TW201420735A - Liquid crystal sealing agent and liquid crystal display cell using same - Google Patents

Liquid crystal sealing agent and liquid crystal display cell using same Download PDF

Info

Publication number
TW201420735A
TW201420735A TW102124978A TW102124978A TW201420735A TW 201420735 A TW201420735 A TW 201420735A TW 102124978 A TW102124978 A TW 102124978A TW 102124978 A TW102124978 A TW 102124978A TW 201420735 A TW201420735 A TW 201420735A
Authority
TW
Taiwan
Prior art keywords
liquid crystal
sealing agent
crystal sealing
component
dropping method
Prior art date
Application number
TW102124978A
Other languages
Chinese (zh)
Inventor
Eiichi Nishihara
Masahiro Kida
Saki Yoshida
Hideyuki Ota
Tsunetoshi Sakano
Original Assignee
Nippon Kayaku Kk
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Kk filed Critical Nippon Kayaku Kk
Publication of TW201420735A publication Critical patent/TW201420735A/en

Links

Classifications

    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Sealing Material Composition (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal (AREA)

Abstract

Provided is a liquid crystal sealing agent for use in a liquid crystal dropping process which, due to the particularly excellent adherence to an organic film such as an oriented film, does not readily peel from upper/lower substrates even in various environments, and further, has excellent fundamental characteristics as a liquid crystal sealing agent, such as low liquid crystal staining properties and heat resistance. This liquid crystal sealing agent is characterized in that, when the strength of adhesive bonding to an ITO substrate at 25 DEG C after curing for 1 hour under an atmosphere of 120 DEG C, following irradiation of 3000 mJ/cm2 ultraviolet rays, is taken as A [MPa], the strength of adhesive bonding at 120 DEG C after said curing is taken as B [MPa], and the strength of adhesive bonding to an ITO substrate at 25 C after curing with only 3000 mJ/cm<SP>2</SP> ultraviolet rays is taken as C [MPa], A, B and C satisfied the relational expressions shown by expressions (1) and (2) below. B ≥ 0.5 A (1) C ≥ 0.3 A (2).

Description

液晶密封劑及使用該液晶密封劑之液晶顯示單元 Liquid crystal sealing agent and liquid crystal display unit using the liquid crystal sealing agent

本發明關於一種使用於液晶滴下工法的液晶密封劑。更詳細而言，是關於一種液晶密封劑及使用該液晶密封劑之液晶顯示單元，該液晶密封劑對定向膜(配向膜)等有機膜之黏著性非常優異。 The present invention relates to a liquid crystal sealing agent used in a liquid crystal dropping method. More specifically, it relates to a liquid crystal sealing agent and a liquid crystal display unit using the liquid crystal sealing agent, which is excellent in adhesion to an organic film such as an alignment film (alignment film).

隨著近年液晶顯示單元的大型化，作為液晶顯示單元的製造方法，提案了一種所謂的液晶滴下工法，其量產性更高(專利文獻1、2)。此液晶滴下工法，具體而言，為在一片基板所形成之由液晶密封劑構成的堰的內側將液晶滴下後，貼合另一片基板，其後將液晶密封劑硬化之製造方法。 In recent years, as a method of manufacturing a liquid crystal display unit, a so-called liquid crystal dropping method has been proposed, which has a higher mass productivity (Patent Documents 1 and 2). Specifically, the liquid crystal dropping method is a manufacturing method in which a liquid crystal sealing agent is cured by dropping a liquid crystal on the inside of a crucible formed of a liquid crystal sealing agent formed on one substrate, bonding the other substrate, and then sealing the liquid crystal sealing agent.

但是，在液晶滴下工法中，由於在液晶密封劑硬化前，液晶與液晶密封劑接觸，所以會由於液晶所致之壓力，而於液晶密封劑發生滲入現象，在最糟糕的情況下，亦有由液晶密封劑構成的堰會潰決的情況發生，而成為問題。為了解決此問題，必須要提高液晶滴下量的精度，但儘管如此，由於在液晶密封劑的硬化步驟亦即加熱時液晶會膨脹，所以不易完全抑制上述滲入現象。 However, in the liquid crystal dropping method, since the liquid crystal is in contact with the liquid crystal sealing agent before the liquid crystal sealing agent is hardened, the liquid crystal sealing agent may be infiltrated due to the pressure caused by the liquid crystal, and in the worst case, there are A flaw caused by a liquid crystal sealant may occur and become a problem. In order to solve this problem, it is necessary to increase the precision of the liquid crystal dropping amount. However, since the liquid crystal expands during the curing step of the liquid crystal sealing agent, that is, the liquid crystal, it is difficult to completely suppress the above-described infiltration phenomenon.

為了抑制上述滲入現象，提案了一種技術，其是用 以提高液晶密封劑的反應速度而實現從低溫時起的快速硬化、或使用膠化劑等而在加熱時增加液晶密封劑的黏度(專利文獻3、4)。此等在液晶密封劑抵抗由於液晶的膨脹所致之壓力這方面為合理的技術，但該壓力無處宣洩的結果，會對上下方向，亦即會對將2片基板剝離的方向增加施力，導致產生基板剝離這樣的新的不佳狀況發生。 In order to suppress the above infiltration phenomenon, a technique is proposed which is used The rapid curing of the liquid crystal sealing agent is achieved by increasing the reaction rate of the liquid crystal sealing agent, or the viscosity of the liquid crystal sealing agent is increased during heating by using a gelling agent or the like (Patent Documents 3 and 4). These are reasonable techniques for the liquid crystal sealing agent to resist the pressure due to the expansion of the liquid crystal, but the pressure is nowhere to vent, and the upper and lower directions, that is, the direction in which the two substrates are peeled off, are increased. A new poor condition that causes substrate peeling occurs.

並且，上述之經提昇反應速度、或添加膠化劑之液晶密封劑，歷時變化大，大多會在易使用性上產生問題。 Further, the liquid crystal sealing agent which has been subjected to the above-mentioned increase in the reaction rate or the addition of the gelling agent has a large change over time, and many of them have problems in ease of use.

又，現在，液晶顯示元件使用於非常多各式各樣的 東西中。因此，必須即使對於大的氣溫變化或高濕度也不產生不佳狀態。此特性為即使對於液晶密封劑亦均等地應用之特性，不因為氣溫的變化而產生基板間之剝離，又，需要在高濕度下具有耐受性、或防止水的滲入之特性。作為解決此問題之方法，提案了一種使用具有特定性質之部分(甲基)丙烯酸化環氧樹脂等之技術(專利文獻5)。然而，還尚未能說是完美。 Also, nowadays, liquid crystal display elements are used in a very wide variety of Something in it. Therefore, it is necessary to produce a poor state even for a large temperature change or high humidity. This property is a characteristic that is applied evenly to the liquid crystal sealing agent, and does not cause peeling between the substrates due to a change in temperature, and is required to have resistance to high humidity or to prevent penetration of water. As a method for solving this problem, a technique of using a partially (meth)acrylated epoxy resin having a specific property or the like has been proposed (Patent Document 5). However, it has not yet been said to be perfect.

又，近年的窄邊框設計之液晶面板，由於液晶密封 劑的線寬變細，黏著強度的問題變得比以前更為嚴重。亦即，由於液晶密封劑的線寬變細，以習知的黏著強度，則會引起在常溫及耐濕可靠性試驗後上下基板剝離的問題。 Moreover, the liquid crystal panel of the narrow frame design in recent years, due to the liquid crystal sealing The line width of the agent becomes thinner, and the problem of adhesion strength becomes more serious than before. That is, since the line width of the liquid crystal sealing agent is reduced, the conventional adhesive strength causes a problem that the upper and lower substrates are peeled off after the normal temperature and moisture resistance reliability test.

並且，最近，液晶密封劑配置在定向膜等之上的液 晶顯示單元之設計變多。然而，在習知的液晶密封劑，對於如此的有機膜之黏著性並不能說充分，而成為要解決的問題。 Moreover, recently, a liquid crystal sealing agent is disposed on a liquid above an orientation film or the like. The design of the crystal display unit has increased. However, in the conventional liquid crystal sealing agent, the adhesion to such an organic film cannot be said to be sufficient, and it becomes a problem to be solved.

如以上所述，液晶滴下工法用之液晶密封劑有各種 的問題，儘管正全力的進行研究，解決該等問題者仍尚未被開發出來。 As described above, there are various liquid crystal sealing agents for liquid crystal dropping methods. The problem, although being fully researched, has not yet been developed to solve these problems.

又，液晶滴下工法用之液晶密封劑，必須在低液晶污染性、高黏著強度等一般特性方面都優異。 Further, the liquid crystal sealing agent for a liquid crystal dropping method must be excellent in general characteristics such as low liquid crystal contamination and high adhesion strength.

[先前技術文獻] [Previous Technical Literature]

(專利文獻) (Patent Literature)

專利文獻1：日本特開昭63-179323號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. SHO63-179323

專利文獻2：日本特開平10-239694號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. Hei 10-239694

專利文獻3：國際公開第2011/061910號 Patent Document 3: International Publication No. 2011/061910

專利文獻4：日本特開2006-23419號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2006-23419

專利文獻5：日本特開2011-221168號公報 Patent Document 5: Japanese Laid-Open Patent Publication No. 2011-221168

本發明提出一種液晶密封劑及使用該液晶密封劑之液晶顯示單元，該液晶密封劑是使用於液晶滴下工法之液晶密封劑，且由於與特別是定向膜等有機膜之黏著性優異，故在各式各樣環境下都不易引起上下基板的剝離，並且低液晶污染性、耐熱性等作為液晶密封劑的基本特性亦優異。 The present invention provides a liquid crystal sealing agent and a liquid crystal display unit using the liquid crystal sealing agent, which is a liquid crystal sealing agent used in a liquid crystal dropping method, and has excellent adhesion to an organic film such as an oriented film, and thus In the various environments, peeling of the upper and lower substrates is less likely to occur, and low liquid crystal contamination, heat resistance, and the like are also excellent as basic characteristics of the liquid crystal sealing agent.

本案發明人，在努力探討的結果，發現一種液晶密封劑對於有機膜的黏著強度非常優異而達成本發明，該液晶密封劑在照射3000mJ/cm2的紫外線後並在120℃環境下予以硬化1小時後，將該硬化後的液晶密封劑於25℃時對於ITO (氧化銦錫)基板的黏著強度設為A〔MPa〕，並將上述硬化後的液晶密封劑於120℃時的黏著強度設為B〔MPa〕，且將僅以3000mJ/cm2的紫外線予以硬化後的液晶密封劑於25℃時對於ITO(氧化銦錫)基板的黏著強度設為C〔MPa〕時，上述A、B、及C具有一定關係。 As a result of intensive investigation, the inventors of the present invention have found that a liquid crystal sealing agent which is excellent in adhesion strength to an organic film which is hardened after being irradiated with ultraviolet rays of 3000 mJ/cm 2 and at 120 ° C. After the aging, the adhesion of the cured liquid crystal sealing agent to the ITO (indium tin oxide) substrate at 25 ° C is set to A [MPa], and the adhesion strength of the cured liquid crystal sealing agent at 120 ° C is set. When the liquid crystal sealing agent which is cured by ultraviolet rays of only 3000 mJ/cm 2 is B [MPa] and the adhesion strength to the ITO (indium tin oxide) substrate is C [MPa] at 25 ° C, the above A, B And C have a certain relationship.

另外，本說明書中，所謂「(甲基)丙烯酸」是指「丙烯酸及/或是甲基丙烯酸」。 In the present specification, the term "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid".

亦即本發明是關於以下的1)~13)。 That is, the present invention relates to the following 1) to 13).

