CN111690355A - Sealant for display and liquid crystal display - Google Patents

Sealant for display and liquid crystal display Download PDF

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Publication number
CN111690355A
CN111690355A CN202010164002.XA CN202010164002A CN111690355A CN 111690355 A CN111690355 A CN 111690355A CN 202010164002 A CN202010164002 A CN 202010164002A CN 111690355 A CN111690355 A CN 111690355A
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sealant
display
component
acrylate
meth
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CN111690355B (en
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武藤正嘉
小渊香津美
内藤正弘
木田昌博
田上胜大
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1341—Filling or closing of cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention relates to a sealant for a display, which is also applicable to a flexible display or a curved display. More specifically, the present invention relates to a sealant for a display, which contains a compound having a specific structure in a molecule. The sealant for display is excellent in adhesion strength to an adherend, and has both flexibility and low moisture permeability, and therefore is useful as a sealant for display, flexible display, and display in a curved shape, which particularly requires adhesion to an organic film. A sealant for display, which comprises (A) a urethane (meth) acrylate obtained by reacting (a) a polyol having an alicyclic structure, (b) an organic polyisocyanate, and (c) a hydroxyl group-containing (meth) acrylate.

Description

Sealant for display and liquid crystal display
Technical Field
The present invention relates to a sealant for a display, which is also applicable to a flexible display or a curved display. This sealing agent for a display can achieve both flexibility and low moisture permeability, and is therefore useful particularly as a sealing agent for a flexible display or a display having a curved shape. Further, the sealant having high flexibility as in the present invention is excellent in adhesive strength to an adherend, and therefore is useful also in applications requiring high adhesive strength.
Background
Examples of the sealant for a display include a sealant for a liquid crystal display (seal), a sealant for an organic-Electroluminescence (EL) display, and an adhesive for a touch panel. These materials have a common aspect in that they are required to have excellent hardenability and also to have a characteristic that the emission gas is small and the display element is not damaged.
Recently, curved displays and flexible displays have been developed and produced. A flexible substrate such as a plastic film is used as a substrate used in such a display instead of a conventional rigid substrate such as glass (patent document 1).
Under such circumstances, the sealant for display is required to have such a property as to follow the flexure of the substrate and the like, that is, to be soft even after curing.
Further, a sealant having excellent flexibility is also advantageous in terms of adhesive strength. For example, peeling or equipment damage caused by impact may be mitigated. From the above-mentioned viewpoint, the demand for imparting flexibility to the sealant has also increased.
On the other hand, in order to improve the flexibility of the cured product, it is effective to reduce the crosslinking density of the cured product. However, the decrease in the crosslinking density generally deteriorates the moisture permeability. This is believed to be due to moisture ingress from loose parts of the network. Therefore, in order to secure low moisture permeability, it is necessary to achieve contradictory properties of improving flexibility without lowering the crosslinking density or lowering the crosslinking density without deteriorating the moisture permeability.
Conventionally, from the viewpoint of improving the adhesive strength, an adhesive for display elements having flexibility has been developed (patent document 2). However, a product having sufficient performance to accommodate the flexible substrate has not been realized.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2012-238005
[ patent document 2] Japanese patent laid-open No. 2016-24240
Disclosure of Invention
[ problems to be solved by the invention ]
The present invention relates to a sealant for a display, which is also applicable to a flexible display or a curved display. More specifically, the present invention relates to a sealant for a display using a urethane (meth) acrylate containing a polyol having an alicyclic structure. The sealant for display has both flexibility and low moisture permeability, and is excellent in adhesive strength, and therefore is useful as a sealant for display.
[ means for solving problems ]
As a result of intensive studies, the present inventors have found that a sealant for a display containing a urethane (meth) acrylate containing a polyol having an alicyclic structure is excellent in flexibility and low moisture permeability, and have completed the present invention.
In the present specification, "(meth) acrylate" means "acrylate" and/or "methacrylate".
That is, the present invention relates to the following [1] to [12 ].
[1]
A sealing agent for a display, comprising (A) a urethane (meth) acrylate obtained by reacting (a) a polyol having an alicyclic structure, (b) an organic polyisocyanate, and (c) a hydroxyl group-containing (meth) acrylate.
[2]
The sealant for display according to the item [1], wherein the component (a) is a polyol having a tricyclodecanedimethanol structure.
[3]
The sealant for display according to the above [1] or [2], wherein the component (A) is obtained by further reacting a polyol other than the component (a) as the component (a-1).
[4]
The sealant for display according to any one of [1] to [3], further comprising a component (B) a curable compound.
[5]
The sealant for display use according to the item [4], wherein the component (B) is a partial epoxy (meth) acrylate.
[6]
The sealant for display use according to any one of [1] to [5], further comprising a component (C) an organic filler.
[7]
The sealant for display according to [6], wherein the component (C) is one or more organic fillers selected from the group consisting of urethane microparticles, acrylic microparticles, styrene olefin microparticles, and silicone microparticles.
[8]
The sealant for display use according to any one of [1] to [7], further comprising an ingredient (D) a thermosetting agent.
