JP4668538B2 - Curable resin composition, sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element - Google Patents
Curable resin composition, sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element Download PDFInfo
- Publication number
- JP4668538B2 JP4668538B2 JP2004044979A JP2004044979A JP4668538B2 JP 4668538 B2 JP4668538 B2 JP 4668538B2 JP 2004044979 A JP2004044979 A JP 2004044979A JP 2004044979 A JP2004044979 A JP 2004044979A JP 4668538 B2 JP4668538 B2 JP 4668538B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- epoxy resin
- meth
- dropping method
- resin composition
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 104
- 238000000034 method Methods 0.000 title claims description 71
- 239000003795 chemical substances by application Substances 0.000 title claims description 43
- 238000007789 sealing Methods 0.000 title claims description 35
- 239000000463 material Substances 0.000 title claims description 12
- 239000011342 resin composition Substances 0.000 title description 41
- 229920000647 polyepoxide Polymers 0.000 claims description 54
- 239000003822 epoxy resin Substances 0.000 claims description 50
- 125000000524 functional group Chemical group 0.000 claims description 25
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 17
- 239000000565 sealant Substances 0.000 claims description 17
- 230000001588 bifunctional effect Effects 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 229920001187 thermosetting polymer Polymers 0.000 claims description 14
- 239000010419 fine particle Substances 0.000 claims description 8
- 239000007870 radical polymerization initiator Substances 0.000 claims description 2
- -1 acrylic acid-modified epoxy resins Chemical class 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 20
- 125000003700 epoxy group Chemical group 0.000 description 18
- 239000000758 substrate Substances 0.000 description 16
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 9
- 244000028419 Styrax benzoin Species 0.000 description 9
- 235000000126 Styrax benzoin Nutrition 0.000 description 9
- 235000008411 Sumatra benzointree Nutrition 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 235000019382 gum benzoic Nutrition 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229960002130 benzoin Drugs 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
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- 238000001723 curing Methods 0.000 description 5
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- 238000002156 mixing Methods 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
- WORJRXHJTUTINR-UHFFFAOYSA-N 1,4-dioxane;hydron;chloride Chemical compound Cl.C1COCCO1 WORJRXHJTUTINR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000004843 novolac epoxy resin Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
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- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical class NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
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- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
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Description
本発明は、滴下工法による液晶表示素子の製造にシール剤として用いた場合にでも、作業性に優れ、かつ、液晶汚染を引き起こしにくく色むらが少ない高品位な画像の液晶表示素子を製造することができる硬化性樹脂組成物、該硬化性樹脂組成物からなる液晶滴下工法用シール剤、上下導通材料及び液晶表示素子に関する。 The present invention is to produce a liquid crystal display element having a high-quality image that is excellent in workability and hardly causes liquid crystal contamination even when used as a sealant in the production of a liquid crystal display element by a dropping method. The present invention relates to a curable resin composition capable of forming a liquid crystal, a sealant for a liquid crystal dropping method comprising the curable resin composition, a vertical conduction material, and a liquid crystal display element.
従来、液晶表示セル等の液晶表示素子は、２枚の電極付き透明基板を、所定の間隔をおいて対向させ、その周囲を硬化性樹脂組成物からなるシール剤で封着してセルを形成し、その一部に設けられた液晶注入口からセル内に液晶を注入し、その液晶注入口をシール剤又は封口剤を用いて封止することにより作製されていた。 Conventionally, a liquid crystal display element such as a liquid crystal display cell forms a cell by facing two transparent substrates with electrodes facing each other at a predetermined interval and sealing the periphery with a sealing agent made of a curable resin composition. However, it was produced by injecting liquid crystal into the cell from a liquid crystal injection port provided in a part thereof, and sealing the liquid crystal injection port with a sealing agent or a sealing agent.
この方法では、まず、２枚の電極付き透明基板のいずれか一方に、スクリーン印刷により熱硬化性シール剤を用いた液晶注入口を設けたシールパターンを形成し、６０〜１００℃でプリベイクを行いシール剤中の溶剤を乾燥させる。次いで、スペーサーを挟んで２枚の基板を対向させてアライメントを行い貼り合わせ、１１０〜２２０℃で１０〜９０分間熱プレスを行いシール近傍のギャップを調整した後、オーブン中で１１０〜２２０℃で１０〜１２０分間加熱しシール剤を本硬化させる。次いで、液晶注入口から液晶を注入し、最後に封口剤を用いて液晶注入口を封止して、液晶表示素子を作製していた。 In this method, first, a seal pattern provided with a liquid crystal injection port using a thermosetting sealant is formed on one of two transparent substrates with electrodes by screen printing, and prebaked at 60 to 100 ° C. Dry the solvent in the sealant. Next, alignment is performed with the two substrates facing each other with a spacer interposed therebetween, and the gap in the vicinity of the seal is adjusted by performing hot pressing at 110 to 220 ° C. for 10 to 90 minutes, and then at 110 to 220 ° C. in an oven. Heat for 10 to 120 minutes to fully cure the sealant. Next, liquid crystal was injected from the liquid crystal injection port, and finally, the liquid crystal injection port was sealed using a sealing agent to produce a liquid crystal display element.
しかし、この作製方法によると、熱歪により位置ズレ、ギャップのバラツキ、シール剤と基板との密着性の低下等が発生する；残留溶剤が熱膨張して気泡が発生しキャップのバラツキやシールパスが発生する；シール硬化時間が長い；プリベイクプロセスが煩雑；溶剤の揮発によりシール剤の使用可能時間が短い；液晶の注入に時間がかかる等の問題があった。とりわけ、近年の大型の液晶表示装置にあっては、液晶の注入に非常に時間がかかることが大きな問題となっていた。 However, according to this manufacturing method, the positional displacement, gap variation, decrease in adhesion between the sealing agent and the substrate, etc. occur due to thermal strain; residual solvent thermally expands to generate bubbles, resulting in cap variation and seal path. The seal curing time is long; the prebaking process is complicated; the usable time of the sealant is short due to the volatilization of the solvent; and it takes time to inject liquid crystal. In particular, in a large liquid crystal display device in recent years, it takes a very long time to inject liquid crystal.
これに対して、光硬化熱硬化併用型シール剤を用いた滴下工法と呼ばれる液晶表示素子の製造方法が検討されている。滴下工法では、まず、２枚の電極付き透明基板の一方に、スクリーン印刷により長方形状のシールパターンを形成する。次いで、シール剤未硬化の状態で液晶の微小滴を透明基板の枠内全面に滴下塗布し、すぐに他方の透明基板を重ねあわせ、シール部に紫外線を照射して仮硬化を行う。その後、液晶アニール時に加熱して本硬化を行い、液晶表示素子を作製する。基板の貼り合わせを減圧下で行うようにすれば、極めて高い効率で液晶表示素子を製造することができる。今後はこの滴下工法が液晶表示装置の製造方法の主流となると期待されている。 On the other hand, a manufacturing method of a liquid crystal display element called a dripping method using a photocuring / thermosetting sealant has been studied. In the dropping method, first, a rectangular seal pattern is formed on one of the two transparent substrates with electrodes by screen printing. Next, fine droplets of liquid crystal are dropped and applied to the entire surface of the transparent substrate frame in an uncured state of the sealant, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with ultraviolet rays for temporary curing. Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency. In the future, this dripping method is expected to become the mainstream of liquid crystal display manufacturing methods.
