TWI801554B - Photopolymerization initiator, sealant for display elements, upper and lower conduction materials, display elements and compounds - Google Patents
Photopolymerization initiator, sealant for display elements, upper and lower conduction materials, display elements and compounds Download PDFInfo
- Publication number
- TWI801554B TWI801554B TW108112686A TW108112686A TWI801554B TW I801554 B TWI801554 B TW I801554B TW 108112686 A TW108112686 A TW 108112686A TW 108112686 A TW108112686 A TW 108112686A TW I801554 B TWI801554 B TW I801554B
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- Taiwan
- Prior art keywords
- meth
- acrylate
- sealant
- display elements
- liquid crystal
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 120
- 239000000565 sealant Substances 0.000 title claims abstract description 68
- 239000003999 initiator Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 16
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 81
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002835 absorbance Methods 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 239000010419 fine particle Substances 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 11
- 238000011109 contamination Methods 0.000 abstract description 21
- 230000009257 reactivity Effects 0.000 abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 109
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- -1 4-( N,N-dimethylamino)benzoyloxy Chemical group 0.000 description 54
- 238000007789 sealing Methods 0.000 description 31
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- 239000000758 substrate Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 18
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- 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 2
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
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- UGJDXRVQCYBXAJ-UHFFFAOYSA-N 4-(dimethylamino)benzoyl chloride Chemical compound CN(C)C1=CC=C(C(Cl)=O)C=C1 UGJDXRVQCYBXAJ-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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Abstract
本發明之目的在於提供一種對於長波長之光之反應性優異之光聚合起始劑。又，本發明之目的在於提供一種顯示元件用密封劑、以及使用該顯示元件用密封劑而成之上下導通材料及顯示元件，該顯示元件用密封劑含有該光聚合起始劑，對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異。進而，本發明之目的在於提供一種構成該光聚合起始劑之化合物。
本發明之光聚合起始劑係具有可經羥基取代之9-氧硫
Description
本發明係關於一種對於長波長之光之反應性優異之光聚合起始劑。又，本發明係關於一種顯示元件用密封劑、以及使用該顯示元件用密封劑而成之上下導通材料及顯示元件，該顯示元件用密封劑含有該光聚合起始劑，對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異。進而，本發明係關於一種構成該光聚合起始劑之化合物。The present invention relates to a photopolymerization initiator excellent in reactivity to long-wavelength light. Also, the present invention relates to a sealant for display elements, and an upper and lower conduction material and a display element using the sealant for display elements. It has excellent curability, and is also excellent in low liquid crystal contamination when used in liquid crystal display elements. Furthermore, the present invention relates to a compound constituting the photopolymerization initiator.
近年，作為液晶顯示單元等液晶顯示元件之製造方法，就縮短生產節拍時間（takt time）、使用液晶量之最佳化等觀點而言，採用如專利文獻1、專利文獻2所揭示之使用光熱併用硬化型密封劑之被稱為滴下工法之液晶滴下方式。
於滴下工法中，首先，藉由滴塗，於2片附電極之透明基板之一者形成框狀之密封圖案。其次，於密封劑未硬化之狀態將液晶之微小滴滴下至透明基板之框內整個面，並立即貼合另一透明基板，對密封部照射紫外線等光進行預硬化。其後，於液晶退火時加熱進行正式硬化，從而製作液晶顯示元件。若於減壓進行基板之貼合，則可以極高之效率製造液晶顯示元件，現在該滴下工法成為液晶顯示元件之製造方法之主流。In recent years, as a method of manufacturing liquid crystal display elements such as liquid crystal display units, from the perspective of shortening the takt time (takt time) and optimizing the amount of liquid crystals used, the use of light and heat as disclosed in
然而，於行動電話、攜帶型遊戲機等各種附液晶面板之可攜式機器普及之現代，裝置之小型化係最為需求之課題。作為裝置之小型化之方法，可列舉液晶顯示部之窄邊緣化，例如進行有將密封部之位置配置於黑矩陣下（以下，亦稱為窄邊緣設計）。However, in modern times when various portable devices with LCD panels such as mobile phones and portable game consoles are popularized, miniaturization of devices is the most demanded issue. As a method of reducing the size of the device, narrowing the edge of the liquid crystal display part can be mentioned, for example, the position of the sealing part is arranged under the black matrix (hereinafter also referred to as narrow edge design).
然而，於窄邊緣設計中，由於密封劑配置於黑矩陣之正下方，故而當進行滴下工法時，存在使密封劑光硬化時所照射之光被遮擋，光無法到達密封劑之內部而使硬化變得不充分之問題。當如上所述密封劑之硬化變得不充分時，存在如下問題：未硬化之密封劑成分溶出於液晶中，由於溶出之密封劑成分而發生之硬化反應於液晶中進行，由此產生液晶污染。However, in the narrow edge design, since the sealant is arranged directly under the black matrix, when the dripping method is performed, the light irradiated when the sealant is hardened by light is blocked, and the light cannot reach the inside of the sealant to harden The problem of becoming inadequate. When the hardening of the sealant becomes insufficient as described above, there is a problem that the unhardened sealant components dissolve into the liquid crystal, and the hardening reaction due to the eluted sealant components proceeds in the liquid crystal, thereby causing contamination of the liquid crystal. .
又，通常，進行紫外線之照射作為使密封劑光硬化之方法，但尤其是於液晶滴下工法中，由於在滴下液晶後使密封劑硬化，故而存在因照射紫外線而導致液晶劣化之問題。因此，為了防止由紫外線所導致之液晶之劣化，進行有藉由介隔截止濾光器等之可見光區域之長波長之光而進行之光硬化。作為藉由長波長之光使密封劑光硬化之方法，考慮組合對於長波長之光之感度高之增感劑與光聚合起始劑而使用之方法。例如，於專利文獻3及專利文獻4中，揭示有組合光聚合起始劑與增感劑進行摻合所得之光硬化性樹脂組成物。然而，於使用該等光硬化性樹脂組成物作為液晶顯示元件用密封劑之情形時，存在如下問題：為了藉由長波長之光充分地進行光硬化，而使光聚合起始劑與增感劑之合計量變多，由此有時會產生液晶污染。
先前技術文獻
專利文獻In addition, ultraviolet irradiation is usually performed as a method of photocuring the sealant, but especially in the liquid crystal dropping method, since the sealant is cured after dropping the liquid crystal, there is a problem that the liquid crystal is degraded by irradiation of ultraviolet rays. Therefore, in order to prevent deterioration of the liquid crystal due to ultraviolet rays, photocuring by long-wavelength light in the visible region through a cut filter or the like is performed. As a method of photocuring a sealant with long-wavelength light, a method of using a combination of a sensitizer and a photopolymerization initiator having high sensitivity to long-wavelength light is conceivable. For example,
專利文獻1：日本特開2001-133794號公報 專利文獻2：國際公開第02/092718號 專利文獻3：日本特開2017-125033號公報 專利文獻4：國際公開第2017/130594號Patent Document 1: Japanese Patent Laid-Open No. 2001-133794 Patent Document 2: International Publication No. 02/092718 Patent Document 3: Japanese Patent Laid-Open No. 2017-125033 Patent Document 4: International Publication No. 2017/130594
[發明所欲解決之課題][Problem to be Solved by the Invention]
本發明之目的在於提供一種對於長波長之光之反應性優異之光聚合起始劑。又，本發明之目的在於提供一種顯示元件用密封劑、以及使用該顯示元件用密封劑而成之上下導通材料及顯示元件，該顯示元件用密封劑含有該光聚合起始劑，對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異。進而，本發明之目的在於提供一種構成該光聚合起始劑之化合物。 [解決課題之技術手段]An object of the present invention is to provide a photopolymerization initiator excellent in reactivity to long-wavelength light. Furthermore, the object of the present invention is to provide a sealant for a display element, and an upper and lower conduction material and a display element using the sealant for a display element. It is excellent in light curability, and also excellent in low liquid crystal contamination when used in liquid crystal display elements. Furthermore, the object of this invention is to provide the compound which comprises this photoinitiator. [Technical means to solve the problem]
本發明係一種光聚合起始劑，其係具有可經羥基取代之9-氧硫
本發明者發現，具有可經羥基取代之9-氧硫
本發明之光聚合起始劑係具有可經羥基取代之9-氧硫
作為上述胺基，就成為對於長波長之光之反應性更優異者而言，較佳為一級胺基或二烷基胺基，更佳為二烷基胺基，進而更佳為二甲基胺基。 又，本發明之光聚合起始劑較佳為具有4-(N,N-二烷基胺基)苯甲醯氧基作為包含上述二烷基胺基之基，更佳為具有4-(N,N-二甲基胺基)苯甲醯氧基。The above-mentioned amine group is preferably a primary amine group or a dialkylamine group, more preferably a dialkylamine group, and still more preferably a dimethyl group, in terms of being more excellent in reactivity to long-wavelength light. Amino. Also, the photopolymerization initiator of the present invention preferably has a 4-(N,N-dialkylamino) benzoyloxy group as a group comprising the above-mentioned dialkylamine group, more preferably has a 4-( N,N-dimethylamino)benzoyloxy.
本發明之光聚合起始劑就低液晶污染性之觀點而言，較佳為具有羥基，更佳為1分子中具有2個以上之羥基。The photopolymerization initiator of the present invention preferably has a hydroxyl group from the viewpoint of low liquid crystal contamination, and more preferably has two or more hydroxyl groups in one molecule.
