JP2021161380A - Coating liquid for forming conductive film - Google Patents
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- 239000007788 liquid Substances 0.000 title claims abstract description 92
- 239000011248 coating agent Substances 0.000 title claims abstract description 89
- 239000002245 particle Substances 0.000 claims abstract description 151
- 239000002904 solvent Substances 0.000 claims abstract description 43
- 238000009835 boiling Methods 0.000 claims abstract description 35
- 238000009826 distribution Methods 0.000 claims abstract description 16
- 238000002296 dynamic light scattering Methods 0.000 claims abstract description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 abstract description 15
- 238000003860 storage Methods 0.000 abstract description 8
- -1 alkoxy silane Chemical compound 0.000 abstract 2
- 229910000077 silane Inorganic materials 0.000 abstract 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
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- 238000000034 method Methods 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
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- 238000004220 aggregation Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- 238000007756 gravure coating Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
Abstract
Description
本発明は、導電粒子とバインダ成分を含んだ導電膜形成用の塗布液に関する。特に、保存安定性に優れた塗布液に関する。 The present invention relates to a coating liquid for forming a conductive film containing conductive particles and a binder component. In particular, the present invention relates to a coating liquid having excellent storage stability.
従来から、導電粒子を含む塗布液を用いて、基板上に導電性被膜が形成されている。例えば、透明導電膜は表示装置、タッチパネル、太陽電池等に利用されている。導電膜形成用の塗布液として、鎖状導電粒子とアルコキシシランオリゴマーを含む組成物が知られている（例えば、特許文献１）。特許文献１では、バインダ成分としてアルコキシシランオリゴマーを用いている。アルコキシシランオリゴマーは鎖状導電粒子と結合し易いため、得られる膜の強度を向上させることができる。 Conventionally, a conductive film has been formed on a substrate by using a coating liquid containing conductive particles. For example, transparent conductive films are used in display devices, touch panels, solar cells, and the like. As a coating liquid for forming a conductive film, a composition containing chain conductive particles and an alkoxysilane oligomer is known (for example, Patent Document 1). Patent Document 1 uses an alkoxysilane oligomer as a binder component. Since the alkoxysilane oligomer easily binds to the chain conductive particles, the strength of the obtained film can be improved.
特許文献１のように、導電粒子とこの導電粒子に結合するバインダ成分を含む塗布液では、時間経過とともに導電粒子の表面がバインダ成分で覆われていく。バインダ成分は絶縁性なので、バインダ成分に覆われた導電粒子を含んだ膜では、多数の導電粒子による導電パスを形成することができなくなり、初期の塗布液によって形成された膜より導電性が低くなる、という課題があった。 As in Patent Document 1, in a coating liquid containing conductive particles and a binder component bonded to the conductive particles, the surface of the conductive particles is covered with the binder component over time. Since the binder component is insulating, a film containing conductive particles covered with the binder component cannot form a conductive path with a large number of conductive particles, and is less conductive than the film formed by the initial coating liquid. There was a problem of becoming.
そこで、本発明の目的は、保存安定性に優れた導電膜形成用の塗布液を提供することにある。 Therefore, an object of the present invention is to provide a coating liquid for forming a conductive film having excellent storage stability.
本発明の導電膜形成用の塗布液は、鎖状導電粒子と、高沸点溶剤と、低沸点溶剤と、鎖状導電粒子に結合可能なアルコキシシランオリゴマーを含んでいる。鎖状導電粒子は、鎖状導電粒子とアルコキシシランオリゴマーの合計量に対して３５〜７５質量％含まれている。また、塗布液を動的光散乱式の粒度分布計で測定した粒子径分布において、平均粒子径が１００ｎｍ以上であり、体積基準で、粒子径の小さい側から累積して１６％になるときの粒子径Ｄ16と８４％になるときの粒子径Ｄ84との差（Ｄ84−Ｄ16）が２００ｎｍ以上である。 The coating liquid for forming a conductive film of the present invention contains chain conductive particles, a high boiling point solvent, a low boiling point solvent, and an alkoxysilane oligomer that can be bonded to the chain conductive particles. The chain conductive particles are contained in an amount of 35 to 75% by mass based on the total amount of the chain conductive particles and the alkoxysilane oligomer. Further, when the average particle size is 100 nm or more in the particle size distribution measured by the dynamic light scattering type particle size distribution meter of the coating liquid, and the cumulative particle size is 16% from the smaller particle size side on a volume basis. The difference (D 84 − D 16 ) between the particle size D 16 and the particle size D 84 when it becomes 84% is 200 nm or more.
さらに、高沸点溶剤と低沸点溶剤の質量比を、１：９〜１：３の範囲とした。さらに、塗布液に含まれる水を５質量%未満とした。 Further, the mass ratio of the high boiling point solvent to the low boiling point solvent was set in the range of 1: 9 to 1: 3. Further, the amount of water contained in the coating liquid was less than 5% by mass.
塗布液には、鎖状導電粒子の質量に対して０．０００５〜０．００８質量部の酸を含むこととした。さらに、アルコキシシランオリゴマーの重量平均分子量を３５００〜５０００とした。 The coating liquid contained 0.0005 to 0.008 parts by mass of the acid with respect to the mass of the chain conductive particles. Further, the weight average molecular weight of the alkoxysilane oligomer was set to 3500 to 5000.
