WO2014153835A1 - 封框胶及其制备方法 - Google Patents

封框胶及其制备方法 Download PDF

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Publication number
WO2014153835A1
WO2014153835A1 PCT/CN2013/076599 CN2013076599W WO2014153835A1 WO 2014153835 A1 WO2014153835 A1 WO 2014153835A1 CN 2013076599 W CN2013076599 W CN 2013076599W WO 2014153835 A1 WO2014153835 A1 WO 2014153835A1
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Prior art keywords
sealant
viscosity
mixture
porous glass
frame
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PCT/CN2013/076599
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English (en)
French (fr)
Inventor
肖昂
汪姗姗
夏登国
Original Assignee
京东方科技集团股份有限公司
北京京东方光电科技有限公司
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Application filed by 京东方科技集团股份有限公司, 北京京东方光电科技有限公司 filed Critical 京东方科技集团股份有限公司
Priority to EP13856066.9A priority Critical patent/EP2980178B1/en
Priority to KR1020147016862A priority patent/KR101883029B1/ko
Priority to JP2016503514A priority patent/JP2016519181A/ja
Priority to US14/361,859 priority patent/US9540534B2/en
Publication of WO2014153835A1 publication Critical patent/WO2014153835A1/zh

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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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

Definitions

  • Embodiments of the invention relate to a frame sealant and a method of making same. Background technique
  • Frame sealant is a key material in the process of liquid crystal panel-to-box.
  • the position of the sealant coating is different.
  • 1 indicates the edge of the entire glass substrate;
  • 2 indicates the outer peripheral sealant of the substrate (ie, the sealant applied to the periphery of the entire substrate), 2 indicates the outer seal of the sub-substrate (ie, sticky) a peripheral sealant for a plurality of small substrates on a substrate for preventing bending deformation of the substrate and the sub-substrate edge due to the weight of the glass itself;
  • 3 indicating a main sealant (ie, a seal applied to the periphery of the liquid crystal)
  • the frame glue plays a role of sealing the liquid crystal panel, reducing the pollution of the liquid crystal inside the box, and bonding the color filter substrate and the array substrate.
  • the color film substrate (or array substrate) coated with the sealant and the array substrate (or the color filter substrate) with the liquid crystal are first placed in a vacuum in a box, and then irradiated by ultraviolet light and Heating to achieve photocuring and heat curing of the sealant to complete the process of the box.
  • a vacuum box it is necessary to ensure that only the liquid crystal is left in the sealed space formed by the main sealant without residual gas. Because the substrate frame sealant and the sub-substrate sealant have no openings, the substrate peripheral sealant 2 and the sub-substrate sealant 2, and between the sub-substrate sealant 2 and the main sealant 3 are It is a vacuum.
  • the sealant Before the ultraviolet ray and heating are irradiated, the sealant is not cured, and the liquid crystal on the inner side of the main sealant applies a certain pressure to the sealant, so that the pressure acting on the inside of the main sealant is greater than the pressure acting on the outside of the main sealant.
  • the pressure difference between the two sides causes the liquid crystal to impact the uncured sealant (the liquid crystal is puncture), which causes the sealant to deform or even break, which causes the adhesive strength of the sealant to decrease, and the liquid crystal is contaminated by the sealant. problem.
  • the opening is designed on the outer frame sealant of the substrate and the outer frame sealant of the sub-substrate, so that the outside air enters from the opening to the inside of the main sealant. All areas, so as to ensure that the pressure on the inner and outer sides of the main sealant is balanced, thereby avoiding or alleviating the above-mentioned liquid crystal puncture problem.
  • the embodiment of the present invention can provide a frame sealant containing a porous glass microsphere treated with a safety gas and a method for preparing the same, which can suppress the occurrence of liquid crystal puncture in the liquid crystal panel and reduce the contamination of the liquid crystal in the cell by the outer layer.
