JP2010103171A - Photoelectric conversion element and composition for optical semiconductor element coating - Google Patents
Photoelectric conversion element and composition for optical semiconductor element coating Download PDFInfo
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- JP2010103171A JP2010103171A JP2008271081A JP2008271081A JP2010103171A JP 2010103171 A JP2010103171 A JP 2010103171A JP 2008271081 A JP2008271081 A JP 2008271081A JP 2008271081 A JP2008271081 A JP 2008271081A JP 2010103171 A JP2010103171 A JP 2010103171A
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- composition
- photoelectric conversion
- semiconductor element
- optical semiconductor
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Landscapes
- Led Devices (AREA)
Abstract
Description
本発明は、光電変換素子などに用いられる高屈折性コート材に用いられる組成物、およびそのコート材を有する光電変換素子に関する。 The present invention relates to a composition used for a highly refractive coating material used for a photoelectric conversion element and the like, and a photoelectric conversion element having the coating material.
発光ダイオード(LED)素子等の光半導体素子は、通常、発光素子の保護や発色変更のために、封止材で覆われている。そして、この光半導体素子を高屈折率な材料でコートすることで光の取り出し効率が高くなる事が知られている。 An optical semiconductor element such as a light emitting diode (LED) element is usually covered with a sealing material in order to protect the light emitting element and change the color. It is known that the light extraction efficiency is increased by coating the optical semiconductor element with a material having a high refractive index.
従来、この封止材に用いられる樹脂としてはエポキシ樹脂が一般であった(たとえば、特許文献1および2参照)が、発光素子として青色LED素子や紫外線LED素子を用いたLED素子では、青色LED素子から発せられる近紫外光や紫外線LED素子から発せられる紫外光により、発光素子近傍でエポキシ樹脂封止材が黄変したり、発光素子の発熱により熱劣化したりするという問題があった。特に、電灯などの高輝度が要求される用途では、青色LED素子や紫外線LED素子からの発光量も多く、黄変や熱劣化が起こり易かった。 Conventionally, an epoxy resin has been generally used as a resin used for this sealing material (see, for example, Patent Documents 1 and 2). However, in an LED element using a blue LED element or an ultraviolet LED element as a light emitting element, a blue LED is used. There has been a problem that the epoxy resin sealing material is yellowed in the vicinity of the light emitting element or is thermally deteriorated due to heat generation of the light emitting element due to near ultraviolet light emitted from the element or ultraviolet light emitted from the ultraviolet LED element. In particular, in applications that require high luminance such as electric lamps, the amount of light emitted from blue LED elements and ultraviolet LED elements is large, and yellowing and thermal degradation are likely to occur.
このため、高輝度環境下においても、近紫外光や紫外光による黄変が発生せず、耐熱性を有する封止材としてシリコーン樹脂封止材が検討されてきた。しかしながら、ジメチルシロキサンからなるシリコーン樹脂は、屈折率が低く、LED素子から発せられた光を効率的に取り出すことが難しいことが言われている。 For this reason, a silicone resin sealing material has been studied as a heat-resistant sealing material that does not cause yellowing due to near-ultraviolet light or ultraviolet light even in a high-luminance environment. However, it is said that the silicone resin made of dimethylsiloxane has a low refractive index, and it is difficult to efficiently extract light emitted from the LED element.
特許文献3および4には、ケイ素原子に結合したアルケニル基を有するシリコーンレジンとSi−H結合を有するオルガノハイドロジェンポリシロキサンとを含有するシリコーン樹脂組成物が開示されている。特許文献3および4では、このシリコーン樹脂組成物をヒドロシリル化反応により架橋させて硬化物を形成している。しかしながら、この硬化物は屈折率が低いことが課題であった。 Patent Documents 3 and 4 disclose a silicone resin composition containing a silicone resin having an alkenyl group bonded to a silicon atom and an organohydrogenpolysiloxane having a Si—H bond. In Patent Documents 3 and 4, this silicone resin composition is crosslinked by a hydrosilylation reaction to form a cured product. However, this cured product has a problem of low refractive index.
ところで、反射防止膜には、高屈折性微粒子とポリシロキサンとを含有する高屈折率膜
が使用されている。特許文献5には、酸化ジルコニウムなどの金属酸化物微粒子とエポキシ基等有するシリコーン化合物とを含有するコーティング剤の硬化物からなる高屈折率層が開示されている。また、特許文献6には、酸化ジルコニウムなどの無機微粒子と、ビニル基含有ポリシロキサンと熱硬化性樹脂とからなるバインダーとを用いた高屈折率層が開示されている。しかしながら、これらのコート材の屈折率は1.6程度と光半導体素子に使用するには十分ではなかった。
By the way, a high refractive index film containing highly refractive fine particles and polysiloxane is used for the antireflection film. Patent Document 5 discloses a high refractive index layer made of a cured product of a coating agent containing metal oxide fine particles such as zirconium oxide and a silicone compound having an epoxy group or the like. Patent Document 6 discloses a high refractive index layer using inorganic fine particles such as zirconium oxide and a binder made of a vinyl group-containing polysiloxane and a thermosetting resin. However, the refractive index of these coating materials is about 1.6, which is not sufficient for use in an optical semiconductor element.
一方、アルコキシシランモノマーを加水分解・縮合して形成したポリシロキサン膜は、厚膜を形成すると割れが発生しやすく、LED用封止材には不適であった。 On the other hand, a polysiloxane film formed by hydrolysis and condensation of an alkoxysilane monomer is liable to crack when a thick film is formed, and is unsuitable for an LED sealing material.
本発明は、上記のような従来技術に伴う問題を解決するものであって、屈折率が高く、透明性に優れ、さらに耐熱性にも優れた光半導体素子コート用組成物、及び、発光効率に優れた光電変換素子を提供することを目的とする。 The present invention solves the problems associated with the prior art as described above, and has a composition having a high refractive index, excellent transparency, and excellent heat resistance, and a luminous efficiency. An object of the present invention is to provide a photoelectric conversion element having excellent resistance.
上記目的を達成するため、本発明者らは鋭意研究を行い、特定の位置に硫黄原子を導入したポリアミック酸のイミド化重合体及び酸化チタン又は酸化ジルコニウムといった金属酸化物微粒子を含有した組成物を光半導体素子のコート材として使用することで、光の取り出し効率に優れた光電変換素子が得られることを見出し、本発明を完成させた。 In order to achieve the above object, the present inventors have conducted intensive research and obtained a composition containing an imidized polymer of polyamic acid having a sulfur atom introduced at a specific position and metal oxide fine particles such as titanium oxide or zirconium oxide. It has been found that a photoelectric conversion element having excellent light extraction efficiency can be obtained by using it as a coating material for an optical semiconductor element, and the present invention has been completed.
即ち、本発明は、下記の光電変換素子、及び、光半導体素子コート用組成物を提供する。
[1]光半導体素子上にコート層を有する光電変換素子であって、前記コート層が(A)下記一般式(1)で示される構造を有するポリアミック酸、及びそのイミド化重合体から選ばれる1種以上、(B)一次粒子径が1〜100nmである酸化チタン又は酸化ジルコニウムを主成分とする粒子、を含有する樹脂組成物から得られる層であることを特徴とする光電変換素子。
[2]前記光半導体素子のコート層の25℃、633nmにおける屈折率が1.70以上であることを特徴とする[1]に記載の光電変換素子。
[3]前記Rが、4価の脂肪族基又は4価の脂環族基であることを特徴とする[1]又は[2]に記載の光電変換素子。
[4]前記Rが、硫黄原子を含む4価の有機基からなる群から選択されることを特徴とする[1]〜[3]のいずれか1に記載の光電変換素子。
[5]前記成分(B)の粒子が、酸化珪素被覆された粒子であることを特徴とする[1]〜[4]のいずれか1に記載の光電変換素子。
[6](A)下記一般式(1)で示される構造を有するポリアミック酸、及びそのイミド化重合体から選ばれる1種以上、(B)酸化チタン又は酸化ジルコニウムを主成分とする一次粒子径が1〜100nmの粒子、を含有する光半導体素子コート用組成物。
[7]前記Rが、4価の脂肪族基又は4価の脂環族基であることを特徴とする[6]に記載の光半導体素子コート用組成物。
[8]前記Rが、硫黄原子を含む4価の有機基であることを特徴とする[6]又は[7]に記載の光半導体素子コート用組成物。
[9]前記成分(B)の粒子が、酸化珪素被覆されていることを特徴とする[6]〜[8]のいずれか1に記載の光半導体素子コート用組成物。
[10]さらに、(C)界面活性剤を含有することを特徴とする[6]〜[9]のいずれか1に記載の光半導体素子コート用組成物。
[11]さらに、前記一般式(1)で示されるポリアミック酸以外のポリアミック酸を含有することを特徴とする[6]〜[10]のいずれか1に記載の光半導体素子コート用組成物。
That is, the present invention provides the following photoelectric conversion element and composition for coating an optical semiconductor element.
[1] A photoelectric conversion element having a coat layer on an optical semiconductor element, wherein the coat layer is selected from (A) a polyamic acid having a structure represented by the following general formula (1), and an imidized polymer thereof. A photoelectric conversion element characterized by being a layer obtained from a resin composition containing at least one kind and (B) particles mainly composed of titanium oxide or zirconium oxide having a primary particle diameter of 1 to 100 nm.
[2] The photoelectric conversion element according to [1], wherein the coating layer of the optical semiconductor element has a refractive index of 1.70 or more at 25 ° C. and 633 nm.
