JP2017134124A5 - Photocurable resin composition, display element sealant, liquid crystal display element sealant, liquid crystal display panel, and liquid crystal display panel manufacturing method - Google Patents
Photocurable resin composition, display element sealant, liquid crystal display element sealant, liquid crystal display panel, and liquid crystal display panel manufacturing method Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 82
- 239000011342 resin composition Substances 0.000 title claims description 33
- 239000000565 sealant Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 26
- 238000007789 sealing Methods 0.000 claims description 19
- 229920001187 thermosetting polymer Polymers 0.000 claims description 19
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N Imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 3
- 230000001678 irradiating Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 231100000489 sensitizer Toxicity 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 methacrylic acid-modified bisphenol F Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- OEZKDMYTQDZSAZ-UHFFFAOYSA-N 1-hydroxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O OEZKDMYTQDZSAZ-UHFFFAOYSA-N 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bis(4-hydroxyphenyl)methane Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000001771 impaired Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Description
本発明は、光硬化性樹脂組成物、表示素子シール剤、液晶表示素子シール剤、液晶表示パネル及び液晶表示パネルの製造方法に関する。 The present invention relates to a photocurable resin composition, a display element sealant, a liquid crystal display element sealant, a liquid crystal display panel, and a method for producing a liquid crystal display panel .
液晶表示パネルは、例えば液晶滴下工法で製造され得る。液晶滴下工法による液晶表示パネルの製造は、（１）透明な基板の内縁に液晶表示素子シール剤を塗布して液晶を充填するための枠を形成し、（２）該枠内に液晶を滴下し、（３）液晶表示素子シール剤が未硬化状態のままで２枚の基板を高真空下で重ね合わせた後、（４）液晶表示素子シール剤を硬化させて行う。 The liquid crystal display panel can be manufactured, for example, by a liquid crystal dropping method. The liquid crystal display panel is manufactured by the liquid crystal dropping method. (1) A liquid crystal display element sealant is applied to the inner edge of a transparent substrate to form a frame for filling the liquid crystal, and (2) liquid crystal is dropped into the frame. (3) After the two substrates are superposed under high vacuum while the liquid crystal display element sealant is in an uncured state, (4) the liquid crystal display element sealant is cured.
このように、液晶滴下工法では、未硬化の液晶表示素子シール剤と液晶とが接触した状態で光硬化又は熱硬化を行う。そのため、液晶表示素子シール剤は、高い硬化性を有するだけでなく、液晶の汚染を低減できることが求められる。 Thus, in the liquid crystal dropping method, photocuring or thermosetting is performed in a state where the uncured liquid crystal display element sealant and the liquid crystal are in contact with each other. Therefore, the liquid crystal display element sealing agent is required not only to have high curability but also to reduce liquid crystal contamination.
液晶滴下工法に用いられる液晶表示素子シール剤として、分子内に（メタ）アクリロイル基を有する化合物と、光重合開始剤としてアントラキノン誘導体とを含む光硬化性樹脂組成物が提案されている（例えば特許文献１）。また、光重合性オリゴマーと、光重合開始剤としてヒドロキシチオキサントンを分子内に２以上のエポキシ基を有する化合物と反応させて得られる化合物Ｂとを含む光硬化性樹脂組成物が提案されている（例えば特許文献２）。さらに、硬化性樹脂と、特定のチオキサントン系重合開始剤と、アミン系増感剤とを含む液晶表示素子用シール剤が提案されている（例えば特許文献３）。 As a liquid crystal display element sealant used in a liquid crystal dropping method, a photocurable resin composition containing a compound having a (meth) acryloyl group in a molecule and an anthraquinone derivative as a photopolymerization initiator has been proposed (for example, a patent) Reference 1). A photocurable resin composition comprising a photopolymerizable oligomer and a compound B obtained by reacting hydroxythioxanthone as a photopolymerization initiator with a compound having two or more epoxy groups in the molecule has been proposed ( For example, Patent Document 2). Furthermore, a sealing agent for liquid crystal display elements including a curable resin, a specific thioxanthone polymerization initiator, and an amine sensitizer has been proposed (for example, Patent Document 3).
