JP4887535B2 - Release agent composition for polyurethane slush molding - Google Patents

Description

  The present invention relates to a release agent composition that is used by being applied to a mold in polyurethane slush molding.

  The slush molding method can easily form products with complicated shapes such as undercut and deep drawing, and has advantages such as uniform wall thickness and good material yield. Widely used in applications such as automotive interior materials such as panels, console boxes and door rims.

  As a material for slush molding, polyvinyl chloride resin has been conventionally used, but recently, a thermoplastic urethane resin excellent in chemical resistance, light resistance and the like has been used. When a molded product is obtained by thermoforming urethane beads, the raw materials to be blended, the molding temperature, etc. are greatly different even when the same slush molding method is used as compared with urethane foam.

  Moreover, the performance of the mold release agent for resin molding varies greatly depending on the resin material to be molded, molding temperature, application state, and the like. Therefore, even with the same resin material, the performance of the release agent varies depending on the molding method and molding temperature. Thermoplastic polyurethane resins have the advantage of being excellent in heat resistance, weather resistance, and chemical resistance, but they have the characteristic of poor release properties, and the improvement of release properties depends on release agents. Become.

  As the mold release agent for the thermoplastic polyurethane resin, there are an internally added mold release agent that is preliminarily blended in polyurethane and an external mold release agent that is applied to a mold during molding. For example, Japanese Patent Application Laid-Open No. 2003-286406 and Japanese Patent Application Laid-Open No. 2000-336220 describe internal addition / release agents containing silicone compounds and resins. However, the current internal mold release agent cannot be said to be a level where the mold release property and sustainability are satisfied, and must be used in combination with an external mold release agent.

  On the other hand, silicone-based or fluorine-based release agents are often used as external release agents. For example, Japanese Patent No. 3438193 describes a silicone-based external mold release agent composed of an organopolysiloxane, a silicone resin, a polyvinyl alcohol derivative, a higher fatty acid salt having a melting point of 50 ° C. or higher, and water. Although the external release agent is excellent in releasability, the gloss of the molded product is increased, which causes transfer to the windshield in the instrument panel.

  In addition, the fluorine-based mold release agent has little influence on the gloss of the molded article, but unless it is applied excessively, the mold release property and the sustainability of the effect are poor, leading to deterioration in workability and work environment. Further, there is a problem that discoloration is likely to occur due to excessive application of a release agent, and the mold life is shortened by increasing the number of times of mold cleaning.

JP 2003-286406 A JP 2000-336220 A Japanese Patent No. 3438193

  The present invention has been made in view of such conventional circumstances, and is excellent in mold releasability in polyurethane slush molding as an external mold release agent, and more excellent in sustainability than conventional mold release agents. Therefore, it is an object of the present invention to provide a release agent composition in which contamination to a molded product is small.

In order to achieve the above object, a release agent composition provided by the present invention is used by being applied to a polyurethane slush molding mold, and contains a fluorine-containing organic phosphorus compound in an organic solvent. The composition contains 0.1 to 10% by mass of at least one selected from perfluoroalkyl phosphorous acid or a salt thereof and a perfluoroalkyl phosphate ester as the fluorine-containing organic phosphorus compound , The organic graft polymerization compound represented by Chemical Formula 2 is contained in an amount of 0.1 to 10% by mass .

The release agent composition for polyurethane slush molding of the present invention may contain 0.1 to 10% by mass of a phosphate ester together with the fluorine-containing organic phosphorus compound and the organic graft polymerization compound .

  According to the present invention, there is provided a release agent composition for polyurethane slush molding that is excellent in mold releasability in polyurethane slush molding, has excellent durability, and hardly contaminates the molded product. be able to.

  In the release agent composition for polyurethane slush molding of the present invention, perfluorophosphorous acid or a salt thereof, which is a fluorine-containing organic phosphorus compound, and perfluoroalkyl phosphate are adsorbing power to a mold as an external release agent. Since it is large and has excellent heat resistance, it is suitable as a mold release agent for molded products at high temperatures in polyurethane slush molding. Moreover, since perfluoroalkyl phosphate ester has a small transfer to a molded product, it is possible to further reduce an increase in gloss caused by the transfer of a release component to the molded product.

Perfluoro phosphorous acid or a salt thereof, the amount of the perfluoroalkyl phosphoric acid ester, in the range of 0.1 to 10 mass% in total as the fluorine-containing organic phosphorus compound, in the range of 0.5 to 5 wt% Is preferred . When the blending amount of the above components is less than 0.1% by mass, release performance is hardly recognized. Moreover, even if it mixes more than 10 mass%, since an effect reaches a peak, it is unpreferable.

The release agent composition for polyurethane slush molding of the present invention contains an organic graft polymerization compound together with the above-described fluorine-containing organic phosphorus compound, and can further contain a phosphate ester . By including an organic graft polymerization compound in addition to the fluorine-containing organic phosphorus compound , and further by including a phosphate ester , the releasability is greatly improved by these synergistic effects.