[3] The photoelectric conversion element according to [1] or [2], wherein R is a tetravalent aliphatic group or a tetravalent alicyclic group.
[4] The photoelectric conversion element according to any one of [1] to [3], wherein R is selected from the group consisting of a tetravalent organic group containing a sulfur atom.
[5] The photoelectric conversion element according to any one of [1] to [4], wherein the particles of the component (B) are particles coated with silicon oxide.
[6] (A) One or more kinds selected from polyamic acid having a structure represented by the following general formula (1) and an imidized polymer thereof, (B) Primary particle diameter mainly composed of titanium oxide or zirconium oxide A composition for coating an optical semiconductor element, comprising particles having a diameter of 1 to 100 nm.
[7] The composition for coating an optical semiconductor element according to [6], wherein R is a tetravalent aliphatic group or a tetravalent alicyclic group.
[8] The composition for coating an optical semiconductor element according to [6] or [7], wherein R is a tetravalent organic group containing a sulfur atom.
[9] The composition for coating an optical semiconductor element according to any one of [6] to [8], wherein the particles of the component (B) are coated with silicon oxide.
[10] The composition for coating an optical semiconductor element according to any one of [6] to [9], further comprising (C) a surfactant.
[11] The composition for coating an optical semiconductor element according to any one of [6] to [10], further comprising a polyamic acid other than the polyamic acid represented by the general formula (1).
本発明によれば、屈折率が高く、透明性及び耐熱性に優れ、光半導体素子のコートに適した組成物を提供することができる。
また、本発明によれば、発光効率の高い光電変換素子を供給することができる。
According to the present invention, a composition having a high refractive index, excellent transparency and heat resistance, and suitable for coating an optical semiconductor element can be provided.
Further, according to the present invention, a photoelectric conversion element with high luminous efficiency can be supplied.
[樹脂組成物]
本発明の光半導体素子コート用組成物(以下、本発明の組成物という)は、下記成分(A)〜(F)を含み得る。これらの成分のうち、成分(A)及び(B)は必須成分であり、それ以外は必要に応じて添加し得る任意成分である。
(A)下記一般式(1)で示される構造を有するポリアミック酸、及びそのイミド化重合体から選ばれる1種以上
(B)酸化チタン又は酸化ジルコニウムを主成分とする、一次粒子径が1〜100nmの範囲内の粒子
(C)界面活性剤
(D)イミド化触媒
(E)有機溶剤
(F)添加剤
以下、各成分について説明する。
[Resin composition]
The composition for optical semiconductor element coating of the present invention (hereinafter referred to as the composition of the present invention) may contain the following components (A) to (F). Among these components, components (A) and (B) are essential components, and the other components are optional components that can be added as necessary.
(A) 1 or more types chosen from the polyamic acid which has a structure shown by following General formula (1), and its imidation polymer
(B) Particles mainly composed of titanium oxide or zirconium oxide and having a primary particle diameter in the range of 1 to 100 nm (C) Surfactant (D) Imidization catalyst (E) Organic solvent (F) additive Each component will be described.
(A)一般式(1)で示される構造を有するポリアミック酸
本発明の組成物の必須成分であるポリアミック酸は、下記一般式(1)で示される構造を有し、それ自体の屈折率(25℃、波長400〜700nm)が非常に高く、高屈折率で、透明性及び耐熱性に優れた硬化物を形成することができる。
式(1)中、R1はそれぞれ独立に炭素数1〜3のアルキル基、アリール基、シアノ基であり、aは基R1の置換数であり、0〜4の整数を示す。aは0(即ち、置換基無し)であるか、又はR1がシアノ基であり、aが1であることが好ましい。
Rは4価の有機基を示し、具体的には、脂肪族、脂環族又は芳香族テトラカルボン酸二無水物から無水物基を除去した残基に相当し、得られる硬化物が透明性に優れることから、脂環族テトラカルボン酸二無水物の残基であることが好ましい。また、Rは、高屈折率が得られることから、硫黄原子を含んでいることも好ましい。
nは1〜4の整数を示し、2〜4の整数であることが好ましい。
mは1〜100000の整数を示し、10〜10000の整数であることが好ましい。
In Formula (1), R 1 is each independently an alkyl group having 1 to 3 carbon atoms, an aryl group, or a cyano group, a is the number of substitutions of the group R 1 , and represents an integer of 0 to 4. It is preferred that a is 0 (ie, no substituent) or R 1 is a cyano group and a is 1.
R represents a tetravalent organic group, and specifically corresponds to a residue obtained by removing an anhydride group from an aliphatic, alicyclic or aromatic tetracarboxylic dianhydride, and the resulting cured product is transparent. Therefore, it is preferably a residue of an alicyclic tetracarboxylic dianhydride. Moreover, since R has a high refractive index, it preferably contains a sulfur atom.
n shows the integer of 1-4 and it is preferable that it is an integer of 2-4.
m represents an integer of 1 to 100,000, and is preferably an integer of 10 to 10,000.
(a)一般式(1)で示される構造を有するポリアミック酸の製造
本発明の成分(A)は、下記一般式(3)で示されるジアミンと、下記一般式(4)で示されるテトラカルボン酸二酸無水物を反応させて得られる。
(b)一般式(3)で示されるジアミン
一般式(3)で示されるジアミンの例としては、例えば、4,4’−(p−フェニレンジスルファニル)ジアニリン、1,3−ビス(4−アミノフェニルスルファニル)ベンゼン、1,3−ビス(4−アミノフェノールスルファニル)5−シアノベンゼン、4,4’−チオビス[(p−フェニレンスルファニル)アニリン]、4,4’−ビス(4−アミノフェニルスルファニル)−p−ジチオフェノキシベンゼン等が挙げられ、4,4’−チオビス[(p−フェニレンスルファニル)アニリン]等が好ましい。
(B) Diamine represented by general formula (3) Examples of the diamine represented by general formula (3) include 4,4 ′-(p-phenylenedisulfanyl) dianiline, 1,3-bis (4- Aminophenylsulfanyl) benzene, 1,3-bis (4-aminophenolsulfanyl) 5-cyanobenzene, 4,4′-thiobis [(p-phenylenesulfanyl) aniline], 4,4′-bis (4-aminophenyl) Sulfanyl) -p-dithiophenoxybenzene and the like, and 4,4′-thiobis [(p-phenylenesulfanyl) aniline] and the like are preferable.
尚、本発明の組成物には、上記一般式(1)で示される構造を有するポリアミック酸以外のポリアミック酸を含有していてもよい。即ち、上記一般式(3)で示されるジアミンの他に、本発明の効果を損なわない範囲内で、硫黄原子を含有しないジアミンを併用することができる。この硫黄原子を含有しないジアミンとしては、例えば、p−フェニレンジアミン、m−フェニレンジアミン、4,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルエタン、4,4’−ジアミノジフェニルスルフィド、4,4’−ジアミノジフェニルスルホン、4,4’−ジアミノジフェニルエーテル、1,5−ジアミノナフタレン、3,3−ジメチル−4,4’−ジアミノビフェニル、4,4’−ジアミノベンズアニリド、3,4’−ジアミノジフェニルエーテル、3,3’−ジアミノベンゾフェノン、3,4’−ジアミノベンゾフェノン、4,4’−ジアミノベンゾフェノン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2−ビス(4−アミノフェニル)ヘキサフルオロプロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]スルホン、1,4−ビス(4−アミノフェノキシ)ベンゼン、1,3−ビス(4−アミノフェノキシ)ベンゼン、1,3−ビス(3−アミノフェノキシ)ベンゼン、9,9−ビス(4−アミノフェニル)−10−ヒドロアントラセン、9,9−ビス(4−アミノフェニル)フルオレン、4,4’−メチレン−ビス(2−クロロアニリン)、2,2’,5,5’−テトラクロロ−4,4’−ジアミノビフェニル、2,2’−ジクロロ−4,4’−ジアミノ−5,5’−ジメトキシビフェニル、3,3’−ジメトキシ−4,4’−ジアミノビフェニル、4,4’−(p−フェニレンジイソプロピリデン)ビスアニリン、4,4’−(m−フェニレンジイソプロピリデン)ビスアニリンを挙げることができる。 The composition of the present invention may contain a polyamic acid other than the polyamic acid having the structure represented by the general formula (1). That is, in addition to the diamine represented by the general formula (3), a diamine that does not contain a sulfur atom can be used in combination as long as the effects of the present invention are not impaired. Examples of the diamine not containing a sulfur atom include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4, 4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 3,4'- Diaminodiphenyl ether, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-Aminophenoxy) phenyl] hexafluoropropyl Pan, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 9,9-bis (4-amino) Phenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4 '-Diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylenediisopropylidene) bisaniline , 4,4 '- (m- phenylene-isopropylidene) can be exemplified bisaniline.
また、上記の硫黄原子を含有しないジアミンの他、ジアミノテトラフェニルチオフェン等のヘテロ原子を有する芳香族ジアミン;1,1−メタキシリレンジアミン、1,3−プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、4,4−ジアミノヘプタメチレンジアミン、1,4−ジアミノシクロヘキサン、イソホロンジアミン、テトラヒドロジシクロペンタジエニレンジアミン、ヘキサヒドロ−4,7−メタノインダニレンジメチレンジアミン、トリシクロ[6,2,1,02.7]−ウンデシレンジメチルジアミン等の脂肪族又は脂環族ジアミンを併用することもできる。 In addition to the above-mentioned diamines not containing sulfur atoms, aromatic diamines having heteroatoms such as diaminotetraphenylthiophene; 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine , Hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7 -Aliphatic or alicyclic diamines such as methanoin danylene dimethylene diamine and tricyclo [6,2,1,0 2.7 ] -undecylenedimethyl diamine may be used in combination.
