TW202124644A - Pressure-sensitive adhesive composition - Google Patents

Abstract

An object of the present invention is to provide a pressure-sensitive adhesive layer and a pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer having sufficient ultraviolet absorption performance even if the film thickness is thin, less occurrence of bleed-out, and less absorption of visible light near a wavelength of 420 nm.

As a solution, the pressure-senstive adhesive composition of the present invention contains a resin (A), a light selective absorption compound (B) which contains a merocyanine structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more, and a light selective absorption compound (C) which contains a polymerizable group in the molecule and exhibits maximum absorption at a wavelength of less than 360 nm. The pressure-sensitive adhesive composition preferably further contains an initiator.

Description

Adhesive composition

The present invention relates to an adhesive composition, an adhesive layer formed by the adhesive composition, and an optical layered body in which the adhesive layer is laminated.

Display devices such as organic electroluminescence displays (organic EL display devices) or liquid crystal display devices (FPD: flat panel displays) use various components such as display elements such as organic EL elements and liquid crystal cells, or optical films such as polarizers. Among these components, since most of the liquid crystal compounds used in organic EL elements or liquid crystal cells use compounds with relatively weak weather resistance, deterioration caused by ultraviolet rays (UV) is likely to become a problem. In order to solve such a problem, Patent Document 1 describes an ultraviolet absorbing (shielding) adhesive composition containing acrylic resin and triazine ultraviolet absorber, and also describes a composition formed from the adhesive composition Adhesive layer with a thickness of 15μm.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] JP 2008-248131 A

In recent years, organic EL display devices or liquid crystal display devices are required to significantly thinner, and members used in organic EL display devices or liquid crystal display devices are also required to be significantly thinner. Therefore, the ultraviolet-absorbing (shielding) adhesive layer itself is also required to be thin. However, if only the ultraviolet absorbing (shielding) adhesive layer is thinned (for example, less than 12 μm), the ultraviolet absorbing performance of the adhesive layer will be reduced. On the other hand, if you want to maintain the UV absorption performance while making the adhesive layer thinner and increase the amount of UV absorber added, it will cause problems such as bleeding of the UV absorber and coloration due to the absorption of visible light with a wavelength of 420 or more.

The present invention includes the following inventions.

[1] An adhesive composition comprising:

Resin (A);

Light-selective absorption compound (B), which contains a merocyanine structure in the molecule and exhibits maximum absorption at a wavelength of 360nm or more; and

The light selective absorption compound (C) contains a polymerizable group in the molecule, and exhibits a maximum absorption at a wavelength of 300 nm or more and a wavelength of less than 360 nm.

[2] The adhesive composition as described in [1], further comprising an initiator (D).

[3] The adhesive composition according to [2], wherein the initiator (D) is a radical generator.

[4] The adhesive composition according to [2] or [3], wherein the initiator (D) is a photo-radical generator.

[5] The adhesive composition according to any one of [2] to [4], wherein the initiator (D) is an oxime ester-based photoradical generator.

[6] The adhesive composition according to any one of [1] to [5], further comprising a radical curable component (E).

[7] The adhesive composition according to [6], wherein the radical curable component (E) is a (meth)acrylate-based compound.

[8] The adhesive composition according to [6] or [7], wherein the radical curable component (E) is a polyfunctional (meth)acrylate compound.

[9] The adhesive composition according to any one of [1] to [8], which further contains a crosslinking agent (F).

[10] The adhesive composition according to [9], wherein the crosslinking agent (F) is an isocyanate-based crosslinking agent.

[11] The adhesive composition according to any one of [1] to [10], wherein the glass transition temperature of the resin (A) is 40°C or less.

[12] The adhesive composition according to [11], wherein the resin (A) is a (meth)acrylic resin having a glass transition temperature of 40°C or less.

[13] The adhesive composition according to any one of [1] to [12], wherein a light selective absorption compound (B) that contains a partial anthocyanin structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more The system satisfies the following formula (1);

ε (380)≧25 (1)

[In formula (1), ε (380) represents the light selective absorption compound (B) which contains a partial anthocyanin structure in the molecule and exhibits maximum absorption at a wavelength of 360nm or more at a wavelength of 380nm; Gram absorption coefficient; The unit is L/(g‧cm)].

[14] The adhesive composition according to any one of [1] to [13], wherein a light selective absorption compound (B) that contains a partial anthocyanin structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more The system satisfies the following formula (2);

ε (380)/ ε (420)≧20 (2)

[In formula (2), ε (380) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 380 nm, which contains a partial anthocyanin structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more;

ε (420) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 420 nm, which contains a partial anthocyanidin structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more].

[15] The adhesive composition according to any one of [1] to [14], wherein a light selective absorption compound (B) that contains a partial anthocyanidin structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more Is a compound represented by formula (Y);

[In formula (Y),

R ^Y3 , R ^Y4 and R ^Y5 each independently represent an electron pulling base;

R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 each independently represent a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a carboxyl group, -SCF ₃ , _{-SF 5} , _{-SF 3} , -SO ₃ H, -SO ₂ H, an aliphatic hydrocarbon group with 1 to 25 carbons that may have a substituent or an aromatic hydrocarbon group with 6 to 18 carbons that may have a substituent, the aliphatic hydrocarbon group or aromatic hydrocarbon group is Contained -CH ₂ -or -CH=can be -NR ^1A -, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -CONR ^2A -, -NR ^{3A -CO-,} -S-, -SO-, -SO ₂ -, -CF ₂ -or -CHF- substitution;

R ^1A , R ^2A and R ^3A each independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms;

R ^Y1 and R ^Y2 can be bonded to each other to form a ring;

R ^Y1 and R ^Y6 can be bonded to each other to form a ring;

R ^Y4 and R ^Y5 may be bonded to each other to form a ring].

[16] The adhesive composition according to any one of [1] to [14], wherein a light selective absorption compound (B) that contains a partial anthocyanidin structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more A compound with a molecular weight of 3000 or less and a partial structure represented by formula (X);

[In formula (X), ring W ¹ represents a ring structure that has at least one double bond as a constituent element of the ring and does not have aromaticity;

R ³ represents a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a carboxyl group, -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, and the number of carbons that may have a substituent An aliphatic hydrocarbon group of 1 to 25 or an aromatic hydrocarbon group of 6 to 18 carbons that may have substituents, the aliphatic hydrocarbon group or aromatic hydrocarbon group containing -CH ₂ -or -CH= may be -O-, -S -, -NR ^1xA -, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CONR ^2xA -, -NR ^3xA -CO-, -O-CO-NR ^4xA -, -NR ^5xA -CO-O-, -NR ^6xA -CO-NR ^7xA -, -CO-S-, -S-CO-S-, -S-CO-NR ^8xA -, -NR ^9xA -CO- S-, -CS-, -O-CS-, ^{-CS-O-, -NR 10xA -CS-} , -NR ^{11xA -CS} -S-, -S-CS-, -CS-S-, -S- CS-S-, -SO- or -SO ₂ -replaced;

R ^1xA , R ^2xA , R ^3xA , R ^4xA , R ^5xA , R ^6xA , R ^7xA , R ^8xA , R ^x9A , R ^10xA and R ^11xA each independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms].

[17] The adhesive composition according to [16], wherein the compound having a molecular weight of 3000 or less and having a partial structure represented by formula (X) is a compound represented by formula (I) to formula (VIII) Any of the compounds;

[In formula (I) to formula (VIII),

Rings W ¹ and R ^{3 have the} same meaning as described above,

The ring W ² , the ring W ³ , the ring W ⁴ , the ring W ⁵ , the ring W ⁶ , the ring W ⁷ , the ring W ⁸ , the ring W ⁹ , the ring W ¹⁰ , the ring W ¹¹ and the ring W ¹² each independently represent at least 1 A ring structure with a double bond as a constituent element of the ring,

Ring W ¹¹¹ represents a ring having at least two nitrogen atoms as constituent elements,

Ring W ¹¹² and ring W ¹¹³ each independently represent a ring having at least one nitrogen atom as a constituent element,

R ¹ , R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁹¹ , R ¹⁰¹ , R ¹¹¹ , R ² , R ¹² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² , R ¹⁰² and R ¹¹² Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a carboxyl group, -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, and may have a substituent The aliphatic hydrocarbon group with 1 to 25 carbons or the aromatic hydrocarbon group with 6 to 18 carbons which may have substituents, the aliphatic hydrocarbon group or the aromatic hydrocarbon group contains -CH ₂ -or -CH = can be -NR ^12A -, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -CONR ^13A -, -NR ^14A -CO-, -S-, -SO-, -CF ₂ -or -CHF -replace,

R ¹³ , R ²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁶³ , R ⁷³ , R ⁸³ , R ⁹³ , R ¹⁰³ and R ¹¹³ each independently represent a heterocyclic group, a halogen atom, a nitro group, a cyano group, and a hydroxyl group , Thiol group, carboxyl group, -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, aliphatic hydrocarbon group with 1 to 25 carbons that may have substituents or 6 to 18 carbons that may have substituents The aromatic hydrocarbon group, the aliphatic hydrocarbon group or the aromatic hydrocarbon group contains -CH ₂ -or -CH= can be -O-, -S-, -NR ^1A -, -CO-, -CO-O-,- O-CO-, -O-CO-O-, -CONR ^2A -, -NR ^3A -CO-, -O-CO-NR ^4A -, -NR ^5A -CO-O-, -NR ^6A -CO-NR ^7A -, -CO-S-, -S- CO-S-, -S-CO-NR ^8A -, -NR ^9A -CO-S-, -CS-, -O-CS-, -CS-O- , -NR ^10A -CS-, -NR ^11A -CS-S-, -S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO ₂ -replaced,

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A , R ^8A , R ^9A , R ^10A , R ^11A , R ^12A , R ^13A and R ^14A each independently represent a hydrogen atom or carbon number 1 to 6 alkyl group,

R ⁴ , R ¹⁴ , R ²⁴ , R ³⁴ , R ⁴⁴ , R ⁵⁴ , R ⁶⁴ , R ⁷⁴ , R ⁸⁴ , R ⁹⁴ , R ¹⁰⁴ , R ¹¹⁴ , R ⁵ , R ¹⁵ , R ²⁵ , R ³⁵ , R ⁷⁵ And R ⁸⁵ each independently represent an electron pull base,

R ¹ and R ² can be bonded to each other to form a ring,

R ⁴¹ and R ⁴² can be bonded to each other to form a ring,

R ⁵¹ and R ⁵² can be bonded to each other to form a ring,

R ⁶¹ and R ⁶² can be bonded to each other to form a ring,

R ⁹¹ and R ⁹² can be bonded to each other to form a ring,

R ¹⁰¹ and R ¹⁰² can be bonded to each other to form a ring,

R ¹¹¹ and R ¹¹² can be bonded to each other to form a ring,

R ² and R ³ can be bonded to each other to form a ring,

R ¹² and R ¹³ can be bonded to each other to form a ring,

R ⁴² and R ⁴³ can be bonded to each other to form a ring,

R ⁵² and R ⁵³ can be bonded to each other to form a ring,

R ⁶² and R ⁶³ can be bonded to each other to form a ring,

R ⁷² and R ⁷³ can be bonded to each other to form a ring,

R ⁸² and R ⁸³ can be bonded to each other to form a ring,

R ⁹² and R ⁹³ can be bonded to each other to form a ring,

R ¹⁰² and R ¹⁰³ can be bonded to each other to form a ring,

R ¹¹² and R ¹¹³ can be bonded to each other to form a ring,

R ⁴ and R ⁵ can be bonded to each other to form a ring,

R ¹⁴ and R ¹⁵ can be bonded to each other to form a ring,

R ²⁴ and R ²⁵ can be bonded to each other to form a ring,

R ³⁴ and R ³⁵ can be bonded to each other to form a ring,

R ⁷⁴ and R ⁷⁵ can be bonded to each other to form a ring,

R ⁸⁴ and R ⁸⁵ can be bonded to each other to form a ring,

R ⁶ and R ⁸ each independently represent a divalent bonding group,

R ⁷ series represents a single bond or a divalent bond group,

R ⁹ and R ¹⁰ each independently represent a trivalent bonding group,

R ¹¹ represents a tetravalent bonding group].

[18] An adhesive layer formed of the adhesive composition described in any one of [1] to [17].

[19] The adhesive layer described in [18] satisfies the following formula (3);

A(380)≧0.60 (3)

[In formula (3), A(380) represents the absorbance at a wavelength of 380nm].

[20] The adhesive layer described in [18] or [19] further satisfies the following formula (4);

A(380)/A(420)≧5 (4)

[In formula (4), A(380) represents the absorbance at a wavelength of 380nm, and A(420) represents the absorbance at a wavelength of 420nm].

[21] The adhesive layer according to any one of [18] to [20], wherein the thickness of the adhesive layer is 10 μm or less.

[22] An adhesive layer-attached optical film, wherein at least one area of the adhesive layer described in any one of [18] to [21] has an optical film.

[23] The optical film with an adhesive layer as described in [22], wherein the optical film is a polarizing plate.

[24] An image display device comprising the optical film with an adhesive layer as described in [22] or [23].

The present invention provides an adhesive layer and an adhesive composition for forming the adhesive layer, and the adhesive layer has sufficient ultraviolet absorption performance even if the film thickness becomes thinner, and the occurrence of exudation is small, near the wavelength of 420nm The visible light absorption is low.

1: Adhesive layer (adhesive layer) formed by the adhesive composition of the present invention

1a: Adhesive layer

2: Peel off the film

3,6: Protective film

4,7: Adhesive layer

5: Polarizing film

8: retardation film

10: Laminated body

10A, 10B: Optical film with adhesive layer

10C, 10D: Optical laminate

30: Light-emitting element

40: Optical film

50: 1/2 wavelength retardation layer

50a, 70: 1/4 wavelength retardation layer

60: Adhesive layer or adhesive layer

80: Positive C layer

100: Polarizing plate

110: retardation film

Fig. 1 shows an example of the layer structure of a laminate in which a release film is provided on the adhesive layer of the present invention.

FIG. 2 shows an example of the layer structure of the optical film with an adhesive layer of the present invention.

FIG. 3 shows an example of the layer structure of the optical film with an adhesive layer 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.

<Adhesive composition>

The adhesive composition of the present invention includes the following (Z-1) to (Z-3).

(Z-1): Resin (A)

(Z-2): Light selective absorption compound (B) (hereinafter, sometimes referred to as light selective absorption compound (B)), which contains a partial anthocyanin structure in the molecule and shows maximum absorption at a wavelength of 360nm or more

(Z-3): Light selective absorption compound (C) (hereinafter, sometimes referred to as light selective absorption compound (C)), which has a polymerizable group in the molecule and displays at a wavelength of 300 nm or more and a wavelength of less than 360 nm Great absorption

<Resin (A)>

The resin (A) of the present invention is not particularly limited as long as it is a resin used in the adhesive composition.

The resin (A) is preferably a resin having a glass transition temperature (Tg) of 40°C or less. The glass transition temperature (Tg) of the resin (A) is more preferably 20°C or less, still more preferably 10°C or less, and particularly preferably 0°C or less. In addition, the glass transition temperature of the resin (A) is usually -80°C or higher, preferably -70°C or higher, more preferably -60°C or higher, even more preferably -55°C or higher, and -50°C or higher It is especially good. If the glass transition temperature of the resin (A) is below 40°C, it is beneficial to improve the adhesion of the adhesive layer formed by the adhesive composition containing the resin (A) to the adherend. In addition, if the glass transition temperature of the resin (A) is above -80°C, it is beneficial to improve the durability of the adhesive layer formed by the adhesive composition containing the resin (A). In addition, the glass transition temperature can be measured by a differential scanning calorimeter (DSC).

In addition, the resin (A) preferably does not show maximum absorption between the wavelengths of 300 nm and 780 nm.

Examples of the resin (A) system include (meth)acrylic resins, silicone resins, rubber resins, urethane resins, and the like, and (meth)acrylic resins are preferred.

The (meth)acrylic resin is preferably a polymer having a structural unit derived from (meth)acrylate as a main component (preferably containing 50% by mass or more). The structural unit derived from (meth)acrylate may contain more than one structure derived from monomers other than (meth)acrylate Unit (for example, a structural unit derived from a monomer having a polar functional group). In addition, in this specification, the term "(meth)acrylic acid" means that it may be either acrylic acid or methacrylic acid, and "(meth)" in the case of (meth)acrylate etc. also has the same meaning.

The (meth)acrylate type includes (meth)acrylate represented by the following formula (a).

[In formula (a), R _1A represents a hydrogen atom or a methyl group, and R _2A represents an alkyl group with 1 to 14 carbons or an aromatic hydrocarbon group with 6 to 20 carbons. The hydrogen atom may be substituted by an alkoxy group having 1 to 10 carbon atoms. ]

In the formula (a), R _{2A is} preferably an alkyl group having 1 to 14 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

The (meth)acrylates represented by formula (a) include:

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, (meth) Base) linear alkyl esters of (meth)acrylic acid such as lauryl acrylate and stearyl (meth)acrylate;

Isopropyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, isohexyl (meth)acrylate, (meth)acrylic acid (Meth) acrylic acid such as 2-ethylhexyl ester, isooctyl (meth)acrylate, isononyl (meth)acrylate, isostearyl (meth)acrylate, isoamyl (meth)acrylate, etc. Branched alkyl ester

Cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, cyclododecyl (meth)acrylate, (meth)acrylate Base) methylcyclohexyl acrylate, trimethylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, α-ethoxycyclohexyl acrylate, etc. (meth)acrylic acid Alkyl esters containing alicyclic skeletons;

(Meth)acrylic acid esters containing aromatic ring skeletons, such as phenyl (meth)acrylate and benzyl (meth)acrylate; etc.

In addition, substituent-containing (meth)acrylates include 2-methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, (Meth) 2-(2-phenoxyethoxy)ethyl acrylate and the like.

The (meth)acrylate type may also include phenoxy diethylene glycol (meth)acrylate, phenoxy poly(ethylene glycol) (meth)acrylate, and the like.

In addition to these (meth)acrylates can be used singly, a plurality of different types can be used.

The resin (A) of the present invention is among the alkyl (meth)acrylates, and preferably contains homopolymers derived from alkyl (meth)acrylates (a1) whose glass transition temperature Tg is less than 0°C The structural unit and the homopolymer have a structural unit derived from alkyl (meth)acrylate (a2) whose Tg is 0°C or higher. This is beneficial to improve the high temperature resistance of the adhesive layer. For the Tg system of the homopolymer of alkyl (meth)acrylate, for example, literature values such as POLYMER HANDBOOK (Wiley-Interscience) can be used.

Specific examples of alkyl (meth)acrylate (a1) include ethyl acrylate, n- and isopropyl acrylate, n- and isobutyl acrylate, n-pentyl acrylate, n- and isohexyl acrylate, n-heptyl acrylate, acrylic acid N- and isooctyl acrylate, 2-ethylhexyl acrylate, n- and isononyl acrylate, propylene Alkyl (meth)acrylates with an alkyl group of about 2 to 12 carbon atoms, such as n- and isodecyl acid and n-dodecyl acrylate.

The alkyl (meth)acrylate (a1) system may use only 1 type, and may use 2 or more types together. Among them, from the viewpoint of followability or heavy workability when laminated on an optical film, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, etc. are preferred.

The alkyl (meth)acrylate (a2) is an alkyl (meth)acrylate other than the alkyl (meth)acrylate (a1). Specific examples of the alkyl (meth)acrylate (a2) include methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, stearyl acrylate, t-butyl acrylate, and the like.

Alkyl (meth)acrylate (a2) system may use only 1 type, and may use 2 or more types together. Among them, from the viewpoint of high temperature resistance, the alkyl (meth)acrylate (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, etc., and more preferably contains methyl acrylate. .

The structural unit derived from (meth)acrylate represented by the formula (a) is in the total structural unit contained in the (meth)acrylic resin, preferably 50% by mass or more, and 60 to 95% by mass More preferably, it is more preferably 65 to 95% by mass or more.

The structural unit derived from a monomer other than (meth)acrylate is preferably a structural unit derived from a monomer having a polar functional group, more preferably a structural unit derived from a (meth)acrylate having a polar functional group . Examples of the polar functional group system include heterocyclic groups such as a hydroxyl group, a carboxyl group, a substituted or unsubstituted amino group, and an epoxy group.

Monosystems with polar functional groups include 1-hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate Hydroxybutyl, 1-hydroxypentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate Base) 2-hydroxypentyl acrylate, 2-hydroxy (meth)acrylate Hexyl ester, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 3-hydroxypentyl (meth)acrylate, 3-hydroxyhexyl (meth)acrylate, (methyl) ) 3-hydroxyheptyl acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, 4-hydroxyhexyl (meth)acrylate, 4-hydroxyheptyl (meth)acrylate Ester, 4-hydroxyoctyl (meth)acrylate, 2-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-(meth)acrylate Hydroxy-3-phenoxypropyl ester, 5-hydroxypentyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, 5-hydroxyheptyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate Hydroxyoctyl ester, 5-hydroxynonyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 6-hydroxyheptyl (meth)acrylate, 6-hydroxyoctyl (meth)acrylate, (meth)acrylate Base) 6-hydroxynonyl acrylate, 6-hydroxydecyl (meth)acrylate, 7-hydroxyheptyl (meth)acrylate, 7-hydroxyoctyl (meth)acrylate, 7-hydroxy(meth)acrylate Nonyl ester, 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, (methyl) ) 9-hydroxydecyl acrylate, 9-hydroxyundecyl (meth)acrylate, 9-hydroxydodecyl (meth)acrylate, 9-hydroxytridecyl (meth)acrylate, (meth) ) 10-hydroxydecyl acrylate, 10-hydroxyundecyl (meth)acrylate, 10-hydroxydodecyl (meth)acrylate, 10-hydroxytridecyl acrylate, 10-hydroxyundecyl (meth)acrylate Hydroxytetradecyl ester, 11-hydroxyundecyl (meth)acrylate, 11-hydroxydodecyl (meth)acrylate, 11-hydroxytridecyl (meth)acrylate, (meth)acrylic acid 11-hydroxytetradecyl ester, 11-hydroxypentadecyl (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, 12-hydroxytridecyl (meth)acrylate, (methyl) ) 12-hydroxytetradecyl acrylate, 13-hydroxypentadecyl (meth)acrylate, 13-hydroxytetradecyl (meth)acrylate, 13-hydroxypentadecyl (meth)acrylate, ( (Meth) acrylate 14-hydroxytetradecyl ester, (meth)acrylate 14-hydroxy pentadecyl Alkyl ester, 15-hydroxypentadecyl (meth)acrylate, 15-hydroxyheptadecanyl (meth)acrylate and other monomers having hydroxyl groups;

(Meth) acrylic acid, carboxyalkyl (meth)acrylate (e.g. carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate), maleic acid, maleic anhydride, fumaric acid, crotonic acid, etc. Monomers with carboxyl groups;

Acrylic morpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, methyl tetrahydrofuran (meth)acrylate, caprolactone modified methyl tetrahydrofuran acrylate, (methyl) ) Monomers with heterocyclic groups such as 3,4-epoxycyclohexyl methyl acrylate, glycidyl (meth)acrylate, 2,5-dihydrofuran;

Monomers with substituted or unsubstituted amino groups such as (meth)aminoethyl acrylate, N,N-dimethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate .

Among them, in terms of the reactivity between the (meth)acrylate polymer and the crosslinking agent, monomers having hydroxyl groups and monomers having carboxyl groups are preferred, and monomers having hydroxyl groups and monomers having carboxyl groups are preferred. Either monomer is more preferable.

