KR20050119374A - Polymer shapings containing aluminosiloxane compound - Google Patents

Abstract

The present invention relates to a polymer molded product and an aluminosiloxane composition in which various physical properties are positively improved by containing an aluminosiloxane compound in a polymer. According to the present invention, the aluminosiloxane compound can be incorporated into the polymer in an amount of 0.01 to 40% by weight.

By using aluminosiloxane instead of the conventional siloxane compound, the disadvantage that the siloxane compound in the polymer is lost by migration over time has been solved. Polymer molding may be in various forms such as fibers, films, sheets, and membranes, and in addition to molding in the form described above, various applications such as coatings, paints, and cosmetics are possible.

Description

Polymer Shapings Containing Aluminosiloxane Compound

The present invention relates to a polymer molded article and an aluminosiloxane composition comprising the aluminosiloxane compound of the following formula (1) or (2).

[Formula 1]

[Formula 2]

Wherein each R is the same or different and represents C ₁ to C ₆ alkyl or phenyl, n is an integer from 6 to 90, M is an alkali metal such as lithium, sodium, potassium, rubidium, cesium, francium Indicates.

The siloxane bond has the advantage of excellent weather resistance that does not deteriorate or decay in the air, but this property has been newly emerged as a pollutant that is difficult to treat due to the nature that cannot be destroyed when used and discarded. Therefore, to solve the pollution problem caused by the discarded silicon compound and further develop the effective decomposition, recovery and separation methods of siloxane bond-containing compounds such as silicone rubber or silicone oil to settle the silicon chemical industry without worrying about waste. Research has been done.

In addition to the decomposition method developed above, many studies have been made on the aluminosiloxane itself. For example, the results of synthesizing aluminosilsesquioxanes by reacting isopropoxyaluminum [(i-PrO) ₃ Al] with trialkoxysilanes are known in the literature. The aluminosylsesquioxane compound is the same as the compound related to the present invention in that aluminum has an AlO ₄ arrangement, but silicon atoms have an RSiO ₃ arrangement unlike the compounds used in the present invention. On the other hand, by treating the aluminum metal surface with ethoxysilane vapor to form = Al-O-Si≡ bonds on the metal surface to prevent corrosion of the metal surface and impart gloss to the surface; A method of forming an Al—O—Si ′ skeleton structure by treating an aluminum metal surface with an alkoxysilane using a sol-gel method; A method of synthesizing a phosphine ruthernium (Rh) complex by reacting isopropoxy aluminum with an alkoxysilane by a sol-gel method; And methods of ultimately producing mullite from aluminium and silicon oxide via aluminosiloxane are known, respectively.

In addition, a dialkyl (or phenyl) siloxane unit (hetero-metal siloxane ("Si-OMO-Si") series containing a metal atom between the siloxane groups) Aluminosiloxane compounds having a long chain of at least 6 or more connected to each other and exhibiting stronger silicone properties, particularly in terms of siloxane reactivity, are disclosed in Korean Patent Publication No. 10-0333404. It has been disclosed.

Due to the nature of the silicon molecule, the polymer / silicone masterbatch causes migration of siloxane molecules to the exterior of the polymer over time. Migration is a phenomenon that inherently degrades the performance of siloxane composites, which reduces the positive effect of introducing siloxane over time. In other words, when the migration phenomenon occurs over time, the composite material is gradually different from the general material, which is a fatal disadvantage of the essential part of the composite material.

Previously, composite materials using siloxane existed, but as time passed, the siloxanes in the composite material gradually disappeared due to the migration phenomenon, and how to fix the siloxane in the composite material was a challenge. Thus, after the elastomer mixed with the siloxane (Elastomer) to form a powder (Powder) finely, it has been used to mix it into the target polymer. However, these methods have not been used for applications such as fibers, films, paints, films, and cosmetics because of their granularity, they have many limitations in processing methods and do not completely solve the migration.

For this reason, products using siloxane mixed materials or siloxane powder mixed materials in fibers, films, paints, films, and cosmetics have not been manufactured.

There have been many attempts to improve the physical properties by adding siloxane in the polymer, but the physical property degradation due to the migration phenomenon siloxane is a problem. By adding aluminosiloxane in the polymer, it is intended to solve the above problems.

The present invention provides a polymer molded body comprising 0.01 to 40% by weight of the aluminosiloxane compound of Formula 1 or Formula 2 in the polymer.

