JPS59166596A - Mold release agent - Google Patents
Mold release agentInfo
- Publication number
- JPS59166596A JPS59166596A JP4189183A JP4189183A JPS59166596A JP S59166596 A JPS59166596 A JP S59166596A JP 4189183 A JP4189183 A JP 4189183A JP 4189183 A JP4189183 A JP 4189183A JP S59166596 A JPS59166596 A JP S59166596A
- Authority
- JP
- Japan
- Prior art keywords
- mold release
- mold
- release agent
- group
- wax
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
本発明は、離型剤に関する。更て詳しくは、離型性成分
を有機媒体または水性媒体中に溶解または分散させてな
る離型剤に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mold release agent. More specifically, the present invention relates to a mold release agent formed by dissolving or dispersing a mold release component in an organic medium or an aqueous medium.
ポリフルオロカーボン基含有リン酸エステルまたはその
塩などの離型性成分を有機媒体または水性媒体中に溶解
または分離させ、その際シリコンオイルなどをそこに共
存さ、せた離型剤は、例えば特公昭５３−２３２７０号
公報、同５３−２３２７１号公報などに記載されている
。しかしながら、オイルを用いた離型剤は、オイル自身
が比較的高価であるばかりではなく、この離型剤を成形
用金型などに用いた場合には、成形品表面にべと付きが
みられるなどの問題点がみられた。A mold release agent in which a mold release component such as a polyfluorocarbon group-containing phosphoric acid ester or its salt is dissolved or separated in an organic medium or an aqueous medium, and silicone oil or the like is present therein, is available, for example, as disclosed by Tokko Sho. It is described in JP 53-23270, JP 53-23271, and the like. However, when using a mold release agent that uses oil, not only is the oil itself relatively expensive, but when this mold release agent is used in a mold, etc., it can cause stickiness on the surface of the molded product. Problems such as these were observed.
離型性成分として、ポリフルオロカーボン基含有リン酸
またはその塩よりも良好４Ｃ離型性能を示すポリフルオ
ロカーボン基含有ホスホン酸またはその塩を用いた場合
も同様であり、更にこの離型剤を塗布した成形用金型を
用いて了りらねた成形品は、後加工性の点でも具合の悪
い点がみられた。The same is true when polyfluorocarbon group-containing phosphonic acid or its salt, which exhibits better 4C mold release performance than polyfluorocarbon group-containing phosphoric acid or its salt, is used as the mold release component, and this mold release agent is further applied. The molded products that were not completed using the molding molds were also found to have poor post-processability.
即ち、成形品、例えばポリウレタン製ダストシールなど
を後加工する場合、成形品表面がシリコンオイル特有の
すべり、つるつるした感じを有し、そのため成形品を固
定して加工する場合、例えばパリ部分の除却、シール部
分の正確な切削などのための後加工のための固定が容易
ではなく、その結果後加工性が著しく損われる結県とな
る。That is, when post-processing a molded product, such as a polyurethane dust seal, the surface of the molded product has a slippery or slippery feel characteristic of silicone oil. It is not easy to fix the seal portion for post-processing such as accurate cutting, and as a result, post-processability is significantly impaired.
しかるに、シリコンオイルなどに代えてワックスを用い
ると、これらの欠点がいずれも効果的に解消されること
が見出された。従って、本発明は離型剤に係り、この離
型剤は、一般式ＲｆＸＰＯ（ＯＨ）、。However, it has been found that by using wax instead of silicone oil or the like, all of these drawbacks can be effectively eliminated. Accordingly, the present invention relates to a mold release agent having the general formula RfXPO(OH).
〔ここで、Ｒｆは炭素数４〜２０のポリフルオロカーボ
ン基であり、Ｘは２価の有機基である〕で表わされるポ
リフルオロカーボン基含有ホスホン酸またはその塩およ
びワックスを有機媒体または水性媒体中に溶解または分
散させてなる。[Here, Rf is a polyfluorocarbon group having 4 to 20 carbon atoms, and X is a divalent organic group] A polyfluorocarbon group-containing phosphonic acid or a salt thereof and a wax are placed in an organic medium or an aqueous medium. It can be dissolved or dispersed.
