KR20190032222A - Adhesive for display - Google Patents

Abstract

The present invention provides an adhesive for a display, having high sensibility on light and sufficiently hardened by light of low energy. The adhesive for a display also has high hardening performance even in a part which the light not sufficiently reaches. The adhesive for a display contains a component (A) which is a photopolymer initiator; and a component (B) which is a photopolymer composite. The photopolymer initiator indicates a substituent indicated by the following formula (1) (In the following formula (1), X indicates a residue in which n numbers of hydrogen atoms are removed from a saturated hydrocarbon including a ring structure, or in the following formula (1-1), R_8 indicates alkylene or arylene. R_9 indicates alkyl of 1 to 4 of carbon or hydrogen atoms. Y indicates oxygen atom or sulfur atom.) In a case where X is a residue in which n numbers of the hydrogen atoms are removed from saturated hydrocarbon including the ring structure, n indicates a whole number of 1 to 6. In a case where X is indicated by the following formula (1-1), n indicates 1. R_1 to R_7 indicates the predetermined substituent.

Description

Adhesive for Display {ADHESIVE FOR DISPLAY}

The present invention relates to a photopolymerization initiator comprising a compound having a specific structure and an adhesive for a display containing a photopolymerizable compound. INDUSTRIAL APPLICABILITY The display adhesive of the present invention is very useful as an adhesive for lamination (adhesion) of an optical substrate and a sealant for various display cells since it has high sensitivity for low energy light and also low outgas.

BACKGROUND ART [0002] Photocurable resin compositions are widely used for encapsulating agents for displays, sealing agents for solar cells, and encapsulating agents for electronic parts such as semiconductor encapsulants. Specific examples of applications of the sealant for display include sealants and sealants for liquid crystals, encapsulants for organic EL displays, and adhesives for touch panels. In these applications, however, And a common characteristic that the display element is not damaged is required.

It is generally known that the photo-curable resin composition has excellent curability and an advantage of less outgas. However, since the curing reaction does not proceed at the portion not exposed to light, it is a great disadvantage that there is a restriction in the degree of freedom in designing a target portion using the photocurable resin composition.

In the application of the liquid crystal sealing agent for liquid crystal dropping method (hereinafter referred to as "liquid crystal sealing agent" or "sealing agent"), by the wiring portion of the array substrate of the liquid crystal display element and the black matrix portion of the color filter substrate, A light shielding portion that does not reach the light source occurs, and the problem of display failure in the vicinity of the sealed portion becomes more serious than before. That is, due to the presence of the light-shielding portion, the primary curing by the light becomes insufficient, and a large amount of uncured components remain in the liquid crystal sealant. In this state, when proceeding to a secondary curing step by heat, the dissolution of the uncured component in the liquid crystal is promoted by heat, resulting in a problem of display failure in the vicinity of the sealing part.

In the use of the adhesive for a touch panel, a touch panel structure is proposed in which a touch sensor, in which a display unit and an optical substrate such as a glass plate on which a transparent electrode is formed are bonded with a transparent protective plate made of glass or resin, In order to improve the contrast of the display image, since the band-shaped shielding portion is formed at the outermost edge, the adhesive of the shielding portion becomes insufficiently cured, resulting in a problem that display unevenness occurs.

In order to solve this problem, various studies for improving the thermal reactivity have been made.

For example, it is an attempt to suppress liquid crystal contamination by rapidly reacting a liquid crystal sealant which is not sufficiently cured by light in the light-shielding portion from a low temperature. Patent Documents 1 and 2 disclose a method of using a thermal radical polymerization initiator. Patent Documents 3 to 5 disclose a method of using a polycarboxylic acid as a curing accelerator.

However, in order for the thermal radical polymerization initiator to efficiently generate radicals, the molecular weight thereof needs to be small to some extent. However, since the low molecular weight compound is excellent in reactivity but is easy to dissolve in liquid crystals, This becomes a problem.

Further, in the case of using a polycarboxylic acid, there is a possibility that the moisture resistance reliability is deteriorated and it may not be usable depending on the application.

Patent Document 6 discloses a technique in which an organic peroxide is contained in an ultraviolet curable resin and curing of the resin in the light shielding portion by heating after irradiation with ultraviolet rays is disclosed. However, the heating process may damage the liquid crystal display device or the like. Further, since a heating step of 60 minutes or more is required in order to set the resin to a sufficiently cured state, there is a problem that the productivity is insufficient.

Patent Document 7 discloses a technique of irradiating ultraviolet rays from the outer side surface of the formation surface of the light-shielding portion to harden the resin of the light-shielding portion. However, depending on the shape of the liquid crystal display device, it is difficult to irradiate ultraviolet rays from the side surface, so that there is a limitation in the method.

Japanese Patent Application Laid-Open No. 2004-126211 Japanese Laid-Open Patent Publication No. 2009-8754 International Publication No. 2007/138870 Japanese Laid-Open Patent Publication No. 2008-15155 Japanese Laid-Open Patent Publication No. 2009-139922 Japanese Patent No. 4711354 Japanese Laid-Open Patent Publication No. 2009-186954

The present invention relates to an adhesive for display which is cured by light irradiation such as ultraviolet rays or visible light rays, and which is highly sensitive to light and sufficiently cured by low energy light. Since the adhesive has high curability at a portion where light does not sufficiently reach and has sufficient curability even in a low energy light irradiation considering damage to another member, the adhesive and sealant of the liquid crystal display cell, And the like.

As a result of intensive studies, the inventors of the present invention have found that the aforementioned problems can be solved by using an adhesive for display (a photocurable resin composition) containing a photopolymerization initiator and a photopolymerizable compound containing a compound having a specific structure, .

That is,

(1) Component (A)

[Chemical Formula 1]

(Wherein X represents a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure,

(2)

(Wherein (1-1), R ₈ represents an alkylene group or arylene group. R ₉ represents a hydrogen atom or an alkyl group having 1 to 4. Y represents an oxygen atom, a sulfur atom or NR _10. R ₁₀ Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

When X is a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure, n represents an integer of 1 to 6. R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group other than the above substituent. R ₂ to R ₆ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a cyano group, , A sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphono group, an amino group, an ammonio group, or an organic group other than the above substituent group, and each of R ₂ to R ₆ . Two or more groups selected from R ₂ to R ₆ present on the same benzene ring may be bonded to each other to form a ring structure. R ₇ represents a hydrogen atom.

When X represents a substituent represented by the formula (1-1), n represents 1. R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group other than the above substituent. R ₂ , R ₃ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, An organic group other than the above-mentioned substituent, and each of R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , ₃ , R ₅ and R ₆ may be the same or different. R ₂ and R ₃ existing on the same benzene ring may be combined to form a ring structure, or R ₅ and R ₆ present on the same benzene ring may be combined to form a ring structure. One of R ₄ represents an organic group containing a thioether bond and the other represents an organic group containing a hydrogen atom or a thioether bond. Furthermore, an organic group containing a thioether bond represented by R ₄ may be bonded to R ₃ or R ₅ to form a ring structure. R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and (B) a display-use adhesive containing a photopolymerizable compound,

(2) The display adhesive according to (1), wherein X is a substituent represented by the formula (1-1)

(3) the adhesive for display according to the above (1), wherein X is a residue obtained by removing n hydrogen atoms from saturated hydrocarbons containing a cyclic structure,

(4) The compound represented by the formula (1)

(3)

(In the formula (2), R ₁ to R ₆ have the same meanings as R ₁ to R ₆ in the formula (1) given in the preceding paragraph (1), A denotes a cycloalkylene group, D denotes an alkylene group (3), which is a compound represented by the following formula

(5) The display adhesive according to any one of items (1) to (4) above, wherein the component (B) comprises the component (B-1)

(6) The display adhesive according to (5), wherein the component (B-1) comprises a (meth) acrylate monomer,

(7) The composition according to the above item (1), wherein the component (B-1) is at least one selected from the group consisting of a urethane (meth) acrylate oligomer, a (meth) acrylate oligomer having a polyisoprene skeleton and a (meth) acrylate oligomer having a polybutadiene skeleton. (5) above, which comprises a (meth) acrylate oligomer of at least one kind selected from the group consisting of

(8) The display adhesive according to any one of items (1) to (4), wherein the component (B) comprises an epoxy compound as the component (B-2)

(9) The display adhesive according to any one of the above items (1) to (4), further containing the component (C) organic filler and / or the component (D)

(10) The display adhesive according to (9), wherein the component (C) comprises at least one organic filler selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles,

(11) The display adhesive according to any one of items (1) to (4), further containing a component (E) silane coupling agent,

(12) An optical member comprising the cured product of the adhesive for display described in any one of (1) to (4)

(13) A touch panel including the optical member described in (12)

(14) A liquid crystal sealing agent or liquid crystal display cell encapsulating agent using the adhesive for display according to any one of the items (1) to (4)

(15) A liquid crystal display cell comprising a cured product of a liquid crystal sealant or a cured product of a sealant for a liquid crystal display cell according to (14)

.

INDUSTRIAL APPLICABILITY Since the display adhesive of the present invention exhibits sufficient curability even with low energy light, it is useful for a display component having a light shielding portion such as a sealant or a sealing agent for a liquid crystal display cell and a touch panel.

1 is a schematic view of a process for manufacturing an embodiment of the optical member of the present invention.
2 is a schematic view showing an example of the structure of the optical member of the present invention.

[Component (A) Photopolymerization initiator containing a compound represented by formula (1)] [

The photopolymerization initiator (component (A)) contained in the adhesive for display of the present invention includes a compound represented by the following formula (1).

[Chemical Formula 4]

In the formula (1), X represents a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure (hereinafter simply referred to as a "saturated hydrocarbon residue") or a substituent represented by the following formula (1-1) .

[Chemical Formula 5]

(Wherein (1-1), R ₈ represents an alkylene group or arylene group. R ₉ represents a hydrogen atom or an alkyl group having 1 to 4. Y represents an oxygen atom, a sulfur atom or NR _10. R ₁₀ Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the case where X represents a saturated hydrocarbon residue in the compound represented by the formula (1) and R ₁ through R ₇ and n represent different from each other in the case of the formula (1-1) ) And (ii).

(i) when X represents a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure,

The ring structure included in the saturated hydrocarbon residue represented by X includes a saturated hydrocarbon having 3 to 10 member rings, and the ring structure included in the saturated hydrocarbon residue may be one or more. Concrete examples of the ring structure contained in the saturated hydrocarbon residue include a structure of a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, an adamantane ring, and the like. The ring structure may have a substituent.