  • Embodiments of the present invention provide a frame sealant comprising, by weight percent, from 1% to 5% of a safety gas treated porous glass microsphere.
  • the sealant of the embodiment of the present invention may contain 60% to 70% of low viscosity epoxy acrylic photocurable resin by weight percentage; 1% to 5% epoxy resin, 0.5% to 1% photoinitiator; % ⁇ 10% heat curing agent; 1% ⁇ 2% coupling agent; 5% ⁇ 10% organic powder; 5% ⁇ 10% inorganic powder; 1% ⁇ 5% porous glass microsphere treated with safety gas.
  • the frame sealant may contain 60% to 70% low viscosity epoxy acrylic photocurable resin; 3% to 5% epoxy resin, 0.5% to 1% photoinitiator; 8% to 10% thermal curing agent; % ⁇ 2% coupling agent; 5% ⁇ 8% organic powder; 7% ⁇ 10% inorganic powder; 2% ⁇ 5% porous glass microsphere treated with safety gas.
  • the gas may account for 3% to 5% of the volume of the porous glass microspheres.
  • the safety gas can be nitrogen, inert gas, carbon dioxide or air.
  • the low-viscosity epoxy acrylate photocurable resin may have the following structural formula I and may have a viscosity of 100 ⁇ 50 Pa-s at room temperature.
  • each R may be the same or different and each represents 11, a thiol or an ethyl group.
  • the sealant of the embodiment of the present invention has a viscosity at room temperature of 250 ⁇ 50 Pa-s.
  • Embodiments of the present invention also relate to a method of preparing the above sealant, comprising the following steps: (1) mixing the components constituting the sealant to obtain a mixture;
  • the above preparation method may further comprise the following steps:
  • Embodiments of the present invention also relate to the use of the above-mentioned frame sealant in the manufacture of a liquid crystal panel.
  • embodiments of the present invention relate to a liquid crystal panel in which the above-mentioned frame sealant is used as a substrate peripheral sealant and/or a sub-substrate peripheral sealant.
  • Fig. 1 is a schematic view showing a coating position of a sealant on a substrate. detailed description
  • the present disclosure provides a frame sealant comprising from 1% to 5% by weight of a porous glass microsphere treated with a safety gas.
  • the sealant may contain 60% to 70% low viscosity epoxy acrylic photocurable resin by weight percentage; 1% to 5% epoxy resin, 0.5% to 1% photoinitiator; 5% to 10% Heat curing agent; 1% ⁇ 2% coupling agent; 5% ⁇ 10% organic powder; 5% ⁇ 10% inorganic powder; 1% ⁇ 5% porous glass microsphere treated with safety gas.
  • the sealant may contain 60% to 70% low viscosity epoxy acrylic photocurable resin; 3% to 5% epoxy resin, 0.5% to 1% photoinitiator; 8% to 10% thermal curing agent; % ⁇ 2% coupling agent; 5% ⁇ 8% organic powder; 7% ⁇ 10% inorganic powder; 2% ⁇ 5% porous glass microsphere treated with safety gas.
  • the sealant of the present disclosure has a viscosity at room temperature in the range of 250 ⁇ 50 Pa's.
  • the safe gas treated porous glass microspheres in the sealant of the present disclosure may be any suitable porous glass microspheres known in the art that can be used for the sealant, wherein the safe gas means A gas that does not react with the components of the sealant and the liquid crystal under the action of light and heat.
  • the safety gas may be nitrogen, inert gas, carbon dioxide, air, or the like.
  • the safety gas It can be nitrogen.
  • the volume percentage of the safety gas in the porous glass sphere may be 3% to 5%. When the volume percentage of the safety gas is less than 3%, the effect of balancing the pressure on the inner and outer sides of the main sealant is not obvious.
  • the volume percentage of the safety gas is higher than 5%, it may cause the coatability of the sealant to be deteriorated, so it is preferable that the volume percentage of the safety gas is not more than 5%.
  • the diameter of the porous glass sphere may be, for example, 1 to 2 Smith.
