JP5763280B2 - Surface sealing agent for organic EL element and cured product thereof - Google Patents
Surface sealing agent for organic EL element and cured product thereof Download PDFInfo
- Publication number
- JP5763280B2 JP5763280B2 JP2014547612A JP2014547612A JP5763280B2 JP 5763280 B2 JP5763280 B2 JP 5763280B2 JP 2014547612 A JP2014547612 A JP 2014547612A JP 2014547612 A JP2014547612 A JP 2014547612A JP 5763280 B2 JP5763280 B2 JP 5763280B2
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- JP
- Japan
- Prior art keywords
- organic
- sealing agent
- surface sealing
- component
- thermosetting composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000007789 sealing Methods 0.000 title claims description 42
- 239000000203 mixture Substances 0.000 claims description 93
- 229920001187 thermosetting polymer Polymers 0.000 claims description 90
- 150000001875 compounds Chemical class 0.000 claims description 78
- 239000003795 chemical substances by application Substances 0.000 claims description 67
- 239000003505 polymerization initiator Substances 0.000 claims description 29
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 28
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 27
- 229920000570 polyether Polymers 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 19
- 125000003700 epoxy group Chemical group 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
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- 125000002091 cationic group Chemical group 0.000 description 28
- 239000010408 film Substances 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
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- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
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- 238000007792 addition Methods 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/105—Onium compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/18—Oxetanes
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Description
本発明は、熱硬化性組成物、有機EL素子用面封止剤およびその硬化物に関する。 The present invention relates to a thermosetting composition, a surface sealing agent for organic EL elements, and a cured product thereof.
有機EL素子は、液晶のバックライトや、自発光性の薄型平面表示デバイスとして期待されている。しかしながら、有機EL素子は、水分や酸素に触れると極めて劣化しやすい。具体的には、金属電極と有機物EL層との界面が水分の影響で剥離したり、金属が酸化して高抵抗化したり、有機物自体が水分によって変質したりする。それにより、有機EL素子が発光しなくなったり、輝度が低下したりすることがある。 The organic EL element is expected as a liquid crystal backlight or a self-luminous thin flat display device. However, organic EL elements are extremely susceptible to deterioration when exposed to moisture and oxygen. Specifically, the interface between the metal electrode and the organic EL layer is peeled off due to the influence of moisture, the metal is oxidized to increase resistance, or the organic matter itself is altered by moisture. As a result, the organic EL element may not emit light or the brightness may be reduced.
有機EL素子を、水分や酸素から保護する方法の一つとして、有機EL素子を透明な樹脂層で面封止する手法がある。この手法では、例えば有機EL素子上に、硬化性樹脂組成物を塗布した後、光硬化または熱硬化させて、有機EL素子を面封止する。このようにして用いられる硬化性樹脂組成物として、例えば光カチオン重合性化合物と、光カチオン重合開始剤と、エーテル結合を有する化合物(硬化制御剤)とを含む光硬化性樹脂組成物(例えば特許文献1)や;エポキシ化合物と、ポリエステル樹脂と、ルイス酸化合物とを含む有機EL素子封止用樹脂組成物(例えば特許文献6)などが提案されている。 One method for protecting the organic EL element from moisture and oxygen is to seal the surface of the organic EL element with a transparent resin layer. In this method, for example, after applying a curable resin composition on an organic EL element, the organic EL element is sealed by photocuring or thermosetting. As the curable resin composition used in this way, for example, a photocurable resin composition (for example, a patent) containing a photocationic polymerizable compound, a photocationic polymerization initiator, and a compound having an ether bond (curing control agent). Document 1) and organic EL element sealing resin compositions (for example, Patent Document 6) containing an epoxy compound, a polyester resin, and a Lewis acid compound have been proposed.
その他の用途の硬化性樹脂組成物として、エポキシ樹脂と、光カチオン重合開始剤と、ポリオキシメチレン高分子化合物とを含む光硬化性樹脂組成物(特許文献2および3)や;エポキシ樹脂と、硬化剤と、硬化促進剤と、ポリオールとを含むエポキシ樹脂粉体塗料(特許文献4)や;エポキシ化合物と、アミノ化合物と、硝酸塩などの触媒と、ポリアルキレンエーテルグリコールとを含む熱硬化性組成物(例えば特許文献5)などが知られている。 As a curable resin composition for other uses, a photocurable resin composition (Patent Documents 2 and 3) containing an epoxy resin, a photocationic polymerization initiator, and a polyoxymethylene polymer compound; and an epoxy resin; An epoxy resin powder coating (Patent Document 4) containing a curing agent, a curing accelerator, and a polyol; a thermosetting composition containing an epoxy compound, an amino compound, a catalyst such as nitrate, and a polyalkylene ether glycol A thing (for example, patent documents 5) etc. is known.
前述の通り、有機EL素子の面封止は、面封止剤を有機EL素子上に塗布した後、硬化させて行う。硬化は、光硬化または加熱硬化でありうるが、光によって素子が劣化する場合には、加熱硬化であることが望まれる。ところが、本発明者らは、面封止剤の塗布および加熱硬化過程;特に加熱硬化過程において、塗膜の温度分布や粘度が変化し、凸凹やハジキが生じやすく、硬化物層表面の平滑性が低くなりやすいとの新たな問題が生じることを見出した。 As described above, the surface sealing of the organic EL element is performed by applying a surface sealing agent on the organic EL element and then curing it. The curing can be photocuring or heat curing, but when the element is deteriorated by light, it is desirable to be heat curing. However, the present inventors have applied the surface sealant and heat-curing process; particularly, in the heat-curing process, the temperature distribution and viscosity of the coating film are changed, and unevenness and repellency are likely to occur, and the surface of the cured product layer is smooth. It has been found that a new problem arises that tends to be low.
有機EL素子を封止する面封止剤の硬化物層表面の平滑性が低いと、例えば凸凹がレンズのように作用し、有機EL素子から取り出される光が面内で不均一になりやすい。また、硬化物層上に無機薄膜などのバリア膜を形成する際に、ピンホールなどの欠陥を生じやすく、均一な無機バリア膜を形成できず、十分なバリア性が得られにくい。 When the smoothness of the surface of the cured product layer of the surface sealing agent that seals the organic EL element is low, for example, unevenness acts like a lens, and light extracted from the organic EL element tends to be non-uniform in the plane. Further, when a barrier film such as an inorganic thin film is formed on the cured product layer, defects such as pinholes are likely to occur, a uniform inorganic barrier film cannot be formed, and sufficient barrier properties are difficult to obtain.
本発明は、上記事情に鑑みてなされたものであり、例えば有機EL素子などの被塗布物上に、凹凸やハジキなどが少なく、表面の平滑性が高い硬化物層を形成できる熱硬化性組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances. For example, a thermosetting composition capable of forming a cured product layer having a high surface smoothness with less unevenness and repellency on an object to be coated such as an organic EL element. The purpose is to provide goods.
[1] (A)1分子内にカチオン重合性官能基を2つ以上有する、カチオン重合性化合物と、(B)熱カチオン重合開始剤と、(C)ポリエーテル化合物(ただし、前記カチオン重合性官能基を有する化合物を除く)と、(D)レベリング剤とを含み、E型粘度計で測定された25℃、2.5rpmにおける粘度が50〜30000mPa・sである、熱硬化性組成物。
[2] 前記(D)成分が、シリコーン系ポリマー、およびアクリレート系ポリマーからなる群より選ばれる化合物である、[1]に記載の熱硬化性組成物。
[3] 前記(C)成分の重量平均分子量が250〜10000である、[1]または[2]に記載の熱硬化性組成物。
[4] 前記(C)成分が、前記(A)成分100質量部に対して10質量部未満含まれる、[1]〜[3]のいずれかに記載の熱硬化性組成物。
[5] 前記カチオン重合性官能基が、エポキシ基、オキセタニル基、およびビニルエーテル基からなる群より選ばれる一種類以上の基である、[1]〜[4]のいずれかに記載の熱硬化性組成物。
[6] 前記(B)成分が、オニウム塩である、[1]〜[5]のいずれかに記載の熱硬化性組成物。
[7] 前記(C)成分が、ポリアルキレンオキサイドである、[1]〜[6]のいずれかに記載の熱硬化性組成物。
[8] 前記(A)成分100質量部に対して、前記(B)成分を0.1〜5質量部、前記(D)成分を0.01〜1質量部含む、[1]〜[7]のいずれかに記載の熱硬化性組成物。
[9] 前記(C)成分を、前記(A)成分100質量部に対して10質量部未満含む、[8]に記載の熱硬化性組成物。[1] (A) a cationically polymerizable compound having two or more cationically polymerizable functional groups in one molecule, (B) a thermal cationic polymerization initiator, and (C) a polyether compound A thermosetting composition containing a functional group) and (D) a leveling agent and having a viscosity at 25 ° C. and 2.5 rpm of 50 to 30000 mPa · s as measured with an E-type viscometer.
[2] The thermosetting composition according to [1], wherein the component (D) is a compound selected from the group consisting of a silicone polymer and an acrylate polymer.
[3] The thermosetting composition according to [1] or [2], wherein the component (C) has a weight average molecular weight of 250 to 10,000.
[4] The thermosetting composition according to any one of [1] to [3], wherein the component (C) is contained in an amount of less than 10 parts by mass with respect to 100 parts by mass of the component (A).
[5] The thermosetting according to any one of [1] to [4], wherein the cationically polymerizable functional group is one or more groups selected from the group consisting of an epoxy group, an oxetanyl group, and a vinyl ether group. Composition.
[6] The thermosetting composition according to any one of [1] to [5], wherein the component (B) is an onium salt.
[7] The thermosetting composition according to any one of [1] to [6], wherein the component (C) is a polyalkylene oxide.
[8] 0.1 to 5 parts by mass of the component (B) and 0.01 to 1 part by mass of the component (D) with respect to 100 parts by mass of the component (A) [1] to [7 ] The thermosetting composition in any one of.
[9] The thermosetting composition according to [8], wherein the component (C) is contained in an amount of less than 10 parts by mass with respect to 100 parts by mass of the component (A).
[10] [1]〜[9]のいずれかに記載の熱硬化性組成物を含む、有機EL素子用面封止剤。
[11] [10]に記載の面封止剤の硬化物。[10] A surface sealing agent for organic EL elements, comprising the thermosetting composition according to any one of [1] to [9].
[11] A cured product of the surface sealing agent according to [10].
本発明によれば、例えば有機EL素子などの被塗布物上に、凹凸やハジキなどが少なく、表面の平滑性が高い硬化物層を形成できる熱硬化性組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the thermosetting composition which can form a hardened | cured material layer with few unevenness | corrugations, repelling, etc. and high surface smoothness on to-be-coated objects, such as an organic EL element, can be provided.
