JPH0378244B2 - - Google Patents
Info
- Publication number
- JPH0378244B2 JPH0378244B2 JP58041891A JP4189183A JPH0378244B2 JP H0378244 B2 JPH0378244 B2 JP H0378244B2 JP 58041891 A JP58041891 A JP 58041891A JP 4189183 A JP4189183 A JP 4189183A JP H0378244 B2 JPH0378244 B2 JP H0378244B2
- Authority
- JP
- Japan
- Prior art keywords
- mold
- mold release
- release agent
- parts
- salt
- 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 - Lifetime
Links
- 239000006082 mold release agent Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 12
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012736 aqueous medium Substances 0.000 claims description 7
- 239000002609 medium Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000001993 wax Substances 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 amine salts Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- UGCSPKPEHQEOSR-UHFFFAOYSA-N 1,1,2,2-tetrachloro-1,2-difluoroethane Chemical compound FC(Cl)(Cl)C(F)(Cl)Cl UGCSPKPEHQEOSR-UHFFFAOYSA-N 0.000 description 1
- 125000005739 1,1,2,2-tetrafluoroethanediyl group Chemical group FC(F)([*:1])C(F)(F)[*:2] 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- JGZVUTYDEVUNMK-UHFFFAOYSA-N 5-carboxy-2',7'-dichlorofluorescein Chemical compound C12=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C2C21OC(=O)C1=CC(C(=O)O)=CC=C21 JGZVUTYDEVUNMK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PCEAEURPWOIORP-UHFFFAOYSA-N OP([O-])=O.CC[NH+](CC)CC Chemical compound OP([O-])=O.CC[NH+](CC)CC PCEAEURPWOIORP-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- UNXNGGMLCSMSLH-UHFFFAOYSA-N dihydrogen phosphate;triethylazanium Chemical compound OP(O)(O)=O.CCN(CC)CC UNXNGGMLCSMSLH-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Lubricants (AREA)
Description
本発明は、離型剤に関する。更に詳しくは、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。
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
オイルなどの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。
離型成分として、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な離型性能を示す
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得られた成形品
は、後加工性の点でも具合の悪い点がみられた。
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
バリ部分の除却、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果となる。
しかるに、シリコンオイルなどに代えてワツク
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。従つて、本発明は
離型剤に係り、この離型剤は、一般式
RfCnH2nPO（OH）2〔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、ｎは１、２ま
たは３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ツクス
を有機媒体または水性媒体中に溶解または分解さ
せてなる。
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
CnH2nとしては、例えば次のようなものが挙げ
られる。
基Rf：ｎ−C4F9 iSo−C4F9 C5F11 C6F13 C8F17
C9F19 C10F21
ClCF2CF2（CF2CF2）o− HCF2CF2
（CF2CF2）o−
ここで、基Rfの炭素数が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、それの合成原料であるRfCnH2nIが固体で
あるため、反応性が劣つている。
RfCnH2nI＋Ｐ（OR′）3→RfCnH2nO（OR′）2＋R′I
基CnH2n：−CH2CH2− −CH2−
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. 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 a mold release agent such as silicone oil is coexisting therewith, for example, according to It is described in Publication No. 23270, Publication No. 53-23271, etc. 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. The same applies when polyfluorocarbon group-containing phosphonic acid or its salt, which exhibits better mold release performance than polyfluorocarbon group-containing phosphoric acid or its salt, is used as a mold release component, and molding coated with this mold release agent. The molded product obtained using the mold also had poor post-processability.
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.
