TW202122537A - Pressure-sensitive adhesive composition - Google Patents

Abstract

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

As a solution, provided is a pressure-sensitive adhesive composition comprising: a resin (A), a light selective absorption compound (B) that exhibits maximum absorption at a wavelength of 360 nm or more and satisfies the following formulas (l) and (2), and at least one selectected from a monomer (C-1) and a resin (C-2), wherein the monomer (C-1) has a polymerizable group in the molecule and exhibits maximum absorption at wavelengths of 300 nm or more and less than 360 nm, and the resin (C-2) exhibits maximum absorption at wavelengths of 300 nm or more and less than 360 nm.

Description

Adhesive composition

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

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

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] JP 2008-248131 A

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

The present invention includes the following inventions.

[1] An adhesive composition comprising:

Resin (A);

The light selective absorption compound (B) shows maximum absorption at a wavelength of 360 nm or more, and satisfies the following formulas (1) and (2); and,

At least one selected from monomer (C-1) and resin (C-2), the monomer (C-1) has a polymerizable group in the molecule and exhibits maximum absorption at a wavelength of 300nm or more and a wavelength of less than 360nm , This resin (C-2) shows maximum absorption at a wavelength of 300nm or more and a wavelength of less than 360nm.

ε(380)≧25 (1)

ε(380)/ε(420)≧20 (2)

[In formulas (1) and (2), ε(380) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 380nm, and ε(420) represents the light selective absorption compound (B) at a wavelength of 420nm Gram absorbance coefficient; the unit of Gram absorbance coefficient is L/(g‧cm). ]

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

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

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

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

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

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

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

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

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

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

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

[13] An adhesive layer formed of the adhesive composition described in any one of [1] to [12].

[14] The adhesive layer described in [13] satisfies the following formula (3).

A(380)≧0.6 (3)

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

[15] The adhesive layer described in [14] further satisfies the following formula (4).

A(380)/A(420)≧5 (4)

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

[16] The adhesive layer according to any one of [13] to [15], wherein the thickness of the adhesive layer is 10 μm or less.

[17] An adhesive layer-attached optical film, wherein at least one area of the adhesive layer described in any one of [13] to [16] has an optical film.

[18] The optical film with an adhesive layer as described in [17], wherein the optical film is a polarizing plate.

[19] An image display device comprising the optical film with an adhesive layer as described in [17] or [18].

The present invention provides an adhesive layer and an adhesive composition for forming the adhesive layer, and the adhesive layer has sufficient ultraviolet absorption performance even if the film thickness becomes thinner (for example, less than 12 μm), and oozes out There is little production and little absorption of visible light near the wavelength of 420nm.

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

1a: Adhesive layer

2: Peel off the film

3,6: Protective film

4,7: Adhesive layer

5: Polarizing film

8: retardation film

10: Laminated body

10A, 10B: Optical film with adhesive layer

10C, 10D: Optical laminate

30: Light-emitting element

40: Optical film

50: 1/2 wavelength retardation layer

50a, 70: 1/4 wavelength retardation layer

60: Adhesive layer or adhesive layer

80: Positive C layer

100: Polarizing plate

110: retardation film

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

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

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

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

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

<Adhesive composition>

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

(Z-1): Resin (A)

(Z-2): Light selective absorption compound (B) (hereinafter, sometimes referred to as light selective absorption compound (B)), which shows maximum absorption at a wavelength of 360 nm or more, and satisfies the following formulas (1) and (2) )

(Z-3): selected from monomer (C-1) (hereinafter, sometimes referred to as light selective absorption compound (C-1)) and resin (C-2) (hereinafter, sometimes referred to as light selective absorption resin (C-2)), the monomer (C-1) has a polymerizable group in the molecule and exhibits maximum absorption at a wavelength of 300nm or more and a wavelength of less than 360nm, and the resin (C-2) is The wavelength is above 300nm and the wavelength is less than 360nm, showing maximum absorption

<Resin (A)>

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

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

In addition, the resin (A) preferably does not show maximum absorption in the wavelength range of 300 nm to 780 nm.

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

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

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

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

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

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

Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate , N-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, (meth) Base) linear alkyl esters of (meth)acrylic acid such as lauryl acrylate and stearyl (meth)acrylate;

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

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

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

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

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

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

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

Specific examples of alkyl (meth)acrylate (a1) include ethyl acrylate, n- and isopropyl acrylate, n- and isobutyl acrylate, n-pentyl acrylate, n- and isohexyl acrylate, n-heptyl acrylate, acrylic acid N- and isooctyl acrylate, 2-ethylhexyl acrylate, n- and isononyl acrylate, n- and isodecyl acrylate, n-dodecyl acrylate and other alkyl groups with carbon numbers of about 2 to 12 (methyl) Alkyl acrylate.

