JP7012415B2 - Wire with terminal - Google Patents

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JP7012415B2
JP7012415B2 JP2019067135A JP2019067135A JP7012415B2 JP 7012415 B2 JP7012415 B2 JP 7012415B2 JP 2019067135 A JP2019067135 A JP 2019067135A JP 2019067135 A JP2019067135 A JP 2019067135A JP 7012415 B2 JP7012415 B2 JP 7012415B2
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terminal
photoreaction initiator
conductor
coating material
coated
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JP2020164669A (en
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裕文 河中
広樹 田中
宏和 高橋
拓郎 山田
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THE FURUKAW ELECTRIC CO., LTD.
Furukawa Automotive Systems Inc
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THE FURUKAW ELECTRIC CO., LTD.
Furukawa Automotive Systems Inc
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Description

本発明は、例えば自動車部品等の防食のために用いられる被膜材、これを用いた樹脂被膜構造及び端子付き電線等に関するものである。 The present invention relates to, for example, a coating material used for corrosion protection of automobile parts and the like, a resin coating structure using the coating material, an electric wire with a terminal, and the like.

従来、自動車、OA機器、家電製品等の分野では、電力線や信号線として、電気導電性に優れた銅系材料からなる電線が使用されている。特に、自動車分野においては、車両の高性能化、高機能化が急速に進められており、車載される各種電気機器や制御機器が増加している。したがって、これに伴い、使用される端子付き電線も増加する傾向にある。 Conventionally, in the fields of automobiles, OA equipment, home appliances and the like, electric wires made of copper-based materials having excellent electrical conductivity have been used as power lines and signal lines. In particular, in the field of automobiles, the performance and functionality of vehicles are rapidly increasing, and the number of various electric devices and control devices mounted on vehicles is increasing. Therefore, along with this, the number of electric wires with terminals used tends to increase.

一方、環境問題が注目される中、自動車の軽量化が要求されている。したがって、ワイヤハーネスの使用量増加に伴う重量増加が問題となる。このため、従来使用されている銅線に代えて、軽量なアルミニウム電線が注目されている。 On the other hand, as environmental problems are attracting attention, weight reduction of automobiles is required. Therefore, an increase in weight due to an increase in the amount of wire harness used becomes a problem. Therefore, instead of the conventionally used copper wire, a lightweight aluminum electric wire is attracting attention.

ここで、このような電線同士を接続する際や機器類等の接続部においては、接続用端子が用いられる。しかし、アルミニウム電線を用いた端子付き電線であっても、接続部の信頼性等のため、端子部には、電気特性に優れる銅が使用される場合がある。このような場合には、アルミニウム電線と銅製の端子とが接合されて使用される。 Here, a connection terminal is used when connecting such electric wires or in a connection portion of equipment or the like. However, even in the case of an electric wire with a terminal using an aluminum electric wire, copper having excellent electrical characteristics may be used for the terminal portion because of the reliability of the connection portion and the like. In such a case, the aluminum electric wire and the copper terminal are joined and used.

しかし、異種金属を接触させると、標準電極電位の違いから、いわゆる電食が発生する恐れがある。特に、アルミニウムと銅との標準電極電位差は大きいため、接触部への水の飛散や結露等の影響により、電気的に卑であるアルミニウム側の腐食が進行する。このため、接続部における電線と端子との接続状態が不安定となり、接触抵抗の増加や線径の減少による電気抵抗の増大、更には断線が生じて電装部品の誤動作、機能停止に至る恐れがある。 However, when dissimilar metals are brought into contact with each other, so-called galvanic corrosion may occur due to the difference in standard electrode potential. In particular, since the standard electrode potential difference between aluminum and copper is large, corrosion on the electrically base aluminum side progresses due to the influence of water scattering and dew condensation on the contact portion. For this reason, the connection state between the electric wire and the terminal at the connection part becomes unstable, and there is a risk that the contact resistance will increase, the electrical resistance will increase due to the decrease in the wire diameter, and the wire will break, resulting in malfunction or malfunction of the electrical components. be.

このため、電線と端子との接続部を樹脂部材で被覆する方法が提案されている。例えば、被覆圧着部と導線圧着部との間に露出する導線等に樹脂部材を塗布して被覆した端子付き電線が提案されている(特許文献1)。 Therefore, a method of covering the connection portion between the electric wire and the terminal with a resin member has been proposed. For example, there has been proposed an electric wire with a terminal coated by applying a resin member to a conductor wire exposed between a coated crimping portion and a conducting wire crimping portion (Patent Document 1).

図5は、従来の端子付き電線の部分断面図である。通常、被覆導線111の先端近傍は、被覆部115が除去されて内部の導線103が露出する。露出した導線103は導線圧着部107で圧着され、被覆部115は、被覆圧着部109で圧着される。被覆圧着部109と導線圧着部107の間のバレル間部108には、導線103の一部が露出するため、バレル間部108から導線圧着部107は、樹脂部材117で被覆される。 FIG. 5 is a partial cross-sectional view of a conventional electric wire with a terminal. Normally, in the vicinity of the tip of the coated conductor wire 111, the covering portion 115 is removed and the inner conductor wire 103 is exposed. The exposed conductor 103 is crimped by the conductor crimping portion 107, and the covering portion 115 is crimped by the covering crimping portion 109. Since a part of the lead wire 103 is exposed in the barrel inter-barrel portion 108 between the cover crimping portion 109 and the conductor crimping portion 107, the conductor crimping portion 107 from the barrel inter-barrel portion 108 is covered with the resin member 117.

しかし、被覆部115の端部と導線103の露出部の境界部において、外径の変化に伴う微小な隙間(図中X)が生じやすい。このような隙間が生じると、被覆圧着部109と被覆部115との間を浸透した水分が、導線103及び導線圧着部107へ浸透する恐れがある。このため、十分な防食性を確保するためには、この隙間Xへも樹脂部材117を浸透させて硬化させる必要がある。 However, at the boundary between the end of the covering portion 115 and the exposed portion of the conducting wire 103, a minute gap (X in the figure) is likely to occur due to a change in the outer diameter. When such a gap is generated, the moisture that has permeated between the coated crimping portion 109 and the coated portion 115 may permeate into the conductor 103 and the conductor crimping portion 107. Therefore, in order to ensure sufficient anticorrosion properties, it is necessary to infiltrate the resin member 117 into the gap X and cure it.

この隙間Xを樹脂部材117で埋める方法としては、例えば塗布する際の樹脂部材117の粘度を調整する方法がある。しかし、隙間Xに樹脂部材117を充填できたとしても、紫外線を照射した際に紫外線が導線103の裏側に行きわたらずに硬化に時間を要するという問題がある。 As a method of filling the gap X with the resin member 117, for example, there is a method of adjusting the viscosity of the resin member 117 at the time of coating. However, even if the resin member 117 can be filled in the gap X, there is a problem that when the ultraviolet rays are irradiated, the ultraviolet rays do not reach the back side of the conducting wire 103 and it takes time to cure.

このように、導線圧着部の深部を硬化させる方法としては、紫外線硬化材料と、ウレタン結合、尿素結合、イソシアネート基から選択される少なくとも1種を含む化合物と含金属化合物から構成される連鎖移動剤を含有させた紫外線硬化組成物が提案されている(例えば特許文献2)。 As described above, as a method for curing the deep portion of the wire crimping portion, a chain transfer agent composed of an ultraviolet curing material, a compound containing at least one selected from a urethane bond, a urea bond, and an isocyanate group, and a metal-containing compound. A UV curable composition containing the above has been proposed (for example, Patent Document 2).

特開2017-102998号公報JP-A-2017-102998 特開2011-123281号公報Japanese Unexamined Patent Publication No. 2011-123281

しかし、特許文献2の方法では、連鎖移動剤として含金属化合物が添加されるため、含金属化合物が紫外線を吸収してしまうという問題がある。このため、硬化させるための紫外線照射時間が長くなるという問題がある。 However, in the method of Patent Document 2, since the metal-containing compound is added as a chain transfer agent, there is a problem that the metal-containing compound absorbs ultraviolet rays. Therefore, there is a problem that the ultraviolet irradiation time for curing becomes long.