Therefore, when a molded product is fixed and processed, it is not easy to fix it for post-processing, such as removing burrs or accurately cutting a sealing part, resulting in a significant loss of post-processability. . However, it has been found that by using wax instead of silicone oil or the like, all of these drawbacks can be effectively eliminated. Therefore, the present invention relates to a mold release agent, which has the general formula
RfCnH 2 nPO(OH) 2 [Here, Rf has a carbon number of 4 to 20
polyfluorocarbon group, n is 1, 2, or 3] or a salt thereof and wax are dissolved or decomposed in an organic medium or an aqueous medium. In the polyfluorocarbon group-containing phosphonic acid represented by the above general formula, the group Rf and the group
Examples of CnH 2 n include the following. Base Rf: n-C 4 F 9 iSo-C 4 F 9 C 5 F 11 C 6 F 13 C 8 F 17
C 9 F 19 C 10 F 21 ClCF 2 CF 2 (CF 2 CF 2 ) o − HCF 2 CF 2
(CF 2 CF 2 ) o − Here, if the number of carbon atoms in the group Rf is less than 4, the desired mold releasability cannot be obtained, while if the number of carbon atoms is more than 20, RfCnH 2 nI, which is the raw material for its synthesis, cannot be obtained. Since it is a solid, it has poor reactivity. RfCnH 2 nI + P (OR') 3 →RfCnH 2 nO (OR') 2 +R'I group CnH 2 n: -CH 2 CH 2 - -CH 2 -
【式】
具体的には、例えば次式で示されるような化合
物が、代表的な化合物として示される。
C8F17（CH2）2PO（OH）2
C10F21（CH2）2PO（OH）2
（CF3）2CF（CF2CF2）2〜4CH2CH2PO（OH）2
（CF3）3C（CF2CF2）2〜4CH2CH2PO（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でその等量点をみながら、上記塩形成剤で
滴定し、酸性の塩とする。
ワツクスとしては、例えばカルナバワツクス、
マイクロワツクス、木ロウ、密ロウ、ステアリン
酸モノグリセリド、オレイン酸モノグリセリド、
ポリエチレンワツクス、ステアリン酸アミド、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。これらのワツクスは、ポリフルオロカーボ
ン基含有ホスホン酸100重量部に対して約10〜500
重量部、好ましくは約30〜300重量部、更に好ま
しくは約50〜150重量部の割合で用いられる。
ポリフルオロカーボン基含有ホスホン酸または
その塩およびワツクスよりなる離型剤は、有機媒
体または水性媒体の溶液または分散液として調製
される。
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950）２：ドデシル硫酸
ナトリウム１よりなる水性液94重量部が、ホスホ
ン酸の酸性塩１重量部およびワツクス５重量部に
対して用いられる。
上記離型剤の調製に用いられる有機溶媒として
は、これ以外に１，１，２−トリフルオロ−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、パークロルエチレン、トリ
クロルエチレン、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。ま
た、水性媒体としては、一般に水またはエチレン
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、
グリセリンなど水溶性溶媒の水溶液が用いられ
る。
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せる。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
れた場合には粘着防止ばかりではなく、汚れの防
止などにも有効である。
次に、実施例について本発明の効果を説明す
る。
実施例
離型剤の調製
ホスホン酸C8F17（CH2）2PO（OH）25ｇをイソプ
ロピルアルコール300mlに溶かし、これに対し1/2
モル量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。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重量部に、カルナバワツクス５重量部およ
び混合溶媒（イソプロピルアルコール５：１，
１，２−トリクロル−１，２，２−トリフルオロ
エタン５：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離型剤を調製した。
離型性テスト
200×100×２mm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
料を入れ、一定時間硬化、加流させる。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。
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Ｃ−4090；ポリエ
ーテル型プレポリマー、−NCO含有量42％）
100部を85℃に加熱し、100mmHgの減圧下で脱
泡する。これとは別に、硬化剤メチレンビス−
Ｏ−クロルアニリン（イハラケミカル製品イハ
ラキユアミン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撹拌下に混合する。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。
アクリルゴム：エチルアクリレート系共重合ゴム
（日本メクトロン製品Noxtite PA−401）100
部、HAFカーボンブラツク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
の一次加流を行なう。
フツ素ゴム：ヘキサフルオロプロペン−フツ化ビ
ニリデン共重合ゴム（デユポン製品バイトン
Ａ）100部、MTカーボンブラツク20部、ビス
フエノールA1部、ベンジルトリフエニルホス
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
の一次加流を行なう。
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迄行ない、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、No.５は、ワツクスの代
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。[Formula] Specifically, for example, a compound represented by the following formula is shown as a representative compound. C 8 F 17 (CH 2 ) 2 PO (OH) 2 C 10 F 21 (CH 2 ) 2 PO (OH) 2 (CF 3 ) 2 CF (CF 2 CF 2 ) 2~4 CH 2 CH 2 PO (OH ) 2 ( CF3 ) 3C ( CF2CF2 ) 2 ~ 4CH2CH2PO (OH)2These polyfluorocarbon group-containing phosphonic acids can be used in the form of metal salts, amine salts or ammonium salts . preferable. Salt formation is carried out using, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, zinc sulfate, zinc acetate, zinc oxide, triethylamine, triethanolamine, tris(2-hydroxyethyl)amine, etc., usually at pH. While checking the equivalence point, titrate with the above salt forming agent to form an acidic salt. Examples of wax include carnauba wax,
Micro wax, wood wax, beeswax, stearic acid monoglyceride, oleic acid monoglyceride,
Polyethylene wax, stearic acid amide, oleic acid amide, etc., mold usage temperature (approx.
