JP2008207444A - Mold release agent composition for molding polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mold release agent composition for molding polyurethane foam which is excellent in mold releasability, and can prevent cell roughening and mold smudging in molding. <P>SOLUTION: The mold release agent composition for molding polyurethane foam comprises wax in content of 0.01-30 pts.wt., oil-soluble oligomer in content of 0.01-20 pts.wt., a lipophilic solvent in content of 0.05-50 pts.wt., a surface active agent in content of 0.01-10 pts.wt., and a hydrophilic solvent in content of 0.05-50 pts.wt., and the residue of water with respect to the whole amount of 100 pts.wt., and W/O type emulsion where aqueous phase is dispersed in a lipophilic solvent phase containing the wax. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a release agent composition for molding polyurethane foam.

  In the molding of polyurethane foam, foaming of the polyurethane foam occurs at the time of molding, so-called cell roughness that causes dents on the surface may occur, and surface characteristics may deteriorate. Moreover, since the resinized mold deposit remains on the surface of the mold, so-called mold contamination occurs, and it is necessary to periodically clean the mold. For this reason, in order to reduce these problems, a mold release agent for preventing adhesion between the polyurethane foam and the mold is widely used in molding the polyurethane foam. When this release agent is used, it is possible to easily remove the polyurethane foam as a molded product from the mold, and it is possible to suppress the cell roughness and mold contamination.

  Silicone, waxes, and the like are known as mold release components contained in the mold release agent. Examples of the mold release agent include an aqueous mold release agent obtained by dissolving or dispersing the mold release component in water, and carbonization. And solvent-based mold release agents dissolved in an organic solvent such as hydrogen oil.

  Here, the water-based mold release agent for molding polyurethane foam has a small influence on the human body or the environment as compared with the solvent-type mold release agent, and maintenance is easy from the viewpoint of the Fire Service Law. (For example, refer to Patent Documents 1 to 4.)

JP 2005-199504 A JP 2001-96541 A JP 2000-265068 A Japanese Patent Laid-Open No. 6-226752

  However, the water-based mold release agent described above is gentle to the human body or the environment, and although there is an excellent merit that the management burden is light on the Fire Service Act, depending on the molding process, the cell roughening prevention effect compared to the solvent-based mold release agent, In addition, the effect of preventing mold contamination was poor, and there were cases where problems remained in product performance. Accordingly, the actual situation is that no water-based mold release agent composition that can be applied to any molding process and has the same performance as that of the solvent-type mold release agent has not yet been found.

  The present invention has been made in view of the above circumstances, and has an excellent cell roughening prevention effect and mold dirt prevention effect, is gentle to the human body or the environment, and has a light management burden. The purpose is to provide.

As a result of earnest research on the relationship between problems (cell roughening, mold contamination, thread generation, etc.) during molding of polyurethane foam and the composition of the release agent, the present inventors have found that the following composition has excellent performance. Has been found to achieve the present invention.
That is, the present invention includes a release component, an oil-soluble oligomer, a lipophilic solvent, a surfactant, a hydrophilic solvent, and water, and the lipophilic solvent phase containing the release component. A release agent composition for molding polyurethane foam (hereinafter, referred to as a release agent composition as appropriate) characterized by presenting a W / O emulsion in which an aqueous phase is dispersed.

  When the mold release agent composition of the W / O emulsion according to the present invention was applied to a mold, it was found that the wettability was very good as compared with the conventional configuration. Moreover, it turned out that it is very excellent compared with the conventional water-type mold release agent about the cell roughening prevention effect, a metal mold | die stain | pollution | contamination prevention effect, and a thread noise reduction effect. In addition, there is a characteristic that drying on the mold is fast. Here, normally, the wax blown last time remains on the surface of the mold, and the oil is attached. For this reason, when the mold release agent composition of the W / O emulsion is applied to the mold in such a state, the outer peripheral surface of the composition is oily, and thus the mutual adhesion is extremely high. It is considered that the wettability is improved. On the other hand, when this inventor analyzed the water-system mold release agent of the conventional structure, it turned out that all are comprised by O / W type | mold emulsion. Thereby, this inventor came to obtain the following views. That is, since the release agent of the O / W emulsion has a structure in which moisture is formed on the outside, the adhesiveness is extremely poor in relation to the mold as described above. For this reason, it is considered that the conventional water-based mold release agent does not sufficiently form a film on the mold, and the performance is not properly exhibited. Moreover, since the O / W type emulsion has a structure in which moisture is formed on the outside as described above, it is considered that drying on the mold is delayed. All of these views are based on the composition of the O / W emulsion.

  Incidentally, an antioxidant or the like may be appropriately added to the above-described present invention. Further, by appropriately changing the blending ratio, it can be used not only for hot-cure urethane foam molding, but also for cold-cure urethane foam molding or for high-elastic urethane foam molding.