このような滴下工法に用いる液晶滴下工法用シール剤として、特許文献１及び特許文献２には、エポキシ基の一部が（メタ）アクリル酸で変性された（メタ）アクリル酸変性エポキシ樹脂からなるものが開示されている。このような（メタ）アクリル酸変性エポキシ樹脂は、光照射、加熱のいずれによっても硬化することから、滴下工法に用いる液晶滴下工法用シール剤として好適である。しかしながら、これらの（メタ）アクリル酸変成エポキシ樹脂は、一般に粘度が高い傾向がある。とりわけ熱硬化剤等として粉状物を併用した場合には、樹脂組成物の粘度が極めて高くなり、液晶滴下工法用シール剤として用いた場合に作業性に劣るという問題があった。 As a sealing agent for a liquid crystal dropping method used in such a dropping method, Patent Document 1 and Patent Document 2 are composed of a (meth) acrylic acid-modified epoxy resin in which a part of an epoxy group is modified with (meth) acrylic acid. Are disclosed. Such a (meth) acrylic acid-modified epoxy resin is suitable as a sealing agent for a liquid crystal dropping method used for the dropping method because it is cured by either light irradiation or heating. However, these (meth) acrylic acid-modified epoxy resins generally tend to have high viscosity. In particular, when a powdered material is used in combination as a thermosetting agent, the viscosity of the resin composition becomes extremely high, and there is a problem that workability is inferior when used as a sealing agent for a liquid crystal dropping method.
そこで従来は、樹脂組成物全体の粘度を低下させるために、低粘度のエポキシ樹脂や低粘度のアクリル酸エステル等を混合することが行われていた。しかしながら、滴下工法では、その工程上、未硬化の状態のシール剤が液晶に直接触れてしまうことから、極性の小さい低粘度のエポキシ樹脂や低粘度のアクリル酸エステルが液晶に溶出してしまうことがあり、得られる液晶表示素子においては、液晶の配向乱れによると思われる色むら等の表示不良が生じやすいという問題点があった。これに対して、液晶の汚染を抑制するために、低粘度のアクリル酸エステルとしてエポキシアクリレートを用いる方法が提案されているが、得られる硬化性樹脂組成物をシール剤として用いた場合に接着強度が劣ってしまうという問題があった。 Therefore, conventionally, in order to reduce the viscosity of the entire resin composition, a low-viscosity epoxy resin, a low-viscosity acrylic ester, or the like has been mixed. However, in the dripping method, the uncured sealant directly touches the liquid crystal in the process, so that low-viscosity epoxy resin with low polarity and low-viscosity acrylic ester are eluted into the liquid crystal. In the obtained liquid crystal display element, there is a problem that display defects such as uneven color are likely to occur due to disordered alignment of the liquid crystal. On the other hand, in order to suppress the contamination of the liquid crystal, a method using an epoxy acrylate as a low-viscosity acrylic ester has been proposed. There was a problem of being inferior.
本発明は、上記現状に鑑み、滴下工法による液晶表示素子の製造に用いた場合にでも、作業性に優れ、かつ、液晶汚染を引き起こしにくく色むらが少ない高品位な画像の液晶表示素子を製造することができる硬化性樹脂組成物、該硬化性樹脂組成物からなる液晶滴下工法用シール剤、上下導通材料及び液晶表示素子を提供することを目的とする。 In view of the above situation, the present invention produces a high-quality liquid crystal display element that is excellent in workability and hardly causes color contamination even when used in the production of a liquid crystal display element by a dropping method. An object of the present invention is to provide a curable resin composition that can be used, a liquid crystal dropping method sealant comprising the curable resin composition, a vertical conduction material, and a liquid crystal display element.
本発明は、１分子内に（メタ）アクリル基とエポキシ基とをそれぞれ少なくとも１つ以上有する化合物、−ＯＨ基及び／又は−ＣＯＮＨ−結合である水素結合性官能基を有し水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である２官能以上の液状エポキシ樹脂（ただし、（メタ）アクリル基を有するものを除く）、熱硬化剤及び光ラジカル重合開始剤を含有する硬化性樹脂組成物である。
以下に本発明を詳述する。
The present invention relates to a compound having at least one (meth) acryl group and an epoxy group in one molecule , a hydrogen bonding functional group having a —OH group and / or —CONH— bond, and a hydrogen bonding functional group. A bifunctional or higher functional liquid epoxy resin having a valence of 1.5 × 10 −3 mol / g or more (excluding those having a (meth) acryl group) , a thermosetting agent, and a radical photopolymerization initiator. It is a curable resin composition.
The present invention is described in detail below.
本発明の硬化性樹脂組成物は、樹脂成分として、１分子内に（メタ）アクリル基とエポキシ基とをそれぞれ少なくとも１つ以上有する化合物と、水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である２官能以上の液状エポキシ樹脂とを含有する。
上記１分子内に（メタ）アクリル基とエポキシ基とをそれぞれ少なくとも１つ以上有する化合物は、光照射、加熱のいずれによっても硬化することから、これを含有する本発明の硬化性樹脂組成物は液晶滴下工法用シール剤として好適である。また、上記液状エポキシ樹脂は、本発明の硬化性樹脂組成物の粘度を調整して液晶滴下工法用シール剤として用いたときの作業性を向上させる役割を有する。
The curable resin composition of the present invention has, as a resin component, a compound having at least one (meth) acryl group and an epoxy group in one molecule, and a hydrogen bondable functional group value of 1.5 × 10 − 2 or more functional liquid epoxy resin which is 3 mol / g or more.
Since the compound having at least one (meth) acryl group and epoxy group in one molecule is cured by either light irradiation or heating, the curable resin composition of the present invention containing the compound is Suitable as a sealing agent for liquid crystal dropping method. Moreover, the said liquid epoxy resin has a role which improves workability | operativity when adjusting the viscosity of the curable resin composition of this invention and using it as a sealing compound for liquid crystal dropping methods.
上記１分子内に（メタ）アクリル基とエポキシ基とをそれぞれ少なくとも１つ以上有する化合物としては特に限定されず、例えば、（メタ）アクリル酸変性エポキシ樹脂、ウレタン変性（メタ）アクリルエポキシ樹脂等が挙げられる。 The compound having at least one (meth) acryl group and epoxy group in one molecule is not particularly limited, and examples thereof include (meth) acrylic acid-modified epoxy resins and urethane-modified (meth) acryl epoxy resins. Can be mentioned.
上記（メタ）アクリル酸変性エポキシ樹脂は、例えば、エポキシ樹脂と（メタ）アクリル酸とを常法に従って塩基性触媒の存在下で反応することにより得ることができる。ここで、エポキシ樹脂と（メタ）アクリル酸との配合量を調節することにより、所望のアクリル化率のエポキシ樹脂を得ることができる。 The (meth) acrylic acid-modified epoxy resin can be obtained, for example, by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. Here, the epoxy resin of a desired acrylation rate can be obtained by adjusting the compounding quantity of an epoxy resin and (meth) acrylic acid.
上記（メタ）アクリル酸変性エポキシ樹脂の原料となるエポキシ樹脂としては、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、トリスフェノールノボラック型エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、２，２’−ジアリルビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、レゾルシノール型エポキシ樹脂、グリシジルアミン類等が挙げられる。 Examples of the epoxy resin used as a raw material for the (meth) acrylic acid-modified epoxy resin include, for example, a phenol novolac epoxy resin, a cresol novolac epoxy resin, a biphenyl novolac epoxy resin, a trisphenol novolac epoxy resin, and a dicyclopentadiene novolac type. Epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, propylene oxide added bisphenol A type epoxy resin, Biphenyl type epoxy resin, naphthalene type epoxy resin, resorcinol type epoxy resin, glycidylamines and the like can be mentioned.