1.熱硬化性組成物
本発明の熱硬化性組成物は、(A)カチオン重合性化合物と、(B)熱カチオン重合開始剤と、(C)ポリエーテル化合物と、(D)レベリング剤とを含む。1. Thermosetting Composition The thermosetting composition of the present invention includes (A) a cationic polymerizable compound, (B) a thermal cationic polymerization initiator, (C) a polyether compound, and (D) a leveling agent. .
(A)カチオン重合性化合物
カチオン重合性化合物は、1分子内に2以上のカチオン重合性官能基を有する化合物でありうる。カチオン重合性官能基は、エポキシ基、オキセタニル基、ビニルエーテル基からなる群より選ばれる一種類以上である。カチオン重合性官能基が複数ある場合、それらは互いに同一であっても異なっていてもよい。(A) Cationic polymerizable compound The cationic polymerizable compound may be a compound having two or more cationic polymerizable functional groups in one molecule. The cationic polymerizable functional group is at least one selected from the group consisting of an epoxy group, an oxetanyl group, and a vinyl ether group. When there are a plurality of cationically polymerizable functional groups, they may be the same as or different from each other.
1分子内に2以上のエポキシ基を有するエポキシ樹脂の例には、ビスフェノールA型、ビスフェノールF型、ビスフェノールE型、ビスフェノールS型、ビスフェノールAD型、および水添ビスフェノールA型等のビスフェノール型エポキシ樹脂;ジフェニルエーテル型エポキシ樹脂;フェノールノボラック型、クレゾールノボラック型、ビフェニルノボラック型、ビスフェノールノボラック型、ナフトールノボラック型、トリスフェノールノボラック型、ジシクロペンタジエンノボラック型等のノボラック型エポキシ樹脂;ビフェニル型エポキシ樹脂;ナフチル型エポキシ樹脂;トリフェノールメタン型、トリフェノールエタン型、トリフェノールプロパン型等のトリフェノールアルカン型エポキシ樹脂などの芳香族エポキシ樹脂;
脂環式エポキシ樹脂;
脂肪族エポキシ樹脂などが含まれる。Examples of epoxy resins having two or more epoxy groups in one molecule include bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol E type, bisphenol S type, bisphenol AD type, and hydrogenated bisphenol A type. Diphenyl ether type epoxy resin; phenol novolak type, cresol novolak type, biphenyl novolak type, bisphenol novolak type, naphthol novolak type, trisphenol novolak type, dicyclopentadiene novolak type and other novolak type epoxy resins; biphenyl type epoxy resin; naphthyl type Epoxy resin; aromatic epoxy resin such as triphenolalkane type epoxy resin such as triphenolmethane type, triphenolethane type, triphenolpropane type;
Alicyclic epoxy resin;
Aliphatic epoxy resins and the like are included.
1分子内に2以上のオキセタニル基を有するオキセタニル化合物の例には、1,3−ビス[(3−エチル−3−オキセタニル)メトキシ]ベンゼン、1,4−ビス{[(3−エチル−3−オキセタニル)メトキシ]メチル}ベンゼンなどの芳香族オキセタン化合物;
1,4−ビス{[(3−エチル−3−オキセタニル)メトキシ]メチル}シクロヘキサン、4,4’−ビス{[(3−エチル−3−オキセタニル)メトキシ]メチル}ビシクロヘキサンなどの脂環式オキセタン化合物;
ジ[1−エチル(3−オキセタニル)]メチルエーテル、ビス(3−エチル−3−オキセタニルメチル)エーテル、トリメチロールプロパントリス(3−エチル−3−オキセタニルメチル)エーテル、ペンタエリスリトールトリス(3−エチル−3−オキセタニルメチル)エーテルなどの脂肪族オキセタン化合物などが含まれる。Examples of oxetanyl compounds having two or more oxetanyl groups in one molecule include 1,3-bis [(3-ethyl-3-oxetanyl) methoxy] benzene, 1,4-bis {[(3-ethyl-3 Aromatic oxetane compounds such as -oxetanyl) methoxy] methyl} benzene;
Alicyclic such as 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} cyclohexane, 4,4′-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} bicyclohexane Oxetane compounds;
Di [1-ethyl (3-oxetanyl)] methyl ether, bis (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl Aliphatic oxetane compounds such as -3-oxetanylmethyl) ether.
1分子内に2以上のビニルエーテル基を有するビニルエーテル化合物の例には、シクロヘキサンジメタノールジビニルエーテルなどの脂環式ビニルエーテル化合物;
エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテルなどの脂肪族ビニルエーテル化合物などが含まれる。Examples of vinyl ether compounds having two or more vinyl ether groups in one molecule include alicyclic vinyl ether compounds such as cyclohexanedimethanol divinyl ether;
Examples include aliphatic vinyl ether compounds such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, and dipropylene glycol divinyl ether.
これらのなかでも、熱硬化性組成物の粘度を調整しやすいことから、25℃で液状のカチオン重合性化合物が好ましい。25℃で液状のカチオン重合性化合物は、被塗布物との接着性が得られやすい点などから、1分子内に2以上のエポキシ基を有するエポキシ樹脂であることが好ましい。エポキシ樹脂は、硬化物の耐湿性を高めやすいことなどから、芳香族エポキシ樹脂が好ましい。 Among these, a cationically polymerizable compound that is liquid at 25 ° C. is preferable because the viscosity of the thermosetting composition can be easily adjusted. The cationically polymerizable compound that is liquid at 25 ° C. is preferably an epoxy resin having two or more epoxy groups in one molecule from the viewpoint that adhesion to an object is easily obtained. The epoxy resin is preferably an aromatic epoxy resin because it easily improves the moisture resistance of the cured product.
芳香族エポキシ樹脂は、ビスフェノール型エポキシ化合物、クレゾールノボラック型エポキシ化合物などが好ましく、ビスフェノール型エポキシ化合物であることがより好ましい。ビスフェノール型エポキシ化合物は、一般式(X)で表される化合物であることが好ましく、好ましい例には、一般式(X')で表される化合物が含まれる。
一般式(X)および(X’)において、Xは、単結合、メチレン基、イソプロピリデン基、−S−または−SO2−を示し;R1は、それぞれ独立して炭素数が1〜5のアルキル基を示し;nは、2以上の整数を示し;Pは、0〜4の整数を示す。nは、2〜4であることが好ましい。In the general formulas (X) and (X ′), X represents a single bond, a methylene group, an isopropylidene group, —S— or —SO 2 —; each R 1 independently has 1 to 5 carbon atoms. N represents an integer of 2 or more; P represents an integer of 0 to 4. n is preferably 2 to 4.
カチオン重合性化合物は、熱硬化性組成物の粘度を後述する範囲に調整しやすく、塗布または硬化時に流動性を確保しやすいことなどから、低分子量であることが好ましい。具体的には、カチオン重合性化合物の重量平均分子量は、200〜800であることが好ましく、300〜700であることがより好ましい。「重量平均分子量(Mw)」は、ポリスチレンを標準物質とするゲルパーミエーションクロマトグラフィー(GPC)により測定される。 The cationic polymerizable compound preferably has a low molecular weight because it is easy to adjust the viscosity of the thermosetting composition to a range described later and to ensure fluidity during coating or curing. Specifically, the weight average molecular weight of the cationic polymerizable compound is preferably 200 to 800, and more preferably 300 to 700. The “weight average molecular weight (Mw)” is measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
カチオン重合性化合物のカチオン重合性官能基当量は、100〜800g/eqであることが好ましい。 The cation polymerizable functional group equivalent of the cation polymerizable compound is preferably 100 to 800 g / eq.
カチオン重合性化合物の、E型粘度計により測定される25℃、2.5rpmにおける粘度は、50〜30000mPa・sであることが好ましい。粘度が上記範囲にあるエポキシ樹脂は、熱硬化性組成物の粘度を後述する範囲に調整しやすいからである。 The viscosity of the cationic polymerizable compound at 25 ° C. and 2.5 rpm measured with an E-type viscometer is preferably 50 to 30000 mPa · s. This is because an epoxy resin having a viscosity in the above range can easily adjust the viscosity of the thermosetting composition to a range described later.
カチオン重合性化合物の含有量は、熱硬化性組成物に対して60質量%以上とすることができ、好ましくは70質量%以上としうる。熱硬化性組成物に含まれる(A)カチオン重合性化合物は、一種類であってもよいし、種類や分子量の異なる二種類以上を組み合わせてもよい。 The content of the cationic polymerizable compound can be 60% by mass or more, preferably 70% by mass or more with respect to the thermosetting composition. One type of (A) cationic polymerizable compound contained in the thermosetting composition may be used, or two or more types having different types and molecular weights may be combined.
(B)熱カチオン重合開始剤
熱カチオン重合開始剤は、加熱によって重合を開始させるカチオン種を発生しうる化合物である。熱カチオン重合開始剤は、特に制限されず、硬化条件やカチオン重合性化合物の種類に応じて適宜選択されうる。例えば、カチオン重合性化合物がエポキシ樹脂である場合、熱カチオン重合開始剤は、4級アンモニウム塩、ホスホニウム塩などのオニウム塩でありうる。(B) Thermal cationic polymerization initiator The thermal cationic polymerization initiator is a compound capable of generating a cationic species that initiates polymerization upon heating. The thermal cationic polymerization initiator is not particularly limited, and may be appropriately selected according to the curing conditions and the type of the cationic polymerizable compound. For example, when the cationically polymerizable compound is an epoxy resin, the thermal cationic polymerization initiator may be an onium salt such as a quaternary ammonium salt or a phosphonium salt.
なかでも、熱硬化性組成物の保存安定性を高めたり、硬化物の着色を抑制したりしうる点から、4級アンモニウム塩が好ましい。4級アンモニウム塩の例には、特定の4級アンモニウムイオンと対アニオンとを含む塩(B1)が含まれる。 Among these, a quaternary ammonium salt is preferable from the viewpoint that the storage stability of the thermosetting composition can be improved and coloring of the cured product can be suppressed. Examples of the quaternary ammonium salt include a salt (B1) containing a specific quaternary ammonium ion and a counter anion.
塩(B1)を構成する4級アンモニウムイオンは、下記一般式(1)で表されうる。
一般式(1)のR1、R2、およびR3は、それぞれ独立に置換基を有してもよい炭素数1〜10のアルキル基、置換基を有してもよい炭素数6〜10のアリール基、または置換基を有してもよい炭素数7〜20のアラルキル基を示す。特に、R1、R2、R3は、それぞれ独立にメチル基、フェニル基、またはベンジル基であることが好ましい。R 1 , R 2 and R 3 in the general formula (1) are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent and 6 to 10 carbon atoms which may have a substituent. Or an aryl group having 7 to 20 carbon atoms which may have a substituent. In particular, R 1 , R 2 and R 3 are preferably each independently a methyl group, a phenyl group or a benzyl group.
