阅读说明：本技术 树脂组合物、膜、滤光器、图像显示装置、固体摄像元件及化合物 (Resin composition, film, optical filter, image display device, solid-state imaging element, and compound ) 是由 佐佐木大辅 原彰宏 儿玉邦彦 深川伸隆 内藤遊 桑原浩树 于 2019-02-18 设计创作，主要内容包括：本发明提供一种包含由通式(1)表示的化合物及树脂的树脂组合物、包含该树脂组合物的膜及滤波器、具备该滤波器的液晶显示装置及固体摄像元件、以及适合作为上述树脂组合物及滤波器的光吸收成分的化合物。通式(1)中,Dye表示从特定结构的方酸化合物中去除n1个氢原子而得的色素结构部。Q<Sup>1</Sup>为最高占据轨道和最低空轨道的能级满足特定条件的结构部。L<Sup>1</Sup>为2价的连接基,n1为1～4的整数。<Image he="131" wi="700" file="DDA0002650088040000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides a resin composition containing a compound represented by general formula (1) and a resin, a film and a filter containing the resin composition, a liquid crystal display device and a solid provided with the filterA body imaging element, and a compound suitable as a light absorbing component of the resin composition and the filter. In the general formula (1), Dye represents a Dye moiety obtained by removing n1 hydrogen atoms from a squarylium compound having a specific structure. Q 1 And a structure portion in which the energy levels of the highest occupied orbit and the lowest unoccupied orbit satisfy a specific condition. L is 1 Is a linking group having a valence of 2, and n1 is an integer of 1 to 4.)

1. A resin composition comprising a compound represented by the following general formula (1) and a resin,

in the general formula (1), Dye represents a Dye structure obtained by removing n1 hydrogen atoms from a compound represented by the following general formula (2),

in the general formula (2), A and B represent aryl, heterocyclic group or-CH ═ G, G represents heterocyclic group,

Q¹represents a structural part satisfying the following (i) and (ii),

(i) the energy level difference between the highest occupied orbit and the lowest empty orbit is more than 2.9eV,

(ii) the absolute value of the lowest unoccupied orbital level is less than the absolute value of the lowest unoccupied orbital level of Dye, or the absolute value of the highest occupied orbital level is less than the absolute value of the highest occupied orbital level of Dye,

L¹is AND Q¹A 2-valent linking group consisting of an alkylene group, or with Q¹The ring of the aliphatic ring constitutes a 2-valent linking group to which carbon atoms are directly bonded,

n1 is an integer of 1 to 4.

2. The resin composition according to claim 1, wherein,

said Q¹Represents a structural part obtained by removing 1 hydrogen atom from a compound represented by any one of the following general formulae (5) to (13),

R⁵～R²⁰、R²²、R²³、R²⁵～R²⁷、R³⁰～R³⁶、R^37a～R^37e、R³⁸～R⁴²represents a hydrogen atom or a substituent group,

R²¹and R²⁴Each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, wherein R is defined as²¹And R²⁴When hydrogen atoms are used, Q¹By removal of the nitrogen atom of the hydrogen atom to the linking group L¹Bonding is carried out on the raw materials,

X¹represents an oxygen atom, a sulfur atom or a carbon atom, and n is an integer of 1 to 3.

3. The resin composition according to claim 1 or 2, wherein,

in the general formula (2), A is a heterocyclic group.

4. The resin composition according to any one of claims 1 to 3, wherein,

dye represents a Dye structure obtained by removing n1 hydrogen atoms from a compound represented by the following general formula (3),

R³and R⁴Represents a hydrogen atom or a substituent, and B is the same as B in the general formula (2).

5. The resin composition according to any one of claims 1 to 4, wherein,

the resin is at least 1 of polystyrene resin, cellulose acylate resin, acrylic resin and cycloolefin resin.

6. A film comprising the resin composition of any one of claims 1 to 5.

7. An optical filter comprising the resin composition according to any one of claims 1 to 5.

8. An image display device comprising the optical filter of claim 7.

9. A solid-state image pickup element comprising the optical filter according to claim 7.

10. A compound represented by the following general formula (IA),

in the general formula (1A), Dye¹Represents a dye structure obtained by removing n1 hydrogen atoms from a compound represented by the following general formula (2A),

in the general formula (2A), a represents a heterocyclic group, B represents an aryl group, a heterocyclic group or-CH ═ G, G represents a heterocyclic group, Q¹Represents a structural part satisfying the following (i) and (ii),

(i) the energy level difference between the highest occupied orbit and the lowest empty orbit is more than 2.9eV,

(ii) the absolute value of the lowest unoccupied orbital level is less than the absolute value of the lowest unoccupied orbital level of Dye, or the absolute value of the highest occupied orbital level is less than the absolute value of the highest occupied orbital level of Dye,

L¹is AND Q¹A 2-valent linking group consisting of an alkylene group, or with Q¹The ring of the aliphatic ring constitutes a 2-valent linking group to which carbon atoms are directly bonded,

n1 is an integer of 1 to 4.

11. The compound of claim 10, wherein,

the Dye¹Represents a dye structure obtained by removing n1 hydrogen atoms from a compound represented by the following general formula (3),

R³and R⁴Represents a hydrogen atom or a substituent, and B is the same as B in the general formula (2A).

Technical Field

The present invention relates to a resin composition suitable as a constituent material of an optical filter, a film and an optical filter using the resin composition, and an image display device and a solid-state imaging element using the optical filter. The present invention also relates to a compound suitable as a light-absorbing component of the resin composition.

Background

Liquid crystal display devices are used in a wide range of applications as image display devices with low power consumption and space saving. In a market such as a television, which requires high-quality images, there is an increasing demand for improvement in color reproducibility in addition to resolution.

The liquid crystal display device is a non-light-emitting type element in which a liquid crystal panel itself displaying an image does not emit light. Therefore, a backlight unit is disposed on the back surface of the liquid crystal panel, and light is supplied to the liquid crystal panel.

In recent years, white Light Emitting Diodes (LEDs) have been used as light sources for backlight units. As a light emitting device using a white LED, a method of generating white light by mixing blue light emitted from a blue LED and light emitted from a yellow phosphor or a green phosphor and a red phosphor is known. However, the above-described method has a problem that the color reproduction region is narrower than that of an Organic Light Emitting Diode (OLED) or the like which is attracting attention as a next-generation display. A new technology is required to overcome this problem, and a technology is proposed in which a coating layer containing a dye is disposed on a diffusion film in a backlight unit to block unnecessary wavelengths of light emitted from a white LED. Further, patent documents 1 and 2 propose color adjusting filters using squarylium dyes having specific substituents.

Prior art documents

Patent document

Patent document 1: international publication No. 2008/090757

Patent document 2: japanese patent laid-open No. 2008-145480

Disclosure of Invention

Technical problem to be solved by the invention

However, as a result of studies on the coloring matters described in patent documents 1 and 2, the present inventors have found that when a filter using these coloring matters is used as, for example, a protective film of a polarizing plate used in a liquid crystal display device, depolarization is caused by fluorescence generated by light absorption of the coloring matters, and the polarization performance of the polarizing plate is lowered (high contrast is not favorably achieved). Further, it was clarified that the light absorption energy of the above-described filter is easily decreased with time due to light irradiation.

Accordingly, an object of the present invention is to provide a film and an optical filter which can block light of a target specific wavelength such as light of an unnecessary wavelength emitted from a white LED or the like, can effectively suppress fluorescence emission, and are excellent in light resistance, a resin composition suitable as a constituent material of the film and the optical filter, and an image display device and a solid-state imaging element including the optical filter. Another object of the present invention is to provide a compound suitable as a light-absorbing component of the resin composition.

Means for solving the technical problem

As a result of intensive studies on the above problems, the present inventors have found the following: a compound of the structure

(a) Has a specific squarylium dye structure, and further,

(b) a structure portion having an energy level difference between the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) of a prescribed or greater value and having a HOMO energy level and/or LUMO energy level having an absolute value lower than the absolute value of the energy level of the corresponding orbital among the squarylium dye structure portions,

when the optical filter is formed by a composition containing a resin and a compound having a structure in which the structures of (a) and (b) are linked by a 2-valent linking group, the squaraine moiety of the compound specifically absorbs and blocks light of a target specific wavelength, and fluorescence emission from the squaraine moiety excited by light absorption can be effectively suppressed, and an optical filter excellent in light resistance can be obtained.

The present invention has been completed through repeated studies based on these findings.

That is, the above problems are solved by the following methods.

〔1〕

A resin composition comprising a compound represented by the following general formula (1) and a resin.

[ chemical formula 1]

In the general formula (1), Dye represents a Dye structure obtained by removing n1 hydrogen atoms from a compound represented by the following general formula (2),

[ chemical formula 2]

In the general formula (2), a and B represent an aryl group, a heterocyclic group, or-CH ═ G. G represents a heterocyclic group.

Q¹Represents a structural part satisfying the following (i) and (ii).

(i) The energy level difference between the highest occupied orbit and the lowest vacant orbit is 2.9eV or more.

(ii) The absolute value of the lowest unoccupied orbital level is less than the absolute value of the lowest unoccupied orbital level of the Dye, or the absolute value of the highest occupied orbital level is less than the absolute value of the highest occupied orbital level of the Dye.

L¹Is AND Q¹A 2-valent linking group consisting of an alkylene group, or with Q¹The ring of the aliphatic ring constitutes a 2-valent linking group to which carbon atoms are directly bonded,

n1 is an integer of 1 to 4.

〔2〕

The resin composition according to [ 1], wherein,

above Q¹Represents a structural part obtained by removing 1 hydrogen atom from a compound represented by any one of the following general formulae (5) to (13).

[ chemical formula 3]

R⁵～R²⁰、R²²、R²³、R²⁵～R²⁷、R³⁰～R³⁶、R^37a～R^37e、R³⁸～R⁴²Represents a hydrogen atom or a substituent.

R²¹And R²⁴Each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, wherein R is defined as²¹And R²⁴When hydrogen atoms are used, Q¹By removal of the nitrogen atom of the hydrogen atom to the linking group L¹Bonding is carried out on the raw materials,

X¹represents an oxygen atom, a sulfur atom or a carbon atom, and n is an integer of 1 to 3.

〔3〕

The resin composition according to [ 1] or [ 2], wherein,

in the general formula (2), A is a heterocyclic group.

〔4〕

The resin composition according to any one of [ 1] to [ 3], wherein,

dye represents a Dye structure obtained by removing n1 hydrogen atoms from a compound represented by the following general formula (3).

[ chemical formula 4]

R³And R⁴Represents a hydrogen atom or a substituent. B is the same as B in the above general formula (2).

