An aqueous mold-releasing agent

Abstract: The present invention provides an aqueous mold-releasing agent which exhibits an excellent mold-releasing property with a small applied amount thereof without causing roughed surfaces of molded articles. Said agent comprises at least one of the fluorine-containing sulfonates in combination with a wax and/or a silicone oil, said sulfonates being represented by the following formula (I): (XSO₃) ℓ M (I) ,wherein X is any one of the following fluorine-containing groups: and C m F 2m+1 (CH₂) n -(n:0 - 2, m:1 - 12), M is an alkali metal, an alkaline earth metal, zinc, an alkylamine, an alkanolamine or ammonium and ℓ is 1 or 2.

Description: The present invention relates to an aqueous mold-releasing agent which exhibits an excellent mold-releasing property with a small applied amount thereof without causing roughed surfaces of molded articles. In a process for preparing molded articles made of resins such as polyurethane and the like, a mold-releasing agent has heretofore been applied on inner walls of a mold prior to a molding in order to facilitate a release of the molded articles from the mold. The commonly used mold-releasing agent is a solvent type agent prepared by blending a wax, a silicone oil or fluorine compounds with an organic solvent. In the case where a mold-releasing agent which contains a wax is used, (i) it is difficult to prepare molded articles having smooth finishing surfaces, (ii) the wax adheres and remains on the surfaces of the molded articles because the agent must be applied in large quantities in order to obtain a sufficient releasing effect and (iii) a working hygienical problem arises because a petroleum solvent is used as a base solvent. When a mold-releasing agent which contains a silicone oil is used, the agent causes trouble in that the adhered silicone oil on the surfaces of the molded articles repels a paint during a process of the secondary treatment. Although a mold-releasing agent which contains fluorine compounds exhibits an excellent releasing property in a small amount and does not cause the working hygienical problem, it has a difficult point in that a use of fluorine group solvents which are the base solvent of said agent will completely be prohibited in the near future from the viewpoint of a global environmental problem wherein the ozonesphere is destroyed by said solvents. Therefore, the development of an aqueous mold-releasing agent which can be substituted for the aforementioned solvent type agents is demanded. However, in the case where the aqueous mold-releasing agent is employed, there are problems that not only the resin components such as diisocyanate of foam urethane and the like which are materials of the molded articles react with the remaining water in the mold thereby leading to rough surfaces of the molded articles but also the mold-releasing property itself is unsatisfactory. In order to reduce these problems, several aqueous mold-releasing agents have already been provided. For example, an aqueous mold-releasing agent containing emulsified wax which cuts off from the remaining water in the mold on the base of a mesomorphism by a nonionic surfactant (Japanese Patent KOKAI No. 22912/1986), a high solid type mold-releasing agent which consists of only mold-releasing ingredients is sprayed by means of an exclusive spray and an aqueous mold-releasing agent which comprises a fluorine-containing phosphate (Japanese Patent KOKOKU No. 23270/1978) or a fluorine-containing phosphonate (Japanese Patent KOKOKU No. 6329/1988 and ibid. No. 6330/1988) are cited. However, in the case of the former two mold-releasing agents, the reactivity between water and resin ingredients cannot sufficiently be prevented and said agents are not put to practical use because the mold-releasing properties thereof are inferior and therefore said agents must be used in large quantities in order to obtain the satisfactory mold-releasing effect. In the case where the aqueous mold-releasing agent which comprises the fluorine-containing phosphate is employed, it is difficult to prepare said mold-releasing agent as an aqueous agent because of low solubility of the phosphate in water and the satisfactory mold-releasing effect has not actually been achieved. EP-A-102 240 discloses organic treating agents including a thermally decomposable polyalkylene glycol and a fluorine containing compound. These agents are used for treating metallic or ceramic surfaces and for treating grooved heaters for yarns. The object of the present invention is to provide an aqueous mold-releasing agent which exhibits an excellent mold-releasing property with a small applied amount thereof without bringing about the roughed surfaces of the molded articles caused by the water contained in the agent. The present invention relates to an aqueous mold-releasing agent consisting of a) 0.1 to 15.0 wt.