The monomer having a hydroxyl group is preferably 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate. In particular, by using 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 5-hydroxypentyl acrylate, good durability can be obtained.

The single system with carboxyl group preferably uses acrylic acid.

From the viewpoint of preventing excessive peeling force of the separation film that can be laminated on the outer surface of the adhesive layer, the (meth)acrylic resin preferably does not substantially contain a structural unit derived from a monomer having an amine group. Here, the term "substantially not contained" means that it is 0.1 parts by mass or less in 100 parts by mass of all structural units constituting the (meth)acrylic resin.

The content of the structural unit derived from the monomer having a polar functional group is relative to 100 parts by mass of all the structural units of the (meth)acrylic resin, preferably 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass Parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, particularly preferably 1 parts by mass or more and 7 parts by mass or less.

The structural unit system derived from monomers other than (meth)acrylate can also be exemplified by the structural unit derived from a monomer having an aromatic group. The single system having an aromatic group includes (meth)acrylates having one (meth)acrylic acid group and one or more aromatic rings (such as benzene ring, naphthalene ring, etc.) in the molecule, for example, Examples include (meth)acrylates having a phenyl group, a phenoxyethyl group, or a benzyl group. The content of the structural unit derived from the monomer having an aromatic group is relative to 100 parts by mass of all the structural units of the (meth)acrylic resin, preferably 20 parts by mass or less, more preferably 4 parts by mass or more and 20 parts by mass Parts or less, more preferably 4 parts by mass or more and 16 parts by mass or less.

The structural unit system derived from monomers other than (meth)acrylate can also include structural units derived from styrene-based monomers, structural units derived from vinyl-based monomers, and derived from within the molecule Structural units of monomers having multiple (meth)acrylic groups, structural units derived from (meth)acrylic amine-based monomers, etc.

Styrene single systems can include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene Alkyl styrenes such as, butyl styrene, hexyl styrene, heptyl styrene, and octyl styrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene ; Nitrostyrene; Acetylstyrene; Methoxystyrene; and Divinylbenzene.

Vinyl single systems include: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate and other fatty acid vinyl esters; vinyl chloride, vinyl bromide, etc. Vinyl halides; vinylidene halides such as vinylidene chloride; nitrogen-containing heteroaromatic vinyls such as vinylpyridine, vinylpyrrolidone, and vinylcarbazole; butadiene, isoprene, chloroprene, etc. Conjugated dienes; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.

The single system having plural (meth)acrylic acid groups in the molecule includes: 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Monomers such as tripropylene glycol di(meth)acrylate have 2 (meth)acrylic acid groups in the molecule; trihydroxymethyl propane tri(meth)acrylate, etc. have 3 (meth) acrylates in the molecule Acrylic monomer.

The (meth)acrylamide system single system includes N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(3-hydroxypropyl) Yl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, N-(5-hydroxypentyl)(meth)acrylamide, N-(6-hydroxyl Hexyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)propylene Amide, N-(3-dimethylaminopropyl)(meth)acrylamide, N-(1,1-dimethyl-3-oxobutyl)(meth)acrylamide , N-[2-(2-Pendant oxy-1-imidazolidinyl) ethyl] (meth) allylamide, 2-propenylamino-2-methyl-1-propane sulfonic 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-(2-ethoxyethyl)(meth)acrylamide, N-(2-propoxyethyl)( Meth)acrylamide, N-[2-(1-methylethoxy)ethyl](meth)acrylamide, N-[2-(1-methylpropoxy)ethyl]( (Meth)acrylic acid Amine, N-[2-(2-methylpropoxy)ethyl](meth)acrylamide, N-(2-butoxyethyl)(meth)acrylamide, N-[2 -(1,1-Dimethylethoxy)ethyl](meth)acrylamide and the like. Among them, preferred are N-(methoxymethyl)acrylamide, N-(ethoxymeth)acrylamide, N-(propoxymeth)acrylamide, N-(butoxy Meth)acrylamide and N-(2-methylpropoxymeth)acrylamide.

The weight average molecular weight (Mw) of the (meth)acrylic resin is preferably 500,000 to 2.5 million. If the weight average molecular weight is more than 500,000, the durability of the adhesive layer in a high-temperature environment will be improved, and it is easy to inhibit the floating and peeling between the adherend and the adhesive layer, or the adhesion failure of the adhesive layer, etc. situation. If the weight average molecular weight is 2.5 million or less, it is advantageous from the viewpoint of coatability. From the viewpoint of taking into account both the durability of the adhesive layer and the coatability of the adhesive composition, the weight average molecular weight is preferably 600,000 to 1.8 million, more preferably 700,000 to 1.7 million, and particularly preferably 1 million to 160 Ten thousand. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 2-10, preferably 3-8, and more preferably 3-6. The weight average molecular weight can be analyzed by gel permeation chromatography and is a value converted from standard polystyrene.

When the (meth)acrylic resin is dissolved in ethyl acetate and set as a solution with a concentration of 20% by mass, the viscosity at 25°C is preferably 20 Pa‧s or less, and more preferably 0.1 to 15 Pa‧s. If the viscosity is in this range, it is advantageous from the viewpoint of coating properties when the adhesive composition is applied to the substrate. In addition, the viscosity can be measured with a Brookfield viscometer.

The (meth)acrylic resin system can be produced by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method, and the solution polymerization method is particularly preferred. The solution polymerization method includes, for example, mixing monomers and organic solvents, adding a thermal polymerization initiator in a nitrogen environment, and stirring at a temperature of 40 to 90°C (preferably 50 to 80°C) for about 3 to 15 hours Of method. In order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization. The monomer or thermal polymerization initiator may be added to an organic solvent. The aforementioned organic solvents include: aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone, etc. As the thermal polymerization initiator, a known thermal polymerization initiator can be used. In addition, a photopolymerization initiator may be used instead of the thermal polymerization initiator, and a polymerization method using ultraviolet rays or the like may be used.

The content of the resin (A) is in 100% by mass of the solid content of the adhesive composition, usually 50% to 99.9% by mass, preferably 60% to 95% by mass, more preferably 70% to 90% by mass %.

<Light selective absorption compound (B)>

The light selective absorption compound (B) is a compound having a partial anthocyanin structure in the molecule.

The so-called merocyanidin structure in the present invention means the partial structure shown by N-C=C-C=C. However, the merocyanidin structure in the present invention does not contain an indole ring. In addition, the merocyanidin structure in the present invention preferably does not contain an aromatic condensed ring (e.g., benzo Triazole ring, benzimidazole ring, isoindole ring, quinoline ring, etc.).

The light selective absorption compound (B) exhibits maximum absorption at a wavelength of 360 nm or more. The light selective absorption compound (B) preferably exhibits a maximum absorption at a wavelength of 360 nm or more and a wavelength of 420 nm or less, and more preferably exhibits a maximum absorption at a wavelength of 370 nm or more and a wavelength of 410 nm or less. By showing great absorption at a wavelength of 360nm or more, even if a small amount of the light selective absorption compound (B) is added, light with a wavelength around 380nm can be efficiently absorbed.

The light selective absorption compound (B) preferably satisfies the following formula (1), and more preferably satisfies the formula (2).

ε (380)≧25 (1)

[In formula (1), ε (380) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 380 nm. The unit of Gram absorbance coefficient is L/(g‧cm). ]

ε (380)/ ε (420)≧20 (2)

[In formula (2), ε (380) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 380 nm; ε (420) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 420 nm. The unit of Gram absorbance coefficient is L/(g‧cm). ]

Preferably the value of ε(380) is more than 30L/(g‧cm), more preferably is more than 35L/(g‧cm), more preferably is more than 50L/(g‧cm), and even more preferably is 100L /(g‧cm) or more, usually 10000L/(g‧cm) or less. The larger the value of ε (380), the easier it is to absorb light with a wavelength of 380nm, and it is easy to exhibit the function of inhibiting deterioration due to ultraviolet rays.

The light selective absorption compound (B) preferably has a value of ε (380)/ ε (420) of 25 or more, more preferably 35 or more, more preferably 50 or more, and particularly preferably 100 or more. The adhesive layer formed by the adhesive composition containing a compound with a large value of ε (380)/ ε (420) does not hinder the color performance of the display device, and absorbs ultraviolet rays near 380 nm. In addition, it is possible to suppress light degradation of display devices such as laminated optical films (retardation films) or organic EL elements.

The light selective absorption compound (B) includes, for example, compounds having a merocyanidin structure described in International Publication No. 2019/073869 and International Publication No. 2019/004046.

In addition, the light selective absorption compound (B) preferably has a structure in which a carbon atom contained in the merocyanidin structure is bonded to an electron withdrawing group. Specifically, the light selective absorption compound (B) preferably has a ^{partial structure represented by NC=C(R Y3} )-C=C (here, R ^Y3 represents an electron withdrawing group).

Examples of the light selective absorption compound (B) having a partial structure represented by NC=C(R ^{Y3 )-C=C include compounds represented by the following formula (Y).}

[In formula (Y), R ^Y3 , R ^Y4 and R ^Y5 each independently represent an electron withdrawing group.

R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 each independently represent a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a carboxyl group, -SCF ₃ , _{-SF 5} , _{-SF 3} , -SO ₃ H, -SO ₂ H, an aliphatic hydrocarbon group with 1 to 25 carbons that may have a substituent or an aromatic hydrocarbon group with 6 to 18 carbons that may have a substituent, the aliphatic hydrocarbon group or aromatic hydrocarbon group is Contained -CH ₂ -or -CH= can be -NR ^1A -, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -CONR ^2A -, -NR ^{3A -CO-} , -S-, -SO-, -SO ₂ -, -CF ₂ -or -CHF- substitution.

R ^1A , R ^2A and R ^3A each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ^Y1 and R ^Y2 can be bonded to each other to form a ring.

R ^Y1 and R ^Y6 can be bonded to each other to form a ring.

R ^Y4 and R ^Y5 can be bonded to each other to form a ring. ]

The electron withdrawing groups represented by R ^Y3 , R ^Y4 and R ^Y5 include halogen atom, nitro group, cyano group, carboxyl group, halogenated alkyl group, halogenated aryl group, -OCF ₃ , -SCF ₃ , _{-SF 5} , -SF _3. -SO ₃ H, -SO ₂ H, the group represented by formula (Y-1).

*-X ¹ -R ²²² (Y-1)

[In formula (Y-1),

X ¹ represents -CO-, -COO-, -OCO-, -CS-, -CSS-, -COS-, -CSO-, -SO ₂ -, -NR ²²³ CO- or -CONR ²²⁴ -.

R ²²² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 25 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms.

R ²²³ and R ²²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

＊Denotes the bonding key. ]

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

The halogenated alkyl system includes, for example, trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosecond butyl, perfluorotertiary butyl, perfluoropentyl Perfluoroalkyl groups such as fluoroalkyl group and perfluorohexyl group are preferred. The carbon number of the halogenated alkyl group is usually 1-25, and the carbon number is preferably 1-12. The halogenated alkyl system may be linear or branched.

Examples of the halogenated aryl group include fluorophenyl, chlorophenyl, bromophenyl, etc., fluoroaryl is preferred, and perfluoroaryl is more preferred. The carbon number of the halogenated aryl group is usually 6 to 18, preferably 6 to 12.

X ¹ is preferably -COO- or -SO ₂ -.

The alkyl group with 1 to 25 carbon atoms represented by R ²²² includes methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, sec-butyl, n-pentyl, and n-hexyl. , 1-methylbutyl, 3-methylbutyl, n-octyl, n-decyl, 2-hexyl-octyl and other linear or branched alkyl groups with 1 to 25 carbon atoms. R ²²² is preferably an alkyl group having 1 to 12 carbon atoms.

Examples of the substituent system that the alkyl group having 1 to 25 carbons represented by R ^{222 may have include a halogen atom and a hydroxyl group.}

The aromatic hydrocarbon groups with 6 to 18 carbons represented by R ²²² include aryl groups with 6 to 18 carbons such as phenyl, naphthyl, anthryl, biphenyl, etc.; benzyl, phenylethyl, naphthalene Alkyl groups having 7 to 18 carbon atoms, such as methyl group, etc.

Examples of the substituent system that the aromatic hydrocarbon group having 6 to 18 carbons represented by R ^{222 may have include a halogen atom and a hydroxyl group.}

R ²²³ and R ^{224 have} a carbon number of 1 to 6 alkyl groups including methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, sec-butyl, and n-pentyl. , N-hexyl, 1-methylbutyl, 3-methylbutyl, etc.

R ^Y3 are diagrams nitro, _{cyano, -F, -OCF 3, -SCF 3} , -SF 5, -SF 3, -SO 2 -R 222 (R 222 represents a hydrogen atom based, may have a substituent group of carbon number 1 to 25 alkyl groups or optionally substituted aromatic hydrocarbon groups with carbon numbers 6 to 18), fluoroalkyl groups (preferably fluoroalkyl groups with carbon numbers 1 to 25) or fluoroaryl groups (preferably carbon numbers 6 to 18 fluoroaryl) is preferred, cyano, -F, -OCF ₃ , -SCF ₃ or fluoroalkyl (preferably a fluoroalkyl with 1 to 25 carbons) is more preferred, and cyano The base is even better.

At least one selected from R ^Y4 and R ^Y5 is preferably cyano, nitro, -OCF ₃ , -SCF ₃ , _{-SF 5} , -CO-OR ²²² , -SO ₂ -R ²²² (R ²²² represents hydrogen Atom, optionally substituted alkyl with 1 to 25 carbons or optionally substituted aromatic hydrocarbon with 6 to 18), fluoroalkyl (preferably fluoroalkyl with 1 to 25 carbons) or Fluoroaryl (preferably a fluoroaryl having 6 to 18 carbons). More preferably, it is cyano, nitro, -CO-OR ²²² or -SO ₂ -R ²²² , and still more preferably is cyano.

R ^Y4 and R ^Y5 preferably have the same structure.

R ^Y4 and R ^Y5 can be bonded to each other to form a ring. The ring system formed by R ^Y4 and R ^Y5 bonding to each other may be a single ring or a condensed ring, but a single ring is preferred. In addition, ^{the ring system formed by R Y4} and R ^Y5 bonded to each other may contain heteroatoms (nitrogen atom, oxygen atom, sulfur atom) and the like as the constituent elements of the ring.

The ring formed by bonding R ^Y4 and R ^{Y5 to} each other is usually a 3- to 10-membered ring, preferably a 5- to 7-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

Examples of the ring system formed by bonding R ^Y4 and R ^{Y5 to each other include the structures described below.}

[In the formula, * represents a bond with a carbon atom. R ^1E to R ^16E each independently represent a hydrogen atom or a substituent. ]

The ring system formed by R ^Y4 and R ^Y5 bonded to each other may have a substituent (R ^1E to R ^16E in the above formula).

Examples of the substituent systems represented by R ^1E to R ^16E include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl , Octyl, nonyl and other C1-C12 alkyl groups; fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2 -Trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 1,1,2,2,2-pentafluoroethyl and other C1-C12 halogenated alkyl groups; methoxy, ethoxy , Propoxy, butoxy, pentyloxy, hexyloxy and other alkoxy groups with carbon numbers from 1 to 12; methylthio, ethylthio, propylthio, butylthio, pentyl Alkylthio groups with 1 to 12 carbon atoms such as thio and hexylthio; monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 1,1,2,2 , 2-Pentafluoroethoxy and other fluoroalkoxy groups with carbon numbers from 1 to 12; amino, methylamino, ethylamino, dimethylamino, diethylamino, methyl ethyl Amino groups substituted by alkyl groups having 1 to 6 carbon atoms; methylcarbonyloxy and ethylcarbonyloxy groups having 2 to 12 carbon atoms; methylsulfonyl and ethylsulfonyloxy Alkylsulfonyl with 1 to 12 carbons; arylsulfonyl with 6 to 12 carbons such as phenylsulfonyl; cyano; nitro; hydroxyl; thiol; carboxyl; -SF ₃ ;- SF ₅ and so on.

The aforementioned R ^1E to R ^16E are each independently preferably an alkyl group having 1 to 12 carbons, more preferably an alkyl group having 1 to 6 carbons, and still more preferably a methyl group.

R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 may include aliphatic hydrocarbon groups with 1 to 25 carbon atoms: methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, and Dibutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isotenyl Dialkyl, undecyl, lauryl, myristyl, cetyl, stearyl and other linear or branched chain alkyl groups with carbon numbers from 1 to 25: cyclopropyl, cyclobutyl, Cycloalkyl groups having 3 to 25 carbon atoms such as cyclopentyl and cyclohexyl; cycloalkylalkyl groups having 4 to 25 carbon atoms such as cyclohexylmethyl and the like.

The aliphatic hydrocarbon groups with 1 to 25 carbons represented by R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 are each independently preferably an alkyl group with 1 to 15 carbons, and an alkyl group with 1 to 12 carbons is more preferred. good.

The aliphatic hydrocarbon groups having 1 to 25 carbon atoms shown by R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 may have halogen atoms, hydroxyl groups, nitro groups, cyano groups, -SO ₃ H, and thiol groups. , Amino and so on.

R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 contained in the aliphatic hydrocarbon group with 1 to 25 carbon atoms -CH ₂ -or -CH= can be -NR ^1A -, -SO ₂ -, -CO- , -O-, -COO-, -OCO-, -CONR ^2A -, -NR ^3A -CO-, -S-, -SO-, -CF ₂ -or -CHF- substitution.

_{When -CH 2} -or -CH= contained in the aliphatic hydrocarbon group having 1 to 25 carbon atoms is substituted, it is preferably substituted by -O-, -S-, -COO- or -SO _{2 -.}

_{When -CH 2} -or -CH= is substituted by -O- in the aforementioned aliphatic hydrocarbon group with 1 to 25 carbon atoms ^{, the aliphatic hydrocarbon group is -OR 111} (R ¹¹¹ may have halogen atoms with carbon number from 1 to The alkoxy group represented by the alkyl group of 24) is preferred. In addition, it may be a polyoxyalkylene group such as polyoxyethylene or polyoxypropylene.

_{When -CH 2} -or -CH= is substituted by -S- in the aforementioned aliphatic hydrocarbon group with 1 to 25 carbon atoms ^{, the aliphatic hydrocarbon group is replaced by -SR 111} (R ¹¹¹ may have halogen atoms with carbon number from 1 to The alkylthio group represented by the alkyl group of 24) is preferred.

_{When -CH 2} -or -CH= is substituted by -COO- in the aliphatic hydrocarbon group with carbon number from 1 to 25 ^{, the aliphatic hydrocarbon group is -COO-R 111} (R ¹¹¹ may have a carbon number of halogen atoms The group represented by the alkyl group from 1 to 24) is preferred.

_{When -CH 2} -or -CH= is _{substituted by -SO 2} -in the aforementioned aliphatic hydrocarbon group with 1 to 25 carbon atoms, the aliphatic hydrocarbon group is -SO ₂ -R ¹¹¹ (R ¹¹¹ may have halogen atoms The group represented by the alkyl group having 1 to 24 carbon atoms) is preferred, and can be -SO ₂ CHF ₂ , -SO ₂ CH ₂ F and the like.

基(chrysenyl)、聯三伸苯基、四苯基、芘基、苝基、蒄基(coronenyl)、聯苯基等碳數6至18之芳基；苯甲基、苯基乙基、萘基甲基等碳數7至18的芳烷基等，以碳數6至18之芳基為較佳，以苯基或苯甲基為更佳。 R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 show the aromatic hydrocarbon groups with 6 to 18 carbon atoms: phenyl, naphthyl, anthracenyl, naphthacenyl, pentaphenyl, phenanthrene base,

C6-C18 aryl groups such as chrysenyl, tetraphenylene, pyrenyl, perylene, coronenyl, and biphenyl; benzyl, phenylethyl, naphthalene An aralkyl group having 7 to 18 carbon atoms, such as a methyl group, is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a benzyl group.

Examples of the substituent system that the aromatic hydrocarbon group having 6 to 18 carbons represented by R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 may have: halogen atom; hydroxyl group; thiol group; amine group; nitro group; cyano group; -SO ₃ H base and so on.

R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 _{contain -CH 2} -or -CH= in the aromatic hydrocarbon group with carbon numbers of 6 to 18, which ^{can be -NR 1A} -, -SO ₂ -, -CO- , -O-, -COO-, -OCO-, -CONR ^2A -, -NR ^3A -CO-, -S-, -SO-, -CF ₂ -or -CHF- substitution.

_{When -CH 2} -or -CH= contained in the aforementioned aromatic hydrocarbon group having 6 to 18 carbon atoms is substituted, it is preferably substituted _{by -O- or -SO 2 -.}

_{When -CH 2} -or -CH= contained in the aforementioned aromatic hydrocarbon group with 6 to 18 carbons is substituted by -O-, the aromatic hydrocarbon group is preferably an aryloxy group with 6 to 17 carbons such as phenoxy ; Phenoxy ethyl, phenoxy diethylene glycol, phenoxy polyalkylene glycol aryl alkoxy and the like.

_{When -CH 2} -or -CH= is _{substituted by -SO 2} -in the aforementioned aromatic hydrocarbon group with carbon number 6 to 17, the aromatic hydrocarbon group is -SO ₂ -R ¹¹² (R ¹¹² series means carbon number 6 to The group represented by the 17 aryl group or the aralkyl group having 7 to 17 carbon atoms) is preferred.

The alkyl group having 1 to 6 carbon atoms represented by R ^1A , R ^2A and R ^3A may be the same as the alkyl group having 1 to 6 carbon atoms represented by ^{R 223.}

Examples of the halogen atom system represented by R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

吡基、噻唑基、二

唑基、嗎啉基、噻嗪基(thiazinyl)、三唑基、四唑基、二

環戊基、嗒嗪基(pyridazinyl)、嘧啶基、吡嗪基(pyrazinyl)、吲哚基、異吲哚基、苯并咪唑基、嘌呤基、苯并三唑基、喹啉基、異喹啉基、喹唑啉基、喹

啉基、

啉基(cinnolinyl)、喋啶基(pteridinyl)、苯并哌喃基、蒽基、吖啶基、氧雜蒽基(xanthenyl)、咔唑基、稠四苯基、卟吩基(porphynyl)、氯醌基(chloranil)、膽鹼基、腺嘌呤基(adenyl)、甲脒基(guanyl)、胞密啶基、胸嘧啶基、尿嘧啶基、喹啉基、硫苯基、咪唑基、

唑基、噻唑基等碳數3至16之脂肪族雜環基 及碳數3至16之芳香族雜環基。R¹、R²、R⁶及R⁷所示之雜環基係分別獨立地以吡咯啶基、六氫吡啶基、四氫呋喃甲基、四氫哌喃基、四氫噻吩基、四氫噻喃基或吡啶基為較佳。 The heterocyclic groups represented by R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 include pyridyl, pyrrolidinyl, tetrahydrofuryl methyl, tetrahydrothienyl, pyrrolyl, furyl, thienyl, hexahydropyridyl, Tetrahydropiperanyl, tetrahydrothiopiperanyl, thiopyranyl, imidazolidinone, pyrazolyl,

Pyryl, thiazolyl, two

Azolyl, morpholinyl, thiazinyl, triazolyl, tetrazolyl, two

Cyclopentyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, benzimidazolyl, purinyl, benzotriazolyl, quinolinyl, isoquine Linyl, quinazolinyl, quinoline

Linyl,

Cinnolinyl, pteridinyl, benzopiperanyl, anthracenyl, acridinyl, xanthenyl, carbazolyl, fused tetraphenyl, porphynyl, Chloranil, choline, adenyl, guanyl, cytimidinyl, thymine, uracil, quinolinyl, thiophenyl, imidazolyl,

Aliphatic heterocyclic groups with 3 to 16 carbon atoms and aromatic heterocyclic groups with 3 to 16 carbon atoms such as azole group and thiazolyl group. The heterocyclic groups represented by R ¹ , R ² , R ⁶ and R ⁷ are independently pyrrolidinyl, hexahydropyridyl, tetrahydrofuryl methyl, tetrahydropiperanyl, tetrahydrothienyl, and tetrahydrothiopyran. Pyridyl or pyridyl is preferred.

