JP7342579B2 - Laminate and its manufacturing method - Google Patents

Description

The present invention relates to a laminate and a method for manufacturing the same.

2. Description of the Related Art Conventionally, a technique is known in which a laminate is produced by bonding two base materials together using an ultraviolet curable adhesive. For example, a laminate may be manufactured by bonding a base material including a liquid crystal cured layer formed of a cured product of a liquid crystal compound and a base material including a polarizer layer via an ultraviolet curable adhesive. Such a laminate may be used, for example, as a polarizing plate such as a circularly polarizing plate.

On the other hand, upconversion compounds are known that receive excitation light and emit light with a shorter wavelength than the excitation light (Patent Document 1).

JP2014-35527A

Ultraviolet curable adhesives are usually cured by irradiation with ultraviolet light. However, when a base material with low ultraviolet transmittance is used, the adhesive may not be sufficiently cured, and the laminate may have poor heat resistance.
The present invention was devised in view of the above problems, and an object of the present invention is to provide a laminate having excellent heat resistance and a method for manufacturing the same.

The inventors of the present invention have made extensive studies to solve the above problems. As a result, the present inventor found that when base materials that block ultraviolet rays are adhered to each other via an adhesive layer that includes a combination of an ultraviolet curable adhesive and an upconversion compound that can emit ultraviolet light upon receiving visible light, It was discovered that a laminate having excellent heat resistance can be obtained, and the present invention was completed.
That is, the present invention includes the following.

但し、式（Ｉ）において、
Ａｒは、式（ＩＩＩ－２）で表される基を表し、

Ｒ^ｆは、水素原子ならびに炭素原子数１～６のアルキル基から選ばれる基を表し、
Ｒ^ｇは、水素原子、並びに、置換基を有していてもよい炭素原子数１～３０の有機基からなる群より選ばれる基を表し、
Ｒ^ｈは、炭素原子数６～３０の芳香族炭化水素環及び炭素原子数２～３０の芳香族複素環からなる群より選ばれる１以上の芳香環を有する、有機基を表し、
Ｚ^１及びＺ^２は、それぞれ独立して、単結合、－Ｏ－、－Ｏ－ＣＨ_２－、－ＣＨ_２－Ｏ－、－Ｏ－ＣＨ_２－ＣＨ_２－、－ＣＨ_２－ＣＨ_２－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｓ－、－Ｓ－Ｃ（＝Ｏ）－、－ＮＲ^２１－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－ＮＲ^２１－、－ＣＦ_２－Ｏ－、－Ｏ－ＣＦ_２－、－ＣＨ_２－ＣＨ_２－、－ＣＦ_２－ＣＦ_２－、－Ｏ－ＣＨ_２－ＣＨ_２－Ｏ－、－ＣＨ＝ＣＨ－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－ＣＨ＝ＣＨ－、－ＣＨ_２－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－ＣＨ_２－、－ＣＨ_２－Ｏ－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－ＣＨ_２－、－ＣＨ_２－ＣＨ_２－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－ＣＨ_２－ＣＨ_２－、－ＣＨ_２－ＣＨ_２－Ｏ－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－ＣＨ_２－ＣＨ_２－、－ＣＨ＝ＣＨ－、－Ｎ＝ＣＨ－、－ＣＨ＝Ｎ－、－Ｎ＝Ｃ（ＣＨ_３）－、－Ｃ（ＣＨ_３）＝Ｎ－、－Ｎ＝Ｎ－、及び、－Ｃ≡Ｃ－、からなる群より選ばれるいずれかを表し、Ｒ^２１は、それぞれ独立して、水素原子又は炭素原子数１～６のアルキル基を表し、
Ａ^１、Ａ^２、Ｂ^１及びＢ^２は、それぞれ独立して、置換基を有していてもよい環状脂肪族基、及び、置換基を有していてもよい芳香族基、からなる群より選ばれる基を表し、
Ｙ^１～Ｙ^４は、それぞれ独立して、単結合、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－、－ＮＲ^２２－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－ＮＲ^２２－、－Ｏ－Ｃ（＝Ｏ）－Ｏ－、－ＮＲ^２２－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－ＮＲ^２２－、及び、－ＮＲ^２２－Ｃ（＝Ｏ）－ＮＲ^２３－、からなる群より選ばれるいずれかを表し、Ｒ^２２及びＲ^２３は、それぞれ独立して、水素原子又は炭素原子数１～６のアルキル基を表し、
Ｇ^１及びＧ^２は、それぞれ独立して、炭素原子数１～２０の脂肪族炭化水素基；並びに、炭素原子数３～２０の脂肪族炭化水素基に含まれるメチレン基（－ＣＨ_２－）の１以上が－Ｏ－又は－Ｃ（＝Ｏ）－に置換された基；からなる群より選ばれる有機基を表し、Ｇ^１及びＧ^２の前記有機基に含まれる水素原子は、炭素原子数１～５のアルキル基、炭素原子数１～５のアルコキシ基、または、ハロゲン原子に置換されていてもよく、ただし、Ｇ^１及びＧ^２の両末端のメチレン基（－ＣＨ_２－）が－Ｏ－又は－Ｃ（＝Ｏ）－に置換されることはなく、
Ｐ^１及びＰ^２は、それぞれ独立して、重合性基を表し、
ｐ及びｑは、それぞれ独立して、０又は１を表す。
〔４〕 前記第二基材が、偏光子層を含む、〔１〕～〔３〕のいずれか一項に記載の積層体。
〔５〕 前記接着層が、前記紫外線硬化型接着剤を含むＵＶ接着剤層と、前記アップコンバージョン化合物を含むアップコンバージョン層と、を備える、〔１〕～〔４〕のいずれか一項に記載の積層体。
〔６〕
前記アップコンバージョン化合物が、下記式（ＵＣ１）で表される化合物及び式（ＵＣ２）で表される化合物の組み合わせを含む、〔１〕～〔５〕のいずれか一項に記載の積層体。

〔７〕 第一基材及び第二基材の一方に、未硬化状態の紫外線硬化型接着剤と可視光を受けて紫外線を発光できるアップコンバージョン化合物とを含むアップコンバージョン接着層を形成する工程と、
前記アップコンバージョン接着層と、前記第一基材及び前記第二基材の他方とを貼り合わせる工程と、
前記第一基材及び前記第二基材の少なくとも一方を通して、紫外光及び可視光を含む光を前記アップコンバージョン接着層に照射する工程と、をこの順に含み、
前記第一基材の波長３８０ｎｍにおける光透過率が、１０．０％未満であり、
前記第二基材の波長３８０ｎｍにおける光透過率が、１０．０％未満である、積層体の製造方法。
〔８〕 第一基材及び第二基材の一方に、可視光を受けて紫外線を発光できるアップコンバージョン化合物を含むアップコンバージョン層を形成する工程と、
前記アップコンバージョン層上に、未硬化状態の紫外線硬化型接着剤を含むＵＶ接着剤層を形成する工程と、
前記ＵＶ接着剤層と、前記第一基材及び前記第二基材の他方とを貼り合わせる工程と、
前記第一基材及び前記第二基材の少なくとも一方を通して、紫外光及び可視光を含む光を前記ＵＶ接着剤層に照射する工程と、をこの順に含み、
前記第一基材の波長３８０ｎｍにおける光透過率が、１０．０％未満であり、
前記第二基材の波長３８０ｎｍにおける光透過率が、１０．０％未満である、積層体の製造方法。
〔９〕 前記第一基材が、重合性液晶化合物を含む、〔７〕又は〔８〕に記載の積層体の製造方法。
〔１０〕 前記重合性液晶化合物が、下記式（Ｉ）で表される、〔９〕に記載の積層体の製造方法。

但し、式（Ｉ）において、
Ａｒは、式（ＩＩＩ－２）で表される基を表し、

Ｒ^ｆは、水素原子ならびに炭素原子数１～６のアルキル基から選ばれる基を表し、
Ｒ^ｇは、水素原子、並びに、置換基を有していてもよい炭素原子数１～３０の有機基からなる群より選ばれる基を表し、
Ｒ^ｈは、炭素原子数６～３０の芳香族炭化水素環及び炭素原子数２～３０の芳香族複素環からなる群より選ばれる１以上の芳香環を有する、有機基を表し、
Ｚ^１及びＺ^２は、それぞれ独立して、単結合、－Ｏ－、－Ｏ－ＣＨ_２－、－ＣＨ_２－Ｏ－、－Ｏ－ＣＨ_２－ＣＨ_２－、－ＣＨ_２－ＣＨ_２－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｓ－、－Ｓ－Ｃ（＝Ｏ）－、－ＮＲ^２１－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－ＮＲ^２１－、－ＣＦ_２－Ｏ－、－Ｏ－ＣＦ_２－、－ＣＨ_２－ＣＨ_２－、－ＣＦ_２－ＣＦ_２－、－Ｏ－ＣＨ_２－ＣＨ_２－Ｏ－、－ＣＨ＝ＣＨ－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－ＣＨ＝ＣＨ－、－ＣＨ_２－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－ＣＨ_２－、－ＣＨ_２－Ｏ－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－ＣＨ_２－、－ＣＨ_２－ＣＨ_２－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－ＣＨ_２－ＣＨ_２－、－ＣＨ_２－ＣＨ_２－Ｏ－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－ＣＨ_２－ＣＨ_２－、－ＣＨ＝ＣＨ－、－Ｎ＝ＣＨ－、－ＣＨ＝Ｎ－、－Ｎ＝Ｃ（ＣＨ_３）－、－Ｃ（ＣＨ_３）＝Ｎ－、－Ｎ＝Ｎ－、及び、－Ｃ≡Ｃ－、からなる群より選ばれるいずれかを表し、Ｒ^２１は、それぞれ独立して、水素原子又は炭素原子数１～６のアルキル基を表し、
Ａ^１、Ａ^２、Ｂ^１及びＢ^２は、それぞれ独立して、置換基を有していてもよい環状脂肪族基、及び、置換基を有していてもよい芳香族基、からなる群より選ばれる基を表し、
Ｙ^１～Ｙ^４は、それぞれ独立して、単結合、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－、－ＮＲ^２２－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－ＮＲ^２２－、－Ｏ－Ｃ（＝Ｏ）－Ｏ－、－ＮＲ^２２－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－ＮＲ^２２－、及び、－ＮＲ^２２－Ｃ（＝Ｏ）－ＮＲ^２３－、からなる群より選ばれるいずれかを表し、Ｒ^２２及びＲ^２３は、それぞれ独立して、水素原子又は炭素原子数１～６のアルキル基を表し、
Ｇ^１及びＧ^２は、それぞれ独立して、炭素原子数１～２０の脂肪族炭化水素基；並びに、炭素原子数３～２０の脂肪族炭化水素基に含まれるメチレン基（－ＣＨ_２－）の１以上が－Ｏ－又は－Ｃ（＝Ｏ）－に置換された基；からなる群より選ばれる有機基を表し、Ｇ^１及びＧ^２の前記有機基に含まれる水素原子は、炭素原子数１～５のアルキル基、炭素原子数１～５のアルコキシ基、または、ハロゲン原子に置換されていてもよく、ただし、Ｇ^１及びＧ^２の両末端のメチレン基（－ＣＨ_２－）が－Ｏ－又は－Ｃ（＝Ｏ）－に置換されることはなく、
Ｐ^１及びＰ^２は、それぞれ独立して、重合性基を表し、
ｐ及びｑは、それぞれ独立して、０又は１を表す。
〔１１〕 前記第二基材が、偏光子層を含む、〔７〕～〔１０〕のいずれか一項に記載の積層体の製造方法。 [1] A first base material, an adhesive layer, and a second base material in this order,
The light transmittance of the first base material at a wavelength of 380 nm is less than 10.0%,
The light transmittance of the second base material at a wavelength of 380 nm is less than 10.0%,
The laminate, wherein the adhesive layer includes an ultraviolet curable adhesive and an upconversion compound capable of emitting ultraviolet light upon receiving visible light.
[2] The laminate according to [1], wherein the first base material contains a polymerizable liquid crystal compound.
[3] The laminate according to [2], wherein the polymerizable liquid crystal compound is represented by the following formula (I).

However, in formula (I),
Ar represents a group represented by formula (III-2),

R ^f represents a group selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms,
R ^g represents a group selected from the group consisting of a hydrogen atom and an organic group having 1 to 30 carbon atoms which may have a substituent,
R ^h represents an organic group having one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms;
Z ¹ and Z ² are each independently a single bond, -O-, -O-CH ₂ -, -CH ₂ -O-, -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ - O-, -C(=O)-O-, -OC(=O)-, -C(=O)-S-, -S-C(=O)-, -NR ²¹ -C(= O)-, -C(=O)-NR ²¹ -, -CF ₂ -O-, -O-CF ₂ -, -CH ₂ -CH ₂ -, -CF ₂ -CF ₂ -, -O-CH ₂ -CH ₂ -O-, -CH=CH-C(=O)-O-, -OC(=O)-CH=CH-, -CH ₂ -C(=O)-O-, -O -C(=O)-CH ₂ -, -CH ₂ -O-C(=O)-, -C(=O)-O-CH ₂ -, -CH ₂ -CH ₂ -C(=O)- O-, -OC(=O)-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -OC(=O)-, -C(=O)-O-CH ₂ -CH ₂ - , -CH=CH-, -N=CH-, -CH=N-, -N=C(CH ₃ )-, -C(CH ₃ )=N-, -N=N-, and -C≡ C-, each R ²¹ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A ¹ , A ² , B ¹ and B ² are each independently a group consisting of a cycloaliphatic group which may have a substituent and an aromatic group which may have a substituent. represents a group selected from
Y ¹ to Y ⁴ are each independently a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NR ²² -C(=O)-, -C(=O)-NR ²² -, -OC(=O)-O-, -NR ²² -C(=O)-O-, -OC(= represents one selected from the group consisting of O)-NR ²² - and -NR ²² -C(=O)-NR ²³ -, and R ²² and R ²³ are each independently a hydrogen atom or a carbon represents an alkyl group having 1 to 6 atoms,
G ¹ and G ² are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and a methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group having 3 to 20 carbon atoms; represents an organic group selected from the group consisting of a group in which one or more of is substituted with -O- or -C(=O)-, and the hydrogen atom contained in the organic group of G ¹ and G ² is a carbon atom It may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, provided that the methylene group (-CH ₂ -) at both ends of G ¹ and G ² is -O- or -C(=O)- is not substituted,
P ¹ and P ² each independently represent a polymerizable group,
p and q each independently represent 0 or 1.
[4] The laminate according to any one of [1] to [3], wherein the second base material includes a polarizer layer.
[5] The adhesive layer according to any one of [1] to [4], wherein the adhesive layer includes a UV adhesive layer containing the ultraviolet curable adhesive and an upconversion layer containing the upconversion compound. laminate.
[6]
The laminate according to any one of [1] to [5], wherein the upconversion compound includes a combination of a compound represented by the following formula (UC1) and a compound represented by the formula (UC2).

[7] Forming on one of the first base material and the second base material an upconversion adhesive layer containing an uncured ultraviolet curable adhesive and an upconversion compound capable of emitting ultraviolet light upon receiving visible light; ,
bonding the upconversion adhesive layer to the other of the first base material and the second base material;
irradiating the upconversion adhesive layer with light containing ultraviolet light and visible light through at least one of the first base material and the second base material,
The light transmittance of the first base material at a wavelength of 380 nm is less than 10.0%,
A method for manufacturing a laminate, wherein the second base material has a light transmittance of less than 10.0% at a wavelength of 380 nm.
[8] Forming on one of the first base material and the second base material an upconversion layer containing an upconversion compound capable of emitting ultraviolet light upon receiving visible light;
forming a UV adhesive layer containing an uncured ultraviolet curable adhesive on the upconversion layer;
bonding the UV adhesive layer to the other of the first base material and the second base material;
irradiating the UV adhesive layer with light containing ultraviolet light and visible light through at least one of the first base material and the second base material,
The light transmittance of the first base material at a wavelength of 380 nm is less than 10.0%,
A method for manufacturing a laminate, wherein the second base material has a light transmittance of less than 10.0% at a wavelength of 380 nm.
[9] The method for producing a laminate according to [7] or [8], wherein the first base material contains a polymerizable liquid crystal compound.
[10] The method for producing a laminate according to [9], wherein the polymerizable liquid crystal compound is represented by the following formula (I).

However, in formula (I),
Ar represents a group represented by formula (III-2),

R ^f represents a group selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms,
R ^g represents a group selected from the group consisting of a hydrogen atom and an organic group having 1 to 30 carbon atoms which may have a substituent,
R ^h represents an organic group having one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms;
Z ¹ and Z ² are each independently a single bond, -O-, -O-CH ₂ -, -CH ₂ -O-, -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ - O-, -C(=O)-O-, -OC(=O)-, -C(=O)-S-, -S-C(=O)-, -NR ²¹ -C(= O)-, -C(=O)-NR ²¹ -, -CF ₂ -O-, -O-CF ₂ -, -CH ₂ -CH ₂ -, -CF ₂ -CF ₂ -, -O-CH ₂ -CH ₂ -O-, -CH=CH-C(=O)-O-, -OC(=O)-CH=CH-, -CH ₂ -C(=O)-O-, -O -C(=O)-CH ₂ -, -CH ₂ -O-C(=O)-, -C(=O)-O-CH ₂ -, -CH ₂ -CH ₂ -C(=O)- O-, -OC(=O)-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -OC(=O)-, -C(=O)-O-CH ₂ -CH ₂ - , -CH=CH-, -N=CH-, -CH=N-, -N=C(CH ₃ )-, -C(CH ₃ )=N-, -N=N-, and -C≡ C-, each R ²¹ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A ¹ , A ² , B ¹ and B ² are each independently a group consisting of a cycloaliphatic group which may have a substituent and an aromatic group which may have a substituent. represents a group selected from
Y ¹ to Y ⁴ are each independently a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NR ²² -C(=O)-, -C(=O)-NR ²² -, -OC(=O)-O-, -NR ²² -C(=O)-O-, -OC(= represents one selected from the group consisting of O)-NR ²² - and -NR ²² -C(=O)-NR ²³ -, and R ²² and R ²³ are each independently a hydrogen atom or a carbon represents an alkyl group having 1 to 6 atoms,
G ¹ and G ² are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and a methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group having 3 to 20 carbon atoms; represents an organic group selected from the group consisting of a group in which one or more of is substituted with -O- or -C(=O)-, and the hydrogen atom contained in the organic group of G ¹ and G ² is a carbon atom It may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, provided that the methylene group (-CH ₂ -) at both ends of G ¹ and G ² is -O- or -C(=O)- is not substituted,
P ¹ and P ² each independently represent a polymerizable group,
p and q each independently represent 0 or 1.
[11] The method for producing a laminate according to any one of [7] to [10], wherein the second base material includes a polarizer layer.

According to the present invention, a laminate having excellent heat resistance and a method for manufacturing the same can be provided.