  • the low viscosity epoxy acrylic photocurable resin in the sealant of the present disclosure may have the following structural formula I (see, for example, CN102766047A), and has a viscosity of 100 ⁇ 50 Pa-s at room temperature,
  • each R may be the same or different and may respectively represent H, an alkyl group having 1 to 4 carbon atoms, such as an anthracenyl group or an ethyl group.
  • the epoxy resin of the frame sealant of the present disclosure may be an epoxy resin generally used in the art, such as epoxy resin E-41, E-51, or an epoxy resin having the following structural formula II.
  • n an integer from 1 to 4.
  • thermosetting agent such as ⁇ , ⁇ -diethoxyacetophenone, ⁇ -hydroxyalkylphenone or a-aminoalkylphenone
  • a thermosetting agent may use a diamino group.
  • a polybasic aliphatic amine such as diphenyl decane
  • the coupling agent may be a silane coupling agent ⁇ 550, ⁇ 560 or 570 570 (manufactured by U.S. Carbon Corporation)
  • the resin may be an elastic microsphere or the like
  • the inorganic powder may be a silica microsphere or the like.
  • the present disclosure also relates to a method of preparing the above-mentioned frame sealant, which method may include the following steps:
  • the mixture may be kneaded 2 to 3 times at 30 to 50 ° C, and the kneading time may be appropriately determined depending on the weight of the final sealant.
  • the mixing time can be from about 30 minutes to 60 minutes.
  • the kneaded mixture may be defoamed one or more times.
  • the defoaming chamber may have a pressure of less than 500 Pa and the defoaming time may be about 20 min to 40 min.
  • the above preparation method may further include the following steps:
  • the viscosity of the mixture after defoaming was adjusted so that the viscosity at room temperature was 250 ⁇ 50 Pa-s.
  • the viscosity of the defoamed mixture can be finely adjusted by using a low viscosity epoxy acrylic photocurable resin of different viscosity and an organic or inorganic powder within the range of the content of each component of the open sealant to make the viscosity of the sealant. The specified value is reached.
  • the present disclosure also relates to the use of the above-mentioned frame sealant in the manufacture of a liquid crystal panel.
  • the above-mentioned frame sealant is used as the substrate peripheral sealant and/or the sub-substrate peripheral sealant.
  • the sealant of the present disclosure contains porous glass microspheres treated with a safety gas. Therefore, when the frame sealant of the present disclosure is used as the substrate peripheral sealant and/or the sub-substrate peripheral sealant, during the vacuum pressing of the cartridge and during the ultraviolet irradiation and heating immediately after the vacuum is applied to the cartridge
  • the sealant glue can release the safety gas to resist the pressure generated by the liquid crystal inside the main sealant, thereby suppressing the occurrence of the liquid crystal puncture phenomenon in the liquid crystal panel, thereby reducing the external pollution of the liquid crystal in the box.
  • the frame sealant of Example 1 was obtained.
  • the sealant has a viscosity in the range of 250 ⁇ 50 Pa.s at 23 °C - 25 °C.
  • the frame sealant of Example 2 was obtained.
  • the sealant has a viscosity at 23-25 ° C in the range of 250 ⁇ 50 Pa.s.
  • the frame sealant of Example 3 was obtained.
  • the sealant has a viscosity in the range of 250 ⁇ 50 Pa.s at 23 to 25 °C.
  • a 3.97-inch liquid crystal panel was prepared by using the frame sealant of Examples 1 to 3 of the present disclosure, and the puncture was observed under a microscope.
  • the frame sealant of the embodiments 1 to 3 of the present disclosure is used as the substrate peripheral sealant and the sub-substrate sealant, and the conventional sealant UR-2920 (manufactured by Mitsui Chemicals, Japan) is used as the main sealant.
  • the coating was applied at a coating speed of 120 mm/sec and dried to a width of 0.5 ⁇ 0.2 mm.