% of a fluorine-containing sulfonate represented by the formula (I) (XSO 3 ) l M wherein X is any one of the following fluorine-containing groups or C m F 2m+1 -(CH 2 ) n - (m: 1-12; n: 0-2) M is an alkali metal, an alkaline earth metal, zinc, an alkylamine, an alkanol amine or ammonium and l is 1 or 2, b) 0.5 to 30 wt.% of a wax and/or a silicone oil c) optionally an emulsifying agent, an organic solvent and other additives, and d) water, with the proviso that component c) does not stand for 50% by weight or more of a polyalkylene glycol or a derivative thereof thermally decomposable at 150°C or above in air. The aqueous mold-releasing agent according to the present invention comprises 0.1 to 15.0 wt.% of at least one of the fluorine-containing sulfonates represented by the following general formula (I) together with 0.5 to 30 wt.% of the wax and/or the silicone oil: (XSO 3 ) ℓ M In the general formula (I), X shows the fluorine-containing groups such as and C m F 2m+1 (CH 2 ) n -, wherein n shows 0,1 or 2 and m shows 1 - 12, preferably 3 - 9. The perfluoroalkenyl groups or perfluoroalkyl groups of the aforesaid fluorine-containing groups may have a branched chain. In the general formula (I), M represents an alkali metal, an alkaline earth metal, zinc, an alkylamine, an alkanolamine or ammonium and ℓ is an integer of 1 or 2. The preferred alkali metals are sodium and potassium and the preferred alkaline earth metals are calcium and magnesium. As an alkylamine, primary, secondary and tertiary amines having 1 - 12 carbon atoms including cyclic amines are exemplified. Monoethanolamine, diethanolamine, triethanolamine and the like are exemplified as an alkanolamine. Particularly suitable sulfonates represented by the formula (I) are as follows: Two or more of the aforementioned sulfonates may jointly be used as the occasion may demand. As the wax used in the present invention, mineral waxes (e.g., montan wax or ozokerite), petroleum waxes (e.g., paraffin wax, microcrystalline wax or petrolatum), synthetic waxes (e.g., polyethylene wax or polyvinylether waxes) and modified waxes of the natural wax derivatives are exemplified. Two or more of these waxes may be used at the same time, if necessary. As the silicone oil used in the present invention, polysiloxanes having alkyl groups, phenyl groups or fluoroalkyl groups at their side chains and the like are exemplified. Two or more of these silicone oils may jointly be used as the occasion may demand. Additives such as silicone resin and the like may be added to the silicone oil. The blending amounts of the aforementioned ingredients of the aqueous mold-releasing agent according to the present invention may suitably be determined depending on the kinds of resin materials of the molded articles, molding temperature, surface conditions of the molded articles, the kinds of the mold-releasing ingredients and the like. Under normal conditions, 0.1 - 15 percent by weight, preferably 0.5 - 5.0 percent by weight of a fluorine-containing sulfonate of formula (I) and 0.5 - 30 percent by weight, preferably 1 - 15 percent by weight of the wax and/or the silicone oil are blended. The aqueous mold-releasing agent according to the present invention may be prepared by solubilizing and/or emulsifying the aforesaid mold-releasing ingredients in water. As an auxiliary agent for emulsifying the aforesaid mold-releasing ingredients in water, aqueous polar organic solvents having a low boiling point which dry easily may be employed as the occasion may demand. As the aqueous polar organic solvents, methanol, ethanol, propanol, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, acetone, 2-butanone and the like are exemplified. As an emulsifying agent, the publicly known surfactants may suitably be employed. The surfactants which may be used in the