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

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

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

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

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

Monosystems with polar functional groups include 1-hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate Hydroxybutyl, 1-hydroxypentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate Base) 2-hydroxypentyl acrylate, 2-hydroxyhexyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 3-hydroxy (meth)acrylate Amyl ester, 3-hydroxyhexyl (meth)acrylate, 3-hydroxyheptyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, (methyl) ) 4-hydroxyhexyl acrylate, 4-hydroxyheptyl (meth)acrylate, 4-hydroxyoctyl (meth)acrylate, 2-chloro-2-hydroxypropyl (meth)acrylate, (meth)acrylic acid 3-chloro-2-hydroxypropyl ester, (meth)acrylic acid 2-hydroxy-3- Phenoxypropyl, 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-hydroxyhexyl (meth)acrylate -Hydroxynonyl ester, 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, (meth)acrylic acid 8-hydroxydecyl ester, 8-hydroxyundecyl (meth)acrylate, 8-hydroxydodecyl (meth)acrylate, 9-hydroxynonyl (meth)acrylate, 9-(meth)acrylate Hydroxydecyl ester, 9-hydroxyundecyl (meth)acrylate, 9-hydroxydodecyl (meth)acrylate, 9-hydroxytridecyl (meth)acrylate, 10-(meth)acrylate Hydroxydecyl ester, 10-hydroxyundecyl (meth)acrylate, 10-hydroxydodecyl (meth)acrylate, 10-hydroxytridecyl acrylate, 10-hydroxytetradecyl (meth)acrylate Esters, 11-hydroxyundecyl (meth)acrylate, 11-hydroxydodecyl (meth)acrylate, 11-hydroxytridecyl (meth)acrylate, 11-hydroxydecyl (meth)acrylate Tetraalkyl ester, 11-hydroxypentadecyl (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, 12-hydroxytridecyl (meth)acrylate, 12-hydroxytridecyl (meth)acrylate Hydroxytetradecyl ester, 13-hydroxypentadecyl (meth)acrylate, 13-hydroxytetradecyl (meth)acrylate, 13-hydroxypentadecyl (meth)acrylate, (meth)acrylic acid 14-hydroxytetradecyl ester, 14-hydroxypentadecyl (meth)acrylate, 15-hydroxypentadecyl (meth)acrylate, 15-hydroxyheptadedecyl (meth)acrylate, etc. have a hydroxyl group monomer;

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

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

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

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

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

The single system with carboxyl group preferably uses acrylic acid.

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

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

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

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

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

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

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

The (meth)acrylamide system single system includes N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(3-hydroxypropyl) Yl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, N-(5-hydroxypentyl)(meth)acrylamide, N-(6-hydroxyl Hexyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)propylene Amide, N-(3-dimethylaminopropyl)(meth)acrylamide, N-(1,1-dimethyl-3-oxobutyl)(meth)acrylamide , N-[2-(2-Pendant oxy-1-imidazolidinyl) ethyl] (meth) allylamide, 2-propenylamino-2-methyl-1-propane sulfonic acid, N -(Methoxymethyl)acrylamide, N-(ethoxymethyl)(meth)acrylamide, N-(propoxymethyl)(meth)acrylamide, N-(1 -Methylethoxymethyl)(meth)acrylamide, N-(1-methylpropoxymethyl)(meth)acrylamide, N-(2-methylpropoxymethyl) )(Meth)acrylamide, N-(butoxymethyl)(meth)acrylamide, N-(1,1-dimethylethoxymethyl)(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N-(2-ethoxyethyl)(meth)acrylamide, N-(2-propoxyethyl)( Meth)acrylamide, N-[2-(1-methylethoxy)ethyl](meth)acrylamide, N-[2-(1-methylpropoxy)ethyl]( Meth)acrylamide, N-[2-(2-methylpropoxy)ethyl](meth)acrylamide, N-(2-butoxyethyl)(meth)acrylamide , N-[2-(1,1-dimethylethoxy)ethyl](meth)acrylamide, etc. Among them, N-(methoxymethyl)acrylamide, N-(ethoxy (Methyl)acrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, and N-(2-methylpropoxymethyl)acrylamide .

The weight average molecular weight (Mw) of the (meth)acrylic resin is preferably 500,000 to 2.5 million. If the weight average molecular weight is more than 500,000, the durability of the adhesive layer in a high-temperature environment will be improved, and it is easy to inhibit the floating and peeling between the adherend and the adhesive layer, or the adhesion failure of the adhesive layer, etc. situation. If the weight average molecular weight is 2.5 million or less, it is advantageous from the viewpoint of coatability. From the viewpoint of the coexistence of the durability of the adhesive layer and the coatability of the adhesive composition, the weight average molecular weight is preferably 600,000 to 1.8 million, more preferably 700,000 to 1.7 million, and particularly preferably 1 million to 1 million. 1.6 million. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 2-10, preferably 3-8, and more preferably 3-6. The weight average molecular weight can be analyzed by gel permeation chromatography and is a value converted from standard polystyrene.

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

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

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

<Light selective absorption compound (B)>

The light selective absorption compound (B) exhibits maximum absorption at a wavelength of 360 nm or more. The light selective absorption compound (B) preferably exhibits a maximum absorption at a wavelength of 360 nm or more and a wavelength of 420 nm or less, and more preferably exhibits a maximum absorption at a wavelength of 370 nm or more and a wavelength of 410 nm or less. By showing great absorption above the wavelength of 360nm, even a small amount of addition can efficiently absorb light near the wavelength of 380nm.

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

ε(380)≧25 (1)

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

ε(380)/ε(420)≧20 (2)

[In formula (2), ε(380) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 380nm;

ε(420) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 420nm.

