CN111690355B - Sealant for display and liquid crystal display - Google Patents

Sealant for display and liquid crystal display Download PDF

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Publication number
CN111690355B
CN111690355B CN202010164002.XA CN202010164002A CN111690355B CN 111690355 B CN111690355 B CN 111690355B CN 202010164002 A CN202010164002 A CN 202010164002A CN 111690355 B CN111690355 B CN 111690355B
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sealant
component
display
acrylate
meth
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CN111690355A (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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    • 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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (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 device, which contains a compound having a specific structure in a molecule. The sealant for display has excellent adhesion strength to an adherend, and has both flexibility and low moisture permeability, and is therefore useful as a sealant for display, flexible display, or curved display, in which adhesion to an organic film is particularly required. A sealant for displays, which contains (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. The sealant for display is useful as a sealant for flexible display or curved display, in particular, because of being compatible with flexibility and low moisture permeability. Further, the sealant having flexibility as in the present invention is excellent in adhesion strength to an adherend, and therefore is useful in applications requiring high adhesion strength.
Background
Examples of the sealant for display include a sealant (seal) for liquid crystal display, a sealant for organic Electroluminescence (EL) display, and an adhesive for touch panel. These materials are required to have excellent hardenability and, at the same time, to have a characteristic that little outgas is emitted and no damage is caused to the display element.
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 for such a display instead of a rigid substrate such as glass in the related art (patent document 1).
Under such circumstances, a display sealant is required to have such a property as to follow the deflection of a substrate or the like, that is, to be soft even after curing.
In addition, a sealant excellent in flexibility is also advantageous in terms of adhesive strength. For example, peeling or fixture damage caused by impact can be reduced. From the above point of view, the demand for imparting flexibility to the sealant has also become high.
On the other hand, in order to improve the flexibility of the cured product, it is an effective means to reduce the crosslink density of the cured product. However, the decrease in the crosslinking density generally deteriorates the moisture permeability. This is believed to be due to the intrusion of moisture from the loose parts of the network. Therefore, in order to secure low moisture permeability, it is necessary to realize the opposite property of improving flexibility without decreasing 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 achieved.
[ Prior Art literature ]
[ patent literature ]
Patent document 1 japanese patent laid-open publication 2012-238005
[ patent document 2] Japanese patent laid-open publication 2016-24240
Disclosure of Invention
[ problem 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 a display has both flexibility and low moisture permeability, and is excellent in adhesive strength, and therefore is useful as a sealant for a display.
[ means of solving the 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 terms of flexibility and low moisture permeability, and have completed the present invention.
In addition, 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 sealant for a display, which contains (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 a display according to the item [1], wherein the component (a) is a polyol having a tricyclodecane dimethanol structure.
[3]
The sealant for a 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 a display according to any one of [1] to [3], further comprising a component (B) curable compound.
[5]
The sealant for a display according to the item [4], wherein the component (B) is a partial epoxy (meth) acrylate.
[6]
The sealant for a display according to any one of the [1] to [5], further comprising a component (C) organic filler.
[7]
The sealant for a display according to item [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 a display according to any one of the [1] to [7], further comprising a component (D) a thermal hardening agent.
[9]
The sealant for a display according to any one of the above [1] to [8], further comprising a component (E) a photo radical polymerization initiator.
[10]
The sealant for a display according to any one of the [1] to [9], further comprising a component (F) a thermal radical polymerization initiator.
[11]
The sealant for a 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 sealing agent for liquid crystal dropping method according to the item [11 ].
[ Effect of the invention ]
The sealant for a display of the present invention has both flexibility and low moisture permeability, and also has excellent adhesive strength, and is therefore useful as a sealant for a 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)") which contains (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 peculiar to the urethane structure, and further, a polyol having an alicyclic structure is used, whereby the cured product has a soft and low moisture permeability characteristic, and has high adhesive strength not only on the glass substrate but also on the alignment film.
Regarding the flexibility, the modulus of elasticity of the cured product can be used as an index. As the irradiation of ultraviolet rays, 3000mJ/cm 2 The elastic modulus of a cured product of 100 μm thickness which is cured at 130℃for 40 minutes after the curing (measurement wavelength: 365 nm) is preferably 200MPa to 3000MPa, more preferably 400MPa to 2000MPa, particularly preferably 600MPa to 1500MPa. It can be said that the display adhesive in the above range follows the stress applied to the display, and is therefore preferable.