本發明之光聚合起始劑就低液晶污染性之觀點而言，分子量較佳為200以上，更佳為400以上。 本發明之光聚合起始劑之分子量之較佳之上限並無特別，但實質之上限為3萬。 再者，於本說明書中，上述「分子量」就分子結構特定之化合物而言係由結構式求得之分子量，但就聚合度之分佈較廣之化合物及改質部位未特定之化合物而言存在使用數量平均分子量表示之情形。又，於本說明書中，上述「數量平均分子量」係藉由凝膠滲透層析法（GPC）使用四氫呋喃作為溶劑進行測定並藉由聚苯乙烯換算所求得之值。作為藉由GPC測定由聚苯乙烯換算所獲得之數量平均分子量時所使用之管柱，例如可列舉：Shodex LF-804（昭和電工公司製造）等。The photopolymerization initiator of the present invention has a molecular weight of preferably 200 or more, more preferably 400 or more, from the viewpoint of low liquid crystal contamination. There is no particular upper limit on the molecular weight of the photopolymerization initiator of the present invention, but the actual upper limit is 30,000. Furthermore, in this specification, the above-mentioned "molecular weight" refers to the molecular weight obtained from the structural formula for a compound with a specific molecular structure, but it exists for a compound with a wide distribution of polymerization degrees and a compound with an unspecified modified site. The situation represented by the number average molecular weight. In addition, in this specification, the said "number average molecular weight" is the value calculated|required by the polystyrene conversion measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. As a column used when measuring the number average molecular weight obtained by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko Co., Ltd.) etc. are mentioned, for example.
本發明之光聚合起始劑以濃度成為0.1 mg/mL之方式溶解於乙腈時之在波長420 nm之吸光度為0.10以上。藉由使上述波長420 nm之吸光度為0.10以上，本發明之光聚合起始劑可良好地用於藉由可見光區域之長波長之光進行硬化之顯示元件用密封劑等。 上述吸光度更佳為0.15以上。 上述吸光度可使用分光光度計於光程長度1 cm之條件進行測定。作為上述分光光度計，例如可列舉：U-3900（Hitachi High-Tech Science公司製造）等。When the photopolymerization initiator of the present invention is dissolved in acetonitrile at a concentration of 0.1 mg/mL, the absorbance at a wavelength of 420 nm is 0.10 or more. The photoinitiator of this invention can be favorably used for the sealing compound for display elements etc. which harden|cure with the light of the long wavelength of a visible light region by making the absorbance of the said wavelength 420 nm 0.10 or more. The above-mentioned absorbance is more preferably at least 0.15. The above-mentioned absorbance can be measured using a spectrophotometer under the condition that the optical path length is 1 cm. As said spectrophotometer, U-3900 (made by Hitachi High-Tech Science Co., Ltd.) etc. are mentioned, for example.
本發明之光聚合起始劑具體而言較佳為下述式（1-1）或（1-2）所表示之化合物，更佳為下述式（2-1）、（2-2）或（2-3）所表示之化合物。下述式（2-1）、（2-2）或（2-3）所表示之化合物亦為本發明之一。Specifically, the photopolymerization initiator of the present invention is preferably a compound represented by the following formula (1-1) or (1-2), more preferably the following formula (2-1), (2-2) Or the compound represented by (2-3). A compound represented by the following formula (2-1), (2-2) or (2-3) is also one of the present invention.
式（1-1）及（1-2）中，R1 為可經羥基取代之碳數1~20之伸烷基、或可經羥基取代之碳數1~20之(聚)伸烷氧基，R2 分別獨立為氫原子或胺基，且至少1個R2 為胺基。 作為上述R2 所表示之胺基，較佳為一級胺基、二甲基胺基或二乙基胺基。In formulas (1-1) and (1-2), R 1 is an alkylene group with 1 to 20 carbons which may be substituted by hydroxyl, or a (poly)alkylene oxide with 1 to 20 carbons which may be substituted by hydroxyl group, R 2 are each independently a hydrogen atom or an amine group, and at least one R 2 is an amine group. The amino group represented by R 2 above is preferably a primary amino group, a dimethylamine group or a diethylamine group.
含有硬化性樹脂與本發明之光聚合起始劑之顯示元件用密封劑亦為本發明之一。 本發明之顯示元件用密封劑由於含有本發明之光聚合起始劑，故而對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異。即，本發明之顯示元件用密封劑可作為液晶顯示元件用密封劑而良好地用於液晶顯示元件。The sealing compound for display elements containing curable resin and the photoinitiator of this invention is also one of this invention. Since the sealing compound for display elements of this invention contains the photoinitiator of this invention, it is excellent in the curability with respect to the light of a long wavelength, and it is also excellent in low liquid crystal contamination property when used for a liquid crystal display element. That is, the sealing compound for display elements of this invention can be used favorably for a liquid crystal display element as a sealing compound for liquid crystal display elements.
作為本發明之顯示元件用密封劑中之本發明之光聚合起始劑之含量，相對於硬化性樹脂100重量份，較佳之下限為0.01重量份，較佳之上限為5重量份。藉由使本發明之光聚合起始劑之含量為該範圍，獲得之顯示元件用密封劑對於長波長之光之硬化性更加優異，且於用於液晶顯示元件之情形時使兼具對於長波長之光之硬化性及低液晶污染性之效果更加優異。本發明之光聚合起始劑之含量之更佳之下限為0.5重量份，更佳之上限為3重量份。The content of the photopolymerization initiator of the present invention in the sealant for display elements of the present invention is preferably 0.01 parts by weight in the lower limit and 5 parts by weight in the upper limit relative to 100 parts by weight of the curable resin. By making content of the photopolymerization initiator of this invention into this range, the sealing compound for display elements obtained is more excellent in the hardening property with respect to the light of a long wavelength, and when using it for a liquid crystal display element, it can make it compatible with a long-term. The curability of the wavelength of light and the effect of low liquid crystal contamination are more excellent. The more preferable lower limit of the content of the photopolymerization initiator of the present invention is 0.5 parts by weight, and the more preferable upper limit is 3 parts by weight.
本發明之顯示元件用密封劑含有硬化性樹脂。 上述硬化性樹脂較佳為含有(甲基)丙烯酸化合物。 作為上述(甲基)丙烯酸化合物，例如可列舉：(甲基)丙烯酸酯化合物、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺酯等。其中，較佳為環氧(甲基)丙烯酸酯。又，上述(甲基)丙烯酸化合物就反應性之觀點而言，較佳為分子中具有2個以上之(甲基)丙烯醯基者。 再者，於本說明書中，上述「(甲基)丙烯酸」意指丙烯酸或甲基丙烯酸，上述「(甲基)丙烯酸化合物」意指具有(甲基)丙烯醯基之化合物，上述「(甲基)丙烯醯基」意指丙烯醯基或甲基丙烯醯基。又，上述「(甲基)丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯。進而，上述「環氧(甲基)丙烯酸酯」表示使環氧化合物中之所有環氧基與(甲基)丙烯酸反應所得之化合物。The sealing compound for display elements of this invention contains curable resin. The above curable resin preferably contains a (meth)acrylic compound. As said (meth)acryl compound, a (meth)acrylate compound, epoxy (meth)acrylate, (meth)acrylate amine, etc. are mentioned, for example. Among them, epoxy (meth)acrylate is preferred. Moreover, the above-mentioned (meth)acrylic compound preferably has two or more (meth)acryl groups in the molecule from the viewpoint of reactivity. Furthermore, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, the above-mentioned "(meth)acrylic acid compound" means a compound having a (meth)acryl group, and the above-mentioned "(meth)acrylic acid compound" means a compound having a (meth)acryl group, and the above-mentioned "(meth)acrylic acid "Acryl" means acryl or methacryl. In addition, the above-mentioned "(meth)acrylate" means acrylate or methacrylate. Furthermore, the said "epoxy (meth)acrylate" means the compound obtained by reacting all the epoxy groups in an epoxy compound with (meth)acrylic acid.
作為上述(甲基)丙烯酸酯化合物中之單官能者，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、醯亞胺(甲基)丙烯酸酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、鄰苯二甲酸2-(甲基)丙烯醯氧基乙基2-羥基丙酯、磷酸2-(甲基)丙烯醯氧基乙酯、(甲基)丙烯酸縮水甘油酯等。Examples of the monofunctional ones among the above-mentioned (meth)acrylate compounds include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , Isononyl (meth)acrylate, Isodecyl (meth)acrylate, Lauryl (meth)acrylate, Isomyristyl (meth)acrylate, Stearyl (meth)acrylate, (Meth) 2-Hydroxyethyl acrylate, 2-Hydroxypropyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, Cyclohexyl (meth)acrylate, ( Isocamphoryl methacrylate, Dicyclopentenyl (meth)acrylate, Benzyl (meth)acrylate, 2-Methoxyethyl (meth)acrylate, 2-Ethoxy (meth)acrylate Ethyl ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Meth)acrylate, Phenoxy Diethylene Glycol (Meth) Acrylate, Phenoxy Polyethylene Glycol (Meth) Acrylate, Tetrahydrofurfuryl (Meth) Acrylate, Ethyl Carbitol ( Meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H (meth)acrylate - Octafluoropentyl ester, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryl Oxyethylsuccinic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid, 2-(meth)acryloxyethyl 2-hydroxypropyl phthalate, phosphoric acid 2 -(meth)acryloxyethyl ester, glycidyl (meth)acrylate, etc.
