Resin and adhesive composition

文档序号：816728 发布日期：2021-03-26 浏览：30次中文

阅读说明：本技术 树脂及粘合剂组合物 (Resin and adhesive composition ) 是由浅津悠司小泽昭一国见信孝于 2019-08-01 设计创作，主要内容包括：一种含有具有吲哚结构的结构单元的树脂(A)。树脂(A)优选为含有在侧链具有吲哚结构的结构单元的树脂,玻璃化转变温度优选为40℃以下。另外,树脂(A)优选为满足式(1)的树脂。ε(405)≥0.02(1)[式(1)中,ε(405)表示波长405nm处的树脂(A)的克吸光系数。克吸光系数的单位为L/(g·cm)。]。(A resin (A) containing a structural unit having an indole structure. The resin (a) is preferably a resin containing a structural unit having an indole structure in a side chain, and the glass transition temperature is preferably 40 ℃ or lower. Further, the resin (a) is preferably a resin satisfying the formula (1). ε (405) ≥ 0.02(1) [ in formula (1),. epsilon. (. epsilon.). 405) represents the gram absorption coefficient of the resin (A) at a wavelength of 405 nm. The unit of the gram absorption coefficient is L/(g.cm). ].)

1. A resin A containing a structural unit having an indole structure.

2. The resin according to claim 1, wherein,

the glass transition temperature of the resin A is 40 ℃ or lower.

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

the resin A is a resin satisfying the following formula (1):

ε(405)≥0.02 (1)

in the formula (1), ε (405) represents the gram absorption coefficient of resin A at a wavelength of 405 nm; the unit of the gram absorption coefficient is L/(g.cm).

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

the resin A is a resin satisfying the following formula (2):

ε(405)/ε(440)≥5 (2)

in the formula (2), ε (405) represents the gram absorption coefficient of the resin A at a wavelength of 405nm, and ε (440) represents the gram absorption coefficient of the resin at a wavelength of 440 nm.

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

the resin a is a resin containing a structural unit having an indole structure in a side chain.

6. The resin according to claim 5, wherein,

the structural unit having an indole structure in a side chain is a structural unit derived from a light selective absorbing compound having a polymerizable group and an indole structure.

7. The resin according to claim 6, wherein,

the light selective absorbing compound having a polymerizable group and an indole structure is a compound satisfying the following formula (1-a):

ε(405)≥5 (1-a)

in the formula (1-a), ε (405) represents the gram absorption coefficient of a compound having a polymerizable group and an indole structure at a wavelength of 405 nm; the unit of the gram absorption coefficient is L/(g.cm).

8. The resin according to claim 7, wherein,

the light selective absorbing compound having a polymerizable group and an indole structure is a compound satisfying the following formula (2-a):

ε(405)/ε(440)≥10 (2-a)

in the formula (2-a), ε (405) represents the gram absorption coefficient of a compound having a polymerizable group and an indole structure at a wavelength of 405nm, and ε (440) represents the gram absorption coefficient of a compound having a polymerizable group and an indole structure at a wavelength of 440 nm.

9. The resin according to claim 5, wherein,

the structural unit having an indole structure in a side chain is a structural unit derived from a compound represented by the formula (I) or a structural unit derived from a compound represented by the formula (II):

in the formula (I), R¹、R²、R³、R⁴、R⁵And R⁶Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms-CH contained in an aliphatic hydrocarbon group₂-optionally substituted by-NR^1A-、-SO₂-, -CO-, -O-, -S-or-CF₂-；

R^1ARepresents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms;

E¹represents an electron-withdrawing group;

z represents a linking group;

a represents a polymerizable group;

in the formula (II), R¹²And R¹⁷Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein-CH is contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group₂-optionally substituted by-NR^11A-、-SO₂-, -CO-, -O-, -S-or-CF₂-；

R¹¹、R¹³、R¹⁴、R¹⁵And R¹⁶Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a group containing a polymerizable group, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein-CH is contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group₂-optionally substituted by-NR^12A-、-SO₂-, -CO-, -O-, -S-or-CF₂-；

Wherein R is¹¹、R¹³、R¹⁴、R¹⁵And R¹⁶At least one of (a) represents a group containing a polymerizable group;

R^11Aand R^12AEach independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms;

E¹¹represents an electron-withdrawing group.

10. The resin according to claim 9, wherein,

R²is phenyl.

11. The resin according to claim 9, wherein,

the compound shown in the formula (I) is a compound shown in a formula (III):

R¹、R³、R⁴、R⁵、R⁶and E¹Denotes the same meaning as above;

R⁷represents a hydrogen atom, a cyano group, a methyl group or a phenyl group;

Z¹represents an alkanediyl group having 1 to 12 carbon atoms, a 2-valent aromatic hydrocarbon group having 6 to 18 carbon atoms, -O-R^2A-＊1、-S-R^2B-. 1 or-NR^1D-R^2C-＊1；

Z²Represents a single bond, O2-CO-O-, O2-O-CO-, or O2-S (═ O)₂-、＊2-O-SO₂-、＊2-CO-NR^1B-、＊2-NR^1C-CO-、＊2-R^2DO-P(＝O)-OR^2E-、＊2-NR^1E-CO-O-、＊2-O-CO-NR^1F-、＊2-(OR^2F)_s1-,. 2-CO-S-,. 2-S-CO-or a C1-4 perfluoroalkyl group;

R^1B、R^1C、R^1D、R^1Eand R^1FEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

R^2A、R^2B、R^2C、R^2D、R^2Eand R^2FEach independently represents a C1-18 valence-2 hydrocarbon group;

1 represents and Z²The bonding end of (1);

2 represents and Z¹The bonding terminal of (1).

12. The resin according to any one of claims 1 to 11,

the resin a further has at least 1 structural unit selected from the structural units described in the following group a:

group A: a structural unit derived from a (meth) acrylate, a structural unit derived from a styrene monomer, a structural unit derived from a vinyl monomer, a structural unit derived from an epoxy compound, a structural unit represented by formula (a), a structural unit represented by formula (b), and a structural unit represented by formula (c)

In the formula, R^a1Represents a 2-valent hydrocarbon group;

R^b1and R^b2Each independently represents a hydrogen atom or a hydrocarbon group;

R^c1and R^c2Each independently represents a 2-valent hydrocarbon group.

13. The resin according to claim 12, wherein,

the content of at least 1 structural unit selected from the structural units described in group a is 50% by mass or more with respect to the total structural units of the resin a.

14. An adhesive composition comprising the resin of any one of claims 1-13.

15. The adhesive composition of claim 14, further comprising a crosslinker B.

16. An adhesive layer formed from the adhesive composition of claim 14 or 15.

17. The adhesive layer according to claim 16, which satisfies the following formula (3):

A(405)≥0.5 (3)

in the formula (3), A (405) represents the absorbance at a wavelength of 405 nm.

18. The adhesive layer of claim 17, further satisfying the following formula (4):

A(405)/A(440)≥5 (4)

in the formula (4), A (405) represents the absorbance at a wavelength of 405nm, and A (440) represents the absorbance at a wavelength of 440 nm.

19. An optical laminate comprising an optical film laminated on at least one side of the adhesive layer according to any one of claims 16 to 18.

20. The optical stack of claim 19,

the optical film is a polarizing plate.

21. An image display device comprising the optical stack of claim 20.

22. A compound represented by formula (I) or formula (IV),

in the formula (I), R¹、R²、R³、R⁴、R⁵And R⁶Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein-CH is contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group₂-optionally substituted by-NR^1A-、-SO₂-, -CO-, -O-, -S-or-CF₂-；

R^1ARepresents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms;

E¹represents an electron-withdrawing group;

z represents a linking group;

a represents a polymerizable group;

in the formula (IV), R¹²And R¹⁷Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein-CH is contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group₂-optionally substituted by-NR^11A-、-SO₂-, -CO-, -O-, -S-or-CF₂-；

Wherein R is¹³、R¹⁴、R¹⁵And R¹⁶At least one of (a) represents a group containing a polymerizable group;

R^11Aand R^12AEach independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms;

E¹¹represents an electron-withdrawing group.

23. The compound of claim 22, wherein,

R²is phenyl.

24. The compound of claim 22, wherein,

the compound shown in the formula (I) is a compound shown in a formula (III):

R¹、R³、R⁴、R⁵、R⁶and E¹Denotes the same meaning as above;

R⁷represents a hydrogen atom, a cyano group, a methyl group or a phenyl group;

Z¹represents an alkanediyl group having 1 to 12 carbon atoms, a 2-valent aromatic hydrocarbon group having 6 to 18 carbon atoms, -O-R^2A-＊1、-S-R^2B-. 1 or-NR^1D-R^2C-＊1；

Z²Represents a single bond, O2-CO-O-, O2-O-CO-, or O2-S (═ O)₂-、＊2-O-SO₂-、

＊2-CO-NR^1B-、＊2-NR^1C-CO-、＊2-R^2DO-P(＝O)-OR^2E-、＊2-NR^1E-CO-O-、＊2-O-CO-NR^1F-、＊2-(OR^2F)_s1-,. 2-CO-S-,. 2-S-CO-or a C1-4 perfluoroalkyl group;

R^1B、R^1C、R^1D、R^1Eand R^1FEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

R^2A、R^2B、R^2C、R^2D、R^2Eand R^2FEach independently represents a C1-18 valence-2 hydrocarbon group;

1 represents and Z²The bonding end of (1);

2 represents and Z¹The bonding terminal of (1).

25. The compound according to any one of claims 22 to 24,

E¹is cyano.

Technical Field

The present invention relates to a resin, a pressure-sensitive adhesive composition containing the resin, and an optical laminate in which a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is laminated.

Background

In display devices (FPD: flat panel display) such as organic electroluminescent displays (organic EL display devices) and liquid crystal display devices, various members such as display elements such as organic EL elements and liquid crystal cells, and optical films such as polarizing plates are used. Among these members, since organic EL light-emitting elements, liquid crystal compounds, and the like are organic substances, deterioration by Ultraviolet (UV) rays is likely to be a problem. Further, it has been found that a liquid crystal retardation film and an organic EL light-emitting device obtained by aligning and photocuring a polymerizable liquid crystal compound tend to be deteriorated not only by ultraviolet light but also by visible light having a short wavelength. In order to solve the above problem, it is known to provide a layer containing a compound that absorbs short-wavelength visible light. For example, patent document 1 describes a polarizing plate with an adhesive layer, which is formed from an adhesive composition containing a copolymer containing N-butyl acrylate, 2-hydroxyethyl acrylate, and N, N-dimethylacrylamide, and an indole-based ultraviolet absorber.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2017-48340

Disclosure of Invention

Problems to be solved by the invention

However, it has been found that when the pressure-sensitive adhesive layer containing an ultraviolet absorber described in patent document 1 is formed into an optical laminate, deterioration due to ultraviolet rays or short-wavelength visible light can be suppressed, but another problem occurs in that the optical properties are impaired by the transfer of the ultraviolet absorber to another layer. Among them, in the laminate with the liquid crystal retardation film, it was found that the deterioration of the optical properties (change in retardation value) due to the transfer of the ultraviolet absorber to other layers becomes remarkable.

Means for solving the problems

The present invention includes the following inventions.

[1] A resin (A) containing a structural unit having an indole structure.

[2] The resin according to [1], wherein the glass transition temperature of the resin (A) is 40 ℃ or lower.

[3] The resin according to [1] or [2], wherein the resin (A) satisfies the following formula (1).

ε(405)≥0.02 (1)

[ in the formula (1),. epsilon. (. 405) represents the gram absorption coefficient of the resin (A) at a wavelength of 405 nm. The unit of the gram absorption coefficient is L/(g.cm). ]

[4] The resin according to any one of [1] to [3], wherein the resin (A) satisfies the following formula (2).

ε(405)/ε(440)≥5 (2)

[ in the formula (2),. epsilon. (405) represents the gram absorption coefficient of the resin (A) at a wavelength of 405nm, and. epsilon. (440) represents the gram absorption coefficient of the resin at a wavelength of 440 nm. ]

[5] The resin according to any one of [1] to [4], wherein the resin (A) contains a structural unit having an indole structure in a side chain.

[6] The resin according to [5], wherein the structural unit having an indole structure in a side chain is a structural unit derived from a light selective absorbing compound having a polymerizable group and an indole structure.

[7] The resin according to [6], wherein the light selective absorbing compound having a polymerizable group and an indole structure is a compound satisfying the following formula (1-a).

ε(405)≥5 (1-a)

[ in the formula (1-a),. epsilon. (405) represents the gram absorption coefficient of a compound having a polymerizable group and an indole structure at a wavelength of 405 nm. The unit of the gram absorption coefficient is L/(g.cm). ]

[8] The resin according to [7], wherein the light selective absorbing compound having a polymerizable group and an indole structure is a compound satisfying the following formula (2-a).

ε(405)/ε(440)≥10 (2-a)

[ in the formula (2-a), [ epsilon ] (405) represents the gram absorption coefficient of the compound having a polymerizable group and an indole structure at a wavelength of 405nm, and epsilon (440) represents the gram absorption coefficient of the compound having a polymerizable group and an indole structure at a wavelength of 440 nm.

[9] The resin according to [5], wherein the structural unit having an indole structure in a side chain is a structural unit derived from a compound represented by the formula (I) or a structural unit derived from a compound represented by the formula (II).

[ in the formula (I), R¹、R²、R³、R⁴、R⁵And R⁶Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein-CH is contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group₂-optionally substituted by-NR^1A-、-SO₂-, -CO-, -O-, -S-or-CF₂-。

R^1ARepresents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

E¹Represents an electron-withdrawing group.