The ring system formed by R ^Y1 and R ^Y2 bonded to each other includes a nitrogen atom as a constituent element of the ring. The ring system formed by R ^Y1 and R ^Y2 bonded to each other may be a single ring or a condensed ring, but a single ring is preferred. The ring system formed by R ^Y1 and R ^Y2 bonded to each other may further include heteroatoms (oxygen atoms, sulfur atoms, nitrogen atoms, etc.) as the constituent elements of the ring. The ring formed by R ^Y1 and R ^Y2 bonded to each other is preferably a ring that does not have an unsaturated bond.

The ring formed by bonding R ^Y1 and R ^{Y2 to} each other is usually a 3- to 10-membered ring, preferably a 5- to 7-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

The ring system formed by R ^Y1 and R ^Y2 bonded to each other may have a substituent. Examples of the substituent system are the same as the substituents represented by ^{R 1E.}

Examples of the ring system formed by bonding R ^Y1 and R ^{Y2 to each other include the rings described below.}

R ^Y1 and R ^Y2 are each independently preferably an alkyl group having 1 to 25 carbons, more preferably an alkyl group having 1 to 12 carbons, and a linear alkyl group having 1 to 6 carbons. More preferably, methyl, ethyl, n-propyl or n-butyl is particularly preferred.

R ^Y6 and R ^Y7 are each independently preferably an alkyl group having 1 to 25 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and a branched chain alkyl group having 1 to 6 carbon atoms. Even more preferably, isopropyl, isobutyl, and tertiary butyl are particularly preferred.

The compound represented by the formula (Y) includes the compound represented by the formula (Y-1) described below to the compound represented by the formula (Y-136).

The compound (Y) is, for example, a compound represented by formula (YA) (hereinafter, sometimes referred to as compound (YA)) and a compound represented by formula (YB) (hereinafter, sometimes referred to as compound (YB) ) Obtained by reaction.

[In the formula, R ^Y1 to R ^Y7 represent the same meanings as described above. ]

The reaction of compound (Y-A) and compound (Y-B) is usually carried out by mixing compound (Y-A) and compound (Y-B), and compound (Y-B) is preferably added to compound (Y-A).

In addition, the reaction between compound (Y-A) and compound (Y-B) is preferably to mix compound (Y-A) and compound (Y-B) in the presence of a base and a methylating agent.

Preferably, the mixed compound (Y-A), compound (Y-B), base and methylating agent are preferred,

It is more preferable to mix the compound (Y-B) and the base in the mixture of the compound (Y-A) and the methylating agent,

It is even more preferable to add a mixture of compound (Y-B) and a base to the mixture of compound (Y-A) and methylating agent.

Examples of alkalis include: sodium hydroxide, lithium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide and other metal hydroxides (preferably alkali metal hydroxides) ); metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, sodium isopropoxide, sodium tertiary butoxide, potassium tertiary butoxide (preferably Alkali metal alkoxides); metal hydrides such as lithium hydride, sodium hydride, potassium hydride, lithium aluminum hydride, sodium borohydride, aluminum hydride, and sodium aluminum hydride; metal oxides such as calcium oxide and magnesium oxide; sodium bicarbonate, carbonic acid Metal carbonates such as sodium and potassium carbonate (preferably alkaline earth metal carbonates); n-butyl lithium, tertiary lithium, methyl lithium, Grignard reagent and other organic alkyl metal compounds; ammonia, three Ethylamine, diisopropylethylamine, ethanolamine, pyrrolidine, hexahydropyridine, diazabicycloundecene, diazabicyclononene, guanidine, tetramethylammonium hydroxide, tetraethylammonium hydroxide , Pyridine, aniline, dimethoxyaniline, ammonium acetate, β-alanine and other amine compounds (preferably tertiary amines such as triethylamine and diisopropylethylamine); lithium diisopropylamine, amine group Sodium, potassium hexamethyldisilazide (potassium hexamethyldisilazide) and other metal amide compounds (preferably alkali metal amide); trimethyl sulfonium hydroxide and other sulfonium compounds; diphenyl sulfonium hydroxide and other sulfonium compounds ; Phosphazene (Phosphazene) base and so on.

The usage amount of the base is relative to 1 mol of compound (Y-A), usually 0.1 to 5 mol, preferably 0.5 to 2 mol.

Methylating agents include methyl iodide, dimethyl sulfate, methyl methanesulfonate, methyl fluorosulfonate, methyl p-toluenesulfonate, methyl trifluoromethanesulfonate, trimethyloxonium tetrafluoromethane Borate (Trimethyloxonium Tetrafluoroborate) and so on.

The amount of the methylating agent used is relative to 1 mol of compound (Y-A), usually 0.1 to 5.0 mol, preferably 0.5 to 2.0 mol.

The reaction time of compound (Y-A) and compound (Y-B) is usually 0.1 to 10 hours, preferably 0.2 to 3 hours.

The reaction temperature of compound (Y-A) and compound (Y-B) is usually -50 to 150°C, preferably -20 to 100°C.

Relative to 1 mol of compound (Y-A), the amount of compound (Y-B) used is usually 0.1 to 10 mol, preferably 0.5 to 5 mol.

Examples of the compound (Y-A) include the compounds described below.

As the compound (Y-B), a commercially available product can be used, and the following compounds and the like can be mentioned.

The compound (YA) is, for example, a compound represented by formula (YC) (hereinafter, sometimes referred to as compound (YC)) and a compound represented by formula (YD) (hereinafter, sometimes referred to as compound (YD)) can be reacted And get.

[In formula (YC), R ^Y1 , R ^Y2 , R ^Y3 , R ^Y6 and R ^{Y7 have the} same meanings as described above. The E ₁ series represents the break away from the base. ]

Examples of the leaving group represented by E ₁ include a halogen atom, a p-toluenesulfonyl group, and a trifluoromethylsulfonyl group.

The reaction of the compound (Y-C) and the compound (Y-D) is carried out by mixing the compound (Y-C) and the compound (Y-D).

Relative to 1 mol of compound (Y-C), the amount of compound (Y-D) used is usually 0.1 to 5 mol, preferably 0.5 to 2 mol.

The reaction of the compound (Y-C) and the compound (Y-D) can be carried out in the presence of a solvent. The solvent system can include acetonitrile, benzene, toluene, acetone, ethyl acetate, chloroform, dichloroethane, monochlorobenzene, methanol, ethanol, isopropanol, tertiary butanol, 2-butanone, tetrahydrofuran, diethyl Ether, dimethyl sulfide, N,N-dimethylacetamide, N,N-dimethylformamide, water, etc. Preferred are acetonitrile, tetrahydrofuran, chloroform, dichloromethane, and diethyl ether, more preferred are acetonitrile, tetrahydrofuran, and chloroform, and still more preferred are methanol, ethanol, isopropanol, and acetonitrile.

The reaction time between compound (Y-C) and compound (Y-D) is usually 0.1 to 10 hours.

The reaction temperature of the compound (Y-C) and the compound (Y-D) is usually -50 to 150°C.

Examples of the compound (Y-C) include the compounds described below.

As the compound (Y-D), a commercially available product can be used. For example, cyanogen chloride, cyanogen bromide, p-toluene sulfonate cyanide, trifluoromethane sulfonate cyanide, 1-chloromethyl-4-fluoro-1,4-diazide bicyclo[2.2.2] octane bis (Tetrafluoroborate) (also known as Selectfluor (registered trademark of Air Products and Chemicals)), benzyl (phenylhydroiodide) (trifluoromethanesulfonyl) methanide, 2,8-bis Fluoro-5-(trifluoromethyl)-5H-dibenzo[b,d]thiophene-5-sulfur trifluoromethanesulfonate, N-bromosuccinimide, N-chlorosuccinimide, N -Iodine succinimide, etc.

The compound (YC) can be obtained by combining a compound represented by formula (YE) (hereinafter, sometimes referred to as compound (YE)) and a compound represented by formula (YF) (hereinafter, sometimes referred to as compound (YF)) Obtained by reaction.

[In the formula, R ^Y1 , R ^Y2 , R ^Y6 and R ^{Y7 have the} same meaning as described above. ]

The reaction of the compound (Y-E) and the compound (Y-F) is carried out by mixing the compound (Y-E) and the compound (Y-F).

Relative to 1 mol of compound (Y-E), the usage amount of compound (Y-F) is usually 0.1 to 5 mol, preferably 0.5 to 2 mol.

The reaction of the compound (Y-E) and the compound (Y-F) can be carried out in the presence of a solvent. Examples include acetonitrile, benzene, toluene, acetone, ethyl acetate, chloroform, dichloroethane, monochlorobenzene, methanol, ethanol, isopropanol, tertiary butanol, 2-heptanone, tetrahydrofuran, diethyl ether, Dimethyl sulfide, N,N-dimethylacetamide, N,N-dimethylformamide, water, etc. Preferred are benzene, toluene, ethanol, and acetonitrile.

The reaction time of the compound (Y-E) and the compound (Y-F) is usually 0.1 to 10 hours.

The reaction temperature of the compound (Y-E) and the compound (Y-F) is usually -50 to 150°C.

Examples of the compound (Y-E) include the compounds described below.

The compound (YF) system includes: primary amines such as methylamine, ethylamine, ethanolamine, 4-hydroxybutylamine; dimethylamine, diethylamine, dibutylamine, pyrrolidine, hexahydropyridine, Secondary amines such as 3-hydroxypyrrolidine and 4-hydroxyhexahydropyridine.

In addition, the light selective absorption compound (B) is also preferably a compound having a part of the merocyanidin structure as a constituent element of the ring. Examples of compounds having a part of the merocyanidin structure as a constituent element of the ring include compounds in which the carbon-carbon bonding structure part of the merocyanidin structure becomes a constituent element of the ring.

The light selective absorption compound (B) having a part of the merocyanidin structure as a constituent element of the ring includes, for example, a compound having a partial structure represented by the following formula (X) (hereinafter, sometimes referred to as compound (X) ).

[In the formula (X), the ring W ¹ represents a ring structure that has at least one double bond as a constituent element of the ring and does not have aromaticity.

R ³ represents a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a carboxyl group, -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, and the number of carbons that may have a substituent The aliphatic hydrocarbon group of 1 to 25 or the aromatic hydrocarbon group of 6 to 18 carbons which may have substituents, the aliphatic hydrocarbon group or the aromatic hydrocarbon group contains -CH ₂ -, -CH= series may be -O-,- S-, -NR ^1xA -, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CONR ^2xA -, -NR ^3xA -CO-, -O-CO-NR ^4xA -, -NR ^5xA -CO-O-, -NR ^6xA -CO-NR ^7xA -, -CO-S-, -S-CO-S-, -S-CO-NR ^8xA -, -NR ^9xA -CO -S-, -CS-, -O-CS-, ^{-CS-O-, -NR 10xA -CS-} , -NR ^{11xA -CS} -S-, -S-CS-, -CS-S-, -S -CS-S-, -SO- or -SO ₂ -replaced.

R ^1xA , R ^2xA , R ^3xA , R ^4xA , R ^5xA , R ^6xA , R ^7xA , R ^8xA , R ^9xA , R ^10xA and R ^11xA each independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms. ]

The ring W ¹ is not particularly limited as long as it has one or more double bonds as a ring constituent element, and does not have an aromatic ring. The ring W ¹ system may be a single ring or a condensed ring.

The ring W ¹ may be a heterocyclic ring containing a hetero atom (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) as a constituent element of the ring, or may be an aliphatic hydrocarbon ring composed of a carbon atom and a hydrogen atom.

The ring W ¹ has more than one double bond as a constituent element of the ring, but ^{the double bond contained in the ring W 1} is usually 1 to 4, preferably 1 to 3, and more preferably 1 or 2 , 1 is better.

The ring W ¹ is usually a ring with 5 to 18 carbon atoms, preferably a 5- to 7-membered ring structure, and more preferably a 6-membered ring structure.

The ring W ¹ is preferably a single ring.

The ring W ¹ system may have a substituent. Examples of the aforementioned substituent system include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; carbon numbers such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl 1 to 12 alkyl; fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1 ,2,2-Tetrafluoroethyl, 1,1,2,2,2-pentafluoroethyl and other C1-C12 halogenated alkyl groups; methoxy, ethoxy, propoxy, butoxy , Pentyloxy, hexyloxy and other C1-C12 alkoxy; methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio and other carbons Alkylthio with 1 to 12; monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 1,1,2,2,2-pentafluoroethoxy Fluoroalkoxy with 1 to 12 carbons; amino, methylamino, ethylamino, dimethylamino, diethylamino, methylethyl and other carbons 1 to 6 Alkyl-substituted amine groups; alkylcarbonyloxy groups with carbon numbers from 2 to 12 such as methylcarbonyloxy and ethylcarbonyloxy; alkyl groups with carbon numbers from 1 to 12 such as methylsulfonyl and ethylsulfonyloxy Sulfonyl; arylsulfonyl having 6 to 12 carbons such as phenylsulfonyl; cyano; nitro; hydroxyl; thiol; carboxyl; -SF ₃ ; -SF ₅ and the like.

The substituent that ring W ¹ may have is preferably an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, an alkylthio group with 1 to 12 carbons, or an alkyl group with 1 to 6 carbons. Substituted amine group.

Examples of the ring W ¹ system include the groups described below.

[In the formula, *1 represents a bond with a nitrogen atom, and *2 represents a bond with a carbon atom. ]

Examples of the heterocyclic group represented by R ³ are the same as those of the heterocyclic group represented by ^{R Y1 in formula (Y).}

The heterocyclic group represented by R ^{3 is} preferably pyrrolidinyl, hexahydropyridyl, tetrahydrofuranyl, tetrahydropiperanyl, tetrahydrothienyl, tetrahydrothiopyranyl or pyridyl.

The aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by R ³ is the same as the aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by ^{R Y1 in the formula (Y).}

The aliphatic hydrocarbon group having 1 to 25 carbons represented by R ³ is preferably an alkyl having 1 to 15 carbons, and more preferably an alkyl having 1 to 12 carbons.

Examples of the substituent system that the aliphatic hydrocarbon group represented by R ³ may have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, and -SO ₃ H.

_{The -CH 2} -or -CH= system contained in the aliphatic hydrocarbon group with 1 to 25 carbons represented by R ³ can be -O-, -S-, -NR ^1xA -, -CO-, -CO-O- , -O-CO-, -O-CO-O-, -CONR ^2xA -, -NR ^3xA -CO-, -O-CO-NR ^4xA -, -NR ^5xA -CO-O-, -NR ^6xA -CO -NR ^7xA -, -CO-S-, -S-CO-S-, -S-CO-NR ^8xA -, -NR ^9xA -CO-S-, -CS-, -O-CS-, -CS- O-, -NR ^{10xA -CS-} , -NR ^{11xA -CS} -S-, -S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO ₂ -replaced.

_{When -CH 2} -or -CH= contained in the aliphatic hydrocarbon group having 1 to 25 carbon atoms is substituted, it is preferably substituted by -O-, -S-, -CO-O- or -SO ₂ -.

_{When -CH 2} -or -CH= is substituted by -O- in the aforementioned aliphatic hydrocarbon group with 1 to 25 carbon atoms, it is represented by -OR (R is an alkyl group with 1 to 24 carbon atoms that may have a halogen atom) The alkoxy group, polyethylene glycol or polypropylene glycol is preferred.

_{When -CH 2} -or -CH= is substituted by -S- in the aforementioned aliphatic hydrocarbon group with 1 to 25 carbons, it is represented by -SR (R is an alkyl group with 1 to 24 carbons that may have a halogen atom) The alkylthio group is preferred.

_{When -CH 2} -or -CH= is substituted by -COO- in the aforementioned aliphatic hydrocarbon group with 1 to 25 carbon atoms ^{, use -COO-R 111} (R ¹¹¹ is an alkane with 1 to 24 carbon atoms which may have a halogen atom). The base shown in (base) is preferred.

_{When -CH 2} -or -CH= is _{substituted by -SO 2} -in the aforementioned aliphatic hydrocarbon group with 1 to 25 carbon atoms _{, use -SO 2} -R ¹¹² (R ¹¹² may have halogen atoms with carbon number 1 to 24 The group represented by the alkyl group) is preferred.

R ^1xA , R ^2xA , R ^3xA , R ^4xA , R ^5xA , R ^6xA , R ^7xA , R ^8xA , R ^9xA , R ^10xA and R ^11xA alkyl groups with carbon numbers 1 to 6 shown by formula (Y The alkyl groups with 1 to 6 carbons represented by ^{R 1A} in) are the same.

The aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ³ is the same as the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by ^{R Y1 in the formula (Y).}

The aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ³ is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a benzyl group.

Examples of the substituent systems that the aromatic hydrocarbon group having 6 to 25 carbons represented by R ³ may have include halogen atoms; hydroxyl groups; thiol groups; amine groups; nitro groups; cyano groups; -SO ₃ H groups and the like.

_{The -CH 2} -or -CH= system contained in the aromatic hydrocarbon group with 6 to 18 carbons represented by R ³ can be -O-, -S-, -NR ^1xA -, -CO-, -CO-O- , -O-CO-, -O-CO-O-, -CONR ^2xA -, -NR ^3xA -CO-, -O-CO-NR ^4xA -, -NR ^5xA -CO-O-, -NR ^6xA -CO -NR ^7xA -, -CO-S-, -S-CO-S-, -S-CO-NR ^8xA -, -NR ^9xA -CO-S-, -CS-, -O-CS-, -CS- O-, -NR ^{10xA -CS-} , -NR ^{11xA -CS} -S-, -S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO ₂ -replaced.

_{When -CH 2} -or -CH= contained in the aforementioned aromatic hydrocarbon group having 6 to 18 carbon atoms is substituted, it is preferably substituted _{by -O- or -SO 2 -.}

_{When -CH 2} -or -CH= contained in the aforementioned aromatic hydrocarbon group having 6 to 18 carbon atoms is substituted by -O-, aryloxy groups having 6 to 26 carbon atoms such as phenoxy group are preferred.

_{When -CH 2} -or -CH= is _{substituted by -SO 2} -in the aforementioned aromatic hydrocarbon group with carbon number 6 to 18 _{, -SO 2} -R (R series represents an aryl group with carbon number 6 to 18 or carbon number The group represented by the aralkyl group from 7 to 18) is preferred.

R ³ line to a nitro group; a cyano group; a halogen _{atom; -OCF 3; -SCF 3; -SF} 5; -SF 3; fluoroalkyl group having a carbon number of 1 to 25; an aryl group having a carbon number of 6 to 18 fluorine of; - CO-OR ^111xA or -SO ₂ -R ^112xA (R ^111xA and R ^112xA each independently represent an alkyl group having 1 to 24 carbon atoms which may have a halogen atom) is preferably,

With a cyano group; a fluorine atom; a chlorine atom; -OCF ₃ ; -SCF ₃ ; a fluoroalkyl group with 1 to 12 carbon atoms; -CO-OR ^111xA or -SO ₂ -R ^112xA (R ^111xA and R ^112xA are each independently represented The alkyl group having 1 to 24 carbon atoms which may have a halogen atom) is more preferred,

Cyano is particularly preferred.

The molecular weight of the compound (X) is preferably 2500 or less, more preferably 2000 or less, still more preferably 1500 or less, particularly preferably 1000 or less. Furthermore, it is preferably 100 or more, 150 or more, or 200 or more.

If the compound (X) has a molecular weight of 3000 or less, it may be a homopolymer or a copolymer, but a monomer is preferred.

The compound (X) is preferably any one of the compound represented by formula (I) to the compound represented by formula (VIII), and the compound represented by formula (I) is more preferable.

[In formulas (I) to (VIII), rings W ¹ and R ^{3 have the} same meanings as described above.

The ring W ² , the ring W ³ , the ring W ⁴ , the ring W ⁵ , the ring W ⁶ , the ring W ⁷ , the ring W ⁸ , the ring W ⁹ , the ring W ¹⁰ , the ring W ¹¹ and the ring W ¹² each independently represent at least 1 A ring structure in which a double bond is a constituent element of the ring.

The ring W ¹¹¹ represents a ring having at least two nitrogen atoms as constituent elements.

Ring W ¹¹² and ring W ¹¹³ each independently represent a ring having at least one nitrogen atom as a constituent element.

R ¹ , R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁹¹ , R ¹⁰¹ , R ¹¹¹ , R ² , R ¹² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² , R ¹⁰² and R ¹¹² Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a carboxyl group, -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, and may have a substituent The aliphatic hydrocarbon group with 1 to 25 carbons or the aromatic hydrocarbon group with 6 to 18 carbons which may have substituents. The aliphatic hydrocarbon group or aromatic hydrocarbon group contains -CH ₂ -or -CH= which can be -NR ^12A -, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -CONR ^13A -, -NR ^14A -CO-, -S-, -SO-, -CF ₂ -or- CHF-replaced.

R ¹³ , R ²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁶³ , R ⁷³ , R ⁸³ , R ⁹³ , R ¹⁰³ and R ¹¹³ each independently represent a heterocyclic group, a halogen atom, a nitro group, a cyano group, and a hydroxyl group , Thiol group, carboxyl group, -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, aliphatic hydrocarbon group with 1 to 25 carbons that may have substituents or 6 to 18 carbons that may have substituents The aromatic hydrocarbon group, the aliphatic hydrocarbon group or the aromatic hydrocarbon group contains -CH ₂ -or -CH= series can be -O-, -S-, -NR ^1A -, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CONR ^2A -, -NR ^3A -CO-, -O-CO-NR ^4A -, -NR ^5A -CO-O-, -NR ^6A -CO- NR ^7A -, -CO-S-, -S-CO-S-, -S-CO-NR ^8A -, -NR ^9A -CO-S-, -CS-, -O-CS-, -CS-O -, -NR ^10A -CS-, -NR ^11A -CS-S-, -S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO ₂ -replaced.

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A , R ^8A , R ^9A , R ^10A , R ^11A , R ^12A , R ^13A and R ^14A each independently represent a hydrogen atom or carbon number 1 to 6 alkyl group.

R ⁴ , R ¹⁴ , R ²⁴ , R ³⁴ , R ⁴⁴ , R ⁵⁴ , R ⁶⁴ , R ⁷⁴ , R ⁸⁴ , R ⁹⁴ , R ¹⁰⁴ , R ¹¹⁴ , R ⁵ , R ¹⁵ , R ²⁵ , R ³⁵ , R ⁷⁵ And R ⁸⁵ each independently represent an electron withdrawing group.

R ¹ and R ² may be bonded to each other to form a ring.

R ⁴¹ and R ⁴² may be bonded to each other to form a ring.

R ⁵¹ and R ⁵² may be bonded to each other to form a ring.

R ⁶¹ and R ⁶² can be bonded to each other to form a ring.

R ⁹¹ and R ⁹² can be bonded to each other to form a ring.

R ¹⁰¹ and R ¹⁰² may be bonded to each other to form a ring.

R ¹¹¹ and R ¹¹² may be bonded to each other to form a ring.

The R ² and R ³ systems may be bonded to each other to form a ring.