When X represents a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure, n represents an integer of 1 to 6. Preferably, n is 2 (integer).

R ₁ to R ₇ in the case where X represents a residue obtained by removing n hydrogen atoms from saturated hydrocarbons containing a cyclic structure will be described.

In the formula (1), R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group other than the above substituent.

The alkoxy group represented by R _{1 in the} formula (1) is preferably an alkoxy group having 1 to 18 carbon atoms, and specific examples thereof include a methoxy group, ethoxy group, n-propoxy group, iso- Iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group and n-dodecyloxy group.

Specific examples of the organic group represented by R _{1 in the} formula (1) include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, An aryl group having 7 to 18 carbon atoms, a nitro group, a cyano group, an alkylthio group having 1 to 18 carbon atoms and a halogen atom, and a substituted or unsubstituted amino group.

Examples of the alkyl group having 1 to 18 carbon atoms as a specific example of the organic group represented by R _{1 in the} formula (1) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n- butyl group, an isobutyl group, , n-pentyl group, n-pentyl group, n-pentyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Or cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, and is preferably an alkyl group having 2 to 6 carbon atoms, and is preferably an alkyl group having 2 to 6 carbon atoms More preferably a linear or branched alkyl group.

Specific examples of the organic group represented by R _{1 in the} formula (1) include an alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group, a 1-butenyl group, an isobutenyl group, Methyl-1-butenyl, 2-methyl-2-butenyl, 2,2-dicyanovinyl, 2-cyano-2-methylcarboxylvinyl and 2 -Cyano-2-methylsulfone vinyl group, and the like.

As specific examples of the organic group represented by R _{1 in the} formula (1), an alkynyl group having 2 to 18 carbon atoms includes an ethynyl group, a 1-propynyl group and a 1-butynyl group.

Examples of the aryl group having 6 to 12 carbon atoms as a specific example of the organic group represented by R _{1 in the} formula (1) include a phenyl group, a naphthyl group and a tolyl group, and preferably an aryl group having 6 to 10 carbon atoms.

Examples of the acyl group having 1 to 18 carbon atoms as a specific example of the organic group represented by R _{1 in the} formula (1) include an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an isopropylcarbonyl group, Carbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2-methylbutylcarbonyl group and nitrobenzylcarbonyl group.

Examples of the aroyl group having 7 to 18 carbon atoms as a specific example of the organic group represented by R _{1 in the} formula (1) include a benzoyl group, a toluoyl group, a naphthoyl group and a phthaloyl group.

As specific examples of the organic group represented by R _{1 in the} formula (1), an alkylthio group having 1 to 18 carbon atoms includes methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, iso -Butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, isopentylthio group, 2-methylbutylthio group, , 2-dimethylpropylthio group, and 1,1-dimethylpropylthio group.

Examples of the halogen atom as a specific example of the organic group represented by R _{1 in the} formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ₁ in the formula (1) is preferably a hydroxyl group, an alkoxy group or a dialkyl substituted amino, and is preferably a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms or a dialkyl substituted amino group (the number of carbon atoms of one substituted alkyl is 1 to 12) More preferably a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms or a dialkyl substituted amino group (having 1 to 6 carbon atoms in one substituted alkyl group), more preferably a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms or a dialkyl substituted amino group (The number of carbon atoms of one substituted alkyl is 1 to 4) is particularly preferable, and a hydroxyl group is most preferable.

In formula (1), R ₂ to R ₆ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, An organic group other than the above-mentioned substituent group, and each of R ₂ to R (s) present in plural form is a group represented by R ₁ , R ₂ , R ₃ , R _{4, 6} may be the same or different. Two or more groups selected from R ₂ to R ₆ present on the same benzene ring may be bonded to each other to form a ring structure, and the ring structure may contain a heteroatom bond.

Examples of the halogen atom represented by R ₂ to R ₆ in the formula (1) include the same halogen atoms as the specific examples of the organic group represented by R _{1 in the} formula (1).

The alkoxy group represented by R ₂ to R ₆ in the formula (1) includes the same alkoxy group represented by R _{1 in the} formula (1).

Specific examples of the organic group represented by R ₂ to R _{6 in} the formula (1) include an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, an isocyanato group, a cyanato group, an isocyanato group, a thiocyanato group, A thiocarbamoyl group, a carboxyl group, a carboxylate group, an acyl group, an acyloxy group, a hydroxyimino group, and the like.

Examples of the alkyl group, aryl group and acyl group as specific examples of the organic group represented by R ₂ to R ₆ in the formula (1) include the same alkyl groups, aryl groups and acyl groups as the specific examples of the organic group represented by R _{1 in the} formula (1) .

These organic groups may contain a hetero atom or the like other than hydrocarbon in the organic group, and the organic group may have a substituent other than a hydrocarbon group, and they may be linear or branched. The organic group for R ₂ to R ₆ is usually a monovalent organic group, but may be a divalent or higher-valent organic group in the case of forming a cyclic structure described below.

The bond other than the hydrocarbon group that the organic group represented by R ₂ to R _{6 in} the formula (1) may include in the structure is not particularly limited as long as the effect of the present invention is not impaired, but for example, an ether bond, A carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, a sulfonyl bond, a sulfinyl bond, and an azo bond. Examples of the "organic group containing a bond other than the hydrocarbon group" in the case where the alkyl group as the organic group includes a thioether bond include an alkylthio group, an alkylthioalkylene group and a thiol substituted alkyl group. In terms of heat resistance, examples of the bond other than the hydrocarbon group in the organic group include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, -R) -, -C (= NR) -: wherein R is a hydrogen atom or an organic group, a carbonate bond, a sulfonyl bond or a sulfinyl bond.

Substituents other than the hydrocarbon group that the organic group represented by R ₂ to R _{6 in} the formula (1) may contain in the structure are not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include a halogen atom, An alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a carbamoyl group, a carbamoyl group, a carbamoyl group, a carbamoyl group, a carbamoyl group, a sulfamoyl group, , A thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group, an acyl group, an acyloxy group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, Saturated or unsaturated alkyl thioether group, aryl ether group, and aryl thioether group, an amino group (-NH ₂ , -NHR, -NRR ': wherein R and R' are each independently a hydrogen atom, R ' And the like can be typically a hydrocarbon group), coming ammonia. The hydrogen atom contained in the substituent may be substituted by a hydrocarbon group. The hydrocarbon group contained in the substituent may be linear, branched, or cyclic. Among them, examples of the substituent other than the hydrocarbon group that the organic group represented by R ₂ to R ₆ may include in the structure include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyanato group, , An isothiocyanato group, an isothiocyanato group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group , An acyl group, an acyloxy group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, a saturated or unsaturated alkyl ether group, An alkylthioether group, an arylether group, and an arylthioether group are preferable.

Two or more of R ₂ to R ₆ may combine to form a cyclic structure. The cyclic structure may be a structure in which two or more members selected from the group consisting of a saturated or unsaturated alicyclic hydrocarbon, a heterocyclic ring, and a condensed ring, and the alicyclic hydrocarbon, heterocyclic ring, and condensed ring are combined . For example, R ₂ to R of two or more of the _six to combine, R ₂ to R ₆ are combined and share the atom on the benzene ring may form a condensed ring such as naphthalene, anthracene, phenanthrene, indene .

When X in the formula (1) is a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure, one or more substituents may be introduced into substituents R ₂ to R ₆ (in other words, R ₂ to R ₆ And all are not hydrogen atoms). That is, when at least one of R ₂ to R ₆ is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, A phosphino group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or a substituent group of an organic group other than the above-mentioned substituent group. By introducing at least one substituent as described above into the substituents R ₂ to R ₆ , the wavelength of the light to be absorbed can be adjusted, and a desired wavelength can be absorbed by introducing a substituent. Further, by introducing a substituent that elongates the conjugated chain of the aromatic ring, the absorption wavelength can be shifted to a long wavelength. Particularly, when a mercapto group or a sulfido group containing a sulfur atom is introduced as the substituent groups R ₂ to R ₆ , the absorption can be significantly long-wavelength-shifted. In some cases, the compatibility with the polymer precursor to be solubilized or combined may be improved. Thereby, it may be possible to improve the sensitivity of the composition of the adhesive for display while considering the absorption wavelength of the polymer precursor to be combined.

Specific examples of the organic group represented by R ₂ to R _{6 in} the formula (1) include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group; an aryl group having 4 to 23 carbon atoms such as a cyclopentyl group and a cyclohexyl group; A cycloalkenyl group having 4 to 23 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group, an aryloxyalkyl group having 7 to 26 carbon atoms such as a phenoxymethyl group, a 2-phenoxyethyl group and a 4-phenoxybutyl group, An aryl group having 7 to 20 carbon atoms such as a benzyl group and a 3-phenylpropyl group, an alkyl group having 2 to 21 carbon atoms having a cyano group such as a cyanomethyl group and a? -Cyanoethyl group, a hydroxyl group such as a hydroxymethyl group An alkoxy group having 1 to 20 carbon atoms such as an alkyl group having 1 to 20 carbon atoms, a methoxy group or an ethoxy group, an acetamide group, a benzenesulfonamide group (C ₆ H ₅ SO ₂ NH ₂ -), An amide group of methylthio, ethyl (-SR group) having 1 to 20 carbon atoms such as an alkyl group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms such as an acetyl group and a benzoyl group, an ester group having a carbon number of 2 to 21 such as a methoxycarbonyl group or an acetoxy group, An aryl group having 6 to 20 carbon atoms such as a phenyl group, a biphenyl group, and a tolyl group, an aryl group having 6 to 20 carbon atoms substituted with an electron-donating group and / or an electron-withdrawing group, Benzyl group, cyano group, and methylthio group (-SCH ₃ ) substituted with a cyano group and / or an electron-withdrawing group. The alkyl moiety may be linear, branched, or cyclic.

In addition, the R ₂ to R _6, the combined two or more of them, R ₂ to R ₆ in the case where X in the formula (1), the residue obtained by removing an n number of hydrogen atoms from a saturated hydrocarbon group comprising a ring structure The condensed ring such as naphthalene, anthracene, phenanthrene, or indene is formed by sharing an atom on the benzene ring to which it is bonded is also preferable in that the absorption wavelength becomes long.