The unit of Gram absorbance coefficient is L/(g‧cm). ]

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

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

The light selective absorption compound (B) preferably does not contain a merocyanidin structure in the molecule.

The so-called merocyanidin structure in the present invention means the partial structure shown by N-C=C-C=C. However, the merocyanidin structure in the present invention does not contain all aromatic condensed rings (for example, indole ring, benzotriazole ring, benzene And imidazole ring, isoindole ring, quinoline ring, etc.). That is, the light selective absorption compound (B) may include all aromatic condensed rings in which the partial structure represented by N-C=C-C=C is the constituent element of the ring in the molecule.

As the light selective absorption compound (B), a commercially available product can be used, and examples thereof include FUV-002B (manufactured by Fuji Film Co., Ltd.).

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

<Light selective absorption compound (C-1)>

The light selective absorption compound (C-1) is a resin that has a polymerizable group in the molecule and exhibits maximum absorption at a wavelength of 300 nm or more and a wavelength of less than 360 nm.

The light selective absorption compound (C-1) preferably exhibits a maximum absorption at a wavelength of 320 or more and a wavelength of 355 nm or less, and more preferably has a maximum absorption at a wavelength of 330 nm or more and 350 nm or less.

唑啉基、氮環丙烷基、乙烯醚基等陽離子性聚合性基；乙烯性不飽和基等自由基性聚合性基。光選擇吸收化合物(C-1)所具有之聚合性基較佳係乙烯性不飽和基等之自由基性聚合性基。作為乙烯性不飽和基之具體例，可列舉：乙烯基、α-甲基乙烯基、丙烯醯基、甲基丙烯醯基、烯丙基、苯乙烯基、(甲基)丙烯醯胺基、乙烯碸基、(甲基)丙烯醯氧基等乙烯性不飽和基。 Examples of the polymerizable group possessed by the light selective absorption compound (C-1) include epoxy groups, oxetanyl groups,

Cationic polymerizable groups such as oxazoline groups, aziridine groups, and vinyl ether groups; radical polymerizable groups such as ethylenic unsaturated groups. The polymerizable group possessed by the light selective absorption compound (C-1) is preferably a radical polymerizable group such as an ethylenically unsaturated group. Specific examples of ethylenically unsaturated groups include vinyl groups, α-methylvinyl groups, acryloyl groups, methacryloyl groups, allyl groups, styryl groups, (meth)acryloylamino groups, Ethylene unsaturated groups such as vinylene and (meth)propylene oxy groups.

骨架的化合物、在分子內具有聚合性基與二苯基酮骨架的化合物、在分子內具有聚合性基與不具有聚合性之氰基丙烯酸酯骨架的化合物等。 The light selective absorption compound (C-1) includes, for example, a compound having a polymerizable group and a benzotriazole skeleton in the molecule, a compound having a polymerizable group and a benzimidazole skeleton in the molecule, and a compound having a polymerizable group in the molecule. Sex base and three

A compound having a skeleton, a compound having a polymerizable group and a benzophenone skeleton in the molecule, a compound having a polymerizable group and a non-polymerizable cyanoacrylate skeleton in the molecule, and the like.

Examples of the light selective absorption compound (C-1) include the compounds described below.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

2-hydroxy-4-acryloyloxybenzophenone,

2-hydroxy-4-methacryloxy benzophenone,

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

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

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

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

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

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

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

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

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

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

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

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

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

In addition, the light selective absorption compound (C-1) may be the compound shown below.

In addition, commercially available products can be used as the light selective absorption compound (C-1). Specifically, "RUVA-93" (Otsuka Chemical Co., Ltd.), "CHISORB 5687" (Double Bond Chemical Co., Ltd.), and "Tinuvin R 796" can be used. "(BASF) and so on.

骨架的化合物、在分子內具有聚合性基與二苯基酮骨架的化合物。 The light selective absorption compound (C-1) is preferably: a compound having a polymerizable group and a benzotriazole skeleton in the molecule, a polymerizable group and a triazole in the molecule

A compound having a skeleton, a compound having a polymerizable group and a benzophenone skeleton in the molecule.

<Light selective absorption resin (C-2)>

The light selective absorption resin (C-2) is a resin that exhibits maximum absorption at a wavelength of 300 nm or more and a wavelength less than 360 nm. The light selective absorption resin (C-2) preferably exhibits a maximum absorption at a wavelength of 320 nm or more and a wavelength of 355 nm or less, and more preferably has a maximum absorption at a wavelength of 330 nm or more and a wavelength of 350 nm or less.

As the light selective absorption resin (C-2), for example, a resin containing a structural unit (hereinafter, sometimes referred to as a structural unit (C-1)) derived from the above-mentioned light selective absorption compound (C-1), and the like. The light selective absorption resin (C-2) may be a homopolymer or a copolymer containing the structural unit (C-1). The light selective absorption resin (C-2) is preferably a copolymer containing the structural unit (C-1).

The light selective absorption resin (C-2) is based on all the structural units of the structural unit (C-1), preferably 0.1 to 90% by mass, more preferably 1 to 75% by mass, and even more preferably 5 Up to 60% by mass, particularly good range from 10 to 50% by mass.

