoms. mA and mB each independently represent an integer of 0 to 4, and at least one of mA and mB represents an integer of 1 or more. * represents a bond. )

[0015]

[0016] (Z ａ represents a hydrogen atom, a benzene ring, or a benzene ring wherein a hydrogen atom on the ring is substituted with a hydroxy group, -(CH ２ ) ａ -COOH (a represents an integer of 0 to 4), an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Z ｂ represents a hydrogen atom, a hydroxy group, -(CH ２ ) ｃ -COOH (c represents an integer of 0 to 4), a halogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. R Ａ and R Ｂ each independently represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 3 carbon atoms. za represents an integer of 0 to 12. * represents a bond to the benzene ring. ) Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

[0017] According to the present invention, a retardation material that exhibits high retardation even when the heat treatment temperature is low, has no turbidity, high transparency and excellent reliability can be obtained. Therefore, a liquid crystal display element and an organic EL element excellent in display quality can be provided.

[0018] The mechanism by which the present invention yields a liquid crystal display element with the above-mentioned excellent characteristics is not entirely clear, but it is presumed to be approximately as follows.

[0019] To enhance the optical properties of phase-difference materials, it is necessary to promote the photodimerization or photoisomerization reaction of photoreactive sites in specific polymers during the orientation treatment process, specifically the ultraviolet irradiation process, when forming the phase-difference material using a phase-difference material composition. However, due to interactions between specific polymers and shrinkage associated with curing during the phase-difference material formation process, the energy required to induce reorientation increases as the distance between specific polymers decreases.

[0020] In contrast to these, the specific structure of the present invention has X in its side chain portion. Ａ and X Ｂ These X have the structure. Ａ and X Ｂ This acts as a steric hindrance, preventing the distance between specific polymers from becoming too close, thus promoting reorientation. Also, the specific structure is X Ａ and X Ｂ Having this structure lowers the Tg (glass transition temperature), i.e., the crystallinity, of the specific polymer, thereby suppressing the occurrence of localized defects. Furthermore, as mentioned above, the increased distance between the specific polymers also helps to suppress the occurrence of localized defects.

[0021] Furthermore, X Ａ and X Ｂ Since it is an alkyl group with 1 to 3 carbon atoms that does not contain an unstable polar group, it has higher thermal stability compared to groups that have a polar group, such as an alkoxy group that has an ether group.

[0022] From the above points, when using the phase difference material composition of the present invention, a phase difference material can be obtained that exhibits a high phase difference even at low heat treatment temperatures, is free from turbidity, has high transparency, and is highly reliable.

[0023] The following describes in detail a phase difference material composition containing a specific polymer and a phase difference material obtained using said phase difference material composition. However, the description of the constituent elements described is merely an example of one embodiment of the present invention and is not limited to these contents.

[0024] In this invention, the main chain of a polymer (specific polymer) refers to the "stem" portion of the polymer, which consists of the longest chain of atoms. The side chains of a polymer (specific polymer) refer to the portions that branch off from the "stem" of the polymer.

[0025] <Specific Structure / Specific Polymer> A specific polymer is a polymer that has a specific structure in its side chains.

[0026] The specific polymer preferably has a main chain composed of at least one radical polymerizable group selected from (meth)acrylate, (meth)acrylamide, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, or norbornene, and siloxane.

[0027] The specific structure is the structure shown in formula [1] above.

[0028] X in equation [1] １ , X ２ , X Ａ , X Ｂ , mA and mB, and Z in formulas [1A] and [1B] ａ Z ｂ , R Ａ , R Ｂ And za are as defined above, but among them, the following are preferred: X １ is, -CH ２ -, -O-, -COO-, or -OCO- are preferred. More preferred are -COO- or -OCO-. ２ is, -(CH ２ ) ａ -COOH (where a is an integer from 0 to 4), formula [1A], or formula [1B] are preferred.

[0029] X Ａ and X Ｂ Each of these is preferably a methyl group or an ethyl group. More preferably, each of these is preferably a methyl group. mA and mB are each preferably 0 or 1, and either mA or mB is 1. More preferably, from the viewpoint of suitably obtaining the effects of the present invention, mA is 1 and mB is 0. Z ａThis refers to a hydrogen atom, a benzene ring, or a hydrogen atom on a ring that forms a hydroxyl group, -(CH ２ ) ａ A benzene ring substituted with -COOH (where a is an integer from 0 to 4), an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms is preferred. More preferably, a hydrogen atom or a cyclic hydrogen atom is -(CH ２ ) ａ This is a benzene ring substituted with -COOH (where a is an integer from 0 to 4). ｂ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｃ -COOH (where c is an integer from 0 to 4), a C1-C3 alkyl group, or a C1-C3 alkoxy group are preferred.

[0030] R Ａ and R Ｂ Each of these is preferably a hydrogen atom or a methyl group. Za is preferably an integer from 2 to 8. In formula [1], the benzene ring and X Ａ The coupling position is, from the viewpoint of the optical properties of the phase difference material, X １ It is preferable that the bond position is in the meta position relative to the bond position of the benzene ring and X Ｂ The coupling position is, from the viewpoint of the optical properties of the phase difference material, X １ It is preferable that the bond position is in the para position relative to the bond position.

[0031] A more specific example of a particular structure is the structure shown in the following formula [1a].

[0032]

[0033] X １ is, -CH ２ -, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) indicates CO-. In particular, -CH ２ -, -O-, -COO-, or -OCO- are preferred. More preferred are -COO- or -OCO-.

[0034] X ２is a hydrogen atom, a hydroxyl group, -(CH ２ ) ａ -COOH (where a is an integer from 0 to 4), a cyano group, and the structure shown by formula [1A] or formula [1B] above. In particular, -(CH ２ ) ａ -COOH (where a is an integer from 0 to 4), formula [1A], or formula [1B] are preferred.

[0035] In equations [1A] and [1B], Z ａ This refers to a hydrogen atom, a benzene ring, or a hydrogen atom on a ring that forms a hydroxyl group, -(CH ２ ) ａ -COOH (where a is an integer from 0 to 4), represents a benzene ring substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. In particular, a hydrogen atom, a benzene ring, or a hydrogen atom on the ring being a hydroxyl group, -(CH ２ ) ａ A benzene ring substituted with -COOH (where a is an integer from 0 to 4), an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms is preferred. More preferably, a hydrogen atom or a cyclic hydrogen atom is -(CH ２ ) ａ This is a benzene ring substituted with -COOH (where a is an integer from 0 to 4).

[0036] Z ｂ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｃ -COOH (where c is an integer from 0 to 4), halogen atom, C1-C8 alkyl group, or C1-C8 alkoxy group. In particular, hydrogen atom, hydroxyl group, -(CH ２ ) ｃ -COOH (where c is an integer from 0 to 4), a C1-C3 alkyl group, or a C1-C3 alkoxy group are preferred.

[0037] R Ａ and R Ｂeach independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. Among these, each independently is preferably a hydrogen atom or a methyl group. za represents an integer of 0 to 12. Among these, an integer of 2 to 8 is preferable. * represents a bonding site to a benzene ring.

[0038] X ３ and X ４ each independently represent a single bond, -O-, -COO- or -OCO-. Among these, each independently is preferably a single bond or -O-. X Ａ and X Ｂ each independently represent an alkyl group having 1 to 3 carbon atoms. Among these, each independently is preferably a methyl group or an ethyl group. More preferably, each is independently a methyl group. ma represents an integer of 1 to 12. Among these, an integer of 2 to 8 is preferable. mA and mB each independently represent an integer of 0 to 4, and at least one of mA and mB represents an integer of 1 or more. Among these, each is independently preferably 0 or 1, and one of mA and mB represents 1. More preferably, from the viewpoint of suitably obtaining the effects of the present invention, mA is 1 and mB is 0. * represents a bonding site to the main chain of the polymer.

[0039] In formula [1a], the bonding positions between the benzene ring and X ４ and X Ａ are, from the viewpoint of the optical properties of the retardation material, X ４ is para to the bonding position of X １ , and X Ａ is preferably meta to the bonding position of X １ . In addition, the bonding positions between the benzene ring and X ２ and X Ｂ are, from the viewpoint of the optical properties of the retardation material, X ２ is para to the bonding position of X １ , and X Ｂ is preferably para to the bonding position of X １ .

[0040] More specifically, examples include structures represented by any one of the following formulas [1aa] to [1af], and it is preferable to use these in the present invention.

[0041]

[0042]

[0043] X １ａ and X ２ａ each independently represent a single bond, -O-, -COO- or -OCO-. Among these, a single bond or -O- is preferred for each independently. X ３ａ represents a hydrogen atom, a hydroxy group, -(CH ２ ) ａ -COOH (wherein a represents an integer of 0 to 4) or a cyano group. Among these, a hydrogen atom, a hydroxy group or -(CH ２ ) ａ -COOH (wherein a represents an integer of 0 to 4) is preferred.

[0044] X ４ａ represents a single bond or an alkylene group having 1 to 12 carbon atoms. Among these, a single bond or an alkylene group having 2 to 8 carbon atoms is preferred. X ５ａ represents a hydrogen atom, a benzene ring, or a benzene ring substituted with a hydroxy group, -(CH ２ ) ａ -COOH (wherein a represents an integer of 0 to 4), an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Among these, a hydrogen atom, a benzene ring, or a benzene ring substituted with a hydroxy group, -(CH ２ ) ａ -COOH (wherein a represents an integer of 0 to 4), an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is preferred. More preferred is a hydrogen atom or a benzene ring substituted with -(CH ２ ) ａ -COOH (wherein a represents an integer of 0 to 4) on the ring.