［１］ 分子内にエチレン性不飽和二重結合を有する硬化性化合物（Ａ）と、
下記一般式（１）で表される化合物（Ｂ）と、
を含む、光硬化性樹脂組成物。
Ｒ１〜Ｒ８の少なくとも１つは、−Ｓ−Ｗ（Ｗは、置換されていてもよい炭素数１〜８のアルキル基、置換されていてもよい炭素数１〜８のアルケニル基、又は置換されていてもよいアリール基）であり、
それ以外のＲ１〜Ｒ８は、水素原子、水酸基、置換されていてもよい炭素数１〜８のアルキル基、置換されていてもよい炭素数１〜８のアルケニル基、又は置換されていてもよいアリール基であり、且つ
Ｒ１〜Ｒ８の少なくとも１つは、水酸基、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルキル基、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルケニル基、水酸基若しくは水酸基含有基で置換されたアリール基、又は−Ｓ−Ｘ（Ｘは、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルキル基、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルケニル基、又は水酸基若しくは水酸基含有基で置換されたアリール基）である］
［２］ 前記化合物（Ｂ）が、下記一般式（２）で表される、［１］に記載の光硬化性樹脂組成物。
Ｘは、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルキル基、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルケニル基、又は水酸基若しくは水酸基含有基で置換されたアリール基である）
［３］ 前記化合物（Ｂ）が、下記一般式（２’）で表される、［１］又は［２］に記載の光硬化性樹脂組成物。
Ｘは、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルキル基、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルケニル基、又は水酸基若しくは水酸基含有基で置換されたアリール基である）
［４］ アミン系増感剤（Ｃ）をさらに含む、［１］〜［３］のいずれか一項に記載の光硬化性樹脂組成物。
［５］ 前記化合物（Ｂ）の含有量が、前記硬化性化合物（Ａ）に対して０．０１〜１０質量％である、［１］〜［４］のいずれか一項に記載の光硬化性樹脂組成物。
［６］ 前記硬化性化合物（Ａ）が、分子内にエポキシ基をさらに有する、［１］〜［５］のいずれか一項に記載の光硬化性樹脂組成物。
［７］ 分子内にエポキシ基を有する熱硬化性化合物（Ｄ）（但し、前記熱硬化性化合物（Ｄ）は、前記硬化性化合物（Ａ）とは異なるものとする）
熱硬化剤（Ｅ）とをさらに含む、［１］〜［６］のいずれか一項に記載の光硬化性樹脂組成物。
［８］ 前記熱硬化剤（Ｅ）が、ジヒドラジド系熱潜在性硬化剤、イミダゾール系熱潜在性硬化剤、アミンアダクト系熱潜在性硬化剤、及びポリアミン系熱潜在性硬化剤からなる群より選ばれる１以上である、［７］に記載の光硬化性樹脂組成物。
［９］ 無機充填剤又は有機充填剤をさらに含む、［１］〜［８］のいずれか一項に記載の光硬化性樹脂組成物。
［１０］ ［１］〜［９］のいずれか一項に記載の光硬化性樹脂組成物からなる、表示素子シール剤。
［１１］ ［１］〜［９］のいずれか一項に記載の光硬化性樹脂組成物からなる、液晶表示素子シール剤。
［１２］ ［１１］に記載の液晶表示素子シール剤を用いて、一方の基板にシールパターンを形成する工程と、前記シールパターンが未硬化の状態において、前記シールパターンの領域内、又は前記一方の基板と対になる他方の基板に液晶を滴下する工程と、前記一方の基板と前記他方の基板とを、前記シールパターンを介して重ね合わせる工程と、前記シールパターンを硬化させる工程とを含む、液晶表示パネルの製造方法。
［１３］ 前記シールパターンを硬化させる工程は、前記シールパターンに光を照射して前記シールパターンを硬化させる工程を含む、［１２］に記載の液晶表示パネルの製造方法。
［１４］ 前記シールパターンに照射する光は、可視光領域の光を含む、［１３］に記載の液晶表示パネルの製造方法。
［１５］ 前記シールパターンを硬化させる工程は、光が照射された前記シールパターンを加熱して硬化させる工程をさらに含む、［１３］又は［１４］に記載の液晶表示パネルの製造方法。
［１６］ 一対の基板と、前記一対の基板の間に配置された枠状のシール部材と、前記一対の基板の間の前記シール部材で囲まれた空間に充填された液晶層とを含み、前記シール部材が、［１１］に記載の液晶表示素子シール剤の硬化物である、液晶表示パネル。
[1] A curable compound (A) having an ethylenically unsaturated double bond in the molecule;
Compound (B) represented by the following general formula (1),
A photocurable resin composition comprising:
At least one of R 1 to R 8 is —S—W (W is an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 1 to 8 carbon atoms, or An optionally substituted aryl group),
Other R 1 to R 8 are a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 1 to 8 carbon atoms, or a substituted group. And at least one of R 1 to R 8 is a hydroxyl group, a C 1-8 alkyl group substituted with a hydroxyl group or a hydroxyl group-containing group, a carbon number substituted with a hydroxyl group or a hydroxyl group-containing group 1-8 alkenyl group, a hydroxyl group or a hydroxyl group-containing aryl group substituted by group, or -S-X (X is a hydroxyl group or a hydroxyl group-containing substituted alkyl group having 1 to 8 carbon atoms in the group, a hydroxyl group or a hydroxyl group-containing A C1-C8 alkenyl group substituted with a group, or an aryl group substituted with a hydroxyl group or a hydroxyl group-containing group ]
[2] The photocurable resin composition according to [1], wherein the compound (B) is represented by the following general formula (2).
