JP3500459B2 - Release agent for vulcanized rubber - Google Patents
Release agent for vulcanized rubberInfo
- Publication number
- JP3500459B2 JP3500459B2 JP11196894A JP11196894A JP3500459B2 JP 3500459 B2 JP3500459 B2 JP 3500459B2 JP 11196894 A JP11196894 A JP 11196894A JP 11196894 A JP11196894 A JP 11196894A JP 3500459 B2 JP3500459 B2 JP 3500459B2
- Authority
- JP
- Japan
- Prior art keywords
- release agent
- mol
- hose
- mandrel
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Moulds For Moulding Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は、加硫ゴム用離型剤に関
し、更に詳しくは、ゴムホースの製造などに用いる成形
ホース用マンドレルに使用可能な離型剤で、挿入性、引
抜き性（離型性）に優れた加硫ゴム用離型剤である。
【０００２】
【従来の技術】本発明離型剤は、加硫ゴム用のものであ
るが、以下その代表としてゴムホースを例にとって説明
する。
【０００３】自動車やその他の分野において、ゴムホー
スは多く使用されており、形状としては直管又は曲がり
管と呼ばれるものがある。これらの成形ホースの製造
は、所定の形状に成形されたマンドレルを用いてゴムを
加硫成形した後、加硫ゴムホースをマンドレルから引き
抜く必要があり、この引抜き工程を容易にするため、離
型剤が用いられる。
【０００４】次にこの離型剤の使用工程を説明する。所
定のマンドレル（ステンレス、アルミニウム等）に未加
硫ホースを挿入する前に、予め離型剤を塗布する。塗布
方法としては所定の濃度に調整した離型剤溶液をハケ塗
り、又はスプレー塗布する。また、未加硫ゴムホースの
先端を離型剤溶液に浸漬する方法もある。更に、２つの
方法を組み合わせてもよい。
【０００５】次に、所定の形状のマンドレルに未加硫ゴ
ムホースを差し込み、１５０℃〜１８０℃で３０分〜１
時間加硫を行なう。加硫後、ホースをマンドレルから引
き抜き、その引き抜いた加硫ホースを溶剤による洗浄及
び水洗又は湯洗を行なえばホースができるのである。
【０００６】この様な成形ホースの製造に用いられるマ
ンドレル用離型剤に求められる特性は、次の通りであ
る。
マンドレルへの未加硫ホースの挿入性が良好である
こと。
マンドレルからの加硫ホースの引抜き性が良好であ
ること。
加硫ホース内面に付着した離型剤が容易に洗浄除去
できること。
【０００７】そして、現在使用されている成形ホース用
マンドレル離型剤としては、ポリプロピレングリコー
ル、ポリエチレングリコールの多価アルコール系化合
物、ポリオキシアルキレングリコール系化合物及び石鹸
等の界面活性剤やジメチルシリコーン、変性シリコーン
オイル等が使用される。
【０００８】
【発明が解決しようとする課題】しかし、このような従
来の離型剤では次のような欠点があった。最近の曲がり
ゴムホースは、新規なゴム素材、例えばアクリルゴム、
ハイパロンエピクロルヒドリンゴム等が使用されている
ため、従来の離型剤では満足する性能は得られなかっ
た。その要因として、
離型剤のマンドレル及び未加硫ゴムホースへの付着
性が不足することによる離型性不足
生産の合理化に伴い、加硫条件の高温化によって離
型剤の耐熱性が不足することによる離型性不足
加硫ホースの洗浄方法の変化として、溶剤から水洗
（湯洗）に移行しつつあり、そのための洗浄性不足
このため、本業界では、マンドレル及び各種ゴムへの付
着性、耐熱性及び離型性に優れ、水洗により洗浄可能な
離型剤が待望されていた。
【０００９】
【課題を解決するための手段】 そこで、本発明者は、
鋭意研究の結果本発明離型剤を完成させたものであり、
その特徴とするところは、下記一般式化１で示されるジ
アミンのアルキレンオキサイド付加物からなる点にあ
る。
【化１】〔ただし、２≦Ａ≦６であり、
０≦al, a2, a3, a4≦２０
１≦bl, b2, b3, b4≦１２
０≦cl, c2, c3, c4≦２０
０≦dl, d2, d3, d4≦１２
４≦al＋a2＋a3＋a4＋cl＋c2＋c3＋c4≦８０
４≦bl＋b2＋b3＋b4＋dl＋d2＋d3＋d4≦５０である。〕
【００１０】ここで、前記一般式中の、プロピレンオキ
サイドの合計付加モル数が４以下の場合、マンドレル用
離型剤としての潤滑性に乏しく、生産工程においてホー
スを挿入、離型する性能を有しない。一方、それが８０
より大きい場合、その製造コストが高くなり、さらには
水による洗浄性が悪くなる。離型剤としての具備条件及
び製造コストを考慮した場合、プロピレンオキサイドの