As the low moisture permeability, it is preferable that the moisture permeability in the cured product having a thickness of 300 μm is 60g/m 2 * And 24 hours 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 component (b) is preferably reacted in an amount of 1.1 to 2.0 equivalents, particularly preferably 1.3 to 2.0 equivalents, relative to 1 equivalent of the hydroxyl group of component (a). The reaction temperature is preferably room temperature (25 ℃) to 100 ℃.
The hydroxyl group in component (c) is preferably reacted in an amount of 0.95 to 1.1 equivalent per 1 equivalent of the isocyanate group in the reaction product of component (a) and component (b). The reaction temperature is preferably room temperature (25 ℃) to 100 ℃.
The polyol having an alicyclic structure as the component (a) is not particularly limited as long as it has an alicyclic structure within the polyol structure.
Specific examples of the component (a) include cyclohexanedimethanol, norbornanedimethanol, norbornene dimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, adamantanedimethanol, hydrogenated bisphenol a, hydrogenated bisphenol F, hydrogenated terpene diphenol, and Ethylene Oxide (EO), propylene Oxide (PO), caprolactone modified products thereof. In terms of improving the adhesiveness, it is preferable to use an alicyclic structure having 20 or less carbon atoms, and it is preferable to use tricyclodecanedimethanol from the viewpoint of balance between low moisture permeability and flexibility. Examples of the commercial product of tricyclodecanedimethanol include TCD alcohol DM available from Celanese (Celanese).
Further, from the viewpoint of improving the water resistance, a diol having a crosslinked structure such as norbornadiene dimethanol, norbornene dimethanol, tricyclodecanedimethanol, adamantane dimethanol or the like is preferable.
In the present invention, the use of a polyol other than the component (a) as the component (a-1) is also a preferred embodiment. Specific examples of the component (a-1) include: hydrogenated polybutadiene polyol, 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
Ethoxy diol, bisphenol A poly->
Figure BDA0002406006930000052
And polyester diols (a-1-2) which are reaction products of diols (a-1-1) such as propoxylated diols and diols (a-1-1) with dibasic acids or anhydrides thereof (for example, succinic acid, adipic acid, azelaic acid, dimer acids, isophthalic acid, terephthalic acid, phthalic acid or anhydrides thereof). Preferably, 3-methyl-1, 5-pentanediol and polyester diol thereof are exemplified.
When the component (a) and the component (a-1) are used together, the component (a) is usually 3 to 95% by weight, preferably 5 to 50% by weight, and more preferably 8 to 20% by weight, based on the total amount of the component (a) and the component (a-1).
Specific examples of the organic polyisocyanate (b) 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. Toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate are preferably mentioned.
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, epsilon-caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenylpropyl (meth) acrylate, and the like. Preferably, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate are exemplified.
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, based on the total amount of the sealant for display.
[ (B) curable Compound ]
The sealant for display of the present invention contains a curable compound (hereinafter also referred to simply as "component (B)") 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 component (B-1) (meth) acrylate (hereinafter also simply referred to as component (B-1)), and examples thereof include (meth) acrylate and epoxy (meth) acrylate.
[ (B-1) (meth) acrylate ]
Specific examples of the (meth) acrylic acid ester include: n-acryloyloxyethyl hexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane-1, 4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl polyethoxy (meth) acrylate, 2-hydroxy-3-phenylpropyloxy (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, and tribromophenyl oxyethyl (meth) acrylate, dicyclopentanyl alkenyl (meth) acrylate, dicyclopentanyloxyethyl (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, monomers such as polyethylene glycol di (meth) acrylate, tri (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the diacrylate of esters of neopentyl glycol and hydroxylmethacetic acid or the diacrylate of epsilon-caprolactone adduct of neopentyl glycol and hydroxylmethacetic acid. Preferred examples thereof include N-acryloyloxyethyl hexahydrophthalimide, phenoxyethyl (meth) acrylate, and dicyclopentadienyloxyethyl (meth) acrylate.