X is an alkyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, an alkenyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, or an aryl substituted with a hydroxyl group or a hydroxyl group-containing group Base)
[3] The photocurable resin composition according to [1] or [2], wherein the compound (B) is represented by the following general formula (2 ′).
X is an alkyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, an alkenyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, or an aryl substituted with a hydroxyl group or a hydroxyl group-containing group Base)
[4] The photocurable resin composition according to any one of [1] to [3], further including an amine sensitizer (C).
[5] The photocuring according to any one of [1] to [4], wherein the content of the compound (B) is 0.01 to 10% by mass with respect to the curable compound (A). Resin composition.
[6] The photocurable resin composition according to any one of [1] to [5], wherein the curable compound (A) further has an epoxy group in the molecule.
[7] Thermosetting compound (D) having an epoxy group in the molecule (provided that the thermosetting compound (D) is different from the curable compound (A))
The photocurable resin composition according to any one of [1] to [6], further comprising a thermosetting agent (E).
[8] The thermosetting agent (E) is selected from the group consisting of a dihydrazide thermal latent curing agent , an imidazole thermal latent curing agent, an amine adduct thermal latent curing agent, and a polyamine thermal latent curing agent. 1 or more, The photocurable resin composition as described in [7].
[9] The photocurable resin composition according to any one of [1] to [8], further including an inorganic filler or an organic filler.
[10] A display element sealing agent comprising the photocurable resin composition according to any one of [1] to [9].
[11] A liquid crystal display element sealing agent comprising the photocurable resin composition according to any one of [1] to [9] .
[ 12 ] A step of forming a seal pattern on one substrate using the liquid crystal display element sealant according to [ 11 ], and the seal pattern in an uncured state, or in the region of the seal pattern or the one A step of dropping liquid crystal on the other substrate paired with the substrate, a step of superimposing the one substrate and the other substrate through the seal pattern, and a step of curing the seal pattern And manufacturing method of liquid crystal display panel.
[ 13 ] The method for manufacturing a liquid crystal display panel according to [ 12 ], wherein the step of curing the seal pattern includes a step of irradiating the seal pattern with light to cure the seal pattern.
[ 14 ] The method for manufacturing a liquid crystal display panel according to [ 13 ], wherein the light applied to the seal pattern includes light in a visible light region.
[ 15 ] The method for manufacturing a liquid crystal display panel according to [ 13 ] or [ 14 ], wherein the step of curing the seal pattern further includes a step of heating and curing the seal pattern irradiated with light.
[ 16 ] including a pair of substrates, a frame-shaped sealing member disposed between the pair of substrates, and a liquid crystal layer filled in a space surrounded by the sealing member between the pair of substrates, The liquid crystal display panel whose said sealing member is the hardened | cured material of the liquid crystal display element sealing agent as described in [ 11 ].
本発明によれば、例えば表示素子シール剤、特に液晶表示素子シール剤として用いた際に、可視光に対しても十分な硬化性を有し、且つ液晶の汚染を高度に抑制できる光硬化性樹脂組成物を提供することができる。 According to the present invention, for example, when used as a display element sealant, particularly a liquid crystal display element sealant, it has sufficient curability for visible light and can highly suppress contamination of liquid crystal. A resin composition can be provided.