特に、端子付き電線に樹脂部材を塗布して硬化させる場合には、塗布した樹脂部材は視認可能であることが望ましい。これは、樹脂部材で確実に導線が覆われているかを目視で確認するためである。このため、完全に透明な樹脂部材ではなく、着色等による有色の樹脂部材が用いられる場合がある。しかし、このように樹脂部材の視認性を向上させるために着色すると、紫外線が深部まで届きにくくなるという問題がある。 In particular, when a resin member is applied to an electric wire with terminals and cured, it is desirable that the applied resin member be visible. This is to visually confirm whether the conductor is surely covered with the resin member. Therefore, instead of a completely transparent resin member, a colored resin member such as colored resin member may be used. However, if coloring is performed in order to improve the visibility of the resin member in this way, there is a problem that it becomes difficult for ultraviolet rays to reach deep parts.

本発明は、このような問題に鑑みてなされたもので、着色して用いられる場合であっても、含金属化合物を使用することなく、深部の樹脂の硬化時間を短くすることが可能な被膜材、これを用いた樹脂被膜構造及び端子付き電線を提供することを目的とする。 The present invention has been made in view of such a problem, and a coating film capable of shortening the curing time of a deep resin without using a metal-containing compound even when used in a colored manner. It is an object of the present invention to provide a material, a resin coating structure using the material, and an electric wire with a terminal.

前述した目的を達するために本発明は、被覆材が、被覆対象部材に塗布されて硬化している樹脂被膜構造において、前記被覆対象部材が被覆導線と端子とが接続された端子付き電線であって、前記被覆導線は、被覆部と、前記被覆部の先端から露出する導線とを具備し、前記端子は、端子本体と圧着部とを有し、前記圧着部は、前記導線が圧着される導線圧着部と、前記被覆部が圧着される被覆圧着部と、前記導線圧着部と前記被覆圧着部との間のバレル間部と、を具備し、少なくとも、前記バレル間部から前記導線圧着部までの前記導線が露出する部位が前記被膜材で覆われており、前記被覆材は、母材の樹脂に光反応開始剤が添加されており、前記光反応開始剤は、紫外線領域の光を照射することによってラジカルを発生するアミノケトン系の第1光反応開始剤と、紫外線領域の光に対しフォトブリーチング性を有する第2光反応開始剤とを含み、前記第1光反応開始剤は、365nm~405nmの波長領域の光を照射することでラジカルを発生し、前記第2光反応開始剤は、アシルフォスフィンオキサイド系光反応開始剤または、オキシムエステル系光反応開始剤の少なくとも一方を含み、紫外線領域の光で励起され、前記第1光反応開始剤に電子供与することで、365nm~405nmでのラジカル発生を増強するチオキサントン系増感剤を含むことを特徴とする端子付き電線。 In order to achieve the above-mentioned object, the present invention comprises a resin coating structure in which a covering material is applied to a covering target member and cured, and the coating target member is a terminal-equipped electric wire in which a covering lead wire and a terminal are connected. The covered lead wire includes a covered portion and a lead wire exposed from the tip of the covered portion, the terminal has a terminal body and a crimping portion, and the crimping portion is crimped with the lead wire. It is provided with a lead wire crimping portion, a coated crimping portion to which the covering portion is crimped, and a barrel inter-barrel portion between the lead wire crimping portion and the covering crimping portion, and at least the lead wire crimping portion is provided from the barrel inter-barrel portion. The portion where the radicals are exposed is covered with the coating material, the coating material has a photoreaction initiator added to the resin of the base material, and the photoreaction initiator emits light in the ultraviolet region. The first photoreaction initiator comprises an aminoketone-based first photoreaction initiator that generates radicals by irradiation and a second photoreaction initiator having photobleaching property with respect to light in the ultraviolet region. Radicals are generated by irradiating light in the wavelength range of 365 nm to 405 nm, and the second photoreaction initiator contains at least one of an acylphosphine oxide-based photoreaction initiator or an oxime ester-based photoreaction initiator. , An electric wire with a terminal, which is excited by light in the ultraviolet region and contains a thioxanthone-based sensitizer that enhances radical generation in 365 nm to 405 nm by donating electrons to the first photoreaction initiator .

発明によれば、導線の下部まで被膜材が塗布されて硬化した端子付き電線を得ることができる。
また、光反応開始剤が、アミノケトン系の第1光反応開始剤を含み、光反応開始剤が、フォトブリーチング性を有する第2光反応開始剤を含むため、光を照射した際に、硬化が開始した樹脂の吸光度を下げることができ、仮に被膜材が着色されていても、より深くまで光を到達させて硬化を進行させることができる。このため、短時間で深部まで被膜材を硬化させることができる。
According to the present invention, it is possible to obtain an electric wire with a terminal which is hardened by applying a coating material to the lower part of the conducting wire.
Further , since the photoreaction initiator contains an aminoketone-based first photoreaction initiator and the photoreaction initiator contains a second photoreaction initiator having photobleaching property, it cures when irradiated with light. It is possible to reduce the absorbance of the resin that has started, and even if the coating material is colored, it is possible to allow light to reach deeper and proceed with curing. Therefore, the coating material can be cured to a deep part in a short time.

特に、第1光反応開始剤が、365nm~405nmの波長領域の光を照射することでラジカルを発生することで、紫外線領域の光の照射によって確実に被膜材を照射させることができる。 In particular, the first photoreaction initiator generates radicals by irradiating light in a wavelength region of 365 nm to 405 nm, so that the coating material can be reliably irradiated by irradiation with light in an ultraviolet region.

また、紫外線領域の光で励起され、第1光反応開始剤に電子供与することで、365nm~405nmでのラジカル発生を増強するチオキサントン系増感剤を含むことで、アミノケトン系の光反応開始剤の吸収波長を長波長側にシフトさせることができる。たとえば、α-アミノケトン系の吸収帯域である320nmを長波長側シフトすることで、より長波長の光によっても硬化させることができる。したがって、385nmの光源や405nmの光源、もしくは両方を含む光源を用いることで、より硬化性を向上させることができる。 In addition, an aminoketone-based photoreaction initiator is contained by containing a thioxanthone-based sensitizer that is excited by light in the ultraviolet region and donates electrons to the first photoreaction initiator to enhance radical generation at 365 nm to 405 nm. The absorption wavelength of the light can be shifted to the long wavelength side. For example, by shifting the absorption band of the α-aminoketone system of 320 nm to the long wavelength side, it can be cured even by light having a longer wavelength. Therefore, the curability can be further improved by using a light source having a light source of 385 nm, a light source having a diameter of 405 nm, or a light source containing both.

また、第2光反応開始剤が、アシルフォスフィンオキサイド系光反応開始剤または、オキシムエステル系光反応開始剤の少なくとも一方を含むことで365~380nm周辺の波長において、より確実にフォトブリーチング性を発揮させることができる。 Further, since the second photoreaction initiator contains at least one of the acylphosphine oxide-based photoreaction initiator and the oxime ester-based photoreaction initiator, the photobleaching property is more reliably obtained at a wavelength around 365 to 380 nm. Can be demonstrated.

前記バレル間部において表面部の前記被膜材と、前記導線の裏側における端子底面側の前記被膜材との、赤外光吸収に基づき算出される硬化反応率の差が3%以内であることが望ましい。 The difference in the curing reaction rate calculated based on infrared light absorption between the coating material on the surface portion and the coating material on the bottom surface side of the terminal on the back side of the conducting wire in the inter-barrel portion is within 3%. desirable.

第3の発明によれば、導線の下部まで被膜材が塗布されて硬化した端子付き電線を得ることができる。 According to the third invention, it is possible to obtain an electric wire with a terminal which is hardened by applying a coating material to the lower part of the conducting wire.

特に、バレル間部における表面部の被膜材と、導線の裏側における端子底面側の被膜材との、赤外光吸収に基づき算出される硬化反応率の差が3%以内であれば、被膜材の表面と深部との硬化反応率の差が小さいため、冷熱衝撃試験において、被膜材の劣化等を抑制することができる。 In particular, if the difference in the curing reaction rate calculated based on infrared light absorption between the coating material on the surface portion between the barrels and the coating material on the bottom surface side of the terminal on the back side of the conducting wire is within 3%, the coating material. Since the difference in the curing reaction rate between the surface and the deep part of the surface is small, deterioration of the coating material can be suppressed in the thermal shock test.

本発明によれば、着色して用いられる場合であっても、含金属化合物を使用することなく、深部の樹脂の硬化時間を短くすることが可能な被膜材、これを用いた樹脂被膜構造及び端子付き電線を提供することができる。 According to the present invention, a coating material capable of shortening the curing time of a deep resin without using a metal-containing compound even when used in color, a resin coating structure using the coating material, and a resin coating structure using the coating material. Wires with terminals can be provided.

