JP2004071448A - Holder for waterproof connector, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new holder for a waterproof connector allowing a packing part formed of a gel material to be easily integrally molded by insert molding by using a rear holder part formed of a resin as an insert, and causing little compression set without generating inconvenience in molding. <P>SOLUTION: This holder for a waterproof connector is composed by integrating a packing part formed of a gel material and having a packing part terminal insertion hole for inserting a wire with a terminal inserted into the waterproof connector with a holder part having a holder part terminal insertion hole for inserting the wire with the terminal into the waterproof connector and used for keeping the packing part in the waterproof connector. <P>COPYRIGHT: (C)2004,JPO

Description

【００５２】
［実施例２］
粘度１００００ｍＰａ・ｓの分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン１００重量部、およびジメチルジクロロシランで表面処理されたＢＥＴ比表面積２００ｍ^２／ｇのヒュームドシリカ２０重量部を混合した後、減圧下、加熱混合して液状シリコーンゲルベースを調製した。
【００５３】
次に、この液状シリコーンゲルベース１２０重量部、粘度１００ｍＰａ・ｓの分子鎖両末端トリメチルシロキシ基封鎖ジメチルポリシロキサン１４０重量部、粘度５ｍＰａ・ｓの分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体（上記シリコーンゲルベースに含まれているジメチルポリシロキサン中のビニル基１モルに対して、ケイ素原子結合水素原子が１．４モルとなる量）、白金の１，３−ジビニルテトラメチルジシロキサン錯体（上記シリコーンゲルベース中のジメチルポリシロキサン１００万重量部に対して、白金金属が３５重量部となる量）、３，５−ジメチル−１−ヘキシン−３−オール０．１２重量部、およびフタロシアニン銅微粉末１重量部を混合してシリコーンゲル組成物を調製した。
【００５４】
このシリコーンゲル組成物を硬化して得られるシリコーンゲルのアスカーＣ硬度、および圧縮永久ひずみ、及び、また実施例１で用いたものと同じ２種のリアホルダ部をそれぞれインサートとしてパッキング部と一体となった防水コネクタ用ホルダを成形してその金型離型性及びリアホルダ部との接着性を次のようにして評価した。それらの結果を表２に示した。
【００５５】
［金型離型性］
シリコーンゲル組成物を、実施例１で用いたものと同じポリブチレンテレフタレート樹脂製及びポリエチレンテレフタレート樹脂製の２種のリアホルダ部をそれぞれインサートとして、図２に示したようなゲル状材からなるパッキング部と一体となった防水コネクタ用ホルダが得られるキャビティを有するクロームメッキした鋼鉄製の金型中に注型し、１２０℃、１０分の条件で硬化させた。得られたこれら防水コネクタ用ホルダを金型から取り出す際に、その取り出しが容易かどうかを評価した。
【００５６】
［アスカーＣ硬度］
プレス硬化（１次加硫）後のシリコーンゲルの硬さをアスカーＣ硬度計により測定した。
［圧縮永久ひずみ］
シリコーンゲル組成物を１２０℃、１０分の条件で硬化させ、ＪＩＳ　Ｋ　６２４９に規定の方法に準じた圧縮永久ひずみ測定用テストピースを作製した。次に、これをＪＩＳ　Ｋ　６２４９に規定の方法に準じて、１５０℃で７０時間圧縮した際の圧縮永久ひずみを測定した。
【００５７】
［比較例３］
実施例２と同様にして調製した液状シリコーンゲルベース１２０重量部、粘度１００００ｍＰａ・ｓの分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン１００重量部、粘度５ｍＰａ・ｓの分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体（上記シリコーンゲルベースに含まれているジメチルポリシロキサン中のビニル基１モルに対して、ケイ素原子結合水素原子が０．６モルとなる量）、白金の１，３−ジビニルテトラメチルジシロキサン錯体（上記シリコーンゲルベース中のジメチルポリシロキサン１００万重量部に対して、白金金属が１０重量部となる量）、３，５−ジメチル−１−ヘキシン−３−オール０．１重量部、およびフタロシアニン銅微粉末１重量部を混合してシリコーンゲル組成物を調製した。
【００５８】
実施例２と同様にして、このシリコーンゲル組成物を硬化して得られるシリコーンゲルのアスカーＣ硬度、および圧縮永久ひずみを測定して、それらの結果を表２に併せて示した。
【００５９】
［比較例４］
実施例２と同様にして調製した液状シリコーンゲルベース１２０重量部、粘度１００ｍＰａ・ｓの分子鎖両末端トリメチルシロキシ基封鎖ジメチルポリシロキサン５０重量部、粘度５ｍＰａ・ｓの分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体（上記シリコーンゲルベースに含まれているジメチルポリシロキサン中のビニル基１モルに対して、ケイ素原子結合水素原子が０．９モルとなる量）、白金の１，３−ジビニルテトラメチルジシロキサン錯体（上記シリコーンゲルベース中のジメチルポリシロキサン１００万重量部に対して、白金金属が１０重量部となる量）、３，５−ジメチル−１−ヘキシン−３−オール０．１重量部、およびフタロシアニン銅微粉末１重量部を混合してシリコーンゲル組成物を調製した。
【００６０】
実施例２と同様にして、このシリコーンゲル組成物を硬化して得られるシリコーンゲルの金型離型性、アスカーＣ硬度、および圧縮永久ひずみを測定し、また実施例１で用いたものと同じポリブチレンテレフタレート樹脂製のリアホルダ部をインサートとしてパッキング部と一体となった防水コネクタ用ホルダを成形してその金型離型性及びリアホルダ部との接着性を評価した。それらの結果を表２に併せて示した。
【００６１】
【表２】

【００６２】
［コネクタとしての耐久性評価］
実施例１の防水コネクタ用ホルダ（ポリブチレンテレフタレート製リアホルダ部使用のもの）と、これと同形状で、同材質のリアコネクタ部と従来技術に係るシリコーンゲル（レイケム社製）とからなるパッキング部を有する防水コネクタ用ホルダとを用いて、熱履歴前後の防水性を評価した。
【００６３】