[0045] X ６ａ represents a hydrogen atom, a hydroxy group, -(CH ２ ) ｃ -COOH (wherein c represents an integer of 0 to 4), a halogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Among these, a hydrogen atom, a hydroxy group, -(CH ２ )ｃ -COOH (where c is an integer from 0 to 4), a C1-C3 alkyl group, or a C1-C3 alkoxy group are preferred.

[0046] X Ａ１ and X Ａ２ Each independently represents an alkyl group having 1 to 3 carbon atoms. Among these, each independently is preferably a methyl group or an ethyl group. More preferably, each independently is preferably a methyl group. maa represents an integer from 1 to 12. Among these, an integer from 2 to 8 is preferred. mA1 and mA2 each independently represent an integer from 0 to 4, and either mA1 or mA2 represents an integer of 1 or more. Among these, each independently is preferably 0 or 1, and either mA1 or mA2 represents 1. More preferably, from the viewpoint of suitably obtaining the effects of the present invention, mA1 is 1 and mA2 is 0.

[0047] In formulas [1aa] to [1af], the benzene ring and X ２ａ and X Ａ１ The coupling position is, from the viewpoint of the optical properties of the phase difference material, X ２ａ It is in the para position with respect to -OCO- or -COO-, and X Ａ１ It is preferable that the -OCO- or -COO- is in the meta position. * indicates a bond with the main chain of the polymer.

[0048] To introduce a specific structure into a specific polymer, it is preferable to carry out a polymerization reaction using a compound having the specific structure (hereinafter also referred to as "specific compound") as part of the raw materials. In particular, it is preferable to use the compound represented by the following formula [1a-1].

[0049]

[0050] X １ ~X ４ , X Ａ , X Ｂ Details and preferred combinations of ma, mA and mB are as shown in formula [1a] above.

[0051] X ＡＡThis represents a structure shown by any of the following formulas [1a-a] to [1a-d], [1a-h], or [1a-i]. Among these, formulas [1a-a], [1a-b], [1a-c], or [1a-h] are preferred. More preferred are formulas [1a-a] or [1a-b].

[0052]

[0053] A １ is -O-, -NH-, or -N(CH ３ ) indicates -. Among these, -O- is preferred. A ａ Each of these independently represents either a hydrogen atom or a methyl group. Of these, a hydrogen atom is preferred. * represents X １ａ This shows the combination.

[0054] More preferably are compounds represented by any of the following formulas [1aa-1] to [1af-1].

[0055]

[0056]

[0057] X １ａ ~X ６ａ , X Ａ１ , X Ａ２ Details and preferred combinations of maa, ma1, and ma2 are as shown in formulas [1aa] to [1af] above. ＡＡ The details and preferred forms are as shown in the above formula [1a-1].

[0058] Specific examples of the particular compound include compounds represented by any of the following formulas [1-1a] to [1-36a], and it is preferable to use these from the viewpoint of suitably obtaining the effects of the present invention. Among these, formulas [1-1a], [1-2a], [1-7a], [1-8a], [1-13a], [1-14a], [1-19a], [1-20a], [1-25a], [1-26a], [1-31a], or [1-32a] are preferred. In this case, the benzene ring and R ａ From the viewpoint of the optical properties of the phase difference material, the bonding position is preferably meta relative to -OCO- or -COO-.

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065] (R ａ and R ｂ Each of these independently represents either a methyl group or an ethyl group. ｃ is a hydrogen atom, a hydroxyl group, or -(CH ２ ) ｄ -COOH (where d is an integer from 0 to 4). R ｄ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｅ -COOH (where e is an integer from 0 to 4), represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. m is an integer from 2 to 8.

[0066] From the viewpoint of the optical properties of the phase difference material, the proportion of a specific structure (specific compound) used in a specific polymer is preferably 5 to 99 mol%, more preferably 10 to 90 mol%, and particularly preferably 15 to 85 mol%. Furthermore, one or more types of specific structures (specific compounds) can be used in combination, depending on the properties.

[0067] From the viewpoint of the optical properties of the phase difference material, it is preferable that the specific polymer further has at least one structure selected from the structure represented by the following formula [2a] (hereinafter also referred to as "second structure (2a)") and the structure represented by formula [2b] (hereinafter also referred to as "second structure (2b)") in its side chains (hereinafter, the second structure (2a) and the second structure (2b) are collectively referred to as "second structure").

[0068] The second structure (2a) is as follows:

[0069]

[0070] Y１ａ and Y ２ａ These are, independently, single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH) ３ )-, -NHCONH-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) represents CO-. Among these, a single bond, -O-, -COO-, or -OCO- are preferred, each independently. More preferred are a single bond or -O-, each independently.

[0071] Y ３ａ This represents a single bond, a structure shown by formula [2a-A] or formula [2a-B] below. ４ａ The structure is represented by the following formula [2a-C] or formula [2a-D]. Of these, formula [2a-C] is preferred. na represents an integer from 1 to 12. Of these, an integer from 2 to 8 is preferred. * indicates a bond with the main chain of the polymer.

[0072]

[0073] Y １Ａ These are single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) Indicates CO-. Among these, single bonds, -O-, -COO-, or -OCO- are preferred. * is Y ２ａ This shows the combination with Y. ** represents Y ４ａ This shows the combination.

[0074]

[0075] Y ２Ａ This refers to a hydrogen atom, a benzene ring, or a hydrogen atom on a ring that forms a hydroxyl group, -(CH ２ ) ａ -COOH (where a is an integer from 0 to 4), represents a benzene ring substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. In particular, a hydrogen atom, a benzene ring, or a hydrogen atom on the ring being a hydroxyl group, -(CH ２ ) ａA benzene ring substituted with -COOH (where a is an integer from 0 to 4), an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms is preferred. More preferably, a hydrogen atom or a cyclic hydrogen atom is -(CH ２ ) ａ This is a benzene ring substituted with -COOH (where a is an integer from 0 to 4).

[0076] Y ３Ａ This represents a structure comprising at least one selected from the following formulas [2-a] to [2-c]. Among these, formula [2-a] or formula [2-b] is preferred.

[0077] Y ４Ａ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｂ -COOH (where b is an integer from 0 to 4), halogen atom, C1-C8 alkyl group, or C1-C8 alkoxy group. In particular, hydrogen atom, hydroxyl group, -(CH ２ ) ｂ -COOH (where b is an integer from 0 to 4), a C1-C3 alkyl group, or a C1-C3 alkoxy group are preferred.

[0078] Y ａ and Y ｂ Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or a C1-C3 alkyl group. Among these, each independently represents a hydrogen atom or a methyl group. * represents X ３ａ This shows the combination.

[0079]

[0080] nA represents an integer between 1 and 12, preferably between 2 and 8. * indicates a combination.

[0081] The second structure (2a) is more specifically a structure represented by any of the following formulas [2aa] to [2aj], and it is preferable to use these in the present invention.

[0082]

[0083]

[0084] Y ５ａand Y ６ａ Each of these independently represents a single bond, -O-, -COO-, or -OCO-. Among these, a single bond or -O- is preferred. ７ａ This represents a single bond or an alkylene group having 1 to 12 carbon atoms. Among these, a single bond or an alkylene group having 2 to 8 carbon atoms is preferred. ８ａ This refers to a hydrogen atom, a benzene ring, or a hydrogen atom on a ring that forms a hydroxyl group, -(CH ２ ) ａ -COOH (where a is an integer from 0 to 4), represents a benzene ring substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. In particular, a hydrogen atom, a benzene ring, or a hydrogen atom on the ring being a hydroxyl group, -(CH ２ ) ａ A benzene ring substituted with -COOH (where a is an integer from 0 to 4), an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms is preferred. More preferably, a hydrogen atom or a cyclic hydrogen atom is -(CH ２ ) ａ This is a benzene ring substituted with -COOH (where a is an integer from 0 to 4).

[0085] Y ９ａ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｂ -COOH (where b is an integer from 0 to 4), halogen atom, C1-C8 alkyl group, or C1-C8 alkoxy group. In particular, hydrogen atom, hydroxyl group, -(CH ２ ) ｂ -COOH (where b is an integer from 0 to 4), a C1-C3 alkyl group, or a C1-C3 alkoxy group are preferred. naa is an integer from 1 to 12, with 2 to 8 being preferred. * indicates a bond to the polymer's main chain.

[0086] To introduce the second structure (2a) into a specific polymer, it is preferable to carry out a polymerization reaction using a compound having the second structure (2a) (hereinafter also referred to as "the second compound (2a)") as part of the raw materials. In particular, it is preferable to use the compound represented by the following formula [2a-1].

[0087]

[0088] Y １ａ ~Y ４ａ Details and preferred combinations of and na are as shown in formula [2a] above. ＡＡ The details and preferred compounds are as shown in formula [1a-1] above. More preferred are compounds represented by any of the following formulas [2aa-1] to [2aj-1].

[0089]

[0090]

[0091] Y ５ａ ~Y ９ａ Details and preferred combinations of and naa are as shown in formulas [2aa] to [2aj] above. ＡＡ The details and preferred forms are as shown in the above formula [1a-1].

