CN113874455A - Adhesive composition - Google Patents

Adhesive composition Download PDF

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CN113874455A
CN113874455A CN202080038354.9A CN202080038354A CN113874455A CN 113874455 A CN113874455 A CN 113874455A CN 202080038354 A CN202080038354 A CN 202080038354A CN 113874455 A CN113874455 A CN 113874455A
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meth
group
acrylate
adhesive composition
film
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浅津悠司
小泽昭一
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)

Abstract

Provided is an optical film with an adhesive layer, which has good bleeding resistance when the optical film with the adhesive layer, in which the adhesive layer and the optical film are laminated, is stored for a long time. Also provided are an adhesive layer having good bleed-out resistance, and an adhesive composition capable of forming the adhesive layer. An adhesive composition comprising a resin (A), a light selective absorbing compound (B) having a merocyanine structure and a polymerizable group in the molecule, and a photoinitiator (D). The adhesive composition may further contain a photocurable component (C).

Description

Adhesive composition
Technical Field
The present invention relates to an adhesive composition, an adhesive layer formed from the adhesive composition, and an optical film having the adhesive layer laminated thereon.
Background
Display devices (FPD: flat panel display) such as organic EL display devices and liquid crystal display devices use various members such as display elements such as organic EL elements and liquid crystal cells, and optical films such as polarizing plates and retardation films. Among them, organic EL compounds and liquid crystal compounds, which are commonly used in organic EL display devices, are often used as compounds having low weather resistance among organic materials, and thus deterioration due to Ultraviolet (UV) light is likely to be a problem, and deterioration due to visible light having a short wavelength of 420nm or less is also likely to be a problem. In order to solve such problems, patent document 1 describes an adhesive composition containing a (meth) acrylic resin and a light selective absorbing compound having an indole structure (bossorb UA-3911, manufactured by oriental chemical industries, inc.) that selectively absorbs light having a wavelength near 400nm, and an optical film having an adhesive layer formed of the composition.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-165941
Disclosure of Invention
Problems to be solved by the invention
In addition, recently, from the viewpoint of making the film thinner, the optical film used in an organic EL display device among display devices is increasingly a polymer in an aligned state of a polymerizable liquid crystal compound. It is known that an optical film formed of a polymer in an oriented state of a polymerizable liquid crystal compound tends to be more likely to be cracked (broken) and elongated when exposed to an environment in which high-temperature conditions and low-temperature conditions are repeated, as compared with a conventional optical film formed by stretching a resin film.
The optical film described in reference 1, in which the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition is laminated, is not sufficient in suppressing the elongation of the absorption crack even if the deterioration of the visible light having a wavelength of about 420nm can be improved.
Means for solving the problems
The present invention includes the following inventions.
[1] An adhesive composition comprising a resin (A), a photocurable component (C) and a light selective absorbing compound (B) having a merocyanine structure.
[2] The adhesive composition according to [1], which further comprises a photoinitiator (D).
[3] The adhesive composition according to [2], wherein the photoinitiator (D) is a photo radical generator.
[4] The adhesive composition according to any one of [1] to [3], wherein the photocurable component (C) is a photoradically curable component.
[5] The adhesive composition according to [4], wherein the photocurable component (C) comprises a (meth) acrylate compound.
[6] The adhesive composition according to [4] or [5], wherein the photocurable component (C) comprises a polyfunctional (meth) acrylate compound.
[7] The adhesive composition according to any one of [1] to [6], further comprising a crosslinking agent (E).
[8] The adhesive composition according to [7], wherein the crosslinking agent (E) is an isocyanate crosslinking agent.
[9] The adhesive composition according to any one of [1] to [8], wherein the resin (A) has a glass transition temperature of 40 ℃ or lower.
[10] The adhesive composition according to any one of [1] to [9], wherein the resin (A) is a (meth) acrylic resin.
[11] The adhesive composition according to any one of [1] to [10], wherein the resin (A) is a (meth) acrylic resin having a weight average molecular weight of 50 ten thousand or more.
[12] The adhesive composition according to any one of [1] to [11], wherein the light selective absorbing compound (B) having a merocyanine structure satisfies the following formula (1).
ε(405)≥5 (1)
[ in the formula (1),. epsilon. (. 405) represents the molar absorption coefficient of the light selective absorbing compound (B) having a merocyanine structure at a wavelength of 405 nm. The molar absorptivity was expressed in L/(g.cm). ]
[13] The adhesive composition according to any one of [1] to [12], wherein the light selective absorbing compound (B) having a merocyanine structure satisfies the following formula (2).
ε(405)/ε(440)≥20 (2)
[ in the formula (2),. epsilon. (405) represents the molar absorption coefficient of the light selective absorbing compound (B) having a merocyanine structure at a wavelength of 405nm, and. epsilon. (440) represents the molar absorption coefficient of the light selective absorbing compound (B) having a merocyanine structure at a wavelength of 440 nm. ]
[14] The adhesive composition according to any one of [1] to [13], wherein the light selective absorbing compound (B) having a merocyanine structure has no polymerizable group.
[15] The adhesive composition according to any one of [1] to [14], wherein the light selective absorbing compound (B) having a merocyanine structure is a compound represented by formula (I).
Figure BDA0003369733560000031
[ in the formula (I), R1、R2、R3、R4And R5Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 15 carbon atoms or a heterocyclic group, -CH contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group2-may be replaced by-NR1A-、-SO2-, -CO-, -O-or-S-.
R6And R7Each independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an electron-withdrawing group.
R1ARepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R1And R2May be linked to each other to form a ring structure, R2And R3May be linked to each other to form a ring structure, R2And R4May be linked to each other to form a ring structure, R3And R6May be linked to each other to form a ring structure, R5And R7May be linked to each other to form a ring structure, R6And R7May be interconnected to form a ring structure.]
[16] The adhesive composition according to [15], wherein the compound represented by the formula (I) is a compound represented by the formula (II).
Figure BDA0003369733560000041
[ in the formula (II), R11、R12、R13、R14And R15Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 15 carbon atoms or a heterocyclic group, or-CH contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group2-may be replaced by-NR11A-、-SO2-, -CO-, -O-or-S-.
R16And R17Each independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an electron-withdrawing group.
R11ARepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R11And R12May be linked to each other to form a ring structure, R12And R13May be linked to each other to form a ring structure, R12And R14May be interconnected to form a ring structure.]
[17] An adhesive layer comprising the adhesive composition according to any one of [1] to [16 ].
[18] The adhesive layer according to [17], which satisfies the following formula (3).
A(405)≥0.5 (3)
[ in the formula (3), A (405) represents the absorbance at a wavelength of 405 nm. ]
[19] The adhesive layer according to [18], which further satisfies the following formula (4).
A(405)/A(440)≥5 (4)
In the formula (4), A (405) represents the absorbance at a wavelength of 405nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]
[20] An optical film with an adhesive layer, wherein the optical film is laminated on at least one surface of the adhesive layer according to any one of [17] to [19 ].
[21] The optical film with an adhesive layer according to [20], wherein the optical film is a polarizing plate.
[22] An image display device comprising the optical film with an adhesive layer according to [20] or [21 ].
ADVANTAGEOUS EFFECTS OF INVENTION
An optical film including a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has good crack resistance without elongation of cracks (cracks) under an environment of repeated high-temperature conditions and low-temperature conditions.
Drawings
Fig. 1 shows an example of the layer structure of the pressure-sensitive adhesive layer of the present invention.
Fig. 2 shows an example of the layer structure of the optical 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 film with an adhesive layer of the present invention.
Fig. 5 shows an example of the layer structure of the optical film with an adhesive layer of the present invention.
Detailed Description
< adhesive composition >
The adhesive composition of the present invention comprises a resin (a), a light selective absorbing compound (B) having a merocyanine structure, and a photocurable component (C).
The adhesive composition of the present invention may further contain a photoinitiator (D), a crosslinking agent (E), a silane compound, and the like.
< resin (A) >
The resin (a) is not particularly limited as long as it is a resin used for the adhesive composition. The resin (A) is preferably a resin having a glass transition temperature of 40 ℃ or lower. The glass transition temperature (Tg) of the resin (A) is more preferably 20 ℃ or lower, still more preferably 10 ℃ or lower, and still more preferably 0 ℃ or lower. The glass transition temperature of the resin (A) is usually-80 ℃ or higher, preferably-60 ℃ or higher, more preferably-50 ℃ or higher, still more preferably-45 ℃ or higher, and particularly preferably-30 ℃ or higher. When the glass transition temperature of the resin (a) is 40 ℃ or lower, it is advantageous to improve the adhesion between the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition containing the resin (a) and the optical film. Further, if the glass transition temperature of the resin (A) is-80 ℃ or higher, it is advantageous to improve the durability of the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition containing the resin (A) (appearance defects in a high-temperature test: cohesive failure, etc.). The glass transition temperature can be measured by a Differential Scanning Calorimeter (DSC).
Examples of the resin having a glass transition temperature of 40 ℃ or lower include a (meth) acrylic resin, a silicone resin, a rubber resin, and a urethane resin, and a (meth) acrylic resin is preferable.
The (meth) acrylic resin is preferably a polymer containing a structural unit derived from a (meth) acrylate ester as a main component (preferably containing 50 mass% or more). The structural unit derived from a (meth) acrylate ester may contain one or more structural units derived from a monomer other than a (meth) acrylate ester (for example, a structural unit derived from a monomer having a polar functional group). In the present specification, (meth) acrylic acid means any of acrylic acid and methacrylic acid, and "(meth)" in the case of (meth) acrylate and the like is also used in the same manner.
Examples of the (meth) acrylate include (meth) acrylates represented by the following formula (a).
Figure BDA0003369733560000061
[ in the formula (a), R1ARepresents a hydrogen atom or a methyl group, R2ARepresents an alkyl group having 1 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and the hydrogen atom of the alkyl group or the aralkyl group may be substituted with an alkoxy group having 1 to 10 carbon atoms.]
In the formula (a), R2APreferably an alkyl group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.
Examples of the (meth) acrylate represented by the formula (I) include:
linear alkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate;
branched alkyl esters of (meth) acrylic acid such as isopropyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, isohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isostearyl (meth) acrylate, and isoamyl (meth) acrylate;
alicyclic skeleton-containing alkyl esters of (meth) acrylic acid such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclododecyl (meth) acrylate, methylcyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and cyclohexyl α -ethoxyacrylate;
aromatic ring skeleton-containing esters of (meth) acrylic acid such as phenyl (meth) acrylate; and so on.
In addition, there may be mentioned alkyl (meth) acrylates containing a substituent in which a substituent is introduced into an alkyl group in the alkyl (meth) acrylate. The substituent of the alkyl (meth) acrylate having a substituent is a group in which a hydrogen atom of an alkyl group is substituted, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group. Specific examples of the alkyl (meth) acrylate having a substituent include 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2- (2-phenoxyethoxy) ethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and phenoxypoly (ethylene glycol) meth (acrylate).
These (meth) acrylates may be used alone or in combination of two or more.
The (meth) acrylic resin (a) preferably contains a structural unit derived from an alkyl acrylate (a1) having a homopolymer glass transition temperature Tg of less than 0 ℃ and a structural unit derived from an alkyl acrylate (a2) having a homopolymer Tg of 0 ℃ or higher. The inclusion of the structural unit derived from the alkyl acrylate (a1) and the structural unit derived from the alkyl acrylate (a2) is advantageous in improving the high-temperature durability of the adhesive layer. The Tg of the homopolymer of the alkyl (meth) acrylate can be obtained, for example, from literature values of POLYMER HANDBOOK (Wiley-Interscience) and the like.
Specific examples of the alkyl acrylate (a1) include alkyl acrylates having an alkyl group of about 2 to 12 carbon atoms such as ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, isohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl acrylate, isodecyl acrylate, and n-dodecyl acrylate.
The alkyl acrylate (a1) may be used in a single amount of 1 kind, or may be used in combination of 2 or more kinds. Among them, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate and the like are preferable from the viewpoints of the follow-up property and the reworkability when the pressure-sensitive adhesive sheet of the present invention is laminated on an optical film.
The alkyl acrylate (a2) is an alkyl acrylate other than the alkyl acrylate (a 1). Specific examples of the alkyl acrylate (a2) include methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, stearyl acrylate, t-butyl acrylate and the like.
The alkyl acrylate (a2) may be used in a single amount of 1 kind, or may be used in combination of 2 or more kinds. Among them, the alkyl acrylate (a2) preferably includes methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, and the like, and more preferably includes methyl acrylate, from the viewpoint of high-temperature durability.
The structural unit derived from the (meth) acrylate represented by formula (a) is preferably 50% by mass or more, preferably 60 to 95% by mass, and more preferably 65 to 95% by mass or more of the total structural units contained in the (meth) acrylic resin.
The structural unit derived from a monomer other than the (meth) acrylate is preferably a structural unit derived from a monomer having a polar functional group, and more preferably a structural unit derived from a (meth) acrylate having a polar functional group. Examples of the polar functional group include a hydroxyl group, a carboxyl group, a substituted or unsubstituted amino group, a heterocyclic group such as an epoxy group, and the like.