化合物（Ｂ）の１分子中の水酸基の数は、１〜５個であることが好ましく、１〜３個であることがより好ましい。１分子中の水酸基の数が１個以上であると、化合物（Ｂ）の親水性が適度に高められ、光硬化性樹脂組成物を液晶表示素子シール剤として用いた際に化合物（Ｂ）の液晶への溶出を好ましく抑制できる。１分子中の水酸基の数が５個以下であると、硬化物の耐湿性が損なわれにくい。 The number of hydroxyl groups in one molecule of the compound (B) is preferably 1 to 5, and more preferably 1 to 3. When the number of hydroxyl groups in one molecule is 1 or more, the hydrophilicity of the compound (B) is moderately increased, and when the photocurable resin composition is used as a liquid crystal display element sealant, the compound (B) Elution into the liquid crystal can be preferably suppressed. When the number of hydroxyl groups in one molecule is 5 or less, the moisture resistance of the cured product is hardly impaired.
１−４．熱硬化性化合物（Ｄ）
熱硬化性化合物（Ｄ）は、分子内にエポキシ基を有するエポキシ化合物であることが好ましい。但し、熱硬化性化合物（Ｄ）は、硬化性化合物（Ａ）とは異なるものとする。熱硬化性化合物（Ｄ）は、分子内に（メタ）アクリロイル基を有さないエポキシ化合物であることがより好ましい。エポキシ化合物は、モノマー、オリゴマー又はポリマーのいずれであってもよい。エポキシ化合物は、例えば光硬化性樹脂組成物を液晶表示素子シール剤として用いた際に、液晶に対する溶解性や拡散性が低く、得られる液晶パネルの表示特性を良好とするだけでなく、硬化物の耐湿性を高め得る。
1-4. Thermosetting compound (D)
The thermosetting compound (D) is preferably an epoxy compound having an epoxy group in the molecule. However, the thermosetting compound (D) is different from the curable compound (A). The thermosetting compound (D) is more preferably an epoxy compound having no (meth) acryloyl group in the molecule. The epoxy compound may be any of a monomer, an oligomer or a polymer. Epoxy compounds, for example, when using a photocurable resin composition as a liquid crystal display element sealing agent, have low solubility and diffusibility in liquid crystals, and not only improve the display characteristics of the resulting liquid crystal panel, but also cured products. Can improve the moisture resistance.
即ち、本発明の液晶表示パネルは、一対の基板と、該一対の基板の間に配置される枠状のシール部材と、該一対の基板の間の枠状のシール部材で囲まれた空間に充填された液晶層（液晶表示素子）とを含む。シール部材を、本発明の液晶表示素子シール剤の硬化物とし得る。本発明の液晶表示素子シール剤は、本発明の光硬化性樹脂組成物からなる。 That is, the liquid crystal display panel of the present invention includes a space surrounded by a pair of substrates, a frame-shaped seal member disposed between the pair of substrates, and a frame-shaped seal member between the pair of substrates. A filled liquid crystal layer (liquid crystal display element). A sealing member can be made into the hardened | cured material of the liquid crystal display element sealing agent of this invention. The liquid crystal display element sealing agent of the present invention comprises the photocurable resin composition of the present invention.
液晶表示パネルは、本発明の液晶表示素子シール剤を用いて製造される。液晶表示パネルの製造方法には、一般に、液晶滴下工法と、液晶注入工法とがあるが、本発明の液晶表示パネルは、液晶滴下工法で製造されることが好ましい。 A liquid crystal display panel is manufactured using the liquid crystal display element sealing agent of this invention. Generally, there are a liquid crystal dropping method and a liquid crystal injecting method as a method for manufacturing a liquid crystal display panel, but the liquid crystal display panel of the present invention is preferably manufactured by a liquid crystal dropping method.
液晶滴下工法による液晶表示パネルの製造方法は、
１）一方の基板に、本発明の液晶表示素子シール剤のシールパターンを形成する工程と、
２）シールパターンが未硬化の状態において、基板のシールパターンで囲まれた領域内、又はシールパターンで囲まれた領域に対向する他方の基板の領域に、液晶を滴下する工程と、
３）一方の基板と他方の基板とをシールパターンを介して重ね合わせる工程と、
４）シールパターンを硬化させる工程と
を含む。
The manufacturing method of the liquid crystal display panel by the liquid crystal dropping method is
1) forming a seal pattern of the liquid crystal display element sealant of the present invention on one substrate;
2) dropping the liquid crystal in a region surrounded by the seal pattern of the substrate or a region of the other substrate facing the region surrounded by the seal pattern in a state where the seal pattern is uncured;
3) a step of superimposing one substrate and the other substrate through a seal pattern;
4) curing the seal pattern.