端子付き電線10を示す斜視図。The perspective view which shows the electric wire 10 with a terminal. 端子付き電線10を示す断面図。The cross-sectional view which shows the electric wire 10 with a terminal. 圧着前の端子1と被覆導線11を示す図。The figure which shows the terminal 1 and the coated conductor wire 11 before crimping. 端子付き電線10の正圧試験方法を示す図。The figure which shows the positive pressure test method of the electric wire 10 with a terminal. 従来の端子付き電線の部分断面図。Partial cross-sectional view of a conventional electric wire with a terminal.

以下、図面を参照しながら、本発明の実施形態について説明する。図1は、端子付き電線10を示す斜視図であり、図2は断面図である。なお、図1は、被膜材17を透視した図である。端子付き電線10は、端子1と被覆導線11が接続されて構成される。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a perspective view showing an electric wire 10 with a terminal, and FIG. 2 is a sectional view. Note that FIG. 1 is a perspective view of the coating material 17. The electric wire 10 with a terminal is configured by connecting the terminal 1 and the coated conductor wire 11.

被覆導線11は、アルミニウムまたはアルミニウム合金製である導線13と、導線13を被覆する被覆部15からなる。すなわち、被覆導線11は、被覆部15と、その先端から露出する導線13とを具備する。導線13は、例えば、複数の素線が撚り合わせられた撚り線である。 The coated conductor 11 includes a conductor 13 made of aluminum or an aluminum alloy, and a covering portion 15 that covers the conductor 13. That is, the coated conductor 11 includes a coated portion 15 and a conductor 13 exposed from the tip thereof. The conductor 13 is, for example, a stranded wire in which a plurality of strands are twisted together.

端子1は、オープンバレル型であり、銅または銅合金製である。端子1には被覆導線11が接続される。端子1は、端子本体3と圧着部5とがトランジション部4を介して連結されて構成される。圧着部5と端子本体3の間に位置するトランジション部4は、上方が開口する。 The terminal 1 is an open barrel type and is made of copper or a copper alloy. A coated conducting wire 11 is connected to the terminal 1. The terminal 1 is configured by connecting the terminal body 3 and the crimping portion 5 via the transition portion 4. The transition portion 4 located between the crimping portion 5 and the terminal body 3 opens upward.

端子本体3は、所定の形状の板状素材を、断面が矩形の筒体に形成したものである。端子本体3は、内部に、板状素材を矩形の筒体内に折り込んで形成される弾性接触片を有する。端子本体3は、前端部から雄型端子などが挿入されて接続される。なお、以下の説明では、端子本体3が、雄型端子等の挿入タブ(図示省略)の挿入を許容する雌型端子である例を示すが、本発明において、この端子本体3の細部の形状は特に限定されない。例えば、雌型の端子本体3に代えて雄型端子の挿入タブを設けてもよい。 The terminal body 3 is formed by forming a plate-shaped material having a predetermined shape into a tubular body having a rectangular cross section. The terminal body 3 has an elastic contact piece formed by folding a plate-shaped material into a rectangular cylinder. The terminal body 3 is connected by inserting a male terminal or the like from the front end portion. In the following description, an example is shown in which the terminal body 3 is a female terminal that allows insertion of an insertion tab (not shown) such as a male terminal, but in the present invention, the detailed shape of the terminal body 3 is shown. Is not particularly limited. For example, a male terminal insertion tab may be provided instead of the female terminal body 3.

圧着部5は、被覆導線11と圧着される部位であり、圧着前においては、端子1の長手方向に垂直な断面形状が略U字状のバレル形状を有する。端子1の圧着部5は、被覆導線11の先端側に被覆部15から露出する導線13を圧着する導線圧着部7と、被覆導線11の被覆部15を圧着する被覆圧着部9と、導線圧着部7と被覆圧着部9の間のバレル間部8からなる。 The crimping portion 5 is a portion to be crimped to the coated conducting wire 11, and before crimping, the crimping portion 5 has a barrel shape having a substantially U-shaped cross section perpendicular to the longitudinal direction of the terminal 1. The crimping portion 5 of the terminal 1 has a lead wire crimping portion 7 that crimps the lead wire 13 exposed from the coated lead wire 11 to the tip end side of the coated lead wire 11, a coated crimping portion 9 that crimps the coated portion 15 of the coated lead wire 11, and a lead wire crimping portion. It is composed of a barrel-to-barrel portion 8 between the portion 7 and the covering crimping portion 9.

導線圧着部7の内面の一部には、幅方向(長手方向に垂直な方向)に、図示を省略したセレーションが設けられる。このようにセレーションを形成することで、導線13を圧着した際に、導線13の表面の酸化膜を破壊しやすく、また、導線13との接触面積を増加させることができる。 A part of the inner surface of the wire crimping portion 7 is provided with serrations (not shown) in the width direction (direction perpendicular to the longitudinal direction). By forming the serrations in this way, when the conductor 13 is crimped, the oxide film on the surface of the conductor 13 is easily broken, and the contact area with the conductor 13 can be increased.

被覆導線11の先端は、被覆部15が剥離され、内部の導線13が露出する。被覆導線11の被覆部15は、端子1の被覆圧着部9によって圧着される。また、被覆部15が剥離されて露出する導線13は、導線圧着部7により圧着される。導線圧着部7において、導線13と端子1とが電気的に接続される。なお、被覆部15の端面は、被覆圧着部9と導線圧着部7の間のバレル間部8に位置する。 At the tip of the coated conductor 11, the coated portion 15 is peeled off, and the inner conductor 13 is exposed. The coated portion 15 of the coated conductor 11 is crimped by the coated crimping portion 9 of the terminal 1. Further, the conductor 13 exposed by peeling off the covering portion 15 is crimped by the conductor crimping portion 7. In the conductor crimping portion 7, the conductor 13 and the terminal 1 are electrically connected. The end face of the covering portion 15 is located at the barrel-to-barrel portion 8 between the covering crimping portion 9 and the lead wire crimping portion 7.

本発明では、少なくとも、バレル間部8から導線圧着部7までの導線13が露出する部位が被膜材17で覆われている。すなわち、少なくとも、バレル間部8から導線圧着部7までの導線13が露出する部位が被膜材17で覆われており、導線13は、被膜材17によって外部に露出しない。被膜材17は防食材として機能し、被覆対象部材である端子付き電線に塗布して硬化させることで、樹脂被膜構造を構成する。 In the present invention, at least the portion where the conductor 13 from the barrel inter-barrel portion 8 to the conductor crimping portion 7 is exposed is covered with the coating material 17. That is, at least the portion where the conductor 13 from the barrel inter-barrel portion 8 to the conductor crimping portion 7 is exposed is covered with the coating material 17, and the conductor 13 is not exposed to the outside by the coating material 17. The coating material 17 functions as a food-proof material, and forms a resin coating structure by being applied to an electric wire with a terminal, which is a covering target member, and cured.

ここで、被膜材17は、オリゴマー、希釈モノマー、ポリオール、シランカップリング剤のうち必要な成分を含有した母材の樹脂に、光反応開始剤が添加されて構成される。すなわち、被膜材17は、紫外線硬化性を有する。また、本発明の被膜材17には、少なくとも2種類の光反応開始剤が含まれ、紫外線領域の光を照射することによってラジカルを発生するアミノケトン系の第1光反応開始剤と、紫外線領域の光に対しフォトブリーチング性を有する第2光反応開始剤とを含む。なお、本発明の被膜材17には、含金属化合物(金属塩又は金属錯体)は含まれない。また、被膜材17には、増感剤、顔料、染料、滑剤などの添加剤を含んでいてもよい。 Here, the coating material 17 is configured by adding a photoreaction initiator to the resin of the base material containing the necessary components of the oligomer, the diluting monomer, the polyol, and the silane coupling agent. That is, the coating material 17 has ultraviolet curability. Further, the coating material 17 of the present invention contains at least two kinds of photoreaction initiators, and includes an aminoketone-based first photoreaction initiator that generates radicals by irradiating light in an ultraviolet region, and an ultraviolet region. It contains a second photoreaction initiator having photobleaching property with respect to light. The coating material 17 of the present invention does not contain a metal-containing compound (metal salt or metal complex). Further, the coating material 17 may contain additives such as a sensitizer, a pigment, a dye, and a lubricant.