  • the liquid crystal amount per liquid crystal panel was 2.55 mg.
  • the liquid crystal panels 1 to 3 of the embodiment of the present invention were separately prepared.
  • the main frame sealant, the substrate peripheral sealant and the sub-substrate sealant were all made of the conventional sealant UR-2920, and other conditions were the same as above, thereby manufacturing a comparative liquid crystal panel.
  • the inside of the main sealant i.e., the liquid crystal side edge as a whole, showed no liquid crystal puncture.
  • the conventional liquid crystal panel using the conventional sealant UR-2920 as the peripheral sealant of the substrate and the peripheral sealant of the sub-substrate has a dendritic irregular pattern on the liquid crystal side edge of the main sealant, and liquid crystal puncture occurs.
  • This liquid crystal puncture phenomenon causes liquid crystal contamination in the case and affects the peripheral display of the display.
  • the use of the frame sealant of the embodiment of the present invention can effectively prevent liquid crystal puncture, thereby improving the liquid crystal display effect.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明的实施例提供一种封框胶及其制备方法。所述封框胶以重量百分比计含有60%~70%低粘度环氧丙烯酸光固化树脂；1%~5%环氧树脂， 0.5%~1%光引发剂；5%~10%热固化剂；1%~2%偶联剂；5%~10%有机粉末； 5%~10%无机粉末；1%~5%经安全气体处理过的多孔玻璃微球。所述制备方法包括（1）混合构成封框胶的上述各成分，得到混合物；（2）对所述混合物进行混炼；（3）对混炼后的混合物进行脱泡。

Description

封框胶及其制备方法 技术领域
本发明的实施例涉及一种封框胶及其制备方法。 背景技术
封框胶是液晶面板对盒工艺中的关键材料。 封框胶涂覆的位置不同作用 也不同。如图 1所示， 1表示整张玻璃基板的边缘； 2表示基板外围封框胶（即， 涂布在整个基板外围的封框胶）， 2，表示亚基板外围封框胶（即， 粘合在一张 基板上的多个小基板的外围封框胶）， 用于防止基板和亚基板边缘由于玻璃自 身重量导致弯曲形变； 3表示主封框胶（即， 涂布在液晶外围的封框胶）， 发 挥密封液晶面板， 降低外界对盒内液晶产生的污染， 并且粘接彩膜基板和阵 列基板的作用。