２）の工程において、シールパターンが未硬化の状態とは、液晶表示素子シール剤の硬化反応がゲル化点までは進行していない状態を意味する。このため、２）の工程では、液晶表示素子シール剤の液晶への溶解を抑制するために、シールパターンを光照射又は加熱して半硬化させてもよい。 In the step 2), the uncured state of the seal pattern means a state in which the curing reaction of the liquid crystal display element sealant has not progressed to the gel point. For this reason, in the process of 2), in order to suppress dissolution of the liquid crystal display element sealant into the liquid crystal, the seal pattern may be semi-cured by light irradiation or heating.
４）の工程では、光照射による硬化のみを行ってもよいが、光照射による硬化を行った後、加熱による硬化を行ってもよい。即ち、４）の工程は、シールパターンに光を照射してシールパターンを硬化させる工程を含み；液晶表示素子シール剤が前述の熱硬化剤（Ｅ）をさらに含む場合は、光が照射されたシールパターンを加熱して硬化させる工程をさらに含んでもよい。光照射による硬化を行うことで、液晶表示素子シール剤を短時間で硬化させることができるので、液晶への溶解を抑制できる。光照射による硬化と加熱による硬化とを組み合わせることで、光照射による硬化のみの場合と比べて光による液晶層へのダメージを少なくすることができる。 In the step 4), only curing by light irradiation may be performed, but after curing by light irradiation, curing by heating may be performed. That is, the step 4) includes a step of irradiating the seal pattern with light to cure the seal pattern; when the liquid crystal display element sealant further includes the above-described thermosetting agent (E), the light was irradiated. You may further include the process of heating and hardening a seal pattern. Since the liquid crystal display element sealing agent can be cured in a short time by curing by light irradiation, dissolution in the liquid crystal can be suppressed. By combining curing by light irradiation and curing by heating, damage to the liquid crystal layer due to light can be reduced compared to the case of only curing by light irradiation.
光照射エネルギーは、硬化性化合物（Ａ）を硬化させる程度のエネルギーであればよい。光硬化時間は、液晶表示素子シール剤の組成にもよるが、例えば１０分程度である。 Light irradiation energy should just be an energy of the grade which hardens a curable compound (A). The photocuring time is, for example, about 10 minutes although it depends on the composition of the liquid crystal display element sealant.
熱硬化温度は、液晶表示素子シール剤の組成にもよるが、例えば１２０℃であり、熱硬化時間は２時間程度である。 The thermosetting temperature depends on the composition of the liquid crystal display element sealant, but is, for example, 120 ° C., and the thermosetting time is about 2 hours.
本発明の液晶表示素子シール剤は、液晶への溶出が低減されている。従って、本発明の液晶表示素子シール剤の硬化物を有する液晶表示パネルは、液晶の汚染が少なく、高品質の表示性能を有し得る。 The liquid crystal display element sealant of the present invention has reduced elution into the liquid crystal. Therefore, the liquid crystal display panel having a cured product of the liquid crystal display element sealant of the present invention has little liquid crystal contamination and can have high quality display performance.
２．光硬化性樹脂組成物の調製と評価
（硬化性化合物（Ａ））
硬化性化合物（Ａ−１）：
以下の方法で、メタアクリル酸変性ビスフェノールＦ型エポキシ樹脂（９５％部分メタアクリル化物）を合成した。
１６０ｇの液状ビスフェノールＦ型エポキシ樹脂（YDF-8170C、新日鉄住金化学社製、エポキシ当量１６０ｇ／ｅｑ）、重合禁止剤として０．１ｇのｐ-メトキシフェノール、触媒として０．２ｇのトリエタノールアミン、及び８１．７ｇのメタアクリル酸をフラスコ内に仕込み、乾燥空気を送り込んで９０℃で還流攪拌しながら５時間反応させた。得られた反応生成物を、超純水にて２０回洗浄し、メタアクリル酸変性ビスフェノールＦ型エポキシ樹脂（硬化性化合物（Ａ−１））を得た。
下記式で表されるポリエチレングリコールジアクリレート：共栄社化学製、ライトアクリレート１４ＥＧ-Ａ、分子量６００
Curable compound (A-1):
A methacrylic acid-modified bisphenol F type epoxy resin (95% partially methacrylic product) was synthesized by the following method.