R1、R2、およびR3が有しうる置換基は、特に制限されないが、炭素数が1〜10のアルキル基、炭素数が1〜10のアルコキシ基、−F、−Cl、−Br、−I、−NO2、−CN、および下記一般式(2)で表される基からなる群より選ばれる官能基であることが好ましい。
一般式(2)のR13、R14、およびR15は、それぞれ独立に水素基または炭素数1〜10の炭化水素基を示す。なかでも、熱硬化性組成物の保存安定性を高める観点などから、R13、R14、およびR15の全てが炭化水素基であることが好ましい。炭化水素基は、直鎖状、分岐鎖状、もしくは環状の脂肪族基であってもよく、芳香族であってもよい。R <13> , R <14> , and R < 15 > of General formula (2) show a hydrogen group or a C1-C10 hydrocarbon group each independently. Especially, it is preferable that all of R <13> , R <14> , and R < 15 > are hydrocarbon groups from a viewpoint of improving the storage stability of a thermosetting composition. The hydrocarbon group may be a linear, branched or cyclic aliphatic group, or may be aromatic.
一般式(1)のArは、置換基を有してもよい炭素数6〜10のアリール基を示す。Arは、芳香族炭化水素基であることが好ましく、例えばフェニル基、ナフチル基等でありうる。一般式(1)のArが有しうる置換基は、特に制限されず、一般式(1)のR1、R2、およびR3が有しうる置換基と同様のものでありうる。Ar in the general formula (1) represents an aryl group having 6 to 10 carbon atoms which may have a substituent. Ar is preferably an aromatic hydrocarbon group, and may be, for example, a phenyl group or a naphthyl group. The substituent that Ar in the general formula (1) may have is not particularly limited, and may be the same as the substituent that R 1 , R 2 , and R 3 in the general formula (1) may have.
Arに結合する置換基の結合位置や置換基の数は、特に制限されない。例えば、Arに結合する置換基が電子求引性基;例えば−F、−Cl、−Br、−I、−NO2、または−CNである場合は、一般式(1)のArとメチレン基との結合位置に対して、メタ位またはパラ位に置換基が結合することが好ましい。この位置に電子求引性基が結合すると、カチオン重合性化合物の硬化反応が促進されやすい。また、Arに結合する電子求引性基の数は、2以下が好ましい。The bonding position of the substituent bonded to Ar and the number of substituents are not particularly limited. For example, when the substituent bonded to Ar is an electron-withdrawing group; for example, -F, -Cl, -Br, -I, -NO 2 , or -CN, Ar in the general formula (1) and a methylene group It is preferable that the substituent is bonded to the meta position or the para position with respect to the bonding position with. When an electron withdrawing group is bonded to this position, the curing reaction of the cationic polymerizable compound is easily promoted. The number of electron withdrawing groups bonded to Ar is preferably 2 or less.
一方、Arに結合する置換基が電子供与性基;例えばアルキル基、アルコキシ基、または一般式(2)で表される基である場合は、一般式(1)のArとメチレン基との結合位置に対してパラ位に置換基が結合することが好ましい。この位置に電子供与性の基が結合すると、カチオン重合性化合物の硬化反応が促進されやすい。Arに結合する置換基が電子供与性基である場合、電子求引性基である場合よりも、カチオン重合性化合物の硬化反応が促進されやすい。 On the other hand, when the substituent bonded to Ar is an electron donating group; for example, an alkyl group, an alkoxy group, or a group represented by the general formula (2), a bond between Ar in the general formula (1) and a methylene group It is preferred that the substituent is bonded to the para position relative to the position. When an electron donating group is bonded to this position, the curing reaction of the cationic polymerizable compound is easily promoted. When the substituent bonded to Ar is an electron donating group, the curing reaction of the cationically polymerizable compound is more easily promoted than when the substituent is an electron withdrawing group.
一般式(1)で表される4級アンモニウムイオンの好ましい例には、下記のイオンが含まれる。
塩(B1)を構成する対アニオンの例には、[CF3SO3]−、[C4F9SO3]−、[PF6]−、[AsF6]−、[Ph4B]−、Cl−、Br−、I−、[OC(O)R16]−(R16は炭素数1〜10のアルキル基を表す)、[SbF6]−、[B(C6F5)4]−、[B(C6H4CF3)4]−、[(C6F5)2BF2]−、[C6F5BF3]−、または[B(C6H3F2)4]−が含まれる。なかでも、酸解離定数の逆数の対数(pKa)が小さいアニオンが好ましい。pKaが小さいほど、塩(B1)がイオン化しやすく、エポキシ樹脂の硬化反応が促進される。Examples of the counter anion constituting the salt (B1) include [CF 3 SO 3 ] − , [C 4 F 9 SO 3 ] − , [PF 6 ] − , [AsF 6 ] − and [Ph 4 B] −. , Cl − , Br − , I − , [OC (O) R 16 ] — (R 16 represents an alkyl group having 1 to 10 carbon atoms), [SbF 6 ] − , [B (C 6 F 5 ) 4 ] -, [B (C 6 H 4 CF 3) 4] -, [(C 6 F 5) 2 BF 2] -, [C 6 F 5 BF 3] -, or [B (C 6 H 3 F 2 ) 4] - it is included. Among these, an anion having a small logarithm (pKa) of the reciprocal of the acid dissociation constant is preferable. The smaller the pKa, the easier the salt (B1) is ionized and the curing reaction of the epoxy resin is promoted.
塩(B1)の好ましい例には、下記の化合物が含まれる。
塩(B1)を一定以上の温度に加熱すると、塩(B1)の4級アンモニウムイオンのベンジル位のプロトンが脱離して、エポキシ樹脂のエポキシ基にプロトンを供与する。プロトンを供与されたエポキシ樹脂は、エポキシ基が開環し、他の複数のエポキシ樹脂と重合して硬化する。このように、塩(B1)は、一定以上の温度に加熱されることで、エポキシ樹脂の重合反応を開始しうる。一方、低温では、このような反応が生じにくいため、熱硬化性組成物の保存安定性を高めることができる。 When the salt (B1) is heated to a certain temperature or higher, the proton at the benzyl position of the quaternary ammonium ion of the salt (B1) is eliminated, and a proton is donated to the epoxy group of the epoxy resin. In the epoxy resin to which protons are donated, the epoxy group is ring-opened and polymerized with other epoxy resins to be cured. Thus, the salt (B1) can start the polymerization reaction of the epoxy resin by being heated to a certain temperature or higher. On the other hand, since such a reaction hardly occurs at a low temperature, the storage stability of the thermosetting composition can be improved.
4級アンモニウムイオンの反応性は、メチレン基に隣接するアリール基の置換基で調整できる。例えば、アリール基の置換基を電子供与性基とすることで、4級アンモニウムイオンの反応性を高めることができる。 The reactivity of the quaternary ammonium ion can be adjusted by the substituent of the aryl group adjacent to the methylene group. For example, the reactivity of a quaternary ammonium ion can be enhanced by using an aryl group substituent as an electron donating group.
熱カチオン重合開始剤の含有量は、カチオン重合性化合物((A)成分)100質量部に対して0.1〜5質量部であることが好ましく、0.1〜3質量部であることがより好ましい。熱カチオン重合開始剤の含有量が一定以上であると、カチオン重合性化合物を十分に硬化させやすい。一方、熱カチオン重合開始剤の含有量が一定以下であると、保管時の樹脂組成物の安定性が損なわれにくいだけでなく、硬化物中の未反応の熱カチオン重合開始剤の残存量を少なくすることができ、硬化物の耐熱性などを損ないにくい。熱カチオン重合開始剤は、一種の化合物のみで構成されてもよく、二種以上の化合物の組み合わせであってもよい。 The content of the thermal cationic polymerization initiator is preferably 0.1 to 5 parts by mass, and 0.1 to 3 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound (component (A)). More preferred. When the content of the thermal cationic polymerization initiator is a certain level or more, the cationically polymerizable compound is easily cured sufficiently. On the other hand, if the content of the thermal cationic polymerization initiator is below a certain level, not only is the stability of the resin composition during storage difficult to impair, but the residual amount of unreacted thermal cationic polymerization initiator in the cured product is also reduced. It can be reduced, and the heat resistance of the cured product is hardly impaired. The thermal cationic polymerization initiator may be composed of only one kind of compound, or may be a combination of two or more kinds of compounds.
熱カチオン重合開始剤中のアンモニウムイオンの量と、熱硬化性組成物に含まれるカチオン重合性官能基の量との比(当量比(熱カチオン重合開始剤中のアンモニウムイオンの数/熱硬化性組成物中のカチオン重合性官能基の数)×100)が0.5〜10%であることが好ましく、より好ましくは0.5〜1%である。 Ratio of the amount of ammonium ions in the thermal cationic polymerization initiator to the amount of the cationic polymerizable functional group contained in the thermosetting composition (equivalent ratio (number of ammonium ions in the thermal cationic polymerization initiator / thermosetting The number of cationically polymerizable functional groups in the composition) × 100) is preferably 0.5 to 10%, more preferably 0.5 to 1%.
本発明者らは、熱硬化性組成物の塗布および加熱硬化過程;特に加熱硬化過程における凸凹やハジキを抑制するためには、(C)ポリエーテル化合物と(D)レベリング剤とを組み合わせることが有効であることを見出した。 In order to suppress unevenness and repellency in the application and thermosetting process of the thermosetting composition; in particular, the thermosetting process, the present inventors may combine (C) a polyether compound and (D) a leveling agent. I found it effective.
この理由は、必ずしも明らかではないものの、以下のように考えられる。即ち、熱硬化性組成物の加熱硬化過程では、(C)ポリエーテル化合物のエーテル結合部分が、(D)レベリング剤の表面張力調整機能を阻害することなく、(B)熱カチオン重合開始剤のカチオンを捕捉し、(A)カチオン重合性化合物の重合を遅延させうる。それにより、加熱硬化過程での、熱硬化性組成物が流動しうる時間を長くすることができ;その間に、(D)レベリング剤を十分に作用させることができるためと考えられる。 Although this reason is not necessarily clear, it is considered as follows. That is, in the heat curing process of the thermosetting composition, (C) the ether bond portion of the polyether compound does not interfere with the surface tension adjusting function of (D) the leveling agent, and (B) the thermal cationic polymerization initiator The cation can be captured and the polymerization of the (A) cationic polymerizable compound can be delayed. Thereby, the time during which the thermosetting composition can flow during the heat curing process can be lengthened; during this period, (D) the leveling agent can sufficiently act.