合計付加モル数の好ましい範囲は７〜４０である。一
方、エチレンオキサイドの合計付加モル数が４以下の場
合、加硫ホースについた離型剤の洗浄性が乏しいため生
産性が低下する。また、それが５０以上の場合、凝固点
が上昇しマンドレル離型剤としての潤滑性に劣る。そこ
で、離型剤としてエチレンオキサイドの合計付加モル数
の特に好ましい範囲は１０〜４０である。また、アルキ
レンオキサイド付加物を形成するアミンは、エチレンジ
アミン、トリエチレンジアミン、テトラエチレンジアミ
ン、ペンタエチレンジアミン、ヘキサメチレンジアミン
である。
【００１１】この化合物以外に含有してもよい成分とし
ては、水、低級アルコール（炭素数１〜３）等がある。
また、本発明の離型剤は単独でも十分使用可能である
が、公知のポリプロピレングリコール、ポリエチレング
リコール等の多価アルコール系化合物、ポリオキシアル
キレングリコール系化合物及び石鹸等の界面活性剤やジ
メチルシリコーン、変性シリコーンオイル、鉱物油、植
物油及び鉱油等と併用してもよい。
【００１２】
【実施例】実施例１
５０００ｍｌのオートクレーブにエチレンジアミン６
０．１ｇ（１mol)、及びアルカリ触媒として４８％ＫＯ
Ｈ２５ｇを仕込み、チッ素ガスにて置換した後、温度１
０５℃に昇温し、減圧下にて脱水を行なった。次に、プ
ロピレンオキサイド４６４ｇ（８ mol) を徐々に仕込
み、圧力２Kg／cm2 、温度１２０℃に保ちつつ、付加重
合を行なった。次にエチレンオキサイド１３２０ｇ（30
mol)を、同条件で付加重合させた。重合終了後、酢酸を
使用してｐＨを約１０に調整し、加硫ゴム用離型剤を得
た。この得られた化合物は、特許請求の範囲においては
a1, a2, a3, a4＝２、b1, b2, b3, b4＝７．５、Ａ＝
２、他の値は０のものに相当する。
【００１３】実施例２
エチレンジアミン６０．１ｇ（１mol)にプロプレンオキ
サイド１７４０ｇ（30mol)と、エチレンオキサイド１３
２０ｇ（30mol)を同時に仕込み、付加重合を行ない、重
合終了後、実施例と同様の方法で加硫ゴム用離型剤を得
た。この場合には、a1, a2, a3, a4が各７．５、b1, b
2, b3, b4も７．５となり、プロプレンオキサイドとエ
チレンオキサイドがランダムに結合している。勿論、請
求項１の範囲には含まれる。
【００１４】実施例３
トリエチレンジアミン７４ｇ（１mol)に、プロプレンオ
キサイド６９６ｇ（12mol)を仕込み付加重合させ、次に
エチレンオキサイド１５８４ｇ（36mol)を仕込み付加重
合させ、次にプロプレンオキサイド１３９２ｇ（24mol)
を仕込み付加重合を行ない加硫ゴム用離型剤を得た。こ
の得られた化合物は、特許請求の範囲においてはa1, a
2, a3, a4＝３、b1, b2, b3, b4＝９、c1, c2, c3, c4
＝６、Ａ＝３、他の値は０のものに相当する。
【００１５】実施例４
ペンタエチレンジアミン１０２ｇ（１mol)に、エチレン
オキサイド１０５６ｇ（24mol)を仕込み付加重合させ、
次にプロプレンオキサイド１３９２ｇ（24mol)を仕込み
付加重合を行ない加硫ゴム用離型剤を得た。この得られ
た化合物は、特許請求の範囲においてはb1, b2, b3, b4
＝６、c1, c2, c3, c4＝６、Ａ＝５、他の値は０のもの
に相当する。
【００１６】実施例５
エチレンジアミン６０．１ｇ（１mol)に、エチレンオキ
サイド１０５６ｇ（24mol)を仕込み付加重合させ、次に
プロプレンオキサイド１３９２ｇ（24mol)を仕込み付加
重合を行ない、次にエチレンオキサイド３５２ｇ（８mo
l)を仕込み付加重合させ加硫ゴム用離型剤を得た。この
得られた化合物は、特許請求の範囲においてはb1, b2,
b3, b4＝６、c1, c2, c3, c4＝６、d1, d2, d3, d4＝
２、Ａ＝２、他の値は０のものに相当する。
【００１７】比較例１
５０００ｍｌのオートクレーブにエチレンジアミン６
０．１ｇ（１mol)、及びアルカリ触媒として４８％ＫＯ
Ｈ２５ｇを仕込み、チッ素ガスにて置換した後、温度１
０５℃に昇温し、減圧下にて脱水を行なった。次に、プ
ロピレンオキサイド１７４ｇ（３ mol) を徐々に仕込
み、圧力２Kg／cm2 、温度１２０℃に保ちつつ、付加重
合を行なった。次にエチレンオキサイド１４０８ｇ（32
mol)を、同条件で付加重合させた。重合終了後、酢酸を
使用してｐＨを約１０に調整し離型剤を得た。この得ら
れた化合物は、特許請求の範囲の記載方法においてはa
1, a2,a3, a4＝０．７５、b1, b2, b3, b4＝８、Ａ＝
２、他の値は０のものに相当する。
【００１８】比較例２
以下比較例１と同様の方法であるため、使用するアミン
とアルキレンオキサイドのみを記す。エチレンジアミン
６０．１ｇ（１mol)、次にエチレンオキサイド１４０８
ｇ（32mol)、次にプロプレンオキサイド５８００ｇ（10
0 mol)。この得られた化合物は、特許請求の範囲の記載
方法においてはa1, a2, a3, a4＝０、b1, b2, b3, b4＝