Examples of the monomer having a polar functional group include:
1-hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 1-hydroxyheptyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 1-hydroxypentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, 3-hydroxyhexyl (meth) acrylate, 3-hydroxyheptyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, hydroxy-n-yl (meth) acrylate, hydroxy-propyl (meth) acrylate, hydroxy-yl (meth) acrylate, hydroxy-pentyl (meth) acrylate, hydroxy-yl (meth) acrylate, hydroxy-butyl (meth) acrylate, hydroxy-1-hydroxy-pentyl (meth) acrylate, hydroxy-butyl (meth) acrylate, hydroxy-butyl (meth) acrylate, hydroxy-butyl acrylate, 4-hydroxyhexyl (meth) acrylate, 4-hydroxyheptyl (meth) acrylate, 4-hydroxyoctyl (meth) acrylate, 2-chloro-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 5-hydroxyheptyl (meth) acrylate, 5-hydroxyoctyl (meth) acrylate, 5-hydroxynonyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 6-hydroxyheptyl (meth) acrylate, 6-hydroxyoctyl (meth) acrylate, 6-hydroxynonyl (meth) acrylate, 6-hydroxyheptyl (meth) acrylate, and the like, 6-hydroxydecyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 7-hydroxyoctyl (meth) acrylate, 7-hydroxynonyl (meth) acrylate, 7-hydroxydecyl (meth) acrylate, 7-hydroxyundecyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 8-hydroxynonyl (meth) acrylate, 8-hydroxydecyl (meth) acrylate, 8-hydroxyundecyl (meth) acrylate, 8-hydroxydodecyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, 9-hydroxydecyl (meth) acrylate, 9-hydroxyundecyl (meth) acrylate, 9-hydroxydodecyl (meth) acrylate, 9-hydroxytridecyl (meth) acrylate, hydroxy-substituted (9-substituted (meth) acrylate, hydroxy-substituted (meth) acrylate, or their salts, or their corresponding with (meth) acrylate, or their corresponding with (meth) acrylate, or their corresponding with (meth) acrylate, or their corresponding (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 10-hydroxyundecyl (meth) acrylate, 10-hydroxydodecyl (meth) acrylate, 10-hydroxytridecyl acrylate, 10-hydroxytetradecyl (meth) acrylate, 11-hydroxyundecyl (meth) acrylate, 11-hydroxydodecyl (meth) acrylate, 11-hydroxytridecyl (meth) acrylate, 11-hydroxytetradecyl (meth) acrylate, 11-hydroxypentadecyl (meth) acrylate, 12-hydroxydodecyl (meth) acrylate, 12-hydroxytridecyl (meth) acrylate, 12-hydroxytetradecyl (meth) acrylate, 13-hydroxypentadecyl (meth) acrylate, and mixtures thereof, Hydroxyl group-containing monomers such as 13-hydroxytetradecyl (meth) acrylate, 13-hydroxypentadecyl (meth) acrylate, 14-hydroxytetradecyl (meth) acrylate, 14-hydroxypentadecyl (meth) acrylate, 15-hydroxypentadecyl (meth) acrylate, and 15-hydroxyheptadecyl (meth) acrylate;
carboxyl group-containing monomers such as (meth) acrylic acid, carboxyalkyl (meth) acrylate (e.g., carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate), maleic acid, maleic anhydride, fumaric acid, and crotonic acid;
monomers having a heterocyclic group such as acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, 2, 5-dihydrofuran and the like;
monomers having a substituted or unsubstituted amino group such as aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and the like.
Among them, from the viewpoint of reactivity of the (meth) acrylate polymer with the crosslinking agent, the monomer having a hydroxyl group and/or the monomer having a carboxyl group are preferable, and the monomer having a hydroxyl group and the monomer having a carboxyl group are more preferable to be contained in all.
As the monomer having a hydroxyl group, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate are preferable. In particular, by using 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and 5-hydroxypentyl acrylate, good durability can be obtained.
As the monomer having a carboxyl group, acrylic acid is preferably used.
From the viewpoint of preventing a sharp increase in the peeling force of a spacer film that can be laminated on the outer surface of the pressure-sensitive adhesive layer, the (meth) acrylic resin (a) preferably contains substantially no structural unit derived from a monomer having an amino group. The term "substantially not included" means that the amount of the (meth) acrylic resin (a) is 0.1 parts by mass or less per 100 parts by mass of all the structural units.
The content of the structural unit derived from the monomer having a polar functional group is preferably 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, further preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 7 parts by mass or less, with respect to 100 parts by mass of the total structural units of the (meth) acrylic resin (a).
The content of the structural unit derived from the aromatic group-containing monomer is preferably 20 parts by mass or less, more preferably 4 parts by mass or more and 20 parts by mass or less, and further preferably 4 parts by mass or more and 16 parts by mass or less, based on 100 parts by mass of the total structural units of the (meth) acrylic resin (a).
Examples of the structural unit derived from a monomer other than the (meth) acrylate ester include a structural unit derived from a styrene monomer, a structural unit derived from a vinyl monomer, a structural unit derived from a monomer having a plurality of (meth) acryloyl groups in the molecule, and a structural unit derived from a (meth) acrylamide monomer.
Examples of the styrene monomer include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene and the like; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene, etc.; nitrostyrene; acetyl styrene; a methoxystyrene; and divinylbenzene.
Examples of the vinyl monomer include: vinyl esters of fatty acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; nitrogen-containing heteroaromatic vinyl compounds such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated dienes such as butadiene, isoprene and chloroprene; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.
Examples of the monomer having a plurality of (meth) acryloyl groups in the molecule include: monomers having 2 (meth) acryloyl groups in the molecule, such as 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, and tripropylene glycol di (meth) acrylate; a monomer having 3 (meth) acryloyl groups in the molecule, such as trimethylolpropane tri (meth) acrylate.
Examples of the (meth) acrylamide monomer include N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (1, 1-dimethyl-3-oxobutyl) (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (1, 1-dimethyl-3-oxobutyl) (meth) acrylamide, N-2-oxide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxybutyl) (meth) acrylamide, N- (3-1-hydroxy-acrylamide, N-2-hydroxy-2-1-yl (meth) acrylamide, N-2-hydroxy-1-2-one, N-one, and N-one or more, N- [2- (2-oxo-1-imidazolidinyl) ethyl ] (meth) acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) acrylamide, N- (1-methylethoxymethyl) (meth) acrylamide, N- (1-methylpropoxymethyl) (meth) acrylamide, N- (2-methylpropoxymethyl) (meth) acrylamide, N- (butoxymethyl) (meth) acrylamide, N- (1, 1-dimethylethoxymethyl) (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N-isopropylacrylamide, N- (2-ethoxymethyl) (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N- (2-ethoxymethyl) acrylamide, N- (2-propoxymethyl) acrylamide, N, n- (2-ethoxyethyl) (meth) acrylamide, N- (2-propoxyethyl) (meth) acrylamide, N- [2- (1-methylethoxy) ethyl ] (meth) acrylamide, N- [2- (1-methylpropoxy) ethyl ] (meth) acrylamide, N- [2- (2-methylpropoxy) ethyl ] (meth) acrylamide, N- (2-butoxyethyl) (meth) acrylamide, N- [2- (1, 1-dimethylethoxy) ethyl ] (meth) acrylamide and the like. Among them, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) acrylamide, and N- (2-methylpropoxymethyl) acrylamide are preferable.
The weight average molecular weight (Mw) of the (meth) acrylic resin (a) is preferably 50 to 250 ten thousand. When the weight average molecular weight is 50 ten thousand or more, the durability of the pressure-sensitive adhesive layer in a high-temperature environment is improved, and problems such as peeling of an adherend from the pressure-sensitive adhesive layer by lifting and cohesive failure of the pressure-sensitive adhesive sheet are easily suppressed. It is advantageous from the viewpoint of coatability if the weight average molecular weight is 250 ten thousand or less. From the viewpoint of satisfying both the durability of the pressure-sensitive adhesive layer and the coatability of the pressure-sensitive adhesive composition, the weight average molecular weight is preferably 60 to 180 ten thousand, more preferably 70 to 170 ten thousand, and particularly preferably 100 to 160 ten thousand. 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 to 10, preferably 3 to 8, and more preferably 3 to 6. The weight average molecular weight can be analyzed by gel permeation chromatography and is a value in terms of standard polystyrene.
When the (meth) acrylic resin (A) is dissolved in ethyl acetate to form a 20 mass% solution, the viscosity at 25 ℃ is preferably 20 pas or less, and more preferably 0.1 to 15 pas. The viscosity in this range is advantageous from the viewpoint of coatability when the adhesive composition is applied to a substrate. The viscosity can be measured by a brookfield viscometer.
The (meth) acrylic resin (a) can be produced by a known method such as solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization, and the solution polymerization is particularly preferred. The solution polymerization method includes, for example, a method of mixing a monomer and an organic solvent, adding a thermal polymerization initiator under a nitrogen atmosphere, and stirring at a temperature of about 40 to 90 ℃, preferably about 50 to 80 ℃ for about 3 to 15 hours. In order to control the reaction, the monomer or the thermal polymerization initiator may be continuously or intermittently added during the polymerization. The monomer and the thermal polymerization initiator may be added to an organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. As the thermal polymerization initiator, a known thermal polymerization initiator can be used. In addition, instead of the thermal polymerization initiator, a photopolymerization initiator may be used, and a polymerization method using ultraviolet rays or the like may be used.
The content of the resin (a) is usually 50 to 99.9 mass%, preferably 60 to 99 mass%, and more preferably 70 to 95 mass% in 100 mass% of the solid content of the binder composition.
< light selective absorption Compound (B) >)
The light selective absorbing compound (B) is a compound having a merocyanine structure in the molecule.
In the present invention, the merocyanine structure refers to a partial structure represented by > N-C < C. The merocyanine structure of the present invention does not include aromatic condensed rings (e.g., benzotriazole ring, benzimidazole ring, indole ring, isoindole ring, quinoline ring, etc.) having a partial structure represented by > N-C ═ C < as a ring constituent.
In the present invention, the light selective absorbing compound (B) having a merocyanine structure preferably does not contain a polymerizable group in the molecule. Examples of the polymerizable group include an epoxy group; an oxetanyl group; an oxazoline group; an aziridinyl group; and ethylenically unsaturated groups such as vinyl, α -methylvinyl, acryloyl, methacryloyl, allyl, styryl, and (meth) acrylamide.
The light selective absorbing compound (B) having a merocyanine structure in the molecule preferably satisfies the following formula (1), and more preferably also satisfies formula (2).
ε(405)≥5 (1)
[ in the formula (1),. epsilon. (. epsilon.) (405) represents the molar absorption coefficient at a wavelength of 405nm of the light selective absorbing compound (B) having a merocyanine structure. The molar absorptivity was expressed in L/(g.cm). ]
ε(405)/ε(440)≥20 (2)
[ in the formula (2),. epsilon. (. epsilon.) (405) represents the molar absorption coefficient at a wavelength of 405nm of the light selective absorbing compound (B) having a merocyanine structure.
ε (440) represents the molar absorption coefficient at a wavelength of 440nm of the light selective absorbing compound (B) having a merocyanine structure. ]
The value of ∈ (405) of the light selective absorbing compound (B) having a merocyanine structure is preferably 5L/(g · cm) or more, more preferably 10L/(g · cm) or more, still more preferably 20L/(g · cm) or more, still more preferably 30L/(g · cm) or more, and usually 500L/(g · cm) or less. The larger the value of epsilon (405), the more easily the compound absorbs light having a wavelength of 405nm, and the more easily the compound exhibits a function of suppressing deterioration due to ultraviolet light or visible light having a short wavelength.
The value of ∈ (405)/∈ (440) of the light selective absorbing compound (B) having a merocyanine structure is preferably 20 or more, more preferably 40 or more, still more preferably 70 or more, and particularly more preferably 80 or more. The adhesive layer formed from the adhesive composition containing the compound having a large value of epsilon (405)/epsilon (440) absorbs light in the vicinity of wavelength of 405nm without impairing the color expression of the display device. In addition, light degradation of a display device such as an optical film (retardation film) or an organic EL element to be stacked can be suppressed.
Examples of the light selective absorbing compound (B) having a merocyanine structure include compounds represented by formula (I).
Figure BDA0003369733560000141
[ in the formula, R1、R2、R3、R4And R5Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 15 carbon atoms or a heterocyclic group, -CH contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group2-may be replaced by-NR1A-、-SO2-, -CO-, -O-or-S-.
R6And R7Each independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an electron-withdrawing group.
R1ARepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R1And R2May be linked to each other to form a ring structure, R2And R3May be linked to each other to form a ring structure, R2And R4May be linked to each other to form a ring structure, R3And R6May be linked to each other to form a ring structure, R5And R7May be linked to each other to form a ring structure, R6And R7May be interconnected to form a ring structure.]
As R1～R5Examples of the aliphatic hydrocarbon group having 1 to 25 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group, isododecyl groupAnd C1-25 linear or branched alkyl groups such as undecyl, lauryl, myristyl, cetyl, stearyl and the like: cycloalkyl groups having 3 to 25 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; cycloalkyl alkyl group having 4 to 25 carbon atoms such as cyclohexylmethyl group, etc., preferably alkyl group having 4 to 25 carbon atoms.
As R1～R5Examples of the substituent that the aliphatic hydrocarbon group having 1 to 25 carbon atoms may have include a hydroxyl group, a cyano group, a halogen atom, a mercapto group, an amino group, and a nitro group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As R1～R5The aromatic hydrocarbon group having 6 to 15 carbon atoms includes aryl groups having 6 to 15 carbon atoms such as phenyl, naphthyl, anthryl and biphenyl groups; aralkyl groups having 7 to 15 carbon atoms such as benzyl, phenethyl, naphthylmethyl, and phenyl.
As R1～R5Examples of the substituent which may be contained in the aromatic hydrocarbon group having 6 to 15 carbon atoms include a hydroxyl group, a cyano group, a halogen atom, a mercapto group, an amino group, a nitro group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an acyl group, an acyloxy group and a-C (NR)2A)R2B、-CONR3AR3B、-SO2R4A(R2A、R2B、R3AAnd R3BEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R4ARepresents an alkyl group having 1 to 6 carbon atoms. ) And the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkoxy group include alkoxy groups having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group.
The alkylthio group includes alkylthio groups having 1 to 12 carbon atoms such as a methylthio group, an ethylthio group, a propylthio group, and a butylthio group.
Examples of the acyl group include acyl groups having 2 to 13 carbon atoms such as an acetyl group, a propionyl group, and a butyryl group.
Examples of the acyloxy group include acyloxy groups having 2 to 13 carbon atoms such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group and a 2-ethylhexylcarbonyloxy group.
Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 13 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, an undecyloxycarbonyl group, a dodecyloxycarbonyl group and the like.
as-CONR3AR3BExamples thereof include aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, ethylaminocarbonyl group, and methylmethylaminocarbonyl group.
as-C (NR)2A)R2BExamples thereof include methylimino, dimethylimino and methylethylimino.
as-SO2R4AExamples thereof include methylsulfonyl group and ethylsulfonyl group.