第1光反応開始剤のアミノケトン系の光反応開始剤は、365nm~405nmの波長領域の光を照射することでラジカルを発生するものである。アミノケトン系の光反応開始剤は、視認性のために顔料や染料を含んだ紫外線硬化樹脂を硬化させる場合にも、硬化性への影響を受けにくい。このため、完全に無色透明ではない被膜材17を端子付き電線に塗布した場合でも、深部まで硬化させることができるとともに、着色によって被膜材17が塗布されているかどうかを容易に把握することができる。 The aminoketone-based photoreaction initiator of the first photoreaction initiator generates radicals by irradiating light in a wavelength region of 365 nm to 405 nm. The aminoketone-based photoreaction initiator is not easily affected by the curability even when the ultraviolet curable resin containing a pigment or dye is cured for visibility. Therefore, even when the coating material 17 which is not completely colorless and transparent is applied to the electric wire with terminals, it can be cured to a deep part and it can be easily grasped whether or not the coating material 17 is applied by coloring. ..

さらに、紫外線領域の光で励起され、第1光反応開始剤に電子供与することで、365nm~405nmでのラジカル発生を増強するチオキサントン系増感剤を含むことが望ましい。アミノケトン系の光反応開始剤は、チオキサントン系増感剤と混合することで、吸収波長が長波長側にシフトする。すなわち、より長波長側の光源によって硬化させることができる。長波長の光源からの光は、深部に届きやすいため、例えば、385nmの光源や405nmの光源、もしくは両方を含む光源を用いることで、より硬化性を向上させることができる。 Further, it is desirable to include a thioxanthone-based sensitizer that is excited by light in the ultraviolet region and donates electrons to the first photoreaction initiator to enhance radical generation at 365 nm to 405 nm. By mixing the aminoketone-based photoreaction initiator with the thioxanthone-based sensitizer, the absorption wavelength shifts to the long wavelength side. That is, it can be cured by a light source on the longer wavelength side. Since the light from the light source having a long wavelength easily reaches a deep part, for example, by using a light source having a diameter of 385 nm, a light source having a diameter of 405 nm, or a light source containing both, the curability can be further improved.

また、第2光反応開始剤としては、アシルフォスフィンオキサイド系光反応開始剤または、オキシムエステル系光反応開始剤の少なくとも一方を含むことが望ましい。アシルフォスフィンオキサイド系光反応開始剤とオキシムエステル系光反応開始剤は、いずれも、380nm近傍においてフォトブリーチング性を有し、当該波長の光を照射することで、光の透過率が向上する。 Further, it is desirable that the second photoreaction initiator contains at least one of an acylphosphine oxide-based photoreaction initiator or an oxime ester-based photoreaction initiator. Both the acylphosphine oxide-based photoreaction initiator and the oxime ester-based photoreaction initiator have photobleaching properties in the vicinity of 380 nm, and the light transmittance is improved by irradiating light of the wavelength. ..

なお、フォトブリーチング(photobleaching)とは、光退色、光脱色とも書き、環境効果の一つで、励起蛍光分子でまれにみられる光化学的性質を指す。この反応は、励起状態にある蛍光物質が基底状態に比べて化学的に活性化され不安定になるために起こる。この反応の結果、蛍光分子が最終的に低蛍光性の構造に変化することを意味する。本実施形態に係る発明では、光反応開始剤が、ある紫外線領域において光を吸収し、ラジカルを発生させて紫外線硬化樹脂に重合を開始させる際に、ラジカル発生後の光反応開始剤の分子の共役結合が切断され、該紫外線領域における吸光度が低下することを、フォトブリーチングという。その結果、その紫外線領域における光を内部まで透過させることができるため、厚い膜であっても硬化をスムーズに進ませることができる。 Photobleaching is also described as photobleaching and photobleaching, and is one of the environmental effects, and refers to the photochemical properties rarely seen in excited fluorescent molecules. This reaction occurs because the excited fluorescent material is chemically activated and unstable compared to the ground state. As a result of this reaction, it means that the fluorescent molecule eventually changes to a low fluorescence structure. In the invention according to the present embodiment, when the photoinitiator absorbs light in a certain ultraviolet region and generates radicals to initiate polymerization on the ultraviolet curable resin, the molecule of the photoreaction initiator after radical generation is used. The fact that the conjugate bond is broken and the absorbance in the ultraviolet region decreases is called photobleaching. As a result, since the light in the ultraviolet region can be transmitted to the inside, the curing can proceed smoothly even with a thick film.

なお、α-アミノケトン系の光反応開始剤としては、例えば、260~340nmに強い吸収ピークを持つ2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、260~400nmに吸収ピークを持つ2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノンが挙げられる。市販品ではIRGACURE907、IRGACURE369、IRGACURE379(いずれも商品名、BASF社製)が挙げられる。 Examples of the α-aminoketone-based photoinitiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, which has a strong absorption peak at 260 to 340 nm, 260 to. 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1-, which has an absorption peak at 400 nm [4- (4-morpholinyl) phenyl] -1-butanone can be mentioned. Examples of commercially available products include IRGACURE907, IRGACURE369, and IRGACURE379 (trade names, all manufactured by BASF).

また、前記2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン(907)、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1(369)、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン(379)と、チオキサントン系増感剤として、260~410nmに吸収を持つ2,4-ジエチルチオキサントン(市販品としては、カヤキュアDETX-S(商品名、日本化薬社製))を併用することで、405nmにおける吸光係数(ε)が高くなり、より深部硬化に寄与し、より効率良く反応させることができる。 In addition, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- 1 (369), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (379) and a thioxanthone-based sensitizer. By using 2,4-diethylthioxanthone (commercially available, Kayacure DETX-S (trade name, manufactured by Nippon Kayaku Co., Ltd.)) having absorption at 260 to 410 nm, the absorption coefficient (ε) at 405 nm can be increased. It becomes higher, contributes to deeper curing, and can react more efficiently.

また、アシルフォスフィンオキサイド系の光反応開始剤としては、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイドが挙げられる。市販品ではLucirin-TPO、DAROCUR-TPOやIRGACURE819(いずれも商品名、BASF社製)を挙げることができる。 Examples of the acylphosphine oxide-based photoreaction initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Examples of commercially available products include Lucirin-TPO, DAROCUR-TPO, and IRGACURE819 (trade names, all manufactured by BASF).

これらの光反応開始剤は260~440nmに強い吸収ピークを持つため、LEDの波長では365nmよりは385nm及び395nmが有効である。さらに、アシルフォスフィンオキサイド系光反応開始剤は、分解により吸収がなくなるフォトブリーチング効果を示すため、表面だけではなく、深部の硬化度も高くすることができる。すなわち、アシルフォスフィンオキサイド系光反応開始剤は紫外線の照射開始時には長波長域(385nm付近)に吸収があるものの、光重合反応の進行とともに長波長域の吸収が消失する。そのため、光重合反応が進行すると深部まで紫外線が到達するようになり、深部の硬化度を高めることができる。 Since these photoinitiators have strong absorption peaks at 260-440 nm, LED wavelengths of 385 nm and 395 nm are more effective than 365 nm. Further, since the acylphosphine oxide-based photoreaction initiator exhibits a photobleaching effect in which absorption is eliminated by decomposition, it is possible to increase the degree of curing not only on the surface but also in the deep part. That is, although the acylphosphine oxide-based photoreaction initiator absorbs in the long wavelength region (near 385 nm) at the start of irradiation with ultraviolet rays, the absorption in the long wavelength region disappears as the photopolymerization reaction progresses. Therefore, as the photopolymerization reaction proceeds, the ultraviolet rays reach the deep part, and the degree of curing in the deep part can be increased.

なお、着色顔料や染料は、以下のものを使用することができる。シアニン化合物、フタロシアニン化合物、ナフトキノン化合物、ジインモニウム化合物、ナフタロシアニン化合物、スクアリウム色素、キノン系化合物、アゾ化合物、キナクリドン、ジオキザン、ベンスイミダゾロン、カーボンブラックなどを用いることができる。これらの成分は、その1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。着色した紫外線硬化樹脂の表面から深い部分を硬化させるのに有効な光反応開始剤は、例えばα-アミノケトン系光反応開始剤やアシルフォスフィンオキサイド系光反応開始剤である。前述したように、長波長域に吸収ピークを持つα-アミノケトン系光反応開始剤とチオキサントン系増感剤を加えることによって、長波長域(特に上述の405nm)の吸収ピークが高くなる。さらにアシルフォスフィンオキサイド系光反応開始剤を組み合わせることで、表面及び内部の硬化度を効率良く高くすることができる。 The following coloring pigments and dyes can be used. Cyanine compounds, phthalocyanine compounds, naphthoquinone compounds, diimmonium compounds, naphthalocyanine compounds, squalium dyes, quinone compounds, azo compounds, quinacridone, dioxane, bensuimidazolone, carbon black and the like can be used. One of these components may be used alone, or two or more thereof may be used in combination. An effective photoreaction initiator for curing a deep portion from the surface of the colored ultraviolet curable resin is, for example, an α-aminoketone-based photoreaction initiator or an acylphosphine oxide-based photoreaction initiator. As described above, by adding the α-aminoketone-based photoreaction initiator and the thioxanthone-based sensitizer having an absorption peak in the long wavelength region, the absorption peak in the long wavelength region (particularly the above-mentioned 405 nm) is increased. Further, by combining an acylphosphine oxide-based photoreaction initiator, the degree of curing on the surface and inside can be efficiently increased.