成分(A)のポリアミック酸の製造に用いるジアミン類のうち、一般式(3)で示されるジアミンの割合は、50モル%以上であることが好ましく、80モル%以上であることがより好ましく、高屈折率を達成するためには100モル%であることが特に好ましい。 Of the diamines used for the production of the component (A) polyamic acid, the proportion of the diamine represented by the general formula (3) is preferably 50 mol% or more, more preferably 80 mol% or more, In order to achieve a high refractive index, it is particularly preferably 100 mol%.
(c)一般式(4)で示されるテトラカルボン酸二酸無水物
本発明において用いられる酸無水物は上記一般式(4)で表される。式(4)中、Rはテトラカルボン酸二無水物から無水物基を除去した残基に相当する。このような化合物としては、脂肪族、脂環族又は芳香族テトラカルボン酸二無水物が挙げられ、脂肪族及び脂環族テトラカルボン酸二無水物が好ましく、得られる硬化膜が優れた透明性を有することから、脂環族テトラカルボン酸二無水物が特に好ましい。
(C) Tetracarboxylic dianhydride represented by the general formula (4) The acid anhydride used in the present invention is represented by the general formula (4). In the formula (4), R corresponds to a residue obtained by removing the anhydride group from tetracarboxylic dianhydride. Examples of such compounds include aliphatic, alicyclic or aromatic tetracarboxylic dianhydrides, and aliphatic and alicyclic tetracarboxylic dianhydrides are preferred, and the resulting cured film has excellent transparency. In particular, alicyclic tetracarboxylic dianhydride is preferable.
脂肪族及び脂環族テトラカルボン酸二無水物の例としては、例えば、ブタンテトラカルボン酸二無水物、1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2,3,4−シクロペンタンテトラカルボン酸二無水物、4,10−ジオキサトリシクロ[6.3.1.02,7]ドデカン−3,5,9,11−テトラオン、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物、2,3,5−トリカルボキシシクロペンチル酢酸二水和物、3,5,6−トリカルボキシノルボルナン−2−酢酸二無水物、2,3,4,5−テトラヒドロフランテトラカルボン酸二無水物、1,3,3a,4,5,9b−ヘキサヒドロ−5−テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、5−(2,5−ジオキソテトラヒドロフラル)−3−メチル−3−シクロヘキセン−1,2−ジカルボン酸二無水物、ビシクロ[2,2,2]−オクト−7−エン−2,3,5,6−テトラカルボン酸二無水物等の脂肪族及び脂環族テトラカルボン酸二無水物を挙げることができる。これらのうちではブタンテトラカルボン酸二無水物、1,2,3,4−シクロブタンテトラカルボン酸二無水物、4,10−ジオキサトリシクロ[6.3.1.02,7]ドデカン−3,5,9,11−テトラオン、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、5−(2,5−ジオキソテトラヒドロフラル)−3−メチル−3−シクロヘキセン−1,2−ジカルボン酸二無水物及び1,3,3a,4,5,9b−ヘキサヒドロ−5−テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオンが好ましく、1,2,3,4−シクロブタンテトラカルボン酸二無水物、4,10−ジオキサトリシクロ[6.3.1.02,7]ドデカン−3,5,9,11−テトラオン、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物が特に好ましい。 Examples of the aliphatic and alicyclic tetracarboxylic dianhydrides include, for example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4 -Cyclopentanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 2,7 ] dodecane-3,5,9,11-tetraone, 1,2,4,5- Cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dihydrate, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetra Carboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3- Zeon, -(2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5 And aliphatic and alicyclic tetracarboxylic dianhydrides such as 1,6-tetracarboxylic dianhydride. Among these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 2,7 ] dodecane- 3,5,9,11-tetraone, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Acid dianhydride and 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 2,7 ] dodecane-3,5,9,11-tetraone 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride is particularly preferred.
芳香族テトラカルボン酸二無水物の具体例としては、例えば、ピロメリット酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’−ビフェニルスルホンテトラカルボン酸二無水物、1,4,5,8−ナフタレンテトラカルボン酸二無水物、2,3,6,7−ナフタレンテトラカルボン酸二無水物、3,3’,4,4’−ビフェニルエーテルテトラカルボン酸二無水物、3,3’,4,4’−ジメチルジフェニルシランテトラカルボン酸二無水物、3,3’,4,4’−テトラフェニルシランテトラカルボン酸二無水物、1,2,3,4−フランテトラカルボン酸二無水物、4,4’−ビス(3,4−ジカルボキシフェノキシ)ジフェニルスルフィド二無水物、4,4’−ビス(3,4−ジカルボキシフェノキシ)ジフェニルスルホン二無水物、4,4’−ビス(3,4−ジカルボキシフェノキシ)ジフェニルプロパン二無水物、4,4’−(ヘキサフルオロイソプロピリデン)ビス(フタル酸)二無水物、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、ビス(フタル酸)フェニルホスフィンオキサイド二無水物、p−フェニレン−ビス(トリフェニルフタル酸)二無水物、m−フェニレン−ビス(トリフェニルフタル酸)二無水物、ビス(トリフェニルフタル酸)−4,4’−ジフェニルエーテル二無水物、ビス(トリフェニルフタル酸)−4,4’−ジフェニルメタン二無水物等の芳香族テトラカルボン酸二無水物を挙げることができる。これらのうちでは、ピロメリット酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’−ビフェニルスルホンテトラカルボン酸二無水物、4,4’−(ヘキサフルオロイソプロピリデン)ビス(フタル酸)二無水物及び3,3’,4,4’−ビフェニルテトラカルボン酸二無水物が好ましい。 Specific examples of the aromatic tetracarboxylic dianhydride include, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4 ′. -Biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4 '-Biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarbo) Ciphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 4,4 ′-(hexafluoroisopropylidene) bis (phthalic acid) dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis Aromatic tetra such as (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride Carboxylic dianhydrides can be mentioned. Among these, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 4 4,4 '-(Hexafluoroisopropylidene) bis (phthalic acid) dianhydride and 3,3', 4,4'-biphenyltetracarboxylic dianhydride are preferred.
また、より高屈折率のポリアミック酸が得られることから、硫黄原子を含むテトラカルボン酸二無水物を用いることも好ましい。硫黄原子含有酸無水物の例としては、例えば、4,4’−[p−チオビス(フェニレン−スルファニル)]ジフタル酸無水物等が挙げられる。 In addition, since a polyamic acid having a higher refractive index can be obtained, it is also preferable to use a tetracarboxylic dianhydride containing a sulfur atom. Examples of sulfur atom-containing acid anhydrides include 4,4 '-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride.
(d)一般式(3)で示されるジアミンと一般式(4)で示されるテトラカルボン酸二酸無水物の反応
一般に、N−メチル−2−ピロリドン等の非プロトン性有機溶媒中において、ジアミン化合物と酸二無水物とを攪拌混合することによって、成分(A)のポリアミック酸を溶液として得ることができる。例えば、ジアミン化合物を有機溶媒に溶解し、これに酸二無水物を加えて、攪拌混合してもよく、また、ジアミン化合物と酸二無水物との混合物を有機溶媒に加えて、攪拌混合してもよい。反応は、通常、100℃以下、好ましくは、80℃以下の温度で、常圧下に行われる。しかし、反応は、必要に応じて、加圧下又は減圧下に行ってもよい。反応時間は、用いるジアミン化合物と酸二無水物や、有機溶媒、反応温度等によって異なるが、通常、4〜24時間の範囲である。また、有機溶剤に溶解する程度であれば一部がイミド化していてもよい。
(D) Reaction of the diamine represented by the general formula (3) and the tetracarboxylic dianhydride represented by the general formula (4) In general, in the aprotic organic solvent such as N-methyl-2-pyrrolidone, the diamine By mixing the compound and acid dianhydride with stirring, the polyamic acid of component (A) can be obtained as a solution. For example, a diamine compound may be dissolved in an organic solvent, and acid dianhydride may be added thereto and mixed with stirring. Alternatively, a mixture of a diamine compound and acid dianhydride may be added to an organic solvent and mixed with stirring. May be. The reaction is usually performed at a temperature of 100 ° C. or lower, preferably 80 ° C. or lower, under normal pressure. However, the reaction may be performed under pressure or under reduced pressure as necessary. The reaction time varies depending on the diamine compound and acid dianhydride used, the organic solvent, the reaction temperature, etc., but is usually in the range of 4 to 24 hours. Moreover, as long as it melt | dissolves in the organic solvent, a part may be imidized.
本発明の組成物中における成分(A)の配合量は、有機溶剤を除く固形分全量を100重量%としたときに、通常10〜90重量%、好ましくは20〜80重量%、より好ましくは30〜70重量%の範囲内である。成分(A)の配合量が10重量%未満では、十分な屈折率や耐熱性が発現できないおそれがある。
尚、本発明の組成物の必須成分は成分(A)と成分(B)であるが、通常は、成分(A)の製造に用いられる有機溶剤を含み、組成物の塗工性等の観点からも有機溶剤を含有することが好ましい。
The compounding amount of the component (A) in the composition of the present invention is usually 10 to 90% by weight, preferably 20 to 80% by weight, more preferably when the total solid content excluding the organic solvent is 100% by weight. It is in the range of 30 to 70% by weight. If the amount of component (A) is less than 10% by weight, sufficient refractive index and heat resistance may not be exhibited.