図６に示すように防水コネクタハウジングβにこれら防水コネクタ用ホルダをセットし、電線付端子γを挿入した。このとき、１回のみ端子を挿入したサンプルと、端子を挿入後さらに抜き挿しを繰り返し計５回挿入したサンプルを作製した。
また、防水コネクタハウジングβの相手方コネクタとの接合側にエアチューブを挿した後、樹脂で水密に封止した。
【００６４】
これらを水中に沈め、エアチューブから圧縮空気を導入したときに電線とパッキン部との間から空気の漏れが生じる内部の圧力を調べた。なお、このときの圧力２００ｋＰａ以上であれば充分な防水性があると判断される。
これら防水性を調べた後、１２０時間、１５０℃の環境で熱履歴を与え、再度防水性を調べた。結果を表３に併せて示す。
【００６５】
【表３】

【００６６】
表３より、少なくとも（Ａ）１分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン１００重量部、（Ｂ）１分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサンを（Ａ）成分中のアルケニル基１モルに対して、（Ｂ）成分中のケイ素原子結合水素原子が０．５モル以上１０モル以下となる量、（Ｃ）分子中にアルケニル基およびケイ素原子結合水素原子を有さないオルガノポリシロキサン１００重量部以上５００重量部以下、および（Ｄ）白金系硬化用触媒、の４種の原料からなる有するシリコーン組成物を硬化させてなるゲル状のパッキング部を一体に有する実施例１に係る防水コネクタ用リアホルダを用いた場合に端子付電線の挿入を繰り返しても高い防水性を得ることができ、また、熱履歴を受けた後でも高い防水性が維持されることが判る。
【００６７】
【発明の効果】
本発明の防水コネクタ用ホルダはゲル状材からなり、防水コネクタ内に挿入される端子付電線が貫通するパッキング部端子挿入孔を有するパッキング部と、防水コネクタ内に挿入される端子付電線が貫通するホルダ部端子挿入孔を有しかつ上記パッキング部を防水コネクタ内に保持するホルダ部とが一体となっている防水コネクタ用ホルダであり、このようなパッキング部及びホルダ部とが一体となった構造により、従来必要であったパッキングの拘束層が不要となり、パッキングの製作が容易に、かつ、安価で済み、さらに、パッキング部端子挿入孔とホルダ部端子挿入孔とが確実に一致しているために、これら端子挿入口の間にずれが生じることがなく、さらに、このような防水コネクタ用ホルダを防水コネクタハウジングにセットした場合にも、パッキング部端子挿入孔と防水コネクタハウジングの端子収納室とが一致してセットされるため、これら中心が互いにずれて生じる問題が全て解決されるとともに、パッキング部とホルダ部とが予め一体となっているために防水コネクタの組立が極めて容易におこなうことができる。
【図面の簡単な説明】
【図１】本発明の防水コネクタ用ホルダの一例を用いる防水コネクタの組立イメージを示すモデル斜視図である。
【図２】本発明の防水コネクタ用ホルダの一例の組立過程における端子挿入口の状態を示すモデル断面図である。
【図３】本発明の防水コネクタ用ホルダの一例を成形する工程を示すモデル断面図である。
【図４】本発明の防水コネクタ用ホルダの一例を成形する工程を示すモデル断面図である。
【図５】従来技術に係る防水コネクタ用ホルダの一例を用いる防水コネクタの組立イメージを示すモデル斜視図である。
【図６】従来技術に係る防水コネクタにおける問題点を説明するモデル断面図である。
【符号の説明】
１　リアホルダ部
１ａ　ホルダ部端子挿入孔
２　パッキング部
α　本発明に係る防水コネクタ用ホルダ
β　防水コネクタハウジング
γ　端子付電線
３ａ　下金型
３ａ_１　パッキング部端子挿入孔形成ピン
３ｂ　中金型
３ｃ　上金型[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a packing portion made of a gel-like material for water-tightly sealing an opening on a wire side end of a waterproof connector in which a terminal portion of a wire with a terminal is inserted, which is used for a waterproof connector for automobiles and the like. The present invention relates to a waterproof connector holder to be used.
[0002]
[Prior art]
Various waterproof structures have been proposed for the waterproof structure at the wire side end of the wire with terminal inserted inside the waterproof connector.
For example, a technique of sealing with a resin, a technique of waterproofing using rubber packing using elasticity, and the like have been known.
[0003]
Among them, a technique using a gel-like material is proposed in Japanese Patent Publication No. Hei 6-501341. In this method, a packing material in which a gel material is arranged between two constraining layers is set and used in a box-shaped rear holder. In this case, if a gel material made of silicone is used, excellent properties such as vibration absorption, electrical properties, heat resistance, and water resistance can be obtained. These properties are particularly advantageous for waterproof connectors for automobiles, which have particularly large vibrations and are liable to undergo heat history in an engine room or the like.
[0004]
However, according to this technique, since the rear holder and the packing material are not integrated, the number of steps for assembling the connector increases, and the packing material itself is made of three members, which is expensive. was there.