In addition, R ₂ to R when the compound _6, at least one is the hydroxyl group of, R ₂ to compared to the R ₆ do not contain compound to the hydroxyl group, the compound represented by the formula with improved solubility or the like basic aqueous solution, equation (1) It is possible to increase the wavelength of the absorption wavelength.

R ₂ to R ₆ in the formula (1) are all hydrogen atoms, or R ₂ , R ₃ , R ₅ and R ₆ are hydrogen atoms and R ₄ is an organic group containing an alkoxy group or a thioether bond desirable.

More specifically, when X in the formula (1) is a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure, all of R ₂ to R ₆ in the formula (1) are hydrogen atoms or R ₂ , R ₃ , R ₅ and R ₆ are hydrogen atoms and R ₄ is an alkoxy group.

When X in the formula (1) is a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure, R ₇ in the formula (1) represents a hydrogen atom.

(ii) when X represents a substituent represented by the formula (1-1)

First, the substituent represented by the following formula (1-1) represented by X is described.

[Chemical Formula 6]

In the formula (1-1), R ₈ represents an alkylene group or an arylene group.

The alkylene group represented by R _{8 in the} formula (1-1) is a divalent linking group obtained by removing two hydrogen atoms from a saturated hydrocarbon, and the saturated hydrocarbon may be any of linear or branched But is preferably a divalent linking group obtained by removing two hydrogen atoms from a linear or branched saturated hydrocarbon having 1 to 6 carbon atoms and is preferably a divalent linking group obtained by removing hydrogen from a linear or branched saturated hydrocarbon group having 1 to 4 carbon atoms More preferably a divalent linking group obtained by removing two atoms, more preferably a methylene group, an ethylene group or an n-propylene group.

The arylene group represented by R _{8 in the} formula (1-1) is a divalent linking group obtained by removing two hydrogen atoms from an aromatic hydrocarbon compound. Specific examples of the aromatic hydrocarbon compound which can be an arylene group include benzene, naphthalene, anthracene, phenanthrene, pyrene and fluorene.

The alkyl group having 1 to 4 carbon atoms represented by R ₉ in the formula (1-1) is preferably an alkyl group having 1 to 18 carbon atoms in the alkyl group having 1 to 18 carbon atoms as a specific example of the organic group represented by R _{1 in the} formula (1) To 4.

As R ₉ in the formula (1-1), it is preferable that each of R ₉ is independently a hydrogen atom or a methyl group.

In formula (1-1), Y represents an oxygen atom, a sulfur atom or NR ₁₀ , and R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R _{10 include} those having 1 to 4 carbon atoms in the alkyl group described in the item of the alkyl group having 1 to 18 carbon atoms as a specific example of the organic group represented by R _{1 in} formula (1) .

As Y in the formula (1-1), an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.

R ₁ to R ₇ in the case where X is a substituent represented by the formula (1-1) will be described.

When X is a substituent represented by the formula (1-1), R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group other than the above substituent. Specific examples of R ₁ is, those similar to the specific example of the organic group represented by R ₁ "(i) X is given for the case shown the residue obtained by removing an n number of hydrogen atoms from a saturated hydrocarbon group comprising a ring structure" is mentioned in the have.

In a preferred embodiment, when X in the formula (1) is a substituent represented by the formula (1-1), R ₁ in the formula (1) is preferably a hydroxyl group or an alkoxy group, More preferably an alkoxy group, still more preferably a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a hydroxyl group.

When X is a substituent represented by the formula (1-1), R ₂ , R ₃ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a mercapto group, A sulfonyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or a group other than the above substituents, for example, a halogen atom, a cyano group, a nitro group, a nitro group, a cyano group, a sulfino group, Each of R ₂ , R ₃ , R ₅ and R _{6 which} are present may be the same or different from each other. R ₂ and R ₃ present on the same benzene ring may be combined to form a cyclic structure, or R ₅ and R ₆ present on the same benzene ring may be combined to form a cyclic structure.

Specific examples of R ₂ , R ₃ , R ₅ and R ₆ are the same as R ₂ to R ₆ described in "(i) when X represents a residue obtained by removing n hydrogen atoms from saturated hydrocarbons containing a cyclic structure" And the like.

When X in the formula (1) is a substituent represented by the formula (1-1), R ₄ independently represents an organic group containing a hydrogen atom or a thioether bond, but at least one of R ₄ is a thioether bond . That is, one of R ₄ represents an organic group containing a thioether bond and the other represents an organic group containing a hydrogen atom or a thioether bond. Furthermore, an organic group containing a thioether bond represented by R ₄ may be bonded to R ₃ or R ₅ to form a ring structure.

Examples of the organic group include the same organic groups as R ₂ to R ₆ described in "(i) when X represents a residue obtained by removing n hydrogen atoms from saturated hydrocarbons containing a cyclic structure". However, Or an aryl group is preferable. That is, at least one of R ₄ in the case where X in the formula (1) is a substituent represented by the formula (1-1) is preferably an alkylthio group or an arylthio group, and at least one of them is an alkylthio group having 1 to 20 carbon atoms More preferable. When R ₄ is an organic group containing a thioether bond, R ₄ may be bonded to R ₃ or R ₅ to form a cyclic structure. The cyclic structure formed by combining R ₄ and R ₃ or R ₅ is selected from the group consisting of saturated or unsaturated alicyclic hydrocarbon, heterocyclic ring, condensed ring, and the alicyclic hydrocarbon, heterocyclic ring, and condensed ring Or a combination of two or more of them may be used.

When X is a substituent represented by the formula (1-1), R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, when R ₇ is a plurality is present, may each R ₇ can be the same or different. When X in the formula (1) is a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure, R ₇ represents a hydrogen atom.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R _{7 in the} formula (1) include those having 1 to 4 carbon atoms in the alkyl group of the alkyl group having 1 to 18 carbon atoms as a specific example of the organic group represented by R _{1 in} formula (1) .

As R ₇ in the formula (1), it is preferable that each R independently represents a hydrogen atom or a methyl group.

When X is a substituent represented by the formula (1-1), n represents 1 (integer).

[Preferred Embodiment of Formula (1)] [

As the compound represented by the formula (1), a compound represented by the following formula (2) or (3) is more preferable. First, the equation (2) will be described.

(7)

In the formula (2), R ₁ to R ₆ are the same as or different from each other in the formula (1) described in "(i) when X represents a residue obtained by removing n hydrogen atoms from saturated hydrocarbons containing a cyclic structure" ₁ to R &_lt; ₆ >, and preferred examples thereof are the same as those of R &_lt; ₁ > to R &_lt; ₆ > in the formula (1) described above in the case "X represents a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure" Do. A represents a cycloalkylene group. D represents an alkylene group.

The cycloalkylene group represented by A in the formula (2) is a divalent linking group obtained by removing two hydrogen atoms from a saturated cyclic hydrocarbon such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring and an adamantane ring, And is preferably a 1,3-cyclopentylene group or a 1,4-cyclohexylene group, more preferably a 1,4-cyclohexylene group.

The alkylene group represented by D in the formula (2) is a divalent linking group obtained by removing two hydrogen atoms from a saturated aliphatic hydrocarbon (such as methane, ethane, propane, butane, pentane, hexane, heptane and octane) More preferably an alkylene group having 1 to 12 carbon atoms, more preferably a linear alkylene group having 1 to 8 carbon atoms (specifically, a methylene group, an ethylene group, a propylene group, a butylene group , Pentylene group, hexylene group, heptylene group and octylene group), more preferably an alkylene group having 1 to 4 carbon atoms, and most preferably an alkylene group having 1 carbon atom (that is, a methylene group). That is, as the compound represented by the formula (2), a compound represented by the following formula (2-1) is more preferable.

[Chemical Formula 8]

Equation (2-1) of, R ₁ to R ₆ is, R ₁ to R ₆ in the formula (2) (that is, "(i) X is removed, the n number of hydrogen atoms from a saturated hydrocarbon ring structure containing R ₁ to R ₆ in the formula (1) described in " in the case of indicating a residue ", and preferable examples of R ₁ to R ₆ in formula (2) Quot; represents a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure ", R ₁ to R ₆ in (1) described above.

Next, the equation (3) will be described. Equation (3) is as follows.

[Chemical Formula 9]

In the formula (3), R ₁ to R ₃ and R ₅ to R ₆ are as defined in the case of "(i) when X represents a residue obtained by removing n hydrogen atoms from saturated hydrocarbons containing a cyclic structure" if ₁₎ R 1 to R ₃ and R ₅ to represent the same meaning as that of R ₆ in the preferred also, "(i) X represents the residue obtained by removing an n number of hydrogen atoms from a saturated hydrocarbon group comprising a ring structure To R &_lt; ₃ > and R < ₅ > to R < ₆ > in the formula (1) R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms as described in "(ii) when X represents a substituent represented by formula (1-1)", and the same applies to specific examples.

In formula (3), R ₄ represents an organic group containing one thioether bond and the other represents an organic group containing a hydrogen atom or a thioether bond. Furthermore, an organic group containing a thioether bond represented by R ₄ may be bonded to R ₃ or R ₅ to form a ring structure.

Examples of the organic group include the same groups as the organic groups represented by R ₂ to R _{6 in the} above formula (1), but an alkyl group or an aryl group is preferable. That is, as R _{4 in the} formula (1), an alkylthio group or an arylthio group is preferable, and an alkylthio group having 1 to 20 carbon atoms is more preferable.

The cyclic structure formed by combining an organic group containing a thioether bond represented by R ₄ with R ₃ or R ₅ is a saturated or unsaturated alicyclic hydrocarbon, heterocyclic ring, and condensed ring, and the alicyclic hydrocarbon, heterocyclic ring , And a condensed ring, or a combination of two or more selected from the group consisting of condensed rings.

Equation (3) of, R _8, R ₉ and Y (Y represents NR ₁₀ R ₁₀ in) is R ₁₀ in NR ₁₀ represented by the substituents in R _8, R ₉ and Y (Y represented by the formula (1-1) ), And preferable examples thereof are the same as R ₈ , R ₉ and Y (R ₁₀ in NR ₁₀ represented by Y) in the substituent represented by the formula (1-1).

[Reaction of the compound represented by the formula (1)

The compound represented by the formula (1) is subjected to a cleavage reaction and a decarbonation reaction as shown by the following formula upon irradiation with active energy rays to generate a radical and a basic compound, and a polymer precursor having a radical polymerizable group Can initiate radical polymerization of the photopolymerization initiator. In addition, the basic compound generated at the same time as the radical can not only undergo a crosslinking reaction with the polymer precursor described later but also can lower the curing start temperature of the polymer precursor due to the catalytic action of the generated base.