In addition, although the essential component of the composition of this invention is a component (A) and a component (B), it usually contains the organic solvent used for manufacture of a component (A), and viewpoints, such as the coating property of a composition. It is preferable to contain an organic solvent.
(B)酸化チタン又は酸化ジルコニウムを主成分とする、一次粒子径が1〜100nmの範囲内の粒子
成分(B)は酸化チタン又は酸化ジルコニウムを主成分とする粒子である。酸化チタン又は酸化ジルコニウムは屈折率が高いため、これらを主成分とする粒子を添加することにより、得られる硬化物の屈折率をさらに高めることができる。
成分(B)の粒子の一次粒子径は、1〜100nmの範囲内であることが必要であり、1〜50nmの範囲内であることが好ましく、5〜20nmの範囲内であることがより好ましい。粒子の一次粒子径が1nm未満であると、二次凝集が起こり易く硬化膜が白化するおそれがあり、100nmを超えると、薄膜形成時の面均一性が損なわれるおそれがある。ここで、一次粒子径は、透過型電子顕微鏡によって測定することができる。一般に粒径は分布を有するため、配合する粒子の粒径を表すためにメジアン径で表すことができる。成分(B)として好ましいメジアン径は5〜40nmであり、5〜15nmであることがより好ましい。
(B) Particles mainly composed of titanium oxide or zirconium oxide and having a primary particle diameter in the range of 1 to 100 nm Component (B) is particles composed mainly of titanium oxide or zirconium oxide. Since titanium oxide or zirconium oxide has a high refractive index, the refractive index of the resulting cured product can be further increased by adding particles containing these as main components.
The primary particle diameter of the component (B) particles needs to be in the range of 1 to 100 nm, preferably in the range of 1 to 50 nm, and more preferably in the range of 5 to 20 nm. . If the primary particle diameter of the particles is less than 1 nm, secondary aggregation is likely to occur, and the cured film may be whitened. If it exceeds 100 nm, the surface uniformity during the formation of the thin film may be impaired. Here, the primary particle diameter can be measured with a transmission electron microscope. In general, since the particle diameter has a distribution, it can be represented by a median diameter in order to represent the particle diameter of the particles to be blended. A median diameter preferable as the component (B) is 5 to 40 nm, and more preferably 5 to 15 nm.
尚、酸化チタンは、光触媒活性が有るため、そのままでは光学用途に用いることは難しいため、粒子表面を酸化ケイ素で被覆されていてもよい。
また、酸化チタンには、結晶型の違いにより、アナターゼ型とルチル型が存在するが、屈折率が高く、耐光性に優れることからルチル型が好ましい。
In addition, since titanium oxide has photocatalytic activity, it is difficult to use it as it is for optical purposes. Therefore, the particle surface may be coated with silicon oxide.
Titanium oxide has an anatase type and a rutile type depending on the crystal type, but a rutile type is preferred because of its high refractive index and excellent light resistance.
成分(B)として用いる酸化物粒子は、粉体状であってもよいし、溶媒分散ゾルであってもよい。分散媒としては、例えば、メタノール、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、N−メチル−2−ピロリドン、プロピレングレコールモノメチルエーテル等が挙げられる。 The oxide particles used as the component (B) may be in the form of a powder or a solvent-dispersed sol. Examples of the dispersion medium include methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether and the like.
成分(B)として用いることができる粒子の市販品の例としては、例えば、酸化ケイ素被覆アナターゼ型酸化チタン(日揮触媒化成社製ELCOM JX−1021TIV、メジアン径10nm、粒子含量21重量%)、酸化ケイ素被覆−酸化スズ含有ルチル型酸化チタン(テイカ社製TS−103、メジアン径10nm、粒子含量20重量%)、
酸化ジルコニウム(日揮触媒化成社製ELCOM JX−1022ZRV、メジアン径12nm、粒子含量21重量%)等が挙げられる。
Examples of commercially available particles that can be used as the component (B) include, for example, silicon oxide-coated anatase-type titanium oxide (ELCOM JX-1021TIV manufactured by JGC Catalysts & Chemicals, median diameter 10 nm, particle content 21% by weight), oxidation Silicon coating-tin oxide containing rutile type titanium oxide (TS-103 manufactured by Teica, median diameter 10 nm, particle content 20% by weight),
Zirconium oxide (ELCOM JX-1022ZRV manufactured by JGC Catalysts & Chemicals Co., Ltd., median diameter 12 nm, particle content 21% by weight) and the like can be mentioned.
本発明の組成物中における成分(B)の配合量は、有機溶剤を除く成分全量を100重量%としたときに、通常10〜90重量%、好ましくは20〜80重量%、より好ましくは40〜60重量%の範囲内である。成分(B)の配合量が90重量%を超えると、十分な耐熱性が得られないおそれがあり、成分(B)の配合量が10重量%に満たないと本発明の組成物から得られるコート層の屈折率が低下し、光電変換素子の受発光効率が劣るおそれがある。
尚、成分(B)が溶媒分散ゾルである場合には、成分(B)の配合量には分散媒を含まない。
The amount of component (B) in the composition of the present invention is usually 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 40%, when the total amount of the components excluding the organic solvent is 100% by weight. Within the range of ˜60% by weight. If the amount of component (B) exceeds 90% by weight, sufficient heat resistance may not be obtained, and if the amount of component (B) is less than 10% by weight, the composition of the present invention can be obtained. The refractive index of a coat layer falls and there exists a possibility that the light emitting / receiving efficiency of a photoelectric conversion element may be inferior.
In addition, when a component (B) is a solvent dispersion | distribution sol, a dispersion medium is not included in the compounding quantity of a component (B).
(C)界面活性剤
本発明の組成物をスピンコートによって基材等に塗布する場合には、均一な塗膜が得られることから、界面活性剤を配合することが好ましい。
本発明で用いることができる界面活性剤の種類としては、シリコン系界面活性剤、フッ素系界面活性剤等が挙げられ、シリコン系界面活性剤が好ましい。
(C) Surfactant When the composition of the present invention is applied to a substrate or the like by spin coating, it is preferable to incorporate a surfactant because a uniform coating film is obtained.
Examples of the surfactant that can be used in the present invention include silicon-based surfactants and fluorine-based surfactants, and silicon-based surfactants are preferred.
シリコン系の界面活性剤の例としては、例えば、SH28PA(東レダウコーニング社製、ジメチルポリシロキサンポリオキシアルキレン共重合体)、ペインタッド19、54(東レダウコーニング社製、ジメチルポリシロキサンポリオキシアルキレン共重合体)、FM0411(サイラプレーン、チッソ社製)、SF8428(東レダウコーニング社製、ジメチルポリシロキサンポリオキシアルキレン共重合体(側鎖OH含有))、BYK UV3510(ビックケミー・ジャパン社製、ジメチルポリシロキサン−ポリオキシアルキレン共重合体)、DC57(東レ・ダウコーニング・シリコーン社製、ジメチルポリシロキサン−ポリオキシアルキレン共重合体)、DC190(東レ・ダウコーニング・シリコーン社製、ジメチルポリシロキサン−ポリオキシアルキレン共重合体)、サイラプレーンFM−4411、FM−4421、FM−4425、FM−7711、FM−7721、FM−7725、FM−0411、FM−0421、FM−0425、FM−DA11、FM−DA21、FM−DA26、FM0711、FM0721、FM−0725、TM−0701、TM−0701T(チッソ社製)、UV3500、UV3510、UV3530(ビックケミー・ジャパン社製)、BY16−004、SF8428(東レ・ダウコーニング・シリコーン社製)、VPS−1001(和光純薬製)等が挙げられる。特にサイラプレーンFM−7711、FM−7721、FM−7725、FM−0411、FM−0421、FM−0425、FM0711、FM0721、FM−0725、VPS−1001等を挙げることができる。また、エチレン性不飽和基を有する当該シリコーン化合物の市販品としては、例えば、Tego Rad 2300、2200N、テゴ・ケミー社等を挙げることができる。 Examples of silicon surfactants include, for example, SH28PA (Toray Dow Corning, dimethylpolysiloxane polyoxyalkylene copolymer), Paintad 19, 54 (Toray Dow Corning, dimethylpolysiloxane polyoxyalkylene copolymer). Polymer), FM0411 (silaplane, manufactured by Chisso), SF8428 (manufactured by Toray Dow Corning, dimethylpolysiloxane polyoxyalkylene copolymer (containing side chain OH)), BYK UV3510 (manufactured by BYK Chemie Japan, dimethylpoly Siloxane-polyoxyalkylene copolymer), DC57 (manufactured by Toray Dow Corning Silicone, dimethylpolysiloxane-polyoxyalkylene copolymer), DC190 (manufactured by Toray Dow Corning Silicone, dimethylpolysiloxane) Sun-polyoxyalkylene copolymer), Silaplane FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM- DA11, FM-DA21, FM-DA26, FM0711, FM0721, FM-0725, TM-0701, TM-0701T (manufactured by Chisso), UV3500, UV3510, UV3530 (manufactured by Big Chemie Japan), BY16-004, SF8428 ( Toray Dow Corning Silicone Co., Ltd.), VPS-1001 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like. In particular, Silaplane FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM0711, FM0721, FM-0725, VPS-1001, etc. can be mentioned. Moreover, as a commercial item of the said silicone compound which has an ethylenically unsaturated group, Tego Rad 2300, 2200N, Tego Chemie, etc. can be mentioned, for example.