R ¹² and R ¹³ may be bonded to each other to form a ring.

R ⁴² and R ⁴³ can be bonded to each other to form a ring.

R ⁵² and R ⁵³ may be bonded to each other to form a ring.

R ⁶² and R ⁶³ can be bonded to each other to form a ring.

R ⁷² and R ⁷³ can be bonded to each other to form a ring.

R ⁸² and R ⁸³ can be bonded to each other to form a ring.

R ⁹² and R ⁹³ can be bonded to each other to form a ring.

R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring.

R ¹¹² and R ¹¹³ may be bonded to each other to form a ring.

R ⁴ and R ⁵ may be bonded to each other to form a ring.

R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring.

R ²⁴ and R ²⁵ can be bonded to each other to form a ring.

R ³⁴ and R ³⁵ may be bonded to each other to form a ring.

R ⁷⁴ and R ⁷⁵ can be bonded to each other to form a ring.

R ⁸⁴ and R ⁸⁵ can be bonded to each other to form a ring.

R ⁶ and R ⁸ each independently represent a divalent bonding group.

R ⁷ represents a single bond or a divalent bond group.

R ⁹ and R ¹⁰ each independently represent a trivalent bonding group.

R ¹¹ represents a 4-valent bonding group. ]

The ring W ² , the ring W ³ , the ring W ⁴ , the ring W ⁵ , the ring W ⁶ , the ring W ⁷ , the ring W ⁸ , the ring W ⁹ , the ring W ¹⁰ , the ring W ¹¹ and the ring W ¹² are each independently having One or more double bonds may be a ring as a constituent element of the ring, and it is not particularly limited. The ring W ² to the ring W ¹² system may each be a single ring or a condensed ring. In addition, the ring W ² to the ring W ¹² system may be an aliphatic ring or an aromatic ring.

The ring W ² to the ring W ¹² are a heterocyclic ring which may contain a hetero atom (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) as a constituent element of the ring.

Ring W ² to Ring W ¹² have more than one double bond as a constituent element of the ring, but ^{the double bonds contained in Ring W 2} to Ring W ¹² are each independently usually 1 to 4, preferably 1 to 3 , 1 or 2 is more preferable, and 1 is even more preferable.

The ring W ² to the ring W ¹² are each independently a ring having 5 to 18 carbon atoms, preferably a 5 to 7 membered ring structure, and more preferably a 6 membered ring structure.

The ring W ² to the ring W ¹² are each independently preferably a single ring. In addition, it is preferable that the ring W ² to the ring W ¹² are independently a ring having no aromaticity.

The ring W ² to the ring W ¹² system may have a substituent. Examples of the aforementioned substituent system are the same as those that may be possessed by ^{ring W 1.}

The substituents that ring W ² to ring W ¹² may have are preferably an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, an alkylthio group with 1 to 12 carbons, or an alkylthio group with 1 to 12 carbons. 6 is an alkyl substituted amine group.

Specific examples of the ring W ² to the ring W ¹² are the same as those of the ^{ring W 1.}

The ring W ¹¹¹ is a ring containing two nitrogen atoms as a constituent element of the ring. The ring W ¹¹¹ may be a single ring or a condensed ring, but a single ring is preferred.

The ring W ¹¹¹ is usually a 5- to 10-membered ring, preferably a 5- to 7-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

The ring W ¹¹¹ system may have a substituent. The substituents that ring W ¹¹¹ may have include: hydroxyl; thiol group; aldehyde group; alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl groups; and carbon numbers 1 to 6 such as methoxy and ethoxy groups Alkoxy; alkylthio groups with carbon numbers from 1 to 6 such as methylthio and ethylthio; amino groups, methylamino groups, dimethylamino groups, methyl ethyl groups, etc. with carbon number 1 Amino group substituted by alkyl to 6; -CONR ^1f R ^2f (R ^1f and R ^2f each independently represent a hydrogen atom or an alkyl group of 1 to 6 carbons); -COSR ^3f (R ^3f represents a carbon number of 1 to 6 alkyl); -CSSR ^4f (R ^4f represents an alkyl with 1 to 6 carbons); -CSOR ^5f (R ^5f represents an alkyl with 1 to 6 carbons); -SO ₂ R ^6f (R ^5f It represents an aryl group having 6 to 12 carbons or an alkyl group having 1 to 6 carbons which may have a fluorine atom) and the like.

Examples of the ring W ¹¹¹ include the ring described below.

The ring W ¹¹² and the ring W ¹¹³ are each independently a ring including one nitrogen atom as a constituent element of the ring. The ring W ¹¹² and the ring W ¹¹³ may each independently be a single ring or a condensed ring, but a single ring is preferred.

The ring W ¹¹² and the ring W ¹¹³ are each independently usually a 5- to 10-membered ring, preferably a 5- to 7-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

The ring W ¹¹² and the ring W ¹¹³ system may have a substituent. Examples of the substituent system that the ring W ¹¹² and the ring W ¹¹³ may have are the same as the substituent of the ^{ring W 1.}

Examples of the ring W ¹¹² and the ring W ¹¹³ include the rings described below.

R ⁴ , R ¹⁴ , R ²⁴ , R ³⁴ , R ⁴⁴ , R ⁵⁴ , R ⁶⁴ , R ⁷⁴ , R ⁸⁴ , R ⁹⁴ , R ¹⁰⁴ , R ¹¹⁴ , R ⁵ , R ¹⁵ , R ²⁵ , R ³⁵ , R ⁷⁵ The electron withdrawing group represented by ^{R 85} and R 85 may be the same as ^{R Y3 in the formula (Y).}

R ⁴ , R ¹⁴ , R ²⁴ , R3 ⁴ , R ⁴⁴ , R ⁵⁴ , R ⁶⁴ , R ⁷⁴ , R ⁸⁴ , R ⁹⁴ , R ¹⁰⁴ , R ¹¹⁴ , R ⁵ , R ¹⁵ , R ²⁵ , R ³⁵ , R ⁷⁵ And ^{the electron withdrawing groups shown by R 85} are independently nitro, cyano, halogen atom, -OCF ₃ , -SCF ₃ , _{-SF 5} , _{-SF 3} , fluoroalkyl (preferably carbon number 1 to 25), fluoroaryl (preferably with carbon number 6 to 18), -CO-OR ²²² , -SO ₂ -R ²²² or -CO-R ²²² (R ²²² is a hydrogen atom, which may have substituent carbon number An alkyl group of 1 to 25 or an aromatic hydrocarbon group of 6 to 18 carbons which may have a substituent) is preferably,

With nitro group, cyano group, fluorine atom, chlorine atom, -OCF ₃ , -SCF ₃ , fluoroalkyl group, -CO-OR ²²² or -SO ₂ -R ²²² (R ²²² represents a hydrogen atom, which may have a substituent An alkyl group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent) is more preferred, and a cyano group is even more preferred.

At least one of R ⁴ and R ⁵ is preferably a cyano group, more preferably R ⁴ is a cyano group, and R ⁵ is a cyano group, -CO-OR ²²² or -SO ₂ -R ²²² (R ²²² respectively It independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms which may have a halogen atom, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a halogen atom).

The ring system formed by bonding R ⁴ and R ^{5 to} each other may be the same as the ring formed by bonding ^{R Y4} and R ^{Y5 to each other in formula (Y).}

The ring formed by bonding R ⁴ and R ^{5 to} each other is usually a 3 to 10 membered ring, preferably a 5 to 7 membered ring, and more preferably a 5-membered ring or a 6-membered ring.

Examples of the ring system formed by bonding R ⁴ and R ^{5 to each other include the structures described below.}

[In the formula, * represents a bond with a carbon atom. R ^1E to R ^16E each independently represent a hydrogen atom or a substituent. ]

The ring system formed by R ⁴ and R ⁵ bonding to each other may have a substituent (R ^1E to R ^16E in the above formula). Examples of the aforementioned substituent system include the same substituents as the substituents that ^{ring W 1 may have.} The aforementioned R ^1E to R ^16E are each independently preferably an alkyl group having 1 to 12 carbons, more preferably an alkyl group having 1 to 6 carbons, and still more preferably a methyl group.

The ring system formed by bonding R ¹⁴ and R ^{15 to} each other is the same as the ring formed by bonding ^{R 4} and R ^{5 to each other.}

The ring system formed by bonding R ²⁴ and R ^{25 to} each other may be the same as the ring formed by bonding ^{R 4} and R ^{5 to each other.}

The ring system formed by bonding R ³⁴ and R ^{35 to} each other may be the same as the ring formed by bonding ^{R 4} and R ^{5 to each other.}

The ring system formed by bonding R ⁷⁴ and R ^{75 to} each other may be the same as the ring formed by bonding ^{R 4} and R ^{5 to each other.}

The ring system formed by bonding R ⁸⁴ and R ^{85 to} each other may be the same as the ring formed by bonding ^{R 4} and R ^{5 to each other.}

R ¹ , R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁹¹ , R ¹⁰¹ , R ¹¹¹ , R ² , R ¹² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² , R ¹⁰² , R ¹¹² , R ¹³ , R ²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁶³ , R ⁷³ , R ⁸³ , R ⁹³ , R ¹⁰³ and R ^{113 and} the heterocyclic group represented by R 103 and R 113 can be exemplified by R in formula (Y) The heterocyclic groups represented by ^{Y1 are the same.}

R ¹ , R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁹¹ , R ¹⁰¹ , R ¹¹¹ , R ² , R ¹² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² , R ¹⁰² , R ¹¹² , R ¹³ , R ²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁶³ , R ⁷³ , R ⁸³ , R ⁹³ , R ¹⁰³ and R ¹¹³ represent the heterocyclic groups represented by pyrrolidinyl, hexahydro Pyridyl, tetrahydrofuranyl, tetrahydropiperanyl, tetrahydrothienyl, tetrahydrothiopyranyl or pyridyl are preferred.

R ¹ , R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁹¹ , R ¹⁰¹ , R ¹¹¹ , R ² , R ¹² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² , R ¹⁰² , R ¹¹² , R ¹³ , R ²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁶³ , R ⁷³ , R ⁸³ , R ⁹³ , R ^103, and R ¹¹³ show aliphatic hydrocarbon groups with 1 to 25 carbon atoms and formulae In (Y), the aliphatic hydrocarbon groups with carbon numbers 1 to 25 represented by ^{R Y1 are the same.}

The aforementioned aliphatic hydrocarbon group having 1 to 25 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

R ¹ , R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁹¹ , R ¹⁰¹ , R ¹¹¹ , R ² , R ¹² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² , R ¹⁰² , R ¹¹² , R ¹³ , R ²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁶³ , R ⁷³ , R ⁸³ , R ⁹³ , R ^103, and R ¹¹³ may have substituents for the aliphatic hydrocarbon group represented by halogen atoms, Hydroxy, nitro, cyano, -SO ₃ H, etc.

In addition, R ¹ , R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁹¹ , R ¹⁰¹ , R ¹¹¹ , R ² , R ¹² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² , R ¹⁰² , _{The -CH 2} -or -CH= system contained in the aliphatic hydrocarbon group with 1 to 25 carbons represented by R ^{112 can be -NR 12A} -, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -CONR ^13A -, -NR ^14A -CO-, -S-, -SO-, -CF ₂ -or -CHF- substitution.

R ¹³ , R ²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁶³ , R ⁷³ , R ⁸³ , R ⁹³ , R ¹⁰³ and R ¹¹³ represented by the aliphatic hydrocarbon group with 1 to 25 carbons -CH ₂ -Or -CH= can be -O-, -S-, -NR ^1A -, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CONR ^2A -, -NR ^3A -CO-, -O-CO-NR ^4A -, -NR ^5A -CO-O-, -NR ^6A -CO-NR ^7xA -, -CO-S-, -S-CO-S-,- S-CO-NR ^8A -, -NR ^9A -CO-S-, -CS-, -O-CS-, -CS-O-, -NR ^10A -CS-, -NR ^11A -CS-S-,- S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO ₂ -replaced.

_{When -CH 2} -or -CH= contained in the aliphatic hydrocarbon group having 1 to 25 carbon atoms is substituted, it is preferably substituted by -O-, -S-, -CO-O- or -SO ₂ -.

_{When -CH 2} -or -CH= is substituted by -O- in the aforementioned aliphatic hydrocarbon group with 1 to 25 carbon atoms, the aliphatic hydrocarbon group is based on -O-R'(R' system may have a carbon number of halogen atoms The alkoxy represented by 1 to 24 alkyl) is preferred.

In addition, it may be a polyoxyalkylene group such as polyoxyethylene or polyoxypropylene. Examples of the alkoxy system represented by -O-R' include methoxy, ethoxy, and -OCF ₃ groups.

_{When -CH 2} -or -CH= is substituted by -S- in the aforementioned aliphatic hydrocarbon group with 1 to 25 carbon atoms, the aliphatic hydrocarbon group is based on -S-R'(R' system may have a carbon number of halogen atoms The alkylthio group represented by the alkyl group from 1 to 24) is preferred. In addition, it may be a polyalkylene sulfide group such as a polyethylene sulfide group or a polypropylene sulfide group. Examples of the alkylthio group represented by -S-R' include methylthio, ethylthio, -SCF ₃ group, polyvinylthio, polypropylene thio, and the like.

_{When -CH 2} -or -CH= is substituted by -COO- in the aforementioned aliphatic hydrocarbon group with 1 to 25 carbon atoms, the aliphatic hydrocarbon group is replaced by -COO-R'(R' system may have a carbon number of halogen atoms The group represented by the alkyl group from 1 to 24) is preferred.

_{When -CH 2} -or -CH= is _{substituted by -SO 2} -in the aforementioned aliphatic hydrocarbon group with 1 to 25 carbon atoms, the aliphatic hydrocarbon group is replaced by -SO ₂ -R'(R' system may have halogen atoms The group represented by the alkyl group having 1 to 24 carbons) is preferred, and may be -SO ₂ CHF ₂ group, -SO ₂ CH ₂ F group, and the like.

The R ^1A , R ^2A , and R ^3A are as described in formula (Y).

R ^4A , R ^5A , R ^6A , R ^7A , R ^8A , R ^9A , R ^10A , R ^11A , R ^12A , R ^13A, and R ^14A alkyl groups with 1 to 6 carbon numbers shown in the formula (Y The alkyl groups with 1 to 6 carbons represented by ^{R 1A} in) are the same.

R ¹ , R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁹¹ , R ¹⁰¹ , R ¹¹¹ , R ² , R ¹² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² , R ¹⁰² , R ¹¹² , R ¹³ , R ²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁶³ , R ⁷³ , R ⁸³ , R ⁹³ , R ^103, and R ¹¹³ show the aromatic hydrocarbon groups with 6 to 18 carbon atoms and the formulae In (Y), the ^{aromatic hydrocarbon groups with carbon numbers 6 to 18 represented by R Y1} are the same, and aryl groups with carbon numbers 6 to 18 are preferred, and phenyl or benzyl is more preferred.

Examples of the substituent system that the aromatic hydrocarbon group having 6 to 18 carbon atoms may have include a halogen atom; a hydroxyl group; a thiol group; an amino group; a nitro group; a cyano group; a -SO ₃ H group.

R ¹ , R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁹¹ , R ¹⁰¹ , R ¹¹¹ , R ² , R ¹² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² , R ¹⁰² , R ¹¹² _{The -CH 2} -or -CH= system contained in the aromatic hydrocarbon group with carbon number 6 to 18 ^{can be -NR 12A} -, -SO ₂ -, -CO-, -O-, -COO-, -OCO -, -CONR ^13A -, -NR ^14A -CO-, -S-, -SO-, -CF ₂ -or -CHF- substitution.

^{R 13, R 23, R 33} , R 43, R 53, R 63, R 73, the carbon atoms shown in R ^83, R ^93, R ¹⁰³ and R ¹¹³ is an aromatic hydrocarbon group of 6 to 18 contained the -CH ₂ -Or -CH= can be -O-, -S-, -NR ^1A -, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CONR ^2A -, -NR ^3A -CO-, -O-CO-NR ^4A -, -NR ^5A -CO-O-, -NR ^6A -CO-NR ^7A -, -CO-S-, -S-CO-S-,- S-CO-NR ^8A -, -NR ^9A -CO-S-, -CS-, -O-CS-, -CS-O-, -NR ^10A -CS-, -NR ^11A -CS-S-,- S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO ₂ -replaced.

_{When -CH 2} -or -CH= contained in the aforementioned aromatic hydrocarbon group having 6 to 18 carbon atoms is substituted, it is preferably substituted _{by -O- or -SO 2 -.}

_{When -CH 2} -or -CH= contained in the aforementioned aromatic hydrocarbon group having 6 to 18 carbon atoms is substituted by -O-, the aromatic hydrocarbon group is an aryloxy group having 6 to 17 carbon atoms such as phenoxy; benzene An oxyethyl group, a phenoxy diethylene glycol group, an aryl alkoxy group of a phenoxy polyalkylene glycol group, etc. are preferable.

_{When -CH 2} -or -CH= is _{substituted by -SO 2} -in the aforementioned aromatic hydrocarbon group having 6 to 18 carbon atoms, the aromatic hydrocarbon group is -SO ₂ -R "(R" represents the carbon number 6 to The group represented by 17 aryl group or C7-17 aralkyl group) is preferred.

The R ² and R ³ systems may be bonded to each other to form a ring. The constituent elements of the ring formed by the bonding of R ² and R ³ include a double bond ^{constituting ring W 1.} That is, the ring formed by the bonding of ^{R 2} and R ^{3 and the ring W 1} form a condensed ring. Specific examples of the condensed ring formed by the ring formed by the bonding of R ² and R ^{3 and the ring W 1} include the ring structures described below.

The ring system formed by bonding R ¹² and R ^{13 to} each other may be the same as the ring formed by bonding ^{R 2} and R ^{3 to each other.}

The ring system formed by bonding R ⁴² and R ^{43 to} each other may be the same as the ring formed by bonding ^{R 2} and R ^{3 to each other.}

The ring system formed by bonding R ⁵² and R ^{53 to} each other may be the same as the ring formed by bonding ^{R 2} and R ^{3 to each other.}

The ring system formed by bonding R ⁶² and R ^{63 to} each other may be the same as the ring formed by bonding ^{R 2} and R ^{3 to each other.}

The ring system formed by bonding R ⁷² and R ^{73 to} each other may be the same as the ring formed by bonding ^{R 2} and R ^{3 to each other.}

The ring system formed by bonding R ⁸² and R ^{83 to} each other may be the same as the ring formed by bonding ^{R 2} and R ^{3 to each other.}

Examples of the ring system formed by bonding R ⁹² and R ^{93 to} each other are the same as the ring formed by bonding ^{R 2} and R ^{3 to each other.}

The ring system formed by bonding R ¹⁰² and R ^{103 to} each other may be the same as the ring formed by bonding ^{R 2} and R ^{3 to each other.}

The ring system formed by bonding R ¹¹² and R ^{113 to} each other may be the same as the ring formed by bonding ^{R 2} and R ^{3 to each other.}

The ring system formed by R ¹ and R ^{2 being} bonded to each other may be the same as the ring formed by bonding ^{R Y1} and R ^{Y2 to each other in formula (Y).}

The ring formed by bonding R ¹ and R ^{2 to} each other is usually a 3 to 10 membered ring, preferably a 5 to 7 membered ring, and more preferably a 5-membered ring or a 6-membered ring.

The ring system formed by bonding R ¹ and R ^{2 to} each other may have a substituent, and examples thereof include the same substituents that may be possessed by the ring W ² to the ring W ¹² .

The ring system formed by bonding R ⁴¹ and R ^{42 to} each other may be the same as the ring formed by bonding ^{R 1} and R ^{2 to each other.}

The ring system formed by bonding R ⁵¹ and R ^{52 to} each other may be the same as the ring formed by bonding ^{R 1} and R ^{2 to each other.}

The ring system formed by bonding R ⁶¹ and R ^{62 to} each other may be the same as the ring formed by bonding ^{R 1} and R ^{2 to each other.}

The ring system formed by bonding R ⁹¹ and R ^{92 to} each other may be the same as the ring formed by bonding ^{R 1} and R ^{2 to each other.}

The ring system formed by bonding R ¹⁰¹ and R ^{102 to} each other may be the same as the ring formed by bonding ^{R 1} and R ^{2 to each other.}

The ring system formed by bonding R ¹¹¹ and R ^{112 to} each other may be the same as the ring formed by bonding ^{R 1} and R ^{2 to each other.}

The ^{divalent bonding group represented by R 6} , R ⁷ and R ⁸ represents a divalent aliphatic hydrocarbon group with 1 to 18 carbon atoms that may have a substituent or a divalent hydrocarbon group with 6 to 18 carbon atoms that may have a substituent The aromatic hydrocarbon group. _{The -CH 2} -contained in the aforementioned divalent aliphatic hydrocarbon group and divalent aromatic hydrocarbon group can be -O-, -S-, -NR ^1B -(R ^1B represents a hydrogen atom or a carbon number of 1 to 6 Alkyl), -CO-, -SO ₂ -, -SO-, -PO ₃ -substituted.

In addition, examples of the substituent system that the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group may have include a halogen atom, a hydroxyl group, a carboxyl group, and an amino group.

The ^{divalent bonding groups represented by R 6} , R ⁷ and R ⁸ are each independently preferably a divalent aliphatic hydrocarbon group with 1 to 18 carbon atoms which may have a substituent, and a carbon which may have a substituent A divalent aliphatic hydrocarbon group having a number of 1 to 12 is more preferable.

Specific examples of the divalent bonding group represented by R ⁶ , R ⁷ and R ^{8 include the bonding groups described below.} In the formula, * is a bonding bond.

R ⁶ and R ⁷ are each independently preferably a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms or a bonding group represented by the following formula, which may have a substituent, and the carbon number that may have a substituent is 1 A divalent aliphatic hydrocarbon group up to 12 or a bonding group represented by the following formula is more preferable. In the formula, * is a bonding bond.

R ⁸ is preferably a bivalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent or a bonding group represented by the following formula. In the formula, * is a bonding bond.

The ^{trivalent bonding group represented by R 9} and R ¹⁰ each independently includes a trivalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent or 3 carbon atoms having 6 to 18 which may have a substituent Valence aromatic hydrocarbon group. _{The -CH 2} -contained in the aforementioned trivalent aliphatic hydrocarbon group can be -O-, -S-, -CS-, -CO-, -SO-, -NR ^11B -(R ^11B represents a hydrogen atom or carbon number 1 to 6 alkyl) substituted.

Examples of the substituent system that the trivalent aliphatic hydrocarbon group and the trivalent aromatic hydrocarbon group may have include a halogen atom, a hydroxyl group, a carboxyl group, and an amino group.

The ^{trivalent bonding group represented by R 9} and R ¹⁰ is each independently preferably a trivalent aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.

Specific examples of the trivalent bonding group represented by R ⁹ and R ^{10 include the bonding groups described below.} In the formula, * is a bonding bond.

Examples of the tetravalent bonding group system represented by R ¹¹ include a tetravalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent or a tetravalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. _{The -CH 2} -contained in the aforementioned 4-valent aliphatic hydrocarbon group can be -O-, -S-, -CS-, -CO-, -SO-, -NR ^11C -(R ^11C is a hydrogen atom or carbon number 1 to 6 alkyl) substituted.

Examples of the substituent system that the aforementioned tetravalent aliphatic hydrocarbon group and the aforementioned tetravalent aromatic hydrocarbon group may have include a halogen atom, a hydroxyl group, a carboxyl group, and an amino group.

The ^{tetravalent bonding group represented by R 11} is each independently preferably a tetravalent aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.