在对盒工艺中， 通常首先将涂覆有封框胶的彩膜基板（或阵列基板）和 滴有液晶的阵列基板（或彩膜基板）在真空中进行对盒， 然后通过紫外光照 射和加热来实现封框胶的光固化和热固化， 从而完成对盒工艺。 另外， 在真 空对盒时， 需要确保由主封框胶形成的密封空间内只有液晶而不残留气体。 因为基板封框胶和亚基板封框胶无开口， 所以基板外围封框胶 2和亚基板外 围封框胶 2，之间以及亚基板外围封框胶 2，和主封框胶 3之间均为真空。 在照 射紫外线和加热之前， 封框胶尚未固化， 主封框胶内侧的液晶对封框胶施加 一定的压力， 导致作用于主封框胶内侧的压力大于作用于主封框胶外侧的压 力。 两侧的压差使得液晶沖击尚未固化的封框胶（筒称液晶穿刺）， 造成封框 胶发生形变， 甚至断裂， 导致封框胶的粘接力下降， 液晶受到封框胶的污染 等问题。
针对上述主封框胶内外侧存在压差的问题， 目前通过在基板外围封框胶 和亚基板外围封框胶上设计开口， 使外界气体从该开口处进入到除主封框胶 内侧以外的所有区域， 从而确保主封框胶内外两侧的压力趋于平衡， 进而避 免或减轻上述液晶穿刺的问题。
但是为了防止在后续减薄工艺中刻蚀液进入亚基板内腐蚀基板， 需要重 新密封基板外围封框胶和亚基板外围封框胶的开口， 由此使工序复杂并增加 成本。
发明内容
本发明的实施例通过提供一种含有经安全气体处理过的多孔玻璃微球的 封框胶及其制备方法， 能够抑制液晶面板中液晶穿刺现象的发生， 并减少外 界对盒内液晶的污染。 本发明的实施例提供一种封框胶， 其以重量百分比计， 含有 1%~5%经安全气体处理过的多孔玻璃微球。
例如， 本发明实施例的封框胶以重量百分比计， 可含有 60%~70%低粘度 环氧丙烯酸光固化树脂； 1%~5%环氧树脂， 0.5%~1%光引发剂； 5%~10%热 固化剂； 1%~2%偶联剂； 5%~10%有机粉末； 5%~10%无机粉末； 1%~5%经 安全气体处理过的多孔玻璃微球。
例如， 上述封框胶可含有 60%~70%低粘度环氧丙烯酸光固化树脂； 3 %~5%环氧树脂， 0.5%~1%光引发剂； 8%~10%热固化剂； 1%~2%偶联剂； 5%~8%有机粉末； 7%~10%无机粉末； 2%~5%经安全气体处理过的多孔玻璃 微球。
所述经安全气体处理过的多孔玻璃微球中， 气体可占多孔玻璃微球体积 的 3%~5%。
所述安全气体可为氮气、 惰性气体、 二氧化碳或空气。
所述低粘度环氧丙烯酸光固化树脂可具有如下结构式 I , 并且在室温下 的粘度可为 100±50Pa-s,
Figure imgf000004_0001
结构式 I
其中， 各 R可以相同或不同， 分别表示11、 曱基或乙基。
本发明实施例的封框胶在室温下的粘度为 250±50Pa-s。
本发明的实施例还涉及上述封框胶的制备方法， 包括以下步骤: ( 1 )混合构成封框胶的各成分， 得到混合物；
( 2 )对所述混合物进行混炼；
( 3 )对混炼后的混合物进行脱泡。
上述制备方法还可包括下述步骤：
( 4 ) 对脱泡后的混合物进行粘度调节， 使其在室温下的粘度为
Figure imgf000005_0001
本发明的实施例还涉及上述封框胶在液晶面板制作中的应用。
另外， 本发明的实施例涉及一种液晶面板， 在该液晶面板中， 使用上述 封框胶作为基板外围封框胶和 /或亚基板外围封框胶。
附图说明
图 1是表示封框胶在基板上的涂布位置的示意图。 具体实施方式
下面将对本发明实施例中的技术方案进行清楚、 完整地描述， 显然， 所 描述的实施例仅仅是本发明一部分实施例， 而不是全部的实施例。 基于本发 明中的实施例， 本领域普通技术人员在没有做出创造性劳动前提下所获得的 所有其他实施例， 都属于本发明保护的范围。
