JPH0339447B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an emulsion type release agent composition. [Industrial Application Fields] Mold release agents are applied to the inner surface of molds when manufacturing high-molecular polymer molded products so that the molded products can easily be released from the mold, and are used during compression molding or casting.
It is widely used in fields such as [Prior Art] Conventionally used mold release agents are made by diluting mineral oil, natural oil, silicone oil, polymer copolymer (natural or synthetic), etc. with an organic solvent and adjusting it to the desired concentration. It was hot. However, this type of mold release agent composition uses a chlorine-based, naphthenic-based, aromatic-based, or aliphatic-based petroleum solvent as an organic solvent. for that,
In view of the problem of toxicity to the human body and the prevention of fires, in recent years there has been a shift to emulsion-type solvents that use aqueous solvents instead of organic solvents. [Problems to be Solved by the Invention] These emulsion-type mold release agents are desired to have good mold release performance and emulsion stability. In order to obtain a stable emulsion, it is possible to incorporate a salt of a carboxylic acid and an alkali metal or an amine into the polymer.
This has traditionally been done. However, in order to stabilize the emulsion,
When the content of the carboxylic acid salt was increased, the mold release performance tended to deteriorate. That is, in the prior art, improvement in emulsion stability and improvement in mold release performance are contradictory, and there has been no one that can satisfy both simultaneously. Therefore, an object of the present invention is to obtain a mold release agent that has excellent emulsion stability and high mold release performance. The present invention was made in view of the current state of the emulsion type mold release agent technology, and as a result of various studies, it was discovered that the above object can be achieved by coexisting a polyvalent metal complex in the emulsion, and the present invention was achieved. [Means for Solving the Problems] That is, the present invention relates to a mold release agent composition characterized in that a polyvalent metal complex is made to coexist in an emulsion made of polyethylene oxide containing a carboxylic acid salt. . The content of carboxylic acid in the polyethylene oxide used in the present invention can be expressed as an acid value, and the acid value is preferably 5 to 180, for example. Furthermore, the polyethylene oxide has a
A molecular weight in the range of 10,000 is preferred. Further, the carboxylic acid salt can be, for example, a salt of an alkali metal (potassium, sodium, etc.), a salt of an amine (morphylin, diethylaminoethanol, etc.), and the like. The polyvalent metal complex in the present invention is a complex in which the central metal is a polyvalent metal. However, the polyvalent metal used in the present invention is
Refers to metals with a valence of two or more, for example,
Calcium, zinc, cadmium, zirconium,
Mention may be made of magnesium, barium, aluminum, etc., with calcium and zinc being particularly preferred. Furthermore, the ligand of the polyvalent metal complex can be not only a monodentate ligand but also a bidentate or more polydentate ligand. Specific examples of these ligands include carbonate ion, acetate ion, malate ion, hydroxyacetate ion, tartrate ion, gluconate ion,
Examples include nitrilotriacetate ion, ammonia, morpholine, ethylenediamine, diethylaminoether and the like. Examples of polyvalent metal complexes that exhibit particularly preferable performance in the mold release agent of the present invention include zinc carbonate ethylenediamine ammonia, zinc acetate ammonia,
Examples include zinc malate ammonia, calcium carbonate ammonia, and zinc gluconate ammonia. The mold release agent composition of the present invention can be manufactured by a conventional method. For example, polyethylene oxide containing carboxylic acid is melted, a base is added to form a carboxylate salt, and then hot water or the like is added to form an emulsion while stirring with a strong stirrer. An emulsifier may be appropriately added to the molten polyethylene oxide. Next, the polyvalent metal complex is obtained as an aqueous solution by a conventional method, and then the aqueous solution is added to and mixed with the emulsion made of polyethylene oxide containing the carboxylic acid salt described above to obtain the mold release agent of the present invention. A composition can be obtained. There is no limit to the amount of the polyvalent metal complex used as long as good mold release performance is obtained. For example, for carboxylic acid contained in polyethylene oxide, 0.05~