[9]
The sealant for display use according to any one of [1] to [8], further comprising a component (E) a photo radical polymerization initiator.
[10]
The sealant for display use according to any one of [1] to [9], further containing a component (F) a thermal radical polymerization initiator.
[11]
The sealant for display according to any one of [1] to [10], which is a liquid crystal sealant for a liquid crystal dropping method.
[12]
A liquid crystal display sealed with the liquid crystal sealant for liquid crystal dropping method according to [11 ].
[ Effect of the invention ]
The sealant for display of the present invention has both flexibility and low moisture permeability, and is excellent in adhesive strength, and therefore is useful as a sealant for display.
Detailed Description
The sealant for a display of the present invention contains (a) a urethane (meth) acrylate (hereinafter also simply referred to as "component (a)") comprising (a) a polyol having an alicyclic structure, (b) an organic polyisocyanate, and (c) a hydroxyl group-containing (meth) acrylate.
The component (a) has a soft skeleton specific to a urethane structure, and further uses a polyol having an alicyclic structure, thereby imparting the cured product with characteristics of softness and low moisture permeability, and having high adhesive strength not only on a glass substrate but also on an alignment film.
The flexibility can be measured by the modulus of elasticity of the cured product. For irradiating ultraviolet ray, 3000mJ/cm2The elastic modulus of a cured product having a thickness of 100 μm which is cured at 130 ℃ for 40 minutes (measurement wavelength: 365nm) is preferably 200MPa to 3000MPa, more preferably 400MPa to 2000MPa, and particularly preferably 600MPa to 1500 MPa. It can be said thatA range of display adhesives is preferred because they can follow the stress applied to the display.
As the low moisture permeability, it is preferable that the moisture permeability is 60g/m in a cured product having a thickness of 300 μm224h or less.
The component (a) can be obtained by synthesizing (a) a polyol having an alicyclic structure, (b) an organic polyisocyanate, and (c) a hydroxyl group-containing (meth) acrylate by a conventional method.
The isocyanate group of the component (b) is preferably reacted at 1.1 to 2.0 equivalents, particularly preferably at 1.3 to 2.0 equivalents, based on 1 equivalent of the hydroxyl group of the component (a). The reaction temperature is preferably from room temperature (25 ℃) to 100 ℃.
The hydroxyl group in the component (c) is preferably reacted at 0.95 to 1.1 equivalents per 1 equivalent of the isocyanate group in the reaction product of the component (a) and the component (b). The reaction temperature is preferably from room temperature (25 ℃) to 100 ℃.
The component (a) is not particularly limited as long as the polyol having an alicyclic structure has an alicyclic structure in the polyol structure.
Specific examples of the component (a) include cyclohexanedimethanol, norbornanedimethanol, norbornenedimethanol, tricyclodecanedimethanol, pentacyclopentadecane dimethanol, adamantanedimethanol, hydrogenated bisphenol a, hydrogenated bisphenol F, hydrogenated terpene diphenol, Ethylene Oxide (EO) thereof, Propylene Oxide (PO) thereof, and caprolactone-modified products thereof. In order to improve the adhesiveness, an alicyclic structure having 20 or less carbon atoms is preferably used, and tricyclodecanedimethanol is preferably used in view of the balance between low moisture permeability and flexibility. Examples of commercially available products of tricyclodecanedimethanol include TCD alcohol DM from Celanese corporation.
In addition, diols having a crosslinked structure such as norbornanedimethanol, norbornenedimethanol, tricyclodecanedimethanol and adamantanedimethanol are preferable from the viewpoint of improving water resistance.
In the present invention, it is also a preferred embodiment to use a polyol other than the component (a) as the component (a-1). Specific examples of the component (a-1) include: hydrogenated polybutadienePolyhydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, 3-methyl-1, 5-pentanediol, 2, 4-diethyl-1, 5-pentanediol, cyclohexane-1, 4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A poly (ethylene glycol)
Figure BDA0002406006930000051
Ethoxylated glycol, bisphenol A poly
Figure BDA0002406006930000052
Diols (a-1-1) such as propoxydiol, and polyester diols (a-1-2) which are reaction products of these diols (a-1-1) with dibasic acids or anhydrides thereof (for example, succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid, or anhydrides thereof). Preferred examples thereof include 3-methyl-1, 5-pentanediol and its polyester diol.
When the component (a) and the component (a-1) are used in combination, the component (a) is usually 3 to 95% by weight, preferably 5 to 50% by weight, and more preferably 8 to 20% by weight of the total amount of the component (a) and the component (a-1).
Specific examples of (b) the organic polyisocyanate include: toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, xylylene diisocyanate, 4 '-diphenylmethane diisocyanate, 4' -cyclohexylmethane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, dimethyl diisocyanate, 1, 5-naphthalene diisocyanate, 3 '-dimethyl-4, 4' -diphenylene diisocyanate, and the like. Preferred examples thereof include tolylene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
Specific examples of (c) the hydroxyl group-containing (meth) acrylate include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1, 4-butanediol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, a caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. Preferred examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate.
The content of the component (a) is usually 5 to 50% by mass, preferably 5 to 30% by mass, and more preferably 10 to 20% by mass of the total amount of the sealing agent for a display.