[0092] Specific examples of the second compound (2a) include compounds represented by any of formulas [2-1a] to [2-20a], and it is preferable to use these from the viewpoint of suitably obtaining the effects of the present invention.

[0093]

[0094]

[0095]

[0096] (R is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｄ -COOH (where d is an integer from 0 to 4), represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. n is an integer from 2 to 8.

[0097] The second structure (2b) is as follows:

[0098]

[0099] Y １ｂ and Y ２ｂ These are, independently, single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH) ３)-, -NHCONH-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) represents CO-. Among these, a single bond, -O-, -COO-, or -OCO- are preferred, each independently. More preferred are a single bond or -O-, each independently.

[0100] Y ３ｂ This represents a structure shown by any of the following formulas [2b-A] to [2b-G]. Among these, formulas [2b-A], [2b-D] to [2b-G] are preferred. More preferred are formulas [2b-A], [2b-D], or [2b-F]. nb represents an integer from 1 to 12. Among these, an integer from 2 to 8 is preferred.

[0101] * indicates a bond to the polymer's main chain.

[0102]

[0103] Y １Ｂ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｃ -COOH (where c is an integer from 0 to 4) or a cyano group. In particular, a hydrogen atom, a hydroxyl group or -(CH ２ ) ｃ -COOH (where c is an integer from 0 to 4) is preferred.

[0104] Y ２Ｂ These are single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) indicates CO-. Among these, single bonds, -O-, -CO-, -COO-, or -OCO- are preferred. More preferred are single bonds, -O-, -COO-, or -OCO-. * indicates Y ２ｂ This shows the combination.

[0105] The second structure (2b) is more specifically a structure represented by any of the following formulas [2ba] to [2bg], and it is preferable to use these in the present invention.

[0106]

[0107] Y ４ｂ and Y ５ｂ Each of these independently represents a single bond, -O-, -COO-, or -OCO-. Among these, a single bond or -O- is preferred. ６ｂ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｃ -COOH (where c is an integer from 0 to 4) or a cyano group. In particular, a hydrogen atom, a hydroxyl group or -(CH ２ ) ｃ -COOH (where c is an integer from 0 to 4) is preferred.

[0108] nbb represents an integer between 1 and 12, with integers between 2 and 8 being preferred. * indicates a bond with the polymer's main chain.

[0109] To introduce the second structure (2b) into a specific polymer, it is preferable to carry out a polymerization reaction using a compound having the second structure (2b) (hereinafter also referred to as "the second compound (2b)") as part of the raw materials. In particular, it is preferable to use the compound represented by the following formula [2b-1].

[0110]

[0111] Y １ｂ ~Y ３ｂ Details and preferred combinations of and nb are as shown in formula [2b] above. ＡＡ The details and preferred compounds are as shown in formula [1a-1] above. More preferred are compounds represented by any of the following formulas [2ba-1] to [2bg-1].

[0112]

[0113] Y ４ｂ ~Y ６ｂ Details and preferred combinations of nbb are as shown in formulas [2ba] to [2bg] above. ＡＡ The details and preferred forms are as shown in the above formula [1a-1].

[0114] Specific examples of the second compound (2b) include compounds represented by any of the following formulas [2-1b] to [2-14b], and it is preferable to use these from the viewpoint of suitably obtaining the effects of the present invention.

[0115]

[0116]

[0117] (R is a hydrogen atom, a hydroxyl group, or -(CH ２ ) ｃ -COOH (where c is an integer from 0 to 4. n is an integer from 2 to 8.)

[0118] Hereafter, the second compound (2a) and the second compound (2b) will be collectively referred to as "the second compound."

[0119] The proportion of the second structure (second compound) used in a specific polymer is preferably 80 mol% or less, from the viewpoint of the reactivity of the photoreactive site and the optical properties of the phase difference material. More preferably, it is 1 to 70 mol%. Particularly preferred is 1 to 60 mol%. Furthermore, one or more types of the second structure (second compound) can be used in combination, depending on the characteristics.

[0120] The specific polymer may also incorporate structures other than the specific structure and the second structure (hereinafter also referred to as "other structures"). In this case, it is preferable to use the following compounds (hereinafter also referred to as "other compounds").

[0121] Specific examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthyl acrylate, anthyl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthyl methacrylate, anthyl methyl methacrylate Examples include methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, styrene, methylstyrene, chlorostyrene, bromostyrene, maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0122] Furthermore, examples include glycidyl (meth)acrylate, glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, glycidyl α-n-butylacrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxybutyl α-ethylacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 6,7-epoxyheptyl α-ethylacrylate, 3-methyl-3-oxetanylmethyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, 4-hydroxybutyl glycidyl ether (meth)acrylate, and compounds having crosslinking groups such as those shown in formulas [K-1] to [K-3] below. In the present invention, it is preferable to use compounds having these crosslinking groups from the viewpoint of the curability and optical properties of the phase difference material.

[0123]

[0124] The proportion of other structures (other compounds) used in a specific polymer is the remaining proportion when the proportion of the specific structure and the second structure used is less than 100 mol%. Furthermore, one or more types of other structures (other compounds) can be used in combination, depending on their respective properties.

[0125] The polymerization method for a specific polymer is not particularly limited, but it can be synthesized by, for example, free radical polymerization or living radical polymerization (nitroxide-mediated radical polymerization (NMP) using nitroxide as the dormant species), atom transfer radical polymerization (ATRP) using metal complexes, reversible addition-cleavage chain transfer (RAFT) polymerization using sulfur compounds as the dormant species, reversible transfer catalytic polymerization (RTCP) using alkyl iodide compounds as the dormant species and phosphorus compounds or alcohols as catalysts, etc.), or chain transfer polymerization. In this case, when using living radical polymerization, it is preferable to use RAFT polymerization because the inclusion of metal residues or halogen compounds may adversely affect each property.

[0126] A specific polymer can be obtained by a radical polymerization reaction using a specific compound, or a specific compound and a second compound. Known radical initiators can be used in this reaction. Specific examples include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid)dimethyl; organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butylperoxypivalate, and 1,1'-bis(tert-butylperoxy)cyclohexane; and redox initiators consisting of these peroxides and reducing agents. Among these, azo compounds are preferred, and more preferably, 2,2'-azobis(isobutyronitrile) or 2,2'-azobis(isobutyric acid)dimethyl.

[0127] The proportion of the radical initiator used is preferably 0.0001 to 50 parts by mass, relative to 100 parts by mass of all compounds used in the radical polymerization reaction. More preferably, it is 0.0005 to 40 parts by mass.

[0128] Radical polymerization reactions are preferably carried out in an organic solvent. Examples of organic solvents include alcohols, ethers, ketones, amides, esters, and hydrocarbon compounds. Specific examples include tetrahydrofuran, cyclopentanone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethyl sulfoxide, tetramethylurea, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1,Examples include 4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. These organic solvents can be used individually or in combination of two or more.

[0129] The amount of organic solvent used (a) is preferably such that the total amount of all compounds used in the radical polymerization reaction (b) is 0.1 to 50 parts by mass relative to the total amount of polymerization reaction solution used (a + b). Furthermore, since the radical polymerization reaction is inhibited by oxygen, it is preferable to use an organic solvent that has been degassed to the greatest extent possible.

[0130] The reaction temperature for the radical polymerization reaction is preferably 30 to 120°C, more preferably 60 to 110°C. The reaction time is preferably 1 to 36 hours, more preferably 2 to 24 hours.

[0131] The specific polymer can be obtained directly from the reaction solution of the radical polymerization reaction, but it is preferable to remove unreacted compounds and excess radical initiators. Specifically, methods include recovering the specific polymer by adding the reaction solution to a solvent, or using adsorbents such as activated carbon or ion exchange resins. Known methods can be used for these purposes.

[0132] From the viewpoint of the strength of the resulting phase difference material, workability during phase difference material formation, and uniformity of the coating film, the specific polymer preferably has a weight-average molecular weight of 2,000 to 2,000,000 as measured by the GPC (Gel Permeation Chromatography) method. More preferably, it is 2,000 to 1,000,000. Particularly preferred is 5,000 to 500,000.

[0133] <Composition for Phase Difference Material> The composition for phase difference material is a solution for forming a phase difference material, and is a solution containing a specific polymer and a solvent.

[0134] The polymer components do not have to be all specific polymers; other polymers may be mixed in. Specifically, examples include poly(meth)acrylates that do not contain the specific structure, polysiloxanes, polyesters, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-maleic anhydride) copolymers, poly(isobutylene-maleic anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, or poly(styrene-phenylmaleimide) derivatives. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley Co., Ltd.), and GSM301 (manufactured by Gifu Cerates Manufacturing Co., Ltd.). Specific examples of poly(isobutylene-maleic anhydride) copolymers include Isoban-600 (manufactured by Kuraray Co., Ltd.). A specific example of a poly(vinyl ether-maleic anhydride) copolymer is Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland).

[0135] When these specific polymers and other polymers are used as polymer components, the proportion of other polymers used is preferably 90 parts by mass or less, relative to 100 parts by mass of the total polymers contained in the phase difference material composition. More preferably, it is 10 to 90 parts by mass. Most preferably, it is 20 to 80 parts by mass.