[0005]
[Problems to be solved by the invention]
Therefore, the present inventors have developed a packing (reference numeral 2 in FIG. 1) made of a resin-made holder (a model perspective view of one example (rear holder) is shown with reference numeral 1 'in FIG. 5). ') Was used in combination.
[0006]
A packing 2 'is set in a waterproof connector housing (a model perspective view of FIG. 5 is denoted by reference numeral β, and reference numeral γ is an electric wire with a terminal in FIG. 5), and a rear holder 1' is set. Hold the packing 2 'in the waterproof connector.
[0007]
According to such a method, there is an advantage that the process of assembling the waterproof connector does not increase, and the constraining layer required in the technique described in Japanese Patent Application Laid-Open No. 6-501341 is unnecessary and the number of members can be reduced. Was done.
[0008]
However, it has been found that when the packing 2 'made of the gel material as described above is actually set in the connector housing γ, an unexpected problem occurs.
[0009]
As shown in FIG. 6, when the packing 2 ′ made of a silicone gel material is set in the waterproof connector housing β, the packing 2 ′ is very soft and sticky, so that the center is originally The terminal storage chamber βa in the waterproof connector housing β to be matched and the terminal insertion hole of the packing 2 ′ may be shifted and set. As a result, the center is similarly shifted between the terminal storage chamber βa in the waterproof connector housing β and the terminal insertion hole 1a ′ of the rear holder 1 ′.
[0010]
Here, the terminal insertion hole of the packing 2 ′ is thinner than the terminal portion of the terminal-attached electric wire so that the terminal insertion hole is in close contact with the wire covering portion of the terminal-attached electric wire after terminal insertion to form a watertight structure. In the case where the terminal storage chamber βa is displaced between the terminal insertion hole 1a ′ of the rear holder 1 ′ and the terminal insertion port 2a ′ of the packing 2 ′, the terminal is inserted into the terminal storage chamber βa in the waterproof connector housing β. Even if it is not possible, or if it is inserted, the packing is damaged by the metal terminal of the wire with terminal at the time of insertion, so that a sufficient waterproof effect cannot be obtained, or shavings generated as a result of the packing being cut by the terminal However, there arises a problem that the electrical connection with the mating connector is obstructed.
[0011]
[Means for Solving the Problems]
In order to solve the above-mentioned problem, a waterproof connector holder according to the present invention is, as described in claim 1, formed of a gel-like material and has a packing part terminal insertion hole through which a terminal-equipped wire inserted into the waterproof connector penetrates. And a holder unit having a terminal insertion hole through which an electric wire with a terminal inserted into the waterproof connector penetrates, and a holder unit for holding the packing unit in the waterproof connector. . Such a structure in which the packing portion and the holder portion are integrated eliminates the need for a constraining layer of the packing, which was conventionally required, making the packing easy and inexpensive. Since the hole and the holder terminal insertion hole surely coincide with each other, there is no deviation between the terminal insertion holes, and further, when such a waterproof connector holder is set in the waterproof connector housing. Also, since the packing section terminal insertion hole and the terminal storage chamber of the waterproof connector housing are set so as to coincide with each other, all the problems that occur when these centers are shifted from each other are solved, and the packing section and the holder section are integrally formed in advance. As a result, the waterproof connector can be assembled very easily.
[0012]
In the above-mentioned waterproof connector holder, the packing portion of the waterproof connector holder is formed by inserting a preformed molded holder portion as an insert through a holder terminal insertion hole of the holder portion. Molded using a mold that has a pin for forming a packing part terminal insertion hole that protrudes into the cavity, making it easy to manufacture and preventing packing molding gel from entering the holder part terminal insertion port. In addition, since the formation of gel at an unnecessary portion is prevented, it is possible to insert the terminal surely in the case of the waterproof connector, and it is possible to perform the reliable electric connection in the case of the waterproof connector.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
In the waterproof connector holder of the present invention, the holder portion has a holder portion terminal insertion hole through which an electric wire with a terminal inserted into the waterproof connector housing penetrates, and plays a role of holding the packing portion in the waterproof connector, Further, it is possible to prevent the packing made of the soft gel material from being set in the waterproof connector housing in a distorted form (a state in which a gap is generated between the terminal storage chamber and the packing section terminal insertion hole). .
[0014]
In order to obtain such an effect, it is necessary that the packing part and the holder part are integrated. For this purpose, the packing part has a sufficiently high adhesiveness to the holder part and may be integrated by the adhesiveness, or they may be integrated by means of adhesion, fusion or the like. Is also good.
In the case of a method such as adhesion and fusion, it is common to separately create a packing portion and a holder portion, and then perform adhesion or fusion. At this time, a terminal insertion hole between the packing portion and the holder portion is used. It is necessary to perform bonding or fusion so that the values match, and as described above, the packing portion made of a gel-like material is easily deformed, which makes the operation difficult.
[0015]
Also, the packing part and the holder part may be integrated by a fitting structure that fits each other, but the size of the holder part is generally small, and the packing part is made of a gel material having relatively low strength and rigidity. In many cases, a sufficient integration effect cannot be obtained.
In view of the above method, the packing portion of the waterproof connector holder is formed with a preformed holder portion as an insert, and the packing portion terminal insertion hole is formed to penetrate the holder portion terminal insertion hole of the holder portion and protrude into the packing portion forming cavity. The holder portion and the packing portion are integrally insert-molded using a mold having pins (hereinafter, also referred to as “holder insert / integral molding method”), so that the packing portion terminal insertion hole and the holder portion terminal insertion hole are reliably formed. Does not occur between these terminal insertion ports.