1) 1)

一種液晶滴下工法用液晶密封劑，其在照射3000mJ/cm2的紫外線後並在120℃環境下予以硬化1小時後，將該硬化後的液晶密封劑於25℃時對於ITO(氧化銦錫)基板的黏著強度設為A〔MPa〕，並將上述硬化後的液晶密封劑於120℃時的黏著強度設為B〔MPa〕，且將僅以3000mJ/cm2的紫外線予以硬化後的液晶密封劑於25℃時對於ITO(氧化銦錫)基板的黏著強度設為C〔MPa〕時，上述A、B、及C滿足下列式(1)及(2)所表示之關係式：B≧0.5×A (1) A liquid crystal sealing agent for liquid crystal dropping method, which is cured by irradiating ultraviolet rays of 3000 mJ/cm 2 and cured at 120 ° C for 1 hour, and then curing the cured liquid crystal sealing agent at 25 ° C for ITO (indium tin oxide) The adhesive strength of the substrate is A [MPa], and the adhesion strength of the liquid crystal sealing agent after curing at 120 ° C is B [MPa], and the liquid crystal sealing is performed only by ultraviolet rays of 3000 mJ/cm 2 . When the adhesive strength of the ITO (indium tin oxide) substrate is C [MPa] at 25 ° C, the above A, B, and C satisfy the relationship represented by the following formulas (1) and (2): B ≧ 0.5 ×A (1)

C≧0.3×A (2)。 C≧0.3×A (2).

2) 2)

如上述1)所述之液晶滴下工法用液晶密封劑，其中，將僅以3000mJ/cm2的紫外線予以硬化後的液晶密封劑於120℃時對於ITO(氧化銦錫)基板的黏著強度設為D〔MPa〕時，上述A及D滿足下列式(3)所表示之關係式： D≧0.3×A (3)。 The liquid crystal sealing agent for liquid crystal dropping method according to the above-mentioned 1), wherein the liquid crystal sealing agent which has been cured by ultraviolet rays of only 3,000 mJ/cm 2 has an adhesion strength to an ITO (indium tin oxide) substrate at 120 ° C. In the case of D [MPa], the above A and D satisfy the relationship represented by the following formula (3): D ≧ 0.3 × A (3).

3) 3)

如上述1)所述之液晶滴下工法用液晶密封劑，其中含有：成分(a)(甲基)丙烯酸化環氧樹脂、成分(b)光聚合起始劑、成分(c)無機充填劑、及成分(d)有機醯肼化合物。 The liquid crystal sealing agent for liquid crystal dropping method according to the above 1), which comprises: component (a) (meth) acrylated epoxy resin, component (b) photopolymerization initiator, component (c) inorganic filler, And component (d) an organic hydrazine compound.

4) 4)

如上述3)所述之液晶滴下工法用液晶密封劑，其中，更含有成分(e)熱自由基聚合起始劑。 The liquid crystal sealing agent for a liquid crystal dropping method according to the above 3), which further contains a component (e) a thermal radical polymerization initiator.

5) 5)

如上述4)所述之液晶滴下工法用液晶密封劑，其中，上述成分(e)熱自由基聚合起始劑，為1,2-雙(三甲基矽烷氧基)-1,1,2,2-四苯基乙烷。 The liquid crystal sealing agent for liquid crystal dropping method according to the above 4), wherein the component (e) thermal radical polymerization initiator is 1,2-bis(trimethyldecyloxy)-1,1,2 , 2-tetraphenylethane.

6) 6)

如上述3)所述之液晶滴下工法用液晶密封劑，其中，更含有成分(f)環氧樹脂。 A liquid crystal sealing agent for a liquid crystal dropping method according to the above 3), which further comprises a component (f) epoxy resin.

7) 7)

如上述3)所述之液晶滴下工法用液晶密封劑，其中，更含有成分(g)矽烷偶合劑。 The liquid crystal sealing agent for a liquid crystal dropping method according to the above 3), which further contains a component (g) decane coupling agent.

8) 8)

如上述7)所述之液晶滴下工法用液晶密封劑，其中，上述成分(g)為胺基矽烷偶合劑。 The liquid crystal sealing agent for a liquid crystal dropping method according to the above 7), wherein the component (g) is an amino decane coupling agent.

9) 9)

如上述7)所述之液晶滴下工法用液晶密封劑，其中，上 述成分(g)為胺基矽烷偶合劑與環氧基矽烷偶合劑的混合物。 a liquid crystal sealing agent for liquid crystal dropping method according to the above 7), wherein Component (g) is a mixture of an amine decane coupling agent and an epoxy decane coupling agent.

10) 10)

如上述3)所述之液晶滴下工法用液晶密封劑，其中，更含有成分(h)具有酚性羥基之化合物。 The liquid crystal sealing agent for a liquid crystal dropping method according to the above 3), which further contains a compound having a phenolic hydroxyl group as component (h).

11) 11)

如上述10)所述之液晶滴下工法用液晶密封劑，其中，上述成分(h)為酚系酚醛樹脂。 The liquid crystal sealing agent for a liquid crystal dropping method according to the above 10, wherein the component (h) is a phenolic phenol resin.

12) 12)

一種液晶顯示單元之製造方法，其在由2片基板所構成之液晶顯示單元中，於其中一片基板所形成之由如上述1)至11)中任一項所述之液晶滴下工法用液晶密封劑所構成的堰的內側將液晶滴下後，貼合另一片基板，之後藉由紫外線及/或熱來將上述液晶滴下工法用液晶密封劑予以硬化。 A liquid crystal display unit manufacturing method according to any one of the above-mentioned 1) to 11), wherein a liquid crystal display unit comprising two substrates is formed by a liquid crystal dropping method according to any one of the above 1) to 11) After the liquid crystal is dropped on the inside of the crucible formed of the agent, the other substrate is bonded, and then the liquid crystal sealing agent for liquid crystal dropping method is cured by ultraviolet rays and/or heat.

13) 13)

一種液晶顯示單元，是以一種硬化物黏著而成，該硬化物是將如上述1)至11)中任一項所述之液晶滴下工法用液晶密封劑硬化而獲得。 A liquid crystal display unit obtained by curing a liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above 1) to 11), which is obtained by curing a liquid crystal sealing agent according to any one of the above 1) to 11).

本發明之液晶滴下工法用液晶密封劑，與特別是定向膜等有機膜之黏著性非常優異，在各式各樣環境下都不易引起剝離。因此，可實現在各式各樣環境中能使用的液晶顯示單元。又，由於低液晶污染性、耐熱性、耐熱循環性、耐濕性等一般特性亦優異，故可實現長期可靠性優異的液晶顯示單元。 The liquid crystal sealing agent for a liquid crystal dropping method of the present invention is excellent in adhesion to an organic film such as an oriented film, and is not easily peeled off in various environments. Therefore, a liquid crystal display unit that can be used in a wide variety of environments can be realized. Further, since the general characteristics such as low liquid crystal contamination, heat resistance, heat cycle resistance, and moisture resistance are also excellent, a liquid crystal display unit excellent in long-term reliability can be realized.

本發明之液晶滴下工法用液晶密封劑(以下僅稱為「液晶密封劑」)，其在照射3000mJ/cm2的紫外線後並在120℃環境下予以硬化1小時後，將該硬化後的液晶密封劑於25℃時對於ITO(氧化銦錫)基板的黏著強度設為A〔MPa〕，並將上述硬化後的液晶密封劑於120℃時的黏著強度設為B〔MPa〕，且將僅以3000mJ/cm2的紫外線予以硬化後的液晶密封劑於25℃時對於ITO(氧化銦錫)基板的黏著強度設為C〔MPa〕時，上述A、B、及C滿足下列式(1)、(2)所表示之關係式：B≧0.5×A (1) The liquid crystal sealing agent for liquid crystal dropping method of the present invention (hereinafter simply referred to as "liquid crystal sealing agent") is cured by irradiating ultraviolet rays of 3000 mJ/cm 2 and then curing at 120 ° C for 1 hour, and then curing the liquid crystal after curing. When the sealant is at 25 ° C, the adhesion strength to the ITO (indium tin oxide) substrate is A [MPa], and the adhesion strength of the liquid crystal sealing agent after curing at 120 ° C is B [MPa], and only When the liquid crystal sealing agent hardened by ultraviolet rays of 3000 mJ/cm 2 is C [MPa] when the adhesion strength to the ITO (indium tin oxide) substrate is 25 ° C, the above A, B, and C satisfy the following formula (1). (2) The relationship represented by: B≧0.5×A (1)

C≧0.3×A (2)。 C≧0.3×A (2).

上述式(1)是指在照射3000mJ/cm2的紫外線後並在120℃環境下予以硬化1小時後，於120℃環境下的黏著強度為在25℃環境下的黏著強度的5成(50%)以上。具有此特性之液晶密封劑，在液晶顯示單元的製造中的加熱步驟中，可不產生上下基板的剝離而安定地製造。又，如同熱循環試驗，即使在交互地暴露於高溫及低溫的狀態這樣的情況下，也不產生基板剝離，維持安定。 The above formula (1) means that after the irradiation with ultraviolet rays of 3000 mJ/cm 2 and hardening at 120 ° C for 1 hour, the adhesive strength at 120 ° C is 50% of the adhesive strength at 25 ° C (50). %)the above. The liquid crystal sealing agent having such a characteristic can be stably produced without causing peeling of the upper and lower substrates in the heating step in the production of the liquid crystal display unit. Further, as in the case of the heat cycle test, even when the state is exposed to the high temperature and the low temperature alternately, the substrate peeling does not occur and the stability is maintained.

又，上述式(2)是指在僅照射3000mJ/cm2的紫外線予以硬化後於25℃環境下的黏著強度，是在照射3000mJ/cm2的紫外線後並在120℃環境下予以硬化1小時後，於25℃環 境下的黏著強度的3成(30%)以上。具有此特性之液晶密封劑，在液晶顯示單元的製造中的紫外線照射步驟之中的硬化收縮小，亦即，即使在有機膜上，施加在該有機膜上的應力變小，能夠實現優異的黏著性。 Further, the above formula (2) refers to an adhesive strength in an environment of 25 ° C after being cured by irradiation with only ultraviolet rays of 3,000 mJ/cm 2 , and is hardened by irradiation with ultraviolet rays of 3,000 mJ/cm 2 and at 120 ° C for 1 hour. After that, the adhesive strength at 30 ° C was 30% (30%) or more. The liquid crystal sealing agent having such a characteristic has a small hardening shrinkage in the ultraviolet irradiation step in the production of the liquid crystal display unit, that is, even if the stress applied to the organic film is small on the organic film, excellent performance can be achieved. Adhesive.

又，在照射3000mJ/cm2的紫外線後並在120℃環境 下予以硬化1小時後，將該硬化後的液晶密封劑於25℃時對於ITO(氧化銦錫)基板的黏著強度設為A〔MPa〕；將僅以3000mJ/cm2的紫外線予以硬化後的液晶密封劑於120℃時對於ITO(氧化銦錫)基板的黏著強度設為D〔MPa〕。此時，在滿足下列式(3)所表示之關係式的情況，特別顯著地達成本發明之效果。 Further, after irradiating ultraviolet rays of 3,000 mJ/cm 2 and curing in an environment of 120 ° C for 1 hour, the adhesion strength of the cured liquid crystal sealing agent to the ITO (indium tin oxide) substrate at 25 ° C was set to A [ MPa]; The adhesion strength of the liquid crystal sealing agent which was cured by ultraviolet rays of only 3000 mJ/cm 2 to the ITO (indium tin oxide) substrate at 120 ° C was D [MPa]. In this case, the effect of the present invention is particularly remarkable in the case where the relationship expressed by the following formula (3) is satisfied.