(C)ポリエーテル化合物
ポリエーテル化合物は、エーテル結合を有する繰り返し単位を含み、かつ前述のカチオン重合性官能基を含まない化合物である。そのようなポリエーテル化合物は、ポリアルキレンオキサイドやクラウンエーテルなどでありうる。(C) Polyether compound A polyether compound is a compound which contains the repeating unit which has an ether bond, and does not contain the above-mentioned cation polymerizable functional group. Such polyether compounds can be polyalkylene oxides, crown ethers, and the like.
ポリアルキレンオキサイドの構成単位であるアルキレンオキサイドのアルキレン鎖の炭素原子数は2〜4、好ましくは2〜3である。ポリアルキレンオキサイドの例には、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシテトラメチレングリコールなどが含まれ、好ましくはポリエチレングリコールである。ポリアルキレンオキサイドの分子末端は、水酸基であってもよいし、他の化合物でエーテル化またはエステル化されていてもよい。 The number of carbon atoms in the alkylene chain of the alkylene oxide which is a constituent unit of the polyalkylene oxide is 2 to 4, preferably 2 to 3. Examples of the polyalkylene oxide include polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol and the like, and preferably polyethylene glycol. The molecular terminal of the polyalkylene oxide may be a hydroxyl group, or may be etherified or esterified with another compound.
クラウンエーテルの例には、12−クラウン−4、15−クラウン−5、18−クラウン−6などが含まれる。 Examples of crown ethers include 12-crown-4, 15-crown-5, 18-crown-6 and the like.
なかでも、ポリエチレングリコールおよびクラウンエーテルが特に好ましい。これらは、(A)カチオン重合性化合物と混ざりやすいからである。 Of these, polyethylene glycol and crown ether are particularly preferable. This is because they are easily mixed with the (A) cationic polymerizable compound.
ポリエーテル化合物の重量平均分子量は、150〜10000であることが好ましく、250〜10000であることがより好ましく、400〜10000であることがさらに好ましい。ポリエーテル化合物の分子量が一定以上であると、ポリエーテル化合物中にエーテル結合部分が十分に含まれるため、熱カチオン重合開始剤のカチオンを十分に捕捉しやすく、(A)カチオン重合性化合物の重合反応の遅延効果が得られやすい。その結果、加熱硬化過程における、熱硬化性組成物が流動しうる時間を長くしやすく、十分なレベリング効果が得られやすい。一方、ポリエーテル化合物の分子量が一定以下であると、熱硬化性組成物への溶解性の低下や、粘度の増大を生じにくい。 The weight average molecular weight of the polyether compound is preferably 150 to 10,000, more preferably 250 to 10,000, and still more preferably 400 to 10,000. When the molecular weight of the polyether compound is above a certain level, the ether compound portion is sufficiently contained in the polyether compound, so that the cation of the thermal cationic polymerization initiator can be easily captured, and (A) polymerization of the cationic polymerizable compound It is easy to obtain a delayed reaction effect. As a result, it is easy to lengthen the time during which the thermosetting composition can flow in the heat curing process, and a sufficient leveling effect can be easily obtained. On the other hand, when the molecular weight of the polyether compound is below a certain level, it is difficult to cause a decrease in solubility in the thermosetting composition and an increase in viscosity.
ポリエーテル化合物の含有量は、カチオン重合性化合物((A)成分)100質量部に対して10質量部未満であることが好ましく、0.05質量部以上8質量部以下であることがより好ましく、0.5質量部以上5質量部以下であることがさらに好ましい。ポリエーテル化合物の含有量が一定以上であると、エーテル結合部分によって熱カチオン重合開始剤のカチオンを十分に捕捉しやすく、カチオン重合性化合物の重合反応の遅延効果が得られやすい。その結果、熱硬化性組成物を十分にレベリングさせやすい。一方、ポリエーテル化合物の含有量が一定未満であると、熱硬化性組成物に十分に溶解させやすく、さらに組成物を常温で保存した場合に固形化しにくく、組成物の保存安定性を損ないにくい。 The content of the polyether compound is preferably less than 10 parts by mass and more preferably 0.05 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the cationically polymerizable compound (component (A)). More preferably, it is 0.5 parts by mass or more and 5 parts by mass or less. When the content of the polyether compound is not less than a certain value, the cation of the thermal cationic polymerization initiator is easily captured by the ether bond portion, and the effect of delaying the polymerization reaction of the cationic polymerizable compound is easily obtained. As a result, it is easy to sufficiently level the thermosetting composition. On the other hand, if the content of the polyether compound is less than a certain value, it is easy to dissolve sufficiently in the thermosetting composition, and further, it is difficult to solidify when the composition is stored at room temperature, and the storage stability of the composition is not easily impaired. .
ポリエーテル化合物は、前述の通り、加熱硬化過程において熱カチオン重合開始剤のカチオンを捕捉させるなどの目的で添加されうる。従って、ポリエーテル化合物の含有量は、熱カチオン重合開始剤の含有量(モル量)に応じて設定されることが好ましい。具体的には、(ポリエーテル化合物に対して)熱カチオン重合開始剤の含有割合が過剰に多くならないようにすることで、十分な重合遅延効果が得られやすい。一方、(熱カチオン重合開始剤に対して)ポリエーテル化合物の含有割合が過剰に多くならないようにすることで、硬化不良を抑制しうる。 As described above, the polyether compound can be added for the purpose of trapping cations of the thermal cationic polymerization initiator in the heat curing process. Therefore, the content of the polyether compound is preferably set according to the content (molar amount) of the thermal cationic polymerization initiator. Specifically, by preventing the content of the thermal cationic polymerization initiator from increasing excessively (relative to the polyether compound), a sufficient polymerization delay effect can be easily obtained. On the other hand, by preventing the content of the polyether compound from excessively increasing (relative to the thermal cationic polymerization initiator), poor curing can be suppressed.
(D)レベリング剤
レベリング剤は、熱硬化性組成物を加熱硬化させる過程で、熱硬化性組成物の塗膜表面に配向して塗膜の表面張力を均一化し、ハジキなどを生じにくくし、被塗布物上に濡れ広がりやすくする。そのため、レベリング剤は、下記式を満たすように選択されることが好ましい。
S=γv−γA−γI>0
(S:拡張係数、γv:熱硬化性組成物の塗膜の表面張力、γA:レベリング剤の表面張力、γI:熱硬化性組成物とレベリング剤の界面張力)(D) Leveling agent In the process of heat-curing the thermosetting composition, the leveling agent is oriented on the surface of the coating film of the thermosetting composition to make the surface tension of the coating film uniform, making it difficult to cause repelling, Make it easy to spread on the substrate. Therefore, the leveling agent is preferably selected so as to satisfy the following formula.
S = γv−γA−γI> 0
(S: expansion coefficient, γv: surface tension of coating film of thermosetting composition, γA: surface tension of leveling agent, γI: interfacial tension between thermosetting composition and leveling agent)
レベリング剤は、その表面張力(γA)が、加熱硬化工程での熱硬化性組成物の塗膜の表面張力(γv)よりも小さく、熱硬化性組成物とレベリング剤の界面張力(γI)も小さくなるように選択されうる。少ない添加量でも十分なレベリング効果を得るためには、レベリング剤はカチオン重合性化合物と相溶しないことが好ましい。 The leveling agent has a surface tension (γA) that is smaller than the surface tension (γv) of the coating film of the thermosetting composition in the heat curing step, and the interfacial tension (γI) between the thermosetting composition and the leveling agent is also It can be selected to be smaller. In order to obtain a sufficient leveling effect even with a small addition amount, the leveling agent is preferably incompatible with the cationic polymerizable compound.
レベリング剤は、塗膜面の表面張力を調整することで、被塗布物への組成物の濡れ性を改善し、塗膜面の流動性や消泡性を改善して表面を平滑にすることができ;それらの効果は、わずかな添加量で発現することが多い。そのため、例えばフッ素系ポリマーなどと比べて表面改質作用が小さいシリコーン系ポリマーやアクリレート系ポリマーが好ましい。 Leveling agents improve the wettability of the composition to the coating object by adjusting the surface tension of the coating surface, and improve the fluidity and defoaming property of the coating surface to smooth the surface. These effects are often manifested in small additions. For this reason, for example, a silicone polymer or an acrylate polymer having a smaller surface modifying action than a fluorine polymer or the like is preferable.
シリコーン系ポリマーは、下記式で示されるポリジメチルシロキサン由来の構造含むポリマーであることが好ましい。下記式におけるnは、2以上であることが好ましく、2〜140であることがより好ましい。
シリコーン系ポリマーの例には、ポリジメチルシロキサン、ポリエーテル変性ポリジメチルシロキサン、ポリメチルアルキルシロキサンが含まれる。 Examples of the silicone-based polymer include polydimethylsiloxane, polyether-modified polydimethylsiloxane, and polymethylalkylsiloxane.
アクリレート系ポリマーは、アクリル酸アルキルエステルのポリマーであることが好ましい。アクリル酸アルキルエステルのアルキル鎖の炭素数は4以上であることが好ましく、6以上であることがより好ましい。アクリル酸アルキルエステルのアルキル鎖の炭素数の上限は、例えば12でありうる。アクリル酸アルキルエステルの例には、ブチルアクリレート、2−エチルヘキシルアクリレートなどが含まれる。アクリレート系ポリマーは、フッ素原子を含有しないことが好ましい。アクリル酸アルキルエステルは、一種類であっても、二種類以上であってもよい。 The acrylate polymer is preferably a polymer of acrylic acid alkyl ester. The number of carbon atoms in the alkyl chain of the acrylic acid alkyl ester is preferably 4 or more, and more preferably 6 or more. The upper limit of the number of carbon atoms of the alkyl chain of the acrylic acid alkyl ester can be 12, for example. Examples of the acrylic acid alkyl ester include butyl acrylate, 2-ethylhexyl acrylate, and the like. The acrylate polymer preferably does not contain a fluorine atom. The alkyl acrylate ester may be one type or two or more types.
アクリレート系ポリマーの例には、ブチルアクリレートと2−エチルヘキシルアクリレートの共重合体などが含まれる。 Examples of the acrylate polymer include a copolymer of butyl acrylate and 2-ethylhexyl acrylate.