本発明の塗布液は、高沸点溶剤と低沸点溶剤に、鎖状導電粒子とバインダ成分が分散している。ここで、バインダ成分は、鎖状導電粒子の表面に結合可能なアルコキシシランオリゴマーである。この塗布液には、鎖状導電粒子が鎖状導電粒子とバインダ成分の合計質量に対して３５〜７５質量％含まれている。また、塗布液を動的光散乱式の粒度分布計で測定して粒子径分布を得たとき、体積基準で、粒子径の小さい側から累積して１６％になるときの粒子径Ｄ16と８４％になるときの粒子径Ｄ84との差（Ｄ84−Ｄ16）が２００ｎｍ以上であり、平均粒子径が１００ｎｍ以上である。なお、これ以降、上述の粒子径差（Ｄ84−Ｄ16）を粒径分布の幅と称す。 In the coating liquid of the present invention, chain conductive particles and binder components are dispersed in a high boiling point solvent and a low boiling point solvent. Here, the binder component is an alkoxysilane oligomer that can be bonded to the surface of the chain conductive particles. This coating liquid contains 35 to 75% by mass of chain conductive particles with respect to the total mass of the chain conductive particles and the binder component. Further, when the coating liquid was measured with a dynamic light scattering type particle size distribution meter to obtain a particle size distribution, the particle size D 16 was obtained when the cumulative particle size was 16% from the smaller particle size side on a volume basis. The difference (D 84 − D 16 ) from the particle size D 84 when it becomes 84% is 200 nm or more, and the average particle size is 100 nm or more. Hereinafter, the above-mentioned particle size difference (D 84- D 16 ) will be referred to as the width of the particle size distribution.
ここで、高沸点溶剤とは常圧で沸点１００℃以上の溶剤であり、低沸点溶剤とは常圧で沸点１００℃未満の溶剤である。高沸点溶剤と低沸点溶剤の質量比は、１：９〜１３：７が適しており、１：９〜１：３が最も好ましい。高沸点溶剤と低沸点溶剤の合計量に対する高沸点溶剤の質量比で表現すると、０．１０〜０．６５が適しており、０．１０〜０．２５が最も好ましい。この範囲であれば、塗布時の乾燥速度が適切となるため、筋状やムラ等の塗膜の欠陥や、溶媒の膜中への残存等が発生しにくい。そのため、平滑で均一な導電膜を形成できる。 Here, the high boiling point solvent is a solvent having a boiling point of 100 ° C. or higher at normal pressure, and the low boiling point solvent is a solvent having a boiling point of less than 100 ° C. at normal pressure. The mass ratio of the high boiling point solvent to the low boiling point solvent is preferably 1: 9 to 13: 7, and most preferably 1: 9 to 1: 3. Expressed as the mass ratio of the high boiling point solvent to the total amount of the high boiling point solvent and the low boiling point solvent, 0.10 to 0.65 is suitable, and 0.10 to 0.25 is the most preferable. Within this range, the drying speed at the time of application is appropriate, so that defects in the coating film such as streaks and unevenness and residual solvent in the film are unlikely to occur. Therefore, a smooth and uniform conductive film can be formed.
また、鎖状導電粒子は、一次粒子（導電性の無機粒子）が鎖状に３個以上連結した粒子である。粒子が分岐して連結した部分が存在していてもよい。すなわち、主鎖の部分で３個以上の一次粒子が連結した構造であり、分岐部が存在してもかまわない。このとき、一次粒子の平均粒子径は２〜５０ｎｍが好ましい。平均粒子径が小さすぎると、結晶構造が未発達であり、一次粒子そのものの導電性が十分に得られないおそれがある。逆に、平均粒子径が大きすぎると、鎖状構造を発達させることが難しく、鎖状化したとしても導電パスが効果的に形成され難くなり、膜の導電性が十分に得られないおそれがある。 Further, the chain conductive particles are particles in which three or more primary particles (conductive inorganic particles) are linked in a chain shape. There may be a portion where the particles are branched and connected. That is, it has a structure in which three or more primary particles are connected at the main chain portion, and a branched portion may be present. At this time, the average particle size of the primary particles is preferably 2 to 50 nm. If the average particle size is too small, the crystal structure is underdeveloped, and the conductivity of the primary particles themselves may not be sufficiently obtained. On the contrary, if the average particle size is too large, it is difficult to develop a chain structure, and even if it is chained, it is difficult to effectively form a conductive path, and there is a risk that sufficient conductivity of the film cannot be obtained. be.
また、アルコキシシランオリゴマーは、アルコキシシランの少なくとも一部を加水分解して得られる加水分解生成物（部分加水分解物、加水分解重合物等）であり、重量平均分子量が３０００〜６５００が好ましく、３５００〜５０００がより好ましい。ここで、重量平均分子量はＧＰＣで求められるポリスチレンに換算した値である。 The alkoxysilane oligomer is a hydrolysis product (partially hydrolyzed product, hydrolyzed polymer, etc.) obtained by hydrolyzing at least a part of the alkoxysilane, and has a weight average molecular weight of 3000 to 6500, preferably 3500. ~ 5000 is more preferable. Here, the weight average molecular weight is a value converted to polystyrene obtained by GPC.
なお、塗布液中には鎖状導電粒子が、鎖状導電粒子とバインダ成分の合計量に対して３５〜７５質量％含まれている。特に４５〜７０質量％が好ましい。塗布液中の鎖状導電粒子の濃度が少ないと、導電パスの形成が不十分となり、導電膜の導電性が不十分・不均一になるおそれがある。また、鎖状導電粒子の濃度が多すぎても、得られる導電膜の透過率や硬度の低下を生じるおそれがある。 The coating liquid contains 35 to 75% by mass of chain conductive particles with respect to the total amount of the chain conductive particles and the binder component. In particular, 45 to 70% by mass is preferable. If the concentration of the chain conductive particles in the coating liquid is low, the formation of the conductive path is insufficient, and the conductivity of the conductive film may be insufficient or non-uniform. Further, if the concentration of the chain conductive particles is too high, the transmittance and hardness of the obtained conductive film may decrease.