Epoxy (meth) acrylates are obtained by reacting epoxy resins with (meth) acrylic acid in a known manner. The epoxy resin to be used as a raw material is not particularly limited, but epoxy resins having a 2-functional or more group are preferable, and examples thereof include: resorcinol diglycidyl ether, bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having a triphenol methane skeleton, diglycidyl ethers of difunctional phenols such as catechol and resorcinol, diglycidyl ethers of difunctional alcohols, halides and hydrides thereof, and the like. Among these, bisphenol a type epoxy resins or resorcinol diglycidyl ethers 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 step suitability.
In addition, a partial epoxy (meth) acrylate in which a part of the epoxy group is acrylated can be preferably used. The ratio of the acrylic acid in this case is preferably about 30% to 70%.
The component (B-1) may be used alone or in combination of two or more. In the case where the component (B-1) is used in the resin composition of the present invention, the total amount of the resin composition is usually 10 to 80% by mass, preferably 20 to 70% by mass.
[ (B-2) epoxy resin ]
In the embodiment of the present invention, it is preferable that the component (B) further contains a component (B-2) epoxy resin (hereinafter also simply referred to as component (B-2)).
The epoxy resin is not particularly limited, but epoxy resins having 2 or more functions are preferable, and examples thereof include: resorcinol diglycidyl ether, bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having a triphenol methane skeleton, diglycidyl ethers of difunctional phenols such as catechol and resorcinol, diglycidyl ethers of difunctional alcohols, halides and hydrides thereof, and the like. Among these, bisphenol a type epoxy resins or resorcinol diglycidyl ethers are preferable from the viewpoint of liquid crystal contamination.
The component (B-2) may be used alone or in combination of two or more. In the case where component (B-2) is used in the resin composition of the present invention, the amount of the component (B-2) 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 (hereinafter also referred to simply as "component (C)") as component (C). Examples of the organic filler include: urethane microparticles, acrylic microparticles, styrene olefin microparticles, and silicone microparticles. Further, as silicone microparticles, KMP-594, KMP-597, KMP-598 (manufactured by Xinyue chemical industry), and Torilil (torayfil) are preferable RTM E-5500, 9701, EP-2001 (manufactured by Donglikannin (Toray Dow Corning)) and preferably JB-800T, HB-800BK (manufactured by Ind. Co., ltd.) as urethane fine particles and Lavalong (RABALON) as styrene fine particles RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (Mitsubishi chemical manufacturing), and Sitopton (septon) is preferable as styrene olefin fine particles RTM SEPS2004、SEPS2063。
These organic fillers may be used alone or in combination of two or more. Furthermore, two or more kinds of core-shell structures may be used. Among these, acrylic microparticles and silicone microparticles are preferable.
In using the acrylic microparticlesIn the case of (2), the acrylic rubber is preferably a core-shell acrylic rubber comprising two types of acrylic rubber, and particularly preferably a core layer of n-butyl acrylate and a shell layer of methyl methacrylate. As zefiaac (zefiac) RTM F-351 is sold by Aike (AICA) industry Co., ltd.
Examples of the silicone fine particles include organopolysiloxane crosslinked powder and linear dimethylpolysiloxane crosslinked powder. The composite silicone rubber may be formed by coating a silicone resin (for example, a polyorganosilsesquioxane resin) on the surface of the silicone rubber. Of these fine particles, silicone rubber of linear dimethylpolysiloxane crosslinked powder or composite silicone rubber fine particles in which linear dimethylpolysiloxane crosslinked powder is coated with silicone resin are particularly preferable. These may be used alone or in combination of two or more. Furthermore, it is preferable that: the rubber powder is preferably spherical in shape with little thickening of the viscosity after addition. In the case where component (C) is used in the sealant for a display of the present invention, the total amount of the sealant for a display is usually 5 to 50% by mass, preferably 5 to 40% by mass.