FIG. 1 is a cross-sectional view schematically showing an example of a laminate according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing another example of a laminate according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and may be implemented with arbitrary changes within the scope of the claims of the present invention and equivalents thereof.

In the following description, "ultraviolet light" means light having a wavelength of 1 nm or more and less than 380 nm, unless otherwise specified.

In the following description, "visible light" means light with a wavelength of 380 nm or more and 700 nm or less, unless otherwise specified.

In the following explanation, reverse wavelength dispersion of birefringence means that birefringence Δn (450) at a wavelength of 450 nm and birefringence Δn (550) at a wavelength of 550 nm satisfy the following formula (N1), unless otherwise specified. say. A liquid crystal compound capable of exhibiting birefringence with reverse wavelength dispersion is generally capable of exhibiting greater birefringence as the measurement wavelength becomes longer.
Δn(450)<Δn(550) (N1)

In the following explanation, forward wavelength dispersion of birefringence means birefringence in which birefringence Δn (450) at a wavelength of 450 nm and birefringence Δn (550) at a wavelength of 550 nm satisfy the following formula (N2), unless otherwise specified. means. A liquid crystal compound capable of exhibiting birefringence with normal wavelength dispersion is generally capable of exhibiting a smaller birefringence as the measurement wavelength becomes longer.
Δn(450)>Δn(550) (N2)

In the following description, the in-plane retardation Re of a certain film is a value expressed by Re=(nx-ny)×d, unless otherwise specified. Here, nx represents the refractive index in the direction perpendicular to the thickness direction of the film (in-plane direction) and giving the maximum refractive index. ny represents the refractive index in the in-plane direction of the film and perpendicular to the nx direction. d represents the thickness of the film. The measurement wavelength for retardation is 590 nm unless otherwise specified. In-plane retardation Re can be measured using a phase difference meter ("AxoScan" manufactured by Axometrics).

In the following description, a resin with a positive intrinsic birefringence value means a resin whose refractive index in the stretching direction is larger than the refractive index in the direction orthogonal thereto, unless otherwise specified. Furthermore, a resin with a negative intrinsic birefringence value means a resin whose refractive index in the stretching direction is smaller than the refractive index in the direction orthogonal thereto, unless otherwise specified. The intrinsic birefringence value can be calculated from the dielectric constant distribution.

In the following description, the slow axis of a certain layer refers to the slow axis in the in-plane direction, unless otherwise specified.

In the following description, the number of carbon atoms in a group having a substituent does not include the number of carbon atoms in the substituent unless otherwise specified. Therefore, for example, the description "an alkyl group having 1 to 20 carbon atoms which may have a substituent" means that the alkyl group itself has 1 to 20 carbon atoms, not including the number of carbon atoms in the substituent. represents something.

In the following description, unless otherwise specified, the terms "polarizing plate" and "wavelength plate" are used to include flexible films and sheets such as resin films.

In the following description, unless otherwise specified, the term "(meth)acrylic" includes acrylic, methacrylic, and combinations thereof, and the term "(meth)acrylate" includes acrylate, methacrylate, and combinations thereof. do.

[1. Overview of laminate]
FIG. 1 is a cross-sectional view schematically showing an example of a laminate according to an embodiment of the present invention. As shown in FIG. 1, a laminate 100 according to an embodiment of the present invention includes a first base material 110 having a low light transmittance at a wavelength of 380 nm, an adhesive layer 120, and a second base material 110 having a low light transmittance at a wavelength of 380 nm. and the base material 130 in this order in the thickness direction.

The adhesive layer 120 included in the laminate 100 includes a combination of an ultraviolet curable adhesive and an upconversion compound that can emit ultraviolet light upon receiving visible light. In the following description, an adhesive layer containing a combination of an ultraviolet curable adhesive and an upconversion compound in this manner may be appropriately referred to as an "upconversion adhesive layer." Usually, part or all of the ultraviolet curable adhesive included in the upconversion adhesive layer 120 of the laminate 100 is cured.

The first base material 110 and the second base material 130, which have low light transmittance at a wavelength of 380 nm, generally have the ability to block ultraviolet rays. However, although the first base material 110 and the second base material 130 can block UV rays, the up-conversion adhesive layer 120 can effectively progress the curing of the UV curable adhesive. , the UV-curable adhesive can be cured to a sufficiently high level. Therefore, the laminate 100 can have high heat resistance. Furthermore, the laminate 100 can typically have high light resistance.

Although an arbitrary layer (not shown) may be provided between the first base material 110 and the up-conversion adhesive layer 120, as shown in FIG. It is preferable that it be in direct contact with 120. Further, an arbitrary layer (not shown) may be provided between the up-conversion adhesive layer 120 and the second base material 130, but as shown in FIG. It is preferable to be in direct contact with the base material 130. Here, when two elements are "directly in contact", it means that there is no other layer between them.

The ultraviolet curable adhesive and the upconversion compound may be contained in a single upconversion adhesive layer, or may be contained in separate layers. FIG. 2 is a cross-sectional view schematically showing another example of a laminate according to an embodiment of the present invention. As shown in the example shown in FIG. 2, the laminate 200 includes a UV adhesive layer 221 containing an ultraviolet curable adhesive and a UV adhesive layer 221 containing an upconversion compound between the first base material 110 and the second base material 130. The upconversion adhesive layer 220 may have a multilayer structure including a conversion layer 222.

[2. First base material]
The first base material has low light transmittance at a wavelength of 380 nm. The specific light transmittance of the first base material at a wavelength of 380 nm is usually less than 10.0%, preferably less than 8.0%, and more preferably less than 6.0%. The first base material whose light transmittance at a wavelength of 380 nm is as low as described above usually has an excellent ability to block ultraviolet rays. Since the first base material is thus provided with an excellent ability to block ultraviolet rays, the laminate according to the present embodiment can usually have excellent light resistance.

The light transmittance of the first base material at a wavelength of 380 nm can be measured at an incident angle of 0° using a spectrophotometer (eg, "V-500" manufactured by JASCO Corporation).

As a method for reducing the light transmittance of the first base material at a wavelength of 380 nm as described above, for example, a method of appropriately selecting the material of the first base material can be mentioned. For example, by using a material containing an appropriate type of ultraviolet absorber, the light transmittance of the first base material at a wavelength of 380 nm can be lowered. Further, for example, since the liquid crystal compound represented by the formula (I) described below usually has the ability to absorb ultraviolet rays, a liquid crystal cured layer containing a cured product of a liquid crystal composition containing the liquid crystal compound may be used as the first substrate. The light transmittance of the first base material at a wavelength of 380 nm can also be lowered by the method of providing the first base material at a wavelength of 380 nm.

It is preferable that the first base material has high visible light transmittance. Specifically, it is preferable that the total light transmittance measured at a wavelength of 400 nm to 700 nm is high. The specific range of total light transmittance of the first base material is preferably 20% or more, more preferably 30% or more, particularly preferably 40% or more.

The total light transmittance of the first base material can be measured in the wavelength range of 400 nm to 700 nm using an ultraviolet/visible spectrometer.

There are no particular restrictions on the material of the first base material. For example, the material for the first base material includes a cured product of a liquid crystal composition containing a polymerizable liquid crystal compound. A "liquid crystal composition" includes not only a material containing two or more types of components but also a material containing only one type of polymerizable liquid crystal compound. As described above, the first base material using a cured product of a liquid crystal composition containing a polymerizable liquid crystal compound can usually include a layer of the cured product. In the following description, a layer formed of a cured product of a liquid crystal composition containing a polymerizable liquid crystal compound may be referred to as a "cured liquid crystal layer."

Since the polymerizable liquid crystal compound has liquid crystallinity, it can usually exhibit a liquid crystal phase when the polymerizable liquid crystal compound is oriented. In addition, since the polymerizable liquid crystal compound has polymerizability, it polymerizes while exhibiting a liquid crystal phase, and becomes a polymer without changing the direction in which the maximum refractive index is exhibited in the refractive index ellipsoid of molecules in the liquid crystal phase. be able to. During curing of the liquid crystal composition, the polymerization reaction of the polymerizable liquid crystal compound described above can proceed, so that the alignment state of the polymerizable liquid crystal compound can generally be fixed in the liquid crystal cured layer. Therefore, the liquid crystal cured layer can function as a retardation layer having desired retardation. Moreover, the mechanical strength of the liquid crystal cured layer can be increased by increasing the degree of polymerization of the polymerizable liquid crystal compound.

Molecules of a polymerizable liquid crystal compound having polymerizability usually contain a polymerizable group such as an acryloyl group, a methacryloyl group, and an epoxy group. The number of polymerizable groups per molecule of the polymerizable liquid crystal compound may be one, but preferably two or more.

The molecular weight of the polymerizable liquid crystal compound is preferably 300 or more, more preferably 500 or more, particularly preferably 800 or more, and preferably 2000 or less, more preferably 1700 or less, particularly preferably 1500 or less. When using a polymerizable liquid crystal compound having a molecular weight within such a range, the coating properties of the liquid crystal composition can be particularly improved.

As the polymerizable liquid crystal compound, a reverse dispersion liquid crystal compound may be used, a normal dispersion liquid crystal compound may be used, or a combination of a reverse dispersion liquid crystal compound and a normal dispersion liquid crystal compound may be used.

A reverse dispersion liquid crystal compound is a liquid crystal compound that can exhibit reverse wavelength dispersion birefringence. In addition, a liquid crystal compound capable of exhibiting birefringence with reverse wavelength dispersion is a liquid crystal compound that exhibits birefringence with reverse wavelength dispersion when a layer of the liquid crystal compound is formed and the liquid crystal compound is oriented in that layer. means.

A normal dispersion liquid crystal compound is a liquid crystal compound that can exhibit normal wavelength dispersion birefringence. In addition, a liquid crystal compound that can exhibit normal wavelength dispersion birefringence is a liquid crystal compound that exhibits normal wavelength dispersion birefringence when a layer of the liquid crystal compound is formed and the liquid crystal compound is aligned in that layer. means.

Normally, the wavelength dispersion of birefringence exhibited by a liquid crystal compound can be confirmed by examining the wavelength dispersion of birefringence exhibited by a layer of the liquid crystal compound when the liquid crystal compound is homogeneously aligned. Homogeneously aligning a liquid crystal compound means forming a layer containing the liquid crystal compound, and aligning the direction of the maximum refractive index in the refractive index ellipsoid of molecules of the liquid crystal compound in the layer to a certain point parallel to the plane of the layer. It means to orient it in the direction of. Further, the birefringence of the layer is determined from "(in-plane retardation of the layer)/(thickness of the layer)".

Generally, a reverse dispersion liquid crystal compound can exhibit greater birefringence as the measurement wavelength becomes longer. Therefore, the retardation can be made close to the designed ideal value over a wide wavelength range. Therefore, when an inversely dispersed liquid crystal compound is used as the polymerizable liquid crystal compound, deviation from the ideal value of retardation can be reduced.

The birefringence Δn of the polymerizable liquid crystal compound at a measurement wavelength of 590 nm is preferably 0.01 or more, more preferably 0.03 or more, and preferably 0.15 or less, more preferably 0.10 or less. When using a polymerizable liquid crystal compound having birefringence Δn in such a range, it is easy to obtain a cured liquid crystal layer with few alignment defects.

Birefringence of a liquid crystal compound can be measured, for example, by the method described below.
A layer of a liquid crystal compound is produced, and the liquid crystal compound contained in the layer is homogeneously aligned. Then, the in-plane retardation of that layer is measured. Then, the birefringence of the liquid crystal compound can be determined from "(in-plane retardation of the layer) ÷ (thickness of the layer)". At this time, in order to facilitate measurement of in-plane retardation and thickness, the homogeneously aligned liquid crystal compound layer may be cured.

The polymerizable liquid crystal compound preferably has a side chain having an aromatic ring structure. By introducing a side chain having an aromatic ring structure into the structure, birefringence characteristics can be easily designed and high birefringence can be imparted to the polymerizable liquid crystal compound. As a result, the liquid crystal cured layer can be made thinner, and an increase in retardation change due to uneven curing can be suppressed.

One type of polymerizable liquid crystal compound may be used alone, or two or more types may be used in combination in any ratio.

Examples of polymerizable liquid crystal compounds include liquid crystal compounds represented by the following formula (I). The liquid crystal compound represented by formula (I) can usually exhibit reverse wavelength dispersion birefringence.

In formula (I), Ar is an optionally substituted divalent organic group having 6 to 67 carbon atoms and having at least one of an aromatic heterocycle, a heterocycle, and an aromatic hydrocarbon ring. represents. Examples of aromatic heterocycles include 1H-isoindole-1,3(2H)-dione ring, 1-benzofuran ring, 2-benzofuran ring, acridine ring, isoquinoline ring, imidazole ring, indole ring, and oxadiazole ring. , oxazole ring, oxazolopyrazine ring, oxazolopyridine ring, oxazolopyridazyl ring, oxazolopyrimidine ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline ring, thiadiazole ring, thiazole ring, thiazolopyrazine ring, thia Zolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring, naphthyridine ring, pyrazine ring, pyrazole ring, pyranone ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrrole ring, phenanthridine ring, phthalazine ring, furan ring, benzo[c]thiophene ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, benzoxadiazole ring, benzoxazole ring, benzothiadiazole ring, benzothiazole ring, Examples include a benzothiophene ring, a benzotriazine ring, a benzotriazole ring, a benzopyrazole ring, and a penzopyranone ring. Examples of the heterocycle include 1,3-dithiolane ring, pyrrolidine, piperazine, and the like. Examples of the aromatic hydrocarbon ring include a phenyl ring and a naphthalene ring.

Preferred examples of Ar include groups represented by any of the following formulas (II-1) to (II-4). In formulas (II-1) to (II-4), * represents the bonding position with Z ¹ or Z ² . Moreover, it is preferable that Ar has a benzothiazole ring.

In the above formulas (II-1) to (II-4), E ¹ and E ² each independently represent -CR ¹¹ R ¹² -, -S-, -NR ¹¹ -, -CO- and - Represents a group selected from the group consisting of O-. Further, R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Among these, it is preferable that E ¹ and E ² are each independently -S-.

In the above formulas (II-1) to (II-4), D ¹ to D ² each independently represent an acyclic group that may have a substituent. D ¹ and D ² may be taken together to form a ring. The number of carbon atoms in the groups D ¹ to D ² (including the number of carbon atoms in substituents) is usually 1 to 100, each independently.

The number of carbon atoms in the acyclic group in D ¹ to D ² is preferably 1 to 13. Examples of the acyclic group in D ¹ to D ² include an alkyl group having 1 to 6 carbon atoms; a cyano group; a carboxyl group; a fluoroalkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; ;-C(=O)-CH ₃ ;-C(=O)NHPh; -C(=O)-OR ^x ; Among them, the non-cyclic groups include cyano group, carboxyl group, -C(=O)-CH ₃ , -C(=O)NHPh, -C(=O)-OC ₂ H ₅ , -C(=O) -OC ₄ H ₉ , -C(=O)-OCH(CH ₃ ) ₂ , -C(=O)-OCH ₂ CH ₂ CH(CH ₃ )-OCH ₃ , -C(=O)-OCH ₂ CH ₂ C(CH ₃ ) ₂ -OH and -C(=O)-OCH ₂ CH(CH ₂ CH ₃ )-C ₄ H ₉ are preferred. The above Ph represents a phenyl group. Further, R ^x above represents an organic group having 1 to 12 carbon atoms. Specific examples of R ^x include an alkoxy group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxyl group.

Substituents that the acyclic group in D ¹ to D ² may have include, for example, halogen atoms such as fluorine atoms and chlorine atoms; cyano groups; 6 alkyl group; alkenyl group having 2 to 6 carbon atoms such as vinyl group and allyl group; halogenated alkyl group having 1 to 6 carbon atoms such as trifluoromethyl group; carbon atom such as dimethylamino group N,N-dialkylamino group of number 1 to 12; alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, isopropoxy group; nitro group; -OCF ₃ ; -C(=O)-R ^b ;-O-C(=O)-R ^b ;-C(=O)-O-R ^b ;-SO ₂ R ^a ; and the like. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

R ^a is an alkyl group having 1 to 6 carbon atoms; and 6 carbon atoms, which may have an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms as a substituent; Represents a group selected from the group consisting of ~20 aromatic hydrocarbon ring groups.

R ^b is an alkyl group having 1 to 20 carbon atoms which may have a substituent; an alkenyl group having 2 to 20 carbon atoms which may have a substituent; Represents a group selected from the group consisting of a cycloalkyl group having 3 to 12 carbon atoms; and an aromatic hydrocarbon ring group having 6 to 12 carbon atoms which may have a substituent.

The number of carbon atoms in the alkyl group having 1 to 20 carbon atoms in R ^b is preferably 1 to 12, more preferably 4 to 10. Examples of the alkyl group having 1 to 20 carbon atoms in R ^b include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 1-methylpentyl group, 1-ethylpentyl group. , sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group etc.

Examples of substituents that the alkyl group having 1 to 20 carbon atoms in R ^b may include include halogen atoms such as fluorine atoms and chlorine atoms; cyano groups; and dimethylamino groups having 2 to 12 carbon atoms. N,N-dialkylamino group; Alkoxy group having 1 to 20 carbon atoms, such as methoxy group, ethoxy group, isopropoxy group, butoxy group; 1 to 12 carbon atoms, such as methoxymethoxy group, methoxyethoxy group Alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group; Nitro group; Aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group; Triazolyl group, pyrrolyl group, furanyl group, Aromatic heterocyclic groups having 2 to 20 carbon atoms such as thienyl group, thiazolyl group, benzothiazol-2-ylthio group; cycloalkyl having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group Group; Cycloalkyloxy group having 3 to 8 carbon atoms, such as cyclopentyloxy group and cyclohexyloxy group; Cyclic ether having 2 to 12 carbon atoms, such as tetrahydrofuranyl group, tetrahydropyranyl group, dioxolanyl group, dioxanyl group, etc. Group: Aryloxy group having 6 to 14 carbon atoms, such as phenoxy group and naphthoxy group; At least one hydrogen atom is substituted with a fluorine atom, such as trifluoromethyl group, pentafluoroethyl group, -CH ₂ CF ₃ , etc. Examples include a fluoroalkyl group having 1 to 12 carbon atoms; a benzofuryl group; a benzopyranyl group; a benzodioxolyl group; and a benzodioxanyl group. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

The alkenyl group having 2 to 20 carbon atoms in R ^b preferably has 2 to 12 carbon atoms. Examples of the alkenyl group having 2 to 20 carbon atoms in R ^b include vinyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, undecenyl group , dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, and icosenyl group.

Examples of the substituents that the alkenyl group having 2 to 20 carbon atoms in R ^b may have include the same substituents as the substituents that the alkyl group having 1 to 20 carbon atoms in R ^b can have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Examples of the cycloalkyl group having 3 to 12 carbon atoms for R ^b include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. Among these, as the cycloalkyl group, a cyclopentyl group and a cyclohexyl group are preferable.