As R1A、R2A、R3A、R4A、R2B、R3BExamples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl and the like.
As R1～R5Examples of the heterocyclic group include a pyrrolidine ring group, a pyrroline ring group, an imidazolidine ring group, an imidazoline ring group, an oxazoline ring group, a thiazoline ring group, a piperidine ring group, a morpholine ring group, a piperazine ring group, an indole ring group, an isoindoline ring group, a quinoline ring group, a thiophene ring group, a pyrrole ring group, an aliphatic heterocyclic group having 4 to 20 carbon atoms such as a thiazoline ring group and a furan ring group, and an aromatic heterocyclic group having 3 to 20 carbon atoms.
As R6And R7Examples of the alkyl group having 1 to 25 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and n-octylAnd linear or branched alkyl groups having 1 to 25 carbon atoms such as isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group, isododecyl group, undecyl group, lauryl group, myristyl group, cetyl group, stearyl group, and the like.
As R6And R7Examples of the electron-withdrawing group include a cyano group, a nitro group, a halogen atom, an alkyl group substituted with a halogen atom, and a group represented by the formula (I-1).
*-X1-R111 (I-1)
[ in the formula, R111Represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a halogen atom, and at least 1 of methylene groups contained in the hydrocarbon group may be replaced with an oxygen atom.
X1represents-CO-1、-COO-*1、-CS-*1、-CSS-*1、-CSNR112-*1、-CONR113-*1、-CNR114-*1or-SO2-*1。
R112、R113And R114Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group.
*1Is represented by the formula111The connecting bond of (1).
Denotes a bond to a carbon atom. ]
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group substituted with a halogen atom include a perfluoroalkyl group such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. The alkyl group substituted with a halogen atom has usually 1 to 25 carbon atoms, preferably 1 to 12 carbon atoms.
As R111Examples of the hydrocarbon group having 1 to 25 carbon atoms which may have a halogen atom include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, N-butyl, N-hexyl, N-octyl, isooctyl, N-nonyl, N-butyl, N-pentyl, N-hexyl, N-octyl, N-nonyl, N-pentyl, and N-hexyl,Straight-chain or branched alkyl groups having 1 to 25 carbon atoms such as isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, undecyl, lauryl, myristyl, cetyl, stearyl and the like: cycloalkyl groups having 3 to 25 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; a cycloalkylalkyl group having 4 to 25 carbon atoms such as a cyclopropylmethyl group and a cyclohexylmethyl group; aryl groups having 6 to 25 carbon atoms such as phenyl, naphthyl, anthryl and biphenyl groups; aralkyl groups having 7 to 25 carbon atoms such as benzyl, phenethyl, naphthylmethyl and phenyl; a fluoroalkyl group having 1 to 25 carbon atoms such as a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a2, 2, 2-trifluoroethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group; c1-25 chloroalkyl groups such as monochloromethyl, dichloromethyl, trichloromethyl, 2,2, 2-trichloroethyl, perchloroethyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl and the like; bromoalkyls having 1 to 25 carbon atoms, such as monobromomethyl, dibromomethyl, tribromomethyl, 2,2, 2-tribromoethyl, perbromoethyl, perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, and the like; iodoalkyl groups having 1 to 25 carbon atoms such as a monoiodomethyl group, a diiodomethyl group, a triiodomethyl group, a2, 2, 2-triiodoethyl group, a periodoethyl group, a periodopropyl group, a periodobutyl group, a periodopentyl group, and a periodohexyl group.
As R112、R113And R114Examples of the alkyl group having 1 to 6 carbon atoms include the group represented by the formula1AThe alkyl groups having 1 to 6 carbon atoms are the same.
R111Preferably an alkyl group having 4 to 25 carbon atoms which may have a halogen atom, and more preferably an alkyl group having 4 to 12 carbon atoms which may have a halogen atom.
X1preferably-CO-1and-COO-)1。
R6And R7The electron-withdrawing groups shown are each independently preferably a cyano group, a nitro group, a fluoro group, a trifluoromethyl group, and a group represented by the formula (I-1).
As R1And R2Ring structures formed by bonding each other and containing R1And R2Examples of the nitrogen-containing ring structure of the nitrogen atom to which the nitrogen atom is bonded include a nitrogen-containing heterocycle having a four-to ten-membered ring。R1And R2The ring structures formed by connecting them may be monocyclic, polycyclic or condensed. Specific examples thereof include a pyrrolidine ring, a pyrroline ring, an imidazolidine ring, an imidazoline ring, an oxazoline ring, a thiazoline ring, a piperidine ring, a morpholine ring, a piperazine ring, an indole ring, and an isoindole ring. R1And R2The ring formed by bonding may have a substituent, and examples of the substituent include an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group; alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy and butoxy groups.
As R2And R3Ring structures formed by bonding each other and containing R2Examples of the nitrogen-containing ring structure of the nitrogen atom to be bonded include nitrogen-containing heterocycles having four to ten members. R2And R3The ring structures formed by connecting them may be monocyclic, polycyclic or condensed. Specifically, there may be mentioned a pyrrolidine ring, a pyrroline ring, an imidazolidine ring, an imidazoline ring, an oxazoline ring, a thiazoline ring, a piperidine ring, a morpholine ring, a piperazine ring, an indole ring, an isoindole ring and a ring structure represented by the following formula (I-3).
Figure BDA0003369733560000181
[ in the formula (I-3), X represents a nitrogen atom, an oxygen atom or a sulfur atom.
Ring W1Represents a ring having a nitrogen atom and X as constituent elements.
Denotes a bond. ]
Ring W1Preferably a five-membered ring or a six-membered ring having nitrogen atoms and X as constituent elements.
Specific examples of the ring structure represented by the formula (I-3) include the following rings.
Figure BDA0003369733560000191
[ in the formula, a represents a bond. ]
R2And R3The ring structure formed by bonding may have a substituent, and examples of the substituent include an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group; alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy and butoxy groups.
R2And R3The ring structures bonded to each other are preferably ring structures represented by the following formula (I-4).
Figure BDA0003369733560000192
[ in the formula (I-4), R1The same meaning as above is indicated. m2 represents an integer of 1 to 7.
R11a、R11b、R11cAnd R11dEach independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
Denotes a bond to a carbon atom. ]
m2 is preferably 2 or 3, more preferably 2.
As R2And R4Examples of the ring structure formed by bonding to each other include a nitrogen-containing ring structure having four to ten members, and preferably a nitrogen-containing ring structure having five to nine members. R2And R4The ring structures formed by bonding to each other may be monocyclic or polycyclic. These rings may have a substituent. Examples of such a ring structure include an azole ring, an indole ring, a pyrimidine ring, and the following rings.
Figure BDA0003369733560000201
R2And R4The ring structure formed by bonding may have a substituent, and examples of the substituent include an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group; alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy and butoxy; amino, methylamino, dimethylamino and the like-NR22AR22BThe group shown (R)22AAnd R22BEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms); alkylthio groups having 1 to 12 carbon atoms such as a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, and the like; and a C4-9 heterocyclic group such as a pyrrolidinyl group, a piperidinyl group, or a morpholinyl group.
As R3And R6The ring structures formed by the mutual connection are R3－C＝C－C＝C－R6The ring structure forming the backbone of the ring. For example, phenyl group and the like are mentioned.
As R5And R7Examples of the ring structures formed by connecting the two to each other include the following ring structures. R5And R7The ring structure formed by bonding may have a substituent, and examples of the substituent include an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group; alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy and butoxy groups.
Figure BDA0003369733560000202
As R6And R7Examples of the ring structures formed by connecting the two to each other include the ring structures described below. R6And R7The ring structures formed by bonding may have a substituent (R in the following formula)1～R16) Examples of the substituent include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, and isobutyl group; alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy and butoxy; an ethylenically unsaturated group described later, and the like.
Figure BDA0003369733560000211
[ in the formula, a represents a bond to a carbon atom. ]
Preferably, R is6And R7At least any one of them is an electron withdrawing group.
The compound represented by the formula (I) is preferably a compound represented by the formula (II).
Figure BDA0003369733560000212
[ in the formula (II), R11、R12、R13、R14And R15Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 15 carbon atoms or a heterocyclic group, or-CH contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group2-may be replaced by-NR11A-、-SO2-, -CO-, -O-or-S-.
R16And R17Each independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an electron-withdrawing group.
R11ARepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R11And R12May be linked to each other to form a ring structure, R12And R13May be linked to each other to form a ring structure, R12And R14May be interconnected to form a ring structure.]
As R11～R15Examples of the optionally substituted C1-25 aliphatic hydrocarbon group include1The aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent is the same.
As R11～R15The aromatic hydrocarbon group having 6 to 15 carbon atoms which may have a substituent(s) is represented by1The aromatic hydrocarbon group having 6 to 15 carbon atoms which may have a substituent is the same.
As R11～R15Examples of the heterocyclic ring include the heterocyclic ring with R1The heterocyclic rings shown are the same heterocyclic rings.
As R16And R17Examples of the alkyl group having 1 to 25 carbon atoms include the group represented by the formula6The alkyl groups having 1 to 25 carbon atoms are the same.
As R16And R17Examples of the electron-withdrawing group include those with R6The electron withdrawing groups shown are the same groups.
As R11AExamples of the alkyl group having 1 to 6 carbon atoms include the group represented by the formula1AThe alkyl groups having 1 to 6 carbon atoms are the same.
As R11And R12Examples of the ring structure capable of being formed by connecting to each other include a ring structure with R1And R2The ring structures are connected to each other to form the same ring structure.
As R12And R13Examples of the ring structure capable of being formed by connecting to each other include a ring structure with R2And R3The ring structures are connected to each other to form the same ring structure. R12And R13The ring structure that can be formed by connecting them is preferably a single ring structure.
As R12And R14Examples of the ring structure capable of being formed by connecting to each other include a ring structure with R2And R4The ring structures are connected to each other to form the same ring structure. R12And R14The ring structure that can be formed by connecting them is preferably a single ring structure. R12And R14The ring structure that can be formed by connecting the rings to each other is preferably an aromatic ring, and more preferably a pyrimidine ring structure.
R11、R13And R15Each independently is preferably an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, more preferably an alkyl group having 1 to 25 carbon atoms which may have a substituent, and still more preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent.
Especially as R11The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably a methyl group.
Preferably, R is12And R14Each independently is an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or R12And R14Are connected to each other to form a ring structure.
R12And R13Preferably interconnected to form a ring structure, orOne step is preferably a ring structure represented by the above formula (I-4). Among the ring structures represented by the formula (I-4), preferred is a ring structure represented by the formula (I-4-1) or a ring structure represented by the formula (I-4-2), and particularly preferred is a ring structure represented by the formula (I-4-1). The ring structure represented by the formula (I-4), the formula (I-4-1) or the formula (I-4-2) may further have a substituent.
Figure BDA0003369733560000231
Preferably, R is16And R17Either of which is an ethylenically unsaturated group and the other of which is an electron withdrawing group.
R16And R17The electron-withdrawing groups shown are each independently preferably a cyano group, a nitro group, a fluoro group, a trifluoromethyl group, and a group represented by the formula (I-1). Cyano is particularly preferred.
R16And R17The ethylenically unsaturated groups shown are each independently preferably a vinyl group, an acryloyl group, a methacryloyl group, and a group represented by the formula (I-2). Further preferred is-CO-O- (CH)2)n-X2(X2And n represents an integer of 1 to 10 (preferably n is an integer of 2 to 6).
As R12And R13The compound represented by the formula (II) which is linked to each other to form a ring structure is preferably a compound represented by the formula (II-A-1) or a compound represented by the formula (II-A-2). As R12And R14The compound represented by the formula (II) which is linked to each other to form a ring structure is preferably a compound represented by the formula (II-B-1).
Figure BDA0003369733560000232
[ formula (II-A-1), formula (II-A-2) and formula (II-B-1) wherein R11、R14、R15、R16And R17Each represents the same meaning as above.
R11e、R11f、R11g、R11h、R11k、R11m、R11nEach independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
R11qAnd R11pEach independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, -NR22AR22BThe group shown (R)22AAnd R22BEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) or a heterocycle.]
Examples of the light selective absorbing compound (B) having a merocyanine structure include the following compounds.
Figure BDA0003369733560000241
Figure BDA0003369733560000251
Figure BDA0003369733560000261
Figure BDA0003369733560000271
Figure BDA0003369733560000281
Figure BDA0003369733560000291
Figure BDA0003369733560000301
A light selective absorbing compound having a merocyanine structure in the molecule can be produced by the method described in Japanese patent laid-open publication No. 2017-142412 and International publication No. 2019/004046.
The content of the light selective absorbing compound (B) having a merocyanine structure is usually 0.1 to 50 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 2 to 7 parts by mass, based on 100 parts by mass of the resin (A).
The light selective absorbing compound (B) having a merocyanine structure may contain 2 or more species.
< photocurable component (C) >)
The adhesive composition of the present invention may contain a photocurable component (C).
The photocurable component (C) may be a photoradically curable component such as a compound or oligomer that is cured by radical polymerization reaction under irradiation with light. Further, the composition may be a photo cation curable component such as a compound or oligomer that is cured by a cation polymerization reaction under irradiation with light. Here, the light is preferably active energy rays such as visible light, ultraviolet rays, X-rays, or electron rays.
The photocurable component (C) is preferably a photoradically curable component from the viewpoint of reactivity of the photoselective absorption compound (B) having a merocyanine structure in the molecule.
< photo radical polymerizable component >
Examples of the photo radical polymerizable component include radical polymerizable (meth) acrylic compounds.
Examples of the (meth) acrylic compound include compounds containing a (meth) acryloyl group such as a (meth) acrylate monomer having at least 1 (meth) acryloyloxy group in the molecule, a (meth) acrylamide monomer, and a (meth) acrylic oligomer having at least 2 (meth) acryloyl groups in the molecule. The (meth) acrylic oligomer is preferably a (meth) acrylate oligomer having at least 2 (meth) acryloyloxy groups in the molecule. The (meth) acrylic compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the (meth) acrylate monomer include a monofunctional (meth) acrylate monomer having 1 (meth) acryloyloxy group in the molecule, a difunctional (meth) acrylate monomer having 2 (meth) acryloyloxy groups in the molecule, and a polyfunctional (meth) acrylate monomer having 3 or more (meth) acryloyloxy groups in the molecule.