上記一般式で表わされるポリフルオロカーボン基含有ホ
スホン酸において、基Ｒｆおよび基Ｘとしては、例えば
次のようなものが挙げられる。In the polyfluorocarbon group-containing phosphonic acid represented by the above general formula, examples of the group Rf and the group X include the following.
基Ｒｆ： ｎ −０４Ｆ、 ：１Ｓｏ−０４Ｆ、
０５Ｆ’、、 ０６Ｆ’、３０８ Ｆ１７ ０９ Ｆ
１９ ０１０ Ｆ２１ＯＦ３０Ｆ。Group Rf: n-04F, :1So-04F,
05F',, 06F', 308 F17 09 F
19 010 F21OF30F.
０、ｅＯＦ２０Ｆ２（０Ｆ２０Ｆ２）ｎ−ＨＪＦＯＦ２
０Ｆ２（ＣＦ２０Ｆ２）ｎ−ここで、基Ｒｆのｒ＃素数
が４より少ないと所望の離型性が得られず、一方２０よ
り多い炭素数のものは、そわの合成原料であるＲｆＸＩ
が固体であるため、反応性が劣っている。0, eOF20F2 (0F20F2)n-HJFOF2
0F2(CF20F2)n-Here, if the r# prime number of the group Rf is less than 4, the desired mold releasability cannot be obtained, whereas if the number of carbon atoms is more than 20, RfXI, which is a raw material for the synthesis of foam
Since it is a solid, it has poor reactivity.
ＲｆＸＩ 十Ｐ（ＯＲ’）３←ＲｆＸＰＯ（ＯＲ’）２
＋Ｒ’■具体的には、例えば次式で示さｉするような化
合物が、代表的なｆヒ合物として示される。RfXI 10P(OR')3←RfXPO(OR')2
+R'■ Specifically, for example, a compound represented by the following formula i is shown as a typical f compound.
０８Ｆ１．（ＯＨ２）２ＰＯ（ＯＨ）２Ｃ４゜Ｆ２．（
ＣＨ２）２ＰＯ（ＯＨ）２（ＣＦ３）２０Ｆ（ＯＦ２０
Ｆ２）２Ｎ４０Ｈ２ａＨ２ＰＯ（ＯＨ）、。08F1. (OH2)2PO(OH)2C4°F2. (
CH2)2PO(OH)2(CF3)20F(OF20
F2) 2N40H2aH2PO(OH).
（０Ｆ３） ３０（ＯＦ２０Ｆ２）２Ｎ４０Ｈ２０Ｈ２
ＰＯ（ＯＨ）２これらのポリフルオロカーボン基含有ホ
スホン酸は、金属塩、アミン塩またはアンモニウム塩の
形で用いることが好ましい。塩の形成は、例えば水酸化
ナトリウム、水酸化カリウム、水酸化アンモニウム、硫
酸亜鉛、酢酸亜鉛、酸化亜鉛、トリエチルアミン、トリ
エタノールアミン、トリス（２゜−ヒドロキシエチル）
アミンなどを用い、通常はｐＨでその等散点をみながら
、上記塩形成剤で滴定し、酸性の塩とする。(0F3) 30(OF20F2)2N40H20H2
PO(OH)2 These polyfluorocarbon group-containing phosphonic acids are preferably used in the form of metal salts, amine salts or ammonium salts. Salt formation is possible, for example, with sodium hydroxide, potassium hydroxide, ammonium hydroxide, zinc sulfate, zinc acetate, zinc oxide, triethylamine, triethanolamine, tris(2°-hydroxyethyl)
Using an amine or the like, titration is performed with the above-mentioned salt-forming agent, usually while checking its equidispersity point based on pH, to form an acidic salt.