８、c1, c2, c3, c4＝２５、Ａ＝２、他の値は０のもの
に相当する。
【００１９】比較例３
トリエチレンジアミン６４ｇ（１mol)、次にプロプレン
オキサイド１７４０ｇ（30mol)、次にエチレンオキサイ
ド１３２ｇ（３mol)、。この得られた化合物は、特許請
求の範囲の記載方法においてはa1, a2, a3, a4＝７．
５、b1, b2, b3,b4＝０．７５、Ａ＝３、他の値は０の
ものに相当する。
【００２０】比較例４
エチレンジアミン６０．１ｇ（１mol)、次にプロプレン
オキサイド１７４０ｇ（30mol)、次にエチレンオキサイ
ド２６４０ｇ（60mol)。この得られた化合物は、特許請
求の範囲の記載方法においてはa1, a2, a3, a4＝７．
５、b1, b2, b3,b4＝１５、Ａ＝２、他の値は０のもの
に相当する。
【００２１】離型性の評価
成形ホース用マンドレルの外表面に、表に示す離型剤を
塗布し、更に未加硫ホース先端に離型剤を浸漬後、マン
ドレルに挿入する。次に、これを１５０℃で３０分蒸気
加硫する。その後、マンドレルから加硫したホースを引
抜き、離型性（引抜き性）を評価した。評価基準は次の
通りである。
◎：作業がきわめて容易である。
○：作業が容易である。
△：作業効率が悪い。
×：作業効率がきわめて悪い。
【００２２】洗浄性の評価
上記加硫ホースを各温水（３０℃、６０℃）で洗浄し、
離型剤の除去性を評価した。評価基準は次の通りであ
る。
◎：きわめて容易に離型剤が除去される。
○：簡単な洗浄で離型剤が除去される。
×：離型剤が除去できない。
【００２３】
【発明の効果】以上の結果を表１に示す。この表から、
本発明が従来品よりも優れ、離型性、洗浄性の両面にお
いて問題がないことが分かる。
【表１】 Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a release agent for vulcanized rubber, and more particularly to a release agent usable for a mandrel for a molded hose used for producing a rubber hose. It is a release agent for vulcanized rubber with excellent insertability and pull-out properties (release properties). [0002] The release agent of the present invention is for vulcanized rubber, and a representative example thereof will be described below using a rubber hose as an example. [0003] Rubber hoses are widely used in automobiles and other fields, and have a shape called a straight pipe or a bent pipe. In the production of these molded hoses, it is necessary to vulcanize and mold the rubber using a mandrel molded into a predetermined shape, and then to pull out the vulcanized rubber hose from the mandrel. Is used. Next, the process of using the release agent will be described. Before inserting the unvulcanized hose into a predetermined mandrel (stainless steel, aluminum, etc.), a release agent is applied in advance. As a coating method, a release agent solution adjusted to a predetermined concentration is brush-coated or spray-coated. There is also a method of immersing the tip of an unvulcanized rubber hose in a release agent solution. Further, the two methods may be combined. [0005] Next, an unvulcanized rubber hose is inserted into a mandrel of a predetermined shape, and is heated at 150 ° C to 180 ° C for 30 minutes to 1 hour.