  Here, examples of the release component include mainly waxes. Examples of the waxes include linear / branched polyethylene wax, ethylene / propylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, montan wax, and higher α-olefin polymer. Other examples include silicone oils, fatty acid metal soaps, ester waxes, fluorine compounds, and organophosphorus compounds.

  Further, the oil-soluble oligomer acts as a dispersant for a release component, for example, an average number of amorphous olefin oligomer, liquid polybutene, liquid polybutadiene, liquid polyisoprene, liquid butyl rubber, or liquid polyisobutylene. Liquid medium and low molecular weight compounds having a molecular weight of 2000 or less are used.

  Examples of the lipophilic solvent include hydrocarbons, halogenated hydrocarbons, ethers, amines, alcohols, glycol ethers, ketones, fatty acids, and esters.

  In other words, the surfactant is a W / O emulsion emulsifier, for example, sucrose fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, amphoteric surfactant, or polyoxyethylene alkyl. An amine etc. are mentioned.

  Examples of the hydrophilic solvent include alcohols, ethers, morpholine, amines, glycol ethers, ketones, fatty acids, and esters.

  Furthermore, in the above configuration, when the total amount is 100 parts by weight, the content of the release component is 0.01 to 30 parts by weight, the content of the oil-soluble oligomer is 0.01 to 20 parts by weight, and lipophilic The solvent content is 0.05 to 50 parts by weight, the surfactant content is 0.01 to 10 parts by weight, the hydrophilic solvent content is 0.05 to 50 parts by weight, and the balance is water, and A configuration is proposed that presents a W / O type emulsion in which an aqueous phase is dispersed in a lipophilic solvent phase containing the release component.

  By setting it as this structure, a W / O type emulsion will be hold | maintained stably. In addition, when creating a W / O type emulsion using surfactant, HLB value will be about 3-8. On the other hand, if it is about 8 to 16, it becomes an O / W type emulsion.

  In addition, when the said mold release component is less than 0.01 weight part, a mold release property is not exhibited but it is unpreferable. On the other hand, if it exceeds 30.0 parts by weight, the W / O emulsion becomes unstable, which is not preferable. The optimum range is 0.01 parts by weight or more and 10.0 parts by weight or less. Here, if it exceeds 10.0 parts by weight, a dilution operation is required at the time of use, and the workability is slightly inferior in the polyurethane foam molding process.

  If the oil-soluble oligomer is less than 0.01 parts by weight, the W / O emulsion becomes unstable, which is not preferable. On the other hand, if it exceeds 20.0 parts by weight, the releasability is deteriorated and handling is difficult, which is not preferable.

  If the lipophilic solvent is less than 0.05 parts by weight, the W / O emulsion becomes unstable, which is not preferable. On the other hand, if it exceeds 50.0 parts by weight, it is not preferable from the viewpoint of environmental protection or storage management.

  If the surfactant is less than 0.01 part by weight, the W / O emulsion becomes unstable, which is not preferable. Further, when the amount exceeds 10.0 parts by weight, the W / O emulsion becomes unstable and is not preferable. The optimum range is not less than 0.01 parts by weight and not more than 2 parts by weight. When the amount is 2 parts by weight or less, the W / O emulsion is extremely stable.

  If the hydrophilic solvent is less than 0.05 parts by weight, the W / O emulsion becomes unstable, which is not preferable. Further, when the amount exceeds 50.0 parts by weight, the W / O emulsion becomes unstable, which is not preferable.

  The water is preferably 40.0 parts by weight to 90.0 parts by weight. If it is less than 40.0 parts by weight, the release agent composition will not be classified as water-soluble, which is not preferable from the viewpoint of environmental protection or storage management. On the other hand, if it exceeds 90.0 parts by weight, the W / O emulsion becomes unstable, which is not preferable.

  The release agent composition for molding polyurethane foam according to the present invention comprises a release component, an oil-soluble oligomer, a lipophilic solvent, a surfactant, a hydrophilic solvent, and water, and is a W / O type. Since it exhibits an emulsion, there are advantages that it is possible to prevent the occurrence of cell roughening and mold contamination and to reduce thread noise. For this reason, even if it repeats a shaping | molding process in the same metal mold | die, there exists an effect which can manufacture a molded article excellent in the surface characteristic in large quantities.

  Moreover, in the said invention, content of a mold release component is 0.01-30 weight part, Content of an oil-soluble oligomer is 0.01-20 weight part, Content of lipophilic solvent is 0.05-50. Part by weight, 0.01 to 10 parts by weight of surfactant, 0.05 to 50 parts by weight of hydrophilic solvent, and water as the balance, and a W / O emulsion. In this case, there is an effect that the W / O type emulsion is stabilized. Moreover, since it becomes a composition as an aqueous release agent, safety management is facilitated in accordance with the Fire Service Law, and the problem of measures against VOC can be solved, and the amount of carbon dioxide generated can be suppressed.