本公开提供一种封框胶， 其以重量百分比计， 含有 1%~5%经安全气体处 理过的多孔玻璃微球。 例如， 该封框胶以重量百分比计， 可含有 60%~70%低 粘度环氧丙烯酸光固化树脂； 1%~5%环氧树脂， 0.5%~1%光引发剂； 5%~10%热固化剂； 1%~2%偶联剂； 5%~10%有机粉末； 5%~10%无机粉 末； 1%~5%经安全气体处理过的多孔玻璃微球。 例如， 该封框胶可含有 60%~70%低粘度环氧丙烯酸光固化树脂； 3%~5%环氧树脂， 0.5%~1%光引 发剂； 8%~10%热固化剂； 1%~2%偶联剂； 5%~8%有机粉末； 7%~10%无机 粉末； 2%~5%经安全气体处理过的多孔玻璃微球。 另外， 本公开的封框胶在 室温下的粘度在 250±50Pa's范围内。
本公开封框胶中的经安全气体处理过的多孔玻璃微球可以是本领域已知 的可以用于封框胶的任何适宜的多孔玻璃微球，其中，所述的安全气体是指， 在光和热的作用下不与封框胶各成分以及液晶发生反应的气体。 例如， 所述 安全气体可以为氮气、 惰性气体、 二氧化碳、 空气等。 例如， 所述安全气体 可以为氮气。 并且， 所述安全气体在多孔玻璃 球中所占的体积百分比可为 3%~5%。 当安全气体的体积百分比低于 3%时，其平衡主封框胶内外两侧的压 力的效果不明显。 当安全气体的体积百分比高于 5%时， 其可能会导致封框胶 的涂布性变差， 因此优选安全气体的体积百分比不高于 5%。 另外， 所述多孔 玻璃 球的直径例如可以为 1 -2 史米。
本公开封框胶中的低粘度环氧丙烯酸光固化树脂可以具有如下结构式 I (例如参见 CN102766047A ), 并且在室温下的粘度为 100±50Pa-s,
Figure imgf000006_0001
结构式 I
其中， 各 R可以相同或不同， 可以分别表示 H、 碳原子数为 1-4的烷基， 例如曱基或乙基。
本公开封框胶的环氧树脂可以使用本领域通常使用的环氧树脂， 例如环 氧树脂 E-41、 E-51 , 还可以是具有下述结构式 II的环氧树脂，
Figure imgf000006_0002
结构式 π
其中， n表示 1-4的整数。
另外， 用于本公开封框胶的光引发剂、 热固化剂、 偶联剂、 有机粉末以 及无机粉末， 可以分别使用本领域通常使用的物质。 例如， 作为光引发剂， 可以使用 α , α -二乙氧基苯乙酮、 α -羟烷基苯酮或 a -氨烷基苯酮等烷基苯酮 类； 热固化剂可以使用二氨基二苯基曱烷等多元脂肪胺类； 偶联剂可以是硅 烷偶联剂 ΚΗ550、 ΚΗ560或 ΚΗ 570 (由美国联合碳公司制造）等； 有机粉末 树脂可以是弹性微球等； 无机粉末可以是二氧化硅微球等。
本公开还涉及上述封框胶的制备方法， 该方法可包括以下步骤：
( 1 ) 混合构成封框胶的各成分， 得到混合物；
( 2 )对所述混合物进行混炼；
( 3 )对混炼后的混合物进行脱泡。
例如，可以在 30~50°C下对所述混合物进行 2~3次混炼，并可根据最终封 框胶的重量适当确定混炼时间。 例如， 混炼时间可以是约 30min~60min。 另 夕卜， 可对混炼后的混合物进行一次或多次脱泡， 例如， 脱泡箱内压强可小于 500Pa , 脱泡时间可以是约 20min~40min。
例如， 上述制备方法还可包括下述步骤：
( 4 )对脱泡后的混合物进行粘度调节，使其室温下的粘度为 250±50Pa-s。 通常情况下， 在公开封框胶各成分的含量范围内， 可以利用不同粘度的 低粘度环氧丙烯酸光固化树脂以及有机或无机粉末对脱泡后的混合物粘度进 行微调， 使封框胶的粘度达到规定数值。
本公开还涉及上述封框胶在液晶面板制作中的应用。 在本公开的液晶面 板中， 使用上述封框胶作为基板外围封框胶和 /或亚基板外围封框胶。