Specific examples of the tetravalent bonding group represented by R ^{11 include the bonding groups described below.} In the formula, * is a bonding bond.

R ¹ is preferably an alkyl group having 1 to 15 carbons, and more preferably an alkyl group having 1 to 10 carbons.

R ² is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.

R ¹ and R ² are preferably bonded to each other to form a ring, more preferably to form an aliphatic ring, and even more preferably an aliphatic ring without unsaturated bonding, to have a pyrrolidine ring or hexahydro The pyridine ring structure is particularly preferred.

R ³ system to a nitro group, a cyano group, a halogen _{atom, -OCF 3, -SCF 3, -SF} 5, -SF 3, fluoroalkyl group (preferably having a carbon number 1 to 25 lines), fluoro-aryl group (preferably based Carbon number 6 to 18), -CO-OR ^111A or -SO ₂ -R ^112A (R ^111A and R ^112A each independently represent an alkyl group with carbon number 1 to 24), preferably,

With cyano group, fluorine atom, chlorine atom, -OCF ₃ , -SCF ₃ , fluoroalkyl group, -CO-OR ^111A or -SO ₂ -R ^112A (R ^111A and R ^112A each independently represent a carbon that may have a halogen atom An alkyl group having a number of 1 to 24) is more preferred, a cyano group or a fluorine atom is even more preferred, and a cyano group is particularly preferred.

R ⁴ and R ⁵ are each independently a nitro group, a cyano group, a halogen atom, -OCF ₃ , -SCF ₃ , _{-SF 5} , _{-SF 3} , fluoroalkyl, fluoroaryl, -CO-OR ^{222 or-} SO ₂ -R ²²² (R ²²² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 25 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms) is preferred,

With nitro group, cyano group, fluorine atom, chlorine atom, -OCF ₃ , -SCF ₃ , fluoroalkyl group, -CO-OR ²²² or -SO ₂ -R ²²² (R ²²² represents a hydrogen atom, which may have a substituent An alkyl group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent) is more preferred,

Take cyano group, -CO-OR ²²² or -SO ₂ -R ²²² (R ²²² is a hydrogen atom, an alkyl group with 1 to 25 carbon atoms that may have substituents, or an aromatic group with 6 to 18 carbon atoms that may have substituents Group hydrocarbon group) is even more preferable, and cyano group is particularly preferable.

At least one of R ⁴ and R ⁵ is preferably a cyano group, more preferably R ⁴ is a cyano group, and R ⁵ is a cyano group, -CO-OR ²²² or -SO ₂ -R ²²² (R ²²² series It represents a hydrogen atom, an optionally substituted alkyl group having 1 to 25 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms).

R ⁴ and R ⁵ preferably have the same structure.

Both R ⁴ and R ⁵ are preferably cyano groups.

R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁹¹ , R ¹⁰¹ and R ¹¹¹ are each independently preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.

R ¹² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² , R ¹⁰² and R ¹¹² are each independently preferably an alkyl group having 1 to 15 carbons, and preferably having 1 to 10 carbons. The alkyl group is more preferable.

R ⁴¹ and R ⁴² are preferably bonded to each other to form a ring, more preferably to form an aliphatic ring, more preferably an aliphatic ring without unsaturated bonding, and particularly preferably a pyrrolidine ring or The structure of the hexahydropyridine ring.

R ⁵¹ and R ⁵² are preferably bonded to each other to form a ring, more preferably to form an aliphatic ring, and even more preferably an aliphatic ring without unsaturated bonding, and particularly preferably a pyrrolidine ring or The structure of the hexahydropyridine ring.

R ⁶¹ and R ⁶² are preferably bonded to each other to form a ring, more preferably to form an aliphatic ring, more preferably an aliphatic ring without an unsaturated bond, and particularly preferably a pyrrolidine ring or The structure of the hexahydropyridine ring.

R ⁹¹ and R ⁹² are preferably bonded to each other to form a ring, more preferably to form an aliphatic ring, more preferably an aliphatic ring without unsaturated bonding, and particularly preferably a pyrrolidine ring or The structure of the hexahydropyridine ring.

R ¹⁰¹ and R ¹⁰² are preferably bonded to each other to form a ring, more preferably to form an aliphatic ring, more preferably an aliphatic ring without an unsaturated bond, and particularly preferably a pyrrolidine ring or The structure of the hexahydropyridine ring.

R ¹¹¹ and R ¹¹² are preferably bonded to each other to form a ring, more preferably to form an aliphatic ring, more preferably an aliphatic ring without an unsaturated bond, particularly preferably having a pyrrolidine ring or The structure of the hexahydropyridine ring.

R ¹³ , R ²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁶³ , R ⁷³ , R ⁸³ , R ⁹³ , R ¹⁰³ and R ¹¹³ are each independently a nitro group; cyano group; halogen atom; -OCF ₃ ; _{-SCF 3; -SF 5; -SF 3} ; fluoroalkyl group having a carbon number of 1 to 25; an aryl group having a carbon number of 6 to 18 fluorine of; -CO-oR ^111A or -SO ₂ -R ^112A (R ^111A R ^112A and Each independently represents an alkyl group having 1 to 24 carbon atoms which may have a halogen atom) is preferably,

With a cyano group; a fluorine atom; a chlorine atom; -OCF ₃ ; -SCF ₃ ; a fluoroalkyl group with 1 to 12 carbon atoms; -CO-OR ^111A or -SO ₂ -R ^112A (R ^111A and R ^112A each independently represent The alkyl group having 1 to 24 carbon atoms which may have a halogen atom) is more preferred,

Cyano is particularly preferred.

R ¹⁴ , R ²⁴ , R ³⁴ , R ⁴⁴ , R ⁵⁴ , R ⁶⁴ , R ⁷⁴ , R ⁸⁴ , R ⁹⁴ , R ¹⁰⁴ , R ¹¹⁴ , R ¹⁵ , R ²⁵ , R ³⁵ , R ⁷⁵ and R ⁸⁵ are independent to the nitro group, a cyano group, a halogen _{atom, -OCF 3, -SCF 3, -SF} 5, -SF 3, -CO-OR 222, (R 222 represents a system may have a halogen -SO ₂ -R ²²² carbon atoms Preferably, an alkyl group having 1 to 25), a fluoroalkyl group having 1 to 25 carbon atoms, or a fluoroaryl group having 6 to 18 carbon atoms,

With nitro group, cyano group, fluorine atom, chlorine atom, -OCF ₃ , -SCF ₃ , fluoroalkyl group, -CO-OR ²²² or -SO ₂ -R ²²² (R ²²² represents the number of carbon atoms that may have halogen atoms 1 To 25 alkyl) is more preferred,

A cyano group, -CO-OR ²²² or -SO ₂ -R ²²² (R ²²² represents an alkyl group with 1 to 25 carbon atoms that may have a halogen atom) is even more preferable,

Cyano is particularly preferred.

R ¹⁴ and R ¹⁵ preferably have the same structure.

R ²⁴ and R ²⁵ preferably have the same structure.

R ³⁴ and R ³⁵ preferably have the same structure.

R ⁷⁴ and R ⁷⁵ preferably have the same structure.

R ⁸⁴ and R ⁸⁵ preferably have the same structure.

The compound represented by formula (I) (hereinafter, sometimes referred to as compound (I)) is a compound represented by formula (I-1A), a compound represented by formula (I-2A) or a compound represented by formula (I-3A) Any one of the compounds shown is more preferable.

[In the formula, Rx ₁ , Rx ₂ , Rx ₃ , Rx ₄ , Rx ₅ , Rx ₆ , Rx ₇ and Rx ₈ each independently represent a hydrogen atom or a substituent. ]

Examples of the substituent systems represented by Rx ₁ to Rx _{8 are the same} ^{as the substituents that the ring W 1} may have.

Examples of the compound (I) include the compounds described below.

Compound (I) is preferably formula (1-1) to formula (1-4), formula (1-7), formula (1-8), formula (1-10), formula (1-12), formula (1-20) to formula (1-25), formula (1-54) to formula (1-57), formula (1-59), formula (1-63) to formula (1-68), formula ( 1-70) to formula (1-78), formula (1-80), formula (1-124) to formula (1-132), formula (1-135), formula (1-137) to formula (1 -142), compounds represented by formula (1-158) to formula (1-172), formula (1-218) to formula (1-227),

More preferably, formula (1-4), formula (1-7), formula (1-10), formula (1-12), formula (1-20), formula (1-22), formula (1-54) ), formula (1-55), formula (1-56), formula (1-59), formula (1-63) to formula (1-65), formula (1-66), formula (1-71) , Formula (1-124), formula (1-125), formula (1-126), formula (1-128), formula (1-131), formula (1-158), formula (1-160), Compounds represented by formula (1-164), formula (1-169), formula (1-218) to formula (1-228),

More preferably, formula (1-55), formula (1-56), formula (1-59), formula (1-64), formula (1-125), formula (1-218) to formula (1- 228) The compound shown in.

The compound represented by formula (II) (hereinafter, sometimes referred to as compound (II)) is, for example, the compounds described below.

Compound (II) is preferably formula (2-1), formula (2-2), formula (2-5) to formula (2-12), formula (2-24) to formula (2-28), formula (2-32), formula (2-33), formula (2-38) to formula (2-44), formula (2-70), formula (2-71), formula (2-103), formula ( The compound shown in 2-104) is more preferably formula (2-1), formula (2-2), formula (2-5) to formula (2-10), formula (2-103), formula (2) -104), the compound represented by the formula (2-105), and the formula (2-106).

The compound represented by formula (III) (hereinafter, sometimes referred to as compound (III)) is, for example, the compounds described below.

The compound represented by formula (IV) (hereinafter, sometimes referred to as compound (IV)) is, for example, the compounds described below.

The compound represented by formula (V) (hereinafter, sometimes referred to as compound (V)) is, for example, the compounds described below.

Compound (V) is preferably from formula (5-1) to formula (5-3), formula (5-6), formula (5-7), formula (5-9), formula (5-15), formula (5-21), formula (5-23), formula (5-25), formula (5-26), formula (5-32), formula (5-36), formula (5-38) The compound is more preferably a compound represented by formula (5-1) to formula (5-3), formula (5-21), formula (5-25), and formula (5-36).

The compound represented by formula (VI) (hereinafter, sometimes referred to as compound (VI)) is, for example, the compounds described below.

Compound (VI) is preferably formula (6-1), formula (6-2), formula (6-4), formula (6-5), formula (6-7), formula (6-8), formula (6-9), formula (6-12), formula (6-15), formula (6-18), formula (6-19), formula (6-22), formula (6-23), formula ( 6-50), formula (6-57), formula (6-69), formula (6-80), formula (6-85), formula (6-94), more preferably the compound represented by formula (6- 1) Compounds represented by formula (6-2), formula (6-4), formula (6-8), formula (6-15), formula (6-22), and formula (6-80).

The compound represented by the formula (VII) (hereinafter, sometimes referred to as compound (VII)) is, for example, the compounds described below.

Compound (VII) is preferably from formula (7-1) to formula (7-9), formula (7-12), formula (7-14), formula (7-17), formula (7-42) to formula The compounds represented by (7-44) and formula (7-57) are more preferably the compounds represented by formula (7-1) to formula (7-8).

The compound represented by formula (VIII) (hereinafter, sometimes referred to as compound (VIII)) is, for example, the compounds described below.

Compound (VIII) is preferably formula (8-1), formula (8-2), formula (8-4), formula (8-5), formula (8-11), formula (8-13) to formula Compounds represented by (8-17), formula (8-25), formula (8-26), formula (8-47), and formula (8-48), More preferred are compounds represented by formula (8-1), formula (8-4), formula (8-5), formula (8-15), formula (8-17), and formula (8-25).

<Production method of compound (I)>

Compound (I) can be produced in the same manner as the method for producing compound (Y) except that compound (Y-A) is substituted with a compound represented by formula (I-A) (hereinafter, sometimes referred to as compound (I-A)).

[In the formula, rings W ¹ and R ¹ to R ^{3 have the} same meanings as described above. ]

Examples of the compound (I-A) include the compounds described below.

The compound (IA) can react a compound represented by formula (IC) (hereinafter, sometimes referred to as compound (IC)) with a compound represented by formula (ID) (hereinafter, sometimes referred to as compound (ID)), and get.

[In the formula, rings W ¹ , R ¹ , R ² and R ^{3 have the} same meanings as described above. The E ₁ series represents the break away from the base. ]

Examples of the leaving group represented by E ₁ include a halogen atom, a p-toluenesulfonyl group, and a trifluoromethylsulfonyl group.

The reaction of compound (I-C) and compound (I-D) is carried out by mixing compound (I-C) and compound (I-D).

Relative to 1 mol of compound (I-C), the usage amount of compound (I-D) is usually 0.1 to 5 mol, preferably 0.5 to 2 mol.

The reaction of compound (I-C) and compound (I-D) can be carried out in the presence of a solvent. Examples of the solvent system include the same solvents used in the reaction of the compound (Y-C) and the compound (Y-D).

The reaction time of compound (I-C) and compound (I-D) is usually 0.1 to 10 hours.

The reaction temperature of compound (I-C) and compound (I-D) is usually -50 to 150°C.

Examples of the compound (I-C) include the compounds described below.

As the compound (I-4), a commercially available product can be used, and examples of the compound (Y-D) are the same as those of the compound (Y-D).

The compound (IC) can be obtained by combining a compound represented by formula (IE) (hereinafter, sometimes referred to as compound (IE)) and a compound represented by formula (IF) (hereinafter, sometimes referred to as compound (IF)) Obtained by reaction.

[In the formula, W ¹ , R ¹ , and R ^{2 have the} same meaning as described above. ]

The reaction system of compound (I-E) and compound (I-F) can be carried out by mixing compound (I-E) and compound (I-F).

The amount of compound (I-F) used is usually 0.1 to 5 mol relative to 1 mol of compound (I-E), preferably 0.5 to 2 mol.

The reaction of compound (I-E) and compound (I-F) can be carried out in the presence of a solvent. Examples of the solvent system include the same solvents used in the reaction of the compound (Y-E) and the compound (Y-F).

The reaction time between compound (I-E) and compound (I-F) is usually 0.1 to 10 hours.

The reaction temperature of the compound (I-E) and the compound (I-F) is usually -50 to 150°C.

Examples of the compound (I-E) include the compounds described below.

As the compound (I-F), the same as the compound (Y-F) can be mentioned.

Compound (I) can also be obtained by using a compound represented by formula (IG) (hereinafter, sometimes referred to as compound (IG)) and compound (IF) instead of using the above-mentioned compound (IA) and compound (YB) .

[In the formula (IG), the rings W ¹ , R ³ , R ⁴ and R ^{5 have the} same meanings as described above. ]

Examples of the compound (I-G) include the compounds described below.

<Production method of compound (II) to compound (VIII)>

Compound (II) can be obtained by, for example, reacting 2 molar equivalents of compound (I-G) with 1 molar equivalent of compound represented by formula (II-1).

[In the formula, R ² , R ¹² and R ^{6 have the} same meaning as described above. ]

Examples of the compound system represented by the formula (II-1) include the compounds described below.

Compound (III) can be obtained, for example, by reacting 2 molar equivalents of compound (I-G) with 1 molar equivalent of compound represented by formula (III-1).

[In the formula, the ring W ¹¹¹ represents the same meaning as described above. ]

Examples of the compound system represented by the formula (III-1) include the compounds described below.

Compound (IV) can be obtained, for example, by reacting 2 molar equivalents of compound (I-G) with 1 molar equivalent of compound represented by formula (IV-1).

[In the formula, ring W ¹¹² , ring W ¹¹³ , and R ^{7 have the} same meaning as described above. ]

Examples of the compound system represented by formula (IV-1) include the compounds described below.

The compound (V) can be obtained, for example, by reacting 2 molar equivalents of the compound (I-A) with 1 molar equivalent of the compound represented by the formula (V-1).

[In the formula, R ⁴ , R ⁸ and R ^{44 have the} same meaning as described above. ]

Examples of the compound system represented by formula (V-1) include the compounds described below.

Compound (VI) can be obtained, for example, by reacting 3 molar equivalents of compound (I-A) with 1 molar equivalent of compound represented by formula (VI-1).

[In the formula, R ⁴ , R ⁸ , R ⁵⁴ and R ^{64 have the} same meaning as described above. ]

Examples of the compound system represented by formula (VI-1) include the compounds described below.

Compound (VII) can be obtained, for example, by reacting 3 molar equivalents of compound (I-G) with 1 molar equivalent of compound represented by formula (VII-1).

[In the formula, R ² , R ¹⁰ , R ⁷² and R ^{82 have the} same meaning as described above. ]

Examples of the compound represented by formula (VII-1) include the compounds described below.

Compound (VIII) can be obtained, for example, by reacting 4 molar equivalent of compound (I-A) with 1 molar equivalent of compound represented by formula (VIII-1).

[In the formula, R ⁴ , R ¹¹ , R ⁹⁴ , R ¹⁰⁴ and R ^{114 have the} same meaning as described above. ]

Examples of the compound system represented by the formula (VIII-1) include the compounds described below.

Relative to 100 parts by mass of the resin (A), the content of the light selective absorption compound (B) is usually 0.01 to 50 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, particularly preferred 1.0 to 5 parts by mass.

<Light selective absorption compound (C)>

The light selective absorption compound (C) is a monomer having a polymerizable group in the molecule and exhibiting maximum absorption at a wavelength of 300 nm or more and a wavelength of less than 360 nm. The light selective absorption compound (C) preferably exhibits a maximum absorption at a wavelength of 320 nm or more and a wavelength of 355 nm or less, and more preferably has a maximum absorption at a wavelength of 330 nm or more and 350 nm or less.

唑啉基、氮丙啶基(aziridino)、乙烯基醚基等陽離子性聚合性基；乙烯性不飽和基等自由基性聚合性基。光選擇吸收化合物(C)所具有的聚合性基較佳係乙烯性不飽和基等自由基性聚合性基。作為乙烯性不飽和基之具體例，可列舉乙烯基、α-甲基乙烯基、丙烯醯基、甲基丙烯醯基、烯丙基、苯乙烯基、(甲基)丙烯醯胺基、乙烯碸基、(甲基)丙烯醯氧基等。 The light selective absorption compound (C) has a polymerizable group. Examples of polymerizable groups include epoxy groups, oxetanyl groups,

Cationic polymerizable groups such as oxazoline, aziridino, and vinyl ether groups; radical polymerizable groups such as ethylenically unsaturated groups. The polymerizable group possessed by the light selective absorption compound (C) is preferably a radical polymerizable group such as an ethylenically unsaturated group. Specific examples of ethylenically unsaturated groups include vinyl, α-methylvinyl, acryl, methacryl, allyl, styryl, (meth)acrylamido, ethylene Sulfonyl, (meth)acryloyloxy and the like.

The light selective absorption compound (C) system includes, for example, a compound having a polymerizable group and a benzotriazole skeleton in the molecule, and a compound having a polymerizable group and a benzimidazole skeleton in the molecule. Compounds, compounds having a polymerizable group and a triazine skeleton in the molecule, compounds having a polymerizable group and a benzophenone skeleton in the molecule, a compound having a polymerizable group and a non-polymerizable cyanoacrylate skeleton in the molecule Compound etc.

Examples of the light selective absorption compound (C) include the compounds described below.

2-[2-(2,4-Dihydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl methacrylate,

2-[2-(4-Ethoxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl methacrylate,

2-[2-(4-Butoxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl methacrylate,

2-[2-(4-Benzyloxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl methacrylate,

4-[2-(2,4-Dihydroxyphenyl)-2H-benzotriazol-5-yloxy]butyl methacrylate,

4-[2-(4-ethoxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]butyl methacrylate,

4-[2-(4-Butoxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]butyl methacrylate,

4-[2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazol-5-yloxy]butyl methacrylate,

4-[2-(4-Benzyloxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]butyl methacrylate,

2-[2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazol-5-yloxy]ethyl methacrylate,

2-[2-(4-octyloxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl methacrylate,

2-[2-(4-Methoxy-5-tert-butyl-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl methacrylate,

2-[2-(4-Methoxy-3-tert-butyl-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl methacrylate,

2-[2-(4-Methoxy-3-methyl-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl methacrylate,

2-[2-Hydroxy-5-(methacryloxyethyl)phenyl]-2H-benzotriazole,

2-[2-Hydroxy-5-(methacryloyl)phenyl]-2H-benzotriazole,

2-[2-Hydroxy-5-(methacryloxypropyl)phenyl]-5-chloro-2H-benzotriazole,

2-[2-hydroxy-5-(methacryloxypropyl)phenyl]-2H-benzotriazole,

N-[3-Benzotriazol-2-yl-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)-benzyl]-2-methylmethacrylic acid amine,

2-[2-(2,4-Dihydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate,

2-[2-(4-Ethoxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate,

2-[2-(4-Butoxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate,

2-[2-(4-Benzoyloxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate,

4-[2-(2,4-Dihydroxyphenyl)-2H-benzotriazol-5-yloxy]butyl acrylate,

4-[2-(4-ethoxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]butyl acrylate,

4-[2-(4-Butoxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]butyl acrylate,

4-[2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazol-5-yloxy]butyl acrylate,

2-[2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate,

4-[2-(4-Benzoyloxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]butyl acrylate,

2-[2-(4-octyloxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate,

2-[2-(4-Methoxy-5-tert-butyl-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate,

2-[2-(4-Methoxy-3-tert-butyl-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate,

2-[2-(4-methoxy-3-methyl-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate,

2-[2-hydroxy-5-(propenyloxyethyl)phenyl]-2H-benzotriazole,

2-[2-hydroxy-5-(propenyl)phenyl]-2H-benzotriazole,

2-[2-Hydroxy-5-(methacryloxypropyl)phenyl]-5-chloro-2H-benzotriazole,

2-[2-hydroxy-5-(methacryloxypropyl)phenyl]-2H-benzotriazole,

N-[3-Benzotriazol-2-yl-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)-benzyl]-2-methacrylamide,

2-hydroxy-4-acryloyloxybenzophenone,

2-hydroxy-4-methacryloxy benzophenone,

2-hydroxy-4-(2-propenyloxy)ethoxybenzophenone,

2-hydroxy-4-(2-methacryloyloxy)ethoxybenzophenone,

2-hydroxy-4-(2-methyl-2-propenyloxy)ethoxybenzophenone,

2,4-Diphenyl-6-[2-hydroxy-4-(2-methacryloxyethoxy)phenyl]-s-triazine,

2,4-Diphenyl-6-[2-hydroxy-4-(2-propenyloxyethoxy)phenyl]-s-triazine,

2,4-bis(2-methylphenyl)-6-[2-hydroxy-4-(3-methylpropenyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,

2,4-bis(2-methylphenyl)-6-[2-hydroxy-4-(3-propenyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,

2,4-bis(2-methoxyphenyl)-6-[2-hydroxy-4-(2-propenyloxyethoxy)phenyl]-s-triazine,

2,4-bis(2-methoxyphenyl)-6-[2-hydroxy-4-(2-methacryloxyethoxy)phenyl]-s-triazine,

2,4-bis(2-ethylphenyl)-6-[2-hydroxy-4-(2-methacryloxyethoxy)phenyl]-s-triazine,

2,4-bis(2-ethylphenyl)-6-[2-hydroxy-4-(2-propenyloxyethoxy)phenyl]-s-triazine,

2,4-bis(2-ethoxyphenyl)-6-[2-hydroxy-4-(2-methacryloxyethoxy)phenyl]-s-triazine,

2,4-Bis(2-ethoxyphenyl)-6-[2-hydroxy-4-(2-propenyloxyethoxy)phenyl]-s-triazine and the like.