[ (B) curable Compound ]
The sealant for display of the present invention contains a curable compound as the component (B) (hereinafter also referred to simply as "component (B)").
The component (B) is not particularly limited as long as it is a compound that is cured by light, heat or the like, and is preferably a (meth) acrylate (component (B-1) (hereinafter also simply referred to as component (B-1)), and examples thereof include a (meth) acrylate and an epoxy (meth) acrylate.
[ (B-1) (meth) acrylate ]
Specific examples of the (meth) acrylic acid ester include: n-acryloyloxyethylhexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane-1, 4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenylpolyethoxy (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, orthophenylphenol monoethoxy (meth) acrylate, orthophenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tribromophenoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and mixtures thereof, Dicyclopentenyloxyethyl (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxy di (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, tricyclodecane, Trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, diacrylate of an ester diacrylate of neopentyl glycol and hydroxytrimethylacetic acid or a diacrylate of a caprolactone adduct of an ester of neopentyl glycol and hydroxytrimethylacetic acid. Preferred examples thereof include N-acryloyloxyethylhexahydrophthalimide, phenoxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
Epoxy (meth) acrylates are obtained in a known manner by reaction of epoxy resins with (meth) acrylic acid. The epoxy resin to be used as a raw material is not particularly limited, but is preferably a 2-functional or higher epoxy resin, and examples thereof include: resorcinol diglycidyl ether, bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol a novolac epoxy resin, bisphenol F novolac epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, hydantoin epoxy resin, isocyanurate epoxy resin, phenol novolac epoxy resin having a triphenol methane skeleton, and diglycidyl etherate of bifunctional phenols such as catechol and resorcinol, diglycidyl etherate of bifunctional alcohols, halides and hydrides thereof, and the like. Of these, bisphenol a type epoxy resins and resorcinol diglycidyl ether are preferable from the viewpoint of liquid crystal contamination. The ratio of the epoxy group to the (meth) acryloyl group is not limited, and is appropriately selected from the viewpoint of process suitability.
In addition, a partially epoxy (meth) acrylate in which a part of the epoxy group is acrylated may be preferably used. The ratio of the acrylation at this time is preferably about 30% to 70%.
The component (B-1) may be used alone or in combination of two or more. When the component (B-1) is used in the resin composition of the present invention, the content is usually 10 to 80% by mass, preferably 20 to 70% by mass, based on the total amount of the resin composition.
[ (B-2) epoxy resin ]
In an embodiment of the present invention, it is more preferable that the component (B) further contains an epoxy resin as the component (B-2) (hereinafter, also simply referred to as the component (B-2)).
The epoxy resin is not particularly limited, but is preferably a 2-functional or higher epoxy resin, and examples thereof include: resorcinol diglycidyl ether, bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol a novolac epoxy resin, bisphenol F novolac epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, hydantoin epoxy resin, isocyanurate epoxy resin, phenol novolac epoxy resin having a triphenol methane skeleton, and diglycidyl etherate of bifunctional phenols such as catechol and resorcinol, diglycidyl etherate of bifunctional alcohols, halides and hydrides thereof, and the like. Of these, bisphenol a type epoxy resins and resorcinol diglycidyl ether are preferable from the viewpoint of liquid crystal contamination.
The component (B-2) may be used alone or in combination of two or more. When the component (B-2) is used in the resin composition of the present invention, the content is usually 5 to 50% by mass, preferably 5 to 30% by mass, based on the total amount of the resin composition.
[ (C) organic Filler ]
The sealant for display of the present invention may contain an organic filler as the component (C) (hereinafter also simply referred to as "component (C)").Examples of the organic filler include: urethane fine particles, acrylic fine particles, styrene olefin fine particles, and silicone fine particles. The silicone microparticles are preferably KMP-594, KMP-597, KMP-598 (manufactured by shin-Etsu chemical industries), and Toyofia (torayfil)RTME-5500, 9701, EP-2001 (Toray Dow Corning) is preferable as urethane fine particles, JB-800T, HB-800BK (Kogyo Co., Ltd.) is preferable as styrene fine particles, Ravalone (RABALON) is preferableRTMT320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (manufactured by mitsubishi chemical corporation), and preferable styrene olefin fine particles are septon (septon)RTMSEPS2004、SEPS2063。
These organic fillers may be used alone or in combination of two or more. Also, two or more kinds of core-shell structures may be used. Of these, acrylic microparticles and silicone microparticles are preferable.
When the acrylic fine particles are used, acrylic rubber having a core-shell structure containing two types of acrylic rubber is preferable, and particularly preferable is one having a core layer of n-butyl acrylate and a shell layer of methyl methacrylate. It acts as zefil ak (zefiac)RTMF-351, and sold by Aike (AICA) industries, Inc.