Examples of substituents that the cycloalkyl group having 3 to 12 carbon atoms in R ^b include halogen atoms such as fluorine atoms and chlorine atoms; cyano groups; and 2 to 12 carbon atoms such as dimethylamino groups. N,N-dialkylamino group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group; alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, etc. groups; nitro groups; and aromatic hydrocarbon ring groups having 6 to 20 carbon atoms, such as phenyl groups and naphthyl groups. Among these, substituents for cycloalkyl groups include halogen atoms such as fluorine atoms and chlorine atoms; cyano groups; alkyl groups having 1 to 6 carbon atoms such as methyl groups, ethyl groups, and propyl groups; methoxy groups and ethoxy groups; and an alkoxy group having 1 to 6 carbon atoms such as isopropoxy group; a nitro group; and an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Examples of the aromatic hydrocarbon ring group having 6 to 12 carbon atoms in R ^b include phenyl group, 1-naphthyl group, 2-naphthyl group, and the like. Among these, a phenyl group is preferred as the aromatic hydrocarbon ring group.

Examples of the substituents that the aromatic hydrocarbon ring group having 6 to 12 carbon atoms in R ^b may include include halogen atoms such as fluorine atoms and chlorine atoms; cyano groups; dimethylamino groups, etc.; 2 to 12 N,N-dialkylamino groups; alkoxy groups with 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropoxy, butoxy; carbon atoms, such as methoxymethoxy and methoxyethoxy groups; Alkoxy group having 1 to 12 carbon atoms substituted with 1 to 12 alkoxy groups; Nitro group; Aromatic heterocyclic group having 2 to 20 carbon atoms such as triazolyl group, pyrrolyl group, furanyl group, thiophenyl group; Cycloalkyl groups with 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl; cycloalkyloxy groups with 3 to 8 carbon atoms such as cyclopentyloxy and cyclohexyloxy; tetrahydrofuranyl and tetrahydrofuranyl groups; Cyclic ether groups with 2 to 12 carbon atoms, such as pyranyl, dioxolanyl, and dioxanyl groups; aryloxy groups with 6 to 14 carbon atoms, such as phenoxy and naphthoxy groups; trifluoromethyl, pentafluoroethyl a fluoroalkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, such as -CH ₂ CF ₃ ; -OCF ₃ ; benzofuryl group; benzopyranyl group; benzodioxolyl group; Examples include benzodioxanyl group; and the like. Among these, substituents for aromatic hydrocarbon ring groups include halogen atoms such as fluorine atoms and chlorine atoms; cyano groups; methoxy groups, ethoxy groups, isopropoxy groups, and butoxy groups having 1 to 20 carbon atoms; Alkoxy group; Nitro group; Aromatic heterocyclic group having 2 to 20 carbon atoms, such as furanyl group and thiophenyl group; Cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl group, cyclopentyl group, and cyclohexyl group; A fluoroalkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are replaced with a fluorine atom, such as a trifluoromethyl group, a pentafluoroethyl group, and -CH ₂ CF ₃ ; -OCF ₃ ; is preferred. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

When D ¹ and D ² are combined to form a ring, D ¹ and D ² form an organic group containing a ring. Examples of this organic group include groups represented by the following formulas. In the following formula, * represents the position where each organic group is bonded to the carbon to which D ¹ and D ² are bonded.

R ^* represents an alkyl group having 1 to 3 carbon atoms.
R ^** represents a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a phenyl group which may have a substituent.
R ^*** represents a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a phenyl group which may have a substituent.
R ^*** represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, and ^-COOR13 . R ¹³ represents an alkyl group having 1 to 3 carbon atoms.
Examples of substituents that a phenyl group may have include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an acyloxy group, a cyano group, and an amino group. can be mentioned. Among these, as the substituent, a halogen atom, an alkyl group, a cyano group, and an alkoxy group are preferable. The number of substituents that the phenyl group has may be one or more. Furthermore, the plurality of substituents may be the same or different.

In the above formulas (II-1) to (II-4), D ³ is -C(R ^f )=N-N(R ^g )R ^h , -C(R ^f )=N-N=C (R ^g ) represents a group selected from the group consisting of R ^h and -C(R ^f )=N-N=R ⁱ . The number of carbon atoms of the group represented by D ³ (including the number of carbon atoms of substituents) is usually 3 to 100.

R ^f represents a group selected from the group consisting of a hydrogen atom; and an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.

R ^g represents a group selected from the group consisting of a hydrogen atom; and an organic group having 1 to 30 carbon atoms which may have a substituent.

Examples of the organic group having 1 to 30 carbon atoms which may have a substituent in ^Rg include an alkyl group having 1 to 20 carbon atoms which may have a substituent; At least one of -CH ₂ - contained in the 20 alkyl groups is -O-, -S-, -O-C(=O)-, -C(=O)-O-, or -C(= O)--substituted group (excluding cases in which two or more -O- or -S- are interposed adjacent to each other); alkenyl group having 2 to 20 carbon atoms that may have a substituent ; Alkynyl group having 2 to 20 carbon atoms which may have a substituent; Cycloalkyl group having 3 to 12 carbon atoms which may have a substituent; Carbon which may have a substituent Aromatic hydrocarbon ring group having 6 to 30 atoms; Aromatic heterocyclic group having 2 to 30 carbon atoms which may have a substituent; -G ^x -Y ^x -F ^x ; -SO ₂ R ^a ;-C(=O)-R ^b ;-CS-NH-R ^b ; The meanings of R ^a and R ^b are as described above.

The preferred range of the number of carbon atoms and examples of the alkyl group having 1 to 20 carbon atoms in R ^g are the same as the alkyl group having 1 to 20 carbon atoms in R ^b .

Examples of the substituents that the alkyl group having 1 to 20 carbon atoms in ^Rg may include include halogen atoms such as fluorine atoms and chlorine atoms; cyano groups; and dimethylamino groups having 2 to 12 carbon atoms. N,N-dialkylamino group; Alkoxy group having 1 to 20 carbon atoms, such as methoxy group, ethoxy group, isopropoxy group, butoxy group; 1 to 12 carbon atoms, such as methoxymethoxy group, methoxyethoxy group Alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group; Nitro group; Aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group; Triazolyl group, pyrrolyl group, furanyl group, Aromatic heterocyclic groups having 2 to 20 carbon atoms such as thiophenyl group; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group; cyclopentyloxy group, cyclohexyloxy group, etc. , a cycloalkyloxy group having 3 to 8 carbon atoms; a cyclic ether group having 2 to 12 carbon atoms such as a tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxolanyl group, and a dioxanyl group; a carbon group such as a phenoxy group and a naphthoxy group; Aryloxy group having 6 to 14 atoms; fluoroalkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom; benzofuryl group; benzopyranyl group; benzodioxolyl group; benzodioxanyl Groups; --SO ₂ R ^a ; --SR ^b ; C1-12 alkoxy groups substituted with --SR ^b ; hydroxyl groups; and the like. The meanings of R ^a and R ^b are as described above. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

The preferred range of the number of carbon atoms and examples of the alkenyl group having 2 to 20 carbon atoms in R ^g are the same as the alkenyl group having 2 to 20 carbon atoms in R ^b .

Examples of the substituents that the alkenyl group having 2 to 20 carbon atoms in R ^g may have include the same substituents as the substituents that the alkyl group having 1 to 20 carbon atoms in R ^g can have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Examples of the alkynyl group having 2 to 20 carbon atoms in R ^g include ethynyl group, propynyl group, 2-propynyl group (propargyl group), butynyl group, 2-butynyl group, 3-butynyl group, pentynyl group, 2- Examples include pentynyl group, hexynyl group, 5-hexynyl group, heptynyl group, octynyl group, 2-octynyl group, nonanyl group, decanyl group, 7-decanyl group and the like.

Examples of the substituents that the alkynyl group having 2 to 20 carbon atoms in R ^g may have include the same substituents that the alkyl group having 1 to 20 carbon atoms in R ^g can have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Examples of the cycloalkyl group having 3 to 12 carbon atoms in R ^g include the same examples as the cycloalkyl group having 3 to 12 carbon atoms in R ^b .

Examples of the substituents that the cycloalkyl group having 3 to 12 carbon atoms in R ^g may have include the same substituents as the substituents that the alkyl group having 1 to 20 carbon atoms in R ^g can have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Examples of the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R ^g include, for example, a phenyl group, a naphthyl group, and the like. Among these, a phenyl group is more preferable as the aromatic hydrocarbon ring group.

Examples of the substituent that the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R ^g may include are the same as the substituents that the acyclic group in D ¹ to D ² may have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Examples of the aromatic heterocyclic group having 2 to 30 carbon atoms in ^Rg include 1-benzofuranyl group, 2-benzofuranyl group, imidazolyl group, indolinyl group, furazanyl group, oxazolyl group, quinolyl group, thiadiazolyl group, and thiazolyl group. , thiazolopyrazinyl group, thiazolopyridyl group, thiazolopyridazinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyridinyl group, pyrazinyl group, pyrazolyl group, pyranyl group, pyridyl group, Pyridazinyl group, pyrimidinyl group, pyrrolyl group, phthalazinyl group, furanyl group, benzo[c]thienyl group, benzo[b]thienyl group, benzisoxazolyl group, benzisothiazolyl group, benzimidazolyl group, benzoxadiazolyl group , benzoxazolyl group, benzothiadiazolyl group, benzothiazolyl group, benzotriazinyl group, benzotriazolyl group, and benzopyrazolyl group. Among them, examples of aromatic heterocyclic groups include monocyclic aromatic heterocyclic groups such as furanyl group, pyranyl group, thienyl group, oxazolyl group, furazanyl group, thiazolyl group, and thiadiazolyl group; Zolyl group, quinolyl group, 1-benzofuranyl group, 2-benzofuranyl group, phthalimide group, benzo[c]thienyl group, benzo[b]thienyl group, thiazolopyridyl group, thiazolopyrazinyl group, benzisoxazoli More preferred are fused-ring aromatic heterocyclic groups such as a benzoxadiazolyl group, a benzoxadiazolyl group, and a benzothiadiazolyl group.

Examples of substituents that the aromatic heterocyclic group having 2 to 30 carbon atoms in R ^g may include the same substituents as the substituents that the acyclic group in D ¹ to D ² may have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

G ^x is a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; and a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. At least one of -CH ₂ - contained in the aliphatic hydrocarbon group is -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC( =O)-O-, -NR ¹⁴ -C(=O)-, -C(=O)-NR ¹⁴ -, -NR ¹⁴ -, or a group substituted with -C(=O)- (provided that , -O- or -S- (excluding the case where two or more of them are interposed adjacent to each other); represents an organic group selected from the group consisting of; R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The "divalent aliphatic hydrocarbon group" is preferably a divalent chain aliphatic hydrocarbon group, and more preferably an alkylene group.

Y ^x is -O-, -C(=O)-, -S-, -C(=O)-O-, -O-C(=O)-, -O-C(=O)-O -, -C(=O)-S-, -S-C(=O)-, -NR ¹⁵ -C(=O)-, -C(=O)-NR ¹⁵ -, -OC(= O) represents a group selected from the group consisting of -NR ¹⁵ -, -NR ¹⁵ -C(=O)-O-, -N=N-, and -C≡C-. R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among these, -O-, -OC(=O)-O- and -C(=O)-O- are preferable as Y ^x .

F ^x represents an organic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle. The number of carbon atoms in this organic group is preferably 2 or more, more preferably 7 or more, still more preferably 8 or more, particularly preferably 10 or more, and preferably 30 or less. The number of carbon atoms in the organic group does not include carbon atoms in substituents.

Examples of the aromatic hydrocarbon ring in F ^x include aromatic hydrocarbon rings having 6 to 30 carbon atoms, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and a fluorene ring. When F ^x has a plurality of aromatic hydrocarbon rings, the plurality of aromatic hydrocarbon rings may be the same or different.

The aromatic hydrocarbon ring in F ^x may have a substituent. Examples of substituents that the aromatic hydrocarbon ring in F ^x may include include halogen atoms such as fluorine atoms and chlorine atoms; cyano groups; Alkyl group having 2 to 6 carbon atoms, such as vinyl group and allyl group; Halogenated alkyl group having 1 to 6 carbon atoms, such as trifluoromethyl group and pentafluoroethyl group; Dimethylamino group, etc. N,N-dialkylamino group having 2 to 12 carbon atoms; alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, isopropoxy group; nitro group; -OCF ₃ ; -C(= O)-R ^b ;-C(=O)-O-R ^b ;-O-C(=O)-R ^b ; and the like. The meaning of R ^b is as described above. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Examples of the aromatic heterocycle in ^F Diazole ring, oxazole ring, oxazolopyrazine ring, oxazolopyridine ring, oxazolopyridazyl ring, oxazolopyrimidine ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline ring, thiadiazole ring, thiazole ring, thiazolopyrazine ring, thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring, naphthyridine ring, pyrazine ring, pyrazole ring, pyranone ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, Pyrrole ring, phenanthridine ring, phthalazine ring, furan ring, benzo[c]thiophene ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, benzoxadiazole ring, benzoxazole ring, benzothiadiazole ring, benzo Examples include aromatic heterocycles having 2 to 30 carbon atoms, such as a thiazole ring, benzothiophene ring, benzotriazine ring, benzotriazole ring, benzopyrazole ring, and penzopyranone ring. When F ^x has a plurality of aromatic heterocycles, the plurality of aromatic heterocycles may be the same or different.

The aromatic heterocycle in F ^x may have a substituent. Examples of the substituents that the aromatic heterocycle in F ^x can have include the same substituents as the substituents that the aromatic hydrocarbon ring in F ^x can have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

A preferable example of F ^x includes "a cyclic group having 2 to 20 carbon atoms, which has at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, and which may have a substituent." Hereinafter, this cyclic group may be referred to as a "cyclic group (a)" as appropriate.

Examples of the substituents that the cyclic group (a) may have include the same substituents as the substituents that the aromatic hydrocarbon ring in F ^x may have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Preferred examples of the cyclic group (a) include a hydrocarbon cyclic group having 6 to 20 carbon atoms which has at least one aromatic hydrocarbon ring having 6 to 18 carbon atoms and which may have a substituent. Can be mentioned. This hydrocarbon ring group may be appropriately referred to as a "hydrocarbon ring group (a1)" hereinafter.

Examples of the hydrocarbon ring group (a1) include a phenyl group (6 carbon atoms), a naphthyl group (10 carbon atoms), an anthracenyl group (14 carbon atoms), a phenanthrenyl group (14 carbon atoms), and a pyrenyl group. (16 carbon atoms), fluorenyl group (13 carbon atoms), indanyl group (9 carbon atoms), 1,2,3,4-tetrahydronaphthyl group (10 carbon atoms), 1,4-dihydronaphthyl group Examples include aromatic hydrocarbon ring groups having 6 to 18 carbon atoms, such as (having 10 carbon atoms).

Specific examples of the hydrocarbon ring group (a1) include groups represented by the following formulas (1-1) to (1-21). Moreover, these groups may have a substituent. In the following formula, "-" represents a bond with Y ^x extending from any position of the ring.

Another preferred example of the cyclic group (a) is a group having one or more aromatic rings selected from the group consisting of aromatic hydrocarbon rings having 6 to 18 carbon atoms and aromatic heterocycles having 2 to 18 carbon atoms. , a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. This heterocyclic group may be appropriately referred to as a "heterocyclic group (a2)" hereinafter.

Examples of the heterocyclic group (a2) include a phthalimide group, a 1-benzofuranyl group, a 2-benzofuranyl group, an acridinyl group, an isoquinolinyl group, an imidazolyl group, an indolinyl group, a furazanyl group, an oxazolyl group, an oxazolopyrazinyl group, and an oxazolyl group. Zolopyridinyl group, oxazolopyridazinyl group, oxazolopyrimidinyl group, quinazolinyl group, quinoxalinyl group, quinolyl group, cinnolinyl group, thiadiazolyl group, thiazolyl group, thiazolopyrazinyl group, thiazolopyridinyl group , thiazolopyridazinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyridinyl group, pyrazinyl group, pyrazolyl group, pyranonyl group, pyranyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrrolyl group, Phenantridinyl group, phthalazinyl group, furanyl group, benzo[c]thienyl group, benzisoxazolyl group, benzisothiazolyl group, benzimidazolyl group, benzoxazolyl group, benzothiadiazolyl group, benzothiazolyl group, Aromatic heterocyclic groups having 2 to 18 carbon atoms such as benzothiophenyl group, benzotriazinyl group, benzotriazolyl group, benzopyrazolyl group, benzopyranonyl group; xanthenyl group; 2,3-dihydroindolyl group ; 9,10-dihydroacridinyl group; 1,2,3,4-tetrahydroquinolyl group; dihydropyranyl group; tetrahydropyranyl group; dihydrofuranyl group; and tetrahydrofuranyl group.

Specific examples of the heterocyclic group (a2) include groups represented by the following formulas (2-1) to (2-51). Moreover, these groups may have a substituent. In the following formula, "-" represents a bond with Y ^x extending from any position of the ring. In the following formula, X represents -CH ₂ -, -NR ^c -, oxygen atom, sulfur atom, -SO- or -SO ₂ -. Y and Z each independently represent -NR ^c -, an oxygen atom, a sulfur atom, -SO- or -SO ₂ -. E represents -NR ^c -, an oxygen atom or a sulfur atom. Here, R ^c represents a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. (However, in each formula, oxygen atoms, sulfur atoms, -SO-, and -SO ₂ - are not adjacent to each other.)

Another preferable example of ^F and an alkyl group having 1 to 18 carbon atoms, in which a hydrogen atom is substituted and which may have a substituent other than the above-mentioned cyclic group. This substituted alkyl group may be appropriately referred to as a "substituted alkyl group (b)" hereinafter.

Examples of the alkyl group having 1 to 18 carbon atoms in the substituted alkyl group (b) include methyl group, ethyl group, propyl group, and isopropyl group.

In the substituted alkyl group (b), "a cyclic group having 2 to 20 carbon atoms and optionally having a substituent and having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle" includes, for example, a cyclic Examples of the group (a) include the groups described above.

In the substituted alkyl group (b), "at least one of an aromatic hydrocarbon ring and an aromatic heterocycle" may be directly bonded to a carbon atom of an alkyl group having 1 to 18 carbon atoms, and may be a linking group. may be connected via. Examples of the linking group include -S-, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -O-C(=O )-O-, -C(=O)-S-, -SC(=O)-, -NR ¹⁵ -C(=O)-, -C(=O)-NR ¹⁵ , and the like. The meaning of R ¹⁵ is as described above. Therefore, in the substituted alkyl group (b), "a cyclic group having 2 to 20 carbon atoms and optionally having a substituent and having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle" includes a fluorenyl group. , a group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, such as a benzothiazolyl group; an optionally substituted aromatic hydrocarbon ring group; an optionally substituted aromatic heterocyclic group; a linking group A group consisting of an optionally substituted aromatic hydrocarbon ring having a linking group; a group consisting of an optionally substituted aromatic heterocycle having a linking group;

Preferred examples of the aromatic hydrocarbon ring group in the substituted alkyl group (b) include carbonated aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, and fluorenyl group. Examples include hydrogen ring groups.