Particularly, in the case of the compound represented by the formula (3), since the primary or secondary amine of the basic compound generated together with the radical also has reactivity with the polymer precursor, it is strongly accepted in the bridge structure of the cured product, Can be prevented.

[Chemical formula 10]

The compound represented by the formula (1) can be produced by a known method, for example, J. Photopolym. Sci. Technol 27, 2, 2014, which is incorporated herein by reference. For example, a benzoin derivative represented by the following formula (21) is reacted with paraformaldehyde at room temperature for 30 minutes in the presence of a metal hydroxide to give an intermediate compound represented by the formula (22) Or lead in the presence of a catalyst of an organic compound, the method of synthesizing the compound represented by the formula (1) is not limited to the above method. For the purification method, the crystallization method is suitable for the compound having high crystallinity. Or by washing with a solvent or the like. In addition, formula (21) and (22) X, R ₁ to R ₇ and n of shows an X, R ₁ to R _7, and the same meaning as n in formula (1).

(11)

Specific examples of the compound represented by the formula (1) are shown in the following formulas (a) to (t), but the present invention is not limited thereto.

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

Examples of the preferable isocyanates having an ethylenically unsaturated group to be used when synthesizing a compound in which X in the formula (1) is a substituent represented by the formula (1-1) include 2-isocyanatoethyl methacrylate and 2-isocyanato Isocyanatoalkyl esters of carboxylic acids having ethylenic unsaturation such as ethyl acrylate, acryloyl isocyanates such as methacryloyl isocyanate, and other ethylenes such as those described in US Pat. No. 5,130,347 (Mitra) Unsaturated isocyanate functional monomers. Among these isocyanates having an ethylenic unsaturated group, 2-isocyanatoethyl methacrylate (IEM) is preferable because of its availability. It will be apparent to those skilled in the art that many orthophilic and nucleophilic functional group pairs can be used in preparing isocyanates having ethylenically unsaturated groups.

The component (A) may be used alone in the adhesive for display of the present invention, or two or more kinds thereof may be mixed and used. In the case of mixing two or more kinds of them, two or more kinds of compounds contained in the formula (1) may be mixed and used. If the effect of the present invention is not impaired, a photopolymerization initiator other than the formula (1) It may be mixed and used.

Examples of the photopolymerization initiator which can be used in combination with the compound represented by the formula (1) include 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by BASF), 2-hydroxy-2-methyl Phenyl-2-hydroxy-2-methyl-1-propane-1-one (Darocure 1173; BASF), 1- [4- (2- hydroxyethoxy) 1-one (Irgacure 2959; manufactured by BASF), phenylglyoxylic acid methyl ester (Darocure MBF; manufactured by BASF), and the like.

The compound represented by the formula (1) may be mixed with a hydrogen-drawing type photo-radical polymerization initiator. The hydrogen-drawing type photo-radical polymerization initiator is a photopolymerization initiator that generates radicals by extracting hydrogen from other molecules by irradiation with ultraviolet light or visible light. The photo-initiator is a photo-radical type polymerization initiator such as a compound represented by formula (1) The mechanisms by which the radicals are generated are different. By using a mixture of the photopolymerization initiators having different radical generation mechanisms, it is possible to increase the photoreactivity of the adhesive for display of the present invention.

Examples of the hydrogen-drawing type photo radical polymerization initiator include benzophenone, acridone, 2-ethylthraquinone, 2-chlorothioxanthone, 2-isopropyl anthraquinone, 2,4- .

Further, for example, a thiazonthone compound having a reactive group in a molecule described in International Publication No. 2012/011220 can also be used in combination with a compound represented by the formula (1).

The content of the component (A) in the adhesive for display of the present invention is usually 0.1 to 95 mass%, preferably 0.5 to 60 mass%, in the solid content of the adhesive for display (component from which the solvent is removed). When the content of the photopolymerization initiator is less than 0.1% by mass, there is a possibility that the contrast of the solubility between the exposed portion and the unexposed portion can not be sufficiently increased. When the content exceeds 95% by mass, various properties of the cured product of the photosensitive resin composition are difficult to manifest There is a concern.

The content of the component (A) when a basic compound generated by light irradiation from a component (A) containing a compound represented by the formula (1) is used as a curing agent, such as in the case of combining with an epoxy compound described later, Is usually from 0.1 to 95 mass%, preferably from 0.5 to 60 mass%, in the solid content of the adhesive for use.

[Component (B) photopolymerizable compound]

The adhesive for a display of the present invention contains a photopolymerizable compound (hereinafter also simply referred to as "component (B)") as the component (B).

The component (B) is not particularly limited as long as it is a compound which cures by light or heat, but it preferably contains the (B-1) (meth) acrylic compound. Examples of the component (B-1) include (meth) acrylate monomers, urethane (meth) acrylate oligomers, (meth) acrylate oligomers having a polyisoprene skeleton, (meth) acrylate oligomers having a polybutadiene skeleton , (Meth) acrylic ester compounds and epoxy (meth) acrylate compounds.

In the present specification, "(meth) acryl" means "acryl and / or methacryl", and "(meth) acryloyl group" means "acryloyl group and / or methacryloyl group" do.

[Component (B-1) (meth) acrylic compound]

Component (B-1) The (meth) acrylate monomer as the (meth) acrylic compound is preferably a (meth) acrylate having one (meth) acryloyl group in one molecule and a (Meth) acrylate.

Specific examples of the (meth) acrylate having one (meth) acryloyl group in one molecule include isooctyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (Meth) acrylate such as stearyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (Meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acryloylmorpholine, phenylglycidyl (meth) acrylate, tricyclodecane Acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl acrylate, 2-methyl (meth) acrylate, dicyclopentenyl -2-ada Adamantyl methacrylate, polypropylene oxide-modified nonylphenyl (meth) acrylate, dicyclopentadienooxyethyl (meth) acrylate, and the like (Meth) acrylate having a cyclic skeleton, a hydroxyl group-containing alkyl (meth) acrylate having 5 to 7 carbon atoms, ethoxydiethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polypropylene oxide (Meth) acrylate such as nonylphenyl (meth) acrylate, ethylene oxide modified phenoxyphosphoric acid (meth) acrylate, ethylene oxide modified butoxyphosphoric acid (meth) acrylate, and ethylene oxide modified octyloxyphosphoric acid (Meth) acrylate, caprolactone-modified tetrafurfuryl (meth) acrylate, and the like.

Specific examples of the (meth) acrylate having a plurality of (meth) acryloyl groups in one molecule include tricyclodecane dimethylol di (meth) acrylate, dioxane glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, polytetramethylene glycol di (meth) acrylate, alkylene oxide modified bisphenol A type di (meth) acrylate, caprolactone modified hydroxypivalic acid neopentyl glycol di Trimethylol such as trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and trimethylolooctane tri (meth) acrylate; alkane tri (meth) acrylate having 2 to 10 carbon atoms; trimethylolpropane polyethoxy tri (Meth) acrylate, trimethylolpropane polypropoxytri (meth) acrylate, trimethylolpropane polyethoxypolypropoxy Trimethylol C2-C10 alkane polyalkoxytri (meth) acrylate such as trimethylolpropane tri (meth) acrylate, tris [(meth) acroyloxyethyl] isocyanurate, pentaerythritol tri (meth) acrylate, ethylene oxide Alkylene oxide-modified trimethylolpropane tri (meth) acrylate pentaerythritol polyethoxytetra (meth) acrylate such as modified trimethylol propane tri (meth) acrylate and propylene oxide modified trimethylol propane tri (meth) (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Component (B-1) The urethane (meth) acrylate oligomer as the (meth) acrylic compound is obtained by reacting a polyhydric alcohol, a polyisocyanate and a hydroxyl group-containing (meth) acrylate.

Examples of the polyhydric alcohol include polybutadiene glycol, hydrogenated polybutadiene glycol, polyisoprene glycol, hydrogenated polyisoprene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, Alkylene glycols having 1 to 10 carbon atoms such as 1,4-butanediol and 1,6-hexanediol, triols such as trimethylolpropane and pentaerythritol, tricyclodecane dimethylol, bis- [hydroxymethyl] -cyclo (Such as succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride and the like) such as polyhydric alcohols and alcohols having a cyclic skeleton such as hexane , A caprolactone alcohol obtained by the reaction of a polyhydric alcohol and? -Caprolactone, a polycarbonate polyol (for example, 1,6-hexanediol and di (E.g., a polycarbonate diol obtained by a reaction of a phenol carbonate and a phenyl carbonate) or a polyether polyol (e.g., polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A and the like). From the viewpoints of adhesion strength and moisture resistance, propylene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, polyisoprene glycol, and hydrogenated polyisoprene glycol are preferable as the polyhydric alcohol. From the viewpoint of transparency and flexibility, Propylene glycol, hydrogenated polybutadiene glycol and hydrogenated polyisoprene glycol having 2,000 or more are particularly preferable. Hydrogenated polybutadiene glycol is preferable from the viewpoints of discoloration such as heat resistance and compatibility and compatibility. The upper limit of the weight average molecular weight at this time is not particularly limited, but is preferably 10,000 or less, more preferably 5,000 or less. If necessary, two or more polyhydric alcohols may be used in combination.

Examples of the organic polyisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, dicyclopentanyl isocyanate, and the like. Among them, isophorone diisocyanate is preferable from the viewpoint of toughness.

Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates having 2 to 4 hydroxy carbon atoms such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (Meth) acrylate, dimethylolcyclohexyl mono (meth) acrylate, hydroxycaprolactone (meth) acrylate, and hydroxyl group-terminated polyalkylene glycol (meth) acrylate.

The reaction for obtaining the urethane (meth) acrylate oligomer is carried out, for example, as follows. That is, the polyol is mixed with the organic polyisocyanate per 1 equivalent of the hydroxyl group so that the isocyanate group is preferably 1.1 to 2.0 equivalents, more preferably 1.1 to 1.5 equivalents, and the reaction temperature is preferably 70 to 90 ° C And a urethane oligomer is synthesized. Subsequently, the hydroxy (meth) acrylate compound is mixed so that the hydroxyl group is preferably 1 to 1.5 equivalents per equivalent of the isocyanate group of the urethane oligomer, and the reaction is carried out at 70 to 90 ° C to obtain the objective urethane (meth) Late oligomers can be obtained.