また、オキシムエステル系の光反応開始剤としては、1.2-オクタンジオン,1-[4-(フェニルチオ)-,2-(0-ベンゾイルオキシム)]、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(0-アセチルオキシム)が挙げられる。市販品ではIRGACURE OXE01やIRGACURE OXE02(いずれも商品名、BASF社製)を挙げることができるが、IRGACURE OXE01(商品名、BASF社製)はフォトブリーチング性を有する。 Examples of the oxime ester-based photoreaction initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (0-benzoyloxime)], etanone, 1- [9-ethyl-6. -(2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime) can be mentioned. Examples of commercially available products include IRGACURE OXE01 and IRGACURE OXE02 (both trade names, manufactured by BASF), but IRGACURE OXE01 (trade name, manufactured by BASF) has photobleaching properties.

このように、着色している紫外線硬化樹脂を表面から深い部分を硬化させるのに有効なα-アミノケトン系光反応開始剤にチオキサントン系増感剤を加えることで、長波長域(特に上述の405nm)の吸収ピークが高くすることができ、さらにアシルフォスフィンオキサイド系等の光反応開始剤を組み合わせてフォトブリーチングを利用することで、光を照射した表面から硬化が開始され、硬化した部位においては透過率が上昇するため、より深い部位まで光が到達し、短時間で被膜材17を硬化させることができる。 In this way, by adding a thioxanthone-based sensitizer to the α-aminoketone-based photoreaction initiator effective for curing a deep portion of the colored ultraviolet curable resin from the surface, a long wavelength region (particularly the above-mentioned 405 nm) is added. ) Can have a high absorption peak, and by using photobleaching in combination with a photoreaction initiator such as an acylphosphine oxide system, curing is started from the surface irradiated with light, and at the cured site. Since the transmittance increases, the light reaches a deeper part and the coating material 17 can be cured in a short time.

なお、前述したように、紫外線硬化樹脂の主反応はラジカル重合であり、紫外線の作用で、光反応開始剤が分解して生じたラジカルが変性アクリレートの二重結合を攻撃し、ラジカル重合が開始される。ベース樹脂は、変性アクリレートであって、エポキシ、ポリエステル、ウレタンなどの主鎖の両末端にアクリル基を付加させたもので、このアクリル基が紫外線により重合する反応基となる。また、紫外線硬化樹脂の主成分である変性アクリレートが持つ他の機能を付与することにより、紫外線が届き難い部分も紫外線照射と同時に硬化させたり、あるいは工程中に硬化させることができる。例えば、変性アクリレートは、紫外線硬化性と湿気硬化性、熱硬化性、嫌気硬化性をそれぞれ付与することが可能である。紫外線硬化と、湿気硬化乃至は、嫌気硬化、この両方の性質をバランスよく付与させることで、深部硬化性を付与することもできる。 As described above, the main reaction of the ultraviolet curable resin is radical polymerization, and the radical generated by the decomposition of the photoreaction initiator by the action of ultraviolet rays attacks the double bond of the modified acrylate to initiate radical polymerization. Will be done. The base resin is a modified acrylate in which acrylic groups are added to both ends of a main chain such as epoxy, polyester, or urethane, and the acrylic groups serve as reaction groups to be polymerized by ultraviolet rays. Further, by imparting other functions of the modified acrylate which is the main component of the ultraviolet curable resin, the portion where the ultraviolet rays are difficult to reach can be cured at the same time as the ultraviolet irradiation, or can be cured during the process. For example, the modified acrylate can impart ultraviolet curability, moisture curability, thermosetting, and anaerobic curability, respectively. Deep curability can also be imparted by imparting both properties of ultraviolet curing, moisture curing, or anaerobic curing in a well-balanced manner.

例えば、湿気硬化はシリコン変性アクリレートが好適に使用され、紫外線硬化終了後に、湿気によりさらに硬化させることができる。また、熱硬化は、熱硬化性のエポキシ変性アクリレートを併用することによって、紫外線を照射することによって、熱硬化しにくい樹脂表面を硬化させ、さらに加熱により、紫外線が届き難い部分を短時間で完全硬化させることができる。嫌気硬化については、金属イオンが介在する条件で、紫外線による硬化の際の照射熱による嫌気硬化促進や、紫外線硬化による表面部分の空気遮断により、比較的速やかに硬化が完了する。 For example, silicon-modified acrylate is preferably used for moisture curing, and can be further cured by moisture after UV curing is completed. In addition, thermosetting cures the surface of the resin that is difficult to heat cure by irradiating it with ultraviolet rays by using it in combination with a thermosetting epoxy-modified acrylate, and further heats it to completely cover the parts that are difficult to reach by ultraviolet rays in a short time. Can be cured. With regard to anaerobic curing, under the condition that metal ions intervene, curing is completed relatively quickly by promoting anaerobic curing by irradiation heat at the time of curing by ultraviolet rays and by blocking air on the surface portion by ultraviolet curing.

なお、母材樹脂に対する光反応開始剤の添加量は、0.5質量%以上3.0質量%以下であることが望ましい。光反応開始剤の添加量は、例えば紫外線吸収スペクトル分析で光反応開始剤の吸収波長を測定することで特定することができる。 The amount of the photoreaction initiator added to the base metal resin is preferably 0.5% by mass or more and 3.0% by mass or less. The amount of the photoreaction initiator added can be specified, for example, by measuring the absorption wavelength of the photoreaction initiator by ultraviolet absorption spectrum analysis.

また、本実施形態において、バレル間部8における表面部の被膜材17と、導線13の裏側における端子1の底面側の被膜材17との、赤外光吸収に基づき算出される硬化反応率の差は3%以内であることが望ましい。 Further, in the present embodiment, the curing reaction rate of the coating material 17 on the surface portion of the inter-barrel portion 8 and the coating material 17 on the bottom surface side of the terminal 1 on the back side of the conducting wire 13 is calculated based on infrared light absorption. The difference is preferably within 3%.

ここで、被膜材17の硬化反応率は、波長1506~1570cm-1に現れるピークを参照ピークとして、波数1407cm-1の赤外光吸収ピークを計測することにより以下のようにして測定することができる。 Here, the curing reaction rate of the coating material 17 can be measured as follows by measuring the infrared light absorption peak having a wave number of 1407 cm -1 with the peak appearing at a wavelength of 1506 to 1570 cm -1 as a reference peak. can.

用意した被膜材につき、FT-IR法による顕微ATR(Attenuated Total Reflection)測定によって紫外線硬化樹脂のアクリル二重結合反応率を測定し、その硬化反応率を評価する。ATR測定とは、試料よりも屈折率が大きい結晶を用いて試料に接触させ、赤外光を試料に入射し、試料に吸収され結晶で反射したスペクトルを測定する、試料の深さ方向に対する定量測定である。なお、屈折率の異なる結晶を使用することで、試料の深さ方向への潜り込み量を変更することができる。潜り込み量は、下式に示すスネルの法則を用いて算出することができる。 For the prepared coating material, the acrylic double bond reaction rate of the ultraviolet curable resin is measured by microscopic ATR (Attenuated Total Reflection) measurement by the FT-IR method, and the curing reaction rate is evaluated. ATR measurement is a quantitative measurement in the depth direction of a sample, in which a crystal having a higher refractive index than the sample is brought into contact with the sample, infrared light is incident on the sample, and the spectrum absorbed by the sample and reflected by the crystal is measured. It is a measurement. By using crystals having different refractive indexes, the amount of submergence of the sample in the depth direction can be changed. The amount of sneaking can be calculated using Snell's law shown in the following equation.