Melt at 130℃). Those that are solid at room temperature are used. These waxes contain approximately 10 to 500 parts by weight of polyfluorocarbon group-containing phosphonic acid.
The amount used is preferably about 30 to 300 parts by weight, more preferably about 50 to 150 parts by weight. A mold release agent consisting of a polyfluorocarbon group-containing phosphonic acid or its salt and wax is prepared as a solution or dispersion in an organic or aqueous medium. 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, instead of the mixed organic solvent, for example, 94 parts by weight of an aqueous liquid consisting of 100 parts water: 2 parts surfactant (Kao soap products Emulgen 950): 1 part sodium dodecyl sulfate, It is used for 1 part by weight of an acid salt of phosphonic acid and 5 parts by weight of wax. In addition to this, organic solvents used for preparing the above mold release agent include 1,1,2-trifluoro-1,
2,2-trichloroethane, 1,2-difluorotetrachloroethane, perchlorethylene, trichlorethylene, methylene chloride, decalin, n-
Octane, isooctane, toluene, xylene,
One or more of butyl acetate, ethyl acetate, isopropyl alcohol, etc. are used. In addition, the aqueous medium generally includes water, ethylene glycol, cellosolves, tetrahydrofuran, dioxane, alcohols, glycols,
An aqueous solution of a water-soluble solvent such as glycerin is used. 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. ensure it. This mold release agent also
When applied to the surface of rubber fabric, etc., it is effective in preventing the fabric from sticking. When applied to the surface of paper, wood, etc., it is effective not only in preventing adhesion, but also in preventing stains. Next, the effects of the present invention will be explained with reference to Examples. Example Preparation of mold release agent Dissolve 5 g of phosphonic acid C 8 F 17 (CH 2 ) 2 PO (OH) 2 in 300 ml of isopropyl alcohol, and add 1/2
A molar amount of triethylamine is added and after half neutralization the isopropyl alcohol is distilled off. To 1 part by weight 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,
94 parts by weight of 1,2-trichloro-1,2,2-trifluoroethane (5) and trichloroethylene (10) were added, and the mixture was dissolved by heating to prepare a mold release agent. Mold releasability test The above-mentioned mold release agent is applied to the inner surface of a mold for molding a 200 x 100 x 2 mm test piece, a resin molding material is put there, and the molding material is cured and heated for a certain period of time. Specifically, it was carried out as follows depending on the type of each resin molding material. Polyurethane: Polyurethane prepolymer (Japan Polyurethane Product Coronate C-4090; polyether type prepolymer, -NCO content 42%)
100 parts are heated to 85°C and degassed under reduced pressure of 100mmHg. Separately, the curing agent methylene bis-
12.7 parts of O-chloroaniline (Ihara Chemical product Ihara Kiyuamine MT) is heated and melted, and mixed with the above defoamed polyurethane prepolymer while stirring, while being careful not to incorporate air bubbles. Pour this molten mixture into a mold and
Cure for 1 hour at °C. Acrylic rubber: Ethyl acrylate copolymer rubber (Nippon Mektron product Noxtite PA-401) 100
50 parts HAF carbon black, 1 part sulfur,
0.2 parts of sodium stearate, 0.1 parts of potassium stearate, and 5 parts of lead sulfate are kneaded with a roll, placed in a mold, and subjected to primary flow at 180°C for 10 minutes. Fluorine rubber: 100 parts of hexafluoropropene-vinylidene fluoride copolymer rubber (DuPont product Viton A), 20 parts of MT carbon black, 1 part of bisphenol A, 0.2 parts of benzyl triphenylphosphonium chloride, 10 parts of calcium oxide
1 part and 5 parts of magnesium oxide are kneaded with a roll, placed in a mold, and subjected to primary flow at 200°C for 7 minutes. Such molding operations are repeated, but the mold release agent is only applied to the inner surface of the mold once,
From the second time onwards, the molding operation is repeated without applying a new release agent, and this operation is repeated until the molded product no longer releases from the mold, and the number of times the molded product can be released from the mold is measured. The results obtained are shown in Table 1 below. Note that No. 5 is a reference example in which silicone oil of the same concentration was used instead of wax.