Perform time vulcanization. After vulcanization, the hose is pulled out from the mandrel, and the pulled-out vulcanized hose is washed with a solvent and washed with water or hot water to form a hose. The characteristics required of a release agent for a mandrel used for manufacturing such a molded hose are as follows. Good insertion of unvulcanized hose into mandrel. Good pullability of the vulcanized hose from the mandrel. The release agent attached to the inner surface of the vulcanized hose can be easily washed and removed. [0007] Mandrel release agents for molded hoses currently used include surfactants such as polypropylene glycol, polyhydric alcohol compounds of polyethylene glycol, polyoxyalkylene glycol compounds, soaps and the like, dimethyl silicone, and denaturing agents. Silicone oil or the like is used. [0008] However, such a conventional release agent has the following disadvantages. Recent bent rubber hoses are made of new rubber materials such as acrylic rubber,
Since hypalone epichlorohydrin rubber and the like are used, satisfactory performance was not obtained with a conventional release agent. This is due to insufficient release properties due to insufficient adhesion of the release agent to the mandrel and unvulcanized rubber hose.Insufficient heat resistance of the release agent due to high temperature vulcanization conditions accompanying rationalization of production. Insufficient mold releasability Due to changes in vulcanized hose cleaning methods, there is a shift from solvent to water washing (hot water washing), and therefore insufficient washing properties. Therefore, in the industry, adhesion to mandrel and various rubbers, heat resistance There has been a long-awaited demand for a release agent which has excellent properties and releasability and can be washed with water. Means for Solving the Problems Accordingly, the present inventor has
As a result of intensive research, the mold release agent of the present invention has been completed.
The feature is that it is composed of an alkylene oxide adduct of a diamine represented by the following general formula 1. Embedded image [However, 2 ≦ A ≦ 6, 0 ≦ al, a2, a3, a4 ≦ 201 1 ≦ bl, b2, b3, b4 ≦ 120 0 ≦ cl, c2, c3, c4 ≦ 200 0 ≦ dl, d2, d3, d4 ≦ 124 4 ≦ al + a2 + a3 + a4 + cl + c2 + c3 + c4 ≦ 804 4 ≦ bl + b2 + b3 + b4 + dl + d2 + d3 + d4 ≦ 50. Here, when the total number of moles of propylene oxide in the above general formula is 4 or less, the lubricating properties as a release agent for a mandrel are poor, and the performance of inserting and releasing a hose in a production process is poor. Do not have. On the other hand, it is 80
If it is larger, the production cost becomes higher, and further, the cleaning property with water becomes worse. In consideration of the conditions for the release agent and the production cost, a preferable range of the total addition mole number of propylene oxide is 7 to 40. On the other hand, when the total number of added moles of ethylene oxide is 4 or less, the productivity is reduced due to poor cleaning properties of the release agent attached to the vulcanized hose. If it is 50 or more, the freezing point increases, and the lubricating properties as a mandrel release agent are poor. Therefore, a particularly preferred range of the total added mole number of ethylene oxide as the release agent is from 10 to 40. The amine forming the alkylene oxide adduct is ethylenediamine, triethylenediamine, tetraethylenediamine, pentaethylenediamine, or hexamethylenediamine. As components other than this compound which may be contained, there are water, lower alcohol (having 1 to 3 carbon atoms) and the like.
The release agent of the present invention can be used singly, but known polyols such as polypropylene glycol and polyethylene glycol, surfactants such as polyoxyalkylene glycol-based compounds and soaps, dimethyl silicone, You may use together with modified silicone oil, mineral oil, vegetable oil, mineral oil, etc. EXAMPLE 1 In a 5000 ml autoclave, ethylenediamine 6 was added.