The silicone fine particles include organopolysiloxane crosslinked powder, linear dimethylpolysiloxane crosslinked powder, and the like. Further, the composite silicone rubber may be one in which a silicone resin (for example, polyorganosilsesquioxane resin) is coated on the surface of the silicone rubber. Among these fine particles, particularly preferred are silicone rubber fine particles of a linear dimethylpolysiloxane crosslinked powder or composite silicone rubber fine particles of a linear dimethylpolysiloxane crosslinked powder coated with a silicone resin. These may be used alone or in combination of two or more. Further, it is preferable that: the shape of the rubber powder is preferably spherical, which is less viscous after addition. When the component (C) is used in the sealant for a display of the present invention, the content is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the sealant for a display.
[ (D) Heat-curing agent ]
The display sealing agent of the present invention can be added with a thermosetting agent (hereinafter also simply referred to as "component (D)") as the component (D) to improve the reactivity.
Examples of the component (D) include compounds having a carboxyl group bonded to an aromatic ring in the molecule, polyamines, polyphenols, and organic acid hydrazides. However, the present invention is not limited to these examples. Examples thereof include: aromatic hydrazides include terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2, 6-naphthalene carboxylic acid dihydrazide, 2, 6-pyridine dihydrazide, 1, 2, 4-benzene trihydrazide, 1, 4, 5, 8-naphthalene carboxylic acid tetrahydrazide, and pyromellitic acid tetrahydrazide. Further, if it is an aliphatic hydrazide, for example, there are mentioned: formyl hydrazine, acetyl hydrazine, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, sebacic acid dihydrazide, 1, 4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N '-hexamethylenebis semicarbazide (N, N' -hexamethylenebissemicarbazide), citric acid trihydrazide, nitroacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1, 3-bis (hydrazinocarboethyl) -5-isopropylhydantoin and the like hydantoin skeletons, preferably dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate having a valinyl hydantoin (valinehydatoin) skeleton (skeleton in which the carbon atom of the hydantoin ring is substituted with an isopropyl group), Tris (1-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate, and the like. From the viewpoint of the balance between curing reactivity and latent property, isophthalic dihydrazide, malonic dihydrazide, adipic dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate are preferable, and tris (2-hydrazinocarbonylethyl) isocyanurate is particularly preferable.
As the component (D), a compound having a carboxyl group bonded to an aromatic ring in the molecule is preferably used, and examples thereof include 4-hydroxybenzoic acid, thiosalicylic acid, terephthalic acid, citrazinic acid, 4-aminobenzoic acid, 4- (aminomethyl) benzoic acid, and 2-mercaptonicotinic acid.
The component (D) may be used alone or in combination of two or more. When the component (D) is used in the sealant for a display of the present invention, the content is usually 0.1 to 10% by mass, preferably 0.1 to 5% by mass, based on the total amount of the sealant for a display.
The reactivity of the sealant for display device of the present invention can be further improved by adding a curing catalyst. The curing catalyst includes amines and imidazoles, and imidazoles are particularly preferable. As imidazoles, there may be mentioned: 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2, 4-diamino-6 (2 '-methylimidazole (1')) ethyl-s-triazine, 2, 4-diamino-6 (2 '-undecylimidazole (1')) ethyl-s-triazine, 2, 4-diamino-6 (2 '-ethyl-4-methylimidazole (1')) ethyl-s-triazine, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-, 2, 4-diamino-6 (2 '-methylimidazole (1')) ethyl-s-triazine isocyanuric acid adduct, 2: 3 adduct of 2-methylimidazole isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3, 5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3, 5-dicyanoethoxymethylimidazole and the like.
[ (E) photo radical polymerization initiator ]
The sealant for display of the present invention may contain a photo radical polymerization initiator as the component (E) (hereinafter also simply referred to as "component (E)"). The photo radical polymerization initiator is not particularly limited as long as it is a compound that generates a radical or an acid by irradiation of ultraviolet rays or visible light to initiate a chain polymerization reaction, and examples thereof include: benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methyl propiophenone, 2-methyl- [4- (methyl) ketalThio) phenyl]2-morpholino-1-propane, 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyl disulfide, etc. Specific examples thereof include: yanjiaguo (IRGACURE)RTM651. 184, 2959, 127, 907, 369, 379EG, 819, 784, 754, 500, OXE01, OXE02, OXE03, OXE04, Dacrore (DAROCURE)RTM1173. Luxirui (LUCIRIN)RTMTPO (both manufactured by BASF corporation), Seikukol (SEIKUOL)RTMZ, BZ, BEE, BIP, BBI (all manufactured by Seiko chemical Co., Ltd.), and the like. Of these, preferred is brilliant solid (IRGACURE) as an oxime ester initiatorRTMOXE01、OXE02、OXE03、OXE04。
Further, from the viewpoint of liquid crystal contamination, those having a (meth) acrylic group in the molecule are preferably used, and for example, a reaction product of 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one is preferably used. This compound can be produced by the method described in International publication No. 2006/027982.
When the component (E) is used in the sealant for a display of the present invention, the content is usually 0.001 to 3% by mass, preferably 0.002 to 2% by mass, based on the total amount of the sealant for a display.
[ (F) thermal radical polymerization initiator ]
The sealant for display of the present invention may contain (F) a thermal radical polymerization initiator (hereinafter also simply referred to as "component (F)") to improve the curing speed and curability.
The thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating to initiate a chain polymerization reaction, and examples thereof include organic peroxides, azo compounds, benzoin ether compounds, acetophenone compounds, Benzopinacol (Benzopinacol), and the like, and Benzopinacol is preferably used. For example, as the organic peroxide, Kayamak (kayamak)RTMA. M, R, L, LH, SP-30C, Parka Chox (PERKADOX) CH-50L, BC-FF, Kadax (Cadox) B-40ES, Parka Chox (PERKADOX)14, Dow Chongo (TRIGONOX)RTM22-70E, 23-C70, 121-50E, 121-LS50E, 21-LS50E, 42LS, Kayaestetre (KayaEother)RTMP-70, TMPO-70, CND-C70, OO-50E, AN, Kayabuyu road (kayabutyl)RTMB. Parkatoches (PERKADOX)16, Kaya Carlubao (Kayacarbon)RTMBIC-75, AIC-75 (manufactured by Kayaku AKZO CO., LTD.) and Permek (chemical Agents of Aksu Co., Ltd.)RTMN, H, S, F, D, G Parhaik Pizza (PERHEXA)RTMH. HC, TMH, C, V, 22, MC, Pacure (Percure)RTMAH. AL, HB, PabutyL road (perbutyl)RTMH. C, ND, L, Parkumilo (PERCUMYL)RTMH. D, Palaoylu (PEROYL)RTMIB. IPP, PaoKuta (PEROCTA)RTMND (manufactured by Nichigan oil Co., Ltd.) and the like are available as commercially available products.
Further, as azo compounds, VA-044, 086, V-070, VPE-0201, VSP-1001 (manufactured by Wako pure chemical industries, Ltd.) and the like are commercially available.
The content of the component (F) is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass, and particularly preferably 0.001 to 3% by mass of the total amount of the sealant for a display of the present invention.
The sealing agent for a display of the present invention may further contain additives such as an inorganic filler, a silane coupling agent, a radical polymerization inhibitor, a pigment, a leveling agent, a defoaming agent, and a solvent, as required.
[ inorganic Filler ]
As the inorganic filler, there may be mentioned: 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, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, and asbestos. These inorganic fillers may be used by mixing two or more kinds.
If the average particle size of the inorganic filler is too large, it becomes a factor of failure to form a gap smoothly when the upper and lower glass substrates are bonded to each other in the production of a narrow gap (gap) liquid crystal display cell, and therefore 2000nm or less is suitable, preferably 1000nm or less, and more preferably 300nm or less. The lower limit is preferably about 10nm, and more preferably about 100 nm. The particle diameter can be measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by Seishin corporation, Ltd.; LMS-30).
When the inorganic filler is used in the sealant for display of the present invention, the content is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the sealant for display. When the content of the inorganic filler is less than 5% by mass, the adhesion strength to the glass substrate is reduced, and the moisture resistance reliability is also poor, so that the reduction in adhesion strength after moisture absorption may be large. When the content of the inorganic filler is more than 50% by mass, the filler content is too large, and thus the liquid crystal cell may be difficult to break and a gap between the liquid crystal cells may not be formed.
[ silane coupling agent ]
Examples of the silane coupling agent include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) -3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane and the like. These silane coupling agents are sold as KBM series, KBE series, and the like by shin-Etsu chemical industries, Ltd, and thus are readily available from the market. When a silane coupling agent is used in the sealing agent for a display of the present invention, the amount is preferably 0.05 to 3% by mass based on the total amount of the sealing agent for a display.
[ radical polymerization inhibitor ]
The radical polymerization inhibitor is not particularly limited as long as it is a compound that prevents polymerization by reacting with a radical generated by a photo radical polymerization initiator, a thermal radical polymerization initiator, or the like, and quinone, piperidine, hindered phenol, nitroso, or the like can be used. Specifically, there may be mentioned: naphthoquinone, 2-hydroxynaphthoquinone, 2-menadione, 2-methoxynaphthoquinone, 2, 6, 6-tetramethylpiperidine-1-oxyl, 2, 6, 6-tetramethyl-4-hydroxypiperidine-1-oxyl, 2, 6, 6-tetramethyl-4-methoxypiperidine-1-oxyl, 2, 6, 6-tetramethyl-4-phenoxypiperidine-1-oxyl, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, p-benzoquinone, butylated hydroxyanisole, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butylcresol, stearyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-methoxynaphthoquinone, 2, 6, 6-tetramethylpiperidine-1-oxyl, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, p-benzoquinone, butylated hydroxyanisol, 2, 2 ' -methylenebis (4-ethyl-6-tert-butylphenol), 4 ' -thiobis (3-methyl-6-tert-butylphenol), 4 ' -butylidenebis (3-methyl-6-tert-butylphenol), 3, 9-bis [1, 1-dimethyl-2- [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ], 2, 4, 8, 10-tetraoxaspiro [5, 5] undecane, tetrakis- [ methylene-3- (3 ', 5 ' -di-tert-butyl-4 ' -hydroxyphenylpropionate ] methane ], 1, 3, 5-tris (3 ', 5 ' -di-tert-butyl-4 ' -hydroxybenzyl) -triazine (sec-triazine) -2, 4, 6- (1H, 3H, 5H) trione, p-methoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, an aluminum salt of N-nitrosophenylhydroxylamine, a product name of Adekastab (Adekastab) LA-81, a product name of Adekastab (Adekastab) LA-82 (manufactured by Adekaka, Inc.), and the like, but the present invention is not limited thereto. Among these, naphthoquinone-based, hydroquinone-based, nitroso-based, and piperazine-based radical polymerization inhibitors are preferable, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2, 6-di-tert-butyl-P-cresol, bolitep (POLYSTOP)7300P (manufactured by boston gmbh) is more preferable, and bolitep (POLYSTOP)7300P (manufactured by boston gmbh) is most preferable.