[ (D) thermal hardener ]
The sealant for display of the present invention can be added with a thermosetting agent as component (D) (hereinafter also simply referred to as "component (D)") to improve 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 include: terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2, 6-naphthoic acid dihydrazide, 2, 6-pyridine dihydrazide, 1,2, 4-benzene tricarbazide, 1,4,5, 8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide, and the like as aromatic hydrazides. Further, in the case of aliphatic hydrazides, examples thereof include: hydantoin, dihydrazide propionate, dihydrazide oxalate, dihydrazide malonate, dihydrazide succinate, dihydrazide glutarate, dihydrazide adipate, dihydrazide pimelate, dihydrazide sebacate, 1, 4-cyclohexanedihydrazide, dihydrazide tartrate, dihydrazide malate, dihydrazide iminodiacetate, N '-hexamethylenebis-semicarbazide (N, N' -hexamethylenebishydrazide), dihydrazide citrate, dihydrazide nitroacetate, dihydrazide cyclohexane tricarboxylic acid, 1, 3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, dihydrazide having a valine hydantoin (skeleton in which a carbon atom of the hydantoin ring is substituted with isopropyl), tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-ylcarbonylethyl) isocyanurate, tris (1-ylcarbonylethyl) isocyanurate, tris (3-ethylcarbonyl) isocyanurate, bis (2-ethylcarbazide) isocyanurate, etc. From the viewpoint of balance between hardening reactivity and potential, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, and particularly, tris (2-hydrazinocarbonylethyl) isocyanurate are 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. In the case where component (D) is used in the sealant for a display of the present invention, the total amount of the sealant for a display is usually 0.1 to 10% by mass, preferably 0.1 to 5% by mass.
The sealant for a display of the present invention may further improve the reactivity by adding a hardening catalyst. Examples of the curing catalyst include amines and imidazoles, and imidazoles are particularly preferred. Examples of imidazoles include: 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, 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-cyano-2-ethyl-3, 5-dimethylimidazole, etc.
[ (E) photo radical polymerization initiator ]
The sealant for display of the present invention may contain a photo radical polymerization initiator (hereinafter also simply referred to as "component (E)") as component (E). The photo radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals or acids by irradiation with ultraviolet rays or visible light to initiate chain polymerization, and examples thereof include: benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethyl anthraquinone, 2-hydroxy-2-methyl propiophenone, 2-methyl- [4- (methylthio) phenyl ]]-2-morpholino-1-propane, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, camphorquinone, 9-fluorenone, diphenyl disulfide, and the like. Specifically, there may be mentioned: yanjia solid (IRGACURE) RTM 651. 184, 2959, 127, 907, 369, 379EG, 819, 784, 754, 500, OXE01, OXE02, OXE03, OXE04, dacroure (DAROCURE) RTM 1173. Lu Xirui (LUCIRIN) RTM TPO (manufactured by BASF), siebold (SEIKUOL) RTM Z, BZ, BEE, BIP, BBI (all manufactured by Seiko chemical Co., ltd.) and the like. Among these, preferred is the yanjia solid (IRGACURE) as an oxime ester initiator RTM OXE01、OXE02、OXE03、OXE04。
Further, from the viewpoint of liquid crystal contamination, a (meth) acrylic acid group is 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.
In the case where component (E) is used in the sealant for a display of the present invention, the total amount of the sealant for a display is usually 0.001 to 3% by mass, preferably 0.002 to 2% by mass.
[ (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 curing property.
The thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating to initiate chain polymerization, 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, kayamike (kayamak) as an organic peroxide RTM A. M, R, L, LH, SP-30C, pakadax (PERKADOX) CH-50L, BC-FF, kadax (Cadox) B-40ES, pakadax (PERKADOX) 14, tao Ligao Rhododendron (TRIGONOX) RTM 22-70E, 23-C70, 121-50E, 121-LS50E, 21-LS50E, 42LS, kayaEsther path Ai Sitai (KayaEsther) RTM P-70, TMPO-70, CND-C70, OO-50E, AN, kayabu its way (kayabutyl) RTM B. Packdax (PERKADOX) 16, kaya card Lu Bao (Kayacarbon) RTM BIC-75, AIC-75 (manufactured by Kayaku AKZO CO., LTD.), pa Mei Ke (permek) RTM N, H, S, F, D, G Pahexesa (PERCEXA) RTM H. HC, TMH, C, V, 22, MC, parthence (perture) RTM AH. AL, HB, parbloc way (perbutyl) RTM H. C, ND, L, parabane Mi Lu (PERCUMYL) RTM H. D, paloeri road (PEROYL) RTM IB. IPP, paaokuta (PEROCTA) RTM ND (manufactured by Nitro oil Co., ltd.) and the like are commercially available.
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, based on the total amount of the sealant for display of the present invention.