Examples of the monofunctional (meth) acrylate monomer include alkyl (meth) acrylates. In the alkyl (meth) acrylate, when the number of carbon atoms in the alkyl group is 3 or more, the alkyl group may be any of linear, branched, and cyclic. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
Examples of the monofunctional (meth) acrylate monomer include aralkyl (meth) acrylates such as benzyl (meth) acrylate; (meth) acrylic acid esters of terpene alcohols such as isobornyl (meth) acrylate; (meth) acrylates having a tetrahydrofurfuryl structure such as tetrahydrofurfuryl (meth) acrylate; (meth) acrylates having a cycloalkyl group at the alkyl moiety, such as cyclohexyl (meth) acrylate, cyclohexylmethyl methacrylate, dicyclopentyl acrylate, dicyclopentenyl (meth) acrylate, and 1, 4-cyclohexanedimethanol monoacrylate; aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylates having an ether bond at the alkyl moiety, such as 2-phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, and phenoxypolyethylene glycol (meth) acrylate; and so on.
Further, examples of the monofunctional (meth) acrylate monomer include monofunctional (meth) acrylates having a hydroxyl group at an alkyl position; a monofunctional (meth) acrylate having a carboxyl group at an alkyl site. Examples of the monofunctional (meth) acrylate having a hydroxyl group at an alkyl portion include 2-hydroxyethyl (meth) acrylate, 2-or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, and pentaerythritol mono (meth) acrylate. Examples of the monofunctional (meth) acrylate having a carboxyl group at an alkyl portion include 2-carboxyethyl (meth) acrylate, ω -carboxy-polycaprolactone (N ═ 2) mono (meth) acrylate, 1- [2- (meth) acryloyloxyethyl ] phthalate, 1- [2- (meth) acryloyloxyethyl ] hexahydrophthalate, 1- [2- (meth) acryloyloxyethyl ] succinate, 4- [2- (meth) acryloyloxyethyl ] trimellitate, and N- (meth) acryloyloxy-N ', N' -dicarboxymethyl-p-phenylenediamine.
The (meth) acrylamide monomer is preferably a (meth) acrylamide having a substituent at the N-position. A typical example of the substituent at the N-position thereof is an alkyl group, but may form a ring together with the nitrogen atom of (meth) acrylamide, and the ring may have an oxygen atom as a ring-constituting unit in addition to a carbon atom and the nitrogen atom of (meth) acrylamide. Further, a substituent such as an alkyl group or an oxo group (═ O) may be bonded to a carbon atom constituting the ring.
Examples of the N-substituted (meth) acrylamide include N-alkyl (meth) acrylamides such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-N-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, and N-hexyl (meth) acrylamide; n, N-dialkyl (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide, and the like. The N-substituent may be an alkyl group having a hydroxyl group, and examples thereof include N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, and the like. Specific examples of the N-substituted (meth) acrylamide forming the five-membered ring or the six-membered ring include N-acryloylpyrrolidine, 3-acryloyl-2-oxazolidinone, 4-acryloylmorpholine, N-acryloylpiperidine, and N-methacryloylpiperidine.
Examples of the difunctional (meth) acrylate monomer include:
alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, 1, 3-butylene glycol di (meth) acrylate, 1, 4-butylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate;
polyoxyalkylene glycol di (meth) acrylates such as 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, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate;
di (meth) acrylates of halogen-substituted alkylene glycols such as tetrafluoroethylene di (meth) acrylate;
di (meth) acrylates of aliphatic polyhydric alcohols such as trimethylolpropane di (meth) acrylate, ditrimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate and the like;
hydrogenated dicyclopentadiene or tricyclodecanedialkanol di (meth) acrylates such as hydrogenated biscyclopentadienyl di (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate;
1, 3-dioxane-2, 5-diylbis (meth) acrylate [ alternative name: dioxane diol or dioxane di (meth) acrylate of dioxane dialkanol such as dioxane diol di (meth) acrylate ];
di (meth) acrylates of alkylene oxide adducts of bisphenol a or bisphenol F such as bisphenol a ethylene oxide adduct diacrylate and bisphenol F ethylene oxide adduct diacrylate;
epoxy di (meth) acrylates of bisphenol a or bisphenol F such as acrylic acid adducts of bisphenol a diglycidyl ether and acrylic acid adducts of bisphenol F diglycidyl ether; silicone di (meth) acrylate;
di (meth) acrylate of neopentyl glycol hydroxypivalate;
2, 2-bis [4- (meth) acryloyloxyethoxyethoxyphenyl ] propane; 2, 2-bis [4- (meth) acryloyloxyethoxyethoxyethoxycyclohexyl ] propane;
di (meth) acrylate of 2- (2-hydroxy-1, 1-dimethylethyl) -5-ethyl-5-hydroxymethyl-1, 3-dioxane ];
tris (hydroxyethyl) isocyanurate di (meth) acrylate; and so on.
Examples of the trifunctional or higher multifunctional (meth) acrylate monomer include trifunctional or higher multifunctional (meth) acrylates of aliphatic polyhydric alcohols such as glycerol tri (meth) acrylate, alkoxylated glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; poly (meth) acrylates of trifunctional or higher halogen-substituted polyols; tri (meth) acrylates of alkylene oxide adducts of glycerol; tri (meth) acrylate of alkylene oxide adduct of trimethylolpropane; 1,1, 1-tris [ (meth) acryloyloxyethoxyethoxy ] propane; tris (hydroxyethyl) isocyanurate tri (meth) acrylate, and the like.
Further, commercially available products can be used. Examples of commercially available products include A-DPH-12E, A-TMPT and A-9300 (manufactured by Ninghamu chemical Co., Ltd.).
Examples of the (meth) acrylic oligomer include urethane (meth) acrylic oligomer, polyester (meth) acrylic oligomer, and epoxy (meth) acrylic oligomer.
The urethane (meth) acrylic oligomer refers to a compound having a urethane bond (-NHCOO-) and at least 2 (meth) acryloyl groups in a molecule. Specifically, it may be: a urethanization reaction product of a hydroxyl group-containing (meth) acrylic monomer having at least 1 (meth) acryloyl group and at least 1 hydroxyl group, respectively, in a molecule, and a polyisocyanate; a urethane-formed reaction product of a urethane compound having a terminal isocyanate group obtained by reacting a polyol with a polyisocyanate and a (meth) acrylic monomer having at least 1 (meth) acryloyl group and at least 1 hydroxyl group in the molecule, respectively.
The hydroxyl group-containing (meth) acrylic monomer used in the above-mentioned urethanization reaction may be, for example, a hydroxyl group-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, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate. Specific examples of the hydroxyl group-containing (meth) acrylate monomer other than the hydroxyl group-containing (meth) acrylate monomer include N-hydroxyalkyl (meth) acrylamide monomers such as N-hydroxyethyl (meth) acrylamide and N-hydroxymethyl (meth) acrylamide.
Examples of the polyisocyanate to be subjected to the urethane-forming reaction with the hydroxyl group-containing (meth) acrylic monomer include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates (e.g., hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, etc.), di-or triisocyanates such as triphenylmethane triisocyanate and dibenzylbenzene triisocyanate, and polyisocyanates obtained by polymerizing the above diisocyanates.
As the polyol used for forming the isocyanate group-terminated urethane compound by the reaction with the polyisocyanate, a polyester polyol, a polyether polyol, or the like can be used in addition to the aromatic, aliphatic, or alicyclic polyol. Examples of the aliphatic and alicyclic polyhydric alcohols include 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerin, hydrogenated bisphenol a, and the like.
The polyester polyol is obtained by a dehydration condensation reaction of the above polyol with a polycarboxylic acid or an anhydride thereof. As examples of the polycarboxylic acid or anhydride thereof, when the substance which may be an anhydride is denoted by "(anhydride)", there are succinic acid (anhydride), adipic acid, maleic acid (anhydride), itaconic acid (anhydride), trimellitic acid (anhydride), pyromellitic acid (anhydride), phthalic acid (anhydride), isophthalic acid, terephthalic acid, hexahydrophthalic acid (anhydride), and the like.
The polyether polyol may be a polyalkylene glycol, a polyoxyalkylene-modified polyol obtained by the reaction of the above polyol or dihydroxybenzene with an alkylene oxide, or the like.
The polyester (meth) acrylate oligomer means an oligomer having an ester bond and at least 2 (meth) acryloyloxy groups in the molecule.
The polyester (meth) acrylate oligomer can be obtained by, for example, subjecting (meth) acrylic acid, a polycarboxylic acid or an anhydride thereof, and a polyol to dehydration condensation reaction.
Examples of the polycarboxylic acid or anhydride thereof include succinic anhydride, adipic acid, maleic anhydride, itaconic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, phthalic acid, succinic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid.
Examples of the polyhydric alcohol include 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerol, hydrogenated bisphenol a, and the like.
The epoxy (meth) acrylic oligomer can be obtained by addition reaction of a polyglycidyl ether and (meth) acrylic acid. The epoxy (meth) acrylic oligomer has at least 2 (meth) acryloyloxy groups in the molecule.
Examples of the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, and bisphenol a diglycidyl ether.
The photoradically curable component preferably contains a (meth) acrylate compound, and more preferably contains a polyfunctional (meth) acrylate compound.
< Photocationically curable component >
Examples of the photocationic curable component include an epoxy compound, an oxetane compound, and a vinyl compound.
Examples of the epoxy compound include alicyclic epoxy compounds, aromatic epoxy compounds, hydrogenated epoxy compounds, and aliphatic epoxy compounds.
The alicyclic epoxy compound is a compound having 1 or more epoxy groups bonded to an alicyclic ring in a molecule. Examples of the epoxy group bonded to the alicyclic ring include an oxabicyclohexyl group and an oxabicycloheptyl group. The alicyclic epoxy compound may include 1 alicyclic epoxy group, or may include 2 or more alicyclic epoxy groups.
Examples of the alicyclic epoxy compound include 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl 3, 4-epoxy-6-methylcyclohexanecarboxylate, ethylenebis (3, 4-epoxycyclohexanecarboxylate), bis (3, 4-epoxycyclohexylmethyl) adipate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, diethylene glycol bis (3, 4-epoxycyclohexylmethyl ether), ethylene glycol bis (3, 4-epoxycyclohexylmethyl ether), 2,3,14, 15-diepoxy-7, 11,18, 21-tetraoxatrispiro [5.2.2.5.2.2] heneicosane, 3- (3, 4-epoxycyclohexyl) -8, 9-epoxy-1, 5-dioxaspiro [5.5] undecane, 4-vinylcyclohexene dioxide, limonene dioxide, bis (2, 3-epoxycyclopentyl) ether, dicyclopentadiene dioxide, and the like.
The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in a molecule. Examples of the aromatic epoxy compound include bisphenol type epoxy compounds such as diglycidyl ether of bisphenol a, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S, and oligomers thereof; phenol novolac type epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac epoxy resin, and the like; polyfunctional epoxy compounds such as glycidyl ethers of 2,2 ', 4, 4' -tetrahydroxydiphenylmethane and glycidyl ethers of 2,2 ', 4, 4' -tetrahydroxybenzophenone; and polyfunctional epoxy resins such as epoxidized polyvinylphenol.
The hydrogenated epoxy compound is a glycidyl ether of a polyhydric alcohol having an alicyclic ring, and may be a compound obtained by glycidyl etherification of a nuclear hydrogenated polyhydric compound obtained by selective hydrogenation of an aromatic ring of an aromatic polyhydric alcohol under pressure in the presence of a catalyst. Specific examples of the aromatic polyol include bisphenol compounds such as bisphenol a, bisphenol F and bisphenol S; phenol novolac resins such as phenol novolac resin, cresol novolac resin, hydroxybenzaldehyde phenol novolac resin, and the like; and polyfunctional compounds such as tetrahydroxydiphenylmethane, tetrahydroxybenzophenone, and polyvinyl phenol. Glycidyl ethers can be produced by reacting epichlorohydrin with an alicyclic polyol obtained by hydrogenating the aromatic ring of an aromatic polyol. Among the hydrogenated epoxy compounds, preferred compounds include hydrogenated diglycidyl ethers of bisphenol a.
The aliphatic epoxy compound is a compound having at least 1 oxirane ring (ternary cyclic ether) bonded to an aliphatic carbon atom in the molecule. Examples include: monofunctional epoxy compounds such as butyl glycidyl ether and 2-ethylhexyl glycidyl ether; difunctional epoxy compounds such as 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and the like; trifunctional or higher epoxy compounds such as trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether; 4-vinylcyclohexene dioxide, limonene dioxide, and the like, epoxy compounds having 1 epoxy group directly bonded to an alicyclic ring and an oxirane ring bonded to an aliphatic carbon atom, and the like.
The oxetane compound is a compound having 1 or more oxetane rings (oxetanyl groups) in the molecule. Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, 1, 4-bis [ { (3-ethyloxetan-3-yl) methoxy } methyl ] benzene, 3-ethyl-3 [ { (3-ethyloxetan-3-yl) methoxy } methyl ] oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, and 3- (cyclohexyloxy) methyl-3-ethyloxetane.
Examples of the vinyl compound include aliphatic or alicyclic vinyl ether compounds. Examples of the vinyl compound include vinyl ethers of alkyl or alkenyl alcohols having 5 to 20 carbon atoms such as n-amyl vinyl ether, isoamyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, n-dodecyl vinyl ether, stearyl vinyl ether, oleyl vinyl ether and the like; hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether and 4-hydroxybutyl vinyl ether; vinyl ethers of monoalcohols having an aliphatic ring or an aromatic ring, such as cyclohexyl vinyl ether, 2-methylcyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, and benzyl vinyl ether; mono-to polyvinyl ethers of polyhydric alcohols such as glycerol monovinyl ether, 1, 4-butanediol divinyl ether, 1, 6-hexanediol divinyl ether, neopentyl glycol divinyl ether, pentaerythritol tetravinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, 1, 4-dihydroxycyclohexane monovinyl ether, 1, 4-dihydroxycyclohexane divinyl ether, 1, 4-dihydroxymethylcyclohexane monovinyl ether, 1, 4-dihydroxymethylcyclohexane divinyl ether, and the like; polyalkylene glycol mono-divinyl ethers such as diethylene glycol divinyl ether, triethylene glycol divinyl ether, and diethylene glycol monobutyl monovinyl ether; glycidyl vinyl ether, ethylene glycol vinyl ether methacrylate, and the like.