Figure 0007012415000001
Figure 0007012415000001

ここで、dpは潜り込み量、λは赤外光の波長、nは結晶の屈折率、nは試料の屈折率、θは赤外光の入射角である。式1から明らかなように、赤外光の波数とATR測定による潜り込み量の関係は使用する結晶に依存する。代表的なATR結晶の屈折率は、KRS-5:2.40、ZnSe:2.41、Ge:4.01、ダイヤモンド:2.37、Si:3.41である。ダイヤモンド結晶を用いてATR測定を行った場合、例えば波数1407cm-1において、潜り込み量は1.4μmとなる。波数810cm-1において、潜り込み量は2.4μmとなる。 Here, dp is the amount of diving, λ is the wavelength of infrared light, n 1 is the refractive index of the crystal, n 2 is the refractive index of the sample, and θ is the incident angle of infrared light. As is clear from Equation 1, the relationship between the wavenumber of infrared light and the amount of submergence by ATR measurement depends on the crystal used. The refractive index of a typical ATR crystal is KRS-5: 2.40, ZnSe: 2.41, Ge: 4.01, diamond: 2.37, Si: 3.41. When ATR measurement is performed using a diamond crystal, for example, at a wave number of 1407 cm -1 , the amount of submergence is 1.4 μm. At a wave number of 810 cm -1 , the amount of submergence is 2.4 μm.

FT-IR法による顕微ATR測定により、硬化後の表面及び深部のそれぞれから被膜材を取り出して評価する。FT-IR法による評価結果から、表面と深部のそれぞれの被膜材における、赤外光の吸収ピーク及び参照ピークを得ることができる。そしてこれら表面と深部の吸収ピーク及び参照ピークから、式2を用いて、表面と深部の反応率差を求めることができる。 By microscopic ATR measurement by the FT-IR method, the coating material is taken out from each of the surface and the deep part after curing and evaluated. From the evaluation results by the FT-IR method, it is possible to obtain an infrared light absorption peak and a reference peak in each of the surface and deep coating materials. Then, from these absorption peaks and reference peaks in the surface and the deep part, the reaction rate difference between the surface and the deep part can be obtained by using Equation 2.

硬化反応率差(%)
=(1-(SAbs./SRef.)/(DAbs./DRef.))×100 ・・・式2
但しSAbs.は、表面における被膜材の吸収ピーク、SRef.は、表面における被膜材の参照ピーク、DAbs.は、深部における被膜材の吸収ピーク、DRef.は、深部における被膜材の参照ピークである。
Curing reaction rate difference (%)
= (1- (S Abs. / S Ref. ) / (DA Abs. / D Ref. )) × 100 ... Equation 2
However, S Abs. Is the absorption peak of the coating material on the surface, S Ref. Is the reference peak of the coating material on the surface, D Abs. Is the absorption peak of the coating material in the deep part, and D Ref. Is the absorption peak of the coating material in the deep part. It is a reference peak.

赤外光吸収に基づき算出される硬化反応率の差が3%以内であれば、表面と深部との被膜材の硬化反応率にほとんど差がないため、耐サーマルショック性能を高めることができる。 When the difference in the curing reaction rate calculated based on the infrared light absorption is within 3%, there is almost no difference in the curing reaction rate between the surface and the deep portion of the coating material, so that the thermal shock resistance can be improved.

次に、端子付き電線10の製造方法について説明する。まず、図3に示すように、端子1と、被覆部15の先端部を剥離して導線13を露出させた被覆導線11を準備する。 Next, a method of manufacturing the electric wire 10 with a terminal will be described. First, as shown in FIG. 3, a coated conductor 11 is prepared by peeling off the terminal 1 and the tip of the coated portion 15 to expose the conductor 13.

次に、被覆導線11の導線13を導線圧着部7に配置し、被覆部15を被覆圧着部9に配置する。この際、被覆部15の先端部がバレル間部8に位置する。次に、導線13を導線圧着部7で圧着するとともに、被覆部15を被覆圧着部9で圧着し、被覆導線11と端子1とを圧着により接続する。 Next, the conductor 13 of the coated conductor 11 is arranged in the conductor crimping portion 7, and the covering portion 15 is arranged in the coated crimping portion 9. At this time, the tip end portion of the covering portion 15 is located at the barrel inter-barrel portion 8. Next, the conductor 13 is crimped by the wire crimping portion 7, the coated portion 15 is crimped by the coated crimping portion 9, and the coated conductor 11 and the terminal 1 are connected by crimping.

次に、少なくとも、バレル間部8から導線圧着部7までの導線13が露出する部位に被膜材17を例えばディスペンサ等で塗布して、硬化させる。以上により、端子付き電線10を得ることができる。 Next, at least the coating material 17 is applied to the exposed portion of the conductor wire 13 from the barrel inter-barrel portion 8 to the conductor wire crimping portion 7 with a dispenser or the like and cured. From the above, the electric wire 10 with a terminal can be obtained.

なお、塗布時の被膜材17の粘度は、300~3000mPa・sであることが望ましい。被膜材17の粘度が高すぎると、導線13に浸透させて、導線13の下部に被膜材17を浸透させることが困難となる。一方、被膜材17の粘度が低すぎると、塗布した被膜材17が流れてしまい、所望の厚みを確保することが困難となる。 The viscosity of the coating material 17 at the time of coating is preferably 300 to 3000 mPa · s. If the viscosity of the coating material 17 is too high, it becomes difficult to allow the coating material 17 to penetrate into the conducting wire 13 and to penetrate the lower portion of the conducting wire 13. On the other hand, if the viscosity of the coating material 17 is too low, the applied coating material 17 will flow, making it difficult to secure a desired thickness.

以上説明したように、本実施形態によれば、光反応開始剤として、アミノケトン系の第1光反応開始剤を含むため、着色剤などにより樹脂が着色している場合でも、効率良く硬化させることができるとともに、紫外線領域の光に対しフォトブリーチング性を有する第2光反応開始剤を含むため、光が照射されて硬化が開始すると、フォトブリーチングによって樹脂の吸光度が下がり、より深部まで光を到達させることができる。このように、本実施形態では、アミノケトン系の第1光反応開始剤と、フォトブリーチング性を有する第2光反応開始剤とを併用することで、例えば視認性のために着色している場合であっても、被膜材17の深部までを効率良く硬化させることができる。なお、本実施形態の被膜材17は、着色剤等の添加によって着色を行う場合以外にも、樹脂自体が有色の場合にも効果的であり、さらに、樹脂の変色等の可能性がある場合や、塗布時に着色される場合など、製造時や保管時においては無色透明である場合にも当然に有効である。 As described above, according to the present embodiment, since the photoreaction initiator contains an aminoketone-based first photoreaction initiator, even when the resin is colored by a colorant or the like, it can be efficiently cured. Since it contains a second photoreaction initiator that has photobleaching properties against light in the ultraviolet region, when light is applied and curing starts, the absorbance of the resin decreases due to photobleaching, and the light goes deeper. Can be reached. As described above, in the present embodiment, the aminoketone-based first photoreaction initiator and the second photoreaction initiator having photobleaching property are used in combination to, for example, colorize for visibility. Even so, it is possible to efficiently cure the deep portion of the coating material 17. The coating material 17 of the present embodiment is effective not only when coloring is performed by adding a colorant or the like, but also when the resin itself is colored, and when there is a possibility of discoloration of the resin or the like. Of course, it is also effective when it is colorless and transparent during manufacturing and storage, such as when it is colored at the time of application.

また、チオキサントン系増感剤を混合することで、アミノケトン系光反応開始剤の吸収波長を長波長側にシフトさせ、例えば、405nm近傍での吸収を高めることができる。このため、より波長の長い光源を使用して、被膜材17を硬化させることができるため、より深部まで光を到達させることができる。 Further, by mixing the thioxanthone-based sensitizer, the absorption wavelength of the aminoketone-based photoreaction initiator can be shifted to the long wavelength side, and the absorption in the vicinity of, for example, 405 nm can be enhanced. Therefore, the coating material 17 can be cured by using a light source having a longer wavelength, so that the light can reach a deeper part.