Examples of the light selective absorption resin (C-2) that include structural units other than the structural unit (C-1) include the above-mentioned structural units derived from the monomer forming the resin (A). Specifically, the above-mentioned structural unit derived from the (meth)acrylate represented by formula (a), the above-mentioned structural unit derived from a monomer having a polar functional group, and the above-mentioned structural unit derived from benzene The structural unit of the vinyl monomer, the structural unit derived from the vinyl monomer described above, the structural unit derived from the (meth)acrylamide monomer described above, and the like.

As the light selective absorption resin (C-2) to contain structural units other than the structural unit (C-1), the structural unit derived from the (meth)acrylate represented by the formula (a), the above-mentioned It is derived from the structural unit of a monomer having a polar functional group, and more preferably the above-mentioned structural unit derived from the (meth)acrylate represented by the formula (a), a monomer having a hydroxyl group, and is derived from The structural unit of (meth)acrylamide-based monomers, etc. Particularly preferred ones are derived from structural units such as n-butyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate.

The light selective absorption resin (C-2) may be a commercially available product, or it may be synthesized by a known method (for example, JP 2012-25811 A).

Specific examples of the light selective absorption resin (C-2) include resins described in JP 2012-25811 A. In addition, as a commercially available product of the light selective absorption resin (C-2), Vanare Resin UVR Series (Shin Nakamura Chemical Industry Co., Ltd.) and the like can be cited.

The content of the light selective absorption compound (C-1) or the light selective absorption resin (C-2) is usually 0.1 to 70 parts by mass relative to 100 parts by mass of the resin (A), preferably 1.0 to 50 parts by mass, It is more preferably 5.0 to 30 parts by weight, still more preferably 7.5 to 25 parts by weight, and particularly preferably 10 to 20 parts by weight.

In addition, when both the light selective absorption compound (C-1) and the light selective absorption resin (C-2) are included, the total may be within the above-mentioned range.

The content ratio (mass ratio) of the light selective absorption compound (C-1) and the light selective absorption compound (B) is usually the light selective absorption compound (C-1)/the light selective absorption compound (B) = 1/1 to 10/ 1. Preferably from 2/1 to 5/1.

The content ratio (mass ratio) of the light selective absorption resin (C-2) and the light selective absorption compound (B) is usually the light selective absorption resin (C-2)/the light selective absorption compound (B) = 1/1 to 10/ 1. Preferably from 2/1 to 5/1.

When both the light selective absorption compound (C-1) and the light selective absorption resin (C-2) are included, the total of the light selective absorption compound (C-1) and the light selective absorption resin (C-2) and the light The content ratio (mass ratio) of the selective absorption compound (B) is usually the total of the light selective absorption compound (C-1) and the light selective absorption resin (C-2)/the light selective absorption compound (B) = 1/1 to 10 /1, preferably 2/1 to 5/1.

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

<Initiator (D)>

The initiator (D) should just be a compound that causes the light selective absorption compound (C-1) or the radical curable component (E) contained as needed to cause a polymerization reaction. The initiator (D) can be any of a compound that causes a polymerization reaction by absorbing the energy of heat (thermal polymerization initiator), or a compound that causes a polymerization reaction by absorbing the energy of light (photopolymerization initiator). One. In addition, the light system is preferably active energy rays such as visible rays, ultraviolet rays, X-rays, or electron rays.

Examples of thermal polymerization initiators include compounds that generate free radicals by heating or the like (thermal radical generators), compounds that generate acids by heating and the like (thermal acid generators), and compounds that generate alkali by heating and the like (heat Alkali generator) and so on.

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

The initiator (D) is preferably selected to be suitable for the polymerization reaction of the light selective absorption compound (C-1) or the radical hardening component (E), preferably a free radical generator, and light free radical The generating agent is more preferable. Examples of the radical generator system include thermal radical generators and photo radical generators.

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

Examples of the radical generator system include alkylphenone compounds, benzoin compounds, benzophenone compounds, oxime ester compounds, and phosphine compounds. The radical generator is preferably a photo-radical generator, and from the viewpoint of the reactivity of the polymerization reaction, an oxime ester-based photo-radical generator is more preferred. By using an oxime ester-based radical generator, the reaction rate of the light selective absorption compound (C-1) or the radical hardening component (E) can be increased even under hardening conditions with weak illuminance or light intensity.

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

The α-amino alkyl phenone compound system includes 2-methyl-2-morpholinyl-1-(4-methylthiophenyl) propane-1-one and 2-dimethylamino-1 -(4-morpholinylphenyl)-2-benzylbutane-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-(4-methyl Phenylmethyl) butane-1-one and the like, preferably 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propane-1-one, 2-di Methylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one and the like. α-Aminoalkylphenone compounds can use IRGACURE (registered trademark) 127, 184, 369, 369E, 379EG, 651, 907, 1173, 2959, (above, made by BASF JAPAN Co., Ltd.), SEIKUOL (registered trademark) ) Commercial products such as BEE (manufactured by Seiko Chemical Co., Ltd.).

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

The benzophenone compound system includes, for example, benzophenone, o-benzophenone methyl benzoate, 4-phenylbenzophenone, 4-benzophenone-4'-methyldiphenyl sulfide Ether, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. Commercially available benzophenone compounds can be used.