0.1 g (1 mol) and 48% KO as an alkali catalyst
After charging 25 g of H2 and purging with nitrogen gas,
The temperature was raised to 05 ° C., and dehydration was performed under reduced pressure. Next, 464 g (8 mol) of propylene oxide was gradually charged, and addition polymerization was performed while maintaining the pressure at 2 kg / cm 2 and the temperature at 120 ° C. Next, 1320 g of ethylene oxide (30
mol) was subjected to addition polymerization under the same conditions. After the polymerization was completed, the pH was adjusted to about 10 using acetic acid to obtain a release agent for vulcanized rubber. This resulting compound is claimed in the claims
a1, a2, a3, a4 = 2, b1, b2, b3, b4 = 7.5, A =
2, other values correspond to those of 0. EXAMPLE 2 1740 g (30 mol) of propylene oxide and 60.1 g (1 mol) of ethylenediamine and 130.1 g of ethylene oxide
20 g (30 mol) were simultaneously charged and addition polymerization was carried out. After the completion of the polymerization, a release agent for vulcanized rubber was obtained in the same manner as in Example. In this case, a1, a2, a3, a4 are each 7.5, b1, b
2, b3 and b4 are also 7.5, and propylene oxide and ethylene oxide are randomly bonded. Of course, it is included in the scope of claim 1. Example 3 696 g (12 mol) of propylene oxide was charged to 74 g (1 mol) of triethylenediamine to carry out addition polymerization, and then 1584 g (36 mol) of ethylene oxide was charged to carry out addition polymerization, and then 1392 g (24 mol) of propylene oxide
To obtain a release agent for vulcanized rubber. The obtained compound is referred to in the claims as a1, a
2, a3, a4 = 3, b1, b2, b3, b4 = 9, c1, c2, c3, c4
= 6, A = 3, other values correspond to 0. Example 4 1056 g (24 mol) of ethylene oxide was charged into 102 g (1 mol) of pentaethylenediamine and subjected to addition polymerization.
Next, 1392 g (24 mol) of propylene oxide was charged and subjected to addition polymerization to obtain a release agent for vulcanized rubber. The obtained compound is referred to as b1, b2, b3, b4 in the claims.
= 6, c1, c2, c3, c4 = 6, A = 5, other values correspond to zero. Example 5 1056 g (24 mol) of ethylene oxide was charged to 60.1 g (1 mol) of ethylenediamine and subjected to addition polymerization. Then, 1392 g (24 mol) of propylene oxide was charged and subjected to addition polymerization. Then, 352 g of ethylene oxide (8 mol
l) was added and subjected to addition polymerization to obtain a release agent for vulcanized rubber. The obtained compound is referred to as b1, b2,
b3, b4 = 6, c1, c2, c3, c4 = 6, d1, d2, d3, d4 =
2, A = 2, other values correspond to 0. Comparative Example 1 Ethylenediamine 6 was added to a 5000 ml autoclave.
0.1 g (1 mol) and 48% KO as an alkali catalyst
After charging 25 g of H2 and purging with nitrogen gas,
The temperature was raised to 05 ° C., and dehydration was performed under reduced pressure. Next, 174 g (3 mol) of propylene oxide was gradually charged, and addition polymerization was performed while maintaining the pressure at 2 kg / cm 2 and the temperature at 120 ° C. Next, 1408 g of ethylene oxide (32
mol) was subjected to addition polymerization under the same conditions. After the completion of the polymerization, the pH was adjusted to about 10 using acetic acid to obtain a release agent. The obtained compound is represented by a in the method described in the claims.
1, a2, a3, a4 = 0.75, b1, b2, b3, b4 = 8, A =
2, other values correspond to those of 0. Comparative Example 2 Since the method is the same as in Comparative Example 1, only the amine and alkylene oxide used will be described. 60.1 g (1 mol) of ethylenediamine and then 1408 of ethylene oxide
g (32 mol), and then 5800 g of propylene oxide (10
0 mol). In the method described in the claims, the obtained compound is represented by a1, a2, a3, a4 = 0, b1, b2, b3, b4 =
8, c1, c2, c3, c4 = 25, A = 2, other values correspond to those of 0. COMPARATIVE EXAMPLE 3 64 g (1 mol) of triethylenediamine, then 1740 g (30 mol) of propylene oxide, and then 132 g (3 mol) of ethylene oxide. In the method described in the claims, the obtained compound is a1, a2, a3, a4 = 7.
5, b1, b2, b3, b4 = 0.75, A = 3, and other values correspond to those of 0. Comparative Example 4 60.1 g (1 mol) of ethylenediamine, 1740 g (30 mol) of propylene oxide, and then 2640 g (60 mol) of ethylene oxide. In the method described in the claims, the obtained compound is a1, a2, a3, a4 = 7.