  Hereinafter, the release agent composition for molding polyurethane foam according to the present invention (hereinafter referred to as a release agent composition) will be specifically described with reference to Examples and Comparative Examples.

(About preparation of mold release agent composition)
100 parts by weight of the whole was added to each component in the proportions shown in Table 1 to prepare release agent compositions according to Examples 1 to 3 (invention product) and Comparative Examples 1 to 4.

Examples 1-3
Based on the predetermined ratio shown in Table 1, A) a mold release component, B) an oil-soluble oligomer, C) a lipophilic solvent, D) a surfactant, E) a hydrophilic solvent, and water are mechanically emulsified, and W It is a water-based mold release agent composition made into / O type emulsion. In the present application, the aqueous release agent composition corresponds to a release agent composition containing water at least 40% or more of the total amount.

Comparative Example 1
Based on the predetermined ratio shown in Table 1, A) mold release component, C) lipophilic solvent, D) surfactant and water-based mold release agent composition obtained by mechanically emulsifying water to form an O / W emulsion. It is.

Comparative Example 2
Based on the predetermined ratio shown in Table 1, A) mold release component, C) lipophilic solvent, D) surfactant, E) hydrophilic solvent, and water were mechanically emulsified to form an O / W emulsion. It is an aqueous release agent composition.

Comparative Examples 3 and 4
A solvent-based mold release agent composition prepared by heating and melting a solution comprising A) a mold release component and C) a lipophilic solvent at 100 ° C. and cooling based on the predetermined ratio shown in Table 1.

  By the way, in Table 1, specific products used as each component are as follows.

A) Wax a (linear / branched polyethylene wax): Toyo Petrolite Co., Ltd., trade name “Polywax”
A) Wax b (ethylene / propylene copolymer wax): Toyo Petrolite Co., Ltd., trade name “Petrolite”
A) Wax c: Fischer-Tropsch wax A) Silicone: GE Toshiba Silicones Co., Ltd., TSF451-100
B) Liquid polybutene: manufactured by Nippon Petrochemical Co., Ltd., trade name “HV-100”
・ C) Mineral turpentine: Nippon Oil Co., Ltd., trade name “Clensol”
・ C) Aromatic hydrocarbon: Commercially available xylol ・ D) Polyoxyethylene alkylamine: manufactured by Kao Corporation, trade name “AMIET”
・ D) Sorbitan fatty acid ester: manufactured by Kao Corporation, trade name “Leodol”
E) Glycol ether: Commercially available diethylene glycol dimethyl ether E) Alcohol: Commercially available N-propyl alcohol

(About performance test)
The following performance tests were performed on the release agent compositions according to Examples 1 to 3 and Comparative Examples 1 to 4 described above.

○ Performance test 1
Subject: Example 1, Comparative Example 1
Evaluation performance: Cell roughening, mold contamination Content: After spray-coating the release agent composition of Example 1 and Comparative Example 1 on an iron mold (170 × 115 × 21 mm) at 35 ° C., it was dried for 40 seconds. It was. Next, commercially available raw materials for cold urethane foam were used, mixed at a predetermined mixing ratio, poured into a mold, and reacted at 35 ° C. for 5 minutes. Thereafter, the surface state (presence / absence of cell roughness) of the removed polyurethane foam molded article was visually observed and evaluated. In the evaluation display of Table 1, “◎” indicates a state where there is no cell roughening, “◯” indicates a state where the cell diameter tends to be enlarged, and “x” indicates a state where the cell is rough.
In addition, the mold after molding was washed with a mineral turpent, and the amount of resin reaction product remaining on the mold was visually observed to evaluate the degree of mold contamination. In Table 1, “◯” indicates a state with metallic luster and little dirt, and “x” indicates a state with much dirt.

○ Performance test 2
Subject: Examples 2 and 3, Comparative Examples 2 to 4
Evaluation performance: Cell roughening, mold contamination Content: After spray-applying the release agent compositions of Examples 2 and 3 and Comparative Examples 2 to 4 to a 65 ° C. iron mold (170 × 115 × 21 mm), Dry for 1 minute. Next, using a commercially available raw material for high elasticity (HR) urethane foam, the mixture was mixed at a predetermined blending ratio, poured into a mold, and reacted at 65 ° C. for 7 minutes. Thereafter, the surface state (presence / absence of cell roughness) of the removed polyurethane foam molded article was visually observed and evaluated. The display of evaluation in Table 1 is the same as in performance test 1.
In addition, the mold after molding was washed with a mineral turpent, and the amount of resin reaction product remaining on the mold was visually observed to evaluate the degree of mold contamination. The display of evaluation in Table 1 is the same as in performance test 1.