〔5〕

The resin composition according to any one of [ 1] to [ 4], wherein,

the resin is at least 1 of polystyrene resin, cellulose acylate resin, acrylic resin and cycloolefin resin.

〔6〕

A film comprising the resin composition according to any one of [ 1] to [ 5 ].

〔7〕

An optical filter comprising the resin composition according to any one of [ 1] to [ 5 ].

〔8〕

An image display device comprising the filter [ 7 ].

〔9〕

A solid-state imaging element comprising the optical filter according to [ 7 ].

〔10〕

A compound represented by the following general formula (IA).

[ chemical formula 5]

In the general formula (1A), Dye¹Represents a dye structure obtained by removing n1 hydrogen atoms from a compound represented by the following general formula (2A).

[ chemical formula 6]

In the general formula (2A), A represents a heterocyclic group. B represents aryl, heterocyclyl or-CH ═ G. G represents a heterocyclic group.

Q¹Represents a structural part satisfying the following (i) and (ii).

(i) The energy level difference between the highest occupied orbit and the lowest vacant orbit is 2.9eV or more.

(ii) The absolute value of the lowest unoccupied orbital level is less than the absolute value of the lowest unoccupied orbital level of the Dye, or the absolute value of the highest occupied orbital level is less than the absolute value of the highest occupied orbital level of the Dye.

L¹Is AND Q¹A 2-valent linking group consisting of an alkylene group, or with Q¹The ring of the aliphatic ring constitutes a 2-valent linking group to which carbon atoms are directly bonded,

n1 is an integer of 1 to 4.

〔11〕

The compound according to [ 10], wherein,

dye as described above¹Represents a dye structure obtained by removing n1 hydrogen atoms from a compound represented by the following general formula (3).

[ chemical formula 7]

R³And R⁴Represents a hydrogen atom or a substituent. B is the same as B in the general formula (2A).

In the present invention, in the compound (dye) represented by the chemical structural formula described in the present specification, a cation exists in a delocalized manner, and a plurality of tautomeric structures exist. Therefore, in the present invention, when at least one tautomer structure of a certain pigment is applied to the chemical structural formula specified by each general formula, the pigment is set as the pigment represented by each general formula. Therefore, the pigment represented by the specific general formula can also be referred to as a pigment whose at least one tautomeric structure can be represented by the specific general formula. In the present invention, the pigment represented by the general formula may adopt any tautomeric structure as long as at least one of its tautomeric structures is applied to the general formula.

In the present invention, the numerical range represented by "to" is intended to include the numerical values recited before and after the range as the lower limit value and the upper limit value.

In the present invention, the presence of a plurality of substituents, linkers, etc. (hereinafter referred to as "substituents" etc.) represented by specific symbols, or the simultaneous or selective specification of a plurality of substituents, etc., means that the substituents may be the same or different from each other. The same applies to the number of substituents and the like. When a plurality of substituents are close to each other (particularly adjacent to each other), these may be connected to each other or fused to form a ring.

In the present invention, the expression of the compound is used as meaning including a salt thereof and an ion thereof, in addition to the meaning of the compound itself. Further, the term "partially modified" means that the structure is partially modified within a range in which the intended effect is not impaired. Examples of the salt of the compound include an acid addition salt of the compound formed from the compound and an inorganic acid or an organic acid, and a base addition salt of the compound formed from the compound and an inorganic base or an organic base. Examples of the ions of the compound include ions generated by dissolving a salt of the compound in water, a solvent, or the like.

In the present specification, a substituent which is not explicitly described as substituted or unsubstituted (the same applies to the linking group) means that the group may have any substituent as long as the desired effect is not impaired. This also applies to compounds or repeating units which are not explicitly described as substituted or unsubstituted.

In the present invention, when the number of carbon atoms of a certain group is specified, the number of carbon atoms refers to the number of carbon atoms of the whole group. That is, when the group is in a form further having a substituent, the number of carbon atoms in the whole group including the substituent is meant.

In the present invention, when a group is capable of forming an acyclic skeleton and a cyclic skeleton, a group includes a group of the acyclic skeleton and a group of the cyclic skeleton unless otherwise specified. For example, unless otherwise specified, alkyl is meant to encompass straight chain alkyl, branched chain alkyl, and cyclic (cyclo) alkyl groups. When a group forms a cyclic skeleton, the lower limit of the number of carbon atoms in the group of the cyclic skeleton is preferably 3 or more, and more preferably 5 or more, regardless of the lower limit of the number of carbon atoms specifically described in a group.

In the present invention, the term "(meth) acrylic acid" is used to have a meaning including both methacrylic acid and acrylic acid.

Effects of the invention

The film and the optical filter of the present invention can block light of a target specific wavelength such as light of an unnecessary wavelength emitted from a white LED or the like, can effectively suppress fluorescence emission, and are excellent in light resistance. The liquid crystal display device and the solid-state imaging element of the present invention have excellent image contrast. The resin composition of the present invention is suitable as a material for forming the optical filter of the present invention. The compound of the present invention is also suitable as a light-absorbing component of the resin composition of the present invention.

Drawings

Fig. 1 is a schematic view showing an embodiment of a liquid crystal display device including a polarizing plate having the optical filter of the present invention in a backlight.

Detailed Description

[ resin composition ]

The resin composition of the present invention contains a pigment compound having a specific structure and a resin as a binder. The dye compound is formed by connecting a structural part of a squarylium dye having absorption in a specific wavelength region of visible light and a structural part which suppresses fluorescence emission when the squarylium dye structural part is excited by light absorption, by a specific connecting structure. The resin composition of the present invention is suitable as a constituent material of the optical filter (filter containing a dye compound and a resin) of the present invention.

< pigment >

The pigment compound used in the resin composition of the present invention is represented by the following general formula (1).

[ chemical formula 8]

In general formula (1), Dye represents a Dye structure obtained by removing n1 hydrogen atoms from a compound represented by general formula (2).

[ chemical formula 9]

In the general formula (2), a and B represent an aryl group, a heterocyclic group, or-CH ═ G. G represents a heterocyclic group.

L¹Is AND Q¹A 2-valent linking group consisting of an alkylene group, or with Q¹The ring of the aliphatic ring constitutes a 2-valent linking group to which carbon atoms are directly bonded. The linking group having a valence of 2 is also preferably an alkylene group, and is also preferably a group in which an alkylene group and a group having a hetero atom (for example, an oxygen atom, a sulfur atom, or a nitrogen atom) are combined. L is¹The molecular weight of (A) is preferably 14 to 300, more preferably 14 to 100.

In the general formula (1), L¹Is a 2-valent linking group as described above, and is not a single bond. If Dye is AND Q¹In the form of a single bond connection, then Q¹This is not preferable because it may affect the hue of Dye.

As useful as L¹Examples of the 2-valent linking group in (a) include an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a 2-valent heterocyclic group obtained by removing 2 hydrogens from a heterocyclic ring, -CH ═ CH-, -CO-, -CS-, -NR- (R represents a hydrogen atom or a 1-valent substituent), -O-, -S-, -SO₂or-N ═ CH-or a 2-valent linking group formed by combining a plurality of the same (preferably an integer of 2 to 10). Preferably, the alkylene group having 1 to 8 carbon atoms, the arylene group having 6 to 12 carbon atoms, or the like is selected from the group consisting of-CH-CH-, -CO-, -NR- (R is as defined above), -O-, -S-, -SO₂A 2-valent linking group formed by combining groups of-and-N ═ CH-or groups of 2 or more (preferably an integer of 2 to 10) selected from the group, and the number of carbon atoms is particularly preferred1 to 4 alkylene groups, phenylene groups, alkylene groups selected from the group consisting of-CO-, -NH-, -O-and-SO₂A linking group formed by combining 2 or more (preferably an integer of 2 to 10) groups selected from the group (a) above. Specific examples of the combined 2-valent linking group include-COO-, -OCO-, -CONH-, -NHCOO-, -NHCONH-, -SO₂NH-, and-CO-, -COO-or-CONH-in combination with an alkylene or arylene group.

As useful as L¹Or L¹The alkylene group in a part of (1) is not particularly limited as long as it is a group having 1 to 20 carbon atoms. And, as useful as L¹Or L¹Examples of the arylene group and the heterocyclic group in part of (a) include a group obtained by further removing 1 hydrogen atom from each of the groups exemplified as the aryl group having 6 to 20 carbon atoms usable as a in the general formula (2) and a group obtained by further removing 1 hydrogen atom from each of the groups exemplified as the heterocyclic group usable as a. The substituent usable as R is not particularly limited, and has the same meaning as the substituent X that A in the general formula (2) may have.

L¹May have 1 or more substituents. As L¹The substituent which may be present is not particularly limited, and is, for example, the same as the substituent X described above. When L is¹When a plurality of substituents are present, the substituents bonded to adjacent atoms may be bonded to each other to further form a ring structure.

n1 is an integer of 1 to 4. n1 is preferably 1 to 3, and more preferably 1 or 2.

Q¹Represents a structural part satisfying the following (i) and (ii).

(i) The difference in energy level between the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) is 2.9eV or more.

(ii) The absolute value of the energy level of the LUMO is smaller than the absolute value of the energy level of the LUMO in the above Dye, and/or the absolute value of the energy level of the HOMO is smaller than the absolute value of the energy level of the HOMO in the above Dye.

The condition (i) above represents Q¹The optical film has a property of not absorbing light in the visible light region. I.e., if Q¹To satisfy the above (i), and via L¹To DyeThe structure does not substantially affect the hue of the Dye (specific and effective light absorption).

The condition (ii) is a condition for suppressing fluorescence emitted when the Dye in an excited state returns to a background state by absorption of light. I.e. when Q is¹When the absolute value of the energy level of the LUMO in (b) is smaller than the absolute value of the energy level of the LUMO in (b), electrons transferred to the LUMO by excitation of (b) are preferentially transferred to Q¹The LUMO of (1). That is, a phenomenon in which an electron moved to LUMO by excitation of Dye directly moves to HOMO of the Dye and the Dye returns to a ground state can be effectively suppressed. As a result, fluorescence emission of Dye is suppressed.

And when Q is¹When the absolute value of the energy level of the HOMO in (b) is smaller than the absolute value of the energy level of the HOMO in (b), electrons are emitted from Q¹Moves to the HOMO of Dye where one electron vacancy occurs due to excitation, and the HOMO of Dye fills and stabilizes. As a result, the electrons transferred to the LUMO by the excitation of Dye are transferred to Q¹The LUMO of (1). That is, a phenomenon in which electrons moved to LUMO by excitation of Dye are directly returned to HOMO of Dye can be effectively suppressed, and fluorescence emission of Dye can be suppressed.