160 g of liquid bisphenol F type epoxy resin ( YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq), 0.1 g of p-methoxyphenol as a polymerization inhibitor, 0.2 g of triethanolamine as a catalyst, And 81.7 g of methacrylic acid were charged into the flask, dried air was fed, and the mixture was reacted at 90 ° C. with reflux stirring for 5 hours. The obtained reaction product was washed 20 times with ultrapure water to obtain a methacrylic acid-modified bisphenol F type epoxy resin (curable compound (A-1)).
Polyethylene glycol diacrylate represented by the following formula: manufactured by Kyoeisha Chemical Co., Ltd., light acrylate 14EG-A, molecular weight 600
（熱硬化性化合物（Ｄ））
エポキシ樹脂：三菱化学社製、ｊＥＲ１００４、軟化点９７℃
(Thermosetting compound (D))
Epoxy resin: Mitsubishi Chemical Corporation, jER 1004, softening point 97 ° C
（その他成分（Ｆ））
シリカ粒子：日本触媒社製、Ｓ−１００
熱可塑性樹脂粒子：アイカ工業社製、Ｆ３５１、軟化点１２０℃、平均粒子径０．３μｍ
γ-グリシドキシプロピルトリメトキシシラン：信越化学工業社製、ＫＢＭ-４０３）
(Other components (F))
Silica particles: Nippon Shokubai Co., Ltd., S-100
Thermoplastic resin particles: manufactured by Aika Industries, F351, softening point 120 ° C., average particle diameter 0.3 μm
γ-glycidoxypropyltrimethoxysilane: Shin-Etsu Chemical Co., Ltd., KBM-403)
（実施例１）
硬化性化合物（Ａ）として硬化性化合物（Ａ−１）を４２０質量部と、ポリエチレングリコールジアクリレート（共栄社化学製、ライトアクリレート１４ＥＧ−Ａ）を２００質量部と、化合物（Ｂ）として合成例１で得られた化合物（Ｂ−１）を１０質量部と、熱硬化性化合物（Ｄ）としてエポキシ樹脂（三菱化学社製、ｊＥＲ１００４）を５０質量部と、熱硬化剤（Ｅ）としてアジピン酸ジヒドラジド（日本化成社製ＡＤＨ）を９０質量部と、充填剤としてシリカ粒子（日本触媒社製、Ｓ−１００）を１３０質量部と、熱可塑性樹脂粒子としてＦ３５１（アイカ工業社製）を７０質量部と、シランカップリング剤としてγ-グリシドキシプロピルトリメトキシシラン（信越化学工業社製、ＫＢＭ−４０３）を２０質量部とを、三本ロールミルを用いて均一な液となるように十分に混合して、光硬化性樹脂組成物を得た。
Example 1
Synthesis Example 1 using 420 parts by mass of the curable compound (A-1) as the curable compound (A), 200 parts by mass of polyethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate 14EG-A), and the compound (B). 10 parts by mass of the compound (B-1) obtained in the above, 50 parts by mass of epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER 1004) as the thermosetting compound (D), and adipic acid as the thermosetting agent (E) and dihydrazide (manufactured by Nippon Kasei Chemical Co., Ltd. ADH) to 90 parts by weight, silica particles (Nippon touch Nakadachisha Co., S-100) as filler and 130 parts by weight, the thermoplastic resin particles F351 (the Aika Kogyo Co., Ltd.) 70 3 parts by mass of 20 parts by mass of γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) as a silane coupling agent. It was mixed in sufficient a uniform liquid was used to obtain a photocurable resin composition.
本発明は、例えば表示素子シール剤、特に液晶表示素子シール剤として用いた際に、可視光に対しても十分な硬化性を有し、且つ液晶の汚染を高度に抑制できる光硬化性樹脂組成物を提供することができる。 The present invention is a photocurable resin composition that has sufficient curability for visible light and can highly suppress contamination of liquid crystal when used as, for example, a display element sealant, particularly a liquid crystal display element sealant. Things can be provided.