ワックスとしては、例えばカルナバワックス、マイクロ
ワックス、木ロウ、密ロウ、ステアリン酸モノグリセリ
ド、オレイン酸モノゲリセリド、ポリエチレンワックス
、ステアリン酔アミド、オレイン酸アミドなど、金型の
使用温度（約８０〜１３０℃）で融解する、常温で固体
のものが用いられる。こわらのワックスは、ポリフルオ
ロカーボン基含有ホスホン陣１００重量部に対して約１
０〜５００重は部、好ましくは約３０〜３００重量部、
更【好ましくけ約１０〜５００置部の割合で用いられる
。Examples of wax include carnauba wax, microwax, wood wax, beeswax, stearic acid monoglyceride, oleic acid monoglyceride, polyethylene wax, stearic acid amide, oleic acid amide, etc. at the mold usage temperature (approximately 80 to 130°C). Those that melt and are solid at room temperature are used. The amount of Kowara wax is approximately 1 part by weight per 100 parts by weight of the polyfluorocarbon group-containing phosphonic group.
0 to 500 parts by weight, preferably about 30 to 300 parts by weight,
It is preferably used in a proportion of about 10 to 500 parts.
ポリフルオロカーボン基含有ホスホン酸またはその塩お
よびワックスよりなる離型剤は、有機媒体または水性媒
体の溶液寸たは分散液として調製される。A mold release agent consisting of a polyfluorocarbon group-containing phosphonic acid or its salt and a wax is prepared as a solution or dispersion in an organic or aqueous medium.
有機媒体を用いての離型剤溶液の調製は、例えば後記実
施例記載の如き方法で行われる。有機媒体の代りに水性
媒体が用いられる場合には、混合有機溶媒の代りに、例
えば水１００；界面活性剤（花王石鹸製品エマルゲン９
５（１）２ニドデシル硫酸ナトリウム１よりなる水性液
９４重置部が、ホスホン酸の酸性Ｊａ１重）Ｊｔ部およ
びワックス５重量部に対して用いられる。The release agent solution using an organic medium is prepared, for example, by a method as described in Examples below. When an aqueous medium is used instead of an organic medium, for example water 100%; surfactant (Kao soap product Emulgen 9%
94 parts by weight of an aqueous solution consisting of 1 part by weight of 5(1)2 sodium nidodecyl sulfate are used for 1 part by weight of acidic Ja of phosphonic acid and 5 parts by weight of wax.
上記離型剤の調製に用いられる有機溶媒としては、こり
、以外に１．１．２−）リフルオロ−１，２，２−トリ
クロルエタン、１，２−ジフルオロテトラクロルエタン
レン、塩化メチレン、デカリン、ｎ−オクタン、イソオ
クタン、トルエン、キシレン、酢酸ブチル、酢酸エチル
、イソプロピルアルコールなどの１種または２種以上が
用いられる。′ｆた、水性奴体としては、一般に水、エ
チレングリコール、セロソルブ類、テトラヒドラフラン
、ジオキサン、アルコール類、グリコール類、グリセリ
ンなどが用いらり．る。Examples of organic solvents used in the preparation of the above mold release agent include 1.1.2-)lifluoro-1,2,2-trichloroethane, 1,2-difluorotetrachloroethanelene, methylene chloride, and decalin, in addition to chloride. , n-octane, isooctane, toluene, xylene, butyl acetate, ethyl acetate, isopropyl alcohol, or the like. In general, water, ethylene glycol, cellosolves, tetrahydrofuran, dioxane, alcohols, glycols, glycerin, etc. are used as the aqueous substance. Ru.
このようにして調製された離型剤は、それを成形用金型
に塗布して使用した場合、得られた成形品表面にヌメリ
感がなく、このことは成形品に良好な後加工性を確保さ
ゼる。この離型剤はまた、ゴム生地などに表面塗布され
た場合に生地の粘着防止に有効であり、紙や木材などの
表面に塗布さＪまた場合てけ粘着防止ばかりではなく、
汚ねの防止などにも有効である。When the mold release agent prepared in this way is applied to a mold for molding, there is no slimy feeling on the surface of the molded product, which gives the molded product good post-processability. Secured. This mold release agent is also effective in preventing adhesion of materials when applied to surfaces such as rubber materials, and is effective in preventing adhesion when applied to surfaces such as paper or wood.