[Formula 1]

[Formula 2]

In the above formula

Each R is the same or different and represents C ₁ to C ₆ alkyl or phenyl,

n is an integer from 6 to 90,

M represents alkali metals, such as lithium, sodium, potassium, rubidium, cesium, and francium.

In the present invention, the polymer is polyethylene terephthalate (PET), polypropylene (PP), epoxy, polyethylene, polyurethane, polystyrene, polycarbonate, polyvinyl alcohol, phenol resin, urea resin, melamine resin, acetal resin and nylon It provides a polymer molded product, characterized in that one or two or more polymers selected from the group consisting of.

The present invention also provides a polymer molded article characterized in that the processing form of the polymer molded article is a fiber, a film, a sheet or a film.

In another aspect, the present invention provides a coating agent comprising 0.01 to 40% by weight of the aluminosiloxane compound of Formula 1 or Formula 2 in the polymer.

In addition, the present invention provides a paint, characterized in that it comprises 0.01 to 40% by weight of the aluminosiloxane compound of Formula 1 or Formula 2 in the polymer.

In addition, the present invention provides a cosmetic comprising a 0.01 to 40% by weight of the aluminosiloxane compound of Formula 1 or Formula 2 in the polymer.

Hereinafter, the present invention will be described in more detail.

The aluminosiloxane may be synthesized using silicon as a starting material, and may have various structures such as the following Chemical Formulas 1 to 2 as aluminum compounds having the siloxane as the main axis of the molecular skeleton.

[Formula 1]

[Formula 2]

Wherein each R is the same or different and represents C ₁ to C ₆ alkyl or phenyl, n is an integer from 6 to 90, M is an alkali metal such as lithium, sodium, potassium, rubidium, cesium, francium Indicates.

In particular, the aluminosiloxane compounds of Chemical Formulas 1 and 2 have been patented by the inventors of the present invention in Korea, the United States, Europe, etc. (KR0333404, US6495708, EP1189909). The alumino siloxane used in the present invention is the aluminosiloxane of the formula (1) or (2), and as shown in the above formula, the aluminum atom is present in the center at the coordination bond and the siloxane unit ( ) Is a compound consisting of two rings. This compound has good compatibility with various polymers, does not participate in the main skeleton bonding of polymers, and has no migration phenomenon in which silicone flows out from the final product. .

The aluminosiloxane compound of Formula 1 or Formula 2 used in the present invention is soluble in nonpolar organic solvents such as n -hexane, benzene, toluene, tetrahydrofuran, stable in specific gravity of 0.94 to 0.98, and also as a gel solid. Although stable in the air, it is unstable in the presence of an electron acceptor (H ⁺ = proton) and exhibits easily dissociated properties as shown in Scheme 1 below.

Scheme 1

Therefore, due to the above properties, organic and inorganic substances containing hydroxyl groups or epoxy groups at the terminal, such as thermosetting resin, cellulose, sucrose, epoxy, etc., and various products such as epoxy and optionally in the presence of an acid catalyst It is thought that the condensation reaction as shown in Scheme 2 proceeds very actively.

Scheme 2

However, when the compound containing a hydroxy group in the reaction scheme 2 is a hydrocarbon compound, if the product is a structure of ['Si-O-C'], this bond is unstable in the air, and thus easily dissociates again. However, in a thermosetting network resin such as phenol, melamine, urea, epoxy resin, or in a macromolecule such as cellulose, the siloxane forms a hybrid structure or dissociates [Si-OC≡] bonds, causing the silicon atoms to dissociate. Recombines into siloxane bonds [Si-O-Si≡] again in the molecule to form an interpenetrating polymer network (IPN) in the polymer, thus becoming in a stable state. Therefore, these thermosetting resins or macromolecules having It is expected that it can be used very usefully as a siloxane agent. In other words, in the final step of preparing macromolecules such as thermosetting resins or cellulose, the aluminosiloxane compound of the formula (1) or (2) is treated with gloss, flexibility, water repellency, heat resistance, and weather resistance, thereby improving physical properties of the finished product. It helps.

In addition, the aluminosiloxane compound of the formula (1) or (2) may be usefully used as a siloxane agent for the surface of the supervolume composed of metallic silicate. Degradation of the aluminosiloxane in the presence of an acid has a reactive functional group such as ≡Al-O-R or ≡Si-O-R (where R is hydrogen or alkyl), so that the HO-Si≡ group This is because it reacts easily to form a strong bond.