【表】
No.１〜５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つた
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つた。いずれにしても、
この結果から、ワツ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度の離型性能が得
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×
10×10mm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つたところ、室温
でNo.１の場合には70°の角度で搭載物が滑り出し
たのに対し、No.５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。
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
が用いられ、同様に離型回数の測定が行われた。
得られた結果は、次の表２に示される。[Table] Further observation of the mold release performance of Nos. 1 to 5 shows that
In either case, the mold could be easily released up to 5 times, and no molded product residue remained in the mold, but after 6 times, it became gradually difficult to release the mold, and each As the final number of times the mold was released approached, it became easier for molded product residue to adhere to the mold. In any case,
From this result, it was found that when wax was used, the same level of mold release performance was obtained as when silicone oil was used; 10×
When a 10 x 10 mm aluminum cube was mounted and one end of the molded product was gradually lifted, the mounted object began to slide at an angle of 70° in the case of No. 1 at room temperature, but in the case of No. 5. In some cases, the mold began to slide as early as 45°, which indicates that the use of the mold release agent of the present invention provides good post-processability. Comparative Example In place of the mixed solvent solution of phosphonic acid triethylamine salt used in the example, a corresponding mixed solvent solution of phosphoric acid triethylamine salt was used, and the number of times of mold release was similarly measured.
The results obtained are shown in Table 2 below.
【表】
No.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れた。
これらの結果と前記実施例の結果とを対比する
と、ワツ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酸またはその塩を用い
たときよりもポリフルオロカーボン基含有ホスホ
ン酸またはその塩を用いた方が、離型性能の点で
格段とすぐれていることが分る。[Table] Further observation of the mold release performance of Nos. 1 to 4 shows that
In all cases, it became difficult to release from the mold after 4 times, and it was observed that residue of the molded product began to adhere to the mold around 7 times. Comparing these results with the results of the above examples, it is found that in the case of a mold release agent using wax, the amount of polyfluorocarbon group-containing phosphonic acid or its salt is higher than in the case of using polyfluorocarbon group-containing phosphonic acid or its salt. It can be seen that the mold release performance is much better when used.
Claims (1)
素数４〜20のポリフルオロカーボン基であり、ｎ
は１、２または３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
びワツクスを有機媒体または水性媒体中に溶解ま
たは分解させてなる離型剤。1 General formula RfCnH 2 nPO(OH) 2 [Here, Rf is a polyfluorocarbon group having 4 to 20 carbon atoms, and n
is 1, 2 or 3] A mold release agent obtained by dissolving or decomposing a polyfluorocarbon group-containing phosphonic acid or a salt thereof and wax 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 JPS59166596A (en) | 1984-09-19 |
| JPH0378244B2 true 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 (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995031321A1 (en) * | 1994-05-11 | 1995-11-23 | Daikin Industries, Ltd. | Molding method and diluent for mold release agent |
| WO2010140652A1 (en) | 2009-06-05 | 2010-12-09 | ユニマテック株式会社 | Mold release agent |
| WO2011030776A1 (en) | 2009-09-11 | 2011-03-17 | ユニマテック株式会社 | Mold release agent |
| JP4666093B2 (en) * | 2009-03-13 | 2011-04-06 | ユニマテック株式会社 | Process for producing polyfluoroalkylphosphonic acid ester |
| WO2011055609A1 (en) | 2009-11-04 | 2011-05-12 | ユニマテック株式会社 | Polyfluoroalkyl phosphonate salt emulsifying agent and mold release agent comprising same as active ingredient |
| WO2011148795A1 (en) | 2010-05-25 | 2011-12-01 | ユニマテック株式会社 | Aqueous dispersion of fluorine-containing polymer |
| WO2012036036A1 (en) | 2010-09-13 | 2012-03-22 | ユニマテック株式会社 | Fluorine-containing copolymer |
| CN102482304A (en) * | 2009-07-10 | 2012-05-30 | 优迈特株式会社 | Polyfluoroalkylphosphonic acid esters and processes for production of same |
| JP2013194229A (en) * | 2012-03-22 | 2013-09-30 | Neos Co Ltd | Aqueous release agent composition |