Z represents a linking group.

A represents a polymerizable group.

In the formula (II), R¹²And R¹⁷Each independently represents a hydrogen atom, a heterocycleA halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein-CH is contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group₂-optionally substituted by-NR^11A-、-SO₂-, -CO-, -O-, -S-or-CF₂-。

Wherein R is¹¹、R¹³、R¹⁴、R¹⁵And R¹⁶At least one of (a) represents a group containing a polymerizable group.

R^11AAnd R^12AEach independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

E¹¹Represents an electron-withdrawing group.]

[10]According to [9]]The resin according to (1), wherein R²Is phenyl.

[11] The resin according to [9], wherein the compound represented by the formula (I) is a compound represented by the formula (III).

[R¹、R³、R⁴、R⁵、R⁶And E¹The same meaning as above is indicated.

R⁷Represents a hydrogen atom, a methyl group or a phenyl group.

Z¹Represents a carbon number of 112-alkanediyl group, 2-valent aromatic hydrocarbon group having 6 to 18 carbon atoms, -O-R^2A-*1、-S-R^2B-. 1 or-NR^1D-R^2C-*1。

Z²Represents a single bond, { character pullout (X2-CO-O- }, { character pullout (X2-O-CO-) }, and { character pullout (X2-S) }, }₂-、*2-O-SO₂-、*2-CO-NR^1B-、*2-NR^1C-CO-、*2-R^2DO-P(＝O)-OR^2E-、*2-NR^1E-CO-O-、*2-O-CO-NR^1F-、*2-(OR^2F)_s1-, [ 2-CO-S- ], [ 2-S-CO- ], or a C1-4 perfluoroalkanediyl group.

R^1B、R^1C、R^1D、R^1EAnd R^1FEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R^2A、R^2B、R^2C、R^2D、R^2EAnd R^2FEach independently represents a C1-18 hydrocarbon group having a valence of 2.

1 denotes with Z²The bonding terminal of (1).

2 denotes with Z¹The bonding terminal of (1).]

[12] The resin according to any one of [1] to [11], wherein the resin (A) further comprises at least 1 structural unit selected from the structural units described in the following group A.

Group A: a structural unit derived from a (meth) acrylate, a structural unit derived from a styrene monomer, a structural unit derived from a vinyl monomer, a structural unit derived from an epoxy compound, a structural unit represented by formula (a), a structural unit represented by formula (b), and a structural unit represented by formula (c)

[ in the formula, R^a1Represents a 2-valent hydrocarbon group.

R^b1And R^b2Each independently represents a hydrogen atom or a hydrocarbon group.

R^c1And R^c2Each independently represents a 2-valent hydrocarbon group.]

[13] The resin according to [12], wherein the content of at least 1 structural unit selected from the structural units described in group A is 50% by mass or more based on the total structural units of the resin (A).

[14] An adhesive composition comprising the resin according to any one of [1] to [13 ].

[15] The adhesive composition according to [14], further comprising a crosslinking agent (B).

[16] An adhesive layer comprising the adhesive composition according to [14] or [15 ].

[17] The pressure-sensitive adhesive layer according to [16], which satisfies the following formula (3).

A(405)≥0.5 (3)

[ in the formula (3), A (405) represents the absorbance at a wavelength of 405 nm. ]

[18] The pressure-sensitive adhesive layer according to [17], which further satisfies the following formula (4).

A(405)/A(440)≥5 (4)

In the formula (4), A (405) represents the absorbance at a wavelength of 405nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]

[19] An optical laminate comprising an optical film laminated on at least one surface of the pressure-sensitive adhesive layer according to any one of [16] to [18 ].

[20] The optical laminate according to [19], wherein the optical film is a polarizing plate.

[21] An image display device comprising the optical laminate according to [20 ].

[22] A compound represented by formula (I) or formula (IV).

[ in the formula (I), R¹、R²、R³、R⁴、R⁵And R⁶Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, or an optionally substituted aliphatic hydrocarbon groupA substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or-CH contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group₂-optionally substituted by-NR^1A-、-SO₂-, -CO-, -O-, -S-or-CF₂-。

R^1ARepresents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

E¹Represents an electron-withdrawing group.

Z represents a linking group.

A represents a polymerizable group.

In the formula (IV), R¹²And R¹⁷Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein-CH is contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group₂-optionally substituted by-NR^11A-、-SO₂-, -CO-, -O-, -S-or-CF₂-。

Wherein R is¹³、R¹⁴、R¹⁵And R¹⁶At least one of (a) represents a group containing a polymerizable group.

R^11AAnd R^12AEach independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

E¹¹Represents an electron-withdrawing group.]

[23]According to [22]]The compound of (1), wherein R²Is benzeneAnd (4) a base.

[24] The compound according to [22], wherein the compound represented by the formula (I) is a compound represented by the formula (III).

[R¹、R³、R⁴、R⁵、R⁶And E¹The same meaning as above is indicated.

R⁷Represents a hydrogen atom, a cyano group, a methyl group or a phenyl group.

Z¹Represents an alkanediyl group having 1 to 12 carbon atoms, a 2-valent aromatic hydrocarbon group having 6 to 18 carbon atoms, -O-R^2A-*1、-S-R^2B-. 1 or-NR^1D-R^2C-*1。

Z²Represents a single bond, { character pullout (X2-CO-O- }, { character pullout (X2-O-CO-) }, and { character pullout (X2-S) }, }₂-、*2-O-SO₂-、

*2-CO-NR^1B-、*2-NR^1C-CO-、*2-R^2DO-P(＝O)-OR^2E-、*2-NR^1E-CO-O-、*2-O-CO-NR^1F-、*2-(OR^2F)_s1-, [ 2-CO-S- ], [ 2-S-CO- ], or a C1-4 perfluoroalkanediyl group.

R^1B、R^1C、R^1D、R^1EAnd R^1FEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R^2A、R^2B、R^2C、R^2D、R^2EAnd R^2FEach independently represents a C1-18 hydrocarbon group having a valence of 2.

1 denotes with Z²The bonding terminal of (1).

2 denotes with Z¹The bonding terminal of (1).]

[25]According to [22]]～[24]The compound according to any one of (1), wherein E¹Is cyano.

Effects of the invention

The invention provides an adhesive layer capable of inhibiting deterioration of an organic EL light-emitting element and a liquid crystal phase difference film, and an adhesive composition for forming the adhesive layer. Further, a resin capable of forming a binder composition capable of favorably suppressing deterioration of an organic EL light-emitting element and a retardation film is provided.

Drawings

Fig. 1 shows an example of the layer structure of the pressure-sensitive adhesive layer of the present invention.

Fig. 2 shows an example of the layer structure of the optical laminate of the present invention.

Fig. 3 shows an example of the layer structure of the optical laminate of the present invention.

Fig. 4 shows an example of the layer structure of the optical laminate of the present invention.

Fig. 5 shows an example of the layer structure of the optical laminate of the present invention.

Detailed Description

< adhesive composition >

The adhesive composition of the present invention contains a resin (a) containing a structural unit having an indole structure. The pressure-sensitive adhesive composition of the present invention may further contain a crosslinking agent (B), a silane compound (D), an antistatic agent, and the like.

< resin (A) >

The resin (a) of the present invention is a resin containing a structural unit having an indole structure, and preferably a resin containing a structural unit derived from a light selective absorbing compound having an indole structure.

The glass transition temperature (Tg) of the resin (A) is preferably 40 ℃ or lower, more preferably 20 ℃ or lower, still more preferably 10 ℃ or lower, and particularly preferably 0 ℃ or lower. The glass transition temperature of the resin (A) is usually-80 ℃ or higher, preferably-60 ℃ or higher, and more preferably-50 ℃ or higher. When the glass transition temperature of the resin (a) is 40 ℃ or lower, it is advantageous to improve the adhesion of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition containing the resin (a) to an adherend. When the glass transition temperature of the resin (a) is-80 ℃ or higher, it is advantageous to improve the durability of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition containing the resin (a). The glass transition temperature can be measured by a Differential Scanning Calorimeter (DSC).

The resin (a) is preferably a resin satisfying the following formula (1).

ε(405)≥0.02(1)

[ in the formula (1),. epsilon. (. 405) represents the gram absorption coefficient of the resin at a wavelength of 405 nm. The unit of the gram absorption coefficient is L/(g.cm). ]

The gram absorbance coefficient of the resin (a) can be measured by the method described in examples.

The larger the value of ε (405) of resin (A), the more easily the resin (A) absorbs light having a wavelength of 405 nm. The value of ε (405) is preferably 0.02L/(g · cm) or more, more preferably 0.1L/(g · cm) or more, still more preferably 0.2L/(g · cm) or more, and usually 10L/(g · cm) or less.

When the adhesive composition containing the resin (a) is applied to a display device such as an organic EL display device or a liquid crystal display device, if ∈ (405) of the resin (a) is 0.02L/(g · cm) or more, the absorption performance of visible light in the vicinity of 400nm is good, and therefore, degradation of a retardation film or an organic EL light-emitting element used in the display device such as the organic EL display device or the liquid crystal display device due to visible light can be suppressed.

The resin (a) is preferably a resin satisfying the following formula (2).

ε(405)/ε(440)≥5 (2)

[ in the formula (2),. epsilon. (405) represents the gram absorption coefficient of the resin at a wavelength of 405nm, and. epsilon. (440) represents the gram absorption coefficient of the resin at a wavelength of 440 nm. ]

The larger the value of ε (405)/ε (440) of the resin (A), the more selectively light having a wavelength of about 400nm can be absorbed. The value of ε (405)/ε (440) is preferably 5 or more, more preferably 10 or more, and still more preferably 30 or more.

When epsilon (405)/epsilon (440) of the resin (a) is 5 or more, when the adhesive composition containing the resin (a) is applied to a display device such as an organic EL display device or a liquid crystal display device, light of around 400nm can be absorbed without hindering the color expression of the display device, and the light degradation of the retardation film can be suppressed.

The resin (a) may contain a structural unit having an indole structure in the main chain, or may contain a structural unit having an indole structure in the side chain. The resin (a) preferably contains a structural unit having an indole structure in a side chain.

The structural unit having an indole structure in a side chain is not particularly limited, but is preferably a structural unit derived from a compound having a polymerizable group and an indole structure. The structural unit derived from the compound having a polymerizable group and an indole structure is preferably a structural unit derived from a light selective absorbing compound having a polymerizable group and an indole structure.

The light selective absorbing compound having a polymerizable group and an indole structure preferably satisfies the following formula (1-a), and more preferably satisfies the formula (2-a).

ε(405)≥5 (1-a)

ε(405)/ε(440)≥10 (2-a)

The value of ∈ (405) of the compound having a polymerizable group and an indole structure is preferably 5L/(g · cm) or more, more preferably 10L/(g · cm) or more, still more preferably 20L/(g · cm) or more, still more preferably 30L/(g · cm) or more, and usually 500L/(g · cm) or less. The larger the value of ε (405), the more easily the compound absorbs light having a wavelength of 405nm, and the more easily the compound exhibits a function of suppressing deterioration due to ultraviolet light or visible light having a short wavelength.

The value of epsilon (405)/epsilon (440) of the compound having a polymerizable group and an indole structure is preferably 10 or more, more preferably 15 or more. The larger the value of epsilon (405)/epsilon (440), the more the compound absorbs light near 405nm without hindering the color expression of the display device, and the more the light degradation of the display device such as a retardation film or an organic EL element is suppressed.

The structural unit having an indole structure in a side chain is preferably a structural unit derived from the compound represented by formula (I) or a structural unit derived from the compound represented by formula (II), and more preferably a structural unit derived from the compound represented by formula (I).

R^1ARepresents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

E¹Represents an electron-withdrawing group.

Z represents a linking group.

A represents a polymerizable group.

In the formula (II), R¹²And R¹⁷Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein-CH is contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group₂-optionally substituted by-NR^11A-、-SO₂-, -CO-, -O-, -S-or-CF₂-。

R¹¹、R¹³、R¹⁴、R¹⁵And R¹⁶Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a group containing a polymerizable group, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atomsA hydrocarbon group, -CH contained in the aliphatic or aromatic hydrocarbon group₂-optionally substituted by-NR^12A-、-SO₂-, -CO-, -O-, -S-or-CF₂-。

Wherein R is¹¹、R¹³、R¹⁴、R¹⁵And R¹⁶At least one of (a) represents a group containing a polymerizable group.

R^11AAnd R^12AEach independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

E¹¹Represents an electron-withdrawing group.]

As E¹And E¹¹Examples of the electron-withdrawing group include a cyano group, a nitro group, a halogen atom, an alkyl group substituted with a halogen atom, a group represented by the formula (I-1), and the like.

^*-X¹-R¹¹¹ (I-1)

[ in the formula, R¹¹¹Represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms, and at least 1 of methylene groups contained in the alkyl group is optionally replaced by an oxygen atom.

X¹represents-CO- '3, -COO-' 3, -CS- '3, -CSS-' 3, -CSNR¹¹²-*3、-CONR¹¹³-*3、-CNR¹¹⁴- [3] or-SO₂-*3。

R¹¹²、R¹¹³And R¹¹⁴Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

3 denotes with R¹¹¹The bonding terminal of (1).