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

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

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

The aromatic iodonium salt is a compound having a diaryl iodonium cation, and the cation typically includes a diphenyl iodonium cation. Aromatic sulfonium salt is a compound with triarylsulfonium cation, Typical examples of the cation include triphenyl sulfide cation, 4,4'-bis(diphenyl sulfide) diphenyl sulfide cation, and the like. The aromatic diazonium salt is a compound having a diazonium cation, and the cation typically includes a benzenediazonium cation. In addition, the iron-aromatic hydrocarbon complex is typically a cyclopentadienyl iron (II) aromatic hydrocarbon cation complex salt.

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

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

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

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

The quaternary ammonium compound system that becomes the photobase generator includes, for example, 1-(4-phenylthiobenzylmethyl)-1-azone-4-azabicyclo[2,2,2]octane Tetraphenylborate, 5-(4-phenylthiobenzylmethyl)-1-aza-5-azabicyclo[4,3,0]-5-nonenetetraphenylboron Ester, 8-(4-phenylthiobenzylmethyl)-1-aza-8-azone heterobicyclo[5,4,0]-7-undecenetetraphenylborate, etc. .

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

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

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

<Free radical hardening component (E)>

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

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

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

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

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

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

In addition, the monofunctional (meth)acrylate monomers can also include aralkyl (meth)acrylates such as benzyl (meth)acrylate; (meth) terpene alcohols such as isobornyl (meth)acrylate. ) Acrylic esters; (meth)acrylates having a tetrahydrofuran methyl structure such as tetrahydrofuran methyl (meth)acrylate; cyclohexyl (meth)acrylate, cyclohexyl methyl methacrylate, dicyclopentyl acrylate, ( (Meth)acrylates having a cycloalkyl group at the alkyl group such as dicyclopentenyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, etc.; (meth)acrylate N,N-dimethyl (Meth)aminoalkyl acrylates such as ethyl amino ethyl; (former Base) 2-phenoxy ethyl acrylate, dicyclopentenyl oxy ethyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylic acid (Meth)acrylate etc. which have an ether bond in an alkyl part, such as an ester.

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

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

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

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

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

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

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

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

Aliphatic polyhydric alcohols such as trihydroxymethylpropane di(meth)acrylate, ditrihydroxymethylpropane di(meth)acrylate, neopentylerythritol di(meth)acrylate and other aliphatic polyol di(meth)acrylic acid ester;

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

烷-2,5-二基二(甲基)丙烯酸酯〔別名：二

烷二醇二(甲基)丙烯酸酯〕等二

烷二醇或二

烷二烷醇之二(甲基)丙烯酸酯； 1,3-two

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

Alkyl glycol di(meth)acrylate] etc.

Alkanediol or di

Alkanediol di(meth)acrylate;

Bisphenol A ethylene oxide adduct diacrylate, bisphenol F ethylene oxide adduct diacrylate and other di(meth)acrylates of bisphenol A or bisphenol F alkylene oxide adducts ；

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

Polysiloxane di(meth)acrylate;

Di(meth)acrylate of neopentyl glycol hydroxytrimethyl acetate;

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

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

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

Alkane] bis(meth)acrylate;

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

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

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

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

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

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

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

Moreover, in addition to aromatic, aliphatic or alicyclic polyols, polyesters can also be used for polyols used to form urethane compounds containing isocyanate groups by reaction with polyisocyanates. Polyol, polyether polyol, etc. Aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, three Hydroxymethylethane, trimethylolpropane, bis(trimethylolpropane), neopentylerythritol, dineopentylerythritol, dimethylolheptane, dimethylolpropanoic acid, dimethylol Butyric acid, glycerin, hydrogenated bisphenol A, etc.

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

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

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

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

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

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

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

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

The styrene-based compound system may include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, Alkylstyrenes such as butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; Acetylstyrene; Acetylstyrene; Methoxystyrene; and Divinylbenzene.

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

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

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

<Crosslinking agent (F)>

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

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

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

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

The silane compound (G) system includes, for example, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, 3-glycidoxy propyl trimethoxy Silane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropane Trimethoxysilane, 3-Hydroxythiopropyltrimethoxysilane, etc.

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

3-Hydroxythiopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-hydrothiopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-hydrothiopropyltri Ethoxysilane-tetramethoxysilane oligomer, 3-hydrosulfanyl propyl triethoxysilane-tetraethoxysilane oligomer and other oligomers containing sulfhydryl propyl group; sulfhydryl group Methyltrimethoxysilane-tetramethoxysilane oligomer, thiomethyltrimethoxysilane-tetraethoxysilane oligomer, thiomethyltriethoxysilane-tetramethoxysilane Silane oligomers, thiomethyltriethoxysilane-tetraethoxysilane oligomers and other oligomers containing thiomethyl; 3-glycidoxypropyltrimethoxysilane-tetra Methoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-glycidol Oxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-glycidoxysilane copolymer Propylmethyldiethoxysilane-tetraethoxysilane copolymer and other copolymers containing 3-glycidoxypropyl; 3-methacryloxypropyl trimethoxysilane-tetramethoxy Silane oligomer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane Oligomer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane Oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane -Tetramethoxysilane oligomers, 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomers and other oligomers containing methacryloxypropyl groups ; 3-propenyloxypropyl trimethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropyl trimethoxysilane-tetraethoxysilane Oligomers, 3-propenyloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-propenyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-propenyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer, etc. Oligomers containing propylene oxypropyl groups; vinyl trimethoxysilane-tetramethoxysilane oligomers, vinyl trimethoxysilane-tetraethoxysilane oligomers, vinyl triethoxy Silane-tetramethoxysilane oligomer, vinyl triethoxysilane-tetraethoxysilane oligomer, vinyl methyl dimethoxysilane-tetramethoxysilane oligomer, vinyl methyl Dimethoxysilane-tetraethoxysilane oligomer, vinylmethyldiethoxysilane-tetramethoxysilane oligomer, vinylmethyldiethoxysilane-tetraethoxysilane oligomer Oligomers and other oligomers containing vinyl groups; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-Aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethyldimethyl Oxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethyl Amine group-containing copolymers, such as oxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc.