上記（メタ）アクリル酸変性エポキシ樹脂の原料となるエポシキ樹脂のうち市販されているものとしては、例えば、フェノールノボラック型としては、エピクロンＮ−７４０、エピクロンＮ−７７０、エピクロンＮ−７７５（以上、大日本インキ化学社製）、エピコート１５２、エピコート１５４（以上、ジャパンエポキシレジン社製）が挙げられ、クレゾールノボラック型としては、エピクロンＮ−６６０、エピクロンＮ−６６５、エピクロンＮ−６７０、エピクロンＮ−６７３、エピクロンＮ−６８０、エピクロンＮ−６９５、エピクロンＮ−６６５−ＥＸＰ、エピクロンＮ−６７２−ＥＸＰ（以上、大日本インキ化学社製）等が挙げられ、ビフェニルノボラック型エポキシ樹脂としては、ＮＣ−３０００Ｓ（日本化薬社製）が挙げられ、トリスフェノールノボラック型エポキシ樹脂としては、ＥＰＰＮ−５０１Ｈ、ＥＰＰＮ−５０１Ｈ（以上、日本化薬社製）が挙げられ、ジシクロペンタジエンノボラック型エポキシ樹脂としては、ＮＣ−７０００Ｌ（日本化薬社製）が挙げられ、ビスフェノールＡ型エポキシ樹脂としては、エピクロン８４０Ｓ、エピクロン８５０ＣＲＰ（以上、大日本インキ化学工業社製）が挙げられ、ビスフェノールＦ型エポキシ樹脂としては、エピコート８０７（ジャパンエポキシレジン社製）、エピクロン８３０（大日本インキ化学工業社製）が挙げられ、２，２’−ジアリルビスフェノールＡ型エポキシ樹脂としては、ＲＥ３１０ＮＭ（日本化薬社製）が挙げられ、水添ビスフェノール型エポキシ樹脂としては、エピクロン７０１５（大日本インキ化学工業社製）が挙げられ、プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂としては、エポキシエステル３００２Ａ（共栄社化学社製）が挙げられ、ビフェニル型エポキシ樹脂としては、エピコートＹＸ−４０００Ｈ、ＹＬ−６１２１Ｈ（以上、ジャパンエポキシレジン社製）が挙げられ、ナフタレン型エポキシ樹脂としては、エピクロンＨＰ−４０３２（大日本インキ化学社製）が挙げられ、レゾルシノール型エポキシ樹脂としては、デナコールＥＸ−２０１（ナガセケムテックス社製）が挙げられ、グリシジルアミン類としては、エピクロン４３０（大日本インキ化学社製）、エピコート６３０（ジャパンエポキシレジン社製）等が挙げられる。 Examples of commercially available epoxy resins used as raw materials for the (meth) acrylic acid-modified epoxy resin include, for example, as a phenol novolak type, Epicron N-740, Epicron N-770, Epicron N-775 (or more, Dainippon Ink Chemical Co., Ltd.), Epicoat 152, Epicoat 154 (above, Japan Epoxy Resin Co., Ltd.), and cresol novolak types include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N- 673, Epicron N-680, Epicron N-695, Epicron N-665-EXP, Epicron N-672-EXP (manufactured by Dainippon Ink and Chemicals, Inc.) and the like. As the biphenyl novolac type epoxy resin, NC- 3000S (Nippon Kayaku Co., Ltd.) Examples of the trisphenol novolac type epoxy resin include EPPN-501H and EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.). Examples of the dicyclopentadiene novolac type epoxy resin include NC-7000L (manufactured by Nippon Kayaku Co., Ltd.). Examples of the bisphenol A type epoxy resin include Epicron 840S and Epicron 850CRP (manufactured by Dainippon Ink and Chemicals, Inc.). Examples of the bisphenol F type epoxy resin include Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.) and Epicron. 830 (manufactured by Dainippon Ink & Chemicals, Inc.), and 2,2′-diallyl bisphenol A type epoxy resin includes RE310NM (manufactured by Nippon Kayaku Co., Ltd.), and hydrogenated bisphenol type epoxy resin includes epiclone. 7015 (Dainippon Inn Chemical Industry Co., Ltd.), propylene oxide-added bisphenol A type epoxy resin includes epoxy ester 3002A (manufactured by Kyoeisha Chemical Co., Ltd.), and biphenyl type epoxy resins include Epicoat YX-4000H, YL-6121H (above) , Manufactured by Japan Epoxy Resin Co., Ltd.), as the naphthalene type epoxy resin, Epiklon HP-4032 (produced by Dainippon Ink & Chemicals) is used, and as the resorcinol type epoxy resin, Denacol EX-201 (Nagase ChemteX Corporation) is used. Examples of the glycidylamines include Epicron 430 (Dainippon Ink Chemical Co., Ltd.) and Epicoat 630 (Japan Epoxy Resin Co., Ltd.).
上記エポキシ樹脂の部分（メタ）アクリル化物は、例えば、エポキシ樹脂と（メタ）アクリル酸とを、常法に従って塩基性触媒の存在下で反応することにより得られる。エポキシ樹脂と（メタ）アクリル酸との配合量を適宜変更する事により所望のアクリル化率のエポキシ樹脂を得る事が可能である。 The partially (meth) acrylated product of the epoxy resin can be obtained, for example, by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. It is possible to obtain an epoxy resin having a desired acrylation rate by appropriately changing the blending amount of the epoxy resin and (meth) acrylic acid.
上記ウレタン変成（メタ）アクリルエポキシ樹脂は、例えば、以下の方法によって得られるものである。（１）２官能以上のイソシアネートに水酸基を有する（メタ）アクリルモノマー及びグリシドールを反応させる方法（この場合、用いる２官能以上のイソシアネートはあらかじめポリオールと反応させて分子量を増大させておいてもよい）。（２）イソシアネート基を有する（メタ）アクリレートにグリシドールを反応させる方法。具体的には例えば、トリメチロールプロパン１モルとイソホロンジイソシアネート３モルとをスズ触媒下で反応させ、更にヒドロキシアクリレート２モルとグリシドール１モルとを加えて反応させることによって得ることができる。 The urethane-modified (meth) acrylic epoxy resin is obtained, for example, by the following method. (1) A method of reacting a (meth) acrylic monomer having a hydroxyl group with a bifunctional or higher isocyanate and glycidol (in this case, the bifunctional or higher isocyanate to be used may be reacted with a polyol in advance to increase the molecular weight) . (2) A method in which glycidol is reacted with (meth) acrylate having an isocyanate group. Specifically, for example, it can be obtained by reacting 1 mol of trimethylolpropane and 3 mol of isophorone diisocyanate in the presence of a tin catalyst, and further adding 2 mol of hydroxyacrylate and 1 mol of glycidol for reaction.
上記ポリオールとしては特に限定されず、例えば、エチレングリコール、グリセリン、ソルビトール、トリメチロールプロパン、（ポリ）プロピレングリコール等が挙げられる。上記イソシアネートとしては、２官能以上であれば特に限定されず、例えば、イソホロンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート（ＭＤＩ）、水添ＭＤＩ、ポリメリックＭＤＩ、１，５−ナフタレンジイソシアネート、ノルボルナンジイソシネート、トリジンジイソシアネート、キシリレンジイオシアネート（ＸＤＩ）、水添ＸＤＩ、リジンジイソシアネート、トリフェニルメタントリイソシアネート、トリス（イソシアネートフェニル）チオフォスフェート、テトラメチルキシレンジイソシアネート、１，６，１０−ウンデカントリイソシアネート等が挙げられる。 It does not specifically limit as said polyol, For example, ethylene glycol, glycerol, sorbitol, a trimethylol propane, (poly) propylene glycol etc. are mentioned. The isocyanate is not particularly limited as long as it is bifunctional or higher. For example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate , Tris (isocyanatephenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate, etc. It is below.
上記水酸基を有する（メタ）アクリルモノマーとしては特に限定されず、例えば、分子内に水酸基を１つ有するモノマーとしては、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート等が挙げられ、分子内に水酸基を２つ以上有するモノマーとしては、ビスフェノールＡ変性エポキシ（メタ）アクリレート等のエポキシ（メタ）アクリレートが挙げられる。これらは、単独で用いても、２種以上を併用してもよい。 The (meth) acrylic monomer having a hydroxyl group is not particularly limited, and examples of the monomer having one hydroxyl group in the molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Examples of the monomer having two or more hydroxyl groups in the molecule include epoxy (meth) acrylates such as bisphenol A-modified epoxy (meth) acrylate. These may be used alone or in combination of two or more.