present invention are as follows: anionic surfactants (e.g., alkylbenzene sulfonates such as decylbenzene sulfonate, dodecylbenzene sulfonate and cetylbenzene sulfonate, polyoxyethylene monoalkylether sulfates such as lauryl ether sulfate having 2 -4 moles of added ethylene oxide, alkylnaphthyl sulfonates and the like), cationic surfactants (e.g., quaternary ammonium hydroxides and salts thereof such as octyltrimethyl ammonium hydroxide, dodecyltrimethyl ammonium hydroxide, octyldimethylbenzyl ammonium hydroxide, decyldimethylbenzyl ammonium hydroxide, didodecyldimethyl ammonium hydroxide, dioctadecyldimethyl ammonium hydroxide, beef tallow trimethyl ammonium hydroxide and coconut oil trimethyl ammonium hydroxide) and nonionic surfactants (e.g., polyoxyethylene alkylenealkyl ether, polyoxyethylene alkylenealkylphenol ether, polyoxyethylene alkylenealkyl ester, polyoxyalkylene sorbitan alkyl ester and polyoxyethylene fatty acid amides having C 10 - C 18 -lipophilic groups and 1 - 20 moles of added ethylene oxide). Two or more of these surfactants may suitably be used, if necessary. These surfactants may be used in such an amount that the aforementioned mold-releasing ingredients can be emulsified in water and therefore the amounts of the surfactants to be used are not limitative. Under normal conditions, 2 - 75 parts by weight, preferably 10 - 30 parts by weight of the surfactants may be used, said amounts being based on 100 parts by weight of the mold-releasing ingredients mentioned above. Suitable organic solvents such as cyclohexane and the like may be admixed with the aqueous mold-releasing agent according to the present invention in order to improve a levelling property of the wax, if necessary. In addition, other additives such as rust preventives and preservatives may be added to the aqueous mold-releasing agent according to the present invention as the occasion may demand. The present invention is illustrated by the following examples. Example 1 One part by weight of polyoxyethylene oleyl ether (HLB:12) and 40 parts by weight of warm water (50 - 60°C) were admixed with a solution prepared by solubilizing 5 parts by weight of polyvinyl ether wax in 10 parts by weight of cyclohexane under heating. The wax emulsion was prepared by adding 2 parts by weight of polyoxyethylene oleyl ether (HLB:10) and 42 parts by weight of water to the aforesaid mixture under agitation. The aqueous mold-releasing agent (1) was prepared by admixing 3 g of 30 % - methanolic solution of the fluorine - containing sulfonate I with 30 g of the wax emulsion. The obtained aqueous mold-releasing agent (1) was subjected to the following mold-releasing power test. Mold-releasing power test: The mold-releasing agent is applied uniformly on the inner walls of the warmed (50 °C) apparatus made of aluminum for testing a mold-releasing power of a molded article (13 cm x 10 cm x 1 cm) produced therein by foaming under pressure by means of TI - 506N model spray gun having a nozzle diameter of 0.9 mm (Hokushin Seiki Inc.), said spray gun being 10 - 15 cm away from said inner walls. The polyol is blended with the diisocyanate under agitation for 5 - 7 seconds and then the mixture is poured into the apparatus. After 5 minutes, the hook of the apparatus is pulled by means of the push-pull scale and a necessary load to release a molded article of semi-rigid urethane foam from the apparatus (mold-releasing power) is measured. The applied amount of the aqueous mold-releasing agent is also measured by determining a weight difference of the spray gun before and after application of said agent. The mold-releasing power and the applied amount of the aqueous mold-releasing agent are shown in Table 1. The footnotes appeared in Table 1 are as follows: 1) Average molecular weight: 3000; melting point: 45 - 48 °C 2) Average molecular weight: 2500; melting point: 45 - 50 °C 3) Branched dimethyl polysiloxane (viscosity: 3500 - 5500 cs) 4) Alkylated silicone (viscosity: 500 cp) 5) Calcium perfluorohexenyloxy benzenesulfonate 6) Sodium perfluorohexenyloxy benzenesulfonate 7) Sodium 2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentyl benzenesulfonate 8) Mixture of calcium perfluorohexenyloxy benzenesulfonate and sodium perfluorooctyl sulfonate in a weight ratio of 2 : 1 9) Zinc bis 4-perfluorononenyloxy benzenesulfonate 10) Diethanolamine 