However, the mechanism of suppressing fluorescence emission is merely an estimation, and the present invention is not limited to the above mechanism.

Further, the compound of the general formula (1) used in the present invention is also excellent in light resistance. In general, in an electron-transfer quenching system (a system in which a fluorescent dye and a quencher coexist), the dye is in a state of an anionic radical or a cationic radical due to electron transfer, and thus light resistance is generally deteriorated. However, the compound of the general formula (1) (Dye and Q are connected by a 2-valent linker) used in the present invention¹While Dye and Q¹A compound incorporated in the same molecule) is excellent in light resistance.

In the compound of the general formula (1), Dye is obtained by reacting L with the structure of the general formula (2)¹A structure in which the conjugated structure is cut by the connection. For example, in the case of compound A-1, the squaric acid structure on the right side of the squaric acid structure corresponding to general formula (2) corresponds to the structureAnd Q¹Linker of the connecting moiety of (1)¹The vinyl group(s) in the conjugated structure. Here, the conjugated structure refers to a structure forming a bond p orbital system having delocalized electrons on single bonds and multiple bonds at alternating positions, and also includes a p orbital electron donating group, a p orbital electron donating atom, or a structure including a p orbital electron donating group and a p orbital electron donating atom. Examples of the p orbital electron donating group include a carbonyl group and a sulfonyl group. The p orbital donor atom means an atom having 2 lone electron pairs, one of which occupies the p orbital, and examples of the atom capable of serving as the p orbital donor atom include an oxygen atom, a nitrogen atom, a sulfur atom, and the like. When the p-orbital electron donating group and the p-orbital electron donating atom are contained, a structure in which a plurality of (preferably an integer of 2 to 10) p-orbital electron donating atoms and p-orbital electron donating groups are combined, for example, a structure composed of-O-CO-, -NH-SO₂The 2-valent group represented by-NH-CO-NH-, etc. is a group forming a conjugated structure. However, in the present invention, when a 2-valent group represented by — O — C (═ O) -or — NH-C (═ O) -is directly bonded to a ring-constituting atom of an aromatic ring in a squaric acid structure, it is interpreted that a conjugated structure of the aromatic ring is cleaved by the 2-valent group. In this explanation, the direction in which the-O-C (═ O) -and-NH-C (═ O) -are bonded to the ring-constituting atoms of the aromatic ring is not limited.

And, in the compound of the general formula (1), Q¹The structure of (2) is roughly classified into 2 forms (there are also structures applicable to both of the 2 forms).

In one form, across L¹A structural part facing the Dye and facing the L¹And (ii) an alkylene group, and satisfies the forms (i) and (ii). In other words, in the interval of L¹In the structure portion facing the Dye, an alkylene group is present in the structure from the end of the structure portion toward the Dye with L interposed therebetween¹When the whole structural part from the end of the structural part facing the Dye to the front of the alkylene group satisfies the above (i) and (ii), the alkylene group constitutes L¹(i.e., Q)¹The structure of (2) is cleaved just before the alkylene group. ).

For example, when compound A-1 is taken as an example, the right methoxy group isA structural portion of a phenylene group or more to an ether group is bonded to a vinyl group (alkylene group), and also satisfies the above (i) and (ii), and is Q¹。

According to the above description, in the compound A-1, with Dye, L¹And Q¹The corresponding structures are as follows. In the present specification, a symbol denotes a connection site.

[ chemical formula 10]

Q¹Is based on the following: and is separated by L¹Whether or not the feature facing the Dye is in contact with L¹The alkylene linkages present independently have an aliphatic ring. In this case, the ring constituent atom on the Dye side of the aliphatic ring is a carbon atom. And if from L¹(iii) when the end of the moiety facing the Dye and the entire moiety from the ring-constituting carbon atom satisfy the above (i) and (ii), the Dye side is L as compared with the ring-constituting carbon atom¹. I.e. from the side with L¹The structural part from the end of the structural part facing the Dye to the ring-constituting carbon atom is Q¹. In addition, the above ring-constituting carbon atom may be bonded to L¹The alkylene bond of (b) also corresponds to the above-mentioned original form in this case. In the compound A-2, with Dye, L¹And Q¹The corresponding structures are as follows.

[ chemical formula 11]

Following the same rule, the following compounds are also shown together with Dye and L in Compound A-3¹And Q¹And corresponding structures.

[ chemical formula 12]

In the above A-3, Q¹Of the endsOH is linked to an alkylene group. However, since OH does not satisfy the above conditions (i) and (ii), Q¹Is not cleaved by the alkylene group (OH is Q)¹)。

In the present invention, Q is determined¹When it is spaced by L¹When the structural part facing the Dye has an alicyclic ring, the structural part may have a structure L¹The alkylene group having a structure of bonding the above-mentioned "Q" is also mentioned¹"or a further form thereof¹The determination method of (3) is set to priority.

In the present invention, in the above (i) and (ii), Q is a pair¹The energy levels of HOMO and LUMO and the energy levels of HOMO and LUMO of Dye are defined. The energy levels of HOMO and LUMO are generally the concept of a compound. In the present invention, Dye, L of the compound is determined according to the above-mentioned rule¹And Q¹And it is assumed that the group of Dye and L is substituted with methyl¹And the energy levels of HOMO and LUMO in the compound of the structure substituted with the methyl group are defined as the energy levels of HOMO and LUMO in Dye.

For Q¹It is also assumed that Q will be substituted by methyl¹And L¹And the energy levels of HOMO and LUMO in the compound having the structure substituted with the methyl group are defined as Q¹HOMO and LUMO in (b).

In addition, although the linking site is substituted with a methyl group in the above description, in practice, the values of HOMO and LUMO are not affected if the linking site is not a methyl group, but is an alkyl group having about 1 to 4 carbon atoms or the like. That is, instead of substituting the linking site with a methyl group, for example, the HOMO and LUMO of a compound having a linking site substituted with an ethyl group or a propyl group are used as Dye or Q¹There is virtually no problem with HOMO and LUMO.

In the present invention, Dye and Q¹The energy level difference between HOMO and LUMO can be changed from methyl to methyl¹The intersection of the fluorescence spectrum and the absorption spectrum of each compound at the junction of (2) is determined.

Among the energy levels of HOMO and LUMO of Dye, the oxidation potential of a compound in which the Dye connecting site is substituted with a methyl group is measured by cyclic voltammetry, and the obtained value is taken as the energy level of HOMO, so that the LUMO of Dye can be obtained from the energy level difference.

And, Q¹In the respective energy levels of HOMO and LUMO, with respect to the substitution of Q with a methyl group¹The compound of the linking site (b) can be obtained by measuring either the oxidation potential or the reduction potential by cyclic voltammetry, setting the value obtained when measuring the oxidation potential as the energy level of HOMO, and the value obtained when measuring the reduction potential as the energy level of LUMO, and determining the other energy level from the energy level difference.

Dye and Q in the general formula (1)¹Preferred structures of (a) and (b) will be described in detail.

(Dye in the general formula (1))

Dye in general formula (1) represents a Dye moiety having a structure obtained by removing n1 hydrogen atoms from a compound represented by general formula (2). The moiety from which the hydrogen atom is removed is represented by the formula¹The bonding portion of (1).

The mode of removing a hydrogen atom from the Dye is not particularly limited, and may be a hydrogen atom that can be used as a hydrogen atom (a hydrogen atom directly bonded to an atom constituting the ring structure of the aryl group or the heterocyclic group) of the aryl group or the heterocyclic group of a or B of the general formula (2), or a hydrogen atom that can be used as a substituent bonded to the aryl group or the heterocyclic group.

[ chemical formula 13]

In the general formula (2), a and B represent an aryl group, a heterocyclic group, or-CH ═ G. G represents a heterocyclic group.

In the general formula (2), A and B may be the same or different. Also, A is preferably a heterocyclic group. This results in a deeper oxidation potential and improved light resistance.

The aryl group that can be used as a or B is not particularly limited, and may be a group including a single ring or a group including a condensed ring. The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. Examples of the aryl group include groups containing a benzene ring and a naphthalene ring, and more preferably a group containing a benzene ring.

The heterocyclic group that can be used as a or B is not particularly limited, and includes a group containing an aliphatic heterocyclic ring or an aromatic heterocyclic ring, preferably a group containing an aromatic heterocyclic ring. Examples of the heteroaryl group of the aromatic heterocyclic group include heteroaryl groups which can be used as the substituent X described later. The aromatic heterocyclic group which may be used as A or B is preferably a 5-or 6-membered ring, more preferably a nitrogen-containing 5-membered ring. Specifically, a group including a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, an oxazole ring, a triazole ring, an indole ring, an indolenine ring, a indoline ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a benzothiazole ring, a benzoxazole ring, and a pyrazolotriazole can be suitably exemplified. Among them, preferred is a group including a pyrrole ring, a pyrazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring or a pyrazolotriazole. The pyrazolotriazole ring contains a condensed ring of a pyrazole ring and a triazole ring, and means a condensed ring obtained by at least one-by-one condensation of these rings.

G in-CH ═ G usable as a or B represents a heterocyclic group which may have a substituent, and for example, A, B is suitably listed. Among them, preferred are groups containing a benzoxazole ring, a benzothiazole ring, an indoline ring, and the like.

A. B and G may each have a substituent X, and when having a substituent X, adjacent substituents may be bonded to each other to further form a ring structure. Also, a plurality of substituents may be present.

Examples of the substituent X include R which can be used as the following general formula (4)¹Specific examples of the substituent(s) include a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group and-OR^10a、-COR^11a、-COOR^12a、-OCOR^13a、-NR^14aR^15a、-NHCOR^16a、-CONR^17aR^18a、-NHCONR^19aR^20a、-NHCOOR^21a、-SR^22a、-SO₂R^23a、-SO₃R^24a、-NHSO₂R^25aor-SO₂NR^26aR^27a。

R^10a～R^27aAre respectively independentAnd (b) represents a hydrogen atom, an aliphatic group, an aromatic group or a hetero atom-containing cyclic group. Can be used as R^10a～R^27aThe aliphatic group and the aromatic group of (3) are not particularly limited, and can be suitably used as R of the general formula (4) from the following¹Is selected from the group consisting of. Among them, the aliphatic group is preferably an alkyl group or an alkenyl group, and the aromatic group is preferably an aryl group. Can be used as R^10a～R^27aThe heteroatom-containing ring group (C) may be aliphatic or aromatic, and can be suitably used as R of the general formula (4) as described later¹The heteroaryl group or the heteroatom-containing cyclic group of (a).