In the sealant for display of the present invention, 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 may be further blended as necessary.
[ inorganic filler ]
The inorganic filler may be exemplified by: 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, asbestos, and the like are preferably exemplified by fused silica, crystalline silica, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, aluminum hydroxide, calcium silicate, aluminum silicate, preferably silica, alumina, talc. These inorganic fillers may be used in a mixture of two or more.
If the average particle diameter of the inorganic filler is too large, it becomes a bad factor that a gap or the like cannot be smoothly formed when upper and lower glass substrates are bonded in manufacturing a liquid crystal display unit with a narrow gap (gap), so that 2000nm or less is preferable, 1000nm or less is preferable, and 300nm or less is more preferable. The lower limit is preferably about 10nm, more preferably about 100 nm. Particle size can be measured by a laser diffraction/scattering particle size distribution analyzer (dry) (manufactured by Seishin corporation; LMS-30).
In the case where the inorganic filler is used in the sealant for a display of the present invention, the total amount of the sealant for a display is usually 5 to 50% by mass, and preferably 5 to 40% by mass. When the content of the inorganic filler is less than 5% by mass, the adhesion strength to the glass substrate is lowered, and the moisture resistance reliability is also poor, so that the decrease in the adhesion strength after moisture absorption may be also large. In addition, when the content of the inorganic filler is more than 50 mass%, the filler content is too large, and therefore it may be difficult to break, and a gap of the liquid crystal cell may not be formed.
[ silane coupling agent ]
The silane coupling agent may be exemplified by: 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, N-phenyl-gamma-aminopropyl trimethoxysilane, N- (2-aminoethyl) 3-aminopropyl methyl dimethoxy silane, N- (2-aminoethyl) -3-aminopropyl methyl trimethoxysilane, 3-aminopropyl triethoxy silane, 3-mercaptopropyl trimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) -3-aminopropyl trimethoxysilane hydrochloride, 3-methacryloxypropyl trimethoxysilane, 3-chloropropylmethyl dimethoxy silane, 3-chloropropyl trimethoxysilane, and the like. These silane coupling agents are commercially available as KBM series, KBE series, etc. from the company of the Xinyue chemical industries, inc., and are therefore readily available on the market. In the case of using a silane coupling agent in the sealant for a display of the present invention, the amount of the silane coupling agent is preferably 0.05 to 3% by mass based on the total amount of the sealant for a display.
[ free radical polymerization inhibitor ]
The radical polymerization inhibitor is not particularly limited as long as it is a compound that reacts with radicals generated by a photo radical polymerization initiator, a thermal radical polymerization initiator, or the like to prevent polymerization, and quinone, piperidine, hindered phenol, nitroso, or the like can be used. Specifically, there may be mentioned: naphthoquinone, 2-hydroxynaphthoquinone, 2-menaquinone, 2-methoxynaphthoquinone, 2, 6-tetramethylpiperidin-1-oxy, 2, 6-tetramethyl-4-hydroxypiperidin-1-oxy, 2, 6-tetramethyl-4-methoxypiperidin-1-oxy 2, 6-tetramethyl-4-phenoxypiperidin-1-oxy, hydroquinone, 2-methyl hydroquinone, 2-methoxy hydroquinone, p-benzoquinone, butylated hydroxyanisole, 2, 6-di-tert-butyl-4-ethylphenol 2, 6-di-tert-butylcresol, stearyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 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- [ β - (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' -hydroxyphenyl propionate ] methane ] 1,3, 5-tris (3 ',5' -di-tert-butyl-4 ' -hydroxybenzyl) -s-triazine (sec-triazine) -2,4,6- (1H, 3H, 5H) trione, p-methoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, aluminum salts of N-nitrosophenyl hydroxylamine, trade name Adekatab LA-81, trade name Adekatab LA-82 (Ai Dike (manufactured by Adeka Co., ltd.), and the like, but are 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-t-butyl-P-cresol, and wave Li Site P (POLYSTOP) 7300P (manufactured by Boehringer Co., ltd.) are more preferable, and wave Li Site P (POLYSTOP) 7300P (manufactured by Boehringer Co., ltd.) is most preferable.
The content of the radical polymerization inhibitor in the total amount of the sealant for a display of the present invention 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.