本発明による塗布液中で、鎖状導電粒子は、それぞれが単独で存在しているだけではなく、沈殿しない凝集体も形成している。また、この塗布液には、連結しない形態のままの一次粒子も存在し得る。このような塗布液は動的光散乱式の粒度分布計によって、平均粒子径が１００ｎｍ以上かつ粒径分布の幅が２００ｎｍ以上と測定される。このような沈殿しない凝集体を含んでいる塗布液では、鎖状導電粒子がバインダ成分と反応し得る（水酸基などを持った）表面積が比較的小さいため、鎖状導電粒子の表面が絶縁性のバインダ成分で覆われにくい。また、塗布液を塗布することで形成された導電膜中で導電パスが十分に形成されやすい。一方、上述の粒径分布を持たない塗布液では、鎖状導電粒子の分散性が高いため、鎖状導電粒子同士の導電パスが形成され難く、また、鎖状導電粒子の表面積が大きいため、粒子とバインダ成分との反応が速やかに進行し、粒子の表面が絶縁成分で覆われやすい。そのため、保存安定性に優れた導電膜形成用の塗布液にはならない。 In the coating liquid according to the present invention, the chain conductive particles not only exist independently, but also form aggregates that do not precipitate. In addition, the coating liquid may also contain primary particles that remain unconnected. Such a coating liquid is measured by a dynamic light scattering type particle size distribution meter to have an average particle size of 100 nm or more and a particle size distribution width of 200 nm or more. In the coating liquid containing such non-precipitating aggregates, the surface area of the chain conductive particles that can react with the binder component (having a hydroxyl group or the like) is relatively small, so that the surface of the chain conductive particles is insulating. Hard to be covered with binder components. In addition, the conductive path is likely to be sufficiently formed in the conductive film formed by applying the coating liquid. On the other hand, in the coating liquid having no particle size distribution as described above, since the chain conductive particles have high dispersibility, it is difficult to form a conductive path between the chain conductive particles, and the surface area of the chain conductive particles is large. The reaction between the particles and the binder component proceeds rapidly, and the surface of the particles is easily covered with the insulating component. Therefore, it does not become a coating liquid for forming a conductive film having excellent storage stability.
また、本塗布液は、鎖状導電粒子とアルコキシシランオリゴマーの合計の固形分濃度（全体固形分濃度）が０．１〜１５質量％の範囲にあることが好ましく、０．５〜１０質量％の範囲にあることがより好ましい。全体固形分濃度が上述の範囲にあると、通常の塗布条件で得られる膜厚を適切な厚さに制御できる。また、塗布液の保存安定性も十分となるため、得られる導電膜の膜厚、導電性、硬度等といった特性が安定的に得られる。 Further, in this coating liquid, the total solid content concentration (total solid content concentration) of the chain conductive particles and the alkoxysilane oligomer is preferably in the range of 0.1 to 15% by mass, and 0.5 to 10% by mass. It is more preferable that it is in the range of. When the total solid content concentration is in the above range, the film thickness obtained under normal coating conditions can be controlled to an appropriate thickness. Further, since the storage stability of the coating liquid is also sufficient, characteristics such as the film thickness, conductivity, and hardness of the obtained conductive film can be stably obtained.
また、本塗布液の２０℃における粘度は０．５〜２０ｍＰａ・ｓの範囲にあることが好ましく、１〜１０ｍＰａ・ｓの範囲にあることがより好ましい。２０℃における粘度が上述の範囲にあると、一般的な塗布方法で得られる膜厚を適切な厚さに制御できる。 Further, the viscosity of the present coating liquid at 20 ° C. is preferably in the range of 0.5 to 20 mPa · s, and more preferably in the range of 1 to 10 mPa · s. When the viscosity at 20 ° C. is in the above range, the film thickness obtained by a general coating method can be controlled to an appropriate thickness.
さらに、本塗布液は鎖状導電粒子の凝集体を含んでいるため、低濃度の状態から濃縮する際に粘度が増加しやすい。粘度の増加を示す塗布液では、導電膜を形成する際に、鎖状導電粒子同士凝集が解れ難く、導電パスが形成されやすい。具体的には、全体固形分が３０％となるように濃縮した際、２０℃における粘度が１０〜３００ｍＰａ・ｓの範囲にあることが好ましく、２０〜１００ｍＰａ・ｓの範囲にあることがより好ましい。 Further, since the present coating liquid contains agglomerates of chain conductive particles, the viscosity tends to increase when the coating liquid is concentrated from a low concentration state. In the coating liquid showing an increase in viscosity, when the conductive film is formed, it is difficult for the chain conductive particles to disaggregate with each other, and a conductive path is likely to be formed. Specifically, when concentrated so that the total solid content is 30%, the viscosity at 20 ° C. is preferably in the range of 10 to 300 mPa · s, and more preferably in the range of 20 to 100 mPa · s. ..