The weight average molecular weight of the urethane (meth) acrylate oligomer is preferably about 7,000 to 100,000, more preferably 10,000 to 60,000. If the weight average molecular weight is less than 7,000, the shrinkage becomes large, and if the weight average molecular weight is more than 100,000, the hardenability becomes insufficient.

Component (B-1) The (meth) acrylate oligomer having a polyisoprene skeleton as the (meth) acrylic compound has a (meth) acryloyl group at the terminal or side chain of the polyisoprene molecule. The (meth) acrylate oligomer having a polyisoprene skeleton is available as " UC-203 " (Kuraray Co., Ltd.).

Similarly, the (meth) acrylate oligomer having the polybutadiene skeleton as the component (B-1) (meth) acrylic compound has a (meth) acryloyl group at the terminal or side chain of the polybutadiene molecule. The (meth) acrylate oligomer having a polybutadiene skeleton is available as " BAC-45 " (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

The (meth) acrylate oligomer having a polyisoprene skeleton and the (meth) acrylate oligomer having a polybutadiene skeleton preferably have a number average molecular weight in terms of polystyrene of 1,000 to 50,000, more preferably 25,000 to 45,000.

In the present invention, the (meth) acrylate oligomer having a polyisoprene skeleton also includes a (meth) acrylate oligomer having a hydrogenated polyisoprene skeleton and a (meth) acrylate oligomer having a polybutadiene skeleton The category also includes (meth) acrylate oligomers having a hydrogenated polybutadiene backbone.

Specific examples of the (meth) acrylic ester compound as the component (B-1) (meth) acrylic compound include N-acryloyloxyethylhexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl (Meth) acrylate, tetrahydrofuran (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane-1,4-dimethanol mono (Meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobonyl (meth) acrylate, tribromophenyloxyethyl ) Acrylate, dicyclopentenyloxyethyl (meth Acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecanedimethanol (meth) acrylate, 1,4-butanediol di (meth) acrylate, (Meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, tripentaerythritol hexa (meth) Monomers such as trimethylolpropane tetra (meth) acrylate, ester diacrylate of neopentyl glycol and hydroxy diacid, diacrylate of? -Caprolactone adduct of esters of neopentyl glycol and hydroxypivalic acid, . Preferred are N-acryloyloxyethylhexahydrophthalimide, phenoxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.

Component (B-1) The epoxy (meth) acrylate compound as the (meth) acrylic compound is obtained by a known method by the reaction of an epoxy compound with (meth) acrylic acid. The epoxy compound to be used as the raw material is not particularly limited, but is preferably an epoxy compound having two or more functional groups, and examples thereof include resorcin diglycidyl ether, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type Epoxy compounds, phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds, bisphenol F novolak type epoxy compounds, alicyclic epoxy compounds, aliphatic chain type epoxy compounds, glycidyl ester type epoxy Compounds such as glycidylamine type epoxy compounds, hydantoin type epoxy compounds, isocyanurate type epoxy compounds, phenol novolak type epoxy compounds having triphenol methane skeleton, bifunctional compounds such as catechol, resorcinol, etc. Diglycidyl ether compounds of phenols, diglycidyl ether compounds of bifunctional alcohols, Halogen may be mentioned a cargo, such as hydrogenated products. Among them, bisphenol A type epoxy compounds and resorcin diglycidyl ether are preferable from the viewpoint of liquid crystal staining property. The ratio of the epoxy group to the (meth) acryloyl group is not limited, but may be appropriately selected from the viewpoint of process suitability. However, when the display adhesive of the present invention is used for liquid crystal sealing applications or encapsulants for liquid crystal display cells , Epoxies (meth) acrylates in which a part of the epoxy groups are acryl esterified are suitably used. In this case, the ratio of acrylation is preferably about 30 to 70%.

[Component (B-2) epoxy compound]

It is also preferable that the component (B) contains an epoxy compound of the component (B-2).

The epoxy compound is not particularly limited but is preferably a bifunctional or more epoxy compound, and examples thereof include resorcinol diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol Novolac epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, bisphenol F novolac epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester epoxy resin, Dicyclopentadiene epoxy resins, diallylamine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, phenol novolak type epoxy resins having a triphenol methane skeleton, and diglycidyl ethers of bifunctional phenols such as catechol and resorcinol Diglycidyl ether compounds of bifunctional alcohols, and their halides, hydrogenated products and the like. Among them, bisphenol A type epoxy resin and resorcin sodium glycidyl ether are preferable from the viewpoint of liquid crystal staining property.

The component (B) may be used alone or in combination of two or more in the adhesive for display of the present invention. However, the component (B) may be a mixture of the components (B- (Meth) acrylate oligomer, a (meth) acrylate oligomer having a polyisoprene skeleton, a (meth) acrylate oligomer having a polybutadiene skeleton and an epoxy compound And (meth) acrylate oligomer are mixed and used.

The content of the component (B) in the adhesive for a display of the present invention is usually 5 to 80% by mass, preferably 5 to 70% by mass, more preferably 5 to 70% by mass, in the solid component 5 to 50% by mass.

[Component (C) organic filler]

When the adhesive for display of the present invention is used for applications such as a liquid crystal sealant, it may contain an organic filler as component (C) (hereinafter, simply referred to as "component (C)"). Examples of the organic filler include urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles and silicon fine particles. As the silicon fine particles, KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), Torayfil ^RTM E-5500, 9701 and EP-2001 (manufactured by Toray Dow Corning) -800T, HB-800BK (you US industries, Ltd.), styrene fine particles with La Balon ^{RTM T320C, T331C, SJ4400, SJ5400} , SJ6400, SJ4300C, SJ5300C, SJ6300C ( manufactured by Mitsubishi Chemicals) are preferred, and styrene-olefin-fine particles are septon ^RTM SEPS2004 and SEPS2063 are preferred.

These organic fillers may be used alone or in combination of two or more kinds. Two or more types may be used to form a core shell structure. Of these, preferred are acrylic fine particles and silicon fine particles.

When acrylic fine particles are used, acrylic rubber having a core shell structure composed of two types of acrylic rubber is preferable, and it is particularly preferable that the core layer is n-butyl acrylate and the shell layer is methyl methacrylate. This is sold by Aika Kogyo Co., Ltd. as Zephyr ^RTM F-351.

Examples of the silicon fine particles include crosslinked organopolysiloxane powder and dimethylpolysiloxane crosslinked powder of linear chain. As the composite silicone rubber, a silicone rubber (for example, a polyorganosilsesquioxane resin) is coated on the surface of the silicone rubber. Particularly preferred among these fine particles are composite silicone rubber microparticles of dimethylpolysiloxane crosslinked powder of a linear chain, silicone rubber or silicone resin-coated linear dimethylpolysiloxane crosslinked powder. These may be used alone or in combination of two or more. Preferably, the shape of the rubber powder is spherical with a small viscosity increase after the addition.

The content of the component (C) in the adhesive for a display of the present invention is usually 50 mass% or less, preferably 5 to 40 mass%, in the solid content of the adhesive for display (component from which the solvent is removed).

[Component (D) Inorganic filler]

When the display adhesive of the present invention is used for applications such as a liquid crystal sealant, it may contain an inorganic filler as the component (D) (hereinafter, simply referred to as component (D)). Examples of the inorganic filler include silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, magnesium hydroxide, Examples of the inorganic filler include aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide and asbestos, and preferably fused silica, crystalline silica, silicon nitride, boron nitride, , Calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate and aluminum silicate, preferably silica, alumina and talc. These inorganic fillers may be used by mixing two or more kinds.

When the inorganic filler is too large, it becomes a factor of failure such that the gap can not be formed well when the upper and lower glass substrates are coalesced when the liquid crystal display cell with a narrow gap is manufactured. Therefore, the average particle diameter is preferably 2,000 nm or less Preferably 1,000 nm or less, more preferably 300 nm or less. The lower limit of the average particle diameter is preferably about 10 nm, and more preferably about 100 nm. The particle size can be measured by a laser diffraction / scattering type particle size distribution analyzer (dry type) (LMS-30, manufactured by Seishin Co., Ltd.).

The content of the component (D) in the adhesive for a display of the present invention is usually 50 mass% or less, preferably 5 to 40 mass%, in the solid content of the adhesive for display (component from which the solvent is removed). When the content of the inorganic filler is more than 50 mass%, there is a possibility that a desired cell gap can not be formed because the content of the filler is too large. The component (D) may be used in combination with the component (C).

[Component (E) Silane coupling agent]

The adhesive for a display of the present invention can improve adhesion strength and moisture resistance by adding a silane coupling agent as the component (E) (hereinafter, simply referred to as component (E)).

Examples of the component (E) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) Aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride , 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, and the like. These silane coupling agents are commercially available from Shin-Etsu Chemical Industry Co., Ltd. as KBM series, KBE series, etc., and are readily available from the market.

The content of the component (E) in the adhesive for a display of the present invention is usually 5 mass% or less, preferably 0.05 to 3 mass%, in the solid content (component from which the solvent is removed) of the adhesive for display.

The adhesive for a display of the present invention may further contain, as optional components, a heat curing agent, a curing accelerator, a thermal radical polymerization initiator, a photopolymerization initiator, a coupling agent, an organic solvent, an antioxidant, a light stabilizer, And various additives such as components. These additives may be those conventionally known in accordance with the purpose, without any particular limitation.

The content of these additives in the adhesive for a display of the present invention is not particularly limited as long as the effect of the present invention is not impaired. However, the content of the additives is usually not more than 75% by mass, And preferably about 0.1 to 75% by mass.

The adhesive for display of the present invention can be obtained by mixing the above-mentioned essential components and optionally added optional components at room temperature to 80 캜, and removing the impurities by filtration or the like, if necessary. In mixing, a known mixing device such as a three-roll, sand mill, ball mill or the like may be used as necessary, and the filtration method may be suitably selected according to a known method after taking into account the composition of the adhesive for display. In mixing, it is preferable to appropriately adjust the blending amount of each component in consideration of the specific use of the adhesive for display, handling in handling, and the like.

Next, the manufacturing process of the optical member using the adhesive for display of the present invention will be described.

In the method for producing an optical member of the present invention, it is preferable that at least two optical substrates are bonded by the following steps 1 to 3. Further, when it is judged that sufficient adhesive strength can be ensured in the step of the step 2, the step 3 may be omitted.