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

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

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

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

The silane compound system represented by the formula (g1) includes, for example, (trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl) Yl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1 ,4-bis(triethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,5-bis(triethoxysilyl) Yl)pentane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,6-bis(tripropoxysilyl)hexane Alkane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, 1,8-bis(tripropoxysilyl)octane, etc. (Tri-C1-5 alkoxysilyl) C1-10 alkane; 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) Alkyl) octane, 1,8-bis (dimethoxyethylsilyl) octane and other bis (di C1-5 alkoxy C1-5 alkylsilyl) C1-10 alkanes; 1,6-bis (Methoxydimethylsilyl)hexane, 1,8-bis(methoxydimethylsilyl)octane and other bis(mono-C1-5 alkoxy-diC1-5 alkylsilyl) C1-10 alkanes and so on. Among these, 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane and other bis(triC1- 3Alkoxysilyl)C1-10alkane is preferred, especially 1,6-bis(trimethoxysilyl)hexane and 1,8-bis(trimethoxysilyl)octane are more preferred .

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

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

The adhesive layer of the present invention is formed by dissolving or dispersing the adhesive composition of the present invention in a solvent to form an adhesive composition containing the solvent, and then coating the adhesive composition After being spread on the surface of the substrate and dried, it is formed by irradiation with active energy rays. The adhesive layer of the present invention may also refer to the light-cured material of the adhesive composition.

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

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

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

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

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

A(380)≧0.6 (3)

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

A(380)/A(420)≧5 (4)

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

The larger the value of A(380), the higher the absorption at the wavelength of 380nm. If the value of A(380) is less than 0.6, the absorption at the wavelength of 380nm is low, and it is easily degraded by light near ultraviolet rays. Components (for example, display devices such as organic EL elements, liquid crystal retardation films, etc.) are likely to cause deterioration. The value of A(380) is preferably 0.75 or more, more preferably 0.85 or more, and particularly preferably 1.0 or more. The upper limit is not particularly limited, but is usually 10 or less.

The value of A(380)/A(420) represents the magnitude of absorption at a wavelength of 380nm relative to the magnitude of absorption at a wavelength of 420nm. The larger the value, the more specific absorption in the wavelength region near ultraviolet rays. The value of A(380)/A(420) is preferably 5 or more, more preferably 20 or more, even more preferably 50 or more, and particularly preferably 100 or more.

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

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

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

<Optical film with adhesive layer>

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

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

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

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

The light-concentrating film is used for the purpose of controlling the optical path, etc., and can be a scalloped array sheet or a lens array sheet, a sheet with convex points, etc.

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

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

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

The degree of saponification of the polyvinyl alcohol resin is usually 85 mol% to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin can be modified, for example, it can be polyvinyl methyl modified by aldehyde Aldehydes or polyvinyl acetal, etc. The degree of polymerization of the polyvinyl alcohol resin is usually 1,000 to 10,000, preferably 1,500 to 5,000.

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

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

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

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

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

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

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

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

When the protective film is laminated on at least one side of the polarizing film, the protective film is preferably a protective film composed of polyolefin resin or cellulose resin. By using these films, the shrinkage of the polarizing film in a high temperature environment can be effectively suppressed without damaging the optical properties of the polarizing film. In addition, the protective film may be an oxygen shielding layer.

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

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

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

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

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

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

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

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

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

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

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

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

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

When the retardation film is a layer composed of a polymer in which a polymerizable liquid crystal compound is in an aligned state (hereinafter, sometimes referred to as an "optically anisotropic layer"), the retardation film preferably has reverse wavelength dispersion. The so-called reverse wavelength dispersion is an optical characteristic in which the retardation value in the liquid crystal alignment plane of short wavelength is smaller than the retardation value in the liquid crystal alignment plane of long wavelength. Preferably, the retardation film satisfies the following equations (7) and (8) ). In addition, Re(λ) represents the value of the in-plane phase difference with respect to the light of the wavelength 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 in the first form and has reverse wavelength dispersion, the coloration during black display of the display device is reduced, so it is preferable. In the aforementioned formula (7), 0.82≦Re(450)/Re(550)≦0.93 is more preferable. Furthermore, 120≦Re(550)≦150 is preferable.