又，作為上述(甲基)丙烯酸酯化合物中之2官能者，例如可列舉：1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、2-正丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷加成雙酚A二(甲基)丙烯酸酯、環氧丙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚F二(甲基)丙烯酸酯、二(甲基)丙烯酸二羥甲基二環戊二烯酯、環氧乙烷改質異三聚氰酸二(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、碳酸酯二醇二(甲基)丙烯酸酯、聚醚二醇二(甲基)丙烯酸酯、聚酯二醇二(甲基)丙烯酸酯、聚己內酯二醇二(甲基)丙烯酸酯、聚丁二烯二醇二(甲基)丙烯酸酯等。In addition, examples of bifunctional ones among the above-mentioned (meth)acrylate compounds include: 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di (meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl di(meth)acrylate Alcohol di(meth)acrylate, Ethylene oxide added bisphenol A di(meth)acrylate, Propylene oxide added bisphenol A di(meth)acrylate, Ethylene oxide added bisphenol F di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylic acid 2-Hydroxy-3-(meth)acryloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate Acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.
又，作為上述(甲基)丙烯酸酯化合物中之3官能以上者，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成異三聚氰酸三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、環氧丙烷加成甘油三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、磷酸三(甲基)丙烯醯氧基乙酯、二(三羥甲基丙烷)四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等。In addition, examples of trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(methyl ) acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric Acid tri(meth)acrylate, Glycerin tri(meth)acrylate, Propylene oxide added glycerol tri(meth)acrylate, Neopentylthritol tri(meth)acrylate, Phosphate tri(meth)acrylate Acryloxyethyl ester, bis(trimethylolpropane)tetra(meth)acrylate, neopentylthritol tetra(meth)acrylate, dipenteoerythritol penta(meth)acrylate, dinew Pentaerythritol hexa(meth)acrylate, etc.
作為上述環氧(甲基)丙烯酸酯，例如可列舉藉由按照慣例於鹼性觸媒之存在下使環氧化合物與(甲基)丙烯酸進行反應而獲得者等。As said epoxy (meth)acrylate, the thing obtained by making an epoxy compound and (meth)acrylic acid react conventionally in the presence of an alkaline catalyst, etc. are mentioned, for example.
作為成為用於合成上述環氧(甲基)丙烯酸酯之原料之環氧化合物，例如可列舉：雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚S型環氧化合物、2,2'-二烯丙基雙酚A型環氧化合物、氫化雙酚型環氧化合物、環氧丙烷加成雙酚A型環氧化合物、間苯二酚型環氧化合物、聯苯型環氧化合物、硫醚型環氧化合物、二苯醚型環氧化合物、二環戊二烯型環氧化合物、萘型環氧化合物、酚系酚醛清漆型環氧化合物、鄰甲酚酚醛清漆型環氧化合物、二環戊二烯酚醛清漆型環氧化合物、聯苯酚醛清漆型環氧化合物、萘酚系酚醛清漆型環氧化合物、縮水甘油胺型環氧化合物、烷基多元醇型環氧化合物、橡膠改質型環氧化合物、縮水甘油酯化合物等。As an epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2 ,2'- Diallyl bisphenol A type epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide addition bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type ring Oxygen compounds, thioether-type epoxy compounds, diphenyl ether-type epoxy compounds, dicyclopentadiene-type epoxy compounds, naphthalene-type epoxy compounds, phenolic novolak-type epoxy compounds, o-cresol novolak-type rings Oxygen compounds, dicyclopentadiene novolak-type epoxy compounds, biphenyl novolak-type epoxy compounds, naphthol-based novolac-type epoxy compounds, glycidylamine-type epoxy compounds, alkyl polyol-type epoxy compounds , rubber-modified epoxy compounds, glycidyl ester compounds, etc.
作為上述雙酚A型環氧化合物中之市售者，例如可列舉：jER828EL、jER1004（皆為三菱化學公司製造）、Epiclon 850CRP（DIC公司製造）等。 作為上述雙酚F型環氧化合物中之市售者，例如可列舉：jER806、jER4004（皆為三菱化學公司製造）等。 作為上述雙酚S型環氧化合物中之市售者，例如可列舉：Epiclon EXA1514（DIC公司製造）等。 作為上述2,2'-二烯丙基雙酚A型環氧化合物中之市售者，例如可列舉：RE-810NM（日本化藥公司製造）等。 作為上述氫化雙酚型環氧化合物中之市售者，例如可列舉：Epiclon EXA7015（DIC公司製造）等。 作為上述環氧丙烷加成雙酚A型環氧化合物中之市售者，例如可列舉：EP-4000S（ADEKA公司製造）等。 作為上述間苯二酚型環氧化合物中之市售者，例如可列舉：EX-201（Nagase chemteX公司製造）等。 作為上述聯苯型環氧化合物中之市售者，例如可列舉：jER YX-4000H（三菱化學公司製造）等。 作為上述硫醚型環氧化合物中之市售者，例如可列舉：YSLV-50TE（NIPPON STEEL Chemical & Material公司製造）等。 作為上述二苯醚型環氧化合物中之市售者，例如可列舉：YSLV-80DE（NIPPON STEEL Chemical & Material公司製造）等。 作為上述二環戊二烯型環氧化合物中之市售者，例如可列舉：EP-4088S（ADEKA公司製造）等。 作為上述萘型環氧化合物中之市售者，例如可列舉：Epiclon HP4032、Epiclon EXA-4700（皆為DIC公司製造）等。 作為上述酚系酚醛清漆型環氧化合物中之市售者，例如可列舉：Epiclon N-770（DIC公司製造）等。 作為上述鄰甲酚酚醛清漆型環氧化合物中之市售者，例如可列舉：Epiclon N-670-EXP-S（DIC公司製造）等。 作為上述二環戊二烯酚醛清漆型環氧化合物中之市售者，例如可列舉：Epiclon HP7200（DIC公司製造）等。 作為上述聯苯酚醛清漆型環氧化合物中之市售者，例如可列舉：NC-3000P（日本化藥公司製造）等。 作為上述萘酚系酚醛清漆型環氧化合物中之市售者，例如可列舉：ESN-165S（NIPPON STEEL Chemical & Material公司製造）等。 作為上述縮水甘油胺型環氧化合物中之市售者，例如可列舉：jER630（三菱化學公司製造）、Epiclon 430（DIC公司製造）、TETRAD-X（三菱瓦斯化學公司製造）等。 作為上述烷基多元醇型環氧化合物中之市售者，例如可列舉：ZX-1542（NIPPON STEEL Chemical & Material公司製造）、Epiclon 726（DIC公司製造）、Epolight 80MFA（共榮社化學公司製造）、DENACOL EX-611（Nagase chemteX公司製造）等。 作為上述橡膠改質型環氧化合物中之市售者，例如可列舉：YR-450、YR-207（皆為NIPPON STEEL Chemical & Material公司製造）、Epolead PB（Daicel公司製造）等。 作為上述縮水甘油酯化合物中之市售者，例如可列舉：DENACOL EX-147（Nagase chemteX公司製造）等。 作為上述環氧化合物中之其他市售者，例如可列舉：YDC-1312、YSLV-80XY、YSLV-90CR（皆為NIPPON STEEL Chemical & Material公司製造）、XAC4151（旭化成公司製造）、jER1031、jER1032（皆為三菱化學公司製造）、EXA-7120（DIC公司製造）、TEPIC（日產化學公司製造）等。As what is marketed among the said bisphenol A type epoxy compounds, jER828EL, jER1004 (all are the Mitsubishi Chemical Corporation make), Epiclon 850CRP (the DIC company make), etc. are mentioned, for example. As what is marketed among the said bisphenol F type epoxy compounds, jER806, jER4004 (all are the Mitsubishi Chemical Corporation make), etc. are mentioned, for example. As what is marketed among the said bisphenol S type epoxy compounds, Epiclon EXA1514 (made by DIC company) etc. are mentioned, for example. As what is marketed among the said 2,2'- diallyl bisphenol A type epoxy compounds, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said hydrogenated bisphenol type epoxy compounds, Epiclon EXA7015 (made by DIC company) etc. are mentioned, for example. As what is marketed among the said propylene oxide addition bisphenol A type epoxy compounds, EP-4000S (made by ADEKA company) etc. are mentioned, for example. As what is marketed among the said resorcinol type epoxy compounds, EX-201 (made by Nagase ChemteX company) etc. are mentioned, for example. As what is marketed among the said biphenyl type epoxy compounds, jER YX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example. As what is marketed among the said thioether type epoxy compounds, YSLV-50TE (made by a Nippon Steel Chemical & Material company) etc. are mentioned, for example. As what is marketed among the said diphenyl ether type epoxy compounds, YSLV-80DE (made by Nippon Steel Chemical & Material company) etc. are mentioned, for example. As what is marketed among the said dicyclopentadiene type epoxy compounds, EP-4088S (made by ADEKA company) etc. are mentioned, for example. As what is marketed among the said naphthalene type epoxy compounds, Epiclon HP4032, Epiclon EXA-4700 (all are the DIC company make), etc. are mentioned, for example. As what is marketed among the said phenolic novolak type epoxy compounds, Epiclon N-770 (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said o-cresol novolac type epoxy compounds, Epiclon N-670-EXP-S (made by DIC company) etc. are mentioned, for example. As what is marketed among the said dicyclopentadiene novolac type epoxy compounds, Epiclon HP7200 (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said biphenyl novolac type epoxy compounds, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said naphthol-type novolak-type epoxy compounds, ESN-165S (made by Nippon Steel Chemical & Material Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said glycidylamine type epoxy compounds, jER630 (made by Mitsubishi Chemical Corporation), Epiclon 430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemical Corporation), etc. are mentioned, for example. As what is marketed among the said alkyl polyol type epoxy compounds, ZX-1542 (made by NIPPON STEEL Chemical & Material Co., Ltd.), Epiclon 726 (made by DIC Corporation), Epolight 80MFA (made by Kyoeisha Chemical Co., Ltd.) are mentioned, for example. ), DENACOL EX-611 (manufactured by Nagase ChemteX Co., Ltd.), etc. As what is marketed among the said rubber-modified epoxy compounds, YR-450, YR-207 (all are the Nippon Steel Chemical & Material company make), Epolead PB (Daicel company make), etc. are mentioned, for example. As what is marketed among the said glycidyl ester compounds, Denacol EX-147 (made by Nagase ChemteX Co., Ltd.) etc. are mentioned, for example. Examples of other commercially available epoxy compounds include: YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NIPPON STEEL Chemical & Material), XAC4151 (manufactured by Asahi Kasei), jER1031, jER1032 ( All are manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), etc.