Denotes a bonding end to a carbon atom. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group substituted with a halogen atom include halogenated alkyl groups such as a monofluoromethyl group, a monofluoroethyl group, a monochloromethyl group, a monochloroethyl group, a monobromomethyl group, a monobromoethyl group, a monoiodomethyl group, a monoiodoethyl group, a difluoromethyl group, a difluoroethyl group, a dichloromethyl group, a dichloroethyl group, a dibromomethyl group, a dibromoethyl group, a diiodomethyl group, a diiodoethyl group, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group. The number of carbon atoms of the alkyl group substituted with a halogen atom is usually 1 to 25.

As R¹¹¹Examples of the hydrocarbon group having 1 to 25 carbon atoms include straight-chain or branched alkyl groups having 1 to 25 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, undecyl, tetradecyl, hexadecyl, and octadecyl groups: cycloalkyl groups having 3 to 25 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; a C4-25 cycloalkylalkyl group such as a cyclopropylmethyl group or a cyclohexylmethyl group; aryl groups having 6 to 25 carbon atoms such as phenyl, naphthyl, anthryl and biphenyl groups; aralkyl groups having 7 to 25 carbon atoms such as benzyl, phenethyl, naphthylmethyl and phenyl.

As R¹¹²、R¹¹³And R¹¹⁴Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and a sec-butyl group.

The linking group represented by Z is not particularly limited as long as it is a 2-valent linking group.

The polymerizable group represented by a is not particularly limited. For example, the polymerizable group may be a cationically polymerizable group, an anionically polymerizable group, or a radically polymerizable group. More specifically, an alkynyl group such as an ethynyl group; an epoxy group; an oxetanyl group; a vinyl ether group; an acrylonitrile group; a methacrylonitrile group; and ethylenically unsaturated groups such as vinyl, α -methylvinyl, acryloyl, methacryloyl, allyl, styryl, acrylamido, and methacrylamido groups.

As R¹～R⁶、R¹¹～R¹⁷Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As R¹～R⁶、R¹¹～R¹⁷Shown as being mixedExamples of the cyclic group include those obtained by removing one hydrogen atom from a heterocyclic ring. Specifically, examples thereof include aliphatic heterocyclic groups having 4 to 30 carbon atoms such as pyrrolidine ring group, pyrroline ring group, imidazolidine ring group, imidazoline ring group, oxazoline ring group, thiazoline ring group, piperidine ring group, morpholine ring group, piperazine ring group, indole ring group, isoindole ring group, quinoline ring group, thiophene ring group, pyrrole ring group, thiazoline (Japanese patent No. チアゾリン) ring group, furan ring group, pyridine ring group, dioxane ring group, morpholine ring group, thiazine ring group, triazole ring group, tetrazole ring group, dioxyfuran (Japanese patent No. ジオキソフラン) ring group, pyrazine ring group, purine ring group and the like, aromatic heterocyclic groups having 3 to 20 carbon atoms and the like. These heterocyclic groups may have a structure in which an unsaturated bond is hydrogenated, or a structure in which a cyclic skeleton is further fused (for example, a benzziamide ring (a ring having ベンゾイミダール in Japanese), a benzimidazole ring), and a hydrogen atom on a heterocyclic ring may be further substituted with a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or the like.

As R¹～R⁶、R¹¹～R¹⁷Examples of the aliphatic hydrocarbon group having 1 to 25 carbon atoms include straight-chain or branched alkyl groups having 1 to 25 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, undecyl, tetradecyl, hexadecyl, and octadecyl groups: cycloalkyl groups having 3 to 25 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; and C4-25 cycloalkylalkyl groups such as cyclopropylmethyl and cyclohexylmethyl, and branched alkyl groups having 3-25 carbon atoms such as 2-ethylhexyl and 2-butyloctyl are preferable from the viewpoint of solubility.

As R¹～R⁶、R¹¹～R¹⁷Examples of the optional substituent of the aliphatic hydrocarbon group having 1 to 25 carbon atoms include a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an acetamido group, an amino group, and a C1 to E12, and the like. Examples of the heterocyclic group include the groups represented by the formula and R¹The heterocyclic groups shown are the same groups.

As R¹～R⁶、R¹¹～R¹⁷The aromatic hydrocarbon group having 6 to 18 carbon atoms includes aryl groups having 6 to 18 carbon atoms such as phenyl, naphthyl, anthryl, biphenyl, methylphenyl and the like; aralkyl groups having 7 to 18 carbon atoms such as benzyl, phenylethyl, naphthylmethyl, phenoxy, and the like. As R¹～R⁶、R¹¹～R¹⁷-CH contained in the aromatic hydrocarbon group having 6 to 18 carbon atoms₂-by-SO₂-, -CO-, -O-, -S-or-CF₂Examples of the-substituted group include aryloxy groups such as phenoxy and naphthoxy. From the viewpoint of wavelength selectivity, as R¹～R⁶、R¹¹～R¹⁷The aromatic hydrocarbon group having 6 to 18 carbon atoms is preferably an aralkyl group having 7 to 18 carbon atoms or an aryloxy group having 6 to 18 carbon atoms, and more preferably a benzyl group or an aryloxy group having 6 to 18 carbon atoms.

As R¹～R⁶、R¹¹～R¹⁷The aromatic hydrocarbon group having 6 to 18 carbon atoms optionally has a substituent, and examples thereof include a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an acetylamino group, an amino group, an alkylamino group having 1 to 12 carbon atoms, and the like. Examples of the heterocyclic group include the groups represented by the formula and R¹The heterocyclic groups shown are the same groups.

As R¹¹、R¹³、R¹⁴、R¹⁵And R¹⁶The group containing a polymerizable group is not particularly limited as long as it has a polymerizable group at the end, but specifically, a group represented by the formula (I-2) can be exemplified.

*-R¹¹⁵-X² (I-2)

[ in the formula (I-2), X²Represents a polymerizable group.

R¹¹⁵Represents an alkanediyl group having 1 to 12 carbon atoms, wherein-CH is contained in the alkanediyl group₂Optionally substituted by-O-, -CO-, -CS-or-NR¹¹⁶-。

R¹¹⁶Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Represents a bonding end to a carbon atom or a nitrogen atom. ]

As X²The polymerizable group is the same as the polymerizable group shown in A, and preferably an ethylenically unsaturated group such as a vinyl group, an α -methylvinyl group, an acryloyl group, a methacryloyl group, an allyl group, a styryl group, an acrylamide group, or a methacrylamide group.

As R¹¹⁵Examples of the alkanediyl group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, a hexane-1, 6-diyl group, an ethane-1, 1-diyl group, a propane-1, 2-diyl group, a butane-1, 3-diyl group, a 2-methylpropane-1, 2-diyl group, a pentane-1, 4-diyl group, and a 2-methylbutane-1, 4-diyl group.

As R¹¹⁶Examples of the alkyl group having 1 to 6 carbon atoms include the group represented by the formula¹¹²The alkyl groups having 1 to 6 carbon atoms are the same.

R¹¹、R¹³、R¹⁴、R¹⁵And R¹⁶At least one of (a) represents a group containing a polymerizable group.

Preferably R¹³、R¹⁴、R¹⁵And R¹⁶At least one of them is a group containing a polymerizable group, more preferably R¹³、R¹⁴、R¹⁵Or R¹⁶Any of (a) and (b) is a group containing a polymerizable group.

R²Preferably an aromatic hydrocarbon group or a heterocyclic group having 6 to 18 carbon atoms, more preferably an aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 18 carbon atoms or 3 to 20 carbon atoms.

The polymerizable group represented by a is preferably an ethylenically unsaturated group.

E¹And E¹¹Preferably each independently cyano.

The compound represented by the formula (I) is preferably a compound represented by the formula (III).

[R¹、R³、R⁴、R⁵、R⁶And E¹The same meaning as above is indicated.

R⁷Represents a hydrogen atom, a cyano group, a methyl group or a phenyl group.

Z¹Represents an alkanediyl group having 1 to 12 carbon atoms, a 2-valent aromatic hydrocarbon group having 6 to 18 carbon atoms, -O-R^2A-*1、-S-R^2B-. 1 or-NR^1D-R^2C-*1。

R^1B、R^1C、R^1D、R^1EAnd R^1FEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R^2A、R^2B、R^2C、R^2D、R^2EAnd R^2FEach independently represents a C1-18 hydrocarbon group having a valence of 2.

1 denotes with Z²The bonding terminal of (1).

2 denotes with Z¹The bonding terminal of (1).]

As Z¹Examples of the alkanediyl group having 1 to 12 carbon atoms include the group represented by formula (I) and R¹¹⁵The alkanediyl group having 1 to 12 carbon atoms.

As Z¹Examples of the aromatic hydrocarbon group having a valence of 2 and 6 to 18 carbon atoms include phenylene and naphthylene.

As R^1B、R^1C、R^1D、R^1EAnd R^1FExamples of the alkyl group having 1 to 6 carbon atoms includeR¹¹²The alkyl groups having 1 to 6 carbon atoms are the same.

As R^2A、R^2B、R^2C、R^2D、R^2EAnd R^2FExamples of the C1-18 divalent hydrocarbon group include a C1-18 alkanediyl group such as a methylene group, an ethylene group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, a hexane-1, 6-diyl group, an ethane-1, 1-diyl group, a propane-1, 2-diyl group, a butane-1, 3-diyl group, a 2-methylpropane-1, 2-diyl group, a pentane-1, 4-diyl group, and a 2-methylbutane-1, 4-diyl group; and a 2-valent aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenylene group and a naphthylene group.

Z¹Is preferably-O-R^2A-. 1 (more preferably R)^2AAn alkanediyl group having 1 to 8 carbon atoms, more preferably an alkanediyl group having 4 to 8 carbon atoms).

Z²Preferably 2-O-CO-, 2-O-SO₂-、*2-NR^1C-CO- (more preferably R)^1CIs a hydrogen atom).

The compound represented by the formula (II) is preferably a compound represented by the formula (IV).

[R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷And E¹¹The same meaning as above is indicated. Wherein R is¹³、R¹⁴、R¹⁵And R¹⁶At least one of (a) represents a group containing a polymerizable group.]

Examples of the compound represented by the formula (I) include the following compounds.

Examples of the compound represented by the formula (II) include the following compounds.

The compound represented by the formula (I) wherein A is an ethylenically unsaturated group can be obtained, for example, by reacting a compound represented by the formula (Ia) with a compound represented by the formula (c 1).

[ R in the formula (Ia) ]¹、R²、R³、R⁴、R⁵、R⁶And E¹The same meaning as above is indicated. Z in the formula (c)³Represents a 2-valent linking group, A¹Represents an ethylenic polymerizable group.]

The amount of the compound represented by formula (c1) used is preferably 0.5 to 5 moles based on 1 mole of the compound represented by formula (Ia).

The reaction of the compound represented by the formula (Ia) with the compound represented by the formula (c1) can be carried out by a known esterification reaction, preferably in the presence of a base and a carbodiimide condensing agent. Examples of the base include triethylamine, diisopropylethylamine, pyridine, piperidine, pyrrolidine, proline, and N, N-dimethylaminopyridine. Examples of the carbodiimide condensing agent include N, N-dicyclohexylcarbodiimide, N-diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. The amount of the base used is preferably 0.001 to 0.5 mol based on 1 mol of the compound represented by the formula (Ia). The amount of the carbodiimide condensing agent used is preferably 0.5 to 5 moles based on 1 mole of the compound represented by the formula (Ia).

The reaction of the compound represented by the formula (Ia) with the compound represented by the formula (c1) is preferably carried out in an organic solvent. Examples of the organic solvent include toluene, acetonitrile, dichloromethane, and chloroform.

In order to inhibit the reaction between the ethylenically unsaturated groups contained in the compound represented by the formula (c1), a polymerization inhibitor may be added. Examples of the polymerization inhibitor include 2, 6-di-tert-butyl-4-methylphenol (BHT), 4-methoxyphenol and the like.

The reaction of the compound represented by the formula (Ia) with the compound represented by the formula (c1) is carried out by mixing the compound represented by the formula (Ia) with the compound represented by the formula (c 1).

The reaction temperature of the compound represented by the formula (Ia) and the compound represented by the formula (c1) is preferably-20 to 120 ℃, and the reaction time is preferably 1 to 50 hours.

Examples of the compound represented by the formula (Ia) include the following compounds.

Examples of the compound represented by the formula (c1) include 4-hydroxybutyl acrylate and 2-hydroxyethyl acrylate.

The compound represented by the formula (Ia) can be obtained by reacting a compound represented by the formula (Ib) with a compound represented by the formula (c 2).

[ R in the formula¹、R²、R³、R⁴、R⁵、R⁶And E¹The same meaning as above is indicated.]

The amount of the compound represented by formula (c2) used is preferably 0.5 to 5 moles per 1 mole of the compound represented by formula (Ib).

The reaction of the compound represented by the formula (Ib) with the compound represented by the formula (c2) is preferably carried out in the presence of a base. Examples of the base include pyridine, pyrrolidine, piperidine, triethylamine, diisopropylethylamine and the like. The amount of the base used is preferably 0.5 to 5 moles based on 1 mole of the compound represented by the formula (Ib).

The reaction of the compound represented by the formula (Ib) with the compound represented by the formula (c2) is preferably carried out in an organic solvent. Examples of the organic solvent include acetonitrile, isopropanol, toluene, chloroform, and dichloromethane.

The reaction of the compound represented by the formula (Ib) with the compound represented by the formula (c2) is carried out by mixing the compound represented by the formula (Ia) with the compound represented by the formula (c 1).

The reaction temperature of the compound represented by the formula (Ia) and the compound represented by the formula (c1) is preferably 0 to 120 ℃, and the reaction time is preferably 1 to 50 hours.