The content of the radical polymerization inhibitor is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and particularly preferably 0.01 to 0.2% by mass, based on the total amount of the sealant for display of the present invention.
As an example of a method for obtaining the sealant for a display of the present invention, there is a method described below. First, the component (E) is dissolved in the components (a) and (B) by heating as necessary. Subsequently, the mixture is cooled to room temperature, and then, if necessary, the components (C), (D), and (F), the inorganic filler, the silane coupling agent, the defoaming agent, the leveling agent, the solvent, and the like are added, uniformly mixed by a known mixing device such as a three-roll mill, a sand mill, a ball mill, and the like, and filtered by a metal mesh, whereby the sealant for a display of the present invention can be produced.
The sealant for display of the present invention is very useful as an adhesive for liquid crystal display cells, particularly as a liquid crystal sealant. An example of a liquid crystal display cell in the case where the sealant for a display of the present invention is used as a liquid crystal sealant is described below.
A liquid crystal display cell manufactured using the adhesive for a liquid crystal display cell of the present invention is obtained by arranging a pair of substrates having predetermined electrodes formed on the substrates in opposition to each other at a predetermined interval, sealing the surroundings with the liquid crystal sealant of the present invention, and sealing liquid crystal in the gap between the substrates. The type of the liquid crystal to be sealed is not particularly limited. Here, the substrate includes a combination of a substrate having light-transmitting properties and at least one of glass, quartz, plastic, silicon, and the like. As a method for producing the same, a spacer (gap control material) such as glass fiber is added to the liquid crystal sealing agent of the present invention, and then the liquid crystal sealing agent is applied to one of the pair of substrates using a dispenser, a screen printer, or the like, and then pre-cured at 80 to 120 ℃. Then, liquid crystal is dropped inside the dam of the liquid crystal sealing agent, and another glass substrate is stacked in vacuum to form a gap. After gap formation, at 90 deg.CCured at 130 ℃ for 30 minutes to 2 hours, whereby the liquid crystal display cell of the present invention can be obtained. When used as a photo-thermal type, the liquid crystal sealing agent portion is photo-cured by irradiating the liquid crystal sealing agent portion with ultraviolet rays using an ultraviolet ray irradiation machine. The ultraviolet irradiation dose is preferably 500mJ/cm2～6000mJ/cm2More preferably 1000mJ/cm2～4000mJ/cm2(measurement wavelength: 365 nm). Thereafter, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ℃ for 30 minutes to 2 hours, if necessary. The liquid crystal display cell of the present invention thus obtained has no display defects due to liquid crystal contamination, and is excellent in adhesion and moisture resistance reliability. Examples of the spacer include glass fiber, silica beads, and polymer beads. The diameter thereof varies depending on the purpose, and is usually 2 to 8 μm, preferably 4 to 7 μm. The amount of the liquid crystal sealing agent used is usually about 0.1 to 4 parts by mass, preferably about 0.5 to 2 parts by mass, and more preferably about 0.9 to 1.5 parts by mass, per 100 parts by mass of the liquid crystal sealing agent of the present invention.
The sealant for display of the present invention is very suitable for use in an adhesive in a field where curability, adhesion to different adherends, and reliability against moist heat are required. Examples of the sealant include a liquid crystal sealant, a sealant for organic EL, and an adhesive for touch panel.
[ examples ]
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples. Unless otherwise specified, "part" and "%" in this document are based on mass.
[ Synthesis example 1]
A flask equipped with a thermometer, a cooling tube and a stirrer was charged with 987.9g of polyester polyol (P-2050 manufactured by Korea (Kuraray) Co., Ltd., hydroxyl value 56.8mgKOH/g), 987.9g of 3-methyl-1, 5-pentanediol and sebacic acid, 98.2g of tricyclodecanedimethanol (TCD alcohol DM manufactured by Celanese Co., Ltd., molecular weight 196.3), and 444.6g of isophorone diisocyanate (Nautat (VESTAN) IPDI manufactured by Evonik (Evonik) Co., Ltd., molecular weight 222.3) and reacted at 80 ℃.
The isocyanate content at this time was determined by adding an excess of amine and back-titrating with hydrochloric acid, and it was confirmed that the value was within plus or minus 2% of the residual amount of isocyanate determined from the calculated value.