As an example of a method for obtaining the sealant for a display of the present invention, the following method is given. First, the components (A) and (B) are heated as needed to dissolve the component (E). After cooling to room temperature, the components (C), (D) and (F), inorganic filler, silane coupling agent, defoaming agent, leveling agent, solvent and the like are added as needed, and the mixture is 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, thereby producing the sealant for a display of the present invention.
The sealant for a display of the present invention is useful as an adhesive for a liquid crystal display unit, particularly as a liquid crystal sealant. Examples of the liquid crystal display unit in the case where the sealant for a display of the present invention is used as a liquid crystal sealant are shown below.
The liquid crystal display unit manufactured using the adhesive for a liquid crystal display unit of the present invention is formed by disposing a pair of substrates having predetermined electrodes formed thereon at predetermined intervals in a manner that the substrates are opposed to each other, sealing the periphery with the liquid crystal sealing agent of the present invention, and sealing liquid crystal in the gap. The type of the liquid crystal to be sealed is not particularly limited. Here, the substrate includes a substrate having a combination of light transmittance of 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 by using a dispenser, a screen printing apparatus, or the like, and then, if necessary, pre-cured at 80 to 120 ℃. Thereafter, liquid crystal is dropped inside the dam of the liquid crystal sealing agent, and another glass substrate is overlapped in vacuum to form a gap. After the formation of the gap, the liquid crystal display unit of the present invention can be obtained by curing at 90 to 130℃for 30 minutes to 2 hours. When the liquid crystal sealing material is used as a combination of both light and heat, the liquid crystal sealing material is irradiated with ultraviolet rays by an ultraviolet irradiation machine to be cured. The ultraviolet irradiation amount is preferably 500mJ/cm 2 ～6000mJ/cm 2 More preferably 1000mJ/cm 2 ～4000mJ/cm 2 (measurement wavelength: 365 nm). Thereafter, the cured product is cured at 90 to 130℃for 30 minutes to 2 hours, as required, to obtain the liquid crystal display unit of the present invention. The liquid crystal display unit of the present invention thus obtained is free from display failure due to liquid crystal contamination, and is excellent in adhesion and moisture resistance reliability. Examples of the spacer include glass fibers, silica beads, and polymer beads. The diameter thereof varies depending on the purpose, and is usually 2 μm to 8. Mu.m, preferably 4 μm to 7. Mu.m. The amount of the compound is usually 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, and more preferably about 0.9 to 1.5 parts by mass, based on 100 parts by mass of the liquid crystal sealing agent of the present invention。
The sealant for a display of the present invention is very suitable for adhesive applications in the fields where hardenability, adhesion to various adherends, and reliability against moist heat are required. Such as a liquid crystal sealant, an organic EL sealant, and an adhesive for touch panels.
Examples (example)
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. Unless otherwise specified, parts and% are based on mass.
Synthesis example 1
A flask equipped with a thermometer, a cooling tube, and a stirring device was charged with 987.9g of a polyester polyol (P-2050, 56.8mgKOH/g, manufactured by Karl Co., ltd., hydroxyl value), 98.2g of TCD alcohol DM, 196.3 g, manufactured by Sanyclodecane dimethanol (Celanese Co., ltd., molecular weight: 196.3), wei Dalian (VESTANAT) IPDI, manufactured by Evonik Co., ltd., molecular weight: 222.3) 444.6g, and isophorone diisocyanate (manufactured by Evonik Co., ltd.) and reacted at 80 ℃.
The isocyanate content at this time was determined by adding an excessive amount of amine and back-titrating with hydrochloric acid, and it was confirmed that the value was within a range of 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, and the mixture was stirred at 80℃to react until the isocyanate group was absorbed by the infrared absorption spectrum (2280 cm -1 ) Until disappearing, 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 stirring device was charged with 1979.2g of Polycaprolactone diol (Placcel) 220, hydroxyl value 56.7mgKOH/g, manufactured by Daicel Co., ltd.) and 400.1g of isophorone diisocyanate (Wei Dalian (VESTANAT) IPDI, manufactured by Evonik Co., ltd., molecular weight 222.3) to carry out a reaction at 80 ℃.
The isocyanate content at this time was determined by adding an excessive amount of amine and back-titrating with hydrochloric acid, and it was confirmed that the value was within a range of plus or minus 2% of the residual amount of isocyanate determined from the calculated value.