本発明の硬化性樹脂組成物は、上記水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である２官能以上の液状エポキシ樹脂を含有する。
本明細書において液状とは常温で液状であることを意味する。また、本明細書において水素結合性官能基価とは下記式により算出される値を意味する。
水素結合性官能基価＝（１分子中の水素結合性官能基の数）／（分子量）
The curable resin composition of this invention contains the bifunctional or more functional liquid epoxy resin whose said hydrogen bondable functional group value is 1.5 * 10 < -3 > mol / g or more.
In this specification, liquid means liquid at room temperature. Moreover, in this specification, a hydrogen bondable functional group value means the value computed by a following formula.
Hydrogen bondable functional group value = (number of hydrogen bondable functional groups in one molecule) / (molecular weight)
水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である上記２官能以上の液状エポキシ樹脂は、極性が高いことから、本発明の硬化性樹脂組成物を液晶滴下工法用シール剤に用いた場合にでも液晶に溶出しにくく、液晶を汚染することがない。 Since the bifunctional or higher functional liquid epoxy resin having a hydrogen bondable functional group value of 1.5 × 10 −3 mol / g or more has high polarity, the curable resin composition of the present invention is sealed for a liquid crystal dropping method. Even when used as an agent, it is difficult to elute into the liquid crystal and does not contaminate the liquid crystal.
上記水素結合性官能基としては特に限定されないが、例えば、−ＯＨ基、−ＣＯＮＨ−結合等が挙げられる。なかでも、製造が容易であり、また、安定性に優れることから、−ＯＨ基を有することが好ましい。 Although it does not specifically limit as said hydrogen bondable functional group, For example, -OH group, -CONH-bond, etc. are mentioned. Especially, since it is easy to manufacture and has excellent stability, it is preferable to have an —OH group.
上記水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である２官能以上の液状エポキシ樹脂は、２５℃における粘度が１００Ｐａ・ｓ以下であることが好ましい。このような低粘度の液状エポキシ樹脂を配合することにより、本発明の硬化性樹脂組成物は、高粘度の１分子内に（メタ）アクリル基とエポキシ基とをそれぞれ少なくとも１つ以上有する化合物を含有するにも係わらず全体としての粘度が低く、液晶滴下工法用シール剤として用いる場合の作業性に優れる。１００Ｐａ・ｓを超えると、得られる硬化性樹脂組成物の粘度を充分に下げることができず、液晶滴下工法用シール剤として用いる場合の作業性が劣ることがある。
なお、上記エポキシ（メタ）アクリレートの２５℃における粘度は、Ｅ型粘度計（１ｒｐｍ）を用いて測定することができる。
The hydrogen-bonding functional group value is 1.5 × 10 -3 mol / g or more at a 2 or more functional groups of the liquid epoxy resin is preferably a viscosity at 25 ° C. is not more than 100 Pa · s. By blending such a low-viscosity liquid epoxy resin, the curable resin composition of the present invention comprises a compound having at least one (meth) acryl group and epoxy group in one molecule of high viscosity. Despite being contained, the overall viscosity is low, and the workability when used as a sealing agent for liquid crystal dropping method is excellent. When it exceeds 100 Pa · s , the viscosity of the resulting curable resin composition cannot be sufficiently lowered, and workability when used as a sealing agent for liquid crystal dropping method may be inferior.
The viscosity of the epoxy (meth) acrylate at 25 ° C. can be measured using an E-type viscometer (1 rpm).
上記水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である２官能以上の液状エポキシ樹脂を製造する方法としては特に限定されず、例えば３価以上のアルコールを部分エポキシ化する方法、ジイソシアネートに２当量のグリシドールを反応させる方法、ジカルボン酸に２当量のグリシドールを反応させる方法、エポキシ樹脂を自己付加反応させる方法等が挙げられる。なかでも３価以上のアルコールを部分エポキシ化する方法およびジイソシアネートに２当量のグリシドールを反応させる方法が簡便であり好適である。 The method for producing a bifunctional or higher functional liquid epoxy resin having a hydrogen bondable functional group value of 1.5 × 10 −3 mol / g or more is not particularly limited. For example, partial epoxidation of a trivalent or higher alcohol is performed. Examples thereof include a method, a method of reacting diisocyanate with 2 equivalents of glycidol, a method of reacting dicarboxylic acid with 2 equivalents of glycidol, and a method of self-adding an epoxy resin. Among them, the method of partially epoxidizing a trivalent or higher alcohol and the method of reacting 2 equivalents of glycidol with a diisocyanate are simple and preferable.
上記３価以上のアルコールとしては特に限定されず、例えば、ペンタエリスリトール、トリメチロールプロパン、２，２−ビス（ヒドロキシメチル）オクタン−１−オール、ソルビトール、マンニトール、グリセリン、ジグリセリン、ポリグリセリン等が挙げられる。上記３価以上のアルコールを部分エポキシ化する方法としては、具体的には例えば、ペンタエリスリトール１モルに、２モルのエピクロロヒドリンを反応させ、水酸化ナトリウム処理する方法等が挙げられる。 The trihydric or higher alcohol is not particularly limited, and examples thereof include pentaerythritol, trimethylolpropane, 2,2-bis (hydroxymethyl) octan-1-ol, sorbitol, mannitol, glycerin, diglycerin, polyglycerin and the like. Can be mentioned. Specific examples of the method of partially epoxidizing the trivalent or higher alcohol include a method of reacting 1 mol of pentaerythritol with 2 mol of epichlorohydrin and treating with sodium hydroxide.
上記ジイソシアネートに２当量のグリシドールを反応させる方法としては、具体的には例えば、イソホロンジイソシアネート１モルとグリシドール２モルをスズ触媒下で反応させる方法等が挙げられる。
上記ジイソシアネートとしては、例えば、イソホロンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート（ＭＤＩ）、水添ＭＤＩ、ポリメリックＭＤＩ、１，５−ナフタレンジイソシアネート、ノルボルナンジイソシネート、トリジンジイソシアネート、キシリレンジイオシアネート（ＸＤＩ）、水添ＸＤＩ、リジンジイソシアネート等が挙げられる。
Specific examples of the method of reacting 2 equivalents of glycidol with the diisocyanate include a method of reacting 1 mol of isophorone diisocyanate and 2 mol of glycidol under a tin catalyst.
Examples of the diisocyanate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), and hydrogenated MDI. , Polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate and the like.
上記水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である２官能以上の液状エポキシ樹脂としては、例えば、エピクロンＥＸＡ−７１２０（大日本インキ社製）等の市販のものを用いることもできる。 Examples of the bifunctional or higher functional liquid epoxy resin having a hydrogen bonding functional group value of 1.5 × 10 −3 mol / g or more include commercially available products such as Epicron EXA-7120 (manufactured by Dainippon Ink and Co., Ltd.). It can also be used.
本発明の硬化性樹脂組成物における上記水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である２官能以上の液状エポキシ樹脂の含有量の好ましい下限は、上記１分子内に（メタ）アクリル基とエポキシ基とをそれぞれ少なくとも１つ以上有する化合物１００重量部に対して１０重量部、好ましい上限は２００重量部である。１０重量部未満であると、得られる硬化性樹脂組成物の粘度が充分に低下せず、液晶滴下工法用シール剤として用いたときの作業性が劣ることがあり、２００重量部を超えると、接着強度が不充分となり液晶滴下工法用シール剤として用いることができないことがある。より好ましい下限は２０重量部、より好ましい上限は１００重量部である。 The preferable lower limit of the content of the bifunctional or higher liquid epoxy resin having a hydrogen bondable functional group value of 1.5 × 10 −3 mol / g or more in the curable resin composition of the present invention is within the above-mentioned one molecule. 10 parts by weight with respect to 100 parts by weight of the compound having at least one (meth) acrylic group and epoxy group, and the preferred upper limit is 200 parts by weight. When it is less than 10 parts by weight, the viscosity of the resulting curable resin composition is not sufficiently lowered, and workability when used as a sealing agent for a liquid crystal dropping method may be inferior. Adhesive strength may be insufficient and cannot be used as a sealant for liquid crystal dropping method. A more preferred lower limit is 20 parts by weight, and a more preferred upper limit is 100 parts by weight.