D≧0.3×A (3) D≧0.3×A (3)

所謂在25℃時對於ITO(氧化銦錫)基板的黏著強度，是指在25℃的環境下的黏著強度。黏著強度的測定方法，是使用剪切方向的黏著強度。例如，先在5cm見方的ITO(氧化銦錫)基板上塗布少量液晶密封劑，然後使用鑷子，將1.5mm見方的玻璃晶片(將EAGLE XG：CORNING公司製切成1.5mm見方)貼合。對此試驗片照射紫外線3000mJ/cm2後，放置於設定在120℃之熱風烤箱中1小時，進行加熱硬化。針對此試驗片(予以貼合之玻璃晶片)，能夠使用黏著強度試驗機(bond tester)(SS-30WD：西進商事股份有限公司)測定黏著強度。在本案中，是將如此而得之黏著強度的值定義為A〔MPa〕。又，使用的ITO(氧化銦錫)基板，是將470×370×0.7SP30ITO(GEOMATEC股份有限公司製)切斷成 5cm見方而使用。 The adhesion strength to an ITO (indium tin oxide) substrate at 25 ° C means the adhesion strength in an environment of 25 ° C. The method of measuring the adhesion strength is to use the adhesion strength in the shear direction. For example, a small amount of a liquid crystal sealing agent is applied onto a 5 cm square ITO (indium tin oxide) substrate, and then a 1.5 mm square glass wafer (cut by EAGLE XG: CORNING Co., Ltd., 1.5 mm square) is bonded using a tweezers. The test piece was irradiated with ultraviolet rays of 3000 mJ/cm 2 , placed in a hot air oven set at 120 ° C for 1 hour, and heat-hardened. For this test piece (a glass wafer to be bonded), the adhesion strength can be measured using a bond tester (SS-30WD: Sejin Corporation). In the present case, the value of the adhesive strength thus obtained is defined as A [MPa]. In addition, the ITO (indium tin oxide) substrate used was cut into 5 cm squares and cut into 470 × 370 × 0.7 SP30 ITO (manufactured by GEOMATEC Co., Ltd.).

所謂於120℃時的黏著強度，是在將硬化後的試驗 片加熱到120℃的狀態測定之黏著強度，測定方法本身與上述相同。作為加熱到120℃的方法，將黏著強度之測定裝置的測定載台加熱到120℃之方法係為簡便。在本案中，是將如此而得之黏著強度的值定義為B〔MPa〕。 The so-called adhesive strength at 120 ° C is the test after hardening The adhesion strength measured by heating the sheet to 120 ° C was measured in the same manner as described above. As a method of heating to 120 ° C, the method of heating the measurement stage of the measuring device of the adhesion strength to 120 ° C is simple. In the present case, the value of the adhesive strength thus obtained is defined as B [MPa].

所謂僅以3000mJ/cm2的紫外線予以硬化後的液晶 密封劑於25℃時對於ITO(氧化銦錫)基板的黏著強度，是針對在試驗片的製作過程中未進行液晶密封劑的加熱硬化而製成之試驗片所測定的黏著強度，是在25℃的環境下所測定的值。又，測定本身是與上述同樣地進行。在本案中，是將如此而得之黏著強度的值定義為C〔MPa〕。 The adhesion strength of the liquid crystal sealing agent which is hardened by ultraviolet rays of only 3000 mJ/cm 2 to the ITO (indium tin oxide) substrate at 25 ° C is that the liquid crystal sealing agent is not heat-hardened during the production of the test piece. The adhesive strength measured by the prepared test piece was a value measured in an environment of 25 °C. Further, the measurement itself was carried out in the same manner as described above. In the present case, the value of the adhesive strength thus obtained is defined as C [MPa].

所謂僅以3000mJ/cm2的紫外線予以硬化後的液晶 密封劑於120℃時對於ITO(氧化銦錫)基板的黏著強度，是針對在試驗片的製作過程中未進行液晶密封劑的加熱硬化而製成之試驗片所測定的黏著強度，是在120℃的環境下所測定的值。又，測定本身是與上述同樣地進行。在本案中，是將如此而得之黏著強度的值定義為D〔MPa〕。 The adhesion strength of the liquid crystal sealing agent which is hardened by ultraviolet rays of only 3000 mJ/cm 2 to the ITO (indium tin oxide) substrate at 120 ° C is that the liquid crystal sealing agent is not heat-hardened during the production of the test piece. The adhesive strength measured by the prepared test piece was a value measured in an environment of 120 °C. Further, the measurement itself was carried out in the same manner as described above. In the present case, the value of the adhesive strength thus obtained is defined as D [MPa].

本發明是液晶滴下工法用之液晶密封劑。在液晶滴 下工法中，於液晶顯示單元的製造步驟中，一般具有紫外線照射的步驟，在以此步驟所硬化之液晶密封劑與定向膜等有機膜之間蓄積了很大的應力。因此，當在進行如此的液晶滴下工法時，使用本發明之液晶密封劑為非常有效。 The present invention is a liquid crystal sealing agent for a liquid crystal dropping method. In the liquid crystal drop In the lower working method, in the manufacturing step of the liquid crystal display unit, there is generally a step of irradiating ultraviolet rays, and a large stress is accumulated between the liquid crystal sealing agent hardened in this step and the organic film such as the alignment film. Therefore, when such a liquid crystal dropping method is carried out, it is very effective to use the liquid crystal sealing agent of the present invention.

本發明之液晶密封劑，若為具有上述特性的液晶滴 下工法用之液晶密封劑雖無特別限定，但含有成分(a)(甲基)丙烯酸化環氧樹脂、成分(b)光聚合起始劑、成分(c)無機充填劑、以及成分(d)有機醯肼(organic acid hydrazide)化合物的情況為特佳的態樣。含有此等成分的液晶密封劑，對於液晶的污染性低，具有對液晶滴下工法而言為優異的特性。 The liquid crystal sealing agent of the present invention is a liquid crystal droplet having the above characteristics The liquid crystal sealing agent used in the following method is not particularly limited, but contains components (a) (meth)acrylated epoxy resin, component (b) photopolymerization initiator, component (c) inorganic filler, and component (d). The case of an organic acid hydrazide compound is a particularly preferred aspect. The liquid crystal sealing agent containing these components has low contamination property with respect to liquid crystals, and is excellent in the liquid crystal dropping method.

成分(a)(甲基)丙烯酸化環氧樹脂，可藉由環氧 樹脂與(甲基)丙烯酸之周知的反應而得。例如，藉由在環氧樹脂中添加特定當量比之(甲基)丙烯酸與觸媒(例如苯甲基二甲胺、三乙胺、苯甲基三甲基氯化銨、三苯膦、三苯銻等)、與聚合抑制劑(例如甲氧苯酚、對苯二酚、甲基對苯二酚、啡噻(phenothiazine)、二丁基羥基甲苯等)，進行例如80~110℃酯化反應而得。作為當作原料的環氧樹脂，並沒有特別限定，但較佳為2官能以上之環氧樹脂，例如可舉出間苯二酚(雷瑣辛)之二縮水甘油醚、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、雙酚A酚醛型環氧樹脂、雙酚F酚醛型環氧樹脂、脂環式環氧樹脂、脂肪族鏈狀環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、乙內醯脲型環氧樹脂、異氰尿酸型環氧樹脂、三酚甲烷骨架之酚系酚醛型環氧樹脂，其他還有二官能酚類之二縮水甘油醚化物、二官能醇類之二縮水甘油醚化物、及該等之鹵化物、氫化物等。此等之中，從液晶污染性的觀點而言，更佳為雙酚型環氧樹脂、酚醛型環氧樹脂、間苯二酚(雷瑣辛)之二縮水甘 油醚。 The component (a) (meth) acrylated epoxy resin can be obtained by a well-known reaction of an epoxy resin and (meth)acrylic acid. For example, by adding a specific equivalent ratio of (meth)acrylic acid to a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, three) Benzoquinone, etc., with polymerization inhibitors (eg methoxyphenol, hydroquinone, methyl hydroquinone, thiophene (phenothiazine), dibutylhydroxytoluene, etc., obtained by, for example, an esterification reaction at 80 to 110 °C. The epoxy resin to be used as a raw material is not particularly limited, and is preferably a bifunctional or higher epoxy resin, and examples thereof include diglycidyl ether of resorcinol (Resorcin) and bisphenol A type ring. Oxygen resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A phenol type epoxy resin, bisphenol F phenol type epoxy Resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, intramethylene urea resin, isocyanuric epoxy resin, A phenolic novolac type epoxy resin of a trisphenol methane skeleton, and a diglycidyl ether compound of a difunctional phenol, a diglycidyl ether compound of a difunctional alcohol, and a halide or a hydride thereof. Among these, from the viewpoint of liquid crystal contamination, a bisphenol type epoxy resin, a novolac type epoxy resin, and a diglycidyl ether of resorcin (resorcin) are more preferable.

上述成分(a)(甲基)丙烯酸化環氧樹脂的含量， 係考慮所得之液晶密封劑的作業性、物性而適當決定，通常在液晶密封劑中是25~80質量%左右，較佳為25~75質量%。 The content of the above component (a) (meth) acrylated epoxy resin, In view of the workability and physical properties of the obtained liquid crystal sealing agent, the liquid crystal sealing agent is usually about 25 to 80% by mass, preferably 25 to 75% by mass.

成分(b)光聚合起始劑，只要是藉由紫外線或可見 光的照射來產生自由基而啟動連鎖聚合反應的化合物，則無特別限定，例如，能舉出苯甲基二甲基縮酮、1-羥基環己基苯基酮、二乙基硫雜蒽酮、二苯甲酮、2-乙基蒽醌、2-羥基-2-甲基苯丙酮、2-甲基-〔4-(甲硫基)苯基〕-2-(N-嗎啉基)-1-丙烷、2,4,6-三甲基苯甲醯基二苯基氧化膦、樟腦醌、9-茀酮、二苯基二硫醚等。具體而言，能舉出IRGACURERTM 651、184、2959、127、907、396、379EG、819、784、754、500、OXE01、OXE02、DAROCURERTM 1173、LUCIRINRTM TPO(以上為BASF公司製)；SEIKUOLRTM Z、BZ、BEE、BIP、BBI(以上為精工化學股份有限公司製)等。另外，本說明書中上標的「RTM」係指註冊商標。 The component (b) photopolymerization initiator is not particularly limited as long as it is a compound that initiates a chain polymerization reaction by irradiation of ultraviolet rays or visible light, and examples thereof include, for example, benzyldimethylketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethyl hydrazine, 2-hydroxy-2-methylpropiophenone, 2-methyl-[4-(A Thio)phenyl]-2-(N-morpholinyl)-1-propane, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyl Dithioethers and the like. Specifically, IRGACURE RTM 651, 184, 2959, 127, 907, 396, 379EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE RTM 1173, LUCIRIN RTM TPO (above, BASF); SEIKUOL RTM Z, BZ, BEE, BIP, BBI (above, manufactured by Seiko Chemical Co., Ltd.). In addition, the "RTM" superscripted in this manual means a registered trademark.

又，從液晶污染性之觀點而言，較佳為使用分子內具有(甲基)丙烯酸基者，例如合適地使用2-甲基丙烯醯氧乙基異氰酸酯與1-〔4-(2-羥基乙氧基)-苯基〕-2-羥基-2-甲基-1-丙烷-1-酮的反應生成物。此化合物能夠以國際公開第2006/027982號記載之方法來製造而得。 Further, from the viewpoint of liquid crystal contamination, it is preferred to use a (meth)acrylic group in the molecule, and for example, 2-methylpropenyloxyethyl isocyanate and 1-[4-(2-hydroxyl) are suitably used. A reaction product of ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one. This compound can be produced by the method described in International Publication No. 2006/027982.

在本發明之液晶密封劑所能使用之上述成分(b)光聚合起始劑的含量，將液晶密封劑全體設為100質量%時，通常為0.01~15質量%，較佳為0.02~10質量%。 The content of the component (b) photopolymerization initiator which can be used in the liquid crystal sealing agent of the present invention is usually 0.01 to 15% by mass, preferably 0.02 to 10%, when the entire liquid crystal sealing agent is 100% by mass. quality%.