[0136] The solvent content in the phase difference material composition can be appropriately selected from the viewpoint of the application method of the phase difference material composition and the desired film thickness. In particular, from the viewpoint of forming a uniform phase difference material by application, the solvent content in the phase difference material composition is preferably 50 to 99.9% by mass. More preferably 60 to 99% by mass. Particularly preferred is 65 to 99% by mass.

[0137] The solvent used in the phase difference material composition is not particularly limited as long as it is a solvent that dissolves the specific polymer. In particular, the following solvents (hereinafter also referred to as "Solvent Class A") are preferred. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N,N-dimethylpropionamide, tetramethylurea, N,N-diethylacetamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethyl Examples include lupropanamide, 3-butoxy-N,N-dimethylpropanamide, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone (hereinafter collectively referred to as "good solvents"). Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, or γ-butyrolactone are particularly preferred. These may be used individually or in combination of two or more.

[0138] If the specific polymer has high solubility in a solvent, the following solvents (hereinafter also referred to as "solvents of type B") can be used.For example, diisopropyl ether, diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy) Examples include xy)-1-propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, ethylene glycol monoethyl ether, n-butyl acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, 4-methyl-2-pentyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, or diisobutyl ketone (2,6-dimethyl-4-heptanone).In particular, it is preferable to use diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone. These may be used individually or in combination of two or more.

[0139] In the present invention, from the viewpoint of the coating properties of the phase difference material, it is preferable to use a solvent that combines solvent A and solvent B. When solvent A and solvent B are used in combination, solvent B is preferably 1 to 99% by mass of the total solvent contained in the phase difference material composition. More preferably, it is 10 to 99% by mass. Most preferably, it is 20 to 95% by mass.

[0140] In order to enhance the film strength of the phase difference material composition, it is preferable to introduce a compound having at least one structure selected from epoxy groups, isocyanate groups, oxetanyl groups, oxazoline groups, cyclocarbonate groups, hydroxyl groups, hydroxyalkyl groups, lower alkoxyalkyl groups, and polymerizable unsaturated groups (hereinafter collectively referred to as "crosslinkable compounds"). In this case, the compound must contain two or more of these groups.

[0141] Specific examples of crosslinkable compounds having epoxy groups or isocyanate groups include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, bisphenol A type epoxy resins such as Epicote 828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resins such as Epicote 807 (manufactured by Mitsubishi Chemical Corporation), and YX-8000 (manufactured by Mitsubishi Chemical Corporation). Compounds in which a tertiary nitrogen atom is bonded to an aromatic carbon atom, such as hydrogenated bisphenol A epoxy resins like YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), biphenyl skeleton-containing epoxy resins like EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), (o,m,p-) cresol novolac epoxy resins like EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), tetrakis(glycidyloxymethyl)methane, N,N,N',N'-tetraglycidyl-1,4-phenylenediamine, N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis[4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane;N,N,N',N'-tetraglycidyl-1,2-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,3-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,4-diaminocyclohexane, bis(N,N-diglycidyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-2-methyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane, 1 Examples include compounds in which a tertiary nitrogen atom is bonded to an aliphatic carbon atom, such as 3-bis(N,N-diglycidylaminomethyl)benzene, 1,4-bis(N,N-diglycidylaminomethyl)benzene, 1,3,5-tris(N,N-diglycidylaminomethyl)cyclohexane, and 1,3,5-tris(N,N-diglycidylaminomethyl)benzene; isocyanurate compounds such as triglycidyl isocyanurate (manufactured by Nissan Chemical Corporation); and those described in paragraph

[0037] of Japanese Patent Publication No. 10-338880 and paragraphs

[0051] to

[0054] of WO2017 / 170483.

[0142] Specific examples of crosslinkable compounds having an oxetanyl group include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (Aronoxetane OXT-121 (XDO)), bis[2-(3-oxetanyl)butyl]ether (Aronoxetane OXT-221 (DOX)), 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene (CTOX), and those described in paragraphs

[0170] to

[0175] of WO2011 / 132751.

[0143] Specific examples of crosslinkable compounds having an oxazoline group include compounds such as 2,2'-bis(2-oxazoline) and 2,2'-bis(4-methyl-2-oxazoline), polymers and oligomers having an oxazoline group such as Epocross (manufactured by Nippon Shokubai Co., Ltd.), and those described in paragraph

[0115] of Japanese Patent Publication 2007-286597.

[0144] Specific examples of crosslinkable compounds having a cyclocarbonate group include N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N'-di[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-phenylenediamine, and those described in paragraphs

[0025] to

[0030] and paragraph

[0032] of WO2011 / 155577.

[0145] Specific examples of crosslinkable compounds having a blocked isocyanate group include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals, Inc.), and those described in paragraphs

[0046] to

[0047] of Japanese Patent Publication No. 2014-224978 and paragraphs

[0119] to

[0120] of WO2015 / 141598.

[0146] Specific examples of crosslinkable compounds having a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group include N,N,N',N'-tetrakis(2-hydroxyethyl)adipoamide, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane, and those described in paragraph

[0058] of Japanese Patent Publication No. 2016-118753, paragraph

[0055] of Japanese Patent Publication No. 2016-200798, and paragraphs

[0017] to

[0029] of WO2010 / 074269.

[0147] Specific examples of crosslinkable compounds having polymerizable unsaturated groups include glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-,1,3-compound mixture), glycerin tris(meth)acrylate, glycerol 1,3-diglycerolate di(meth)acrylate, pentaerythritol tri(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, pentaethylene glycol mono(meth)acrylate, and hexaethylene glycol mono(meth)acrylate.

[0148] In particular, from the viewpoint of the optical properties of the phase difference material, it is preferable to use the following crosslinkable compounds. Specifically, these include NK ester A-DCP, A-BPE-4, A-BPE-10, APG-100, APG-200, APG-400, A-9300, A-DPH, A-GLY-9E, A-GLY-20E, DCP, 4G, 9G, BPE-100, BPE-200, 9PG, and TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0149] The amount of crosslinkable compound used in the phase difference material composition is preferably 0.1 to 100 parts by mass per 100 parts by mass of all polymer components. More preferably, from the viewpoint of allowing the crosslinking reaction to proceed and the desired effect to be achieved, it is 0.1 to 50 parts by mass. Particularly preferred is 1 to 30 parts by mass.

[0150] The composition for the phase difference material may also use compounds that improve the uniformity of the film thickness and surface smoothness of the phase difference material, and compounds that improve the adhesion between the phase difference material and the substrate. Examples of compounds that improve the uniformity of the film thickness and surface smoothness of the phase difference material include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. A specific example is the surfactant described in paragraph

[0122] of WO2014 / 171493. The usage ratio is preferably 0.01 to 2 parts by mass per 100 parts by mass of all polymer components. More preferably, it is 0.01 to 1 part by mass.

[0151] Specific examples of compounds that improve the adhesion between the phase difference material and the substrate include the compounds described in paragraph

[0123] of WO2014 / 171493. The preferred usage ratio is 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all polymer components.

[0152] <Phase Difference Material> The phase difference material according to the present invention can be manufactured, for example, by a method including the following steps (1) to (3).

[0153] [Step (1): Step of forming a phase difference material by applying a phase difference material composition onto a substrate] Step (1) is the step of applying a phase difference material composition onto a substrate.

[0154] The substrate is not particularly limited, and examples include silicon / silicon dioxide coated substrates, silicon nitride substrates, glass substrates coated with aluminum, molybdenum, or chromium, quartz substrates, and ITO (Indium Tin Oxide) substrates. Furthermore, plastic substrates such as TAC (triacetylcellulose) substrates, cycloolefin polymer substrates, PET (polyethylene terephthalate) substrates, acrylic substrates, and polycarbonate substrates, as well as films thereof, can be used.

[0155] The method of applying the phase difference material composition is not particularly limited. Industrially, examples include the dip method, flow coating method, roll coating method, bar coating method, slit coating method, spinner method, spray method, screen printing, offset printing, flexographic printing, or inkjet method. These application methods are used according to the purpose, such as the film thickness of the phase difference material.

[0156] After applying the phase difference material composition to the substrate, the solvent can be evaporated using a heating means such as a hot plate, a hot air circulation oven, or an IR (infrared) oven to form a coating film. The temperature at which this is applied can be selected from 50 to 200°C, preferably 50 to 150°C, depending on the type of substrate and the solvent used in the phase difference material composition.

[0157] [Step (2): Step of irradiating the coating film with polarized ultraviolet light] Step (2) is a step of irradiating the coating surface of the coating film obtained in step (1) with polarized ultraviolet light, and is a step of irradiating the coating film with polarized ultraviolet light from a certain direction via a polarizing plate.

[0158] Ultraviolet light with a wavelength of 100 to 400 nm can be used. In this case, ultraviolet light with a wavelength of 290 to 400 nm is preferred so that the photocrosslinking reaction of specific polymers can be selectively induced. Furthermore, it is preferable to use a filter that can select the optimal wavelength depending on the phase difference material used. Specifically, this could be a bandpass filter with a central wavelength of 365 nm or a long-wave pass filter that transmits wavelengths longer than 313 nm.

[0159] The ultraviolet light source is not particularly limited and can include low-pressure mercury lamps, high-pressure mercury lamps, deep UV lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, mercury xenon lamps, excimer lasers, fluorescent lamps, LED lamps, halogen lamps, or microwave-excited electrodeless lamps.