The content of the photocurable component (C) is usually 0.1 to 300 parts by mass, preferably 0.5 to 100 parts by mass, more preferably 1 to 50 parts by mass, and still more preferably 5 to 30 parts by mass, based on 100 parts by mass of the resin (a).
< photoinitiator (D) >
The adhesive composition of the present invention preferably further comprises a photoinitiator (D).
The photoinitiator (D) is a compound (polymerization initiator) that absorbs energy of light to thereby initiate polymerization reaction. Here, the light is preferably active energy rays such as visible light, ultraviolet rays, X-rays, or electron rays.
Specific examples of the photoinitiator (D) include: a compound that absorbs energy of light to thereby generate radicals (photo radical generator), a compound that absorbs energy of light to thereby generate cations (acids) (photo cation generator), and a compound that absorbs energy of light to thereby generate anions (bases) (photo base generator).
The photoinitiator (D) may contain 2 or more species, and a photoradical generator and a photocation generator may be used in combination.
The photoinitiator (D) is preferably a photoradical generator from the viewpoint of reactivity of the polymerization reaction.
Examples of the photo radical generator include alkylphenone compounds, benzoin compounds, benzophenone compounds, oxime ester compounds, and phosphine compounds.
Examples of the alkylphenone compound include an α -aminoalkylphenylketone compound, an α -hydroxyalkylphenylketone compound, and an α -alkoxyalkylphenone compound.
Examples of the α -aminoalkylphenylketone compound include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, and the like, preferred examples thereof include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. Commercially available products such as IRGACURE (registered trademark) 127, 184, 369E, 379EG, 651, 907, 1173, 2959 (manufactured by BASF japan ltd.), SEIKUOL (registered trademark) BEE (manufactured by seiki chemical).
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
Examples of the benzophenone compound include benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone. The benzophenone compound may be a commercially available compound.
Examples of the oxime ester compounds include N-benzoyloxy-1- (4-phenylthiophenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine, n-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxopentylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, and the like. As the oxime compound, commercially available products such as IRGACURE OXE-01, OXE-02, OXE-03 (BASF, Japan Co., Ltd.), N-1919, NCI-730, NCI-831, NCI-930(ADEKA, Ltd.), PBG3057(TRONLY, Ltd.) and the like can be used.
Examples of the phosphine compound include acylphosphine oxides such as phenyl (2,4, 6-trimethylbenzoyl) phosphine oxide and diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide. Examples of the phosphine compound include IRGACURE (registered trade product) TPO and IRGACURE 819 (manufactured by BASF Japan K.K.).
The photoradical generator is preferably an oxime ester compound.
Examples of the photo cation generator include onium salts such as aromatic iodonium salts and aromatic sulfonium salts; an aromatic diazonium salt; iron-arene complexes, and the like.
The aromatic iodonium salt is a compound having a diaryliodonium cation, and typical examples of the cation include diphenyliodonium cation. The aromatic sulfonium salt is a compound having a triarylsulfonium cation, and typical examples of the cation include a triphenylsulfonium cation, a 4, 4' -bis (diphenylsulfonium) diphenylsulfide cation, and the like. The aromatic diazonium salt is a compound having a diazonium cation, and the cation is typically a benzenediazonium cation. Additionally, the iron-arene complex is typically a cyclopentadienyl iron (II) arene cation complex salt.
The cations shown above are paired with anions (anion) to constitute a photo cation generator. Examples of the anion constituting the photo cation generator include a specific phosphorus anion [ (Rf)nPF6-n]-Hexafluorophosphate anion PF6 -Hexafluoroantimonate anion SbF6 -Pentafluoro hydroxy antimonate anion SbF5(OH)-Hexafluoroarsenate anion AsF6 -Tetrafluoroborate anion BF4 -Tetrakis (pentafluorophenyl) borate anion B (C)6F5)4 -And the like. Among them, a specific phosphorus anion [ (Rf) is preferable from the viewpoints of curability of the cationically polymerizable compound and safety of the obtained photo-selective absorption layernPF6-n]-Hexafluorophosphate anion PF6 -Tetrakis (pentafluorophenyl) borate anion B (C)6F5)4 -。
The content of the photoinitiator (D) is usually 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.2 to 3 parts by mass, based on 100 parts by mass of the resin (a).
< crosslinking agent (E) >)
The adhesive composition of the present invention may contain a crosslinking agent (E).
Examples of the crosslinking agent (E) include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, and the like, and particularly, from the viewpoints of pot life of the adhesive composition, durability of the adhesive layer, crosslinking speed, and the like, an isocyanate crosslinking agent is preferable.
The isocyanate-based crosslinking agent is preferably a compound having at least 2 isocyanate groups (-NCO) in the molecule, and examples thereof include aliphatic isocyanate-based compounds (e.g., hexamethylene diisocyanate), alicyclic isocyanate-based compounds (e.g., isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate), aromatic isocyanate-based compounds (e.g., toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, etc.), and the like. The crosslinking agent (E) may be an adduct (adduct) of the isocyanate compound with a polyol compound [ for example, an adduct of glycerin, trimethylolpropane or the like ], an isocyanurate compound, a biuret compound, a urethane prepolymer type isocyanate compound obtained by addition reaction with a polyether polyol, a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol or the like, or the like. The crosslinking agent (B) may be used alone or in combination of two or more. Among these, typically, aromatic isocyanate compounds (e.g., toluene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (e.g., hexamethylene diisocyanate), adducts thereof based on polyol compounds (e.g., glycerin, trimethylolpropane), or isocyanurate compounds can be cited. If the crosslinking agent (B) is an aromatic isocyanate-based compound and/or an adduct thereof based on a polyol compound or an isocyanurate compound, it is possible to improve the durability of the adhesive layer because it is advantageous to form an optimum crosslinking density (or crosslinking structure). Particularly, if the adhesive layer is a toluene diisocyanate-based compound and/or an adduct thereof based on a polyol compound, the durability can be improved even when the adhesive layer is applied to a polarizing plate or the like.
The content of the crosslinking agent (E) is usually 0.01 to 15 parts by mass, preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the resin (A).
The adhesive composition of the present invention may further contain a silane compound (F).
Examples of the silane compound (F) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
The silane compound (D) may be a silicone oligomer. Specific examples of the silicone oligomer are as follows when the silicone oligomer is expressed as a combination of monomers.
Mercaptopropyl-containing oligomers such as 3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomer; mercapto methyl group-containing oligomers such as mercapto methyltrimethoxysilane-tetramethoxysilane oligomer, mercapto methyltrimethoxysilane-tetraethoxysilane oligomer, mercapto methyltriethoxysilane-tetramethoxysilane oligomer, and mercapto methyltriethoxysilane-tetraethoxysilane oligomer; 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyl group-containing copolymers such as 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane oligomer, methacryloxypropyl-containing oligomers such as 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, and 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer; 3-acryloxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-acryloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-acryloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-acryloxypropyltriethoxysilane-tetraethoxysilane oligomer, acryloxypropyl-containing oligomers such as 3-acryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-acryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, and 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer; vinyl group-containing oligomers such as vinyltrimethoxysilane-tetramethoxysilane oligomer, vinyltrimethoxysilane-tetraethoxysilane oligomer, vinyltriethoxysilane-tetramethoxysilane oligomer, vinyltriethoxysilane-tetraethoxysilane oligomer, vinylmethyldimethoxysilane-tetramethoxysilane oligomer, vinylmethyldimethoxysilane-tetraethoxysilane oligomer, vinylmethyldiethoxysilane-tetramethoxysilane oligomer, and vinylmethyldiethoxysilane-tetraethoxysilane oligomer; amino group-containing copolymers such as 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.
The silane compound (F) may be a silane compound represented by the following formula (F1).
Figure BDA0003369733560000441
(wherein A represents a C1-20 alkanediyl group or a C3-20 divalent alicyclic hydrocarbon group, -CH constituting the alkanediyl group and the alicyclic hydrocarbon group2-may be replaced by-O-or-CO-, R41Represents an alkyl group having 1 to 5 carbon atoms, R42、R43、R44、R45And R46Each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. )
Examples of the alkanediyl group having 1 to 20 carbon atoms represented by A include a methylene group, a1, 2-ethanediyl group, a1, 3-propanediyl group, a1, 4-butanediyl group, a1, 5-pentanediyl group, a1, 6-hexanediyl group, a1, 7-heptanediyl group, a1, 8-octanediyl group, a1, 9-nonanediyl group, a1, 10-decanediyl group, a1, 12-dodecanediyl group, a1, 14-tetradecanediyl group, a1, 16-hexadecanediyl group, a1, 18-octadecanediyl group and a1, 20-eicosanediyl group. Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a1, 3-cyclopentanediyl group and a1, 4-cyclohexanediyl group. as-CH constituting the alkanediyl group and the alicyclic hydrocarbon group2Examples of the group in which-is replaced by-O-or-CO-, include-CH2CH2-O-CH2CH2-、-CH2CH2-O-CH2CH2-O-CH2CH2-、-CH2CH2-O-CH2CH2-O-CH2CH2-O-CH2CH2-、-CH2CH2-CO-O-CH2CH2-、-CH2CH2-O-CH2CH2-CO-O-CH2CH2-、-CH2CH2CH2CH2-O-CH2CH2-and-CH2CH2CH2CH2-O-CH2CH2CH2CH2-。
As R41～R45Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and pentyl, and R is42～R45Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group and a pentyloxy group.
Examples of the silane compound represented by the formula (f1) include (trimethoxysilyl) methane, 1, 2-bis (trimethoxysilyl) ethane, 1, 2-bis (triethoxysilyl) ethane, 1, 3-bis (trimethoxysilyl) propane, 1, 3-bis (triethoxysilyl) propane, 1, 4-bis (trimethoxysilyl) butane, 1, 4-bis (triethoxysilyl) butane, 1, 5-bis (trimethoxysilyl) pentane, 1, 5-bis (triethoxysilyl) pentane, 1, 6-bis (trimethoxysilyl) hexane, 1, 6-bis (triethoxysilyl) hexane, 1, 6-bis (tripropoxysilyl) hexane, 1, 8-bis (trimethoxysilyl) octane, 1, 2-bis (trimethoxysilyl) ethane, 1, 2-bis (triethoxysilyl) ethane, 1, 4-bis (triethoxysilyl) butane, 1, 5-bis (trimethoxysilyl) pentane, 1, 5-bis (triethoxysilyl) pentane, 1, 6-bis (trimethoxysilyl) hexane, Bis (tri-C1-5 alkoxysilyl) C1-10 alkanes such as 1, 8-bis (triethoxysilyl) octane and 1, 8-bis (tripropoxysilyl) octane; bis (di-C1-5 alkoxy C1-5 alkylsilyl) C1-10 alkanes such as bis (dimethoxymethylsilyl) methane, 1, 2-bis (dimethoxymethylsilyl) ethane, 1, 2-bis (dimethoxyethylsilyl) ethane, 1, 4-bis (dimethoxymethylsilyl) butane, 1, 4-bis (dimethoxyethylsilyl) butane, 1, 6-bis (dimethoxymethylsilyl) hexane, 1, 6-bis (dimethoxyethylsilyl) hexane, 1, 8-bis (dimethoxymethylsilyl) octane and 1, 8-bis (dimethoxyethylsilyl) octane; and bis (mono C1-5 alkoxydiC 1-5 alkylsilyl) C1-10 alkanes such as 1, 6-bis (methoxydimethylsilyl) hexane and 1, 8-bis (methoxydimethylsilyl) octane. Among these, bis (tri C1-3 alkoxysilyl) C1-10 paraffins such as 1, 2-bis (trimethoxysilyl) ethane, 1, 3-bis (trimethoxysilyl) propane, 1, 4-bis (trimethoxysilyl) butane, 1, 5-bis (trimethoxysilyl) pentane, 1, 6-bis (trimethoxysilyl) hexane, 1, 8-bis (trimethoxysilyl) octane, and particularly preferably 1, 6-bis (trimethoxysilyl) hexane and 1, 8-bis (trimethoxysilyl) octane are preferable.
The content of the silane compound (F) is usually 0.01 to 10 parts by mass, preferably 0.03 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, and still more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the resin (A).
The adhesive composition may further contain an antistatic agent.
Examples of the antistatic agent include a surfactant, a silicone compound, a conductive polymer, an ionic compound, and the like, and an ionic compound is preferable. The ionic compound may be a conventional ionic compound. Examples of the cation component constituting the ionic compound include an organic cation and an inorganic cation. Examples of the organic cation include a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, an imidazolium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation. Examples of the inorganic cation include alkali metal cations such as lithium cation, potassium cation, sodium cation, and cesium cation, and alkaline earth metal cations such as magnesium cation and calcium cation. In particular, from the viewpoint of compatibility with the (meth) acrylic resin, a pyridinium cation, an imidazolium cation, a pyrrolidinium cation, a lithium cation, and a potassium cation are preferable. The anionic component constituting the ionic compound may be any of inorganic anions and organic anions, and is preferably an anionic component containing a fluorine atom from the viewpoint of antistatic performance. Examples of the anion component containing a fluorine atom include hexafluorophosphate anion (PF)6 -) Bis (trifluoromethanesulfonyl) imide anion [ (CF)3SO2)2N-]Bis (fluorosulfonyl) imide anion [ (FSO)2)2N-]Tetrakis (pentafluorophenyl) borate anion [ (C)6F5)4B-]And the like. These ionic compounds may be used alone or in combination of two or more. Particular preference is given to the bis (trifluoromethanesulfonyl) imide anion [ (CF)3SO2)2N-]Bis (fluorosulfonyl) imide anion [ (FSO)2)2N-]Tetrakis (pentafluorophenyl) borate anion [ (C)6F5)4B-]。
From the viewpoint of the stability with time of the antistatic performance of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, an ionic compound which is solid at room temperature is preferable.