The aromatic hydrocarbon ring group in the substituted alkyl group (b) may have a substituent. Examples of this substituent include the same substituents that the aromatic hydrocarbon ring in F ^x can have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Preferred examples of the aromatic heterocyclic group in the substituted alkyl group (b) include phthalimide group, 1-benzofuranyl group, 2-benzofuranyl group, acridinyl group, isoquinolinyl group, imidazolyl group, indolinyl group, furazanyl group, oxazolyl group, and oxazolyl group. Zolopyrazinyl group, oxazolopyridinyl group, oxazolopyridazinyl group, oxazolopyrimidinyl group, quinazolinyl group, quinoxalinyl group, quinolyl group, cinnolinyl group, thiadiazolyl group, thiazolyl group, thiazolopyrazinyl group , thiazolopyridyl group, thiazolopyridazinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyridinyl group, pyrazinyl group, pyrazolyl group, pyranonyl group, pyranyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrrolyl group, phenanthridinyl group, phthalazinyl group, furanyl group, benzo[c]thienyl group, benzisoxazolyl group, benzisothiazolyl group, benzimidazolyl group, benzoxadiazolyl group, benzoxazolyl group aromatic heterocyclic groups having 2 to 20 carbon atoms, such as benzothiadiazolyl group, benzothiazolyl group, benzothienyl group, benzotriazinyl group, benzotriazolyl group, benzopyrazolyl group, and benzopyranonyl group. .

The aromatic heterocyclic group in the substituted alkyl group (b) may have a substituent. Examples of this substituent include the same substituents that the aromatic hydrocarbon ring in F ^x can have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Examples of the "group consisting of an aromatic hydrocarbon ring having a linking group" and the "group consisting of an aromatic heterocycle having a linking group" in the substituted alkyl group (b) include phenylthio group, naphthylthio group, anthracenylthio group. , phenanthrenylthio group, pyrenylthio group, fluorenylthio group, phenyloxy group, naphthyloxy group, anthracenyloxy group, phenanthrenyloxy group, pyrenyloxy group, fluorenyloxy group, benzisoxazolylthio group, Benzisothiazolylthio group, benzoxadiazolylthio group, benzoxazolylthio group, benzothiadiazolylthio group, benzothiazolylthio group, benzothienylthio group, benzisoxazolyloxy group, benzisothiazolyl Examples include oxy group, benzoxadiazolyloxy group, benzoxazolyloxy group, benzothiadiazolyloxy group, benzothiazolyloxy group, benzothienyloxy group, and the like.

The "group consisting of an aromatic hydrocarbon ring having a linking group" and the "group consisting of an aromatic heterocycle having a linking group" in the substituted alkyl group (b) may each have a substituent. Examples of this substituent include the same substituents that the aromatic hydrocarbon ring in F ^x can have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Examples of substituents other than the cyclic group that the substituted alkyl group (b) may have include the same substituents that the aromatic hydrocarbon ring in F ^x may have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Specific examples of the substituted alkyl group (b) include groups represented by the following formulas (3-1) to (3-11). Moreover, these groups may have a substituent. In the following formula, "-" represents a bond with Y ^x extending from any position of the ring. Moreover, in the following formula, * represents a bonding position.

In particular, when Ar is represented by formula (II-2), F ^x is preferably a group represented by any of the following formulas (i-1) to (i-9). In addition, especially when Ar is represented by formula (II-3) or formula (II-4), F ^x is a group represented by any of the following formulas (i-1) to (i-13). It is preferable that The groups represented by the following formulas (i-1) to (i-13) may have a substituent. Moreover, in the following formula, * represents a bonding position.

Furthermore, when Ar is represented by formula (II-2), it is particularly preferable that F ^x is a group represented by any of the following formulas (ii-1) to (ii-18). Furthermore, when Ar is represented by formula (II-3) or formula (II-4), F ^x is a group represented by any of the following formulas (ii-1) to (ii-24). It is particularly preferable. The groups represented by the following formulas (ii-1) to (ii-24) may have a substituent. In the following formula, the meaning of Y is as described above. Moreover, in the following formula, * represents a bonding position.

When Ar is represented by formula (II-2), the total number of π electrons contained in the ring structure in F ^x is preferably 8 or more, more preferably 10 or more, and 20 or less. It is preferably 18 or less, and more preferably 18 or less. Furthermore, when Ar is represented by formula (II-3) or formula (II-4), the total number of π electrons contained in the ring structure in F ^x is preferably 4 or more, and 6 or more. It is more preferable that it is 20 or less, and it is more preferable that it is 18 or less.

Among the above, R ^g is an alkyl group having 1 to 20 carbon atoms which may have a substituent; at least one of -CH ₂ - contained in the alkyl group having 1 to 20 carbon atoms; -O-, -S-, -O-C(=O)-, -C(=O)-O-, or -C(=O)- (provided that -O- or - cycloalkyl group having 3 to 12 carbon atoms which may have a substituent; 6 to 12 carbon atoms which may have a substituent 30 aromatic hydrocarbon ring groups; an aromatic heterocyclic group having 2 to 30 carbon atoms which may have a substituent; and -G ^x -Y ^x -F ^x ; are preferred. Among them, R ^g is an alkyl group having 1 to 20 carbon atoms which may have a substituent; at least one of -CH ₂ - contained in the alkyl group having 1 to 20 carbon atoms is -O -, -S-, -O-C(=O)-, -C(=O)-O-, or -C(=O)- (provided that -O- or -S- ); an aromatic hydrocarbon ring group having 6 to 30 carbon atoms which may have a substituent; and -G ^x -Y ^x -F ^x ; Particularly preferred.

R ^h represents an organic group having one or more aromatic rings selected from the group consisting of aromatic hydrocarbon rings having 6 to 30 carbon atoms and aromatic heterocycles having 2 to 30 carbon atoms.

Preferred examples of R ^h include (1) a hydrocarbon ring group having 6 to 40 carbon atoms having one or more aromatic hydrocarbon rings having 6 to 30 carbon atoms; This hydrocarbon ring group having an aromatic hydrocarbon ring may be appropriately referred to as "(1) hydrocarbon ring group" hereinafter. (1) Specific examples of the hydrocarbon ring group include the following groups.

(1) The hydrocarbon ring group may have a substituent. (1) Substituents that the hydrocarbon ring group may have include, for example, halogen atoms such as fluorine atoms and chlorine atoms; cyano groups; Alkyl group; Alkenyl group having 2 to 6 carbon atoms such as vinyl group and allyl group; Halogenated alkyl group having 1 to 6 carbon atoms such as trifluoromethyl group; 2 carbon atoms such as dimethylamino group ~12 N,N-dialkylamino groups; alkoxy groups with 1 to 6 carbon atoms, such as methoxy, ethoxy, and isopropoxy; nitro groups; 6 to 20 carbon atoms, such as phenyl and naphthyl groups; Aromatic hydrocarbon ring group; -OCF ₃ ; -C(=O)-R ^b ; -OC(=O)-R b ; -C(=O ⁾ -O-R ^b ; -SO ₂ R ^a ; and the like. The meanings of R ^a and R ^b are as described above. Among these, halogen atoms, cyano groups, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms are preferred. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Another preferred example of R ^h is (2) having one or more aromatic rings selected from the group consisting of aromatic hydrocarbon rings having 6 to 30 carbon atoms and aromatic heterocycles having 2 to 30 carbon atoms. , a heterocyclic group having 2 to 40 carbon atoms. This heterocyclic group having an aromatic ring may be appropriately referred to as "(2) heterocyclic group" hereinafter. (2) Specific examples of the heterocyclic group include the following groups. Each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

(2) The heterocyclic group may have a substituent. (2) Examples of the substituents that the heterocyclic group may have include the same substituents as (1) the substituents that the hydrocarbon ring group may have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Still another preferred example of R ^h is (3) one or more groups selected from the group consisting of an aromatic hydrocarbon ring group having 6 to 30 carbon atoms and an aromatic heterocyclic group having 2 to 30 carbon atoms. Examples include alkyl groups having 1 to 12 carbon atoms substituted with . This substituted alkyl group may be appropriately referred to as "(3) substituted alkyl group" hereinafter.

(3) Examples of the "alkyl group having 1 to 12 carbon atoms" in the substituted alkyl group include methyl group, ethyl group, propyl group, and isopropyl group.
(3) Examples of the "aromatic hydrocarbon ring group having 6 to 30 carbon atoms" in the substituted alkyl group include the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in ^Rg .
(3) Examples of the "aromatic heterocyclic group having 2 to 30 carbon atoms" in the substituted alkyl group include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in ^Rg .

(3) The substituted alkyl group may further have a substituent. (3) Examples of the substituents that the substituted alkyl group may have include the same substituents as the substituents that (1) the hydrocarbon ring group may have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Still another preferred example of R ^h is (4) one or more groups selected from the group consisting of an aromatic hydrocarbon ring group having 6 to 30 carbon atoms and an aromatic heterocyclic group having 2 to 30 carbon atoms. Examples include alkenyl groups having 2 to 12 carbon atoms substituted with . This substituted alkenyl group may hereinafter be appropriately referred to as "(4) substituted alkenyl group."

(4) Examples of the "alkenyl group having 2 to 12 carbon atoms" in the substituted alkenyl group include a vinyl group and an allyl group.
(4) Examples of the "aromatic hydrocarbon ring group having 6 to 30 carbon atoms" in the substituted alkenyl group include the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in ^Rg .
(4) Examples of the "aromatic heterocyclic group having 2 to 30 carbon atoms" in the substituted alkenyl group include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in ^Rg .

(4) The substituted alkenyl group may further have a substituent. (4) Examples of the substituents that the substituted alkenyl group may have include the same substituents as the substituents that (1) the hydrocarbon ring group may have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Still another preferable example of R ^h is (5) one or more groups selected from the group consisting of an aromatic hydrocarbon ring group having 6 to 30 carbon atoms and an aromatic heterocyclic group having 2 to 30 carbon atoms. Examples include alkynyl groups having 2 to 12 carbon atoms substituted with . This substituted alkynyl group may be appropriately referred to as "(5) substituted alkynyl group" hereinafter.

(5) Examples of the "alkynyl group having 2 to 12 carbon atoms" in the substituted alkynyl group include ethynyl group and propynyl group.
(5) Examples of the "aromatic hydrocarbon ring group having 6 to 30 carbon atoms" in the substituted alkynyl group include the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in ^Rg .
(5) Examples of the "aromatic heterocyclic group having 2 to 30 carbon atoms" in the substituted alkynyl group include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in ^Rg .

(5) The substituted alkynyl group may further have a substituent. (5) Examples of the substituents that the substituted alkynyl group may have include the same substituents as the substituents that (1) the hydrocarbon ring group may have. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Preferred specific examples of R ^h include the following groups.

More preferable specific examples of R ^h include the following groups.

Particularly preferred specific examples of R ^h include the following groups.

The specific examples of R ^h mentioned above may further have a substituent. This substituent includes, for example, a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group; a vinyl group, an allyl group, etc. , an alkenyl group having 2 to 6 carbon atoms; a halogenated alkyl group having 1 to 6 carbon atoms, such as a trifluoromethyl group; an N,N-dialkylamino group having 2 to 12 carbon atoms, such as a dimethylamino group; ; Alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, isopropoxy group; Nitro group; -OCF ₃ ; -C(=O)-R ^b ; -O-C(=O)-R ^b ;-C(=O)-O-R ^b ;-SO ₂ R ^a ; and the like. The meanings of R ^a and R ^b are as described above. Among these, halogen atoms, cyano groups, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms are preferred. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

R ⁱ represents an organic group having one or more aromatic rings selected from the group consisting of aromatic hydrocarbon rings having 6 to 30 carbon atoms and aromatic heterocycles having 2 to 30 carbon atoms.

Preferred examples of R ⁱ include a hydrocarbon ring group having 6 to 40 carbon atoms and having one or more aromatic hydrocarbon ring having 6 to 30 carbon atoms.
Another preferred example of R ⁱ is one or more aromatic rings selected from the group consisting of aromatic hydrocarbon rings having 6 to 30 carbon atoms and aromatic heterocycles having 2 to 30 carbon atoms. Examples include heterocyclic groups having 2 to 40 carbon atoms.

Particularly preferred specific examples of R ⁱ include the following groups. The meaning of R is as described above.

The group represented by any one of formulas (II-1) to (II-4) may further have a substituent in addition to D ¹ to D ³ . Examples of this substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, and an N-alkylamino group having 1 to 6 carbon atoms. group, N,N-dialkylamino group having 2 to 12 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylsulfinyl group having 1 to 6 carbon atoms, carboxyl group, thioalkyl group having 1 to 6 carbon atoms , an N-alkylsulfamoyl group having 1 to 6 carbon atoms, and an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Preferred examples of Ar in formula (I) include groups represented by formulas (III-1) to (III-7) below. Furthermore, the groups represented by formulas (III-1) to (III-7) may have an alkyl group having 1 to 6 carbon atoms as a substituent. In the following formula, * represents the bonding position. Among these, Ar is preferably a group represented by formula (III-2).

Particularly preferred specific examples of formula (III-1) include the following groups. In the following formula, * represents the bonding position.

In formula (I), Z ¹ and Z ² each independently represent a single bond, -O-, -O-CH ₂ -, -CH ₂ -O-, -O-CH ₂ -CH ₂ -, - CH ₂ -CH ₂ -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-S-, -S-C(=O)-, - NR ²¹ -C(=O)-, -C(=O)-NR ²¹ -, -CF ₂ -O-, -O-CF ₂ -, -CH ₂ -CH ₂ -, -CF ₂ -CF ₂ - , -O-CH ₂ -CH ₂ -O-, -CH=CH-C(=O)-O-, -O-C(=O)-CH=CH-, -CH ₂ -C(=O) -O-, -OC(=O)-CH ₂ -, -CH ₂ -OC(=O)-, -C(=O)-O-CH ₂ -, -CH ₂ -CH ₂ - C(=O)-O-, -OC(=O)-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-C(=O)-, -C(=O)-O- CH ₂ -CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH ₃ )-, -C(CH ₃ )=N-, -N=N- , and -C≡C-. R ²¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In formula (I), A ¹ , A ² , B ¹ and B ² are each independently a cycloaliphatic group which may have a substituent, and an aromatic group which may have a substituent. Represents a group selected from the group consisting of group groups. The number of carbon atoms of the groups represented by A ¹ , A ² , B ¹ and B ² (including the number of carbon atoms of substituents) is usually 3 to 100, each independently. Among them, A ¹ , A ² , B ¹ and B ² each independently have a cycloaliphatic group having 5 to 20 carbon atoms, which may have a substituent, or a substituent. Aromatic groups having 2 to 20 carbon atoms are preferred.

Examples of the cycloaliphatic group for A ¹ , A ² , B ¹ and B ² include a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cycloheptane-1,4-diyl group, Cycloalkanediyl groups having 5 to 20 carbon atoms such as cyclooctane-1,5-diyl; carbon atoms such as decahydronaphthalene-1,5-diyl and decahydronaphthalene-2,6-diyl groups; Examples include 5 to 20 bicycloalkanediyl groups; and the like. Among these, an optionally substituted cycloalkanediyl group having 5 to 20 carbon atoms is preferred, a cyclohexanediyl group is more preferred, and a cyclohexane-1,4-diyl group is particularly preferred. The cycloaliphatic group may be in the trans form, the cis form, or a mixture of the cis form and the trans form. Among these, trans isomer is more preferred.

Examples of the substituent that the cycloaliphatic group in A ¹ , A ² , B ¹ and B ² may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, Examples include nitro group and cyano group. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

Examples of the aromatic group in A ¹ , A ² , B ¹ and B ² include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1, Aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as 5-naphthylene group, 2,6-naphthylene group, 4,4'-biphenylene group; furan-2,5-diyl group, thiophene-2,5 -diyl group, pyridine-2,5-diyl group, pyrazine-2,5-diyl group, and other aromatic heterocyclic groups having 2 to 20 carbon atoms; and the like. Among these, aromatic hydrocarbon ring groups having 6 to 20 carbon atoms are preferred, phenylene groups are more preferred, and 1,4-phenylene groups are particularly preferred.

The substituents that the aromatic groups in A ¹ , A ² , B ¹ and B ² may have are the same as the substituents that the cycloaliphatic groups in A ¹ , A ² , B ¹ and B ² may have, for example. An example is given. The number of substituents may be one or more. Furthermore, the plurality of substituents may be the same or different.

In formula (I), Y ¹ to Y ⁴ each independently represent a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O )-, -NR ²² -C(=O)-, -C(=O)-NR ²² -, -OC(=O)-O-, -NR ²² -C(=O)-O-, Represents one selected from the group consisting of -OC(=O)-NR ²² - and -NR ²² -C(=O)-NR ²³ -. R ²² and R ²³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In formula (I), G ¹ and G ² each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and a methylene group contained in the aliphatic hydrocarbon group having 3 to 20 carbon atoms; Represents an organic group selected from the group consisting of a group in which one or more of (-CH ₂ -) is substituted with -O- or -C(=O)-. The hydrogen atoms contained in the organic groups G ¹ and G ² may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. However, the methylene groups (-CH ₂ -) at both ends of G ¹ and G ² are not substituted with -O- or -C(=O)-.

Specific examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in G ¹ and G ² include alkylene groups having 1 to 20 carbon atoms.

Specific examples of the aliphatic hydrocarbon group having 3 to 20 carbon atoms in G ¹ and G ² include alkylene groups having 3 to 20 carbon atoms.

In formula (I), P ¹ and P ² each independently represent a polymerizable group. Examples of the polymerizable group in P ¹ and P ² include a group represented by CH ₂ =CR ³¹ -C(=O)-O- such as an acryloyloxy group and a methacryloyloxy group; a vinyl group; a vinyl ether group; p-stilbene group; acryloyl group; methacryloyl group; carboxyl group; methylcarbonyl group; hydroxyl group; amide group; alkylamino group having 1 to 4 carbon atoms; amino group; epoxy group; oxetanyl group; aldehyde group; isocyanate group; thio Isocyanate group; and the like. R ³¹ represents a hydrogen atom, a methyl group, or a chlorine atom. Among them, a group represented by CH ₂ =CR ³¹ -C(=O)-O- is preferable, such as CH ₂ =CH-C(=O)-O- (acryloyloxy group), CH ₂ =C(CH ₃ )-C(=O)-O-(methacryloyloxy group) is more preferred, and acryloyloxy group is particularly preferred.

In formula (I), p and q each independently represent 0 or 1.

The liquid crystal compound represented by formula (I) can be produced, for example, by the reaction of a hydrazine compound and a carbonyl compound as described in International Publication No. 2012/147904.

Specific examples of the liquid crystal compound represented by formula (I) include compounds represented by the following formula.