[0160] [Step (3): Step of heating the ultraviolet-irradiated coating] Step (3) is a step of heating the ultraviolet-irradiated coating obtained in step (2). This heating imparts orientation control ability to the phase difference material.

[0161] The heating means described in step (1) above can be used to heat the coating film. The heating temperature can be appropriately selected according to the temperature at which the phase difference material exhibits liquid crystalline properties. In particular, it is preferable that the temperature is within the temperature range at which a specific polymer exhibits liquid crystalline properties (hereinafter also referred to as the "liquid crystal exhibiting temperature"). More preferably, the temperature range is set with the lower limit of the liquid crystal exhibiting temperature range as the lower limit and the upper limit being 10°C lower than the upper limit of that liquid crystal exhibiting temperature range.

[0162] The liquid crystal emergence temperature is defined as a temperature above the liquid crystal transition temperature at which a specific polymer or phase difference material surface undergoes a phase transition from the solid phase to the liquid crystal phase, and below the isotropic phase transition temperature (Tiso) at which a phase transition occurs from the liquid crystal phase to the isotropic phase. For example, exhibiting liquid crystal properties at 130°C or below means that the liquid crystal transition temperature at which the phase transition from the solid phase to the liquid crystal phase occurs is 130°C or below.

[0163] The thickness of the phase difference material obtained in step (3) can be appropriately selected depending on the step height of the substrate used and the optical properties of the phase difference material. Among these, 0.5 to 10 μm is preferred.

[0164] The phase difference material of the present invention can also be manufactured by a method that includes the following step (4) in addition to the above steps (1) to (3). In this method, the thickness of the phase difference material obtained by step (3) is preferably 5 to 300 nm. More preferably, it is 10 to 200 nm.

[0165] [Step (4): Step to form the liquid crystal layer] Step (4) is a step in which polymerizable liquid crystal is applied to the phase difference material obtained in step (3) and cured to form a liquid crystal layer.

[0166] Polymerizable liquid crystals are polymerizable liquid crystal compounds or liquid crystal compositions that polymerize by at least one of the following treatments: heat treatment or ultraviolet irradiation. Known materials such as nematic liquid crystals, cholesteric liquid crystals, discotic liquid crystals, and twisted nematic oriented liquid crystals containing chiral agents can be used.

[0167] Polymerizable liquid crystal compounds preferably have polymerizable functional groups that can be three-dimensionally crosslinked within the molecule.

[0168] Polymerizable functional groups include those that polymerize by ionizing radiation such as ultraviolet light or electron beams, or by heat. Specifically, these include radical polymerizable functional groups and cationic polymerizable functional groups. Radical polymerizable functional groups include functional groups having at least one addition polymerizable ethylenically unsaturated double bond, such as vinyl groups with or without substituents, and acrylate groups (a general term encompassing acryloyl groups, methacryloyl groups, acryloyloxy groups, and methacryloyloxy groups). Cationic polymerizable functional groups include epoxy groups. Other polymerizable functional groups include isocyanate groups and unsaturated triple bonds.

[0169] In the present invention, from the viewpoint of manufacturing a phase difference material, the polymerizable functional group is preferably a functional group having an ethylenically unsaturated double bond, and it is preferable to use a polymerizable liquid crystal compound having a polymerizable functional group at its terminal end.

[0170] The polymerizable liquid crystal may be a mixture of multiple liquid crystal compounds, and may also contain liquid crystal compounds other than the polymerizable liquid crystal compound, polymerizable compounds, polymerization initiators, surfactants, photosensitizers, chain transfer agents, antioxidants, ultraviolet absorbers, radical scavengers, light stabilizers, optically active compounds, silane coupling agents, or solvents.

[0171] Examples of commercially available polymerizable liquid crystals include RMS03-013C and RMS16-089 (both manufactured by Merck). The coating method described in step (1) above can be used to coat the polymerizable liquid crystal.

[0172] After coating with polymerizable liquid crystal, a liquid crystal layer is formed by curing treatment using heat or ultraviolet irradiation. Good orientation can be obtained by performing both heating and ultraviolet irradiation. The heating conditions are appropriately selected depending on the type of polymerizable liquid crystal. For example, 40-80°C for 0.5-5 minutes. For ultraviolet irradiation, unpolarized ultraviolet light with a wavelength of 200-500 nm is used, with an irradiation dose of 50-10,000 mJ / cm². ２ This is preferable. More preferably, 100 to 5,000 mJ / cm². ２ That is the case.

[0173] The phase difference material of the present invention has optical properties suitable for applications such as display elements and recording materials, and is particularly suitable for optical compensation films such as polarizers and phase difference plates for liquid crystal displays and organic EL displays.

[0174] The present invention will be further described in detail below with reference to examples, but it is not limited to these examples.

[0175] The abbreviations used in the synthesis examples, examples, and comparative examples, and the methods for measuring each physical property are as follows: <Solvent> THF: Tetrahydrofuran MeCN: Acetonitrile DMAc: N,N-dimethylacetamide CPN: Cyclopentanone NMP: N-methyl-2-pyrrolidone <Polymerization initiator> AIBN: 2,2'-azobisisobutyronitrile <Polymerization regulator> T1: Dodecane-1-thiol R1: Compound represented by the following formula [R1]

[0176]

[0177] <Specific Compounds> 1-1M to 1-6M: Compounds represented by the following formulas [1-1M] to [1-6M] 1-1A to 1-7A: Compounds represented by the following formulas [1-1A] to [1-7A]

[0178]

[0179] <Second Compound> 2-1M to 2-4M: Compounds represented by the following formulas [2-1M] to [2-4M]

[0180]

[0181] <Other Compounds> 3-1M: Compound represented by the following formula [3-1M]

[0182]

[0183] "Synthesis of Compounds" The compound represented by formula [1-1M] was synthesized with reference to Japanese Patent Publication No. 2023-167636, the compound represented by formula [1-7A] was synthesized with reference to Foelen. Yari, et al. Advanced Optical Materials (2022), 10(22), 2201462., the compound represented by formula [2-1M] was synthesized with reference to N. Kawatsuki et al. Polymer, 2011, 52(25), 5788-5794., the compound represented by formula [2-2M] was synthesized with reference to WO2013-189171, the compound represented by formula [2-3M] was synthesized with reference to WO2014-054785, and the compounds represented by formulas [2-4M] and [3-1M] were synthesized with reference to WO2023171760. The structure of the compound described in the following examples is: １ Identified by 1H-NMR analysis.

[0184] Equipment: Fourier transform superconducting nuclear magnetic resonance spectrometer (FT-NMR) "AVANCE III" (manufactured by BRUKER) 500 MHz, Solvent: Deuterated dimethyl sulfoxide (DMSO-d ６ Standard substance: tetramethylsilane) <Example 1: Synthesis of the compound represented by formula [1-2M]>

[0185]

[0186] 4-hydroxybenzoic acid (25.0 g, 181 mol) was weighed into a 1 L four-necked flask, and THF (250 g) was added and stirred to dissolve. Then, triethylamine (Et) was added. ３N) (27.5 g, 272 mol) was gently added dropwise. The mixture was cooled to an internal temperature of 10°C or below with ice, and chloromethyl methyl ether (MOM-Cl) (16.0 g, 199 mmol) was added dropwise. The mixture was stirred at an internal temperature of 10°C or below for 2 hours. After the reaction was complete, ethyl acetate (500 g) was added to the reaction mixture and washed three times with deionized water (200 g). The organic layer was separated and the solvent was removed by distillation under reduced pressure to obtain a pale yellow liquid. Next, 4-((6-(methylloyloxy)hexyl)oxy)-2-methylbenzoic acid (49.3 g, 154 mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) (44.2 g, 231 mmol), 4-dimethylaminopyridine (DMAP) (1.88 g, 15.4 mmol), and THF (500 g) were added, and the mixture was stirred at 25°C for 18 hours. After the reaction was complete, ethyl acetate (1000 g) was added, and the mixture was washed three times with deionized water (500 g). The organic layer was separated, and the solvent was removed by vacuum distillation to obtain formula [1-2M-1] (pale yellow liquid, 52.1 g, yield 59.4%).

[0187] 52.1 g, 108 mmol of formula [1-2M-1] was weighed into a 1 L four-necked flask, formic acid (420 g) was added, and the mixture was stirred at 60°C for 2 hours. After the reaction was complete, 400 g of deionized water was added to the reaction solution to precipitate a solid, and the precipitate was filtered off. Ethyl acetate (200 g) was added to the obtained precipitate, and after recrystallization, the precipitate was filtered and dried to obtain formula [1-2M] (white solid, 38.6 g, yield 81.5%).