本発明の硬化性樹脂組成物は、更に、熱硬化剤を含有する。
上記熱硬化剤は、加熱により硬化性樹脂組成物中のエポキシ基や（メタ）アクリル基を反応させ、架橋させるためのものであり、硬化後の硬化性樹脂組成物の接着性、耐湿性を向上させる役割を有する。
The curable resin composition of the present invention further contains a thermosetting agent.
The above-mentioned thermosetting agent is for reacting and crosslinking the epoxy group and (meth) acryl group in the curable resin composition by heating, and the adhesiveness and moisture resistance of the curable resin composition after curing are improved. Have a role to improve.
このような熱硬化剤としては、１，３−ビス［ヒドラジノカルボノエチル−５−イソプロピルヒダントイン］等のヒドラジド化合物、ジシアンジアミド、グアニジン誘導体、１−シアノエチル−２−フェニルイミダゾール、Ｎ−［２−（２−メチル−１−イミダゾリル）エチル］尿素、２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジン、Ｎ，Ｎ’−ビス（２−メチル−１−イミダゾリルエチル）尿素、Ｎ，Ｎ’−（２−メチル−１−イミダゾリルエチル）−アジポアミド、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール等のイミダゾール誘導体、変性脂肪族ポリアミン、テトラヒドロ無水フタル酸、エチレングリコールービス（アンヒドロトリメリテート）等の酸無水物、各種アミンとエポキシ樹脂との付加生成物等が挙げられる。これらは、単独で用いても、２種類以上が用いられてもよい。 Examples of such thermosetting agents include hydrazide compounds such as 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin], dicyandiamide, guanidine derivatives, 1-cyanoethyl-2-phenylimidazole, N- [2- (2-Methyl-1-imidazolyl) ethyl] urea, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, N, N′-bis (2-methyl -1-imidazolylethyl) urea, N, N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethyl Imidazole derivatives such as imidazole, modified aliphatic polyamines, tetrahydrophthalic anhydride, ethylene glycol Acid anhydrides such as bis (anhydrotrimellitate), addition products such as the various amines and epoxy resins. These may be used alone or in combination of two or more.
上記熱硬化剤としては、固体熱硬化剤粒子の表面が微粒子により被覆されている被覆熱硬化剤も好適である。このような被覆熱硬化剤を用いれば、予め熱硬化剤を配合していても高い保存安定性を有する硬化性樹脂組成物が得られる。 As the thermosetting agent, a coated thermosetting agent in which the surface of solid thermosetting agent particles is coated with fine particles is also suitable. When such a coating thermosetting agent is used, a curable resin composition having high storage stability can be obtained even if a thermosetting agent is blended in advance.
本発明の硬化性樹脂組成物は、光ラジカル重合開始剤を含有する。
上記光ラジカル重合開始剤としては特に限定されないが、反応性二重結合と光反応開始部とを有するものが好適である。このような光ラジカル重合開始剤を用いれば、本発明の硬化性樹脂組成物に充分な反応性を付与することができるとともに、液晶中に溶出して液晶を汚染することがない。なかでも、反応性二重結合と水酸基及び／又はウレタン結合とを有するベンゾイン（エーテル）類化合物が好適である。なお、ベンゾイン（エーテル）類化合物とは、ベンゾイン類及びベンゾインエーテル類を表す。
The curable resin composition of the present invention contains a radical photopolymerization initiator.
Although it does not specifically limit as said radical photopolymerization initiator, What has a reactive double bond and a photoreaction start part is suitable. If such a radical photopolymerization initiator is used, sufficient reactivity can be imparted to the curable resin composition of the present invention, and it does not elute into the liquid crystal and contaminate the liquid crystal. Of these, benzoin (ether) compounds having a reactive double bond and a hydroxyl group and / or a urethane bond are preferred. The benzoin (ether) compounds represent benzoins and benzoin ethers.
上記反応性二重結合としては、アリル基、ビニルエーテル基、（メタ）アクリル基等の残基が挙げられるが、反応性の高さから（メタ）アクリル残基が好適である。このような反応性二重結合を有することにより、本発明の液晶表示素子用硬化性樹脂組成物の耐候性が向上する。 Examples of the reactive double bond include residues such as an allyl group, a vinyl ether group, and a (meth) acryl group, and a (meth) acryl residue is preferable because of its high reactivity. By having such a reactive double bond, the weather resistance of the curable resin composition for a liquid crystal display element of the present invention is improved.
上記ベンゾイン（エーテル）類化合物は、水酸基とウレタン結合とのどちらか１つを有していればよく、両方を有していてもよい。上記ベンゾイン（エーテル）類化合物が水酸基とウレタン結合のいずれも有していない場合には、液晶に溶出してしまうことがある。 The said benzoin (ether) type compound should just have any one of a hydroxyl group and a urethane bond, and may have both. If the benzoin (ether) compound has neither a hydroxyl group nor a urethane bond, it may elute into the liquid crystal.
上記ベンゾイン（エーテル）類化合物において、上記反応性二重結合及び水酸基及び／又はウレタン結合は、ベンゾイン（エーテル）骨格のどの部分に位置していてもよいが、下記一般式（１）で表される分子骨格を有するものが好適である。かかる分子骨格を有する化合物を、光ラジカル重合開始剤として用いれば、残存物が少なくなり、アウトガスの量を少なくすることができる。 In the benzoin (ether) compound, the reactive double bond and the hydroxyl group and / or the urethane bond may be located at any part of the benzoin (ether) skeleton, and are represented by the following general formula (1). Those having a molecular skeleton are preferred. If a compound having such a molecular skeleton is used as a radical photopolymerization initiator, the amount of residue is reduced and the amount of outgas can be reduced.
一般式（１）で表される分子骨格を有するベンゾイン（エーテル）類化合物としては、例えば、下記一般式（２）で表される化合物が挙げられる。 Examples of benzoin (ether) compounds having a molecular skeleton represented by general formula (1) include compounds represented by the following general formula (2).
上記光ラジカル重合開始剤としては、他にも例えば、ベンゾフェノン、２，２−ジエトキシアセトフェノン、ベンジル、ベンゾイルイソプロピルエーテル、ベンジルジメチルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、チオキサントン等を用いることができる。これらの光ラジカル重合開始剤は単独で用いてもよく、２種以上を併用してもよい。 Other examples of the photo radical polymerization initiator include benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, and thioxanthone. These radical photopolymerization initiators may be used alone or in combination of two or more.
本発明の硬化性樹脂組成物は、シランカップリング剤を含有していてもよい。シランカップリング剤を含有することにより、本発明の硬化性樹脂組成物を液晶滴下工法用シール剤として用いた場合に、シール剤と基板との接着性を向上させることができる。
上記シランカップリング剤としては特に限定されないが、基板等との接着性向上効果に優れ、硬化性樹脂と化学結合することにより液晶材料中への流出を防止するとができることから、例えば、γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−イソシアネートプロピルトリメトキシシラン等や、スペーサー基を介してイミダゾール骨格とアルコキシシリル基とが結合した構造を有するイミダゾールシラン化合物からなるもの等が好適に用いられる。これらのシランカップリング剤は単独で用いてもよく、２種以上を併用してもよい。
The curable resin composition of the present invention may contain a silane coupling agent. By containing the silane coupling agent, the adhesive property between the sealing agent and the substrate can be improved when the curable resin composition of the present invention is used as a sealing agent for a liquid crystal dropping method.