Preferably it is 0.8 chemical equivalent. As the emulsifier that can be used in forming the emulsion, any emulsifier that can be used in forming an O/W emulsion can be used without any problem. For example, synthetic surfactants such as nonionic surfactants can be used. In addition, when an emulsion made of a polyvalent metal salt of the carboxylic acid contained in the polyethylene oxide mentioned above (therefore, it is not an emulsion in which a polyvalent metal coexists as a complex) is used as a mold release agent, the acid Even if the value was high, the mold release performance was good. However, the stability of the emulsion was considerably inferior to that of conventionally known emulsions. Therefore, it is essential that the polyvalent metal in the present invention forms a complex with a suitable ligand in the emulsion. The mold release agent of the present invention can be used in a conventional manner. For example, it can be used successfully by applying or spraying a certain amount onto the mold surface and drying it. Although it is not intended to be bound by theory, the good mold release performance of the mold release agent of the present invention is due to the fact that when the mold release agent is dried, the polyvalent metal forming the complex is contained in the polymer compound. It is presumed that it is obtained because it functions as a crosslinking agent that connects two or more carboxylic acids. Hereinafter, the present invention will be explained in more detail with reference to Examples. Incidentally, the units of the blending ratios of various raw materials, etc. described in the tables described later are weight %. Reference example 1 (Preparation of emulsion) 20g of polyethylene oxide A is mixed with 5g of emulsifier (polyoxyethylene nonyl phenyl ether), and the temperature is 10°C higher than the softening point of polyethylene oxide A.
It was heated to 120°C and dissolved. After dissolution, 0.5 g of a base (morpholine) was added to neutralize the carboxylic acid contained in polyethylene oxide A to form a salt. Next, while stirring with a strong stirrer, 74.5 g of hot water (90 to 100°C) was gradually added, followed by immediate rapid cooling to obtain emulsifier A (E). Emulsifiers B(E), C(E) and D(E) were prepared according to the manufacturing method of A(E) so as to have the compositions shown in Table 2.
However, regarding D(E), polymer compound D was dissolved by heating to 105°C. Table 1 shows the properties of each polyethylene oxide, and Table 2 shows the types of emulsifiers and bases and the amounts used of each raw material.
Shown below. [Table] A is polyethylene wax (trade name: AC-680) made by Atride Chemical Co., Ltd. in the United States. B is oxidized Sasol wax (trade name: Kazol A4) manufactured by Sasol Corporation in the Republic of South Africa. C is an oxidized polyethylene wax (product name: Hoechst Wax PED522) manufactured by Hoechst in West Germany. D is an oxidized polyethylene wax (product name: Hoechst Wax PED136) manufactured by West Germany's Hoechst Company = D-1, and a montan-based wax (product name: Hoechst Wax KSL) manufactured by West Germany's Hoechst Company = D -2 mixture. However, D-1 and D
The mixing ratio of -2 was 80:20. [Table] Reference Example 2 (Manufacture of polyvalent metal complex aqueous solution) (a) Zinc carbonate ethylenediamine ammonia aqueous solution Pour 60.3 g of water into a container equipped with a stirrer, gradually add 10 g of zinc oxide while stirring, and add zinc oxide to the water. dispersed into Then 28% ammonia water 7.7
g, ethylenediamine 7.7g, ammonium carbonate
14.3 g were added one after another and stirring was continued until dissolved to obtain an aqueous zinc carbonate ethylenediamine-ammonia solution. (b) Zinc acetate ammonia aqueous solution Place 55 g of water in a container equipped with a stirrer, add 15 g of zinc acetate to the water while stirring, dissolve, and then add
30 g of 28% ammonia water was added and stirred until the solution became homogeneous to obtain a zinc acetate ammonia aqueous solution. (c) Zinc malate ammonia Put 43.5 g of water into a container equipped with a stirrer, add 10 g of zinc acetate to the water while stirring, disperse, then add 16.5 g of malic acid to make zinc malate, and then add 28% 30 g of ammonia water was added and stirred until the solution became homogeneous to obtain a zinc malate ammonia aqueous solution. (d) Calcium carbonate ammonia Put 54g of water in a container equipped with a stirrer, add 10g of calcium oxide to the water while stirring, and disperse.