The resin (a) may be a homopolymer having a structural unit having an indole structure, or may be a copolymer containing a structural unit having an indole structure and another structural unit. The resin (a) is preferably a copolymer.

Examples of the structural unit that may be contained in the resin (a) other than the structural unit having an indole structure include structural units described in the following group a.

[ in the formula, R^a1Represents a 2-valent hydrocarbon group.

R^b1And R^b2Each independently represents a hydrogen atom or a hydrocarbon group.

R^c1And R^c2Each independently represents a 2-valent hydrocarbon group.]

Examples of the (meth) acrylic acid ester include linear alkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, lauryl (meth) acrylate, and octadecyl (meth) acrylate;

branched alkyl esters of (meth) acrylic acid such as isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, isohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isostearyl (meth) acrylate, and isoamyl (meth) acrylate;

alkyl esters containing an alicyclic skeleton of (meth) acrylic acid such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclododecyl (meth) acrylate, methylcyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and cyclohexyl α -ethoxyacrylate;

aromatic ring skeleton-containing esters of (meth) acrylic acid such as phenyl (meth) acrylate; and the like.

The structural unit derived from a (meth) acrylate may be an alkyl (meth) acrylate having a substituent in which a substituent is introduced into an alkyl group of the alkyl (meth) acrylate. The substituent of the alkyl (meth) acrylate having a substituent is a group which substitutes for a hydrogen atom of an alkyl group, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group. Specific examples of the alkyl (meth) acrylate having a substituent include 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2- (2-phenoxyethoxy) ethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and phenoxypoly (ethylene glycol) meth (acrylate).

These (meth) acrylates may be used alone or in different forms.

The resin (a) of the present invention preferably contains a constituent unit derived from an alkyl (meth) acrylate (a1) having a glass transition temperature Tg of less than 0 ℃ and derived from a homopolymer of an alkyl (meth) acrylate (a2) having a Tg of 0 ℃ or higher. This practice is advantageous in improving the high-temperature durability of the adhesive layer. The Tg of the homopolymer of the alkyl (meth) acrylate can be obtained, for example, from literature values of POLYMER HANDBOOK (Wiley-Interscience) and the like.

Specific examples of the alkyl (meth) acrylate (a1) include alkyl (meth) acrylates having an alkyl group of about 2 to 12 carbon atoms such as ethyl acrylate, n-and iso-propyl acrylate, n-and iso-butyl acrylate, n-pentyl acrylate, n-and iso-hexyl acrylate, n-heptyl acrylate, n-and iso-octyl acrylate, 2-ethylhexyl acrylate, n-and iso-nonyl acrylate, n-and iso-decyl acrylate, and n-dodecyl acrylate.

The alkyl (meth) acrylate (a1) may be used in only 1 kind, or may be used in combination of 2 or more kinds. Among them, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate and the like are preferable from the viewpoint of followability and reworkability when laminated on an optical film.

The alkyl (meth) acrylate (a2) is an alkyl (meth) acrylate other than the alkyl (meth) acrylate (a 1). Specific examples of the alkyl (meth) acrylate (a2) include methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, octadecyl acrylate, tert-butyl acrylate, and the like.

The alkyl (meth) acrylate (a2) may be used in only 1 kind, or may be used in combination of 2 or more kinds. Among them, the alkyl (meth) acrylate (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, and the like, and more preferably contains methyl acrylate, from the viewpoint of high-temperature durability.

Further, as the structural unit derived from a (meth) acrylate, a structural unit derived from a (meth) acrylate having a polar functional group can be also mentioned.

Examples of the (meth) acrylate monomer having a polar functional group include:

1-hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 1-hydroxyheptyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 1-hydroxypentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, 3-hydroxyhexyl (meth) acrylate, 3-hydroxyheptyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, hydroxy-n-yl (meth) acrylate, hydroxy-yl (, 4-hydroxyhexyl (meth) acrylate, 4-hydroxyheptyl (meth) acrylate, 4-hydroxyoctyl (meth) acrylate, 2-chloro-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 5-hydroxyheptyl (meth) acrylate, 5-hydroxyoctyl (meth) acrylate, 5-hydroxynonyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 6-hydroxyheptyl (meth) acrylate, 6-hydroxyoctyl (meth) acrylate, 6-hydroxynonyl (meth) acrylate, 6-hydroxyheptyl (meth) acrylate, and the like, 6-hydroxydecyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 7-hydroxyoctyl (meth) acrylate, 7-hydroxynonyl (meth) acrylate, 7-hydroxydecyl (meth) acrylate, 7-hydroxyundecyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 8-hydroxynonyl (meth) acrylate, 8-hydroxydecyl (meth) acrylate, 8-hydroxyundecyl (meth) acrylate, 8-hydroxydodecyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, 9-hydroxydecyl (meth) acrylate, 9-hydroxyundecyl (meth) acrylate, 9-hydroxydodecyl (meth) acrylate, 9-hydroxytridecyl (meth) acrylate, hydroxy-substituted (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 10-hydroxyundecyl (meth) acrylate, 10-hydroxydodecyl (meth) acrylate, 10-hydroxytridecyl acrylate, 10-hydroxytetradecyl (meth) acrylate, 11-hydroxyundecyl (meth) acrylate, 11-hydroxydodecyl (meth) acrylate, 11-hydroxytridecyl (meth) acrylate, 11-hydroxytetradecyl (meth) acrylate, 11-hydroxypentadecyl (meth) acrylate, 12-hydroxydodecyl (meth) acrylate, 12-hydroxytridecyl (meth) acrylate, 12-hydroxytetradecyl (meth) acrylate, 13-hydroxypentadecyl (meth) acrylate, and mixtures thereof, And alkyl (meth) acrylates having a hydroxyl group such as 13-hydroxytetradecyl (meth) acrylate, 13-hydroxypentadecyl (meth) acrylate, 14-hydroxytetradecyl (meth) acrylate, 14-hydroxypentadecyl (meth) acrylate, 15-hydroxypentadecyl (meth) acrylate, and 15-hydroxyheptadecyl (meth) acrylate.

Examples of the styrene monomer include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene and the like; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene, etc.; nitrostyrene; acetyl styrene; a methoxystyrene; and divinylbenzene.

Examples of the vinyl monomer include vinyl esters of fatty acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; nitrogen-containing heteroaromatic vinyl compounds such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated dienes such as butadiene, isoprene and chloroprene; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.

The epoxy compound is a compound having an epoxy group in the molecule. The epoxy group may be an epoxy group bonded to an alicyclic ring such as an epoxycyclopentane structure or an epoxycyclohexane structure.

Examples of the epoxy compound include 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl 3, 4-epoxy-6-methylcyclohexylmethylcyclohexanecarboxylate, ethylenebis (3, 4-epoxycyclohexanecarboxylate), bis (3, 4-epoxycyclohexylmethyl) adipate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, diethyleneglycol bis (3, 4-epoxycyclohexylmethyl ether), ethyleneglycol bis (3, 4-epoxycyclohexylmethyl ether), 2, 3, 14, 15-diepoxy-7, 11, 18, 21-tetraoxatrispiro [5.2.2.5.2.2] heneicosane, 3- (3, 4-epoxycyclohexyl) -8, 9-epoxy-1, 5-dioxaspiro [5.5] undecane, 4-vinylcyclohexene dioxide, limonene dioxide, bis (2, 3-epoxycyclopentyl) ether, dicyclopentadiene dioxide, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and the like.

The compound which gives the structural unit represented by the formula (a) can be synthesized, for example, by reacting a diisocyanate compound with a polyol.

The compound having the structural unit represented by the formula (b) can be synthesized, for example, by reacting a halosilane or a silane having a hydroxyl group.

The compound having the structural unit represented by formula (c) can be synthesized, for example, by a reaction between a polycarboxylic acid and a polyol.

The structural unit selected from the structural units described in group a is preferably a structural unit derived from a (meth) acrylate. The structural unit derived from a (meth) acrylate is preferably an alkyl (meth) acrylate or an alkyl (meth) acrylate having a hydroxyl group.

The resin (a) of the present invention may further contain another structural unit (sometimes referred to as a structural unit (aa)). Specifically, a structural unit derived from a (meth) acrylamide monomer, a structural unit derived from a monomer having a carboxyl group, a structural unit derived from a monomer having a heterocyclic group, a structural unit derived from a monomer having a substituted or unsubstituted amino group, and the like can be given.

Examples of the (meth) acrylamide monomer include N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (1, 1-dimethyl-3-oxobutyl) (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (, N- [ 2- (2-oxo-1-imidazolidinyl) ethyl ] -acrylamide, 2-acryloylamino-2-methyl-1-propanesulfonic acid, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) acrylamide, N- (1-methylethoxymethyl) (meth) acrylamide, N- (1-methylpropoxymethyl) (meth) acrylamide, N- (2-methylpropoxymethyl) (meth) acrylamide, N- (butoxymethyl) (meth) acrylamide, N- (1, 1-dimethylethoxymethyl) (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N-acryloylamino-2-methyl-1-propanesulfonic acid, N- (ethoxymethyl) (meth) acrylamide, N- (1-dimethylethoxymethyl) (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N- (2-ethoxymethyl) propanesulfonic acid, N- (methoxymethyl, N- (2-ethoxyethyl) (meth) acrylamide, N- (2-propoxyethyl) (meth) acrylamide, N- [ 2- (1-methylethoxy) ethyl ] -meth (acrylamide, N- [ 2- (1-methylpropoxy) ethyl ] -meth (acrylamide), N- [ 2- (2-methylpropoxy) ethyl ] -meth (acrylamide, N- (2-butoxyethyl) (meth) acrylamide, N- [ 2- (1, 1-dimethylethoxy) ethyl ] -meth (meth) acrylamide and the like. Among them, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) acrylamide and N- (2-methylpropoxymethyl) acrylamide are preferable.

Examples of the monomer having a carboxyl group include (meth) acrylic acid, carboxyalkyl (meth) acrylates (e.g., carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate), maleic acid, maleic anhydride, fumaric acid, crotonic acid, and the like, and acrylic acid is preferable.

Examples of the monomer having a heterocyclic group include acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, and 2, 5-dihydrofuran.

Examples of the monomer having a substituted or unsubstituted amino group include aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and the like.

The structural unit (aa) other than the structural units selected from group a and the structural unit having an indole structure is preferably a monomer having a carboxyl group.

The content of the structural unit having an indole structure is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the total structural units contained in the resin (a).

The content of at least 1 kind of structural unit selected from the structural units described in group a is preferably 50 parts by mass or more, more preferably 55 to 99.99 parts by mass, and still more preferably 60 to 85 parts by mass, based on 100 parts by mass of all the structural units of the resin (a).

When the resin (a) contains the structural unit (aa), it is preferably 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, further preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 7 parts by mass or less, based on 100 parts by mass of the total structural units of the resin (a).

When the resin (a) contains a structural unit derived from an alkyl (meth) acrylate having a hydroxyl group, the content of the structural unit is preferably 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, further preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 7 parts by mass or less, based on 100 parts by mass of the total structural units of the resin (a).

From the viewpoint of preventing the release force of the separator that can be laminated on the outer surface of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition from increasing, it is preferable that the separator contains substantially no monomer having an amino group. The term "substantially not containing a monomer having an amino group" as used herein means that the content of a structural unit derived from a monomer having an amino group is 0.1 parts by mass or less per 100 parts by mass of all the structural units constituting the resin (a).

From the viewpoint of reactivity between the resin (a) and the crosslinking agent (B) described later, the resin (a) preferably contains a structural unit derived from a hydroxyl group-containing alkyl (meth) acrylate or a structural unit derived from a carboxyl group-containing monomer, and more preferably contains both a structural unit derived from a hydroxyl group-containing alkyl (meth) acrylate and a structural unit derived from a carboxyl group-containing monomer. As the alkyl (meth) acrylate having a hydroxyl group, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate are preferable. In particular, by using 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and 5-hydroxypentyl acrylate, good durability can be obtained. As the monomer having a carboxyl group, acrylic acid is preferably used.

The weight average molecular weight (Mw) of the resin (a) of the present invention is preferably 30 to 250 ten thousand, and more preferably 50 to 200 ten thousand. When the weight average molecular weight is 30 ten thousand or more, the durability of the pressure-sensitive adhesive layer in a high-temperature environment is improved, and troubles such as peeling of an adherend from the pressure-sensitive adhesive layer and cohesive failure of the pressure-sensitive adhesive layer are easily suppressed. If the weight average molecular weight is 250 ten thousand or less, it is advantageous from the viewpoint of coatability when the adhesive composition is processed into, for example, a sheet form (coated on a substrate). From the viewpoint of satisfying both the durability of the pressure-sensitive adhesive layer and the coatability of the pressure-sensitive adhesive composition, the weight average molecular weight is preferably 60 to 180 ten thousand, more preferably 70 to 170 ten thousand, and further preferably 100 to 160 ten thousand. The molecular weight distribution (Mw/Mn) expressed by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 2 to 10, preferably 3 to 8. The weight average molecular weight can be analyzed by gel permeation chromatography and is a value in terms of standard polystyrene.

When the resin (A) of the present invention is dissolved in ethyl acetate to give a 20 mass% solution, the viscosity at 25 ℃ is preferably 20 pas or less, and more preferably 0.1 to 15 pas. A viscosity in this range is advantageous from the viewpoint of coatability when the adhesive composition is applied to a substrate. The viscosity can be measured by a brookfield viscometer.