作為成分(c)無機充填劑，可舉出熔融二氧化矽、 結晶二氧化矽、碳化矽、氮化矽、氮化硼、碳酸鈣、碳酸鎂、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氧化鎂、氧化鋯、氫氧化鋁、氫氧化鎂、矽酸鈣、矽酸鋁、矽酸鋰鋁、矽酸鋯、鈦酸鋇、玻璃纖維、碳纖維、二硫化鉬、石棉等，較佳為熔融二氧化矽、結晶二氧化矽、氮化矽、氮化硼、碳酸鈣、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氫氧化鋁、矽酸鈣、矽酸鋁，更佳為熔融二氧化矽、結晶二氧化矽、氧化鋁、滑石。此等無機充填劑亦可混合2種以上使用。 特別是在作為下列液晶顯示單元用黏著劑使用的情況，由於其平均粒徑若過大時，造成在窄間隙之液晶顯示單元製造時，貼合上下玻璃基板時的間隙形成不易等不良因素，故3μm以下為適當，較佳為2μm以下。粒徑能夠利用雷射繞射/散射式粒徑分析儀(乾式)(SEISHIN企業股份有限公司製；LMS-30)來測定。 As the component (c) inorganic filler, molten cerium oxide, Crystalline cerium oxide, cerium carbide, cerium nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesia, zirconia, aluminum hydroxide, magnesium hydroxide , calcium citrate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably molten cerium oxide, crystalline cerium oxide, cerium nitride Boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium citrate, aluminum citrate, more preferably molten cerium oxide, crystalline cerium oxide, aluminum oxide ,talc. These inorganic fillers may be used in combination of two or more kinds. In particular, when it is used as an adhesive for the following liquid crystal display unit, when the average particle diameter is too large, it is difficult to form a gap when the upper and lower glass substrates are bonded during the manufacture of the liquid crystal display unit with a narrow gap, so that 3 μm or less is suitable, and preferably 2 μm or less. The particle size can be measured by a laser diffraction/scattering particle size analyzer (dry type) (manufactured by SEISHIN Co., Ltd.; LMS-30).

上述成分(c)無機充填劑的含量，在將本發明之液 晶密封劑全體設為100質量%時，通常為1~60質量%，較佳為5~50質量%。上述成分(c)無機充填劑的含量過少的情況，由於黏著強度低落且耐濕可靠性亦變差，所以有吸濕後的黏著強度亦大幅低落的情況。另一方面，上述成分(c)無機充填劑的含量過多的情況，在作為液晶顯示單元用黏著劑使用時，有無法形成單元間隙的情況。 The content of the above component (c) inorganic filler, in the liquid of the present invention When the total amount of the crystal sealant is 100% by mass, it is usually 1 to 60% by mass, preferably 5 to 50% by mass. When the content of the component (c) inorganic filler is too small, the adhesive strength is lowered and the moisture resistance reliability is also deteriorated, so that the adhesion strength after moisture absorption is also largely lowered. On the other hand, when the content of the component (c) inorganic filler is too large, when it is used as an adhesive for a liquid crystal display unit, a cell gap may not be formed.

所謂成分(d)有機醯肼化合物，是以使肼與有機酸進行反應而得的方式，具有-NHNH2這類官能基之芳香族或是 脂肪族之化合物。作為芳香族醯肼，能夠舉出對苯二甲酸二醯肼、間苯二甲酸二醯肼、2,6-萘甲酸二醯肼、2,6-吡啶二醯肼、1,2,4-苯三醯肼、1,4,5,8-萘甲酸四醯肼、苯均四酸四醯肼等。又，作為脂肪族醯肼化合物，例如能夠舉出甲醯肼、乙醯肼、丙醯肼、乙二酸二醯肼、丙二酸二醯肼、丁二酸二醯肼、戊二酸二醯肼、己二酸二醯肼、庚二酸二醯肼、癸二酸二醯肼、1,4-環己烷二醯肼、酒石酸二醯肼、蘋果酸二醯肼、亞胺基二乙酸二醯肼、N,N’-六亞甲基雙半卡肼、檸檬酸三醯肼、氮基三乙酸三醯肼、環己烷三羧酸三醯肼、1,3-雙(肼基羰基乙基)-5-異丙基乙內醯脲等具有乙內醯脲骨架、較佳為具有纈胺酸乙內醯脲骨架(乙內醯脲環之碳原子經以異丙基取代之骨架)之二醯肼化合物、具有異氰尿酸骨架之化合物等。作為具有異氰尿酸骨架之化合物，例如能夠舉出參(1-肼基羰基甲基)異氰尿酸酯、參(2-肼基羰基乙基)異氰尿酸酯、參(2-肼基羰基乙基)異氰尿酸酯、參(3-肼基羰基丙基)異氰尿酸酯、雙(2-肼基羰基乙基)異氰尿酸酯等。從硬化反應性與潛在性的平衡來看，較佳為間苯二甲酸二醯肼、丙二酸二醯肼、己二酸二醯肼、參(1-肼基羰基甲基)異氰尿酸酯、參(2-肼基羰基乙基)異氰尿酸酯、參(2-肼基羰基乙基)異氰尿酸酯、參(3-肼基羰基丙基)異氰尿酸酯，特佳為丙二酸二醯肼、癸二酸二醯肼、參(2-肼基羰基乙基)異氰尿酸酯。 就使用上述成分(d)有機醯肼化合物時的含量而言，在將成分(a)(甲基)丙烯酸化環氧樹脂的總量設為100質量份的情況下，含有1~20質量份的情況為佳，更佳為2~10質量 份，亦可混合2種以上使用。 The component (d) organic ruthenium compound is an aromatic or aliphatic compound having a functional group such as -NHNH 2 in such a manner that ruthenium is reacted with an organic acid. Examples of the aromatic hydrazine include diterpene terephthalate, diammonium isophthalate, diammonium 2,6-naphthoate, 2,6-pyridine dioxime, 1,2,4- Benzoquinone, tetramethylphosphonium 1,4,5,8-naphthoate, tetrabenzal tetrahydrofuranate, and the like. Further, examples of the aliphatic hydrazine compound include formazan, acetamidine, acetonide, bismuth oxalate, diammonium malonate, diterpene succinate, and glutaric acid. Bismuth, diammonium adipate, diammonium pimelate, diterpene sebacate, 1,4-cyclohexanedioxime, diterpenic tartrate, diterpenic acid malate, iminodiyl Diterpene acetate, N, N'-hexamethylene bis-semicarbazone, triterpenoid citrate, trimethyl sulfatriacetate, triterpene Cyclohexane tricarboxylate, 1,3-double (肼Carbocarbonylethyl)-5-isopropylhydantoin or the like having an intramethylene uregar skeleton, preferably having a carbendazim urea skeleton (the carbon atom of the uremone ring is replaced by an isopropyl group) a bismuth compound, a compound having an isocyanuric acid skeleton, and the like. Examples of the compound having an isocyanuric acid skeleton include ginseng (1-fluorenylcarbonylmethyl)isocyanurate, ginseng (2-mercaptocarbonylethyl)isocyanurate, and ginseng (2-oxime). Alkylcarbonylethyl)isocyanurate, ginseng (3-mercaptocarbonylpropyl)isocyanurate, bis(2-mercaptocarbonylethyl)isocyanurate, and the like. From the balance of hardening reactivity and potential, it is preferably diammonium isophthalate, diammonium malonate, diterpene adipate, ginseng (1-mercaptocarbonylmethyl) isocyanuric acid. Acid ester, ginseng (2-mercaptocarbonylethyl) isocyanurate, ginseng (2-mercaptocarbonylethyl) isocyanurate, ginseng (3-mercaptocarbonylpropyl) isocyanurate Particularly preferred are diammonium malonate, diterpene sebacate, and bis(2-mercaptocarbonylethyl)isocyanurate. When the total amount of the component (a) (meth) acrylated epoxy resin is 100 parts by mass, the content of the component (d) organic cerium compound is 1 to 20 parts by mass. The case is preferably 2 to 10 parts by mass, and may be used in combination of 2 or more types.

本發明之液晶密封劑，依照需要亦可含有成分(e)熱自由基聚合起始劑。 The liquid crystal sealing agent of the present invention may further contain a component (e) a thermal radical polymerization initiator as needed.

成分(e)熱自由基聚合起始劑，只要是藉由加熱來產生自由基而啟動連鎖聚合反應的化合物則無特別限定，可舉出有機過氧化物、偶氮化合物、苯偶姻化合物、苯偶姻醚化合物、苯乙酮化合物、苯頻哪醇(benzopinacol)等，適合使用苯頻哪醇。例如，作為有機過氧化物，可購入KayamekRTM A、M、R、L、LH、SP-30C、Perkadox CH-50L、BC-FF、Cadox B-40ES、Perkadox 14、TrigonoxRTM 22-70E、23-C70、121、121-50E、121-LS50E、21-LS50E、42、42LS、KayaesterRTM P-70、TMPO-70、CND-C70、OO-50E、AN、KayabutylRTM B、Perkadox 16、KayacarbonRTM BIC-75、AIC-75(以上為化藥Akzo股份有限公司製)；PERMEKRTM N、H、S、F、D、G、PERHEXARTM H、HC、TMH、C、V、22、MC、PERCURERTM AH、AL、HB、PERBUTYLRTM H、C、ND、L、PERCUMYLRTM H、D、PEROYLRTM IB、IPP、PEROCTARTM ND(以上為日油股份有限公司製)等市售品。又，作為偶氮化合物，可購入VA-044、V-070、VPE-0201、VSP-1001等(以上為和光純藥工業股份有限公司製)等市售品。 The component (e) thermal radical polymerization initiator is not particularly limited as long as it is a compound which initiates a chain polymerization reaction by generating a radical by heating, and examples thereof include an organic peroxide, an azo compound, and a benzoin compound. A benzoin ether compound, an acetophenone compound, a benzopinacol or the like is preferably used as the benzopinacol. For example, as an organic peroxide, Kayamek RTM A, M, R, L, LH, SP-30C, Perkadox CH-50L, BC-FF, Cadox B-40ES, Perkadox 14, Trigonox RTM 22-70E, 23 can be purchased. -C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl RTM B, Perkadox 16, Kayacarbon RTM BIC-75, AIC-75 (above is made by Akzo Co., Ltd.); PERMEK RTM N, H, S, F, D, G, PERHEXA RTM H, HC, TMH, C, V, 22, MC, PERCURE Commercial products such as RTM AH, AL, HB, PERBUTYL RTM H, C, ND, L, PERCUMYL RTM H, D, PEROYL RTM IB, IPP, PEROCTA RTM ND (above, Nippon Oil Co., Ltd.). Further, as the azo compound, commercially available products such as VA-044, V-070, VPE-0201, VSP-1001, etc. (the above is manufactured by Wako Pure Chemical Industries, Ltd.) can be purchased.