The liquid crystal composition may contain arbitrary components in combination with the polymerizable liquid crystal compound. One type of arbitrary components may be used alone, or two or more types may be used in combination in any ratio.

For example, the liquid crystal composition may include a crosslinking agent as an optional component. A crosslinking agent can usually react with a polymerizable liquid crystal compound to form a crosslinking bond. However, the crosslinking agent does not include the polymerizable liquid crystal compound. One type of crosslinking agent may be used alone, or two or more types may be used in combination in any ratio.

The amount of the crosslinking agent is preferably 1 part by weight or more, more preferably 3 parts by weight or more, particularly preferably 5 parts by weight or more, and preferably 30 parts by weight or less, more preferably 3 parts by weight or more, based on 100 parts by weight of the polymerizable liquid crystal compound. The amount is preferably 25 parts by weight or less, particularly preferably 20 parts by weight or less. When the amount of the crosslinking agent is within the above range, the heat resistance and mechanical strength of the cured liquid crystal layer can be effectively increased.

For example, the liquid crystal composition may include a surfactant as an optional component. By using a surfactant, the orientation of the polymerizable liquid crystal compound can be improved, so that the surface condition of the cured liquid crystal layer can be improved and the occurrence of orientation defects can be suppressed. As the surfactant, nonionic surfactants are preferred. Further, as the surfactant, a surfactant containing a fluorine atom in the molecule is preferable. One type of surfactant may be used alone, or two or more types may be used in combination in any ratio.

The amount of the surfactant is preferably 0.005 parts by weight or more, more preferably 0.010 parts by weight or more, and preferably 1.00 parts by weight or less, more preferably is 0.50 parts by weight or less. When the amount of the surfactant is within the above range, the surface condition of the cured liquid crystal layer can be improved and the occurrence of alignment defects can be suppressed.

For example, the liquid crystal composition may include a polymerization initiator as an optional component. By using a polymerization initiator, polymerization of the polymerizable liquid crystal compound can be promoted. As the polymerization initiator, either a thermal polymerization initiator or a photopolymerization initiator may be used. Among these, from the viewpoint of significantly obtaining the desired effects of the present invention, it is preferable to use a photopolymerization initiator. One type of polymerization initiator may be used alone, or two or more types may be used in combination in any ratio.

The amount of the polymerization initiator is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and preferably 30 parts by weight or less, more preferably 10 parts by weight, based on 100 parts by weight of the polymerizable liquid crystal compound. Parts by weight or less. When the amount of the polymerization initiator is within the above range, polymerization can proceed efficiently.

For example, the liquid crystal composition may include an ultraviolet absorber as an optional component. By using an ultraviolet absorber, the light resistance of the liquid crystal cured layer can be effectively improved. One type of ultraviolet absorber may be used alone, or two or more types may be used in combination in any ratio.

The amount of the ultraviolet absorber is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, and preferably 4 parts by weight or less, more preferably 3 parts by weight, based on 100 parts by weight of the polymerizable liquid crystal compound. Parts by weight or less. When the amount of the ultraviolet absorber is at least the lower limit of the above range, the light resistance of the cured liquid crystal layer can be effectively improved. Furthermore, when the amount of the ultraviolet absorber is below the upper limit of the above range, coloring of the cured liquid crystal layer can be effectively suppressed.

For example, the liquid crystal composition may include an antioxidant as an optional component. By using an antioxidant, gelation of an uncured liquid crystal composition can be suppressed, so the pot life of the liquid crystal composition can be extended. One type of antioxidant may be used alone, or two types of antioxidants may be used in combination in any ratio.

The amount of the antioxidant is preferably 0.001 parts by weight or more, more preferably 0.005 parts by weight or more, particularly preferably 0.010 parts by weight or more, based on 100 parts by weight of the polymerizable liquid crystal compound. is 5 parts by weight or less, more preferably 2 parts by weight or less, particularly preferably 1 part by weight or less.

For example, the liquid crystal composition may include a solvent as an optional component. The boiling point of the solvent is preferably 60°C to 250°C, more preferably 60°C to 150°C, from the viewpoint of excellent handling properties. One type of solvent may be used alone, or two or more types may be used in combination in any ratio. The amount of the solvent is preferably 100 parts by weight or more and 1000 parts by weight or less based on 100 parts by weight of the polymerizable liquid crystal compound.

Other optional components that may be included in the liquid crystal composition include, for example, metals; metal complexes; metal oxides such as titanium oxide; colorants such as dyes and pigments; luminescent materials such as fluorescent materials and phosphorescent materials; leveling agents; Examples include thixotropic agents; gelling agents; polysaccharides; infrared absorbers; antioxidants; ion exchange resins; and the like. The amount of each of these components may be 0.1 parts by weight to 20 parts by weight based on a total of 100 parts by weight of the polymerizable liquid crystal compound.

Curing of the above-mentioned liquid crystal composition is generally achieved by progressing a polymerization reaction of a polymerizable compound contained in the liquid crystal composition. Therefore, a cured product of a liquid crystal composition usually contains a polymer of some or all of the components contained in the liquid crystal composition. Therefore, the cured product of the liquid crystal composition may contain a polymer of the polymerizable liquid crystal compound. However, normally, a part of the polymerizable liquid crystal compound contained in the liquid crystal composition is not polymerized and may remain in the cured product as an unreacted polymerizable liquid crystal compound. Therefore, since the liquid crystal cured layer may contain an unreacted polymerizable liquid crystal compound, the first base material including the liquid crystal cured layer may contain an unreacted polymerizable liquid crystal compound.

It can be confirmed that the cured product of the liquid crystal composition contains an unreacted polymerizable liquid crystal compound by immersing the cured product of the liquid crystal composition in tetrahydrofuran and analyzing the resulting solution by liquid chromatography.

In a cured product of a liquid crystal composition, the fluidity that the liquid crystal composition had is generally lost. Therefore, in a cured product of a liquid crystal composition, the alignment state of the polymerizable liquid crystal compound and its polymer can be usually fixed. For example, when a polymerizable liquid crystal compound is polymerized to become a polymer, the orientation direction of the polymer cannot be changed, so that the orientation state can be fixed. Therefore, the cured liquid crystal layer containing the cured product of the liquid crystal composition can have retardation depending on the alignment state.

The specific in-plane retardation range of the liquid crystal cured layer can be arbitrarily set depending on the use of the laminate. For example, the in-plane retardation Re (590) of the liquid crystal cured layer at a wavelength of 590 nm is preferably larger than 100 nm, more preferably larger than 120 nm, particularly preferably larger than 130 nm, and preferably smaller than 200 nm, more preferably 180 nm. less than 160 nm, particularly preferably less than 160 nm. A liquid crystal hardened layer having such an in-plane retardation Re (590) can normally function as a quarter wavelength plate.

The ratio Re(450)/Re(550) of the in-plane retardation Re(450) of the liquid crystal hardened layer at a wavelength of 450 nm and the in-plane retardation Re(550) of the liquid crystal hardened layer at a wavelength of 550 nm is less than 1.00. It is preferable that In detail, the ratio of in-plane retardation Re(450)/Re(550) is preferably less than 1.00, more preferably less than 0.95, particularly preferably less than 0.90, and also preferably It is 0.70 or more, more preferably 0.72 or more, particularly preferably 0.75 or more. A liquid crystal cured layer with an in-plane retardation ratio Re(450)/Re(550) within the above range can exhibit reverse wavelength dispersion, so it can be used as a quarter-wave plate, a half-wave plate, etc. In optical applications, it can exhibit functions uniformly over a wide wavelength range. A liquid crystal cured layer exhibiting reverse wavelength dispersion can be obtained, for example, by using a reverse dispersion liquid crystal compound as a polymerizable liquid crystal compound.

In the direction perpendicular to the thickness direction of the cured liquid crystal layer (in-plane direction), the orientation direction of the molecules of the polymerizable liquid crystal compound and its polymer is usually uniform. Therefore, the liquid crystal cured layer usually has a slow axis parallel to the orientation direction of the molecules of the polymerizable liquid crystal compound and its polymer when the liquid crystal cured layer is viewed from the thickness direction. On the other hand, in the thickness direction of the liquid crystal cured layer, the orientation direction of the molecules of the polymerizable liquid crystal compound and its polymer is arbitrary. For example, in the thickness direction of the liquid crystal cured layer, the orientation direction of the molecules of the polymerizable liquid crystal compound and its polymer may be parallel to the layer plane of the liquid crystal cured layer, or may be non-parallel. Further, in the thickness direction of the liquid crystal cured layer, the orientation direction of the molecules of the polymerizable liquid crystal compound and its polymer may be uniform or nonuniform. To give a specific example, the molecules of the polymerizable liquid crystal compound and its polymer may be oriented in a certain direction parallel to the layer plane of the cured liquid crystal layer (homogeneous alignment). Furthermore, the molecules of the polymerizable liquid crystal compound and its polymer may be oriented in a direction perpendicular to the layer plane of the cured liquid crystal layer (vertical alignment). Furthermore, the molecules of the polymerizable liquid crystal compound and its polymer may be oriented in one direction that is neither parallel nor perpendicular to the layer plane of the cured liquid crystal layer (tilted orientation). Furthermore, the molecules of the polymerizable liquid crystal compound and its polymer are such that the angle of inclination that the molecules of the polymerizable liquid crystal compound and its polymer make with respect to the layer plane of the liquid crystal hardening layer becomes smaller as it approaches one side of the liquid crystal hardening layer. , the orientation may be such that the farther from the one side the larger the orientation (hybrid orientation).

The thickness of the liquid crystal cured layer can be appropriately set so that properties such as retardation can be within a desired range. Specifically, the thickness of the liquid crystal cured layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, and preferably 10 μm or less, more preferably 7 μm or less.

The first base material may have a single layer structure including only one layer, or may have a multilayer structure including two or more layers. Therefore, when the first base material includes the liquid crystal cured layer, the first base material may include any layer in combination with the liquid crystal cured layer. Optional layers include, for example, a support used for manufacturing a liquid crystal cured layer; a stretched or unstretched resin film; an adhesive layer and a pressure-sensitive adhesive layer for adhering to other members; a mat that improves the slipperiness of the film. layers; hard coat layers such as impact-resistant polymethacrylate resin layers; antireflection layers; antifouling layers; and the like. When the first base material includes a combination of a liquid crystal hardening layer and an arbitrary layer, it is preferable that an up-conversion adhesive layer is provided on the liquid crystal hardening layer side of the first base material, and the liquid crystal hardening layer and the up-conversion adhesive layer are provided on the liquid crystal hardening layer side of the first base material. It is more preferable that they are in direct contact with each other.

Examples of the first base material other than the base material containing the liquid crystal cured layer include, for example, the polarizer layer, the protective film layer, and the combination of the polarizer layer and the protective film layer described in the section of the second base material. Examples include. Furthermore, as the first base material, base materials other than those exemplified above, such as a resin film and a glass sheet, may be used, for example, depending on the use of the laminate.

The haze of the first base material is preferably small. The specific haze of the first base material is preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less. Haze can be measured using a haze meter.

There are no particular restrictions on the method for manufacturing the first base material. For example, the first base material including the liquid crystal hardening layer is
(i) forming a layer of liquid crystal composition;
(ii) curing the layer of liquid crystal composition;
It can be manufactured by a manufacturing method including. This manufacturing method will be explained below.

Step (i) typically involves forming a layer of liquid crystal composition on a suitable support surface. Any surface capable of supporting a layer of liquid crystal composition can be used as the supporting surface. From the viewpoint of improving the surface condition of the liquid crystal cured layer, it is preferable to use a flat surface without concave portions or convex portions as the supporting surface. Moreover, from the viewpoint of increasing the productivity of the liquid crystal cured layer, it is preferable to use the surface of a long support as the support surface. Here, "long" refers to a shape that has a length of 5 times or more, preferably 10 times or more of the width, and specifically, a shape that is wound into a roll. The shape of a film that is long enough to be stored or transported. The upper limit of the length is not particularly limited, and may be, for example, 10,000 times the width or less.

As the support, a resin film or a glass plate is usually used. In particular, when performing orientation treatment or heat treatment, it is preferable to select a support that can withstand the treatment temperature. Thermoplastic resin is usually used as the resin. Among these, from the viewpoints of high alignment regulating power, high mechanical strength, and low cost, the resin is preferably a resin having a positive intrinsic birefringence value. Furthermore, it is preferable to use a resin containing an alicyclic structure-containing polymer, such as a norbornene resin, because it has excellent transparency, low moisture absorption, dimensional stability, and light weight. Preferred examples of resins contained in the support are given by trade name, such as "Zeonor" manufactured by Nippon Zeon Co., Ltd., which is a norbornene resin.

The surface of the support serving as the support surface is preferably subjected to a treatment for imparting an alignment regulating force in order to promote alignment of the polymerizable liquid crystal compound in the layer of the liquid crystal composition. The alignment regulating force refers to the property of a surface that can align a liquid crystal compound such as a polymerizable liquid crystal compound contained in a liquid crystal composition. Examples of the treatment for imparting alignment regulating force to the support surface include alignment film forming treatment, photo alignment treatment, rubbing treatment, ion beam alignment treatment, stretching treatment, and the like.

In step (i) of forming a layer of liquid crystal composition, the liquid crystal composition is usually prepared in a fluid state. Therefore, a layer of the liquid crystal composition is usually formed by coating the support surface with a liquid crystal composition. Examples of methods for applying the liquid crystal composition include curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, and gravure coating method. Examples include coating methods, die coating methods, gap coating methods, and dipping methods.

After the step (i) of forming the layer of the liquid crystal composition, a step (iii) of orienting the polymerizable liquid crystal compound contained in the layer of the liquid crystal composition may be performed. When performing alignment treatment, the layer of the liquid crystal composition is usually maintained at a predetermined temperature condition for a predetermined period of time. As a result, a liquid crystal compound such as a polymerizable liquid crystal compound is aligned in the layer of the liquid crystal composition. Conditions for this alignment treatment can be appropriately set depending on the properties of the liquid crystal composition used. To give a specific example of the alignment treatment conditions, the treatment may be performed at a temperature of 50° C. to 160° C. for 30 seconds to 5 minutes.

After step (i), further perform step (iii) of orienting the polymerizable liquid crystal compound as necessary, and then perform step (ii) of curing the layer of the liquid crystal composition to obtain a cured liquid crystal layer. . In step (ii), the layer of the liquid crystal composition is usually cured by polymerizing a polymerizable compound contained in the liquid crystal composition. Therefore, part or all of the polymerizable liquid crystal compound is polymerized in this step (ii). Since the fluidity before curing is lost by curing, the orientation state of the polymerizable liquid crystal compound and its polymer can usually be fixed in the obtained liquid crystal cured layer.

As the polymerization method, a method suitable for the properties of the components contained in the liquid crystal composition can be selected. Examples of the polymerization method include a method of irradiating active energy rays and a thermal polymerization method. Among these, the method of irradiating active energy rays is preferable because it does not require heating and allows the polymerization reaction to proceed at room temperature. Here, the active energy rays to be irradiated may include any energy rays such as visible light, ultraviolet light, infrared light, and electron beams.

Among these, a method of irradiating light such as ultraviolet light is preferred because it is easy to operate. The temperature during ultraviolet irradiation is preferably at most the glass transition temperature of the support, preferably at most 150°C, more preferably at most 100°C, particularly preferably at most 80°C. The lower limit of the temperature during ultraviolet irradiation may be 15° C. or higher. The irradiation intensity of ultraviolet rays is preferably 0.1 mW/cm ² or more, more preferably 0.5 mW/cm ² or more, and preferably 10000 mW/cm ² or less, more preferably 5000 mW/cm ² or less. The amount of ultraviolet irradiation is preferably 0.1 mJ/cm ² or more, more preferably 0.5 mJ/cm ² or more, and preferably 10000 mJ/cm ² or less, more preferably 5000 mJ/cm ² or less.

The method for manufacturing the first base material according to the example described above may further include an arbitrary step.
For example, according to the manufacturing method according to the example described above, a first base material including a support and a cured liquid crystal layer is obtained. Therefore, the manufacturing method described above may include a step of peeling off the support. By peeling off the support, the cured liquid crystal layer itself can be obtained as the first base material. Furthermore, for example, the manufacturing method described above may include a step of transferring the liquid crystal cured layer formed on the support to an arbitrary film. To give a specific example, in the above-mentioned manufacturing method, after bonding a liquid crystal cured layer formed on a support and an arbitrary film, the support is peeled off as necessary, and the liquid crystal cured layer and any film are bonded together. The method may include a step of obtaining a first base material having a multilayer structure including a film of. At this time, an appropriate pressure-sensitive adhesive or adhesive may be used for bonding.

Furthermore, the above-described manufacturing method may include, for example, a step of drying the liquid crystal composition layer before the step (ii) of curing the liquid crystal composition layer. Such drying can be achieved by drying methods such as natural drying, heat drying, reduced pressure drying, and reduced pressure heat drying. Such drying allows the solvent to be removed from the layer of the liquid crystal composition.

Furthermore, the manufacturing method described above may include a step (iv) of subjecting the obtained liquid crystal cured layer to a heat treatment. The heat treatment temperature is preferably 80°C or higher, more preferably 90°C or higher, particularly preferably 100°C or higher, and preferably 180°C or lower, more preferably 170°C or lower, particularly preferably 160°C or lower. Further, the heat treatment time is preferably 1 second or more, more preferably 2 seconds or more, particularly preferably 3 seconds or more, and preferably 15 minutes or less, more preferably 12 minutes or less, particularly preferably 10 minutes or less. By performing heat treatment, the heat resistance of the liquid crystal cured layer can be improved.

[3. Second base material]
The second base material has low light transmittance at a wavelength of 380 nm. The specific light transmittance of the second base material at a wavelength of 380 nm is usually less than 10.0%, preferably less than 6.0%, and more preferably less than 2.0%. The second base material, which has a low light transmittance at a wavelength of 380 nm as described above, usually has an excellent ability to block ultraviolet rays. Since the second base material is thus provided with an excellent ability to block ultraviolet rays, the laminate according to this embodiment can usually have excellent light resistance.

The light transmittance of the second base material at a wavelength of 380 nm can be measured by the same method as the method of measuring the light transmittance of the first base material.

As a method for reducing the light transmittance of the second base material at a wavelength of 380 nm as described above, for example, a method of appropriately selecting a material for the second base material can be mentioned. For example, by using a material containing an appropriate type of ultraviolet absorber, the light transmittance of the second base material at a wavelength of 380 nm can be lowered.

It is preferable that the second base material has high visible light transmittance. Specifically, it is preferable that the total light transmittance measured at a wavelength of 400 nm to 700 nm is high. The specific range of total light transmittance of the second base material may be the same as the range of total light transmittance of the first base material. However, the total light transmittance of the second base material and the total light transmittance of the first base material may be the same or different. The total light transmittance of the second base material can be measured by the same method as the method of measuring the total light transmittance of the first base material.