塗布液に含まれる水は、５質量％未満が好ましい。塗布液が５質量%以上の水を含む場合、アルコキシシランオリゴマーの加水分解反応が促進し、さらに、鎖状導電粒子の表面とアルコキシシランオリゴマーの反応が促進し、鎖状導電粒子の表面が絶縁成分で覆われるおそれがある。このような状態の鎖状導電粒子を含む導電膜は、膜中で導電パスが十分に形成されず、良好な導電性が得られないおそれがある。 The amount of water contained in the coating liquid is preferably less than 5% by mass. When the coating liquid contains 5% by mass or more of water, the hydrolysis reaction of the alkoxysilane oligomer is promoted, the reaction between the surface of the chain conductive particles and the alkoxysilane oligomer is promoted, and the surface of the chain conductive particles is insulated. May be covered with ingredients. In the conductive film containing the chain conductive particles in such a state, the conductive path is not sufficiently formed in the film, and good conductivity may not be obtained.
以下、塗布液を構成する各成分について詳細に説明する。 Hereinafter, each component constituting the coating liquid will be described in detail.
＜アルコキシシランオリゴマー＞
アルコキシシランオリゴマーの重量平均分子量は３５００〜５０００が好ましい。アルコキシシランオリゴマーは、以下の式（１）で表されるアルコキシシランの加水分解重合物であり、ここでは、ｎは０〜２の整数である。ｎが３の場合は、２分子間の結合しかできないため、重量平均分子量が３５００以上のオリゴマーを形成することができない。ここでは、ｎが小さいほど好ましく、ｎが０のアルコキシシランを用いることが最も好ましい。このようなアルコキシシランを用いれば、アルコキシシラン同士が密な３次元網目構造を形成することとなり、膜全体の硬度を強くすることができる。
<Alkoxysilane oligomer>
The weight average molecular weight of the alkoxysilane oligomer is preferably 3500 to 5000. The alkoxysilane oligomer is a hydrolyzed polymer of alkoxysilane represented by the following formula (1), where n is an integer of 0 to 2. When n is 3, only two molecules can be bonded to each other, so that an oligomer having a weight average molecular weight of 3500 or more cannot be formed. Here, the smaller n is, the more preferable, and it is most preferable to use an alkoxysilane in which n is 0. When such an alkoxysilane is used, the alkoxysilanes form a dense three-dimensional network structure, and the hardness of the entire film can be increased.
R1 n-Si(OR2)4-n ・・・（１）
ここでR1およびR2は水素原子、ハロゲン原子、炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。なお、一般的にｎは０〜３の整数である。
R 1 n -Si (OR 2 ) 4-n・ ・ ・ (1)
Here, R 1 and R 2 are hydrogen atoms, halogen atoms, and unsubstituted or substituted hydrocarbon groups having 1 to 10 carbon atoms, which may be the same as or different from each other. In general, n is an integer of 0 to 3.
また、塗布液中に存在するアルコキシシランオリゴマーは、固形分として１．２〜３．３質量％、さらには１．５〜２．８質量％が好ましい。アルコキシシランオリゴマーの濃度が低いと、膜のバインダ成分が少なくなり、膜中の鎖状導電粒子同士の密着が不十分になり十分な硬度が得られないおそれがある。また、濃度が高すぎると、塗布液中で鎖状導電粒子の表面との反応が過剰に進み、保存安定性が低下するおそれがある。 The solid content of the alkoxysilane oligomer present in the coating liquid is preferably 1.2 to 3.3% by mass, more preferably 1.5 to 2.8% by mass. If the concentration of the alkoxysilane oligomer is low, the binder component of the film is reduced, and the chain conductive particles in the film are inadequately adhered to each other, which may result in insufficient hardness. On the other hand, if the concentration is too high, the reaction with the surface of the chain conductive particles in the coating liquid may proceed excessively, and the storage stability may decrease.
アルコキシシランの具体例を表１に示す。 Specific examples of alkoxysilanes are shown in Table 1.
＜鎖状導電粒子＞
前述の通り、鎖状導電粒子とは、一次粒子が鎖状に３個以上連結した粒子である。一次粒子とは、単分散状態の導電性の無機粒子である。一次粒子の平均粒子径は２〜５０ｎｍである。透過型電子顕微鏡（ＴＥＭ）で撮影した画像から、任意の１００個の一次粒子について粒子径を測定し、その平均値を一次粒子の平均粒子径とする。さらに、この画像から任意の粒子を５０個選択し、各粒子の連結数を計測する。５０個の粒子の連結数の平均値を平均連結数とした。平均連結数は３以上が好ましく、特に５以上が好ましい。一次粒子の平均連結数が少ないと、導電性の向上効果が十分に得られないおそれがある。
<Chain conductive particles>
As described above, the chain conductive particles are particles in which three or more primary particles are linked in a chain shape. The primary particles are conductive inorganic particles in a monodisperse state. The average particle size of the primary particles is 2 to 50 nm. The particle size of any 100 primary particles is measured from an image taken with a transmission electron microscope (TEM), and the average value thereof is taken as the average particle size of the primary particles. Further, 50 arbitrary particles are selected from this image, and the number of connected particles is measured. The average value of the number of connected 50 particles was taken as the average number of connected particles. The average number of connections is preferably 3 or more, and particularly preferably 5 or more. If the average number of primary particles connected is small, the effect of improving conductivity may not be sufficiently obtained.
ここで、一次粒子としては、導電性を有する粒子であればよい。例えば、金属酸化物粒子等を用いることができる。膜の用途により透明性が求められる場合もある。このような金属酸化物粒子として酸化インジウム、酸化スズ等が挙げられる。また、１種類以上の金属酸化物を主成分として、スズ、アンチモンがドープされた粒子、例えば、アンチモンドープ酸化スズ（ＡＴＯ）、スズドープ酸化インジウム（ＩＴＯ）も使用できる。透明性、導電性及び化学特性に優れている点から、ＡＴＯとＩＴＯの少なくとも一方を含む粒子が好ましく、特にＡＴＯ粒子が好ましい。 Here, the primary particles may be particles having conductivity. For example, metal oxide particles and the like can be used. Transparency may be required depending on the application of the film. Examples of such metal oxide particles include indium oxide and tin oxide. Further, tin and antimony-doped particles containing one or more kinds of metal oxides as main components, for example, antimony-doped tin oxide (ATO) and tin-doped indium oxide (ITO) can also be used. Particles containing at least one of ATO and ITO are preferable, and ATO particles are particularly preferable, because they are excellent in transparency, conductivity, and chemical properties.