作為上述成分(e)熱自由基聚合起始劑，較佳為苯頻哪醇系的熱自由基聚合起始劑(包含將苯頻哪醇進行化學性修飾者)。具體而言，可舉出苯頻哪醇、1,2-二甲氧基-1,1,2,2-四苯基乙烷、1,2-二乙氧基-1,1,2,2-四苯基乙烷、1,2-二苯氧 基-1,1,2,2-四苯基乙烷、1,2-二甲氧基-1,1,2,2-四(4-甲基苯基)乙烷、1,2-二苯氧基-1,1,2,2-四(4-甲氧基苯基)乙烷、1,2-雙(三甲基矽烷氧基)-1,1,2,2-四苯基乙烷、1,2-雙(三乙基矽烷氧基)-1,1,2,2-四苯基乙烷、1,2-雙(三級丁基二甲基矽烷氧基)-1,1,2,2-四苯基乙烷、1-羥基-2-三甲基矽烷氧基-1,1,2,2-四苯基乙烷、1-羥基-2-三乙基矽烷氧基-1,1,2,2-四苯基乙烷、1-羥基-2-三級丁基二甲基矽烷氧基-1,1,2,2-四苯基乙烷等。較佳為1-羥基-2-三甲基矽烷氧基-1,1,2,2-四苯基乙烷、1-羥基-2-三乙基矽烷氧基-1,1,2,2-四苯基乙烷、1-羥基-2-三級丁基二甲基矽烷氧基-1,1,2,2-四苯基乙烷、1,2-雙(三甲基矽烷氧基)-1,1,2,2-四苯基乙烷，更佳為1-羥基-2-三甲基矽烷氧基-1,1,2,2-四苯基乙烷、1,2-雙(三甲基矽烷氧基)-1,1,2,2-四苯基乙烷，特佳為1,2-雙(三甲基矽烷氧基)-1,1,2,2-四苯基乙烷。 As the component (e) thermal radical polymerization initiator, a benzopinacol-based thermal radical polymerization initiator (including a chemical modification of benzopinacol) is preferred. Specific examples thereof include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, and 1,2-diethoxy-1,1,2. 2-tetraphenylethane, 1,2-diphenyloxide Base-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetrakis(4-methylphenyl)ethane, 1,2-di Phenoxy-1,1,2,2-tetrakis(4-methoxyphenyl)ethane, 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenyl Ethane, 1,2-bis(triethyldecyloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tertiary butyldimethylmethylalkoxy)-1 1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethyldecane Oxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tributylbutylmethyloxyl-1,1,2,2-tetraphenylethane, and the like. Preferred is 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethyldecyloxy-1,1,2,2 -tetraphenylethane, 1-hydroxy-2-tributyl dimethyl decyloxy-1,1,2,2-tetraphenylethane, 1,2-bis(trimethyldecyloxy) -1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane, 1,2- Bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, particularly preferably 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetra Phenylethane.

上述苯頻哪醇為販售自東京化成工業股份有限公司、和光純藥工業股份有限公司等。又，對苯頻哪醇之羥基進行醚化而得的化合物，可藉由周知的方法輕易合成。又，對苯頻哪醇之羥基進行矽烷基醚化而得的化合物，能夠藉由將對應的苯頻哪醇與各種矽烷化劑在吡啶等鹼性觸媒下予以加熱之方法進行合成而得。作為矽烷化劑，可舉出一般所知的三甲基矽烷化劑亦即三甲基氯矽烷(TMCS)、六甲基二矽氮烷(HMDS)、N,O-雙(三甲基矽烷基)三氟乙醯胺(BSTFA)、和三乙基矽烷化劑亦即三乙基氯矽烷(TECS)、三級丁基二甲基矽烷化劑亦即三級丁基甲基矽烷(TBMS)等。此等試劑 能夠由矽衍生物製造商等之市場輕易購入。就矽烷化劑之反應量而言，相對於1莫耳對象化合物的羥基，以1.0~5.0倍莫耳為佳。更佳為1.5~3.0倍莫耳。若比1.0倍莫耳少，由於反應效率差而反應時間變長，所以會促進熱分解。若比5.0倍莫耳多，在回收時分離變差、或變得不易精製。 The above benzopinacol is sold from Tokyo Chemical Industry Co., Ltd., and Wako Pure Chemical Industries Co., Ltd., and the like. Further, a compound obtained by etherifying a hydroxyl group of benzopinacol can be easily synthesized by a known method. Further, a compound obtained by subjecting a hydroxyl group of a benzopinacol to a decyl ether can be synthesized by heating a corresponding benzopinacol with various decylating agents under an alkaline catalyst such as pyridine. . The decylating agent may, for example, be a trimethyl chloroalkylene (TMCS), hexamethyldioxane (HMDS) or N,O-bis(trimethylnonane) which is generally known. Trifluoroacetamide (BSTFA), and triethyl decylating agent, namely triethyl chlorodecane (TECS), tertiary butyl dimethyl methacrylate, ie, tertiary butyl methyl decane (TBMS), etc. . These reagents It can be easily purchased by the market of bismuth derivative manufacturers and the like. The amount of the reaction of the alkylating agent is preferably 1.0 to 5.0 times the molar amount of the hydroxyl group of the compound of 1 mole. More preferably 1.5 to 3.0 times Mo. If it is less than 1.0 times Moule, the reaction time becomes long due to poor reaction efficiency, and thus thermal decomposition is promoted. If it is more than 5.0 times Mo, the separation deteriorates or becomes difficult to refine at the time of recovery.

成分(e)熱自由基聚合起始劑，較佳為將粒徑縮小 且均勻地分散。其平均粒徑若過大時，造成在窄間隙之液晶顯示單元製造時，貼合上下玻璃基板時的間隙形成不易等不良因素，故較佳為5μm以下，更佳為3μm以下。又，雖然無限制地縮小也無妨，但通常下限為0.1μm左右。粒徑能夠利用雷射繞射/散射式粒徑分析儀(乾式)(SEISHIN企業股份有限公司製；LMS-30)來測定。 Ingredient (e) a thermal radical polymerization initiator, preferably a particle size reduction And dispersed evenly. When the average particle diameter is too large, it is difficult to form a gap when the liquid crystal display unit having a narrow gap is formed, and the gap is not easily formed when the upper and lower glass substrates are bonded. Therefore, it is preferably 5 μm or less, and more preferably 3 μm or less. Further, although it may be reduced without limitation, the lower limit is usually about 0.1 μm. The particle size can be measured by a laser diffraction/scattering particle size analyzer (dry type) (manufactured by SEISHIN Co., Ltd.; LMS-30).

成分(e)熱自由基聚合起始劑的含量，將本發明之 液晶密封劑全體設為100質量%的情況下，較佳為0.001~0.5質量%左右。 The content of the component (e) thermal radical polymerization initiator, which will be the present invention When the total amount of the liquid crystal sealing agent is 100% by mass, it is preferably about 0.001 to 0.5% by mass.

本發明之液晶密封劑，亦可依需要而含有成分(f) 環氧樹脂。 The liquid crystal sealing agent of the present invention may further contain a component (f) as needed Epoxy resin.

成分(f)環氧樹脂雖然沒有特別限定，但以對液晶的污染性、溶解性低者為佳。作為適宜的環氧樹脂之例，可舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、間苯二酚(雷瑣辛)的二縮水甘油醚、苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、雙酚A酚醛型環氧樹脂、雙酚F酚醛型環氧樹脂、脂環式環氧樹脂、脂肪族鏈狀環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、乙內醯脲型環 氧樹脂、異氰尿酸型環氧樹脂、具有三酚甲烷骨架之酚系酚醛型環氧樹脂，其他還有二官能酚類之二縮水甘油醚化物、二官能醇類之二縮水甘油醚化物、以及該等之鹵化物、氫化物等。 The component (f) epoxy resin is not particularly limited, but is preferably one which is less polluting or solubility to liquid crystal. Examples of suitable epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and diglycidyl ether of resorcinol (redozin). , phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, shrinkage Glyceride type epoxy resin, glycidylamine type epoxy resin, intramethylene urea cycle Oxygen resin, isocyanuric acid type epoxy resin, phenolic novolac type epoxy resin having a trisphenol methane skeleton, and other diglycidyl ether compounds of difunctional phenols, diglycidyl ether of difunctional alcohols, And such halides, hydrides, and the like.

成分(f)環氧樹脂的含量，係考慮液晶密封劑的作 業性、物性而適當決定，通常在液晶密封劑中為25~80質量%左右，較佳為25~75質量%。又，成分(a)(甲基)丙烯酸化環氧樹脂與成分(f)環氧樹脂的總和之中，成分(f)環氧樹脂占1~30質量%是本發明的較佳態樣之一，更佳為5質量%~15質量%。 The content of the component (f) epoxy resin is considered as the liquid crystal sealant The liquid crystal sealing agent is usually about 25 to 80% by mass, preferably 25 to 75% by mass, depending on the industrial properties and physical properties. Further, among the sum of the component (a) (meth) acrylated epoxy resin and the component (f) epoxy resin, the component (f) epoxy resin accounts for 1 to 30% by mass, which is a preferred aspect of the present invention. First, it is more preferably 5 mass% to 15 mass%.

本發明之液晶密封劑，能夠使用成分(g)矽烷偶合 劑，來謀求黏著強度更進一步的提升。作為成分(g)矽烷偶合劑，可舉出胺基矽烷偶合劑、環氧基矽烷偶合劑、巰基矽烷偶合劑、乙烯基矽烷偶合劑、丙烯酸矽烷偶合劑、甲基丙烯酸矽烷偶合劑、脲基矽烷偶合劑等。在這之中，較佳為胺基矽烷偶合劑、環氧基矽烷偶合劑，在併用胺基矽烷偶合劑與環氧基矽烷偶合劑的情況，更顯著地達成本發明之效果。 就矽烷偶合劑的具體例而言，作為環氧基矽烷偶合劑，可舉出3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷等，作為胺基矽烷偶合劑，可舉出N-苯基-γ-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)3-胺基丙基甲基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基 三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-(2-(乙烯基苯甲基胺基)乙基)3-胺基丙基三甲氧基矽烷塩酸塩等，作為巰基矽烷偶合劑可舉出3-巰基丙基三甲氧基矽烷等，作為乙烯基矽烷偶合劑可舉出乙烯基三甲氧基矽烷等，作為丙烯酸矽烷偶合劑，可舉出3-丙烯醯氧基丙基三甲氧基矽烷等，作為甲基丙烯酸矽烷偶合劑可舉出3-甲基丙烯醯氧基丙基三甲氧基矽烷等，作為脲基矽烷偶合劑，可舉出3-脲基丙基三乙氧基矽烷等。此等矽烷偶合劑，由於已以KBM系列、KBE系列等由信越化學工業股份有限公司等販賣，故可容易從市場購入。此等之中，較佳的矽烷偶合劑為N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷(KBM-603信越化學工業股份有限公司製)、3-縮水甘油氧基丙基三甲氧基矽烷(S-510 CHISSO股份有限公司製)，併用兩者時更佳。成分(g)矽烷偶合劑的含量，將本發明之液晶密封劑的全體設為100質量%時，0.05~3質量%為宜。 The liquid crystal sealing agent of the present invention can be used as component (g) decane coupling Agent, to seek further improvement in adhesion strength. Examples of the component (g) decane coupling agent include an amino decane coupling agent, an epoxy decane coupling agent, a decyl decane coupling agent, a vinyl decane coupling agent, a decyl methacrylate coupling agent, a decane methacrylate coupling agent, and a ureido group. A decane coupling agent or the like. Among these, an amine decane coupling agent and an epoxy decane coupling agent are preferable, and the effect of the present invention is more remarkably obtained in the case where an amino decane coupling agent and an epoxy decane coupling agent are used in combination. Specific examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane and 3-glycidoxypropylmethyldimethoxydecane as the epoxy decane coupling agent. 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc., as the amine decane coupling agent, N-benzene --γ-aminopropyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)3-amine Propylmethyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyl Trimethoxy decane, 3-aminopropyltriethoxy decane, N-(2-(vinylbenzylamino)ethyl) 3-aminopropyltrimethoxydecane ruthenate, etc. Examples of the decane coupling agent include 3-mercaptopropyltrimethoxydecane. Examples of the vinyl decane coupling agent include vinyltrimethoxydecane. Examples of the decane coupling agent include 3-propenyloxypropane. Examples of the decyl methacrylate coupling agent include 3-methacryloxypropyltrimethoxydecane and the like, and the ureido decane coupling agent may, for example, be 3-ureidopropyltriene. Ethoxy decane and the like. Since these decane coupling agents have been sold by Shin-Etsu Chemical Co., Ltd., etc. in KBM series, KBE series, etc., they can be easily purchased from the market. Among these, a preferred decane coupling agent is N-2-(aminoethyl)-3-aminopropyltrimethoxydecane (KBM-603 Shin-Etsu Chemical Co., Ltd.), 3-glycidol Ethoxypropyltrimethoxydecane (manufactured by S-510 CHISSO Co., Ltd.) is more preferably used in combination. When the total amount of the liquid crystal sealing agent of the present invention is 100% by mass, the content of the component (g) of the decane coupling agent is preferably 0.05 to 3% by mass.