作為上述環氧(甲基)丙烯酸酯中之市售者，例如可列舉：Daicel-Allnex公司製造之環氧(甲基)丙烯酸酯、新中村化學工業公司製造之環氧(甲基)丙烯酸酯、共榮社化學公司製造之環氧(甲基)丙烯酸酯、Nagase chemteX公司製造之環氧(甲基)丙烯酸酯等。 作為上述Daicel-Allnex公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3708、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182等。 作為上述新中村化學工業公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020等。 作為上述共榮社化學公司製造之環氧(甲基)丙烯酸酯，例如可列舉：環氧酯M-600A、環氧酯40EM、環氧酯70PA、環氧酯200PA、環氧酯80MFA、環氧酯3002M、環氧酯3002A、環氧酯1600A、環氧酯3000M、環氧酯3000A、環氧酯200EA、環氧酯400EA等。 作為上述Nagase chemteX公司製造之環氧(甲基)丙烯酸酯，例如可列舉：DENACOL ACRYLATE DA-141、DENACOL ACRYLATE DA-314、DENACOL ACRYLATE DA-911等。As what is marketed among the said epoxy (meth)acrylates, the epoxy (meth)acrylate by Daicel-Allnex company, the epoxy (meth)acrylate by Shin-Nakamura Chemical Industry Co., Ltd. are mentioned, for example , Epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase ChemteX Co., Ltd., and the like. Examples of epoxy (meth)acrylates manufactured by Daicel-Allnex include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182, etc. As epoxy (meth)acrylate by said Shin-Nakamura Chemical Industry Co., Ltd., EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 etc. are mentioned, for example. Examples of the epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. include epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester Oxyester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA, etc. As an epoxy (meth)acrylate by the said Nagase ChemteX company, Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 etc. are mentioned, for example.
上述(甲基)丙烯酸胺酯例如可藉由於觸媒量之錫系化合物存在下使具有羥基之(甲基)丙烯酸衍生物對異氰酸酯化合物進行反應而獲得。The said amine (meth)acrylate can be obtained by making the (meth)acrylic acid derivative which has a hydroxyl group react with an isocyanate compound, for example in the presence of the tin compound of catalytic amount.
作為上述異氰酸酯化合物，例如可列舉：異佛爾酮二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯（MDI）、氫化MDI、聚合MDI、1,5-萘二異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二甲基二異氰酸酯（XDI）、氫化XDI、離胺酸二異氰酸酯、三苯基甲烷三異氰酸酯、硫代磷酸三(異氰酸基苯基)酯、四甲基苯二甲基二異氰酸酯、1,6,11-十一烷三異氰酸酯等。Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, Phenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzylidine diisocyanate, xylylene diisocyanate (XDI) , hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethylxylylene diisocyanate, 1,6,11-undecane Triisocyanate etc.
又，作為上述異氰酸酯化合物，亦可使用藉由多元醇與過量之異氰酸酯化合物之反應所獲得之經鏈伸長之異氰酸酯化合物。 作為上述多元醇，例如可列舉：乙二醇、丙二醇、甘油、山梨醇、三羥甲基丙烷、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己內酯二醇等。In addition, as the above-mentioned isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyhydric alcohol with an excess of isocyanate compound can also be used. Examples of the above-mentioned polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.
作為上述具有羥基之(甲基)丙烯酸衍生物，例如可列舉：單(甲基)丙烯酸羥烷基酯、二元醇之單(甲基)丙烯酸酯、三元醇之單(甲基)丙烯酸酯或二(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等。 作為上述單(甲基)丙烯酸羥烷基酯，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等。 作為上述二元醇，例如可列舉：乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、聚乙二醇等。 作為上述三元醇，例如可列舉：三羥甲基乙烷、三羥甲基丙烷、甘油等。 作為上述環氧(甲基)丙烯酸酯，例如可列舉：雙酚A型環氧丙烯酸酯等。Examples of (meth)acrylic acid derivatives having a hydroxyl group include hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of diol, and mono(meth)acrylic acid of triol. ester or di(meth)acrylate, epoxy(meth)acrylate, etc. Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, etc. As said dihydric alcohol, ethylene glycol, 1, 2- propanediol, 1, 3-propanediol, 1, 3- butanediol, 1, 4- butanediol, polyethylene glycol etc. are mentioned, for example. As said trivalent alcohol, trimethylolethane, trimethylolpropane, glycerin etc. are mentioned, for example. As said epoxy (meth)acrylate, a bisphenol A epoxy acrylate etc. are mentioned, for example.
作為上述(甲基)丙烯酸胺酯中之市售者，例如可列舉：東亞合成公司製造之(甲基)丙烯酸胺酯、Daicel-Allnex公司製造之(甲基)丙烯酸胺酯、根上工業公司製造之(甲基)丙烯酸胺酯、新中村化學工業公司製造之(甲基)丙烯酸胺酯、共榮社化學公司製造之(甲基)丙烯酸胺酯等。 作為上述東亞合成公司製造之(甲基)丙烯酸胺酯，例如可列舉：M-1100、M-1200、M-1210、M-1600等。 作為上述Daicel-Allnex公司製造之(甲基)丙烯酸胺酯，例如可列舉：EBECRYL210、EBECRYL220、EBECRYL230、EBECRYL270、EBECRYL1290、EBECRYL2220、EBECRYL4827、EBECRYL4842、EBECRYL4858、EBECRYL5129、EBECRYL6700、EBECRYL8402、EBECRYL8803、EBECRYL8804、EBECRYL8807、EBECRYL9260等。 作為上述根上工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：Artresin UN-330、Artresin SH-500B、Artresin UN-1200TPK、Artresin UN-1255、Artresin UN-3320HB、Artresin UN-7100、Artresin UN-9000A、Artresin UN-9000H等。 作為上述新中村化學工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6HA、U-6LPA、U-10H、U-15HA、U-108、U-108A、U-122A、U-122P、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4000、UA-4100、UA-4200、UA-4400、UA-5201P、UA-7100、UA-7200、UA-W2A等。 作為上述共榮社化學公司製造之(甲基)丙烯酸胺酯，例如可列舉：AH-600、AI-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T等。As what is marketed among the above-mentioned amine (meth)acrylates, the (meth)amine acrylate manufactured by Toagosei Co., Ltd., the amine (meth)acrylate manufactured by Daicel-Allnex, and the product manufactured by Negami Kogyo Co., Ltd. are mentioned, for example. Amino (meth)acrylate, amine (meth)acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., amine (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., etc. As the amine (meth)acrylate manufactured by the said Toagosei Co., Ltd., M-1100, M-1200, M-1210, M-1600 etc. are mentioned, for example. Examples of the amine (meth)acrylate manufactured by Daicel-Allnex include: EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRY YL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 etc. Examples of the amine (meth)acrylate manufactured by Negami Industry Co., Ltd. include: Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H, etc. Examples of the amine (meth)acrylates manufactured by Shin-Nakamura Chemical Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U -10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000 , UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, etc. Examples of the above-mentioned amine (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA -306T etc.
上述硬化性樹脂以提高獲得之顯示元件用密封劑之接著性等為目的，較佳為含有環氧化合物。作為上述環氧化合物，例如可列舉：成為用於合成上述環氧(甲基)丙烯酸酯之原料之環氧化合物、或部分(甲基)丙烯醯基改質環氧化合物等。 再者，於本說明書中，上述部分(甲基)丙烯醯基改質環氧化合物意指1分子中分別具有1個以上之環氧基與(甲基)丙烯醯基之化合物，例如可藉由使1分子中具有2個以上之環氧基的環氧化合物之一部分環氧基與(甲基)丙烯酸反應而獲得。The said curable resin is for the purpose of improving the adhesiveness etc. of the sealant for display elements obtained, and it is preferable to contain an epoxy compound. As said epoxy compound, the epoxy compound used as the raw material for synthesizing the said epoxy (meth)acrylate, a partial (meth)acryl group modified epoxy compound, etc. are mentioned, for example. Furthermore, in this specification, the above-mentioned partially (meth)acryl group-modified epoxy compound means a compound having one or more epoxy groups and (meth)acryl groups in one molecule, for example, by It is obtained by reacting some epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid.