また、鎖状導電粒子は、上述の式（１）で示したアルコキシシランで表面処理されていることが好ましい。表面処理を行うことにより、鎖状導電粒子が元の一次粒子に再度分散するのを防止するほか、塗布液中での分散性を向上させ、沈降するような凝集の発生を抑制することができる。 Further, the chain conductive particles are preferably surface-treated with the alkoxysilane represented by the above formula (1). By performing the surface treatment, it is possible to prevent the chain conductive particles from being dispersed again in the original primary particles, improve the dispersibility in the coating liquid, and suppress the occurrence of aggregation such as sedimentation. ..
ここで用いられるアルコキシシランとしては、表１で示したものの他に、ｎ＝３のトリメチルクロロシラン等が挙げられ、これらは単独または２種以上組み合わせて用いることもできる。 Examples of the alkoxysilane used here include trimethylchlorosilane having n = 3 in addition to those shown in Table 1, and these can be used alone or in combination of two or more.
このようなアルコキシシランの使用量は、アルコキシシランの種類、鎖状導電粒子の粒子径などによって異なるが、鎖状導電粒子とアルコキシシランとの量比（加水分解性有機珪素化合物／鎖状導電粒子、重量比）が０．０１〜０．５、さらには０．０２〜０．３の範囲にあることが好ましい。鎖状導電粒子とアルコキシシランとの量比が下限未満の場合は、鎖状に連結した粒子が、塗布液中で元の一次粒子に戻る場合があり、連結を維持したとしても塗料中での分散性が不充分となることがある。このため、この塗料を用いて形成された被膜はヘーズが高く、帯電防止性能が不充分となることがある。鎖状導電粒子とアルコキシシランとの量比が上限を超えると、鎖状導電粒子の表面がアルコキシシランの加水分解物で厚く被覆されるようになり、導電性が低下することがある。 The amount of such alkoxysilane used varies depending on the type of alkoxysilane, the particle size of the chain conductive particles, etc., but the amount ratio of the chain conductive particles to the alkoxysilane (hydrolytable organic silicon compound / chain conductive particles). , Weight ratio) is preferably in the range of 0.01 to 0.5, more preferably 0.02 to 0.3. If the amount ratio of the chain conductive particles to the alkoxysilane is less than the lower limit, the chain-linked particles may return to the original primary particles in the coating liquid, and even if the connection is maintained, the particles are in the paint. Dispersibility may be inadequate. Therefore, the film formed by using this paint has a high haze, and the antistatic performance may be insufficient. When the amount ratio of the chain conductive particles to the alkoxysilane exceeds the upper limit, the surface of the chain conductive particles is thickly coated with the hydrolyzate of the alkoxysilane, and the conductivity may decrease.
＜溶剤＞
ここで使用する溶剤は、塗布後に乾燥工程等によって除去できればよい。高沸点溶剤として、１−メトキシ−２−プロパノール、ジアセトンアルコール、エチレングリコール、ジエチレングリコール等が、低沸点溶剤として、メタノール、エタノール、イソプロピルアルコール、アセトン等が挙げられる。
<Solvent>
The solvent used here may be removed by a drying step or the like after coating. Examples of the high boiling point solvent include 1-methoxy-2-propanol, diacetone alcohol, ethylene glycol and diethylene glycol, and examples of the low boiling point solvent include methanol, ethanol, isopropyl alcohol and acetone.
高沸点溶剤と低沸点溶剤は、混合物として存在していることが好ましく、高沸点溶剤と高沸点溶剤と低沸点溶剤の合計量との質量比は、０．１０〜０．６５が適している。このような混合溶剤を用いると、塗布液を塗布する際の乾燥速度が適切となる。この質量比は０．１０〜０．４０がより好ましく、０．１０〜０．２５が最も好ましい。 The high boiling point solvent and the low boiling point solvent are preferably present as a mixture, and the mass ratio of the total amount of the high boiling point solvent, the high boiling point solvent and the low boiling point solvent is preferably 0.10 to 0.65. .. When such a mixed solvent is used, the drying speed at the time of applying the coating liquid becomes appropriate. This mass ratio is more preferably 0.10 to 0.40, most preferably 0.10 to 0.25.