本發明之液晶密封劑，能夠使用成分(h)具有酚性 羥基之化合物，來謀求黏著強度更進一步的提升。作為具有酚性羥基之化合物，可舉出雙酚A、四溴雙酚A、雙酚F、雙酚S、4,4-聯苯基酚、2,2,6,6-四甲基-4,4-聯苯基酚、2,2-亞甲基-雙(4-甲基-6-三級丁基苯酚)、參(羥基苯基)甲烷、鄰苯三酚、具有二亞異丙基骨架之酚類、1,1-二-4-羥基苯基茀等具有茀骨架之酚類；酚化聚丁二烯等聚酚化合物；以苯酚、甲酚類、乙基苯酚類、丁基苯酚類、辛基苯酚類、雙酚A、烯丙基苯酚類、溴化雙酚A、雙酚F、雙酚S、萘酚類等各種 酚作為原料的酚醛樹脂；具有苯二甲基骨架之酚系酚醛樹脂、具有雙環戊二烯骨架之酚系酚醛樹脂、具有茀骨架之酚系酚醛樹脂等酚系酚醛樹脂；苯酚、甲酚類、乙基苯酚類、丁基苯酚類、辛基苯酚類等。此等之中較佳為酚系酚醛樹脂。 The liquid crystal sealing agent of the present invention can be phenolic using component (h) A compound of a hydroxyl group is used to further improve the adhesion strength. Examples of the compound having a phenolic hydroxyl group include bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, 4,4-biphenylphenol, and 2,2,6,6-tetramethyl- 4,4-biphenylphenol, 2,2-methylene-bis(4-methyl-6-tertiary butylphenol), ginseng (hydroxyphenyl)methane, pyrogallol, with diamethylene a phenol having a fluorenyl skeleton, a phenol having an anthracene skeleton such as a phenol skeleton, a polyphenol compound such as a phenolated polybutadiene, or a phenol, a cresol or an ethylphenol; Various kinds of butyl phenols, octyl phenols, bisphenol A, allyl phenols, brominated bisphenol A, bisphenol F, bisphenol S, naphthols, etc. Phenolic resin having phenol as a raw material; phenolic phenol resin having a benzene dimethyl skeleton; phenolic phenol resin having a dicyclopentadiene skeleton; phenolic phenol resin such as a phenolic phenol resin having an anthracene skeleton; phenol, cresol , ethyl phenols, butyl phenols, octyl phenols, and the like. Among these, a phenolic phenol resin is preferred.

本發明之液晶密封劑中，依進一步的需要，亦可使 用(甲基)丙烯酸酯的單體以及/或是寡聚體。作為那樣的單體、寡聚體，例如可舉出二季戊四醇(dipentaerythritol)與(甲基)丙烯酸之反應物，二季戊四醇-己內酯與(甲基)丙烯酸之反應物等，只要是對液晶的污染性低者則無特別限制。 In the liquid crystal sealing agent of the present invention, according to further needs, Monomers of (meth) acrylate and/or oligomers are used. Examples of such monomers and oligomers include a reaction product of dipentaerythritol and (meth)acrylic acid, a reaction product of dipentaerythritol-caprolactone and (meth)acrylic acid, and the like, as long as it is a liquid crystal. There are no special restrictions on the low polluting people.

本發明之液晶密封劑中，依進一步的需要，能調配 有機酸和咪唑等硬化促進劑、有機填充物、或是顏料、塗平劑、消泡劑、溶劑等添加劑。 In the liquid crystal sealing agent of the present invention, it can be formulated according to further needs A hardening accelerator such as an organic acid or imidazole, an organic filler, or an additive such as a pigment, a coating agent, an antifoaming agent, or a solvent.

作為獲得本發明之液晶密封劑之方法的一個例子， 有如下所示之方法。首先，在成分(a)(甲基)丙烯酸化環氧樹脂中，加熱溶解成分(b)光聚合起始劑，依需要加熱溶解成分(f)環氧樹脂、成分(h)具有酚性羥基之化合物。冷卻至室溫後，添加成分(c)無機充填劑、成分(d)有機醯肼化合物，依需要添加成分(e)熱自由基聚合起始劑、成分(g)矽烷偶合劑，進一步添加有機填充物、消泡劑、及塗平劑、溶劑等，藉由以眾所皆知的混合裝置，例如三輥磨機、混砂機、球磨機等來均勻混合，並以金屬網過濾，而能夠製造本發明之液晶密封劑。 As an example of a method of obtaining the liquid crystal sealing agent of the present invention, There are ways as shown below. First, in the component (a) (meth) acrylated epoxy resin, the dissolved component (b) photopolymerization initiator is heated, and the dissolved component (f) epoxy resin is heated as needed, and the component (h) has a phenolic hydroxyl group. Compound. After cooling to room temperature, the component (c) inorganic filler, component (d) organic hydrazine compound is added, and if necessary, component (e) thermal radical polymerization initiator, component (g) decane coupling agent is added, and organic is further added. The filler, the antifoaming agent, the leveling agent, the solvent, and the like are uniformly mixed by a well-known mixing device such as a three-roll mill, a sand mixer, a ball mill, etc., and are filtered by a metal mesh to enable The liquid crystal sealing agent of the present invention is produced.

本發明之液晶顯示單元，是以特定的間隔來對向地配置已形成有特定電極的一對基板，以本發明之液晶密封劑 來將周圍密封，將液晶密封在其間隙內而成。被密封的液晶種類沒有特別限定。在此，所謂基板，是由組合基板所構成，該組合基板是由玻璃、石英、塑膠、矽等所構成且至少一邊具有透光性。作為其製法，在本發明之液晶密封劑中，添加玻璃纖維等間隔物(間隙控制材料)後，於該一對基板其中一片基板，使用分配器(dispenser)、網版印刷裝置(screen printing apparatus)等將該液晶密封劑塗布後，依需要在80~120℃進行預硬化。之後，於由該液晶密封劑構成的堰的內側將液晶滴下，在真空中將另一片玻璃基板重疊，進行間隙成形。間隙形成後，藉由在90~130℃進行1~2小時硬化，能夠獲得本發明之液晶顯示單元。又，作為光熱併用型來使用時，以紫外線照射機對液晶密封劑照射紫外線予以光硬化。 紫外線照射量較佳為500~6000mJ/cm2，更佳為1000~4000mJ/cm2。之後依需要，藉由以90~130℃進行硬化1~2小時，能夠獲得本發明之液晶顯示單元。如此而獲得的本發明之液晶顯示單元，沒有由於液晶污染所導致的顯示不良，且黏著性、耐濕可靠性優異。作為間隔物，例如可舉出玻璃纖維、二氧化矽珠粒、聚合物珠粒等。其直徑，雖然依目的而不同，但通常為2~8μm，較佳為4~7μm。其使用量，相對於本發明之液晶密封劑，通常為0.1~4質量%，較佳為0.5~2質量%，更佳為0.9~1.5質量%左右。 In the liquid crystal display unit of the present invention, a pair of substrates on which specific electrodes have been formed are disposed oppositely at a predetermined interval, and the liquid crystal sealing agent of the present invention is used to seal the periphery and seal the liquid crystal in the gap. The type of liquid crystal to be sealed is not particularly limited. Here, the substrate is composed of a combination substrate which is made of glass, quartz, plastic, tantalum or the like and has at least one side having light transmissivity. In the liquid crystal sealing agent of the present invention, after a spacer such as a glass fiber (gap control material) is added, a dispenser or a screen printing apparatus is used for one of the pair of substrates. After the liquid crystal sealing agent is applied, it is pre-cured at 80 to 120 ° C as needed. Thereafter, the liquid crystal was dropped on the inside of the crucible composed of the liquid crystal sealing agent, and another glass substrate was superposed in a vacuum to form a gap. After the gap is formed, the liquid crystal display unit of the present invention can be obtained by hardening at 90 to 130 ° C for 1 to 2 hours. Moreover, when it is used as a photothermal type, the liquid crystal sealing agent is irradiated with ultraviolet rays by an ultraviolet irradiation machine, and it is photocured. The ultraviolet irradiation amount is preferably from 500 to 6,000 mJ/cm 2 , more preferably from 1,000 to 4,000 mJ/cm 2 . Thereafter, the liquid crystal display unit of the present invention can be obtained by curing at 90 to 130 ° C for 1 to 2 hours as needed. The liquid crystal display unit of the present invention thus obtained has no display failure due to liquid crystal contamination, and is excellent in adhesion and moisture resistance reliability. Examples of the spacer include glass fibers, ceria beads, polymer beads, and the like. The diameter, although depending on the purpose, is usually 2 to 8 μm , preferably 4 to 7 μm . The amount of use is usually from 0.1 to 4% by mass, preferably from 0.5 to 2% by mass, more preferably from 0.9 to 1.5% by mass, based on the liquid crystal sealing agent of the present invention.

本發明之液晶密封劑，由於紫外線所致之硬化後的黏著強度高，又在常溫下的黏著強度與在加熱環境下的黏著強度之差異小，所以對定向膜等有機膜的黏著性優異，可製 造安定的液晶顯示單元，以及實現長期可靠性優異的液晶顯示單元。又，本發明之液晶密封劑之硬化物，由於對於熱循環試驗亦安定，並且耐熱性、耐濕性亦優異，所以能夠實現可靠性優異的液晶顯示單元。另外，耐熱性能夠藉由測定玻璃轉移溫度來確認，而耐濕性能夠以測定置於高濕度環境下後的黏著強度來確認。並且，本發明之液晶密封劑，構成成分對液晶的溶出亦極少，可降低液晶顯示單元的顯示不良。又，由於保存安定性亦優異，所以適合液晶顯示單元的製造。又，使用本發明之液晶密封劑而製成的液晶顯示單元，電壓保持率高、離子密度低之類的作為液晶顯示單元必要之特性亦充足。 The liquid crystal sealing agent of the present invention has high adhesion strength after hardening due to ultraviolet rays, and has a small difference in adhesion strength at normal temperature and adhesion strength in a heating environment, and therefore has excellent adhesion to an organic film such as an alignment film. Can be made A stable liquid crystal display unit and a liquid crystal display unit excellent in long-term reliability. Further, since the cured product of the liquid crystal sealing agent of the present invention is stable in the heat cycle test and excellent in heat resistance and moisture resistance, it is possible to realize a liquid crystal display unit having excellent reliability. Further, the heat resistance can be confirmed by measuring the glass transition temperature, and the moisture resistance can be confirmed by measuring the adhesion strength after being placed in a high humidity environment. Further, in the liquid crystal sealing agent of the present invention, the constituent components have little elution of the liquid crystal, and the display failure of the liquid crystal display unit can be reduced. Moreover, since it is excellent in storage stability, it is suitable for manufacture of a liquid crystal display unit. Further, the liquid crystal display unit produced by using the liquid crystal sealing agent of the present invention has sufficient characteristics such as high voltage holding ratio and low ion density as a liquid crystal display unit.

[實施例] [Examples]

以下，藉由實施例、比較例來更詳細說明本發明，但本發明並不限定於實施例。另外，只要無特別之記載，本文中所記載之「份」以及「%」為質量基準。 Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples. In addition, the "parts" and "%" described herein are based on quality unless otherwise stated.