The resin (a) of the present invention can be produced by a known method such as solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization, and the solution polymerization is particularly preferred. The solution polymerization method includes, for example, a method of mixing a monomer having an indole structure, a monomer which is used as needed to derive the structural unit described in group a, and an organic solvent, adding a thermal polymerization initiator under a nitrogen atmosphere, and stirring at a temperature of about 40 to 90 ℃, preferably about 50 to 80 ℃ for about 3 to 15 hours. In order to control the reaction, a monomer or a thermal polymerization initiator may be continuously or intermittently added during the polymerization. The monomer and the thermal initiator may be added to the organic solvent.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like is used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone and the like. Examples of the thermal polymerization initiator include azo compounds such as 2, 2 ' -azobisisobutyronitrile, 2 ' -azobis (2-methylbutyronitrile), 1 ' -azobis (cyclohexane-1-carbonitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), dimethyl 2, 2 ' -azobis (2-methylpropionate), and 2, 2 ' -azobis (2-hydroxymethylpropionitrile); organic peroxides such as lauroyl peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, and (3, 5, 5-trimethylhexanoyl) peroxide; and inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide. In addition, redox initiators using a combination of a peroxide and a reducing agent, and the like can also be used.

The proportion of the polymerization initiator is about 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of the monomers constituting the resin (A). Polymerization using active energy rays (e.g., ultraviolet rays) can be used for polymerization of the resin (a).

Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

The content of the resin (a) is usually 60 to 99.99 mass%, preferably 70 to 99.9 mass%, and more preferably 80 to 99.7 mass% in 100 mass% of the solid content of the binder composition.

< crosslinking agent (B) >)

The adhesive composition of the present invention may contain a crosslinking agent (B).

The crosslinking agent (B) includes isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, and the like, and particularly, isocyanate crosslinking agents are preferable from the viewpoints of the pot life of the adhesive composition (japanese text: ポットライフ), the durability of the adhesive layer, the crosslinking speed, and the like.

The isocyanate compound is preferably a compound having at least 2 isocyanate groups (-NCO) in the molecule, and examples thereof include aliphatic isocyanate compounds (e.g., hexamethylene diisocyanate), alicyclic isocyanate compounds (e.g., isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate), aromatic isocyanate compounds (e.g., toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like). The crosslinking agent (B) may be an adduct (adduct) of the isocyanate compound with a polyol compound [ for example, an adduct of glycerin, trimethylolpropane or the like ], an isocyanurate compound, a biuret compound, a urethane prepolymer type isocyanate compound obtained by addition reaction with a polyether polyol, a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol or the like, or the like. The crosslinking agent (B) may be used alone or in combination of two or more. Of these, typical examples include aromatic isocyanate compounds (e.g., toluene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (e.g., hexamethylene diisocyanate), adducts of these compounds with a polyol compound (e.g., glycerin, trimethylolpropane), and isocyanurate compounds. If the crosslinking agent (B) is an aromatic isocyanate compound and/or an adduct thereof using a polyol compound or an isocyanurate compound, the durability of the pressure-sensitive adhesive layer may be improved because it is advantageous to form an optimum crosslinking density (or crosslinking structure). In particular, when the adhesive layer is a toluene diisocyanate based compound and/or an adduct thereof using a polyol compound, the durability can be improved even when the adhesive layer is applied to a polarizing plate or the like.

The content of the crosslinking agent (B) is usually 0.01 to 15 parts by mass, preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the resin (A).

The adhesive composition of the present invention may further contain a silane compound (D).

Examples of the silane compound (D) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.

The silane compound (D) may also be a silicone oligomer. Specific examples of the silicone oligomer are shown below when the silicone oligomer is expressed as a combination of monomers.

Mercaptopropyl-containing oligomers such as 3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomer; mercapto methyl group-containing oligomers such as mercapto methyltrimethoxysilane-tetramethoxysilane oligomer, mercapto methyltrimethoxysilane-tetraethoxysilane oligomer, mercapto methyltriethoxysilane-tetramethoxysilane oligomer, and mercapto methyltriethoxysilane-tetraethoxysilane oligomer; 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyl group-containing copolymers such as 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane oligomer, methacryloxypropyl-containing oligomers such as 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, and 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer; 3-acryloxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-acryloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-acryloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-acryloxypropyltriethoxysilane-tetraethoxysilane oligomer, acryloxypropyl-containing oligomers such as 3-acryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-acryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, and 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer; vinyl group-containing oligomers such as vinyltrimethoxysilane-tetramethoxysilane oligomer, vinyltrimethoxysilane-tetraethoxysilane oligomer, vinyltriethoxysilane-tetramethoxysilane oligomer, vinyltriethoxysilane-tetraethoxysilane oligomer, vinylmethyldimethoxysilane-tetramethoxysilane oligomer, vinylmethyldimethoxysilane-tetraethoxysilane oligomer, vinylmethyldiethoxysilane-tetramethoxysilane oligomer, and vinylmethyldiethoxysilane-tetraethoxysilane oligomer; amino group-containing copolymers such as 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.

The silane compound (D) may be a silane compound represented by the following formula (D1).

(in the formula, A)¹Represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, -CH constituting the alkanediyl group and the alicyclic hydrocarbon group₂-may be replaced by-O-or-CO-, R⁴¹Represents an alkyl group having 1 to 5 carbon atoms, R⁴²、R⁴³、R⁴⁴、R⁴⁵And R⁴⁶Each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. )

As A¹Examples of the alkanediyl group having 1 to 20 carbon atoms include a methylene group, a1, 2-ethanediyl group, a1, 3-propanediyl group, a1, 4-butanediyl group, a1, 5-pentanediyl group, a1, 6-hexanediyl group, a1, 7-heptanediyl group, a1, 8-octanediyl group, a1, 9-nonanediyl group, a1, 10-decanediyl group, a1, 12-dodecanediyl group, a1, 14-tetradecanediyl group, a1, 16-hexadecanediyl group, a1, 18-octadecanediyl group and a1, 20-eicosanediyl group. Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include 1, 3-cyclopentadienyl and 1, 4-cycloadienyl. as-CH to constitute the alkanediyl group and the alicyclic hydrocarbon group₂Examples of the group substituted by-O-or-CO-include-CH₂CH₂-O-CH₂CH₂-、-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-、-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-、-CH₂CH₂-CO-O-CH₂CH₂-、-CH₂CH₂-O-CH₂CH₂-CO-O-CH₂CH₂-、-CH₂CH₂CH₂CH₂-O-CH₂CH₂-and-CH₂CH₂CH₂CH₂-O-CH₂CH₂CH₂CH₂-。

As R⁴¹～R⁴⁵Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group and a pentyl group, and R is⁴²～R⁴⁵Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group and a pentyloxy group.

Examples of the silane compound represented by the formula (d1) include (trimethoxysilyl) methane, 1, 2-bis (trimethoxysilyl) ethane, 1, 2-bis (triethoxysilyl) ethane, 1, 3-bis (trimethoxysilyl) propane, 1, 3-bis (triethoxysilyl) propane, 1, 4-bis (trimethoxysilyl) butane, 1, 4-bis (triethoxysilyl) butane, 1, 5-bis (trimethoxysilyl) pentane, 1, 5-bis (triethoxysilyl) pentane, 1, 6-bis (trimethoxysilyl) hexane, 1, 6-bis (triethoxysilyl) hexane, 1, 6-bis (tripropoxysilyl) hexane, 1, 8-bis (trimethoxysilyl) octane, 1, 2-bis (trimethoxysilyl) ethane, 1, 2-bis (triethoxysilyl) ethane, 1, 4-bis (triethoxysilyl) butane, 1, 5-bis (, Bis (tri-C1-5 alkoxysilyl) C1-10 alkanes such as 1, 8-bis (triethoxysilyl) octane and 1, 8-bis (tripropoxysilyl) octane; bis (di-C1-5 alkoxy C1-5 alkylsilyl) C1-10 alkanes such as bis (dimethoxymethylsilyl) methane, 1, 2-bis (dimethoxymethylsilyl) ethane, 1, 2-bis (dimethoxyethylsilyl) ethane, 1, 4-bis (dimethoxymethylsilyl) butane, 1, 4-bis (dimethoxyethylsilyl) butane, 1, 6-bis (dimethoxymethylsilyl) hexane, 1, 6-bis (dimethoxyethylsilyl) hexane, 1, 8-bis (dimethoxymethylsilyl) octane and 1, 8-bis (dimethoxyethylsilyl) octane; and bis (mono C1-5 alkoxy-di C1-5 alkylsilyl) C1-10 alkanes such as 1, 6-bis (methoxydimethylsilyl) hexane and 1, 8-bis (methoxydimethylsilyl) octane. Among them, bis (tri C1-3 alkoxysilyl) C1-10 alkanes such as 1, 2-bis (trimethoxysilyl) ethane, 1, 3-bis (trimethoxysilyl) propane, 1, 4-bis (trimethoxysilyl) butane, 1, 5-bis (trimethoxysilyl) pentane, 1, 6-bis (trimethoxysilyl) hexane, 1, 8-bis (trimethoxysilyl) octane and the like are preferable, and 1, 6-bis (trimethoxysilyl) hexane and 1, 8-bis (trimethoxysilyl) octane are particularly preferable.

The content of the silane compound (D) is usually 0.01 to 10 parts by mass, preferably 0.03 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, and still more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the resin (A).

The adhesive composition may further contain an antistatic agent.

Examples of the antistatic agent include a surfactant, a silicone compound, a conductive polymer, an ionic compound, and the like, and an ionic compound is preferable. The ionic compound may be a conventional ionic compound. Examples of the cation component constituting the ionic compound include an organic cation and an inorganic cation. Examples of the organic cation include a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, an imidazolium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation. Examples of the inorganic cation include alkali metal cations such as lithium cation, potassium cation, sodium cation, and cesium cation, and alkaline earth metal cations such as magnesium cation and calcium cation. In particular, from the viewpoint of compatibility with the (meth) acrylic resin, a pyridinium cation, an imidazolium cation, a pyrrolidinium cation, a lithium cation, and a potassium cation are preferable. As the anionic component constituting the ionic compound, there may be mentionedAlthough the anion is either an inorganic anion or an organic anion, an anion component containing a fluorine atom is preferable from the viewpoint of antistatic performance. Examples of the anion component containing a fluorine atom include hexafluorophosphate anion (PF)₆ ^-) Bis (trifluoromethanesulfonyl) imide anion [ (CF)₃ SO₂)₂N^-]Bis (fluorosulfonyl) imide anion [ (FSO)₂)₂N^-]Tetrakis (pentafluorophenyl) borate anion [ (C)₆F₅)₄B^-]And the like. These ionic compounds may be used alone or in combination of two or more. Particular preference is given to the bis (trifluoromethanesulfonyl) imide anion [ (CF)₃SO₂)₂N^-]Bis (fluorosulfonyl) imide anion [ (FSO)₂)₂N^-]Tetrakis (pentafluorophenyl) borate anion [ (C)₆F₅)₄B^-]。

From the viewpoint of the stability with time of the antistatic property of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, an ionic compound which is solid at room temperature is preferable.

The content of the antistatic agent is, for example, 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 1 to 7 parts by mass, based on 100 parts by mass of the resin (A).

The adhesive composition may contain 1 or 2 or more kinds of additives such as a solvent, a crosslinking catalyst, a tackifier, a plasticizer, a softener, a pigment, a rust inhibitor, an inorganic filler, and light-scattering fine particles.

< adhesive layer >

The pressure-sensitive adhesive layer of the present invention can be formed, for example, by dissolving or dispersing the pressure-sensitive adhesive composition in a solvent to prepare a pressure-sensitive adhesive composition containing a solvent, applying the pressure-sensitive adhesive composition to the surface of a substrate, and drying the applied pressure-sensitive adhesive composition.

The substrate is preferably a plastic film, and specifically, a release film subjected to a release treatment is exemplified. Examples of the release film include a film obtained by subjecting one surface of a film containing a resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate to a mold release treatment such as a silicone treatment.

The pressure-sensitive adhesive layer of the present invention is preferably a pressure-sensitive adhesive layer satisfying the following formula (3), and more preferably a pressure-sensitive adhesive layer also satisfying the formula (4).

A(405)≥0.5 (3)

[ in the formula (3), A (405) represents the absorbance at a wavelength of 405 nm. ]

A(405)/A(440)≥5 (4)

In the formula (4), A (405) represents the absorbance at a wavelength of 405nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]

The larger the value of A (405), the higher the absorption at a wavelength of 405 nm. If the value of a (405) is less than 0.5, the absorption at a wavelength of 405nm is low, and the organic EL light-emitting element and the liquid crystal retardation film are likely to be deteriorated by light near 400 nm. The value of a (405) is preferably 0.6 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more. The upper limit is not particularly limited, but is usually 10 or less.

The value of A (405)/A (440) represents the magnitude of absorption at wavelength 405nm relative to the magnitude of absorption at wavelength 440 nm. The larger the value of a (405)/a (440), the more specific the absorption in the wavelength region around 405nm, and when the pressure-sensitive adhesive layer of the present invention is applied to a display device such as an organic EL display device or a liquid crystal display device, it is possible to absorb light around 400nm without hindering the color expression of the display device, and to suppress the light degradation of the organic EL light-emitting element and the liquid crystal retardation film. The value of a (405)/a (440) is preferably 10 or more, more preferably 30 or more, and further preferably 60 or more.

The thickness of the adhesive layer of the present invention is usually 0.1 to 100. mu.m, preferably 3 to 50 μm, and more preferably 4 to 25 μm.

< optical laminate >

The pressure-sensitive adhesive composition of the present invention and the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition can be used, for example, for bonding an optical film.