於含有上述(甲基)丙烯酸化合物與上述環氧化合物作為上述硬化性樹脂之情形時、或於含有上述部分(甲基)丙烯醯基改質環氧化合物作為上述硬化性樹脂之情形時，較佳為使上述硬化性樹脂中之(甲基)丙烯醯基與環氧基之合計中之(甲基)丙烯醯基之比率成為30莫耳%以上95莫耳%以下。藉由使上述(甲基)丙烯醯基之比率為該範圍，於將獲得之顯示元件用密封劑用於液晶顯示元件之情形時，抑制液晶污染之產生並且接著性更加優異。In the case of containing the above-mentioned (meth)acrylic compound and the above-mentioned epoxy compound as the above-mentioned curable resin, or in the case of containing the above-mentioned partially (meth)acryl group-modified epoxy compound as the above-mentioned curable resin, the Preferably, the ratio of the (meth)acryl group in the total of the (meth)acryl group and the epoxy group in the curable resin is 30 mol % or more and 95 mol % or less. When the obtained sealing compound for display elements is used for a liquid crystal display element by making the ratio of the said (meth)acryloyl group into this range, generation|occurrence|production of liquid crystal contamination is suppressed and it is excellent in adhesiveness further.
上述硬化性樹脂就抑制液晶污染等觀點而言，較佳為具有-OH基、-NH-基、-NH2 基等氫鍵結性單元者。The aforementioned curable resin preferably has hydrogen-bonding units such as -OH group, -NH- group, and -NH 2 group from the viewpoint of suppressing liquid crystal contamination.
上述硬化性樹脂可單獨使用，亦可組合2種以上使用。These curable resins may be used alone or in combination of two or more.
本發明之顯示元件用密封劑亦可於不妨礙本發明之目的之範圍內含有熱聚合起始劑。 作為上述熱聚合起始劑，例如可列舉：偶氮化合物、有機過氧化物等。其中，較佳為高分子偶氮化合物。 上述熱聚合起始劑可單獨使用，亦可組合2種以上使用。 再者，於本說明書中，上述「高分子偶氮化合物」意指具有偶氮基且藉由熱而生成可使(甲基)丙烯醯氧基硬化之自由基之數量平均分子量為300以上之化合物。The sealing compound for display elements of this invention may contain a thermal-polymerization initiator within the range which does not interfere with the object of this invention. As said thermal-polymerization initiator, an azo compound, an organic peroxide, etc. are mentioned, for example. Among them, polymeric azo compounds are preferred. The above thermal polymerization initiators may be used alone or in combination of two or more. In addition, in this specification, the above-mentioned "polymeric azo compound" refers to a compound having an azo group and generating free radicals capable of hardening (meth)acryloxy groups by heat, and having a number average molecular weight of 300 or more. compound.
上述高分子偶氮化合物之數量平均分子量之較佳之下限為1000，較佳之上限為30萬。藉由使上述高分子偶氮化合物之數量平均分子量為該範圍，於將獲得之顯示元件用密封劑用於液晶顯示元件之情形時，可抑制液晶污染並且容易地與硬化性樹脂混合。上述高分子偶氮化合物之數量平均分子量之更佳之下限為5000，更佳之上限為10萬，進而較佳之下限為1萬，進而較佳之上限為9萬。The preferable lower limit of the number average molecular weight of the above-mentioned polymeric azo compound is 1,000, and the preferable upper limit is 300,000. When the obtained sealing compound for display elements is used for a liquid crystal display element by making the number average molecular weight of the said high molecular weight azo compound into this range, liquid crystal contamination can be suppressed and it can mix with curable resin easily. The lower limit of the number average molecular weight of the above-mentioned polymer azo compound is preferably 5000, the upper limit is 100,000, the lower limit is 10,000, and the upper limit is 90,000.
作為上述高分子偶氮化合物，例如可列舉具有經由偶氮基而鍵結有多個聚環氧烷或聚二甲基矽氧烷等單元之結構者。 作為上述具有經由偶氮基而鍵結有多個聚環氧烷等單元之結構之高分子偶氮化合物，較佳為具有聚環氧乙烷結構者。 作為上述高分子偶氮化合物，具體而言，例如可列舉：4,4'-偶氮雙(4-氰基戊酸)與聚伸烷基二醇之縮聚物、或4,4'-偶氮雙(4-氰基戊酸)與末端具有胺基之聚二甲基矽氧烷之縮聚物等。 作為上述高分子偶氮化合物中之市售者，例如可列舉：VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001（皆為FUJIFILM Wako Pure Chemical公司製造）等。 又，作為非高分子之偶氮化合物，例如可列舉：V-65、V-501（皆為FUJIFILM Wako Pure Chemical公司製造）等。As said high molecular weight azo compound, the thing which has the structure which unites, such as a polyalkylene oxide or polydimethylsiloxane, couple|bonded via an azo group, is mentioned, for example. As the polymeric azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group, one having a polyethylene oxide structure is preferable. Specific examples of the polymeric azo compound include: a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'- Condensation product of nitrogen bis(4-cyanovaleric acid) and polydimethylsiloxane with amino groups at the end, etc. As what is marketed among the said high molecular weight azo compounds, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all are the FUJIFILM Wako Pure Chemical company make) etc. are mentioned, for example. Moreover, as a non-polymer azo compound, V-65, V-501 (all are made by FUJIFILM Wako Pure Chemical Co., Ltd.), etc. are mentioned, for example.
作為上述有機過氧化物，例如可列舉：過氧化酮、過氧縮酮、過氧化氫、過氧化二烷基、過氧酯、過氧化二醯基、過氧化二碳酸酯等。Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate and the like.
上述熱聚合起始劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為0.05重量份，較佳之上限為10重量份。藉由使上述熱聚合起始劑之含量為0.05重量份以上，本發明之顯示元件用密封劑成為熱硬化性更加優異者。藉由使上述熱聚合起始劑之含量為10重量份以下，本發明之顯示元件用密封劑成為保存穩定性更加優異者，且於用於液晶顯示元件之情形時成為低液晶污染性亦更加優異者。上述熱聚合起始劑之含量之更佳之下限為0.1重量份，更佳之上限為5重量份。The content of the thermal polymerization initiator is preferably 0.05 parts by weight at the lower limit and 10 parts by weight at the upper limit relative to 100 parts by weight of the curable resin. By making content of the said thermal-polymerization initiator 0.05 weight part or more, the sealing compound for display elements of this invention becomes what is more excellent in thermosetting property. By making the content of the above-mentioned thermal polymerization initiator 10 parts by weight or less, the sealant for display elements of the present invention is more excellent in storage stability, and when used in a liquid crystal display element, it becomes more low in liquid crystal contamination. Excellent. A more preferable lower limit of the content of the thermal polymerization initiator is 0.1 parts by weight, and a more preferable upper limit is 5 parts by weight.
本發明之顯示元件用密封劑亦可含有熱硬化劑。 作為上述熱硬化劑，例如可列舉：有機酸醯肼、咪唑衍生物、胺化合物、多酚系化合物、酸酐等。其中，較佳使用有機酸醯肼。 上述熱硬化劑可單獨使用，亦可組合2種以上使用。The sealing compound for display elements of this invention may contain a thermosetting agent. As said thermosetting agent, organic acid hydrazide, an imidazole derivative, an amine compound, a polyphenol type compound, an acid anhydride, etc. are mentioned, for example. Among them, organic acid hydrazide is preferably used. The above thermosetting agents may be used alone or in combination of two or more.
作為上述有機酸醯肼，例如可列舉：癸二醯肼、間苯二甲醯肼、己二醯肼、丙二醯肼等。 作為上述有機酸醯肼中之市售者，例如可列舉：大塚化學公司製造之有機酸醯肼、Ajinomoto Fine-Techno公司製造之有機酸醯肼等。 作為上述大塚化學公司製造之有機酸醯肼，例如可列舉：SDH、ADH等。 作為上述Ajinomoto Fine-Techno公司製造之有機酸醯肼，例如可列舉：Amicure VDH、Amicure VDH-J、Amicure UDH、Amicure UDH-J等。Examples of the organic acid hydrazide include decanoyl hydrazine, isophthalyl hydrazine, adipic hydrazine, and malonyl hydrazine. As what is marketed among the said organic acid hydrazides, the organic acid hydrazide by Otsuka Chemical Co., Ltd., the organic acid hydrazide by Ajinomoto Fine-Techno company, etc. are mentioned, for example. Examples of the organic acid hydrazide produced by the aforementioned Otsuka Chemical Co., Ltd. include SDH, ADH, and the like. Examples of the organic acid hydrazide manufactured by the aforementioned Ajinomoto Fine-Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J.