○ Performance test 3
Subject: Examples 1-3, Comparative Examples 1-4
Evaluation performance: Thread sound Contents: After the molded product which has been subjected to the performance test 1 is allowed to stand at 25 ° C. for one day, the arcuate part (¢ 4 mm) of the S-shaped spring is used under the conditions of a contact angle of 45 degrees and a load of 87 gf The noise generated by rubbing was measured with a microphone sound level meter (SA-27, 1/3 octave real time analyzer: manufactured by Rion Corporation) at a distance of 10 cm.

(About performance results)
The results of the above performance tests 1 to 3 are as shown in Table 1.
1 of the accompanying drawings shows the surface state of the polyurethane foam molded using Example 2, FIG. 2 shows the surface state of the polyurethane foam molded using Comparative Example 2, and FIG. FIG. 4 shows the surface state of the polyurethane foam molded using Comparative Example 4. FIG.

(Discussion 1: Cell roughening and mold contamination)
Each of the release agent compositions of Examples 1 to 3 can reduce mold contamination after molding as compared with Comparative Examples 1 and 2, and no cell roughness is observed, and a good surface. A molded product in a state (polyurethane foam) can be obtained. For example, no defective portion is found on the surface of the polyurethane foam molded using Example 2 shown in FIG. 1, but the surface condition of the molded product molded using Comparative Example 2 shown in FIG. Is occasionally seen.
Here, it can be seen that the cell roughening prevention effect and the mold contamination prevention effect of Examples 1 to 3 are almost the same as those of Comparative Example 4, which is a solvent-based release agent, and are good. For example, the surface state of the molded product molded using Example 2 is almost the same as the surface state of the molded product molded using Comparative Example 4 (see FIGS. 1 and 4). In addition, as shown in FIG. 3, in the molded product molded using Comparative Example 3, defective portions x are scattered, and when Example 2 and Comparative Example 3 are compared, Example 2 is much more remarkable. Good products can be obtained (see FIGS. 1 and 3).

(Consideration 2: Thread sound)
Moreover, each release agent composition of Examples 1-3 has implement | achieved reduction of the thread noise of a molded article compared with Comparative Examples 1-4. Specifically, the thread sound according to Examples 1 to 3 is about 70% of the thread sound of Comparative Examples 1 to 4.

(Other)
Examples 1 to 3 (product of the present invention) have a viscosity of about 1000 cps, and Comparative Examples 1 to 4 (conventional product) have a viscosity of about 20 cps. Therefore, the product of the present invention has an advantage that the release agent itself is difficult to separate (for example, it is not separated for at least 3 months). Although the product of the present invention has a higher viscosity than the conventional product, there is no problem in workability because it can be suitably injected with a known spray gun.

  In addition, in the above-described embodiment, the technique according to Japanese Patent No. 3723810 is used to effectively attach the film thickness as a mold release agent to the mold and to efficiently disperse the solvent and moisture. This is particularly effective.

  It goes without saying that the embodiments described so far can be modified as appropriate without departing from the scope of the present invention. In addition, the release agent composition according to the present invention can of course be used while being appropriately adjusted by known techniques that can be known by those skilled in the art. For example, the mold release agent composition can be used while being properly agitated to hold the W / O emulsion.

2 is a photograph showing the surface state of a polyurethane foam molded using Example 2. FIG. 4 is a photograph showing a surface state of a polyurethane foam molded using Comparative Example 2. FIG. 6 is a photograph showing a surface state of a polyurethane foam molded using Comparative Example 3. FIG. 6 is a photograph showing the surface state of a polyurethane foam molded using Comparative Example 4. FIG.

Claims (2)

  W in which a water phase is dispersed in a lipophilic solvent phase containing a release component, an oil-soluble oligomer, a lipophilic solvent, a surfactant, a hydrophilic solvent, and water, and containing the release component A release agent composition for molding polyurethane foam, which exhibits a / O type emulsion.   When the total amount is 100 parts by weight, the release component content is 0.01 to 30 parts by weight, the oil-soluble oligomer content is 0.01 to 20 parts by weight, and the lipophilic solvent content is 0.05. A parent containing 0.01-50 parts by weight of a surfactant, 0.01-10 parts by weight of a surfactant, 0.05-50 parts by weight of a hydrophilic solvent, and the balance water, and containing the release component 2. The release agent composition for molding polyurethane foam according to claim 1, which exhibits a W / O emulsion in which an aqueous phase is dispersed in an oily solvent phase.