In addition, the light selective absorption compound (C) can also include the compounds shown below and the like.

The light selective absorption compound (C) can be commercially available. Specifically, "RUV-93" (Otsuka Chemical Co., Ltd.), "CHISORB 5687" (Double Bond Chemical Co., Ltd.), and "Tinuvin R 796" (BASF Co., Ltd.) can be used. )Wait.

The light selective absorption compound (C) is preferably a compound having a polymerizable group and a benzotriazole skeleton in the molecule, a compound having a polymerizable group and a triazine skeleton in the molecule, or a compound having a polymerizable group and a two A compound of the benzophenone skeleton.

Relative to 100 parts by mass of the resin (A), the content of the light selective absorption compound (C) is usually 0.1 to 70 parts by mass, preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, and 7.5 to 7.5 to 25 parts by mass is still more preferable, particularly preferably 10 to 20 parts by weight.

The content ratio (mass ratio) of the light selective absorbing compound (C) and the light selective absorbing compound (B) is usually the light selective absorbing compound (C)/the light selective absorbing compound (B)=100/5 to 100/30, with 100 /5 to 100/25 is preferred.

The adhesive composition of the present invention may further contain an initiator (D), a radical curable component (E), and a crosslinking agent (F).

<Initiator (D)>

The initiator (D) should just be a compound that causes the polymerization reaction of the light selective absorption compound (C) or the radical curable component (E) contained as needed. The initiator (D) can be a compound that causes polymerization by absorbing the energy of heat (thermal polymerization initiator), and can cause polymerization by absorbing the energy of light Any of the reacted compounds (photopolymerization initiator). In addition, the light system is preferably active energy rays such as visible rays, ultraviolet rays, X-rays, or electron rays.

Examples of thermal polymerization initiators include compounds that generate free radicals by heating and the like (thermal radical generators), compounds that generate acids by heating and the like (thermal acid generators), and those that generate bases by heating and the like. Compounds (hot alkali generators), etc.

Examples of photopolymerization initiators include compounds that generate free radicals by absorbing the energy of light (photo-radical generators), compounds that generate acids by absorbing the energy of light (photoacid generators), and those that generate acid by absorbing light energy. The energy to produce alkali compounds (photobase generators) and so on.

The initiator (D) is preferably selected to be suitable for the polymerization reaction of the light selective absorption compound (C) or the free radical hardening component (E), preferably a free radical generator, and a light free radical generator For better. Examples of the radical generator system include thermal radical generators and photo radical generators.

The initiator (D) may contain two or more types, and a photo radical generator and a thermal radical generator may be used in combination.

Examples of the radical generator system include alkylphenone compounds, benzoin compounds, benzophenone compounds, oxime ester compounds, and phosphine compounds. The radical generator is preferably a photo-radical generator, and from the viewpoint of the reactivity of the polymerization reaction, an oxime ester-based photo-radical generator is more preferred. By using an oxime ester-based radical generator, the reaction rate of the light selective absorption compound (C) or the radical hardening component (E) can be increased even under hardening conditions with weak illuminance or light intensity.

Examples of the alkylphenone compound system include α-aminoalkylphenone compounds, α-hydroxyalkylphenone compounds, and α-alkoxyalkylphenone compounds.

α-Amino alkyl phenone compounds include 2-methyl-2-morpholino-1-(4-methylthiophenyl) propane-1-one (2-methyl-2-morpholino-1 -(4-methylsulfanylphenyl)propan-1- one), 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-dimethylamino-1-(4-morpholine Phenyl)-2-(4-methylphenylmethyl)butan-1-one and the like, preferably 2-methyl-2-morpholinyl-1-(4-methylsulfanyl Phenyl) propane-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one and the like. α-Aminoalkylphenone compounds can use IRGACURE (registered trademark) 127, 184, 369, 369E, 379EG, 651, 907, 1173, 2959, (above, made by BASF JAPAN Co., Ltd.), SEIKUOL (registered trademark) ) Commercial products such as BEE (manufactured by Seiko Chemical Co., Ltd.).

Examples of the benzoin compound system include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

The benzophenone compound system includes, for example, benzophenone, methyl phthalate, 4-phenylbenzophenone, and 4-benzophenone-4'-methyl diphenyl sulfide , 3,3',4,4'-Tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. Commercially available benzophenone compounds can be used.

The oxime ester compound system includes N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl) (4-Phenylthiophenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)- 9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl -2,4-Dioxopentylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine and the like. The oxime compound system can use IRGACURE OXE-01, OXE-02, OXE-03 (all of which are made by BASF JAPAN), N-1919, NCI-730, NCI-831, NCI-930 (made by ADEKA), PBG3057 ( Commercial products such as those manufactured by TRONLY.

Phosphine compound systems include phenyl (2,4,6-trimethylbenzyl) phosphine oxide, diphenyl (2,4,6-trimethylbenzyl) phosphine oxide, etc. . The phosphine compound system includes IRGACURE (registered product) TPO, IRGACURE 819 (manufactured by BASF JAPAN Co., Ltd.), and the like.

Examples of the acid generator system include onium salts such as aromatic iodonium salts and aromatic sulfonium salts; aromatic diazonium salts; iron-aromatic hydrocarbon complexes and the like.

The aromatic iodonium salt is a compound having a diaryl iodonium cation, and the cation typically includes a diphenyl iodonium cation. The aromatic sulfonium salt is a compound having a triarylsulfonium cation, and the cation typically includes triphenylsulfonium cation and 4,4'-bis(diphenylsulfonium)diphenylsulfide cation. The aromatic diazonium salt is a compound having a diazonium cation, and the cation typically includes a benzenediazonium cation. In addition, the iron-aromatic hydrocarbon complex is typically a cyclopentadienyl iron (II) aromatic hydrocarbon cation complex salt.

The cation system shown above is paired with anion (anion) to form a photocation generator. , A hexafluorophosphate anion PF ₆ ^{- -} If an anion constituting the optical cation generator of embodiment, the phosphorus-based special anion _{[(Rf) n PF 6-} n] include, hexafluoroantimonate anion SbF ₆ ^-, pentafluoro hydroxy antimony anion SbF ₅ (OH) ^-, hexafluoroarsenate anion AsF ₆ ^-, tetrafluoroborate anion ₄ BF ^-, tetrakis (pentafluorophenyl) borate anion _{B (C 6 F 5) 4} - and the like. From the viewpoint of safety of curable cationic polymerizable compound and the resulting adhesive layer, the phosphorus-based special anion _{[(Rf) n PF 6-} n] -, hexafluorophosphate anion PF ₆ ^- , Si (pentafluorophenyl) borate anion B(C ₆ F ₅ ) ₄ ^- and hexafluoroantimonate anion SbF ₆ ^- are preferred.

Examples of the photobase generator system include urethane compounds, α-aminoketone compounds, quaternary ammonium compounds, O-acetoxime compounds, and aminocyclic acetone compounds.

The urethane compound system includes, for example, 1-(2-anthraquinone) ethyl 1-hexahydropyridine carboxylate, 1-(2-anthraquinone) ethyl 1H-2-ethylimidazole-1- Carboxylate, 9-anthrylmethyl 1-hexahydropyridine carboxylate, 9-anthrylmethyl N,N-diethyl carbamate, 9-anthrylmethyl N-propyl carbamate Ester, 9-anthrylmethyl N-cyclohexyl carbamate, 9-anthrylmethyl 1H-imidazole-1-carboxylate, 9-anthrylmethyl N,N-dioctyl carbamate , 9-anthrylmethyl 1-(4-hydroxyhexahydropyridine) carboxylate, 1-pyrenylmethyl 1-hexahydropyridine carboxylate, bis[1-(2-anthryl)ethyl] 1 ,6-Hexanediyl biscarbamate, bis(9-anthrylmethyl) 1,6-hexanediyl biscarbamate, etc.

The α-aminoketone compound system is known, for example, as follows. Examples include 1-phenyl-2-(4-morpholinylbenzyl)-2-dimethylaminobutane, 2-(4-methylthiobenzyl)-2-morpholinyl Propane etc.

Examples of quaternary ammonium compounds that become photobase generators include 1-(4-phenylthiobenzylmethyl)-1-azone-4-azabicyclo[2,2,2]octane Tetraphenylborate, 5-(4-phenylthiobenzylmethyl)-1-aza-5-azabicyclo[4,3,0]-5-nonenetetraphenylboron Ester, 8-(4-phenylthiobenzylmethyl)-1-aza-8-azone heterobicyclo[5,4,0]-7-undecenetetraphenylborate, etc. .

The amino cycloacetone compound system that becomes the photobase generator includes, for example, 2-diethylamino-3-phenylcycloacetone, 2-diethylamino-3-(1-naphthyl)cycloacetone, 2 -Pyrrolidinyl-3-phenylcycloacetone, 2-imidazolyl-3-phenylcycloacetone, 2-isopropylamino-3-phenylcycloacetone, etc.

Thermal base generators include 2-(4-biphenyl)-2-propyl carbamate and 1,1-dimethyl-2-cyanoethyl carbamate and other carbamate derivatives. Products, urea or N,N,N'-trimethylurea and other urea derivatives, 1,4-dihydronicotinamide and other dihydropyridine derivatives, dicyandiamide, organic or inorganic salts, etc. Salts composed of acids and bases, etc.

Relative to 100 parts by mass of the resin (A), the content of the initiator (D) is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and 1 to 3 The mass part is even better.

<Free radical hardening component (E)>

Examples of the radical curable component (E) include monomers or oligomers that are cured by radical polymerization.

Examples of the radical curable component (E) system include monofunctional or polyfunctional (meth)acrylate-based compounds, styrene-based compounds, and vinyl-based compounds.

The adhesive composition system of the present invention may contain two or more kinds of radical curable components (E).

The (meth)acrylate-based compound system includes (meth)acrylate monomers having at least one (meth)acryloyloxy group in the molecule, (meth)acrylamide monomers, and molecular Compounds containing (meth)acrylic groups such as (meth)acrylic oligomers having at least two (meth)acrylic groups in the interior. The (meth)acrylic oligomer is preferably a (meth)acrylate oligomer having at least two (meth)acryloxy groups in the molecule. (Meth)acrylic compound system may be used individually by 1 type, and may use 2 or more types together.

The (meth)acrylate single system includes monofunctional (meth)acrylate monomers having one (meth)acryloyloxy group in the molecule, and two (meth)acrylic acid ester monomers in the molecule. A bifunctional (meth)acrylate monomer of an acyloxy group, and a polyfunctional (meth)acrylate monomer having 3 or more (meth)acryloxy groups in the molecule.

The monofunctional (meth)acrylate single system includes alkyl (meth)acrylate. In the alkyl (meth)acrylate, when the number of carbon atoms in the alkyl group is 3 or more, it may be linear, branched, or cyclic. (Meth) acrylate alkyl ester series include methyl (meth)acrylate, ethyl (meth)acrylate, (former Base) isopropyl acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.

In addition, the monofunctional (meth)acrylate monomers can also be exemplified: (meth) aralkyl (meth)acrylates such as benzyl (meth)acrylate; (meth) terpene alcohols (meth) ) Acrylic esters; (meth)acrylates having a tetrahydrofuran methyl structure such as tetrahydrofuran methyl (meth)acrylate; cyclohexyl (meth)acrylate, cyclohexyl methyl methacrylate, dicyclopentyl acrylate, ( (Meth)acrylates having a cycloalkyl group at the alkyl group such as dicyclopentenyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, etc.; (meth)acrylate N,N-dimethyl (Meth)aminoethyl acrylate; 2-phenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethyl (meth)acrylate (Meth)acrylates etc. which have an ether bond in an alkyl part, such as a base carbitol ester and a phenoxy polyethylene glycol (meth)acrylate.

Furthermore, the monofunctional (meth)acrylate monosystem includes: monofunctional (meth)acrylate having a hydroxyl group at the alkyl part; monofunctional (meth)acrylate having a carboxyl group at the alkyl part. Monofunctional (meth)acrylates having a hydroxyl group at the alkyl portion include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 4-(meth)acrylate Hydroxybutyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, trihydroxymethylpropane mono(meth)acrylate, neopenteritol mono(meth)acrylate. Monofunctional (meth)acrylates having a carboxyl group at the alkyl portion include 2-carboxyethyl (meth)acrylate, ω-carboxy-polycaprolactone (n=2) mono(meth)acrylate, 1-[2-(Meth)acryloyloxyethyl]phthalic acid, 1-[2-(meth)acryloyloxyethyl]hexahydrophthalic acid, 1-[2-( (Meth)acryloyloxyethyl]succinic acid, 4-[2-(meth)acryloyloxyethyl] trimellitic acid, N-(meth)acryloyloxy-N',N' -Dicarboxymethyl-p-phenylenediamine, etc.

The (meth)acrylamide monomer is preferably (meth)acrylamide having a substituent at the N-position. A typical example of the substituent at the N-position is an alkyl group, but it can also form a ring together with the nitrogen atom of (meth)acrylamide, except for the carbon atom and the nitrogen atom of (meth)acrylamide In addition, it may have an oxygen atom as a member of the ring. Furthermore, the carbon atom system constituting the ring may be bonded to a substituent such as an alkyl group or a pendant oxy group (=O).

唑啶酮(3-acryloyl-2-oxazolidinone)、4-丙烯醯基嗎啉、N-丙烯醯基六氫吡啶、N-甲基丙烯醯基六氫吡啶等。 Examples of N-substituted (meth)acrylamide series include: N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide Amine, N-butyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-alkyl(meth)acrylamide of N-hexyl(meth)acrylamide Amines; such as N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide and N,N-dialkyl(meth)acrylamide, etc. In addition, the N-substituent may be an alkyl group having a hydroxyl group. Examples of the N-substituent include N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide and the like. Furthermore, specific examples of the above-mentioned N-substituted (meth)acrylamide forming a 5-membered ring or a 6-membered ring include N-propenylpyrrolidine and 3-propenyl-2-

3-acryloyl-2-oxazolidinone, 4-acryloylmorpholine, N-acryloylhexahydropyridine, N-methacryloylhexahydropyridine, etc.

The bifunctional (meth)acrylate single system can be enumerated:

Ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di( Alkyl glycol di(meth)acrylates such as meth)acrylate, 1,9-nonanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate;

Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate Meth)acrylate, Polyoxyalkylene glycol di(meth)acrylate such as polypropylene glycol di(meth)acrylate and polytetramethylene glycol di(meth)acrylate;

Halogen-substituted di(meth)acrylate of alkanediol such as tetrafluoroethylene glycol di(meth)acrylate;

Di(meth)acrylic acid ester;

Hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate and other hydrogenated dicyclopentadiene or tricyclodecane dialkyl alcohol di(meth)acrylic acid ester;

烷-2,5-二基二(甲基)丙烯酸酯[別名：二

烷二醇二(甲基)丙烯酸酯]等二

烷二醇或二

烷二烷醇之二(甲基)丙烯酸酯； 1,3-two

Alkyl-2,5-diyl di(meth)acrylate [alias: two

Alkanediol di(meth)acrylate] etc.

Alkanediol or di

Alkanediol di(meth)acrylate;

Bisphenol A ethylene oxide adduct diacrylate, bisphenol F ethylene oxide adduct diacrylate, and other bisphenol A or bisphenol F alkylene oxide adducts Acrylate;

Acrylic acid adduct of bisphenol A diglycidyl ether, acrylic acid adduct of bisphenol F diglycidyl ether, bisphenol A or bisphenol F di(meth)acrylate epoxy ester;

Polysiloxane di(meth)acrylate;

Di(meth)acrylate of neopentyl glycol hydroxytrimethyl acetate;

2,2-bis[4-(meth)propenyloxyethoxyethoxyphenyl]propane;

2,2-bis[4-(meth)propenyloxyethoxyethoxycyclohexyl]propane;

烷]之二(甲基)丙烯酸酯； 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-di

Alkyl]bis(meth)acrylate;

Ginseng (hydroxyethyl) trimeric isocyanate di(meth)acrylate; etc.

Examples of multifunctional (meth)acrylate monomer systems with more than three functions include: glycerol tri(meth)acrylate, alkoxylated glycerol tri(meth)acrylate, trimethylolpropane tri(methyl) Acrylic Ester, di(trimethylolpropane) tri(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, neopentyl erythritol tri(meth)acrylate, neopentyl tetrakis Alcohol tetra (meth) acrylate, dineopentaerythritol tetra (meth) acrylate, dineopentaerythritol penta (meth) acrylate, dineopentaerythritol hexa (meth) acrylate and other trifunctional The poly(meth)acrylate of the above aliphatic polyol; the poly(meth)acrylate of the halogen-substituted polyol with more than three functions; the tri(meth)acrylate of the alkylene oxide adduct of glycerin; three Tris(meth)acrylate of alkylene oxide adduct of hydroxymethylpropane; 1,1,1-parameter [(meth)acryloyloxyethoxyethoxy]propane; parameter (hydroxyethyl) ) Trimeric isocyanate tri(meth)acrylate, etc.

In addition, commercially available products can be used. Examples of commercially available products include A-DPH-12E, A-TMPT, and A-9300 (manufactured by Shinnakamura Chemical Co., Ltd.).

The (meth)acrylic oligomer system includes urethane (meth)acrylic oligomers, polyester (meth)acrylic oligomers, epoxy (meth)acrylic oligomers, and the like.

The so-called amine ester (meth)acrylic oligomer is a compound having an amine ester bond (-NHCOO-) and at least two (meth)acrylic groups in the molecule. Specifically, it can be the product of the amination reaction product of a hydroxyl-containing (meth)acrylic monomer having at least one (meth)acrylic acid group and at least one hydroxyl group in the molecule and polyisocyanate , Or a amine ester compound containing an isocyanate group at the end obtained by reacting a polyol with a polyisocyanate, and a (meth)acrylic acid having at least one (meth)acrylic acid group and at least one hydroxyl group in the molecule Monomer amine esterification reaction product, etc.

The hydroxyl-containing (meth)acrylic monomer system used in the above-mentioned amine esterification reaction may be, for example, a hydroxyl-containing (meth)acrylate monomer, and specific examples thereof include 2-hydroxyethyl (meth)acrylate , 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol di(meth)acrylate, three Hydroxymethylpropane bis(methyl) Acrylate, neopentylerythritol tri(meth)acrylate, dineopentylerythritol penta(meth)acrylate. Specific examples other than hydroxyl-containing (meth)acrylate monomers include N-hydroxyalkyl (meth)acrylamide, such as N-hydroxyethyl (meth)acrylamide, and N-hydroxymethyl (meth)acrylamide. Base) acrylamide monomer.

The polyisocyanate system supplied to the amination reaction with hydroxyl-containing (meth)acrylic monomers includes hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, Toluene diisocyanate, xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates (for example, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, etc.), triphenyl Di- or tri-isocyanates such as methane triisocyanate and benzhydryl benzene triisocyanate, and polyisocyanates obtained by multimerizing the above-mentioned diisocyanates, etc.

In addition, in addition to aromatic, aliphatic or alicyclic polyols, polyester polyols, Polyether polyols, etc. Aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, three Hydroxymethylethane, trimethylolpropane, bis(trimethylolpropane), neopentylerythritol, dineopentylerythritol, dimethylolheptane, dimethylolpropanoic acid, dimethylol Butyric acid, glycerin, hydrogenated bisphenol A, etc.

The polyester polyol is obtained by the dehydration condensation reaction of the above-mentioned polyol and polycarboxylic acid or its anhydride. If the example of polycarboxylic acid or its anhydride can be acid anhydride, it is indicated by "(anhydride)", there are succinic acid (anhydride), adipic acid, maleic acid (anhydride), itaconic acid (anhydride), Trimellitic acid (anhydride), pyromellitic acid (anhydride), hexahydrophthalic acid (anhydride), isophthalic acid, terephthalic acid, hexahydrophthalic acid (anhydride), etc.

In addition to the polyether polyol-based polyalkylene glycol, polyoxyalkylene-modified polyols obtained by the reaction of the above-mentioned polyols or dihydroxybenzenes with alkylene oxides may also be used.

The so-called polyester (meth)acrylate oligomer means an oligomer having an ester bond and at least two (meth)acryloyloxy groups in the molecule.

The polyester (meth)acrylate oligomer system can be obtained by dehydration condensation reaction of (meth)acrylic acid, polycarboxylic acid or its anhydride, and polyhydric alcohol, for example.

Polycarboxylic acid or its anhydride series may include succinic anhydride, adipic acid, maleic anhydride, itaconic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, phthalic acid, succinic acid , Maleic acid, itaconic acid, trimesic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, etc.

Polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolethane Methylolpropane, di(trimethylolpropane), neopentylerythritol, dineopentylerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutanoic acid, glycerin, hydrogenated di Phenol A and so on.

The epoxy (meth)acrylic oligomer can be obtained by the addition reaction of polyglycidyl ether and (meth)acrylic acid. The epoxy (meth)acrylic oligomer has at least two (meth)acryloxy groups in the molecule.

Polyglycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether. Glyceryl ether and so on.

Styrene compounds include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene Alkyl styrenes such as ene, butyl styrene, hexyl styrene, heptyl styrene, and octyl styrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene ; Nitrostyrene; Acetylstyrene; Methoxystyrene; and Divinylbenzene.

Vinyl single systems include: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate and other fatty acid vinyl esters; vinyl chloride, vinyl bromide and other vinyl halides; Vinylidene chloride and other vinyl halides; nitrogen-containing heteroaromatic vinyl such as vinyl pyridine, vinyl pyrrolidone, and vinyl carbazole; butadiene, isoprene, chloroprene and other conjugated dienes; And unsaturated nitriles such as acrylonitrile and methacrylonitrile.

The radical curable component (E) is preferably a (meth)acrylate compound, and more preferably a polyfunctional (meth)acrylate compound. The polyfunctional (meth)acrylate compound is preferably trifunctional or higher.

Relative to 100 parts by mass of the resin (A), the content of the radical curable component (E) is usually 0.5 to 100 parts by mass, preferably 1 to 70 parts by mass, more preferably 3 to 50 parts by mass, and 5 It is more preferably to 30 parts by mass, and particularly preferably 7.5 to 20 parts by mass.

<Crosslinking agent (F)>

The cross-linking agent (F) series can include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, metal chelate-based cross-linking agents, etc., in particular, from the handling of the adhesive composition From the viewpoints of time, durability of the adhesive layer, crosslinking speed, etc., an isocyanate-based crosslinking agent is preferred.

The isocyanate-based crosslinking agent is preferably a compound having at least two isocyanate groups (-NCO) in the molecule, for example, aliphatic isocyanate-based compounds (e.g., hexamethylene diisocyanate, etc.), alicyclic isocyanate-based compounds ( Such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate), aromatic isocyanate compounds (examples Such as toluene diisocyanate, xylylene diisocyanate diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.). In addition, the crosslinking agent (F) may be an adduct produced with the polyol compound of the aforementioned isocyanate compound [for example, an adduct produced with glycerin, trimethylolpropane, etc.], Trimeric isocyanate, biuret type compound, and polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol and other amine ester preforms obtained by addition reaction Derivatives such as polymer isocyanate compounds. The crosslinking agent (F) can be used alone or in combination of two or more kinds. Among these, representative systems include aromatic isocyanate compounds (for example, toluene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (for example, hexamethylene diisocyanate), or these polyol compounds (For example, glycerol, trimethylolpropane) produced adduct, or trimeric isocyanate body. If the crosslinking agent (F) is an aromatic isocyanate compound and/or these polyol compounds, or an adduct produced by a trimeric isocyanate body, it is beneficial to form an optimal crosslink density (or crosslink structure) , So it can improve the durability of the adhesive layer. In particular, if it is an adduct produced from a toluene diisocyanate compound and/or these polyol compounds, even when, for example, an adhesive layer is applied to a polarizing plate, the durability can be improved.