The silane coupling agent is not particularly limited, but is excellent in the effect of improving adhesion to a substrate and the like, and can be prevented from flowing into the liquid crystal material by chemically bonding with a curable resin. Propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, etc., and the structure in which the imidazole skeleton and alkoxysilyl group are bonded via a spacer group What consists of the imidazole silane compound which has is used suitably. These silane coupling agents may be used alone or in combination of two or more.
本発明の硬化性樹脂組成物は、応力分散効果による接着性の改善、線膨張率の改善等の目的でフィラーを含有してもよい。上記フィラーとしては特に限定されず、例えば、シリカ、珪藻土、アルミナ、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、水酸化マグネシウム、水酸化アルミニウム、炭酸マグネシウム、硫酸バリウム、石膏、珪酸カルシウム、タルク、ガラスビーズ、セリサイト活性白土、ベントナイト、窒化アルミニウム、窒化珪素等の無機フィラー等が挙げられる。 The curable resin composition of the present invention may contain a filler for the purpose of improving the adhesiveness due to the stress dispersion effect and improving the linear expansion coefficient. The filler is not particularly limited. For example, silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, gypsum, calcium silicate , Talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride, and other inorganic fillers.
本発明の硬化性樹脂組成物を製造する方法としては特に限定されず、上記１分子内に（メタ）アクリル基とエポキシ基とをそれぞれ少なくとも１つ以上有する化合物、水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である２官能以上の液状エポキシ樹脂、熱硬化剤、光ラジカル重合開始剤、及び、必要に応じて添加する添加剤等を、従来公知の方法により混合する方法等が挙げられる。このとき、イオン性の不純物を除去するために層状珪酸塩鉱物等のイオン吸着性固体と接触させてもよい。 The method for producing the curable resin composition of the present invention is not particularly limited. The compound having at least one (meth) acryl group and an epoxy group in one molecule, and the hydrogen bondable functional group value is 1. A bifunctional or higher functional liquid epoxy resin that is 5 × 10 −3 mol / g or more, a thermosetting agent, a radical photopolymerization initiator, and an additive that is added as necessary are mixed by a conventionally known method. Methods and the like. At this time, in order to remove ionic impurities, it may be brought into contact with an ion-adsorbing solid such as a layered silicate mineral.
本発明の硬化性樹脂組成物は、上述の構成よりなることから、液晶滴下工法用シール剤として用いた場合に、極めて作業性に優れ、また、液晶汚染を引き起こしにくく、色むらが少ない高品位な画像の液晶表示素子を製造することができる。
本発明の硬化性樹脂組成物からなる液晶滴下工法用シール剤もまた、本発明の１つである。
Since the curable resin composition of the present invention has the above-described configuration, when used as a sealing agent for a liquid crystal dropping method, the curable resin composition is extremely excellent in workability, hardly causes liquid crystal contamination, and has high quality with little color unevenness. A liquid crystal display element with a good image can be manufactured.
The sealing agent for liquid crystal dropping method comprising the curable resin composition of the present invention is also one aspect of the present invention.
本発明の液晶滴下工法用シール剤は、硬化後おけるガラス転移温度の好ましい下限が８０℃、好ましい上限が１５０℃である。８０℃未満であると、本発明の液晶滴下工法用シール剤を用いて液晶表示素子を製造した場合に、耐湿性（耐高温高湿性）に劣ることがあり、１５０℃を超えると、剛直に過ぎ基板との密着性に劣ることがある。
なお、上記ガラス転移温度は、ＤＭＡ法により昇温速度５℃／分、周波数１０Ｈｚの条件で測定した値である。
In the sealing agent for liquid crystal dropping method of the present invention, the preferable lower limit of the glass transition temperature after curing is 80 ° C., and the preferable upper limit is 150 ° C. When it is less than 80 ° C., when the liquid crystal display element is produced using the liquid crystal dropping method sealing agent of the present invention, it may be inferior in moisture resistance (high temperature and high humidity resistance). It may be inferior in adhesion to the substrate.
In addition, the said glass transition temperature is the value measured on conditions with a temperature increase rate of 5 degree-C / min and a frequency of 10 Hz by DMA method.
本発明の硬化性樹脂組成物及び／又は本発明の液晶滴下工法用シール剤に、導電性微粒子を配合することにより、上下導通材料を製造することができる。このような上下導通材料を用いれば、液晶を汚染することなく透明基板の電極を導電接続することができる。
本発明の硬化性樹脂組成物及び／又は本発明の液晶滴下工法用シール剤と、導電性微粒子とを含有する上下導通材料もまた、本発明の１つである。
A vertical conduction material can be manufactured by mix | blending electroconductive fine particles with the curable resin composition of this invention and / or the sealing compound for liquid crystal dropping methods of this invention. By using such a vertical conduction material, the electrodes of the transparent substrate can be conductively connected without contaminating the liquid crystal.
The vertical conduction material containing the curable resin composition of the present invention and / or the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.
上記導電性微粒子としては特に限定されず、金属ボール、樹脂微粒子の表面に導電金属層を形成したもの等を用いることができる。なかでも、樹脂微粒子の表面に導電金属層を形成したものは、樹脂微粒子の優れた弾性により、透明基板等を損傷することなく導電接続が可能であることから好適である。 The conductive fine particles are not particularly limited, and metal balls, those obtained by forming a conductive metal layer on the surface of resin fine particles, and the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
本発明の液晶滴下工法用シール剤及び／又は本発明の上下導通材料を用いてなる液晶表示素子もまた、本発明の１つである。 The liquid crystal display element using the sealing compound for liquid crystal dropping method of the present invention and / or the vertical conduction material of the present invention is also one aspect of the present invention.
本発明によれば、滴下工法による液晶表示素子の製造に用いた場合にでも、作業性に優れ、かつ、液晶汚染を引き起こしにくく色むらが少ない高品位な画像の液晶表示素子を製造することができる硬化性樹脂組成物、該硬化性樹脂組成物からなる液晶滴下工法用シール剤、上下導通材料及び液晶表示素子を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, even when it uses for manufacture of the liquid crystal display element by a dripping method, it is excellent in workability | operativity, and can produce the liquid crystal display element of a high quality image which is hard to cause liquid-crystal contamination and has few color irregularities. A curable resin composition, a sealing agent for liquid crystal dropping method, a vertical conduction material, and a liquid crystal display element comprising the curable resin composition can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（１分子内に（メタ）アクリル基とエポキシ基とをそれぞれ少なくとも１つ以上有する化合物の調製）
フェノールノボラック型エポキシ樹脂（大日本インキ社製「Ｎ−７７０」）１９０ｇをトルエン５００ｍＬに溶解し、これにトリフェニルホスフィン０．１ｇを加えて、均一な溶液とした。この溶液にアクリル酸３５ｇを還流撹拌下２時間かけて滴下した後、更に還流撹拌を６時間行った。反応後トルエンを除去することによって、１分子内に（メタ）アクリル基とエポキシ基とをそれぞれ少なくとも１つ以上有する化合物を得た。
得られた１分子内に（メタ）アクリル基とエポキシ基とをそれぞれ少なくとも１つ以上有する化合物について、塩酸−ジオキサン溶液に溶解させた後、エポキシ基によって消費された塩酸量を滴定する方法により測定したところ、原料として用いたフェノールノボラック型エポキシ樹脂のエポキシ基の５０％が（メタ）アクリル酸で変性されていた。
(Preparation of a compound having at least one (meth) acryl group and epoxy group in one molecule)
190 g of phenol novolac type epoxy resin (“N-770” manufactured by Dainippon Ink Co., Ltd.) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added thereto to obtain a uniform solution. To this solution, 35 g of acrylic acid was added dropwise over 2 hours with stirring under reflux, and then stirring under reflux was further performed for 6 hours. After the reaction, toluene was removed to obtain a compound having at least one (meth) acryl group and epoxy group in one molecule.