In addition, -COOR^12aR of (A) to (B)^12aIn the case of a hydrogen atom (i.e., a carboxyl group), the hydrogen atom may be dissociated (i.e., a carbonate group) or may be in the form of a salt. and-SO₃R^24aR of (A) to (B)^24aIn the case of a hydrogen atom (i.e., a sulfo group), the hydrogen atom may be dissociated (i.e., a sulfonate group) or may be in the form of a salt.

Examples of the halogen atom which can be used as X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The number of carbon atoms of the alkyl group which can be used as X is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 8. The number of carbon atoms of the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and further preferably 2 to 8. The number of carbon atoms of the alkynyl group is preferably 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 25. The alkyl group, the alkenyl group and the alkynyl group may be each linear, branched or cyclic, and are preferably linear or branched.

Aryl groups comprise monocyclic or fused ring groups. The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12.

The alkyl portion of the aralkyl group (alkyl-substituted aryl) is the same as the alkyl group described above. The aryl portion of the aralkyl group is the same as the aryl group described above. The number of carbon atoms of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and still more preferably 7 to 25.

The heteroaryl group includes a group having a single ring or condensed rings, preferably a single ring or a group having 2 to 8 condensed rings, more preferably a single ring or a group having 2 to 4 condensed rings. The number of hetero atoms constituting the ring of the heteroaryl group is preferably 1 to 3. Examples of the hetero atom constituting the ring of the heteroaryl group include a nitrogen atom, an oxygen atom, a sulfur atom and the like. The heteroaryl group is preferably a group containing a 5-or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12. Examples of the heteroaryl group include groups containing a pyridine ring, a piperidine ring, a furan (furan) ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an indole ring, an imidazole ring, a pyrazole ring, a carbazole ring, a phenothiazine ring, a phenoxazine ring, an indoline ring, a thiazole ring, a pyrazine ring, a thiadiazole ring, a benzoquinoline ring, and a thiadiazole ring.

Examples of the substituent X include an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, and a heteroaryl group, each of which may have a further substituent or may be unsubstituted. The substituent which may be further contained is not particularly limited, and is preferably a substituent selected from the group consisting of an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an aromatic heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aromatic heterocyclic thio group, a sulfonyl group, a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group and a carboxyl group, and more preferably a substituent selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aromatic heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkylthio group, an. These groups can be suitably used as R of the general formula (4) from the following¹Is selected from the group consisting of.

As a preferred embodiment of the dye represented by the above general formula (2), a dye represented by the following general formula (3) can be exemplified.

[ chemical formula 14]

In the general formula (3), R³And R⁴Each independently represents a hydrogen atom or a substituent. As useful as R³And R⁴The substituent(s) is not particularly limited, and those usable as R in the following general formula (4) can be mentioned¹The same substituents as in (1).

Wherein, can be used as R³The substituent(s) is preferably an alkyl group, an alkoxy group, an amino group, an amide group, a sulfonamide group, a cyano group, a nitro group, an aryl group, a heteroaryl group, a hetero atom-containing cyclic group, an alkoxycarbonyl group, a carbamoyl group or a halogen atom, more preferably an alkyl group, an aryl group or an amino group, and still more preferably an alkyl group.

As useful as R⁴The substituent(s) of (b) is preferably an alkyl group, an aryl group, a heteroaryl group, a heteroatom-containing cyclic group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amido group, a carbamoyl group, an amino group or a cyano group, more preferably an alkyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group or an aryl group, and still more preferably an alkyl group.

Can be used as R³And R⁴The alkyl group (b) may be linear, branched or cyclic, and is preferably linear or branched.

Can be used as R³The alkyl group (C) preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and most preferably 1 to 6 carbon atoms. Examples thereof include methyl, ethyl, n-propyl, isopropyl, tert-butyl, 2-methylbutyl, 2-ethylhexyl, tert-pentyl, neopentyl, 3,5, 5-trimethylhexyl, cyclopentyl, cyclohexyl, hexyl, octyl, 1-cyclohexylethyl, 1-cyclohexylpropyl, dicyclohexylmethyl, decyl, dodecyl, hexyldecyl, hexyloctyl and the like, and methyl, ethyl, n-propyl, isopropyl, tert-butyl, 2-methylbutyl, cyclopentyl, cyclohexyl or hexyl is preferred.

Can be used as R⁴The alkyl group (C) preferably has 1 to 24 carbon atoms, more preferably 3 to 18 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a 2-methylbutyl group, a 2-ethylhexyl group, a tert-pentyl group, a neopentyl group, a 3,5, 5-trimethylhexyl group, a cyclopentyl group, a cyclohexyl group, a hexyl group, an octyl group, a 1-cyclohexylethyl group, a 1-cyclohexylpropyl group, a dicyclohexylmethyl group, a decyl group, a dodecyl group, and the likeHexyldecyl group, hexyloctyl group and the like, preferably isopropyl group, tert-butyl group, tert-pentyl group, neopentyl group, cyclohexyl group, dicyclohexylmethyl group or 2-ethylhexyl group.

Further, the alkyl group may have a substituent, and for example, as a substituent thereof, it can be arbitrarily selected from the groups usable as the substituent X described above.

In the general formula (3), B has the same meaning as that of B in the general formula (2).

As a preferred embodiment of the dye represented by the above general formula (2) or (3), a dye represented by the following general formula (4) can be exemplified.

[ chemical formula 15]

In the general formula (4), R¹And R²Each independently represents a hydrogen atom or a substituent. R¹And R²Each of which may be the same or different, and may be bonded to each other to form a ring.

As useful as R¹And R²The substituent(s) is not particularly limited, and examples thereof include alkyl (e.g., methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, hexyl, octyl, dodecyl, and trifluoromethyl), cycloalkyl (e.g., cyclopentyl and cyclohexyl), alkenyl (e.g., vinyl and allyl), alkynyl (e.g., ethynyl and propargyl), aryl (e.g., phenyl and naphthyl), heteroaryl (e.g., furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazolyl, imidazolyl, pyrazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, quinazolinyl, and phthaloyl), heteroatom-containing cyclic group (also referred to as heterocyclic group, e.g., pyrrolidinyl, imidazolidinyl, morpholinyl, and oxazolidinyl), alkoxy (e.g., methoxy, ethoxy, and propoxy), cycloalkoxy (cyclopentyloxy, and the like), Cyclohexyloxy and the like), aryloxy (phenoxy, naphthyloxy and the like), heteroaryloxy (aromatic heterocyclic oxy), alkylthio (methylthio, ethylthio, propylthio and the like), cycloalkylthio (cyclopentylthio, cyclohexylthio and the like), arylthio (phenylthio, naphthylthio and the like)Examples thereof include a heteroaryl group, a heteroarylthio group (an aromatic heterocyclic thio group), an alkoxycarbonyl group (a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, etc.), an aryloxycarbonyl group (a phenoxycarbonyl group, a naphthyloxycarbonyl group, etc.), a phosphoryl group (a dimethoxyphosphono group, a diphenylphosphoryl group, etc.), a sulfamoyl group (an aminosulfonyl group, a methylaminosulfonyl group, a dimethylaminosulfonyl group, a butylaminosulfonyl group, a cyclohexylaminosulfonyl group, an octylaminosulfonyl group, a phenylaminosulfonyl group, etc.), an acyl group (an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a cyclohexylcarbonyl group, an octylcarbonyl group, a 2-ethylhexylcarbonyl group, a phenylcarbonyl group, a naphthylcarbonyl group, a pyridylcarbonyl group, etc.), an acyloxy group (, Acylamino (acetylamino, ethylcarbonylamino, butylcarbonylamino, octylcarbonylamino, phenylcarbonylamino, etc.), acylamino (methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.), sulfonamido (methylsulfonylamino, octylsulfonylamino, 2-ethylhexylsulfonylamino, trifluoromethylsulfonylamino, etc.), carbamoyl (aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, etc.), acylamino (methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, 2-ethylhexylcarbonylamino, 2-ethylhexylaminocarbonyl, 2-ethylhexylaminocarbo, Naphthylaminocarbonyl, 2-pyridylaminocarbonyl, etc.), ureido (methylureido, ethylureido, pentylureido, cyclohexylureido, octylureido, dodecylureido, phenylureido, naphthylureido, 2-pyridylaminoureido, etc.), alkylsulfonyl (methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, etc.), arylsulfonyl (phenylsulfonyl, naphthylsulfonyl, 2-pyridylsulfonyl, etc.), amino (amino, ethylamino, dimethylamino, butylamino, dibutylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilineA naphthyl amino group, a 2-pyridylamino group, etc.), an alkylsulfonyloxy group (methanesulfonyloxy group), a cyano group, a nitro group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxyl group, a sulfo group, a carboxyl group, etc.

Among them, an alkyl group, an alkenyl group, an aryl group, or a heteroaryl group is preferable, an alkyl group, an aryl group, or a heteroaryl group is more preferable, and an alkyl group is further preferable.

Can be used as R¹And R²The substituent (2) may further have a substituent. As the substituent which may further have, there may be mentioned those which can be used as R¹And R²The above-mentioned substituent of (1). And, R¹And R²Can be with each other or with B²Or B³The substituents are bonded to form a ring. The ring formed at this time is preferably a heterocyclic ring or a heteroaryl ring, and the size of the ring formed is not particularly limited, and is preferably a 5-membered ring or a 6-membered ring.

In the general formula (4), B¹、B²、B³And B⁴Each independently represents a carbon atom or a nitrogen atom. Comprising B¹、B²、B³And B⁴The ring (2) is an aromatic ring. B is¹～B⁴Of (A), at least 2 or more are preferably carbon atoms, more preferably B¹～B⁴All being carbon atoms.

Can be used as B¹～B⁴Has a hydrogen atom or a substituent. Can be used as B¹～B⁴The number of carbon atoms having a substituent is not particularly limited, but is preferably 0, 1 or 2, and more preferably 1. In particular, B¹And B⁴Is a carbon atom, and preferably at least one of them has a substituent.

As useful as B¹～B⁴The substituent(s) having carbon atom(s) in (3) is not particularly limited, and there may be mentioned those usable as R¹And R²The above-mentioned substituent of (1). Among them, preferred is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an acyl group, an amido group, a sulfonamido group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an amino group, a cyano group, a nitro group, a halogen atom or a hydroxyl group, and more preferred is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl groupAn acyl group, an amide group, a sulfonamide group, a carbamoyl group, an amino group, a cyano group, a nitro group, a halogen atom or a hydroxyl group.