(Step 1) In Step 1, at least one optical substrate is coated with the adhesive for display to form a coating layer, and ultraviolet rays are irradiated to the coating layer to form a coating layer on the optical substrate side ( (Hereinafter referred to as a " cured portion of a cured layer " or simply a " cured portion ") present on the side of the optical substrate (Hereinafter, referred to as " uncured portion of the cured layer " or simply " uncured portion ") existing in the uncured portion (hereinafter referred to as the uncured portion). In the step 1, the curing rate of the coating layer after irradiation with ultraviolet rays is not particularly limited, and it is only required that uncured portions are present on the surface opposite to the optical substrate side (upper side of the coating layer, usually on the air side) . After irradiating ultraviolet rays, it is possible to judge that a liquid component is adhered to a finger by contacting the opposite side of the optical substrate side (the upper side of the coated layer, usually the atmosphere side) with fingers and having an uncured portion.

(Step 2) In Step 2, a different optical substrate is bonded to the uncured portion of the cured layer of the optical substrate obtained in Step 1, or the uncured portion of the cured layer of another optical substrate obtained by Step 1 .

(Step 3) Step 3 is a step of irradiating ultraviolet rays through an optical substrate having a light-shielding portion to a cured layer having an uncured portion in the bonded optical substrate to cure the cured layer.

Hereinafter, with reference to the drawings, a description will be given of a specific embodiment of a method for manufacturing an optical member of the present invention via steps 1 to 3, wherein a liquid crystal display unit and a transparent substrate having a light shielding portion are bonded.

Here, the adhesive for a display of the present invention is applied in a liquid state to at least one substrate when two or more substrates are bonded together, and in a state (semi-cured state) having a liquid or an uncured portion with respect to the other substrate It is particularly preferable to use in such a case because it is possible to exhibit a particularly excellent adhesive effect and to prevent the air from intervening when curing is carried out by ultraviolet rays after bonding.

1 is a schematic view of a process for producing an embodiment of an optical member using the adhesive for a display of the present invention.

This method is a method of obtaining an optical member by bonding the liquid crystal display unit 1 and the transparent substrate 2 together.

The liquid crystal display unit 1 refers to a liquid crystal material sealed between a pair of substrates on which an electrode is formed and provided with a polarizing plate, a driving circuit, a signal input cable, and a backlight unit.

The transparent substrate 2 is a transparent substrate such as a glass plate, a polymethyl methacrylate (PMMA) plate, a polycarbonate (PC) plate, or an alicyclic polyolefin polymer (COP) plate.

Here, the transparent substrate 2 preferably has a black frame-like shielding portion 4 on the surface of the transparent substrate. The light shielding portion 4 may be formed by applying a tape, And the like. In the present invention, the present invention can be applied to a case in which the light-shielding portion 4 is not provided. In the following embodiments, a case where the light-shielding portion 4 is provided will be described as a specific example. In the case where the light-shielding portion 4 is not provided, the "transparent substrate having the light-shielding portion" may be replaced with a "transparent substrate", and the light-shielding portion may be omitted.

(Step 1)

First, as shown in Fig. 1 (a), a display adhesive is applied to the surface of the liquid crystal display unit 1 where the light shielding portion 4 of the transparent substrate 2 having the light shielding portion 4 is formed And a display adhesion layer 5 is formed. Examples of the application method include a slit coater, a roll coater, a spin coater, and a screen printing method. Here, the adhesive for display to be applied to the surface of the transparent substrate 2 having the liquid crystal display unit 1 and the light shielding portion 4 may be the same or different adhesive for display may be used. Normally, both are preferably the same adhesive for display.

The film thickness of the cured product of the adhesive for each display is adjusted so that the cured resin layer 7 after the curing is 50 to 500 μm, preferably 50 to 350 μm, more preferably 100 to 350 μm. Here, the film thickness of the cured layer of the adhesive for display present on the surface of the transparent substrate 2 having the light-shielding portion 4 may vary depending on the film thickness thereof, but usually the thickness of the liquid crystal display unit 1 It is preferable that the thickness is equal to or larger than the film thickness of the cured layer of the adhesive for display present on the surface. This is because, in the later step 3, even after irradiating ultraviolet rays, the portion remaining unchanged in the uncured state is minimized, thereby eliminating the possibility of poor curing.

The ultraviolet rays 8 are applied to the applied adhesive layer 5 for display to form a cured portion (not shown in the drawing) existing on the lower side of the coating layer (on the liquid crystal display unit side or the transparent substrate side as viewed from the display adhesive) A cured layer 6 having an uncured portion (not shown in the drawing) existing on the upper side (the side opposite to the liquid crystal display unit side or the side opposite to the transparent substrate side) of the layer (on the atmosphere side in air) is obtained. The irradiation dose is preferably 5 to 2,000 mJ / cm2, particularly preferably 10 to 1,000 mJ / cm2. If the irradiation amount is too small, the degree of curing of the resin of the finally joined optical member may become insufficient, and if the irradiation amount is excessively large, the amount of uncured components becomes small and the liquid crystal display unit 1 and the transparent substrate 2 having the light- There is a possibility that the coupling becomes poor.

In the present invention, " uncured " indicates a state of fluidity at 25 캜. When the cured layer 6 having the uncured portion is irradiated with ultraviolet rays and the liquid component is adhered to the finger, it is judged to have an uncured portion.

For curing by ultraviolet irradiation from ultraviolet to ultraviolet radiation, a lamp that irradiates ultraviolet light from ultraviolet light does not matter regardless of the light source. For example, low-pressure, high-pressure or ultra-high-pressure mercury lamps, metal halide lamps, (pulse) xenon lamps, or electrodeless lamps can be cited.

In the step 1 of the present invention, the wavelength of ultraviolet light to be irradiated to the adhesive for display is not particularly limited, but when the maximum illuminance in the range of 320 to 450 nm is 100, the ratio of the maximum illuminance at 200 to 320 nm (Light intensity ratio) is preferably 30 or less, particularly preferably 200 to 320 nm, and the illuminance is 10 or less. When the maximum illuminance in the range of 320 to 450 nm is taken as 100 and the ratio of the maximum illuminance in 200 to 320 nm (illuminance ratio) is more than 30, the adhesive strength of the finally obtained optical member is reduced. This is because if the illuminance at a low wavelength is high, the display adhesive is excessively cured at the time of curing in the step 1, and the contribution to the adhesion at the time of curing in the irradiation of ultraviolet rays in the step 3 is reduced It is thought that it is done.

Here, the method of irradiating the ultraviolet rays to the illuminance ratio is, for example, a method of applying a lamp that meets the conditions of the illuminance ratio, (Such as a short-wave ultraviolet cut filter, a glass plate, a film, or the like) that cuts ultraviolet rays of short wavelength at the time of irradiating Step 1, it is possible to irradiate with such a light intensity ratio. Examples of the substrate for adjusting the ultraviolet ray intensity ratio include, but are not limited to, a glass plate subjected to a short-wave ultraviolet ray cutting treatment, soda lime glass, a PET film, and the like. In addition, a damping plate or the like obtained by subjecting the surface of quartz glass or the like to irregularities is not very effective. These are not suitable for selectively reducing the illuminance of a short wavelength of 320 nm or less because the light is scattered to lower the illuminance.

In the step 1, the ultraviolet ray irradiation is carried out usually in the air on the upper side of the application side (the side opposite to the liquid crystal display unit 1 side or the side opposite to the transparent substrate 2 side as viewed from the adhesive for display) Surface). It is also possible to irradiate ultraviolet rays while spraying a hardening inhibiting gas on the upper surface of the coating layer after vacuuming. When the adhesive for display is cured in the atmosphere, the side opposite to the side of the liquid crystal display unit 1 or the side opposite to the side of the transparent substrate 2 is the atmosphere side. When it is desired to increase the tackiness of the surface of the coating layer formed in Step 1, ultraviolet rays may be irradiated under a vacuum environment or in an environment of a gas which does not cause inhibition of curing such as nitrogen.

On the other hand, in the case of omitting step 3, it is possible to suitably carry out curing in vacuum or while spraying a gas (for example, nitrogen) promoting curing. Thus, even if Step 3 is omitted, sufficient adhesion can be performed.

By irradiating oxygen or ozone to the surface of the adhesive layer for display 5 (coating layer) during ultraviolet irradiation, the state of the uncured portion and the film thickness of the uncured portion can be adjusted. In other words, since oxygen or ozone is sprayed on the surface of the coating layer, oxygen hardening of the adhesive for display 5 is inhibited on the surface thereof, so that the degree of curing of the surface can be controlled, Can be thickened.

(Step 2)

Next, as shown in Fig. 1 (b), the liquid crystal display unit 1 and the transparent substrate 2 having the light shielding portion 4 are bonded to each other in such a manner that the uncured portions are opposed to each other. The bonding can be performed either in air or in vacuum. Here, in order to prevent air bubbles from forming at the time of curing, it is preferable to perform bonding in vacuum. As described above, when a layer of the adhesive 5 for display having a cured portion and an uncured portion is formed on each of the liquid crystal display unit 1 and the transparent substrate 2 and then laminated, an improvement in adhesion can be expected. The bonding can be carried out by pressing, pressing or the like.

(Step 3)

Next, as shown in Fig. 1 (c), an ultraviolet ray 8 (8) is emitted from the side of the transparent substrate 2 having the light-shielding portion 4 to the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 ) To cure the display adhesive layer 5 (coating layer). The dose of ultraviolet rays is preferably about 100 to 4,000 mJ / cm2, particularly preferably about 200 to 3,000 mJ / cm2, in terms of accumulated light quantity. Regarding a light source used for curing by ultraviolet to near-ultraviolet irradiation, a lamp that emits ultraviolet rays or extreme ultraviolet rays may be used regardless of the light source. For example, low-pressure, high-pressure or ultra-high-pressure mercury lamps, metal halide lamps, (pulse) xenon lamps, or electrodeless lamps can be cited. Thus, an optical member as shown in Fig. 2 can be obtained.