＜酸＞
また、塗布液は、酸を含むことが好ましい。酸としては、塩酸、硝酸、酢酸、リン酸などが挙げられる。このような酸は、鎖状導電粒子同士の凝集を促進し、塗布液中での導電パスの形成を促進する。酸の量は、鎖状導電粒子の質量に対して０．０００５〜０．００８質量部含まれることが好ましく、０．００１〜０．００４質量部がより好ましい。酸の量が多いと、鎖状導電粒子が過剰に凝集し、鎖状導電粒子の沈殿が発生するおそれがある。このような塗布液から形成された導電膜はヘーズが高くなるおそれがあり、透明導電膜としては適さない。酸の量が少ないと、鎖状導電粒子の凝集が十分に起こらず、また、アルコキシシランオリゴマーと鎖状導電粒子との結合が促進され、鎖状導電粒子の表面が絶縁成分で覆われるおそれがある。このような塗布液を用いて形成された導電膜は、膜中で導電パスが十分に形成されない場合があり、初期のコーティング液から形成された導電性膜より低い導電性を示す場合がある。
<Acid>
Further, the coating liquid preferably contains an acid. Examples of the acid include hydrochloric acid, nitric acid, acetic acid, phosphoric acid and the like. Such an acid promotes the aggregation of the chain conductive particles and promotes the formation of a conductive path in the coating liquid. The amount of the acid is preferably 0.0005 to 0.008 parts by mass, more preferably 0.001 to 0.004 parts by mass, based on the mass of the chain conductive particles. If the amount of acid is large, the chain conductive particles may be excessively aggregated and precipitation of the chain conductive particles may occur. A conductive film formed from such a coating liquid may have a high haze and is not suitable as a transparent conductive film. If the amount of acid is small, the agglomeration of the chain conductive particles does not occur sufficiently, the bond between the alkoxysilane oligomer and the chain conductive particles is promoted, and the surface of the chain conductive particles may be covered with an insulating component. be. The conductive film formed by using such a coating liquid may not sufficiently form a conductive path in the film, and may exhibit lower conductivity than the conductive film formed from the initial coating liquid.
以下、塗布液の製造方法を詳細に説明する。 Hereinafter, the method for producing the coating liquid will be described in detail.
はじめに、導電性の無機酸化物からなる鎖状導電粒子が分散された分散液を用意する。このような分散液は、特開２００６−３３９１１３号公報に開示されている方法などにより調製することができる。鎖状導電粒子の濃度は２０質量％以上が好ましい。 First, a dispersion liquid in which chain conductive particles made of a conductive inorganic oxide are dispersed is prepared. Such a dispersion liquid can be prepared by the method disclosed in Japanese Patent Application Laid-Open No. 2006-339113. The concentration of the chain conductive particles is preferably 20% by mass or more.
次に、この鎖状導電粒子の分散液に、高沸点溶剤と低沸点溶剤の少なくとも一方を含む第一の溶剤と、前述のアルコキシシランオリゴマーとを混合する。このとき、分散液１００質量部に対して、鎖状導電粒子とアルコキシシランオリゴマーを合計で８．５〜１５質量部混合する。なお、鎖状導電粒子の分散液とアルコキシシランオリゴマーを混合した後で第一の溶剤を加えてもよい。このようにして得られた混合液を、室温から第一の溶剤の沸点未満の温度で１時間攪拌する。 Next, the first solvent containing at least one of the high boiling point solvent and the low boiling point solvent and the above-mentioned alkoxysilane oligomer are mixed in the dispersion liquid of the chain conductive particles. At this time, a total of 8.5 to 15 parts by mass of the chain conductive particles and the alkoxysilane oligomer are mixed with 100 parts by mass of the dispersion liquid. The first solvent may be added after mixing the dispersion liquid of the chain conductive particles and the alkoxysilane oligomer. The mixed solution thus obtained is stirred at a temperature from room temperature to a temperature lower than the boiling point of the first solvent for 1 hour.
次に、この混合液に、高沸点溶剤と低沸点溶剤の少なくとも一方を含む第二の溶剤を加え、塗布液が得られる。第一の溶剤と第二の溶剤は同一でも異なっていてもよいが、得られた塗布液には高沸点溶剤と低沸点溶剤が共に含まれている。このとき、塗布液１００質量部に対して、鎖状導電粒子とアルコキシシランオリゴマーを合計で３．５〜１０質量部になるようにする。 Next, a second solvent containing at least one of a high boiling point solvent and a low boiling point solvent is added to this mixed liquid to obtain a coating liquid. The first solvent and the second solvent may be the same or different, but the obtained coating liquid contains both a high boiling point solvent and a low boiling point solvent. At this time, the total amount of the chain conductive particles and the alkoxysilane oligomer is adjusted to 3.5 to 10 parts by mass with respect to 100 parts by mass of the coating liquid.
以下、塗布液を硬化させて得られる導電膜について説明する。液膜を加熱することにより溶剤を除去し、鎖状無機導電粒子とアルコキシシランオリゴマーの脱水縮合反応を進める。導電性膜は、優れた導電性等の高い電気的特性を持ち、光学特性と電気特性を要求される部品に適している。 Hereinafter, the conductive film obtained by curing the coating liquid will be described. The solvent is removed by heating the liquid film, and the dehydration condensation reaction between the chain-like inorganic conductive particles and the alkoxysilane oligomer proceeds. The conductive film has high electrical characteristics such as excellent conductivity, and is suitable for parts that require optical characteristics and electrical characteristics.
基材は特に限定されず、ガラス、プラスチックなど、均一な液膜を形成し、硬化温度に耐えられるものを用いることができる。塗布方法も特に限定されず、バーコーター法、ディップ法、スプレー法、スピナー法、ロールコート法、グラビアコート法、スリットコート法、加圧塗布法等を用いることができる。膜の平均膜厚は、用途に応じて適宜選択できる。塗布による成膜の場合、平均膜厚は８０〜３００ｎｍが好ましい。 The base material is not particularly limited, and a material such as glass or plastic that can form a uniform liquid film and can withstand the curing temperature can be used. The coating method is not particularly limited, and a bar coater method, a dip method, a spray method, a spinner method, a roll coating method, a gravure coating method, a slit coating method, a pressure coating method and the like can be used. The average film thickness of the film can be appropriately selected depending on the application. In the case of film formation by coating, the average film thickness is preferably 80 to 300 nm.