It is also effective in preventing stains.
次に、実強例について本発明の詳細な説明する。Next, a detailed explanation of the present invention will be given regarding a practical example.
実１布例
離型剤の調製
＊ スホンｉｆｆ Ｏ８Ｆ、、（ＯＨ２）２Ｐｎ（ＯＨ
）２５９をイソプロピルアルコール３００１ηＰに溶か
し、これＩＣ対し１４モル喰のトリエチルアミンを加え
、半分中和した後イソプロピルアルコールを留去する。Example 1: Preparation of mold release agent*
) 259 is dissolved in 3001 ηP of isopropyl alcohol, and 14 molar portions of triethylamine are added to the solution to half neutralize it, and then the isopropyl alcohol is distilled off.
このようにして得られ、たホスホン酸の酸性トリエチル
アミン塩１市晴部に、カルナバワックス５重量部および
混合溶媒（イソプロピルアル：ｌ −ル５ ： １，１
．２−トリクロル−１，２，２−）リフルオロエタン５
ニトリクロルエチレン１０）９４重量部を加え、混合物
を加熱溶解させて削型剤を調製した。To 1 part of the acidic triethylamine salt of phosphonic acid thus obtained, 5 parts by weight of carnauba wax and a mixed solvent (isopropyl alcohol: 5:1,1
．． 2-Trichloro-1,2,2-)lifluoroethane 5
94 parts by weight of nitrichlorethylene (10) was added, and the mixture was heated and dissolved to prepare a cutting agent.
離型性テスト
２００ ｘ １００ Ｘ ２制の、試験片を成形するた
めの金型の内面に前記離型剤を塗布し、そこに樹脂成形
材料を入；ｈｌ、一定時間硬化、加硫させる。具体的に
は、各樹脂成形材料の種類に応じて、次のようにして行
われた。Mold release property test: The above mold release agent is applied to the inner surface of a mold for molding a 200 x 100 x 2 test piece, and a resin molding material is put therein, and the resin molding material is cured and vulcanized for a certain period of time. Specifically, it was carried out as follows depending on the type of each resin molding material.
ポリウレタン：ポリウレタンプレポリマー （日本ポリ
ウレタン製品コロネートａ −４０９０；ポリエーテル
型プレポリマー、−ＮＯＱ含有量４２％）１００部を８
５℃に加熱し、１００ｗｎＨｇの減圧下で脱泡する。こ
れとは別に、硬化剤メチレンビス−〇−クロルアニリン
（イハラケミカル製品イハラキュアミンＭＴ）１２．７
部を加熱溶融し、気泡をまき込まないようにしながら、
上記脱泡ポリウレタンプレポリマーと攪拌下に混合する
。この溶融混合物を、成形金型内に流し込み、１２０℃
で１時間硬化させる。Polyurethane: 100 parts of polyurethane prepolymer (Japan Polyurethane Products Coronate A-4090; polyether type prepolymer, -NOQ content 42%) 8 parts
Heat to 5°C and defoam under reduced pressure of 100wnHg. Separately, the curing agent methylenebis-〇-chloroaniline (Ihara Chemical product Iharacuamine MT) 12.7
Heat and melt the parts, while being careful not to introduce air bubbles.
Mix with the above defoamed polyurethane prepolymer while stirring. This molten mixture was poured into a mold and heated to 120°C.
Let harden for 1 hour.