As useful as B¹And B⁴The substituent of the carbon atom(s) in (b) is more preferably an alkyl group, an alkoxy group, a hydroxyl group, an amide group, a sulfonamide group or a carbamoyl group, particularly preferably an alkyl group, an alkoxy group, a hydroxyl group, an amide group or a sulfonamide group, and most preferably a hydroxyl group, an amide group or a sulfonamide group.

As useful as B²And B³The substituent of the carbon atom(s) in (b) is more preferably an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an amino group, a cyano group, a nitro group or a halogen atom, and particularly preferably any of the substituents is an electron-withdrawing group (e.g., an alkoxycarbonyl group, an acyl group, a cyano group, a nitro group or a halogen atom).

In the general formula (4), R³And R⁴Each independently represents a hydrogen atom or a substituent, and R in the general formula (3)³And R⁴The meaning is the same.

The squarylium compound used in the present invention is not particularly limited as long as it is a squarylium dye represented by any one of general formula (2), and further general formulae (3) and (4). Examples thereof include compounds described in Japanese patent laid-open Nos. 2006-160618, 2004/005981, 2004/007447, Dyes and Pigment, 2001, 49, p.161-179, 2008/090757, 2005/121098 and 2008-275726.

Preferred specific examples of the dye represented by the general formula (2) are shown below. However, the present invention is not limited to these examples.

In the following specific examples, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.

[ chemical formula 16]

In addition to the above specific examples, specific examples of the dye represented by the general formula (2) are also listed below. The substituent Bs in the following table represents the following structure. In the following structures and tables, Me represents a methyl group, Et represents an ethyl group, i-Pr represents an isopropyl group, Bu represents an n-butyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group. In the following structures, a represents a bonding portion with a carbon four-membered ring in each general formula.

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

General formula (3)

[ chemical formula 20]

The squaric acid compound used in the present invention includes, in addition to the above, a compound (instead of L) derived from a squaraine dye structure contained in an exemplary compound described later, which is represented by the general formula (1)¹A compound having a hydrogen atom added thereto), and compounds described in, for example, japanese patent laid-open nos. 2002-097383 and 2015-068945.

(Q in the general formula (1))¹)

Q in the formula (1)¹The preferable structure of (2) is a structural site including a structure in which 1 hydrogen atom is removed from a compound represented by any one of the following general formulae (5) to (13). The moiety from which the hydrogen atom is removed is represented by the formula¹The bonding portion of (1).

The mode of removing a hydrogen atom from a compound represented by each general formula described below is not particularly limited, and may be a symbol R (R) that can be used as a symbol in each general formula⁵～R²⁰、R²²、R²³、R²⁵～R²⁷、R³⁰～R³⁶、R^37a～R^37e、R³⁸～R⁴²) May be R⁵～R²⁷、R³⁰～R³⁶、R^37a～R^37eAnd R³⁸～R⁴²May further have a hydrogen atom of each substituent.

[ chemical formula 21]

In each formula, R⁵～R²⁰、R²²、R²³、R²⁵～R²⁷、R³⁰～R³⁶、R^37a～R^37e、R³⁸～R⁴²Each independently represents a hydrogen atom or a substituent. As R⁵～R²⁰、R²²、R²³、R²⁵～R²⁷、R³⁰～R³⁶、R^37a～R^37e、R³⁸～R⁴²The substituents which may be taken individually are not particularly limited, and there may be mentioned as R which can be used as the general formula (4)¹The substituent(s) of (a) is (are) preferably an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, a heteroatom-containing cyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, a hydroxyl group, an amino group, a halogen atom, an acyl group, an acyloxy group, an acylamino group, a cyano group, a sulfo group or a carboxyl group.

R²¹And R²⁴Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Wherein, when a hydrogen atom is used as R²¹And R²⁴When the nitrogen atom of the hydrogen atom is removed from the group with the linking group L¹Bonding is carried out on the raw materials,

can be used as R²¹And R²⁴Alkyl and aryl of (A) and R useful as general formula (4)¹And alkyl and aryl have the same meaning. Can be used as R²¹And R²⁴The heterocyclic group of (A) includes heteroaryl and heteroatom-containing cyclic groups, which are useful as R¹The heteroaryl and the heteroatom-containing cyclic group have the same meanings.

In the general formula (13), X¹Represents an oxygen atom, a sulfur atom or a carbon atom. In the compound represented by the general formula (13), the linkage-X¹Curve representation of and N with-X¹-C-N-together form a group of atoms of the ring. The atom group is not particularly limited, and includes a carbon atom, a nitrogen atom, a sulfur atom, and the like as ring-constituting atoms, and a hydrogen atom and the like bonded to these atoms. In the compound represented by the general formula (13), as containing-X¹The ring formed of an — C ═ N-group includes an aliphatic heterocyclic ring and an aromatic heterocyclic ring, and may be a monocyclic ring or a condensed ring. The number of ring members forming a monocyclic or fused ring which can be used as the ring is not particularly limited, and is, for example, 5 to 7 members, preferably 5 or 6 members. As containing-X¹The ring formed by the group-C ═ N-is not particularly limited, and examples thereof include R of the general formula (4)¹And a ring forming a hetero atom-containing cyclic group and a ring forming a heteroaryl group, preferably a ring forming a heteroaryl group, more preferably a 2-benzothiazole ring.

n is an integer of 1 to 3, preferably 1.

R⁵～R²⁷、R³⁰～R³⁶、R^37a～R^37eAnd R³⁸～R⁴²When adjacent to each other, they may be bonded to form a ring.

Specific examples of the compound represented by the general formula (1) are shown below. However, the present invention is not limited to these examples.

In the following specific examples, Me represents a methyl group and Et represents an ethyl group.

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

[ chemical formula 25]

The compound represented by the general formula (1) can be synthesized using known methods, for example, according to the synthesis methods described in the examples below.

The content of the compound represented by the general formula (1) used in the resin composition of the present invention is preferably 0.005 part by mass or more and 5 parts by mass or less, more preferably 0.01 part by mass or more and 3 parts by mass or less, and further preferably 0.1 part by mass or more and 1.5 parts by mass or less, relative to 100 parts by mass of a binder resin described later.

When the filter contains 2 or more kinds of pigments, the above content is the total content thereof.

In addition, when the optical filter of the present invention also serves as a polarizing plate protective film or an adhesive layer described later, the content of the compound represented by the general formula (1) may be within the above range.

< resin >

The resin composition of the present invention contains a resin (binder) (the binder may contain any conventional component other than the polymer. The resin used in the present invention is preferably transparent. Herein, the term "transparent" means a resin having a total light transmittance of usually 70% or more, preferably 80% or more, and more preferably 90% or more, as measured by forming a test piece having a thickness of 1 mm. Examples of the resin used as the binder of the resin composition of the present invention include polystyrene resin, cycloolefin resin, cellulose acylate resin, and acrylic resin, and these resins can be suitably used as general examples of optical filters. Among them, a polystyrene resin or a cycloolefin resin is preferable, and a polystyrene resin is particularly preferable, from the viewpoint of further reducing the fluorescence quantum yield.

Preferred forms are explained for polystyrene resin and cycloolefin resin which are preferable as the resin used in the present invention.

(polystyrene resin)

The polystyrene contained in the polystyrene resin is a resin containing 50 mass% or more of a styrene component. In the present invention, only 1 kind of polystyrene may be used, or 2 or more kinds may be used in combination. Here, the styrene component is a structural unit derived from a monomer having a styrene skeleton in its structure.

In order to control the resin composition or the optical filter to a preferred photoelastic coefficient and to a preferred moisture absorption, the polystyrene more preferably contains 70 mass% or more of a styrene component, and even more preferably 85 mass% or more. Further, the polystyrene is preferably composed of only a styrene component.

Examples of the polystyrene include homopolymers of styrene compounds and copolymers of 2 or more styrene compounds. Here, the styrene compound is a compound having a styrene skeleton in its structure, and means a compound including a portion in which a substituent is introduced to an ethylenically unsaturated bond of styrene in addition to styrene. Examples of the styrene compound include styrene; alkylstyrenes such as alpha-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 3, 5-dimethylstyrene, 2, 4-dimethylstyrene, o-ethylstyrene, p-ethylstyrene, t-butylstyrene; for example, a substituted styrene obtained by introducing a hydroxyl group, an alkoxy group, a carboxyl group, a halogen or the like into the benzene nucleus of a styrene such as hydroxystyrene, tert-butoxystyrene, vinylbenzoic acid, o-chlorostyrene or p-chlorostyrene. Among them, the polystyrene used in the present invention is preferably a homopolymer of styrene (i.e., polystyrene) from the viewpoints of easy availability, material price, and the like.

The structural component other than the styrene component contained in the polystyrene is not particularly limited. That is, the polystyrene may be a styrene-diene copolymer or a styrene-polymerizable unsaturated carboxylic acid ester copolymer. Also, a mixture of polystyrene and a synthetic rubber (for example, polybutadiene, polyisoprene, or the like) can also be used. Further, High Impact Polystyrene (HIPS) obtained by graft polymerizing styrene and a synthetic rubber is also preferable. Further, a polystyrene obtained by dispersing a rubbery elastomer in a continuous phase of a polymer containing a styrene component (for example, a copolymer of a styrene component and a (meth) acrylate component) and graft-polymerizing the copolymer with the rubbery elastomer (referred to as a graft-type high-impact polystyrene "graft HIPS") is also preferable. Further, so-called styrene-based elastomers can also be suitably used.

Also, the above polystyrene may be hydrogenated (may be hydrogenated polystyrene). The hydrogenated polystyrene is not particularly limited, but is preferably a hydrogenated styrene-diene copolymer such as a hydrogenated styrene-butadiene-styrene block copolymer (SEBS) or a hydrogenated styrene-isoprene-styrene block copolymer (SEPS) as a resin obtained by adding hydrogen to SBS or SIS. The hydrogenated polystyrene may be used in only 1 kind, or may be used in 2 or more kinds.

The molecular weight of the polystyrene used in the present invention may be appropriately selected depending on the purpose of use, but the mass average molecular weight measured by gel permeation chromatography using a tetrahydrofuran solution (toluene solution when the polymer is not dissolved) is usually 5000 to 500000, preferably 8000 to 200000, and more preferably 10000 to 100000. The polymer having a molecular weight within the above range can achieve both the mechanical strength and the moldability of the molded article at a high level and in a balanced manner.

As the polystyrene, a plurality of kinds different in composition, molecular weight, and the like can be used at the same time.

The polystyrene resin can be obtained by a well-known anionic, bulk, suspension, emulsion or solution polymerization method. Also, in the polystyrene resin, unsaturated double bonds of benzene rings of the conjugated diene or styrene monomer may be hydrogenated. The hydrogenation rate can be measured by Nuclear Magnetic Resonance (NMR).