シリコーン系ポリマーやアクリレート系ポリマーの分子量は、1000〜10000程度としうる。分子量が一定以上であると、レベリング剤が硬化物から染み出しにくくしうる。一方、分子量が一定以下であると、レベリング剤が熱硬化性組成物の塗膜表面に配向しやすく、十分なレベリング効果が得られやすい。 The molecular weight of the silicone polymer or acrylate polymer can be about 1000 to 10,000. When the molecular weight is a certain level or more, the leveling agent may be difficult to exude from the cured product. On the other hand, when the molecular weight is below a certain level, the leveling agent is easily oriented on the coating film surface of the thermosetting composition, and a sufficient leveling effect is easily obtained.
レベリング剤の含有量は、カチオン重合性化合物((A)成分)100質量部に対して0.01〜1質量部であることが好ましく、0.05〜0.5質量部であることがより好ましい。レベリング剤の含有量が一定以上であると、硬化性樹脂組成物の塗膜表面に十分な量のレベリング剤が配向しやすく、十分なレベリング効果が得られやすい。一方、レベリング剤の含有量が一定以下であると、レベリング剤とカチオン重合性化合物との相溶性や硬化物の透明性が損なわれにくい。 The content of the leveling agent is preferably 0.01 to 1 part by mass and more preferably 0.05 to 0.5 part by mass with respect to 100 parts by mass of the cationic polymerizable compound (component (A)). preferable. When the content of the leveling agent is a certain level or more, a sufficient amount of the leveling agent is easily oriented on the coating film surface of the curable resin composition, and a sufficient leveling effect is easily obtained. On the other hand, when the content of the leveling agent is below a certain level, the compatibility between the leveling agent and the cationic polymerizable compound and the transparency of the cured product are difficult to be impaired.
レベリング剤(D)のポリエーテル化合物(C)に対する含有比率(D)/(C)(質量比)は、0.002〜20であることが好ましく、0.01〜10であることがより好ましく、0.03〜5であることがさらにより好ましい。 The content ratio (D) / (C) (mass ratio) of the leveling agent (D) to the polyether compound (C) is preferably 0.002 to 20, and more preferably 0.01 to 10. 0.03 to 5 is even more preferable.
(E)その他の任意成分
本発明の熱硬化性組成物は、本発明の効果を損なわない範囲で、(E)その他の任意成分をさらに含んでもよい。その他の任意成分の例には、前記(A)以外の他の樹脂成分、カップリング剤、充填剤、改質剤、酸化防止剤、安定剤、溶媒などが含まれる。(E) Other optional components The thermosetting composition of the present invention may further contain (E) other optional components as long as the effects of the present invention are not impaired. Examples of other optional components include resin components other than the above (A), coupling agents, fillers, modifiers, antioxidants, stabilizers, solvents, and the like.
他の樹脂成分の例には、固体状のカチオン重合性化合物(例えば、固体状のエポキシ樹脂など)、ポリアミド、ポリアミドイミド、ポリウレタン、ポリブタジエン、ポリクロロプレン、ポリエーテル、ポリエステル、スチレン−ブタジエン−スチレンブロック共重合体、石油樹脂、キシレン樹脂、ケトン樹脂、セルロース樹脂、フッ素系オリゴマー、シリコン系オリゴマー、ポリスルフィド系オリゴマー等が含まれる。熱硬化性組成物に含まれる他の樹脂成分は、一種のみであってもよいし、二種以上であってもよい。 Examples of other resin components include solid cationic polymerizable compounds (eg, solid epoxy resins), polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block. Copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, fluorine-based oligomers, silicon-based oligomers, polysulfide-based oligomers and the like are included. One type of other resin component contained in a thermosetting composition may be sufficient, and 2 or more types may be sufficient as it.
カップリング剤の例には、シランカップリング剤、チタン系カップリング剤、ジルコニウム系カップリング剤、アルミニウム系カップリング剤などが含まれる。カップリング剤は、有機ELデバイスの基板等との密着性を高めうる。 Examples of coupling agents include silane coupling agents, titanium coupling agents, zirconium coupling agents, aluminum coupling agents, and the like. The coupling agent can enhance the adhesion with the substrate of the organic EL device.
シランカップリング剤の例には、1)エポキシ基を有するシランカップリング剤、2)エポキシ基と反応可能な官能基を有するシランカップリング剤、および3)その他のシランカップリング剤が含まれる。シランカップリング剤は、硬化膜中に、低分子量成分を残存させない観点などから、熱硬化性組成物中のエポキシ樹脂と反応するシランカップリング剤であることが好ましい。エポキシ樹脂と反応するシランカップリング剤は、1)エポキシ基を有するシランカップリング剤、もしくは2)エポキシ基と反応可能な官能基を有するシランカップリング剤であることが好ましい。エポキシ基と反応するとは、エポキシ基と付加反応することなどをいう。 Examples of the silane coupling agent include 1) a silane coupling agent having an epoxy group, 2) a silane coupling agent having a functional group capable of reacting with an epoxy group, and 3) other silane coupling agents. The silane coupling agent is preferably a silane coupling agent that reacts with the epoxy resin in the thermosetting composition from the viewpoint of preventing the low molecular weight component from remaining in the cured film. The silane coupling agent that reacts with the epoxy resin is preferably 1) a silane coupling agent having an epoxy group, or 2) a silane coupling agent having a functional group capable of reacting with an epoxy group. Reacting with an epoxy group means an addition reaction with an epoxy group.
1)エポキシ基を有するシランカップリング剤の例には、γ-グリシドキシプロピルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランなどが含まれる。2)エポキシ基と反応可能な官能基には、1級アミノ基、2級アミノ基等のアミノ基;カルボキシル基等が含まれるほか、エポキシ基と反応可能な官能基に変換される基(例えば、メタクリロイル基、イソシアネート基など)も含まれる。このようなエポキシ基と反応可能な官能基を有するシランカップリング剤の例には、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルトリメトキシシランなどが含まれる。3)その他のシランカップリング剤の例には、ビニルトリアセトキシシラン、ビニルトリメトキシシランなどが含まれる。これらのシランカップリング剤は、熱硬化性組成物に1種のみ含まれてもよく、2種以上含まれてもよい。 1) Examples of the silane coupling agent having an epoxy group include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. 2) Functional groups capable of reacting with epoxy groups include amino groups such as primary amino groups and secondary amino groups; carboxyl groups and the like, and groups that can be converted into functional groups capable of reacting with epoxy groups (for example, Methacryloyl group, isocyanate group, etc.). Examples of such a silane coupling agent having a functional group capable of reacting with an epoxy group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3- Aminopropylmethyltrimethoxysilane and the like are included. 3) Examples of other silane coupling agents include vinyltriacetoxysilane and vinyltrimethoxysilane. One kind of these silane coupling agents may be contained in the thermosetting composition, or two or more kinds thereof may be contained.
シランカップリング剤の分子量は、80〜800であることが好ましい。シランカップリング剤の分子量が800を超えると、密着性が低下することがある。 The molecular weight of the silane coupling agent is preferably 80 to 800. When the molecular weight of the silane coupling agent exceeds 800, the adhesion may be lowered.
シランカップリング剤の含有量は、熱硬化性組成物100質量部に対して、0.05〜30質量部であることが好ましく、0.1〜20質量部であることがより好ましく、0.3〜10質量部であることがさらに好ましい。 The content of the silane coupling agent is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the thermosetting composition. More preferably, it is 3-10 mass parts.
充填剤の例には、ガラスビーズ、スチレン系ポリマー粒子、メタクリレート系ポリマー粒子、エチレン系ポリマー粒子、プロピレン系ポリマー粒子等が含まれる。改質剤の例には、重合開始助剤、老化防止剤、界面活性剤、可塑剤等が含まれる。安定剤の例には、紫外線吸収剤、防腐剤、抗菌剤等が含まれる。 Examples of the filler include glass beads, styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, propylene polymer particles, and the like. Examples of the modifier include polymerization initiation assistants, antiaging agents, surfactants, plasticizers, and the like. Examples of stabilizers include ultraviolet absorbers, preservatives, antibacterial agents and the like.
酸化防止剤とは、プラズマ照射や日光照射により発生するラジカルを失活させるもの(Hindered Amine Light Stabilizer, HALS)や、過酸化物を分解するものなどをいう。酸化防止剤を含む熱硬化性組成物の硬化物は、変色が抑制されうる。酸化防止剤の例には、Tinuvin123(ビス(1−オクチロキシ−2,2,6,6−テトラメチル−4−ピペリジル)セバシン酸)、Tinuvin765(ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)セバシン酸とメチル 1,2,2,6,6−ペンタメチル−4−ピペリジルセバシン酸との混合物)などが含まれる。 Antioxidants refer to those that deactivate radicals generated by plasma irradiation or sunlight irradiation (Hindered Amine Light Stabilizer, HALS), and those that decompose peroxides. Discoloration of the cured product of the thermosetting composition containing the antioxidant can be suppressed. Examples of antioxidants include Tinuvin 123 (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacic acid), Tinuvin 765 (bis (1,2,2,6,6-pentamethyl). -4-piperidyl) sebacic acid and a mixture of methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacic acid) and the like.
溶剤は、各成分を均一に分散または溶解させうる。溶剤は、有機溶剤であり、その例には、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒;エチレングリコ−ルモノアルキルエーテル、エチレングリコ−ルジアルキルエーテル、プロピレングリコールジアルキルエーテル等のエーテル類;N−メチルピロリドン等の非プロトン性極性溶媒;酢酸エチル、酢酸ブチル等のエステル類等が含まれる。 The solvent can uniformly disperse or dissolve each component. Solvent is an organic solvent, examples of which include acetone, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone; ethylene glycol - monoalkyl ethers, ethylene glycol - Le dialkyl ethers, ethers such as propylene glycol distearate alkyl ethers; Examples include aprotic polar solvents such as N-methylpyrrolidone; esters such as ethyl acetate and butyl acetate.
熱硬化性組成物の物性
本発明の熱硬化性組成物の、E型粘度計により25℃、2.5rpmで測定される粘度は、50〜30000mPa・sであることが好ましく、100〜10000mPa・sであることがより好ましい。熱硬化性組成物の粘度が上記範囲であると、塗工性(例えばスクリーン印刷性)が高まる。熱硬化性組成物の粘度は、E型粘度計(東機産業製 RC−500)によって測定される。Physical properties of thermosetting composition The viscosity of the thermosetting composition of the present invention measured by an E-type viscometer at 25 ° C and 2.5 rpm is preferably 50 to 30,000 mPa · s, and preferably 100 to 10000 mPa · s. More preferably, it is s. When the viscosity of the thermosetting composition is within the above range, coatability (for example, screen printability) is enhanced. The viscosity of the thermosetting composition is measured with an E-type viscometer (RC-500 manufactured by Toki Sangyo).