In the holder insert / integral molding method, the resin used for the holder portion is a resin having excellent adhesion to the silicone gel material forming the packing portion, and the molding conditions when performing the insert molding of the packing portion. Must be a resin having sufficient heat resistance.
[0016]
Examples of such a resin include ordinary olefin polymerization thermoplastic resins and condensation polymerization thermoplastic resins, and specifically, ABS (acrylonitrile-butadiene-styrene copolymer) resin, styrene resin, polyethylene resin, and polypropylene. It may be a resin, an acrylic resin, a polycarbonate resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyphenylene oxide resin, a polyphenylene sulfide resin, a polystyrene resin, a polyamide (nylon) resin, a liquid crystal resin, or a mixture thereof.
[0017]
The gel material used to form the packing portion used in such a holder insert / integral molding method must have extremely good adhesion to the holder portion and be easily released from the mold. is there.
[0018]
Examples of the gel material forming such a packing portion include (A) 100 parts by weight of an organopolysiloxane having at least two alkenyl groups in one molecule, and (B) at least two silicon atoms in one molecule. The amount of the organopolysiloxane having an atom-bonded hydrogen atom is such that the silicon-bonded hydrogen atom in the component (B) is 0.5 mol or more and 10 mol or less per 1 mol of the alkenyl group in the component (A), (C A) a silicone composition comprising four kinds of raw materials: 100 parts by weight or more and 500 parts by weight or less of an organopolysiloxane having no alkenyl group and no silicon-bonded hydrogen atom in the molecule; and (D) a platinum-based curing catalyst. And those obtained by curing.
[0019]
The organopolysiloxane of the component (A) used in the above silicone composition is a main component of the silicone composition and needs to have at least two alkenyl groups in one molecule.
[0020]
Here, examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. Examples of the organic group bonded to a silicon atom other than the alkenyl group in the component (A) include an alkyl group such as a methyl group, an ethyl group and a propyl group; an aryl group such as a phenyl group and a tolyl group; Examples include a halogenated alkyl group such as a 3-trifluoropropyl group. The molecular structure of the component (A) includes, for example, linear, partially branched linear, branched, reticulated, and dendritic. The viscosity of the component (A) at 25 ° C. is not limited, but is preferably in the range of 100 to 1,000,000 mPa · s.
[0021]
Examples of such an organopolysiloxane of the component (A) include dimethylpolysiloxane having dimethylvinylsiloxy groups at both ends of molecular chains, dimethylsiloxane / methylvinylsiloxane copolymer having dimethylvinylsiloxy groups at both ends of molecular chains, and molecular chains. Trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends, formula: (CH ₃ ) ₃ SiO _{l / 2} And a siloxane unit represented by the formula: (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 And a siloxane unit represented by the formula: SiO _4/2 An organopolysiloxane comprising a siloxane unit represented by the formula: an alkyl group such as an ethyl group and a propyl group; a aryl group such as a phenyl group and a tolyl group; -An organopolysiloxane substituted with a halogenated alkyl group such as a trifluoropropyl group, an organopolysiloxane in which part or all of the vinyl groups of these organopolysiloxanes are substituted with an alkenyl group such as an allyl group or a propenyl group, and the like. And mixtures of two or more of these organopolysiloxanes.
[0022]
The organopolysiloxane of the component (B) used in the above silicone composition is a curing agent and needs to have at least two silicon-bonded hydrogen atoms in one molecule.
[0023]
Examples of the organic group bonded to the silicon atom in the component (B) include, for example, an alkyl group such as a methyl group, an ethyl group, and a propyl group; an aryl group such as a phenyl group and a tolyl group; And a halogenated alkyl group such as a group. The molecular structure of the component (B) may be, for example, linear, partially branched linear, branched, reticulated, or dendritic. The viscosity of the component (B) at 25 ° C is not limited, but is preferably in the range of 1 to 1,000,000 mPa · s.
[0024]
Examples of the organopolysiloxane of the component (B) include dimethylpolysiloxane having dimethylhydrogensiloxy groups at both ends of molecular chains, methylhydrogenpolysiloxane having trimethylsiloxy groups at both ends of molecular chains, and trimethylsiloxy at both ends of molecular chains. Group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, cyclic methylhydrogenpolysiloxane, Formula: (CH ₃ ) ₂ HSi0 _1/2 And a siloxane unit represented by the formula: SiO _4/2 An organopolysiloxane comprising a siloxane unit represented by the formula: an alkyl group such as an ethyl group and a propyl group; a aryl group such as a phenyl group and a tolyl group; -Organopolysiloxanes substituted with halogenated alkyl groups such as trifluoropropyl groups, and mixtures of two or more of these organopolysiloxanes.
[0025]
In the silicone composition used in the present invention, the content of the component (B) is such that the silicon-bonded hydrogen atom in the component (B) is 0.5 to 10 mol per 1 mol of the alkenyl group in the component (A). The amount falls within the range, preferably the amount falls within the range of 1.0 to 5.0 mol. This is because if the content of the component (B) is less than the lower limit of the above range, the resulting silicone gel composition tends to be insufficiently cured, while if the content exceeds the upper limit of the above range, This is because the obtained silicone gel has a strong adhesiveness to the mold, and the mold releasability tends to decrease.
[0026]
The organopolysiloxane (C) is used to improve the mold release properties of the silicone gel obtained by curing the above silicone composition composition, and to provide sufficient flexibility while keeping the compression set low. And must have no alkenyl group and no silicon-bonded hydrogen atom in the molecule.