Next, 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, and the mixture was stirred at 80℃to react until the absorption spectrum of isocyanate groups (2280 cm -1 ) Until disappearing, 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 stirring device was charged with 835.0g of hydrogenated polybutadiene polyol (GI-1000, hydroxyl value 67.2mgKOH/g, manufactured by Selaginella Co., ltd.), 98.2g of tricyclodecane dimethanol (TCD alcohol DM, molecular weight 196.3, manufactured by Celanese Co., ltd.), 444.6g of isophorone diisocyanate (Wei Dalian (VESTANAT) IPDI, manufactured by Evonik Co., ltd., molecular weight 222.3, manufactured by Evonik Co., ltd.) and reacted at 80 ℃.
The isocyanate content at this time was determined by adding an excessive amount of amine and back-titrating with hydrochloric acid, and it was confirmed that the value was within a range of 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, and the mixture was stirred at 80℃to react until the isocyanate group was absorbed by the infrared absorption spectrum (2280 cm -1 ) Until disappeared, a urethane acrylate with 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 Co., ltd.) was dissolved in 350 parts of dimethyl formaldehyde. To this was added 32 parts (0.4 mol) of pyridine as a base catalyst and 150 parts (0.58 mol) of Bastetter (BSTFA) (manufactured by Xinyue chemical industry) as a silylating agent, and the mixture was heated to 70℃and stirred for 2 hours. The obtained reaction solution was cooled, 200 parts of water was added while stirring, and the resultant was precipitated while inactivating the unreacted silylating agent. The precipitated product was filtered off and washed thoroughly with water. Then, the obtained product was dissolved in acetone, and water was added thereto to recrystallize the product, followed by purification. 105.6 parts of the target 1, 2-bis (trimethylsiloxy) -1, 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 in the proportions shown in table 1 below, and the component (F) was heated and dissolved at 90 ℃, then cooled to room temperature, and the components (C), (D), (E) and (O) were added, stirred, dispersed by a three-roll mill, and filtered through a metal mesh (635 mesh) to prepare a sealant for display.
[ evaluation ]
[ adhesive Strength ]
The alignment film liquid (RN 2880, manufactured by Nissan chemical industry Co., ltd.) was spin-coated on a glass substrate, and baked in a heating plate at 80℃for 3 minutes and baked in an oven at 230℃for 30 minutes. Further, the substrate with alignment film was irradiated with 500mJ/cm by a UV irradiation machine 2 (measurement wavelength: 254 nm), and further calcined in an oven at 230℃for 30 minutes.
To 100g of the display sealant manufactured in examples and comparative examples, 1g of 5 μm glass fiber was added as a spacer, and the mixture was stirred. The sealant for display was applied to the glass substrate coated with the alignment film in such a manner that the corner portions of 1cm×1cm were reproduced, the opposite alignment film-coated substrates were bonded, and 3000mJ/cm was irradiated with an Ultraviolet (UV) irradiation machine 2 (measurement wavelength: 365 nm), and then put into an oven, and thermally cured at 130℃for 40 minutes. The peel adhesion strength of the oriented film-coated glass substrate was measured in the form of a pressed corner portion using a bond tester (bond tester) (manufactured by West business Co., ltd.: SS-30 WD). The intensities are shown in Table 1.
The results of the adhesion strength measured on the glass substrate without the alignment film are also shown in table 1.
[ moisture permeability ]
The sealants for displays produced in examples and comparative examples were sandwiched between polyethylene terephthalate (PET) films to prepare films having a thickness of 300. Mu.m, and the films were irradiated with a UV irradiation machine at 3000mJ/cm 2 (measurement wavelength: 365 nm), then put into an oven, thermally cured at 130℃for 40 minutes, and after curing, the PET film was peeled off to prepare a sample. The moisture permeability of the sample at 60℃of 90% was measured by a moisture permeability measuring machine (manufactured by Lyssy Co., ltd.: L80-5000). The results are shown in Table 1.