フッ素系の界面活性剤の例として、例えば、メガファックF−114、F410、F411、F450、F493、F494、F443、F444、F445、F446、F470、F471、F472SF、F474、F475、R30、F477、F478、F479、F480SF、F482、F483、F484、F486、F487、F172D、F178K、F178RM、ESM−1、MCF350SF、BL20、R08、R61、R90(DIC社製)が挙げられる。 Examples of the fluorosurfactant include, for example, Megafac F-114, F410, F411, F450, F493, F494, F443, F444, F445, F446, F470, F471, F472SF, F474, F475, R30, F477, F478, F479, F480SF, F482, F483, F484, F486, F487, F172D, F178K, F178RM, ESM-1, MCF350SF, BL20, R08, R61, R90 (manufactured by DIC) can be mentioned.
本発明の組成物中における成分(C)の配合量は、有機溶剤を除く成分全量を100重量%としたときに、通常0〜10重量%、好ましくは0.1〜5重量%、より好ましくは0.5〜3重量%の範囲内である。成分(C)の配合量が10重量%を超えると、屈折率が低下するおそれがある。 The amount of component (C) in the composition of the present invention is usually 0 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 100% by weight based on the total amount of components excluding organic solvents. Is in the range of 0.5 to 3% by weight. If the amount of component (C) exceeds 10% by weight, the refractive index may be lowered.
(D)イミド化触媒
本発明の組成物は、加熱によって成分(A)のポリアミック酸がイミド化重合体となることにより硬化するものであるが、この熱硬化反応を促進するためにイミド化触媒を添加することもできる。
(D) Imidization catalyst The composition of the present invention cures when the polyamic acid of component (A) becomes an imidized polymer by heating, but the imidization catalyst is used to promote this thermosetting reaction. Can also be added.
イミド化触媒としては、例えば、無水酢酸−ピリジン混合溶液等が挙げられる。また、無水酢酸−トリエチルアミン混合溶液や、無水トリフルオロ酢酸、ジシクロヘキシルカルボジイミドも使用できる。 As an imidation catalyst, an acetic anhydride-pyridine mixed solution etc. are mentioned, for example. Moreover, an acetic anhydride-triethylamine mixed solution, trifluoroacetic anhydride, and dicyclohexylcarbodiimide can also be used.
また、成分(D)として、光の照射によって酸又は塩基を発生させる化合物である光酸発生剤又は光塩基発生剤を用いることにより、本発明の組成物をパターニング可能な材料とすることができる。これにより、不要な部分に塗布された組成物を容易に除去することができ、光電変換素子の設計がより容易になる。
光塩基発生剤としては、例えば、カルバマート型光塩基発生剤等が挙げられる。具体的には、下記のような構造式で示される化合物が光塩基発生剤の例として挙げられる。
Examples of the photobase generator include carbamate type photobase generators. Specifically, examples of the photobase generator include compounds represented by the following structural formula.
本発明の組成物中における成分(D)の配合量は、有機溶剤を除く成分全量を100重量%としたときに、通常0〜20重量%、好ましくは1〜10重量%、より好ましくは1〜5重量%の範囲内である。成分(D)の配合量が20重量%を超えると、貯蔵安定性が低下するおそれがある。 The amount of component (D) in the composition of the present invention is usually 0 to 20% by weight, preferably 1 to 10% by weight, more preferably 1 when the total amount of the components excluding the organic solvent is 100% by weight. Within the range of -5% by weight. If the blending amount of component (D) exceeds 20% by weight, storage stability may be lowered.
(E)有機溶剤
本発明の組成物は、通常、成分(A)のポリアミック酸製造の際に用いる溶剤を含有する。また、成分(B)の酸化物粒子として粒子の溶媒分散ゾルを用いる場合には、その分散媒も本発明の組成物中に含有される。その他、組成物の粘度を調整し、均一な塗膜を形成するための組成物の塗布性を改善するために、別途、有機溶剤を添加することができる。
(E) Organic solvent The composition of this invention normally contains the solvent used in the case of manufacture of the polyamic acid of a component (A). When a solvent dispersion sol of particles is used as the oxide particles of component (B), the dispersion medium is also contained in the composition of the present invention. In addition, in order to adjust the viscosity of the composition and improve the coating property of the composition for forming a uniform coating film, an organic solvent can be added separately.
本発明で用いる有機溶剤としては、特に制限されないが、非プロトン系有機溶剤が好ましい。非プロトン系有機溶剤としては、例えば、N−メチル−2−ピロリドン(NMP)、ジメチルホルムアミド(DMF)、シクロヘキサノン、N,N−ジメチルアセトアミド(DMAc)等が好ましい。これら以外にもN,N−ジメチルホルムアミド、N、N−ジエチルアセトアミド、N,N−ジメトキシアセトアミド、1,3−ジメチル−2−イミダゾリジノン、N−メチルカプロラクタム、1,2−ジメトキシエタン、1,2−ジメトキシエタン、ビス(2−メトキシエチル)エーテル、1,2−ビス(2−メトキシエトキシ)エタン、ビス〔2−(2−メトキシエトキシ)エチル〕エーテル、テトラヒドロフラン、1,3−ジオキサン、1,4−ジオキサン、ピロリン、ピコリン、ジメチルスルホキシド、ジメチルスルホン、テトラメチル尿素、ヘキサメチルホスホルアミド、フェノール、o−クレゾール、m−クレゾール、p−クレゾール、m−クレゾール酸、p−クロロフェノール、アニソール、ベンゼン、トルエン、キシレン等を挙げることができる。これらの有機溶剤は単独で、又は2種類以上の混合物として用いられる。 The organic solvent used in the present invention is not particularly limited, but an aprotic organic solvent is preferable. As the aprotic organic solvent, for example, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), cyclohexanone, N, N-dimethylacetamide (DMAc) and the like are preferable. Besides these, N, N-dimethylformamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, 1 , 2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyrroline, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresolic acid, p-chlorophenol, Anisole, benzene, toluene, xylene, etc. It can gel. These organic solvents are used alone or as a mixture of two or more.
本発明の組成物中における成分(E)有機溶剤の配合量は、有機溶剤を除く成分全量100重量部に対して、通常100〜9900重量部、好ましくは300〜1900重量部、より好ましくは400〜1900重量部の範囲内である。有機溶剤の配合量が100重量部未満では、スピンコート塗布ができなくなるおそれがあり、9900重量部を超えると、必要膜厚が発現できないおそれがある。
尚、成分(E)の配合量には、成分(A)のポリアミック酸溶液に由来する溶剤及び成分(B)の酸化物粒子分散ゾルの分散媒として持ち込まれる溶剤を含む。
The compounding amount of the component (E) organic solvent in the composition of the present invention is usually 100 to 9900 parts by weight, preferably 300 to 1900 parts by weight, more preferably 400 parts per 100 parts by weight of the total component excluding the organic solvent. Within the range of ˜1900 parts by weight. If the blending amount of the organic solvent is less than 100 parts by weight, spin coating may not be possible, and if it exceeds 9900 parts by weight, the required film thickness may not be exhibited.
In addition, the compounding quantity of a component (E) contains the solvent brought in as a dispersion medium of the solvent derived from the polyamic acid solution of a component (A), and the oxide particle dispersion | distribution sol of a component (B).
(F)添加剤
本発明の組成物には、本発明の効果を損なわない範囲内で、各種の添加剤を配合することができる。このような添加剤としては、例えば、上記成分以外の硬化性化合物、酸化防止剤等が挙げられる。
(F) Additives Various additives can be blended in the composition of the present invention within a range not impairing the effects of the present invention. Examples of such additives include curable compounds other than the above components, and antioxidants.
硬化性化合物には、熱硬化性化合物及び光硬化性化合物を含む。これらの化合物を配合することにより、得られる硬化物の硬度を高めることができる。
熱硬化性化合物としては、例えば、メラミン化合物、アルコキシシラン等が挙げられる。
光硬化性化合物としては、例えば、(メタ)アクリロイル基を有する化合物、ビニル基を有する化合物等が挙げられる。
The curable compound includes a thermosetting compound and a photocurable compound. By blending these compounds, the hardness of the resulting cured product can be increased.
Examples of the thermosetting compound include melamine compounds and alkoxysilanes.
Examples of the photocurable compound include a compound having a (meth) acryloyl group, a compound having a vinyl group, and the like.
[コート層]
前述のとおり、本発明の組成物を光半導体素子にコートすることで、受発光効率が高くなる。これは、空気の屈折率が1であり、高屈折率な層が光半導体素子と空気の間に介在することで、広範囲に広がろうとする光を集光するためである。また、本発明の光電変換素子はコート層を形成した後に、さらに封止することもできる。封止材として一般にエポキシ樹脂等の有機樹脂が使用されるが、これらの有機樹脂は1.5〜1.6程度の屈折率を有しているため、受発光効率を高めるために、コート層の屈折率は1.7以上、好ましくは1.75以上、より好ましくは、1.8以上であることが要求される。屈折率は高い方が好ましいが、上限は使用する材料から自ずと制限される。即ち、本発明の組成物に使用される材料で最も高屈折率であるのは屈折率2.4の酸化チタンであるため、コート層の屈折率の上限も2.4となる。
[Coat layer]
As described above, the light receiving and emitting efficiency is increased by coating the optical semiconductor element with the composition of the present invention. This is because the refractive index of air is 1, and a high refractive index layer is interposed between the optical semiconductor element and air, thereby condensing light that is to spread over a wide range. Moreover, after forming the coat layer, the photoelectric conversion element of the present invention can be further sealed. Generally, an organic resin such as an epoxy resin is used as the sealing material. Since these organic resins have a refractive index of about 1.5 to 1.6, a coating layer is used to increase the light receiving and emitting efficiency. The refractive index is required to be 1.7 or more, preferably 1.75 or more, more preferably 1.8 or more. A higher refractive index is preferred, but the upper limit is naturally limited by the material used. That is, the highest refractive index of the material used in the composition of the present invention is titanium oxide having a refractive index of 2.4, so the upper limit of the refractive index of the coat layer is also 2.4.