[0027]
Examples of the organic group bonded to the silicon atom in the component (C) include an alkyl group such as a methyl group, an ethyl group, and a propyl group; an aryl group such as a phenyl group and a tolyl group; and 3,3,3-trifluoropropyl. And a halogenated alkyl group such as a group.
[0028]
The molecular structure of the component (C) includes, for example, linear, partially branched linear, branched, and cyclic. The viscosity of the component (C) at 25 ° C. is not limited, but is preferably in the range of 50 to 50,000 mPa · s.
This is because if the viscosity of the component (C) is less than the lower limit of the above range, it tends to volatilize from the obtained silicone gel. This is because the adhesion to the mold tends to increase.
[0029]
Examples of the organopolysiloxane of the component (C) include dimethylpolysiloxane having trimethylsiloxy groups at both ends of molecular chains, dimethylsiloxane / methylphenylsiloxane copolymer having trimethylsiloxy groups at both ends, and both ends of molecular chains. Trimethylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer, molecular chain terminal dimethylphenylsiloxy group-blocked dimethylpolysiloxane, molecular chain terminal dimethylphenylsiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, and organopolysiloxanes thereof Mixtures of two or more siloxanes are included.
[0030]
In the above silicone composition, the content of the component (C) is in the range of 100 to 500 parts by weight, preferably 100 to 300 parts by weight, per 100 parts by weight of the component (A). This is because if the content of the component (C) is less than the lower limit of the above range, the mold release property of the obtained silicone gel tends to decrease, while if it exceeds the upper limit of the above range, This is because the mechanical strength of the obtained silicone gel tends to decrease.
[0031]
The platinum-based curing catalyst of the component (D) is a catalyst for accelerating the curing of the silicone composition, and includes, for example, platinum fine powder, platinum black, chloroplatinic acid, platinum tetrachloride, an alcohol solution of chloroplatinic acid, Platinum catalysts such as olefin complexes of platinum, alkenylsiloxane complexes of platinum, and carbonyl complexes of platinum; and rhodium catalysts and palladium catalysts.
[0032]
The content of the component (D) in the silicone composition is not particularly limited as long as the composition can be cured. Preferably, the platinum-based metal in the component (D) is used in an amount of 1,000,000 parts by weight of the component (A). Is in the range of 0.1 to 500 parts by weight.
[0033]
In order to improve the mechanical strength of the obtained silicone gel, the silicone composition used in the present invention further contains silica fine powder as a component (E) in addition to the components (A) to (D). Is also good. As the component (E), for example, fumed silica, precipitated silica, calcined silica, crushed quartz, and fine powders of these silicas were surface-treated with an organosilicon compound such as organoalkoxysilane, organohalosilane, or organosilazane. Fine powder. In particular, in order to sufficiently improve the mechanical strength of the obtained silicone gel, as the component (E), a BET specific surface area of 50 m ² / G or more is preferably used.
[0034]
In the above silicone composition, the content of the component (E) is optional, but in order to improve the mechanical strength of the obtained silicone gel, a range of 1 to 100 parts by weight based on 100 parts by weight of the component (A). And more preferably in the range of 1 to 50 parts by weight.
[0035]
The silicone composition may contain other optional components as long as the object of the present invention is not impaired. Such optional components include, for example, inorganic fillers such as fumed titanium oxide, carbon black, diatomaceous earth, iron oxide, aluminum oxide, aluminosilicate, calcium carbonate; and the like. Fillers treated with silicon compounds; alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-phenyl-1-putin-3-ol, Curing retarders such as enein compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne, and tetramethyltetrahexenylcyclotetrasiloxane and benzotriazole; phthalocyanine Copper, chlorinated phthalocyanine copper, etc., compression set enhancers; other reinforcing agents, viscosity modifiers, heat resistance agents, flame retardant Imparting agents, thermally conductive fillers, conductivity imparting agents, adhesion imparting agent.
[0036]
The method for preparing the silicone composition is not limited, and can be prepared by mixing the components (A) to (D) and an optional component, and the composition contains the component (E). In this case, the components (B) to (D) may be added to the silicone gel base prepared by heating and mixing the components (A) and (E), or the components (A) and (C) may be added in advance. It is preferable to add the component (B), the remaining components (C) and (D) to a silicone gel base prepared by heating and mixing a part or all of the component and the component (E). In addition, when it is necessary to add other optional components, it may be blended when preparing the silicone gel base, and when this is deteriorated by heating and mixing, the components (B) and (D) may be added. It is preferable to add at the time of addition. When preparing the silicone gel base, the surface of the component (E) may be treated in-situ by adding the aforementioned organosilicon compound.
[0037]
The silicone composition cures to form a silicone gel having excellent mold release properties and a small compression set. The hardness of the silicone gel is not limited, but preferably the Asker C hardness is 0 to 30 °. And more preferably in the range of 1 to 30 °. This Asker C hardness can be measured by an Asker C hardness meter corresponding to a spring hardness tester specified in JIS S6050 (1994).
[0038]
The waterproof connector holder of the present invention includes a resin holder and a packing part made of a gel-like material for keeping the electric wire side end of the waterproof connector in which the terminal part of the electric wire with a terminal is inserted therein watertight. Is an integral part of the holder for a waterproof connector. For example, the holder may be integrated with the connector housing as a part of the connector housing via a flexible connecting portion or the like, and such a case also belongs to the present invention.
[0039]
【Example】
EXAMPLES The waterproof connector holder of the present invention will be described in detail with reference to examples. In addition, the viscosity in an Example is a value in 25 degreeC.