[0188] １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 13.01 (s, 1H), 8.09-8.11 (d, 1H), 8.02-8.04 (d, 2H), 7.38-7.39 (m, 2H), 6.95-6.96 (m, 2H), 6.01 (s, 1H), 5.65 (s , 1H), 4.01-4.11 (m, 4H), 3.31 (s, 3H), 2.58 (s, 3H), 1.88 (s, 3H), 1.73-1.77 (m, 2H), 1.64-1.66 (m, 2H), 1.41-1.45 (m, 4H). <Example 2: Synthesis of compound represented by formula [1-3M]>

[0189] ​

[0190] 4-hydroxy-3-methylbenzoic acid (25.0 g, 164 mol) was weighed into a 1 L four-necked flask, and THF (250 g) was added and stirred until dissolved. Then Et ３ N (24.9 g, 246 mol) was gently added dropwise. This mixture was cooled to an internal temperature of 10°C or below with ice, MOM-Cl (14.6 g, 181 mmol) was added dropwise, and the mixture was stirred at an internal temperature of 10°C or below for 2 hours. After the reaction was complete, ethyl acetate (500 g) was added to the reaction mixture and washed three times with deionized water (200 g). The organic layer was separated and the solvent was removed by vacuum distillation to obtain an orange liquid. Subsequently, 4-((6-(Methacryloyloxy)hexyl)oxy)benzoic acid (42.8 g, 140 mmol), EDC (40.2 g, 209 mmol), DMAP (1.71 g, 14.0 mmol), and THF (500 g) were added, and the mixture was stirred at 25°C for 18 hours. After the reaction was complete, ethyl acetate (1000 g) was added and the mixture was washed three times with deionized water (500 g). The organic layer was separated and the solvent was removed by vacuum distillation to obtain formula [1-3M-1] (orange liquid, 40.9 g, yield 51.4%).

[0191] 40.9 g, 84.4 mmol of formula [1-3M-1] was weighed into a 1 L four-necked flask, formic acid (330 g) was added, and the mixture was stirred at 60°C for 2 hours. After the reaction was complete, 400 g of deionized water was added to the reaction solution to precipitate a solid, and the precipitate was filtered off. Ethyl acetate (200 g) was added to the obtained precipitate, and after recrystallization, the precipitate was filtered and dried to obtain formula [1-3M] (white solid, 21.6 g, yield 58.1%).

[0192] １ H-NMR (500MHz) in DMSO-d ６ ​δ(ppm) = 12.98 (s, 1H), 8.09–8.11 (t, 2H), 7.93 (d, 1H), 7.84–7.86 (m, 1H), 7.32–7.34 (d, 1H), 7.12–7.14 (m, 2H), 6.02 (s, 1H), 5.66 (s, 1H), 4.10–4.14 (m, 4H), 2.21 (s, 1H), 1.88 (s, 1H), 1.75–1.78 (m, 2H), 1.63–1.65 (m, 2H), 1.40–1.49 (m, 4H). <Example 3: Synthesis of the compound represented by formula [1-4M]>

[0193]

[0194] 25.0 g (150 mol) of 3-(4-hydroxyphenyl)propionic acid was weighed into a 1 L four-necked flask, and 250 g of THF was added and stirred until dissolved. Then, Et ３ N (22.8 g, 226 mol) was gently added dropwise. This mixture was cooled to an internal temperature of 10°C or below with ice, MOM-Cl (13.3 g, 165 mmol) was added dropwise, and the mixture was stirred at an internal temperature of 10°C or below for 2 hours. After the reaction was complete, ethyl acetate (500 g) was added to the reaction mixture and washed three times with deionized water (200 g). The organic layer was separated and the solvent was removed by vacuum distillation to obtain an orange liquid. Subsequently, 4-((6-(methylloyloxy)hexyl)oxy)-3-methylbenzoic acid (41.0 g, 128 mmol), EDC (36.8 g, 192 mmol), DMAP (1.56 g, 12.8 mmol), and THF (500 g) were added, and the mixture was stirred at 25°C for 18 hours. After the reaction was complete, ethyl acetate (1000 g) was added and the mixture was washed three times with deionized water (500 g). The organic layer was separated and the solvent was removed by vacuum distillation to obtain formula [1-4M-1] (orange liquid, 48.8 g, yield 63.3%).

[0195] 48.8 g, 95.2 mmol of the compound [1-4M-1] was weighed into a 1 L four-necked flask, and formic acid (330 g) was added. The mixture was stirred at 60°C for 2 hours. After the reaction was complete, 400 g of deionized water was added to the reaction solution to precipitate a solid, which was then filtered off. Ethyl acetate (200 g) was added to the precipitate, and after recrystallization, the product was filtered and dried to obtain the compound [1-4M] (white solid, 38.8 g, yield 87.0%).

[0196] １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 12.14 (s, 1H), 7.90-7.96 (m, 2H), 7.20-7.31 (d, 2H), 7.11-7.15 (m, 3H), 6.01 (s, 1H), 5.65 (s, 1H), 4.10-4.11 (m, 4H), 3.31 (s, 3H), 2.85 (t, 2H), 2.56 (t, 2H), 1.82 (m, 3H), 1.76-1.82 (m, 2H), 1.63-1.69 (m, 2H), 1.47-1.51 (m, 4H). <Example 4: Synthesis of compound represented by formula [1-5M]>

[0197]

[0198] 25.0 g (150 mol) of 3-(4-hydroxyphenyl)propionic acid was weighed into a 1 L four-necked flask, and 250 g of THF was added and stirred until dissolved. Then, Et ３ N (22.8 g, 226 mol) was gently added dropwise. This mixture was cooled to an internal temperature of 10°C or below with ice, MOM-Cl (13.3 g, 165 mmol) was added dropwise, and the mixture was stirred at an internal temperature of 10°C or below for 2 hours. After the reaction was complete, ethyl acetate (500 g) was added to the reaction mixture and washed three times with deionized water (200 g). The organic layer was separated and the solvent was removed by vacuum distillation to obtain an orange liquid. Subsequently, 4-((6-(methylloyloxy)hexyl)oxy)-2-methylbenzoic acid (41.0 g, 128 mmol), EDC (36.8 g, 192 mmol), DMAP (1.56 g, 12.8 mmol), and THF (500 g) were added, and the mixture was stirred at 25°C for 18 hours. After the reaction was complete, ethyl acetate (1000 g) was added and the mixture was washed three times with deionized water (500 g). The organic layer was separated and the solvent was removed by vacuum distillation to obtain formula [1-5M-1] (orange liquid, 40.1 g, yield 56.9%).

[0199] ​40.1 g, 85.6 mmol of formula [1-5M-1] was weighed into a 1 L four-necked flask, formic acid (330 g) was added, and the mixture was stirred at 60°C for 2 hours. After the reaction was complete, 400 g of deionized water was added to the reaction solution to precipitate a solid, and the precipitate was filtered off. Ethyl acetate (200 g) was added to the obtained precipitate, and after recrystallization, the precipitate was filtered and dried to obtain formula [1-5M] (white solid, 24.1 g, yield 60.1%).