本発明の熱硬化性組成物の含水率は、0.1質量%以下であることが好ましく、0.06質量%以下であることがより好ましい。有機EL素子は水分により劣化しやすい。したがって、熱硬化性組成物の含水率をできるだけ低減することが好ましい。熱硬化性組成物の含水率は、試料サンプルを約0.1g計量し、カールフィッシャー水分計にて150℃に加熱し、その際に発生する水分量を測定することで求められる(固体気化法)。 The water content of the thermosetting composition of the present invention is preferably 0.1% by mass or less, and more preferably 0.06% by mass or less. Organic EL elements are easily degraded by moisture. Therefore, it is preferable to reduce the water content of the thermosetting composition as much as possible. The moisture content of the thermosetting composition can be obtained by weighing about 0.1 g of a sample sample, heating to 150 ° C. with a Karl Fischer moisture meter, and measuring the amount of water generated at that time (solid vaporization method). ).
本発明の熱硬化性組成物の反応活性発現温度は、面封止する素子の耐熱温度により適宜調整され、70〜150℃であることが好ましく、80〜110℃であることがより好ましく、90〜100℃であることがさらに好ましい。反応活性発現温度は、熱硬化性組成物の硬化可能温度と密接な関係がある。反応活性発現温度が150℃以下であれば、熱硬化性組成物を150℃以下で加熱硬化が可能であり、面封止時に、有機EL素子に影響を及ぼす可能性が少ない。一方、反応活性発現温度が70℃以上であれば、組成物の保存時にカチオン重合性化合物((A)成分)の不要な硬化反応が生じにくく、保存安定性が良好となる。 The reaction activity expression temperature of the thermosetting composition of the present invention is appropriately adjusted depending on the heat resistance temperature of the element to be surface-sealed, preferably 70 to 150 ° C., more preferably 80 to 110 ° C., 90 More preferably, it is -100 degreeC. The reaction activity expression temperature is closely related to the curing temperature of the thermosetting composition. If the reaction activity expression temperature is 150 ° C. or lower, the thermosetting composition can be heat-cured at 150 ° C. or lower, and there is little possibility of affecting the organic EL element during surface sealing. On the other hand, when the reaction activity expression temperature is 70 ° C. or higher, an unnecessary curing reaction of the cationic polymerizable compound (component (A)) hardly occurs during storage of the composition, and storage stability is improved.
反応活性発現温度は、示差走査熱量測定(DSC)で測定される発熱ピークの立ち上がりの値として測定されうる。反応活性発現温度は、(A)カチオン重合性化合物や(B)熱カチオン重合開始剤の種類、好ましくは(B)熱カチオン重合開始剤に含まれる4級アンモニウムイオンの構造によって調整されうる。 The reaction activity onset temperature can be measured as the value of the rise of the exothermic peak measured by differential scanning calorimetry (DSC). The reaction activity expression temperature can be adjusted by the structure of (A) the cationic polymerizable compound or (B) the thermal cationic polymerization initiator, preferably the structure of the quaternary ammonium ion contained in (B) the thermal cationic polymerization initiator.
本発明の熱硬化性組成物の硬化物は、可視光の透過性が高いことが好ましい。膜厚10μmの熱硬化性組成物を、100℃で30分硬化させた硬化膜の、380nmの波長領域(可視・紫外光)の平行光線透過率が80%以上、より好ましくは90%以上、さらに好ましくは95%以上である。平行光線透過率を80%以上とすると、熱硬化性組成物の硬化物を介して有機EL素子が発する光を効率よく取り出すことができる。ただし、本発明の熱硬化性組成物をバックエミッション型の有機EL素子に用いる場合は、その硬化物の透明性は特に限定されない。硬化物の平行光線透過率は、(有)東京電色社製 全自動ヘーズメーター TC−H III DPKにより測定することができる。 The cured product of the thermosetting composition of the present invention preferably has high visible light permeability. A cured film obtained by curing a thermosetting composition having a thickness of 10 μm at 100 ° C. for 30 minutes has a parallel light transmittance in a wavelength region of 380 nm (visible / ultraviolet light) of 80% or more, more preferably 90% or more, More preferably, it is 95% or more. When the parallel light transmittance is 80% or more, light emitted from the organic EL element can be efficiently extracted through the cured product of the thermosetting composition. However, when the thermosetting composition of the present invention is used for a back emission type organic EL device, the transparency of the cured product is not particularly limited. The parallel light transmittance of the cured product can be measured with a fully automatic haze meter TC-H III DPK manufactured by Tokyo Denshoku Co., Ltd.
本発明の熱硬化性組成物は、例えば上記各成分を、不活性ガス環境下で反応活性発現温度よりも低い温度(例えば60℃以下)で混合する工程を経て製造されうる。各成分の混合は、各成分をフラスコに装入して攪拌する方法や、三本ロールミルで混練する方法などで行うことができる。 The thermosetting composition of the present invention can be produced, for example, through a step of mixing each of the above components at a temperature lower than the reaction activity expression temperature (for example, 60 ° C. or lower) in an inert gas environment. The mixing of each component can be performed by a method of charging each component in a flask and stirring, or a method of kneading with a three roll mill.
本発明の熱硬化性組成物は、光半導体の面封止剤として好ましく用いられうる。光半導体とは、例えば電気を光に変換して発光する素子であり、その例には無機LED素子、有機EL素子などが含まれ、好ましくは有機EL素子である。即ち、本発明の熱硬化性組成物は、有機EL素子の面封止剤として好ましく用いられる。 The thermosetting composition of the present invention can be preferably used as a surface sealing agent for optical semiconductors. An optical semiconductor is, for example, an element that converts electricity into light and emits light. Examples thereof include inorganic LED elements, organic EL elements, and the like, and preferably organic EL elements. That is, the thermosetting composition of the present invention is preferably used as a surface sealing agent for organic EL devices.
2.有機ELデバイス
図1は、有機ELパネルを構成しうる有機ELデバイスの一例を示す模式図である。図1に示されるように、有機ELデバイス20は、有機EL素子24が配置された表示基板22と、対向基板26と、少なくとも有機EL素子24と対向基板26との間に配置され、有機EL素子24を封止するシール部材28とを含む。シール部材28は、有機EL素子24の周囲を覆っており(面封止しており)、本発明の面封止剤(熱硬化性組成物)の硬化物で構成される。2. Organic EL Device FIG. 1 is a schematic diagram showing an example of an organic EL device that can constitute an organic EL panel. As shown in FIG. 1, the
表示基板22および対向基板26は、通常、ガラス基板または樹脂フィルムなどであり、表示基板22と対向基板26の少なくとも一方は、透明なガラス基板または透明な樹脂フィルムである。このような透明な樹脂フィルムの例には、ポリエチレンテレフタレート等の芳香族ポリエステル樹脂等が含まれる。
The
有機EL素子24がトップエミッション型である場合、有機EL素子24は、表示基板22側から、画素電極層30(アルミニウムや銀などからなる)と、有機EL層32と、対向電極層34(ITO(インジウムと錫の酸化物)やIZO(インジウムと亜鉛の酸化物)などからなる)とを含む。画素電極層30、有機EL層32および対向電極層34は、真空蒸着やスパッタなどで成膜されうる。
When the
有機ELデバイスは、例えば、1)基板上に配置された有機EL素子を準備する工程と、2)有機EL素子を面封止剤で覆う工程と、3)面封止剤を加熱硬化させる工程とを経て製造されうる。有機EL素子を面封止剤で覆う工程は、液状の面封止剤を塗布するか、固形状(シート状)の面封止剤を熱圧着して行うことができ、なかでも液状の面封止剤を塗布して行うことが好ましい。 An organic EL device is, for example, 1) a step of preparing an organic EL element disposed on a substrate, 2) a step of covering the organic EL element with a surface sealing agent, and 3) a step of heating and curing the surface sealing agent. It can be manufactured through. The step of covering the organic EL element with the surface sealing agent can be performed by applying a liquid surface sealing agent or by thermocompression bonding a solid (sheet-like) surface sealing agent. It is preferable to carry out by applying a sealant.
図2は、有機ELデバイスの製造プロセスの一例を示す模式図である。有機ELデバイス20は、1)有機EL素子24が積層された表示基板22を準備する工程(図2(A))と、2)本発明の面封止剤を有機EL素子24上に塗布して面封止剤の塗膜28Aを形成する工程(図2(B))と、3)面封止剤の塗膜28A上に、対向基板26を配置し、面封止剤の塗膜28Aを加熱硬化させてシール部材28とし、かつ対向基板26を貼り合わせる(図2(C))。このようにして、有機ELデバイス20を得ることができる。
FIG. 2 is a schematic diagram illustrating an example of a manufacturing process of an organic EL device. The
面封止剤の塗布は、スクリーン印刷、ディスペンサー塗布、スリットコーティング、スプレーコーティングなどの手法で行うことができる。 The surface sealing agent can be applied by techniques such as screen printing, dispenser application, slit coating, and spray coating.
面封止剤の加熱硬化は、比較的低い温度で行うことができる。加熱硬化温度は、面封止剤中の(B)熱カチオン重合開始剤が活性化する温度であればよく、70〜150℃が好ましく、より好ましくは80〜110℃であり、さらに好ましくは90〜100℃である。加熱硬化温度が70℃以上であると、十分に(B)熱カチオン重合開始剤を活性化しやすく、(A)カチオン重合性化合物を十分に硬化させやすい。加熱硬化温度が150℃以下であると、加熱硬化時に有機EL素子に影響を及ぼす可能性を少なくできる。 The surface sealing agent can be cured by heating at a relatively low temperature. The heat curing temperature may be a temperature at which (B) the thermal cationic polymerization initiator in the surface sealing agent is activated, preferably 70 to 150 ° C, more preferably 80 to 110 ° C, and still more preferably 90. ~ 100 ° C. When the heat curing temperature is 70 ° C. or higher, (B) the thermal cationic polymerization initiator is sufficiently activated, and (A) the cationic polymerizable compound is sufficiently cured. When the heat curing temperature is 150 ° C. or lower, the possibility of affecting the organic EL element during heat curing can be reduced.
加熱硬化は、例えばオーブンやホットプレートによる加熱等、公知の方法で行うことができる。加熱時間は、10〜120分であることが好ましく、20〜90分であることがより好ましく、さらに好ましくは30〜60分である。 The heat curing can be performed by a known method such as heating with an oven or a hot plate. The heating time is preferably 10 to 120 minutes, more preferably 20 to 90 minutes, and further preferably 30 to 60 minutes.