アクリルゴム：エチルアクリレート系共重合コム（日本
メクトロン製品Ｎｏｘｔｉｔｅ ＰＡ ４０１ ）
１００部、ＨＡ１！Ｉカーボンブラック５０部、イオウ
１部、ステアリン酸ナトリウム０．２部、ステアリン酸
カリウム０．１部および硫酸鉛５部をロールで練り、こ
れを成形金型内に入れ、１８０℃で１０分間の一次加硫
を行なう。Acrylic rubber: Ethyl acrylate copolymer comb (Nippon Mektron product Noxtite PA 401)
100 copies, HA1! 50 parts of I carbon black, 1 part of sulfur, 0.2 parts of sodium stearate, 0.1 part of potassium stearate and 5 parts of lead sulfate were kneaded with a roll, put into a mold, and heated at 180°C for 10 minutes. Perform primary vulcanization.
フッ素ゴム：ヘキサフルオロプロペン−フッ化ビニリデ
ン共重合ゴム（デュポン製品パイトンＡ）１００部、Ｍ
Ｔカーボンブラック２０部、ビスフェノールＡ１部、ベ
ンジルトリフェニルホスホニウムクロライド０．２部、
酸化カルシウム１０部および酸化マグネシウム５部をロ
ールで練り、これを成形金型内に入れ、２００℃で７分
間の一次加硫を行なう。Fluororubber: 100 parts of hexafluoropropene-vinylidene fluoride copolymer rubber (DuPont product Piton A), M
20 parts of T carbon black, 1 part of bisphenol A, 0.2 part of benzyltriphenylphosphonium chloride,
10 parts of calcium oxide and 5 parts of magnesium oxide are kneaded with a roll, put into a mold, and primary vulcanization is performed at 200° C. for 7 minutes.
このような成形操作がくり返されるが、成形金型内面へ
の離型剤の塗布は最初の１回のみとし、２回目からは離
型剤を新たに塗布することなく成形操作をくり返し、こ
のような操作を成形品が成形金型から離型しなくなる進
行ない、離型することができた回数を測定する。得られ
た結果は、次の表１に示される。なお、Ａ５は、ワック
スの代りに同濃度のシリコンオイルが用いられた参考例
である。Such a molding operation is repeated, but the mold release agent is only applied to the inner surface of the molding die the first time, and from the second time onwards, the molding operation is repeated without applying a new mold release agent. The number of times the molded product can be released from the mold without progressing to the point where the molded product cannot be released from the mold is measured. The results obtained are shown in Table 1 below. Note that A5 is a reference example in which silicone oil of the same concentration was used instead of wax.
表１
１ 木ロウ ２５ １０
１１２ カルナバワックス ２３ １
１ １２３ 密ロウ ２１
１．０ １１４ マイクロワックス
２０ ９ １０５ シリコン
オイル ２２ １１ １２
Ａ１〜５の離型性能について更に観察すると、いずわも
離型回数が５回迄は容易に離型することができ、金型に
は成形品のかすが残らなかったが、離型回数が６回以降
は離型が次第にしずらくなり、各最終離型回数に近ずく
につれて金型に成形品のかすが付き易くなった。いずれ
にしても、この結果から、ワックスを用いた場合には、
シリコンオイルを用いた場合と同程咽の離型性能が得ら
れることが分り、一方成形品表面のべとつきやつるつる
した感じの判定では、成形品表面に１０×１０×１０ｍ
ｍの立方体状アルミニウムを搭載し、成形品の一端を徐
々に持ち上げていったところ、室温で屋１の場合には７
０６の角度で搭載物が滑り出したのに対し、Ａ５の場合
には早くも４５°で滑り出したことから、本発明の離型
剤を用いると、後加工性が良好であることが分る。Table 1 1 Wood wax 25 10
112 Carnauba wax 23 1
1 123 Hitsuwa 21
1.0 114 Micro wax
20 9 105 Silicone oil 22 11 12
Further observation of the mold release performance of A1 to A5 revealed that the molds could be easily released up to 5 times, and no residue of the molded product remained in the mold. After the 6th mold release, it became gradually more difficult to release the mold, and as each final mold release number approached, it became easier for molded product residue to adhere to the mold. In any case, from this result, when using wax,
It was found that the same level of mold release performance as when using silicone oil was obtained, and on the other hand, when judging the stickiness or smoothness of the surface of the molded product, it was found that the surface of the molded product was 10×10×10 m
When one end of the molded product was gradually lifted up with a cubic aluminum cube of
The loaded object began to slide at an angle of 06 degrees, whereas in the case of A5 it began to slide at an angle of 45 degrees, which indicates that the use of the mold release agent of the present invention provides good post-processability.