The manufacturing process is the same as the manufacturing method of the optical member in which the display adhesive layer 5 is formed on both the liquid crystal display unit 1 and the transparent substrate 3 having the light shield 4 A method of bonding the transparent substrate 3 having the light shielding portion 4 after the adhesive layer 5 for display is formed only on the liquid crystal display unit 1 or a method of bonding the transparent substrate 3 having the light shielding portion 4 ), And then the liquid crystal display unit 1 is bonded after the adhesive layer 5 for display has been formed only on the display surface of the liquid crystal display unit 1. It is also possible to use various members described below as optical substrates instead of the liquid crystal display unit 1, or to use various members described later as optical substrates as the transparent substrate 2.

The optical substrate such as the liquid crystal display unit 1 and the transparent substrate 2 may be provided with various kinds of optical members such as a film or another optical member bonded on a cured layer of a display adhesive Substrate layer) may be used.

The method of forming the adhesive layer for display (5) described in the embodiment, the thickness of the resin cured product, the amount of irradiation at the time of ultraviolet irradiation and the light source, and the method of spraying oxygen or nitrogen or ozone And the method of adjusting the film thickness of the uncured portion by the method of the present invention are not limited to the above embodiments but can be applied to any manufacturing method included in the present invention.

Specific embodiments of the optical member that can be manufactured in the above embodiment, including the liquid crystal display unit, are shown below.

(i) the optical substrate having a light-shielding portion is at least one optical substrate selected from the group consisting of a transparent glass substrate having a light-shielding portion, a transparent resin substrate having a light-shielding portion, and a glass substrate having a light- Is an at least one display unit selected from the group consisting of a liquid crystal display unit, a plasma display unit and an organic EL unit, and the obtained optical member is a display unit having an optical substrate having the light shielding portion.

(ii) an optical member in which one of the optical substrates is a protective substrate having a light shielding portion and the other optical substrate to which the optical substrate is bonded is a display unit having a touch panel or a touch panel, A touch panel having a substrate or a display unit having the touch panel.

In this case, in the step 1, it is preferable to apply the above-mentioned adhesive for display to the surface of the protective substrate having the shielding portion on which the light shielding portion is formed or the surface of the touch panel, or both surfaces thereof.

(iii) A mode in which one optical substrate is an optical substrate having a light-shielding portion, the other optical substrate to be bonded thereto is a display unit, and the optical member to which at least two optical substrates are bonded is a display unit having an optical substrate having a light- shielding portion.

In this case, it is preferable to apply the adhesive for display to the one or both of the surface of the optical substrate having the light-shielding portion on which the light-shielding portion is formed or the display surface of the display unit in Step 1.

Specific examples of the optical substrate having the light-shielding portion include a protective plate for a display screen having a light-shielding portion or a touch panel having a protective substrate having a light-shielding portion formed thereon.

The side of the optical substrate having the light-shielding portion on which the light shielding portion is formed is, for example, the side of the shielding plate on which the light shielding portion is formed when the optical substrate having the light shielding portion is a shielding plate for a display screen having a light shielding portion. When the optical substrate having the light-shielding portion is a touch panel having the protective substrate having the light-shielding portion, since the surface having the light-shielding portion is bonded to the touch surface of the touch panel, The side of the formed side means the base surface of the touch panel opposite to the touch surface of the touch panel.

In the present invention, the term " optical substrate " means both an optical substrate having no light-shielding portion on its surface and an optical substrate having a light-shielding portion on its surface, and a transparent plate, a sheet, a touch panel, .

As the material of the optical substrate, various materials can be used. Specifically, resins such as PET, PC, PMMA, a complex of PC and PMMA, glass, COC, COP, plastic (acrylic resin, etc.) Examples of the optical substrate, such as a transparent plate or sheet, used in the present invention include a film such as a polarizing plate or a sheet or a laminate in which a plurality of sheets are laminated, a sheet or a transparent plate not laminated, and a transparent Plate (an inorganic glass plate and a work product thereof, for example, a lens, a prism, and an ITO glass).

The optical substrate used in the present invention may be a laminate composed of a plurality of functional plates or sheets such as a touch panel (touch panel input sensor) or a display unit described below (hereinafter referred to as " functional laminate &Quot;).

Examples of the sheet usable as the optical substrate used in the present invention include an icon sheet, a decorative sheet and a protective sheet. Examples of the plate (transparent plate) that can be used in the method for producing an optical member of the present invention include a bright plate and a protective plate. As materials of these sheets or plates, those listed as materials of transparent plates can be applied.

Examples of the material of the surface of the touch panel which can be used as the optical substrate used in the present invention include glass, PET, PC, PMMA, a complex of PC and PMMA, COC and COP.

Preferred examples of the optical member obtained by the production method of the present invention include a plate-shaped or sheet-shaped transparent optical substrate having a light-shielding portion and an optical member in which the functional laminate is formed by a cured product of a display adhesive of the present invention.

Further, in the manufacturing method of the present invention, by using a display unit such as a liquid crystal display as one of the optical substrates and using an optical functional material as another optical substrate, a display unit (hereinafter, ) Can be produced. Examples of the display unit include a display device such as an LCD, an EL display, an EL light, an electronic paper, a plasma display, or the like in which a polarizer is attached to a glass. Examples of optically functional materials include transparent plastic plates such as acrylic plates, PC plates, PET plates, and PEN plates, tempered glass, and touch panel input sensors.

Preferred examples of the optical member obtained by the production method of the present invention include the following (i) to (vii).

(i) An optical member in which an optical substrate having a light-shielding portion and the functional laminate are stacked using a cured product of a display adhesive of the present invention.

(ii) the optical substrate having the light-shielding portion is an optical substrate selected from the group consisting of a transparent glass substrate having a light-shielding portion, a transparent resin substrate having a light-shielding portion, and a glass substrate having a light-shielding material and a transparent electrode formed thereon, The optical member according to (i) above, wherein the optical member is a display unit or a touch panel.

(iii) The optical member according to (ii), wherein the display unit is any one of a liquid crystal display unit, a plasma display unit and an organic EL display unit.

(iv) A touch panel (or touch panel input sensor) in which a plate-like or sheet-like optical substrate having a light shielding portion is bonded to a surface of a touch panel side of the touch panel using a cured product of an adhesive for display of the present invention.

(v) A display panel in which a plate-like or sheet-like optical substrate having a light shielding portion is adhered onto a display screen of a display unit using a cured product of an adhesive for display of the present invention.

(vi) A display panel according to the above (v), wherein the plate-like or sheet-like optical substrate having the light-shielding portion is a protective substrate or a touch panel for protecting the display screen of the display unit.

(vii) The optical member, the touch panel or the display panel according to any one of (i) to (vi), wherein the adhesive for display is the display adhesive according to any one of (1) to (18).

The optical member including the display unit and the optical substrate having the light-shielding portion obtained by the manufacturing method of the present invention can be mounted on an electronic device such as a television, a small game machine, a cellular phone, or a personal computer.

INDUSTRIAL APPLICABILITY The display adhesive of the present invention is very useful as a sealing agent for electronic parts such as an adhesive for flexible printed circuit boards, an adhesive for TAB, an adhesive for semiconductors and an adhesive for various displays, or an encapsulating agent for liquid crystal display cells, particularly a liquid crystal sealing agent. Hereinafter, a liquid crystal display cell using the adhesive for a display of the present invention as a liquid crystal sealant will be described.

A liquid crystal display cell manufactured using the adhesive for a display of the present invention is a liquid crystal display cell manufactured by using a pair of substrates provided with a predetermined electrode on a substrate so as to face each other at a predetermined interval and sealing the periphery thereof with the adhesive for display, Liquid crystal is encapsulated. The type of the liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a combination substrate made of glass, quartz, plastic, silicon or the like and having at least one light transmitting property. In this method, a spacer (gap control material) such as glass fiber is added to the adhesive for display, and the display adhesive is applied to one of the pair of substrates using a dispenser or a screen printing apparatus Then, temporary curing is carried out at 80 to 120 占 폚, if necessary. Thereafter, liquid crystal is dropped on the inner side of the weir of the adhesive for display, and the other glass substrate is superimposed in vacuum, and gap filling is performed. After forming the gap, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 캜 for 1 to 2 hours. In addition, when it is used as a photothermal additive type, ultraviolet rays are irradiated to the adhesive portion for display with an ultraviolet ray irradiator to effect photo-curing. The ultraviolet irradiation dose is preferably 500 to 6,000 mJ / cm 2, more preferably 1,000 to 4,000 mJ / cm 2. Thereafter, if necessary, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C for 1 to 2 hours. The liquid crystal display cell of the present invention thus obtained is free from display defects due to liquid crystal contamination, and is excellent in adhesion and humidity resistance reliability. Examples of the spacer include glass fibers, silica beads, polymer beads, and the like. The diameter varies depending on the purpose, but is usually 2 to 8 占 퐉, preferably 4 to 7 占 퐉. The amount thereof is usually 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, and more preferably 0.9 to 1.5 parts by mass based on 100 parts by mass of the adhesive for a display of the present invention.

INDUSTRIAL APPLICABILITY The display adhesive of the present invention is very suitable for use in an electronic component of a design having a light shielding portion or in an encapsulant which needs to be cured with low energy light such as visible light. For example, a liquid crystal sealing agent, an encapsulating agent for an organic EL, and an adhesive for a touch panel, which are used under the light shielding portion.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" and "%" in the text are based on mass.

Synthesis Example 1 (Synthesis of compound (component (A)) represented by formula (1)

(A-1) represented by the formula (1) was obtained in accordance with the description of Example 6 of JP-A-2017-105749.

Synthesis Example 2 (Synthesis of compound (A-2) for comparison)

According to the description of Synthesis Example 1 of International Publication No. 2006/027982, a copolymer of 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- -1-propan-1-one.

Synthesis Example 3 (Synthesis of photopolymerizable compound (component (B)) [

140 parts of resorcine diglycidyl ether resin were dissolved in 160 parts of toluene, 0.48 parts of dibutylhydroxytoluene as a polymerization inhibitor was added, and the temperature was raised to 60 占 폚. Thereafter, 100 parts of acrylic acid (corresponding to an equivalent equivalent to the epoxy group in the glycidyl ether resin) was added and the temperature was further raised to 80 DEG C, and 0.96 part of trimethylammonium chloride as a reaction catalyst was added thereto. Lt; / RTI > The obtained reaction solution was washed with water, and toluene was distilled off to obtain 241 parts of resorcin epoxyacrylate (B-1).