For a compound having at least one (meth) acrylic group and epoxy group in one molecule obtained, dissolved in a hydrochloric acid-dioxane solution, and then measured by a method of titrating the amount of hydrochloric acid consumed by the epoxy group As a result, 50% of the epoxy group of the phenol novolac type epoxy resin used as a raw material was modified with (meth) acrylic acid.
（水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である２官能以上の液状エポキシ樹脂の調整）
トルエン１５０ｍＬにペンタエリスリトール１３６ｇを溶解させ、１００℃還流状態でエピクロロヒドリン１８４ｇを撹拌しながら２時間かけて滴下した後、更に１２０℃で５時間撹拌を行った。次いで、水酸化ナトリウム溶液を加え、１２時間撹拌した後、分液して有機相を分離した。得られた有機相を数回蒸留水を用いて洗浄をした後、クロロホルムを除いて、常温において液状の水酸基を有するエポキシ樹脂Ａを得た。
得られた水酸基を有するエポキシ樹脂Ａについて、塩酸−ジオキサン溶液に溶解させた後、エポキシ基によって消費された塩酸量を滴定する方法により測定したところ、水酸基の５０％がエポキシに変換されていることを確認した（水素結合性官能基価８．１×１０−３）。また、Ｅ型粘度計（１ｒｐｍ）を用いて２５℃における粘度を測定したところ、１０Ｐａ・ｓであった。
(Adjustment of a bifunctional or higher functional liquid epoxy resin having a hydrogen bondable functional group value of 1.5 × 10 −3 mol / g or higher)
In 150 mL of toluene, 136 g of pentaerythritol was dissolved, and 184 g of epichlorohydrin was added dropwise over 2 hours with stirring at 100 ° C., followed by further stirring at 120 ° C. for 5 hours. Then, a sodium hydroxide solution was added and stirred for 12 hours, followed by liquid separation to separate the organic phase. The obtained organic phase was washed several times with distilled water, and then chloroform was removed to obtain an epoxy resin A having a liquid hydroxyl group at room temperature.
The obtained epoxy resin A having a hydroxyl group was dissolved in a hydrochloric acid-dioxane solution and then measured by a method of titrating the amount of hydrochloric acid consumed by the epoxy group, and 50% of the hydroxyl group was converted to epoxy. (Hydrogen bondable functional group value 8.1 × 10 −3 ) was confirmed. Moreover, it was 10 Pa.s when the viscosity in 25 degreeC was measured using the E-type viscosity meter (1 rpm).
クロロホルム１５０ｍＬにヘキサメチレンジイソシアネート８４ｇ及びジラウリン酸ジブチルスズ０．５ｇを溶解し、４０℃に保った状態でクロロホルム１００ｍＬとグリシドール７５ｇの混合液を２時間かけて滴下し、更に８０℃で５時間撹拌を行った。次いで、５００ｍＬの氷水を加え、良くかき混ぜた後、分液して有機相を分離した。得られた有機相を数回蒸留水を用いて洗浄をした後、クロロホルムを除いて、常温において液状のウレタン結合を有するエポキシ樹脂Ｂを得た。
得られたウレタン結合を有するエポキシ樹脂Ｂについて、塩酸−ジオキサン溶液に溶解させた後、エポキシ基によって消費された塩酸量を滴定する方法により測定したところ、エポキシ当量は１５８であった（水素結合性官能基価６．３×１０−３）。
また、Ｅ型粘度計（１ｒｐｍ）を用いて２５℃における粘度を測定したところ、３５Ｐａ・ｓであった。
In 150 mL of chloroform, 84 g of hexamethylene diisocyanate and 0.5 g of dibutyltin dilaurate were dissolved, and a mixture of 100 mL of chloroform and 75 g of glycidol was added dropwise over 2 hours while maintaining the temperature at 40 ° C., and further stirred at 80 ° C. for 5 hours. It was. Next, 500 mL of ice water was added, and the mixture was stirred well and separated to separate the organic phase. The obtained organic phase was washed several times with distilled water, and then chloroform was removed to obtain an epoxy resin B having a liquid urethane bond at room temperature.
About the epoxy resin B which has the obtained urethane bond, after making it melt | dissolve in hydrochloric acid-dioxane solution, when measuring by the method of titrating the amount of hydrochloric acid consumed by the epoxy group, the epoxy equivalent was 158 (hydrogen bonding property) Functional group value 6.3 × 10 −3 ).
Moreover, it was 35 Pa.s when the viscosity in 25 degreeC was measured using the E-type viscosity meter (1 rpm).
市販のエピクロンＥＸＡ−７１２０（大日本インキ社製）を用いた。
エピクロンＥＸＡ−７１２０について、塩酸−ジオキサン溶液に溶解させた後、エポキシ基によって消費された塩酸量を滴定する方法により測定したところ、エポキシ当量は２５８であった（水素結合性官能基価１．９３×１０−３）
また、Ｅ型粘度計（１ｒｐｍ）を用いて２５℃における粘度を測定したところ、１０Ｐａ・ｓであった。
Commercially available Epicron EXA-7120 (manufactured by Dainippon Ink Co., Ltd.) was used.
About Epicron EXA-7120, it was dissolved in a hydrochloric acid-dioxane solution and then the amount of hydrochloric acid consumed by the epoxy group was measured by a titration method. As a result, the epoxy equivalent was 258 (hydrogen bonding functional group value 1.93). × 10-3 )
Moreover, it was 10 Pa.s when the viscosity in 25 degreeC was measured using the E-type viscosity meter (1 rpm).
（実施例１〜３）
得られた１分子内に（メタ）アクリル基とエポキシ基とをそれぞれ少なくとも１つ以上有する化合物及び液状エポキシ樹脂を用い、表１に示した各原材料を遊星式撹拌機を用いて混合後、更に３本ロールを用いて混合させることにより硬化性樹脂組成物を作製し、これを液晶滴下工法用シール剤とした。
(Examples 1-3)
Using the compound and liquid epoxy resin each having at least one (meth) acrylic group and epoxy group in the obtained molecule, and mixing the raw materials shown in Table 1 using a planetary stirrer, A curable resin composition was prepared by mixing using three rolls, and this was used as a sealing agent for a liquid crystal dropping method.
２枚の透明電極付き透明基板の一方に、得られた液晶滴下工法用シール剤を長方形の枠を描くようにディスペンサーで塗布した。次いで、液晶（チッソ社製、「ＪＣ−５００４ＬＡ」）の微小滴を透明基板の枠内全面に滴下塗布し、直ちにもう一方の透明基板を重ね合わせてシール部に高圧水銀ランプを用い紫外線を５０ｍＷ／ｃｍ２で２０秒照射した。その後液晶アニールを１２０℃、１時間行い同時に液晶滴下工法用シール剤を熱硬化させて液晶表示用素子を得た。 The obtained liquid crystal dropping method sealing agent was applied to one of the two transparent substrates with a transparent electrode with a dispenser so as to draw a rectangular frame. Next, fine droplets of liquid crystal (manufactured by Chisso Corporation, “JC-5004LA”) are applied to the entire surface of the frame of the transparent substrate, and the other transparent substrate is immediately overlaid, and a high pressure mercury lamp is used as a seal portion to apply 50 mW of ultraviolet light. Irradiated at / cm 2 for 20 seconds. Thereafter, liquid crystal annealing was performed at 120 ° C. for 1 hour, and at the same time, the sealing agent for the liquid crystal dropping method was thermally cured to obtain a liquid crystal display element.