コート層の膜厚は特に限定されないが、素子の種類により、例えば50nm〜100μmの範囲から適宜選択することができる。 The film thickness of the coat layer is not particularly limited, but can be appropriately selected from the range of, for example, 50 nm to 100 μm depending on the type of element.
[光電変換素子およびその製造方法]
本発明の光電変換素子に用いられる光半導体素子は特に制限されず、たとえば発光ダイオード、半導体レーザー、フォトダイオード、フォトトランジスタ、エレクトロルミネセンス素子、CCD、C−MOS、太陽電池等が挙げられる。
[Photoelectric conversion element and manufacturing method thereof]
The optical semiconductor element used in the photoelectric conversion element of the present invention is not particularly limited, and examples thereof include a light emitting diode, a semiconductor laser, a photodiode, a phototransistor, an electroluminescence element, a CCD, a C-MOS, and a solar cell.
本発明の光電変換素子はその使用用途に合わせ、硫黄を含有するポリアミック酸およびそのイミド化重合体の少なくとも一方である成分(A)、酸化チタン又は酸化ジルコニウムを主成分とする粒子である成分(B)、必要に応じて任意成分を混合して組成物を調製し、光半導体素子に該組成物をコートして硬化し、必要に応じて封止材で封止することによって製造することができる。 The photoelectric conversion element of the present invention is a component (A) that is at least one of a polyamic acid containing sulfur and an imidized polymer thereof, and a component that is a particle containing titanium oxide or zirconium oxide as a main component (in accordance with the intended use) B) A composition can be prepared by mixing arbitrary components as necessary, and can be produced by coating an optical semiconductor element with the composition, curing, and sealing with a sealing material as necessary. it can.
本発明の組成物をコートする方法としては、特に限定されないが、スピンコート、ディップコート、ポッティング、インクジェット等の方法を、製造する光電変換素子の形状等を考慮して選択することができる。 A method for coating the composition of the present invention is not particularly limited, and a method such as spin coating, dip coating, potting, and inkjet can be selected in consideration of the shape of the photoelectric conversion element to be manufactured.
本発明において使用される光半導体素子が発光ダイオードの場合は、例えば、GaAs、GaAlAs、GaP、GaAsP、ZnSe、ZnS、GaN等の化合物半導体を用いたものを挙げることができる。また、発光ダイオードの発光色についても特に制限はなく、赤、緑、青、黄、橙、黄緑、白などである。 When the optical semiconductor element used in the present invention is a light emitting diode, for example, a semiconductor using a compound semiconductor such as GaAs, GaAlAs, GaP, GaAsP, ZnSe, ZnS, or GaN can be used. Further, the emission color of the light emitting diode is not particularly limited, and examples thereof include red, green, blue, yellow, orange, yellow green, and white.
以下、本発明を実施例によってさらに具体的に説明するが、本発明はこれらの実施例によって何ら制限されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
合成例1
4,4’−(p−フェニレンジスルファニル)ジアニリン
4,4 '-(p-phenylenedisulfanyl) dianiline
収量:24.6g
収率:75.8%
融点:164.9℃(DSC)
FT−IR(KBr、cm−1):3417.2、3316.9、1627.6、1589.0、1496.5、1288.2、1172.5、1095.4、825.4
1H−NMR(300MHz、DMSO−d6、ppm):5.39(s、4H)、6.60−6.63(d、4H)、6.96−6.97(d、4H)、7.13−7.16(d、4H)
13C−NMR(300MHz、DMSO−d6、ppm):150.6、137.6、136.7、128.4、116.5、115.8
元素分析:計算値 C18H16N2S2:C、66.63%;H、4.97%;N、8.63%
測定値 C、66.42%;H、5.11%;N、8.47%
Yield: 24.6g
Yield: 75.8%
Melting point: 164.9 ° C. (DSC)
FT-IR (KBr, cm −1 ): 3417.2, 3316.9, 1627.6, 1589.0, 1496.5, 1288.2, 1172.5, 1095.4, 825.4
1 H-NMR (300 MHz, DMSO-d 6 , ppm): 5.39 (s, 4H), 6.60-6.63 (d, 4H), 6.96-6.97 (d, 4H), 7.13-7.16 (d, 4H)
13 C-NMR (300MHz, DMSO -d 6, ppm): 150.6,137.6,136.7,128.4,116.5,115.8
Calcd C 18 H 16 N 2 S 2 : C, 66.63%; H, 4.97%; N, 8.63%
Measurement C, 66.42%; H, 5.11%; N, 8.47%
合成例2
1,3−ビス(4−アミノフェニルスルファニル)ベンゼン
1,3-bis (4-aminophenylsulfanyl) benzene
収量:17.7g
収率:68.2%
融点:110.0℃(DSC)
FT−IR(KBr、cm−1):3424.9、3340.1、1619.9、1565.9、1496.5、1465.6、1288.2、1172.5、1118.5、825.4
1H−NMR(300MHz、DMSO−d6、ppm):5.44(s、4H)、6.60−6.63(m、5H)、6.72−6.75(m、2H)、7.09−7.12(m、5H)
元素分析:計算値 C18H16N2S2:C、66.63%;H、4.97%;N、8.63%
測定値 C、66.44%;H、5.08%;N、8.52%
Yield: 17.7g
Yield: 68.2%
Melting point: 110.0 ° C. (DSC)
FT-IR (KBr, cm −1 ): 3424.9, 3340.1, 1619.9, 1565.9, 1496.5, 1465.6, 1288.2, 1172.5, 118.5, 825.4
1 H-NMR (300MHz, DMSO -d 6, ppm): 5.44 (s, 4H), 6.60-6.63 (m, 5H), 6.72-6.75 (m, 2H), 7.09-7.12 (m, 5H)
Calcd C 18 H 16 N 2 S 2 : C, 66.63%; H, 4.97%; N, 8.63%
Measurement C, 66.44%; H, 5.08%; N, 8.52%
合成例3
1,3−ビス(4−アミノフェノールスルファニル)5−シアノベンゼン
1,3-bis (4-aminophenolsulfanyl) 5-cyanobenzene
収量:20.2g
収率:72.1%
融点:184.5℃(DSC)
FT−IR(KBr、cm−1):3432.7,3347.8,2229.3,1627.6,1596.8,1550.5,1496.5,1411.6,1288.2,1172.5,825.4,671.1
1H−NMR(300MHz、DMSO−d6、ppm):5.56(s、4H)、6.63−6.66(d、4H)、6.77−6.78(s、1H)、7.05−7.13(m、6H)
元素分析:計算値 C19H15N3S2:C、65.30%;H、4.33%;N、12.02%
測定値 C、65.14%;H、4.67%;N、11.86%
Yield: 20.2g
Yield: 72.1%
Melting point: 184.5 ° C (DSC)
FT-IR (KBr, cm −1 ): 3432.7, 3347.8, 2229.3, 1627.6, 1596.8, 1550.5, 1496.5, 1411.6, 1288.2, 1172.5 , 825.4, 671.1
1 H-NMR (300 MHz, DMSO-d 6 , ppm): 5.56 (s, 4H), 6.63-6.66 (d, 4H), 6.77-6.78 (s, 1H), 7.05-7.13 (m, 6H)
Calcd C 19 H 15 N 3 S 2 : C, 65.30%; H, 4.33%; N, 12.02%
Measurement C, 65.14%; H, 4.67%; N, 11.86%
合成例4
4,4’−ビス(4−ニトロフェニルスルファニル)ジフェニルスルフィド
4,4'-bis (4-nitrophenylsulfanyl) diphenyl sulfide
収量:16.9g
収率:86.1%
融点:137〜138℃(DSC)
FT−IR(KBr、cm−1):1581.3、1511.9、1342.2、1079.9、1010.5、848.5、740.5
1H−NMR(300MHz、DMSO−d6、ppm):7.38−7.40(d、4H)、7.49−7.51(d、4H)、7.57−7.59(d、4H)、8.15−8.17(d、4H)
元素分析:計算値 C24H16N2O4S3:C、58.52%;H、3.27%;N、5.69%
測定値 C、58.96%;H、3.60%;N、5.67%
Yield: 16.9g
Yield: 86.1%
Melting point: 137-138 ° C (DSC)
FT-IR (KBr, cm −1 ): 1581.3, 1511.9, 1342.2, 1079.9, 1010.5, 848.5, 740.5
1 H-NMR (300MHz, DMSO -d 6, ppm): 7.38-7.40 (d, 4H), 7.49-7.51 (d, 4H), 7.57-7.59 (d 4H), 8.15-8.17 (d, 4H)
Calcd C 24 H 16 N 2 O 4 S 3: C, 58.52%; H, 3.27%; N, 5.69%
Measurement C, 58.96%; H, 3.60%; N, 5.67%
合成例5
4,4’−チオビス[(p−フェニレンスルファニル)アニリン]
4,4′-thiobis [(p-phenylenesulfanyl) aniline]
収量:10.2g
収率:84.0%
融点:142〜143℃(DSC)
FT−IR(KBr、cm−1):3428.8、3382.5、1619.9、1592.9、1496.5、1473.3、1292.0、1176.4、1099.2、1010.5、825.4
1H−NMR(300MHz、DMSO−d6、ppm):5.46(s、4H)、6.62−6.64(d、4H)、6.98−7.01(d、4H)、7.15−7.19(m、8H)
元素分析:計算値 C24H20N2S3:C、66.63%;H、4.66%;N、6.48%
測定値 C、66.59%;H、4.77%;N、6.34%
Yield: 10.2 g
Yield: 84.0%
Melting point: 142-143 ° C. (DSC)
FT-IR (KBr, cm −1 ): 3428.8, 3382.5, 1619.9, 1592.9, 1496.5, 1473.3, 1292.0, 1176.4, 1099.2, 1010.5 , 825.4
1 H-NMR (300 MHz, DMSO-d 6 , ppm): 5.46 (s, 4H), 6.62-6.64 (d, 4H), 6.98-7.01 (d, 4H), 7.15-7.19 (m, 8H)
Calcd C 24 H 20 N 2 S 3 : C, 66.63%; H, 4.66%; N, 6.48%
Measurement C, 66.59%; H, 4.77%; N, 6.34%
合成例6
4,4’−ビス(4−アミノフェニルスルファニル)−p−ジチオフェノキシベンゼン
収量:50.86g
収率:70.0%
Synthesis Example 6
4,4′-bis (4-aminophenylsulfanyl) -p-dithiophenoxybenzene
Yield: 50.86g
Yield: 70.0%
得られた黄色の固体(36.33g、0.10mol)にp−アミノチオフェノール(25.03g、0.2mol)無水炭酸カリウム(12.72g、0.092mol)、そしてN,N−ジメチルホルムアミド(DMF)(100mL)を加え、130〜140℃で5〜24時間反応させた。析出した黄色の固体を濾取し水洗した。得られた黄色の個体はエタノールを用いて再結晶し精製した。
収量:44.34g
収率:82.0%
The resulting yellow solid (36.33 g, 0.10 mol) was added to p-aminothiophenol (25.03 g, 0.2 mol) anhydrous potassium carbonate (12.72 g, 0.092 mol), and N, N-dimethylformamide. (DMF) (100 mL) was added and reacted at 130-140 ° C. for 5-24 hours. The precipitated yellow solid was collected by filtration and washed with water. The obtained yellow solid was recrystallized and purified using ethanol.