[Example 1]
100 parts by weight of a dimethylsiloxane / methylvinylsiloxane copolymer having a viscosity of 10,000 mPa · s and both ends of a molecular chain and a trimethylsiloxy group blocked, a BET specific surface area of 200 m ² / G of fumed silica, 5 parts by weight of hexamethyldisilazane as a silica treating agent, and 2 parts by weight of water, and then heat-mixed under reduced pressure to prepare a liquid silicone gel base.
[0040]
Next, 140 parts by weight of this liquid silicone gel base, 230 parts by weight of a dimethylpolysiloxane having a viscosity of 3000 mPa · s and capped at both ends of a molecular chain, and dimethylsiloxane and methylhydrochloride having a viscosity of 10 mPa · s capped at both ends of a molecular chain. Gensiloxane copolymer (an amount in which silicon-bonded hydrogen atoms are 1.6 moles per mole of vinyl groups in the dimethylsiloxane / methylvinylsiloxane copolymer contained in the silicone gel base), platinum 1,3-divinyltetramethyldisiloxane complex (35 parts by weight of platinum metal based on 1 million parts by weight of dimethylsiloxane / methylvinylsiloxane copolymer in the silicone gel base), and 3,5 -Dimethyl-1-hexyn-3-ol 0.12 layers Part were mixed to prepare a silicone gel composition.
[0041]
The Asker C hardness and compression set of the silicone gel obtained by curing the silicone gel composition, and the mold releasability of the packing portion made of the silicone gel obtained by curing the silicone gel composition are as follows. And the adhesiveness to the rear holder was also confirmed, and the results of these evaluations are shown in Table 1.
[0042]
[Evaluation method for mold release property]
FIG. 2 shows a rear holder portion (made of polybutylene terephthalate resin (hereinafter also referred to as “PBT”) or polyethylene terephthalate resin (hereinafter also referred to as “PET”)) whose model is shown in FIG. 1 as an insert. It was poured into a steel mold having a cavity in which a holder for a waterproof connector integrated with a packing portion made of such a gel material was obtained, and press-cured at 150 ° C. for 10 minutes.
[0043]
3 (a) to 3 (c) and FIGS. 4 (a) to 4 (c) schematically show steps of manufacturing the waterproof connector holder.
The lower mold is indicated by reference numeral 3a in FIG. In the lower mold 3a, a packing part terminal insertion hole forming pin 3a that penetrates through the holder part terminal insertion hole 1a of the holder part 1 and projects into the packing part formation cavity. ₁ Is provided.
[0044]
The holder 1 is inserted into the lower mold 3a, and the pin 3a ₁ Is set so as to pass through the holder terminal insertion hole 1a (see FIG. 3B).
Then, in the case of this example, the middle mold 3b having the same thickness as the packing part to be formed is set on the lower mold 3a (see FIG. 3 (c)), and the silicone gel composition is formed in the formed cavity. 2 ₁ (See FIG. 4A).
[0045]
The mold is clamped by the upper mold 3c (see FIG. 4B), and after curing, the mold is opened to take out the waterproof connector holder in which the holder 1 and the packing 2 are integrated (see FIG. 4C). ).
[0046]
At this time, when taking out the waterproof connector holder from the mold, it was evaluated whether or not the removal was easy. If the adhesion between the packing part 2 and the mold is unnecessarily high, the middle mold 3b or the pin 3a for forming the packing part terminal insertion hole is used. ₁ The packing part is damaged when the holder part 1 is removed, or peeling occurs between the holder part 1 and the packing part 2.
In this example, the size of the packing portion was 15 mm × 15 mm × 4 mm.
[0047]
On the other hand, the hardness of the separately press-cured (primary vulcanized) silicone gel was measured with an Asker C hardness meter. Furthermore, the hardness of the silicone gel after heating (second vulcanization) at 200 ° C. for 4 hours was measured in the same manner.
[0048]
The silicone gel composition was cured at 150 ° C. for 10 minutes to prepare a test piece for measuring compression set in accordance with the method specified in JIS K249, and this was further subjected to a second application at 200 ° C. for 4 hours. Vulcanized. After that, the compression set was measured when this was compressed at 150 ° C. for 70 hours in accordance with the method specified in JIS K6249.
[0049]
[Comparative Example 1]
140 parts by weight of a liquid silicone gel base prepared in the same manner as in Example 1, dimethylvinylsiloxy groups at both ends of molecular chains having a viscosity of 40,000 mPa · s 100 parts by weight of dimethylpolysiloxane blocked at both ends of molecular chains, and trimethylsiloxy groups at both ends of molecular chains having a viscosity of 10 mPa · s Blocked dimethylsiloxane / methylhydrogensiloxane copolymer (0.5 mole of silicon-bonded hydrogen atom per mole of vinyl group in dimethylsiloxane / methylvinylsiloxane copolymer contained in the silicone gel base) And platinum 1,3-divinyltetramethyldisiloxane complex (an amount such that platinum metal is 10 parts by weight based on 1,000,000 parts by weight of the dimethylsiloxane / methylvinylsiloxane copolymer in the silicone gel base) ), And 3,5-dimethyl-1-hexyl 3 by mixing all 0.1 part by weight to prepare a silicone gel composition. Asker C hardness and compression set of the silicone gel obtained by curing this silicone gel composition were measured in the same manner as in Example 1, and the same two kinds of rear holders (the same as those used in Example 1) were used. Using a polybutylene terephthalate resin or a polyethylene terephthalate resin) as inserts, a waterproof connector holder integrated with the packing part was molded, and the mold releasability and adhesion to the rear holder part were evaluated. The results are shown in Table 1.