  Phosphate ester is excellent in adsorption to molds, and has the effect of helping adsorption of perfluorophosphorous acid or its salt, or perfluoroalkyl phosphate ester to molds. Is extremely large. Moreover, the compounding quantity of phosphate ester has the preferable range of 0.1-10 mass%. If the blending amount of the phosphate ester is less than 0.1% by mass, the effect of improving the releasability is not obtained by addition, and if it exceeds 10% by mass, the gloss increases due to the transfer effect to the product and the product contamination is large. Since it is considered, it is not preferable.

  Examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, dicresyl phenyl phosphate, cresyl diphenyl phosphate, dimethyl phosphate, At least one selected from diethyl phosphate, dibutyl phosphate, di-2-ethylhexyl phosphate, dibutoxyethyl phosphate, diphenyl phosphate, dicresyl phosphate and cresyl phenyl phosphate is preferred.

  Further, the organic graft polymerization compound used in the present invention has a structural formula shown in the following chemical formula 3. This organic graft polymerization compound, like the phosphate ester, has a strong adsorption power to the mold, and has an effect of assisting the adsorption of perfluorophosphorous acid or a salt thereof, or perfluoroalkyl phosphate ester to the mold. .

The amount of the organic graft polymerization compound, in the range of 0.1 to 10 mass%. If the blending amount is less than 0.1% by mass, the effect of addition is not achieved, and if it exceeds 10% by mass, the peeling performance tends to decrease on the contrary, such being undesirable.

  In addition, the organic solvent used in the present invention is not particularly limited as long as it can dissolve the above-described components, but aliphatic hydrocarbons such as n-heptane, n-hexane, and isohexane, ethanol, isopropyl alcohol, and the like. These alcohols can be preferably used.

[Example 1]
Perfluoroalkyl phosphorous acid, tricresyl phosphate which is phosphate ester, organic graft polymerization compound of the above chemical formula 3, perfluoroalkyl acrylic oligomer (abbreviated as PFAA oligomer), perfluoroalkyl ethylene oxide adduct (abbreviated as PFAEO adduct) ), At least one kind of dimethyl silicone, and at least one kind of organic solvent n-heptane, acetone, isopropyl alcohol were weighed, mixed and stirred to obtain each composition of Samples 1 to 6 shown in Table 1 below. .

  Each composition of Samples 1 to 6 was subjected to a peel resistance test in order to evaluate the releasability and sustainability. That is, each of the above compositions was applied to a flat mold and heated to 270 ° C. Thermoplastic polyurethane powder was inserted into the mold, and the resulting product was flattened so as to have a thickness of 1 mm. Thereafter, the mold was quenched in a water bath to obtain a polyurethane molded product.

  The obtained polyurethane molded product was cut into 25 mm squares while being in close contact with the mold, and used as a test piece for a peel resistance test. One end corner of each test piece was peeled off, and the peeled one end corner was pulled with a push-pull gauge (manufactured by IMADA, push-pull scale) to measure the peeling resistance when releasing. Thereafter, the same molding and peeling test as described above were carried out 9 times continuously without applying the composition to the same mold, and the peeling resistance obtained in each test for a total of 10 times is shown in Table 2 below. Incidentally, the sample 6 of the comparative example could not be peeled off already in the first test.

As can be seen from the results of the peel test, the compositions of Sample 3 of the present invention and Samples 1 and 2 of the reference example have the same initial peel resistance as compared with Samples 4 to 5 which are comparative examples. However, the increase in the peel resistance accompanying the increase in the number of tests, that is, the increase in the number of molding and demolding is small. This indicates that the release agent composition of the present invention is superior not only in release properties but also in sustainability compared to a conventional release agent composition which is a comparative example.

[Example 2]
Using each composition of Samples 1 to 5 shown in Table 1 above, a polyurethane molded product was obtained in the same manner as in Example 1. The obtained polyurethane molded product was peeled off, and the gloss of the molded product was measured using a gloss meter (by micro-TRI-gloss manufactured by BYK Gardner) at an incident angle of light of 60 °. The obtained results are shown in Table 3 below. Incidentally, the measured value by the gloss meter increases in proportion to the gloss level of the molded product, and a product having a large gloss can be regarded as having a large product contamination by the release agent.

From the results of the above gloss test, the gloss of the sample 3 according to the present invention and the samples 1 and 2 of the reference example are the same level as the sample 4 of the fluorine-based mold release agent as a comparative example, and the sample of the silicone mold release agent A value smaller than 5 was shown. Therefore, it can be seen that the release agent composition for urethane slush molding of the present invention is much less contaminated with the product than the silicone release agent and has the same level of product contamination as the fluorine release agent.

Claims (2)

A release agent composition that is applied to a polyurethane slush mold and contains a fluorine-containing organic phosphorus compound in an organic solvent, and the fluorine-containing organic phosphorus compound is perfluoroalkyl phosphorous acid or a salt thereof, And 0.1 to 10% by mass of at least one selected from perfluoroalkyl phosphate esters, and 0.1 to 10% by mass of an organic graft polymerization compound represented by the following chemical formula 1. A release agent composition for polyurethane slush molding.

The release agent composition for polyurethane slush molding according to claim 1, comprising 0.1 to 10% by mass of a phosphate ester together with the fluorine-containing organic phosphorus compound and the organic graft polymerization compound .