上述熱硬化劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為1重量份，較佳之上限為50重量份。藉由使上述熱硬化劑之含量為該範圍，可於不使獲得之顯示元件用密封劑之塗佈性等變差之情況下使熱硬化性更加優異。上述熱硬化劑之含量之更佳之上限為30重量份。With respect to 100 parts by weight of the above-mentioned curable resin, the content of the thermosetting agent has a preferable lower limit of 1 part by weight, and a preferable upper limit of 50 parts by weight. By making content of the said thermosetting agent into this range, it becomes possible to make thermosetting property more excellent, without deteriorating applicability, etc. of the sealant for display elements obtained. The more preferable upper limit of the content of the said thermosetting agent is 30 weight part.
以黏度之提高、由應力分散效果所引起之接著性之改善、線膨脹率之改善等為目的，本發明之顯示元件用密封劑較佳為含有填充劑。The sealant for display elements of the present invention preferably contains a filler for the purpose of improving viscosity, improving adhesiveness due to stress dispersion effect, improving linear expansion coefficient, and the like.
作為上述填充劑，可使用無機填充劑或有機填充劑。 作為上述無機填充劑，例如可列舉：二氧化矽、滑石、玻璃珠、石棉、石膏、矽藻土、膨潤石、膨潤土、蒙脫石、絹雲母、活性白土、氧化鋁、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、碳酸鈣、碳酸鎂、氫氧化鎂、氫氧化鋁、氮化鋁、氮化矽、硫酸鋇、矽酸鈣等。 作為上述有機填充劑，例如可列舉：聚酯微粒子、聚胺酯微粒子、乙烯聚合物微粒子、丙烯酸聚合物微粒子等。 上述填充劑可單獨使用，亦可組合2種以上使用。As said filler, an inorganic filler or an organic filler can be used. Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, and iron oxide. , magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc. As said organic filler, polyester fine particle, polyurethane fine particle, vinyl polymer fine particle, acrylic polymer fine particle etc. are mentioned, for example. These fillers may be used alone or in combination of two or more.
本發明之顯示元件用密封劑100重量份中之上述填充劑的含量之較佳之下限為10重量份，較佳之上限為70重量份。藉由使上述填充劑之含量為該範圍，而於不使塗佈性等變差之情況下使接著性之改善等效果更加優異。上述填充劑之含量之更佳之下限為20重量份，更佳之上限為60重量份。The preferable lower limit of the content of the said filler in 100 weight part of sealing agents for display elements of this invention is 10 weight part, and a preferable upper limit is 70 weight part. By making content of the said filler into this range, the effects, such as the improvement of adhesiveness, will become more excellent, without deteriorating applicability etc. The more preferable lower limit of the content of the above filler is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.
本發明之顯示元件用密封劑較佳為含有矽烷偶合劑。上述矽烷偶合劑主要具有用以良好地接著密封劑與基板等之作為接著助劑之作用。The sealing compound for display elements of the present invention preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly functions as an adhesive auxiliary agent for good adhesion between the sealant and the substrate.
作為上述矽烷偶合劑，可良好地使用3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷等。該等提高與基板等之接著性之效果優異，且與硬化性樹脂進行化學鍵結，藉此於將獲得之顯示元件用密封劑用於液晶顯示元件之情形時可抑制硬化性樹脂向液晶中流出。 上述矽烷偶合劑可單獨使用，亦可組合2種以上使用。As the above-mentioned silane coupling agent, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-isocyanato Propyltrimethoxysilane, etc. These are excellent in the effect of improving the adhesion with the substrate, etc., and chemically bond with the curable resin, thereby suppressing the outflow of the curable resin into the liquid crystal when the obtained sealant for a display element is used in a liquid crystal display element . The above-mentioned silane coupling agents may be used alone or in combination of two or more.
本發明之顯示元件用密封劑100重量份中之上述矽烷偶合劑之含量之較佳之下限為0.1重量份，較佳之上限為10重量份。藉由使上述矽烷偶合劑之含量為該範圍，於將獲得之顯示元件用密封劑用於液晶顯示元件之情形時，抑制液晶污染之產生並且提高接著性之效果更加優異。上述矽烷偶合劑之含量之更佳之下限為0.3重量份，更佳之上限為5重量份。The preferred lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for display elements of the present invention is 0.1 parts by weight, and the upper limit is preferably 10 parts by weight. By making content of the said silane coupling agent into this range, when using the obtained sealing compound for display elements for a liquid crystal display element, it suppresses generation|occurrence|production of liquid crystal contamination and the effect of improving adhesiveness is more excellent. The more preferable lower limit of the content of the above-mentioned silane coupling agent is 0.3 parts by weight, and the more preferable upper limit is 5 parts by weight.
本發明之顯示元件用密封劑亦可含有遮光劑。藉由含有上述遮光劑，本發明之顯示元件用密封劑可良好地用作遮光密封劑。 本發明之顯示元件用密封劑由於含有對於長波長之光之反應性優異的本發明之光聚合起始劑，故而即便於含有上述遮光劑之情形時，對於長波長之光之硬化性亦優異。The sealing compound for display elements of this invention may contain a light-shielding agent. By containing the said light-shielding agent, the sealing compound for display elements of this invention can be used favorably as a light-shielding sealing compound. Since the sealing agent for display elements of the present invention contains the photopolymerization initiator of the present invention which is excellent in reactivity to long-wavelength light, it is excellent in curability to long-wavelength light even when the above-mentioned light-shielding agent is contained. .
作為上述遮光劑，例如可列舉：氧化鐵、鈦黑、苯胺黑、花青黑（cyanine black）、富勒烯、碳黑、樹脂被覆型碳黑等。其中，較佳為絕緣性較高之物質，更佳為鈦黑。As said light-shielding agent, iron oxide, titanium black, aniline black, cyanine black (cyanine black), fullerene, carbon black, resin-coated carbon black etc. are mentioned, for example. Among them, a substance with higher insulating properties is preferable, and titanium black is more preferable.
上述鈦黑即便為未經表面處理者亦發揮充分之效果，亦可使用表面經偶合劑等有機成分處理者、或經氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分被覆者等經表面處理之鈦黑。其中，經有機成分處理者就可進一步提高絕緣性之方面而言較佳。 又，使用含有上述鈦黑作為遮光劑之本發明之顯示元件用密封劑所製造之顯示元件由於具有充分之遮光性，故而可實現無光之漏出而具有較高之對比度、且具有優異之圖像顯示品質之顯示元件。The above-mentioned titanium black can exert a sufficient effect even if it is not surface-treated, and it can also use the surface treated with organic components such as coupling agent, or the surface treated with inorganic components such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide. Titanium black with surface treatment such as component coating. Among them, those treated with an organic component are preferable in that the insulating properties can be further improved. Also, the display element manufactured by using the sealant for display element of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding property, so it can realize no light leakage, have high contrast, and have excellent image quality. Display components with display quality.
作為上述鈦黑中之市售者，例如可列舉：12S、13M、13M-C、13R-N、14M-C（皆為Mitsubishi Materials公司製造）、Tilack D（赤穗化成公司製造）等。As what is marketed among the said titanium blacks, 12S, 13M, 13M-C, 13R-N, 14M-C (all are manufactured by Mitsubishi Materials Co., Ltd.), Tilack D (made by Ako Kasei Co., Ltd.), etc. are mentioned, for example.
上述鈦黑之比表面積之較佳之下限為13 m2 /g，較佳之上限為30 m2 /g，更佳之下限為15 m2 /g，更佳之上限為25 m2 /g。 又，上述鈦黑之體積電阻之較佳之下限為0.5 Ω・cm，較佳之上限為3 Ω・cm，更佳之下限為1 Ω・cm，更佳之上限為2.5 Ω・cm。The lower limit of the specific surface area of the titanium black is preferably 13 m 2 /g, the upper limit is 30 m 2 /g, the lower limit is 15 m 2 /g, and the upper limit is 25 m 2 /g. In addition, the lower limit of the volume resistance of the titanium black is preferably 0.5 Ω·cm, the upper limit is 3 Ω·cm, the lower limit is 1 Ω·cm, and the upper limit is 2.5 Ω·cm.
上述遮光劑之一次粒徑只要為顯示元件之基板間之距離以下，則無特別限定，較佳之下限為1 nm，較佳之上限為5000 nm。藉由使上述遮光劑之一次粒徑為該範圍，而可於不使獲得之顯示元件用密封劑之描繪性等變差之情況下使遮光性更加優異。上述遮光劑之一次粒徑之更佳之下限為5 nm，更佳之上限為200 nm，進而較佳之下限為10 nm，進而較佳之上限為100 nm。 再者，上述遮光劑之一次粒徑可使用NICOMP 380ZLS（PARTICLE SIZING SYSTEMS公司製造）使上述遮光劑分散於溶劑（水、有機溶劑等）中而進行測定。The primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the display device, but the lower limit is preferably 1 nm, and the upper limit is preferably 5000 nm. By making the primary particle diameter of the said light-shielding agent into this range, it becomes possible to make light-shielding property more excellent, without deteriorating drawing property, etc. of the sealing compound for display elements obtained. The lower limit of the primary particle size of the above-mentioned sunscreen agent is preferably 5 nm, the upper limit is 200 nm, the lower limit is 10 nm, and the upper limit is 100 nm. In addition, the primary particle diameter of the said light-shielding agent can be measured by dispersing the said light-shielding agent in a solvent (water, an organic solvent, etc.) using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS).