[0050]
[Comparative Example 2]
140 parts by weight of a liquid silicone gel base prepared in the same manner as in Example 1, dimethylpolysiloxane blocked at both ends of a molecular chain having a viscosity of 3000 mPa · s 70 parts by weight of dimethylpolysiloxane, and blocked at both ends of a molecular chain having a viscosity of 10 mPa · s at a trimethylsiloxy group Dimethylsiloxane / methylhydrogensiloxane copolymer (0.9 moles of silicon-bonded hydrogen atoms per mole of vinyl groups in the dimethylsiloxane / methylvinylsiloxane copolymer contained in the silicone gel base) Amount), platinum 1,3-divinyltetramethyldisiloxane complex (an amount in which platinum metal is 10 parts by weight based on 1,000,000 parts by weight of the dimethylsiloxane / methylvinylsiloxane copolymer in the silicone gel base) , And 3,5-dimethyl-1-hexyne-3- It was prepared silicone gel composition by mixing Lumpur 0.1 parts by weight. Asker C hardness and compression set of a silicone gel obtained by curing this silicone gel composition were measured in the same manner as in Example 1, and the same polybutylene terephthalate resin as used in Example 1 was measured. A waterproof connector holder integrated with the packing part was formed using the rear holder part as an insert, and the mold releasability and adhesion to the rear holder part were evaluated. The results are shown in Table 1.
[0051]
[Table 1]

[0052]
[Example 2]
100 parts by weight of dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends of molecular chain having a viscosity of 10,000 mPa · s, and a BET specific surface area of 200 m, which is surface-treated with dimethyldichlorosilane ² / G of fumed silica / g, and then heat-mixed under reduced pressure to prepare a liquid silicone gel base.
[0053]
Next, 120 parts by weight of this liquid silicone gel base, 140 parts by weight of a dimethylpolysiloxane having a viscosity of 100 mPa · s and capped at both ends of a molecular chain, and dimethylsiloxane and a methylhydrochloride having a viscosity of 5 mPa · s capped at both ends of a molecular chain. Gensiloxane copolymer (an amount in which silicon-bonded hydrogen atoms are 1.4 mol per 1 mol of vinyl groups in dimethylpolysiloxane contained in the silicone gel base), 1,3-divinyl of platinum Tetramethyldisiloxane complex (an amount of 35 parts by weight of platinum metal with respect to 1 million parts by weight of dimethylpolysiloxane in the silicone gel base), 3,5-dimethyl-1-hexyn-3-ol 0.12 Parts by weight and 1 part by weight of phthalocyanine copper fine powder The Narubutsu was prepared.
[0054]
The Asker C hardness and compression set of the silicone gel obtained by curing this silicone gel composition, and the same two types of rear holders as those used in Example 1 were respectively integrated with the packing part as inserts. The waterproof connector holder was molded, and its mold releasability and adhesion to the rear holder portion were evaluated as follows. Table 2 shows the results.
[0055]
[Mold release property]
A packing part made of a gel-like material as shown in FIG. 2 using the silicone gel composition as an insert and using two kinds of rear holder parts made of the same polybutylene terephthalate resin and polyethylene terephthalate resin as those used in Example 1. It was poured into a chrome-plated steel mold having a cavity in which a holder for a waterproof connector integrated with the above was obtained, and cured at 120 ° C. for 10 minutes. When removing the obtained waterproof connector holder from the mold, it was evaluated whether or not the removal was easy.
[0056]
[Asker C hardness]
The hardness of the silicone gel after press curing (primary vulcanization) was measured with an Asker C hardness meter.
[Compression set]
The silicone gel composition was cured at 120 ° C. for 10 minutes to prepare a test piece for measuring compression set according to the method specified in JIS K6249. Next, according to the method specified in JIS K6249, the compression set at the time of compression at 150 ° C. for 70 hours was measured.
[0057]
[Comparative Example 3]
120 parts by weight of a liquid silicone gel base prepared in the same manner as in Example 2, 100 parts by weight of a dimethylpolysiloxane blocked at both ends of a molecular chain having a viscosity of 10,000 mPa · s, and trimethylsiloxy groups at both ends of a molecular chain having a viscosity of 5 mPa · s Blocked dimethylsiloxane / methylhydrogensiloxane copolymer (amount of silicon-bonded hydrogen atoms to be 0.6 mol per 1 mol of vinyl groups in dimethylpolysiloxane contained in the silicone gel base), platinum 1,3-divinyltetramethyldisiloxane complex (10 parts by weight of platinum metal based on 1 million parts by weight of dimethylpolysiloxane in the silicone gel base), 3,5-dimethyl-1-hexyne- 0.1 parts by weight of 3-ol and 1 part by weight of phthalocyanine copper fine powder Mixed to prepare a silicone gel composition.
[0058]
Asker C hardness and compression set of the silicone gel obtained by curing this silicone gel composition were measured in the same manner as in Example 2, and the results are shown in Table 2.
[0059]
[Comparative Example 4]
120 parts by weight of a liquid silicone gel base prepared in the same manner as in Example 2, 50 parts by weight of a dimethylpolysiloxane capped at both ends of a molecular chain having a viscosity of 100 mPa · s, and capped with a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 5 mPa · s Dimethylsiloxane / methylhydrogensiloxane copolymer (an amount in which silicon-bonded hydrogen atoms are 0.9 moles per mole of vinyl groups in dimethylpolysiloxane contained in the silicone gel base) and platinum 1,3-divinyltetramethyldisiloxane complex (an amount of 10 parts by weight of platinum metal with respect to 1 million parts by weight of dimethylpolysiloxane in the silicone gel base), 3,5-dimethyl-1-hexyne-3 -0.1 part by weight of all and 1 part by weight of phthalocyanine copper fine powder The Rikongeru composition was prepared.