The content of the antistatic agent is, for example, 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 1 to 7 parts by mass, based on 100 parts by mass of the resin (A).
The pressure-sensitive adhesive composition may further contain 1 or 2 or more kinds of additives selected from the group consisting of solvents, crosslinking catalysts, tackifiers, plasticizers, softeners, pigments, rust inhibitors, inorganic fillers, light-scattering fine particles, and the like.
< adhesive layer >
The adhesive layer of the present invention can be formed, for example, as follows: the adhesive composition of the present invention is formed by dissolving or dispersing the adhesive composition in a solvent to prepare a solvent-containing adhesive composition, applying the adhesive composition to the surface of a substrate, drying the adhesive composition, and then irradiating the adhesive composition with active energy rays. The pressure-sensitive adhesive layer of the present invention can also be said to be a photo-cured product of the pressure-sensitive adhesive composition.
The substrate is preferably a plastic film, and specifically, a release film subjected to a release treatment is exemplified. Examples of the release film include: a film obtained by subjecting one surface of a film containing a resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate to a mold release treatment such as a silicone treatment.
The conditions (drying temperature and drying time) for drying the coating film formed from the binder composition containing a solvent may be appropriately set depending on the composition and concentration thereof, and are preferably 60 to 150 ℃ for 1 to 60 minutes.
The active energy ray irradiation after drying of the coating film is preferably ultraviolet ray irradiation. The illuminance of the ultraviolet ray to be irradiated is preferably 10mW/cm2～3000mW/cm2. The cumulative amount of ultraviolet light is preferably 10mJ/cm2～5000mJ/cm2。
The ultraviolet lamp for ultraviolet irradiation may be a mercury lamp, a metal halide lamp, or an LED lamp.
The pressure-sensitive adhesive layer of the present invention is preferably a pressure-sensitive adhesive layer satisfying the following formula (3), and more preferably a pressure-sensitive adhesive layer also satisfying the formula (4).
A(405)≥0.5 (3)
[ in the formula (3), A (405) represents the absorbance at a wavelength of 405 nm. ]
A(405)/A(440)≥5 (4)
In the formula (4), A (405) represents the absorbance at a wavelength of 405nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]
A larger value of A (405) indicates a higher absorption at a wavelength of 405 nm. If the value of a (405) is less than 0.5, absorption at a wavelength of 405nm is low, and deterioration of a member (for example, a display device such as an organic EL element, a liquid crystal retardation film, or the like) which is easily deteriorated by light having a wavelength of 400nm or so tends to occur. The value of a (405) is preferably 0.6 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more. There is no specific upper limit, and it is usually 10 or less.
The value of A (405)/A (440) represents the magnitude of absorption at a wavelength of 405nm relative to the magnitude of absorption at a wavelength of 440nm, and a larger value indicates more specific absorption in a wavelength region around the wavelength of 405 nm. The value of a (405)/a (440) is preferably 10 or more, more preferably 30 or more, further preferably 75 or more, and particularly preferably 100 or more.
The thickness of the adhesive layer of the present invention is usually 0.1 to 30 μm, preferably 0.5 to 25 μm, more preferably 1 to 15 μm, and particularly preferably 2.5 to 10 μm.
The gel fraction of the adhesive layer of the present invention is usually 50 to 99.9 mass%, preferably 60 to 99 mass%, more preferably 70 to 95 mass%, and still more preferably 75 to 90 mass%.
< optical film with adhesive layer >
The adhesive composition of the present invention and the adhesive layer formed from the adhesive composition can be used for, for example, bonding an optical film.
An optical film with an adhesive layer in which an optical film is laminated on at least one side of the adhesive layer of the present invention is also included in the present invention.
The optical film with an adhesive layer of the present invention can be formed by dissolving or dispersing the adhesive composition in a solvent to prepare a solvent-containing adhesive composition, applying the adhesive composition to the surface of an optical film, drying the adhesive composition, and then irradiating the optical film with an active energy ray. Alternatively, the pressure-sensitive adhesive layer may be formed on the release film in the same manner, and the pressure-sensitive adhesive layer may be laminated (transferred) on the surface of the optical film.
The optical film has optical functions of transmitting, reflecting, and absorbing light. The optical film may be a single-layer film or a multilayer film. Examples of the optical film include a polarizing film, a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, and a light-collecting film, and a polarizing film, a retardation film, and a laminated film thereof are preferable.
The condensing film is used for the purpose of optical path control or the like, and may be a prism array sheet, a lens array sheet, a sheet provided with a dot matrix, or the like.
The brightness enhancement film is used for the purpose of improving the brightness of a liquid crystal display device to which a polarizing plate is applied. Specifically, there may be mentioned: a reflective polarization separation sheet designed to have a reflectance anisotropy by laminating a plurality of films having different refractive index anisotropies, an alignment film of a cholesteric liquid crystal polymer, a circularly polarized light separation sheet in which an alignment liquid crystal layer thereof is supported on a base film, and the like.
The polarizing film is a film having the following properties: the polarizing film is a film that absorbs linearly polarized light having a plane of vibration parallel to the absorption axis thereof and transmits linearly polarized light having a plane of vibration orthogonal to the absorption axis (parallel to the transmission axis), and for example, a film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol resin film can be used.
Examples of the dichroic dye include iodine and a dichroic organic dye.
The saponification degree of the polyvinyl alcohol resin is usually 85 mol% to 100 mol%, and preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and may be, for example, polyvinyl formal, polyvinyl acetal, or the like, which is obtained by modifying an aldehyde. The polymerization degree of the polyvinyl alcohol resin is usually 1000 to 10000, preferably 1500 to 5000.
A film formed of a polyvinyl alcohol resin is generally used as a raw material film of a polarizing film. The polyvinyl alcohol resin can be formed into a film by a known method. The thickness of the raw material film is usually 1 to 150 μm, and preferably 10 μm or more in consideration of ease of stretching and the like.
The polarizing film is produced, for example, by subjecting a raw material film to uniaxial stretching, dyeing the film with a dichroic dye to adsorb the dichroic dye, treating the film with an aqueous boric acid solution, washing the film with water, and finally drying. The thickness of the polarizing film is usually 1 to 30 μm, and from the viewpoint of making a film of the optical laminate with an adhesive layer thinner, the thickness is preferably 20 μm or less, more preferably 15 μm or less, and particularly 10 μm or less.
The polarizing plate is preferably provided with a protective film on at least one surface of the polarizing film via an adhesive.
As the adhesive, a known adhesive can be used, and an aqueous adhesive or an active energy ray-curable adhesive can be used.
Examples of the aqueous adhesive include conventional aqueous adhesives (for example, adhesives comprising an aqueous polyvinyl alcohol resin solution, aqueous two-component urethane emulsion adhesives, aldehyde compounds, epoxy compounds, melamine compounds, methylol compounds, isocyanate compounds, amine compounds, crosslinking agents such as polyvalent metal salts, and the like). Among them, an aqueous adhesive comprising a polyvinyl alcohol resin aqueous solution can be suitably used. In the case of using the water-based adhesive, it is preferable to perform a drying step after the polarizing film and the protective film are bonded to each other in order to remove water contained in the water-based adhesive. After the drying step, a curing step of curing at a temperature of, for example, about 20 to 45 ℃ may be provided. The adhesive layer formed of the aqueous adhesive is usually 0.001 to 5 μm.
The active energy ray-curable adhesive is an adhesive which is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron ray, and examples thereof include a curable composition containing a polymerizable compound and a photopolymerization initiator, a curable composition containing a photoreactive resin, a curable composition containing a binder resin and a photoreactive crosslinking agent, and the like, and an ultraviolet ray-curable adhesive is preferable.
Examples of the method for bonding the polarizing film and the protective film include: and a method of performing a surface activation treatment such as saponification, corona treatment, or plasma treatment on at least one of the surfaces to be bonded. When the protective films are laminated on both surfaces of the polarizing film, the adhesives used for laminating the resin films may be the same type of adhesive or different types of adhesives.
The protective film is preferably a film made of a transparent thermoplastic resin. Specifically, examples include polyolefin-based resins; a cellulose-based resin; a polyester resin; (meth) acrylic resins; or mixtures, copolymers, etc. thereof. When protective films are provided on both sides of the polarizing film, the protective films used may be films containing different thermoplastic resins or films containing the same thermoplastic resin.
When a protective film is laminated on at least one surface of the polarizing film, the protective film is preferably a protective film containing a polyolefin resin or a cellulose resin. By using these films, shrinkage of the polarizing film in a high-temperature environment can be effectively suppressed without impairing the optical characteristics of the polarizing film. The protective film may be an oxygen barrier layer.
A preferable structure of the polarizing plate is one in which a protective film is laminated on at least one surface of a polarizing film via an adhesive layer. When the protective film is laminated on only one surface of the polarizing film, it is more preferably laminated on the visible side. The protective film laminated on the visible side is preferably a protective film containing a triacetyl cellulose resin or a cycloolefin resin. The protective film may be an unstretched film or may be stretched in any direction to have a retardation. The surface of the protective film laminated on the visible side may be provided with a surface treatment layer such as a hard coat layer or an antiglare layer.
When the protective films are laminated on both sides of the polarizing film, the protective film on the panel side (the side opposite to the visible side) is preferably a protective film or a retardation film comprising a triacetyl cellulose resin, a cycloolefin resin, or an acrylic resin. The retardation film may be a zero retardation film described later.
The retardation film is an optical film exhibiting optical anisotropy, and examples thereof include: and stretched films obtained by stretching a polymer film containing polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycycloolefin, polystyrene, polysulfone, polyethersulfone, polyvinylidene fluoride/polymethyl methacrylate, acetyl cellulose, a saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, or the like by a factor of about 1.01 to 6. Among the stretched films, a polymer film obtained by uniaxially or biaxially stretching an acetyl cellulose, polyester, polycarbonate film, or cycloolefin resin film is preferable. The retardation film may be one in which a liquid crystalline compound is applied to a substrate and aligned to exhibit optical anisotropy.
In the present specification, the retardation film includes a zero retardation film, and includes films such as a uniaxial retardation film, a low photoelastic coefficient retardation film, and a wide-angle retardation film.
Zero retardation film means that the front retardation R iseRetardation R with respect to the thickness directionthAll of them are-15 to 15nm and optically isotropic films. The zero retardation film may be a resin film containing a cellulose-based resin, a polyolefin-based resin (e.g., a chain polyolefin-based resin or a polycycloolefin-based resin), or a polyethylene terephthalate-based resin, and is preferably a cellulose-based resin or a polyolefin-based resin from the viewpoint of easy control of retardation value and easy availability. A zero retardation film may also be used as the protective film. Examples of the zero retardation film include: "Z-TAC" (trade name) sold by Fuji film corporation, "Zero TAC (registered trademark)" sold by Konica Minolta corporation, "ZF-14" (trade name) sold by Nippon Rieger Co., Ltd.
In the optical film of the present invention, the retardation film is preferably a retardation film in which a liquid crystalline compound is applied and aligned to exhibit optical anisotropy.
Examples of the film exhibiting optical anisotropy by application and alignment of a liquid crystalline compound include the following first to fifth embodiments.
The first mode is as follows: a retardation film in which the rod-like liquid crystal compound is oriented in a horizontal direction with respect to the supporting substrate,
The second mode is as follows: a retardation film in which the rod-like liquid crystal compound is aligned in a direction perpendicular to the supporting substrate,
A third mode: a retardation film in which the orientation direction of the rod-like liquid crystal compound changes in a spiral shape in a plane,
A fourth formula: a retardation film in which a discotic liquid crystal compound is oriented obliquely,
The fifth mode is: a biaxial retardation film in which a discotic liquid crystal compound is aligned in a direction perpendicular to a support base.
For example, the first, second, and fifth embodiments are suitable as optical films used in organic electroluminescent displays. Alternatively, a retardation film of these types may be laminated and used.
When the retardation film is a layer containing a polymer in an aligned state of a polymerizable liquid crystal compound (hereinafter, sometimes referred to as "optically anisotropic layer"), the retardation film preferably has reverse wavelength dispersibility. The reverse wavelength dispersibility is an optical property that a retardation value in a liquid crystal alignment plane at a short wavelength is smaller than that at a long wavelength, and it is preferable that the retardation film satisfies the following formulas (7) and (8). Re (λ) represents an in-plane phase difference value with respect to light having a wavelength λ nm.
Re(450)/Re(550)≤1 (7)
1≤Re(630)/Re(550) (8)
In the optical film of the present invention, when the retardation film is of the first aspect and has reverse wavelength dispersibility, coloration in black display in a display device is reduced, and therefore, it is preferable that 0.82. ltoreq. Re (450)/Re (550). ltoreq.0.93 is more preferable in the above formula (7). Furthermore, 120. ltoreq. Re (550). ltoreq.150 is preferred.
Examples of the polymerizable liquid crystal compound in the case where the retardation film is a film having an optically anisotropic layer include: examples of the polymerizable liquid crystal compounds include compounds having a polymerizable group among compounds described in "3.8.6 network (completely crosslinked type)" and "6.5.1 liquid crystal material b" which are available from "liquid crystal materials" published by the editorial committee for liquid crystal accessibility (12 years, 10 months, 30 days) "and" polymerizable nematic liquid crystal materials ", and polymerizable liquid crystal compounds described in japanese patent application laid-open nos. 2010-31223, 2010-270108, 2011-6360, 2011-207765, 2011-162678, 2016-81035, international publication nos. 2017/043438 and 2011-765.
Examples of a method for producing a retardation film from a polymer in an aligned state of a polymerizable liquid crystal compound include the method described in jp 2010-31223 a.