〔合成例1〕 [Synthesis Example 1] 〔雙酚A型環氧樹脂之環氧丙烯酸酯的合成〕 [Synthesis of epoxy acrylate of bisphenol A epoxy resin]

將雙酚A型環氧樹脂282.5g(製品名：YD-8125，新日鐵化學股份有限公司製)溶解於甲苯266.8g中，於其中加入二丁基羥基甲苯0.2g作為聚合抑制劑，昇溫至60℃。之後，加入環氧基100%當量的丙烯酸117.5g，進一步昇溫至80℃，於其中添加反應觸媒亦即三甲基氯化銨0.2g，於98℃攪拌約30小時，獲得反應液。藉由對此反應液進行水洗，並餾去甲 苯，獲得作為目的之雙酚A型的環氧丙烯酸酯540g。 282.5 g of bisphenol A type epoxy resin (product name: YD-8125, manufactured by Nippon Steel Chemical Co., Ltd.) was dissolved in 266.8 g of toluene, and 0.2 g of dibutylhydroxytoluene was added thereto as a polymerization inhibitor. Up to 60 ° C. Then, 117.5 g of 100% equivalent of acrylic acid of epoxy group was added, and the temperature was further raised to 80 ° C, and 0.2 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C for about 30 hours to obtain a reaction liquid. By washing the reaction liquid and distilling off Benzene obtained 540 g of a bisphenol A type epoxy acrylate as a target.

〔合成例2〕 [Synthesis Example 2] 〔雙酚A型環氧樹脂之環氧甲基丙烯酸酯的合成〕 [Synthesis of Epoxy Methacrylate of Bisphenol A Type Epoxy Resin]

將雙酚A型環氧樹脂282.5g(製品名：YD-8125，新日鐵化學股份有限公司製)溶解於甲苯266.8g中，於其中加入二丁基羥基甲苯0.2g作為聚合抑制劑，昇溫至60℃。之後，加入環氧基100%當量的甲基丙烯酸141.1g，進一步昇溫至80℃，於其中添加反應觸媒亦即三甲基氯化銨0.2g，於98℃攪拌約30小時，獲得反應液。藉由對此反應液進行水洗，並餾去甲苯，獲得作為目的之雙酚A型的環氧甲基丙烯酸酯540g。 282.5 g of bisphenol A type epoxy resin (product name: YD-8125, manufactured by Nippon Steel Chemical Co., Ltd.) was dissolved in 266.8 g of toluene, and 0.2 g of dibutylhydroxytoluene was added thereto as a polymerization inhibitor. Up to 60 ° C. Then, 141.1 g of methacrylic acid having 100% equivalent of an epoxy group was added, and the temperature was further raised to 80 ° C, and 0.2 g of a reaction catalyst, that is, trimethylammonium chloride was added thereto, and the mixture was stirred at 98 ° C for about 30 hours to obtain a reaction liquid. . The reaction liquid was washed with water, and toluene was distilled off to obtain 540 g of a desired bisphenol A type epoxy methacrylate.

〔合成例3〕 [Synthesis Example 3] 〔間苯二酚二縮水甘油醚之環氧丙烯酸酯的合成〕 [Synthesis of epoxy acrylate of resorcinol diglycidyl ether]

將間苯二酚二縮水甘油醚181.2g(Nagase ChemteX股份有限公司製)溶解於甲苯266.8g中，於其中添加二丁基羥基甲苯0.8g作為聚合抑制劑，昇溫至60℃。之後，加入環氧基100%當量的丙烯酸117.5g，進一步昇溫至80℃，於其中添加反應觸媒亦即三甲基氯化銨0.6g，於98℃攪拌約30小時，獲得反應液。藉由對此反應液進行水洗，並餾去甲苯，獲得作為目的之間苯二酚二縮水甘油醚的環氧丙烯酸酯293g。 181.2 g of resorcinol diglycidyl ether (manufactured by Nagase ChemteX Co., Ltd.) was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene was added thereto as a polymerization inhibitor, and the temperature was raised to 60 °C. Then, 117.5 g of 100% equivalent of acrylic acid of epoxy group was added, and the temperature was further raised to 80 ° C, and 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C for about 30 hours to obtain a reaction liquid. The reaction liquid was washed with water, and toluene was distilled off to obtain 293 g of an epoxy acrylate as the intended meta- benzenediol diglycidyl ether.

〔實施例1~3、比較例1~2〕 [Examples 1-3, Comparative Examples 1-2]

以下列表1所示之比例，在成分(a)(甲基)丙烯酸化 環氧樹脂中加熱溶解成分(b)光聚合起始劑、成分(f)環氧樹脂、成分(h)具有酚性羥基之化合物，並冷卻至室溫後，添加成分(c)無機充填劑、成分(d)有機醯肼化合物、成分(e)熱自由基聚合起始劑、成分(g)矽烷偶合劑，用三輥磨機均勻地混合。其次，藉由以金屬網過濾而製備實施例1~3之液晶密封劑。又，以同樣的步驟，混合表1所示之材料，製備比較例1~2之液晶密封劑。 The ratio shown in the following Table 1 is acrylated in the component (a) (meth) Heating the dissolved component in the epoxy resin (b) photopolymerization initiator, component (f) epoxy resin, component (h) having a phenolic hydroxyl group, and cooling to room temperature, adding component (c) inorganic filler The component (d) organic hydrazine compound, component (e) thermal radical polymerization initiator, and component (g) decane coupling agent were uniformly mixed by a three-roll mill. Next, the liquid crystal sealing agents of Examples 1 to 3 were prepared by filtration through a metal mesh. Further, the materials shown in Table 1 were mixed in the same manner to prepare liquid crystal sealing agents of Comparative Examples 1 and 2.

〔對ITO(氧化銦錫)基板之黏著強度測定〕 [Measurement of Adhesion Strength of ITO (Indium Tin Oxide) Substrate]

於獲得的液晶密封劑100g中添加5μm之玻璃纖維(PF-50S：日本電氣硝子股份有限公司製)1g作為間隔物，進行混合攪拌。將此液晶密封劑塗布於50mm×50mm之ITO(氧化銦錫)基板(470×370×0.7SP30ITO：GEOMATEC股份有限公司製)上，於該液晶密封劑上貼合1.5mm×1.5mm的玻璃片(將EAGLE XG：CORNING公司製者切成1.5mm見方)，以求取上述A〔MPa〕、B〔MPa〕、C〔MPa〕、D〔MPa〕之條件來測定剪切黏著強度。將結果顯示於表1。 1 g of a glass fiber (PF-50S: manufactured by Nippon Electric Glass Co., Ltd.) of 5 μm was added as a spacer to 100 g of the obtained liquid crystal sealing agent, and the mixture was stirred and mixed. This liquid crystal sealing agent was applied onto a 50 mm × 50 mm ITO (Indium Tin Oxide) substrate (470 × 370 × 0.7 SP30 ITO: manufactured by GEOMATEC Co., Ltd.), and a glass piece of 1.5 mm × 1.5 mm was attached to the liquid crystal sealing agent. (The EAGLE XG: manufactured by CORNING Co., Ltd. was cut into 1.5 mm squares), and the shear adhesion strength was measured under the conditions of A [MPa], B [MPa], C [MPa], and D [MPa]. The results are shown in Table 1.

〔對有機膜之黏著強度〕 [Adhesion strength to organic film]

於玻璃基板以旋轉塗布機塗布定向膜液(PIA-5540-05A；CHISSO股份有限公司製)，在60℃加熱板進行90秒的預烤，以220℃烤箱焙燒1小時。將此附定向膜之玻璃基板切成25mm×25mm、25mm×30mm之2種類，以紫外光臭氧清洗裝置(UVD-25U03：日本UV machine有限公 司製)進行80秒的清洗。紫外光臭氧處理後，於25mm×25mm附定向膜之玻璃基板，以分配器或是網版印刷機塗布液晶密封劑，貼合25mm×30mm附定向膜之玻璃基板，用UV照射機照射3000mJ/cm2的紫外線後，置入烤箱中於120℃予以熱硬化1小時。對獲得之試驗片，用黏著強度試驗機(SS-30WD：西進商事股份有限公司)，以測針壓住直線距離為距密封端2mm的位置來測定黏著強度。將結果顯示於表1。 The alignment film solution (PIA-5540-05A; manufactured by CHISSO Co., Ltd.) was applied to a glass substrate by a spin coater, and the plate was preheated at 60 ° C for 90 seconds, and baked at 220 ° C for 1 hour. The glass substrate with the oriented film was cut into two types of 25 mm × 25 mm and 25 mm × 30 mm, and washed with an ultraviolet ozone cleaning device (UVD-25U03: manufactured by Nippon UV Machine Co., Ltd.) for 80 seconds. After ultraviolet ozone treatment, a 25 mm × 25 mm glass substrate with an orientation film was applied, and a liquid crystal sealing agent was applied by a dispenser or a screen printing machine, and a 25 mm × 30 mm glass substrate with an orientation film was attached thereto, and irradiated with a UV irradiation machine at 3000 mJ/ After ultraviolet light of cm 2 , it was placed in an oven and heat-hardened at 120 ° C for 1 hour. For the obtained test piece, the adhesion strength was measured by an adhesion strength tester (SS-30WD: Xijin Commercial Co., Ltd.) with the stylus pressed against the straight line distance of 2 mm from the sealed end. The results are shown in Table 1.

①根據合成例1合成 1 synthesized according to Synthesis Example 1

②根據合成例2合成 2 synthesized according to Synthesis Example 2

③根據合成例3合成 3 synthesized according to Synthesis Example 3

④根據國際公開第2006/027982號記載之方法合成 4 Synthesized according to the method described in International Publication No. 2006/027982

⑤SS-15(大阪化成股份有限公司製) 5SS-15 (made by Osaka Chemical Industry Co., Ltd.)

⑥SPC(C.I.化成股份有限公司) 6SPC (C.I. Chemical Co., Ltd.)

⑦IXE-100(東亞合成股份有限公司) 7IXE-100 (East Asia Synthetic Co., Ltd.)

⑧D-600(日本滑石股份有限公司製) 8D-600 (made by Japan Talc Co., Ltd.)

⑨SDH(日本FINECHEM股份有限公司製) 9SDH (made by Japan FINECHEM Co., Ltd.)

⑩以國際公開第2011/06190號記載之方法合成 10 Synthesized by the method described in International Publication No. 2011/06190

⑪YD-8125(新日鐵化學股份有限公司製) 11YD-8125 (manufactured by Nippon Steel Chemical Co., Ltd.)

⑫KBM-603(信越化學工業股份有限公司) 12KBM-603 (Shin-Etsu Chemical Industry Co., Ltd.)

⑬Sila-Ace S-510(CHISSO股份有限公司製) 13Sila-Ace S-510 (manufactured by CHISSO Co., Ltd.)

⑭PN-152(日本化藥股份有限公司製) 14PN-152 (manufactured by Nippon Kayaku Co., Ltd.)

⑮Paraloid EXL-2655(Rohm and Haas公司製) 15Paraloid EXL-2655 (manufactured by Rohm and Haas)

⑯PET-30(日本化藥股份有限公司製) 16PET-30 (made by Nippon Kayaku Co., Ltd.)

根據表1的結果，確認到實施例1~3之液晶密封劑，對定向膜，亦即對有機膜之黏著強度非常強。因此，本發明之液晶密封劑，即使是將其塗布於定向膜上之液晶顯示單元的設計，仍可實現可靠性優異的液晶顯示單元。 According to the results of Table 1, it was confirmed that the liquid crystal sealing agents of Examples 1 to 3 had a very strong adhesion to the oriented film, that is, to the organic film. Therefore, the liquid crystal sealing agent of the present invention can realize a liquid crystal display unit excellent in reliability even in the design of a liquid crystal display unit which is applied to an alignment film.