比較例
実施例において、そこで用いられたホスホン酸トリエチ
ルアミン塩の混合溶媒溶液の代りに、相当するリン酸ト
リエチルアミン塩の混合溶媒溶液が用いらｈ１同様Ｖ（
離型回数の測定が行われた。Comparative Example In place of the mixed solvent solution of phosphonic acid triethylamine salt used therein, a corresponding mixed solvent solution of phosphoric acid triethylamine salt was used.
The number of times the mold was released was measured.
得られた結果は、次の表２に示ざわる。The results obtained are shown in Table 2 below.
表２
１ 木ロウ １３７８
２ カルナバワックス １５ ８
８３ 密ロウ １１７７
４ マイクロワックス １２ ７
８屋１〜４の離型性能について更に観察すると
、いずれも離型回数が４回以降離型がしずらくなり、離
型回数７回前後で金型に成形品のかすが付き始めるのが
認めら′ｈだ。Table 2 1 Wood wax 1378 2 Carnauba wax 15 8
83 Hitsuwa 1177 4 Microwax 12 7
When we further observed the mold release performance of 8-Ya 1 to 4, it was found that in all cases, it became difficult to release the mold after the 4th mold release, and that residue of the molded product began to adhere to the mold around the 7th mold release. It's ra'h.
これらの結果と前記実施例の結果とを対比すると、ワッ
クスを用いた離型剤の場合には、ポリフルオロカーボン
基含有リン重重たはその塩を用いたときよりもポリフル
オロカーボン基含有ホスホン重重たはその填を用いた方
が、離型性能の点で格段とずぐシ］ていることが分る。Comparing these results with the results of the above examples, it can be seen that in the case of a mold release agent using wax, the release agent has a higher release rate than when using a polyfluorocarbon group-containing phosphor group or its salt. It can be seen that the mold release performance is much better when this filler is used.
代理人
弁理士 吉 １）俊 夫
ｒｌｌ）
手 続 廼 正 書 （自発）特許庁長官
若 杉 和 夫 殿
１事件の表示
昭和５８年持重願第４１８９１号
２、発明の名称
離型剤
３、補正をする者
事件との関係 特許出願人
名称 日本メクトロン株式会社
４、代 理 人
住 所 東京都港区芝大門１−２−７ 阿灰ビル５
０１号明細書の発明の詳細な説明の間
６、補正の内容
（１）第６頁第９行の１水、」を「水または」に訂正す
る。Representative Patent Attorney Yoshi 1) Toshio rll) Procedures Proceedings (Voluntary) Commissioner of the Patent Office
Kazuo Wakasugi 1 Indication of the case No. 41891 of 1989 2 Name of the invention Mold release agent 3 Relationship with the case of the person making the amendment Patent applicant name Nippon Mectron Co., Ltd. 4 Agent address Ahai Building 5, 1-2-7 Shiba Daimon, Minato-ku, Tokyo
Part 6 of the Detailed Explanation of the Invention in Specification No. 01, Contents of Amendment (1) On page 6, line 9, 1 "water" is corrected to "water or".
’（，２）第６頁第１１行の１など」の後に「水溶性溶
媒の水溶液」を挿入する。Insert "aqueous solution of water-soluble solvent" after '(,2) 1 etc. on page 6, line 11.'