In the case of the second mode, the front phase difference Re (550) may be adjusted to a range of 0 to 10nm, preferably 0 to 5nm, and the phase difference R in the thickness directionthIt is adjusted to a range of-10 to-300 nm, preferably-20 to-200 nm. Thickness-direction phase difference value R representing thickness-direction refractive index anisotropythThe phase difference value R can be measured by tilting the fast axis in the plane by 50 degrees50Phase difference value R from plane0And (6) calculating. Namely, the phase difference value R in the thickness directionthCan be calculated as follows: according to the in-plane phase difference value R0And a phase difference value R measured by tilting the fast axis by 50 DEG as a tilt axis50Thickness d of retardation film, and average refractive index n of retardation film0N is obtained by the following equations (10) to (12)x、nyAnd nzThen, they are calculated by substituting them into the formula (9).
Rth＝[(nx+ny)/2-nz]×d (9)
R0＝(nx-ny)×d (10)
R50＝(nx-ny')×d/cos(φ) (11)
(nx+ny+nz)/3＝n0 (12)
Here, the number of the first and second electrodes,
φ＝sin-1[sin(40°)/n0]
ny'＝ny×nz/[ny 2×sin2(φ)+nz 2×cos2(φ)]1/2
examples of the film exhibiting optical anisotropy by application and alignment of a liquid crystalline compound and the film exhibiting optical anisotropy by application of an inorganic layered compound include: a FILM called a temperature compensation type phase difference FILM, "NH FILM" (trade name; obliquely oriented FILM of rod-like liquid crystal) sold by JX rijie energy corporation, "WV FILM" (trade name; obliquely oriented FILM of discotic liquid crystal) sold by fuji FILM corporation, "FILM" (trade name; completely biaxially oriented FILM) sold by sumitomo chemical corporation, "new VAC FILM" (trade name; biaxially oriented FILM) sold by sumitomo chemical corporation, and the like.
The retardation film may be a multilayer film having two or more layers. Examples thereof include: a film obtained by laminating a protective film on one or both surfaces of a retardation film, or a film obtained by laminating two or more retardation films with an adhesive or a bonding agent interposed therebetween.
Fig. 1 to 5 show an example of the layer structure of the pressure-sensitive adhesive layer of the present invention and the optical laminate of the present invention.
The optical film with an adhesive layer 10 shown in fig. 1 is a state in which a release film (spacer film) 2 is bonded to the surface of the adhesive layer 1 in order to temporarily protect the surface of the adhesive layer 1 formed of the adhesive composition of the present invention.
The optical film with an adhesive layer 10A shown in fig. 2 is an optical film with an adhesive layer including a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer 1 formed of the adhesive composition of the present invention, and a release film 2. The protective film 3 may have a phase difference. Further, a hard coat layer or the like may be further stacked on the protective film 3.
The optical film with an adhesive layer 10B shown in fig. 3 is an optical film with an adhesive layer including a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer 7, a protective film 6, an adhesive layer 1 formed of the adhesive composition of the present invention, and a retardation film 8.
The optical laminate 10C shown in fig. 4 and the optical laminate 10D shown in fig. 5 are optical laminates each including a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer 1 formed from the adhesive composition of the present invention, an adhesive layer 7, a retardation film 110, an adhesive layer 1a, and a light-emitting element 30 (liquid crystal cell, organic EL cell). The pressure-sensitive adhesive layer 1a may be a pressure-sensitive adhesive layer formed from a known pressure-sensitive adhesive composition, or may be a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
When the retardation film shown in fig. 4 and 5 is a multilayer film, examples thereof include, as shown in fig. 4: the retardation film 110 is composed of a 1/4 wavelength retardation layer 50 which imparts a retardation of 1/4 wavelength parts to transmitted light and a 1/2 wavelength retardation layer 70 which imparts a retardation of 1/2 wavelength parts to transmitted light, which are laminated via an adhesive layer or an adhesive layer 60. As shown in fig. 5, there may be mentioned: the optical film comprises an optical film 40 in which an 1/4 wavelength retardation layer 50a and a positive C layer 80 are laminated via an adhesive layer or a pressure-sensitive adhesive layer 60.
The 1/4 wavelength retardation layer 50 that imparts a retardation of 1/4 wavelength parts and the 1/2 wavelength retardation layer 70 that imparts a retardation of 1/2 wavelength parts to transmitted light in fig. 4 may be the optical film of the first embodiment or the optical film of the fifth embodiment. In the case of the configuration of fig. 4, at least one of them is more preferably the fifth aspect.
In the case of the configuration of fig. 5, the 1/4-wavelength retardation layer 50a is preferably an optical film of the first embodiment, and more preferably satisfies the expressions (7) and (8).
< liquid crystal display device >
The resin of the present invention, the adhesive composition containing the resin, and the optical laminate containing the adhesive layer formed from the adhesive composition can be used for display devices such as organic EL display devices and liquid crystal display devices by being laminated on display devices such as organic EL devices and liquid crystal cells.
Examples
The present invention will be described in further detail below with reference to examples and comparative examples. In examples and comparative examples, "%" and "part(s)" are "% by mass" and "part(s) by mass" unless otherwise specified.
Synthesis example 1: synthesis of light-selective absorbing Compound (1) having a merocyanine Structure within the molecule
Figure BDA0003369733560000541
In a 200mL four-necked flask equipped with a Dimrot condenser and a thermometer, 10g of the compound represented by the formula (aa) synthesized with reference to Japanese unexamined patent publication No. 2014-194508, 3.6g of acetic anhydride (manufactured by Wako pure chemical industries, Ltd.), 10g of 2-butyloctyl cyanoacetate (manufactured by Tokyo Kasei Co., Ltd.), and 60g of acetonitrile (manufactured by Wako pure chemical industries, Ltd.) were charged under a nitrogen atmosphere, and stirred with a magnetic stirrer. 4.5g of DIPEA (manufactured by Tokyo chemical industry Co., Ltd.) was added dropwise to the obtained mixture at an internal temperature of 25 ℃ over 1 hour, and the mixture was further kept at an internal temperature of 25 ℃ for 2 hours. Thereafter, acetonitrile was removed by a reduced pressure evaporator, and the resulting product was subjected to purification by column chromatography (silica gel), and the solvent was removed from the effluent containing the compound represented by formula (UVA-1) by a reduced pressure evaporator, whereby yellow crystals were obtained. The crystals were dried under reduced pressure at 60 ℃ to obtain 4.6g of a compound represented by the formula (UVA-1) as a yellow powder. The yield was 56%.
< determination of molar absorptivity ∈ >
A2-butanone solution (concentration; 0.006g/L) of the compound represented by the formula (UVA-1) was added to a 1cm quartz cuvette, which was set in a spectrophotometer UV-2450 (manufactured by Shimadzu corporation), and the absorbance was measured in a wavelength range of 300 to 800nm in 1nm steps by a two-beam method. The molar absorption coefficient for each wavelength was calculated from the obtained absorbance value, the concentration of the compound represented by the formula (UVA-1) in the solution, and the optical path length of the quartz cuvette.
ε(λ)＝A(λ)/CL
[ in the formula,. epsilon. (. lamda.) represents the molar absorption coefficient (L/(g. cm)) of the resin (A) at a wavelength of. lamda.,. lambda.,. C represents the concentration (g/L)), and L represents the optical path length (cm) of the quartz cuvette. ]
The compound represented by the formula (UVA-1) obtained had an ε (405) of 45L/(g.cm) and ε (440) of 0.1L/(g.cm).
[ polymerization example 1 ]: preparation of acrylic resin (A-1)
A reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer was charged with a mixed solution of 150 parts of ethyl acetate, 96 parts of butyl acrylate, 3 parts of 2-hydroxyethyl acrylate and 1 part of acrylic acid as a solvent, and the internal temperature was raised to 60 ℃. Then, 0.4 part of azobisisobutyronitrile (polymerization initiator) was dissolved in 10 parts of ethyl acetate to prepare a total amount of solution. The resulting mixture was maintained at 60 ℃ for 1 hour, ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts/hr while maintaining the internal temperature at 50 to 70 ℃, the addition of ethyl acetate was stopped when the concentration of the acrylic resin reached 35%, and the mixture was kept at that temperature for 12 hours from the start of the addition of ethyl acetate. Finally, ethyl acetate was added to adjust so that the concentration of the acrylic resin reached 20%, thereby preparing an ethyl acetate solution of the acrylic resin. The weight-average molecular weight Mw of the obtained acrylic resin was 148 ten thousand and Mw/Mn was 3.45 in terms of polystyrene based on GPC. This was used as resin (A-1). The glass transition temperature based on DSC was-45 ℃. The monomer composition in the obtained acrylic resin was 96 mass% of butyl acrylate, 3 mass% of 2-hydroxyethyl acrylate, and 1 mass% of acrylic acid.
< preparation of adhesive composition >
[ example 1 ]: preparation of adhesive composition (1)
In the ethyl acetate solution (resin concentration: 20%) of the resin (A-1) obtained above, 2.5 parts of the compound represented by formula (UVA-1), 1 part of a photoinitiator (product name "NCI-730" manufactured by ADEKA), 10 parts of a photocurable component (product name "A-DPH-12E" manufactured by Ninghamu chemical Co., Ltd.), 0.3 part of a crosslinking agent (product name "CORONATE L", isocyanate-based compound, solid content 75%) and 0.28 part of a silane compound (product name "KBM-3066" manufactured by shin-Etsu chemical Co., Ltd.) were mixed with 100 parts of the solid content of the solution, and 2-butanone was added so that the solid content concentration became 14%, thereby obtaining an adhesive composition (1). The amount of the crosslinking agent (CORONATE L) is the mass part based on the active ingredient.
[ comparative example 1 ]: preparation of adhesive composition (2)
In an ethyl acetate solution (resin concentration: 20%) of the resin (A-1), 2.5 parts of the compound represented by (UVA-1), 0.3 parts of a crosslinking agent (trade name "CORONATE L", isocyanate-based compound, solid content 75%) and 0.28 parts of a silane compound (trade name "KBM-3066", manufactured by shin-Etsu chemical industry) were mixed with 100 parts of the solid content of the solution, and 2-butanone was added so that the solid content concentration became 14%, thereby obtaining an adhesive composition (2). The amount of the crosslinking agent (CORONATE L) is the mass part based on the active ingredient.
[ comparative example 2 ]: preparation of adhesive composition (3)
In an ethyl acetate solution (resin concentration: 20%) of the resin (A-1), 1 part of an indole-based light selective absorbing compound (BONASORB UA-3911 manufactured by Oriental chemical industries, Ltd.), 0.3 part of a crosslinking agent (trade name "CORONATE L", isocyanate-based compound, solid content 75%) and 0.28 part of a silane compound (trade name "KBM-3066" manufactured by shin-Etsu chemical industries, Ltd.) were mixed with 100 parts of the solid content of the solution, and 2-butanone was further added so that the solid content concentration became 14%, thereby obtaining an adhesive composition (3). The amount of the crosslinking agent (CORONATE L) is the mass part based on the active ingredient.
[ production example 1 ]: preparation of adhesive composition (4)
To an ethyl acetate solution (resin concentration: 20%) of the resin (A-1), 0.3 parts of a crosslinking agent (product name "CORONATE EL", isocyanate-based compound, solid content: 75%) and 0.28 parts of a silane compound (product name "KBM-3066", manufactured by shin-Etsu chemical industry) were mixed with 100 parts of the solid content of the solution, and 2-butanone was further added so that the solid content concentration became 14%, to obtain a pressure-sensitive adhesive composition (4). The amount of the crosslinking agent (CORONATE L) is the mass part based on the active ingredient.
< production of adhesive layer-1 >
The adhesive composition of example 1 was applied to a release-treated surface of a release-treated spacer film formed of a polyethylene terephthalate film [ trade name "PLR-382190" obtained from linetec corporation ] subjected to release treatment using an applicator (applicator) so that the thickness after drying was 5 μm, and dried at 100 ℃ for 1 minute. Then, the pressure-sensitive adhesive layer (1) (pressure-sensitive adhesive sheet) with the interlayer separator was prepared by irradiating the separator with ultraviolet light from the side of the separator while adjusting the illuminance of UV-A (wavelength 320 to 390nm) with an ultraviolet irradiation device (electrodeless UV Lamp System H Bulb, manufactured by Fusion UV Systems Co., Ltd.) to 500 mJ.
< production of adhesive layer-2 >
The adhesive compositions of comparative examples 1 and 2 were applied to release-treated surfaces of release films (trade name "PLR-382190" obtained from linec corporation) of spacers formed of polyethylene terephthalate films, which were subjected to release treatment, using applicators (applicators) so that the thickness after drying was 5 μm, and dried at 100 ℃ for 1 minute, to obtain adhesive layers with separators between tapes. The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of comparative example 1 was defined as the pressure-sensitive adhesive layer (2), and the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of comparative example 2 was defined as the pressure-sensitive adhesive layer (3).
< production of adhesive layer-3 >
The adhesive composition of preparation example 1 was applied to a release-treated surface of a release film of polyethylene terephthalate film (trade name "PLR-382190" obtained from linetec corporation) subjected to release treatment so that the thickness after drying became 25 μm using an applicator (applicator), and dried at 100 ℃ for 1 minute, to obtain an adhesive layer (4) with an interlayer separator.
< determination of gel fraction of adhesive layer >
The gel fraction in the pressure-sensitive adhesive layer of the present invention is a value measured in accordance with the following (a) to (d). The larger the gel fraction is, the more crosslinking reaction proceeds in the adhesive, and this can be used as an index of the crosslinking density. The gel fractions of the pressure-sensitive adhesive layers (1) to (3) were measured in accordance with the following (a) to (d). The results are shown in Table 1.
(a) An adhesive sheet having an area of about 8cm × about 8cm was bonded to a metal mesh (weight: Wm) made of SUS304 having an area of about 10cm × about 10 cm.
(b) The bonded product obtained in (a) above was weighed to obtain a mass of Ws, and then folded 4 times in such a manner as to wrap the adhesive sheet, and fixed by a stapler (stapler) to obtain a mass of Wb.
(c) The net fixed by the stapler in (b) was placed in a glass container, and 60mL of ethyl acetate was added to impregnate the net, and then the glass container was stored at room temperature for 3 days.