| WO2018174041A1 (en) | 2017-03-22 | 2018-09-27 | ユニマテック株式会社 | Polyfluoroalkyl phosphoric acid ester or salt thereof, and release agent having same as active ingredient |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4006688A1 (en) * | 1990-03-03 | 1991-09-05 | Kali Chemie Ag | COMPOSITIONS WITH DICHLORPENTAFLUOROPROPANES |
| JPH05301228A (en) * | 1992-04-28 | 1993-11-16 | Daikin Ind Ltd | Release agent |
| CA2753117C (en) | 2009-03-13 | 2013-12-31 | Unimatec Co., Ltd. | Polyfluoroalkylphosphonic acid, method for producing the same and mold-releasing agent comprising the same as active ingredient |
| CN102458789B (en) | 2009-06-04 | 2014-09-03 | 优迈特株式会社 | Graft copolymer and mold release agent comprising same as active ingredient |
| EP2476687B1 (en) * | 2009-09-11 | 2013-12-25 | Unimatec Co., Ltd. | Polyfluoroalkylphosphonic acid oxyalkylene ester, method for producing same and release agent containing same as active ingredient |
| JP4737328B2 (en) * | 2009-09-11 | 2011-07-27 | ユニマテック株式会社 | Release agent |
| JP4711011B2 (en) * | 2009-09-11 | 2011-06-29 | ユニマテック株式会社 | Polyfluoroalkylphosphonic acid oxyalkylene 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 |
| JP7333278B2 (en) * | 2020-01-10 | 2023-08-24 | 三菱マテリアル電子化成株式会社 | Release liquid 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 (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995031321A1 (en) * | 1994-05-11 | 1995-11-23 | Daikin Industries, Ltd. | Molding method and diluent for mold release agent |
| JP4666093B2 (en) * | 2009-03-13 | 2011-04-06 | ユニマテック株式会社 | Process for producing polyfluoroalkylphosphonic acid ester |
| WO2010140652A1 (en) | 2009-06-05 | 2010-12-09 | ユニマテック株式会社 | Mold release agent |
| CN102482304A (en) * | 2009-07-10 | 2012-05-30 | 优迈特株式会社 | Polyfluoroalkylphosphonic acid esters and processes for production of same |
| WO2011030776A1 (en) | 2009-09-11 | 2011-03-17 | ユニマテック株式会社 | Mold release agent |
| WO2011055609A1 (en) | 2009-11-04 | 2011-05-12 | ユニマテック株式会社 | Polyfluoroalkyl phosphonate salt emulsifying agent and mold release agent comprising same as active ingredient |
| WO2011148795A1 (en) | 2010-05-25 | 2011-12-01 | ユニマテック株式会社 | Aqueous dispersion of fluorine-containing polymer |
| WO2012036036A1 (en) | 2010-09-13 | 2012-03-22 | ユニマテック株式会社 | Fluorine-containing copolymer |
| JP2013194229A (en) * | 2012-03-22 | 2013-09-30 | Neos Co Ltd | Aqueous release agent composition |
| WO2018174041A1 (en) | 2017-03-22 | 2018-09-27 | ユニマテック株式会社 | Polyfluoroalkyl phosphoric acid ester or salt thereof, and release agent having same as active ingredient |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59166596A (en) | 1984-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0378244B2 (en) | ||
| US4585829A (en) | Internal mold release for reaction injection molded polyurethanes | |
| GB1567327A (en) | Mould release agent | |
| JPH06511505A (en) | Coating composition and printing method for pad printing | |
| US4592930A (en) | Perfluorocarbon based polymeric coatings having low critical surface tensions | |
| AU2011219566A1 (en) | Associative acrylic emulsion containing a monomer based on oxo alcohol, production method thereof, and method for thickening an aqueous formulation produced from said emulsion | |
| JPH0245572B2 (en) | ||
| JPH044923B2 (en) | ||
| EP2497566B1 (en) | Polyfluoroalkyl phosphonate salt emulsifying agent and mold release agent comprising same as active ingredient | |
| US3558540A (en) | Plastic impression compositions | |
| JPH0411366B2 (en) | ||
| CN102361880B (en) | Phosphate surfactants | |
| JPH0245571B2 (en) | ||
| US2472901A (en) | 2,2' (2-ethylhexanamido) diethyl di (2-ethylhexanoate) | |
| JPH0348846B2 (en) | ||
| JP2844366B2 (en) | Rubber composition for mold cleaning | |
| JPS6234341B2 (en) | ||
| US4666518A (en) | Inside and outside tire paint for green tires | |
| US982572A (en) | Process for casting. | |
| JP3252419B2 (en) | Release agent composition | |
| JP3423975B2 (en) | Release agent | |
| JPS59152961A (en) | Primer composition | |
| JP2001096541A (en) | Aqueous mold release agent for urethane foam | |
| US1906437A (en) | Coating composition | |
| DE711731C (en) | Plastic abrasives |