なお、本実施形態においては、被覆対象部材が、被覆導線11と端子1とが接続される端子付き電線10であり、被膜材17が、被覆対象部材である端子付き電線10に塗布されて硬化する例について説明したが、本発明はこれに限られない。防食や保護のために樹脂皮膜を形成し、より深い部位まで被膜材17を浸透させる必要があるような被覆対象部材であれば、被膜材17は、その他の分野にも利用可能である。例えば、光ファイバの被覆工程、電子部品や光ピックアップの樹脂塗布工程、プリントレジスト硬化工程、各種部材の貼り合せ時における樹脂塗布工程など、被覆対象部材に樹脂を塗布する工程であれば、いずれの分野でも利用可能である。 In the present embodiment, the member to be covered is the electric wire 10 with a terminal to which the coated conductor 11 and the terminal 1 are connected, and the coating material 17 is applied to the electric wire 10 with a terminal to be a member to be covered and cured. However, the present invention is not limited to this. The coating material 17 can also be used in other fields as long as it is a covering target member that needs to form a resin film for corrosion protection and protection and allow the coating material 17 to penetrate deeper into the portion. For example, any of the processes for applying resin to the member to be coated, such as an optical fiber coating process, a resin coating process for electronic parts and optical pickups, a print resist curing process, and a resin coating process when bonding various members. It is also available in the field.

次に、複数の被膜材を用いて端子付き電線を試作し、各試料について試験を行ったので以下に説明する。 Next, a prototype electric wire with a terminal was made using a plurality of coating materials, and each sample was tested. This will be described below.

前述したように、端子の圧着部で被覆導線を圧着し、導線の露出部に被膜材を塗布して硬化させた。この際、塗布する被膜材の種類や粘度を変えて、種々の端子付き電線を得た。各条件および結果を表1に示す。 As described above, the coated conductor was crimped at the crimping portion of the terminal, and the coating material was applied to the exposed portion of the conductor and cured. At this time, various electric wires with terminals were obtained by changing the type and viscosity of the coating material to be applied. Table 1 shows each condition and result.

Figure 0007012415000002
Figure 0007012415000002

表中の樹脂配合は、母材樹脂に混合する光反応開始剤等の種類を示し、アミノケトン系光反応開始剤としては、IRGACURE 379(商品名、BASF社製)を用い、チオキサントン系増感剤としては、カヤキュアDETX-S(商品名、日本化薬社製)を用い、アシルフォスフィンオキサイド系光反応開始剤としては、IRGACURE 379(表中A)及びLucirin-TPO9(表中B)(いずれも商品名、BASF社製)を用い、オキシムエステル系光反応開始剤としては、IRGACURE OXE01(商品名、BASF社製)を用いた。また、その他の光反応開始剤として、ヒドロキシケトン系光反応開始剤(IRGACURE 184(商品名、BASF社製))と、アルキフェノン系光反応開始剤(IRGACURE 1173(商品名、BASF社製))を用いた。なお、ドロキシケトン系光反応開始剤と、アルキフェノン系光反応開始剤は、紫外線領域におけるフォトブリーチング性は有さない。また、一部の樹脂には、着色剤としてPigment Red 122(キナクリドン) を2質量%配合して着色した。 The resin formulation in the table indicates the type of photoreaction initiator, etc. to be mixed with the base resin, and IRGACURE 379 (trade name, manufactured by BASF) is used as the aminoketone-based photoreaction initiator, and a thioxanthone-based sensitizer. KayaCure DETX-S (trade name, manufactured by Nippon Kayaku Co., Ltd.) was used as the initiator, and IRGACURE 379 (A in the table) and Lucirin-TPO9 (B in the table) were used as the acylphosphine oxide-based photoreactive initiators. Also used (trade name, manufactured by BASF), and IRGACURE OXE01 (trade name, manufactured by BASF) was used as the oxime ester-based photoreaction initiator. In addition, as other photoreaction initiators, a hydroxyketone-based photoreaction initiator (IRGACURE 184 (trade name, manufactured by BASF)) and an alkiferone-based photoreaction initiator (IRGACURE 1173 (trade name, manufactured by BASF)). Was used. The droxyketone-based photoreaction initiator and the alkiferone-based photoreaction initiator do not have photobleaching properties in the ultraviolet region. Further, some resins were colored by blending 2% by mass of Pigment Red 122 (quinacridone) as a colorant.

また、それぞれの波長によって被膜材を硬化させた端子付き電線を解体して、バレル間部における表面部及び深部の被膜材(バレル間部において表面部と、導線の裏側における端子底面側の被膜材)をそれぞれ採取し、FT-IR法による顕微ATR測定を行った。FT-IR法の顕微ATR測定用の装置として、VARIAN社(現Agilen Technologies社)の660/610IRを使用した。また、検出器として、銀・カドミウム・テルル化合物(MCT)検出器を使用した。測定条件として、スキャン速度を25kHz、入射角を45度、分解能を4cm-1、開口寸法を100μm×100μmに設定した。 In addition, the electric wire with a terminal whose coating material is hardened according to each wavelength is disassembled, and the coating material on the surface portion and the deep portion in the inter-barrel portion (the surface portion in the inter-barrel portion and the coating material on the bottom surface side of the terminal on the back side of the conducting wire). ) Was collected and microscopic ATR measurement was performed by the FT-IR method. As a device for microscopic ATR measurement of the FT-IR method, 660/610IR of VARIAN (currently Agilent Technologies) was used. In addition, a silver / cadmium / telluride compound (MCT) detector was used as the detector. As the measurement conditions, the scan speed was set to 25 kHz, the incident angle was set to 45 degrees, the resolution was set to 4 cm -1 , and the aperture size was set to 100 μm × 100 μm.

FT-IR法による評価結果から、表面と深部のそれぞれにおける、赤外光の吸収ピーク及び参照ピークを得て前述した式2を用いて、表面と深部での硬化度差(硬化反応率差)を求めた。硬化度差が3%以下の物を〇とし、3%を超え10%以下のものを△とし、10%を超えたものを×とした。 From the evaluation results by the FT-IR method, the absorption peak and the reference peak of infrared light were obtained on the surface and the deep part, respectively, and the above-mentioned formula 2 was used to obtain the difference in the degree of curing between the surface and the deep part (difference in curing reaction rate). Asked. Those having a curing degree difference of 3% or less were evaluated as ◯, those having a curing degree difference of more than 3% and 10% or less were evaluated as Δ, and those having a curing degree difference of more than 10% were evaluated as x.

また、それぞれの端子付き電線に対し、120℃×30分~-40℃×30分を1000サイクルとした冷熱衝撃試験を行い、冷熱衝撃試験後の端子付き電線について正圧でのシール性を評価した。なお、冷熱衝撃試験に供したサンプルは、385nmの光を照射して硬化させたものを用いた。 In addition, a cold shock test was conducted on each wire with terminals at 120 ° C x 30 minutes to -40 ° C x 30 minutes for 1000 cycles, and the sealing performance of the wire with terminals after the cold shock test was evaluated at positive pressure. did. The sample used for the thermal shock test was cured by irradiating it with light of 385 nm.

図4は、正圧試験方法の概要を示す。水を入れた水槽21中に端子付き電線10の一端を入れ、被覆導線11の端部から端子1に向かってレギュレータ22によって加圧空気を送った。なお、エア圧は49kPaとした。正圧でのシール性は、端子付き電線の被覆導線から端子に向かって空気を送り、端子1から空気が漏れるか否かについて評価した。 FIG. 4 shows an outline of the positive pressure test method. One end of the electric wire 10 with a terminal was put into a water tank 21 filled with water, and pressurized air was sent from the end of the coated conducting wire 11 toward the terminal 1 by a regulator 22. The air pressure was 49 kPa. The sealing property at positive pressure was evaluated as to whether or not air was sent from the coated conductor of the electric wire with a terminal toward the terminal and air leaked from the terminal 1.

表中の「冷熱試験後の正圧試験」は、前述した冷熱衝撃試験後の正圧試験において漏れのなかったものを〇とし、一部にでも漏れがあったものを×とした。 In the "positive pressure test after the cold test" in the table, those having no leakage in the positive pressure test after the above-mentioned cold impact test were marked with ◯, and those with some leaks were marked with x.

また、それぞれの端子付き電線について、被膜材硬化後の「視認性」について確認を行った。被膜材で導線が完全に被覆されていることを容易に把握できたものを〇とし、被膜材の有無が分かりにくいものを×とした。 In addition, we confirmed the "visibility" of each electric wire with terminals after the coating material was cured. Those in which it was easy to grasp that the conducting wire was completely covered with the coating material were marked with ◯, and those in which the presence or absence of the coating material was difficult to understand were marked with x.

総合評価としては、冷熱試験後の正圧試験と視認性の両方の項目で〇のものを、〇評価とし、視認性と冷熱試験後の正圧試験のいずれかが×のものを×評価とした。 As a comprehensive evaluation, 〇 is evaluated for both the positive pressure test and visibility after the cold test, and x is evaluated for either the visibility or the positive pressure test after the cold test. did.