(d) The net was taken out of the glass container, dried at 120 ℃ for 24 hours, weighed, and the gel fraction was calculated based on the following formula with the mass thereof set to Wa.
Gel fraction (% by mass) [ { Wa- (Wb-Ws) -Wm }/(Ws-Wm) ] × 100
< measurement of Absorbance of adhesive layer >
The obtained pressure-sensitive adhesive layers (1) to (3) were respectively bonded to glass, and after the spacers were peeled off, a cycloolefin polymer (COP) film (ZF-14, manufactured by japan rayleigh corporation) was bonded to the pressure-sensitive adhesive layers, thereby producing a laminate having a structure of COP film/pressure-sensitive adhesive layer/glass. The laminate thus prepared was mounted on a spectrophotometer UV-2450 (manufactured by Shimadzu corporation), and the absorbance was measured in a wavelength range of 300 to 800nm by a two-beam method in 1nm steps. The absorbance of the prepared adhesive layer is shown in table 1. The absorbance of the glass at the wavelength of 405nm and the absorbance of the glass at the wavelength of 440nm and the absorbance of the COP film were both 0. The results are shown in Table 1.
[ TABLE 1]
Figure BDA0003369733560000591
< production of optical film >
[ example 2 ]: production of optical film (1)
(i) Production of polarizing film (polarizing plate)
A polyvinyl alcohol FILM ("KURARAY POVAL FILM VF-PE # 3000", manufactured by KURARAY corporation) having an average polymerization degree of about 2400 and a saponification degree of 99.9 mol% and a thickness of 30 μm was immersed in pure water at 37 ℃, and then immersed in an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio): 0.04/1.5/100) at 30 ℃. Thereafter, impregnation was performed at 56.5 ℃ in an aqueous solution containing potassium iodide and boric acid (potassium iodide/boric acid/water (weight ratio) ═ 12/3.6/100). Then, the film was washed with pure water at 10 ℃ and dried at 85 ℃ to obtain a polarizing film a having a thickness of about 12 μm in which iodine was adsorbed and oriented in polyvinyl alcohol. The stretching was mainly performed in the steps of iodine dyeing and boric acid treatment, and the total stretching magnification was 5.3 times.
(ii) Fabrication of polarizing plates
A transparent protective film ("25 KCHCN-TC", manufactured by letterpress printing) obtained by applying a hard coat layer of 7 μm to a triacetyl cellulose film of 25 μm in thickness was laminated on one surface of the polarizing film obtained in (i) with an adhesive comprising an aqueous solution of a polyvinyl alcohol resin. On the surface opposite to the transparent protective film, a cycloolefin resin film ("ZF 14-023", manufactured by japan rayleigh corporation) having a thickness of 23 μm was laminated by an adhesive agent comprising an aqueous solution of a polyvinyl alcohol resin to prepare a polarizing plate (thickness 67 μm).
(iii) Production of the 1 st retardation layer
As the 1 st retardation layer (1 st liquid crystal cured film layer), a layer obtained by curing a nematic liquid crystal compound, an alignment film, and a layer giving a retardation of λ/4 formed of a transparent substrate are used. The total thickness of the layer obtained by curing the nematic liquid crystal compound and the alignment layer was 2 μm.
(iv) Production of the 2 nd phase difference layer
As the composition for forming an alignment layer, 10 parts by mass of polyethylene glycol di (meth) acrylate (A-600, manufactured by Ningmura chemical industries Co., Ltd.), 10 parts by mass of trimethylolpropane triacrylate (A-TMPT, manufactured by Ningmura chemical industries Co., Ltd.), 10 parts by mass of 1, 6-hexanediol di (meth) acrylate (A-HD-N, manufactured by Ningmura chemical industries Co., Ltd.), and 1.5 parts by mass of IRGACURE 907 (Irg-907, manufactured by BASF) as a photopolymerization initiator were dissolved in 70 parts by mass of methyl ethyl ketone as a solvent to prepare a coating liquid for forming an alignment layer.
As a base material film, a long cycloolefin resin film (manufactured by japan regen corporation) having a thickness of 20 μm was prepared, and the obtained coating liquid for forming an alignment layer was applied to one surface of the base material film by a bar coater.
The coated layer was subjected to a heat treatment at 80 ℃ for 60 seconds and then irradiated with 220mJ/cm2And ultraviolet rays (UVB) of (4) are polymerized and cured to form an alignment layer 1 having a thickness of 2.3 μm on the base film.
As a composition for forming a retardation layer, 20 parts by mass of a photopolymerizable nematic liquid crystal compound (RMM 28B, Merck) and 1 part by mass of IRGAC URE907 (Irg-907, BASF) as a photopolymerization initiator were dissolved in 80 parts by mass of propylene glycol monomethyl ether acetate as a solvent to prepare a coating liquid for forming a retardation layer.
The retardation layer-forming coating liquid was applied to the alignment layer 1 thus obtained, and the applied layer was subjected to a heat treatment at 80 ℃ for 60 seconds. Thereafter, the sample was irradiated at 220mJ/cm2And ultraviolet rays (UVB) for polymerizing and curing the composition for forming a retardation layer to form a retardation layer having a thickness of 0.7 μm on the alignment layer. Thereby obtaining a polymer on the substrate filmAnd a2 nd retardation layer (2 nd liquid crystal cured film layer, thickness 3 μm) formed on the layer 1 and the retardation layer 1. The 2 nd retardation layer is a positive C layer.
(v) Bonding of 1 st phase difference layer and 2 nd phase difference layer
The 1 st retardation layer and the 2 nd retardation layer were bonded to each other with an ultraviolet-curable adhesive (thickness: 1 μm) using a liquid crystal layer surface (surface opposite to the transparent substrate) as a bonding surface. Subsequently, the ultraviolet-curable adhesive is cured by irradiation with ultraviolet rays. This operation was performed to produce a retardation layer including 2 retardation layers of the 1 st liquid crystal layer and the 2 nd liquid crystal layer. The transparent substrate was peeled from both sides of the retardation layer to obtain a retardation film. The thickness of the liquid crystal layer including 2 layers of the 1 st liquid crystal layer and the ultraviolet curable adhesive layer and the 2 nd liquid crystal layer was 6 μm.
(vi) Lamination of polarizing plate and retardation film
The adhesive layer (1) with an interlayer separator was laminated on the cycloolefin resin film of the polarizing plate obtained in (ii). The spacer film was peeled off from the pressure-sensitive adhesive layer (1), and the pressure-sensitive adhesive layer (1) was laminated so as to be in contact with the 1 st retardation layer side of the retardation film obtained in formula (v), thereby obtaining an optical film (1).
< evaluation of crack resistance >
A2 nd retardation layer of an optical film (1) and an adhesive layer (4) with an interlayer separator are laminated. The interlayer film was peeled off, and the pressure-sensitive adhesive layer (4) and alkali-free glass [ trade name "EAGLE XG" manufactured by corning corporation ] were laminated to obtain an optical film (1A). The obtained optical film (1A) had a structure of triacetyl cellulose film/polarizing film/cycloolefin film/pressure-sensitive adhesive layer (1)/1 st phase difference layer/ultraviolet-curable pressure-sensitive adhesive layer/2 nd phase difference layer/pressure-sensitive adhesive layer (4)/alkali-free glass.
The tip of an Ellickeron pen (model 318 made by Erichsen) set at a load of 10N was pressed from the triacetyl cellulose film side of the optical film (1A) as the starting point of the crack. Thereafter, a cold thermal shock test was conducted for 150 cycles with-40 ℃ for 30 minutes and 85 ℃ for 30 minutes as 1 cycle. After the cold-heat shock test, the crack resistance was determined by confirming how much mm the crack was elongated from the starting point by a microscope. The results are shown in Table 1.
[ comparative example 3 ]: production of optical films (2) and (2A)
An optical film (2) and an optical film (2A) were obtained by performing the same operation except that the pressure-sensitive adhesive layer (1) was changed to the pressure-sensitive adhesive layer (2). The same procedure as described above was carried out to evaluate the crack resistance. The results are shown in Table 1.
[ comparative example 4 ]: production of optical films (3) and (3A)
An optical film (3) and an optical film (3A) were obtained by performing the same operation except that the pressure-sensitive adhesive layer (1) was changed to the pressure-sensitive adhesive layer (3). The same procedure as described above was carried out to evaluate the crack resistance. The results are shown in Table 1.
[ TABLE 2]
Optical film Adhesive composition Crack resistance
Example 2 Optical film (1A) Adhesive composition (1) 4
Comparative example 3 Optical film (2A) Adhesive composition (2) >80
Comparative example 4 Optical film (3A) Adhesive composition (3) >80
The optical film with an adhesive layer comprising an adhesive layer formed from the adhesive composition of the present invention had an elongation of crack of 4 mm. On the other hand, the optical film with an adhesive layer formed from the adhesive composition of comparative example had an elongation of crack of 80mm or more. The optical film with an adhesive layer, which includes the adhesive layer formed from the adhesive composition of the present invention, has good crack resistance.
Industrial applicability
The resin of the present invention, the adhesive composition containing the resin, and the optical laminate containing the adhesive layer formed from the adhesive composition are suitably used for liquid crystal panels and liquid crystal display devices.
Description of the symbols
1 adhesive layer formed from the adhesive composition of the present invention
1a adhesive layer
2 Release film
10. 10A, 10B, 10C, 10D optical film with adhesive layer
3.6 protective film
4. 7 adhesive layer
5 polarizing film
8 phase difference film
30 light emitting element
40 optical film
50. 50a 1/4 wavelength phase difference layer
60 adhesive layer or adhesive layer
701/2 wavelength phase difference layer
80 positive C layer
100 polarizing plate
110 phase difference film.

Claims (22)

1. An adhesive composition comprising a resin (A), a photocurable component (C) and a light selective absorbing compound (B) having a merocyanine structure.
2. The adhesive composition of claim 1,
further comprising a photoinitiator (D).
3. The adhesive composition according to claim 2, wherein the photoinitiator (D) is a photo radical generator.
4. The adhesive composition according to any one of claims 1 to 3, wherein the photocurable component (C) is a photoradical curable component.
5. The adhesive composition of claim 4,
the photocurable component (C) contains a (meth) acrylate compound.
6. The adhesive composition according to claim 4 or 5,
the photocurable component (C) contains a polyfunctional (meth) acrylate compound.
7. The adhesive composition according to any one of claims 1 to 6,
further comprising a crosslinking agent (E).
8. The adhesive composition of claim 7,
the crosslinking agent (E) is an isocyanate crosslinking agent.
9. The adhesive composition according to any one of claims 1 to 8,
the resin (A) has a glass transition temperature of 40 ℃ or lower.
10. The adhesive composition according to any one of claims 1 to 9,
the resin (a) is a (meth) acrylic resin.
11. The adhesive composition according to any one of claims 1 to 10,
the resin (a) is a (meth) acrylic resin having a weight average molecular weight of 50 ten thousand or more.
12. The adhesive composition according to any one of claims 1 to 11,
the light selective absorbing compound (B) having a merocyanine structure satisfies the following formula (1),
ε(405)≥5(1)
in the formula (1), ε (405) represents the molar absorption coefficient of the light selective absorbing compound (B) having a merocyanine structure at a wavelength of 405nm, and the unit of the molar absorption coefficient is L/(g · cm).
13. The adhesive composition according to any one of claims 1 to 12,
the light selective absorbing compound (B) having a merocyanine structure satisfies the following formula (2),
ε(405)/ε(440)≥20(2)
in the formula (2), ε (405) represents the molar absorption coefficient of the light selective absorbing compound (B) having a merocyanine structure at a wavelength of 405nm, and ε (440) represents the molar absorption coefficient of the light selective absorbing compound (B) having a merocyanine structure at a wavelength of 440 nm.
14. The adhesive composition according to any one of claims 1 to 13,
the light selective absorbing compound (B) having a merocyanine structure has no polymerizable group.
15. The adhesive composition according to any one of claims 1 to 14,
the light selective absorbing compound (B) having a merocyanine structure is a compound represented by the formula (I),
Figure FDA0003369733550000021
in the formula (I), R1、R2、R3、R4And R5Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 15 carbon atoms or a heterocyclic group, and-CH contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group2-is optionally substituted by-NR1A-、-SO2-, -CO-, -O-or-S-,
R6and R7Each independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an electron-withdrawing group,
R1Arepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
R1and R2Optionally joined to each other to form a ring structure, R2And R3Optionally joined to each other to form a ring structure, R2And R4Optionally joined to each other to form a ring structure, R3And R6Optionally joined to each other to form a ring structure, R5And R7Optionally joined to each other to form a ring structure, R6And R7Optionally interconnected to form a ring structure.
16. The adhesive composition of claim 15,
the compound shown in the formula (I) is a compound shown in a formula (II),
Figure FDA0003369733550000031
in the formula (II), R11、R12、R13、R14And R15Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 15 carbon atoms or a heterocyclic group-CH contained in aliphatic or aromatic hydrocarbon group2-is optionally substituted by-NR11A-、-SO2-, -CO-, -O-or-S-,
R16and R17Each independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an electron-withdrawing group,
R11Arepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
R11and R12Optionally joined to each other to form a ring structure, R12And R13Optionally joined to each other to form a ring structure, R12And R14Optionally interconnected to form a ring structure.
17. An adhesive layer formed from the adhesive composition of any one of claims 1 to 16.
18. The adhesive layer according to claim 17, which satisfies the following formula (3),
A(405)≥0.5 (3)
in the formula (3), A (405) represents the absorbance at a wavelength of 405 nm.
19. The adhesive layer of claim 18, further satisfying the following formula (4),
A(405)/A(440)≥5 (4)
in the formula (4), A (405) represents the absorbance at a wavelength of 405nm, and A (440) represents the absorbance at a wavelength of 440 nm.
20. An optical film with an adhesive layer, wherein,
an optical film laminated on at least one side of the adhesive layer of any one of claims 17 to 19.
21. The optical film with an adhesive layer according to claim 20,
the optical film is a polarizing plate.
22. An image display device comprising the optical film with an adhesive layer of claim 20 or 21.
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