シール部材28の厚みは、有機EL素子24を十分に覆うことができる厚みであればよく、例えば0.1〜20μm程度としうる。
The thickness of the sealing
シール部材28上に、必要に応じてパッシベーション膜をさらに形成してもよい。パッシベーション膜は、シール部材28の全面を覆うものであってもよく、一部のみを覆うものであってもよい。パッシベーション膜は、例えばプラズマCVD法で成膜された無機化合物膜でありうる。パッシベーション膜の材質は、透明な無機化合物であることが好ましく、窒化ケイ素、酸化ケイ素、SiONF、SiONなどが例示されるが、特に限定されない。パッシベーション膜の厚みは、0.1〜5μmであることが好ましい。
A passivation film may be further formed on the
本発明の面封止剤は(C)ポリエーテル化合物を含むことから、面封止剤の加熱硬化過程において、(D)レベリング剤の効果を損なうことなく、面封止剤が流動しうる時間を長くすることができる。それにより、面封止剤の加熱硬化過程において、(D)レベリング剤が作用する時間を長くすることができる。それにより、有機EL素子上に、凸凹やハジキが少なく、表面平滑性が高い硬化物層を形成することができると推測される。 Since the surface sealing agent of the present invention contains (C) a polyether compound, the time during which the surface sealing agent can flow without impairing the effect of the (D) leveling agent in the heat curing process of the surface sealing agent. Can be lengthened. Thereby, in the process of heat-curing the surface sealing agent, the time during which (D) the leveling agent acts can be lengthened. Thereby, it is estimated that the hardened | cured material layer with few unevenness | corrugations and repellency and high surface smoothness can be formed on an organic EL element.
以下において、実施例を参照して本発明をより詳細に説明する。これらの実施例によって、本発明の範囲は限定して解釈されない。 In the following, the invention will be described in more detail with reference to examples. These examples do not limit the scope of the present invention.
1.熱硬化性組成物の材料
(A)カチオン重合性化合物
ビスフェノールF型エポキシ樹脂(重量平均分子量338、エポキシ当量165〜175g/eq、E型粘度(@25℃、2.5rpm)3000〜4000mPa・s、1分子内のカチオン重合性官能基の数:2個):YL983U、ジャパンエポキシレジン社製1. Material of thermosetting composition (A) Cationic polymerizable compound Bisphenol F type epoxy resin (weight average molecular weight 338, epoxy equivalent 165 to 175 g / eq, E type viscosity (@ 25 ° C., 2.5 rpm) 3000 to 4000 mPa · s 1) Number of cationically polymerizable functional groups in one molecule: 2): YL983U, manufactured by Japan Epoxy Resin Co., Ltd.
(B)熱カチオン重合開始剤
下記式で表される4級アンモニウム塩:CXC−1612、King industry社製
(C)ポリエーテル化合物
(ポリエチレングリコール)
PEG#400:重量平均分子量445
PEG#1000:重量平均分子量1030
PEG#2000:重量平均分子量2180
PEG#4000:重量平均分子量3220
PEG#6000:重量平均分子量8450
(クラウンエーテル)
18−クラウン−6−エーテル:分子量264(C) Polyether compound (polyethylene glycol)
PEG # 400: weight average molecular weight 445
PEG # 1000: weight average molecular weight 1030
PEG # 2000: weight average molecular weight 2180
PEG # 4000: weight average molecular weight 3220
PEG # 6000: weight average molecular weight 8450
(Crown ether)
18-crown-6-ether: molecular weight 264
(D)レベリング剤
シリコーン系ポリマー:LS−460、楠本化成社製(D) Leveling agent Silicone polymer: LS-460, manufactured by Enomoto Kasei Co., Ltd.
(E)カップリング剤
3-グリシドキシプロピルトリメトキシシラン(分子量236):KBM-403、信越化学工業社製(E) Coupling agent 3-glycidoxypropyltrimethoxysilane (molecular weight 236): KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.
2.熱硬化性組成物の作製
(実施例1)
窒素で置換したフラスコで、エポキシ樹脂(YL983U)100質量部と、2質量部の4級アンモニウム塩(CXC−1612)と、2質量部のポリエーテル化合物(PEG#400)と、0.3質量部のレベリング剤(LS−460)と、1質量部のシランカップリング剤(KBM−403)とを、50℃で攪拌混合して、熱硬化性組成物を得た。2. Preparation of thermosetting composition (Example 1)
In a flask replaced with nitrogen, 100 parts by mass of epoxy resin (YL983U), 2 parts by mass of a quaternary ammonium salt (CXC-1612), 2 parts by mass of a polyether compound (PEG # 400), 0.3 parts by mass Part of the leveling agent (LS-460) and 1 part by mass of the silane coupling agent (KBM-403) were stirred and mixed at 50 ° C. to obtain a thermosetting composition.
(実施例2〜9、比較例1〜2)
熱硬化性組成物の組成を、表1に示されるように変更した以外は実施例1と同様にして熱硬化性組成物を得た。(Examples 2-9, Comparative Examples 1-2)
A thermosetting composition was obtained in the same manner as in Example 1 except that the composition of the thermosetting composition was changed as shown in Table 1.
得られた熱硬化性組成物の粘度、保存安定性、および硬化物表面の平滑性を、以下の方法で評価した。 The viscosity, storage stability, and smoothness of the cured product surface of the obtained thermosetting composition were evaluated by the following methods.
(粘度)
得られた熱硬化性組成物の粘度を、E型粘度計(東機産業製 RC−500)を用いて、25℃、2.5rpmで測定した。(viscosity)
The viscosity of the obtained thermosetting composition was measured at 25 ° C. and 2.5 rpm using an E-type viscometer (RC-500 manufactured by Toki Sangyo).
(保存安定性)
得られた熱硬化性組成物を所定量採取し、23℃で24時間保存した後、熱硬化性組成物の白濁および流動性の低下の有無を観察した。保存後の熱硬化性組成物が白濁せず、流動性も低下しなかったものを「無」;保存後の熱硬化性組成物が白濁し、流動性が著しく低下したものを「有」とした。(Storage stability)
A predetermined amount of the obtained thermosetting composition was collected and stored at 23 ° C. for 24 hours, and then the presence or absence of white turbidity and fluidity of the thermosetting composition was observed. "No" if the thermosetting composition after storage was not cloudy and fluidity was not reduced; "Yes" if the thermosetting composition after storage was cloudy and fluidity was significantly reduced did.
(硬化物層表面の平滑性)
得られた熱硬化性組成物を、予めオゾン処理によって洗浄したガラス基板(7cm×7cm×0.7mm厚)に、スクリーン印刷機(Screen Printer Model 2200、MITANI製)を用いて印刷した。熱硬化性組成物の塗布は、乾燥状態で5cm×5cm×10μm厚となるように行った。印刷したガラス基板を、100℃に加熱したホットプレート上で30分間加熱して、硬化物層を得た。そして、得られた硬化物層を目視観察した。硬化物層に塗布欠陥(ハジキ)や凸凹がなく、表面が平滑であるものを○;硬化物層に塗布欠陥(ハジキ)や凸凹があり、表面が平滑でないものを×とした。(Smoothness of cured product layer surface)
The obtained thermosetting composition was printed on a glass substrate (7 cm × 7 cm × 0.7 mm thickness) previously cleaned by ozone treatment using a screen printer (Screen Printer Model 2200, manufactured by MITANI). Application | coating of the thermosetting composition was performed so that it might become 5 cm x 5 cm x 10 micrometers thickness in a dry state. The printed glass substrate was heated on a hot plate heated to 100 ° C. for 30 minutes to obtain a cured product layer. And the obtained hardened | cured material layer was visually observed. The cured product layer had no coating defects (repels) or irregularities, and the surface was smooth. A: The cured product layer had application defects (repels) or irregularities, and the surface was not smooth.
実施例1〜9および比較例1〜2の評価結果を表1に示す。なお、表1の組成の欄の数値の単位は「質量部」である。
表1に示されるように、ポリエーテル化合物とレベリング剤の両方を含む実施例1〜9の熱硬化性組成物の硬化物層は、いずれも塗布欠陥(ハジキ)や凸凹がなく、表面の平滑性が高いことがわかる。これに対して、ポリエーテル化合物を含まない比較例1の熱硬化性組成物、およびレベリング剤を含まない比較例2の熱硬化性組成物の硬化物層は、いずれも塗布欠陥(ハジキ)や凸凹があり、表面の平滑性が低いことがわかる。 As shown in Table 1, the cured layers of the thermosetting compositions of Examples 1 to 9 containing both the polyether compound and the leveling agent are free from coating defects (repels) and unevenness, and have a smooth surface. It turns out that the nature is high. On the other hand, the thermosetting composition of Comparative Example 1 that does not contain a polyether compound and the cured product layer of the thermosetting composition of Comparative Example 2 that does not contain a leveling agent both have coating defects (repellency) and It can be seen that there are irregularities and the surface smoothness is low.
実施例1〜9の熱硬化性組成物の硬化物層表面の平滑性が高められた理由は、必ずしも明らかではないが、以下のように考えられる。即ち、熱硬化性組成物を加熱硬化させる過程で、ポリエーテル化合物のエーテル結合部分が熱カチオン重合開始剤のカチオンを捕捉し、エポキシ樹脂のカチオン重合反応を遅延させ、熱硬化性組成物が流動しうる時間を長くすることができる。それにより、熱硬化性組成物の加熱硬化過程において、レベリング剤を十分に作用させることができたためと考えられる。 The reason why the smoothness of the cured layer surface of the thermosetting compositions of Examples 1 to 9 is improved is not necessarily clear, but is considered as follows. That is, in the process of thermosetting the thermosetting composition, the ether bond portion of the polyether compound captures the cation of the thermal cationic polymerization initiator, delays the cationic polymerization reaction of the epoxy resin, and the thermosetting composition flows. The possible time can be lengthened. This is considered to be because the leveling agent was able to sufficiently act in the heat curing process of the thermosetting composition.
本出願は、2013年6月10日出願の特願2013−121808に基づく優先権を主張する。当該出願明細書および図面に記載された内容は、すべて本願明細書に援用される。 This application claims the priority based on Japanese Patent Application No. 2013-121808 of an application on June 10, 2013. The contents described in the application specification and the drawings are all incorporated herein.
本発明によれば、例えば有機EL素子などの被塗布物上に、凹凸やハジキなどが少なく、表面の平滑性が高い硬化物層を形成できる熱硬化性組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the thermosetting composition which can form a hardened | cured material layer with few unevenness | corrugations, repelling, etc. and high surface smoothness on to-be-coated objects, such as an organic EL element, can be provided.