Thus, the compounds of formula 1 or formula 2 are much more useful than silanes containing conventional functional groups as siloxanes for the surface of thermosetting resins, celluloses, epoxies, metal silicates, pigments composed of various metal oxides and other fine inorganics. Can be used. In particular, dialkyl (or phenyl) siloxane units ( ) Is siloxaneized in a minimum of 6 to a maximum of 90 units, the siloxane-treated material exhibits a characteristic that the properties of the siloxane are well expressed.

Aluminosiloxane compounds with n less than 6 are not well synthesized, and if n is greater than 90, they have a liquid-like state, which is not easy to handle.

It is possible to mix the aluminosiloxane compound prepared as described above in a polymer such as PET, PP, nylon and to shape the product using the same. After the polymerization of the polymer resin is finished, the aluminosiloxane compound may be uniformly mixed in the polymer resin when the fluid is still present, and the product may be molded. In the case where the polymer is a thermoplastic resin, even if the fluidity disappears, heat is applied again to obtain fluidity. Thus, the aluminosiloxane compound may be mixed and used. That is, after melt | dissolving a polymeric resin, an aluminosiloxane compound may be thrown in and blended here. Polymers that can be prepared in this way include nylon, polyethylene, polyurethane, polyethylene terephthalate (PET), polypropylene, polystyrene, acetal resin, polycarbonate and the like.

However, when siloxane of the material forming the IPN structure in the siloxane process, such as PVA or epoxy resin, the aluminosiloxane compound and the epoxy resin according to the present invention is 9: 1 to 5: 5, preferably 8: 2 The mixture may be mixed in a weight ratio of 7: 3 to first form a copolymer, and then the copolymer may be appropriately mixed with an epoxy resin to perform siloxane. That is, when the aluminosiloxane compound and the epoxy resin are dissolved in a solvent such as toluene and xylene, and then heated to 140 ° C. to 160 ° C., a reaction occurs to give a semi-solid phase intermediate between the gel and the solid phase. do.

Preferred amounts of use when used as siloxane agents can be readily determined by one skilled in the art depending on the substance of siloxane and the structure and siloxane purpose of the siloxane agent, but are usually 2 to 10 based on the siloxane target. The siloxane agent is used in an amount of, by weight, preferably 2 to 6% by weight. If it is out of this range it is because it is not possible to change the physical properties of the target material in an undesirable direction, or achieve the desired degree of siloxane.

Thermosetting resins such as phenol resins, melamine resins and urea resins are slightly different. The intermediate of the thermosetting resin is pulverized, the solid filler is mixed and pulverized, and an appropriate amount of the aluminosiloxane compound is added thereto (1% or less), mixed in a high speed mixer, and then manufactured by heating and pressing with a mold.

The content of the aluminosiloxane compound is preferably used 0.01 to 40% by weight. When the content of the aluminosiloxane compound is less than 0.01% by weight, it is difficult to expect various positive effects due to the aluminosiloxane compound, that is, antifouling property, increased dispersion effect, and improved touch and drape properties. If the content of more than 40% by weight is economically disadvantageous.

The processing form of the polymer incorporating the aluminosiloxane compound may have various forms such as fibers, films, sheets, membranes, and the like. It can also be used in coatings, cosmetics, paints and the like.

Incorporation of the aluminosiloxane compound into polyester fibers, nylon fibers, polypropylene fibers, acrylic fibers, polyurethane fibers, etc., significantly improves the feel and drape, and has positive effects such as improvement of antifouling properties and shrinkage properties. In addition, the dispersibility is improved, and it is easy to mix antimicrobial agents, adsorbents, electromagnetic wave blocking agents, anion generators, and sunscreen agents, and anti-allergic properties can be expected.

When mixed with paints painted on the lower part of the ship, due to their antifouling properties, they are very useful for the removal of plants and animals that often cling to the bottom of the ship. In addition, when applied to the surface of various objects, the feel is significantly improved, especially when used in mobile phones and the like contributes greatly to the improvement of product value.

The use of aluminosiloxane compounds in cosmetics prevents the metal oxides used in cosmetics from becoming hydroxides in water, thereby reducing the biological effects and improving the biophysical properties. In addition, it does not bleed or bleed well due to water, sweat, etc., so it can maintain the feeling of the first makeup and can be used regardless of season, place, and situation, thereby improving consumer satisfaction.

In addition to this, it is possible to use as a coating agent. The aluminosiloxane compound of the present invention is mixed with a polymer, an inorganic substance, and a metal additive as a coating agent and applied to the surface, thereby improving the water repellency, releasability, and dispersibility.

Hereinafter, the structure and effects of the present invention will be described in more detail with specific examples and comparative examples, but these examples are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention.