The content of the crosslinking agent (F) is relative to 100 parts by mass of the resin (A). The content of the crosslinking agent (F) is usually 0.01 to 25 parts by mass, preferably 0.1 to 15 parts by mass, more preferably 0.15 to 7 Parts by mass, more preferably 0.2 to 5 parts by mass, particularly preferably 0.25 to 2 parts by mass.

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

The silane compound (G) system includes, for example, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, 3-glycidoxy propyl trimethoxy Silane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ethyl trimethoxy Silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-hydrothiopropyltrimethoxysilane Silane and so on.

The silane compound (G) may be a polysiloxane oligomer. If the specific example of the polysiloxane oligomer is expressed in the form of a combination of monomers, it is as follows.

3-Hydroxythiopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-hydrothiopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-hydrothiopropyltri Ethoxysilane-tetramethoxysilane oligomer, 3-hydrosulfanyl propyl triethoxysilane-tetraethoxysilane oligomer and other oligomers containing sulfhydryl propyl group; sulfhydryl group Methyltrimethoxysilane-tetramethoxysilane oligomer, thiomethyltrimethoxysilane-tetraethoxysilane oligomer, thiomethyltriethoxysilane-tetramethoxysilane Silane oligomers, thiomethyltriethoxysilane-tetraethoxysilane oligomers and other oligomers containing thiomethyl; 3-glycidoxypropyltrimethoxysilane-tetra Methoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-glycidol Oxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-glycidoxysilane copolymer Propylmethyldiethoxysilane-tetraethoxysilane copolymer and other copolymers containing 3-glycidoxypropyl; 3-methacryloxypropyl trimethoxysilane-tetramethoxy Silane oligomer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane Oligomer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane Silane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3- Methacryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer Oligomers containing methacryloxypropyl; 3-propyleneoxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-propyleneoxypropyltrimethoxysilane -Tetraethoxysilane oligomer, 3-propenyloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropyltriethoxysilane-tetraethoxy -Based silane oligomer, 3-propenyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldimethoxysilane-tetraethoxy -Based silane oligomer, 3-propenyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldiethoxysilane-tetraethoxy Oligomers containing acryloxy propyl groups such as vinyl silane oligomers; vinyl trimethoxysilane-tetramethoxysilane oligomers, vinyl trimethoxysilane-tetraethoxysilane oligomers, Vinyltriethoxysilane-tetramethoxysilane oligomer, vinyltriethoxysilane-tetraethoxysilane oligomer, vinylmethyldimethoxysilane-tetramethoxysilane oligomer Polymer, vinyl methyl dimethoxy silane-tetraethoxy silane oligomer, vinyl methyl diethoxy silane-tetramethoxy silane oligomer, vinyl methyl diethoxy silane oligomer -Tetraethoxysilane oligomer and other vinyl-containing oligomers; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethyl Oxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-amino Propylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethyl Amine group-containing copolymers such as oxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc.

The silane compound (G) may be a silane compound represented by the following formula (g1).

[In the formula, A represents an alkanediyl group with 1 to 20 carbons or a divalent alicyclic hydrocarbon group with 3 to 20 carbons, and the -CH ₂ -system constituting the alkanediyl group and the alicyclic hydrocarbon group can be- O- or -CO- substituted, R ⁴¹ represents an alkyl group with 1 to 5 carbons, R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent an alkyl group with 1 to 5 carbons or carbon number Alkoxy from 1 to 5. ]

The alkanediyl system with 1 to 20 carbon atoms shown in A includes methylene, 1,2-ethanediyl, 1,3-propanediyl, 1,4-butanediyl, 1,5- Pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl, 1,12-dodecanediyl, 1,14-tetradecanediyl, 1,16-hexadecanediyl, 1,18-octadecanediyl and 1,20-eicosanediyl. Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include 1,3-cyclopentanediyl and 1,4-cyclohexanediyl. _{The -CH 2} -that constitutes the alkanediyl group and the alicyclic hydrocarbon group is substituted by -O- or -CO-, and examples include -CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -CO-O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -CO-O-CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ -And -CH ₂ CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ CH ₂ CH ₂ -.

Examples of the alkyl groups having 1 to 5 carbon atoms represented by R ⁴¹ to R ⁴⁶ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl and pentyl, and R ⁴² to The alkoxy groups with carbon numbers 1 to 5 shown by R ⁴⁶ include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tertiary butoxy and pentoxy. Oxy.

The silane compound system represented by the formula (g1) includes, for example, (trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl) Yl)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(trimethyl) Oxysilyl)octane, 1,8-bis(triethoxysilyl)octane, 1,8-bis(tripropoxysilyl)octane and other bis(tri-C1-5 alkoxides) Group) C1-10 alkane; bis(dimethoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane, 1,2-bis(dimethoxyethyl) Silyl)ethane, 1,4-bis(dimethoxymethylsilyl)butane, 1,4-bis(dimethoxyethylsilyl)butane, 1,6-bis(dimethylsilyl)butane Oxymethylsilyl)hexane, 1,6-bis(dimethoxyethylsilyl)hexane, 1,8-bis(dimethoxymethylsilyl)octane, 1,8- Bis(dimethoxyethylsilyl)octane and other bis(diC1-5 alkoxy C1-5 alkylsilyl)C1-10 alkanes; 1,6-bis(methoxydimethylsilyl) ) Bis(mono-C1-5 alkoxy-diC1-5 alkylsilyl) C1-10 alkanes such as hexane, 1,8-bis(methoxydimethylsilyl)octane, etc. Among these, 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 other bis(triC1- 3Alkoxysilyl)C1-10 alkane is preferred, especially 1,6-bis(trimethoxysilyl)hexane and 1,8-bis(trimethoxysilyl)octane are more preferred .

Relative to 100 parts by mass of the resin (A), the content of the silane compound (G) is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.15 to 7 parts by mass, and still more preferably 0.2 to 5 parts by mass. Parts by mass, particularly preferably 0.25 to 2 parts by mass.

The adhesive composition can further contain one or more kinds of antistatic agents, solvents, crosslinking catalysts, tackifiers, plasticizers, softeners, pigments, rust inhibitors, inorganic fillers, light scattering properties Additives such as fine particles.

The adhesive layer of the present invention is, for example, the adhesive composition of the present invention is dissolved or dispersed in a solvent to form an adhesive composition containing the solvent, and then the adhesive composition is coated on the surface of the substrate and dried After that, it is formed by irradiation with active energy rays. The adhesive layer of the present invention may also refer to the light-cured material of the adhesive composition.

The base material is suitably a plastic film, and specifically, a release film subjected to a release treatment can be cited. Examples of peeling films include: applying release treatment such as silicone treatment on one side of a film made of resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarylate. Become.

The conditions (drying temperature, drying time) for drying the coating film formed by the solvent-containing adhesive composition can be appropriately set according to its composition or concentration, but are preferably 60 to 150° C. for 1 to 60 minutes.

The active energy ray irradiation of the coating film after drying is preferably ultraviolet irradiation. Department of ultraviolet irradiation illuminance at 10mW / cm ² to 3000mW / cm ² is preferred. In addition, the cumulative amount of ultraviolet light is preferably 10 m J/cm ² to 5000 m J/cm ² .

The ultraviolet lamps for ultraviolet irradiation can be mercury lamps, metal halide lamps, and LED lamps.

The adhesive layer of the present invention preferably satisfies the adhesive layer of the following formula (3), and more preferably, the adhesive layer satisfies the formula (4).

A(380)≧0.60 (3)

[In formula (3), A(380) represents the absorbance at a wavelength of 380nm. ]

A(380)/A(420)≧5 (4)

[In formula (4), A(380) represents the absorbance at a wavelength of 380nm, and A(420) represents the absorbance at a wavelength of 420nm. ]

The larger the value of A(380), the higher the absorption at the wavelength of 380nm. If the value of A(380) is less than 0.60, the absorption at the wavelength of 380nm is low, and the components (such as display devices such as organic EL elements or liquid crystal retardation films) that are easily degraded by light near ultraviolet rays are likely to cause degradation. The value of A(380) is preferably 0.75 or more, more preferably 0.85 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(380)/A(420) represents the magnitude of absorption at a wavelength of 380nm relative to the magnitude of absorption at a wavelength of 420nm. The larger the value, the more specific the absorption in the wavelength region near ultraviolet rays. The value of A(380)/A(420) is preferably 5 or more, more preferably 20 or more, even more preferably 50 or more, and particularly preferably 100 or more.

The thickness of the adhesive layer of the present invention is usually less than 200 μm, preferably less than 100 μm, more preferably less than 20 μm, still more preferably less than 12 μm or less than 12 μm, still more preferably less than 10 μm, particularly preferably less than 7 μm . Also, it is usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, and still more preferably 2 μm or more.

According to the present invention, even if it is an adhesive layer of a film of less than 12 μm, it can sufficiently absorb ultraviolet rays, which is advantageous from the viewpoint of thinning of the display device.

The gel fraction of the adhesive layer of the present invention is usually 50 to 99.9% by mass, preferably 60 to 99% by mass, more preferably 70 to 95% by mass, and still more preferably 75 to 90% by mass.

<Optical film with adhesive layer>

The adhesive composition of the present invention and the adhesive layer formed by the adhesive composition can be used, for example, for bonding optical films.

The optical film with the adhesive layer of the optical film layered on at least one area of the adhesive layer of the present invention is also included in the present invention.

The adhesive layer-attached optical film system of the present invention can dissolve or disperse the aforementioned adhesive composition in a solvent to form an adhesive composition containing the solvent, and then apply the adhesive composition on the surface of the optical film and make After drying, it is formed by irradiation with active energy rays. In addition, an adhesive layer may be formed on the release film in the same manner, and the adhesive layer may be laminated (transferred) on the surface of the optical film.

The optical film is a film that has optical functions such as light penetration, reflection, and absorption. The optical film can be a single-layer film or a multi-layer film. Examples of the optical film system include a polarizing film, a retardation film, a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffuser film, a light-concentrating film, etc., and a polarizing film, a retardation film, or these laminated films are preferred.

The light-concentrating film is used for the purpose of controlling the optical path. It can be a prismaticprism array sheet or a lens array sheet, a dot-attached sheet, etc.

The brightness enhancement film is used for the purpose of enhancing the brightness of the liquid crystal display device using the polarizing plate. Specifically, it can be a reflection type polarizing separator designed to produce anisotropy in reflectance by laminating a plurality of thin films with mutually different refractive index anisotropies, and a cholesteric liquid crystal polymer supported on a substrate film. Circularly polarized light separation sheet of alignment film or alignment liquid crystal layer, etc.

The polarizing film is a film that absorbs linearly polarized light with a vibration surface parallel to its absorption axis, and transmits linearly polarized light with a vibration surface orthogonal to the absorption axis (parallel to the transmission axis). For example, it can be used in The polyvinyl alcohol resin film absorbs and aligns the film with dichroic pigments.

Examples of the dichroic dye system include iodine and dichroic organic dyes.

The degree of saponification of the polyvinyl alcohol resin is usually 85 mol% to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, for example, polyvinyl formaldehyde or polyvinyl acetal modified by aldehydes. The degree of polymerization of the polyvinyl alcohol resin is usually 1,000 to 10,000, preferably 1,500 to 5,000.

Generally, a polarizing film is used as an embryo film formed by forming a polyvinyl alcohol-based resin into a film. The polyvinyl alcohol-based resin system can be formed into a film by a known method. The thickness of the embryonic membrane is usually 1 to 150 μm, and if the ease of extension is considered, it is preferably 10 μm or more.

For example, the polarizing film is implemented: the step of uniaxially extending the embryonic membrane; the step of dyeing the film with a dichroic pigment to adsorb the dichroic pigment; the step of treating the film with an aqueous solution of boric acid; and the step of washing the film; Finally, it is manufactured by drying. The thickness of the polarizing film is usually 1 to 30 μm. From the viewpoint of thinning the optical film with the adhesive layer, it is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less.

Preferably, it is a polarizing plate in which a protective film is provided on at least one side of the polarizing film with an adhesive interposed therebetween.

A well-known adhesive is used for the adhesive system, and it may be a water-based adhesive or an active energy ray hardening type adhesive.

Examples of water-based adhesives include commonly used water-based adhesives (for example, adhesives composed of polyvinyl alcohol-based resin aqueous solutions, water-based two-component urethane emulsion adhesives, aldehyde compounds, Crosslinking agents such as epoxy compounds, melamine compounds, methylol compounds, isocyanate compounds, amine compounds, polyvalent metal salts, etc.). Among these, an aqueous adhesive composed of a polyvinyl alcohol-based resin aqueous solution can be suitably used. In addition, when using a water-based adhesive, after bonding the polarizing film and the protective film, it is preferable to perform a step of drying to remove the water contained in the water-based adhesive. After the drying step, for example, the temperature can be set at a temperature of about 20 to 45° C. to perform the aging step of aging. The adhesive layer formed by the water-based adhesive is usually 0.001 to 5 μm.

The so-called active energy ray curable adhesive refers to an adhesive that is cured by irradiating active energy rays such as ultraviolet rays or electron rays. The curable composition of a curable resin, a curable composition containing a binder resin and a photoreactive crosslinking agent, etc., are preferably an ultraviolet curable adhesive.

The method of bonding the polarizing film and the protective film includes a method of applying a surface activation treatment such as saponification treatment, corona treatment, and plasma treatment to the bonding surface of at least any one of these films. When the protective film is attached to both sides of the polarizing film, the adhesive system used to attach these resin films can be the same type of adhesive or different types of adhesives.

The protective film is preferably a film formed of a thermoplastic resin having translucency. Specifically, the system includes: polyolefin-based resin; cellulose-based resin; polyester-based resin; (meth)acrylic resin; or a film composed of a mixture or copolymer thereof. When a protective film is provided on both sides of the polarizing film, the protective film used may be a film made of different thermoplastic resins, or a film made of the same thermoplastic resin.

When the protective film is laminated on at least one side of the polarizing film, the protective film is preferably a protective film composed of polyolefin resin or cellulose resin. By using these films, the optics of the polarizing film can be harmless In the case of characteristics, it can effectively suppress the shrinkage of the polarizing film in a high temperature environment. In addition, the protective film may be an oxygen shielding layer.

A preferable configuration of the polarizing plate is a polarizing plate in which a protective film is laminated on at least one side of the polarizing film with an adhesive layer interposed therebetween. When the protective film is laminated on only one side of the polarizing film, it is better to laminate on the identification side. The protective film laminated on the recognition side is preferably a protective film composed of triacetyl cellulose resin or cycloolefin resin. The protective film may be an unstretched film, or it may extend in any direction to have a phase difference. The surface of the protective film laminated on the identification side may be provided with a surface treatment layer such as a hard coat layer or an anti-glare layer.

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

The so-called retardation film is an optical film exhibiting optical anisotropy, for example: The polymer film composed of styrene, polyether, polyether, polyvinylidene fluoride/polymethyl methacrylate, acetyl cellulose, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, etc. extends to Stretched film obtained by about 1.01 to 6 times. Among the stretched films, a polymer film formed by uniaxially or biaxially stretched acetyl cellulose, polyester, polycarbonate film or cycloolefin resin film is preferred. In addition, the retardation film system may be a retardation film in which a liquid crystal compound is applied to a substrate and aligned to express optical anisotropy.

In addition, in this specification, the retardation film system includes zero retardation films, and also includes films called uniaxial retardation films, low photoelasticity retardation films, and wide viewing angle retardation films.

A front retardation film called zero delay means R delays the thickness direction R _e are all of _th -15 to 15nm, and a film of isotropic optically. Examples of zero-retardation films include resin films composed of cellulose resins, polyolefin resins (chain polyolefin resins, polycyclic olefin resins, etc.), or polyethylene terephthalate resins. In terms of controlling the retardation value and also being easy to obtain, cellulose-based resin or polyolefin-based resin is preferable. The zero delay film can also be used as a protective film. The zero delay film system can include "Z-TAC" (trade name) sold by Fuji Film Co., Ltd., "ZeroTAC (registered trademark)" sold by KONICA MINOLTA OPTO Co., Ltd., and "ZeroTAC (registered trademark)" sold by ZEON Co., Ltd. ZF-14" (trade name) and so on.

Among the optical films of the present invention, the retardation film is preferably a retardation film that exhibits optical anisotropy by coating/alignment of a liquid crystal compound.

The film system that exhibits optical anisotropy by coating/aligning a liquid crystalline compound can include the following first to fifth aspects.

The first form: a phase difference film in which a rod-shaped liquid crystal compound is aligned in the horizontal direction with respect to the supporting substrate

Second form: Retardation film with rod-shaped liquid crystal compound oriented in the vertical direction with respect to the supporting substrate

The third form: a phase difference film in which the rod-shaped liquid crystal compound changes the alignment direction in the plane into a spiral shape

Fourth form: the discotic liquid crystal compound is a retardation film with oblique alignment

Fifth aspect: A biaxial retardation film in which a discotic liquid crystal compound is aligned in the vertical direction with respect to the supporting substrate

For example, the first form, the second form, and the fifth form are suitable for the optical film system used in the organic electroluminescence display. Alternatively, retardation films of these forms can be laminated and used.

When the retardation film is a layer composed of a polymer in which a polymerizable liquid crystal compound is in an aligned state (hereinafter, sometimes referred to as an "optically anisotropic layer"), the retardation film has a reverse wavelength Dispersion is better. The so-called reverse wavelength dispersion is an optical characteristic in which the retardation value in the liquid crystal alignment plane of short wavelength is smaller than the retardation value in the liquid crystal alignment plane of long wavelength. Preferably, the retardation film satisfies the following equations (7) and (8) ). In addition, Re(λ) represents the value of the in-plane phase difference with respect to the light of the wavelength λnm.

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 in the first form and has reverse wavelength dispersion, the coloration during black display of the display device is reduced, so it is preferable. In the aforementioned formula (7), 0.82≦Re(450)/Re(550)≦0.93 is more preferable. Furthermore, 120≦Re(550)≦150 is preferable.

When the retardation film is a film with an optically anisotropic layer, the polymerizable liquid crystal compound system may include liquid crystal stool (Edited by the Liquid Crystal System Editing Committee, issued by Maruzen Co., Ltd. on October 30, 2012) "3.8.6 Mesh Polymer (fully crosslinked type)", "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material" among the compounds described in the compound having a polymerizable group, as well as those described in JP 2010-31223 A, Japan JP 2010-270108, JP 2011-6360, JP 2011-207765, JP 2011-162678, JP 2016-81035, International Publication No. 2017/043438 No. and the polymerizable liquid crystal compound described in Japanese Patent Application Laid-Open No. 2011-207765, etc.

As a method of manufacturing a retardation film from a polymer in which the polymerizable liquid crystal compound is in an aligned state, for example, the method described in JP 2010-31223 A, etc. can be cited.

In the case of the second aspect, if the frontal retardation value Re (550) is adjusted to the range of 0 to 10 nm (preferably the range of 0 to 5 nm), the retardation value R _{th in the} thickness direction may be adjusted to -10 to- The range of 300 nm (preferably the range of -20 to -200 nm) is sufficient. _{The thickness direction retardation value R th} , which shows the meaning of the refractive index anisotropy in the thickness direction _{, can be measured from the retardation value R 50} and the in-plane retardation value measured by tilting 50 degrees with the fast axis in the plane as the tilt axis R ₀ to calculate. That is, the retardation value R _{th in the} thickness direction can be measured from the in-plane retardation value R ₀ , the retardation value R ₅₀ , the thickness of the retardation film d, And the average refractive index n _{0 of the retardation film is calculated by obtaining n x} , n _y, and n _z from the following equations (10) to (12), and substituting these into equation (9).

R _th =[(n _x +n _y )/2-n _z ]×d (9)

R ₀ =(n _x -n _y )×d (10)

) (11) R ₅₀ =(n _x -n _y ')×d/cos(

) (11)

(n _x +n _y +n _z )/3=n ₀ (12)

here,

=sin^-1[sin(40°)/n₀]

=sin ^-1 [sin(40°)/n ₀ ]

)+n_z ²×cos²(

)]^1/2 n _y '=n _y ×n _z /[n _y ² ×sin ² (

)+n _z ² ×cos ² (

)] ^1/2

A film that exhibits optical anisotropy by coating or aligning liquid crystal compounds, or a film that exhibits optical anisotropy by coating an inorganic layered compound, includes a film called temperature-compensated retardation film , "NH film" (trade name; film with obliquely aligned rod-shaped liquid crystal) sold by JX Nippon Oil & Energy Co., Ltd., "WV film" (trade name; disc-shaped film) sold by Fuji Film Co., Ltd. Liquid crystal tilted alignment film), "VAC film" sold by Sumitomo Chemical Co., Ltd. (trade name; fully biaxially aligned film), "new VAC film" sold by Sumitomo Chemical Co., Ltd. (trade name; Two-axis alignment type film) and so on.

The retardation film may be a multilayer film having two or more layers. For example, a protective film is layered on one side or two areas of the retardation film, or a retardation film of two or more layers is laminated with an adhesive or an adhesive interposed therebetween.

An example of the layer structure of a laminate provided with a release film on the adhesive layer of the present invention, an optical film with an adhesive layer of the present invention, and an optical laminate are shown in FIGS. 1 to 5.

The laminate 10 with a release film on the adhesive layer described in FIG. 1 is to temporarily protect the surface of the adhesive layer 1 formed by the adhesive composition of the present invention, and a release film is attached to the surface of the adhesive layer 1 ( Separation membrane) 2 state.

The optical film 10A with an adhesive layer described in FIG. 2 includes a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer formed of the adhesive composition of the present invention, and an adhesive layer of the release film 2的optical film. The protective film 3, the adhesive layer 4, and the polarizing film 5 constitute the polarizing plate 100 (optical film 40). The protective film 3 may have a phase difference. In addition, a hard coat layer or the like may be further laminated on the protective film 3.

The optical film 10B with an adhesive layer described in FIG. 3 includes a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer 7, a protective film 6, and an adhesive layer 1 formed from the adhesive composition of the present invention , And the optical film with the adhesive layer of the retardation film 8. The protective film 3, the adhesive layer 4, the polarizing film 5, the adhesive layer 7, and the protective film 6 constitute the polarizing plate 100 (optical film 40).

The optical laminate 10C described in FIG. 4 and the optical laminate 10D described in FIG. 5 include a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer formed of the adhesive composition of the present invention, and a retardation film Optical laminate of 110 (optical film 40), adhesive layer 1a, and light-emitting element 30 (liquid crystal cell, organic EL cell). The protective film 3, the adhesive layer 4, and the polarizing film 5 constitute the polarizing plate 100 (optical film 40). The adhesive layer 1a may be an adhesive layer formed of a known adhesive composition, or an adhesive layer formed of the adhesive composition of the present invention.

As shown in Figures 4 and 5, when the retardation film is a multilayer film, as shown in FIG. The 1/4-wavelength retardation layer 70 that gives a 1/4-wavelength retardation, and the phase that imparts a 1/2-wavelength portion to the transmitted light The half-wavelength retardation layer 50 of the level difference is laminated with an adhesive layer or an adhesive layer 60 interposed therebetween. In addition, as shown in FIG. 5, a configuration including a retardation film 110 (optical film 40) can also be cited, and the retardation film 110 has an adhesive layer between the quarter-wave retardation layer 50a and the positive C layer 80. Or the adhesive layer 60 is laminated.