本公开的封框胶含有经安全气体处理过的多孔玻璃微球。 因此， 当使用 本公开的封框胶作为基板外围封框胶和 /或亚基板外围封框胶时， 在真空对盒 的挤压过程中以及真空对盒后立即进行的紫外线照射和加热过程中， 所述封 框胶可放出所述安全气体， 对抗主封框胶内侧因液晶产生的压力， 从而抑制 液晶面板中液晶穿刺现象的发生， 进而减少外界对盒内液晶的污染。
下面通过具体实施例对本发明的封框胶进行说明。 所述实施例仅仅是示 例性的， 不应解释为对本公开内容进行限制。 需要说明的是， 以下所述百分 比， 在没有特别说明的情况下， 都表示重量百分比。
实施例 1
在室温下，混合 60%下述结构式 III所示的低粘度环氧丙烯酸光固化树脂、 5%环氧树脂 E-41 (由江苏扬农制造）、 0.5%作为光引发剂的 α,α-二乙氧基苯 乙酮、 10%作为热固化剂的二氨基二苯基曱烷、 1.5%硅烷偶联剂 ΚΗ550 (由 美国联合碳公司制造）、 8%作为有机粉末的树脂弹性微球 (由美国 MSE公司 制造）、 10%作为无机粉末的二氧化硅微球（由美国 3Μ公司制造）、 5%经气 体处理过的玻璃微球（美国 3M公司制造， G200 ), 使得最终封框胶的总重量 为 200g。将上述混合物在室温下搅拌 30~60分钟（在该实施例中约为 40分钟 ) 后， 在 30~50°C (在该实施例中约为 40°C ) 下混炼两次， 每次 30min~60min (该实施例中约为 30分钟）。 将混炼后的混合物在室温下进行 20分钟脱泡， 并使脱泡箱内压强小于 500帕斯卡。 由此得到实施例 1的封框胶。 该封框胶 在 23 °C -25 °C下的粘度在 250 ± 50Pa.s范围内。
Figure imgf000008_0001
结构式 in
实施例 2
在室温下，混合 66%上述结构式 III所示的低粘度环氧丙烯酸光固化树脂、 3%环氧树脂 E-41 (由江苏扬农制造）、 1%作为光引发剂的 α,α-二乙氧基苯乙 酮、 8%作为热固化剂的二氨基二苯基曱烷、 2%硅烷偶联剂 ΚΗ550、 8%作为 有机粉末的树脂弹性微球、 7%作为无机粉末的二氧化硅微球、 5%经气体处理 过的玻璃微球（美国 3Μ公司制造， G200 ),使得最终封框胶的总重量为 200g。 将上述混合物在室温下搅拌 30~60分钟（在该实施例中约为 30分钟）后， 在 30-50 °C (在该实施例中约为 50 °C )下混炼两次， 每次 30min~60min (该实施 例中约为 40分钟）。 将混炼后的混合物在室温下进行 30分钟脱泡， 并使脱泡 箱内压强小于 500帕斯卡。 由此得到实施例 2的封框胶。该封框胶在 23-25 °C 下的粘度在 250士 50Pa.s范围内。
实施例 3
在室温下，混合 70%上述结构式 III所示的低粘度环氧丙烯酸光固化树脂、 5%环氧树脂 E-41、 1%作为光引发剂的 α,α-二乙^ 苯乙酮、 8%作为热固化 剂的二氨基二苯基曱烷、 1%硅烷偶联剂 KH550、 5%作为有机粉末的树脂弹 性微球、 8%作为无机粉末的二氧化硅微球、 2%经气体处理过的玻璃微球（美 国 3M公司制造， G200 ), 使得最终封框胶的总重量为 200g。 将上述混合物 在室温下搅拌 30~60分钟 (在该实施例中约为 40分钟）后， 在 30~50°C (在 该实施例中约为 40 °C )下混炼两次， 每次 30min~60min (该实施例中约为 30 分钟）。 将混炼后的混合物在室温下进行 20分钟脱泡， 并使脱泡箱内压强小 于 500帕斯卡。 由此得到实施例 3的封框胶。该封框胶在 23~25°C下的粘度在 250 ± 50Pa.s范围内。
抗穿刺测试
利用本公开实施例 1~3的封框胶制备 3.97英寸液晶面板，显微镜下观察 穿刺情况。 例如， 分别利用本公开实施例 1~3的封框胶作为基板外围封框胶 和亚基板外围封框胶， 而利用传统封框胶 UR-2920 (日本三井化学制造）作 为主封框胶， 以 120 mm/sec的涂布速度进行涂布， 并使其干燥后宽度控制在 0.5 ± 0.2mm。 另夕卜， 每个液晶面板的液晶量为 2.55mg。 由此分别制备得到本 发明实施例的液晶面板 1~3。