以下、酸を含む塗布液の実施例を詳細に説明する。 Hereinafter, examples of the coating liquid containing an acid will be described in detail.
［実施例１］
はじめに、アルコキシシランオリゴマー（固形分濃度９．８質量％）２３．０gと、鎖状導電粒子（固形分濃度２０．５質量％）１３．４ｇを混合し、６０分間攪拌した。この溶液のアルコキシシランオリゴマーと鎖状導電粒子の合計固形分濃度は１３．７質量％であった。ここで使用したアルコキシシランオリゴマーは、テトラメトキシシランを加水分解して得られた物で、分子量は３８１０である。また、固形分質量に対して塩酸を０．００２質量部含んでいる。鎖状導電粒子は、テトラエトキシシランで表面処理されたＡＴＯ粒子を一次粒子として鎖状に連結された粒子である。
[Example 1]
First, 23.0 g of an alkoxysilane oligomer (solid content concentration 9.8% by mass) and 13.4 g of chain conductive particles (solid content concentration 20.5% by mass) were mixed and stirred for 60 minutes. The total solid content concentration of the alkoxysilane oligomer and the chain conductive particles in this solution was 13.7% by mass. The alkoxysilane oligomer used here is obtained by hydrolyzing tetramethoxysilane and has a molecular weight of 3810. Further, it contains 0.002 parts by mass of hydrochloric acid with respect to the mass of solid content. The chain conductive particles are particles in which ATO particles surface-treated with tetraethoxysilane are linked in a chain as primary particles.
この混合溶液に攪拌しながらイソプロピルアルコール４３．６ｇを添加し、５分間攪拌した。ついで、１−メトキシ−２−プロパノール２０．０ｇを混合し、１５分間攪拌した後、濾過することにより、全体固形分濃度５質量％の塗布液を調製した。塗布液の調製条件を表２に、得られた塗布液の物性を表３に示す。 43.6 g of isopropyl alcohol was added to the mixed solution with stirring, and the mixture was stirred for 5 minutes. Then, 20.0 g of 1-methoxy-2-propanol was mixed, stirred for 15 minutes, and then filtered to prepare a coating liquid having a total solid content concentration of 5% by mass. Table 2 shows the preparation conditions of the coating liquid, and Table 3 shows the physical characteristics of the obtained coating liquid.
この塗布液を、バーコーター法でガラス基板上に塗布し、８０℃で１分間乾燥し、ついで１３０℃の乾燥機内で３０分間加熱した。得られた膜付基材の表面抵抗を測定した。結果を表２に示す。 This coating liquid was applied onto a glass substrate by a bar coater method, dried at 80 ° C. for 1 minute, and then heated in a dryer at 130 ° C. for 30 minutes. The surface resistance of the obtained substrate with a film was measured. The results are shown in Table 2.
また、この塗布液を水温４０℃に調整した浴槽の中に２４時間静置した。この加温処理後の塗布液をスピンコーター法でガラス基板上に塗布し、室温で１分間乾燥し、ついで１３０℃の乾燥機内で３０分間加熱した。得られた膜付基材の表面抵抗を測定した。結果を表４に示す。 Further, this coating liquid was allowed to stand in a bathtub adjusted to a water temperature of 40 ° C. for 24 hours. The coating liquid after this heating treatment was applied onto a glass substrate by a spin coater method, dried at room temperature for 1 minute, and then heated in a dryer at 130 ° C. for 30 minutes. The surface resistance of the obtained substrate with a film was measured. The results are shown in Table 4.
なお、後述の実施例や比較例についても、塗布液と膜付基材の各物性を以下のように測定し、評価した。 In the examples and comparative examples described later, the physical characteristics of the coating liquid and the substrate with a film were measured and evaluated as follows.
（平均粒子径、粒径分布の幅）
動的光散乱方式粒度分布計（ＭＩＣＲＯＴＲＡＣ社製ＮＡＮＯＴＲＡＣ Ｗａｖｅ ２−ＵＴ１５１）を用いて塗布液を測定し、塗布液の平均粒子径と粒径分布の幅（粒子径差：Ｄ84−Ｄ16）を求めた。表３には、この粒径分布幅の半分の値を記入した。
(Average particle size, width of particle size distribution)
The coating liquid was measured using a dynamic light scattering type particle size distribution meter (NANOTRAC Wave 2-UT151 manufactured by MICROTRAC), and the average particle size and the width of the particle size distribution of the coating liquid (particle size difference: D 84- D 16 ). Asked. In Table 3, the value of half of this particle size distribution width is entered.
（粘度）
Ｅ型粘度計（東機産業社製ＴＶ‐２５型）を用いて２０℃における粘度を測定した。全体固形分濃度５質量％の塗布液と、これを全体固形分３０％に濃縮した塗布液について粘度を測定した。
(viscosity)
The viscosity at 20 ° C. was measured using an E-type viscometer (TV-25 type manufactured by Toki Sangyo Co., Ltd.). The viscosities of the coating liquid having a total solid content concentration of 5% by mass and the coating liquid concentrated to a total solid content of 30% were measured.
（表面抵抗）
表面抵抗を表面抵抗測定機（三菱化学アナリテック社製ハイレスターＵＸ ＭＣＰ−ＨＴ８００）を用いて測定した。
(Surface resistance)
The surface resistance was measured using a surface resistance measuring machine (High Leicester UX MCP-HT800 manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
（保存安定性）
保存安定性は、（加温処理後の塗布液による膜付基材の表面抵抗値）／（初期の塗布液による膜付基材の表面抵抗値）で求められる比に基づいて評価した。
(Storage stability)
The storage stability was evaluated based on the ratio obtained by (the surface resistance value of the film-coated substrate by the coating liquid after the heating treatment) / (the surface resistance value of the film-coated substrate by the initial coating liquid).