The 1/4 wavelength retardation layer 70 of FIG. 4 that imparts a retardation of 1/4 wavelength and the 1/2 wavelength retardation layer 50 that imparts a retardation of 1/2 wavelength to the transmitted light may be the above-mentioned first The optical film of one form may also be the optical film of the fifth form. In the case of the configuration of FIG. 4, it is more preferable that at least one of them is the fifth form.

In the case of the configuration of FIG. 5, the 1/4 wavelength retardation layer 50a is preferably the optical film of the above-mentioned first form, and it is more preferable to satisfy the formulas (7) and (8).

<Liquid crystal display device>

The adhesive composition of the present invention and the adhesive layer-attached optical film system including the adhesive layer formed by the aforementioned adhesive composition can be used as an optical laminate laminated on display elements such as organic EL elements and liquid crystal cells, and Used in display devices such as organic EL display devices or liquid crystal display devices.

[Example]

Hereinafter, examples and comparative examples are shown to describe the present invention more specifically, but the present invention is not limited to these examples. In the examples, the percentages and parts from the content to the usage amount are the basis of quality as long as there is no special statement.

(Synthesis Example 1) Synthesis of the compound represented by formula (UVA-1)

Set the 500mL-four-necked flask equipped with Dimroth condenser and thermometer to nitrogen environment, and fill with 20 parts of 5,5-dimethyl-1,3-cyclohexanedione (dimedone) and pyrrolidine 11.2 parts and 200 parts of toluene, stir and reflux for 5 hours. The solvent was distilled off from the obtained mixture and purified to obtain 27.4 parts of the compound represented by the formula (M-3).

1.0 part of the obtained compound represented by formula (M-3), 2.8 parts of p-toluenesulfonyl cyanide, and 10 parts of acetonitrile were mixed in a nitrogen environment. The resulting mixture was stirred at 0 to 5°C for 5 hours. The solvent was distilled off from the obtained mixture and purified to obtain 0.6 part of the compound represented by formula (M-4).

In a nitrogen environment, 4.8 parts of the compound represented by formula (M-4), 4.6 parts of methyl trifluoromethanesulfonate, and 24 parts of acetonitrile are mixed, and stirred at 20 to 30°C for 3 hours. To the obtained mixture, 1.9 parts of malononitrile, 3 parts of triethylamine, and 24 parts of acetonitrile were added and stirred at 20 to 30°C for 3 hours. The solvent was distilled off from the obtained mixture and purified to obtain 2.9 parts of a compound represented by formula (UVA-1) (hereinafter, sometimes referred to as compound (UVA-1)).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that the compound (UVA-1) was produced.

¹ H-NMR(CDCl ₃ )δ: 0.99(s, 6H), 1.90-1.96(m, 4H), 2.48-2.51(m, 4H), 3.70-3.88(dt, 4H)

LC-MS; [M+H] ⁺ =267.5

<Measurement of maximum absorption wavelength and Gram absorption coefficient ε>

Place the 2-butanone solution (0.006 g/L) of the obtained compound (UVA-1) in a 1 cm quartz cell, and install the quartz cell on a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation) , Measure the absorbance in the wavelength range of 300 to 800 nm by the double beam method every 1 nm step. From the obtained absorbance value, the concentration of the compound (UVA-1) in the solution, and the optical path length of the quartz cell, the Gram absorbance coefficient of each wavelength is calculated.

ε (λ)=A(λ)/CL

[In the formula, ε (λ) represents the Gram absorbance coefficient (L/(g‧cm)) of the compound (UVA-1) at the wavelength λnm, A(λ) represents the absorbance at the wavelength λnm, and C represents the solution The concentration (g/L) of the compound (UVA-1), L represents the optical path length (cm) of the quartz cell. ]

The maximum absorption wavelength of the obtained compound (UVA-1) was 380.2 nm. The ε (380) of the obtained compound (UVA-1) was 184.8L/(g‧cm), the ε (420) was 0.5L/(g‧cm), and the ε (380)/ ε (420) was 369.6.

(Polymerization example 1): Preparation of acrylic resin (A1)

In a reaction vessel equipped with a condenser, a nitrogen introduction tube, a thermometer, and a stirrer, a mixture of 81.8 parts of ethyl acetate, 96 parts of butyl acrylate, 3 parts of 2-hydroxyethyl methyl acrylate, and 1 part of acrylic acid are filled as a solvent The solution is replaced by the air in the device under nitrogen to be oxygen-free, and the internal temperature is increased to 55°C. After that, 0.14 parts of azobisisobutyronitrile (polymerization initiator) was dissolved in 10 parts of ethyl acetate, and the entire amount was added. After adding the initiator, keep it at this temperature for 1 hour, Then, while maintaining the internal temperature at 54 to 56°C, ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts/hr, and the addition of ethyl acetate was stopped at the point when the concentration of the acrylic resin became 35%. , Keep the temperature at this temperature within 12 hours from the start of the addition of ethyl acetate. Finally, add ethyl acetate to adjust the concentration of the acrylic resin to 20%, and prepare an ethyl acetate solution of the acrylic resin. The weight average molecular weight Mw of the obtained acrylic resin in terms of polystyrene measured by GPC was 1.47 million, and Mw/Mn was 5.5. This was used as acrylic resin (A1). In addition, the obtained acrylic resin (A1) showed a maximum absorption in the wavelength range of 300 nm to 780 nm.

(Example 1): Production of adhesive composition (1)

100 parts of the solid content of the ethyl acetate solution (resin concentration: 20%) of the acrylic resin (A1) as the resin (A) was mixed with a crosslinking agent (F) (manufactured by Tosoh Co., Ltd.: trade name "Coronate L") , Isocyanate compound, solid content 75%) 0.3 part, silane compound (G) (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name "KBM3066") 0.28 part, radical curable component (E) (Shin-Nakamura Chemical Industry Co., Ltd.) Co., Ltd. product: brand name "A-DPH-12E", 6-functional (meth)acrylate compound) 10 parts, initiator (D) (ADEKA Co., Ltd. product: brand name "NCI-730", as Optical radical generator of oxime ester compound) 1.5 parts, light selective absorption compound (B) (compound (UVA-1)) 1.5 parts, light selective absorption compound (C) (manufactured by Otsuka Chemical Co., Ltd.: trade name " RUVA-93", 10 parts of 2-[2'-hydroxy-5'-(methacryloxyethyl)phenyl]benzotriazole), and add ethyl acetate so that the solids concentration becomes 14% to obtain the adhesive composition (1). In addition, the blending amount of the above-mentioned crosslinking agent is the mass part of the effective ingredient.

Examples 2 to 12 and Comparative Examples 1 to 7

The adhesive composition (2) to the adhesive composition (19) were produced in the same manner as in Example 1, except that each component and the content of each component were changed as shown in Table 1 or Table 2. In addition, the blending amount of the crosslinking agent is the part by mass of the active ingredient, and the acrylic resin (A1) is the part by mass of the solid.

[Table 1]

[Table 2]

In addition, the abbreviations in Table 1 and Table 2 respectively indicate those described below. Furthermore, ε (380) and ε (420) of SB107, SB707, KB111 and EU-1990 are measured in the same way as the above method.

<Resin (A)>

Acrylic resin (A1): Acrylic resin (A1) made in polymerization example 1

<Light selective absorption compound (B)>

Compound (UVA-1): The compound represented by formula (UVA-1) synthesized in Synthesis Example 1

<Light selective absorption compound (C)>

RUVA-93: manufactured by Otsuka Chemical Co., Ltd., ultraviolet absorber, trade name: RUVA-93, maximum absorption wavelength λ max=337nm, a compound having a polymerizable group and a benzotriazole skeleton in the molecule

<Initiator (D)>

NCI-730: manufactured by ADEKA Co., Ltd., trade name: NCI-730, oxime ester-based light radical generator

PBG3057: manufactured by TRONLY (Changzhou Qiang Electronic New Materials Co., Ltd. (China)), trade name: TR-PBG-3057, oxime ester-based photo-radical generator

<Free radical sclerosing component (E)>

A-DPH-12E: manufactured by Shinnakamura Chemical Industry Co., Ltd., trade name: A-DPH-12E, 6-functional (meth)acrylate compound

<Crosslinking agent (F)>

Coronate L: manufactured by Tosoh Co., Ltd., trade name: Coronate L, isocyanate-based crosslinking agent

<Silane Compound (G)>

KBM3066: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM3066, silane coupling agent

<Ultraviolet Absorber>

SB107: manufactured by Shipro Chemical Co., Ltd., UV absorber without merocyanidin structure, trade name: SEESORB 107, maximum absorption wavelength λ max = 350 nm, ε (380) = 22.4, ε (420) = 1.6, ε (380)/ ε (420)=14.0

SB707: manufactured by Shipro Chemical Co., Ltd., an ultraviolet absorber without a merocyanidin structure, trade name: SEESORB 707, maximum absorption wavelength λ max=343nm, ε (380)=5.8, ε (420)=0

KB111: manufactured by CHEMIPRO Chemical Co., Ltd., UV absorber without merocyanidin structure, trade name: KEMISORB 111, maximum absorption wavelength λ max=328nm, ε (380)=9.8, ε (420)=0

EU-1990: manufactured by EUTEC CHEMICAL, an ultraviolet absorber without a merocyanidin structure, maximum absorption wavelength λ max = 373 nm, ε (380) = 123.9, ε (420) = 7.5, ε (380)/ ε ( 420)=16.5

<Making of Adhesive Layer>

On the release surface of the separation membrane composed of polyethylene terephthalate film [from the trade name of LINTEC Co., Ltd. "PLR-382190"] that has been subjected to release treatment, use a thin coater to remove Each of the adhesive compositions prepared above was applied so that the thickness after drying became 5 μm, and dried at 100°C for 1 minute. Then, from the side of the separation membrane, an ultraviolet irradiation device ("Electrodeless UV Lamp System H BULB" manufactured by FUSION UV SYSTEMS) was used to adjust the UV-A (wavelength 320 to 390nm) to an illuminance of 500mW and a cumulative light intensity of 500mJ. By irradiating ultraviolet rays, an adhesive layer (adhesive sheet) is produced.

<Measurement of absorbance of adhesive layer>

The obtained adhesive layers were attached to the glass respectively, and after the separation film was peeled off, a cycloolefin polymer (COP) film (ZF-14 manufactured by ZEON Co., Ltd., Japan) was attached to the adhesive layer to produce a COP film/adhesive Laminated body composed of agent layer/glass. The produced laminate was mounted on a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and the absorbance was measured by the double beam method in the wavelength range of 300 to 800 nm in steps of 1 nm. The prepared adhesive layer has absorbance A (300) at a wavelength of 300 nm, absorbance A (330) at a wavelength of 330 nm, absorbance A (350) at a wavelength of 350 nm, absorbance A (380) at a wavelength of 380 nm, and absorbance A (at a wavelength of 420 nm). 420) is shown in Table 3. In addition, the absorbance of the glass with a wavelength of 300 nm, a wavelength of 330 nm, a wavelength of 350 nm, a wavelength of 380 nm, and a wavelength of 420 nm and the absorbance of the COP film are all zero. The results are shown in Table 3.

<Evaluation of Bleeding Resistance of Adhesive Layer>

A separation film is further laminated on the surface of the obtained adhesive layer to obtain an adhesive layer with a separation film on both sides. The obtained adhesive layer with separation membranes on both sides was stored in the air at 23 to 25°C for 1 month. Use a microscope on the adhesive layer with separation film on both sides after storage to confirm whether the compound in the surface has crystallized. If there is no crystal precipitation, it is rated as "○", and if there is crystal precipitation, it is rated as "X". The evaluation results are shown in Table 3.

[table 3]

The adhesive composition of the examples showed a good absorbance of 0.6 or more regardless of the wavelength of 300 nm, 330 nm, 350 nm, and 380 nm, and showed sufficient ultraviolet absorber performance. In addition, when the absorbance at a wavelength of 420 nm is less than 0.1, it shows high transmittance. Furthermore, the adhesive composition of the present invention has no crystal precipitation and exhibits good exudation resistance.

The adhesive layer formed by the adhesive composition of the present invention exhibits high absorbance at a wavelength of 300 nm to around 380 nm, and on the other hand, a wavelength of 420 nm The light penetrates, so it will not hinder the color performance of the display device and has good ultraviolet absorption performance. In addition, the exudation resistance is also good.

Even if the adhesive layer formed by the adhesive composition of the present invention is a thin layer with a thickness of less than 12 μm, it has sufficient ultraviolet absorption performance and good exudation resistance.

[Industrial availability]

The adhesive composition of the present invention and the adhesive layer-attached optical film including the adhesive layer formed by the aforementioned adhesive composition are suitable for use in liquid crystal panels and liquid crystal display devices.

Claims (24)

An adhesive composition containing: Resin (A); Light selective absorption compound (B), which contains a merocyanidin structure in the molecule and exhibits maximum absorption at a wavelength of 360nm or more; and The light selective absorption compound (C) contains a polymerizable group in the molecule and exhibits a maximum absorption at a wavelength of 300 nm or more and a wavelength of less than 360 nm. The adhesive composition according to claim 1, further comprising an initiator (D). The adhesive composition according to claim 2, wherein the initiator (D) is a radical generator. The adhesive composition according to claim 2 or 3, wherein the initiator (D) is a light radical generator. The adhesive composition according to any one of claims 2 to 4, wherein the initiator (D) is an oxime ester-based photoradical generator. The adhesive composition according to any one of claims 1 to 5 further contains a radical curable component (E). The adhesive composition according to claim 6, wherein the radical curable component (E) is a (meth)acrylate compound. The adhesive composition according to claim 6 or 7, wherein the radical curable component (E) is a polyfunctional (meth)acrylate compound. The adhesive composition according to any one of claims 1 to 8, further comprising a crosslinking agent (F). The adhesive composition according to claim 9, wherein the crosslinking agent (F) is an isocyanate-based crosslinking agent. The adhesive composition according to any one of claims 1 to 10, wherein the glass transition temperature of the resin (A) is 40°C or less. The adhesive composition according to claim 11, wherein the resin (A) is a (meth)acrylic resin having a glass transition temperature of 40°C or less. The adhesive composition according to any one of claims 1 to 12, wherein the light selective absorption compound (B) that contains a merocyanidin structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more satisfies the following formula ( 1); ε (380)≧25 (1) In formula (1), ε (380) represents the light selective absorption compound (B) with a partial anthocyanin structure in the molecule and exhibits maximum absorption at a wavelength of 360nm or more. The Gram absorption coefficient at a wavelength of 380nm; the unit of Gram absorption coefficient It is L/(g‧cm). The adhesive composition according to any one of claims 1 to 13, wherein the light selective absorption compound (B) that contains a merocyanidin structure in the molecule and shows maximum absorption at a wavelength of 360 nm or more satisfies the following formula ( 2); ε (380)/ ε (420)≧20 (2) In the formula (2), ε (380) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 380 nm, which contains a partial anthocyanin structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more; ε (420) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 420 nm, which contains a partial anthocyanin structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more. The adhesive composition according to any one of claims 1 to 14, wherein the light selective absorption compound (B) that contains a moiety anthocyanidin structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more is of formula (Y) The compound shown;

In formula (Y), R ^Y3 , R ^Y4 and R ^Y5 each independently represent an electron pulling base; R ^Y1 , R ^Y2 , R ^Y6 and R ^Y7 each independently represent a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a carboxyl group, -SCF ₃ , _{-SF 5} , _{-SF 3} , -SO ₃ H, -SO ₂ H, an aliphatic hydrocarbon group with 1 to 25 carbons that may have a substituent or an aromatic hydrocarbon group with 6 to 18 carbons that may have a substituent, the aliphatic hydrocarbon group or aromatic hydrocarbon group is Contained -CH ₂ -or -CH=can be -NR ^1A -, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -CONR ^2A -, -NR ^{3A -CO-,} -S-, -SO-, -SO ₂ -, -CF ₂ -or -CHF- substitution; R ^1A , R ^2A and R ^3A each independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms; R ^Y1 and R ^Y2 can be bonded to each other to form a ring; R ^Y1 and R ^Y6 can be bonded to each other to form a ring; R ^Y4 and R ^Y5 can be bonded to each other to form a ring. The adhesive composition according to any one of claims 1 to 14, wherein the light selective absorption compound (B) which contains a moiety anthocyanidin structure in the molecule and exhibits maximum absorption at a wavelength of 360 nm or more has a molecular weight of 3000 or less And a compound having a partial structure represented by formula (X);

In formula (X), ring W ¹ represents a ring structure that has at least one double bond as a constituent element of the ring and does not have aromaticity; R ³ represents a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a carboxyl group, -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, and the number of carbons that may have a substituent An aliphatic hydrocarbon group of 1 to 25 or an aromatic hydrocarbon group of 6 to 18 carbons that may have substituents, the aliphatic hydrocarbon group or aromatic hydrocarbon group containing -CH ₂ -or -CH= may be -O-, -S -, -NR ^1xA -, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CONR ^2xA -, -NR ^3xA -CO-, -O-CO-NR ^4xA -, -NR ^5xA -CO-O-, -NR ^6xA -CO-NR ^7xA -, -CO-S-, -S-CO-S-, -S-CO-NR ^8xA -, -NR ^9xA -CO- S-, -CS-, -O-CS-, ^{-CS-O-, -NR 10xA -CS-} , -NR ^{11xA -CS} -S-, -S-CS-, -CS-S-, -S- CS-S-, -SO- or -SO ₂ -replaced; R ^1xA , R ^2xA , R ^3xA , R ^4xA , R ^5xA , R ^6xA , R ^7xA , R ^8xA , R ^9xA , R ^10xA and R ^11xA each independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms. The adhesive composition according to claim 16, wherein the compound having a molecular weight of 3000 or less and having a partial structure represented by formula (X) is a compound represented by formula (I) to a compound represented by formula (VIII) Either

In formula (I) to formula (VIII), Rings W ¹ and R ^{3 have the} same meaning as described above, The ring W ² , the ring W ³ , the ring W ⁴ , the ring W ⁵ , the ring W ⁶ , the ring W ⁷ , the ring W ⁸ , the ring W ⁹ , the ring W ¹⁰ , the ring W ¹¹ and the ring W ¹² each independently represent at least 1 A ring structure with a double bond as a constituent element of the ring, Ring W ¹¹¹ represents a ring having at least two nitrogen atoms as constituent elements, Ring W ¹¹² and ring W ¹¹³ each independently represent a ring having at least one nitrogen atom as a constituent element, R ¹ , R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁹¹ , R ¹⁰¹ , R ¹¹¹ , R ² , R ¹² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² , R ¹⁰² and R ¹¹² Each independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a carboxyl group, -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, and may have a substituent The aliphatic hydrocarbon group with 1 to 25 carbons or the aromatic hydrocarbon group with 6 to 18 carbons which may have substituents, the aliphatic hydrocarbon group or the aromatic hydrocarbon group contains -CH ₂ -or -CH = can be -NR ^12A -, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -CONR ^13A -, -NR ^14A -CO-, -S-, -SO-, -CF ₂ -or -CHF -replace, R ¹³ , R ²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁶³ , R ⁷³ , R ⁸³ , R ⁹³ , R ¹⁰³ and R ¹¹³ each independently represent a heterocyclic group, a halogen atom, a nitro group, a cyano group, and a hydroxyl group , Thiol group, carboxyl group, -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, aliphatic hydrocarbon group with 1 to 25 carbons that may have substituents or 6 to 18 carbons that may have substituents The aromatic hydrocarbon group, the aliphatic hydrocarbon group or the aromatic hydrocarbon group contains -CH ₂ -or -CH= can be -O-, -S-, -NR ^1A -, -CO-, -CO-O-,- O-CO-, -O-CO-O-, -CONR ^2A -, -NR ^3A -CO-, -O-CO-NR ^4A -, -NR ^5A -CO-O-, -NR ^6A -CO-NR ^7A -, -CO-S-, -S-CO-S-, -S-CO-NR ^8A -, -NR ^9A -CO-S-, -CS-, -O-CS-, -CS-O- , -NR ^10A -CS-, -NR ^11A -CS-S-, -S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO ₂ -replaced, R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A , R ^8A , R ^9A , R ^10A , R ^11A , R ^12A , R ^13A and R ^14A each independently represent a hydrogen atom or carbon number 1 to 6 alkyl group, R ⁴ , R ¹⁴ , R ²⁴ , R ³⁴ , R ⁴⁴ , R ⁵⁴ , R ⁶⁴ , R ⁷⁴ , R ⁸⁴ , R ⁹⁴ , R ¹⁰⁴ , R ¹¹⁴ , R ⁵ , R ¹⁵ , R ²⁵ , R ³⁵ , R ⁷⁵ And R ⁸⁵ each independently represent an electron pull base, R ¹ and R ² can be bonded to each other to form a ring, R ⁴¹ and R ⁴² can be bonded to each other to form a ring, R ⁵¹ and R ⁵² can be bonded to each other to form a ring, R ⁶¹ and R ⁶² can be bonded to each other to form a ring, R ⁹¹ and R ⁹² can be bonded to each other to form a ring, R ¹⁰¹ and R ¹⁰² can be bonded to each other to form a ring, R ¹¹¹ and R ¹¹² can be bonded to each other to form a ring, R ² and R ³ can be bonded to each other to form a ring, R ¹² and R ¹³ can be bonded to each other to form a ring, R ⁴² and R ⁴³ can be bonded to each other to form a ring, R ⁵² and R ⁵³ can be bonded to each other to form a ring, R ⁶² and R ⁶³ can be bonded to each other to form a ring, R ⁷² and R ⁷³ can be bonded to each other to form a ring, R ⁸² and R ⁸³ can be bonded to each other to form a ring, R ⁹² and R ⁹³ can be bonded to each other to form a ring, R ¹⁰² and R ¹⁰³ can be bonded to each other to form a ring, R ¹¹² and R ¹¹³ can be bonded to each other to form a ring, R ⁴ and R ⁵ can be bonded to each other to form a ring, R ¹⁴ and R ¹⁵ can be bonded to each other to form a ring, R ²⁴ and R ²⁵ can be bonded to each other to form a ring, R ³⁴ and R ³⁵ can be bonded to each other to form a ring, R ⁷⁴ and R ⁷⁵ can be bonded to each other to form a ring, R ⁸⁴ and R ⁸⁵ can be bonded to each other to form a ring, R ⁶ and R ⁸ each independently represent a divalent bonding group, R ⁷ series represents a single bond or a divalent bond group, R ⁹ and R ¹⁰ each independently represent a trivalent bonding group, The R ¹¹ series represents a tetravalent bonding group. An adhesive layer formed by the adhesive composition described in any one of claims 1-17. The adhesive layer described in claim 18 satisfies the following formula (3), A(380)≧0.60 (3) In formula (3), A(380) represents the absorbance at a wavelength of 380nm. The adhesive layer described in claim 18 or 19 further satisfies the following formula (4), A(380)/A(420)≧5 (4) In formula (4), A(380) represents the absorbance at a wavelength of 380nm, and A(420) represents the absorbance at a wavelength of 420nm. The adhesive layer according to any one of claims 18 to 20, wherein the adhesive layer has a film thickness of 10 μm or less. An optical film with an adhesive layer, wherein at least one area of the adhesive layer according to any one of claims 18 to 21 has an optical film. The optical film with an adhesive layer according to claim 22, wherein the optical film is a polarizing plate. An image display device comprising the optical film with an adhesive layer described in claim 22 or 23.

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