An optical laminate in which an optical film is laminated on at least one side of the adhesive layer of the present invention is also included in the present invention.

The optical laminate of the present invention can be formed by dissolving or dispersing the pressure-sensitive adhesive composition in a solvent to prepare a solvent-containing pressure-sensitive adhesive composition, applying the solvent-containing pressure-sensitive adhesive composition to the surface of an optical film, and drying the applied solvent-containing pressure-sensitive adhesive composition. Alternatively, the pressure-sensitive adhesive layer may be formed on a release film in the same manner, and the pressure-sensitive adhesive layer may be laminated (transferred) on the surface of the optical film.

An optical laminate including the pressure-sensitive adhesive layer of the present invention will be described with reference to the drawings.

Fig. 1 to 5 show an example of the layer structure of the pressure-sensitive adhesive layer of the present invention and the optical laminate of the present invention.

The pressure-sensitive adhesive layer 1 shown in fig. 1 is a state in which a release film 2 is bonded to the pressure-sensitive adhesive layer surface 1 for temporary protection of the pressure-sensitive adhesive layer surface.

The optical laminate 10A shown in fig. 2 is an optical laminate including an optical film 40, a pressure-sensitive adhesive layer 1 of the present invention, and a release film 2.

The optical laminate 10B shown in fig. 3 is an optical laminate including a protective film 8, an adhesive layer 7, a polarizing film 9, an adhesive layer 7, a protective film 8, a pressure-sensitive adhesive layer 1 of the present invention, and a release film 2.

The optical laminate 10C shown in fig. 4 and the optical laminate 10D shown in fig. 5 are optical laminates including a protective film 8, an adhesive layer 7, a polarizing film 9, an adhesive layer 7, a protective film 8, an adhesive layer 1 of the present invention, a retardation film 110, an adhesive layer 7a, and a light-emitting element 30 (a liquid crystal cell, an organic EL cell).

The optical film 40 has optical functions of transmitting, reflecting, and absorbing light. The optical film 40 may be a single-layer film or a multilayer film. Examples of the optical film 40 include a polarizing film, a phase difference film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a light-collecting film, and a window film, and preferably a polarizing film, a phase difference film, a window film, or a laminated film thereof.

The condensing film is a film used for the purpose of controlling an optical path and the like, and may be a prism array sheet, a lens array sheet, a sheet with dots attached thereto, or the like.

The brightness enhancement film is a film used for the purpose of improving the brightness of a liquid crystal display device to which a polarizing plate is applied. Specifically, there are a reflective polarization separation sheet designed to laminate a plurality of films having different refractive index anisotropy to generate anisotropy in reflectance, an alignment film in which a cholesteric liquid crystal polymer is supported on a base film, and a circularly polarized light separation sheet in which a liquid crystal layer is aligned.

The window film is a front panel of a flexible display device such as a flexible display, and is generally disposed on the outermost surface of the display device. Examples of the window film include resin films containing polyimide resins. The window film may be a composite film of an organic material and an inorganic material, such as a resin film containing polyimide and silica. The window film may have a hard coat layer disposed on the surface thereof for imparting functions of surface hardness, stain resistance, and fingerprint resistance. Examples of the window film include films described in jp 2017-94488 a.

The polarizing film is a film having properties of absorbing linearly polarized light having a vibration plane parallel to the absorption axis thereof and transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis (parallel to the transmission axis), and for example, a film in which a polyvinyl alcohol resin film is aligned by adsorbing a dichroic dye thereto may be used.

Examples of the dichroic dye include iodine and a dichroic organic dye.

The saponification degree of the polyvinyl alcohol resin is usually 85 mol% to 100 mol%, and preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and examples thereof include polyvinyl formal, polyvinyl acetal, and the like modified with an aldehyde. The polymerization degree of the polyvinyl alcohol resin is usually 1000 to 10000, preferably 1500 to 5000.

In general, a film obtained by forming a polyvinyl alcohol resin film is used as a material film of a polarizing film. The polyvinyl alcohol resin can be formed into a film by a known method. The thickness of the raw material film is usually 1 to 150 μm, and preferably 10 μm or more in consideration of ease of stretching and the like.

The polarizing film is produced, for example, by subjecting a raw material film to uniaxial stretching, dyeing the film with a dichroic dye to adsorb the dichroic dye, treating the film with an aqueous boric acid solution, washing the film with water, and finally drying the film. The thickness of the polarizing film is usually 1 to 30 μm, and from the viewpoint of making a thin optical laminate with an adhesive layer, the thickness is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less.

At least one surface of the polarizing film is preferably a polarizing plate provided with a protective film via an adhesive.

As the adhesive, a known adhesive is used, and may be a water-based adhesive or an active energy ray-curable adhesive.

Examples of the aqueous adhesive include conventional aqueous adhesives (for example, adhesives comprising an aqueous polyvinyl alcohol resin solution, aqueous two-part urethane emulsion adhesives, aldehyde compounds, epoxy compounds, melamine compounds, methylol compounds, isocyanate compounds, amine compounds, crosslinking agents such as polyvalent metal salts, and the like). Among them, an aqueous adhesive comprising a polyvinyl alcohol resin aqueous solution can be suitably used. In the case of using an aqueous adhesive, it is preferable to perform a step of drying the polarizing film in order to remove water contained in the aqueous adhesive after the polarizing film and the protective film are bonded to each other. After the drying step, a curing step of curing at a temperature of, for example, about 20 to 45 ℃ may be provided. The adhesive layer formed of the aqueous adhesive is usually 0.001 to 5 μm.

The active energy ray-curable adhesive is an adhesive which is cured by irradiation with an active energy ray such as ultraviolet ray or electron beam, and examples thereof include a curable composition containing a polymerizable compound and a photopolymerization initiator, a curable composition containing a photoreactive resin, a curable composition containing a binder resin and a photoreactive crosslinking agent, and the like, and an ultraviolet ray-curable adhesive is preferable.

Examples of the method for bonding the polarizing film and the protective film include a method in which at least one of the surfaces to be bonded is subjected to surface activation treatment such as saponification treatment, corona treatment, and plasma treatment. When the protective films are bonded to both surfaces of the polarizing film, the adhesives used for bonding the resin films may be the same type of adhesive or different types of adhesives.

The protective film is preferably a film made of a light-transmitting thermoplastic resin. Specifically, examples thereof include polyolefin-based resins; a cellulose-based resin; a polyester resin; (meth) acrylic resins; or mixtures, copolymers, etc. thereof. When protective films are provided on both sides of the polarizing film, the protective films to be used may be films containing different thermoplastic resins or films containing the same thermoplastic resin.

When a protective film is laminated on at least one surface of the polarizing film, the protective film is preferably a protective film containing a polyolefin resin or a cellulose resin. By using these films, shrinkage of the polarizing film in a high-temperature environment can be effectively suppressed without impairing the optical characteristics of the polarizing film. The protective film may be an oxygen barrier layer.

A preferable configuration of the polarizing plate is one in which a protective film is laminated on at least one surface of a polarizing film via an adhesive layer. When a protective film is laminated on only one surface of the polarizing film, it is more preferably laminated on the visible side. The protective film laminated on the visible side is preferably a protective film containing a triacetylcellulose-based resin or a cycloolefin-based resin. The protective film may be an unstretched film or may be stretched in an optional direction to have a retardation. A surface treatment layer such as a hard coat layer or an antiglare layer may be provided on the surface of the protective film laminated on the visible side.

When protective films are laminated on both sides of the polarizing film, the protective film on the panel side (the side opposite to the viewing side) is preferably a protective film or a retardation film comprising a triacetyl cellulose resin, a cycloolefin resin, or an acrylic resin. The retardation film may be a zero retardation film described later.

The retardation film is an optical film exhibiting optical anisotropy, and examples thereof include a stretched film obtained by stretching a polymer film containing polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycycloolefin, polystyrene, polysulfone, polyethersulfone, polyvinylidene fluoride/polymethyl methacrylate, acetyl cellulose, a saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, or the like by about 1.01 to 6 times. Among the stretched films, preferred are polymer films obtained by uniaxially or biaxially stretching an acetylcellulose film, a polyester film, a polycarbonate film, or a cycloolefin resin film. The retardation film may be one in which optical anisotropy is exhibited by applying a liquid crystalline compound to a substrate and aligning the liquid crystalline compound.

In the present specification, the retardation film includes a zero retardation film, and also includes films such as a uniaxial retardation film, a low photoelastic modulus retardation film, and a large viewing angle retardation film.

The zero retardation film means a front retardation R_eRetardation R with respect to the thickness direction_thAll of them are-15 to 15nm and optically isotropic films. The zero retardation film may be a resin film containing a cellulose-based resin, a polyolefin-based resin (e.g., a chain polyolefin-based resin or a polycycloolefin-based resin), or a polyethylene terephthalate-based resin, and the cellulose-based resin or the polyolefin-based resin is preferable in terms of easy control of retardation value and easy acquisition. The zero retardation film may also be used as a protective film. Examples of the zero retardation film include "Z-TAC" (trade name) sold by fuji film (strain), "Zerotac (registered trademark) sold by Konica Minolta Opto (strain)," ZF-14 "(trade name) sold by japan ZEON (strain), and the like.

In the optical film of the present invention, the retardation film is preferably a retardation film which exhibits optical anisotropy by coating a liquid crystalline compound and aligning the liquid crystalline compound.

Examples of the film which exhibits optical anisotropy by application and alignment of a liquid crystalline compound include the following first to fifth embodiments.

The first mode is as follows: retardation film in which rod-like liquid crystal compound is oriented in horizontal direction with respect to supporting substrate

The second mode is as follows: retardation film in which rod-like liquid crystal compound is aligned in the vertical direction with respect to supporting substrate

A third mode: retardation film in which rod-like liquid crystal compound changes orientation direction in plane in spiral manner

A fourth formula: retardation film having discotic liquid crystal compound obliquely aligned

The fifth mode is: biaxial retardation film in which discotic liquid crystal compound is oriented in a direction perpendicular to support base

For example, the first, second, and fifth embodiments can be suitably used as an optical film used for an organic electroluminescent display. Alternatively, these types of retardation films may be used in a stacked state.

When the retardation film is a layer containing a polymer in an aligned state of a polymerizable liquid crystal compound (hereinafter, sometimes referred to as "optically anisotropic layer"), the retardation film preferably has reverse wavelength dispersibility. The reverse wavelength dispersibility is an optical property that the in-plane retardation value of the liquid crystal alignment film at the short wavelength is smaller than the in-plane retardation value of the liquid crystal alignment film at the long wavelength, and the retardation film preferably satisfies the following formulae (7) and (8). Re (λ) represents an in-plane phase difference value with respect to light having a wavelength λ nm.

Re(450)/Re(550)≤1 (7)

1≤Re(630)/Re(550) (8)

In the optical film of the present invention, when the retardation film is of the first mode and has reverse wavelength dispersibility, it is preferable that 0.82. ltoreq. Re (450)/Re (550). ltoreq.0.93 in the above formula (7) is more preferable because coloring at the time of black display in a display device is reduced. Furthermore, 120. ltoreq. Re (550). ltoreq.150 is preferred.

Examples of polymerizable liquid crystal compounds when the retardation film is a film having an optically anisotropic layer include a compound having a polymerizable group among compounds described in "3.8.6 network (completely crosslinked type)" and "6.5.1 liquid crystal material b. polymerizable nematic liquid crystal material" in the liquid crystal display (published by the editorial committee for liquid crystal display, published by kakken for 12 years, 10 months and 30 days), and polymerizable liquid crystal compounds described in japanese patent application laid-open nos. 2010-31223, 2010-270108, 2011-6360, 2011-207765, 2011-162678, 2016-81035, 2017/043438, and 2011-207765.

Examples of a method for producing a retardation film from a polymer in an aligned state of a polymerizable liquid crystal compound include the method described in jp 2010-31223 a.

In the case of the second embodiment, the front phase difference Re (550) may be adjusted to a range of 0 to 10nm, preferably 0 to 5nm, and the phase difference R in the thickness direction_thIt is only necessary to adjust the particle diameter to a range of-10 to-300 nm, preferably a range of-20 to-200 nm. Phase difference value R in thickness direction for expressing refractive index anisotropy in thickness direction_thThe phase difference value R can be measured by tilting 50 degrees about the fast axis in the plane as the tilt axis₅₀Phase difference value R in sum plane₀And (6) calculating. I.e. the phase difference value R for the thickness direction_thCan be based on the in-plane phase difference value R₀And a phase difference value R measured by tilting the fast axis by 50 degrees as a tilt axis₅₀Thickness d of retardation film, and average refractive index n of retardation film₀N is obtained by the following equations (10) to (12)_x、n_yAnd n_zThese are calculated by substituting them into the formula (9).

R_th＝[(n_x+n_y)/2-n_z]×d (9)

R₀＝(n_x-n_y)×d (10)

R₅₀＝(n_x-n_y')×d/cos(φ) (11)

(n_x+n_y+n_z)/3＝n₀ (12)

Here, the number of the first and second electrodes,

φ＝sin^-1〔sin(40°)/n₀〕

n_y'＝n_y×n_z/〔n_y ²×sin²(φ)+n_z ²×cos²(φ)〕^1/2

examples of the FILM exhibiting optical anisotropy by coating and alignment of a liquid crystal compound and the FILM exhibiting optical anisotropy by coating of an inorganic layered compound include a FILM called a temperature compensation type retardation FILM, "NH FILM" (trade name; FILM in which rod-like liquid crystal is obliquely oriented) sold by JX ri maishi energy (strain), a "WV FILM" (trade name; FILM in which discotic liquid crystal is obliquely oriented) sold by fuji FILM (strain), a "VAC FILM" (trade name; FILM of a completely biaxial orientation type) sold by sumitomo chemical (strain), and a "newVAC FILM" sold by sumitomo chemical (strain); biaxially oriented type film), and the like.