Example 1 and Comparative Example 1

900 g of acetal resin (Kepital F20-03) was mixed with 100 g of aluminosiloxane to make a master batch, and the master batch was mixed with acetal resin bulk to prepare a sample such that the total aluminosiloxane content was 5%.

In addition, a master batch was prepared by mixing 100 g of a conventional siloxane to 900 g of the same acetal resin as described above, and a sample was prepared by mixing the master batch in acetal resin bulk so that the total siloxane content was 5% as above.

As a result of testing each sample by leaving the prepared sample at room temperature and atmospheric pressure for 4 weeks, the polymer containing the conventional siloxane compound leaked to the surface in the form of oil, but the aluminosiloxane compound was mixed by the method according to the present invention. No leakage of aluminosiloxane in the form of oil or the like on the surface of the polymer was observed at all. Therefore, although the migration phenomenon occurs in the polymer incorporating the conventional siloxane compound, it was found that in the polymer incorporating the aluminosiloxane compound by the method according to the present invention, the migration phenomenon does not occur at all.

In addition, as a result of continuing the test by leaving the polymer incorporating the aluminosiloxane compound for 3 years at room temperature and atmospheric pressure for 3 years, no migration phenomenon was observed, and thus, no migration phenomenon occurred.

In addition, it was confirmed that the effect of improving the tensile elongation and Izod impact strength. In addition, it was confirmed that the weather resistance is excellent.

Example 2

900 g of PET resin is mixed with 100 g of alumino siloxane to make a master batch, and the master batch is mixed with PET resin bulk to prepare a sample so that the alumino siloxane content is 2% as a whole, and the sample is used to make 70D / 36F. Spinning. As a result, the result shown in Table 1 was obtained.

Table 1.

burglar Shinto Water repellency Modulus Normal PET 4.7 42 30 82.1 AS 2% PET 4.4 45 25 70

On the other hand, it was confirmed that the touch and drape properties are also greatly improved.

Example 3

900 g of nylon 6 resin is mixed with 100 g of alumino siloxane to make a master batch, and the master batch is mixed with nylon 6 resin bulk to prepare a sample so that the alumino siloxane content is 3% as a whole, and using the sample, 70D / 68F It was radiated to be. As a result, the result shown in Table 2 was obtained.

Table 2.

5% strength 10% strength 30% strength 40% strength Plain nylon 1.01 1.72 3.68 4.47 AS 3% nylon 0.89 1.50 3.37 4.14

Overall modulus was reduced by 10 to 12%, and it was determined that the drape was good and the touch was excellent.

Example 4

100 g of phenolic resin (Novolac) powder, 10 g of alumino siloxane, cellulose powder, and 40 g of solid filler made of an inorganic filler were mixed in a super mixer, put into a mold, and hot press molded at 200 to 250 ° C. As a result, a good product with good release property and surface gloss was obtained.

Example 5 and Comparative Example 2

20 g of epoxy resin (Kukdo Chemical YD-014MX) was dissolved in 100 ml of xylene, 80 g of alumino siloxane was dissolved in 200 ml of xylene, and these were mixed and heated and reacted at 140 to 160 ° C. to obtain 100 g of a milky semi-solid product. 50 g of the product thus obtained was taken, dissolved in 200 ml of xylene again, a curing agent was added thereto, stirred well, and then applied to a metal specimen within 30 minutes.

Further, 20 g of the same epoxy resin was dissolved in 100 ml of xylene, 80 g of a conventional siloxane was dissolved in 200 ml of xylene, and these were mixed and heated and reacted at 140 to 160 ° C. to obtain 100 g of a milky semi-solid product. 50 g of the product thus obtained was taken, dissolved in 200 ml of xylene again, a curing agent was added thereto, stirred well, and then applied to a metal specimen within 30 minutes.

As a result of testing each sample by leaving the prepared sample at room temperature and atmospheric pressure for 4 weeks, the polymer containing the conventional siloxane compound leaked to the surface in the form of oil, but the aluminosiloxane compound was mixed by the method according to the present invention. No leakage of aluminosiloxane in the form of oil or the like on the surface of the polymer was observed at all. Therefore, although the migration phenomenon occurs in the polymer incorporating the conventional siloxane compound, it was found that in the polymer incorporating the aluminosiloxane compound by the method according to the present invention, the migration phenomenon does not occur at all.

In addition, as a result of continuing the test by leaving the polymer incorporating the aluminosiloxane compound for 3 years at room temperature and atmospheric pressure for 3 years, no migration phenomenon was observed, and thus, no migration phenomenon occurred.