There are no particular restrictions on the material of the second base material. Further, the second base material may have a single layer structure including only one layer, or may have a multilayer structure including two or more layers. Preferably, the second base material includes a polarizer layer. By using the second base material provided with a polarizer layer, a laminate that can function as a polarizing plate can be obtained.

As a polarizer layer, for example, a film obtained by adsorbing iodine or a dichroic dye on a polyvinyl alcohol film and then uniaxially stretching it in a boric acid bath; adsorbing iodine or a dichroic dye on a polyvinyl alcohol film; A linear polarizer layer such as a film obtained by stretching the polyvinyl alcohol unit and further modifying a part of the polyvinyl alcohol units in the molecular chain into polyvinylene units can be mentioned. Further, other examples of the polarizer layer include polarizers having a function of separating polarized light into reflected light and transmitted light, such as a grid polarizer and a multilayer polarizer. Among these, a polarizer containing polyvinyl alcohol is preferable as the polarizer layer.

When natural light is incident on a polarizer layer, usually only one polarized light is transmitted. The degree of polarization of this polarizer layer is not particularly limited, but is preferably 98% or more, more preferably 99% or more. Further, the thickness of the polarizer layer is preferably 5 μm to 80 μm.

When the second base material includes the polarizer layer described above, the second base material may include any layer in combination with the polarizer layer. An example of such an arbitrary layer is a protective film layer. Usually, the polarizer layer and the protective film layer are provided so that the polarizer layer and the protective film layer are lined up in this order from the upconversion adhesive layer side.

As the protective film layer, for example, a resin film layer can be used. This resin film layer preferably has excellent transparency, mechanical strength, thermal stability, and moisture shielding properties. Examples of such resins include acetate resins such as triacetylcellulose, polyester resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, norbornene resins, and (meth)acrylic resins. Among these, acetate resins, norbornene resins, and (meth)acrylic resins are preferred because of their low birefringence, and norbornene resins are particularly preferred from the viewpoints of transparency, low hygroscopicity, dimensional stability, and light weight.

It is preferable that the protective film layer contains an ultraviolet absorber. A protective film layer containing an ultraviolet absorber can normally function as an ultraviolet cut film having the ability to block ultraviolet light. Moreover, the second base material provided with the protective film layer containing the ultraviolet absorber can usually have low light transmittance at a wavelength of 380 nm. The type and amount of the ultraviolet absorber can be appropriately selected so that the light transmittance of the second base material at a wavelength of 380 nm can be kept within the above range.

Moreover, the second base material may further contain an arbitrary layer in combination with the polarizer layer and the protective film layer. Examples of the arbitrary layer include an adhesive layer and a pressure-sensitive adhesive layer for bonding the polarizer layer and the protective film layer together.

Examples of the second base material other than the base material containing the polarizer layer include, for example, the liquid crystal cured layer described in the section of the first base material, and a combination of the liquid crystal cured layer and any layer. . Furthermore, as the second base material, base materials other than those exemplified above, such as a resin film or a glass sheet, may be used, for example, depending on the use of the laminate.

The haze of the second base material is preferably small. The specific haze range of the second base material may be the same as the haze range of the first base material. However, the haze of the second base material and the haze of the first base material may be the same or different. The haze of the second base material can be measured by the same method as the method of measuring the haze of the first base material.

There are no particular restrictions on the method for manufacturing the second base material. For example, the second base material including the polarizer layer and the protective film layer can be manufactured by a manufacturing method including bonding the polarizer layer and the protective film layer together. An adhesive or a pressure-sensitive adhesive may be used for bonding, if necessary.

[4. Upconversion adhesive layer]
The upconversion adhesive layer includes a UV curable adhesive and an upconversion compound.

An ultraviolet curable adhesive is a type of adhesive that can be cured by exposure to ultraviolet light. Typically, an ultraviolet curable adhesive is applied to one or both of two interfaces to be bonded and, if necessary, is dried appropriately to form an uncured adhesive layer. After that, the objects to be bonded are bonded together through this uncured adhesive layer, and then the adhesive layer is irradiated with ultraviolet rays to be cured and exhibit final adhesive ability. Therefore, the UV-curable adhesive can be included in the upconversion adhesive layer of the laminate in a cured state.

In an uncured state, an ultraviolet curable adhesive usually contains one or more polymerizable compounds that can be polymerized by irradiation with ultraviolet rays. Such polymerizable compounds are generally monomers or oligomers. When the ultraviolet curable adhesive is cured, the polymerization reaction of the polymerizable compound described above can proceed. Therefore, the UV-curable adhesive in a cured state may contain a polymer obtained by polymerizing the polymerizable compound. There are no restrictions on the type of polymerizable compound. Preferred examples of the polymerizable compound include (meth)acrylates described in JP-A No. 2013-29827. Moreover, one type of polymerizable compound may be used alone, or two or more types may be used in combination. The amount of the polymerizable compound or its polymer relative to 100% by weight of the solid content of the ultraviolet curable adhesive is not particularly limited, but is preferably 5% by weight or more, more preferably 10% by weight or more, and preferably is 90% by weight or less, more preferably 60% by weight or less.

The ultraviolet curable adhesive may contain a polymerization initiator that can generate active species upon receiving ultraviolet light. There are no restrictions on the type of polymerization initiator. As a preferable example of the polymerization initiator, those described in JP-A No. 2013-29827 can be used. Moreover, one type of polymerization initiator may be used alone, or two or more types may be used in combination. The amount of the polymerization initiator relative to 100% by weight of the solid content of the ultraviolet curable adhesive is not particularly limited, but is preferably 0.5% by weight or more, more preferably 1% by weight or more, and preferably 10% by weight. The content is more preferably 5% by weight or less.

The ultraviolet curable adhesive may further contain arbitrary components. These arbitrary components may be used alone or in combination of two or more. Optional components that the UV-curable adhesive may contain include, for example, a photosensitizer; a solvent; a monomer containing an isocyanate group in the molecule, a monomer containing a mercapto group in the molecule, etc. to improve adhesive strength; Components: Cationic polymerization curable components such as epoxy compounds, vinyl ether compounds, oxetane compounds, cationic polymerization initiators; Crosslinking agents; Inorganic fillers; Polymerization inhibitors; Coloring agents such as pigments and dyes; Antifoaming agents; Leveling agents ; dispersant; light diffusing agent; plasticizer; antistatic agent; surfactant; non-reactive polymer (inactive polymer); viscosity modifier; near-infrared absorbing material; and the like. For these examples and amounts, reference may be made to, for example, the description in JP-A No. 2013-29827.

Upconversion compounds have the ability to receive visible light and emit ultraviolet light. This ability is not necessarily achieved by one type of compound, but may be achieved by a combination of two or more types of compounds. Thus, upconversion compounds may include a combination of compounds that have the ability to receive visible light and emit ultraviolet light.

Specific examples of the upconversion compound include a combination of a compound represented by formula (UC1) and a compound represented by formula (UC2). In the following description, the compound represented by formula (UC1) may be referred to as a "donor compound (UC1)." Furthermore, the compound represented by formula (UC2) is sometimes referred to as an "acceptor compound (UC2)." In this combination, the donor compound (UC1) absorbs the energy of visible light, and the absorbed energy is supplied to the acceptor compound (UC2), which can then emit ultraviolet light.

In the above combination, the amount of the acceptor compound (UC2) relative to 100 parts by weight of the donor compound (UC1) is preferably 200 parts by weight or more, more preferably 300 parts by weight or more, particularly preferably 400 parts by weight or more, and preferably The amount is 800 parts by weight or less, more preferably 700 parts by weight or less, particularly preferably 600 parts by weight or less. When the quantitative ratio of the donor compound (UC1) and the acceptor compound (UC2) falls within the above range, the upconversion compound containing them can effectively emit ultraviolet rays. Therefore, since the ultraviolet curing adhesive can be effectively cured, the heat resistance of the laminate can be effectively improved.

In the upconversion adhesive layer, the amount of the upconversion compound relative to 100 parts by weight of the solid content of the ultraviolet curable adhesive is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, particularly preferably 1.0 parts by weight. The amount is at least 10 parts by weight, preferably at most 10 parts by weight, more preferably at most 7.5 parts by weight, particularly preferably at most 5.0 parts by weight. When the amount of the upconversion compound is at least the lower limit of the above range, the upconversion compound can emit a sufficient amount of ultraviolet light to promote curing of the ultraviolet curable adhesive. Therefore, since the ultraviolet curing adhesive can be effectively cured, the heat resistance of the laminate can be effectively improved. Moreover, when the amount of the up-conversion compound is below the upper limit of the range, it is possible to suppress the color of the up-conversion compound from affecting the hue of the laminate.

There are no restrictions on the layer structure of the upconversion adhesive layer. Therefore, the upconversion adhesive layer may have a single layer structure including only one layer, or may have a multilayer structure including two or more layers.

If the upconversion adhesive layer has a single layer structure, the single upconversion adhesive layer can include both a UV curable adhesive and an upconversion compound. In this case, the composition of the upconversion adhesive layer may be uniform.

When the upconversion adhesive layer has a multilayer structure, the upconversion adhesive layer may include a combination of a UV adhesive layer containing an ultraviolet curable adhesive and an upconversion layer containing an upconversion compound. In this case, the upconversion adhesive layer may include an upconversion layer and a UV adhesive layer in this order from the first base material side. Further, the up-conversion adhesive layer may include a UV adhesive layer and an up-conversion layer in this order from the first base material side. Furthermore, the upconversion adhesive layer may include a first upconversion layer, a UV adhesive layer, and a second upconversion layer in this order from the first base material side.

The thickness of the upconversion adhesive layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, particularly preferably 0.3 μm or more, and preferably 20 μm or less, more preferably 15 μm or less, particularly preferably 10 μm or less. be. When the thickness of the up-conversion adhesive layer is equal to or greater than the lower limit of the above range, the up-conversion adhesive layer can exhibit high adhesive strength, so that the first base material and the second base material can be strongly bonded. Furthermore, when the thickness of the up-conversion adhesive layer is less than or equal to the upper limit of the above-mentioned range, the ultraviolet curable adhesive in the up-conversion adhesive layer can be effectively cured, so that heat resistance can be effectively increased. I can do it.

When the upconversion adhesive layer has a multilayer structure including a combination of a UV adhesive layer and an upconversion layer, the ratio of the thickness of the UV adhesive layer to the thickness of the upconversion layer (UV adhesive layer/upconversion layer) is , preferably 100/100 or more, more preferably 100/75 or more, particularly preferably 100/50 or more, preferably 100/1 or less, more preferably 100/2.5 or less, particularly preferably 100/5 or less It is. When the thickness ratio (UV adhesive layer/upconversion layer) is at least the lower limit of the above range, the UV adhesive layer can exhibit high adhesive strength, so the first base material and the second base material are strongly bonded. Can be attached to. In addition, when the thickness ratio (UV adhesive layer/upconversion layer) is below the upper limit of the above range, the curing of the ultraviolet curable adhesive in the upconversion adhesive layer can be effectively progressed, so heat resistant It can effectively improve your sexuality.

[5. [any layer]
The laminate according to this embodiment may further include an arbitrary layer in combination with the first base material, second base material, and upconversion adhesive layer described above. Examples of the optional layer include a masking film layer for protecting the laminate when the laminate is wound up.

[6. Characteristics of laminate]
The above-described laminate has excellent heat resistance. In particular, when at least one of the first base material and the second base material is a base material containing a polymerizable liquid crystal compound, such as a base material provided with a liquid crystal hardening layer, the heat resistance of the laminate is determined by the polymerizable liquid crystal compound. It can be expressed by a change in retardation of a substrate containing a compound. Specifically, it can be evaluated that the smaller the change in retardation of a base material containing a polymerizable liquid crystal compound in a high-temperature environment is, the better the heat resistance is. For example, when the first base material includes a liquid crystal cured layer, the first base material may correspond to the above-mentioned "base material containing a polymerizable liquid crystal compound."

More specifically, the heat resistance can be expressed by the absolute value of the rate of change in in-plane retardation ΔRe _H (%) of the base material containing the polymerizable liquid crystal compound in a heat resistance test in which the laminate is heated at 85° C. for 100 hours. can. In one example, the absolute value of the rate of change in in-plane retardation ΔRe _H (%) of the base material containing the polymerizable liquid crystal compound according to the heat resistance test is preferably 2.4% or less, more preferably 2.0% or less, particularly Preferably it is 1.5% or less.

The rate of change in in-plane retardation ΔRe _H (%) determined by the heat resistance test described above can be measured by the following method.
Before the heat resistance test, the in-plane retardation Re _H0 of the base material containing the polymerizable liquid crystal compound included in the laminate is measured. Thereafter, the laminate is subjected to a heat resistance test in which it is heated at 85° C. for 100 hours. After this heat resistance test, the in-plane retardation Re _H100 of the base material containing the polymerizable liquid crystal compound included in the laminate is measured. Using the in-plane retardation Re _H0 before the heat resistance test and the in-plane retardation Re _H100 after the heat resistance test, calculate the rate of change in in-plane retardation ΔRe _H (%) due to the heat resistance test using the following formula (T1). can.
ΔRe _H (%) = {(Re _H100 - Re _H0 )/Re _H0 }×100 (T1)

The above-mentioned laminate usually has excellent light resistance. In particular, when at least one of the first base material and the second base material is a base material containing a polymerizable liquid crystal compound, such as a base material provided with a liquid crystal hardening layer, the light resistance of the laminate is determined by the polymerizable liquid crystal compound. It can be expressed by a change in retardation of a substrate containing a compound. Specifically, it can be evaluated that the smaller the change in retardation of the base material containing the polymerizable liquid crystal compound, the better the light resistance.

More specifically, light resistance is determined by a light resistance test in which the laminate is irradiated with light with an irradiation intensity of 50 mW/cm ² for 300 hours from a high-pressure mercury lamp in an environment at a temperature of 63°C. It can be expressed by the absolute value of the rate of change in retardation ΔRe _L (%). In one example, the absolute value of the rate of change in in-plane retardation ΔRe _L (%) of the substrate containing the polymerizable liquid crystal compound according to the light fastness test is preferably 2.5% or less, more preferably 2.0% or less, particularly Preferably it is 1.5% or less.

The rate of change in in-plane retardation ΔRe _L (%) determined by the light fastness test described above can be measured by the following method.
Before the light resistance test, the in-plane retardation Re _L0 of the base material containing the polymerizable liquid crystal compound included in the laminate is measured. Thereafter, the laminate is subjected to a light resistance test in which it is irradiated with light at an irradiation intensity of 50 mW/cm ² for 300 hours from a high-pressure mercury lamp in an environment at a temperature of 63°C. After this light fastness test, the in-plane retardation Re _L100 of the base material containing the polymerizable liquid crystal compound included in the laminate is measured. Using the in-plane retardation Re _L0 before the light resistance test and the in-plane retardation Re _L100 after the light resistance test, calculate the rate of change in in-plane retardation ΔRe _L (%) due to the light resistance test using the following formula (T2). can.
ΔRe _L (%) = {(Re _L100 - Re _L0 )/Re _L0 }×100 (T2)

The present inventor conjectures that the mechanism by which the laminate according to this embodiment has the excellent heat resistance and light resistance as described above is as follows. However, the technical scope of the present invention is not limited to the mechanism described below, and the present invention may be implemented with arbitrary changes within the scope of the claims.

Conventionally, when bonding multiple base materials with an ultraviolet curable adhesive, the substrates are pasted together via a layer of ultraviolet curable adhesive, and then ultraviolet rays are applied to the layer of the ultraviolet curable adhesive. It was common to cure by irradiation. However, when a base material with low ultraviolet transmittance is used, a sufficient amount of ultraviolet rays may not be delivered to the ultraviolet curable adhesive, resulting in insufficient curing of the ultraviolet curable adhesive. In addition, due to insufficient curing of the ultraviolet curable adhesive as described above, the heat resistance of the laminate could be lowered.

On the other hand, in the laminate according to the present embodiment, the first base material and the second base material are bonded together by an up-conversion adhesive layer containing an up-conversion compound in combination with an ultraviolet curable adhesive. Since the up-conversion compound can emit ultraviolet light upon receiving visible light, it is possible to create a UV-curable adhesive by not only the ultraviolet light transmitted through the first or second base material but also by the ultraviolet light emitted by the up-conversion compound. The curing of the agent can proceed. Therefore, even if the ultraviolet ray transmittance of the first base material and the second base material is low, the ultraviolet curable adhesive can be sufficiently cured. Therefore, a laminate with excellent heat resistance can be obtained.

Further, since the first base material and the second base material included in the laminate according to the present embodiment can usually block ultraviolet rays, damage to the laminate due to the ultraviolet rays can be suppressed. Therefore, a laminate having excellent light resistance can be obtained. For example, when a liquid crystal hardening layer is included in the first base material or the second base material, it is possible to suppress the entry of ultraviolet rays into the polymerizable liquid crystal compound or its polymer contained in the liquid crystal hardening layer, so that changes in the molecular structure due to ultraviolet rays can be suppressed. can be suppressed. Therefore, it is possible to suppress the retardation of the base material containing the polymerizable liquid crystal compound from changing due to ultraviolet rays.

The laminate according to this embodiment may function as a circularly polarizing plate. A laminate that can function as a circularly polarizing plate, for example, by using a first base material containing one of a liquid crystal cured layer and a polarizer layer, and a second base material containing the other of a liquid crystal cured layer and a polarizer layer, Obtainable. At this time, the adhesion angle of the first base material and the second base material should be adjusted so that the angle between the transmission axis of the polarizer layer and the slow axis of the liquid crystal hardening layer is 45° or close to it. is preferred. Specifically, the above angle is preferably 40° or more, more preferably 41° or more, particularly preferably 42° or more, and preferably 50° or less, more preferably 49° or less, particularly preferably It is 48° or less.

[7. Manufacturing method of laminate]
There are no restrictions on the method of manufacturing the laminate according to this embodiment. Typically, a laminate is produced by bonding a first base material and a second base material via an up-conversion adhesive layer containing an uncured ultraviolet curable adhesive, and irradiating the up-conversion adhesive layer with light. and curing the ultraviolet curable adhesive contained in the up-conversion adhesive layer, in this order.

In the above manufacturing method, it is preferable to use light containing visible light as the light irradiated to the up-conversion adhesive layer, and it is preferable to use light containing visible light and ultraviolet light. Light including visible light refers to light including light rays with one or more wavelengths in the visible wavelength range of 380 nm or more and 700 nm or less. Furthermore, light including ultraviolet light refers to light including one or more wavelengths in the ultraviolet wavelength range of 1 nm or more and less than 380 nm, preferably light rays with one or more wavelengths in the wavelength range of 200 nm or more and less than 380 nm. Represents the light that contains. Light, including visible light, can be transmitted through the first substrate and the second substrate and thus can be absorbed by the upconversion compound in the upconversion adhesive layer. The upconversion compound emits ultraviolet light using the energy of the visible light it absorbs, and the ultraviolet light can cure the ultraviolet curable adhesive in the upconversion adhesive layer. Therefore, even if the first base material and the second base material have the ability to block ultraviolet rays, the curing of the ultraviolet curable adhesive can proceed effectively, so that the laminate can be manufactured smoothly. Furthermore, if the light irradiated to the up-conversion adhesive layer contains ultraviolet rays, a portion of the ultraviolet rays will pass through the first base material or the second base material and cause the UV-curable adhesive in the up-conversion adhesive layer to Can be used for curing. Therefore, the curing of the ultraviolet curable adhesive can proceed more effectively, so that the laminate can be manufactured particularly efficiently.