［実施例２］
本実施例では、アルコキシシランオリゴマーの添加量を２０．４ｇ、鎖状導電粒子の添加量を１４．６ｇ、イソプロピルアルコールの添加量を４５．０ｇとした。これ以外は実施例１と同様にして、塗布液と膜付基材を調製、評価した。
[Example 2]
In this example, the amount of the alkoxysilane oligomer added was 20.4 g, the amount of chain conductive particles added was 14.6 g, and the amount of isopropyl alcohol added was 45.0 g. Except for this, a coating liquid and a substrate with a film were prepared and evaluated in the same manner as in Example 1.
［実施例３］
本実施例では、アルコキシシランオリゴマーの添加量を２８．１ｇ、鎖状無機導電性粒子の添加量を１１．１ｇ、イソプロピルアルコールの添加量を４０．８ｇとした。これ以外は実施例１と同様にして、塗布液と膜付基材を調製、評価した。
[Example 3]
In this example, the amount of the alkoxysilane oligomer added was 28.1 g, the amount of the chain inorganic conductive particles added was 11.1 g, and the amount of the isopropyl alcohol added was 40.8 g. Except for this, a coating liquid and a substrate with a film were prepared and evaluated in the same manner as in Example 1.
［比較例１］
イソプロピルアルコール４３．６gに、実施例１と同じ鎖状導電粒子（固形分濃度２０．５質量％）１３．４gを添加し、５分間攪拌した。ついで、１−メトキシ−２−プロパノール２０．０gを混合し、１５分間攪拌した。実施例１と同じアルコキシシランオリゴマー２３．０gを混合し、６０分間攪拌した。このときのアルコキシシランオリゴマーと鎖状導電粒子の合計固形分濃度は５質量％であった。その後１μｍナイロンフィルターで濾過し、全体固形分濃度５質量％の塗布液を調製した。得られた塗布液における各成分の濃度等を表１に示す。これ以外は、実施例１と同様に調製、評価した。
[Comparative Example 1]
To 43.6 g of isopropyl alcohol, 13.4 g of the same chain conductive particles (solid content concentration 20.5% by mass) as in Example 1 was added, and the mixture was stirred for 5 minutes. Then, 20.0 g of 1-methoxy-2-propanol was mixed and stirred for 15 minutes. 23.0 g of the same alkoxysilane oligomer as in Example 1 was mixed and stirred for 60 minutes. At this time, the total solid content concentration of the alkoxysilane oligomer and the chain conductive particles was 5% by mass. Then, it was filtered through a 1 μm nylon filter to prepare a coating liquid having an overall solid content concentration of 5% by mass. Table 1 shows the concentrations of each component in the obtained coating liquid. Other than this, it was prepared and evaluated in the same manner as in Example 1.
［比較例２］
イソプロピルアルコールの添加量を４５．０ｇ、実施例１と同じ鎖状導電粒子の添加量を１４．６ｇに、実施例１と同じアルコキシシランオリゴマーの添加量を２０．４ｇとした。これ以外は、比較例１と同様にして、塗布液と膜付基材を調製、評価した。
[Comparative Example 2]
The addition amount of isopropyl alcohol was 45.0 g, the addition amount of the same chain conductive particles as in Example 1 was 14.6 g, and the addition amount of the same alkoxysilane oligomer as in Example 1 was 20.4 g. Except for this, a coating liquid and a substrate with a film were prepared and evaluated in the same manner as in Comparative Example 1.
［比較例３］
イソプロピルアルコールの添加量を４０．８ｇ、実施例１と同じ鎖状導電粒子の添加量を１１．１ｇに、実施例１と同じアルコキシシランオリゴマーの添加量を２８．１ｇとした。これ以外は、比較例１と同様にして、塗布液と膜付基材を調製、評価した。
[Comparative Example 3]
The addition amount of isopropyl alcohol was 40.8 g, the addition amount of the same chain conductive particles as in Example 1 was 11.1 g, and the addition amount of the same alkoxysilane oligomer as in Example 1 was 28.1 g. Except for this, a coating liquid and a substrate with a film were prepared and evaluated in the same manner as in Comparative Example 1.
Claims (7)
前記塗布液には、前記鎖状導電粒子が前記鎖状導電粒子と前記アルコキシシランオリゴマーの合計量に対して３５〜７５質量％含まれており、
前記塗布液を動的光散乱式の粒度分布計で測定した粒子径分布において、平均粒子径が１００ｎｍ以上であり、体積基準で、粒子径の小さい側から累積して１６％になるときの粒子径Ｄ16と８４％になるときの粒子径Ｄ84との差（Ｄ84−Ｄ16）が２００ｎｍ以上である塗布液。 A coating liquid for forming a conductive film, which comprises chain conductive particles, a high boiling point solvent, a low boiling point solvent, and an alkoxysilane oligomer that can be bonded to the chain conductive particles.
The coating liquid contains 35 to 75% by mass of the chain conductive particles with respect to the total amount of the chain conductive particles and the alkoxysilane oligomer.
Particles when the average particle size is 100 nm or more and the cumulative particle size is 16% from the smaller particle size side on a volume basis in the particle size distribution measured by the dynamic light scattering type particle size distribution meter of the coating liquid. A coating liquid in which the difference (D 84 − D 16 ) between the particle diameter D 16 and the particle diameter D 84 when the diameter is 84% is 200 nm or more.
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