Next, 18g of ammonium carbonate and 28% ammonia water
18 g was added and stirring was continued until dissolved to obtain an aqueous solution of potassium ammonia carbonate. (e) Zinc gluconate ammonia A zinc gluconate ammonia aqueous solution was obtained in the same manner as in (c) except that gluconic acid was used instead of malic acid in (c). Table 3 shows the proportions of each raw material used in (a) to (e). [Table] [Table] Example 1 (Preparation of mold release agent) Adding to the emulsion prepared in Reference Example 1, while stirring,
The polyvalent metal complex aqueous solution prepared in Reference Example 2 was added together with water and further stirred to obtain release agents 2, 3, 5, 6, 8, 9, 11, and 12 as uniform emulsifiers. However, the amount of polyvalent metal complex added is as follows:
For mold release agents 5, 8, and 11, the amount was 0.3 chemical equivalent relative to the carboxylic acid, and for mold release agents 3, 6, 9, and 12, the amount was 0.5 chemical equivalent relative to the carboxylic acid. Table 4 shows the types and usage ratios of raw materials for each mold release agent. Comparative Example 1 (Preparation of Mold Release Agent) Water was added to the emulsion prepared in Reference Example 1 and stirred to obtain Mold Release Agents 1, 4, 7, and 10 as uniform emulsions. The type and amount of emulsion and the amount of water are shown in Table 4.
Shown below. Furthermore, mold release agents 13 to 20 of comparative examples shown in Table 4
was produced using polyvalent metals. Examples 2-1 to 8 (Mold release performance evaluation) 40g of mold release agent was applied with a brush, and the inner dimension was 250.
It was applied to the inner surface of an aluminum casting mold measuring 250 x 70 mm (length x width x height) and thoroughly dried. Next, the foamable polyurethane solution was poured into the mold and foamed. After the curing time has elapsed, attach a spring clamp to a point 20mm inside from the diagonal corner of the top surface of the polyurethane foam resin (250mm x 250mm) and lift it at a speed of 20mm/sec to obtain the maximum traction required for the polyurethane foam resin to release from the mold. The weight was measured as the weight at the time of demolding. However, the mold release agents used were 2, 3, 5, 6, 8, 9, 11, and 12 containing polyvalent metal complexes shown in Table 4. The measurement results obtained are shown in Table 5. (Blend of foamable polyurethane solution) (Parts by weight) Polyether (Sannixtriol GP-3000)
(Note-1) 100.0 Water 4.0 Triethylenediamine 0.1 Toray Silicone SH-190 (Note-2) 1.0 Stanus Octoate 0.4 TD1-80 Index 105.0 (Note-1) Polyether product name for urethane foam manufactured by Sanyo Chemical Industries (Note-1) -2) Comparative examples 2-1 to 12 (Mold release performance evaluation) As mold release agents, 1, 4, 7, 10 shown in Table 4 were used.