For example, the laminate is
forming an upconversion adhesive layer containing an uncured ultraviolet curable adhesive and an upconversion compound on one of the first base material and the second base material;
a step of bonding the upconversion adhesive layer to the other of the first base material and the second base material;
irradiating the upconversion adhesive layer with light containing ultraviolet light and visible light through at least one of the first base material and the second base material;
may be included in this order. The manufacturing method according to this first example will be explained below.

In the method for producing a laminate according to the first example, an upconversion adhesive layer containing an uncured ultraviolet curable adhesive and an upconversion compound is formed on one of the first base material and the second base material. I do. Usually, an adhesive composition containing an uncured ultraviolet curable adhesive and an upconversion compound is prepared, and a layer of this adhesive composition is applied to the surface of one of the first base material and the second base material for upconversion. Form an adhesive layer.

The adhesive composition may include an uncured UV curable adhesive and an upconversion compound, as well as optional ingredients. If the adhesive composition includes a solvent as an optional component, the solvent may volatilize after formation of the layer of adhesive composition, but some of the solvent may remain in the upconversion adhesive layer after drying.

The adhesive composition is usually prepared as a liquid composition. Therefore, the layer of adhesive composition can be formed by coating the adhesive composition. Examples of coating methods include curtain coating, extrusion coating, roll coating, spin coating, dip coating, bar coating, spray coating, slide coating, print coating, gravure coating, and die coating. method, gap coating method, and dipping method. Further, after forming the layer of the liquid crystal composition, a drying step may be performed in order to remove volatile components such as a solvent from the layer.

After that, a step of bonding the upconversion adhesive layer formed on one of the first base material and the second base material to the other of the first base material and the second base material is performed. In order to prevent air bubbles from forming at the interface between the upconversion adhesive layer and the other of the first and second base materials, the first and second base materials are pressed together using a pressing tool such as a nip roll. You may go while doing so. In addition, when the first base material and the second base material are thin film-like members, in order to suppress the occurrence of wrinkles, the first base material and the second base material are bonded together under tension. You may go.

Thereafter, a step of irradiating the upconversion adhesive layer with light including ultraviolet light and visible light is performed through at least one of the first base material and the second base material. The ultraviolet curable adhesive included in the upconversion adhesive layer can be cured by irradiation with light. At this time, the UV-curable adhesive can be cured not only by the irradiated UV rays, but also by the UV rays emitted by the upconversion compound that has received visible light, so that the curing of the UV-curable adhesive can proceed sufficiently. be able to. Therefore, a laminate having high heat resistance can be obtained.

Also, for example, the laminate is
forming an upconversion layer containing an upconversion compound on one of the first base material and the second base material;
forming a UV adhesive layer containing an uncured ultraviolet curable adhesive on the upconversion layer;
a step of laminating the UV adhesive layer and the other of the first base material and the second base material;
irradiating the UV adhesive layer with light containing ultraviolet light and visible light through at least one of the first base material and the second base material;
may be included in this order. The manufacturing method according to this second example will be explained below.

In the method for manufacturing a laminate according to the second example, a step of forming an upconversion layer containing an upconversion compound on one of the first base material and the second base material is performed. There are no restrictions on the method of forming the upconversion layer. For example, an upconversion compound solution containing an upconversion compound and a solvent is prepared, and this upconversion compound solution is applied to one surface of a first base material and a second base material, and dried to form an upconversion layer. may be formed.

The upconversion compound solution may contain an upconversion compound, a solvent, and optional components if necessary. The solvent is preferably a solvent that can dissolve the upconversion compound. The specific type of solvent can be selected depending on the type of upconversion compound. Moreover, one type of solvent may be used alone, or two or more types may be used in combination in any ratio. The method for applying the upconversion compound solution is not limited, and for example, the same method as exemplified as the method for applying the adhesive composition can be employed. Further, the drying method may be, for example, natural drying, heat drying, reduced pressure drying, reduced pressure heat drying, or the like.

Thereafter, a step of forming a UV adhesive layer containing an uncured ultraviolet curable adhesive is performed on the upconversion layer. There are no restrictions on the method of forming the UV adhesive layer. For example, the UV adhesive layer may be formed by applying an uncured UV curable adhesive onto the upconversion layer. The method for applying the ultraviolet curable adhesive is not limited, and for example, the same method as exemplified as the method for applying the adhesive composition can be employed.

After that, a step of bonding the UV adhesive layer formed on the up-conversion layer and the other of the first base material and the second base material is performed. This bonding may be performed while pressing the first base material and the second base material with a pressing tool, as explained in the manufacturing method according to the first example, or the first base material and the second base material may be bonded together. The process may be performed with tension applied to the base material. This achieves bonding of the first base material and the second base material via the up-conversion adhesive layer including the up-conversion layer and the uncured UV adhesive layer.

Thereafter, a step of irradiating the UV adhesive layer with light including ultraviolet light and visible light is performed through at least one of the first base material and the second base material. The ultraviolet curable adhesive contained in the UV adhesive layer can be cured by irradiation with light. Thereby, as in the manufacturing method according to the first example, the curing of the ultraviolet curable adhesive can be sufficiently progressed, so that a laminate having high heat resistance can be obtained.

Furthermore, the method for manufacturing the laminate is not limited to the manufacturing method according to the example described above. For example, in the manufacturing method according to the second example, a step of forming a UV adhesive layer containing an uncured ultraviolet curable adhesive on the upconversion layer was performed; A step of forming a UV adhesive layer containing a UV curable adhesive on the other of the first base material and the second base material may be performed. Therefore, for example, the laminate is
forming an upconversion layer containing an upconversion compound on one of the first base material and the second base material;
forming a UV adhesive layer containing an uncured ultraviolet curable adhesive on the other of the first base material and the second base material;
a step of laminating an up-conversion layer and a UV adhesive layer;
irradiating the UV adhesive layer with light containing ultraviolet light and visible light through at least one of the first base material and the second base material;
It may be manufactured by a manufacturing method including.

Furthermore, the method for manufacturing a laminate may include any steps other than those described above. For example, the method for manufacturing a laminate may include a step of subjecting the surfaces of the first base material and the second base material to surface treatment such as corona treatment. Furthermore, for example, when long members are used as the first base material and the second base material, a long laminate is obtained, so the method for manufacturing the laminate involves rolling up the long laminate. It may also include a step of collecting it.

[8. Applications of laminate]
There are no restrictions on the uses of the laminate. For example, the laminate can be used for optical applications. To give a specific example, a laminate including a first base material including a liquid crystal cured layer and a second base material including a polarizer layer can be used as a polarizing plate. Such a polarizing plate can be provided, for example, in an image display device such as a liquid crystal display device or an organic electroluminescent display device.

In particular, when the laminate can function as a circularly polarizing plate, it is preferable to provide the laminate on the screen of an organic electroluminescent display device. Since the laminate provided on the screen of the organic electroluminescent display device can function as a reflection-suppressing film, it can suppress reflection of external light. Image display devices are sometimes used in environments that can reach high temperatures, such as the interior of a vehicle, but since the laminate has excellent heat resistance, the laminate can function as a anti-reflection film even in high-temperature environments. It is possible to demonstrate this. Furthermore, since the first base material and the second base material have the ability to block ultraviolet rays, the laminate protects elements in the organic electroluminescent display device (organic electroluminescent elements, etc.) from ultraviolet rays contained in external light. Is possible.

The present invention will be specifically described below with reference to Examples. However, the present invention is not limited to the examples shown below, and may be implemented with arbitrary changes within the scope of the claims of the present invention and equivalents thereof.

In the following description, "%" and "part" expressing amounts are based on weight, unless otherwise specified.
Further, the operations described below were performed at normal temperature and normal pressure in the atmosphere unless otherwise specified.
Furthermore, in the measurement of in-plane retardation described below, the measurement wavelength was 590 nm unless otherwise specified.
Further, in the actual examples and comparative examples described below, a glass plate and an adhesive material are used, but since these have optical isotropy, they do not affect the measurement of retardation described later.

[Evaluation method]
Hereinafter, evaluation methods performed in each example and comparative example will be explained.

(Method of measuring light transmittance)
Using a spectrophotometer (“V-500” manufactured by JASCO Corporation), the transmission absorption spectrum was measured at an incident angle of 0° and a measurement wavelength in the range of 200 nm to 800 nm. The light transmittance at a measurement wavelength of 380 nm was read from the measured transmission absorption spectrum.

(Heat resistance evaluation method)
The in-plane retardation Re _H0 of the liquid crystal hardened layers of the samples obtained in Examples and Comparative Examples was measured using a retardation meter ("AxoScan" manufactured by Axometrics). The above-mentioned retardation meter "AxoScan" is a device that can measure the in-plane retardation of only the liquid crystal hardened layer as a part of the layers included in the laminate, using a laminate containing multiple layers as a sample. there were.
Thereafter, the samples were subjected to a heat resistance test. In this heat resistance test, a sample was placed in an oven at 85°C and taken out after 100 hours.
Thereafter, the in-plane retardation Re _H100 of the liquid crystal cured layer of the sample after the heat resistance test was measured using a phase difference meter ("AxoScan" manufactured by Axometorics).

Using the in-plane retardation Re _H0 before the heat resistance test and the in-plane retardation Re _H100 after the heat resistance test, calculate the rate of change in in-plane retardation ΔRe _H (%) due to the heat resistance test using the following formula (T1). did. The smaller the absolute value of this rate of change ΔRe _H (%), the better the heat resistance.
ΔRe _H (%) = {(Re _H100 - Re _H0 )/Re _H0 }×100 (T1)

(Evaluation method of light resistance)
The in-plane retardation Re _L0 of the liquid crystal hardened layers of the samples obtained in the Examples and Comparative Examples was measured using a retardation meter ("AxoScan" manufactured by Axometrics).
Thereafter, the samples were subjected to a light resistance test. In this light resistance test, the glass plate side surface of the sample was irradiated with light at an irradiation intensity of 50 mW/cm ² for 300 hours from the same high-pressure mercury lamp as used in Examples and Comparative Examples in an environment at a temperature of 63°C.
Thereafter, the in-plane retardation Re _L100 of the liquid crystal cured layer of the sample after the light resistance test was measured using a retardation meter ("AxoScan" manufactured by Axometrics).

Using the in-plane retardation Re _L0 before the light resistance test and the in-plane retardation Re _L100 after the light resistance test, calculate the rate of change in in-plane retardation ΔRe _L (%) due to the light resistance test using the following formula (T2). did. The smaller the absolute value of this rate of change ΔRe _L (%), the better the light resistance is.
ΔRe _L (%) = {(Re _L100 - Re _L0 )/Re _L0 }×100 (T2)

[Production Example 1. Production of a multilayer liquid crystal film with a liquid crystal cured layer as a first base material]
(Preparation of liquid crystal composition)
19.42 parts of a polymerizable liquid crystal compound represented by the following formula (X1), 1.94 parts of a crosslinking agent (tricyclodecane dimethanol diacrylate; "NK Ester A-DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.), and a surfactant (DIC). 0.06 parts of photopolymerization initiator ("Irgacure OXE03" manufactured by BASF), 0.85 parts of antioxidant (2,6-di-t-butyl-p-cresol) ;BHT) and 77.50 parts of a mixed solvent of 1,3-dioxolane and cyclopentanone (1,3-dioxolane:cyclopentanone=60:40 (weight ratio)), A liquid crystal composition was obtained. The polymerizable liquid crystal compound represented by formula (X1) is an inversely dispersed liquid crystal compound.

(Preparation of support)
A pellet-shaped thermoplastic norbornene resin (manufactured by Nippon Zeon Co., Ltd., glass transition temperature Tg=126°C) containing an alicyclic structure-containing polymer was dried at 90°C for 5 hours. The dried resin was fed into an extruder and melted within the extruder. The molten resin was passed through a polymer pipe and a polymer filter, and then extruded into a sheet from a T-die onto a casting drum. The extruded resin was cooled to obtain a long unstretched film. This unstretched film was wound up while being protected with a masking film ("FF1025" manufactured by Tredegar) to obtain a roll of unstretched film having a thickness of 80 μm and a width of 1490 mm.

The unstretched film was unstretched from the roll, and was subjected to the following treatments while being conveyed in the longitudinal direction.
The masking film was continuously peeled off from the unstretched film that had been fed out, and the film was supplied to a tenter stretching machine. Using this tenter stretching machine, the pre-stretched film is stretched diagonally to form a long support having a slow axis making an angle of 45° with respect to the width direction (45° with respect to the longitudinal direction). Got the film. Thereafter, both ends of the support film in the width direction were trimmed to adjust the width to 1350 mm. The obtained support film had an in-plane retardation of 143 nm at a measurement wavelength of 590 nm, and a thickness of 77 μm. The obtained support film was wound up while being protected with a new masking film ("FF1025" manufactured by Tredegar) to obtain a roll of support film.

(Formation of liquid crystal hardened layer)
The support film was unwound from the roll, and the following treatments were performed while conveying it in the longitudinal direction.
The masking film was continuously peeled off from the unwound support film. The above-mentioned liquid crystal composition was directly applied to the surface of the support film on which the masking film had been bonded using a die coater to form a layer of the liquid crystal composition. Here, when the liquid crystal composition is applied "directly" to the surface of the support film, it means that there is no other layer between the surface of the support film and the liquid crystal composition. Thereafter, the layer of the liquid crystal composition on the support film was heated at 110° C. for 4 minutes. By this heating, alignment treatment for aligning the polymerizable liquid crystal compound contained in the layer of the liquid crystal composition was performed. Further, by this heating, a drying process was performed to remove the solvent contained in the layer of the liquid crystal composition. Thereafter, under a nitrogen atmosphere, with the support film supported by support rolls at a temperature of 40°C, ultraviolet rays with an integrated illuminance of 800 mJ/cm ² (irradiation intensity 400 mW/cm ² ) or more are applied to the layer of the liquid crystal composition. Irradiated. As the ultraviolet light source, a ``mercury lamp'' manufactured by Eye Graphic was used. By this irradiation with ultraviolet rays, polymerization of the polymerizable liquid crystal compound progressed, and the layer of the liquid crystal composition was cured. Thereafter, the layer of the cured liquid crystal composition and the support film are heated together at 110°C for 8 minutes to form a long multilayer liquid crystal film including the cured liquid crystal layer (thickness: 80 μm) and the support film. Obtained.

The light transmittance at 380 nm of the obtained multilayer liquid crystal film was measured using the measurement method described above. As a result of the measurement, the light transmittance at 380 nm was 5.0%. Since the above support film has a light transmittance of 100% at a wavelength of 380 nm, the value of the light transmittance of the above multilayer liquid crystal film was adopted as the light transmittance of the liquid crystal cured layer at a wavelength of 380 nm.

[Production Example 2. Preparation of adhesive composition C1]
An upconversion compound was obtained by mixing 1 part of a donor compound represented by formula (UC1) and 5 parts of an acceptor compound represented by formula (UC2). This upconversion compound was mixed with an uncured ultraviolet curable adhesive (CRB series manufactured by Toyochem Co., Ltd.) to obtain an adhesive composition C1. The amounts of the upconversion compound and the UV-curable adhesive are determined based on the solid content of the UV-curable adhesive (100% by weight). ) was adjusted so that the total amount with the acceptor compound represented by ) was 3% by weight.

[Production Example 3. Preparation of adhesive composition C2]
The amounts of the upconversion compound and the UV-curable adhesive are determined based on the solid content of the UV-curable adhesive (100% by weight). ) was adjusted so that the total amount with the acceptor compound represented by ) was 0.50% by weight. Adhesive composition C2 was obtained by the same method as Production Example 2 except for the above matters.

[Production Example 4. Preparation of upconversion compound solution]
An upconversion compound was obtained by mixing 1 part of a donor compound represented by formula (UC1) and 5 parts of an acceptor compound represented by formula (UC2). This upconversion compound was dissolved in N,N-dimethylformamide to obtain an upconversion compound solution.

[Example 1]
(1-1. Preparation of second base material)
An ultraviolet cut film F1 capable of cutting light having a wavelength of 390 nm or less was prepared. This ultraviolet cut film F1 was a thermoplastic norbornene resin film containing an ultraviolet absorber. Further, the light transmittance of this ultraviolet cut film at a wavelength of 380 nm was 1.0%.

A polarizer film made of polyvinyl alcohol resin and the above-mentioned ultraviolet cut film F1 were bonded together via an adhesive material ("LUCIAS CS9861US" manufactured by Nitto Denko Corporation). As a result, a linearly polarizing film having the layer structure of "ultraviolet cut film F1/adhesive material/polarizer film" was obtained as the second base material.

The light transmittance of the obtained second base material at a measurement wavelength of 380 nm was measured by the measurement method described above. As a result of the measurement, the light transmittance at a measurement wavelength of 380 nm was 1.0%.

(1-2. Manufacture of laminate)
Coating the adhesive composition C1 produced in Production Example 2 on the polarizer film side surface of the second base material so that the thickness of the up-conversion adhesive layer obtained after curing is 0.5 μm, A layer of adhesive composition C1 was formed. This layer of adhesive composition C1 and the surface of the multilayer liquid crystal film produced in Production Example 1 on the liquid crystal cured layer side were bonded together. This bonding was performed so that the transmission axis of the polarizer film and the slow axis of the liquid crystal cured layer formed an angle of 45° when viewed from the thickness direction. As a result, an intermediate product having a layer structure of "ultraviolet cut film F1/adhesive material/polarizer film/layer of adhesive composition C1/cured liquid crystal layer/support film" was obtained.

Thereafter, the layer of adhesive composition C1 was irradiated with light through the second base material by irradiating the surface of the intermediate product on the ultraviolet cut film F1 side with light using a high-pressure mercury lamp. The high-pressure mercury lamp used is a light source that emits both ultraviolet rays and visible light, and specifically, it emits strong light at wavelengths of 365 nm, 440 nm, 550 nm, and 580 nm. Further, the above-mentioned light irradiation was performed under the conditions of an irradiation intensity of 400 mW/cm ² and an integrated illuminance of 800 mJ/cm ² . By irradiating with this light, the ultraviolet curable adhesive was cured, and an upconversion adhesive layer containing the cured ultraviolet curable adhesive and an upconversion compound was formed.