In addition, it was confirmed that the adhesion to metal was excellent, and the touch, surface glossiness, and stain resistance were excellent.

Example 6

30 g of DOP (Dioctylphthalate), which is used as a polymer plasticizer, was sufficiently dissolved in 80 ml of THF, and 0.5 g of alumino siloxane was dissolved together. The solution prepared as above is placed in an oven and dried sufficiently at 50 ° C. to obtain the remaining alumino siloxane coated DOP without evaporation. The alumino siloxane coated DOP obtained as described above was used for the polymerization of PET using 2% by weight relative to the weight of PET. As a result, it was confirmed that the dispersibility of the plasticizer DOP significantly improved.

Example 7 and Comparative Example 3

In a 500 ml Erlenmeyer flask, add 16 g of Bee Wax, 1.0 g of Carnauba Wax, 6 g of ethanol, 6.2 g of castor oil, 6 g of lanolin, 1 g of aluminosiloxane, and 50 mg of para-hydroxybenzoate. The mixture was slowly heated and melted with stirring, and then, when completely dissolved, 0.1 g of an appropriate amount of the pigment was added thereto, and the mixture was stirred well to mix evenly. 200 mg of di-menthol was added thereto, stirred until completely dissolved, and then put into a suitable mold and cooled to prepare a lipstick.

Instead of using 1 g of aluminosiloxane, a lipstick was prepared using the same method as above except using 1 g of conventional siloxane.

As a result of testing each sample by leaving the prepared sample at room temperature and atmospheric pressure for 4 weeks, the polymer containing the conventional siloxane compound leaked to the surface in the form of oil, but the aluminosiloxane compound was mixed by the method according to the present invention. No leakage of aluminosiloxane in the form of oil or the like on the surface of the polymer was observed at all. Therefore, although the migration phenomenon occurs in the polymer incorporating the conventional siloxane compound, it was found that in the polymer incorporating the aluminosiloxane compound by the method according to the present invention, the migration phenomenon does not occur at all.

In addition, as a result of continuing the test by leaving the polymer incorporating the aluminosiloxane compound for 3 years at room temperature and atmospheric pressure for 3 years, no migration phenomenon was observed, and thus, no migration phenomenon occurred.

In addition, it was confirmed that glossiness is maintained even after a long time and the resistance to moisture is stronger than that of the conventional lipstick.

According to the present invention, when the aluminosiloxane compound is incorporated into a polymer and used, various positive effects can be obtained.

Since the migration phenomenon of the siloxane compound does not occur at all, stable physical properties can be secured, and since there is no limitation in processability, it can be used for various applications such as fibers, films, films, coating agents, and paints.

When used in textile products, it is possible to obtain antifouling properties, feel and drape, and when used in paint products, it is useful for antifouling properties and feel. In particular, when used in cosmetics can improve the biocompatibility, ensure the activity of the user can significantly improve the product satisfaction of consumers. In addition, it can be used as a coating agent having excellent releasability and water repellency and dispersibility.

Claims (5)

A polymer molded article characterized in that no migration occurs by including 0.01-40% by weight of the aluminosiloxane compound of Formula 1 or Formula 2 in the polymer. [Formula 1] [Formula 2] In the above formula Each R is the same or different and represents C ₁ to C ₆ alkyl or phenyl, n is an integer from 6 to 90, M represents alkali metals, such as lithium, sodium, potassium, rubidium, cesium, and francium. The method of claim 1, The polymer is in the group consisting of polyethylene terephthalate (PET), polypropylene (PP), epoxy, polyethylene, polyurethane, polystyrene, polycarbonate, polyvinyl alcohol, phenol resin, urea resin, melamine resin, acetal resin and nylon A polymer molded product characterized by being one or two or more polymers selected. The method of claim 1, Processed form of the polymer molded product is a polymer molded product, characterized in that the fiber, film, sheet or film. The polymer composition, characterized in that the migration phenomenon does not occur by including 0.01 to 40% by weight of the aluminosiloxane compound of Formula 3 or Formula 4 in the polymer. [Formula 3] [Formula 4] In the above formula Each R is the same or different and represents C ₁ to C ₆ alkyl or phenyl, n is an integer from 6 to 90, M represents alkali metals, such as lithium, sodium, potassium, rubidium, cesium, and francium. The method of claim 4, wherein Polymer composition, characterized in that the polymer composition is a coating agent, paint, or cosmetics.