Yield: 44.34g
Yield: 82.0%
合成例7
4,4’−[p−チオビス(フェニレン−スルファニル)]ジフタル酸無水物
4,4 ′-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride
収量:7.8g
収率:71.9%
融点:175.2℃(DSC)
FT−IR(KBr、cm−1):1847.5、1778.0、1604.4、1473.3、1326.8、1257.4、902.5、817.7、732.0
1H−NMR(300MHz、DMSO−d6、ppm):7.45−7.49(d、4H)、7.52−7.55(d、4H)、7.56(s、2H)、7.60−7.63(d、2H)、7.83−7.85(d、2H)
元素分析:計算値 C28H14O6S3:C、61.98%;H、2.60%
測定値 C、62.23%;H、2.97%
Yield: 7.8g
Yield: 71.9%
Melting point: 175.2 ° C (DSC)
FT-IR (KBr, cm < -1 >): 1847.5, 1778.0, 1604.4, 1473.3, 1326.8, 1257.4, 902.5, 817.7, 732.0
1 H-NMR (300 MHz, DMSO-d 6 , ppm): 7.45-7.49 (d, 4H), 7.52 to 7.55 (d, 4H), 7.56 (s, 2H), 7.60-7.63 (d, 2H), 7.83-7.85 (d, 2H)
Calcd C 28 H 14 O 6 S 3 : C, 61.98%; H, 2.60%
Measured value C, 62.23%; H, 2.97%
製造例1
窒素導入管を備えた反応容器に、4,4’−チオジアニリン(40mmol)(以下、SDAという)にN,N−ジメチルアセトアミド(25g)(以下、DMAcという)を加え、室温で攪拌し完全に溶解させた。次に、1,2,3,4−シクロブタンテトラカルボン酸二無水物(40mmol)(以下、CBDAという)とDMAc(15g)を添加し、40℃で4.5時間攪拌した。次に反応液にDMAc(93g)を加えて希釈し、ピリジン(40mmol)と無水酢酸(40mmol)を添加後、110℃で5時間反応させた。エバポレーターを使用してDMAcからγ―ブチロラクトン(以下、GBLという)に溶剤置換し、ポリアミック酸のGBL溶液を得た。
Production Example 1
To a reaction vessel equipped with a nitrogen introduction tube, 4,4′-thiodianiline (40 mmol) (hereinafter referred to as SDA) is added N, N-dimethylacetamide (25 g) (hereinafter referred to as DMAc), and the mixture is stirred completely at room temperature. Dissolved. Next, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (40 mmol) (hereinafter referred to as CBDA) and DMAc (15 g) were added and stirred at 40 ° C. for 4.5 hours. Next, DMAc (93 g) was added to the reaction solution for dilution, and pyridine (40 mmol) and acetic anhydride (40 mmol) were added, followed by reaction at 110 ° C. for 5 hours. Using an evaporator, the solvent was substituted from DMAc to γ-butyrolactone (hereinafter referred to as GBL) to obtain a GBL solution of polyamic acid.
製造例2〜5
実施例1で用いたCHDAの代わりに、表に示す酸無水物を用いた他は、製造例1と同様の方法で重合を行い、ポリアミック酸のGBL溶液を得た。
Production Examples 2-5
Polymerization was performed in the same manner as in Production Example 1 except that the acid anhydrides shown in the table were used instead of CHDA used in Example 1, to obtain a GBL solution of polyamic acid.
製造例7〜9
製造例1で用いたCHDAの代わりに表に示す酸無水物を、SDAの代わりに表に示すジアミンを用いた他は、製造例1と同様の方法で重合を行い、ポリアミック酸のGBL溶液を得た。
Production Examples 7-9
Polymerization was carried out in the same manner as in Production Example 1, except that the acid anhydrides shown in the table were used instead of CHDA used in Production Example 1 and the diamines shown in the table were used instead of SDA, and a GBL solution of polyamic acid was added. Obtained.
比較製造例1
製造例1で用いたSDAの代わりにODAを用いた他は、製造例1と同様の方法で重合を行い、ポリアミック酸のGBL溶液を得た。
Comparative production example 1
Polymerization was carried out in the same manner as in Production Example 1 except that ODA was used instead of SDA used in Production Example 1 to obtain a GBL solution of polyamic acid.
製造例10
窒素導入管を備えた反応容器に、製造例1で得られたポリアミック酸のGBL溶液(ポリアミック酸含有量25重量%)26.2gに、GBL(4.2g)とプロピレングレコールモノメチルエーテル(2.3g)とジメチルポリシロキサンポリオキシアルキレン共重合体のプロピレングレコールモノメチルエーテル溶液(東レダウコーニング社製界面活性剤SH28PA、固形分濃度3重量%)0.7gを加え溶解させた。次に酸化ケイ素被覆ルチル型酸化チタンのプロピレングレコールモノメチルエーテル(テイカ社製TS−103、粒子含量20重量%)66.6gを滴下した。その後、室温で1時間攪拌し組成物10を得た。
Production Example 10
In a reaction vessel equipped with a nitrogen inlet tube, 26.2 g of the polyamic acid GBL solution (polyamic acid content 25 wt%) obtained in Production Example 1 was added to GBL (4.2 g) and propylene glycol monomethyl ether (2 .3 g) and a propylene glycol monomethyl ether solution of dimethylpolysiloxane polyoxyalkylene copolymer (surfactant SH28PA manufactured by Toray Dow Corning Co., Ltd., solid content concentration 3 wt%) 0.7 g was added and dissolved. Next, 66.6 g of propylene glycol monomethyl ether of silicon oxide-coated rutile type titanium oxide (TS-103 manufactured by Teika Co., Ltd., particle content 20% by weight) was added dropwise. Then, it stirred at room temperature for 1 hour and obtained the composition 10.
製造例11〜17、20〜21
製造例10で用いたポリアミック酸のGBL溶液の代わりに、表に示すポリアミック酸のGBL溶液を用いた他は、製造例10と同様の方法で調製を行い、各組成物を得た。
Production Examples 11-17, 20-21
Each composition was obtained in the same manner as in Production Example 10, except that the GBL solution of polyamic acid shown in the table was used instead of the GBL solution of polyamic acid used in Production Example 10.
製造例18
製造例10で用いた酸化ケイ素被覆ルチル型酸化チタンのプロピレングレコールモノメチルエーテルゾル代わりに、表に示す酸化ケイ素被覆アナターゼ型チタンのプロピレングレコールモノメチルエーテルゾル(日揮触媒化成社製ELCOM JX−1021TIV、粒子含量21%)を用いた他は、製造例10と同様の方法で調製を行い、各組成物を得た。
Production Example 18
Instead of the propylene glycol monomethyl ether sol of silicon oxide-coated rutile titanium oxide used in Production Example 10, the propylene glycol monomethyl ether sol of silicon oxide-coated anatase titanium shown in the table (ELCOM JX-1021TIV manufactured by JGC Catalysts & Chemicals, Inc., Each composition was obtained in the same manner as in Production Example 10 except that the particle content was 21%.