[0060]
The mold release property, Asker C hardness, and compression set of the silicone gel obtained by curing this silicone gel composition were measured in the same manner as in Example 2, and the same as that used in Example 1 was measured. Using a rear holder made of polybutylene terephthalate resin as an insert, a waterproof connector holder integrated with the packing was molded, and its mold releasability and adhesion to the rear holder were evaluated. The results are also shown in Table 2.
[0061]
[Table 2]

[0062]
[Evaluation of durability as a connector]
A packing part comprising a holder for a waterproof connector of Embodiment 1 (using a rear holder part made of polybutylene terephthalate), a rear connector part having the same shape and the same material, and a silicone gel (manufactured by Raychem Corporation) according to the prior art The waterproof property before and after the heat history was evaluated using a waterproof connector holder having the following.
[0063]
As shown in FIG. 6, these waterproof connector holders were set in the waterproof connector housing β, and the terminals with electric wires γ were inserted. At this time, a sample in which the terminal was inserted only once and a sample in which the terminal was inserted and then further inserted and removed repeatedly to insert the terminal five times in total were produced.
An air tube was inserted into the waterproof connector housing β on the joint side with the mating connector, and then sealed with resin in a watertight manner.
[0064]
These were submerged in water, and the internal pressure at which air leaked from between the electric wires and the packing portion when compressed air was introduced from an air tube was examined. If the pressure at this time is 200 kPa or more, it is determined that there is sufficient waterproofness.
After examining these waterproof properties, a heat history was given in an environment of 150 ° C. for 120 hours, and the waterproof properties were examined again. The results are shown in Table 3.
[0065]
[Table 3]

[0066]
According to Table 3, at least (A) 100 parts by weight of an organopolysiloxane having at least two alkenyl groups in one molecule, and (B) an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule are represented by ( The amount of the silicon-bonded hydrogen atom in the component (B) to be 0.5 mol or more and 10 mol or less per 1 mol of the alkenyl group in the component (A), and the alkenyl group and the silicon-bonded hydrogen atom in the molecule (C). A gel-like packing part obtained by curing a silicone composition comprising 100 parts by weight or more and 500 parts by weight or less of atom-free organopolysiloxane and (D) a platinum-based curing catalyst, which is composed of four kinds of raw materials, is integrated. In the case where the waterproof connector rear holder according to the first embodiment is used, high waterproofness can be obtained even when the insertion of the terminal-equipped wire is repeated, and It is understood that high water resistance even after subjected to thermal history is maintained.
[0067]
【The invention's effect】
The waterproof connector holder of the present invention is made of a gel material, and has a packing portion having a terminal insertion hole through which a terminal-equipped wire inserted into the waterproof connector penetrates, and a terminal-equipped wire inserted into the waterproof connector. A waterproof connector holder having a holder portion terminal insertion hole to be inserted and a holder portion for holding the packing portion in the waterproof connector, and the packing portion and the holder portion are integrated. The structure eliminates the need for the constraining layer of the packing, which has been required conventionally, making the packing easy and inexpensive, and ensures that the packing part terminal insertion hole and the holder part terminal insertion hole coincide with each other. Therefore, there is no deviation between the terminal insertion ports, and furthermore, such a waterproof connector holder is set in the waterproof connector housing. In this case as well, the terminal insertion hole of the packing portion and the terminal storage chamber of the waterproof connector housing are set so as to coincide with each other, so that all the problems that occur when the centers are shifted from each other are solved, and the packing portion and the holder portion are previously set. Since they are integrated, the waterproof connector can be assembled very easily.
[Brief description of the drawings]
FIG. 1 is a model perspective view showing an assembly image of a waterproof connector using an example of a waterproof connector holder of the present invention.
FIG. 2 is a model sectional view showing a state of a terminal insertion opening in an assembling process of an example of a waterproof connector holder according to the present invention.
FIG. 3 is a model sectional view showing a step of forming an example of the waterproof connector holder of the present invention.
FIG. 4 is a model cross-sectional view showing a step of forming an example of the waterproof connector holder of the present invention.
FIG. 5 is a model perspective view showing an assembly image of a waterproof connector using an example of a conventional waterproof connector holder.
FIG. 6 is a model cross-sectional view illustrating a problem in the waterproof connector according to the related art.
[Explanation of symbols]
1 Rear holder
1a Holder terminal insertion hole
2 Packing part
α Holder for waterproof connector according to the present invention
β waterproof connector housing
Wire with γ terminal
3a Lower mold
3a ₁ Packing part terminal insertion hole forming pin
3b middle mold
3c Upper mold

Claims (2)

A packing part made of a gel-like material and having a packing part terminal insertion hole through which an electric wire with a terminal inserted into the waterproof connector penetrates, and a holder part terminal insertion hole through which an electric wire with a terminal inserted into the waterproof connector penetrates. And a holder for holding the packing portion in the waterproof connector is integrated with the holder for the waterproof connector. A metal having a packing part terminal insertion hole forming pin projecting through a holder part terminal insertion hole of the holder part and projecting into a packing part formation cavity by using a holder part in which a packing part of the waterproof connector holder is formed in advance as an insert. 2. The waterproof connector holder according to claim 1, wherein the holder is formed using a mold.

Images