結果より、フォトブリーチング性を有する光反応開始剤とアミノケトン系光反応開始剤とチオキサントン系増感剤を含む実施例1~3は、着色されていても、冷熱試験後の正圧試験が〇となり、着色されているため視認性も〇となり、総合評価で〇となった。これは、フォトブリーチング性を有する光反応開始剤による効果と、着色されていてもその影響を受けにくいアミノケトン系光反応開始剤の吸収波長を長波長側にシフトさせた効果とで、特に長波長側の光の照射によって深部まで硬化することができたためである。 From the results, in Examples 1 to 3 containing a photochemical initiator, an aminoketone-based photoreaction initiator, and a thioxanthone-based sensitizer, even if they were colored, the positive pressure test after the cold test was 〇. Because it was colored, the visibility was 〇, and the overall evaluation was 〇. This is particularly long due to the effect of the photochemical initiator having photobleaching property and the effect of shifting the absorption wavelength of the aminoketone-based photoreaction initiator, which is not easily affected by it even if it is colored, to the longer wavelength side. This is because it was possible to cure deeply by irradiating light on the wavelength side.

一方、フォトブリーチング性を有する光反応開始剤のみである比較例1~4においては、着色されている場合(比較例1、3、4)では、冷熱試験後の正圧試験が×であり、着色されていない場合(比較例2)では、視認性が×となった。これは、樹脂が着色されていない場合には、フォトブリーチング効果によって、深部まで硬化が十分に進むが、着色があると、アミノケトン系光反応開始剤と比較して、その影響を受けやすいため、深部の硬化が若干弱くなったものと考えられる。 On the other hand, in Comparative Examples 1 to 4, which are only photoreaction initiators having photobleaching properties, in the case of being colored (Comparative Examples 1, 3 and 4), the positive pressure test after the cold test is ×. In the case of not being colored (Comparative Example 2), the visibility was x. This is because when the resin is not colored, the photobleaching effect sufficiently promotes curing to a deep part, but when it is colored, it is more susceptible to the effect than the aminoketone-based photoreaction initiator. It is probable that the hardening in the deep part was slightly weakened.

また、アミノケトン系の光反応開始剤のみである比較例5~7においては、着色の有無によらず、冷熱試験後の正圧試験が×であった。これは、フォトブリーチング性を有する光反応開始剤と比較すると、アミノケトン系の光反応開始剤のみでは、深部硬化性が低いためである。なお、詳細は割愛するが、チオキサントン系の増感剤を添加することで、硬化度差の数値は小さくなり、深部硬化性は改善された。 Further, in Comparative Examples 5 to 7 in which only the aminoketone-based photoreaction initiator was used, the positive pressure test after the cold test was x regardless of the presence or absence of coloring. This is because the deep curability is lower only with the aminoketone-based photoreaction initiator as compared with the photoreaction initiator having photobleaching property. Although details are omitted, the addition of a thioxanthone-based sensitizer reduced the value of the difference in the degree of curing and improved the deep curability.

また、アミノケトン系光反応開始剤を用いずに、フォトブリーチング性を有さない光反応開始剤のみである比較例8~9は、いずれの波長でも、表面と深部での硬化度差が10%を超え、深部まで硬化が進んでいない結果となった。 Further, in Comparative Examples 8 to 9, which are only photoreaction initiators having no photobleaching property without using an aminoketone-based photoreaction initiator, the difference in curing degree between the surface and the deep part is 10 at any wavelength. The result was that the curing did not proceed to the deep part, exceeding%.

以上、添付図を参照しながら、本発明の実施の形態を説明したが、本発明の技術的範囲は、前述した実施の形態に左右されない。当業者であれば、特許請求の範囲に記載された技術的思想の範疇内において各種の変更例または修正例に想到し得ることは明らかであり、それらについても当然に本発明の技術的範囲に属するものと了解される。 Although the embodiments of the present invention have been described above with reference to the attached drawings, the technical scope of the present invention does not depend on the above-described embodiments. It is clear that a person skilled in the art can come up with various modifications or modifications within the scope of the technical ideas described in the claims, and these are naturally within the technical scope of the present invention. It is understood that it belongs to.

1………端子
3………端子本体
4………トランジション部
5………圧着部
7………導線圧着部
8………バレル間部
9………被覆圧着部
10……端子付き電線
11………被覆導線
13………導線
15………被覆部
17………被膜材
21………水槽
22………レギュレータ
103………導線
107………導線圧着部
108………バレル間部
109………被覆圧着部
111………被覆導線
115………被覆部
117………樹脂部材
1 ………… Terminal 3 ………… Terminal body 4 ………… Transition part 5 ………… Crimping part 7 ………… Conductor crimping part 8 ………… Barrel-to-barrel part 9 ………… Covered crimping part 10 …… Wire with terminal 11 ………… Covered lead wire 13 ………… Lead wire 15 ………… Covered part 17 ………… Coating material 21 ………… Water tank 22 ………… Regulator 103 ………… Lead wire 107 ………… Lead wire crimping part 108 ………… Barrel Inter-covered part 109 ………… Covered crimping part 111 ………… Covered conductor 115 ………… Covered part 117 ………… Resin member

Claims (2)

被覆材が、被覆対象部材に塗布されて硬化している樹脂被膜構造において、前記被覆対象部材が被覆導線と端子とが接続された端子付き電線であって、
前記被覆導線は、被覆部と、前記被覆部の先端から露出する導線とを具備し、
前記端子は、端子本体と圧着部とを有し、前記圧着部は、前記導線が圧着される導線圧着部と、前記被覆部が圧着される被覆圧着部と、前記導線圧着部と前記被覆圧着部との間のバレル間部と、を具備し、少なくとも、前記バレル間部から前記導線圧着部までの前記導線が露出する部位が前記被膜材で覆われており、
前記被覆材は、母材の樹脂に光反応開始剤が添加されており、
前記光反応開始剤は、紫外線領域の光を照射することによってラジカルを発生するアミノケトン系の第1光反応開始剤と、紫外線領域の光に対しフォトブリーチング性を有する第2光反応開始剤とを含み、
前記第1光反応開始剤は、365nm~405nmの波長領域の光を照射することでラジカルを発生し、
前記第2光反応開始剤は、アシルフォスフィンオキサイド系光反応開始剤または、オキシムエステル系光反応開始剤の少なくとも一方を含み、
紫外線領域の光で励起され、前記第1光反応開始剤に電子供与することで、365nm~405nmでのラジカル発生を増強するチオキサントン系増感剤を含むことを特徴とする端子付き電線。
In a resin coating structure in which a covering material is applied to a covering target member and cured , the covering target member is an electric wire with a terminal in which a coated conductor and a terminal are connected.
The coated conductor includes a coated portion and a conductor exposed from the tip of the coated portion.
The terminal has a terminal body and a crimping portion, and the crimping portion includes a conductor crimping portion to which the conductor is crimped, a coated crimping portion to which the coated portion is crimped, and the conductor crimping portion and the coated crimping portion. It is provided with a barrel-to-barrel portion between the portions, and at least a portion from the barrel-to-barrel portion to the conductor crimping portion where the conductor is exposed is covered with the coating material.
The coating material has a photoreaction initiator added to the resin of the base material.
The photoreaction initiator includes an aminoketone-based first photoreaction initiator that generates radicals by irradiating light in the ultraviolet region and a second photoreaction initiator having photobleaching property with respect to light in the ultraviolet region. Including
The first photoreaction initiator generates radicals by irradiating light in a wavelength region of 365 nm to 405 nm.
The second photoreaction initiator contains at least one of an acylphosphine oxide-based photoreaction initiator or an oxime ester-based photoreaction initiator.
An electric wire with a terminal , which is excited by light in the ultraviolet region and contains a thioxanthone-based sensitizer that enhances radical generation in 365 nm to 405 nm by donating electrons to the first photoreaction initiator .
前記バレル間部において表面部の前記被膜材と、前記導線の裏側における端子底面側の前記被膜材との、赤外光吸収に基づき算出される硬化反応率の差が3%以内であることを特徴とする請求項に記載の端子付き電線。 The difference in the curing reaction rate calculated based on infrared light absorption between the coating material on the surface portion and the coating material on the bottom surface side of the terminal on the back side of the conducting wire in the inter-barrel portion is within 3%. The electric wire with a terminal according to claim 1 .
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