Example 1 (Preparation of adhesive for display of the present invention)

(A-1), (B-1) and (B-2) were mixed in the ratios shown in the following Table 1, and the temperature was raised to 90 占 폚 and then (C-1) was dissolved. The obtained mixture was cooled to room temperature, and (D-1) and (E-1) were added and stirred, followed by further dispersing with a three-roll mill. The obtained composition was filtered with a metal mesh (635 mesh) to obtain an adhesive for display of the present invention.

Comparative Example 1 (Preparation of Comparative Display Adhesive)

(A-1) was obtained by reacting 2-methacryloyloxyethyl isocyanate obtained in Synthesis Example 2 with 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- -1-one was changed to the reaction product (A-2), and a composition for comparison was obtained in accordance with Example 1 except that the composition shown in Table 1 was used.

[Evaluation of hardenability of shielding part]

To each of the adhesives obtained in Example 1 and Comparative Example 1, 1% by mass of glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) of 4 탆 was added and mixed, and a line of 50 탆 comprising a chromium etched film and a line of 10 탆 Was alternately applied to the glass substrate, and then a black matrix substrate was bonded as an opposing substrate to obtain a sample for evaluation. Ultraviolet light of 3,000 mJ / cm 2 (for 30 seconds at 100 mW / cm 2) was irradiated from the glass substrate side on which the line / space was formed to the above obtained sample with a metal halide lamp, and then the cured portion of each sample was observed under a microscope. Further, each of the samples irradiated with the ultraviolet rays was further subjected to heat treatment at 120 占 폚 for 1 hour, and then the cured portion of each sample was observed under a microscope. The results are shown in Table 1.

As shown in Table 1, the adhesive for display according to the present invention had curability equivalent to that of ultraviolet rays even in the visible light as compared with the adhesive of Comparative Example 1, and had curability in the deep portion (low energy irradiated portion) Respectively. That is, excellent curability at low energy.

Synthesis Example 4 (Synthesis of compound (component (A)) represented by formula (1)

(Step 1) Synthesis of intermediate compound represented by formula (31)

To 1.9 parts of potassium cyanide, 10 parts of water and 53 parts of ethanol were added and dissolved, and the reaction solution was subjected to deaeration by ultrasonic treatment in a nitrogen atmosphere. 10 parts of 4- (methylthio) benzaldehyde represented by the following formula (30) was added dropwise to this solution, and the reaction was started by heating at 80 占 폚. After stirring for 30 minutes, the reaction solution was cooled to 3 캜 and the precipitated crystals were collected by suction filtration. The recovered crystals were purified by recrystallization using a large amount of ethanol to obtain 7.6 parts of an intermediate compound represented by the following formula (31).

[Chemical Formula 17]

(Step 2) Synthesis of intermediate compound represented by formula (32)

In a flask equipped with a stirrer, a reflux condenser and a stirrer, 9.0 parts of paraformaldehyde and 170 parts of dimethylsulfoxide were added and stirred. Then, a solution prepared by dissolving 1.4 parts of potassium hydroxide in 5 parts of ethanol was added dropwise and paraformaldehyde Stir until complete dissolution. A solution of 50 parts of the intermediate compound represented by the formula (31) obtained in the step 1 in 30 parts of dimethyl sulfoxide was added dropwise to the resulting dimethylsulfoxide solution over 30 minutes, and the mixture was stirred at room temperature for 2 hours. Then, 2.6 parts of 35% hydrochloric acid was added dropwise to neutralize the reaction to complete the reaction. Toluene and saturated brine were added to the reaction solution to extract the reaction product from the organic layer, and the separated and concentrated organic layer was crystallized to obtain 40 parts of an intermediate compound represented by the following formula (32).

[Chemical Formula 18]

(Step 3) Synthesis of compound (A-3) represented by the following formula (A-3)

10.0 parts of the intermediate compound represented by the formula (32) obtained in the step 2, 28 parts of toluene and 0.08 part of tin octylate were placed in a flask and refluxed with stirring until the mixture became homogeneous. Then, 5.6 parts of 2-methacryloyloxyethyl isocyanate (Carlene MOI, manufactured by Showa Denko K.K.) was added at a liquid temperature of 60 占 폚, stirring was continued for 3 hours and the reaction solution was crystallized by cooling to obtain the following formula ) Was obtained in an amount of 10.7 parts.

[Chemical Formula 19]

Synthesis Example 5 (Synthesis of compound (component (A)) represented by formula (1)

(Step 4) Synthesis of compound (A-4) represented by the following formula (A-4)

(A-4) shown below was obtained in the same manner as in Step 3 except that 2-acryloyloxyethyl isocyanate (Carrel AOI, manufactured by Showa Denko K.K.) was used instead of 2-methacryloyloxyethyl isocyanate A-4) was obtained in an amount of 6.4 parts.

[Chemical Formula 20]

Examples 2 to 4 (Preparation of Display Adhesive of the Present Invention)

(A-1), (A-3) or (A-4), (B-1) and (B-2) were mixed in the proportions shown in Tables 2 or 3, C-1) was dissolved. The obtained mixture was cooled to room temperature, and (D-1) and (E-1) were added and stirred, followed by further dispersing with a three-roll mill. The obtained composition was filtered with a metal mesh (635 mesh) to obtain an adhesive for display of the present invention.

Comparative Example 2 (Preparation of Comparative Adhesive)

(A-2), (B-1) and (B-2) were mixed in the proportions shown in the following Table 3 and the temperature was raised to 90 占 폚 and then (C-1) was dissolved. The obtained mixture was cooled to room temperature, and (D-1) and (E-1) were added and stirred, followed by further dispersing with a three-roll mill. The resulting composition was filtered with a metal mesh (635 mesh) to obtain a comparative display adhesive.

[Evaluation of hardenability of shielding part]

To each of the adhesives obtained in Examples 2 to 4 and Comparative Example 2, 1% by mass of glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) of 4 탆 was added and mixed, and a line of 50 탆 comprising an etching film of chromium After coating on a glass substrate having a space of 10 占 퐉 alternately formed thereon, a black matrix substrate was laminated as an opposing substrate to obtain a sample for evaluation. Ultraviolet light of 3,000 mJ / cm 2 (for 30 seconds at 100 mW / cm 2) was irradiated to the obtained sample from a glass substrate side on which a line / space was formed with a metal halide lamp, and then a cured portion of each sample was observed under a microscope. Further, each of the samples irradiated with the ultraviolet rays was further subjected to heat treatment at 120 占 폚 for 1 hour, and then the cured portion of each sample was observed under a microscope. The results are shown in Tables 2 and 3.

As shown in Tables 2 and 3, the adhesive for a display of the present invention has curability equivalent to ultraviolet rays even in the visible light as compared with the adhesive of Comparative Example 2, and has a curability in the deep portion (low energy irradiated portion) Respectively. That is, excellent curability at low energy.

INDUSTRIAL APPLICABILITY Since the display adhesive of the present invention exhibits sufficient curability even with low energy light, it is useful for a display component having a light shielding portion such as a sealant or a sealing agent for a liquid crystal display cell and a touch panel.

1: Liquid crystal display unit
2: a transparent substrate having a light shielding portion
3: transparent substrate
4:
5: Adhesive for display
6: a cured layer having an uncured portion
7: Cured resin layer
8: Ultraviolet ray

Claims (15)

Component (A)
[Chemical Formula 1]

(Wherein X represents a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure,
(2)

(Wherein (1-1), R ₈ represents an alkylene group or arylene group. R ₉ represents a hydrogen atom or an alkyl group having 1 to 4. Y represents an oxygen atom, a sulfur atom or NR _10. R ₁₀ Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
When X is a residue obtained by removing one n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure, n represents an integer of 1 to 6. R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group other than the above substituent. R ₂ to R ₆ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a cyano group, , A sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphono group, an amino group, an ammonio group, or an organic group other than the above substituent group, and each of R ₂ to R ₆ . Two or more groups selected from R ₂ to R ₆ present on the same benzene ring may be bonded to each other to form a ring structure. R ₇ represents a hydrogen atom.
When X represents a substituent represented by the formula (1-1), n represents 1. R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group other than the above substituent. R ₂ , R ₃ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, An organic group other than the above-mentioned substituent, and each of R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , ₃ , R ₅ and R ₆ may be the same or different. R ₂ and R ₃ existing on the same benzene ring may be combined to form a ring structure, or R ₅ and R ₆ present on the same benzene ring may be combined to form a ring structure. One of R ₄ represents an organic group containing a thioether bond and the other represents an organic group containing a hydrogen atom or a thioether bond. Furthermore, an organic group containing a thioether bond represented by R ₄ may be bonded to R ₃ or R ₅ to form a ring structure. And R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and a component (B) a photopolymerizable compound. The method according to claim 1,
And X is a substituent represented by the formula (1-1). The method according to claim 1,
And X is a residue obtained by removing n hydrogen atoms from a saturated hydrocarbon containing a cyclic structure. The method of claim 3,
Wherein the compound represented by the formula (1)
(3)

(Formula (2) of, R ₁ to R ₆ have the same meanings as R ₁ to R ₆ in the formula (1) as set forth in claim 5. A represents a cycloalkylene. D represents an alkylene group ). ≪ / RTI > 5. The method according to any one of claims 1 to 4,
Wherein the component (B) comprises a component (B-1) (meth) acrylic compound. 6. The method of claim 5,
Wherein the component (B-1) comprises a (meth) acrylate monomer. 6. The method of claim 5,
Wherein the component (B-1) is at least one compound selected from the group consisting of a urethane (meth) acrylate oligomer, a (meth) acrylate oligomer having a polyisoprene skeleton and a (meth) acrylate oligomer having a polybutadiene skeleton (Meth) acrylate oligomer. 5. The method according to any one of claims 1 to 4,
Wherein the component (B) comprises an epoxy compound of the component (B-2). 5. The method according to any one of claims 1 to 4,
Further, an adhesive for display comprising a component (C) an organic filler and / or a component (D) an inorganic filler. 10. The method of claim 9,
Wherein the component (C) comprises at least one organic filler selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicon fine particles. 5. The method according to any one of claims 1 to 4,
Further, an adhesive for display, which contains the component (E) silane coupling agent. An optical member comprising the cured product of the adhesive for display according to any one of claims 1 to 4. A touch panel comprising the optical member according to claim 12. A liquid crystal sealing agent or an encapsulating agent for a liquid crystal display cell using the adhesive for display according to any one of claims 1 to 4. A liquid crystal display cell comprising the cured product of the liquid crystal sealant or the cured product of the encapsulating agent for a liquid crystal display cell according to claim 14.

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