[0200] １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 12.16 (s, 1H), 8.08-8.12 (d, 1H), 8.02-8.04 (d, 2H), 7.38-7.39 (m, 2H), 6.95-6.96 (m, 2H), 6.00 (s, 1H), 5.64 (s, 1H), 4 09-4.12 (m, 4H), 3.30 (s, 3H), 2.86 (t, 2H), 2.54 (t, 2H), 1.81 (m, 3H), 1.75-1.83 (m, 2H), 1.62-1.70 (m, 2H), 1.46-1.50 (m, 4H). <Example 14: Synthesis of compound represented by formula [1-1A]> Formula [1-1A-1] was obtained by synthesizing in the same manner as formula [1-4M-1] in Example 3, except that 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid was used instead of 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid, and 4-hydroxybenzoic acid was used instead of 3-(4-hydroxyphenyl)propionic acid. Next, formula [1-1A] was obtained by synthesizing in the same manner as formula [1-4M] in Example 3, except that formula [1-1A-1] was used instead of formula [1-4M-1]. １ ​H-NMR (500MHz)in DMSO-d6: δ (ppm) = 12.71 (s, 1H), 8.15-8.17 (d, 2H), 8.00-8.02 (d, 2H), 7.60-7.62 (d, 2H), 6.42-6.38 (d, 1H), 6.12-6.14 (d, 1H), 5.82-5.84 (d, 1H), 3.95-4.06 (m, 4H), 2.16 (s, 3H), 1.74-1.77 (t, 2H), 1.40-1.63 (m, 6H). <Example 15: Synthesis of compound represented by formula [1-6M]> Formula [1-6M-1] was obtained by synthesizing in the same manner as formula [1-3M-1] in Example 2, except that 4-hydroxy-3-methylbenzenepropionic acid was used instead of 4-hydroxy-3-methylbenzoic acid. Next, formula [1-6M] was obtained by synthesizing in the same manner as formula [1-3M] in Example 2, except that formula [1-6M-1] was used instead of formula [1-3M-1]. １ H-NMR (500MHz) in DMSO-d ６ δ(ppm) = 12.03 (s, 1H), 8.08–8.13 (d, 2H), 7.10–7.18 (m, 5H), 6.01 (s, 1H), 5.65 (s, 1H), 3.97–7.06 (m, 4H), 2.73 (t, 2H), 2.51 (t, 2H), 2.15 (s, 3H), 2.01 (s, 3H), 1.63–1.77 (t, 2H), 1.51–1.60 (m, 6H). <Example 16: Synthesis of the compound represented by formula [1-2A]> Formula [1-2A-1] was obtained by synthesizing in the same manner as formula [1-2M-1] in Example 1, except that 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid was used instead of 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid. Next, formula [1-2A] was obtained by synthesizing in the same manner as formula [1-2M] in Example 1, except that formula [1-2A-1] was used instead of formula [1-2M-1]. １ H-NMR (500MHz) in DMSO-d ６δ(ppm) = 12.71 (s, 1H), 8.13–8.17 (t, 3H), 7.62 (d, 2H), 6.98–7.01 (d, 2H), 6.41 (d, 1H), 6.12 (d, 1H), 5.83 (d, 1H), 3.97–4.06 (m, 4H), 2.48 (s, 3H), 1.75–1.77 (t, 2H), 1.51–1.60 (m, 6H). <Example 17: Synthesis of the compound represented by formula [1-3A]> Formula [1-3A-1] was obtained by synthesizing in the same manner as formula [1-3M-1] in Example 2, except that 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid was used instead of 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid. Next, formula [1-3A] was obtained by synthesizing in the same manner as formula [1-3M] in Example 2, except that formula [1-3A-1] was used instead of formula [1-3M-1]. １ H-NMR (500MHz) in DMSO-d ６ δ(ppm) = 12.74 (s, 1H), 8.06–8.13 (m, 4H), 7.11 (d, 2H), 6.38–6.40 (d, 1H), 6.12 (d, 1H), 5.80–5.83 (d, 1H), 3.96–4.10 (m, 4H), 2.15 (s, 3H), 1.75–1.77 (t, 2H), 1.43–1.60 (m, 6H). <Example 18: Synthesis of the compound represented by formula [1-4A]> Formula [1-4A-1] was obtained by synthesizing in the same manner as formula [1-4M-1] in Example 3, except that 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid was used instead of 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid. Next, formula [1-4A] was obtained by synthesizing in the same manner as formula [1-4M] in Example 3, except that formula [1-4A-1] was used instead of formula [1-4M-1]. １ H-NMR (500MHz) in DMSO-d ６δ(ppm) = 12.04 (s, 1H), 8.00–8.01 (d, 2H), 7.20–7.21 (d, 4H), 7.06 (d, 1H), 6.38–6.40 (d, 1H), 6.10 (d, 1H), 5.82–5.84 (d, 1H), 3.95–4.09 (m, 4H), 2.70–2.73 (t, 2H), 2.49–2.51 (t, 2H), 2.16 (s, 5H), 1.74–1.77 (t, 2H), 1.42–1.62 (m, 6H). <Example 19: Synthesis of the compound represented by formula [1-5A]> Formula [1-5A-1] was obtained by synthesizing in the same manner as formula [1-5M-1] in Example 4, except that 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid was used instead of 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid. Next, formula [1-5A] was obtained by synthesizing in the same manner as formula [1-5M] in Example 4, except that formula [1-5A-1] was used instead of formula [1-5M-1]. １ H-NMR (500MHz) in DMSO-d ６ δ(ppm) = 12.03 (s, 1H), 8.10–8.13 (d, 1H), 7.20–7.21 (m, 4H), 6.98–7.00 (d, 2H), 6.38–6.40 (d, 1H), 6.11 (d, 1H), 5.82–5.85 (d, 1H), 3.97–4.06 (m, 4H), 2.70–2.73 (t, 2H), 2.48–2.52 (m, 5H), 1.75–1.77 (d, 2H), 1.44–1.61 (m, 6H). <Example 20: Synthesis of the compound represented by formula [1-6A]> Formula [1-6A-1] was obtained by synthesizing in the same manner as formula [1-6M-1] in Example 14, except that 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid was used instead of 4-((6-(Acryloyloxy)hexyl)oxy)-2-methylbenzoic acid. Next, formula [1-6A] was obtained by synthesizing in the same manner as formula [1-6M] in Example 14, except that formula [1-6A-1] was used instead of formula [1-6M-1]. １H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 12.04 (s, 1H), 8.10-8.14 (s, 2H), 7.10-7.18 (m, 4H), 6.38-6.41 (d, 1H), 6.10-6.13 (d, 1H), 5.82-5.84 (d , 1H), 3.95-4.03 (m, 4H), 269-2.71 (t, 2H), 2.47-2.50 (t, 2H), 2.15 (s, 3H), 1.75-1.77 (d, 2H), 1.43-1.61 (m, 6H).

[0201] "Synthesis of Polymers" <Synthesis Example 1> 1-1M (6.18 g, 14.0 mmol), 2-1M (1.40 g, 4.21 mmol), 2-2M (3.01 g, 9.83 mmol), AIBN (46.1 mg, 0.281 mmol) and NMP (19.3 g) were added to a 50 mL two-necked flask and stirred at 25°C for 20 minutes to dissolve.

[0202] The reaction solution was purged with nitrogen and heated and stirred for 18 hours in an oil bath set to 60°C. Then, methanol (150 g) was added to the reaction solution, the precipitate was filtered off, washed three times with methanol, and dried to obtain polymer powder (P-1). The weight-average molecular weight (hereinafter also referred to as "Mw") of this polymer powder was 236,100, and the polydispersity (hereinafter also referred to as "PDI"), calculated from the weight-average molecular weight / number-average molecular weight ratio, was 3.5.

[0203] <Synthesis Examples 2-20> As shown in Tables 1 and 2 below, polymer powders (P-2) to (P-20) were obtained by performing the same procedure as in Synthesis Example 1, except that the type and amount of compounds used, the type and amount of polymerization control agent, and the amount of AIBN were changed. The specifications of the polymer powders are shown in Tables 1 and 2.

[0204]

[0205]

[0206] "Manufacturing of Phase Difference Material Compositions" Examples 5 to 13, Examples 21 to 28, and Comparative Examples 1 to 3 described below illustrate examples of the manufacturing of phase difference material compositions. These phase difference material compositions are used for "production of phase difference materials," "evaluation of phase difference," "evaluation of transparency," and "evaluation of reliability."

[0207] The specifications for the phase difference material compositions are shown in Tables 3 and 4.

[0208] "Preparation of Phase Difference Materials" Phase difference materials were prepared using the phase difference material compositions prepared by the methods of the Examples and Comparative Examples. Specifically, the phase difference material composition obtained by the method of the Synthesis Example was applied to a COP (cycloolefin polymer) film using a bar coater to a thickness of 3.6 μm. Then, it was baked in a hot air circulating oven at 70°C for 3 minutes to obtain a coating film. Polarized ultraviolet light at 365 nm, mediated by a 325 nm low-cut filter and polarizer, was applied to the surface of the obtained coating film using a high-pressure mercury lamp at a rate of 100 mJ / cm². ２ The film was irradiated and then heated in an infrared heating furnace at 120°C for 5 minutes to obtain a COP film with a phase difference material.

[0209] "Evaluation of Phase Difference" The phase difference of the phase difference material was evaluated using a COP film with a phase difference material fabricated using the method described above. Specifically, the linear phase difference at a wavelength of 550 nm was measured using an AxoScan (manufactured by Axometrics). A higher phase difference value was considered to indicate better performance in this evaluation.

[0210] The results are shown in Tables 5 and 6.

[0211] "Evaluation of Transparency" The transparency of the phase difference material was evaluated using the COP film with phase difference material described in the "Evaluation of Phase Difference" above. Specifically, the haze of this film was measured using a haze meter (HZ-V3: manufactured by Suga Test Instruments Co., Ltd.). A lower haze value was considered to indicate better performance in this evaluation.

[0212] The results are shown in Tables 5 and 6.

[0213] "Evaluation of Reliability" The reliability of the phase difference material was evaluated using the COP film with phase difference material described in "Evaluation of Phase Difference" above.

[0214] Specifically, the amount of ultraviolet radiation is 100 mJ / cm². ２ The phase difference of a COP film with a phase difference material, prepared under the condition of a heat treatment temperature of 120°C, was measured. Then, this COP film with the phase difference material was left in a constant temperature bath set at 105°C for 200 hours, and the phase difference was measured again. In this evaluation, the closer the phase difference values ​​before and after being left in the constant temperature bath, the higher the thermal stability and the better the reliability.

[0215] More specifically, the smaller the value obtained from [(phase difference value after being left in the constant temperature bath) ÷ (phase difference value before being left in the constant temperature bath) × 100 - 100] (hereinafter also referred to as "rate of change (%)"), the better the evaluation was considered to be.

[0216] The results are shown in Tables 5 and 6.

[0217] <Example 5> 0.70 g of polymer powder (P-1) obtained by the method of Synthesis Example 1 was mixed with CPN (4.30 g), stirred at 25°C for 3 hours, and filtered through a 5.0 μm pore size filter to obtain a phase difference material composition (PD-1). No abnormalities such as turbidity or precipitate formation were observed in this phase difference material composition, confirming that it was a homogeneous solution. Furthermore, the obtained phase difference material composition (PD-1) was used to perform "preparation of phase difference material," "evaluation of phase difference," "evaluation of transparency," and "evaluation of reliability."

[0218] <Examples 6 to 13, Examples 21 to 28 and Comparative Examples 1 to 3> As shown in Tables 3 and 4 below, phase difference material compositions (PD-2) to (PD-20) were obtained by performing the same procedure as in Example 5, except that the type of polymer powder used was changed. No abnormalities such as turbidity or precipitate formation were observed in any of the obtained phase difference material compositions, and it was confirmed that they were uniform solutions. Furthermore, "preparation of phase difference material," "evaluation of phase difference," "evaluation of transparency," and "evaluation of reliability" were performed using the phase difference material compositions (PD-2) to (PD-20). Note that "evaluation of reliability" was performed in Examples 5 to 7, Example 9, Example 10, Example 12, Example 13, Example 21 to 28, and Comparative Examples 1 to 3.