製造例19
製造例10で用いた酸化ケイ素被覆ルチル型酸化チタンのプロピレングレコールモノメチルエーテルゾル代わりに、表に示すジルコニアのプロピレングレコールモノメチルエーテル(日揮触媒化成社製ELCOM JX−1022ZRV、粒子含量21%)を用いた他は、製造例10と同様の方法で調製を行い、各組成物を得た。
Production Example 19
Instead of the propylene glycol monomethyl ether sol of silicon oxide-coated rutile type titanium oxide used in Production Example 10, zirconia propylene glycol monomethyl ether (ELCOM JX-1022ZRV manufactured by JGC Catalysts & Chemicals, particle content 21%) shown in the table was used. Other than using, preparation was carried out in the same manner as in Production Example 10 to obtain each composition.
比較製造例2
製造例10で用いたポリアミック酸のGBL溶液の代わりに、表に示すポリアミック酸のGBL溶液を用いた他は、製造例10と同様の方法で調製を行い、各組成物を得た。
Comparative production example 2
Each composition was obtained in the same manner as in Production Example 10, except that the GBL solution of polyamic acid shown in the table was used instead of the GBL solution of polyamic acid used in Production Example 10.
<硬化膜の作製>
4インチ径の溶融石英基板もしくはシリコンウエハ上に、実施例10〜21及び比較例2で調製した組成物をディスペンスし、厚さ約1μmになるようにスピンコート塗布し、120℃×5分及び250℃×5分加熱して硬化膜を作製した。
<Production of cured film>
The composition prepared in Examples 10 to 21 and Comparative Example 2 was dispensed onto a 4 inch diameter fused quartz substrate or silicon wafer, and spin coated to a thickness of about 1 μm, and 120 ° C. × 5 minutes. A cured film was prepared by heating at 250 ° C. for 5 minutes.
<硬化膜の特性評価>
上記のようにして作製した硬化膜について、下記特性を測定、評価した。結果を表に示す。
<Characteristic evaluation of cured film>
The cured film produced as described above was measured and evaluated for the following characteristics. The results are shown in the table.
(1)屈折率
Metricon社のPC−2000型プリズムカプラーを使用して、25℃における波長633nmの光の屈折率を測定した。
(1) Refractive Index Using a Metricon PC-2000 prism coupler, the refractive index of light having a wavelength of 633 nm at 25 ° C. was measured.
(2)透過率
日本分光社製の自記分光光度計を使用して、上記で得られた硬化膜(膜厚1μm)の波長400nmにおける透過率(%)をそれぞれ測定した。
(2) Transmittance Using a self-recording spectrophotometer manufactured by JASCO Corporation, the transmittance (%) at a wavelength of 400 nm of the cured film (film thickness 1 μm) obtained above was measured.
(3)光電変換素子発光効率の向上率
AlGaInP系赤色発光素子(発光波長:555nm)を、表に記載の各組成物に浸し引き上げた後、80℃、120℃、175℃及び190℃の各温度のオーブンでそれぞれ30分間加熱してコート層を形成した。その後、エポキシ樹脂(ナガセケムテックス製EX−314とダイセルサイテック製EB3700を2:1で混合した液にトリメリット酸を1%添加)を注入した型にコート層を形成した発光ダイオードを浸し、型ごと100℃のオーブンに移して3時間加熱し、その後120℃で5時間アフターキュアを行い、測定用の発光ダイオードを得た。また、発光効率の基準として上記コート層を設けていない発光ダイオードを作成した。発光ダイオードから20cmの距離に輝度計を設置し、コート層を設けていない発光ダイオードとの輝度を比較し、発光効率の向上率とした。なお、発光のための電圧は2.0Vとした。
(3) Increasing rate of photoelectric conversion element luminous efficiency An AlGaInP-based red light emitting element (emission wavelength: 555 nm) was immersed in each composition described in the table and pulled up, and then each of 80 ° C., 120 ° C., 175 ° C. and 190 ° C. Each was heated for 30 minutes in a temperature oven to form a coat layer. Thereafter, a light emitting diode having a coating layer is immersed in a mold in which epoxy resin (extracted by 2% trimellitic acid in a mixture of Nagase ChemteX EX-314 and Daicel Cytec EB3700 at a ratio of 2: 1) is immersed in the mold. Each was transferred to an oven at 100 ° C. and heated for 3 hours, and then after-cured at 120 ° C. for 5 hours to obtain a light emitting diode for measurement. Moreover, the light emitting diode which did not provide the said coating layer as a reference | standard of luminous efficiency was created. A luminance meter was installed at a distance of 20 cm from the light-emitting diode, and the luminance was compared with that of the light-emitting diode not provided with a coating layer, and the luminous efficiency was improved. The voltage for light emission was 2.0V.
表1中の略号は下記のものを表す。
(ジアミン類)
SDA:4,4’−チオジアニリン
2SPDA:4,4’−(p−フェニレンジスルファニル)ジアニリン;合成例1
3SDA:4,4’−チオビス[(p−フェニレンスルファニル)アニリン];合成例5
4SDA:4,4’−ビス(4−アミノフェニルスルファニル)−p−ジチオフェノキシベンゼン;合成例6
m2SDA:1,3−ビス(4−アミノフェニルスルファニル)ベンゼン;合成例2
CySDA:1,3−ビス(4−アミノフェノールスルファニル)5−シアノベンゼン;合成例3
ODA:ビス(p−アミノフェニル)エーテル
(酸無水物類)
3SDEA:4,4’−[p−チオビス(フェニレン−スルファニル)]ジフタル酸無水物;合成例7
CBDA:1,2,3,4−シクロブタンテトラカルボン酸二無水物
CHDA:1,2,4,5−シクロヘキサンテトラカルボン酸二無水物
MBDA:ブタンテトラカルボン酸二無水物
ODPA:4,4’−オキシジフタル酸二無水物
TCA:4,10−ジオキサトリシクロ[6.3.1.02,7]ドデカン−3,5,9,11−テトラオン
(粒子類)
酸化ケイ素被覆アナターゼ型酸化チタン:日揮触媒化成社製ELCOM JX−1021TIV、メジアン径10nm、粒子含量21重量%
酸化ケイ素被覆−酸化スズ含有ルチル型酸化チタン:テイカ社製TS−103、メジアン径10nm、粒子含量20重量%
酸化ジルコニウム:日揮触媒化成社製ELCOM JX−1022ZRV、メジアン径12nm、粒子含量21重量%
SH28PA:東レダウコーニング社製界面活性剤、ジメチルポリシロキサンポリオキシアルキレン共重合体
Abbreviations in Table 1 represent the following.
(Diamines)
SDA: 4,4′-thiodianiline 2SPDA: 4,4 ′-(p-phenylenedisulfanyl) dianiline; Synthesis Example 1
3SDA: 4,4′-thiobis [(p-phenylenesulfanyl) aniline]; Synthesis Example 5
4SDA: 4,4′-bis (4-aminophenylsulfanyl) -p-dithiophenoxybenzene; Synthesis Example 6
m2SDA: 1,3-bis (4-aminophenylsulfanyl) benzene; Synthesis Example 2
CySDA: 1,3-bis (4-aminophenolsulfanyl) 5-cyanobenzene; Synthesis Example 3
ODA: bis (p-aminophenyl) ether (acid anhydrides)
3SDEA: 4,4 ′-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride; Synthesis Example 7
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride CHDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride MBDA: butanetetracarboxylic dianhydride ODPA: 4,4′- Oxydiphthalic dianhydride TCA: 4,10-dioxatricyclo [6.3.1.0 2,7 ] dodecane-3,5,9,11-tetraone (particles)
Silicon oxide-coated anatase-type titanium oxide: ELCOM JX-1021TIV manufactured by JGC Catalysts & Chemicals, median diameter of 10 nm, particle content of 21% by weight
Silicon oxide coating-tin oxide-containing rutile titanium oxide: TS-103 manufactured by Teika, median diameter 10 nm, particle content 20% by weight
Zirconium oxide: ELCOM JX-1022ZRV manufactured by JGC Catalysts & Chemicals, median diameter 12 nm, particle content 21% by weight
SH28PA: Toray Dow Corning surfactant, dimethylpolysiloxane polyoxyalkylene copolymer
表の結果から、本発明の組成物から得られる硬化膜は波長633nmにおける屈折率が1.77〜1.90と非常に高く、波長400nmにおける透過率が非常に高く、耐熱性にも優れていることがわかる。
さらに、実施例の組成物から得られる硬化膜を光半導体素子上に形成し、発光効率を測定したところ、硬化膜のない場合と比較して顕著な発光効率の向上が確認された。
From the results in the table, the cured film obtained from the composition of the present invention has a very high refractive index of 1.77 to 1.90 at a wavelength of 633 nm, a very high transmittance at a wavelength of 400 nm, and excellent heat resistance. I understand that.
Furthermore, when the cured film obtained from the composition of an Example was formed on the optical semiconductor element and the luminous efficiency was measured, the remarkable improvement in luminous efficiency was confirmed compared with the case without a cured film.
本発明の光電変換素子は、発光素子としては高輝度が必要な光源として、また、受光素子としては高感度なイメージセンサーとして有用である。また、本発明の組成物は、光半導体素子用コート材として有用である。 The photoelectric conversion element of the present invention is useful as a light source that requires high luminance as a light emitting element and as a highly sensitive image sensor as a light receiving element. The composition of the present invention is useful as a coating material for optical semiconductor elements.
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