Claims (16)
下記一般式（１）で表される化合物（Ｂ）と、
を含む、光硬化性樹脂組成物。
Ｒ１〜Ｒ８の少なくとも１つは、−Ｓ−Ｗ（Ｗは、置換されていてもよい炭素数１〜８のアルキル基、置換されていてもよい炭素数１〜８のアルケニル基、又は置換されていてもよいアリール基）であり、
それ以外のＲ１〜Ｒ８は、水素原子、水酸基、置換されていてもよい炭素数１〜８のアルキル基、置換されていてもよい炭素数１〜８のアルケニル基、又は置換されていてもよいアリール基であり、且つ
Ｒ１〜Ｒ８の少なくとも１つは、水酸基、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルキル基、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルケニル基、水酸基若しくは水酸基含有基で置換されたアリール基、又は−Ｓ−Ｘ（Ｘは、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルキル基、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルケニル基、又は水酸基若しくは水酸基含有基で置換されたアリール基）である］ A curable compound (A) having an ethylenically unsaturated double bond in the molecule;
Compound (B) represented by the following general formula (1),
A photocurable resin composition comprising:
At least one of R 1 to R 8 is —S—W (W is an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 1 to 8 carbon atoms, or An optionally substituted aryl group),
Other R 1 to R 8 are a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 1 to 8 carbon atoms, or a substituted group. And at least one of R 1 to R 8 is a hydroxyl group, a C 1-8 alkyl group substituted with a hydroxyl group or a hydroxyl group-containing group, a carbon number substituted with a hydroxyl group or a hydroxyl group-containing group 1-8 alkenyl group, a hydroxyl group or a hydroxyl group-containing aryl group substituted by group, or -S-X (X is a hydroxyl group or a hydroxyl group-containing substituted alkyl group having 1 to 8 carbon atoms in the group, a hydroxyl group or a hydroxyl group-containing A C1-C8 alkenyl group substituted with a group, or an aryl group substituted with a hydroxyl group or a hydroxyl group-containing group ]
Ｘは、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルキル基、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルケニル基、又は水酸基若しくは水酸基含有基で置換されたアリール基である） The photocurable resin composition according to claim 1, wherein the compound (B) is represented by the following general formula (2).
X is an alkyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, an alkenyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, or an aryl substituted with a hydroxyl group or a hydroxyl group-containing group Base)
Ｘは、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルキル基、水酸基若しくは水酸基含有基で置換された炭素数１〜８のアルケニル基、又は水酸基若しくは水酸基含有基で置換されたアリール基である） The photocurable resin composition according to claim 1 or 2, wherein the compound (B) is represented by the following general formula (2 ').
X is an alkyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, an alkenyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, or an aryl substituted with a hydroxyl group or a hydroxyl group-containing group Base)
熱硬化剤（Ｅ）と
をさらに含む、請求項１〜６のいずれか一項に記載の光硬化性樹脂組成物。 Thermosetting compound (D) having an epoxy group in the molecule (provided that the thermosetting compound (D) is different from the curable compound (A))
The photocurable resin composition according to any one of claims 1 to 6, further comprising a thermosetting agent (E).
前記シールパターンが未硬化の状態において、前記シールパターンの領域内、又は前記一方の基板と対になる他方の基板に液晶を滴下する工程と、
前記一方の基板と前記他方の基板とを、前記シールパターンを介して重ね合わせる工程と、
前記シールパターンを硬化させる工程と、
を含む、液晶表示パネルの製造方法。 Using the liquid crystal display element sealant according to claim 11 to form a seal pattern on one substrate;
In the uncured state of the seal pattern, dropping the liquid crystal on the other substrate that is paired with the one substrate in the region of the seal pattern;
Superimposing the one substrate and the other substrate through the seal pattern;
Curing the seal pattern;
A method for manufacturing a liquid crystal display panel, comprising:
前記一対の基板の間に配置された枠状のシール部材と、
前記一対の基板の間の前記シール部材で囲まれた空間に充填された液晶層とを含み、
前記シール部材が、請求項１１に記載の液晶表示素子シール剤の硬化物である、液晶表示パネル。 A pair of substrates;
A frame-shaped sealing member disposed between the pair of substrates;
A liquid crystal layer filled in a space surrounded by the seal member between the pair of substrates,
The liquid crystal display panel whose said sealing member is the hardened | cured material of the liquid crystal display element sealing agent of Claim 11 .
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| PCT/JP2016/087394 WO2017130594A1 (en) | 2016-01-25 | 2016-12-15 | Photocurable resin composition, display element sealant, liquid crystal display element sealant, and liquid crystal display panel and production method therefor |
| CN201680079862.5A CN108495869B (en) | 2016-01-25 | 2016-12-15 | Photocurable resin composition, display element sealant, liquid crystal display panel, and method for producing same |
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