20 有機ELデバイス
22 表示基板
24 有機EL素子
26 対向基板
28A 面封止剤の塗膜
28 シール部材
30 画素電極層
32 有機EL層
34 対向電極層DESCRIPTION OF
Claims (9)
(B)熱カチオン重合開始剤と、
(C)ポリアルキレンオキサイド及びクラウンエーテルからなる群より選ばれる、重量平均分子量250〜10000のポリエーテル化合物と、
(D)レベリング剤とを含み、
E型粘度計で測定された25℃、2.5rpmにおける粘度が50〜30000mPa・sである熱硬化性組成物を含む、有機EL素子用面封止剤。 (A) a cationically polymerizable compound having two or more epoxy groups in one molecule;
(B) a thermal cationic polymerization initiator;
(C) a polyether compound having a weight average molecular weight of 250 to 10,000 selected from the group consisting of polyalkylene oxide and crown ether ;
(D) a leveling agent,
A surface sealing agent for organic EL devices, comprising a thermosetting composition having a viscosity of 50 to 30000 mPa · s at 25 ° C. and 2.5 rpm measured with an E-type viscometer.
前記(B)成分を0.1〜5質量部、
前記(D)成分を0.01〜1質量部含む、請求項1〜6のいずれか一項に記載の有機EL素子用面封止剤。 For 100 parts by mass of component (A),
0.1 to 5 parts by mass of the component (B),
The surface sealing agent for organic EL elements as described in any one of Claims 1-6 containing 0.01-1 mass part of said (D) components.
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Cited By (3)
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KR20210021455A (en) | 2018-06-15 | 2021-02-26 | 린텍 가부시키가이샤 | Encapsulant composition, encapsulation sheet and encapsulant |
CN114555653A (en) * | 2019-11-18 | 2022-05-27 | 电化株式会社 | Composition, cured product, sealing material for organic electroluminescent display element, and organic electroluminescent display device |
US11667786B2 (en) | 2020-03-19 | 2023-06-06 | Samsung Display Co., Ltd. | Encapsulating or filling composition for electronic devices and electronic apparatus |
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TWI691588B (en) * | 2014-12-09 | 2020-04-21 | 日商三井化學股份有限公司 | Surface sealing material for organic EL element and its hardened product |
TWI565117B (en) * | 2015-06-10 | 2017-01-01 | Wisechip Semiconductor Inc | Organic light emitting diode module with optical signal transmission |
DE102015212058A1 (en) * | 2015-06-29 | 2016-12-29 | Tesa Se | Adhesive, in particular for encapsulating an electronic device |
JP6776609B2 (en) * | 2016-02-22 | 2020-10-28 | デクセリアルズ株式会社 | Anisotropic conductive film |
KR20240010091A (en) * | 2016-02-22 | 2024-01-23 | 데쿠세리아루즈 가부시키가이샤 | Anisotropic conductive film |
JP6822863B2 (en) * | 2016-03-31 | 2021-01-27 | 三井化学株式会社 | Thermosetting composition, encapsulant containing the same, frame encapsulant for organic EL element, surface encapsulant for organic EL element, and cured product thereof. |
CN105957977B (en) * | 2016-05-13 | 2019-02-05 | 京东方科技集团股份有限公司 | A kind of encapsulating material, encapsulation cover plate, agglomerating plant, sintering method and display device |
KR102008177B1 (en) * | 2016-05-24 | 2019-08-07 | 삼성에스디아이 주식회사 | Composition for encapsulating organic light emitting device and organic light emitting display using prepared the same |
WO2018062930A2 (en) | 2016-09-30 | 2018-04-05 | 주식회사 엘지화학 | Adhesive composition |
KR102118365B1 (en) | 2017-04-21 | 2020-06-04 | 주식회사 엘지화학 | Composition for encapsulating organic electronic element |
JP6894290B2 (en) * | 2017-05-17 | 2021-06-30 | 東京応化工業株式会社 | Method for manufacturing curable composition, cured film, display panel, and cured product |
TW201936877A (en) * | 2018-01-26 | 2019-09-16 | 日商味之素股份有限公司 | Curable resin composition for sealing |
JP2019130719A (en) * | 2018-01-30 | 2019-08-08 | 株式会社ミマキエンジニアリング | Printer and printing method |
DE102018202545A1 (en) | 2018-02-20 | 2019-08-22 | Tesa Se | Composition for producing an adhesive, in particular for encapsulating an electronic device |
CN108873536B (en) * | 2018-06-01 | 2022-01-18 | Oppo广东移动通信有限公司 | Shell, preparation method thereof and electronic equipment |
JP7128716B2 (en) * | 2018-10-22 | 2022-08-31 | アイカ工業株式会社 | Photo cationic curable epoxy resin composition |
WO2020110859A1 (en) | 2018-11-28 | 2020-06-04 | 積水化学工業株式会社 | Curable resin composition, cured product and organic el display element |
KR20220016941A (en) * | 2019-07-05 | 2022-02-10 | 미쓰이 가가쿠 가부시키가이샤 | Encapsulant for organic EL display element and organic EL display device |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005240005A (en) * | 2004-01-30 | 2005-09-08 | Dainippon Ink & Chem Inc | Curable resin composition, transfer material, and protective layer forming method |
JP2008031424A (en) * | 2006-07-06 | 2008-02-14 | Daicel Chem Ind Ltd | Alicyclic diepoxy compound, epoxy resin composition and cured product |
JP2009203431A (en) * | 2008-02-29 | 2009-09-10 | Kyocera Chemical Corp | Epoxy resin composition for casting and highly heat conductive coil |
JP2010100736A (en) * | 2008-10-24 | 2010-05-06 | Toyo Ink Mfg Co Ltd | Ultraviolet-curable coating composition for can and its use |
JP2010248387A (en) * | 2009-04-16 | 2010-11-04 | Sekisui Chem Co Ltd | Photocurable resin composition for optical member, adhesive and touch panel |
JP2012057124A (en) * | 2010-09-13 | 2012-03-22 | Jsr Corp | Liquid curable resin composition for coating outermost layer of optical fiber, and the optical fiber |
JP2012211327A (en) * | 2005-04-22 | 2012-11-01 | Sun Chemical Bv | Inkjet ink |
JP2013018921A (en) * | 2011-07-13 | 2013-01-31 | Daicel Corp | Curable epoxy resin composition |
JP2013241568A (en) * | 2012-04-27 | 2013-12-05 | Jsr Corp | Substrate treating method, temporary fixing composition and semiconductor device |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4397998A (en) | 1981-12-14 | 1983-08-09 | Shell Oil Company | Curable epoxy compositions suitable for use in RIM processes |
US6306926B1 (en) * | 1998-10-07 | 2001-10-23 | 3M Innovative Properties Company | Radiopaque cationically polymerizable compositions comprising a radiopacifying filler, and method for polymerizing same |
JP2003246850A (en) | 2001-12-19 | 2003-09-05 | Sekisui Chem Co Ltd | Photocurable composition, and article coated, attached or enclosed using photocurable composition |
JP3820147B2 (en) | 2001-12-26 | 2006-09-13 | 積水化学工業株式会社 | Photo-curable composition |
JP2004067828A (en) | 2002-08-05 | 2004-03-04 | Nippon Perunotsukusu Kk | Epoxy resin powder coating |
JP4384509B2 (en) | 2003-01-09 | 2009-12-16 | 積水化学工業株式会社 | Method for sealing organic electroluminescent element and organic electroluminescent element |
CN100404578C (en) * | 2003-08-12 | 2008-07-23 | 三井化学株式会社 | Photo-curable resin composition and sealing agent for flat panel display using the same |
JP4804922B2 (en) * | 2003-08-12 | 2011-11-02 | 三井化学株式会社 | Photo-curable resin composition and sealing agent for flat panel display using the same |
US7192991B2 (en) * | 2003-11-26 | 2007-03-20 | 3M Innovative Properties Company | Cationically curable composition |
JP4795779B2 (en) * | 2005-11-09 | 2011-10-19 | 株式会社アルバック | Organic electroluminescence display panel |
JP5697048B2 (en) | 2012-06-15 | 2015-04-08 | 古河電気工業株式会社 | Resin composition for sealing organic electroluminescent element, sealing film for organic electroluminescent element, gas barrier film for organic electroluminescent element, and organic electroluminescent element using the same |
-
2014
- 2014-06-10 CN CN201480012025.1A patent/CN105026493B/en active Active
- 2014-06-10 KR KR1020157025702A patent/KR101697892B1/en active IP Right Grant
- 2014-06-10 TW TW103120041A patent/TWI601783B/en active
- 2014-06-10 JP JP2014547612A patent/JP5763280B2/en active Active
- 2014-06-10 WO PCT/JP2014/003074 patent/WO2014199626A1/en active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005240005A (en) * | 2004-01-30 | 2005-09-08 | Dainippon Ink & Chem Inc | Curable resin composition, transfer material, and protective layer forming method |
JP2012211327A (en) * | 2005-04-22 | 2012-11-01 | Sun Chemical Bv | Inkjet ink |
JP2008031424A (en) * | 2006-07-06 | 2008-02-14 | Daicel Chem Ind Ltd | Alicyclic diepoxy compound, epoxy resin composition and cured product |
JP2009203431A (en) * | 2008-02-29 | 2009-09-10 | Kyocera Chemical Corp | Epoxy resin composition for casting and highly heat conductive coil |
JP2010100736A (en) * | 2008-10-24 | 2010-05-06 | Toyo Ink Mfg Co Ltd | Ultraviolet-curable coating composition for can and its use |
JP2010248387A (en) * | 2009-04-16 | 2010-11-04 | Sekisui Chem Co Ltd | Photocurable resin composition for optical member, adhesive and touch panel |
JP2012057124A (en) * | 2010-09-13 | 2012-03-22 | Jsr Corp | Liquid curable resin composition for coating outermost layer of optical fiber, and the optical fiber |
JP2013018921A (en) * | 2011-07-13 | 2013-01-31 | Daicel Corp | Curable epoxy resin composition |
JP2013241568A (en) * | 2012-04-27 | 2013-12-05 | Jsr Corp | Substrate treating method, temporary fixing composition and semiconductor device |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20210021455A (en) | 2018-06-15 | 2021-02-26 | 린텍 가부시키가이샤 | Encapsulant composition, encapsulation sheet and encapsulant |
CN114555653A (en) * | 2019-11-18 | 2022-05-27 | 电化株式会社 | Composition, cured product, sealing material for organic electroluminescent display element, and organic electroluminescent display device |
US11667786B2 (en) | 2020-03-19 | 2023-06-06 | Samsung Display Co., Ltd. | Encapsulating or filling composition for electronic devices and electronic apparatus |
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WO2014199626A1 (en) | 2014-12-18 |
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