Claims (1)
数４〜２０のポリフルオロカーボン基であり、Ｘは２価
の有機基である〕で表わされるポリフルオロカーボン基
含有ホスホン酸またはその塩およびワックスを有機媒体
または水性媒体中に溶解または分散させてなる離型剤。[Claims] 1. A polyfluorocarbon group represented by the general formula RfXPO(○H)2 [where Rf is a polyfluorocarbon group having 4 to 20 carbon atoms, and X is a divalent organic group] A mold release agent comprising a phosphonic acid or a salt thereof and a wax dissolved or dispersed in an organic medium or an aqueous medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4189183A JPS59166596A (en) | 1983-03-14 | 1983-03-14 | Mold release agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4189183A JPS59166596A (en) | 1983-03-14 | 1983-03-14 | Mold release agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59166596A true JPS59166596A (en) | 1984-09-19 |
| JPH0378244B2 JPH0378244B2 (en) | 1991-12-13 |
Family
ID=12620904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4189183A Granted JPS59166596A (en) | 1983-03-14 | 1983-03-14 | Mold release agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59166596A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0452632A2 (en) * | 1990-03-03 | 1991-10-23 | Kali-Chemie Aktiengesellschaft | Dichloro-pentafluoropropanes-containing compositions |
| EP0597115A4 (en) * | 1992-04-28 | 1994-03-08 | Daikin Ind Ltd | Parting agent. |
| WO2011030775A1 (en) * | 2009-09-11 | 2011-03-17 | ユニマテック株式会社 | Polyfluoroalkylphosphonic acid oxyalkylene ester, method for producing same and release agent containing same as active ingredient |
| JP2011057632A (en) * | 2009-09-11 | 2011-03-24 | Unimatec Co Ltd | Polyfluoroalkylphosphonic acid oxyalkylene ester and method for producing the same |
| JP2011056835A (en) * | 2009-09-11 | 2011-03-24 | Unimatec Co Ltd | Release agent |
| US8197586B2 (en) | 2009-03-13 | 2012-06-12 | Unimatec Co., Ltd. | Polyfluoroalkylphosphonic acid, method for producing the same and mold-releasing agent comprising the same as active ingredient |
| US8313573B2 (en) | 2009-09-11 | 2012-11-20 | Unimatec Co., Ltd. | Mold-releasing agent |
| US8361215B2 (en) | 2009-11-04 | 2013-01-29 | Unimatec Co., Ltd. | Polyfluoroalkylphosphonic acid salt emulsifier and mold-releasing agent comprising the same as active ingredient |
| US8377187B2 (en) | 2009-06-04 | 2013-02-19 | Unimatec Co., Ltd. | Graft copolymer and mold-releasing agent comprising same as active ingredient |
| US8454738B2 (en) | 2009-06-05 | 2013-06-04 | Unimatec Co., Ltd. | Mold-releasing agent |
| US8987397B2 (en) | 2010-09-13 | 2015-03-24 | Unimatec Co., Ltd. | Fluorine-containing copolymer |
| US9068059B2 (en) | 2010-05-25 | 2015-06-30 | Unimatec Co., Ltd. | Fluorine-containing polymer aqueous dispersion |
| US9120833B2 (en) | 2009-03-13 | 2015-09-01 | Unimatec Co., Ltd. | Polyfluoroalkylphosphonic acid ester and process for producing the same |
| US9610634B2 (en) | 2009-09-17 | 2017-04-04 | Unimatec Co., Ltd. | Emulsion and mold-releasing agent using the same |
| US10836780B2 (en) | 2017-03-22 | 2020-11-17 | Unimatec Co., Ltd | Polyfluoroalkyl phosphoric acid ester or salt thereof, and mold-releasing agent comprising the same as an active ingredient |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07304043A (en) * | 1994-05-11 | 1995-11-21 | Daikin Ind Ltd | Molding method and diluent for releasant |
| CN102482304B (en) * | 2009-07-10 | 2014-09-03 | 优迈特株式会社 | Polyfluoroalkylphosphonic acid esters and processes for production of same |