[產業利用性] [Industry Utilization]

本發明之液晶密封劑，與特別是定向膜等有機膜之黏著性非常優異，即使在各式各樣環境下也不易引起剝離。因此，可實現在各式各樣環境中能使用的液晶顯示單元。又，由於低液晶污染性、耐熱性、耐熱循環性、耐濕性等一般特性亦優異，故可實現長期可靠性優異的液晶顯示單元。 The liquid crystal sealing agent of the present invention is excellent in adhesion to an organic film such as an oriented film, and is not easily peeled off even in various environments. Therefore, a liquid crystal display unit that can be used in a wide variety of environments can be realized. Further, since the general characteristics such as low liquid crystal contamination, heat resistance, heat cycle resistance, and moisture resistance are also excellent, a liquid crystal display unit excellent in long-term reliability can be realized.

Claims (13)

一種液晶滴下工法用液晶密封劑，其在照射3000mJ/cm2的紫外線後並在120℃環境下予以硬化1小時後，將該硬化後的液晶密封劑於25℃時對於ITO(氧化銦錫)基板的黏著強度設為A〔MPa〕，並將前述硬化後的液晶密封劑於120℃時的黏著強度設為B〔MPa〕，且將僅以3000mJ/cm2的紫外線予以硬化後的液晶密封劑於25℃時對於ITO(氧化銦錫)基板的黏著強度設為C〔MPa〕時，前述A、B、及C滿足下列式(1)及(2)所表示之關係式：B≧0.5×A (1) C≧0.3×A (2)。 A liquid crystal sealing agent for liquid crystal dropping method, which is cured by irradiating ultraviolet rays of 3000 mJ/cm 2 and cured at 120 ° C for 1 hour, and then curing the cured liquid crystal sealing agent at 25 ° C for ITO (indium tin oxide) The adhesion strength of the substrate is A [MPa], and the adhesion strength of the liquid crystal sealing agent after curing at 120 ° C is B [MPa], and the liquid crystal sealing is performed by curing only ultraviolet rays of 3000 mJ/cm 2 . When the adhesive strength of the ITO (indium tin oxide) substrate is C [MPa] at 25 ° C, the above A, B, and C satisfy the relationship represented by the following formulas (1) and (2): B ≧ 0.5 ×A (1) C≧0.3×A (2). 如請求項1所述之液晶滴下工法用液晶密封劑，其中，將僅以3000mJ/cm2的紫外線予以硬化後的液晶密封劑於120℃時對於ITO(氧化銦錫)基板的黏著強度設為D〔MPa〕時，前述A及D滿足下列式(3)所表示之關係式：D≧0.3×A (3)。 The liquid crystal sealing agent for liquid crystal dropping method according to claim 1, wherein the liquid crystal sealing agent which has been cured by ultraviolet rays of only 3000 mJ/cm 2 has an adhesion strength to an ITO (indium tin oxide) substrate at 120 ° C. In the case of D [MPa], the above A and D satisfy the relationship represented by the following formula (3): D ≧ 0.3 × A (3). 如請求項1所述之液晶滴下工法用液晶密封劑，其中含有：成分(a)(甲基)丙烯酸化環氧樹脂、成分(b)光聚合起始劑、成分(c)無機充填劑、及成分(d)有機醯肼化合物。 The liquid crystal sealing agent for liquid crystal dropping method according to claim 1, which comprises: component (a) (meth) acrylated epoxy resin, component (b) photopolymerization initiator, component (c) inorganic filler, And component (d) an organic hydrazine compound. 如請求項3所述之液晶滴下工法用液晶密封劑，其中，更含有成分(e)熱自由基聚合起始劑。 The liquid crystal sealing agent for a liquid crystal dropping method according to claim 3, further comprising a component (e) a thermal radical polymerization initiator. 如請求項4所述之液晶滴下工法用液晶密封劑，其中，前述成分(e)熱自由基聚合起始劑為1,2-雙(三甲基矽烷氧基) -1,1,2,2-四苯基乙烷。 The liquid crystal sealing agent for liquid crystal dropping method according to claim 4, wherein the component (e) thermal radical polymerization initiator is 1,2-bis(trimethyldecyloxy) -1,1,2,2-tetraphenylethane. 如請求項3所述之液晶滴下工法用液晶密封劑，其中，更含有成分(f)環氧樹脂。 The liquid crystal sealing agent for liquid crystal dropping method according to claim 3, further comprising a component (f) epoxy resin. 如請求項3所述之液晶滴下工法用液晶密封劑，其中，更含有成分(g)矽烷偶合劑。 The liquid crystal sealing agent for liquid crystal dropping method according to claim 3, further comprising a component (g) decane coupling agent. 如請求項7所述之液晶滴下工法用液晶密封劑，其中，前述成分(g)矽烷偶合劑為胺基矽烷偶合劑。 The liquid crystal sealing agent for a liquid crystal dropping method according to claim 7, wherein the component (g) decane coupling agent is an amino decane coupling agent. 如請求項7所述之液晶滴下工法用液晶密封劑，其中，前述成分(g)矽烷偶合劑為胺基矽烷偶合劑與環氧基矽烷偶合劑的混合物。 The liquid crystal sealing agent for liquid crystal dropping method according to claim 7, wherein the component (g) decane coupling agent is a mixture of an amino decane coupling agent and an epoxy decane coupling agent. 如請求項3所述之液晶滴下工法用液晶密封劑，其中，更含有成分(h)具有酚性羥基之化合物。 The liquid crystal sealing agent for a liquid crystal dropping method according to claim 3, further comprising a compound having a phenolic hydroxyl group as component (h). 如請求項10所述之液晶滴下工法用液晶密封劑，其中，前述成分(h)具有酚性羥基之化合物為酚系酚醛樹脂。 The liquid crystal sealing agent for a liquid crystal dropping method according to claim 10, wherein the compound having a phenolic hydroxyl group in the component (h) is a phenolic phenol resin. 一種液晶顯示單元之製造方法，其在由2片基板所構成之液晶顯示單元中，於其中一片基板所形成之由如請求項1至11中任一項所述之液晶滴下工法用液晶密封劑所構成的堰的內側將液晶滴下後，貼合另一片基板，之後藉由紫外線及/或熱來將前述液晶滴下工法用液晶密封劑予以硬化。 A liquid crystal display unit manufacturing method for liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 11, wherein a liquid crystal display unit comprising two substrates is formed in one of the substrates. After the liquid crystal is dropped on the inside of the crucible, the other substrate is bonded, and then the liquid crystal sealing agent for liquid crystal dropping method is cured by ultraviolet rays and/or heat. 一種液晶顯示單元，是以一種硬化物黏著而成，該硬化物是將如請求項1至11中任一項所述之液晶滴下工法用液晶密封劑硬化而獲得。 A liquid crystal display unit obtained by curing a liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 11, which is obtained by curing a liquid crystal sealing agent according to any one of claims 1 to 11.
TW102124978A 2012-07-12 2013-07-11 Liquid crystal sealing agent and liquid crystal display cell using same TW201420735A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2012156706 2012-07-12

Publications (1)

Publication Number Publication Date
TW201420735A true TW201420735A (en) 2014-06-01

Family

ID=49916170

Family Applications (1)

Application Number Title Priority Date Filing Date
TW102124978A TW201420735A (en) 2012-07-12 2013-07-11 Liquid crystal sealing agent and liquid crystal display cell using same

Country Status (5)

Country Link
JP (1) JP6249946B2 (en)
KR (1) KR20150036253A (en)
CN (1) CN104428710A (en)
TW (1) TW201420735A (en)
WO (1) WO2014010731A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6478788B2 (en) * 2015-04-24 2019-03-06 日本化薬株式会社 Liquid crystal sealing agent and liquid crystal display cell using the same
CN114369210A (en) * 2021-12-25 2022-04-19 天津市新丽华色材有限责任公司 Acrylic acid modified epoxy resin, preparation method thereof, copper-free silver mirror back protective coating and preparation method thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2846842B2 (en) * 1995-06-22 1999-01-13 松下電器産業株式会社 Liquid crystal sealing material and liquid crystal display device
JPH1171458A (en) * 1996-08-14 1999-03-16 Asahi Optical Co Ltd Transparent resin and composite with adhesiveness, ultraviolet-curable composition for coating film formation, anti-reflection glass with scattering prevention function, cushioning material, ultraviolet-cutting sheet, ultraviolet-cutting filter for television, filter for vdt, and high-refractive-index primer composition and production of lens with primer using the primer composition
JP2002317172A (en) * 2001-04-20 2002-10-31 Nippon Kayaku Co Ltd Sealing medium resin composition for liquid crystal display
JP4532883B2 (en) * 2003-06-04 2010-08-25 積水化学工業株式会社 Photocurable resin composition, liquid crystal display element sealing agent, liquid crystal display element sealing agent, liquid crystal display element vertical conduction material, and liquid crystal display device
JP4391177B2 (en) * 2003-09-17 2009-12-24 株式会社リコー Sealant for photo-curable display element
JP4645804B2 (en) * 2004-10-06 2011-03-09 株式会社スリーボンド Curable composition for liquid crystal display device
JP4639684B2 (en) * 2004-07-26 2011-02-23 株式会社スリーボンド Sealant for liquid crystal display
CN102428138B (en) * 2009-05-19 2014-03-26 法国阿科玛 Encapsulant compositions, methods of manufacture and uses thereof
KR101618397B1 (en) * 2009-07-01 2016-05-04 니폰 가야꾸 가부시끼가이샤 Liquid crystal sealing agent for liquid crystal dropping method and liquid crystal display cell using same
WO2011063082A2 (en) * 2009-11-20 2011-05-26 3M Innovative Properties Company Surface-modified adhesives
KR20130140544A (en) * 2010-07-20 2013-12-24 니폰 가야꾸 가부시끼가이샤 Liquid crystal sealing agent and liquid crystal display cell using same

Also Published As

Publication number Publication date
JPWO2014010731A1 (en) 2016-06-23
KR20150036253A (en) 2015-04-07
JP6249946B2 (en) 2017-12-20
CN104428710A (en) 2015-03-18
WO2014010731A1 (en) 2014-01-16

Similar Documents

Publication Publication Date Title
JP6478313B2 (en) Liquid crystal sealant and liquid crystal display cell using the same
TWI362542B (en)
TW201420736A (en) Liquid-crystal sealant and LCD cell using same
JP2018104662A (en) Photocurable resin composition and electronic component sealant
TW201512748A (en) Liquid crystal sealing agent and liquid crystal display cell using the same
TWI506347B (en) Sealant for liquid crystal and liquid crystal display cell using the same
TW201609931A (en) Liquid crystal sealant and liquid crystal display cell using the same
JP2016024243A (en) Liquid crystal sealant and liquid crystal cell using the same
TWI543992B (en) A liquid crystal sealant and a liquid crystal display unit using the liquid crystal sealant
WO2007148518A1 (en) Liquid crystal sealing agent and liquid crystal display cell utilizing the same
TW201529654A (en) Method for producing resin composition
JP5645765B2 (en) Liquid crystal sealant and liquid crystal display cell using the same
TW201619213A (en) Liquid crystal sealing agent and liquid crystal display cell using same
TW201420735A (en) Liquid crystal sealing agent and liquid crystal display cell using same
JP5773782B2 (en) Novel (meth) acrylic resin and resin composition using the same
TWI429997B (en) A liquid crystal sealant and a liquid crystal display unit using the same
JP5748273B2 (en) Liquid crystal sealant and liquid crystal display cell using the same
KR20180076338A (en) Liquid crystal sealing agent, and liquid crystal display cell using the same
TW201615795A (en) Liquid crystal sealing agent and liquid crystal display cell using the same
JP7136536B2 (en) display sealant
JP6659417B2 (en) Liquid crystal sealant and liquid crystal display cell using the same
TW201619285A (en) Liquid crystal sealing agent and liquid crystal display cell using the same and manufacturing method for liquid crystal display cell
JP2018105989A (en) Sealing agent for display device and display device using the same
TW201708490A (en) Liquid crystal sealing agent and liquid crystal display cell using the same
JP6478788B2 (en) Liquid crystal sealing agent and liquid crystal display cell using the same