The retardation film may be a multilayer film having two or more layers. Examples of the retardation film include a retardation film in which a protective film is laminated on one surface or both surfaces of the retardation film, and a retardation film in which two or more retardation films are laminated with an adhesive or an adhesive interposed therebetween.

When the retardation film is a multilayer film, as a configuration of an optical laminate including the optical film of the present invention, as shown in fig. 4, there is a configuration including a retardation film 110 in which a 1/4 wavelength retardation layer 50 which imparts a retardation of 1/4 wavelengths to transmitted light and a 1/2 wavelength retardation layer 70 which imparts a retardation of 1/2 wavelengths to transmitted light are laminated via an adhesive layer or an adhesive layer 60. As shown in fig. 5, an optical film 40 including an 1/4-wavelength retardation layer 50a and a positive C layer 80 laminated via an adhesive layer or a pressure-sensitive adhesive layer 60 may be used.

The 1/4 wavelength retardation layer 50 which imparts a retardation of 1/4 wavelengths in fig. 4 and the 1/2 wavelength retardation layer 70 which imparts a retardation of 1/2 wavelengths to transmitted light may be the optical film of the first embodiment or the optical film of the fifth embodiment. In the case of the configuration of fig. 4, at least one of them is more preferably the fifth aspect.

In the case of the configuration of fig. 5, the 1/4-wavelength retardation layer 50a is preferably the optical film of the first embodiment, and more preferably satisfies the expressions (7) and (8).

The adhesive layer 7a in fig. 4 and 5 is a layer formed of an adhesive composition. The adhesive layer 7a may be formed using a known adhesive composition, or may be formed using the adhesive composition of the present invention.

< liquid crystal display device >

The resin of the present invention, the adhesive composition containing the resin, and the optical laminate containing the adhesive layer formed from the adhesive composition can be used in display devices (FPD: flat panel display) such as organic EL display devices and liquid crystal display devices by laminating them on display devices such as organic EL devices and liquid crystal cells.

Examples

The present invention will be described in further detail below with reference to examples and comparative examples. In examples, comparative examples and polymerization examples, "%" and "parts" are "% by mass" and "parts by mass" unless otherwise specified.

[ example 1 ]: synthesis of light selective absorbing Compound having indole Structure and polymerizable group

A1000 mL four-necked flask equipped with a Dimrot condenser and a thermometer was charged with a nitrogen atmosphere, 100 parts of the compound represented by formula (1) (1-methyl-2-phenyl-1H-indole-3-carbaldehyde), 40 parts of cyanoacetic acid, 76 parts of piperidine and 300 parts of acetonitrile were added, and the mixture was stirred and kept at 80 ℃ for 4 hours. Crystals precipitated from the resulting mixture were separated by filtration and taken out. The resulting crystals were mixed with 500 parts of 5% sulfuric acid, and kept at 80 ℃ for 1 hour while stirring. The resulting mixture was filtered to give a solid. The obtained solid was washed with 300 parts of water and dried to obtain 116 parts of a compound represented by formula (2) (2-cyano-3- (1-methyl-2-phenyl-1H-indol-3-yl) -2-acrylic acid).

Identification of Compound represented by formula (2)

¹H-NMR(CDCl₃)δ：3.70(s、3H)、7.30-7.42(dt、2H)、7.50-7.55(m、2H)、7.60-7.64(m、3H)、7.68(d、1H)、7.93(s、1H)、8.26(d、1H)

After a nitrogen atmosphere was replaced in a 100mL four-necked flask equipped with a thermometer, 5 parts of the compound represented by formula (2), 2.3 parts of 4-hydroxybutyl acrylate, 0.4 part of N, N-dimethyl-4-aminopyridine, 0.2 part of 2, 6-di-tert-butyl-4-methylphenol, and 50 parts of chloroform were added thereto and the mixture was cooled to 0 ℃. To the resulting mixture, 2.2 parts of N, N' -diisopropylcarbodiimide was added dropwise while maintaining the temperature at 0 to 5 ℃. After the dropwise addition, the resulting mixture was incubated at 10 ℃ for 4 hours. The resulting mixture was filtered to obtain a filtrate. The resulting filtrate was concentrated to give an oil. To the oil thus obtained, 50 parts of toluene and 50 parts of water were mixed and separated to obtain a toluene layer. The resulting toluene layer was concentrated to give yellow crude crystals. The crude crystal was recrystallized from isopropanol to obtain 4.9 parts of a compound represented by formula (3) (2-cyano-3- (1-methyl-2-phenyl-1H-indol-3-yl) -2-acrylic acid-4-acryloyloxybutyl ester). The maximum absorption wavelength of the compound represented by the formula (3) is 386 nm.

Identification of Compound represented by formula (3)

¹H-NMR(CDCl₃)δ：1.75-1.80(m、4H)、3.70(s、3H)、4.15-4.20(t、2H)、4.23-4.27(t、2H)、5.78-5.82(dd、1H)、6.06-6.14(dd、1H)、6.36-6.41(dd、1H)7.35-7.43(m、5H)、7.54-7.57(m、3H)、8.12(s、1H)、8.42-8.45(m、1H)

The obtained methyl ethyl ketone solution (0.006g/L) of the compound represented by the formula (3) was placed in a 1cm quartz cell, the quartz cell was set in a spectrophotometer UV-2450 (manufactured by Shimadzu corporation), and the absorbance was measured in a wavelength range of 300 to 800nm in 1nm step by a two-beam method. The gram absorption coefficient for each wavelength was calculated from the obtained absorbance value, the concentration of the compound in the solution, and the optical path length of the quartz cell. As a result, ∈ (405) — 34.9L/(g · cm), ∈ (440) — 2.0L/(g · cm), and ∈ (405)/∈ (440) — 17.5.

ε(λ)＝A(λ)/CL

[ in the formula, [ epsilon ] (lambda) ] represents the gram absorption coefficient L/(g · cm) of the compound represented by formula (3) at a wavelength of lambda nm, A (lambda) represents the absorbance at the wavelength of lambda nm, C represents the concentration g/L, and L represents the optical path length cm of the quartz cell. Angle (c)

[ example 2 ]: synthesis of light selective absorbing Compound having indole Structure and polymerizable group

4.3 parts of a compound represented by the formula (4) (2-cyano-3- (1-methyl-2-phenyl-1H-indol-3-yl) -2-propenoic acid-2-acryloyloxyethyl ester) was obtained in the same manner as in example 1, except that 2.3 parts of 2-hydroxyethyl acrylate was used in place of 2.3 parts of 4-hydroxybutyl acrylate. The maximum absorption wavelength of the compound represented by the formula (4) was 388 nm. As a result of determining the gram absorption coefficient in the same manner as in example 1, ∈ (405) was 45.4L/(g · cm), ∈ (440) was 1.0L/(g · cm), and ∈ (405)/∈ (440) was 45.4.

Identification of Compound represented by formula (4)

¹H-NMR(CDCl₃)δ：3.70(s、3H)、4.38-4.43(dt、2H)、4.43-4.48(dt、2H)、5.83-5.86(dd、1H)、6.09-6.17(dd、1H)、6.4-6.45(dd、1H)7.35-7.45(m、5H)、7.52-7.58(m、3H)、8.12(s、1H)、8.42-8.45(m、1H)

[ example 3 ]: synthesis of resin (A-1) containing structural Unit having indole Structure

A mixed solution of 141 parts of ethyl acetate, 94 parts of butyl acrylate, 3 parts of 2-hydroxyethyl acrylate and 3 parts of a compound represented by the formula (3) as a solvent was charged into a reaction vessel equipped with a condenser, a nitrogen inlet, a thermometer and a stirrer, and the air in the apparatus was replaced with nitrogen gas to set the internal temperature to 60 ℃ while oxygen was not contained. To the resulting mixture, the entire amount of a solution prepared by dissolving 0.63 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. The resultant mixture was kept at 60 ℃ for 7 hours, and then the whole amount of a solution obtained by dissolving 0.0012 part of 4-methoxyphenol (polymerization inhibitor) in 5 parts of ethyl acetate was added to the resultant mixture. To the resulting mixture was added ethyl acetate and adjusted in such a manner that the concentration of the resin (A-1) having an indole structure was 20%, to prepare an ethyl acetate solution of the resin (A-1) having an indole structure. The weight average molecular weight Mw of the obtained resin (A-1) having an indole structure was 74 ten thousand in terms of polystyrene equivalent by GPC, and Mw/Mn was 5.2. The glass transition temperature based on DSC was-51 ℃.

< g absorptivity ε measurement >

The obtained methyl ethyl ketone solution (0.011g/L) of the resin (A-1) was put into a 1cm quartz cell, the quartz cell was set in a spectrophotometer UV-2450 (manufactured by Shimadzu corporation), and the absorbance was measured in a wavelength range of 300 to 800nm at a step length of 1nm by a two-beam method. The gram absorption coefficient for each wavelength was calculated from the obtained absorbance value, the concentration of the resin (A) in the solution, and the optical path length of the quartz cell. As a result, the resin (a-1) had ∈ (405) of 0.442L/(g · cm), ∈ (440) of 0.008L/(g · cm), and ∈ (405)/∈ (440) of 53.3.

ε(λ)＝A(λ)/CL

[ in the formula, [ epsilon ] (lambda) ] represents the gram absorption coefficient L/(g cm) of the resin (A) at a wavelength of lambda nm, A (lambda) represents the absorbance at the wavelength of lambda nm, C represents the concentration g/L, and L represents the optical path length cm of the quartz cell. Angle (c)

[ example 4 ]: synthesis of resin (A-2) containing structural Unit having indole Structure

A mixed solution of 141 parts of ethyl acetate, 94 parts of butyl acrylate, 3 parts of 2-hydroxyethyl acrylate and 3 parts of a compound represented by the formula (4) as a solvent was charged into a reaction vessel equipped with a condenser, a nitrogen inlet, a thermometer and a stirrer, and the air in the apparatus was replaced with nitrogen gas to set the internal temperature to 60 ℃ while oxygen was not contained. To the resulting mixture, the entire amount of a solution prepared by dissolving 0.63 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. The resultant mixture was kept at 60 ℃ for 7 hours, and then the whole amount of a solution obtained by dissolving 0.0012 part of 4-methoxyphenol (polymerization inhibitor) in 5 parts of ethyl acetate was added to the resultant mixture. To the resulting mixture, ethyl acetate was added and adjusted in such a manner that the concentration of the resin (A-2) having an indole structure was 20%, to prepare an ethyl acetate solution of the resin (A-2) having an indole structure. The weight average molecular weight Mw of the obtained resin (A-2) having an indole structure was 67 ten thousand in terms of polystyrene equivalent by GPC, and Mw/Mn was 4.9. The glass transition temperature based on DSC is-50 ℃. As a result of measuring the gram absorption coefficient of the resin (a-2) by the same method as in example 3, epsilon (405) was 0.336L/(g · cm), epsilon (440) was 0.035L/(g · cm), and epsilon (405)/epsilon (440) was 9.5.

[ polymerization example 1 ]: preparation of acrylic resin (A-3)

141 parts of ethyl acetate, 94 parts of butyl acrylate and 3 parts of 2-hydroxyethyl acrylate were added thereto, and the atmosphere in the apparatus was replaced with nitrogen gas to thereby obtain a non-oxygen atmosphere and an internal temperature of 60 ℃. To the resulting mixture, the entire amount of a solution prepared by dissolving 0.63 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. The resultant mixture was kept at 60 ℃ for 7 hours, and then the whole amount of a solution obtained by dissolving 0.0012 part of 4-methoxyphenol (polymerization inhibitor) in 5 parts of ethyl acetate was added to the resultant mixture. To the resulting mixture was added ethyl acetate and adjusted so that the concentration of the acrylic resin (a-3) was 20%, to prepare an ethyl acetate solution of the acrylic resin (a-3). The weight average molecular weight Mw of the resulting acrylic resin (A-3) was 60 ten thousand in terms of polystyrene equivalent by GPC, and Mw/Mn was 6.0. The glass transition temperature based on DSC was-49 ℃. Further, the gram absorption coefficient was measured in the same manner as in example 3, and as a result, there was no absorption at a wavelength of 405nm and a wavelength of 440nm, and both absorbances were 0.

< production of adhesive composition and adhesive layer >

(a) Preparation of adhesive composition

[ example 5 ]: preparation of adhesive composition (1)

To an ethyl acetate solution (resin concentration: 20%) of the obtained resin (A-1) having an indole structure was mixed 0.5 part of a crosslinking agent (CORONATE L, solid content 75%: TOSOH) and 0.5 part of a silane compound (KBM-403, manufactured by shin-Etsu chemical industries, to 100 parts of the solid content of the solution, and 2-butanone was added so that the solid content concentration became 14%, to obtain a pressure-sensitive adhesive composition (1). The amount of the crosslinking agent (CORONATE L) is the mass part based on the active ingredient.

[ example 6 ]: preparation of adhesive composition (2)

To an ethyl acetate solution (resin concentration: 20%) of the obtained resin (A-2) having an indole structure was mixed 0.5 part of a crosslinking agent (CORONATE L, solid content 75%: TOSOH) and 0.5 part of a silane compound (KBM-403, manufactured by shin-Etsu chemical industries, to 100 parts of the solid content of the solution, and 2-butanone was added so that the solid content concentration became 14%, to obtain a pressure-sensitive adhesive composition (2). The amount of the crosslinking agent (CORONATE L) is the mass part based on the active ingredient.