| JP5840044B2 (en) * | 2012-03-22 | 2016-01-06 | 株式会社ネオス | An aqueous release agent composition. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5252188A (en) * | 1975-10-24 | 1977-04-26 | Shinnitsutou Kagaku Kk | F-cont. surfactants |
| JPS5340052A (en) * | 1976-09-24 | 1978-04-12 | Daikin Ind Ltd | Mold releasing agent |
-
1983
- 1983-03-14 JP JP4189183A patent/JPS59166596A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5252188A (en) * | 1975-10-24 | 1977-04-26 | Shinnitsutou Kagaku Kk | F-cont. surfactants |
| JPS5340052A (en) * | 1976-09-24 | 1978-04-12 | Daikin Ind Ltd | Mold releasing agent |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0452632A2 (en) * | 1990-03-03 | 1991-10-23 | Kali-Chemie Aktiengesellschaft | Dichloro-pentafluoropropanes-containing compositions |
| EP0597115A4 (en) * | 1992-04-28 | 1994-03-08 | Daikin Ind Ltd | Parting agent. |
| EP0597115A1 (en) * | 1992-04-28 | 1994-05-18 | Daikin Industries, Ltd. | Parting agent |
| US5525150A (en) * | 1992-04-28 | 1996-06-11 | Daikin Industries Ltd. | Mold release agent |
| US9120833B2 (en) | 2009-03-13 | 2015-09-01 | Unimatec Co., Ltd. | Polyfluoroalkylphosphonic acid ester and process for producing the same |
| US8197586B2 (en) | 2009-03-13 | 2012-06-12 | Unimatec Co., Ltd. | Polyfluoroalkylphosphonic acid, method for producing the same and mold-releasing agent comprising the same as active ingredient |
| US8377187B2 (en) | 2009-06-04 | 2013-02-19 | Unimatec Co., Ltd. | Graft copolymer and mold-releasing agent comprising same as active ingredient |
| US8454738B2 (en) | 2009-06-05 | 2013-06-04 | Unimatec Co., Ltd. | Mold-releasing agent |
| WO2011030775A1 (en) * | 2009-09-11 | 2011-03-17 | ユニマテック株式会社 | Polyfluoroalkylphosphonic acid oxyalkylene ester, method for producing same and release agent containing same as active ingredient |
| US8313573B2 (en) | 2009-09-11 | 2012-11-20 | Unimatec Co., Ltd. | Mold-releasing agent |
| US8377188B2 (en) | 2009-09-11 | 2013-02-19 | Unimatec Co., Ltd. | Polyfluoroalkylphosphonic acid oxyalkylene ester, method for producing the same, and mold-releasing agent comprising the same as active ingredient |
| JP2011056835A (en) * | 2009-09-11 | 2011-03-24 | Unimatec Co Ltd | Release agent |
| JP2011057632A (en) * | 2009-09-11 | 2011-03-24 | Unimatec Co Ltd | Polyfluoroalkylphosphonic acid oxyalkylene ester and method for producing the same |
| US9610634B2 (en) | 2009-09-17 | 2017-04-04 | Unimatec Co., Ltd. | Emulsion and mold-releasing agent using the same |
| US9937551B2 (en) | 2009-09-17 | 2018-04-10 | Unimatec Co., Ltd. | Emulsion and mold-releasing agent using the same |
| US8361215B2 (en) | 2009-11-04 | 2013-01-29 | Unimatec Co., Ltd. | Polyfluoroalkylphosphonic acid salt emulsifier and mold-releasing agent comprising the same as active ingredient |
| US9068059B2 (en) | 2010-05-25 | 2015-06-30 | Unimatec Co., Ltd. | Fluorine-containing polymer aqueous dispersion |
| US8987397B2 (en) | 2010-09-13 | 2015-03-24 | Unimatec Co., Ltd. | Fluorine-containing copolymer |
| US10836780B2 (en) | 2017-03-22 | 2020-11-17 | Unimatec Co., Ltd | Polyfluoroalkyl phosphoric acid ester or salt thereof, and mold-releasing agent comprising the same as an active ingredient |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0378244B2 (en) | 1991-12-13 |
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