[0219]

[0220]

[0221]

[0222]

[0223] The phase difference material obtained using the phase difference material composition of the embodiment of the present invention exhibits a high phase difference even at a low heat treatment temperature of 120°C, and also has low haze and excellent transparency. Specifically, this involves comparing the embodiment using the specific compound with the comparative example that does not use it, i.e., comparing Examples 5 to 7 with Comparative Example 1, and comparing Examples 9 to 10 with Comparative Example 2.

[0224] Furthermore, the phase difference material in the examples showed excellent reliability, with minimal change in phase difference value even when exposed to high temperatures of 100°C or higher for extended periods. Specifically, this involved comparing examples using a specific compound with comparative examples that did not use it, i.e., comparing Examples 5 to 7 with Comparative Example 3. In particular, it involved comparing Example 5 with Comparative Example 3, as the structures of the compounds were similar.

[0225] From the above points, the examples using the specific compound having the specific structure of the present invention were able to satisfy all of the effects of the present application.

[0226] In this invention, similar effects were obtained even when the polymer synthesis method was changed. Specifically, the same effects as described above were obtained in Example 5 using the free radical polymerization method, Example 12 using the raft polymerization method, and Example 13 using the chain transfer polymerization method.

[0227] In the present invention, in the specific structure of formula [1], X Ａ However, it is located on a benzene ring close to the main chain of the polymer, and its position relative to that benzene ring is X １The more meta the bond position relative to the bond position, the lower the haze and the better the transparency of the resulting phase difference material. Specifically, this involves a comparison between examples using 1-1M and 1-4M, which are specific compounds that meet the above criteria, and examples using 1-2M, 1-3M, and 1-5M, which are specific compounds that do not meet the above criteria. More specifically, this involves a comparison between Example 1 using 1-1M and Examples 2 and 3 using 1-2M and 1-3M, and a comparison between Example 5 using 1-4M and Example 6 using 1-5M.

[0228] By using a phase difference material composition containing the specific polymer of the present invention, a high phase difference can be achieved even at low heat treatment temperatures, providing a phase difference material that is free from turbidity, highly transparent, and highly reliable. In particular, because this effect can be obtained even at low heat treatment temperatures, low heat-resistant materials such as plastic substrates can be used as the substrate for the phase difference material, and furthermore, it is excellent from the perspective of ESG and SDGs. For this reason, the phase difference material of the present invention is useful for display elements such as organic EL elements.

[0229] Furthermore, the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2025-054623, filed on March 27, 2025, are incorporated herein by reference as disclosure of the specification of the present invention.

Claims

1. A composition for a retardation material, comprising a polymer having, in a side chain thereof, a structure represented by the following formula [1]. (X １ is -CH ２ -, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-, -NHCO- or -N(CH ３ )CO-. X ２ represents a hydrogen atom, a hydroxy group, -(CH ２ ) ａ -COOH (a represents an integer of 0 to 4), a cyano group, or a structure represented by the following formula [1A] or the following formula [1B]. X Ａ and X Ｂ each independently represent an alkyl group having 1 to 3 carbon atoms. mA and mB each independently represent an integer of 0 to 4, and at least one of mA and mB represents an integer of 1 or more. * represents a bonding site.) (Z ａ represents a hydrogen atom, a benzene ring, or a benzene ring substituted with a hydroxy group, -(CH ２ ) ａ -COOH (a represents an integer of 0 to 4), an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. Z ｂ represents a hydrogen atom, a hydroxy group, -(CH ２ ) ｃ -COOH (c represents an integer of 0 to 4), a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. R Ａ and R Ｂ each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. za represents an integer of 0 to 12. * represents a bonding site to a benzene ring.) 2. The phase difference material composition according to claim 1, wherein the structure represented by formula [1] is the structure represented by formula [1a] below. (X １ is, -CH ２ -, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) Indicates CO-. X ２ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ａ -COOH (where a is an integer from 0 to 4), a cyano group, and a structure represented by formula [1A] or formula [1B]. X ３ and X ４ Each of these independently represents a single bond, -O-, -COO-, or -OCO-. Ａ and X Ｂ Each of the following independently represents an alkyl group having 1 to 3 carbon atoms. ma represents an integer from 1 to 12. mA and mB each independently represent an integer from 0 to 4, with either mA or mB being an integer of 1 or greater. * indicates a bond to the polymer's main chain.

3. The phase difference material composition according to claim 2, wherein the structure represented by formula [1a] is a structure represented by any of the following formulas [1aa] to [1af]. (X １ａ and X ２ａ Each of these independently represents a single bond, -O-, -COO-, or -OCO-. ３ａ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｃ -COOH (where c is an integer from 0 to 4) or indicates a cyano group. X ４ａ This represents a single bond or an alkylene group having 1 to 12 carbon atoms. ５ａ This refers to a hydrogen atom, a benzene ring, or a hydrogen atom on a ring that forms a hydroxyl group, -(CH ２ ) ａ -COOH (where a is an integer from 0 to 4), represents a benzene ring substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. X ６ａ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｂ -COOH (where b is an integer from 0 to 4), halogen atom, C1-C8 alkyl group, or C1-C8 alkoxy group. X Ａ１ and X Ａ２ Each of the following independently represents an alkyl group having 1 to 3 carbon atoms. maa represents an integer from 1 to 12. mA1 and mA2 each independently represent an integer from 0 to 4, with either mA1 or mA2 being an integer of 1 or greater. * indicates a bond to the polymer's main chain.

4. The phase difference composition according to any one of claims 1 to 3, wherein the polymer further has at least one structure selected from the following formulas [2a] and [2b] in its side chains. (Y １ａ and Y ２ａ These are, independently, single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH) ３ )-, -NHCONH-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) Indicates CO-. Y ３ａ This represents a single bond, a structure shown by formula [2a-A] or formula [2a-B] below. ４ａ The structure shown is represented by formula [2a-C] or formula [2a-D] below. na represents an integer from 1 to 12. * indicates a bond to the polymer's main chain. (Y １Ａ These are single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) indicates CO-. * is Y ２ａ This shows the combination with Y. ** represents Y ４ａ (This shows the combination.) (Y ２Ａ This refers to a hydrogen atom, a benzene ring, or a hydrogen atom on a ring that forms a hydroxyl group, -(CH ２ ) ａ -COOH (where a is an integer from 0 to 4), represents a benzene ring substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Y ３Ａ This represents a structure that includes at least one selected from the following formulas [2-a] to [2-c]. Y ４Ａ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｂ -COOH (where b is an integer from 0 to 4), halogen atom, C1-C8 alkyl group, or C1-C8 alkoxy group. Y ａ and Y ｂ Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. * represents X ３ａ (This shows the combination.) (nA represents an integer between 1 and 12. * indicates a combination.) (Y １ｂ and Y ２ｂ These are, independently, single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH) ３ )-, -NHCONH-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) Indicates CO-. Y ３ｂ The structure is represented by one of the following formulas [2b-A] to [2b-G]. nb is an integer from 1 to 12. * indicates a bond to the polymer's main chain. (Y １Ｂ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｃ -COOH (where c is an integer from 0 to 4) or indicates a cyano group. Y ２Ｂ These are single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) indicates CO-. * is Y ２ｂ (This shows the combination.) 5. The composition for a retardation material according to claim 4, wherein the structure represented by the above formula [2a] is a structure represented by any one of the following formulas [2aa] to [2aj]. (Y ５ａ and Y ６ａ each independently represent a single bond, -O-, -COO- or -OCO-. Y ７ａ represents a single bond or an alkylene group having 1 to 12 carbon atoms. Y ８ａ represents a hydrogen atom, a benzene ring, or a benzene ring substituted with a hydroxy group, -(CH ２ ) ａ a-COOH (a represents an integer of 0 to 4), an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Y ９ａ represents a hydrogen atom, a hydroxy group, -(CH ２ ) ｂ b-COOH (b represents an integer of 0 to 4), a halogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. naa represents an integer of 1 to 12. * represents a bonding site to the main chain of the polymer.) 6. The phase difference material composition according to claim 4, wherein the structure represented by formula [2b] is a structure represented by any of the following formulas [2ba] to [2bg]. (Y ４ｂ and Y ５ｂ These independently represent a single bond, -O-, -COO-, or -OCO-. ６ｂ is a hydrogen atom, a hydroxyl group, -(CH ２ ) ｃ -COOH (where c is an integer from 0 to 4) or a cyano group. nbb is an integer from 1 to 12. * indicates a bond to the polymer's main chain.

7. The phase difference composition according to claim 1 or 2, wherein the polymer has a main chain composed of (meth)acrylate.

8. A phase difference material obtained from the phase difference material composition according to claim 1 or 2.

9. A method for manufacturing a phase difference material, comprising the following steps (1) to (3). (1) A step of applying the phase difference material composition according to claim 1 or 2 onto a substrate to form a coating film. (2) A step of irradiating the coating film with polarized ultraviolet light. (3) A step of heating the coating film that has been irradiated with ultraviolet light.

10. A method for manufacturing a phase difference material, comprising the following steps (1) to (4). (1) A step of applying the phase difference material composition according to claim 1 or 2 onto a substrate to form a coating film. (2) A step of irradiating the coating film with polarized ultraviolet light. (3) A step of heating the coating film that has been irradiated with ultraviolet light. (4) A step of forming a liquid crystal layer on the coating film.

11. Compounds represented by any of the following formulas [1-2M] to [1-6M].

12. A compound represented by any of the following formulas [1-1A] to [1-6A].

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