[ comparative example 1 ]: preparation of adhesive composition (3)

To an ethyl acetate solution (resin concentration: 20%) of the acrylic resin (A-3), 0.5 parts of a crosslinking agent (CORONATE L, 75% of solid content: TOSOH) and 0.5 parts of a silane compound (KBM-403, manufactured by shin-Etsu chemical industry Co., Ltd.) and 3 parts of a light absorbing compound (ultraviolet light absorber; BONASORB UA-3911, manufactured by ORIENT chemical industry Co., Ltd.) were mixed with 100 parts of the solid content of the solution, and 2-butanone was added so that the solid content concentration became 14%, to obtain an adhesive composition (3). The amount of the crosslinking agent (CORONATE L) is the mass part based on the active ingredient.

Production example 1: preparation of adhesive composition (4)

(b) Production of adhesive layer

The pressure-sensitive adhesive compositions prepared in (a) were applied to a release-treated surface of a polyethylene terephthalate film (SP-PLR 382050 manufactured by LINTEC, Ltd., hereinafter, simply referred to as a "separator") subjected to release treatment using a coater, and dried at 100 ℃ for 1 minute to prepare pressure-sensitive adhesive layers. The thickness of the resulting adhesive layer was 15 μm.

The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition obtained in example 5 was referred to as pressure-sensitive adhesive layer (1), the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition obtained in example 6 was referred to as pressure-sensitive adhesive layer (2), the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition obtained in comparative example 1 was referred to as pressure-sensitive adhesive layer (3), and the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition obtained in preparation example 1 was referred to as pressure-sensitive adhesive layer (4).

< measurement of Absorbance of adhesive layer >

The obtained pressure-sensitive adhesive layer (1) was bonded to alkali-free glass (trade name "EAGLE XG" manufactured by CORNING corporation), the separator was peeled off, and then a cycloolefin resin film (ZF-14 manufactured by ZEON corporation, japan) was bonded to the pressure-sensitive adhesive layer (1), to prepare a laminate for pressure-sensitive adhesive layer evaluation. The prepared pressure-sensitive adhesive layer evaluation laminate was set in a spectrophotometer UV-2450 (manufactured by shimadzu corporation), and absorbance was measured in a wavelength range of 300 to 800nm by a two-beam method at 1nm step. The absorbance of the alkali-free glass monomer and the cycloolefin resin film monomer at wavelengths of 405nm and 440nm were both 0.

The absorbances of the pressure-sensitive adhesive layer (2) and the pressure-sensitive adhesive layer (3) were also measured in the same manner. The absorbance of the pressure-sensitive adhesive layers (1) to (3) is shown in table 1.

[ Table 1]

< production of optical layered body >

(i) Production of polarizing film

A polyvinyl alcohol Film having an average polymerization degree of about 2400 and a saponification degree of 99.9 mol% and a thickness of 30 μm ("Kuraray Poval Film VF-PE # 3000", manufactured by Kuraray) was immersed in pure water at 37 ℃ and then immersed in an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio): 0.04/1.5/100) at 30 ℃. Thereafter, the resultant was immersed in an aqueous solution containing potassium iodide and boric acid (potassium iodide/boric acid/water (weight ratio) ═ 12/3.6/100) at 56.5 ℃. Then, the film was washed with pure water at 10 ℃ and dried at 85 ℃ to obtain a polarizing film A having a thickness of about 12 μm in which iodine was adsorbed and oriented by polyvinyl alcohol. The stretching was mainly performed in the steps of iodine dyeing and boric acid treatment, and the total stretching magnification was 5.3 times.

(ii) Fabrication of polarizing plates

A transparent protective film ("25 KCHCN-TC", manufactured by letterpress printing Co., Ltd.) obtained by applying a hard coat layer of 7 μm to a triacetyl cellulose film of 25 μm thickness was laminated on one surface of the polarizing film obtained in (i) via an adhesive agent comprising a polyvinyl alcohol resin aqueous solution, and a cycloolefin resin film ("ZF 14-023", manufactured by ZEON Co., Ltd.) having a thickness of 23 μm was laminated on the opposite surface to the transparent protective film, thereby producing an optical film A (polarizing plate, thickness 67 μm).

(iii) Preparation of composition for forming photo-alignment film

A compound having the following structure was synthesized by the method described in Japanese patent application laid-open No. 2013-33248. The following compound 5 parts and cyclopentanone 95 parts were mixed as components, and the resulting mixture was stirred at 80 ℃ for 1 hour to obtain a composition for forming a photoalignment film.

(iv) Preparation of composition containing polymerizable liquid Crystal Compound

A polymerizable liquid crystal compound A having the following structure was synthesized by the method described in Japanese patent application laid-open No. 2010-31223. The maximum absorption wavelength λ max (LC) of the polymerizable liquid crystal compound A was 350 nm.

A composition containing a polymerizable liquid crystal compound was obtained by mixing 12 parts of polymerizable liquid crystal compound A having the following structure, 0.12 part of a polyacrylate compound (leveling agent, BYK-361N manufactured by BYK-Chemie Co., Ltd.), 0.72 part of a polymerization initiator (Irgacure 369 manufactured by Ciba Specialty Chemicals Co., Ltd.) and 100 parts of cyclopentanone.

(v) Production of optically anisotropic layer

The cycloolefin resin film (ZF-14 manufactured by ZEON K.K.) was treated 1 time with a corona treatment device (AGF-B10, manufactured by spring Motor Co., Ltd.) under conditions of an output of 0.3kW and a treatment speed of 3 m/min. (iv) the photo-alignment film-forming composition obtained in (iii) was applied to the corona-treated surface using a bar coater, dried at 80 ℃ for 1 minute, and irradiated at 100mJ/cm using a polarized UV irradiation apparatus (SPOT CURE SP-7; manufactured by USHIO Motor Co., Ltd.)²The cumulative amount of light of (a) is subjected to polarized UV exposure. The thickness of the alignment film was measured by an ellipsometer and found to be 100 nm.

Next, a coating liquid containing the composition A containing the polymerizable liquid crystal compound obtained in (iv) was applied onto an alignment film BY using a bar coater, dried at 120 ℃ for 1 minute, and then irradiated with ultraviolet light (cumulative light amount at wavelength 313nm under nitrogen atmosphere: 500 mJ/cm) from the side coated with the composition containing the polymerizable liquid crystal compound BY using a high pressure mercury lamp (manufactured BY UNICURE VB-15201BY-A, USHIO Motor Co., Ltd.)²) Thereby forming an optical film including the optically anisotropic layer 1. The thickness of the obtained optically anisotropic layer 1 was measured by a laser microscope, and was 2 μm.

[ example 7 ]: production of optical laminate (1)

The pressure-sensitive adhesive layer (1) was bonded to the cycloolefin resin film surface of the polarizing plate produced in the above (ii), and the separator was peeled off. The surface of the pressure-sensitive adhesive layer (1) from which the separator was peeled was bonded to the surface of the optically anisotropic layer produced in (v) opposite to the cycloolefin resin film surface, and the cycloolefin resin film was peeled. The adhesive layer (4) with a separator is bonded to the surface of the optically anisotropic layer from which the cycloolefin resin film was peeled, thereby obtaining an optical laminate (1).

[ example 8 ]: production of optical laminate (2)

An optical laminate (2) was obtained in the same manner as in example 7, except that the pressure-sensitive adhesive layer (1) was replaced with the pressure-sensitive adhesive layer (2).

[ comparative example 2 ]: production of optical laminate (3)

An optical laminate (3) was obtained in the same manner as in example 7, except that the pressure-sensitive adhesive layer (1) was replaced with the pressure-sensitive adhesive layer (3).

[ production example 2 ]: production of optical laminate (4)

An optical laminate (4) was obtained in the same manner as in example 5, except that the pressure-sensitive adhesive layer (1) was replaced with the pressure-sensitive adhesive layer (4).

< evaluation of bleeding resistance of adhesive layer >

The optical laminate (1) thus obtained was cut into a size of 40mm × 40mm, and the separator laminated on the pressure-sensitive adhesive layer (4) was peeled off and bonded to alkali-free glass [ available under the trade name "EAGLE XG" manufactured by CORNING corporation ]. The obtained optical laminate with glass was examined by using a microscope to confirm the precipitation of crystals of the compound in the plane. Thereafter, the obtained optical layered body with glass was put into an oven at a temperature of 23 ℃ and 60% for 500 hours, and the precipitation of the crystals of the compound on the surface was confirmed using a microscope, and the presence or absence of the increase in the precipitation of the crystals of the compound was confirmed. The evaluation results are shown in table 2.

The bleeding resistance of the pressure-sensitive adhesive layer was evaluated in the same manner as described above, except that the optical laminate (1) was replaced with the optical laminate (2). The evaluation results are shown in table 2.

< confirmation of influence of phase difference change of optically anisotropic layer by adhesive layer >

The optical laminate (1) thus obtained was cut into a size of 40mm × 40mm, and the separator laminated on the pressure-sensitive adhesive layer (4) was peeled off and bonded to alkali-free glass [ available under the trade name "EAGLE XG" manufactured by CORNING corporation ]. The retardation value at a wavelength of 450nm of the resulting optical laminate with glass was measured by a birefringence measurement device (KOBRA-WR; manufactured by Oji scientific instruments Co., Ltd.). Thereafter, the optical laminate with glass was put into an oven at a temperature of 80 ℃ for 120 hours, taken out, left to stand at 23 ℃ for 24 hours at 50%, and the phase difference value at a wavelength of 450nm was measured again.

The optical laminate (1) was replaced with the optical laminate (4) in the same manner as described above, and then the measurement was performed.

The retardation value change of the optical laminate (1) at a wavelength of 450nm before and after the durability is obtained by subtracting the retardation value change of the optical laminate (4) at a wavelength of 450nm before and after the durability from the change amount of the retardation value of the optical laminate (1) at a wavelength of 450nm before and after the durability. The phase difference change values are shown in table 2.

The influence of the pressure-sensitive adhesive layer on the change in retardation of the optically anisotropic layer was confirmed in the same manner as described above, except that the optical laminate (1) was replaced with the optical laminate (2). Table 2 shows the values of the change in retardation before and after the durability.

The influence of the pressure-sensitive adhesive layer on the change in retardation of the optically anisotropic layer was confirmed in the same manner as described above, except that the optical laminate (1) was replaced with the optical laminate (3). Table 2 shows the values of the change in retardation before and after the durability.

< measurement of Absorbance of optical film >

The optical laminate (1) thus obtained was cut into a size of 40mm × 40mm, and the separator laminated on the pressure-sensitive adhesive layer (4) was peeled off and bonded to alkali-free glass [ available under the trade name "EAGLE XG" manufactured by CORNING corporation ]. The obtained measurement sample was measured for the transmission spectrum in the transmission axis direction and the absorption axis direction of the optical laminate (1) in the wavelength range of 380 to 780nm using an integrating sphere-equipped spectrophotometer [ product name "V7100" manufactured by JASCO corporation ], and the absorbance at a wavelength of 405nm of the optical laminate (1) was calculated from the transmission spectrum in the transmission axis direction of the optical laminate (1). The absorbance at a wavelength of 350nm, at a wavelength of 405nm, and at a wavelength of 440nm of each of the TAC film monomer, the COP film monomer, and the alkali-free glass monomer is 0.

< evaluation of weather resistance >

The optical laminate (1) was put into a SUNSHINE weather resistance test box (model SUNSHINE WEATHER METER S80, manufactured by Suga test machine Co., Ltd.) at 63 ℃ under 50% humidity for 24 hours, and a weather resistance test was performed for 24 hours. The absorbance of the sample taken out was measured by the same method as the above-mentioned < absorbance measurement of optical film >. From the measured absorbance, the absorbance retention of the sample at a wavelength of 405nm was determined based on the following formula. The results are shown in table 1. The higher the absorbance retention, the less the light selective absorption function is deteriorated, and the better weather resistance is exhibited.

Absorbance retention rate (a (405) after durability test/a (405) before durability test) x 100

[ Table 2]

When a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition containing the resin (a) of the present invention is laminated on an optical film, a change in retardation is suppressed. This is considered to be because, by adding a light selective absorbing compound having a polymerizable group and an indole structure to a resin, the migration of the light selective absorbing compound having an indole structure can be suppressed as compared with an adhesive composition containing a light selective absorbing compound having an indole structure alone.

In addition, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition containing the resin (a) of the present invention shows no increase in precipitation of compounds even after being used in a heat resistance test at 85 ℃ for 120 hours, and has good bleeding resistance. In addition, the value of a (405)/a (440) of the adhesive layer formed from the adhesive composition containing the resin (a) of the present invention is good.

Industrial applicability

The resin of the present invention, the adhesive composition containing the resin, the adhesive layer formed from the adhesive composition, and the optical laminate containing the adhesive layer can be suitably used in a liquid crystal panel and a liquid crystal display device.

Description of the reference numerals

1 pressure-sensitive adhesive layer, 2-release film, 10A, 10B, 10C, 10D optical laminate, 8-protective film, 7-adhesive layer, 7 a-pressure-sensitive adhesive layer, 9-polarizing film, 30-light-emitting element, 40-optical film, 50A 1/4-wavelength retardation layer, 60-adhesive layer or pressure-sensitive adhesive layer, 701/2-wavelength retardation layer, 80-positive C layer, 100-polarizing plate, 110-retardation film.

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