本發明之顯示元件用密封劑100重量份中之上述遮光劑之含量的較佳之下限為5重量份，較佳之上限為80重量份。藉由使上述遮光劑之含量為該範圍，而可於不使獲得之顯示元件用密封劑之對基板之接著性或硬化後之強度或描繪性降低之情況下發揮更加優異之遮光性。上述遮光劑之含量之更佳之下限為10重量份，更佳之上限為70重量份，進而較佳之下限為30重量份，進而較佳之上限為60重量份。The preferable lower limit of the content of the said light-shielding agent in 100 weight part of sealing agents for display elements of this invention is 5 weight part, and a preferable upper limit is 80 weight part. By making content of the said light-shielding agent into this range, it becomes possible to exhibit more excellent light-shielding property without reducing the adhesiveness to the board|substrate of the sealing compound for display elements obtained, or the intensity|strength after hardening, and drawing property. The lower limit of the content of the sunscreen agent is more preferably 10 parts by weight, the upper limit is 70 parts by weight, the lower limit is 30 parts by weight, and the upper limit is 60 parts by weight.
本發明之顯示元件用密封劑亦可視需要進而含有反應性稀釋劑、觸變劑、間隔劑、硬化促進劑、消泡劑、調平劑、聚合抑制劑等添加劑。The sealant for display elements of the present invention may further contain additives such as reactive diluents, thixotropic agents, spacers, hardening accelerators, defoamers, leveling agents, and polymerization inhibitors, if necessary.
作為製造本發明之顯示元件用密封劑之方法，例如可列舉：使用混合機將硬化性樹脂、光聚合起始劑及視需要添加之矽烷偶合劑等加以混合之方法等。 作為上述混合機，例如可列舉：勻相分散機、均質攪拌機、萬能混合機、行星式混合機、捏合機、三輥研磨機等。As a method of manufacturing the sealing compound for display elements of this invention, the method of mixing curable resin, a photoinitiator, and the silane coupling agent added as needed etc. are mentioned, for example using a mixer. As said mixer, a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, etc. are mentioned, for example.
可藉由將導電性微粒子摻合於本發明之顯示元件用密封劑中而製造上下導通材料。含有本發明之顯示元件用密封劑與導電性微粒子之上下導通材料亦為本發明之一。A vertical conduction material can be produced by mixing conductive fine particles into the sealant for display elements of the present invention. The top-bottom conduction material comprising the sealant for display elements of the present invention and conductive fine particles is also one of the present invention.
作為上述導電性微粒子，可使用金屬球、於樹脂微粒子之表面形成有導電金屬層者等。其中，於樹脂微粒子之表面形成有導電金屬層者可藉由樹脂微粒子之優異之彈性而於不損傷透明基板等之情況下進行導電連接，因此較佳。As said electroconductive microparticles|fine-particles, what formed the electroconductive metal layer on the surface of a metal ball, the resin microparticles, etc. can be used. Among them, those having a conductive metal layer formed on the surface of the resin fine particles are preferable since they can be electrically connected without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.
使用本發明之顯示元件用密封劑或本發明之上下導通材料而成之顯示元件亦為本發明之一。 作為本發明之顯示元件，較佳為液晶顯示元件，更佳為窄邊緣設計之液晶顯示元件。具體而言，較佳為液晶顯示部之周圍之框部分之寬度為2 mm以下。 又，製造窄邊緣設計之液晶顯示元件作為本發明之顯示元件時，本發明之顯示元件用密封劑之塗佈寬度較佳為1 mm以下。A display element using the sealant for a display element of the present invention or the upper and lower conduction material of the present invention is also one of the present invention. As the display element of the present invention, it is preferably a liquid crystal display element, more preferably a liquid crystal display element with a narrow edge design. Specifically, it is preferable that the width of the frame portion around the liquid crystal display portion is 2 mm or less. Also, when manufacturing a liquid crystal display element with a narrow edge design as the display element of the present invention, the coating width of the sealant for display element of the present invention is preferably 1 mm or less.
作為製造液晶顯示元件作為本發明之顯示元件之方法，可良好地使用液晶滴下工法，具體而言，例如可列舉具有以下之各步驟之方法等。 首先，進行如下步驟：於具有ITO薄膜等電極及配向膜之2片透明基板之一者，藉由網版印刷、分注器塗佈等塗佈本發明之顯示元件用密封劑而形成框狀之密封圖案。其次，進行如下步驟：於本發明之顯示元件用密封劑未硬化之狀態下，將液晶之微小滴滴下塗佈至基板之密封圖案之框內，於真空重疊另一透明基板。其後，進行如下步驟：藉由介隔截止濾光器等對本發明之顯示元件用密封劑之密封圖案部分照射長波長之光，而使密封劑光硬化，藉由進行上述步驟之方法，可獲得液晶顯示元件。又，除了上述使密封劑光硬化之步驟以外，亦可進行加熱密封劑使之熱硬化之步驟。 [發明之效果]As a method of manufacturing a liquid crystal display element as the display element of the present invention, a liquid crystal dropping method can be used favorably, and specifically, a method having the following steps is exemplified. First, the following steps are carried out: On one of the two transparent substrates having electrodes such as ITO thin films and an alignment film, the sealant for display elements of the present invention is coated by screen printing, dispenser coating, etc. to form a frame shape The seal pattern. Next, the following steps are carried out: in the uncured state of the sealant for display elements of the present invention, tiny drops of liquid crystal are applied dropwise to the frame of the seal pattern on the substrate, and another transparent substrate is superimposed in vacuum. Thereafter, the following steps are carried out: irradiating long-wavelength light to the sealing pattern portion of the sealant for display elements of the present invention through a cut-off filter or the like to light-cure the sealant. By performing the above steps, it is possible to obtain Liquid crystal display element. Moreover, in addition to the above-mentioned step of photocuring the sealing agent, a step of heating and thermosetting the sealing agent may also be performed. [Effect of Invention]
根據本發明，可提供一種對於長波長之光之反應性優異之光聚合起始劑。又，根據本發明，可提供一種顯示元件用密封劑、以及使用該顯示元件用密封劑而成之上下導通材料及顯示元件，該顯示元件用密封劑含有該光聚合起始劑，對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異。進而，根據本發明，可提供一種構成該光聚合起始劑之化合物。According to the present invention, it is possible to provide a photopolymerization initiator excellent in reactivity with respect to long-wavelength light. Also, according to the present invention, there can be provided a sealant for a display element, and an upper and lower conduction material and a display element using the sealant for a display element, wherein the sealant for a display element contains the photopolymerization initiator and is effective for long wavelengths. It is excellent in light curability, and also excellent in low liquid crystal contamination when used in liquid crystal display elements. Furthermore, according to this invention, the compound which comprises this photoinitiator can be provided.
以下揭示實施例進一步詳細地說明本發明，但本發明不僅限定於該等實施例。Examples are disclosed below to illustrate the present invention in further detail, but the present invention is not limited to these examples.
（合成例1）
（式（2-1）所表示之化合物之製作）
於二氯甲烷100重量份中加入4-(二甲基胺基)苯甲醯氯10重量份、及作為觸媒之吡啶0.5重量份，於0℃之環境滴下去水甘油1重量份，放冷後，於室溫整夜攪拌。自獲得之反應液去除二氯甲烷，藉此獲得反應產物。於N,N-二甲基甲醯胺100重量份中添加獲得之反應產物10重量份、及2-羥基-9H-硫
（合成例2）
（式（2-2）所表示之化合物之製作）
將2-羥基-9H-硫
（合成例3） （式（2-3）所表示之化合物之製作） 將4-(二甲基胺基)苯甲醯氯變更為3,5-雙-(二甲基胺基)苯甲醯氯，除此以外，以與合成例1相同之方式獲得上述式（2-3）所表示之化合物。 再者，獲得之上述式（2-3）所表示之化合物之結構藉由1 H-NMR、13 C-NMR及FT-IR進行確認。 又，使獲得之式（2-3）所表示之化合物以濃度成為0.1 mg/mL之方式溶解於乙腈。對於獲得之乙腈溶液，使用分光光度計（Hitachi High-Tech Science公司製造，「U-3900」），於光程長度1 cm之條件測定300 nm以上800 nm以下之範圍之吸收光譜。其結果為，確認到式（2-3）所表示之化合物於420 nm之吸光度為0.10以上。(Synthesis Example 3) (Preparation of Compound Represented by Formula (2-3)) Change 4-(dimethylamino)benzoyl chloride to 3,5-bis-(dimethylamino)benzyl The compound represented by the above-mentioned formula (2-3) was obtained in the same manner as in Synthesis Example 1 except for acetyl chloride. Furthermore, the structure of the obtained compound represented by the above formula (2-3) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR. Also, the compound represented by the obtained formula (2-3) was dissolved in acetonitrile so that the concentration became 0.1 mg/mL. The obtained acetonitrile solution was measured with a spectrophotometer (manufactured by Hitachi High-Tech Science Co., Ltd., "U-3900") to measure the absorption spectrum in the range of 300 nm to 800 nm with an optical path length of 1 cm. As a result, it was confirmed that the absorbance at 420 nm of the compound represented by the formula (2-3) was 0.10 or more.
（實施例1~7及比較例1~4） 依照表1所記載之摻合比，使用行星式攪拌機（Thinky公司製造，「Awatori Rentaro」）將各材料進行混合後，進而使用三輥研磨機進行混合，藉此製備實施例1~7及比較例1~4之顯示元件用密封劑。(Examples 1-7 and Comparative Examples 1-4) According to the blending ratio recorded in Table 1, each material was mixed using a planetary mixer (manufactured by Thinky Corporation, "Awatori Rentaro"), and then mixed using a three-roll mill to prepare Examples 1 to 7 and comparison Sealants for display elements in Examples 1-4.