Examples of the polystyrene resin include commercially available products such as "CLEAREN 530L", "CLEAREN 730L", "TUFPRENE 126S", "ASAPRENE T411" manufactured by Asahi Kasei Corporation, "Clayton D1102A", "Clayton D1116A", "Styrolux S", "Styrolux T" manufactured by Styrolysis Corporation, "ASahi Kasei Chemicals Corporation," ASAFLEX840 "," ASAFLEX 860 "(SBS) manufactured by Styrolysis Corporation," 679 "," HF77 "," SGP-10 ", DICSTYRENE XC-515" manufactured by DIC Corporation, "DICSTYRENE XC-535" (GPPS) manufactured by PS Corporation, "D", "H0103", "HT" manufactured by "DICSTYRENE GH-DIC 8300-5" (HIPS) manufactured by Denka Company Limited. Examples of the hydrogenated polystyrene-based resin include "TUFTEC H series" manufactured by Asahi Kasei Chemicals Corporation, "Clayton G series" (SEBS) manufactured by Shell Japan Ltd., "DYNAR 0N" (hydrogenated styrene-butadiene random copolymer) manufactured by JSR Corporation, "KURAAYCO", and "SEPT 0N" (SEPS) manufactured by LTD. Examples of the modified polystyrene-based resin include "TUFTEC M series" manufactured by Asahi Kasei Chemicals Corporation, "EP 0 FREE D" manufactured by Daicel Corporation, "polar group-modified DYNAR 0N" manufactured by JSRcorporation, "TOAGOSEI CO., LTD" RESEDA "manufactured by LTD.

(cycloolefin resin)

The cyclic olefin compound forming the cycloolefin polymer (also referred to as cyclic polyolefin) contained in the cycloolefin resin is not particularly limited as long as it is a compound having a ring structure containing a carbon-carbon double bond, and examples thereof include norbornene compounds, monocyclic cyclic olefin compounds other than norbornene compounds, cyclic conjugated diene compounds, and vinyl alicyclic hydrocarbon compounds.

Examples of the cycloolefin polymer contained in the cycloolefin resin include (1) a polymer containing a structural unit derived from a norbornene compound, (2) a polymer containing a structural unit derived from a monocyclic cyclic olefin compound other than the norbornene compound, (3) a polymer containing a structural unit derived from a cyclic conjugated diene compound, (4) a polymer containing a structural unit derived from a vinyl alicyclic hydrocarbon compound, and hydrogenated products of polymers containing structural units derived from the respective compounds (1) to (4). In the present invention, the polymer containing a structural unit derived from a norbornene compound and the polymer containing a structural unit derived from a monocyclic cyclic olefin compound contain a ring-opened polymer of each compound.

The cycloolefin polymer contained in the cycloolefin resin is not particularly limited, and is preferably a polymer having a structural unit derived from a norbornene compound represented by the following general formula (a-II) or (a-III). The polymer having a structural unit represented by the following general formula (A-II) is an addition polymer of a norbornene compound, and the polymer having a structural unit represented by the following general formula (A-III) is a ring-opened polymer of a norbornene compound.

[ chemical formula 26]

In the general formula, m is an integer of 0 to 4, preferably 0 or 1.

R³～R⁶Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

In the present invention, the hydrocarbon group is not particularly limited as long as it is a group containing a carbon atom and a hydrogen atom, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group (aromatic hydrocarbon group). Among them, preferred is an alkyl group or an aryl group.

X²And X³、Y²And Y³Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, - (CH)₂)nCOOR¹¹、-(CH₂)nOCOR¹²、-(CH₂)nNCO、-(CH₂)nNO₂、-(CH₂)nCN、-(CH₂)nCONR¹³R¹⁴、-(CH₂)nNR¹³R¹⁴、-(CH₂)nOZ、-(CH₂) nW or X²And Y²Or X³And Y³Bonded to each other to form (-CO)₂O or (-CO)₂NR¹⁵。

Herein, R is¹¹～R¹⁵Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, Z represents a hydrocarbon group or a halogen-substituted hydrocarbon group, and W represents Si (R)¹⁶)_pD_(3-p)(R¹⁶A hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom or-OCOR¹⁷OR-OR¹⁷(R¹⁷Represents a hydrocarbon group having 1 to 10 carbon atoms). p is an integer of 0 to 3). n is an integer of 0 to 10, preferably 0 to 8, and more preferably 0 to 6.

In the general formula (A-II) or (A-III), R³～R⁶Are each preferably a hydrogen atom or-CH₃From the viewpoint of moisture permeability, hydrogen atoms are more preferable.

X²And X³Are each preferably a hydrogen atom, -CH₃、-C₂H₅From the viewpoint of moisture permeability, hydrogen atoms are more preferable.

Y²And Y³Each is preferably a hydrogen atom, a halogen atom (particularly a chlorine atom) or- (CH)₂)nCOOR¹¹(especially-COOCH)₃) From the viewpoint of moisture permeability, hydrogen atoms are more preferable.

Other groups may be appropriately selected.

The polymer having a structural unit represented by the general formula (A-II) or (A-III) may further contain at least one or more structural units represented by the following general formula (A-I).

[ chemical formula 27]

In the general formula, R¹And R²Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X¹And Y¹Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, - (CH)₂)nCOOR¹¹、-(CH₂)nOCOR¹²、-(CH₂)nNCO、-(CH₂)nNO₂、-(CH₂)nCN、-(CH₂)nCONR¹³R¹⁴、-(CH₂)nNR¹³R¹⁴、-(CH₂)nOZ、-(CH₂) nW or X¹And Y¹Bonded to each other to form (-CO)₂O or (-CO)₂NR¹⁵。

Herein, R is¹¹～R¹⁵Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, Z represents a hydrocarbon group or a halogen-substituted hydrocarbon group, and W represents Si (R)¹⁶)_pD_(3-p)(R¹⁶A hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom or-OCOR¹⁷OR-OR¹⁷(R¹⁷Represents a hydrocarbon group having 1 to 10 carbon atoms). p is an integer of 0 to 3). n represents an integer of 0 to 10.

The cyclic polyolefin having a structural unit represented by the general formula (a-II) or (a-III) contains the structural unit derived from the norbornene compound in an amount of 90% by mass or less, more preferably 30 to 85% by mass, still more preferably 50 to 79% by mass, and most preferably 60 to 75% by mass, based on the total mass of the cyclic polyolefin, from the viewpoint of adhesion to a polarizer. Here, the ratio of the structural unit derived from the norbornene compound represents an average value in the cyclic polyolefin.

Addition (co) polymers of norbornene compounds are described in Japanese patent laid-open No. 10-007732, Japanese unexamined patent publication No. 2002-504184, U.S. Pat. No. 2004/229157A1, International publication No. 2004/070463 and the like.

As the polymer of the norbornene compound, it is obtained by addition polymerization of norbornene compounds (for example, polycyclic unsaturated compounds of norbornene) with each other.

Further, as the polymer of the norbornene compound, there can be mentioned, as necessary, a copolymer obtained by addition polymerization of the norbornene compound and an olefin such as ethylene, propylene or butene, a conjugated diene such as butadiene or isoprene, a non-conjugated diene such as ethylidene norbornene, acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, acrylic ester, methacrylic ester, maleimide, vinyl acetate or an ethylenically unsaturated compound such as vinyl chloride. Among them, a copolymer with ethylene is preferable.

As such addition (co) polymers of norbornene compounds, there may be mentioned those sold under the trade name Appel by Mitsui Chemicals, Inc. and different in glass transition temperature (Tg) from each other, for example, APL8008T (Tg70 ℃ C.), APL6011T (Tg105 ℃ C.), APL6013T (Tg125 ℃ C.), or APL6015T (Tg145 ℃ C.), and the like. Also, particles such as TOPAS8007, TOPAS6013, TOPAS6015, etc. are sold by polyplasticsco. Further, Appear3000 is sold by Ferrania corporation.

As the polymer of the norbornene compound, a commercially available product can be used. For example, it is sold by JSR under the trade name Arton G or Arton F, and by Zeon Corporation under the trade name Zeonor ZF14, ZF16, Zeonex 250, or Zeonex 280.

The hydrogenated product of the polymer of the norbornene compound can be synthesized by subjecting the norbornene compound or the like to addition polymerization or metathesis ring-opening polymerization, followed by hydrogenation. Synthetic methods are described in, for example, Japanese patent application laid-open Nos. H1-240517, H7-196736, H60-026024, H62-019801, H2003-159767, and H2004-309979.

The molecular weight of the cycloolefin polymer used in the present invention can be appropriately selected depending on the purpose of use, but the mass average molecular weight in terms of polyisoprene or polystyrene measured by gel permeation chromatography of a cyclohexane solution (toluene solution when the polymer is not dissolved) is usually 5000 to 500000, preferably 8000 to 200000, and more preferably 10000 to 100000. The polymer having a molecular weight within the above range can achieve both the mechanical strength and the moldability of the molded article at a high level and in a balanced manner.

The resin composition of the present invention preferably contains 50% by mass or more of the binder resin, more preferably 70% by mass or more, and particularly preferably 90% by mass or more, from the viewpoint of the sharpness and light resistance of the absorbed waveform.

The binder resins may be 2 or more, and binders having different composition ratios and/or molecular weights may be used together. In this case, the total content of the binder resins is within the above range.

< additive >

The resin composition of the present invention may contain an additive within a range not impairing the effects of the present invention. For example, additives that can be blended with plastic films in general may be contained as necessary. Examples of such additives include antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, and fillers, and the content thereof can be selected within a range not impairing the object of the present invention. Examples of the additives include known plasticizers, organic acids, polymers, retardation regulators, ultraviolet absorbers, antioxidants, matting agents, and the like. For these, reference can be made to the descriptions in paragraphs [0062] to [0097] of Japanese patent laid-open No. 2012 and 155287, which are incorporated in the present specification. Further, examples of the additive include a peeling accelerator, an organic acid, and a polycarboxylic acid derivative. For these, reference can be made to the descriptions in paragraphs [0212] to [0219] of international publication No. 2015/005398, and these contents are incorporated into the present specification. Further, as the additive, a radical scavenger, a deterioration inhibitor, and the like, which will be described later, can be mentioned.

The content of the additive (when two or more additives are contained in the resin composition, the total content thereof) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 5 to 30 parts by mass, per 100 parts by mass of the binder resin.

(antioxidant)

As one of the preferable additives, an antioxidant can also be cited. As the antioxidant, the contents of paragraphs [0143] to [0165] of International publication No. 2015/005398 can be referred to, and these contents are incorporated in the present specification.