Next, 0.9g of methoquinone (polymerization inhibitor), 239.2g of 2-hydroxyethyl acrylate (molecular weight: 116.1), and 0.5g of dibutyltin dilaurate (catalyst) were added thereto, and the mixture was stirred at 80 ℃ to effect a reaction until the absorption spectrum of the isocyanate group in the infrared absorption spectrum (2280 cm)-1) Until disappeared, a urethane acrylate having a weight average molecular weight of 6600 was obtained.
[ Synthesis example 2]
A flask equipped with a thermometer, a cooling tube and a stirrer was charged with 1979.2g of polycaprolactone diol (Placcel 220 and hydroxyl value 56.7mgKOH/g, manufactured by Daicel corporation) and 400.1g of isophorone diisocyanate (VestaNAT IPDI and molecular weight 222.3, manufactured by Evonik corporation), and reacted at 80 ℃.
The isocyanate content at this time was determined by adding an excess of amine and back-titrating with hydrochloric acid, and it was confirmed that the value was within plus or minus 2% of the residual amount of isocyanate determined from the calculated value.
Then, 1.3g of methoquinone (polymerization inhibitor), 191.4g of 2-hydroxyethyl acrylate (molecular weight 116.1), and 0.8g of dibutyltin dilaurate (catalyst) were added thereto, and the mixture was stirred at 80 ℃ to carry out a reaction until the absorption spectrum of the isocyanate group in the infrared absorption spectrum (2280 cm)-1) Until disappeared, a urethane acrylate having a weight average molecular weight of 11100 was obtained.
[ Synthesis example 3]
A flask equipped with a thermometer, a cooling tube and a stirrer was charged with 835.0g of hydrogenated polybutadiene polyol (GI-1000 manufactured by Nippon Caodan Co., Ltd., hydroxyl value: 67.2mgKOH/g), 98.2g of tricyclodecanedimethanol (TCD alcohol DM manufactured by Celanese Co., Ltd., molecular weight: 196.3), and 444.6g of isophorone diisocyanate (VestaNAT IPDI manufactured by Yingwa (Evonik) Co., Ltd., molecular weight: 222.3) and reacted at 80 ℃.
The isocyanate content at this time was determined by adding an excess of amine and back-titrating with hydrochloric acid, and it was confirmed that the value was within plus or minus 2% of the residual amount of isocyanate determined from the calculated value.
Next, 0.8g of methoquinone (polymerization inhibitor), 239.2g of 2-hydroxyethyl acrylate (molecular weight: 116.1), and 0.5g of dibutyltin dilaurate (catalyst) were added thereto, and the mixture was stirred at 80 ℃ to effect a reaction until the absorption spectrum of the isocyanate group in the infrared absorption spectrum (2280 cm)-1) Until disappeared, a urethane acrylate having a weight average molecular weight of 5700 was obtained.
[ Synthesis example 4]
100 parts (0.28 mol) of commercially available benzopinacol (manufactured by tokyo chemical synthesis) was dissolved in 350 parts of dimethyl formaldehyde. To this, 32 parts (0.4 mol) of pyridine as a base catalyst and 150 parts (0.58 mol) of BSTFA (manufactured by shin-Etsu chemical Co., Ltd.) as a silylating agent were added, and the mixture was heated to 70 ℃ and stirred for 2 hours. The obtained reaction solution was cooled, and 200 parts of water was added thereto while stirring to precipitate a product and deactivate the unreacted silylation agent. The precipitated product was separated by filtration and washed with water. The obtained product was dissolved in acetone, and water was added thereto to recrystallize it, followed by purification. 105.6 parts of the aimed 1, 2-bis (trimethylsilyloxy) -1, 1, 2, 2-tetraphenylethane were obtained (yield 88.3%).
Examples 1 to 2 and comparative examples 1 to 2
The components (a), (B), and (O) were mixed at the ratios shown in table 1 below, the component (F) was dissolved by heating at 90 ℃, and then cooled to room temperature, the components (C), (D), (E), and (O) were added, and after stirring, the mixture was dispersed by a three-roll mill, and filtered by a metal mesh (635 mesh) to prepare a sealant for a display.
[ evaluation ]
[ adhesive Strength ]
Spin-coating the orientation film solution (RN 2880 manufactured by Nissan chemical industries, Ltd.) on a glass substrate, pre-baking for 3 minutes by using a 80 ℃ heating plate, and calcining in a 230 ℃ ovenFor 30 minutes. Further, the substrate with the alignment film was irradiated with 500mJ/cm of light by a UV irradiation machine2(measurement wavelength: 254nm) and further calcined in an oven at 230 ℃ for 30 minutes.
To 100g of the sealing agent for display produced in examples and comparative examples, 1g of 5 μm glass fiber was added as a spacer, and mixed and stirred, the sealing agent for display was applied to a glass substrate coated with an alignment film so as to reproduce a corner portion of 1cm × 1cm, the opposing alignment film-coated substrates were bonded, and irradiated with 3000mJ/cm by an Ultraviolet (UV) irradiation machine2(measurement wavelength: 365nm), and then put into an oven to be thermally cured at 130 ℃ for 40 minutes. The peel adhesion strength of the alignment film coated glass substrate was measured as a pressed angle portion using a bond tester (bondtester) (manufactured by western incorporated by reference: SS-30 WD). The strength is shown in Table 1.