在对比试验中， 主封框胶、 基板外围封框胶和亚基板外围封框胶均采用 传统封框胶 UR-2920, 其他条件与上述相同， 由此来制造对比液晶面板。 抗穿刺测试结果
在使用本发明实施例的封框胶的液晶面板 1~3中， 主封框胶的内侧， 即 液晶侧边缘整体， 均未见液晶穿刺现象。 而使用传统封框胶 UR-2920作为基 板外围封框胶和亚基板外围封框胶的对比液晶面板， 在主封框胶的液晶侧边 缘有树枝状不规则图形， 发生液晶穿刺现象。 该液晶穿刺现象会造成盒内液 晶污染， 影响显示屏的周边显示。 由此可见使用本发明实施例的封框胶能够 有效地防止液晶穿刺， 从而提高液晶显示效果。 发明的构思和范围。 这样， 倘若本发明的这些修改和变型属于本发明权利要 求及其等同技术的范围之内， 则本发明也意图包含这些改动和变型在内。

Claims

权利要求书
1、 一种封框胶， 其以重量百分比计含有 1%~5%经安全气体处理过的多 孔玻璃微球。
2、根据权利要求 1所述的封框胶， 其中， 所述封框胶，以重量百分比计, 含有 60%~70%低粘度环氧丙烯酸光固化树脂； 1 %~5%环氧树脂， 0.5%~ 1 % 光引发剂； 5%~10%热固化剂； 1%~2%偶联剂； 5%~10%有机粉末； 5%~10% 无机粉末； 1%~5%经安全气体处理过的多孔玻璃敫球。
3、 根据权利要求 1或 2所述的封框胶， 其中， 所述封框胶， 以重量百分 比计， 含有 60%~70%低粘度环氧丙烯酸光固化树脂； 3%~5%环氧树脂， 0.5%~1%光引发剂； 8%~10%热固化剂； 1%~2%偶联剂； 5%~8%有机粉末； 7%~10%无机粉末； 2%~5%经安全气体处理过的多孔玻璃 球。
4、 根据权利要求 1至 3中任一项所述的封框胶， 其中， 所述经安全气体 处理过的多孔玻璃敫球中， 气体占多孔玻璃微球体积的 3%~5%。
5、 根据权利要求 1至 4中任一项所述的封框胶， 其中， 所述安全气体为 氮气、 惰性气体、 二氧化碳或空气。
6、 根据权利要求 1至 5中任一项所述的封框胶， 其中， 低粘度环氧丙婦 酸光固化树脂具有如下结构式 I , 并且在室温下的粘度为 100±50Pa-s,
Figure imgf000010_0001
结构式 I
其中， 各 R相同或不同， 分别表示11、 曱基或乙基。
7、 根据权利要求 1至 6中任一项所述的封框胶， 其中， 所述封框胶在室 温下的粘度为 250±50Pa-s。
8、制备权利要求 1至 7中任一项所述的封框胶的方法，其包括以下步骤: ( 1 )混合构成封框胶的各成分， 得到混合物； ( 2 )对所述混合物进行混炼；
(3)对混炼后的混合物进行脱泡。
9、 根据权利要求 8所述的方法， 还包括下述步骤：
( 4 ) 对脱泡后的混合物进行粘度调节， 使其在室温下的粘度为
Figure imgf000011_0001
10、 一种液晶面板， 其使用权利要求 1至 7中任一项所述的封框胶作为 基板外围封框胶和 /或亚基板外围封框胶。
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EP2980178B1 (en) 2019-08-14
KR20140126293A (ko) 2014-10-30
KR101883029B1 (ko) 2018-07-27
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CN103205216A (zh) 2013-07-17
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