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

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

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

R _th =[(n _x +n _y )/2-n _z ]×d (9)

R ₀ =(n _x -n _y )×d (10)

R ₅₀ =(n _x -n _y ')×d/cos(φ) (11)

(n _x +n _y +n _z )/3=n ₀ (12)

here,

φ=sin ^-1 [sin(40°)/n ₀ ]

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

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

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

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

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

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

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

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

As shown in FIGS. 4 and 5, when the retardation film is a multilayer film, as shown in FIG. 4, a structure including a retardation film 110 (optical film 40) can be cited. Give 1/4 The 1/4 wavelength retardation layer 70 of the retardation of the wavelength component and the 1/2 wavelength retardation layer 50 that imparts the retardation of the 1/2 wavelength component to the transmitted light are laminated with the adhesive layer or the adhesive layer 60 interposed therebetween. Winner. In addition, as shown in FIG. 5, a structure including a retardation film 110 (optical film 40) can also be cited, and the retardation film 110 has the 1/4 wavelength retardation layer 50a and the positive C layer 80 interposed by an adhesive. Layers or adhesive layers 60 are laminated.

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

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

<Liquid crystal display device>

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

[Example]

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

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

Put the 2-butanone solution (0.006g/L) of "FUV002B" (manufactured by Fujifilm Co., Ltd.) into a 1cm quartz cell, and install the quartz cell on the spectrophotometer UV-2450 (Shimadzu Manufacturing Co., Ltd.) Manufacture), the absorbance in the wavelength range of 300 to 800 nm was measured every 1 nm step by the double beam method. Calculate the Gram absorbance coefficient of each wavelength from the obtained absorbance value, the concentration of "FUV002B" in the solution, and the optical path length of the quartz cell.

ε(λ)=A(λ)/CL

[In the formula, ε(λ) represents the Gram absorbance coefficient of "FUV002B" at wavelength λ nm (L/(g‧cm)), A(λ) represents the absorbance at wavelength λ nm, and C represents the absorbance in solution The concentration of "FUV002B" (g/L), L represents the optical path length of the quartz cell (cm). ]

The maximum absorption wavelength of "FUV002B" is 370nm. The ε(380) of "FUV002B" is 108.9L/(g‧cm), ε(420) is 0.2L/(g‧cm), and ε(380)/ε(420) is 544.5.

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

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

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

100 parts of the solid content of the ethyl acetate solution (resin concentration: 20%) of the acrylic resin (A1) as the resin (A) was mixed with a crosslinking agent (F) (manufactured by Tosoh Co., Ltd.: trade name "Coronate L") , Isocyanate compound, solid content 75%) 0.3 part, silane compound (G) (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name "KBM3066") 0.28 part, radical curable component (E) (Shin-Nakamura Chemical Industry Co., Ltd.) Co., Ltd. product: brand name "A-DPH-12E", 6-functional (meth)acrylate compound) 10 parts, initiator (D) (ADEKA Co., Ltd. product: brand name "NCI-730", as Optical radical generator of oxime ester compound) 1.5 parts, light selective absorption compound (B) (manufactured by Fujifilm Co., Ltd.; trade name "FUV002B") 2.5 parts, light selective absorption compound (C-1) (Otsuka Chemical) Co., Ltd. product: trade name "RUVA-93", 10 parts of 2-[2'-hydroxy-5'-(methacryloxyethyl)phenyl]benzotriazole), and add acetic acid The ethyl ester had a solid content concentration of 14% to obtain the adhesive composition (1). In addition, the blending amount of the above-mentioned crosslinking agent is the mass part of the effective ingredient.

Examples 2 to 5 and Comparative Examples 1 to 11

The adhesive composition (2) to the adhesive composition (16) were produced in the same manner as in Example 1, except that each component and the content of each component were changed as shown in Table 1 or Table 2. In addition, the blending amount of the crosslinking agent is the part by mass of the active ingredient, and the acrylic resin (A1) is the part by mass of the solid.

In addition, the abbreviations in Table 1 indicate the following descriptions, respectively. In addition, ε(380) and ε(420) in RUVA-93, SB107, SB707 and EU-1990 are measured in the same way as the above method.

<Resin (A)>

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

<Light selective absorption compound (B)>

FUV-002B: manufactured by Fujifilm Co., Ltd.; trade name: FUV002B, maximum absorption wavelength λ max=370nm, ε(380)=108.9, ε(420)=0.2, ε(380)/ε(420)=544.5

<Light selective absorption compound (C-1)>

RUVA-93: manufactured by Otsuka Chemical Co., Ltd.; trade name: RUVA-93, ε(380)=1.5, ε(420)=0, has a polymerizable group and a benzotriazole skeleton in the molecule, and has a maximum absorption wavelength ( λ max) is 337 nm.

<Initiator (D)>

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

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

<Free radical sclerosing component (E)>

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

<Crosslinking agent (F)>

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

<Silane Compound (G)>

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

<Ultraviolet Absorber>

SB107: manufactured by Shipro Chemical Co., Ltd., benzophenone-based ultraviolet absorber, trade name: SEESORB107, maximum absorption wavelength λ max=350nm, ε(380)=22.4, ε(420)=1.6, ε(380)/ ε(420)=14.0

SB707: manufactured by Shipro Chemical Co., Ltd., benzotriazole ultraviolet absorber, trade name: SEESORB707, maximum absorption wavelength λ max=343nm, ε(380)=5.8, ε(420)=0

EU-1990: manufactured by EUTEC; trade name: EUSORB-1990, maximum absorption wavelength λ max=373nm, ε(380)=123.9, ε(420)=7.5, ε(380)/ε(420)=16.5