5, b1, b2, b3, b4 = 15, A = 2, and other values correspond to those of 0. Evaluation of Release Property The release agent shown in the table is applied to the outer surface of a mandrel for a molded hose, and the release agent is immersed in the tip of an unvulcanized hose and then inserted into the mandrel. Next, this is steam-vulcanized at 150 ° C. for 30 minutes. Thereafter, the vulcanized hose was pulled out from the mandrel, and the releasability (pullability) was evaluated. The evaluation criteria are as follows. A: Work is extremely easy. ：: Work is easy. Δ: Work efficiency is poor. X: The working efficiency is extremely poor. Evaluation of Detergency The vulcanized hose was washed with warm water (30 ° C., 60 ° C.)
The removability of the release agent was evaluated. The evaluation criteria are as follows. A: The release agent is very easily removed. ：: The release agent is removed by simple washing. ×: The release agent cannot be removed. The above results are shown in Table 1. From this table,
It can be seen that the present invention is superior to the conventional product, and there is no problem in both the releasing property and the cleaning property. [Table 1]
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B29C 33/62 - 33/66 C08L 71/02 - 71/03 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) B29C 33/62-33/66 C08L 71/02-71/03 CA (STN)
Claims (1)
ルキレンオキサイド付加物からなることを特徴とする成
形ホース製造用のマンドレル用離型剤、 【化１】〔ただし、２≦Ａ≦６であり、 ０≦al, a2, a3, a4≦２０ １≦bl, b2, b3, b4≦１２ ０≦cl, c2, c3, c4≦２０ ０≦dl, d2, d3, d4≦１２ ４≦al＋a2＋a3＋a4＋cl＋c2＋c3＋c4≦８０ ４≦bl＋b2＋b3＋b4＋dl＋d2＋d3＋d4≦５０である。〕(57) [Claim 1] A release agent for a mandrel for producing a molded hose, comprising a diamine alkylene oxide adduct represented by the following general formula 1: [However, 2 ≦ A ≦ 6, 0 ≦ al, a2, a3, a4 ≦ 201 1 ≦ bl, b2, b3, b4 ≦ 120 0 ≦ cl, c2, c3, c4 ≦ 200 0 ≦ dl, d2, d3, d4 ≦ 124 4 ≦ al + a2 + a3 + a4 + cl + c2 + c3 + c4 ≦ 804 4 ≦ bl + b2 + b3 + b4 + dl + d2 + d3 + d4 ≦ 50. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11196894A JP3500459B2 (en) | 1994-04-26 | 1994-04-26 | Release agent for vulcanized rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11196894A JP3500459B2 (en) | 1994-04-26 | 1994-04-26 | Release agent for vulcanized rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07292236A JPH07292236A (en) | 1995-11-07 |
| JP3500459B2 true JP3500459B2 (en) | 2004-02-23 |
Family
ID=14574658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11196894A Expired - Fee Related JP3500459B2 (en) | 1994-04-26 | 1994-04-26 | Release agent for vulcanized rubber |
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| Country | Link |
|---|---|
| JP (1) | JP3500459B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008201010A (en) * | 2007-02-21 | 2008-09-04 | Ipposha Oil Ind Co Ltd | Releasing agent for vulcanized rubber |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4547248B2 (en) * | 2004-12-21 | 2010-09-22 | 倉敷化工株式会社 | Method and apparatus for cleaning molded rubber hose |
| JP6240710B2 (en) * | 2016-05-13 | 2017-11-29 | 第一工業製薬株式会社 | Mold release agent for vulcanized rubber molding |
| JP6240709B2 (en) | 2016-05-13 | 2017-11-29 | 第一工業製薬株式会社 | Mold release agent for vulcanized rubber molding |
| JP2018103579A (en) * | 2016-12-28 | 2018-07-05 | 日華化学株式会社 | Mold release agent for vulcanized rubber |
| JP6937225B2 (en) * | 2017-11-08 | 2021-09-22 | 第一工業製薬株式会社 | Release agent for vulcanized rubber molding |
| JP7007896B2 (en) * | 2017-12-22 | 2022-01-25 | 日華化学株式会社 | Release agent for vulcanized rubber |
| JP7045272B2 (en) * | 2018-06-29 | 2022-03-31 | 日華化学株式会社 | Release agent for vulcanized rubber |
-
1994
- 1994-04-26 JP JP11196894A patent/JP3500459B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008201010A (en) * | 2007-02-21 | 2008-09-04 | Ipposha Oil Ind Co Ltd | Releasing agent for vulcanized rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07292236A (en) | 1995-11-07 |
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