4-perfluorononenyloxy benzylphosphonate 11) Polyoxyethylene oleyl ether (HLB:12) which is commercially available from Daiichi Kogyo Inc. as "Noygen ET 129" 12) Polyoxyethylene oleyl ether (HLB:10) which is commercially available from Daiichi Kogyo Inc. as "Noygen ET 109" 13) Unit of the blending amounts of the ingredient is percent by weight. Examples 2 - 10 The aqueous mold-releasing agents (2) - (10) were prepared on the basis of the blending ratios of the ingredients shown in Table 1 in accordance with the procedure described in Example 1. These agents were subjected to the aforementioned mold-releasing power test. The mold-releasing powers and the applied amounts of these agents are summarized in Table 1. Comparative Examples 1 - 5 The aqueous mold-releasing agents (1') - (5') were prepared on the basis of the blending ratios of the ingredients shown in Table 2 in accordance with the procedure described in Example 1. These agents were subjected to the aforesaid mold-releasing power test. The mold-releasing powers and the applied amounts of these agents are summarized in Table 2. The footnotes of Table 2 are the same as that appeared in Table 1. The aqueous mold-releasing agent according to the present invention exhibits an excellent mold-releasing property with a small applied amount thereof without bringing about the roughed surfaces of the molded articles caused by the water contained in said agent. The working hygienical problems are not caused by said agent. Approximately same productivity as that achieved by employing the solvent type mold-releasing agent can be obtained by using the aqueous mold-releasing agent according to the present invention. The aqueous mold-releasing agents 13) (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) Polyvinylether wax 1) 4.5 4.3 4.3 4.4 - 4.3 4.1 4.3 4.0 4.3 Polyethylene wax 2) - - - - 4.3 - - - - - Silicone oil I 3) - 1.7 1.7 1.8 1.7 - 1.7 1.7 1.6 1.7 Silicone oil II 4) - - - - - 1.8 - - - - F-containing sulfonate I 5) 2.7 2.6 2.6 1.8 2.6 2.6 - - - - F-containing sulfonate II 6) - - - - - - 2.5 - - - F-containing sulfonate III 7) - - - - - - - 2.6 - - F-containing sulfonate IV 8) - - - - - - - - 2.4 - F-containing sulfonate V 9) - - - - - - - - - 2.6 F-containing phosphonate 10) - - - - - - - - - - Methanol 6.4 6.1 6.1 4.2 6.1 6.1 6.1 6.1 6.8 6.1 Cyclohexane 9.0 8.6 8.6 8.9 8.6 8.6 9.9 8.6 8.0 8.6 nonionic surfactant I 11) 0.9 0.9 0.9 0.9 0.9 0.8 0.8 0.9 0.8 0.9 nonionic surfactant II 12) 1.8 1.7 1.7 1.8 1.7 1.7 1.7 1.7 1.6 1.7 Water 74.7 74.1 74.1 76.2 74.1 74.1 73.2 74.1 74.8 74.1 Applied amount (g) 1.03 1.02 1.56 0.94 1.02 0.88 0.99 0.97 1.29 1.18 Mold-releasing power (kgf) 6.8 2.2 0.9 5.4 3.0 3.8 8.0 11.0 1.7 3.5 The aqueous mold-releasing agents 13) (1') (2') (3') (4') (5') Polyvinylether wax 1) 5.0 4.7 8.6 - 4.3 Polyethylene wax 2) - - - - - Silicone oil I 3) - 1.9 - - 1.7 Silicone oil II 4) - - - - - F-containing sulfonate I 5) - - - - - F-containing sulfonate II 6) - - - 8.6 - F-containing sulfonate III 7) - - - - - F-containing sulfonate IV 8) - - - - - F-containing sulfonate V 9) - - - - - F-containing phosphonate 10) - - - - 1.7 Methanol - - - - - Cyclohexane 10.0 9.2 17.2 - 8.6 nonionic surfactant I 11) 1.0 0.9 0.9 - 0.9 nonionic surfactant II 12) 2.0 1.9 1.7 - 1.7 Water 82.0 81.4 71.6 92.4 81.1 Applied amount (g) 1.0< 0.98 1.36 1.28 1.29 Mold-releasing power (kgf) 20< 14 13 20< 20.0<

Claims: An aqueous mold-releasing agent consisting of a) 0.1 to 15.0 wt.% of a fluorine-containing sulfonate represented by the formula (I) (XSO 3 ) l M wherein X is any one of the following fluorine-containing groups or C m F 2m+1 -(CH 2 ) n - (m: 1-12; n: 0-2) M is an alkali metal, an alkaline earth metal, zinc, an alkylamine, an alkanol amine or ammonium and l is 1 or 2, b) 0,5 to 30 wt.% of a wax and/or a silicone oil c) optionally an emulsifying agent, an organic solvent and other additives, and d) water, with the proviso that component c) does not stand for 50% by weight or more of a polyalkylene glycol or a derivative thereof thermally decomposable at 150°C or above in air.

Inventors: BUTSUGAN HITONARI, HIGO MISAKO, KOHAMA HIROYUKI, TACHIIRI NOBUHIKO, BUTSUGAN, HITONARI, HIGO, MISAKO, KOHAMA, HIROYUKI, TACHIIRI, NOBUHIKO
Applicants: NEOS KK, KABUSHIKI KAISHA NEOS
Application year: 1991
Main classification: B29C33
IPC codes: C09K3, B29K75, B29C33