(radical scavenger)

As one of the preferred additives, a radical scavenger can also be cited. As for the radical scavenger, reference can be made to the descriptions in paragraphs [0166] to [0199] of International publication No. 2015/005398, and these contents are incorporated in the present specification.

(deterioration inhibitor)

As one of the preferable additives, a deterioration inhibitor can be also cited. The deterioration inhibitor can be described in international publication nos. 2015/005398 [0205] to [0206], and the contents thereof are incorporated in the present specification.

(ultraviolet absorber)

In the present invention, an ultraviolet absorber may be added to the optical filter from the viewpoint of preventing deterioration. As the ultraviolet absorber, an ultraviolet absorber having a small absorption of visible light having a wavelength of 400nm or more is preferably used from the viewpoint of excellent absorption of ultraviolet light having a wavelength of 370nm or less and good liquid crystal display properties. Specific examples of the ultraviolet absorber preferably used in the present invention include hindered phenol compounds, hydroxybenzophenone compounds, benzotriazole compounds, salicylate compounds, benzophenone compounds, cyanoacrylate compounds, and nickel complex salt compounds.

Examples of the hindered phenol compound include 2, 6-di-tert-butyl-p-cresol, pentaerythritol-tetrakis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, and the like.

Examples of the benzotriazole-based compound include 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2-methylenebis (4- (1,1,3, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), (2, 4-bis- (N-octylthio) -6- (4-hydroxy-3, 5-di-tert-butylanilino) -1,3, 5-triazine, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], N ' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamide) ], and, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 2(2 '-hydroxy-3', 5 '-di-tert-butylphenyl) -5-chlorobenzotriazole, (2 (2' -hydroxy-3 ', 5' -di-tert-amylphenyl) -5-chlorobenzotriazole, 2, 6-di-tert-butyl-p-cresol, pentaerythritol-tetrakis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol, and the like.

[ optical Filter ]

The film formed using the resin composition of the present invention is suitable as an optical filter. That is, the optical filter of the present invention is a film comprising the resin composition of the present invention. The content of each component in the optical filter and the film is the same as that in the resin composition of the present invention.

Hereinafter, a method for manufacturing the optical filter will be described.

< method for manufacturing optical filter >

The method for producing the optical filter is not particularly limited except for using the resin composition of the present invention, and can be suitably produced by a general molding method.

The optical filter of the present invention can be manufactured by, for example, a solution casting film forming method. In the solution casting film forming method, a film is produced using a solution (dope, one form of the resin composition of the present invention) in which at least the compound represented by the general formula (1) and the binder resin are dissolved in an organic solvent.

The organic solvent is not particularly limited as long as it can dissolve the compound represented by the general formula (1) and the binder resin. For example, a solvent selected from the group consisting of C1-4 alcohols, C3-12 ethers, C3-12 ketones, C3-12 esters, and C1-6 halogenated hydrocarbons can be used.

The above ethers, ketones and esters may have a cyclic structure. Further, a compound having 2 or more functional groups (i.e., -O-, -CO-, and-COO-) of the ether, ketone, and ester can also be used as the organic solvent. The organic solvent may have other functional groups such as alcoholic hydroxyl group. In the case of an organic solvent having 2 or more functional groups, the number of carbon atoms thereof is preferably within the above-described preferred range of the number of carbon atoms of the solvent having any functional group.

The content of the binder resin in the solution is preferably adjusted to 10 to 40 mass%, and more preferably 10 to 30 mass%. The organic solvent (main solvent) may contain any of the additives described above.

As a drying method in the solution casting film-forming method, U.S. Pat. No. 2,336,310, U.S. Pat. No. 2,367,603, U.S. Pat. No. 2,492,078, U.S. Pat. nos. 2,492, 977, U.S. Pat. No. 2,492,978, U.S. Pat. No. 2,607,704, U.S. Pat. No. 2,739,069 and U.S. Pat. No. 2,739,070, U.K. Pat. No. 640731 and U.K. Pat. No. 736892, and japanese patent publication nos. 45-004554, 49-005614, 60-176834, 60-203430 and 62-115035 can be referred to. The drying on the endless belt can be performed by blowing an inert gas such as air or nitrogen.

The prepared solution (dope) can be cast into a film in 2 or more layers. The dope is cast onto the endless belt, and the solvent is evaporated to form on the film. The dope solution before casting is preferably adjusted so that the concentration thereof is in the range of 10 to 40 mass% in terms of solid content. The surface of the endless belt is preferably finished in a mirror-finished state.

When casting a plurality of cycloolefin resin solutions of 2 layers or more, a film can be produced while casting and laminating solutions containing cycloolefin resins from a plurality of casting ports provided at intervals in the traveling direction of the support. For example, the methods described in Japanese patent application laid-open Nos. 61-158414, 1-122419 and 11-198285 can be used. Further, the cycloolefin resin solution can be made into a film by casting from 2 casting ports. For example, the methods described in Japanese patent publication No. 60-27562, Japanese patent publication No. 61-94724, Japanese patent publication No. 61-947245, Japanese patent publication No. 61-104813, Japanese patent publication No. 61-158413, and Japanese patent publication No. 6-134933 can be used. Further, a casting method of a resin film described in jp 56-162617 a, which wraps the flow of a high viscosity resin solution with a low viscosity resin solution and simultaneously extrudes the high/low viscosity resin solution, can also be used.

Further, it is also possible to produce a film by peeling off the film formed on the support through the first casting port using 2 casting ports and performing the second casting on the side in surface contact with the support. For example, the method described in Japanese patent publication No. 44-020235 can be cited.

The same solution may be used for the solution to be cast, or 2 or more different solutions may be used. In order to impart a multilayer function, a solution corresponding to the function may be extruded from each casting port. The solution casting film formation may be performed simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, an ultraviolet absorbing layer, a polarizing layer, and the like).

The compound (dye) represented by the general formula (1) can be added to the solution, for example, by mixing the solution with a binder resin in an organic solvent during the preparation of a dope.

(drying treatment)

The steps from the casting of the dope to the post-drying may be performed in an air atmosphere, or may be performed in an inert gas atmosphere such as nitrogen. The winder used for manufacturing the optical filter of the present invention may be a commonly used winder, and can be wound by a winding method such as a constant tension method, a constant torque method, a taper tension method, or a programmed tension control method in which an internal stress is constant.

(stretching treatment)

The filter may be subjected to a stretching process. The desired retardation can be imparted to the filter by the stretching process. The stretching direction of the filter is preferably either the width direction or the longitudinal direction.

Methods of stretching in the width direction are described in, for example, Japanese patent laid-open Nos. 62-115035, 4-152125, 4-284211, 4-298310, and 11-48271.

The stretching of the film (the filter before the stretching treatment) is performed under heating. The film can be stretched in a process in drying, and is effective particularly in the case where a solvent remains. In the case of stretching in the longitudinal direction, for example, if the speed of the film on the transport roller is adjusted so that the film winding speed is faster than the film peeling speed, the film is stretched. In the case of stretching in the width direction, the film can be stretched by conveying the film while maintaining the width of the film by a tenter and gradually expanding the width of the tenter. Stretching may be performed using a stretcher (preferably, uniaxial stretching using a long stretcher) after the film is dried.

The method of forming the optical filter is not particularly limited, and the optical filter can be produced as described above, and any of a heat-melting molding method and a solution casting method can be used. The heat melt molding method can be classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method, and the like in more detail, but among these methods, in order to obtain a film excellent in mechanical strength, surface accuracy, and the like, the extrusion molding method, the inflation molding method, and the press molding method are preferable, and the extrusion molding method is most preferable. The molding conditions may be appropriately selected depending on the purpose of use and the molding method, and when the heating melt molding method is used, the temperature of the drum is appropriately set within a range of usually 150 to 400 ℃, preferably 200 to 350 ℃, and more preferably 230 to 330 ℃. When the polymer temperature is too low, the fluidity is deteriorated, and sink marks or deformation are generated in the film, and when the polymer temperature is too high, voids or silver streaks due to thermal decomposition of the polymer may be generated, and molding defects such as yellowing of the film may be generated.

(Properties and Properties of optical Filter)

Preferable physical properties and characteristics of the optical filter of the present invention will be described.

The thickness of the optical filter is usually 5 to 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm in consideration of improvement in productivity due to reduction in handleability and drying time during lamination.

The wetting tension of the surface of the optical filter is preferably 40mN/m or more, more preferably 50mN/m or more, and still more preferably 55mN/m or more. When the wetting tension of the surface is in the above range, the adhesion strength of the optical filter to the polarizer is improved. For example, corona discharge treatment, ozone blowing, ultraviolet irradiation, flame treatment, chemical treatment, and other known surface treatments can be performed to adjust the wetting tension of the surface.

The phase difference (retardation) of the optical filter of the present invention will be explained. The in-plane retardation value Ro at 589nm of the optical filter of the present invention is preferably 0 to 20nm, more preferably 0 to 10 nm. The retardation value Rth in the thickness direction is preferably-20 to 50nm, more preferably-10 to 20 nm.

In general, the retardation can be controlled by the retardation and stretching ratio of the film before stretching, the stretching temperature, and the thickness of the stretched oriented film. When the film thickness before stretching is constant, the absolute value of retardation tends to increase in a film having a large stretching magnification, and therefore, a stretch-oriented film having a desired retardation can be obtained by changing the stretching magnification.

When the optical filter is subjected to a stretching treatment, the thickness of the optical filter before stretching is preferably about 50 to 500 μm, and the smaller the thickness variation, the more preferably within ± 8%, preferably within ± 6%, and more preferably within ± 4% over the entire surface.

The stretching ratio is preferably 1.1 to 10 times, more preferably 1.3 to 8 times, and the desired retardation may be within this range.

The filter thus obtained is capable of orienting the molecules by stretching so that it has a retardation of a desired magnitude.

The smaller the variation in retardation, the more preferable the variation in retardation is, the smaller the variation in retardation in the in-plane direction and in the thickness direction is, the smaller the variation in retardation at a wavelength of 589nm is, the smaller the variation in retardation at a wavelength of usually within ± 50nm, preferably within ± 30nm, and more preferably within ± 20 nm.

In addition to using these small films before stretching, variations in retardation in the in-plane and thickness directions and thickness unevenness of the optical filter can be reduced by uniformly applying stress to the film during stretching. Therefore, the stretching is preferably performed in an environment of preferably ± 5 ℃ or less, more preferably ± 2 ℃ or less, and particularly preferably controlled to ± 0.5 ℃ or less, with a uniform temperature distribution.