(without polyvalent metal complexes), and 13 to 20 (containing polyvalent metals: 0.3 chemical equivalent to carboxylic acid for 13, 15, 17, and 19, and carboxylic acid for 14, 16, 18, and 20) The maximum pulling weight required for demolding the polyurethane foam resin was measured as the weight at the time of demolding in the same manner as in Example 4-1 except that 0.5 chemical equivalent to the acid was used. The measurement results obtained are shown in Table 5. Examples 3-1 to 8 and Comparative Examples 3-1 to 12 (Stability of emulsion) The mold release agent obtained in Example 1 and Comparative Example 1 was
After being left in an oven at 1.5° C. for 30 days, the emulsion state was observed and the increase in viscosity due to coalescence of particles in the emulsion was measured as an indicator of emulsion instability. The results obtained are shown in Table 6. [Table] [Table] [Table] [Table] [Table] [Table] Reference example 3 (Adjustment of floor polish) 1 Adjustment of acrylic polymer emulsion (monomer) (% by weight) Methyl methacrylate (MMA) 40 Ethyl acrylate (EA) 45 Methacrylic acid (MAA) 15 Sodium lauryl sulfate was used as an emulsifier in the above monomer mixture, and a polymer emulsion with a solid content of 40% was obtained by emulsion polymerization in a conventional manner. The molecular weight of the polymer was 800,000 as measured by GPC, and the acid value was 98. 2. Preparation of alkali-soluble resin solution A styrene-maleic acid copolymer having an acid value of 200, a molecular weight of 1800, and a softening point of 170°C was neutralized with ammonia to prepare a solution with a solid content of 15%. Comparative Example 4 (Mold release agent: Preparation of floor polish composition) The polyvalent metal complex aqueous solution prepared in Reference Example 2 was added to the acrylic polymer emulsion prepared in Reference Example 3-1 with water while stirring. . The alkali-soluble resin solution prepared in Reference Example 3-2 was added therein, and the polyethylene wax emulsion prepared in Reference Example 1 was also added thereto. A coalescing agent, a plasticizer, and a fluorine-containing surfactant were further added to this preparation to obtain a floor polish composition. Table 7 shows the blending ratio of the mold release agent in Comparative Example 4. [Table] [Table] The blending ratio is shown in parts by weight.
Regarding Comparative Example 4-1 and Comparative Example 4-2 using acrylic polymer, the mold release performance was evaluated in the same manner as Example 4-1, but both could not be released from the mold and were completely useless as a mold release agent. It was appropriate. Furthermore, when the emulsion stability was examined using the same evaluation criteria as in Table 6, the results shown in Table 8 were obtained. [Table] From the results shown in Table 8, it can be seen that the comparative example using an acrylic polymer had poor emulsion stability. [Effects of the Invention] As shown in Table 5, the mold release agent of the present invention has the ability to release a molded article from a mold with less weight than conventional products having the same acid value. Furthermore, as shown in Table 6, the stability of the emulsion does not change due to the addition of the polyvalent metal complex, and therefore, the mold release agent of the present invention stabilizes the emulsion at least as much as the conventional products. It is something that has a nature. That is, the mold release agent of the present invention simultaneously satisfies two properties, which have not been possible in the past: high mold release performance and excellent emulsion stability. Furthermore, the mold release agent of the present invention can be produced by simply adding and mixing a polyvalent metal complex obtained from relatively inexpensive and easily available raw materials to an emulsion conventionally used as a mold release agent. Easy to prepare;
Moreover, it has the advantage that the mold release performance can be greatly improved with an extremely small amount (of the polyvalent metal complex) added.

Claims (1)

[Scope of Claims] 1. A mold release agent composition characterized in that a polyvalent metal complex is allowed to coexist in an aqueous emulsion made of polyethylene oxide containing a carboxylic acid salt. 2. The mold release agent composition according to claim 1, wherein the polyvalent metal of the polyvalent metal complex is calcium or zinc. 3. The mold release agent composition according to claim 1, wherein the polyvalent metal complex is a member selected from the group consisting of zinc carbonate ethylenediamine ammonia, zinc acetate ammonia, zinc malate ammonia, calcium carbonate ammonia, and zinc gluconate ammonia. thing. 4. The mold release agent composition according to any one of claims 1 to 3, wherein the polyethylene oxide containing the carboxylic acid salt has an acid value of 5 to 180. 5. The mold release agent composition according to any one of claims 1 to 4, wherein the polyethylene oxide containing the carboxylate has a molecular weight of 200 to 10,000. 6 Claims 1 to 5, in which a polyvalent metal complex of 0.05 to 0.8 chemical equivalents is made to coexist with respect to the carboxylic acid of polyethylene oxide containing a carboxylate salt.
The mold release agent composition according to any one of Items 1 to 9.