＜評價＞ 針對實施例及比較例中所獲得之各顯示元件用密封劑，進行以下之評價。將結果示於表1。＜Evaluation＞ The following evaluation was performed about each sealing compound for display elements obtained in the Example and the comparative example. The results are shown in Table 1.
（光硬化性） 使間隔劑微粒子（積水化學工業公司製造，「Micropearl SI-H050」）1重量份分散於實施例及比較例中所獲得之各顯示元件用密封劑100重量份。其次，將密封劑填充於滴塗用注射器（Musashi Engineering公司製造，「PSY-10E」），進行脫泡處理後，藉由分注器（Musashi Engineering公司製造，「SHOTMASTER300」）塗佈於玻璃基板上。藉由真空貼合裝置於5 Pa之減壓對該基板貼合同尺寸之玻璃基板。使用金屬鹵化物燈對貼合之玻璃基板之密封劑部分照射100 mW/cm2 之光10秒。光照射係介隔截止波長400 nm以下之光之截止濾光器（400 nm截止濾光器）而進行。 使用紅外分光裝置（BIORAD公司製造，「FTS3000」）進行密封劑之FT-IR測定，測定源自(甲基)丙烯醯基之峰值之光照射前後之變化量。於光照射後，將源自(甲基)丙烯醯基之峰值減少85%以上之情形設為「◎」，將減少70%以上且未達85%之情形設為「○」，將減少60%以上且未達70%之情形設為「Δ」，將光照射後之源自(甲基)丙烯醯基之峰值之減少未達60%之情形設為「×」，從而評價光硬化性。(Photocurability) 100 parts by weight of each sealant for a display element obtained in Examples and Comparative Examples was dispersed in 1 part by weight of spacer fine particles ("Micropearl SI-H050", manufactured by Sekisui Chemical Co., Ltd.). Next, the sealant is filled in a dripping syringe (manufactured by Musashi Engineering, "PSY-10E"), degassed, and applied to the glass substrate with a dispenser (manufactured by Musashi Engineering, "SHOTMASTER300") superior. A glass substrate of the same size was bonded to the substrate at a reduced pressure of 5 Pa by a vacuum bonding device. A metal halide lamp was used to irradiate 100 mW/cm 2 light for 10 seconds to the sealant portion of the bonded glass substrate. Light irradiation was performed through a cut filter (400 nm cut filter) that cuts light with a cutoff wavelength of 400 nm or less. FT-IR measurement of the sealant was performed using an infrared spectrometer (manufactured by BIORAD, "FTS3000"), and the amount of change before and after irradiation with light originating from the peak of the (meth)acryl group was measured. After light irradiation, the case where the peak derived from (meth)acryl group was reduced by more than 85% was marked as "◎", and the case where the peak was reduced by more than 70% but less than 85% was marked as "○", and the peak was reduced by 60% The case where it is more than % and less than 70% is set as "Δ", and the case where the peak value derived from the (meth)acryl group after light irradiation does not reach 60% is set as "X" to evaluate the photocurability .
（低液晶污染性）
使間隔劑微粒子（積水化學工業公司製造，「Micropearl SI-H050」）1重量份分散於實施例及比較例中所獲得之各顯示元件用密封劑100重量份。其次，藉由分注器以線寬成為1 mm之方式將分散有間隔劑微粒子之密封劑塗佈於經摩擦過之配向膜及附透明電極之基板。
繼而，將液晶（Chisso公司製造，「JC-5004LA」）之微小滴滴下塗佈至附透明電極之基板之密封劑之框內整個面，且立即貼合附透明電極之彩色濾光片基板。其後，使用金屬鹵化物燈對密封劑部分照射100 mW/cm2
之光30秒使之硬化，進而，於120℃加熱1小時，從而獲得液晶顯示元件。光照射係介隔截止波長400 nm以下之光之截止濾光器（400 nm截止濾光器）而進行。
液晶顯示元件係藉由分注器控制密封劑之塗佈位置，製作光完全照射至密封劑之液晶顯示元件（無遮光部）、及將密封劑以覆及線寬之50%之方式塗佈於彩色濾光片基板之黑矩陣所得之液晶顯示元件（有遮光部）之2種。圖3係示意性地表示使用實施例及比較例中所獲得之各顯示元件用密封劑以無遮光部之狀態製作之液晶顯示元件之剖視圖，圖4係示意性地表示使用實施例及比較例中所獲得之各顯示元件用密封劑以有遮光部之狀態製作之液晶顯示元件之剖視圖。如圖3所示，密封劑1上無遮光部之狀態者係光完全照射至密封劑1之狀態，另一方面，密封劑1上有遮光部之狀態者如圖4所示，光被黑矩陣2遮蔽而幾乎不會到達與液晶3接觸之部分之密封劑1。
對於獲得之液晶顯示元件，進行100小時動作試驗後，藉由目視確認到於80℃設為1000小時電壓施加狀態後之液晶配向混亂（顯示不均）。
將於液晶顯示元件完全未看到顯示不均之情形設為「◎」，將於液晶顯示元件之密封劑附近（周邊部）看到少量較淡之顯示不均之情形設為「○」，將於周邊部存在明顯較厚之顯示不均之情形設為「Δ」，將明顯較厚之顯示不均不僅存在於周邊部且亦擴散至中央部之情形設為「×」，從而評價低液晶污染性。
再者，評價為「◎」、「○」之液晶顯示元件係實際應用中完全無問題之等級，評價為「Δ」之液晶顯示元件係視顯示設計而可能成為問題之等級，評價為「×」之液晶顯示元件係不耐於實際應用之等級。(Low Liquid Crystal Contamination) 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each sealant for display elements obtained in Examples and Comparative Examples. Next, the sealant dispersed with spacer particles was applied to the rubbed alignment film and the substrate with transparent electrodes by a dispenser so that the line width became 1 mm. Next, micro-droplets of liquid crystal (manufactured by Chisso, "JC-5004LA") were applied dropwise to the entire surface of the frame of the sealant of the transparent electrode-attached substrate, and immediately attached to the transparent electrode-attached color filter substrate. Thereafter, the sealant portion was irradiated with light of 100 mW/cm 2 for 30 seconds using a metal halide lamp to be cured, and further heated at 120° C. for 1 hour to obtain a liquid crystal display element. Light irradiation was performed through a cut filter (400 nm cut filter) that cuts light with a cutoff wavelength of 400 nm or less. The liquid crystal display element uses a dispenser to control the coating position of the sealant to make a liquid crystal display element (no light-shielding part) that fully irradiates the sealant with light, and coat the sealant in such a way that it covers 50% of the line width Two types of liquid crystal display elements (with light-shielding parts) obtained from the black matrix of the color filter substrate. Fig. 3 schematically shows a cross-sectional view of a liquid crystal display device produced without a light-shielding portion using the sealants for display devices obtained in Examples and Comparative Examples, and Fig. 4 schematically shows the use of Examples and Comparative Examples A cross-sectional view of a liquid crystal display element produced in a state where each sealant for a display element obtained in has a light-shielding portion. As shown in Figure 3, the state where there is no light-shielding part on the
[表1]
根據本發明，可提供一種對於長波長之光之反應性優異之光聚合起始劑。又，根據本發明，可提供一種顯示元件用密封劑、以及使用該顯示元件用密封劑而成之上下導通材料及顯示元件，該顯示元件用密封劑對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異。進而，根據本發明，可提供一種構成該光聚合起始劑之化合物。According to the present invention, it is possible to provide a photopolymerization initiator excellent in reactivity with respect to long-wavelength light. Also, according to the present invention, there can be provided a sealant for a display element, an upper and lower conduction material using the sealant for a display element, and a display element, the sealant for a display element being excellent in curability to long-wavelength light, and It is also excellent in low liquid crystal contamination when used in liquid crystal display elements. Furthermore, according to this invention, the compound which comprises this photoinitiator can be provided.
1‧‧‧密封劑
2‧‧‧黑矩陣
3‧‧‧液晶1‧‧‧
圖1係合成例1中所獲得之式（2-1）所表示之化合物之1 H-NMR光譜。 圖2係合成例1中所獲得之式（2-1）所表示之化合物之吸收光譜。 圖3係示意性地表示使用實施例及比較例中所獲得之各顯示元件用密封劑以無遮光部之狀態製作之液晶顯示元件之剖視圖。 圖4係示意性地表示使用實施例及比較例中所獲得之各顯示元件用密封劑以有遮光部之狀態製作之液晶顯示元件之剖視圖。Fig. 1 is the 1 H-NMR spectrum of the compound represented by the formula (2-1) obtained in Synthesis Example 1. Fig. 2 is the absorption spectrum of the compound represented by the formula (2-1) obtained in Synthesis Example 1. 3 is a cross-sectional view schematically showing a liquid crystal display element produced in a state without a light-shielding portion using each sealing compound for a display element obtained in Examples and Comparative Examples. 4 is a cross-sectional view schematically showing a liquid crystal display element produced in a state having a light-shielding portion using each sealing compound for a display element obtained in Examples and Comparative Examples.
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