Thereafter, the support film was peeled off to obtain a laminate having a layer structure of "ultraviolet cut film F1/adhesive material/polarizer film/up conversion adhesive layer/cured liquid crystal layer". The surface of the ultraviolet cut film F1 side of this laminate is pasted onto a flat glass plate via an adhesive material ("LUCIAS CS9861US" manufactured by Nitto Denko Corporation), and the "glass plate/adhesive material/ultraviolet cut film A sample having a layer structure of "F1/adhesive material/polarizer film/up conversion adhesive layer/cured liquid crystal layer" was obtained. Using the sample thus obtained, the heat resistance and light resistance of the laminate were evaluated by the method described above.

[Example 2]
The upconversion compound solution produced in Production Example 4 was applied by spin coating to the liquid crystal hardened layer side surface of the multilayer liquid crystal film produced in Production Example 1, and dried to form an upconversion layer with a thickness of 0.1 μm. Formed. After that, an uncured UV curable adhesive (CRB series manufactured by Toyochem Co., Ltd.) is coated on the upconversion layer so that the thickness of the UV adhesive layer after curing is 0.5 μm. A UV adhesive layer containing a curable adhesive was formed.

The polarizer film side surface of the second base material as a linearly polarizing film produced by the same method as step (1-1) of Example 1 and the UV adhesive layer formed on the up-conversion layer are bonded together. Ta. This bonding was performed so that the transmission axis of the polarizer film and the slow axis of the liquid crystal cured layer formed an angle of 45° when viewed from the thickness direction. As a result, an intermediate product having a layer structure of "ultraviolet cut film F1/adhesive material/polarizer film/UV adhesive layer/up conversion layer/cured liquid crystal layer/support film" was obtained.

Thereafter, the UV adhesive layer was irradiated with light through the second base material by irradiating the surface of the intermediate product on the ultraviolet cut film F1 side with light using a high-pressure mercury lamp. This light irradiation was performed under the same conditions as the light irradiation in Example 1. By irradiating this light, the ultraviolet curable adhesive was cured, and an upconversion adhesive layer having a layer structure of "cured UV adhesive layer/upconversion layer" was formed.

Thereafter, the support film was peeled off to obtain a laminate having a layer structure of "ultraviolet cut film F1/adhesive material/polarizer film/UV adhesive layer/up conversion layer/cured liquid crystal layer". The surface of the ultraviolet cut film F1 side of this laminate is pasted onto a flat glass plate via an adhesive material ("LUCIAS CS9861US" manufactured by Nitto Denko Corporation), and the "glass plate/adhesive material/ultraviolet cut film A sample having a layer structure of "F1/adhesive material/polarizer film/UV adhesive layer/up conversion layer/cured liquid crystal layer" was obtained. Using the sample thus obtained, the heat resistance and light resistance of the laminate were evaluated by the method described above.

[Example 3]
The upconversion compound solution produced in Production Example 4 was applied by spin coating to the polarizer film side surface of the second base material as a linearly polarizing film produced by the same method as Step (1-1) of Example 1. This was then dried to form an upconversion layer with a thickness of 0.1 μm.

After that, an uncured UV curable adhesive (CRB series manufactured by Toyochem Co., Ltd.) is coated on the upconversion layer so that the thickness of the UV adhesive layer after curing is 0.5 μm. A UV adhesive layer containing a curable adhesive was formed. This UV adhesive layer and the surface of the multilayer liquid crystal film produced in Production Example 1 on the liquid crystal cured layer side were bonded together. This bonding was performed so that the transmission axis of the polarizer film and the slow axis of the liquid crystal cured layer formed an angle of 45° when viewed from the thickness direction. As a result, an intermediate product having a layer structure of "ultraviolet cut film F1/adhesive material/polarizer film/up conversion layer/UV adhesive layer/cured liquid crystal layer/support film" was obtained.

Thereafter, the UV adhesive layer was irradiated with light through the second base material and the up-conversion layer by irradiating the surface of the intermediate product on the UV cut film F1 side with light using a high-pressure mercury lamp. This light irradiation was performed under the same conditions as the light irradiation in Example 1. By irradiating this light, the ultraviolet curable adhesive was cured, and an upconversion adhesive layer having a layer structure of "upconversion layer/cured UV adhesive layer" was formed.

Thereafter, the support film was peeled off to obtain a laminate having a layer structure of "ultraviolet cut film F1/adhesive material/polarizer film/up conversion layer/UV adhesive layer/cured liquid crystal layer". The surface of the ultraviolet cut film F1 side of this laminate is pasted onto a flat glass plate via an adhesive material ("LUCIAS CS9861US" manufactured by Nitto Denko Corporation), and the "glass plate/adhesive material/ultraviolet cut film A sample having a layer structure of "F1/adhesive material/polarizer film/up conversion layer/UV adhesive layer/liquid crystal hardening layer" was obtained. Using the sample thus obtained, the heat resistance and light resistance of the laminate were evaluated by the method described above.

[Example 4]
The upconversion compound solution produced in Production Example 4 was applied by spin coating to the liquid crystal cured layer side surface of the multilayer liquid crystal film produced in Production Example 1, and dried to form an upconversion layer with a thickness of 0.05 μm. Formed.

The upconversion compound solution produced in Production Example 4 was applied by spin coating to the polarizer film side surface of the second base material as a linearly polarizing film produced by the same method as Step (1-1) of Example 1. This was then dried to form an upconversion layer with a thickness of 0.05 μm.

Thereafter, an uncured ultraviolet curable adhesive (Toyochem Co., Ltd. A UV adhesive layer containing an ultraviolet curable adhesive was formed by applying CRB series (manufactured by Co., Ltd.). This UV adhesive layer and the up-conversion layer formed on the surface of the multilayer liquid crystal film on the liquid crystal cured layer side were bonded together. This bonding was performed so that the transmission axis of the polarizer film and the slow axis of the liquid crystal cured layer formed an angle of 45° when viewed from the thickness direction. As a result, an intermediate product having a layer structure of "ultraviolet cut film F1/adhesive material/polarizer film/up conversion layer/UV adhesive layer/up conversion layer/cured liquid crystal layer/support film" was obtained.

Thereafter, the UV adhesive layer was irradiated with light through the second base material and the up-conversion layer by irradiating the surface of the intermediate product on the UV cut film F1 side with light using a high-pressure mercury lamp. This light irradiation was performed under the same conditions as the light irradiation in Example 1. By this light irradiation, the ultraviolet curable adhesive was cured, and an upconversion adhesive layer having a layer structure of "upconversion layer/cured UV adhesive layer/upconversion layer" was formed.

Thereafter, the support film was peeled off to obtain a laminate having a layer structure of "UV cut film F1/adhesive material/polarizer film/up conversion layer/UV adhesive layer/up conversion layer/cured liquid crystal layer". . The surface of the ultraviolet cut film F1 side of this laminate is pasted onto a flat glass plate via an adhesive material ("LUCIAS CS9861US" manufactured by Nitto Denko Corporation), and the "glass plate/adhesive material/ultraviolet cut film A sample having a layer structure of "F1/adhesive material/polarizer film/up conversion layer/UV adhesive layer/up conversion layer/liquid crystal hardening layer" was obtained. Using the sample thus obtained, the heat resistance and light resistance of the laminate were evaluated by the method described above.

[Example 5]
When coating the adhesive composition C1 on the polarizer film side of the second base material, the coating amount of the adhesive composition C1 is adjusted so that the thickness of the up-conversion adhesive layer obtained after curing is 1.0 μm. Changed to Except for the above matters, a sample having the layer structure of "glass plate/adhesive material/ultraviolet cut film F1/adhesive material/polarizer film/up conversion adhesive layer/cured liquid crystal layer" was manufactured using the same method as in Example 1. did. Using the sample thus obtained, the heat resistance and light resistance of the laminate were evaluated by the method described above.

[Example 6]
An ultraviolet cut film F2 capable of cutting light having a wavelength of 380 nm or less was prepared. This ultraviolet cut film F2 was a thermoplastic norbornene resin film containing an ultraviolet absorber, and had a lower ability to block ultraviolet light than the ultraviolet cut film F1 prepared in Example 1.

"Glass plate/adhesive material/ultraviolet cut film F2/adhesive material/polarizer" was prepared in the same manner as in Example 1 except that the ultraviolet cut film F2 prepared in Example 6 was used instead of the ultraviolet cut film F1. A sample having a layer structure of "film/up-conversion adhesive layer/liquid crystal hardening layer" was manufactured. Using the sample thus obtained, the heat resistance and light resistance of the laminate were evaluated by the method described above.

[Comparative example 1]
Instead of the adhesive composition C1 containing an upconversion compound, an uncured ultraviolet curable adhesive (CRB series manufactured by Toyochem Co., Ltd.) containing no upconversion compound was used. Except for the above, a sample having the layer structure of "glass plate/adhesive material/ultraviolet cut film F1/adhesive material/polarizer film/UV adhesive layer/cured liquid crystal layer" was manufactured using the same method as in Example 1. did. Using the sample thus obtained, the heat resistance and light resistance of the laminate were evaluated by the method described above.

[Comparative example 2]
An ultraviolet cut film F3 capable of cutting light having a wavelength of 380 nm or less was prepared. This ultraviolet cut film F3 is a thermoplastic norbornene resin film containing an ultraviolet absorber, and has a lower ability to block ultraviolet light than the ultraviolet cut films F1 and F2 prepared in Examples 1 and 6. Ta.

"Glass plate/adhesive material/ultraviolet cut film F3/adhesive material/polarizer" was prepared in the same manner as in Example 1 except that the ultraviolet cut film F3 prepared in Comparative Example 2 was used instead of the ultraviolet cut film F1. A sample having a layer structure of "film/up-conversion adhesive layer/liquid crystal hardening layer" was manufactured. Using the sample thus obtained, the heat resistance and light resistance of the laminate were evaluated by the method described above.

[result]
The results of the above-mentioned Examples and Comparative Examples are shown in the table below. In the table below, the meanings of abbreviations are as follows.
T(380): Light transmittance at a wavelength of 380 nm.
UC adhesive layer: upconversion adhesive layer.
UC layer: Up conversion layer.
UC compound: upconversion compound.
UC1: Donor compound represented by formula (UC1).
UC2: an acceptor compound represented by formula (UC2).

100 Laminate 110 First base material 120 Up-conversion adhesive layer 130 Second base material 200 Laminate 220 Up-conversion adhesive layer 221 UV adhesive layer 222 Up-conversion layer

Claims (10)

comprising a first base material, an adhesive layer, and a second base material in this order,
The first base material includes a cured liquid crystal layer formed of a cured product of a liquid crystal composition containing a polymerizable liquid crystal compound,
the adhesive layer and the liquid crystal hardening layer are in direct contact with each other,
The light transmittance of the first base material at a wavelength of 380 nm is less than 10.0%,
The light transmittance of the second base material at a wavelength of 380 nm is less than 10.0%,
The laminate, wherein the adhesive layer includes an ultraviolet curable adhesive and an upconversion compound capable of emitting ultraviolet light upon receiving visible light. The laminate according to claim 1, wherein the polymerizable liquid crystal compound is represented by the following formula (I).

However, in formula (I),
Ar represents a group represented by formula (III-2),

R ^f represents a group selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms,
R ^g represents a group selected from the group consisting of a hydrogen atom and an organic group having 1 to 30 carbon atoms which may have a substituent,
R ^h represents an organic group having one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms;
Z ¹ and Z ² are each independently a single bond, -O-, -O-CH ₂ -, -CH ₂ -O-, -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ - O-, -C(=O)-O-, -OC(=O)-, -C(=O)-S-, -S-C(=O)-, -NR ²¹ -C(= O)-, -C(=O)-NR ²¹ -, -CF ₂ -O-, -O-CF ₂ -, -CH ₂ -CH ₂ -, -CF ₂ -CF ₂ -, -O-CH ₂ -CH ₂ -O-, -CH=CH-C(=O)-O-, -OC(=O)-CH=CH-, -CH ₂ -C(=O)-O-, -O -C(=O)-CH ₂ -, -CH ₂ -O-C(=O)-, -C(=O)-O-CH ₂ -, -CH ₂ -CH ₂ -C(=O)- O-, -OC(=O)-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -OC(=O)-, -C(=O)-O-CH ₂ -CH ₂ - , -CH=CH-, -N=CH-, -CH=N-, -N=C(CH ₃ )-, -C(CH ₃ )=N-, -N=N-, and -C≡ C-, each R ²¹ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A ¹ , A ² , B ¹ and B ² are each independently a group consisting of a cycloaliphatic group which may have a substituent and an aromatic group which may have a substituent. represents a group selected from
Y ¹ to Y ⁴ are each independently a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NR ²² -C(=O)-, -C(=O)-NR ²² -, -OC(=O)-O-, -NR ²² -C(=O)-O-, -OC(= represents one selected from the group consisting of O)-NR ²² - and -NR ²² -C(=O)-NR ²³ -, and R ²² and R ²³ are each independently a hydrogen atom or a carbon represents an alkyl group having 1 to 6 atoms,
G ¹ and G ² are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and a methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group having 3 to 20 carbon atoms; represents an organic group selected from the group consisting of a group in which one or more of is substituted with -O- or -C(=O)-, and the hydrogen atom contained in the organic group of G ¹ and G ² is a carbon atom It may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, provided that the methylene group (-CH ₂ -) at both ends of G ¹ and G ² is -O- or -C(=O)- is not substituted,
P ¹ and P ² each independently represent a polymerizable group,
p and q each independently represent 0 or 1. The laminate according to claim 1 or 2, wherein the second base material includes a polarizer layer. The adhesive layer includes a UV adhesive layer containing the ultraviolet curable adhesive and an upconversion layer containing the upconversion compound,
The laminate according to any one of claims 1 to 3, wherein the UV adhesive layer and the liquid crystal cured layer are in direct contact. The laminate according to any one of claims 1 to 4, wherein the upconversion compound includes a combination of a compound represented by the following formula (UC1) and a compound represented by the formula (UC2).

forming an upconversion adhesive layer on one of the first base material and the second base material, which includes an uncured ultraviolet curable adhesive and an upconversion compound capable of emitting ultraviolet light upon receiving visible light;
bonding the upconversion adhesive layer to the other of the first base material and the second base material;
A method for manufacturing a laminate, comprising, in this order, irradiating the upconversion adhesive layer with light containing ultraviolet light and visible light through at least one of the first base material and the second base material,
The first base material includes a cured liquid crystal layer formed of a cured product of a liquid crystal composition containing a polymerizable liquid crystal compound,
In the laminate, the liquid crystal hardening layer and the upconversion adhesive layer are in direct contact with each other,
The light transmittance of the first base material at a wavelength of 380 nm is less than 10.0%,
A method for manufacturing a laminate, wherein the second base material has a light transmittance of less than 10.0% at a wavelength of 380 nm. forming an upconversion layer on the second base material that includes an upconversion compound that can receive visible light and emit ultraviolet light;
forming a UV adhesive layer containing an uncured ultraviolet curable adhesive on the upconversion layer;
bonding the UV adhesive layer and a first base material;
A method for producing a laminate, the method comprising the steps of: irradiating the UV adhesive layer with light containing ultraviolet light and visible light through at least one of the first base material and the second base material,
The first base material includes a cured liquid crystal layer formed of a cured product of a liquid crystal composition containing a polymerizable liquid crystal compound,
In the laminate, the liquid crystal cured layer and the UV adhesive layer are in direct contact with each other,
The light transmittance of the first base material at a wavelength of 380 nm is less than 10.0%,
A method for manufacturing a laminate, wherein the second base material has a light transmittance of less than 10.0% at a wavelength of 380 nm. forming an upconversion layer on the second base material that includes an upconversion compound that can receive visible light and emit ultraviolet light;
forming a UV adhesive layer containing an uncured ultraviolet curable adhesive on the first base material;
bonding the upconversion layer and the UV adhesive layer;
A method for producing a laminate, the method comprising: irradiating the UV adhesive layer with light containing ultraviolet light and visible light through at least one of the first base material and the second base material,
The first base material includes a cured liquid crystal layer formed of a cured product of a liquid crystal composition containing a polymerizable liquid crystal compound,
In the laminate, the liquid crystal cured layer and the UV adhesive layer are in direct contact with each other,
The light transmittance of the first base material at a wavelength of 380 nm is less than 10.0%,
A method for manufacturing a laminate, wherein the second base material has a light transmittance of less than 10.0% at a wavelength of 380 nm. The method for producing a laminate according to any one of claims 6 to 8, wherein the polymerizable liquid crystal compound is represented by the following formula (I).

However, in formula (I),
Ar represents a group represented by formula (III-2),

R ^f represents a group selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms,
R ^g represents a group selected from the group consisting of a hydrogen atom and an organic group having 1 to 30 carbon atoms which may have a substituent,
R ^h represents an organic group having one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms;
Z ¹ and Z ² are each independently a single bond, -O-, -O-CH ₂ -, -CH ₂ -O-, -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ - O-, -C(=O)-O-, -OC(=O)-, -C(=O)-S-, -S-C(=O)-, -NR ²¹ -C(= O)-, -C(=O)-NR ²¹ -, -CF ₂ -O-, -O-CF ₂ -, -CH ₂ -CH ₂ -, -CF ₂ -CF ₂ -, -O-CH ₂ -CH ₂ -O-, -CH=CH-C(=O)-O-, -OC(=O)-CH=CH-, -CH ₂ -C(=O)-O-, -O -C(=O)-CH ₂ -, -CH ₂ -O-C(=O)-, -C(=O)-O-CH ₂ -, -CH ₂ -CH ₂ -C(=O)- O-, -OC(=O)-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -OC(=O)-, -C(=O)-O-CH ₂ -CH ₂ - , -CH=CH-, -N=CH-, -CH=N-, -N=C(CH ₃ )-, -C(CH ₃ )=N-, -N=N-, and -C≡ C-, each R ²¹ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A ¹ , A ² , B ¹ and B ² are each independently a group consisting of a cycloaliphatic group which may have a substituent and an aromatic group which may have a substituent. represents a group selected from
Y ¹ to Y ⁴ are each independently a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NR ²² -C(=O)-, -C(=O)-NR ²² -, -OC(=O)-O-, -NR ²² -C(=O)-O-, -OC(= represents one selected from the group consisting of O)-NR ²² - and -NR ²² -C(=O)-NR ²³ -, and R ²² and R ²³ are each independently a hydrogen atom or a carbon represents an alkyl group having 1 to 6 atoms,
G ¹ and G ² are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and a methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group having 3 to 20 carbon atoms; represents an organic group selected from the group consisting of a group in which one or more of is substituted with -O- or -C(=O)-, and the hydrogen atom contained in the organic group of G ¹ and G ² is a carbon atom It may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, provided that the methylene group (-CH ₂ -) at both ends of G ¹ and G ² is -O- or -C(=O)- is not substituted,
P ¹ and P ² each independently represent a polymerizable group,
p and q each independently represent 0 or 1. The method for producing a laminate according to any one of claims 6 to 9, wherein the second base material includes a polarizer layer.

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