The results of the adhesion strength measurement on the glass substrate on which the alignment film was not applied are also shown in table 1.
[ moisture permeability ]
The sealants for displays manufactured in examples and comparative examples were sandwiched between polyethylene terephthalate (PET) films to prepare films having a thickness of 300 μm, and the films were irradiated with 3000mJ/cm using a UV irradiator2(measurement wavelength: 365nm), and then put into an oven, and heat-cured at 130 ℃ for 40 minutes, and after curing, the PET film was peeled off to prepare a sample. The moisture permeability of a sample at 60 ℃ of 90% was measured by a moisture permeability measuring apparatus (manufactured by Lyssy, Inc.: L80-5000). The results are shown in Table 1.
[ modulus of elasticity ]
The sealants for displays manufactured in examples and comparative examples were sandwiched between polyethylene terephthalate (PET) films to prepare films having a thickness of 100 μm, and the films were irradiated with 3000mJ/cm by a UV irradiation machine2(measurement wavelength: 365nm), and then put into an oven, and heat-cured at 130 ℃ for 40 minutes, and after curing, the PET film was peeled off to prepare a sample. Using Tencilon universal tester (A)&RTG-1210) The tensile test was carried out on the sample at room temperature (22 ℃ C.) at a test speed of 5 mm/min. The results are shown in Table 1.
[ Table 1]
Figure BDA0002406006930000171
A-1: urethane acrylate obtained in Synthesis example 1
B-1-1: partially acrylated bisphenol A epoxy resins
(Synthesis example by a general synthetic method: reacting 50% equivalent of acrylic acid in Japanese patent laid-open publication No. 2016 & lt- & gt 24243.)
B-1-2: o-Phenylphenoxyethyl acrylate (manufactured by Midanson (MIWON) Co., Ltd.: Milamor (Miramer) M-1142)
C-1: polymethylacrylate organic microparticles (trade name "F-351S" manufactured by Aike (aica) industries, Ltd.)
D-1: micro-pulverization of tri (2-hydrazinocarbonylethyl) isocyanurate
(HCIC, produced by Generan Farken (Finechem) Ltd., Japan, finely pulverized with a jet mill to an average particle diameter of 1.5 μm)
E-1: brilliant good fixation (Irgacure) OXE04 (manufactured by BASF corporation)
E-2: 2, 4-Diethylthioxanthone (product name "Kayacure (Kayacure) DETX-S" manufactured by Nippon Chemicals Co., Ltd.)
F-1: 1, 2-bis (trimethylsilyloxy) -1, 1, 2, 2-tetraphenylethane
(Synthesis example 4 obtained by fine grinding with a jet mill to an average of 1.9 μm)
O-1: urethane acrylate obtained in Synthesis example 2
O-2: urethane acrylate obtained in Synthesis example 3
O-3: nitroso-series piperidine derivative (Polystop 7300P, manufactured by Bondong Ltd.)
O-4: tris (3-carboxyethyl) isocyanurate (CIC acid, product of Siguo Kagaku Co., Ltd.)
O-5: 3-glycidoxypropyltrimethoxysilane (Sila-Ace S-510 manufactured by JNC Co., Ltd.)
From the results of table 1, it was confirmed that: the sealant for display of the present invention has both flexibility and low moisture permeability, and is excellent in adhesive strength.
[ industrial applicability ]
The sealant for display of the present invention has excellent adhesive strength with an adherend, and combines flexibility with low moisture permeability, and is therefore useful as a sealant for display, flexible display, or display in a curved shape, which particularly requires adhesiveness with an organic film.

Claims (12)

1. A sealant for a display, comprising a urethane (meth) acrylate as a component A, which is obtained by reacting a polyol having an alicyclic structure as a component a, an organic polyisocyanate as a component b, and a hydroxyl group-containing (meth) acrylate as a component c.
2. The sealant for display use according to claim 1, wherein the component a is a polyol having a tricyclodecane dimethanol structure.
3. The sealant for display use according to claim 1 or 2, wherein the component a is obtained by further reacting a polyol other than the component a as the component a-1.
4. The sealant for display according to claim 1 or 2, further comprising a component B curable compound.
5. The sealant for display use according to claim 4, wherein the component B is a partial epoxy (meth) acrylate.
6. The sealant for display use according to claim 1 or 2, further comprising a component C organic filler.
7. The sealant for display according to claim 6, wherein the component C is one or more organic fillers selected from the group consisting of urethane fine particles, acrylic fine particles, styrene olefin fine particles, and silicone fine particles.
8. The sealant for display use according to claim 1 or 2, further comprising a component D heat hardener.
9. The sealant for display use according to claim 1 or 2, further comprising a component E photo radical polymerization initiator.
10. The sealant for display use according to claim 1 or 2, further comprising a component F thermal radical polymerization initiator.
11. The sealant for display according to claim 1 or 2, which is a liquid crystal sealant for liquid crystal dropping method.
12. A liquid crystal display sealed with the sealant as claimed in claim 11.
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