（比較例１）
表１に示したように、水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である２官能以上の液状エポキシ樹脂の代わりにライトアクリレート１．６ＨＸ−Ａ（１，６ヘキサンジオールのアクリル酸エステル、粘度０．８、共栄社化学社製）を用いた以外は実施例１と同様の方法により硬化性樹脂組成物を作製し、これを液晶滴下工法用シール剤として用いて液晶表示用素子を製造した。
(Comparative Example 1)
As shown in Table 1, instead of a bifunctional or higher functional liquid epoxy resin having a hydrogen bonding functional group value of 1.5 × 10 −3 mol / g or more, light acrylate 1.6HX-A (1,6 hexane A curable resin composition was prepared in the same manner as in Example 1 except that diol acrylate ester, viscosity 0.8, manufactured by Kyoeisha Chemical Co., Ltd.) was used, and this was used as a sealing agent for liquid crystal dropping method. A display element was manufactured.
（比較例２）
表１に示したように、水素結合性官能基価が１．５×１０−３ｍｏｌ／ｇ以上である２官能以上の液状エポキシ樹脂の代わりにエピクロン８５０Ｓ（ビスフェノールＡ型エポキシ樹脂：粘度８、大日本インキ化学社製）を用いた以外は実施例１と同様の方法により硬化性樹脂組成物を作製し、これを液晶滴下工法用シール剤として用いて液晶表示用素子を製造した。
(Comparative Example 2)
As shown in Table 1, instead of a bifunctional or higher functional liquid epoxy resin having a hydrogen bonding functional group value of 1.5 × 10 −3 mol / g or more, Epicron 850S (bisphenol A type epoxy resin: viscosity 8, A curable resin composition was prepared in the same manner as in Example 1 except that Dainippon Ink Chemical Co., Ltd. was used, and a liquid crystal display element was produced using this as a sealing agent for the liquid crystal dropping method.
実施例１〜３、比較例１、２で得られた液晶滴下工法用シール剤及び液晶表示素子について、以下の方法により評価を行った。
結果を表１に示した。
The sealing agents for liquid crystal dropping method and liquid crystal display elements obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated by the following methods.
The results are shown in Table 1.
（１）液晶滴下工法用シール剤の描画性評価
液晶滴下工法用シール剤５ｇを１０ｍＬシリンジ（武蔵エンジニアリング社製、ノズル径０．２ｍｍ）に充填した後、ショットマスター３００（武蔵エンジニアリング社製）を用いて、塗布圧３ｋｇ、速度５０ｍｍ／ｓｅｃの条件で直線に描画した。このときの描画性について以下の基準で評価した。
◎：綺麗な直線を描けた
○：シール切れすることなく直線を描けた
△：直線は描けたものの、シール切れが所々に見られた
×：ほとんど描画できなかった（シリンジから吐出できなかった）
(1) Drawability evaluation of liquid crystal dropping method sealant After filling 5 g of liquid crystal dropping method sealant into a 10 mL syringe (manufactured by Musashi Engineering Co., Ltd., nozzle diameter 0.2 mm), Shot Master 300 (manufactured by Musashi Engineering Co., Ltd.) is used. Using this, a straight line was drawn under conditions of a coating pressure of 3 kg and a speed of 50 mm / sec. The drawability at this time was evaluated according to the following criteria.
◎: Draw a beautiful straight line ○: Draw a straight line without cutting the seal △: Draw a straight line, but there were some broken seals X: Did not draw almost (cannot be discharged from the syringe)
（２）液晶滴下工法用シール剤の接着強度の評価
液晶滴下工法用シール剤１００重量部に対して平均粒径５μｍのポリマービーズ（積水化学工業社製「ミクロパールＳＰ」）３重量部を遊星式撹拌装置によって分散させ均一な液とし、これを大きさ２０ｍｍ×５０ｍｍ、厚さ１．１ｍｍのガラス板（コーニング社製「１７３７」の中央部に塗布した後、同型のガラスをその上に重ね合わせてを押し広げ、紫外線を５０ｍＷ／ｃｍ２の強度で６０秒間照射した。その後、１２０℃、１時間の加熱を行い、接着試験片を得た。得られた接着試験片について、テンションゲージを用いて接着強度を測定した。
(2) Evaluation of Adhesive Strength of Liquid Crystal Drop Method Sealant 3 parts by weight of polymer beads (“Micropearl SP” manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 5 μm per 100 parts by weight of liquid crystal drop method sealant Disperse with a stirrer to form a uniform liquid, which is applied to the center of a 20 mm × 50 mm, 1.1 mm thick glass plate (“1737” manufactured by Corning), and the same type of glass is stacked on it. The two pieces were spread together and irradiated with ultraviolet rays at an intensity of 50 mW / cm 2 for 60 seconds, and then heated at 120 ° C. for 1 hour to obtain an adhesive test piece. Used to measure the adhesive strength.
（３）液晶表示素子の表示ムラの評価
得られた液晶表示素子のシール部周辺の液晶に生じる色むらを目視にて観察し、以下の基準により評価した。
◎：色むらが全くない
○：色むらがほとんどない
△：少し色むらがある
×：色むらがかなりある
(3) Evaluation of display unevenness of liquid crystal display element Color unevenness generated in the liquid crystal around the seal portion of the obtained liquid crystal display element was visually observed and evaluated according to the following criteria.
◎: No color unevenness ○: Little color unevenness △: Some color unevenness ×: There is considerable color unevenness
（４）エージング後の液晶表示素子の表示ムラの評価
得られた液晶表示素子に５Ｖの直流電圧を印加した状態で８０℃雰囲気下、１００時間放置後のシール部周辺の液晶に生じる色むらを目視にて観察し、以下の基準により評価した。
◎：色むらが全くない
○：色むらがほとんどない
△：少し色むらがある
×：色むらがかなりある
(4) Evaluation of display unevenness of liquid crystal display element after aging The color unevenness generated in the liquid crystal around the seal portion after being left in an 80 ° C. atmosphere for 100 hours in a state where a DC voltage of 5 V is applied to the obtained liquid crystal display element. It observed visually and evaluated by the following references | standards.
◎: No color unevenness ○: Little color unevenness △: Some color unevenness ×: There is considerable color unevenness
本発明によれば、滴下工法による液晶表示素子の製造に用いた場合にでも、作業性に優れ、かつ、液晶汚染を引き起こしにくく色むらが少ない高品位な画像の液晶表示素子を製造することができる硬化性樹脂組成物、該硬化性樹脂組成物からなる液晶滴下工法用シール剤、上下導通材料及び液晶表示素子を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, even when it uses for manufacture of the liquid crystal display element by a dripping method, it is excellent in workability | operativity, and can produce the liquid crystal display element of a high quality image which is hard to cause liquid-crystal contamination and has few color irregularities. A curable resin composition, a sealing agent for liquid crystal dropping method, a vertical conduction material, and a liquid crystal display element comprising the curable resin composition can be provided.
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| JP5149487B2 (en) * | 2006-02-22 | 2013-02-20 | 三井化学株式会社 | Liquid crystal sealant and liquid crystal display panel using the same |
| JP5184361B2 (en) * | 2006-09-07 | 2013-04-17 | 三井化学株式会社 | Liquid crystal sealant, liquid crystal display panel manufacturing method using the same, and liquid crystal display panel |
| JP5098009B2 (en) * | 2006-10-25 | 2012-12-12 | 北川工業株式会社 | Conductive heat conductive material |
| JP5172321B2 (en) * | 2006-12-26 | 2013-03-27 | 三井化学株式会社 | Liquid crystal sealant |
| JP2009155589A (en) * | 2007-12-28 | 2009-07-16 | Three Bond Co Ltd | Curable composition |
| JP5547642B2 (en) * | 2008-09-30 | 2014-07-16 | 三井化学株式会社 | Liquid crystal sealant, liquid crystal display panel using the same, manufacturing method thereof, and liquid crystal display device |
| JP5876972B1 (en) | 2014-03-31 | 2016-03-02 | 協立化学産業株式会社 | Curable resin excellent in flexibility after curing, (meth) acrylated curable resin, and liquid crystal sealant composition |
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