<Making of Adhesive Layer>

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

<Measurement of absorbance of adhesive layer>

The obtained adhesive layers were attached to the glass respectively, and after the separation film was peeled off, a cycloolefin polymer (COP) film (ZF-14 manufactured by ZEON Co., Ltd., Japan) was attached to the adhesive layer to produce a COP film/adhesive Laminated body composed of agent layer/glass. The produced laminate was mounted on a spectrophotometer UV-2450 (manufactured by Shimadzu Co., Ltd.), and the absorbance was measured by the dual beam method in the wavelength range of 300 to 800 nm in steps of 1 nm. The prepared adhesive layer has absorbance A (300) at a wavelength of 300 nm, absorbance A (330) at a wavelength of 330 nm, absorbance A (350) at a wavelength of 350 nm, absorbance A (380) at a wavelength of 380 nm, and absorbance A (at a wavelength of 420 nm). 420) is shown in Table 2. In addition, the absorbance of the glass and the absorbance of the COP film at a wavelength of 300 nm, a wavelength of 330 nm, a wavelength of 350 nm, a wavelength of 380 nm, and a wavelength of 420 nm are all zero. The results are shown in Table 2.

<Evaluation of Bleeding Resistance of Adhesive Layer>

A separation film is further laminated on the surface of the obtained adhesive layer to obtain an adhesive layer with a separation film on both sides. The obtained adhesive layer with separation membranes on both sides was stored in the air at 23 to 25°C for 1 month. Use a microscope on the adhesive layer with separation membranes on both sides after storage to confirm whether or not the compound in the surface has crystallized. If there is no crystal precipitation, it is rated as "○", and if there is crystal precipitation, it is rated as "X". The evaluation results are shown in Table 2.

The adhesive composition of the example showed an absorbance of 0.6 or more even in any of the wavelength of 300 nm, 330 nm, 350 nm, and 380 nm, and showed good ultraviolet absorber performance. In addition, when the absorbance at a wavelength of 420 nm is less than 0.10 (preferably less than 0.01), a high transmittance is shown. Furthermore, the adhesive composition of the present invention has no crystal precipitation and exhibits good exudation resistance.

The adhesive layer formed by the adhesive composition of the present invention exhibits high absorbance for wavelengths from 300nm to 380nm. On the other hand, since light with a wavelength of 420nm penetrates, it does not hinder the color performance of the display device and has a good UV absorption performance. In addition, the exudation resistance is also good.

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

[Industrial availability]

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

Claims (19)

An adhesive composition containing: Resin (A); The light selective absorption compound (B) shows maximum absorption at a wavelength of 360 nm or more, and satisfies the following formulas (1) and (2); and At least one selected from monomer (C-1) and resin (C-2), the monomer (C-1) has a polymerizable group in the molecule and exhibits maximum absorption at a wavelength of 300nm or more and a wavelength of less than 360nm , The resin (C-2) shows great absorption at wavelengths above 300nm and below 360nm; ε(380)≧25 (1) ε(380)/ε(420)≧20 (2) In formulas (1) and (2), ε(380) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 380nm, and ε(420) represents the Gram absorption coefficient of the light selective absorption compound (B) at a wavelength of 420nm Absorbance coefficient: The unit of Gram absorbance coefficient is L/(g‧cm). The adhesive composition according to claim 1, further comprising an initiator (D). The adhesive composition according to claim 2, wherein the initiator (D) is a radical generator. The adhesive composition according to claim 2 or 3, wherein the initiator (D) is a light radical generator. The adhesive composition according to any one of claims 2 to 4, wherein the initiator (D) is an oxime ester-based photoradical generator. The adhesive composition according to any one of claims 1 to 5 further contains a radical curable component (E). The adhesive composition according to claim 6, wherein the radical curable component (E) contains a (meth)acrylate compound. The adhesive composition according to claim 6 or 7, wherein the radical curable component (E) contains a polyfunctional (meth)acrylate compound. The adhesive composition according to any one of claims 1 to 8, further comprising a crosslinking agent (F). The adhesive composition according to claim 9, wherein the crosslinking agent (F) is an isocyanate-based crosslinking agent. The adhesive composition according to any one of claims 1 to 10, wherein the glass transition temperature of the resin (A) is 40°C or less. The adhesive composition according to claim 11, wherein the resin (A) is a (meth)acrylic resin having a glass transition temperature of 40°C or less. An adhesive layer formed by the adhesive composition according to any one of claims 1 to 12. The adhesive layer described in claim 13 satisfies the following formula (3); A(380)≧0.6 (3) In formula (3), A(380) represents the absorbance at a wavelength of 380nm. The adhesive layer described in claim 14 further satisfies the following formula (4); A(380)/A(420)≧5 (4) In formula (4), A(380) represents the absorbance at a wavelength of 380nm, and A(420) represents the absorbance at a wavelength of 420nm. The adhesive layer according to any one of claims 13 to 15, wherein the adhesive layer has a film thickness of 10 μm or less. An optical film with an adhesive layer, wherein at least one area of the adhesive layer according to any one of claims 13 to 16 has an optical film. The optical film with an adhesive layer according to claim 17, wherein the optical film is a polarizing plate. An image display device comprising the optical film with an adhesive layer described in claim 17 or 18.

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