[ modulus of elasticity ]
The sealants for displays produced in examples and comparative examples were sandwiched between polyethylene terephthalate (PET) films to give films having a thickness of 100. Mu.m, and the films were irradiated with 3000mJ/cm using a UV irradiation machine 2 (measurement wavelength: 365 nm), then put into an oven, thermally cured at 130℃for 40 minutes, and after curing, the PET film was peeled off to prepare a sample. Universal tester (A) using Tensilon (Tensilon)&Manufactured by D corporation, RTG-1210) was subjected to a tensile test at room temperature (22 ℃) at a test speed of 5 mm/min, and the measurement was performed. The results are shown in Table 1.
TABLE 1
Figure BDA0002406006930000171
A-1: the urethane acrylate obtained in Synthesis example 1
B-1-1: part of acrylic acid compound of bisphenol A type epoxy resin
( Synthesis example Using a general Synthesis method: 50% equivalent of acrylic acid of Japanese patent application laid-open No. 2016-24243 was reacted )
B-1-2: o-phenylphenoxyethyl acrylate (Miwen (Miwon) company: mi Lamo (Miramer) M-1142)
C-1: polymethacrylate organic microparticle (trade name "F-351S" manufactured by Aike (aica) Industrial Co., ltd.)
D-1: micro-pulverization of tris (2-hydrazinocarbonylethyl) isocyanurate
( Manufactured by finechhem, inc., japan: HCIC, and pulverized to an average particle size of 1.5 μm by a jet mill )
E-1: yanjia solid (Irgacure) OXE04 (manufactured by Basf Co., ltd.)
E-2:2, 4-Diethylthioxanthone (manufactured by Japanese chemical Co., ltd. "Kayacure (Kayacure) DETX-S)"
F-1:1, 2-bis (trimethylsiloxy) -1, 2-tetraphenylethane
Synthesis example 4 micronization with a jet mill to an average size of 1.9. Mu.m
O-1: the urethane acrylate obtained in Synthesis example 2
O-2: the urethane acrylate obtained in Synthesis example 3
O-3: nitroso piperidine derivative (Bodhisattva manufactured by Bodhisattva Co., ltd.: bo Li Site P (polystop) 7300P)
O-4: tris (3-carboxyethyl) isocyanurate (CIC acid, manufactured by four national chemical industries Co., ltd.)
O-5: 3-glycidoxypropyl trimethoxysilane (JNC Co., ltd.: sila-Ace) S-510
From the results in table 1, it was confirmed that: the sealant for a display of the present invention has both flexibility and low moisture permeability, and also has excellent adhesive strength.
[ Industrial applicability ]
The sealant for a display of the present invention has excellent adhesion strength to an adherend, and combines flexibility with low moisture permeability, and is therefore useful as a sealant for a display, a flexible display, or a curved display, in which adhesion to an organic film is particularly required.

Claims (9)

1. A sealant for a display, comprising a component A urethane (meth) acrylate obtained by reacting a polyol having an alicyclic structure as a component a, a component a-1 other than the polyol as the component a, a component B organic polyisocyanate, and a component c hydroxyl group-containing (meth) acrylate,
the component a-1 comprises a component a-1-2 polyester diol, and
the ratio of the acrylic acid of a part of the epoxy groups in the partial epoxy (meth) acrylate is 30 to 70%.
2. The sealant for display according to claim 1, wherein the component a is a polyol having a tricyclodecanedimethanol structure.
3. The sealant for display according to claim 1 or 2, further comprising a component C organic filler.
4. The sealant for display according to claim 3, 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.
5. The sealant for display according to claim 1 or 2, further comprising a component D thermosetting agent.
6. The sealant for display according to claim 1 or 2, further comprising a component E photo radical polymerization initiator.
7. The sealant for display according to claim 1 or 2, further comprising a component F thermal radical polymerization initiator.
8. The sealant for a display according to claim 1 or 2, which is a liquid crystal sealant for a liquid crystal dropping method.
9. A liquid crystal display sealed with the sealant for display according to claim 8.
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JP6478313B2 (en) 2014-07-17 2019-03-06 日本化薬株式会社 Liquid crystal sealant and liquid crystal display cell using the same
JP2016024243A (en) 2014-07-17 2016-02-08 日本化薬株式会社 Liquid crystal sealant and liquid crystal cell using the same
JP2016109997A (en) 2014-12-10 2016-06-20 日本化薬株式会社 Liquid crystal sealant and liquid crystal cells using the same
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