[ image display apparatus ]

Examples of the image display device of the present invention include a liquid crystal display device and an organic electroluminescence display device. The image display device of the present invention will be described by taking a liquid crystal display device of a preferred embodiment (also referred to as a "liquid crystal display device of the present invention") as an example.

A liquid crystal display device of the present invention is characterized by comprising at least one optical filter of the present invention. The optical filter of the present invention can be used as a polarizer protective film and/or an adhesive layer as described later, and can also be included in a backlight unit for a liquid crystal display device.

The liquid crystal display device preferably includes an optical filter, a polarizing plate including a polarizer and a polarizing plate protective film, an adhesive layer, and a liquid crystal cell, and the polarizing plate is preferably bonded to the liquid crystal cell via the adhesive layer. In the liquid crystal display device, the optical filter may also serve as a polarizer protective film or an adhesive layer. That is, liquid crystal display devices are classified into those including a polarizing plate, an adhesive layer, and a liquid crystal cell, each including a polarizer and an optical filter (polarizing plate protective film), and those including a polarizing plate, an optical filter (adhesive layer), and a liquid crystal cell, each including a polarizer and a polarizing plate protective film.

Fig. 1 is a schematic diagram showing an example of a liquid crystal display device of the present invention. In fig. 1, a liquid crystal display device 10 includes a liquid crystal cell having a liquid crystal layer 5, and liquid crystal cell upper electrode substrates 3 and liquid crystal cell lower electrode substrates 6 disposed above and below the liquid crystal layer 5, and upper polarizing plates 1 and lower polarizing plates 8 disposed on both sides of the liquid crystal cell. A color filter layer may be stacked on the upper electrode substrate 3 or the lower electrode substrate 6. A backlight is disposed on the rear surface of the liquid crystal display device 10. The light source of the backlight is not particularly limited. For example, a light-emitting device using a white LED can be used.

The upper polarizing plate 1 and the lower polarizing plate 8 each have a structure in which polarizers are laminated so as to be sandwiched by two polarizing plate protective films, and in the liquid crystal display device 10 of the present invention, at least one polarizing plate is preferably a polarizing plate including the optical filter of the present invention.

In the liquid crystal display device 10 of the present invention, the liquid crystal cell and the polarizing plate (the upper polarizing plate 1 and/or the lower polarizing plate 8) may be bonded to each other through an adhesive layer (not shown). In this case, the optical filter of the present invention can also serve as the aforementioned adhesive layer.

The liquid crystal display device 10 includes an image direct-view type, an image projection type, and a light modulation type. In the present invention, an active matrix liquid crystal display device using a 3-terminal or 2-terminal semiconductor element such as a TFT or an MIM is effective. Of course, the present invention is also effective for a passive matrix liquid crystal display device represented by an STN mode called time division driving.

When the optical filter of the present invention is included in a backlight unit, the polarizing plate of a liquid crystal display device may be a normal polarizing plate (a polarizing plate not including the optical filter of the present invention) or a polarizing plate including the optical filter of the present invention. The adhesive layer may be a normal adhesive layer (not the optical filter of the present invention) or may be an adhesive layer based on the optical filter of the present invention.

The IPS mode liquid crystal display device described in paragraphs 128 to 136 of jp 2010-102296 a is preferable as the liquid crystal display device of the present invention.

< polarizing plate >

The polarizing plate used in the present invention includes a polarizer and at least one polarizing plate protective film.

The polarizing plate used in the present invention preferably has a polarizer and polarizing plate protective films on both sides of the polarizer, and preferably includes the optical filter of the present invention on at least one side as a polarizing plate protective film. The polarizer may have a normal polarizer protective film on the side opposite to the side having the optical filter (polarizer protective film) of the present invention.

The thickness of the polarizer protective film used in the present invention is 5 μm or more and 120 μm or less, and more preferably 10 μm or more and 100 μm or less. A thin film is preferable because display unevenness is less likely to occur after a lapse of time at high temperature and high humidity when the film is mounted on a liquid crystal display device. On the other hand, if the thickness is too thin, it is difficult to stably transport the film or the polarizing plate during production. When the optical filter of the present invention is used as a polarizer protective film, the thickness of the optical filter preferably satisfies the above range.

Shape, composition

The shape of the polarizing plate used in the present invention includes not only a polarizing plate cut into a sheet having a size capable of being directly attached to a liquid crystal display device but also a polarizing plate manufactured in a long form by continuous production and wound into a roll shape (for example, a form having a roll length of 2500m or more or 3900m or more). For use in a large-screen liquid crystal display device, the width of the polarizing plate is preferably set to 1470mm or more.

The polarizing plate used in the present invention is composed of a polarizer and at least one polarizing plate protective film, and is preferably also composed by further laminating a separation film on the surface of one surface of the polarizing plate.

The separation film is used to protect the polarizing plate during shipment of the polarizing plate and product inspection. The separation film is used for the purpose of covering the adhesive layer bonded to the liquid crystal panel, and is used for bonding the polarizing plate to the surface side of the liquid crystal panel.

(polarizer)

A polarizer used for the polarizing plate of the present invention will be explained.

As a polarizer that can be used for the polarizing plate used in the present invention, a polyvinyl alcohol (PVA) and dichroic molecules are preferable, and as described in japanese patent application laid-open No. 11-248937, a polyvinylene polarizer in which a polyene structure is formed by dehydration and dechlorination of PVA or polyvinyl chloride and oriented can be used.

Film thickness of polarizer

The thickness of the polarizer before stretching is not particularly limited, but is preferably 1 μm to 1mm, and particularly preferably 5 to 200 μm, from the viewpoint of stability of film holding and uniformity of stretching. Further, as described in Japanese patent laid-open No. 2002-236212, a thin PVA film can be used, in which the stress generated when the film is stretched 4 to 6 times in water is 10N or less.

Method for producing polarizer

The method for producing the polarizer is not particularly limited, and for example, it is preferable to form the polarizer by forming the PVA into a film and then introducing dichroic molecules. The production of PVA films can be carried out by referring to the methods described in [ 0213 ] to [ 0237 ] of Japanese patent laid-open No. 2007-086748, the specification of Japanese patent No. 3342516, Japanese patent laid-open No. 09-328593, Japanese patent laid-open No. 2001-302817, Japanese patent laid-open No. 2002-144401, and the like.

(method of laminating polarizer and polarizing plate protective film)

The polarizing plate used in the present invention is produced by bonding (laminating) at least one polarizing plate protective film (preferably, the optical filter of the present invention) to at least one surface of the polarizer.

Preferably, the polarizer is produced by a method in which a polarizer produced by subjecting a polarizer protective film to an alkali treatment and stretching a polyvinyl alcohol film by immersing the polarizer in an iodine solution is laminated to both surfaces of the polarizer using a completely saponified polyvinyl alcohol aqueous solution.

Examples of the adhesive used for bonding the treated surface of the polarizer protective film to the polarizer include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, and vinyl latexes such as acrylic films.

In the method of attaching the polarizer protective film used for the polarizer of the present invention to the polarizer, the polarizer is preferably attached so that the transmission axis of the polarizer and the slow axis of the polarizer protective film are substantially parallel to each other, orthogonal to each other, or 45 °.

The measurement of the slow axis can be performed by various known methods, for example, by using a birefringence meter (KOBRADH, Oji Scientific Instruments co., ltd).

Here, the substantially parallel means that the direction of the principal refractive index nx of the polarizer protective film and the direction of the transmission axis of the polarizer intersect each other at an angle within ± 5 °, preferably within ± 1 °, and more preferably within ± 0.5 °. When the angle of intersection is within 1 °, the polarization performance under crossed nicols of the polarizing plate is not easily deteriorated, and light leakage is not easily generated, which is preferable.

The direction of the principal refractive index nx orthogonal to or at 45 ° to the direction of the transmission axis means that the angle at which the direction of the principal refractive index nx intersects the direction of the transmission axis is within a range from a strict angle concerning the orthogonality and 45 ° to ± 5 °, and the error from the strict angle is preferably within a range of ± 1 °, and more preferably within a range of ± 0.5 °.

(functionalization of polarizing plate)

The polarizing plate used in the present invention is also preferably used as a functional polarizing plate combined with an optical film having functional layers such as an antireflection film, a brightness enhancement film, a hard coat layer, a front scattering layer, an antiglare (anti-glare) layer, an antifouling layer, and an antistatic layer for improving the visibility of a display. An antireflection film, a brightness enhancement film, another functional optical film, a hard coat layer, a front scattering layer, and an antiglare layer for functionalization can be produced based on the descriptions in [ 0257 ] to [ 0276 ] of jp 2007-a 086748 a.

(adhesive layer)

In the liquid crystal display device of the present invention, the polarizing plate is preferably bonded to the liquid crystal cell via an adhesive layer. The optical filter of the present invention can also serve as the adhesive layer. When the optical filter of the present invention does not serve as an adhesive layer as well, a general adhesive layer can be used as the adhesive layer.

The pressure-sensitive adhesive layer is not particularly limited as long as it can bond the polarizing plate and the liquid crystal cell, and is preferably acrylic, urethane, polyisobutylene, or the like, for example.

When the optical filter of the present invention is used also as an adhesive layer, the adhesive layer contains the pigment and the adhesive, and further contains a crosslinking agent, a coupling agent, and the like to impart adhesiveness.

When the optical filter is used as the adhesive layer, the adhesive layer preferably contains 90 to 100 mass%, preferably 95 to 100 mass% of the adhesive. The content of the pigment is as described above.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is, for example, preferably 1 to 50 μm, and more preferably 3 to 30 μm.

(liquid Crystal cell)

The liquid crystal cell is not particularly limited, and a general liquid crystal cell can be used.

[ solid-state imaging element ]

The solid-state imaging device of the present invention includes the optical filter of the present invention. The structure of the solid-state imaging device of the present invention is not particularly limited as long as it is a structure that includes the optical filter of the present invention and functions as a solid-state imaging device. The solid-state imaging device of the present invention is excellent in color tone and color reproducibility of an image when used for a long period of time, because it includes the optical filter (color filter) of the present invention having excellent weather resistance and contrast.

The structure of the solid-state imaging element is not particularly limited as long as it is a structure that includes the color filter of the present invention and functions as a solid-state imaging element. For example, the following configurations can be mentioned: the color filter of the present invention is provided on a support body having a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (such as a CCD image sensor and a CMOS image sensor) and a light receiving element made of polysilicon or the like, and on a light receiving element formation surface side (for example, a portion other than the light receiving portion, a color adjusting pixel portion, and the like) of the support body or on a side opposite to the formation surface.